JP2011518245A - Overbased metal carboxylate precursor and process for producing the same - Google Patents

Abstract

  By reacting an alkaline earth metal base with a carboxylic acid in the presence of a hydrocarbon liquid, a polyol and an alcohol, a fluid liquid capable of long-term storage of an overbased alkaline earth metal salt is prepared. The resulting overbased alkaline earth metal salt has an alkaline earth metal content of at least about 14.5% and a non-volatile content of at least about 95%.

Description

  This international patent application claims priority to US patent application Ser. No. 12 / 106,358, filed Apr. 21, 2008.

  The present invention relates to a fluid liquid capable of long-term storage of an alkaline earth metal salt of a fatty acid and a method for preparing the liquid. More particularly, the present invention relates to a long-term storable flowable precursor of an overbased alkaline earth metal carboxylate and a method for preparing the precursor. More particularly, the present invention relates to a long-term storable fluid precursor of an overbased calcium carboxylate and a method for preparing the precursor.

  The preparation of overbased calcium or barium salts of carboxylic acids, alkylphenols and sulfonic acids is described in US Pat. Nos. 2,616,904; 2,760,970; 2,767,164; No. 2,802,816; No. 3,027,325; No. 3,031,284; No. 3,342,733; No. 3,533,975; No. 3,773,664 No .; and 3,779,922. The use of these overbased metal salts in halogen-containing organic polymers is described in the following US Pat. Nos. 4,159,973; 4,252,698; and 3,194,823. Yes. In recent years, the use of overbased barium salts in stabilizer formulations has increased. This is mainly due to the fact that overbased barium salts have performance advantages over neutral barium salts. The performance advantages associated with overbased barium salts are low plate-out, excellent color retention, sufficient long-term thermal stability performance, sufficient compatibility with stabilizer components, and the like. Unfortunately, most overbased barium salts are dark in color, and these dark overbased barium salts are effective stabilizers for halogen-containing organic polymers, but the dark color changes the final product. Let This feature substantially prohibits the use of dark overbased barium salts in applications where a light polymer product is desired.

  According to the teachings of U.S. Pat. No. 4,665,117, light colored alkali or alkaline earth metal salts are prepared using alkylphenols as promoters. However, alkylphenols are also a major cause of color development in the final product. This problem is overcome by the use of propylene oxide. Propylene oxide limits the generation of colored species by replacing the hydrogen of the phenolic hydroxyl group. However, this method has drawbacks mainly due to the toxicity of propylene oxide. Propylene oxide has been classified as a potential carcinogen and evidence of its association with cancer has been found in studies inhaled by laboratory animals. Propylene oxide has also been cited as a severe eye irritant and can cause permanent eye damage if exposed to propylene oxide vapor for extended periods of time. Furthermore, propylene oxide is essentially highly flammable and explosive under certain conditions. Propylene oxide boils at 94 ° F. and ignites at −20 ° F. As a result, maximum care is required to handle propylene oxide at the plant site. Propylene oxide requires special storage equipment and other safety facilities. US Pat. No. 4,665,117 describes the use of propylene oxide at 150 ° C. At this temperature, propylene oxide is in the gas phase. Under these operating conditions, propylene oxide leaks from the reaction mixture, so that more than the theoretical amount of propylene oxide is required to complete the reaction, which necessitates handling of excess propylene oxide.

  Overbased metal carboxylate liquids are also used in the preparation of greases. In particular, the manufacture of greases includes multi-step manufacturing methods and numerous additives to improve properties, which are increasingly greater for formulators of special, food and biological greases. Presents challenges. The resulting grease performance is also highly dependent on processing conditions such as temperature, pressure, residence time, and saponification stoichiometry.

  Contains thixotropic greases or grease-like overbased metal carboxylates or other overbased metals that have corrosion-inhibiting properties and are useful for a variety of applications, such as undercoating for cars and truck bodies, as well as various other purposes Compositions are known in the art. Such greases or grease-like compositions are used fairly extensively on their own or mixed with other ingredients, producing compositions for use in a variety of environments. Furthermore, in general, they are characterized by very good ultra-high pressure and wear resistance, high dropping point, quite good mechanical fracture resistance, salt spray and water corrosion resistance, high temperature thermal stability, and other desirable properties. To do.

