CN103740438A - High-temperature oxidant for ester oil and preparation method of oxidant - Google Patents
High-temperature oxidant for ester oil and preparation method of oxidant Download PDFInfo
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Abstract
The invention belongs to the technical field of lubricating oil additives, and particularly relates to a high-temperature oxidant for ester oil and a preparation method of the oxidant. The general formula of the oxidant is (img file=' 317369dest_path_image001.TIF' wi='212' he='63'/), in the formula, R is C1-8 alkoxy or C2-8 oligo-ether; the general formula of the C2-8 oligo-ether is (img file='2013107468234100004dest_path_image002.TIF' wi='136' he='23'/); R position is one or more of ortho-position, para-position or meta-position. The preparation method comprises the following steps: with 2-chlorine phenothiazine and substituted aniline as raw materials, using an aprotic solvent under protection of an inert gas; and carrying out one-step synthesis, separation and purification in the presence of a catalyst, so as to obtain a target product. According to the oxidant and the preparation method thereof disclosed by the invention, phenothiazine with outstanding high-temperature antioxidant ability is taken as a parent; an aniline structure is introduced, so as to form a bifunctional antioxidant. Meanwhile, the solubleness in the ester oil is enhanced by the introduced alkoxy or oligo-ether, and the excellent high-temperature oxidant for the ester oil is obtained by two antioxidant groups in the same antioxidant molecules. The high-temperature oxidant is simple in synthetic method, rapid in reaction speed and high in product purity.
Description
Technical field
The invention belongs to lubricating oil additive technical field, particularly a kind of ester class oil high-temperature anti-oxidant and preparation method thereof.
Background technology
The glossy lubricating oil of ester class has following characteristic: 1) good viscosity-temperature characteristics, 2) high and low temperature performance is good, and 3) oxidative stability is good, and 4) oilness is good.Therefore be applied to the fields such as precision instrumentation lubricating oil, SYNTHETIC COMPRESSOR OIL, metal processing oil solution and fine chemistry industry.Particularly at aerospace field, at present aircraft engine lubricating oil almost all use be lubricating oil in esters.
Oxidation inhibitor is the important lubricating oil additive of a class, for extending lubricating oil life cycle and guaranteeing that lubricating oil oxidation stability at high temperature has irreplaceable effect.Along with the development of modern science and technology, the running environment of mechanical means moving parts is more and more harsher, and use temperature is more and more higher, and to antioxidant for lubricant oil, particularly high-temperature antioxidant has proposed more and more higher requirement, like this equally for lubricating oil in esters.
The high-temperature antioxidant of domestic and international various documents and patent report is mainly aniline, naphthylamines, phenols, sulfur-bearing compounds etc. at present.As US Patent No. 4764299 is used one or more in hindered phenols, arylamine, alkyl sulfur compounds, dithiocar-bamate etc. as ester class oil high-temperature antioxidant.US Patent No. 5073278 has been reported and in mineral oil and synthesizing ester oil, has been used thiodiphenylamine etc. as high-temperature anti-oxidant.Chinese patent CN101117609A has reported that antioxidants such as using alkyl diphenylamine works at 280 ℃ as the antioxidant of synthesizing ester oil.
Summary of the invention
The object of the invention is to provide a kind of ester class oil high-temperature anti-oxidant and preparation method thereof, and the high-temperature anti-oxidant high-temperature behavior of gained is excellent, is particularly suitable for each ester class oil under hot conditions and uses.
The technical solution used in the present invention is as follows:
An ester class oil high-temperature anti-oxidant, general formula is:
, in formula, R is C1-8 alkoxyl group or the oligomeric ether of C2-8, the oligomeric ether general formula of C2-8 is
; R position is one or more in ortho position, contraposition or a position.High-temperature anti-oxidant, as well known to those skilled in the art referring to can be at the antioxidant of 250 ℃ of above work.
