Use of a compound as a lubricant gelator, supramolecular gel lubricant and method for the preparation thereof
By preparing phosphate ester-functionalized perfluoropolyether gelling agents, the problems of creep migration and high friction coefficient of perfluoropolyether lubricants were solved, thereby improving lubrication performance and protecting the environment.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- LANZHOU INSTITUTE OF CHEMICAL PHYSICS CHINESE ACADEMY OF SCIENCES
- Filing Date
- 2022-06-30
- Publication Date
- 2026-06-26
AI Technical Summary
Perfluoropolyether lubricants have a high coefficient of friction, poor wettability, scarce additives, and are insoluble in other lubricants under actual working conditions, leading to creep migration and environmental pollution problems. Furthermore, existing gelling agents have failed to significantly improve their friction reduction and anti-wear properties.
A phosphate-functionalized perfluoropolyether gel factor with the structure shown in Formula I was prepared by a co-heating reaction to form a self-assembled network structure, which prevents the crawling and migration of lubricating oil. Furthermore, the friction-reducing and anti-wear element P was introduced through the phosphate ester structure to improve lubrication performance.
It effectively prevents leakage and creep migration of perfluoropolyether lubricating oil, reduces resource waste and environmental pollution, and significantly improves friction reduction and anti-wear performance, exhibiting excellent thermodynamic stability and rheological properties.
Smart Images
Figure CN117362335B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of lubricating materials technology, specifically relating to the application of a compound as a lubricant gelling factor, supramolecular gel lubricant and its preparation method. Background Technology
[0002] Perfluoropolyether lubricants are perfluorinated polymers composed of only three elements: carbon, phosphorus, and oxygen. They possess excellent oxidation stability, high temperature resistance, corrosion resistance, radiation resistance, non-flammability, and chemical stability, and are widely used in fields requiring high-performance lubrication, such as chemical engineering, aerospace, electronics, nuclear industry, military, and computer big data processing. Examples include rocket nozzles, missile catapult systems, compressors and valves in corrosive gas environments, centrifugal bearings, and magnetic recording devices.
[0003] However, perfluoropolyether lubricants exhibit problems such as high coefficient of friction, poor wettability, scarcity of additives, and insolubility with other lubricants under actual operating conditions. In particular, the scarcity of additives and poor solubility with organic matter severely restrict further improvements in the performance of perfluoropolyether lubricants. Furthermore, the low surface tension of perfluoropolyether lubricants makes them prone to creep migration during use, which can easily lead to environmental and equipment pollution.
[0004] Supramolecular gels are substances that exist in an intermediate state between lubricating oils and greases, possessing both the fluidity of lubricating oils and the anti-creep and anti-migration properties of greases. Supramolecular gel lubricants utilize the self-assembled three-dimensional network structure of gelling agents to spatially confine the base lubricating oil, thereby preventing its creep and migration.
[0005] Chinese Patent 201911157376.2 discloses a fluorinated functionalized gelling agent that is not only soluble in perfluoropolyether lubricating oil, ester base oil and organic solvents, but also has good gelling properties and can effectively prevent lubricating oil leakage and creep. However, the fluorinated functionalized gelling agent disclosed in Chinese Patent 201911157376.2, as an additive, does not significantly improve the friction reduction and anti-wear properties of perfluoropolyether lubricating oil. Summary of the Invention
[0006] The purpose of this invention is to provide an application of a compound as a lubricant gelling agent, a supramolecular gel lubricant, and a method for its preparation. The compound with the structure shown in Formula I provided by this invention, as a phosphate ester-functionalized perfluoropolyether gelling agent, can not only effectively constrain the creeping migration behavior of perfluoropolyether lubricants at the friction interface, but also improve the friction-reducing and anti-wear properties of perfluoropolyether lubricants.