  Whether the overbased carboxylic acid metal salt liquid is used in a halogen-containing organic polymer or in the preparation of a grease, the volatile component (volatile organic compound (VOC) of the overbased carboxylic acid metal salt is used. )) Should be as low as possible for health, safety and environmental reasons.

  Despite the state of the art described herein, further improvements to the preparation of overbased alkaline earth metal salts of fatty acids for use in halogen-containing organic polymers and for use in the preparation of greases. is required. That is, the overbased alkaline earth metal salt needs to be improved so that the level of volatile components in the final product is significantly reduced.

  In general, one aspect of the present invention is to provide a long-term storable liquid of an overbased alkaline earth metal salt of a fatty acid. The alkaline earth metal salt has an alkaline earth metal content of at least about 14.5% and a non-volatile content of at least about 95%.

  In yet another aspect of the invention, a long-term storable flowable liquid of an overbased alkaline earth metal salt of a fatty acid is provided. The liquid includes at least one hydrocarbon liquid, a polyol, an alcohol having at least 8 carbon atoms, and an overbased alkaline earth metal salt of a fatty acid, the alkaline earth metal salt being at least It has an alkaline earth metal content of about 14.5% and a non-volatile content of at least about 95%.

In another aspect of the invention, a method of preparing a long-term storable fluid liquid of an overbased alkaline earth metal salt of a fatty acid is provided. This method
(A) preparing a precursor mixture comprising a carboxylic acid that is a fatty acid, at least one hydrocarbon liquid, a polyol, and an alcohol having at least 8 carbon atoms;
(B) neutralizing the carboxylic acid with an initial amount of alkaline earth metal base to form a precursor mixture of a carboxylic acid alkaline earth metal salt;
(C) heating the carboxylic acid alkaline earth metal salt precursor mixture;
(D) adding an additional amount of an alkaline earth metal base to the carboxylic acid alkaline earth metal salt precursor mixture;
(E) carbonating the precursor mixture to neutrality;
(F) filtering the precursor mixture;
(G) distilling the precursor mixture until an alkaline earth metal content of at least about 14.5% and a non-volatile content of at least about 95% is obtained.

  The above and other advantages and novel features of the invention will be more fully understood from the following description, along with the details of the illustrated embodiment.

1 is a graph of thermogravimetric analysis of a fluid liquid that can be stored for a long period of an overbased alkaline earth metal salt of a fatty acid in one embodiment of the present invention.

  In one embodiment of the invention, the long-term storable flowable liquid of the fatty acid overbased alkaline earth metal salt prepared from the precursor comprises an alkaline earth metal carbonate, a carboxylic acid alkaline earth metal salt of a fatty acid, A liquid hydrocarbon and an alcohol having at least 8 carbon atoms, the liquid having an alkaline earth metal content of at least about 14.5% and a non-volatile content of at least about 95%.

  The alkaline earth metal of the overbased alkaline earth metal salt of the fatty acid precursor can be selected from the group consisting of calcium, barium, magnesium and strontium. These metals may be derived from metal oxides and hydroxides, and in some cases, may be derived from metal sulfides and hydrosulfides. For example, the alkaline earth metal salt may include calcium carboxylate.

The carboxylic acid portion of the overbased alkaline earth metal salt precursor includes C ₈ -C ₃₀ saturated and unsaturated carboxylic acids consisting of ₈ to ₃₀ carbon atoms, alone or in combination with each other, or of carboxylic acids Mention may be made of fatty acids, including reactive equivalents. Examples of useful carboxylic acids and fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, myristoleic acid, 2-ethylhexanoic acid, decanoic acid, dodecanoic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, stearic acid , 12-hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, linoleic acid, arachidic acid, gadoleic acid, behenic acid, erucic acid, and any mixture of these acids.

