CN115960651A - Antioxidant composition and preparation method thereof - Google Patents
Antioxidant composition and preparation method thereof Download PDFInfo
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- CN115960651A CN115960651A CN202111187038.0A CN202111187038A CN115960651A CN 115960651 A CN115960651 A CN 115960651A CN 202111187038 A CN202111187038 A CN 202111187038A CN 115960651 A CN115960651 A CN 115960651A
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- 239000000203 mixture Substances 0.000 title claims abstract description 74
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 61
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 9
- -1 amine compound Chemical class 0.000 claims abstract description 66
- 239000010687 lubricating oil Substances 0.000 claims abstract description 49
- 230000003647 oxidation Effects 0.000 claims abstract description 44
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 44
- 230000007797 corrosion Effects 0.000 claims abstract description 26
- 238000005260 corrosion Methods 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 150000002148 esters Chemical class 0.000 claims abstract description 15
- 239000012964 benzotriazole Substances 0.000 claims abstract description 13
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000009471 action Effects 0.000 claims abstract description 7
- 239000003377 acid catalyst Substances 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 60
- 229910052799 carbon Inorganic materials 0.000 claims description 59
- 229910052739 hydrogen Inorganic materials 0.000 claims description 42
- 239000007795 chemical reaction product Substances 0.000 claims description 34
- 150000003141 primary amines Chemical class 0.000 claims description 29
- 239000000047 product Substances 0.000 claims description 27
- 150000003973 alkyl amines Chemical class 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 17
- 239000002199 base oil Substances 0.000 claims description 13
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- 239000000194 fatty acid Substances 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
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- 150000001412 amines Chemical class 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
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- 239000004973 liquid crystal related substance Substances 0.000 claims 1
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- 238000006243 chemical reaction Methods 0.000 description 33
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- 238000010521 absorption reaction Methods 0.000 description 21
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- 239000007788 liquid Substances 0.000 description 14
- ZLUHLPGJUZHFAR-UHFFFAOYSA-N n-[4-(2,4,4-trimethylpentan-2-yl)phenyl]naphthalen-1-amine Chemical compound C1=CC(C(C)(C)CC(C)(C)C)=CC=C1NC1=CC=CC2=CC=CC=C12 ZLUHLPGJUZHFAR-UHFFFAOYSA-N 0.000 description 13
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- 125000004404 heteroalkyl group Chemical group 0.000 description 6
- 125000005842 heteroatom Chemical group 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
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- 238000010438 heat treatment Methods 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- LBPABMFHQYNGEB-UHFFFAOYSA-N benzene;2h-triazole Chemical compound C=1C=NNN=1.C1=CC=CC=C1 LBPABMFHQYNGEB-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
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- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 3
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- 238000005292 vacuum distillation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
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- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 239000012208 gear oil Substances 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
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- 230000035484 reaction time Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
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- 238000001228 spectrum Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
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- ZHKBLALOBMBJLL-UHFFFAOYSA-N 1-hexylperoxyhexane Chemical compound CCCCCCOOCCCCCC ZHKBLALOBMBJLL-UHFFFAOYSA-N 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- QVXGKJYMVLJYCL-UHFFFAOYSA-N 2,3-di(nonyl)-N-phenylaniline Chemical compound C(CCCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCCC QVXGKJYMVLJYCL-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- CJXFOEBYWJIGOE-UHFFFAOYSA-N C(CC(C=C1)=CC=C1NC1=CC=CC2=CC=CC=C12)C1=CC=CC=C1 Chemical compound C(CC(C=C1)=CC=C1NC1=CC=CC2=CC=CC=C12)C1=CC=CC=C1 CJXFOEBYWJIGOE-UHFFFAOYSA-N 0.000 description 1
- UNHDTFMBWASCAI-UHFFFAOYSA-N CC(C)(C)N(C(C)(C)C)C(SCSC(N(C(C)(C)C)C(C)(C)C)=S)=S Chemical compound CC(C)(C)N(C(C)(C)C)C(SCSC(N(C(C)(C)C)C(C)(C)C)=S)=S UNHDTFMBWASCAI-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- SXSVTGQIXJXKJR-UHFFFAOYSA-N [Mg].[Ti] Chemical compound [Mg].[Ti] SXSVTGQIXJXKJR-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
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- 230000029936 alkylation Effects 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- WMUIZUWOEIQJEH-UHFFFAOYSA-N benzo[e][1,3]benzoxazole Chemical compound C1=CC=C2C(N=CO3)=C3C=CC2=C1 WMUIZUWOEIQJEH-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
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- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
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- 125000001624 naphthyl group Chemical group 0.000 description 1
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- VWSUVZVPDQDVRT-UHFFFAOYSA-N phenylperoxybenzene Chemical compound C=1C=CC=CC=1OOC1=CC=CC=C1 VWSUVZVPDQDVRT-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 230000003595 spectral effect Effects 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
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Abstract
The invention provides an antioxidant composition and a preparation method thereof. The antioxidant composition comprises an amine compound and a multifunctional oily agent, wherein the structure of the amine compound is shown as the formula (I):
Description
Technical Field
The invention relates to an antioxidant composition, in particular to an antioxidant composition which can be used in aviation synthetic ester lubricating oil and has high-temperature oxidation and corrosion resistance.
Background
The high-temperature corrosion and oxidation stability of the lubricating oil of the aero-engine refers to the high-temperature oxidation resistance and high-temperature deposition alleviation capability of the lubricating oil in the using process, and is an important embodiment of the high-temperature oxidation resistance of the aero-engine oil. Under the induction of high-temperature oxygen and the action of metal catalysis, a series of chemical changes such as oxidation, polymerization, alkylation, decomposition and the like occur in a short period of time to cause a great amount of sediments such as oil sludge and the like generated by engine oil to be attached to metal accessories, pistons adhere to rings, seriously corrode equipment, shorten the service life of the equipment and seriously affect the normal working and running of an aeroengine. The improvement of the high-temperature corrosion and oxidation stability of the aircraft engine oil has important significance for improving the working efficiency and the service life of lubricating system equipment.
With the development of the aviation industry and the increase in the flight speed of aircraft, the service temperature of the main body of turbojet oil increases from 80 ℃ in the early stage to 220 ℃ at present, and the temperature of the main body of next generation aircraft engine oil is expected to exceed 350 ℃. The environmental characteristics of high temperature, high speed and high load of the aero-engine put increasing demands on the performance of the aero-engine lubricating oil. When the outlet temperature of the aircraft engine is more than 200 ℃, the oxidation speed of the common engine lubricating oil is multiplied, so that the viscosity of the lubricating oil is increased, the total acid value is increased, the corrosivity is strong, and a large amount of sediments are generated. To effectively alleviate these problems, it is necessary to improve the high temperature corrosion and oxidation stability of an aircraft engine lubricating oil, which are directly related to the service life of the aircraft engine lubricating oil and the performance of the engine lubrication system components.
