CN111978494A - Super-hydrophobic polyimide material based on atom transfer radical polymerization and preparation method thereof - Google Patents
Super-hydrophobic polyimide material based on atom transfer radical polymerization and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of polyimide superhydrophobicity and discloses a superhydrophobic polyimide material based on atom transfer radical polymerization, wherein 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane containing phenolic hydroxyl and a dianhydride monomer are subjected to copolymerization and thermal imidization treatment to obtain polyimide containing hydroxyl, the hydroxyl reacts with 2-bromoisobutyryl bromide to obtain 2-bromoisobutyryl esterified polyimide, the 2-bromoisobutyryl esterified polyimide is used as a macromolecular initiator, bromine atoms are used as an initiation active center, and alkenyl nano SiO is initiated by atom transfer radical polymerization2And the alkenyl of the perfluoroacrylate are subjected to free radical copolymerization on the molecular chain of the polyimide, and the polyimide contains-CF3Radical, and C-F bond, remarkably reduce the surface energy of the material, and nano SiO2Uniformly modified by chemical bond modificationA layer of uniform nano-papillary structure with high roughness is formed on the surface of the polyimide, and the polyimide is endowed with special super-hydrophobic performance under the synergistic action.
Description
Technical Field
The invention relates to the field of polyimide superhydrophobicity, in particular to a superhydrophobic polyimide material based on atom transfer radical polymerization and a preparation method thereof.
Background
The wettability is an important physical and chemical property of the solid surface, the wettability is influenced by chemical components and a surface geometric microstructure, the wettability is characterized by a contact angle of liquid on the solid surface, when the water contact angle is between 0 and 90 degrees, the solid surface shows hydrophilicity, and when the water contact angle exceeds 150 degrees, the super-hydrophobicity is shown, the super-hydrophobic material is a novel functional material, has the characteristics of special self-cleaning, water and rain resistance, pollution resistance, corrosion resistance and the like, and has a wide application prospect.
The product mainly comprises polyimide films, coatings, fibers, plastics, adhesives and the like, and is widely applied to the fields of separation membranes, microelectronics, aerospace and the like, but the traditional polyimide material does not have super-hydrophobic performance, and the conventional modification method for the polyimide mainly comprises structural modification, blending modification, copolymerization modification, filling modification and the like in order to further improve the performance of the polyimide and expand the application field.
The atom transfer free radical polymerization is an effective way for realizing active polymerization, can synthesize polymers with controllable molecular weight and narrow molecular weight distribution, realizes the active controllable free radical polymerization of various monomers, is a novel high-efficiency high-molecular organic polymerization method,
technical problem to be solved
Aiming at the defects of the prior art, the invention provides a super-hydrophobic polyimide material based on atom transfer radical polymerization and a preparation method thereof, and solves the problem that the traditional polyimide material does not have super-hydrophobic performance.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a super-hydrophobic polyimide material based on atom transfer radical polymerization is prepared by the following steps:
(1) adding a mixed solvent of distilled water and ethanol into a reaction bottle in a volume ratio of 1:30-50, and adding nano SiO2Uniformly dispersing by ultrasonic wave, adding vinyl silane coupling agent, uniformly stirring at 80-100 deg.C for 6-12h, filtering to removeSolvent, washing by using distilled water and ethanol and drying to prepare the alkenyl nano SiO2。
(2) Adding an N-methyl pyrrolidone solvent, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and a dianhydride monomer into a reaction bottle in an argon atmosphere, placing the mixture into a constant temperature oil bath instrument, reacting for 12-24h at 20-40 ℃, adding a catalyst pyridine and a dehydrating agent, heating to 100 ℃ and 120 ℃, uniformly stirring for reacting for 4-10h, cooling the solution in an ice water bath, adding distilled water until a large amount of precipitate is separated out, filtering out the solvent, washing with distilled water and drying, and performing thermal imidization treatment to obtain the hydroxyl-containing polyimide.
(3) Adding pyridine as a solvent and polyimide containing hydroxyl into a reaction bottle, stirring uniformly, slowly dropwise adding 2-bromoisobutyryl bromide, reacting at-5 ℃ for 2-3h, heating to 20-30 ℃, stirring at a constant speed for reaction for 10-20h, cooling the solution in an ice water bath, adding a methanol solvent until a large amount of precipitate is separated out, filtering out the solvent, washing with methanol and drying to prepare the 2-bromoisobutyryl esterified polyimide.
