Fluororesin, preparation method thereof and full-dry lubricant
By preparing a fully dry lubricant that combines fluororesin with solid lubricants, the adhesion and migration problems of traditional lubricants in areas of contact with the human body are solved, excellent lubrication, anti-wear properties and high temperature resistance are achieved, and the compatibility of the substrate is improved.
Patent Information
- Application Number
- CN202510892676.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-30
- Publication Date
- 2025-10-10
AI Technical Summary
Traditional dry lubricants are prone to adhesion and migration contamination in areas of contact with the human body, and have poor compatibility with the substrate and lubrication and anti-wear properties.
Fluororesin is used as the base material and prepared through addition reaction. It is combined with solid lubricants and fluorine solvents to prepare a fully dry lubricant. Fluororesin has good compatibility with solid lubricants and has excellent lubrication, anti-wear and high temperature resistance.
The fully dry lubricant prepared does not adhere or migrate after the substrate surface becomes completely dry. It has excellent lubrication, anti-wear and high temperature resistance, solves the adhesion and migration problems of traditional lubricants, and improves the compatibility and lubrication performance of the substrate.
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Figure CN120757685A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of lubricants, in particular to a fluororesin, a preparation method thereof and a full dry type lubricant. BACKGROUND
[0002] Dry film lubricant is a kind of lubricant containing polytetrafluoroethylene (PTFE) solid lubricating particles. The lubricant will rapidly evaporate on the surface of the lubricated part (the surface of most parts to be lubricated such as metal, paper, wood, rubber, plastic, glass, etc.) and form a uniform lubricating film, while playing the roles of waterproof, moisture-proof, corrosion-proof and cleaning.
[0003] The dry film lubricant can penetrate and bond to the surface of leather, metal, paper, wood, rubber, plastic, glass or other most parts to be lubricated, forming a non-sticky lubricating oil film to prevent direct contact of the friction surface, thereby reducing friction and noise, etc.
[0004] With the rapid development of science and technology, the competition is becoming more and more fierce, and the requirements for traditional optical machines and automotive interiors are becoming higher and higher. Although the traditional dry film lubricant can play a good lubricating and noise reduction role on leather, metal and plastic, etc., it will form an oil film on the surface of leather, metal and plastic, which will stick to the skin or other objects when the skin or other objects come into contact with the oil film, and even the oil film will climb to other positions on its own, causing pollution.
[0005] In order to solve the shortcomings of the traditional dry lubricant, it is urgent to develop a full dry type dry lubricant which will not penetrate and transfer printing, can be used in places where people can touch, and has very superior lubricating performance and wear resistance. SUMMARY
[0006] In order to overcome the shortcomings and deficiencies in the prior art, the purpose of the present application is to provide a fluororesin and a preparation method thereof. The fluororesin can be used to prepare a lubricant, has good non-stickiness, wear resistance and lubricating performance, and the prepared full dry type lubricant has excellent lubricating wear resistance and high temperature resistance, and after being completely dried on the surface of the substrate, it will not cause oil film adhesion or migration pollution. The problems of poor compatibility of the existing dry film lubricant with the coated substrate and poor lubricating wear resistance can be effectively solved. The preparation method of the fluororesin is simple and easy to control, the product quality is stable, the comprehensive performance is superior, and it is beneficial to industrialized mass production.
[0007] Another purpose of the present application is to provide a lubricant. The lubricant has fluororesin as a base material, has excellent lubricating wear resistance and high temperature resistance, and after being completely dried on the surface of the substrate, it will not cause oil film adhesion or migration pollution. The compatibility of the fluororesin with the raw materials such as solid lubricant in the lubricant is good, and the comprehensive performance is superior.
[0008] The present application is achieved by the following technical scheme: a fluororesin, the molecular structure formula of the fluororesin is shown as formula I, formula II, formula III, formula IV or formula V:
[0009]
[0010] Wherein, R1 is -H, one of the molecular structure formula VI, the molecular structure formula VII or the molecular structure formula VIII:
[0011]
[0012] In the formula, n is a natural number of 1-100;
[0013] R2, R3 is one of the following molecular structure formula IX or X:
[0014]
[0015] In the formula, n, m is a natural number of 1-100.