Preparation method: take 2-chloro phenothiazine, substituted aniline is raw material, under protection of inert gas, uses non-protonic solvent, under catalyzer exists, after one-step synthesis, separation and purification target product; The general formula of wherein said substituted aniline is:
, in formula, R is C1-8 alkoxyl group or the oligomeric ether of C2-8, the oligomeric ether general formula of C2-8 is
; R position is one or more in ortho position, contraposition or a position.
Further, the mol ratio of 2-chloro phenothiazine and substituted aniline is 1:1.1-1:1.4, and the best is 1:1.2, the mol ratio of non-protonic solvent and substituted aniline is 1:2-1:5, the best is 1:4, and the mol ratio of catalyzer and 2-chloro phenothiazine is 1:80-1:120, and the best is 1:100.
Further, described non-protonic solvent is Isosorbide-5-Nitrae-dioxane.
Further, the structural formula of described catalyzer is:
, R=i-Pr in formula.This catalyzer can reference (Jingya Li, Mengjun Cui, Ajuan Yu, Yangjie Wu. Journal of Organometallic Chemistry. 692 (17): method preparation 3732-3742).
Further, described rare gas element is argon gas or nitrogen.
Further, when synthetic, temperature required is 100-120 ℃, and the best is 110 ℃, and required time is 3-6h, and the best is 4h.
The present invention is that to take the outstanding thiodiphenylamine of high temperature antioxidant capacity be parent, introduce aniline structure, form bifunctional oxidation inhibitor, to strengthen its antioxidant capacity, alkoxyl group or the oligomeric ether introduced have strengthened the solvability in ester class oil simultaneously, realize two antioxidant groups in same oxidation inhibitor molecule, obtained the good high temperature ester class oil antioxidant of a class; Synthetic method is simple, and speed of response is fast, and product purity is high.
Accompanying drawing explanation
Fig. 1 is molecular structure and the IR collection of illustrative plates of embodiment 1 product.
Fig. 2 is embodiment 1 product
1h NMR collection of illustrative plates.
Fig. 3 is the thermogravimetric analysis collection of illustrative plates of embodiment 1 product.
Fig. 4 is the rotary oxygen bomb test result of the diisooctyl sebacate containing 0.5wt% embodiment 1 product.
Embodiment
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited to this, wherein the structural formula of catalyzer is:
, R=i-Pr in formula.This catalyzer can reference (Jingya Li, Mengjun Cui, Ajuan Yu, Yangjie Wu. Journal of Organometallic Chemistry. 692 (17): method preparation 3732-3742).
Embodiment 1
In 25ml Schlenk reaction flask, add 0.552 gram of (0.0024mol) 2-chloro phenothiazine, 0.324 gram of (0.0028mol) 3,4-dimethoxyaniline, 0.02 gram of (0.000024mol) catalyzer, nitrogen replacement 3 times, under room temperature, stir 10min, inject 7ml1,4-dioxane, seals lower 110 ℃ of reaction 4h, naturally cool to room temperature, add 10ml shrend to go out, 10ml dichloromethane extraction 3 times, dry, methylene dichloride column chromatography wash-out, obtains 0.24 gram of white needle-like crystals.
Fig. 1 is molecular structure and the IR collection of illustrative plates of embodiment 1 product.IR (KBr, vmax): wave number (cm
-1) at 3362,3394 places, occurring that 2 spikes are N-H absorption peak, 2982 places are methoxyl group C-H absorption peak, 1466,1511 the bimodal of appearance are aromatic nucleus C-S-C charateristic avsorption band.
Fig. 2 is embodiment 1 product
1h NMR collection of illustrative plates.
1h NMR (400 MHz, CDCl
3): δ=7.7,8.5 (s, 2H, 2 secondary amine hydrogen), 6.4-7.0 (m, 10H, Ar-H), 3.7 (s, 6H, CH
3-).From collection of illustrative plates, seen the product of the designed molecular structure of the present invention, and product purity is high.