  The fluid liquid capable of long-term storage of the overbased alkaline earth metal salt of the fatty acid precursor of the present invention can further contain an alcohol that promotes the formation of the overbased carboxylic acid alkaline earth metal salt. Alcohols include aliphatic alcohols containing at least 8 carbon atoms. In one example, an aliphatic alcohol having in the range of about 8 to about 18 carbon atoms can be used. Examples of such aliphatic alcohols include isodecanol, dodecanol, octanol, tridecanol, tetradecanol or mixtures thereof. It has been found that the use of higher aliphatic alcohols in the manufacture of overbased products can exclude phenol as an accelerator from the reaction.

  The long-term storable liquid of the overbased alkaline earth metal salt of the fatty acid precursor of the present invention may further contain a polyol. The polyol can be a glycol or glycol ether. The glycol or glycol ether is from the group consisting of diethylene glycol monobutyl ether (butyl Carbitol®), triethylene glycol, hexylene glycol, propylene glycol, dipropylene glycol, diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and mixtures thereof. You can choose.

  In another embodiment of the invention, a liquid base oil can also be used to prepare the overbased precursor material. The base oil can be a hydrocarbon liquid that generally includes any hydrocarbon diluent. Most commonly, the liquefied hydrocarbon is selected from the group consisting of hydrocarbon oils, mineral spirits, non-aromatic hydrocarbons and polyalphaolefins (PAO). In one embodiment of the present invention, suitable hydrocarbon liquids include SHELLSOL ™ D70 and D80 commercially available from Shell Chemical. In yet another embodiment, PAO is used alone or in combination with other liquefied hydrocarbons as liquefied hydrocarbons suitable for the preparation of overbased precursor materials. This is because PAO has flexible branched alkyl groups on every other carbon of the polymer backbone. These alkyl groups can take many forms, making it very difficult for the macromolecules to be ordered. In addition, many PAOs are relatively stable at higher temperatures and usually tend to not crystallize or solidify at lower temperatures because PAO can exist as an oily viscous liquid.

  In yet another embodiment of the present invention, a method of preparing a long-term storable liquid of an overbased alkaline earth metal salt of a fatty acid precursor comprises: at least one liquefied carbonization of an alkaline earth metal base and a fatty acid. Reacting in the presence of hydrogen, alcohol and glycol ether in an equivalent ratio of metal base to fatty acid exceeding 1: 1. This mixture can be acidified and carbonated to produce amorphous alkaline earth metal carbonate in the mixture. A stable haze-free liquid reaction by adding a relative amount of a dispersion containing an alkaline earth metal base, a liquefied hydrocarbon and an alcohol having at least 8 carbon atoms at a controlled base addition rate during carbonation. A product can be produced. During this reaction, water is removed from the reaction product to produce a fluid liquid overbased alkaline earth metal salt that can be stored for a long time. In general, the entire process can be performed in the absence of free oxygen, and a nitrogen environment can be used for this purpose.

  Throughout this specification and claims, the term “basic” or “overbased” as applied to alkaline earth metal salts is a ratio of the total metal to the fatty acid moiety contained in the metal composition. Used to refer to a metal composition that is greater than the stoichiometric ratio of the neutral metal salt. That is, the number of metal equivalents is greater than the number of equivalents of fatty acids. In some cases, the degree to which excess metal is present in the basic metal salt is described as the “metal ratio”. As used herein, the metal ratio refers to the ratio between the total alkaline earth metal in the oil-soluble composition and the equivalent number of fatty acids or organic moieties. Basic metal salts are often referred to in the art as “overbased” or “superbasic” to indicate the presence of excess basic components.

