CN114752426A - 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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CN114752426A
CN114752426A CN202110032551.6A CN202110032551A CN114752426A CN 114752426 A CN114752426 A CN 114752426A CN 202110032551 A CN202110032551 A CN 202110032551A CN 114752426 A CN114752426 A CN 114752426A
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calcium sulfonate
acid
grease
lubricating grease
calcium
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CN114752426B (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 calcium sulfonate complex grease with high water resistance, low starting friction and low running friction and a preparation method thereof. The high-water-spray-resistance composite calcium sulfonate-based lubricating grease comprises the following components in percentage by mass: 30-70% of base oil; 20-40% of ultrahigh base number synthetic calcium sulfonate; 0.5-2% of an antioxidant; 1-18% of a phase transfer agent; 1-5% of macromolecular acid; 1-5% of a water repellent agent; 1-5% of organic molybdenum friction reducer and 1-10% of amide friction improver. Compared with the traditional product, the production process of the invention reduces the usage amount of phase transfer agents such as alcohols, ethers and the like, and reduces the environmental pollution; the efficiency of converting the Newtonian high-base-number calcium sulfonate into the non-Newtonian high-base-number calcium sulfonate is improved, the phase inversion is relatively thorough, and the production process is simpler. Meanwhile, the material has excellent high temperature resistance, good mechanical stability and excellent energy-saving and friction-reducing properties; 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 a high-performance and high-water-spray-resistance composite calcium sulfonate-based lubricating grease by adopting a traditional phase transfer agent and macromolecular acid together.
Background
The composite calcium sulfonate-based lubricating grease is one of a few high-performance lubricating greases at present, has high temperature resistance, extreme pressure abrasion resistance, shear stability, low-temperature pumping property, rust resistance and water resistance, is called as 'new-generation high-efficiency lubricating grease', has wide application prospects in various severe working condition environments such as dusty, watery and high-load environments, and is applied to large-scale enterprises in various industries such as home and abroad steel, paper making, bearings and the like.
The rolling mill is widely applied in China, the plate shape control capability of the rolling mill is stronger and stronger, the structure of the rolling mill is more complex, the stress state of a bearing of a working roll is harsh, and higher requirements are put forward on the extreme pressure and water resistance of lubricating grease. When the working roll of the rolling mill rotates at a high speed, the lubricating grease of the bearing can be quickly lost due to the internal pressure borne by the bearing seat of the working roll and the washing of cooling water of the high-pressure roll, so that the lubricating 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 is burnt and the roll is held is sometimes caused; meanwhile, the cooling water of the roller can bring impurities such as iron scales into the bearing seat, abrasive wear is formed inside the bearing, and pitting corrosion and fatigue peeling are caused. If the bearing is not maintained timely, the bearing can be directly scrapped. In view of the above, the grease consumption is large because the bearing must be replenished with new grease before each mounting. With the increasing importance of domestic iron and steel enterprises on equipment lubrication, the lubrication management tends to be delicate, and lubricating grease with long service life and excellent comprehensive performance is urgently needed to meet the use requirement of the rolling mill working roller bearing on no grease supplementation in multiple cycles. The compound calcium sulfonate grease has comprehensive and excellent performance, particularly keeps the consistency unchanged basically after meeting water, has excellent extreme pressure abrasion resistance, small usage amount and long service life, can meet the nearly harsh working condition of a rolling mill bearing, and gradually becomes the first choice of the lubricating grease for the working roller bearing of the hot rolling broad band steel rolling mill.
