CN115477968B - Low-oil-content and wear-resistant fluorine grease and preparation method thereof - Google Patents
Low-oil-content and wear-resistant fluorine grease and preparation method thereof Download PDFInfo
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- CN115477968B CN115477968B CN202211259994.XA CN202211259994A CN115477968B CN 115477968 B CN115477968 B CN 115477968B CN 202211259994 A CN202211259994 A CN 202211259994A CN 115477968 B CN115477968 B CN 115477968B
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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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
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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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/10—Compounds containing silicon
- C10M2201/105—Silica
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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
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/06—Perfluoro polymers
- C10M2213/0606—Perfluoro polymers used as base material
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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
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/06—Perfluoro polymers
- C10M2213/062—Polytetrafluoroethylene [PTFE]
- C10M2213/0626—Polytetrafluoroethylene [PTFE] used as thickening agents
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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
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
- C10M2229/051—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing halogen
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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
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
- C10M2229/052—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing nitrogen
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- 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
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- 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
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
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- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention provides low-oil-fraction and wear-resistant fluorine grease and a preparation method thereof. The fluorine grease comprises the following components in percentage by weight: 50 to 80wt%, preferably 55 to 75wt% of perfluoropolyether base oil; 20 to 50wt percent of polytetrafluoroethylene thickening agent, preferably 25 to 40wt percent; 0-10wt% of a first additive; 0-10wt% of a second additive; and, the sum of the weight percentages of the first additive and the second additive is > 0.
Description
Technical Field
The invention relates to the technical field of fluorine-containing lubricating materials, in particular to low-oil-content and wear-resistant fluorine grease and a preparation method thereof.
Background
The hydrogen atoms in the molecule structure of the perfluoropolyether are completely replaced by fluorine atoms, so that the perfluoropolyether has excellent oxidation resistance; the C-O-C ether bond contained in the main chain of the perfluoropolyether structure endows the perfluoropolyether structure with good viscosity-temperature characteristics and low condensation point; the molecule chain of the perfluoropolyether contains a large number of C-F bonds with higher bond energy, so that the thermal decomposition temperature is higher and the evaporation loss is low. Therefore, the perfluoropolyether has wide market application value. However, perfluoropolyethers, because of their specific molecular structure, exhibit non-polarity, resulting in weak intermolecular forces and low surface tension, which is also a key factor in causing the perfluoropolyether base oil to migrate across the substrate surface. The climbing of perfluoropolyether base oils limits the thickness of the lubricant film, thus affecting the antiwear properties of such greases, as well as affecting the colloidal stability of the fluorochemical greases.
Chinese patent application CN11110724B discloses a perfluoropolyether grease with good colloid stability and a preparation method thereof, wherein the colloid modifier selected by the grease provided by the patent application is a fluorine-containing soap base derivative, and the fluorine-containing soap base derivative is used as an additive to improve the colloid stability of the perfluoropolyether grease, but the research on the wear resistance of the grease is not involved. Chinese patent application CN103781886a discloses a perfluoropolyether-based grease in which fumed silica is selected for thickening the perfluoropolyether compound, i.e. the fumed silica serves as a thickening agent; the effect of fumed silica on the noise and kinetic properties of perfluoropolyether greases was studied in this patent application, but the effect on the colloidal stability of the perfluoropolyether greases was unknown.
How to effectively improve the wear resistance of the fluorine grease based on the perfluoropolyether base oil, reduce the oil distribution, improve the colloid stability of the fluorine grease, so as to better meet the performance requirements of special working conditions such as high temperature, high rotating speed and the like, is one of the technical difficulties to be broken through by the technicians in the field.
Disclosure of Invention
Based on the technical scheme provided by the invention, the low-oil-content and wear-resistant fluorine grease can improve the wear resistance of the fluorine grease and reduce the oil content, and has good colloid stability.
