CN103695078A - Hydroxy-containing thiadiazole derivative, and preparation method and application thereof - Google Patents
Hydroxy-containing thiadiazole derivative, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a hydroxy-containing thiadiazole derivative. The hydroxy-containing thiadiazole derivative has a structural formula shown in the specification, R in the structural formula is also shown in the specification, and R1 and R2 in the formula of R are respectively independently selected from C1-C30 straight-chain or branched-chain or C3-C30 cycloalkyl groups. The introduction of a hydroxy-containing oil-soluble carbon chain into the hydroxy-containing thiadiazole derivative makes the hydroxy-containing thiadiazole derivative well compatible with grease, and the hydroxy group can be effectively adsorbed by the surface of a metal, and can enhance the extreme pressure wear resistance.
Description
Technical field
The present invention relates to a kind of organic compound and preparation method thereof, particularly a kind of hydroxyl thiadiazoles derivative and preparation method thereof and in the application as in extreme pressure anti-wear additives.
Background technology
Friction and wear when lubricating grease (oil) can reduce mechanical movement, prevent gummed, improve mechanical efficiency, reduce energy consumption, the prolonged mechanical life-span, so be widely used in all departments of national economy.Mineral base grease (oil) degradation capability in physical environment is very poor, in environment, accumulates, and can cause very large pollution to animals and plants and the mankind's living environment.Abroad, from the 20 century 70s environmental friendly lubricant that begins one's study, tempo is nearly ten years more rapid.Up to the present, existing a large amount of matured products come out.China starts late for the research of environmental friendly lubricant, and also the product of rare maturation occurs at present, and relevant research report is also fewer.
Lubricating grease, as a kind of lubricant, includes the performance of base oil, thickening material and other functional additives.Compare with lubricating oil, lubricating grease has the former unexistent many special performances, such as good stopping property, corrosion-inhibiting, damping property and noise abatement etc.Early stage grease product, does not manyly add other additives and directly uses.
Modern industry is produced more and more higher to the requirement of grease product performance, so the kind of grease additive is also enriched gradually.Wherein, extreme-pressure anti-friction additive is a most important class active additive.And as the additive of environmentally friendly grease (oil), in basic fat (oil), have good responsiveness on the one hand, consider again on the other hand its impact on ecotope.The regulation of this class additive being done according to " (BLUE ANGEL) Blue Angel " tissue, the existing most additives that are applied in mineral fat (oil) are not all suitable in environmentally friendly grease (oil), and this just requires to carry out the development research of new additive agent.
Existing research shows, the nitrogen-containing hetero lopps additive of containing metal element is not the good multifunctional type lubricating grease of class (oil) additive, it meets the environment protection requirement of " ashless ", " without phosphorus ", expects that it will have a good application prospect in green lubrication fat (oil).In heterogeneous ring compound, thiadiazoles has higher cloud density and abundant active element S, N.Therefore when design additive, can reduce the requirement that active element is introduced.Thiadiazoles derivative and vegetable seed wet goods environmental friendliness base oil have good synergistic effect.Its many derivatives, if carboxylic acid derivative, dimercapto derivative are except having outstanding antiwear and friction reduction property, also there is very excellent metal passivity energy processed, be developed to multi-functional lubricating oil additive and be widely used in the severe rugged environments such as Seatask unit.
CN00801801.4 and CN00802316.6 disclose thiadiazoles dimer and have been used as extreme-pressure additive with reaction product and the adducts of poly-(ether) glycol, CN200480029627.4 discloses the lubricating composition of molybdate compound and thiadiazoles, on thiadiazoles parent, introduced oxyalkyl chain, there is good wear-resistant and anti-extreme pressure energy, but halohydrocarbon has been used in its preparation, do not meet the requirement of environmental protection.Therefore fat (oil) the dissolubility thiadiazoles derivative that is necessary to develop a kind of preparation technology's environmental protection is as extreme pressure anti-wear additives.
Summary of the invention
The object of the present invention is to provide a kind of ashless without phosphorus hydroxyl thiadiazoles derivative, it,, as lubricating grease (oil) additive, has good wear-resistant and anti-extreme pressure energy.
The preparation method who another object of the present invention is to provide this hydroxyl thiadiazoles derivative, has technique simple, and reaction conditions is gentle, the cheap feature that is easy to get and meets Atom economy of raw material of use.
An also object of the present invention is to provide this hydroxyl thiadiazoles derivative in the application as in extreme pressure anti-wear additives.