The complex calcium sulfonate-based grease mainly undergoes three processes. In the first stage, in 1950, Sproule et al found that the use of calcium sulfonate as a thickener to make grease and its use with calcium soap of fatty acid increased the dropping point of grease, but the thickening ability of this calcium sulfonate based grease was very low; in the second stage, in the 60 s of the 20 th century, people find a method for converting the Newtonian calcium sulfonate into the non-Newtonian calcium sulfonate with the thixotropic property, and meanwhile, the calcium sulfonate-based lubricating grease has outstanding performances in the aspects of high temperature resistance, shear stability and the like, but has the defect that the thickening agent is high in content, so that the low-temperature pumping property is poor, and the large-scale industrial application of the lubricating grease is prevented; in the third stage, in the middle of the 80's in the 20 th century, Ronald J M firstly invented the compounding of calcium borate soap and fatty acid calcium soap in the preparation process of calcium sulfonate grease, and the compound calcium sulfonate grease not only has the advantages of the original calcium sulfonate grease, but also eliminates the weak point of poor low-temperature pumping property of the original grease.
Ron Muir et al, Witco Chemical company, 1985, invented a novel process for producing a composite calcium sulfonate-based grease, with patent numbers: US 4560489. Ron Muir et al, based on the former low base number calcium sulfonate synthesis process, convert the high base number calcium sulfonate, and add 12-hydroxystearic acid and boric acid to improve the colloid stability and tribological properties of the grease, and produce the real complex calcium sulfonate grease in the laboratory.
John f.barnes et al, NCH corporation, 1992, invented a process for producing a complex calcium sulfonate-based grease, with the patent numbers: US 5126062. Barnes et al prepared a composite calcium sulfonate-based lipid using isopropyl alcohol and phosphoric acid instead of ethylene glycol monomethyl ether and acetic acid. In the components of the composite calcium sulfonate-based lubricating grease, 12-hydroxystearic acid is also added to improve the performances of the colloid, the tribology and the like of the lubricating grease.
William D.Olson et al, 1994, Witco Chemical, invented a complex calcium sulfonate based grease, U.S. Pat. No. US 5338467. This patent does not use alcohols such as ethylene glycol monomethyl ether and isopropyl alcohol as phase inversion promoters, and uses stearic acid as a phase inversion promoter.
The invention discloses a preparation method of a high-performance lubricating grease mixed with lithium-calcium sulfonate lubricating grease, which is invented by plum blossom, China petrochemical company and the like in 2003, and the patent numbers are as follows: CN 1616612 a. The main purpose of the patent is to prepare a complex lithium-based grease containing overbased calcium sulfonate. The lubricating grease has the characteristics of two lubricating greases, makes up for the deficiencies of the two lubricating greases, and has good mechanical stability, colloid stability, water resistance, rust resistance and high-temperature service performance under the condition of not adding additives (except an antioxidant and an adhesive). The preparation process comprises the following steps:
The preparation method of the ultrahigh-key-value composite calcium sulfonate-based lubricating grease invented by anyhaiman and the like of the 2007 Wuxi Gaolujie chemical company Limited has the following patent numbers: CN 1001153239A. The main purpose of the patent is to prepare the complex calcium sulfonate grease by using ultra-high base number T106. The prepared lubricating grease has good mechanical stability, colloid stability, water resistance and rust resistance without adding additives (except an antioxidant and an adhesive), outstanding shear resistance and excellent pumping performance, and trial applications in multiple motor manufacturers, steel plants, paper mills and the like prove that the grease changing times are reduced under the same working conditions, and the service life of equipment is prolonged.
The most critical step of the production process of the compound calcium sulfonate-based lubricating grease is to convert Newtonian high-base-number calcium sulfonate into non-Newtonian compound calcium sulfonate-based lubricating grease, and if the phase inversion is unsuccessful or incomplete, the lubricating grease is soft, the dropping point is lower, and the extreme pressure wear resistance of the lubricating grease is poor. The above patents all adopt alcohols, ethers, low molecular acids and the like as phase transfer agents, after the conversion is finished, the phase transfer agents such as the alcohols and the ethers are directly discharged into the atmosphere, so that the environmental pollution is caused, and the problems of incomplete conversion, unstable conversion process and the like exist, so that how to reduce the usage amount of the phase transfer agents and improve the conversion effect is achieved, thereby effectively reducing the environmental pollution and improving the product performance becomes the focus of attention in the field.
