BR112021009539B1 - METHOD FOR MANUFACTURING A COMPLEX SULFONATE-BASED GREASE - Google Patents

Abstract

SULFONATE-BASED GREASE COMPOSITION, AND, METHOD FOR MANUFACTURING SULFONATE-BASED GREASE COMPOSITION. A sulfonate-based grease composition and method of manufacture comprising adding one or more glycerol derivatives. The glycerol derivative acts to optimally disperse the thickener in the grease so that the conventional grease grinding step may not be necessary. The glycerol derivative reacts with water to form in situ complexing acids, which can replace at least some of the complexing acids normally used to react with calcium-containing bases. Greases according to preferred embodiments have a high dripping point, an improved thickening yield and a faster conversion time.

Description

CROSS REFERENCE TO RELATED ORDER

[01] This application claims the benefit of U.S. provisional patent application No. 62/769,704, filed on November 20, 2018.

BASICS OF THE INVENTION 1. Field of invention

[02] This invention relates to superbasified calico sulfonate greases and superbasified calcium magnesium sulfonate greases manufactured by adding a glycerol derivative to improve thickening yield, increase the dripping point, reduce conversion time , and/or obtain a final grease that does not require grinding.

2. Description of the related technique

[03] Superbase calcium sulfonate greases have been a proven grease category for many years. A known process for manufacturing such greases is a two-step process involving “promotion” and “conversion” steps. Typically the first step (“promotion”) is to react a stoichiometrically excess amount of calcium oxide (CaO) or calcium hydroxide (Ca(OH)2), as the base source, with an alkylbenzenesulfonic acid, carbon dioxide (CO2), and with other components to produce an oil-soluble superbasified calcium sulfonate with amorphous calcium carbonate dispersed therein. These superbasified oil-soluble calcium sulfonates are typically transparent and shiny and have Newtonian rheology. In some cases they may be somewhat cloudy, but such variations do not preclude their use in the manufacture of superbase calcium sulfonate greases. For the purposes of this description, the terms “super-based oil-soluble calcium sulfonate” and “super-based oil-soluble calcium sulfonate” and “super-based calcium sulfonate” refer to any super-based calcium sulfonate suitable for manufacturing oil sulfonate greases. calcium.

[04] Typically the second step (“conversion”) is to add a converting agent or converting agents to the product from the promotion step, together with a suitable base oil (such as mineral oil), if necessary, to prevent the initial grease from become very hard, to convert the amorphous calcium carbonate contained in the superbasified calcium sulfonate into a very finely divided dispersion of crystalline calcium carbonate (calcite). Prior art converting agents include water and conventional non-aqueous converting agents such as propylene glycol, isopropyl alcohol, formic acid or acetic acid. When acetic acid or other acids are used as a converting agent, typically water and another conventional non-aqueous converting agent (a third converting agent, such as an alcohol) are also used; alternatively only water (without the third converting agent) is added, but the conversion then typically takes place in a pressurized vessel. The most common conventional non-aqueous converting agents are monohydroxyalcohols or polyhydroxyalcohols. Glycols (dihydroxyalcohols) are one of the most frequently used of this family of conventional non-aqueous converting agents.

[05] Because an excess of calcium hydroxide or calcium oxide is used to achieve superbasification, a small amount of residual calcium oxide or calcium hydroxide may also be present as part of the soluble superbasified calcium sulfonate in oil and will be dispersed in the initial grease structure. The extremely finely divided calcium carbonate formed by the conversion, also known as a colloidal dispersion, interacts with the calcium sulfonate to form a grease-like consistency. Such superbase calcium sulfonate greases produced by the two-step process have become known as “simple calcium sulfonate greases” and are described, for example, in U.S. Patent Nos. 3,242,079; 3,372,115; 3,376,222. 3,377,283; and 3,492,231.

[06] It is also known in the prior art to combine these two steps, by carefully controlling the reaction, in a single step. In this one-step process, simple calcium sulfonate grease is manufactured by reacting with either calcium hydroxide or calcium oxide in the presence of carbon dioxide and a system of reagents that simultaneously act as both a promoting agent (creating superbasification of carbonate amorphous calcium by reacting carbon dioxide with an excess amount of calcium oxide or calcium hydroxide) or as a converting agent (converting amorphous calcium carbonate into very finely divided crystalline calcium carbonate). In this way, the grease-like consistency is formed in a single step in which the overbase, oil-soluble calcium sulfonate (the product of the first step in the two-step process) is never actually formed and isolated as a separate product. This one-step process is described, for example, in U.S. Patent Nos. 3,661,622; 3,671,012; 3,746,643; and 3,816,310.

[07] Conversion into superbasified calcium sulfonate greases is typically determined by IVTF (Fourier Transform Infrared Spectroscopy) analysis. An TFIV spectrum showing a peak at 862 cm-1 indicates the amorphous calcium carbonate contained in the superbasified calcium sulfonate will be converted to dispersed crystalline calcium carbonate. An intermediate peak at 874 cm-1 is commonly observed during the conversion process of calcium sulfonate-based greases, at least when the conversion process occurs under conditions open to atmospheric pressure. Depending on small variations in the grease being manufactured, this intermediate peak can be observed within the range of about 872 cm-1 to 877 cm-1. Complete conversion to the desirable dispersion of crystalline calcium carbonate (calcite) has typically been evidenced in the prior art by the elimination of the original amorphous calcium carbonate peak at 862 cm-1 and any intermediate peaks during the conversion process and confirmation of a single new peak at about 882 cm-1.

[08] In addition to simple calcium sulfonate greases, complex calcium sulfonate greases are also known in the art. These complex greases are typically produced by adding a strong calcium-containing base, such as calcium hydroxide or calcium oxide, to simple calcium sulfonate grease, produced by either the two-step process or the one-step process, and reacting with quantities to stoichiometrically equivalent complexing acids such as 12-hydroxystearic acid, boric acid, acetic acid (which can also be a converting agent when added before conversion), or phosphoric acid. The claimed advantages of calcium sulfonate complex grease over simple grease include reduced stickiness, improved pumpability, and improved high temperature utility. Calcium sulfonate complex greases are described, for example, in U.S. Patent Nos. 4,560,489; 5,126,062; 5,308,514; and 5,338,467. In the manufacture of a calcium sulfonate complex grease, the complexing acids may be added directly or may be formed in situ by the addition of any compound that would be expected to react with water to produce a short-chain or long-chain carboxylic acid that acts as a complexing acid. For example, as described in U.S. Patent No. 9,273,265, which is incorporated herein by reference, acetic anhydride may be added which will react with water to form acetic acid to be used as a complexing acid. Likewise, methyl 12-hydroxystearate can be added which will react with water to form 12-hydroxystearic acid to be used as a complexing acid.

[09] Additionally, it is desirable to have a complex calcium sulfonate grease composition and a manufacturing method that results in both improved thickening yield (by requiring a lower percentage of overbase calcium sulfonate in the final grease) and drip point. improved. The term “thickener yield,” as used herein, refers to the concentration of superbase oil-soluble calcium sulfonate required to provide a grease with a specific desired consistency as measured by the ASTM D217 or D1403 standard penetration tests commonly used in the manufacture of lubricating greases. The term “drip point,” as used herein, refers to the value obtained by using the ASTM D2265 standard drip point test commonly used in the manufacture of lubricating greases. Many of the prior art methodologies and compositions require an amount of superbasified calcium sulfonate of at least 36% (by weight of the final grease product) to obtain a grease suitable in NLGI category #2 with a demonstrated drip point of at least 302°C (575°F). Superbase oil-soluble calcium sulfonate is one of the most expensive ingredients in the manufacture of calcium sulfonate grease. Therefore, it is desirable to reduce the amount of this ingredient while maintaining a desired level of firmness in the final grease (thus improving thickening performance).

[10] There are several known compositions and several known methods that result in improved thickening yield while maintaining a sufficiently high drip point. For example, for the purpose of achieving a substantial reduction in the amount of superbasified calcium sulfonate used, many prior art references utilize a pressurized reactor. It is desirable to have an overbase calcium sulfonate grease in which the percentage of overbase oil-soluble calcium sulfonate is less than 36% and the drip point is consistently 302°C (575°F) or higher when the consistency is within of an NLGI grade No. 2 (or worked penetration measured at 60 strokes of grease is between 265 and 295), without requiring a pressurized reactor. Higher drip points are considered desirable because the drip point is the first and most easily determined guide to the high temperature usefulness limitations of a lubricating grease.

[11] Superbase calcium sulfonate greases that require less than 36% superbase calcium sulfonate are also obtained using the compositions and methods described in U.S. patents Nos. 9,273,265 and 9,458,406. The '265 and '406 patents teach the use of added crystalline calcium carbonate and/or added calcium hydroxyapatite (either with or without added calcium hydroxide or added calcium oxide) as the calcium-containing bases for reacting with complexing acids in manufacturing of superbasified calcium sulfonate complex greases. Prior to these patents, the known prior art has always taught the use of calcium oxide or calcium hydroxide as the basic calcium sources for the production of calcium sulfonate greases or as a component required to react with complexing acids to form complex greases. of calcium sulfonate. The known prior art has also taught that the addition of calcium hydroxide or calcium oxide needs to be in a sufficient amount (when added to the amount of calcium hydroxide or calcium oxide present in the superbasified oil-soluble calcium sulfonate) to provide a total calcium hydroxide or calcium oxide content sufficient to completely react with complexing acids. The known prior art has also generally taught that the presence of calcium carbonate (as a separate ingredient or as an "impurity" in calcium hydroxide or calcium oxide, other than the presence of amorphous calcium carbonate dispersed in calcium sulfonate after carbonation), should be avoided for at least two reasons. The first being that calcium carbonate is generally considered to be a weak base, unsuitable for reacting with complexing acids to form optimal grease structures. The second being that the presence of unreacted solid calcium compounds (including calcium carbonate, calcium hydroxide or calcium oxide) interferes with the conversion process, resulting in inferior greases if unreacted solids are not removed prior to conversion or before until the conversion is complete. However, as described in the '265 and '406 patents, Applicant has found that the addition of calcium carbonate as a separate ingredient (in addition to the amount of calcium carbonate contained in superbasified calcium sulfonate), calcium hydroxyapatite, or a combination thereof, either with or without added calcium hydroxide or added calcium oxide, as ingredients to react with complexing acids, produces superior grease.

[12] In addition to the '265 and '406 patents, there are some prior art references that describe the addition of crystalline calcium carbonate as a separate ingredient (in addition to the amount of calcium carbonate contained in superbasified calcium sulfonate), but those greases have poor thickening performance (as the prior art teaches) or require nanometer-sized particles of calcium carbonate. For example, U.S. Patent No. 5,126,062 describes the addition of 5% to 15% calcium carbonate as a separate ingredient in forming a complex grease, but also requires the addition of calcium hydroxide to react with complexing acids. The added calcium carbonate in the '062 patent is not the only calcium-containing base added to react with complexing acids as it is in the '265 patent. Additionally, the resulting NLGI No. 2 grease in the '062 patent contains from 36% to 47.4% superbase calcium sulfonate, which is a substantial amount of this expensive ingredient. In another example, Chinese publication No. CN101993767, describes the addition of nanosized calcium carbonate particles (sized between 5 nm and 300 nm) being added to superbasified calcium sulfonate, although the reference does not indicate that the nanosized carbonate particles of calcium are added as a reagent, or the single calcium-containing base added separately, to react with complexing acids. The use of nanosized particles would increase the thickening of the grease to keep it firm, very similar to the fine dispersion of crystalline calcium carbonate formed by the conversion of amorphous calcium carbonate contained in superbasified calcium sulfonate (which can be about 20 A to 5,000 A or from about 2 nm to 500 nm according to the '467 patent), but would also substantially increase costs over larger particle sizes of added calcium carbonate. The Chinese patent application greatly emphasizes the absolute necessity of the added calcium carbonate to have a true nanometer particle size. As shown in the example greases according to the invention described in the '265 patent, superior greases can be formed by adding micrometer calcium carbonate (preferably 1 micrometer to 20 micrometers) without requiring the use of the very expensive nanometer particles when using calcium carbonate added as one of or the only calcium-containing base added to react with complexing acids.

[13] There are also prior art references to the use of tricalcium phosphate as an additive in lubricating greases. For example, all U.S. Patent Nos. 4,787,992; 4,830,767; 4,902,435; 4,904,399; and 4,929,371 teach the use of tricalcium phosphate as an additive to lubricating greases. However, it is believed that prior to the '406 patent, no prior art references taught the use of calcium hydroxyapatite having the formula Ca5(PO4)3OH or a mathematically equivalent formula with a melting point of about 1,100°C ( or excluding mixtures of tricalcium phosphate and calcium hydroxide), as a calcium-containing base for reaction with acids to manufacture lubricating greases, including calcium sulfonate-based greases. There are several prior art references attributed to Showa Shell Sekiyu in Japan, including publication of U.S. patent application No. 2009/0305920, which describes greases containing tricalcium phosphate, Ca3(PO4)2, and mention of a “hydroxyapatite” having the formula [Ca3(PO4)2]3^Ca(OH)2 as a source of tricalcium phosphate. This mention of “hydroxyapatite” is described as a mixture of tricalcium phosphate and calcium hydroxide, which is not the same as the calcium hydroxyapatite described and claimed in the '406 patent and herein having the formula Ca5(PO4)3OH or a formula mathematically equivalent with a melting point of about 1,100°C. Despite the imprecise nomenclature, calcium hydroxyapatite, tricalcium phosphate, and calcium hydroxide are each different chemical compounds, with different chemical formulas, different chemical structures, and different melting points. When mixed together, the two different crystalline compounds tricalcium phosphate (Ca3(PO4)2) and calcium hydroxide (Ca(OH)2) will not react with each other, or otherwise produce the different crystalline compound calcium hydroxyapatite. (Ca5(PO4)3OH). The melting point of tricalcium phosphate (having the formula Ca3(PO4)2) is 1670°C. Calcium hydroxide does not have a melting point, but instead loses a water molecule to form calcium oxide at 580°C. The calcium oxide thus formed has a melting point of 2,580°C. Calcium hydroxyapatite (having the formula Ca5(PO4)3OH or a mathematically equivalent formula) has a melting point of about 1,100°C. Therefore, regardless of how imprecise the nomenclature may be, calcium hydroxyapatite is not the same chemical compound as tricalcium phosphate, and it is not a simple mixture of tricalcium phosphate and calcium hydroxide.

[14] In the manufacture of superbase calico sulfonate greases, much of the prior art, which uses the two-step method, teaches the addition of all converting agents (water and conventional non-aqueous converting agents) at the same time and usually before the heating. However, U.S. Patent Nos. 9,976,101 and 9,976,102, which are incorporated herein by reference, describe a method where there is a delay between the addition of at least a portion of a conventional non-aqueous converting agent that results in thickening yield. improved and improved drip point. Prior to the '101 and '102 patents, some prior art references describe a time interval (although always unsatisfactorily defined or not defined at all) between the addition of water and the addition of at least part of the agent(s). ) conventional non-aqueous converter(s). For example, U.S. Patent No. 4,560,489 describes a process (Examples 1 to 3) wherein base oil and superbase calcium carbonate are heated to about 65.6°C (150oF), then water is added, the mixture is then heated to about 87.8°C (190oF) before adding acetic acid and Methyl-Cellosolve (a highly toxic ethylene glycol monomethyl ether). The resulting grease contains more than 38% superbase calcium sulfonate and the '489 patent emphasizes that the ideal amount of superbase calcium sulfonate for the processes described therein is about 41% to 45%, because, according to '489 patent, use of less than 38% results in a soft grease. The resulting grease from example 1 in the '489 patent has a drip point of only about 299°C (570oF). The '489 patent does not state the length of delay between the addition of water and the addition of conventional non-aqueous converting agents, but it does indicate that the addition was immediately after a heating period of 65.6°C (150°F) for exactly 87.8°C (190°F). The drip point and thickening yield in the '489 patent are not desirable.

[15] Additionally, U.S. Patent Nos. 5,338,467 and 5,308,514 describe the use of a fatty acid, such as 12-hydroxystearic acid, as a converting agent used together with acetic acid and methanol, where there is no delay for addition of the fatty acid but some interval between the addition of water and the addition of acetic acid and methanol. Both example B in the '514 patent and example 1 in the '467 patent describe a process where water and the fatty acid-based converting agent are added to the other ingredients (including the superbasified calcium sulfonate and the base oil), then heated. to about 60.0°C to 62.8°C (140°F to 145°F) before adding acetic acid followed by methanol. The mixture is then heated to about 65.6°C to 71.1°C (150°F to 160°F) until complete conversion. The amount of superbasified calcium sulfonate in the final grease products in both examples is 32.2, which is greater than desirable. These patents do not state the length of delay between the addition of water and fatty acid and the addition of acetic acid and methanol, but indicate that the addition was immediate after an unspecified heating period. Similar processes are described in example A of the '467 patent and example C of the '514 patent except that all of the fatty acid was added after conversion, so that only the conventional non-aqueous converting agents used were added acetic acid and methanol. after the mixture with water is heated to 60.0°C to 62.8°C (140°F to 145°F). The amount of superbasified calcium sulfonate in these examples is even higher than in the previous examples at 40%. In addition to not achieving ideal thickening yield results, all of these processes use methanol as a converting agent, which has environmental disadvantages. The use of volatile alcohols as converting agents can result in the release of these ingredients into the atmosphere as a later part of the grease manufacturing process, which is prohibited in many parts of the world. If not released to the atmosphere, alcohols must be recovered by scrubbing with water or water traps, which results in hazardous material removal costs. As such, there is a need for a process that achieves better thickening yields, preferably without requiring the use of alcohols as converting agents.

[16] Better thickening yields are achieved in example 10 of the '514 patent, but the use of excess lime is taught as a requirement to achieve those results. In that example, water and excess lime are added together with other ingredients, the mixture is heated to 82.2°C to 87.8°C (180°F to 190°F) while slowly adding acetic acid over the period of heating. The resulting grease contained 23% superbasified calcium sulfonate. Although this thickening yield is better than the others, there is still room for great improvement without requiring the use of excess lime, which the '514 patent teaches as a requirement.

[17] The other examples in the '514 and '467 patents where thickening yields of 23% or less either involve the use of a pressurized vessel during conversion are like most other prior art where there is no "delay" between the addition of water and conventional non-aqueous converting agents or both. These examples involve adding water and a fatty acid-based converting agent, mixing for 10 minutes without heating, and then adding acetic acid, in either a pressurized or non-pressurized vessel. None of these patents recognize any benefit or advantage of the 10 minute delay for adding acetic acid, or the other heating delays in the examples discussed above; rather, these patents emphasize the use of a fatty acid as a converting agent and the benefits of the addition of the fatty acid prior to conversion, or both as the reason for any improvements in yield observed. Additionally, as discussed below, this 10 minute mixing interval without any heating is not a “converting agent delay” as the term is used herein, but is considered to be the same as adding the ingredients at the same time, recognizing that adding each ingredient takes at least some time and cannot occur simultaneously.

[18] It is also known to add alkali metal hydroxides to simple calcium soap greases, such as greases thickened with anhydrous calcium soap. But prior to the disclosure in U.S. Patent No. 9,976,102, which is incorporated herein by reference, it was not known to add an alkali metal hydroxide to a calcium sulfonate grease to provide improved thickening yield and high drip point, because that addition would be considered unnecessary by a person commonly skilled in the art. The reaction for adding an alkali metal hydroxide, such as sodium hydroxide, to simple calcium soap greases is that the commonly used calcium hydroxide has low solubility in water and is a weaker base than the highly soluble sodium hydroxide. in water. Because of this, the small amount of sodium hydroxide dissolved in the added water is said to react quickly with the soap-forming fatty acid (usually 12-hydroxystearic acid or a mixture of 12-hydroxystearic acid and a non-hydroxylated fatty acid such as oleic acid). ) to form sodium soap. This quick reaction is considered to “get the ball rolling”. However, the direct reaction of calcium-containing greases such as calcium hydroxide with fatty acids has never been a problem when manufacturing complex calcium sulfonate greases. The reaction occurs very easily, probably due to the high detergency/dispersity of the large amount of calcium sulfonate present. As such, it is not known in the prior art to use an alkali metal hydroxide in a calcium sulfonate grease as a way to obtain complexing acids to react with calcium hydroxide.

[19] Several other improvements in superbase calcium sulfonate greases have been described in recent years. These include the addition of a superbase calcium sulfonate to a superbase calcium sulfonate grease, including a delayed addition of magnesium sulfonate relative to the addition of water or one or more other reactive ingredients and/or a split addition of magnesium sulfonate. , as described in U.S. Patent No. 10,087,387; the use of a facilitating acid delay method as described in U.S. Patent No. 10,087,388; and the exclusion of conventional non-aqueous converting agents as described in U.S. Patent No. 10,087,391. Each of these patents is incorporated herein by reference.

[20] All prior art sulfonate-based greases require grinding, using a mechanical mill, as one of the final steps in manufacturing the grease. Typically, before a grease is milled, it is already thickened with a grease structure and its thickening system is dispersed in a relatively less ordered configuration throughout the continuous phase (base oil and components dissolved in it). Mechanical grinding provides increased dispersion and ordered structure to the thickener, resulting in a firmer grease consistency. Most sulfonate-based greases will achieve only a moderate additional thickening effect with grinding, but some calcium and magnesium sulfonate greases described in the '387 patent (such as Example 27 in the '387 patent) are extremely fluid before grinding and they only acquire a structure similar to grease after grinding (or shearing).

[21] It is known in the prior art to add various glycerides (glycerol derivatives), such as various vegetable oils as sources of fatty acids, in the manufacture of lithium-based greases. Lithium-based greases are a type of grease that uses a lithium soap-based thickening system, which is different from the calcite-based thickening system dispersed in sulfonate-based greases. In lithium greases, the reaction of lithium hydroxide and water hydrolyzes the glyceride structure of vegetable oil, thereby forming corresponding long-chain fatty (carboxylic) acids and glycerol. The fatty acids then react with lithium hydroxide to form the lithium soap-based thickener, leaving glycerol within the final grease. However, modern high dripping point lithium complex greases preferably use 12-hydroxystearic acid in place of vegetable oils (such as hydrogenated castor oil). When manufacturing such lithium complex greases with 12-hydroxystearic acid, glycerol is never formed and is therefore not included in the final grease. This is the main difference between the manufacture of lithium complex greases that use 12-hydroxystearic acid and lithium complex greases that use glycerides (glycerol derivatives). Some prior art references to lithium greases, such as U.S. patents Nos. 3,681,242, 3,758,407, and U.S. Nos. 3,791,973, also teach that the direct or indirect inclusion of a glycol is not desired in lithium greases. lithium base because such materials can make the final grease more prone to oxidation and reduce its water resistance. Glycols are commonly used as a conventional non-aqueous converting agent in the manufacture of a sulfonate-based grease. It is emphasized that glycols (dihydroxyalcohols) are not the same as glycerol (a trihydroxyalcohol), and glycols are not derived from glycerol.

[22] Similarly, calcium soap-thickened greases (which are another type of grease with a different thickening system compared to sulfonate-based greases) have also been manufactured using various glycerides (glycerol derivatives), such as various vegetable oils. as sources of fatty acids. Most calcium soap-thickened greases today use 12-hydroxystearic acid in place of such vegetable oils because this allows a much narrower range of long-chain fatty (carboxylic) acids to be used. Additionally, some research has shown adverse results from the use of glycerols and glycols in calcium soap greases. For example, Auld, S. J. M., et.al. Proc. 3rd World Petroleum Congress, Vol 7, p 355, (1951) demonstrated that the intentional use of glycerol or glycols resulted in unstable grease structures unless water was also present in the final grease. In contrast, water is removed in the manufacture of sulfonate-based greases. Additionally, Bondi, A., et.al. Proc. 3rd World Petroleum Congress, Vol 7, p 355, (1951) and Smith, G. J. Journal Am. Oil Chem. Soc., Vol. 24, p 353, (1947) demonstrated that all hydroxylated compounds (which include glycerol and glycols) increase the oil solubility of soap-thickened systems (decreases the thickening power) and lower the phase transformation temperature (temperature at which the thickener melts), neither of which are beneficial to a lubricating grease.

[23] Although it is known to add a glycerol derivative in the manufacture of a lithium grease or a calcium soap grease, it was not previously known to add a glycerol derivative in the manufacture of a sulfonate-based grease. The adverse behavior due to glycols in lithium greases and due to glycerols and glycols in calcium soap greases would result in a person of ordinary skill in the art not considering the glycerol-based ingredients used in lithium greases and calcium soap greases. calcium to improve performance in other greases, such as sulfonate-based greases (particularly because sulfonate-based greases commonly use glycols as conventional non-aqueous converting agents). However, Applicant has surprisingly found that glycerol derivatives provide improved thickening yield, higher drip point, and/or can eliminate the need for grinding in sulfonate-based greases.

[24] Furthermore, it was not previously known to combine the addition of a glycerol derivative with one or more of the following: (1) the addition of a superbasified calcium sulfonate; (2) a facilitating acid delay period; (3) a delayed addition of magnesium sulfonate relative to the addition of water or one or more other reactive ingredients; (4) a divided addition of magnesium sulfonate; (5) the addition of calcium hydroxyapatite and/or added crystalline calcium carbonate or a combination thereof (with or without added calcium hydroxide or added calcium oxide) as calcium-containing bases (also called basic calcium compounds) for reaction with complexing acids; (6) adding an alkali metal hydroxide; (7) the delayed addition of conventional non-aqueous converting agents; or (8) any combination of these methods and ingredients. It was also not previously known to add a glycerol derivative to a sulfonate-based grease so that grinding is not required.

SUMMARY OF THE INVENTION

[25] This invention relates to sulfonate-based greases and methods for making such greases using an added glycerol derivative to produce a grease (1) having improved thickening yield, (2) having a higher drip point, and /or (3) that does not require grinding. As used herein, a calcium sulfonate grease (or superbase calcium sulfonate grease) containing superbase magnesium sulfonate is sometimes called a calcium magnesium sulfonate grease or a superbase calcium magnesium sulfonate grease. As used herein a “sulfonate-based grease” or a “super-based sulfonate-based grease” refers to a calcium sulfonate grease (or super-based calcium sulfonate) and/or a magnesium sulfonate grease ( or superbasified magnesium sulfonate).

[26] According to a preferred embodiment, a sulfonate-based grease is manufactured by adding a glycerol derivative before conversion, during conversion, after conversion, or a combination thereof. According to another preferred embodiment, a sulfonate-based grease comprises added glycerol derivative and less than 37% super-based calcium sulfonate by weight of the final grease, more preferably less than 30% super-based calcium sulfonate, and with maximum preferably less than 26% superbasified calcium sulfonate.

[27] According to another preferred embodiment, the glycerol derivative comprises one or more of hydrogenated castor oil, glyceryl monostearate, glyceryl monostearate, and glycerol monooleate. According to another preferred embodiment, the glycerol derivative comprises one or more of a monoacylglyceride, a diacylglyceride, or a triacylglyceride.

[28] When a glycerol derivative is added, it has surprisingly been found that mechanical or physical grinding of the grease may not be required to obtain a satisfactory grease structure. This way, when a glycerol derivative is added, the typical step of mechanically grinding the grease can be eliminated while still having a smooth, homogeneous and sufficiently hardened grease structure. According to another preferred embodiment, a sulfonate-based grease is manufactured with added glycerol derivative and the grease is unmilled. According to another preferred embodiment, the unmilled grease has a drip point of 304°C (580°F) or higher, more preferably 332°C (630°F) or higher, and most preferably of 343°C (650°F) or higher.

[29] According to another preferred embodiment, grinding is not required when a glycerol derivative is added and (1) a facilitating acid delay method is used or (2) a converting agent delay method is used or ( 3) both. According to another preferred embodiment, grinding is not required when a glycerol derivative is added and the facilitating acid delay method is not used.

[30] According to another preferred embodiment, the sulfonate-based grease with an added glycerol derivative has a first penetration value in an unmilled state and a second penetration value in a milled state and wherein the first penetration value penetration and the second penetration value are within 15 points of each other. According to another preferred embodiment, the sulfonate-based grease with an added glycerol derivative has a first penetration value in an unmilled state and a second penetration value in a milled state and wherein the first penetration value and the second penetration value are in the same range as NLGI grade. According to another preferred embodiment, the sulfonate-based grease with an added glycerol derivative has a first penetration value in an unmilled state that is lower than a second penetration value in a milled state.

[31] According to another preferred embodiment, the sulfonate-based grease with an added glycerol derivative has an TFIV spectrum having two peaks, one between 872 cm-1 and 877 cm-1 and the other at about 882 cm -1. According to another preferred embodiment, the sulfonate-based grease with an added glycerol derivative has a TFIV spectrum having one or more of the following: (1) a doublet where the peak is between 872 cm-1 and 877 cm-1 is the dominant peak; (2) a doublet where the peak at about 882 cm-1 is the dominant peak; (3) an uneliminated shoulder at about 862 cm-1, (4) a dominant peak at about 882 cm-1, and a shoulder between 872 cm-1 and 877 cm-1, where the height of the shoulder is about 33% to 95% of the peak height at 882 cm-1; or (5) a peak between 872 cm-1 and 877 cm-1 with a shoulder at about 882 cm-1.

[32] According to another preferred embodiment, the added glycerol derivative reacts with water to preferably form a long-chain fatty acid, but short-chain fatty acids can also be formed, which act as a complexing acid. A glycerol derivative may be added to replace some or all of the complexing acids normally used in the manufacture of a sulfonate grease.

[33] According to another preferred embodiment, the dripping point of a sulfonate-based grease is improved by the addition of a glycerol derivative compared to the dripping point of the same grease manufactured without the addition of a glycerol derivative. According to another preferred embodiment, improved thickening yield and sufficiently high dripping points are achieved when a glycerol derivative is added to different conventional prior art sulfonate-based grease compositions and methods, even when overbasified calcium sulfonate is considered to be of “poor” quality as described and defined in the '406 patent.

[34] According to another embodiment, all water added in the manufacture of the sulfonate-based grease with added glycerol derivative is removed by heating and is not present in the final grease. According to another preferred embodiment an upper conversion heating temperature is 127°C (260°F). According to another preferred embodiment an upper conversion heating temperature is between 87.8°C (190°F) and 93.3°C (200°F). According to another preferred embodiment, a conventional non-aqueous converting agent is added immediately after reaching the temperature range of 87.8°C (190°F) to 93.3°C (200°F). According to another preferred embodiment, the total time for a conversion step in the manufacture of a sulfonate-based grease with added glycerol derivative is less than 75 minutes, more preferably about 60 minutes or less.

[35] According to still other preferred embodiments, the addition of a glycerol derivative is combined with one or more of the following: (1) the addition of crystalline calcium carbonate as the only added calcium-containing base (also called a compound calcium basic) for reaction with complexing acids; (2) the addition of calcium hydroxyapatite (with or without added calcium carbonate, added calcium hydroxide, and/or added calcium oxide) as calcium-containing bases for reaction with complexing acids; (3) a converting agent delay period; (4) the addition of an alkali metal hydroxide; (5) the addition of a superbasified magnesium sulfonate; (6) a delayed addition of magnesium sulfonate relative to the addition of water or one or more other reactive ingredients; (7) a divided addition of magnesium sulfonate; (8) a facilitating acid delay period; and/or (9) the exclusion of any conventional non-aqueous converting agents (which cannot be combined with (3)). These additional methods and ingredients are described in U.S. Patent Nos. 9,273,265, 9,458,406, 9,976,101, 9,976,102, 10,087,387, 10,087,388, and 10,087,391, which are incorporated herein by reference. For ease of reference, a method/delay period with respect to the addition of a conventional non-aqueous converting agent as described in U.S. Patent Nos. 9,976,101 and 9,976,102 will be referred to as a converting agent delay period or a method of converter agent delay (or similar phrasing); a delay with respect to the addition of superbasified magnesium sulfonate as described in U.S. Patent No. 10,087,387 will be called a magnesium sulfonate delay period or a magnesium sulfonate delay method (or similar phrasing); and a delay with respect to a facilitating acid as described in U.S. Patent No. 10,087,388 will be called a facilitating acid delay period or a facilitating acid delay (or phrasing) method.

[36] According to another preferred embodiment, when a glycerol derivative is combined with calcium carbonate added as the only calcium-containing base to react with complexing acids, the sulfonate-based grease comprises less than 37% superbasified calcium sulfonate , more preferably less than 30% super-based calcium sulfonate, and most preferably less than 25% super-based calcium sulfonate, by weight of the final grease. According to another preferred embodiment, when a glycerol derivative is combined with calcium carbonate added as the sole calcium-containing base to react with complexing acids, the sulfonate-based grease has a drip point greater than 282°C (540°C). F), more preferably greater than 304°C (580°F) and most preferably greater than 343°C (650°F). According to another preferred embodiment, when a glycerol derivative is combined with calcium carbonate added as the sole calcium-containing base to react with complexing acids, the unmilled sulfonate-based grease has a drip point of 282°C (540°C). °F) or higher.

[37] According to another preferred embodiment, when a glycerol derivative is combined with calcium hydroxyapatite as one of the calcium-containing bases to react with complexing acids, the sulfonate-based grease comprises less than 30% superbasified calcium sulfonate and more preferably less than 25% superbasified calcium sulfonate by weight of the final grease. According to another preferred embodiment, when a glycerol derivative is combined with calcium hydroxyapatite as one of the calcium-containing bases to react with complexing acids, the sulfonate-based grease has a drip point greater than 343°C (650°F). ).

BRIEF DESCRIPTION OF FIGURES

[38] The composition and method of the invention are further described and explained in relation to the following drawings in which: FIGURE 1 is a graph showing the results of an oscillatory rheometry amplitude sweep at 25°C of the unmilled and milled greases of the Example 10; FIGURE 2 is a graph showing the results of an oscillatory rheometry amplitude sweep at 25°C of the unmilled and milled greases of Example 12; FIGURE 3 is a graph showing the results of an oscillatory rheometry amplitude sweep at 25°C of the unmilled and milled/agitated greases of Example 15; FIGURE 4 is a graph showing the results of an oscillatory rheometry amplitude sweep at 25°C of the unmilled and milled/agitated greases of Example 16; FIGURE 5 is a graph showing the results of an oscillatory rheometry amplitude sweep at 25°C of the unmilled greases of Examples 17 and 18; FIGURE 6 is a graph showing the results of an oscillatory rheometry amplitude sweep at 25°C of the milled greases of Examples 17 and 18; FIGURE 7 is a graph showing the results of an oscillatory rheometry amplitude sweep at 25°C of the unmilled and milled/stirred greases of Example 22; and FIGURE 8 is a graph showing the results of an oscillatory rheometry amplitude sweep at 25°C of the unmilled and milled/stirred greases of Example 23.

DESCRIPTION OF PREFERRED MODALITIES Sulfonate-based grease compositions

[39] According to a preferred embodiment of the invention, a simple or complex sulfonate-based grease composition comprises superbasified calcium sulfonate, and one or more glycerol derivatives. Most preferably, a sulfonate-based grease also comprises one or more converting agents (preferably water and optionally one or more separately added conventional non-aqueous converting agents, which may not be necessary if superbasified magnesium sulfonate is one of the ingredients), one or more calcium-containing bases, and one or more complexing acids (for a complex grease). Most preferably, a sulfonate-based grease composition also optionally includes superbasified magnesium sulfonate, a facilitating acid, and/or base oil.

[40] According to a preferred embodiment, the glycerol derivative helps in creating a smooth grease with well-dispersed thickener so that the usual step of grinding the grease is not required. According to another preferred embodiment, the glycerol derivative can act as a source of a complexing acid (by the formation of a complexing acid after hydrolysis), replacing some or all of the complexing acid normally used in the manufacture of a complex grease. The glycerol derivative will react with water to form a complexing acid in situ. The glycerol derivative can be added before conversion, during conversion, after conversion, or a combination thereof. Most preferably, the glycerol derivative is added prior to conversion or a portion is added prior to conversion and another portion is added during conversion.

[41] According to various preferred embodiments, a calcium sulfonate grease composition or a calcium magnesium sulfonate grease composition, with a conventional non-aqueous converting agent and without a conventional non-aqueous converting agent, comprises the following ingredients percent by weight of the final grease product (although some ingredients, such as water, acids, and calcium-containing bases, may not be in the final grease product or may not be in the concentrations indicated for addition). TABLE 1A - Preferred compositions when a Conventional non-aqueous converting agent is used TABLE 1B - Preferred compositions when conventional non-aqueous converting agent is not used

[44] Other preferred amounts are set forth in the other tables and Examples herein and in the other U.S. patent documents incorporated herein by reference. Some or all of any specific ingredient, including converting agents, added calcium-containing bases, and glycerol derivatives may not be in the final finished product due to evaporation, volatilization, or reaction with other ingredients during manufacturing. These quantities are when a grease is manufactured in an open vessel. Even lower amounts of superbase calcium sulfonate can be used when a sulfonate-based grease is manufactured in a pressurized vessel.

[45] Preferred glycerol derivatives are monoacylglycerides, diacylglycerides, or triacylglycerides. Most preferably, the glycerol derivative is one or more of hydrogenated castor oil, glyceryl monostearate, glyceryl monostearate, and glycerol monooleate. Hydrogenated castor oil is essentially triacylglyceride where all of the fatty acid ester groups in the glycerol backbone are 12-hydroxystearic groups. According to a preferred embodiment, a glycerol derivative and a conventional non-aqueous converting agent are both added prior to conversion. According to another preferred embodiment, magnesium sulfonate and a glycerol derivative are added and conventional non-aqueous converting agent is not added before conversion. According to another preferred embodiment, two or more different glycerol derivatives, either with or without any conventional non-aqueous converting agent, are added before conversion.

[46] The optionally added glycerol derivative may replace some or all of the complexing acids normally used to react with the one or more calcium-containing bases (separately added or which may be included in the superbasified calcium sulfonate), to reduce production costs. ingredients while still maintaining good thickening performance and high dripping point. The glycerol derivative will react with water to form a complexing acid in situ. Water may be added before, after, or substantially simultaneously with the glycerol derivative.

[47] According to another preferred embodiment, a calcium magnesium sulfonate grease comprises superbasified calcium sulfonate and superbasified magnesium sulfonate as ingredients in a ratio range of 100:0.1 to 60:40, more preferably in a ratio range of 99:1 to 70/30, and with utmost preference in a ratio range of 90:10 to 80:20. According to another preferred embodiment, a sulfonate-based grease composition prior to conversion comprises the following ingredients: superbasified calcium sulfonate, superbasified magnesium sulfonate, water, optionally one or more glycerol derivatives (which may be added during conversion , before conversion, or both), and optional base oil, and wherein water is the only conventional converting agent in the composition before conversion. In other words, water, superbasified magnesium sulfonate, and optionally any dual function converting-acid complexing agents are the only converting agent ingredients added to the composition. According to another preferred embodiment, a sulfonate-based grease composition prior to conversion comprises superbasified calcium sulfonate and superbasified magnesium sulfonate as ingredients in a ratio range of 100:0.1 to 60:40, more preferably in a ratio range of 99:1 to 70/30, and with utmost preference in a ratio range of 90:10 to 80:20.

[48] The highly superbasified oil-soluble calcium sulfonate (also referred to herein, for brevity, simply as “calcium sulfonate” or “superbasified calcium sulfonate”) used in accordance with these embodiments of the invention to manufacture a highly superbasified oil-soluble calcium sulfonate calcium can be anything typical of that documented in the prior art, as in U.S. Patent Nos. 4,560,489; 5,126,062; 5,308,514; and 5,338,467. Highly superbasic oil-soluble calcium sulfonate can be produced in situ according to such known methods or can be purchased as a commercially available product. Such highly superbasified oil-soluble calcium sulfonates will have a Total Base Number (NBT) value of not less than 200, preferably not less than 300, and most preferably about 400 or higher. Commercially available superbasified calcium sulfonates of this type include, but are not limited to, the following: Hybase C401 as supplied by Chemtura USA Corporation; Syncal OB 400 and Syncal OB405-WO as supplied by Kimes Technologies International Corporation; Lubrizol 75GR, Lubrizol 75NS, Lubrizol 75P, and Lubrizol 75WO as supplied by Lubrizol Corporation. Superbase calcium sulfonate contains about 28% to 40% dispersed amorphous calcium carbonate by weight of superbase calcium sulfonate, which is converted to crystalline calcium carbonate during the manufacturing process of calcium sulfonate grease. Superbasified calcium sulfonate also contains about 0% to 8% residual calcium oxide or residual calcium hydroxide by weight of the superbasified calcium sulfonate. Most superbasified calcium sulfonates will also contain about 40% base oil as a diluent, to prevent the superbasified calcium sulfonate from becoming so thick that it is difficult to handle and process. The amount of base oil in superbase calcium sulfonate may make it unnecessary to add additional base oil (as a separate ingredient) prior to conversion to obtain an acceptable grease.

[49] The superbasified calcium sulfonate used may be of a “good” quality or a “poor” quality as in the '406 patent and defined herein. Certain overbase oil-soluble calcium sulfonates marketed and sold for the manufacture of calcium sulfonate-based greases may provide products with unacceptably low drip points when prior art calcium sulfonate technologies are used. Such overbased oil-soluble calcium sulfonates are referred to as “poor quality” overbased oil-soluble calcium sulfonates throughout this application. When all ingredients are the same except the commercially available batch of superbasified calcium sulfonate used, the superbasified oil-soluble calcium sulfonates that produce greases using the calcium carbonate technology of the '265 patent have higher dripping points (above 302°C (575°F)) are considered to be “good” quality calcium sulfonates for the purposes of this invention and those that produce greases having lower drip points are considered to be “poor” quality for the purposes of this invention. invention. Several examples of this are provided in the '406 patent, which is incorporated herein by reference. Although comparative chemical analyzes of good-quality and poor-quality superbasified oil-soluble calcium sulfonates have been carried out, it is believed that the precise reason for this low dripping point problem has not been proven. Although many commercially available superbasified calcium sulfonates are considered to be of good quality, it is desirable that both improved thickening yield and higher drip points be achieved regardless of whether the calcium sulfonate used is of a good quality or a poor quality. It has been found that both improved thickening yield and higher dripping point can be achieved with calcium sulfonate of either good quality or poor quality when glycerol derivative is added, particularly in combination with the delayed converting agent method and/or the delayed facilitator acid delay method.

[50] Any petroleum-based naphthenic or paraffinic mineral oils commonly used and well known in the art of manufacturing greases can be used as the base oil according to the invention. Base oil is added as needed because most commercial superbasified calcium sulfonates will already contain about 40% base oil as a diluent to prevent the superbasified sulfonate from being so thick that it cannot be easily handled. Similarly, superbasified magnesium sulfonate will also contain base oil as a diluent. With the amount of base oil in superbase calcium sulfonate and superbase magnesium sulfonate, it may be unnecessary to add additional base oil depending on the desired consistency of the grease immediately after conversion and also the desired consistency of the final grease. Synthetic base oils can also be used in the greases of the present invention. Such synthetic base oils include polyalphaolefins (PAO), diesters, polyol esters, polyethers, alkylated benzenes, alkylated naphthalenes, and silicone fluids. In some cases, synthetic base oils may have an adverse effect if present during the conversion process as will be understood by those commonly skilled in the art. In such cases, those synthetic base oils should not be initially added, but added to the grease process at a stage when adverse effects will be eliminated or minimized, such as after conversion. Naphthenic and paraffinic mineral base oils are preferred due to their lower cost and availability. The total amount of base oil added (including that initially added and any that may be added later in the grease manufacturing process to achieve the desired consistency) is preferably in the ranges indicated in Table 1, above, based on the final weight of the grease. Typically, the amount of base oil added as a separate ingredient will increase as the amount of superbase calcium sulfonate decreases. Combinations of different base oils, as described above, may also be used in the invention, as will be understood by those commonly skilled in the art.

[51] The superbasified magnesium sulfonate (also referred to herein, for brevity, simply as “magnesium sulfonate”) used in accordance with these embodiments of the invention for a calcium magnesium sulfonate grease may be any typical of that documented or known in the art. previous technique. Superbasified magnesium sulfonate can be manufactured in situ or any commercially available superbasified magnesium sulfonate can be used. The superbasified magnesium sulfonate will typically comprise a neutral magnesium alkylbenzenesulfonate and a superbasified amount of which a substantial amount is in the form of magnesium carbonate. It is believed that magnesium carbonate typically is in an amorphous (non-crystalline) form. There may also be a portion of the superbasification that is in the form of magnesium oxide, magnesium hydroxide, or a mixture of magnesium oxide and magnesium hydroxide. The total base number (NBT) of the superbase magnesium sulfonates is preferably at least 400 mg KOH/g, but lower NBT values may also be acceptable and in the same ranges as indicated for the NBT values for calcium sulfonate. superbasified above.

[52] A small amount of a facilitating acid is preferably added to the mixture before conversion. A facilitating acid is required when the addition of a glycerol derivative is combined with a facilitating acid delay method, but is otherwise optional. Suitable facilitating acids, such as alkylbenzenesulfonic acid, having an alkyl chain length typically between 8 and 16 carbon atoms, can help facilitate efficient grease structure formation. Most preferably, this alkylbenzenesulfonic acid comprises a mixture of alkyl chain lengths that are predominantly about 12 carbons in length. Such benzenesulfonic acids are typically called dodecylbenzenesulfonic acid (“ADDBS”). Commercially available benzenesulfonic acids of this type include JemPak 1298 Sulfonic Acid as supplied by JemPak GK Inc., Calsoft LAS-99 as supplied by Pilot Chemical Company, and Biosoft S-101 as supplied by Stepan Chemical Company. When alkylbenzenesulfonic acid is used in the present invention, it is added before conversion and preferably in an amount in the ranges indicated herein in the Tables and Examples. If calcium sulfonate or magnesium sulfonate is manufactured in situ using alkylbenzenesulfonic acid, the facilitating acid added in accordance with this embodiment is in addition to that required to produce the calcium sulfonate or magnesium sulfonate.

[53] Water is added in preferred embodiments of the invention as a converting agent. One or more conventional non-aqueous converting agents is/are also preferably added in certain embodiments of the invention. Conventional non-aqueous converting agents include any previously known converting agent other than water, such as alcohols, ethers, glycols, glycol ethers, glycol polyethers, carboxylic acids, inorganic acids, organic nitrates, other polyhydric alcohols and derivatives thereof, and any other compounds containing either active hydrogen or tautomeric hydrogen that merely function as converting agents (rather than dual-function acid complexing-converting agents) and are added to the composition prior to conversion. Conventional non-aqueous converting agents also include those agents that contain some water as a diluent or an impurity. Such ingredients can be added after conversion, if desired, and are not considered in this case as “conventional non-aqueous converting agents” because they would not be acting as converting agents for the conversion to be complete.

[54] Although they can be used as conventional non-aqueous converting agents, it is preferred not to use alcohols, such as methanol or isopropyl alcohol or lower molecular weight (i.e. more volatile) alcohols, because of environmental concerns and restrictions related to gases released into the atmosphere during the grease manufacturing process or the removal of hazardous waste from purified alcohols. The total amount of water added as a converting agent, based on the final weight of the grease, is preferably in the ranges indicated herein in the Tables and Examples. Additional water may be added after conversion. Also, if the conversion occurs in an open vessel at a temperature high enough to volatilize a significant portion of the water during the conversion, additional water may be added to replace the water that was lost. The total amount of one or more conventional non-aqueous converting agents added, based on the final weight of the grease, is preferably in the ranges indicated herein in the Tables and Examples. Typically, the amount of conventional non-aqueous converting agent used will decrease as the amount of superbasified calcium sulfonate decreases. Depending on the converting agents used, some or all of them may be removed by volatilization during the manufacturing process. Particularly preferred are lower molecular weight glycols such as hexylene glycol and propylene glycol. It should be noted that some converting agents can also serve as complexing acids to produce sulfonate-based complex grease in accordance with an embodiment of the invention. Such materials will simultaneously provide both conversion and complexation functions.

[55] According to another preferred embodiment, conventional non-aqueous converting agents are not used as ingredients. Conventional non-aqueous converting agents can be added after conversion is complete, if desired, within the scope of such preferred embodiments of the invention because they will not act as converting agents if added after conversion; however, it is preferred that all of them be omitted in these preferred embodiments.

[56] One or more calcium-containing bases are also added as ingredients in preferred embodiments of sulfonate-based grease composition according to the invention. These calcium-containing bases react with complexing acids to form a calcium magnesium sulfonate complex grease. Calcium-containing bases may include calcium hydroxyapatite, added calcium carbonate, added calcium hydroxide, added calcium oxide, or a combination of one or more of those previously mentioned. According to a preferred embodiment, added calcium carbonate can be used as the only added calcium-containing base, as described in the '265 patent. The preferred amounts of ingredients when calcium carbonate is the only calcium-containing base added, with or without any conventional non-aqueous converting agent, in accordance with these embodiments, are in the following tables. Amounts are percent by weight of the final grease product (although these bases and other ingredients will not be present in the final grease product). TABLE 2A - Calcium carbonate when a conventional non-aqueous converting agent is used TABLE 2B - Calcium carbonate when conventional non-aqueous converting agent is not used

[57] According to another preferred embodiment, calcium hydroxyapatite is added as a calcium-containing base as described in the '406 patent. Most preferably added calcium hydroxyapatite and added calcium carbonate are used together, together with a small amount of added calcium hydroxide. The preferred amounts of ingredients when calcium hydroxyapatite is added as a calcium-containing base (preferably with added calcium carbonate and added calcium hydroxide), with or without any conventional non-aqueous converting agent, in accordance with these embodiments, are in the following tables. . Amounts are percent by weight of the final grease product (although these bases and other ingredients will not be present in the final grease product). TABLE 3A - Calcium hydroxyapatite when a conventional non-aqueous converting agent is used TABLE 3B - Calcium hydroxyapatite when conventional non-aqueous converting agent is not used

[58] The calcium-containing base(s) to react with complexing acids according to preferred embodiments may be added before conversion, after conversion, or a portion is added before conversion and a portion is added after conversion.

[59] Added calcium carbonate used as a calcium-containing base, either alone (as described in the '265 patent) or in combination with another calcium-containing base or with other calcium-containing bases (such as calcium hydroxyapatite), in accordance with these embodiments of the invention, is finely divided with an average particle size of about 1 to 20 micrometers, preferably about 1 to 10 micrometers, most preferably about 1 to 5 micrometers. Additionally, the added calcium carbonate is preferably crystalline calcium carbonate (most preferably calcite) of sufficient purity so as to have abrasive contaminants such as silica and alumina in a sufficiently low content so as not to significantly influence the antiwear properties of the resulting grease. Ideally, for best results, calcium carbonate should be either food grade or United States Pharmacopeia grade. The amount of added calcium carbonate added is preferably in the ranges indicated herein in the Tables and Examples, particularly in Tables 2A and 2B. These amounts are added as a separate ingredient in addition to the amount of dispersed calcium carbonate contained in the superbasified calcium sulfonate. According to another preferred embodiment of the invention, added calcium carbonate is added prior to conversion as the only calcium-containing base ingredient to react with complexing acids. Additional calcium carbonate can be added to embodiments of the invention of either simple grease or complex grease after conversion, and after the entire reaction with complexing acids is complete in the case of a complex grease. However, references herein to added calcium carbonate refer to calcium carbonate as one of the calcium-containing base(s) added for reaction with complexing acids when preparing a complex grease according to the invention.

[60] Calcium hydroxyapatite added according to preferred embodiments is most preferably finely divided with an average particle size of about 1 to 20 micrometers, preferably about 1 to 10 micrometers, most preferably about 1 to 5 micrometers. Additionally, the calcium hydroxyapatite will be of sufficient purity so as to have abrasive contaminants such as silica and alumina at a sufficiently low level not to significantly influence the antiwear properties of the resulting grease. Ideally, for best results, calcium hydroxyapatite should be either food grade or United States Pharmacopeia grade. The amount of calcium hydroxyapatite added will preferably be in the ranges indicated herein in the Tables and Examples, particularly in Tables 3A and 3B, although more may be added, if desired, after conversion and the entire reaction with complexing acids is complete.

[61] According to another preferred embodiment of the invention, calcium hydroxyapatite can be added in an amount that is stoichiometrically insufficient to completely react with the complexing acids. In this embodiment, finely divided calcium carbonate as an added, solid, oil-insoluble calcium-containing base may be added, preferably before conversion, in an amount sufficient to completely react with and neutralize the portion of any subsequently added complexing acids not neutralized by calcium hydroxyapatite. Alternatively, in this embodiment, finely divided calcium hydroxide or finely divided calcium oxide as a solid, oil-insoluble calcium-containing base may be added, preferably before conversion, in an amount sufficient to completely react with and neutralize the portion of any complexing acids. subsequently added not neutralized by co-added calcium hydroxyapatite. According to yet another preferred embodiment, a combination of added calcium carbonate and added calcium hydroxide (or added calcium oxide) is used when the amount of calcium hydroxyapatite is stoichiometrically insufficient.

[62] According to yet another preferred embodiment, when calcium hydroxyapatite is used in combination with calcium hydroxide added as calcium-containing bases to react with complexing acids to make a calcium magnesium sulfonate grease, a smaller amount of calcium hydroxyapatite Calcium is required compared to the calcium sulfonate greases described in the '406 patent. In the '406 patent, the added calcium hydroxide and/or the added calcium oxide are preferably present in an amount not greater than 75% of the hydroxide-equivalent basicity provided by the total of the added calcium hydroxide and/or the calcium oxide. added and calcium hydroxyapatite. In other words, calcium hydroxyapatite preferably contributes at least 25% of the total added hydroxide equivalents (both calcium hydroxyapatite and added calcium hydroxide and/or added calcium oxide) in the calcium sulfonate greases described in the patent. '406, particularly when a poor quality overbasified calcium sulfonate is used. If less than that amount of calcium hydroxyapatite is used, the drip point of the final calcium sulfonate grease may be impaired. However, with the addition of superbasified magnesium sulfonate to the composition according to various embodiments of this invention, less calcium hydroxyapatite can be used while still maintaining sufficiently high drip points. The amount of calcium hydroxyapatite used in accordance with preferred embodiments of this invention may be less than 25%, and even less than 10% of the hydroxide equivalent basicity, even when a poor quality superbasified calcium sulfonate is used. This is an indication that the presence of superbasified magnesium sulfonate in the finished grease has resulted in a surprising change and improved chemical structure. Since calcium hydroxyapatite is typically much higher in cost compared to added calcium hydroxide, this results in a potential additional cost reduction of the final grease without any significant reduction in drip point.

[63] In another embodiment, calcium carbonate can also be added with calcium hydroxyapatite, calcium hydroxide and/or calcium oxide, with calcium carbonate being added either before or after the reaction with complexing acids. , or added both before and after the reaction with complexing acids. When the amounts of calcium hydroxyapatite, calcium hydroxide, and/or calcium oxide are not sufficient to neutralize the added complexing acid or added complexing acids, calcium carbonate is preferably added in an amount that is greater than the amount enough to neutralize any remaining complexing acid or any remaining complexing acids.

[64] The calcium hydroxide added and/or calico oxide added before conversion or after conversion according to another embodiment is, most preferably, finely divided with an average particle size of about 1 to 20 micrometers. , preferably about 1 to 10 micrometers, most preferably about 1 to 5 micrometers. Additionally, the calcium hydroxide and calcium oxide will be of sufficient purity so as to have abrasive contaminants such as silica and alumina at a sufficiently low level so as not to significantly influence the antiwear properties of the resulting grease. Ideally, for best results, calcium hydroxide and calcium oxide should be either food grade or United States Pharmacopeia grade. The total amount of calcium hydroxide and/or calcium oxide will preferably be in the ranges indicated herein in the Tables and Examples, particularly in Tables 3A and 3B. These amounts are added as separate ingredients in addition to the amount of residual calcium hydroxide or residual calcium oxide contained in the superbasified calcium sulfonate. Most preferably, an excess amount of calcium hydroxide relative to the total amount of complexing acids used is not added prior to conversion. According to yet another embodiment, it is not necessary to add any calcium hydroxide or calcium oxide to react with complexing acids and either added calcium carbonate or added calcium hydroxyapatite (or both) can be used as the single calcium-containing base(s) added for such a reaction or may be used in combination for such a reaction.

[65] One or more alkali metal hydroxides are also optionally added as ingredients in a preferred embodiment of sulfonate-based grease composition according to the invention. Optional added alkali metal hydroxides comprise sodium hydroxide, lithium hydroxide, potassium hydroxide, or a combination thereof. Most preferably, sodium hydroxide is the alkali metal hydroxide used with the sulfonate-based greases according to one embodiment of the invention. The total amount of alkali metal hydroxide added is preferably in the ranges indicated herein in the Tables and Examples. As with calcium-containing bases, alkali metal hydroxide reacts with complexing acids resulting in an alkali metal salt of a complexing acid present in the final grease product. The preferred amounts indicated herein in the Tables and Examples are amounts added as raw ingredients relative to the weight of the final grease product, although alkali metal hydroxide will not be present in the final grease.

[66] According to a preferred embodiment of a method for manufacturing a superbasified calcium magnesium sulfonate grease, the alkali metal hydroxide is dissolved in water before being added to the other ingredients. The water used to dissolve alkali metal hydroxide can be water used as a converting agent or water added after conversion. It is most preferred to dissolve the alkali metal hydroxide in water before adding it to the other ingredients, but it can also be directly added to the other ingredients without first being dissolved in water.

[67] One or more complexing acids, such as long-chain carboxylic acids, short-chain carboxylic acids, boric acid, and phosphoric acid are also preferably separately added, according to some preferred embodiments of the invention, when a complex grease of calcium and magnesium sulfonate. Most preferably, the complexing acids comprise 12-hydroxystearic acid, acetic acid, phosphoric acid, boric acid, or a combination thereof. The preferred range of separately added total complexing acids and the preferred amounts of the specific types of separately added complexing acids as ingredients in weight percent of the final grease product (although these acids will react with the bases and will not be present in the final grease product ) are here in the Tables and Examples.

[68] The amount of added short-chain or long-chain fatty acids can be reduced or eliminated when one or more glycerol derivatives are added according to a preferred embodiment of the invention. As used herein, references to “separately added complexing acids” or similar phrasing refer to complexing acids that are added as separate ingredients or formed in situ by a reaction of ingredients other than a reaction of an added glycerol derivative and water.

[69] Long-chain carboxylic acids suitable for use according to the invention comprise aliphatic carboxylic acids with at least 12 carbon atoms. Preferably, the long-chain carboxylic acids comprise aliphatic carboxylic acids having at least 16 carbon atoms. Most preferably, the long chain carboxylic acid is 12-hydroxystearic acid.

[70] Short-chain carboxylic acids suitable for use according to the invention comprise aliphatic carboxylic acids with no more than 8 carbon atoms, and preferably no more than 4 atoms. Most preferably, the short chain carboxylic acid is acetic acid. Suitable for use is any compound that can be expected to react with water or other components used in the production of a grease according to this invention, with such reaction generating a short-chain or long-chain carboxylic acid. For example, the use of acetic anhydride would form, by reaction with the water present in the mixture, acetic acid to be used as a complexing acid. Likewise, the use of methyl 12-hydroxystearate would form, by reaction with the water present in the mixture, 12-hydroxystearic acid to be used as a complexing acid. Alternatively, additional water may be added to the mixture for reaction with such components to form the necessary complexing acid if sufficient water is not already present in the mixture. Additionally, acetic acid and other carboxylic acids can be used as a converting agent or complexing acid or both, depending on when it is added. Similarly, some complexing acids (such as 12-hydroxystearic acid in the '514 and '467 patents) can also be used as converting agents.

[71] If boric acid is used as a complexing acid according to this embodiment, the boric acid can be added after first being dissolved or slurried in water, or it can be added without water. Preferably, boric acid will be added during the manufacturing process so that water is still present. Alternatively, any of the well-known inorganic salts of boron acid can be used instead of boric acid. Likewise, any of the proven borated organic compounds such as borated amines, borated amides, borated esters, borated alcohols, borated glycols, borated ethers, borated epoxides, borated ureas and the like can be used instead of boric acid.

[72] The percentages of various complexing acids described here refer to the pure, active compounds. If any of these complexing acids are available in a diluted form, they may still be available for use in the present invention. However, the percentages of such diluted complexing acids will need to be adjusted in order to take into account the dilution factor and bring the actual active material within the specified percentage ranges.

[73] Other additives commonly recognized within the art of manufacturing greases can also be added to either the simple grease embodiment of the invention or the complex grease embodiment of the invention. Such additives include rust and corrosion inhibitors, metal deactivators, metal passivators, antioxidants, extreme pressure additives, antiwear additives, chelating agents, polymers, tackifiers, dyes, chemical markers, fragrance giving agents, and solvents. evaporative. The latter category can be particularly useful when manufacturing open gear lubricants and braided wire cable lubricants. The inclusion of any such additives should be understood as still within the scope of the present invention. All ingredient percentages are based on the final weight of the finished grease unless otherwise noted, although that amount of the ingredient may not be in the final grease product due to reaction or volatilization.

[74] The sulfonate-based complex greases according to these preferred embodiments are most preferably an NLGI grade No. 2 grease having a drip point of at least 302°C (575°F) more preferably 343° C (650°F) or greater, but greases with other NLGI grades from No. 000 to No. 3 may also be manufactured in accordance with these embodiments with modifications that will be understood by those commonly skilled in the art. The use of the preferred methods and ingredients according to the invention appears to improve the thickening yield and drip point compared to sulfonate-based greases manufactured without an added glycerol derivative.

Methods for manufacturing sulfonate-based greases

[75] Preferred sulfonate grease compositions are manufactured in accordance with preferred methods of the invention described herein and in the references incorporated herein by reference. In a preferred embodiment, the method comprises: (1) mixing superbasified calcium sulfonate and optionally a base oil; (2) optionally adding and mixing superbasified magnesium sulfonate; (3) adding and mixing one or more glycerol derivatives; (4) adding and mixing one or more converting agents (water and optionally one or more conventional non-aqueous converting agents); (5) heating some combination of these ingredients until conversion has occurred; and (6) mixing and heating to a temperature high enough to ensure removal of water. Most preferably, the method also comprises: (7) optionally adding and mixing one or more facilitating acids; (8) adding and mixing one or more calcium-containing bases; (9) adding and mixing one or more complexing acids; and (10) optionally adding and mixing an alkali metal hydroxide, preferably sodium hydroxide pre-dissolved in water before adding to the other ingredients. Most preferably, the method also comprises a facilitating acid delay method and/or a converting agent delay method. Additional optional steps comprise: (11) optionally mixing additional base oil as needed after conversion; (12) mixing and heating to a sufficiently high temperature to ensure removal of any volatile reaction byproducts and optimize the quality of the final product; (13) cool the grease while adding additional base oil as needed; and (14) adding the remaining desired additives as are well known in the art.

[76] Typically, one of the final steps in manufacturing a sulfonate-based grease is to grind the grease to obtain a final smooth homogeneous product. According to a preferred embodiment, grinding of the grease is not required when a glycerol derivative is added, because grinding confers little or no improvement in thickening as determined by the penetration value (and corresponding thickening yield) or structural smoothness. . According to another preferred embodiment, the grease is milled even when a glycerol derivative is added.

[77] Any of the above steps may be modified by, or with the use of, any one or more of the following additional ingredients or steps: (a) by adding superbasified magnesium sulfonate all at once before conversion; (b) adding magnesium sulfonate using a split addition method (c) using a magnesium sulfonate delay period; (d) use of a combination of split addition and magnesium sulfonate delay period(s); (e) use of one or more acid facilitator delay periods; (f) excluding the addition of any conventional non-aqueous converting agents prior to conversion; (g) adding calcium hydroxyapatite and/or calcium carbonate added as calcium-containing bases to react with complexing acids, either with or without separate addition of added calcium hydroxide and/or calcium oxide added as calcium-containing bases; or (h) the delayed addition of conventional non-aqueous converting agents (a converter agent delay method). These additional methods and ingredients are described in U.S. Patent Nos. 9,273,265, 9,458,406, 9,976,101, 9,976,102, 10,087,387, 10,087,388, and 10,087,391), which are incorporated herein by reference.

[78] The temperature for conversion heating in step (5) is preferably 87.8°C to 93.3°C (190°F to 200°F). In some embodiments, it may be preferred to heat to a temperature of about 127°C (260°F) during step (5). The converting agents in step (4) may include one or more conventional non-aqueous converting agents, water, or any combinations thereof. Water, if added before conversion, can act as a converting agent. If superbasified magnesium sulfonate is added in step (2), it is not necessary to add any conventional non-aqueous converting agent in step (6) (unless a conversion agent delay method is used), but a non-aqueous converting agent Conventional can be further added (with or without a converter agent delay method). The complexing acids in step (9) may be separately added complexing acids or may be a complexing acid formed in situ by the reaction of an added glycerol derivative and water. All or a portion of one or more glycerol derivatives may be added before conversion or after conversion or any combination thereof. Most preferably, at least a portion of a glycerol derivative is added prior to conversion.

[79] The glycerol derivative in step (3) can be added before conversion, during conversion, after conversion, or a combination thereof. Most preferably at least some glycerol derivative is added before conversion. Each of the ingredients in steps (8 - calcium-containing bases), (9 - complexing acids) and (10 - alkali metal hydroxide) can be added before conversion, after conversion, or a portion added before and another portion added after the conversion. Any facilitating acid added in step (7) is preferably added before conversion. If a facilitating acid and alkali metal hydroxide are used, the facilitating acid is preferably added to the mixture before the alkali metal hydroxide is added. Most preferably, the specific ingredients and specific amounts used in the methods of the invention are in accordance with the preferred embodiments of the compositions described herein. Although some ingredients are preferably added before other ingredients, the order of addition of ingredients relative to the other ingredients in preferred embodiments of the invention is not critical (unlike water which is added before a conventional non-aqueous converting agent if a delay method of converting agent is used).

[80] Although the order and temporal synchronization of step (6) and final steps 11 to 14 are not critical, it is preferred that water be removed quickly after conversion. Generally, the grease is heated to remove the water that was initially added as a converting agent, and also any water formed by the chemical reactions during the formation of the grease. The existence of water in the grease batch for prolonged periods of time during manufacturing can result in degradation of thickening yield, dripping point, or both, and such adverse effects can be avoided by removing the water quickly. If polymeric additives are added to the grease, they should preferably not be added until the grease temperature reaches 149°C (300°F). Polymeric additives can, if added in sufficient concentration, prevent effective water volatilization. Therefore, polymeric additives should preferably be added to the grease only after all the water has been removed. If during manufacturing it can be determined that all water has been removed before the temperature of the grease has reached the preferred value of 149°C (300°F), then any polymeric additives may preferably be added at any later time.

[81] Preferred embodiments of the methods herein can occur in either an open or closed vessel as is commonly used for the manufacture of greases. The conversion process can be carried out at normal atmospheric pressure or under pressure in a closed vessel. Open vessel (non-pressure vessel) manufacturing is preferred because such grease manufacturing equipment is commonly available. For the purposes of this invention an open vessel is any vessel with or without a lid or top hatch provided that any such lid or top hatch is not steam tight so that significant pressure cannot be generated during heating. The use of such an open vessel with the lid or top hatch closed during the conversion process will help retain the required water content as a converting agent while generally allowing a conversion temperature at or even above the boiling point of water. Such higher conversion temperatures can result in further improvements of thickening yield for both simple and complex calcium magnesium sulfonate greases, as will be understood by those commonly skilled in the art. Manufacturing in pressurized vessels can also be used and can result in even greater improvements in thickening yield, but pressurized processes can be more complicated and difficult to control. Additionally, manufacturing calcium and magnesium sulfonate greases in pressurized vessels can result in productivity problems. The use of pressurized reactions can be important for certain types of greases (such as polyurea greases) and most grease manufacturing facilities will only have a limited number of pressurized vessels available. Using a pressurized vessel to manufacture calcium and magnesium sulfonate greases, where pressurized reactions are not as important, may limit the ability of a manufacturing facility to manufacture other greases where those reactions are important. These problems are avoided with open vessels.

[82] A converting agent delay used in some preferred embodiments is a period of time between the initial addition of water before conversion and the addition before conversion of at least a portion of a non-aqueous converting agent. A converting agent delay period may be a converting agent temperature adjustment delay period or a converting agent retention delay period or both. If additional water is added prior to conversion to replace evaporation losses during the manufacturing process, those additions are not used in resetting or in determining conversion agent delay periods, and only the first addition of water is used as the starting point. initiation in determining converter agent delay periods. A converting agent temperature adjustment delay period is the amount of time after the initial water is added that it takes to heat the mixture to a temperature or range of temperatures. A converting agent retention delay period is the amount of time that the mixture is held at one temperature (including room temperature) before being heated or cooled to another temperature or before adding at least a portion of a converting agent not aqueous. There may be multiple converting agent temperature adjustment delay periods and multiple converting agent retention delay periods or a combination of both. For example, the mixture comprising the initial water may be held at room temperature for 30 minutes prior to addition of a non-aqueous converting agent (a first hold delay period) and may continue to be held at room temperature for another hour before addition. addition of the same or a different non-aqueous converting agent (a second retention delay period). Additionally, the mixture comprising the initial water may be heated or cooled to a first temperature after which a non-aqueous converting agent is added (a first temperature adjustment period) and then the mixture is heated or cooled to a second temperature after the which the same or a different non-aqueous converting agent is added (a second temperature adjustment period, without any interim maintenance period). Although a converting agent delay period may involve a retention delay period that does not involve heating, a short period of time of less than 15 minutes between the addition of the initial water as a converting agent and the addition of the entire converting agent(s) (s) non-aqueous converter(s) without any heating during that period of time is not a “converting agent delay” or a “converting agent delay period” as used herein. A delay for adding any or all of the non-aqueous converting agent(s) without heating during the delay period should be at least about 20 minutes and more preferably at least about 20 minutes. least about 30 minutes.

[83] A facilitating acid lag period used in some preferred embodiments is a period of time between the addition of a facilitating acid and (1) the next subsequently added ingredient or (2) a subsequently added reactive ingredient (superbasified magnesium sulfonate ), even if it is not the next ingredient added (one or more other ingredients is/are added between the facilitating acid and the reactive ingredient) if there is heating between additions. A facilitating acid delay may be a facilitating acid temperature adjustment delay period or a facilitating acid retention delay period or both, similar to the previously described converting agent delay periods. A facilitating acid delay may follow the addition of all of the facilitating acid or a facilitating acid delay may follow the addition of a portion of a facilitating acid. For example, a facilitating acid temperature adjustment delay period is the amount of time after one or more facilitating acids are added and before the addition of the next ingredient (or a portion thereof) that it takes to heat the mixture to a temperature or range of temperatures. A facilitating acid retention lag period is the amount of time that the mixture is held at one temperature (which may be room temperature) before being heated or cooled to another temperature or before adding the next ingredient or portion. of a facilitating acid. A delay between the addition of a facilitating acid and the next ingredient of 30 minutes or more, preferably 40 minutes or more, is a facilitating acid delay, regardless of which ingredient the next added ingredient is. A delay may be shorter than 30 minutes if there is a temperature adjustment between the addition of the facilitating acid and the next added ingredient. Additionally, if the next added ingredient is reactive with the facilitating acid (such as superbasified magnesium sulfonate), then a Facilitating acid delay period can be as little as 30 minutes as about 20 minutes even without any heating. If a reactive ingredient is added after the facilitating acid and there is a temperature adjustment between the addition of the facilitating acid and the reactive ingredient, then there is a facilitating acid delay period even if the reactive ingredient is not the immediately next added ingredient (i.e. is, the reactive ingredient is added as the second, third, fourth, etc. ingredient added after the facilitating acid) and even if there is no delay period between the facilitating acid and the next ingredient added (the ingredient first added after the facilitating acid) because it is added less than 30 minutes after the facilitating acid without any interim temperature adjustment. If the reactive ingredient is superbasified magnesium sulfonate, then there is a magnesium sulfonate delay period as described below.

[84] All facilitating acid delay periods end upon addition of the next added ingredient, unless a facilitating acid reactive ingredient (such as magnesium sulfonate) must be added at a later point in the process (such as the second, third, etc. ingredient added after the facilitating acid), then the facilitating acid delay continues until the addition of that reactive ingredient (such as superbasified magnesium sulfonate). In that case, the facilitating acid delay or delays is/are determined by whether there is a temperature adjustment or the time held at a temperature between the addition of the facilitating acid and magnesium sulfonate. For example, if you add the facilitating acid and then immediately add three other ingredients without a change in temperature, then add the superbasified magnesium sulfonate, there is a single facilitating acid retention delay, which is the amount of time between adding the acid facilitator and magnesium sulfonate, although magnesium sulfonate was the fourth ingredient added. When magnesium sulfonate is the last added reactive ingredient, there will also be a magnesium sulfonate delay (as discussed further below), which overlaps the facilitating acid delay period.

[85] A magnesium sulfonate lag period used in some preferred embodiments is a period of time between the addition of water or other reactive ingredients (such as acids, bases, or non-aqueous converting agents) and the subsequent addition of at least a portion of superbasified magnesium sulfonate. Magnesium sulfonate delay periods can be a magnesium sulfonate temperature adjustment delay period or a magnesium sulfonate retention delay period or both, similar to converting agent delays and facilitating acid delays. If there is a temperature adjustment delay or a retention delay between the addition of a facilitating acid and the subsequent addition of superbasified magnesium sulfonate, then the delay is a facilitating acid delay and a magnesium sulfonate delay.

[86] According to another preferred embodiment, a sulfonate-based grease manufactured with a glycerol derivative has final (converted) grease IVTF spectra that are different from the IVTF spectra of prior art sulfonate-based greases. As previously described, prior art superbasified calcium sulfonate greases have various IVTF spectra during the conversion course. An TFIV spectrum showing a peak at 862 cm-1 indicates the amorphous calcium carbonate contained in the superbasified calcium sulfonate will be converted to dispersed crystalline calcium carbonate. An intermediate peak at about 874 cm-1 is commonly observed during the conversion process of calcium sulfonate-based greases. Depending on small variations in the grease being manufactured, this intermediate peak can be observed within the range of about 872 cm-1 to 877 cm-1. Complete conversion to the desirable dispersion of crystalline calcium carbonate (calcite) is typically evidenced by the elimination of both the original amorphous calcium carbonate peak at 862 cm-1 and the intermediate peak (as formed during, but before, completion of the conversion process) and confirmation of a new single peak at around 882 cm-1.

[87] When added powdered calcium carbonate is used in accordance with the '265 patent or in an amount that is in excess of that which would react with complexing acid(s), a final grease IVTF spectrum is observed ( converted) a little different. In sulfonate-based greases comprising added calcium carbonate, complete conversion will be evidenced by a TFIV spectrum showing a single peak at about 882 cm-1 with a small shoulder at about 874 cm-1. This is because unreacted micronized dispersed crystalline calcium carbonate (calcite) has the characteristic IVTF peak at about 874 cm-1 rather than at about 882 cm-1 (the much smaller calcium carbonate particles formed from conversion of amorphous calcium carbonate).

[88] When adding a glycerol derivative that is added in accordance with preferred embodiments of the invention, new IVTF spectra of final (converted) grease comprising one or more of: (1) two different peaks (also referred to herein as a doublet) one between 872 cm-1 and 877 cm-1 and an a of about 882 cm-1, where the peak between 872 cm-1 and 877 cm-1 is the dominant peak, (2) a doublet where the peak at about 882 cm-1 is the dominant peak, (3) an uneliminated shoulder at about 862 cm-1, (4) a dominant peak at about 882 cm-1 and a shoulder between 872 cm-1 and 877 cm-1, where the shoulder height is about 33% - 95% of the peak height at 882 cm-1, or (5) a peak between 872 cm-1 and 877 cm-1 with a shoulder at about 882 -1 cm-1

[89] The sulfonate-based grease composition and methods for manufacturing such compositions in accordance with various embodiments of the invention are further described and explained in relation to the following examples. Examples 1 to 6 are baseline examples that do not include the addition of a glycerol derivative in accordance with preferred embodiments of the invention. Examples 1 to 16 use crystalline calcium carbonate added as the only calcium-containing base added to react with complexing acids, as described in U.S. Patent No. 9,273,265 (and further described in the '101, '102, '387,' patents. 388, and '391). Examples 17 to 23 use calcium hydroxyapatite, added calcium carbonate, and added calcium hydroxide as calcium-containing bases to react with complexing acids as described in U.S. Patent No. 9,458,406 (and further described in the '101, '102 patents , '387, '388, and '391). Calcium carbonate technology was selected by Examples 7 and 9 to 16 in accordance with preferred embodiments of the invention as a threshold for the beneficial results that can be achieved by adding a glycerol derivative.

[90] Example 1 - This Example is the same as Example 27 of U.S. Patent No. 10,087,387 and uses added calcium carbonate as described in U.S. Patent No. 9,273,265. The ratio of superbasified calcium sulfonate to superbasified magnesium sulfonate was about 90/10. The delayed non-aqueous converting agent technique was used. The facilitating acid delay method was not used. All superbasified magnesium sulfonate was added at the beginning.

[91] The grease was manufactured as follows: 310.14 grams of superbasified oil-soluble calcium sulfonate of NBT 400 was added to an open mixing vessel followed by 345.89 grams of a neutral solvent type paraffinic base oil from the group 1 having a viscosity of about 600 SUS at 37.8°C (100°F). NBT 400 superbase oil soluble calcium sulfonate was a calcium sulfonate of good quality as defined by our recently published U.S. Patent No. 9,458,406. Unheated mixing began using a planetary mixer with paddles. Then 31.60 grams of superbasified magnesium sulfonate A was added and allowed to mix for 15 minutes. This superbasified magnesium sulfonate A is that described in U.S. Patent No. 10,087,387. Then 31.20 grams of a predominantly C12-alkyl benzenesulfonic acid (facilitating acid) was added. After mixing for 20 minutes, 75.12 grams of finely divided calcium carbonate with an average particle size below 5 microns was added and allowed to mix for 20 minutes. Then 0.84 grams of glacial acetic acid and 8.18 grams of 12-hydroxystearic acid were added. The mixture was stirred for 10 minutes. Then 40.08 grams of water were added, and the mixture was heated with continuous mixing to a temperature of 87.8°C (190°F) to 93.3°C (200°F). This represents a temperature adjustment delay. The mixture was mixed in this temperature range for 30 minutes. This represents a retention delay. During that time, significant thickening had occurred, with a grease structure being formed. Fourier Transform Infrared Spectroscopy (FTIV) indicated that water was being lost due to evaporation. Another 70 mL of water was added. IVTF spectroscopy also indicated that conversion had partially occurred although hexylene glycol (non-aqueous converting agent) had not yet been added. After the 30 minute holding delay at 87.8°C (190°F) to 93.3°C (200°F), 15.76 grams of hexylene glycol was added. Immediately after this, IVTF spectroscopy indicated that the conversion of amorphous calcium carbonate into crystalline calcium carbonate (calcite) had occurred. However, the batch seemed to soften a little after the addition of glycol. Another 20 mL of water was added followed by 2.57 grams of glacial acetic acid and 16.36 grams of 12-hydroxystearic acid. These two complexing acids were allowed to react for 10 minutes. Then 16.60 grams of a 75% solution of phosphoric acid in water was slowly added and allowed to mix and react.

[92] The grease was then heated to 199°C (390°F) to 204°C (400°F). As the mixture was heated, the grease continued to become increasingly thin and fluid. The heating mantle was removed from the mixer and the grease was allowed to cool while it continued to be mixed. The mixture was very thin and had no significant grease texture. When the temperature was below 76.7°C (170°F), a sample was removed from the mixer and passed through a three-roll mill. The milled grease had an unworked penetration of 189. This result was extremely surprising and indicated that a very unusual and highly rheopetic structure had been formed. Three more portions of the same base oil totaling 116.02 grams were added. The grease was then removed from the mixer and passed three times through a three-roll mill to achieve a final smooth homogeneous structure. The grease had a worked penetration measured at 60 strokes of 290. The percentage of overbase oil-soluble calcium sulfonate in the final grease was 31.96%. The drip point was 325°C (617°F).

[93] Example 2 - This Example is the same as Example 13 of U.S. Patent No. 10,087,388 and was manufactured similar to the grease of previous Example 1 of the present invention. Like the grease in Example 1, the ratio of superbasified calcium sulfonate to superbasified magnesium sulfonate was about 90/10, and all of the superbasified magnesium sulfonate was added before conversion, and the non-aqueous converting agent technique was used late. However, there were several significant changes regarding other aspects of this grease compared to the grease of Example 1. The superbasified magnesium sulfonate was not added at the beginning, but after the predominantly C12-alkyl-benzenesulfonic acid (facilitating acid) was added and mixed during an intentional 20-minute delay. This represents a facilitating acid delay method. It also represents a method of delayed addition of superbasified magnesium sulfonate relative to the facilitating acid. It also illustrates that the technique of delayed addition of superbasified magnesium sulfonate does not always need to be relative to the addition of water, but can be relative to any other reactive component. In this case, it was related to the addition of the facilitating acid. A second portion of powdered calcium carbonate was added after conversion but before the second portion of complexing acids was added. Also, this grease used a higher content of 12-hydroxystearic acid after conversion. Finally, phosphoric acid was not used as a complexing acid after conversion. Boric acid was used instead.

[94] The grease was manufactured as follows: 310.79 grams of NBT 400 superbasified oil-soluble calcium sulfonate was added to an open mixing vessel followed by 310.47 grams of a neutral solvent type paraffinic base oil from the group 1 having a viscosity of about 600 SUS at 37.8°C (100°F). NBT 400 superbase oil soluble calcium sulfonate was a calcium sulfonate of good quality as defined by our recently published U.S. Patent No. 9,458,406. This superbasified calcium sulfonate was also the same as that used in previous Example 1. Unheated mixing began using a planetary paddle mixer. Then 31.53 grams of a predominantly C12-alkyl-benzenesulfonic acid were added and allowed to mix for 20 minutes. Then 31.24 grams of superbasified magnesium sulfonate A was added and allowed to mix. After mixing for 20 minutes, 75.08 grams of finely divided calcium carbonate with an average particle size below 5 microns was added and allowed to mix for 20 minutes. Then 0.91 grams of glacial acetic acid and 8.09 grams of 12-hydroxystearic acid were added. The mixture was stirred for 10 minutes. Then 40.51 grams of water were added, and the mixture was heated with continuous mixing to a temperature of 87.8°C (190°F) to 93.3°C (200°F). This represents a temperature adjustment delay. The mixture was mixed in this temperature range for 30 minutes. This represents a retention delay. During that time, significant thickening had occurred, with a grease structure being formed. Fourier Transform Infrared Spectroscopy (IVTF) indicated that the conversion had partially occurred although hexylene glycol (non-aqueous converting agent) had not yet been added. After the 30 minute holding delay at 87.8°C (190°F) to 93.3°C (200°F), 30 mL of water and 15.50 grams of hexylene glycol were added. Immediately after this, IVTF spectroscopy indicated that the conversion of amorphous calcium carbonate into crystalline calcium carbonate (calcite) had occurred. The batch was stirred for 45 minutes. During that time the batch did not soften but actually became a little harder. Another 40 mL of water was added followed by another 25.02 grams of the same calcium carbonate. After mixing for 20 minutes, 1.57 grams of glacial acetic acid, 31.94 grams of 12-hydroxystearic acid, and 10 mL of water were added. These two complexing acids were allowed to react for 10 minutes. Then 25.0 grams of boric acid in 50 mL of hot water was slowly added and allowed to mix and react.

[95] The grease was then heated to 171°C (340°F). As the mixture was heated, the grease did not soften significantly. The heating mantle was removed from the mixer and the grease was allowed to cool while it continued to be mixed. The batch retained a grease structure as it cooled. This was an obvious difference in behavior between this grease and the grease of previous Example 1. When the grease was cooled to 93.3°C (200°F), 2.20 grams of an arylamine-based antioxidant was added. When the temperature was below 76.7°C (170°F), a sample was removed from the mixer and passed through a three-roll mill. The milled grease had an unworked penetration of 219. Again, this result was extremely surprising when compared to the behavior of the grease from previous Example 1. Although the grease from previous Example 1 was much more fluid at this point in the procedure (no significant grease texture), it showed surprising rheopectic properties due to the fact that it was ground to a much harder consistency. This indicates that the structure of this Example 2 grease is significantly less rheopetic than the structure of the Example 1 grease. Four more portions of the same base oil totaling 133.53 grams were added. The grease was then removed from the mixer and passed three times through a three-roll mill to achieve a final smooth homogeneous structure. The grease had a worked penetration measured at 60 strokes of 283. The percentage of overbase oil-soluble calcium sulfonate in the final grease was 30.27%. The drip point was >343°C (650°F). Using the customary inverse linear relationship between worked penetration and percentage superbase calcium sulfonate concentration, the grease in this example would have had a percent superbase calcium sulfonate concentration of 29.5% if additional base oil had been added to drive the penetration worked to the same value as that of the grease in previous Example 1. As can be seen, this grease had an improved thickening performance compared to the previous grease of Example 1.

[96] Example 3 - This Example is the same as Example 14 of US Patent No. 10,087,388 and Example 2 of US Patent No. 10,087,391), and was manufactured similar to the grease of previous Example 1 of the present invention. However, there were some differences. First, this grease used the poor quality superbasified calcium sulfonate used in most examples of US Patent No. 10,087,387. Second, the superbasified magnesium sulfonate was intentionally not added until the initial base oil, the superbasified calcium sulfonate, and the facilitating acid had been added and mixed for 20 minutes without any heat applied. This represents a delay period of facilitating acid, such as that used in the pregrease of Example 2. Also like Example 2, this is also considered a method of delayed addition of superbasified magnesium sulfonate with a retention delay and without a delay of temperature adjustment. Typically, such short retention delays (20 minutes) are not considered a true retention delay. However, since the facilitating acid will react even at room temperature with either a superbasified calcium sulfonate or a superbasified magnesium sulfonate, such a delay is considered here to be a magnesium sulfonate delay period. Note again that this same technique of delayed addition of superbasified magnesium sulfonate was performed on the previous grease of Example 2. However, in a similar manner to Example 1, this grease used an addition of 16.52 grams of a 75% solution of phosphoric acid in water instead of the addition of boric acid in water (as used in Example 2). The final milled grease of Example 3 had a worked penetration measured at 60 strokes of 293. The percentage of overbase oil-soluble calcium sulfonate in the final grease was 26.78%. However, the drip point was 271°C (520°F). It should be noted that, except for the inclusion of superbasified magnesium sulfonate, this grease had a composition that was essentially the same as the greases of Examples 6 to 9 of US Patent No. 9,458,406. Those four greases also used the same poor quality overbase calcium sulfonate. The dripping points of those four greases were 258°C (496°F), 251°C (483°F), 254°C (490°F), and 265°C (509°C); the average value was 257°C (495°F). Although the dripping point of this grease of Example 3 was low, it was somewhat higher than those of the four greases of US Patent No. 9,458,406. A summary of Examples 1 to 3 is provided below in Table 4. TABLE 4 - Summary of Examples 1 to 3

[97] Example 4 - This Example is the same as Example 3 of U.S. Patent No. 10,087,391 and was manufactured similar to the grease of previous Example 1 of the present invention. Like the grease of Example 1, this grease had a ratio of superbase calcium sulfonate to superbase magnesium sulfonate that was about 90/10. No facilitating acid delay method was used. All of the superbasified magnesium sulfonate was added at the beginning along with the superbasified calcium sulfonate, before the addition of facilitating acid. This Example 4 grease used the same good quality superbasified calcium sulfonate as the Example 1 grease.

[98] The only difference between this grease and the grease of Example 1 was that this grease did not have any conventional non-aqueous converting agent added. Water was added as required to replace any water loss due to evaporation during the conversion process. The conversion was monitored by IVTF spectra and took 2 hours to complete. The conversion occurred solely due to the water, the superbasified magnesium sulfonate, and any effects due to the initial amounts of pre-conversion complexing acids that were added. As the grease was heated to its maximum temperature, it significantly softened in a manner similar to the grease from Example 1. The texture of the grease recovered after grinding, in the same way as was observed in the grease from Example 1. This extreme rheopetic property has the same potential utility as mentioned in Example 1

[99] Example 5 - This Example is the same as Example 4 of U.S. Patent No. 10,087,391 and was manufactured similar to the grease of previous Example 4 of the present invention. The only significant difference was that a poor quality superbasified calcium sulfonate was used. The poor quality superbasified calcium sulfonate was the same as that used in the grease of previous Example 3. The conversion was monitored by IVTF spectra and took 7 hours to complete.

[100] Example 6 - This Example is the same as Example 5 of US Patent No. 10,087,391 and was manufactured similar to the grease of previous Example 5 of the present invention. The only significant difference was that only about half the amount of superbasified magnesium sulfonate was used. This grease used the same poor quality superbase calcium sulfonate as that which was used in the previous examples of this document. The conversion was monitored by TFIV spectra and took 10.5 hours to complete. A summary of Examples 4 to 6 is provided below in Table 5. TABLE 5 - Summary of Examples 4 to 6

[101] Except for the inclusion of superbasified magnesium sulfonate, the greases of Examples 4 to 6 of the present invention had essentially the same composition as the greases of Examples 6 to 9 of U.S. Patent No. 9,458,406. The greases of Examples 6 to 9 of U.S. Patent No. 9,458,406 used the same poor quality superbasified calcium sulfonate as the greases of Examples 5 and 6. The only compositional difference was that the greases of Examples 4 to 6 of the present invention contained superbasified magnesium sulfonate. Although the drip points of the greases of Examples 5 and 6 of the present invention (which contained the poor quality superbasified calcium sulfonate) were quite low, they were much improved compared to the greases of Examples 6 to 9 of U.S. Patent No. ° 9,458,406 (which also contained the same poor quality superbasified calcium sulfonate). This again demonstrates the drip point enhancement which is due to the inclusion of a superbasified magnesium sulfonate. It was evident that the conversion process took much longer when poor quality calcium sulfonate was used instead of good quality. However, the beneficial effect of superbasified magnesium sulfonate on conversion was evident by comparing the conversion times required for Examples 5 and 6 of the present invention. When the concentration of superbasified magnesium sulfonate was significantly reduced, the conversion time significantly increased. This shows that superbasified magnesium sulfonate is having a positive effect on conversion. Also, the dripping point of both greases of Examples 5 and 6 of the present invention improved after the grease was sheared at 150°C, as indicated by rolling stability test data. This again shows the potential beneficial effect of superbasified magnesium sulfonate on enhancing high-temperature structural stability when used at higher temperatures.

[102] Another important observation is made by comparing the dripping point of the grease from Example 3 (271°C (520°F)) with the dripping points of the greases from Example 5 (292°C (558°F)) and of Example 6 (294°C (562°F)). All three greases were compositionally similar. They all contained the same poor quality overbasified calcium sulfonate and the same overbasified magnesium sulfonate. They also contained the same complexing acids added in a similar manner. There was only one significant compositional difference: the grease of Example 3 contained a conventional non-aqueous converting agent while the greases of Examples 5 and 6 did not. Furthermore, the drip points of the greases of Examples 5 and 6 were significantly higher than that of the grease of Example 3. This demonstrates that when a calcium sulfonate/magnesium sulfonate complex grease is manufactured using certain process techniques without a conventional converter, a higher dripping point is surprisingly possible compared to the dripping point of a similar grease manufactured with a conventional converting agent.

[103] Example 7 - Another calcium magnesium sulfonate grease was manufactured similar to the grease of previous Example 5 of the present invention, using calcium carbonate as described in U.S. Patent No. 9,273,265, a ratio of superbasified calcium sulfonate and superbasified magnesium sulfonate of about 90/10, and addition of all the superbasified magnesium sulfonate at the beginning. However, there were two significant differences. First, 12-hydroxystearic acid was not added. Instead, hydrogenated castor oil (ORH) was added in a total amount that provided a molar equivalent amount of 12-hydroxystearic acid groups, assuming that the triacylglyceride structure of ORH was completely composed of 12-hydroxystearate groups. The amount of ORH added before conversion was 33% of the total amount of ORH, with the remaining amount added after conversion but before heating to maximum temperature. Second, a small amount of sodium hydroxide was dissolved in the water that was added to the grease after the conversion process. The concentration of sodium hydroxide (on an unreacted basis) in the final grease was 0.05%. This is a form of the technique described in U.S. Patent No. 9,976,102. Note that the addition of alkali metal hydroxide was not used in any of the greases in the previous examples. Additionally, the batch size of this grease was about 50% larger than that of the previous examples.

[104] Like the grease of Example 5 of the present invention, this grease did not use any hexylene glycol as a conventional non-aqueous converting agent. Also like the grease of Example 5, this grease did not have the superbasified calcium sulfonate and the superbasified magnesium sulfonate added with an initial amount of the base oil. Then the predominantly C12-alkyl-benzenesulfonic acid (facilitating acid) was added.

[105] The grease was manufactured as follows: 465.7 grams of NBT 400 superbase oil-soluble calcium sulfonate was added to an open mixing vessel. Then 47.9 grams of superbasified magnesium sulfonate A were added and allowed to mix for 15 minutes followed by 521.0 grams of a group 1 neutral solvent type paraffinic base oil having a viscosity of about 600 SUS at 37.8° C (100°F). Note that the order of addition of magnesium sulfonate and base oil was reversed in relation to previous examples. This variation will have no effect on the final grease because only non-reactive mixing must occur at this point in the procedure. NBT 400 superbasified oil-soluble calcium sulfonate was a calcium sulfonate of poor quality as defined by our recently published U.S. Patent No. 9,458,406. Unheated mixing began using a planetary mixer with paddles. Then 46.3 grams of a predominantly C12-alkyl benzenesulfonic acid (facilitating acid) were added. After mixing for 20 minutes, 114.6 grams of finely divided calcium carbonate with an average particle size below 5 micrometers was added and allowed to mix for 20 minutes. Then 12.64 grams of hydrogenated castor oil (ORH) was added followed by 1.26 grams of glacial acetic acid. Then 65.0 grams of water was added and the batch was heated to 87.8°C (190°F) to 93.3°C (200°F). Almost as soon as heating began, the batch visibly thickened. However, it thinned approximately by the time the temperature had reached 65.6°C (150°F). Once the batch temperature reached 87.8°C (190°F), over the next approximately 5.5 hours, nine portions of water totaling 214 grams were added to the batch as IVTF spectroscopy indicated that the water was being decreased due to evaporation.

[106] During this time, IVTF indicated that the conversion was occurring slowly but was not complete. When the batch had first reached 87.8°C (190°F), the IVTF spectrum showed a dominant peak at about 874 cm-1 with an evident shoulder at 862 cm-1 and the beginnings of a shoulder at 882 cm-1. After 5.5 hours of mixing at 87.8°C (190°F) to 93.3°C (200°F), the shoulder at 882 cm-1 had grown to the primary peak. The peak at 874 cm-1 had decreased significantly and was only very poorly resolved. The shoulder at 862 cm-1 (representing the original amorphous calcium carbonate) was insignificant, indicating that most of the amorphous calcium carbonate had converted to crystalline calcium carbonate.

[107] The intermediate peak at 874 cm-1 is commonly observed during the conversion process of calcium sulfonate-based greases. Depending on small variations in the grease being manufactured, this intermediate peak can be observed within the range of about 872 cm-1 to 877 cm-1. For ease of documentation, this intermediate peak will henceforth be assigned a value of 874 cm-1 with the understanding that the previously mentioned variation is normal within batches of calcium sulfonate-based grease. Complete conversion to the desirable dispersion of crystalline calcium carbonate (calcite) is typically evidenced by the elimination of the original amorphous calcium carbonate peak at 862 cm-1, and confirmation of a single new peak at about 882 cm-1. The intermediate peak at about 874 cm-1 that occurs during the conversion process is typically first formed and then eliminated when the conversion is complete. However, added powdered calcium carbonate as used in these examples will form a peak at about 874 cm-1 in calcium sulfonate-based greases. Thus, when powdered calcium carbonate is added before conversion, complete conversion will be evidenced by a TFIV spectrum showing a single peak at about 882 cm-1 with a small shoulder at about 874 cm-1. The heat was removed and the batch was cooled to 71.1°C (160°F). Then the mixing was stopped, and the batch remained at rest for about 16 hours.

[108] The following morning the batch was heated again to 87.8°C (190°F) to 93.3°C (200°F) with mixing. When the target temperature range was reached, the IVTF spectrum did not change. In an effort to drive the conversion, as shown by the IVTF spectrum, to completeness, another 25.53 grams of ORH was added followed by 60.0 grams of water in which 0.6 grams of sodium hydroxide had been dissolved. After about 2 hours and 45 minutes of mixing at 87.8°C (190°F) to 93.3°C (200°F), IVTF spectroscopy indicated that only modest progress in conversion had occurred. The primary peak at 882 cm-1 and the small, very poorly resolved peak at 872 cm-1 were still present and appeared unchanged from the previous IVTF spectrum. However, most of the remaining amorphous calcium carbonate was converted. This was evidenced by the fact that the shoulder at 862 cm-1 was almost eliminated. The total time to conduct the conversion process to this point was approximately 9 hours and 12 minutes.

[109] Despite the conflicting IVTF results, the decision was made to proceed with the next step in manufacturing this grease. Consequently, 2.46 grams of glacial acetic acid was added and allowed to mix in the grease for 30 minutes. Then 24.61 grams of a 75% solution of phosphoric acid in water was slowly added and allowed to mix and react. The grease was then heated to 199°C (390°F) to 204°C (400°F). During this time, the batch did not thin but retained an evident grease texture. In this respect, this grease of Example 7 was different from previous examples that had the observed and surprising rheopectic property. When the grease reached the target maximum temperature, the heating blanket was removed from the mixer and the grease was allowed to cool while continuing to mix. When the temperature was about 71.1°C (160°F), a portion of the batch was removed and allowed to cool at rest. The unworked penetration of this unmilled sample was 265. The remaining batch was allowed to cool without mixing until the next morning. Then the batch was heated to about 71.1°C (160°F) and then passed once through a laboratory-scale colloidal mill with a clearance setting of 127 micrometers (0.005 inch). Once the ground grease had cooled, the unworked and worked penetrations at 60 strokes were measured. The milled grease had an unworked penetration of 255 and a worked penetration measured at 60 strokes of 279. The drip points of the unmilled and milled greases were 305°C (581°F) and 304°C (580°F), respectively . The percentage of superbasified oil-soluble calcium sulfonate in the final grease was 36.88%.

[110] Three things that must be emphasized regarding the grease in this example. First, although the thickening performance was not as good as that of any of the greases in the previous examples, the dripping point was significantly improved compared to those greases in which the same poor quality superbasified calcium sulfonate was used. As already discussed in relation to the grease of Example 6, the use of superbasified magnesium sulfonate can improve the drip point in greases in which poor quality superbasified calcium sulfonate is used and in which the complexing acids are those used in that grease (acid 12-hydroxystearic acid, acetic acid, and phosphoric acid). The Example 7 grease of the present invention used the same poor quality superbasified calcium sulfonate and used the same complexing acids as the Example 6 grease. However, this Example 7 grease demonstrates that even so, further improvement of the drip point can be obtained when ORH is incorporated into the grease in the manner described.

[111] A second thing to emphasize is that the previously observed rheopectic property was not observed in this grease of Example 7. On the contrary, the unmilled and milled greases had similar penetration consistencies, indicating minimal grinding effect. This may be considered to be the opposite effect to that which was observed in the greases of Examples 1, 3, 4, 5, and 6. In those examples, the unmilled grease had little or no significant grease texture, but became a very thick grease. fine when ground. Grinding had a profound effect on the penetration consistency of those greases. Even in typical prior art sulfonate-based greases (in which the surprising rheopectic property has not been verified) grinding is typically required to achieve a smooth grease finish and impart some increase in thickening as evidenced by the penetration value. However, this was not the case with the grease from Example 7, which did not benefit from milling. Thus, the use of a glycerol derivative (ORH in this example) provides the potential advantage of providing an optimally dispersed thickening system in the grease without the typically required grinding process step.

[112] The third thing to emphasize is that the IVTF spectra during the manufacture of this grease, and also the IVTF spectra of the final grease, indicated that most of the ORH had hydrolyzed with the resulting 12-hydroxystearic acid that reacts with calcium carbonate to form the corresponding calcium salt-based thickening component.

[113] Example 8 - Another calcium sulfonate/magnesium sulfonate complex grease was manufactured similar to the grease of previous Example 5 of the present invention. However, there were two significant differences. First, 12-hydroxystearic acid was not added. Instead, glycerol monooleate (MOG) was added in a total amount that provided oleic acid groups in an amount that was the molar equivalent of the 12-hydroxystearic groups in the grease of Example 5. The amount of MOG added before conversion was 33% of the total amount of MOG added, with the remaining amount added after conversion but before heating to maximum temperature. Second, a small amount of sodium hydroxide was dissolved in the water that was added to the grease after the conversion process. The concentration of sodium hydroxide (on an unreacted basis) in the final grease was 0.04%. This is a form of the alkali metal hydroxide addition method described in U.S. Patent No. 9,976,102, which was also used in the grease of Example 7, but not in the manufacture of the greases of Examples 1 to 6 of the present invention.

[114] Additionally, the batch size of this grease was about twice that of the greases of Examples 1 to 6. Like the greases of Examples 5 and 7, this grease did not use any hexylene glycol as a conventional non-aqueous converting agent. Also like the greases of Examples 5 and 7, this grease did not have the superbasified calcium sulfonate and the superbasified magnesium sulfonate added with an initial amount of the base oil. Then the alkyl-predominantly-C12-benzenesulfonic acid (facilitating acid) was added.

[115] The grease was manufactured as follows: 618.6 grams of NBT 400 superbase oil-soluble calcium sulfonate was added to an open mixing vessel. Then 61.26 grams of superbasified magnesium sulfonate A were added and allowed to mix for 15 minutes followed by 680.1 grams of a group 1 neutral solvent type paraffinic base oil having a viscosity of about 600 SUS at 37.8° C (100°F). Note that the order of addition of magnesium sulfonate and base oil was reversed in relation to previous examples. This variation will have no effect on the final grease because only non-reactive mixing must occur at this point in the procedure. NBT 400 superbasified oil-soluble calcium sulfonate was a calcium sulfonate of poor quality as defined by our recently published U.S. Patent No. 9,458,406. Unheated mixing began using a planetary mixer with paddles. Then 62.52 grams of a predominantly C12-alkyl benzenesulfonic acid (facilitating acid) were added. After mixing for 20 minutes, 151.51 grams of finely divided calcium carbonate with an average particle size below 5 microns was added and allowed to mix for 20 minutes. Then 17.12 grams of glycerol monooleate (MOG) was added followed by 1.81 grams of glacial acetic acid. Then 81.49 grams of water was added and the batch was heated to 87.8°C (190°F) to 93.3°C (200°F). When heating began, the batch quickly thickened. However, it quickly thinned out when the temperature reached 71.1°C (160°F). Another 10.0 grams of water was added while it was being heated to 87.8°C (190°F) to 93.3°C (200°F). Approximately by the time the batch had reached the target temperature range, it had become very thin with no significant grease texture. Approximately by the time the batch had reached the target temperature range, it had become very thin with no significant grease texture.

