CN102234557B - Zirconium-based lubricating grease and preparation method thereof - Google Patents
Zirconium-based lubricating grease and preparation method thereof Download PDFInfo
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- CN102234557B CN102234557B CN 201010152752 CN201010152752A CN102234557B CN 102234557 B CN102234557 B CN 102234557B CN 201010152752 CN201010152752 CN 201010152752 CN 201010152752 A CN201010152752 A CN 201010152752A CN 102234557 B CN102234557 B CN 102234557B
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Abstract
The invention provides a zirconium-based lubricating grease and a preparation method thereof. On the basis of the weight of the lubricating grease, the lubricating grease comprises 50 to 95 percent of basic oil, 5 to 50 percent of zirconium-based thickening agent and the balance of additive, wherein the zirconium-based thickening agent is zirconium sceps prepared by reacting a mixture of monocarboxylic acid and dicarboxylic acid with ZrO(OH)2.xH2O. The zirconium-based lubricating grease has high colloid stability, mechanical stability and abrasion resistance to the extreme pressure, and can be used for lubricating high-speed heavy-load bearings for oil field drilling and the like.
Description
Technical field
The invention belongs to lubricant, is exactly lubricating grease.
Background technology
Zirconium belongs to IVB family as a kind of transition metal, is positioned at for the 5th cycle.Zirconium-containing compound has good lubrication, is often used as slip additive, as CN101113382 and JP1973038444, the oxide compound of zirconium has been improved abradability as lubricant additive; WO2007143414 and US20060063682 have introduced zirconium tetrafluoride and can be used as wear reducing additive and become one of component of lubricant; US20060254823 finds that the lubricant that contains the 2 ethyl hexanoic acid zirconates shows good anti-heavy loading and abrasion resistance; US20050043189 finds that fluozirconate such as fluorine zirconic acid aluminium can be used as oxidation retarder and is used in lubricant; DE102004021812 can improve abrasion resistance inside finding the inorganic salt such as zirconium carbonate, sulfonic acid zirconium or zirconium phosphate are joined lubricating grease.
As the patent that viscosifying agent prepares the zirconium base grease, US4189387 is arranged with zirconates, viscosifying agent is to be made by organic Hypophosporous Acid, 50 or monocarboxylic acid and zirconium hydroxide reaction, and prepared fat has extreme pressure property preferably, has used C in embodiment
10F
21COOH monoprotic acid.
Summary of the invention
The present invention aims to provide a kind of zirconium base grease, and this lubricating grease has good colloid stability, but also has the good characteristics such as extreme pressure anti-wear.
The present invention also provides the preparation method of above-mentioned zirconium base grease.
Lubricating grease provided by the invention take lubricating grease weight as benchmark, comprises: base oil 50～95%, and preferred 65～92%, more preferably 75～90%, zirconium base viscosifying agent 5～50%, preferred 8～35%, more preferably 10～25%, the additive surplus.
100 ℃ of viscosity of described base oil are 2～150mm
2/ s, preferred 5～100mm
2/ s is preferably 8～50mm
2/ s can be mineral oil, ester class oil, synthetic hydrocarbon (as poly alpha olefine synthetic oil etc.) or plant wet goods.
Described zirconium base viscosifying agent is the zirconium soap that is formed by the reaction of the wet hydrogen zirconium white of the mixture of monocarboxylic acid and di-carboxylic acid and new system.
The wet hydrogen zirconium white of described new system is typically expressed as ZrO (OH)
2XH
2O, wherein x represents the number of crystal water, it can pass through ZrOX
2GH
2O (X is F, Cl, Br or I) or ZrO (NO
3)
22H
2O etc. obtain with alkali reaction, and alkali wherein can be NaOH, KOH, strong aqua etc., preferred ZrOCl
28H
2O and NaOH reaction.
Described monocarboxylic acid structural formula is R
1-(CHOH)-R
2-COOH or R
3-COOH, wherein R
1And R
3Can be the alkyl or aryl of H, alkyl, thiazolinyl, alkynyl, aryl, fluoro or perfluoro, R
2Can be the alkyl or aryl of alkyl, thiazolinyl, alkynyl, aryl, fluoro or perfluoro.Monocarboxylic molecular weight is 170～1050, and is preferred 220～330, can be selected from one or more in lauric acid, oleic acid, stearic acid, 12-oxystearic acid etc., preferred 12-oxystearic acid.