[0007] To achieve the above objectives, the present invention provides the following technical solution:
[0008] This invention provides a method for preparing a compound with the structure shown in Formula I, comprising the following steps:
[0009] A mixture of 1H,1H,2H,2H-perfluoro-1-decanol and phosphorus pentoxide was subjected to a co-heating reaction to obtain a compound with the structure shown in Formula I, wherein the molar ratio of 1H,1H,2H,2H-perfluoro-1-decanol and phosphorus pentoxide was 4:1.
[0010]
[0011] Preferably, the co-heating reaction includes the following steps: heating the mixture to a first temperature for a first heat-holding reaction to obtain a first reactant; heating the first reactant to a second temperature for a second heat-holding reaction to obtain a second reactant; heating the second reactant to a third reaction temperature for a third heat-holding reaction to obtain a compound with the structure shown in Formula I; the first temperature is 60°C, and the first heat-holding reaction time is 2 hours; the second temperature is 75°C, and the second heat-holding reaction time is 2 hours; the third temperature is 95°C, and the third heat-holding reaction time is 24 hours.
[0012] Preferably, after the co-heating reaction, the product of the co-heating reaction is washed to obtain a compound with the structure shown in Formula I; the washing solvent includes acetonitrile.
[0013] This invention provides the application of compounds with the structure shown in Formula I as lubricant gelling agents.
[0014]
[0015] Preferably, the compound with the structure shown in Formula I is prepared by the preparation method described in the above technical solution.
[0016] This invention provides a supramolecular gel lubricant, comprising a base lubricating oil and a gelling agent, wherein the gelling agent is a compound with the structure shown in Formula I:
[0017]
[0018] Preferably, the gelling factor is prepared by the preparation method described in the above technical solution.
[0019] Preferably, the base lubricant comprises a perfluoropolyether lubricant.
[0020] Preferably, the mass percentage of gelling agent in the supramolecular gel lubricant is 5-10%.
[0021] This invention provides a method for preparing the supramolecular gel lubricant described above, comprising the following steps:
[0022] The gelling agent is dissolved in a base lubricating oil by heating, and then cooled to obtain a supramolecular gel lubricant; the heating and dissolution temperature is ≥150℃.
[0023] This invention provides a method for preparing a compound with the structure shown in Formula I, comprising the following steps: subjecting a mixture of 1H,1H,2H,2H-perfluoro-1-decanol and phosphorus pentoxide to a co-heated reaction to obtain a compound with the structure shown in Formula I, wherein the molar ratio of 1H,1H,2H,2H-perfluoro-1-decanol to phosphorus pentoxide is 4:1. The preparation method provided by this invention successfully prepares the compound with the structure shown in Formula I by controlling the molar ratio of 1H,1H,2H,2H-perfluoro-1-decanol to phosphorus pentoxide to 4:1, and the steps are simple, low-cost, and easily applicable to industrial production.
[0024] This invention provides the application of compounds with the structure shown in Formula I as lubricant gelling agents. The compounds with the structure shown in Formula I of this invention, as phosphate ester-functionalized perfluoropolyether gelling agents, use fluorine atoms to partially replace hydrogen atoms on the carbon chains of the gelling agent. The resulting perfluorinated gelling agent can completely dissolve in perfluoropolyether lubricating oil to form a stable gel. Simultaneously, this invention connects the two carbon chains of the gelling agent through the phosphate ester structure. Functional modification through the phosphate ester structure not only enables the gelling agent provided by this invention to self-assemble into a network structure, confining the perfluoropolyether lubricating oil, thereby effectively preventing lubricant leakage and creep, reducing the waste of expensive perfluoropolyether lubricating oil resources, but also effectively reducing mechanical and environmental pollution caused by leakage. Furthermore, the phosphate ester structure introduces the friction-reducing and anti-wear element P, thereby improving the friction-reducing and anti-wear properties of the perfluoropolyether lubricating oil. The results of the examples show that, through SRV micro-motion friction and wear testing machine and optical microscopic three-dimensional profilometry, the phosphate ester functionalized perfluoropolyether gelling agent provided by the present invention, as a lubricating additive, improves the friction reduction, anti-wear, and tribological properties of perfluoropolyether lubricating oil under extreme pressure conditions; as a gelling agent, it gels the perfluoropolyether lubricating oil to obtain a solid-like supramolecular gel lubricant, which prevents the creep migration behavior of the perfluoropolyether lubricating oil, and at the same time breaks through the bottleneck of the high friction coefficient of perfluoropolyether lubricating oil.
