KR20110059561A - Overbased metal carboxylate complex grease and process for making - Google Patents

Abstract

Complex greases of high basic alkaline earth metal carboxylates are prepared by reacting a high basic alkaline earth metal salt of a fatty acid with a converting agent to form a grease precursor, the alkaline earth metal salt having an alkaline earth metal content of at least 14.5% and a ratio of 95% Has a volatile content. The formed grease precursor reacts with the complexing agent to form a permanent bacterite-containing modified non-Newtonian type high basic metal carboxylate complex grease.

Description

High basic metal carboxylate complex grease and its manufacturing method {OVERBASED METAL CARBOXYLATE COMPLEX GREASE AND PROCESS FOR MAKING}

The present invention is filed with the US Receiving Office as a PCT application claiming priority of US Patent Provisional Application No. 61 / 094,598 of September 5, 2008, the contents of which are incorporated herein by reference.

The present invention relates to composite greases prepared from high basic alkaline earth metal soaps of fatty acids. More specifically, the present invention relates to vatite greases prepared from high basic metal carboxylates using one or more complexing agents in the production process.

The preparation of highly basic alkaline earth metal soap greases includes a one or two step process. In a conventional two-step process, an amorphous high basic alkali metal soap, which is a carboxylate, sulfonate, phenonate or other organic acid salt or mixtures thereof, is first isolated and then converted to crystalline form. Amorphous high basic alkali metal soaps are usually in the form of microcrystalline (microseled) structures in which an amorphous carbonate core is dispersed in a hydrocarbon liquid having an appropriate viscosity. These liquid grease precursors usually have high TBN values of 200-400 mg KOH / gm or more. In a one-step process, amorphous high basic alkali metal soaps are not separated and the conversion from amorphous form to crystalline form is carried out as is in the same reactor or in a single step in a grease vessel. In addition to the morphological change from amorphous to crystalline, the initial high base material changes from a Newtonian liquid to a non-Newtonian gel or thixotropic grease. Unlike most neutral or near-neutral metal soap thickening greases, which are either single metal soap greases or complex soap greases, the high TBN high basic metal soap thickening greases described above possess a number of advantageous functional properties without additives. These functional properties include excellent anti-wear resistance, load resistance, dropping point, excellent shear stability or mechanical strength, many other features depending on the nature of the high base metal soap thickener, and chemical processability associated with grease production. Include.

An important step in grease production is the formation of thickener microstructures. The microstructure or matrix of the crystalline material contained in the grease assists the absorption and release of the lubricant. This is particularly important for greases containing high base metal soap thickeners, which not only allow the thickener microstructure to allow absorption and release of lubricating oil, but also the thickener itself serves as a performance additive and also contributes to the final grease product. This is because it provides various performances. Processing conditions such as temperature, pressure, residence time and saponification stoichiometry, etc., have a great influence on the microstructure of the thickener produced. The grease production method also features a single step or a multistep process consisting of a conversion step, an ignition step and a finishing step based on the physical changes and chemical reactions involved in the grease production process. Thus, processing conditions and processing steps determine the various performances of the final grease product.

Thixotropic grease or grease type high basic metal carboxylates, or other high base metal containing compositions having acid neutralization and detergent properties and having various applications such as anti-rust undercoat for automobiles and truck bodies or other purposes. Known. These greases or grease-like compositions are used as such for a wide range of applications or mixed with other ingredients to produce compositions for a variety of environments, which typically have good extreme pressure and antiwear properties, high dropping point, good resistance to mechanical breakage, Salt spraying, corrosion resistance, high temperature thermal stability, and other desirable properties.

Highly basic metal carboxylates are usually prepared by carbonating a mixture of hydrocarbons, carboxylic acids, metal oxides (such as calcium oxide) or metal hydroxides (such as calcium hydroxide) with accelerators such as methanol and water. In the carbonation reaction, calcium oxide or calcium hydroxide reacts with carbon dioxide gas to form calcium carbonate. The carboxylic acid is neutralized with excess CaO or Ca (OH) ₂ to form carboxylates. A high alkaline material having a TBN value of at least 300 mg KOH / gm is prepared according to the conventionally known high base of calcium carboxylate. TBN is a measure of alkaline storage and refers to a potassium hydroxide value in milligrams equal to the amount of acid required to neutralize the alkaline component present per gram of sample. Additives having a total number of bases greater than can be obtained from stoichiometrically prepared calcium carboxylate alone are usually referred to as "highly basic" or "superbasic".

The addition of a converting agent to a high basic Newtonian liquid or other highly basic metal containing material of calcium sulfonate during heating and / or with strong stirring mixing forms a non-Newtonian colloidal dispersion system. There are various types of such converting agents, among which water; Methanol, isobutanol, n-pentanol and other kinds of alcohols or mixtures thereof or mixtures of alcohols and water; Alkylene glycols; Mono-lower alkyl ethers of alkylene glycols such as monomethyl ether of ethylene glycol; Many lower aliphatic carboxylic acids such as acetic acid and propionic acid; Ketones; Aldehydes; Amines; Phosphoric acid; Alkyl and aromatic amines; Some imidazolines; Alkanolamines; In addition, carbon dioxide and a combination of water and the like can be given. The resulting non-Newtonian colloidal dispersion system may be in the form of gel or grease depending on the specific conditions, relative ratios and component types used in the preparation.

In the conventional high basic calcium-containing Newtonian solution, the calcium carbonate formed during the preparation of the Newtonian solution generally exhibits an amorphous form, while the dissolved Newtonic solution is converted to a non-Newtonian colloidal dispersion system. The calcium salt or its complex salt is transformed into solid crystal grains of calcium carbonate such as calsite. It grows again to a size in the range of 40 to 50 angstroms or more, such as up to 1000 kV or 5000 kV. The calcium carbonate component of the high basic metal carboxylate forms the core of the metal carboxylate microcrystalline structure.

In high basic alkaline earth metal carboxylates of higher carboxylic acids, such as oleic acid, when calcium and carbonates are added to a Newtonian solution of amorphous calcium carbonate and calcium carbonate, amorphous calcium carbonate becomes crystalline calcium carbonate. Is converted to vaterite, which is a spherical form of, and no calsite is formed. Highly basic calcium sulfonates, in contrast, form a mixture of calsite or calsite and batite from amorphous high basic calcium sulfonates upon conversion.

