CN101768120A - Biphosphonate polyethoxy diimidazole salt compound as energy-saving antiwear agent and preparation method thereof - Google Patents
Biphosphonate polyethoxy diimidazole salt compound as energy-saving antiwear agent and preparation method thereof Download PDFInfo
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- CN101768120A CN101768120A CN200810142995A CN200810142995A CN101768120A CN 101768120 A CN101768120 A CN 101768120A CN 200810142995 A CN200810142995 A CN 200810142995A CN 200810142995 A CN200810142995 A CN 200810142995A CN 101768120 A CN101768120 A CN 101768120A
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Abstract
The invention discloses a biphosphonate polyethoxy diimidazole salt compound as an energy-saving antiwear agent and a preparation method thereof. The compound is a room-temperature ionic liquid and has the molecular structure of a formula I. The compound is generated through the reaction of a polyethoxy diimidazole compound and phosphoric acid ester. The compound has the characteristics of good temperature resistance, oxidation resistance, low freezing point and the like, the decomposition temperature thereof can be higher than 300 DEG C, the freezing point can be lower than minus 30 DEG C, and meanwhile, the compound has excellent oil solubility and water solubility. The compound can be used as the energy-saving antiwear agent, can form a layer of firm protective layer on the surface of a friction pair in the friction process and performs the actions of antifriction and wearing resistance.
Description
Technical field
The present invention relates to two imidazole salts compounds of a kind of energy-saving antiwear agent biphosphonate poly oxyethyl group and preparation method thereof.
Background technology
Ionic liquid at room temperature has purposes very widely, mainly as solvent, catalyzer and lubricant etc.Ionic liquid is meant mainly by organic cation and inorganic or organic anion constitutes and at the molten salt system that is in a liquid state below 100 ℃.Green Chemistry solvent characteristics such as they have that kind is many, not flammable, liquid journey wide ranges, steam are forced down, electrochemical window is wide, solubility property is adjustable.In recent years, in the ascendant to ion liquid research, ionic liquid has caused people's very big concern as the potential high performance lubricant.Wherein more as the tribological Properties of lubricant to the alkyl imidazole tetrafluoroborate ion liquid, find that it has good lubrication, anti-wear and wear-resistant performance to multiple friction pair.
Summary of the invention
The object of the present invention is to provide two imidazole salts compounds of a kind of energy-saving antiwear agent biphosphonate poly oxyethyl group and preparation method thereof.
The two imidazole salts compounds of a kind of energy-saving antiwear agent biphosphonate poly oxyethyl group, this compound is a kind of ionic liquid at room temperature, has formula I molecular structure
Wherein R represents that carbon number is the alkyl of 2-8, and n represents the diethoxy number, is the integer of 2-10.
The two imidazole salts compounds of biphosphonate poly oxyethyl group that we have prepared representative novelty have:
The two imidazole salts of bis phosphoric acid diethyl ester poly oxyethyl group, the two imidazole salts of bis phosphoric acid dibutyl ester poly oxyethyl group, the two imidazole salts of bis phosphoric acid dihexyl poly oxyethyl group.
The principle that this compound synthesizes is shown in reaction equation:
Wherein: n is an oxyalkyl chain joint number amount, equals 2-10; R represents that carbon number is the alkyl of 1-8.
The preparation method of the two imidazole salts compounds of a kind of biphosphonate poly oxyethyl group, it is characterized in that: this method mixes poly oxyethyl group double imidazole compound and phosphoric acid ester according to chemical dosage ratio, feed argon gas, under 50-200 ℃, react the two imidazole salts compounds of generation product biphosphonate poly oxyethyl group.
In the preparation method of the two imidazole salts compounds of biphosphonate poly oxyethyl group, the reaction times is 2-24 hour.
Among the preparation method of the present invention, reaction finishes the back and adopts ordinary method to isolate the two imidazole salts compounds of product poly oxyethyl group.
About poly oxyethyl group double imidazole compound, it has poly oxyethyl group ether and two glyoxaline structure, and its molecular weight is 100-400, and molecular structure is represented with formula II:
N representation alkoxy chain link quantity equals 3-10 among the formula II.
The poly oxyethyl group double imidazole compound that we use is selected from the two imidazoles of three polyethoxyies, the two imidazoles of four polyethoxyies, the two imidazoles of six polyethoxyies or the two imidazoles of ten polyethoxyies.
About the preparation method of poly oxyethyl group double imidazole compound, it comprises A and two reactions steps of B successively:
A, reactant adopt polyoxyethylene glycol, phosphorus tribromide or thionyl chloride,, carry out back flow reaction and generate the poly-second diether of dihalo as reaction solvent with benzene;
B, reactant adopt the poly-second diether of dihalo, imidazoles,, carry out back flow reaction and generate poly oxyethyl group double imidazole compound as reaction solvent with the ethanolic soln that contains sodium ethylate.