(4) Adding N, N-dimethylformamide solvent, 2-bromoisobutyryl esterified polyimide and alkenyl nano SiO into a reaction bottle in argon atmosphere2And (2) uniformly dispersing the perfluoro acrylate by ultrasonic, adding an accelerant 2, 2-bipyridine, a catalyst cuprous chloride and a cocatalyst copper chloride, carrying out liquid nitrogen quick freezing-unfreezing treatment for 3-5 times, reacting for 10-20h at 55-75 ℃, carrying out liquid nitrogen quick freezing, adding a distilled aqueous solvent in an air atmosphere, carrying out quenching reaction, filtering out the solvent, washing by using distilled water and ethanol, and drying to prepare the super-hydrophobic polyimide material based on atom transfer radical polymerization.
Preferably, the vinyl silane coupling agent in the step (1) is any one of vinyl trimethoxy silane and vinyl triethoxy silane, and the nano SiO2The mass ratio of (A) to (B) is 10-30: 100.
Preferably, the dianhydride monomer in the step (2) is any one of 3,3',4,4' -biphenyl tetracarboxylic dianhydride or pyromellitic anhydride or 3,3',4,4' -benzophenone tetracarboxylic dianhydride, and the mass ratio of the 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane to the dianhydride monomer, pyridine to acetic anhydride is 100:60-90:220-300: 500-600.
Preferably, the constant temperature oil bath appearance includes the oil bath pot, and oil bath pot below is provided with the constant temperature heating pipe, the inside both sides fixedly connected with screw rod of oil bath pot, screw rod swing joint have the guide pulley, the inside swing joint of guide pulley has the support lever, and bracing piece swing joint has the fixation clamp, and fixation clamp swing joint has the reaction bottle.
Preferably, the mass ratio of the hydroxyl polyimide to the 2-bromoisobutyryl bromide in the step (3) is 100: 200-250.
Preferably, the tridecyl acrylate or 1H, 1H-perfluorooctyl methacrylate or perfluoroacrylate in the step (4) is any one of perfluorooctyl ethyl acrylate or perfluorooctyl ethyl methacrylate.
Preferably, in the step (4), 2-bromoisobutyryl esterified polyimide and alkenyl nano SiO are adopted2The mass ratio of the perfluoroacrylate to the 2, 2-bipyridine to the copper chloride to the cuprous chloride is 100:5-15:2-8:25-35:10-15: 0.65-1.
(III) advantageous technical effects
Compared with the prior art, the invention has the following experimental principles and beneficial technical effects:
the super-hydrophobic polyimide material based on atom transfer radical polymerization is prepared by using 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane containing phenolic hydroxyl as a diamine monomer, copolymerizing the diamine monomer with a dianhydride monomer and carrying out thermal imidization treatment to obtain polyimide with an aromatic ring containing hydroxyl, carrying out substitution reaction on the hydroxyl and an acyl bromide group of 2-bromoisobutyryl bromide in a pyridine system to obtain 2-bromoisobutyryl esterified polyimide, using the 2-bromoisobutyryl esterified polyimide as a macromolecular initiator and using a bromine atom as an initiation active center, and initiating alkenyl nano SiO by an atom transfer radical polymerization method2And the alkenyl group of the perfluoroacrylate is subjected to radical copolymerization on the polyimide molecular chain.
The super-hydrophobic polyimide material based on atom transfer radical polymerization is prepared from 2, 2-bis (3-amino-4-hydroxyphenyl) hexa-in polyimideThe fluoropropane contains-CF3The radical perfluoroacrylate contains rich C-F bonds, can obviously reduce the surface energy of the polyimide material, and the nano SiO2The surface of the polyimide is uniformly modified through chemical bond modification, so that the nano SiO is improved2The nano-emulsion is dispersed in polyimide, forms a layer of uniform nano-emulsion-like structure with high roughness, and endows the polyimide with special super-hydrophobic performance under the synergistic action.
Drawings
FIG. 1 is a schematic front view of a constant temperature oil bath apparatus;
FIG. 2 is a schematic top view of a thermostatic heating tube;
FIG. 3 is a schematic view of a screw configuration;
FIG. 4 is a schematic view of idler adjustment.