In spite of the above-described state of the art, various functionalities such as shear stability, anti-wear resistance, extreme pressure or load resistance, dropping point, and useful temperature range are improved in the preparation of the varite-containing grease modified by the complexing agent. There is a need to improve the production process so that the yield is improved in terms of good oil incorporation.

In general, one aspect of the present invention is to provide a high basic metal carboxylate complex grease. The high basic metal carboxylate complex grease includes a high basic alkaline earth metal salt of a fatty acid, wherein the alkaline earth metal salt has an alkaline earth metal content of at least 14.5% and a nonvolatile material content of at least 95%, and the grease is a hydrocarbon liquid. , A conversion agent comprising water, limestone, glycol and short-chain carboxylic acids selected from the group consisting of acetic acid and propionic acid, and also groups consisting of phosphoric acid, boric acid, C ₁₂ -C ₂₄ aliphatic monocarboxylic acids and C ₁₂ -C ₂₄ fatty acids It includes at least one complexing agent selected from.

Another aspect of the present invention is to provide a method for producing a composite grease. This way:

Providing a high basic alkaline earth metal salt of fatty acid having an alkaline earth metal content of at least 14.5% and a nonvolatile material content of at least 95%;

A high basic alkaline earth metal salt of the fatty acid is reacted with a converting agent to form a Newton-type grease precursor, wherein the converting agent is a short-chain carboxylic acid selected from the group consisting of hydrocarbon liquid, water, limestone, polyol and acetic acid and propionic acid It contains; Also

Reacting the Newtonian grease precursor with at least one complexing agent to form a non-Newtonian complex grease, wherein the at least one complexing agent is phosphoric acid, boric acid, C ₁₂ -C ₂₄ aliphatic monocarboxylic acid and C _It is characterized in that it is selected from the group consisting of ₁₂ -C ₂₄ fatty acids.

Another aspect of the present invention is to provide a method for producing another composite grease. This way:

Providing a high basic alkaline earth metal salt of fatty acid having an alkaline earth metal content of at least 14.5% and a nonvolatile material content of at least 95%;

A high basic alkaline earth metal salt of the fatty acid is reacted with a conversion agent to form a thixotropic non-Newtonian gel grease precursor, wherein the conversion agent is selected from the group consisting of hydrocarbon solution, water, limestone, polyol and acetic acid and propionic acid. Contains chain carboxylic acids; Also

Reacting the non-Newtonian grease precursor with at least one complexing agent to form a non-Newtonian complex grease, wherein the at least one complexing agent is phosphoric acid, boric acid, C ₁₂ -C ₂₄ aliphatic monocarboxylic acid and It is characterized in that the selected from the group consisting of C ₁₂ -C ₂₄ fatty acids.

1 shows a representative X-ray diffraction spectrum of a bacterite calcium carbonate;
2 shows a representative X-ray diffraction spectrum of calsite type calcium carbonate;
3 shows representative X-ray diffraction spectra of high basic calcium oleate carboxylates used in the preparation of high basic calcium oleate composite greases;
4 shows a representative X-ray diffraction spectrum of a highly basic calcium oleate composite grease according to one embodiment of the present invention;
FIG. 5 shows representative FTIR spectra of high basic calcium sulphonate grease, high basic calcium oleate carboxylate used to prepare high basic calcium oleate composite grease, and also high basic calcium oleate composite grease according to one embodiment of the present invention. and;
6A-6E show representative FTIR spectra of various highly basic calcium oleate composite greases, respectively;
FIG. 7 shows representative FTIR spectra of high basic calcium oleate carboxylates used for preparing high basic calcium oleate composite grease and high basic calcium oleate composite grease according to one embodiment of the invention, respectively; FIG.
8A-8D show representative FTIR spectra of commercially available high basic calcium sulfonate greases, respectively;
9 shows representative FTIR spectra of commercially available calcium sulfonate composite grease (A), calcium oleate composite grease (B), and Newtonian type high basic calcium oleate material (C), respectively; Also
FIG. 10 shows a representative FTIR spectrum showing the conversion of amorphous to crystalline calcium carbonate upon formation of calcium oleate composite grease.

In the process of preparing a composite grease, a high base grease precursor, which is an intermediate, is reacted when a New Uton type high basic alkaline earth metal carboxylate reacts with a water, limestone, hydrocarbon solution, glycol and a conversion agent containing short chain carboxylic acids such as acetic acid and propionic acid. Material is formed. The high base grease precursor is used alone or in combination with a complex salt comprising fatty acids or aliphatic monocarboxylic acids such as phosphoric acid, boric acid and / or C ₁₂ -C ₂₄ acid. Upon reaction with the conversion agent, the Newtonian type high basic alkaline earth metal carboxylates are converted to thixotropic non-Newtonian type gel grease precursors containing mainly batterite. When combined with a complexing agent, the vaterite-containing grease precursor is modified again to improve the yield in terms of oil content, and also to improve the basic properties such as resistance to mechanical shear, extreme pressure, anti-wear resistance and dropping point temperature. Form a composite grease.

In another composite grease preparation process, the Newton-type high basic alkaline earth metal carboxylate is reacted with a converting agent and subsequently a complexing agent, and then the conversion from the Newton-type high basic grease precursor to the non-Newtonian grease is completed. Conversion agents include water, limestone, hydrocarbon solutions, glycols and short chain carboxylic acids such as acetic acid or propionic acid. Complexing agents also include fatty acids or aliphatic monocarboxylic acids such as phosphoric acid, boric acid and / or C ₁₂ -C ₂₄ acids. When reacted with both a converting agent and a complexing agent, the Newton-type high basic alkaline earth metal carboxylates are converted to non-Newton-type composite grease containing mainly batterite according to the one-stage reaction, thus improving production efficiency and processing Simplification can be achieved. Vaterite-containing composite grease formed by the fasting reaction has improved properties such as mechanical shear resistance, extreme pressure, anti-wear resistance, and dropping point temperature.

In one embodiment of the present invention, the method for preparing a composite grease is a two-step process, in which the first step is a process for preparing a suitable Newtonian type high basic metal soap solution, and the second step is for Fasting reaction to convert to Newtonian grease. In the fasting reaction, the Newton-type high basic alkaline earth metal carboxylate and the converting agent are reacted for a predetermined time in the form of the intermediate high basic grease precursor remaining the Newton-type solution. Subsequent addition of the complex salt converts the Newtonian intermediate high basic grease precursor into a modified non-Newtonian high basic calcium carboxylate complex grease containing mainly batterite.

