TW200424306A - Lubricant compositions containing an overbased amorphous alkaline earth metal salt as a metal protectant - Google Patents

Abstract

Lubricant compositions are made containing, as a metal protectant additive, an overbased amorphous alkaline earth metal salt of fatty acid. The additive is added in either a liquid or powdered form to the base oil in the composition. The overbased additive in the lubricating composition serves as a metal protectant to provide detergency, friction-modifying and acid-neutralizing properties to the compositions.

Description

2004243 06 发明 Description of the invention: [Related Cases] This case is US Patent Application No. 09/861, 39 filed on May 18, 2001 3. It was filed on March 3, 2003 and is now the US Patent No. 1/10/3 79,048 'and a portion of consecutive applications filed on August 18, 2003, ι〇 / 643,137. The entire disclosures of these applications are incorporated herein by reference. [Technical field to which the invention belongs] The present invention relates to a lubricant composition containing a highly alkaline fatty acid amorphous alkaline earth metal salt as a metal protective agent additive. The highly-experienced additive in the lubricating composition serves as a metal protective agent to provide the composition with cleaning power, friction modification property, and acid neutrality. [Previously] The production method of the sodium or barium salt of the carboxylic acid, alkylphenol and sulfonic acid exceeding the standard is disclosed in the following US patents: No. 2,616,904; No. 2,760,970; No. 2,767,164; and No. 2,798,852 ; 2,802,816; 3,027,325; 3,031,284; 3,342,733; 3,533,975; 3,773,664; and 3,779,922. The use of these overbased metal salts in the halogen-containing organic polymer is described in the following U.S. patents: 4,159,973; 4,252,698; and 3,194,823. According to the teachings of U.S. Patent No. 4,665,117, light-colored alkali or alkaline earth metal salts are prepared, in which the pyroylphenol can be used as an accelerator. With the development trend of replacing heavy metals in various compositions, liquid calcium products have been developed. The low metal concentration, poor compatibility and turbidity in transparent products O: \ 90 \ 9073O.DOC -6- 2004243 06 has severely limited the universal acceptance of liquid compositions containing mainly calcium. The stability of these compositions can cause problems once left to stand or shot. The storage stability should be attributed to the incompatibility between the metal salts used in the composition, and after two, two, ten, and two lapse of time, the turbidity, viscosity, or insoluble solids appeared. As a result, the liquid composition is no longer homogeneous, or it is easy to fall down, so special treatment is required before use. U.S. Patent No. 5, Cut Milk is a stabilizing composition of a mixed metal salt with improved storage stability. According to the patent, a compounding agent is added to the mixed metal carboxylate, and Wenliang is left to stand. The complexing agents disclosed in this patent include phosphine, arsenic i, aromatic cyanides, aromatic compounds, Chiang and other chemicals. U.S. Patent Nos. 5,830,935 and 5,859,267 have also been published in relation to: A method for improving the basic metal composition. U.S. Patent Nos. 3,766,066 (, 〇66) and 3,766, 〇67 (, 〇67) disclosed in " converter " (e.g., water and alcohol) self-homogenizing carbonation approximately high sensitivity Method for preparing micella micelle complex containing solids by osmium salt. The 〇67 patent teaches that in order not to prepare the desired micelle complex from the highly susceptible salt, first, I: homogenize these salt-refining organic liquid diluent solutions, and produce alcohol-water mixtures in the presence of 1 The 'violent ... calcite' gelatinizes, phenomenon, so it is possible to prepare crystalline particles with the same x-ray diffraction pattern as that of the salt solution. However, this initial dance. In fact, extensive research shows that there is no crystal In fact, the 066 patent teaches that it exists—it seems to be amorphous. According to the fact that, when the endoplasmic effect of the valley fluid, the non-aqueous material present in the material is homogeneous. Sun-shaped metal salt or compound

O: \ 90 \ 90730.DOC 2004243 06 It is bound to change k into crystalline particles. U.S. Patent No. 5,534,169 also teaches that in order to prepare a material that can be used to reduce friction, a Newtonian overbased calcium carboxylate is converted into a dispersion of non-Newtonian calcite particles. U.S. Patent No. 5,830,832 also discloses a method for preparing a powdery calcium overbased soap from a branched chain oxygen-containing acid. Lubricant compositions have used overbased metal components. For example, conventionally basic metal sulfonates have been used as cleaning agents. Although the newly developed method is exemplified by the above-mentioned patent and the latest method at present, the use of the overbased alkaline earth metal salt in the lubricating oil composition still needs to be further improved. [Summary of the Invention] The present invention relates to a lubricating oil composition containing a metal protective agent additive, which is a basic amorphous alkaline earth metal salt of a fatty acid. The overbased non-crystalline gold metal salt can be added as a liquid or powder type without turbidity. These versions can be prepared by special methods as described in our earlier patent applications Nos. 09 / 861,393 and 10/37 9,048, both of which are incorporated herein by reference. An opaque overbased liquid additive can be prepared by this method, and the powdered additive can be prepared from the overbased liquid. The lubricating composition contains the metal protective agent additive, and its content can effectively protect the metal during lubrication. The overbased metal additive has been found to impart three related properties to the lubricant composition, including cleaning power, friction modifier, and acid neutrality. Based on the total weight of the lubricant composition as the reference juice, when the effective content of the active overbased metal salt additive contained in the lubricant composition is about 0.5 to about 7% by weight, or even up to 15% by weight, the disclosure of the present invention can be obtained. At point k, it is also found that the southern testing additive of the present invention is better than

O: \ 90 \ 9O73O.DOC 2004243 06 The standard additive (overbased metal sulfonate) of the lubricant composition is much better. For example, unlike these other overbased metal additives which have been shouldered by lubricants, the significant advantages of the delta hai additive of the present invention are the neutralizing effect of the inverse acidic portion in the composition, the improvement of cleaning ability, and abrasion resistance. When the overbased metal liquid is used as an additive, it is contained in the liquid hydrocarbon. According to the method of the present invention, the liquid hydrocarbon has been used to prepare the highly experimental metal liquid. The liquid type contains the additive in a stable, non-turbid liquid state suitable for addition to the lubricating oil. When the powder type additive has been isolated, it can be added directly to the lubricating oil composition. The content of the basic metal salt in the two types of the lubricating oil is preferably about 0.5 to about 7% by weight. The lubricating oil can use a higher content of the additive (up to about. Reset%) 'However, according to the intended use of the lubricating composition, a higher content is necessary to obtain the cleaning ability, acid neutralization and resistance Abrasion is not particularly helpful. Compared with other overbased lubricant additives (which may include an adverse increase in the viscosity or rheology of the lubricating oil), the overbased metal additive of the present invention can provide each of the improved properties without adversely affecting the viscosity and Purpose. The above advantages, benefits and further understanding of the present invention will be made clear by reference to the following detailed description and preferred specific embodiments. [Embodiment] The liquid or powder additive of the present invention has been amorphous alkaline earth metal carbonate particles compounded with an amorphous alkaline earth metal carboxylate of a fatty acid. In the following, some powders or liquids are sometimes simply referred to as "powder or liquid overbased amorphous soil test metal salts (groups) or" powder or liquid overbased amorphous earth test metals

O: \ 90 \ 90730.DOC 2004243 06 Carboxylate (group) / carbonate (group g ^ It is preferred to provide overbased amorphous calcium and barium salts and to use the preferred method of the present invention as a two-material method. The additive is basically free of phenol or phenol-based organisms. The powder amorphous salt is essentially a solid particle, which is a kind of metal carbonate, like the metal carbonate, which can- The amorphous metal is slow-capped ^. Sub-isolated 3. The size of the cohesive particles is usually about 50 microns. The method for preparing the liquid or powder-identifying aann non-positive soil-testing metal salt includes the presence of liquid hydrocarbons. Now, iM i ^ μ reacts more alkaline earth metal bases with fatty acids, and the equivalent ratio of metal bases to fatty acids is greater than · | ·; 1 · 1. The use of surfactants and catalysts to promote the reaction. Preferably by carbonation The mixture is used to acidify the mixture to prepare an amorphous soil test metal carbon a double salt. In a preferred method, during carbonation, an alkaline earth metal base, a liquid hydrocarbon, and a fatty alcohol having at least 8 carbon atoms are added relatively. .Dispersion to prepare stable non-turbid liquid reaction products Water is removed from the reaction product to obtain a stable, non-turbid liquid overbased alkaline earth metal salt. For the liquid hydrocarbon / alcohol of the non-turbid liquid, the powder can then be isolated by adding enough solvent. Highly qualitative amorphous salt makes the particles of the highly basic amorphous salt cohesive and separate. Then the cohesive particles are isolated by filtration and dried to the extent that the particles can be treated as a solid powder. As we did in the early days As described in Patent Application No. 09 / 861,393 (filed on May 18, 2001), it has been found that it is important to add the metal in a relative amount at a controlled rate during carbonation, and the liquid hydrocarbon fat Alcohol dispersion to prepare the stable non-turbid liquid reaction product. There are many methods to form stable non-turbid liquid. The stable non-turbid liquid can be filtered to remove impurities and by-products of the reaction. According to the principles of the present invention, O: \ 90 \ 9073O.DOC -10- 2004243 06