[0016] The preparation method of the above fluororesin comprises the following steps:
[0017] (1) taking initiator and functional monomer, adding butyl acetate in a four-necked flask equipped with stirring motor, dropping funnel, spherical condenser and thermometer, and heating to polymerization temperature, then loading the initiator and functional monomer into the dropping funnel after stirring and mixing uniformly, to obtain mixed monomer, starting to drop the mixed monomer, and completing the dropping within 60-120 min, finally keeping the system temperature at 70-150 DEG C, and reacting for 100-150 min to obtain mixture A;
[0018] (2) loading the remaining functional monomer into the dropping funnel, and dropping into the mixture A, completing the dropping within 100-120 min to obtain mixture B;
[0019] (3) keeping the mixture B at constant temperature of 70-150 DEG C for 100-150 min, then adding the remaining initiator to continue the reaction for 100-120 min, to obtain the fluororesin.
[0020] The present application prepares fluororesin through functional monomer addition reaction, the prepared fluororesin has high temperature stability, non-stickiness, anti-wear and lubricating properties; the full dry lubricant prepared by the fluororesin has good compatibility with other components of the lubricant, and improves the non-stickiness and anti-wear lubricating properties of the lubricant.
[0021] Further, the polymerization temperature is 70-140 DEG C.
[0022] Further, the initiator includes, but is not limited to, at least one of phenyl chloroethane, butyl peroxyl benzoate or benzoyl peroxide.
[0023] Further, in step (1), the functional monomer includes, but is not limited to, at least one of olefin, unsaturated ether, alkyl acrylate or fluorine-containing acrylate monomer.
[0024] Further, the olefin includes, but is not limited to, decene; the unsaturated ether includes, but is not limited to, vinyl ethyl ether; the alkyl acrylate includes, but is not limited to, at least one of methyl methacrylate or methyl acrylate isooctyl; and the fluorine-containing acrylate monomer includes, but is not limited to, at least one of 2-(trifluoromethyl) methyl acrylate, trifluoroethyl acrylate or fluorine-containing acrylate monomer A.
[0025] Further, the preparation method of the fluorine-containing acrylate monomer A includes the following steps: adding fluorine-containing alkyl iodine, acrylate, organic weak base catalyst, polymerization inhibitor and alcohol solution into a reaction container, performing esterification reaction under the conditions of temperature of 150-200℃ and pressure of 0.5-1.5 Mpa, reacting for 6-10 h, filtering and distilling under reduced pressure after the reaction is completed, to obtain the fluorine-containing acrylate monomer A.
[0026] Further, the molar ratio of the fluorine-containing alkyl iodine, acrylate, organic weak base catalyst and polymerization inhibitor is 1:1-2:0.002-0.1:0.001-0.1; and the amount of the alcohol solvent is 5-20 times of the mass of the fluorine-containing alkyl iodine.
[0027] Further, the fluorine-containing alkyl iodine is at least one of CF3(CF2) n O(CH2) m I or CF3(CF2) n (CH2) m I, wherein n and m are natural numbers of 1-100.
[0028] Further, the acrylate includes, but is not limited to, at least one of potassium acrylate, sodium acrylate, lithium acrylate, potassium methacrylate, sodium methacrylate or lithium methacrylate; the organic base catalyst includes, but is not limited to, at least one of ethylamine, triethylamine or pyridine; the polymerization inhibitor includes, but is not limited to, at least one of hydroquinone, p-hydroxyanisole, phenothiazine or copper chloride; and the alcohol solvent includes, but is not limited to, at least one of propanol, butanol or tert-butanol.
[0029] Further, the mass ratio of the functional monomer added in step (1) to the functional monomer added in step (2) is 3-6:4-7; and the mass ratio of the initiator added in step (1) to the initiator added in step (3) is 6-8:2-4.
[0030] The preparation method of the fluororesin of the present invention is simple to operate, easy to control, has low production cost, and is conducive to large-scale industrial production.
[0031] Another object of the present invention is achieved through the following technical solution: a fully dry lubricant, comprising the following components by mass fraction: 1%-10% fluororesin, 0.5%-10% solid lubricant, and the balance being fluorosolvent.
[0032] Furthermore, the solid lubricant is at least one of PTFE with a median particle size of 0.5 to 50 μm or molybdenum disulfide with a median particle size of 0.5 to 50 μm.
[0033] Furthermore, the fluorine solvent is at least one of trifluorotrichloroethane, hydrofluoroether, perfluorobutyl cyclic ether, pentafluorobutane, hexafluoropropylene trimer, hexafluoropropylene dimer, perfluorocyclohexane, perfluorohexane, perfluoromethylhexane, ethoxy nonafluorobutyl ether or methoxy nonafluorobutyl ether.
[0034] Furthermore, the present invention also provides a method for preparing the above-mentioned fully dry lubricant, comprising the following steps:
[0035] Fluororesin, solid lubricant and fluorine solvent are weighed according to mass fraction and added into a container, and dispersed at a high speed of 9000-11000 r / min for 4-6 minutes to obtain a fully dry lubricant.