In another embodiment of the present invention, the method for producing a composite grease is a two-step process in which the first step comprises the preparation of a suitable Newtonian type high basic metal soap solution and the second step comprises a two-stage reaction. In the two-stage reaction, the first reaction comprises reacting the Newton-type high basic alkaline earth metal carboxylate with the conversion agent for a predetermined time such that an intermediate high basic grease precursor is obtained in the form of a thixotropic non-Newtonian gel concentrate. do. The second reaction involves adding and reacting a conversion agent to the grease precursor to convert the thick, non-Newtonian intermediate high base grease precursor to a modified high base calcium carbonate composite grease containing mainly batterite.

The alkaline earth metal of the carboxylate salt is selected from the group consisting of calcium, barium, magnesium and strontium. This metal is derived from metal oxides and hydroxides, in some cases metal sulfides and hydrogen sulfides. For example, the grease precursor may comprise high basic calcium carboxylate.

The carboxylic acid portion of the metal carboxylate contains C ₈ -C ₃₀ saturated, unsaturated carboxylic acids having 8 to 30 carbon atoms alone or in the form of a mixture of two or more or the reactivity of the carboxylic acid. Include equivalents. Examples of the carboxylic acid and fatty acid that can be used include, but are not particularly limited to, 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, linolenic acid, arachidic acid, gadoleic acid, behenic acid, erucic acid And mixtures thereof.

Formation of metal carboxylates also includes alcohols that promote the formation of highly basic alkaline earth metal carboxylates. Alcohols include aliphatic alcohols having at least eight carbon atoms. In one embodiment, aliphatic alcohols having 8 to 14 or more carbon atoms can be used. Examples of such aliphatic alcohols include isodecanol, dodecanol, octanol, tridecanol, tetradecanol or mixtures thereof. It has been found that phenol can be excluded from the reaction as a promoter when higher aliphatic alcohols are used to prepare the high basic product.

The high basic metal carboxylates used in the preparation of the composite greases are prepared to contain calcium which is at least 12.5% by weight of alkaline earth metal. In the preparation of high metal, high basic products containing, for example, at least 15% by weight of metal, polyols have been found suitable for use. The polyol may be glycol or glycol ether. The glycol or glycol ether is selected from the group consisting of diethylene glycol monobutyl ether [butyl carbitol ^® ], triethylene glycol, dipropylene glycol, diethylene glycol monomethyl ether, ethylene monobutyl ether and mixtures thereof.

The preparation method of the highly basic calcium carboxylate to be used in the preparation of the composite grease is in the presence of at least one liquid hydrocarbon, alcohol and glycol ether such as polyol such as alkaline earth metal base and fatty acid as the equivalent ratio of the metal base to the fatty acid of 1: 1 or more. And reacting in proportion. The mixture is acidified and carbonated to produce amorphous alkaline earth metal carbonates in the mixture. A dispersion may be added during the carbonation reaction, and a stable liquid reaction product is prepared by reacting a mixture containing an alkaline earth metal base, a liquid hydrocarbon and an alcohol having at least eight carbon atoms in a relative amount at a predetermined acid addition reaction rate. During the reaction, water is removed from the reaction product to prepare a room temperature stable flowing liquid high basic alkaline earth metal salt. In general, the entire process is carried out in the absence of oxygen, using a nitrogen atmosphere for this purpose.

In the present specification and claims, "acidic gas" refers to a gas that reacts with water to produce an acid. Such gases include sulfur dioxide, sulfur trioxide, carbon dioxide, carbon disulfide, hydrogen sulfide and the like and are examples of acidic gases useful for preparing the high basic metal carboxylates disclosed herein. The use of carbon dioxide forms alkaline earth metal carbonates. When sulfur gas is used, sulfates, sulfides and sulfites are formed.

In the carbonation reaction of the high base material, the mixture may be heated to a temperature sufficient to partially evaporate the water produced in the reaction of the water or base contained in the mixture and the carboxylic acid may be retained in the high base reaction. Mixture treatment with carbon dioxide is preferably carried out at elevated temperatures and the temperature applied in this step is in the range of about 75 ° C. (about 165 ° F.) to 200 ° C. (about 390 ° F.) above room temperature. High temperatures above 250 ° C. (about 480 ° F.) can also be used, but high temperature applications have no particular advantage. Typically a temperature of about 80 ° C. (about 175 ° F.) to 150 ° C. (about 300 ° F.) is appropriate.

 After water is removed from alkaline earth metal bases, fatty acids, polyols, liquid hydrocarbons and alcohols, the highly basic material is distilled or decomposed at temperatures up to 165 ° C. (about 330 ° F.) to separate the volatile components in the reaction product. In the term distillation process, "decomposition (striping)" refers to the removal of volatile components from low volatility materials. The decomposition under reduced pressure is carried out until the measured alkaline earth metal content in the final product is at least 14.5% and the nonvolatile material content is at least 95%.

The high base material used in the preparation of the composite grease is a thermodynamically stable microfluid. Microfluidics have microcrystals (microels) and continuous phases. Microcrystals consist of alkaline earth metal carbonates and alkaline earth metal carboxylates of fatty acids. The continuous phase of the microfluid is composed of liquid hydrocarbons and alcohols.

Suitable conversion agents utilized in the preparation of the highly basic thixotropic non-Newtonian gel grease precursors are water; In straight chain or branched aliphatic hydrocarbon group having a saturated ring structure, mineral spirits, non-aromatic hydrocarbons and polyalphaolefins (PAOs), and the like, as a suitable example be mentioned drive kejol ^® 600 liquid hydrocarbon; Limestone (CaOH ₂ ); Alcohols such as methanol, isobutanol, n-pentanol and the like, or mixtures thereof, or mixtures of alcohol and water; Alkylene glycols; Mono-lower alkyl ethers of monomethyl ether alkylene and propylene glycol, such as monomethyl ethyl ether of ethylene glycol and propylene glycol; It also contains a number of other substances, such as lower aliphatic carboxylic acids, including acetic acid and propionic acid.

Suitable complexing agents which will be added to the highly basic thixotropic non-Newtonian gel grease precursor to form the composite grease include water; Phosphorus containing acids such as phosphoric acid; Alkyl and aromatic amines; Boron-based acids such as boric acid, tetraboric acid, metaboric acid, and the like; Esters of such boric acids; Also included are fatty acids or aliphatic acids having 12 to 24 carbon atoms, such as dodecanoic acid, partic acid, stearic acid, oleic acid, ricinoleic acid, 12-hydroxystearic acid, and the like. Hydrogenated fatty acids, especially hydroxystearic acid, have generally increased grease thickening compared to unsubstituted fatty acids.

In one embodiment of the present invention, the fasting reaction for the preparation of the composite grease is carried out by heating a Newtonian type high basic calcium oleate material together with a conversion agent, under conditions suitable to form calcium carbonate crystals in the form of vatite crystals instead of calsite. Forming a Newtonian type high basic grease precursor, wherein the converting agent contains water, limestone, hydrocarbon solvents, propylene glycol and acetic acid. The Newtonian type high basic grease precursor is in combination with at least one complex salt containing water, phosphoric acid, boric acid and / or 12-hydroxystearic acid. When combined with at least one complexing agent, the Newtonian grease precursor is converted to concentrated non-Newtonian complex grease containing mainly batterite.

In another embodiment of the present invention, the two-stage reaction for the preparation of the composite grease is carried out with a converting agent of a Newtonian type high basic calcium oleate material with a converting agent, under conditions suitable for forming calcium carbonate crystals in the form of vatite crystals instead of calsite. Heating to form thixotropic intermediate non-Newtonian gel grease precursors, wherein the conversion agent contains water, limestone, hydrocarbon solvents, propylene glycol and acetic acid. The grease precursor is again combined with at least one complexing agent containing water, phosphoric acid, boric acid and / or 12-hydroxystearic acid. When combined with the complexing agent, the thixotropic intermediate non-Newtonian gel grease precursor is converted back into the non-Newtonian composite grease containing mainly batterite.

The following examples mainly illustrate the amounts and components of composite grease containing batelite, but the scope of the invention is not limited to these examples.

Example

Vaterite  Containing denaturation High basic Calcium oleate  Two stage fast process for the production of composite grease

Example 1

In a 3 gallon Herbert mixer, 1000.02 g of Drakezol ^® 600, 2000.14 g of 15.0% high basic calcium oleate (96.2% nonvolatile (NVM) and total base value of 330 (TBN)), 100.09 g of limestone (CaOH ₂ ) And also a conversion agent of 200.06 g of water, 100.05 g of propylene glycol and 150.07 g of acetic acid. The mixture was heated to 104 ° C. (220 ° F.) with stirring for about 1 hour 30 minutes to form an intermediate Newtonian grease precursor. The complexing agent was then added to the rich intermediate non-Newtonian grease precursor. The second conversion agent contained 100.13 g of water, 149.99 g of 12-hydroxystearic acid and 100.02 g of phosphoric acid. The mixture was heated to 104 ° C. (220 ° F.) with stirring for about 1 hour to form non-Newtonian type calcium 12-hydroxystearate and calcium phosphate modified high basic calcium oleate composite grease containing mainly batterite. This compound grease is considered an edible compound grease.

The obtained product was confirmed by X-ray diffraction analysis and found no detectable amount of calsite or aragonite.

Example 2

In a 3 gallon Herbert mixer, 1012.50 g of Drakezol ^® 600, 2000.00 g of 15.0% high basic calcium oleate (96.2% NVM and 330 TBN), 100.00 g of limestone (CaOH ₂ ), also 200.01 g of water, 100.00 g Was converted to propylene glycol and 150.07 g of acetic acid. The mixture was heated to 104 ° C. (220 ° F.) with stirring for about 1 hour 30 minutes to form an intermediate Newtonian grease precursor. The complexing agent was then added to the intermediate Newtonian grease precursor. This complex salt contained 100.01 g of water, 150.0 g of 12-hydroxystearic acid and 100.00 g of boric acid. The mixture was heated to 104 ° C. (220 ° F.) for about 1 hour with stirring to form non-Newtonian type calcium 12-hydroxystearate and calcium borate modified high basic calcium oleate composite grease containing mainly batterite.

The obtained product was confirmed by X-ray diffraction analysis and found no detectable amount of calsite or aragonite.

Example 3

In a 3 gallon Herbert mixer, 1000.02 g of Drakezol ^® 600, 2000.03 g of 15.0% high basic calcium oleate (96.2% NVM and 330 TBN), 100.13 g of limestone (CaOH ₂ ), also 200.00 g of water, 100.02 g Was converted to propylene glycol and 150.03 g of acetic acid. The mixture was heated to 104 ° C. (220 ° F.) with stirring for about 1 hour and 15 minutes to form an intermediate Newtonian grease precursor. The complexing agent was then added to the intermediate Newtonian grease precursor. This complex salt contained 100.04 g of water and 150.03 g of 12-hydroxystearic acid. The mixture was heated to 104 ° C. (220 ° F.) to 138 ° C. (280 ° F.) with stirring for about 1 hour and 45 minutes to prepare calcium 12-hydroxystearate modified non-Newtonian type high basic calcium oleate complex grease containing mainly batterite. Formed. This compound grease is considered an edible compound grease.

The obtained product was confirmed by X-ray diffraction analysis and found no detectable amount of calsite or aragonite.

Example 4

In a 3 gallon Herbert mixer, 1000.00 g of Drakezol ^® 600, 2000.11 g of 15.0% high basic calcium oleate (96.2% NVM and 330 TBN), 75.03 g of limestone (CaOH ₂ ), also 203.00 g of water, 100.05 g Was converted to propylene glycol and 175.02 g of acetic acid. The mixture was heated to 104 ° C. (220 ° F.) with stirring for about 1 hour and 15 minutes to form an intermediate Newtonian grease precursor. The complexing agent was then added to the intermediate Newtonian grease precursor. This complex salt contained 100.02 g of water and 150.00 g of 12-hydroxystearic acid. The mixture was heated to 104 ° C. (220 ° F.) to 138 ° C. (280 ° F.) with stirring for about 2 hours to form calcium 12-hydroxystearate modified non-Newtonian type high basic calcium oleate composite grease containing mainly batterite. . This compound grease is considered an edible compound grease.