In order to realize the object of the invention, hydroxyl thiadiazoles derivative of the present invention, it has following structural formula:
In formula, R is
R wherein
1, R
2independently be selected from respectively C
1~ C
30straight chain, side chain or C
3~ C
30cycloalkyl; Be preferably R
1, R
2independently be selected from respectively C
1~ C
12straight chain, side chain or C
3~ C
8cycloalkyl.
Most preferred is 2-(2 '-hydroxypropyl) sulfydryl-5-sulfydryl-1,3,4-thiadiazoles or 2,5-bis-(2 '-hydroxyl dodecyl) sulfydryl-1,3,4-thiadiazoles.
Concrete structure is as follows:
The preparation method of hydroxyl thiadiazoles derivative of the present invention, comprises the steps:
By 0.05 mole 2,5-dimercapto-1,3,4-thiadiazoles joins in organic solvent, after being uniformly mixed, then drips 0.05 ~ 0.1 mole of epoxy compounds, be warming up to 50 ~ 100 ℃ of reactions 12 ~ 24 hours, after reaction finishes, through aftertreatment, obtain hydroxyl thiadiazoles derivative.
The chemical structural formula of described epoxy compounds is as follows:
R wherein
1, R
2define same as above.
Described aftertreatment adopts reaction solution is chilled to room temperature, and filters to remove insolubles, then steams except organic solvent.
Described organic solvent is acetone, benzene, toluene, chloroform, ethyl acetate, DMF, tetrahydrofuran (THF), dioxane, methyl-sulphoxide or C
1~ C
4fatty alcohol.
Specifically, the synthetic method of hydroxyl thiadiazoles derivative of the present invention can represent with chemical equation below:
Hydroxyl thiadiazoles derivative of the present invention has been owing to having introduced the oil soluble carbochain of hydroxyl, makes this hydroxyl thiadiazoles derivative can be well compatible with lubricating grease, and hydroxyl can be adsorbed in metallic surface effectively, strengthens extreme-pressure anti-wear effect.
The addition of hydroxyl thiadiazoles derivative of the present invention in lubricating grease (oil) is 0.1wt% ~ 15wt%; Be preferably 3wt% ~ 10wt%, most preferably be 3wt% ~ 5wt%.
Hydroxyl thiadiazoles derivative extreme pressure anti-wear additives of the present invention can be used separately and add in lubricating grease (oil), can obtain the lubricating system of good wear-resistant and anti-extreme pressure energy, and it can improve P in biodegradable lithium soap grease
bvalue 100.3% ~ 135.4%, improves P
dvalue 56.3% ~ 287.5% left and right, reduces wear scar diameter 11.2% ~ 34.5%.Also can with other lubricating grease (oil) additive compound use, can reach synergy synergy.
Accompanying drawing explanation
Fig. 1 is 2-(2 '-hydroxypropyl that embodiment 1 obtains) sulfydryl-5-sulfydryl-1, the infrared spectra spectrogram of 3,4-thiadiazoles.
Fig. 2 be embodiment 2 obtain 2,5-bis-(2 '-hydroxyl dodecyl) sulfydryl-1, the infrared spectra spectrogram of 3,4-thiadiazoles.
Fig. 3 is 2-(2 '-hydroxypropyl that embodiment 1 obtains) sulfydryl-5-sulfydryl-1, the proton nmr spectra spectrogram of 3,4-thiadiazoles.
Fig. 4 be embodiment 2 obtain 2,5-bis-(2 '-hydroxyl dodecyl) sulfydryl-1, the proton nmr spectra spectrogram of 3,4-thiadiazoles.
Embodiment
Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.
Get 7.5 grams of (0.05 moles) 2,5-dimercapto-1,3,4-thiadiazole, in 150 milliliters of three-necked flasks, then adds 50 milliliters of tetrahydrofuran (THF)s to make solvent.After being stirred under room temperature and mixing, more slowly drip 2.9 grams of (0.05 mole) propylene oxide.After dropwising, be warming up to 80 ℃ of reactions 24 hours.After reaction finishes, be chilled to room temperature, reacting liquid filtering, to remove insolubles, then is steamed except organic solvent, obtain hydroxyl thiadiazoles derivative extreme pressure anti-wear additives.Product 2-(2 '-hydroxypropyl) sulfydryl-5-sulfydryl-1,3,4-thiadiazoles quality is 9.6 grams, productive rate is 92.3%.Fig. 1 is the Infrared spectroscopy of product, and analytical results is as follows: IR(cm
-1): 3399.27(O-H), 2968.96,2923.94(-CH
3,-CH
2-), 1667.35(C=N), 1489.04,1419.20(Thiadiazole skeleton), 1265.86(O-H), 1119.02,1052.00(C-O), 713.13(C-S).Fig. 3 is the hydrogen nuclear magnetic resonance spectrum analysis of product, and analytical results is as follows: H
1-NMR(ppm): 1.310 ~ 1.367(-CH
3), 2.358(-SH), 3.128 ~ 3.344(-CH
2-), 4.131 ~ 4.159(-CH=).
