CN100487093C - Phosphamide ester extreme pressure anti-wear additives and preparation and application thereof - Google Patents
Phosphamide ester extreme pressure anti-wear additives and preparation and application thereof Download PDFInfo
- Publication number
- CN100487093C CN100487093C CNB2006100657377A CN200610065737A CN100487093C CN 100487093 C CN100487093 C CN 100487093C CN B2006100657377 A CNB2006100657377 A CN B2006100657377A CN 200610065737 A CN200610065737 A CN 200610065737A CN 100487093 C CN100487093 C CN 100487093C
- Authority
- CN
- China
- Prior art keywords
- extreme pressure
- pressure anti
- wear additives
- add
- 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.)
- Active
Links
Images
Abstract
The invention provides a extreme pressure antiwear agent with structure of right general formula, wherein R, R' is same or different alkyl group with C1-C20 linear chain or branched chain, asphalt base, aromatic group or aralkyl, R'' is amino or alkyl group with C1-C18 linear chain or branched chain, aromatic group, aralkyl or asphalt base. The antiwear agent is reacted by phosphorus trichloride and C1-C20 alcohol, hydrazine hydrate or C4-C18 orgnic amine. The antiwear agent of the invention can be used in lubrication oil and lubricant grease with 0.1-3.0 w% of recommeding amount.
Description
Technical field
The present invention relates to a kind of extreme pressure anti-wear additives that is used for lubricating oil and lubricating grease, and its production and application method.
Technical background
At present, the wear preventive additive of widely used lubricating oil (fat) mainly contains di-n-butyl phosphite (T304), tritolyl phosphate (T306), sulphur phosphoric acid-formaldehyde-amine condenses (T305), the multiple ester amine salt (T307) of sulphur phosphoric acid etc., kind is few, and shortcoming is arranged respectively, too high as the di-n-butyl phosphite activity, corrosion is more serious in the use; The tritolyl phosphate oil film strength is not high; The multiple ester amine salt of sulphur phosphoric acid-formaldehyde-amine condenses sulphur phosphoric acid has very smelly smell etc.
CN 1156482C has synthesized a kind of Spirocyclophophorousamine amine, is used for asymmetric catalytic hydrogenation, and chemical formula is
US 5919967 has reported a kind of synthetic method of phosphoramidite, and as the intermediate of preparation phosphoric acid ester, reaction formula is as follows, and R ＇ is pyridine, pyroles heterocyclic group in the formula.
Summary of the invention
The invention provides a kind of good phosphamide ester extreme pressure wear preventive additive of abrasion resistance of low smell.
The present invention also provides the preparation method of above-mentioned additive.
The present invention also provides above-mentioned Application of Additives method.
Extreme pressure anti-wear additives provided by the invention is a kind of phosphoramidite (hydrazine) ester, has following formula:
R, R ＇ are C identical or inequality in the formula
1～C
20The alkyl of straight or branched, cycloalkyl, aryl or aralkyl, preferred C
4～C
16Alkyl, R " is amino (NH
2) or C
1～C
18Alkyl, aralkyl, aryl or the cycloalkyl of straight or branched, preferred amino or C
4～C
16Alkyl, phenyl or cycloalkyl.
The preparation method of extreme pressure anti-wear additives provided by the invention comprises:
Make phosphorus trichloride and C
1～C
20Alcohols reacts down at-20 ℃～20 ℃ and generates the inferior phosphinylidyne dichloro of intermediate; Add C again
1～C
20Alcohols is kept-20 ℃～20 ℃ and is continued reaction to generating the inferior phosphoryl chloride of intermediate; In inferior phosphoryl chloride, add hydrazine hydrate or C
4～C
18Organic amine is warming up to 80 ℃～140 ℃ afterreactions to generating phosphoramidite (hydrazine) ester.
Specifically, anti-wear agent provided by the invention can prepare in accordance with the following methods:
(1) in the presence of organic solvent, by phosphorus trichloride, C
1～C
20Alcohols reacts down in-20 ℃～20 ℃ and generates the inferior phosphinylidyne dichloro of intermediate.This step reaction is quick thermopositive reaction, in order to ensure the purity of final product, preferably controls phosphorus trichloride and C
1～C
20The mole number of alcohol is identical.
(2) in the presence of organic solvent, make inferior phosphinylidyne dichloro of intermediate and C
1～C
20Alcohols mixes, and adds acid binding agent in case of necessity, keeps-20 ℃～20 ℃ to generating the inferior phosphoryl chloride of intermediate; This step also is quick thermopositive reaction, adds the hydrogenchloride that acid binding agent can neutralization reaction generates, and promotes that molecular balance moves to the product direction, improves the yield of final product.In order to ensure the purity of final product, preferably control inferior phosphinylidyne dichloro of intermediate and C
1～C
20The mole number of alcohol is identical.