The liquid avoids unwanted calcium carbonate crystals to such results. It is believed that the metal alkali slurry or by-product is formed in the desired overbased metal salt. These unwanted parts can prevent the formation of the filterability, stability, and turbidity-free products. In other words, the metal inspection slurry is added at a controlled rate that does not exceed the reaction rate at which the desired product is formed. Compared to a method of reacting the metal base (e.g., lime) and forming a by-product, the reaction can be controlled by continuously or incrementally adding the metal so that the calcium ion is immediately applicable to the desired reaction. Excessive by-products or lime coated with calcium carbonate made the liquid product impossible to filter. By using this program, the pH can be controlled during the reaction, so the fatty acid can be neutralized, and the yang can be raised to about 10-12 by continuous addition of a base to prepare a dissolved metal ion. During carbonation, it It can be reacted with C02 to prepare the desired product. If the reaction is uncontrolled and cannot dissolve the base, then the solid base can react with calcium carbonate (or be coated with carbonic acid) to form unwanted by-products. The unwanted formation of by-products in this reaction makes the final product unstable and cannot be filtered. It was found that the powdery overbased amorphous salt can be prepared from the turbid liquid of the highly soil-testing metal fatty acid salt. With the liquid or powdery additive and method of the present invention, many problems can be obtained. The liquid and powder can be used to obtain a stable and stable alkaline alkaline metal fatty acid salt. In more detail, the liquid and powder containing no phenol and a phenol-based derivative (e.g., an age-based reaction product) can be left to stand by. Due to the concerns of the environment O: \ 90 \ 9O73O.DOC -11-2004243 06, as far as the bank is striving to remove such phenolic products, this point is # 别 希望 之 优 十The point is also 'as mentioned above, this phenol is a source of color development. In more detail, after a long period of time, the liquid high-alkali sulfonic acid fatty acid salt available to Muco showed turbidity or opacity, and the liquid or powder additive was found to maintain stability. The liquid and isolated powder of the present invention are also easy to handle and store. The powder can be dispersed in oil or liquid smoke and other solvents to form a non-turbid liquid. Therefore, the redispersibility of the powder is not limited to a specific medium. The accelerator and reactive diluent are removed from the powder. Similarly, upon redispersion, higher concentrations of calcium, for example, up to about 25% are available. A. Liquid or powder additive for highly-experimental amorphous soil-testing metal ^ In the preferred embodiment, the powder or liquid highly-experimental amorphous salt is derived from an amorphous overbased alkaline earth metal salt of a fatty acid Stable, non-turbid liquid, including an alkaline earth metal carbonate, an alkaline earth metal carboxylate of a fatty acid, a liquid smoke, and a fatty alcohol having at least 8 carbon atoms, and the liquid is preferably free of phenol or phenol Derivatives, for example, phenolic reaction products. In the case of alcohols and diols that are liquid, liquid, and / or may be present, a solvent or a liquid precipitant (for example, isopropyl alcohol) is used to isolate the powder from the liquid overbased salt back to the basic amorphous form. Salt, and the solid particles of the basic salt are formed by the cohesion of the amorphous particles. The high-alkali t raw salt cohesive particles are then obtained by filtration and drying. The solid is preferably precipitated from the liquid salt, which does not require O: \ 90 \ 9073Q.doc -12- 2004243 06 to treat the transponder or use special wounds by, for example, spraying, micronizing and collecting the powder. The size of the cohesive particles of the overbased amorphous salt is 50 microns, but the particle size is not important. It has also been found that these powders can be dispersed in liquid hydrocarbons and other solvents to prepare turbid liquids with a variety of intended uses, as described below. Other solvents or liquid precipitants (e.g., methanol, ethanol, propanol, butanol, and glycol ethers) can be used to precipitate the powder or cohesive particles from the liquid overbased salt. Lower alcohols are preferred because they can be easily removed from the considered product via a drying step. This solvent or liquid has been used as a "converting agent" to convert this Newtonian overbased liquid into a non-Newtonian colloidal system, and as described in the prior art of the present invention, U.S. Patent Nos. 3,766, 〇66 and I ·· No. 2 separates the crystalline calcite particles. On the contrary, according to the present invention, the overbased amorphous salt has been isolated by adding an excessive amount of the solvent in terms of the alcohol phase of the turbidity-free liquid. By treating the turbidity-free overbased liquid of the present invention in this manner, it is found that the powdery overbased amorphous salt is greatly different from the crystalline calcite powder containing the above-mentioned prior patent. Therefore, when a sufficient amount of the solvent is added to the non-turbid overbased liquid (which is used in a ratio of 1 to about 5 to 1), the overbased amorphous salt can be agglomerated to prepare the meal-like two bases of the present month. Amorphous product. It is believed that this method can perform solvent extraction of the liquid hydrocarbon from the liquid highly sensitive complex. The fatty acids of the highly volatile liquid carboxylate are usually C12 to C22 fatty acids of saturated fatty acids, which include, for example, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid, and behenic acid. Unsaturated fatty acids include palmitoleic acid, oleic acid, linoleic acid and linolenic acid. Among these fatty acids,

O: \ 90 \ 90730.DOC -13- 2004243 06 At present, oleic acid is preferably used to prepare the overbased liquid carboxylate. The alkaline earth metal of the salt is selected from the group consisting of calcium, barium, magnesium and thallium. For example, powdered overbased calcium oleate has been prepared. These powdered overbased calcium salts contain amorphous calcium carbonate that has been complexed with calcium oleate. In the method for preparing a liquid overbased salt (from which the powdery amorphous salt can be derived), it is important to have a fatty alcohol containing at least 8 carbon atoms, and more preferably to have a fatty alcohol containing 8 to 14 carbon atoms. Alcohols, for example, isodecanol, dodecanol, octanol, tridecanol and tetradecanol. Isodecanol is currently preferred. It was found that when a carbon fatty alcohol is used to prepare the liquid overbased product, phenol may not be used as a promoter for the reaction. This is a more special feature of the present invention, and it is preferable that the powdery overbased amorphous salt does not contain phenol or a phenolic product when it is prepared or used. Although the full text is not limited to theory, it is believed that the fatty acid is a liquid high-alkali soil test salt-a kind of thermodynamically stable microemulsion. The microemulsion has micelles and a continuous phase. The micelle is composed of an amorphous soil test carbonate of the fatty acid and an amorphous soil test metal sulfonium salt. The continuous phase of the microemulsion is composed of the liquid hydrocarbon and the lenol or possibly diol. The present invention relates to a method for isolating particles (which are cohesive micelles of the amorphous salt) to form the powdery highly sensitive salt. A powdery highly amorphous amorphous metal salt containing at least 8% by weight or more (up to about 70% by weight) of the alkaline earth metal has been prepared. For this high testability, it is about salt and contains up to about 8 weight, and for barium salt, it contains up to about 30% by weight. When the apparatus contains 'e.g., a high-carbon, high-assay product of about 15 to 70% by weight of metal', it is found that a glycol or glycolic acid and the high-carbon fatty alcohol are suitable for use.