The invention provides the following technical scheme for achieving the purpose:
the invention provides low-oil-content and wear-resistant fluorine grease, which comprises the following components in percentage by weight: 50 to 80wt%, preferably 55 to 75wt% of perfluoropolyether base oil; 20 to 50wt percent of polytetrafluoroethylene thickening agent, preferably 25 to 40wt percent; 0 to 10wt% (preferably 0.1 to 10 wt%) of a first additive; 0 to 10wt% (preferably 0.1 to 10 wt%) of a second additive; and, the sum of the weight percentages of the first additive and the second additive is > 0; the first additive is selected from nano inorganic powder; the second additive is selected from the group consisting of compounds of the following structural formula (III):
wherein R in the structural formula (III) F Is CF (CF) 3 —O—[(CF 3 )CFCF 2 O] x —CF 2 -or CF 3 —O—[CF 2 CF 2 O] y —CF 2 -wherein x = 18-25 and y = 36-49; r is R S Is- (CH) 2 ) 3 Si(OCH 3 ) 3 、—(CH 2 ) 3 Si(OCH 2 CH 3 ) 3 Or- (CH) 2 ) 2 NH(CH 2 ) 3 Si(OCH 3 ) 3 。
The perfluoropolyether base oil adopts one or more of perfluoropolyethers of the following structural formulas (I) and (II);
wherein the average molecular weight of the structural formula (I) and the structural formula (II) is 1000-20000, m/n=20-50, and p/q=0.5-2 respectively.
The present inventors have found that a low-oil-content and excellent antiwear performance of a fluorine grease can be obtained by incorporating inorganic nano-powder as a first additive and/or a compound having a specific structural formula (III) as a second additive in a specific ratio in a system combined with polytetrafluoroethylene thickener in a specific ratio using perfluoropolyether of the specific molecular weight range of the above-described specific structural formula (I) and structural formula (II) as a perfluoropolyether base oil, and not incorporating the above-described first additive and second additive. When the first additive is introduced alone in the formulation of the present invention, there is a lower oil split than when the second additive is introduced alone; when the second additive is independently introduced into the formula system, the anti-wear performance is superior to that of the first additive; when the first additive and the second additive are simultaneously introduced into the formula system, compared with the independent introduction of the first additive or the second additive, the oil distribution amount can be further obviously reduced, the wear resistance can be improved, and the oil distribution amount and the wear resistance of the fluorine grease can be synergistically improved.
In the specific formula system, the inorganic nano powder is introduced to play a role of a colloid stabilizer, so that the oil distribution amount can be remarkably reduced; however, in the conventional art of fluorocarbon grease formulations, the effect of incorporating inorganic powders is often limited to thickening and does not provide a significant reduction in grease split.
In a preferred embodiment, in the fluorine grease of the present invention, the first additive is selected from one or more of nano silica, hydrophobic white carbon black, nano silicon nitride, nano silicon carbide and nano molybdenum silicide; by adopting the nano inorganic powder as the first additive, the invention can play a good role in colloid stabilization in the formula system, can improve the colloid stability of the fluorine grease, can obviously reduce the oil distribution amount and inhibit the climbing of the fluorine oil.
The compound of the structural formula (III) is introduced into the fluorine grease as the second additive, so that the performance of the fluorine grease can be obviously improved, and particularly, excellent anti-wear performance improvement effect can be exerted. Preferably, the average molecular weight of the compound of the structural formula (III) is 3300-6100, and the adoption of the second additive with the preferable molecular weight is beneficial to remarkably improving the performance of the fluorine grease provided by the invention, in particular to remarkably improving the wear resistance.
In the present invention, the perfluoropolyether base oils of formula (I) and formula (II) can be prepared by existing processes (e.g., by photo-oxidative polymerization processes) or are commercially available.
