KR20180101478A - Preparation of calcium sulphonate grease using alkali metal hydroxide and using delayed addition of non-aqueous conversion agent - Google Patents

Abstract

(A) calcium hydroxyapatite used as a calcium-containing base for reaction with a complexing acid and / or calcium carbonate added and / or (b) addition of water as a conversion agent, and addition of a non-aqueous And an alkali metal hydroxide added in combination with at least one delay period between addition of a portion of the conversion agent. The delay period may involve a time period for adjusting the temperature of the mixture, a period of time during which the mixture is maintained at or within a certain temperature range, and any combination of these. These calcium sulphonate greases are particularly suitable for use as greases prepared without the delay between the addition of the alkali metal hydroxide and water and the non-aqueous conversion agent, especially the improved thickener oils and greases, as compared to greases when low- Lt; / RTI >

Description

Preparation of calcium sulphonate grease using alkali metal hydroxide and using delayed addition of non-aqueous conversion agent

Cross reference of related application

This patent application claims priority to U.S. Patent Application No. 15 / 130,422, filed April 15, 2016, and U.S. Patent Application No. 14 / 990,473, filed January 7, 2016, U.S. Patent Application No. 13 / 664,768, filed October 31, 2008, which claims the benefit of U.S. Provisional Patent Application No. 61 / 553,674, filed October 31, 2011 U.S. Patent No. 9,458,406) and 13 / 664,574 (U.S. Patent No. 9,273,265, issued March 1, 2016).

1. Invention Field

The present invention is based on the fact that even when the oil-soluble and calcium sulfonated calcium sulfonates used for producing grease are considered to be of poor quality, they are proved by thickener yield and dropping point To an overbased calcium sulfonic acid calcium grease prepared by the addition of an alkali metal hydroxide, which provides an improvement in both the expected high temperature availability. The present invention relates to an overbased calcium sulfonic acid calcium grease prepared using both the use of an added alkali metal hydroxide and the delayed addition of a non-aqueous conversion agent.

2. Description of related technical field

The overbased calcium sulphonate calcium grease was a Greek category established over the years. One known method for making such greases is a two-step process involving "facilitating" and "converting" steps. In general, the first step ( "promoted") is a stoichiometric excess of calcium oxide (CaO), or oxide of calcium hydroxide (Ca (OH) ₂₎ as a base source, alkyl benzene sulfonic acid, carbon dioxide (CO ₂₎ and allowed to react, the inner To react with other components to produce an oil-soluble, overbased calcium sulfonate containing amorphous calcium carbonate dispersed in the calcium carbonate. Such perchlorinated oil-soluble calcium sulfonates are generally transparent, bright, and have Newtonian rheology. In some cases, they may be slightly turbid, but such differences do not prevent their use in the manufacture of the overbased calcium sulfonic acid calcium grease. For the purposes of this specification, the terms " overbased vaporizable calcium sulfonate "and" calcium hypochlorite sulfonate "and" calcium perchlorate sulfonate "refer to any overbased calcium sulfonate suitable for the manufacture of calcium sulfonate .

In general, the second step ("conversion") is to ensure that the initial grease can not convert the amorphous calcium carbonate contained in the calcium perchlorate sulfonate into a finely divided dispersion of crystalline calcium carbonate (calcite) (Such as propylene glycol, isopropyl alcohol, water, formic acid or acetic acid) with a suitable base oil (e. G. Mineral oil), if necessary to avoid too much of the impurities Lt; / RTI > When acetic acid or another acid is used as the conversion agent, generally water and another non-aqueous conversion agent (a third conversion agent such as an alcohol) is used, or only water is added (without the third conversion agent) The conversion takes place in a pressure vessel. Since excessive calcium hydroxide or calcium oxide is used to achieve overbasing, a small amount of residual calcium oxide or calcium hydroxide may be present as part of the usable perchlorate calcium sulfonate and dispersed in the initial grease structure. The extremely finely divided calcium carbonate, aka colloidal dispersion formed by the conversion, interacts with calcium sulphonate to form a grease-like consistency. Such overbased calcium sulfonic acid calcium greases prepared by the two step process will also be known as "simple calcium sulfonate ", for example, U.S. Patent Nos. 3,242,079, 3,372,115, 3,376,222, 3,377,283, 3,492,231.

It is known in the prior art to combine these two steps into a single step by careful control of the reaction. In this one-step process, carbon dioxide, and an accelerator (which produces amorphous calcium carbonate that is overbased by the reaction of carbon dioxide with excess calcium oxide or calcium hydroxide) and a finely divided crystalline calcium carbonate By reacting with a suitable sulfonic acid with calcium hydroxide or calcium oxide in the presence of a reactant system which reacts simultaneously as both of the conversion agent Thus, an overbased, oil-soluble calcium sulfonate (the product of the first step of the two-step process) is never actually formed, and a grease-like roughness is formed in a single step which is isolated as a separate product. This one-step method is disclosed, for example, in U.S. Patent Nos. 3,661,622, 3,671,012, 3,746,643, and 3,816,310.

In addition to the simple sulfonic acid calcium grease, calcium sulfonate complex is known in the prior art of Christ. Such a composite grease is generally prepared by adding a calcium-containing strong base, such as calcium hydroxide or calcium oxide, to a simple sodium sulfonic acid grease prepared by a two-stage or one-stage process and adding a maximum stoichiometric equivalent of a complex acid, Hydroxystearic acid, boric acid, acetic acid (which may be a conversion agent if added prior to conversion), or phosphoric acid. The claimed benefits of calcium sulfonate complex greases for simple greases include reduced tackiness, improved pumpability, and improved high temperature utilization. Calcium sulfonate complex grease is disclosed, for example, in U.S. Patent Nos. 4,560,489, 5,126,062, 5,308,514, and 5,338,467.

Many known prior art methods using the two step process teach simultaneous and generally addition of all the conversion agents (water and non-aqueous conversion agents) prior to heating. However, some prior art documents disclose the time interval between the addition of water and the addition of at least a portion of the non-aqueous conversion agent (s), even though it is always insufficiently defined or not defined at all. For example, U.S. Pat. No. 4,560,489 discloses a process in which water is added after the base oil and the overbased calcium carbonate are heated to about 150 ° F and then water is added prior to the addition of acetic acid and methyl cellosolve (a highly toxic monomethyl ether of ethylene glycol) Lt; RTI ID = 0.0 > 190 F < / RTI > (Examples 1 to 3). The resulting grease contains over 38% of the overbased calcium sulfonate calcium, and according to the '489 patent, the use of up to 38% of the overbased calcium sulfonate causes soft grease, The ideal amount of calcium phosphonate is about 41 to 45%. The grease produced in Example 1 of the '489 patent has a mere point of about 570 ° F. It does not refer to the delay period between the addition of the '489 patent and the addition of the non-aqueous conversion agent, but it is immediately after the heating period from 150 ° F to 190 ° F. The redox and thickener bonds in the '489 patent are undesirable.

In addition, U.S. Patent Nos. 5,338,467 and 5,308,514 disclose the use of fatty acids such as 12-hydroxystearic acid as a conversion agent for use with acetic acid and methanol, wherein there is no delay in the addition of the fatty acid, There is some spacing between the addition and the addition of acetic acid and methanol. Both Example B of the '514 patent and Example 1 of the' 467 patent were prepared by adding water and a fatty acid conversion agent to the other ingredients (including the overbased calcium sulfonate and base oil) and then adding acetic acid followed by methanol RTI ID = 0.0 > 145 F < / RTI > The mixture is then heated to about 150 to 160. Until conversion is complete. The amount of overbased calcium sulfonate in the final grease product in both examples was 32.2 higher than desired. These patents do not mention the delay period between the addition of water and fatty acids and the addition of acetic acid and methanol, but mention that the addition is immediately after an indefinite heating period. A similar method was used in the examples of the '467 patent, except that the entire fatty acid was added after the conversion and the mixture containing water was heated to 140 to 145 후 and the only non-aqueous conversion agent used was acetic acid and methanol, A and the '514 patent. The amount of perbrominated sulfonic acid in this example is 40% higher than in the previous examples. In addition to not achieving ideal thickener results, all of these methods use methanol as a conversion agent, which has environmental problems. The use of volatile alcohols as a conversion agent can cause the release of these components into the atmosphere as a later part of the grease manufacturing process, which is prohibited in many parts of the world. If it is not evacuated, the alcohol should be recovered by water scrubbing or water trap which causes the cost of treating harmful substances. Thus, there is a need for a method that achieves a better thickener load, preferably without requiring the use of volatile alcohols as a conversion agent.

Although a better thickener is achieved in Example 10 of the '514 patent, the use of excess lime is considered a prerequisite to achieving such results. In this embodiment, water and excess lime are added with the other ingredients, and the mixture is heated to 180-190 DEG F while acetic acid is slowly added during the heating period. The resulting grease contains 23% of an overbased calcium sulphonate. While these thickener oils are better than others, there is still room for better improvement that does not require the use of excessive amounts of lime, as taught by the '514 patent.

Other embodiments of the '514 and' 467 patents having a viscosity agent of 23% or less include other prior art techniques that involve the use of a pressurized kettle during the conversion or that do not have a "delay" between the addition of water and a non- Similar to more parts. These embodiments involve the step of adding water and a fatty acid conversion agent, the mixing step for 10 minutes without heating, and then the step of adding acetic acid in a pressurized kettle or without pressurization. These patents, as a reason for all observed yield improvements, concentrate on the use of fatty acids as a conversion agent and the benefit of the addition of, before, after, or both of the fatty acid additions, none of these patents discloses the addition of acetic acid Or any other benefit or advantage over other heating intervals for the above-described embodiments. Also, as discussed below, the 10 minute mixing interval without such heating is not "retarded" as the term is used herein, and is considered to be the same as the simultaneous addition of components, It consumes some time and recognizes what can not happen at the same time.

In addition, the known prior art teaches the use of calcium oxide or calcium hydroxide as a source of basic calcium for making calcium sulphonate grease, or as a necessary component for reaction with a complex acid to form calcium sulphonate composite grease. Known prior art needs to be an amount sufficient to provide a sufficient level of calcium hydroxide or calcium oxide sufficient to fully react with the complexing acid (in addition to the amount of calcium hydroxide or calcium oxide present in the overbased oxyalkylated calcium sulfonate) The addition of calcium hydroxide or calcium oxide is taught. As is disclosed in U.S. Provisional Patent Application Serial No. 13 / 664,768 ("'768 patent application") and U.S. Patent No. 9,273,265, it is generally known that prior art should be avoided for at least two reasons (As "impurities" in calcium hydroxide or calcium oxide) as the individual components other than the presence of the amorphous calcium carbonate present. First, calcium carbonate is generally regarded as a weak base that is inadequate to react with the complex acid to form the optimal grease structure. The second is that the presence of unreacted solid calcium compounds (including calcium carbonate, calcium hydroxide or calcium oxide) interferes with the conversion process, leading to the inferiority of the unreacted solids, Because it causes Greece. However, Applicants have found that the addition of calcium carbonate, calcium hydroxyapatite, or combinations thereof as individual components as ingredients for reacting with a complexing acid, with or without added calcium hydroxide or calcium oxide is described in the '574 and' 768 patent applications To produce an excellent grease as disclosed in U.S. Pat.

Although there are several prior art documents that disclose the addition of crystalline calcium carbonate as an individual component (in addition to the amount of calcium carbonate contained in the calcium perchlorate sulfonate), these greases are insufficient (as taught in the prior art) Thickener beads, or nano-sized particles of calcium carbonate. For example, U.S. Pat. No. 5,126,062 discloses the addition of 5-15% calcium carbonate as a discrete component in the formation of the composite grease, but also requires the addition of calcium hydroxide to react with the complexing acid. The added calcium carbonate is not the only added calcium-containing base to react with the complex acid in the '062 patent. In fact, the added calcium carbonate is not particularly added as a basic reactant for reacting with a complexing acid. Instead, calcium hydroxide is added which is added as a specific calcium-containing base to react with all the complex acids. Further, the NGLI No. 2 grease contains 36 to 47.4% of the perchlorinated calcium sulfonate, which is a significant amount of such expensive components. In yet another example, Chinese Published Application CN101993767 discloses the addition of calcium carbonate of nanosized (5 to 300 nm in size) particles added to calcium perchlorate sulfonic acid, while the reference discloses that nanoparticulate calcium carbonate Does not indicate that it is added as the reactant, or as the only calcium-containing base added separately for reaction with the complexing acid. The use of nano-sized particles can be achieved by a finely divided dispersion of crystalline calcium carbonate (which may be from about 20 to 5000 A, or from about 2 to 500 nm, according to the '467 patent) formed by converting amorphous calcium carbonate contained in calcium perchlorate sulfonate, , It will increase the gas ignition of the grease and keep it firm but it will increase the cost considerably according to the added calcium carbonate of the larger size particles. These Chinese patent applications highly emphasize the absolute necessity of adding calcium carbonate with an accurate nanoparticle size. By the addition of micro-sized calcium carbonate which does not require the use of very expensive nano-sized particles and, as shown in the example grease disclosed in the '574 co-pending application, Or calcium carbonate added as a sole added calcium-containing base, an excellent grease can be formed.

There are also prior art references on the use of tricalcium phosphate as an additive to lubricating greases. For example, U.S. Patent Nos. 4,787,992, 4,830,767, 4,902,435, 4,904,399, 4,929,371 both teach the use of tricalcium phosphate as an additive for lubricating grease. However, as a calcium-containing base for reacting with an acid for producing a lubricating grease including a calcium sulfonate-based grease, a compound represented by the formula Ca ₅ (PO ₄ ) ₃ OH or a mathematically equivalent formula having a melting point of about 1100 ° C, There is no prior reference to teach the use of calcium hydroxyapatite having < RTI ID = 0.0 > Hydroxyapatite "which is a reference material having the chemical formula [Ca ₃ (PO ₄ ) ₂ ] ₃ .Ca (OH) ₂ as a source of grease and tricalcium phosphate containing Ca ₃ (PO ₄ ) ₂ , which is tricalcium phosphate, A number of prior art documents, including U.S. Published Patent Application No. 2009/0305920, which belong to Showa Shell Sekiyu of Japan. This reference to "hydroxyapatite" is disclosed as a mixture of tricalcium phosphate and calcium hydroxide, which has the chemical formula Ca ₅ (PO ₄ ) ₃ OH, as disclosed in the '768 patent application, Is not the same as that of calcium hydroxyapatite having a mathematical equivalent expression. Despite the misreading of the nomenclature, calcium hydroxyapatite, tricalcium phosphate, and calcium hydroxide are chemical compounds that are distinguished by different chemical structures, structures, and melting points, respectively. When mixed together, the two distinct crystalline compounds tricalcium phosphate (Ca ₃ (PO ₄ ) ₂ ) and calcium hydroxide (Ca (OH) ₂ ) either do not react with one another, or alternatively different crystalline compounds calcium hydroxyapatite (Ca ₅ (PO ₄ ) ₃ OH). The melting point of tricalcium phosphate (having the formula Ca ₃ (PO ₄ ) ₂ ) is 1670 ° C. Calcium hydroxide does not have a melting point, but instead, water molecules are lost at 580 ° C to form calcium oxide. The calcium oxide thus formed has a melting point of 2580 캜. Calcium hydroxyapatite (having the formula Ca ₅ (PO ₄ ) ₃ OH or a mathematical equivalent expression) has a melting point of about 1100 ° C. Thus, regardless of how inaccurate the nomenclature is, calcium hydroxyapatite is the same chemical compound as tricalcium phosphate and is not a simple blend of tricalcium phosphate and calcium hydroxide.

It is also desirable to have a calcium sulphonate composite grease composition and process that results in both an improved thickener viscosity and an improved redness. A number of known prior art compositions have been found to have NGLI < RTI ID = 0.0 > No. < / RTI > To achieve a second class of suitable greases, an overbased calcium sulphonate calcium sulphate in an amount of at least 36 wt% (based on the final grease product) is required. Calcium sulfonate is one of the most costly materials in the manufacture of calcium sulphonate grease, and therefore reduces the amount of these ingredients while still maintaining the desired strength of the final grease (thereby improving the thickener oil) . To achieve a significant reduction in the amount of overbased calcium sulfonate used, a number of prior art documents employ pressurized reactors. Without the need for a pressurized reactor, (Or a perchlorate-free calcium sulfonate percentage of less than 36%, and a greasy 60-stroke 60 stroke penetration of between 265 and 295) It is preferable to have calcium sulfonate calcium sulfonate. Since the enemy is the first and easiest measured guide to the high temperature availability limit of the lubricating grease, a higher score is deemed desirable.

Addition of alkali metal hydroxides in simple calcium soap greases such as anhydrous calcium-soap thickened grease is also known. However, it is not known to add alkali metal hydroxides in calcium sulphonate grease to provide improved thickener viscosity and high tack, since such additions are perceived to be unnecessary for those skilled in the art. The reason for adding an alkali metal hydroxide such as sodium hydroxide to simple calcium soap grease is that the commonly used calcium hydroxide has insufficient water solubility, which is weaker than the highly soluble sodium hydroxide. Due to this, the small amount of sodium hydroxide dissolved in the added water reacts rapidly with soap-forming fatty acids (usually a mixture of 12-hydroxystearic acid or non-hydroxylated fatty acids such as 12-hydroxystearic acid and oleic acid) It is said to form soap. This quick reaction is thought to be "ball rolling". However, the direct reaction with a calcium-containing base such as calcium hydroxide and a fatty acid is not a problem in the production of calcium sulfonate composite grease. Due to the high washing power / dispersibility of the presence of large amounts of calcium sulfonate, the reaction takes place very easily. Thus, it is not known in the art to use alkali metal hydroxides in calcium sulphonate grease as a way to obtain a complexed acid to react with calcium hydroxide.

The combination of various ingredients and methodologies in the preparation of calcium sulphonate greases having improved thickener and higher loading, for example, the addition of alkali metal hydroxides can be carried out by (1) adding a calcium containing base for basic reaction The use of calcium hydroxyapatite as a calcium compound (also referred to as a calcium compound), crystalline calcium carbonate to be added, or a combination thereof (with or without added calcium hydroxide or calcium oxide); (2) delayed addition of a non-aqueous conversion agent; Or (3) a combination of the above-mentioned (1) and (2).

The present invention relates to a process for the preparation of an overbased vaporizer for the improvement of both the viscosity agent (which maintains acceptable admixture readings and at the same time requires a smaller amount of overbased calcium sulfonate) Calcium calcium phosphate and a process for producing such a grease. According to one preferred embodiment of the present invention, the composite calcium sulfonate calcium grease composition comprises an alkali metal hydroxide. According to another preferred embodiment, the composite calcium sulfonate calcium grease composition comprises an alkali metal hydroxide and calcium hydroxyapatite as a calcium-containing base (also referred to as a basic calcium compound) to be added for reaction with the complexing acid, calcium carbonate to be added, Includes all. According to another preferred embodiment, the complex calcium sulfonate calcium sulphate composition comprises (1) up to 36% (based on the weight of final grease) of calcium perchlorate; (2) calcium hydroxyapatite, calcium carbonate added, calcium hydroxide, calcium oxide, or any combination thereof; (3) one or more alkali metal hydroxides; (4) one or more conversion agents; And (5) at least one complexing acid. According to another preferred embodiment, the final grease composition comprises from about 0.005 to 0.5% alkali metal hydroxide.

According to a preferred method of preparing the complex sodium sulfonate calcium grease, the alkali metal hydroxide is added to the other components prior to or after conversion. Most preferably, the process comprises the steps of: (a) mixing an overbased calcium sulfonate with a base oil; (b) adding and mixing one or more calcium-containing bases; (c) dissolving the alkali metal hydroxide in water, adding and mixing the solution to the other components; (d) adding and mixing the one or more converting agents, wherein the one or more converting agents, which, if added prior to conversion, can comprise water from step (c); (e) adding and mixing one or more complexing acids; And (f) heating some combinations of these components until conversion occurs. Each of the components in step (b), step (c) and step (e) may be added prior to conversion, after conversion, or prior to conversion, with one fraction added and another fraction added, Their order for these is not critical to this aspect of the method.

According to another preferred embodiment, a first fraction of water is added as a conversion agent prior to conversion, a second fraction of water after conversion is added, and an alkali metal hydroxide is added to the first fraction of the water or the second fraction of the water or both Composite calcium sulfonate complexes are prepared by reacting and mixing certain compounds according to the outlined steps, except that they are dissolved. According to another preferred embodiment, there is provided a process for the preparation of a compound of formula (I) according to the invention which comprises at least two separate additions of water, as a conversion agent, between the first addition of water and the second addition of water as a conversion agent, , The alkali metal hydroxide is dissolved in the initial addition or primary addition of water as a conversion agent or in the secondary addition or subsequent addition of water as a conversion agent or both.

According to another preferred embodiment, the process for preparing the complex calcium sulfonate calcium sulphate comprises the above outlined steps, including preferred variants, wherein said conversion agent comprises water and at least one non-aqueous conversion agent, There is at least one delay period between the addition of water as the agent and the addition of at least one fraction of the non-aqueous conversion agent. Advantageously, said at least one delay period is a temperature adjustment delay period or a maintenance delay period, or both, as further described below. As used herein, "non-aqueous conversion agent " means any conversion agent other than water and includes a conversion agent that may contain some water as a diluent or impurity.