[0036] The fully dry lubricant of the present invention uses fluororesin as its base material, and has excellent lubrication, anti-wear and high-temperature resistance. After it is applied to the surface of the substrate and completely dries, there will be no oil film adhesion or migration contamination. Fluororesin has good compatibility with raw materials such as solid lubricants and has excellent comprehensive performance.
[0037] The present invention has the beneficial effects of being able to prepare lubricants with excellent non-stick, anti-wear, and lubricating properties. The resulting fully dry lubricant exhibits excellent lubrication, anti-wear, and high-temperature resistance. Furthermore, after being applied to a substrate and completely dried, it does not exhibit oil film adhesion or migration contamination. This effectively addresses the issues of existing dry film lubricants, which suffer from poor compatibility with the substrates they are applied to and poor lubrication and anti-wear properties. The fluororesin preparation method is simple to operate and easy to control, resulting in stable product quality and superior overall performance, making it suitable for large-scale industrial production. DETAILED DESCRIPTION
[0038] In order to facilitate understanding by those skilled in the art, the present invention will be further described below with reference to the embodiments. The contents mentioned in the embodiments are not intended to limit the present invention.
[0039] Example 1
[0040] This embodiment provides a fluororesin, the structure of which is shown in Formula I below:
[0041]
[0042] The preparation method of the fluororesin comprises the following steps:
[0043] (1) In a 1000 ml four-necked flask equipped with a stirring motor, a dropping funnel, a spherical condenser and a thermometer, 300 ml of butyl acetate was added, and after condensed water was connected, the temperature was started to rise to 80° C., and then 15 g of methyl 2-(trifluoromethyl)acrylate and 0.4 g of initiator were stirred and mixed uniformly and then loaded into the dropping funnel to obtain a mixed monomer; the mixed monomer was added dropwise and the addition was completed within 90 minutes. Finally, the system temperature was maintained at 110° C. and the reaction was carried out for 125 minutes to obtain a mixture A;
[0044] (2) The remaining 15 g of methyl 2-(trifluoromethyl)acrylate was loaded into a dropping funnel and added dropwise to mixture A over 110 min to obtain mixture B;
[0045] (3) Mixture B was reacted at 110°C for 125 minutes, and then the remaining 0.1g of initiator was added and the reaction was continued for 110 minutes to obtain a fluororesin. The reaction formula is as follows:
[0046]
[0047] Furthermore, the initiator is benzoyl peroxide.
[0048] This embodiment also provides a fully dry lubricant, which includes the following components by mass fraction: 2% fluororesin, 1% solid lubricant, 20% trichlorotrifluoroethane, and the balance being hydrofluoroether, wherein the solid lubricant is PTFE with a median particle size of 1 μm.
[0049] Furthermore, the preparation method of the fully dry lubricant includes the following steps: weighing 2g of the above-mentioned fluororesin, 1g of PTFE with a median particle size of 1μm, 20g of trifluorotrichloroethane and 77g of hydrofluoroether into a container, and dispersing them at a high speed of 10000r / min for 5min to obtain a fully dry lubricant.
[0050] Example 2
[0051] This embodiment provides a fluororesin, the structure of which is shown in Formula II below:
[0052]
[0053] The preparation method of the fluororesin comprises the following steps:
[0054] (1) In a 1000 ml autoclave, 200 ml of alcohol solution, 0.5 mol of fluoroalkyl iodide, 0.8 mol of sodium acrylate, 0.002 mol of organic weak base catalyst and 0.002 mol of polymerization inhibitor were added, and an esterification reaction was carried out at a temperature of 160° C. and a pressure of 1.0 MPa for 8 hours. After the reaction was complete, the mixture was filtered and distilled under reduced pressure to obtain a fluoroacrylate monomer A for standby use; wherein the fluoroalkyl iodide was CF3CF2CH2I, and the reaction formula was as follows:
[0055]
[0056] (2) In a 1000 ml four-necked flask equipped with a stirring motor, a dropping funnel, a spherical condenser and a thermometer, 300 ml of butyl acetate was added, and after the condensed water was connected, the temperature was started to be raised to 135° C., and then 25 g of methyl methacrylate, 2 g of the fluorinated acrylate monomer A obtained in step (1), and 0.4 g of the initiator butyl peroxybenzoate were stirred and mixed uniformly and loaded into the dropping funnel to obtain a mixed monomer; the mixed monomer was added dropwise and the addition was completed within 90 min. Finally, the system temperature was maintained at 125° C. and the reaction was carried out for 125 min to obtain a mixture A;
[0057] (3) The remaining 2.5 g of the fluorinated acrylate monomer A prepared in step (1) was loaded into a dropping funnel and added dropwise to the mixture A within 110 min to obtain a mixture B;
[0058] (4) Mixture B was reacted at 125°C for 125 minutes, and the remaining 0.1 g of initiator was added and the reaction was continued for 110 minutes to obtain a fluororesin. The reaction formula is as follows:
[0059]
[0060] Furthermore, the initiator is butyl perbenzoate; the alcohol solution is tert-butyl alcohol; the organic weak base catalyst is triethylamine; and the inhibitor is hydroquinone.