In the formula system of the invention, the second additive of the structural formula (III) can be obtained by modifying perfluoro polyether acyl fluoride with a silane coupling agent. For example by distillation under reduced pressure, hydrolysis, esterification and modification of the silane coupling agent of the perfluoropolyether acyl fluoride. Exemplary, specific synthetic routes are shown in scheme (1) below:
wherein R is F And R in the structural formula (III) F Corresponding, rs corresponds to Rs in structural formula (III). The silane coupling agent is preferably at least one of 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane and N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane. Wherein the perfluoropolyether acyl fluorideCan be obtained commercially or can be prepared according to existing processes (e.g., photo-oxidative polymerization). As an example, conditions of reduced pressure distillation include, for example: the temperature is 120-220 ℃ and the pressure is 20-40 Pa; the conditions for hydrolysis include: the hydrolysis temperature is 35-45 ℃, for example, the hydrolysis time is 5h; the reaction conditions for esterification include: the esterification temperature is 50-100 ℃, for example, the esterification time is 10 hours; the conditions for reaction with the silane coupling agent include: the reaction temperature is 60-100 ℃, the reaction time is 6-10h, and the mass ratio of the perfluoropolyether methyl ester to the silane coupling agent obtained in the esterification process is 10/1-5/1.
In a preferred embodiment, the first additive is present in the fluorochemical grease according to the present invention in an amount of 0 to 5wt%, preferably 0.1 to 5wt%, the sum of the weight percentages of the first additive and the second additive being > 0. The inventor discovers that the addition amount of the preferable first additive is favorable for further reducing the oil distribution amount of the fluorine grease, improving the colloid stability of the fluorine grease and avoiding influencing the lubrication effect due to overlarge consistency of the grease.
In a more preferred embodiment, in the fluorine grease, the weight percentage of the first additive is 0.1-5wt% and the weight percentage of the second additive is 0.1-10wt%, so that the fluorine grease with better performance can be obtained, and the abrasion resistance can be obviously improved and the oil distribution amount can be obviously reduced simultaneously.
In a preferred embodiment, the average molecular weight of the perfluoropolyether base oil of the formulation of the present invention is 5200 to 16000. The formula system of the invention can obtain the fluorine grease with good antiwear performance and oil distribution without using perfluoro polyether base oil with higher molecular weight.
Preferably, the perfluoropolyether base oil used in the formulation of the present invention has an evaporation degree of less than 1.0% (200 ℃ C./24 h).
In some embodiments, the polytetrafluoroethylene thickener has a specific surface area of 0.5 to 10m 2 /g。
The invention also provides a preparation method of the fluorine grease, which comprises the following steps:
a) When the second additive is not added to the fluorine grease, the fluorine grease is prepared according to the following method one:
stirring and mixing the perfluoropolyether base oil, the polytetrafluoroethylene thickening agent and the first additive at the temperature of 30-60 ℃; grinding to obtain the fluorine grease;
b) When the second additive is added to the fluorine grease, the fluorine grease is prepared according to the following method II:
heating the perfluoropolyether base oil to 100-150 ℃, adding the second additive into the perfluoropolyether base oil, stirring and mixing the mixture, cooling the mixture to 50-90 ℃, and then adding the rest components into the mixture for stirring and mixing; and grinding to obtain the fluorine grease.
In some preferred embodiments, in the first method, the polytetrafluoroethylene thickener and the first additive are mixed at 40-50 ℃ with stirring; in the second method, the perfluoropolyether base oil is heated to 120-140 ℃, and then the second additive is added; the temperature of the cooling is 60-70 ℃.
In some embodiments, a) the method-specifically may be performed as follows:
1) Firstly, drying and pre-treating a polytetrafluoroethylene thickening agent;
2) Heating the perfluoropolyether base oil to 30-60 ℃ (preferably 40-50 ℃) and stirring;
3) Mixing the thickening agent in the step 1) with the first additive, stirring uniformly, slowly adding the mixture into the base oil in the step 2), and stirring to obtain a blend;
4) And 3) cooling the blend obtained in the step 3) to room temperature, and grinding for 3-5 times by using a three-roll mill to obtain the white grease.
b) The second method can be specifically carried out according to the following steps:
1) Firstly, drying and pre-treating a polytetrafluoroethylene thickening agent;
2) Heating the perfluoropolyether base oil to 100-150 ℃ (preferably 120-140 ℃) and stirring;
3) Dripping the second additive into the base oil in the step 2), stirring at 100-150 ℃ (preferably 120-140 ℃) to fully mix the second additive, then reducing the temperature to 50-90 ℃ (preferably 60-70 ℃) and keeping the temperature to obtain yellowish transparent oil;
4) Fully stirring and uniformly mixing the polytetrafluoroethylene thickening agent and other components (such as a first additive) possibly existing, slowly adding the mixture into the oil in the step 3), and stirring to obtain a blend;
5) And 4) cooling the blend obtained in the step 4) to room temperature, and grinding for 3-5 times by using a three-roll mill to obtain the white grease.
