CN113249160B - Natural gas engine lubricating oil composition and preparation method thereof - Google Patents

Natural gas engine lubricating oil composition and preparation method thereof Download PDF

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CN113249160B
CN113249160B CN202010090373.8A CN202010090373A CN113249160B CN 113249160 B CN113249160 B CN 113249160B CN 202010090373 A CN202010090373 A CN 202010090373A CN 113249160 B CN113249160 B CN 113249160B
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lubricating oil
oil composition
reaction
composition
base
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CN113249160A (en
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庄敏阳
何懿峰
张倩
孙文斌
武志强
钟锦声
张峰
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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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
    • C10M169/04—Mixtures of base-materials and additives
    • 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
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/045—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular compounds
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/0206—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers 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
    • 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
    • C10M2215/065—Phenyl-Naphthyl 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
    • C10M2215/086—Imides
    • 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
    • C10M2215/28—Amides; Imides
    • 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
    • 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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/088—Neutral 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
    • 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
    • C10M2223/049—Phosphite
    • 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
    • C10M2227/09—Complexes with metals

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

The invention provides a natural gas engine lubricating oil composition and a preparation method thereof. The natural gas engine lubricating oil composition comprises a lubricating oil biodegradation accelerator, a high-molecular succinimide ashless dispersant, a mono-succinimide ashless dispersant, a calcium sulfonate detergent, a sulfurized calcium alkyl phenate detergent, a naphthylamine antioxidant, zinc dialkyl dithiophosphate, an organic molybdenum friction improver, a viscosity index improver and lubricating oil base oil, wherein the lubricating oil biodegradation accelerator has a structure shown in a general formula (I):

Description

Natural gas engine lubricating oil composition and preparation method thereof
Technical Field
The invention relates to a lubricating oil composition, in particular to a natural gas engine lubricating oil composition with excellent biodegradability.
Background
At present, the pollution of automobile exhaust emission to the environment is increasingly serious, and the development and application of clean energy are trending. Compared with the traditional gasoline and diesel oil, the natural gas used as the automobile fuel is safer to burn, and can reduce the CO emission by 97 percent, the HC emission by 72 percent, the NOx emission by 39 percent and the SO2The emissions were reduced by 90% and very little emitted particulate was produced. Therefore, the gas automobile is considered to be an effective way for solving the problem of automobile emission pollution at present, and the development prospect is bright.
The internal combustion engine oil is subjected to high-temperature oxidation, external fuel oil, moisture, metal and mechanical impurities in the using process, and oil products are oxidized and deteriorated, so that the engine oil needs to be replaced by new engine oil after being used for a period of time. The waste internal combustion engine oil contains hydrocarbons, additives, sludge and other organic or inorganic substances harmful to animals and plants. In the national records of hazardous waste, used oil belongs to hazardous waste (HW08), and the pollution to water and soil is particularly serious. In China, waste engine oil is difficult to effectively recycle due to the fact that the waste engine oil is distributed and dispersed, so that efficient lubricating oil biodegradation accelerators and antioxidants are applied to the internal combustion engine oil, the service cycle of oil products is prolonged, and the influence of the waste engine oil on the environment is reduced, which is always the aim of the technical staff in the field.
Disclosure of Invention
The invention provides a natural gas engine lubricating oil composition and a preparation method thereof.
Specifically, the present invention relates to the following aspects.
In a first aspect, the present invention provides a natural gas engine lubricating oil composition.
The natural gas engine lubricating oil composition comprises a lubricating oil biodegradation accelerator, a high-molecular succinimide ashless dispersant, a mono-succinimide ashless dispersant, a calcium sulfonate detergent, a sulfurized calcium alkyl phenate detergent, a naphthylamine antioxidant, zinc dialkyl dithiophosphate, an organic molybdenum friction improver, a viscosity index improver and lubricating oil base oil, wherein the lubricating oil biodegradation accelerator has a structure shown in a general formula (I):
Figure BDA0002383509450000021
wherein X is phosphorus or boron, R1Each independently selected from methyl, ethyl, propyl, isopropyl, butyl, 2-methylpropyl, 1-methylpropyl, benzyl and hydrogen, R2Is selected from C8-C18Linear or branched alkyl.