O: \ 90 \ 90730.DOC -14- 2004243 06 —Alcohol or glycol test can choose free diethylene glycol monobutyl ether (butyl carbitol (Carbitol) 'diethylene glycol' dipropylene glycol, diethylene glycol Group consisting of alcohol monomethyl ether, ethylene glycol monobutyl ether, and mixtures thereof B. Alkali method and important features for preparing the alkaline liquid and powder additive of the present invention The method for preparing alkaline earth metal salt with high sensitivity of fatty acid according to the present invention The method for shelving the oil additive of stable, non-turbid liquid includes reacting an alkaline earth metal base with a fatty acid in the presence of a liquid hydrocarbon mixture, and the ratio of the metal base to the fatty acid is greater than 1: 1. Surfactant and contact The mixture can promote the reaction. The mixture is acidified, and preferably carbonated to prepare an amorphous alkaline earth metal carbonate. During the carbonation reaction, the alkaline earth metal base is added at a controlled rate at a controlled addition rate, A dispersion of a liquid hydrocarbon and a fatty alcohol having at least 8 carbon atoms to prepare a stable non-turbid liquid reaction product. Water is removed from the reaction product to prepare a stable non-turbid liquid overbased alkaline earth metal salt. Generally, The whole This method is preferably carried out without free oxygen, and for this purpose, nitrogen can be used. As mentioned above, a major feature of this method is that it is added at a controlled rate during the carbonation reaction during the carbonation reaction. A step of preparing a stable non-turbid liquid containing a dispersion of an alkaline earth metal base, a liquid hydrocarbon and a fatty alcohol having at least 8 carbon atoms. It was found that the addition of the alkaline dispersion in the liquid hydrocarbon and fatty alcohol can protect or passivate The base can thus form a stable, non-turbid liquid reaction product. By protecting or purifying the base, a carbonation reaction is performed to prepare an amorphous soil test metal carbonate. Surprisingly, the reaction can be performed without removing water. And it can produce a very stable non-turbid liquid reaction product. At the end of the reaction, water is removed. As far as the stable liquid overbased salt is concerned, the water content is better. O: \ 90 \ 9073O.DOC -15- 2004243 06 less than 1%, more preferably less than 0.3% or 0.1%. The water added during the reaction must be removed or the water formed by the reaction must be removed because it will form a product that hinders the reaction or settles. Sexual turbidity A separate phase of the body is formed. Other features of the method include filtering the reaction product to prepare a shelving or thermodynamic female qualitative liquid with a product filtration rate of at least about 3 milliliters per 10 minutes. In a preferred form of the invention, The product prepared is filtered to remove unwanted by-products and enhance the shelf stability of the overbased liquid. For example, under a vacuum of about 25.30 inches Hg, use Whatman No. 1 The filter material and the Buchner funnel (15 cm diameter) of the diatomite filter adjuvant (Celite® 512-577) can filter the product at a satisfactory rate. A major finding of the method of the present invention is The reaction product can be filtered using a filtration rate that could not be completed in the past to form a stable, non-turbid liquid. This filtering advantage is particularly needed when the metal content in the overbased liquid (especially overbased calcium liquid) is desired to be higher. Therefore, filtration can remove impurities, including silica, iron oxide and other metal species, unreacted calcium hydroxide, calcium carbonate, and other halide compounds that can cause lack of stability. The content of these by-products or impurities accounts for up to about 6% of the by-products of the reaction. The description of the patent and the scope of the patent application range from beginning to end. When the term, "experimental" or "highly alkaline," is used to describe the In the case of an alkaline earth metal salt, it means that the ratio of the total metal to the fatty acid portion contained in the metal composition is greater than the stoichiometric ratio of the neutral metal salt. That is, the metal equivalent number is greater than the fatty acid equivalent number. In some examples, the excess metal content found in the basic metal salt is referred to as the '' metal ratio '. As used herein, the metal ratio indicates the oil solubility

O: \ 90 \ 9073O.DOC -16- 2004243 06 The ratio of the total alkaline earth metal to the equivalent number of fatty acid or organic part in the composition. In this technique, the basic metal salt is generally referred to as "overalkaline," or, "excessive π" means the presence of an excess of the basic component. The method of the present invention can be used to prepare a stable liquid and The amorphous alkaline earth metal carboxylate powder of the fatty acid that has been isolated. As described above, the method can be carried out without using a phenol accelerator or a phenol-based reaction product. Therefore, in order to obtain a stable and non-turbid liquid, it is not necessary to use phenol or The phenol-based reaction product can be used to prepare liquid and powdered overbased barium fatty acid carboxylates. In this case, liquid and powdered overbased calcium fatty acid carboxylates do not use phenols, and they can be placed on hold. The basic product is a fatty alcohol having 8 carbon atoms. The alkaline earth metal base as a reaction component can be derived from any alkaline earth metal, and more particularly calcium and barium base. The metal base includes Metal oxides and hydroxides, in some examples, also include the sulfide, hydrogen sulfide, etc. Although the reaction can be performed without using a component or a reactant, but in terms of liquid, each product, The phenol or alkylphenol is included to prepare a liquid overbased product. As described above, the fatty acid or a mixture thereof as identified above can be used in the reaction mixture. For example, a surfactant that can promote the reaction can be formed on the spot The alkaline earth metal carboxylate of the fatty acid may include its surface active agent, for example, a general purpose surfactant called Tween, which is a local purpose of fatty acid of sorbitan anhydride and polyisobutylene succinic acid. Polyoxyethylene derivatives (especially the mono- and di-oleate of ethoxylated sorbitol). Also, it is preferable to include a catalyst that can promote the reaction speed, such as propionate citric acid, acetic acid And adipic acid. Hydrocarbon liquids used in this method

O: \ 90 \ 9073O.DOC -17-2004243 06 and the liquid reaction products _,, _ include any hydrocarbon diluent. The liquid hydrocarbon is preferably selected from the group of oil, mineral spirits and non-aromatic hydrocarbons. C. The content of the reactant and catalyst used to prepare the alkaline salt is used in an amount of more than one equivalent of the fatty acid or organic portion of the test, and more preferably enough to obtain at least one equivalent of the acid. 3 equivalents of the amount of metal test. Higher amounts can be used to form more test compounds, and the amount of the metal base can be any amount that can no longer effectively increase the proportion of the metal in the product. When preparing the mysterious mixture σ, in addition to obtaining an alkaline product, the equivalent ratio of the scopolamine of the other component compositions in the mixture should be greater than 1: 丨, and the content of the fatty acid and the alcohol in the mixture is equal to Not important: the equivalent ratio is more preferably at least 3: 1. In these examples where phenol can be used to prepare overbased calcium, the equivalent ratio of the monocarboxylic acid to phenol should be at least about hl: i; that is, the content of the monocarboxylic acid is higher than the content of the phenol. The content range of the hydrocarbon oil, fatty alcohol (preferably isodecanol), butyl carbitol and triethylene glycol has been selected. Therefore, the alkaline earth fatty acid salt (also That is, in the presence of calcium oleate, the mixture can form a stable inverse microemulsion of the metal carbonate, water and surfactant (internal phase) and surfactant, co-surfactant, and hydrocarbon (outer continuous phase). . The acceptable ratio of the hydrocarbon oil to the co-surfactant fatty alcohol (isodecanol) is about 2: 1 to about 4: 1, preferably about 2: 1. The use amount of the glycol ether is about 1-15% of the final product, the use amount of the butyl carbitol is preferably about 6%, and the use amount of the triethylene glycol is about 0_2%, preferably about 0.6%. The lime slurry added to the oleic acid of the reaction is prepared into an easy O: \ 90 \ 9O73O.DOC -18-2004243 06 fruit extraction mixture, which generally has a composition of about 40-50% lime and about 25-40% hydrocarbons. Oil, about 10-25% isodecanol, and about 0-10% butylcarbitol. The amount of butylcarbitol required to prepare a pumpable slurry increases as the lime% in the slurry increases. After adding the slurry and carbonation by carbon dioxide, the reaction mixture of the overbased oleic acid word preferably has the following composition range: oleic acid feed (surfactant) about 15_30% carbonic acid # 5 about 9-35% hydrocarbon oil about 30-35% isodecanol (co-surfactant) about 15-18% butyl carbitol about 4-6% triethylene glycol about 0-0.8% of this catalyst, propionic acid or low-carbon fatty acid, The amount of di- or tricarboxylic acid used is about 0. 0. 1 o / Q of the final reaction mixture. The sodium of the overbased salt may be replaced with magnesium, scandium or barium based on the equivalent weight of the metal hydroxide. According to this final reaction mixture, the following contents can be used:

