阅读说明：本技术 一种耐腐蚀聚芳醚树脂、耐腐蚀分离膜及其制备方法 (Corrosion-resistant polyarylether resin, corrosion-resistant separation membrane and preparation method thereof ) 是由 张刚 邓萧 杨杰 毛其泽 陆浩然 严光明 严永刚 王孝军 于 2021-01-04 设计创作，主要内容包括：本发明涉及一种耐腐蚀聚芳醚树脂、耐腐蚀分离膜及其制备方法,属于高分子材料领域。本发明提供一种耐腐蚀聚芳醚树脂,其原料由以下组分组成：含硫或含氧单体56～400重量份,侧链含叔胺二卤代单体5～309重量份,二卤代芳香化合物1～500重量份,溶剂600～5000重量份,碱1～200重量份,催化剂1～100重量份,脱水剂0～100重量份。本发明所得耐腐蚀聚芳醚树脂及采用其制成的分离膜,所得具有优异的分离效率、超耐腐蚀性、抗污染性能、良好的机械性能和极其优异的膜孔大尺度范围内的可逆转换切换和膜再生性能,可用于制备高性能、多功能型分离膜,具有广泛的应用前景。(The invention relates to a corrosion-resistant polyarylether resin, a corrosion-resistant separation membrane and a preparation method thereof, belonging to the field of high polymer materials. The invention provides a corrosion-resistant polyarylether resin which comprises the following raw materials in parts by weight: 56-400 parts of sulfur-containing or oxygen-containing monomer, 5-309 parts of side-chain tertiary amine-containing dihalogenated monomer, 1-500 parts of dihalogenated aromatic compound, 600-5000 parts of solvent, 1-200 parts of alkali, 1-100 parts of catalyst and 0-100 parts of dehydrating agent. The corrosion-resistant polyarylether resin and the separation membrane prepared from the corrosion-resistant polyarylether resin have excellent separation efficiency, super corrosion resistance, pollution resistance, good mechanical property and extremely excellent reversible switching and membrane regeneration performance in a large-scale range of membrane pores, can be used for preparing high-performance and multifunctional separation membranes, and have wide application prospects.)

1. The corrosion-resistant polyarylether resin is characterized by comprising the following raw materials:

wherein the side chain tertiary amine-containing dihalogenated monomer is any one of the compounds shown in the following structural formula:

2. the corrosion-resistant polyarylether resin of claim 1, wherein the sulfur-or oxygen-containing monomer is any one of compounds represented by the following structural formula:

further, the dihalo-aromatic compound has a structural formula of Y-Ar-Y, Y ═ F or Cl,

wherein m is 2,4, 6, 8 or 10.

3. The corrosion-resistant polyarylether resin of claim 1 or 2, wherein the side chain tertiary amine-containing dihalo-monomer is prepared by a preparation method comprising the steps of:

(1) preparation of dihalogenated monomer containing tertiary amine at side chain

Sequentially adding 88-136 parts by weight of amine containing a tertiary amine structure, 40 parts by weight of alkali and 1-30 parts by weight of surfactant into 300-1500 parts by weight of deionized water, and dissolving at room temperature to obtain an amine solution containing a tertiary amine structure; uniformly mixing 176-209 parts by weight of 3, 5-dihalogenated formyl chloride and 500-3000 parts by weight of organic solvent, adding the mixture into a reaction vessel, dropwise adding the prepared tertiary amine structure-containing amine solution into the reaction vessel, and continuously reacting for 3-10 h at room temperature after dropwise adding the tertiary amine structure-containing amine solution to generate a side chain tertiary amine-containing dihalogenated monomer;

(2) purification of dihalogenated monomers having tertiary amine in side chain

Evaporating the organic solvent in the side chain tertiary amine-containing dihalogenated monomer, collecting heavy components, washing oily heavy components or solids for 3-6 times by using deionized water, removing water-soluble impurities, and performing water separation and drying to obtain the side chain tertiary amine-containing dihalogenated monomer;

further, the amine containing the tertiary amine structure is any one of N, N-dimethyl-p-phenylenediamine, N-dimethyl-ethylenediamine or N, N-dimethyl-propylenediamine;

further, the alkali is NaOH, KOH, LiOH, Na₂CO₃、K₂CO₃、Li₂CO₃Triethylamine or trimethylamine;

further, the surfactant is at least one of triethyl ammonium bromide, dodecyl triethyl ammonium chloride, hexadecyl dimethyl ammonium bromide, sodium sulfanilate, tetrabutyl ammonium bromide, benzyl triethyl ammonium chloride, dodecyl benzene sulfonate, sodium alginate or dodecyl sodium sulfonate and sodium stearate;

further, the organic solvent is any one of 1, 2-dichloroethane, dichloromethane, chloroform, chlorobenzene, m-dichlorobenzene, o-dichlorobenzene, cyclohexane, n-hexane, petroleum ether, or n-octane.