[0061] This embodiment also provides a fully dry lubricant, which has the following components by mass fraction: 2% fluororesin, 1% solid lubricant, 20% trichlorotrifluoroethane, and the balance being hydrofluoroether, wherein the solid lubricant is PTFE with a median particle size of 1 μm.
[0062] Furthermore, the preparation method of the fully dry lubricant includes the following steps: weighing 2g of the above-mentioned fluororesin, 1g of PTFE with a median particle size of 1μm, 20g of trifluorotrichloroethane and 77g of hydrofluoroether into a container, and dispersing them at a high speed of 10000r / min for 5min to obtain a fully dry lubricant.
[0063] Example 3
[0064] The present embodiment provides a fluororesin, the structure of which is shown in the following formula III:
[0065]
[0066] The preparation method of the fluororesin comprises the following steps:
[0067] (1) In a 1000ml high-pressure reactor, 200ml alcohol solution, 0.5mol fluorine-containing alkyl iodide, 0.8mol sodium acrylate, 0.002mol organic weak base catalyst and 0.002mol polymerization inhibitor are added, and esterification reaction is carried out at a temperature of 160℃ and a pressure of 1.0Mpa for 8h. After the reaction is completed, filtration and reduced pressure distillation are carried out to obtain fluorine-containing propenoic acid ester monomer A for standby use; wherein the fluorine-containing alkyl iodide is CF3CF2CH2I; the reaction formula is as follows:
[0068]
[0069] (2) In a 1000ml four-necked flask equipped with a stirring motor, a dropping funnel, a spherical condenser and a thermometer, 300ml butyl acetate is added, and after connecting the condensing water, the temperature is raised to 135℃. Then 15g of fluorine-containing propenoic acid ester monomer A prepared in step (1) and 0.4g of initiator are stirred and mixed uniformly, and then loaded into the dropping funnel to obtain a mixed monomer. The mixed monomer is started to be added dropwise, and the addition is completed within 90min. Finally, the temperature of the system is maintained at 125℃, and the reaction is carried out for 125min to obtain a mixture A;
[0070] (3) The remaining 10g of fluorine-containing propenoic acid ester monomer A prepared in step (1) is loaded into the dropping funnel and added dropwise to the mixture A, and the addition is completed within 110min to obtain a mixture B;
[0071] (4) The mixture B is kept at a constant temperature of 125℃ for 125min, and then 0.1g of the remaining initiator is added for further reaction for 110min to obtain the fluororesin. The reaction formula is as follows:
[0072]
[0073] Further, the initiator is selected from butyl peroxybenzoate; the alcohol solution is selected from tert-butyl alcohol; the organic weak base catalyst is selected from triethylamine; and the polymerization inhibitor is selected from hydroquinone.
[0074] The present embodiment also provides a full-dry type lubricant, which comprises the following components in mass fraction: 2% of fluororesin, 1% of solid lubricant, 20% of trifluorotrichloroethane, and the balance of hydrofluoroether, wherein the solid lubricant is PTFE with a median particle size of 1μm.
[0075] Further, the preparation method of the full dry type lubricant comprises the following steps: weighing 2 g of the fluororesin, 1 g of PTFE with a median particle size of 1 μm, 20 g of trifluorotrichloroethane and 77 g of hydrofluoroether into a container, and dispersing at a high speed of 10000 r / min for 5 min to obtain the full dry type lubricant.