It has been found that it is important to add a relative amount of a dispersion of metal base, liquefied hydrocarbon and aliphatic alcohol at a controlled rate during carbonation to produce a stable reaction product. There are several reasons that may contribute to the production of a stable liquid. This stable liquid can later be filtered to remove impurities and reaction by-products. It has been found that these results can be achieved by the continuous addition of a base dispersion or slurry during carbonation. The metal base slurry is believed to prevent the formation of undesirable calcium carbonate crystals or by-products in the desired overbased metal salt. These undesirable components prevent the production of a filterable stable product. Thus, the metal base slurry is added at a controlled rate that does not exceed the rate of reaction producing the desired product. Whereas metal bases (such as lime) react to produce by-products, this reaction can be performed continuously or in small portions so that calcium ions are immediately available for the desired reaction. It is controlled by adding. It is believed that excess by-product or lime coated with calcium carbonate renders the liquid product unfilterable. This method is used to control the pH during the reaction. As a result, the fatty acid is neutralized, and subsequently the base is added to raise the pH to about 7 to 10 to produce dissolved metal ions. This metal ion reacts with CO ₂ during carbonation to produce the desired product. Without controlling the reaction rate and not dissolving the base, the solid base reacts with or is coated with calcium carbonate to form undesirable by-products. When undesirable reaction by-products are formed, the final product becomes unstable and unfilterable.

  As explained in detail above, one of the features of the method is that during carbonation, a dispersion consisting of an alkaline earth metal base, a polyol, a liquefied hydrocarbon, and an alcohol having at least 8 carbon atoms is controlled. Adding at the determined base addition rate to produce a stable flowable liquid. It has been found that the addition of liquefied hydrocarbons and aliphatic alcohols with a dispersed base protects or passivates the base, thereby making it possible to produce a stable fluid liquid reaction product. By protecting or passivating the base, carbonation proceeds to produce amorphous alkaline earth metal carbonate. Surprisingly, this reaction proceeds without the need to remove water during the reaction, and a liquid reaction product that can be stored for a long time is obtained.

  The amount of alkaline earth metal base used in the preparation of the basic salt is an amount exceeding 1 equivalent of base per equivalent of fatty acid or organic component. More generally, this amount is sufficient to provide at least 3 equivalents of metal base per equivalent of acid. Higher amounts can be used to produce more basic compounds, and the amount of metal base included is any amount up to an amount that is no longer effective to increase the proportion of metal in the product. be able to. When preparing a mixture, it is desirable that the amount of fatty acid and alcohol contained in the mixture be greater than 1: 1 to form a basic product. More generally, the equivalent ratio is at least 3: 1.

  In one embodiment of the present invention, the ratio of hydrocarbon oil to alcohol (dodecanol) is from about 2: 1 to about 4: 1. Glycol ether can be used in about 1-15% of the final product.

  The lime slurry added to oleic acid during the reaction has a general composition consisting of about 40-50% lime, about 25-40% hydrocarbon oil, about 10-25% dodecanol, and about 0-10% propylene glycol. Formulated as a pumpable mixture with. The amount of propylene glycol required to produce a pumpable slurry increases as the proportion of lime in the slurry increases.

  A method for preparing a fluid overbased calcium carboxylate precursor that can be stored for a long period of time includes the step of combining an alkaline earth metal base and a carboxylic acid in the presence of a liquefied hydrocarbon, an aliphatic alcohol, and a glycol ether. Reacting with an acid equivalent ratio greater than 1: 1 to form a carboxylic acid alkaline earth metal salt mixture. In one embodiment, the carboxylic acid is a fatty acid (the fatty acid is oleic acid), the liquefied hydrocarbon is SHELLSOL ™ D80, the alcohol is dodecanol, and the glycol ether is propylene glycol. This mixture is acidified by a carbonation process to produce an amorphous alkaline earth metal carbonate, such as calcium carbonate. The carbonation step includes treating the above mixture with acid gas in the absence of free oxygen until a titerable basicity is determined using phenolphthalein. Generally, this titratable basicity is reduced to a base number of less than about 10. These mixing and carbonation steps require no special operating conditions other than eliminating free oxygen.