(3) in inferior phosphoryl chloride, drip hydrazine hydrate or C
4～C
18Organic amine slowly is warming up to 80 ℃～140 ℃ and continues reaction 0.1～4 hour.In order to improve the yield of final product, can add acid binding agent in the reaction system.
Reaction finishes, and obtains the target compound crude product behind washing, drying, the desolventizing.Crude product can separate purification with silica gel column chromatography or underpressure distillation.
The add-on of the middle acid binding agent in step (2) and (3) can be 1～4 times of phosphorus trichloride mole number, phosphorus trichloride and hydrazine hydrate or C
4～C
18The theoretical molar ratio of organic amine is 1:1, but hydrazine hydrate or C
4～C
18Organic amine can be excessive 5～10%, so that inferior phosphoryl chloride complete reaction.
Said organic solvent is the solvent that can dissolve phosphorus trichloride, for example one or more in ether, tetrahydrofuran (THF), the toluene.The consumption of solvent is advisable with complete solubilizing reaction thing.
Said acid binding agent can be organic bases or mineral alkali, for example one or more in sodium hydroxide, Tetrabutyl amonium bromide, the triethylamine.
Among the said preparation method of the present invention, the intermediate of reaction also can separate earlier, carries out the next step again.
The recommendation consumption of anti-wear agent of the present invention in lubricating oil, lubricating grease is 0.1～3.0w%, is benchmark with the weight of lubricating oil, lubricating grease.
Anti-wear agent of the present invention is a kind of phosphorous, nitrogen additive, has the chemically reactive of appropriateness, and oil soluble is good, with other additive good compatibleness is arranged, and does not contain element sulphur, and no specific peculiar smell can reduce the pollution to air.Anti-wear agent supporting capacity of the present invention is much higher than tritolyl phosphate (T306), have rust-preventing characteristic and copper corrosion rejection simultaneously, it is a kind of multipurpose additive, be applied in gear oil and the antiwear hydraulic oil, have good wear resistance, also can be applicable in lubricating grease, automobile automatic drive liquid and the hydraulic efficiency oil simultaneously.
Description of drawings
Fig. 1 is the infrared spectrogram of the inferior phosphinylidyne hydrazine of the n-octyl dodecyl ester of example 1 preparation.Infrared spectrogram to the inferior phosphinylidyne hydrazine of n-octyl dodecyl is made a concrete analysis of, wherein, and 991.6,1062.6 and 1202.7cm
-1Be that (the absorption peak scope of P-O-C is at 970～1150cm for the absorption peak of P-O-C and P-N
-1, the absorption peak scope of P-N is at 930～1110cm
-1), 1633.4cm
-1Be NH
2The formation vibration peak.2924.8,2851.5,1464.0,1379.2cm
-1Be-CH
3Absorption peak, 3338.0cm
-1Be the NH stretching vibration peak, 724.6cm
-1Be NH
2Absorption peak.By Infrared spectroscopy, can roughly determine the structure of the inferior phosphinylidyne hydrazine of n-octyl dodecyl ester.
Fig. 2 is the infrared spectrogram of the inferior phosphinylidyne hydrazine of the di-n-octyl ester of example 2 preparations.Among Fig. 2, the infrared spectrogram shape basically identical of the inferior phosphinylidyne hydrazine of the n-octyl dodecyl ester among the inferior phosphinylidyne hydrazine ester of di-n-octyl and Fig. 1 shows that the two is same compounds.
Fig. 3 is the infrared spectrogram of the inferior phosphinylidyne amino dodecane of the di-n-butyl ester of example 3 preparations.Among Fig. 3,1066.4,978.3 and 1030.2cm
-1Be that (the absorption peak scope of P-O-C is at 970～1150cm for the absorption peak of P-O-C and P-N
-1, the absorption peak scope of P-N is at 930～1110cm
-1), 1640.9cm
-1Be NH
2The formation vibration peak.2958.4,2873.2,1465.5 and 1379.8cm
-1Be-CH
3Absorption peak, 725.9cm
-1Be NH
2Absorption peak.By Infrared spectroscopy, can roughly determine the structure of the inferior phosphinylidyne amino dodecane of di-n-butyl ester.