The technical scheme provided by the invention has the following beneficial effects:
the fluorine grease provided by the invention can be used for combining good antiwear performance and relatively low oil separation rate, and has good colloid stability. In the preferred embodiment, when the first additive and the second additive are simultaneously introduced into the formula system, compared with the independent introduction of the first additive or the second additive, the oil distribution amount can be further obviously reduced, the wear resistance can be improved, and the oil distribution amount and the wear resistance of the fluorine grease can be synergistically improved.
Detailed Description
In order that the invention may be readily understood, a further description of the invention will be provided with reference to the following examples. It should be understood that the following examples are only for better understanding of the present invention and are not meant to limit the present invention to the following examples.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The term "and/or" as may be used herein includes any and all combinations of one or more of the associated listed items.
The following description is given of the performance detection methods involved or likely to be involved in the examples or comparative examples as follows:
| test item | Test conditions | Unit (B) | Test standard |
| Appearance of | — | — | Visual inspection |
| 1/4 working cone penetration | — | 0.1mm | GB/T 269 |
| Oil separating device for steel mesh | 204℃，24h | ％ | NB/SH/T 0324 |
| Degree of evaporation | 200℃，24h | ％ | SH/T 0337 |
| Corrosion by corrosion | T2 copper sheet, x 24h at 100 DEG C | Stage | GB/T 7326 |
| Diameter of four ball mill spots | 75℃，60min，392N，1200rpm | mm | SH/T 0204 |
Some of the raw materials used in the following examples are described below:
the perfluoropolyether base oil of formula (I) (average molecular weight 5800, m/n=28), the perfluoropolyether base oil of formula (I) (average molecular weight 12790, m/n=27), the perfluoropolyether base oil of formula (I) (average molecular weight 16000, m/n=31), the perfluoropolyether base oil of formula (II) (average molecular weight 9920, p/q=0.5) and the perfluoropolyether base oil of formula (II) (average molecular weight 5200, p/q=2.0) are commercially available from chinese petrochemical lubricating oil limited.
Second additive S1 of formula (III) (average molecular weight 6100, R F Is CF (CF) 3 —O—[CF 2 CF 2 O] y —CF 2 —，y＝49；R S Is- (CH) 2 ) 2 NH(CH 2 ) 3 Si(OCH 3 ) 3 ) A second additive S2 of formula (III) (average molecular weight 4500, R) F Is CF (CF) 3 —O—[CF 2 CF 2 O] y —CF 2 —，y＝36；R S Is- (CH) 2 ) 3 Si(OCH 2 CH 3 ) 3 ) A second additive S3 of formula (III) (average molecular weight 4500, R) F Is CF (CF) 3 —O—[(CF 3 )CFCF 2 O] x —CF 2 —，x＝25；R S Is- (CH) 2 ) 3 Si(OCH 3 ) 3 ) And a second additive S4 of formula (III) (average molecular weight 3300, R) F Is CF (CF) 3 —O—[(CF 3 )CFCF 2 O] x —CF 2 —，x＝18；R S Is- (CH) 2 ) 2 NH(CH 2 ) 3 Si(OCH 3 ) 3 ) Corresponding perfluoropolyether acyl fluoride pass-through silaneThe coupling agent is modified, wherein the corresponding perfluoropolyether acyl fluoride used for preparing the second additive S1-S4 is commercially available (can be purchased from China petrochemical lubricating oil Co., ltd.), the silane coupling agent used for preparing the second additive S1 is N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane, the silane coupling agent used for preparing the second additive S2 is 3-aminopropyl triethoxysilane, the silane coupling agent used for preparing the second additive S3 is 3-aminopropyl trimethoxysilane, and the silane coupling agent used for preparing the second additive S4 is N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane. Taking the preparation of the second additive S1 as an example, the preparation process comprises the following steps: carrying out reduced pressure distillation on the perfluoropolyether acyl fluoride corresponding to the second additive S1 at 200-220 ℃ and 20 Pa; then hydrolysis is carried out, and the hydrolysis conditions comprise: the temperature is 40 ℃ and the time is 5 hours; after that, esterification was carried out according to the following procedure: the esterification temperature is 80 ℃ and the esterification time is 10 hours; then reacting with a silane coupling agent under the following reaction conditions: the reaction temperature is 80 ℃, the reaction time is 8 hours, and the mass ratio of the perfluoropolyether methyl ester to the silane coupling agent is 8/1; and then washing and suction filtering to obtain the second additive S1. The other second additives S2 to S4 can be obtained by referring to the preparation process of the second additive S1, and are mainly different in that the silane coupling agent used therein is changed, and will not be described again.
