CN111778084B - Antioxidant composition for lubricating oil - Google Patents
Antioxidant composition for lubricating oil Download PDFInfo
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- CN111778084B CN111778084B CN202010563611.2A CN202010563611A CN111778084B CN 111778084 B CN111778084 B CN 111778084B CN 202010563611 A CN202010563611 A CN 202010563611A CN 111778084 B CN111778084 B CN 111778084B
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- antioxidant
- ionic liquid
- lubricating oil
- phosphate ionic
- oil
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
-
- 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
- C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
- C10M2207/0225—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
- C10M2215/065—Phenyl-Naphthyl amines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
The invention discloses an antioxidant composition for lubricating oil, which is prepared from amine antioxidant and tetraalkyl phosphonium phosphate ionic liquid in a weight ratio of 1: 100-100: 1 proportion, the lubricating oil antioxidant composition provided by the invention has excellent antioxidant performance in synthetic ester base oil, can remarkably prolong the oxidation induction period of the base oil, prolongs the service life of lubricating oil, and is particularly suitable for lubricating working conditions with harsh high-temperature requirements.
Description
Technical Field
The invention relates to a lubricating oil antioxidant composition, belonging to the technical field of lubrication.
Background
With the development of modern mechanical equipment design towards small volume, high speed, high load and high power, the working conditions of lubricating oil are increasingly harsh, and higher requirements are put forward on the oxidation stability of the lubricating oil, so that efficient, novel, multifunctional and composite antioxidants need to be developed to meet the requirements. The composite antioxidant has the advantages of good effect, good comprehensive performance and full synergistic effect of various additives, can often obtain the service performance which can not be achieved by a single agent, and can meet the requirement of harsher service conditions on the oxidation resistance of the lubricant. The development of the composite antioxidant is more and more important in the antioxidant of the lubricating oil, and is also the development trend of the antioxidant in the future.
The complex antioxidant composition is generally a complex of an amine antioxidant and a hindered phenol antioxidant, or a complex of an amine (phenol) antioxidant and a hydroperoxide decomposer. For example: an antioxidant additive composition reported in patent CN102206532B, when bismuth compound and arylamine compound are used together in base oil with a certain composition, the initial oxidation temperature and oxidation induction period of the base oil are both improved to a certain extent. Patent CN108026467A reports an antioxidant composition comprising methylenebis (di-n-butyldithiocarbamate), alkylated diphenylamine derivatives of triazoles. The antioxidant composition reported in patent CN104059717A comprises alkylated diphenylamine, phenothiazine and sulfurized hindered phenol, has less high-temperature thermal volatilization loss, can obviously improve the oxidation stability of lubricating oil under high-temperature conditions and metal ion catalysis conditions, and effectively prolongs the service life of the lubricating oil. Patent CN106604980A reports that a liquid ashless antioxidant additive for lubricating compositions whose composition includes an alkylated-phenyl-alpha-naphthylamine, an alkylated diphenylamine derivative of benzotriazole and methylenebis (di-n-butyldithiocarbamate) can significantly increase the oxidation induction time.
The tetraalkyl phosphonium phosphate ionic liquid has been proved to be an Antiwear agent with excellent performance (anti wear performance and mechanism of an oil-mixed ionic liquid as a solvent additive. ACS Appl Mater Inter 2012), and the trihexyl tetradecyl phosphonium dioctyl phosphate and tetraoctyl phosphonium dioctyl phosphate ionic liquid reported in the patent US 2015/0232777A 1 have lower abrasion in synthetic natural gas oil than ZDDP. Because the quaternary alkyl phosphonium phosphate ionic liquid has no antioxidant performance, the potential value of the quaternary alkyl phosphonium phosphate ionic liquid used as a composite antioxidant component is not found and is not reported.
Disclosure of Invention
The invention provides a lubricating oil antioxidant composition, which is different from antioxidant compositions in the prior art, solves the technical problem of high-temperature oxidation of lubricating oil in the prior art, has excellent antioxidant performance, prolongs the oxidation induction period of the lubricating oil, prolongs the service life of the lubricating oil, and achieves the purposes of energy conservation and consumption reduction.
The invention is realized by the following steps: the lubricating oil antioxidant composition comprises an amine antioxidant and a tetraalkyl phosphonium phosphate ionic liquid.
As a preferred embodiment, the weight ratio of the amine antioxidant to the tetraalkyl phosphonium phosphate ionic liquid is 1: 100-100: 1.
as a preferred embodiment, the weight ratio of the amine antioxidant to the tetraalkyl phosphonium phosphate ionic liquid is 1: 10-10: 1.
in a preferred embodiment, the amine antioxidant is one of a linear or branched alkyl substituted diphenylamine or an alkylated phenyl-alpha-naphthylamine.
As a preferred embodiment, the linear or branched alkyl-substituted diphenylamine or alkylated phenyl- α -naphthylamine is one of butyl/octyl diphenylamine, dioctyl diphenylamine, N-phenyl- α -naphthylamine, octyl phenyl- α -naphthylamine, and polymers of dioctyl diphenylamine and octyl phenyl- α -naphthylamine.