Fig. 3 is the thermogravimetric analysis collection of illustrative plates of embodiment 1 product.At N
2under atmosphere, thermogravimetric analysis result shows 300 ℃ of heat decomposition temperature starting temperatures, and 390 ℃ of final decomposition temperatures, have very high thermostability.And the thermolysis starting temperature of thiodiphenylamine sterling is 180 ℃, 300 ℃ of final decomposition temperatures, than pure thiodiphenylamine, product heat decomposition temperature of the present invention has improved 90 ℃.
By standard SH/T 0193-2008, test rotary oxygen bomb oxidation induction period, Fig. 4 is the rotary oxygen bomb test result of the diisooctyl sebacate containing 0.5wt% embodiment 1 product { wt%=embodiment product/(dioctyl sebacate+embodiment product) }.Result shows: the oxidation induction period that contains the diisooctyl sebacate of 0.5wt% embodiment 1 product reaches 1500min, and the oxidation induction period of the sterling of diisooctyl sebacate is only 48min, in conjunction with thermogravimetric analysis result, show that the product of synthesized of the present invention has excellent high temperature antioxidant capacity.
Embodiment 2
In 25ml Schlenk reaction flask, add 0.552 gram of (0.0024mol) 2-chloro phenothiazine, 0.344 gram of (0.0028mol) m-anisidine, 0.02 gram of (0.000024mol) catalyzer, nitrogen replacement 3 times, stirs 10min under room temperature, injects 7ml1,4-dioxane, seal lower 110 ℃ of reaction 4h, naturally cool to room temperature, add 10ml shrend to go out, 10ml dichloromethane extraction 3 times, dry, methylene dichloride column chromatography wash-out, obtains 0.20 gram of white needle-like crystals.
Embodiment 3
In 25ml Schlenk reaction flask, add 0.552 gram of (0.0024mol) 2-chloro phenothiazine, 0.344 gram of (0.0028mol) P-nethoxyaniline, 0.02 gram of (0.000024mol) catalyzer, nitrogen replacement 3 times, stirs 10min under room temperature, injects 7ml1,4-dioxane, seal lower 110 ℃ of reaction 4h, naturally cool to room temperature, add 10ml shrend to go out, 10ml dichloromethane extraction 3 times, dry, methylene dichloride column chromatography wash-out, obtains 0.26 gram of white needle-like crystals.
In 25ml Schlenk reaction flask, add 0.552 gram of (0.0024mol) 2-chloro phenothiazine, 0.324 gram of (0.0028mol) 3,5-dimethoxyaniline, 0.02 gram of (0.000024mol) catalyzer, nitrogen replacement 3 times, under room temperature, stir 10min, inject 7ml1,4-dioxane, seals lower 110 ℃ of reaction 4h, naturally cool to room temperature, add 10ml shrend to go out, 10ml dichloromethane extraction 3 times, dry, methylene dichloride column chromatography wash-out, obtains 0.38 gram of white needle-like crystals.
Embodiment 5
In 25ml Schlenk reaction flask, add 0.552 gram of (0.0024mol) 2-chloro phenothiazine, 0.507 gram of (0.0028mol) 3,5-diethoxy aniline, 0.02 gram of (0.000024mol) catalyzer, nitrogen replacement 3 times, under room temperature, stir 10min, inject 7ml1,4-dioxane, seals lower 110 ℃ of reaction 4h, naturally cool to room temperature, add 10ml shrend to go out, 10ml dichloromethane extraction 3 times, dry, methylene dichloride column chromatography wash-out, obtains 0.63 gram of white needle-like crystals.
Embodiment 6
In 25ml Schlenk reaction flask, add 0.552 gram of (0.0024mol) 2-chloro phenothiazine, 0.501 gram (0.0028mol) to pentyloxy aniline, 0.02 gram of (0.000024mol) catalyzer, nitrogen replacement 3 times, under room temperature, stir 10min, inject 7ml1,4-dioxane.Seal lower 110 ℃ of reaction 4h, naturally cool to room temperature, add 10ml shrend to go out, 10ml dichloromethane extraction 3 times, dry, methylene dichloride column chromatography wash-out, obtains 0.53 gram of white needle-like crystals.
