JP6511199B2 - Production of calcium sulfonate grease by using alkali metal hydroxide and delayed addition of non-aqueous conversion agent - Google Patents

Description

[Reference to Related Application]
This application claims priority to US Patent Application No. 15 / 130,422 filed on April 15, 2016 and US Patent Application No. 14 / 990,473 filed on January 7, 2016 U.S. patent application Ser. No. 13 / 664,768 (now U.S. Pat. No. 9,458,406 issued Oct. 4, 2016) and U.S. patent application Ser. No. 13 / 664,574. (Currently, it is a partially continuing application of US Pat. No. 9,273,265 issued on March 1, 2016). These two U.S. Patent Applications are both filed October 31, 2012, and claim the benefit of U.S. Provisional Patent Application No. 61 / 553,674, filed October 31, 2011.

[1. Technical field]
The present invention relates to overbased calcium sulfonate greases made with the addition of alkali metal hydroxides, both for thickener yield and for expected high temperature practicability represented by the dropping point. It is an improvement even if the oil soluble overbased calcium sulfonate used to make it is perceived as poor quality. The invention further relates to an overbased calcium sulfonate grease made using both an added alkali metal hydroxide and a delayed addition of a non-aqueous conversion agent.

[2. Description of Related Art]
Overbased calcium sulfonate greases are a category of greases that have been established for many years. One known method of producing such greases is a two-step process that includes the steps of "promotion" and "conversion". In general, the first step ( "promoted") is a stoichiometric excess of calcium oxide (CaO) or calcium hydroxide (Ca _{(OH) 2)} as a base source, alkyl benzene sulfonic acid, carbon dioxide (CO ₂ ) And other components to form an oil-soluble overbased calcium sulfonate in which amorphous calcium carbonate is dispersed. These overbased oil-soluble calcium sulfonates are generally clear and bright and have Newtonian rheology. They may be slightly hazy, but such variations do not preclude their use in the preparation of overbased calcium sulfonate greases. For the purposes of the present disclosure, the terms "overbased oil-soluble calcium sulfonate" and "oil-soluble overbased calcium sulfonate" and "overbased calcium sulfonate" refer to any perfusate suitable for producing calcium sulfonate greases. Refers to basic calcium sulfonate.

  In general, the second step ("conversion"), if necessary, with propylene glycol, isopropyl alcohol, water, formic acid or with a suitable base oil (such as mineral oil) to avoid the initial grease becoming very hard. A converting agent such as acetic acid is added to the product of the accelerating step to convert the amorphous calcium carbonate contained in the overbased calcium sulfonate into a very finely divided crystalline calcium carbonate dispersion (calcite) It is a thing. When acetic acid or other acids are used as converting agents, typically, water and another non-aqueous converting agent (a third converting agent such as an alcohol) are additionally used. Alternatively, if only water is added (without a third converting agent), the conversion typically occurs in a pressurized vessel. Since excess calcium hydroxide or calcium oxide is used to make it overbased, a small amount of remaining calcium oxide or calcium hydroxide is also present as part of the oil-soluble overbased calcium sulfonate They may disperse in the initial grease structure. The very finely divided calcium carbonate formed by conversion, also known as colloidal dispersion, interacts with calcium sulfonate to form a grease-like consistency. Such overbased calcium sulfonate greases produced through a two-step process are known as "simple calcium sulfonate greases" and are described, for example, in U.S. Pat. No. 3,242,079, U.S. Pat. U.S. Pat. No. 3,372,115, U.S. Pat. No. 3,376,222, U.S. Pat. No. 3,377,283 and U.S. Pat. No. 3,492,231.

  It is also known in the art to combine these two steps into a single step by carefully controlling the reaction. In this one-step process, simple calcium sulfonate grease comprises carbon dioxide, and an accelerator (amorphous calcium carbonate overbasing is caused by the reaction of carbon dioxide with excess calcium oxide or calcium hydroxide), An appropriate sulfonic acid is either calcium hydroxide or calcium oxide in the presence of a reactant system which simultaneously acts as both a converting agent (converting amorphous calcium carbonate into very finely divided crystalline calcium carbonate). It is prepared by reacting. Thus, the grease-like consistency is formed in a single step such that the overbased oil-soluble calcium sulfonate (product of the first step in the two-step process) does not actually form and separate as a separate product Be done. This one-step process is disclosed, for example, in US Pat. Nos. 3,661,622, 3,671,012, 3,746,643 and 3,816,310. ing.

  In addition to simple calcium sulfonate greases, calcium sulfonate complex greases are also known in the prior art. These complex greases generally comprise a calcium-containing strong base, such as calcium hydroxide or calcium oxide, added to a simple calcium sulfonate grease made by either a two-step or one-step treatment, to a stoichiometric equivalent , 12-hydroxystearic acid, boric acid, acetic acid, or a complexing acid such as phosphoric acid (which may be a conversion agent if added before conversion). The advantages of the calcium sulfonate complex grease claimed over simple greases include reduced tackiness, improved pumpability, and improved high temperature practicability. Calcium sulfonate complex greases are disclosed in U.S. Patent No. 4,560,489, U.S. Patent No. 5,126,062, U.S. Patent No. 5,308,514 and U.S. Patent No. 5,338,467 .

  Most of the known prior art using a two-step process teaches the simultaneous addition of all conversion agents (water and non-aqueous conversion agents), usually prior to heating. However, in some prior art documents, the time interval between the addition of water and the addition of at least part of the non-aqueous converter (without exception, not well defined or not at all defined) is It is disclosed. For example, U.S. Pat. No. 4,560,489 heats the base oil and overbased calcium carbonate to about 150.degree. F., then adds water and then heats the mixture to about 190.degree. And processes of adding methyl cellosolve (highly toxic monomethyl ether of ethylene glycol) (Examples 1 to 3). The resulting grease contains over 38% of overbased calcium sulfonate. The use of less than 38% hydrogen peroxide according to the '489 patent gives a soft grease, so the' 489 patent states that the ideal amount of overbased calcium sulfonate in the process disclosed therein is It is pointed out that it is about 41 to 45%. The grease obtained in Example 1 of the '489 patent only has a drop point of about 570 ° F. The '489 patent does not mention the delay time between the addition of water and the addition of non-aqueous conversion agent, but indicates that the addition was just after heating from 150F to just 190F. Drop point and thickener yields of the '489 patent are undesirable.

  In addition, U.S. Pat. Nos. 5,338,467 and 5,308,514 disclose the use of fatty acids such as 12-hydroxystearic acid as conversion agents for use with acetic acid and methanol. There is no delay in the addition of fatty acids, but there are some intervals between the addition of water and the addition of acetic acid and methanol. Example B of the '514 patent and Example 1 of the' 467 patent both add water and a fatty acid conversion agent to the other ingredients (including overbased calcium sulfonate and base oil), and then add about 140 to 145 Disclosed is a process of heating to ° F and then adding acetic acid followed by methanol. 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 is 32.2, which is higher than desired. These patents do not mention the delay period between the addition of water and fatty acid and the addition of acetic acid and methanol, but indicates that the addition is just after heating for an unknown period. A similar process is disclosed in Example A of the '514 patent and in Example C of the' 467 patent, but all fatty acids are added after conversion, and the non-aqueous converting agent used is Acetic acid and methanol were added after the mixture with water was heated to 140-145F. The amount of overbased calcium sulfonate in these examples is 40% higher than in the previous examples. In addition to not achieving the ideal thickener yield results, all of these processes use methanol as a conversion agent and therefore have environmental disadvantages. The use of volatile alcohols as conversion agents can cause these components to vent to the atmosphere at the end of the grease manufacturing process, which is banned in many parts of the world. If not vented, the alcohol must be recovered by water scrubbing or water trapping, resulting in dangerous material disposal costs. As such, there is preferably a need for a method to achieve better thickener yield without the need to use volatile alcohols as conversion agents.

  Although better thickener yield is achieved in Example 10 of the '514 patent, the use of excess lime is taught as a requirement to achieve those results. In that example, water and excess lime are added along with the other ingredients, the mixture is heated to 180-190 F, and acetic acid is added slowly during the heating period. The resulting grease contained 23% overbased calcium sulfonate. Although this thickener yield is superior to others, there is room to improve it so that it does not require the use of excess lime which the '514 patent teaches as a requirement.

  Other examples of the '514 and' 467 patents that have a thickener yield of 23% or less involve the use of a pressurized kettle during conversion, or the addition of water and non-aqueous conversion agents, or both. There is no "delay" between These examples include adding water and a fatty acid conversion agent, mixing for 10 minutes without heating, and then adding acetic acid under pressure kettle or pressureless. None of these patents recognize the benefit or advantage in the 10 minute interval for the addition of acetic acid, or the other heating delays in the above example, but rather, these patents have observed the observed yields. The reasons for the improvement focus on the use of fatty acids as converting agents and the benefits of the addition of fatty acids before conversion, after conversion, or both. Furthermore, as explained below, this 10 minute mixing interval without heating is not a "delay" as used herein, but is considered simultaneous when adding the components simultaneously, each It is recognized that the addition of the components takes at least some time and does not occur instantaneously.

  Furthermore, the known prior art describes as a source of basic calcium for the preparation of calcium sulfonate greases or as a component necessary for the reaction with complexing acids to form calcium sulfonate complex greases. Regularly teaches the use of calcium oxide or calcium hydroxide. The known prior art is that the addition of calcium hydroxide or calcium oxide is sufficient to provide a total level of calcium hydroxide or calcium oxide sufficient to fully react with the complexing acid (overbased oil It teaches that it is necessary to be added to the amount of calcium hydroxide or calcium oxide present in the soluble calcium sulfonate. As disclosed in co-pending U.S. patent application Ser. No. 13 / 664,768 ("the '768 application") and U.S. Pat. No. 9,273,265, the known prior art generally refers to the presence of calcium carbonate. (The presence of amorphous calcium carbonate dispersed in calcium sulfonate after carbonation, as a separate component or as an "impurity" in calcium hydroxide or calcium oxide) is avoided for at least two reasons It teaches that it should be done. The first reason is that calcium carbonate is generally considered to be a weak base and is unsuitable for reacting with complexing acids to form an optimal grease structure. The second reason is that the presence of unreacted solid calcium compounds (including calcium carbonate, calcium hydroxide or calcium oxide) interferes with the conversion process so that unreacted solids are not removed before or before conversion. Is that the grease becomes bad. However, Applicants have added calcium carbonate, calcium hydroxyapatite, or a combination thereof (in addition to the amount of calcium carbonate contained in the overbased calcium sulfonate) as separate components, added calcium hydroxide or calcium oxide. By adding as a component that reacts with the complexing acid, with or without, it has been demonstrated to produce superior greases as described in the '574 and' 768 applications.

  There are two prior art documents which disclose the addition of crystalline calcium carbonate as a separate component (in addition to the amount of calcium carbonate contained in the overbased calcium sulfonate), but (as the prior art teaches) those Grease thickener yields are low or require nanosized calcium carbonate particles. For example, U.S. Pat. No. 5,126,062 discloses adding 5 to 15% calcium carbonate as a separate component in forming a complex grease, but to react with complexing acids It also requires the addition of calcium hydroxide. The added calcium carbonate is not the only added calcium with a base that reacts with the complexing acid in the '062 patent. In practice, the added calcium carbonate is not explicitly added as a basic reactant for the reaction with the complexing acid. Alternatively, added calcium hydroxide is required as a specific calcium-containing base for reaction with all complexing acids. Furthermore, the obtained NGLI No. 2 greases contain 36% to 47.4% overbased calcium sulfonate, and this expensive ingredient is a significant amount. In another example, Chinese Publication CN 101993767 discloses adding nano-sized particles of calcium carbonate (5 to 300 nm in size) to overbased calcium sulfonate but to react with complexing acid It has not been shown that calcium carbonate nano-sized particles are added as a reactant or that only calcium-containing bases are added separately. By using nano-sized particles, the thickening of the grease is increased and remains hard, which is a crystalline carbonate formed by converting amorphous calcium carbonate contained in the overbased calcium sulfonate Similar to the fine dispersion of calcium (it can be about 20 Å to 5000 Å or about 2 nm to 500 nm according to the '467 patent), but at a much higher cost than when the added calcium carbonate is a particle of larger size Will increase. This Chinese patent application greatly emphasizes the absolute need for calcium carbonate with correct nanoparticle size. As shown in the example greases according to the invention described in the co-pending '574 application, without requiring the use of very expensive nano-sized particles, and with complexing acids An excellent grease can be formed by the addition of micron sized calcium carbonate when using an added calcium carbonate as the only added calcium containing base to react.

There are also prior art documents that use tricalcium phosphate as an additive for lubricating greases. For example, U.S. Pat. No. 4,787,992, U.S. Pat. No. 4,830,767, U.S. Pat. No. 4,902,435, U.S. Pat. No. 4,904,399, U.S. Pat. No. all teach the use of tricalcium phosphate as an additive in lubricating greases. However, in order to make a lubricating grease containing a calcium sulfonate based grease, it has a melting point of about 1100 ° C. as a calcium-containing base that reacts with an acid and has the formula Ca ₅ (PO ₄ ) ₃ OH or mathematically equivalent There appears to be no prior art document that teaches the use of calcium hydroxyapatite having the formula: Including US Patent Application Publication No. 2009/0305920, there are several prior art documents belonging to Showa Shell Japan, describes a grease containing tricalcium phosphate and _Ca 3 _{(PO 4) 2,} As a source of tricalcium phosphate, the formula [Ca ₃ (PO ₄ ) ₂ ] ₃ . Reference is made to "hydroxyapatite" with Ca (OH) ₂ . This reference to "hydroxyapatite" is disclosed as a mixture of tricalcium phosphate and calcium hydroxide, and is disclosed and claimed in the '768 application, and the formula Ca ₅ ( PO ₄ ) ₃ OH, or a mathematically equivalent formula, different from calcium hydroxyapatite which has a melting point of about 1100 ° C. Although a misleading term, calcium hydroxyapatite, tricalcium phosphate and calcium hydroxide are different chemical compounds that have different chemical formulas, structures and melting points, respectively. When mixed together, two different crystalline compounds, tricalcium phosphate (Ca ₃ (PO ₄ ) ₂ ) and calcium hydroxide (Ca (OH) ₂ ) do not react with each other or different crystalline compounds calcium hydroxyapatite (Ca Generate ₅ (PO ₄ ) ₃ OH). The melting point of tricalcium phosphate (formula Ca ₃ (PO ₄ ) ₂ ) is 1670 ° C. Calcium hydroxide has no melting point and instead loses water molecules to form calcium oxide at 580 ° C. The calcium oxide thus formed has a melting point of 2580.degree. Calcium hydroxyapatite (with the formula Ca ₅ (PO ₄ ) ₃ OH or mathematically equivalent formula) has a melting point of about 1100 ° C. Thus, regardless of the terminology, calcium hydroxyapatite is not the same compound as tricalcium phosphate and not just a mixture of tricalcium phosphate and calcium hydroxide.

  Further, it would be desirable to have a calcium sulfonate complex grease composition and method of making the same that results in both improved thickener yield and drop point. Many of the known prior art compositions have a drop point of at least 575 ° F. At least 36% (by weight of the final grease product) of overbased calcium sulfonate is required to achieve a grease suitable for the two categories. Overbased oil-soluble calcium sulfonate is one of the most expensive components in the production of calcium sulfonate greases, thus reducing the amount of this component while still maintaining the desired level of hardness in the final grease It is desirable to do so (to increase the thickener yield). Many prior art documents utilize high pressure reactors to substantially reduce the amount of overbased calcium sulfonate used. Specifically, the percentage of overbased oil-soluble calcium sulfonate is less than 36%, and the consistency is NLGI No. 1 To obtain an overbased calcium sulfonate grease having a drop point of always at least 575 F without requiring a high pressure reactor when within two grades (or the 60-round penetration penetration of the grease is 265 to 295) Is desirable. As the dropping point is the first and most easily established guideline for the high temperature service limit of lubricating greases, a higher dropping point is considered desirable.

  It is also known to add alkali metal hydroxides to simple calcium soap greases such as anhydrous calcium-soap thickened greases. However, it is not known that the addition of an alkali metal hydroxide to a calcium sulfonate grease leads to an improvement in thickener yield and a high dropping point. Because this addition would be considered unnecessary by the person skilled in the art. The reason for adding alkali metal hydroxides such as sodium hydroxide to simple calcium soap greases is that commonly used calcium hydroxide is less water soluble and is a weaker base than more water soluble sodium hydroxide It is from. To this end, a small amount of sodium hydroxide dissolved in the added water can be quickly added with soap-forming fatty acids (usually a mixture of 12-hydroxystearic acid or 12-hydroxystearic acid and a nonhydroxylated fatty acid such as oleic acid) It is said to react and form sodium soap. This quick response is considered "get the ball rolling". However, the direct reaction of calcium-containing bases, such as calcium hydroxide, with fatty acids is not a problem in producing calcium sulfonate complex greases. This reaction occurs very easily because of the high surface activity / dispersability of the large amounts of calcium sulfonate present. Thus, in the prior art, it is not known to use alkali metal hydroxides in calcium sulfonate greases to react complexing acids with calcium hydroxide.

  It is also not known to combine various components and techniques in the preparation of calcium sulfonate greases having improved thickener yield and high drop weight. For example, the addition of an alkali metal hydroxide and (1) the use of calcium hydroxyapatite, addition crystalline calcium carbonate, or a combination thereof as a calcium-containing base (also called a basic calcium compound) to react with complexing acids It is not known to combine (with or without added calcium hydroxide or calcium oxide), (2) delayed addition of non-aqueous conversion agents, or (3) combinations of 1 and 2.

  The present invention relates to an overbased calcium sulfonate grease and a method of making such a grease, wherein the thickener yield (less overbased calcium sulfonate required is determined while acceptable consistency is measured Both maintain the value) and the expected high temperature availability as indicated by the dropping point. In one preferred embodiment of the present invention, the complex calcium sulfonate grease composition comprises an alkali metal hydroxide. In another preferred embodiment, the complex calcium sulfonate grease composition comprises an alkali metal hydroxide and calcium hydroxyapatite and an added calcium carbonate as an added calcium containing base (also referred to as a basic calcium compound) that reacts with the complexing acid Or both of them. In yet another preferred embodiment, the complex calcium sulfonate grease composition comprises (1) less than 36% (by weight of the final grease) of overbased calcium sulfonate, and (2) calcium hydroxyapatite, calcium carbonate adduct, water Calcium oxide, calcium oxide, or any combination thereof, (3) one or more alkali metal hydroxides, (4) one or more conversion agents, and (5) one or more complexes And an acid. In yet another preferred embodiment, the final grease composition comprises about 0.005% to 0.5% alkali metal hydroxide.

  According to a preferred method of producing complex calcium sulfonate greases, alkali metal hydroxides are added to the other components before or after conversion. Most preferably, the method comprises the steps of: (a) mixing the overbased calcium sulfonate and the base oil; (b) adding and mixing one or more calcium-containing bases; (c) alkali metal hydroxide The substance is dissolved in water, the other components are added to the solution and mixed, and (d) one or more conversion agents are added and mixed, provided that they are added before conversion Step (c), including the water from step (c), (e) adding and mixing one or more complexing acids, and (f) combining some of these components until conversion occurs. And heating. Each component in step (b), step (c) and step (e) may be added before conversion and after conversion. Alternatively, one part may be added before conversion and another part may be added after conversion, the order relative to one another being unimportant in this embodiment of the method.

  According to yet another preferred embodiment, a complex calcium sulfonate grease is produced by reacting and mixing several compounds according to the outline of the process above, but converting the first part of water before conversion And the second part of water is added after conversion and the alkali metal hydroxide is dissolved in the first part of water or in the second part of water or both. According to yet another preferred embodiment, water is added as a conversion agent in at least two separate pre-conversion steps to provide a first addition of water as a conversion agent and a second addition of water as a conversion agent There is one or more temperature control steps, additional component addition steps, or combinations thereof, with the alkali metal hydroxide being the first or first addition of water as a conversion agent, conversion It dissolves in the second or later addition of water as an agent, or both.

  According to yet another preferred embodiment, the method of producing the complex calcium sulfonate grease comprises the steps outlined above, including the variants of the preferred embodiment, wherein the converting agent is water and at least one non-nonlimiting one. An aqueous converter is included, and there is one or more delay periods between the addition of water as a converter and the addition of at least a portion of the non-aqueous converter. Preferably, as described further below, the one or more delay periods are a temperature adjustment delay period or a holding delay period, or both. As used herein, "non-aqueous conversion agent" means any conversion agent other than water and includes conversion agents that may contain some water as a diluent or impurity.

