Calixarene structural unit-containing polysulfone as well as preparation method and application thereof

Abstract

The invention provides polysulfone containing calixarene structural units as well as a preparation method and application of the polysulfone. The preparation method of the polysulfone containing the calixarene structural unit comprises the following step: in an aprotic polar solvent, in the presence of a salt-forming agent and a water diversion agent, carrying out a reaction on alkyl etherified p-tert-butyl calixarene [n] and dihalogenated diphenyl sulfone to obtain the polysulfone containing the calixarene structural unit. The raw materials are commercially available, the synthesis steps are simple, and industrial stable production is easy to realize. Due to the introduction of a calixarene structural unit, polysulfone has molecular recognition capability, and is more beneficial to realizing high-efficiency filtration and selective enrichment in precise separation of complex multi-component systems (such as heavy metals, organic pollutants or biomolecules); the method is expected to have potential and huge development prospects in the fields of high-value-added industrial wastewater treatment (such as electronic electroplating wastewater and pharmaceutical wastewater), biological medicine purification (such as protein / antibody separation and targeted drug delivery) and resource recovery (such as precious metal / rare element extraction).

Description

Technical Field

[0001] The invention belongs to the technical field of functional and special polymer materials, and particularly relates to a polysulfone containing a calixarene structural unit, and a preparation method and application thereof. Background Art

[0002] Polysulfone (PSU) is a high-performance engineering plastic that is widely used in separation membranes, medical devices, aerospace, and other fields due to its excellent mechanical strength, high temperature resistance, and acid and alkali resistance. The sulfone group and benzene ring structure in its molecular chain give the material excellent dimensional stability and creep resistance. However, traditional polysulfone used as a separation membrane has poor hydrophilicity, low surface energy, and lacks the ability to accurately identify components with similar molecular size or small polarity differences (such as heavy metal ions and monovalent ions, and organic pollutant homologues), which limits its separation efficiency and service life in complex systems.

[0003] Calixarene is a macrocyclic compound (n=4, 6, 8) composed of phenol units linked by methylene bridges. It possesses a three-dimensional nanocavity structure with easily derivatized phenolic hydroxyl groups at the lower edge and para-positioned aromatic ring hydroxyl groups. The cavity size can be customized by adjusting the number of benzene rings and substituents, enabling host-guest recognition and selective inclusion of specific molecules (such as heavy metal ions, small organic molecules, or biomolecules). These properties hold significant potential for applications in adsorption separation, catalytic support, and chemical sensing. However, traditional physical mixing or surface modification methods for introducing calixarene into polymer matrices can lead to uneven distribution or detachment of functional groups due to poor compatibility, hindering the full realization of its molecular recognition advantages.

[0004] In related technologies, most researchers form supramolecular organic frameworks by non-covalent interactions between calixarene macrocyclic host molecules and other guest molecules. However, this supramolecular organic framework enrichment medium lacks sufficient stability, which limits its application in sample adsorption treatment. Summary of the Invention

[0005] In view of the deficiencies in the prior art, the present invention provides a polysulfone containing a calixarene structural unit, and a preparation method and application thereof. The present invention uses calixarene as a raw material, and obtains an alkyl-etherified calixarene by a substitution reaction with a halogenated hydrocarbon. The alkyl-etherified calixarene and dihalogenated diphenyl sulfone are condensed to form a polysulfone containing a calixarene structural unit. The raw materials of the present invention are commercially available, the synthesis steps are simple, and it is easy to achieve industrial and stable production. Due to the introduction of the calixarene structural unit, the polysulfone of the present invention has molecular recognition ability, which is more conducive to achieving efficient filtration and selective enrichment in the precise separation of complex multi-component systems (such as those containing heavy metals, organic pollutants or biological molecules). It is expected to have potential and huge development prospects in the fields of high-value-added industrial wastewater treatment (such as electronic electroplating wastewater, pharmaceutical wastewater), biopharmaceutical purification (such as protein / antibody separation, targeted drug delivery) and resource recovery (such as precious metal / rare element extraction).

[0006] The technical solutions of the present invention are as follows:

[0007] A polysulfone containing a calixarene structural unit, obtained by reacting a hydroxyl group in an alkyl-etherified p-tert-butylcalix[n]arene with a halogen in a dihalogenated diphenyl sulfone;

[0008] Wherein, the alkyl-etherified p-tert-butylcalix[n]arene has a structure shown in the following formula I, formula II or formula III:

[0009]

[0010] wherein R is selected from -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3 or -CH2C6H5.

[0011] According to the present invention, the structure of the polysulfone containing the calixarene structural unit is shown in the following formula IV, formula V or formula VI:

[0012]

[0013] Wherein, X is -F, -Cl or -Br; R is selected from -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3 or -CH2C6H5, and the value of n is in the range of 15-23.

[0014] The preparation method of the polysulfone containing the calixarene structural unit comprises the steps of:

[0015] In a non-protonic polar solvent, in the presence of a salt-forming agent and a water-separating agent, alkyl-etherified p-tert-butylcalix[n]arene and dihalogenated diphenyl sulfone react to obtain polysulfone containing calixarene structural units.

[0016] According to a preferred embodiment of the present invention, the preparation method of alkyl-etherified p-tert-butylcalix[n]arene includes the steps of: in an organic solvent, in the presence of a catalyst, reacting p-tert-butylcalix[n]arene and a halogenated hydrocarbon to obtain alkyl-etherified p-tert-butylcalix[n]arene.

[0017] Preferably, the organic solvent is one or a combination of two or more of benzene, toluene, xylene, cyclohexane, cyclohexanone, toluene-cyclohexanone, chlorobenzene, dichlorobenzene, dichloromethane, ether, propylene oxide, acetone, methyl butyl ketone, methyl isobutyl ketone, acetonitrile or pyridine; the molar amount of p-tert-butylcalix[n]arene and the volume ratio of the organic solvent are 0.01-1 mmol / mL.

[0018] Preferably, the catalyst is one or a combination of two or more of NaOH, KOH, K2CO3, Na2CO3, KHCO3, NaHCO3 or KI; the molar ratio of the catalyst to p-tert-butylcalix[n]arene is 2-5:1.