The high-temperature corrosion and oxidation stability of the aircraft engine oil are closely related to the structures and high-temperature properties of the base oil and the antioxidant. Therefore, the high-temperature corrosion and oxidation stability of the aircraft engine oil is effectively improved, and a high-temperature oxidation and corrosion inhibitor with excellent chemical structure and high-temperature oxidation resistance needs to be synthesized, so that the base oil is effectively protected, the generation of oxidation products is reduced, the oil solubility of the oxidation products is improved, the sediment is reduced, and the problems of oil quality deterioration and sediment of the aircraft engine lubricating oil under the high-temperature condition are effectively solved.
Four centistokes (4 mm) with a kinematic viscosity rating of four centistokes at 100 ℃ in the international famous aviation lubricant specification MIL-PRF-7808L specification 2 And/s) the aircraft engine lubricating oil simultaneously requires good high-temperature oxidation resistance and low-temperature fluidity, thereby ensuring the rapid flight of the aircraft under high temperature, high rotating speed and high load, and ensuring the rapid take-off, flexible maneuvering, high-speed cruising and safe landing of the aircraft in alpine regions. It is desirable to synthesize a high-temperature antioxidant having excellent chemical structure and high-temperature antioxidant property, thereby effectively protecting the base oil, reducing the generation of oxidation products, and reducing the oxidation productsFew deposits and effectively relieves the problems of deterioration and deposition of high-temperature oil of the aircraft engine oil, thereby ensuring the high-temperature safe and stable operation of the aircraft engine. Meanwhile, the lubricating oil composition has lower kinematic viscosity and better low-temperature fluidity at low temperature, and the kinematic viscosity is less than or equal to 20000 (mm) at the temperature of-51 ℃ in accordance with the MIL-PRF-7808L specification 2 The index requirement of/s) is more favorable for the low-temperature lubrication service of lubricating oil and the safe and quick start and flight of the aviation aircraft in a low-temperature environment.
The oiliness agent is used for reducing friction, and is dissolved in lubricating oil to form a firm directional adsorption film on a friction surface, reduce friction and abrasion between moving parts and improve the friction performance of the lubricating oil. The oiliness agent has many kinds, and mainly comprises animal and vegetable oil, higher fatty acid, higher fatty alcohol, amine, amide, ester, sulfurized grease and the like. At present, the common oiliness agents in China comprise sulfurized cottonseed oil, fatty acid ester, benzotriazole fatty acid amine salt and the like. The benzotriazole fatty acid amine salt has the performances of oil solubility, wear resistance, oxidation resistance, corrosion resistance, rust resistance and the like, is added into natural mineral oil and lubricating oil to be used as a rust inhibitor, an antioxidant, a metal passivator, an antiwear agent, a preservative and the like, achieves good effects, can be used in gear oil, hyperbolic gear oil, wear-resistant hydraulic oil, oil film bearing oil and lubricating grease, and can also be used as a rust inhibitor and a gas phase corrosion inhibitor to be used in antirust grease.
There are patents and literatures describing a process for producing a benzotriazole derivative, which is strictly controlled in reaction conditions or difficult in separation and purification and has a low product yield.
The product produced by the prior process is a light yellow flocculent solid, has certain oil solubility, wear resistance, oxidation resistance, corrosion resistance, rust resistance and other properties, and has the defects of poor oil solubility under the low temperature condition, easy precipitation, turbid lubricating oil product, long-term standing precipitation and unfavorable oil product use performance under the low temperature condition. In addition, the flocculent solid benzotriazole fatty ammonium salt is inconvenient for blending oil products in the actual production process of lubricating oil, and the liquid benzotriazole fatty ammonium salt has obvious advantages in this respect.
US 3,697,427 discloses the use of benzotriazole or certain alkylphenyltriazoles as metal deactivators in synthetic lubricating oil compositions. US 3,790,481 discloses the use of methyl bis-benzotriazole, alkylbenzotriazole, naphthoxazole as copper passivators in polyol ester lubricant compositions.
US 5,076,946 discloses the application of a methyl dialkyl benzotriazole dimer derivative as a metal deactivator in lubricating oil, and improves the oxidation stability of the lubricating oil. US 6,743,759B2 discloses a lubricating oil antioxidant extreme pressure antiwear agent with good performance formed by compounding methylene bis-di-tert-butyl-dithiocarbamate with derivatives of alkylbenzene triazole and diphenylamine according to a certain proportion.
Disclosure of Invention
The invention provides an antioxidant composition and a preparation method thereof, which comprises the following aspects.
In a first aspect, the present invention provides an antioxidant composition.
The antioxidant composition comprises an amine compound and a multifunctional oiliness agent, wherein the structure of the amine compound is shown as the formula (I):
the formula (I) is a compound formed by bonding m structural units shown as the formula (II),
in formula (I), m is an integer of 1 to 10, preferably 1 to 5, more preferably 1 to 3; each R is I Each independently selected from H, C 1～10 Straight or branched chain alkyl, preferably selected from H, C 1～5 Straight or branched chain alkyl, more preferably selected from H, C 1～3 A linear or branched alkyl group; each x is independently selected from an integer between 0 and 4, preferably an integer between 0 and 2, more preferably 0 or 1; each R is II Each independently selected from H, C 1～10 Straight or branched chain alkanesPreferably H, C 1～5 Straight or branched chain alkyl, more preferably selected from H, C 1～3 A linear or branched alkyl group; each y is independently selected from an integer between 0 and 2, preferably 0 or 1; each R is III Each independently selected from H, C 1～10 Straight or branched chain alkyl, preferably selected from H, C 1～5 Straight or branched chain alkyl, more preferably selected from H, C 1～3 A linear or branched alkyl group; each z is independently selected from an integer between 0 and 3, preferably an integer between 0 and 2, more preferably 0 or 1;
each L in the formula (II) I 、L II 、L III Each independently H, C 1～4 Alkyl, and L in different structural units I 、L II 、L III A bonded bonding end.
According to the invention, preferably, in formula (I), L in the same structural element I 、L II 、L III Are not bonded with each other.
According to the invention, in formula (I), when m =1, L I 、L II 、L III Each independently is H or C 1～4 An alkyl group.