  In any of the method embodiments described herein, all of the one or more complexing acids may be added before or after conversion. Alternatively, one or more portions of the complexing acids may be added prior to conversion of the complex calcium sulfonate grease and the remainder of one or more complexing acids may be added after conversion. All of the one or more calcium containing bases may be added before or after conversion. Alternatively, part of one or more calcium-containing bases may be added before conversion and the remainder may be added after conversion. Calcium hydroxyapatite, added calcium carbonate, added calcium hydroxide, or a combination thereof may be used as a calcium containing base to react with the complexing acid. Excess amount of calcium hydroxide (for example, calcium hydroxide 50% more than the stoichiometric amount required for reaction with all complexing acids) relative to the total amount of complexing acids used Is preferably not added prior to conversion.

  According to another preferred embodiment of the present invention, enhancement of thickener yield is achieved using an added alkali metal hydroxide, even when overbased calcium sulfonate is considered "poor". Alternatively, it is achieved by using it in combination with at least one delay period for at least part of the non-aqueous denaturing agent. Some overbased oil-soluble calcium sulfonates that are commercially available for the preparation of calcium sulfonate greases provide products with unacceptably low dropping points when the prior art calcium sulfonate technology is used . Such overbased oil-soluble calcium sulfonates are referred to throughout this application as "low quality" overbased oil-soluble calcium sulfonates. Overbased oil-soluble calcium that produces a grease with a higher dropping point (greater than 575 ° F.) when all ingredients and methods are the same except that a commercial batch of overbased calcium sulfonate is used Sulfonates are, for the purposes of the present invention, calcium sulfonates of "high" quality, and those producing greases with lower dropping points are considered to be "low" qualities for the purposes of the present invention. Several examples in this regard are provided in the '768 application, which is incorporated herein by reference. Although comparative chemical analysis of high and low quality overbased oil-soluble calcium sulfonates has been conducted, it seems that the exact reason for this low drop point problem has not been proven. Most commercial overbased calcium sulfonates are considered to be of high quality, but with or without high or low quality calcium sulfonates, the increase in thickener yield and higher drop point It is desirable to achieve both. Both the increase in thickener yield and the higher dropping point, when alkali metal hydroxides are used, especially in combination with the delayed addition method according to the invention, either high or low quality calcium sulfonates. It has been found that either can be achieved. In fact, when using at least some of the preferred embodiments of the present invention, the results of the examples using low quality overbased calcium sulfonate are better than those using high quality overbased calcium sulfonate Shows a thickener yield. In another preferred embodiment, when at least one of the non-aqueous conversion agents is a glycol (eg, propylene glycol or hexylene glycol), all glycols are added after at least one delay period (no addition to water ), Low quality calcium sulfonate is used.

  Manufactured according to the inventive parameters described herein, thickener yield and drop point properties are superior to those of the prior art greases, and a consistently high quality calcium sulfonate grease can be manufactured. The overbased calcium sulfonate complex greases prepared according to the preferred embodiment of the present invention are prepared according to NLGI No. A proportion of overbased oil-soluble calcium sulfonate having 2 grade consistency (or better, ie harder) and a dropping point of 575 ° F (or higher) is produced in an open container (without pressure) If it is about 10 to 45%. More preferably, the amount of overbased oil-soluble calcium sulfonate of the grease made according to the preferred embodiment of the present invention is more preferably at least about 10%, but made in an open container (without pressure) In this case, it is about 36% or less, more preferably about 30% or less, and most preferably about 22% or less. These thickener yield improvements can be achieved with both high and low quality overbased calcium sulfonates. If the grease is produced in a pressurized container, greater thickener yields can be achieved based on the components and process of the present invention. Most preferably, drop points above 650 F are achieved. The lower concentrations in the overbased oil-soluble calcium sulfonates achieved by the present invention are preferred as the cost of the grease is reduced. Other properties such as flowability and pumpability, especially at low temperatures, may also be favorably influenced by the improved thickener yields achieved according to the present invention.

  Without being bound by theory, it is believed that the addition of the alkali metal hydroxide results in a loop metathesis reaction. This affects the conversion process and the reaction with complexing acids, giving rise to these unexpected thickener yields and dropping points in complex calcium sulfonate greases. As discussed above, alkali metal hydroxides are known to be added to simple calcium soap greases, but not to overbased calcium sulfonate greases. This is because calcium hydroxide, which is commonly used in simple calcium soap greases, has low water solubility and is a weak base compared to more water soluble sodium hydroxide. To this end, a small amount of sodium hydroxide dissolved in the added water is combined with a soap-forming fatty acid (usually a mixture of 12-hydroxystearic acid or 12-hydroxystearic acid and a non-hydroxylated fatty acid such as oleic acid) It is said to react quickly and form sodium soap. This rapid response is considered to "break off" in the manufacture of simple calcium soap greases. However, once all that has happened, once a small amount of sodium hydroxide has reacted with a small amount of fatty acid, the remaining reactants (hydroxide as if sodium hydroxide had not been added before) Calcium and most of the remaining fatty acids react. Unreacted calcium hydroxide is still present and will still need to react with the remaining unreacted fatty acids to form a calcium soap thickener.

  A more likely explanation is that a small amount of sodium soap which is formed rapidly reacts further with calcium hydroxide in a metathesis reaction where sodium and calcium exchange. Sodium soap becomes calcium soap and calcium hydroxide becomes sodium hydroxide. This reaction is facilitated by the high water solubility of sodium hydroxide and the very low water solubility of calcium soap to sodium soap. This will allow a small amount of sodium hydroxide to be "regenerated" to react more rapidly with more fatty acids. Thereafter, the metathesis reaction can occur again to produce more calcium soap. This loop reaction sequence continues until all the calcium hydroxide has reacted to form a calcium soap thickener. The loop of this reaction sequence is shown below.

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

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

  The NaOH produced in reaction 2 becomes the reaction product of reaction 1.

  Unlike simple calcium soap greases, the direct reaction of calcium containing bases (e.g. calcium hydroxide) with fatty acids has not been a problem in producing calcium sulfonate complex greases. The reaction takes place very easily, presumably due to the high surfactant activity / dispersability of the large amounts of calcium sulfonate present, which is why the addition of alkali metal hydroxide is either taught or suggested in the prior art calcium sulfonate grease technology That's why not. In fact, due to the high surface activity / dispersability of the large amount of calcium sulfonate present during the reaction of the complexing acid with the calcium-containing base, the person skilled in the art can Would not expect significant benefits to be obtained by the addition of Nevertheless, the reaction of alkali metal hydroxides appears to have an unexpected beneficial effect on the thickener yield of calcium sulfonate greases. The addition of an alkali metal hydroxide is combined with the delayed addition procedure of at least part of the non-aqueous conversion agent and the reaction with complexing acids using calcium hydroxyapatite and / or calcium carbonate as the calcium containing base In the case, the benefits are even greater. Preferred embodiments of the composition and method of the present invention add an alkali metal hydroxide as a component of a complex calcium sulfonate grease, or in combination therewith, to complex (1) calcium hydroxyapatite and / or calcium carbonate Use as a calcium-containing base to be reacted with an acid and / or (2) one or more delay times between the addition of water as conversion agent and the addition of at least part of the non-aqueous conversion agent Use.

[Complex calcium sulfonate grease composition]
According to one preferred embodiment of the invention, the complex calcium sulfonate grease composition comprises the following components: (1) less than 45% (by weight of the final grease) overbased calcium sulfonate; (2) Calcium hydroxyapatite, added calcium carbonate, calcium hydroxide, calcium oxide, or any combination thereof; and (3) alkali metal hydroxides. More preferably, the complex calcium sulfonate grease further comprises (4) one or more conversion agents; and (5) one or more complexing acids. According to another preferred embodiment, the one or more conversion agents comprise water and at least one non-aqueous conversion agent such as propylene glycol or hexylene glycol. If desired, the grease composition may comprise a facilitating acid. Such promoting acids aid in the formation of grease structures. Some or all of the specific components, including the conversion agent and the calcium-containing base, may not be included in the final product due to evaporation, volatilization or reaction with other components during manufacture.

  Highly persalted oil-soluble calcium sulfonates used in these embodiments of the present invention are disclosed in U.S. Patent 4,560,489, U.S. Patent 5,126,062, U.S. Patent 5,308,514 and It may be the general one described in the prior art, such as U.S. Pat. No. 5,338,467. Highly overbased oil-soluble calcium sulfonates may be manufactured in situ according to such known methods and may be purchased as commercial products. Such highly overbased oil-soluble calcium sulfonates will have a total base number (TBN) value of 200 or more, preferably 300 or more, most preferably about 400 or more. Commercially available overbased calcium sulfonates of this type include Hybase C 401 supplied by Chemtura USA Corporation; Syncal OB 400 and Syncal OB 405-WO supplied by Kimes Technologies International Corporation; Lubrizol 75 GR supplied by Lubrizol Corporation. Lubrizol 75NS, Lubrizol 75P, and Lubrizol 75WO are included, but are not limited thereto. Overbased calcium sulfonate contains about 28% to 40% dispersed amorphous calcium carbonate by weight ratio of overbased calcium sulfonate, which is a crystalline calcium carbonate in the process of producing calcium sulfonate grease Converted to The overbased calcium sulfonate also contains about 0% to 8% residual calcium oxide or calcium hydroxide by weight of the overbased calcium sulfonate. The majority of commercially available overbased calcium sulfonates will also contain about 40% base oil as a diluent so that the overbased calcium sulfonates do not become difficult to handle and treat. The amount of base oil in the overbased calcium sulfonate may make it unnecessary to add additional base oil (as a separate component) prior to conversion to achieve an acceptable grease. The overbased calcium sulfonates used may be of high or low quality, as defined herein and in the '768 application.

  The amount of highly overbased oil soluble calcium sulfonate in the final complex grease according to embodiments of the present invention may vary but is generally 10 to 45%. Preferably, the amount of highly overbased oil-soluble calcium sulfonate in the final complex grease according to embodiments of the present invention is less than or equal to about 36% when manufactured in an open container (without pressure), more preferably Not more than about 30%, most preferably not more than about 22%. The proportion achievable when made in pressurized containers is even smaller.

  Any petroleum based naphthenic or paraffinic mineral oil commonly used and widely known in grease manufacture may be used as the base oil of the present invention. The base oil is added as needed. Most of the commercially available overbased calcium sulfonates will already contain about 40% base oil as a diluent to avoid the time when the overbased sulfonates become too thick to handle easily, so immediately after conversion Depending on the desired grease consistency and the desired consistency of the final grease, it is not 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 (PAOs), diesters, polyol esters, polyethers, alkylated benzenes, alkylated naphthalenes, and silicone oils. As can be appreciated by those skilled in the art, synthetic base oils can have adverse effects if present during the conversion process. In such cases, those synthetic base oils are not added initially, but are added to the grease making process in a process where adverse effects are eliminated or minimized, such as after conversion. Naphthenic or paraffinic mineral base oils are preferred in view of their low cost and availability. The total amount of base oil added (including those initially added and those later added to the grease treatment to achieve the desired consistency) is generally 30% to 70%, preferably 45%, based on the final weight of the grease To 75%, most preferably 50% to 70%. Typically, the amount of base oil added as a separate component increases as the amount of overbased calcium sulfonate decreases. As will be appreciated by those skilled in the art, combinations of different base oils as described above may also be used in the present invention.

  Water is added to the preferred embodiment of the present invention as one converting agent. One or more other non-aqueous conversion agents are also preferably added in these embodiments of the invention. Non-aqueous conversion agents include any conversion agent other than water, such as alcohols, ethers, glycols, glycol ethers, glycol polyethers, carboxylic acids, inorganic acids, organic nitrates, or active hydrogens or Included are any other compounds that contain any of the mutagenic hydrogens. Non-aqueous conversion agents also include those agents that contain some water as a diluent or impurity. While they may be used as non-aqueous conversion agents, methanol or isopropyl alcohol or other low molecular weight (ie It is preferred not to use alcohols, such as alcohols, which are more volatile. Based on the final weight of the grease, the total amount of water added as a converting agent is 1.5% to 10%, preferably 2.0% to 5.0%, most preferably 2.2% to 4.5%. %. Additional water may be added after conversion. Also, if the conversion is carried out in an open vessel at a temperature high enough to evaporate a significant amount of water during conversion, additional water may be added to replace the lost water. The total amount of non-aqueous conversion agent (s) added is 0.1% to 5%, preferably 0.3% to 4%, most preferably 0.5%, based on the final weight of the grease To 2.0%. Typically, the amount of non-aqueous converting agent used decreases as the amount of overbased calcium sulfonate decreases. Depending on the conversion agent used, some or all of them may be removed by volatilization during the manufacturing process. Particularly preferred are low molecular weight glycols such as hexylene glycol and propylene glycol. It should be noted that some of the conversion agents may also serve as complexing acids to produce a calcium sulfonate complex grease according to one embodiment of the invention described below. Such materials provide both conversion and complexing functions simultaneously.

  Although not required, according to another embodiment of the present invention, a facilitating acid may be added to the mixture prior to conversion. In general, a suitable accelerating acid such as an alkyl benzene sulfonic acid having an alkyl chain length of 8 to 16 carbons may help to promote efficient grease structure formation. Most preferably, the alkyl benzene sulfonic acid comprises mixed alkyl chain lengths that are mostly about 12 carbons in length. Such benzenesulfonic acid is generally referred to as dodecylbenzenesulfonic acid (DDBSA). Commercially available benzenesulfonic acids of this type include JemPak GK Inc. 1298 Sulfonic Acid, Calsoft LAS-99 supplied by Pilot Chemical Company, and Biosoft S-101 supplied by Stepan Chemical Company. When benzenesulfonic acid is used in the present invention, the benzenesulfonic acid is 0.50% to 5.0%, preferably 1.0% to 4.0%, most preferably 1 based on the final weight of the grease. .3% to 3.6% amount added before conversion. When the calcium sulfonate is produced in situ using an alkyl benzene sulfonic acid, the accelerating acid added in this embodiment is added to the acid necessary for producing the calcium sulfonate.

  In a preferred embodiment of the calcium sulfonate grease composition according to the invention, one or more complexing acids, one or more calcium-containing bases, and one or more alkali metal hydroxides are also added as components. . The calcium-containing base may comprise calcium hydroxyapatite, calcium carbonate addition, calcium hydroxide addition, calcium oxide addition, or a combination of one or more thereof. In this embodiment, calcium hydroxyapatite used as a calcium-containing base to react with the complexing acid may be added before conversion, after conversion, a part is added before conversion and a part is converted It may be added later. Most preferably, the calcium hydroxyapatite is finely divided at an average particle size of about 1 to 20 microns, preferably about 1 to 10 microns, most preferably about 1 to 5 microns. In addition, calcium hydroxyapatite will have abrasive contaminants such as silica and alumina at a level that is sufficiently pure so as not to significantly affect the abrasion resistance properties of the resulting grease. Ideally, calcium hydroxyapatite should be either food grade or USP grade for best results. The amount of calcium hydroxyapatite added is 1.0% to 20%, preferably 2% to 15%, most preferably 3% to 10%, based on the total weight of the grease, but if necessary Further addition may be made after conversion and all reactions with the complexing acid are complete.

  According to another embodiment of the present invention, calcium hydroxyapatite may be added to the above components in an amount insufficient to fully react with the complexing acid. In this embodiment, finely divided calcium carbonate, as an oil-insoluble solid calcium-containing base, preferably completely reacts with the portion not neutralized by calcium hydroxyapatite in any complexing acid added thereafter, prior to conversion. It may be added in an amount sufficient to neutralize.

  According to another embodiment, calcium hydroxyapatite may be added to the above components in an amount insufficient to react completely with the complexing acid. In this embodiment, finely divided calcium carbonate and / or calcium oxide, as an oil-insoluble solid calcium-containing base, is preferably co-added calcium hydroxy in any complexing acid subsequently added before conversion. It may be added in an amount sufficient to completely react and neutralize the portion not neutralized by apatite. In this embodiment, calcium hydroxide and / or calcium oxide represents no more than 75% of the hydroxide equivalent basicity given by the total amount of calcium hydroxyapatite added, calcium hydroxide and calcium oxide. Is preferred. In another embodiment, calcium carbonate may be added along with calcium hydroxyapatite, calcium hydroxide and / or calcium oxide, and calcium carbonate may be added before 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 added complexing acid, calcium carbonate is more than sufficient to neutralize the remaining complexing acid Preferably it is added in amounts.

  In these embodiments of the invention, the added calcium carbonate used as the calcium-containing base, alone or in combination with other calcium-containing bases, is about 1 to 20 microns, preferably about 1 to 10 microns, most preferably It is finely divided with an average particle size of about 1 to 5 microns. Furthermore, it is preferred that the added calcium carbonate be crystalline calcium carbonate (most preferably calcite) of sufficient purity, so low levels of silica and alumina that they do not significantly affect the wear resistance of the resulting grease. Such polishing contaminants. Ideally, calcium carbonate should be either food grade or USP grade for best results. The amount of calcium carbonate added is 1.0% to 20%, preferably 2.0% to 15%, and most preferably 3.0% to 10%, based on the final weight of the grease. These amounts are added as a separate component in addition to the amount of dispersed calcium carbonate contained in the overbased calcium sulfonate. According to another preferred embodiment of the present invention, the added calcium carbonate is added prior to conversion as the only added calcium-containing base component to react with the complexing acid. Additional calcium carbonate may be added to any of the simple or complex grease embodiments of the invention after conversion, and in the case of complex grease may be added after reaction with all complexing acids is complete. . However, as used herein, calcium carbonate added is calcium carbonate, which is one or the only calcium-containing bases that are added prior to conversion and react with the complexing agent when producing the complex grease of the present invention. It is called.

  The added calcium hydroxide and / or calcium oxide added before and after conversion, according to another embodiment, is about 1 to 20 microns, preferably about 1 to 10 microns, most preferably about 1 to 5 microns Finely divided by average particle size. Furthermore, calcium hydroxide and calcium oxide are of sufficient purity and have abrasive contaminants such as silica and alumina at levels that are low enough not to significantly affect the wear resistance properties of the resulting grease. Ideally, calcium hydroxide and calcium oxide should be either food grade or USP grade for best results. The total amount of calcium hydroxide and / or calcium oxide is 0.07% to 1.20%, preferably 0.15% to 1.00%, most preferably 0.18% to 0.1%, based on the total weight of the grease. It is 0.80%. These amounts are added as a separate component in addition to the amount of residual calcium hydroxide or calcium oxide contained in the overbased calcium sulfonate. Most preferably, an excess of calcium hydroxide relative to the total amount of complexing acid used is not added prior to conversion. According to yet another embodiment, it is not necessary to add calcium hydroxide or calcium oxide to react with the complexing acid, either an added calcium carbonate or calcium hydroxyapatite is added for such reaction It may be used as the only calcium containing base and may be used in combination for such reactions.

  The added alkali metal hydroxide comprises sodium hydroxide, lithium hydroxide, potassium hydroxide, or a combination thereof. Most preferably, sodium hydroxide is used as the 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%, most preferably about 0% by weight of the final grease product. .02% to 0.20%. Similar to the calcium-containing base, the alkali metal hydroxide reacts with the complexing acid to form an alkali metal salt of the complexing acid present in the final grease product. The preferred amount indicated here is the amount added as a feed component to the weight of the final grease product, even in the absence of alkali metal hydroxide in the final grease. According to one preferred embodiment, the alkali metal hydroxide is dissolved in water before being added to the other components. The water used to dissolve the alkali metal hydroxide may be water used as a conversion agent or water added after conversion. Most preferably, the alkali metal hydroxide is dissolved in water prior to addition to the other ingredients, but may be added directly to the other ingredients without first dissolving in water.

  The complexing acid used in these embodiments will comprise at least one, preferably two or more of long chain carboxylic acid, short chain carboxylic acid, boric acid and phosphoric acid. Acetic acid and other carboxylic acids may be used as converting agents or complexing acids, or both, depending upon when they are added. Similarly, some complexing acids (such as 12-hydroxystearic acid in the '514 and' 467 patents) may be used as conversion agents. The total amount of complexing acid added is preferably 2.8% to 11% by weight of the final grease. Long chain carboxylic acids suitable for use in the present invention include aliphatic carboxylic acids having at least 12 carbon atoms. Preferably, the long chain carboxylic acid comprises an aliphatic carboxylic acid having at least 16 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 the grease. is there.

