CN112915810B - Pollution-resistant oxygen-permeable film material and preparation method thereof - Google Patents
Pollution-resistant oxygen-permeable film material and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D67/0002—Organic membrane manufacture
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention discloses a pollution-resistant oxygen-permeable film material and a preparation method thereof, wherein the pollution-resistant oxygen-permeable film material comprises the following raw materials in parts by weight: 50-60 parts of a mixture A, 10-14 parts of a powder B, 50-60 parts of chloroform, 0.4-0.6 part of ethyl orthosilicate and 0.1-0.3 part of dibutyltin dilaurate; the pollution-resistant oxygen-permeable film material is prepared by the following steps: firstly, ultrasonically mixing the mixture A, the powder B and chloroform for 1 hour, then adding tetraethoxysilane and dibutyltin dilaurate, and sieving through a 400-mesh sieve after the ultrasonic treatment to obtain a membrane matrix; and secondly, coating the membrane substrate obtained in the first step on a porous polyetherimide support membrane, evaporating the solvent at room temperature, and drying at 80 ℃ to constant weight to obtain the pollution-resistant oxygen-permeable membrane material.
Description
Technical Field
The invention belongs to the technical field of film material preparation, and particularly relates to a pollution-resistant oxygen-permeable film material and a preparation method thereof.
Background
Compared with the conventional methods such as cryogenic separation, pressure swing adsorption and the like, the gas membrane separation process has the advantages of small occupied area, low investment, low energy consumption, no phase change, no secondary pollution, flexible and convenient operation and the like, so that the gas membrane separation process is increasingly paid attention. Gas membrane separation techniques have been widely used in various industrial fields, such as air dehumidification, nitrogen production, refinery gas recovery, ammonia gas purification and separation, waste gas concentration, acid gas treatment, helium gas separation, and organic vapor recovery, and ideal gas separation membranes should have good membrane forming properties, membrane strength, chemical stability, and separation properties.
The invention CN102137709B relates to a process for the preparation of a membrane, in particular a gas separation membrane, wherein the membrane has a selective separation layer. The following steps are carried out here: a) preparing a polymer solution from at least one polymer and at least one polyethylene glycol ether, b) casting the polymer solution into a membrane, c) preparing a selective separation layer from the membrane in a further step, preferably by drying.
Disclosure of Invention
The invention provides a pollution-resistant oxygen-permeable film material and a preparation method thereof.
The technical problems to be solved by the invention are as follows:
the oxygen permeable film material has contact or non-directional combination of proteins during use, which is easy to cause pollution and influences the use effect.
The purpose of the invention can be realized by the following technical scheme:
the pollution-resistant oxygen-permeable film material comprises the following raw materials in parts by weight:
50-60 parts of a mixture A, 10-14 parts of a powder B, 50-60 parts of chloroform, 0.4-0.6 part of ethyl orthosilicate and 0.1-0.3 part of dibutyltin dilaurate;
the pollution-resistant oxygen-permeable film material is prepared by the following steps:
firstly, ultrasonically mixing the mixture A, the powder B and chloroform for 1h under the condition of 40-50kHz, then adding tetraethoxysilane and dibutyltin dilaurate, continuing to perform ultrasonic treatment for 10min, and sieving through a 400-mesh sieve after the ultrasonic treatment is finished to obtain a membrane matrix;
and secondly, coating the membrane substrate obtained in the first step on a porous polyetherimide support membrane, evaporating the solvent at room temperature, and drying at 80 ℃ to constant weight to obtain the pollution-resistant oxygen-permeable membrane material. The prepared anti-pollution oxygen-permeable film material has the advantages of improving the hydrophilic performance, improving the surface hydrophilicity of the film after film formation, reducing the contact and non-directional combination between the surface of the film and trapped molecules, particularly between proteins, thereby reducing the adsorption of pollutants, particularly biological pollutants, and having good anti-pollution performance.
Further, mixture a was prepared by the following steps:
step A11, adding chlorinated trimellitic anhydride and tetrahydrofuran into a three-neck flask, stirring until the chlorinated trimellitic anhydride is completely dissolved, adding pyridine, stirring to separate out a solid, mixing hydroquinone and tetrahydrofuran when the amount of the solid is not increased any more, adding the mixture into the three-neck flask, reacting for 12 hours at 25 ℃, filtering after the reaction is finished, taking filtrate, performing rotary evaporation to obtain a solid, recrystallizing with toluene and acetic anhydride, and drying at 50 ℃ to constant weight to obtain a solid a;
step A21, adding the solid a and 2,2-bis (3-amino-4 hydroxy) hexafluoropropane into a three-neck flask, adding p-chlorophenol, stirring for 16h under the protection of nitrogen and at the set temperature of 190 ℃ and the rotating speed of 400r/min, and imidizing for 14h to obtain a mixture A.
Further, in step a11, the usage ratio of the chlorinated trimellitic anhydride, pyridine, hydroquinone and tetrahydrofuran is 0.06mol:0.06mol:0.03mol:300mL, wherein the dosages of tetrahydrofuran in two times are equal; in the step A21, the dosage ratio of the solid a, 2,2-bis (3-amino-4 hydroxy) hexafluoropropane and p-chlorophenol is 3g:1g:40-50mL.