Embodiment 2
Get 7.5 grams of (0.05 moles) 2,5-dimercapto-1,3,4-thiadiazole, in 150 milliliters of three-necked flasks, then adds 50 milliliters of tetrahydrofuran (THF)s to make solvent.After being stirred under room temperature and mixing, more slowly drip 18.4 grams of (0.1 mole) epoxy dodecanes.After dropwising, be warming up to 80 ℃ of reactions 24 hours.After reaction finishes, be chilled to room temperature, reacting liquid filtering, to remove insolubles, then is steamed except organic solvent, obtain hydroxyl thiadiazoles derivative extreme pressure anti-wear additives.Product 2,5-bis-(2 '-hydroxyl dodecyl) sulfydryl-1,3,4-thiadiazoles quality is 24.5 grams, productive rate is 94.6%.Fig. 2 is the Infrared spectroscopy of product, and analytical results is as follows: IR(cm
-1): 3428.68(O-H), 2920.83,2851.26(-CH
3,-CH
2-), 1642.36(C=N), 1384.75(-CH
3), 1068.25(C-O), 719.75(C-S).Fig. 4 is the hydrogen nuclear magnetic resonance spectrum analysis of product, and analytical results is as follows: H
1-NMR(ppm): 0.853 ~ 0.887(-CH
3), 1.250 ~ 1.306(-CH
2-), on 1.541 ~ 1.579(long-chain with-CH=contiguous-CH
2-), 3.224 ~ 3.245(and S vicinity-CH
2-), 3.498 ~ 3.542(-CH=).
According to the method for embodiment 1 or 2, adopt the epoxy compounds of different substituents can make following compound:
Embodiment 3
The present embodiment is the ultimate analysis of sample.Table 1 has been listed the results of elemental analyses of embodiment 1 ~ 2.From table 1, results of elemental analyses is known, and the measured value of the C of all target compounds, H, N, S element and the theoretical value of calculating by molecular formula meet the requirement of grease additive substantially, and absolute error is in allowed band.Can determine that gained compound is target compound.
Table 1 results of elemental analyses
Embodiment 4
The present embodiment is the extreme pressure and antiwear behavior test to sample.
According to GB3142-82 standard, to basic fat with by the hydroxyl thiadiazoles derivative of example 1,2 preparations, be added in the last non seizure load (P in commercially available biodegradable lithium soap grease
bbe worth) and sintering load (P
dvalue) carried out measuring (addition is 5.0wt%).The MS-10JB type four-ball tester that the four-ball tester that experiment is used produces for Xiamen trier factory, steel ball used is secondary GCr15 standard steel ball (AISI-52100), and its diameter is 12.7mm, and hardness is 59 ~ 61HRC.At room temperature carry out, rotating speed is 1760rpm.The results are shown in table 2.
Last non seizure load and the sintering load of the basic fat of table 2 and the lubricating grease sample that contains additive
Result shows that such hydroxyl thiadiazoles derivative adds to and in lubricating grease, has good extreme pressure property.
The vertical omnipotent friction wear testing machine of MMW-1 of producing with Jinan trier factory to the lubricating grease Specimen Determination of basic fat and the hydroxyl thiadiazoles derivative that contains embodiment 1,2 preparations under 392N load, experimental period is 30 minutes, additive level is 3.0wt%, the wear scar diameter that rotating speed is 1450rpm (WSD).Steel ball used is secondary GCr15 standard steel ball (AISI-52100), and its diameter is 12.7mm, and hardness is 59 ~ 61HRC.Experiment is at room temperature carried out.The results are shown in table 3.
