CN107502412B - High-temperature-resistant magnesium salt lubricating oil detergent and preparation method thereof - Google Patents
High-temperature-resistant magnesium salt lubricating oil detergent and preparation method thereof Download PDFInfo
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- 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
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- C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
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- 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
- C10M2201/16—Carbon dioxide
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- 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
- C10M2203/06—Well-defined aromatic 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
- 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
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- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2211/04—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen, halogen, and oxygen
- C10M2211/044—Acids; Salts or esters thereof
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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
- C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2211/04—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen, halogen, and oxygen
- C10M2211/044—Acids; Salts or esters thereof
- C10M2211/0445—Acids; Salts or esters thereof 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
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/04—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/08—Resistance to extreme temperature
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Abstract
A high-temperature resistant magnesium salt lubricating oil detergent comprises the following raw materials: 2-15 mol% of 12-fluorobenzeneacetyl stearic acid, 3-20 mol% of base oil, 10-50 mol% of active magnesium oxide, 15-45 mol% of solvent, 0.5-5 mol% of accelerator, 1-5 mol% of methanol, 0.5-3 mol% of dispersant and 5-35 mol% of carbon dioxide, wherein the 12-fluorobenzeneacetyl stearic acid has a molecular structure shown in the formula I. The metal magnesium salt lubricating oil detergent disclosed by the invention is strong in hydrophobicity and good in high-temperature carbon deposition resistance, and particularly, the copolymer of fumaric acid and hexafluorobutyl acrylate is used as a hyperdispersant, so that the problems of stable dispersion of alkaline carbonate and self-oxidation to carbon in a high-temperature state are solved.
Description
Technical Field
The invention belongs to the technical field of chemical products, and particularly relates to a high-temperature-resistant magnesium salt lubricating oil detergent and a preparation method thereof.
Background
The lubricating oil is a liquid or semisolid lubricating agent used on various types of automobiles and mechanical equipment to reduce friction and protect machines and workpieces, and mainly plays roles in lubrication, cooling, rust prevention, cleaning, sealing, buffering and the like. However, in the use process of the engine lubricating oil, due to harsh working conditions and high-temperature oxidation, and the absorption of acid gases of nitrogen oxides and sulfur dioxide from the outside, the lubricating oil is prone to oxidative degradation, and a certain amount of acid corrosive substances, such as sulfuric acid, nitric acid, acid sludge and the like, are generated, so that the lubricating effect of the lubricating oil is reduced and the corrosion to equipment is aggravated. Therefore, it is necessary to add a lubricating oil detergent to continuously neutralize acidic substances generated during the use of the lubricating oil and prevent the acidic substances from corroding the engine, so that the purposes of prolonging the service life of the lubricating oil and protecting the engine are achieved.
The metal detergent for lubricating oil is a widely used lubricating oil additive, and can be added to continuously neutralize acidic substances generated by oxidative degradation of engine oil in the using process, so that corrosion of the engine oil to the engine is prevented, and meanwhile, due to the emulsification effect of detergent soap salt to harmful particles, the purposes of slowing down oil deterioration and prolonging service life can be achieved. However, with the development of environment-friendly ester lubricating oils in recent years, higher requirements are also put forward on the environmental protection performance of the lubricating oil, the traditional detergent products such as sulfonate, naphthenate and the like have the disadvantage of poor matching with the ester lubricating oil, the addition of the detergent products can influence the color and the performance of the base oil of the lubricating oil, and meanwhile, the detergent products do not meet the requirements in the aspects of environmental protection, emission regulations and energy conservation, and the development of novel detergent products is imperative.