According to the invention, in formula (I), when m =2, there are 2 structural units as shown in formula (II), L of 2 structural units I 、L II 、L III (when they are both bonded ends) can be bonded to each other, optionally with only one L each between 2 building blocks I 、L II Or L III Inter-bonding, i.e. only one covalent bond is formed between 2 different building blocks.
According to the invention, in formula (I), when m is greater than 2, there are m structural units as shown in formula (II), L of the m structural units I 、L II 、L III (when they are bonded ends) and further optionally, m structural units are 1 end structural unit, (m-2) middle structural unit and 1 other end structural unit which are bonded in sequence, and only one L in each end structural unit exists I 、L II Or L III And L in the intermediate structural unit adjacent thereto I 、L II Or L III Bonding, there being 2L in each structural unit in the middle I 、L II Or L III L in the structural units adjacent to each other I 、L II Or L III Bonding, i.e. the formation of only one covalent bond between each two connected different building blocks.
According to the present invention, examples of the compounds represented by the formula (I) include:
according to the present invention, the preparation method of the amine compound comprises: reacting a compound shown as a formula (alpha) in the presence of peroxide, and collecting a product;
in the formula (. Alpha.), each R I Each independently selected from H, C 1～10 Straight or branched chain alkyl, preferably selected from H, C 1～5 Straight or branched chain alkyl, more preferably selected from H, C 1～3 A linear or branched alkyl group; each x is independently selected from an integer between 0 and 4, preferably an integer between 0 and 2, more preferably 0 or 1; each R is II Each independently selected from H, C 1～10 Straight or branched chain alkyl, preferably selected from H, C 1～5 Straight or branched chain alkyl, more preferably selected from H, C 1～3 A linear or branched alkyl group; each y is independently selected from an integer between 0 and 2, preferably 0 or 1; each R is III Each independently selected from H, C 1～10 Straight or branched chain alkyl, preferably selected from H, C 1～5 Straight or branched chain alkyl, more preferably selected from H, C 1～3 A linear or branched alkyl group; each z is independently selected from an integer between 0 and 3, preferably an integer between 0 and 2, more preferably 0 or 1.
According to the present invention, it is preferable that in the compound represented by the formula (α), a hydrogen atom is present in at least one of the ortho positions of the benzene ring to which the amine group is attached, and each of the carbon atoms in the para-position and the para-position to the amine group on the naphthalene ring to which the amine group is attached contains a hydrogen atom.
According to the invention, the compound of formula (α) may optionally be selected from one or more of the following compounds: n-p-tert-butyl-phenyl-1-naphthylamine, N-p-tert-octyl-phenyl-1-naphthylamine, N-p-phenethyl-phenyl-1-naphthylamine, N-phenyl-1-naphthylamine.
According to the invention, the temperature at which the compound represented by formula (alpha) is reacted is preferably 110 to 200 ℃, more preferably 130 to 190 ℃; the absolute pressure at which the compound represented by the formula (. Alpha.) is reacted is not particularly limited, but is preferably 0.01 to 0.15MPa, more preferably 0.01 to 0.12MPa.
According to the present invention, the reaction time of the compound represented by the formula (α) is generally as long as possible, and is preferably 3 to 12 hours, more preferably 4 to 10 hours.
According to the invention, the peroxide is preferably an organic peroxide. The organic peroxide may be one or more of alkyl peroxide, acyl peroxide, peroxyketal, and peroxyorganic ester.
The alkyl peroxide has the structure: r 1 -O-O-R 2
The structure of acyl peroxides is: (R) 1 ) 2 -C-(O-O-R 2 ) 2
The structure of the peroxyketal is:
the peroxide organic ester has the structure:
wherein each R 1 、R 2 Each group is one or more of alkyl, aryl, alkyl substituted aryl or aryl substituted alkyl with total carbon number of 2-10, preferably total carbon number of 4-6 alkyl and/or phenyl, most preferably tert-butyl and/or phenyl.
According to the invention, the organic peroxide is preferably one or more of the organic peroxyesters tert-butyl-2-ethyl peroxyhexanoate, peroxyketal 2,2-bis (tert-butylperoxy) butane, di-tert-butyl peroxide, dihexyl peroxide and diphenyl peroxide, most preferably di-tert-butyl peroxide.
According to the invention, the molar amount of the peroxide is preferably 0.8 to 1.5 times the molar amount of the compound represented by the formula (. Alpha.).
According to the invention, the peroxide can be used to form the corresponding light molecular compound after the reaction is finished, preferably by distillation under reduced pressure.
According to the invention, the reaction is preferably carried out under the protection of an inert gas, preferably nitrogen.
According to the present invention, preferably, a solvent may be added in the reaction. The solvent is preferably C 6 ～C 20 Alkanes, most preferably C 6 ～C 10 Alkanes, such as n-decane, n-heptane, cyclohexane. The amount of the solvent to be added is not particularly limited from the prior art, and the solvent may be removed by a method known in the art (e.g., distillation) after the reaction is completed.
According to the invention, the product can be subjected to a purification operation in order to increase the purity of the product. Examples of the purification method include washing, recrystallization, and the like, and are not particularly limited.
According to the invention, the product may contain small amounts of unreacted compounds of formula (α), which may otherwise be used alone as conventional antioxidants without isolation from the product.
According to the invention, the product can be a single amine compound or a mixture of a plurality of amine compounds, which are all contemplated by the invention, and the difference of the existing forms does not influence the achievement of the effect of the invention. Therefore, these products are collectively referred to as the amine compounds without distinction in the context of this specification. In view of this, according to the present invention, there is no absolute necessity to further purify the reaction product or to further separate the amine compound of a specific structure from the reaction product. Of course, such purification or isolation is preferable for further improvement of the intended effect of the present invention, but is not essential to the present invention. Nevertheless, as the purification or separation method, for example, purification or separation of the product by a column chromatography method, preparative chromatography or the like can be mentioned.
According to the invention, the multifunctional oily agent is a reaction product of alkyl benzene triazole and/or benzene triazole and mixed alkyl primary amine under the action of an acid catalyst.
According to the invention, the preparation method of the multifunctional oiliness agent comprises the following steps: under the existence of inert gas, the alkylbenzene triazole and/or the benzotriazole and alkyl primary amine react under the action of an acid catalyst, and a product is collected.
According to the invention, the structure of the alkyl benzene triazole and/or the benzene triazole is as follows:
in the formula R 1 ' selected from H, C 1 ～C 12 Straight or branched alkyl, preferably C 1 ～C 8 Straight or branched chain alkyl, most preferably methyl.