The wear scar diameter of the basic fat of table 3 and the lubricating grease sample that contains additive
Result demonstration, compound synthetic in embodiment can effectively reduce WSD value.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements, all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (8)
1. hydroxyl thiadiazoles derivative, is characterized in that, it has following structural formula:
In formula, R is
R wherein
1, R
2independently be selected from respectively C
1~ C
30straight chain, side chain or C
3~ C
30cycloalkyl.
2. hydroxyl thiadiazoles derivative according to claim 1, is characterized in that R
1, R
2independently be selected from respectively C
1~ C
12straight chain, side chain or C
3~ C
8cycloalkyl.
3. hydroxyl thiadiazoles derivative according to claim 1 and 2, is characterized in that, this hydroxyl thiadiazoles derivative is 2-(2 '-hydroxypropyl) sulfydryl-5-sulfydryl-1,3,4-thiadiazoles or 2,5-bis-(2 '-hydroxyl dodecyl) sulfydryl-1,3,4-thiadiazoles.
4. the method for the hydroxyl thiadiazoles derivative described in preparation claim 1-3 any one, is characterized in that, comprises the steps:
By 0.05 mole 2,5-dimercapto-1,3,4-thiadiazoles joins in organic solvent, after being uniformly mixed, then drips 0.05 ~ 0.1 mole of epoxy compounds, be warming up to 50 ~ 100 ℃ of reactions 12 ~ 24 hours, after reaction finishes, through aftertreatment, obtain hydroxyl thiadiazoles derivative.
5. the preparation method of hydroxyl thiadiazoles derivative according to claim 4, is characterized in that, the chemical structural formula of described epoxy compounds is as follows:
R wherein
1, R
2definition is with claim 1-3 any one.
6. according to the preparation method of the hydroxyl thiadiazoles derivative described in claim 4 or 5, it is characterized in that, described organic solvent is acetone, benzene, toluene, chloroform, ethyl acetate, DMF, tetrahydrofuran (THF), dioxane, methyl-sulphoxide or C
1~ C
4fatty alcohol.
7. the hydroxyl thiadiazoles derivative described in claim 1-3 any one is in the application as in extreme pressure anti-wear additives.
8. a lubricating oil, the hydroxyl thiadiazoles derivative described in the claim 1-3 any one that it comprises 0.1wt% ~ 15wt%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109135871A (en) * | 2017-06-27 | 2019-01-04 | 中国石油化工股份有限公司 | A kind of heavy duty automobile gear oil composition and preparation method thereof |
| CN109942510A (en) * | 2019-03-25 | 2019-06-28 | 深圳市优宝新材料科技有限公司 | Thiazole derivative grafted olefin and its preparation method and application |
| CN114507556A (en) * | 2022-01-14 | 2022-05-17 | 中国科学院兰州化学物理研究所 | Thiadiazole lubricating oil anti-wear additive and preparation method thereof |
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| US20060035791A1 (en) * | 2003-10-10 | 2006-02-16 | R.T. Vanderbilt Company, Inc. | Lubricating compositions containing synthetic ester base oil, molybdenum compounds and thiadiazole-based compounds |
| CN101657480A (en) * | 2007-02-08 | 2010-02-24 | Lg化学株式会社 | Alkali-developable resins, its preparation method and comprise the photosensitive composition of this alkali-developable resins |
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2012
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| US20060035791A1 (en) * | 2003-10-10 | 2006-02-16 | R.T. Vanderbilt Company, Inc. | Lubricating compositions containing synthetic ester base oil, molybdenum compounds and thiadiazole-based compounds |
| CN101657480A (en) * | 2007-02-08 | 2010-02-24 | Lg化学株式会社 | Alkali-developable resins, its preparation method and comprise the photosensitive composition of this alkali-developable resins |
Non-Patent Citations (1)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109135871A (en) * | 2017-06-27 | 2019-01-04 | 中国石油化工股份有限公司 | A kind of heavy duty automobile gear oil composition and preparation method thereof |
| CN109942510A (en) * | 2019-03-25 | 2019-06-28 | 深圳市优宝新材料科技有限公司 | Thiazole derivative grafted olefin and its preparation method and application |
| CN114507556A (en) * | 2022-01-14 | 2022-05-17 | 中国科学院兰州化学物理研究所 | Thiadiazole lubricating oil anti-wear additive and preparation method thereof |
| CN114507556B (en) * | 2022-01-14 | 2022-08-30 | 中国科学院兰州化学物理研究所 | Thiadiazole lubricating oil anti-wear additive and preparation method thereof |
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