CN114752426B - Composite calcium sulfonate-based lubricating grease and preparation method thereof - Google Patents

Composite calcium sulfonate-based lubricating grease and preparation method thereof Download PDF

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CN114752426B
CN114752426B CN202110032551.6A CN202110032551A CN114752426B CN 114752426 B CN114752426 B CN 114752426B CN 202110032551 A CN202110032551 A CN 202110032551A CN 114752426 B CN114752426 B CN 114752426B
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calcium sulfonate
acid
agent
grease
phase inversion
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CN114752426A (en
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李建明
仇建伟
刘丽君
毛菁菁
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Petrochina Co Ltd
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Petrochina Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/085—Phosphorus oxides, acids or salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/087—Boron oxides, acids or salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/16—Paraffin waxes; Petrolatum, e.g. slack wax
    • C10M2205/163—Paraffin waxes; Petrolatum, e.g. slack wax used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
    • C10M2207/1285—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof used as thickening agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C10M2219/0466—Overbasedsulfonic acid salts used as thickening agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts

Abstract

The invention discloses a composite calcium sulfonate-based lubricating grease with high water resistance, low starting friction and running friction and a preparation method thereof. The high water spray resistance composite calcium sulfonate base lubricating grease comprises the following components in percentage by mass: 30% -70% of base oil; 20-40% of ultra-high base number synthesized calcium sulfonate; 0.5 to 2 percent of antioxidant; 1-18% of phase inversion agent; 1-5% of macromolecular acid; 1-5% of water repellent agent; 1 to 5 percent of organic molybdenum antifriction agent and 1 to 10 percent of amide friction modifier. Compared with the traditional products, the invention reduces the use amount of phase inversion agents such as alcohols, ethers and the like in the production process and reduces the environmental pollution; the efficiency of converting Newtonian high-base-number calcium sulfonate into non-Newtonian calcium sulfonate is improved, and the phase inversion is thorough, so that the production process is simpler. At the same time, has excellent high temperature resistance good mechanical stability and excellent energy-saving antifriction property; has excellent water resistance.

Description

Composite calcium sulfonate-based lubricating grease and preparation method thereof
Technical Field
The invention relates to a composite calcium sulfonate-based lubricating grease and a preparation method thereof, in particular to a preparation method for preparing high-performance and high-water-spray-resistance composite calcium sulfonate-based lubricating grease by adopting a traditional phase inversion agent and macromolecular acid.
Background
The composite calcium sulfonate grease is one of the high-performance grease with high temperature resistance, extreme pressure abrasion resistance, shear stability, low-temperature pumping performance, rust resistance and water resistance, is called as 'new generation high-efficiency grease', has wide application prospect in various severe working condition environments such as dustiness, water and high load, and is applied to large enterprises in various industries such as steel, papermaking, bearings and the like at home and abroad.
The rolling mill is widely applied in China, the shape control capability of the rolling mill is stronger, the rolling mill structure is more complex, the stress state of a working roll shaft is harsh, and higher requirements on extreme pressure and water resistance of lubricating grease are provided. When the working roll of the rolling mill rotates at a high speed, the bearing grease of the bearing can be quickly lost due to the internal pressure born by the bearing seat and the scouring of the cooling water of the high-pressure roll, so that the lubrication condition required by the working of the bearing can not be ensured, the service life of the bearing is greatly shortened, and the phenomenon that the bearing burns out and holds the roll occurs; meanwhile, the roller cooling water can also bring impurities such as iron scales into the bearing seat, abrasive particle abrasion is formed in the bearing, and pitting corrosion and even fatigue peeling are caused. If the bearing is not maintained timely, the bearing can be directly scrapped. Based on the above, it is required to replenish the bearing with new grease before each start-up, and thus the grease consumption is large. With the increasing importance of domestic iron and steel enterprises on equipment lubrication, the lubrication management trend is careful, and a lubricating grease with long service life and excellent comprehensive performance is needed so as to meet the use requirement of multi-cycle non-grease supplement of a rolling mill working roller bearing. The composite calcium sulfonate grease has comprehensive and excellent performance, particularly has basically unchanged consistency after meeting water, has excellent extreme pressure wear resistance, small usage amount and long service life, can meet the nearly harsh working condition of a rolling mill bearing, and becomes the first choice of grease for the working roller bearing of a hot-rolling wide strip rolling mill.