Fig. 4 is the infrared spectrogram of the inferior phosphinylidyne hexahydroaniline of the normal-butyl n-octyl ester of example 4 preparations.Among Fig. 4,1050.4,978.7cm
-1Be that (the absorption peak scope of P-O-C is at 970～1150cm for the absorption peak of P-O-C and P-N
-1, the absorption peak scope of P-N is at 930～1110cm
-1), 1640.7cm
-1Be NH
2The formation vibration peak.2923.9,2854.0,1467.7 and 1371.1cm
-1Be-CH
3Absorption peak, 3331.5,2958.0 and 721.8cm
-1Be NH
2Absorption peak.By Infrared spectroscopy, can roughly determine the structure of the inferior phosphinylidyne hexahydroaniline of normal-butyl n-octyl ester.
Fig. 5 is the infrared spectrogram of the inferior phosphinylidyne diboronic ester of di-n-octyl of example 5 preparations.Among Fig. 5,1028.0 and 978.1cm
-1Be that (the absorption peak scope of P-O-C is at 970～1150cm for the absorption peak of P-O-C and P-N
-1, the absorption peak scope of P-N is at 930～1110cm
-1), 1615.8cm
-1Be NH
2The formation vibration peak.2959.5,2860.3,1463.0 and 1378.4cm
-1Be-CH
3Absorption peak, 3188.7,771.6 and 728.8cm
-1Be NH
2Absorption peak.By Infrared spectroscopy, can roughly determine the structure of the inferior phosphinylidyne diboronic ester of di-n-octyl.
Embodiment
The invention will be further described below by example, but following example do not limit the invention, and any change that does not exceed design of the present invention and scope all within the scope of the present invention.Spirit of the present invention and protection domain are listed among the claim.
The present invention is about lubricating oil supporting capacity and abrasion resistance pipette method (tetra-ball machine test method, GB/T 3142 and SH/T0189): the supporting capacity of lubricating oil is with last non seizure load P
BValue representation, wear resistance is represented with wear scar diameter.The supporting capacity of lubricating oil is good more, P
BBe worth big more; Wear resistance is good, and wear scar diameter is little.
Example 1
Get the 0.3mol phosphorus trichloride, 200ml toluene, under 0 ± 10 ℃ of temperature, stir adding 0.3mol n-Octanol, stir adding 0.3mo1 lauryl alcohol and 0.6mol triethylamine after 3 hours, add the 0.33mol hydrazine hydrate after stirring in 3 hours, reacted 1 hour every being warmed up to after 2 hours under 110 ± 5 ℃ of temperature, washing, drying is purified, gained water white transparency thick liquid is the inferior phosphinylidyne hydrazine of a wear preventive additive n-octyl dodecyl ester, and code name is A1.A1 is joined in the N46 base oil by 0.50% (m/m), carry out the four-ball tester evaluation, the results are shown in Table 1; Join in the N46 base oil by 1.0% (m/m), carry out the four-ball tester evaluation, the results are shown in Table 2.
Example 2
Get the 0.3mol phosphorus trichloride, the 200ml tetrahydrofuran (THF), under 0 ± 5 ℃ of temperature, stir adding 0.3mol n-Octanol, stir adding 0.3mol n-Octanol and 0.6mol triethylamine after 3 hours, add the 0.33mol hydrazine hydrate after stirring in 3 hours, reacted 1 hour every being warmed up to after 2 hours under 110 ± 5 ℃ of temperature, washing, drying is purified, the gained colourless transparent liquid is the inferior phosphinylidyne hydrazine of a wear preventive additive di-n-octyl ester, and code name is A2.A2 is joined in the N46 base oil by 0.50% (m/m), carry out the four-ball tester evaluation, the results are shown in Table 1; Join in the N46 base oil by 1.0% (m/m), carry out the four-ball tester evaluation, the results are shown in Table 2.
Example 3
Get the 0.3mol phosphorus trichloride, the 150ml ether stirs adding 0.3mol propyl carbinol under 0 ± 10 ℃ of temperature, stirs after 3 hours to add 0.3mol propyl carbinol and 0.4mol triethylamine, after 3 hours, separates, and boils off solvent, obtains the inferior phosphoryl chloride of intermediate.Inferior phosphoryl chloride, 150ml toluene are inserted there-necked flask, add the 0.3mol primene JM-T (Primene81-R), stir and add the 0.3mol triethylamine, reacted 1 hour every being warmed up to after 2 hours under 110 ± 5 ℃ of temperature, washing, drying is purified, the gained yellow transparent liquid is the inferior phosphinylidyne amino dodecane of a wear preventive additive di-n-butyl ester, and code name is A3.A3 is joined in the N46 base oil by 0.50% (m/m), carry out the four-ball tester evaluation, the results are shown in Table 1; Join in the N46 base oil by 1.0% (m/m), carry out the four-ball tester evaluation, the results are shown in Table 2.