[116] Over the next approximately two hours, four portions of water totaling 44 grams were added to the batch as IVTF spectroscopy indicated that water was being reduced due to evaporation. During this time, the IVTF indicated that conversion was occurring slowly. However, only minor thickening was evident. The batch was bubbling in a manner that had not been observed in the grease of previous Example 7. After the two hours of mixing at 87.8°C (190°F) to 93.3°C (200°F), the IVTF spectrum was no longer progressing toward conversion. The IVTF peak at 882 cm-1 was dominant. However, there was a smaller but clear peak at around 874 cm-1. Also, a small amount of the original peak at 862 cm-1 (due to amorphous calcium carbonate) was still present as an observable shoulder. Another 36.24 grams of MOG was added followed by 57.8 grams of water in which 0.68 grams of sodium hydroxide had been dissolved. After almost an hour, IVTF indicated that the conversion process had significantly progressed but was not yet complete. The peaks at 874 cm-1 and 862 cm-1 were smaller but were not being eliminated with additional mixing. The appearance of the batch had also been improved, with a significant grease structure now evident. Since it appeared that the conversion process had stopped with no further progress being made, 2.77 grams of acetic acid was added and allowed to react for 30 minutes. Then 33.96 grams of a 75% solution of phosphoric acid in water was slowly added and allowed to mix and react. The grease was then heated to 199°C (390°F) to 204°C (400°F). During this time, the batch had thinned approximately by the time it had reached 149°C (300°F). After reaching the maximum temperature range, the batch was cooled to about 71.1°C (160°F). The batch was still very thin with almost all of the grease structure gone. The batch was passed once through a laboratory-scale colloidal mill with the gap setting at 127 micrometers (0.005 inch). The final batch had an unworked penetration of 453, indicating that virtually no grease structure was present.

[117] As with the grease of previous Example 7, IVTF spectra during the manufacture of this grease and also the IVTF spectrum of the final product indicated that the MOG had hydrolyzed with the resulting oleic acid which reacts with calcium carbonate to form the corresponding thickening component based on calcium salt.

[118] Example 9 - Since the previous Example 8 failed to provide an acceptable grease structure, another calcium sulfonate/magnesium sulfonate complex grease was manufactured similar to the grease of previous Example 8. Similarly to the grease in Example 8, 12-hydroxystearic acid was not added. Glycerol monooleate (MOG) was added instead. Also like the grease of Example 8, this grease had the superbasified calcium sulfonate and the superbasified magnesium sulfonate added with an initial amount of the base oil. Then the predominantly C12-alkyl-benzenesulfonic acid (facilitating acid) was added.

[119] However, there were several differences between this grease and the grease of previous Example 8. First, sodium hydroxide was not used in this grease. Second, after the conversion process had stopped, hexylene glycol was added as a non-aqueous converting agent. Third, the heating steps during conversion were different, allowing for some higher temperatures for part of the total conversion process. Finally, only the initial MOG portion was added before conversion. No second portion of MOG was added after conversion.

[120] The grease was manufactured as follows: 622.7 grams of NBT 400 superbase oil-soluble calcium sulfonate was added to an open mixing vessel. Then 62.27 grams of superbasified magnesium sulfonate A were added and allowed to mix for 15 minutes followed by 689.0 grams of a group 1 neutral solvent type paraffin base oil having a viscosity of about 600 SUS at 37.8° C (100°F). NBT 400 superbasified oil-soluble calcium sulfonate was a calcium sulfonate of poor quality as defined by our recently published U.S. Patent No. 9,458,406. Unheated mixing began using a planetary mixer with paddles. Then 62.59 grams of an alkyl-predominantly-C12-benzenesulfonic acid (facilitating acid) was added. After mixing for 20 minutes, 152.86 grams of finely divided calcium carbonate with an average particle size below 5 microns was added and allowed to mix for 20 minutes. Then 18.54 grams of glycerol monooleate (MOG) was added followed by 2.04 grams of glacial acetic acid. Then 88.25 grams of water was added and the batch was heated to 87.8°C (190°F) to 93.3°C (200°F). When heating began, the batch quickly thickened. However, it quickly thinned out when the temperature reached 73.9°C (165°F). Approximately by the time the batch had reached the target temperature range, it had become very thin with no significant grease texture. IVTF showed that the dominant conversion-related peak was at 874 cm-1 with most of the original peak at 862 cm-1 still present as a pronounced shoulder. This behavior was similar to the grease of previous Example 8. Over the next approximately 5 hours, six portions of water totaling 267 grams were added to the batch as IVTF spectroscopy indicated that the water was being decreased due to evaporation. During this time, IVTF indicated that the conversion was occurring slowly. After about 45 minutes at 87.8°C (190°F) to 93.3°C (200°F), a peak at about 882 cm-1 began to appear. After 2 hours of the 5 hours of mixing in the target temperature range, the IVTF peak at 882 cm-1 became larger than the intermediate peak at 874 cm-1. The batch became progressively thicker during these 5 hours of mixing. However, there was still a smaller but resolved peak at 874 cm-1. After 5 hours of mixing at 87.8°C (190°F) to 93.3°C (200°F), the batch was heated to 127°C (260°F). During this heating stage, it was evident that the batch bubbled due to the boiling of the water. Then two additions of water totaling 107 grams were added. The peak at 874 cm-1 was only very slightly reduced. The batch was stirred and the heating mantle was removed to allow cooling to occur. Mixing was stopped, and the batch was allowed to stand for 16 hours.

[121] Then the batch was heated back to 110°C (230°F) and 20 grams of water was added. The batch temperature was lowered to about 93.3°C (200°F). After 90 minutes, another 61.3 grams of water was added. An IVTF spectrum indicated that significant additional progress had been made in the conversion process. A 29.65-gram portion of hexylene glycol was added to the batch. Within a few minutes, the batch had noticeably thickened. An IVTF spectrum showed that almost all peaks related to conversion had disappeared except for the peak at 882 cm-1. Only one shoulder observable at 874 cm-1 was present. After adding another 41.89 grams of water and stirring for about 30 minutes, IVTF spectra indicated that the conversion was complete. The total time to conduct the conversion process to this point was about 7 hours and 50 minutes.

[122] Then 3.19 grams of acetic acid was added followed by 32.95 grams of 12-hydroxystearic acid. The batch was allowed to mix at 87.8°C (190°F) to 93.3°C (200°F) for 30 minutes. Then 34.09 grams of a 75% solution of phosphoric acid in water was slowly added and allowed to mix and react. The grease was then heated to 199°C (390°F) to 204°C (400°F). During this time, the batch did not thin like the batch in previous Example 8. After reaching the maximum temperature range, the batch was cooled to about 71.1°C (160°F). The batch was passed once through a laboratory-scale colloidal mill with the gap setting at 127 micrometers (0.005 inch). The final batch had an unworked penetration of 295 and a worked penetration measured at 60 strokes of 315. The drip point was 288°C (500°F). The percentage of superbasified calcium sulfonate in the final grease was 36.42%.

[123] As with previous Example 8, IVTF spectra during the manufacture of this grease and also the IVTF spectrum of the final product indicated that most of the MOG had hydrolyzed with the resulting oleic acid which reacts with the calcium carbonate to form the corresponding thickening component based on calcium salt. As can be seen, this Example 9 grease had a thickening yield much greater than the thickening yield of the previous Example 8 grease. In fact, the thickening yield was essentially the same as that of the grease in Example 7 that used ORH instead of MOG.

[124] Example 10 - Another calcium sulfonate/magnesium sulfonate complex grease was manufactured similar to the grease of previous Example 9 of the present invention. However, there were several important differences. First, glycerol monostearate (MEG) was used instead of glycerol monooleate. Second, 12-hydroxystearate and acetic acid were both added before and after the conversion in the same manner as carried out in the greases of Examples 1 to 6. In making this change, the primary complexing acids both before and after the conversion were acid 12. -hydroxystearic and acetic acid. Any complexing acid forming during MEG hydrolysis (to form stearic acid) was considered to be additional complexing acid rather than a 12-hydroxystearic acid substituent. Like the grease of previous Example 9, hexylene glycol was added as the primary converting agent only after the conversion process had proceeded to the point where no further progress was being made.

[125] The grease was manufactured as follows: 620.18 grams of NBT 400 superbase oil-soluble calcium sulfonate was added to an open mixing vessel. Then 62.26 grams of superbasified magnesium sulfonate A were added and allowed to mix for 15 minutes followed by 689.9 grams of a group 1 neutral solvent type paraffinic base oil having a viscosity of about 600 SUS at 37.8° C (100°F). NBT 400 superbasified oil-soluble calcium sulfonate was a calcium sulfonate of poor quality as defined by our recently published U.S. Patent No. 9,458,406. Unheated mixing began using a planetary mixer with paddles. Then 70.61 grams of an alkyl-predominantly-C12-benzenesulfonic acid (facilitating acid) were added. After mixing for 20 minutes, 155.38 grams of finely divided calcium carbonate with an average particle size below 5 microns was added and allowed to mix for 20 minutes. Then 17.48 grams of glycerol monostearate (MEG) was added. This was followed by the addition of 16.63 grams of 12-hydroxystearic acid and 1.74 grams of glacial acetic acid. Then 80.4 grams of water was added and the batch was heated to 87.8°C (190°F) to 93.3°C (200°F). When heating began, the batch quickly thickened. However, it had thinned out when the temperature reached 90.6°C (195°F). As the batch continued to mix in the target temperature range, it began to thicken. Over the next 3.5 hours, five portions of water totaling 100.0 grams were added. At the end of this time, IVTF spectra showed that the conversion was predominantly complete. However, there was a small but obvious peak at 874 cm-1 that had not yet been eliminated. also, a small but evident shoulder at 662 cm-1 indicated that some of the amorphous calcium carbonate had not yet been converted. A 30.0 gram portion of water and a 28.40 gram portion of hexylene glycol were added to the batch. Within a few minutes, the batch had further thickened. Within 30 minutes, an IVTF spectrum showed that the conversion was essentially complete. The total time to conduct the conversion process to this point was about 4 hours and 34 minutes. The batch was cooled and mixing was stopped.

[126] After 16 hours, the batch was heated back to 87.8°C (190°F) to 93.3°C (200°F). Then 32.46 grams of 12-hydroxystearic acid and 61.25 grams of water were added to the batch and allowed to mix. Then 3.22 grams of acetic acid was added. The batch was mixed for 30 minutes. Then 32.66 grams of a 75% solution of phosphoric acid in water was slowly added and allowed to mix and react. The grease was then heated to 199°C (390°F) to 204°C (400°F) and then cooled to 71.1°C (160°F). During this time, the batch did not thin out. On the contrary, as the batch cooled it became much thicker. Two portions of the same paraffin base oil totaling 181.68 grams were added to the batch. A portion of the batch was passed once through a laboratory-scale colloidal mill with the gap setting at 127 micrometers (0.005 inch). The final unmilled grease had an unworked penetration of 235 and a worked penetration measured at 60 strokes of 235. The drip point was 308°C (587°F). The milled grease had an unworked penetration of 221 and a worked penetration measured at 60 strokes of 247. The drip point was 308°C (587°F). The percentage of superbasified calcium sulfonate in the final grease was 32.4%. Using the customary inverse linear relationship between penetration and percent superbase calcium sulfonate concentration, this unmilled grease of Example 10 would have had a percent superbase calcium sulfonate concentration of 28.7% if its penetration values were those same as those of the grease of previous Example 7. Similarly, this milled grease of Example 10 would have had the same percentage concentration of superbasified calcium sulfonate of 28.7% if its worked penetration value was the same as that of the grease of Example 7.

[127] As with the greases of previous Examples 7 to 9, the IVTF spectra during the manufacture of this grease and also the IVTF spectrum of the final product indicated that the majority of the added glycerol derivative had hydrolyzed with the chain fatty acid resulting long reaction that reacts with calcium carbonate to form the corresponding thickening component based on calcium salt.

[128] Three things must be emphasized concerning the results of this grease. First, on an equal penetration basis, MEG appears to be much more effective than MOG with respect to thickening yield. Second, grinding has little or no effect on the actual thickening yield as evidenced by the similar penetrations of unmilled and milled greases. In fact, using the grease from Example 7 as the basis for comparison, the unmilled and milled grease from Example 10 have exactly the same thickening yield. This is similar to what was observed in Example 7. Finally, once again the drip point is higher than that which has typically been observed when calcium carbonate-based calcium sulfonate complex greases are manufactured with calcium sulfonate. superbasified calcium of poor quality and with 12-hydroxystearic acid, acetic acid, and phosphoric acid as complexing acids. These three observations are surprising and unexpected.

[129] The ability of the glycerol derivative (MEG) to disperse the thickener as grinding does not provide significant additional thickening can also be observed using oscillatory rheometry. FIGURE 1 provides the results of an oscillatory rheometry amplitude sweep at 25°C of the unmilled and milled greases of Example 10. The storage modulus (G') curves represent the structural effect of the dispersed phase (thickening system) of the grease during the test. The loss modulus (G”) curves represent the structural effect of the continuous, non-dispersed phase (base oil system) of the grease during the test. As can be seen, the G' and G" curves of the unmilled grease overlap the G' and G" curves of the milled grease. Additionally, the crossing points for the G' and G" curves, which is a measurement of the mechanical stability of the grease structure, are the same for both unmilled and milled greases. This information confirms the observation that the glycerol derivative has imparted a grinding effect on the grease without the actual use of mechanical grinding.

[130] Example 11 - In order to further determine the role of the conventional non-aqueous converting agent on the properties of the final grease, another batch was manufactured identical to the grease of previous Example 10 except for one thing: the grease used only half the amount of hexylene glycol. The total time to drive the conversion process to its end point was 4 hours and 46 minutes. The final unmilled grease had an unworked penetration of 255 and a worked penetration measured at 60 strokes of 257. The drip point was 282°C (540°F). The milled grease had an unworked penetration of 225 and a worked penetration measured at 60 strokes of 247. The drip point was 297°C (567°F). The percentage of superbasified calcium sulfonate in the final grease was 32.82%. Comparing the penetration values of this grease with the penetration values of the grease from previous Example 10, it can be seen that half the concentration of the non-aqueous converting agent slightly reduced the thickening yield of the unmilled grease, but had no significant effect on the yield. ground grease thickener.

[131] Example 12 - Another calcium sulfonate/magnesium sulfonate grease was manufactured similar to the grease of previous Example 10 of the present invention. However, there were several important differences. First, the facilitating acid was added after the initial base oil and the superbasified calcium sulfonate but before the superbasified magnesium sulfonate. This is a form of the facilitating acid delay method described in U.S. Patent No. 10,087,388. Note that this technique was also used in previous baseline Examples 2 and 3, but was not used in Examples 7 to 11 of the present invention. Second, double the total amount of powdered calcium carbonate was added. The amount before conversion was almost the same as in Example 10. However, a second equal portion was added after conversion. Finally, the total amount of 12-hydroxystearic acid was correspondingly increased.

[132] The grease was manufactured as follows: 616.66 grams of NBT 400 superbasified oil-soluble calcium sulfonate was added to an open mixing vessel followed by 506.64 grams of a neutral solvent-type paraffinic base oil from the group 1 having a viscosity of about 600 SUS at 37.8°C (100°F). NBT 400 superbasified oil-soluble calcium sulfonate was a calcium sulfonate of poor quality as defined by our recently published U.S. Patent No. 9,458,406. Unheated mixing began using a planetary mixer with paddles. Then 61.63 grams of a predominantly C12-alkyl benzenesulfonic acid (facilitating acid) were added. After mixing for 20 minutes, 61.39 grams of superbasified magnesium sulfonate A was added and allowed to mix for 15 minutes. Then 149.27 grams of finely divided calcium carbonate with an average particle size below 5 microns was added and allowed to mix for 20 minutes. Then 17.68 grams of glycerol monostearate (MEG) was added. This was followed by the addition of 54.05 grams of 12-hydroxystearic acid and 1.66 grams of glacial acetic acid. Then 81.70 grams of water was added and the batch was heated to 87.8°C (190°F) to 93.3°C (200°F). When heating began, the batch quickly thickened. However, approximately by the time the batch had reached the target temperature range, it had thinned out.

[133] Over the next 3 hours and 39 minutes, seven portions of water totaling 262.8 grams were added. During this mixing time the batch progressively became thicker until it was very thick. However, IVTF scans had shown that the conversion process had stopped. IVTF spectra at the end of the mixing time of 3 hours and 39 minutes showed only a small peak at 882 cm-1 (representing complete conversion). A larger peak at 874 cm-1 had a large, broad shoulder centered on the original peak at 862 cm-1 (amorphous calcium carbonate). This IVTF spectrum typically indicates only a small amount of conversion with almost no visible grease structure. However, the batch was very thick with a well-developed grease structure. This behavior has never been observed before in any of the prior exemplary greases represented by any of the U.S. patent applications or published patent equivalents thereof mentioned herein. Since the conversion, as represented by IVTF, appeared to be stalled, a 30.1-gram portion of water and a 31.68-gram portion of hexylene glycol were added to the batch. Within a few minutes, the batch had further thickened. Due to the fact that the batch had become too thick, an additional 67.86 grams of the same paraffinic base oil was added. However, after 30 minutes, an IVTF spectrum showed no further change. Because of this, it was determined that the conversion process continued to the point it was likely to reach. The total time to achieve this conversion length was 4 hours and 22 minutes. The batch was cooled and mixing was stopped.

[134] After 16 hours, the batch was heated back to 87.8°C (190°F) to 93.3°C (200°F). Due to the fact that the batch had become too thick, 80.06 grams of the same paraffinic base oil were added. Then 154.56 grams of the same powdered calcium carbonate was added and allowed to mix for 20 minutes. Then 107.15 grams of 12-hydroxystearic acid and 2.87 grams of acetic acid were added to the batch and allowed to mix until no further thickening was observed. During this time, two portions of the same paraffin base oil totaling 194.03 grams were added. Then 32.95 grams of a 75% solution of phosphoric acid in water was slowly added and allowed to mix and react. The grease was then heated to 199°C (390°F) to 204°C (400°F). During this time, the batch thinned somewhat but retained a grease-like consistency. Once the batch temperature reached 199°C (390°F), the heating blanket was removed, and the batch was cooled to 71.1°C (160°F). As the batch cooled, it became thick again. A portion of 82.41 grams of the same paraffinic base oil was added. When the batch reached 71.1°C (160°F), a portion of the batch was passed once through a laboratory-scale colloidal mill with the gap setting at 127 micrometers (0.005 inch). The rest of the batch was stored without grinding. The final unmilled grease had an unworked penetration of 225 and a worked penetration measured at 60 strokes of 267. The drip point was 297°C (567°F). The milled grease had an unworked penetration of 235 and a worked penetration measured at 60 strokes of 273. The drip point was 283°C (541°F). The percentage of superbasified calcium sulfonate in the final grease was 27.75%. The IVTF peaks related to final grease conversion were the same as those that had been observed when conversion had been considered to have reached the point that was possible.

[135] Like the greases of previous Examples 7 to 11 of the present invention, the IVTF spectra during the manufacture of this grease and also the IVTF spectrum of the final product indicated that the majority of the added glycerol derivative had hydrolyzed with the fatty acid resulting long-chain compound that reacts with calcium carbonate to form the corresponding calcium salt-based thickening component.

[136] Four things must be emphasized in regard to the results of these greases. First, this grease had a superior thickening performance compared to all greases in the previous Examples when compared on an equal worked penetration basis. Second, re-milling had little or no effect on the actual thickening yield as evidenced by the similar penetrations of the unmilled and milled greases. This is similar to what was observed in Examples 7, 10, and 11. Third, the good thickening yield occurred despite an IVTF spectrum that would normally be interpreted as evidence of poor conversion by anyone commonly skilled in the art. Finally, once again, the dripping point is higher than that which has typically been observed when calcium carbonate-based calcium sulfonate complex greases are manufactured with poor quality, acid-containing overbase calcium sulfonates. -hydroxystearic acid, acetic acid, and phosphoric acid as complexing acids. In fact, the unmilled grease had a higher drip point than the drip point of the milled grease. These four observations are surprising and unexpected.

[137] Additional information regarding the effect of the glycerol derivative (MEG) on grease thickener dispersion can be observed using oscillatory rheometry. An amplitude sweep was performed at 25°C. Results as provided in FIGURE 2. Each of the G' and G" curves for the unmilled and milled greases do not exactly overlap, but they are very close to each other. This corresponds to the penetration values of the two greases where the ground grease was slightly harder than the unground grease. However, the crossing point of the G' and G" curves for the unmilled and milled greases are almost at the same relative shear strain value, indicating that the structural stabilities of both greases are similar.

[138] Example 13 - Another calcium sulfonate/magnesium sulfonate complex grease was manufactured similar to the grease of previous Example 12 of the present invention. There was only one difference: the delay in the facilitating acid technique used in the grease of previous Example 12 was not used. Instead, the facilitating acid was added after the superbasified calcium sulfonate, the superbasified magnesium sulfonate, and the initial base oil were added and mixed.

[139] It should also be noted that before conversion, this grease of Example 13 is essentially the same as the grease of Example 10 before conversion except for one factor: this grease of Example 13 had a concentration of A12HE (12-hydroxystearic acid ) much higher before conversion compared to the grease from Example 10.

[140] The grease was manufactured as follows: 625.5 grams of superbasified oil-soluble calcium sulfonate of NBT 400 was added to an open mixing vessel followed by 505.7 grams of a neutral solvent type paraffinic base oil from the group 1 having a viscosity of about 600 SUS at 37.8°C (100°F). NBT 400 superbasified oil-soluble calcium sulfonate was a calcium sulfonate of poor quality as defined by our recently published U.S. Patent No. 9,458,406. Unheated mixing began using a planetary mixer with paddles. Then 62.4 grams of superbasified magnesium sulfonate A was added and allowed to mix for 15 minutes. Then 61.2 grams of an alkyl-predominantly-C12-benzenesulfonic acid (facilitating acid) was added. After mixing for 20 minutes, 150.9 grams of finely divided calcium carbonate with an average particle size below 5 micrometers was added and allowed to mix for 20 minutes. Then 17.43 grams of glycerol monostearate (MEG) was added. This was followed by the addition of 52.80 grams of 12-hydroxystearic acid and 1.45 grams of glacial acetic acid. Then 82.10 grams of water was added and the batch was heated to 87.8°C (190°F) to 93.3°C (200°F). When heating began, the batch quickly thickened. However, approximately when the batch reached the target temperature range, it thinned out.

[141] Over the next approximately 6 hours, nine portions of water totaling 270 grams were added. During this mixing time the batch progressively became thicker. However, IVTF scans had shown that the conversion process had stopped. IVTF spectra at the end of the mixing time of almost 6 hours showed only a small peak at 882 cm-1 (representing complete conversion). A larger peak at 874 cm-1 had a large, broad shoulder centered on the original peak at 862 cm-1 (amorphous calcium carbonate). This IVTF spectrum typically indicates only a small amount of conversion with almost no visible grease structure. However, the batch was very thick with a well-developed grease structure. This is the same spectral behavior in IVTF and thickening observed in the grease of previous Example 12. However, as already mentioned, this behavior has never been observed before in any of the exemplary greases represented by any of the U.S. patent applications or published patent equivalents thereof mentioned in this document. The heating mantle was removed, and the batch was allowed to mix for about 25 minutes. Then the mixing was stopped, and the batch remained at rest for 16 hours. The batch was then heated with mixing to 87.8°C (190°F) to 93.3°C (200°F). Since the conversion as represented by IVTF appeared to be stalled, an 80-gram portion of water and a 31.3-gram portion of hexylene glycol were added to the batch. Within a few minutes, the batch had additionally thickened to an excessive amount. Because the batch had become too thick, three portions of the same paraffinic base oil totaling 456.87 grams were added. After one hour, an IVTF spectrum showed that the conversion was virtually complete. The original amorphous calcium carbonate peak at 862 cm-1 was eliminated. Only one shoulder remained discernible at 874 cm-1. The total conversion time from 87.8°C (190°F) to 93.3°C (200°F) to this point was 8 hours and 18 minutes.

[142] After allowing the batch to mix for about an additional hour, 42.02 grams of water and 149.39 grams of the same powdered calcium carbonate were added and allowed to mix for 20 minutes. Then 107.39 grams of 12-hydroxystearic acid and 3.93 grams of acetic acid were added to the batch and allowed to mix until no further thickening was observed. Then 34.61 grams of a 75% solution of phosphoric acid in water was slowly added and allowed to mix and react. The grease was then heated to 199°C (390°F) to 204°C (400°F) and then cooled. As the grease cooled, it appeared to become thicker. Three portions of the same paraffin base oil totaling 212.02 grams were added and allowed to mix into the grease. When the batch reached 71.1°C (160°F), a portion of the batch was passed once through a laboratory-scale colloidal mill with the gap setting at 127 micrometers (0.005 inch). The final unmilled grease had an unworked penetration of 289 and a worked penetration measured at 60 strokes of 293. The drip point was 337.8°C (640°F). The milled grease had an unworked penetration of 161 and a worked penetration measured at 60 strokes of 213. The drip point was 339°C (642°F). The percentage of superbasified calcium sulfonate in the final grease was 25.29%. Interestingly, peaks related to conversion of the final milled grease showed that the shoulder at 874 cm-1 had grown to a very poorly resolved peak of about half the height of the dominant peak at 882 cm-1.

[143] As with the greases of previous Examples 7 to 12, the IVTF spectra during the manufacture of this grease and also the IVTF spectrum of the final product indicated that the majority of the added glycerol derivative had hydrolyzed with the chain fatty acid long product that reacts with calcium carbonate to form the corresponding calcium salt-based thickening component.

