CN104327054B - Water-soluble benzotriazole imidazoline extreme pressure anti-wear additives and preparation method thereof - Google Patents
Water-soluble benzotriazole imidazoline extreme pressure anti-wear additives and preparation method thereof Download PDFInfo
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- CN104327054B CN104327054B CN201410640382.4A CN201410640382A CN104327054B CN 104327054 B CN104327054 B CN 104327054B CN 201410640382 A CN201410640382 A CN 201410640382A CN 104327054 B CN104327054 B CN 104327054B
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- benzotriazole
- water
- imidazole group
- containing imidazole
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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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
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/38—Heterocyclic nitrogen compounds
- C10M133/44—Five-membered ring containing nitrogen and carbon only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
Abstract
The present invention relates to a kind of synthesis technology of Benzotriazole Derivative containing imidazole group and its applications.It is raw material that its synthesis, which is with benzotriazole, it is reacted with monoxone, diethylenetriamine, N- hydroxy-ethylenediamine, ethylenediamine, triethylene tetramine and tetraethylenepentamine, dimethylbenzene or toluene do azeotropic agent, it is 1: 1.1 reaction that benzotriazole acetic acid, which is reacted with amines such as diethylenetriamine, N- hydroxy-ethylenediamines with molar ratio, reaction temperature is 130-160 DEG C and 180-220 DEG C, and the reaction time is respectively 4 hours or so and 2 hours or so.Of the invention is easy to operate, and yield is high, and reaction condition is easily controllable.This product benzotriazole imidazolidine derivatives can be applied to water-based lubricating liquid, copper inhibitor and antirust agent etc..
Description
The present invention relates to the benzotriazole imidazolidine derivatives and preparation method thereof containing imidazole group, may be used as water
Dissolubility antiwear additive also can be used as copper inhibitor, belong to field of chemical technology.
Background technique
Benzotriazole and methyl benzotriazazole are well-known copper corrosion inhibitor.Benzotriazole is in mineral oil
In have good tribological property, extreme pressure, the antiwear additive being often used in lubricating oil, but its oil-soluble and it is water-soluble all compared with
Difference.Benzotriazole as the corrosion inhibiter in aqueous solution should be used cooperatively when in use with other cosolvents, increase its dissolution
Degree, so that benzotriazole is more convenient when in use.When the polar group of general intramolecular is power supply subtype, on central atom
Cloud density it is bigger, corrosion mitigating effect is better.Imidazoline has preferable water solubility, and can be formed and be complexed with metallic element
Object forms good adsorption layer on surface, water soluble functional group is introduced in Benzotriazole Derivative, such as amino and hydroxyl,
Its water solubility can be increased.The properties that this patent comprehensively considers benzotriazole and imidazoline has, in order to make additive
Antiwear and reducing friction, antioxygen or performance are played, the imidazolidine derivatives containing benzotriazole functional group have been synthesized.
Patent CN1837338 has synthesized double 1- (benzotriazole base -1- alkyl) polysulfide, can be used as lubricant grease
Extreme pressure, anticorrosive additive are used alone or are used in combination with other lubricating oil and grease additives, have excellent extreme pressure anti-corrosion
Performance.
Patent CN101205216 has synthesized benzotriazole ammonium salts, as oil solubility lubricant additive.
Patent CN102746279A discloses one kind ionic liquid of group containing benzotriazole and its preparation method and application.
The cation of ionic liquid is glyoxaline cation, and anion is hexafluoro-phosphate radical, tetrafluoroborate or two (trimethyl fluoride sulfonyls)
Amine anion, the cyclosubstituted end group group containing benzotriazole of imidazoles.Ionic liquid is as lube oil additive or lubricating grease
Additive uses.
Summary of the invention
The object of the present invention is to which the problem poor according to solubility of the benzotriazole in lubricating oil and water, provides
A kind of synthesis technology of the Benzotriazole Derivative containing imidazole group, the compound have good extreme pressure, abrasion resistance and
Corrosion resistance, while there is preferable solubility in water base lubricant, and provide the method for synthesis above compound.