1-constant temperature oil bath instrument; 2-oil bath pan; 3-heating a pipe at constant temperature; 4-screw rod; 5-a guide wheel; 6-support rod; 7-a fixing clip; 8-reaction flask.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a super-hydrophobic polyimide material based on atom transfer radical polymerization is prepared by the following steps:
(1) adding a mixed solvent of distilled water and ethanol into a reaction bottle in a volume ratio of 1:30-50, and adding nano SiO2Adding vinyl silane coupling agent after ultrasonic dispersion, wherein the vinyl silane coupling agent is any one of vinyl trimethoxy silane or vinyl triethoxy silane and nano SiO2The mass ratio of (1) to (10-30: 100), reacting at 80-100 deg.C under stirring at constant speed for 6-12h, filtering to remove solvent, washing with distilled water and ethanol, and drying to obtain alkenyl nano SiO2。
(2) Adding N-methyl pyrrolidone solvent, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and dianhydride monomer into a reaction bottle in argon atmosphere, wherein the dianhydride monomer is any one of 3,3',4,4' -biphenyl tetracarboxylic dianhydride or pyromellitic anhydride or 3,3',4,4' -benzophenone tetracarboxylic dianhydride, placing the mixture into a constant temperature oil bath instrument, the constant temperature oil bath instrument comprises an oil bath pot, a constant temperature heating pipe is arranged below the oil bath pot, two sides in the oil bath pot are fixedly connected with screw rods, the screw rods are movably connected with guide wheels, the inner parts of the guide wheels are movably connected with supporting rods, the supporting rods are movably connected with fixing clamps, the fixing clamps are movably connected with the reaction bottle, reacting for 12-24h at the temperature of 20-40 ℃, adding catalyst pyridine and dehydrating agent acetic anhydride, wherein 2, the mass ratio of the 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane to the dianhydride monomer, the pyridine to the acetic anhydride is 100:60-90: 220: 300: 500-.
(3) Adding pyridine serving as a solvent and polyimide containing hydroxyl into a reaction bottle, uniformly stirring, slowly dropwise adding 2-bromoisobutyryl bromide, wherein the mass ratio of the pyridine to the polyimide is 100:200-250, reacting at-5 ℃ for 2-3h, heating to 20-30 ℃, uniformly stirring for reacting for 10-20h, cooling the solution in an ice water bath, adding a methanol solvent until a large amount of precipitate is separated out, filtering out the solvent, washing with methanol and drying to obtain the 2-bromoisobutyryl esterified polyimide.
(4) Adding N, N-dimethylformamide solvent, 2-bromoisobutyryl esterified polyimide and alkenyl nano SiO into a reaction bottle in argon atmosphere2The preparation method comprises the following steps of preparing perfluoroacrylate, wherein the perfluoroacrylate is tridecyl octyl acrylate or methacrylic acid-1H, 1H-perfluorooctyl acrylate or the perfluoroacrylate is perfluorooctyl ethyl acrylate or perfluorooctyl ethyl methacrylate, adding an accelerant 2, 2-bipyridyl, a catalyst cuprous chloride and a cocatalyst cupric chloride after uniform ultrasonic dispersion, and controlling 2-bromoisobutyryl esterified polyimide and alkenyl nano SiO2The mass ratio of the perfluoroacrylic ester to the 2, 2-bipyridine to the copper chloride to the cuprous chloride is 100:5-15:2-8:25-35:10-15:0.65-1, the mixture is subjected to liquid nitrogen quick freezing-unfreezing treatment for 3-5 times, the mixture is reacted for 10-20 hours at the temperature of 55-75 ℃, the mixture is subjected to liquid nitrogen quick freezing, a distilled water solvent is added into the mixture in the air atmosphere for quenching reaction, the solvent is filtered out, the mixture is washed by distilled water and ethanol and dried, and the free radical polymerization based on atom transfer is preparedBased on a polymerized super-hydrophobic polyimide material.
Example 1
(1) Adding a mixed solvent of distilled water and ethanol into a reaction bottle in a volume ratio of 1:30, and adding nano SiO2Adding vinyl trimethoxy silane as coupling agent and nano SiO after ultrasonic dispersion2The mass ratio of (1) to (100) is 10:100, the mixture is stirred at a constant speed and reacted for 6 hours at a temperature of 80 ℃, the solvent is removed by filtration, and the mixture is washed by distilled water and ethanol and dried to prepare the alkenyl nano SiO2。
(2) Adding N-methyl pyrrolidone solvent, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and dianhydride monomer 3,3',4,4' -biphenyl tetracarboxylic dianhydride into a reaction bottle in an argon atmosphere, placing the reaction bottle in a constant-temperature oil bath instrument, wherein the constant-temperature oil bath instrument comprises an oil bath pot, a constant-temperature heating pipe is arranged below the oil bath pot, two sides in the oil bath pot are fixedly connected with screws, the screws are movably connected with guide wheels, the inner parts of the guide wheels are movably connected with supporting rods, the supporting rods are movably connected with fixing clamps, the fixing clamps are movably connected with the reaction bottle, reacting for 12 hours at the temperature of 20 ℃, adding catalyst pyridine and acetic anhydride, wherein 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3',4,4' -biphenyl tetracarboxylic dianhydride, dianhydride, Heating pyridine and acetic anhydride to 100:60:220:500 by mass ratio, uniformly stirring for reaction for 4 hours, cooling the solution in an ice water bath, adding distilled water until a large amount of precipitate is separated out, filtering out the solvent, washing with distilled water, drying, and performing thermal imidization treatment to obtain the hydroxyl-containing polyimide.
(3) Adding pyridine serving as a solvent and polyimide containing hydroxyl into a reaction bottle, uniformly stirring, slowly dropwise adding 2-bromoisobutyryl bromide with the mass ratio of 100:200, reacting for 2 hours at 5 ℃, heating to 20 ℃, uniformly stirring for reaction for 10 hours, cooling the solution in an ice water bath, adding a methanol solvent until a large amount of precipitate is separated out, filtering out the solvent, washing with methanol and drying to prepare the 2-bromoisobutyryl esterified polyimide.
(4) Adding N, N-dimethylformamide solvent, 2-bromoisobutyryl esterified polyimide and alkenyl nano SiO into a reaction bottle in argon atmosphere2PerfluoropropeneThe acid ester tridecafluorooctyl acrylate is ultrasonically dispersed uniformly, and then the accelerant 2, 2-bipyridine, the catalyst cuprous chloride and the cocatalyst cupric chloride are added to control the 2-bromoisobutyryl esterified polyimide and the alkenyl nano SiO2The mass ratio of the tridecyl acrylate to the 2, 2-bipyridyl acrylate to the copper chloride is 100:5:2:25:10:0.65, the mixture is subjected to liquid nitrogen quick freezing-unfreezing treatment for 3 times, reacted at 55 ℃ for 10 hours, quickly frozen by liquid nitrogen, added with distilled water solvent in air atmosphere for quenching reaction, filtered to remove the solvent, washed by distilled water and ethanol and dried to prepare the super-hydrophobic polyimide material 1 based on atom transfer radical polymerization.
Example 2
(1) Adding a mixed solvent of distilled water and ethanol into a reaction bottle in a volume ratio of 1:35, and adding nano SiO2Adding vinyl triethoxysilane as coupling agent and nano SiO after ultrasonic dispersion2The mass ratio of (1) is 15:100, the reaction is carried out for 8 hours at 100 ℃ with uniform stirring, the solvent is removed by filtration, and the alkenyl nano SiO is prepared by washing and drying with distilled water and ethanol2。
(2) Adding N-methyl pyrrolidone solvent, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and dianhydride monomer pyromellitic dianhydride into a reaction bottle in an argon atmosphere, placing the reaction bottle in a constant-temperature oil bath instrument, wherein the constant-temperature oil bath instrument comprises an oil bath pot, a constant-temperature heating pipe is arranged below the oil bath pot, two sides in the oil bath pot are fixedly connected with screws, the screws are movably connected with guide wheels, the inner parts of the guide wheels are movably connected with supporting rods, the supporting rods are movably connected with fixing clamps, the fixing clamps are movably connected with the reaction bottle, reacting for 15 hours at the temperature of 30 ℃, adding catalyst pyridine and acetic anhydride, wherein the mass ratio of the 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, pyromellitic dianhydride, pyridine and acetic anhydride is 100:70:250:520, heating to 120 ℃, stirring at a constant speed for reaction for 4 hours, cooling the solution in an ice-water bath, adding distilled water until a large amount of precipitate is separated out, filtering out the solvent, washing with distilled water, drying, and performing thermal imidization treatment to obtain the hydroxyl-containing polyimide.