As a preferred embodiment, the tetraalkyl phosphonium phosphate ionic liquid has a structural formula shown in formula (1),
wherein R1, R2, R3 and R4 are alkyl groups with 4-14 carbon atoms.
As a preferred embodiment, the tetraalkyl phosphonium phosphate ionic liquid is one of tributyl tetradecyl phosphonium dioctyl phosphate ionic liquid, trihexyl tetradecyl phosphonium dioctyl phosphate ionic liquid and tetraoctyl phosphonium dioctyl phosphate ionic liquid.
The invention has the beneficial effects that: the invention provides an antioxidant composition which is different from patents related in the background art, and solves the problem of high-temperature oxidation of lubricating oil. When the antioxidant composition is used in synthetic ester, the antioxidant performance of the antioxidant composition is higher than that of the antioxidant composition added with amine antioxidants alone, and the antioxidant composition especially obviously prolongs the oxidation induction life of lubricating oil.
The tetraalkyl phosphonium phosphate ionic liquid and the amine antioxidant have efficient synergistic antioxidant effect, when the tetraalkyl phosphonium phosphate ionic liquid and the amine antioxidant are used in combination, the induction period of the lubricating oil is obviously prolonged, the antioxidant performance which is difficult to achieve by independently adding the amine antioxidant is achieved, and the service life of the lubricating oil is prolonged. The lubricating oil can meet the lubricating working conditions with strict high-temperature anti-oxidation requirements, such as high-temperature chain transmission oil, aircraft engine oil, high-temperature lubricating grease and the like, and has wide application prospects.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
Examples 1-5 the commercial example of butyl/octyl diphenylamine is L57 manufactured by BASF Corporation, the commercial example of dioctyl diphenylamine is V81 supplied by Vanderbilt Chemicals LLC, the commercial example of N-phenyl- α -naphthylamine is T531 manufactured by Camerbit chemical Co., Ltd, the commercial example of octyl phenyl- α -naphthylamine is L06 manufactured by BASF Corporation, and the polymer of dioctyl diphenylamine and N-octyl phenyl- α -naphthylamine is AO337 manufactured by NYCO Corporation. The percentages in examples 1 to 5 are by weight.
The test method for the oxidation induction period of the lubricating oil in the examples is as follows: and (3) measuring the time of the sample beginning to perform the automatic catalytic oxidation reaction at 220 ℃ and the oxygen flow rate of 100ml/min by using a high-pressure differential scanning calorimeter, wherein the protective gas of the sample cell is nitrogen and the pressure is 3.5 MPa.
Example 1
The antioxidant properties of the oil samples were evaluated by oxidation induction period using pentaerythritol ester (5750) as the base oil, to which 2% L57, 0.2% tetraoctylphosphonium dioctylphosphate ionic liquid ([ P8888] [ DEHP ]), and a combination thereof were added, respectively, and the results are shown in Table 1.
Table 1 example 1 oil-like oxidative induction period
| Oil sample | Oxidative induction period, min |
| 5750+2％L57 | 53.2 |
| 5750+0.2％[P8888][DEHP] | 0 |
| 5750+2％L57+0.2％[P8888][DEHP] | 67.2 |
Example 2
The antioxidant properties of the oil samples were evaluated by the oxidation induction period using pentaerythritol ester (5750) as the base oil, and 1% T531, 1% tributyltetradecylphosphonium dioctylphosphonate ionic liquid ([ P44414] [ DEHP ]), and a combination of the two, and the results are shown in Table 2.
Table 2 example 2 oil-like oxidative induction period
| Oil sample | Oxidative induction period, min |
| 5750+1％T531 | 44.3 |
| 5750+1％[P44414][DEHP] | 0 |
| 5750+1％T531+1％[P44414][DEHP] | 72.8 |
Example 3
The antioxidant properties of the oil samples were evaluated by oxidation induction period using pentaerythritol ester (5750) as the base oil, with 2% V81, 1% tetraoctylphosphonium dioctylphosphate ionic liquid ([ P8888] [ DEHP ]), and combinations of the two, respectively, and the results are shown in Table 3.
Table 3 example 3 oil-like oxidative induction period
Example 4
The antioxidant properties of the oil samples were evaluated by the oxidation induction period using pentaerythritol ester (5750) as the base oil, with the addition of 0.2% L06, 2% trihexyl tetradecylphosphonium dioctylphosphate ionic liquid ([ P66614] [ DEHP ]), and a combination of the two, and the results are shown in Table 4.
Table 4 example 4 oxidative induction period of oil samples
| Oil sample | Oxidative induction period, min |
| 5750+0.2％L06 | 16.0 |
| 5750+2％[P66614][DEHP] | 0 |
| 5750+0.2％L06+2％[P66614][DEHP] | 19.8 |
Example 5
The antioxidant properties of the oil samples were evaluated by oxidation induction period using pentaerythritol ester (5750) as the base oil, to which 6.6% AO337, 2% tetraoctylphosphonium dioctylphosphate ionic liquid ([ P8888] [ DEHP ]), and a combination of both were added, and the results are shown in Table 5.