Chlorine in the chlorinated trimellitic anhydride reacts with hydroxyl in hydroquinone to prepare solid a, the solid a is a dianhydride substance, an acid anhydride structure in a molecule of the solid a and an amino structure in 2,2-bis (3-amino-4 hydroxyl) hexafluoropropane are subjected to imidization reaction to obtain a mixture A, and the mixture A contains a polymer with an imide ring structure and has good high-temperature resistance and mechanical properties.
Further, powder B was prepared by the following steps:
step S11, adding tetrafluoroterephthalonitrile, anhydrous calcium carbonate and 5,5',6,6' -tetrahydroxy-3,3,3 ',3' -tetramethyl-1,1 ' -spiral biindole into a three-neck flask, adding N, N-dimethylformamide under the protection of nitrogen, stirring uniformly, setting the temperature to 65 ℃ and the rotating speed to 400r/min, stirring for 24 hours, cooling the reaction liquid to room temperature after the reaction is finished, mixing the cooled reaction liquid with isovolumetric deionized water, stirring for 20 minutes under the condition that the rotating speed is 500r/min, decompressing and filtering after the stirring is finished, removing filtrate, washing a filter cake with methanol, trichloromethane and distilled water in sequence, and drying at 120 ℃ to constant weight after the washing is finished to obtain a solid b;
s12, adding the solid b and sodium hydroxide into an ethanol water solution with the mass fraction of 50%, setting the temperature at 120 ℃, carrying out heating hydrolysis reaction for 6 hours, cooling the temperature to room temperature after the reaction is finished, carrying out vacuum filtration, washing the obtained filter cake with deionized water until the washing liquid is neutral, and obtaining a solid c; in the process of preparing the pollution-resistant assistant, N, N-dimethylformamide is used as a solvent, anhydrous calcium carbonate is used as a catalyst, 5,5',6,6' -tetrahydroxy-3,3,3 ',3' -tetramethyl-1,1 ' -spirobiindole and tetrafluoroterephthalonitrile are subjected to polycondensation reaction to prepare a microporous polymer, a molecular chain of the solid b contains a cyano group, and the cyano group is hydrolyzed under the action of sodium hydroxide to generate a carboxyl sodium salt so as to prepare a solid c.
And S13, mixing the pollution-resistant auxiliary agent with deionized water, adding the solid c, setting the temperature at 100 ℃ and the rotating speed at 120-160r/min, reacting for 4-8h, performing reduced pressure suction filtration after the reaction is finished, removing filtrate, and drying the obtained filter cake to constant weight at 40 ℃ to obtain powder B. The method comprises the following steps of carrying out esterification reaction on polyvinyl alcohol and chloroacetyl chloride to remove one molecule of HCl to generate modified polyvinyl alcohol, introducing ester groups and acetyl chloride in the chloroacetyl chloride into a molecular chain of the polyvinyl alcohol, carrying out quaternary phosphorylation reaction on the modified polyvinyl alcohol and triphenylphosphine to generate a pollution-resistant auxiliary agent, wherein the pollution-resistant auxiliary agent contains hydrophilic groups and quaternary phosphonium salts, the quaternary phosphonium salts are used as a novel bactericide and have the performances of high-efficiency and broad-spectrum bactericidal performance, low toxicity, wide pH value application range and the like, and meanwhile, the quaternary phosphonium salts can carry out ion exchange with a sodium carboxylate structure on solid c and are grafted onto polymer molecules of the solid c to prepare powder B.
Further, in step S11, the ratio of the amounts of tetrafluoroterephthalonitrile, anhydrous calcium carbonate, 5,5',6,6' -tetrahydroxy-3,3,3 ',3' -tetramethyl-1,1 ' -spirobiindole and N, N-dimethylformamide is 0.6 to 0.7g:0.8g:1-1.1g:20mL; in step S12, the amount ratio of the solid b, sodium hydroxide, and 50% by mass of an ethanol aqueous solution is 1g:4g:20mL; in the step S13, the dosage ratio of the pollution-resistant auxiliary agent to the deionized water to the solid c is 0.1g:100mL of: 0.5g.
Further, the anti-contamination auxiliary is prepared by the following steps:
step S21, adding chloroacetyl chloride and polyvinyl alcohol into a three-neck flask, setting the temperature to be 0 ℃ and the rotation speed to be 200r/min under the protection of nitrogen, stirring for 5min, then raising the temperature to 30 ℃, keeping the rotation speed unchanged, stirring for reaction for 1-2h, after the reaction is finished, mixing the obtained reaction solution with petroleum ether with the same volume, performing ultrasonic dispersion for 10-15min under the condition of 40-50kHz, standing, removing the supernatant, repeating the operation for 3 times, dissolving the lower-layer insoluble substance with acetone, filtering out the insoluble substance, and then performing reduced pressure concentration to remove the acetone to obtain modified polyvinyl alcohol;
step S22, adding modified polyvinyl alcohol into a three-neck flask, adding dimethyl sulfoxide, setting the temperature to be 100 ℃ and the rotating speed to be 300r/min, stirring for 5min under the condition of nitrogen protection, then adding triphenylphosphine while stirring, after the addition is finished, keeping the temperature and the rotating speed unchanged, continuing stirring for 24h, after the stirring is finished, cooling the obtained reaction liquid to room temperature, washing the reaction liquid for three times with deionized water and acetone in sequence after cooling, after the washing is finished, carrying out vacuum filtration, removing filtrate, and drying the obtained filter cake to constant weight at 50 ℃ to obtain the pollution-resistant auxiliary agent.
