CN112745979A - Grease composition containing thiuram compound and preparation method thereof - Google Patents
Grease composition containing thiuram compound and preparation method thereof Download PDFInfo
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- CN112745979A CN112745979A CN201911039620.5A CN201911039620A CN112745979A CN 112745979 A CN112745979 A CN 112745979A CN 201911039620 A CN201911039620 A CN 201911039620A CN 112745979 A CN112745979 A CN 112745979A
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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
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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
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
- C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
- C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
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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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/02—Well-defined aliphatic compounds
- C10M2203/0206—Well-defined aliphatic compounds 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/02—Well-defined aliphatic compounds
- C10M2203/024—Well-defined aliphatic compounds unsaturated
-
- 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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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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
- 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
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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
- 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
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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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
- 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
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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
- 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
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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
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/02—Unspecified siloxanes; Silicones
- C10M2229/025—Unspecified siloxanes; Silicones used as base material
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- Chemical & Material Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
The invention relates to the field of lithium-based lubricating grease, and discloses a lubricating grease composition containing a thiuram compound and a preparation method thereof. The lubricating grease composition contains base oil, a thickening agent, a thiuram compound and calcium petroleum sulfonate, wherein the thickening agent is a lithium-based thickening agent; the thiuram compound is contained in an amount of 3 to 50g and the calcium petroleum sulfonate is contained in an amount of 3 to 50g per kg of the base oil. The invention also discloses a method for preparing the lubricating grease composition, which comprises the following steps: mixing the thickening agent and part of the base oil, heating, and mixing with the thiuram compound, the calcium petroleum sulfonate and the rest of the base oil. Through the technical scheme, the lubricating grease composition has good extreme pressure wear resistance.
Description
Technical Field
The invention relates to the field of lithium-based lubricating grease, in particular to a lubricating grease composition taking lithium soap as a thickening agent and a preparation method thereof.
Background
In recent years, with the development of automation and intellectualization of mechanical equipment, in order to ensure the running precision and reliability of the equipment, more and more parts are integrated in a combined manner, and such parts are more and more difficult to maintain or even impossible to maintain, so that the parts need to be lubricated by grease with better performance and longer service life. Such as sealed hub bearings, small vibrators, small speed reducers and the like, have increased load in the application process, and the lubricating grease is required to have excellent and long-acting extreme pressure wear resistance so as to ensure that the parts can meet the requirements of long-term application.
The addition of extreme pressure antiwear additive is the main means of improving the bearing capacity and antiwear performance of lubricating grease, and many additives have extreme pressure antiwear performance, for example, the commonly used extreme pressure antiwear additive is liquid sulfur-containing compound, and the sulfur content is usually 20-40 wt%.
Sulfurized isobutylene, sulfurized lard, sulfurized olefin cottonseed oil, thiocarbamate, thiadiazole, etc. are common liquid sulfur-containing compounds, sometimes used in combination with other types of extreme pressure antiwear additives, for example, CN101892114A in lithium grease prepared from mineral oil, sulfurized isobutylene and molybdenum dialkyl dithiophosphate, P of greaseBA value of 755N (GB/T12583); CN105087125A adding sulfurized isobutylene and dithiophosphate as extreme pressure antiwear agent into sodium-based lubricating grease prepared from mineral oil; CN109337749A is added into lithium-calcium grease prepared by mineral oil-olefin oil, at least one of sulfurized isobutylene, molybdenum dialkyl dithiocarbamate, zinc dialkyl dithiophosphate and tricresyl phosphate, and polyisobutylene with molecular weight of 1000-5000-fold, so as to improve the extreme pressure anti-wear performance of the grease; CN109337737A Trimethylphenol phosphate and alkyl thiocarbamate are added into bentonite-calcium complex sulfonate grease prepared from mineral oil-ester oil-olefin oil as extreme pressure antiwear agent.
