CN107573359B - Phenylenediamine monomer containing 1,4:3, 6-dianhydrohexitol side group and preparation and application thereof - Google Patents
Phenylenediamine monomer containing 1,4:3, 6-dianhydrohexitol side group and preparation and application thereof Download PDFInfo
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Abstract
The invention contains 1: 4; a phenylenediamine monomer with a 3: 6-dianhydrohexitol structure, and preparation and application thereof, belonging to the technical field of polymer synthesis. The invention provides a composition containing 1: 4; 3: 6-dianhydrohexitol structure phenylenediamine monomer, preparation and application thereof; 3, 5-dinitrobenzoyl chloride and 1: 4; 3: 6-dianhydrohexitol is reacted by a solvent-free melt process to produce a reaction product containing 1: 4; a benzene dinitro monomer of a 3: 6-dianhydrohexitol structure; reducing to obtain the product with the ratio of 1: 4; a phenylenediamine monomer of a 3: 6-dianhydrohexitol structure; contains 1: 4; the phenylenediamine monomer with a 3: 6-dianhydrohexitol structure and a diacid monomer are subjected to polycondensation reaction to prepare a monomer containing 1: 4; preparing the polyether sulfone hybrid ultrafiltration membrane by using polyamide of 3: 6-dianhydrohexitol and doping the polyamide with polyether sulfone. The product prepared by the invention contains 1: 4; the polyamide of 3: 6-dianhydrohexitol can obviously raise the hydrophilicity, water flux and anti-fouling performance of polyether sulfone ultrafiltration membrane.
Description
Technical Field
The invention relates to the field of polymer synthesis, in particular to a phenylenediamine monomer containing 1,4:3, 6-dianhydrohexitol side group for improving the hydrophilicity and the stain resistance of polyether sulfone resin, and preparation and application thereof.
Background
The membrane technology is widely applied to the fields of food, pharmacy, biotechnology, water treatment and the like due to the advantages of high efficiency, low cost, good selectivity, no phase change and the like. In recent years, polyether sulfone resin has good thermal property, acid and alkali resistance, high mechanical property and good film forming property, so that the polyether sulfone resin is prepared into an ultrafiltration membrane and is applied to industrial water treatment. However, the polyethersulfone resin membrane has strong hydrophobicity, so that organic or inorganic substances often contained in wastewater are easily adsorbed or deposited on the surface or in pores of the membrane, so that membrane pollution is caused, and the flux of the ultrafiltration membrane is directly reduced and the service life of the ultrafiltration membrane is shortened, so that the application of the ultrafiltration membrane is limited. Therefore, the hydrophilic modification of the polyethersulfone resin ultrafiltration membrane is particularly important. At present, a plurality of methods for hydrophilic modification of a polyethersulfone resin ultrafiltration membrane exist, and a blending method is used for doping hydrophilic substances or polymers containing hydrophilic groups with polyethersulfone resin to realize hydrophilic modification of the polyethersulfone resin ultrafiltration membrane, so that the method is a simple and effective method.
1: 4; the 3: 6-dianhydrohexitol is derived from natural cereals and has three isomers, namely isosorbide (1: 4; 3: 6-dianhydro-D-sorbitol), isomannide (1: 4; 3: 6-dianhydro-D-mannitol) and iditol (1: 4; 3: 6-dianhydro-1-iditol). Due to 1: 4; the 3: 6-dianhydrohexitol contains two secondary alcohols and has strong hygroscopicity and hydrophilicity. The polyamide main chain structure contains more amido bonds which are easy to form hydrogen bonds with water molecules, and the hydrophilic performance of the matrix material can be improved by blending the polyamide main chain structure serving as an additive or a doping agent with the polyether sulfone resin material. In recent years, Abbas Shockravi (Jalali A., Shockravi A., Vatanbour V., et al, Microporous & Mesoporous Materials,2016,228: 1-13; Shockravi A., Vatanbour V., Najjar Z., et al, Microporous & Mesoporous Materials,2017,246:24-36) subject groups introduce heteroatoms and bulky naphthalene rings which are liable to form hydrogen bonds with water molecules into the molecular structure of polyamide to increase the hydrophilicity of polyamide, and use the heteroatoms and bulky naphthalene rings as additives to improve the hydrophilicity of polyether sulfone resin.
Disclosure of Invention
The invention aims to solve the technical problems that a separation membrane prepared from the existing polyether sulfone resin material has hydrophobicity and is easy to pollute in application. To solve this problem, the present invention provides a composition comprising 1: 4; a 3: 6-dianhydrohexitol structure and provides the monomer comprising 1: 4; preparation and application of 3: 6-dianhydrohexitol structure phenylenediamine monomer. The invention adopts the technical scheme that the catalyst comprises 1: 4; a phenylenediamine monomer of a 3: 6-dianhydrohexitol structure; the content is 1: 4; the 3: 6-dianhydrohexitol structure phenylenediamine monomer is prepared by reacting 3, 5-dinitrobenzoyl chloride with 1: 4; 3: 6-dianhydrohexitol is reacted by a solvent-free melting method to obtain 1: 4; a benzene dinitro monomer of a 3: 6-dianhydrohexitol structure; 1:4 by hydrazine hydrate and palladium on carbon; reducing the benzene dinitro monomer with a 3: 6-dianhydrohexitol structure into a diamine monomer; the content is 1: 4; the phenylenediamine monomer with a 3: 6-dianhydrohexitol structure and a diacid monomer are subjected to polycondensation reaction to prepare a monomer containing 1: 4; a hydrophilic polyamide with a pendant 3: 6-dianhydrohexitol group; contains 1: 4; the hydrophilic polyamide with 3: 6-dianhydrohexitol lateral group can be used as an additive to prepare the polyether sulfone resin ultrafiltration membrane.
The invention adopts the specific technical scheme that the catalyst comprises 1: 4; a 3: 6-dianhydrohexitol structural phenylenediamine monomer characterized in that said monomer comprises 1: 4; the structural formula of the phenylenediamine monomer with the 3: 6-dianhydrohexitol structure is shown in the specification
Wherein Fr is
One kind of (1).