In any of the preparation method embodiments disclosed herein, one or more complexing acids may be added prior to or after conversion. Alternatively, one fraction of the at least one complexing acid may be added prior to conversion of the complex calcium sulfonate calcium grease, and the remainder of the at least one complexing acid added may be added after conversion. The entire one or more calcium-containing bases may be added prior to or after conversion. Alternatively, a fraction of said one or more calcium-containing bases may be added prior to conversion and the remainder may be added after conversion. Calcium hydroxyapatite, added calcium carbonate, added calcium hydroxide, added calcium oxide, or a combination thereof may be used as the calcium-containing base for reacting with the complexing acid. A large excess of calcium hydroxide (e.g., calcium hydroxide greater than 50% greater than the stoichiometric amount required for reaction with the total complexing acid) is not added prior to conversion relative to the total amount of complexing acid used.

According to another preferred embodiment of the present invention, the improved thickener results show that even if the overbased calcium sulfonate is considered "poor ", the alkali metal hydroxide added alone or in combination with at least one of the non- In combination with at least one delay period for the fraction. Certain overbased, vaporizable, calcium sulfonates, which are marketed and marketed for the manufacture of calcium sulphonic acid greases, can provide products with unacceptably low endpoints when the prior art calcium sulfonate technology is used. Such an overbased vaporizable calcium sulfonate is referred to throughout the text as "low quality" The overbased, oil-soluble calcium sulfonate, which produces a grease having a higher red point (greater than 575 [deg.] F) when all components and methods are identical except for the commercially available batch of the overbased calcium sulfonate used, Quot; quality "quality calcium sulfonate for purposes of the present invention, and an overbased, salt-forming, calcium sulfonate, which produces a grease with a lower endpoint, is considered to be of" low " quality for the purposes of the present invention. A plurality of examples thereof are provided in the '768 patent application, which is incorporated by reference. A comparative chemical analysis of calcium silicate with good quality and low quality of the perchlorinated oil-soluble calcium sulfonate has been conducted, but the exact reason for this low redness problem is believed to be unproven. The most commercially available overbased calcium sulfonates are considered to be of good quality and it is desirable to achieve both an improved thickener bead and a higher redox regardless of whether good quality or low quality calcium sulphonate is used. Both the improved thickener and higher dots can be achieved using alkali metal hydroxides, especially when used in combination with the delayed addition process according to the invention, using calcium sulphonate of good quality or of low quality . In fact, the results of the examples using low-quality, perchlorinated sodium sulfonate calcium proved to be better than the examples using calcium perchlorate of good quality when using at least some of the preferred embodiments of the present invention. According to another preferred embodiment, when at least one of the non-aqueous converting agents is a glycol (e.g., propylene glycol or hexylene glycol), the entire glycol is added after at least one delay period (not added with water ) And low-quality calcium sulfonate are used.

When prepared in accordance with the parameters of the present invention disclosed herein, consistently high quality calcium sulfonic acid greases may be prepared having better viscosity and viscosity properties than prior art greases. The overbased calcium sulfonate complex grease having an overbased vaporization-available calcium sulfonate percentage of about 10 to 45% in an open container (without pressurization), prepared according to a preferred embodiment of the present invention, (Or more than No. 2 grade, i.e., lighter) and 575 F (or more) red. More preferably, the amount of the calcium salt of an overbased vaporizable oil of calcium in the grease prepared according to the preferred embodiment of the present invention is at least about 10% and no more than about 36%, more preferably no more than about 30% or less, and most preferably about 22% or less. These improved thickener binds can be achieved using both of good quality and low quality calcium perchlorate sulfonate. In preparing grease in pressurized containers, larger thickener binds can be achieved using the components and methods of the present invention. Most preferably, a productive point of greater than 650 < 0 > F is achieved. The lower concentration of the perchlorinated oilborne calcium sulfonate achieved by the present invention is preferred because the cost of the grease is reduced. Other properties, especially at lower temperatures, such as fluidity and pumpability, can be beneficially influenced by the improved thickener bonds achieved in accordance with the present invention.

While not intending to be bound by theory, the addition of alkali metal hydroxides leads to a looping metathesis reaction that affects the conversion method, and the reaction using a complex acid to produce these unexpected thickener leads and redox Are believed to cause complex sulfonic acid calcium grease. As discussed above, alkali metal hydroxides are added to simple calcium soap grease, but are not known to be added to complex perbrominated calcium sulfonate calcium grease. This is because the calcium hydroxide used in the simple calcium soap grease is generally poorly soluble and is a weak base compared to highly water soluble sodium hydroxide. Due to this, the small amount of sodium hydroxide dissolved in the water to be added is rapidly reduced with a soap-forming fatty acid (generally a mixture of 12-hydroxystearic acid or 12-hydroxystearic acid and a nonhydroxylated fatty acid, such as oleic acid) It is said to react to form sodium soap. This rapid reaction is thought to be "ball rolling" in the manufacture of simple calcium soap grease. However, after all this has occurred, if a small amount of sodium hydroxide reacts with a small amount of fatty acid, the remaining reactant to be reacted (calcium hydroxide and most of the residue, which is the fatty acid) is left as it is when sodium hydroxide is not added. Unreacted calcium hydroxide will still be present and will react with the remaining unreacted fatty acids to form a calcium soap thickener.

A more similar explanation is that a rapidly formed sodium soap reacts further with calcium hydroxide in the metathesis reaction where a trade of sodium and calcium takes place. The sodium soap becomes the calcium soap, and the calcium hydroxide becomes the sodium hydroxide. This reaction is driven by the high water solubility of the sodium hydroxide and the lower water solubility of the calcium soap than the sodium soap. It can then "regenerate" a small amount of sodium hydroxide to quickly react again with more fatty acids. Thereafter, the above-mentioned metathesis reaction occurs again to produce more calcium soap. This looping reaction sequence continues until the entire calcium hydroxide reacts to form a calcium soap thickener. This response sequence loop is provided as follows:

Reaction 1: NaOH + RCOOH? RCOO ^- Na ⁺

Reaction 2: 2 RCOO ^- Na ⁺ + Ca (OH) ₂ → (RCOO) ₂ Ca + ₂ NaOH

The NaOH formed in Reaction 2 becomes the reactant for Reaction 1.

Unlike simple calcium soap grease, the direct reaction of fatty acids with calcium-containing bases (eg, calcium hydroxide) has never been a problem during the manufacture of calcium sulphonate composite grease. The reaction occurs very easily, which is due to the high washability / dispersibility of the large amount of calcium sulphonate, which is why the addition of alkali metal hydroxide is not considered or suggested in the prior art calcium sulphonic acid grease technology. In fact, due to the high washability / dispersibility of the calcium sulphonate present in large amounts during the reaction with the complex acid and the calcium-containing base, one skilled in the art will appreciate that by adding a small amount of alkali metal hydroxide prior to this reaction, I did not expect it to be obtained. Nevertheless, it is evident that the reaction of the alkali metal hydroxide has an unexpected beneficial effect on the viscosity agent in the calcium sulphonate grease. When the addition of an alkali metal hydroxide is combined with the use of calcium hydroxyapatite and / or calcium carbonate as a calcium-containing base for the delayed addition of at least one fraction of the non-aqueous conversion agent methodology and reaction with the complexing acid, It grows. Preferred embodiments of the compositions and methods of the present invention include the addition of alkali metal hydroxides as a component of the composite sodium sulfonic acid calcium grease, or the addition of the alkali metal hydroxides and (1) as the calcium containing base for reaction with the complexing acid Calcium hydroxyapatite and / or calcium carbonate, and / or (2) one or more delay periods between the addition of water as the conversion agent and the addition of at least a portion of the non-aqueous conversion agent.

complex Calcium sulfonate  Grease composition

According to a preferred embodiment of the present invention, the composite calcium sulfonate calcium sulphate composition comprises (1) up to 45% (based on the weight of the final grease) of calcium perchlorate of calcium sulphonate; (2) calcium hydroxyapatite, calcium carbonate added, calcium hydroxide added, calcium oxide added, or any combination thereof; And (3) an alkali metal hydroxide. More preferably, the complex calcium sulfonic acid grease comprises (4) at least one conversion agent; And (5) at least one complexing acid. According to another preferred embodiment, the at least one conversion agent comprises water and at least one non-aqueous conversion agent, for example propylene glycol or hexylene glycol. Optionally, the grease composition may comprise a facilitating acid. These facilitated acids help form a grease structure. Any or all of the specific ingredients, including the conversion agent and the calcium-containing base, may not be present in the final finished product due to evaporation, volatilization, or reaction with other ingredients during manufacture.

The highly overbased, vaporizable, calcium sulfonates used in accordance with these aspects of the present invention are those of the general elevation type described in the prior art, for example, U.S. Patent Nos. 4,560,489, 5,126,062, 5,308,514, and 5,338,467. And may be an overbased vaporizable oil of calcium sulphonate. The highly perchlorinated oil-soluble calcium sulfonate can be prepared in situ according to this known process, or it can be purchased as a commercially available product. Such highly perchlorinated oilborne calcium sulfonate will have a TBN (Total Base Number) value of at least 200, preferably at least 300, and most preferably at least about 400. Commercially available overbased calcium sulphonate calcium salts of this type include, but are not limited to: Hybase C401 supplied by Chemtura USA Corporation; Syncal OB 400 and Syncal OB405-WO supplied by Kimes Technologies International Corporation; Lubrizol 75GR, Lubrizol 75NS, Lubrizol 75P, and Lubrizol 75WO supplied by Lubrizol Corporation. The overbased calcium sulfonate contains about 28 to 40% of dispersed amorphous calcium carbonate, based on its weight, which is converted to crystalline calcium carbonate during the preparation of the calcium sulfonate sulphate. The overbased calcium sulfonate also contains about 0 to 8% residual calcium oxide or calcium hydroxide, based on its weight. The most commercially available overbased calcium sulfonate will also contain about 40% base oil as a diluent to prevent the calcium salt of the overbased calcium sulfonate from becoming very thick and difficult to process and process. The amount of base oil in the overbased calcium sulfonate can make it unnecessary to add additional base oil (as a separate component) prior to conversion to an acceptable grease. The overbased calcium sulfonate used may be of good quality or of low quality as defined herein and in the '768 patent application.

The amount of highly overbased, vaporizable, calcium sulphonate in the final composite grease according to embodiments of the present invention may vary, but is typically 10 to 45%. Preferably, the amount of highly overbased, vaporizable, calcium sulphonate in the final composite grease according to embodiments of the present invention is in the range of from about 36, which is less than what is achievable in manufacture in a pressurized vessel, Or less, more preferably about 30% or less, and most preferably about 22% or less.

Any petroleum naphthenic acid or paraffinic mineral oil commonly used and well known in the art of grease manufacture may be used as a base oil in accordance with the present invention. To prevent the overbased sulfonate from becoming too thick and easily untreatable, the base oil is added as necessary as the most commercially available overbased calcium sulfonate calcium will already contain about 40% base oil as a diluent, Depending on the desired intensity of the grease and the desired intensity of the final grease, it may not be necessary to add additional base oil. Synthetic base oils may 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 adverse effects when present during the conversion process, as will be appreciated by those skilled in the art. In some cases, this synthetic base oil does not need to be added initially but is added to the grease manufacturing process at a stage where the adverse effect is eliminated or minimized, e.g. after conversion. Naphthenic acid and paraffinic mineral base oils are preferred due to their lower cost and availability. The total amount of base stock (including any amount initially added and any amount that can later be added in the preparation of grease to achieve the desired finish) is generally from 30 to 70%, based on the total weight of the grease, , Preferably 45 to 70%, and most preferably 50 to 70%. Generally, the amount of base oil added as a separate component will increase as the amount of the overbased calcium sulfonate decreases. As will be understood by those skilled in the art, the combinations of different base oils disclosed above may be used in the present invention.

Water is added as one conversion agent according to the preferred embodiments of the present invention. Preferably, one or more other non-aqueous conversion systems are added in these aspects of the invention. The non-aqueous conversion agent can be any of the conversion agents other than water such as alcohols, ethers, glycols, glycol ethers, glycol polyethers, carboxylic acids, inorganic acids, organic nitrates, and any other compounds containing active or tautomeric hydrogen . Non-aqueous conversion agents also include formulations containing some water as a diluent or impurity. Although they can be used as non-aqueous converting agents, it is desirable not to use alcohols such as methanol or isopropyl alcohol or other low molecular weight (i.e. more volatile) alcohols, Due to environmental concerns and environmental regulations associated with the treatment of hazardous wastes of scrubbed alcohol. The total amount of water added as a conversion agent is 1.5 to 10%, preferably 2.0 to 5.0%, and most preferably 2.2 to 4.5%, based on the final weight of the grease. Additional water can be added after conversion. Further, when the conversion is carried out in an open vessel of sufficiently high temperature to volatize a significant fraction of the water during the conversion, additional water may be added to replace the lost water. The total amount of one or more non-aqueous conversion agents added is from 0.1 to 5%, preferably from 0.3 to 4%, most preferably from 0.5 to 2.0%, based on the final weight of the grease. In general, the amount of non-aqueous conversion agent used will decrease as the amount of calcium perchlorate sulfonate is reduced. Depending on the conversion agent 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, as discussed below, some of the conversion agent may also act as a complexing acid to prepare the calcium sulfonate complex grease according to one embodiment of the present invention. These materials will provide both the functions of conversion and compounding at the same time.

Although not required, according to another embodiment of the present invention, a small amount of promoted acid may be added to the mixture prior to conversion. Suitable promoting acids, for example, alkylbenzenesulfonic acids, generally having an alkyl chain length of 8 to 16 carbon atoms, can help promote efficient formation of grease structures. Most preferably, such alkylbenzenesulfonic acids comprise a mixture of alkyl chain lengths of mainly about 12 carbon atoms. Such benzenesulfonic acids are generally represented by dodecylbenzene sulfonic acid ("DDBSA"). This type of commercially available benzenesulfonic acid is commercially available from JemPak GK Inc. JemPak 1298 Sulfonic Acid, supplied by the Company, Calsoft LAS-99 supplied by Pilot Chemical Company, and Biosoft S-101 supplied by Stepan Chemical Company. When alkyl benzene sulfonic acid is used in the present invention, it is added in an amount of about 0.50 to 5.0%, preferably 1.0 to 4.0%, and most preferably 1.3 to 3.6%, based on the final weight of the grease, before conversion. If the calcium sulfonate is prepared in situ using an alkyl benzene sulfonic acid, the promoted acid added in accordance with this aspect is an additional requirement for the production of calcium sulfonate.

One or more complexing acids, one or more calcium containing bases, and one or more alkali metal hydroxides are also added to the components in preferred embodiments of the calcium sulphonic acid grease according to the present invention. The calcium-containing base may include one or more of calcium hydroxyapatite, calcium carbonate added, calcium hydroxide added, calcium oxide added, or a combination of the above. The calcium hydroxyapatite used as the calcium-containing base for reacting with the complex acid according to this embodiment may be added before, after, or after the conversion, one fraction may be added and one fraction after conversion may be added. Most preferably, the calcium hydroxyapatite is finely divided to an average particle size of about 1 to 20 microns, preferably about 1 to 10 microns, and most preferably about 1 to 5 microns. In addition, calcium hydroxyapatite will be of sufficient purity to have abrasive contaminants such as silica and alumina at levels sufficiently low to not significantly affect the abrasion resistance properties of the resulting grease. Ideally, for best results, calcium hydroxyapatite should be a food grade or US Pharmacopoeia grade. The amount of calcium hydroxyapatite added may be from 1.0 to 20%, preferably from 2 to 15%, based on the total weight of the grease, although, if desired, greater amounts may be added after all reactions with the converted and complexed acid are completed, %, And most preferably from 3 to 10%.

According to another embodiment of the present invention, calcium hydroxyapatite may be added to the components in an amount insufficient to fully react with the complexing acid. In this embodiment, finely divided calcium carbonate as an oil soluble solid calcium containing base is added in an amount sufficient to completely react with and neutralize a fraction of any subsequently added complexing acid which is not neutralized by calcium hydroxyapatite , Preferably before the conversion.

According to another embodiment, calcium hydroxyapatite may be added to the components in amounts insufficient to fully react with the complexing acid. In this embodiment, the finely divided calcium hydroxide and / or calcium oxide as the oil soluble solid calcium containing base is added to the fraction of any subsequently added complexing acid which is not neutralized by the co-added calcium hydroxyapatite In an amount sufficient to fully react with and neutralize it, preferably before conversion. In this embodiment, the calcium hydroxide and / or calcium oxide preferably exhibits a hydroxide equivalent weight of not less than 75%, which is provided by the entirety of calcium hydroxyapatite, calcium hydroxide, and calcium oxide to be added. In another embodiment, the calcium carbonate may be added together with calcium carbonate, which is added before or after the reaction with the complexing acid, together with calcium hydroxyapatite, calcium hydroxide and / or calcium oxide. If the amount of calcium hydroxyapatite, calcium hydroxide, and / or calcium oxide is not sufficient to neutralize the complexing acid or acids to which it is added, the calcium carbonate is preferably present in an amount sufficient to neutralize any remaining complexing acids or acids Lt; / RTI >

According to these aspects of the invention, the added calcium carbonate used as the calcium-containing base, either alone or in combination with another calcium-containing base or bases, is used in an amount of about 1 to 20 microns, preferably about 1 to 10 microns, Most preferably from about 1 to about 5 microns. In addition, the added calcium carbonate is preferably calcined to have a polishing contour such as silica and alumina to a sufficiently low degree so as not to significantly affect the abrasion resistance properties of the resulting grease, preferably crystalline calcium carbonate of sufficient purity (most preferably calcite )to be. Ideally, for optimal results, calcium carbonate should be a food grade or US Pharmacopoeia grade. The amount of added calcium carbonate to be added is 1.0 to 20%, preferably 2.0 to 15%, and most preferably 3.0 to 10% based on the final weight of the grease. This amount is added as a separate component in addition to the amount of dispersed calcium carbonate contained in the calcium salt of the overbased calcium sulfonate. According to another preferred embodiment of the present invention, the added calcium carbonate is added prior to conversion as a calcium-containing base component added singly to react with the complexing acid. Additional calcium carbonate may be added to the simple or complex grease embodiment of the present invention after conversion and, in the case of a complex grease, after all reactions with the complex acid have been completed. However, the indication for calcium carbonate added here is added prior to the conversion in the preparation of the composite grease according to the invention, and is added either as one of the calcium-containing bases added for reaction with the complexing acid or as a calcium-containing base ≪ / RTI >

According to another embodiment, the added calcium hydroxide and / or calcium oxide added prior to or after the conversion may have a mean particle size of about 1 to 20 microns, preferably about 1 to 10 microns, and most preferably about 1 to 5 microns, Lt; / RTI > In addition, calcium hydroxide and calcium oxide will have sufficient purity to have abrasive contaminants such as silica and alumina to a sufficiently low level so as not to significantly affect the abrasion resistance properties of the resulting grease. Ideally, for best results, calcium hydroxide and calcium oxide should be food grade or US Pharmacopoeia grades. The total amount of calcium hydroxide and / or calcium oxide will be from 0.07 to 1.20%, preferably from 0.15 to 1.00%, and most preferably from 0.18 to 0.80%, based on the total weight of the grease. This amount is added as a separate component other than the amount of residual calcium hydroxide or calcium oxide contained in the calcium salt of the overbased calcium sulfonate. Most preferably, calcium hydroxide which is excessive relative to the total amount of complexing acid used is not added prior to conversion. According to another embodiment, there is no need to add any calcium hydroxide or calcium oxide to react with the complexing acid, and the added calcium carbonate or calcium hydroxyapatite can be used as the sole added calcium containing base for this reaction, May be used in combination for the reaction.

The alkali metal hydroxide added includes sodium hydroxide, lithium hydroxide, potassium hydroxide, or a combination thereof. Most preferably, sodium hydroxide is used as an alkali metal hydroxide. The total amount of alkali metal hydroxide added is preferably from about 0.005 to 0.5%, more preferably from about 0.01 to 0.4%, and most preferably from about 0.02 to 0.20%, based on the weight of the final grease product. Including the calcium-containing base, the alkali metal hydroxide reacts with the complexing acid to give an alkali metal salt of the complexing acid present in the final grease product. Preferred amounts given herein are amounts added as raw materials to the weight of the final grease product, even if the alkali metal hydroxide is not present in the final grease. According to one preferred embodiment, the alkali metal hydroxide is dissolved in water prior to addition to the other ingredients. The water used to dissolve the alkali metal hydroxide may be water used as a conversion agent or water added after conversion. Although it is most preferred to dissolve the alkali metal hydroxide in water prior to adding it to the other ingredients, it may be added directly to other ingredients without primary dissolution in water.

The complex acid used in these embodiments will comprise at least one, preferably two or more of: long chain carboxylic acids, short chain carboxylic acids, boric acid and phosphoric acid. Acetic acid and other carboxylic acids may be used as a converting agent or a complexing acid, or both, as they are added. Similarly, some complexing acids (e.g., 12-hydroxystearic acid in the '514 and' 467 patent) can be used as the conversion agent. The total amount of the complexing acid to be added is preferably 2.8 to 11%, based on the weight of the final grease. Suitable long chain carboxylic acids for use in accordance with the present invention include aliphatic carboxylic acids having 12 or more carbon atoms. Preferably, the long chain carboxylic acid comprises an aliphatic carboxylic acid having 16 or more carbon atoms. Most preferably, the long chain carboxylic acid is 12-hydroxystearic acid. The amount of long chain carboxylic acid is from 0.5 to 5.0%, preferably from 1.0 to 4.0%, most preferably from 2.0 to 3.0%, based on the final weight of the grease.