According to the invention, the synthesis method of the lubricating oil biodegradation accelerant comprises the following steps: (1) tartaric acid and a compound of a formula (II) are mixed in a first solvent for carrying out a primary reaction to obtain a first intermediate product, wherein R is3Is methyl or ethyl;
Figure BDA0002383509450000022
(2) mixing a halogenated reagent and a compound shown in a formula (III) in a second solvent, placing the mixture in a reactor, and carrying out secondary reaction to obtain a second intermediate product, wherein the halogenated reagent is selected from one or more of phosphorus trichloride, phosphorus tribromide, phosphorus oxychloride, boron tribromide and boron trichloride;
R2OH (III)
(3) mixing the first intermediate product in a third solvent, adding the mixture into a reactor, and carrying out three times of reaction with the second intermediate product to obtain a third intermediate product;
(4) and (3) carrying out hydrolysis reaction on the third intermediate product to obtain the compound shown in the formula (I).
According to the present invention, the first solvent is preferably selected from one or more of dichloromethane, chloroform, acetone, ethyl acetate, N-dimethylformamide, dimethyl sulfoxide and acetonitrile; the second solvent is preferably selected from one or more of tetrahydrofuran, dichloromethane, chloroform, acetone, ethyl acetate, n-hexane, trichloroethylene and acetonitrile; the third solvent is preferably selected from one or more of tetrahydrofuran, dichloromethane, chloroform, acetone, ethyl acetate, n-hexane, trichloroethylene and acetonitrile.
According to the invention, the molar ratio of the tartaric acid to the compound of formula (II) is preferably 1:5 to 5: 1; the concentration of tartaric acid in the primary reaction system is preferably 0.2 mol/l to 1.0 mol/l.
According to the invention, optionally, a condensing agent is added to the primary reaction system, the condensing agent is preferably selected from one or more of dicyclohexylcarbodiimide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylallyl tryptophan, and the molar ratio of the tartaric acid to the condensing agent is preferably 1: 3-3: 1.
according to the invention, optionally, a racemization inhibitor is added into the primary reaction system, the racemization inhibitor is preferably selected from one or more of 1-hydroxybenzotriazole, N-hydroxysuccinimide, 1-hydroxy-7-azobenzotriazol and 3-hydroxy-1, 2, 3-benzotriazin-4 (3H) -one, the molar ratio of the tartaric acid to the racemization inhibitor is preferably 1: 3-3: 1.
according to the invention, optionally, the molar ratio of tartaric acid to the halogenating agent is preferably (0.95-1.05): 1, and the molar ratio of the halogenating agent to the compound of formula (III) is preferably 1: 3-3: 1.
According to the invention, the reaction temperature of the primary reaction is preferably-20-40 ℃, and the reaction time of the primary reaction is preferably 1-48 h; the reaction temperature of the secondary reaction is preferably-20-40 ℃, and the reaction time of the secondary reaction is preferably 0.1-30 h; the temperature of the three reactions is preferably-20 ℃ to 40 ℃, and the reaction time of the three reactions is preferably 0.1h to 30 h.
According to the invention, the lubricating oil biodegradation accelerator accounts for 0.1-10% (preferably 0.5-3%) of the total mass of the lubricating oil composition; the ashless macromolecular succinimide dispersant accounts for 1-15% (preferably 2-10%) of the total mass of the lubricating oil composition; the mono-succinimide ashless dispersant accounts for 1-15% (preferably 2-10%) of the total mass of the lubricating oil composition; the calcium sulfonate detergent accounts for 0.2-10% (preferably 1-5%) of the total mass of the lubricating oil composition; the sulfurized calcium alkyl phenate detergent accounts for 0.2-10% (preferably 1-5%) of the total mass of the lubricating oil composition; the naphthylamine antioxidant accounts for 0.5-10% (preferably 1-5%) of the total mass of the lubricating oil composition; the zinc dialkyl dithiophosphate accounts for 0.5 to 10 percent (preferably 1 to 5 percent) of the total mass of the lubricating oil composition; the organic molybdenum friction modifier accounts for 0.01-5% (preferably 0.05-2%) of the total mass of the lubricating oil composition; the viscosity index improver accounts for 3-15% (preferably 5-10%) of the total mass of the lubricating oil composition; the lubricant base oil constitutes the main component of the lubricating oil composition.