Ca (OH) 2 (lime) about 15-30%

Mg (OH) 2 about 12-24%

Sr (〇H) 2 about 25-50%

Ba (OH) 2 about 35-50% The step of the carbonation reaction includes treating the above-mentioned mixture with an acidic gas without containing free oxygen until the titerability is determined using phenolphthalein. Generally, the titratable alkalinity is reduced to a base number below about 10. O: \ 90 \ 9O73O.DOC -19- 2004243 06 The mixing and carbonation steps of the present invention do not require and better exclude the free state of oxygen, which is an unusual operating condition. The test is first mixed, the fatty acids and liquid hydrocarbons are usually heated, and then the acid dioxide is used for the reverse treatment of the dioxide, and the mixture can be heated to & to drive away the temperature of the wound water contained in the mixture . The carbon dioxide treatment of the mixture is preferably performed at a high temperature, and the temperature range used in the X! Hai step can be any temperature higher than the ambient temperature and up to about 200 ° C, and more preferably from about 100 to about 2 ° C. 〇 Its temperature. Although higher temperatures (for example, 25.0) can be used, there is no obvious advantage in terms of using such high temperatures. Usually, about 80. 〇 to 15〇. 〇 will be satisfactory temperature. D. Lubricating oil composition The overbased additive of the present invention is a compound having a large excess of basic metal ions, wherein the content of the basic metal ion exceeds the amount that can be neutralized by other additives in the lubricant composition . For commercial purposes, the lubricating oil composition can be adjusted for use in internal combustion engine (especially gasoline and diesel engines) 'crankcase lubrication and the like. Therefore, the overbased metal additive of the present invention has excessive alkaline particles, which can interact with acidic species or a part thereof (eg, carbon dioxide), or other acid fuel combustion products (which are corrosive and easily deteriorate the oil and metal) )reaction. The acid derived from the combustion of the fuel or the oxidation of the oil is particularly detrimental to the function of the engine and must therefore be neutralized. It has been found that the southern test additive of the present invention is particularly helpful in avoiding such damage. Moreover, the highly experimental additive of the present invention can provide a friction-improving function in terms of engine and crankcase lubrication effects, that is, improved fuel economy. In addition, the highly sensitive additive can be cleaned by retaining solvents and other pollutants in the suspension O: \ 90 \ 9O73O.DOC -20- 2004243 06 f to passivate it to reduce engine deposits and sludge. Agent = used. Therefore, reference can be made to the following detailed composition and examples to further understand the advantageous properties of the metal protective additive in the lubricant composition of the present invention. (1) Oil component The oil (sometimes referred to as " base oil, ") is a lubricating and viscous oil, and it is the main liquid component of the lubricant, so that additives and possibly other oils are mixed therein. Combined to prepare the final lubricant (referred to herein as " lubricating composition "). The base oil may be selected from natural (vegetable, animal or mineral) and synthetic lubricating oils and their blends. The viscosity is expressed in the range of light Distillate mineral oils to heavy lubricating oils, such as gas engine oils, mineral lubricating oils, motor vehicle oils, and heavy polluting diesel oils. Generally, the viscosity of this oil ranges from 2 to 30 (specifically at 10 ° C 5 to 20) mm2s-i. Natural oils include animal and vegetable oils, liquid petroleum and hydrogenation. Refined, solvent-treated or acid-treated paraffin-based, naphthenic and mixed paraffin-naphthenic minerals Lubricating oils. Lubricating viscosity oils derived from coal or shale are also useful base oils. Synthetic lubricating oils include hydrocarbon oils and halogen-substituted hydrocarbon oils, for example, polymerized and interpolymerized olefins (eg, polybutene, poly Propylene, propylene-isobutylene copolymer, gasified polybutene Polyhexene), -octyl), poly (1-decene)); alkylbenzene (eg, dodecylbenzene, tetradecylbenzene, dinonylbenzene, di (2-ethylhexyl) benzene) Polyphenyls (eg, biphenyls, triphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides and their derivatives; analogs and homologues thereof. Oxygenated polymers and interpolymers and their derivatives (wherein the terminal hydroxyl group has been modified, for example, by g-chemical reactions or etherification reactions) constitute another known synthetic lubricating oil. Another suitable type of synthetic lubricating oil includes Dicarboxylic acid esters. O: \ 90 \ 9O73O.DOC -21-2004243 06 vinegars can also be used as synthetic oils. These vinegars also include these from CdCi2 mono-chinic acid and polyhydric alcohol ethers. S, p 及 ae-I, diisopentaerythritol and m, isoisotetraol oil (for example, the polyalkyl ·, polyaryl / siloxane-based oxane oil and silicon Acid oil) is another kind of ^ 1-oxy-, or polyaryloxy stone; a kind of useful synthetic lubricants. Unrefined, refined and re-refined oil. Miao ^ This lubricant is specified in the lubricant. Purified oil is obtained from the source and does not need to be added-step corpse white ^ oil obtained from steaming oil, directly from. The role of the oil or directly from the esterification method The vinegar oil can be used in further processing, all of which are unrefined oils. Refined oils, similar to the unrefined oils, have been processed by one or more purification steps to improve one or more different properties. This purification method (for example, steam room, solvent extraction, acid or test extraction, percolation, and diafiltration) is known to those skilled in the art. Re-refined oil can be obtained by similar methods to obtain refined oil. This method is suitable for used refined oils. Such re-refined oils are also called recycled oils or reprocessed oils' and are usually processed extra by a method used to remove waste additives and oil breakdown products. (2) Co-additives A known additive may be incorporated into the lubricant composition together with the additive of the present invention. It may include, for example, dispersants; other cleaners, for example, single or mixed cleaner systems; rust inhibitors; antiwear agents; antioxidants; corrosion inhibitors; friction modifiers or friction reducers; pour point suppressors; Anti-foaming agent, viscosity improver; and surfactant. It can be combined in proportions known in the art. Also as this technique is known, certain additives can have multiple functions. O: \ 90 \ 9O73O.DOC -22- 2004243 06 So 'for example, g.j-, the early additive can be used as a dispersant. A more detailed discussion is as follows: Emulsification inhibition sword. (A) Dispersant Dispersant 1 is an additive for lubricants, and its main pollutant is kept in Yangluo County ^ In order to find solids and liquids in 4 kg of liquid, refine it to make it pure and reduce sludge deposition. Because of the accumulation of liquid-oil-insoluble matter (which is obtained from the use of this moisturizer :) = can be coagulated and precipitated in the slag or deposited in the primer = usually " ashless ", which is very different from metal-containing ash-forming materials, which It is a non-metallic organic material. Once burned, it does not substantially form ash. It contains long-chain smoke with a polar front end. The polarity is derived from, for example, N atoms. The hydrocarbon is a kind that has, for example, buckled to A lipophilic group of 1 carbon atom, which can provide oil solubility. Therefore, the ashless dispersant may contain an oil-soluble polymeric hydrocarbon backbone having a functional group that can be combined with the particles to be dispersed. Generally speaking, the dispersant Contains amines, alcohols, ammonium amines, or hydrazines, which are usually connected to the polymer backbone via a bridging group. The ashless agent may be selected from, for example, mono-substituted with long-chain hydrocarbons. And oil-soluble salts, esters, amine esters, amidines, imines, and oxazolines of dicarboxylic acids or their anhydrides; thioacid salt derivatives with long bonds; having a polyamine directly attached to them Chain Fatty Chains' and Mannich (Ma) as described in U.S. Patent No. 3,442,808 nmch) condensation products formed by condensing long-chain substituted phenols using formaldehyde and polyalkylene polyamines. Dispersants include 'for example, metaboic acid derivatives substituted with long-chain hydrocarbons, examples of which are high molecular weight hydrocarbon groups Substituted succinic acid. Famous types of dispersants are