(3) Adding pyridine serving as a solvent and polyimide containing hydroxyl into a reaction bottle, uniformly stirring, slowly dropwise adding 2-bromoisobutyryl bromide, wherein the mass ratio of the two is 100:220, reacting for 2 hours at 0 ℃, heating to 30 ℃, uniformly stirring and reacting for 15 hours, cooling the solution in an ice water bath, adding a methanol solvent until a large amount of precipitate is separated out, filtering out the solvent, washing with methanol and drying to prepare the 2-bromoisobutyryl esterified polyimide.
(4) Adding N, N-dimethylformamide solvent, 2-bromoisobutyryl esterified polyimide and alkenyl nano SiO into a reaction bottle in argon atmosphere2The perfluoroacrylate methacrylic acid-1H, 1H-perfluorooctyl ester is ultrasonically dispersed uniformly, and then the promoter 2, 2-bipyridine, the catalyst cuprous chloride and the cocatalyst cupric chloride are added to control the 2-bromoisobutyryl esterified polyimide and the alkenyl nano SiO21H, 1H-perfluorooctyl methacrylate, 2-bipyridine, copper chloride and cuprous chloride in a mass ratio of 100:8:4:28:11:0.72, subjected to liquid nitrogen quick freezing-thawing treatment for 5 times, reacted at 75 ℃ for 20 hours, subjected to liquid nitrogen quick freezing, quenched in air by adding a distilled water solvent, filtered to remove the solvent, washed with distilled water and ethanol, and dried to prepare the superhydrophobic polyimide material 2 based on atom transfer radical polymerization.
Example 3
(1) Adding a mixed solvent of distilled water and ethanol into a reaction bottle in a volume ratio of 1:43, and adding nano SiO2Adding vinyl triethoxysilane as coupling agent and nano SiO after ultrasonic dispersion2The mass ratio of (1) to (100) is 22:100, the mixture is stirred at a constant speed for reaction for 10 hours at the temperature of 90 ℃, the solvent is removed by filtration, and the mixture is washed by distilled water and ethanol and dried to prepare the alkenyl nano SiO2。
(2) Adding N-methylpyrrolidone solvent, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and dianhydride monomer 3,3',4,4' -benzophenone tetracarboxylic dianhydride into a reaction bottle in an argon atmosphere, placing the reaction bottle in a constant-temperature oil bath instrument, wherein the constant-temperature oil bath instrument comprises an oil bath pot, a constant-temperature heating pipe is arranged below the oil bath pot, two sides in the oil bath pot are fixedly connected with screws, the screws are movably connected with guide wheels, the inner parts of the guide wheels are movably connected with supporting rods, the supporting rods are movably connected with fixing clamps, the fixing clamps are movably connected with the reaction bottle, reacting for 18h at the temperature of 30 ℃, adding catalyst pyridine and acetic anhydride, wherein the mass ratio of 2, 2-dehydrating agent bis (3-amino-4-hydroxyphenyl) hexafluoropropane to dianhydride monomer to pyridine to acetic anhydride is 100:80:270:560, heating to 110 ℃, stirring at a constant speed for reaction for 8 hours, cooling the solution in an ice-water bath, adding distilled water until a large amount of precipitate is separated out, filtering out the solvent, washing with distilled water, drying, and performing thermal imidization treatment to obtain the hydroxyl-containing polyimide.
(3) Adding pyridine serving as a solvent and polyimide containing hydroxyl into a reaction bottle, uniformly stirring, slowly dropwise adding 2-bromoisobutyryl bromide, wherein the mass ratio of the two is 100:235, reacting for 2.5 hours at 0 ℃, heating to 25 ℃, uniformly stirring and reacting for 15 hours, cooling the solution in an ice water bath, adding a methanol solvent until a large amount of precipitate is separated out, filtering the solvent, washing with methanol and drying to prepare the 2-bromoisobutyryl esterified polyimide.