The nanometer silicon dioxide, the hydrophobic white carbon black and the nanometer silicon nitride are all commercial products (Hefei Xinwancheng environmental protection technology Co., ltd.).
Example 1 (addition of first additive only)
75g of branched perfluoropolyether base oil (average molecular weight is 5800, m/n=28) shown in the structural formula (I) is taken, heated to 40 ℃, and stirred at constant temperature for 0.5h; 23g of the dried and pretreated polytetrafluoroethylene thickener (specific surface area of 8.5 m) 2 (g), fully stirring and mixing with 2g of hydrophobic white carbon black (first additive), slowly adding into the perfluoropolyether base oil, and mechanically stirring for 1h to obtain a blend; and (5) after cooling to room temperature, grinding for 5 times by using a three-roller mill to obtain the finished grease.
Example 2 (addition of only the second additive)
55g of branched chain shown in structural formula (I) is takenPerfluoropolyether base oil (average molecular weight 12790, m/n=27), heated to 140 ℃, and thermostatted; 10g of a second additive S1 (average molecular weight 6100, R) of formula (III) F Is CF (CF) 3 —O—[CF 2 CF 2 O] y —CF 2 —，y＝49；R S Is- (CH) 2 ) 2 NH(CH 2 ) 3 Si(OCH 3 ) 3 ) Slowly adding the mixture into the perfluoropolyether base oil, mechanically stirring for 1h at 140 ℃, fully and uniformly mixing, and cooling to 70 ℃ to obtain yellowish transparent oil; 35g of the dried and pretreated polytetrafluoroethylene thickener (specific surface area of 4.5m was taken 2 Slowly adding the mixture into the perfluoropolyether base oil, and mechanically stirring for 1h to obtain a blend; and (3) after cooling to room temperature, grinding for 3 times by using a three-roller mill, and obtaining the finished grease.
Example 3 (addition of first and second additives)
65g of branched perfluoropolyether base oil (average molecular weight is 5800, m/n=28) shown in the structural formula (I) is taken and heated to 120 ℃ and kept at constant temperature; 10g of a second additive S2 of formula (III) (average molecular weight 4500, R) F Is CF (CF) 3 —O—[CF 2 CF 2 O] y —CF 2 —，y＝36；R S Is- (CH) 2 ) 3 Si(OCH 2 CH 3 ) 3 ) Slowly adding the mixture into the perfluoropolyether base oil, mechanically stirring at 120 ℃ for 0.5h, fully and uniformly mixing, and cooling to 60 ℃ to obtain yellowish transparent oil; 23g of the dried and pretreated polytetrafluoroethylene thickener (specific surface area of 8.5 m) 2 (g), fully stirring and mixing with 2g of hydrophobic white carbon black (first additive), slowly adding into the perfluoropolyether base oil, and mechanically stirring for 1h to obtain a blend; and (3) after cooling to room temperature, grinding for 5 times by using a three-roller mill, and obtaining the finished grease.
