CN104277887A - High-temperature antifriction antiwear extreme-pressure lubrication additive and preparation method thereof - Google Patents
High-temperature antifriction antiwear extreme-pressure lubrication additive and preparation method thereof Download PDFInfo
- Publication number
- CN104277887A CN104277887A CN201310274565.4A CN201310274565A CN104277887A CN 104277887 A CN104277887 A CN 104277887A CN 201310274565 A CN201310274565 A CN 201310274565A CN 104277887 A CN104277887 A CN 104277887A
- Authority
- CN
- China
- Prior art keywords
- temperature
- additive
- extreme
- formula
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Lubricants (AREA)
Abstract
The invention discloses a high-temperature antifriction antiwear extreme-pressure lubrication additive and a preparation method thereof. The additive is an aryl phosphate ester compound. Through molecule design, the phosphorus content and the molecular weight of the molecule self are increased, and the antiwear/extreme pressure performances and the heat stability of the molecule are enhanced. By adding the compound into polyether, especially at the temperature of 200 DEG C, excellent antifriction and antiwear performances and good extreme-pressure bearing capability can be obtained. The addition amount of the compound in polyether is 1%-4% by mass of polyether.
Description
Technical field
The present invention relates to a kind of high-temperature antifriction/wear-resistant/extreme boundary lubrication additive and preparation method thereof.
Background technology
Along with science and technology and industrial expansion, modern industry just develops towards extreme severe rugged environment, such as high speed, heavy lift and high-temperature condition.Particularly hot environment has important impact to the wear rate of friction pair under lubricating status.When lubricating temperature change, not only the viscosity characteristics of lubricant is changed, and the mechanical features of friction pair also can be changed.Under the lubricant applications environment of reality, there are many actual condition temperature higher than 100
?c, such as aerospace, mining industry and iron and steel processing industry etc.This special operating mode will cause lubricant deterioration and inefficacy, and lubricant and slip additive are faced the challenge.Also have many efficient synthesis basal liquids now, such as poly-a alkene (PAO), synthetic ester and polyethers (PAG) are developed to solve high temperature lubricating problem.But, only have a small amount of high temperature lubricating additive particularly wear-resistant/extreme boundary lubrication additive be commercially used, which has limited the application of high temperature lubricant.Therefore study the slip additive used in high temperature environments to be very important.
Tritolyl Phosphate (TCP) is widely used in industry oil as wear-resistant/extreme-pressure additive, the fields such as machining oil, lubricating grease and aviation engine lubricating oil.But be difficult in the industrial production to obtain high-quality cresols raw material because of it and it can cause nervosa poisoning, people need the less triaryl phosphate more easily obtained of exploitation toxicity.In addition, at aerospace field, although TCP as the anti-wear agent of jet engine oil by use many years, research of today concentrates on has more high molecular, on the material of more low volatility.Based on above reason, heat-resisting phenyl ring and the good phosphoric acid ester of abrasion resistance are combined in a molecule by we, have devised tetraphenyl Resorcinol biphosphonate (HDP).This material is not seen in report, only has European patent EP 0521628A2 to report Resorcinol tetraphenylphosphonium acid esters (it is the isomers of HDP) as fuel and lubrication oil additives, and determines its wear scar diameter at room temperature.
Summary of the invention
The object of the invention is to provide a kind of high-temperature antifriction abrasion resistant extreme-pressure slip additive and preparation method thereof.
The present invention is achieved by the following measures:
We have prepared a kind of at high temperature excellent lubricating properties, antifriction/wear-resistant/extreme boundary lubrication additive that preparation method is easy, by the method for molecular designing, we introduce Resorcinol in traditional phosphor-included additive TPP, molecular weight is obviously increased, thermostability strengthens, and this is favourable uses it as high-temperature antifriction/wear-resistant/extreme-pressure additive.
A kind of high-temperature antifriction abrasion resistant extreme-pressure slip additive, is characterized in that additive is for the aryl phosphate ester such as shown in formula III,
It is light yellow viscous liquid.
A kind of preparation method of high-temperature antifriction abrasion resistant extreme-pressure slip additive, it is characterized in that the method uses the triphenyl of formula (I) and the Resorcinol of formula (II), using aluminum trichloride (anhydrous) or Magnesium Chloride Anhydrous as catalyzer, 120 ~ 180 DEG C of Depressor responses 1 ~ 2 hour, the ester exchange offspring of production (III), adopts reliever to remove by-product phenol in whole process, the phenol that nitrogen purging removing is afterwards residual, be cooled to 120 DEG C, heat filtering; It is high-temperature antifriction abrasion resistant extreme-pressure slip additive that filtrate obtains light yellow viscous liquid 60 DEG C of washings.