Because common ionic liquid adopts tetrafluoroborate or hexafluoro-phosphate radical as negatively charged ion more, this ion can produce hydrofluoric acid in the presence of water, and then can corrode the generation of steel body when using as lubricating oil, limit its application.And adopt phosphoric acid ester as negatively charged ion, imidazoles in use can not produce acidic substance as cationic ionic liquid, just can not produce corrosive nature to the steel body yet, phosphoric acid ester has very excellent lubricating property simultaneously, so this ionic liquid should have very outstanding use properties.And yet there are no report for the research of the two imidazole salts of biphosphonate poly oxyethyl group.
The two imidazole ion liquids of biphosphonate poly oxyethyl group have characteristics such as temperature tolerance is good, anti-oxidant, zero pour is low, and its decomposition temperature can be up to more than 300 ℃, and zero pour can have good oil soluble and water-soluble simultaneously less than-30 ℃.Can be used as energy-saving antiwear agent and use, it can form layer of firm protective layer at surface of friction pair in friction process, play the effect of antifriction antiwear.Early stage ionic liquid to adopt imidazoles be its cationic components more, but it exists that oil soluble is poor, easy shortcoming such as oxidation under the hot conditions.And the two imidazole salts of biphosphonate poly oxyethyl group have good oil soluble and water-soluble, and stability at elevated temperature is good.Because this ionic liquid has two imidazoles and biphosphonate structure, and its whole nitrogen content and phosphorus content are higher, the oxygen level height has good antioxygenation simultaneously, and friction process is also had good promoter action in addition.
Description of drawings
Fig. 1 is synthetic ionic liquid and polyalphaolefin synthetic oil wear scar diameter under the same conditions, experiment condition: 1450 rev/mins of rotating speeds, and the time: 30 minutes, load: 392 Ns, temperature: room temperature
Embodiment
The two imidazole salts of embodiment 1. bis phosphoric acid diethyl ester poly oxyethyl groups
Get 70g (1mol) imidazoles and be dissolved in the ethanolic soln that contains sodium ethylate, other gets the poly-second diether 160g of two bromos, and (0.5mol n=4) is added in this system, stirred under the room temperature 3 hours, reflux afterwards, and keep and stir 12 hours postcooling, remove by filter precipitation, add the water termination reaction.With trichloromethane above-mentioned product being extracted repeatedly repeatedly at last, and be moving phase with the trichloromethane, is that chromatographic column is separated with silica gel, can obtain the two imidazoles products of poly-second diether after distillation removes and desolvates after the collection respective components.
(0.1mol n=4) mixes with triethyl phosphate 38g (0.2mol), feeds argon gas afterwards, under agitation is heated to 120 ℃ again, and reaction was carried out 18 hours, and it is fully reacted to get the two imidazoles 50g of poly oxyethyl group.Viscosity by the monitoring reaction system changes therebetween, and till viscosity was constant, proved response finished.After this be cooled to room temperature, remove the compound of not participating in reaction with the anhydrous diethyl ether extraction, then, distillation is removed ether and can be obtained target product.Productive rate 85%.
This product has following character:
Density: 0.9135g/cm
3
Refractive index: 1.472
Viscosity: 437cst
Zero pour: less than-40 ℃
Solvability: water soluble, ethanol, acetone etc.
The two imidazole salts of embodiment 2. bis phosphoric acid dibutyl ester poly oxyethyl groups
Get 70g (1mol) imidazoles and be dissolved in the ethanolic soln that contains sodium ethylate, other gets the poly-second diether 307g of two bromos, and (0.5mol n=10) is added in this system, stirred under the room temperature 3 hours, reflux afterwards, and keep and stir 12 hours postcooling, remove by filter precipitation, add the water termination reaction.With trichloromethane above-mentioned product being extracted repeatedly repeatedly at last, and be moving phase with the trichloromethane, is that chromatographic column is separated with silica gel, can obtain the two imidazoles products of poly-second diether after distillation removes and desolvates after the collection respective components.
(0.1mol n=10) mixes with triethyl phosphate 55g (0.2mol), feeds argon gas afterwards, under agitation is heated to 130 ℃ again, and reaction was carried out 12 hours, and it is fully reacted to get the two imidazoles 60g of poly oxyethyl group.Viscosity by the monitoring reaction system changes therebetween, and till viscosity was constant, proved response finished.After this be cooled to room temperature, remove the compound of not participating in reaction with the anhydrous diethyl ether extraction, then, distillation is removed ether and can be obtained the heavy-gravity target product.Productive rate 94%.
This product has following character:
Density: 0.9012g/cm
3
Refractive index: 1.415
Viscosity: 358cst
Zero pour: less than-40 ℃
Solvability: water soluble, ethanol, acetone etc.