[0025] This invention provides a supramolecular gel lubricant, comprising a base lubricating oil and a gelling agent, wherein the gelling agent is a compound with the structure shown in Formula I. The supramolecular gel lubricant provided by this invention exhibits good thermodynamic stability and rheological properties, and compared with liquid base oil, demonstrates excellent resistance to lubricating oil leakage and creep. When the base lubricant is a perfluoropolyether lubricating oil, the resulting supramolecular gel lubricant exhibits excellent friction-reducing and anti-wear properties. Attached Figure Description
[0026] Figure 1The gelling properties of the phosphate ester-functionalized perfluoropolyether supramolecular gel prepared in the embodiments of the present invention;
[0027] Figure 2 The synthesis flowchart of the phosphate ester-functionalized perfluoropolyether supramolecular gel provided in the embodiments of the present invention is shown. Detailed Implementation
[0028] This invention provides a method for preparing a compound with the structure shown in Formula I, comprising the following steps:
[0029] A mixture of 1H,1H,2H,2H-perfluoro-1-decanol and phosphorus pentoxide was subjected to a co-heating reaction to obtain a compound with the structure shown in Formula I, wherein the molar ratio of 1H,1H,2H,2H-perfluoro-1-decanol and phosphorus pentoxide was 4:1.
[0030]
[0031] In this invention, unless otherwise specified, all raw materials / components used in the preparation are commercially available products well known to those skilled in the art.
[0032] In this invention, the molar ratio of 1H,1H,2H,2H-perfluoro-1-decyl alcohol and phosphorus pentoxide is preferably 4:1.
[0033] In this invention, the co-heating reaction is preferably carried out in an anhydrous environment.
[0034] In this invention, prior to the co-heating reaction, it is preferable to remove moisture from the co-heating reaction vessel by purging with nitrogen.
[0035] In this invention, the co-heating reaction preferably includes the following steps: heating the mixture of 1H,1H,2H,2H-perfluoro-1-decyl alcohol and phosphorus pentoxide to a first temperature for a first heat preservation reaction to obtain a first reactant; heating the first reactant to a second temperature for a second heat preservation reaction to obtain a second reactant; and heating the second reactant to a third reaction temperature for a third heat preservation reaction to obtain a compound with the structure shown in Formula I.
[0036] In this invention, the first temperature is preferably 60°C, and the first heat preservation reaction time is preferably 2 hours. In this invention, the first heat preservation reaction is preferably carried out under stirring conditions, and specifically, the stirring is preferably magnetic stirring.
[0037] In this invention, the second temperature is preferably 75°C, and the second heat preservation reaction time is preferably 2 hours.
[0038] In this invention, the third temperature is preferably 95°C, and the third heat preservation reaction time is preferably 24 hours.
[0039] In this invention, after the co-heating reaction, the invention preferably further includes washing the product material of the co-heating reaction to obtain a compound with the structure shown in Formula I.
[0040] In this invention, the product of the co-heating reaction is a pale yellow solid at room temperature.
[0041] The present invention preferably involves cooling the product of the co-heated reaction to room temperature before performing the washing.
[0042] In this invention, the product of the co-heating reaction is a solid after being cooled to room temperature.
[0043] In this invention, the solvent used for washing preferably includes acetonitrile.
[0044] In this invention, the washing is preferably performed 3 times.
[0045] The present invention preferably removes 1H,1H,2H,2H-perfluoro-1-decyl alcohol from the co-heated reaction materials by washing with acetonitrile.
[0046] In this invention, after washing, the product is preferably dried to obtain a compound with the structure shown in Formula I. In this invention, the drying is preferably vacuum drying, the drying temperature is preferably 80°C, and the drying time is preferably 8 hours.