[144] Several things must be emphasized concerning the results of this grease. First, the behavior during conversion was the same as the grease of previous Example 12 until the conventional non-aqueous converting agent (hexylenic glycol) was added. However, when hexylene glycol was added, this grease of Example 13 quickly advanced the conversion process, at least as indicated by the IVTF spectra, to a nearly complete state. In contrast, the IVTF spectra of the grease from previous Example 12 did not change significantly after the addition of the non-aqueous converting agent. Second, this grease had a significantly higher thickening performance than the grease of previous Example 12. This was true for both the unmilled grease and the milled grease. In fact, using the customary inverse linear relationship between the worked penetration and the percent concentration of superbase calcium sulfonate, the milled grease of Example 13 would have a percent concentration of superbase calcium sulfonate of 19.2% if additional base oil had been added. has been added to drive the worked penetration to a value of 280 (a penetration value in the center of the penetration variation range for a Grade 2 grease). This value is higher (lower) than any other value of any calcium carbonate-based calcium sulfonate grease documented in the previously mentioned patent applications and published patent equivalents thereof. This includes all greases in those patent applications regardless of whether or not they used superbase magnesium sulfonate or a conventional non-aqueous converting agent. Third, the thickening yield of the milled grease of Example 13 was much better than the thickening yield of the corresponding unmilled grease. Although this is normal behavior of prior art sulfonate-based greases, this is not what has been observed in the greases of previous Examples 7 to 12 that use an added glycerol derivative. Finally, the drip points were very high for both the unmilled and milled greases of Example 13. These are the highest drip point values for any calcium carbonate-based calcium sulfonate grease documented in any of the applications. previously mentioned patents and published patent equivalents thereof when a poor quality superbasified calcium sulfonate was used and when the complexing acids were 12-hydroxystearic acid, acetic acid, and phosphoric acid. This includes all such previously documented greases whether or not they used superbase magnesium sulfonate or a conventional non-aqueous converting agent.

[145] The only difference in the manufacturing process between this grease of Example 13 and the grease of previous Example 12 was the relative order of addition of the superbasified magnesium sulfonate and the facilitating acid, that is, whether it was used or not used. the delay technique after addition of facilitating acid described in U.S. Patent No. 10,087,388. Therefore, all of the above differences between these two greases have to be due to whether or not that process technique was used. Why this is so has not yet been determined. Certainly, these differences with respect to improvements in thickening yield, IVTF spectral behavior, dripping point, and optimal thickener dispersion without grinding (when present) are surprising and would not have been assumed by a person commonly skilled in the art.

[146] Example 14 - Since the ground grease of previous Example 13 had a very hard consistency, a 759.3 gram portion of it was returned to the mixer after it was cleaned. The ground grease was stirred and heated to about 71.1°C (160°F). Then two portions of the same paraffinic base oil totaling 85.1 grams were added and allowed to mix in the grease for 45 minutes. Once complete mixing had occurred, the grease was removed and allowed to cool until the next day. The grease had an unworked penetration of 299. Its worked penetration measured at 60 strokes was also 299. The drip point was 337°C (638°F). The percentage of superbasified calcium sulfonate was 22.8%. Using the customary inverse linear relationship between worked penetration and percent concentration of superbase calcium sulfonate, the grease of Example 14 would have had a percent concentration of superbase calcium sulfonate of 24.3% if the same base oil had been added so driving the worked penetration to a value of 280 (a penetration value in the center of the penetration variation range for a Grade 2 grease, which was used as a comparison value in Example 13). Although this value is not as good a thickening yield as the estimated 19.2% value calculated in previous Example 13 (which may be due to the softening that occurred in the milled grease of Example 13 during stirring when additional base oil was added) , the final thickening yield of this grease of Example 14 is one of the best values reported for any calcium carbonate-based calcium sulfonate grease documented in any of the previously mentioned patent applications and published patent equivalents thereof. This includes all greases in those patent applications regardless of whether or not they used superbase magnesium sulfonate or a conventional non-aqueous converting agent.

[147] Example 15 - Another grease was manufactured similar to previous Example 12 of the present invention. There were only three significant differences between this grease and the grease from Example 12 above. First, when this grease was heated to 87.8°C (190°F) to 93.3°C (200°F), the conversion process was not continued until it stopped (or appeared to stop from IVTF spectra) before addition of the primary non-aqueous converting agent hexylene glycol). In contrast, hexylene glycol was immediately added when the temperature reached 87.8°C (190°F). Second, when this grease was manufactured, only a first portion of powdered calcium carbonate was added before conversion. A second portion of powdered calcium carbonate was not added after conversion. Third, boric acid was also used in this grease as a complexing acid after conversion. Boric acid was not used in the grease of previous Example 12.

[148] The grease was manufactured as follows: 618.2 grams of NBT 400 superbasified oil-soluble calcium sulfonate was added to an open mixing vessel followed by 505.48 grams of a neutral solvent-type paraffinic base oil from the group 1 having a viscosity of about 600 SUS at 37.8°C (100°F). NBT 400 superbasified oil-soluble calcium sulfonate was a calcium sulfonate of poor quality as defined by our recently published U.S. Patent No. 9,458,406. Unheated mixing began using a planetary mixer with paddles. Then 62.90 grams of an alkyl-predominantly-C12-benzenesulfonic acid (facilitating acid) were added. After mixing for 20 minutes, 63.20 grams of superbasified magnesium sulfonate A was added and allowed to mix for 15 minutes. Then 150.53 grams of finely divided calcium carbonate with an average particle size below 5 microns was added and allowed to mix for 20 minutes. Then 17.42 grams of glycerol monostearate (MEG) was added. This was followed by the addition of 52.84 grams of 12-hydroxystearic acid and 1.66 grams of glacial acetic acid. Then 79.81 grams of water was added and the batch was heated to 87.8°C (190°F) to 93.3°C (200°F). When heating began, approximately when the temperature had reached 37°C (98°F), a visible grease structure was evident. This grease structure continued to thicken as the temperature increased to 60.0°C (140°F). As the temperature continued to increase beyond 60.0°C (140°F), the batch began to become thicker. At approximately the time the temperature reached 87.8°C (190°F), no significant grease structure was visible.

[149] Once the batch reached 87.8°C (190°F), a 30.1-gram portion of hexylene glycol was added to the batch. IVTF spectra indicated that the batch was still full of water, so no additional water was added. The batch began to visibly thicken within a few minutes. After 20 minutes, the batch was extremely thickened. IVTF spectra showed a dominant peak at 882 cm-1 (representing complete conversion) and a very small but resolved peak at 874 cm-1 with the original peak at 862 cm-1 (amorphous calcium carbonate) having been eliminated. An additional 42 grams of water was added to replace water that had apparently been lost due to heating. Then two portions of the same paraffin base oil totaling 116.96 grams were added due to extreme thickening of the grease. After about 45 minutes, IVTF spectra indicated no further change except that water was not evident. The total conversion time from 87.8°C (190°F) to 93.3°C (200°F) to this point was 62 minutes.

[150] A 42.1-gram portion of water was added followed by 107.37 grams of 12-hydroxystearic acid and 3.26 grams of acetic acid. After no further reaction or further thickening was evident from these two complexing acids, 17.04 grams of boric acid slurried in 50 grams of hot water were added and allowed to react. Due to the increased thickening of the batch, another 70.96 grams of the same paraffinic base oil was added. Then 32.93 grams of a 75% solution of phosphoric acid in water was slowly added and allowed to mix and react. The mixture was then heated while continuing to mix. When the grease reached 149°C (300°F), 39.99 grams of a styrene-alkylene copolymer was added as a solid in crumbled form. The grease was further heated to about 199°C (390°F) by which time all of the polymer had melted and completely dissolved in the grease mixture. The heating mantle was removed and the grease was allowed to cool under continued stirring in open air. When the grease cooled to 149°C (300°F), 100.04 grams of food grade anhydrous calcium sulfate having an average particle size below 5 micrometers was added. When the grease temperature cooled to 200°F (93.3°C), 3.84 grams of an arylamine-based antioxidant was added. Then three portions of the same paraffin base oil totaling 248.41 grams were added. Immediately after this, 19.57 grams of PAO was added and allowed to mix into the grease. PAO had a viscosity of about 4 mm2/s (4 cSt) at 100°C. The heating mantle was removed and stirring was stopped. The batch was cooled and remained at rest for 16 hours.

[151] The next morning, the batch was heated to about 65.6°C (150°F) with stirring. Then four portions of the same paraffinic base oil totaling 235.45 grams were added and allowed to mix into the grease. A portion of the batch was removed without grinding and stored in a steel can. The remaining portion of the batch was passed once through a laboratory-scale colloidal mill with the gap setting at 127 micrometers (0.005 inch). The ground grease was then removed into a new clean mixing vessel and stirred at 65.6°C (150°F) for about 40 minutes. Then the ground and stirred grease was removed and stored in a steel can. The final unmilled grease had an unworked penetration of 245 and a worked penetration measured at 60 strokes of 259. The drip point was greater than 343°C (650°F). The ground and stirred grease had an unworked penetration of 259 and a worked penetration measured at 60 strokes of 271. The drip point was greater than 343°C (650°F). The percentage of superbasified calcium sulfonate in both grease samples was 24.75%.

[152] As with the previous examples, IVTF spectra during the manufacture of this grease and also the IVTF spectrum of the final product indicated that most of the added glycerol derivative had hydrolyzed with the resulting long-chain fatty acid that reacts with calcium carbonate to form the corresponding calcium salt-based thickening component.

[153] Four things must be emphasized concerning the results of this grease. First, this grease had a superior thickening performance compared to all the greases of the previous Examples except the grease of previous Example 14 when compared on an equal worked penetration basis. More specifically, this grease of Example 15 had a significantly higher thickening yield compared to the grease of Example 12. As mentioned at the beginning of this example, a main difference between Examples 12 and 15 is that in Example 15 hexylene glycol was added immediately after reach 87.8°C (190°F). In the grease of Example 12, hexylene glycol was not added until the conversion process at 87.8°C (190°F) to 93.3°C (200°F) had stopped according to the IVTF spectra after being heated for more than 3 hours. The immediate addition of the primary converting agent, hexylene glycol, is the likely reason for the improved yield. Second, the IVTF spectrum of this grease from Example 15 after the conversion process was significantly different from the IVTF spectrum of the grease from Example 12. The IVTF spectra from Example 15 indicated a more complete conversion as evidenced by only a small peak at 874 cm-1 remaining. This is in agreement with the improved yield of Example 15 compared to Example 12. Third, grinding once again had little effect on the actual thickening yield as evidenced by the similar worked penetrations measured at 60 strokes of the unmilled and milled greases. This is similar to what was observed in Examples 7, 10, 11, and 12. In fact, the unmilled grease of Example 15 had slightly harder penetration values than the milled grease of Example 15. Finally, high drip points were obtained regardless of whether the grease was ground or not.

[154] Again, the ability of the glycerol derivative (MEG) to disperse the thickener to the extent that grinding does not provide significant additional thickening can be observed using oscillatory rheometry. FIGURE 3 provides the results of an oscillatory rheometry amplitude sweep at 25°C of the unmilled and milled/agitated greases of Example 15. As can be seen, the G' and G” curves of the unmilled greases overlapped almost exactly. the G' and G” curves of the ground grease. Additionally, the crossing points for the G' and G" curves are the same for both unmilled and milled greases. This information confirms the observation that the glycerol derivative has imparted a grinding effect on the grease without the actual use of a mechanical mill.

[155] Example 16 - Another grease was manufactured similar to the grease of previous Example 15, with two notable exceptions. First, hydrogenated castor oil (ORH) was used instead of glycerol monostearate (MOG). The ORH was the same material used in the grease of previous Example 7. It was added at a level that provided approximately the same equivalence of 12-hydroxystearic acid as the MEG that was added in Example 15. Second, a first portion of calcium carbonate was added before conversion and a second portion was added after conversion. , instead of all the calcium carbonate being added before conversion as in Example 15.

[156] The grease was manufactured as follows: 618.4 grams of superbasified oil-soluble calcium sulfonate of NBT 400 was added to an open mixing vessel followed by 500.02 grams of a neutral solvent-type paraffinic base oil from the group 1 having a viscosity of about 600 SUS at 37.8°C (100°F). NBT 400 superbasified oil-soluble calcium sulfonate was a calcium sulfonate of poor quality as defined by our recently published U.S. Patent No. 9,458,406. Unheated mixing began using a planetary mixer with paddles. Then 61.73 grams of a predominantly C12-alkyl benzenesulfonic acid (facilitating acid) were added. After mixing for 20 minutes, 63.53 grams of superbasified magnesium sulfonate A was added and allowed to mix for 15 minutes. Then 150.00 grams of finely divided calcium carbonate with an average particle size below 5 microns was added and allowed to mix for 20 minutes. Then 20.33 grams of hydrogenated castor oil (ORH) was added. This was followed by the addition of 52.78 grams of 12-hydroxystearic acid and 1.54 grams of glacial acetic acid. Then 81.00 grams of water was added and the batch was heated to 87.8°C (190°F) to 93.3°C (200°F). When heating began, at approximately the time the temperature had reached 37°C (99°F), a remarkable gelatinous structure had formed. As the batch temperature reached 62.8°C (145°F), this gelatinous structure began to thin. At approximately the time the temperature reached 71.1°C (160°F), the batch was very thin with no notable gel or grease structure evident.

[157] Once the batch reached 87.8°C (190°F), IVTF spectra indicated that the original peak at 862 cm-1 had diminished and that a larger peak at 874 cm-1 had already been formed. A 30.3-gram portion of hexylene glycol was added to the batch. After 10 minutes, a visible grease structure had formed. After another 36 minutes, IVTF spectra showed a dominant peak at 882 cm-1 (representing complete conversion) and a smaller but resolved peak at 874 cm-1 with the original peak at 862 cm-1 (amorphous calcium carbonate). deleted. Then four portions of the same paraffinic base oil totaling 242.12 grams were added due to extreme thickening of the grease. Another 42 grams of water was also added to replace the water that had been lost due to evaporation. The batch became noticeably thicker, so that another 27.94 grams of the same paraffinic base oil was added. After another 10 minutes, two more portions of the same paraffin base oil totaling 69.13 grams were added along with 61 grams of water. The batch was heated to 104°C (220°F), then 80 grams of water was added. After 5 minutes, IVTF spectra indicated that no further changes had occurred. The entire original peak at 862 cm-1 (amorphous calcium carbonate) was eliminated. The dominant peak was at 882 cm-1 (representing complete conversion), and a smaller but resolved peak at 874 cm-1 was still present. The total time from 87.8°C (190°F) to 93.3°C (200°F) before adding the second portion of powdered calcium carbonate was 1 hour and 53 minutes. However, the conversion-related peaks in IVTF reached their final state only after about 67 minutes. Therefore, the total conversion time was no more than 67 minutes.

[158] A portion of 149.84 grams of the same powdered calico carbonate was added and allowed to mix into the grease. Due to continued thickening of the batch, another 48.08 grams of the same paraffinic base oil was added. Then 107.27 grams of 12-hydroxystearic acid and 3.12 grams of acetic acid were added. Significant additional thickening occurred, so that 39.44 grams of the same paraffinic mineral oil was added. After no reaction or further thickening from these two complexing acids was evident, 16.92 grams of boric acid slurried in 50 grams of hot water were added and allowed to react. Then 32.17 grams of a 75% solution of phosphoric acid in water was slowly added and allowed to mix and react. The mixture was then heated while continuing to mix. When the grease reached 149°C (300°F), 40.05 grams of a styrene-alkylene copolymer was added as a solid in crumbled form. The grease was further heated to about 199°C (390°F) at which time all of the polymer was melted and completely dissolved in the grease mixture. The heating mantle was removed and the grease was allowed to cool by continued stirring in open air. When the grease cooled to 149°C (300°F), 100.59 grams of food-grade anhydrous calcium sulfate having an average particle size below 5 micrometers was added. Then 19.35 grams of a PAO were added. PAO had a viscosity of about 4 mm2/s (4 cSt) at 100°C. When the temperature of the grease was cooled to about 93.3°C (200°F), 4.08 grams of an arylamine-based antioxidant was added. Then three portions of the same paraffinic base oil totaling 153.61 grams were added and allowed to mix into the grease. The heating mantle was removed and stirring was stopped. The batch cooled down and remained at rest for 16 hours.

[159] The next morning, the batch was heated to about 65.6°C (150°F) with stirring. Then four portions of the same paraffin base oil totaling 204.17 grams were added and allowed to mix into the grease. A portion of the batch was removed without grinding and stored in a steel can. The remaining portion of the batch was passed once through a laboratory-scale colloidal mill with the gap setting at 127 micrometers (0.005 inch). The ground grease was then removed into a new clean mixing vessel and stirred at 65.6°C (150°F) for about 45 minutes. Then the ground and stirred grease was removed and stored in a steel can. The final unmilled grease had an unworked penetration of 247 and a worked penetration measured at 60 strokes of 263. The drip point was greater than 343°C (650°F). The milled and stirred grease had an unworked penetration of 255 and a worked penetration measured at 60 strokes of 263. The drip point was greater than 343°C (650°F). The percentage of superbasified calcium sulfonate in both grease samples was 22.44%.

[160] As with the previous examples, IVTF spectra during the manufacture of this grease and also the IVTF spectrum of the final product indicated that most of the added glycerol derivative (ORH) had hydrolyzed with the resulting long-chain fatty acid. which reacts with calcium carbonate to form the corresponding calcium salt-based thickening component.

[161] Four things must be emphasized concerning the results of this grease. First, this grease had a superior thickening performance compared to all greases from the previous Examples including the milled grease from previous Example 14 when compared on an equal worked penetration basis. Comparing this grease of Example 16 specifically to the grease of Example 14, the grease of Example 16 had a worked penetration that was more than 30 points harder than the milled grease of Example 14 even though the percentage of superbasic calcium sulfonate in both greases was essentially the same value. This is all the more remarkable because this is true for the unmilled grease of Example 16. Second, the IVTF spectrum of this grease of Example 16 after the conversion process was similar to that of the grease of Example 15. Both the excellent yield and the peak Unusual doublet conversion rates were characteristic of the grease of Example 15 (using MEG) and the grease of Example 16 (using ORH). Third, grinding, again, had no effect on the actual thickening yield as evidenced by the similar worked penetrations measured at 60 strokes of the unmilled and milled greases. This is similar to what was observed in Examples 7, 9, 10, 11, 12, and 15. Finally, high drip points were obtained regardless of whether the grease was ground or not.

[162] Again, the ability of the glycerol derivative (MEG) to disperse the thickener to the extent that milling provides no significant thickening can also be observed using oscillatory rheometry. FIGURE 4 provides the results of an oscillatory rheometry amplitude sweep at 25°C of the unmilled and milled/agitated greases of Example 16. As can be seen, the G' and G” curves of the unmilled greases overlap the of G' and G” of the ground grease. Additionally, the crossing points of the G’ and G” curves are the same for both unmilled and milled greases. This information continues to confirm the observation that the glycerol derivative has imparted a grinding effect on the grease without the actual use of a mechanical mill.

[163] A summary of the greases of Examples 7 to 16 is provided below in Tables 5 to 9. Table 5 provides a summary of compositional information, Table 6 a summary of processing methods used, Table 7 a summary of data and IVTF conversion behavior, and Table 8 is a summary of penetration values and drip points for each example before grinding (unmilled grease) and after grinding, but when the grease was initially manufactured and after a period of storage. Additional testing was performed on the greases of Examples 12 to 16. The results of that test are provided below in Table 9.

[164] As can be seen from the data in Tables 5 to 9, certain embodiments of the various compositional and process variables of the present invention provide better performance and structural stability characteristics than other embodiments. The greases of Examples 15 and 16 are notable in this respect, as those of ordinary skill in the art will recognize.

[165] Example 17 is another baseline example that does not include an addition of glycerol derivative in accordance with preferred embodiments of the invention. Examples 17 to 23 use calcium hydroxyapatite added as a calcium-containing base to react with complexing acids, as described in U.S. Patent No. 9,458,406 (and further described in the '101, '102, '387, '388, and '391).

[166] Example 17 - A grease was manufactured based on a calcium hydroxyapatite technology from U.S. patent No. 9,458,406. This grease serves as a baseline for comparison. This grease did not use any added glycerol derivative. Also, this grease did not use any superbase magnesium sulfonate. Only superbasified calcium sulfonate was used. The delayed addition method of converting agent was not used. A different commercially available superbasified calcium sulfonate was used for this grease compared to the previous examples. Also, a different commercially available base oil was used. Different non-aqueous converting agent (propylene glycol) was used. Boric acid was not used. Much less of the styrene-alkylene copolymer was used. The grease was heated to a maximum temperature of just 171°C (340°F). Finally, an amine phosphate-based additive and a different antioxidant were added near the end of the manufacturing procedure.

[167] The grease was manufactured as follows: 544.0 grams of superbasified oil-soluble calcium sulfonate of NBT 400 was added to an open mixing vessel with 661.7 grams of a white paraffinic mineral base oil of purity according to the Pharmacopoeia from the United States of America having a viscosity of about 352 SUS at 37.8°C (100°F). The superbasified calcium sulfonate was an NSF HX-1 approved food grade superbasified calcium sulfonate suitable for manufacturing NSF H-1 approved food grade greases and was of good quality as defined by the '406 patent. Unheated mixing began using a planetary mixer with paddles. Then 48.91 grams of a predominantly C12-alkyl-benzenesulfonic acid were added. After mixing for 20 minutes, 91.98 grams of calcium hydroxyapatite having an average particle size below 5 micrometers and 7.44 grams of food grade purity calcium hydroxide having an average particle size below 5 micrometers were added. and allowed to mix for about 30 minutes. Then 1.73 grams of glacial acetic acid and 21.76 grams of 12-hydroxystearic acid were added and allowed to mix for 10 minutes. Then 100.56 grams of finely divided calcium carbonate with an average particle size below 5 microns was added and allowed to mix for about 5 minutes. Then, 70.6 grams of water and 27.05 grams of propylene glycol were added. The mixture was heated until the temperature reached 87.8°C (190°F) to 93.3°C (200°F). Visible thickening began when the temperature reached about 74.4°C (166°F). An IVTF spectrum obtained at that time showed a dominant peak at 882 cm-1 (representing complete conversion) and a smaller but resolved peak at 874 cm-1 with a very pronounced shoulder at 862 cm-1 (representing amorphous calcium carbonate original).

[168] When the temperature reached 90.6°C (195°F), IVTF spectra showed that the dominant peak at 882 cm-1 (representing complete conversion) had increased. The peak at 874 cm-1 was still resolved but had decreased. The shoulder at 862 cm-1 (representing the original amorphous calcium carbonate) had also decreased. For the next four hours the temperature was maintained at 87.8°C (190°F) to 93.3°C (200°F). During this time seven more portions of water totaling 243 grams were added to replace the water lost due to evaporation. The IVTF spectra continued to progress during this time until the shoulder at 862 cm-1 was eliminated, indicating that conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) had occurred. However, when the final amount of this amorphous calcium carbonate was eliminated, the intermediate peak at 874 cm-1 increased until it was as large as the peak at 882 cm-1. These two peaks appeared like a very poorly resolved doublet. Since this IVTF spectrum had not changed during the final 20 minutes, the conversion process was considered complete. The total conversion time, based on mixing time from 87.8°C (190°F) to 93.3°C (200°F), was 3 hours and 14 minutes.

[169] Then 32.2 grams of water and 15.14 grams of the same calcium hydroxide were added and allowed to mix for 10 minutes. Then 55.45 grams of 12-hydroxystearic acid were added and allowed to react. Due to significant thickening, two portions of the same paraffin base oil totaling 191.22 grams were added and allowed to mix. Then 3.22 grams of acetic acid was added. After these two complexing acids had reacted, 38.00 grams of a 75% solution of phosphoric acid in water was slowly added and allowed to mix and react. The mixture was then heated with an electric heating mantle while continuing to stir. When the grease reached 149°C (300°F), 40.13 grams of a styrene-alkylene copolymer was added as a solid in crumbled form. The grease was further heated to about 171°C (340°F) at which time all of the polymer was melted and completely dissolved in the grease mixture. The heating mantle was removed and the grease was allowed to cool by continued stirring in open air. When the grease cooled to 149°C (300°F), 59.61 grams of food grade anhydrous calcium sulfate having an average particle size below 5 micrometers was added. As the grease continued to cool, it became increasingly thick. An additional 112.13 grams of the same paraffin base oil was added. When the temperature of the grease cooled to 93.3°C (200°F), 11.11 grams of a mixture of a high molecular weight phenolic antioxidant and arylamine-based antioxidant and 11.67 grams of a phosphate-based antioxidant of amine/an anti-rust additive were added. Two portions of the same base oil totaling 63.62 grams were added. Mixing continued until the grease reached a temperature of 65.6°C (150°F).

[170] A portion of the batch was removed without grinding and stored in a steel can. A portion of this unmilled grease was spread onto a clean thin steel plate and allowed to cool to about 25°C (77°F). This portion of the unmilled grease had an unworked penetration of 269 and a worked penetration measured at 60 strokes of 287. The remaining portion of the batch that was still in the mixer was passed once through a laboratory scale colloidal mill with the setting of space in 127 micrometers (0.005 inch). A portion of this ground grease was spread onto a clean thin steel plate and allowed to cool under air to about 25°C (77°F). This portion of the milled grease had an unworked penetration of 253 and a worked penetration measured at 60 strokes of 267. The remaining milled grease was then transferred to a new clean mixing vessel and stirred at 65.6°C (150°F). for approximately 45 minutes. A portion of this ground and stirred grease was spread onto a clean thin steel plate and allowed to cool under air to about 25°C (77°F). This portion of the ground and stirred grease had an unworked penetration of 261 and a worked penetration measured at 60 strokes of 281. The remaining portion of the ground and stirred grease was removed and stored in a steel can. About 24 hours later, both greases (unmilled and milled/shaken) in the cans were reassessed for penetration. The final unmilled grease had an unworked penetration of 245 and a worked penetration measured at 60 strokes of 285. The drip point was greater than 343°C (650°F). The ground and stirred grease had an unworked penetration of 267 and a worked penetration measured at 60 strokes of 279. The drip point was greater than 343°C (650°F). The percentage of superbasified calcium sulfonate in both grease samples was 25.85%.