(4) Adding N, N-dimethylformamide solvent, 2-bromoisobutyryl esterified polyimide and alkenyl nano SiO into a reaction bottle in argon atmosphere2The perfluoro acrylate is perfluoro octyl ethyl acrylate, after ultrasonic dispersion is uniform, promoter 2, 2-bipyridine, catalyst cuprous chloride and cocatalyst cupric chloride are added, and 2-bromoisobutyryl esterified polyimide and alkenyl nano SiO are controlled2And the perfluorinated acrylate is perfluorooctyl ethyl acrylate, 2-bipyridyl, copper chloride and cuprous chloride in a mass ratio of 100:12:6:21:13:0.85, and is subjected to quick freezing-unfreezing treatment by liquid nitrogen for 4 times, reaction is carried out for 10-20h at 65 ℃, the reaction is quenched by liquid nitrogen and adding a distilled water solvent in an air atmosphere, the solvent is filtered out, and the mixture is washed by distilled water and ethanol and dried to prepare the super-hydrophobic polyimide material 3 based on atom transfer radical polymerization.
Example 4
(1) Adding a mixed solvent of distilled water and ethanol into a reaction bottle in a volume ratio of 1:50, and adding nano SiO2Adding vinyl trimethoxy silane as coupling agent and nano SiO after ultrasonic dispersion2The mass ratio of (1) to (100) is 30:100, the mixture is stirred at a constant speed for reaction for 12 hours at the temperature of 100 ℃, the solvent is removed by filtration, and the mixture is washed by distilled water and ethanol and dried to prepare the alkenyl nano SiO2。
(2) Adding N-methyl pyrrolidone solvent, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and dianhydride monomer into a reaction bottle in an argon atmosphere, wherein the dianhydride monomer pyromellitic dianhydride is placed in a constant-temperature oil bath instrument which comprises an oil bath pot, a constant-temperature heating pipe is arranged below the oil bath pot, two sides in the oil bath pot are fixedly connected with screws, the screws are movably connected with guide wheels, the inner part of each guide wheel is movably connected with a supporting rod, the supporting rod is movably connected with a fixing clamp, the fixing clamp is movably connected with the reaction bottle, reacting is carried out for 24 hours at the temperature of 40 ℃, then adding catalyst pyridine and dehydrating agent acetic anhydride, wherein the mass ratio of the 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, the pyromellitic dianhydride, the pyridine and the acetic anhydride is 100:90:300:600, heating to 120 ℃, uniformly stirring for reaction for 10 hours, cooling the solution in ice-water bath, adding distilled water until a large amount of precipitate is separated out, filtering out the solvent, washing with distilled water, drying, and performing thermal imidization treatment to obtain the hydroxyl-containing polyimide.
(3) Adding pyridine serving as a solvent and polyimide containing hydroxyl into a reaction bottle, uniformly stirring, slowly dropwise adding 2-bromoisobutyryl bromide, wherein the mass ratio of the pyridine to the polyimide is 100:250, reacting for 3 hours at-5 ℃, heating to 30 ℃, uniformly stirring and reacting for 20 hours, cooling the solution in an ice water bath, adding a methanol solvent until a large amount of precipitate is separated out, filtering the solvent, washing with methanol and drying to prepare the 2-bromoisobutyryl esterified polyimide.
(4) Adding N, N-dimethylformamide solvent, 2-bromoisobutyryl esterified polyimide and alkenyl nano SiO into a reaction bottle in argon atmosphere2The perfluorooctyl ethyl methacrylate is ultrasonically dispersed uniformly, then the promoter 2, 2-bipyridine, the catalyst cuprous chloride and the cocatalyst cupric chloride are added, and the 2-bromoisobutyryl esterified polyimide and the alkenyl nano SiO are controlled2The mass ratio of the perfluorooctyl ethyl methacrylate to the 2, 2-bipyridine to the copper chloride to the cuprous chloride is 100:15:8:35:151, performing quick freezing-unfreezing treatment for 5 times by liquid nitrogen, reacting for 20 hours at 75 ℃, quickly freezing by liquid nitrogen, adding a distilled water solvent into the mixture in an air atmosphere to quench the reaction, filtering the solvent, washing the mixture by using distilled water and ethanol, and drying the mixture to prepare the super-hydrophobic polyimide material 4 based on atom transfer radical polymerization.