Contains 1: 4; the preparation method of the phenylenediamine monomer with the 3: 6-dianhydrohexitol structure comprises the following specific synthetic steps:
(1) under normal temperature and pressure, 1:4 of 3, 5-dinitrobenzoyl chloride; 3, adding 6-dianhydrohexitol and a phase transfer catalyst into a three-neck round-bottom flask provided with a mechanical stirrer, a condenser and a thermometer, heating to 60 ℃ for melting, and continuing stirring for 10-20 minutes; adding an organic solvent 1 into the system, quickly stirring, cooling to room temperature, separating out a product after 20-120 minutes, carrying out suction filtration, washing the separated solid with deionized water for 3-5 times, drying for 10 hours at 80 ℃, and recrystallizing with methanol to obtain a product with the content of 1: 4; a benzene dinitro monomer of a 3: 6-dianhydrohexitol structure; 1: 4; the 3: 6-dianhydrohexitol is preferably one of isosorbide, isomannide and iditol; 3, 5-dinitrobenzoyl chloride, 1: 4; the molar ratio of the 3: 6-dianhydrohexitol to the phase transfer catalyst to the organic solvent 1 is 1: 2.0-10.0: 0.1: 5; the phase transfer catalyst is preferably one of 18-crown-6, 15-crown-5 and cyclodextrin; the organic solvent 1 is preferably one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone;
(2) mixing the solution containing 1: 4; 3, dissolving a benzene dinitro monomer with a 6-dianhydrohexitol structure in an organic solvent 2, adding 10 percent by mass of palladium carbon under the protection of nitrogen, heating to reflux, and dropwise adding hydrazine hydrate by using a constant-pressure dropping funnel at the speed of 0.20-0.35 mL/min; after the hydrazine hydrate is dripped, refluxing for 10-20 minutes; filtering to remove palladium carbon while hot, cooling the filtrate in nitrogen atmosphere, slowly pouring into distilled water, filtering, vacuum drying at 80 deg.C for 10 hr, and recrystallizing with methanol to obtain a filtrate containing 1: 4; 3: 6-dianhydrohexitol structure phenylenediamine monomer; the content is 1: 4; the benzene dinitro monomer with a 3: 6-dianhydrohexitol structure, the organic solvent 2, 10% by mass of palladium-carbon, water and hydrazine are in a molar ratio of 1: 1.2-3: 0.5: 2-10; the organic solvent 2 is preferably one of methanol, ethanol and 1, 4-dioxane.
The content is 1: 4; the synthetic route of the phenylenediamine monomer with a 3: 6-dianhydrohexitol structure is as follows:
wherein Fr is 1: 4; three isomers of 3: 6-dianhydrohexitols have the groups remaining after removal of the terminal hydroxyl groups.
One contains 1: 4; 3: 6-dianhydroThe application of the phenylenediamine monomer with the hexitol structure comprises the following steps of 1: 4; the phenylenediamine monomer with 3: 6-dianhydrohexitol structure and diacid monomer are condensed to obtain the product with 1:4 content; a hydrophilic polyamide having pendant 3: 6-dianhydrohexitol groups, said polyamide having 1: 4; the structural formula of the hydrophilic polyamide with the 3: 6-dianhydrohexitol lateral group is shown in the specification
Wherein Fr is
N is an integer between 10 and 90; ar is
One kind of (1).
One contains 1: 4; the application of the phenylenediamine monomer with a 3: 6-dianhydrohexitol structure is characterized in that the phenylenediamine monomer contains 1: 4; the synthesis of the hydrophilic polyamide with the 3: 6-dianhydrohexitol side group comprises the following steps: introducing nitrogen into a three-neck flask provided with a magneton, a nitrogen inlet and a nitrogen outlet and a thermometer, and adding the mixture with the concentration of 1: 4; 3: 6-dianhydrohexitol structure phenylenediamine monomers and diacid monomers; then adding N-methyl pyrrolidone, triphenyl phosphite, pyridine and CaCl2(ii) a Heating to 120 ℃ under the condition of stirring, reacting for 3 hours, cooling to room temperature after the reaction is finished, and discharging to methanol to obtain a white fibrous crude product; refluxing and washing the white fibrous crude product with ethanol for 30 minutes, refluxing and washing with water for 10 minutes, refluxing and washing with ethanol for 30 minutes, and vacuum-drying at 100 ℃ to obtain a product containing 1: 4; a hydrophilic polyamide with a pendant 3: 6-dianhydrohexitol group; wherein, the ratio of the content of the organic acid to the organic acid is 1: 4; 3: 6-dianhydrohexitol structure phenylenediamine monomer, diacid monomer, N-methyl pyrrolidone, triphenyl phosphite, pyridine and CaCl2In a molar ratio of 1:1:30:4:6: 1.5; 1: 4; the 3: 6-dianhydrohexitol structural phenylenediamine monomer is preferably selected from the group consisting of 2-hydroxy-5- (3, 5-diaminobenzoyl) isosorbide, 2-hydroxy-5- (3, 5-diaminobenzoyl) isomannide and 2-hydroxy-5- (3, 5-diaminobenzoyl) isosorbideBase) one of iditol, its structural formula is
Fr is respectively
The diacid monomer is preferably one of terephthalic acid, 4-diacid diphenyl ether, 4-biphenyldicarboxylic acid, 2-bis (4-carboxyphenyl) hexafluoropropane and trans cyclohexanedicarboxylic acid.
The synthetic route is as follows:
wherein n is an integer between 10 and 90; ar is
One kind of (1).
One contains 1: 4; the application of the phenylenediamine monomer with a 3: 6-dianhydrohexitol structure is characterized in that the phenylenediamine monomer contains 1: 4; 3: 6-dianhydrohexitol lateral group hydrophilic polyamide and polyether sulfone resin are sequentially dissolved in N, N-dimethyl formamide (DMF), stirred for 10 hours at the temperature of 60 ℃, filtered and kept stand for defoaming for 10 hours at the temperature of 50 ℃ under the vacuum condition to obtain a defoamed casting solution; uniformly scraping the defoamed casting solution on a glass plate by using a self-made scraper, and standing in air for 30 seconds; immersing the glass plate into deionized water at room temperature to form a solid film; continuously immersing the solid film in deionized water for 48 hours, and replacing water every 6 hours to obtain a solution containing 1: 4; 3: 6-dianhydrohexitol lateral group hydrophilic polyamide modified polyether sulfone resin flat ultrafiltration membrane; wherein, the ratio of the content of the organic acid to the organic acid is 1: 4; the mass ratio of the hydrophilic polyamide with the 3: 6-dianhydrohexitol side group, the polyether sulfone resin and the N, N-Dimethylformamide (DMF) is 1-15: 17:83; contains 1: 4; the structural formula of the hydrophilic polyamide with the 3: 6-dianhydrohexitol lateral group is shown in the specification
Fr is
One of (1); n is an integer of 10-90; ar is
One kind of (1).
The product prepared by the invention contains 1: 4; the hydrophilic polyamide with the 3: 6-dianhydrohexitol side group can be used as an additive to be doped with the polyethersulfone resin, so that the hydrophilic performance and the antifouling performance of the polyethersulfone resin ultrafiltration membrane are improved.