[171] It should be noted that the doublet peak in IVTF observed at the end of the conversion process of this grease was retained in the final grease. However, compared to other greases manufactured using this specific batch of superbasified calcium sulfonate in previous tests, this unusual behavior is believed to be due to the aging of the superbasified calcium sulfonate used. At the time of these tests, the batch of superbasified calcium sulfonate was about 3 years old (it was new at the time of the previous tests).

[172] Example 18 - Another complex calcium sulfonate grease was manufactured similar to the baseline grease of previous Example 17. There were only two significant differences: ORH was added before conversion in a manner similar to Example 16; and a second portion of propylene glycol (non-aqueous converting agent) was added about 53 minutes after the target conversion temperature range was reached.

[173] The grease was manufactured as follows: 541.6 grams of NBT 400 superbasified oil-soluble calcium sulfonate was added to an open mixing vessel with 662.5 grams of a white paraffinic mineral base oil of U.S. Pharmacopoeia purity. United States of America having a viscosity of about 352 SUS at 37.8°C (100°F). The superbasified calcium sulfonate was an NSF HX-1 approved food grade superbasified calcium sulfonate suitable for manufacturing NSF H-1 approved food grade greases and was of good quality as defined by our recently published U.S. Patent No. 9,458,406. Unheated mixing began using a planetary mixer with paddles. Then 49.11 grams of an alkyl-predominantly-C12-benzenesulfonic acid were added. After mixing for 20 minutes, 92.03 grams of calcium hydroxyapatite having an average particle size below 5 micrometers and 7.32 grams of food grade purity calcium hydroxide having an average particle size below 5 micrometers were added. and allowed to mix for about 30 minutes. Then 2.00 grams of glacial acetic acid and 21.61 grams of 12-hydroxystearic acid were added and allowed to mix for 10 minutes. Then 100.11 grams of finely divided calcium carbonate with an average particle size below 5 microns was added and allowed to mix for about 5 minutes. Then 20.14 grams of hydrogenated castor oil (ORH) was added and allowed to mix into the grease. Then, 72.4 grams of water and 26.22 grams of propylene glycol were added. The heating blanket was applied and the heating process began. An initial TFIV spectrum was obtained within the first two minutes. The spectrum indicated that the conversion process had already begun with a large peak at about 874 cm-1. The original peak at 862 cm-1 (representing the original amorphous calcium carbonate) appeared as a large, broad shoulder almost as high as the peak at 874 cm-1. The peak at 874 cm-1 had a very small onset of a shoulder at about 882 cm-1.

[174] The mixture was heated until the temperature reached 87.8°C (190°F) to 93.3°C (200°F). When the batch temperature had reached 87.8°C (190°F), another IVTF spectrum was obtained. The results show a dominant peak at 882 cm-1 (representing complete conversion) and a smaller but resolved peak at 874 cm-1 with a very pronounced shoulder at 862 cm-1 (representing the original amorphous calcium carbonate). This IVTF spectrum appeared very similar to the IVTF spectrum of the previous baseline grease at this point in the manufacturing process. During the following 53 minutes of mixing two portions of water totaling 64.3 grams were added to replace the water lost due to evaporation. The IVTF spectrum had not changed. Consequently, another 15.92 grams of propylene glycol was added. About an hour after the second addition of propylene glycol, and after another addition of 43 grams of water, the IVTF spectra began to change. The intermediate peak at 874 cm-1 began to increase, and the shoulder at 862 cm-1 began to decrease. When the batch had been mixed at 87.8°C (190°F) to 93.3°C (200°F) for another 6 hours after the second addition of propylene glycol, and after another eleven additions of water totaling about of 536 grams, IVTF spectra indicated that the conversion had reached its final state. The original amorphous calcium carbonate peak was eliminated. A very poorly resolved doublet peak remained at about 882 cm-1 and 874 cm-1. The peak at 874 cm-1 was almost as high as the peak at 882 cm-1. During these 6 hours of mixing, nine portions of the same paraffinic base oil totaling 284.24 grams were added due to the progressively increasing thickening of the batch. The total conversion time, based on the mixing temperature of 87.8°C (190°F) to 93.3°C (200°F), was just less than 7 hours.

[175] Then 20.26 grams of water and 15.04 grams of the same calcium hydroxide were added and allowed to mix for about 10 minutes. Then 55.52 grams of 12-hydroxystearic acid were added and allowed to react. Due to significant thickening, three portions of the same paraffinic base oil totaling 110.59 grams were added and allowed to mix. Then 3.00 grams of acetic acid was added. Due to further thickening, another 38.23 grams of the same paraffinic base oil was added and allowed to mix. After these two complexing acids had reacted, 37.31 grams of a 75% solution of phosphoric acid in water was slowly added and allowed to mix and react. The mixture was then heated with an electric heating mantle while continuing to stir. When the grease reached 149°C (300°F), 4.99 grams of a styrene-alkylene copolymer was added as a solid in crumbled form. The grease was further heated to about 171°C (340°F) at which time all of the polymer was melted and completely dissolved in the grease mixture. The heating mantle was removed and the grease was allowed to cool by continued stirring in open air. When the grease cooled to 149°C (300°F), 60.00 grams of food grade anhydrous calcium sulfate having an average particle size below 5 micrometers was added. When the temperature of the grease was cooled to about 200°F (93.3°C), 9.65 grams of a mixture of a high molecular weight phenolic antioxidant and arylamine-based antioxidant and 10.04 grams of a base antioxidant amine phosphate base/an anti-rust additive were added. Two portions of the same base oil totaling 143.83 grams were added. Mixing continued until the grease reached a temperature of 65.6°C (150°F). Two portions of the same base oil totaling 46.45 grams were added and allowed to mix into the grease. The heating mantle was removed and stirring was stopped. The batch cooled down and remained at rest for 16 hours.

[176] The next morning, the batch was heated to about 65.6°C (150°F) with stirring. Since the batch was still very thick, another two portions of the same base oil totaling 66.8 grams were added and allowed to mix into the grease. A portion of the batch was removed without grinding and stored in a steel can. A portion of this unmilled grease was spread onto a clean thin steel plate and allowed to cool to about 25°C (77°F). This portion of the unmilled grease had an unworked penetration of 273 and a worked penetration measured at 60 strokes of 281. The remaining portion of the batch that was still in the mixer was passed once through a laboratory scale colloidal mill with the setting of space in 127 micrometers (0.005 inch). The total amount of this ground grease that was collected was 997.5 grams. A portion of this ground grease was spread onto a clean thin steel plate and allowed to cool under air to about 25°C (77°F). This portion of the ground grease had an unworked penetration of 255 and a worked penetration measured at 60 strokes of 263. The air-cooled sample was returned to the mixing vessel with the rest of the collected ground grease. An additional 57.62 grams of the same paraffinic base oil was added and allowed to mix at 65.6°C (150°F) for 45 minutes. A portion of this ground and stirred grease was spread onto a clean thin steel plate and allowed to cool under air to about 25°C (77°F). This portion of the ground and stirred grease had an unworked penetration of 291 and a worked penetration measured at 60 strokes of 299. The remaining portion of the ground and stirred grease was removed and stored in a steel can.

[177] About 24 hours later, both greases (unmilled and milled/shaken) in the cans were retested for penetration. The final unmilled grease had an unworked penetration of 263 and a worked penetration measured at 60 strokes of 285. The drip point was 327°C (621°F). The milled and stirred grease had an unworked penetration of 279 and a worked penetration measured at 60 strokes of 291. The drip point was 327°C (621°F). The percentage of superbasified calcium sulfonate in the unmilled grease was 22.49%. The percentage of superbasified calcium sulfonate in the ground grease was 21.26%.

[178] The IVTF spectrum of the final product indicated that a very small amount of unhydrolyzed glycerol derivative (ORH) was still present.

[179] Two things are notable about this grease of Example 18 compared to the baseline grease of Example 17. First, like the previous Example 17 grease, the doublet peak in IVTF observed at the end of the processing process conversion of this grease was retained in the final grease. Again, this is unusual behavior for such complex calcium sulfonate greases manufactured with this particular superbase calcium sulfonate, but it is believed to be due to aging of the superbase calcium sulfonate. Second, the conversion time for this grease was much longer than that of the baseline grease in Example 17.

[180] Additional information regarding the greases of Examples 17 and 18 can be provided by oscillatory rheometry. FIGURE 5 shows the results of an amplitude sweep of the unmilled greases of Examples 17 and 18. The effect of the glycerol derivative (ORH) on the grease of Example 18 can be seen in several ways. First, the initial values of G' and G" of both unmilled greases are almost identical although the grease of Example 18 had significantly less thickener (better yield). This compares the worked penetration values of these two greases. Also, the crossing points of the G’ and G” curves for both unmilled greases occur at almost the same relative shear strain. However, it appears that there is more structure formation in the base oil portion (G”) of the Example 18 grease compared to the Example 17 grease as shear strain increases. This is a likely effect of the ORH in this grease.

[181] FIGURE 6 shows the results of an amplitude sweep of the milled greases of Examples 17 and 18. Again, the effect of the glycerol derivative (ORH) on the grease of Example 18 can be seen in several ways . First, the initial values of G’ and G” of both milled greases reflect the small difference in their penetration values. Also, the crossing points of the G’ and G” curves of both milled greases occur at almost the same relative shear strain. Finally, structure formation in the base oil portion (G”) of the grease of Example 18 is much less than that observed in the unmilled grease.

[182] Example 19 - Another complex calcium sulfonate grease was manufactured similar to the grease of previous Example 18. There was only one significant difference: only 25% of the total required ORH was added before conversion. The remaining ORH was added immediately when the conversion process was considered complete.

[183] The grease was manufactured as follows: 545.0 grams of NBT 400 superbasified oil-soluble calcium sulfonate was added to an open mixing vessel with 663.1 grams of a white paraffinic mineral base oil of U.S. Pharmacopoeia purity. United States of America having a viscosity of about 352 SUS at 37.8°C (100°F). The superbasified calcium sulfonate was an NSF HX-1 approved food grade superbasified calcium sulfonate suitable for manufacturing NSF H-1 approved food grade greases and was of good quality as defined by our recently published U.S. Patent No. 9,458,406. Unheated mixing began using a planetary mixer with paddles. Then 49.34 grams of an alkyl-predominantly-C12-benzenesulfonic acid were added. After mixing for 20 minutes, 92.11 grams of calcium hydroxyapatite having an average particle size below 5 micrometers and 7.36 grams of food grade purity calcium hydroxide having an average particle size below 5 micrometers were added. and allowed to mix for about 30 minutes. Then 1.66 grams of glacial acetic acid and 21.66 grams of 12-hydroxystearic acid were added and allowed to mix for 10 minutes. Then 100.75 grams of finely divided calcium carbonate with an average particle size below 5 microns was added and allowed to mix for about 5 minutes. Then 5.00 grams of hydrogenated castor oil (ORH) was added and allowed to mix into the grease. Then, 71.47 grams of water and 26.59 grams of propylene glycol were added. The heating blanket was applied and the heating process began. During heating to 87.8°C (190°F), IVTF behavior was virtually identical to that of the batch of previous Example 18.

[184] When the batch temperature had reached 87.8°C (190°F), another IVTF spectrum was obtained. The results show a dominant peak at 882 cm-1 (representing complete conversion) and a smaller but resolved peak at 874 cm-1 with a very pronounced shoulder at 862 cm-1 (representing the original amorphous calcium carbonate). This IVTF spectrum appeared essentially identical to the IVTF spectrum of the previous Example 18 grease at this point in the manufacturing process. During the following 2 hours and 40 minutes ten portions of water totaling about 486 grams were added to replace the water that was being lost due to evaporation as the grease was being stirred at about 87.8°C (190°F). ). During that time, four portions of the same paraffinic base oil totaling 188.46 grams were also added as the batch continued to thicken. After 4 hours and 4 minutes at about 87.8°C (190°F), the conversion process was considered complete at the point that no additional changes were occurring in the IVTF spectra. The IVTF at this point was similar to that of the grease from previous Example 18 at this point - a very poorly resolved doublet.

[185] The remaining amount of required ORH, 15.04 grams, was added and allowed to melt and mix in the batch. Then 30.0 grams of water and 15.00 grams of the same calcium hydroxide were added and allowed to mix for about 10 minutes. Then 55.84 grams of 12-hydroxystearic acid were added and allowed to react. Due to significant thickening, 64.25 grams of the same paraffinic base oil was added and allowed to mix. Then 3.20 grams of acetic acid was added. After these two complexing acids had reacted, 37.13 grams of a 75% solution of phosphoric acid in water was slowly added and allowed to mix and react. The mixture was then heated with an electric heating mantle while continuing to stir. When the grease reached 149°C (300°F), 5.32 grams of a styrene-alkylene copolymer was added as a solid in crumbled form. The grease was further heated to about 171°C (340°F) at which time all of the polymer was melted and completely dissolved in the grease mixture. The heating mantle was removed and the grease was allowed to cool by continued stirring in open air. When the grease cooled to 149°C (300°F), 60.68 grams of food grade anhydrous calcium sulfate having an average particle size below 5 micrometers was added. When the temperature of the grease was cooled to about 93.3°C (200°F), 10.14 grams of a mixture of a high molecular weight phenolic antioxidant and arylamine-based antioxidant and 9.51 grams of a base antioxidant amine phosphate base/an anti-rust additive were added.

[186] The batch was cooled and allowed to stand for 16 hours. The next morning it was stirred and heated to about 54.4°C (130°F). Three portions of the same paraffinic base oil totaling 189.03 grams were added and allowed to mix in the grease for about 45 minutes. A portion of the batch was removed without grinding and stored in a steel can. The remaining portion of the batch that was still in the mixer was passed once through a laboratory-scale colloidal mill with the gap setting at 127 micrometers (0.005 inch). The ground grease was returned to the mixer and mixed at about 54.4°C (130°F) for 45 minutes. Then it was stored in a steel can.

[187] About 24 hours later, both greases (unmilled and milled/shaken) from the cans were evaluated for penetration and drip point. The final unmilled grease had an unworked penetration of 243 and a worked penetration measured at 60 strokes of 275. The drip point was >343°C (650°F). The ground and stirred grease had an unworked penetration of 233 and a worked penetration measured at 60 strokes of 259. The drip point was 341°C (646°F). The percentage of superbasified calcium sulfonate in both grease samples was 25.16%.

[188] The IVTF spectrum of the final product indicated that only a very small amount of unhydrolyzed glycerol derivative (ORH) was still present.

[189] Two things are notable about the grease of Example 19. First, the behavior in IVTF was almost identical to that of the greases of previous Examples 17 and 18. Second, the conversion time was significantly shortened for this grease compared to the grease of previous Example 18. By comparing the conversion times of the greases in Examples 17 to 19, it appears that the presence of ORH pre-conversion slows down the conversion process. When less ORH is added before starting the conversion process (Example 19), the conversion occurs in a shorter time. When more ORH is added before starting the conversion process (Example 18), the conversion takes longer. However, when the full amount of ORH is added before conversion, the thickening yield is significantly improved compared to adding only 25% of the total amount of ORH before conversion (Example 18 compared to Example 17). Also, when the full amount of ORH was added before conversion (Example 18), a second portion of the non-aqueous converting agent was required. This was not the case when only 25% of the total ORH was added before conversion (Example 19).

[190] A summary of the greases of Examples 17 to 19 is provided below in Table 10.

[191] Example 20 - Due to the fact that the superbasified calico sulfonate used in Example 17 (and 18 and 19) was aged and resulted in a long conversion time and a final doublet conversion peak pattern in IVTF that is not Consistent with the previous test, a new baseline example was fabricated in Example 20. The superbasified calcium sulfonate used in Example 20 was a newly manufactured supply of the same commercially available superbasified calcium sulfonate, supplied by the same manufacturer, as that used in Examples 17 to 19.

[192] This grease behaved very differently compared to the grease of previous Example 17. Approximately by the time the batch temperature had reached 87.8°C (190°F), a very firm grease structure had already formed. The IVTF spectrum showed only a single peak at about 882 cm-1 with a very small shoulder close to this peak. Virtually the entire peak at 862 cm-1 of the original amorphous calcium carbonate was eliminated. After 44 minutes at 87.8°C (190°F), the conversion was complete. The batch was completed in the same manner as the grease in previous Example 17.

[193] A portion of the batch was removed without grinding and stored in a steel can. The remaining portion of the batch that was still in the mixer was passed once through a laboratory-scale colloidal mill with the gap setting at 127 micrometers (0.005 inch). The ground grease was returned to the mixer and mixed at about 54.4°C (139°F) for 45 minutes. Then it was stored in a steel can.

[194] About 24 hours later, both greases (unmilled and milled/shaken) from the cans were evaluated for penetration and drip point. The final unmilled grease had an unworked penetration of 275 and a worked penetration measured at 60 strokes of 298. The drip point was >343°C (650°F). The ground and stirred grease had an unworked penetration of 267 and a worked penetration measured at 60 strokes of 289. The drip point was >343°C (650°F). The percentage of superbasified calcium sulfonate in both grease samples was 28.58%.

[195] Although the thickening performance of this grease of Example 20 was not as good as that of the grease of previous Example 17, it was similar to that of other identical batches of grease manufactured in previous years with samples of the same superbasified calcium sulfonate when those samples of the sulfonate of superbasified calcium have recently been manufactured. Similarly, the IVTF behavior during conversion of this batch of Example 20 was that which had previously been observed when similar grease batches were manufactured with newly manufactured superbasified calcium sulfonate. Consequently, this grease from Example 20 was used as the new baseline for comparison. The greases of Examples 17 to 19 were no longer used for such comparisons because it was obvious that the heavily aged superbasified calcium sulfonate had somehow caused unusual results. The following three examples used the new sample of superbasified calcium sulfonate that was used in this Example 20 grease.

[196] Example 21 - Another complex calcium sulfonate grease was manufactured that was similar to the grease of previous Example 18. ORH in its full quantity was added before the conversion process began. However, about 50% more of the primary non-aqueous converting agent (propylene glycol) was added with the initial water.

[197] The grease was manufactured as follows: 540.07 grams of NBT 400 superbasified oil-soluble calcium sulfonate was added to an open mixing vessel with 668.0 grams of a white paraffinic mineral base oil of U.S. Pharmacopoeia purity. United States of America having a viscosity of about 352 SUS at 37.8°C (100°F). The superbasified calcium sulfonate was an NSF HX-1 approved food grade superbasified calcium sulfonate suitable for manufacturing NSF H-1 approved food grade greases and was of good quality as defined in U.S. Patent No. 9,458,406. Unheated mixing began using a planetary mixer with paddles. Then 49.27 grams of a predominantly C12-alkyl-benzenesulfonic acid were added. After mixing for 20 minutes, 91.98 grams of calcium hydroxyapatite having an average particle size below 5 micrometers and 7.38 grams of food grade purity calcium hydroxide having an average particle size below 5 micrometers were added. and allowed to mix for about 30 minutes. Then 1.94 grams of glacial acetic acid and 21.59 grams of 12-hydroxystearic acid were added and allowed to mix for 10 minutes. Then 100.04 grams of finely divided calcium carbonate with an average particle size below 5 microns was added and allowed to mix for about 5 minutes. Then 20.00 grams of hydrogenated castor oil (ORH) was added and allowed to mix into the grease. Then, 71.35 grams of water and 39.95 grams of propylene glycol were added. The heating blanket was applied and the heating process began.

[198] When the batch temperature had reached 87.8°C (190°F), the IVTF spectrum showed a dominant peak at 882 cm-1 (representing complete conversion) and a shoulder at 874 cm-1 that was about half the height of the dominant peak. Also, there was a low shoulder at 862 cm-1 (representing the original amorphous calcium carbonate). After 30 minutes at 87.8°C (190°F), the amorphous shoulder at 862 cm-1 was eliminated. The shoulder peak at 874 cm-1 had increased in height to almost the same height as that of the peak at 882 cm-1. Both peaks had joined together to the point that they almost looked like a single peak. After one hour of mixing at 87.8°C (190°F), the IVTF peak conversion profile did not change. The conversion time was judged to be no more than one hour. During this one hour of mixing at about 87.8°C (190°F), three portions of water totaling 127.8 grams were added to replace the water lost due to evaporation. Also, 86.56 grams of the same paraffinic base oil was added due to increased thickening of the grease structure. For about an additional hour, the batch was stirred while maintaining the temperature between 87.8°C (190°F) and about 93.3°C (200°F). During this time, two more portions of the same paraffin base oil totaling 121.3 grams were added as the batch continued to thicken. Also, two portions of water totaling 87.14 grams were added to replace the water lost due to evaporation. At the end of this one hour, the IVTF spectrum had not changed.

[199] Then 42.88 grams of water and 15.02 grams of the same calcium hydroxide were added and allowed to mix for about 10 minutes. Then 55.63 grams of 12-hydroxystearic acid and 3.03 grams of acetic acid were added and allowed to react. Due to further thickening, another 91.23 grams of the same paraffinic base oil was added and allowed to mix. After these two complexing acids had reacted, 37.04 grams of a 75% solution of phosphoric acid in water was slowly added and allowed to mix and react. The mixture was then heated with an electric heating mantle while continuing to stir. When the grease reached 149°C (300°F), 5.01 grams of a styrene-alkylene copolymer was added as a solid in crumbled form. The grease was further heated to about 171°C (340°F) at which time all of the polymer was melted and completely dissolved in the grease mixture. The heating mantle was removed and the grease was allowed to cool by continued stirring in open air. When the grease cooled to 149°C (300°F), 59.96 grams of food-grade anhydrous calcium sulfate having an average particle size below 5 micrometers was added. When the temperature of the grease was cooled to about 200°F (93.3°C), 11.74 grams of a mixture of a high molecular weight phenolic antioxidant and arylamine-based antioxidant and 12.15 grams of a base antioxidant amine phosphate base/an anti-rust additive were added. Two portions of the same base oil totaling 93.87 grams were added. Mixing continued until the grease reached a temperature of 65.6°C (150°F). The heating mantle was removed and stirring was stopped. The batch cooled down and remained at rest for 16 hours.

[200] The next morning, the batch was heated to about 60.0°C (140°F) with stirring. A portion of the batch was removed without grinding and stored in a steel can. The remaining portion of the batch that was still in the mixer was passed once through a laboratory-scale colloidal mill with the gap setting at 127 micrometers (0.005 inch). The ground grease was returned to the mixer and mixed at about 54.4°C (139°F) for 45 minutes. Then it was stored in a steel can.

[201] About 24 hours later, both greases (unmilled and milled/shaken) from the cans were evaluated for penetration and drip point. The final unmilled grease had an unworked penetration of 239 and a worked penetration measured at 60 strokes of 275. The drip point was >343°C (650°F). The ground and stirred grease had an unworked penetration of 245 and a worked penetration measured at 60 strokes of 265. The drip point was >343°C (650°F). The percentage of superbasified calcium sulfonate in both grease samples was 25.32%.

[202] The IVTF spectrum of the final product indicated that only a very small amount of unhydrolyzed glycerol derivative (ORH) was still present.

[203] Four things are notable about this grease of Example 21 when compared with the baseline grease of previous Example 20. First, the thickening performance of this grease has been improved. Second, the conversion time was just a little longer. Third, ORH changed the conversion process as evidenced by the change in the final conversion peak profile. Finally, the penetration values of the unmilled and milled greases were almost the same. Therefore, grinding was not required to provide optimal dispersion of the thickening system, at least as determined by initial penetration values.

[204] Example 22 - Another complex calcium sulfonate grease was manufactured that was similar to the grease of previous Example 21. The only significant difference was that the delayed addition technique of non-aqueous converting agent was used. Propylene glycol was not added with the water initially added. Instead, it was added once the batch temperature had reached 87.8°C (190°F).

[205] During the initial heating and initial conversion, the IVTF spectrum behaved slightly different from that of the grease from previous Example 21. About 30 minutes after reaching 87.8°C (190°F), the conversion peak area showed an obvious doublet at about 882 cm-1 and 874 cm-1 with a significant low shoulder at 862 cm-1. After a total of 96 minutes of mixing at about 87.8°C (190°F), the shoulder at 862 cm-1 was eliminated. The final IVTF conversion peak profile showed that the peak at 874 cm-1 had actually become slightly taller in height than the peak at 882 cm-1. Instead of the peak at 874 cm-1 being a shoulder of the peak at 882 cm-1 (as was the case for the grease in Example 21), the peak at 882 cm-1 was a shoulder of the dominant peak at 874 cm-1 . Both peaks had joined together to the point that they almost looked like a single peak. Thus, the peak IVTF conversion profile of this grease from Example 22 was the mirror image of the peak IVTF conversion profile of the grease from Example 21. Further heating with additional amounts of water added to replace the water lost to evaporation did not additionally changed the conversion process. Consequently the batch was finished in the same manner as the previous Example 21.

[206] The next morning, the batch was heated to about 60.0°C (140°F) with stirring. A portion of the batch was removed without grinding and stored in a steel can. The remaining portion of the batch that was still in the mixer was passed once through a laboratory-scale colloidal mill with the gap setting at 127 micrometers (0.005 inch). The ground grease was returned to the mixer and mixed at about 54.4°C (139°F) for 45 minutes. Then it was stored in a steel can.

[207] About 24 hours later, both greases (unmilled and milled/shaken) from the cans were evaluated for penetration and drip point. The final unmilled grease had an unworked penetration of 247 and a worked penetration measured at 60 strokes of 269. The drip point was >343°C (650°F). The ground and stirred grease had an unworked penetration of 255 and a worked penetration measured at 60 strokes of 269. The drip point was >343°C (650°F). The percentage of superbasified calcium sulfonate in both grease samples was 22.21%.

[208] The IVTF spectrum of the final product indicated that only a very small amount of unhydrolyzed glycerol derivative (ORH) was still present.

[209] Three things are remarkable regarding this Example. First, the thickening performance of this grease was much more improved than that of the grease of previous Example 21. Second, as was commonly observed in previous Examples, the addition, prior to conversion, of a glycerol derivative (ORH) resulted in more than one final IVTF conversion peak. The conversion peak profile of this grease was the mirror image of the grease from previous Example 21 where the delayed addition technique of non-aqueous converting agent was not used. Finally, grinding had no effect on the worked penetration of the grease. The same improved thickening yield resulted regardless of whether or not the grease was milled.