  The term “acid gas” as used herein and in the claims means a gas that reacts with water to produce an acid. Accordingly, gases such as sulfur dioxide, sulfur trioxide, carbon dioxide, carbon disulfide, and hydrogen sulfide are representative acid gases useful for the preparation of the disclosed overbased metal carboxylates. When carbon dioxide is used, an alkaline earth carbonate is formed. With sulfur gas, sulfates, sulfides and sulfites are formed.

  During carbonation, relative amounts of alkaline earth metal base, polyol, liquefied hydrocarbon and alcohol can be added at a controlled base addition rate. In one embodiment of the invention, dry alkaline earth metal base, polyol, liquefied hydrocarbon and alcohol can be slurried to facilitate mixing during the carbonation process. Water is removed from the reaction product to produce a flowable liquid that can be stored for a long time of an alkaline earth metal salt of a fatty acid. Generally, this process is performed in the absence of free oxygen and a nitrogen environment is used for this purpose.

  During carbonation, the mixture is heated to a temperature sufficient to drive off a portion of the water contained in the mixture, i.e., the water formed during the reaction of the base with the carboxylic acid and retained during the overbasing reaction. can do. Treatment of the mixture with carbon dioxide is preferably performed at an elevated temperature, and the temperature range used for this step ranges from about 75 ° C. (about 165 ° F.) to about 200 ° C. (about 390 ° F.). It can be any temperature above the temperature. Higher temperatures such as 250 ° C. (about 480 ° F.) can be used, but there is no obvious advantage to using such a high temperature. A temperature of about 80 ° C. (about 175 ° F.) to 150 ° C. (about 300 ° F.) is usually sufficient.

  Other features of this method include filtering the reaction product at a product filtration rate of at least about 300 ml per 10 minutes to produce a liquid precursor that can be stored for a long time. In one embodiment of the present invention, the produced product can be filtered to remove unwanted by-products and enhance the storage stability of the overbased liquid. For example, using a Buchner funnel under a vacuum of about 25-30 inches Hg, Whatman No. Using 1 filter paper and diatomaceous earth filter aid, the product can be filtered at a sufficient rate. Thus, filtration removes undesirable impurities including silica, iron oxide and other metal species, unreacted calcium hydroxide, calcium carbonate, and other oxides that may result in a lack of stability.

  In another aspect of the invention, the liquid overbased alkaline earth salt of the fatty acid precursor is considered to be a thermodynamically stable microemulsion. This microemulsion has a micelle and a continuous phase. This micelle consists of an alkaline earth metal carbonate and a carboxylic acid alkaline earth metal salt of a fatty acid. The continuous phase of the microemulsion consists of liquefied hydrocarbon and alcohol.

  In yet another embodiment of the present invention, after removing water from the alkaline earth metal base, fatty acid, polyol, liquefied hydrocarbon and alcohol precursor, the precursor removes the volatile components of the reaction product. And distillation or vacuum stripping at a temperature up to about 165 ° C. (about 330 ° F.). In the distillation terminology, “stripping” is the removal of volatile components from less volatile materials. Vacuum stripping is performed until the final product has an alkaline earth metal content measurement of at least about 14.5% and a non-volatile content of at least about 95%.

  In yet another embodiment of the present invention, vacuum stripping of the precursor yielded unexpected results. In particular, it has previously been believed that both the continuous phase liquefied hydrocarbon and alcohol components are required in the final reaction product to maintain a stable microemulsion of liquid overbased alkaline earth salts of fatty acids. It was. However, the following was unexpectedly observed when the precursor was vacuum stripped. That is, the final product not only maintained long-term storable and fluid liquid properties, but the final product had a final non-volatile content of at least 95% and a flash point greater than 93 ° C (about 200 ° F). It became clear to have.

The reaction mixture for overbased calcium oleate after adding the slurry and carbonating with carbon dioxide and vacuum stripping has the following compositional range:
About 15-40% calcium oleate
About 9 to 35% by weight of calcium carbonate
Hydrocarbon oil about 25-35% by weight
Dodecanol (co-surfactant) Less than about 5% by weight Propylene glycol Less than about 1% by weight

Replacement of the overbased salt calcium with magnesium, strontium, or barium is done on an equivalent basis of metal hydroxide. Based on the final reaction mixture before vacuum stripping, the following amounts can be used:
Ca (OH) ₂ (lime) about 15 to 35% by weight
Mg (OH) ₂ about 12-24% by weight
Sr (OH) ₂ about 25-50% by weight
Ba (OH) ₂ about 35-50% by weight

  The following examples illustrate the preparation of long-term storable haze-free liquids of overbased salts according to the method of the present invention, but these examples are considered to limit the scope of the present invention. Should not. Unless otherwise indicated in the following examples and others herein and in the claims, all parts and percentages are parts by weight and percentages by weight and all temperatures are in degrees Fahrenheit.

Generation of Overbased Calcium Oleate Precursor I A 15% overbased calcium oleate / calcium carbonate was prepared according to this example. A mixture of about 274.3 g oleic acid, about 270.0 g D-80, about 140.3 g dodecanol, about 50.0 g propylene glycol, and about 25.0 g water was stirred at about 88 ° C. (about 190 ° F). To the stirred mixture, a dispersion consisting of about 140.4 g D-80, about 85.0 g dodecanol, about 25.0 g propylene glycol, and about 276.7 g lime is continuously added for about 50 minutes, and olein is added to the mixture. A solution of calcium acid was produced. At this point in the reaction, the result of testing the mixture with phenolphthalein was basic (pH about 10-12). The stirred mixture was then continuously treated with carbon dioxide at 1.5 SCFH, about 93 ° C. (about 200 ° F.) over about 3 hours. The basicity of the reaction was checked to maintain the basicity during the reaction. When the reaction mixture was almost neutral when tested with phenolphthalein, the carbon dioxide addition was discontinued. The reaction mixture was then heated to about 149 ° C. (about 300 ° F.) and a total of 85.2 g of water was removed via the Dean-Stark trap. The resulting product mixture was stirred and 24.00 g of filter aid (diatomaceous earth) was added. As described above in the specification, over 500 ml of product mixture per 10 minutes was suction filtered to obtain a long-term storage fluid liquid filtrate of overbased calcium oleate / calcium carbonate. The filtrate could be stored for a long time even when cooled to room temperature.

Vacuum stripping of overbased calcium oleate precursor I The precursor obtained in Example 1 was charged into a 250 ml three-necked round bottom flask. The three-necked round bottom flask was then equipped with a nitrogen inlet to the mixture at one of the flasks, a temperature probe at the other of the flask, and a vacuum line at the other of the flask. Vacuum filtration was performed at a temperature of about 149 ° C. (about 300 ° F.) to about 163 ° C. (about 325 ° F.) while supplying nitrogen gas at a rate of 6 cubic feet per hour (SCFH). A total of about 678.6 g of distillate was recovered, resulting in a non-volatile content of about 84.2%. Further, as a result of analysis of the filtrate, about 14.8% by weight of calcium was contained. To this mixture was added about 50.0 g of 6.0 centistokes PAO followed by further vacuum filtration as described above. After an additional 3 hours of filtration, the mixture had a non-volatile content of about 99.4% and analysis of the filtrate revealed that it contained about 15.7% calcium by weight. The final product had the following physical properties:
Flash point-> 200 ° C (about 392 ° F)
Specific gravity-about 1.162
Weight per gallon-9.68
Volatile content-<1% by volume
Volatile content-<1% by weight
As seen in FIG. 1, a thermogravimetric analysis (TGA) graph of the vacuum stripped final product is provided. This analysis was performed using a Seiko 5200 TG / DTA. Samples were evaluated from about 30 ° C. (about 86 ° F.) to about 550 ° C. (about 1022 ° F.) at a rate of 10 ° C./min. The final product thermogram (TG%) reveals the degradation of the final product as a function of temperature. The weight loss profile indicated by the inflection point on the TG% curve of the final product is 86.3% at 298.2 ° C. (about 568 ° F.) and 56.99% at 436.9 ° C. (about 819 ° F.). And 48.6% at 496.0 ° C. (about 925 ° F.). Inflection points are on curves where the curvature of the graph changes sign upon decomposition of the various components of the final product (if present, including various forms of calcium carbonate including calcite, vaterite, and / or aragonite) Represents a point or temperature. The inflection point is represented by the first derivative curve (DTG% / min). These results show that when measured at 200 ° C. (approximately 392 ° F.), the vacuum stripped end product of a flowable overbased alkaline earth salt of fatty acids that is long-term storable is greater than 95% It is suggested that it has.

Generation of Overbased Calcium Oleate Precursor II 15% overbased calcium oleate / calcium carbonate was prepared according to this example. A mixture of about 274.3 g of oleic acid, about 270.0 g of D-80, about 140.3 g of dodecanol, about 50.0 g of propylene glycol, about 100.0 g of 6.0 centistokes PAO, and about 25.0 g of water, Heat to about 88 ° C. (about 190 ° F.) with stirring under a nitrogen atmosphere. To the stirred mixture, a dispersion consisting of about 140.4 g D-80, about 85.0 g dodecanol, about 25.0 g propylene glycol, about 50.0 g 6.0 centistokes PAO, and about 277.0 g lime. Added continuously for about 50 minutes to form a solution of calcium oleate in the mixture. At this point in the reaction, the result of testing the mixture with phenolphthalein was basic (pH about 10-12). The stirred mixture was then continuously treated with carbon dioxide at 1.5 SCFH, about 93 ° C. (about 200 ° F.) over about 3 hours. The basicity of the reaction was checked to maintain the basicity during the reaction. The carbon dioxide addition was stopped when the reaction mixture was almost neutral when tested with phenolphthalein. The reaction mixture was then heated to about 149 ° C. (about 300 ° F.) and a total of 110.0 g of water was removed via the Dean-Stark trap. The resulting product mixture was stirred and 26.00 g of filter aid (diatomaceous earth) was added. As described above in the specification, about 1000 ml of product mixture at about 5.5 minutes and about 1225 ml of product mixture at about 7 minutes are suction filtered to provide a long-term storage fluid liquid of overbased calcium oleate / calcium carbonate. A filtrate was obtained. The filtrate could be stored for a long time even when cooled to room temperature.

Vacuum Stripping of Overbased Calcium Oleate Precursor II The process of Example 3 was repeated and the filtrates from both processes (a total of about 2032 g of product was obtained) were combined for vacuum stripping. Prepared. A three-neck round bottom flask was charged with the precursor material obtained in the two preparations of Example 3. The three-necked round bottom flask was then equipped with a nitrogen inlet to the mixture at one of the flasks, a temperature probe at the other of the flask, and a vacuum line at the other of the flask. Vacuum filtration was performed at a temperature of about 149 ° C. (about 300 ° F.) to about 163 ° C. (about 325 ° F.) while supplying nitrogen gas at a rate of 6 cubic feet per hour (SCFH). About 7.5 hours after vacuum stripping of the sample, the non-volatile content was found to be about 95.3%. As a result of analyzing the filtrate, about 15.7% by weight of calcium was contained. To this mixture was added approximately 25.0 g of 6.0 centistokes polyalphaolefin (PAO) followed by further vacuum filtration as described above. After a further 4 hours of filtration, the mixture had a non-volatile content of about 98.2% and analysis of the filtrate revealed that it contained about 15.7% calcium by weight. An additional 45.0 g of 6.0 centistokes PAO was added to the mixture to adjust the final calcium content measurement to about 15.3% by weight calcium. The final product had the following physical properties:
Flash point-> 200 ° C (about 392 ° F)
Specific gravity-about 1.144
Weight per gallon -9.53
Volatile content-<1% by volume
Volatile content-<1% by weight

  Based on the above disclosure, it is now clear that the above objectives are achieved by an overbased long-term storable flowable liquid of an alkaline earth metal salt of a fatty acid described herein and a method for preparing the liquid. It was. Accordingly, any obvious modifications may fall within the scope of the claimed invention, and thus the selection of particular components may be determined without departing from the spirit of the invention disclosed and described herein. Will be understood.