The invention provides a synthesis method of polyamide containing 1,4:3, 6-dianhydrohexitol side group for improving hydrophilic and anti-fouling performance of polyether sulfone resin. Firstly, 1: 4; the 3: 6-dianhydrohexitol is derived from natural grains, has rich raw materials and low price, can be biodegraded, saves energy and is environment-friendly; secondly, based on 1: 4; the preparation of the 3: 6-dianhydrohexitol mono-substituted and derived diamine monomer containing the benzene structure adopts a solvent-free melting method, is simple to operate, non-toxic and harmless, is environment-friendly, and is suitable for large-scale industrial production; thirdly, the five-membered oxygen heterocycle which is wedge-shaped on the side chain of the polyamide can increase the molecular chain spacing of the polyamide, thereby improving the solubility of the polymer; finally, 1: 4; the hydrophilic polyamide of the 3: 6-dianhydrohexitol side group as the additive has the advantages that amido bonds on a main chain and secondary alcohol hydroxyl and oxygen heterocyclic rings on the side chain are easy to form hydrogen bonds with water molecules, so when the hydrophilic polyamide is doped with the polyether sulfone resin, the existence of the polyamide can directly increase the hydrogen bonding effect of the molecular chains and the water molecules, a hydration layer is formed on the surface of the polyether sulfone resin ultrafiltration membrane, the hydrophilicity of the polyether sulfone resin ultrafiltration membrane is improved, and meanwhile, organic pollutants are difficult to attach to the hydration layer and easy to clean due to the existence of the surface hydration layer, so that the anti-fouling performance of the polyether sulfone resin ultrafiltration membrane is enhanced. In addition, the pendant hydroxyl of the pendant polyamide side group can also form a hydrogen bond between molecular chains with ether bonds and sulfone groups on the main chain of the polyether sulfone resin, and the pendant hydroxyl and the ether bonds and the sulfone groups are retained in a membrane matrix, so that the aim of being hydrophilic and insoluble in water is fulfilled, and the defect of easily soluble water additives such as PEG, PVP and the like is overcome.
Drawings
FIG. 1 Nuclear magnetic spectrum of 2-hydroxy-5- (3, 5-diaminobenzoyl) isomannide hydrogen in example 1.
FIG. 2 carbon nuclear magnetic spectrum of 2-hydroxy-5- (3, 5-diaminobenzoyl) isomannide in example 1.
FIG. 3 Infrared Spectrum of 2-hydroxy-5- (3, 5-dinitrobenzoyl) isomannide (a) in example 1 and 2-hydroxy-5- (3, 5-diaminobenzoyl) isomannide (b) in example 1.
FIG. 4 shows the hydrogen nuclear magnetic spectrum of the polyamide containing the isomannide pendant group in example 4.
FIG. 5 is an infrared spectrum of a polyamide containing pendant isomannide groups from example 4.
FIG. 6 Electron micrograph of cross section of polyamide modified polyethersulfone flat ultrafiltration membrane containing isomannide of example 13.
FIG. 7 scanning electron micrograph of upper surface of polyamide modified polyethersulfone flat ultrafiltration membrane containing isomannide of example 13.
Detailed Description
The present invention will be described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
(1) Adding 20mmol of 3, 5-dinitrobenzoyl chloride, 200mmol of isomannide and 2mmol of 15-crown-5 into a three-neck round-bottom flask provided with a mechanical stirrer, a condenser and a thermometer at normal temperature and pressure, heating to 60 ℃ for melting, and continuing stirring for 20 minutes; adding 100mL of N, N-dimethylformamide into the system, quickly stirring, cooling to room temperature, separating out a product after 60 minutes, carrying out suction filtration, washing the separated solid with deionized water for 5 times, drying at 80 ℃ for 10 hours, and recrystallizing with methanol to obtain 18.5mmol of light yellow 1: 4; 3: 6-dianhydrohexitol structure of a benzene dinitro monomer: 2-hydroxy-5- (3, 5-dinitrobenzoyl) isomannide;
(2) dissolving 10mmol of 2-hydroxy-5- (3, 5-dinitrobenzoyl) isomannide in 30mmol of ethanol, adding 2mmol of palladium-carbon with the mass fraction of 10% under the protection of nitrogen, heating to reflux, and dropwise adding 100mmol of hydrazine hydrate by using a constant-pressure dropping funnel at the speed of 0.35 mL/min; refluxing for 20 minutes after the hydrazine hydrate is dripped; filtering to remove palladium carbon while hot, cooling the filtrate under nitrogen atmosphere, slowly pouring into distilled water, filtering, vacuum drying at 80 deg.C for 10 hr, and recrystallizing with methanol to obtain 8.5mmol pure white solution containing 1: 4; phenylenediamine monomer of 3: 6-dianhydrohexitol Structure: 2-hydroxy-5- (3, 5-diaminobenzoyl) isomannide with the structural formula
The yield was 85%.
FIGS. 1 and 2 show the hydrogen nuclear magnetic spectrum (FIG. 1) and carbon nuclear magnetic spectrum (FIG. 2) of 2-hydroxy-5- (3, 5-diaminobenzoyl) isomannide, respectively, with good hydrogen and carbon assignments for each environment; FIG. 3, spectral line a, shows the infrared spectrum of 2-hydroxy-5- (3, 5-diaminobenzoyl) isomannide at 1337-1341 cm-1In the presence of Ar-NO2Disappearance of the expansion vibration peak and the length of the expansion vibration peak being 3218-3475 cm-1The sum of the N-H stretching vibration peak and the sum of the N-H stretching vibration peak is 1610 cm to 1635cm-1The appearance of an N-H bending characteristic absorption peak indicates that the 2-hydroxy-5- (3, 5-dinitrobenzoyl) isomannide is completely reduced, and the successful synthesis of the compound containing 1:4 is proved; a 3: 6-dianhydrohexitol structure phenylenediamine monomer.
Example 2
(1) Adding 20mmol of 3, 5-dinitrobenzoyl chloride, 40mmol of isosorbide and 2mmol of 18-crown-6 into a three-neck round-bottom flask provided with a mechanical stirrer, a condenser and a thermometer at normal temperature and pressure, heating to 60 ℃ for melting, and continuing stirring for 10 minutes; adding 100mL of N, N-dimethylacetamide into the system, rapidly stirring, cooling to room temperature, separating out a product after 20 minutes, performing suction filtration, washing the separated solid with deionized water for 3 times, drying at 80 ℃ for 10 hours, and recrystallizing with methanol to obtain 18mmol of light yellow 1: 4; 3: 6-dianhydrohexitol structure of a benzene dinitro monomer: 2-hydroxy-5- (3, 5-dinitrobenzoyl) isosorbide;
(2) dissolving 10mmol of 2-hydroxy-5- (3, 5-dinitrobenzoyl) isosorbide in 12mmol of 1, 4-dioxane, adding 2mmol of palladium-carbon with the mass fraction of 10% under the protection of nitrogen, heating to reflux, and dropwise adding 20mmol of hydrazine hydrate by using a constant-pressure dropping funnel at the speed of 0.20 mL/min; refluxing for 10 minutes after the hydrazine hydrate is dripped; filtering to remove palladium carbon while hot, cooling the filtrate in nitrogen atmosphere, slowly pouring into distilled water, filtering, vacuum drying at 80 deg.C for 10 hr, and recrystallizing with methanol to obtain 8mmol pure white solution containing 1: 4; phenylenediamine monomer of 3: 6-dianhydrohexitol Structure: 2-hydroxy-5- (3, 5-diaminobenzoyl) isosorbide with the structural formula
The yield was 80%.