4. The method for preparing the corrosion-resistant polyarylether resin of any one of claims 1 to 3, wherein the preparation is as follows: taking a sulfur or oxygen-containing monomer, a dihalogenated monomer with a side chain containing tertiary amine and a dihalogenated aromatic compound as raw materials, and carrying out polymerization reaction under the protection of inert gas at 140-230 ℃ under the action of alkali, a catalyst, a solvent and a dehydrating agent to obtain a polyarylether resin crude product with the side chain containing tertiary amine; purifying the obtained crude product to obtain the corrosion-resistant polyarylether resin; wherein, the proportion of the sulfur or oxygen-containing monomer, the side chain tertiary amine-containing dihalogenated monomer and the dihalogenated aromatic compound is as follows: 56-400 parts by weight of a sulfur-or oxygen-containing monomer, 5-309 parts by weight of a dihalogenated monomer having a tertiary amine in a side chain, and 1-500 parts by weight of a dihalogenated aromatic compound;

further, the crude product of the side chain tertiary amine-containing polyarylether resin is prepared by adopting the following method: adding 56-400 parts by weight of a sulfur or oxygen-containing monomer, 5-309 parts by weight of a side-chain tertiary amine-containing dihalogenated monomer, 1-500 parts by weight of a dihalogenated aromatic compound, 1-200 parts by weight of alkali, 1-100 parts by weight of a catalyst, 600-5000 parts by weight of a solvent and 0-100 parts by weight of a dehydrating agent into a reaction kettle, performing dehydration reaction for 0.5-3 h at 140-230 ℃ under the protection of inert gas, then performing reaction for 0.5-12 h at 150-230 ℃, and finally pouring the obtained polymer mixed solution into water while stirring to obtain a side-chain tertiary amine-containing polyarylether resin crude product;

further, the purification method comprises the following steps: crushing the obtained polyarylether resin crude product containing the side chain tertiary amine, washing the crushed crude product with water and ethanol for 3-5 times, filtering, recovering and recycling filtrate, and drying the collected filter cake at the temperature of 80-120 ℃ for 8-24 hours to obtain the corrosion-resistant polyarylether resin;

further, the solvent is dimethylacetamide, N-methylpropionamide, hexamethylphosphoric triamide, N-methylcaprolactam, N-dimethylpropyleneurea, N, any one of N' -tetramethylurea, 1, 3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, N-cyclohexylpyrrolidone, 2-pyrrolidone quinoline, isoquinoline, diphenylsulfone, benzophenone, sulfolane, dimethylsulfone, dimethylsulfoxide, 2, 4-dimethylsulfolane, N-phenylmorpholine, dimethyl phthalate, diethyl phthalate, 1-methyl-3-propylimidazole bromide salt, 1-methyl-3-isopropylimidazole bromide salt, or 1, 3-dipropylimidazolium bromide salt;

further, the base is any one of lithium hydroxide, sodium hydroxide, calcium hydroxide, potassium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, barium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, calcium bicarbonate, barium bicarbonate, triethylamine, tripropylamine, or tri-t-butylamine;

further, the catalyst is lithium oxalate, sodium oxalate, potassium oxalate, zinc oxalate, lithium malonate, sodium malonate, potassium malonate, zinc malonate, lithium succinate, sodium succinate, potassium succinate, zinc succinate adipate, sodium adipate, potassium adipate, zinc adipate, lithium terephthalate, sodium terephthalate, potassium terephthalate, zinc terephthalate, lithium formate, sodium formate, potassium formate, zinc formate, lithium acetate, sodium acetate, potassium acetate, zinc acetate, lithium benzoate, sodium benzoate, potassium benzoate, zinc benzoate, lithium ethylenediamine tetraacetate, sodium ethylenediamine tetraacetate, potassium ethylenediamine tetraacetate, zinc ethylenediamine tetraacetate, lithium ethylenediamine tetraacetate, trisodium ethylenediamine tetraacetate, tripotassium ethylenediamine tetraacetate, lithium chloride, lithium phosphate, sodium phosphate, potassium phosphate, lithium tartrate, sodium oxalate, potassium, Sodium tartrate, potassium tartrate, zinc tartrate, sodium lactate, lithium sorbate, sodium sorbate, potassium sorbate, lithium lysinate, sodium lysinate, potassium lysinate, lithium cystinate, sodium cystinate, potassium cystinate, lithium citrate, sodium citrate, potassium citrate, zinc citrate, lithium 6-aminocaproate, sodium 6-aminocaproate, potassium 6-aminocaproate, zinc 6-aminocaproate, lithium nitrilotriacetate, sodium nitrilotriacetate, potassium nitrilotriacetate, zinc nitrilotriacetate, lithium hydroxyacetate, sodium hydroxyacetate, potassium hydroxyacetate, zinc hydroxyacetate, lithium gluconate, sodium gluconate, potassium gluconate, zinc gluconate, lithium diethylenetriaminepentacarboxylate, sodium diethylenetriaminepentacarboxylate, lithium heptonate, sodium heptonate, potassium heptonate, lithium glycocholate, sodium glycocholate, potassium glycolate, potassium glycocholate, potassium, At least one of zinc glycocholate, lithium dioctylsuccinate, sodium dioctylsuccinate, potassium dioctylsuccinate, lithium ethylenediamineterepthalate, sodium ethylenediamineterepthalate, potassium ethylenediamineterepthalate, lithium alginate, sodium alginate, potassium alginate, zinc alginate, lithium p-aminobenzenesulfonate, sodium p-aminobenzenesulfonate, potassium p-aminobenzenesulfonate, zinc p-aminobenzenesulfonate, lithium p-methylbenzenesulfonate, sodium p-methylbenzenesulfonate, potassium p-methylbenzenesulfonate, 15-crown-5, 18-crown-6, sodium stearate, potassium stearate, or zinc stearate;