[0076] Example 4
[0077] The present embodiment provides a fluororesin, and the structure of the fluororesin is shown in the following formula IV:
[0078]
[0079] The preparation method of the fluororesin comprises the following steps:
[0080] (1) 200 ml of an alcohol solution, 0.5 mol of fluorine-containing alkyl iodide, 0.8 mol of sodium acrylate, 0.002 mol of an organic weak base catalyst and 0.002 mol of a polymerization inhibitor are added into a 1000 ml high-pressure reaction kettle, and esterification is carried out at a temperature of 160℃ and a pressure of 1.0 Mpa for 8 h, and after the reaction is completed, filtration and reduced pressure distillation are carried out to obtain fluorine-containing acrylate monomer A for standby; wherein the fluorine-containing alkyl iodide is CF3CF2CH2I; the reaction formula is as follows:
[0081]
[0082] (2) 300 ml of butyl acetate is added into a 1000 ml four-necked flask equipped with a stirring motor, a dropping funnel, a spherical condenser and a thermometer, and after the condensate water is connected, the temperature is increased to 135℃, and then 5 g of the fluorine-containing acrylate monomer A prepared in step (1), 5 g of trifluoroethyl acrylate and 0.4 g of an initiator are uniformly stirred and mixed, and then loaded into the dropping funnel to obtain a mixed monomer; the mixed monomer is started to be added dropwise, and the addition is completed within 90 min, and finally the temperature of the system is maintained at 110℃, and the reaction is carried out for 125 min to obtain a mixture A;
[0083] (3) the remaining 5 g of the fluorine-containing acrylate monomer A prepared in step (1) and the remaining 5 g of trifluoroethyl acrylate are loaded into the dropping funnel and added dropwise into the mixture A, and the addition is completed within 110 min to obtain a mixture B;
[0084] (4) the mixture B is kept at a constant temperature of 125℃ for 125 min, and then the remaining 0.1 g of the initiator is added to continue the reaction for 110 min to obtain the fluororesin. The reaction formula is as follows:
[0085]
[0086] Further, the initiator is selected from benzoyl peroxide butyl; the alcohol solution is selected from tert-butyl alcohol; the weak organic base catalyst is selected from triethylamine; and the polymerization inhibitor is selected from hydroquinone.
[0087] The present embodiment also provides a full dry type lubricant comprising the following components in mass fraction: 2% of the fluororesin, 1% of the solid lubricant, 30% of ethoxy nonafluorobutyl ether, and the balance of hexafluoropropylene trimer, wherein the solid lubricant is PTFE with a median particle size of 1 μm.
[0088] Further, the preparation method of the full dry type lubricant comprises the following steps: weighing 2 g of the fluororesin, 1 g of PTFE with a median particle size of 1 μm, 30 g of ethoxy nonafluorobutyl ether, and 67 g of hexafluoropropylene trimer into a container, and dispersing at a high speed of 10,000 r / min for 5 min to obtain the full dry type lubricant.
[0089] Embodiment 5
[0090] The present embodiment provides a fluororesin, the structure of which is shown in the following formula V:
[0091]
[0092] The preparation method of the fluororesin comprises the following steps:
[0093] (1) In a 1000 ml high-pressure reactor, 200 ml of an alcohol solution, 0.5 mol of fluorine-containing alkyl iodide, 0.8 mol of sodium acrylate, 0.002 mol of a weak organic base catalyst, and 0.002 mol of a polymerization inhibitor are added, and esterification is carried out at a temperature of 160°C and a pressure of 1.0 Mpa for 8 h. After the reaction is completed, filtration and vacuum distillation are performed to obtain fluorine-containing acrylate monomer A for standby; wherein the fluorine-containing alkyl iodide is CF3CF2CF2OCH2CH2I; the reaction formula is as follows:
[0094]
[0095] (4) In a 1000 ml four-necked flask equipped with a stirring motor, a dropping funnel, a spherical condenser, and a thermometer, 300 ml of butyl acetate is added, and after connecting the condenser water, the temperature is raised to 110°C. Then, 25 g of methacrylate isooctyl ester, 5 g of the fluorine-containing acrylate monomer A prepared in step (1), and 0.4 g of an initiator are stirred and uniformly mixed, and then loaded into the dropping funnel to obtain a mixed monomer. The mixed monomer is added dropwise, and the addition is completed within 90 min. Finally, the temperature of the system is maintained at 110°C, and the reaction is carried out for 125 min to obtain a mixture A.
[0096] (5) The remaining 2.5 g of the fluorinated acrylate monomer A prepared in step (1) was loaded into a dropping funnel and added dropwise to the mixture A within 110 min to obtain a mixture B;
[0097] (4) Mixture B was reacted at 110°C for 125 minutes, and the remaining 0.1 g of initiator was added and the reaction was continued for 110 minutes to obtain a fluororesin. The reaction formula is as follows:
[0098]
[0099] Furthermore, the initiator is butyl perbenzoate; the alcohol solution is tert-butyl alcohol; the organic weak base catalyst is triethylamine; and the inhibitor is hydroquinone.