[0047] In this invention, the compound with the structure shown in Formula I is a white powder.
[0048] The compound of Formula I provided by this invention is completely soluble in perfluoropolyether lubricating oil under high temperature conditions and spontaneously forms a gel when cooled to room temperature.
[0049] The compound with the structure shown in Formula I provided by this invention has excellent friction reduction and anti-wear effects compared with perfluoropolyether lubricating oil.
[0050] The compound of Formula I provided by this invention can prevent leakage and creep of perfluoropolyether lubricants, thereby reducing the waste of expensive perfluoropolyether lubricants and the pollution of the environment or operating parts.
[0051] This invention provides the application of compounds with the structure shown in Formula I as lubricant gelling agents.
[0052]
[0053] In this invention, the compound with the structure shown in Formula I is preferably prepared by the preparation method described in the above technical solution.
[0054] The compound with the structure shown in Formula I provided by this invention serves as a phosphate ester-functionalized perfluoropolyether gelling agent, which is a small molecule gelling agent. The functional modification using the phosphate ester structure not only enables the compound with the structure shown in Formula I provided by this invention to self-assemble into a network structure as a gelling agent, thereby confining the perfluoropolyether lubricant and effectively preventing lubricant leakage and creep; but also introduces the friction-reducing and anti-wear element P through the phosphate ester structure, thereby improving the friction-reducing and anti-wear properties of the perfluoropolyether lubricant.
[0055] This invention provides a supramolecular gel lubricant, comprising a base lubricating oil and a gelling agent, wherein the gelling agent is a compound with the structure shown in Formula I:
[0056]
[0057] In this invention, the gelling factor is preferably prepared by the preparation method described in the above technical solution.
[0058] In this invention, the base lubricating oil preferably comprises a perfluoropolyether lubricating oil.
[0059] In this invention, the mass percentage of gelling factor in the supramolecular gel lubricant is preferably 5-10%, more preferably 5%.
[0060] This invention provides a method for preparing the supramolecular gel lubricant described above, comprising the following steps:
[0061] The gelling agent is dissolved in a base lubricating oil by heating, and then cooled to obtain a supramolecular gel lubricant; the heating and dissolution temperature is ≥150℃.
[0062] The present invention does not have special requirements for the heating time, as long as the gelling agent is completely dissolved; the cooling is preferably natural cooling.
[0063] The phosphate-functionalized perfluoropolyether gel factor provided by the present invention can be completely dissolved in perfluoropolyether lubricating oil at ≥150℃, preferably 150℃. After cooling, a semi-solid supramolecular gel lubricant is obtained. The supramolecular gel lubricant provided by the present invention has good friction reduction and anti-wear properties, and improves the tribological properties of perfluoropolyether lubricating oil.
[0064] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below with reference to the accompanying drawings and embodiments, but these should not be construed as limiting the scope of protection of the present invention.
[0065] Example 1
[0066] according to Figure 2The synthetic flow chart shown indicates that 0.04 mol of 1H,1H,2H,2H-perfluoro-1-decyl alcohol and 0.01 mol of phosphorus pentoxide were added to a 100 mL three-necked flask. Nitrogen gas was purged to remove moisture from the reaction environment. The mixture was heated to 60 °C and allowed to stand for 10 min at 60 °C. The mixture was then stirred magnetically for 2 h, heated to 75 °C for 2 h, and then heated to 95 °C for 24 h. The mixture was washed three times with acetonitrile and finally dried in a vacuum drying oven at 80 °C for 8 h to obtain a white powder, which is the compound with the structure shown in Formula I. This compound can be used as a phosphate ester-functionalized perfluoropolyether gelling agent.
[0067]
[0068] The NMR data are as follows: 1 HNMR(400MHz,CD4O,TMS)δ:4.33–4.26(m,4H),2.7–4.26(m,4H).