According to the invention, the number average molecular weight of the polyisobutylene part in the high molecular succinimide ashless dispersant is preferably 1600-4000; the number average molecular weight of the polyisobutene part in the mono-succinimide ashless dispersant is preferably 500-1500; the calcium sulfonate detergent is preferably selected from one or more of low-base-number calcium sulfonate, medium-base-number calcium sulfonate and high-base-number calcium sulfonate, and in order to better control the sulfated ash content of an oil product, the calcium sulfonate detergent is preferably medium-base-number calcium sulfonate with the base number of (130-200) mgKOH/g; the sulfurized calcium alkyl phenate detergent is preferably selected from one or more of low-base-number sulfurized calcium alkyl phenate, medium-base-number sulfurized calcium alkyl phenate and high-base-number sulfurized calcium alkyl phenate, and in order to better control sulfated ash of an oil product, the sulfurized calcium alkyl phenate detergent is preferably medium-base-number sulfurized calcium alkyl phenate with the base number of (130-200) mgKOH/g; the alkyl group of the zinc dialkyldithiophosphate is preferably selected from C1～12One or more of primary alkyl, secondary alkyl and aryl; the organo-molybdenum friction modifier is preferably selected from one or more of molybdenum dialkyldithiocarbamates, molybdenum dialkyldithiophosphates, oxymolybdenum dialkyldithiophosphates, molybdenum xanthates, and molybdates; the viscosity index improver is preferably an OCP type viscosity index improver; the lubricating oil base oil is selected from one or more of API I, II, III, IV and V base oilsAnd (4) seed preparation.
According to the invention, the ashless dispersant of the macromolecular succinimide can be selected from T161 produced by additive factory of Kanz petrochemical company, LZL157 produced by Lubrizol additive limited company, LZ6418B produced by Lubrizol Corporation, and the like; the mono-succinimide ashless dispersant can be selected from T151 produced by additive factory of Jinzhou petrochemical company, southern additive factory without tin, LZL151A produced by Lubrizol additive limited company, LZ894 produced by Lubrizol Corporation, and the like; the calcium sulfonate detergent can be selected from T105, T106 and T104 produced by additive factories of petrochemical company of Jinzhou, T102, T103 and T107B produced by additive factories of Shanghai, LZ6478, LZ58B, LZ75 and LZ6446 produced by Lubrizol Corporation, C9353 and C9330 produced by Infineum company and the like; the sulfurized calcium alkyl phenolate can be selected from S206 and T121 produced by a tin-free south additive factory, LZL115A and LZL115B produced by Lubrizol additive limited company, LZ6499 and LZ6500 produced by Lubrizol Corporation, C9391 and C9394 produced by Infineum, and the like; the naphthylamine antioxidant can be Irganox L106 produced by Ciba-Geigy Ltd, T531 produced by Tianjin Pengyi chemical plant, etc.; the zinc dialkyl dithiophosphate can be T202, T203, T205 and the like produced by a tin-free south additive factory and an additive factory of Jinzhou petrochemical company; the organic molybdenum friction modifier can be Molyvan 807, Molyvan 822, Molyvan 855, Molyvan 856B and the like which are produced by Vanderbilt company; the viscosity index improver may be JINEX 9100, JINEX 9300, JINEX 9600, available from Jinzhou lubricating oil additives Co., Ltd., LZ7065, LZ7067, LZ7077, LZ7070, available from Lubrizol Corporation, etc.; the lubricating oil base oil is preferably one or more of hydrogenated base oil, polyolefin synthetic base oil, alkylbenzene base oil and ester synthetic base oil.
In a second aspect, the present invention provides a method for preparing the aforementioned natural gas engine lubricating oil composition.
The method for producing the natural gas engine lubricating oil composition of the present invention includes a step of mixing various additives in the lubricating oil composition with a lubricating base oil. The mixing temperature is preferably 40 ℃ to 90 ℃ and the mixing time is preferably 1 hour to 6 hours.