[0100] This embodiment also provides a fully dry lubricant, which has the following components by mass fraction: 2% fluororesin, 1% solid lubricant, 0.5% molybdenum disulfide, 30% ethoxy nonafluorobutyl ether, and the balance being hydrofluoroether, wherein the solid lubricant is PTFE with a median particle size of 1 μm, and the median particle size of molybdenum disulfide is 1 μm.
[0101] Furthermore, the preparation method of the fully dry lubricant includes the following steps: weighing 2g of the above-mentioned fluororesin, 1g of PTFE with a median particle size of 1μm, 0.5g of molybdenum disulfide with a median particle size of 1μm, 30g of ethoxy nonafluorobutyl ether and 66.5g of hydrofluoroether into a container, and dispersing them at a high speed of 10000r / min for 5min to obtain a fully dry lubricant.
[0102] Example 6
[0103] This embodiment provides a fluororesin, the structure of which is shown in Formula II below:
[0104]
[0105]
[0106] The preparation method of the fluororesin comprises the following steps:
[0107] (1) In a 1000 ml autoclave, 200 ml of alcohol solution, 0.5 mol of fluorinated alkyl iodide, 0.8 mol of sodium acrylate, 0.002 mol of an organic weak base catalyst, and 0.002 mol of a polymerization inhibitor were added, and an esterification reaction was carried out at a temperature of 160° C. and a pressure of 1.0 MPa for 8 hours. After the reaction was complete, the mixture was filtered and distilled under reduced pressure to obtain a fluorinated acrylate monomer A for standby use; wherein the fluorinated alkyl iodide was CF3CF2CH2I; the reaction formula was as follows:
[0108]
[0109] (6) In a 1000ml four-necked flask equipped with a stirring motor, a dropping funnel, a spherical condenser and a thermometer, 300ml of butyl acetate was added, and after connecting the condensing water, the temperature was raised to 135℃, then 25g of vinyl ether, 2g of the fluorine-containing propenyl ester monomer A prepared in step (1) and 0.4g of the initiator were stirred and mixed uniformly, and then loaded into the dropping funnel to obtain a mixed monomer; the mixed monomer was started to be added dropwise, and was completed within 90min, and finally the temperature of the system was maintained at 110℃, and reacted for 125min to obtain a mixture A;
[0110] (7) The remaining 2.5g of the fluorine-containing propenyl ester monomer A prepared in step (1) was loaded into the dropping funnel and added dropwise to the mixture A, and was completed within 110min to obtain a mixture B;
[0111] (4) The mixture B was kept at 125℃ for 125min, and then 0.1g of the remaining initiator was added to continue the reaction for 110min to obtain the fluorine resin. The reaction formula is as follows:
[0112]
[0113] Further, the initiator is selected from butyl peroxybenzoate; the alcohol solution is selected from tert-butyl alcohol; the organic weak base catalyst is selected from triethylamine; and the polymerization inhibitor is selected from hydroquinone.
[0114] The embodiment also provides a full-dry type lubricant, which comprises the following components in mass fraction: 2% of the fluorine resin, 1% of the solid lubricant, 20% of trifluorotrichloroethane, and the balance of methoxynonafluorobutyl ether, wherein the solid lubricant is PTFE with a median particle size of 1μm.
[0115] Further, the preparation method of the full-dry type lubricant comprises the following steps: weighing 2g of the fluorine resin, 1g of PTFE with a median particle size of 1μm, 20g of trifluorotrichloroethane and 77g of methoxynonafluorobutyl ether into a container, and dispersing at a high speed of 10000r / min for 5min to obtain the full-dry type lubricant.
[0116] Example 7
[0117] The embodiment provides a fluorine resin, and the structure of the fluorine resin is shown in the following formula II:
[0118]
[0119] The preparation method of the fluorine resin comprises the following steps:
[0120] (1) In a 1000ml high-pressure reactor, 200ml alcohol solution, 0.5mol fluorine-containing alkyl iodine, 0.8mol sodium acrylate, 0.002mol organic weak base catalyst and 0.002mol polymerization inhibitor were added, and esterification reaction was carried out at a temperature of 160℃ and a pressure of 1.0Mpa for 8h. After the reaction was completed, filtration and vacuum distillation were carried out to obtain fluorine-containing propenoic acid ester monomer A for standby use; wherein the fluorine-containing alkyl iodine is CF3CF2CH2I; the reaction formula is as follows:
[0121]
[0122] (8) In a 1000ml four-necked flask equipped with a stirring motor, a dropping funnel, a spherical condenser and a thermometer, 300ml butyl acetate was added, and then the temperature was raised to 135℃ after connecting the condensing water. Then 25g decene, 2g fluorine-containing propenoic acid ester monomer A prepared in step (1) and 0.4g initiator were uniformly stirred and mixed, and then loaded into the dropping funnel to obtain a mixed monomer. The mixed monomer was started to be added dropwise, and the addition was completed within 90min. Finally, the temperature of the system was maintained at 110℃, and the reaction was carried out for 125min to obtain a mixture A.