According to the invention, the alkyl primary amine is C 16 ～C 22 The primary alkyl amine of the formula R 2 ’CH 2 NH 2 Wherein R is 2 ' is C 15 ～C 21 Linear or branched alkyl.
According to the invention, the primary alkylamine is preferably C 16 ～C 22 The mixed primary alkyl amine of (1), which is a mixture of a linear primary amine and a branched primary amine.
According to the invention, based on the total mole number of the mixed alkyl primary amine, the alkyl is divided into the following components in mole percentage: said C 16 ～C 22 Mixed alkyl of (2)The primary amine contains 55-90% of C 16 ～C 22 Linear alkyl primary amine and 10-45% of C 16 ～C 22 Preferably contains 55% to 80% of C 16 ～C 22 Linear alkyl primary amine and 20-45% of C 16 ～C 22 Branched primary alkyl amines of (1).
According to the invention, based on the total mole number of the mixed alkyl primary amine, the carbon-containing fraction is as follows in mole percentage: said C 16 ～C 22 Mixed primary alkyl amines of (1) 16 ～C 18 The content of alkyl primary amine is 45-85 percent, C 19 ～C 22 The content of the primary alkylamine of (2) is 15% to 55%, preferably C 16 ～C 18 The content of alkyl primary amine is 55-75 percent, C 19 ～C 22 The content of alkyl primary amine is 25-45%.
According to the invention, based on the total mole number of the mixed alkyl primary amine, the alkyl group is divided into the following types by the carbon number and the alkyl group in mole percentage: in said C 16 ～C 22 In the mixed alkyl primary amines of (1), C 16 ～C 18 The content of the linear primary amine is 40 to 70 percent, C 19 ～C 22 The content of the linear primary amine (C) is 15 to 40 percent 16 ～C 18 The content of branched primary amine is 5-35 percent, C 19 ～C 22 The content of the branched primary amine is 5 to 30 percent; preferably C 16 ～C 18 The content of the linear primary amine is 45 to 60 percent, C 19 ～C 22 The content of the linear primary amine is 20 to 35 percent, C 16 ～C 18 The content of branched primary amine is 5-25%, C 19 ～C 22 The content of the branched primary amine is 5 to 30 percent.
According to the invention, the acidic catalyst is preferably glacial acetic acid, sulfuric acid, hydrochloric acid, phosphoric acid, SO 3 And P 2 O 5 Preferably sulfuric acid and/or glacial acetic acid or an aqueous solution thereof, most preferably glacial acetic acid or acetic acid in a mass percentage of 60% to 100%.
According to the invention, the molar ratio between the alkylbenzotriazole and/or benzotriazole and the primary alkylamine is 1:0.5 to 1, preferably 1:0.8 to 1.
According to the invention, the mass ratio of the acidic catalyst to the alkylbenzene triazole and/or the benzene triazole is 1:0.5 to 5, preferably 1:0.8 to 4.
According to the invention, the reaction temperature of the alkyl benzene triazole and/or the benzene triazole and the alkyl primary amine under the action of the acid catalyst is 60-100 ℃, preferably 80-100 ℃, and the reaction time is usually better as long as possible, generally 2-8 h, preferably 3-6 h.
According to the present invention, preferably, in the antioxidant composition, the mass ratio between the amine compound and the multifunctional oily agent is 10 to 60:1, preferably 15 to 50:1, and more preferably 20-45. The antioxidant composition can obviously improve the oxidation stability, the high-temperature corrosion resistance, the low-temperature viscosity and the low-temperature fluidity of lubricating oil (especially synthetic lubricating oil), is especially suitable for aviation synthetic lubricating oil (especially four centistokes-grade aviation lubricating oil), can effectively protect base oil, reduce the generation of oxidation products and sediments and effectively relieve the problems of deterioration and sedimentation of high-temperature oil of aviation engine oil.
In a second aspect, the present invention provides a process for the preparation of the antioxidant composition as hereinbefore described.
According to the invention, the preparation method of the antioxidant composition comprises the step of mixing the amine compound and the multifunctional oily agent. The mixing temperature is preferably 50-100 ℃; more preferably 60 ℃ to 90 ℃; the mixing time is preferably 0.5-5 h; more preferably 1 to 4 hours.
In a third aspect, the present invention provides the use of an antioxidant composition as described in the preceding aspects.
The antioxidant composition can be used as a high-temperature antioxidant and a free radical scavenger, can remarkably improve the high-temperature oxidation resistance and thermal degradation resistance of lubricating oil, particularly ester base oil, remarkably reduces the viscosity change rate of the lubricating oil before and after oxidation, the change of the total acid value, the generation of sediments and the quality change of metal test pieces before and after oxidation, can prolong the service time of the ester oil, and reduce the oil change frequency.
In a fourth aspect, the present invention provides a lubricating oil composition.
The lubricating oil composition of the invention comprises lubricating base oil and the antioxidant composition. The antioxidant composition accounts for 0.5-10% of the total mass of the lubricating oil composition, and preferably accounts for 1.5-8% of the total mass of the lubricating oil composition. The lubricating base oil is preferably a synthetic hydrocarbon and/or a synthetic ester. Other types of additives, such as viscosity index improvers, anti-wear agents, pour point depressants, rust inhibitors, and the like, may also be added to the lubricating oil compositions of the present invention.
The lubricating oil composition has excellent oxidation stability and high-temperature corrosion resistance. The preferable lubricating oil composition can keep excellent low-temperature viscosity and low-temperature fluidity at the temperature of-51 ℃, and can ensure safe and stable work of an aeroengine at high temperature and safe and quick start at low temperature.
In a fifth aspect, the present invention also provides a method for improving the antioxidant and corrosion resistance of a lubricating oil composition, which comprises adding the antioxidant composition as described above to a lubricating base oil.
The invention also provides a method for improving the oxidation resistance and corrosion resistance of the lubricating oil composition, which is to add the antioxidant composition into lubricating base oil, wherein the antioxidant composition accounts for 3-15 percent of the total mass of the lubricating oil composition, and preferably 5-10 percent of the total mass of the lubricating oil composition. The lubricating base oil is selected from synthetic hydrocarbons and/or synthetic esters, preferably C 4 -C 8 Polyols and C 3 -C 12 Esters formed by the reaction of fatty acids, most preferably trimethylolpropane and/or pentaerythritol esters.