The obtained product was confirmed by X-ray diffraction analysis and found no detectable amount of calsite or aragonite.

Example 5

In a 3 gallon Herbert mixer, 1000.03 g of Drakezol ^® 600, 2000.15 g of 15.0% high basic calcium oleate (96.2% NVM and 330 TBN), 100.4 g of limestone (CaOH ₂ ), also 200.43 g of water, 100.01 g Was converted to propylene glycol and 150.03 g of acetic acid. The mixture was heated to 104 ° C. (220 ° F.) with stirring for about 1 hour and 15 minutes to form an intermediate Newtonian grease precursor. The complexing agent was then added to the intermediate Newtonian grease precursor. This complex salt contained 100.03 g of water and 200.05 g of 12-hydroxystearic acid. The mixture was heated to 104 ° C. (220 ° F.) to 138 ° C. (280 ° F.) with stirring for about 2 hours to form calcium 12-hydroxystearate modified non-Newtonian type high basic calcium oleate composite grease containing mainly batterite. . This compound grease is considered an edible compound grease.

The obtained product was confirmed by X-ray diffraction analysis and found no detectable amount of calsite or aragonite.

Example 6

In a 3 gallon Herbert mixer, 1003.86 g of Drakezol ^® 600, 2000.10 g of 15.0% high basic calcium oleate (96.2% NVM and 330 TBN), 75.02 g of limestone (CaOH ₂ ), also 200.02 g of water, 100.03 g Was converted to propylene glycol and 175.00 g of acetic acid. The mixture was heated to 104 ° C. (220 ° F.) with stirring for about 1 hour and 15 minutes to form an intermediate Newtonian grease precursor. The complexing agent was then added to the intermediate Newtonian grease precursor. This complex salt contained 100.03 g of water and 200.06 g of 12-hydroxystearic acid. The mixture was heated to 104 ° C. (220 ° F.) to 138 ° C. (280 ° F.) with stirring for about 2 hours to form calcium 12-hydroxystearate modified non-Newtonian type high basic calcium oleate composite grease containing mainly batterite. . This compound grease is considered an edible compound grease.

The obtained product was confirmed by X-ray diffraction analysis and found no detectable amount of calsite or aragonite.

Example 7

In a 3 gallon Herbert mixer, 1000.07 g of Drakezol ^® 600, 2000.050 g of 15.0% high basic calcium oleate (96.2% NVM and 330 TBN), 75.04 g of limestone (CaOH ₂ ), also 200.06 g of water, 100.05 g Was converted to propylene glycol and 175.03 g of acetic acid. The mixture was heated to 104 ° C. (220 ° F.) with stirring for about 1 hour 20 minutes to form an intermediate Newtonian grease precursor. The complexing agent was then added to the intermediate Newtonian grease precursor. This complex salt contained 100.00 g of water and 250.01 g of 12-hydroxystearic acid. The mixture was heated to 104 ° C. (220 ° F.) to 138 ° C. (280 ° F.) with stirring for about 2 hours and 5 minutes to prepare calcium 12-hydroxystearate modified non-Newtonian type high basic calcium oleate composite grease containing mainly batterite. Formed. This compound grease is considered an edible compound grease.

The obtained product was confirmed by X-ray diffraction analysis and found no detectable amount of calsite or aragonite.

Example 8

In a 3 gallon Herbert mixer, 1000.00 g of Drakezol ^® 600, 2000.04 g of 15.0% high basic calcium oleate (96.2% NVM and 330 TBN), 100.00 g of limestone (CaOH ₂ ), also 200.12 g of water, 100.00 g Was converted to propylene glycol and 175.01 g of acetic acid. The mixture was heated to 104 ° C. (220 ° F.) with stirring for about 1 hour 10 minutes to form an intermediate Newtonian grease precursor. The complexing agent was then added to the intermediate Newtonian grease precursor. This complex salt contained 100.05 g of water and 200.00 g of 12-hydroxystearic acid. The mixture was heated to 104 ° C. (220 ° F.) to 138 ° C. (280 ° F.) with stirring for about 2 hours to form calcium 12-hydroxystearate modified non-Newtonian type high basic calcium oleate composite grease containing mainly batterite. . This compound grease is considered an edible compound grease.

The obtained product was confirmed by X-ray diffraction analysis and found no detectable amount of calsite or aragonite.

Example 9

In a 3 gallon Herbert mixer, 1000.02 g of Drakezol ^® 600, 2000.00 g of 15.0% high basic calcium oleate (96.2% NVM and 330 TBN), 49.99 g of limestone (CaOH ₂ ), also 200.04 g of water, 100.12 g Was converted to propylene glycol and 175.04 g of acetic acid. The mixture was heated to 104 ° C. (220 ° F.) with stirring for about 1 hour 45 minutes to form an intermediate Newtonian grease precursor. The complexing agent was then added to the intermediate Newtonian grease precursor. This complex salt contained 100.02 g of water and 200.03 g of 12-hydroxystearic acid. The mixture was heated to 104 ° C. (220 ° F.) to 138 ° C. (280 ° F.) with stirring for about 2 hours to form calcium 12-hydroxystearate modified non-Newtonian type high basic calcium oleate composite grease containing mainly batterite. . This compound grease is considered an edible compound grease.

The obtained product was confirmed by X-ray diffraction analysis and found no detectable amount of calsite or aragonite.

Example 10

In a 3 gallon Herbert mixer, 1000.10 g of Drakezol ^® 600, 2000.00 g of 15.0% high basic calcium oleate (96.2% NVM and 330 TBN), 75.00 g limestone (CaOH ₂ ), also 200.00 g of water, 100.00 g Was converted to propylene glycol and 250.00 g of acetic acid. The mixture was heated to 104 ° C. (220 ° F.) with stirring for about 1 hour 10 minutes to form an intermediate Newtonian grease precursor. The complexing agent was then added to the intermediate Newtonian grease precursor. This complex salt contained 100.01 g of water and 200.10 g of 12-hydroxystearic acid. The mixture is heated to 104 ° C. (220 ° F.) to 138 ° C. (280 ° F.) with stirring for about 2 hours and 30 minutes to prepare calcium 12-hydroxystearate modified non-Newtonian type high basic calcium oleate complex grease containing mainly batterite. Formed. This compound grease is considered an edible compound grease.

The obtained product was confirmed by X-ray diffraction analysis and found no detectable amount of calsite or aragonite.