Further, the amount ratio of acetyl chloride to polyvinyl alcohol in step S21 is 1g:20mL; in the step S22, the dosage ratio of the modified polyvinyl alcohol to the dimethyl sulfoxide to the triphenylphosphine is 1g:20mL of: 0.5-1g.
Further, the preparation method of the pollution-resistant oxygen-permeable film material comprises the following steps:
firstly, ultrasonically mixing the mixture A, the powder B and chloroform for 1h under the condition of 40-50kHz, then adding tetraethoxysilane and dibutyltin dilaurate, continuing to perform ultrasonic treatment for 10min, and sieving through a 400-mesh sieve after the ultrasonic treatment is finished to obtain a membrane matrix;
and secondly, coating the membrane substrate obtained in the first step on a porous polyetherimide support membrane, evaporating the solvent at room temperature, and drying at 80 ℃ to constant weight to obtain the pollution-resistant oxygen-permeable membrane material.
The invention has the beneficial effects that:
chlorine in the chlorinated trimellitic anhydride reacts with hydroxyl in hydroquinone to prepare solid a, the solid a is a dianhydride substance, an acid anhydride structure in a molecule of the solid a and an amino structure in 2,2-bis (3-amino-4 hydroxyl) hexafluoropropane are subjected to imidization reaction to obtain a mixture A, and the mixture A contains a polymer with an imide ring structure and has good high-temperature resistance and mechanical properties.
In the process of preparing the pollution-resistant assistant, N, N-dimethylformamide is used as a solvent, anhydrous calcium carbonate is used as a catalyst, 5,5',6,6' -tetrahydroxy-3,3,3 ',3' -tetramethyl-1,1 ' -spiral biindole and tetrafluoroterephthalonitrile are subjected to polycondensation reaction to prepare a microporous polymer, a molecular chain of the solid b contains a cyano group, and the cyano group is hydrolyzed under the action of sodium hydroxide to generate a carboxyl sodium salt so as to prepare a solid c. The method comprises the following steps of carrying out esterification reaction on polyvinyl alcohol and chloroacetyl chloride to remove a molecule of HCl to generate modified polyvinyl alcohol, introducing ester groups and acetyl chloride in the chloroacetyl chloride on a molecular chain of the polyvinyl alcohol, carrying out quaternary phosphorylation reaction on the modified polyvinyl alcohol and triphenylphosphine to generate a pollution-resistant assistant, wherein the pollution-resistant assistant contains hydrophilic groups and quaternary phosphonium salt, the quaternary phosphonium salt is used as a novel bactericide and has the performances of high-efficiency and broad-spectrum sterilization performance, low toxicity, wide pH value use range and the like, and meanwhile, the quaternary phosphonium salt can carry out ion exchange with a sodium carboxylate structure on solid c and is grafted onto polymer molecules of the solid c to prepare powder B, so that the powder B is endowed with hydrophilic, antibacterial and bacteriostatic effects.
The prepared anti-pollution oxygen-permeable film material has the advantages of improving the hydrophilic property, improving the surface hydrophilicity of the film after film forming, reducing the contact and non-directional combination between the surface of the film and trapped molecules, particularly between proteins, and further reducing the adsorption of pollutants, particularly biological pollutants, thereby having good anti-pollution property.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A pollution-resistant oxygen-permeable film material comprises the following raw materials in parts by weight:
50 parts of a mixture A, 10 parts of a powder B, 50 parts of chloroform, 0.4 part of ethyl orthosilicate and 0.1 part of dibutyltin dilaurate;
the pollution-resistant oxygen-permeable film material is prepared by the following steps:
firstly, ultrasonically mixing the mixture A, the powder B and chloroform for 1h under the condition of 40kHz, then adding tetraethoxysilane and dibutyltin dilaurate, continuing to perform ultrasonic treatment for 10min, and sieving through a 400-mesh sieve after the ultrasonic treatment is finished to obtain a membrane matrix;
and secondly, coating the membrane substrate obtained in the first step on a porous polyetherimide support membrane, evaporating the solvent at room temperature, and drying at 80 ℃ to constant weight to obtain the pollution-resistant oxygen-permeable membrane material.