Example 4
Get the 0.3mol phosphorus trichloride, the 150ml ether stirs adding 0.3mol propyl carbinol under 0 ± 5 ℃ of temperature, stirs after 3 hours to add 0.3mol n-Octanol and 0.4mol triethylamine, after 3 hours, separates, and boils off solvent, obtains the inferior phosphoryl chloride of intermediate.Inferior phosphoryl chloride, 150ml toluene are inserted there-necked flask; add the 0.3mol hexahydroaniline; stir and add the 0.3mol triethylamine; reacted 1 hour every being warmed up to after 2 hours under 110 ± 5 ℃ of temperature; washing, drying is purified; gained yellow transparent thick liquid is the inferior phosphinylidyne hexahydroaniline of a wear preventive additive normal-butyl n-octyl ester, and code name is A4.A4 is joined in the N46 base oil by 0.50% (m/m), carry out the four-ball tester evaluation, the results are shown in Table 1; Join in the N46 base oil by 1.0% (m/m), carry out the four-ball tester evaluation, the results are shown in Table 2.
Example 5
Get the 0.3mol phosphorus trichloride, 200ml toluene, under 0 ± 5 ℃ of temperature, stir adding 0.3mol n-Octanol, stir adding 0.3mol n-Octanol and 0.6mol triethylamine after 3 hours, add 0.3mol aniline after stirring in 3 hours, reacted 1 hour every being warmed up to after 2 hours under 110 ± 5 ℃ of temperature, washing, drying is purified, the brown transparent liquid of gained is the inferior phosphinylidyne diboronic ester of wear preventive additive di-n-octyl, and code name is A5.A5 is joined in the N46 base oil by 0.50% (m/m), carry out the four-ball tester evaluation, the results are shown in Table 1; Join in the N46 base oil by 1.0% (m/m), carry out the four-ball tester evaluation, the results are shown in Table 2.
Table 1 adds the four-ball tester evaluation result of 0.5w% anti-wear agent
| Oil sample * | Anti-wear agent | P BValue (N) | Wear scar diameter (mm) |
| The N46 base oil | A1 | 1176 | 0.44 |
| The N46 base oil | A2 | 980 | 0.42 |
| The N46 base oil | A3 | 931 | 0.45 |
| The N46 base oil | A4 | 931 | 0.39 |
| The N46 base oil | A5 | 980 | 0.49 |
| The N46 base oil | T306 | 637 | 0.67 |
| The N46 base oil | T307 | 980 | 0.49 |
*The condition of measuring wear scar diameter is load 392N, rotating speed 1200rpm, time 60min.
Table 2 adds 1.0w% anti-wear agent four-ball tester evaluation result
| Oil sample * | Anti-wear agent | P BValue (N) | Wear scar diameter (mm) |
| The N46 base oil | A1 | 1421 | 0.44 |
| The N46 base oil | A2 | 1078 | 0.44 |
| The N46 base oil | A3 | 980 | 0.46 |
| The N46 base oil | A4 | 980 | 0.40 |
| The N46 base oil | A5 | 1127 | 0.47 |
| The N46 base oil | T306 | 637 | 0.62 |
| The N46 base oil | T307 | 1078 | 0.48 |
*The condition of measuring wear scar diameter is load 392N, rotating speed 1200rpm, time 60min.
Claims (8)
1. phosphoramidite extreme pressure anti-wear additives has following formula:
R, R ' are C identical or inequality in the formula
1～C
20The alkyl of straight or branched, cycloalkyl, aryl or aralkyl, R " is amino or C
1～C
18Alkyl, aryl, aralkyl or the cycloalkyl of straight or branched.
2. according to the described extreme pressure anti-wear additives of claim 1, it is characterized in that R, R ' are C
4～C
16Alkyl, R " is amino or C
4～C
16Alkyl, phenyl or cycloalkyl.
3. the preparation method of the described extreme pressure anti-wear additives of claim 1, comprising: (1) makes phosphorus trichloride and C in the presence of organic solvent
1～C
20Alcohols reacts down at-20 ℃～20 ℃ and generates the inferior phosphinylidyne dichloro of intermediate; (2) add C
1～C
20Alcohols is kept-20 ℃～20 ℃ reactions to generating the inferior phosphoryl chloride of intermediate; (3) add hydrazine hydrate or C
4～C
18Organic amine is warming up to 80 ℃～140 ℃ reactions to generating phosphoramidite or phosphinylidyne hydrazine ester.
