KR102095188B1 - Preparation of calcium sulfonate grease using alkali metal hydroxide and delayed addition of non-aqueous converting agent - Google Patents

Abstract

Addition of alkali metal hydroxide alone or (a) calcium hydroxyapatite used as a calcium-containing base for reaction with complexed acid and / or calcium carbonate added and / or (b) addition and non-aqueous addition of water as a converting agent. A composition and method for producing a overbased calcium sulfonate grease comprising an alkali metal hydroxide added in combination with at least one delay period between the addition of a portion of the converting agent. The delay period may involve a period of time for adjusting the temperature of the mixture, a period of time during which the mixture is maintained at or within a constant temperature range, and any combination thereof. These calcium sulfonate greases have improved thickener yields and higher than greases prepared without delay between the addition of added alkali metal hydroxides and water and non-aqueous converting agents, particularly greases when low-quality overbased calcium sulfonate is used. Have a dropping point.

Description

Preparation of calcium sulfonate grease using alkali metal hydroxide and delayed addition of non-aqueous converting agent

Cross reference of related applications

This patent application claims priority to U.S. Patent Application No. 15 / 130,422 filed on April 15, 2016 and U.S. Patent Application No. 14 / 990,473 filed on January 7, 2016, the applications being filed in 2012 U.S. Patent Application No. 13 / 664,768 (currently filed on October 4, 2016), filed on October 31, claiming the benefit of U.S. Provisional Patent Application No. 61 / 553,674, filed on October 31, 2011 U.S. Pat.Nos. 9,458,406) and 13 / 664,574 (current U.S. Pat.

1. Field of invention

The present invention is demonstrated by thickener yield and dropping point, even when the oil-soluble overbased calcium sulfonate used to make the grease is considered to be of poor quality. The present invention relates to overbased calcium sulfonate greases prepared with the addition of alkali metal hydroxides, providing improvements in both of the expected high temperature utility. The present invention relates to overbased calcium sulfonate greases prepared using both the use of added alkali metal hydroxides and the delayed addition of non-aqueous converting agents.

2. Description of related technical fields

Perbasic calcium sulfonate grease has been a category of grease established for many years. One known method for preparing such greases is a two-step method involving "accelerating" and "conversion" steps. In general, the first step ("acceleration") reacts a stoichiometric excess of calcium oxide (CaO) or calcium hydroxide (Ca (OH) ₂ ) with an alkyl benzene sulfonic acid, carbon dioxide (CO ₂ ) as a base source, and internally It is to react with other components to produce an oil-soluble overbased calcium sulfonate containing amorphous calcium carbonate dispersed in it. These overbased oil-soluble calcium sulfonates are generally transparent, bright, and have Newtonian rheology. In some cases, they may be slightly cloudy, but this difference does not prevent their use in the production of overbased calcium sulfonate grease. For the purposes of the present specification, the terms "perbase-soluble calcium sulfonate" and "useful perbase calcium sulfonate" and "perbase calcium sulfonate" refer to any perbase calcium sulfonate suitable for the manufacture of calcium sulfonate grease. Shows.

Generally, the second step ("conversion") is that the initial grease cannot convert the amorphous calcium carbonate contained in the overbased calcium sulfonate to a very finely divided dispersion of crystalline calcium carbonate (calcite). The accelerator step, if necessary, so as not to be too hard to the extent, converting agents or converting agents, such as propylene glycol, isopropyl alcohol, water, formic acid or acetic acid, with a suitable base oil (e.g. mineral oil). It is to be added to the product. If acetic acid or other acid is used as the converting agent, water and another non-aqueous converting agent (third converting agent such as alcohol) are also generally used, or only water (without the third converting agent) is added, but thereafter, the As such, the conversion takes place in a pressurized vessel. Since excess calcium hydroxide or calcium oxide is used to achieve overbase, a small amount of residual calcium oxide or calcium hydroxide may be present as part of the useful overbased calcium sulfonate and will be dispersed in the initial grease structure. The extremely finely divided calcium carbonate, aka colloidal dispersion formed by conversion, interacts with calcium sulfonate to form a grease-like consistency. Such overbased calcium sulfonate grease prepared through the two-step method will also be known as "simple calcium sulfonate grease", for example, US Pat. Nos. 3,242,079, 3,372,115, 3,376,222, 3,377,283, and 3,492,231.

It is known from the prior art to combine these two steps into a single step by carefully controlling the reaction. In this one-step method, carbon dioxide, and an accelerator (which produces amorphous calcium carbonate that is overbased by the reaction of carbon dioxide with an excess of calcium oxide or calcium hydroxide), and crystalline calcium carbonate (which divides the amorphous calcium carbonate very finely) The simple calcium sulfonate grease is prepared by reaction of a suitable sulfonic acid with calcium hydroxide or calcium oxide in the presence of a reactant system that reacts simultaneously as both converting agents). Thus, overbased 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 that is isolated as a separate product. Such one-step methods are disclosed, for example, in US Pat. Nos. 3,661,622, 3,671,012, 3,746,643 and 3,816,310.

In addition to simple calcium sulfonate greases, calcium sulfonate composites are known in the prior art. These complex greases are usually added with a calcium-containing strong base, such as calcium hydroxide or calcium oxide, to simple calcium sulfonate greases prepared by a two-step or one-step method, with a maximum stoichiometric equivalent of the complex acid, for example 12- It can be prepared by reaction with hydroxystearic acid, boric acid, acetic acid (which may also be a conversion agent if added before conversion), or phosphoric acid. The claimed benefits of calcium sulfonate composite grease over simple greases include reduced tackiness, improved pumpability, and improved high temperature utilization. Calcium sulfonate composite greases are disclosed, for example, in US Pat. Nos. 4,560,489, 5,126,062, 5,308,514 and 5,338,467.

Many known prior art using a two-step method teach the addition of all converting agents (water and non-aqueous converting agents) simultaneously and generally prior to heating. However, some prior art documents disclose the time interval between the addition of water (always inadequately defined or not defined at all) and the addition of at least a portion of the non-aqueous conversion agent (s). For example, U.S. Patent No. 4,560,489 adds water after the base oil and the overbased calcium carbonate have been heated to about 150 ° F., followed by the addition of acetic acid and methyl cellosolve (a highly toxic monomethyl ether of ethylene glycol). A method of heating the mixture to about 190 ° F. (Examples 1 to 3) is disclosed. The resulting grease contains at least 38% calcium overbased sulfonate, and according to the '489 patent, the use of over 38% overbased calcium sulfonate leads to soft grease, so the overbased sulfide for the method disclosed therein The ideal amount of calcium phonate is about 41-45%. The grease produced in Example 1 of the '489 patent has a dropping point of only about 570 ° F. The '489 patent does not mention the delay period between the addition of water and the addition of the non-aqueous conversion agent, but indicates that the addition is immediately after the heating period from 150 ° F to 190 ° F. The dropping and thickening agents in the '489 patent are undesirable.

In addition, U.S. Pat. There is a slight gap 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 show that after the addition of water and fatty acid converting agents to other components (including calcium persulfate sulfonate and base oil), the acetic acid is followed by the addition of methanol. A method of heating to 140 to 145 ° F. is disclosed. The mixture is then heated to about 150-160 ° F. 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 unspecified heating period. A similar method is the embodiment of the '467 patent, except that the entire fatty acid is added after conversion, and the only non-aqueous conversion agent used after heating the mixture containing water to 140 to 145 ° F. is added. A and '514 in Example C. The amount of overbased sulfonic acid in this example is 40%, which is higher than the previous examples. In addition to not achieving the ideal thickener yield results, all of these methods use methanol as the converting agent, which has environmental problems. The use of volatile alcohols as a converting agent can cause exhaustion of these components to the atmosphere as a later part of the process of making grease, which is forbidden in many parts of the world. If not exhausted, the alcohol must be recovered by water scrubbing or water trap, which incurs the cost of treating the hazardous substances. As such, there is a need for a method to achieve a better thickener yield, preferably without the use of volatile alcohols as a converting agent.

A better thickener yield is achieved in Example 10 of the '514 patent, but the use of excess lime is considered a requirement to achieve this result. In this embodiment, water and excess lime are added together with other ingredients, and the mixture is heated to 180 to 190 ° F. while acetic acid is slowly added during the heating period. The resulting grease contains 23% calcium overbased sulfonate. While this thickener yield is better than others, there is still room for better improvement that does not require the use of excess lime as the '514 patent teaches as a requirement.

Other embodiments of the '514 and' 467 patents, with a thickener yield of 23% or less, involve the use of a pressurized kettle during conversion, or other prior art that has no "delay" between the addition of water and a non-aqueous conversion agent or both. Similar to more parts. These examples involve adding water and a fatty acid converting agent, mixing for 10 minutes without heating, and then adding acetic acid in a pressurized kettle or without pressurization. These patents focus on the benefits of the use of fatty acids as a converting agent and the pre-conversion, post-conversion, or both of the fatty acids as a reason for all observed yield improvement, but none of these patents add acetic acid It does not recognize any benefit or advantage over a 10 minute interval for or other heating intervals for the disclosed embodiments. Also, as discussed below, a 10 minute mixing interval that does not include such heating is not a “delay” as the term is used herein, and is considered to be the same as the simultaneous addition of components, wherein the addition of each component is at least It takes some time and recognizes things that cannot 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 to prepare calcium sulfonate grease, or as a component required for reaction with complexed acid to form calcium sulfonate complex grease. The known prior art needs to be in an amount sufficient to provide an overall level of calcium hydroxide or calcium oxide sufficient to fully react with the complexed acid (when added to the amount of calcium hydroxide or calcium oxide present in the overbased useful calcium sulfonate). Teach the addition of calcium hydroxide or calcium oxide. As disclosed in U.S. Continuing Application Nos. 13 / 664,768 ("'768 Patent Application") and U.S. Patent No. 9,273,265, generally known prior art should be avoided for at least two reasons (dispersed in calcium sulfonate after carbonation) Teach the presence of calcium carbonate as an individual component other than the presence of amorphous calcium carbonate, or as "impurities" in calcium hydroxide or calcium oxide. The first is because calcium carbonate is generally considered a weak base that is inadequate to react with the complexing acid to form an optimal grease structure. The second is inferior if the presence of unreacted solid calcium compounds (including calcium carbonate, calcium hydroxide or calcium oxide) interferes with the conversion method, such that unreacted solids are not removed prior to or before conversion is complete. Because it causes grease. However, the applicant has filed the '574 and' 768 patents for the addition of calcium carbonate, calcium hydroxyapatite, or combinations thereof as individual components as components for reacting with complexed acids, with or without added calcium hydroxide or calcium oxide. It has been found to produce excellent grease as disclosed in.

Several prior art documents exist that disclose the addition of crystalline calcium carbonate as an individual component (other than the amount of calcium carbonate contained in the overbased calcium sulfonate), but these greases are insufficient (as the prior art teaches). It has a thickening agent or requires nano-sized particles of calcium carbonate. For example, U.S. Patent No. 5,126,062 discloses the addition of 5 to 15% calcium carbonate as an individual component in the formation of a complex 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 complexed acid in the '062 patent. In fact, the added calcium carbonate is not particularly added as a basic reactant for reacting with the complexed acid. Instead, it requires calcium hydroxide to be added as a specific calcium-containing base to react with all complexed acids. In addition, NGLI No. 2 Grease contains 36 to 47.4% of overbased calcium sulfonate, which is a significant amount of these expensive components. In another example, Chinese published application CN101993767 discloses the addition of calcium carbonate of nano-sized (5 to 300 nm size) particles added to the overbased calcium sulfonate, whereas the reference is that the nano-particle sized calcium carbonate is It does not indicate that it is added as a reactant or as the only calcium-containing base added separately to react with the complexed acid. The use of nano-sized particles is a fine dispersion of crystalline calcium carbonate formed by converting the amorphous calcium carbonate contained in the overbased calcium sulfonate (may be from about 20 to 5000 A or from about 2 to 500 nm according to the '467 patent) As such, it will increase the thickening of the grease to keep it robust, but will significantly increase the cost depending on the added calcium carbonate of the larger sized particles. This Chinese patent application greatly emphasizes the absolute need for added calcium carbonate with the correct nanoparticle size. Example according to the invention disclosed in the '574 Continuation Application As shown in Greece, by addition of micro-sized calcium carbonate which does not require the use of very expensive nano-sized particles, and one for reaction with complexed acids Or when using calcium carbonate added as the only added calcium-containing base, excellent grease can be formed.

There are also prior art documents on the use of tricalcium phosphate as an additive for lubricating grease. For example, U.S. Patent Nos. 4,787,992, 4,830,767, 4,902,435, 4,904,399, and 4,929,371 all teach the use of tricalcium phosphate as an additive for lubricating greases. However, as a calcium-containing base for reacting with an acid to produce lubricating grease, including calcium sulfonate-based grease, a mathematically equivalent formula having a melting point of formula Ca ₅ (PO ₄ ) ₃ OH or about 1100 ° C. It is believed that there is no prior reference teaching the use of calcium hydroxyapatite having. "Hydroxyapatite", a reference substance having the formula [Ca ₃ (PO ₄ ) ₂ ] ₃ · Ca (OH) ₂ as a source of tricalcium phosphate, Ca ₃ (PO ₄ ) ₂ containing grease and tricalcium phosphate. A number of prior art documents, including U.S. Published Patent Application No. 2009/0305920, are disclosed in Showa Shell Sekiyu of Japan. This reference to “hydroxyapatite” is disclosed as a mixture of tricalcium phosphate and calcium hydroxide, which is filed in the '768 patent and disclosed and claimed herein, of the formula Ca ₅ (PO ₄ ) ₃ OH or a melting point of about 1100 ° C. It is not the same as calcium hydroxyapatite, which has a mathematical equivalent formula. Despite the misreading of the nomenclature, calcium hydroxyapatite, tricalcium phosphate, and calcium hydroxide are chemical compounds that are distinguished by different chemical formulas, 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 ), do not react with each other, or differently different crystalline compounds calcium hydroxyapatite (Ca ₅ (PO ₄ ) ₃ OH). The melting point of tricalcium phosphate (having the chemical formula Ca ₃ (PO ₄ ) ₂ ) is 1670 ° C. Calcium hydroxide does not have a melting point, but instead loses water molecules at 580 ° C to form calcium oxide. The calcium oxide thus formed has a melting point of 2580 ° C. Calcium hydroxyapatite (with the formula Ca ₅ (PO ₄ ) ₃ OH or a mathematical equivalent) has a melting point of about 1100 ° C. Therefore, regardless of how inaccurate the nomenclature can be, 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 sulfonate composite grease composition and method for producing both improved thickener yields and dropping points. Many of the known prior art compositions have NGLI No. In order to achieve two classes of suitable greases, an overbased calcium sulfonate sulfonate in an amount of at least 36 wt% (based on the final grease product) is required. Overbased oil-soluble calcium sulfonate is one of the most expensive substances in the manufacture of calcium sulfonate grease, thus reducing the amount of these ingredients while still maintaining the desired level of firmness of the final grease (thereby improving the thickener yield). It is desirable to do. To achieve a significant reduction in the amount of overbased calcium sulfonate used, a number of prior art literature uses pressurized reactors. NLGI No. Persistence of 575 ° F or higher continuously within 2 grades (or if the perbase usefulness of calcium sulfonate has a percentage of 36% or less, and the grease has a worked 60 stroke penetration of 265 to 295) It is preferred to have a vaporized calcium sulfonate grease. Since the dropping point is the first and easiest guide to measure the high temperature utilization limits of lubricating grease, a higher dropping point is considered desirable.

The addition of alkali metal hydroxides in simple calcium soap grease such as anhydrous calcium-soap thickened grease is also known. However, it is not known to add alkali metal hydroxide in calcium sulfonate grease to provide improved thickener yields and high dropping points, as such additions are recognized as unnecessary to those skilled in the art. The reason for adding alkali metal hydroxides such as sodium hydroxide to simple calcium soap grease is that calcium hydroxide, which is commonly used, has insufficient water solubility, which is a weaker base than sodium hydroxide, which is highly water soluble. Due to this, a small amount of sodium hydroxide dissolved in the added water reacts rapidly with soap-forming fatty acids (generally 12-hydroxystearic acid or a mixture of 12-hydroxystearic acid and non-hydroxylated fatty acids such as oleic acid), resulting in sodium It is said to form soap. This fast reaction is thought to be "ball rolling." However, the direct reaction of a calcium-containing base such as calcium hydroxide with a fatty acid is not a problem when producing a calcium sulfonate complex grease. Due to the high washability / dispersibility of the presence of large amounts of calcium sulfonate, the reaction occurs very easily. As such, it is not known in the art to use alkali metal hydroxide in calcium sulfonate grease as a way to obtain a complexed acid for reacting with calcium hydroxide.

Combining various components and methodologies in the manufacture of calcium sulfonate grease with improved thickener yield and high dripping, for example, addition of alkali metal hydroxides (1) Calcium-containing base (basic) for reaction with complexed acid Use of calcium hydroxyapatite, crystalline calcium carbonate added, or a combination thereof (with or without added calcium hydroxide or calcium oxide) as a calcium compound); (2) delayed addition of non-aqueous converting agents; Or (3) it is not known to combine the combination of (1) and (2) above.

The present invention is based on a superbase to provide improvements in both the thickener yield (requiring a smaller amount of overbased calcium sulfonate) while maintaining acceptable miscibility measurements and the expected high temperature utility demonstrated by dropping. Calcium phonate grease and a method for manufacturing the grease. According to one preferred aspect of the present invention, the composite calcium sulfonate grease composition comprises an alkali metal hydroxide. According to another preferred embodiment, the composite calcium sulfonate grease composition is a calcium-containing base (also referred to as a basic calcium compound) added for reaction with the complexed acid, alkali metal hydroxide and calcium hydroxyapatite, calcium carbonate added, or these All inclusive. According to another preferred embodiment, the composite calcium sulfonate grease composition comprises (1) up to 36% calcium persulfate sulfonate (based on the weight of the final grease); (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 converting agents; And (5) one or more complexed acids. According to another preferred embodiment, the final grease composition comprises about 0.005 to 0.5% alkali metal hydroxide.