  Short-chain carboxylic acids suitable for use in accordance with the present invention include aliphatic carboxylic acids having up to 8, preferably up to 4 carbon atoms. Most preferably, the short chain carboxylic acid is acetic acid. The amount of 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. is there. Also suitable for use are any compounds which can be expected to react with water or other components used to produce the grease according to the invention to form long chain carboxylic acids or short chain carboxylic acids. For example, using acetic anhydride will produce acetic acid to be used as a complexing acid in reaction with water present in the mixture. Similarly, using methyl 12-hydroxystearate will produce 12-hydroxystearic acid for use as a complexing acid in reaction with water present in the mixture. Alternatively, if sufficient water is not present in the mixture, additional water may be added to the mixture and reacted with those components to form the necessary complexing acid.

  When boric acid is used as the complexing acid in this embodiment, it is 0.3% to about 4.0%, preferably 0.5% to 3.0%, and most preferably, based on the final weight of the grease. Add an amount of 0.6% to 2.0%. The boric acid may be added first dissolved or suspended in water or without water. Preferably, boric acid will be added while the water remains in the manufacturing process. Alternatively, any of the known inorganic borates may be used in place of boric acid. Similarly, borated amine, borated amide, borated ester, borated alcohol, borated glycol, borated ether, borated epoxide, borated urea, borated carboxylic acid, borated sulfonic acid, borated epoxide, borated epoxide Existing borated organic compounds, such as oxidized peroxides, may be used instead of boric acid. When phosphoric acid is used as the complexing acid, it is 0.4% to 4.0%, preferably 0.6% to 3.0%, most preferably 0.8% to 2%, based on the final weight of the grease. Add 0% amount. The percentages of the various complexing acids described herein refer to the pure active compounds. If any of these complexing acids are available in diluted form, they may still be suitable for use in the present invention. However, the proportion of such diluted complexing acid may need to be adjusted to take the specified proportion of the actual active ingredient, taking into account the dilution factor.

  Other additives generally recognized in the grease manufacturing art can also be added to either the simple grease embodiment or the complex grease embodiment of the present invention. Such additives include rust and corrosion inhibitors, metal deactivators, metal passivators, antioxidants, extreme pressure additives, antiwear additives, chelating agents, polymers, tackifiers Agents, dyes, chemical markers, odorants, and evaporable solvents. The latter category may be particularly useful in producing open gear lubricants and braided wire rope lubricants. It should be understood that the inclusion of such optional additives is still within the scope of the present invention. The proportions of the components are based on the final weight of the finished grease, unless otherwise indicated, but that amount of components may not be present in the final grease product by reaction or volatilization.

[Method for producing complex calcium sulfonate grease using alkali metal hydroxide]
The calcium sulfonate grease composition is preferably manufactured according to the process of the present invention as described herein. In one preferred embodiment, the method comprises the steps of: (1) mixing the overbased calcium sulfonate and the base oil; (2) dissolving the alkali metal hydroxide in water and mixing with the other components ( 3) adding and mixing one or more types of calcium-containing bases, and (4) adding and mixing one or more types of conversion agents, in the case where they are added before conversion, c) heating the process, which may include water, (5) adding and mixing one or more complexing acids, and (6) heating some combination of these components until conversion occurs. And a process. In this preferred embodiment, the addition of water as a conversion agent (if water is used as a conversion agent) and the addition of any portion of any non-aqueous conversion agent (if a non-aqueous conversion agent is used) There is no delay between In another preferred embodiment, the process of the invention comprises the same steps as these, but the conversion agent comprises water and at least one non-aqueous conversion agent, the addition of water before conversion, It differs in that there is one or more delay periods between the addition of at least a portion of one or more other non-aqueous conversion agents. For ease of reference, the term "alkali addition method" refers to all the preferred embodiments of the process according to the invention, wherein the alkali metal hydroxide is added without delayed addition of the non-aqueous conversion agent. Used to describe. And the term "alkali / delayed addition method" means that both alkali metal hydroxides are added, the addition of water as a conversion agent and the addition of at least part of a non-aqueous conversion agent. It is used to describe all the preferred embodiments of the method according to the invention, such that there is at least one delay period in between. The term "delayed addition method" is used to denote the delayed non-aqueous converter method of the '476 application without alkali metal hydroxide addition.

  In both the preferred alkali addition method and the alkali / delayed addition method, each component in step (2), step (3) and step (5) may be added before conversion, after conversion, or part of Before, another part may be added after conversion. If desired, an accelerating acid may be added, preferably mixed with the components prior to conversion. If an accelerating acid is used, it is also preferred to add it to the mixture before adding the alkali metal hydroxide. Alternatively, the alkali metal hydroxide can be added to the other components without first dissolving in water, but it is most preferable to pre-dissolve in water. Most preferably, the specific components and amounts used in the present method are based on the preferred embodiments of the compositions described herein.

  The addition of the components of step (2), step (3), and step (5) in any of the preferred alkali addition method and alkali / delayed addition method, the order with respect to each other, step (1) and step (4) The order for the components of) and the order for the timing of heating are not important. However, it is preferred, as described below, to add some components before and / or after the other components and / or before or after heating. Furthermore, the order of addition of conversion agents is crucial in the alkali / delayed addition method, as described further below.

  According to yet another preferred embodiment of the alkali addition method and the alkali / delayed addition method, the complex calcium sulfonate grease is produced by reacting and mixing certain compounds according to the above steps, but before the conversion One part is added as a conversion agent, the second part of water is added after conversion, and the alkali metal hydroxide differs in that it dissolves in the first part of water or in the second part of water, or both. According to yet another preferred embodiment of the alkali addition method and the alkali / delay addition method, water is added as a conversion agent in at least two separate pre-conversion steps, and the first addition of water as a conversion agent and the conversion agent There is one or more temperature control steps, the addition of further components, or a combination thereof, between the second addition of water as The alkali metal hydroxide is dissolved in the first or first addition of water as a conversion agent, or the second or subsequent addition of water as a conversion agent, or both.

According to yet another preferred embodiment of the alkali addition method and the alkali / lag addition method, at least a portion of the complexing acid is added prior to heating. According to another preferred embodiment, all complexing acids are added prior to heating. According to yet another preferred embodiment of the alkali addition method and the alkali / delay addition method, calcium carbonate is added prior to the complexing acid when it is added as an addition calcium-containing base that reacts with the complexing acid. . According to yet another preferred embodiment of the alkali addition method and the alkali / delay addition method, calcium hydroxyapatite, added calcium hydroxide and added calcium carbonate are all used as calcium-containing bases which react with complexing acids. In this embodiment, where the complexing acid is added prior to conversion, calcium hydroxyapatite and at least a portion of the calcium hydroxide are added prior to adding any complexing acid to Most preferably, calcium carbonate is added after at least a portion has been added. According to another preferred embodiment of the alkali addition method and the alkali / delay addition method, the water in which the alkali metal hydroxide is dissolved is part of the complexing acid after addition of the calcium-containing base and / or before conversion. Is added after being added. According to another preferred embodiment, the water having dissolved alkali metal hydroxide (or separately added alkali metal hydroxide) is added prior to adding at least a portion of one or more complexing acids. Is added to

In some other embodiments of the alkali addition method and the alkali / delayed addition method, the steps are the same as the previous embodiment, but step (3) (addition of a calcium-containing base) is one of the following steps: (A) mixing finely powdered calcium hydroxyapatite before conversion as the only calcium-containing base to be added; (b) finely powdered calcium hydroxy according to one embodiment Mixing the apatite and calcium carbonate in an amount sufficient to completely react and neutralize the complexing acid to be added thereafter;
(C) mixing fine calcium hydroxyapatite and calcium hydroxide and / or calcium oxide in an amount sufficient to completely react and neutralize the complexing acid to be added later The calcium hydroxide and / or calcium oxide is preferably in an amount of 75% or less of the hydroxide equivalent basicity given by the total amount of calcium hydroxide and / or calcium oxide and calcium hydroxyapatite added. (D) mixing the added calcium carbonate after conversion according to another embodiment of the present invention; (e) converting calcium hydroxyapatite after conversion according to still another embodiment of the present invention Mixed in an amount sufficient to completely react and neutralize any complexing acid added after conversion Step (f) Fine powder calcium hydroxide is mixed as a non-oil-soluble solid calcium-containing base before conversion, and then in an amount insufficient to sufficiently react with and neutralize the complexing acid added thereafter. In the step of mixing calcium apatite and calcium hydroxide and / or calcium oxide, calcium hydroxide and / or calcium oxide is preferably added calcium hydroxide and / or calcium oxide and calcium hydroxyapatite in total. Calcium hydroxyapatite and calcium hydroxide in any complexing acid subsequently added, which is present in an amount of 75% or less of the hydroxide equivalent basicity given the total amount of Portions not neutralized by calcium and / or calcium oxide and complete Adding in a sufficient amount to react and neutralize, a process.

  In 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 portion of one or more other non-aqueous conversion agents. The first delay period starts after the first addition of water as a converting agent. If additional water is added prior to conversion to compensate for evaporation during the manufacturing process, those additions are not used to restart or determine the lag period, only the first addition departs for the lag period determination Used as a point. It is most preferable that the one or more delay periods (the time between the pre-conversion addition of water and the addition of at least a portion of the non-water conversion agent) be a temperature adjustment delay period or a holding delay period or both. . The delay periods may include multiple temperature adjustment delay periods and multiple hold delay periods.

  For example, the first temperature adjustment delay period is the time after the water has been added that is required to change the temperature of the mixture (typically by heating) to the desired temperature or temperature range (first temperature) . The first holding delay period is the time during which the mixture is held at the first temperature. The second temperature adjustment delay period is the time after the first holding delay period required to heat or cool the mixture to another temperature or temperature range (second temperature). If another component (eg, a complexing acid) is added after reaching the first temperature, but there is no delay period before the heating or cooling is continued to the second temperature after the temperature is reached, The delay period may be the time after the first temperature adjustment delay period to heat or cool the mixture to another temperature or temperature range (second temperature). The second holding delay time is the time during which the mixture is held at the second temperature. The additional temperature adjustment delay period and the holding delay period (ie, the third temperature adjustment delay period) follow the same pattern. The first temperature may be ambient temperature or elevated temperature. The subsequent temperature may be higher or lower than the previous temperature. The final pre-conversion temperature will typically be about 190 ° F. to 220 ° F., or up to 230 ° F., as the temperature at which conversion in the open kettle takes place. Although the final pre-conversion temperature may be less than 190 F, such process conditions will usually significantly increase conversion time and reduce thickener yield. The final pre-conversion temperature and temperature range at which conversion occurs may be different in a closed vessel. Any combination of temperature adjustment delay periods and / or hold delay periods may be used. Most preferably, the mixture of components prior to conversion is heated to a temperature or temperature range during at least one or each delay period.

  Typically, the holding delay period is followed by a temperature adjustment delay period, ie, the holding delay period precedes the temperature adjustment delay period, and vice versa, but two holding delay periods are consecutive or two temperature adjustment periods. May be continuous. For example, the mixture may be held at ambient temperature for 30 minutes (first holding delay time) before adding one non-aqueous conversion agent, and also before adding the same or different non-aqueous conversion agent. It may continue to be held at ambient temperature for an additional hour (second holding delay time). Furthermore, after heating or cooling the mixture to the first temperature, a non-aqueous conversion agent may be added (first temperature control period). The mixture is then heated or cooled to a second temperature, after which the same or different non-aqueous conversion agent is added (second temperature adjustment period, no intermediate holding period). Furthermore, it is not necessary to add a portion of the non-aqueous conversion agent after each delay period, but the delay period before or between additions may be omitted. For example, the mixture may be heated to a temperature (first temperature adjustment delay period) and held at that temperature for a period of time (first retention delay period) before adding any non-aqueous conversion agent.

  If the non-aqueous conversion agent or part thereof is added immediately after reaching the temperature or temperature range, there is no retention delay time for that particular temperature and part of the non-aqueous conversion agent. However, if another portion is added after holding for a period of time at that temperature or temperature range, there is a retention time delay for that temperature and that portion of the non-aqueous conversion agent. A portion of one or more non-aqueous conversion agents may be added after any temperature adjustment delay period or holding delay period, another portion of the same or different non-aqueous conversion agent may be another temperature adjustment delay It may be added after a period or hold delay period. Typically, the duration of each temperature adjustment delay period is about 30 minutes to 24 hours, or more typically about 30 minutes to 5 hours. However, it will be appreciated by those skilled in the art that the duration of any temperature adjustment delay period will vary depending on the size of the grease batch, the equipment used to mix and heat the batch, and the temperature difference between the start and end temperatures. It will be clear to you.

  Various variations of the delay period may also be used in various preferred embodiments of the alkali / delayed addition method. For example, each of the following is a separate preferred embodiment: (a) at least a portion of the non-aqueous conversion agent is added (substantially simultaneously) with the first addition of water, the same non-aqueous conversion agent and / or Or at least another portion of a different non-aqueous conversion agent is added after the at least one delay period; (b) not adding the non-aqueous conversion agent substantially simultaneously with the water, at least one delay time being non- (C) at least a portion of the non-aqueous conversion agent is a final pre-conversion temperature range of the mixture between about 190 F and 230 F (the temperature range where conversion occurs in an open vessel. Closed). If done in a vessel, the mixture is heated after being heated to a suitable temperature range where conversion takes place); (d) at least one non-aqueous converting agent is a glycol (eg propylene glycol) Or When it is xylene glycol), part of the glycol is added substantially simultaneously with water, another part of the glycol and all other optional non-aqueous converting agents are added after at least one delay period (E) If acetic acid is added prior to conversion, it is added substantially simultaneously with the water, and another (different) non-aqueous transconversion agent is added after the delay period; (f) 1 Or at least a portion of the plurality of non-aqueous conversion agents is added at the end of the one or more delay periods, and another portion of the same and / or different non-aqueous conversion agents may be added to the earlier one or more delays. (G) all one or more non-aqueous conversion agents are added at the end of one or more delay periods.

  According to one preferred embodiment of the alkaline / delayed addition method, all or part of the non-aqueous conversion agent is after the delay period (as opposed to the continuous addition over the delay period as described below , All at once in batch mode. However, it should be noted that in large scale or commercial scale practice it will take time to complete the batch addition of such non-aqueous converter to the grease batch due to the amount of material involved. In batch addition, the time taken to add the non-aqueous conversion agent to the grease mixture is not considered a lag period. In that case, the delay before adding the non-aqueous conversion agent or a portion thereof ends at the beginning of the batch addition of the non-aqueous conversion agent. In another preferred embodiment, at least a portion of one non-aqueous conversion agent is added continuously during the delay period (either a temperature adjustment delay period or a holding delay period). Such continuous additions may be non-aqueous conversion agents by repetitive, discrete, incremental additions at substantially stable flow rates or during temperature adjustment delay periods, holding delay periods, or both. May be added slowly. In that case, the time required to completely add the non-aqueous conversion agent is included in the delay period which ends when the addition of the non-aqueous conversion agent is completed. According to yet another preferred embodiment of the alkali / delayed addition method, at least a portion of one non-aqueous conversion agent is added in batch mode after the delay period and at least another of the same or different non-aqueous conversion agents. Some are added continuously during the delay period. According to another preferred embodiment of the alkali / delayed addition method, no alcohol is used as a non-aqueous conversion agent.

  The delay period within the scope of the present invention may include a holding delay period without heating (for example, if the mixture is held at ambient temperature during the first holding delay period before heating), but as a conversion agent A short time of less than 15 minutes without heating during that period between the addition of water and the addition of all non-aqueous conversion agents is a "delay" or "delay period" as used herein. "is not. For purposes of the present invention, the delay for adding any or all of the non-aqueous conversion agent without heating during the delay period should be at least about 20 minutes, more preferably at least about 30 minutes. is there. The interval of less than 20 minutes between the addition of water and the addition of a portion of the non-aqueous conversion agent is then heated to less than 20 minutes, followed by a longer holding delay period or subsequent heating If, after that, part of the non-aqueous conversion agent is added or part or all of the different non-aqueous conversion agents are added, the “delay period” within the scope of the present invention is concerned. In that case, the first short interval is not a "delay period", but the subsequent longer holding delay or temperature adjustment delay prior to the addition of the non-aqueous conversion agent is the holding delay period or temperature adjustment delay period for the purposes of the present invention. It is. Furthermore, all or part of one or more non-aqueous conversion agents may be added slowly during one or more temperature control delay periods or holding delay periods, or both. This slow addition may comprise substantially continuous addition of the non-aqueous converter during the delay period or repeated incremental additions during the delay period.

  Furthermore, if acetic acid or 12-hydroxystearic acid is added prior to conversion, these acids will play a dual role as both a converting agent and a complexing acid. When these acids are added along with other non-aqueous converting agents that are more active (for example, glycols), the acid mainly plays the role of a complexing acid, and the more active agent thinks that it mainly plays the role of a converting agent. Can be Thus, if acetic acid or 12-hydroxystearic acid is added prior to conversion with the more active converting agent, the elapsed time between the addition of water and the addition of any portion of acetic acid or 12-hydroxystearic acid is It is not considered to be a delay as the term is used herein. In that case, only the temperature adjustment delay period or holding delay period between the preconversion addition of water and the preconversion addition of any portion of the other non-aqueous conversion agent is considered as the delay for the purpose of the present invention. If acetic acid or 12-hydroxystearic acid or a combination thereof is the only non-aqueous converting agent used, the pre-conversion addition of water and the pre-conversion addition of any portion of acetic acid or 12-hydroxystearic acid The temperature adjustment delay period or holding delay period between them is the delay for the purpose of the present invention.

  One preferred embodiment of the alkali / delayed addition method according to the present invention comprises the following steps: (1) In a suitable grease making container, a high excess containing water as a conversion agent and dispersed amorphous calcium carbonate Basic oil-soluble calcium sulfonate, (if necessary) optionally suitable amounts of a suitable base oil, one or more alkali metal hydroxides and optionally at least one non-aqueous Mixing with at least a portion of the conversion agent to form a first mixture; (2) mixing or stirring while maintaining the first mixture within a temperature or temperature range during one or more delay periods; And / or adjusting the temperature of the first mixture to heat or cool it to another temperature or temperature range; (3) optionally at least a portion of one or more non-aqueous conversion agents One or more late Mixing with the first mixture after or during the period to form a second mixture; (4) the first mixture (the second mixture if a non-aqueous conversion agent is added in step (3)) Heating to a conversion temperature (preferably in the range of 190F to 230F, and in the case of an open vessel, higher than the typical range of 190F to 220F) during the last of one or more delay periods (5) mixing all or one or more (if any) remaining non-aqueous converting agents after (5) or during the step of forming the third mixture; (5) Step (6) temperature in the conversion temperature range (preferably 190F to 230F in the case of an open container) until the amorphous calcium carbonate contained in the overbased calcium sulfonate is converted to very finely divided crystalline calcium carbonate Keep the Converting the third mixture by continuing mixing; (7) mixing one or more calcium-containing bases; (8) mixing an accelerating acid as required; and (9) one or more Mixing the appropriate complexing acid of the species. This process results in the preferred complex calcium sulfonate grease. Step (7) may be performed before or after conversion, or part or all of one or more calcium-containing bases may be added before conversion, a part of one or more calcium-containing bases Or all may be added after conversion. Step (8) may be performed at any time prior to conversion. Step (9) may be performed before or after conversion. Alternatively, part or all of one or more complexing acids may be added before conversion, and part or all of one or more complexing acids may be added after conversion. Most preferably, this alkali / delayed addition method is carried out in an open vessel but may also be carried out in a pressure vessel. Most preferably, one or more alkali metal hydroxides are dissolved in the water used as conversion agent before adding them in step (1). Alternatively, the alkali metal hydroxide may be omitted in step (1), dissolved in water and the solution may be added before or after conversion.