[0019] Preferably, the halogenated hydrocarbon is one of ethyl chloride, ethyl bromide, propyl chloride, propyl bromide, butyl chloride, butyl bromide or benzyl chloride.

[0020] Preferably, the molar ratio of the phenolic hydroxyl group to the halogenated hydrocarbon in the p-tert-butylcalix[n]arene is n:(n-2), wherein n is 4, 6 or 8.

[0021] Preferably, the reaction temperature is 50-100° C., the reaction time is 3-7 h, and the reaction is carried out under stirring and reflux conditions.

[0022] Preferably, the post-treatment method of the reaction solution obtained by the reaction is as follows: the reaction solution is filtered, the filtrate is subjected to rotary evaporation to remove the solvent, the residue is dissolved in chloroform, washed with sodium chloride aqueous solution, the oil phase is taken, the oil phase is dried over anhydrous sodium sulfate, rotary evaporated, and recrystallized to obtain alkyl-etherified p-tert-butylcalix[n]arene.

[0023] According to a preferred embodiment of the present invention, the aprotic polar solvent is one or a combination of two or more of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, or sulfolane. The molar amount of the alkyl-etherified p-tert-butylcalix[n]arene and the volume ratio of the aprotic polar solvent are 0.1-0.5 mmol / mL.

[0024] According to the preferred embodiment of the present invention, the salt-forming agent is one of NaOH, K2CO3 or Na2CO3. The molar ratio of the salt-forming agent to the alkyl-etherified p-tert-butylcalix[n]arene is 2-3:1.

[0025] According to the present invention, the water-separating agent is preferably one or a combination of two or more of toluene, xylene, mesitylene, o-trimethylbenzene, or ethylbenzene. The volume ratio of the molar amount of p-tert-butylcalix[n]arene or alkyl-etherified calix[n]arene to the water-separating agent is 0.1-1 mmol / mL.

[0026] According to the present invention, preferably, the dihalogenated diphenyl sulfone is 4,4'-difluorodiphenyl sulfone; and the molar ratio of the alkyl-etherified p-tert-butylcalix[n]arene to the dihalogenated diphenyl sulfone is 1:1.

[0027] According to the preferred embodiment of the present invention, the reaction conditions are as follows: stirring and reflux reaction at 150-170° C. for 1-3 hours, distilling off water, and then stirring and reacting at the boiling point of the aprotic polar solvent for 24-48 hours.

[0028] According to a preferred embodiment of the present invention, the post-treatment method of the reaction liquid obtained by the reaction is as follows: the reaction liquid is cooled to room temperature, filtered to remove inorganic salts, and then the product is precipitated with a precipitating agent, filtered, washed with water, filtered, and dried to obtain a polysulfone containing a calixarene structural unit; the precipitating agent used is one or a combination of two or more of methanol, ethanol or water.

[0029] Application of the above-mentioned polysulfone containing calixarene structural units in nanofiltration membranes.

[0030] According to the preferred embodiment of the present invention, the application method includes the steps of: dissolving polysulfone containing calixarene structural units and nonionic surfactant polyoxyethylene nonylphenyl ether in N-methylpyrrolidone, wherein the mass ratio of polysulfone containing calixarene structural units to nonionic surfactant polyoxyethylene nonylphenyl ether is 3-5:1, and the volume ratio of the mass of polysulfone containing calixarene structural units to N-methylpyrrolidone is 0.1-0.5 g / mL, and stirring at room temperature for 10-15 hours; coating on a glass plate; transferring the glass plate to distilled water, performing immersion precipitation phase conversion treatment, until the phase separation process is completed; immersing the obtained membrane in distilled water for 20-30 hours to completely precipitate the soluble components, and then sandwiching it between filter papers and drying at room temperature to obtain a nanofiltration membrane.

[0031] The reaction scheme of the present invention is shown as follows:

[0032]

[0033] In the formula, X1 and X are each independently selected from -F, -Cl or -Br; R1 is selected from -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3 or -CH2C6H5.

[0034] The technical features and beneficial effects of the present invention are as follows:

[0035] (1) In the present invention, p-tert-butylcalix[n]arene is used as a raw material and undergoes a substitution reaction with a halogenated hydrocarbon to obtain an alkyl-etherified p-tert-butylcalix[n]arene. The alkyl-etherified p-tert-butylcalix[n]arene and dihalogenated diphenyl sulfone are then polycondensed via a Farnham nucleophilic substitution reaction to form a polysulfone containing a calixarene structural unit. The raw materials of the present invention are commercially available, the synthesis steps are simple, and stable industrial production can be easily achieved.

[0036] (2) The present invention embeds calixarene into the polysulfone backbone in the form of a covalent bond. And by selecting the size of the calixarene ring ([4] / [6] / [8]) and etherification modification, the cavity size can be precisely controlled. The present invention is the first report to use calixarene as a raw material to design and synthesize polysulfone containing calixarene structural units. The nanocavity of calixarene has adjustable cavity size, selective adsorption, structural stability, and host-guest recognition capabilities. The synergistic effect of the hydrophobic cavity and hydrophilic edge of calixarene can dynamically control the wettability of the polysulfone surface and reduce the probability of pollutant adhesion. At the same time, the covalent bonding strategy ensures the high stability of the functional group and can maintain structural integrity in extreme pH or high salt environments.

[0037] (3) Compared with traditional polysulfones, the polysulfone of the present invention has molecular recognition ability due to the introduction of calixarene structural units, which is more conducive to achieving efficient filtration and selective enrichment in the precise separation of complex multi-component systems (such as those containing heavy metals, organic pollutants or biological molecules). It is expected to have potential and huge development prospects in the fields of high-value-added industrial wastewater treatment (such as electronic electroplating wastewater, pharmaceutical wastewater), biopharmaceutical purification (such as protein / antibody separation, targeted drug delivery) and resource recovery (such as precious metal / rare element extraction). BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 This is the GPC spectrum of the polysulfone PSUC4-1 containing the calixarene structural unit in Example 1;

[0039] Figure 2 This is the infrared spectrum of the polysulfone PSUC4-1 containing the calixarene structural unit in Example 1;

[0040] Figure 3 This is the H NMR spectrum of the polysulfone PSUC4-1 containing the calixarene structural unit in Example 1.