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

According to another preferred embodiment, prior to conversion, a first fraction of water is added as a converting agent, after conversion a second fraction of water is added, and an alkali metal hydroxide is added to the first fraction of water or the second fraction of water or both. A complex calcium sulfonate grease is prepared by reacting and mixing certain compounds according to the steps outlined above, except that they dissolve. According to another preferred embodiment, the at least two separate, having at least one temperature adjustment step, the addition step of another component (s), or a combination thereof between the primary addition of water as the converting agent and the secondary addition of water as the converting agent. In the pre-conversion step, water is added as the converting agent, and the alkali metal hydroxide is dissolved in the initial or primary addition of water as the converting agent, or in the secondary or subsequent addition of water as the converting agent, or both.

According to another preferred embodiment, the method for preparing a complex calcium sulfonate grease comprises the outlined steps, including preferred modifications, wherein the converting agent comprises water and at least one non-aqueous converting agent, and converting There is one or more delay periods between the addition of water as a zero and the addition of at least a fraction of the non-aqueous conversion agent. Preferably, the one or more delay periods are the temperature adjustment delay period or the maintenance delay period, or both, as further described below. As used herein, “non-aqueous converting agent” means any converting agent other than water and includes a converting agent that may contain some water as a diluent or impurity.

In any of the preparative aspects disclosed herein, one or more of the complexed acids may be added prior to or after conversion. Alternatively, a fraction of the one or more complexed acids may be added prior to conversion of the complex calcium sulfonate grease, and the remainder of the added one or more complexed acids may be added after conversion. All of the one or more calcium-containing bases can be added prior to or after conversion. Alternatively, a fraction of the one or more calcium-containing bases may be added prior to conversion and the rest added after conversion. Calcium hydroxyapatite, calcium carbonate added, calcium hydroxide added, calcium oxide added, or a combination thereof can be used as the calcium-containing base for reacting with the complexed acid. A large excess of calcium hydroxide relative to the total amount of complexed acid used (eg, calcium hydroxide in an amount greater than 50% greater than the stoichiometric amount required for reaction with the total complexed acid) is not added prior to conversion.

According to another preferred embodiment of the present invention, the improved thickener yield results include the addition of the alkali metal hydroxide alone or at least one of the non-aqueous converting agents, even when the overbased calcium sulfonate is considered "low quality". This is achieved by using in combination with at least one delay period for the fraction. Certain overbased oil-soluble calcium sulfonates, which are promoted and marketed for the manufacture of calcium sulfonate-based greases, can provide products with unacceptably low dropping points when prior art calcium sulfonate techniques are used. This overbased oil-soluble calcium sulfonate is referred to throughout this application as "low quality" overbased oil-soluble calcium sulfonate. When all the ingredients and methods are the same except for the commercially available batch of the overbased calcium sulfonate used, the overbased oil-soluble calcium sulfonate producing a grease with a higher dropping point (over 575 ° F.) For the purpose of is considered "good" quality of calcium sulfonate, and overbased oil-soluble calcium sulfonate to produce a grease with a lower dropping point is considered to be of "low" quality for the purposes of the present invention. Multiple examples of this are provided in the '768 patent application, the above references being incorporated by reference. Comparative chemical analysis of good quality and low quality overbased useful calcium sulfonate has been conducted, but it is believed that the exact reason for this low dropping point problem has not been proven. The most commercially available overbased calcium sulfonate is considered to be of good quality, while it is desirable to achieve both improved thickener yield and higher dropping points, whether good or low quality calcium sulfonate is used. Both improved thickener yields and higher dropping points can be achieved using good or low quality calcium sulfonate when alkali metal hydroxides are used, especially when used in combination with the delayed addition method according to the present invention. . In fact, the results of examples using low quality calcium persulfate sulfonate also demonstrate better thickener yields than those using good quality calcium persulfate sulfonate when using at least some of the preferred aspects of the invention. According to another preferred embodiment, if at least one of the non-aqueous converting agents is glycol (eg, 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.

When prepared according to the parameters of the present invention disclosed herein, the consistently high quality calcium sulfonate grease can be prepared with superior thickener yield and dropping properties over prior art greases. Manufactured in accordance with a preferred embodiment of the present invention, the overbased calcium sulfonate complex grease having an overbased oil-soluble calcium sulfonate percentage of about 10 to 45% when prepared in an open container (without pressure) is NLGI No. It has a roughness of 2 grade (or No. 2 grade or higher, ie harder) and a dropping point of 575 ° F (or higher). More preferably, the amount of overbased oil-soluble calcium sulfonate in grease prepared according to a preferred embodiment of the present invention, when prepared in an open container (without pressure), is about 10% or more and about 36% or less, more preferably about 30% or less, most preferably about 22% or less. This improved thickener yield can be achieved using both good and low quality calcium overbased sulfonates. When preparing grease in a pressurized container, greater thickener yields can be achieved using the ingredients and methods of the present invention. Most preferably, a dropping point above 650 ° F. is achieved. The lower concentration of overbased soluble calcium sulfonate achieved by the present invention is preferred because the cost of grease is reduced. Other properties, particularly at lower temperatures, such as flowability and pumpability, can be advantageously influenced by the improved thickener yield achieved according to the invention.

Without wishing to be bound by theory, the addition of alkali metal hydroxides results in a looping metathesis reaction that affects the conversion method, and reactions using complexed acids to produce these unexpected thickener yls and dropping points. Is believed to cause complex calcium sulfonate grease. As discussed above, it is known that alkali metal hydroxide is added to simple calcium soap grease, but not to complex overbased calcium sulfonate grease. This is because the calcium hydroxide used in the simple calcium soap grease generally has low water solubility and is a weak base compared to highly water-soluble sodium hydroxide. Due to this, a small amount of sodium hydroxide dissolved in the added water is rapidly formed with soap-forming fatty acids (generally 12-hydroxystearic acid or a mixture of 12-hydroxystearic acid and non-hydroxylated fatty acids, for example oleic acid). It is said to react and form sodium soap. This rapid reaction is thought to be "to perform ball rolling" in the manufacture of simple calcium soap grease. However, after all of this has occurred, if a small amount of sodium hydroxide reacts with a small amount of fatty acid, it leaves a residual reactant (calcium hydroxide and most of the fatty acid residue) to react as if sodium hydroxide was not added. Unreacted calcium hydroxide will continue to exist and will react with the remaining unreacted fatty acids to form a calcium soap thickener.

A more similar explanation is that a small amount of quickly formed sodium soap reacts further with calcium hydroxide in a metathesis reaction in which a trade of sodium and calcium occurs. Sodium soap becomes calcium soap, and calcium hydroxide becomes sodium hydroxide. This reaction is driven by the high water solubility of the sodium hydroxide and the low water solubility of the calcium soap than the sodium soap. Thereafter, it can “regenerate” a small amount of sodium hydroxide and react quickly with more fatty acids again. Thereafter, the metathesis reaction may occur again to generate more calcium soap. This roofing reaction sequence is continued until all calcium hydroxide reacts to form a calcium soap thickener. This reaction sequence loop is provided as follows:

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

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

NaOH formed in reaction 2 becomes a reactant for reaction 1.

Unlike simple calcium soap grease, the direct reaction of calcium-containing base (eg calcium hydroxide) with fatty acids has never been a problem in the manufacture of calcium sulfonate complex greases. The reaction occurs very easily, which is due to the high washability / dispersibility of calcium sulfonate present in large quantities, which is why the addition of alkali metal hydroxide is not considered or suggested in the prior art calcium sulfonate grease technology. In fact, due to the high washability / dispersibility of calcium sulfonate, which is present in large quantities during the reaction of the complexed acid with the calcium-containing base, those skilled in the art may add a small amount of alkali metal hydroxide prior to this reaction to achieve any significant benefit. I hadn't expected to get it. However, nevertheless, it is clear that the reaction of alkali metal hydroxides has an unexpectedly beneficial effect on the thickener yield in calcium sulfonate grease. If the addition of alkali metal hydroxide is combined with the delayed addition of at least a fraction of the non-aqueous converting agent methodology and the use of calcium hydroxyapatite and / or calcium carbonate as a calcium-containing base for reaction with the complexing acid, the benefit is even more It grows. Preferred aspects of the compositions and methods of the present invention include the use of an alkali metal hydroxide alone as a component of the complex calcium sulfonate grease, or as the calcium-containing base for the reaction of the alkali metal hydroxide with (1) the complexed acid. One or more delay periods between the use of calcium hydroxyapatite and / or calcium carbonate and / or (2) the addition of water as a conversion agent and the addition of at least a portion of a non-aqueous conversion agent are used in combination.

complex Calcium sulfonate  Grease composition

According to a preferred embodiment of the present invention, the composite calcium sulfonate grease composition comprises the following components: (1) 45% or less (based on the weight of the final grease) of overbased calcium sulfonate sulfonate; (2) calcium hydroxyapatite, calcium carbonate added, calcium hydroxide added, calcium oxide added, or any combination thereof; And (3) alkali metal hydroxide. More preferably, the complex calcium sulfonate grease comprises (4) one or more converting agents; And (5) one or more complexed acids. According to another preferred embodiment, the at least one converting agent comprises water and at least one non-aqueous converting agent, for example propylene glycol or hexylene glycol. Optionally, the grease composition may also include a facilitating acid. These facilitating acids help to form the grease structure. All or part of any particular component, including the converting agent and calcium-containing base, may not be present in the final finished product due to evaporation during production, volatilization, or reaction with other components.

The highly overbased oil-soluble calcium sulfonates used in accordance with these aspects of the present invention are of general altitude as reported in the art, for example U.S. Pat.Nos. 4,560,489, 5,126,062, 5,308,514 and 5,338,467. It may be an overbased oil-soluble calcium sulfonate. The highly overbased oil-soluble calcium sulfonate can be prepared in situ according to these known methods or can be purchased as a commercially available product. This highly overbased usable calcium sulfonate will have a total base number (TBN) value of at least 200, preferably at least 300, and most preferably at least about 400. Commercially available calcium overbased sulfonates 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, based on its weight, contains about 28 to 40% dispersed amorphous calcium carbonate, which is converted to crystalline calcium carbonate during the preparation of calcium sulfonate grease. The overbased calcium sulfonate also contains about 0 to 8% residual calcium oxide or calcium hydroxide, based on its weight. Most commercial overbased calcium sulfonate will also contain about 40% base oil as a diluent to prevent 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 obviate the need to add additional base oil (as a separate component) prior to conversion to acceptable grease. The overbased calcium sulfonate used may be of good or low quality as defined herein and in the '768 patent application.

The amount of highly overbased oil-soluble calcium sulfonate in the final composite grease according to embodiments of the present invention may vary, but is generally 10-45%. Preferably, the amount of highly overbased oil-soluble calcium sulfonate in the final composite grease according to aspects of the present invention is about 36, which is a lower percentage than achievable in manufacturing in an open vessel (without pressurization) and in a pressurized vessel. % Or less, more preferably about 30% or less, and most preferably about 22% or less.

Any petroleum-based naphthenic acid or paraffinic acid mineral oil generally used and well known in the field of grease manufacturing can be used as base oil according to the present invention. To prevent the overbased sulfonate from becoming too thick to be easily processed, the most commercial calcium overbased sulfonate will already contain about 40% base oil as a diluent, so add the base oil as needed and immediately after conversion. Depending on the desired roughness of the grease and the desired roughness of the final grease, it may not be necessary to add additional base oil. Synthetic base oils can also be used in the greases of the present invention. Such synthetic base oils include polyalphaolefins (PAO), diesters, polyol esters, polyethers, alkylated benzenes, alkylated naphthalenes, and silicone fluids. In some cases, synthetic base oils can have adverse effects when present during the conversion process, as will be understood by those skilled in the art. In some cases, these synthetic base oils need not be added initially, but are added to the grease manufacturing process at a stage where adverse effects are eliminated or minimized, eg after conversion. Naphthenic and paraffinic mineral base oils are preferred due to their lower cost and availability. The total amount of base oil added (including the amount added initially and any amount that can be added later in the grease preparation to achieve the desired roughness) is generally 30 to 70% based on the total weight of the grease. , Preferably 45 to 70%, most preferably 50 to 70%. Generally, the amount of base oil added as a separate component will increase as the amount of overbased calcium sulfonate decreases. As will be appreciated by those skilled in the art, combinations of the different base oils disclosed above may be used in the present invention.

Water is added as one converting agent according to preferred embodiments of the present invention. Preferably, one or more other non-aqueous conversion agents are also added in these aspects of the invention. Non-aqueous converting agents include any converting agent 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 Includes Non-aqueous converting agents also include preparations containing some water as diluents or impurities. Although they can be used as non-aqueous converting agents, it is preferred not to use alcohols, such as methanol or isopropyl alcohol or other low molecular weight (ie, more volatile) alcohols, which may be exhausted during the grease manufacturing process, or This is due to environmental concerns and environmental regulations related to the disposal of hazardous waste from scrubbed alcohol. The total amount of water added as the converting agent is 1.5 to 10%, preferably 2.0 to 5.0%, most preferably 2.2 to 4.5%, based on the final weight of the grease. Additional water can be added after conversion. In addition, if the conversion is carried out in an open vessel at a sufficiently high temperature to volatilize a significant fraction of water during conversion, additional water may be added to replace the lost water. The total amount of one or more non-aqueous converting agents added is 0.1 to 5%, preferably 0.3 to 4%, most preferably 0.5 to 2.0%, based on the final weight of the grease. Generally, the amount of non-aqueous converting agent used will decrease as the amount of overbased calcium sulfonate decreases. Depending on the conversion agent used, some or all of these may be removed by volatilization during the manufacturing process. Lower molecular weight glycols such as hexylene glycol and propylene glycol are particularly preferred. It should be noted that, as discussed below, some converting agents may also act as complexing acids to prepare a calcium sulfonate complex grease according to one aspect of the present invention. These materials will provide both the function of conversion and complexation simultaneously.

Although not required, a small amount of accelerated acid may be added to the mixture prior to conversion according to another aspect of the invention. Suitable facilitating acids, for example alkyl benzene sulfonic acids having alkyl chain lengths of generally 8 to 16 carbon atoms, can help promote efficient grease structure formation. Most preferably, this alkyl benzene sulfonic acid mainly comprises a mixture of alkyl chain lengths of about 12 carbons. This benzene sulfonic acid is generally referred to as dodecylbenzene sulfonic acid (“DDBSA”). Commercially available benzene sulfonic acids of this type are available from JemPak GK Inc. JemPak 1298 sulfonic acid supplied by the company, Calsoft LAS-99 supplied by the Pilot Chemical Company, and Biosoft S-101 supplied by the Stepan Chemical Company. When alkyl benzene sulfonic acid is used in the present invention, it is added before conversion in an amount of about 0.50 to 5.0%, preferably 1.0 to 4.0%, most preferably 1.3 to 3.6%, based on the final weight of the grease. When calcium sulfonate is prepared in situ using alkyl benzene sulfonic acid, the accelerated acid added according to this aspect is additionally required for the production of calcium sulfonate.

At least one complexed acid, at least one calcium-containing base, and at least one alkali metal hydroxide are also added as components in a preferred embodiment of the calcium sulfonate grease according to the 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 those mentioned above. According to this aspect, the calcium hydroxyapatite used as a calcium-containing base for reacting with the complexed acid may be added before or after conversion, or one fraction before conversion and one fraction after conversion may be added. Most preferably, calcium hydroxyapatite is finely divided into 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 low enough to not significantly affect the wear resistance properties of the resulting grease. Ideally, for best results, calcium hydroxyapatite should be food grade or US Pharmacopoeia grade. The amount of calcium hydroxyapatite to be added is 1.0 to 20%, preferably 2 to 15, based on the total weight of the grease, although a larger amount may be added after all reactions with the conversion and complexing acids are completed, if desired. %, Most preferably 3 to 10%.

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

According to another aspect, calcium hydroxyapatite may be added to the components in an amount insufficient to fully react with the complexing acid. In this embodiment, the finely divided calcium hydroxide and / or calcium oxide as an oil-soluble solid calcium-containing base is a fraction of any subsequently added complexed acid that is not neutralized by co-added calcium hydroxyapatite. It may be added in an amount sufficient to fully react with and neutralize it, preferably before conversion. In this embodiment, the calcium hydroxide and / or calcium oxide exhibits a hydroxyl equivalent basicity provided by the calcium hydroxyapatite added, calcium hydroxide, and calcium oxide as a whole, preferably up to 75%. In another embodiment, calcium carbonate may be added together with calcium hydroxyapatite, calcium hydroxide and / or calcium oxide, with calcium carbonate added prior to or after reaction with the complexing acid. If the amount of calcium hydroxyapatite, calcium hydroxide, and / or calcium oxide is not sufficient to neutralize the complexed acid or acids to which it is added, calcium carbonate is preferably at least an amount sufficient to neutralize any residual complexed acid or acids. It is added in quantity.

According to these aspects of the invention, the added calcium carbonate used as a calcium-containing base, alone or in combination with another calcium-containing base or base, is about 1 to 20 microns, preferably about 1 to 10 microns, Most preferably it is finely divided into an average particle size of about 1 to 5 microns. In addition, the added calcium carbonate is preferably crystalline calcium carbonate (most preferably calcite) of sufficient purity to have abrasive contaminants such as silica and alumina to a sufficiently low degree so as not to significantly affect the abrasion resistance properties of the resulting grease. )to be. Ideally, for optimal results, calcium carbonate should be food grade or US Pharmacopoeia grade. The amount of calcium carbonate to be added is 1.0 to 20%, preferably 2.0 to 15%, 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 overbased calcium sulfonate. According to another preferred aspect of the invention, the calcium carbonate to be added is added prior to conversion as a calcium-containing base component added alone to react with the complexing acid. Additional calcium carbonate can be added to the simple or complex grease aspect of the present invention after conversion and, in the case of complex grease, after all reactions with the complexing acid are complete. However, the indication for calcium carbonate added herein is added prior to conversion in the manufacture of the composite grease according to the present invention, either as one of the added calcium-containing bases for reaction with the complexed acid or as the only added calcium-containing base. It shows as calcium carbonate as.

According to another aspect, the added calcium hydroxide and / or added calcium oxide added before or after conversion is fine with an average particle size of about 1 to 20 microns, preferably about 1 to 10 microns, most preferably about 1 to 5 microns. Is divided. In addition, calcium hydroxide and calcium oxide will have sufficient purity to have abrasive contaminants such as silica and alumina at levels low enough to not significantly affect the wear resistance properties of the resulting grease. Ideally, for best results, calcium hydroxide and calcium oxide should be food grade or US Pharmacopoeia grade. The total amount of calcium hydroxide and / or calcium oxide will be 0.07 to 1.20%, preferably 0.15 to 1.00%, most preferably 0.18 to 0.80%, based on the total weight of the grease. This amount is added as separate book ingredients in addition to the amount of residual calcium hydroxide or calcium oxide contained in the overbased calcium sulfonate. Most preferably, calcium hydroxide in excess of the total amount of complexing acid used is not added prior to conversion. According to another aspect, 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 only added calcium containing base for this reaction, or It can be used in combination for a reaction.