Thiuram compounds also belong to the polysulfide family of solid compounds, with a low odor. Although thiuram compounds have also been reported, they are generally used only in lubricating oils, for example, CN104024389A discloses that lubricating oil compositions having lower friction coefficients and wear scar diameters by adding certain amounts of molybdenum dialkyldithiocarbamate, tetrabenzylthiuram disulfide and organic amine to base oil. CN86101764A discloses a cold rolling lubricant for metal materials, which is used by adding 0.1-3 wt% of tetraalkyl thiuram monosulfide, tetraalkyl thiuram disulfide and the like as sulfur type antioxidant.
However, the grease obtained by the above method has poor extreme pressure wear resistance, and particularly, the extreme pressure wear resistance of lithium grease cannot be effectively improved.
Disclosure of Invention
The invention aims to overcome the problem of poor effect in the prior art and provides a lubricating grease composition containing a thiuram compound and a preparation method thereof.
In order to achieve the above object, an aspect of the present invention provides a grease composition containing a thiuram compound, the grease composition containing a base oil, a thickener, a thiuram compound, and calcium petroleum sulfonate, wherein the thickener is a lithium-based thickener; the thiuram compound is contained in an amount of 3 to 50g and the calcium petroleum sulfonate is contained in an amount of 3 to 50g per kg of the base oil.
In a second aspect the present invention provides a method of preparing said grease composition, the method comprising: mixing the thickening agent and part of the base oil, heating, and mixing with the thiuram compound, the calcium petroleum sulfonate and the rest of the base oil.
Through the technical scheme, the lubricating grease composition has good extreme pressure wear resistance and shows that the maximum non-seizure load is higher. Moreover, each component used in the invention is not easy to volatilize and has small smell.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The lubricating grease composition containing the thiuram compound comprises base oil, a thickening agent, at least one thiuram compound and calcium petroleum sulfonate, wherein the thickening agent is a lithium-based thickening agent; the thiuram compound is present in an amount of 3 to 50g, preferably 5 to 40g (e.g. 5g, 10g, 11g, 15g, 17g, 20g, 22g, 25g, 28g, 30g, 35g, 37g, 40g or any value therebetween) per kg of base oil; the calcium petroleum sulfonate is present in an amount of 3 to 50g, preferably 5 to 35g (e.g. 5g, 10g, 11g, 12g, 15g, 17g, 18g, 20g, 22g, 25g, 27g, 30g, 35g or any value therebetween).
According to the invention, the thiuram compound may be of any conventional type
(x is an integer of 1 to 10) a skeletal structure, but preferably, the thiuram compound has the formula:
wherein R is1、R2、R3And R4Each independently is C1-C10 alkyl, C6-C14 aryl or C3-C10 cycloalkyl, or R1And R2Cyclizing to a three-to ten-membered azacyclic ring and R3And R4Each independently is C1-C10 alkyl, C6-C14 aryl or C3-C10 cycloalkyl, or R1And R2Each independently is C1-C10 alkyl, C6-C14 aryl or C3-C10 cycloalkyl and R3And R4Cyclized to a three-to ten-membered azacyclic ring, or R1And R2Cyclizing to a three-to ten-membered azacyclic ring and R3And R4Cyclizing to form a three-to ten-membered nitrogen heterocycle,
wherein x is an integer of 1 to 10.
The term "alkyl" used alone or in combination with other terms includes straight or branched chain C1-C10 alkyl, which means a monovalent alkyl group having 1-10 carbon atoms. The term may cite the following groups: such as methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i-butyl, t-butyl, n-pentyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl.
The term "aryl" means an unsaturated aromatic carbocyclic group of 6 to 14 carbon atoms with a single ring (e.g., phenyl) or multiple condensed rings (e.g., indenyl, naphthyl). Examples of aryl groups include phenyl, naphthyl, anthryl, phenanthryl, and the like.
The term "cycloalkyl" refers to a saturated carbocyclic group of 3 to 10 carbon atoms having a single ring (e.g., cyclohexyl) or multiple condensed rings (e.g., norbornyl). Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, norbornyl, and the like.
R1And R2(or R)3And R4) Cyclizing to a three-to ten-membered azacyclic ring means R1And R2(or R)3And R4) Can form ternary, quaternary, quinary, hexabasic, heptabasic, octabasic, nonabasic or decabasic nitrogen heterocycles, especially monoazacyclo.