The natural gas engine lubricating oil composition has excellent biodegradability, wear resistance, high-temperature oxidation resistance, dispersibility and corrosion resistance, and can meet the requirements of high-performance natural gas engine lubricating oil.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.
The properties in examples and comparative examples were evaluated as follows.
(1) Biodegradability
The lubricating oil compositions prepared in the examples or comparative examples were evaluated for biodegradability as test samples according to the OECD302B method.
(2) Thermal oxidation stability
The lubricating oil compositions prepared in examples or comparative examples were used as test samples, and the thermo-oxidative stability of the test samples was evaluated by a Pressurized Differential Scanning Calorimetry (PDSC) test, as expressed by the oxidation induction period of the test samples. The PDSC test was carried out at a temperature of 210 ℃ and a pressure of 0.5MPa with an oxygen flow rate of 100 mL/min.
(3) Oil sludge dispersibility
The method comprises the steps of uniformly mixing test oil and oil sludge, then dropping the mixture on filter paper, measuring the diameter of an oil sludge diffusion ring and the diameter of a lubricating oil diffusion ring after 24 hours, calculating the ratio of the diameter of the oil sludge diffusion ring to the diameter of the lubricating oil diffusion ring to obtain a dispersion index, and identifying the dispersion performance of an oil product, wherein the larger the ratio is, the better the dispersion performance is.
(4) Evaluation of abrasion resistance
The lubricating oil compositions produced in the examples or comparative examples were evaluated for anti-wear properties as test samples according to SH/T0189 standard method. The test conditions of the abrasion resistance test are 392N (40kg), the oil groove temperature is 75 ℃, the heading speed is 1200r/min, and the time is 60 min. The abrasion resistance of the sample was evaluated by the average value of the wear-mark diameters of the following three balls.
(5) Evaluation of copper sheet corrosion inhibition performance
The lubricating oil compositions produced in the examples or comparative examples were subjected to a copper sheet corrosion test as test samples with reference to the ASTM D130 standard method. And immersing the polished copper sheet in the sample, heating to the test temperature of 121 ℃, keeping for 3 hours, taking out the copper sheet after the test is finished, and comparing the copper sheet with a corrosion standard color plate after washing to determine the corrosion grade.
Example 1
Synthesis of 2,2' - ((2-dodecyloxy) -1,3, 2-dioxolane-4, 5-dicarbonyl) -diamino-bis (3-methylbutyric acid) (see Structure I-a).
Figure BDA0002383509450000061
1) To the reactor were added sequentially 100mL of DMF, tartaric acid (33.3mmol, 5g), L-valine methyl ester hydrochloride (73.2mmol, 12.27g), 1-hydroxybenzotriazole (79.9mmol, 10.8g), pyridine (8mL), cooled to 0 deg.C, DCC (79.9mmol, 16.5g) was added, and the reaction was allowed to proceed overnight. The reaction mixture was filtered with suction, the solid was washed with 300mL ethyl acetate, the organic phases were combined, washed twice with saturated sodium bicarbonate solution, twice with 10% hydrochloric acid solution, once with saturated brine, dried over anhydrous magnesium sulfate for 2h, filtered and spin-dried to give a white solid.
2) Phosphorus trichloride (40mmol, 5.48g) was dissolved in 5mL of n-hexane, the temperature was reduced to 4 ℃, triethylamine (40mmol, 4.04g) was dissolved in 25mL of trichloroethylene, lauryl alcohol (27mmol, 5g) was dissolved in 40mL of trichloroethylene, and the solution was slowly added dropwise to the reactor. After the addition, the temperature was raised to room temperature and stirring was continued for 1 hour.
3) Taking the white solid (30mmol, 10.44g) obtained in the step 1), adding 50mL of dichloromethane and 8mL of pyridine, cooling to 0 ℃, slowly dropping the reaction liquid obtained in the step 2) into the reactor, reacting at room temperature overnight after dropping, filtering to remove the solid, washing the filtrate twice with 10% hydrochloric acid solution, washing once with saturated saline solution, drying for 2h with anhydrous magnesium sulfate, filtering, and spin-drying to obtain the white solid.