[0069] Example 2
[0070] Take 0.5g of the compound with the structure shown in Formula I prepared in Example 1 as a phosphate ester-functionalized perfluoropolyether gelling agent. Add 9.5g of perfluoropolyether lubricating oil to a sample vial. Stir the powdered gelling agent at 150°C for 30 minutes until it completely dissolves in the perfluoropolyether lubricating oil, resulting in a transparent liquid, as shown below. Figure 1 As shown, the non-flowing phosphate ester-functionalized perfluoropolyether gel factor, which was cooled to room temperature, was removed and used as an added supramolecular gel lubricant.
[0071] Example 3
[0072] To illustrate the thermal stability of the phosphate-functionalized perfluoropolyether supramolecular gel lubricant prepared in Example 2 of this invention, the phase transition temperature and thermal decomposition temperature of supramolecular gel lubricants (prepared according to the method of Example 2) containing 5 wt%, 6 wt%, and 7 wt% phosphate-functionalized perfluoropolyether gel factor of Formula I prepared in Example 1 were analyzed using differential scanning calorimetry and thermogravimetric analysis. The results are shown in Table 1. From the data in Table 1, it is clear that the phase transition temperatures of the supramolecular gel lubricants prepared using the phosphate-functionalized perfluoropolyether gel factor of Formula I prepared in Example 1 as an additive are all around 110°C, indicating that they exhibit a stable gel state below 110°C. Furthermore, the corresponding thermal decomposition temperatures are all around 226°C, indicating that the supramolecular gel lubricant containing the phosphate-functionalized perfluoropolyether gel factor of Formula I prepared in Example 2 of this invention also possesses high thermal stability, similar to perfluoropolyether lubricating oils.
[0073] Table 1 shows the phase transition temperature and thermodynamic properties of the supramolecular gel lubricant provided by this invention.
[0074] Phosphate-functionalized perfluoropolyether supramolecular gel <![CDATA[T g-sol (℃)]]> <![CDATA[T g (℃)]]> Gel (5wt%) 110 226 Gel (6wt%) 110 226 Gel (7wt%) 110 226
[0075] Example 4
[0076] The extreme pressure performance of the phosphate ester functionalized perfluoropolyether supramolecular gel lubricant prepared in Example 2 was evaluated using an SRV-V micro-vibration friction and wear tester manufactured by Optimol Grease GmbH, Germany, and compared with PFPE lubricating oil.
[0077] The specific experimental procedure is as follows:
[0078] The extreme pressure properties of the perfluoropolyether lubricant and the phosphate-functionalized perfluoropolyether supramolecular gel lubricant prepared in Example 2 were evaluated using an Optimol SRV-V fretting and wear testing machine. The extreme pressure properties of the perfluoropolyether lubricant and the phosphate-functionalized perfluoropolyether supramolecular gel lubricant prepared in Example 2 were evaluated at a temperature of 25°C, an amplitude of 1 mm, and a frequency of 25 Hz. The contact form of the friction pair was ball-disk point contact, with the upper test ball being a 10 mm diameter GCr15 (SAE52100) steel ball and the lower test disk being steel.
[0079] Table 2 shows the extreme pressure performance of perfluoropolyether lubricating oil and phosphate ester-functionalized perfluoropolyether supramolecular gel lubricants with mass concentrations of 5 wt%, 6 wt%, and 7 wt%. As can be seen from Table 2, the extreme pressure performance of the phosphate ester-functionalized perfluoropolyether supramolecular gel lubricant is significantly greater than that of the perfluoropolyether lubricating oil. Table 2 Extreme Pressure Performance of Perfluoropolyether Lubricating Oil and Phosphate Ester-Functionalized Perfluoropolyether Supramolecular Gel Lubricants at Different Concentrations
[0080] project PFPE oil Gel (5wt%) Gel (6wt%) Gel (7wt%) Extreme pressure parameters 300N 1350N 950N 1100N
[0081] Example 5
[0082] The friction-reducing properties of phosphate ester-functionalized perfluoropolyether supramolecular gel lubricant were evaluated using the SRV-V micro-vibration friction and wear tester manufactured by Optimol Grease GmbH, Germany, and compared with PFPE lubricating oil.