Comparative example 1
(1) Adding a mixed solvent of distilled water and ethanol into a reaction bottle in a volume ratio of 1:50, and adding nano SiO2Adding vinyl triethoxysilane as coupling agent and nano SiO after ultrasonic dispersion2The mass ratio of (1) is 6:100, the mixture is stirred at a constant speed at 100 ℃ for reaction for 12 hours, the solvent is removed by filtration, and the alkenyl nano SiO is prepared by washing and drying the mixture by using distilled water and ethanol2。
(2) Adding N-methyl pyrrolidone solvent, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and dianhydride monomer 3,3',4,4' -biphenyl tetracarboxylic dianhydride into a reaction bottle in an argon atmosphere, placing the reaction bottle in a constant-temperature oil bath instrument, wherein the constant-temperature oil bath instrument comprises an oil bath pot, a constant-temperature heating pipe is arranged below the oil bath pot, two sides in the oil bath pot are fixedly connected with screws, the screws are movably connected with guide wheels, the inner parts of the guide wheels are movably connected with supporting rods, the supporting rods are movably connected with fixing clamps, the fixing clamps are movably connected with the reaction bottle, reacting for 15 hours at the temperature of 30 ℃, adding catalyst pyridine and acetic anhydride, wherein 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3',4,4' -biphenyl tetracarboxylic dianhydride, dianhydride, Heating pyridine and acetic anhydride to 110: 180:450 by mass ratio, uniformly stirring for reacting for 8 hours, cooling the solution in an ice water bath, adding distilled water until a large amount of precipitate is separated out, filtering out the solvent, washing with distilled water, drying, and performing thermal imidization treatment to obtain the hydroxyl-containing polyimide.
(3) Adding pyridine serving as a solvent and polyimide containing hydroxyl into a reaction bottle, uniformly stirring, slowly dropwise adding 2-bromoisobutyryl bromide, wherein the mass ratio of the two is 100:180, reacting at 0 ℃ for 3 hours, heating to 20 ℃, uniformly stirring and reacting for 20 hours, cooling the solution in an ice water bath, adding a methanol solvent until a large amount of precipitate is separated out, filtering the solvent, washing with methanol and drying to prepare the 2-bromoisobutyryl esterified polyimide.
(4) Adding N, N-dimethylformamide solvent, 2-bromoisobutyryl esterified polyimide and alkenyl nano SiO into a reaction bottle in argon atmosphere2The perfluoroacrylate methacrylic acid-1H, 1H-perfluorooctyl ester is ultrasonically dispersed uniformly, and then the promoter 2, 2-bipyridine, the catalyst cuprous chloride and the cocatalyst cupric chloride are added to control the 2-bromoisobutyryl esterified polyimide and the alkenyl nano SiO21H, 1H-perfluorooctyl methacrylate, 2-bipyridine, copper chloride and cuprous chloride in a mass ratio of 100:3:1:20:8:0.5, subjected to rapid freezing-thawing treatment by liquid nitrogen for 5 times, reacted at 65 ℃ for 12 hours, rapidly frozen by liquid nitrogen, quenched in air by adding a distilled water solvent, filtered off the solvent, washed with distilled water and ethanol, and dried to prepare a superhydrophobic polyimide material based on atom transfer radical polymerization, comparative example 1.
The experimental example and the comparative example were tested for water contact of the super-hydrophobic polyimide materials based on atom transfer radical polymerization using JC2000DM surface contact angle measuring instrument, with the test standard GB/T30693-2014.
| Testing | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
| Water contact angle | 150.4° | 153.8° | 157.2° | 151.7° | 120.8° |
Claims (7)
1. A super-hydrophobic polyimide material based on atom transfer radical polymerization is characterized in that: the preparation method of the super-hydrophobic polyimide material based on atom transfer radical polymerization comprises the following steps:
(1) adding nano SiO into the mixed solvent of distilled water and ethanol with the volume ratio of 1:30-502Uniformly dispersing by ultrasonic, adding vinyl silane coupling agent, stirring and reacting for 6-12h at 80-100 ℃, filtering, washing and drying to obtain the alkenyl nano SiO2；
(2) Adding 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and a dianhydride monomer into an N-methylpyrrolidone solvent in an argon atmosphere, placing the mixture into a constant temperature oil bath instrument, reacting for 12 to 24 hours at the temperature of between 20 and 40 ℃, adding a catalyst pyridine and a dehydrating agent acetic anhydride, heating to the temperature of 100 ℃ and 120 ℃, reacting for 4 to 10 hours, cooling, precipitating, filtering, washing and drying, and performing thermal imidization treatment to prepare polyimide containing hydroxyl;
(3) adding polyimide containing hydroxyl into a pyridine solvent, stirring uniformly, slowly dropwise adding 2-bromoisobutyryl bromide, reacting for 2-3h at-5 to 5 ℃, heating to 20-30 ℃, stirring at a constant speed for reacting for 10-20h, cooling the solution in an ice water bath, adding a methanol solvent until a large amount of precipitate is separated out, filtering out the solvent, washing with methanol and drying to prepare 2-bromoisobutyryl esterified polyimide;
(4) adding N, N-dimethylformamide solvent, 2-bromoisobutyryl esterified polyimide and alkenyl nano SiO into a reaction bottle in argon atmosphere2Dispersing perfluoro acrylate by ultrasonic wave, adding 2, 2-dipyridine as promoter and catalyst for chlorinationCuprous and a cocatalyst copper chloride are subjected to liquid nitrogen quick freezing-unfreezing treatment for 3-5 times, the reaction is carried out for 10-20h at the temperature of 55-75 ℃, the reaction is carried out by quick freezing through liquid nitrogen, a distilled water solvent is added in the air atmosphere for quenching reaction, and the super-hydrophobic polyimide material based on atom transfer radical polymerization is prepared by filtering, washing and drying.