The alkali metal hydroxide added includes sodium hydroxide, lithium hydroxide, potassium hydroxide, or a combination thereof. Most preferably sodium hydroxide is used as alkali metal hydroxide. The total amount of alkali metal hydroxide added is preferably about 0.005 to 0.5%, more preferably about 0.01 to 0.4%, and most preferably about 0.02 to 0.20%, based on the weight of the final grease product. Alkali metal hydroxides, including calcium-containing bases, react with the complexing acid, resulting in an alkali metal salt of the complexing acid present in the final grease product. The preferred amount shown herein is an amount added as a raw material to the weight of the final grease product, even if 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 being added to other components. The water used for dissolving the alkali metal hydroxide may be water used as a converting agent or water added after conversion. It is most preferred to dissolve the alkali metal hydroxide in water prior to adding it to other components, but it can also be added directly to other components without primary dissolution in water.

The complexing acid used in these embodiments will include at least one of the following, preferably two or more: long chain carboxylic acids, short chain carboxylic acids, boric acid and phosphoric acid. Acetic acid and other carboxylic acids can be used as conversion agents or complexed acids or both, depending on the time of addition. Similarly, some complexed acids (e.g. 12-hydroxystearic acid of '514 and' 467 patents) can be used as converting agents. The total amount of the complexing acid added is preferably 2.8 to 11% based on the weight of the final grease. Long-chain carboxylic acids suitable 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 0.5 to 5.0%, preferably 1.0 to 4.0%, most preferably 2.0 to 3.0%, based on the final weight of grease.

Short chain carboxylic acids suitable for use in accordance with the present invention include aliphatic carboxylic acids having 8 or less carbons, preferably 4 or fewer carbons. 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%, most preferably 0.15 to 0.5%, based on the final weight of the grease. Any compound that can be expected to react with water or other components used in the preparation of the grease according to the invention, including reactions that produce long or short chain carboxylic acids, is also suitable for use. For example, using acetic anhydride will form acetic acid to be used as a complexing acid by reaction with water present in the mixture. Similarly, using methyl 12-hydroxystearate will form 12-hydroxystearic acid to be used as complexing acid by reaction with water present in the mixture. Alternatively, if sufficient water is not already present in the mixture, additional water can be added to the mixture to react with these components to form the required complexing acid.

When boric acid is used as the complexing acid according to this aspect, an amount of 0.3 to about 4.0%, preferably 0.5 to 3.0%, most preferably 0.6 to 2.0%, based on the final weight of the grease, is added. Boric acid may be added after first dissolving in water or slurried, or it may be added without water. Preferably, boric acid will be added during the manufacturing process so that water continues to be present. Alternatively, any well-known inorganic boric acid salt can be used instead of boric acid. Similarly, any established boric organic compounds, such as borated amines, borated amides, borated esters, boric alcohols, boric glycol, boric ethers, boric epoxides, urea borate, boric acid A carboxylic acid, boron sulfonic acid, boric epoxide, boric peroxide, etc. can 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%, most preferably 0.8 to 2.0%, based on the final weight of grease, is added. The percentages of the various complexed acids disclosed herein are presented for purely active compounds. If any of these complexed acids can be in diluted form, they may be suitable for use as such in the present invention. However, the percentage of this diluted complexed acid will need to be adjusted to include the dilution factor and bring the actual active substance to a certain percentage range.

Other additives generally recognized in the field of grease manufacturing may be added to the simple grease aspect or the composite grease aspect of the present invention. These additives are rust and corrosion inhibitors, metal inert agents, metal passivating agents, antioxidants, extreme pressure additives, anti-wear additives, chelating agents, polymers, tackifiers, dyes, chemical markers, fragrance imparter, and evaporation Sex solvents. The rear class can 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 components are based on the final weight of the finished grease, unless stated otherwise, even though the amount of the component may not be present in the final grease product due to reaction or volatilization.

Composite containing alkali metal hydroxide Calcium sulfonate  Method of manufacturing grease

The calcium sulfonate grease composition is preferably prepared according to the methods of the present invention disclosed herein. In one preferred embodiment, the method comprises: (1) mixing the overbased calcium sulfonate and base oil; (2) dissolving alkali metal hydroxide in water and adding and mixing the mixture with other components; (3) adding and mixing one or more calcium-containing bases; (4) adding and mixing one or more converting agents which may include water from step c, if added prior to conversion; (5) adding and mixing one or more complexed acids; And (6) heating some combination of these ingredients until conversion occurs. In this preferred embodiment, there is no delay between the addition of water as a converting agent (if water is used as the converting agent) and the addition of any fraction of any non-aqueous converting agent (if a non-aqueous converting agent is used). In another preferred embodiment, the method comprises one or more delay periods between the addition of water and at least one non-aqueous conversion agent, and the addition of at least one fraction of one or more other non-aqueous conversion agents. These same steps are included, except that they exist. For ease of reference, the term "alkali addition method" will be used to describe all preferred aspects of the methods according to the invention in which an alkali metal oxide is added without any delayed addition of a non-aqueous converting agent, and the term "alkali / "Delayed Addition Method" means that all of the methods according to the present invention, in which an alkali metal hydroxide is added, there is at least one delay period between the addition of water as a conversion agent and the addition of at least a portion of the non-aqueous conversion agent (s). It will be used to describe preferred aspects. The term "delayed addition method" will be used to denote the '476 patented delayed non-aqueous converting agent method without any alkali metal hydroxide addition.

In both the preferred alkali addition method and the alkali / delayed addition method, each of the components of step (2), step (3) and step (5) can be added before conversion, after conversion, or in a fraction before conversion. This is added and another fraction can be added after conversion. Optionally, the facilitating acid may be added and mixed with the components, preferably prior to conversion. When using an accelerated acid, it is also preferred that the alkali metal hydroxide is added to the mixture before it is added. Alternatively, 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 particular ingredients and amounts used in the method are in accordance with preferred aspects of the composition disclosed herein.

In both the preferred alkali addition method and the alkali / delayed addition method, the components in step (2), step (3) and step (5) are added to each other and the components in steps (1) and (4) The order of addition to the fields and the timing of the heating of the components is 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 converting agent is important in the alkali / delayed addition method as further described below.

According to another preferred embodiment of both the alkali addition method and the alkali / delayed addition method, the complex calcium sulfonate grease is added with a first fraction of water added as a converting agent prior to conversion, and a second fraction of water added after conversion. , Prepared by reacting and mixing certain compounds according to the steps outlined above, except that the alkali metal hydroxide is dissolved in the first fraction of the water or the second fraction of the water, or both. According to another preferred embodiment of both the alkali addition method and the alkali / delayed addition method, between the primary addition of water as the converting agent and the secondary addition of water as the converting agent, at least one temperature adjustment step, another component (s) Using the addition step or a combination thereof, water is added as at least two separate pre-conversion steps as a converting agent, and the alkali metal hydroxide is dissolved in the initial or primary addition of water as the converting agent, or the water is used as the converting agent. Dissolve in the second or subsequent addition, or both.

According to another preferred embodiment of both the alkali addition method and the alkali / delayed addition method, at least a portion of the complexing acid is added prior to heating. According to another preferred embodiment, the entire complexed acid (s) is added prior to heating. According to another preferred embodiment of both the alkali addition method and the alkali / delayed addition method, when the calcium carbonate to be added is used as a calcium-containing base added to react with the complexing acid, it is added with any complexing acid (s). It is added before the reaction. According to another preferred embodiment of both the alkali addition method and the alkali / delayed addition method, calcium hydroxyapatite, calcium hydroxide added and calcium carbonate added are all used as calcium-containing bases to react with the complexing acid. In this embodiment, adding at least a fraction of calcium hydroxyapatite and calcium hydroxide prior to the addition of any complexing acid, and if complexing acid is added prior to conversion, calcium carbonate is added after at least a portion of the complexing acid is added It is most desirable to do. According to another preferred aspect of both the alkali addition method and the alkali / delayed addition method, the water comprising dissolved alkali metal hydroxide is added to the complexed acid (s) after the calcium-containing base (s) are added and / or before conversion. ) Is added after a fraction is added. According to another preferred embodiment, the water in which the alkali metal hydroxide (or alkali metal hydroxide added separately) is dissolved is added after the addition of at least a fraction of one or more complexed acids.

According to a number of different aspects of both the alkali addition method and the alkali / delayed addition method, the method, except for step (3) (addition of calcium-containing base (s)), involving one or more of the following: , Same as the above embodiments: (a) mixing the finely divided calcium hydroxyapatite as the only added calcium-containing base prior to conversion; (b) according to one embodiment, mixing the finely divided calcium hydroxyapatite and calcium carbonate in an amount sufficient to fully react with and neutralize the subsequently added complexing acid; (c) According to another aspect of the present invention, finely divided calcium hydroxyapatite and calcium hydroxide and / or calcium oxide are added, in an amount sufficient to fully react with and neutralize the complexing acid that is subsequently added. And / or mixing with calcium hydroxide and / or calcium oxide present in an amount of hydroxide equivalent basicity, preferably 75% or less, provided by the calcium oxide and calcium hydroxyapatite as a whole; (d) according to another aspect of the invention, after conversion, mixing the calcium carbonate added; (e) according to another aspect of the invention, after conversion, reacting completely with any complexing acid added after conversion and mixing calcium hydroxyapatite in an amount sufficient to neutralize it; (f) Finely divided calcium hydroxyapatite and calcium hydroxide in an insufficient amount to mix and finely partition the finely divided calcium carbonate as an oil-soluble solid calcium-containing base prior to conversion, and to fully react and neutralize the subsequently added complexing acid and And / or calcium hydroxide and / or calcium oxide and calcium hydroxide present in the amount of preferably equal to or less than 75% of the hydroxide equivalents provided by the calcium hydroxide and / or calcium oxide and calcium hydroxyapatite added. Reacting completely with a fraction of apatite and any subsequently added complexing acid not neutralized by calcium hydroxide and / or calcium oxide and mixing with said added calcium carbonate added in an amount sufficient to neutralize it.

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

For example, the first temperature adjustment delay period is the period of time it takes to change the temperature of the mixture to a desired temperature or temperature range (first temperature) (typically by heating) after water is added. The first holding delay period is the amount of time to keep the mixture at the first temperature. The second temperature adjustment delay period is a period of time 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 is to heat or cool the mixture to another temperature or temperature range (second temperature) when another component (e.g., complexed acid) is added after reaching the first temperature. It may be the amount of time after the first temperature adjustment delay period for, but there is no delay period between reaching the first temperature and successive heating or cooling to the second temperature. The second holding delay period is the amount of time 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 ambient temperature or elevated temperature. Any subsequent temperature can be higher or lower than the previous temperature. The final pre-conversion temperature is about 190 to 220 ° F. or up to 230 ° F., such as the temperature at which conversion typically occurs in an open kettle. will be. The temperature before final conversion may be below 190 ° F., but these process conditions will generally result in significantly longer conversion times, and thickener yields may be reduced. The temperature and temperature range before the final conversion in which conversion takes place may be different in a closed vessel. Any combination of temperature adjustment delay period and / or maintenance delay period can be used. Most preferably, the mixture of pre-conversion components is heated to a constant temperature or a range of temperatures for at least one delay period or for each delay period.

Generally, the maintenance delay period will be followed or preceded by a temperature adjustment delay period, and vice versa, but there may be two maintenance delay periods continuously or two two temperature adjustment periods continuously. For example, the mixture can be maintained at ambient temperature for 30 minutes prior to the addition of one non-aqueous conversion agent (first retention delay period), another time prior to the addition of the same or different non-aqueous conversion agent. Can be maintained at ambient temperature for the second time (second maintenance delay period). In addition, the mixture may be heated or cooled to a first temperature after the non-aqueous converting agent is added (first temperature adjustment period), and then, the mixture may be added at the second temperature after the same or different non-aqueous converting agent is added. The furnace is heated or cooled (a second temperature adjustment period without any intermediate holding period). In addition, the fraction of the non-aqueous converting agent need not be added after every delay period, and the delay period prior to or between additions can be omitted. For example, the mixture can be heated to a constant temperature (first temperature adjustment delay period), and then maintained at that temperature for a period of time before the addition of any non-aqueous conversion agent (first retention delay). term).

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

Depending on the various preferred aspects of the alkali / delayed addition method, different modifications to the delay period can also be used. For example, each of the following is a separate preferred embodiment: (a) at least a fraction of the non-aqueous conversion agent is added (almost simultaneously) including the primary addition of water and the same non-aqueous conversion agent and / or different ratios as above. Another fraction of the aqueous conversion agent is added after at least one delay period; (b) no amount of non-aqueous conversion agent is added at the same time as water, and there is at least one delay period prior to the addition of any non-aqueous conversion agent; (c) At least a fraction of the non-aqueous conversion agent is converted to a temperature range of about 190 to 230 ° F. before the final conversion of the mixture (as a temperature range in which conversion occurs in an open container, or when produced in a closed container). Heated to the temperature range that occurs) is added after heating; (d) When at least one of the non-aqueous converting agents is glycol (eg, propylene glycol or hexylene glycol), a fraction of the glycol is added almost simultaneously with water, another fraction of glycol and any other All of the non-aqueous converting agents are added after at least one delay period; (e) When acetic acid is added before conversion, it is added almost simultaneously with water, another (different) non-aqueous conversion agent is added after a delay period; (f) at least a fraction of the one or more non-aqueous conversion agents is added at the end of the final period of one or more delay periods, and another fraction of the same and / or different non-aqueous conversion agent is one or more previous delay periods. Is added after lifting; Or (g) all of the one or more non-aqueous converting agents are added at the end of the final period of one or more delay periods.

According to one preferred embodiment of the alkali / delayed addition method, all or one fraction of the non-aqueous conversion agents are batched after a delay period (as opposed to continuous addition according to the delay period process described below, all at once). Is added. However, in large or commercial scale operations, due to the volume of materials involved, it will take some time to complete the batch addition of this non-aqueous conversion agent to the grease batch. In batch addition, the time taken to add the non-aqueous conversion agent to the grease mixture is not considered a delay period. In this case, any delay prior to the addition of the non-aqueous conversion agent or its addition ends at the start time of the batch addition of the non-aqueous conversion agent. According to another preferred embodiment, at least one or a fraction of one of the non-aqueous converting agents is added in a continuous manner during a delay period (temperature adjustment delay period or maintenance delay period). This continuous addition can be accomplished by slowly adding the non-aqueous conversion agent at a fairly constant flow rate, or by repeated separate and increased additions during the temperature adjustment delay period, maintenance delay period, or both. In this case, the time required to completely add the non-aqueous converting agent is included in the delay period, and the period ends upon completion of the addition of the non-aqueous converting agent. According to another preferred embodiment of the alkali / delayed addition method, 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 different non-aqueous conversion agent is delayed. It is added in a continuous manner for a period. According to another preferred aspect of the alkali / delayed addition method, alcohol is not used as a non-aqueous converting agent.

Although the delay period within the scope of the present invention may involve a maintenance delay period without heating (eg, the mixture was maintained at ambient temperature during the first maintenance delay period prior to heating), the addition of water as a converting agent and A short period of time of 15 minutes or less without any heating between the addition of the entire non-aqueous conversion agent (s) is not a "delay" or "delay period" as used herein. The delay for the addition of all or any of the non-aqueous converting agent (s) without heating during the delay period should be at least about 20 minutes, more preferably at least about 30 minutes, for purposes of the present invention. Between the addition of water and the addition of a non-aqueous converting agent, but not including heating, to another fraction of the same non-aqueous converting agent (s) as above or to the addition of some or all of the different non-aqueous converting agent (s) An interval of 20 minutes or less, which includes a subsequent longer holding delay period or subsequent heating, does not involve a “delay period” within the scope of the present invention. In this case, the initial short-term interval is not a “delay period”, but the subsequent longer holding delay or temperature adjusting delay prior to the addition of the non-aqueous converting agent is the holding delay period or temperature adjusting delay period for purposes of the present invention. In addition, all or some fractions of one or more non-aqueous converting agents may be added slowly during one or more temperature controlled delay periods or sustained delay periods, or both. Such slow addition may include a fairly continuous addition of the non-aqueous converting agent during the delayed period (s) or repeated increasing additions during the delayed period (s).

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

One preferred embodiment of the alkali / delayed addition method according to the present invention comprises the following steps: (1) mixing the following components in a suitable grease making container: containing water, dispersed amorphous calcium carbonate as a converting agent. Highly overbased oil-soluble calcium sulfonate, optionally, at least a fraction of a suitable amount of a suitable base oil (if necessary), one or more alkali metal hydroxides, and, optionally, one or more non-aqueous converting agents to form the first mixture; (2) Mixing or stirring / mixing or stirring the first mixture while maintaining it within a certain temperature or within a certain temperature range, or the temperature of the first mixture to another temperature (s) or temperature range for one or more delay periods. Adjusting to be heated or cooled; (3) optionally, mixing at least a fraction of one or more non-aqueous conversion agents with the first mixture after one or more delay periods or during the period to form a second mixture; (4) the first mixture (or the second mixture if a non-aqueous converting agent is added in step (3)) for a final period of one or more delay periods, the conversion temperature (preferably, for an open vessel, a general range) Heating to a range of 190 to 230 ° F. higher than 190 to 220 ° F.) to form a third mixture; (5) after step (4) or during step (4), mixing one or more non-aqueous converting agents all or any remaining portion (if present); And (6) the temperature of the conversion until the conversion of the amorphous calcium carbonate contained in the overbased calcium sulfonate to the very finely divided crystalline calcium carbonate is completed. To 230 ° F.) while continuously mixing to convert the third mixture; (7) mixing one or more calcium-containing bases; (8) optionally, mixing a facilitating acid; And (9) mixing one or more suitable complexing acids. This method produces the desired complex calcium sulfonate grease. Step (7) may be performed prior to or after conversion, or some 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. You can. Step (8) may be carried out at any time prior to the conversion. Step (9) may be carried out prior to or after conversion, or some or all of the fractions or all of the complexed acids may be added prior to conversion, and some or all of the complexed acids may be added after conversion. You can. Most preferably, this alkali / delayed addition method is carried out in an open vessel, but may also be carried out in a pressurized vessel. Most preferably, the at least one alkali metal hydroxide is dissolved in water to be used as a converting agent prior to adding them in step (1). Alternatively, the alkali metal hydroxide can be removed in step (1) and dissolved in water, and the solution is added before or after conversion later.