Described di-carboxylic acid structural formula is (HOOC)-R
4-(COOH), R wherein
4Can be the alkyl or aryl of alkyl, thiazolinyl, alkynyl, aryl, fluoro or perfluoro.The molecular weight of di-carboxylic acid is 90～600, preferred 170～220, can be selected from one or more in oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, bay diacid etc., one or more in preferred hexanodioic acid, nonane diacid, sebacic acid.
Di-carboxylic acid and monocarboxylic mol ratio are 0.2～1.2: 1, preferred 0.5～1: 1.
The contained H of di-carboxylic acid and monocarboxylic acid in theory
+The mole number sum equal the wet hydrogen zirconium white ZrO (OH) of new system
2XH
2The contained OH of O
-Mole number, but wet hydrogen zirconium white ZrO (OH)
2XH
2The mole number of O can excessive 1～5%.
Can contain or not contain additive in lubricating grease of the present invention.Described additive can be one or more in oxidation inhibitor, anti-wear agent, rust-preventive agent, extreme pressure agent etc., can also be other additive.
Preparation of greases method of the present invention comprises: at first part base oil (account for whole base oil weight 30～60%) is mixed at normal temperatures with monocarboxylic acid and di-carboxylic acid, be warming up to 60～90 ℃, add the zirconium hydroxide precipitation ZrO (OH) of new system
2XH
2O, the draining saponification is warmed up to 160～210 ℃, adds the surplus base oil, and cooling adds additive in case of necessity, and in 80～120 ℃ of 2 grinding homogenizing, obtains the zirconium base grease.
Zirconium base grease provided by the invention has good colloid stability, mechanical stability and extreme pressure anti-wear.This lubricating grease can be used for the bearing lubrication such as high speed, heavy loading running, oil drilling.
Embodiment
Embodiment 1
48g ZrOCl
28H
2O is dissolved in 250g water, 150g is contained the aqueous solution of 12g NaOH, slowly adds above-mentioned ZrOCl
2The aqueous solution in, rapid stirring has a large amount of white precipitates to occur immediately, filtration is precipitated, precipitation is washed rear standby with massive laundering.
With 280g 500SN oil (100 ℃ of viscosity 11mm
2/ s), 45g 12-oxystearic acid and 15g sebacic acid add in normal oleosterin still, stir, become the homogeneous system after being warmed up to 90 ℃, slowly add the precipitation of above-mentioned new system wherein this moment, is warming up to 105 ℃ of draining saponification 2 hours, after be warming up to 205 ℃, add 180g quenching oil 500SN, stir cooling, and the normal temperature grinding, the zirconium base grease obtained.Grease composition: base oil 86%, viscosifying agent 14%, wherein diprotic acid and monoprotic acid mol ratio are 0.5: 1.Each physicochemical property of gained fat sees following table for details.
Embodiment 2
48g ZrOCl
28H
2O is dissolved in 250g water, 150g is contained the aqueous solution of 17g KOH, slowly adds above-mentioned ZrOCl
2The aqueous solution in, rapid stirring has a large amount of white precipitates to occur immediately, filtration is precipitated, precipitation is washed rear standby with massive laundering.
With 500g 150BS (100 ℃ of viscosity 31mm
2/ s), 34.6g 12-oxystearic acid and 17.4g nonane diacid add in normal oleosterin still, stir, become the homogeneous system after being warmed up to 90 ℃, slowly add the precipitation of above-mentioned new system wherein this moment, is warming up to 105 ℃ of draining saponification 2 hours, after be warming up to 205 ℃, add 250g quenching oil 150BS, stir cooling, and the normal temperature grinding, the zirconium base grease obtained.Grease composition: base oil 92%, viscosifying agent 8%, wherein diprotic acid and monoprotic acid mol ratio are 0.8: 1.Each physicochemical property of gained fat sees following table for details.
Embodiment 3
48g ZrOCl
28H
2O is dissolved in 250g water, and 50g is contained 12g NH
3H
2The concentrated ammonia solution of O slowly adds above-mentioned ZrOCl
2The aqueous solution in, rapid stirring has a large amount of white precipitates to occur immediately, filtration is precipitated, precipitation is washed rear standby with massive laundering.