Suitable short chain carboxylic acids for use in accordance with the present invention include aliphatic carboxylic acids having up to 8 carbon atoms, preferably up to 4 carbon atoms. Most preferably, the short chain carboxylic acid is acetic acid. The amount of the short chain carboxylic acid is 0.05 to 2.0%, preferably 0.1 to 1.0%, and most preferably 0.15 to 0.5%, based on the final weight of the grease. Any compound which is expected to react with water or other ingredients used in the preparation of the greases according to the invention, including reactions which produce long chain or short chain carboxylic acids, is also suitable for use. For example, the use of acetic anhydride will form acetic acid to be used as a complexing acid by reaction with water present in the mixture. Similarly, the use of methyl 12-hydroxystearate will form 12-hydroxystearic acid to be used as the complexing acid by reaction with water present in the mixture. Alternatively, if sufficient water is not already present in the mixture, additional water may be added to the mixture to react with these components to form the required complex acid.

When boric acid is used as a complexing acid according to this embodiment, an amount of 0.3 to about 4.0%, preferably 0.5 to 3.0%, and most preferably 0.6 to 2.0%, based on the final weight of the grease, is added. The boric acid may first be added to the water after it has been dissolved or slurried, or it may be added without water. Preferably, the boric acid will be added during the manufacturing process so that water is still present. Alternatively, any of the well-known inorganic borate salts may be used instead of boric acid. Similarly, any of the established boronated organic compounds such as, for example, borated amines, borated amides, borated esters, borated alcohols, borated glycols, borated ethers, borated epoxides, borated ureas, Hydroxycarboxylic acid, boronated sulfonic acid, borated epoxide, borated peroxide, etc. may be used instead of boric acid. When phosphoric acid is used as the complexing acid, an amount of 0.4 to 4.0%, preferably 0.6 to 3.0%, and most preferably 0.8 to 2.0%, based on the final weight of the grease, is added. The percentages of the various conjugated acids disclosed herein are relative to the pure active compound. If any of these complexing acids can be in diluted form, they may be suitable for use as is in the present invention. However, the percentage of this diluted complex acid will need to be adjusted to include the diluent factor and bring the actual active material to the specified percentage range.

Other additives commonly recognized within the field of grease manufacture may be added to the simple grease or complex grease embodiment of the present invention. These additives may include rust and corrosion inhibitors, metal deactivators, metal passivators, antioxidants, extreme pressure additives, antiwear additives, chelating agents, polymers, tackifiers, dyes, chemical markers, fragrance importers, And may include a sex sterile solvent. Back classes may be particularly useful in the manufacture of open gear lubricants and braided wire rope lubricants. It will be understood that the inclusion of any such additives is still within the scope of the present invention. All percentages of the ingredients are based on the final weight of the finished grease, unless otherwise stated, although the amount of the ingredients may not be present in the final grease product due to reaction or volatilization.

Compound containing alkali metal hydroxide Calcium sulfonate  How to make grease

The calcium sulphonate grease composition is preferably prepared according to the process of the invention disclosed herein. In one preferred embodiment, the method comprises: (1) mixing an overbased calcium sulfonate with a base oil; (2) dissolving the alkali metal hydroxide in water and adding and mixing the mixture with other ingredients; (3) adding and mixing one or more calcium-containing bases; (4) when added prior to conversion, adding and mixing one or more conversion agents, which may comprise water from step c; (5) adding and mixing at least one complexing acid; And (6) heating some combination of these components until conversion occurs. In this preferred embodiment, there is no delay between the addition of water as a conversion agent (if water is used as the conversion agent) and the addition of any fraction of any non-aqueous conversion agent (if a non-aqueous conversion agent is used). In another preferred embodiment, the method is characterized in that the conversion agent comprises water and at least one non-aqueous conversion agent, wherein at least one delay period between the addition of at least one fraction of one or more other non- Except for the presence of the < / RTI > For ease of reference, the term " alkali addition process "will be used to describe all preferred embodiments of the processes according to the invention in which the alkali metal oxide is added without any delayed addition of the non-aqueous conversion agent, Delayed addition method "means that all of the processes according to the invention, in which the alkali metal hydroxide is added and at least one delay period is present between the addition of water as the conversion agent and the addition of at least a part of the non-aqueous conversion agent (s) Will be used to describe preferred embodiments. The term " delayed addition method "will be used to describe the delayed non-aqueous conversion method of the '476 patent application without any alkali metal hydroxide addition.

In both the preferred alkali addition process and the alkali / delayed addition process, each of the components of step (2), step (3) and step (5) may be added after conversion, prior to conversion, And another fraction may be added after the conversion. Optionally, the promoting acid may be added and mixed with the components preferably prior to conversion. If a promoting acid is used, it is also preferred that the alkali metal hydroxide is added to the mixture before it is added. Alternatively, the alkali metal hydroxide can be added to other components without primary dissolution in water, but it is most preferred to pre-dissolve in water. Most preferably, the specific ingredients and amounts used in the process are in accordance with the preferred embodiments of the compositions disclosed herein.

In both the preferred alkali addition process and the alkali / delayed addition process, the addition sequence for the components of step (2), step (3) and step (5) The order of addition to the components, and the order of heating timing of the components are not important. However, the addition of some components before or after other components and / or before or after heating is preferred as disclosed below. In addition, the order of addition of the conversion agent is important in the alkali / delayed addition process as further described below.

According to another preferred embodiment of both the alkali addition process and the alkali / delayed addition process, the complex calcium sulfonate calcium grease is prepared by adding a first fraction of water as a conversion agent prior to conversion and a second fraction of water being added after conversion Is prepared by reacting and mixing certain compounds according to the above outlined steps except that the alkali metal hydroxide is dissolved in the first fraction of water or the second fraction of water or both. According to another preferred embodiment of both the alkali addition process and the alkali / delayed addition process, one or more temperature adjustment steps, between the first addition of water as the conversion agent and the second addition of water as the conversion agent, The water is added as a conversion agent in at least two separate pre-conversion stages, the alkali metal hydroxide is dissolved in the initial or primary addition of water as the conversion agent, or the water as the conversion agent Dissolved in the second or subsequent addition, or dissolved in both of these additions.

According to another preferred embodiment of both the alkali addition method and the alkali / delay addition method, at least a part of the complex acid is added prior to heating. According to another preferred embodiment, the entire complexing acid (s) are added prior to heating. According to another preferred embodiment of both the alkali addition method and the alkali / delayed addition method, when the added calcium carbonate is used as the calcium-containing base to be added to react with the complexing acid, Lt; / RTI > According to another preferred embodiment of both the alkali addition method and the alkali / delayed addition method, calcium hydroxyapatite, added calcium hydroxide and added calcium carbonate are both used as a calcium-containing base for reacting with the complexing acid. In this embodiment, the addition of at least one fraction of calcium hydroxyapatite and calcium hydroxide prior to the addition of any complexing acid, and the addition of at least a portion of the complexing acid, . According to another preferred embodiment of both the alkali addition process and the alkali / delayed addition process, the water comprising the dissolved alkali metal hydroxide is added after the addition of the calcium containing base (s) and / ) Is added. According to another preferred embodiment, the water in which the alkali metal hydroxide (or the alkali metal hydroxide added separately) is dissolved is added after the addition of at least one fraction of the at least one complexing acid.

According to a number of different aspects of both an alkali addition process and an alkali / delay addition process, the process comprises the following steps (3) (addition of the calcium-containing base (s)) which involve one or more of the following , The same as the embodiments above: (a) mixing finely divided calcium hydroxyapatite as the sole added calcium containing base prior to conversion; (b) admixing the finely divided calcium hydroxyapatite and calcium carbonate in an amount sufficient to completely react and neutralize the subsequently added complex acid according to one embodiment; (c) According to another embodiment of the present invention, finely divided calcium hydroxyapatite and calcium hydroxide and / or calcium oxide are added in an amount sufficient to completely react with the subsequently added complex acid and neutralize it, And / or calcium hydroxide and / or calcium oxide, present in an amount of preferably not more than 75% of the hydroxide equivalent base strength provided by calcium oxide and calcium hydroxyapatite as a whole; (d) mixing calcium carbonate added after conversion, according to another embodiment of the present invention; (e) mixing calcium hydroxyapatite in an amount sufficient to completely react with and neutralize any complexing acid added after conversion, after conversion, according to another embodiment of the present invention; (f) mixing the finely divided calcium carbonate as an oil-soluble solid calcium-containing base prior to conversion, finely divided calcium hydroxyapatite and calcium hydroxide in an amount insufficient to fully react and neutralize the subsequently added complexing acid and / Or calcium oxide with calcium hydroxide and / or calcium oxide, which are present in an amount of preferably not more than 75% of the hydroxide basicity of the hydroxide and / or calcium oxide to be added and the hydroxide basicity provided by the whole calcium hydroxyapatite, With the addition of calcium carbonate added in an amount sufficient to completely react with and neutralize the fraction of any subsequently added complex acid which is not neutralized by apatite and calcium hydroxide and / or calcium oxide.

For the alkali / delayed addition process, there is at least one delay period between the pre-conversion addition of water and the pre-conversion addition of at least one fraction of one or more other non-aqueous conversion agents. The first delay period is initiated after the first addition of water as a conversion agent. If additional water is added prior to the conversion to compensate for evaporation losses during the manufacturing process, such additives are not used in the resumption or determination of the delay period and only the first addition of water is used as the starting point of the determination of the delay period do. Most preferably, the one or more delay periods (the time between addition of water and at least one fraction of non-aqueous conversion agent) is a temperature-controlled delay period or a maintenance delay period, or both. The delay period may involve multiple temperature adjustment delay periods and multiple sustain delay periods.

For example, the first temperature adjustment delay period is a period of time required to change the temperature of the mixture to a desired temperature or temperature range (first temperature) (typically by heating) after the addition of water. The first holding delay period is the amount of time to maintain the mixture at the first temperature. The second temperature regulation delay period is the time period required to heat or cool the mixture to another temperature or temperature range (second temperature) after the first maintenance delay. The second temperature adjustment delay period may be selected such that the temperature of the mixture is raised to a further temperature or temperature range (second temperature) or cooled when another component (for example, a complex acid) is added after the first temperature is reached But there is no delay period between the arrival at the first temperature and the continuation of heating or cooling to the second temperature. The second retention delay period is the amount of time that the mixture is maintained at the second temperature. The additional temperature adjustment delay period and the maintenance delay period (i.e., the third temperature adjustment delay period) follow the same format. The first temperature may be an ambient temperature or an elevated temperature. Any subsequent temperature may be higher or lower than the previous temperature. The final pre-conversion temperature may range from about 190 to 220 [deg.] F or up to 230 [deg.] F will be. The final pre-conversion temperature may be below 190 있지만, but these process conditions will generally result in significantly longer conversion times, and the viscosity agent may be reduced. The final pre-conversion temperature and temperature range at which the conversion takes place may be different in closed vessels. Any combination of the temperature adjustment delay period and / or the maintenance delay period may be used. Most preferably, the mixture of components before the conversion is heated to a constant temperature or a constant temperature range for at least one delay period or for each delay period.

In general, the holding delay period may be followed or preceded by a temperature adjusting delay period, and vice versa, but two holding delay periods may be continuous or two of the two temperature adjusting periods may be consecutive. For example, the mixture may be maintained at ambient temperature for 30 minutes prior to the addition of one non-aqueous conversion agent (first retention delay period) and at another time prior to the addition of the same or different non-aqueous conversion agent Lt; / RTI > (second retention delay period). The mixture may also be heated or cooled to a first temperature after the addition of the non-aqueous conversion agent (first temperature adjustment period), and then the mixture is heated to a second temperature after the addition of the same or different non- (A second temperature adjustment period without any intermediate maintenance period). Also, the fraction of the non-aqueous conversion agent need not be added after every delay period, and the delay period between additions or between additions may be omitted. For example, the mixture can be heated to a constant temperature (first temperature adjustment delay period) and then maintained at the temperature for a period of time prior to the addition of any non-aqueous conversion agent term).

If a non-aqueous conversion agent or a portion thereof is added immediately after reaching a certain temperature or constant temperature range, then there is no maintenance delay time for said specific temperature and said non-aqueous conversion fraction; If another fraction is added after being maintained in the temperature or temperature range for a period of time, then there is a maintenance delay period for the temperature and the non-aqueous conversion fraction. One fraction of one or more non-aqueous conversion agents may be added after any temperature controlled delay period or retention delay period and another fraction of the same or different non-aqueous conversion agent may be added to another temperature controlled delay period or retention delay period Can be added later. Generally, each temperature adjustment delay period will be about 30 minutes to 24 hours, or more usually about 30 minutes to 5 hours. However, any temperature adjustment delay period may vary depending on the size of the grease batch, the equipment used to mix and heat the batch, and the temperature difference between the starting temperature and the final temperature, as will be appreciated by those skilled in the art. something to do.

Depending on the various preferred aspects of the alkali / delayed addition process, different variants for the delay period can be used. For example, each of the following is a separate preferred embodiment: (a) at least one fraction of the non-aqueous conversion agent is added (nearly simultaneously) including a first addition of water and the same non-aqueous conversion agent and / Another fraction of the aqueous conversion agent is added after at least one delay period; (b) no amount of the non-aqueous conversion agent is added at approximately the same time as the water, and there is at least one delay period prior to the addition of any non-aqueous conversion agent; (c) at least one fraction of the non-aqueous conversion agent is added to the mixture at a temperature in the range of from about 190 to about 230 DEG F before the final conversion, Heated to a temperature range in which it occurs); (d) when at least one of the non-aqueous converting agents is a glycol (e. g., propylene glycol or hexylene glycol), a fraction of the glycol is added at approximately the same time as water and another fraction of the glycol and any other The total of the non-aqueous converting agents is added after at least one delay period; (e) when acetic acid is added before the conversion, it is added at about the same time as water and another (different) non-aqueous conversion agent is added after the delay period; (f) at least one fraction of one or more non-aqueous converting agents is added at the end of the last period of one or more delay periods, and another fraction of the same and / or the same or different non- Lt; / RTI > Or (g) the entire one or more non-aqueous converting agents are added at the end of the last period of one or more delay periods.

According to one preferred embodiment of the alkali / delayed addition process, all or one fraction of the non-aqueous converting agents are added in batch mode after the delay period (all at once, in contradistinction to the continuous addition according to the delay period process described below) . However, in large or commercial scale operations, due to the volume of material involved, it will take some time to complete the batch addition of this non-aqueous conversion agent in the grease preparation. In the batch addition, the time taken to add the non-aqueous conversion agent to the grease mixture is not considered to be a delay period. In this case, any delay prior to the non-aqueous conversion agent or its addition is terminated at the start time of the batch addition of the non-aqueous conversion agent. According to another preferred embodiment, at least one or one fraction of one non-aqueous conversion agent is added in a continuous manner during a delay period (temperature controlled delay period or retention delay period). Such continuous addition may be achieved by the slow addition of the non-aqueous conversion agent at a substantially constant flow rate, or by repeated, separate, increased additions during the temperature adjustment delay period, the maintenance delay period, or both. In this case, the time required to fully add the non-aqueous conversion agent is included in the delay period, and the period ends upon completion of the addition of the non-aqueous conversion agent. According to another preferred embodiment of the alkali / delayed addition process, at least one fraction of one non-aqueous conversion agent is added in a batch mode after a delay period, and at least another fraction of the same or a different non- For a period of time. According to another preferred embodiment of the alkali / delayed addition process, the alcohol is not used as a non-aqueous conversion agent.

Although the delay period within the scope of the present invention may be accompanied by a maintenance delay period without heating (e.g. the mixture is maintained at ambient temperature during the first retention delay period prior to heating) The short time period of 15 minutes or less without any heating between additions of the entire non-aqueous transition agent (s) is not a "delay" or "delay time " The delay for any or all of the non-aqueous conversion agent (s) without heating during the delay period should be at least about 20 minutes, more preferably at least about 30 minutes, for the purposes of the present invention. (S) between the addition of water and the addition of the non-aqueous conversion agent, but not heating, but the addition of some or all of the other non-aqueous conversion agent (s) A subsequent interval of less than 20 minutes, including a longer holding delay period or subsequent heating, does not involve a "lag period" within the scope of the present invention. In this case, the initial short term interval is not a "delay period ", but subsequent longer holding delay or temperature regulation delay prior to addition of the non-aqueous conversion agent is a maintenance delay period or temperature adjustment delay period for the purposes of the present invention. In addition, all or a portion of one or more non-aqueous conversion agents may be added slowly over one or more of the temperature-controlled delay period or the maintenance delay period, or both. This slow addition may involve a substantially continuous addition of a non-aqueous conversion agent during repeated increasing additions during the delay period (s) or delay period (s).

In addition, when acetic acid or 12-hydroxystearic acid is added prior to the conversion, these acids will have a dual role as both a converting agent and a complexing acid. When these acids are added with another more active non-aqueous conversion agent (e.g., glycol), the acid first acts as a complexing acid and the more active agent acts as a primary agent of the conversion agent . Thus, when acetic acid or 12-hydroxystearic acid is added prior to conversion with a more active conversion agent, any elapsed time between the addition of water and any fraction of acetic acid or 12-hydroxystearic acid can be used herein It is not regarded as a delay as a used term. In this case, only the temperature-regulated delay period or the maintenance delay period between the addition of the water before the conversion and the addition before the conversion of any fraction of the other non-aqueous conversion agent is regarded as a delay for the purpose of the present invention. When acetic acid or 12-hydroxystearic acid or a combination thereof is the only non-aqueous conversion agent (s) used, the temperature between the addition of the pre-conversion of water and the addition of acetic acid or any fraction of 12- The adjustment delay period or the maintenance delay period may be a delay for the purpose of the present invention.

One preferred embodiment of the alkali / delayed addition process according to the present invention comprises the following steps: (1) mixing the following ingredients in a suitable grease preparation vessel: water as the conversion agent, water containing dispersed amorphous calcium carbonate At least a portion of at least one fraction of at least one non-aqueous conversion agent to form a first mixture; optionally, a suitable amount of a suitable base oil (if necessary), one or more alkali metal hydroxides, and optionally; (2) mixing and stirring / mixing or stirring the first mixture while maintaining the first mixture at a constant temperature or a predetermined temperature range, or (2) heating the first mixture to a temperature To be heated or cooled; (3) optionally, mixing at least one fraction of the at least one non-aqueous conversion agent with the first mixture after the at least one delay period or during the period to form a second mixture; (4) the first mixture (or the second mixture if the non-aqueous conversion agent is added in step (3)) during the final period of the one or more delay periods is at a transition temperature (preferably, To a temperature in the range of 190 to 230 DEG F higher than 190 to 220 DEG F) to form a third mixture; (5) mixing, after step (4) or during step (4), one or more non-aqueous transition agents or any remaining part (s); And (6) converting the amorphous calcium carbonate contained in the overbased calcium sulfonate to the finely divided crystalline calcium carbonate until the temperature is maintained within the conversion temperature range (preferably 190 ≪ / RTI > to < RTI ID = 0.0 > 230 F) < / RTI > (7) mixing one or more calcium-containing bases; (8) optionally, mixing the promoting acid; And (9) mixing one or more suitable complexing acids. This method produces the preferred composite calcium sulfonic acid grease. Step 7 may be carried out prior to or after conversion, or some fraction or all of the one or more calcium-containing bases may be added prior to conversion, and some or all of the one or more calcium-containing bases may be added after conversion . Step (8) may be performed at any time prior to conversion. Step (9) may be carried out prior to or after conversion, or some fraction or all of the one or more of the complexing acids may be added prior to conversion, and some or all of the one or more of the complexing acids may be added after conversion . Most preferably, such an alkali / delayed addition process is carried out in an open container, but may also be carried out in a pressurized container. Most preferably, the one or more alkali metal hydroxides are dissolved in water to be used as a conversion agent prior to their addition in step (1). Alternatively, the alkali metal hydroxide may be removed in step (1) and dissolved in water, and the solution is added later before or after conversion.

For any of the preferred embodiments of the alkali / delayed addition method disclosed herein, any fraction of the non-aqueous conversion agent added in step (1), step (3) and / or step (5) Or may be the same as the non-aqueous conversion agent added in the steps or may be different from any non-aqueous conversion agent added in another step or steps. When added at least after a delay period of at least one non-aqueous conversion agent (in step (3) or step (5)), another fraction of the same non-aqueous conversion agent or non-aqueous conversion agents and / Or at least one fraction of non-aqueous converting agents may be added in any combination of step (1), step (3) and / or step (5). According to another preferred embodiment of the alkali / delayed addition process, the one or more of the non-aqueous conversion agents are added after step (5) in the final conversion period, without being added during step (1) or step (3) Mixed. According to another preferred embodiment of the alkali / delayed addition process, at least one fraction of the one or more non-aqueous conversion agents is added with the first mixture in step (1) prior to any retardation, and the same or different non- At least one fraction of the conversion agent is added in step (3) and / or step (5). According to another preferred embodiment of the alkali / delayed addition process, the non-aqueous conversion agent is not added to the first mixture and at least one fraction of the at least one non-aqueous conversion agent is added in step (3) or step (5) . According to another preferred embodiment of the alkali / delayed addition process, at least one fraction of the at least one non-aqueous conversion agent is added after one delay period or during the period in step (3), and the same or different non- At least one fraction of the agent is added after another delay period or during the period (the second delay period of step (3) and / or the last delay period of step (5)). According to another preferred embodiment of the alkali / delayed addition process, at least one fraction of the one or more non-aqueous conversion agents is added after one or more delays of step (3), but after the last delay period of step (5) No conversion agent is added.