For example, CN 104263457A discloses a 12-isooctanoate magnesium stearate detergent prepared by using 12-isooctanoate stearic acid and magnesium oxide to achieve a neutralization overbasing reaction by mechanical stirring. CN 105238500A discloses a metal magnesium salt lubricating oil detergent, which comprises the following raw materials: 0.5-2 parts of 12-butyryloxy stearic acid, 2-4 parts of pentaerythritol tetraheptanoate base oil, 1-5 parts of magnesium hydroxide, 15-30 parts of solvent, 0.1-1 part of methanol, 0.5-5 parts of concentrated ammonia water and 0.5-3 parts of carbon dioxide. CN 103265995A discloses a lubricating oil detergent and a preparation method thereof, wherein the detergent comprises the following raw materials in parts by mass: 1 part of linoleic acid, 1-2 parts of neutral oil, 1-6 parts of calcium hydroxide, 0.2-1 part of calcium oxide, 0-0.1 part of calcium chloride, 3-10 parts of solvent, 0.2-1 part of methanol, 0.1-0.5 part of water and 0.1-0.4 part of carbon dioxide.
However, the conventional lubricating oil detergent and the lubricating oil detergent are basically prepared by dispersing alkaline components in diluent oil by using organic acids with common carbon chains, such as dodecylbenzene sulfonic acid, alkyl salicylic acid, oleic acid, linoleic acid and the like, through reaction, the diluent oil is mainly common lubricating oil base oil, such as 150SN, 250SN, 350SN and other types of base oil, which is a product refined from petroleum, or common synthetic ester base oil, but the raw materials, namely the organic acid and the diluent oil, are compounds of common carbon steel, so that the high temperature resistance is poor, the organic acid and the diluent oil are easily degraded under the action of high temperature, carbon deposition is further generated, and the carbon deposition resistance is poor.
Disclosure of Invention
Therefore, the invention aims to provide a high-temperature resistant magnesium salt lubricating oil detergent which has excellent high-temperature resistance and anti-carbon deposition performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-temperature resistant magnesium salt lubricating oil detergent comprises the following raw materials:
wherein the 12-fluorophenylacetyl stearic acid has a molecular structure as shown in formula I:
preferably, the high temperature resistant magnesium salt lubricating oil detergent of the invention comprises the following raw material components:
preferably, the 12-fluorophenylacetyl stearic acid is obtained by reacting 2,3, 4-trifluorophenylacetic acid with 12-hydroxystearic acid.
Preferably, the molar ratio of 2,3, 4-trifluorophenylacetic acid to 12-hydroxystearic acid is 1:0.5-2, preferably 1: 1.
Preferably, the reaction is catalyzed using stannous chloride and xylene as the water-carrying agent.
Preferably, the reaction temperature is 120-160 ℃ and the reaction time is 1-5 h.
Preferably, the 12-fluorophenylacetylstearic acid is obtained by removing the water-carrying agent after the reaction. The removal of the water-carrying agent is preferably carried out under reduced pressure.
One preferred embodiment of the preparation of 12-fluorophenylacetyl stearic acid of the present invention is: the 12-fluorobenzeneacetyl stearic acid is prepared by reacting 2,3, 4-trifluorophenylacetic acid and 12-hydroxystearic acid in a molar ratio of 1:1 under the catalysis of stannous chloride and xylene as a water-carrying agent at 160 ℃ for 1-5h, and removing a xylene solvent under reduced pressure to obtain the 12-fluorobenzeneacetyl stearic acid. The synthesis process and the molecular structure are as follows:
preferably, the base oil is trimethylolpropane tris (trifluoropentanoate) ester having a molecular structure of formula II below:
the metal magnesium salt lubricating oil detergent disclosed by the invention uses fluorine-containing compounds such as 12-fluorobenzene acetyl stearic acid and trimethylolpropane tri (trifluoro valeric acid) ester as raw materials, and the prepared product has strong hydrophobicity and good high-temperature carbon deposition resistance.
Preferably, the trimethylolpropane tris (trifluoropentanoate) ester is obtained by reacting trimethylolpropane with 5,5, 5-trifluoropentanoic acid.
Preferably, the molar ratio of trimethylolpropane to 5,5, 5-trifluoropentanoic acid is 1:2-4, preferably 1: 3.
Preferably, the reaction is catalyzed with tetrabutyl titanate using toluene as a water-carrying agent.
Preferably, the reaction temperature is 110-130 ℃ and the reaction time is 2-8 h.
Preferably, removal of the water-carrying agent after the reaction yields trimethylolpropane tris (trifluoropentanoic acid) ester, and removal of the water-carrying agent is preferably carried out under reduced pressure.