[0083] The specific experimental procedure is as follows:
[0084] The tribological properties of perfluoropolyether lubricants and phosphate-functionalized perfluoropolyether supramolecular gel lubricants were evaluated using an Optimol SRV-V fretting and wear testing machine. Specific experimental conditions were as follows: temperature 25℃, amplitude 1 mm, frequency 25 Hz, period 30 min, and loads of 200 N, 300 N, and 400 N. The contact type of the friction pair was ball-disk point contact, with the upper test ball being a 10 mm diameter GCr15 (SAE52100) steel ball and the lower test disk being steel.
[0085] Table 3 shows the coefficients of friction of perfluoropolyether lubricating oil and phosphate-functionalized perfluoropolyether supramolecular gel lubricants with mass concentrations of 5 wt%, 6 wt%, and 7 wt% under different load conditions. As can be seen from Table 3, the phosphate-functionalized perfluoropolyether supramolecular gel lubricant exhibits a lower coefficient of friction than the perfluoropolyether lubricating oil under the same frictional environment, demonstrating excellent friction-reducing performance.
[0086] Table 3. Coefficients of friction for perfluoropolyether lubricants and phosphate ester-functionalized perfluoropolyether supramolecular gel lubricants
[0087] project PFPE oil Gel (5wt%) Gel (6wt%) Gel (7wt%) 200N 0.144 0.138 0.138 0.136 300N 0.144 0.133 0.133 0.134 400N 0.145 0.132 0.132 0.131
[0088] Example 6
[0089] The anti-wear properties of perfluoropolyether lubricants and phosphate-functionalized perfluoropolyether supramolecular gel lubricants under different load conditions were evaluated using a non-contact three-dimensional surface profilometer from KLA-Tencor.
[0090] The specific experimental procedure is as follows:
[0091] The volume of wear scars under different load conditions was analyzed using a non-contact three-dimensional surface profilometer from KLA-Tencor, and the results are shown in Table 4. Table 4 shows that the wear volume under 200N, 300N, and 400N conditions is smaller than that of the perfluoropolyether lubricant, exhibiting excellent anti-wear performance.
[0092] Table 4 Wear Volume of Perfluoropolyether Lubricants and Phosphate Ester Functionalized Perfluoropolyether Supramolecular Gel Lubricants
[0093] <![CDATA[Wear volume (mm 3 )]]> PFPE oil Gel (5wt%) Gel (6wt%) Gel (7wt%) 200N <![CDATA[0.98x10 -3 ]]> <![CDATA[0.50x10 -3 ]]> <![CDATA[0.78x10 -3 ]]> <![CDATA[0.63x10 -3 ]]> 300N <![CDATA[3.02x10 -3 ]]> <![CDATA[0.52x10 -3 ]]> <![CDATA[0.69x10 -3 ]]> <![CDATA[0.30x10 -3 ]]> 400N <![CDATA[6.85x10 -3 ]]> <![CDATA[0.85x10 -3 ]]> <![CDATA[0.81x10 -3 ]]> <![CDATA[0.37x10 -3 ]]>
[0094] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. Other embodiments can be obtained based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.
Claims
1. Application of compounds with the structure shown in Formula I as lubricant gelling agents. Equation I.
2. A supramolecular gel lubricant, characterized in that, It includes a base lubricant and a gelling agent, wherein the gelling agent is a compound with the structure shown in Formula I: Equation I.
3. The supramolecular gel lubricant according to claim 2, characterized in that, The base lubricant includes perfluoropolyether lubricant.
4. The supramolecular gel lubricant according to claim 2 or 3, characterized in that, The mass percentage of gelling agent in the supramolecular gel lubricant is 5-10%.
5. The method for preparing the supramolecular gel lubricant according to any one of claims 2 to 4, characterized in that, Includes the following steps: The gelling agent is dissolved in a base lubricating oil by heating, and then cooled to obtain a supramolecular gel lubricant; the heating and dissolution temperature is ≥150℃.