[0123] (9) The remaining 2.5g fluorine-containing propenoic acid ester monomer A prepared in step (1) was loaded into the dropping funnel and added dropwise to the mixture A, and the addition was completed within 110min to obtain a mixture B.
[0124] (4) The mixture B was reacted at a constant temperature of 125℃ for 125min, and then 0.1g of the remaining initiator was added for further reaction for 110min to obtain a fluororesin. The reaction formula is as follows:
[0125]
[0126] Further, the initiator is selected from butyl peroxybenzoate; the alcohol solution is selected from tert-butyl alcohol; the organic weak base catalyst is selected from triethylamine; and the polymerization inhibitor is selected from hydroquinone.
[0127] The embodiment also provides a full-dry type lubricant, which comprises the following components in mass fraction: 2% of the fluororesin, 1% of the solid lubricant, 20% of trifluorotrichloroethane, and the balance of methoxynonafluorobutyl ether, wherein the solid lubricant is PTFE with a median particle size of 1μm.
[0128] Further, the preparation method of the full-dry type lubricant comprises the following steps: weighing 2g of the fluororesin, 1g of PTFE with a median particle size of 1μm, 20g of trifluorotrichloroethane and 77g of methoxynonafluorobutyl ether into a container, and dispersing at a high speed of 10000r / min for 5min to obtain the full-dry type lubricant.
[0129] Comparative Example 1
[0130] The present comparative example provides a full dry type lubricant with the following components in mass fraction: 3% of fluorine oil, 1% of solid lubricant, 30% of ethoxy nonafluorobutyl ether, and the balance of hexafluoropropylene trimer, wherein the solid lubricant is PTFE with a median particle size of 1 μm, and the fluorine oil is Solvay Y1800.
[0131] Further, the preparation method of the full dry type lubricant is as follows: 3 g of the above fluorine oil, 1 g of PTFE with a median particle size of 1 μm, 30 g of ethoxy nonafluorobutyl ether, and 67 g of hexafluoropropylene trimer are weighed into a container, and high-speed dispersion is performed at 10,000 r / min for 5 min to obtain a dry lubricant.
[0132] Comparative Example 2
[0133] The present comparative example provides a full dry type lubricant without adding fluororesin, and the rest of the content is the same as that of Example 4. That is, the full dry type lubricant has the following components in mass fraction: 1% of solid lubricant, 30% of ethoxy nonafluorobutyl ether, and the balance of hexafluoropropylene trimer, wherein the solid lubricant is PTFE with a median particle size of 1 μm.
[0134] Performance test
[0135] The full dry type lubricants prepared in Examples 1-7 and Comparative Examples 1-2 are subjected to performance determination, and the determined performances are shown in the following table:
[0136]
[0137]
[0138] Among them, the reciprocating friction coefficient test is tested by a reciprocating friction and wear tester. The prepared lubricant is coated on an ABS plate, and the test is started after the lubricant is completely dried for 30 min. The ABS plate is fixed on the workbench of the tester, and a φ10 mm stainless steel ball is installed on the clamp, vertically aligned with the center position of the ABS plate. The test parameters are set as follows: load 2 kg, stroke 50 mm, reciprocation 2000 times, speed 2000 mm / min, and the dynamic friction coefficient is tested.
[0139] The adhesion test is to coat the prepared lubricant on the plastic surface, and the test is started after the lubricant is completely dried for 30 min. Then, the hand is touched to check whether it is sticky.
[0140] The fluororesin of the present invention can be used to prepare a fully dry lubricant. The fluororesin has excellent oil solubility, high and low temperature resistance, anti-wear, and lubricating properties. The resulting fully dry lubricant has excellent non-stick, anti-wear, and lubricating properties. Furthermore, the resulting fully dry lubricant exhibits excellent lubrication, anti-wear, and high-temperature resistance. Furthermore, after being applied to a substrate and completely dried, the fully dry lubricant will not exhibit oil film adhesion or migration contamination. This effectively addresses the issues of poor compatibility with the substrates and poor lubrication and anti-wear properties of existing dry film lubricants. The preparation method of the fluororesin is simple to operate, easy to control, and produces stable product quality with superior overall performance, making it suitable for large-scale industrial production.