With 280g poly ﹠ Alpha ,-olefin oil PAO 10 (100 ℃ of viscosity 11mm
2/ s), 28g stearic acid and 20g sebacic acid add in normal oleosterin still, stir, become the homogeneous system after being warmed up to 90 ℃, slowly add the precipitation of above-mentioned new system wherein this moment, is warming up to 105 ℃ of draining saponification 2 hours, after be warming up to 205 ℃, add 180g quenching oil 500SN, stir cooling, and the normal temperature grinding, the zirconium base grease obtained.Grease composition: base oil 88%, viscosifying agent 12%, wherein diprotic acid and monoprotic acid mol ratio are 1: 1.Each physicochemical property of gained fat sees following table for details.
Embodiment 4
48g ZrOCl
28H
2O is dissolved in 250g water, 150g is contained the aqueous solution of 12g NaOH, slowly adds above-mentioned ZrOCl
2The aqueous solution in, rapid stirring has a large amount of white precipitates to occur immediately, filtration is precipitated, precipitation is washed rear standby with massive laundering.
With 200g poly ﹠ Alpha ,-olefin oil PAO 40 (100 ℃ of viscosity 41mm
2/ s), 30g 12-oxystearic acid and 20g sebacic acid add in normal oleosterin still, stir, become the homogeneous system after being warmed up to 90 ℃, slowly add the precipitation of above-mentioned new system wherein this moment, is warming up to 105 ℃ of draining saponification 2 hours, after be warming up to 205 ℃, add 100g quenching oil 500SN, stir cooling, and the normal temperature grinding, the zirconium base grease obtained.Grease composition: base oil 82%, viscosifying agent 18%, wherein diprotic acid and monoprotic acid mol ratio are 1: 1.Each physicochemical property of gained fat sees following table for details.
Comparative Examples 1
48g ZrOCl
28H
2O is dissolved in 250g water, 150g is contained the aqueous solution of 12g NaOH, slowly adds above-mentioned ZrOCl
2The aqueous solution in, rapid stirring has a large amount of white precipitates to occur immediately, filtration is precipitated, precipitation is washed rear standby with massive laundering.
With 280g 500SN oil (100 ℃ of viscosity 11mm
2/ s), 90g 12-oxystearic acid adds in normal oleosterin still, stir, become the homogeneous system after being warmed up to 90 ℃, slowly add the precipitation of above-mentioned new system wherein this moment, is warming up to 105 ℃ of draining saponification 2 hours, after be warming up to 205 ℃, add 180g quenching oil 500SN, stir cooling, and the normal temperature grinding, the zirconium base grease obtained.Grease composition: base oil 81%, viscosifying agent 19%.Each physicochemical property of gained fat sees following table for details.
Comparative Examples 2
With 280g 500SN oil (100 ℃ of viscosity 11mm
2/ s), 45g 12-oxystearic acid and 15g sebacic acid add in normal oleosterin still, stirs, becoming the homogeneous system after being warmed up to 90 ℃, be dissolved with 12.3gLiOHH with 50g this moment
2The aqueous solution of O slowly adds wherein, is warming up to 105 ℃ of draining saponification 2 hours, after be warming up to 205 ℃, add 180g quenching oil 500SN, stir cooling, and normal temperature grinds, obtain the zirconium base grease.Grease composition: base oil 88%, viscosifying agent 12%, wherein diprotic acid and monoprotic acid mol ratio are 0.5: 1.Each physicochemical property of gained fat sees following table for details.
Table 1 lubricating grease physicochemical property
As can be seen from Table 1, the lubricating grease of the inventive method preparation has good colloid stability and excellent extreme pressure and antiwear behavior.For Comparative Examples 1, all better by lubricating grease various aspects of performance of the present invention.For Comparative Examples 2, at P
DIn the situation that value and grinding defect diameter approach, press the P of the lubricating grease of the inventive method preparation
BValue is well a lot, and colloid stability simultaneously is better.Can add on this basis various additives to obtain the lubricating grease of better performance.
Claims (10)
1. zirconium base grease take lubricating grease weight as benchmark, comprising: base oil 50～95%, and zirconium base viscosifying agent 5～50%, the additive surplus, described zirconium base viscosifying agent is by the mixture of monocarboxylic acid and di-carboxylic acid and ZrO (OH)
2XH
2The zirconium soap that the O reaction generates, described base oil are selected from one or more in mineral oil, ester class oil, poly alpha olefine synthetic oil or vegetables oil, and described monocarboxylic acid structural formula is R
1-(CHOH)-R
2-COOH or R
3-COOH, wherein R
1And R
3Be H, alkyl, thiazolinyl, alkynyl or aryl, R
2Be alkyl, thiazolinyl, alkynyl or aryl, described di-carboxylic acid structural formula is (HOOC)-R
4-(COOH), R wherein
4Be alkyl, thiazolinyl, alkynyl or aryl.