The technical scheme is that benzotriazole acetic acid is formed with chloroacetate reaction using benzotriazole as raw material,
Then dehydration cyclization is carried out with diethylenetriamine, N-hydroxyethyl-ethylenediamine, ethylenediamine, triethylene tetramine and tetraethylenepentamine etc. again
Reaction generates benzotriazole imidazoline, and reaction condition is easily controllable, and yield is high.
The synthesis of Benzotriazole Derivative according to the present invention containing imidazole group can use following chemical reaction
Equation indicates:
Wherein, Y is diethylenetriamine, N-hydroxyethyl-ethylenediamine, ethylenediamine, triethylene tetramine and tetraethylenepentamine；X is phase
Answer terminated radical.
Benzotriazole Derivative of the present invention containing imidazole group can be used as a kind of multifunctional water based lubricating oil
Additive can also be used as corrosion inhibiter.
The beneficial effect of the present invention compared with the prior art is that the compound of the present invention can be used alone, and can also be added
It is added in water base basal liquid and uses, there is good water-soluble and good extreme pressure, abrasion resistance, while also having erosion-resisting
Ability.As additive in use, its additive amount is 0.1wt%~5.0wt%.
Present invention Benzotriazole Derivative containing imidazole group can also be used in combination with other lubricating oil and grease additives, can
Reach synergy synergistic effect.
Benzotriazole Derivative of the present invention containing imidazole group is that a kind of very effective multifunctional lubricant (rouge) adds
Add agent and corrosion inhibiter, what is specifically synthesized has:
Synthesis；
Synthesis；
Synthesis.
Product of the present invention the water-based lubricating liquids such as water, water-ethylene glycol, water-glycerol, polyethylene glycol, polyethers suitable for doing
Additive improves the extreme pressure, abrasion resistance and erosion-resisting ability of water-based lubricating liquid.
Specific embodiment
For a better understanding of the present invention, it is illustrated by three examples:
Example 1: being added the benzotriazole of 20g in the three-necked flask of 1 250ml, and the water that 100ml is added makees solvent,
The NaOH of 8.0g is added, is stirred to react 3h at 90 DEG C, the chloroethene aqueous acid of 18g, 90 DEG C of reactions are continuously added dropwise in half an hour
3h, product room temperature is cooling and HCl is added until there is a large amount of white precipitates, filtering washing chloride ion, obtained benzotriazole
11.24g is obtained after acetic acid is dry, then dimethylbenzene is separately added into the three-necked flask of 250ml and makees solvent and azeotropic agent,
The diethylenetriamine of 8ml reacts 4h at 140-160 DEG C except the water generated in dereaction, removes dereaction in 190-210 DEG C of reaction 2h
The water of middle generation is evaporated under reduced pressure to get light yellowish brown viscous liquid benzotriazole acetic acid imidazole radicals ethamine is arrived.
Example 2: being added the benzotriazole of 20g in the three-necked flask of 1 250ml, and the water that 100ml is added makees solvent,
The NaOH of 8.0g is added, is stirred to react 3h at 90 DEG C, the chloroethene aqueous acid of 18.0g is continuously added dropwise in half an hour, 90 DEG C anti-
3h is answered, product room temperature is cooling and HCl is added until there is a large amount of white precipitates, filtering washing chloride ion, obtained three nitrogen of benzo
11.09g is obtained after zole acetic acid is dry, then dimethylbenzene is separately added into the three-necked flask of 250ml and makees solvent and azeotropic agent,
The N-hydroxyethyl-ethylenediamine of 8ml reacts 4h at 140-160 DEG C except the water generated in dereaction, in 190-210 DEG C of 2~3h of reaction
Except the water generated in dereaction, it is evaporated under reduced pressure to get light yellowish brown viscous liquid benzotriazole acetic acid imidazole radicals ethyl alcohol is arrived.