Wherein, the mixture A is prepared by the following steps:
step A11, adding chlorinated trimellitic anhydride and tetrahydrofuran into a three-neck flask, stirring until the chlorinated trimellitic anhydride is completely dissolved, adding pyridine, stirring to separate out a solid, mixing hydroquinone and tetrahydrofuran when the amount of the solid is not increased any more, adding the mixture into the three-neck flask, reacting for 12 hours at 25 ℃, filtering after the reaction is finished, taking filtrate, performing rotary evaporation to obtain a solid, recrystallizing with toluene and acetic anhydride, and drying at 50 ℃ to constant weight to obtain a solid a;
step A21, adding the solid a and 2,2-bis (3-amino-4 hydroxy) hexafluoropropane into a three-neck flask, adding p-chlorophenol, stirring for 16h under the protection of nitrogen and at the set temperature of 190 ℃ and the rotating speed of 400r/min, and imidizing for 14h to obtain a mixture A.
In the step A11, the dosage ratio of the chlorinated trimellitic anhydride to the pyridine to the hydroquinone to the tetrahydrofuran is 0.06mol:0.06mol:0.03mol:300mL, wherein the amount of tetrahydrofuran used in two times is equal; in the step A21, the dosage ratio of the solid a, 2,2-bis (3-amino-4 hydroxy) hexafluoropropane and p-chlorophenol is 3g:1g:40mL.
Wherein powder B is prepared by the following steps:
step S11, adding tetrafluoroterephthalonitrile, anhydrous calcium carbonate and 5,5',6,6' -tetrahydroxy-3,3,3 ',3' -tetramethyl-1,1 ' -spiral biindole into a three-neck flask, adding N, N-dimethylformamide under the protection of nitrogen, stirring uniformly, setting the temperature to 65 ℃ and the rotating speed to 400r/min, stirring for 24 hours, cooling the reaction liquid to room temperature after the reaction is finished, mixing the cooled reaction liquid with isovolumetric deionized water, stirring for 20 minutes under the condition that the rotating speed is 500r/min, decompressing and filtering after the stirring is finished, removing filtrate, washing a filter cake with methanol, trichloromethane and distilled water in sequence, and drying at 120 ℃ to constant weight after the washing is finished to obtain a solid b;
s12, adding the solid b and sodium hydroxide into an ethanol water solution with the mass fraction of 50%, setting the temperature to be 120 ℃, carrying out heating hydrolysis reaction for 6 hours, cooling the temperature to room temperature after the reaction is finished, carrying out vacuum filtration, washing the obtained filter cake with deionized water until the washing liquid is neutral, and obtaining a solid c;
and S13, mixing the pollution-resistant auxiliary agent with deionized water, adding the solid c, setting the temperature at 100 ℃ and the rotating speed at 120r/min, reacting for 4 hours, performing vacuum filtration after the reaction is finished, removing filtrate, and drying the obtained filter cake at 40 ℃ to constant weight to obtain powder B.
Wherein, the dosage ratio of the tetrafluoroterephthalonitrile, the anhydrous calcium carbonate, the 5,5',6,6' -tetrahydroxy-3,3,3 ',3' -tetramethyl-1,1 ' -spirobiindole and the N, N-dimethylformamide in the step S11 is 0.6g:0.8g:1g:20mL; in step S12, the amount ratio of the solid b, sodium hydroxide, and 50% by mass of an ethanol aqueous solution is 1g:4g:20mL; in the step S13, the dosage ratio of the pollution-resistant auxiliary agent to the deionized water to the solid c is 0.1g:100mL of: 0.5g.
Wherein the anti-pollution auxiliary agent is prepared by the following steps:
step S21, adding chloroacetyl chloride and polyvinyl alcohol into a three-neck flask, setting the temperature to be 0 ℃ and the rotating speed to be 200r/min under the protection of nitrogen, stirring for 5min, then raising the temperature to 30 ℃, keeping the rotating speed unchanged, stirring for reaction for 1h, mixing the obtained reaction solution with petroleum ether with the same volume after the reaction is finished, performing ultrasonic dispersion for 10min under the condition of 40kHz, standing, removing the supernatant, repeating the operation for 3 times, dissolving the lower-layer insoluble substance with acetone, filtering out the insoluble substance, and then performing reduced pressure concentration to remove the acetone to obtain modified polyvinyl alcohol;
step S22, adding modified polyvinyl alcohol into a three-neck flask, adding dimethyl sulfoxide, setting the temperature to be 100 ℃ and the rotating speed to be 300r/min, stirring for 5min under the protection of nitrogen, then adding triphenylphosphine while stirring, keeping the temperature and the rotating speed unchanged after the addition is finished, continuing stirring for 24h, cooling the obtained reaction liquid to room temperature after the stirring is finished, washing the reaction liquid for three times by deionized water and acetone in sequence after the cooling, reducing pressure and filtering to remove filtrate after the washing is finished, and drying the obtained filter cake to constant weight at 50 ℃ to obtain the pollution-resistant assistant.
Wherein the dosage ratio of acetyl chloride to polyvinyl alcohol in the step S21 is 1g:20mL; in the step S22, the dosage ratio of the modified polyvinyl alcohol to the dimethyl sulfoxide to the triphenylphosphine is 1g:20mL of: 0.5g.