Preferably, the activated magnesium oxide is activated-60 magnesium oxide and/or activated-80 magnesium oxide, preferably activated-80 magnesium oxide.
Preferably, the solvent comprises a combination of 1 or 2 or more of benzene solvents and water, preferably comprises 80 to 99.5 mol% of benzene solvents and 0.5 to 20 mol% of water, and further preferably comprises 85 to 99 mol% and 1 to 15 mol% of water.
Preferably, the benzene-based solvent is toluene and/or xylene.
Preferably, the promoter is triethylamine.
Preferably, the cosolvent is methanol.
Preferably, the dispersing agent is a copolymer of fumaric acid and hexafluorobutyl acrylate, and the weight-average molecular weight is preferably 1200-1500. The copolymer of fumaric acid and hexafluorobutyl acrylate is used as the hyperdispersant, so that the problem of stable dispersion of basic carbonate and the problem of self oxidation to carbon under a high temperature state are solved, and the lubricating oil detergent disclosed by the invention has excellent high temperature resistance and anti-carbon deposition performance, and particularly excellent high temperature resistance and anti-carbon deposition performance when the weight-average molecular weight of the copolymer is 1200-1500. The preparation method of the copolymer of fumaric acid and hexafluorobutyl acrylate is the existing free radical polymerization method, the initiator can be AIBN and/or BPO, preferably BPO, and the dosage of the initiator is 1 percent of the total mass of the materials.
Preferably, the high temperature resistant magnesium salt lubricating oil detergent of the invention comprises the following raw material components:
the sum of the contents of the components is less than or equal to 100 percent.
The metal magnesium salt lubricating oil detergent disclosed by the invention adopts the fluorinated organic acid as a raw material, the copolymer of fumaric acid and hexafluorobutyl acrylate as a hyperdispersant, the finally prepared product is strong in hydrophobicity and good in high-temperature carbon deposition resistance, and particularly the copolymer of fumaric acid and hexafluorobutyl acrylate is used as the hyperdispersant, so that the stable dispersion problem of basic carbonate and the problem of self-oxidation into carbon under a high-temperature state are ensured.
One of the objectives of the present invention is to provide a method for preparing the high temperature resistant magnesium salt lubricating oil detergent of the present invention, comprising the following steps:
(1) mixing raw materials of 12-fluoro phenylacetyl stearic acid, base oil, magnesium oxide, a dispersant, a solvent, an accelerant and a cosolvent at the temperature of 30-55 ℃ for neutralization for more than 0.5 hour;
(2) heating and introducing carbon dioxide gas;
(3) removing residues and the solvent to obtain the lubricating oil detergent.
Preferably, the time for neutralization in step (1) is 1 to 5 hours.
The mixing can be carried out with stirring.
Preferably, the deslagging in step (3) may be performed by centrifugation or filtration.
Preferably, the desolventizing agent can be removed by distillation under reduced pressure.
Preferably, the preparation method of the metal magnesium salt lubricating oil detergent comprises the following steps:
A. adding organic acid, base oil, active magnesium oxide, solvent, promoter, cosolvent and dispersant in formula ratio into a reactor, and stirring for fully mixing;
B. neutralizing at 30-55 deg.c for 1-5.0 hr;
C. then heating to 60-80 ℃, introducing carbon dioxide gas with the formula amount, wherein the aeration rate is 50-200mL/min, and preferably 100 mL/min;
D. centrifuging or filtering to remove residue, and distilling under reduced pressure to remove solvent to obtain lubricating oil detergent.