The order of steps (2) to (6) for producing the composite grease is an important aspect of the present invention with respect to aspects including an alkali / delayed addition method. Certain other aspects of the method are not critical in obtaining the preferred calcium sulfonate composition of the present invention. For example, the order in which calcium-containing bases are added to one another is not important. Also, although the temperature at which water and the calcium-containing base as a conversion agent are added to obtain an acceptable grease is not critical, it is also important that the temperature reaches 190 to 200 ℉ (or other temperature range where conversion occurs in the closed vessel) It is preferable that they are added beforehand. When one or more complex acids are used, the order in which they are added before or after conversion is generally not important.

Another preferred embodiment of the alkali / delayed addition process comprises: mixing water, one or more alkali metal hydroxides, up to 45% of an overbased calcium sulfonate containing dispersed amorphous calcium carbonate, and optionally a base oil, Forming a first mixture; Adding at least one fraction of one or more non-aqueous conversion agents to the first mixture after at least one delay period or during the period to form a mixture before conversion; Wherein the first mixture or the pre-conversion mixture comprises at least one of the delay periods during which a maintenance delay time is maintained within a predetermined temperature or a constant temperature range during the maintenance delay period, wherein the at least one of the amorphous calcium carbonate Heating to the conversion to crystalline calcium carbonate until the conversion of the pre-conversion mixture to the converted mixture. In another embodiment, one or more alkali metal hydroxides are added after conversion instead of before conversion, or one fraction before conversion and one fraction after conversion. The pre-conversion and post-conversion additions may be the addition of the same or different alkali metal hydroxides.

Another preferred embodiment of the alkali / delayed addition process comprises: mixing water, one or more alkali metal hydroxides, up to 36% of an overbased calcium sulfonate containing dispersed amorphous calcium carbonate, and optionally a base oil, Forming a first mixture; Adding at least one fraction of one or more non-aqueous conversion agents to the first mixture after at least one delay period or during the period to form a mixture before conversion; Converting the amorphous calcium carbonate contained in the calcium perchlorate sulfonate by heating until the completion of the conversion to calcium carbonate is converted to the converted mixture. In another embodiment, one or more alkali metal hydroxides are added after conversion instead of before conversion, or one fraction is added prior to conversion and one fraction is added after conversion. The pre-conversion and post-conversion additions may be the addition of the same or different alkali metal hydroxides.

Another preferred embodiment of the alkali / delayed addition process comprises the following steps: In a suitable grease preparation vessel, a high degree of overbased salt of calcium carbonate containing amorphous calcium carbonate is mixed with a suitable amount of suitable base oil (if necessary) , ≪ / RTI > Thereafter, one or more facilitating acids are added, preferably mixed for about 20 to 30 minutes. Thereafter, one part of the calcium hydroxide is added to the entire calcium hydroxyapatite, and then the entire calcium carbonate is added and mixed for another 20 to 30 minutes. Next, one fraction of acetic acid and one fraction of 12-hydroxystearic acid are added and mixed for another 20-30 minutes (these components may be conversion agents, but since they are added before water, there is a delay period associated with them I did not notice it). Thereafter, water used as a conversion agent, including a small amount of alkali metal hydroxide dissolved therein, is added and mixed while being heated to a temperature of 190 to 230 ° F (first temperature adjustment delay period and final delay period). Thereafter, the entire hexylene glycol is added as a non-aqueous conversion agent. The mixture is maintained in the conversion temperature range (preferably 190 to 230 의 for open vessels) until the conversion of the amorphous calcium carbonate contained in the overbased calcium sulfonate to the finely divided crystalline calcium carbonate is completed, Lt; RTI ID = 0.0 > temperature. ≪ / RTI > After conversion, the remaining calcium hydroxide is added and mixed for about 20 to 30 minutes. The remaining acetic acid and the remaining 12-hydroxystearic acid are then added and mixed for about 30 minutes. Then, boric acid dispersed in water is added, and then phosphoric acid is slowly added slowly. The mixture is then heated to remove water and volatiles, cooled, more base oil is added as needed, and the grease is milled as described below. Additional additives may be added during the final heating or cooling step. According to another preferred embodiment of the alkali / delayed addition process, the steps and components are heated to about 160 ℉ (after addition of water as a conversion agent and prior to the addition of hexylene glycol as a non-aqueous conversion agent (The first holding delay period), and the temperature is maintained at the above temperature for about 30 minutes before continuing the heating (the second temperature adjustment delay period and the last delay period) to 190 to 230 ° F , ≪ / RTI >

Preferred embodiments of both the alkali addition process and the alkali / delay addition process which can be carried out in an open or closed kettle are generally used for the production of grease. The conversion method can be accomplished under normal atmospheric pressure or in a closed kettle under pressure. Manufacture in an open kettle (non-pressurized vessel) is preferred because such grease-making equipment is generally available. For purposes of the present invention, an open container is any container that does or does not include an upper cover or hatch, and may be vapor-tight so that significant pressure can not be generated during heating of such an upper cover or hatch, Is not. The use of such an open container, including a sealed fossil cover or hatch during the conversion process, will generally help keep the shear temperature above the boiling point of water and at the same time maintain the required level of water as a conversion agent. This higher conversion temperature can cause additional thickener improvements in both the simple and complex calcium sulfonate phosphates, as will be appreciated by those skilled in the art. The preparation in a pressurized kettle may also be used, which may lead to a better improvement of the thickener head, but the method of pressurization may be more complex and difficult to control. In addition, the production of calcium sulphonate grease in a pressurized kettle can cause productivity problems. The use of a pressurized reaction may be important for certain types of grease (e.g., polyurea grease), and most grease plants may have only a limited number of pressure vessels. The use of a pressurized kettle to produce calcium sulphonate grease, where the pressurization response is not critical, may limit the ability of other greases to be produced in plants where pressurization is important. These problems are avoided by using open containers.

Most preferably, both the alkaline addition process and the alkali / delayed addition process for producing the complex calcium sulfonate sulphate include the following steps: (a) after the conversion, mixing the additional base oil and the complexing acid as necessary ; (b) mixing and heating to a temperature sufficiently high to ensure removal of water and all volatile reaction by-products and to optimize final product quality; (c) cooling the grease while adding additional base oil as needed; (d) adding other desired additives as is well known in the art; And, if necessary, (e) milling the final grease as desired to obtain a final, smooth, homogeneous product. Although the order and timing of these final steps are not critical, it is desirable that the water be quickly removed after conversion. Generally, in order to remove water initially added as a conversion agent, and all water formed by the chemical reaction during the formation of the grease, the grease (preferably under pressure, but under pressure, under pressure) To 250 to 300,, preferably to 300 to 380,, and most preferably to 380 to 400.. Having water in the grease batch for an extended period of time during manufacture can cause degradation of thickener stares, red spots, or both, and this adverse effect can be avoided by quickly removing the water. When polymeric additives are added to the grease, they should preferably not be added until the grease temperature reaches 300 ℉. Polymeric additives can interfere with effective evaporation of water when added in sufficient concentrations. Thus, the polymeric additive should preferably be added to the grease only after all the water has been removed. If, during manufacture, it is possible to determine that all the water has been removed before the grease temperature has reached, preferably 300 DEG F, preferably any polymer additive may be added at all subsequent times.

Examples 1 to 18 of U.S. Patent No. 9,273,265 and Examples 1 to 29 of the '768 patent application are incorporated herein by reference. The overbased calcium sulfonate grease composition according to the present invention and the method for preparing such a composition are further disclosed and explained with reference to the following examples.

Example 1A (Baseline Example-no alkaline addition process, no alkali / delayed addition process): Calcium sulfonate composite grease according to the composition of the '768 patent application was prepared as follows: 264.61 g of 400 TBN overbased vaporization oil Following calcium sulphonate, 327.55 g of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 및 and 11.70 g of PAO having a viscosity of 4 cSt at 100 캜 were added to the open mixing vessel. The 400 TBN overbased fluorosurfactant calcium sulfonate was a low quality calcium sulfonate similar to that used in Example 10 and Example 11 of the '768 patent application described above. Mixing without heating was initiated using a planetary mixing paddle. Thereafter, 23.94 g of alkylbenzenesulfonic acid, mainly C12, was added. After mixing for 20 minutes, 50.65 g of calcium hydroxyapatite having an average particle size of about 1 to 5 microns and 3.63 g of calcium hydroxide of food grade purity having an average particle size of about 1 to 5 microns were added, Mixed. The amount of calcium hydroxide to be added as a separate component is an amount other than the amount of the residual calcium hydroxide contained in the calcium perchlorate sulfonate. Then, 0.88 g of glacial acetic acid and 10.53 g of 12-hydroxystearic acid were added and allowed to mix for 10 minutes. Then, 55.03 g of finely divided calcium carbonate having an average particle size of about 1 to 5 microns was added and allowed to mix for 5 minutes. The amount of calcium carbonate added as a separate component is an amount other than the amount of the dispersed calcium carbonate contained in the calcium carbonate. Then, 13.20 g of hexylene glycol (non-aqueous conversion agent) and 38.22 g of water were added at substantially the same time (without delay period). The mixture was heated until the temperature reached 190 ° F. The temperature was maintained at 190 to 200 DEG F for 45 minutes until the Fourier Transform Infrared (FTIR) spectroscopy indicated that conversion of the amorphous calcium carbonate to crystalline calcium carbonate (calcite) occurred.

Due to the heaviness of the converted grease, another 56.07 g of the same paraffinic base oil was added. Thereafter, 7.36 g of the same calcium hydroxide as above was added and mixed for 10 minutes. Then, 1.52 g of glacial acetic acid was added followed by 27.30 g of 12-hydroxystearic acid. As these acids reacted and the grease was further thickened, 111.07 g of paraffinic base oil was added. Then, 9.28 g of boric acid were mixed in 50 g of hot water and the mixture was added to the grease. Another 54.47 g of paraffinic base oil followed by 17.92 g of a 75% solution of phosphoric acid in water was added. The mixture was then heated with continued stirring using an electric heating mantle. When the grease reached 300 ℉, 22.22 g of styrene-ethylene-propylene copolymer was added as a crumb-formed solid. The entire polymer was dissolved and the grease was further heated to about 390 [deg.] F when fully 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 was cooled to 300 ℉, 33.01 g of food grade anhydrous calcium sulfate having an average particle size of about 1 to 5 microns was added. When the temperature of the grease was cooled to 200 ℉, 4.43 g of polyisobutylene polymer was added. Mixing was continued until the grease reached a temperature of 170 < 0 > F. The grease was then removed from the mixer and passed three times through a three roll mill to achieve a final smooth and homogeneous texture. The grease had a 287 sixty reciprocating blending lead. Percent salt in the final grease was 23.9% calcium perchlorate. The redness was > 650 [deg.] F. In this embodiment, calcium hydroxyapatite and calcium carbonate were added prior to conversion according to aspects of the '768 patent application. In addition, 33% of the total calcium hydroxide was added prior to conversion, followed by 35% of the total amount of glacial acetic acid and 28% of the total amount of 12-hydroxystearic acid. The remaining amount of calcium hydroxide, glacial acetic acid, 12-hydroxystearic acid was added after conversion.

Example 1B (Method of delayed addition of '476 patent application, without addition of alkali): Another calcium composite grease was prepared in the same manner as in Examples 1A and 1B except that there was a delay in the addition of a non-aqueous conversion agent (hexylene glycol) Using the same equipment, raw materials, quantity, and manufacturing method. The other initial components (including water) were mixed and heated to a temperature of about 190 ° F (first temperature regulated delay period) and hexylene glycol was added immediately after reaching 190 ° F (no retention delay period). When hexylene glycol was added, the conversion occurred rapidly. The grease was maintained at 190 to 200 DEG F for an additional 45 minutes. Thereafter, the remaining process was the same as that of the grease of Example 1 above. Final Greece had 290 60 roundtrip blends. The percentage of the final grease was 21.4% for the perchlorinated oil-soluble calcium sulfonate. The redness was > 650 [deg.] F. As can be seen, the grease of this example had an improved thickener bead compared to the grease of Example 1, as evidenced by the lower final percentage of the overbased calcium sulfonate as compared to the blend lead.

Example 2 (mode of alkali / delayed addition process): Another calcium sulfonate complex grease was prepared by adding the alkali metal hydroxide to the water in Example 1B Similar to Greece. The grease was prepared as follows: 240.35 g of 400 TBN perchlorinated oil of calcium sulfonate followed by 345.33 g of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100, and 10.79 g of 100 The PAO having a viscosity of 4 cSt at < RTI ID = 0.0 > 0 C < / RTI > The 400 TBN overbased fluorosurfactant calcium sulfonate was a low quality calcium sulfonate similar to that described above and used in Example 10 and Example 11 of U.S. Patent Application No. 13 / 664,768. Mixing without heating was initiated using planetary mix paddles. Thereafter, 21.81 g of alkylbenzenesulfonic acid, mainly C12, was added. After 20 minutes of mixing, 46.14 g of calcium hydroxyapatite having an average particle size of 5 microns or less and 3.34 g of calcium hydroxide of food grade purity having an average particle size of 5 microns or less were added and allowed to mix for 30 minutes. Subsequently, 50.20 g of finely divided calcium carbonate having an average particle size of 5 microns or less was added and allowed to mix for 5 minutes. Thereafter, 35 g of water in which 0.41 g of powdered sodium hydroxide was dissolved was added.

The mixture was heated to about 180 < 0 > F. Then, 0.76 g of glacial acetic acid and 9.63 g of 12-hydroxystearic acid were added (initially as a complexing acid, since glycol was later added as a non-aqueous conversion agent). It is noted that the 12-hydroxystearic acid rapidly melts, melts, and reacts at a temperature of about 180 ° F where the acid is added. Immediately after the addition of the two complexing acids, the mixture began to develop into the appearance of a whipped cream. This appearance generally does not occur when the water to be added does not contain a small amount of alkali metal hydroxide, which may in some way relate to the faster formation of the calcium salt of the complexing acids. Without wishing to be bound by theory, one possible explanation for the whipping cream appearance is that, once the sodium fatty acid salt is formed, a small steady state concentration is maintained until the calcium fatty acid salt is formed to be. Sodium fatty acid salts are well known to be water and surface active, and can cause foaming that can cause a whip cream appearance.

The mixture was stirred (first temperature adjustment delay period) while being heated to a temperature of 190 to 200 계속. Upon reaching a temperature range of 190 to 200 ° F, the appearance of the whipped cream subsided. Then, 12.46 g of hexylene glycol was added as a non-aqueous conversion agent. After 1 hour and 10 minutes, a visible transition has not yet occurred. FTIR also indicated that most of the initially added water was lost due to evaporation. An additional 35 ml of water and another 12.47 g of hexylene glycol were added. Another hour and 20 minutes later, a visible transition occurred.

The grease continued to thicken over time. In order to prevent the grease from becoming too heavy for effective stirring, a total of 100.93 g of two nearly identical fractions of the same paraffinic base oil were added. If additional evaporation seems to have stopped, another 30 ml of water was added due to evaporative loss. Fourier Transform Infrared (FTIR) spectroscopy showed that the conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) occurred. Then, 6.80 g of the same calcium hydroxide as above was added and mixed for 10 minutes. Thereafter, 1.45 g of glacial acetic acid was added followed by 24.76 g of 12-hydroxystearic acid. The grease was stirred at 190 to 200 ° F. As the grease thickened, immediately after adding 49.65 g of the same paraffinic base oil, another 54.28 g of the same base oil as above was added. Then, 8.50 g of boric acid was mixed with 30 g of hot water and the mixture was added to the grease. After allowing the boric acid to react, a solution of 75% phosphoric acid in 16.25 g of water was slowly added, mixed and allowed to react. As the grease continued to harden, another 49.47 g of paraffinic base oil was added. The mixture was then heated with continued stirring using an electric heating mantle. When the grease reached 300 ℉, 20.64 g of the styrene-alkylene copolymer was added as a slab-like solid. The grease was further heated to a target temperature of 390 [deg.] F. However, the overtemperature was overshoot to 429 ° F. The heating mantle was removed and the grease was allowed to cool by continued stirring in open air. When the maximum temperature reached, the polymer was melted and completely dissolved in the grease mixture. When the grease was cooled to 300 ℉, 30.29 g of food grade anhydrous calcium sulfate having an average particle size of 5 microns or less was added. Upon cooling the grease to 200 ℉, 2.23 g of arylamine antioxidant and 4.18 g of polyisobutylene polymer were added. An additional 49.92 g of the same paraffinic base oil as above was added.

Mixing was continued until the grease reached a temperature of 170 < 0 > F. The grease was then removed from the mixer and passed three times through a three roll mill to achieve a final smooth and homogeneous texture. The grease had 281 60 reciprocating blends. Percent salt in the final grease was 20.49% calcium perchlorate-soluble. The redness was > 650 [deg.] F. As can be seen, these grease thickeners were superior to the two example greases. Using a conventional semi-linear relationship between the mixing lead and the percontent hydrogencarbonate calcium sulfonate concentration, the grease of this example would be 19.85 < RTI ID = 0.0 > % Calcium perchlorate percents. The result, which is known to have a potentially harmful effect on the thickener oil, is more surprising because the grease of Example 2 above has been heated to about 29 ° F. The amount of sodium hydroxide to the initial unreacted weight in the final grease product was 0.06%. It should be understood that the reference to the percentage of alkali metal hydroxide in the final grease of the present invention is indicative of the amount of alkali metal hydroxide added as a constituent in the preparation of the grease which means that the alkali metal hydroxide reacts with the complexing acid to form a salt And will not be present in the final grease as the initial unreacted hydroxide. However, for ease of reference, the concentration in the final grease is expressed as the amount of alkali metal hydroxide added as a component to the weight of the final grease product.

Example 3 (mode of alkali / delayed addition method): Another calcium sulfonate composite grease was prepared in a manner similar to the grease of Example 2 above. The only significant difference was that the initial fractions of acetic acid and 12-hydroxystearic acid were added at the beginning of the process, while maintaining the mixture at ambient laboratory temperature (prior to any heating). Similar to the grease of Example 2 above, this grease uses an embodiment of the alkali / delayed addition method. Also, care was taken to ensure that the batch was not overheated during the final heating step.

The grease of Example 3 was prepared as follows: 240.31 g of 400 TBN perchlorinated oil, calcium sulfonate followed by 345.09 g of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100,, and 10.03 g Of PAO having a viscosity of 4 cSt at 100 DEG C was added to an open mixing vessel. The 400 TBN overbased fluorosurfactant calcium sulfonate was a low quality calcium sulfonate similar to that described above and used in Example 10 and Example 11 of U.S. Patent Application No. 13 / 664,768. Mixing without heating was initiated using planetary mix paddles. Thereafter, 21.83 g of alkylbenzenesulfonic acid, mainly C12, was added. After 20 minutes of mixing, 46.03 g of calcium hydroxyapatite having an average particle size of 5 microns or less and 3.30 g of calcium hydroxide of food grade purity having an average particle size of 5 microns or less were added and allowed to mix for 30 minutes. Then 0.76 g of glacial acetic acid and 9.80 g of 12-hydroxystearic acid were added and allowed to mix for 15 minutes. Thereafter, 50.29 g of finely divided calcium carbonate having an average particle size of 5 microns or less was added and allowed to mix for 5 minutes. Thereafter, 35.0 g of water in which 0.40 g of powdered sodium hydroxide was dissolved was added. The mixture was heated (first temperature adjustment delay period) until the temperature reached 190-200 [deg.] F. During heating to this temperature range, the whip cream appearance became evidence when the temperature reached about 150 ° F. The whipped cream appearance submerged shortly after reaching a temperature range of 190 to 200 < 0 > F. Upon reaching a temperature range of 190 to 200 [deg.] F, 24.17 g of hexylene glycol was added (there was no maintenance delay period). This amount is an amount corresponding to the approximate total amount of hexylene glycol added to the two separate fractions in the Example Grease. However, in this embodiment of the invention, they are all added at once because the addition of alkali metal hydroxides containing water modifies the conversion process and often appears to require additional non-aqueous conversion agents. An additional 20 ml of water was also added and the mixture was stirred for about 1 hour until visible conversion occurred.

Subsequently, an additional 10 ml of water followed by a total of 99.73 g of two nearly identical fractions of the same paraffinic base oil were added. This was done in order to prevent the grease from becoming thick enough to prevent the grease from mixing effectively. Fourier Transform Infrared (FTIR) spectroscopy showed that conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) occurred. Thereafter, 6.75 g of the same calcium hydroxide as above was added and mixed. An additional 30 ml of water was added to replace the water lost due to evaporation. Thereafter, as the grease mixture continued to thicken, another 55.22 g of the same base oil was added. Another 1.47 g of glacial acetic acid was added followed by 24.70 g of 12-hydroxystearic acid. Thereafter, the grease was mixed for 15 minutes. The grease mixture was still thickened and 43.38 g was added followed by another 53.97 g of the same base oil.