Example 2
The pollution-resistant oxygen-permeable film material comprises the following raw materials in parts by weight:
55 parts of a mixture A, 12 parts of a powder B, 55 parts of chloroform, 0.5 part of ethyl orthosilicate and 0.2 part of dibutyltin dilaurate;
the pollution-resistant oxygen-permeable film material is prepared by the following steps:
firstly, ultrasonically mixing the mixture A, the powder B and chloroform for 1h under the condition of 45kHz, then adding tetraethoxysilane and dibutyltin dilaurate, continuing to perform ultrasonic treatment for 10min, and sieving through a 400-mesh sieve after finishing the ultrasonic treatment to obtain a membrane matrix;
and secondly, coating the membrane substrate obtained in the first step on a porous polyetherimide support membrane, evaporating the solvent at room temperature, and drying at 80 ℃ to constant weight to obtain the pollution-resistant oxygen-permeable membrane material.
Wherein, the mixture A is prepared by the following steps:
step A11, adding chlorinated trimellitic anhydride and tetrahydrofuran into a three-neck flask, stirring until the chlorinated trimellitic anhydride is completely dissolved, adding pyridine, stirring to separate out a solid, mixing hydroquinone and tetrahydrofuran when the amount of the solid is not increased any more, adding the mixture into the three-neck flask, reacting for 12 hours at 25 ℃, filtering after the reaction is finished, taking filtrate, performing rotary evaporation to obtain a solid, recrystallizing with toluene and acetic anhydride, and drying at 50 ℃ to constant weight to obtain a solid a;
step A21, adding the solid a and 2,2-bis (3-amino-4 hydroxy) hexafluoropropane into a three-neck flask, adding p-chlorophenol, stirring for 16h under the protection of nitrogen and at the set temperature of 190 ℃ and the rotating speed of 400r/min, and imidizing for 14h to obtain a mixture A.
In the step A11, the dosage ratio of the chlorinated trimellitic anhydride to the pyridine to the hydroquinone to the tetrahydrofuran is 0.06mol:0.06mol:0.03mol:300mL, wherein the dosages of tetrahydrofuran in two times are equal; the dosage ratio of the solid a, 2,2-bis (3-amino-4 hydroxy) hexafluoropropane and p-chlorophenol in the step A21 is 3g:1g:45mL.
Wherein powder B is prepared by the following steps:
step S11, adding tetrafluoroterephthalonitrile, anhydrous calcium carbonate and 5,5',6,6' -tetrahydroxy-3,3,3 ',3' -tetramethyl-1,1 ' -spiral biindole into a three-neck flask, adding N, N-dimethylformamide under the protection of nitrogen, stirring uniformly, setting the temperature to 65 ℃ and the rotating speed to 400r/min, stirring for 24 hours, cooling the reaction liquid to room temperature after the reaction is finished, mixing the cooled reaction liquid with isovolumetric deionized water, stirring for 20 minutes under the condition that the rotating speed is 500r/min, decompressing and filtering after the stirring is finished, removing filtrate, washing a filter cake with methanol, trichloromethane and distilled water in sequence, and drying at 120 ℃ to constant weight after the washing is finished to obtain a solid b;
s12, adding the solid b and sodium hydroxide into an ethanol water solution with the mass fraction of 50%, setting the temperature to be 120 ℃, carrying out heating hydrolysis reaction for 6 hours, cooling the temperature to room temperature after the reaction is finished, carrying out vacuum filtration, washing the obtained filter cake with deionized water until the washing liquid is neutral, and obtaining a solid c;
and S13, mixing the pollution-resistant auxiliary agent with deionized water, adding the solid c, setting the temperature at 100 ℃ and the rotating speed at 140r/min, reacting for 6 hours, performing vacuum filtration after the reaction is finished, removing filtrate, and drying the obtained filter cake at 40 ℃ to constant weight to obtain powder B.
Wherein, the dosage ratio of the tetrafluoroterephthalonitrile, the anhydrous calcium carbonate, the 5,5',6,6' -tetrahydroxy-3,3,3 ',3' -tetramethyl-1,1 ' -spiro-biindole and the N, N-dimethylformamide in the step S11 is 0.g:0.8g:1g:20mL; in step S12, the amount ratio of the solid b, sodium hydroxide, and 50% by mass of an ethanol aqueous solution is 1g:4g:20mL; in the step S13, the dosage ratio of the pollution-resistant auxiliary agent to the deionized water to the solid c is 0.1g:100mL of: 0.5g.
Wherein the anti-pollution auxiliary agent is prepared by the following steps:
step S21, adding chloroacetyl chloride and polyvinyl alcohol into a three-neck flask, setting the temperature to be 0 ℃ and the rotating speed to be 200r/min under the protection of nitrogen, stirring for 5min, then raising the temperature to 30 ℃, keeping the rotating speed unchanged, stirring for reaction for 1.5h, after the reaction is finished, mixing the obtained reaction solution with petroleum ether with the same volume, performing ultrasonic dispersion for 12min under the condition of 45kHz, standing, removing the supernatant, repeating the operation for 3 times, dissolving the lower-layer insoluble substance with acetone, filtering the insoluble substance, and then performing reduced pressure concentration to remove the acetone to obtain modified polyvinyl alcohol;
step S22, adding modified polyvinyl alcohol into a three-neck flask, adding dimethyl sulfoxide, setting the temperature to be 100 ℃ and the rotating speed to be 300r/min, stirring for 5min under the protection of nitrogen, then adding triphenylphosphine while stirring, keeping the temperature and the rotating speed unchanged after the addition is finished, continuing stirring for 24h, cooling the obtained reaction liquid to room temperature after the stirring is finished, washing the reaction liquid for three times by deionized water and acetone in sequence after the cooling, reducing pressure and filtering to remove filtrate after the washing is finished, and drying the obtained filter cake to constant weight at 50 ℃ to obtain the pollution-resistant assistant.