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

The order of steps (2) to (6) for preparing the composite grease is an important aspect of the invention with respect to aspects including an alkali / delayed addition method. Certain other aspects of the method are not important in obtaining the preferred calcium sulfonate grease composition according to the present invention. For example, the order in which calcium-containing bases are added to each other is not important. Also, the temperature at which water and calcium-containing bases as the converting agent are added to obtain acceptable grease is not critical, but the temperature reaches 190 to 200 ° F. (or other temperature range in which conversion occurs during manufacture in a closed container). It is preferred that they are added before. When using more than one complexed acid, the order in which they are added before or after conversion is also generally not important.

Another preferred embodiment of the alkali / delayed addition method includes: water, one or more alkali metal hydroxides, up to 45%, perbasic calcium sulfonate containing dispersed amorphous calcium carbonate, and optionally a base oil, by mixing. Forming a first mixture; Adding at least a fraction of one or more non-aqueous converting agents to the first mixture after one or more delay periods or during the period to form a pre-conversion mixture; The amorphous calcium carbonate contained in the overbased calcium sulfonate, including at least one delay period, which is a sustain delay period in which the first mixture or the pre-conversion mixture is maintained at a constant temperature or within a predetermined temperature range during a sustain delay period. Converting the pre-conversion mixture to the converted mixture by heating until conversion to crystalline calcium carbonate occurs. In other embodiments, one or more alkali metal hydroxides are added after conversion instead of before conversion, or a fraction is added before conversion and a fraction is added after conversion. The pre-conversion and post-conversion additions can be the same or different additions of alkali metal hydroxides as above.

Another preferred embodiment of the alkali / delayed addition method includes: water, one or more alkali metal hydroxides, up to 36%, overbased calcium sulfonate containing dispersed amorphous calcium carbonate, and optionally a base oil, by mixing. Forming a first mixture; Adding at least a fraction of one or more non-aqueous converting agents to the first mixture after one or more delay periods or during the period to form a pre-conversion mixture; Converting the pre-conversion mixture into a converted mixture by heating until the conversion of amorphous calcium carbonate contained in the overbased calcium sulfonate to crystalline calcium carbonate is completed. In other embodiments, one or more alkali metal hydroxides are added after conversion instead of before conversion, or a fraction is added before conversion and a fraction is added after conversion. The pre-conversion and post-conversion additions can be the same or different additions of alkali metal hydroxides as above.

Another preferred embodiment of the alkali / delayed addition method includes the following steps: In a suitable grease making vessel, mix a high amount of highly overbased oil-soluble calcium sulfonate with dispersed amorphous calcium carbonate and a suitable amount of suitable base oil (if necessary). , Initiating mixing. Thereafter, one or more accelerated acids are added, preferably mixed for about 20 to 30 minutes. Thereafter, one portion of calcium hydroxide followed by the entire calcium hydroxyapatite, and then the entire calcium carbonate is added and mixed for another 20 to 30 minutes. Next, a fraction of acetic acid and a fraction of 12-hydroxystearic acid are added and mixed for another 20 to 30 minutes (these components may be converting agents, but there are delays associated with them since they are added before water) (Not noticed). Thereafter, water used as a converting agent, including a small amount of alkali metal hydroxide dissolved in water, is added and mixed while heated to a temperature of 190 to 230 ° F. (first temperature adjusting delay period and final delay period). Thereafter, the entire hexylene glycol is added as a non-aqueous converting agent. The mixture has a temperature range of conversion until the conversion of the amorphous calcium carbonate contained in the overbased calcium sulfonate to a very finely divided crystalline calcium carbonate is completed (in the case of an open container, preferably 190 to 230 ° F.) It is switched by continuing mixing while maintaining the furnace temperature. After conversion, the remaining calcium hydroxide is added and mixed for about 20 to 30 minutes. Then, the remaining acetic acid and the remaining 12-hydroxystearic acid are added and mixed for about 30 minutes. Subsequently, after adding boric acid dispersed in water, phosphoric acid is slowly and slowly added. Thereafter, the mixture is heated to remove water and volatiles, cooled, more base oil is added as necessary, 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 method, the steps and components are heated to about 160 ° F. after the addition of water as a converting agent and before addition of hexylene glycol as a non-aqueous converting agent. 1 temperature adjustment delay period), except that it is maintained at the temperature for about 30 minutes (the first maintenance delay period) before continuing heating to 190 to 230 ° F. (second temperature adjustment delay period and final delay period) , Same as outlined.

Preferred embodiments of both the alkali addition method and the alkali / delayed addition method, which can be carried out in open or closed kettles, are generally used for grease production. The conversion method can be achieved under normal atmospheric pressure or under pressure in a closed kettle. Manufacturing in open kettles (non-pressurized containers) is preferred because such grease making equipment is generally available. For the purposes of the present invention, an open container is any container with or without a top cover or hatch, and such top cover or hatch is vapor-tight so that no significant pressure can be generated during heating. This is not. The use of such open vessels, which contain a closed female cover or hatch during the conversion process, will generally help to maintain the required level of water as the converting agent while at the same time setting the shear temperature above the boiling point of water. This higher conversion temperature can lead to further thickener yield improvement for both simple and complex calcium sulfonate greases, as will be understood by those skilled in the art. Manufacturing in a pressurized kettle can also be used, which can lead to a better improvement of the thickener yield, but the pressurization method can be more complicated and difficult to control. In addition, the production of calcium sulfonate grease in a pressurized kettle can cause productivity problems. The use of a pressurized reaction can be important for certain types of grease (eg polyurea grease), and most grease plants will only have a limited number of pressurized kettles. The use of a pressurized kettle to prepare calcium sulfonate grease, where pressurization reaction is not critical, may limit the ability of other greases in plants where pressurization reaction is important. These problems are avoided by using open containers.

Most preferably, both the alkali addition method and the alkali / delayed addition method for preparing the complex calcium sulfonate grease also include the following steps: (a) after conversion, mixing the additional base oil and the complexing acid as necessary. ; (b) mixing and heating to a temperature high enough to ensure removal of water and all volatile byproducts and optimize final product quality; (c) cooling the grease while adding additional base oil as necessary; (d) adding the remaining desired additives as is well known in the art; And, if necessary, (e) milling the final grease as desired to obtain a final smooth and uniform product. Although the order and timing of these final steps is not important, it is desirable that water is quickly removed after conversion. Generally, to remove water initially added as a converting agent, and all water formed by a chemical reaction during the formation of grease, the grease is (preferably under open conditions, not under pressure but under pressure). It is heated to 250 to 300 ° F, preferably 300 to 380 ° F, most preferably 380 to 400 ° F. Having water in the grease batch for an extended period of time during manufacture can cause degradation of the thickener yield, dropping point, 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 ° F. The polymeric additive, when added at a sufficient concentration, can prevent effective evaporation of water. Therefore, the polymeric additive should preferably be added to the grease only after all water has been removed. During manufacture, if it is possible to measure that all water has been removed before the grease temperature has preferably reached 300 ° F., preferably any polymer additive can be added at any time thereafter.

Examples 1 to 18 of US 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 a method of making such a composition are further disclosed and described with reference to the following examples.

Example 1A (Baseline Example-No Alkali Addition Method, No Alkali / Delayed Addition Method): A calcium sulfonate composite grease according to the composition of the '768 patent application was prepared according to the following: 264.61 g 400 TBN overbased usefulness Following calcium sulfonate, 327.55 g of a solvent neutral group 1 paraffinic acid base oil having a viscosity of about 600 SUS at 100 ° F. and PAO having a viscosity of 4 cSt at 100 ° C. of 11.70 g were added to an open mixing vessel. The 400 TBN overbased oil-soluble calcium sulfonate was low quality calcium sulfonate similar to that used in Examples 10 and 11 of the above disclosed and '768 patent applications. Mixing without heating was initiated using a planetary mixing paddle. Thereafter, 23.94 g of mainly C12 alkylbenzene sulfonic acid was added. After 20 minutes of mixing, 50.65 g of calcium hydroxyapatite having an average particle size of about 1 to 5 microns, and 3.63 g of food grade purity calcium hydroxide having an average particle size of about 1 to 5 microns are added, and 30 minutes Let it mix. The amount of calcium hydroxide added as a separate component is an amount other than the amount of residual calcium hydroxide contained in the overbased calcium sulfonate. Thereafter, 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 with 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 dispersed calcium carbonate contained in the overbased calcium sulfonate. Thereafter, 13.20 g of hexylene glycol (non-aqueous converting agent) and 38.22 g of water were added substantially simultaneously (without a delay period). The mixture was heated until the temperature reached 190 ° F. The temperature was maintained at 190-200 ° F. for 45 minutes until 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 allowed to mix 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. Thereafter, 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 was added followed by 17.92 g of a 75% solution of phosphoric acid in water. The mixture was then heated with continued stirring using an electric heating mantle. When the grease reached 300 ° F., 22.22 g of styrene-ethylene-propylene copolymer was added as a crumb-formed solid. When the entire polymer was dissolved and completely dissolved in the grease mixture, the grease was further heated to about 390 ° F. The heating mantle was removed and the grease was stirred continuously in open air to allow it to cool. When the grease was cooled to 300 ° F., 33.01 g of food grade anhydrous calcium sulfate with an average particle size of about 1 to 5 microns was added. When the temperature of the grease was cooled to 200 ° F., 4.43 g of polyisobutylene polymer was added. Mixing was continued until the grease reached a temperature of 170 ° F. Thereafter, the grease was removed from the mixer and three roll mills were passed through three times to achieve a final smooth and homogeneous texture. The grease had 287 round trip mixing. The percent overbased oil-soluble calcium sulfonate in the final grease was 23.9%. The dropping point was> 650 ° F. In this example, calcium hydroxyapatite and calcium carbonate were added prior to conversion according to aspects of the '768 patent application. In addition, 33% of the total age of calcium hydroxide was added before 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 and 12-hydroxystearic acid was added after conversion.

Example 1B ('476 patent application delayed addition method, no alkali addition): Another calcium composite grease, except that there was a delay in the addition of a non-aqueous conversion agent (hexylene glycol) and Example 1A Manufactured using the same equipment, raw materials, amounts, and manufacturing method. Other initial ingredients (including water) were mixed, heated to a temperature of about 190 ° F. (first temperature adjustment delay period), and hexylene glycol was added as soon as 190 ° F. was reached (no retention delay period). When hexylene glycol was added, the conversion occurred quickly. The grease was held at 190-200 ° F. for an additional 45 minutes. Thereafter, the rest of the process was the same as the grease in Example 1. The final grease had 60 round trips of 290 rounds. The percent overbased oil-soluble calcium sulfonate in the final grease was 21.4%. The dropping point was> 650 ° F. As can be seen, the grease of this example had an improved thickener yield as compared to the grease of Example 1, as evidenced by the lower final percentage of overbased calcium sulfonate as compared to the miscibility.

Example 2 (Alkali / Delayed Addition Method Aspect): Another calcium sulfonate composite grease, including delayed addition of a non-aqueous conversion agent, except that an alkali metal hydroxide was also added to water, Example 1B Made similar to grease. The grease was prepared as follows: 240.35 g of 400 TBN overbased oil-soluble calcium sulfonate followed by 345.33 g of solvent neutral group 1 paraffinic acid base oil having a viscosity of about 600 SUS at 100 ° F., and 10.79 g, 100 PAO having a viscosity of 4 cSt at ℃ was added to the open mixing vessel. The 400 TBN overbased oil-soluble calcium sulfonate was low quality calcium sulfonate similar to that used in Examples 10 and 11 of those disclosed above and US Patent Application No. 13 / 664,768. Planetary mixing paddles were used to initiate mixing without heating. Thereafter, 21.81 g of mainly C12 alkylbenzene sulfonic acid was added. After 20 minutes of mixing, 46.14 g of calcium hydroxyapatite with an average particle size of 5 microns or less and 3.34 g of food grade purity calcium hydroxide with an average particle size of 5 microns or less were added and allowed to mix for 30 minutes. Thereafter, 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 ° F. Then, 0.76 g of glacial acetic acid and 9.63 g of 12-hydroxystearic acid were added (because glycol is later added as a non-aqueous converting agent, initially as a complexing acid). It is noted that 12-hydroxystearic acid rapidly melts, dissolves, and reacts at a temperature of about 180 ° F. to which the acid is added. Immediately after the addition of the two complexed acids, the mixture began to develop in 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 somehow be associated with a faster formation of the calcium salt of the complexing acids. Without wishing to be bound by theory, one possible explanation of the whip 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 entirely formed. to be. Sodium fatty acid salts are well known to be water and surface active and can cause foaming that can lead to whip cream appearance.

The mixture was stirred while still heating to a temperature of 190-200 ° F. (first temperature adjustment delay period). Upon reaching the temperature range of 190-200 ° F., the whip cream appearance subsided. Thereafter, 12.46 g of hexylene glycol was added as a non-aqueous converting agent. After 1 hour and 10 minutes, no visible conversion has yet occurred. FTIR also showed that most of the initially added water was lost due to evaporation. Another 35 ml of water and another 12.47 g of hexylene glycol were added. After another 1 hour and 20 minutes, a visible conversion occurred.

The grease continued to thicken over time. To prevent the grease from becoming too heavy to stir effectively, a total of 100.93 g of two nearly identical fractions of the same paraffinic base oil were added. If further thickening appeared to be 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. Thereafter, 6.80 g of the same calcium hydroxide as above was added and allowed to mix 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 190-200 ° 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 was added. Thereafter, 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 75% solution of phosphoric acid in 16.25 g of water was added slowly, mixed and allowed to react. Another 49.47 g of paraffinic base oil was added as the grease continued to harden. The mixture was then heated with continued stirring using an electric heating mantle. When the grease reached 300 ° F., 20.64 g of styrene-alkylene copolymer was added as a flaky solid. The grease was further heated to a target temperature of 390 ° F. However, the upper temperature was overshot to 429 ° F. The heating mantle was removed and the grease was continuously stirred in open air to cool. When the highest temperature was reached, the polymer was melted and completely dissolved in the grease mixture. When the grease was cooled to 300 ° F., 30.29 g of food grade anhydrous calcium sulfate with an average particle size of 5 microns or less was added. Upon cooling of the grease to 200 ° F., 2.23 g of aryl amine 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 ° F. Thereafter, the grease was removed from the mixer and three roll mills were passed through three times to achieve a final smooth and homogeneous texture. The grease had a reciprocal mixing degree of 281 60 times. The percent overbased oil-soluble calcium sulfonate in the final grease was 20.49%. The dropping point was> 650 ° F. As can be seen, this thickener yield of grease was superior to the two example greases above. Using the conventional semi-linear relationship between the degree of miscibility and the percent overbased calcium sulfonate concentration, the grease of this example is 19.85 when additional base oil is added to bring the miscibility to the same value as Example 1B grease. It will have a percentage of overbased calcium sulfonate percentage. As the above Example 2 grease was overheated to about 29 ° F., the result, which is an effect known to have a potentially detrimental effect on the thickener yield, is more surprising. In the final grease product, the amount of sodium hydroxide relative to the initial unreacted weight 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 represents the amount of alkali metal hydroxide added as a component in the preparation of the grease, which alkali metal hydroxide reacts with the complexing acid to form a salt. Will, 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 relative to the weight of the final grease product.

Example 3 (Alkali / Delayed Addition Method Aspect): Another calcium sulfonate composite grease was prepared in a similar manner to Example 2 grease above. The only important difference was that the initial fractions of the complexed acids acetic acid and 12-hydroxystearic acid were added at the beginning of the method, while maintaining the mixture at ambient laboratory temperature (prior to any heating). Similar to Example 2 grease above, this grease used an aspect of the alkali / delayed addition method. In addition, care was taken to ensure that the batch did not overheat during the final heating step.

The grease of Example 3 was prepared as follows: 240.31 g of 400 TBN overbased oil-soluble calcium sulfonate followed by 345.09 g of solvent neutral group 1 paraffinic acid base oil having a viscosity of about 600 SUS at 100 ° F., and 10.03 g. A PAO having a viscosity of 4 cSt at 100 ° C. was added to an open mixing vessel. The 400 TBN overbased oil-soluble calcium sulfonate was low quality calcium sulfonate similar to that used in Examples 10 and 11 of those disclosed above and US Patent Application No. 13 / 664,768. Planetary mixing paddles were used to initiate mixing without heating. Thereafter, 21.83 g of mainly C12 alkylbenzene sulfonic acid 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 food grade purity calcium hydroxide having an average particle size of 5 microns or less were added and allowed to mix for 30 minutes. Thereafter, 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 until the temperature reached 190-200 ° F. (first temperature adjustment delay period). During heating to this temperature range, the whip cream appearance became evidence when the temperature reached about 150 ° F. The whip cream appearance settled shortly after reaching the temperature range of 190-200 ° F. Upon reaching the temperature range of 190 to 200 ° F., 24.17 g of hexylene glycol was added (there was no retention delay period). This amount corresponds to the approximate total amount of hexylene glycol added to the example grease in two separate fractions. However, in this example grease, they are all added at once, because the addition of alkali metal hydroxides containing water modifies the conversion process, often resulting in the need for 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.

Then, an additional 10 ml of water was added followed by a total of 99.73 g of two nearly identical fractions of the same paraffinic base oil. This was carried out to prevent the grease from being thickened to the extent that the grease could not be effectively mixed. Fourier transform infrared (FTIR) spectroscopy showed that the 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 allowed to mix. An additional 30 ml of water was added to replace the water lost due to evaporation. Then, as the grease mixture continued to thicken, another 55.22 g of the same base oil as above 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 continued to thicken, adding 43.38 g followed by another 53.97 g of the same base oil as above.

Thereafter, 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, mixed and allowed to react. The mixture was then heated with continued stirring using an electric heating mantle. When the grease reached 300 ° F., 20.24 g of styrene-alkylene copolymer was added as a flaky solid. The grease was further heated to about 390 ° F. when the entire polymer melted and was completely dissolved in the grease mixture. The heating mantle was removed and the grease was continuously stirred in open air to allow it to cool. When the grease was cooled to 300 ° F., 30.39 g of food grade anhydrous calcium sulfate with an average particle size of 5 microns or less was added. When the temperature of the grease was cooled to 200 ° F., 2.06 g of aryl amine antioxidant and 4.46 g of polyisobutylene polymer were added. A total of 132.79 g of three consecutive fractions of the same base oil as above were added and allowed to mix in the grease. Mixing was continued until the grease reached a temperature of 170 ° F. Thereafter, the grease was removed from the mixer and three roll mills were passed through three times to achieve a final smooth and homogeneous texture.