Example 3
(1) Adding 20mmol of 3, 5-dinitrobenzoyl chloride, 100mmol of iditol and 2mmol of cyclodextrin into a three-neck round-bottom flask provided with a mechanical stirrer, a condenser and a thermometer at normal temperature and pressure, heating to 60 ℃ for melting, and continuing stirring for 15 minutes; adding 100mL of N-methylpyrrolidone into the system, quickly stirring, cooling to room temperature, separating out a product after 120 minutes, carrying out suction filtration, washing the separated solid with deionized water for 4 times, drying at 80 ℃ for 10 hours, and then recrystallizing with methanol to obtain 17mmol of light yellow 1: 4; a benzene dinitro monomer with a 6-dianhydrohexitol structure, namely 2-hydroxy-5- (3, 5-dinitrobenzoyl) iditol;
(2) dissolving 10mmol of 2-hydroxy-5- (3, 5-dinitrobenzoyl) idose in 15mmol of methanol, adding 2mmol of palladium-carbon with the mass fraction of 10% under the protection of nitrogen, heating to reflux, and dropwise adding 50mmol of hydrazine hydrate by using a constant-pressure dropping funnel at the speed of 0.30 mL/min; refluxing for 15 minutes after the hydrazine hydrate is dripped; filtering to remove palladium carbon while hot, cooling the filtrate in nitrogen atmosphere, slowly pouring into distilled water, filtering, vacuum drying at 80 deg.C for 10 hr, and recrystallizing with methanol to obtain 6.8mmol pure white solution containing 1: 4; phenylenediamine monomer of 3: 6-dianhydrohexitol Structure: 2-hydroxy-5- (3, 5-diaminobenzoyl) iditol with the structural formula
The yield was 68%.
Example 4
Introducing nitrogen into a three-necked flask equipped with magnetons, a nitrogen inlet/outlet and a thermometer, and adding 1.5mmol (0.4202g) of 2-hydroxy-5- (3, 5-diaminobenzoyl) isomanninol and 1.5mmol (0.3873g) of 4, 4-diacid diphenyl ether; then 45mmol of N-methylpyrrolidone, 6mmol of triphenyl phosphite, 9mmol of pyridine and 2.25mmol of CaCl are added2(ii) a Heating to 120 ℃ under the condition of stirring, reacting for 3 hours, cooling to room temperature after the reaction is finished, and discharging to methanol to obtain a white fibrous crude product; the white fibrous crude product was washed with ethanol under reflux for 30 minutes, with water under reflux for 10 minutes, with ethanol under reflux for 30 minutes, and dried under vacuum at 100 ℃ to give 0.7543g containing 1: 4; hydrophilic polyamides with pendant 3: 6-dianhydrohexitol groups: isomannitol-containing pendant polyamides having a weight average molecular weight of 18840, a number average molecular weight of 169900, and n of 40.
FIG. 4 is a hydrogen nuclear magnetic spectrum of polyamide containing isomannide side groups, and it can be seen that the hydrogen chemical shift range of two five-membered rings in isomannide fragments is 4.5-5.3 ppm, hydrogen atoms on amide bonds appear at 10.5ppm to prove that polyamide is generated, and hydrogen in each environment on the rest aromatic rings is well ascribed; FIG. 5 is an infrared spectrum of polyamide containing isomannide pendant group, wave number 1663cm-1And C ═ O stretching vibration peak appears on amido bond, which indicates that the polyamide containing the isomannide side group is successfully prepared again.
Example 5
Example 4 was repeated, substituting 1.5mmol (0.2492g) of terephthalic acid for 4, 4-diacid diphenyl ether, to give a mixture containing 1: 4; hydrophilic polyamides with pendant 3: 6-dianhydrohexitol groups: 0.6025g of polyamide containing the isomannide side group, the weight-average molecular weight is 23200, the number-average molecular weight is 20880, and n is 50.
Example 6
Example 4 was repeated using 1.5mmol (0.3633g) of 4, 4-biphenyldicarboxylic acid instead of 4, 4-diacid diphenyl ether to give a composition containing 1: 4; hydrophilic polyamides with pendant 3: 6-dianhydrohexitol groups: the polyamide containing the isomannide side group 0.7012g, the weight-average molecular weight was 32400, the number-average molecular weight was 29160, and n was 60.
Example 7
Example 4 was repeated using 1.5mmol (0.5884g) of 2, 2-bis (4-carboxyphenyl) hexafluoropropane instead of 4, 4-diacid diphenyl ether to give a mixture containing 1: 4; hydrophilic polyamides with pendant 3: 6-dianhydrohexitol groups: the polyamide containing the isomannide side group 0.9431g, the weight-average molecular weight is 47460, the number-average molecular weight is 42714, and n is 70.
Example 8
Example 4 was repeated using 1.5mmol (0.2580g) of trans-cyclohexanedicarboxylic acid instead of 4, 4-diacid diphenyl ether to give a mixture containing 1: 4; hydrophilic polyamides with pendant 3: 6-dianhydrohexitol groups: 0.6549g of polyamide containing side isomannide groups, the weight-average molecular weight of 42300, the number-average molecular weight of 38070 and n equal to 90.
Example 9
Example 4 was repeated using 1.5mmol (0.4202g) of 2-hydroxy-5- (3, 5-diaminobenzoyl) isosorbide in place of 2-hydroxy-5- (3, 5-diaminobenzoyl) isomannide to give a mixture containing 1: 4; hydrophilic polyamides with pendant 3: 6-dianhydrohexitol groups: the polyamide containing isosorbide side group 0.7384g, had a weight average molecular weight of 20016, a number average molecular weight of 18014, and n was 40.
Example 10
Example 4 was repeated using 1.5mmol (0.4202g) of 2-hydroxy-5- (3, 5-diaminobenzoyl) isosorbide in place of 2-hydroxy-5- (3, 5-diaminobenzoyl) isomannide and 1.5mmol (0.2492g) of terephthalic acid in place of 4, 4-diacid diphenyl ether to give a composition containing 1: 4; hydrophilic polyamides with pendant 3: 6-dianhydrohexitol groups: 0.6450g of polyamide containing isosorbide side groups, the weight average molecular weight is 23200, the number average molecular weight is 19720, and n is 50.
Example 11
Example 4 was repeated using 1.5mmol (0.4202g) of 2-hydroxy-5- (3, 5-diaminobenzoyl) isosorbide in place of 2-hydroxy-5- (3, 5-diaminobenzoyl) isomannide and 1.5mmol (0.3633g) of 4, 4-biphenyldicarboxylic acid in place of 4, 4-diacid diphenyl ether to give a composition 1: 4; hydrophilic polyamides with pendant 3: 6-dianhydrohexitol groups: the polyamide containing isosorbide side groups 0.7538g had a weight average molecular weight of 32400, a number average molecular weight of 27540, and n 60.
Example 12
Example 4 was repeated using 1.5mmol (0.4202g) of 2-hydroxy-5- (3, 5-diaminobenzoyl) isosorbide in place of 2-hydroxy-5- (3, 5-diaminobenzoyl) isomannide and 1.5mmol (0.5884g) of 2, 2-bis (4-carboxyphenyl) hexafluoropropane in place of 4, 4-diacid diphenyl ether to give a mixture containing 1: 4; hydrophilic polyamides with pendant 3: 6-dianhydrohexitol groups: 0.9671g of polyamide containing isosorbide side groups, the weight average molecular weight is 54240, the number average molecular weight is 46104, and n is 80.