Claims (20)

A fluid liquid capable of long-term storage of an overbased alkaline earth metal salt of a fatty acid,
At least one hydrocarbon liquid;
Polyols,
An alcohol having at least 8 carbon atoms;
An overbased alkaline earth metal salt of a fatty acid,
The liquid wherein the alkaline earth metal salt has an alkaline earth metal content of at least about 14.5% and a non-volatile content of at least about 95%. The liquid according to claim 1, wherein the fatty acid is a C _{12 to} C ₂₂ fatty acid.   The liquid according to claim 2, wherein the fatty acid is oleic acid.   The liquid according to claim 1, wherein the alkaline earth metal of the overbased alkaline earth metal salt is selected from the group consisting of calcium, barium, magnesium and strontium.   The liquid of claim 1, wherein the overbased alkaline earth metal salt is calcium oleate.   The liquid according to claim 1, wherein the alcohol is an aliphatic alcohol composed of at least 14 carbon atoms.   The polyol is a glycol or glycol ether selected from the group consisting of diethylene glycol monobutyl ether, propylene glycol, hexylene glycol, triethylene glycol, dipropylene glycol, diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and mixtures thereof; The liquid according to claim 1. A method of preparing a long-term storable fluid liquid of an overbased alkaline earth metal salt of a fatty acid, comprising:
(A) preparing a precursor mixture comprising a carboxylic acid that is a fatty acid, at least one hydrocarbon liquid, a polyol, and an alcohol having at least 8 carbon atoms;
(B) neutralizing the carboxylic acid with an initial amount of alkaline earth metal base to form a carboxylic acid alkaline earth metal salt precursor mixture;
(C) heating the carboxylic acid alkaline earth metal salt precursor mixture;
(D) adding an additional amount of an alkaline earth metal base to the carboxylic acid alkaline earth metal salt precursor mixture;
(E) carbonating the precursor mixture to neutrality;
(F) filtering the precursor mixture;
(G) distilling the precursor mixture until an alkaline earth metal content of at least about 14.5% and a non-volatile content of at least about 95% are obtained. The method of claim 8, wherein the fatty acid is a C ₁₂ -C ₂₂ fatty acid.   The method of claim 9, wherein the fatty acid is oleic acid.   9. The method of claim 8, wherein the alkaline earth metal is selected from the group consisting of calcium, barium, magnesium and strontium.   9. The method of claim 8, wherein the alkaline earth metal carboxylate salt mixture comprises calcium oleate and calcium carbonate.   9. A method according to claim 8, wherein the alcohol is an aliphatic alcohol consisting of at least 12 carbon atoms.   The polyol is a glycol or glycol ether selected from the group consisting of diethylene glycol monobutyl ether, propylene glycol, hexylene glycol, triethylene glycol, dipropylene glycol, diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and mixtures thereof; The method of claim 8.   The method of claim 8, wherein the precursor mixture is distilled by vacuum stripping. A fluid liquid capable of long-term storage of an overbased alkaline earth metal salt of a fatty acid,
At least one hydrocarbon liquid;
Propylene glycol,
Dodecanol,
With overbased calcium oleate,
The liquid wherein the overbased calcium oleate has an alkaline earth metal content of at least about 14.5% and a non-volatile content of at least about 95%.   17. The liquid of claim 16, wherein the at least one liquefied hydrocarbon liquid is selected from the group consisting of hydrocarbon oils, mineral spirits, non-aromatic hydrocarbons and polyalphaolefins (PAO).   17. The liquid of claim 16, wherein the overbased calcium oleate has an alkaline earth metal content of at least about 15.0% by weight calcium.   The liquid of claim 16, wherein the liquid has a non-volatile content of at least about 97%.   17. A liquid according to claim 16, wherein the liquid comprises a form of calcium carbonate selected from the group consisting of calcite, vaterite and aragonite.

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