Preferably, the sulfur element in the thiuram compound is not less than 50% by weight, preferably 50 to 60% by weight.
According to a more preferred embodiment of the present invention, the thiuram compound is at least one of tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide and dipentamethylenethiuram hexasulfide.
According to the present invention, calcium petroleum sulfonate is a substance in which carboxyl hydrogen in petroleum sulfonic acid is substituted with calcium. The calcium petroleum sulfonate may be a conventional choice in the art, such as TBN 150. Preferably, the total base number (TBN value) of the petroleum calcium sulfonate is not more than 200mg KOH/g, preferably 100-200mg KOH/g. In the present invention, the test criteria for "total base number" are: SH/T0251, "method of measuring the base number of Petroleum products (Perchloric acid potentiometry"), indicates the amount of perchloric acid required to neutralize all of the basic components in a 1g sample (calcium petroleum sulfonate), expressed in milligrams of equivalent potassium hydroxide.
According to the present invention, the content of the base oil is not particularly limited, and for example, the content of the base oil may be 75 to 97 wt%, preferably 80 to 95 wt% (e.g., 80 wt%, 82 wt%, 83 wt%, 84 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 95 wt%, or any value therebetween), based on the total weight of the grease composition.
According to the present invention, the base oil may be various base oils used in greases, such as mineral oils, synthetic oils (silicone oils, olefin oils, and/or ester oils), vegetable oils, or mixtures thereof. Preferably, the base oil has a kinematic viscosity at 100 ℃ of 4 to 100mm2(ii) fats and oils in s. In the present invention, "kinematic viscosity" is measured with reference to GB/T265-1988.
According to the present invention, the amount of the thickener is not particularly limited, and may be 30 to 200g, preferably 50 to 165g (e.g., 50g, 55g, 60g, 65g, 70g, 75g, 78g, 80g, 85g, 88g, 90g, 95g, 100g, 102g, 105g, 110g, 115g, 118g, 120g, 130g, 135g, 140g, 145g, 150g, 155g, 160g, 165g, or any value therebetween) per kg of the base oil.
According to the present invention, the thickener may be various conventional lithium-containing thickeners, such as lithium soaps. Preferably, the thickener is a lithium fatty acid, more preferably lithium stearate and/or lithium 12-hydroxystearate.
According to the present invention, the grease composition may further contain an auxiliary such as a rust inhibitor, an oiliness agent, and an antioxidant. The antioxidant can further improve the oxidation resistance of the lubricating grease composition, so that the service life of the lubricating grease composition is prolonged, and the antioxidant can be aromatic amine antioxidant, such as at least one of diphenylamine, phenyl-alpha-naphthylamine and diisooctyldiphenylamine. The antioxidant may be present in an amount of 0.01 to 5 wt.%, based on the total weight of the grease composition.
The oiliness agent can further improve the lubricating property of the friction pair surface, and can be higher fatty acid (such as oleic acid and stearic acid), higher alcohol (such as stearyl alcohol), alkylamine (such as phenyltriazolyl stearyl amine) and the like. The content of the oiliness agent may be 0.01 to 4.5% by weight based on the total weight of the grease composition.
The antirust agent can further improve the rust resistance of the lubricating grease composition and can be at least one of barium petroleum sulfonate, sodium petroleum sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid. The rust inhibitor may be contained in an amount of 0.01 to 4.5% by weight, based on the total weight of the grease composition.
According to a preferred embodiment of the present invention, the grease composition consists of only the above-mentioned ingredients.
The method for preparing the lubricating grease composition comprises the following steps: mixing the thickening agent and part of the base oil, heating, and mixing with the thiuram compound, the calcium petroleum sulfonate and the rest of the base oil.