The final grease of Example 3 had a 282 60 round trip mixing. The percent overbased oil-soluble calcium sulfonate in the final grease was 19.20%. The dropping point was> 650 ° F. As can be seen, the grease had an improved thickener yield over the greases of Examples 1A and 1B. In fact, this grease had an improved thickener yield over all of the example greases of the '473 patent application, the' 768 patent application and US Patent No. 9,273,265. This is believed to be the best thickener yield achieved for the calcium sulfonate composite grease in open mixer / kettle (non-pressurized) systems recorded in the published literature. When prepared in a sealed press kettle, it is believed that the thickener yield will be better than 19.2%.

Example 4 (Baseline Example-No Alkali Metal Hydroxide, No Delay Period): Another calcium sulfonate composite grease, using different base oils, using different non-aqueous converting agents, without boric acid, It was prepared in a similar manner to the example greases above, except that no alkali metal hydroxide was added and there was no delay between the addition of water and non-aqueous converting agent. This example grease serves as a baseline for comparison with other example greases disclosed herein where an alkali metal hydroxide is added and there is at least one delay period between the addition of water and a non-aqueous conversion agent.

The grease of Example 4 was prepared as follows: 297.25 g of 400 TBN overbased oil-soluble calcium sulfonate followed by 373.60 g of USP pure white paraffinic acid mineral base oil having a viscosity of about 352 SUS at 100 ° F. in an open mixing vessel. Put on The overbased calcium sulfonate was NSF HX-1 food grade approved overbased calcium sulfonate suitable for making NSF H-1 approved food grade grease and was of good quality as defined in the '768 patent application. Planetary mixing paddles were used to initiate mixing without heating. Thereafter, 26.99 g of mainly C12 alkylbenzene sulfonic acid was added. After 20 minutes of mixing, 50.58 g of calcium hydroxyapatite having an average particle size of 5 microns or less and 4.06 g of food grade purity calcium hydroxide having an average particle size of 5 microns or less were added and allowed to mix for 30 minutes. Thereafter, 0.96 g of glacial acetic acid and 11.94 g of 12-hydroxystearic acid were added and allowed to mix for 10 minutes. Thereafter, 55.19 g of finely divided calcium carbonate with an average particle size of 5 microns or less was added and allowed to mix for 5 minutes. Then 37.2 g of water and 14.89 g of propylene glycol (as a non-aqueous converting agent) were added without any delay. The mixture was heated until the temperature reached 190-200 ° F. Conversion and visible thickening was initiated before reaching the target temperature range. The temperature was maintained at 190-200 ° F. for 1 hour 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 showed the conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite). Since thickening began to occur, an additional 54.07 g of the same base oil as above was added. Thereafter, 25 ml of water and 8.35 g of the same calcium hydroxide as above were added and allowed to mix for 10 minutes. Thereafter, 1.82 g of glacial acetic acid was added followed by 30.60 g of 12-hydroxystearic acid. After these two complexed acids 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 20.27 g of 75% phosphoric acid in water was slowly added, mixed and allowed to react. The mixture was then heated with continued stirring using an electric heating mantle. When the grease reached 300 ° F., 2.86 g of styrene-alkylene copolymer was added as a flaky solid. The grease was further heated to about 390 ° F. when the entire polymer melted and was completely dissolved in the grease mixture. The heating mantle was removed and the grease was continuously stirred in open air to allow it to cool. When the grease was cooled to 300 ° F., 33.10 g of food grade anhydrous calcium sulfate with an average particle size of 5 microns or less was added. When the temperature of the grease was cooled to 200 ° F., 5.60 g of a mixture of aryl amine 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 was added followed by another 29.39 g of the same base oil. Mixing was continued until the grease reached a temperature of 170 ° F. Thereafter, the grease was removed from the mixer and three roll mills were passed through three times to achieve a final smooth and homogeneous texture. The grease had a reciprocal mixing degree of 281 60 times. The percent overbased oil-soluble calcium sulfonate in the final grease was 26.29%. The dropping point was> 650 ° F.

Example 5 (Alkali / Delayed Addition Method Aspect): Another calcium sulfonate composite grease was carried out above, except that there was a delay between adding alkali metal hydroxide and adding water and a non-aqueous conversion agent. Example 4 Prepared in a similar manner to grease. The alkali metal hydroxide used was sodium hydroxide, and its concentration in the final grease was 0.03%. In addition, the amount of the non-aqueous converting agent (propylene glycol) was approximately twice as compared to Example 4 above, as observed in the Example 2 and Example 3 greases in which an aspect of the alkali / delayed addition method was used.

The grease of Example 5 was prepared as follows: 298.15 g of 400 TBN overbased oil-soluble calcium sulfonate followed by 360.45 g of USP pure white paraffinic acid mineral base oil having a viscosity of about 352 SUS at 100 ° F. in an open mixing vessel. Put on The overbased calcium sulfonate was 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. Planetary mixing paddles were used to initiate mixing without heating. Thereafter, 27.10 g of mainly C12 alkylbenzene sulfonic acid was added. After 20 minutes of mixing, 50.61 g of calcium hydroxyapatite with an average particle diameter of 5 microns or less and 4.09 g of food grade purity calcium hydroxide with an average particle diameter of 5 microns or less were added and allowed to mix for 30 minutes. Thereafter, 0.96 g of glacial acetic acid and 11.92 g of 12-hydroxystearic acid were added and allowed to mix for 15 minutes. Thereafter, 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 with continued mixing until the temperature reached 190-200 ° F. (first temperature adjustment delay period). It was noted that when the temperature reached about 170 ° F., whip cream appearance was observed. After reaching 190-200 ° F., an additional 20 ml of water was added to replace the water lost due to evaporation. After mixing for 35 minutes at 190 to 200 ° F. (first retention delay period), 29.88 g of propylene glycol was added, and it was observed that the whip cream appearance subsided prior to the addition of the non-aqueous conversion agent. After about 10 minutes, visible conversion and thickening began to be observed. As the grease continued to thicken, 51.33 g of the same base oil as above was added along 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 showed that almost all of the water had disappeared, an additional 40 ml of water was added.

After about 2 hours at 190 to 200 ° F. (2 hours after addition of propylene glycol), Fourier Transform Infrared (FTIR) spectroscopy showed the conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite). Then, 40 ml of water and 8.12 g of the same calcium hydroxide as above were added and allowed to mix for 10 minutes. Another 52.07 g of the same base oil as above was added as the grease continued to thicken. Then, 2.85 g of glacial acetic acid was added followed by 31.35 g of 12-hydroxystearic acid. After these two complexed acids reacted, another 52.11 g of the same base oil as above was added due to the increased hardness of the grease mixture. Then another 20 ml of water was added followed by another 54.11 g of the same base oil as above. Then, a solution of 20.14 g of 75% phosphoric acid in water was added slowly, mixed and allowed to react. As the grease continued to harden, another 52.50 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 ° F., 2.75 g of styrene-alkylene copolymer was added as a flaky solid. The grease was further heated to about 390 ° F. when the entire polymer melted and was completely dissolved in the grease mixture. The heating mantle was removed and the grease was continuously stirred in open air to allow it to cool. When the grease was cooled to 300 ° F., 33.16 g of food grade anhydrous calcium sulfate with an average particle size of 5 microns or less was added. When the temperature of the grease was cooled to 200 ° F., 5.62 g of a mixture of aryl amine 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 were added. Mixing was continued until the grease reached a temperature of 170 ° F. Thereafter, the grease was removed from the mixer and three roll mills were passed through three times to achieve a final smooth and homogeneous texture. The grease had a reciprocal mixing degree of 288 times. The percent overbased oil-soluble calcium sulfonate in the final grease was 21.78%. The dropping point was> 650 ° F. As can be seen, the thickener yield of this grease is more improved than in Example 4 grease above and again demonstrates the noticeable effect of the alkali / delayed addition method aspect.

Example 6 (Alkali / Delayed Addition Method Aspect) : Another calcium sulfonate composite grease was prepared in a similar manner to Example 5 grease, except that the amount of sodium hydroxide was doubled. The sodium hydroxide concentration in the final grease was 0.06%. The grease was prepared as follows: 297.40 g of 400 TBN perbase oil soluble calcium sulfonate followed by 360.93 g of USP purity white paraffinic acid mineral oil having a viscosity of about 352 SUS at 100 ° F. was added to the open mixing vessel. The overbased calcium sulfonate was NSF HX-1 food grade approved overbased calcium sulfonate suitable for making NSF H-1 approved food grade grease, and was of good quality as defined in the '768 patent application. Planetary mixing paddles were used to initiate mixing without heating. Thereafter, 27.13 g of mainly C12 alkylbenzene sulfonic acid was added. After 20 minutes of mixing, 50.63 g of calcium hydroxyapatite with an average particle size of 5 microns or less and 4.20 g of food grade purity calcium hydroxide with an average particle size of 5 microns or less were added and allowed to mix for 30 minutes. Thereafter, 0.95 g of glacial acetic acid and 11.92 g of 12-hydroxystearic acid were added and allowed to mix for 15 minutes. Thereafter, 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 while mixing until the temperature reached 190-200 ° F. (first temperature adjustment delay period). It was noted that when the temperature reached about 184 ° F., whip cream appearance was observed. After mixing for 35 minutes at 190-200 ° F. (first retention delay period), an additional 20 ml of water was added to replace the water lost due to evaporation. Immediately thereafter, the whip cream appearance subsided, and 30.25 g of propylene glycol was added as a non-aqueous converting agent. After 20 minutes, visible conversion and thickening began. Another 10 ml of water was added due to evaporation loss.

As the grease continued to thicken, 51.96 g of the same base oil as above followed by another 57.48 g of the same base oil as above. When the conversion and thickening process of amorphous calcium carbonate to crystalline calcium carbonate (calcite) appeared to be complete, 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 as above was added. Then, 1.83 g of glacial acetic acid was added, followed by 30.54 g of 12-hydroxystearic acid. After the reaction of these two complexed acids, 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. Then another 10 ml of water was added slowly followed by a 75% solution of phosphoric acid in 20.30 g of water, allowed to mix and react. As the grease became harder, a total of 99.63 g of two fractions of the same base oil as above were added. The mixture was then heated with continued stirring using an electric heating mantle. When the grease reached 300 ° F., 2.91 g of styrene-alkylene copolymer was added as piece solid. The grease was further heated to about 390 ° F. when the polymer melted and was completely dissolved in the grease mixture. The heating mantle was removed and the grease continued to heat in open air to allow it to cool. When the grease was cooled to 300 ° F., 33.11 g of food grade anhydrous calcium sulfate with an average particle size of 5 microns or less was added. When the grease temperature was cooled to 200 ° F., 5.78 g of a mixture of aryl amine 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 ° F. Thereafter, the grease was removed from the mixer and three roll mills were passed through three times to achieve a final smooth and homogeneous texture. The grease had 295 round trip mixing. The percent overbased oil-soluble calcium sulfonate in the final grease was 20.78%. The dropping point was> 650 ° F. As can be seen, the thickener yield of the present grease is more improved than in Example 4 grease above and again demonstrates the noticeable effect of the aspect of the alkali / delayed addition method. Using the conventional inverse relationship between the degree of miscibility and the percent overbased calcium sulfonate concentration, the grease of this example would have a percent oversalt of 21.3% if the base oil had the same degree of miscibility as the grease of Example 5 above. It would have had a vaporized calcium sulfonate concentration. Thus, doubling the amount of sodium hydroxide in this Example 6 grease appears to give some additional improvement in thickener yield compared to Example 5 grease above, in the best case.

Example 7 (Alkali / Delayed Addition Method Aspect) : Another calcium sulfonate composite grease was prepared in a similar manner to Example 6 grease above. The only important difference between this grease and the above Example 6 grease is that the grease was maintained at 160 to 170 ° F. for 1 hour during the initial heating period. The grease was prepared as follows: 297.79 g of 400 TBN overbased oil-soluble calcium sulfonate followed by 362.02 g of USP purity white paraffinic acid mineral oil having a viscosity of about 352 SUS at 100 ° F. was added to the open mixing vessel. The overbased calcium sulfonate is NSF HX-1 food grade approved overbased calcium sulfonate suitable for making NSF H-1 approved food grade grease, and is of good quality as defined by the '768 patent application. Planetary mixing paddles were used to initiate mixing without heating. Thereafter, 27.01 g of mainly C12 alkylbenzene sulfonic acid was added. After 20 minutes of mixing, 50.64 g of calcium hydroxyapatite having an average particle size of 5 microns or less and 4.14 g of food grade purity calcium hydroxide having an average particle size of 5 microns or less were added and allowed to mix for 30 minutes. Thereafter, 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. Then, 39.1 g of water in which 0.88 g of powdered sodium hydroxide was dissolved was added. The mixture was heated while mixing until the temperature reached 160-170 ° F. (first temperature adjustment delay period). During this time, it was noted that the whip cream appearance developed. After mixing for 1 hour at 160 to 170 ° F. (first retention delay period), the mixture was heated to 190 to 200 ° 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 thickening began. Then another 30 ml of water was added due to 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 as above were added. After 10 minutes, another 10 ml of water and 56.33 g of the same base oil as above were added. After another 25 minutes, when the conversion and thickening process of amorphous calcium carbonate to crystalline calcium carbonate (calcite) appears to be complete, 8.18 g of the same calcium hydroxide and another 30 ml of water are added and mixed for 10 minutes. I made it. Then, 1.84 g of glacial acetic acid was added, followed by 30.57 g of 12-hydroxystearic acid. After these two complexed 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 20.22 g of 75% phosphoric acid in water was added slowly, mixed and allowed to react. As the grease continued to harden further, 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 ° F., 2.77 g of styrene-alkylene copolymer was added as a flaky solid. The grease was further heated to about 390 ° F. when the entire polymer melted and was completely dissolved in the grease mixture. The heating mantle was removed and the grease was continuously stirred in open air to allow it to cool.

When the grease was cooled to 300 ° F., 33.21 g of food grade anhydrous calcium sulfate with an average particle size of 5 microns or less was added. When the grease temperature was cooled to 200 ° F., 5.61 g of a mixture of aryl amine 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 ° F. Thereafter, the grease was removed from the mixer and three roll mills were passed through three times to achieve a final smooth and homogeneous texture. The grease had 309 60 round trip blends. The percent overbased oil-soluble calcium sulfonate in the final grease was 23.43%. The dropping point was> 650 ° F.

Using the conventional inverse relationship between the degree of miscibility and the percent overbased calcium sulfonate concentration, less base oil was added to give the degree of miscibility, the same value as in Example 4 grease, where no alkali metal hydroxide was added and there was no delay. If this were to be done, the Example 7 grease would have a percent overbased calcium sulfonate concentration of 25.76%. By comparing these values with the results of Example 4, Example 5 and Example 6 grease, the present example was obtained by having 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 clear that most of the thickener yield improvement in Greece has been eliminated. In Examples 12 and 17 of the '476 patent application, having a first holding delay period in the first temperature range of 160 to 170 ° F. prior to heating to 190 to 200 ° F. Even if the retention delay period was 2.5 hours, it showed improvement in thickener yield when no alkali metal hydroxide was added (20.36% and 20.59%, respectively). By comparison with the example grease in the patent application, the addition of a very small amount of alkali metal hydroxide (e.g. 0.07 wt% of the final grease in Example 7) does not affect the conversion process, and the alkali / delayed addition method While it is advantageous to use aspects, it is evident that the benefits of certain combinations of '476 patent delay periods are not necessarily achieved when combined with the addition of alkali metal hydroxide. This result was unexpected and surprising. While Example 7 grease showed some thickener yield improvement over the grease of baseline Example 4, most of the yield improvement seen in Example 5 and Example 6 grease was not observed, which is a specific combination in Example 7. Because of the delay period and temperature range. Thus, when alkali metal hydroxide is added, the grease is not heated to a first temperature range of 160 to 170 ° F., including any retention delay period in the first temperature range as part of the delayed non-aqueous converting agent method. It is most preferred.

Example 8 (Alkali / Delayed Addition Method Aspect): Similar to Example 6 Grease except that another calcium sulfonate composite grease was used as the alkali metal hydroxide added instead of sodium hydroxide monohydrate. Prepared in a manner. The concentration of lithium hydroxide according to the monohydrate form in the final grease was 0.06%. The grease was prepared as follows: 298.61 g of 400 TBN overbased oil-soluble calcium sulfonate followed by 362.54 g of USP purity white paraffinic acid mineral base oil having a viscosity of about 352 SUS at 100 ° F. was added to the open mixing vessel. The overbased calcium sulfonate was NSF HX-1 food grade approved overbased calcium sulfonate suitable for making NSF H-1 approved food grade grease and was of good quality as defined by the '768 patent application. Planetary mixing paddles were used to initiate mixing without heating. Thereafter, 27.03 g of mainly C12 alkylbenzene sulfonic acid was added. After 20 minutes of mixing, 50.62 g of calcium hydroxyapatite having an average particle size of 5 microns or less and 4.11 g of food grade purity calcium hydroxide having an average particle size of 5 microns or less were added and allowed to mix for 30 minutes. Thereafter, 0.97 g of glacial acetic acid and 11.96 g of 12-hydroxystearic acid were added and allowed to mix for 15 minutes. Subsequently, 55.05 g of finely divided calcium carbonate with 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 while mixing until the temperature reached 190-200 ° F. (first temperature adjustment delay period). It was noted that when the temperature reached about 170 ° F., whip cream appearance was observed. After mixing for 45 minutes at 190-200 ° F. (first retention delay period), an additional 30 ml of water was added to replace water lost due to evaporation, and 30.01 g of propylene glycol was added. At this time, it was observed that the appearance of the whip cream sank.