The complex calcium sulfonate grease mainly undergoes three processes. In the first stage, sproule and the like found that calcium sulfonate can be used as a thickening agent to prepare lubricating grease in 1950, and the calcium sulfonate can be used together with fatty acid calcium soap to improve the dropping point of the lubricating grease, but the thickening capability of the calcium sulfonate-based lubricating grease is very small; in the second stage, in the 60 th century, a method for converting Newtonian calcium sulfonate into non-Newtonian calcium sulfonate with thixotropic property is found, and meanwhile, the calcium sulfonate-based lubricating grease has outstanding high temperature resistance, shear stability and other aspects, but has the defects of high content of a thickening agent, poor low-temperature pumpability and interference in large-scale industrialized application of the lubricating grease; in the third stage, in the middle 80 th century, ronald J M firstly invents the complex of calcium borate soap and fatty acid calcium soap added in the preparation process of calcium sulfonate grease, and the complex calcium sulfonate grease not only has the advantage of original calcium sulfonate grease, but also eliminates the weakness of poor low-temperature pumping property of the original grease.
In 1985, ron Muir et al from Witco Chemical company invented a novel process for producing complex calcium sulfonate grease, the patent number is: US4560489. On the basis of the former low-base-number calcium sulfonate synthesis process, ron Muir et al convert high-base-number calcium sulfonate, and add 12-hydroxystearic acid and boric acid to improve the colloid stability and tribological properties of the grease, so that the true composite calcium sulfonate-based grease is produced in a laboratory.
John F.Barnes et al, NCH corporation, 1992, invented a process for producing a complex calcium sulfonate-based grease, having the following patent numbers: US 5126062.John f. Barnes et al used isopropanol and phosphoric acid instead of ethylene glycol monomethyl ether and acetic acid to prepare complex calcium sulfonate esters. In the components of the composite calcium sulfonate grease, 12-hydroxystearic acid is also added to improve the colloid performance and tribology of the grease.
William D.olson et al, witco Chemical Co., 1994, invented a complex calcium sulfonate-based grease, U.S. Pat. No. 3,182. The patent does not use alcohols such as ethylene glycol monomethyl ether and isopropanol as phase inversion promoters, but uses stearic acid as a phase inversion promoter.
Li Xianqiu et al of chinese petrochemical company in 2003 invented a method for preparing a high-performance grease mixed with lithium-calcium sulfonate grease, the patent number of which is: CN 1616612a. The main purpose of the patent is to prepare the composite lithium-based lubricating grease containing the overbased calcium sulfonate. The grease has the characteristics of two kinds of grease, has the advantages of good mechanical stability, colloid stability, water resistance, rust resistance and high-temperature service performance under the condition of no addition of additives (except antioxidants and adhesion agents). The preparation process is as follows:
the invention discloses a preparation method of ultra-high bond value composite calcium sulfonate-based lubricating grease, which is invented by any sea span et al of tin-free Gao Runjie chemical Co., ltd in 2007, and has the following patent numbers: CN 1001153239a. The main purpose of the patent is to prepare the composite calcium sulfonate-based lubricating grease by adopting T106 with ultra-high base number. The prepared lubricating grease has good mechanical stability, colloid stability, water resistance and rust resistance under the condition of no addition of additives (except antioxidants and adhesives), outstanding shearing resistance and excellent pumping performance, and the number of times of grease change is reduced and the service life of equipment is prolonged under the same working condition as proved by trial experiments of multi-household electrical appliance production enterprises, steel works, paper factories and the like.
The most critical step in the production process of the composite calcium sulfonate grease is to convert the high-base-number calcium sulfonate of Newtonian into the composite calcium sulfonate grease of non-Newtonian, and if the phase inversion is unsuccessful or incomplete, the grease is softer, the dropping point is lower, and the extreme pressure abrasion resistance of the grease is poorer. The above patents all adopt alcohols, ethers, low molecular acids and the like as phase inversion agents, and after the phase inversion agents are converted, the alcohols, ethers and the like are directly discharged into the atmosphere to cause environmental pollution, and the problems of incomplete conversion, unstable conversion process and the like exist, so that how to reduce the use amount of the phase inversion agents and improve the conversion effect, thereby effectively reducing the environmental pollution and improving the product performance, and the method is a focus of attention in the field.
Disclosure of Invention
The invention aims to solve the defects of the composite calcium sulfonate grease and the preparation method thereof, reduce the use amount of a phase inversion agent and improve the conversion effect, thereby effectively reducing environmental pollution and improving products, and provides the high-performance composite calcium sulfonate grease and the preparation method thereof. Meanwhile, the problems that domestic composite calcium sulfonate is used in rolling mill bearings with poor sealing performance, a large amount of water is washed in an oil groove between the bearings, the composite calcium sulfonate is washed away by the water or swells when meeting the water, and therefore the content of lubricating grease in the oil groove between the bearings is reduced due to extrusion from the oil groove between the bearings, and bearing abrasion and sintering are caused are solved.
In order to achieve the purpose, the invention provides composite calcium sulfonate grease, which comprises the following components in percentage by mass:
the composite calcium sulfonate-based lubricating grease provided by the invention, wherein the phase inversion agent is one or more of water, small molecular acid and alcohol; the macromolecular acid is one or more of maleic acid, lactic acid, citric acid, oleic acid, lauric acid, stearic acid and 12-hydroxystearic acid.
The invention relates to a composite calcium sulfonate grease, wherein small molecular acid is one or more of formic acid, acetic acid, propionic acid, boric acid, monoalkyl substituted boric acid and phosphoric acid; the alcohol is one or more of isopropanol, butanol, ethylene glycol, propylene glycol and 1, 6-hexanediol.
The composite calcium sulfonate-based lubricating grease of the invention, wherein the kinematic viscosity of the base oil at 40 ℃ is 50-2000 mm 2 /s。
The base oil of the composite calcium sulfonate grease is one or more of dibasic acid diester, dioctyl sebacate, dioctyl adipate, neopentyl polyol ester, isooctyl adipate, dioctyl phthalate, dibutyl phthalate, trimethylolpropane trioctanoate, trimethylolpropane trioleate, triisopropylphenyl phosphate, methyl silicone oil, methyl phenyl silicone oil, poly alpha-olefin synthetic oil and cycloalkyl mineral oil.
The composite calcium sulfonate-based lubricating grease provided by the invention has the advantages that the base number of the ultrahigh base number synthetic calcium sulfonate is 380-420 mgKOH/g.
The composite calcium sulfonate grease of the invention also contains 0.5 to 8 weight percent of C12 to C24 fatty acid, 0.5 to 4 weight percent of boric acid or monoalkyl substituted boric acid and 0.5 to 2 weight percent of calcium hydroxide.
The invention relates to a composite calcium sulfonate grease, wherein the general formula of monoalkyl substituted boric acid is R-B (OH) 2 Wherein R is one or more of alkyl, cycloalkyl and aryl.
The composite calcium sulfonate grease of the invention, wherein the antioxidant is one or more of zinc dialkyl dithiophosphate, zinc alkyl dithiocarbamic acid, phenyl alpha-naphthylamine dialkyl diphenylamine and di-tert-butyl-p-cresol; the water repellent agent is one or more of ammonium zirconium carbonate, cuprous chloride, polyamine polyamide, modified melamine formaldehyde resin and fumed silica.
The invention relates to a composite calcium sulfonate base lubricating grease, wherein an organic molybdenum antifriction agent is composed of one or two of dialkyl dithio phosphothiomolybdenum, dialkyl dithio carbamic acid molybdenum and sulfur phosphorus nitrogen molybdenum complex in a proportion of 1:5-5:1.
The composite calcium sulfonate grease is characterized in that the amide friction improvement consists of one or two of oleamide, erucamide, stearic acid amide and palmitic acid amide in a ratio of 1:10-10:1.
The composite calcium sulfonate grease of the invention can separate water with concentration of not less than 85% and consistency of not more than 20 units after being tested by a high-temperature roller at 80 ℃ for 50 hours under the condition of containing 200% of water.
The invention also provides a preparation method for preparing the high water spray resistant composite calcium sulfonate base lubricating grease, which comprises the following steps:
step S1: adding super high base number synthesized calcium sulfonate, a part of base oil and a phase inversion agent into a stirring kettle, uniformly mixing, heating to 60-95 ℃, and continuously stirring for 0.1-1.5 hours;
step S2: adding macromolecular acid, continuously stirring, keeping the temperature at 60-95 ℃ for 0.2-2 hours, and adding the rest of base oil after the whole system is thickened into a grease shape;
step S3: heating to 95-120 ℃, adding aqueous solution of hydroxy fatty acid, boric acid and calcium hydroxide, stirring for reaction, and keeping the temperature for 0.2-1 hour;
step S4: continuously heating to 130-150 ℃ to dehydrate for 0.5-2 hours;
step S5: adding 0.5-2% of antioxidant, heating to 160-220 ℃ and refining for 0.1-1 hour;
step S6: when the temperature is reduced to below 150-100 ℃, water repellent agent, antioxidant, organic molybdenum antifriction agent and amide friction modifier are added, stirred for 0.5-1 hour at the temperature, homogenized and degassed to obtain the finished product.
The invention can be further described as follows:
the technical scheme for solving the technical problems of the invention can be as follows:
a high-performance composite calcium sulfonate-based lubricating grease and a preparation method thereof are provided, wherein base oil is one of dibasic acid diester, dioctyl sebacate, dioctyl adipate, neopentyl polyol ester, isooctyl adipate, dioctyl phthalate, dibutyl phthalate, trimethylolpropane trioctanoate, trimethylolpropane trioleate, triisopropylphosphate, methyl silicone oil, methyl phenyl silicone oil, poly alpha-olefin synthetic oil or cycloalkyl mineral oil, the ultrahigh base number of the ultrahigh base number composite calcium sulfonate is 380-420 mgKOH/g, the composite component of the composite calcium sulfonate is 0.5-8% of C12-C24 hydroxy fatty acid, 0.5-4% boric acid and 0.5-2% calcium hydroxide, and the phase inversion agent is composed of macromolecular acid and one of acetic acid, ethanol, isopropanol, water and C12-C22 hydroxy fatty acid or a mixture thereof. The antioxidant is one or a mixture of zinc dialkyl dithiophosphate, zinc alkyl dithiocarbamic acid, phenyl alpha-naphthylamine dialkyl diphenylamine and di-tert-butyl-p-cresol. The water repellent agent is one or a mixture of ammonium zirconium carbonate, cuprous chloride, polyamine polyamide, modified melamine formaldehyde resin and fumed silica. The organic molybdenum antifriction agent is one or two of dialkyl dithio molybdenum oxysulfide phosphate, dialkyl dithio carbamic acid molybdenum and sulfur phosphorus nitrogen molybdenum complex in a ratio of 1:5-5:1. The amide friction improvement consists of one or two of oleamide, erucamide, stearic acid amide and palmitic acid amide in a ratio of 1:10-10:1.
The beneficial effects of the invention are as follows:
1. compared with the complex calcium sulfonate grease prepared by the traditional process, the complex calcium sulfonate grease has excellent high temperature resistance, good mechanical stability, excellent extreme pressure wear resistance and antifriction property, particularly has excellent high water spray resistance, and almost no loss and expansion of the grease in the environment with water more than 100%; the wear amount of the bearing can be reduced to 0 wear.
2. In the production process, as a plurality of macromolecular acids are added, the use amount of phase inversion agents such as alcohols, ethers and the like is reduced, and the environmental pollution is reduced;
3. the efficiency of converting Newtonian high-base-number calcium sulfonate into non-Newtonian calcium sulfonate is improved, and the conversion is thorough, so that the production process is simpler.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention and are not limiting of the claims of the invention.
The saponification kettles selected in the following examples had the following properties: the volume is 5L, the stirring is carried out by open oil bath, the stirring is carried out under normal pressure at the rotating speed of 2-100 rpm.
The invention relates to a preparation method of high-performance composite calcium sulfonate grease, which comprises the following steps:
step A: adding 20-40% of ultra-high base number synthetic calcium sulfonate with total base number of 380-420 mgKOH/g, 50-70% of base oil and 1-18% of liquid phase inversion agent, mixing, stirring and heating to 60-95 ℃, and continuously stirring for 0.1-1.5 hours;
and (B) step (B): adding a part of macromolecular acid, continuously stirring, keeping the temperature at 60-95 ℃ for 0.2-2 hours, and adding the rest of base oil after the whole system is thickened into a grease shape;
step C: heating to 95-120 ℃, adding an aqueous solution of C12-C24 hydroxy fatty acid accounting for 0.5-8% of the total mass, boric acid accounting for 0.5-4% and calcium hydroxide accounting for 0.5-2%, stirring, and keeping the temperature for 0.2-1 hour;
step D: continuously heating to 130-150 ℃ to dehydrate for 0.5-2 hours;
step E: adding antioxidant with the mass ratio of 0.5-2%, heating to 160-220 ℃ and refining for 0.1-1 hour;
step F: when the temperature is reduced to below 150-100 ℃, adding a water repellent agent, stirring for 0.5-1 hour at the temperature, homogenizing, and degassing to obtain a finished product.
The conversion mechanism of calcium sulfonate is as follows: the acid in the phase inversion agent reacts with the calcium carbonate in the phase inversion agent to generate CO 2 ，CO 2 Then reacts with amorphous calcium carbonate and water in the system to generate soluble calcium bicarbonate, the calcium bicarbonate is extremely unstable, and the crystalline calcium carbonate is precipitated again after being heated and is rapidly aggregated into large-particle crystalline calcium carbonate crystal stacks, and the reaction equation is as follows:
macromolecular acids are capable of stably producing CO 2 The closed environment can well lead CO to 2 The amorphous calcium carbonate is more favorable for converting amorphous calcium carbonate into crystalline calcium carbonate when the amorphous calcium carbonate exists on the surface of liquid, so that the speed of converting Newtonian calcium sulfonate into non-Newtonian high-base-number calcium sulfonate is faster, the conversion is more thorough, the use amount of phase inversion agents such as alcohols, ethers and the like can be reduced, and the environmental pollution is reduced.
Example one
The high-performance complex calcium sulfonate grease has high viscosity (the kinematic viscosity at 40 ℃ is 50-2000 mm) 2 And/s) paraffin-based mineral oil, high-base calcium sulfonate (380-420 mgKOH/g) and composite calcium soap are used as thickening agents, and water repellent agents, antioxidants, organic molybdenum friction reducers and amide friction improvers are added into the thickening agents to prepare the high-base calcium sulfonate friction oil, wherein the mass ratio of the components is as follows:
base oil: 43%
High base number calcium sulfonate: 35%
Liquid phase inversion agent (isopropanol and ethanol mixture): 4%
Macromolecular acid: 2%
Boric acid: 3%
12-hydroxy fatty acid: 5%
Calcium hydroxide; 1%
Phenyl alpha-naphthylamine: 1%
Water repellent agent: 2%
Organic molybdenum friction reducer: 3%
Amide friction modifiers: 5%
Mixing and stirring base oil, high-base-number calcium sulfonate and a liquid phase inversion agent, heating to 65 ℃, stirring at constant temperature for 30 minutes, adding macromolecular acid, thickening, adding 12-hydroxy fatty acid, boric acid and calcium hydroxide, heating to 130 ℃, conducting compound saponification for 1 hour, heating to 150 ℃ for dehydration for 2 hours, adding phenyl alpha-naphthylamine dialkyl diphenylamine, heating to 210 ℃ for refining, cooling to 110 ℃ after keeping for 10 minutes, adding a water repellent agent, continuously stirring for 0.5 hour, cooling to below 10 ℃, adding an antioxidant, an organic molybdenum friction reducer and an amide friction modifier, continuously stirring for 0.5 hour, homogenizing and degassing to obtain the finished product.
Example two:
the high-performance complex calcium sulfonate grease has high viscosity (the kinematic viscosity at 40 ℃ is 50-2000 mm) 2 And/s) using a composite soap formed by paraffin-based mineral oil, high-base-number calcium sulfonate (380-420 mgKOH/g) and composite calcium soap as a thickening agent, and adding an antioxidant and a water repellent agent, wherein the weight ratio of the components is as follows:
base oil: 35%
High base number calcium sulfonate: 32%
Liquid phase inversion agent (isopropanol and ethanol mixture): 4%
Macromolecular acid: 1.5%
Phenylboronic acid: 2%
12-hydroxystearic acid: 6%
Calcium hydroxide: 1.5%
Dioctyl diphenylamine: 1%
A water repellent agent; 3%
Organic molybdenum friction reducer: 3%
Amide friction modifiers: 3%
The performance index of examples one and two is shown in Table 1.
Table 1 performance index for examples one and two
As can be seen from the test results in Table 1, the product has excellent water resistance in addition to excellent colloid stability, mechanical stability and frictional wear properties, and is mainly characterized in that more than 100% of water can be separated after a high-temperature roller test at 80 ℃ for 50 hours, and the consistency of the product does not change by more than 20 units. And the SRV test shows that the curve trend is very stable.

Claims (9)

1. The composite calcium sulfonate grease is characterized by comprising the following components in percentage by mass:
30% -70% of base oil;
20-40% of ultra-high base number synthesized calcium sulfonate;
0.5 to 2 percent of antioxidant;
1-18% of phase inversion agent;
1-5% of macromolecular acid;
1-5% of water repellent agent;
1-5% of organic molybdenum antifriction agent;
1-10% of amide friction modifier;
the macromolecular acid is one or more of maleic acid, lactic acid, citric acid, lauric acid and stearic acid;
the phase inversion agent is one or more of water, small molecular acid and alcohol; the small molecular acid is one or more of formic acid, acetic acid, propionic acid, boric acid, monoalkyl substituted boric acid and phosphoric acid; the alcohol is one or more of butanol, ethylene glycol, propylene glycol and 1, 6-hexanediol;
the water repellent agent is one or more of ammonium zirconium carbonate, cuprous chloride, polyamine polyamide, modified melamine formaldehyde resin and fumed silica;
the organic molybdenum antifriction agent is composed of one or two of dialkyl dithio molybdenum oxysulfide phosphate, dialkyl dithio carbamic acid molybdenum and sulfur phosphorus nitrogen molybdenum complex in a ratio of 1:5-5:1;
the amide friction modifier consists of one or two of oleamide, erucamide, stearic acid amide and palmitic acid amide in the ratio of 1:10-10:1.
2. The complex calcium sulfonate grease according to claim 1, wherein the base oil has a kinematic viscosity at 40 ℃ of 50 to 2000mm 2 /s。
3. The complex calcium sulfonate grease according to claim 1, wherein the base oil is one or more of dioctyl sebacate, dioctyl adipate, neopentyl polyol ester, isooctyl adipate, dioctyl phthalate, dibutyl phthalate, trimethylolpropane trioctanoate, trimethylolpropane trioleate, triisopropylphenyl phosphate, methyl silicone oil, methyl phenyl silicone oil, poly-alpha-olefin synthetic oil and cycloalkyl mineral oil.
4. The complex calcium sulfonate grease according to claim 1, wherein the base number of the ultra-high base number synthetic calcium sulfonate is 380 to 420mgKOH/g.
5. The complex calcium sulfonate grease according to claim 1, further comprising 0.5 to 8wt% of a C12 to C24 hydroxy fatty acid, 0.5 to 4wt% of boric acid or a mono-alkyl substituted boric acid, and 0.5 to 2wt% of calcium hydroxide.
6. The complex calcium sulfonate grease of claim 5, wherein the mono alkyl substituted boric acid has the general formula R-B (OH) 2 Wherein R is one or more of alkyl, cycloalkyl and aryl.
7. The complex calcium sulfonate grease of claim 1, wherein the antioxidant is one or more of zinc dialkyldithiophosphate, zinc alkyl dithiocarbamate, phenyl alpha-naphthylamine, dialkyldiphenylamine and di-tert-butyl-p-cresol.
8. The complex calcium sulfonate grease according to claim 1, wherein the complex calcium sulfonate grease is capable of separating not less than 85% of water and has a consistency of not more than 20 units after being subjected to a high temperature roller test at 80 ℃ for 50 hours under a condition of containing 200% of water.
9. A method for preparing the complex calcium sulfonate grease according to claim 5 or 6, characterized in that the preparation method comprises the steps of:
step S1: adding super high base number synthesized calcium sulfonate, a part of base oil and a phase inversion agent into a stirring kettle, uniformly mixing, heating to 60-95 ℃, and continuously stirring for 0.1-1.5 hours;
step S2: adding macromolecular acid, continuously stirring, keeping the temperature at 60-95 ℃ for 0.2-2 hours, and adding the rest of base oil after the whole system is thickened into a grease shape;
step S3: heating to 95-120 ℃, adding aqueous solution of C12-C24 hydroxy fatty acid, boric acid and calcium hydroxide, stirring for reaction, and keeping the temperature for 0.2-1 hour;
step S4: continuously heating to 130-150 ℃ to dehydrate for 0.5-2 hours;
step S5: adding 0.5-2% of antioxidant, heating to 160-220 ℃ and refining for 0.1-1 hour;
step S6: when the temperature is reduced to below 150-100 ℃, water repellent agent, amide friction modifier and organic molybdenum antifriction agent are added, stirring is carried out for 0.5-1 hour at the temperature, and homogenization and degassing are carried out to obtain the finished product.
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CN101319164A (en) * 2008-07-18 2008-12-10 杭州得润宝油脂有限公司 Composite calcium sulphonic consistent grease and preparation method thereof
CN101824357A (en) * 2010-05-27 2010-09-08 李墨菊 High-performance complex calcium sulfonate grease and preparation method thereof
CN108611159A (en) * 2016-12-12 2018-10-02 中国石油天然气股份有限公司 Boracic complex calcium sulfonate grease composition and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101319164A (en) * 2008-07-18 2008-12-10 杭州得润宝油脂有限公司 Composite calcium sulphonic consistent grease and preparation method thereof
CN101824357A (en) * 2010-05-27 2010-09-08 李墨菊 High-performance complex calcium sulfonate grease and preparation method thereof
CN108611159A (en) * 2016-12-12 2018-10-02 中国石油天然气股份有限公司 Boracic complex calcium sulfonate grease composition and preparation method thereof

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