The triphenyl of formula of the present invention (I) and the mol ratio of Resorcinol are 2.0 ~ 2.1:1.
The usage quantity of catalyzer of the present invention is 0.2% ~ 1% of reactant total mass.
Formula of the present invention (III) compound adds in polyethers (PAG), especially can obtain excellent antifriction, abrasion resistance at the temperature of 200 DEG C, good extreme pressure supporting capacity.
Formula of the present invention (III) compound is 1% ~ 4% of polyether quality as the high-temperature antifriction/wear-resistant/addition of extreme boundary lubrication additive in polyethers.
Accompanying drawing explanation
Fig. 1 is embodiment 1 product pyrolysis temperature curve.
Fig. 2 to Fig. 6 is that concentration is respectively 0%, 1%, 2%, embodiment 1 product of 3%, 4% adds polyethers (PAG) in 200 DEG C on the micro-vibration friction abrasion testing machine of SRV-IV, frequency 25Hz, 100N, amplitude 1mm, the relation curve of frictional coefficient change under the operating mode of long mill 30min.
Fig. 7 is that concentration is respectively 0%, 1%, 2%, 3%, and embodiment 1 product of 4% adds polyethers (PAG) in 200 DEG C on the micro-vibration friction abrasion testing machine of SRV-IV, frequency 25Hz, 100N, amplitude 1mm, the wear volume under the operating mode of long mill 30min.
Fig. 8 to be concentration be 4% embodiment 1 product add PAG at the micro-vibration friction abrasion testing machine of SRV-IV in 200 DEG C, the relation curve of the friction coefficient load change under frequency 25Hz, amplitude 1mm operating mode.
Embodiment
Embodiment 1
Thermometer is being housed, in the 100mL there-necked flask of nitrogen access equipment and vacuum distillation apparatus, is adding 45.7g(140mmol) triphenyl, 7.3g(67mmol) Resorcinol and 0.15g(1.1mmol) aluminum trichloride (anhydrous).When being warming up to 80 DEG C under decompression, mixture melts, and continues have liquid phenol to steam when being warming up to 120 DEG C.Reduce pressure stirring reaction 30min at this temperature.Be warming up to 180 ~ 190 DEG C again, have a large amount of phenol to flow out.Now pass into nitrogen purging 90 ~ 120min under decompression, residual phenol is removed.Be cooled to 120 DEG C, suction filtration, filtrate obtains light yellow viscous liquid 32.5g(productive rate for twice, 81.2% 60 DEG C of washings), be target product III.
Embodiment 2
Thermometer is being housed, in the 100mL there-necked flask of nitrogen access equipment and vacuum distillation apparatus, is adding 45.7g(140mmol) triphenyl, 7.3g(67mmol) Resorcinol and 0.16g(1.67mmol) Magnesium Chloride Anhydrous.When being warming up to 80 DEG C under decompression, mixture melts, and continues have liquid phenol to steam when being warming up to 120 DEG C.Reduce pressure stirring reaction 30min at this temperature.Be warming up to 180 ~ 190 DEG C again, have a large amount of phenol to flow out.Now pass into nitrogen purging 90 ~ 120min under decompression, residual phenol is removed.Be cooled to 120 DEG C, suction filtration, filtrate obtains light yellow viscous liquid 31.2g(productive rate for twice, 78.0% 60 DEG C of washings), be target product III.
Embodiment 3
Thermometer is being housed, in the 100mL there-necked flask of nitrogen access equipment and vacuum distillation apparatus, is adding 43.68g(134mmol) triphenyl, 7.3g(67mmol) Resorcinol and 0.15g(1.1mmol) aluminum trichloride (anhydrous).When being warming up to 80 DEG C under decompression, mixture melts, and continues have liquid phenol to steam when being warming up to 120 DEG C.Reduce pressure stirring reaction 30min at this temperature.Be warming up to 180 ~ 190 DEG C again, have a large amount of phenol to flow out.Now pass into nitrogen purging 90 ~ 120min under decompression, residual phenol is removed.Be cooled to 120 DEG C, suction filtration, filtrate obtains light yellow viscous liquid 31.8g(productive rate for twice, 79.5% 60 DEG C of washings), be target product III.