O: \ 90 \ 9O73O.DOC -23- 2004243 06 Hydrocarbon-substituted succinimine, for example, via the above-mentioned acid (or a derivative thereof) and a nitrogen-containing compound (preferably a polyalkylene polyamine, such as , Polyethylene polyamine) reaction. Even more preferred are as described in US Patent Nos. 3,202,678; 3,154,560; 3,172,892; 3,024,195; 3,024,237; 3,219,666; and 3,216,936; and BE_A-66,875 The reaction product of a polyalkylene polyamine and an alkenyl succinic anhydride, which can be post-treated to improve its properties', such as a greenhouse acidification treatment (such as U.S. Patent Nos. 3 § 7 9 36 and 3,254,025 No.) 'after gasification or oxidation treatment. For example, the fluorination reaction can be performed by treating a fluorenyl nitrogen-containing dispersant with a side compound selected from the group consisting of boron oxide, boron halide, boric acid, and boric acid ester. (b) Antiwear and antioxidants. The metal can be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper. Based on the total weight of the lubricant, the zinc salt is most often used in the lubricating oil at 0.1 to 10 (preferably 0.2 to 2) mass%. Kegen = a known method for preparing this salt, the first step is to form a dihydrocarbyl dithiophosphoric acid (DDPA) (usually made by reacting one or more alcohols or hoping with ρ · _.2 s.sub.5) The DDpA formed is then neutralized with a zinc compound. The zinc dihydrocarbyl dithiophosphate can be made from a mixed DDPA, which is sequentially made from a mixed alcohol. Alternatively, a plurality of dihydrocarbyl dithiophosphates can be prepared and then mixed. The following example illustrates the method for preparing the turbid liquid-free ageing salt additive (example is money) and the powder form derived therefrom according to the method of the present invention: an experimental amorphous metal salt (example 7_MU_12). These examples are not intended to limit the scope of the invention. In the following examples and this patent specification MO: \ 90 \ 9073O.DOC -24- 2004243 06 Please anywhere in the patent scope Unless otherwise specified, all parts and percentages are expressed by weight ratio, all temperatures are expressed in degrees Fahrenheit . Example 1 10% overbased oleic acid / carbonate dance According to this example, a 10% overbased calcium oleate / calcium carbonate without phenol was prepared. Under nitrogen cyanide, '308.42 g of oleic acid (1.100 moles), 213.15 g of mineral oil, 154.14 g of isodecanol' 63.08 g of butylcarbitol, 8.70 g of triethylene glycol, 26.97 A mixture of grams of water and 0.87 grams of propionic acid was heated to 190 ° C while stirring. Continue adding a dispersion containing 38.98 grams of mineral oil, 13.86 grams of isodecanol, 3.71 grams of butylcarbitol, and 43.28 grams of lime (0.5498 moles) to the stirred mixture. 'It took about 33 minutes to prepare calcium oleate The mixture solution. The dispersion was added at a rate of about 3 grams per minute. At this point, within the reaction, the mixture was tested to be alkaline with phenolphthalein (about 10-12 pH). Then, a dispersion containing 276.25 g of mineral oil, 98.23 g of isodecanol, 26.31 g of butylcarbitol, and 3 06.75 g of lime (3.897 mol) was continuously added to the stirred mixture for about 3 hours and 56 minutes. At the same time, the mixture was treated with an emulsified carbon at 1.5SCFH at 195-200T. The dispersion was also added at a rate of about 3 grams per minute. The basicity of the reaction was checked during the reaction to maintain the basicity. When the reaction mixture was nearly neutral as tested by phenolphthalein, the addition of carbon dioxide was stopped. The reaction mixture was then heated to 300 ° F and a total of 99.36 grams of water was removed by a Dean-Stark tray. The product mixture formed was stirred and 24.00 g of filter aid (diatomaceous earth) was added. At a rate of about 30 milliliters per 10 minutes, as described above, the product mixture is filtered through suction to produce a clear, amber, overbased calcium oleate / calcium carbonate flowing liquid filtrate. Cold O: \ 90 \ 9073O.DOC -25- 2004243 06 When it reaches room temperature, it can keep clear. The filtrate was analyzed to contain 10.4% by weight # 5. Example 2 14 ° / 〇 Overbased calcium oleate / calcium carbonate According to this example, a phenol-free overbased calcium oleate / 14% by weight calcium was prepared. Calcium carbonate. Add 1700 grams of 9.89% overbased calcium oleate / calcium carboxylate made by the previous example method, and 42.5 grams of deionized water to 3 liters. Equipped with a pot stirrer, two gas inlet tubes, thermocouple, heating jacket , And resin pot with Dean Stark plate with condenser. Under a nitrogen atmosphere, the mixture was heated to a temperature of 195 T with stirring, and 385 grams of slaked lime (94% calcium hydride), 231 grams of hydrocarbon oil, and 96.25 grams of isocyanate were added at a rate of 3.42 grams per minute for 3 hours and 45 minutes. A slurry of decanol and 57.75 g of butylcarbitol. After the slurry was added for 5 minutes, carbon dioxide was added to the reaction at a rate of 1.2 standard cubic feet per hour. During the carbonation reaction, a temperature of 195-200 T was maintained, and the pH was monitored as in Example 1. After the end of the slurry addition, carbon dioxide was continuously added until the reaction mixture became neutral (expressed as a colorless sample when tested with phenolphthalein). The reaction mixture was then heated to 30 ° F, and the added water and the water produced in the reaction were removed by the Dean Stark tray. Add gram of diatomite to the dehydrated reaction product and, as described in Example 丨, filter the product through suction to produce a clear, amber, overbased calcium oleate / calcium carboxylate mobile fluid filtrate Once the cold part reaches room temperature, it can still remain clear. After analysis, the filtrate contained 14.5% by weight of calcium. Example 3 O: \ 90 \ 9073O.DOC -26- 2004243 06 10% high test oleic acid approx./carbon _, GRAS indirect food additive formula is widely used as a safety indirect food additive containing only phenol-free 1 high The basic calcium oleate / carbonate is prepared as follows: A mixture containing 520 · 6 g of oleic acid (1.85 moles), 522 g of shellflexTM 61u light mineral oil, 259 g of dodecanol, and 32.4 g of propylene glycol is heated to 18 〇 卞, and added 2.0 grams of propionic acid and bo grams of water. A slurry containing 3,456 grams of hellflex 6111'1, 728.8 grams of dodecanol, 21.6 grams of propylene glycol, and 540 grams of lime (94% calcium hydroxide) was continuously added to the stirred reaction mixture at a rate of 4.0 grams per minute. After 41 minutes of slurry, '', force, and force, the oleic acid was neutralized, excess lime was present, and partial dissolution resulted in an apparent pH of 1 1 · 4. Then at a rate of about 495 milliliters per minute

Carbon dioxide gas enters the reaction mixture through the sub-surface addition tube to generate and maintain lOiU pH ', which takes time to add the slurry (about an hour), while maintaining the reaction temperature between 19-192 ° F and gentle cooling. When about 1080 grams of slurry has been added, the slurry addition is stopped, and the dilute carbon is continuously added until the pH of the reaction drops to 7.5 (about 7 minutes). The reaction was placed under a vacuum of 22.5 Torr and heated to 3100 Torr for 175 hours while removing the added water and the water produced by the reaction through a Dean-Stark tube. The reaction was maintained at 3 ° F and 30 grams of diatomaceous earth filter aid was added. At a rate of 545 strokes per minute, as described in the previous example, the hot product was filtered through suction, and a clear, yellow amber overbased calcium oleate / calcium carbonate was filtered out. Once it is cooled to room temperature, it can still keep clear. After analysis, the filtrate s had 10.5% by weight of calcium. The infrared spectrum of the substance shows a sharp peak at the penultimate point of 864 cm, which is characteristic of amorphous calcium carbonate. !! Example 4

O: \ 90 \ 9O73O.DOC -27- 2004243 06 1 5% high oleic acid approx./carbonic acid can be prepared by the following procedure with 15.4% by weight of calcium overbased calcium oleate / calcium carboxylate. 50 grams of water was added to 1 700 grams of the overbased calcium oleate / calcium carbonate liquid mixture prepared according to the previous example, and the mixture was stirred at 1000 rpm to heat the mixture to 190 ° F. At a rate of 3.97 grams per minute, 720 grams of 500 grams of lime (94% argon oxide) obtained from 3 hours and 40 minutes were added, 3200 grams of 31 ^ 11, 11 ^ 6111 light mineral oil, and 16 grams of dodecanol , And a slurry of 20 g of propylene glycol into the mixture. After the slurry was added for 2 minutes, carbon dioxide gas was introduced into the reaction mixture at a rate of 10.5-11 (approximately 45 (M50 ml) per minute) at which the apparent pH of the reaction mixture can be maintained. After the time required to add the required amount of the lime slurry, stop adding the slurry, and continue to add the carbon dioxide until the pH of the reaction drops to 7.5 (about 10 minutes). Then at 22.5 " vacuum The reaction was heated and then sub-slowly heated to 310 F. The added water and the water produced by the reaction were removed by a Dean-Stark tray. The reaction mixture was then filtered through a bed of diatomaceous earth (filter aid). 'A clear, amber overbased calcium oleate / calcium carbonate flow-through was obtained. After analysis, the material contained 15.4% by weight of calcium. The infrared spectrum of the material was significantly less than 864 cm. The characteristic spikes of crystalline calcium carbonate. Example 5 A 14% overbased oleic acid / carbonic acid can be prepared by the following procedure with a total of about 14% strontium without phenol strontium oleate / carbonic acid. It contains 4 丨 3 grams of oleic acid, 600 g ShellflexTMfe ore , 300 g isodecanol '40 g of carbitol than alcohol, and 4 g of a mixture of triethylene glycol was heated to ι76