Example 4 (addition of only the second additive)
60g of linear perfluoropolyether base oil (average molecular weight 9920, p/q=0.5) of formula (II) was taken and heated to 120 ℃; taking 5g of a second additive S3 (average molecular weight is that of the formula (III)4500，R F Is CF (CF) 3 —O—[(CF 3 )CFCF 2 O] x —CF 2 —，x＝25；R S Is- (CH) 2 ) 3 Si(OCH 3 ) 3 ) Slowly adding the mixture into the perfluoropolyether base oil, mechanically stirring at 120 ℃ for 0.5h, fully and uniformly mixing, and cooling to 60 ℃ to obtain yellowish transparent oil; 35g of the dried and pretreated polytetrafluoroethylene thickener (specific surface area of 7.3m was taken 2 Slowly adding the mixture into the perfluoropolyether base oil, and mechanically stirring for 1h to obtain a blend; and (3) after cooling to room temperature, grinding for 3 times by using a three-roller mill, and obtaining the finished grease.
Example 5 (addition of first additive only)
70g of linear perfluoropolyether base oil (average molecular weight is 5200, p/q=2.0) shown in the structural formula (II) is taken, heated to 40 ℃, and stirred at constant temperature for 0.5h; 25g of the polytetrafluoroethylene thickener (specific surface area of 7.3 m) after the drying pretreatment is taken 2 (g), fully stirring and mixing with 5g of nano silicon dioxide (first additive), slowly adding into the perfluoropolyether base oil, and mechanically stirring for 1h to obtain a blend; and (3) after cooling to room temperature, grinding for 5 times by using a three-roller mill, and obtaining the finished grease.
Example 6 (addition of first and second additives)
70g of linear perfluoropolyether base oil (average molecular weight is 5200, p/q=2.0) shown in the structural formula (II) is taken and heated to 120 ℃ and kept at a constant temperature; taking 5g of a second additive S4 of formula (III) (average molecular weight 3300, R) F Is CF (CF) 3 —O—[(CF 3 )CFCF 2 O] x —CF 2 —，x＝18；R S Is- (CH) 2 ) 2 NH(CH 2 ) 3 Si(OCH 3 ) 3 ) Slowly adding the mixture into the perfluoropolyether base oil, mechanically stirring at 120 ℃ for 0.5h, fully and uniformly mixing, and cooling to 60 ℃ to obtain yellowish transparent oil; 20g of the polytetrafluoroethylene thickener (specific surface area of 8.5 m) after the drying pretreatment is taken 2 Per g), and 5g of nano silicon dioxide (first additive) are fully stirred and mixed, and then slowly added into the perfluoropolyether base oilMechanically stirring for 1h to obtain a blend; and (3) after cooling to room temperature, grinding for 5 times by using a three-roller mill, and obtaining the finished grease.
Comparative example 1 (without addition of the first and second additives)
70g of branched-chain perfluoropolyether base oil (average molecular weight is 16000, m/n=31) shown in the structural formula (I) is taken, heated to 50 ℃, and stirred at constant temperature for 0.5h; 30g of the polytetrafluoroethylene thickener (specific surface area of 5.2 m) after the drying pretreatment is taken 2 Slowly adding the mixture into the base oil, fully stirring for 1h, and cooling to room temperature; and then grinding for 3 times by using a three-roller mill to obtain the finished grease.
Comparative example 2 (without addition of the first and second additives)
60g of linear perfluoropolyether base oil (average molecular weight is 5200, p/q=2.0) shown in the structural formula (II) is taken, heated to 40 ℃, and stirred at constant temperature for 0.5h; 40g of the polytetrafluoroethylene thickener (specific surface area of 8.5 m) after the drying pretreatment is taken 2 Slowly adding the mixture into the base oil, fully stirring for 1h, and cooling to room temperature; and then grinding for 3 times by using a three-roller mill to obtain the finished grease.
The results of the performance test of the fluorine grease samples obtained in examples 1 to 6 and comparative examples 1 to 2 described above are shown in Table 1.