Then, 8.49 g of boric acid was mixed with 30 ml of hot water, and the mixture was added to the grease. After allowing the boric acid to react, a 75% solution of phosphoric acid in 16.30 g of water was slowly added and allowed to mix and react. The mixture was then heated with continued stirring using an electric heating mantle. When the grease reached 300 DEG F, 20.24 g of the styrene-alkylene copolymer was added as a slab-like solid. The grease was further heated to about 390 [deg.] F when the entire polymer melted and was 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 was cooled to 300 ℉, 30.39 g of food grade anhydrous calcium sulfate having an average particle size of 5 microns or less was added. When the temperature of the grease was cooled to 200 ℉, 2.06 g of arylamine antioxidant and 4.46 g of polyisobutylene polymer were added. A total of 132.79 g of three identical fractions of the same base oil were added and allowed to mix in the grease. Mixing was continued until the grease reached a temperature of 170 < 0 > F. The grease was then removed from the mixer and passed three times through a three roll mill to achieve a final smooth and homogeneous texture.

The final grease of Example 3 had 282 60 reciprocating blending runs. Percent of the final grease was 19.20% of the perchlorinated oil-soluble calcium sulfonate. The redness was > 650 [deg.] F. As can be seen, the grease had an improved thickener bead compared to the greases of Examples 1A and 1B. In fact, this grease has an improved thickener bead compared to the '473 patent application, the' 768 patent application, and all the example greases of US Pat. No. 9,273,265. This is believed to be the best thickener achievable for the calcium sulfonate composite grease in an open mixer / kettle (non-pressure) system recorded in the published literature. In the case of manufacturing in a hermetically sealed pressure kettle, the thickener is considered to be better than 19.2%.

Example 4 (Baseline example-no alkali metal hydroxide, no delay period): Another calcium sulfonate complex grease was prepared using different base oils, using different non-aqueous conversion agents, without using boric acid, Except that no alkali metal hydroxide was added and there was no delay between the addition of water and a non-aqueous conversion agent. This example grease acts as a baseline for comparison with the other example grease disclosed herein in which an alkali metal hydroxide is added and at least one delay period exists between the addition of water and a non-aqueous conversion agent.

The grease of Example 4 was prepared as follows: 297.25 grams of 400 TBN perchlorinated oil soluble calcium sulfonate followed by 373.60 grams of USP purity white paraffinic mineral base oil having a viscosity of about 352 SUS at 100 DEG F, . The overbased calcium sulfonate calcium was an NSF HX-1 food grade approved overbased calcium sulfonate calcium suitable for making NSF H-1 approved food grade grease and was of good quality as defined in the '768 patent application. Mixing without heating was initiated using planetary mix paddles. Thereafter, 26.99 g of alkylbenzenesulfonic acid, mainly C12, was added. After mixing for 20 minutes, 50.58 g of calcium hydroxyapatite having an average particle size of 5 microns or less and 4.06 g of calcium hydroxide of food grade purity having an average particle size of 5 microns or less were added and allowed to mix for 30 minutes. Then 0.96 g of glacial acetic acid and 11.94 g of 12-hydroxystearic acid were added and allowed to mix for 10 minutes. Subsequently, 55.19 g of finely divided calcium carbonate having an average particle size of 5 microns or less was added and allowed to mix for 5 minutes. Thereafter, 37.2 g of water and 14.89 g of propylene glycol (as a non-aqueous conversion agent) were added without any delay. The mixture was heated until the temperature reached 190-200 [deg.] F. Conversion and visible vaporization were initiated before reaching the target temperature range. The temperature was maintained at 190 to 200 DEG F for 1 hour and 10 minutes. During this time another 15 ml of water was added to replace the water lost due to evaporation.

After 1 hour and 10 minutes, Fourier Transform Infrared (FTIR) spectroscopy indicated that the conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) occurred. As the ignition started to take place, an additional 54.07 g of the same base oil as above was added. Then, 25 ml of water and 8.35 g of the same calcium hydroxide as above were added and mixed for 10 minutes. Then, 1.82 g of glacial acetic acid was added followed by 30.60 g of 12-hydroxystearic acid. After these two complex acids had reacted, another 52.86 g of the same base oil was added due to the increased hardness of the grease mixture. Then, a solution of 75% phosphoric acid in 20.27 g of water was added slowly, mixed and allowed to react. The mixture was then heated with continued stirring using an electric heating mantle. When the grease reached 300 ℉, 2.86 g of the styrene-alkylene copolymer was added as a piecewise solid. The entire polymer was melted and the grease was further heated to about 390 된 when it was 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 was cooled to 300 ℉, 33.10 g of food grade anhydrous calcium sulfate having an average particle size of 5 microns or less was added. When the temperature of the grease was cooled to 200 ℉, 5.60 g of a mixture of arylamine and high molecular weight phenolic antioxidant and 5.50 g of amine phosphate antioxidant / rust inhibitor were added. An additional 50.70 g of the same base oil as above was added followed by another 29.39 g of the same base oil. Mixing was continued until the grease reached a temperature of 170 < 0 > F. The grease was then removed from the mixer and passed three times through a three roll mill to achieve a final smooth and homogeneous texture. The grease had 281 60 reciprocating blends. Percent salt of the final grease was 26.29% calcium perchlorate. The redness was > 650 [deg.] F.

Example 5 (mode of alkali / delayed addition process): Another calcium sulphonate composite grease was prepared in the same manner as in Example 1, except that the alkali metal hydroxide was added and there was a delay between the addition of water and the non- Example 4 Manufactured in a manner similar to grease. The alkali metal hydroxide used was sodium hydroxide, and the concentration thereof in the final grease was 0.03%. In addition, the amount of non-aqueous conversion agent (propylene glycol) was approximately twice that of Example 4, as observed in the above Example 2 and Example 3 greases in which the mode of the alkali / delayed addition method was used.

The grease of Example 5 was prepared as follows: 298.15 grams of 400 TBN perchlorinated oil soluble calcium sulfonate followed by 360.45 grams of USP purity white paraffinic mineral base oil having a viscosity of about 352 SUS at 100 DEG F, . The overbased calcium sulfonate was an NSF HX-1 food grade approved overbased calcium sulfonate suitable for the manufacture of NSF H-1 approved food grade grease and was of good quality as defined in the '768 patent application. Mixing without heating was initiated using planetary mix paddles. Thereafter, 27.10 g of alkylbenzenesulfonic acid, mainly C12, was added. After mixing for 20 minutes, 50.61 g of calcium hydroxyapatite having an average particle diameter of 5 microns or less and 4.09 g of calcium hydroxide of food grade purity having an average particle diameter of 5 microns or less were added and allowed to mix for 30 minutes. Then 0.96 g of glacial acetic acid and 11.92 g of 12-hydroxystearic acid were added and allowed to mix for 15 minutes. Then, 55.04 g of finely divided calcium carbonate having an average particle size of 5 microns or less was added and allowed to mix for 5 minutes. Thereafter, 39.1 g of water in which 0.44 g of powdered sodium hydroxide was dissolved was added. The mixture was heated while continuously mixing until the temperature reached 190 to 200 DEG F (first temperature adjustment delay period). It was noted that when the temperature reached about 170 F, a whip cream appearance was observed. After reaching 190 to 200 [deg.] F, an additional 20 ml of water was added to replace the water lost due to evaporation. After mixing for 35 minutes (first retention period) at 190 to 200 ° F, 29.88 g of propylene glycol was added and the appearance of the whipped cream subsided prior to the addition of the non-aqueous conversion agent. Approximately 10 minutes later, visible transitions and increased ignition began to be observed. As the grease continued to thicken, 51.33 g of the same base oil was added along with 5 ml of water. Finally, another 51.25 g of the same base oil as above was added to prevent the grease from becoming excessively hardened. When Fourier Transform Infrared (FTIR) spectroscopy indicated almost all the water had disappeared, an additional 40 ml of water was added.

Fourier Transform Infrared (FTIR) spectroscopy showed conversion to amorphous calcium carbonate to crystalline calcium carbonate (calcite) after about 2 hours at 190-200 [deg.] F (2 hours after the addition of propylene glycol). Then, 40 ml of water and 8.12 g of the same calcium hydroxide as above were added and mixed for 10 minutes. As the grease continued to thicken, another 52.07 g of the same base oil was added. Then, 2.85 g of glacial acetic acid was added followed by 31.35 g of 12-hydroxystearic acid. After these two complexing acids reacted, another 52.11 g of the same base oil was added, due to the increased hardness of the grease mixture. Thereafter, another 20 ml of water was added followed by another 54.11 g of the same base oil. Then, a solution of 75% phosphoric acid in 20.14 g of water was added slowly, mixed and allowed to react. As the grease continued to become harder, another 52.50 g of the same base oil was added. The mixture was then heated with continued stirring using an electric heating mantle. When the grease reached 300 DEG F, 2.75 g of the styrene-alkylene copolymer was added as a piecewise solid. The grease was further heated to about 390 [deg.] F when the entire 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 was cooled to 300 ℉, 33.16 g of food grade anhydrous calcium sulfate having an average particle size of 5 microns or less was added. When the temperature of the grease was cooled to 200 ℉, 5.62 g of a mixture of arylamine and high molecular weight phenolic antioxidant and 5.68 g of amine phosphate antioxidant / rust inhibitor were added. A total of 107.41 g of three fractions of the same base oil as above were added. Mixing was continued until the grease reached a temperature of 170 < 0 > F. The grease was then removed from the mixer and passed three times through a three roll mill to achieve a final smooth and homogeneous texture. The grease had 288 sixty reciprocating blending runs. The percentage of the final grease was 21.78% for the perchlorinated oil-soluble calcium sulfonate. The redness was > 650 [deg.] F. As can be seen, the thickener of the present grease has been improved over the grease of Example 4 above and reaffirmed the noticeable effect of the alkali / delayed addition process.

Example 6 (mode of alkali / delayed addition method) : Another calcium sulfonate composite grease was prepared in a manner similar to that of Example 5 above, except that the amount of sodium hydroxide was doubled. The concentration of sodium hydroxide in the final grease was 0.06%. The grease was prepared as follows: 297.40 g of 400 TBN perchlorinated oilborne calcium sulfonate followed by 360.93 g of USP purity white paraffinic mineral base oil having a viscosity of about 352 SUS at 100 를 was added to an open mixing vessel. The overbased calcium sulfonate calcium was an NSF HX-1 food grade approved perbrominated calcium sulfonate suitable for making NSF H-1 approved food grade grease and was of good quality as defined in the '768 patent application. Mixing without heating was initiated using planetary mix paddles. Thereafter, 27.13 g of alkylbenzenesulfonic acid, mainly C12, was added. After mixing for 20 minutes, 50.63 g of calcium hydroxyapatite having an average particle size of 5 microns or less and 4.20 g of calcium hydroxide of food grade purity having an average particle size of 5 microns or less were added and allowed to mix for 30 minutes. Then 0.95 g of glacial acetic acid and 11.92 g of 12-hydroxystearic acid were added and allowed to mix for 15 minutes. Subsequently, 55.14 g of finely divided calcium carbonate having an average particle size of 5 microns or less was added and allowed to mix for 5 minutes. Thereafter, 39.2 g of water in which 0.88 g of powdered sodium hydroxide was dissolved was added. The mixture was heated with continuous mixing until the temperature reached 190-200 [deg.] F (first temperature adjustment delay period). It was noted that when the temperature reached about 184,, a whip cream appearance was observed. After 35 minutes of mixing (first retention time period) at 190 to 200 ° F, an additional 20 ml of water was added to replace the water lost due to evaporation. Immediately thereafter, the appearance of the whipped cream subsided, and 30.25 g of propylene glycol was added as a non-aqueous conversion agent. Twenty minutes later, visible conversion and explosion began. Another 10 ml of water was added due to the evaporation loss.

As the grease continued to thicken, another 57.48 g of the same base oil as above was added, followed by 51.96 g of the same base oil. When conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) and the process of increasing the viscosity were completed, 8.12 g of the same calcium hydroxide as above was added and allowed to mix for 10 minutes. As the grease continued to thicken, another 51.85 g of the same base oil was added. Thereafter, 1.83 g of glacial acetic acid was added, followed by 30.54 g of 12-hydroxystearic acid. After these two complexing acids reacted, since the hardness of the grease mixture increased, a total of 107.53 g of two or more fractions of the same base oil as above were added. Subsequently, another 10 ml of water was added followed by slowly adding a 75% solution of phosphoric acid in 20.30 g of water, mixed and allowed to react. As the grease became more hardened, a total of 99.63 grams of two fractions of the same base oil were added. Thereafter, the mixture was continuously heated with stirring using an electric heating mantle. When the grease reached 300 ℉, 2.91 g of the styrene-alkylene copolymer was added as a piecewise solid. The grease was further heated to about 390 [deg.] F when the polymer melted and was completely dissolved in the grease mixture. The heating mantle was removed and the grease was allowed to cool by continued heating in open air. When the grease was cooled to 300 ℉, 33.11 g of food grade anhydrous calcium sulfate having an average particle size of 5 microns or less was added. When the temperature of the grease was cooled to 200 ℉, 5.78 g of a mixture of arylamine and high molecular weight phenolic antioxidant and 5.78 g of amine phosphate antioxidant / rust inhibitor were added. A total of 114.78 g of three fractions of the same base oil as above were added. Mixing was continued until the grease reached a temperature of 170 < 0 > F. The grease was then removed from the mixer and passed three times through a three roll mill to achieve a final smooth and homogeneous texture. The grease had a 60 reciprocating blending lead of 295. Percent salt in the final grease was 20.78% calcium perchlorate. The redness was > 650 [deg.] F. As can be seen, the viscosity of the grease of the present grease is improved compared to the grease of Example 4 above and again proves the noticeable effect of the embodiment of the alkali / delayed addition process. Using the usual inverse linear relationship between the mixing lead and the percent perchloric acid calcium sulfonate concentration, the grease of the present example shows a 21.3% percent perineum salt breakthrough when the base oil makes the mixing lead the same value as the grease of Example 5 above. Would have had a calcium sulphonate calcium concentration. Thus, doubling the amount of sodium hydroxide in this Example 6 grease seems to have, in the best case, given some additional improvement over the thickening agent compared to Example 5 Grease.

Example 7 (mode of alkali / delayed addition method) : Another calcium sulfonate composite grease was prepared in a manner similar to the grease of Example 6 above. The only significant difference between this grease and the grease of Example 6 above was that the grease was maintained at 160 to 170 1 for one hour during the initial heating period. The grease was prepared as follows: 297.79 g of 400 TBN perchlorinated oil, calcium sulfonate followed by 362.02 g of USP purity white paraffinic mineral base oil having a viscosity of about 352 SUS at 100 를 was added to the open mixing vessel. The overbased calcium sulfonate calcium is an NSF HX-1 food grade approved perbrominated calcium sulfonate suitable for making NSF H-1 approved food grade grease and has good quality as defined by the '768 patent application. Mixing without heating was initiated using planetary mix paddles. Thereafter, 27.01 g of alkylbenzenesulfonic acid, mainly C12, was added. After mixing for 20 minutes, 50.64 g of calcium hydroxyapatite having an average particle size of 5 microns or less and 4.14 g of calcium hydroxide of food grade purity having an average particle size of 5 microns or less were added and allowed to mix for 30 minutes. Then 0.94 g of glacial acetic acid and 11.92 g of 12-hydroxystearic acid were added and allowed to mix for 15 minutes. Thereafter, 55.37 g of finely divided calcium carbonate having an average particle size of 5 microns or less was added and allowed to mix for 5 minutes. Thereafter, 39.1 g of water in which 0.88 g of powdered sodium hydroxide was dissolved was added. The mixture was heated while continuing to mix until the temperature reached 160-170 DEG F (first temperature adjustment delay period). During this time, I noticed that the whipped cream appearance developed. After 1 hour of mixing at 160 to 170 DEG F (first retention delay period), the mixture was heated to 190 to 200 DEG F (second temperature adjustment delay period) and 30.14 g of propylene glycol was added as a non-aqueous conversion agent .

After 40 minutes, visible conversion and ignition started. Then another 30 ml of water was added due to the evaporation loss. As the grease continued to thicken, 53.10 g of the same base oil as above was added. After 25 minutes another 20 ml of water and 51.91 g of the same base oil were added. After 10 minutes thereafter, another 10 ml of water and 56.33 g of the same base oil were added. When another 25 minutes later the conversion of the amorphous calcium carbonate to calcined calcium carbonate (calcite) and the superheat process seemed to be complete, 8.18 g of the same calcium hydroxide and another 30 ml of water were added and mixed for 10 minutes . Then, 1.84 g of glacial acetic acid was added, followed by 30.57 g of 12-hydroxystearic acid. After these two complex acids reacted, a total of 105.14 g of two fractions of the same base oil as above were added due to the increased hardness of the grease mixture. Then, a solution of 75% phosphoric acid in 20.22 g of water was added slowly, mixed and allowed to react. As the grease continued to become harder, 55.31 g of the same base oil as above was added. The mixture was then heated with continued stirring using an electric heating mantle. When the grease reached 300 DEG F, 2.77 g of the styrene-alkylene copolymer was added as a piecewise solid. The grease was further heated to about 390 [deg.] F when the entire 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 was cooled to 300 ℉, 33.21 g of food grade anhydrous calcium sulfate having an average particle size of 5 microns or less was added. When the temperature of the grease was cooled to 200 ℉, 5.61 g of a mixture of arylamine and high molecular weight phenolic antioxidant and 5.90 g of amine phosphate antioxidant / rust inhibitor were added. Mixing was continued until the grease reached a temperature of 170 < 0 > F. The grease was then removed from the mixer and passed three times through a three roll mill to achieve a final smooth and homogeneous texture. The grease had a 60 reciprocal blending lead of 309. Percent salt of the final grease was 23.43% calcium perchlorate. The redness was > 650 [deg.] F.

Using a conventional inverse linear relationship between the mixing lead and percent calcium perchlorate sodium salt, less base oil was added and the miscibility led to the same value as the grease of Example 4 above, which had no alkali metal hydroxide added and no delay period , The grease of this Example 7 will have a percontent calcium sulfonate concentration of 25.76%. By comparing these values to the results of Example 4, Example 5, and Example 6 grease, it is possible to have a first holding delay period in the first temperature range of 160 to 170 ° F prior to heating to 190 to 200 ° F, 7 It is obvious that most of the grease thickener of the grease has been eradicated. In Examples 12 and 17 of the '476 patent application, having a first retention delay period in a first temperature range of 160 to 170 ° F prior to heating to 190 to 200 ° F, Even with a maintenance delay time of 2.5 hours, improvement of the viscosity agent (20.36% and 20.59%, respectively) was observed when no alkali metal hydroxide was added. It does not affect the conversion process of very small amounts of alkali metal hydroxide (e.g., 0.07 wt% of the final grease of Example 7) by comparison with the Example Grease in the above patent application, and the addition of the alkali / It is clear that the benefit of certain combinations of retardation periods of the '476 patent application is not necessarily achieved when combined with the addition of an alkali metal hydroxide. These results were unexpected and surprising. Example 7 While most of the yield improvements identified in Example 5 and Example 6 greases are not observed, while the grease exhibits some thickener benefit improvement compared to the grease of the baseline Example 4, And the temperature range. Thus, when an alkali metal hydroxide is added, the grease is not heated to a first temperature range of 160-170 ° F, including any retention delay period in the first temperature range as part of the delayed non-aqueous conversion method Is most preferable.

Example 8 (Modification of alkali / delayed addition method): Another calcium sulfonate composite grease was prepared in the same manner as in Example 6, except that lithium hydroxide monohydrate was used as an alkali metal hydroxide instead of sodium hydroxide. ≪ / RTI > The concentration of lithium hydroxide according to the monohydrate type in the final grease was 0.06%. The grease was prepared as follows: 298.61 g of 400 TBN perchloric oil soluble calcium sulfonate followed by 362.54 g of USP purity white paraffinic mineral base oil having a viscosity of about 352 SUS at 100 를 was added to the open mixing vessel. The overbased calcium sulfonate calcium was an NSF HX-1 food grade approved perbrominated calcium sulfonate suitable for making NSF H-1 approved food grade grease and was of good quality as defined by the '768 patent application. Mixing without heating was initiated using planetary mix paddles. Thereafter, 27.03 g of alkylbenzenesulfonic acid, mainly C12, was added. After mixing for 20 minutes, 50.62 g of calcium hydroxyapatite having an average particle size of 5 microns or less and 4.11 g of calcium hydroxide of food grade purity having an average particle size of 5 microns or less were added and allowed to mix for 30 minutes. Then 0.97 g of glacial acetic acid and 11.96 g of 12-hydroxystearic acid were added and allowed to mix for 15 minutes. Thereafter, 55.05 g of finely divided calcium carbonate having an average particle size of 5 microns or less was added and allowed to mix for 5 minutes. Thereafter, 39.55 g of water in which 0.88 g of powdered lithium hydroxide monohydrate was dissolved was added. The mixture was heated with continuous mixing until the temperature reached 190-200 [deg.] F (first temperature adjustment delay period). It was noted that when the temperature reached about 170 F, a whip cream appearance was observed. After 45 minutes of mixing at 190 to 200 ° F (first retention delay period), an additional 30 ml of water was added to replace the water lost due to evaporation, and 30.01 g of propylene glycol was added. At this time, the appearance of the whipped cream was also observed.