4) The above white solid (20mmol, 11.81g) was dissolved in 200mL of a mixed solution of tetrahydrofuran and water 2:1, and a lithium hydroxide solid (200mmol, 5g) was added thereto, reacted at room temperature overnight, and then the tetrahydrofuran was removed by rotary evaporation, acidified to pH 4 with a 10% hydrochloric acid solution, and filtered by suction to obtain a white solid. Acetone recrystallization yielded 2,2' - ((2-dodecyloxy) -1,3, 2-dioxolane-4, 5-dicarbonyl) -diamino-bis (3-methylbutyric acid) (formula I-a).
Wherein the nuclear magnetic test result of the compound shown in the formula I-a is as follows:
1H NMR(400MHz,CDCl3)δ11.75(br,2H),8.01(s,2H),4.71(d,J＝6.8Hz,2H),4.32(d,J＝7.2Hz,2H),3.76(t,J＝6.4Hz,2H),2.03-1.88(m,2H),1.77-1.59(m,4H),1.33-1.17(m,16H),0.99(d,J＝7.2Hz,12H),0.80(t,J＝7.0Hz,3H)；.HRMS(FT-ICRMS)calcd for C26H45N2O9P(M-2H):280.1437,found:280.1441.
the compound is identified as the target compound 2,2' - ((2-dodecyloxy) -1,3, 2-dioxaphospholane-4, 5-dicarbonyl) -diamino-di (3-methylbutyric acid) (shown in structural formula I-a).
Example 2
Synthesis of 2,2' - ((2-tetradecyloxy) -1,3, 2-dioxaphospholane-4, 5-dicarbonyl) -diamino-bis (3-methylbutyric acid) (see Structure I-b).
Figure BDA0002383509450000071
1) 100mL of DMF, tartaric acid (33.3mmol, 5g), L-valine methyl ester hydrochloride (73.2mmol, 12.27g), 1-hydroxybenzotriazole (79.9mmol, 10.8g) and pyridine (8mL) were sequentially added to the reactor, the temperature was reduced to 0 ℃, DCC (79.9mmol, 16.5g) was added, and the reaction was allowed to proceed overnight. The reaction mixture was filtered with suction, the solid was washed with 300mL ethyl acetate, the organic phases were combined, washed twice with saturated sodium bicarbonate solution, twice with 10% hydrochloric acid solution, once with saturated brine, dried over anhydrous magnesium sulfate for 2h, filtered and spin-dried to give a white solid.
2) Phosphorus trichloride (40mmol, 5.48g) was dissolved in 5mL of n-hexane, the temperature was reduced to 4 ℃, triethylamine (40mmol, 4.04g) was dissolved in 25mL of trichloroethylene, myristyl alcohol (27mmol, 5.78g) was dissolved in 40mL of trichloroethylene, and the solution was slowly added dropwise to the reactor. After the addition, the temperature was raised to room temperature and stirring was continued for 1 hour.
3) Taking the white solid (30mmol, 10.44g) obtained in the step 1), adding 50mL of dichloromethane and 8mL of pyridine, cooling to 0 ℃, slowly dropping the reaction liquid obtained in the step 2) into the reactor, reacting at room temperature overnight after dropping, filtering to remove the solid, washing the filtrate twice with 10% hydrochloric acid solution, washing once with saturated saline solution, drying for 2h with anhydrous magnesium sulfate, filtering, and spin-drying to obtain the white solid.
4) The above white solid (20mmol, 11.81g) was dissolved in 200mL of a mixed solution of tetrahydrofuran and water 2:1, and a lithium hydroxide solid (200mmol, 5g) was added thereto, reacted at room temperature overnight, and then the tetrahydrofuran was removed by rotary evaporation, acidified to pH 4 with a 10% hydrochloric acid solution, and filtered by suction to obtain a white solid. Acetone recrystallization yields 2,2' - ((2-tetradecyloxy) -1,3, 2-dioxaphospholane-4, 5-dicarbonyl) -diamino-bis (3-methylbutyric acid) (formula I-b).