Evaluation of Thermal Stability
Thermostability is measured by STA 449 C Jupiter simultaneous TG-DSC.Tetraphenyl Resorcinol biphosphonate (HDP) 5mg embodiment 1 prepared puts into sample pool, and probe temperature is from 20 ~ 800 DEG C, and temperature increase rate is 10 DEG C/min, measures under air ambient.Result as shown in Figure 1.HDP does not show mass loss below 200 DEG C.Its heat decomposition temperature (
t d) be 406.7 DEG C.Show that this material has extraordinary thermal stability.
The tribological property evaluation of product:
Tetraphenyl Resorcinol biphosphonate embodiment 1 prepared is dissolved in polyethers, and being mixed with concentration is 1%, 2%, 3%, 4% solution, its tribological property of comprehensive evaluation:
1. the micro-vibration friction abrasion testing machine test concentrations of SRV-IV adopting German Optimol grease company to produce is respectively 0%, 1%, 2%, the polyether solutions of embodiment 1 product of 3%, 4% at 200 DEG C, frequency 25Hz, amplitude 1mm, frictional coefficient f under the operating mode of load 100N during long mill 30min, test the GCr15 bearing steel that steel ball used is F=10mm, lower sample is the GCr15 bloom of F24 × 7.9mm.The results are shown in accompanying drawing 2 ~ 6.As seen from the figure, under 200 DEG C of high temperature, during 100N load lower slip, this compound well can lubricate steel-steel frictional pair as additive, and frictional coefficient significantly reduces, and friction reducing effect is very obvious.
2. adopt MicroXAM 3D non-contacting Surface Tester test concentrations to be respectively 0%, 1%, 2%, 3%, the polyether solutions of embodiment 1 product of 4% at 200 DEG C, frequency 25Hz, the mill spot volume under the operating mode of amplitude 1mm, load 100N after long mill 30min.As shown in Figure 7, after adding this additive, the wear volume of mill spot is obviously by low for test result.Show that this additive has good anti-wear effect.
3. the micro-vibration friction abrasion testing machine test concentrations of SRV-IV adopting German Optimol grease company to produce is respectively the polyether solutions of embodiment 1 product of 0% and 4% at 200 DEG C, frequency 25Hz, under the operating mode of amplitude 1mm, frictional coefficient f is with the relation curve of load change, test the GCr15 bearing steel that steel ball used is F=10mm, lower sample is the GCr15 bloom of F24 × 7.9mm.The results are shown in accompanying drawing 8.As seen from the figure, in the process that program loads, polyethers is 500N without seizing load under this operating mode, after adding embodiment 1 product of 4%, its maximum bearing load is increased to 930N, shows that this phosphor-included additive at high temperature has very excellent extreme pressure property.
Claims (4)
1. a high-temperature antifriction abrasion resistant extreme-pressure slip additive, is characterized in that additive is for the aryl phosphate ester such as shown in formula III,
It is light yellow viscous liquid.
2. the preparation method of high-temperature antifriction abrasion resistant extreme-pressure slip additive as claimed in claim 1, it is characterized in that the method uses the triphenyl of formula (I) and the Resorcinol of formula (II), using aluminum trichloride (anhydrous) or Magnesium Chloride Anhydrous as catalyzer, 120 ~ 180 DEG C of Depressor responses 1 ~ 2 hour, the ester exchange offspring of production (III), adopts reliever to remove by-product phenol in whole process, the phenol that nitrogen purging removing is afterwards residual, be cooled to 120 DEG C, heat filtering; It is high-temperature antifriction abrasion resistant extreme-pressure slip additive that filtrate obtains light yellow viscous liquid 60 DEG C of washings:
。
3. method as claimed in claim 2, is characterized in that the triphenyl of formula (I) and the mol ratio of Resorcinol are 2.0 ~ 2.1:1.
4. method as claimed in claim 2, is characterized in that the usage quantity of catalyzer is 0.2% ~ 1% of reactant total mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310274565.4A CN104277887A (en) | 2013-07-02 | 2013-07-02 | High-temperature antifriction antiwear extreme-pressure lubrication additive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310274565.4A CN104277887A (en) | 2013-07-02 | 2013-07-02 | High-temperature antifriction antiwear extreme-pressure lubrication additive and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104277887A true CN104277887A (en) | 2015-01-14 |
Family
ID=52253238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310274565.4A Pending CN104277887A (en) | 2013-07-02 | 2013-07-02 | High-temperature antifriction antiwear extreme-pressure lubrication additive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104277887A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9777021B2 (en) | 2016-02-02 | 2017-10-03 | Qatar Foundation | Lubricant additives |
| CN110914391A (en) * | 2018-01-24 | 2020-03-24 | 出光兴产株式会社 | Lubricating oil composition and composition for refrigerator |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0521628A2 (en) * | 1991-06-14 | 1993-01-07 | Ethyl Petroleum Additives, Inc. | Organic phosphates and their preparation |
-
2013
- 2013-07-02 CN CN201310274565.4A patent/CN104277887A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0521628A2 (en) * | 1991-06-14 | 1993-01-07 | Ethyl Petroleum Additives, Inc. | Organic phosphates and their preparation |
Non-Patent Citations (1)
| Title |
|---|
| 杨智中等: "四苯基对苯二酚双磷酸酯的合成与应用研究", 《南京师大学报(自然科学版)》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9777021B2 (en) | 2016-02-02 | 2017-10-03 | Qatar Foundation | Lubricant additives |
| CN110914391A (en) * | 2018-01-24 | 2020-03-24 | 出光兴产株式会社 | Lubricating oil composition and composition for refrigerator |
| CN110914391B (en) * | 2018-01-24 | 2022-11-18 | 出光兴产株式会社 | Lubricating oil composition and composition for refrigerator |
| US11542455B2 (en) | 2018-01-24 | 2023-01-03 | Idemitsu Kosan Co., Ltd. | Lubricating oil composition and composition for refrigerator |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gusain et al. | Halogen-free ionic liquids: effect of chelated orthoborate anion structure on their lubrication properties | |
| CN105254663B (en) | A kind of chain alkyl imidazoles phosphate ion liquid and its preparation method and application | |
| JP7084794B2 (en) | Ionic liquids and lubricant compositions | |
| CN104513126A (en) | Preparation method and applications of alkyl multi-benzyl toluene or alkyl dibenzyl toluene | |
| CN104312701A (en) | Lubrication oil | |
| CN102807908A (en) | Wide temperature range polyol ester lubricating oil composition suitable for aircraft engine | |
| CN105523924B (en) | Six additions [60] fullerene derivate and its application in lubricating area | |
| CN104293420B (en) | The new application of extreme pressure anti-wear additives, the composition containing the material and application thereof | |
| JP2013023580A (en) | Antiwear agent composition for lubricant oil | |
| CN105385487A (en) | Low-cost and long-service-life lubricating oil | |
| CN104277887A (en) | High-temperature antifriction antiwear extreme-pressure lubrication additive and preparation method thereof | |
| WO2014069670A1 (en) | Alkylated diphenyl ether compound and lubricating oil containing said compound | |
| CN102260572A (en) | P-N extreme pressure and anti-wear additive and preparation method thereof | |
| CN106458838B (en) | The ester of pentaerythrite and its used in different tridecanoic acid | |
| Wu et al. | Tribological properties of naphthyl phenyl diphosphates as antiwear additive in polyalkylene glycol and polyurea grease for steel/steel contacts at elevated temperature | |
| CN104507900B (en) | Alkylated diphenyl ethers compound and the lubricating oils containing this compound | |
| Guo et al. | Friction and wear properties of halogen-free and halogen-containing ionic liquids used as neat lubricants, lubricant additives and thin lubricant layers | |
| CN104694210A (en) | High-temperature-resistant, extreme pressure and antiwear additive for lubricating grease and preparation method thereof | |
| CN104817594B (en) | A kind of boric ester derivative containing molybdenum and its preparation method and application | |
| CN104177406B (en) | Bis-phosphite and preparation method thereof, purposes and lubricant oil composite | |
| CN104694209A (en) | High temperature grease extreme pressure antiwear additive and its preparation method | |
| CN111662760B (en) | Screw compressor oil and preparation method thereof | |
| CN115651734A (en) | Wear-resistant silicon oil composite lithium-based lubricating grease and preparation process thereof | |
| CN106432333A (en) | Sulfur-containing phosphate ionic liquid and preparation method and application thereof | |
| CN102041142B (en) | Fluorine-containing lubricating oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150114 |
|
| WD01 | Invention patent application deemed withdrawn after publication |