Example 13
Example 4 was repeated using 1.5mmol (0.4202g) of 2-hydroxy-5- (3, 5-diaminobenzoyl) isosorbide in place of 2-hydroxy-5- (3, 5-diaminobenzoyl) isomannide and 1.5mmol (0.2580g) of trans cyclohexanedicarboxylic acid in place of 4, 4-diacid diphenyl ether to give a mixture containing 1: 4; hydrophilic polyamides with pendant 3: 6-dianhydrohexitol groups: the polyamide containing isosorbide side group 0.6530g, weight average molecular weight 42300, number average molecular weight 35955, n is 90.
Example 14
Example 4 was repeated using 1.5mmol (0.4202g) of 2-hydroxy-5- (3, 5-diaminobenzoyl) iditol in place of 2-hydroxy-5- (3, 5-diaminobenzoyl) isomannide to give a solution containing 1: 4; hydrophilic polyamides with pendant 3: 6-dianhydrohexitol groups: pendant iditol-containing polyamide 0.7160g, weight average molecular weight 16680, number average molecular weight 15846, and n equal to 30.
Example 15
Example 4 was repeated using 1.5mmol (0.4202g) of 2-hydroxy-5- (3, 5-diaminobenzoyl) iditol in place of 2-hydroxy-5- (3, 5-diaminobenzoyl) isomannide and 1.5mmol (0.2492g) of terephthalic acid in place of 4, 4-diacid diphenyl ether to give a mixture containing 1: 4; hydrophilic polyamides with pendant 3: 6-dianhydrohexitol groups: the pendant iditol-containing polyamide was 0.6352g, had a weight average molecular weight of 18560, a number average molecular weight of 17632, and n was 40.
Example 16
Example 4 was repeated using 1.5mmol (0.4202g) of 2-hydroxy-5- (3, 5-diaminobenzoyl) iditol in place of 2-hydroxy-5- (3, 5-diaminobenzoyl) isomannide and 1.5mmol (0.3633g) of 4, 4-biphenyldicarboxylic acid in place of 4, 4-diacid diphenyl ether to give a composition 1: 4; hydrophilic polyamides with pendant 3: 6-dianhydrohexitol groups: the pendant iditol-containing polyamide was 0.7297g, with a weight average molecular weight of 27000, a number average molecular weight of 25650, and n of 50.
Example 17
Example 4 was repeated using 1.5mmol (0.4202g) of 2-hydroxy-5- (3, 5-diaminobenzoyl) iditol in place of 2-hydroxy-5- (3, 5-diaminobenzoyl) isomannide and 1.5mmol (0.5884g) of 2, 2-bis (4-carboxyphenyl) hexafluoropropane in place of 4, 4-diacid diphenyl ether to give a composition containing 1: 4; hydrophilic polyamides with pendant 3: 6-dianhydrohexitol groups: the pendant iditol-containing polyamide was 0.9368g, had a weight average molecular weight of 40680 and a number average molecular weight of 38646, with n being 60.
Example 18
Example 4 was repeated using 1.5mmol (0.4202g) of 2-hydroxy-5- (3, 5-diaminobenzoyl) iditol in place of 2-hydroxy-5- (3, 5-diaminobenzoyl) isomannide and 1.5mmol (0.2580g) of trans cyclohexane in place of 4, 4-diacid diphenyl ether to give a mixture containing 1: 4; hydrophilic polyamides with pendant 3: 6-dianhydrohexitol groups: pendant iditol-containing polyamide 0.6483g, weight average molecular weight 32900, number average molecular weight 31255, and n 70.
Example 19
Dissolving 1.7g of polyether sulfone in 8.3g N, N-Dimethylformamide (DMF), stirring for 10 hours at 60 ℃, filtering, standing and defoaming for 10 hours at 50 ℃ under a vacuum condition to obtain a defoamed casting solution; uniformly scraping the defoamed casting solution on a glass plate by using a self-made scraper, and standing in air for 30 seconds; immersing the glass plate into deionized water at room temperature to form a solid film; the solid membrane was immersed in deionized water for an additional 48 hours and the water was changed every 6 hours to give a polyethersulfone flat plate ultrafiltration membrane (PES-PA 0%) with a membrane thickness of (100. + -. 5) μm.
Example 20
0.017g of the isomannide-containing polyamide prepared in example 4 and 1.7g of polyethersulfone were sequentially dissolved in 8.3g of N, N-Dimethylformamide (DMF), stirred at 60 ℃ for 10 hours, filtered, and then allowed to stand under vacuum condition at 50 ℃ for deaeration for 10 hours to obtain a deaerated casting solution; scraping the defoamed casting solution on a glass plate by using a self-made scraper at a constant speed, and standing in air for 30 seconds; immersing the glass plate into deionized water at room temperature to form a solid film; the solid membrane was further immersed in deionized water for 48 hours and the water was changed every 6 hours to give an isomannide-containing polyamide-modified polyethersulfone flat plate ultrafiltration membrane (PES-PA 1%) having a membrane thickness of (100 ± 5) μm.
Example 21
Example 20 was repeated using 0.051g of the isomannide-containing polyamide prepared in example 4 instead of 0.017g of the isomannide-containing polyamide to obtain an isomannide-containing polyamide-modified polyethersulfone flat plate ultrafiltration membrane (PES-PA 3%) having a membrane thickness of (100. + -.5) μm.
Example 22
Example 20 was repeated using 0.085g of the isomannide-containing polyamide prepared in example 4 instead of 0.017g of the isomannide-containing polyamide to obtain an isomannide-containing polyamide-modified polyethersulfone flat plate ultrafiltration membrane (PES-PA 5%) having a membrane thickness of (100. + -.5) μm.
Example 23
Example 20 was repeated using 0.17g of the isomannide-containing polyamide prepared in example 4 instead of 0.017g of the isomannide-containing polyamide to obtain an isomannide-containing polyamide-modified polyethersulfone flat plate ultrafiltration membrane (PES-PA 10%) having a membrane thickness of (100. + -.5) μm.
As can be seen from fig. 6 and 7, when the amount of the polyamide containing isomannide added in the polyethersulfone casting solution is 10%, the cross section and the surface of the PES-PA 10% hybrid membrane have porous morphology, which is mainly attributed to the instant phase separation during the membrane formation process, resulting in porous morphology. The porous morphology also determines that the PES-PA 10% hybrid membrane has higher water flux.
Example 24
Example 20 was repeated using 0.225g of the isomannide-containing polyamide prepared in example 4 instead of 0.017g of the isomannide-containing polyamide to obtain an isomannide-containing polyamide-modified polyethersulfone flat plate ultrafiltration membrane (PES-PA 15%) having a membrane thickness of (100. + -.5) μm.
Example 25
Example 20 was repeated using 0.17g of the isomannide-containing polyamide prepared in example 5 instead of 0.017g of the isomannide-containing polyamide to obtain an isomannide-containing polyamide-modified polyethersulfone flat plate ultrafiltration membrane (PES-PA 10%) having a membrane thickness of (100. + -.5) μm.
Example 26
Example 20 was repeated using 0.17g of the isomannide-containing polyamide prepared in example 6 instead of 0.017g of the isomannide-containing polyamide to obtain an isomannide-containing polyamide-modified polyethersulfone flat plate ultrafiltration membrane (PES-PA 10%) having a membrane thickness of (100. + -.5) μm.