O: \ 90 \ 9O73O.DOC -28- 2004243 06 F ′ and looog lithium hydroxide octahydrate was added. The reaction mixture was heated to 275 ° F over 2.5 hours while removing 550 grams of water via a Dean-Stark tray by means of a nitrogen purge with 2.0 SCFH. The rate at which the water is removed is changed, and then the nitrogen spraying step is stopped, and carbon dioxide gas is added to the reaction through the subsurface addition tube at a rate of 450 ml per minute, and the formed water is continuously removed. After adding carbon dioxide for 7 hours at 250-275T, the addition of carbon dioxide was stopped to raise the reaction temperature to 300T, and the remaining water was removed by means of nitrogen spray washing with 2.0 SCFH. The thermal reaction was then filtered through suction with the aid of a rhenium to produce the overbased oleic acid / strontium carbonate in the form of a pale yellow, clear flowing fluid. Upon analysis, the product contained 14.25% by weight total. Example 6 4.5% high oleic acid / carbonate ball. A phenol-free magnesium oleate / carbonate ball containing about 4.5% magnesium can be prepared by the following procedure. A mixture containing 529.3 g of oleic acid, 600 g of ShellflexTM 6111 light mineral oil, 400 g of isopropanol, 350 g of isodecanol, and 400 g of water was heated to 400 ° C, and 400 g of magnesium hydroxide was added. Neutralizing the acid with the magnesium hydroxide will increase the temperature to 167T. At a rate of 225 milliliters per minute, carbon monoxide was introduced into the reaction mixture via a subsurface addition tube, which took 6 hours, at which time the temperature was gradually increased to 223 ° F, and 720 milliliters of water and isopropanol were removed. Of a mixture. The temperature was raised to 305 ° F, and the remaining water was removed by the addition of the carbon dioxide. The addition of the carbon dioxide was stopped, and the hot reaction mixture was filtered through suction with the aid of a filter aid to produce the overbased magnesium product in the form of a clear light yellow flowing liquid. After analysis, the product contained 4.5 * O: \ 90 \ 9O73O.DOC -29- 2004243 06% magnesium. Example 7 · 2 1 · 38% highly crystalline amorphous oleic acid / carbonic acid powder in a stable flow pattern, 200 g of an overbased calcium oleate / calcium carbonate liquid containing 10.5 wt% The product prepared by the method of Example 3) to 1000 grams of rapidly stirred isopropanol. The mixture was stirred at room temperature for 1 hour 'and then filtered through suction. This filter cake was washed with 2 × 100 g of isopropanol, blotted as far as possible ’and then allowed to dry overnight at room temperature. The obtained powder showed no crystallinity through an X-ray powder pattern, and it was easily dispersed in mineral oil 'to produce a clear, isotropic, non-sticky dispersion. The powder has been found to contain 21.38% by weight of calcium. The infrared spectrum of the powder (nujoi mull) showed a sharp peak at the reciprocal of 866 cm, which is characteristic of amorphous calcium carbonate. -Example 8 20.2% highly crystalline amorphous calcium oleate / calcium carbonate powder A powdery highly crystalline amorphous oleic acid / calcium carbonate was prepared according to the following example. Add 500 grams of overbased oleic acid solution / calcium citrate liquid (such as the product of the above example 1) containing 1 .76 weight% calcium to 1 500 grams of isopropanol over 15 minutes, quickly stir and heat to reflux . The mixture was refluxed for another half an hour, then allowed to cool to 90 ° F and filtered through suction. Approximately 2 x 125 g of isopropanol was washed off the collected solid and blotted as dry as possible. The solid product was dried overnight at room temperature to yield 262 g of an off-white solid which, when analyzed, contained 202% by weight calcium. This substance is very suitable for dispersing in mineral oil in the form of 70% solids to obtain a clear, flowing dispersion with a calcium content of 13.83% by weight. The powder (nujoi mull) O: \ 90 \ 9073O.DOC -30- 2004243 06 shows a red peak spectrum with a sharp peak at the reciprocal of 866 cm, which is a characteristic of the amorphous carbonic acid. The average particle diameter of the powder particles dispersed in the mineral essence was 0112 m. Example 9 A 28% overbased amorphous calcium oleate / calcium carbonate powder. Eight powders were prepared according to the following examples to prepare a highly amorphous amorphous oleate / calcium carbonate, which was added in a steady stream within 5 knives. 0 g of an overbased calcium oleate / calcium carbonate liquid dispersion (made by the method of Example 4 above) containing wt% calcium to i) 100 g of fast isopropyl alcohol. The mixture was stirred at room temperature for one hour, then filtered through suction, washed with 2 x 100 ml of isopropanol, and dried as much as possible. The product was air-dried overnight at room temperature to produce a non-flowing off-white powder 'which was analyzed to contain about 28% by weight. The powder scoops. !! The infrared spectrum of mull) shows a sharp peak at the reciprocal of 866 cm, which shows the characteristics of amorphous calcium carbonate. The X-ray powder chart shows only broad peaks and / or peaks derived from calcite (crystalline calcium carbonate). The powder, which had been dispersed in mineral spirits, showed an average particle diameter of 0.5566 microns. Example 10 φ 30% rain-proof amorphous barium oleate / barium carbonate 纩 A non-experienced amorphous barium oleate / barium carbonate was prepared according to the following example. Under a slow nitrogen stream, 502.5 g of oleic acid, 581 g of HVI mineral oil, 200.0 g of EPalTm 14-18 (a fatty alcohol mixture containing 14 to 18 carbon atoms), and 102 g of butylcarbitol (monoethyl ether) A mixture of diol monobutyl ether) and 10.2 grams of triethylene glycol was heated to 178F. 1034.1 g of barium hydroxide monohydrate was added to the heater's reaction mixture in 3 minutes in 45 minute increments. The temperature of the O: \ 90 \ 9073O.DOC -31-2004243 06 reaction mixture was raised to 280 ° C in one hour, and 75.6 grams of water was removed via the Dean Stark tray by means of the nitrogen stream of 2 SCFH. . The nitrogen flow was reduced to 1 SCFH, and carbon dioxide was added at a rate of about 300 ml per minute through a subsurface addition tube at 5½ hours. At this time, the temperature was gradually increased from 280 to 300T, and at After 2 hours, water was removed via a Dean-Stark tray at a rate of about 75 grams every 15 minutes. At the end of the carbon dioxide addition time, the reaction was carefully placed under a 22-inch vacuum and the remaining water and a small amount of butylcarbitol were removed. The total amount of water removed was 210 grams. After 30 minutes, the vacuum was released, and 40 grams of filter aid (Satite) was added. The mineral was subjected to suction filtration to obtain a clear, amber-colored, flowing liquid which was analyzed to contain 29.7 wt% barium. Example 11 45.2% high facial amorphous barium oleate / carbonate lock powder will contain 297% by weight of phenol-free overbased barium oleate / barium carbonate in a slow flow pattern within 5 minutes (made by Example 10) Into) 1000 grams of isopropanol, and quickly stirred. The mixture was stirred at room temperature for one hour, then filtered through suction, washed with 2 x 100 g of isopropanol, blotted as far as possible, and allowed to air dry. Upon analysis, the product (off-white powder) contained 45 2% by weight barium. Example 12 4 5 · 5% high-face amorphous amorphous barium oleate / aged barium / barium carbonate powder According to Example 10, a phenol-containing overbased amorphous barium oleate / barium phenol / barium carbonate solution containing 45.5% barium was prepared, and As described in U.S. Pat. No. 5,83,935, age was added to the reaction mixture. At room temperature, 200 g of this high-barium oleate / barium phenolate / barium carbonate was added to 1000 g of rapidly stirred isopropyl alcohol over 5 minutes. O: \ 90 \ 9O73O.DOC -32- 2004243 06 Mix the mixture for 1½ hours, then filter it with suction, wash with 2x100 g of isopropanol, blot as dry as possible, and let it air dry. After analysis, the product (pink powder) contained 45.5% by weight of barium. 1 The physical state of the calcium carbonate in each of the substances prepared in each of the examples was analyzed for crystallinity by an X-ray powder chart, and was analyzed by infrared spectroscopy. According to the paper "Infrared Spectra of Amorphous and Crystalline Calcium Carbonate" by Andersen and Brecevic, Acta 011 € 111 Qin118〇 & 11 (^ 11 & ¥ Huawang45 (1991) 1018-1024 households, amorphous carbonate feed The infrared absorption effect occurs at the reciprocal of 864 cm. The corresponding infrared absorption effect of calcium carbonate, calcite, vermiculite and other crystalline polymorphs of spherical calcite occurs at the reciprocal of 877, 856, and 877 cm, respectively. Lubricant. Composition Formulation In order to illustrate the beneficial properties of the lubricant composition of the present invention containing the highly protective additive of the metal protective agent, many formulations were prepared and evaluated. In preparing the full lubricant composition, a common method is to form a concentrate Additives are introduced into a suitable carrier (for example, lubricating oil) or other suitable solvents. Aliphatic hydrocarbons, naphthenes, and aromatic hydrocarbons are examples of suitable carrier fluids for the additive concentrate. The concentrate formulated below is called " DI Packaging ". The final packaging includes the DI packaging formulation with the base oil or other viscosity modifier. Therefore, in Table 1, as shown in Table 丨Prepared in Packing Sample B, the liquid overbased oleic calcium / calcium carbonate of Example 1 mentioned above can be used as the metal protective agent additive of the present invention, and the final lubricant composition includes adding the packaged additives to In the lubricating oil described in Table 1. The content of the overbased calcium oleate / calcium carbonate in the final lubricant composition is about 0 7% by weight of the composition.