2. The super-hydrophobic polyimide material based on atom transfer radical polymerization as claimed in claim 1, wherein: the vinyl silane coupling agent in the step (1) is any one of vinyl trimethoxy silane or vinyl triethoxy silane and nano SiO2The mass ratio of (A) to (B) is 10-30: 100.
3. The super-hydrophobic polyimide material based on atom transfer radical polymerization as claimed in claim 1, wherein: the dianhydride monomer in the step (2) is any one of 3,3',4,4' -biphenyl tetracarboxylic dianhydride or pyromellitic anhydride or 3,3',4,4' -benzophenone tetracarboxylic dianhydride, and the mass ratio of the 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane to the dianhydride monomer, the pyridine to the acetic anhydride is 100:60-90:220-300: 500-600.
4. The super-hydrophobic polyimide material based on atom transfer radical polymerization as claimed in claim 1, wherein: constant temperature oil bath appearance includes the oil bath pot, and oil bath pot below is provided with the constant temperature heating pipe, the inside both sides fixedly connected with screw rod of oil bath pot, screw rod swing joint have the guide pulley, the inside swing joint of guide pulley has the support lever, bracing piece swing joint has the fixation clamp, fixation clamp swing joint has the reaction bottle.
5. The super-hydrophobic polyimide material based on atom transfer radical polymerization as claimed in claim 1, wherein: the mass ratio of the hydroxyl polyimide to the 2-bromoisobutyryl bromide in the step (3) is 100: 200-250.
6. The super-hydrophobic polyimide material based on atom transfer radical polymerization as claimed in claim 1, wherein: in the step (4), the tridecyl octyl acrylate or the methacrylic acid-1H, 1H-perfluorooctyl acrylate or the perfluoroacrylate is any one of perfluorooctyl ethyl acrylate or perfluorooctyl ethyl methacrylate.
7. The super-hydrophobic polyimide material based on atom transfer radical polymerization as claimed in claim 1, wherein: in the step (4), 2-bromoisobutyryl esterified polyimide and alkenyl nano SiO2The mass ratio of the perfluoroacrylate to the 2, 2-bipyridine to the copper chloride to the cuprous chloride is 100:5-15:2-8:25-35:10-15: 0.65-1.
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| CN112552817A (en) * | 2020-12-10 | 2021-03-26 | 桐乡市鑫皓科技有限公司 | Nano TiO based on click chemistry2Modified polyurethane coating and preparation method thereof |
| CN112794955A (en) * | 2020-12-28 | 2021-05-14 | 长沙新材料产业研究院有限公司 | Low-water-absorption polyimide resin and preparation method thereof |
| CN114180906A (en) * | 2021-11-22 | 2022-03-15 | 蒋雨炎 | Environment-friendly pervious concrete and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112552817A (en) * | 2020-12-10 | 2021-03-26 | 桐乡市鑫皓科技有限公司 | Nano TiO based on click chemistry2Modified polyurethane coating and preparation method thereof |
| CN112794955A (en) * | 2020-12-28 | 2021-05-14 | 长沙新材料产业研究院有限公司 | Low-water-absorption polyimide resin and preparation method thereof |
| CN114180906A (en) * | 2021-11-22 | 2022-03-15 | 蒋雨炎 | Environment-friendly pervious concrete and preparation method thereof |
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