Example 27
Example 20 was repeated using 0.17g of the isomannide-containing polyamide prepared in example 7 instead of 0.017g of the isomannide-containing polyamide to obtain an isomannide-containing polyamide-modified polyethersulfone flat plate ultrafiltration membrane (PES-PA 10%) having a membrane thickness of (100. + -.5) μm.
Example 28
Example 20 was repeated using 0.17g of the isomannide-containing polyamide prepared in example 8 instead of 0.017g of the isomannide-containing polyamide to obtain an isomannide-containing polyamide-modified polyethersulfone flat plate ultrafiltration membrane (PES-PA 10%) having a membrane thickness of (100. + -.5) μm.
Example 29
Example 20 was repeated using 0.17g of the isosorbide-containing polyamide prepared in example 9 instead of 0.017g of the isomannide-containing polyamide to obtain an isosorbide-containing polyamide-modified polyethersulfone flat plate ultrafiltration membrane (PES-PA 10%) having a membrane thickness of (100. + -. 5) μm.
Example 30
Example 20 was repeated using 0.17g of the isosorbide-containing polyamide prepared in example 10 instead of 0.017g of the isomannide-containing polyamide to obtain an isosorbide-containing polyamide-modified polyethersulfone flat plate ultrafiltration membrane (PES-PA 10%) having a membrane thickness of (100. + -. 5) μm.
Example 31
Example 20 was repeated using 0.17g of the isosorbide-containing polyamide prepared in example 11 in place of 0.017g of the isomannide-containing polyamide to obtain an isosorbide-containing polyamide-modified polyethersulfone flat plate ultrafiltration membrane (PES-PA 10%) having a membrane thickness of (100. + -. 5) μm.
Example 32
Example 20 was repeated using 0.17g of the isosorbide-containing polyamide prepared in example 12 instead of 0.017g of the isomannide-containing polyamide to obtain an isosorbide-containing polyamide-modified polyethersulfone flat plate ultrafiltration membrane (PES-PA 10%) having a membrane thickness of (100. + -. 5) μm.
Example 33
Example 20 was repeated using 0.17g of the isosorbide-containing polyamide prepared in example 13 instead of 0.017g of the isomannide-containing polyamide to obtain an isosorbide-containing polyamide-modified polyethersulfone flat plate ultrafiltration membrane (PES-PA 10%) having a membrane thickness of (100. + -. 5) μm.
Example 34
Example 20 was repeated using 0.17g of iditol-containing polyamide prepared in example 14 instead of 0.017g of isomannide-containing polyamide to obtain an iditol-containing polyamide modified polyethersulfone flat plate ultrafiltration membrane (PES-PA 10%) having a membrane thickness of (100. + -.5) μm.
Example 35
Example 20 was repeated using 0.17g of iditol-containing polyamide prepared in example 15 instead of 0.017g of isomannide-containing polyamide to obtain an iditol-containing polyamide modified polyethersulfone flat plate ultrafiltration membrane (PES-PA 10%) having a membrane thickness of (100. + -.5) μm.
Example 36
Example 20 was repeated using 0.17g of iditol-containing polyamide prepared in example 16 instead of 0.017g of isomannide-containing polyamide to obtain an iditol-containing polyamide modified polyethersulfone flat plate ultrafiltration membrane (PES-PA 10%) having a membrane thickness of (100. + -.5) μm.
Example 37
Example 20 was repeated using 0.17g of iditol-containing polyamide prepared in example 17 instead of 0.017g of isomannide-containing polyamide to obtain an iditol-containing polyamide modified polyethersulfone flat plate ultrafiltration membrane (PES-PA 10%) having a membrane thickness of (100. + -.5) μm.
Example 38
Example 20 was repeated using 0.17g of iditol-containing polyamide prepared in example 18 instead of 0.017g of isomannide-containing polyamide to obtain an iditol-containing polyamide modified polyethersulfone flat plate ultrafiltration membrane (PES-PA 10%) having a membrane thickness of (100. + -.5) μm.
Table 1 examples 19-24 polyamide modified polyethersulfone flat ultrafiltration membranes containing isomannide have hydrophilicity, water flux and rejection.
As can be seen from table 1, the contact angle of the PES membrane surface gradually decreased with the increase in PA content in the membrane casting solution, from which it can be demonstrated that the hydrophilicity of the PES ultrafiltration membrane gradually increased with the increase in hydrophilic polyamide content in the membrane casting solution. Meanwhile, it can be seen that as the PA content in the membrane casting solution increases from 0% to 10%, the pure water flux and the BSA solution flux of the ultrafiltration membrane gradually increase, which is mainly due to the fact that as the PA content increases, the amide bond alcoholic hydroxyl groups and the oxacyclo groups in the membrane, which are easy to form hydrogen bonds with water, increase, and they are easier to form hydrogen bonds with water molecules, which leads to the increase of water flux, and at the same time, the increase of PA content also increases the porosity of the ultrafiltration membrane and reduces the thickness of the dense layer of the membrane, so that the water flux increases. When the PA content reaches 15%, the pure water flux and the BSA flux of the PA content are reduced on the contrary, mainly because the viscosity of the casting solution is increased due to more PA, delayed phase separation occurs, a compact structure is easily formed on the surface of the membrane, the porosity is reduced, and the flux is reduced. And the PA content is increased from 0% to 15%, the retention rate of the ultrafiltration membrane is always kept above 95%, and high and stable retention performance is shown.
Table 2 examples 19-24 fouling resistance parameters of polyamide modified polyethersulfone flat ultrafiltration membranes containing isomannide.
As can be seen from table 2, as the content of the isomannide-containing polyamide in the polyethersulfone casting solution gradually increases, the recovery rate and reversible contamination degree of the hybrid membrane gradually increase, and the corresponding total contamination degree and irreversible contamination degree gradually decrease, thereby showing that the contamination resistance of the hybrid membrane gradually increases, mainly because as the content of the isomannide-containing polyamide in the casting solution increases, more amide bonds, hydroxyl groups, hydrogen bonds between the oxygen heterocycle and water molecules are formed in the hybrid membrane, a hydration layer is formed on the membrane surface, the adhesion of organic contaminants such as proteins on the membrane surface is reduced due to the existence of the hydration layer, and the membrane surface is easier to clean due to the existence of the hydration layer. Meanwhile, compared with the first cycle, in the second cycle ultrafiltration experiment, the recovery rate and reversible pollution degree of each hybrid membrane are obviously lower than those of the first cycle, and the total pollution degree and irreversible pollution degree of each corresponding hybrid membrane are obviously higher than those of the first cycle, so that the pollution degree of each membrane is obviously increased, mainly because part of protein is adhered to the surface of the membrane after the first cycle, so that when protein solution passes through the ultrafiltration membrane again, the electrostatic attraction between protein molecules enables the surface of the membrane to be easier to adsorb. But the recovery rate of the hybrid membrane PES-PA 5%, PES-PA 10% and PES-PA 15% after the second cycle can still reach more than 80%, thereby proving that the addition of the polyamide containing the isomannide can improve the anti-pollution performance of the polyether sulfone ultrafiltration membrane.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. It should be understood by those skilled in the art that various changes and substitutions may be made in accordance with the technical solution and the inventive concept of the present invention, and the same properties or uses should be considered as the protection scope of the present invention.