O: \ 90 \ 9O73O.DOC -33- 2004243 06 DIS " H-646 (Jinping § H 丨 611 (Miao Xia Xue Chuanbei) H-614 (Invite to the Miao Phosphorus Carving) ss I ^ a K-2000 (车 镞 涔 w # j) N-438L (^ lub salt) Star 4 (lacquer 11 green ^ > ®: ^ -pfaA (^ pf # J) stari (1) ^: DI & Wei Viscoplex (VI ^ L ^ l) > 5 ^^ Star4 ~ tt: 500 L50 L40 P75 100 L75 0 · 75 0 · 40 10 ppm79 · 95 1105 90 A 87 · 50 24.50 13 · 13 17.50 30.S 13 · 13 70 00175 SS3 193.38 ί57 · 50 175000 ^ 06.13 Β 87.50 24.50 13 · 13 Π · 50 30.S 13.13 70 00175 1399 · 13 § • 300 157.50 175000 1406.13 η 87 · 50 24.50 13.13 17.50 13.13 37¾ 00175 SS3 193.38 157.50 175000 S6.75 13.13 17.50 13.13 62.13 00175 S9.13 19138 157.50 175000 142.25 D 007.50 Use of blend: Component c ^ 3 Y Blend percentage 1750.0 2046.8 Normal oil positive control 1750.0 2046.8 S ^ ^ 5 green 1750.0 2046.8 5 also 0 way ω 8 full 1750.0 2046.8 no FM or detergent negative control 1750.0 2046.8 O: \ 90 \ 90730.DOC 34- 2004243 06 For Table 1, the following is another confirmation of each component: H- 611 (High alkaline sulfonic acid) HiTec -611 * OB calcium sulfonate Ethyl H-614 (neutral sulfonate) HiTec-614 * neutral calcium sulfonate Ethyl H-7169 (antiwear agent) HiTec-7169 * zinc dialkyl dithiophosphate Ethyl K- 2000 (friction modifier) Kemester 2000 Glycerin monooleate Crompton N-438L (antioxidant) N-438L Nonylated diphenylamine Crompton Star 4 oil (II group base oil) Star 4 oil plus rat treatment Series mineral oil Motiva Antifoam A (Defoamer) Antifoam nA ”Octamethylcyclotetrasiloxane Dow Viscoplex (VI improver) ak Viscoplex 6-917 Acrylic polymer / Neutral oil Degussa This additive has mineral Oil and petroleum distillates are used as a diluent with reference to Table 1, and the sample B is compared with the overbased calcium sulfonate / obcocarbonate (OBCO) additive of the present invention and the overbased calcium sulfonate of common oil (sample A) ( OBCS) additives. For sample B, the cleaning ability of the 0BC0 was evaluated in the presence of a friction modifier. Similarly, in the sample C without the friction modifier, the lubricity of the OBCO was evaluated. For this sample D as a negative control, OBCO, OBCS and friction modifiers were not used. The Panel coker test was used to determine the cleanability of Samples A-D in Table 1. The Panel Coker test is a fast laboratory method to determine the relative deposit formation of the lubricant. This can be accomplished by splashing lubricant on the heated metal sheet. The Panel Coker test isolates engine cleaning variables with high temperature stability and surface activity, and prevents any oxidized substances from depositing from the bulk oil. The UEC Panel Coker test results are shown in Table 2. The procedure is to measure the deposits caused by the heat and oxidative stress of lubricant degradation under the test conditions of 330 ml samples at a high temperature of 600 ° F and a test time of 6 hours. weight. O: \ 90 \ 9073O.DOC -35- 2004243 06 Table 2

Panel Coker test results-Sediment (mg) Blend test 1 Experiment 2 Average annotation A 205 235 220 OBCS B 133 124 128 OBCO C 167 189 OBCO / FM-free D 289 252 270 OBCO-free / FM-free Test conditions: 600 ° F, 330 ml sample, refer to Table 2 for 6 hours, test each formulation in Table 1, and complete the following observations. The lubricant composition containing the 0BC0 metal protective agent of the present invention showed good results. The average test results of samples B and C were 128 and 178 mg of deposit, respectively. In contrast, the common oil containing 0BCS produced an average of 220 mg of sediment (Sample A) and 270 mg of sediment (Sample D). Therefore, the 0BC0 of the present invention has more excellent cleaning ability compared with the common ordinary oils having OBCS and other compositions containing no overbased additives or friction modifiers. The lubricating composition of the present invention was tested for its oxidation stability or stability against the corrosiveness or acidic portion generated from oxidation of the fuel composition or oil. An analysis of the oxidation characteristics of the lubricant composition was performed according to ASTM D943. This procedure was used to evaluate the oxidative stability of samples A-D at high temperature (95 ° C) in the presence of tritium, water, iron salts and copper salts. The ASTM D943 test is a low-temperature oxidation-corrosion test for lubricants (for example, steam turbine oils and hydraulic oils, which are expected to encounter wet conditions but also to last a long time). Therefore, the D943 test conditions are based on liquid water (which is in contact with the copper and iron metal catalyst sample embryos and has the ability to foam in the mixture as the oxygen O: \ 90 \ 9O73O.DOC -36- 2004243 06 It is carried out at 95t in the presence of a pure oxygen gas of a chemical agent. The success of the ASTM D943 test requires that the lubricant formulations provide the significant thinning effect of the iron and copper metals 'and a retentive retention that lasts long enough to reach the 1000 hour minimum time', among which the alkali retention It can be used up and the oil reaches an acid number of 2. The test results of comparing the OBCO of the additive of the present invention with the OBCS prepared as shown in Table 1 are shown in Table 3. Table 3 Time’hour acid value, ASTM D 3339

OBCS of Table 1 OBCO of Table 1

Sample A Sample B — 〇2.13 Cloud T Water υ 1.93 500 0.58 668 0.66 1.26 836 0.69 1.43 ~ 1000 1.59 1004__ 0.74 * 1172 1.26 1196 1.40 1340 1.56 1508 1.67 1.57 1676 ^ 2.58 ^ 1.72 1844 1.70 2012 「96 2180 1.98 ^ 2348 Γ64 ~ '25 16 Γ36 2852 1.73 3020 1.84 35 00 2.14 With reference to Table 3, in the low temperature oxidation application, the OBCO metal protective agent additive in the lubricating composition of the present invention proves to be more suitable as an inspection source than the OBcs. More specifically, Table 3 shows that the OBCO oleate additive of the present invention requires almost three times as long as the OBCS sulfonate additive to reach O: \ 90 \ 9O73O.DOC -37- 2004243 06 2.0 acid. For the OBCS, the acid value reached 2.58 after 1676 hours of testing, and the acid value of the OBCO was 2.14 after 3,500 hours of testing. It has been assumed that the TAN value of the OBCO sample at the beginning of the test is more stable. High indicates that a buffering effect can be formed by the oleate (not the sulfonate). Therefore, at the beginning of the test, the 1,2 TAN value of the oleate was about twice the TAN value of the sulfonate. However, the long-term nature of the OBCO oleate Can far exceed the long-term performance of the OBCS sulfonate. Therefore, from the viewpoint of resisting damage to acids (acid damage will affect the engine function and reduce the quality of the lubricant), the lubricating oil of the present invention containing a unique OBCO additive The performance of the agent composition is much better than the performance of the existing common oil composition. Test Table 1 The OBCS and OBCO samples A and B and the sample E prepared according to the method of the present invention are substituted with isostearic acid for Example 1. High test made of oleic acid. Calcium isostearate / calcium carbonate. Once tested according to ASTM D-5706 and D-5707 the OBCS, OBCO and OBIS (overbased isostearate / carbonate) It is found that the performance of the additive of the present invention is better than that of the OBCS sample when the friction is improved. More specifically, according to ASTM D-5706, the OBCO and OBIS additive of the present invention has higher load for a longer time. Better than the OBCS sample. Similarly, in the ASTM D-5707 friction and wear test, the OBCO and OBIS additive of the present invention is superior to the OBCS additive. The above description provides specific implementation of the present invention and also discloses the content, without intending to limit it This invention. So this The invention is not limited to the specific embodiments described above, but it must be understood by those skilled in the art that other specific embodiments within the scope of the invention can be understood in view of the above description. O: \ 90 \ 9O73O.DOC -38-