The antioxidant composition can obviously improve the oxidation resistance and corrosion resistance of lubricating oil, particularly synthetic lubricating oil, and is particularly suitable for aviation synthetic ester lubricating oil.
Drawings
FIG. 1 is a superimposed infrared spectrum of a reaction raw material p-tert-octyl-phenyl-1-naphthylamine (L06) and a reaction product A1.
Detailed Description
In the context of the present specification, the expression "number + valence + group" or the like refers to a group obtained by removing the number of hydrogen atoms represented by the number from the basic structure (such as a chain, a ring, a combination thereof, or the like) to which the group corresponds, and preferably refers to a group obtained by removing the number of hydrogen atoms represented by the number from a carbon atom (preferably a saturated carbon atom and/or a non-identical carbon atom) contained in the structure. For example, "3-valent straight or branched alkyl" refers to a group obtained by removing 3 hydrogen atoms from a straight or branched alkane (i.e., the base chain to which the straight or branched alkyl corresponds), and "2-valent straight or branched heteroalkyl" refers to a group obtained by removing 2 hydrogen atoms from a straight or branched heteroalkane (preferably from a carbon atom contained in the heteroalkane, or further, from a non-identical carbon atom).
In the context of the present specification, the heteroalkyl group refers to a group obtained by interrupting the carbon chain structure of an alkyl group with one or more (e.g., 1 to 5, 1 to 4, 1 to 3, 1 to 2, or 1) hetero groups selected from the group consisting of-Sx-, -O-, and-NR "", wherein x is an integer between 1 and 5 (preferably an integer between 1 and 4, more preferably 1,2, or 3). From the viewpoint of structural stability, it is preferable that, when a plurality of hetero groups are present, any two of the hetero groups are not directly bonded to each other. It is apparent that the hetero group is not at the end of the carbon chain of the hydrocarbyl group. For convenience of description, the number of carbon atoms of the alkyl group prior to the interruption is still used to refer to the number of carbon atoms of the heteroalkyl group after the interruption. For example, C 4 Straight chain alkyl (CH) 3 -CH 2 -CH 2 -CH 2 -) interrupted by a hetero-group-O-to obtain CH 3 -O-CH 2 -CH 2 -CH 2 -、CH 3 -CH 2 -O-CH 2 -CH 2 -or CH 3 -CH 2 -CH 2 -O-CH 2 -equal C 4 The linear heteroalkyl, interrupted by two hetero radicals-S-, giving CH 3 -S-CH 2 -S-CH 2 -CH 2 -、CH 3 -CH 2 -S-CH 2 -S-CH 2 -or CH 3 -S-CH 2 -CH 2 -S-CH 2 -etc. C 4 The straight-chain heteroalkyl, interrupted by three hetero groups-S-, giving CH 3 -S-CH 2 -S-CH 2 -S-CH 2 -equal C 4 A straight chain heteroalkyl group.
The percentages and ratios mentioned below are percentages by mass or ratios by mass unless otherwise stated.
The raw materials used were as follows:
antioxidant L06, p-tert-octyl-phenyl-1-naphthylamine, basff Corp., purity > 98%
VANLUBEV81, van der Bilt, USA, purity > 98%
VANLUBENA, van der Bilt, USA, purity > 98%
Antirust agent, 5-methylbenzotriazole, shanghai chemical plant, chemical purity
C16-C22 alkyl primary amine monomer with purity of more than 97% and purchased from chemical institute of Chinese academy of sciences
Antioxidant T534, antioxidant alkyldiphenylamine, kyop, institute of petrochemical technology
Antioxidant T501,2,6-di-tert-butyl-4-methylphenol, liyunnangning chemical Co., ltd
Antioxidant T558, dinonyldiphenylamine, liaoning Tianhe Fine chemical Co., ltd
Antioxidant T531, N-phenyl-1-naphthylamine, mitsu Toyobo chemical Co., ltd
Pentaerythritol ester, zhejiang Quzhou chemical Co., ltd., kinematic viscosity at 100 ℃ of 5.02mm 2 /s.
Saturated acid ester of a tetra-centis polyol, having a kinematic viscosity of 3.82mm at 100 ℃ from Shanto Ruijie chemical Co., ltd 2 /s。
Trimethylolpropane ester, chongqing Branch of China petrochemical great wall lubricating oil, the product code of which is great wall 5101 high-temperature synthetic lubricating oil, the kinematic viscosity at 100 ℃ is 5.05mm 2 /s。
Dipentaerythritol ester, shanto Ruijie chemical Co., ltd., kinematic viscosity at 100 ℃ of 7.0mm 2 /s。
Di-tert-butyl peroxide, jiangsu Qiangsheng functional Chemicals GmbH, chemically pure EXAMPLE 1
Adding 130g of raw material p-tert-octyl-phenyl-1-naphthylamine into 130g of n-dodecane, heating, stirring and dissolving a mixed system in the presence of nitrogen, maintaining the mixed system at 145 ℃, adding 72g of di-tert-butyl peroxide into the reaction system, reacting for 4 hours at the constant temperature of 145 +/-2 ℃, then distilling at the temperature of 145 +/-2 ℃ and the constant temperature of 0.02MPa for 30 minutes under reduced pressure, then increasing the vacuum degree to be less than or equal to 0.005MPa, gradually increasing the temperature to 175 ℃, distilling under reduced pressure for more than 40 minutes, cooling and cooling the product in a nitrogen environment after the distillation is finished, and finally obtaining 122g of reaction product A1, wherein the reaction product A1 mainly comprises compounds of structural formula (I-1), structural formula (I-2), structural formula (I-3) and structural formula (I-4).
And preparing a sodium hydroxide aqueous solution with the mass concentration of 18% and a glacial acetic acid solution with the mass concentration of 88%. 0.3mol (35.7 g) of methylbenzotriazole, 0.2mol (64.6 g) of primary alkylamine and 100g of 18% sodium hydroxide solution were successively charged into a three-necked flask, and heated with stirring, wherein the primary alkylamine had a composition of: based on the total molar amount of the alkyl primary amine, C 16 ～C 18 The molar percentage of primary amine is 65% in total, C 19 ～C 20 The mole percentage of primary amine is 35 percent in total, wherein C 16 ～C 18 、C 19 ～C 20 The mole percentage of the linear chain primary amine is 50 percent, 20 percent in sequence, C 16 ～C 18 、C 19 ～C 20 The mole percentage content of the branched primary amine is 15 percent and 15 percent in sequence. When the temperature of the reaction mixture reaches 85 ℃, 20g of 88% acetic acid solution is dripped into the three-neck flask for 15min, and the reaction is carried out at 80-85 ℃ for 5h. After the reaction is finished, washing the upper liquid of the liquid reaction product with distilled water at the temperature of 80 ℃ to be neutral, shaking the mixed liquid, standing, cooling and layering, and carrying out temperature-controlled reduced-pressure vacuum distillation on the upper liquid obtained by the reaction to obtain 80g of a completely transparent orange liquid reaction product, namely the multifunctional oily agent B1.