  In any preferred embodiment of the alkali / delayed addition method described herein, any portion of the non-aqueous conversion agent added in step (1), step (3), and / or step (5) May be the same non-aqueous conversion agent as added in a separate step and may be different from any non-aqueous conversion agent added in a separate step. If at least a portion of the at least one non-aqueous conversion agent is added after a delay period (in step (3) or step (5)), another portion of the same non-aqueous conversion agent and / or different At least a portion of one or more non-aqueous conversion agents may be added in any combination of step (1), step (3) and / or step (5). According to another preferred embodiment of the alkali / delayed addition method, all one or more of the one or more non-aqueous conversion agents are mixed after the delay period of step (5), to obtain step (1) or ( In 3) nothing is added. According to another preferred embodiment of the alkali / delayed addition method, at least a portion of one or more non-aqueous conversion agents are added together with the first mixture in step (1) prior to the delay, same or different At least a portion of the non-aqueous conversion agent is added in step (3) and / or step (5). In another preferred embodiment of the alkaline / delayed addition method, the non-aqueous conversion agent is not added with the first mixture, and at least a portion of the one or more non-aqueous conversion agents comprises steps (3) and (5). Is added. In another preferred embodiment of the alkali / delayed addition method, at least a portion of one or more non-aqueous conversion agents is added after or during one delay period in step (3) and is the same or different At least a portion of the aqueous converting agent is added after or during another delay period (the second delay period of step (3) and / or the final delay period of step (5)). According to another preferred embodiment of the alkali / delayed addition method, at least a portion of one or more non-aqueous conversion agents is added after the one or more delays of step (3); After the final delay period of), the non-aqueous conversion agent is not added.

  The sequence of steps (2) to (6) of producing the complex grease is an important feature of the present invention with respect to the embodiment including the alkali / delayed addition method. Several other features of the process are not important to obtain the preferred calcium sulfonate grease composition according to the present invention. For example, the order in which multiple calcium-containing bases are added to one another is not important. Also, the temperature at which water and calcium-containing base as conversion agents are added is not critical to obtain an acceptable grease, but temperatures between 190 F and 200 F (if conversion takes place when done in a closed vessel) Preferably, they are added prior to reaching other temperature ranges). If two or more complexing acids are used, the order in which they are added either before or after conversion is also usually not critical.

  Another preferred embodiment of the alkali / delayed addition method comprises optionally water, less than 45% of an overbased calcium sulfonate containing one or more alkali metal hydroxides and dispersed amorphous calcium carbonate, optionally Selectively mixing with the base oil to form a first mixture, and adding at least a portion of the one or more non-aqueous conversion agents to the first mixture after or during one or more delay periods Converting the pre-mixture into a conversion mixture by heating until the conversion of the amorphous calcium carbonate contained in the overbased calcium sulfonate to crystalline calcium carbonate occurs. And at least one of the delay periods is a retention delay period in which the first mixture or mixture after conversion is maintained at a temperature or within a temperature range for a period of time. In another embodiment, one or more alkali metal hydroxides are added after conversion but not before conversion, or some are added before conversion and some are added after conversion. The pre-conversion and post-conversion additions can be the same or different alkali metal hydroxides.

  Another preferred embodiment of the alkali / delayed addition method comprises optionally water, less than 36% of an overbased calcium sulfonate containing one or more alkali metal hydroxides and dispersed amorphous calcium carbonate, optionally Selectively mixing with the base oil to form a first mixture, and adding at least a portion of the one or more non-aqueous conversion agents to the first mixture after or during one or more delay periods. Forming a pre-conversion mixture and heating until conversion of amorphous calcium carbonate contained in the overbased calcium sulfonate to crystalline calcium carbonate occurs to convert the pre-conversion mixture into a conversion mixture; It contains. In another embodiment, one or more alkali metal hydroxides are added after conversion but not before conversion, or some are added before conversion and some are added after conversion. The pre-conversion and post-conversion additions can be the same or different alkali metal hydroxides.

  Another preferred embodiment of the alkali / delayed addition method is a highly overbased oil-soluble calcium sulfonate comprising dispersed amorphous calcium carbonate in a suitable grease making vessel and (if necessary) a suitable base oil And mixing and starting mixing. Next, one or more accelerating acids are added and mixed, preferably for about 20 to 30 minutes. Next, all of the calcium hydroxyapatite, followed by some of the calcium hydroxide and then all of the calcium carbonate are added and mixed for an additional 20-30 minutes. Next, a portion of acetic acid and a portion of 12-hydroxystearic acid are added and mixed for an additional 20 to 30 minutes (these components may be converting agents but are added before water. (There is no delay period for them). Next, it contains a small amount of alkali metal hydroxide dissolved in water, and water used as a conversion agent is added and mixed while heating to a temperature of 190 ° F. to 230 ° F. (first temperature Adjustment delay period and final delay time). And all hexylene glycol is added as a non-aqueous conversion agent. While maintaining the temperature in the conversion temperature range (preferably 190 ° F. to 230 ° F.) until conversion of the amorphous calcium carbonate contained in the overbased calcium sulfonate to very fine powder of calcium carbonate is complete. By mixing continuously, the mixture is transformed. After conversion, the remaining calcium hydroxide is added and mixed for about 20-30 minutes. Next, add the remaining acetic acid and the remaining 12-hydroxystearic acid and mix for about 30 minutes. Then boric acid dispersed in water is added followed by slow and gradual addition of phosphoric acid. The mixture is then heated to remove water and volatiles, allowed to cool, more base oil is added as needed, and the grease is milled as described below. Additional additives may be added during the final heating or cooling step. In another preferred embodiment of the alkali / delayed addition method, the steps and components are the same as those described above, but after addition of water as conversion agent and addition of all of hexylene glycol as non-aqueous conversion agent Before heating, the mixture is heated to about 160.degree. F. (first temperature adjustment delay period) and held at that temperature for about 30 minutes (first holding delay period) to 190.degree. F. to 230.degree. F. It differs in that heating is continued (second temperature adjustment delay period and final delay period).

  Preferred embodiments of both the alkali addition method and the alkali / delayed addition method may be performed with either an open or closed kettle as commonly used in grease manufacture. The conversion process can be accomplished under normal atmospheric pressure or under pressure in a closed kettle. As such grease making devices are commonly available, manufacture in open kettles (containers not under pressure) is preferred. For the purposes of the present invention, an open container is any container with or without a top cover or hatch, but such a top cover or hatch is not steam tight and has a noticeable pressure during heating Does not occur. Using such an open vessel with the top cover or hatch closed during the conversion process allows the conversion temperature of the boiling point or higher of water to be approximately achieved while maintaining the required level of water as conversion agent Help to make Such higher conversion temperatures can further improve the thickener yield of simple and complex calcium sulfonate greases, as will be appreciated by those skilled in the art. Production in a pressurized kettle may also be utilized, which may lead to even greater improvement in thickener yield, but the pressurization process may be more complex and difficult to control. In addition, manufacturing calcium sulfonate greases with pressurized kettles can create productivity problems. The use of pressurized reactions is important for certain types of greases (such as polyurea greases) and in most grease plants only a limited number of pressurized vessels will be available. Using a pressurized kettle to make calcium sulfonate greases where the pressure reaction is less important can limit the ability of the plant to make other greases where these reactions are important. These problems are avoided in open containers.

  Most preferably, both the alkali addition method and the alkali / lag addition method for producing calcium sulfonate greases comprise: (a) mixing additional base oil and complexing acid, if necessary, after conversion (b C.) Mixing and heating to a temperature high enough to optimize the quality of the final product, ensuring the removal of water and any volatile reaction by-products, and (c) additional groups as required Cooling the grease while adding the oil, (d) adding the remaining desired additives known in the art, and (e) milling the final grease, if necessary, to make it smooth and And b. Obtaining a homogeneous final product. The order and timing of these final steps is not critical, but it is preferable to remove water quickly after conversion. Typically, the grease is heated to 250 F to 300 F, preferably 300 F to 380 F, most preferably 380 F to 400 F (preferably under open conditions but not under pressure, but may be pressurized) The water initially added as a conversion agent and the water formed by the chemical reaction during the formation of the grease may be removed. Placing water in the grease batch for an extended period during manufacture reduces thickener yield, drop point, or both. Such adverse effects can be avoided by removing the water quickly. When a polymer additive is added to the grease, it is preferred not to be added until the grease temperature reaches 300F. Polymeric additives can interfere with the effective volatilization of water when added in sufficient concentrations. Hence, polymer additives should preferably be added to the grease only after all the water has been removed. If during manufacture it can be determined that all the water has been removed before the temperature of the grease reaches the preferred 300F, it is preferable to add the polymer additive afterwards.

  Examples 1-18 of US Pat. No. 9,273,265 and Examples 1-29 of the '768 application are incorporated herein by reference. The overbased calcium sulfonate grease compositions according to the present invention and methods of making such compositions are further described and illustrated in connection with the following examples.

[Example 1A (Reference Example-no alkali addition method, no alkali / delayed addition method)]
A calcium sulfonate complex grease based on the composition of the '768 application was made as follows. Add 264.61 grams of 400 TBN overbased oil-soluble calcium sulfonate to an open mixing vessel, followed by 127.55 g of solvent neutral Group 1 paraffinic base oil with a viscosity of about 600 SUS at 100 F and 4 cSt at 100 ° C. The solution was added with 11.70 g of PAO having a viscosity of The 400 TBN overbased oil-soluble calcium sulfonate was a low quality calcium sulfonate similar to those previously described and used in Examples 10 and 11 of the 768 application. Without heating, mixing was initiated using a planetary mixing paddle. Next, 23.94 grams of main C12 alkyl benzene sulfonic acid was added. After mixing for 20 minutes, 50.65 grams of calcium hydroxyapatite having an average particle size of about 1 to 5 microns and 3.63 grams of food grade purity calcium hydroxide having an average particle size of about 1 to 5 microns Was added and mixed for 30 minutes. The amount of calcium hydroxide added as a separate component is added to the amount of residual calcium hydroxide contained in the overbased calcium sulfonate. Next, 0.88 grams of glacial acetic acid and 10.53 grams of 12-hydroxystearic acid were added and mixed for 10 minutes. Next, 55.03 grams of finely divided calcium carbonate having an average particle size of about 1 to 5 microns was added and mixed for 5 minutes. The amount of calcium carbonate added as a separate component is added to the amount of dispersed calcium carbonate contained in the overbased calcium sulfonate. Next, 13.20 grams of hexylene glycol (non-aqueous converter) and 38.22 grams of water were added substantially simultaneously (without a delay period). The mixture was heated until the temperature reached 190F. The temperature was held between 190F and 200F for 45 minutes, until Fourier transform infrared (FTIR) spectroscopy indicated that conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) occurred.

  An additional 56.07 grams of the same paraffinic base oil was added because the converted grease is heavy. Next, 7.36 grams of the same calcium hydroxide was added and mixed for 10 minutes. Next, 1.52 grams of glacial acetic acid was added, followed by 27.30 grams of 12-hydroxystearic acid. As these acids reacted and the grease further thickened, 111.07 grams of paraffinic base oil was added. Then 9.28 grams of boric acid was mixed into 50 grams of hot water and the mixture was added to the grease. An additional 54.47 grams of paraffinic base oil was added followed by 17.92 grams of 75% aqueous phosphoric acid. The mixture was then heated with an electrical heating mantle while stirring. When the grease reached 300 F, 22.22 grams of a styrene-ethylene-propylene copolymer was added as a crumb-formed solid. The grease was further heated to about 390 F, at which point all the polymer melted and completely dissolved in the grease mixture. The heating mantle was removed and the grease was allowed to continue stirring and cooling in the open air. As the grease cooled to 300 F, 33.01 grams of food grade anhydrous calcium sulfate having an average particle size of about 1 to 5 microns was added. When the temperature of the grease cooled to 200 F, 4.43 grams of polyisobutylene polymer was added. Mixing was continued until the grease reached a temperature of 170F. The grease was then removed from the mixer and passed through a three roll mill three times to finally achieve a smooth and even texture. The 60-round penetration penetration of this grease was 287. The percentage of overbased oil-soluble calcium sulfonate in the final grease was 23.9%. The dropping point was> 650F. In this example, based on the embodiment of the '768 application, calcium hydroxyapatite and calcium carbonate were added prior to conversion. Also, 33% of the total calcium hydroxide was added prior to conversion, followed by a total of 35% glacial acetic acid and 28% 12-hydroxystearic acid. The remaining amounts of calcium hydroxide, glacial acetic acid, and 12-hydroxystearic acid were added after conversion.

Example 1 B (Delayed Addition Method of the '476 Application, No Alkali Addition)
Another calcium complex grease was prepared using the same equipment, ingredients, amounts and preparation method as the grease of Example 1A, but the addition of the non-aqueous conversion agent (hexylene glycol) was delayed. The other starting components (including water) were mixed and heated to a temperature of about 190 ° F. (first temperature adjustment delay period) and hexylene glycol was added immediately after reaching 190 ° F. (no retention delay period) ). The conversion occurred rapidly when hexylene glycol was added. The grease was held at 190-200F for an additional 45 minutes. The remaining process thereafter was the same as the grease of Example 1 above. The 60 grease penetration of the final grease was 290. The percentage of overbased oil-soluble calcium sulfonate in the final grease was 21.4%. The dropping point was> 650F. Thus, the grease of this example is improved compared to the grease of Example 1 above, as evidenced by the lower final percentage of the overbased calcium sulfonate as compared to the degree of penetration. It had a thickener yield.

[Example 2 (embodiment of alkali / delayed addition method)]
Another calcium sulfonate complex grease was prepared in the same manner as the grease of Example 1 B, except that the addition of the non-aqueous conversion agent was delayed except that the alkali metal hydroxide was added to water. The grease was made as follows. Add 240.35 g of 400 TBN overbased oil-soluble calcium sulfonate to an open mixing vessel followed by 345.33 g of solvent neutral Group 1 paraffinic base oil with viscosity of about 600 SUS at 100 F and viscosity of 4 cSt at 100 ° C. Was added with 10.79 grams of PAO. The 400 TBN overbased oil-soluble calcium sulfonate was a low quality calcium sulfonate similar to that previously described and used in Examples 10 and 11 of US Patent Application No. 13 / 664,768. Mixing without heating was initiated using a planetary stir paddle. Next, 21.81 grams of main C12 alkyl benzene sulfonic acid was added. After mixing for 20 minutes, add 46.14 grams of calcium hydroxyapatite with an average particle size of less than 5 microns and 3.34 grams of food grade purity calcium hydroxide with an average particle size of less than 5 microns, Mix for 30 minutes. Next, 50.20 grams of finely divided calcium carbonate having an average particle size of less than 5 microns was added and mixed for 5 minutes. Next, 35 grams of water in which 0.41 grams of sodium hydroxide powder was dissolved was added.

  The mixture was heated to about 180F. Thereafter, 0.76 grams of glacial acetic acid and 9.63 grams of 12-hydroxystearic acid were added (mostly as complexing acids, as glycol is later added as a non-aqueous conversion agent). Note that 12-hydroxystearic acid melts, dissolves and reacts quickly at the temperature of about 180 F to which it is added. Immediately after adding the two complexing acids, the mixture began to develop the appearance of a whipped cream. This appearance usually does not occur if the added water does not contain a small amount of alkali metal hydroxide, and it is believed that something is related to the more rapid formation of the calcium salt of the complexing acid. Without being bound by theory, one possible explanation for the appearance of whipped cream is that fatty acid sodium salts are formed first, so small steady-state concentrations are required until all fatty acid calcium salts are formed. It is to be maintained. Fatty acid sodium salts are well known to be surfactant with water and can cause foaming and lead to the appearance of a whipped cream.

  The mixture was stirred while continuing to heat to a temperature of 190 F to 200 F (first temperature adjustment delay period). When the temperature range of 190F to 200F was reached, the appearance of the whipped cream has subsided. Next, 12.46 grams of hexylene glycol was added as a non-aqueous conversion agent. After one hour and ten minutes, no visible conversion had occurred yet. Also, FTIR showed that most of the water originally added was lost due to evaporation. A further 35 ml of water and 12.47 g of hexylene glycol were added. After another hour and 20 minutes, a visible conversion occurred.

  The grease thickened with time. A total of 100.93 grams of two approximately equal parts of the same paraffinic base oil was added to avoid the grease becoming too heavy to be effectively agitated. Once thickening appeared to stop, an additional 30 ml of water was added for evaporation loss. Fourier transform infrared (FTIR) spectroscopy showed that conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) occurred. Next, 6.80 g of the same calcium hydroxide was added and mixed for 10 minutes. Next, 1.45 grams of glacial acetic acid was added, followed by 24.76 grams of 12-hydroxystearic acid. The grease was stirred at 190F to 200F. As the grease thickened, 49.65 grams of the same paraffinic base oil was added, followed immediately after by another 54.28 grams of the same base oil. Next, 8.50 grams of boric acid was mixed into 30 grams of boiling water and the mixture was added to the grease. After reacting the boric acid, 16.25 g of a 75% aqueous phosphoric acid solution was slowly added and mixed to react. As the grease continues to harden, 49.47 grams of paraffinic base oil was added. The mixture was then heated with an electrical heating mantle while stirring. When the grease reached 300 F, 20.64 grams of styrene-alkylene copolymer was added as a crumb-forming solid. The grease was further heated to a target temperature of 390F. However, the maximum temperature overshooted to a value of 429F. The heating mantle was removed and the grease was kept stirring in the open air and allowed to cool. When the maximum temperature was reached, the polymer melted and completely dissolved in the grease mixture. When the grease cooled to 300 F, 30.29 grams of food grade anhydrous calcium sulfate having an average particle size of less than 5 microns was added. When the grease cooled to 200 F, 2.23 grams of an arylamine antioxidant and 4.18 grams of polyisobutylene polymer were added. 49.92 g of the same paraffinic base oil were further added.

  Stirring was continued until the grease reached a temperature of 170F. The grease was then removed from the mixer and passed through a three roll mill three times to finally achieve a smooth and even texture. The 60-round penetration penetration of this grease was 281. The percentage of overbased oil-soluble calcium sulfonate in the final grease was 20.49%. The dropping point was> 650F. Thus, the thickener yield of this grease was superior to either of the previous two greases. Using the conventional inverse linear relationship between the worked penetration and the percentage of overbased calcium sulfonate, the grease of this example is added to bring the worked penetration to the same value as the previous example 1B grease. Would have resulted in an overbased calcium sulfonate concentration of 19.85%. This result is even more pronounced because the grease of this Example 2 was heated by about 29 F, an effect known to adversely affect the yield of thickener. The amount of sodium hydroxide based on the initial unreacted weight in the final grease product was 0.06%. It should be understood that reference to the proportion of alkali metal hydroxide in the final grease of the present invention refers to the amount of alkali metal hydroxide added as a component in producing the grease. Because the alkali metal hydroxide reacts with the complexing acid to form a salt, it will not be present as the initial unreacted hydroxide in the final grease. However, for ease of reference, its 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 (embodiment of alkali / delayed addition method)]
Another calcium sulfonate complex grease was prepared in the same manner as the grease of Example 2 above. The only significant difference is that at the beginning of the process, the first part of the complexing acid acetic acid and 12-hydroxystearic acid is added while the mixture is still at ambient laboratory temperature (before any heating) It was done. Similar to the grease of Example 2 above, this grease used the alkali / delayed addition embodiment. Furthermore, care was taken that the batch was not overheated during the final heating step.

  The grease of Example 3 was produced as follows. Add 240.31 g of 400 TBN overbased oil-soluble calcium sulfonate to an open mixing vessel followed by 345.09 g of solvent neutral Group 1 paraffinic base oil with a viscosity of about 600 SUS at 100 F and a viscosity of 4 cSt at 100 ° C. Was added with 10.03 grams of PAO. The 400 TBN overbased oil-soluble calcium sulfonate was a poor quality calcium sulfonate similar to that previously described and used in Examples 10 and 11 of US Patent Application No. 13 / 664,768. The mixing was started using a planetary mixing paddle without heating. Next, 21.83 grams of main C12 alkyl benzene sulfonic acid was added. After mixing for 20 minutes, add 46.03 grams of calcium hydroxyapatite with an average particle size of less than 5 microns and 3.30 grams of food grade purity calcium hydroxide with an average particle size of less than 5 microns, 30 Mix for a minute. Next, 0.76 grams of glacial acetic acid and 9.80 grams of 12-hydroxystearic acid were added and mixed for 15 minutes. Next, 50.29 grams of finely divided calcium carbonate having an average particle size of less than 5 microns was added and mixed for 5 minutes. Next, 35.0 g of water in which 0.40 g of sodium hydroxide was dissolved was added. The mixture was heated until the temperature was 190F to 200F (first temperature adjustment delay time). While heating to this temperature range, the appearance of the whipped cream was revealed when the temperature reached about 150F. The appearance of the whipped cream subsided immediately after reaching the temperature range of 190-200F. When the temperature range of 190-200 F was reached, 24.17 grams of hexylene glycol was added (no hold time delay). This amount corresponds to the total amount of hexylene glycol added in two separate parts in the grease of the previous example. However, with the grease of this example, the addition of the alkali metal hydroxide with water changes the conversion process and may require additional non-aqueous conversion agents, so it was added at once. After another 20 ml of water was added and the mixture was stirred for about 1 hour, visible conversion occurred.