After 35 minutes, visible conversion and thickening began. Another 15 ml of water was added due to evaporation loss. As the grease continued to thicken, 58.52 g of the same base oil as above was added, followed by another 51.15 g of the same base oil as above. When the conversion and thickening process of amorphous calcium carbonate to crystalline calcium carbonate (calcite) appeared to be complete, 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 followed by 30.53 g of 12-hydroxystearic acid were added. After about 15 minutes, when these two complexed acids appeared to have reacted, another 69.37 g of the same base oil 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 as above were added. Thereafter, another 5 ml of water was added, followed by the slow addition of a 75% solution of phosphoric acid in 20.16 g of water to allow mixing and reaction. As the grease continued to harden, 38.24 g 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 ° F., 2.85 g of styrene-alkylene copolymer was added as a flaky solid. The grease was further heated to about 390 ° 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 continuing stirring in open air. When the grease was cooled to 300 ° F., 33.21 g of food grade anhydrous calcium sulfate with an average particle diameter of 5 microns or less was added. When the grease temperature was cooled to 200 ° F., 5.78 g of a mixture of aryl amine and high molecular weight phenolic antioxidant and 6.10 g of amine phosphate antioxidant / rust inhibitor were added. A total of 112.37 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 ° F. Thereafter, the grease was provided from the mixer and three roll mills were passed through three times to achieve a final smooth and homogeneous texture. The grease had 295 round trip mixing. The percent overbased oil-soluble calcium sulfonate in the final grease was 21.79%. The dropping point was> 650 ° F. As can be seen, the thickener yield of the present grease was improved over the above Example 4 grease, which again demonstrates the noticeable effect of utilizing aspects of the alkali / delayed addition method. By further comparing the grease with Example 6 grease having the same first temperature adjustment delay period as above and a first maintenance delay period substantially equal to the above (35 minutes vs. 45 minutes), the effect of improving the thickener yield of lithium hydroxide is improved. It is clear that is not as effective as sodium hydroxide.

Example 9 (Alkali / Delayed Addition Method Aspects): Another calcium sulfonate composite grease was prepared in a similar manner to Example 6 grease, except that potassium hydroxide was used as the alkali metal hydroxide added in place of sodium hydroxide. Potassium hydroxide was introduced in the form of a 47.9% solution in water. The amount of the solution added was adjusted to compensate for both the concentration of potassium hydroxide and the difference in molecular weight between sodium hydroxide and potassium hydroxide. By completing this, as in Example 6 grease, a molar amount approximately equal to the hydroxide added to the grease was provided. The potassium hydroxide concentration in the final grease was 0.20%. The grease was prepared as follows: 302.52 g of 400 TBN overbased oil-soluble calcium sulfonate followed by 357.60 g of USP purity white paraffinic acid mineral base oil having a viscosity of about 352 SUS at 100 ° F. was added to the open mixing vessel. The overbased calcium sulfonate was NSF HX-1 food grade approved overbased calcium sulfonate suitable for making NSF H-1 approved food grade grease and was of good quality as defined by the '768 patent application. Planetary mixing paddles were used to initiate mixing without heating. Thereafter, 27.04 g of mainly C12 alkylbenzene sulfonic acid was added. After 20 minutes of mixing, 50.63 g of calcium hydroxyapatite having an average particle size of 5 microns or less and 4.09 g of food grade purity calcium hydroxide having an average particle size of 5 microns or less were added and allowed to mix for 30 minutes. Thereafter, 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 potassium hydroxide 47.9% aqueous solution was added.

The mixture was heated while continuing to mix until the temperature reached 190-200 ° F. It was noted that when the temperature reached about 170-180 ° F., the whip cream appearance developed. Heating was continued until the grease reached 200 ° F. (first temperature adjustment delay period), then 15 ml of water and 29.72 g of propylene glycol were added (no retention delay period). At this time, it was observed that the appearance of the whip cream sank. When visible conversion and thickening was initiated, 65.89 g of the same base oil and 10 ml of water were added. As the thickening 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 the conversion and thickening process of amorphous calcium carbonate to crystalline calcium carbonate (calcite) seemed to be complete, 8.27 g of the same calcium hydroxide as above was added and allowed to mix for 10 minutes. Thereafter, 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 thicken, 88.20 g of the same base oil as above followed by 5 ml of water. Then, as the grease became harder, another 15.73 g of the same base oil as above was added. Then, a solution of 20.81 g of 75% phosphoric acid in water was slowly added, mixed and allowed to react. As the grease continued to harden further, 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 ° F., 2.75 g of styrene-alkylene copolymer was added as a flaky solid. When the entire polymer melted and completely dissolved in the grease, the grease was further heated to about 390 ° F. The heating mantle was removed and the grease was continuously stirred in open air to allow it to cool.

When the grease was cooled to 300 ° F., 33.19 g of food grade anhydrous calcium sulfate with an average particle size of 5 microns or less was added. When the temperature of the grease was cooled to 200 ° F., 5.93 g of a mixture of aryl amine 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 ° F. Thereafter, the grease was removed from the mixer and three roll mills were passed through three times to achieve a final smooth and homogeneous texture. The grease had a 292 round trip mixing. The percent overbased oil-soluble calcium sulfonate in the final grease was 23.03%. The dropping point was> 650 ° F. As can be seen, the thickener yield of the present grease is significantly improved over the Example 4 grease above, which again demonstrates the noticeable effect of using an aspect of the alkali / delayed addition method. By further comparing this grease to Example 6 and Example 8 greases, it is clear that the effect of improving potassium hydroxide thickeners 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 additional tests involving different variations of the delay periods for the addition of the non-aqueous converting agent may seem different.

Example 10 (Alkali / Delayed Addition Method Aspects): Another calcium sulfonate composite grease, more base oil added initially, overbased calcium sulfonate, C12 alkylbenzene sulfonic acid, propylene glycol converting agent, 12 -Prepared in a similar manner to Example 6 grease, except that the amount of hydroxystearic acid and acetic acid was reduced in proportion to the amount of calcium hydroxide added, calcium hydroxyapatite, calcium carbonate added, and phosphoric acid. did. The grease was prepared as follows: 233.60 g of 400 TBN overbased oil-soluble calcium sulfonate followed by 422.48 g of USP pure white paraffinic acid mineral oil having a viscosity of about 352 SUS at 100 ° F. was added to the open mixing vessel. The overbased calcium sulfonate was NSF HX-1 food grade approved overbased calcium sulfonate suitable for making NSF H-1 approved food grade grease and was of good quality as defined in the '768 patent application. Planetary mixing paddles were used to initiate mixing without heating. Thereafter, 21.04 g of mainly C12 alkylbenzene sulfonic acid was added. After 20 minutes of mixing, 50.69 g of calcium hydroxyapatite having an average particle size of 5 microns or less and 4.10 g of food grade purity calcium hydroxide having an average particle size of 5 microns or less were added and allowed to mix for 30 minutes. Thereafter, 0.72 g of glacial acetic acid and 9.32 g of 12-hydroxystearic acid were added and allowed to mix for 15 minutes. Thereafter, 55.22 g of finely divided calcium carbonate with an average particle size of 5 microns or less was added and allowed to mix for 5 minutes. Then, 39.1 g of water in which 0.88 g of powdered sodium hydroxide was dissolved was added. The mixture was heated while mixing until the temperature reached 190-200 ° F. (first temperature adjustment delay period). It was noted that when the temperature reached about 180 ° F., whip cream appearance was observed. After 40 minutes of mixing at 190 to 200 ° F. (first retention delay period), an additional 20 ml of water was added to replace water lost due to evaporation, and 23.13 g of propylene glycol was added. At this time, the appearance of the whip cream was observed to sink.

After 2 hours and 30 minutes, thickening continued to occur. The temperature was increased to 230 ° F. and FTIR showed little water left. Another 30 ml of water was added and the temperature was maintained at 230 ° F. 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 ° F. Thereafter, 8.22 g of the same calcium hydroxide as above was added and allowed to mix for 10 minutes. Thereafter, 1.37 g of glacial acetic acid was added followed by 23.68 g of 12-hydroxystearic acid. After these two complexed acids reacted, a solution of 20.53 g of 75% phosphoric acid in water was slowly added, mixed and allowed to react. Thereafter, the grease was continuously heated with stirring using an electric heating mantle. When the grease reached 300 ° F., 2.79 g of styrene-alkylene copolymer was added as a flaky solid. The grease was further heated to about 390 ° F. when the entire polymer melted and completely dissolved in the grease mixture. The heating mantle was removed and the grease was continuously stirred in open air to allow it to cool. When the grease was cooled to 300 ° F., 33.15 g of food grade anhydrous calcium sulfate with an average particle size of 5 microns or less was added. When the grease temperature was cooled to 200 ° F., 5.89 g of a mixture of aryl amine 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 ° F. Thereafter, the grease was removed from the mixer and passed through three roll mills three times to provide a final smooth and homogeneous texture. The grease had 289 round trip mixing. The percent overbased oil-soluble calcium sulfonate in the final grease was 22.76%. The dropping point was 621 ° F. As can be seen, the thickener yield of the grease was further improved compared to Example 4 baseline grease, which again demonstrates the noticeable effect of the aspect of the alkali / delayed addition method.

The results of Examples 1 to 10 herein and the methods used herein are summarized in Table 1 below. The amount of overbased calcium sulfonate indicated in parentheses is the overbased estimated when additional base oil is added to dilute the sample grease to achieve the same miscibility as described above and the example number shown after the dash. The amount of calcium sulfonate. Combining these early ten examples, by utilizing aspects of the alkali / delayed method of the present invention, in particular, calcium hydroxyapatite and added calcium carbonate are reacted with the complexing acid as disclosed in the '768 patent application. It is strongly demonstrated that the thickener yield is improved by using it as a calcium-containing base. In addition, thickener yield is improved utilizing aspects of the alkali / delayed method of the present invention using both low quality and good quality overbased calcium sulfonate. Composite grease also demonstrates excellent dropping point.

The following examples add excellent properties of the present invention overbased calcium sulfonate grease, which can be achieved utilizing aspects of the alkali / delayed method of the present invention, including modifications to the point of addition of the alkali metal hydroxide. Prove with.

Example 11 (Baseline Example-No alkali metal hydroxide added, no delay period): Another calcium sulfonate composite grease was prepared similarly as disclosed in US Pat. No. 4,560,489 (patented by Witco Corporation on December 24, 1985), and Example 18 of the '476 patent application. As disclosed in the '489 patent, the only calcium-containing base added for reaction with complexed acids in the grease was calcium hydroxide. The grease serves as a baseline for the following two embodiments.

The grease of Example 11 was prepared as follows: 440.02 g of 400 TBN overbased oil-soluble calcium sulfonate followed by 390.68 g of solvent neutral group 1 paraffinic acid base oil having a viscosity of about 600 SUS at 100 ° F. into an open mixing vessel. Applied. Planetary mixing paddles were used to initiate mixing without heating. The 400 TBN overbased oil-soluble calcium sulfonate was of good quality calcium sulfonate similar to that used in Examples 4 and 12 of the above disclosed and '768 patent applications. Thereafter, 17.76 g of mainly C12 alkylbenzene sulfonic acid 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 mixing until the temperature reached 190 ° F. When the temperature reached 190 ° F., 5.75 g of glacial acetic acid was added. If visible conversion to the grease structure is observed, the temperature is raised to 190-200 ° F. until the Fourier Transform Infrared (FTIR) spectroscopy indicates that the conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) has occurred. Kept for a minute. Thereafter, 15.37 g of food grade purity calcium hydroxide 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 complexed acids. Then, 28.59 g of 12-hydroxystearic acid were added, allowed to melt and 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. Thereafter, the heating mantle was removed, and the grease was continuously stirred in open air to cool. When the grease cooled to 170 ° F., it was removed from the mixer and passed through three roll mills three times to achieve a final smooth and homogeneous texture. The grease had 291 round trip mixing. The percent overbased oil-soluble calcium sulfonate in the final grease was 46.92%. The dropping point was> 650 ° F.

Example 12 (Alkali / Delayed Addition Method Aspect) : Another grease, except that the grease has a delayed non-aqueous converting agent hexylene glycol upon its addition until the mixture is heated to 190-200 ° F. , Prepared in a similar manner to the above grease. In addition, the grease had a small amount of sodium hydroxide dissolved in a second fraction of water added at 190-200 ° F. after the initial conversion had occurred and before calcium hydroxide, 12-hydroxystearic acid, or acetic acid was added. The sodium hydroxide concentration in the final grease was 0.08%. The grease was prepared as follows: 430.36 g of 400 TBN overbased oil-soluble calcium sulfonate followed by 386.79 g of solvent neutral group 1 paraffinic acid base oil having a viscosity of about 600 SUS at 100 ° F. was added to the open mixing vessel. Planetary mixing paddles were used to initiate mixing without heating. The 400 TBN overbased oil-soluble calcium sulfonate was of good quality calcium sulfonate similar to that used in Examples 4 and 12 of the above disclosed and '768 patent applications. Thereafter, 17.64 g of mainly C12 alkylbenzene sulfonic acid was added.

After mixing for 20 minutes, 44.48 g of water was added as a converting agent. The batch was then heated while mixing was continued until the temperature reached 190-200 ° 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 190-200 ° F. Since the interval of 5 minutes between reaching the first temperature range of 190 to 200 ° F. and the addition of the non-aqueous conversion agent is too short, it is not considered as a holding delay period. If visible conversion to the grease structure is observed, the temperature is raised to 190-200 ° F. until the Fourier Transform Infrared (FTIR) spectroscopy indicates that the conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) has occurred. Kept for a minute. Thereafter, 15.41 g of food grade purity calcium hydroxide 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 complexed acids. Then, 44.04 g of water (secondary addition of water) in which 0.88 g of powdered sodium hydroxide was dissolved was added and allowed to mix into the grease. Then, 28.60 g of 12-hydroxystearic acid was added, allowed to melt and 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.

Thereafter, the grease was heated to 390 to 400 ° F. Thereafter, the heating mantle was removed, and the grease was continuously stirred in open air to cool. When the grease was cooled to 200 ° F., 2.40 g of aryl amine 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 allowed to mix into the grease. When the grease cooled to 170 ° F., it was removed from the mixer and passed through three roll mills three times to achieve a final smooth and homogeneous texture. The grease had 290 round trip mixing. The percent overbased oil-soluble calcium sulfonate in the final grease was 39.38%. The dropping point was> 650 ° F. As can be seen, the present grease essentially had the same miscibility as in Example 11 grease. However, as indicated by the lower percentage of overbased calcium sulfonate in this grease compared to Example 11 grease above, the thickener yield was significantly improved.

Example 13 (Alkali / Delayed Addition Method Aspect): Another grease was prepared in a similar manner to the grease by delaying the addition of the non-aqueous conversion agent hexylene glycol until the mixture was heated to 190-200 ° F. (first temperature controlled delay period). However, in this grease, before heating of the batch started, a small amount of sodium hydroxide was dissolved at ambient temperature in the initial fraction of water added. Once again, the sodium hydroxide concentration in the final grease was 0.08%. The grease was prepared as follows: 440.24 g of 400 TBN overbased oil-soluble calcium sulfonate followed by 385.62 g of solvent neutral group 1 paraffinic acid base oil having a viscosity of about 600 SUS at 100 ° F. was added to the open mixing vessel. Planetary mixing paddles were used to initiate mixing without heating. The 400 TBN overbased oil-soluble calcium sulfonate was a good quality calcium sulfonate similar to that used in Examples 4 and 12 of the above disclosed and '768 patent applications. Thereafter, 17.61 g of mainly C12 alkylbenzene sulfonic acid was added. After mixing for 20 minutes, 44.48 g of water in which 0.88 g of powdered sodium hydroxide was dissolved was added. Thereafter, the batches were continuously mixed and heated until the temperature reached 190-200 ° F. (first temperature adjustment delay period). 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 190-200 ° F. Again, the interval of 5 minutes between reaching the first temperature range of 190 to 200 ° F. and adding the non-aqueous converting agent was too short, so it was not considered a holding delay period. When a visible conversion to the grease structure is observed, the temperature is raised from 190 to 200 ° F. for 45 minutes until Fourier Transform Infrared (FTIR) spectroscopy indicates the conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite). Maintained.

Thereafter, 30.1 g of water and 15.41 g of food grade pure calcium hydroxide 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 complexed acids. Thereafter, 28.66 g of 12-hydroxystearic acid was added, allowed to melt and 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. Thereafter, the grease was heated to a temperature of 390 to 400 ° F. Thereafter, the heating mantle was removed, and the grease was continuously stirred in open air to cool. When the grease was cooled to 200 ° F., 2.69 g of aryl amine 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 allowed to mix into the grease.

When the grease cooled to 170 ° F., it was removed from the mixer and passed through three roll mills three times to achieve a final smooth and homogeneous texture. The grease had 284 round trip mixing. The percent overbased oil-soluble calcium sulfonate in the final grease was 38.74%. The dropping point was> 650 ° F. Again, the thickener yield was significantly improved, as indicated by a lower percentage of the overbased calcium sulfonate in this grease compared to Example 11 grease above. This example grease and the above example 12 grease are used when only calcium hydroxide is used for the reaction with the complexed acid (in the above examples and as described in the '768 patent application, calcium hydroxyapatite and / or calcium carbonate added) Contrary to the addition), utilizing the aspect of the alkali / delayed addition method seems to provide a very significant thickener yield improvement. The thickener yl of Example 13 in which alkali metal hydroxide is added to the initial water is better than the thickener yl of Example 12 in which the alkali metal hydroxide is added to the secondary addition of water, at least calcium hydroxide being the only calcium-containing base added In that case, it is preferred to add alkali metal hydroxide to the initial addition of water. However, both Example 12 and Example 13 show significant improvement in thickener yield compared to Example 11 where no alkali metal hydroxide is added.

It was also noted that the concentrations of the non-aqueous converting agents of Example 12 and Example 13 grease (both utilizing aspects of the alkali / delayed addition method) were the same as Example 11 baseline grease. The prior art calcium sulfonate grease technique disclosed in the '489 patent comprising calcium hydroxide as the only added calcium containing base, when used in combination with an aspect of the alkali / delayed addition method, achieves useful grease with improved thickener yield In order to do so, it is not necessary to increase the amount of the non-aqueous conversion agent. In contrast, an increase in the amount of the non-aqueous converting agent is used in combination with the addition of calcium hydroxyapatite, and calcium carbonate added as an additional calcium-containing base to react with the complexed acid, Examples 2 to 3 , And appear to be needed in Examples 5-10, but the thickener yield in these Examples was significantly better than in Examples 12 and 13. Since the overbased calcium sulfonate used in these greases is an expensive component, even if additional amounts of some components are required, an alkali / delayed addition method in combination with added calcium hydroxyapatite and added calcium carbonate It is most preferred to use the aspect of.

Example 14 (Baseline example, no alkali metal addition and no delay period): 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 was 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 comparative baseline according to the following example grease. The grease was prepared as follows: 310.25 g of 400 TBN overbased oil-soluble calcium sulfonate followed by 368.14 g of solvent neutral group 1 paraffinic acid base oil having a viscosity of about 600 SUS at 100 ° F. was added to the open mixing vessel. The 400 TBN overbased oil-soluble calcium sulfonate was a good quality calcium sulfonate similar to that used in Examples 4 and 12 of the above disclosed and '768 patent applications. Planetary mixing paddles were used to initiate mixing without heating. Thereafter, 31.31 g of mainly C12 alkylbenzene sulfonic acid was added. After 20 minutes of mixing, 75.03 g of finely divided crystalline calcium carbonate with 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 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 period) were added and the mixture was heated to a temperature of 190 to 200 ° F. while continuing to mix. It was noted that during the heating step, the mixture was visibly converted to a grease structure at about 160 ° F. When the grease reached 190-200 ° F., Fourier Transform Infrared (FTIR) spectroscopy showed that most water was 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 showed that the conversion of amorphous calcium carbonate contained in the overbased calcium sulfonate to crystalline calcium carbonate (calcite) occurred. Thereafter, 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. Thereafter, a solution of 75% phosphoric acid in 16.49 g of water was added slowly, allowed to mix and react. Thereafter, the grease was heated to 390 to 400 ° F. The heating mantle was removed from the mixer and cooled while allowing the grease to continue mixing. When the temperature was below 200 ° F., 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 ° F. Thereafter, the grease was removed from the mixer and three roll mills were passed through three times to achieve a final smooth and homogeneous texture. The grease had 283 round trip mixing. The percent overbased oil-soluble calcium sulfonate in the final grease was 32.68%. The dropping point was 617 ° F.

Example 15 (baseline example, no alkali metal hydroxide added, no delay period): Another calcium sulfonate composite grease was prepared in the same manner and composition as Example 14 grease. This Example 15 grease and the above Example 14 grease provide a comparative baseline for the following two greases. The grease was prepared as follows: 310.19 g of 400 TBN overbased oil-soluble calcium sulfonate followed by 367.82 g of solvent neutral group 1 paraffinic acid base oil having a viscosity of about 600 SUS at 100 ° F. was added to the open mixing vessel. The 400 TBN overbased oil-soluble calcium sulfonate was good quality calcium sulfonate similar to that used in Examples 4 and 12 of the above disclosed and '768. Planetary mixing paddles were used to initiate mixing without heating. Thereafter, 31.28 g of mainly C12 alkylbenzene sulfonic acid was added. After 20 minutes of mixing, 75.31 g of finely divided crystalline calcium carbonate with an average particle size of 5 microns or less was added and allowed to mix for 20 minutes. In addition to the amount of amorphous calcium carbonate contained in the overbased calcium sulfonate, this calcium carbonate was added. 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. Thereafter, 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 ° F. It was noted that during the heating step, the mixture was visibly converted to a grease structure at about 170 ° F. When the grease reached 190-200 ° F., Fourier Transform Infrared (FTIR) spectroscopy showed that most water was lost due to evaporation. Another 20 ml of water was added.

After mixing for 45 minutes at 190-200 ° F., Fourier Transform Infrared (FTIR) spectroscopy showed that the conversion of amorphous calcium carbonate contained in perbasic calcium sulfonate to crystalline calcium carbonate (calcite) occurred. Thereafter, 1.57 g of glacial acetic acid and 16.44 g of 12-hydroxystearic acid were added and allowed to react for 30 minutes. Then, a solution of 75% phosphoric acid in 16.60 g of water was added slowly, allowed to mix and react. Thereafter, the grease was heated to 390 to 400 ° F. The heating mantle was removed from the mixer and allowed to cool while continuing to mix the grease. When the temperature was below 200 ° F., 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 ° F. Thereafter, the grease was removed from the mixer and three roll mills were passed through three times to achieve a final smooth and homogeneous texture. The grease had a mixing cycle of 280 60 times. The percent overbased oil-soluble calcium sulfonate in the final grease was 32.66%. The dropping point was 583 ° F. As can be seen, the thickener yield of the grease is essentially the same as in Example 14 grease. Together, these two greases establish a baseline for the calcium sulfonate complex grease using this particular technique and overbased useful calcium sulfonate.

Example 16 : Another calcium sulfonate composite grease was prepared similarly to the above two greases. However, the non-aqueous conversion agent hexylene glycol was not initially added to the water. Instead, the mixture was added after heating to 190-200 ° F. (first temperature adjustment delay period) and maintained in the temperature range for 1 hour (first maintenance delay period). No alkali metal hydroxide was added to the grease. The grease was prepared as follows: 310.27 g of 400 TBN overbased oil-soluble calcium sulfonate followed by 368.06 g of solvent neutral group 1 paraffinic acid base oil having a viscosity of about 600 SUS at 100 ° F. was added to the open mixing vessel. The 400 TBN overbased oil-soluble calcium sulfonate was of good quality calcium sulfonate similar to that used in Examples 4 and 12 of the above disclosed and '768 patent applications. Planetary mixing paddles were used to initiate mixing without heating. Thereafter, 31.18 g of mainly C12 alkylbenzene sulfonic acid was added. After 20 minutes of mixing, 75.29 g of finely divided crystalline calcium carbonate with an average particle size of 5 microns or less was added and allowed to mix for 20 minutes. In addition to the amount of amorphous calcium carbonate contained in the overbased calcium sulfonate, this calcium carbonate was added. 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. Thereafter, 41.2 g of water was added as a converting agent, and the mixture was heated to a temperature of 190 to 200 ° F. while continuing mixing (first temperature adjustment delay period). The mixture was mixed at this temperature range for 1 hour (first retention delay period). During this time, Fourier Transform Infrared (FTIR) spectroscopy showed water loss due to evaporation. Another 30 ml of water was added.

After 1 hour at 190-200 ° F., 15.66 g of hexylene glycol was added as a non-aqueous converting agent. Immediately after hexylene glycol was added, the mixture was visibly converted to grease. After mixing for 45 minutes at 190 to 200 ° F., Fourier Transform Infrared (FTIR) spectroscopy showed that the conversion of amorphous calcium carbonate contained in the overbased calcium sulfonate to crystalline calcium carbonate (calcite) occurred. Another 30 ml of water was added, followed by 1.55 g of glacial acetic acid and 16.39 g of 12-hydroxystearic acid. The two complexed acids were allowed to react for 30 minutes. Then, a solution of 16.99 g of 75% phosphoric acid in water was added slowly, allowed to mix and react. Thereafter, the grease was heated to 390 to 400 ° F. The heating mantle was removed from the mixer and cooled while allowing the grease to continue mixing. When the temperature was below 200 ° F., 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 ° F. Thereafter, the grease was removed from the mixer and three roll mills were passed through three times to achieve a final smooth and homogeneous texture. The grease had 286 round trip mixing. The percent overbased oil-soluble calcium sulfonate in the final grease was 31.77%. The dropping point was> 650 ° F. As can be seen, the thickener yield of the grease was slightly improved over Example 14 and Example 15 grease.

Example 17 (Aspect of the alkali / delayed addition method) : Another calcium sulfonate composite grease was prepared similarly to Example 16 above. However, this grease used an aspect of the alkali / delayed addition method. The non-aqueous conversion agent hexylene glycol was not initially added to water, but was added after the mixture was heated to 190-200 ° F. (first temperature adjustment delay period). Also, the water initially added contained very little sodium hydroxide. The sodium hydroxide concentration in the final grease was 0.08%. It was noted that the batch size of this grease was increased by 50% compared to Examples 14 to 16 grease. However, the percentage of each component and the details of the different method steps were not significantly different.

The grease was prepared as follows: 465.31 g of 400 TBN overbased oil-soluble calcium sulfonate followed by 367.68 g of solvent neutral group 1 paraffinic acid base oil having a viscosity of about 600 SUS at 100 ° F. was added to the open mixing vessel. The 400 TBN overbased oil-soluble calcium sulfonate was of good quality calcium sulfonate similar to that used in Examples 4 and 12 of the above disclosed and '768. Planetary mixing paddles were used to initiate mixing without heating. Thereafter, 46.64 g of mainly C12 alkylbenzene sulfonic acid was added. After mixing for 20 minutes, finely divided crystalline calcium carbonate with an average particle size of 5 microns or less of 112.50 g was added and allowed to mix for 20 minutes. In addition to the amount of amorphous calcium carbonate contained in the overbased calcium sulfonate, this calcium carbonate was added. 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. Then, 1.20 g of powdered sodium hydroxide dissolved 41.2 g of water was added, and the mixture was heated to 190 to 200 ° F. while continuing to mix (first temperature adjustment delay period). It was noted that when the temperature reached about 176 ° F., some foaming began to appear during the heating step. When the mixture reached 190-200 ° F., 42.13 g hexylene glycol was added (without a maintenance delay). Immediately after hexylene glycol was added, the mixture was visibly converted to grease.

After mixing for about 20 minutes, another 76.61 g of the same base oil as above was added because the grease was extremely heavy. The grease was mixed at 190-200 ° F. for another 45 minutes. During that time, Fourier transform infrared (FTIR) spectroscopy showed that the water had evaporated, so another 40 ml of water was added. At the end of the 45 minute mixing, the grease was significantly ground. Fourier transform infrared spectroscopy showed the conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite). Then, 2.36 g of glacial acetic acid and 24.58 g of 12-hydroxystearic acid were added. These two complexed acids were allowed to react for 30 minutes. Thereafter, 24.74 g of a 75% solution of phosphoric acid in water was slowly added, allowed to mix and react. Thereafter, the grease was heated to 390 to 400 ° F. The heating mantle was removed from the mixer and cooled while allowing the grease to continue mixing. As the grease cooled, it thickened to an extreme amount.

When the temperature was below 200 ° F., a total of 284.40 g of four fractions of the same base oil as above were added. Mixing was continued until the grease reached a temperature of 170 ° F. Thereafter, the grease was removed from the mixer and three roll mills were passed through three times to achieve a final smooth and homogeneous texture. The grease had a round trip mixing of 274 times. The percent overbased oil-soluble calcium sulfonate in the final grease was 31.84%. The dropping point was> 650 ° F. Using a conventional inverse relationship between the degree of miscibility and the percent overbased calcium sulfonate concentration, this example grease is 30.52% if additional base oil is added to bring the miscibility to the same value as in Example 16 grease above. Would have a percent overbased calcium sulfonate concentration. Thus, the use of aspects of the alkali / delayed addition method in this grease provided some improvement in thickener yield as compared to the two baseline greases of Examples 14 and 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 actually due to the rapid reaction of sodium hydroxide and complexed acid followed by metathesis of sodium fatty acid salts and calcium hydroxide, followed by the absence of calcium hydroxide, which significantly influences 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 11-17 herein and the methods used herein are summarized in Table 2 below. All of these examples used good quality overbased calcium sulfonate.

The following examples further demonstrate the superior properties of the overbased calcium sulfonate greases of the present invention that can be achieved using aspects of the alkali / delayed addition method, including modifications at the time of alkali metal addition.

Example 18 (Baseline Example-No Alkali Metal Hydroxide Added, No Delay Period): Calcium sulfonate complex grease, at least a portion of the long chain fatty acid is added prior to conversion and can act as a conversion agent, only calcium hydroxide or calcium oxide Added as a calcium-containing base to react with this complexed acid (without calcium hydroxyapatite or calcium carbonate added as in the '768 patent application), US Pat. Nos. 5,308,514 and 5,338,467 (May 3, 1994 and It was manufactured according to the scope of Witco Corporation patented 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 all of glacial acetic acid are added prior to conversion. Following the remaining amount of 12-hydroxystearic acid, a mixture of calcium hydroxide and boric acid water was added after conversion. Further, no alkali metal hydroxide was added, and there was no delay between the addition of water and the primary non-aqueous converting agent. The grease serves as a baseline for comparison.

The grease of Example 18 was prepared as follows: 380.73 g of 400 TBN overbased oil-soluble calcium sulfonate followed by 604.50 g of solvent neutral group 1 paraffinic acid base oil having a viscosity of about 600 SUS at 100 ° F. in an open mixing vessel. Put on Planetary mixing paddles were used to initiate mixing without heating. The 400 TBN overbased oil-soluble calcium sulfonate was of good quality calcium sulfonate similar to that used in Examples 4 and 12 of the above disclosed and '768 patent applications. Thereafter, 21.66 g of mainly C12 alkylbenzene sulfonic acid was added. After mixing for 20 minutes, 21.59 g of 12-hydroxystearic acid followed by 18.16 g of hexylene glycol and 38.0 g of water were added. After mixing for 10 minutes, 2.40 g of glacial acetic acid was added. The batch was then heated while mixing continuously until the temperature reached 190 ° F. The temperature was maintained at 190-200 ° F. for 45 minutes. The batch was mixed until Fourier transform infrared (FTIR) spectroscopy indicated that the conversion of amorphous calcium carbonate contained in overbased calcium sulfonate to crystalline calcium carbonate (calcite) occurred.

An additional 249.94 g paraffinic acid base oil was added followed by 18.21 g 12-hydroxystearic acid. The temperature was maintained at 190-200 ° F. and allowed to mix for 15 minutes. Thereafter, 38.02 g of finely divided food grade purity calcium hydroxide with an average particle size of 5 microns or less was mixed with 50 g of water, and the mixture was added to the grease. Thereafter, 23.02 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 ° F. Thereafter, the heating mantle was removed, and the grease was continuously stirred in open air to cool. When the grease cooled to 170 ° F., it was removed from the mixer and passed through three roll mills three times to achieve a final smooth and homogeneous texture. The grease had a 339 round trip mixing. The percent overbased oil-soluble calcium sulfonate in the final grease was 27.62%. The dropping point was 640 ° F.

Example 19 (Delayed Addition Method of '476 Patent Application, No Alkali Metal Hydroxide Added) : Delay Period of First Temperature Adjustment Between Addition of Another Calcium Complex Grease, Hexylene Glycol as Water and Non-Aqueous Conversion Agent ( It was prepared using the same equipment, raw material, amount, and manufacturing method as in Example 18, except that the heating was performed at 190 to 200) and the first holding delay period (holding at 190 to 200 for 1 hour) was present. . No alkali metal hydroxide was added. When hexylene glycol was added, the grease was maintained at 190-200 ° F. until conversion appeared to be complete. Thereafter, the rest of the procedure was the same as in Example 18 grease. The final grease had 60 round trips of 281 rounds. The percent overbased oil-soluble calcium sulfonate in the final grease was 27.60%. The dropping point was> 650 ° F. As can be seen, the grease of this example was improved over the grease of Example 18, as evidenced by a more robust permeation, although essentially having the same percentage of the overbased useful calcium sulfonate. Had a thickener job. Indeed, using the normal inverse relationship between the degree of miscibility and the percent overbased calcium sulfonate concentration, Example 19 is overbased sulfonic acid in grease when diluted with sufficient base oil to achieve the same miscibility as in Example 18 The expected percentage of calcium was 24.2%.

Example 20 (Alkali / Delayed Addition Method Aspect) : Another grease is similar to Example 19 grease by delaying the addition of the non-aqueous conversion agent hexylene glycol until the mixture is heated to 190-200 ° F. Prepared in a manner. However, in this grease, a small amount of sodium hydroxide was dissolved in the initial fraction of water at ambient temperature before heating of the batch started. In addition, when the temperature range of 190 to 200 ° F. was reached, there was no 1 hour holding delay period. Instead, hexylene glycol was added as soon as the temperature range was achieved. This was completed as observed in Example 7 grease above, where it was observed that when alkali metal hydroxide was also added, the temperature delay retention for the non-aqueous conversion agent did not provide the highest thickener yield improvement.

The grease was prepared as follows: 380.79 g of 400 TBN overbased oil-soluble calcium sulfonate followed by 589.33 g of solvent neutral group 1 paraffinic acid base oil having a viscosity of about 600 SUS at 100 ° F. was added to the open mixing vessel. Planetary mixing paddles were used to initiate mixing without heating. The 400 TBN overbased oil-soluble calcium sulfonate was of good quality calcium sulfonate similar to that used in Examples 4 and 12 of the above disclosed and '768 patent applications. Thereafter, 21.63 g of mainly C12 alkylbenzene sulfonic acid 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. The batch was then heated while mixing continuously until the temperature reached 190-200 ° F. (first temperature adjustment period). It was noted that when the temperature reached about 180 ° F., foaming was observed. When the temperature reached 190-200 ° F., 27.57 g hexylene glycol was added (without any retention delay). After about 10 minutes, the batch was visibly converted to a grease structure.

The batch was then mixed for an additional 45 minutes until Fourier Transform Infrared (FTIR) spectroscopy indicated the conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite). During the 45 minutes of mixing, 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 190-200 ° F. Then, 38.04 g of finely divided food grade purity calcium hydroxide with an average particle size of 5 microns or less was mixed with 50 g of water, and the mixture was added to the grease. Thereafter, 23.04 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 ° F. Thereafter, the heating mantle was removed, and the grease was continuously stirred in open air to cool. During the cooling, the grease thickened considerably. A total of 253.87 g of three approximately equal fractions of the same base oil as above were added into the grease and allowed to mix. When the grease cooled to 170 ° F., it was removed from the mixer and passed through three roll mills three times to achieve a final smooth and homogeneous texture. The grease had a mixing cycle of 280 60 times. The dropping point was> 650 ° F. The percent overbased oil-soluble calcium sulfonate in the final grease was 27.65%. The sodium hydroxide concentration in the final grease was 0.06%.

Example 21 (alkali / delayed mode of addition method): Another grease was prepared substantially the same as Example 20 grease above. The only important difference was that after the conversion was complete, a sodium hydroxide mixture in water was added. Thereafter, a second fraction of 12-hydroxystearic acid and a mixture of boric acid in hot water were added. The final grease had 285 round trips. The dropping point was> 650 ° F. The percent overbased oil-soluble calcium sulfonate in the final grease was 27.40%. The sodium hydroxide concentration in the final grease was 0.06%. As can be seen, the thickener yields of Example 19, Example 20, and Example 21 grease were all significantly superior to Example 18 baseline grease. However, the use of an aspect of the alkali / delayed addition method does not provide a further thickener yield improvement over that imparted only by the delayed addition method of the '476 patent application, when using good quality overbased calcium sulfonate. Did. When using low quality calcium overbased sulfonates instead of good quality overbased calcium sulfonates, it appears to indicate that the best thickener yield improvement can be achieved using alkali metal hydroxide additions and / or delayed non-aqueous converting methods.