Disclosure of Invention
The invention aims to solve the defects of the composite calcium sulfonate-based lubricating grease and the preparation method thereof, reduce the using amount of a phase inversion agent, improve the conversion effect, effectively reduce the environmental pollution and improve the product, and provides the high-performance composite calcium sulfonate-based lubricating grease and the preparation method thereof. Meanwhile, the problems that the domestic compound calcium sulfonate is used in a rolling mill bearing with poor sealing performance, the inside of an oil groove between bearings is washed by a large amount of water, and the compound calcium sulfonate is washed away by water or expands when meeting water, so that the content of lubricating grease in the oil groove between the bearings is less and less due to extrusion from the inside of the oil groove between the bearings, the bearings are abraded and sintered and the like are solved.
In order to achieve the purpose, the invention provides a composite calcium sulfonate-based lubricating grease which comprises the following components in percentage by mass:
Figure BDA0002891291620000041
the composite calcium sulfonate-based lubricating grease disclosed by the invention is characterized in that the phase transfer agent is one or more of water, micromolecular 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 composite calcium sulfonate-based lubricating grease disclosed by the invention is characterized in that the micromolecular 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 disclosed by the invention has the kinematic viscosity of 50-2000 mm at 40 ℃ of base oil2/s。
The composite calcium sulfonate-based lubricating grease disclosed by the invention is characterized in that the base oil is one or more of dibasic acid diester, dioctyl sebacate, dioctyl adipate, neopentyl polyol ester, isooctyl adipate, dioctyl phthalate, dibutyl phthalate, trimethylolpropane tricaprylate, 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 disclosed by the invention has the base number of 380-420 mgKOH/g in the ultrahigh base number synthetic calcium sulfonate.
The composite calcium sulfonate-based lubricating grease further comprises 0.5-8 wt% of C12-C24 fatty acid, 0.5-4 wt% of boric acid or monoalkyl substituted boric acid and 0.5-2 wt% of calcium hydroxide.
The general formula of the composite calcium sulfonate grease of the invention is R-B (OH)2Wherein R is one or more of alkyl, cycloalkyl and aryl.
The composite calcium sulfonate-based lubricating grease disclosed by the invention is characterized in that the antioxidant is one or more of zinc dialkyl dithiophosphate, zinc alkyl dithiocarbamate, 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 composite calcium sulfonate-based lubricating grease disclosed by the invention is characterized in that the organic molybdenum antifriction agent is formed by mixing one or two of dialkyl molybdenum dithiophosphate sulfo-oxo-molybdenum, dialkyl molybdenum dithiocarbamate and sulfur-phosphorus-nitrogen-molybdenum complexes in a ratio of 1: 5-5: 1.
The composite calcium sulfonate-based lubricating grease is characterized in that the amide friction improvement is formed by mixing 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-based lubricating grease disclosed by the invention can separate more than 85% of water after being tested by a high-temperature roller at 80 ℃ for 50h under the condition of containing 200% of water, and the consistency change is not more than 20 units.
The invention also provides a preparation method of the high-water-spray-resistance composite calcium sulfonate-based lubricating grease, which comprises the following steps:
step S1: adding the ultra-high base number synthetic calcium sulfonate, a part of base oil and a phase transfer 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 constant at 60-95 ℃ for 0.2-2 hours, and adding the rest of base oil after the whole system is thickened into a lubricating 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 ℃ for dewatering 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 ℃, adding a water repellent agent, an antioxidant, an organic molybdenum friction reducer and an amide friction improver, stirring for 0.5-1 hour at the temperature, homogenizing and degassing to obtain a finished product.