The results of nuclear magnetic testing of the compounds of formula I-b are as follows:
1H NMR(400MHz,CDCl3)δ11.79(br,2H),8.11(s,2H),4.77(d,J＝6.4Hz,2H),4.37(d,J＝7.0Hz,2H),3.75(t,J＝6.4Hz,2H),2.05-1.89(m,2H),1.79-1.57(m,4H),1.34-1.18(m,16H),0.98(d,J＝7.2Hz,16H),0.81(t,J＝7.0Hz,3H)；.HRMS(FT-ICRMS)calcd for C28H49N2O9P(M-2H):294.1593,found:294.1601.
the obtained compound is identified as the target compound 2,2' - ((2-tetradecyloxy) -1,3, 2-dioxaphospholane-4, 5-dicarbonyl) -diamino-di (3-methylbutyric acid) (shown in the structural formula I-b).
Example 3
Synthesis of 2,2' - ((2-tetradecyloxy) -1,3, 2-dioxaphospholane-4, 5-dicarbonyl) -diamino-dipropionic acid (see structure I-c).
Figure BDA0002383509450000081
1) To the reactor were added sequentially 100mL of DMF, tartaric acid (33.3mmol, 5g), L-alanine methyl ester hydrochloride (73.2mmol, 10.21g), 1-hydroxybenzotriazole (79.9mmol, 10.8g), pyridine (8mL), cooled to 0 deg.C, DCC (79.9mmol, 16.5g) was added, and the reaction was allowed to proceed overnight. The reaction mixture was filtered with suction, the solid was washed with 300mL ethyl acetate, the organic phases were combined, washed twice with saturated sodium bicarbonate solution, twice with 10% hydrochloric acid solution, once with saturated brine, dried over anhydrous magnesium sulfate for 2h, filtered and spin-dried to give a white solid.
2) Phosphorus trichloride (40mmol, 5.48g) was dissolved in 5mL of n-hexane, the temperature was reduced to 4 ℃, triethylamine (40mmol, 4.04g) was dissolved in 25mL of trichloroethylene, myristyl alcohol (27mmol, 5.78g) was dissolved in 40mL of trichloroethylene, and the solution was slowly added dropwise to the reactor. After the addition, the temperature was raised to room temperature and stirring was continued for 1 hour.
3) Taking the white solid (30mmol, 9.61g) obtained in the step 1), adding 50mL of dichloromethane and 8mL of pyridine, cooling to 0 ℃, slowly dropping the reaction liquid obtained in the step 2) into the reactor, reacting at room temperature overnight after dropping, filtering to remove the solid, washing the filtrate twice with 10% hydrochloric acid solution, washing once with saturated saline solution, drying for 2h with anhydrous magnesium sulfate, filtering, and spin-drying to obtain the white solid.
4) The above white solid (20mmol, 11.25g) was dissolved in 200mL of a mixed solution of tetrahydrofuran and water 2:1, and a lithium hydroxide solid (200mmol, 5g) was added thereto, reacted at room temperature overnight, and then the tetrahydrofuran was removed by rotary evaporation, acidified to pH 4 with a 10% hydrochloric acid solution, and filtered by suction to obtain a white solid. Acetone is recrystallized to obtain 2,2' - ((2-tetradecyloxy) -1,3, 2-dioxaphospholane-4, 5-dicarbonyl) -diamino-dipropionic acid (shown in a formula I-c).
Wherein the compound has the following nuclear magnetic test results of formula I-c:
1H NMR(400MHz,CDCl3)δ11.91(br,2H),8.11(s,2H),4.75(d,J＝7.0Hz,2H),4.59-4.34(m,2H),3.71(t,J＝6.8Hz,2H),1.59-1.40(m,4H),1.33-1.17(m,26H),0.84(t,J＝7.2Hz,3H)；.HRMS(FT-ICRMS)calcd for C24H41N2O9P(M-2H):266.1280,found:266.1287.
the obtained compound is identified as the target compound 2,2' - ((2-tetradecyloxy) -1,3, 2-dioxaphospholane-4, 5-dicarbonyl) -diamino-dipropionic acid (shown in structural formula I-c).
The main sources of additives used in the compositions of the invention are as follows:
t161, ashless dispersant of high molecular succinimide, stannless southern additive plant
T151, ashless dispersant monobutyldiimide, tin-free southern additive plant
T105, medium-base calcium sulfonate, California petrochemicals
T121, medium-basicity sulfurized calcium alkyl phenate, stanneless southern additive plant
Irganox L106, naphthylamine antioxidant, Ciba-Geigy Ltd
T202, zinc butyl/isooctyl dithiophosphate, tin-free south additive plant
Molyvan 855, organo-molybdenum friction modifier, Vanderbilt Corp
LZ7067, OCP viscosity index improver, Lubrizol Corporation
Examples I-1 to I-3 and comparative examples ID-1 to ID-2
The formulation compositions of examples I-1 to I-3 and comparative example ID-1 are shown in Table 1, and examples and comparative examples were prepared by mixing the formulations at 50 ℃ for 2 hours to give lubricating oil compositions for natural gas engines, respectively. Comparative example ID-2 is a commercially available natural gas engine lubricating oil.
The lubricating oil compositions of the above examples and comparative examples were used as test samples, and the biodegradability, antiwear properties, high-temperature antioxidant properties, dispersibility, and corrosion resistance were evaluated, respectively, with the evaluation results shown in table 2.
As can be seen from Table 2, the lubricating oil composition of the present invention has excellent biodegradability, antiwear properties, high-temperature antioxidant properties, dispersancy properties and anti-corrosion properties.
TABLE 1
Figure BDA0002383509450000101
TABLE 2
Figure BDA0002383509450000102

Claims (11)

1. A natural gas engine lubricating oil composition comprises a lubricating oil biodegradation accelerator, a high-molecular succinimide ashless dispersant, a mono-succinimide ashless dispersant, a calcium sulfonate detergent, a sulfurized calcium alkyl phenate detergent, a naphthylamine antioxidant, zinc dialkyl dithiophosphate, an organic molybdenum friction improver, a viscosity index improver and lubricating oil base oil, wherein the lubricating oil biodegradation accelerator has a structure shown in a general formula (I):
Figure DEST_PATH_IMAGE002
（I）
wherein X is phosphorus or boron, R1Each independently selected from methyl, ethyl, propyl, isopropyl, butyl, 2-methylpropyl, 1-methylpropyl, benzyl and hydrogen, R2Is selected from C8-C18Linear or branched alkyl.
2. The composition of claim 1, wherein the process for synthesizing the biodegradation accelerator for lubricating oils comprises the steps of:
(1) tartaric acid and a compound of a formula (II) are mixed in a first solvent for carrying out a primary reaction to obtain a first intermediate product, wherein R is3Is methyl or ethyl;
Figure DEST_PATH_IMAGE004
（II）
(2) mixing a halogenated reagent and a compound shown in a formula (III) in a second solvent, placing the mixture in a reactor, and carrying out secondary reaction to obtain a second intermediate product, wherein the halogenated reagent is selected from one or more of phosphorus trichloride, phosphorus tribromide, phosphorus oxychloride, boron tribromide and boron trichloride;
R2OH （III）
(3) mixing the first intermediate product in a third solvent, adding the mixture into a reactor, and carrying out three times of reaction with the second intermediate product to obtain a third intermediate product;
(4) and (3) carrying out hydrolysis reaction on the third intermediate product to obtain the compound shown in the formula (I).
3. The composition of claim 2, wherein the first solvent is selected from one or more of dichloromethane, chloroform, acetone, ethyl acetate, N-dimethylformamide, dimethyl sulfoxide, and acetonitrile; or the second solvent is selected from one or more of tetrahydrofuran, dichloromethane, chloroform, acetone, ethyl acetate, n-hexane, trichloroethylene and acetonitrile; or the third solvent is selected from one or more of tetrahydrofuran, dichloromethane, chloroform, acetone, ethyl acetate, n-hexane, trichloroethylene and acetonitrile.
4. The composition of claim 2, wherein the molar ratio of tartaric acid to the compound of formula (II) is 1:5 to 5: 1; the concentration of the tartaric acid in the primary reaction system is 0.2 mol/L-1.0 mol/L.
5. The composition according to claim 2, wherein a condensing agent selected from one or more of dicyclohexylcarbodiimide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylallyltryptophan is added to the primary reaction system.