2. according to lubricating grease claimed in claim 1, wherein, take lubricating grease weight as benchmark, comprising: base oil 65～92%, zirconium base viscosifying agent 8～35%, additive surplus.
3. according to lubricating grease claimed in claim 1, wherein, take lubricating grease weight as benchmark, comprising: base oil 75～90%, zirconium base viscosifying agent 10～25%, additive surplus.
4. according to lubricating grease claimed in claim 1,100 ℃ of viscosity of described base oil are 2～150mm
2/ s.
5. according to lubricating grease claimed in claim 1,100 ℃ of viscosity of described base oil are 5～100mm
2/ s.
6. according to lubricating grease claimed in claim 1,100 ℃ of viscosity of described base oil are 8～50mm
2/ s.
7. according to lubricating grease claimed in claim 1, wherein, monocarboxylic molecular weight is 170～1050, and the molecular weight of di-carboxylic acid is 90～600, and di-carboxylic acid is 0.2～1.2: 1 with the ratio of monocarboxylic amount of substance.
8. according to lubricating grease claimed in claim 1, wherein, monocarboxylic molecular weight is 220～500, and the molecular weight of di-carboxylic acid is 170～300, and di-carboxylic acid is 0.5～1: 1 with the ratio of monocarboxylic amount of substance.
9. according to lubricating grease claimed in claim 1, wherein, monocarboxylic acid is selected from one or more in lauric acid, oleic acid, stearic acid, 12-oxystearic acid, and di-carboxylic acid is selected from one or more in oxalic acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, bay diacid.
10. the described preparation of greases method of one of claim 1～9, comprising: the part base oil is mixed at normal temperatures with monocarboxylic acid and di-carboxylic acid, be warming up to 60～90 ℃, add the zirconium hydroxide precipitation ZrO (OH) of new system
2XH
2O, the draining saponification is warmed up to 160～210 ℃, adds the surplus base oil, and cooling adds additive, and in 80～120 ℃ of grinding homogenizing, obtains the zirconium base grease.
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|---|---|---|---|
| CN 201010152752 CN102234557B (en) | 2010-04-22 | 2010-04-22 | Zirconium-based lubricating grease and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010152752 CN102234557B (en) | 2010-04-22 | 2010-04-22 | Zirconium-based lubricating grease and preparation method thereof |
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|---|---|
| CN102234557A CN102234557A (en) | 2011-11-09 |
| CN102234557B true CN102234557B (en) | 2013-06-05 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104513690B (en) * | 2013-09-30 | 2017-04-26 | 中国石油化工股份有限公司 | Composite calcium-zirconium-based lubricating grease and preparation method thereof |
| CN104513689B (en) * | 2013-09-30 | 2017-04-26 | 中国石油化工股份有限公司 | Calcium-zirconium-based lubricating grease and preparation method thereof |
| CN111100722B (en) * | 2018-10-25 | 2022-10-21 | 中国石油化工股份有限公司 | Composite calcium-based lubricating grease and preparation method thereof |
| CN111100733B (en) * | 2018-10-25 | 2022-10-21 | 中国石油化工股份有限公司 | Polymer-based lubricating grease and preparation method thereof |
| CN111100731B (en) * | 2018-10-25 | 2022-10-21 | 中国石油化工股份有限公司 | Lubricating grease and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4189387A (en) * | 1978-08-31 | 1980-02-19 | King James P | Lubricant compositions based on zirconium polymers |
| CN1055384A (en) * | 1990-11-02 | 1991-10-16 | 天津汉沽石油化学厂 | Composite lithium-based lubricating grease composition |
-
2010
- 2010-04-22 CN CN 201010152752 patent/CN102234557B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4189387A (en) * | 1978-08-31 | 1980-02-19 | King James P | Lubricant compositions based on zirconium polymers |
| CN1055384A (en) * | 1990-11-02 | 1991-10-16 | 天津汉沽石油化学厂 | Composite lithium-based lubricating grease composition |
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