The invention can also be detailed as follows:
the technical scheme for solving the technical problem of the invention can also be as follows:
a high-performance composite calcium sulfonate-based lubricating grease and a preparation method thereof, wherein the base oil is one of dibasic acid diester, dioctyl sebacate, dioctyl adipate, neopentyl polyol ester, isooctyl adipate, dioctyl phthalate, dibutyl phthalate, trimethylolpropane tricaprylate, trimethylolpropane trioleate, triisopropylphenyl phosphate, methyl silicone oil, methyl phenyl silicone oil, poly alpha-olefin synthetic oil or naphthenic mineral oil, the ultrahigh-base-number synthetic calcium sulfonate, the ultrahigh base number is 380-420 mgKOH/g, and the composite components of the synthetic calcium sulfonate are 0.5-8% of C12-C24 hydroxy fatty acid, 0.5-4% of boric acid and 0.5-2% of calcium hydroxide respectively, the phase transfer agent is composed of one or a mixture of acetic acid, ethanol, isopropanol, water and C12-C22 hydroxy fatty acid and macromolecular acid. The antioxidant is one or a mixture of zinc dialkyl dithiophosphate, zinc alkyl dithiocarbamate, 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 friction reducer is formed by mixing one or two of dialkyl dithio-phospho-molybdic acid, dialkyl dithio-carbamic acid molybdenum and sulfur-phosphorus-nitrogen-molybdenum complexes in a ratio of 1: 5-5: 1. The amide friction improvement is formed by mixing one or two of oleamide, erucamide, stearic acid amide and palmitic acid amide in a ratio of 1: 10-10: 1.
The invention has the beneficial effects that:
1. compared with the composite calcium sulfonate-based lubricating grease prepared by the traditional process, the composite calcium sulfonate-based lubricating grease disclosed by the invention has excellent high-temperature resistance, good mechanical stability, excellent extreme pressure wear resistance and friction reduction property, and particularly has very good high water-spraying resistance, and the lubricating grease hardly runs off and expands in an environment with more than 100% of water; the amount of wear of the bearing can be reduced to 0 wear.
2. In the production process, due to the addition of some macromolecular acids, the use amount of phase transfer agents such as alcohols, ethers and the like is reduced, and the environmental pollution is reduced;
3. the efficiency of converting the Newtonian high-base-number calcium sulfonate into the non-Newtonian high-base-number calcium sulfonate is improved, the conversion is thorough, and the production process is simpler.
Detailed Description
For a further understanding of the invention, reference will now be made to the following examples describing preferred embodiments of the invention, but it is to be understood that the description is intended to illustrate further features and advantages of the invention and is not intended to limit the scope of the claims.
The saponification kettle selected for the following examples had the following properties: the volume is 5L, the stirring paddle is heated in an open oil bath at normal pressure and at the rotating speed of 2-100 r/min.
The invention relates to a preparation method of high-performance composite calcium sulfonate-based lubricating grease, which comprises the following steps:
step A: adding 20-40% by mass of ultrahigh-base-number synthetic calcium sulfonate with a total base number of 380-420 mgKOH/g, 50-70% by mass of base oil and 1-18% by mass of liquid phase transfer agent, mixing, stirring, heating to 60-95 ℃, and continuously stirring for 0.1-1.5 hours;
and B: adding a part of macromolecular acid, continuously stirring, keeping the temperature constant at 60-95 ℃ for 0.2-2 hours, and adding the rest of base oil after the whole system is thickened into a lubricating grease shape;
and C: heating to 95-120 ℃, adding 0.5-8% of C12-C24 hydroxy fatty acid, 0.5-4% of boric acid and 0.5-2% of calcium hydroxide aqueous solution in percentage by mass, stirring, and keeping the temperature for 0.2-1 hour;
step D: continuously heating to 130-150 ℃ for dewatering for 0.5-2 hours;
step E: adding an antioxidant with the mass ratio of 0.5-2%, heating to 160-220 ℃, and refining for 0.1-1 hour;
step F: and adding a water repellent agent when the temperature is reduced to below 150-100 ℃, stirring for 0.5-1 hour at the temperature, homogenizing, and degassing to obtain a finished product.