Claims (5)
1. One contains 1: 4; a 3: 6-dianhydrohexitol structural phenylenediamine monomer characterized in that said monomer comprises 1: 4; the structural formula of the phenylenediamine monomer with the 3: 6-dianhydrohexitol structure is shown in the specification
Wherein Fr is
One kind of (1).
2. A composition of claim 1 comprising 1: 4; the preparation method of the phenylenediamine monomer with the 3: 6-dianhydrohexitol structure comprises the following specific synthetic steps:
(1) under normal temperature and pressure, 1:4 of 3, 5-dinitrobenzoyl chloride; 3, adding 6-dianhydrohexitol and a phase transfer catalyst into a three-neck round-bottom flask provided with a mechanical stirrer, a condenser and a thermometer, heating to 60 ℃ for melting, and continuing stirring for 10-20 minutes; adding an organic solvent 1 into the system, quickly stirring, cooling to room temperature, separating out a product after 20-120 minutes, carrying out suction filtration, washing the separated solid with deionized water for 3-5 times, drying for 10 hours at 80 ℃, and recrystallizing with methanol to obtain a product with the content of 1: 4; a benzene dinitro monomer of a 3: 6-dianhydrohexitol structure; 1: 4; the 3: 6-dianhydrohexitol is one of isosorbide, isomannide and iditol; 3, 5-dinitrobenzoyl chloride, 1: 4; the molar ratio of the 3: 6-dianhydrohexitol to the phase transfer catalyst to the organic solvent 1 is 1: 2.0-10.0: 0.1: 5; the phase transfer catalyst is one of 18-crown-6, 15-crown-5 and cyclodextrin; the organic solvent 1 is one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone;
(2) mixing the solution containing 1: 4; 3, dissolving a benzene dinitro monomer with a 6-dianhydrohexitol structure in an organic solvent 2, adding 10 percent by mass of palladium carbon under the protection of nitrogen, heating to reflux, and dropwise adding hydrazine hydrate by using a constant-pressure dropping funnel at the speed of 0.20-0.35 mL/min; after the hydrazine hydrate is dripped, refluxing for 10-20 minutes; filtering to remove palladium carbon while hot, cooling the filtrate in nitrogen atmosphere, slowly pouring into distilled water, filtering, vacuum drying at 80 deg.C for 10 hr, and recrystallizing with methanol to obtain a filtrate containing 1: 4; 3: 6-dianhydrohexitol structure phenylenediamine monomer; the content is 1: 4; the benzene dinitro monomer with a 3: 6-dianhydrohexitol structure, the organic solvent 2, and the palladium-carbon with the mass fraction of 10% and the hydrazine hydrate are in a molar ratio of 1: 1.2-3: 0.5: 2-10; the organic solvent 2 is one of methanol, ethanol and 1, 4-dioxane.
3. A composition of claim 1 comprising 1: 4; the application of the phenylenediamine monomer with a 3: 6-dianhydrohexitol structure is characterized in that the phenylenediamine monomer contains 1: 4; the phenylenediamine monomer with 3: 6-dianhydrohexitol structure and diacid monomer are condensed to obtain the product with 1:4 content; a hydrophilic polyamide having pendant 3: 6-dianhydrohexitol groups, said polyamide having 1: 4; the structural formula of the hydrophilic polyamide with the 3: 6-dianhydrohexitol lateral group is shown in the specification
Wherein Fr is
N is an integer between 10 and 90; ar is
One kind of (1).
4. A composition of claim 3 comprising 1: 4; the application of the phenylenediamine monomer with a 3: 6-dianhydrohexitol structure is characterized in that the phenylenediamine monomer contains 1: 4; the synthesis of the hydrophilic polyamide with the 3: 6-dianhydrohexitol side group comprises the following steps:
(1) under normal temperature and pressure, 1:4 of 3, 5-dinitrobenzoyl chloride; 3, adding 6-dianhydrohexitol and a phase transfer catalyst into a three-neck round-bottom flask provided with a mechanical stirrer, a condenser and a thermometer, heating to 60 ℃ for melting, and continuing stirring for 10-20 minutes; adding an organic solvent 1 into the system, quickly stirring, cooling to room temperature, separating out a product after 20-120 minutes, carrying out suction filtration, washing the separated solid with deionized water for 3-5 times, drying for 10 hours at 80 ℃, and recrystallizing with methanol to obtain a product with the content of 1: 4; a benzene dinitro monomer of a 3: 6-dianhydrohexitol structure; 1: 4; the 3: 6-dianhydrohexitol is one of isosorbide, isomannide and iditol; 3, 5-dinitrobenzoyl chloride, 1: 4; the molar ratio of the 3: 6-dianhydrohexitol to the phase transfer catalyst to the organic solvent 1 is 1: 2.0-10.0: 0.1: 5; the phase transfer catalyst is one of 18-crown-6, 15-crown-5 and cyclodextrin; the organic solvent 1 is one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone;
(2) mixing the solution containing 1: 4; 3, dissolving a benzene dinitro monomer with a 6-dianhydrohexitol structure in an organic solvent 2, adding 10 percent by mass of palladium carbon under the protection of nitrogen, heating to reflux, and dropwise adding hydrazine hydrate by using a constant-pressure dropping funnel at the speed of 0.20-0.35 mL/min; after the hydrazine hydrate is dripped, refluxing for 10-20 minutes; filtering to remove palladium carbon while hot, cooling the filtrate in nitrogen atmosphere, slowly pouring into distilled water, filtering, vacuum drying at 80 deg.C for 10 hr, and recrystallizing with methanol to obtain a filtrate containing 1: 4; 3: 6-dianhydrohexitol structure phenylenediamine monomer; the content is 1: 4; the benzene dinitro monomer with a 3: 6-dianhydrohexitol structure, the organic solvent 2, and the palladium-carbon with the mass fraction of 10% and the hydrazine hydrate are in a molar ratio of 1: 1.2-3: 0.5: 2-10; the organic solvent 2 is one of methanol, ethanol and 1, 4-dioxane;
(3) introducing nitrogen into a three-neck flask provided with a magneton, a nitrogen inlet and a nitrogen outlet and a thermometer, and adding the mixture with the concentration of 1: 4; 3: 6-dianhydrohexitol structure phenylenediamine monomers and diacid monomers; then adding N-methyl pyrrolidone, triphenyl phosphite, pyridine and CaCl2(ii) a Heating to 120 ℃ under the condition of stirring, reacting for 3 hours, cooling to room temperature after the reaction is finished, and discharging to methanol to obtain a white fibrous crude product; refluxing and washing the white fibrous crude product with ethanol for 30 minutes, refluxing and washing with water for 10 minutes, refluxing and washing with ethanol for 30 minutes, and vacuum-drying at 100 ℃ to obtain a product containing 1: 4; a hydrophilic polyamide with a pendant 3: 6-dianhydrohexitol group; wherein, the ratio of the content of the organic acid to the organic acid is 1: 4; 3: 6-dianhydrohexitol structure phenylenediamine monomer, diacid monomer, N-methyl pyrrolidone, triphenyl phosphite, pyridine and CaCl2In a molar ratio of 1:1:30:4:6: 1.5; 1: 4; the phenylenediamine monomer of the 3: 6-dianhydrohexitol structure is 2-hydroxylOne of (E) -5- (3, 5-diaminobenzoyl) isosorbide, 2-hydroxy-5- (3, 5-diaminobenzoyl) isomannide and 2-hydroxy-5- (3, 5-diaminobenzoyl) iditol, and the structural formula is shown in the specification
Fr is respectively
The diacid monomer is one of terephthalic acid, 4-diacid diphenyl ether, 4-biphenyl dicarboxylic acid or 2, 2-bis (4-carboxyphenyl) hexafluoropropane.