The reaction product A1 and the reaction product B1 are proportioned according to the mass ratio of 25 to 40.
The reaction raw material p-tert-octyl-phenyl-1-naphthylamine (L06) and the reaction product A1 are subjected to infrared analysis and characterization, and the obtained spectrogram is shown in figure 1.
Fig. 1 is a superimposed infrared spectrum of the reaction raw material p-tert-octyl-phenyl-1-naphthylamine (L06) and the reaction product A1, wherein the upper spectrum is an infrared spectrum of the reaction raw material p-tert-octyl-phenyl-1-naphthylamine (L06), and the lower spectrum is an infrared spectrum of the reaction product A1.
The statistical list of spectral peaks in fig. 1 is as follows.
Statistical comparison table of absorption peaks of infrared spectrogram of reaction raw material and reaction product
The analysis of FIG. 1 and the above table is as follows.
As can be seen from FIG. 1 and the above table, the typical absorption peak of the reaction raw material is 35; the typical absorption peak of the reaction product is 25; the infrared absorption peak is obviously reduced; strong infrared absorption peak of secondary amino group 3411.7cm -1 Obviously weakened, and conforms to the typical characteristics of the infrared spectrum of the polymer and the infrared spectrum absorption peaks of the monomer compounds thereof, which indicates that the oligomerization reaction is actually carried out and the corresponding oligomer is generated.
Comparing the infrared spectrogram of the reaction product A1 and the reaction raw material L06, wherein after the reaction raw materials are subjected to chemical reaction, the strong infrared absorption peak of the secondary amino group on the reaction raw material molecule is 3411.7cm -1 Obviously weakened and blunted, and the corresponding moderate intensity absorption peak on the molecule of the reaction product is 3395.53cm -1 And simultaneously indicates that more secondary amino groups still exist in the product; the infrared absorption peak band of the reaction product is (2957.1-2863.2) cm -1 The infrared absorption peak band (2954.1-2866.32) cm is larger than that of the reaction raw material -1 The apparent widening becomes dull. 1612cm in the reaction product -1 Absorption peak (medium intensity), 1586cm -1 Absorption Peak (Medium intensity), 1464cm -1 Absorption peak (moderate intensity) is typical aromatic ring v C＝C Characteristic absorption peak determined as main body structure in reaction productBut is an aromatic secondary amine structure.
1612cm in the reaction raw material L06 -1 Absorption Peak (Medium intensity), 1586cm -1 Absorption Peak (Medium intensity), 1464cm -1 Typical benzene ring v in absorption peak aromatic secondary amine structure C＝C A characteristic absorption peak; 1586.68cm of reaction product -1 Comparison of the peak with the 1606 peak of starting material L06 shows that the intensity of the key characteristic peak of the polymer is relatively low. 827cm of the same reaction product -1 823cm of peak and starting Material L06 -1 The peak contrast shows that the intensity of the key characteristic peak of the polymer is relatively low.
Absorption peak band (1465-1610) cm -1 The infrared absorption peak of the product is 1612cm which is an important characteristic of the infrared spectrum of the aromatic compound -1 、1586cm -1 Is obviously higher than the infrared absorption peak 1613cm of the raw material -1 、1578cm -1 Weakening, and the difference of the forms of infrared spectrogram peak bands also proves that the reaction raw materials are subjected to oligomerization to form an oligomeric compound with polyaromatic rings; the existence of a large amount of aromatic secondary amine in the polymer proves that the alkylated arylamine is subjected to oligomerization reaction of aryl ring free radical substitution.
Example 2
180g of the starting p-tert-octyl-phenyl-1-naphthylamine were added to 150g of n-decane. Heating, stirring and dissolving the mixed system in the presence of nitrogen, maintaining the mixed system at 140 ℃, adding 98g of di-tert-butyl peroxide into the reaction system, reacting at 140 +/-2 ℃ for 3h, then carrying out reduced pressure distillation at 140 +/-2 ℃ for 30min at 0.02MPa, then raising the vacuum degree to be less than or equal to 0.005MPa, simultaneously gradually raising the temperature to be less than or equal to 175 ℃, carrying out reduced pressure distillation for more than 40min, after the reduced pressure distillation is finished, cooling and cooling the product in a nitrogen environment, and finally obtaining 172g of a reaction product A2, wherein the reaction product mainly comprises compounds with structural formulas (I-1), (I-2), (I-3) and (I-4). And preparing a sodium hydroxide aqueous solution with the mass concentration of 15% and a glacial acetic acid solution with the mass concentration of 90%. 0.3mol (35.7 g) of methylbenzotriazole, 0.1mol (64.6 g) of primary alkylamine and 100g of 15% sodium hydroxide solution were added to a three-necked flask in this order, and heating was carried out with stirring, wherein the primary alkylamine had a composition of: by alkyl radicalsBased on the total molar amount of amine, C 16 ～C 18 The molar percentage of primary amine is 65% in total, C 19 ～C 20 The molar percentage of primary amines was 35% in total, where C 16 ～C 18 、C 19 ～C 20 The mole percentage content of the linear chain primary amine is 45 percent and 25 percent in sequence; c 16 ～C 18 、C 19 ～C 20 The mole percentage content of the branched primary amine is 20 percent and 10 percent in sequence. When the temperature of the reaction mixture reaches 85 ℃, 20g of 90% acetic acid solution is dripped into the three-neck flask for 20min, and the reaction is carried out for 5h at the temperature of 80-85 ℃. After the reaction is finished, washing the upper liquid of the liquid reaction product with distilled water at the temperature of 80 ℃ to be neutral, standing and layering the mixed solution, and carrying out temperature-controlled reduced pressure vacuum distillation on the upper liquid obtained by the reaction to obtain 77.5g of a completely transparent bright orange liquid reaction product, namely the multifunctional oiliness agent B2;
and (3) uniformly stirring the reaction product A2 and the reaction product B2 at a mass ratio of 25 to 40, namely, stirring uniformly at the temperature of 80 ℃ to prepare an antioxidant composition C3 and an antioxidant composition C4.
Example 3
Adding 200g of raw material p-tert-octyl-phenyl-1-naphthylamine into 200g of n-decane, heating and stirring a mixed system in a nitrogen environment, maintaining the temperature of the system at 150 +/-2 ℃, adding 90g of di-tert-butyl peroxide into the reaction system, performing 3h at 150 +/-2 ℃, performing reduced pressure distillation at 150 +/-2 ℃ and 0.02MPa for more than 40min, cooling and cooling the product in the nitrogen environment after the reduced pressure distillation is finished, and finally obtaining 190g of reaction product A2, wherein the reaction product A2 mainly comprises compounds with structural formulas mainly comprising structural formula (I-1), structural formula (I-2), structural formula (I-3) and structural formula (I-4). And preparing a sodium hydroxide aqueous solution with the mass concentration of 15% and a glacial acetic acid solution with the mass concentration of 70%. 0.15mol (17.85 g) of methylbenzotriazole, 0.1mol (32.3 g) of primary alkylamine and 50g of 15% sodium hydroxide solution were successively charged into a three-necked flask, and stirred and heated, wherein the primary alkylamine had a composition comprising C based on the total molar amount of the primary alkylamine 16 ～C 18 、C 19 ～C 20 Moles of Linear Primary amineThe molar percentage content is 40 percent and 25 percent in sequence; c 16 ～C 18 、C 19 ～C 20 The mole percentage content of the branched primary amine is 25 percent and 10 percent in sequence. When the temperature of the reaction mixture reaches 75 ℃, 20g of 90% acetic acid solution is dripped into the three-neck flask for 15min, and the reaction is carried out at 70-75 ℃ for 5h. After the reaction is finished, washing the upper liquid of the liquid reaction product with distilled water at 70 ℃ to be neutral, standing and layering the mixed solution, and carrying out temperature-controlled reduced pressure vacuum distillation on the upper liquid obtained by the reaction to obtain 36.27g of a completely transparent bright orange liquid reaction product, namely the multifunctional oily agent B3;
and (3) proportioning the reaction product A3 and the reaction product B3 according to the mass ratio of 25.
Evaluation of oxidation stability and high temperature corrosion resistance
Respectively adding antioxidant compositions C1-C6, comparative antioxidants V81, T534, T531, L06 and tricresyl phosphate (TCP) of the invention into a mixture with kinematic viscosity =5.02mm at 100 DEG C 2 Examples 4 to 9 and comparative examples 1 to 4, in which the tricresyl phosphate ester was 1% by mass, were prepared by heating and stirring a pentaerythritol saturated acid ester lubricating base oil to give lubricating oil compositions. The formulation compositions of examples 4-9 and comparative examples 1-4 of the lubricating oil compositions of the present invention are shown in Table 1.
Evaluation of high temperature Corrosion and Oxidation stability
The lubricating oil compositions in Table 1 were evaluated for high-temperature corrosion and oxidation stability by the methods FEDSTD-791-5308 designated by SAE5780B and MIL-PRF-23699G, and by the methods 563-1988, method for measuring corrosion and oxidation stability of light-weight aviation lubricating oil, designated by GJB 1263-1991, synthetic lubricating oil for aviation turbine engines. The experimental conditions were: introducing dry air at a constant temperature of 204 ℃ for oxidizing for 72h, and testing experimental data of 3 temperature points; the oxygen flow is 50-83 mL/min; the metal test piece is steel, silver, titanium (copper) aluminum and titanium (magnesium) with specific specifications, and the change of 25 ℃ total acid value of lubricating oil, the change of 40 ℃ viscosity and the formation amount of 100mL oil deposit before and after oxidation are examined.
The evaluation indexes of the method are as follows: total acid value change (delta TAN/mgKOH. G) before and after oil sample oxidation -1 ) (ii) a Viscosity change at 40 ℃ (Δ Viscosity%); 100mL test oil sample Deposit formation (Deposit/mg (100 mL) -1 ) (ii) a The mass per unit area of the metal test piece such as copper, aluminum, steel, silver, titanium, etc. The invention evaluates the experimental result by the quality change data of the copper sheet. The test results are shown in Table 2.
TABLE 1 examples 4-9 and comparative examples 1-4 of lubricating oil compositions
TABLE 2 evaluation test results of high temperature corrosion and oxidation stability
Comparing the technical index requirements of the FEDSTD-791-5308 evaluation method with the results of the corrosion and oxidation stability evaluation data in Table 2, it can be seen that the lubricating oil compositions of examples 4-9 of 5 centistokes grade added with the antioxidant composition of the present invention have significant advantages over the lubricating oil compositions of comparative examples in terms of sheet metal mass change, total acid value change, viscosity change rate, and deposit formation, and the high temperature oxidation resistance thereof is significantly better than that of comparative examples 1-4, and the comparative examples 1-4 do not meet the requirements of corrosion and oxidation stability. The antioxidant composition can better control the change of total acid value of oil products, viscosity change rate and sediment generation amount before and after the oxidation of lubricating oil, and well meets the index requirements of corrosion and oxidation stability of FEDSTD-791-5308. The antioxidant composition has good high-temperature oxidation resistance and sediment formation resistance, is obviously superior to a monomer arylamine antioxidant, and cannot meet the technical indexes of corrosion and oxidation stability, namely the technical indexes of an FEDSTD-791-5308 evaluation method, specified by the latest aviation engine oil specification SAE5780B and MIL-PRF-23699G.
Claims (16)
1. The antioxidant composition comprises an amine compound and a multifunctional oily agent, wherein the structure of the amine compound is shown as the formula (I):
the formula (I) is a compound formed by bonding m structural units shown as the formula (II),
in formula (I), m is an integer of 1 to 10, preferably 1 to 5, more preferably 1 to 3; each R is I Each independently selected from H, C 1～10 Straight or branched chain alkyl, preferably selected from H, C 1～5 Straight or branched chain alkyl, more preferably selected from H, C 1～3 A linear or branched alkyl group; each x is independently selected from an integer between 0 and 4, preferably an integer between 0 and 2, more preferably 0 or 1; each R is II Each independently selected from H, C 1～10 Straight or branched chain alkyl, preferably selected from H, C 1～5 Straight or branched chain alkyl, more preferably selected from H, C 1～3 A linear or branched alkyl group; each y is independently selected from an integer between 0 and 2, preferably 0 or 1; each R is III Each independently selected from H, C 1～10 Straight or branched chain alkyl, preferably selected from H, C 1～5 Straight or branched chain alkyl, more preferably selected from H, C 1～3 A linear or branched alkyl group; each z is independently selected from an integer between 0 and 3, preferably an integer between 0 and 2, more preferably 0 or 1;
each L in the formula (II) I 、L II 、L III Each independently H, C 1～4 Alkyl, and L in different structural units I 、L II 、L III A bonded bonding end.
2. Antioxidant according to claim 1Agent composition, characterized in that, in formula (I), when m =1, L I 、L II 、L III Each independently is H or C 1～4 An alkyl group; when m =2, there are 2 structural units represented by formula (II), L of the 2 structural units I 、L II 、L III Are mutually bonded; when m is greater than 2, m structural units shown as the formula (II) exist, and L in m structural units I 、L II 、L III Are bonded with each other.
3. The antioxidant composition of claim 1, wherein the compound of formula (I) comprises:
4. the antioxidant composition as claimed in claim 1, wherein the amine compound is prepared by a method comprising: reacting a compound represented by formula (alpha) in the presence of a peroxide (preferably an organic peroxide, more preferably one or more of an alkyl peroxide, an acyl peroxide, a peroxyketal and a peroxyorganic ester), and collecting a product;
in the formula (. Alpha.), each R I Each independently selected from H, C 1～10 Straight or branched chain alkyl, preferably selected from H, C 1～5 Straight or branched chain alkyl, more preferably selected from H, C 1～3 A linear or branched alkyl group; each x is independently selected from an integer between 0 and 4, preferably an integer between 0 and 2, more preferably 0 or 1; each R is II Each independently selected from H, C 1～10 Straight or branched chain alkyl, preferably selected from H, C 1～5 Straight or branched chain alkyl, more preferably selected from H, C 1～3 A linear or branched alkyl group; each y isEach independently selected from integers between 0 and 2, preferably 0 or 1; each R is III Each independently selected from H, C 1～10 Straight or branched chain alkyl, preferably selected from H, C 1～5 Straight or branched chain alkyl, more preferably selected from H, C 1～3 A linear or branched alkyl group; each z is independently selected from an integer between 0 and 3, preferably an integer between 0 and 2, more preferably 0 or 1.
5. The antioxidant composition according to claim 4, wherein the compound represented by the formula (α) is reacted at a temperature of 110 to 200 ℃.
6. Antioxidant composition according to claim 1, characterized in that the multifunctional oily agent is the reaction product of alkylbenzotriazole and/or benzotriazole, mixed alkyl primary amine under the action of an acidic catalyst.
7. The antioxidant composition as claimed in claim 1, wherein the multifunctional oily agent is prepared by the method comprising: under the existence of inert gas, the alkylbenzene triazole and/or the benzotriazole and alkyl primary amine react under the action of an acid catalyst, and a product is collected.
8. The antioxidant composition of claim 7, wherein the alkylbenzotriazole and/or benzotriazole has the structure:
in the formula R 1 ' selected from H, C 1 ～C 12 Straight or branched chain alkyl (preferably C) 1 ～C 8 Straight or branched chain alkyl, most preferably methyl); the alkyl primary amine is C 16 ～C 22 The primary alkyl amine of the formula R 2 ’CH 2 NH 2 Wherein R is 2 ' is C 15 ～C 21 Linear or branched alkyl.
9. The antioxidant composition of claim 8, wherein the primary alkyl amine is C 16 ～C 22 The mixed primary alkyl amine of (1), which is a mixture of a linear primary amine and a branched primary amine.
10. The antioxidant composition as claimed in claim 9,
based on the total mole number of the mixed alkyl primary amine, according to the alkyl type, the alkyl type is as follows: said C 16 ～C 22 The mixed alkyl primary amine of (2) contains 55 to 90 percent of C 16 ～C 22 Linear alkyl primary amine and 10-45% of C 16 ～C 22 Branched primary alkyl amines (preferably containing 55% to 80% C) 16 ～C 22 Linear alkyl primary amine and 20-45% of C 16 ～C 22 Branched primary alkyl amines of (1); alternatively, the first and second liquid crystal display panels may be,
based on the total mole number of the mixed alkyl primary amine, the carbon-containing fraction is as follows in mole percentage: said C 16 ～C 22 Mixed primary alkyl amines of (1) 16 ～C 18 The content of alkyl primary amine is 45-85 percent, C 19 ～C 22 The content of the primary alkylamine of (C) is 15 to 55 percent (preferably C) 16 ～C 18 The content of alkyl primary amine is 55% -75%, C 19 ～C 22 The content of alkyl primary amine is 25-45%); alternatively, the first and second electrodes may be,
based on the total mole number of the mixed alkyl primary amine, according to the mole percentage, the carbon number and the alkyl type are as follows: in said C 16 ～C 22 In the mixed alkyl primary amines of (1), C 16 ～C 18 The content of the linear primary amine is 40 to 70 percent, C 19 ～C 22 The content of the linear primary amine (C) is 15 to 40 percent 16 ～C 18 The content of branched primary amine is 5-35 percent, C 19 ～C 22 The content of the branched primary amine (C) is preferably 5 to 30% (C) 16 ～C 18 The content of the linear primary amine is 45 to 60 percent, C 19 ～C 22 Primary of a linear chain of20 to 35 percent of amine and C 16 ～C 18 The content of branched primary amine is 5-25%, C 19 ～C 22 The content of the branched primary amine of (2) is 5% to 30%).
11. The antioxidant composition as claimed in claim 7, wherein the molar ratio between the alkylbenzotriazole and/or benzotriazole and the primary alkylamine is 1:0.5 to 1.
12. The antioxidant composition as claimed in any one of claims 1 to 11, wherein the mass ratio between said amine compound and said multifunctional oily agent in said antioxidant composition is 10 to 60:1.
13. the method for preparing the antioxidant composition as claimed in any one of claims 1 to 12, comprising the step of mixing the amine-based compound and the multifunctional oily agent.
14. Use of the antioxidant composition of any of claims 1 to 12 as a high temperature antioxidant, radical scavenger.
15. Lubricating oil composition comprising a lubricating base oil (preferably a synthetic hydrocarbon and/or a synthetic ester), an antioxidant composition as claimed in any one of claims 1 to 12.
16. A method for improving the oxidation and corrosion resistance of a lubricating oil composition comprising adding an antioxidant composition as claimed in any one of claims 1 to 12 to a lubricating base oil (preferably a synthetic hydrocarbon and/or a synthetic ester, more preferably C) 4 -C 8 Polyols and C 3 -C 12 Esters of fatty acids, most preferably trimethylolpropane esters and/or pentaerythritol esters).
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