4. according to the described preparation method of claim 3, it is characterized in that add acid binding agent in step (2) and (3), add-on is 1～4 times of phosphorus trichloride mole number.
5. according to the described preparation method of claim 4, it is characterized in that said acid binding agent is organic bases or mineral alkali.
6. according to the described preparation method of claim 5, it is characterized in that said acid binding agent is one or more in sodium hydroxide, Tetrabutyl amonium bromide, the triethylamine.
7. according to the described preparation method of claim 3, it is characterized in that said organic solvent is one or more in ether, tetrahydrofuran (THF), the toluene.
8. the application of the described extreme pressure anti-wear additives of claim 1 in lubricating oil, lubricating grease, the consumption of extreme pressure anti-wear additives in lubricating oil, lubricating grease is 0.1～3.0w%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100657377A CN100487093C (en) | 2006-03-15 | 2006-03-15 | Phosphamide ester extreme pressure anti-wear additives and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100657377A CN100487093C (en) | 2006-03-15 | 2006-03-15 | Phosphamide ester extreme pressure anti-wear additives and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101037637A CN101037637A (en) | 2007-09-19 |
| CN100487093C true CN100487093C (en) | 2009-05-13 |
Family
ID=38888814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100657377A Active CN100487093C (en) | 2006-03-15 | 2006-03-15 | Phosphamide ester extreme pressure anti-wear additives and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100487093C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109370739B (en) * | 2018-12-05 | 2021-08-03 | 武汉轻工大学 | Non-classical tribology isostere with hydrazide group as phosphate group |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5919967A (en) * | 1997-04-11 | 1999-07-06 | Epix Medical, Inc. | Process for synthesizing phosphodiesters |
-
2006
- 2006-03-15 CN CNB2006100657377A patent/CN100487093C/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5919967A (en) * | 1997-04-11 | 1999-07-06 | Epix Medical, Inc. | Process for synthesizing phosphodiesters |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101037637A (en) | 2007-09-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102504913B (en) | Extreme pressure antiwear additive and preparation method and application thereof | |
| CN100487094C (en) | Phosphamide ester extreme pressure anti-wear additives and preparation and application thereof | |
| CN101993766B (en) | Total synthesis shock absorber oil with high viscosity index | |
| CN101575548B (en) | Lubricating grease special for constant-speed universal joint and preparing method thereof | |
| CN102834493B (en) | Lubricant additive and lubricant composition containing lubricant additive | |
| KR101252867B1 (en) | Additive for lubricant | |
| CN100567335C (en) | Single site palladium catalyst complexes | |
| CN101830865B (en) | Hydroxyl-containing thiadiazole derivate as well as preparation method and application thereof | |
| EP1364955B1 (en) | Phosphorothionates | |
| CN100487093C (en) | Phosphamide ester extreme pressure anti-wear additives and preparation and application thereof | |
| CN103509057A (en) | Oil-soluble molybdenum dialkyldithiocarbamate additive preparation method | |
| CN102260572B (en) | P-N extreme pressure and anti-wear additive and preparation method thereof | |
| WO2018139326A1 (en) | Alkanolamine, friction-reducing agent, and lubricating oil composition | |
| CN101235334A (en) | 2-alkylxanthate-N-substituted acetanilide used for lubricating oil additive and preparation method thereof | |
| Iyer et al. | The effects of sulfur substitution for the nucleophile and bridging oxygen atoms in reactions of hydroxyalkyl phosphate esters | |
| CN106543099A (en) | A kind of Biodegradable lube oil additive 2,5 dialkyl acetamides, 1,3,4 thiadiazoles and preparation method thereof | |
| WO2015026566A1 (en) | Lubricant having improved antiwear properties | |
| CN104817594A (en) | Molybdenum containing borate derivative, preparation method and application thereof | |
| CN102887918A (en) | Preparation and application of dialkyl dithiophosphate hydroxyl derivative and boric acid ester thereof | |
| CN100355871C (en) | Prepn of nitrogen sulfate phosphate type phosphorus-containing agent | |
| CN103183626B (en) | Dithiocarbamic acid-containing hydroxyl derivative, boric acid ester of dithiocarbamic acid-containing hydroxyl derivative, and preparation method and application thereof | |
| WO1999018112A1 (en) | Sulfur-containing organophosphorus compounds | |
| CN111057102B (en) | Organophosphorus compounds, preparation method and application thereof | |
| JP2007070348A (en) | Method for producing sulfur-containing phosphate compound | |
| CN104177405A (en) | Bis-phosphite amine salt, preparation method and application and lubricating oil composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |