CN112011389A - Engine lubricating oil composition - Google Patents
Engine lubricating oil composition Download PDFInfo
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- CN112011389A CN112011389A CN201910449789.1A CN201910449789A CN112011389A CN 112011389 A CN112011389 A CN 112011389A CN 201910449789 A CN201910449789 A CN 201910449789A CN 112011389 A CN112011389 A CN 112011389A
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- 239000000203 mixture Substances 0.000 title claims abstract description 94
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 76
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 43
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 31
- 239000002199 base oil Substances 0.000 claims abstract description 22
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- 239000003599 detergent Substances 0.000 claims abstract description 12
- 230000000994 depressogenic effect Effects 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 8
- 239000003831 antifriction material Substances 0.000 claims abstract description 6
- 230000001050 lubricating effect Effects 0.000 claims abstract description 4
- -1 isopropyl isooctyl zinc dithiophosphate Chemical compound 0.000 claims description 29
- 239000003638 chemical reducing agent Substances 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 229960002317 succinimide Drugs 0.000 claims description 16
- 150000001412 amines Chemical class 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000011575 calcium Substances 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 229960001860 salicylate Drugs 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- 229920002367 Polyisobutene Polymers 0.000 claims description 8
- 239000010705 motor oil Substances 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000008186 active pharmaceutical agent Substances 0.000 claims description 6
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 6
- 229940077388 benzenesulfonate Drugs 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 5
- 229920013639 polyalphaolefin Polymers 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 125000005456 glyceride group Chemical group 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- DMBHHRLKUKUOEG-UHFFFAOYSA-N N-phenyl aniline Natural products C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 2
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 229940083037 simethicone Drugs 0.000 claims description 2
- XEOXZSREIVIEIP-UHFFFAOYSA-N trizinc [butyl(octyl)-lambda4-sulfanylidene]-dioxido-sulfido-lambda5-phosphane Chemical compound C(CCC)S(=P([S-])([O-])[O-])CCCCCCCC.[Zn+2].C(CCC)S(=P([S-])([O-])[O-])CCCCCCCC.[Zn+2].[Zn+2] XEOXZSREIVIEIP-UHFFFAOYSA-N 0.000 claims description 2
- GBEDXBRGRSPHRI-UHFFFAOYSA-L zinc;octoxy-octylsulfanyl-oxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCCCCOP([O-])(=S)SCCCCCCCC.CCCCCCCCOP([O-])(=S)SCCCCCCCC GBEDXBRGRSPHRI-UHFFFAOYSA-L 0.000 claims description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims 1
- 239000012990 dithiocarbamate Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 53
- 238000012360 testing method Methods 0.000 abstract description 28
- 230000000694 effects Effects 0.000 abstract description 23
- 239000000446 fuel Substances 0.000 abstract description 16
- 239000003795 chemical substances by application Substances 0.000 abstract description 14
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- 239000000654 additive Substances 0.000 description 20
- 238000004088 simulation Methods 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 12
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- 230000000996 additive effect Effects 0.000 description 10
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- 230000005764 inhibitory process Effects 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000010711 gasoline engine oil Substances 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical class [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 3
- CLKAQWSCGDNHHJ-UHFFFAOYSA-N OP(O)(S)=S.CCCCCCCC[Zn]CCCCCCCC Chemical compound OP(O)(S)=S.CCCCCCCC[Zn]CCCCCCCC CLKAQWSCGDNHHJ-UHFFFAOYSA-N 0.000 description 2
- WBRJQOHIFXIMCO-UHFFFAOYSA-N P(=S)(S)(O)O.C(CCC)[Zn]CCCCCCCC Chemical compound P(=S)(S)(O)O.C(CCC)[Zn]CCCCCCCC WBRJQOHIFXIMCO-UHFFFAOYSA-N 0.000 description 2
- 230000003254 anti-foaming effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000009897 systematic effect Effects 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000007866 anti-wear additive Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- AVVIDTZRJBSXML-UHFFFAOYSA-L calcium;2-carboxyphenolate;dihydrate Chemical compound O.O.[Ca+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O AVVIDTZRJBSXML-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229940008099 dimethicone Drugs 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
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- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical group C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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Images
Classifications
-
- 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
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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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 engine lubricating oil composition prepared by the invention comprises a metal detergent, an ashless dispersant, an antioxidant antiwear agent, an antifriction agent, a sticking agent, a pour point depressant, an antifoaming agent and base oil. The composition meets the requirements of API SN and ILSAC GF-5 standards, shows excellent energy-saving performance in standard VID bench tests, and particularly has excellent energy-saving effect after oil product aging. The composition can be used for lubricating engines with SN and GF-5 quality grade requirements, and is also particularly suitable for lubricating parts which have harsh requirements on fuel economy and need energy-saving long-acting property.
Description
Technical Field
The invention belongs to the technical field of lubricating oil, and particularly relates to engine lubricating oil with the performance meeting API SN and ILSAC GF-5 standard requirements. The present invention belongs to the class of hydrogenated lubricating compositions.
Background
With the rapid development of national economy, the continuous change of the specifications of engine oil and the stricter emission regulations, the development of high-grade internal combustion engine oil becomes the main direction of the research and development of lubricating oil, and lubricating oil products also change from the direction of protecting engines to the direction of simultaneously protecting the environment and saving energy.
SN/GF-5 is proposed in 10 months in 2009 by American API and ILSAC organizations according to the change of engine design, environmental protection requirements and energy conservation, and oil products with the specifications not only provide more rigorous requirements on the protection of catalytic converters, fuel economy durability, oil sludge inhibition, carbon deposition inhibition and other performances, but also newly increase the performance requirements of the oil products on the compatibility of sealing materials, the compatibility of biological fuels (such as E85) and the like, and can meet the higher-level emission standards of Euro VI and the like. The specification of SN/GF-55W-30 requires that the content of phosphorus element is within a certain level range and has certain phosphorus retention, which limits the dosage of ZDDP, but on the basis, the anti-oxidation and high temperature deposit inhibition performance of the oil product is improved, which needs to balance the performances. Compared with the specification of SM engine oil, VG and IIIG indexes of SN are more rigorous, GF-5 grade oil products are compared with the specification of GF-4 engine oil, the rigorous degree of VID fuel economy test is higher than that of VIB, and higher requirements are provided for fuel economy after oil products are aged.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the engine lubricating oil composition which has the quality meeting the requirements of SN/GF-5 standard and has excellent energy-saving effect, particularly excellent energy-saving property after oil product aging.
In order to meet the technical requirements, various types of metal detergents, ashless dispersants and antioxidant antiwear agents in the lubricating oil composition are carefully screened, the interaction and relationship among the components are comprehensively and systematically researched, the energy-saving property of the oil product is purposefully improved as the key point of research, the formula system between the antioxidant antiwear agent and the antifriction agent of the conventional gasoline engine oil is broken through, and the lubricating oil composition has excellent fuel economy and meets the oil energy-saving requirement.
The invention provides an engine lubricating oil composition, which comprises the following components in percentage by weight based on the total mass of the composition:
the balance being base oil.
The component C of the engine lubricating oil composition provided by the invention is a mixture consisting of any four or five of butyl octyl zinc dithiophosphate, dioctyl zinc dithiophosphate, isopropyl isooctyl zinc dithiophosphate, amine ashless antioxidant, phenol ashless antioxidant and ester ashless antioxidant.
The component D is amine friction reducing agent and/or ester friction reducing agent.
The present invention provides engine lubricating oil compositions wherein the amine ashless antioxidant includes, but is not limited to, alkyl diphenylamine ashless antioxidants; the phenolic ashless antioxidants include, but are not limited to, ester group-containing phenolic ashless antioxidants; the ester ashless antioxidants include, but are not limited to, dialkyldithiocarbamate ashless antioxidants; the amine based friction reducing agents include, but are not limited to, diamine ester based friction reducing agents; the ester type friction reducing agent includes, but is not limited to, a hindered phenol-containing glyceride type friction reducing agent.
The invention provides an engine lubricating oil composition, wherein the component A is a mixture consisting of any two or three of alkyl salicylate, alkyl benzene sulfonate and sulfurized alkyl phenate.
The present invention provides engine lubricating oil compositions, the alkyl salicylates including, but not limited to, calcium alkyl salicylate, magnesium alkyl salicylate; the alkylbenzene sulfonate includes, but is not limited to, calcium alkylbenzene sulfonate, magnesium alkylbenzene sulfonate; the sulfurized alkylphenates include, but are not limited to, calcium sulfurized alkylphenate.
The component B of the engine lubricating oil composition provided by the invention is one or two of macromolecular succinimide, polyisobutylene mono-succinimide and polyisobutylene di-succinimide.
The component E of the lubricating oil composition for the engine provided by the invention is a styrene-isoprene copolymer and/or an undispersed allyl ethylene copolymer.
The component F is alkyl naphthalene and/or poly alpha-olefin.
The component G of the engine lubricating oil composition provided by the invention is one or two of simethicone, alkyl acrylic acid copolymer and alkyl polyamide.
The base oil is two or more than two high-viscosity-index hydrogenated base oil compositions with the performance meeting the standard requirement of API III base oil.
Preferably, the engine lubricating oil composition provided by the invention comprises the following components in percentage by total mass:
the balance being base oil.
Next, the present invention provides a method for preparing the above engine lubricating oil composition, comprising the steps of:
(1) adding base oil with required amount into a stainless steel blending kettle with a stirrer, heating to 60-70 ℃, stirring for 1-2 hours, adding an antifoaming agent into the blending kettle, and continuing stirring for 1-2 hours;
(2) sequentially adding the pour point depressant and the viscosity index improver into the blending kettle, and continuously stirring for 1-2 hours;
(3) and sequentially adding the ashless dispersant, the antioxidant, the metal detergent and the antifriction agent into a blending kettle, and continuously stirring for 3-4 hours at the temperature of 60-70 ℃ until the mixture is uniform, thus obtaining the engine lubricating oil composition.
Preferably, the engine lubricating oil composition provided by the invention comprises, by weight, 0.20-0.30 wt% of sulfur, 0.07-0.08 wt% of phosphorus, 0.08-0.10 wt% of nitrogen, 6.5-8.0 mgKOH/g of base number, and 0.75-0.9 wt% of sulfated ash.
The engine lubricating oil composition provided by the invention has good application in the field of lubricating oil.
The present invention can be described in detail as follows:
the invention relates to an engine lubricating oil composition which comprises the following components:
at least two metal detergents A can be any two or three of calcium alkyl salicylate, magnesium alkyl salicylate, calcium alkyl benzene sulfonate, magnesium alkyl benzene sulfonate and calcium sulfurized alkylphenol. About 1.0 to about 3.0% by weight of the total composition, with a preferred suitable range of about 1.5 to about 3.0%.
B at least one ashless dispersant which may be a polymeric succinimide or a polyisobutylene mono-succinimide or a polyisobutylene di-succinimide or a mixture of any of the two. About 2.0 to 4.0% by weight of the total composition, preferably in the range of about 2.0 to 3.0% by weight.
C at least four oxidation, corrosion and abrasion resistant agents can be any four or five of zinc butyl octyl dithiophosphate, zinc dioctyl dithiophosphate, isopropyl isooctyl dithiophosphate, amine ashless antioxidant, phenol ashless antioxidant and ester ashless antioxidant. About 1.5 to about 2.5 weight percent of the total composition, with a preferred suitable range being from about 2.0 to about 2.5 weight percent.
D at least one friction reducer, which may be an amine friction reducer, an ester friction reducer, or a combination of both. About 0.1 to about 1.0% by weight of the total composition, preferably in the range of about 0.3 to about 0.8% by weight.
E at least one viscosity index improver which may be a styrene-isoprene copolymer or a non-dispersed ethylene propylene copolymer or a combination of both. About 4.0 to about 10.0% by weight of the total composition, preferably 5.0 to about 8.0% by weight.
F at least one pour point depressant, which may be an alkyl naphthalene type or a polyalphaolefin or a combination of any two of the foregoing. About 0.2 to about 0.5 weight percent, preferably in the appropriate range of about 0.2 to about 0.4 weight percent, based on the total weight of the composition.
G at least one anti-foaming agent, which may be a dimethicone or an alkyl acrylic copolymer or an alkyl polyamide or a combination of any two of the above. About 0.001-0.010% by weight of the total composition, preferably in the range of 0.003-0.005%.
H at least two base oils, and may be two or more high viscosity index hydrogenated base oil compositions having properties meeting API group III base oil standards. About 79-91.2% by weight of the total composition, preferably in the range of about 82.3-89%.