[0041] Figure 4 This is the TGA diagram of the polysulfone PSUC4-1 containing the calixarene structural unit in Example 1. DETAILED DESCRIPTION

[0042] The present invention will be further described below with reference to specific embodiments, but is not limited thereto.

[0043] Meanwhile, the experimental methods described in the following examples, unless otherwise specified, are conventional methods; the reagents and materials, unless otherwise specified, can be obtained from commercial channels.

[0044] Example 1

[0045] Preparation of polysulfone (PSUC4-1) with a calix[4]arene structure containing an ethyl ether group. The specific reaction route is as follows:

[0046]

[0047] The preparation steps of polysulfone (PSUC4-1) with a calix[4]arene structure containing an ethyl ether group are as follows:

[0048] 10 mmol of p-tert-butylcalix[4]arene, 25 mmol of potassium carbonate, and 3.6 mmol of potassium iodide were added to a three-necked flask equipped with a condenser, a magnet, and a thermometer. 100 ml of acetonitrile was then added and the mixture was stirred and refluxed under a N2 atmosphere for 0.5 h. 20 mmol of ethyl bromide was added to the flask and the mixture was stirred and refluxed at 85°C for 4 h. After filtering, the filtrate was obtained and the solvent was removed by rotary evaporation. The remaining viscous liquid was dissolved in chloroform. After washing with sodium chloride aqueous solution, the mixture was separated into two layers to remove the aqueous phase. The remaining chloroform solution was dried over anhydrous sodium sulfate and rotary evaporated to remove most of the chloroform. The resulting precipitate was recrystallized (chloroform / methanol volume ratio 3:7) to obtain a calix[4]arene solid containing an ethyl ether group (C4-1) with a yield of 77.3%.

[0049] 10 mmol of calix[4]arene (C4-1) containing ethyl etherification groups, 10 mmol of 4,4'-difluorodiphenyl sulfone, and 25 mmol of sodium hydroxide were dissolved in 20 mL of toluene and 80 mL of N-methylpyrrolidone. The mixture was placed in a four-necked flask equipped with a spherical condenser, a water separator, a mechanical stirring device, and a constant pressure dropping funnel. The mixture was heated at 170°C under reflux and stirred for 2 h, and then the water was removed by azeotropic distillation. The temperature was then raised to 200°C, and the mixture was reacted under reflux and mechanical stirring for 24 h. The reaction mixture was cooled to room temperature and filtered to remove inorganic salts. The product was then precipitated with distilled water. The precipitate was filtered and washed with water three times. The viscous solid was obtained by suction filtration and dried in a vacuum drying oven for 24 h to obtain a powdery solid, namely, calix[4]arene polysulfone (PSUC4-1) containing ethyl etherification groups. The yield was 81.9%. GPC: M n =16000, PDI=1.7. Specific structural characterization results are shown in Figure 1-3 .

[0050] Depend on Figure 1The results show that the GPC curve of PSUC4-1 polymer shifts significantly toward the high molecular weight side compared with the p-tert-butylcalix[4]arene curve, and the elution curve is multi-peaked, indicating that a mixture of a polymer with a molecular weight of 16,000 g / mol and oligomers with molecular weights of 3,000 g / mol, 2,300 g / mol, and 800 g / mol is obtained.

[0051] Depend on Figure 2 The results show that 1242cm -1 The peak at 1147 cm is the stretching vibration peak of Ar-O-Ar. -1 The peak at is the symmetric stretching vibration peak of sulfone group (-SO2-); Figure 3 It can be seen that the characteristic methylene peaks a of calixarene appear at δ=3.37ppm and 2.37ppm, and the characteristic methyl peaks of p-tert-butyl appear at δ=1.21ppm and 1.19ppm, indicating the successful synthesis of the target product.

[0052] Figure 4 The TGA diagram of polysulfone PSUC4-1 is shown in Figure 2. Figure 4 It can be seen that the temperature (T d5 ) is 367℃, the temperature of 10% weight loss (T d10 ) is 406℃. The results of thermal stability study show that polysulfone containing calixarene structural units has high thermal stability.

[0053] Example 2

[0054] The preparation steps of polysulfone (PSUC4-2) with a calix[4]arene structure containing a propyl etherified group are as follows:

[0055] 10 mmol of p-tert-butylcalix[4]arene, 25 mmol of potassium carbonate, and 3.6 mmol of potassium iodide were added to a three-necked flask equipped with a condenser, a magnet, and a thermometer. 100 ml of acetonitrile was then added and the mixture was stirred and refluxed under a N2 atmosphere for 0.5 h. 20 mmol of bromopropane was added to the flask and the mixture was stirred and refluxed at 85°C for 4 h. After filtering, the filtrate was obtained and the solvent was removed by rotary evaporation. The remaining viscous liquid was dissolved in chloroform. After washing with sodium chloride aqueous solution, the mixture was separated into two layers to remove the aqueous phase. The remaining chloroform solution was dried over anhydrous sodium sulfate and rotary evaporated to remove most of the chloroform. The resulting precipitate was recrystallized (chloroform / methanol volume ratio 3:7) to obtain a calix[4]arene solid (C4-2) containing a propyl ether group with a yield of 82.1%.

[0056] 10 mmol of calix[4]arene (C4-2) containing propyl etherification groups, 10 mmol of 4,4'-difluorodiphenyl sulfone, and 25 mmol of sodium hydroxide were dissolved in 20 mL of toluene and 80 mL of N-methylpyrrolidone. The mixture was placed in a four-necked flask equipped with a spherical condenser, a water separator, a mechanical stirring device, and a constant pressure dropping funnel. The mixture was heated at 170°C under reflux and stirred for 2 h, and then the water was removed by azeotropic distillation. The temperature was then raised to 200°C, and the mixture was reacted under reflux and mechanical stirring for 24 h. The reaction mixture was cooled to room temperature and filtered to remove inorganic salts. The product was then precipitated with distilled water. The precipitate was filtered and washed with water three times. The viscous solid was then filtered to obtain a powdered solid. The solid was dried in a vacuum oven for 24 h to obtain a calix[4]arene polysulfone (PSUC4-2) containing propyl etherification groups. The yield was 81.3%. GPC: M n =15000, PDI=1.9.