Wherein the dosage ratio of acetyl chloride to polyvinyl alcohol in the step S21 is 1g:20mL; in the step S22, the dosage ratio of the modified polyvinyl alcohol to the dimethyl sulfoxide to the triphenylphosphine is 1g:20mL of: 0.8g.
Example 3
The pollution-resistant oxygen-permeable film material comprises the following raw materials in parts by weight:
60 parts of a mixture A, 14 parts of a powder B, 60 parts of chloroform, 0.6 part of ethyl orthosilicate and 0.3 part of dibutyltin dilaurate;
the pollution-resistant oxygen-permeable film material is prepared by the following steps:
firstly, ultrasonically mixing the mixture A, the powder B and chloroform for 1 hour under the condition of 50kHz, then adding tetraethoxysilane and dibutyltin dilaurate, continuing to perform ultrasonic treatment for 10 minutes, and sieving through a 400-mesh sieve after the ultrasonic treatment is finished to obtain a membrane matrix;
and secondly, coating the membrane substrate obtained in the first step on a porous polyetherimide support membrane, evaporating the solvent at room temperature, and drying at 80 ℃ to constant weight to obtain the pollution-resistant oxygen-permeable membrane material.
Wherein, the mixture A is prepared by the following steps:
step A11, adding chlorinated trimellitic anhydride and tetrahydrofuran into a three-neck flask, stirring until the chlorinated trimellitic anhydride is completely dissolved, adding pyridine, stirring to separate out a solid, when the amount of the solid is not increased any more, mixing hydroquinone and tetrahydrofuran, adding the mixture into the three-neck flask, reacting for 12 hours at 25 ℃, after the reaction is finished, performing suction filtration, taking filtrate, performing rotary evaporation to obtain a solid, recrystallizing the solid with toluene and acetic anhydride, and drying the solid at 50 ℃ to constant weight to obtain a solid a;
step A21, adding the solid a and 2,2-bis (3-amino-4 hydroxy) hexafluoropropane into a three-neck flask, adding p-chlorophenol, stirring for 16h under the protection of nitrogen and at the set temperature of 190 ℃ and the rotating speed of 400r/min, and imidizing for 14h to obtain a mixture A.
In the step A11, the dosage ratio of the chlorinated trimellitic anhydride to the pyridine to the hydroquinone to the tetrahydrofuran is 0.06mol:0.06mol:0.03mol:300mL, wherein the dosages of tetrahydrofuran in two times are equal; the dosage ratio of the solid a, 2,2-bis (3-amino-4 hydroxy) hexafluoropropane and p-chlorophenol in the step A21 is 3g:1g:50mL.
Wherein powder B is prepared by the following steps:
s11, adding tetrafluoroterephthalonitrile, anhydrous calcium carbonate and 5,5',6,6' -tetrahydroxy-3,3,3 ',3' -tetramethyl-1,1 ' -spiral biindole into a three-neck flask, adding N, N-dimethylformamide under the protection of nitrogen, stirring uniformly, setting the temperature to 65 ℃ and the rotating speed to 400r/min, stirring for 24 hours, cooling the reaction liquid to room temperature after the reaction is finished, mixing the cooled reaction liquid with isometric deionized water, stirring for 20 minutes under the condition that the rotating speed is 500r/min, performing suction filtration under reduced pressure after the stirring is finished, removing filtrate, washing a filter cake with methanol, trichloromethane and distilled water in sequence, and drying at 120 ℃ to constant weight after the washing is finished to obtain a solid b;
s12, adding the solid b and sodium hydroxide into an ethanol water solution with the mass fraction of 50%, setting the temperature at 120 ℃, carrying out heating hydrolysis reaction for 6 hours, cooling the temperature to room temperature after the reaction is finished, carrying out vacuum filtration, washing the obtained filter cake with deionized water until the washing liquid is neutral, and obtaining a solid c;
and S13, mixing the pollution-resistant auxiliary agent with deionized water, adding the solid c, setting the temperature at 100 ℃ and the rotating speed at 160r/min, reacting for 8 hours, performing vacuum filtration after the reaction is finished, removing filtrate, and drying the obtained filter cake at 40 ℃ to constant weight to obtain powder B.