The traditional lubricating oil detergent basically uses common carbon chain organic acids, such as dodecyl benzene sulfonic acid, alkyl salicylic acid, oleic acid and the like, alkaline components are dispersed in diluent oil through reaction, the diluent oil is mainly common lubricating oil base oil, such as 150SN, 250SN, 350SN and other types of base oil, which is a product refined from petroleum, or common synthetic ester base oil, but the raw materials, namely the organic acids and the diluent oil, are common carbon steel compounds, so that the high temperature resistance is poor, the carbon deposition is easily generated under the action of high temperature, and the carbon deposition resistance is poor; the invention adopts fluoro organic acid with excellent hydrophobicity and high temperature resistance, preferably matches fluoro dispersant and fluoro synthetic ester base oil as raw materials, adopts fluoro compound in the main organic raw material, and can better ensure the high temperature resistance and the carbon deposition resistance of the final product.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
Example 1
A high-temperature resistant magnesium salt lubricating oil detergent comprises the following raw materials: 5mol of 12-fluorophenylacetyl stearic acid, 10mol of trimethylolpropane tris (trifluoropentanoate) base oil and 35mol of active-80 magnesium oxide (Shanghai Dunhuang chemical plant); 25mol of xylene, 2mol of triethylamine, 2mol of methanol, 1mol of a copolymer (weight average molecular weight 1300) of fumaric acid and hexafluorobutyl acrylate, 1mol of water and 19mol of carbon dioxide. The preparation method comprises the following steps:
A. adding 12-fluorobenzeneacetyl stearic acid, 4-trifluoromethoxybenzoic acid, magnesium oxide, a dispersing agent, a solvent, an accelerant and a cosolvent into a reactor according to the formula amount, and stirring and fully mixing;
B. neutralizing at 30-55 deg.c for 1-5.0 hr;
C. then heating to 60-80 ℃, and introducing carbon dioxide gas with the formula amount at the aeration rate of 100 mL/min;
D. centrifuging or filtering to remove residue, and distilling under reduced pressure to remove solvent to obtain lubricating oil detergent.
Example 2
A high-temperature resistant magnesium salt lubricating oil detergent comprises the following raw materials: 8mol of 12-fluorophenylacetyl stearic acid, 20mol of trimethylolpropane tris (trifluoropentanoate) base oil and 40mol of active-80 magnesium oxide (Shanghai Dunhuang chemical plant); 15mol of dimethylbenzene, 5mol of triethylamine, 1mol of methanol, 0.5mol of a copolymer (weight average molecular weight 1200) of fumaric acid and hexafluorobutyl acrylate, 0.5mol of water and 10mol of carbon dioxide.
The preparation method is the same as example 1.
Example 3
A high-temperature resistant magnesium salt lubricating oil detergent comprises the following raw materials: 15mol of 12-fluorophenylacetyl stearic acid, 5mol of trimethylolpropane tris (trifluoropentanoate) base oil and 20mol of active-80 magnesium oxide (Shanghai Dunhuang chemical plant); 40mol of toluene, 0.5mol of triethylamine, 5mol of methanol, 3mol of a copolymer (weight average molecular weight 1500) of fumaric acid and hexafluorobutyl acrylate, 2mol of water and 9.5mol of carbon dioxide.
The preparation method is the same as example 1.
Example 4
A high-temperature resistant magnesium salt lubricating oil detergent comprises the following raw materials: 15mol of 12-fluorophenylacetyl stearic acid, 20mol of trimethylolpropane tris (trifluoropentanoic acid) ester base oil, 20mol of active-80 magnesium oxide (Shanghai Dunhuang chemical plant), 20mol of xylene, 4mol of triethylamine, 3mol of methanol, 2mol of a copolymer (weight average molecular weight 1400) of fumaric acid and hexafluorobutyl acrylate, 1mol of water and 15mol of carbon dioxide.
The preparation method is the same as example 1.
Example 5
A high-temperature resistant magnesium salt lubricating oil detergent comprises the following raw materials: 13mol of 12-fluorophenylacetyl stearic acid, 10mol of trimethylolpropane tris (trifluoropentanoate) base oil, 10mol of active-80 magnesium oxide (Shanghai Dunhuang chemical plant), 30mol of toluene, 3mol of triethylamine, 4mol of methanol, 3mol of a copolymer of fumaric acid and hexafluorobutyl acrylate (weight-average molecular weight 1360), 2mol of water, and 25mol of carbon dioxide.
The preparation method is the same as example 1.
The appearance of the product made in the above example: a light yellow transparent liquid; base number: 320-380 mgKOH/g; viscosity of 30-50mm2And s. Specific results are shown in table 1 below.