Example 11

In a 3 gallon Herbert mixer, 1600.00 g of Drakezol ^® 600, 3200.00 g of 15.0% high basic calcium oleate (96.2% NVM and 330 TBN), 120.00 g of limestone (CaOH ₂ ), also 320.00 g of water, 160.00 g Was converted to propylene glycol and 280.00 g of acetic acid. The mixture was heated to 104 ° C. (220 ° F.) with stirring for about 1 hour and 35 minutes to form an intermediate Newtonian grease precursor. The complexing agent was then added to the intermediate Newtonian grease precursor. This complexing agent contained 160.02 g of water and 320.04 g of 12-hydroxystearic acid. The mixture was heated to 104 ° C. (220 ° F.) to 138 ° C. (280 ° F.) with stirring for about 1 hour and 45 minutes to prepare calcium 12-hydroxystearate modified non-Newtonian type high basic calcium oleate complex grease containing mainly batterite. Formed. This compound grease is considered an edible compound grease.

The obtained product was confirmed by X-ray diffraction analysis and found no detectable amount of calsite or aragonite.

Vaterite  Containing denaturation High basic Calcium oleate  Two steps for the production of composite grease Two-stage  fair

Example 12

In a three gallon Herbert mixer, 1000.04 g of Drakezol ^® 600, 2000.06 g of 15.0% high basic calcium oleate (96.2% NVM and 330 TBN), 100.02 g of limestone (CaOH ₂ ), also 200.03 g of water, 100.26 g Was converted to propylene glycol and 150.01 g of acetic acid. The mixture was heated to 104 ° C. (220 ° F.) for about 2 hours with stirring to form the thixotropic intermediate non-Newtonian gel grease precursor. A complexing agent was then added to the thixotropic intermediate non-Newtonian gel grease precursor. The second conversion agent contained 100.03 g of water and 200.03 g of 12-hydroxystearic acid. The mixture is heated to 104 ° C. (220 ° F.) to 138 ° C. (280 ° F.) with stirring for about 1 hour and 20 minutes to prepare calcium 12-hydroxystearate-modified non-Newtonian type high basic calcium oleate complex grease containing mainly batterite. Formed. This compound grease is considered an edible compound grease.

The obtained product was confirmed by X-ray diffraction analysis and found no detectable amount of calsite or aragonite.

Example 13

In a three gallon Herbert mixer, 1600.25 g of Drakezol ^® 600, 3200.06 g of 15.0% high basic calcium oleate (96.2% NVM and 330 TBN), 160.00 g of limestone (CaOH ₂ ), also 320.04 g of water, 160.00 g Was converted to propylene glycol and 240.00 g of acetic acid. The mixture was heated to 104 ° C. (220 ° F.) for about 2 hours with stirring to form the thixotropic intermediate non-Newtonian gel grease precursor. The complexing agent was then added to the thixotropic intermediate non-Newtonian gel grease precursor. This complex salt contained 160.00 g of water and 320.11 g of 12-hydroxystearic acid. The mixture was heated to 104 ° C. (220 ° F.) to 138 ° C. (280 ° F.) with stirring for about 2 hours to form calcium 12-hydroxystearate modified non-Newtonian type high basic calcium oleate composite grease containing mainly batterite. . This compound grease is considered an edible compound grease.

The obtained product was confirmed by X-ray diffraction analysis and found no detectable amount of calsite or aragonite.

Example 14

In a 3 gallon Herbert mixer, 1000.33 g of Drakezol ^® 600, 2000.04 g of 15.0% high basic calcium oleate (96.2% NVM and 330 TBN), 50.04 g of limestone (CaOH ₂ ), also 200.00 g of water, 100.03 g Was converted to propylene glycol and 150.02 g of acetic acid. The mixture was heated to 104 ° C. (220 ° F.) for about 2 hours with stirring to form the thixotropic intermediate non-Newtonian gel grease precursor. The complexing agent was then added to the thixotropic intermediate non-Newtonian gel grease precursor. This complex salt contained 100.01 g of water and 200.02 g of 12-hydroxystearic acid. The mixture is heated to 104 ° C. (220 ° F.) to 138 ° C. (280 ° F.) with stirring for about 1 hour and 15 minutes to disperse calcium 12-hydroxystearate modified non-Newtonian type high basic calcium oleate composite grease containing mainly batterite. Formed. This compound grease is considered an edible compound grease.

The obtained product was confirmed by X-ray diffraction analysis and found no detectable amount of calsite or aragonite.

Example 15

In a 3 gallon Herbert mixer, 1000.07 g of Drakezol ^® 600, 2000.03 g of 15.0% high basic calcium oleate (96.2% NVM and 330 TBN), 99.99 g of limestone (CaOH ₂ ), also 200.01 g of water, 100.02 g Was converted to propylene glycol and 122.03 g of acetic acid. The mixture was heated to 104 ° C. (220 ° F.) for about 2 hours with stirring to form the thixotropic intermediate non-Newtonian gel grease precursor. The complexing agent was then added to the thixotropic intermediate non-Newtonian gel grease precursor. This complex salt contained 100.00 g of water and 200.03 g of 12-hydroxystearic acid. The mixture was heated to 104 ° C. (220 ° F.) to 138 ° C. (280 ° F.) with stirring for about 1 hour and 30 minutes to prepare calcium 12-hydroxystearate-modified non-Newtonian type high basic calcium oleate composite grease containing mainly batterite. Formed. This compound grease is considered an edible compound grease.

The obtained product was confirmed by X-ray diffraction analysis and found no detectable amount of calsite or aragonite.

Among the characteristics of the highly basic calcium oleate composite grease prepared as described above, calcium carbonate crystals mainly in the form of vatite crystals are formed in the composite grease instead of calsite. As shown in Figures 1 and 2, X-ray diffraction (XRD) spectra are shown for both vaterite and calsite, respectively. For comparison purposes, FIG. 3 shows the XRD spectrum of the 15% high basic calcium oleate carboxylate used in the preparation of the high basic calcium oleate composite grease, and FIG. 4 shows the XRD spectrum of the high basic calcium oleate composite grease, respectively. . Based on the XRD data of FIG. 3, it is determined that the 15% high basic calcium oleate carboxylate mainly contains amorphous calcium carbonate and substantially limited calcium carbonate content detectable as calsite and / or batite. Also, as shown in FIG. 4, XRD data of the highly basic calcium oleate composite grease shows that the vaterite is the main calcium carbonate form of the grease. This means that calcium carbonate in the form of calsite is not present in grease.