Example 3: being added the benzotriazole of 20g in the three-necked flask of 1 250ml, and the water that 100ml is added makees solvent,
The NaOH of 8.0g is added, is stirred to react 3h at 90 DEG C, the chloroethene aqueous acid of 18.0g is continuously added dropwise in half an hour, 90 DEG C anti-
3h is answered, product room temperature is cooling and HCl is added until there is a large amount of white precipitates, filtering washing chloride ion, obtained three nitrogen of benzo
11.19g is obtained after zole acetic acid is dry, then dimethylbenzene is separately added into the three-necked flask of 250ml and makees solvent and azeotropic agent,
The triethylene tetramine of 8.2ml reacts 4~6h at 140-160 DEG C except the water generated in dereaction, in 190-210 DEG C of 2~3h of reaction
Except the water generated in dereaction, it is evaporated under reduced pressure to get light yellowish brown viscous liquid benzotriazole acetic acid imidazole radicals ethamine is arrived
Base ethamine.
All target compounds determine that synthetic has the life of imidazole ring by Spectrum One type infrared spectrometer
At C, H of additive, the results are shown in Table 1 for N element analysis.The elemental analysis result from table 1 is it is found that all target compounds
C, H, N element measured value be consistent substantially with the theoretical value calculated by molecular formula, absolute error is within the allowable range.It can be true
Fixed gained compound is target compound.
The elemental analysis result (being calculated value in bracket) of the various examples of table 1
| Example | C% | H% | N% |
| Example 1 | 58.37(59.01) | 6.68(6.55) | 34.11(34.42) |
| Example 2 | 58.15(58.77) | 6.16(6.12) | 27.80(28.57) |
| Example 3 | 58.17(58.53) | 6.99(7.32) | 34.78(34.15) |
The performance evaluation of target compound:
Since the density and viscosity of water is low, freezing point is higher, and in order to expand its use scope, second two is usually added in water
The polyalcohols such as alcohol, glycerine, polyethylene glycol reduce its freezing point and improve its viscosity.Herein with deionized water and ethylene glycol with matter
Amount is used as basal liquid than 1: 1, and additive is configured to the solution of 0.5wt%, 1.0wt%, 1.5wt%, 2.0wt%.
The MRS-10A type friction wear testing machine produced using Jinan testing machine factory contains miaow to prepared by example 1, example 2
The maximum nonseizure load (PB value) of the Benzotriazole Derivative of oxazolyl group is determined, test period 10s.According to
SH/T0189-92 (392N) standard carries out long mill, experimental condition are as follows: revolving speed 1450r/min, room temperature (20 DEG C or so), when test
Between 30min, the wear scar diameter (WSD) tried under 3 is measured using reading microscope (precision 0.01), takes its average value as mill
Spot diameter measured value.Second level GCr15 standard steel ball (AISI-52100) of the steel ball for the production of Shanghai Bearing Factory, diameter 12.7mm,
Hardness HRC is 59-61.
PBThe result of wear scar diameter (WSD) is listed in table 2 under value and 392N.
Such imidazole radicals Benzotriazole Derivative is added in water based lubrication basal liquid with excellent table 2 as the result is shown
Solubility property, extreme pressure property and abrasion resistance.
Maximum nonseizure load (the P of 2 base oil of table and various additivesBValue)
In addition, determining the corrosion resistance of example 2, the product prepared in example 4 by GB5096-85 standard method.Through
Measurement it is found that two kinds of production concentrations be 1.0wt% polyethylene glycol at 100 DEG C constant temperature 3h be 1A grades to the corrosion of copper sheet.