After 35 minutes, visual conversion and explosion began. Another 15 ml of water was added due to the evaporation loss. As the grease continued to thicken, 58.52 g of the same base oil was added, followed by another 51.15 g of the same base oil. When conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) and the process of increasing the viscosity were completed, 8.12 g of the same calcium hydroxide as above was added and allowed to mix for 10 minutes. Thereafter, 1.78 g of glacial acetic acid was added followed by 30.53 g of 12-hydroxystearic acid. After about 15 minutes, when the two complexed acids appeared to have reacted, another 69.37 g of the same base oil as above was added to prevent the thickener from becoming too hard. Another 10 ml of water was added. As the grease continued to harden, a total of 90.53 g of two additional fractions of the same base oil were added. Thereafter, another 5 ml of water was added, followed by slow addition of a 75% solution of phosphoric acid in 20.16 g of water, followed by mixing and reaction. As the grease continued to become harder, 38.24 grams of the same base oil as above was added. The mixture was then heated while continuing to harden using an electric heating mantle. When the grease reached 300 ℉, 2.85 g of the styrene-alkylene copolymer was added as a slab-like solid. The entire polymer was melted and the grease was further heated to about 390 된 when it was 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 was cooled to 300 ℉, 33.21 g of food grade anhydrous calcium sulfate having an average particle diameter of 5 microns or less was added. When the temperature of the grease was cooled to 200 ℉, 5.78 g of a mixture of arylamine and high molecular weight phenolic antioxidant and 6.10 g of amine phosphate antioxidant / rust inhibitor were added. A total of 112.37 grams of two or more fractions of the same base oil as above were added. Mixing was continued until the grease reached a temperature of 170 < 0 > F. The grease was then fed from the mixer and passed three times through a three roll mill to achieve a final smooth and homogeneous texture. The grease had a 60 reciprocating blending lead of 295. Percent salt in the final grease was 21.79% calcium perchlorate-usable calcium sulfonate. The redness was > 650 [deg.] F. As can be seen, the grease thickener of the present grease was further improved compared to the grease of Example 4 above, again demonstrating the noticeable effect of utilizing embodiments of the alkali / delayed addition process. The present grease is further improved in Example 6 grease having the same first temperature regulation delay period and the same first holding delay period (35 minutes vs. 45 minutes) as described above to improve the viscosity improvement effect of the thickener of lithium hydroxide Lt; / RTI > is not as effective as sodium hydroxide.

Example 9 (mode of alkali / delayed addition process): Another calcium sulfonate composite grease was prepared in a manner similar to that of Example 6 above, except that potassium hydroxide was used as the alkali metal hydroxide added instead of sodium hydroxide. Potassium hydroxide was introduced in the form of a 47.9% solution in water. The amount of the added solution was adjusted to compensate for both the concentration of potassium hydroxide and the difference in molecular weight of sodium hydroxide and potassium hydroxide. This was done to give approximately the same molar amount as the hydroxides added to the grease, as in Example 6 grease. The concentration of potassium hydroxide in the final grease was 0.20%. The grease was prepared as follows: 302.52 g of 400 TBN perchlorinated oil soluble calcium sulfonate followed by 357.60 g of USP purity white paraffinic mineral base oil having a viscosity of about 352 SUS at 100 를 was added to an open mixing vessel. The overbased calcium sulfonate calcium was an NSF HX-1 food grade approved perbrominated calcium sulfonate suitable for making NSF H-1 approved food grade grease and was of good quality as defined by the '768 patent application. Mixing without heating was initiated using planetary mix paddles. Thereafter, 27.04 g of alkylbenzenesulfonic acid, mainly C12, was added. After mixing for 20 minutes, 50.63 g of calcium hydroxyapatite having an average particle size of 5 microns or less and 4.09 g of calcium hydroxide of food grade purity having an average particle size of 5 microns or less were added and allowed to mix for 30 minutes. Then, 0.96 g of glacial acetic acid and 11.94 g of 12-hydroxystearic acid were added and allowed to mix for 15 minutes. Thereafter, 55.00 g of finely divided calcium carbonate having an average particle size of 5 microns or less was added and allowed to mix for 5 minutes. Thereafter, 39.00 g of water mixed with 2.67 g of a 47.9% aqueous solution of potassium hydroxide was added.

The mixture was heated while continuing to mix until the temperature reached 190-200 [deg.] F. It was noted that when the temperature reached about 170 to 180 DEG F, a whipped cream appearance developed. The heating was continued until the grease reached 200 DEG F (first temperature adjustment delay period), then 15 mL of water and 29.72 g of propylene glycol were added (no maintenance delay period). At this time, the appearance of the whipped cream was also observed. Upon the onset of visible conversion and evaporation, 65.89 g of the same base oil and 10 ml of water were added. As the ignition continued, 36.32 g of the same base oil and 10 ml of water were added. Then another 51.67 g of the same base oil as above was added. When conversion of the amorphous calcium carbonate into crystalline calcium carbonate (calcite) and the process of increasing the viscosity were deemed complete, 8.27 g of the same calcium hydroxide as above was added and allowed to mix for 10 minutes. Then, 1.79 g of glacial acetic acid was added followed by 30.57 g of 12-hydroxystearic acid. As these two complexing acids reacted and the grease continued to evaporate, 5 ml of water was added followed by 88.20 g of the same base oil. Then, as the grease became harder, another 15.73 g of the same base oil as above was added. Thereafter, a solution of 75% phosphoric acid in 20.81 g of water was added slowly, mixed and allowed to react. As the grease continued to become harder, 51.66 g of the same base oil as above was added. The mixture was then heated with continued stirring using an electric heating mantle. When the grease reached 300 DEG F, 2.75 g of the styrene-alkylene copolymer was added as a piecewise solid. When the entire polymer melted and completely dissolved in the grease, the grease was further heated to about 390.. The heating mantle was removed and the grease was allowed to cool by continued stirring in open air.

When the grease was cooled to 300 ℉, 33.19 g of food grade anhydrous calcium sulfate having an average particle size of 5 microns or less was added. When the temperature of the grease was cooled to 200 ℉, 5.93 g of a mixture of arylamine and high molecular weight phenolic antioxidant and 6.78 g of amine phosphate antioxidant / rust inhibitor were added. Another 51.59 g of the same base oil as above was added. Mixing was continued until the grease reached a temperature of 170 < 0 > F. The grease was then removed from the mixer and passed three times through a three roll mill to achieve a final smooth and homogeneous texture. The grease had 292 60 reciprocating blends. Percent of the final grease was 23.03% of the perchlorinated oil-soluble calcium sulfonate. The redness was > 650 [deg.] F. As can be seen, the thickener of the present grease was significantly improved compared to the grease of Example 4 above, again demonstrating the noticeable effect of using the embodiment of the alkali / delayed addition process. By further comparing this grease with Example 6 and Example 8 grease, it is clear that the effect of improving the viscosity of the thickener of potassium hydroxide is not as effective as sodium hydroxide or lithium hydroxide. It is believed that sodium hydroxide is the most preferred alkali metal hydroxide prior to lithium hydroxide and potassium hydroxide, although further tests involving other variations of delay periods for the addition of non-aqueous conversion agents may seem different.

Example 10 Alkaline / delayed addition mode: Another calcium sulphonate composite grease was prepared by adding more base oil initially and containing overbased calcium sulphonate, C12 alkyl benzene sulphonic acid, propylene glycol conversion, 12 -Hydroxystearic acid, and acetic acid was reduced in proportion to the amount of calcium hydroxide, calcium hydroxyapatite, calcium carbonate added, and phosphoric acid to be added, did. The grease was prepared as follows: 233.60 g of 400 TBN perchlorinated oilborne calcium sulfonate followed by 422.48 g of USP purity white paraffinic mineral base oil having a viscosity of about 352 SUS at 100 를 was added to the open mixing vessel. The overbased calcium sulfonate calcium was an NSF HX-1 food grade approved perbrominated calcium sulfonate suitable for making NSF H-1 approved food grade grease and was of good quality as defined in the '768 patent application. Mixing without heating was initiated using planetary mix paddles. Thereafter, 21.04 g of alkylbenzenesulfonic acid, mainly C12, was added. After mixing for 20 minutes, 50.69 g of calcium hydroxyapatite having an average particle size of 5 microns or less and 4.10 g of calcium hydroxide of food grade purity having an average particle size of 5 microns or less were added and allowed to mix for 30 minutes. Then 0.72 g of glacial acetic acid and 9.32 g of 12-hydroxystearic acid were added and allowed to mix for 15 minutes. Subsequently, 55.22 g of finely divided calcium carbonate having an average particle size of 5 microns or less was added and allowed to mix for 5 minutes. Thereafter, 39.1 g of water in which 0.88 g of powdered sodium hydroxide was dissolved was added. The mixture was heated with continuous mixing until the temperature reached 190-200 [deg.] F (first temperature adjustment delay period). It was noted that when the temperature reached about 180 DEG F, a whip cream appearance was observed. After mixing for 40 minutes (first retention delay period) at 190 to 200 ° F, an additional 20 ml of water was added to replace the water lost due to evaporation, and 23.13 g of propylene glycol was added. At this time, the appearance of the whipped cream was observed to sink.

After 2 hours and 30 minutes, the ignition continued to occur. The temperature was increased to 230 < 0 > F and the FTIR showed little water remaining. Another 30 ml of water was added and the temperature was maintained at 230.. After 30 minutes, another 35 ml of water was added. After another 25 minutes, another 35 ml of water was added. The temperature was reduced to about 220 < 0 > F. Thereafter, 8.22 g of the same calcium hydroxide as above was added and mixed for 10 minutes. Then, 1.37 g of glacial acetic acid was added followed by 23.68 g of 12-hydroxystearic acid. After these two complex acids reacted, a 75% solution of phosphoric acid in 20.53 g of water was added slowly, mixed and allowed to react. The grease was then heated with continued stirring using an electric heating mantle. When the grease reached 300 ℉, 2.79 g of the styrene-alkylene copolymer was added as a piecewise solid. The grease was further heated to about 390 [deg.] F when the entire polymer melted and was 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 was cooled to 300 ℉, 33.15 g of food grade anhydrous calcium sulfate having an average particle size of 5 microns or less was added. When the temperature of the grease was cooled to 200 ℉, 5.89 g of a mixture of arylamine and high molecular weight phenolic antioxidant and 5.83 g of amine phosphate antioxidant / rust inhibitor were added. A total of 103.66 g of two fractions of the same base oil as above were added. Mixing was continued until the grease reached a temperature of 170 < 0 > F. The grease was then removed from the mixer and passed three times through a three roll mill to provide a final smooth and homogeneous texture. The grease had 289 60 reciprocating blends. Percent of the final grease was 22.76% of the perchlorinated oil-soluble calcium sulfonate. The melting point was 621 [deg.] F. As can be seen, the viscosity of the thickener of the grease was improved in comparison with the grease of Example 4 above, which again proves the noticeable effect of the embodiment of the alkali / delayed addition process.

The results of Examples 1 to 10 herein and the methods used herein are summarized in Table 1 below. The amount of the overbased calcium sulfonate shown in parentheses is determined by the number of Examples shown after dash and the overbased vaporization which is estimated when additional base oil is added to dilute the sample grease to achieve the same miscibility as described above The amount of calcium sulphonate. Taking advantage of these early ten embodiments, by utilizing embodiments of the alkaline / delayed method of the present invention, particularly, calcium hydroxyapatite and added calcium carbonate can be used for the reaction with a complexing acid as disclosed in the '768 patent application ≪ / RTI > as a calcium-containing base for < RTI ID = 0.0 > a < / RTI > In addition, the thickener is improved utilizing aspects of the alkali / delayed method of the present invention that use both low quality and good quality perchlorinated calcium sulfonate. Composite grease proves to be excellent.

The following examples further illustrate the excellent properties of the inventive perchlorinated calcium sulfonic acid calcium grease, which can be achieved utilizing aspects of the alkali / delayed process of the present invention, including modifications to the point of addition of the alkali metal hydroxide .

Example 11 (Baseline Example-no alkali metal hydroxide added, no delay period): Another calcium sulfonate composite grease was prepared analogous to that described in U.S. Patent No. 4,560,489 (issued December 24, 1985 to Witco Corporation) and in Example 18 of the '476 patent application. As disclosed in the '489 patent, the only calcium-containing base added for the reaction with the complexing acid in the grease was calcium hydroxide. The grease acts as a baseline for the following two embodiments.

The grease of Example 11 was prepared as follows: 440.02 g of 400 TBN of perchlorinated oil soluble calcium sulfonate followed by 390.68 g of solvent having a viscosity of about 600 SUS at 100 DEG F. Neutral group 1 paraffinic base oil was added to an open mixing vessel He said. Mixing without heating was initiated using planetary mix paddles. The 400 TBN overbased fluorosurfactant calcium sulfonate was a good quality calcium sulfonate similar to that used in Example 4 and Example 12 of the '768 patent application described above. Thereafter, 17.76 g of alkylbenzenesulfonic acid, mainly C12, was added. After mixing for 20 minutes, 44.41 g of water was added followed by 14.37 g of hexylene glycol. The batch was then heated while continuing to mix until the temperature reached 190 ° F. When the temperature reached 190 ℉, 5.75 g of glacial acetic acid was added. When a visible transition to the grease structure is observed, the temperature is increased from 190 to 200 DEG F to 45 DEG C until the Fourier Transform Infrared (FTIR) spectroscopy shows that conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) Minute. Thereafter, 15.37 g of calcium hydroxide of food grade purity having an average particle size of 5 microns or less was added and allowed to mix for 10 minutes. This calcium hydroxide was the only added calcium-containing base for reaction with the complexing acid. Thereafter, 28.59 g of 12-hydroxystearic acid was added, melted and allowed to react. Thereafter, 25.33 g of boric acid was mixed with 50 ml of hot water and the mixture was added to the grease. The grease was then heated to 330 ° F. The heating mantle was then removed and the grease was allowed to cool by continued stirring in open air. When the grease was cooled to 170 ° F, it was removed from the mixer and passed three times through a three roll mill to achieve a final smooth and homogeneous texture. The grease had 291 60 reciprocating blending leads. Percent salt of calcium in the final grease was 46.92%. The redness was > 650 [deg.] F.

Example 12 (Modification of the Alkali / Delayed Addition Process) : Another grease is added to the mixture, except that the grease has a non-aqueous conversion hexyleneglycol which is delayed in its addition until the mixture is heated to 190 to 200 DEG F. , In a manner similar to the above grease. The grease also had a small amount of sodium hydroxide dissolved in the second fraction of water added at 190-200 ° F after the initial conversion and before addition of calcium hydroxide, 12-hydroxystearic acid, or acetic acid. The concentration of sodium hydroxide in the final grease was 0.08%. The grease was prepared as follows: 430.36 g of 400 TBN perchlorinated oil soluble calcium sulfonate followed by 386.79 g of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 를 was added to an open mixing vessel. Mixing without heating was initiated using planetary mix paddles. The 400 TBN overbased fluorosurfactant calcium sulfonate was a good quality calcium sulfonate similar to that used in Example 4 and Example 12 of the '768 patent application described above. Thereafter, 17.64 g of alkylbenzenesulfonic acid, mainly C12, was added.

After mixing for 20 minutes, 44.48 g of water was added as the conversion agent. Thereafter, the batch was heated while continuing to mix until the temperature reached 190 to 200 DEG F (first temperature adjustment delay period). When the temperature reached 190 ° F, 5.52 g of glacial acetic acid was added and allowed to mix for 5 minutes. Thereafter, 14.32 g of hexylene glycol was added while maintaining the temperature at 190 to 200.. The interval of 5 minutes between the arrival of the first temperature range of 190 to 200 DEG F and the addition of the non-aqueous conversion agent is too short, so that the maintenance delay period is not considered. When a visible transition to the grease structure is observed, the temperature is increased from 190 to 200 DEG F to 45 DEG C until the Fourier Transform Infrared (FTIR) spectroscopy shows that conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) Minute. Thereafter, 15.41 g of calcium hydroxide of food grade purity having an average particle size of 5 microns or less was added and allowed to mix for 10 minutes. The calcium hydroxide was the only added calcium-containing base for reaction with the complexing acid. Thereafter, 44.04 g of water (secondary addition of water) in which 0.88 g of powdered sodium hydroxide was dissolved was added and mixed into the grease. Then, 28.60 g of 12-hydroxystearic acid was added, melted and allowed to react. After the grease was stirred for 45 minutes, 25.30 g of boric acid was mixed with 50 ml of hot water and the mixture was added to the grease.

The grease was then heated to 390 to 400.. The heating mantle was then removed and the grease was allowed to cool by continued stirring in open air. When the grease was cooled to 200 ℉, 2.40 g of arylamine antioxidant was added. Thereafter, a total of 165.54 g of two or more fractions of the same base oil as above were added and mixed into the grease. When the grease was cooled to 170 ° F, it was removed from the mixer and passed three times through a three roll mill to achieve a final smooth and homogeneous texture. The grease had a 60-round reciprocating blending lead of 290. Percent of the final grease was 39.38% of the perchlorinated oil-soluble calcium sulfonate. The redness was > 650 [deg.] F. As can be seen, this grease essentially had the same miscibility with the grease of Example 11 above. However, as shown by the lower percentage of calcium perchlorate sulfonic acid in the present grease compared to the grease of Example 11 above, the thickener oil was significantly improved.

Example 13 (mode of alkali / delayed addition method): Another grease was prepared in a similar manner to the grease, delayed in addition of the non-aqueous conversion hexylene glycol until the mixture was heated to 190-200 [deg.] F (first temperature adjustment delay period). However, in this grease, a small amount of sodium hydroxide was dissolved in the initial fraction of water to be added at ambient temperature before heating of the batch was started. Again, the concentration of sodium hydroxide in the final grease was 0.08%. The grease was prepared as follows: 440.24 g of 400 TBN perchlorinated oil soluble calcium sulfonate followed by 385.62 g of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 를 was added to the open mixing vessel. Mixing without heating was initiated using planetary mix paddles. The 400 TBN overbased fluorosurfactant calcium sulfonate was a good quality calcium sulfonate similar to that used in Example 4 and Example 12 of the '768 patent application described above. Thereafter, 17.61 g of alkylbenzenesulfonic acid, mainly C12, was added. After mixing for 20 minutes, 44.48 g of water dissolved with 0.88 g of powdered sodium hydroxide was added. Thereafter, the batch was continuously mixed and heated (first temperature adjustment delay period) until the temperature reached 190 to 200.. When the temperature reached 190 ° F, 5.50 g of glacial acetic acid was added and allowed to mix for 5 minutes. Thereafter, 14.64 g of hexylene glycol was added while maintaining the temperature at 190 to 200.. Again, the interval of 5 minutes between the arrival of the first temperature range of 190 to 200 ° F and the addition of the non-aqueous conversion agent was too short, so the retention delay period was not considered. If a visible transition to the grease structure is observed, the FTIR spectroscopy can be performed at a temperature of from 190 to 200 DEG F for 45 minutes until the conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) I kept it.

Then, 30.1 g of water and 15.41 g of calcium hydroxide of food grade purity having an average particle size of 5 microns or less were added and allowed to mix for 10 minutes. Again, the calcium hydroxide was the only added calcium-containing base for reaction with the complexing acid. Thereafter, 28.66 g of 12-hydroxystearic acid was added, melted and allowed to react. After the grease was stirred for 45 minutes, 25.41 g of boric acid was mixed with 50 ml of hot water, and the mixture was added to the grease. The grease was then heated to a temperature of 390 to 400.. Thereafter, the heating mantle was removed and the grease was allowed to cool by continued stirring in open air. When the grease was cooled to 200 ℉, 2.69 g of arylamine antioxidant was added. Thereafter, a total of 172.32 g of three or more fractions of the same base oil as above were added and mixed into the grease.

When the grease was cooled to 170 ° F, it was removed from the mixer and passed three times through a three roll mill to achieve a final smooth and homogeneous texture. The grease had 284 60 reciprocating blends. Percent of the final grease was 38.74% of the perchlorinated oil-soluble calcium sulfonate. The redness was > 650 [deg.] F. Again, the viscosity builder was significantly improved, as indicated by a lower percentage of calcium perchlorate sulfonate in the grease as compared to the grease of Example 11 above. This Example Grease and the Example 12 Grease were prepared in such a way that only calcium hydroxide was used for the reaction with the complexing acid (in the above Examples and in the calcium hydroxyapatite as disclosed in the '768 patent application and / (As opposed to addition), it appears that utilizing the embodiment of the alkali / delayed addition process provides a very significant thickener improvement. The thickener of Example 13 in which the alkali metal hydroxide is added to the initial water is better than the thickener of Example 12 in which the alkali metal hydroxide is added to the secondary addition of water so that at least calcium hydroxide is the only calcium- , It is preferable to add an alkali metal hydroxide to the initial addition of water. However, both Example 12 and Example 13 show a significant improvement in the viscosity agent compared to Example 11 where no alkali metal hydroxide is added.