Comparative example 1
Otherwise, as in example 1, only 12-fluorophenylacetylstearic acid was replaced with a commercially available alkylbenzenesulfonic acid, a commercial product, which was obtained from Nanjing Seisaku chemical Co., Ltd.
Comparative example 2
Otherwise, as in example 1, only 12-fluorophenylacetylstearic acid was replaced with commercially available purified naphthenic acid, which was commercially available from chemical Co., Ltd.
Comparative example 3
Otherwise as in example 1, only 12-fluorophenylacetylstearic acid was replaced with commercially available alkylsalicylic acid, commercial available from san Jose Chemicals, Inc., of California.
Comparative example 4
Otherwise, just as in example 1, the trimethylolpropane tris (trifluoropentanoate) base oil was replaced with a conventional commercially available diluent oil (150SN base oil), which was purchased from oil products, Inc., Possent, Suzhou.
Comparative example 5
Otherwise, just as in example 1, the trimethylolpropane tris (trifluoropentanoate) base oil was replaced with a conventional commercially available diluent oil (350SN base oil), which was purchased from oil products, Inc., of Sazhou Hessent.
Comparative example 6
Otherwise, as in example 1, the commercial dispersant polyethylene glycol (PEG-1000) commercial product was replaced with a copolymer of fumaric acid and hexafluorobutyl acrylate (molecular weight 1300) and purchased from Haian petrochemical plant of Jiangsu province.
Comparative example 7
The procedure is as in example 1 except that the molecular weight of the copolymer of fumaric acid and hexafluorobutyl acrylate is 1000.
Comparative example 8
The procedure is as in example 1 except that the molecular weight of the copolymer of fumaric acid and hexafluorobutyl acrylate is 2000.
The lubricating oil detergents prepared in the examples and comparative examples were tested for base number, viscosity, thermal stability and colloidal matter precipitation, as follows, and the results are shown in Table 1 below.
The test method comprises the following steps: the base number determination is carried out according to SH/T0251-1993 petroleum product base number determination method (perchloric acid potentiometric titration method); the viscosity measurement is based on GB/T265-88 petroleum product kinematic viscosity measurement method and dynamic viscometer algorithm; the thermal stability and colloidal precipitation were determined by SH/T0300-92 crankcase simulation test method (QZX method).
TABLE 1
The invention uses fluoro organic acid, fluoro base oil and fluoro dispersant to make the fluoro magnesium salt detergent product with excellent high temperature resistance, while the organic acid raw materials of the main detergent product in the market, such as alkyl benzene sulfonic acid, naphthenic acid, alkyl salicylic acid, etc., and the diluent oil, such as 150SN base oil, 250SN base oil, 350SN base oil, etc., are all common carbon chain structures, and have insufficient self oxidation resistance, the use of these raw materials can cause the high temperature resistance to be reduced, the precipitation of colloid is obvious, see the comparison of comparative examples 1-5 and example 1 in detail. The copolymer (molecular weight 1200-1500) of fumaric acid and hexafluorobutyl acrylate, which is the fluoro dispersant, used in the invention has good compatibility with a system, so that the copolymer is easier to play a role of dispersing colloidal carbonate in the fluoro system, and the overall stability of a detergent system is better, therefore, the common commercially available dispersant polyethylene glycol (PEG-1000) has poor compatibility with the fluoro system, so that the dispersing ability is poor, and colloidal substances are easy to precipitate. As can be seen from comparison of comparative examples 7 and 8 with example 1, the molecular weight of the copolymer of fumaric acid and hexafluorobutyl acrylate is not in the range of 1200-1500, and the overall properties of the obtained product are significantly inferior to those of the product obtained with the molecular weight of the copolymer in the range of 1200-1500.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A high-temperature resistant magnesium salt lubricating oil detergent comprises the following raw materials:
the dispersing agent is a copolymer of fumaric acid and hexafluorobutyl acrylate;
wherein the 12-fluorophenylacetyl stearic acid has a molecular structure as shown in formula I:
2. the magnesium salt lubricating oil detergent of claim 1, wherein the 12-fluorophenylacetyl stearic acid is obtained by reacting 2,3, 4-trifluorophenylacetic acid with 12-hydroxystearic acid.