The two imidazole salts of embodiment 3. bis phosphoric acid dihexyl poly oxyethyl groups
Get 70g (1mol) imidazoles and be dissolved in the ethanolic soln that contains sodium ethylate, other gets the poly-second diether 230g of two bromos, and (0.5mol n=6) is added in this system, stirred under the room temperature 3 hours, reflux afterwards, and keep and stir 12 hours postcooling, remove by filter precipitation, add the water termination reaction.With trichloromethane above-mentioned product being extracted repeatedly repeatedly at last, and be moving phase with the trichloromethane, is that chromatographic column is separated with silica gel, can obtain the two imidazoles products of poly-second diether after distillation removes and desolvates after the collection respective components.
(0.1mol n=6) mixes with tri hexyl phosphate 70g (0.2mol), feeds argon gas afterwards, under agitation is heated to 180 ℃ again, and reaction was carried out 12 hours, and it is fully reacted to get the two imidazoles 43g of poly oxyethyl group.Viscosity by the monitoring reaction system changes therebetween, and till viscosity was constant, proved response finished.After this be cooled to room temperature, remove the compound of not participating in reaction with the anhydrous diethyl ether extraction, then, distillation is removed ether and can be obtained the heavy-gravity target product.Productive rate 90%.
This product has following character:
Density: 0.9053g/cm
3
Refractive index: 1.473
Viscosity: 513cst
Zero pour: less than-35 ℃
Solvability: water soluble, ethanol, acetone etc.
Rub(bing)test
Test adopts four-ball tester to carry out, and measuring method is GB3142-82.Used steel ball is an II level GCr15 standard steel ball, and loading load is 392 Ns, 1450 rev/mins of rotating speeds, room temperature, atmospheric condition, fraction time 30 minutes.Product prepared among the embodiment 1 and 2 and polyalphaolefin synthetic oil rub(bing)test have under the same conditions been carried out in the test.Its result as shown in Figure 1, as can be seen, prepared product has very excellent abrasion resistance.Its wear scar diameter polyalphaolefin synthetic oil of comparing can reduce more than 50%.
Claims (6)
1. two imidazole salts compounds of an energy-saving antiwear agent biphosphonate poly oxyethyl group, this compound is a kind of ionic liquid at room temperature, has formula I molecular structure
Wherein R represents that carbon number is the alkyl of 2-8, and n represents the diethoxy number, is the integer of 2-10.
2. compound as claimed in claim 1 is characterized in that compound is selected from the two imidazole salts of bis phosphoric acid diethyl ester poly oxyethyl group, the two imidazole salts of bis phosphoric acid dibutyl ester poly oxyethyl group or the two imidazole salts of bis phosphoric acid dihexyl poly oxyethyl group.
3. the preparation method of the two imidazoles phosphate ester salt compounds of alkyl as claimed in claim 1, it is characterized in that: this method mixes poly oxyethyl group double imidazole compound and phosphoric acid ester according to chemical dosage ratio, feed argon gas, under 50-200 ℃, react the two imidazole salts compounds of generation product biphosphonate poly oxyethyl group.
4. method as claimed in claim 3 is characterized in that: the reaction times is 2-24 hour.
5. method as claimed in claim 3 is characterized in that: poly oxyethyl group double imidazole compound, and it has poly oxyethyl group ether and two glyoxaline structure, and its molecular weight is 100-400, and molecular structure is represented with formula II:
N representation alkoxy chain link quantity equals 3-10 among the formula II.
6. method as claimed in claim 5 is characterized in that: poly oxyethyl group double imidazole compound is selected from the two imidazoles of three polyethoxyies, the two imidazoles of four polyethoxyies, the two imidazoles of six polyethoxyies or the two imidazoles of ten polyethoxyies.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190624A (en) * | 2010-03-10 | 2011-09-21 | 中国人民解放军63975部队 | Sulfur-containing/nitrogen-group-containing ionic liquid and preparation method thereof |
| CN104311490A (en) * | 2014-10-29 | 2015-01-28 | 江苏国泰超威新材料有限公司 | Preparation method of imidazoline-type phosphate electrolyte salt |
-
2008
- 2008-12-29 CN CN200810142995A patent/CN101768120A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190624A (en) * | 2010-03-10 | 2011-09-21 | 中国人民解放军63975部队 | Sulfur-containing/nitrogen-group-containing ionic liquid and preparation method thereof |
| CN102190624B (en) * | 2010-03-10 | 2015-01-07 | 中国人民解放军63975部队 | Sulfur-containing/nitrogen-group-containing ionic liquid and preparation method thereof |
| CN104311490A (en) * | 2014-10-29 | 2015-01-28 | 江苏国泰超威新材料有限公司 | Preparation method of imidazoline-type phosphate electrolyte salt |
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Application publication date: 20100707 |