In the present invention, when the thickener is lithium fatty acid, the thickener may be synthesized in situ, and thus, the method may include: mixing fatty acid and a lithium source in the presence of part of base oil, heating to raise the temperature, introducing the rest base oil, cooling, introducing a thiuram compound and calcium petroleum sulfonate, continuously cooling, and introducing an optional auxiliary agent. More specifically, the method may include: mixing part of base oil with fatty acid, heating to 80-90 ℃, introducing a water solution of a lithium source, stirring and heating to 200-210 ℃, introducing the rest base oil, cooling and cooling the materials, introducing a thiuram compound and calcium petroleum sulfonate when the temperature is reduced to 110-130 ℃, stirring for 10-20min, continuously cooling to 80-90 ℃, and introducing an optional auxiliary agent. Generally, the mixture finally obtained should also be subjected to a grinding treatment to make the material dispersion more uniform.
Wherein the lithium source may be at least one of lithium oxide, lithium hydroxide, and lithium alkoxide (such as methoxy compound, ethoxy compound, etc.) (with water as solvent). The alkoxy compound may have the formula Li+(OR)-Wherein, R can be C1-C10 alkyl, preferably C2-C6 alkyl, such as methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl or tert-pentyl. Further, the lithium source is preferably lithium hydroxide. The fatty acid may be stearic acid and/or 12-hydroxystearic acid.
The present invention will be described in detail below by way of examples. In the following examples:
mineral oil 1 (kinematic viscosity at 100 ℃ C. of 10 mm)2S) and mineral oil 2 (kinematic viscosity at 100 ℃ of 30 mm)2/s) from the Beijing Yanshan petrochemical;
olefin oil 1 (kinematic viscosity at 100 ℃ C. of 6 mm)2S) and olefin oil 2 (kinematic viscosity at 100 ℃ of 40mm2/s) from Exxon Mobil;
silicone oil (kinematic viscosity at 100 ℃ of 40 mm)2/s) purchased from Sichuan Chen photochemistry;
thiuram 1 was tetramethylthiuram disulfide (sulfur content 53.3 wt%), thiuram 2 was dipentamethylenethiuram hexasulfide (sulfur content 57 wt%), thiuram 3 was dipentamethylenethiuram tetrasulfide (sulfur content 50 wt%), thiuram 4 was dipentamethylenethiuram hexasulfide (sulfur content 57 wt%), all available from henna Longji chemical Co., Ltd;
the TBN value of the petroleum calcium sulfonate 1 is 50mgKOH/g, the TBN value of the petroleum calcium sulfonate 2 is 100mgKOH/g, the TBN value of the petroleum calcium sulfonate 3 is 150mgKOH/g, the TBN value of the petroleum calcium sulfonate 4 is 200mgKOH/g, and the TBN values are purchased from Handan Ningong lubricating oil additive limited company;
12-Hydroxystearic acid was purchased from Tongliaoxing science and technology, Inc.;
lithium hydroxide was purchased from Sichuan national lithium materials, Inc.;
the rust inhibitor is zinc naphthenate (brand T704) which is purchased from Jinzhou Kangtai lubricating oil additive GmbH;
the antioxidant was diisooctyldiphenylamine (trade name V81) available from Van der Bill Limited.
Examples 1 to 14
According to the mixture ratio shown in table 1 and table 2 (weight percentage of the total weight of the grease composition, the calculation mode of the lithium fatty acid is (mass of 12-hydroxy fatty acid/molecular weight of 12-hydroxy fatty acid x molecular weight of 12-hydroxy fatty acid)/total weight of the composition x 100%, in a reaction kettle, base oil with about 2/3 of base oil and 12-hydroxystearic acid are added, the temperature is raised to 85 +/-5 ℃, lithium hydroxide aqueous solution is added, the temperature is raised to 205 +/-5 ℃, the rest base oil with about 1/3 is added, the material is cooled, when the temperature is lowered to about 130 ℃, thiuram compound and calcium petroleum sulfonate are added, the stirring is carried out for about 15min, the temperature is further lowered to 85 +/-5 ℃, the rest auxiliary agents (antirust agent and antioxidant) are added, the material is ground by three-wheel mill to be uniformly dispersed, grease composition samples were prepared.
Example 15
A sample of grease composition was prepared according to the method of example 1, except that the thiuram compound was replaced with tetraisobutylthiuram disulfide (sulfur content 31.3 wt%).
Example 16
A sample of grease composition was prepared as in example 1, except that calcium petroleum sulfonate was replaced with calcium petroleum sulfonate having a TBN of 300mg KOH/g.