5. A composition of claim 1 comprising 1: 4; the application of the phenylenediamine monomer with a 3: 6-dianhydrohexitol structure is characterized in that,
(1) under normal temperature and pressure, 1:4 of 3, 5-dinitrobenzoyl chloride; 3, adding 6-dianhydrohexitol and a phase transfer catalyst into a three-neck round-bottom flask provided with a mechanical stirrer, a condenser and a thermometer, heating to 60 ℃ for melting, and continuing stirring for 10-20 minutes; adding an organic solvent 1 into the system, quickly stirring, cooling to room temperature, separating out a product after 20-120 minutes, carrying out suction filtration, washing the separated solid with deionized water for 3-5 times, drying for 10 hours at 80 ℃, and recrystallizing with methanol to obtain a product with the content of 1: 4; a benzene dinitro monomer of a 3: 6-dianhydrohexitol structure; 1: 4; the 3: 6-dianhydrohexitol is one of isosorbide, isomannide and iditol; 3, 5-dinitrobenzoyl chloride, 1: 4; the molar ratio of the 3: 6-dianhydrohexitol to the phase transfer catalyst to the organic solvent 1 is 1: 2.0-10.0: 0.1: 5; the phase transfer catalyst is one of 18-crown-6, 15-crown-5 and cyclodextrin; the organic solvent 1 is one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone;
(2) mixing the solution containing 1: 4; 3, dissolving a benzene dinitro monomer with a 6-dianhydrohexitol structure in an organic solvent 2, adding 10 percent by mass of palladium carbon under the protection of nitrogen, heating to reflux, and dropwise adding hydrazine hydrate by using a constant-pressure dropping funnel at the speed of 0.20-0.35 mL/min; after the hydrazine hydrate is dripped, refluxing for 10-20 minutes; filtering to remove palladium carbon while hot, cooling the filtrate in nitrogen atmosphere, slowly pouring into distilled water, filtering, vacuum drying at 80 deg.C for 10 hr, and recrystallizing with methanol to obtain a filtrate containing 1: 4; 3: 6-dianhydrohexitol structure phenylenediamine monomer; the content is 1: 4; the benzene dinitro monomer with a 3: 6-dianhydrohexitol structure, the organic solvent 2, and the palladium-carbon with the mass fraction of 10% and the hydrazine hydrate are in a molar ratio of 1: 1.2-3: 0.5: 2-10; the organic solvent 2 is one of methanol, ethanol and 1, 4-dioxane;
(3) introducing nitrogen into a three-neck flask provided with a magneton, a nitrogen inlet and a nitrogen outlet and a thermometer, and adding the mixture with the concentration of 1: 4; 3: 6-dianhydrohexitol structure phenylenediamine monomers and diacid monomers; then adding N-methyl pyrrolidone, triphenyl phosphite, pyridine and CaCl2(ii) a Heating to 120 ℃ under the condition of stirring, reacting for 3 hours, cooling to room temperature after the reaction is finished, and discharging to methanol to obtain a white fibrous crude product; refluxing and washing the white fibrous crude product with ethanol for 30 minutes, refluxing and washing with water for 10 minutes, refluxing and washing with ethanol for 30 minutes, and vacuum-drying at 100 ℃ to obtain a product containing 1: 4; a hydrophilic polyamide with a pendant 3: 6-dianhydrohexitol group; wherein, the ratio of the content of the organic acid to the organic acid is 1: 4; 3: 6-dianhydrohexitol structure phenylenediamine monomer, diacid monomer, N-methyl pyrrolidone, triphenyl phosphite, pyridine and CaCl2In a molar ratio of 1:1:30:4:6: 1.5; 1: 4; the phenylenediamine monomer with a 3: 6-dianhydrohexitol structure is one of 2-hydroxy-5- (3, 5-diaminobenzoyl) isosorbide, 2-hydroxy-5- (3, 5-diaminobenzoyl) isomannide and 2-hydroxy-5- (3, 5-diaminobenzoyl) iditol, and the structural formula is shown in the specification
Fr is respectively
The diacid monomer is one of terephthalic acid, 4-diacid diphenyl ether, 4-biphenyldicarboxylic acid or 2, 2-bis (4-carboxyphenyl) hexafluoropropane;
(4) mixing the mixture containing 1: 4; sequential dissolution of hydrophilic polyamide and polyether sulfone resins with 3: 6-dianhydrohexitol side groupDissolving in N, N-dimethylformamide, stirring for 10 hours at 60 ℃, filtering, standing and defoaming for 10 hours at 50 ℃ under a vacuum condition to obtain a defoamed casting solution; uniformly scraping the defoamed casting solution on a glass plate by using a self-made scraper, and standing in air for 30 seconds; immersing the glass plate into deionized water at room temperature to form a solid film; continuously immersing the solid film in deionized water for 48 hours, and replacing water every 6 hours to obtain a solution containing 1: 4; 3: 6-dianhydrohexitol lateral group hydrophilic polyamide modified polyether sulfone resin flat ultrafiltration membrane; wherein, the ratio of the content of the organic acid to the organic acid is 1: 4; the mass ratio of hydrophilic polyamide with a 3: 6-dianhydrohexitol side group, polyether sulfone resin and N, N-dimethylformamide is 1-15: 17: 83; contains 1: 4; the structural formula of the hydrophilic polyamide with the 3: 6-dianhydrohexitol lateral group is shown in the specification
Fr is
One of (1); n is an integer of 10-90; ar is
One kind of (1).
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Non-Patent Citations (4)
| Title |
|---|
| A new high performance polyamide as an effective additive for modification of antifouling properties and morphology of asymmetric PES blend ultrafiltration membranes;Abbas Shockravi等;《Microporous and Mesoporous Materials》;20170313;第246卷;24-36 * |
| Preparation and characterization of novel microporous ultrafiltration PES membranes using synthesized hydrophilic polysulfide-amide copolymer as an additive in the casting solution;Aazam Jalali等;《Microporous and Mesoporous Materials》;20160320;第228卷;1-13 * |
| 二胺结构对聚酰胺复合纳滤膜性能的影响;王丽红等;《化学研究与应用》;20110331;第23卷(第3期);340-344 * |
| 成膜条件对聚醚砜超滤膜性能和结构的影响;姚亮等;《化学研究与应用》;20081031;第20卷(第10期);1304-1307 * |
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