Another evidence showing that the bacterite type calcium carbonate is present in the highly basic calcium oleate composite grease is shown in FIG. 5. Fourier-modified infrared spectroscopy (FTIR) spectra are shown for three kinds of materials. The main feature of these spectra is the presence of peaks in the 860-880 cm ^-1 region. The peak in this region corresponds to the form of calcium carbonate. Typically the peak at 858 to 862 cm ⁻¹ is amorphous calcium carbonate; Peaks at 880 to 885 cm ⁻¹ are calcitic calcium carbonate; In addition, the peaks at 875 to 877 cm ⁻¹ correspond to the bacterite type calcium carbonate, respectively. As seen in FIG. 5, the spectra with peaks at 885.1 cm ⁻¹ correspond to commercially available high basic calcium sulfonate greases, which look predominantly like calcitic calcium carbonate. The spectra with peaks at 856.7 cm ⁻¹ correspond to commercially available liquid high basic calcium oleate carboxylates, which mainly contain amorphous calcium carbonate. The spectrum with a peak at 875.9 cm ⁻¹ also corresponds to the high basic calcium oleate composite grease according to one embodiment of the invention, which mainly contains the baritelite calcium carbonate.

As shown in FIG. 7, another FTIR spectrum is for comparison with the measured value of the liquid high basic calcium oleate carboxylate used in the preparation of the high basic calcium oleate composite grease. The spectrum with a peak at 858.6 cm ⁻¹ corresponds to a commercially available liquid high basic calcium oleate carboxylate containing mainly amorphous calcium carbonate. The spectrum with a peak at 875.0 cm ⁻¹ also corresponds to a high basic calcium oleate composite grease according to an embodiment of the invention containing mainly batite calcium carbonate.

As shown in Figures 8A-8D, another FTIR spectrum is shown for commercially available high basic calcium sulfonate composite greases. These figures show that the peaks for calcium carbonate are in the region of 880.8 to 884.7 cm ⁻¹ , respectively, and these peaks are within a range corresponding to calcitic calcium carbonate.

Infrared analysis was also used to monitor and characterize the complex grease conversion process. The infrared absorption peaks at about 863 cm ^-1 , 877 cm ^-1 and 882 cm ^-1 are those that characterize amorphous, batterite and calsite calcium carbonate, respectively. The FTIR spectrum of FIG. 9 clearly showed that the Newtonian type high basic calcium oleate had a representative broad peak centered at 860 cm ⁻¹ . Peak position and wide area are evidence of the amorphous properties of calcium carbonate contained in the highly basic calcium oleate material. When a high basic calcium oleate material with conversion ratio nyuwoo teonhyeong calcium oleate complex grease wide peak of 860cm ^-1 disappeared and instead a new peak was confirmed that the peak appears at 875cm ^-1 from the FTIR spectrum. This is consistent with the conversion of amorphous calcium carbonate to batelite crystalline calcium carbonate. For the purpose of comparison, the FTIR spectrum of commercial edible calcium sulfonate composite grease is shown in FIG. 9. The main peak here appears at 885 cm ⁻¹ , indicating calcite crystalline calcium carbonate.

In addition, as shown in Fig. 10, the composite grease manufacturing process was recorded from the start to the end through infrared analysis. These FTIR spectra were recorded at 20 minute intervals for samples taken in grease containers. The FTIR spectrum showed a single broad peak at 860 cm ⁻¹ from room temperature to 210 ° F. when the high basic calcium oleate material was in the Newtonian liquid form. And also from 220 to 225 ℉ a basic calcium oleate material is converted to a thixotropic ratio nyuwoo teonhyeong gel grease precursor, just before the complex reaction is started, the FTIR spectrum showed two peaks at 860cm ^-1 and 875cm ^-1. When the grease vessel was heated below 225 ° F. and the grease reaction was led to the final complex salt reaction step, the FTIR spectrum showed only one peak at 875 cm ⁻¹ . When the entire heating process, 875cm ^- the wavelength of a value beyond a ^first infrared absorption band is not observed. Thus, from the infrared analysis, it can be judged that in the case of the highly basic calcium oleate material, the amorphous calcium carbonate is converted to the bacterite type calcium carbonate exceptionally when it is converted into grease.

High base chemistry provides grease formulations that can be registered as edible, biodegradable and biobased. Highly basic complex greases include accelerators prepared from calcium oleate, propylene glycol-containing materials, as well as conversion agents containing water, limestone, 12-hydroxystearic acid and acetic acid, all of which are "incidental". food contact). The hydrocarbon solvent used in the grease formulation can be synthetic or natural. The gel material can be obtained with HI edible grease by adjusting to NLGI grade grease with an appropriate oil. Plant-derived formulations are adapted to NLGI # 2 grease using natural soybean oil, resulting in biodegradable grease. Greases can be classified as biosystems and biodegradable when manufactured using oils consisting of plant-derived oleic acid and vegetable oils such as canola oil or palm oil.

Since oleic acid is a natural monounsaturated fatty acid, an antioxidant additive can optionally be used to improve the antioxidant properties of the composite grease. In one embodiment, amine antioxidants can be utilized to prepare highly basic composite greases. Amine type antioxidants may be added, for example, in amounts typically less than 1.0% by weight of the total amount of the composite grease formulation. In yet another embodiment, the amine antioxidant may be added in an amount of about 0.5% by weight of the total amount of the composite grease formulation.

Conventional grease function tests were conducted on greases of experimental edible grade among calcium oleate composite greases containing 3.5% 12-hydroxystearic acid as the complexing agent. The greases above were optimized with respect to the relative ratio of the highly basic calcium oleate grease starting material to the 12-hydroxystearic acid complexing agent. It was also optimized with regard to the relative ratio of the total amount of calcium hydroxide to the amount of acid added in the grease processing. All other test results were collected on raw grease containing no functional additives except for the data collected in the 500 hour grease oxidation stability test (ASTM D942) for the raw grease supplemented with 0.5% amine antioxidant. . The results from the selected grease functional tests are shown in Table 2. For comparison purposes, general functional data for commercial calcium sulfonate complex greases of edible grade (H1) are also listed in Table 2.