3. The magnesium salt lubricating oil detergent of claim 2, wherein the molar ratio of 2,3, 4-trifluorophenylacetic acid to 12-hydroxystearic acid is 1: 0.5-2;
the reaction is catalyzed by stannous chloride, and dimethylbenzene is used as a water-carrying agent;
the reaction temperature is 120-160 ℃, and the reaction time is 1-5 h;
removing the water-carrying agent after the reaction to obtain the 12-fluorophenylacetyl stearic acid.
4. The magnesium salt lubricating oil detergent of claim 1, wherein the base oil is trimethylolpropane tris (trifluoropentanoate) ester having a molecular structure of formula II:
5. the magnesium salt lubricating oil detergent of claim 4, wherein the trimethylolpropane tris (trifluoropentanoate) is obtained by reacting trimethylolpropane with 5,5, 5-trifluoropentanoic acid.
6. The magnesium salt lubricating oil detergent of claim 5, wherein the molar ratio of trimethylolpropane to 5,5, 5-trifluoropentanoic acid is 1: 2-4;
the reaction is catalyzed by tetrabutyl titanate, and toluene is used as a water-carrying agent;
the reaction temperature is 110-130 ℃, and the reaction time is 2-8 h;
removing the water-carrying agent after the reaction to obtain the trimethylolpropane tri (trifluoro valeric acid) ester.
7. The magnesium salt lubricating oil detergent of claim 1, wherein the active magnesium oxide is active-60 magnesium oxide and/or active-80 magnesium oxide.
8. The magnesium salt lubricating oil detergent of claim 1, wherein the solvent comprises a combination of 1 or 2 or more of benzene-based solvents and water;
the benzene solvent is toluene and/or xylene.
9. The magnesium salt lubricating oil detergent of claim 1, wherein the accelerator is triethylamine; the cosolvent is methanol; the weight average molecular weight of the dispersant is 1200-1500.
10. A method of making a high temperature tolerant magnesium salt lubricant detergent as claimed in any of claims 1 to 9, comprising the steps of:
(1) mixing raw materials of 12-fluoro phenylacetyl stearic acid, base oil, magnesium oxide, a dispersant, a solvent, an accelerant and a cosolvent at the temperature of 30-55 ℃ for neutralization for more than 0.5 hour;
(2) heating and introducing carbon dioxide gas;
(3) removing residues and the solvent to obtain the lubricating oil detergent.
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| CN108795538B (en) * | 2018-07-10 | 2021-03-23 | 黄山学院 | Fluoro-polyester type detergent, preparation method and lubricating oil composition prepared from fluoro-polyester type detergent |
| CN116478749A (en) * | 2022-01-14 | 2023-07-25 | 中国石油天然气股份有限公司 | Preparation method of ultrahigh-base-number calcium sulfonate |
| CN116515543B (en) * | 2023-04-12 | 2024-04-02 | 湖南鸿福实业有限公司 | High-dispersion stable lubricating oil metal detergent and preparation method thereof |
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| CN1403435A (en) * | 2001-08-24 | 2003-03-19 | 中国石油天然气股份有限公司 | Prepn process of magnesium naphthenate with superhigh base number |
| CN103131520A (en) * | 2011-11-25 | 2013-06-05 | 中国石油天然气股份有限公司 | Metal detergent accelerant, preparation and applications thereof |
| CN105238500A (en) * | 2015-11-17 | 2016-01-13 | 黄山学院 | Metal magnesium salt lubricating oil detergent and preparation method thereof |
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| US5468399A (en) * | 1992-11-18 | 1995-11-21 | Institut Francais Du Petrole | Colloidal products containing sulfur and/or phosphorus and/or boron, their preparation and their utilization as additives for lubricants |
| CN1403435A (en) * | 2001-08-24 | 2003-03-19 | 中国石油天然气股份有限公司 | Prepn process of magnesium naphthenate with superhigh base number |
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