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

Additional examples showing the results of the addition of alkali metal hydroxide in simple calcium sulfonate grease are identified in the examples below.

Example 22 (Baseline Example-No alkali metal hydroxide added, no delay period): For use as a baseline for comparison with the following three greases, simple calcium sulfonate grease, without any delay or addition of alkali metal hydroxide , US Pat. Nos. 3,377,283 and 3,492,231 (patented by Lubrizol Corporation on April 9, 1968 and January 27, 1970, respectively). The grease was prepared as follows: 496.49 g of 400 TBN overbased oil-soluble calcium sulfonate followed by 394.45 g of solvent neutral group 1 paraffinic acid base oil having a viscosity of about 600 SUS at 100 ° F. was added to the open mixing vessel. Planetary mixing paddles were used to initiate mixing without heating. The 400 TBN overbased oil-soluble calcium sulfonate was of good quality calcium sulfonate similar to that used in Examples 4 and 12 of the above disclosed and '768 patent applications. Thereafter, 20.23 g of mainly C12 alkylbenzene sulfonic acid was added. After 20 minutes of mixing, 44.23 g of water followed by 16.57 g of hexylene glycol (primary converting agent) were added. The batch was then heated while mixing continuously until the temperature reached 190 ° F. When the temperature reached 190 ° F., 6.20 g of glacial acetic acid was added. When visible conversion to the grease structure was observed, Fourier Transform Infrared (FTIR) spectroscopy indicated that conversion of amorphous calcium carbonate contained in the overbased calcium sulfonate to crystalline calcium carbonate (calcite) occurred, The temperature was maintained at 190-200 ° F. for 45 minutes. During this time, an additional 10 ml of water was added. The resulting grease was then heated to 330 ° F. Thereafter, the heating mantle was removed and the grease was allowed to cool while still stirring in open air. When the temperature reached 200 ° F., 2.34 g of aryl amine antioxidant was added. When the grease cooled to 170 ° F., it was removed from the mixer and passed through three roll mills three times to achieve a final smooth and homogeneous texture. The grease had a reciprocal mixing degree of 331 times. The percent overbased oil-soluble calcium sulfonate in the final grease was 53.03% and the dropping point was> 650 ° F.

Example 23 (Delayed Addition Method of '476 Patent Application, No Alkali Addition): Another simple calcium sulfonate grease was carried out above, except that there was a delay period between the addition of water and a non-aqueous conversion agent. Example 22 Manufactured in a similar manner to grease. No alkali metal hydroxide was added in this example. The grease was prepared as follows: 495.41 g of 400 TBN overbased oil-soluble calcium sulfonate followed by 391.96 g of solvent neutral group 1 paraffinic acid base oil having a viscosity of about 600 SUS at 100 ° F. was added to the open mixing vessel. Planetary mixing paddles were used to initiate mixing without heating. The 400 TBN overbased oil-soluble calcium sulfonate was of good quality calcium sulfonate similar to that used in Examples 4 and 12 of the above disclosed and '768 patent applications. Then, 19.65 g of mainly C12 alkylbenzene sulfonic acid was added. After mixing for 20 minutes, 44.42 g of water was added. The mixture was then heated to 160 ° F. (first temperature adjustment delay period) and held at 160 to 170 ° F. for 2 hours and 30 minutes (first maintenance delay period). During this time, an additional 50 ml of water was added because most of the water originally added was evaporated. The batch was then heated to 190 ° F. (second temperature adjustment delay period), 16.53 g of hexylene glycol (primary conversion agent) followed by 6.34 g of glacial acetic acid.

When a visible conversion to the grease structure is observed, the temperature is 45 at 190-200 ° F. until Fourier Transform Infrared (FTIR) spectroscopy indicates the conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite). Kept for a minute. During this time an additional 10 ml of water was added. The resulting grease was then heated to 330 ° F. Thereafter, the heating mantle was removed, and the grease was continuously stirred in open air to cool. When the temperature reached 200 ° F., 2.32 g of aryl amine antioxidant was added. When the grease cooled to 170 ° F., it was removed from the mixer and passed through three roll mills three times to achieve a final smooth and homogeneous texture. Example 21 The dropping point for grease was> 650 ° F. The grease had 290 round trip mixing. The percent overbased oil-soluble calcium sulfonate in the final grease was 53.14%.

It was noted that the present grease and the above Example 22 grease essentially had the same percentage of the overbased calcium sulfonate. However, the blending lead of Greece was harder by 41 points. Therefore, the delayed glycol procedure used in this grease resulted in improved thickener yield. Indeed, using the normal inverse relationship between the degree of miscibility and the percent overbased calcium sulfonate concentration, this example of the overbased formulation of Example 23 grease, when diluted with a suitable base oil to obtain the same miscibility as Example 22 grease The expected percentage of calcium phonate is 46.6%. In addition, a very high dropping point was maintained.

Example 24 (alkali addition and delayed addition): Another simple calcium sulfonate grease was prepared in a similar manner to Example 23 grease, except using a different delay period between the addition of water and the non-aqueous converting agent and adding a small amount of sodium hydroxide. . The sodium hydroxide concentration in the final grease was 0.09%. The grease was prepared as follows: 495.18 g of 400 TBN overbased oil-soluble calcium sulfonate followed by 392.56 g of solvent neutral group 1 paraffinic acid base oil having a viscosity of about 600 SUS at 100 ° F. was added to the open mixing vessel. Planetary mixing paddles were used to initiate mixing without heating. The 400 TBN overbased oil-soluble calcium sulfonate was of good quality calcium sulfonate similar to that used in Examples 4 and 12 of the above disclosed and '768 patent applications. Then, 20.31 g of mainly C12 alkylbenzene sulfonic acid 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 adjustment delay period), and 16.73 g of hexylene glycol and 6.16 g of glacial acetic acid were added.

When a visible conversion to the grease structure is observed, the temperature is 45 at 190-200 ° F. until Fourier Transform Infrared (FTIR) spectroscopy indicates the conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite). Kept for a minute. During this time an additional 20 ml of water was added. The resulting grease was then heated to 330 ° F. Thereafter, the heating mantle was removed, and the grease was continuously stirred in open air to cool. When the temperature reached 200 ° F., 3.35 g of aryl amine antioxidant was added. When the grease cooled to 170 ° F., it was removed from the mixer and passed through three roll mills three times to achieve a final smooth and homogeneous texture. Example 24 The dropping point for grease was 478 ° F. The grease had 311 round trip mixing. The percent overbased oil-soluble calcium sulfonate in the final grease was 52.95%.

Comparing this grease to Example 23 grease, it is clear that the benefits observed by using aspects of the alkali / delayed addition method in the grease examples are not observed in this grease. In this Example 24 grease compared to the above Example 23 grease, the thickener yield was significantly reduced and the dropping point was lower. Again, without wishing to be bound by theory, it seems that the addition of alkali hydroxides primarily improves the thickener yield, which is due to the reaction with the complexing acid used in the production of complex calcium sulfonate grease, but the simple grease is Since it does not involve addition, this benefit is not achieved using a simple grease, and even adding alkali metal hydroxides to the simple grease composition appears to be detrimental to thickener yield. The results of Examples 22-24 are summarized in Table 4 below.

The composite grease examples show that utilizing aspects of the alkali / delayed addition method consistently improved the thickener yield regardless of which calcium sulfonate based grease technique used in previous documents was used. In addition, improvement in the thickener yield is observed regardless of the good or low quality of the overbased calcium sulfonate used as defined in the '768 patent application, but rather is of low quality sulfonic acid within the scope of the example compositions included in the present invention. Greater improvement was achieved using calcium (as opposed to expected).

Example greases prepared according to the alkali / delayed addition method of the present invention disclosed above also have various comparison sets of the above examples, compared to example greases in which the addition of all or part of the non-aqueous conversion agent is not delayed. Although the ingredients and amounts used in the fields are the same or fairly similar, they show different physical properties. Using Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM) to test the samples of the example greases were greases prepared using the delayed addition according to the invention with greases of similar compositions prepared without the delay. It proves that it can be distinguished from. For example, there are differences in adsorption curve profiles and differences in particle size and configuration.

The embodiments provided herein are primarily NLGI No. 1, No. 2, or No. Even if it corresponds to the 3rd grade, it is No. It is most preferred to have a grade 2, the scope of the present invention is No. It should be further understood that all NLGI consistency classes that are harder or softer than class 2 are included. However, as will be understood by those skilled in the art, NLGI No. For these greases according to the present invention which are not Class 2, their properties are more or less used base oils No. It is consistent with what is obtained when providing a grade 2 product.

Although the present invention mainly deals with grease prepared in open containers, and although all of the above embodiments are in open containers, the composite calcium sulfonate grease composition and method may also be used in closed containers where heating under pressure is performed. The use of such a pressurized container can result in a better thickener yield than those disclosed in the embodiments herein. For the purposes of the present invention, an open container is any container with or without a top cover or hatch, unless any top cover or hatch is not vapor-tight so that significant pressure can be created during heating. Using such an open container, which includes a closed top cover or hatch during the conversion process, will generally help to hold the required level of water as the conversion agent while at the same time bringing the conversion temperature above the boiling point of water. As will be appreciated by those skilled in the art, these higher conversion temperatures can lead to further thickener yield improvement for both simple and complex calcium sulfonate greases.

As used in the subject invention, the term "thickener id" as used herein, has a specific desired roughness as defined by ASTM D217 or D1403, which is a conventional meaning, that is, the standard miscibility test commonly used in the manufacture of lubricating greases. It is the high concentration of overbased usable calcium sulfonate required to provide grease. In a similar manner, the “dropping point” of grease as used herein refers to the value obtained using ASTM D2265, a standard dropping test commonly used in the manufacture of lubricating grease. As used herein, reference to the addition of a component immediately after reaching a certain temperature means that the component is added as soon as it reaches the physically possible temperature when the amount added and the equipment is used, but preferably The components are added within a short period of time, 10 minutes or less, more preferably 5 minutes or less after the mixture has approximately reached the indicated temperature.

As used in the present invention, (1) the amount of dispersed calcium carbonate (or amorphous calcium carbonate) or residual calcium oxide or calcium hydroxide contained in the overbased calcium sulfonate is based on the weight of the overbased calcium sulfonate; (2) Some components are added in two or more separate fractions, each fraction can be expressed as a percentage of the total amount of the component; (3) The specific component (e.g., water that reacts with other components, or a calcium-containing base or alkali metal hydroxide) may or may not be present in the final grease, or present in the final grease in an amount defined for addition as a component. Even if not, all other amounts (including the total amount) of the components, defined as percentages or parts, are amounts added as components based on the weight of the final grease product. As used herein, "additional calcium carbonate" means crystalline calcium carbonate added as a separate component in addition to the amount of dispersed calcium carbonate contained in the overbased calcium sulfonate. As used herein, "additional calcium hydroxide" and "additional calcium oxide" refer to calcium hydroxide and calcium oxide added as separate components in addition to the amount of residual calcium hydroxide and / or calcium oxide that may be contained in the overbased sulfonate, respectively. it means. Calcium hydroxyapatite, as used herein to describe the present invention (as opposed to how the following terms are used in some prior art literature), comprises (1) a compound having the formula Ca ₅ (PO ₄ ) ₃ OH or ( 2) It means the specific exclusion of (a) a mathematical equivalent formula having a melting point of about 1100 ° C or (b) a mixture of tricalcium phosphate and calcium hydroxide by the mathematical equivalent formula. Those skilled in the art upon reading the present specification, including the examples included herein, modifications and variations to the composition and methodology for preparing the composition are made within the scope of the present invention, and disclosed herein. It will be understood that the scope of the invention is limited only by the broadest interpretation of the appended claims to which the inventor has legal rights.

Claims (44)

As a method for preparing a complex overbased calcium sulfonate grease,
A certain amount of oil-soluble calcium sulfonate with amorphous calcium carbonate dispersed therein is mixed with a base oil and one or more converting agents to prepare a pre-conversion mixture. Forming;
Heating the mixture before conversion until the conversion of the amorphous calcium carbonate to crystalline calcium carbonate occurs, thereby converting the mixture into a converted mixture;
Mixing a predetermined amount of alkali metal hydroxide with the pre-conversion mixture, or the converted mixture, or both; And
Mixing a predetermined amount of one or more complexing acids with the pre-conversion mixture, or the converted mixture, or both;
Here, the amount of the overbased oil-soluble calcium sulfonate is 10 to 45% of the final grease weight, a method for producing a complex overbased calcium sulfonate grease. The method according to claim 1, wherein the amount of the alkali metal hydroxide is 0.005 to 5% of the final grease weight. The method of claim 1, wherein one or more 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, or A method of manufacturing, further comprising mixing with both of these. The method according to claim 1, wherein the alkali metal hydroxide is sodium hydroxide, lithium hydroxide, potassium hydroxide or a combination thereof. The method according to claim 2, wherein the alkali metal hydroxide is sodium hydroxide, and the amount of the sodium hydroxide is 0.01 to 0.4% of the final grease weight. The method 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. The method according to claim 1, wherein the overbased calcium sulfonate is a poor quality calcium sulfonate and the grease has a dropping point of 575 ° F or higher. The method of claim 1, wherein the converting agent comprises water and at least one non-aqueous converting agent, the method comprising:
Mixing the water with the overbased calcium sulfonate and base oil to form a first mixture; And
During the one or more delay periods or after the one or more delay periods, further comprising mixing at least a portion of the one or more non-aqueous converting agents with the first mixture to form the pre-conversion mixture, Manufacturing method. The preparation according to claim 8, wherein the alkali metal hydroxide is dissolved in the water used as a converting agent to form a solution, and the solution is mixed with the overbased calcium sulfonate and base oil to form the first mixture. Way. 9. 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 the first mixture, or the pre-conversion mixture, or the converted mixture, or combinations thereof. Mixed with, manufacturing method. 9. The converted mixture of claim 8, wherein all or part of at least one complexed acid is mixed with the first mixture or with the pre-conversion mixture, and at least all or part of the complexed acid is the same or different from the complexed acid. Mixed with, manufacturing method. 12. The method 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. The method of claim 8, wherein the conversion step,
Heating the pre-conversion mixture to a conversion temperature range of 190 to 230 ° F. in an open container or to another temperature range in which conversion occurs in a closed container; And
And maintaining the temperature in the above range until conversion of the amorphous calcium carbonate to crystalline calcium carbonate occurs. 12. The method of claim 11, wherein the complexed 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 A process in which 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 whole of the boric acid, phosphoric acid, or both is mixed with the converted mixture. 15. The method of claim 14, wherein the non-aqueous converting agent is hexylene glycol, which is mixed with the first mixture after a temperature adjustment delay period. The method according to claim 14, wherein the alkali metal hydroxide is mixed with the first mixture. The method according to claim 1, wherein the calcium sulfonate grease has a dropping point of 575 ° F. or higher, and the amount of the overbased calcium sulfonate is 10 to 32% of the final grease weight. The method according to claim 8, wherein the calcium sulfonate grease has a dropping point of 575 ° F. or higher, and the amount of the overbased calcium sulfonate is 10 to 32% of the final grease weight. The method of claim 8, wherein at least a portion of one or more of the non-aqueous conversion agents,
Further comprising adding to the mixture of one or more of the first mixture before any delay period, the first mixture during the delay period or after the delay period, or the mixture before or during one or more delay periods or after one or more delay periods. The manufacturing method. 21. The method of claim 20, wherein acetic acid is not added as a non-aqueous converting agent for any delay period. The method of claim 8, wherein the calcium hydroxyapatite, calcium hydroxide added, calcium oxide added, calcium carbonate added, or any combination thereof, the first mixture, or the pre-conversion mixture, or The method further comprises the step of mixing with the converted mixture, or any combination thereof. The method according to claim 8, wherein at least one of the non-aqueous converting agents is glycol, glycol ether, or glycol polyether. 24. The method of claim 23, wherein the glycol is hexylene glycol. 25. The method of claim 24, wherein a 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 agent after one or more delay periods or for one or more delay periods. 1 A mixture or a method of preparation, which is mixed with the mixture before conversion. 9. The method of claim 8, wherein there are at least two delay periods, wherein one of the delay periods is a temperature adjustment delay period, wherein the first mixture or the pre-conversion mixture is heated or cooled, and at least one other delay period is present. Is a retention delay period, wherein the first mixture or the pre-conversion mixture is maintained at a constant temperature or within a predetermined temperature range for a period of time. 9. The method according to claim 8, wherein the overbased calcium sulfonate is low quality calcium overbased sulfonate. 23. The method of claim 22, wherein the overbased calcium sulfonate comprises 0-8% residual calcium hydroxide and / or calcium oxide by weight of the overbased calcium sulfonate, wherein additional calcium oxide or calcium hydroxide reacts with the complexed acid. It is not added as a calcium-containing base for the production method. The method of claim 8, wherein at least one of the non-aqueous converting agents is methanol, isopropyl alcohol, or another low molecular weight alcohol. The method according to claim 8, wherein methanol, isopropyl alcohol, or another low molecular weight alcohol is not used as the non-aqueous converting agent. The method according to claim 1, wherein the amount of the overbased calcium sulfonate is 10 to 22% of the final grease weight. The method of claim 1, wherein at least a portion of the alkali metal hydroxide is added to the pre-conversion mixture. The method of claim 1, further comprising mixing one or more calcium-containing bases for reaction with the one or more complexed acids, wherein:
The one or more calcium-containing bases are added to the pre-conversion mixture, or to the converted mixture, or both;
At least a portion of the alkali metal hydroxide is added prior to the reaction with the at least one calcium-containing base and the at least one complexed acid. The method of claim 1, further comprising mixing one or more calcium-containing bases for reaction with the one or more complexed acids, wherein:
The one or more calcium-containing bases are added to the pre-conversion mixture, or to the converted mixture, or both;
At least a portion of the at least a portion of the calcium-containing base and the at least a portion of the complexed acid, the alkali metal hydroxide is mixed after the addition of at least a portion of the preparation method. The method of claim 1, wherein at least a portion of the alkali metal hydroxide is added to the pre-conversion mixture, and at least a portion of an alkali metal hydroxide that is the same or different from the alkali metal hydroxide is added to the converted mixture. delete delete delete delete delete delete delete delete delete