[0057] Example 3

[0058] The preparation steps of polysulfone (PSUC4-3) containing a butylated calix[4]arene structure are as follows:

[0059] 10 mmol of p-tert-butylcalix[4]arene, 25 mmol of potassium carbonate, and 3.6 mmol of potassium iodide were added to a three-necked flask equipped with a condenser, a magnet, and a thermometer. 100 ml of acetonitrile was then added and the mixture was stirred and refluxed under N2 atmosphere for 0.5 h. 20 mmol of bromobutane was added to the flask and the mixture was stirred and refluxed at 85°C for 4 h. After filtering, the filtrate was obtained and the solvent was removed by rotary evaporation. The remaining viscous liquid was dissolved in chloroform. After washing with sodium chloride aqueous solution, the mixture was separated into two layers to remove the aqueous phase. The remaining chloroform solution was dried over anhydrous sodium sulfate and rotary evaporated to remove most of the chloroform. The resulting precipitate was recrystallized (chloroform / methanol volume ratio 3:7) to obtain a light yellow butyl ether group-containing calix[4]arene solid (C4-3) with a yield of 84.3%.

[0060] 10 mmol of [4]arene (C4-3) containing butyl ether groups, 10 mmol of 4,4'-difluorodiphenyl sulfone, and 25 mmol of sodium hydroxide were dissolved in 20 mL of toluene and 80 mL of N-methylpyrrolidone. The mixture was placed in a four-necked flask equipped with a spherical condenser, a water separator, a mechanical stirrer, and a constant pressure dropping funnel. The mixture was heated at 170°C under reflux and stirred for 2 h, and then the water was removed by azeotropic distillation. The temperature was then raised to 200°C, and the reaction was continued under reflux and mechanical stirring for 24 h. The reaction mixture was cooled to room temperature and filtered to remove inorganic salts. The product was then precipitated with distilled water. The precipitate was filtered and washed with water three times. The viscous solid was then filtered to obtain a powdered solid. The solid was dried in a vacuum oven for 24 h to obtain a powdered solid, namely [4]arene polysulfone (PSUC4-3) containing butyl ether groups. The yield was 80.1%. GPC: M n =16000, PDI=1.5.

[0061] Example 4

[0062] The preparation steps of polysulfone (PSUC4-4) with a calix[4]arene structure containing a benzyl etherification group are as follows:

[0063] 10 mmol of p-tert-butylcalix[4]arene, 25 mmol of potassium carbonate, and 3.6 mmol of potassium iodide were added to a three-necked flask equipped with a condenser, a magnet, and a thermometer. 100 ml of acetonitrile was then added and the mixture was stirred and refluxed under a N2 atmosphere for 0.5 h. 20 mmol of benzyl chloride was added to the flask and stirred and refluxed at 85°C for 4 h. After filtering, the filtrate was obtained and the solvent was removed by rotary evaporation. The remaining viscous liquid was dissolved in chloroform. After washing with sodium chloride aqueous solution, the mixture was separated into two layers to remove the aqueous phase. The remaining chloroform solution was dried over anhydrous sodium sulfate and rotary evaporated to remove most of the chloroform. The resulting precipitate was recrystallized (chloroform / methanol volume ratio 3:7) to obtain a calix[4]arene solid (C4-4) containing a benzyl etherification group with a yield of 79.9%.

[0064] 10 mmol of benzyl-etherified [4]arene (C4-4), 10 mmol of 4,4'-difluorodiphenyl sulfone, and 25 mmol of sodium hydroxide were dissolved in 20 mL of toluene and 80 mL of N-methylpyrrolidone. The mixture was placed in a four-necked flask equipped with a spherical condenser, a water separator, a mechanical stirring device, and a constant pressure dropping funnel. The mixture was heated at 170°C under reflux and stirred for 2 h, and then the water was removed by azeotropic distillation. The temperature was then raised to 200°C, and the mixture was reacted under reflux and mechanical stirring for 24 h. The reaction mixture was cooled to room temperature and filtered to remove inorganic salts. The product was then precipitated with distilled water. The precipitate was filtered and washed with water three times. The viscous solid was obtained by suction filtration and dried in a vacuum drying oven for 24 h to obtain a powdery solid, namely, benzyl-etherified [4]arene polysulfone (PSUC4-4). The yield was 78.9%. GPC: M n =16000, PDI=1.8.

[0065] Example 5

[0066] The preparation steps of polysulfone (PSUC6-1) containing a calix[6]arene structure and an ethyl etherification group are as follows:

[0067] 10 mmol of p-tert-butylcalix[6]arene, 25 mmol of potassium carbonate, and 3.6 mmol of potassium iodide were added to a three-necked flask equipped with a condenser, a magnet, and a thermometer. 100 ml of acetonitrile was then added and the mixture was stirred and refluxed under a N2 atmosphere for 0.5 h. 40 mmol of ethyl bromide was added to the flask and the mixture was stirred and refluxed at 85°C for 4 h. After filtering, the filtrate was obtained and the solvent was removed by rotary evaporation. The remaining viscous liquid was dissolved in chloroform. After washing with sodium chloride aqueous solution, the mixture was separated into two layers to remove the aqueous phase. The remaining chloroform solution was dried over anhydrous sodium sulfate and rotary evaporated to remove most of the chloroform. The resulting precipitate was recrystallized (chloroform / methanol volume ratio 3:7) to obtain a calix[6]arene solid containing an ethyl ether group (C6-1) with a yield of 74.9%.

[0068] 10 mmol of calix[6]arene (C6-1) containing ethyl etherification groups, 10 mmol of 4,4'-difluorodiphenyl sulfone, and 25 mmol of sodium hydroxide were dissolved in 20 mL of toluene and 80 mL of N-methylpyrrolidone. The mixture was placed in a four-necked flask equipped with a spherical condenser, a water separator, a mechanical stirring device, and a constant pressure dropping funnel. The mixture was heated at 170°C under reflux and stirred for 2 h, and then the water was removed by azeotropic distillation. The temperature was then raised to 200°C, and the mixture was reacted under reflux and mechanical stirring for 24 h. The reaction mixture was cooled to room temperature and filtered to remove inorganic salts. The product was then precipitated with distilled water. The precipitate was filtered and washed with water three times. The viscous solid was then filtered to obtain a powdered solid. The solid was dried in a vacuum oven for 24 h to obtain a powdered solid, namely, calix[6]arene polysulfone (PSUC6-1) containing ethyl etherification groups. The yield was 82.5%. GPC: M n =16000, PDI=1.7.

[0069] Example 6

[0070] The preparation steps of polysulfone (PSUC6-2) with a calix[6]arene structure containing a propyl etherified group are as follows:

[0071] 10 mmol of p-tert-butylcalix[6]arene, 25 mmol of potassium carbonate, and 3.6 mmol of potassium iodide were added to a three-necked flask equipped with a condenser, a magnet, and a thermometer. 100 ml of acetonitrile was then added and the mixture was stirred and refluxed under a N2 atmosphere for 0.5 h. 40 mmol of bromopropane was added to the flask and the mixture was stirred and refluxed at 85°C for 4 h. After filtering, the filtrate was obtained and the solvent was removed by rotary evaporation. The remaining viscous liquid was dissolved in chloroform. After washing with sodium chloride aqueous solution, the mixture was separated into two layers to remove the aqueous phase. The remaining chloroform solution was dried over anhydrous sodium sulfate and rotary evaporated to remove most of the chloroform. The resulting precipitate was recrystallized (chloroform / methanol volume ratio 3:7) to obtain a calix[6]arene solid (C6-2) containing a propyl ether group with a yield of 75.9%.

[0072] 10 mmol of calix[6]arene (C6-2) containing propyl etherification groups, 10 mmol of 4,4'-difluorodiphenyl sulfone, and 25 mmol of sodium hydroxide were dissolved in 20 mL of toluene and 80 mL of N-methylpyrrolidone. The mixture was placed in a four-necked flask equipped with a spherical condenser, a water separator, a mechanical stirring device, and a constant pressure dropping funnel. The mixture was heated at 170°C under reflux and stirred for 2 h, and then the water was removed by azeotropic distillation. The temperature was then raised to 200°C, and the mixture was reacted under reflux and mechanical stirring for 24 h. The reaction mixture was cooled to room temperature and filtered to remove inorganic salts. The product was then precipitated with distilled water. The precipitate was filtered and washed with water three times. The viscous solid was then filtered to obtain a powdered solid. The solid was dried in a vacuum oven for 24 h to obtain a calix[6]arene polysulfone (PSUC6-2) containing propyl etherification groups. The yield was 82.3%. GPC: M n =18000, PDI=1.6.

[0073] Example 7

[0074] The preparation steps of polysulfone (PSUC6-3) containing a butylated calix[6]arene structure are as follows:

[0075] 10 mmol of p-tert-butylcalix[6]arene, 25 mmol of potassium carbonate, and 3.6 mmol of potassium iodide were added to a three-necked flask equipped with a condenser, a magnet, and a thermometer. 100 ml of acetonitrile was then added and the mixture was stirred and refluxed under a N2 atmosphere for 0.5 h. 40 mmol of bromobutane was added to the flask and the mixture was stirred and refluxed at 85°C for 4 h. After filtering, the filtrate was obtained and the solvent was removed by rotary evaporation. The remaining viscous liquid was dissolved in chloroform. After washing with sodium chloride aqueous solution, the mixture was separated into two layers to remove the aqueous phase. The remaining chloroform solution was dried over anhydrous sodium sulfate and rotary evaporated to remove most of the chloroform. The resulting precipitate was recrystallized (chloroform / methanol volume ratio 3:7) to obtain a butyl-etherified calix[6]arene solid (C6-3) with a yield of 72.1%.

[0076] 10 mmol of butylated calix[6]arene (C6-3), 10 mmol of 4,4'-difluorodiphenyl sulfone, and 25 mmol of sodium hydroxide were dissolved in 20 mL of toluene and 80 mL of N-methylpyrrolidone. The mixture was placed in a four-necked flask equipped with a spherical condenser, a water separator, a mechanical stirrer, and a constant pressure dropping funnel. The mixture was heated at 170°C under reflux and stirred for 2 h, and then the water was removed by azeotropic distillation. The temperature was then raised to 200°C, and the mixture was reacted under reflux and mechanical stirring for 24 h. The reaction mixture was cooled to room temperature and filtered to remove inorganic salts. The product was then precipitated with distilled water. The precipitate was filtered and washed with water three times. The viscous solid was then filtered to obtain a powdered solid. The solid was dried in a vacuum oven for 24 h to obtain a butylated calix[6]arene polysulfone (PSUC6-3). The yield was 81.2%. GPC: M n =17000, PDI=1.5.

[0077] Example 8

[0078] The preparation steps of polysulfone (PSUC6-4) with a calix[6]arene structure containing a benzyl etherification group are as follows:

[0079] 10 mmol of p-tert-butylcalix[6]arene, 25 mmol of potassium carbonate, and 3.6 mmol of potassium iodide were added to a three-necked flask equipped with a condenser, a magnet, and a thermometer. 100 ml of acetonitrile was then added and the mixture was stirred and refluxed under a N2 atmosphere for 0.5 h. 40 mmol of benzyl chloride was added to the flask and stirred and refluxed at 85°C for 4 h. After filtering, the filtrate was obtained and the solvent was removed by rotary evaporation. The remaining viscous liquid was dissolved in chloroform. After washing with sodium chloride aqueous solution, the mixture was separated into two layers to remove the aqueous phase. The remaining chloroform solution was dried over anhydrous sodium sulfate and rotary evaporated to remove most of the chloroform. The resulting precipitate was recrystallized (chloroform / methanol volume ratio 3:7) to obtain a calix[6]arene solid (C6-4) containing a benzyl etherification group with a yield of 82.3%.

[0080] 10 mmol of benzyl-etherified calix[6]arene (C6-4), 10 mmol of 4,4'-difluorodiphenyl sulfone, and 25 mmol of sodium hydroxide were dissolved in 20 mL of toluene and 80 mL of N-methylpyrrolidone. The mixture was placed in a four-necked flask equipped with a spherical condenser, a water separator, a mechanical stirrer, and a constant pressure dropping funnel. The mixture was heated at 170°C under reflux and stirred for 2 h, and then the water was removed by azeotropic distillation. The temperature was then raised to 200°C, and the mixture was reacted under reflux and mechanical stirring for 24 h. The reaction mixture was cooled to room temperature and filtered to remove inorganic salts. The product was then precipitated with distilled water. The precipitate was filtered and washed with water three times. The viscous solid was then filtered to obtain a powdered solid. The solid was dried in a vacuum oven for 24 h to obtain a benzyl-etherified calix[6]arene polysulfone (PSUC6-4). The yield was 83.4%. GPC: M n =18000, PDI=1.7.

[0081] Example 9

[0082] The preparation steps of polysulfone (PSUC8-1) containing a calix[8]arene structure and an ethyl etherification group are as follows:

[0083] 10 mmol of p-tert-butylcalix[8]arene, 25 mmol of potassium carbonate, and 3.6 mmol of potassium iodide were added to a three-necked flask equipped with a condenser, a magnet, and a thermometer. 100 ml of acetonitrile was then added and the mixture was stirred and refluxed under a N2 atmosphere for 0.5 h. 60 mmol of ethyl bromide was added to the flask and the mixture was stirred and refluxed at 85°C for 4 h. After filtering, the filtrate was obtained and the solvent was removed by rotary evaporation. The remaining viscous liquid was dissolved in chloroform. After washing with sodium chloride aqueous solution, the mixture was separated into two layers to remove the aqueous phase. The remaining chloroform solution was dried over anhydrous sodium sulfate and rotary evaporated to remove most of the chloroform. The resulting precipitate was recrystallized (chloroform / methanol volume ratio 3:7) to obtain a calix[8]arene solid containing an ethyl ether group (C8-1) with a yield of 67.9%.

[0084] 10 mmol of calix[8]arene (C8-1) containing an ethyl etherification group, 10 mmol of 4,4'-difluorodiphenyl sulfone, and 25 mmol of sodium hydroxide were dissolved in 20 mL of toluene and 80 mL of N-methylpyrrolidone. The mixture was placed in a four-necked flask equipped with a spherical condenser, a water separator, a mechanical stirring device, and a constant pressure dropping funnel. The mixture was heated at 170°C under reflux and stirred for 2 h, and then the water was removed by azeotropic distillation. The temperature was then raised to 200°C, and the mixture was reacted under reflux and mechanical stirring for 24 h. The reaction mixture was cooled to room temperature and filtered to remove inorganic salts. The product was then precipitated with distilled water. The precipitate was filtered and washed with water three times. The viscous solid was then filtered to obtain a powdered solid. The solid was dried in a vacuum oven for 24 h to obtain a polysulfone (PSUC8-1) containing an ethyl etherification group. The yield was 79.3%. GPC: M n =20000, PDI=1.9.

[0085] Example 10

[0086] The preparation steps of polysulfone (PSUC8-2) with a calix[8]arene structure containing a propyl etherification group are as follows:

[0087] 10 mmol of p-tert-butylcalix[8]arene, 25 mmol of potassium carbonate, and 3.6 mmol of potassium iodide were added to a three-necked flask equipped with a condenser, a magnet, and a thermometer. 100 ml of acetonitrile was then added and the mixture was stirred and refluxed under a N2 atmosphere for 0.5 h. 60 mmol of bromopropane was added to the flask and the mixture was stirred and refluxed at 85°C for 4 h. After filtering, the filtrate was obtained and the solvent was removed by rotary evaporation. The remaining viscous liquid was dissolved in chloroform. After washing with sodium chloride aqueous solution, the mixture was separated into two layers to remove the aqueous phase. The remaining chloroform solution was dried over anhydrous sodium sulfate and rotary evaporated to remove most of the chloroform. The resulting precipitate was recrystallized (chloroform / methanol volume ratio 3:7) to obtain a calix[8]arene solid (C8-2) containing a propyl ether group with a yield of 74.5%.

[0088] 10 mmol of calix[8]arene (C8-2) containing propyl etherification groups, 10 mmol of 4,4'-difluorodiphenyl sulfone, and 25 mmol of sodium hydroxide were dissolved in 20 mL of toluene and 80 mL of N-methylpyrrolidone. The mixture was placed in a four-necked flask equipped with a spherical condenser, a water separator, a mechanical stirring device, and a constant pressure dropping funnel. The mixture was heated at 170°C under reflux and stirred for 2 h, and then the water was removed by azeotropic distillation. The temperature was then raised to 200°C, and the mixture was reacted under reflux and mechanical stirring for 24 h. The reaction mixture was cooled to room temperature and filtered to remove inorganic salts. The product was then precipitated with distilled water. The precipitate was filtered and washed with water three times. The viscous solid was obtained by suction filtration. The solid was dried in a vacuum oven for 24 h to obtain a powdery solid, which was polysulfone (PSUC8-2) containing propyl etherification groups. The yield was 85.1%. GPC: M n =18000, PDI=1.7.

[0089] Example 11

[0090] The preparation steps of polysulfone (PSUC8-3) containing a butylated calix[8]arene structure are as follows:

[0091] 10 mmol of p-tert-butylcalix[8]arene, 25 mmol of potassium carbonate, and 3.6 mmol of potassium iodide were added to a three-necked flask equipped with a condenser, a magnet, and a thermometer. 100 ml of acetonitrile was then added and the mixture was stirred and refluxed under a N2 atmosphere for 0.5 h. 60 mmol of bromobutane was added to the flask and the mixture was stirred and refluxed at 85°C for 4 h. After filtering, the filtrate was obtained and the solvent was removed by rotary evaporation. The remaining viscous liquid was dissolved in chloroform. After washing with sodium chloride aqueous solution, the mixture was separated into two layers to remove the aqueous phase. The remaining chloroform solution was dried over anhydrous sodium sulfate and rotary evaporated to remove most of the chloroform. The resulting precipitate was recrystallized (chloroform / methanol volume ratio 3:7) to obtain a butyl etherified group-containing calix[8]arene solid (C8-3) with a yield of 71.4%.