Embodiment 7
In 25ml Schlenk reaction flask, add 0.552 gram of (0.0024mol) 2-chloro phenothiazine, 0.389 gram of (0.0028mol) (methoxyl group) methyl-4
'-aminophenyl ether, 0.02 gram of (0.000024mol) catalyzer, nitrogen replacement 3 times, stirs 10min under room temperature, injects 7ml1,4-dioxane.Seal lower 110 ℃ of reaction 4h, naturally cool to room temperature, add 10ml shrend to go out, 10ml dichloromethane extraction 3 times, dry, methylene dichloride column chromatography wash-out, obtains 0.49 gram of white needle-like crystals.
Claims (9)
2. prepare the method for high-temperature anti-oxidant for ester class oil as claimed in claim 1 for one kind, it is characterized in that: take 2-chloro phenothiazine, substituted aniline is raw material, under protection of inert gas, uses non-protonic solvent, under catalyzer exists, after one-step synthesis, separation and purification, obtain target product; The general formula of wherein said substituted aniline is:
3. preparation method as claimed in claim 2, it is characterized in that: the mol ratio of 2-chloro phenothiazine and substituted aniline is 1:1.1-1:1.4, the mol ratio of non-protonic solvent and substituted aniline is 1:2-1:5, and the mol ratio of catalyzer and 2-chloro phenothiazine is 1:80-1:120.
4. preparation method as claimed in claim 3, is characterized in that: the mol ratio of 2-chloro phenothiazine and substituted aniline is 1:1.2, and the mol ratio of non-protonic solvent and substituted aniline is 1:4, and the mol ratio of catalyzer and 2-chloro phenothiazine is 1:100.
5. the preparation method as described in any one of claim 2-4, is characterized in that: described non-protonic solvent is Isosorbide-5-Nitrae-dioxane.
7. the preparation method as described in any one of claim 2-4, is characterized in that: described rare gas element is argon gas or nitrogen.
8. the preparation method as described in any one of claim 2-4, is characterized in that: when synthetic, temperature required is 100-120 ℃, and required time is 3-6h.
9. preparation method as claimed in claim 8, is characterized in that: temperature is 110 ℃, and the time is 4h.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105505525B (en) * | 2015-10-16 | 2018-09-11 | 中国科学院宁波材料技术与工程研究所 | Phenol amine antioxidants, preparation method and application |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5275746A (en) * | 1990-08-24 | 1994-01-04 | Texaco Inc. | Multifunctional viscosity index improver containing phenothiazine |
US5424366A (en) * | 1991-04-24 | 1995-06-13 | Texaco Inc. | Multifunctional viscosity index improver containing phenothiazine |
CN101082010A (en) * | 2006-05-31 | 2007-12-05 | 中国石油化工股份有限公司 | Liquid alkylated phenthazine and diphenylamine mixture and preparation method and application thereof |
-
2013
- 2013-12-30 CN CN201310746823.4A patent/CN103740438B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5275746A (en) * | 1990-08-24 | 1994-01-04 | Texaco Inc. | Multifunctional viscosity index improver containing phenothiazine |
US5424366A (en) * | 1991-04-24 | 1995-06-13 | Texaco Inc. | Multifunctional viscosity index improver containing phenothiazine |
CN101082010A (en) * | 2006-05-31 | 2007-12-05 | 中国石油化工股份有限公司 | Liquid alkylated phenthazine and diphenylamine mixture and preparation method and application thereof |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105505525B (en) * | 2015-10-16 | 2018-09-11 | 中国科学院宁波材料技术与工程研究所 | Phenol amine antioxidants, preparation method and application |
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Effective date of registration: 20221024 Address after: No.192 Longshoushan Road, Huangdao District, Qingdao City, Shandong Province 266000 Patentee after: QINGDAO COPTON PETROCHEMICAL CO.,LTD. Address before: 475004 Jinming Road, Kaifeng City, Henan Province Patentee before: Henan University |
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