Claims (1)

2004243 06 Scope of patent application: h — a lubricating oil composition containing lubricating oil and an additive as a metal protective agent, which is selected from the group consisting of: ⑷ fatty acid local amorphous amorphous metal carbonate A stable and non-turbid liquid, and (b) a powdery highly crystalline amorphous ochre metal carbonate of a fatty acid isolated from the liquid, the liquid or powdery additive is prepared according to the following steps: Eight (i) In the presence of liquid smoke, 'test the metal test against fatty acids, the metal test to fatty acid equivalent ratio is greater than 1: 1, (ii) carbonate the mixture to prepare an amorphous alkaline earth metal carbonate, (iii) in During the carbonation reaction, it is added at a controlled rate of an alkaline earth metal base to a dispersion containing a relative amount of an alkaline earth metal base, a liquid hydrocarbon, and a fatty alcohol having at least 8 carbon atoms to prepare a stable non-turbid liquid reaction product, and (iv) removing water from the reaction product to obtain the liquid additive or powdery additive. 2. The lubricating oil composition according to item 1 of the scope of the patent application, wherein the liquid reaction product is filtered at a product filtration rate of at least about 300 ml per 10 minutes to prepare a thermodynamically stable liquid. 3. The lubricating oil composition according to item 1 of the application, wherein the fatty acid is a C12-C22 fatty acid. O: \ 90 \ 9O73O.DOC 4 · According to the scope of patent application! The lubricating oil composition of the item, wherein the fatty acid is oleic acid or isostearic acid. 5. The lubricating oil composition according to item i of the patent claim, wherein the water is removed. It is known that the water contains 1 microemulsion product of less than about i% by weight of the total product. 6. The lubricating oil composition according to item 1 of the scope of the patent application, wherein the alkaline earth metal is selected from the group consisting of ma, barium, magnesium and gills. 7. The lubricating oil composition according to item 1 of the scope of patent application, wherein the alkaline earth metal is a J bow. 8. The lubricating oil composition according to item 1 of the scope of the patent application, wherein the overbased salt is oleic acid / carbonic acid. 9. The lubricating oil composition according to item 1 of the scope of the patent application, wherein the overbased salt is substantially free of various derivatives. 10. The lubricating oil composition according to item 1 of the Shenyan patent scope, wherein the fatty alcohol has 8 to 14 carbon atoms. 11. The lubricating oil composition according to item 10 of the application, wherein the alcohol is isodecanol. 12. The lubricating oil composition according to item 11 of the Shenjing patent scope, wherein the dispersant further contains a glycol or a glycol ether. 13. The lubricating oil composition according to item 12 of the scope of the patent application, wherein the diol or diol scale is selected from the group consisting of diethylene glycol monobutyl ether, triethylene glycol, dipropylene glycol, diethylene glycol monomethyl ether, and ethylene glycol. Glycol monobutyl ether and mixtures thereof. 14. The lubricating oil composition according to item 1 of the scope of the patent application, wherein the step of forming the inverse O: \ 90 \ 9O73O.DOC 2004243 06 15. 16. 17. 18. 19. 20. reacting the product is based on the final reaction Based on the mixture, a content of an alkaline earth metal selected from the group consisting of about Γ5-30% calcium hydroxide, about 12-24% magnesium hydroxide, about 25-50% oxychlorine pin, and about 35-50% barium hydroxide Test its mixture reaction. The lubricating oil composition according to item 14 of the application, wherein the alkaline earth metal salt is calcium hydroxide and the fatty acid is oleic acid. The lubricating oil composition according to claim 15 of the application, wherein the turbid liquid calcium oleate is a microemulsion having amorphous calcium carbonate in the microemulsion microparticles. The lubricating oil composition according to item 1 of the scope of patent application, wherein the dispersion is added and carbonized with carbon dioxide, and the mixture contains about 15-30% oleic acid, about 9-35% carbonic acid, and about 30- 35% e-liquid, about 15-18% isodecanol, and about 4-6% glycol or glycol test. The lubricating oil composition according to item 17 of the scope of the patent application, wherein the dispersion contains about 40-50% calcium hydroxide, about 25-40% hydrocarbon oil, about 10_25% isodecanol ', and about 0-10% di Alcohol or glycol ether. According to the lubricating oil composition according to the scope of the patent application, based on the total weight of the oil composition, the amount of the additive can obtain about 0.5 to about 15% by weight of the overbased metal carbonate. According to the lubricating oil composition of the scope of application for item i, wherein the total amount of the oil composition is used as a basis, the amount of the additive can be obtained from Qi 5 to about 7 O: \ 90 \ 9073O.DOC 2004243 06 heavy day 〇 / 〇 This highly sensitive metal carbonate. 21. The lubricating oil composition according to item 1 of the scope of application, wherein the effective amount of H, and additives can protect the metal by neutralizing the acid portion when it is lubricated by the composition. According to claim 1, the lubricating oil composition of the patent scope, wherein the effective amount of the additive can protect the metal by improving the cleaning ability when it is lubricated by the composition. The lubricating oil composition according to item 1 of the scope of patent application, wherein the effective amount of the additive can protect the metal by improving the abrasion resistance when it is lubricated by the composition. 24 · —A lubricating oil composition containing a lubricating oil and a fatty acid powder overbased amorphous amorphous alkaline earth metal carbonate additive as a metal protective agent, wherein the fatty acid powder overbased amorphous alkaline earth metal carbonate additive is basically The upper is composed of an isolated solid cohesive micelle of a complex salt composed of an amorphous alkaline earth metal carbonate and a fatty acid non-crystalline alkaline earth metal slow acid salt. 25. The lubricating oil composition according to item 24 of the patent application, wherein the fatty acid is a C12-C22 fatty acid. 26. The lubricating oil composition according to item 24 of the patent application, wherein the fatty acid is oleic acid or isostearic acid. 27. The lubricating oil composition according to item 24 of the patent application, wherein water is removed to obtain a microemulsion product having a water content of about 1% by weight of the total product. 28. The lubricating oil composition according to item 24 of the application, wherein the alkaline earth metal is selected from the group consisting of calcium, barium, magnesium and gills. 29. The lubricating oil composition according to item 24 of the scope of patent application, wherein the alkaline earth O: \ 90 \ 9O73O.DOC 2004243 06 metal is feed. 30. The turbid oil composition according to item 24 of the patent, wherein the highly sensitive salt is calcium oleate / calcium carbonate. 31. The lubricating oil composition according to item 24 of the scope of patent application, wherein based on the total weight of the oil composition, the amount of the additive can obtain about 0.05 to about 15% by weight of the overbased metal carbonate. 32. The lubricating oil composition according to item 24 of the scope of the patent application, wherein based on the total weight of the oil composition, the amount of the additive can obtain about 7% to about 7% by weight of the highly sensitive metal carbonate. 33. The lubricating oil composition according to claim 24, wherein the effective amount of the additive can protect the metal by neutralizing the acid portion when it is lubricated by the composition. 34. According to No. 24 of the scope of patent application, the lubricant is effective, and the effective additive can protect the metal by improving the cleaning ability when the composition is used for lubrication. 35. Lubricant ^ ^ ^ ^, & according to item 24 of the Chinese Patent Application, wherein the effective additive can be used to improve the wear resistance when it enters A through the composition To protect the metal. 0. \ 90 \ 90730.DOC 2004243 06 柒. Designated representative map: (1) The designated representative map in this case is: (none). (II) Brief description of the representative symbols of the components in this representative diagram: Yang J. If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: (none) O: \ 90 \ 9073O.DOC