Comparative example 1
A grease composition sample was prepared as in example 1, except that calcium petroleum sulfonate was replaced with an equal weight of base oil.
Comparative example 2
A grease composition sample was prepared in accordance with the method of example 1, except that the thiuram compound was replaced with an equal weight of base oil.
Comparative example 3
A grease composition sample was prepared in accordance with the procedure of example 1, except that the thiuram compound and calcium petroleum sulfonate were not used, but replaced with an equal weight of sulfurized isobutylene (code No. T321).
Comparative example 4
A grease composition sample was prepared in accordance with the method of example 1, except that the thiuram compound and calcium petroleum sulfonate were not used, but were replaced with an equal weight of thiocarbamate (code number T323).
Comparative example 5
The molybdenum dialkyldithiocarbamate and the tetrabenzylthiuram disulfide compound of CN104024389A, example 1, were added to the grease composition described in example 1, the specific composition of the grease composition being: 89 percent by weight of mineral oil 1, 10 percent by weight of lithium fatty acid, 0.7 percent by weight of molybdenum dialkyl dithiocarbamate and 0.3 percent by weight of tetra-benzyl thiuram disulfide.
Comparative example 6
A grease composition sample was prepared as in example 1, except that lithium hydroxide was replaced with sodium hydroxide.
Comparative example 7
A sample of grease composition was prepared according to the method of example 1, except that the thiuram compound was present in an amount of 0.2 wt% and the calcium petroleum sulfonate was present in an amount of 1.8 wt%.
Comparative example 8
A sample of grease composition was prepared according to the method of example 1, except that the thiuram compound was present in an amount of 1.8 wt% and the calcium petroleum sulfonate was present in an amount of 0.2 wt%.
Test example 1
The physical and chemical properties of the grease composition samples obtained in the above examples and comparative examples were analyzed as follows:
penetration (25 ℃, 0.1mm, 60 times): GB/T269-1991, the smaller the cone penetration is in 60 times of work, which indicates that the thickening capacity is stronger;
dropping point: GB/T3498-2008, the higher the dropping point, the better the high temperature performance;
extreme pressure Properties (maximum non-seizure load, P)BValue): SH/T0202-;
extreme pressure Properties (sintering load, P)DValue): SH/T0202-;
abrasion resistance (d value): SH/T0204-;
coefficient of friction (f value): SH/T0204-.
Wherein, PBValue sum PDThe larger the value is, the smaller the value d is, the stronger the extreme pressure wear resistance is; the smaller the f-number, the better the lubricating property.
The results are shown in tables 1-3.
TABLE 1
TABLE 2
| Item | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 | Example 13 | Example 14 |
| Mineral oil 1 | 87 | 88 | |||||
| Mineral oil 2 | 83 | ||||||
| Olefin oil 1 | 87 | 85.5 | |||||
| Olefin oil 2 | 89.5 | ||||||
| Silicone oil | 90 | ||||||
| Lithium fatty acid ester | 9 | 12 | 9 | 10 | 6 | 8 | 9 |
| Thiuram 1 | 1 | 2.5 | 0.5 | ||||
| Thiuram 2 | 0.5 | 0.5 | 0.5 | ||||
| Thiuram 3 | 1.5 | 0.5 | 0.5 | ||||
| Thiuram 4 | 1.5 | 1 | 0.5 | ||||
| Petroleum sulfonic acid calcium 1 | 1 | 0.5 | 2.5 | 0.5 | |||
| Petroleum sulfonic acid calcium 2 | 1.5 | 0.5 | |||||
| Calcium petroleum sulfonate 3 | 0.5 | 0.5 | |||||
| Petroleum sulfonic acid calcium 4 | 1.5 | 1 | 0.5 | 0.5 | |||
| Rust inhibitor | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | ||
| Antioxidant agent | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | ||
| Penetration of cone | 277 | 272 | 275 | 271 | 276 | 277 | 276 |
| Dropping Point (. degree.C.) | 190 | 190 | 188 | 187 | 191 | 190 | 189 |
| PBValue (N) | 1098 | 1236 | 1236 | 1098 | 1098 | 1098 | 1098 |
| PDValue (N) | 3923 | 4904 | 4904 | 6080 | 4904 | 4904 | 4904 |
| d value (mm) | 0.39 | 0.43 | 0.42 | 0.40 | 0.41 | 0.41 | 0.42 |
| f value | 0.0611 | 0.0607 | 0.0604 | 0.0622 | 0.0613 | 0.0634 | 0.0629 |
TABLE 3
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. The lubricating grease composition containing the thiuram compound is characterized by comprising base oil, a thickening agent, the thiuram compound and calcium petroleum sulfonate, wherein the thickening agent is a lithium-based thickening agent; the thiuram compound is contained in an amount of 3 to 50g and the calcium petroleum sulfonate is contained in an amount of 3 to 50g per kg of the base oil.