[0092] 10 mmol of butylated calix[8]arene (C8-3), 10 mmol of 4,4'-difluorodiphenyl sulfone, and 25 mmol of sodium hydroxide were dissolved in 20 mL of toluene and 80 mL of N-methylpyrrolidone. The mixture was placed in a four-necked flask equipped with a spherical condenser, a water separator, a mechanical stirrer, and a constant pressure dropping funnel. The mixture was heated at 170°C under reflux and stirred for 2 h, and then the water was removed by azeotropic distillation. The temperature was then raised to 200°C, and the mixture was reacted under reflux and mechanical stirring for 24 h. The reaction mixture was cooled to room temperature and filtered to remove inorganic salts. The product was then precipitated with distilled water. The precipitate was filtered and washed with water three times. The viscous solid was then filtered to obtain a powdered solid. The solid was dried in a vacuum oven for 24 h to obtain a polysulfone (PSUC8-3) containing a butylated calix[8]arene structure. The yield was 83.7%. GPC: M n =17000, PDI=1.8.

[0093] Example 12

[0094] The preparation steps of polysulfone (PSUC8-4) with a calix[8]arene structure containing a benzyl etherification group are as follows:

[0095] 10 mmol of p-tert-butylcalix[8]arene, 25 mmol of potassium carbonate, and 3.6 mmol of potassium iodide were added to a three-necked flask equipped with a condenser, a magnet, and a thermometer. 100 ml of acetonitrile was then added and the mixture was stirred and refluxed under a N2 atmosphere for 0.5 h. 60 mmol of benzyl chloride was added to the flask and stirred and refluxed at 85°C for 4 h. After filtering, the filtrate was obtained and the solvent was removed by rotary evaporation. The remaining viscous liquid was dissolved in chloroform. After washing with sodium chloride aqueous solution, the mixture was separated into two layers to remove the aqueous phase. The remaining chloroform solution was dried over anhydrous sodium sulfate and rotary evaporated to remove most of the chloroform. The resulting precipitate was recrystallized (chloroform / methanol volume ratio 3:7) to obtain a calix[8]arene solid (C8-4) containing a benzyl etherification group with a yield of 73.9%.

[0096] 10 mmol of benzyl-etherified calix[8]arene (C8-4), 10 mmol of 4,4'-difluorodiphenyl sulfone, and 25 mmol of sodium hydroxide were dissolved in 20 mL of toluene and 80 mL of N-methylpyrrolidone. The mixture was placed in a four-necked flask equipped with a spherical condenser, a water separator, a mechanical stirrer, and a constant pressure dropping funnel. The mixture was heated at 170°C under reflux and stirred for 2 h, and then the water was removed by azeotropic distillation. The temperature was then raised to 200°C, and the mixture was reacted under reflux and mechanical stirring for 24 h. The reaction mixture was cooled to room temperature and filtered to remove inorganic salts. The product was then precipitated with distilled water. The precipitate was filtered and washed with water three times. The viscous solid was then filtered to obtain a powdered solid. The solid was dried in a vacuum oven for 24 h to obtain a polysulfone (PSUC8-4) containing a benzyl-etherified calix[8]arene structure. The yield was 82.3%. GPC: M n =17000, PDI=1.9.

[0097] Application Examples

[0098] Preparation of nanofiltration membrane:

[0099] The calixarene polysulfone prepared in Example 1-2 and the nonionic surfactant IGEPAL CO-890 (polyoxyethylene (40) nonylphenyl ether, HLB = 17) were dissolved in N-methylpyrrolidone solvent, wherein the mass ratio of the calixarene polysulfone to the nonionic surfactant IGEPAL CO-890 was 4:1, and the volume ratio of the mass of the calixarene polysulfone to N-methylpyrrolidone was 1:5 g / ml. The mixture was stirred at room temperature for 12 hours to form a homogeneous casting solution. The casting solution was evenly coated on a pretreated glass plate using a scraper with a gap of 300 μm to form a wet film. The glass plate was transferred to a distilled water coagulation bath and subjected to immersion precipitation phase conversion treatment until the main phase separation process was completed. The resulting nascent membrane was immersed in distilled water for 24 hours to completely precipitate the soluble components, and then sandwiched between filter papers and dried at room temperature for 24 hours to obtain a polysulfone flat membrane.

[0100] Test methods for water flux and retention rate:

[0101] The prepared nanofiltration membrane was cut into 5 cm × 5 cm squares and pre-pressed at 0.2 MPa for 30 minutes to stabilize the flux. The water flux and retention rate of the membrane were then measured at 0.2 MPa. The absorbance of the permeate and the original solution was measured using a UV-visible photometer, and the dye concentration was calculated using the concentration-absorbance regression equation.

[0102] The water flux formula of calixarene polysulfone nanofiltration membrane is as follows:

[0103]

[0104] Where, F is water flux, L·m2 ·h -1 ;

[0105] V——permeate liquid volume, L;

[0106] A——effective area of ​​nanofiltration membrane m 2 ;

[0107] T——time, h.

[0108] The retention rate R of the calixarene polysulfone nanofiltration membrane for dyes or metal salts is calculated as follows:

[0109]

[0110] Where, R——retention rate, %;

[0111] c p ——Dye or metal salt concentration of the permeate, g / L;

[0112] c f ——Dye or metal salt concentration in feed solution, g / L

[0113] The water flux and rejection rate of the nanofiltration membrane are shown in Table 1.

[0114] Table 1 Water flux and rejection of PSU-based membrane, PSUC4-1 membrane and PSUC4-2 membrane

[0115]

[0116] Under the test conditions of 0.6 MPa, 25°C, and pH = 7, the retention rate and water flux of the calixarene-modified polysulfone nanofiltration membrane for six types of solutes (Congo red, methyl blue, methylene blue, indigo, Al2(SO4)3, and MgCl2) showed significant differences (Table 1).

[0117] The retention rate of ordinary polysulfone ultrafiltration membrane for neutral small molecules (such as indigo, 147Da) is about 38.6%, and the flux is 17.9L / (m 2 ·h). Due to the specific adsorption effect, the retention rate of methyl blue (800Da) of calixarene polysulfone membrane such as PSUC4-2 can reach 94.3%, and the flux is 13.8L / (m 2 ·h); The rejection rate of PSUC4-1 polysulfone membrane for high-valent salt (Al2(SO4)3) is increased to 94.2%.