Grease Characterization Greek kind Commercial Edible Calcium Sulfonate Complex Grease Laboratory Edible High Basic Calcium Oleate Complex Grease Thickener Calcium Sulfonate Complex Salt Calcium Oleate Complex Salt Basic oils, types 95cSt White Oil 600 SUS white oil Precursor percentage,% N / A 34.50% smell usually usually Bio-based thickener none has exist Grease test ASTM  Way NLGI rating D217 2 2 Penetration, 60 k strike, mm / 10 D217 280 272 Penetrating, 10k blow, mm / 10 D217 277 269 Mechanical Stability 10k Strike,% Change D217 -One -One Rolling stability 2 hours @ 77 ° F,% D1831 2.1 (50% H ₂ O) N / A Dropping Point, ℃ (℉) D2265 318 (604) 349 (660) Flushing @ 175 ℉,% loss D1264 0.5 5.24 Timken OK Load, kg (LBS) D2509 27.2 (60) 20.4 (45) 4-hole wear, mm D2266 0.45 O.43 4-ball EP D2596 Load abrasion index 62 46 Welding, kg 500 400 Oxidative stability D942 100 hour kPa (PSI) loss N / A 70 500 hours kPa (PSI) loss 6 psi @ 1000 hours 2 (0.5% AO *) Antirust / Bearing Corrosion D1743 Pass Pass Copper corrosion D4048 1b 1b Wheel bearing leak, g D1263 1.0 0.2 Oil separation, loss% D1742 0.1 0.03 Evaporation Loss, Loss% @ 99 ℃ D972 N / A 0.65 Grease Mobility, g / mm-18 ° C USS 19.3 4.2 Low temperature torque @ -18 ℃ D1478 Start, g / cm 1404 780 60 minutes, g / cm 247 260

* Note: Edible amine antioxidants were used in amounts of 0.5% by weight.

Based on the above description, it is clear that the composite grease containing the vaterite achieves the above object. Thus, it will be apparent to those skilled in the art that various modifications fall within the scope of the claims of the present invention and that the selection of individual components may be determined without departing from the spirit and scope of the present invention described above.

Claims (22)

High basic alkaline earth metal salts of fatty acids having an alkaline earth metal content of at least 14.5% and a nonvolatile content of at least 95%;
A conversion agent containing a hydrocarbon solution, water, limestone, polyol, and short-chain carboxylic acid selected from the group consisting of acetic acid and propionic acid; Also
A high basic metal carboxylate complex grease comprising at least one complex salt selected from the group consisting of phosphoric acid, boric acid, C ₁₂ -C ₂₄ aliphatic monocarboxylic acids and C ₁₂ -C ₂₄ fatty acids. The method of claim 1,
In Greece, calsite is virtually unmeasured compound grease. The method of claim 1,
A composite grease in which the main form of calcium carbonate contained in the grease is vaterite. The method of claim 1,
Compound grease, wherein the fatty acid of at least one complexing agent is 12-hydroxystearic acid. The method of claim 1,
Compound grease in which the fatty acid of the high basic alkaline earth metal salt is oleic acid. The method of claim 1,
The alkaline earth metal of the high basic alkaline earth metal salt is selected from the group consisting of calcium, barium, magnesium and strontium. The method of claim 1,
The high basic alkaline earth metal salt is calcium oleate. The method of claim 1,
Wherein the polyol is a glycol ether or glycol selected from the group consisting of diethylene glycol monobutyl ether, triethylene glycol, dipropylene glycol, diethylene glycol monomethyl ether, ethylene glycol monobutyl ether and mixtures thereof. As a method for producing a composite grease,
Providing a high basic alkaline earth metal salt of fatty acid having an alkaline earth metal content of at least 14.5% and a nonvolatile material content of at least 95%;
The high basic alkaline earth metal salt of the fatty acid is reacted with a converting agent to form a New Uton-type grease precursor, wherein the converting agent is a short-chain carboxylic acid selected from the group consisting of hydrocarbon liquid, water, limestone, polyol, acetic acid and propionic acid It contains; Also
Reacting the Newtonian grease precursor with at least one complexing agent to form a non-Newtonian complex grease, wherein the complexing agent is phosphoric acid, boric acid, C ₁₂ -C ₂₄ aliphatic monocarboxylic acid and C ₁₂ -C ₂₄ fatty acid is selected from the group consisting of. The method of claim 9,
Wherein the calsite is not substantially measured in Greece. The method of claim 9,
The main form of calcium carbonate present in grease is batterite. The method of claim 9,
The fatty acid of at least one complexing agent is 12-hydroxystearic acid. The method of claim 12,
A fatty acid of a high basic alkaline earth metal salt is oleic acid. The method of claim 9,
The alkaline earth metal of the high basic alkaline earth metal salt is selected from the group consisting of calcium, barium, magnesium and strontium. The method of claim 9,
The high basic alkaline earth metal salt is a method of producing calcium oleate. As a method for producing a composite grease,
Providing a high basic alkaline earth metal salt of fatty acid having an alkaline earth metal content of at least 14.5% and a nonvolatile material content of at least 95%;
The high basic alkaline earth metal salt of the fatty acid is reacted with a converting agent to form a thixotropic non-Newtonian gel grease precursor, wherein the converting agent is selected from the group consisting of hydrocarbon liquid, water, limestone, polyol, acetic acid and propionic acid Contains chain carboxylic acids; Also
Reacting the non-Newtonian grease precursor with at least one complexing agent to form a non-Newtonian composite grease, wherein the complexing agent is phosphoric acid, boric acid, C ₁₂ -C ₂₄ aliphatic monocarboxylic acid and C ₁₂ − C ₂₄ fatty acid is selected from the group consisting of. 17. The method of claim 16,
Wherein the calsite is not substantially measured in Greece. 17. The method of claim 16,
The main form of calcium carbonate present in grease is batterite. 17. The method of claim 16,
The fatty acid of the at least one complexing agent is 12-hydroxystearic acid. The method of claim 19,
The fatty acid of the high basic alkaline earth metal salt is oleic acid. 17. The method of claim 16,
The alkaline earth metal of the high basic alkaline earth metal salt is selected from the group consisting of calcium, barium, magnesium and strontium. 17. The method of claim 16,
The high basic alkaline earth metal salt is calcium oleate.

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