It was also noted that the concentration of the non-aqueous conversion agent of Example 12 and Example 13 grease (both utilizing an embodiment of the alkali / delayed addition method) was the same as that of Example 11 baseline grease. When the prior art calcium sulfonate calcium grease technique disclosed in the '489 patent, which includes calcium hydroxide as the only added calcium containing base, is used in combination with embodiments of the alkali / delayed addition process, a useful grease with improved thickener beads is achieved It is not necessary to increase the amount of the non-aqueous conversion agent. In contrast, the increase in the amount of the non-aqueous conversion agent can be achieved by combining the calcium hydroxyapatite and the addition of calcium carbonate added as an additional calcium-containing base for reacting with the complexing acid, , And Examples 5 to 10, the thickener beads in these Examples were significantly better than in Examples 12 and 13. Since the overbased calcium sulfonate calcium used in such greases is an expensive component, even if an additional amount of some of the ingredients is required, the addition of the calcium hydroxyapatite and the alkali / delayed addition method in combination with the added calcium carbonate Is most preferably used.

Example 14 (Baseline example, no alkali metal addition and no delay period): A calcium sulfonate composite grease was prepared according to the compositions and methods disclosed in U.S. Patent No. 9,273,265, wherein the added calcium carbonate is added to the grease It is a component added separately. The grease does not include the addition of alkali metal hydroxide or any delay period. The grease serves as a comparison base line along the following example grease. The grease was prepared as follows: 310.25 g of 400 TBN perchlorinated oil soluble calcium sulfonate followed by 368.14 g of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 를 was added to the open mixing vessel. The 400 TBN overbased fluorosurfactant calcium sulfonate was a good quality calcium sulfonate similar to that used in Example 4 and Example 12 of the '768 patent application described above. Mixing without heating was initiated using planetary mix paddles. Thereafter, 31.31 g of alkylbenzenesulfonic acid, mainly C12, was added. After mixing for 20 minutes, 75.03 g of finely divided crystalline calcium carbonate having an average particle size of 5 microns or less was added and allowed to mix for 20 minutes. Calcium carbonate was added in addition to the amount of amorphous calcium carbonate contained in the calcium salt of the overbased calcium sulfonate. Then, 0.85 g of glacial acetic acid and 8.09 g of 12-hydroxystearic acid were added. The mixture was stirred for 10 minutes. Thereafter, 15.83 g of hexylene glycol and 40.1 g of water (without any delay) were added and the mixture was heated to a temperature of 190 to 200 ° F with continuous mixing. During the heating step, it was noted that the mixture was visually converted to a grease structure at about 160 ° F. When the grease reached 190-200 [deg.] F, Fourier Transform Infrared (FTIR) spectroscopy showed most of the water lost due to evaporation. Another 20 ml of water was added.

After mixing for 45 minutes at 190 to 200 ° F, Fourier Transform Infrared (FTIR) spectroscopy indicated that conversion of amorphous calcium carbonate contained in the overbased calcium sulfonate to crystalline calcium carbonate (calcite) occurred. Then, 1.57 g of glacial acetic acid and 16.41 g of 12-hydroxystearic acid were added and allowed to react for 30 minutes. Another 20 ml of water was added. Then, a solution of 75% phosphoric acid in 16.49 g of water was added slowly, mixed and allowed to react. The grease was then heated to 390 to 400.. The heating mantle was removed from the mixer and allowed to cool while continuing to mix the grease. When the temperature reached 200 ℉ or less, a total of 105.38 g of two or more fractions of the same base oil as above were added. Mixing was continued until the grease reached a temperature of 170 < 0 > F. The grease was then removed from the mixer and passed three times through a three roll mill to achieve a final smooth and homogeneous texture. The grease had 283 60 reciprocating blends. Percent salt in the final grease was 32.68% calcium perchlorate. The redness was 617 ℉.

Example 15 (Baseline Example, no alkali metal hydroxide added, no delay period): Another calcium sulfonate composite grease was prepared in the same manner and in the same manner as in Example 14 of the above-mentioned grease. This Example 15 grease and the Example 14 grease provide a comparison baseline for the following two greases. The grease was prepared as follows: 310.19 g of 400 TBN perchlorinated oil soluble calcium sulfonate followed by 367.82 g of solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 를 was added to the open mixing vessel. The 400 TBN overbased fluorosurfactant calcium sulfonate was a good quality calcium sulfonate similar to that used in Example 4 and Example 12 of the '768 and described above. Mixing without heating was initiated using planetary mix paddles. Thereafter, 31.28 g of alkylbenzenesulfonic acid, mainly C12, was added. After mixing for 20 minutes, 75.31 g of finely divided crystalline calcium carbonate having an average particle size of 5 microns or less was added and allowed to mix for 20 minutes. This calcium carbonate was added in addition to the amount of amorphous calcium carbonate contained in the calcium salt of the overbased calcium sulfonate. Then, 0.84 g of glacial acetic acid and 8.10 g of 12-hydroxystearic acid were added. The mixture was stirred for 10 minutes. Then 15.73 g of hexylene glycol and 41.2 g of water were added and the mixture was continuously mixed and heated to a temperature of 190 to 200.. During the heating step, it was noted that the mixture was visually converted to a grease structure at about 170 ° F. When the grease reached 190-200 [deg.] F, Fourier Transform Infrared (FTIR) spectroscopy showed most of the water lost due to evaporation. Another 20 ml of water was added.

After mixing for 45 minutes at 190 to 200 ° F, Fourier Transform Infrared (FTIR) spectroscopy indicated that the conversion of amorphous calcium carbonate contained in the overbased calcium sulfonate to crystalline calcium carbonate (calcite) took place. Then, 1.57 g of glacial acetic acid and 16.44 g of 12-hydroxystearic acid were added and allowed to react for 30 minutes. Thereafter, a 75% solution of phosphoric acid in 16.60 g of water was added slowly and mixed and allowed to react. The grease was then heated to 390 to 400.. The heating mantle was removed from the mixer and allowed to cool while continuing to mix the grease. When the temperature reached 200 ℉ or less, a total of 105.79 g of two or more fractions of the same base oil as above were added. Mixing was continued until the grease reached a temperature of 170 < 0 > F. The grease was then removed from the mixer and passed three times through a three roll mill to achieve a final smooth and homogeneous texture. The grease had a 60 reciprocating blending lead of 280. Percent of the final grease was 32.66% calcium perchlorate-soluble calcium sulfonate. The melting point was 583 [deg.] F. As can be seen, the thickener oil of the grease is essentially the same as the grease of Example 14 above. Together, these two greases establish the baseline for the calcium sulfonate complex grease using this particular technique and the perbasic oil-soluble calcium sulfonate.

Example 16 Another calcium sulfonate composite grease was prepared similar to the two greases. However, the non-aqueous conversion hexyleneglycol was not added to water early. Instead, the mixture was heated (190 ° C to 200 ° F) (first temperature adjusted delay period) and maintained at this temperature range for 1 hour (first retention delay period). Alkali metal hydroxide was not added to the grease. This grease was prepared as follows: 310.27 g of 400 TBN perchlorinated oil soluble calcium sulfonate followed by 368.06 g of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 를 was added to the open mixing vessel. The 400 TBN overbased fluorosurfactant calcium sulfonate was a good quality calcium sulfonate similar to that used in Example 4 and Example 12 of the '768 patent application described above. Mixing without heating was initiated using planetary mix paddles. Thereafter, 31.18 g of alkylbenzenesulfonic acid, mainly C12, was added. After mixing for 20 minutes, 75.29 g of finely divided crystalline calcium carbonate having an average particle size of 5 microns or less was added and allowed to mix for 20 minutes. This calcium carbonate was added in addition to the amount of amorphous calcium carbonate contained in the calcium salt of the overbased calcium sulfonate. Then, 0.85 g of glacial acetic acid and 8.11 g of 12-hydroxystearic acid were added. The mixture was stirred for 10 minutes. Then, 41.2 g of water was added as the conversion agent and the mixture was heated to a temperature of 190 to 200 째 F (first temperature adjustment delay period) while continuously mixing. The mixture was mixed in this temperature range for 1 hour (first holding delay period). During this time, Fourier Transform Infrared (FTIR) spectroscopy showed that water was lost due to evaporation. Another 30 ml of water was added.

After 1 hour at 190 to 200 ° F, 15.66 g of hexylene glycol was added as a non-aqueous conversion agent. Immediately after hexylene glycol was added, the mixture was visually converted to grease. After mixing for 45 minutes at 190 to 200 ° F, Fourier Transform Infrared (FTIR) spectroscopy indicated that conversion of amorphous calcium carbonate contained in the overbased calcium sulfonate to crystalline calcium carbonate (calcite) occurred. After another 30 ml of water, 1.55 g of glacial acetic acid and 16.39 g of 12-hydroxystearic acid were added. These two complex acids were allowed to react for 30 minutes. Thereafter, a 75% solution of phosphoric acid in 16.99 g of water was slowly added and allowed to mix and react. The grease was then heated to 390 to 400.. The heating mantle was removed from the mixer and allowed to cool while continuing to mix the grease. When the temperature reached 200 ℉ or less, a total of 132.34 g of two or more fractions of the same base oil as above were added. Mixing was continued until the grease reached a temperature of 170 < 0 > F. The grease was then removed from the mixer and passed three times through a three roll mill to achieve a final smooth and homogeneous texture. The grease had 286 60 reciprocating blends. Percent salt in the final grease was 31.77% calcium perchlorate. The redness was > 650 [deg.] F. As can be seen, the viscosity of the thickener of the grease was slightly improved compared to the greases of Examples 14 and 15.

Example 17 (mode of the above alkali / delayed addition method) : Another calcium sulfonate composite grease was prepared in a manner similar to that of Example 16. However, this grease uses an embodiment of the alkali / delayed addition method. The non-aqueous conversion hexyleneglycol was not initially added to water, but was added after the mixture was heated to 190 to 200 DEG F (first temperature adjustment delay period). In addition, the water initially added contained a very small amount of sodium hydroxide. The concentration of sodium hydroxide in the final grease was 0.08%. It was noted that the grease batch sizes were increased by 50% compared to the greases of Examples 14-16. However, the percentage of each component and other method step details were not significantly different.

The grease was prepared as follows: 465.31 g of 400 TBN perchlorinated oil soluble calcium sulfonate followed by 367.68 g of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 를 was added to the open mixing vessel. The 400 TBN overbased fluorosurfactant calcium sulfonate was a good quality calcium sulfonate similar to that used in Example 4 and Example 12 of the '768 and described above. Mixing without heating was initiated using planetary mix paddles. Thereafter, 46.64 g of alkylbenzenesulfonic acid, mainly C12, was added. After mixing for 20 minutes, 112.50 g of finely divided crystalline calcium carbonate having an average particle size of 5 microns or less was added and allowed to mix for 20 minutes. This calcium carbonate was added in addition to the amount of amorphous calcium carbonate contained in the calcium salt of the overbased calcium sulfonate. Then, 1.26 g of glacial acetic acid and 12.20 g of 12-hydroxystearic acid were added. The mixture was stirred for 10 minutes. Thereafter, 41.2 g of water in which 1.20 g of powdered sodium hydroxide was dissolved was added and the mixture was heated to 190 to 200 째 F (first temperature adjustment delay period) while continuously mixing. It was noted that when the temperature reached about 176 [deg.] F, some foaming had begun to appear during the heating step. When the mixture reached 190-200 [deg.] F, 42.13 g of hexylene glycol (without a maintenance delay period) was added. Immediately after hexylene glycol was added, the mixture was visually converted to grease.

After mixing for about 20 minutes, another 76.61 g of the same base oil was added as the grease was heavily weighted. The grease was mixed at 190 to 200 DEG F for another 45 minutes. During that time, Fourier Transform Infrared (FTIR) spectroscopy indicated that water had evaporated, and another 40 ml of water was added. At the end of the mixing for 45 minutes, the grease was considerably squeezed. Fourier transform infrared spectroscopy indicated that the conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) occurred. Thereafter, 2.36 g of glacial acetic acid and 24.58 g of 12-hydroxystearic acid were added. These two complex acids were allowed to react for 30 minutes. Then, a 75% solution of phosphoric acid in 24.74 g of water was added slowly, mixed and allowed to react. The grease was then heated to 390 to 400.. The heating mantle was removed from the mixer and allowed to cool while continuing to mix the grease. The grease was thickened in an extreme amount as it cooled.

When the temperature was below 200 [deg.] F, a total of 284.40 g of four fractions of the same base oil were added. Mixing was continued until the grease reached a temperature of 170 < 0 > F. The grease was then removed from the mixer and passed three times through a three roll mill to achieve a final smooth and homogeneous texture. The grease had 274 60 reciprocating blends. Percent salt in the final grease was 31.84% calcium perchlorate. The redness was > 650 [deg.] F. Using the conventional inverse linear relationship between the mixing lead and the percontent hydrogencarbonate calcium sulfonate concentration, when additional base oil is added to bring the mixing lead to the same value as the grease lead in Example 16 above, the grease of this Example is 30.52% Percent of calcium perchlorate would have had a calcium sulfonate concentration. Thus, the use of embodiments of the alkali / delayed addition process in the present grease provided some improvement in the thickener beads compared to the two baseline greases of Example 14 and Example 15. [ Nevertheless, the amount of improvement is not as significant as that observed in some of the other example greases. Without wishing to be bound by theory, the lower amount of yield improvement provided by the present grease may be due to the fact that there is no calcium hydroxide added. The effect of a small amount of sodium hydroxide is in fact due to the rapid reaction of sodium hydroxide with the complex acid followed by metathesis of the sodium fatty acid salt and calcium hydroxide, which in turn significantly affects this mechanism. In the grease of Example 17, the metathesis reaction should be a reaction between the sodium fatty acid salt and calcium carbonate, which may not be easy.

The results of Examples 11 to 17 herein and the methods used herein are summarized in Table 2 below. All of these examples used calcium perchlorate sulfonates of good quality.

The following examples further demonstrate the superior properties of the overbased calcium sulphonate calcium phosphates of the present invention which can be achieved using embodiments of the alkali / delayed addition process comprising modifications at the time of alkali metal addition.

Example 18 (Baseline Example-no alkaline metal hydroxide added, no delay period): A calcium sulfonate complex grease was added to at least a portion of the long chain fatty acids prior to conversion and could act as a conversion agent and only calcium hydroxide or calcium oxide U.S. Pat. Nos. 5,308,514 and 5,338,467 (incorporated herein by reference), which are incorporated as calcium-containing bases for reacting with this complex acid (no calcium hydroxyapatite or calcium carbonate added as in the '768 patent application) Manufactured by Witco Corporation on August 16, 1994). This example is the same as Example 6A of the '476 patent application in which 54.1% of the total amount of 12-hydroxystearic acid and the entire glacial acetic acid is added prior to conversion. Following the remaining amount of the 12-hydroxystearic acid, a mixture of calcium hydroxide and water of boric acid was added after conversion. In addition, the alkali metal hydroxide was not added and there was no delay between the addition of water and the primary non-aqueous conversion agent. This grease serves as the baseline for comparison.

The grease of Example 18 was prepared as follows: 380.73 g of 400 TBN of perchlorinated oilborne calcium sulfonate followed by 604.50 g of solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 를 in an open mixing vessel . Mixing without heating was initiated using planetary mix paddles. The 400 TBN overbased fluorosurfactant calcium sulfonate was a good quality calcium sulfonate similar to that used in Example 4 and Example 12 of the '768 patent application described above. Thereafter, 21.66 g of alkylbenzenesulfonic acid, mainly C12, was added. After mixing for 20 minutes, 21.59 g of 12-hydroxystearic acid was added followed by 18.16 g of hexylene glycol and 38.0 g of water. After mixing for 10 minutes, 2.40 g of glacial acetic acid was added. The batch was then heated while continuing to mix until the temperature reached 190 ° F. The temperature was maintained at 190 to 200 DEG F for 45 minutes. The batch was mixed until Fourier Transform Infrared (FTIR) spectroscopy indicated that conversion of the amorphous calcium carbonate contained in the overbased calcium sulfonate calcium to crystalline calcium carbonate (calcite) occurred.

An additional 249.94 g of paraffinic base stock was added followed by 18.21 g of 12-hydroxystearic acid. The mixture was allowed to mix for 15 minutes while maintaining the temperature at 190 to 200.. Thereafter, 38.02 g of finely divided food grade purity calcium hydroxide having an average particle size of 5 microns or less was mixed with 50 g of water and the mixture was added to the grease. Then, 23.02 g of boric acid was mixed with 50 ml of hot water and the mixture was added to the grease. Thereafter, the grease was heated to 390.. The heating mantle was then removed and the grease was allowed to cool by continued stirring in open air. When the grease was cooled to 170 ° F, it was removed from the mixer and passed three times through a three roll mill to achieve a final smooth and homogeneous texture. The grease had 339 sixty reciprocating blending runs. Percent salt in the final grease was 27.62% calcium perchlorate. The redness was 640 ° F.

Example 19 (delayed addition process of the '476 patent application, no alkali metal hydroxide added) : Another calcium complex grease is added to the first temperature controlled delay period ( Example 18 was prepared using the same equipment, raw materials, amount, and manufacturing method as grease, except that there was a first holding delay period (heating to 190 to 200) and a first holding delay period . No alkali metal hydroxide was added. When hexylene glycol was added, the grease was maintained at 190-200 [deg.] F until conversion was complete. Thereafter, the rest of the procedure was the same as in Example 18 Greece. The final Greece had 281 60 round trip blends. Percent salt of the final grease was 27.60% calcium perchlorate-soluble calcium sulfonate. The redness was > 650 [deg.] F. As can be seen, the grease of this example had improved permeability compared to the grease of Example 18, as evidenced by the more rigid permeation despite having essentially the same percentages of perchlorinated oil of calcium sulfonate as above. It had a thickening agent. In fact, when using a conventional inverse linear relationship between the mixing lead and the percontent hydrogencarbonate calcium sulfonate concentration, diluting with sufficient base oil to obtain the same mixing lead as Example 18 grease, The expected percentage of calcium was 24.2%.

Example 20 (Modification of the Alkali / Delayed Addition Process) : Another grease was added to the mixture, delaying the addition of the non-aqueous conversion hexylene glycol until the mixture was heated to 190 to 200 DEG F, ≪ / RTI > However, in the present grease, a small amount of sodium hydroxide was dissolved in the initial fraction of water at ambient temperature before heating of batch was started. Also, when the temperature range of 190 to 200 DEG F was reached, there was no maintenance delay period of 1 hour. Instead, hexylene glycol was added as soon as the temperature range was achieved. This was accomplished as observed in Example 7, Grease, above, where the addition of alkali metal hydroxide also showed that the temperature delay retention for the non-aqueous conversion agent did not provide the highest viscosity improvement.

The grease was prepared as follows: 380.79 g of 400 TBN perchlorinated oil of calcium sulfonate followed by 589.33 g of solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 를 was added to the open mixing vessel. Mixing without heating was initiated using planetary mix paddles. The 400 TBN overbased fluorosurfactant calcium sulfonate was a good quality calcium sulfonate similar to that used in Example 4 and Example 12 of the '768 patent application and described above. Thereafter, 21.63 g of alkylbenzenesulfonic acid, mainly C12, was added. After mixing for 20 minutes, 21.58 g of 12-hydroxystearic acid was added followed by 38.14 g of water in which 0.85 g of powdered sodium hydroxide was dissolved. After mixing for 10 minutes, 2.40 g of glacial acetic acid was added. Thereafter, the batch was heated while continuing to mix (the first temperature adjustment period) until the temperature reached 190 to 200.. It was noted that when the temperature reached about 180 F, foaming was observed. When the temperature reached 190-200 [deg.] F, 27.57 g of hexylene glycol was added (without any maintenance delay). About ten minutes later, the batch was visually converted to a grease structure.

The batch was then mixed for an additional 45 minutes until the Fourier Transform Infrared (FTIR) spectroscopy indicated that conversion of the amorphous calcium carbonate to crystalline calcium carbonate (calcite) took place. During the 45 minute mix, an additional 40 ml of water was added to replace the water lost by evaporation. Thereafter, 18.27 g of 12-hydroxystearic acid was added and allowed to mix for 15 minutes while maintaining the temperature at 190 to 200.. Thereafter, 38.04 g of finely divided food grade purity calcium hydroxide having an average particle size of 5 microns or less was mixed with 50 g of water and the mixture was added to the grease. Then, 23.04 g of boric acid was mixed with 50 ml of hot water, and the mixture was added to the grease. Thereafter, the grease was heated to 390.. The heating mantle was then removed and the grease was allowed to cool by continued stirring in open air. During the cooling, the grease was significantly thickened. A total of 253.87 g of approximately the same fraction of the same base oil as above was added into the grease and mixed. When the grease was cooled to 170 ° F, it was removed from the mixer and passed three times through a three roll mill to achieve a final smooth and homogeneous texture. The grease had a 60 reciprocating blending lead of 280. The redness was > 650 [deg.] F. Percent of the final grease was 27.65% of the perchlorinated oil-soluble calcium sulfonate. The concentration of sodium hydroxide in the final grease was 0.06%.