2. Grease composition according to claim 1, wherein the thiuram compound is present in an amount of 5-40g per kg of base oil.
3. Grease composition according to claim 1 or 2, wherein the thiuram compound has the formula:
wherein R is1、R2、R3And R4Each independently is C1-C10 alkyl, C6-C14 aryl or C3-C10 cycloalkyl, or R1And R2Cyclizing to a three-to ten-membered azacyclic ring and R3And R4Each independently is C1-C10 alkyl, C6-C14 aryl or C3-C10 cycloalkyl, or R1And R2Each independently is C1-C10 alkyl, C6-C14 aryl or C3-C10 cycloalkyl and R3And R4Cyclized to a three-to ten-membered azacyclic ring, or R1And R2Cyclizing to a three-to ten-membered azacyclic ring and R3And R4Cyclizing to form a three-to ten-membered nitrogen heterocycle,
wherein x is an integer of 1 to 10;
preferably, the amount of sulfur element in the thiuram compound is not less than 50 wt%;
more preferably, the thiuram compound is at least one of tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide and dipentamethylenethiuram hexasulfide.
4. Grease composition according to claim 1, wherein the calcium petroleum sulphonate content is from 5 to 35g per kg of base oil.
5. Grease composition according to claim 1 or 4, wherein the total base number of the calcium petroleum sulfonate is not more than 200mg KOH/g.
6. Grease composition according to claim 1, wherein the base oil is present in an amount of 75-97 wt.%, preferably 80-95 wt.%, based on the total weight of the grease composition.
7. A grease composition according to claim 1 or 6, wherein the base oil has a kinematic viscosity at 100 ℃ of 4-100mm2/s。
8. Grease composition according to claim 1, wherein the thickener is present in an amount of 30-200g, preferably 50-165g, per kg of base oil.
9. Grease composition according to claim 1 or 8, wherein the thickener is a lithium fatty acid, preferably lithium stearate and/or lithium 12-hydroxystearate.
10. A method of preparing a grease composition according to any one of claims 1-9, characterized in that the method comprises: mixing the thickening agent and part of the base oil, heating, and mixing with the thiuram compound, the calcium petroleum sulfonate and the rest of the base oil.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB811860A (en) * | 1956-03-08 | 1959-04-15 | Wakefield & Co Ltd C C | Improvements in or relating to lubricating compositions |
| JPS53138407A (en) * | 1977-05-10 | 1978-12-02 | Hitachi Ltd | Lubricating grease |
| JP2018016725A (en) * | 2016-07-28 | 2018-02-01 | 協同油脂株式会社 | Silicone grease composition |
-
2019
- 2019-10-29 CN CN201911039620.5A patent/CN112745979B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB811860A (en) * | 1956-03-08 | 1959-04-15 | Wakefield & Co Ltd C C | Improvements in or relating to lubricating compositions |
| JPS53138407A (en) * | 1977-05-10 | 1978-12-02 | Hitachi Ltd | Lubricating grease |
| JP2018016725A (en) * | 2016-07-28 | 2018-02-01 | 協同油脂株式会社 | Silicone grease composition |
Non-Patent Citations (1)
| Title |
|---|
| 李群芳等: "润滑油金属清净剂(钙盐)的抗磨作用概述", 《润滑油》 * |
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