[0141] The above embodiments are preferred implementation schemes of the present invention. In addition, the present invention can also be implemented in other ways. Any obvious replacement without departing from the concept of the present invention is within the scope of protection of the present invention.
Claims
1. A fluororesin, characterized in that: The molecular structure of the fluororesin is shown in Formula I, Formula II, Formula III, Formula IV or Formula V: Wherein, R1 is -H, one of the molecular structural formula VI, molecular structural formula VII or molecular structural formula VIII: Where n is a natural number from 1 to 100; R2, R3 are one of the following molecular structural formulas IX or X: Wherein n and m are natural numbers ranging from 1 to 100.
2. A method for preparing the fluororesin according to claim 1, characterized in that: The steps include: (1) Initiator and functional monomer are added to a four-necked flask equipped with a stirring motor, a dropping funnel, a spherical condenser, and a thermometer. Butyl acetate is added and the temperature is raised to the polymerization temperature. The initiator and functional monomer are then stirred and mixed uniformly and then loaded into the dropping funnel to obtain a mixed monomer. The mixed monomer is added dropwise and the addition is completed within 60 to 120 minutes. Finally, the system temperature is maintained at 70 to 150° C. and the reaction is carried out for 100 to 150 minutes to obtain a mixture A. (2) The remaining functional monomer is loaded into a dropping funnel and added dropwise to mixture A within 100 to 120 minutes to obtain mixture B; (3) The mixture B is reacted at a constant temperature of 70-150° C. for 100-150 minutes, and then the remaining initiator is added and the reaction is continued for 100-120 minutes to obtain a fluororesin.
3. The method for preparing a fluororesin according to claim 2, wherein: In step (1), the functional monomer is at least one of an olefin, an unsaturated ether, an alkyl acrylate or a fluorine-containing acrylate monomer.
4. The method for preparing a fluororesin according to claim 2, wherein: The olefin includes but is not limited to decaene; the unsaturated ether includes but is not limited to vinyl ethyl ether; the alkyl acrylate includes but is not limited to at least one of methyl methacrylate or isooctyl methacrylate; the fluorine-containing acrylate monomer includes but is not limited to at least one of 2-(trifluoromethyl)methyl acrylate, trifluoroethyl acrylate or fluorine-containing acrylate monomer A.
5. The method for preparing a fluororesin according to claim 2, wherein: The preparation method of the fluorine-containing acrylate monomer A comprises the following steps: adding a fluorine-containing alkyl iodide, an acrylate, an organic weak base catalyst, a polymerization inhibitor and an alcohol solution into a reaction vessel, carrying out an esterification reaction at a temperature of 150 to 200° C. and a pressure of 0.5 to 1.5 MPa for 6 to 10 hours, filtering after the reaction is complete, and performing reduced pressure distillation to obtain the fluorine-containing acrylate monomer A.
6. The method for preparing a fluororesin according to claim 2, wherein: The molar ratio of the fluorinated alkyl iodide, acrylate, organic weak base catalyst and polymerization inhibitor is 1:1-2:0.002-0.1:0.001-0.1; the amount of the alcohol solvent is 5-20 times the mass of the fluorinated alkyl iodide.
7. The method for preparing a fluororesin according to claim 2, wherein: The fluorinated alkyl iodide is CF3(CF2) n O(CH2) m I or CF3 (CF2) n (CH2) m At least one of I, wherein n and m are natural numbers from 1 to 100.
8. A fully dry lubricant, characterized in that: The lubricant comprises the following components in mass fractions: 1%-10% of the fluororesin according to claim 1, 0.5%-10% of a solid lubricant, and the balance being a fluorine solvent.
9. The fully dry lubricant according to claim 8, characterized in that: The solid lubricant is at least one of PTFE with a median particle size of 0.5 to 50 μm or molybdenum disulfide with a median particle size of 0.5 to 50 μm.
10. The fully dry lubricant according to claim 8, characterized in that: The fluorine solvent is at least one of trifluorotrichloroethane, hydrofluoroether, perfluorobutyl cyclic ether, pentafluorobutane, hexafluoropropylene trimer, hexafluoropropylene dimer, perfluorocyclohexane, perfluorohexane, perfluoromethylhexane, ethoxy nonafluorobutyl ether or methoxy nonafluorobutyl ether.