  Next, an additional 10 ml of water was added followed by two approximately equal portions of the same paraffinic base oil which totaled 99.73 g. This is to avoid that the continuously thickening grease is so heavy that it can not be mixed effectively. Fourier transform infrared (FTIR) spectroscopy showed that conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) occurred. Next, 6.75 grams of the same calcium hydroxide was added and mixed. An additional 30 ml of water was added to replace the water lost by evaporation. As the grease mixture continued to thicken, 55.22 grams of the same base oil was added. An additional 1.47 grams of glacial acetic acid was added followed by 24.70 grams of 12-hydroxystearic acid. The grease was then mixed for 15 minutes. As the grease mixture continued to thicken, 43.38 grams were added followed by 53.97 grams of the same base oil.

  Next, 8.49 grams of boric acid was mixed into 30 ml of boiling water and the mixture was added to the grease. After reacting the boric acid, 16.30 grams of 75% aqueous phosphoric acid solution was slowly added and mixed to react. The mixture was then heated with an electrical heating mantle while stirring. When the grease reached 300 F, 20.24 grams of styrene-alkylene copolymer was added as a crumb-forming solid. The grease was further heated to about 390 F, at which point all the polymer melted and was completely dissolved in the grease mixture. The heating mantle was removed and the grease was allowed to continue stirring and cooling in the open air. When the grease cooled to 300 F, 30.39 grams of food grade anhydrous calcium sulfate having an average particle size of less than 5 microns was added. When the grease cooled to 200 F, 2.06 grams of arylamine antioxidant and 4.46 grams of polyisobutylene polymer were added. A total of 132.79 grams of three parts of the same base oil were added sequentially and mixed into the grease. Mixing was continued until the grease reached a temperature of 170F. The grease was then removed from the mixer and passed through a three roll mill three times to finally achieve a smooth and even texture.

  The 60 reciprocating penetration of the final grease of Example 3 was 282. The percentage of overbased oil-soluble calcium sulfonate in the final grease was 19.20%. The dropping point was> 650F. Thus, this grease has an improved thickener yield as compared to the greases of Example 1A and Example 1B. In fact, this grease has an improved yield as compared to the greases of all the examples in the '473 application, the' 768 application, and US Pat. No. 9,273,265. This is believed to be the highest thickener yield ever obtained for calcium sulfonate complex greases in the open mixer / kettle (unpressurized) system described in the published literature. The thickener yield is considered to be better than 19.2% when manufactured in a closed pressure kettle.

Example 4 (Reference Example-Alkali metal hydroxide, no delay period)
Another calcium sulfonate complex grease was made in the same manner as the grease of the previous example, but using different base oils, using different non-aqueous conversion agents, not using boric acid, alkali metal hydroxides There was no lag time between the addition of water and the addition of the non-aqueous conversion agent. The greases of this example have the alkali metal hydroxide added, and at least one delay period between the addition of water and the addition of the non-aqueous conversion agent, with the greases of other examples described herein. Serve as a basis for comparison.

  The grease of Example 4 was produced as follows. 297.25 g of 400 TBN overbased oil-soluble calcium sulfonate was added to the open mixing vessel followed by the addition of 373.60 g of USP pure white paraffinic mineral base oil having a viscosity of about 352 SUS at 100F. Overbased calcium sulfonate is a NSF HX-1 food grade approved overbased calcium sulfonate suitable for producing NSF H-1 approved food grade greases and is as defined in the '768 application. It was quality. The mixing was started using a planetary mixing paddle without heating. Next, 26.99 grams of main C12 alkyl benzene sulfonic acid was added. After mixing for 20 minutes, add 50.58 grams of calcium hydroxyapatite with an average particle size of less than 5 microns and 4.06 grams of food grade purity calcium hydroxide with an average particle size of less than 5 microns, Mix for 30 minutes. Next, 0.96 grams of glacial acetic acid and 11.94 grams of 12-hydroxystearic acid were added and mixed for 10 minutes. Next, 55.19 grams of finely divided calcium carbonate having an average particle size of less than 5 microns was added and mixed for 5 minutes. Next, 37.2 grams of water and 14.89 grams of propylene glycol (as a non-aqueous converter) were added. The mixture was heated to a temperature of 190-200F. Conversion and visible thickening began before the target temperature range was reached. The temperature was held for 1 hour and 10 minutes between 190F and 200F. Meanwhile, an additional 15 ml of water was added to replace the water lost by evaporation.

  After 1 hour and 10 minutes, Fourier Transform Infrared (FTIR) spectroscopy showed that conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) had occurred. An additional 54.07 grams of the same base oil was added as thickening occurred. Next, 25 ml of water and 8.35 g of the same calcium hydroxide were added and mixed for 10 minutes. Next, 1.82 grams of glacial acetic acid was added, followed by 30.60 grams of 12-hydroxystearic acid. After the two complexing acids had reacted, 52.86 grams of the same base oil was added due to the increased hardness of the grease mixture. Next, 20.27 grams of 75% aqueous phosphoric acid was slowly added and mixed to react. The mixture was then heated with an electrical heating mantle while stirring. When the grease reached 300 F, 2.86 grams of styrene-alkylene copolymer was added as a crumb-forming solid. The grease was further heated to about 390 F, at which point all the polymer melted and completely dissolved in the grease mixture. The heating mantle was removed and the grease was allowed to continue stirring and cooling in the open air. As the grease cooled to 300 F, 33.10 grams of food grade anhydrous calcium sulfate with an average particle size of less than 5 microns was added. As the grease cooled to 200 F, a mixture of 5.60 grams of a mixture of arylamine and high molecular weight phenolic antioxidant and 5.50 grams of amine phosphate antioxidant / antirust additive were added. An additional 50.70 grams of the same base oil was added, and another 29.39 grams of the same base oil. Mixing was continued until the grease reached a temperature of 170F. The grease was then removed from the mixer and passed through a three roll mill three times to finally achieve a smooth and even texture. The 60-round penetration penetration of this grease was 281. The percentage of overbased oil-soluble calcium sulfonate in the final grease was 26.29%. The dropping point was> 650F.

[Example 5 (embodiment of alkali / delayed addition method)]
Another calcium sulfonate complex grease was made as in the previous example 4 grease, but with the addition of the alkali metal hydroxide, there was a delay between the addition of water and the addition of the non-aqueous converter. The alkali metal hydroxide used was sodium hydroxide and its concentration in the final grease was 0.03%. Also, the amount of non-aqueous conversion agent (propylene glycol) is consistent with what was measured for the greases of Example 2 and Example 3 above where the alkali / delayed addition embodiment was used, the previous implementation. It was about twice as large as the grease of Example 4.

  The grease of Example 5 was produced as follows. 298.15 grams of 400 TBN overbased oil-soluble calcium sulfonate was added to the open mixing vessel, followed by 360.45 grams of USP pure white paraffinic mineral base oil having a viscosity of about 352 SUS at 100F. Overbased calcium sulfonate is a NSF HX-1 food grade approved overbased calcium sulfonate suitable for producing NSF H-1 approved food grade greases and is of high quality as defined in the '768 application there were. The mixing was started using a planetary mixing paddle without heating. Next, 27.10 grams of main C12 alkyl benzene sulfonic acid was added. After mixing for 20 minutes, add 50.61 grams of calcium hydroxyapatite with an average particle size of less than 5 microns and 4.09 grams of food grade purity calcium hydroxide with an average particle size of less than 5 microns, 30 Mix for a minute. Next, 0.96 grams of glacial acetic acid and 11.92 grams of 12-hydroxystearic acid were added and mixed for 15 minutes. Next, 55.04 grams of finely divided calcium carbonate having an average particle size of less than 5 microns was added and mixed for 5 minutes. Next, 39.1 grams of water in which 0.44 grams of sodium hydroxide powder was dissolved was added. The mixture was heated while continuing to stir until the temperature reached 190 to 200 F (first temperature adjustment delay period). It was noted that when the temperature reached about 170 F, the appearance of the whipped cream was observed. After reaching 190 to 200 F, 20 ml of water was added to replace the water lost by evaporation. After mixing for 35 minutes at 190-200 F (first retention delay period), 29.88 grams of propylene glycol was added and it was observed that the appearance of the whipped cream had settled before 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 grams of the same base oil was added along with 5 milliliters of water. Finally, 51.25 g of the same base oil was added to prevent the grease from becoming too hard. When Fourier Transform Infrared (FTIR) spectroscopy showed that almost all the water was gone, an additional 40 ml of water was added.

  Fourier Transform Infrared (FTIR) spectroscopy showed that conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) occurred after about 2 hours at 190 to 200 F (2 hours after propylene glycol addition) showed that. Next, 40 ml of water and 8.12 g of the same calcium hydroxide were added and mixed for 10 minutes. 52.07 grams of the same base oil was added as the grease continued to thicken. Then 2.85 grams of glacial acetic acid were added followed by 31.35 grams of 12-hydroxystearic acid. After the reaction of the two complexing acids, the hardness of the grease mixture increased, so 52.11 grams of the same base oil were added. Then another 20 ml of water was added followed by 54.11 g of the same base oil. Next, 20.14 grams of 75% aqueous phosphoric acid solution was slowly added and mixed to react. As the grease hardened further, another 52.5 grams of the same base oil was added. The mixture was then heated with an electrical heating mantle while stirring. When the grease reached 300 F, 2.75 grams of styrene-alkylene copolymer was added as a crumb-forming solid. The grease was further heated to about 390 F, at which point all the polymer melted and was completely dissolved in the grease mixture. The heating mantle was removed and the grease was allowed to continue stirring and cooling in the open air. When the grease had cooled to 300 F, 33.16 grams of food grade anhydrous calcium sulfate having an average particle size of less than 5 microns was added. When the grease had cooled to 200 F, a mixture of 5.62 grams of the arylamine and high molecular weight phenolic antioxidant and 5.68 grams of the amine phosphate antioxidant / antirust additive were added. A total of 107.41 grams of three parts of the same base oil was added. Mixing was continued until the grease reached a temperature of 170F. The grease was then removed from the mixer and passed through a three roll mill three times to finally achieve a smooth and even texture. The 60-round penetration penetration of this grease was 288. The percentage of overbased oil-soluble calcium sulfonate in the final grease was 21.78%. The dropping point was> 650F. The thickener yield of this grease is significantly improved compared to the grease of Example 4 above, demonstrating the remarkable effect of the alkali / delayed addition embodiment.

[Example 6 (embodiment of alkali / delayed addition method)]
Another calcium sulfonate complex grease was prepared in the same manner as the grease of Example 5 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 grams of 400 TBN overbased oil-soluble calcium sulfonate was added to the open mixing vessel followed by 360.93 grams of USP pure white paraffinic mineral base oil having a viscosity of about 352 SUS at 100F. Overbased calcium sulfonate is a NSF HX-1 food grade approved overbased calcium sulfonate suitable for producing NSF H-1 approved food grade greases and is of high quality as defined in the '768 application there were. The mixing was started using a planetary mixing paddle without heating. Next, 27.13 grams of main C12 alkyl benzene sulfonic acid was added. After mixing for 20 minutes, add 50.63 grams of calcium hydroxyapatite having an average particle size of less than 5 microns and 4.20 grams of food grade purity calcium hydroxide having an average particle size of less than 5 microns, Mix for 30 minutes. Next, 0.95 grams of glacial acetic acid and 11.92 grams of 12-hydroxystearic acid were added and mixed for 15 minutes. Next, 55.14 grams of finely divided calcium carbonate having an average particle size of less than 5 microns was added and mixed for 5 minutes. Next, 39.2 g of water in which 0.88 g of sodium hydroxide powder was dissolved was added. The mixture was heated while continuing to stir until the temperature reached 190-200 F (first temperature adjustment delay period). It was noted that when the temperature reached about 184 F, the appearance of the whipped cream was observed. After mixing for 35 minutes at 190-200 F (first holding delay period), 20 ml of water was added to replace the water lost by evaporation. Shortly thereafter, the whipped cream's appearance subsided and 30.25 g of propylene glycol was added as a non-aqueous conversion agent. Visible conversion and thickening began after 20 minutes. An additional 10 ml of water was added for evaporation loss.

  As the grease continued to thicken, 51.96 grams of the same base oil was added followed by a further 57.48 grams of the same base oil. Once the conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) and the thickening process appeared complete, 8.12 g of the same calcium hydroxide was added and mixed for 10 minutes. As the grease continued to thicken, 51.85 grams of the same base oil was further added. Next, 1.83 grams of glacial acetic acid was added, followed by 30.54 grams of 12-hydroxystearic acid. After the reaction of these two complexing acids, the hardness of the grease mixture increased, so a total of 107.53 grams of the two parts of the same base oil were further added. Next, 10 ml of water was further added, and then 20.30 g of 75% aqueous phosphoric acid solution was slowly added and mixed to react. As the grease hardened further, a total of 99.63 grams of two parts of the same base oil was added. The mixture was then heated with an electrical heating mantle while stirring. When the grease reached 300 F, 2.91 grams of styrene-alkylene copolymer was added as a crumb-forming solid. The grease was further heated to about 390 F, at which point all the polymer melted and was completely dissolved in the grease mixture. The heating mantle was removed and the grease was allowed to continue stirring and cooling in the open air. When the grease cooled to 300 F, 33.11 grams of food grade anhydrous calcium sulfate with an average particle size of less than 5 microns was added. When the grease cooled to 200 F, a mixture of 5.78 grams of the arylamine and high molecular weight phenolic antioxidant and 5.78 grams of amine phosphate antioxidant / antirust additive were added. A total of 114.78 grams of 3 parts of the same base oil was added. Mixing was continued until the grease reached a temperature of 170F. The grease was then removed from the mixer and passed through a three roll mill three times to finally achieve a smooth and even texture. The 60-round penetration penetration of this grease was 295. The percentage of overbased oil-soluble calcium sulfonic acid in the final grease was 20.78%. The dropping point was> 650F. As is apparent, the thickener yield of this grease is significantly improved compared to the grease of Example 4 above, demonstrating the remarkable effect of the alkali / delayed addition embodiment. Using the conventional inverse linear relationship between the worked consistency and the ratio of the overbased calcium sulfonate concentration, the grease of this example has the same worked consistency as the grease of the previous example 5 If the base oil was withdrawn, the overbased calcium sulfonate concentration would have been 21.3%. Thus, doubling the amount of sodium hydroxide in the grease of this Example 6 appears to at most improve the thickener yield slightly further compared to the grease of the previous Example 5.

[Example 7 (embodiment of alkali / delayed addition method)]
Another calcium sulfonate complex grease was prepared in the same manner as the grease of Example 6 above. The only significant difference between this grease and the grease of Example 6 above was that the grease was held at 160-170 F for one hour during the first heating period. The grease was prepared as follows. 297.79 g of 400 TBN overbased oil-soluble calcium sulfonate was added to the open mixing vessel followed by 362.02 g of USP pure white paraffinic mineral base oil having a viscosity of about 352 SUS at 100F. Overbased calcium sulfonate is a NSF HX-1 food grade approved overbased calcium sulfonate suitable for producing NSF H-1 approved food grade greases and is of high quality as defined in the '768 application there were. The mixing was started using a planetary mixing paddle without heating. Next, 27.01 grams of main C12 alkyl benzene sulfonic acid was added. After mixing for 20 minutes, add 50.64 grams of calcium hydroxyapatite with an average particle size of less than 5 microns and 4.14 grams of food grade purity calcium hydroxide with an average particle size of less than 5 microns, 30 Mix for a minute. Next, 0.94 grams of glacial acetic acid and 11.92 grams of 12-hydroxystearic acid were added and mixed for 15 minutes. Next, 55.37 grams of finely divided calcium carbonate having an average particle size of less than 5 microns was added and mixed for 5 minutes. Next, 39.1 g of water in which 0.88 g of sodium hydroxide powder was dissolved was added. The mixture was heated while continuing to mix until the temperature was 160-170 F (first temperature adjustment delay time). During this time, it was observed that the appearance of the whipped cream was brought about. After mixing for 1 hour at 160 to 170 F (first holding delay period), the mixture was heated to 190 to 200 F (second temperature adjustment delay time), and 30.14 grams of propylene glycol was added as a non-aqueous conversion agent.

  Visible conversion and thickening began after 40 minutes. Then 30 ml of water were added for evaporation loss. As the grease continued to thicken, 53.10 grams of the same base oil was added. After 25 minutes, 20 ml of water and 51.91 g of the same base oil were further added. After a further 10 minutes, 10 ml of water and 56.33 g of the same base oil were then added. After an additional 25 minutes, the conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) and the thickening process appear to be complete: In addition, it was mixed for 10 minutes. Next, 1.84 grams of glacial acetic acid was added followed by 30.57 grams of 12-hydroxystearic acid. After the reaction of these two complexing acids, the hardness of the grease mixture increased, so an additional two parts of 105.14 grams of the same base oil were added. Next, 20.22 g of 75% phosphoric acid aqueous solution was slowly added and mixed to react. As the grease became more hard, 55.31 grams of the same base oil was added. The mixture was then heated with an electrical heating mantle while stirring. When the grease reached 300 F, 2.77 grams of styrene-alkylene copolymer was added as a crumb-forming solid. The grease was further heated to about 390 F, at which point all the polymer melted and was completely dissolved in the grease mixture. The heating mantle was removed and the grease was allowed to continue stirring and cooling in the open air.

  As the grease cooled to 300 F, 33.21 grams of food grade anhydrous calcium sulfate with an average particle size of less than 5 microns was added. When the grease cooled to 200 F, a 5.61 gram mixture of arylamine and high molecular weight phenolic antioxidant and 5.90 grams of amine phosphate antioxidant / rust inhibitor were added. Mixing was continued until the grease reached a temperature of 170F. The grease was then removed from the mixer and passed through a three roll mill three times to finally achieve a smooth and even texture. The 60-round penetration penetration of this grease was 309. The percentage of overbased oil-soluble calcium sulfonate in the final grease was 23.43%. The dropping point was> 650F.

  Using the conventional inverse linear relationship between worked penetration and overbased calcium sulfonate concentration, the same as the previous Example 4 grease with no added alkali metal hydroxide and no lag time The grease of this Example 7 will have a calcium overbased sulfonate concentration of 25.76% if less base oil is added to provide a degree of worked penetration. When this value is compared with the results of the greases of Examples 4, 5 and 6, most of the yield improvement effect of the grease of Example 7 has a first temperature range of 160 to 170 F before heating to 190 to 200. It seems to have been removed by having a temperature holding delay period of In Example 12 and Example 17 of the '476 application, when the alkali metal hydroxide is not added, having a first holding delay period in a first temperature range of 160 to 170 F before heating to 190 to 200 F, Although it was shown to improve thickener yield (20.36% and 20.59% respectively), the first retention delay period in those examples was 2.5 hours. The addition of a very small amount of alkali metal hydroxide (such as 0.07% by weight in the final grease ratio in Example 7), as compared to the greases of the examples of the present application, affects the conversion process While it is beneficial to utilize the alkali / delayed addition embodiment, the benefits of the particular combination of delay periods in the '476 application are not necessarily achieved in combination with the addition of alkali metal hydroxides. looks like. This result is unexpected and surprising. The grease of Example 7 shows some thickener yield improvement as compared to the grease of Reference Example 4, but due to the delay time and temperature range of the particular combination of Example 7 Most of the yield improvement seen with the greases of Example 5 and Example 6 is not observed. Therefore, when adding an alkali metal hydroxide, the grease is heated to a first temperature range of 160 to 170 F as part of the delayed non-aqueous conversion method, and any retention delay period is performed in the first temperature range. It is most preferable not to have.