Claims (4)
1. a kind of Benzotriazole Derivative containing imidazole group, which is characterized in that the benzotriazole containing imidazole group
Derivative, the substance have following structure formula:
X is
2. a kind of preparation method of Benzotriazole Derivative containing imidazole group according to claim 1, feature exist
In:
(1) it is reacted at 90 DEG C 3 hours using benzotriazole with sodium hydrate aqueous solution, monoxone is then slowly added dropwise, instead
It answers 3 hours, takes out reaction solution, it is cooling, hydrochloric acid is added and removes chloride ion until there is a large amount of white precipitates, washing, obtains benzo three
Nitrogen zole acetic acid；
(2) the benzotriazole acetic acid that the first step obtains respectively with N-hydroxyethyl-ethylenediamine, triethylene tetramine and tetraethylenepentamine
It is reacted；
Second step is in the presence of reaction medium, reaction medium are as follows: the nonpolarity of one of toluene, benzene, dimethylbenzene and hexamethylene has
Solvent, dimethylbenzene are azeotropic agent 20%-25% of the total volume；
Reaction temperature is reacted at 130-160 DEG C, and except the moisture generated in dereaction, the time is 3-5 hours, at 180-220 DEG C
Lower reaction, except the moisture generated in dereaction, the time is 2-3 hours；
The molar ratio of benzotriazole acetic acid and N-hydroxyethyl-ethylenediamine, triethylene tetramine is 1: 1.0~1.2.
3. the application of the Benzotriazole Derivative according to claim 1 containing imidazole group, which is characterized in that described to contain
Application of the Benzotriazole Derivative of imidazole group as water-soluble extreme-pressure anti-friction additive, the benzo containing imidazole group
Triazole derivatives are applied in water, water-ethylene glycol, water-glycerol and other water base basal liquids, and can be with other water based lubrications
Additive is used in combination.
4. the application of the Benzotriazole Derivative according to claim 3 containing imidazole group, which is characterized in that described
Benzotriazole Derivative additive amount mass percent containing imidazole group is 0.1%-3.0%.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US9752092B2 (en) * | 2015-10-30 | 2017-09-05 | Chevron Oronite Company Llc | Lubricating oil compositions containing amidine antioxidants |
| CN106632277B (en) * | 2016-11-11 | 2019-04-16 | 西安交通大学 | A kind of matal deactivator and the preparation method and application thereof for preventing active sulfur from corroding |
| CN107253945A (en) * | 2017-07-04 | 2017-10-17 | 华东交通大学 | BTA imidazolidine derivatives and its preparation method and application |
| CN107311931A (en) * | 2017-07-04 | 2017-11-03 | 华东交通大学 | Water-soluble fatty acid imidazoline quinoline and its preparation method and application |
| CN109679717B (en) * | 2017-10-18 | 2022-06-24 | 中国石油化工股份有限公司 | Compressor lubricating oil composition and preparation method thereof |
| CN110845419B (en) * | 2019-11-14 | 2021-09-10 | 安徽金德润滑科技有限公司 | Extreme pressure antiwear agent and road vehicle gear oil containing same |
| CN111423913A (en) * | 2020-04-21 | 2020-07-17 | 中国科学院兰州化学物理研究所 | Plant-based base oil with copper corrosion inhibition function |
| CN114656588B (en) * | 2022-05-06 | 2023-03-28 | 中国科学院兰州化学物理研究所 | Polyion liquid, preparation method and application thereof, lubricating and tackifying additive and supramolecular gel lubricant |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746279A (en) * | 2011-04-19 | 2012-10-24 | 中国科学院兰州化学物理研究所 | Benzotriazole group-containing ionic liquid and its preparation method and use |
| CN103539786A (en) * | 2013-10-25 | 2014-01-29 | 武汉工程大学 | Benzotriazole imidazoline and derivative and synthesis process and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746279A (en) * | 2011-04-19 | 2012-10-24 | 中国科学院兰州化学物理研究所 | Benzotriazole group-containing ionic liquid and its preparation method and use |
| CN103539786A (en) * | 2013-10-25 | 2014-01-29 | 武汉工程大学 | Benzotriazole imidazoline and derivative and synthesis process and application thereof |
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