6. The composition according to claim 2, wherein a racemization inhibitor is added into the primary reaction system, and the racemization inhibitor is selected from one or more of 1-hydroxybenzotriazole, N-hydroxysuccinimide, 1-hydroxy-7-azobenzotriazol and 3-hydroxy-1, 2, 3-benzotriazin-4 (3H) -one.
7. The composition according to claim 2, wherein the molar ratio of the tartaric acid to the halogenating agent is (0.95-1.05): 1 and the molar ratio of the halogenating agent to the compound of formula (III) is 1: 3-3: 1.
8. The composition according to claim 2, wherein the reaction temperature of the primary reaction is-20 ℃ to 40 ℃, and the reaction time of the primary reaction is 1h to 48 h; or the reaction temperature of the secondary reaction is-20 ℃ to 40 ℃, and the reaction time of the secondary reaction is 0.1h to 30 h; or the temperature of the third reaction is-20 ℃ to 40 ℃, and the reaction time of the third reaction is 0.1h to 30 h.
9. The composition of claim 1, wherein the lubricating oil biodegradation accelerator comprises from 0.1% to 10% by weight of the total lubricating oil composition; the ashless macromolecular succinimide dispersant accounts for 1-15% of the total mass of the lubricating oil composition; the mono-succinimide ashless dispersant accounts for 1-15% of the total mass of the lubricating oil composition; the calcium sulfonate detergent accounts for 0.2-10% of the total mass of the lubricating oil composition; the sulfurized calcium alkyl phenate detergent accounts for 0.2-10% of the total mass of the lubricating oil composition; the naphthylamine antioxidant accounts for 0.5-10% of the total mass of the lubricating oil composition; the zinc dialkyl dithiophosphate accounts for 0.5 to 10 percent of the total mass of the lubricating oil composition; the organic molybdenum friction modifier accounts for 0.01-5% of the total mass of the lubricating oil composition; the viscosity index improver accounts for 3-15% of the total mass of the lubricating oil composition; the lubricant base oil constitutes the main component of the lubricating oil composition.
10. The composition of claim 1, wherein the number average molecular weight of the polyisobutylene moiety of the polymeric succinimide ashless dispersant is 1600 to 4000; the mono-succinimide is ashlessThe number average molecular weight of the polyisobutylene part in the dispersing agent is 500-1500; the calcium sulfonate detergent is selected from one or more of low-base-number calcium sulfonate, medium-base-number calcium sulfonate and high-base-number calcium sulfonate; the sulfurized calcium alkyl phenate detergent is preferably selected from one or more of low-base-number sulfurized calcium alkyl phenate, medium-base-number sulfurized calcium alkyl phenate and high-base-number sulfurized calcium alkyl phenate; the alkyl group of the zinc dialkyldithiophosphate is selected from C1~12One or more of primary alkyl groups and secondary alkyl groups; the organic molybdenum friction modifier is selected from one or more of molybdenum dialkyl dithiocarbamate, molybdenum dialkyl dithiophosphate, molybdenum oxygen dialkyl dithiophosphate, molybdenum xanthate and molybdate ester; the viscosity index improver is an OCP type viscosity index improver; the lubricating oil base oil is selected from one or more of API I, II, III, IV and V base oils.
11. A method for preparing a natural gas engine lubricating oil composition as claimed in any one of claims 1 to 10, comprising the step of mixing the various additives in the composition as claimed in any one of claims 1 to 10 with a lubricating base oil.
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CN107760419A (en) * 2016-08-19 2018-03-06 江西福安路润滑材料有限公司 Lubricant composition for gasoline engine and preparation method thereof
CN110317662A (en) * 2018-03-28 2019-10-11 中国石油化工股份有限公司 Diesel engine lubricating oil composite and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005200326A (en) * 2004-01-14 2005-07-28 Sumitomo Chemical Co Ltd Method for producing phosphite compounds
US20110239972A1 (en) * 2008-10-09 2011-10-06 Idemitsu Kosan Co., Ltd. Lubricating oil compositions
US7928267B1 (en) * 2009-06-22 2011-04-19 Eastman Chemical Company Phosphite containing catalysts for hydroformylation processes
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