[Example 8 (embodiment of alkali / delayed addition method)]
A calcium sulfonate complex grease was produced in the same manner as the grease of Example 6, except that alkali hydroxide monohydrate was used as the alkali metal hydroxide in place of sodium hydroxide. The lithium hydroxide concentration based on the monohydrate form in the final grease was 0.06%. The grease was made as follows. 298.61 g of 400 TBN overbased oil-soluble calcium sulfonate was added to the open mixing vessel followed by the addition of 362.54 grams of USP pure white paraffinic mineral base oil having a viscosity of about 352 SUS at 100F. Overbased calcium sulfonate is an NSF HX-1 food grade approved overbased calcium sulfonate suitable for producing NSF H-1 approved food grade greases and is of high quality as defined in the '768 application. The The mixing was started with a planetary mixing paddle without heating. Next, 27.03 grams of main C12 alkyl benzene sulfonic acid was added. After mixing for 20 minutes, add 50.62 grams of calcium hydroxyapatite with an average particle size of less than 5 microns and 4.11 grams of food grade pure calcium hydroxide with an average particle size of less than 5 microns Mixed for 30 minutes. Next, 0.97 grams of glacial acetic acid and 11.96 grams of 12-hydroxystearic acid were added and mixed for 15 minutes. Next, 55.05 grams of finely divided calcium carbonate having an average particle size of less than 5 microns was added and mixed for 5 minutes. Next, 39.55 grams of water in which 0.88 grams of lithium hydroxide monohydrate powder 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, the appearance of the whipped cream was observed. After mixing for 45 minutes at 190-200 F (first retention delay period), 30 ml water was added to replace the water lost to evaporation and 30.01 g propylene glycol was added. In addition, it was observed that the appearance of the whipped cream was settled at that time.

  Visible conversion and thickening began after 35 minutes. 15 ml water was added for evaporation loss. As the grease continued to thicken, 58.52 grams of the same base oil was added followed by 51.15 grams of the same base oil. Once the conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) and the thickening process appeared complete, 8.12 g of the same calcium hydroxide was added and mixed for 10 minutes. Next, 1.78 grams of glacial acetic acid was added followed by 30.53 grams of 12-hydroxystearic acid. After about 15 minutes, when these two complexing acids appeared to react, an additional 69.37 grams of the same base oil was added to prevent the grease from becoming too hard. An additional 10 ml of water was added. As the grease continued to cure, a total of 90.53 grams of the same two parts of the same base oil were added. Next, 5 ml of water was further added, and then 20.16 g of 75% aqueous phosphoric acid solution was slowly added and mixed to react. As the grease continued to harden further, 38.24 grams of the same base oil was added. The mixture was then heated with an electrical heating mantle while stirring. When the grease reached 300 F, 2.85 grams of styrene-alkylene copolymer was added as a crumb-forming solid. The grease was further heated to about 390 F, at which point all the polymer melted and was completely dissolved in the grease mixture. The heating mantle was removed and the grease was allowed to continue to stir and cool in the open air. When the grease had cooled to 300 F, 33.21 grams of food grade anhydrous calcium sulfate having an average particle size of less than 5 microns was added. When the grease had cooled to 200 F, a mixture of 5.78 grams of arylamine and high molecular weight phenolic antioxidant and 6.10 grams of amine phosphate antioxidant / antirust additive were added. A total of 112.37 grams of the same two parts of the same base oil were added. Stirring was continued until the grease reached a temperature of 170F. The grease was then removed from the mixer and passed through a three roll mill three times to finally achieve a smooth and even texture. The 60-round penetration penetration of this grease was 295. The percentage of overbased oil-soluble calcium sulfonate in the final grease was 21.79%. The dropping point was> 650F. Thus, the thickener yield of this grease is significantly improved compared to the grease of Example 4 above, demonstrating the remarkable effect of utilizing the alkali / delayed addition embodiment. There is. Comparing this grease with the grease of Example 6 having the same first temperature adjustment delay period and the same first holding delay time (35 minutes to 45 minutes), the thickening efficiency improvement effect of lithium hydroxide Is considered to be less effective than sodium hydroxide.

[Example 9 (embodiment of alkali / delayed addition method)]
Another calcium sulfonate complex grease was made in the same manner as the grease of Example 6 above, except that potassium hydroxide was used instead of sodium hydroxide as the added alkali metal hydroxide. Potassium hydroxide was introduced in the form of a 47.9% aqueous solution. The amount of this 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. Similar to the grease of Example 6, this was done to make the molar amount of the addition hydroxide of this grease approximately the same. The potassium hydroxide concentration of the final grease was 0.20%. The grease was prepared as follows. 302.52 g of 400 TBN overbased oil-soluble calcium sulfonate was added to the open mixing vessel followed by 357.60 g of USP pure white paraffinic mineral base oil having a viscosity of about 352 SUS at 100F. Overbased calcium sulfonate is a NSF HX-1 food grade approved overbased calcium sulfonate suitable for producing NSF H-1 approved food grade greases and is of high quality as defined in the '768 application. Met. The mixing was started using a planetary mixing paddle without heating. Next, 27.04 grams of main C12 alkyl benzene sulfonic acid was added. After mixing for 20 minutes, add 50.63 grams of calcium hydroxyapatite with an average particle size of less than 5 microns and 4.09 grams of food grade purity calcium hydroxide with an average particle size of less than 5 microns, 30 Mix for a minute. Next, 0.96 grams of glacial acetic acid and 11.94 grams of 12-hydroxystearic acid were added and mixed for 15 minutes. Next, 55.00 grams of finely divided calcium carbonate having an average particle size of less than 5 microns was added and mixed for 5 minutes. Thereafter, 39.00 g of water mixed with 2.67 g of 47.9% aqueous potassium hydroxide solution was added.

  The mixture was heated with continuous mixing until the temperature reached 190-200F. When the temperature reached about 170-180 F, the appearance of the whipped cream developed. Heating was continued until the grease reached 200 F (first temperature adjustment delay period), then 15 ml water and 29.72 g propylene glycol were added (no hold delay time). In addition, it was observed that the appearance of the whipped cream was settled at that time. Once visible conversion and thickening started, 65.89 grams of the same base oil and 10 ml of water were added. As thickening continued, 36.32 grams of the same base oil and 10 ml of water were added. This was followed by the addition of 51.67 grams of the same base oil. When the conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) and the thickening process appeared to be complete, 8.27 grams of the same calcium hydroxide was added and mixed for 10 minutes. Next, 1.79 grams of glacial acetic acid was added followed by 30.57 grams of 12-hydroxystearic acid. As these two complexing acids reacted and the grease continued to thicken, 88.20 grams of the same base oil was added followed by 5 ml of water. Next, as the grease became harder, 15.73 grams of the same base oil was added. Next, 20.81 g of 75% aqueous phosphoric acid solution was slowly added and mixed to react. As the grease continued to harden, 51.66 grams of the same base oil was added. The mixture was then heated with an electrical heating mantle while stirring. When the grease reached 300 F, 2.75 grams of styrene-alkylene copolymer was added as a crumb-forming solid. The grease was further heated to about 390 F, at which point all the polymer melted and was completely dissolved in the grease mixture. The heating mantle was removed and the grease was allowed to continue stirring and cooling in the open air.

  When the grease cooled to 300 F, 33.19 grams of food grade anhydrous calcium sulfate having an average particle size of less than 5 microns was added. Once the grease had cooled to 200 F, a mixture of 5.93 grams of the arylamine and high molecular weight phenolic antioxidant and 6.78 grams of the amine phosphate antioxidant / rust inhibitor were added. An additional 51.59 grams of the same base oil was added. Mixing was continued until the grease reached a temperature of 170F. The grease was then removed from the mixer and passed through a three roll mill three times to finally achieve a smooth and even texture. The 60-round penetration penetration of this grease was 292. The percentage of overbased oil-soluble calcium sulfonate in the final grease was 23.03%. The dropping point was> 650F. The thickener yield of this grease is significantly improved compared to the grease of Example 4 above, demonstrating the remarkable effect of utilizing the alkali / delayed addition embodiment. Further comparing this grease to the greases of Example 6 and Example 8, the yield improving effect of potassium hydroxide appears to be less effective than either sodium hydroxide or lithium hydroxide. The most preferred alkali metal hydroxide is sodium hydroxide, followed by lithium hydroxide and then hydroxide hydroxide, although additional tests with other changes in the delay period of the addition of the non-aqueous conversion agent may be shown separately It is believed to be potassium.

[Example 10 (embodiment of alkali / delayed addition method)]
Another calcium sulfonate complex grease was made similar to the grease of previous example 6, but more base oil is added first, overbased calcium sulfonate, C12 alkyl benzene sulfonic acid, propylene glycol conversion agent, 12 The amount of hydroxystearic acid and acetic acid was relatively reduced compared to the amount of calcium hydroxide added, calcium hydroxyapatite, calcium carbonate added and phosphoric acid. The grease was manufactured as follows. 233.60 grams of 400 TBN overbased oil-soluble calcium sulfonate was added to the open mixing vessel followed by the addition of 422.48 grams of USP pure white paraffinic mineral base oil having a viscosity of about 352 SUS at 100F. Overbased calcium sulfonate is an NSF HX-1 food grade approved overbased calcium sulfonate suitable for producing NSF H-1 approved food grade greases and is of high quality as defined in the '768 application. The The mixing was started using a planetary mixing paddle without heating. Next, 21.04 grams of main C12 alkyl benzene sulfonic acid was added. After mixing for 20 minutes, add 50.69 g of calcium hydroxyapatite with an average particle size of less than 5 microns and 4.10 g of food grade purity calcium hydroxide with an average particle size of less than 5 microns and mix for 30 minutes The Next, 0.72 grams of glacial acetic acid and 9.32 grams of 12-hydroxystearic acid were added and mixed for 15 minutes. Next, 55.22 g of finely divided calcium carbonate having an average particle size of less than 5 microns was added and mixed for 5 minutes. Next, 39.1 g of water in which 0.88 g of sodium hydroxide powder was dissolved was added. The mixture was heated while continuing to mix until the temperature reached 190-200F (first temperature adjustment delay period). It was noted that when the temperature reached about 180 F, the appearance of the whipped cream was observed. After mixing for 40 minutes at 190-200 F (first retention delay period), 20 ml of water to replace the water lost by evaporation was added and 23.13 g of propylene glycol was added. At this point, it was also observed that the appearance of the whipped cream had subsided.

  Thickening still occurred after 2 hours and 30 minutes. The temperature rose to 230 F and FTIR showed very little water left. An additional 30 ml of water was added and the temperature was maintained at 230F. After 30 minutes, an additional 35 ml of water was added. After another 25 minutes, 35 ml of water was added. The temperature dropped to about 220F. Next, 8.22 grams of the same calcium hydroxide was added and mixed for 10 minutes. Next, 1.37 grams of glacial acetic acid was added, followed by 23.68 grams of 12-hydroxystearic acid. After these two complexing acids reacted, 20.53 g of 75% aqueous phosphoric acid solution was slowly added and mixed to react. The grease was then heated with an electrical heating mantle while stirring. When the grease reached 300 F, 2.79 grams of styrene-alkylene copolymer were added as a crumb-forming solid. The grease was further heated to about 390 F, at which point all the polymer melted and was completely dissolved in the grease mixture. The heating mantle was removed and the grease was allowed to continue stirring and cooling in the open air. As the grease cooled to 300 F, 33.15 grams of food grade anhydrous calcium sulfate with an average particle size of less than 5 microns was added. When the grease cooled to 200 F, a mixture of 5.89 grams of a mixture of arylamine and high molecular weight phenolic antioxidant and 5.83 grams of amine phosphate antioxidant / antirust additive were added. A total of 103.66 grams of the two parts of the same base oil was added. Mixing was continued until the grease reached a temperature of 170F. The grease was then removed from the mixer and passed through a three roll mill three times to finally achieve a smooth and even texture. The 60-round penetration penetration of this grease was 289. The percentage of overbased oil-soluble calcium sulfonate in the final grease was 22.76%. The dropping point was 621F. Thus, the thickener yield of this grease is significantly improved compared to the reference grease of Example 4 above, demonstrating the remarkable effect of the alkali / delayed addition embodiment. .

  The results of Examples 1 to 10 herein and the processes used are summarized in Table 1 below. The amount of overbased calcium sulfonate in parenthesis, as described above, when the additional base oil is added to dilute the sample grease to achieve the same consistency as the numbered example shown after the dash. Estimated amount of overbased calcium sulfonate. These first ten examples are particularly useful when calcium hydroxyapatite and added calcium carbonate are used as calcium-containing bases to react with complexing acids as described in the '768 application. It has been demonstrated that thickener yield is improved by utilizing the alkali / delay method embodiment. Furthermore, using the alkali / retardation embodiment of the present invention, the thickener yield is improved with both low and high quality overbased calcium sulfonates. Complex greases also showed excellent dropping points.

  The following examples further vary the timing of the addition of the alkali metal hydroxide to further demonstrate the superior properties of the overbased calcium sulfonate greases of the present invention that can be achieved using embodiments of the alkali / retardation method of the present invention. It shows.

Example 11 (Reference Example-no added alkali metal hydroxide, no delay period)
Another calcium sulfonate complex grease is described in Example 18 of the '476 application, similar to the embodiment of US Pat. No. 4,560,489 (issued to Witco Corporation on Dec. 24, 1985). It was prepared as follows. As disclosed in the '489 patent, the only calcium-containing base added for reaction with the complexing acid in this grease was calcium hydroxide. This grease serves as the basis for the following two examples.

  The grease of Example 11 was produced as follows. 440.02 g of 400 TBN overbased oil-soluble calcium sulfonate was added to the open mixing vessel followed by 390.68 g of solvent neutral grade 1 paraffinic base oil having a viscosity of about 600 SUS at 100F. The mixing was started using a planetary mixing paddle without heating. The 400 TBN overbased oil-soluble calcium sulfonate was a high quality calcium sulfonate similar to that previously described and used in Examples 4 and 12 of the '768 application. Next, 17.76 grams of main C12 alkyl benzene sulfonic acid was added. After mixing for 20 minutes, 44.41 grams of water followed by 14.37 grams of hexylene glycol were added. The batch was then heated while mixing continued until the temperature reached 190F. When the temperature reached 190 F, 5.75 grams of glacial acetic acid was added. If visible conversion to the grease structure is observed, it is possible to use 190F until Fourier transform infrared (FTIR) spectroscopy shows that conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) takes place. The temperature was held for 45 minutes between 200F. Next, 15.37 grams of food grade purity calcium hydroxide having an average particle size of less than 5 microns was added and mixed for 10 minutes. This calcium hydroxide was the only added calcium containing base to react with the complexing acid. Next, 28.59 grams of 12-hydroxystearic acid was added and melted to react. Next, 25.33 g of boric acid was mixed with 50 ml of hot water and the mixture was added to the grease. Then, the grease was heated to 330F. The heating mantle was then removed and the grease was allowed to continue stirring in the open air to cool. Once the grease had cooled to 170 F, it was removed from the mixer and passed through a three roll mill three times to finally achieve a smooth and even texture. The 60-round penetration penetration of this grease was 291. The percentage of overbased oil-soluble calcium sulfonate in the final grease was 46.92%. The dropping point was> 650F.

[Example 12 (embodiment of alkali / delayed addition method)]
Another grease was made in the same manner as the previous grease, but this grease delayed the addition of the non-aqueous conversion agent hexylene glycol until the mixture was heated to 190-200F. Furthermore, this grease is added to the second part of the water added at 190 to 200 F after the first conversion has taken place and before calcium hydroxide, 12-hydroxystearic acid or acetic acid is added. A small amount of sodium hydroxide was dissolved. The sodium hydroxide concentration in the final grease was 0.08%. The grease was made as follows. 430.36 grams of 400 TBN overbased oil-soluble calcium sulfonate was added to the open mixing vessel followed by 383.79 grams of solvent neutral grade 1 paraffinic base oil having a viscosity of about 600 SUS at 100 ° F. The mixing was started using a planetary mixing paddle without heating. The 400 TBN overbased oil-soluble calcium sulfonate was a high quality calcium sulfonate similar to that previously described and used in Examples 4 and 12 of the '768 application. Next, 17.64 grams of main C12 alkyl benzene sulfonic acid was added.

  After mixing for 20 minutes, 44.48 grams of water was added as a conversion agent. Thereafter, the batch was heated while mixing until the temperature reached 190 to 200 F (first temperature adjustment delay period). When the temperature reached 190 F, 5.52 grams of glacial acetic acid was added and mixed for 5 minutes. Next, 14.32 grams of hexylene glycol was added while maintaining the temperature at 190-200F. The 5-minute interval from the first temperature range of 190 to 200 F to the addition of the non-aqueous conversion agent is so short that it is not considered a retention delay period. If visible conversion to a grease structure is observed, the Fourier transform infrared (FTIR) spectroscopy shows that conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) takes place. The temperature was held at 200F for 45 minutes. Next, 15.41 grams of food grade purity calcium hydroxide having an average particle size of less than 5 microns was added and mixed for 10 minutes. This calcium hydroxide was the only added calcium containing base to react with the complexing acid. Next, 44.04 grams of water (second addition of water) in which 0.88 grams of sodium hydroxide powder was dissolved was added and mixed with the grease. Next, 28.60 grams of 12-hydroxystearic acid was added and melted to react. The grease was stirred for 45 minutes, then 25.30 g of boric acid was mixed with 50 ml of boiling water and the mixture was added to the grease.

  The grease was then heated to 390-400F. The heating mantle was then removed and stirring continued in the open air to cool the grease. When the grease cooled to 200 F, 2.40 grams of an aryl amine antioxidant was added. Next, a total of 165.54 grams of the same two parts of the same base oil were added and mixed into the grease. Once the grease had cooled to 170 F, it was removed from the mixer and passed through a three roll mill three times to finally achieve a smooth and even texture. The 60-round penetration penetration of this grease was 290. The percentage of overbased oil-soluble calcium sulfonate in the final grease was 39.38%. The dropping point was> 650F. As can be seen, this grease had essentially the same worked penetration as the grease of the previous example 11. However, the thickener yield was significantly improved as indicated by the much lower proportion of overbased calcium sulfonate in this grease as compared to the grease of Example 11 above.

[Example 13 (embodiment of alkali / delayed addition method)]
Another grease was made in the same manner as the previous grease and the addition of the non-aqueous conversion agent hexylene glycol was delayed until the mixture was heated to 190-200 F (first temperature adjustment delay time). However, in this grease, a small amount of sodium hydroxide was dissolved in the first part of the water added at ambient temperature before the heating of the batch began. Again, the sodium hydroxide concentration in the final grease was 0.08%. The grease was manufactured as follows. 440.24 g of 400 TBN overbased oil-soluble calcium sulfonate was added to the open mixing vessel followed by 385.62 g of solvent neutral grade 1 paraffinic base oil having a viscosity of about 600 SUS at 100F. The mixing was started using a planetary mixing paddle without heating. The 400 TBN overbased oil-soluble calcium sulfonate was a high quality calcium sulfonate similar to that previously described and used in Examples 4 and 12 of the '768 application. Next, 17.61 grams of main C12 alkyl benzene sulfonic acid was added. After mixing for 20 minutes, a solution of 0.88 grams of sodium hydroxide powder in 44.48 grams of water was added. Thereafter, the batch was heated while mixing until the temperature reached 190 to 200 F (first temperature adjustment delay period). When the temperature reached 190 F, 5.50 grams of glacial acetic acid was added and mixed for 5 minutes. Next, 14.64 grams of hexylene glycol was added while maintaining the temperature at 190-200F. Again, the 5-minute interval from reaching the first temperature range of 190-200F to adding the non-aqueous conversion agent is so short that it is not considered a retention delay period. If visible conversion to a grease structure is observed, the Fourier transform infrared (FTIR) spectroscopy shows that conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) takes place. The temperature was maintained at 200F for 45 minutes.

  Next, 30.1 grams of water and 15.41 grams of food grade purity calcium hydroxide having an average particle size of less than 5 microns were added and mixed for 10 minutes. Again, this calcium hydroxide was the only added calcium containing base to react with the complexing acid. Next, 28.66 grams of 12-hydroxystearic acid was added and melted to react. The grease was stirred for 45 minutes, then 25.41 g of boric acid was mixed with 50 ml of hot water and the mixture was added to the grease. The grease was then heated to 390-400F. The heating mantle was then removed and the grease was allowed to continue stirring and cooling in the open air. When the grease cooled to 200 F, 2.69 grams of an aryl amine antioxidant was added. Next, a total of 172.32 grams of the same three parts of the same base oil were added and mixed into the grease.

  Once the grease had cooled to 170 F, it was removed from the mixer and passed through a three roll mill three times to finally achieve a smooth and even texture. The 60-round penetration penetration of this grease was 284. The percentage of oil soluble overbased calcium sulfonate in the final grease was 38.74%. The dropping point was> 650F. Again, the thickener yield was significantly improved as indicated by the very low proportion of overbased calcium sulfonate in this grease as compared to the previous Example 11 grease. The grease of this example and the grease of Example 12 above are alkaline (as opposed to the addition of calcium hydroxyapatite and / or added calcium carbonate as disclosed in the previous example and '768 application) alkaline Demonstrate that using the calcium hydroxide embodiment for the reaction with the complexing acid leads to a very significant increase in the yield of the thickener by utilizing the embodiment of the / delayed addition method There is. The thickener yield is at least at least as Example 13 where the alkali metal hydroxide is added with the first water is better than Example 12 where the alkali metal hydroxide is added with the second addition of water. If calcium hydroxide is the only calcium-containing base, it is preferred to add the alkali metal hydroxide in the first addition of water. However, both Example 12 and Example 13 show a significant improvement in thickener yield as compared to Example 11 where no alkali metal hydroxide was added.

  Also note that the concentration of non-aqueous conversion agent in the greases of Example 12 and Example 13 (both utilizing both alkali / retarded addition embodiments) was the same as the reference grease of Example 11. Of. When the prior art calcium sulfonate grease technology disclosed in the '489 patent is used in combination with the alkali / delayed addition embodiment, using calcium hydroxide as the only additional calcium-containing base, There is no need to increase the amount of non-aqueous conversion agent to achieve a useful grease with improved agent yield. In contrast, in Examples 2 to 3 and 5 to 10 in which the embodiment is used in combination with the addition of calcium hydroxyapatite and calcium carbonate addition as calcium-containing bases that react with complexing acids, nonaqueous conversion Although it appeared that it was necessary to increase the amount of agent, in these examples the thickener yield was significantly better than in Examples 12 and 13. Because the overbased calcium sulfonates used in these greases are expensive components, alkali / alkali in combination with added calcium hydroxyapatite and added calcium carbonate, even when it is necessary to add some of the components. It is most preferred to use the delayed addition method embodiment.

[Example 14 (Reference Example, no addition of alkali metal, no delay period)]
Calcium sulfonate complex greases were made according to the composition and method disclosed in US Pat. No. 9,273,265, where the added calcium carbonate is a separately added component in the grease. This grease did not include the addition or delay period of the alkali metal hydroxide. This grease, together with the following grease, serves as a basis for comparison. The grease was made as follows. 310.25 grams of 400 TBN overbased oil-soluble calcium sulfonate was added to the open mixing vessel followed by 368.14 grams of solvent neutral grade 1 paraffinic base oil having a viscosity of about 600 SUS at 100F. The 400 TBN overbased oil-soluble calcium sulfonate was a high quality calcium sulfonate similar to that described and used above in Examples 4 and 12 of the '768 application. The mixing was started using a planetary mixing paddle without heating. Next, 31.31 grams of main C12 alkyl benzene sulfonic acid was added. After mixing for 20 minutes, 75.03 g of finely divided crystalline calcium carbonate having an average particle size of less than 5 microns was added and mixed for 20 minutes. This calcium carbonate was added in addition to the amount of amorphous calcium carbonate contained in the overbased calcium sulfonate. Next, 0.85 grams of glacial acetic acid and 8.09 grams of 12-hydroxystearic acid were added. The mixture was stirred for 10 minutes. Next, 15.83 grams of hexylene glycol and 40.1 grams of water were added (without a delay period) and the mixture was heated to a temperature of 190F-200F while mixing continued. During the heating step, it was noted that the mixture had been converted to a grease structure at about 160F. When the grease reached 190-200 F, Fourier Transform Infrared (FTIR) spectroscopy showed that most of the water was lost due to evaporation. An additional 20 ml of water was added.

  After mixing for 45 minutes at 190 to 200 F, Fourier Transform Infrared (FTIR) spectroscopy indicated that conversion of the amorphous calcium carbonate contained in the overbased calcium sulfonate to crystalline calcium carbonate (calcite) occurred showed that. Next, 1.57 grams of glacial acetic acid and 16.41 grams of 12-hydroxystearic acid were added and allowed to react for 30 minutes. An additional 20 ml of water was added. Next, 16.49 g of a 75% aqueous phosphoric acid solution was slowly added, mixed and reacted. Thereafter, the grease was heated to 390 to 400F. The heating mantle was removed from the mixer and the grease was allowed to cool as mixing continued. When the temperature was below 200 F, a total of 105.38 grams of the same two parts of the same base oil were added. Mixing was continued until the grease reached a temperature of 170F. The grease was then removed from the mixer and passed through a three roll mill three times to finally achieve a smooth and even texture. The 60-round penetration penetration of this grease was 283. The percentage of overbased oil-soluble calcium sulfonate in the final grease was 32.68%. The dropping point was 617F.

Example 15 (Reference Example, no addition of alkali metal hydroxide, no delay period)
Another calcium sulfonate complex grease was made based on the same method and the same composition as the grease of Example 14 above. The grease of this Example 15 and the grease of the previous Example 14 provide a basis for comparison of the following two greases. The grease was made as follows. 310.19 g of 400 TBN overbased oil-soluble calcium sulfonate was added to the open mixing vessel followed by 367.82 g of solvent neutral grade 1 paraffinic base oil having a viscosity of about 600 SUS at 100F. The 400 TBN overbased oil-soluble calcium sulfonate was a high quality calcium sulfonate similar to that previously described and used in Example 4 and Example 12 of '768. The mixing was started using a planetary mixing paddle without heating. Next, 31.28 grams of main C12 alkyl benzene sulfonic acid was added. After mixing for 20 minutes, 75.31 grams of finely divided crystalline calcium carbonate having an average particle size of less than 5 microns was added and mixed for 20 minutes. This calcium carbonate was added in addition to the amorphous calcium carbonate contained in the overbased calcium sulfonate. Next, 0.84 grams of glacial acetic acid and 8.10 grams of 12-hydroxystearic acid were added. The mixture was stirred for 10 minutes. The mixture was then heated to a temperature of 190F-200F while 15.73 grams of hexylene glycol and 41.2 grams of water were added and mixed. During the heating step, it was noted that the mixture had been converted to a grease structure at about 170 °. When the grease reached 190-200 F, Fourier Transform Infrared (FTIR) spectroscopy showed that most of the water was lost due to evaporation. An additional 20 ml of water was added.

  After mixing for 45 minutes at 190 to 200 F, Fourier transform infrared (FTIR) spectroscopy indicated that conversion of amorphous calcium carbonate contained in the overbased calcium sulfonate to crystalline calcium carbonate (calcite) occurred showed that. Next, 1.57 grams of glacial acetic acid and 16.44 grams of 12-hydroxystearic acid were added and allowed to react for 30 minutes. Next, 16.60 grams of 75% aqueous phosphoric acid was slowly added and mixed to react. Thereafter, the grease was heated to 390 to 400F. The heating mantle was removed from the mixer and the grease was allowed to cool as mixing continued. When the temperature was below 200 F, a total of 105.79 grams of the same two base oils were added. Mixing was continued until the grease reached a temperature of 170F. The grease was then removed from the mixer and passed through a three roll mill three times to finally achieve a smooth and even texture. The 60-round penetration penetration of this grease was 280. The percentage of overbased oil-soluble calcium sulfonate in the final grease was 32.66%. The dropping point was 583F. Thus, the thickener yield of this grease is substantially the same as the grease of Example 14 above. Together, these two greases use this particular approach and overbased oil-soluble calcium sulfonate to establish the baseline thickener yield of calcium sulfonate complex greases.

[Example 16]
Another calcium sulfonate complex grease was made similar to the previous two greases. However, the non-aqueous conversion agent hexylene glycol was not initially added with water. Instead, the mixture was heated to 190-200 F (first temperature adjustment delay period) and held in that temperature range for 1 hour (first retention delay period) before being added. No alkali metal hydroxide was added to this grease. The grease was prepared as follows. 310.27 g of 400 TBN overbased oil-soluble calcium sulfonate was added to the open mixing vessel followed by 368.06 g of solvent neutral grade 1 paraffinic base oil having a viscosity of about 600 SUS at 100F. The 400 TBN overbased oil-soluble calcium sulfonate was a high quality calcium sulfonate similar to that previously described and used in Examples 4 and 12 of the '768 application. The mixing was started using a planetary mixing paddle without heating. Next, 31.18 grams of main C12 alkyl benzene sulfonic acid was added. After mixing for 20 minutes, 75.29 g of finely divided crystalline calcium carbonate having an average particle size of less than 5 microns was added and mixed for 20 minutes. This calcium carbonate was added in addition to the amorphous calcium carbonate contained in the overbased calcium sulfonate. Next, 0.85 grams of glacial acetic acid and 8.11 grams of 12-hydroxystearic acid were added. The mixture was stirred for 10 minutes. Thereafter, 41.2 grams of water was added as a conversion agent and the mixture was heated to a temperature of 190 F to 200 F while mixing (first temperature adjustment delay period). The mixture was mixed at this temperature range for 1 hour (first hold delay time). Meanwhile, Fourier transform infrared (FTIR) spectroscopy showed that water was lost by evaporation. An additional 30 ml of water was added.

  One hour later at 190-200 F, 15.66 grams of hexylene glycol was added as a non-aqueous conversion agent. The mixture was visibly converted to grease immediately after hexylene glycol was added. After mixing for 45 minutes at 190 to 200 F, Fourier transform infrared (FTIR) spectroscopy indicated that conversion of amorphous calcium carbonate contained in the overbased calcium sulfonate to crystalline calcium carbonate (calcite) occurred showed that. An additional 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 complexing acids were allowed to react for 30 minutes. Next, 16.99 grams of 75% phosphoric acid aqueous solution was slowly added and mixed to react. Thereafter, the grease was heated to 390 to 400F. The heating mantle was removed from the mixer and the grease was allowed to cool while continuing to stir. When the temperature was below 200 F, a total of 132.34 grams of the two parts of the same base oil was added. Mixing was continued until the grease reached a temperature of 170F. The grease was then removed from the mixer and passed through a three roll mill three times to finally achieve a smooth and even texture. The 60-round penetration penetration of this grease was 286. The percentage of overbased oil-soluble calcium sulfonate in the final grease was 31.77%. The dropping point was> 650F. Such a thickener yield of this grease was slightly improved as compared to the greases of Example 14 and Example 15.

[Example 17 (embodiment of alkali / delayed addition method)]
Another calcium sulfonate complex grease was made as in Example 16 above. However, this grease used an embodiment of the alkaline / delayed addition method. The non-aqueous conversion agent hexylene glycol was not added initially with water, but was added after heating the mixture to 190-200 F (first thermoregulatory delay period). Also, the water initially added contained a very small amount of sodium hydroxide. The sodium hydroxide concentration in the final grease was 0.08%. Note that the batch size of this grease was increased by 50% as compared to the greases of Examples 14-16. However, there was no significant difference between the proportions of each component and the details of the other process steps.

  The grease was made as follows. 465.31 grams of 400 TBN overbased oil-soluble calcium sulfonate was added to the open mixing vessel followed by 367.68 grams of solvent neutral grade 1 paraffinic base oil having a viscosity of about 600 SUS at 100F. The 400 TBN overbased oil-soluble calcium sulfonate was a high quality calcium sulfonate similar to that previously described and used in Example 4 and Example 12 of 768. The mixing was started using a planetary mixing paddle without heating. Next, 46.64 grams of main C12 alkyl benzene sulfonic acid was added. After mixing for 20 minutes, 112.50 grams of finely divided crystalline calcium carbonate having an average particle size of less than 5 microns was added and mixed for 20 minutes. This calcium carbonate was added in addition to the amorphous calcium carbonate contained in the overbased calcium sulfonate. Next, 1.26 grams of glacial acetic acid and 12.20 grams of 12-hydroxystearic acid were added. The mixture was stirred for 10 minutes. Next, 41.2 g of water in which 1.20 g of sodium hydroxide powder was dissolved was added and heated to a temperature of 190 to 200 F while mixing (first temperature adjustment delay period). During the heating step, it was noted that some bubbling started to appear when the temperature reached about 176F. When the mixture reached 190-200 F, 42.13 grams of hexylene glycol was added (no retention delay period). The mixture was converted to grease as it appeared immediately after hexylene glycol was added.

  After mixing for about 20 minutes, the grease was so heavy that 76.61 grams of the same base oil was added. The grease was mixed for another 45 minutes at 190-200F. Meanwhile, Fourier transform infrared (FTIR) spectroscopy showed that water was lost so an additional 40 ml of water was added. At the end of the 45 minutes of mixing, the grease was noticeably thinner. Fourier transform infrared spectroscopy showed that conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) occurred. Thereafter, 2.36 grams of glacial acetic acid and 24.58 grams of 12-hydroxystearic acid were added. The two complexing acids were allowed to react for 30 minutes. Next, 24.74 grams of 75% aqueous phosphoric acid was slowly added and mixed to react. Thereafter, the grease was heated to 390 to 400F. The heating mantle was removed from the mixer and the grease was allowed to cool as mixing continued. When it cooled down, the grease became extremely sticky.

  When the temperature was below 200 F, a total of 284.40 grams of four parts of the same base oil was added. Continue mixing the grease until the temperature reaches 170F. The grease was then removed from the mixer and passed through a three roll mill three times to finally achieve a smooth and even texture. The 60-round penetration penetration of this grease was 274. The percentage of overbased oil-soluble calcium sulfonate in the final grease was 31.84%. The dropping point was> 650F. Using the conventional inverse linear relationship between the worked penetration and the ratio of the concentration of the overbased calcium sulfonate, the grease of this example adds an additional base oil to achieve a worked penetration of Example 16 above. Would have had an overbased calcium sulfonate concentration of 30.52%. Thus, the use of the alkali / delayed addition embodiment in this grease resulted in some improvement in thickener yield when compared to the two reference greases of Example 14 and Example 15. Nevertheless, the degree of improvement is not as pronounced as observed with some of the other example greases. Without being bound by theory, the lower amount of yield improvement provided by this grease may be attributed to the fact that calcium hydroxide has not been added. If the effect of a small amount of sodium hydroxide is indeed due to the rapid reaction of sodium hydroxide with the complexing acid and the subsequent metathesis of fatty acid sodium salts with sodium hydroxide, the absence of calcium hydroxide is certain Will affect that mechanism. In the grease of Example 17, the metathesis reaction must be between fatty acid sodium salt and calcium carbonate, which will not be easy.

  The results of Examples 11 to 17 herein and the processes used are summarized in Table 2 below. All of these examples used high 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 with embodiments of the alkali / delayed addition method that changes the timing of alkali metal addition.

Example 18 (Reference Example-no addition of alkali metal hydroxide, no delay time)
Calcium sulfonate complex according to the scope of U.S. Pat. Nos. 5,308,514 and 5,338,467 (issued to Witco Corporation on May 3, 1994 and Aug. 16, 1994, respectively) The grease was made. In these patents, at least a portion of the long chain fatty acid is added prior to conversion and can act as a conversion agent, and only calcium hydroxide or calcium oxide is added as a calcium-containing base that reacts with the complexing acid (' Calcium hydroxyapatite or added calcium carbonate as in the 768 application). This example is the same as Example 6A of the '476 application, with 54.1% of the total amount of 12-hydroxystearic acid and all of the glacial acetic acid added prior to conversion. The remaining amount of 12-hydroxystearic acid was added after conversion, followed by the addition of calcium hydroxide and aqueous boric acid mixture. Also, no alkali metal hydroxide was added and there was no delay between the addition of water and the addition of the main non-aqueous conversion agent. This grease serves as a basis for comparison.

  The grease of Example 18 was produced as follows. 380.73 g of 400 TBN overbased oil-soluble calcium sulfonate was added to the open mixing vessel followed by 604.50 g of solvent neutral grade 1 paraffinic base oil having a viscosity of about 600 SUS at 100F. The mixing was started using a planetary mixing paddle without heating. The 400 TBN overbased oil-soluble calcium sulfonate was a high quality calcium sulfonate similar to that previously described and used in Examples 4 and 12 of the '768 application. Next, 21.66 grams of main C12 alkyl benzene sulfonic acid was added. After mixing for 20 minutes, 21.59 grams of 12-hydroxystearic acid was added followed by 18.16 grams of hexylene glycol and 38.0 grams of water. After mixing for 10 minutes, 2.40 grams of glacial acetic acid was added. The batch was then heated with continuous stirring until the temperature reached 190F. The temperature was held at 190F-200F for 45 minutes. The batches were mixed until Fourier Transform Infrared (FTIR) spectroscopy showed that conversion of amorphous calcium carbonate contained in the overbased calcium sulfonate to crystalline calcium carbonate (calcite) had occurred.

  A further 249.94 grams of paraffinic base oil was added followed by 18.21 grams of 12-hydroxystearic acid. This was mixed for 15 minutes while maintaining the temperature at 190F-200F. Next, 38.02 grams of finely divided food grade purity calcium hydroxide having an average particle size of less than 5 microns was mixed with 50 grams of water, and the mixture was added to the grease. Then 23.02 g of boric acid was mixed with 50 ml of hot water and the mixture was added to the grease. The grease was then heated to 390F. The heating mantle was then removed and the grease was allowed to continue stirring in the open air to cool. Once the grease had cooled to 170 F, it was removed from the mixer and passed through a three roll mill three times to finally achieve a smooth and even texture. The 60-round penetration penetration of this grease was 339. The percentage of overbased oil-soluble calcium sulfonate in the final grease was 27.62%. The dropping point was 640F.

Example 19 (Delayed Addition Method of the '476 Application. No Addition of Alkali Metal Hydroxide)
Another calcium complex grease was made using the same equipment, ingredients, amounts and manufacturing process as the grease of Example 18 but at a first temperature between the addition of water and the addition of hexylene glycol as a non-aqueous conversion agent. There was an adjustment delay period (heating to 190-200) and a first holding delay period (one hour hold at 190-200). No alkali metal hydroxide was added. Upon addition of hexylene glycol, the grease was held at 190F to 200F until the conversion appeared to be complete. The remaining process thereafter was the same as the grease of Example 18 above. The final 60-round penetration consistency of the grease was 281. The percentage of overbased oil-soluble calcium sulfonate in the final grease was 27.60%. The dropping point was> 650F. Thus, the grease of this example, despite having essentially the same proportion of overbased oil-soluble calcium sulfonate, demonstrates the previous practice as evidenced by the harder consistency. It had improved thickener yield compared to the grease of Example 18. In fact, using the conventional inverse linear relationship between the worked penetration and the ratio of the concentration of overbased calcium sulfonate, it is diluted with sufficient base oil to achieve the same worked penetration as the grease of Example 18 If obtained, the expected percentage of overbased calcium sulfonate in the grease of Example 19 would be 24.2%.

[Example 20 (embodiment of alkali / delayed addition method)]
Another grease was made in the same manner as the grease of Example 19 above in that the addition of the non-aqueous conversion agent hexylene glycol is delayed until the mixture is heated to 190-200F. However, with this grease, a small amount of sodium hydroxide was dissolved in the first part of the water added at ambient temperature before heating of the batch began. In addition, when the temperature range of 190 to 200 F was reached, there was no holding delay time of 1 hour. Instead, hexylene glycol was added immediately when the temperature range was reached. This is observed with the grease of Example 7 above. It has been observed that with such greases, holding temperature delays for non-aqueous conversion agents do not result in the highest improvement in thickener yield when alkali metal hydroxide is further added.

  The grease was made as follows. 380.79 g of 400 TBN overbased oil-soluble calcium sulfonate was added to the open mixing vessel followed by 589.33 g of solvent neutral grade 1 paraffinic base oil having a viscosity of about 600 SUS at 100F. The mixing was started using a planetary mixing paddle without heating. The 400 TBN overbased oil-soluble calcium sulfonate was a high quality calcium sulfonate similar to that previously described and used in Examples 4 and 12 of the '768 application. Next, 21.63 grams of main C12 alkyl benzene sulfonic acid was added. After mixing for 20 minutes, 21.58 grams of 12-hydroxystearic acid was added followed by 38.14 grams of water in which 0.85 grams of sodium hydroxide powder was dissolved. After mixing for 10 minutes, 2.40 grams of glacial acetic acid was added. The batch was then heated while mixing until the temperature reached 190-200F (first temperature control period). It was noted that foaming was observed when the temperature reached about 180F. When the temperature reached 190-200F, 27.57 grams of hexylene glycol was added (no retention delay). After about 10 minutes, the batch was converted to a grease structure.

  The batch was then mixed for an additional 45 minutes, until Fourier Transform Infrared (FTIR) spectroscopy showed that conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) had occurred. While mixing for 45 minutes, an additional 40 ml of water was added to replace the water lost by evaporation. Next, 18.27 grams of 12-hydroxystearic acid was added and mixed for 15 minutes while maintaining the temperature at 190F-200F. Next, 38.04 grams of finely divided food grade purity calcium hydroxide having an average particle size of less than 5 microns was mixed with 50 grams of water, and the mixture was added to the grease. Then 23.04 g of boric acid was mixed with 50 ml of hot water and the mixture was added to the grease. The grease was then heated to 390F. The heating mantle was then removed and the grease was allowed to continue stirring and cooling in the open air. During cooling, the grease became very sticky. A total of 253.87 grams of three approximately equal parts of the same base oil were added and mixed with the grease. Once the grease had cooled to 170 F, it was removed from the mixer and passed through a three roll mill three times to finally achieve a smooth and even texture. The 60-round penetration penetration of this grease was 280. The dropping point was> 650F. The percentage of overbased oil-soluble calcium sulfonate in the final grease was 27.65%. The concentration of sodium hydroxide in the final grease was 0.06%.

[Example 21 (embodiment of alkali / delayed addition method)]
Another grease was made substantially the same as the grease of Example 20 above. The only significant difference is that a mixture of sodium hydroxide with water was added after the conversion was complete. Next, a second portion of 12-hydroxystearic acid and a mixture of boric acid and hot water were added. The final 60-round penetration consistency of the grease was 285. The dropping point was> 650F. The percentage of overbased oil-soluble calcium sulfonate in the final grease was 27.40%. The concentration of sodium hydroxide in the final grease was 0.06%. Thus, the thickener yields of the greases of Example 19, Example 20, and Example 21 were all significantly superior to the reference grease of Example 18. However, when high quality overbased calcium sulfonate is used, the use of the alkali / delayed addition embodiment results in thickener yields that far exceed those obtained with the delayed addition method of the '476 application alone. Did not bring about an improvement. This is the thickener yield in the alkali metal hydroxide addition and / or delayed non-aqueous converter method when using low quality overbased calcium sulfonate instead of high quality overbased calcium sulfonate It seems to show that it can be improved most.

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

  Further examples showing the results of the addition of alkali metal hydroxides to simple calcium sulfonate greases can be found in the following examples.

[Example 22: (Reference Example-no addition of alkali metal hydroxide; no delay period)]
According to the scope of U.S. Pat. Nos. 3,377,283 and 3,492,231 (issued to Lubrizol Corporation on April 9, 1968 and January 27, 1970, respectively), delayed or alkaline. Simple calcium sulfonate greases were made to be used as a basis for comparison of the following three greases without the addition of metal hydroxides. The grease was manufactured as follows. 496.49 grams of 400 TBN overbased oil-soluble calcium sulfonate were added to the open mixing vessel followed by 394.45 grams of solvent neutral grade 1 paraffinic base oil having a viscosity of about 600 SUS at 100F. The mixing was started using a planetary mixing paddle without heating. The 400 TBN overbased oil-soluble calcium sulfonate was a high quality calcium sulfonate similar to that previously described and used in Examples 4 and 12 of the '768 application. Next, 20.23 grams of main C12 alkyl benzene sulfonic acid was added. After mixing for 20 minutes, 44.23 grams of water were added followed by 16.57 grams of hexylene glycol (the main conversion agent). The batch was then heated with mixing until the temperature reached 190F. When the temperature reached 190 F, 6.20 grams of glacial acetic acid was added. When visible conversion to grease structure is observed, it is Fourier-transformed that conversion of amorphous calcium carbonate contained in overbased calcium sulfonate to crystalline calcium carbonate (calcite) has occurred An additional 10 ml of water was added while the temperature was held between 190 F and 200 F for 45 minutes, until infrared (FTIR) spectroscopy indicated. The resulting grease was then heated to 330F. The heating mantle was then removed and the grease was allowed to continue stirring in the open air to cool. When the temperature reached 200 F, 2.34 grams of an arylamine antioxidant was added. Once the grease had cooled to 170 F, it was removed from the mixer and passed through a three roll mill three times to finally achieve a smooth and even texture. The 60-round penetration penetration of this grease was 331. The percentage of overbased oil-soluble calcium sulfonate in the final grease was 53.03% and the dropping point was> 650F.

Example 23 (Delayed Addition Method of the '476 Application. No Alkali Addition)
Another simple calcium sulfonate grease was made in the same manner as the previous Example 22 grease, except that there was a delay period between the addition of water and the addition of non-aqueous conversion agent. In this example, no alkali metal hydroxide was added. The grease was made as follows. 495.41 grams of 400 TBN overbased oil-soluble calcium sulfonate were added to the open mixing vessel followed by 391.96 grams of solvent neutral grade 1 paraffinic base oil having a viscosity of about 600 SUS at 100F. The mixing was started using a planetary mixing paddle without heating. The 400 TBN overbased oil-soluble calcium sulfonate was a high quality calcium sulfonate similar to those previously described and used in Examples 4 and 12 of the '768 application. Next, 19.65 grams of main C12 alkyl benzene sulfonic acid was added. After mixing for 20 minutes, 44.42 grams of water was added. The mixture was then heated to 160 F (first temperature adjustment delay period) and held between 160 F and 170 F for 2 hours and 30 minutes (first holding delay period). During this time, an additional 50 ml of water was added as most of the water originally added had evaporated. The batch was then heated to 190 F (second temperature adjustment delay time) and 16.53 grams of hexylene glycol (main converting agent) was added followed by 6.34 grams of glacial acetic acid.

  When visible transformation to a grease structure is observed, 190F until Fourier Transform Infrared (FTIR) spectroscopy shows that a conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) has occurred. The temperature was held for 45 minutes at ~ 200F. During this time, another 10 ml of water was added. The resulting grease was then heated to 330F. The heating mantle was then removed and the grease was allowed to continue stirring and cooling in the open air. When the temperature reached 200 F, 2.32 grams of arylamine antioxidant was added. Once the grease had cooled to 170 F, it was removed from the mixer and passed through a three roll mill three times to finally achieve a smooth and even texture. The dropping point of the grease of Example 21 was> 650F. The 60-round penetration penetration of this grease was 290. The percentage of overbased oil-soluble calcium sulfonate in the final grease was 53.14%.

  This grease and the grease of Example 22 above are found to have essentially the same proportion of overbased calcium sulfonate. However, the worked penetration of this grease was hard at 41 points. Thus, the delayed glycol procedure used for this grease resulted in an improvement in thickener yield. In fact, using the conventional inverse linear relationship between the worked penetration and the ratio of the concentration of the overbased calcium sulfonate, it can be diluted with sufficient base oil to achieve the same worked penetration as the grease of Example 22. If obtained, the predicted percentage of overbased calcium sulfonate in the grease of this Example 23 would be 46.6%. In addition, very high drop points were maintained.

Example 24 (Alkali Addition and Delayed Addition)]
Another simple calcium sulfonate grease was made in the same manner as the grease of previous example 23, but using different delay times between the addition of water and the addition of the non-aqueous conversion agent, and a small amount of Sodium hydroxide was added. The concentration of sodium hydroxide in the final grease was 0.09%. The grease was made as follows. 495.18 g of 400 TBN overbased oil-soluble calcium sulfonate was added to the open mixing vessel and 392.56 g of solvent neutral grade 1 paraffinic base oil having a viscosity of about 600 SUS at 100 F was added. The mixing was started using a planetary mixing paddle without heating. The 400 TBN overbased oil-soluble calcium sulfonate was a high quality calcium sulfonate similar to that previously described and used in Examples 4 and 12 of the '768 application. Next, 20.31 grams of main C12 alkyl benzene sulfonic acid was added. After mixing for 20 minutes, 0.88 grams of sodium hydroxide powder was dissolved in 44.0 grams of water and the resulting solution was added. The mixture was then heated to 190 F (first temperature adjustment delay period) and 16.73 grams of hexylene glycol and 6.16 grams of glacial acetic acid were added.

  When visible conversion to grease structure is observed, the temperature is measured until Fourier transform infrared (FTIR) spectroscopy shows that conversion of amorphous calcium carbonate to crystalline calcium carbonate (calcite) has occurred. Was held at 190F to 200F for 45 minutes. An additional 20 ml of water was added during this time. The resulting grease was then heated to 330F. The heating mantle was then removed and the grease was allowed to continue stirring and cooling in the open air. When the temperature reached 200 F, 3.35 grams of an arylamine antioxidant was added. Once the grease had cooled to 170 F, it was removed from the mixer and passed through a three roll mill three times to finally achieve a smooth and even texture. The dropping point of the grease of Example 24 was 478F. The 60-round warm consistency of this grease was 311. The percentage of overbased oil-soluble calcium sulfonate in the final grease was 52.95%.

  Comparing this grease to that of the previous example 23, it is clear that in this grease the benefits observed by using the alkali / delayed addition embodiment in the previous grease example are not observed is there. In the grease of this Example 24, the thickener yield was significantly reduced and the dropping point was reduced as compared to the grease of the previous Example 23. Again, without being bound by theory, the addition of the alkaline hydroxide improves the thickener yield mainly due to the reaction with the complexing acid used to make the complex calcium sulfonate grease Seem. However, simple greases do not involve the addition of complexing agents, so the benefits can not be obtained with simple greases, and adding alkali metal hydroxides to simple grease compositions is detrimental to thickener yield It seems like that. The results of Examples 22-24 are summarized in Table 4 below.

  The example of the complex grease uses the alkali / delayed addition embodiment regardless of whether the previously described calcium sulfonate grease technology is being used consistently with thickener yield. It shows that it improves. In addition, improvements in thickener yield have been observed regardless of whether the overbased calcium sulfonate used is of high or low quality, as defined in the '768 application. Within the exemplary compositions included herein, a lower quality calcium sulfonate achieves greater improvement (which would be contrary to expectations).

  The above-described grease examples made based on the alkali / delayed addition method of the present invention are also compared to the example greases in which the addition of all or part of the non-aqueous conversion agent is not delayed. The components used in the various comparative groups of and the amounts and their components were identical or substantially similar but showed different physical properties. Testing of the samples of the example greases using Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) shows that the greases produced with the delayed addition according to the invention are not delayed. It was demonstrated to be distinguishable from those of similar composition that was made. There are differences in the profiles of the absorption curves, for example differences in particle size and structure.

  Examples provided herein include NLGI no. 1, No. 2 or No. It is classified into 3 grade, No. Although two grades are most preferred, the scope of the present invention is as follows. It should further be understood to include all NLGI consistency grades that are harder or softer than two grades. However, as will be appreciated by those skilled in the art, greases according to the present invention may be prepared according to NLGI no. Even if they are not of two grades, their properties are as good as no. It should be consistent with what would have been obtained when bringing in a 2 grade product.

  Although the present invention deals mainly with greases made in open containers, the examples are all open containers, complex calcium sulfonate grease compositions and methods may be used in closed containers which can be heated under pressure . The use of such pressurized containers can result in better thickener yields than those described in the Examples herein. For the purposes of the present invention, an open container is any container with or without a top cover or hatch, which generates a large pressure during heating unless such a top cover or hatch is airtight. I can not While using such an open container with a closed top cover or hatch during the conversion process helps to maintain the required level of water as a conversion agent, it is usually the boiling point of water or that of Allows conversion temperatures above. Such higher conversion temperatures can further improve the thickener yield of simple and complex calcium sulfonate greases, as will be appreciated by those skilled in the art.

  As used herein, the term "thickener yield" as applied to the present invention has its usual meaning: Standard penetration test ASTM D217 commonly used in lubricating grease manufacture. Or the concentration of highly overbased oil-soluble calcium sulfonate required to give the grease a particular desired consistency, as measured by D1403. Similarly, the "drop point" of a grease refers to the value obtained using the standard drop point test ASTM D2265 commonly used in lubricating grease manufacture. As used herein, references to the immediate addition of components after reaching the temperature are physically possible, given the amount added and the equipment used. It is meant to add the component immediately after it has been reached, but for a short time, less than 10 minutes, more preferably less than 5 minutes.

As used herein, (1) the amount of dispersed calcium carbonate (or amorphous calcium carbonate) or residual calcium or calcium hydroxide contained in the overbased calcium sulfonate is an overbased calcium sulfonate (2) several components are added as two or more separate parts, each part can be described as a percentage of the total amount of the components, and (3) specified by proportions or parts For all other amounts of ingredients (including the total amount), certain ingredients (eg, water reacting with other ingredients, calcium containing bases or alkali metal hydroxides) may not be present in the final grease, or The amount added as a component by weight of the final grease product, even though it may not be present in the final grease in the amount specified to be added as a component. As used herein, "added 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, "added calcium hydroxide" and "added calcium oxide" are each added to the amount of residual calcium hydroxide and / or calcium oxide that may be included in the overbased calcium sulfonate It means calcium hydroxide and calcium oxide added as separate components. As used herein to describe the present invention (apart from how the term is used in some prior art documents), calcium hydroxyapatite has the formula (1) Ca ₅ A compound having (PO ₄ ) ₃ OH, or (2) a compound having a mathematically equivalent formula, wherein (a) has a melting point of about 1100 ° C., or (b) tricalcium phosphate and calcium hydroxide And compounds that specifically exclude the mixture of in the equivalent formula. Those skilled in the art, upon reading the present specification, will make changes and substitutions of the composition and method for producing the composition, including the examples contained herein, within the scope of the present invention. It will be understood that the scope of the invention disclosed herein is intended to be limited only by the broadest interpretation of the appended claims.

Claims (33)

A method of producing a complex overbased calcium sulfonate grease, comprising
Mixing an amount of overbased oil-soluble calcium sulfonate in which amorphous calcium carbonate is dispersed with a base oil and one or more converting agents to form a pre-conversion mixture;
Converting the pre-conversion mixture into a conversion mixture by heating until conversion of amorphous calcium carbonate to crystalline calcium carbonate occurs;
Mixing an amount of an alkali metal hydroxide with the pre-conversion mixture, the conversion mixture, or both;
Mixing an amount of one or more complexing acids with the pre-conversion mixture, the conversion mixture, or both;
Mixing one or more calcium-containing bases with the pre-conversion mixture, the conversion mixture, or both;
Contains and
The one or more calcium-containing bases include calcium hydroxyapatite, calcium added hydroxide, calcium oxide added, calcium carbonate added, or any combination thereof,
The method wherein the amount of overbased oil soluble calcium sulfonate is 10% to 45% of the final grease weight . The method of claim 1, wherein the amount of alkali metal hydroxide is 0.005% to 5% of the final grease weight .   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 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, the conversion mixture, or both. Overbased calcium sulfonate is a low-quality calcium sulfonate grease has to have a dropping point of at least 575 ° F, calcium sulfonate low quality, overbased calcium sulfonate grease, calcium hydroxyapatite or alkali metal A method according to claim 1, wherein the overbased calcium sulfonate grease having a dropping point of less than 575F is made to be made according to prior art methods which do not include the addition of hydroxide . The conversion agent comprises water and one or more non-aqueous conversion agents,
Forming a first mixture by mixing water, an overbased calcium sulfonate, a base oil, and optionally a first portion of one or more non-aqueous conversion agents ;
After one or in a plurality of delay periods, or they, and the first or second parts of the plurality of kinds of nonaqueous conversion agent mixing the first mixture,
Contains and
The delay period is
(1) A temperature adjustment delay period in which the first mixture or the pre-conversion mixture is heated or cooled, or
The method according to claim 1, wherein (2) the first mixture or the pre-conversion mixture comprises a holding delay period maintained for a period of time at or within a temperature range . Alkali metal hydroxide to form a solution dissolved in water used as the conversion agent, the solution is to form a first mixture is mixed with overbased calcium sulfonate and a base oil, to claim 7 Method described. The alkali metal hydroxide to form a second portion was dissolved in the solution of water, the solution is first mixture, the mixture prior to conversion, transformation mixture, or is mixed with a combination thereof, to claim 7 Method described. 8. The method according to claim 7 , wherein at least all or part of a certain complexing acid is mixed with the first mixture or mixture before conversion, and at least all or part of the same or different complexing acid is mixed with the conversion mixture. Method. 11. The method of claim 10 , wherein at least a portion of certain complexing acids are mixed with the first mixture or the pre-conversion mixture prior to any heating. The converting step is
Heating the pre-conversion mixture to a conversion temperature range of 190 ° F. to 230 ° F. for open vessels, or another temperature range where conversion occurs for closed vessels;
Maintaining the temperature in the range until conversion of amorphous calcium carbonate to crystalline calcium carbonate occurs;
The method of claim 7 , comprising: One or more complexing acids comprise acetic acid and 12-hydroxystearic acid, part of both acids being mixed with the first mixture or the pre-conversion mixture, another part of both acids 11. The method of claim 10 , wherein is mixed with the conversion mixture. The method according to claim 1, wherein the complexing acid or acids further comprises boric acid, phosphoric acid, or both, wherein all of the boric acid, phosphoric acid, or both are mixed with the conversion mixture. The method of 13 . 14. The method of claim 13 , wherein the non-aqueous conversion agent is hexylene glycol and is mixed with the first mixture after a temperature adjustment delay period. 14. The method of claim 13 , 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 at least 575 ° F and the amount of overbased calcium sulfonate is 10% to 32% of the final grease weight . The method according to claim 7 , wherein the calcium sulfonate grease has a dropping point of at least 575 ° F and the amount of overbased calcium sulfonate is 10% to 32% of the final grease weight . (1) adding a first portion of one or more non-aqueous conversion agents to the first mixture before any delay period , and (2) a third of one or more non-aqueous conversion agents part of the first mixture after the delay period during or delay period, and further comprising a step of adding the one or the plurality of the delay period, or before conversion mixture after their method of claim 7. 20. The method of claim 19 , wherein the non-aqueous conversion agent comprises acetic acid only if acetic acid is added with water prior to any delay period . 8. The method of claim 7 , wherein at least one of the one or more non-aqueous conversion agents is a glycol, a glycol ether, or a glycol polyether. 22. The method of claim 21 , wherein the glycol is hexylene glycol. Prior to all delay periods, a portion of hexylene glycol is mixed with the first mixture, and after one or more delay periods, another portion of hexylene glycol is the first mixture. 23. The method of claim 22 , wherein the method is mixed with a pre-conversion mixture. The method according to claim 7 , wherein there are at least two delay periods, one of the delay periods being a temperature adjustment delay period and at least one other delay period being a holding delay period. Overbased calcium sulfonate, overbased calcium sulfonate der low quality is, calcium sulfonate low quality, overbased calcium sulfonate grease, include calcium carbonate, the addition of calcium hydroxyapatite or alkali metal hydroxides The method according to claim 7 , wherein the overbased calcium carbonate sulfonate grease having a dropping point of less than 575 ° F is produced when it is manufactured based on the prior art method. The overbased calcium sulfonate contains 0% to 8% of residual calcium hydroxide and / or calcium oxide based on the weight of the overbased calcium sulfonate , and calcium hydroxyapatite, added calcium carbonate, or only their combination , Ru is added as a calcium-containing base to react with complexed acid the method of claim 7. At least one of the one or more non-aqueous conversion agent, methanol, or isopropyl alcohol, The method of claim 7. 8. The method according to claim 7 , wherein only glycols, glycol ethers, glycol polyethers or combinations thereof are used as non-aqueous conversion agents. The method according to claim 1, wherein the amount of overbased calcium sulfonate is 10% to 22% of the final grease weight .   The method according to claim 1, wherein at least a portion of the alkali metal hydroxide is added to the pre-conversion mixture. At least a portion of the A alkali metal hydroxide is added prior to the reaction of one or more calcium containing base and one or more complexes, acid, The method of claim 1. And at least a portion of one or more calcium-containing base, and at least a portion of one or more complexes of acids, at least part of the alkali metal hydroxide after being mixed, are added and mixed, The method of claim 1.   The method according to 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 the same or different alkali metal hydroxide is added to the conversion mixture.