Wherein, in the step S11, the dosage ratio of the tetrafluoroterephthalonitrile, the anhydrous calcium carbonate, the 5,5',6,6' -tetrahydroxy-3,3,3 ',3' -tetramethyl-1,1 ' -spirobiindole and the N, N-dimethylformamide is 0.7g:0.8g:1.1g:20mL; in the step S12, the dosage ratio of the solid b, the sodium hydroxide and the ethanol water solution with the mass fraction of 50% is 1g:4g:20mL; in the step S13, the dosage ratio of the pollution-resistant auxiliary agent, the deionized water and the solid c is 0.1g:100mL of: 0.5g.
Wherein the anti-pollution auxiliary agent is prepared by the following steps:
step S21, adding chloroacetyl chloride and polyvinyl alcohol into a three-neck flask, setting the temperature to be 0 ℃ and the rotating speed to be 200r/min under the protection of nitrogen, stirring for 5min, then raising the temperature to 30 ℃, keeping the rotating speed unchanged, stirring for reaction for 2h, mixing the obtained reaction solution with petroleum ether with the same volume after the reaction is finished, performing ultrasonic dispersion for 15min under the condition of 50kHz, standing, removing the supernatant, repeating the operation for 3 times, dissolving the lower-layer insoluble substance with acetone, filtering out the insoluble substance, and then performing reduced pressure concentration to remove the acetone to obtain modified polyvinyl alcohol;
step S22, adding modified polyvinyl alcohol into a three-neck flask, adding dimethyl sulfoxide, setting the temperature to be 100 ℃ and the rotating speed to be 300r/min, stirring for 5min under the condition of nitrogen protection, then adding triphenylphosphine while stirring, after the addition is finished, keeping the temperature and the rotating speed unchanged, continuing stirring for 24h, after the stirring is finished, cooling the obtained reaction liquid to room temperature, washing the reaction liquid for three times with deionized water and acetone in sequence after cooling, after the washing is finished, carrying out vacuum filtration, removing filtrate, and drying the obtained filter cake to constant weight at 50 ℃ to obtain the pollution-resistant auxiliary agent.
Wherein the dosage ratio of acetyl chloride to polyvinyl alcohol in the step S21 is 1g:20mL; in the step S22, the dosage ratio of the modified polyvinyl alcohol to the dimethyl sulfoxide to the triphenylphosphine is 1g:20mL of: 1g of the total weight of the composition.
Comparative example 1
The anti-fouling assistant in example 1 was not added, and the rest of the raw materials and the preparation process remained unchanged.
Comparative example 2
The comparative example is an oxygen permeable film material commonly available in the market.
The membrane materials prepared in examples 1-3 and comparative examples 1-2 were tested for contamination resistance and mechanical properties, a DSA100 contact angle measuring instrument measures the contact angle of the membrane material to water by the sitting drop method, the separation coefficient is the ratio of the osmotic pressure of oxygen and nitrogen at the two sides of the membrane, and the test results are shown in table 1 below:
TABLE 1
From the above table 1, it can be seen that the contamination-resistant oxygen-permeable film material prepared by the invention has better hydrophilic property, namely better contamination-resistant property, while ensuring the mechanical property and oxygen permeability efficiency of the film material.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (5)
1. The pollution-resistant oxygen-permeable film material is characterized by comprising the following raw materials in parts by weight:
50-60 parts of a mixture A, 10-14 parts of a powder B, 50-60 parts of chloroform, 0.4-0.6 part of ethyl orthosilicate and 0.1-0.3 part of dibutyltin dilaurate;
the pollution-resistant oxygen-permeable film material is prepared by the following steps:
firstly, ultrasonically mixing the mixture A, the powder B and chloroform for 1h under the condition of 40-50kHz, then adding tetraethoxysilane and dibutyltin dilaurate, continuing to perform ultrasonic treatment for 10min, and sieving through a 400-mesh sieve after the ultrasonic treatment is finished to obtain a membrane matrix;
secondly, coating the membrane substrate obtained in the first step on a porous polyetherimide support membrane, evaporating the solvent at room temperature, and drying at 80 ℃ to constant weight to obtain a pollution-resistant oxygen-permeable membrane material;
the mixture A is prepared by the following steps:
step A11, adding chlorinated trimellitic anhydride and tetrahydrofuran into a three-neck flask, stirring until the chlorinated trimellitic anhydride is completely dissolved, adding pyridine, stirring to separate out a solid, mixing hydroquinone and tetrahydrofuran when the amount of the solid is not increased any more, adding the mixture into the three-neck flask, reacting for 12 hours at 25 ℃, filtering after the reaction is finished, taking filtrate, performing rotary evaporation to obtain a solid, recrystallizing with toluene and acetic anhydride, and drying at 50 ℃ to constant weight to obtain a solid a;
step A21, adding solid a and 2,2-bis (3-amino-4 hydroxy) hexafluoropropane into a three-neck flask, adding p-chlorophenol, stirring for 16h under the protection of nitrogen at the set temperature of 190 ℃ and the rotation speed of 400r/min, and imidizing for 14h to obtain a mixture A;