TABLE 1
It will be readily appreciated that the above embodiments are merely examples given for clarity of illustration and are not meant to limit the invention thereto. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. The low-oil-content wear-resistant fluorine grease is characterized by comprising the following components in percentage by weight:
50-80 wt% of perfluoropolyether base oil;
20-50 wt% of thickening agent;
also comprises an additive;
wherein the thickener is polytetrafluoroethylene thickener;
the additive is a second additive with the weight percentage of 0.1-10wt% in the fluorine grease; or the additive is 0.1-5wt% of a first additive and 0.1-10wt% of a second additive in the fluorine grease;
the first additive is selected from nano inorganic powder; the second additive is selected from the group consisting of compounds of the following structural formula (III):
wherein R in the structural formula (III) F Is CF (CF) 3 —O—[(CF 3 )CFCF 2 O] x —CF 2 -or CF 3 —O—[CF 2 CF 2 O] y —CF 2 —，x＝18～25，y＝36～49；R S Is- (CH) 2 ) 3 Si(OCH 3 ) 3 、—(CH 2 ) 3 Si(OCH 2 CH 3 ) 3 Or- (CH) 2 ) 2 NH(CH 2 ) 3 Si(OCH 3 ) 3 ；
The perfluoropolyether base oil adopts one or more of perfluoropolyethers of the following structural formulas (I) and (II);
wherein the average molecular weight of the structural formula (I) and the structural formula (II) is 1000-20000, m/n=20-50, and p/q=0.5-2 respectively.
2. A fluorochemical grease according to claim 1 wherein said perfluoropolyether base oil is present in an amount of 55 to 75% by weight.
3. The fluorocarbon grease as claimed in claim 1, wherein the thickener is 25 to 40% by weight.
4. A fluorochemical grease according to any of claims 1 to 3 wherein said first additive is selected from one or more of nano silica, hydrophobic white carbon black, nano silicon nitride, nano silicon carbide and nano molybdenum silicide.
5. A fluorochemical grease according to any of claims 1 to 3 wherein said compound of formula (III) has an average molecular weight of 3300 to 6100.
6. A fluorochemical grease according to any of claims 1 to 3 wherein said perfluoropolyether base oil has an average molecular weight of from 5200 to 16000.
7. A fluorochemical grease according to claim 6 wherein said perfluoropolyether base oil has an evaporation degree of less than 1.0% and is tested at 200 ℃ for 24 hours.
8. A fluorocarbon grease as claimed in any one of claims 1 to 3, characterized in that the polytetrafluoroethylene thickener has a specific surface area of 0.5 to 10m 2 /g。
9. A method of preparing a fluorogrease as claimed in any one of claims 1 to 8, comprising:
heating the perfluoropolyether base oil to 100-150 ℃, adding the second additive into the perfluoropolyether base oil, stirring and mixing the mixture, cooling the mixture to 50-90 ℃, and then adding the rest components into the mixture for stirring and mixing; and grinding to obtain the fluorine grease.
10. The method of claim 9, wherein the perfluoropolyether base oil is heated to 120 ℃ to 140 ℃ and the second additive is added; the temperature of the cooling is 60-70 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109097163A (en) * | 2018-06-29 | 2018-12-28 | 中国石油化工股份有限公司 | A kind of long-life round-the-clock Perfluoropolyether lubricating grease and its preparation method and application |
| CN113956911A (en) * | 2021-09-03 | 2022-01-21 | 中国石油化工股份有限公司 | Perfluoropolyether lubricating grease of composite thickening agent and preparation method thereof |
| CN115125047A (en) * | 2022-07-07 | 2022-09-30 | 西安交通大学 | Preparation method of modified silicon dioxide used as perfluoropolyether lubricant additive |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109097163A (en) * | 2018-06-29 | 2018-12-28 | 中国石油化工股份有限公司 | A kind of long-life round-the-clock Perfluoropolyether lubricating grease and its preparation method and application |
| CN113956911A (en) * | 2021-09-03 | 2022-01-21 | 中国石油化工股份有限公司 | Perfluoropolyether lubricating grease of composite thickening agent and preparation method thereof |
| CN115125047A (en) * | 2022-07-07 | 2022-09-30 | 西安交通大学 | Preparation method of modified silicon dioxide used as perfluoropolyether lubricant additive |
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