TABLE 5 example 5 oxidative induction period of oil samples
| Oil sample | Oxidative induction period, min |
| 5750+7％AO337 | 143 |
| 5750+2％[P8888][DEHP] | 0 |
| 5750+7％AO337+2％[P8888][DEHP] | 179.1 |
The test results of examples 1 to 5 show that when the amine antioxidant and the tetraalkyl phosphonium phosphate ionic liquid are added into the pentaerythritol ester base oil together, the oxidation induction period is longer than that when the amine antioxidant or the tetraalkyl phosphonium phosphate ionic liquid is added separately.
The invention has the beneficial effects that: the invention provides an antioxidant composition which is different from patents related in the background art, and solves the problem of high-temperature oxidation of lubricating oil. The antioxidant composition has higher oxidation resistance than that of singly added amine antioxidants when used in synthetic ester, and particularly obviously prolongs the oxidation induction life of lubricating oil.
The tetraalkyl phosphonium phosphate ionic liquid and the amine antioxidant have high-efficiency synergistic antioxidant effect, and when the tetraalkyl phosphonium phosphate ionic liquid and the amine antioxidant are used in combination, the induction period of the lubricating oil can be obviously prolonged, the antioxidant performance which is difficult to achieve by independently adding the amine antioxidant is realized, and the service life of the lubricating oil is prolonged. Can meet the lubricating working conditions with harsh requirements on high-temperature oxidation resistance, such as high-temperature chain transmission oil, aircraft engine oil, high-temperature lubricating grease and the like, and has wide application prospect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (6)
1. The antioxidant composition for the lubricating oil is characterized by comprising an amine antioxidant and tetraalkyl phosphonium phosphate ionic liquid, wherein the tetraalkyl phosphonium phosphate ionic liquid can obviously improve the antioxidant performance of the amine antioxidant;
the tetraalkyl phosphonium phosphate ionic liquid is one of tributyl tetradecyl phosphonium dioctyl phosphate ionic liquid, trihexyl tetradecyl phosphonium dioctyl phosphate ionic liquid and tetraoctyl phosphonium dioctyl phosphate ionic liquid.
2. The lubricating oil antioxidant composition of claim 1, wherein the weight ratio of the amine antioxidant to the tetraalkyl phosphonium phosphate ionic liquid is 1: 100-100: 1.
3. the lubricating oil antioxidant composition as claimed in claim 2, wherein the weight ratio of the amine antioxidant to the tetraalkyl phosphonium phosphate ionic liquid is 1: 10-10: 1.
4. the lubricating oil antioxidant composition of claim 2, wherein the amine antioxidant is one of a linear or branched alkyl substituted diphenylamine or an alkylated phenyl-alpha-naphthylamine.
5. The lubricating oil antioxidant composition of claim 4, wherein the linear or branched alkyl-substituted diphenylamine or alkylated phenyl-alpha-naphthylamine is one of butyl/octyl diphenylamine, dioctyl diphenylamine, N-phenyl-alpha-naphthylamine, octyl phenyl-alpha-naphthylamine, and polymers of dioctyl diphenylamine and octyl phenyl-alpha-naphthylamine.
6. The lubricating oil antioxidant composition of claim 1, wherein the tetraalkyl phosphonium phosphate ionic liquid has a structural formula as shown in formula (1),
wherein R1, R2, R3 and R4 are alkyl groups with 4-14 carbon atoms.
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| CN113621425A (en) * | 2021-07-29 | 2021-11-09 | 中国科学院兰州化学物理研究所 | Low-viscosity aviation lubricating oil with good friction-reducing and wear-resisting properties and preparation method thereof |
| CN114574272B (en) * | 2022-03-18 | 2022-09-06 | 中国科学院兰州化学物理研究所 | Lubricating oil composition and preparation method and application thereof |
| CN116143829B (en) * | 2022-12-23 | 2024-05-07 | 中国科学院兰州化学物理研究所 | High extreme pressure proton type ionic liquid, preparation method and application thereof as oil-based additive |
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| CN103160362A (en) * | 2011-12-16 | 2013-06-19 | 中国科学院兰州化学物理研究所 | Ionic liquid synthetic lubricating oil composition |
| US9957460B2 (en) * | 2014-02-20 | 2018-05-01 | Ut-Battelle, Llc | Ionic liquids containing symmetric quaternary phosphonium cations and phosphorus-containing anions, and their use as lubricant additives |
| CN107903285B (en) * | 2017-11-24 | 2020-01-24 | 中国科学院兰州化学物理研究所 | Neutral phosphate ionic liquid and application thereof |
| KR102097232B1 (en) * | 2019-02-28 | 2020-04-06 | 대림산업 주식회사 | Lubricant composition for gear oil |
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