[0118] The retained hydroxyl groups of PSUC4-1 polysulfone enhance the negative charge density on the membrane surface, which greatly improves the electrostatic repulsion of SO4 2-The retention rate of PSUC4-2 polysulfone was 94.2% and 96.5% for negatively charged methyl blue (94.2% and 96.5%), but the rejection capacity for positively charged solute (methyl blue) was weakened (78.9%). After the hydroxyl groups of PSUC4-2 polysulfone were replaced by hydrophobic groups, its cavity structure selectively captured positively charged methyl blue (94.3%) through hydrophobic adsorption, while the pore size contraction caused the flux to decrease (13.8 L / (m 2 ·h)).

[0119] PSUC4-1 polysulfone membrane has strong hydrophilicity due to the retention of hydroxyl groups, which reduces membrane pore blockage and increases the flux of neutral solutes (indigo red) (29.1L / (m 2 ·h)). PSUC4-2 polysulfone membrane has increased hydrophobicity due to the replacement of all hydroxyl groups, and preferentially adsorbs hydrophobic molecules (such as indigo), but the flux is limited (20.6L / (m 2 ·h)).

[0120] The present invention is not limited to the above-mentioned specific implementation methods. Various changes made by ordinary technicians in this field based on the above-mentioned concept without creative work are all within the scope of protection of the present invention.

Claims

1. A polysulfone containing a calixarene structural unit, characterized in that: It is obtained by reacting the hydroxyl group in alkyl-etherified p-tert-butylcalix[n]arene with the halogen in dihalogenated diphenyl sulfone; Wherein, the alkyl-etherified p-tert-butylcalix[n]arene has a structure shown in the following formula I, formula II or formula III: wherein R is selected from -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3 or -CH2C6H5.

2. The polysulfone containing calixarene structural units according to claim 1, characterized in that The structure of the polysulfone containing the calixarene structural unit is shown in Formula IV, Formula V or Formula VI below: Wherein, X is -F, -Cl or -Br; R is selected from -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3 or -CH2C6H5, and the value of n is in the range of 15-23.

3. The method for preparing the polysulfone containing calixarene structural units according to claim 1 or 2, comprising the steps of: In a non-protonic polar solvent, in the presence of a salt-forming agent and a water-separating agent, alkyl-etherified p-tert-butylcalix[n]arene and dihalogenated diphenyl sulfone react to obtain polysulfone containing calixarene structural units.

4. The method for preparing polysulfone containing calixarene structural units according to claim 3, characterized in that: The preparation method of alkyl-etherified p-tert-butylcalix[n]arene comprises the following steps: in an organic solvent, under the action of a catalyst, p-tert-butylcalix[n]arene and a halogenated hydrocarbon are reacted to obtain alkyl-etherified p-tert-butylcalix[n]arene.

5. The method for preparing polysulfone containing calixarene structural units according to claim 4, characterized in that: Include one or more of the following conditions: i. The organic solvent is one or a combination of two or more of benzene, toluene, xylene, cyclohexane, cyclohexanone, toluene-cyclohexanone, chlorobenzene, dichlorobenzene, dichloromethane, ether, propylene oxide, acetone, methyl butyl ketone, methyl isobutyl ketone, acetonitrile or pyridine; the molar amount of p-tert-butylcalix[n]arene and the volume ratio of the organic solvent are 0.01-1 mmol / mL; ii. The catalyst is one or a combination of two or more of NaOH, KOH, K2CO3, Na2CO3, KHCO3, NaHCO3 or KI; the molar ratio of the catalyst to p-tert-butylcalix[n]arene is 2-5:1; iii. The halogenated hydrocarbon is one of ethyl chloride, ethyl bromide, propyl chloride, propyl bromide, butyl chloride, butyl bromide or benzyl chloride; iv. The molar ratio of the phenolic hydroxyl group in the p-tert-butylcalix[n]arene to the halogenated hydrocarbon is n:(n-2), wherein n is 4, 6 or 8; v. The reaction temperature is 50-100°C, the reaction time is 3-7h, and the reaction is carried out under stirring and reflux conditions.

6. The method for preparing polysulfone containing calixarene structural units according to claim 3, characterized in that: Include one or more of the following conditions: i. The aprotic polar solvent is one or a combination of two or more of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide or sulfolane; the molar amount of the alkyl-etherified p-tert-butylcalix[n]arene and the volume ratio of the aprotic polar solvent is 0.1-0.5 mmol / mL; ii. The salt-forming agent is one of NaOH, K2CO3 or Na2CO3; the molar ratio of the salt-forming agent to the alkyl-etherified p-tert-butylcalix[n]arene is 2-3:1; iii. The water-separating agent is one or a combination of two or more of toluene, xylene, mesitylene, o-trimethylbenzene or ethylbenzene; the volume ratio of the molar amount of p-tert-butylcalix[n]arene or alkyl-etherified calix[n]arene to the water-separating agent is 0.1-1 mmol / mL.

7. The method for preparing polysulfone containing calixarene structural units according to claim 3, characterized in that: The dihalogenated diphenyl sulfone is 4,4'-difluorodiphenyl sulfone; and the molar ratio of the alkyl-etherified p-tert-butylcalix[n]arene to the dihalogenated diphenyl sulfone is 1:

1.

8. The method for preparing polysulfone containing calixarene structural units according to claim 3, characterized in that: The reaction conditions are as follows: stirring and refluxing at 150-170° C. for 1-3 hours, distilling off water, and then stirring and reacting at the boiling point of the aprotic polar solvent for 24-48 hours.

9. Use of the polysulfone containing calixarene structural units as claimed in claim 1 or 2 in nanofiltration membrane.

10. The use according to claim 9, characterized in that The application method comprises the following steps: dissolving polysulfone containing calixarene structural units and nonionic surfactant polyoxyethylene nonylphenyl ether in N-methyl pyrrolidone, wherein the mass ratio of polysulfone containing calixarene structural units to nonionic surfactant polyoxyethylene nonylphenyl ether is 3-5:1, and the volume ratio of the mass of polysulfone containing calixarene structural units to N-methyl pyrrolidone is 0.1-0.5 g / mL, stirring at room temperature for 10-15 hours; coating on a glass plate; transferring the glass plate into distilled water, performing immersion precipitation phase conversion treatment, and completing the phase separation process; immersing the obtained membrane in distilled water for 20-30 hours to completely precipitate the soluble components, and then sandwiching between filter papers and drying at room temperature to obtain a nanofiltration membrane.

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