[210] FIGURE 7 provides the results of an oscillatory rheometry amplitude sweep at 25°C of the unmilled and milled/agitated greases of Example 22. As can be seen, the G' curves of both greases essentially overlapped. one over the other. This compares identical worked penetrations of unmilled and milled greases. Perhaps the most interesting aspect of Figure 7 is that the point of intersection of the G' and G" curves of the unmilled greases is actually at a higher relative shear strain than that of the milled grease. This may indicate that the unmilled grease in the Example has more structural stability than the corresponding milled grease.

[211] Example 23 - Another complex calcium sulfonate grease was manufactured that was similar to the grease of previous Example 22. Like Example 22, this grease was manufactured by adding ORH before the conversion process began. This grease also used the converting agent delay method described in U.S. Patent Nos. 9,976,101 and 9,976,102. However, unlike the grease of Example 22, this grease was also manufactured using the facilitating acid delay method as described in U.S. Patent No. 10,087,388.

[212] The grease was manufactured as follows: 544.46 grams of NBT 400 superbasified oil-soluble calcium sulfonate was added to an open mixing vessel with 663.0 grams of a white paraffinic mineral base oil of U.S. Pharmacopoeia purity. United States of America having a viscosity of about 352 SUS at 37.8°C (100°F). The superbasified calcium sulfonate was an NSF HX-1 approved food grade superbasified calcium sulfonate suitable for manufacturing NSF H-1 approved food grade greases and was of good quality as defined by our recently published U.S. Patent No. 9,458,406. Unheated mixing began using a planetary mixer with paddles. Then 50.48 grams of an alkyl-predominantly-C12-benzenesulfonic acid (facilitating acid) was added. The batch was then heated with mixing to 87.8°C (190°F). This represents a delay in temperature adjustment after addition of the facilitating acid.

[213] When the temperature reached 87.8°C (190°F), 91.98 grams of calcium hydroxyapatite with an average particle size below 5 micrometers and 7.44 grams of calcium hydroxide of food grade purity having an average particle size below 5 micrometers were added and allowed to mix for about 30 minutes. These two reagents represented the next reactive ingredients added after the facilitating acid. Then 1.86 grams of glacial acetic acid and 21.64 grams of 12-hydroxystearic acid were added and allowed to mix for 10 minutes. Then 100.74 grams of finely divided calcium carbonate with an average particle size below 5 microns was added and allowed to mix for about 5 minutes. Then 19.99 grams of hydrogenated castor oil (ORH) was added and allowed to mix into the grease. The electric heating blanket was removed from the mixer for 5 minutes to allow the inner wall of the thermal mixer to equilibrate with the grease at about 87.8°C (190°F). Then 71.61 grams of water were added. The heating blanket was applied and the batch was mixed for 30 minutes. This represents a delay period of non-aqueous converting agent retention. When the 30 minute holding delay was finished, 41.02 grams of propylene glycol was added to the batch. Conversion time measurement began at this point, as discussed further below. After 63 minutes, the IVTF conversion peak profile showed a broad peak combined with multiple “humps” corresponding to peaks at 882 cm-1, 874 cm-1, and 862 cm-1. All three humps were of similar heights. During this time 42.4 grams of water were added to replace water lost due to evaporation. After another 30 minutes the original amorphous peak d 862cm-1 was eliminated. The IVTF conversion peak profile included a dominant peak at 882 cm-1 with a shoulder at about 874 cm-1 that was almost as high. This profile was almost identical to the IVTF conversion peak profile of the grease from previous Example 21. During the next 26 minutes, two portions of water totaling 79.07 grams were added to replace the water lost due to evaporation. Also, four portions of the same paraffinic base oil totaling 239.56 grams were added due to the increasing thickening of the grease. The IVTF conversion profile did not change during these 26 minutes. The conversion time was therefore determined to be no more than 159 minutes (2 hours, 39 minutes).

[214] Then 44.22 grams of water and 14.94 grams of the same calcium hydroxide were added and allowed to mix for about 10 minutes. Then 55.69 grams of 12-hydroxystearic acid and 3.19 grams of acetic acid were added and allowed to react. Due to additional thickening, additional portions of the same paraffinic base oil totaling 74.73 grams were added and allowed to mix. After these two complexing acids had reacted, 37.94 grams of a 75% solution of phosphoric acid in water was slowly added and allowed to mix and react. The mixture was then heated with an electric heating mantle while continuing to stir. When the grease reached 149°C (300°F), 5.00 grams of a styrene-alkylene copolymer was added as a solid in crumbled form. The grease was further heated to about 171°C (340°F) at which time all of the polymer was melted and completely dissolved in the grease mixture. The heating mantle was removed and the grease was allowed to cool by continued stirring in open air. When the grease cooled to 149°C (300°F), 60.03 grams of food-grade anhydrous calcium sulfate having an average particle size below 5 micrometers was added. When the temperature of the grease was cooled to about 200°F (93.3°C), 10.41 grams of a mixture of a high molecular weight phenolic antioxidant and arylamine-based antioxidant and 11.90 grams of a base antioxidant amine phosphate base/an anti-rust additive were added. Five more portions of the same base oil totaling 332.52 grams were added. Mixing continued until the grease reached a temperature of 65.6°C (150°F). The heating mantle was removed and stirring was stopped. The batch cooled down and remained at rest for 16 hours.

[215] The next morning, the batch was heated to about 60.0°C (140°F) with stirring. A portion of the batch was removed without grinding and stored in a steel can. The remaining portion of the batch that was still in the mixer was passed once through a laboratory-scale colloidal mill with the gap setting at 127 micrometers (0.005 inch). The ground grease was returned to the mixer. A sample of the ground grease was cooled on a steel plate. Unworked penetration was 245; the worked penetration was 257. This grease sample was returned to the mixer. The total weight of grease in the mixer was 1209.0 grams. Another 35.21 grams of the same paraffinic base oil was added to the mixer and the grease was at about 54.4°C (139°F) for 45 minutes. Then it was stored in a steel can.

[216] About 24 hours later, both greases (unmilled and milled/shaken) from the cans were evaluated for penetration and drip point. The final unmilled grease had an unworked penetration of 263 and a worked penetration measured at 60 strokes of 275. The drip point was >343°C (650°F). The percentage of superbasified calcium sulfonate was 22.8%. The ground and stirred grease had an unworked penetration of 253 and a worked penetration measured at 60 strokes of 265. The drip point was >343°C (650°F). The percentage of superbasified calcium sulfonate was 22.2%.

[217] The IVTF spectrum of the final product indicated that only a very small amount of unhydrolyzed glycerol derivative (ORH) was still present.

[218] FIGURE 8 provides the results of an oscillatory rheometry amplitude sweep at 25°C of the unmilled and milled/agitated greases of Example 23. As can be seen, the G' curves of both greases almost overlapped. one over the other. The G” curve of unmilled grease is actually higher than that of milled/agitated grease. This indicates that the structure provided by the base oil component of the unmilled grease of Example 23 is actually greater than that of the corresponding milled/agitated grease. Additionally, the crossing point of the G' and G" curves of the unmilled greases is actually at a higher relative shear strain than that of the milled grease. This is the same characteristic as that observed in the unmilled and milled greases of Example 22 above. This may indicate that the unmilled grease of Example 23 has greater structural stability than the milled grease of Example 23.

[219] A summary of the greases of Examples 20 to 23 with additional test results is provided in Tables 11 to 14. Table 11 provides a summary of compositional information, Table 12 a summary of processing methods used, Table 13 a summary of data and IVTF conversion behavior, and Table 14 a summary of penetration values and drip points for each example before grinding (unmilled grease) and after grinding, both when the grease was initially manufactured and after a storage period.

[220] For the purposes of consistency in comparison, the conversion times indicated in the Examples were measured from the time a batch reached 87.8°C (190°F) during the initial heating step, although in some cases the conversion may have started before reaching that temperature or may have stopped (or appeared to stop) based on IVTF data even after reaching that temperature. For example, in examples where water and conventional non-aqueous converting agent were added together at room temperature, some conversion would occur before reaching 87.8°C (190°F), but the conversion timer was not started until reaching 87.8°C (190°F). Additionally, in examples where a conventional non-aqueous converting agent was not initially added at 87.8°C (190°F), but rather was only added at 87.8°C (190°F) after the conversion (as determined by IVTF) had begun (or appeared to stop), the conversion timer started as soon as the batch reached 87.8°C (190°F) during the initial heating step, although there was a delay in the conversion process until the conventional non-aqueous converting agent is added.

Morphology of Converted Calcium Carbonate Crystal.

[221] Another interesting aspect of the greases from the previous examples refers to the crystalline morphology of the converted calcium carbonate. Calcium carbonate can potentially exist in three known morphologies: calcite, vaterite, and aragonite. Of these three, only calcite is stable. The other two are very unstable in relation to calcite.

[222] Several recently published research documents have described calcium sulfonate-based greases that have IVTF conversion peaks within the previously described intermediate range of about 872 cm-1 to 877 cm-1. These research documents have claimed that such intermediate peaks indicate that the converted calcium carbonate (originally present as amorphous calcium carbonate in superbasified calcium sulfonate) is vaterite and not calcite. If the IVTF spectrum shows a peak at about 882 cm-1 and another peak (or shoulder) in the middle range, these research documents claim that both calcite and vaterite are present. In all such research documents, this conclusion is based entirely and exclusively on the location of the IVTF peaks. However, such reasoning is extremely wrong, as anyone with a good knowledge of crystallography will understand.

[223] When a material (such as calcium carbonate) can exist in more than one crystalline morphology, IVTF spectroscopy will not provide a reliable method for determining which morphology is present. This is because the locations of the characteristic IVTF peaks can shift significantly depending on the chemical environment in which the dispersed crystals exist. The particle size of the dispersed crystals can also affect the locations of their characteristic IVTF spectral peaks. This may result in the possible wavenumber range of IVTF peaks characteristic of different crystal morphologies overlapping each other. The one reliable method for determining crystalline morphology is X-ray diffraction (XRD). XRD results are not affected by the chemical environment of the crystals or their size (as long as the crystal size is large enough to diffract X-rays). The X-ray diffraction pattern of a given inorganic crystalline material is a fingerprint that will always provide the correct identity of the present morphology or morphologies.

[224] These previous research documents do not report any XRD results on their calcium sulfonate-based greases. They don't even mention XRD. They just used IVTF spectra. In contrast, the exemplary greases in this patent application have been evaluated by XRD. In all such cases evaluated, only calcite was detected. No vaterite or aragonite were detected. Even in greases with extremely unusual and atypical IVTF spectra, such as the grease of Example 12, only calcite was detected by XRD.

[225] Without such XRD data, some might be enticed to consider the behavior of IVTF conversion peaks and theorize that the presence of superbasified magnesium sulfonate and/or glycerol derivative causes the conversion process to generate vaterite that only partially changes to calcite in the final grease. Additionally, they could theorize that the transient intermediate peak formed during the conversion of calcium sulfonate-based greases (without overbased magnesium sulfonate or glycerol derivative) is caused by vaterite or aragonite. However, XRD evaluation of the exemplary greases of this patent application excludes any such theories. Rather, the emergence of an intermediate IVTF peak during the conversion process and (sometimes) in the final grease must be due to calcite that is either from a different particle size range, differently surrounded, or both. This conclusion applies to at least greases within the variety of compositions and processes described within this patent application.

[226] Although the examples provided of the present invention fall predominantly into NLGI grade No. 1, No. 2, or No. 3, with grade No. 2 being the most preferred, it should further be understood that the scope of this present invention includes all NLGI consistency grades harder and softer than a No. 2 grade. However, for such greases in accordance with the present invention that are not of the NLGI No. 2 grade, their properties must be consistent with what would have would have been obtained if more or less base oil had been used to provide a No. 2 grade grease product, as will be understood by those commonly skilled in the art.

[227] Although this invention deals mainly with greases manufactured in open vessels, all examples are in open vessels, the magnesium sulfonate complex grease methods and compositions can also be used in closed vessels where heating under pressure is carried out. The use of pressurized vessels can result in thickening yields even better than those described in the examples of the present invention. For the purposes of this invention an open vessel is any vessel with or without a lid or hatch provided that such lid or top hatch is not steam tight so that significant pressure cannot be generated during heating. The use of such an open vessel with the lid or top hatch closed during the conversion process will help retain the required water content as a converting agent while generally allowing a conversion temperature at or even above the boiling point of water. Such higher conversion temperatures can result in further improvements of thickening yield for both simple and complex calcium sulfonate greases, as will be understood by those commonly skilled in the art.

[228] As used in the present invention: (1) amounts of dispersed calcium carbonate (or dispersed amorphous calcium carbonate) or residual calcium oxide or residual calcium hydroxide contained in the superbasified calcium sulfonate are by weight of the sulfonate superbasified calcium; (2) some ingredients are added in two or more separate portions and each portion may be described as a percentage of the total amount of that ingredient or a percentage by weight of the final grease; and (3) all other quantities (including total quantities) of ingredients identified as percentages or parts are the quantities added as an ingredient by weight of the final grease product, although the specific ingredient (such as water, or calcium-containing bases or hydroxides of alkali metals that react with other ingredients) may not be present in the final grease or may not be present in the final grease in the amount identified for addition as an ingredient. As used in the present invention "added calcium carbonate" means crystalline calcium carbonate that is added as a separate ingredient in addition to the amount of dispersed calcium carbonate contained in the superbasified calcium sulfonate. As used in the present invention "added calcium hydroxide" and "added calcium oxide" mean calcium hydroxide and calcium oxide, respectively, which are added as a separate ingredient in addition to the amount of residual calcium hydroxide and/or oxide. of residual calcium that may be contained in superbasified calcium sulfonate. As used in the present invention "added calcium-containing bases" refers to calcium-containing bases (such as added calcium carbonate and added calcium hydroxide) that are added as a separate ingredient(s).

[229] As used in the present invention to describe the invention (as opposed to how the term is used in prior art references), calcium hydroxyapatite means (1) the compound having the formula Ca5(PO4)3OH or (2) a mathematically equivalent formula (a) having a melting point of about 1,100°C or (b) specifically excluding mixtures of tricalcium phosphate and calcium hydroxide by such equivalent formula. As used in the present invention and the '406 patent, “poor” quality superbasified calcium sulfonate refers to any manufactured or commercially available superbasified calcium sulfonate that results in a superbasified calcium sulfonate grease having a drip point less than 302°C (575°F) when the superbasified calcium sulfonate grease is manufactured using added calcium carbonate as the only calcium-containing base added to react with complexing acids as described in the '265 patent, and similarly a superbasified calcium sulfonate of “Good” quality is one that results in a drip point of 302°C (575°F) or higher when manufactured using added calcium carbonate as described in the '265 patent.

[230] As used in the present invention, the term “thickening yield”, as it applies to the present invention, should have the conventional meaning, namely, the concentration of highly superbasified oil-soluble calcium sulfonate required to provide a grease with a specific desired consistency as measured by standard ASTM D217 or D1403 penetration tests commonly used in the manufacture of lubricating greases. As used in the present invention, “penetration value” refers to a worked penetration value measured at 60 strokes, unless an unworked penetration value is specifically described. Similarly, as used in the present invention, the “dripping point” of a grease should refer to the value obtained by using the ASTM D2265 standard dropping point test as commonly used in the manufacture of lubricating greases. Four Ball EP tests as described in the present invention shall refer to ASTM D2596. Four Ball Wear Tests as described in the present invention shall refer to ASTM D2266. Cone Oil Separation tests as described in the present invention must refer to ASTM D6184. Roll stability tests as described in the present invention must refer to ASTM D1831. As used in the present invention, "non-aqueous converting agent" means any converting agent other than water and includes such conventional converting agents that may contain some water as a diluent or an impurity. Superbasified magnesium sulfonate may be considered a non-aqueous non-conventional converting agent, but references in the present invention to “non-aqueous converting agent” refer to “conventional” non-aqueous converting agents, which do not include superbasified magnesium sulfonate. All amounts of ingredients or ratios of ingredients indicated in the present invention as a range include each individual amount or ratio within those ranges and any and all combinations of subsets within the ranges, including those subsets that overlap from a preferred range to a more preferred range. preferred. Those persons commonly skilled in the art will recognize after reading this specification, including the examples contained therein, that modifications and changes in the composition and in the methodology for manufacturing the composition may be carried out within the scope of the invention and it is intended that the scope of the invention described herein is limited only by the broadest interpretation of the appended claims to which the inventor is legally entitled.

Claims (40)

1. Method for manufacturing a sulfonate-based complex grease, characterized in that the method comprises the steps of: adding and mixing 33% or less of superbasified calcium sulfonate having amorphous calcium carbonate dispersed therein and water; adding and mixing 0.1 to 5% of one or more conventional non-aqueous converting agents after applying a converting agent delay period comprising: (1) a converting agent retention delay period wherein a mixture comprising the superbasified calcium and water is maintained at a temperature or within a range of temperatures for a period of time of at least 20 minutes or (2) a converting agent temperature adjustment delay period where the mixture comprising the calcium sulfonate superbasified and the water is heated or (3) a combination thereof; convert a mixture comprising superbasified calcium sulfonate, water and one or more conventional non-aqueous converting agents into a converted mixture by heating until conversion of the amorphous calcium carbonate, contained in the superbasified calcium sulfonate, into a form crystal clear; adding and mixing 1.25 to 18% of the total of one or more complexing acids before the conversion step, during the conversion step, or after the conversion step; adding and mixing 1 to 20% of the total of one or more calcium-containing bases before the conversion step, during the conversion step, or after the conversion step; and adding and mixing from 0.1 to 6% of the total of one or more glycerol derivatives as a reactive ingredient, one or more glycerol derivatives comprising (1) glycerol monooleate, (2) hydrogenated castor oil, (3 ) glycerol monostearate, (4) glycerol monostearate, or (5) a combination thereof; removing substantially all of the water by heating to a temperature sufficient to remove the water, after the steps of adding and mixing the one or more glycerol derivatives; where all percentages are by weight. 2. Method according to claim 1, characterized in that there is no grinding step. 3. Method according to claim 1, characterized by the fact that the step of adding and mixing one or more glycerol derivatives is prior to the conversion step and forms an acidic reaction product of the hydrolysis of one or more glycerol derivatives. glycerol; and wherein no alkali metal hydroxide is added; and wherein no glycerol derivative is added during or after the conversion step. 4. Method according to claim 1, characterized by the fact that one or more calcium-containing bases comprise added calcium carbonate, the method further comprising: grinding the grease after the water removal step; wherein at least one of the non-aqueous converting agents is hexylene glycol, propylene glycol, a glycol ether or a glycol polyether; wherein one or more added calcium-containing bases consist of calcium carbonate; and wherein, as adjusted to achieve a working penetration value in 60 strokes of 280, less than 25% superbasified calcium sulfonate is added. 5. The method of claim 4, wherein the sulfonate-based complex grease has a first penetration value in an unmilled state that is at least 50 points greater than a second penetration value in an unmilled state. ground. 6. Method according to claim 1, characterized in that the method further comprises adding and mixing a facilitating acid before the conversion step and wherein there is a delay period of the facilitating acid between the addition and mixing of the facilitating acid and an addition of a facilitating acid. next subsequent ingredient that is added after the facilitating acid; and wherein the facilitating acid delay period comprises (1) a facilitating acid retention delay period, wherein a mixture comprising the facilitating acid is maintained at a temperature or range of temperatures for a period of time of (a) 20 minutes or more when the next subsequent ingredient is reactive with the facilitating acid, or (b) 40 minutes or more when the next subsequent ingredient is nonreactive with the facilitating acid, or (2) a facilitating acid temperature adjustment delay period wherein the mixture comprising the facilitating acid is heated or cooled to a temperature or range of temperatures between the addition of the facilitating acid and the addition of the next subsequent ingredient or (c) a combination thereof; and wherein no other ingredient is added between the facilitating acid and the next subsequent ingredient. 7. Method according to claim 1, characterized by the fact that the method further comprises adding and mixing a facilitating acid before the conversion step; wherein the one or more complexing acids comprise 12-hydroxystearic acid, acetic acid and phosphoric acid; wherein the one or more calcium-containing bases comprise calcium hydroxyapatite, added calcium carbonate, added calcium hydroxide or a combination thereof; and wherein one or more conventional non-aqueous converting agents comprise an alcohol, ether, glycol, glycol ether, glycol polyether or combinations thereof. 8. Method according to claim 1, characterized by the fact that the conversion step is completed in less than 75 minutes. 9. The method of claim 1, wherein the sulfonate-based complex grease has an unmilled dropping point of 332°C (630°F) or higher. 10. The method of claim 1, wherein 26% or less of superbasified calcium sulfonate is added and one or more calcium-containing bases comprise calcium hydroxyapatite. 11. The method of claim 1, wherein 23% or less of superbasified calcium sulfonate is added. 12. Method according to claim 3, characterized by the fact that the method further comprises adding and mixing 20% or less of superbasified magnesium sulfonate before the conversion step. 13. Method according to claim 12, characterized by the fact that one or more calcium-containing bases consist of the added calcium carbonate. 14. Method according to claim 13, characterized in that the one or more glycerol derivatives are glycerol monostearate and the superbasified calcium sulfonate is a low quality superbasified calcium sulfonate. 15. Method according to claim 1, characterized by the fact that the method further comprises adding and mixing an alkali metal hydroxide after the conversion step; wherein the step of adding and mixing one or more glycerol derivatives occurs after the conversion step and forms an acidic reaction product of the hydrolysis of one or more glycerol derivatives; wherein no alkali metal hydroxide is added prior to the conversion step; and wherein no glycerol derivative is added prior to the conversion step. 16. Method according to claim 15, characterized by the fact that none of the one or more complexing acids is added between the completion of the conversion step and the addition and mixing of one or more steps of glycerol derivatives. 17. Method according to claim 16, characterized in that one or more complexing acids further comprise boric acid. 18. Method according to claim 1, characterized by the fact that the method further comprises adding and mixing a superbasified magnesium sulfonate before the conversion step. 19. Method according to claim 18, characterized in that one or more calcium-containing bases consist of the added calcium carbonate. 20. Method according to claim 19, characterized by the fact that the one or more glycerol derivatives is glycerol monostearate and the superbasified calcium sulfonate is a low quality superbasified calcium sulfonate. 21. Method according to claim 18, characterized in that the one or more complexing acids comprise 12-hydroxystearic acid, acetic acid and phosphoric acid; wherein a first portion of 12-hydroxystearic acid and a first portion of acetic acid are added before or during the conversion step; and wherein a second portion of the 12-hydroxystearic acid, a second portion of the acetic acid and all of the phosphoric acid are added after the conversion step. 22. Method according to claim 19, characterized in that the added calcium carbonate is added only before the conversion step. 23. The method of claim 19, wherein the one or more conventional non-aqueous converting agents is hexylene glycol. 24. The method of claim 21, wherein the method further comprises adding and mixing a facilitating acid prior to the conversion step and wherein there is an acid delay period between the addition and mixing of the facilitating acid and the addition of a next subsequent ingredient that is added after the facilitating acid, and wherein the facilitating acid delay period comprises (1) a facilitating acid retention delay period wherein a mixture comprising the facilitating acid is retained at a temperature or at a range of temperatures for a period of time prior to the addition of a next subsequently added ingredient, the period of time being (a) 20 minutes or more when the next subsequently added ingredient is reactive with the facilitating acid or (b) 40 minutes or more when the next subsequently added ingredient is nonreactive with the facilitating acid, or (2) a delay period of facilitating acid temperature adjustment in a mixture comprising the facilitating acid is heated or cooled to a temperature or to a range of temperatures before adding the next subsequently added ingredient or (c) a combination thereof, and wherein no other ingredient is added between the facilitating acid and the next subsequent ingredient. 25. The method of claim 24, wherein the next ingredient is subsequently all or a portion of superbasified magnesium sulfonate. 26. The method of claim 25, wherein the added calcium carbonate is added only before the conversion step and wherein the one or more complexing acids further comprise boric acid added after the conversion step. 27. The method of claim 25, wherein a first portion of the added calcium carbonate is added before the conversion step and a second portion of the added calcium carbonate is added after the conversion step. 28. Method according to claim 27, characterized in that the one or more complexing acids additionally comprise boric acid added after the conversion step. 29. Method according to claim 21, characterized by the fact that the method further comprises adding and mixing a facilitating acid before the conversion step; eqm that all of the superbasified magnesium sulfonate is added prior to adding and mixing the facilitating acid and there is no facilitating acid lag period. 30. Method according to claim 29, characterized in that the added calcium carbonate is added only before the conversion step. 31. The method of claim 29, wherein a first portion of the added calcium carbonate is added before the conversion step and a second portion of the added calcium carbonate is added after the conversion step. 32. The method of claim 1, wherein the complex sulfonate-based grease has a drip point of 302°C (575°F) or greater. 33. The method of claim 1, wherein the complex sulfonate-based grease has a drip point of 316°C (600°F) or greater. 34. The method of claim 1, wherein the complex sulfonate-based grease has a drip point of 343°C (650°F) or greater. 35. Method according to claim 1, characterized by the fact that one or more glycerol derivatives comprise glycerol monostearate. 36. Method according to claim 35, characterized by the fact that the superbasified calcium sulfonate is a low quality superbasified calcium sulfonate. 37. Method according to claim 1, characterized by the fact that one or more glycerol derivatives comprise hydrogenated castor oil. 38. Method according to claim 37, characterized by the fact that the superbasified calcium sulfonate is a low quality superbasified calcium sulfonate. 39. Method according to claim 1, characterized by the fact that the superbasified calcium sulfonate is a low quality superbasified calcium sulfonate. 40. Method according to claim 1, characterized by the fact that the complex sulfonate-based grease has a first storage modulus curve G' that has a first crossing point with a first loss modulus curve G" in an unmilled state and a second storage modulus curve G' that has a second crossing point with a second loss modulus curve G” in a milled state and wherein the first crossing point and the second point of; crossing are substantially the same with respect to relative shear stress.