the powder B was prepared by the following steps:
step S11, adding tetrafluoroterephthalonitrile, anhydrous calcium carbonate and 5,5',6,6' -tetrahydroxy-3,3,3 ',3' -tetramethyl-1,1 ' -spiral biindole into a three-neck flask, adding N, N-dimethylformamide under the protection of nitrogen, stirring uniformly, setting the temperature to 65 ℃ and the rotating speed to 400r/min, stirring for 24 hours, cooling the reaction liquid to room temperature after the reaction is finished, mixing the cooled reaction liquid with isovolumetric deionized water, stirring for 20 minutes under the condition that the rotating speed is 500r/min, decompressing and filtering after the stirring is finished, removing filtrate, washing a filter cake with methanol, trichloromethane and distilled water in sequence, and drying at 120 ℃ to constant weight after the washing is finished to obtain a solid b;
s12, adding the solid b and sodium hydroxide into an ethanol water solution with the mass fraction of 50%, setting the temperature at 120 ℃, carrying out heating hydrolysis reaction for 6 hours, cooling the temperature to room temperature after the reaction is finished, carrying out vacuum filtration, washing the obtained filter cake with deionized water until the washing liquid is neutral, and obtaining a solid c;
s13, mixing the pollution-resistant auxiliary agent with deionized water, then adding solid c, setting the temperature to be 100 ℃ and the rotating speed to be 120-160r/min, reacting for 4-8h, after the reaction is finished, carrying out vacuum filtration, removing filtrate, and drying the obtained filter cake to constant weight at 40 ℃ to obtain powder B;
the anti-pollution auxiliary agent is prepared by the following steps:
step S21, adding chloroacetyl chloride and polyvinyl alcohol into a three-neck flask, setting the temperature to be 0 ℃ and the rotating speed to be 200r/min under the protection of nitrogen, stirring for 5min, then raising the temperature to 30 ℃, keeping the rotating speed unchanged, stirring for reaction for 1-2h, after the reaction is finished, mixing the obtained reaction solution with petroleum ether with the same volume, performing ultrasonic dispersion for 10-15min under the condition of 40-50kHz, standing, removing the supernatant, repeating the operation for 3 times, dissolving the lower-layer insoluble substance with acetone, filtering the insoluble substance, and then performing reduced pressure concentration to remove the acetone to obtain modified polyvinyl alcohol;
step S22, adding modified polyvinyl alcohol into a three-neck flask, adding dimethyl sulfoxide, setting the temperature to be 100 ℃ and the rotating speed to be 300r/min, stirring for 5min under the condition of nitrogen protection, then adding triphenylphosphine while stirring, after the addition is finished, keeping the temperature and the rotating speed unchanged, continuing stirring for 24h, after the stirring is finished, cooling the obtained reaction liquid to room temperature, washing the reaction liquid for three times with deionized water and acetone in sequence after cooling, after the washing is finished, carrying out vacuum filtration, removing filtrate, and drying the obtained filter cake to constant weight at 50 ℃ to obtain the pollution-resistant auxiliary agent.
2. The contamination-resistant oxygen-permeable film material according to claim 1, wherein in step a11, the ratio of the amounts of the chlorinated trimellitic anhydride, pyridine, hydroquinone and tetrahydrofuran is 0.06mol:0.06mol:0.03mol:300mL, wherein the amount of tetrahydrofuran used in two times is equal; in the step A21, the dosage ratio of the solid a, 2,2-bis (3-amino-4 hydroxy) hexafluoropropane and p-chlorophenol is 3g:1g:40-50mL.
3. The contamination-resistant oxygen-permeable film material according to claim 1, wherein the ratio of the amounts of tetrafluoroterephthalonitrile, anhydrous calcium carbonate, 5,5',6,6' -tetrahydroxy-3,3,3 ',3' -tetramethyl-1,1 ' -spirobiindole and N, N-dimethylformamide in step S11 is 0.6 to 0.7g:0.8g:1-1.1g:20mL; in step S12, the amount ratio of the solid b, sodium hydroxide, and 50% by mass of an ethanol aqueous solution is 1g:4g:20mL; in the step S13, the dosage ratio of the pollution-resistant auxiliary agent to the deionized water to the solid c is 0.1g:100mL of: 0.5g.
4. The contamination-resistant oxygen-permeable film material according to claim 1, wherein the ratio of the amounts of chloroacetyl chloride and polyvinyl alcohol in step S21 is 1g:20mL; in the step S22, the dosage ratio of the modified polyvinyl alcohol to the dimethyl sulfoxide to the triphenylphosphine is 1g:20mL of: 0.5-1g.
5. The preparation method of the contamination-resistant oxygen-permeable film material as claimed in claim 1, which comprises the following steps:
firstly, ultrasonically mixing the mixture A, the powder B and chloroform for 1h under the condition of 40-50kHz, then adding tetraethoxysilane and dibutyltin dilaurate, continuing to perform ultrasonic treatment for 10min, and sieving through a 400-mesh sieve after the ultrasonic treatment is finished to obtain a membrane matrix;
and secondly, coating the membrane substrate obtained in the first step on a porous polyetherimide support membrane, evaporating the solvent at room temperature, and drying at 80 ℃ to constant weight to obtain the pollution-resistant oxygen-permeable membrane material.
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