Example 21 (mode of alkali / delayed addition method): Another grease was prepared almost the same as the grease of Example 20 above. The only significant difference is that after the conversion is complete, the sodium hydroxide mixture in water is added. A mixture of the second fraction of 12-hydroxystearic acid and hydroboric acid in water was then added. The final Greece had 285 60 roundtrip blends. The redness was > 650 [deg.] F. Percent salt of the final grease was 27.40% calcium perchlorate-soluble calcium sulfonate. The concentration of sodium hydroxide in the final grease was 0.06%. As can be seen, the thickener beads of Example 19, Example 20, and Example 21 grease were significantly superior to those of Example 18 baseline grease. However, the use of embodiments of the alkaline / delayed addition process, when using the high-quality perbrominated calcium sulfonate, does not provide a further additive thickener improvement over that provided only by the delayed addition method of the '476 patent application I did. It appears that the best thickener improvement can be achieved using alkali metal hydroxide additions and / or delayed non-aqueous conversion agent methods when low quality overbased calcium sulfonate calcium is used in place of the high quality calcium perchlorate sulfonate.

The results of Examples 18 to 21 herein and the methods used herein are summarized in Table 3 below. All of these examples used calcium perchlorate sulfonates of good quality.

Further embodiments showing the results of alkali metal hydroxide addition in simple sodium sulfonate calcium grease are identified in the following examples.

Example 22 (Baseline Example-no alkali metal hydroxide added, no delay period): For use as a baseline for comparison with the following three greases, a simple sodium sulfonic acid grease was added to the solution without any delay or alkali metal hydroxide addition , U.S. Pat. Nos. 3,377,283 and 3,492,231, each issued on April 9, 1968 and January 27, 1970, to Lubrizol Corporation. The grease was prepared as follows: 496.49 g of 400 TBN perchlorinated oil of calcium sulfonate followed by 394.45 g of solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 를 was added to the open mixing vessel. Mixing without heating was initiated using planetary mix paddles. The 400 TBN overbased fluorosurfactant calcium sulfonate was a good quality calcium sulfonate similar to that used in Example 4 and Example 12 of the '768 patent application and described above. Thereafter, 20.23 g of alkylbenzenesulfonic acid, mainly C12, was added. After mixing for 20 minutes, 44.23 g of water was added followed by 16.57 g of hexylene glycol (primary conversion agent). The batch was then heated while continuing to mix until the temperature reached 190 ° F. When the temperature reached 190 ℉, 6.20 g of glacial acetic acid was added. When a visible transition to the grease structure was observed, until the Fourier Transform Infrared (FTIR) spectroscopy indicated that the conversion of the amorphous calcium carbonate contained in the overbased calcium sulfonate to crystalline calcium carbonate (calcite) The temperature was maintained at 190 to 200 DEG F for 45 minutes. During this time, an additional 10 ml of water was added. The resulting grease was then heated to 330.. The heating mantle was then removed and the grease allowed to cool while still stirring in open air. When the temperature reached 200 ℉, 2.34 g of arylamine antioxidant was added. When the grease was cooled to 170 ° F, it was removed from the mixer and passed three times through a three roll mill to achieve a final smooth and homogeneous texture. The grease had 331 60 reciprocating blends. The percentage of the final grease was 44.03% for the perchlorinated oil-soluble calcium sulfonate, and the redness was> 650 ° F.

Example 23 (delayed addition method of the '476 patent application, without addition of alkali): Another simple sodium sulfonic acid calcium grease was prepared by the same procedure as in Example 1, except that there was a delay period between the addition of water and a non-aqueous conversion agent. Example 22 < / RTI > In this embodiment, no alkali metal hydroxide was added. The grease was prepared as follows: 495.41 g of 400 TBN perchlorinated oil soluble calcium sulfonate followed by 391.96 g of solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 를 was added to the open mixing vessel. Mixing without heating was initiated using planetary mix paddles. The 400 TBN overbased fluorosurfactant calcium sulfonate was a calcium sulfonate of good quality similar to that described above and used in Example 4 and Example 12 of the '768 patent application. Thereafter, 19.65 g of alkylbenzenesulfonic acid, mainly C12, was added. After mixing for 20 minutes, 44.42 g of water was added. The mixture was then heated to 160 ° F (first temperature regulated delay period) and held at 160 to 170 ° F. for 2 hours and 30 minutes (first retention delay period). During this time, an additional 50 ml of water was added since most of the originally added water had evaporated. Thereafter, the batch was heated to 190 ° F (second temperature regulated delay period) and 16.53 g of hexylene glycol (primary conversion agent) was added followed by 6.34 g of glacial acetic acid.

When a visible transition to the grease structure is observed, the temperature is changed from 190 to 200 DEG F to 45 DEG C until the Fourier Transform Infrared (FTIR) spectroscopy shows that the conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) Minute. During this time an additional 10 ml of water was added. The resulting grease was then heated to 330.. The heating mantle was then removed and the grease was allowed to cool by continued stirring in open air. When the temperature reached 200 ℉, 2.32 g of arylamine antioxidant was added. When the grease was cooled to 170 ° F, it was removed from the mixer and passed three times through a three roll mill to achieve a final smooth and homogeneous texture. Example 21 The redness of the grease was > 650 ° F. The grease had a 60-round reciprocating blending lead of 290. Percent salt in the final grease was 53.14% calcium perchlorate.

It has been noted that the present grease and the above Example 22 grease have essentially the same percentages of the perbrominated calcium sulfonate as the above. However, the Greek blend lead was harder by 41 points. Thus, the delayed glycol procedure used in the present grease caused an improved thickener oil. In fact, when using a conventional inverse linear relationship between the mixing lead and percent perchloric acid calcium sulfonate concentration, when diluting with a suitable base oil to obtain the same mixing lead as Example 22 grease, The expected percentage of calcium phosphate is 46.6%. In addition, very high points were maintained.

Example 24 (alkaline addition and delayed addition): Another simple sodium sulfonic acid calcium grease was prepared in a manner similar to that of Example 23 above except that a different delay period was used between water and the addition of the non-aqueous conversion agent and a small amount of sodium hydroxide was added . The concentration of sodium hydroxide in the final grease was 0.09%. This grease was prepared as follows: 495.18 g of 400 TBN perchlorinated oil soluble calcium sulfonate followed by 392.56 g of a solvent neutral group 1 paraffinic base oil having a viscosity of about 600 SUS at 100 를 was added to the open mixing vessel. Mixing without heating was initiated using planetary mix paddles. The 400 TBN overbased fluorosurfactant calcium sulfonate was a good quality calcium sulfonate similar to that used in Example 4 and Example 12 of the '768 patent application described above. Thereafter, 20.31 g of alkylbenzenesulfonic acid, mainly C12, was added. After mixing for 20 minutes, 0.88 g of powdered sodium hydroxide was dissolved in 44.0 g of water and the resulting solution was added. The mixture was then heated to 190 ° F (first temperature adjusted delay period) and 16.73 g of hexylene glycol and 6.16 g of glacial acetic acid were added.

When a visible transition to the grease structure is observed, the temperature is changed from 190 to 200 DEG F to 45 DEG C until the Fourier Transform Infrared (FTIR) spectroscopy shows that the conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) Minute. During this time an additional 20 ml of water was added. The resulting grease was then heated to 330.. The heating mantle was then removed and the grease was allowed to cool by continued stirring in open air. When the temperature reached 200 ℉, 3.35 g of arylamine antioxidant was added. When the grease was cooled to 170 ° F, it was removed from the mixer and passed three times through a three roll mill to achieve a final smooth and homogeneous texture. Example 24 The redness of the grease was 478 [deg.] F. The grease had 311 60 reciprocating blending runs. Percent salt in the final grease was 52.95% calcium perchlorate.

Comparing this grease to the above Example 23 grease, it is clear that the benefits observed by using the embodiment of the alkali / delayed addition method in the grease embodiment are not observed in the present grease. In Example 24 grease as compared to the grease of Example 23 above, the viscosity of the thickener was significantly reduced and the redness was lower. Again, although not wishing to be bound by theory, it is believed that the addition of an alkali hydroxide mainly improves the viscosity agent, which is due to the reaction with the complex acid used in the preparation of the complex sulfonic acid calcium grease, Since this does not involve addition, this benefit is not achieved with simple greases, and even adding an alkali metal hydroxide to a simple grease composition appears to be detrimental to the thickener. The results of Examples 22 to 24 are summarized in Table 4 below.

Composite grease embodiments show that exploiting aspects of the alkaline / delayed addition method consistently improves the viscosity of the thickener regardless of which of the calcium sulfonate calcium-based grease techniques described in previous documents is used. In addition, the thickener star improvement is observed regardless of the good quality or poor quality of the overbased calcium sulphonate calcium used as defined in the '768 patent application; rather, within the scope of the example compositions included in the present invention, A larger improvement was achieved using calcium (this is the opposite as anticipated).

The example grease prepared according to the alkaline / delayed addition method of the present invention disclosed hereinabove is also characterized in that compared to the greases of the Examples in which the addition of all or part of the non-aqueous conversion agent is not delayed, Although the components and amounts used are the same or substantially similar, they exhibit different physical properties. Using Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM), testing of the samples of the above example greases shows that the greases prepared using the delayed addition according to the invention have a similar grease And the like. For example, there is a difference in the adsorption curve profile and a difference in particle size and configuration.

The embodiments provided herein are predominantly NLGI No. 1, No. 2, or No. Even if it is grade 3, no. 2 is the most preferable. It should further be understood that the NLGI consistency rating, which is more rigid or soft than grade 2, should be further understood. However, as will be appreciated by those skilled in the art, For these greases according to the present invention, which are not of grade 2, their properties are such that more or less base stock is used to reduce the number of greases. 2 < / RTI > grade product.

Although the present invention primarily covers greases made in open vessels, and all of the above embodiments are in open vessels, the composite calcium sulfonate calcium grease composition and method may also be used in hermetically sealed vessels under pressure heating. The use of such pressure vessels may result in better thickener beds than those disclosed in the embodiments herein. For purposes of the present invention, an open container is any container that does or does not include an upper cover or hatch, as long as any top cover or hatch is not gas tight and significant pressure can be produced during heating. Use of such an open container, including a sealed top cover or hatch during the conversion process, will generally help to keep the conversion temperature above the boiling point of the water while at the same time retaining the required level of water as a conversion agent. As will be appreciated by those skilled in the art, this higher conversion temperature may cause additional thickening agent improvements for both simple and complex calcium sulfonate phosphates.

The term "thickener beads " as used herein, as applied to the subject invention, is intended to refer to any material having a specific desired roughness, as measured by ASTM D217 or D1403, which is a standard misconditioning test commonly used in lubricant grease manufacture Is the concentration of the highly perchlorinated oil-soluble calcium sulfonate required to provide grease. In a similar manner, the "redness " of grease used herein represents the value obtained using ASTM D2265, a standardized redox test commonly used in lubricating grease manufacture. As used herein, reference to the addition of any component immediately after reaching a certain temperature means that the component is added as soon as it is added and the physically feasible temperature is reached when the equipment is used, The component is added within a short time after reaching approximately the indicated temperature, within 10 minutes, more preferably within 5 minutes.

As used herein, (1) the amount of dispersed calcium carbonate (or amorphous calcium carbonate) or residual calcium oxide or calcium hydroxide contained in the calcium perchlorate sulfonate is based on the weight of the calcium perchlorate sulfonate; (2) Some ingredients are added in two or more separate fractions, each fraction being expressed as a percentage of the total amount of the ingredients; (3) the specific component (e.g., water reacting with other components, or a calcium-containing base or alkali metal hydroxide) may not be present in the final grease, or may be present in the final grease in an amount defined for inclusion as an ingredient , The total amount of other amounts (including the total amount) of the components defined as percentages or parts is the amount added as a component based on the weight of the final grease product. "Added calcium carbonate" as used herein means crystalline calcium carbonate added as a separate component in addition to the amount of calcium carbonate dispersed in the calcium carbonate. As used herein, "added calcium hydroxide" and "added calcium oxide" refer to calcium hydroxide and calcium oxide, which are added as separate components in addition to the amount of residual calcium hydroxide and / or calcium oxide that may be contained in calcium perchlorate, it means. As used herein to describe the present invention (as opposed to how the following terms are used in some prior art documents), calcium hydroxyapatite is defined as (1) a compound having the formula Ca ₅ (PO ₄ ) ₃ OH, or 2) means a specific exclusion of (a) a mathematical equivalent equation having a melting point of about 1100 ° C, or (b) a mixture of calcium trichloride and calcium hydroxide by the mathematical equivalent equation. It will be apparent to those skilled in the art, upon reading the present disclosure, including the embodiments contained herein, that variations and modifications to the composition and methodology for making the compositions are within the scope of the present invention, It will be understood that the scope of the invention is limited only by the broadest interpretation of the appended claims having a legal right.

Claims (44)

A method for producing a complex overbased calcium sulfonate grease,
A certain amount of an oil-soluble calcium sulfonate having amorphous calcium carbonate dispersed therein is mixed with a base oil and one or more converting agents to form a pre-conversion mixture ;
Converting the pre-conversion mixture to a converted mixture by heating until conversion of the amorphous calcium carbonate to crystalline calcium carbonate takes place;
Mixing an amount of an alkali metal hydroxide with the pre-conversion mixture, or the converted mixture, or both; And
Mixing a quantity of one or more complexing acids with the pre-conversion mixture, or the converted mixture, or both,
Wherein the amount of the perchlorinated oil-soluble calcium sulfonate is about 10 to 45%. The process according to claim 1, wherein the amount of the alkali metal hydroxide is about 0.005 to 5%. The method of claim 1, further comprising mixing at least one of calcium hydroxyapatite, calcium hydroxide added, calcium oxide added, calcium carbonate added, or any combination thereof with the pre-conversion mixture, or the converted mixture, ≪ / RTI > wherein the method further comprises mixing with both. The process according to claim 1, wherein the alkali metal hydroxide is sodium hydroxide, lithium hydroxide, potassium hydroxide or a combination thereof. 3. The process according to claim 2, wherein the alkali metal hydroxide is sodium hydroxide, and the amount of sodium hydroxide is about 0.01 to 0.4%. The process according to claim 1, wherein the alkali metal hydroxide is dissolved in water to form a solution, and the solution is mixed with the pre-conversion mixture, or the converted mixture, or both. 3. The method of claim 1, wherein the overbased calcium sulfonate is poor quality calcium sulphonate and the grease has a dropping point of at least 575 < 0 > F. The method of claim 1, wherein the conversion agent comprises water and at least one non-aqueous conversion agent,
Mixing said water with said perchlorinated calcium sulfonate and base oil to form a first mixture; And
Further comprising mixing at least a portion of said at least one non-aqueous conversion agent with said first mixture during at least one delay period or after said at least one delay period to form said pre-conversion mixture. Gt; 9. The process of claim 8 wherein said alkali metal hydroxide is dissolved in said water used as a conversion agent to form a solution and said solution is mixed with said overbased calcium sulfonate and base oil to form said first mixture. Way. The method of claim 8, wherein the alkali metal hydroxide is dissolved in a second fraction of water to form a solution, and the solution is mixed with the first mixture, or the pre-conversion mixture, or the converted mixture, ≪ / RTI > 9. The method according to claim 8, wherein all or part of one complexing acid is mixed with the first mixture or with the pre-conversion mixture, and at least a part or all of the complexing acid, which is the same as or different from the complexing acid, ≪ / RTI > 12. The process of claim 11, wherein at least a portion of one complexing acid is mixed with the first mixture or the pre-conversion mixture prior to any heating. 9. The method of claim 8,
Heating the mixture prior to the conversion to a transition temperature range of about 190 to 230 DEG F in the case of an open vessel or to a different temperature range where conversion occurs in the case of a closed vessel; And
Maintaining the temperature within said range until conversion of said amorphous calcium carbonate to crystalline calcium carbonate occurs. 12. The method of claim 11, wherein the combined acid comprises acetic acid and 12-hydroxystearic acid, wherein a portion of both of the acids is mixed with the first mixture or with the pre-conversion mixture, And the other part is mixed with the converted mixture. 15. The method of claim 14, wherein the complexed acid further comprises boric acid, phosphoric acid, or both, wherein the entire of the boric acid, phosphoric acid, or both is mixed with the converted mixture. 15. The process of claim 14, wherein the non-aqueous conversion agent is hexylene glycol, which is mixed with the first mixture after a delay in temperature adjustment. 15. The method of claim 14, wherein the alkali metal hydroxide is mixed with the first mixture. The process according to claim 1, wherein the calcium sulfonate has a red point of at least 575 ℉ and the amount of the calcium perchlorate sulfonic acid is about 10 to 32%. 9. The process of claim 8, wherein the calcium sulfonate has a melting point of at least 575 DEG F and the amount of calcium perchlorate is about 10 to 32%. 9. The composition of claim 8, wherein at least a portion of one or more of the non-
Addition of said first mixture before any delay period, said first mixture for a delay period or after a delay period, or a mixture of at least one of said pre-conversion mixture for at least one delay period or more than one delay period Lt; / RTI > 21. The process of claim 20, wherein acetic acid is not added as a non-aqueous conversion agent for any delay period. The method of claim 8, further comprising mixing at least one of calcium hydroxyapatite, calcium hydroxide added, calcium oxide added, calcium carbonate added, or any combination thereof with the first mixture, ≪ / RTI > further comprising the step of mixing with the converted mixture, or any combination thereof. 9. The process of claim 8 wherein at least one of the non-aqueous converting agents is a glycol, a glycol ether, or a glycol polyether. 21. The process according to claim 20, wherein the glycol is hexylene glycol. 25. The method of claim 24, wherein one fraction of the hexylene glycol is mixed with the first mixture prior to any delay period, and another fraction of the hexylene glycol is added to the second mixture after one or more delay periods, 1 < / RTI > mixture. 9. The method of claim 8, wherein at least two delay periods are present, wherein at least one of the delay periods is a temperature regulated delay period wherein the first mixture or the pre-conversion mixture is heated or cooled, Is the retention delay period, wherein the first mixture or the pre-conversion mixture is maintained at a constant temperature or within a temperature range for a period of time. 9. The method of claim 8, wherein the overbased calcium sulfonate is a low-quality overbased calcium sulfonate. 23. The method of claim 22, wherein the overbased calcium sulfonate comprises about 0 to 8% of residual calcium hydroxide and / or calcium oxide, wherein the additional calcium oxide or calcium hydroxide is added as a calcium-containing base for reaction with the complexing acid ≪ / RTI > 9. The process of claim 8, wherein at least one of the non-aqueous conversion agents is methanol, isopropyl alcohol, or another low molecular weight alcohol. The process according to claim 8, wherein methanol, isopropyl alcohol, or another low molecular weight alcohol is not used as a non-aqueous conversion agent. The process according to claim 1, wherein the amount of the perbrominated calcium sulfonate is about 10 to 22%. A complex sulfonic acid calcium grease composition comprising about 10 to 45% of an overbased vaporizable oil of calcium sulphonate and an alkali metal hydroxide component. 33. The composition of claim 32 comprising about 10 to 36% of an overbased vaporizable oil of calcium sulphonate and about 0.005 to 0.5% of an alkali metal hydroxide,
One or more complexing acids; And
Calcium hydroxide base, calcium hydroxide added, calcium oxide added, calcium carbonate added, or any combination thereof, as at least one calcium containing base for reaction with said at least one complexing acid
By weight, based on the total weight of the composition. 33. The composition of claim 32, further comprising:
One or more complexing acids; And
Calcium hydroxide base, calcium hydroxide added, calcium oxide added, calcium carbonate added, or any combination thereof, as at least one calcium containing base for reaction with said at least one complexing acid
≪ / RTI > further comprising a calcium sulfonate complex. 35. The composite calcium sulfonate grease composition of claim 34, wherein the grease has a worked 60 stroke penetration of between 265 and 295 and a melting point of at least 575F. 35. The composition of claim 34, wherein the grease comprises about 10 to 30% of an overbased vaporizable oil of calcium sulphonate. 37. The composition of claim 36, wherein the overbased calcium sulfonate is of a lower quality. 35. The composite calcium sulfonate composition of claim 34, further comprising a facilitating acid. 35. The composite calcium sulfonate composition of claim 34, wherein the components exclude calcium hydroxide to be added and calcium oxide to be added. 35. The composite calcium sulfonate composition of claim 34, further comprising one or more conversion agents. 41. The complex sulfonic acid calcium grease composition of claim 40, wherein the conversion agent comprises water and at least one non-aqueous conversion agent. 42. The composition of claim 41, wherein said at least one non-aqueous conversion agent is selected from the group consisting of alcohols, ethers, glycols, glycol ethers, glycol polyethers, carboxylic acids, inorganic acids,
Wherein the at least one complexing acid is selected from the group consisting of long chain carboxylic acids, short chain carboxylic acids, boric acids, and phosphoric acids. 41. The method of claim 40,
About 1 to 20% calcium hydroxyapatite;
About 1.5 to 10% water;
From about 0.005 to 0.5% of an alkali metal hydroxide;
At least one non-aqueous conversion agent wherein the total amount is from 0.1 to 5%; And
Wherein the total amount of the at least one complexing acid is from 2.8 to 11%. 44. The composition of claim 43, wherein the alkali metal hydroxide comprises sodium hydroxide, lithium hydroxide, potassium hydroxide, or combinations thereof.