The preparation method of the lubricating oil composition of the invention comprises the following steps:
firstly, adding a base oil component (H) with required amount in proportion into a stainless steel blending kettle with a stirrer, heating to 60-70 ℃, stirring for 2 hours, adding an antifoaming agent (G) with required amount in proportion into the blending kettle, continuously stirring for 2 hours, sequentially adding a pour point depressant (F) and a viscosity index improver (E) with required amount in proportion into the blending kettle, continuously stirring for 2 hours, sequentially adding an ashless dispersant (B), an antioxidant, an anti-corrosion and anti-wear agent (C), a metal detergent (A) and an antifriction agent (D) with required amount in proportion, and continuously stirring for 4 hours at 60-70 ℃ until the mixture is uniform.
In order to ensure that the performance of the composition reaches the aim of the invention and the oil product still has excellent energy-saving performance after aging, the invention performs systematic and complicated screening and optimized compounding among different types of additives and among different types of additives with different compositions by various simulation test means on the basis of the action mechanism of the additives, finally solves the key technical problem through MTM simulation test and program VID bench test evaluation, breaks through the types and the proportions of main agents and auxiliary agents in the traditional lubricating oil system by introducing and adjusting the types and the proportions of the additives, improves the synergistic effect among the additives while reducing the inhibition effect among the single agents, greatly reduces the friction coefficient and prepares the lubricating oil composition with excellent fuel economy after aging.
Antioxidant antiwear agent
In order to balance the interaction among additives, especially improve the aging resistance of oil products while considering the limit range of phosphorus element, a large amount of screening and compounding work is carried out on different types of ashless antioxidants, the type and the dosage of ester antioxidants are especially considered, and the formed antioxidant and antiwear additive system has excellent oxidation stability, effectively prolongs the service cycle of oil products and provides antioxidant protection for the function exertion of other additives. The component C of the antioxidant antiwear agent is a mixture of any four or five of butyl octyl zinc dithiophosphate, dioctyl zinc dithiophosphate, isopropyl isooctyl zinc dithiophosphate, amine ashless antioxidant, phenol ashless antioxidant and ester ashless antioxidant. That is, component C contains at least two zinc dithiophosphates and at least two ashless antioxidants because of the synergistic effect between the zinc dithiophosphates and the ashless antioxidants. Zinc dithiophosphates have excellent antioxidant, antiwear and anti-corrosion properties and are generally believed to act as antioxidants by trapping free radicals and decomposing hydroperoxides. Ashless antioxidants can provide hydrogen atoms for peroxide radicals, destroy or prevent chain growth, and generate low-energy stable radicals, and phenolic antioxidants have obvious synergistic effect when used together with amine antioxidants, because phenol contributes to the regeneration of arylamine. The addition of the component C is not particularly limited, and is usually 1.5-2.5% of the total mass of the lubricating oil composition, if the value is less than 1.5%, the dosage is too small, so that the oxidation resistance is reduced, the effect of other functional additives in the lubricating oil cannot be effectively protected, the service life of the oil product is shortened, and if the value is more than 2.5%, the dosage is too large, so that the additive is wasted, even the phosphorus content in the oil product exceeds the standard specification requirement, and no other beneficial effects exist.
Friction reducing agent
In order to ensure that the composition has excellent antifriction performance, the combination of the selection of different types of antifriction antiwear agents and the addition proportion is very critical. For example, the antifriction effect of the organic molybdenum type friction reducing agent is mainly embodied in a boundary lubrication state, and the antifriction performance can be continuously and effectively exerted only by keeping the molybdenum content at a certain content, but the detergency of the oil is reduced while the antifriction performance is improved. Like glycerides and fatty amine friction reducers, the friction reducers with the same type also have the optimal use ratio in different formula systems, if the specific structures of the friction reducers with the same type are different, the friction reducing effect is different, the friction reducers with the type also can reduce the cleaning performance of oil products to a certain extent, and some friction reducers can also cause the reduction of the anti-foaming performance of the oil products. The component D friction reducer in the invention is amine friction reducer and/or ester friction reducer. Organic friction reducers can be generally classified into two types, one being organometallic compounds such as organic molybdenum, organic copper, etc., and the other being ashless type organic compounds such as organic amines and derivatives thereof, polyol esters, etc. Most ashless friction modifiers achieve the purpose of reducing friction by forming an adsorption film which is easy to shear through physical adsorption on a friction surface, and have low consumption in the using process, so that the ashless friction modifiers have strong holding capacity for reducing friction. The organic metal compound is usually influenced by the addition amount, has insignificant anti-wear effect under low dosage, also belongs to a consumption type additive in actual use, and has no ash-free organic anti-friction agent for lasting anti-friction effect on an aged oil product. The invention focuses on developing a lubricating oil with excellent energy-saving effect, so that an ashless friction reducer with long-acting energy-saving effect is selected for product development. The addition amount of the component D is not particularly limited, and is usually 0.1-1.0% of the total mass of the lubricating oil composition, if the value is less than 0.1%, the use amount is too small, so that the friction coefficient of an oil product is large, and the oil product can not pass an energy-saving bench test, and if the value is more than 1.0%, the use amount is too large, so that additive waste is caused, the cleaning performance of the oil product is reduced, and no other beneficial effects are caused.
The present invention also performs a great deal of screening work on other components in the composition.
Base oil
The energy-saving performance of the lubricating oil is related to the type and viscosity of base oil except for functional additives, and the base oil related to the composition can be two or more than two high-viscosity-index hydrogenated base oil compositions with the performance meeting the standard requirement of API III base oil. The amount of the base oil added in the present invention is not particularly limited, but is about 79 to 91.2% by mass of the total mass of the lubricating oil composition, and if the value is less than 79%, the amount is too small, which results in an increase in the amount of the additive and an increase in the cost, and if the value is more than 91.2%, the amount is too large, which results in a decrease in the amount of the functional additive, which does not impart the desired cleaning, dispersing, antioxidant and energy-saving effects to the oil, and has no other advantageous effects.
Finger-sticking agent
The energy saving performance of the lubricating oil is closely related to the type and shear stability of the adhesive, and the invention carries out systematic simulation evaluation on different types and different shear stability of the adhesive, and selects the hydrogenated styrene-isoprene copolymer, the non-dispersed ethylene-propylene copolymer or the mixture of the hydrogenated styrene-isoprene copolymer and the non-dispersed ethylene-propylene copolymer as the adhesive of the composition. The hydrogenated styrene-isoprene copolymer has excellent thickening capacity, shear resistance and low-temperature performance, the non-dispersed ethylene-propylene copolymer also has better thickening capacity and shear resistance, the cost is lower, and the use of the hydrogenated styrene-isoprene copolymer and the non-dispersed ethylene-propylene copolymer is beneficial to improving the viscosity-temperature performance and the cost performance of an oil product. The addition amount of the finger-sticking agent is not particularly limited, and is usually 4.0-10.0% of the total mass of the lubricating oil composition, if the value is lower than 4.0%, the dosage is too small, so that the viscosity is lower, the oil film thickness and the stability are reduced, the abrasion resistance of the oil product is reduced in actual use, and if the value is higher than 10.0%, the dosage is too large, so that the additive is wasted, the viscosity of the oil product is larger, the low-temperature performance and the cleaning performance are reduced, and other beneficial effects are avoided.
Metal detergent
The metal detergent in the lubricating oil composition provided by the invention can be a mixture consisting of any two or three of alkyl salicylate, alkylbenzene sulfonate and sulfurized alkylphenol salt; the alkylbenzene sulfonate has higher base number and antirust property and is a common additive component of the internal combustion engine oil; the salicylate is slightly high in price, but has better high-temperature detergency; the sulfurized alkylphenol salt has better cleaning effect on the top of the piston of the engine at high temperature. Different types of detergents are compounded, so that the additive synergistic effect can be exerted, and the detergent can have better detergency and antirust property while ensuring that an oil product has a certain base number to neutralize acidic substances. The different types of detergents also have different influences on the friction coefficient of an oil product, the lubricating oil has complex formula and various types of additives, and the interaction among the functional agents needs to be balanced by combining experimental means according to the development target of the oil product, so that the optimal use effect is achieved. The addition amount of the metal detergent is not particularly limited, but is usually 1.0-3.0% of the total mass of the lubricating oil composition, if the value is less than 1.0%, the use amount is too small, the detergency of an oil product is reduced, the base number is too low, and the service life of the lubricating oil is shortened, and if the value is more than 3.0%, the use amount is too large, the additive waste is caused, the ash content of the lubricating oil is increased, the exertion of the functions of other functional additives is influenced, and other beneficial effects are not produced.
Ashless dispersants
The ashless dispersant in the lubricating oil composition provided by the invention can be one or two of macromolecular succinimide, polyisobutylene mono-succinimide and polyisobutylene di-succinimide. Ashless dispersants are surfactants that are used primarily to disperse pollutants generated in engines to ensure that the oil is free flowing. The dispersancy of ashless dispersants may help the engine stay clean and, in some cases, help maintain piston cleanliness. The dispersing effects of different dispersants on oil sludge and sediments are different, the macromolecular dispersant generally has a good dispersing effect on sediments generated at high temperature, and the dispersing effect of the dispersant with general molecular weight on oil sludge generated at low temperature is better. The amount of the ashless dispersant added in the present invention is not particularly limited, but is usually 2.0 to 4.0% by mass of the total mass of the lubricating oil composition, and if the amount is less than 2.0%, the amount is too small, resulting in a decrease in oil dispersibility, an increase in surface deposits on engine parts, and a thick oil sump sludge, and if the amount is more than 4.0%, the amount is too large, resulting in a waste of additives, and affecting the effects of other functional additives in the lubricating oil, and there are no other advantageous effects.
Pour point depressant
The pour point depressant in the lubricating oil composition provided by the invention can be alkyl naphthalene type or poly alpha olefin or a composition of any two of the alkyl naphthalene type or the poly alpha olefin. The pour point of the lubricating oil can be reduced by adding the pour point depressant, and the using effect of the oil product in a low-temperature environment is improved. The addition amount of the pour point depressant is not particularly limited in the present invention, and is usually 0.2 to 0.5% by mass of the total mass of the lubricating oil composition, and if the value is less than 0.2%, the amount is too small, which causes the pour point of the lubricating oil to fail the standard requirements, which affects the fluidity in a low-temperature environment, and if the value is more than 0.5%, the amount is too large, which causes the additive to be wasted, and there is no other beneficial effect.
Anti-foaming agent
The anti-foaming agent in the lubricating oil composition provided by the invention can be dimethyl silicone oil, alkyl acrylic acid copolymer, alkyl polyamide or a composition of any two of the dimethyl silicone oil, the alkyl acrylic acid copolymer and the alkyl polyamide, and can reduce the phenomenon that the lubricating oil generates foams due to mechanical stirring in the actual use process, so that the problem that the oil film of parts of engine parts is broken and abraded due to generation of a large amount of foams in use is avoided. The amount of the antifoaming agent to be added in the present invention is not particularly limited, but is usually 0.001 to 0.010% by mass of the total mass of the lubricating oil composition, and if the amount is less than 0.001%, the amount is too small, which results in a decrease in the antifoaming property, and if the amount is more than 0.010%, the amount is too large, which results in a waste of additives, and there is no other advantageous effect.
The prepared lubricating oil composition has the advantages that the sulfur content of the product is 0.20-0.30 percent (mass), the phosphorus content is 0.07-0.08 percent (mass), the nitrogen content is 0.08-0.10 percent (mass), the base number is 6.5-8.0 mgKOH/g, the sulfate ash content is 0.75-0.9 percent (mass), and the lubricating oil composition has excellent fuel economy, oxidation resistance and abrasion resistance.
The invention has the beneficial effects that:
the lubricating oil composition passes VID engine bench tests in GF-5 standard requirements, and the performance meets SN/GF-5 index requirements. The lubricating oil composition of the present invention also exhibited excellent friction reduction in laboratory simulation performance evaluation.
Drawings
FIG. 1 shows MTM test results of new oil
FIG. 2 MTM test results after aging
Detailed Description
The effects of the present invention are further illustrated by the following examples. The following examples are not intended to limit the scope of the invention and any modifications that do not depart from the spirit and scope of the invention are intended to be within the scope of the invention.
In order to screen base oil and additive components, simulation test methods such as heat pipe oxidation, SDT oil sludge dispersibility, MTM friction characteristics, PDSC (induction period) and the like are adopted in a laboratory to respectively evaluate the high-temperature clean dispersibility, the low-temperature oil sludge dispersibility, the antifriction property and the oxidation stability of an oil product. The simulation test conditions are as follows: the heat pipe oxidation test temperature is set to 285 ℃, the SDT oil sludge dispersibility test temperature is set to 150 ℃, an MTM (Mini Traction machine) tester is used for evaluating the friction coefficient of an oil product under the conditions of elastic fluid dynamic pressure lubrication and boundary/mixing, and the method is an important evaluation method of an energy-saving gasoline engine oil product, and the research test sets 50% slip-roll ratio at 140 ℃ and 36N and sets the PDSC oxidation induction period temperature to 210 ℃.
Example 1:
taking 100Kg of the product of the invention as an example, the raw materials and the mass ratio thereof are as follows:
example 2:
taking 100Kg of the product of the invention as an example, the raw materials and the mass ratio thereof are as follows:
example 3:
taking 100Kg of the product of the invention as an example, the raw materials and the mass ratio thereof are as follows:
in the embodiment 1, the calcium alkyl benzene sulfonate with the base number of 300-314 is replaced by the same mass of synthetic calcium salicylate with the base number of 265-298, the single succinimide is replaced by the same mass of double succinimide, and other components and masses are the same.
Example 4:
taking 100Kg of the product of the invention as an example, the raw materials and the mass ratio thereof are as follows:
in the embodiment 2, the calcium alkyl benzene sulfonate with the base number of 395-420 is replaced by the same mass of the synthetic calcium sulfonate with the base number of 300-314, the bis-succinimide is replaced by the same mass of the mono-succinimide, and other components and masses are the same.
To verify the effect of the present invention, the inventors performed laboratory simulation performance evaluation and engine bench test using the engine lubricating oil prepared in the examples of the present invention, and the test results were as follows:
1. laboratory simulation performance evaluation of lubricating oil composition of the invention
TABLE 1 evaluation results of the simulation Properties of lubricating oil compositions of the present invention
As can be seen from the data in table 1, fig. 1 and fig. 2, the lubricating oil of the present invention is similar to the commercially available oil in the simulation test evaluation of the hot tube oxidation, SDT sludge dispersibility and PDSC oxidation induction period, but the friction coefficient is lower than that of the commercially available reference oil in both the new oil and the aged oil, and the lubricating oil has excellent fuel economy compared to the commercially available gasoline engine oil.
2. Example 1 lubricating oil composition of the invention Engine bench test
TABLE 2 bench test results for lubricating oil compositions of inventive example 2
As can be seen from the data in Table 2, the lubricating oil composition of example 1 of the present invention passed the VID engine bench test for SN/GF-5 quality index, and the measured value of the blended 5W-30 engine oil reached the standard requirement of 5W-20, thus having excellent fuel economy.
3. EXAMPLE 2 lubricating oil compositions of the invention NEDC cycle and mechanical loss test investigation
To examine the fuel economy of the lubricating oil compositions of the present invention, NEDC and mechanical loss tests were also conducted. NEDC cycling test: on the basis of a finished automobile fuel consumption test method, the method includes measuring and recording corresponding engine working conditions in finished automobile test cycles, programming test programs on an engine rack to operate corresponding working conditions to simulate an NEDC cycle, operating the cycle and recording fuel consumption, and obtaining the NEDC cycle fuel consumption of the engine. Mechanical loss test: on the basis of the friction loss work measuring method in GB/T18297, the friction loss work of each main part of the engine is obtained by gradually peeling the air inlet and exhaust system, the moving part and the driving accessory to measure the friction work of each system, and a basis is provided for the evaluation and optimization of the friction work of each part of the engine.
TABLE 3 simulation of NEDC Fuel consumption test results
TABLE 4 mechanical loss test results
| Temperature of | 40 |
100℃ | 120℃ |
| Relative SJ10W-30 | The reduction is 5.6 percent | The reduction is 2.55 percent | The reduction is 1.78 percent |
Compared with reference oil SJ10W-30, the mechanical loss of the engine oil at 40 ℃, 100 ℃ and 120 ℃ is reduced, and the fuel saving effect of the NEDC is obvious.
To verify the synergistic effect of the component C of the present invention, the inventors fixed A, B, D, E, F, G, H components in addition to the component C and conducted blending of example 5 and comparative examples 1 and 2, and conducted simulation test evaluation of PDSC.
Example 5:
taking 100Kg of oil product as an example, the used raw materials and the mass ratio thereof are as follows:
comparative example 1:
taking 100Kg of oil product as an example, the used raw materials and the mass ratio thereof are as follows:
comparative example 2:
taking 100Kg of oil product as an example, the used raw materials and the mass ratio thereof are as follows:
4. example 5 and comparative examples 1 and 2 laboratory simulation Performance evaluation
TABLE 5 evaluation results of component C synergy simulation performance
| Item | Example 5 | Comparative example 1 | Comparative example 2 | Test method |
| PDSC(210℃)/％ | 27.1 | 13.1 | 21 | SH/T 0719 |
As can be seen from the data in Table 5, the component C of the present invention is effective in improving the oxidation resistance of the oil.
Claims (10)
1. The engine lubricating oil composition comprises the following components in percentage by total mass:
the component C is a mixture consisting of any four or five of zinc butyl octyl dithiophosphate, zinc dioctyl dithiophosphate, isopropyl isooctyl zinc dithiophosphate, amine ashless antioxidant, phenol ashless antioxidant and ester ashless antioxidant;
the component D is amine friction reducing agent and/or ester friction reducing agent.
2. The lubricating oil composition for engines as claimed in claim 1, wherein the composition is composed of the following components in percent by weight based on the total weight of the composition:
3. the engine lubricating oil composition of claim 1 or 2, wherein the amine ashless antioxidant is an alkyl diphenylamine ashless antioxidant; the phenolic ashless antioxidant is a phenolic ashless antioxidant containing ester groups; the ester ashless antioxidant is dialkyl dithiocarbamate ashless antioxidant; the amine friction reducing agent is diamine ester friction reducing agent; the ester friction reducing agent is a hindered phenol-containing glyceride friction reducing agent.
4. The engine lubricating oil composition as claimed in claim 1 or 2, wherein the component a is a mixture consisting of any two or three of alkyl salicylate, alkyl benzene sulfonate and sulfurized alkyl phenate;
the component B is one or two of macromolecular succinimide, polyisobutylene mono-succinimide and polyisobutylene bis-succinimide.
5. The engine lubricating oil composition of claim 3, wherein the alkyl salicylate is calcium alkyl salicylate or magnesium alkyl salicylate; the alkylbenzene sulfonate is calcium alkylbenzene sulfonate or magnesium alkylbenzene sulfonate; the sulfurized alkylphenol salt is sulfurized calcium alkylphenol.
6. The engine lubricating oil composition according to any one of claims 1 to 4, wherein the component E is a styrene-isoprene copolymer and/or a non-dispersed ethylene-propylene copolymer;
the component F is alkyl naphthalene type and/or poly alpha-olefin;
the component G is one or two of simethicone, alkyl acrylic acid copolymer and alkyl polyamide.
7. The lubricating engine oil composition of any one of claims 1-5, wherein the base oil is a high viscosity index hydrogenated base oil composition having properties meeting API group III base oil standards.
8. A method for producing an engine lubricating oil composition according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) adding base oil with required amount into a stainless steel blending kettle with a stirrer, heating to 60-70 ℃, stirring for 1-2 hours, adding an antifoaming agent into the blending kettle, and continuing stirring for 1-2 hours;
(2) sequentially adding the pour point depressant and the viscosity index improver into the blending kettle, and continuously stirring for 1-2 hours;
(3) and sequentially adding the ashless dispersant, the antioxidant, the metal detergent and the antifriction agent into a blending kettle, and continuously stirring for 3-4 hours at the temperature of 60-70 ℃ until the mixture is uniform, thus obtaining the engine lubricating oil composition.
9. The method for preparing the engine lubricating oil composition according to claim 8, wherein the prepared engine lubricating oil composition has a sulfur content of 0.20 to 0.30 wt%, a phosphorus content of 0.07 to 0.08 wt%, a nitrogen content of 0.08 to 0.10 wt%, a base number of 6.5 to 8.0mgKOH/g, and a sulfated ash content of 0.75 to 0.9 wt%.
10. Use of the engine lubricating oil composition according to any one of claims 1 to 7.
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| CN114752427A (en) * | 2021-01-11 | 2022-07-15 | 中国石油天然气股份有限公司 | Lubricating oil composition |
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