The mechanism of conversion of calcium sulfonate is as follows: the acid in the phase transfer agent reacts with calcium carbonate therein to produce CO 2，CO2Then reacting with amorphous calcium carbonate and water in the system to generate soluble calcium bicarbonate which is extremely unstable, precipitating crystalline calcium carbonate again after being heated, and rapidly aggregating the crystalline calcium carbonate into large-particle crystalline calcium carbonate crystal accumulation bodies, wherein the reaction equation is as follows:
Figure BDA0002891291620000081
macromolecular acid can stably generate CO2And the closed environment can well lead CO to be generated2Existing on the liquid surface, is more beneficial to converting the amorphous calcium carbonate into the crystalline calcium carbonate, so that the speed of converting the Newtonian calcium sulfonate into the non-Newtonian high-base-number calcium sulfonate is higher, the conversion is more thorough, the use amount of phase transfer agents such as alcohols, ethers and the like can be reduced, and the environmental pollution is reduced.
Example one
The high-performance composite calcium sulfonate grease has high viscosity (40 ℃ movement)The viscosity is 50-2000 mm2The paraffin base oil/s) composite soap formed by paraffin base mineral oil, high base number calcium sulfonate (380-420 mgKOH/g) and composite calcium soap is used as a thickening agent, and a water repellent agent, an antioxidant, an organic molybdenum friction reducer and an amide friction modifier are added to form the paraffin base oil/s composite soap, wherein the paraffin base mineral oil/s composite soap comprises the following components in parts by mass:
base oil: 43 percent
High base number calcium sulfonate: 35 percent of
Liquid phase inversion agent (isopropanol and ethanol mixture): 4 percent of
Macromolecular acid: 2 percent of
Boric acid: 3 percent
12-hydroxy fatty acid: 5 percent
Calcium hydroxide; 1 percent
Phenyl α -naphthylamine: 1 percent of
Water repellent agent: 2 percent of
Organic molybdenum friction reducer: 3 percent of
Amide friction modifiers: 5 percent of
Mixing and stirring base oil, high-base-number calcium sulfonate and a liquid phase transfer agent, heating, stirring at a constant temperature for 30 minutes after heating to 65 ℃, adding macromolecular acid, thickening, adding 12-hydroxy fatty acid, boric acid and calcium hydroxide, heating to 130 ℃, performing complex saponification for 1 hour, heating to 150 ℃, dehydrating for 2 hours, adding phenyl alpha-naphthylamine dialkyl diphenylamine, heating to 210 ℃, refining, keeping for 10 minutes, cooling to 110 ℃, 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 a finished product.
Example two:
the high-performance composite calcium sulfonate-based lubricating grease has high viscosity (the kinematic viscosity at 40 ℃ is 50-2000 mm)2The paraffin base oil thickener is prepared by taking composite soap formed by paraffin base 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 components are mixed according to the mass ratio as follows:
base oil: 35 percent of
High base number calcium sulfonate: 32 percent of
Liquid phase inversion agent (isopropanol and ethanol mixture): 4 percent
Macromolecular acid: 1.5 percent
Phenylboronic acid: 2 percent
12-hydroxystearic acid: 6 percent
Calcium hydroxide: 1.5 percent
Dioctyl diphenylamine: 1 percent of
A water repellent agent; 3 percent of
Organic molybdenum friction reducer: 3 percent of
Amide friction modifiers: 3 percent of
The performance indices for examples one and two are shown in table 1.
TABLE 1 Performance index of the first and second samples of examples
Figure BDA0002891291620000101
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 performance, which is mainly shown in that after a high temperature roller test at 80 ℃ for 50h, more than 100% of water can be separated out, and the consistency of the product does not exceed 20 units. And the curve trend is very stable in the SRV test.

Claims (13)

1. The composite calcium sulfonate-based lubricating grease is characterized by comprising the following components in percentage by mass:
Figure FDA0002891291610000011
。
2. the calcium sulfonate complex grease as claimed in claim 1, wherein the phase transfer agent is one or more of water, small molecule 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.
3. The calcium sulfonate complex grease as claimed in claim 2, wherein the small molecular acid is one or more of formic acid, acetic acid, propionic acid, boric acid, mono-alkyl substituted boric acid and phosphoric acid; the alcohol is one or more of isopropanol, butanol, ethylene glycol, propylene glycol and 1, 6-hexanediol.
4. The calcium sulfonate complex grease of claim 1, wherein the base oil has a kinematic viscosity at 40 ℃ of 50 to 2000mm2/s。
5. The calcium complex sulfonate grease as claimed in claim 1, wherein the base oil is one or more of dibasic acid diester, dioctyl sebacate, dioctyl adipate, neopentyl polyol ester, isooctyl adipate, dioctyl phthalate, dibutyl phthalate, trimethylolpropane tricaprylate, trimethylolpropane trioleate, triisopropylphenyl phosphate, methyl silicone oil, methyl phenyl silicone oil, poly-alpha-olefin synthetic oil and cycloalkyl mineral oil.
6. The calcium complex sulfonate grease as claimed in claim 1, wherein the base number of the ultra-high base number synthetic calcium sulfonate is 380 to 420 mgKOH/g.
7. The complex calcium sulfonate grease as claimed in claim 1, further comprising 0.5 to 8 wt% of a C12 to C24 fatty acid, 0.5 to 4 wt% of boric acid or monoalkyl-substituted boric acid, and 0.5 to 2 wt% of calcium hydroxide.
8. The complex calcium sulfonate grease as claimed in claim 7, wherein the monoalkyl boronic acid has the general formula R-B (OH)2Wherein R is one or more of alkyl, cycloalkyl and aryl.
9. The calcium sulfonate complex grease as claimed in claim 1, wherein the antioxidant is one or more of zinc dialkyl dithiophosphate, zinc alkyl dithiocarbamate, 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.
10. The composite calcium sulfonate-based lubricating grease as claimed in claim 1, wherein the organic molybdenum friction reducer is formed by mixing one or two of dialkyl molybdenum dithiophosphate sulfo-oxo, dialkyl molybdenum dithiocarbamate and sulfur-phosphorus-nitrogen-molybdenum complexes in a ratio of 1: 5-5: 1.
11. The composite calcium sulfonate-based grease of claim 1 is characterized in that the amide friction improvement is one or two of oleamide, erucamide, stearamide and palmitamide mixed in a ratio of 1:10 to 10: 1.
12. The calcium sulfonate complex grease as claimed in claim, wherein the calcium sulfonate complex grease is capable of separating not less than 85% of water and has a consistency change of not more than 20 units after roller test at 80 ℃ for 50h under the condition of containing 200% of water.
13. A method for preparing the highly water spray resistant calcium sulfonate complex grease of any one of claims 1-11, which comprises the following steps:
step S1: adding the ultra-high base number synthetic 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 constant at 60-95 ℃ for 0.2-2 hours, and adding the rest base oil after the whole system is thickened into a lubricating grease;
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 ℃ for dewatering 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 ℃, adding a water repellent agent, an antioxidant and an organic molybdenum antifriction agent, stirring for 0.5-1 hour at the temperature, and homogenizing and degassing to obtain a finished product.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116891771A (en) * 2023-06-05 2023-10-17 武汉理工大学 Polyurea grease and preparation method and application thereof
CN116921182A (en) * 2023-07-21 2023-10-24 中铁大桥局集团有限公司 Torque coefficient processing method for chromium-free corrosion-resistant high-strength bolt

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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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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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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116891771A (en) * 2023-06-05 2023-10-17 武汉理工大学 Polyurea grease and preparation method and application thereof
CN116921182A (en) * 2023-07-21 2023-10-24 中铁大桥局集团有限公司 Torque coefficient processing method for chromium-free corrosion-resistant high-strength bolt

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