further, the dehydrating agent is toluene or xylene.

5. The corrosion-resistant polyarylether resin is used for preparing a corrosion-resistant polyarylether ultrafiltration membrane, a corrosion-resistant polyarylether nanofiltration membrane or a corrosion-resistant polyarylether separation membrane with ultrafiltration/nanofiltration reversible conversion, and the corrosion-resistant polyarylether resin is the corrosion-resistant polyarylether resin disclosed by any one of claims 1-3 or prepared by the method disclosed by claim 4.

6. The corrosion-resistant polyarylether ultrafiltration membrane is characterized by being prepared by the following method:

(a) preparing a casting solution:

adding 16-30 parts by weight of corrosion-resistant polyarylether resin and 70-84 parts by weight of solvent into a dissolving kettle, stirring and dissolving at the temperature of 60-200 ℃, centrifuging and filtering after dissolving into a uniform polymer solution, removing solid impurities, defoaming in vacuum at the temperature of 40-100 ℃ for 10-48 hours, and sealing and storing for later use; wherein the corrosion-resistant polyarylether resin is the corrosion-resistant polyarylether resin of any one of claims 1 to 3 or prepared by the method of claim 4;

(b) preparing a polyarylether ultrafiltration membrane containing side chain tertiary amine: preparing a corresponding flat ultrafiltration membrane or hollow fiber ultrafiltration membrane by using the membrane casting solution obtained in the step (a);

(c) passivating a polyarylether ultrafiltration membrane containing side chain tertiary amine: immersing the ultrafiltration membrane obtained in the step (b) into 0.1-100 parts by weight of a thin film passivation treating agent, and carrying out passivation treatment at normal temperature for 0.5-48 h;

(d) purifying and hole-protecting post-treatment of the side-chain tertiary amine-containing polyarylether ultrafiltration membrane: washing and replacing the side chain-containing tertiary amine polyarylether ultrafiltration membrane prepared in the step (c) with water to remove residual solvent, and merging the solvent and recovering the solvent in a solvent recovery system; then immersing the purified separation membrane into a pore-protecting agent for pore-protecting treatment, and airing to obtain the corrosion-resistant polyarylether ultrafiltration membrane;

further, in the step (a), the solvent is any one of 1, 3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide or N, N-dimethylacetamide;

further, in the step (c), the thin film passivation treating agent is at least one of concentrated sulfuric acid, concentrated nitric acid, dilute nitric acid, peroxyacetic acid, hypochlorous acid, sodium hypochlorite, potassium permanganate, manganese dioxide, potassium dichromate, potassium perchlorate, potassium chlorate, hydrogen peroxide, ferric sulfate or silver nitrate solution;

further, in the step (d), the pore-protecting agent is any one of glycerol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600 or polyethylene glycol 800.

7. The corrosion-resistant polyarylether nanofiltration membrane is characterized by being prepared by the following method: immersing the corrosion-resistant polyarylether ultrafiltration membrane into 5-200 parts by weight of an ultra/nanofiltration reversible conversion and nanofiltration treatment agent, and treating at 25-40 ℃ for 0.5-48 h to obtain a corrosion-resistant polyarylether nanofiltration membrane; wherein the corrosion-resistant polyarylether ultrafiltration membrane is the corrosion-resistant polyarylether ultrafiltration membrane of claim 6;

further, the ultra/nanofiltration reversible conversion ultrafiltration conversion treatment agent is at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, ammonium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, ammonia water, trimethylamine, triethylamine, tri-n-propylamine, tri-tert-butylamine, pyridine or piperazine.

8. An ultrafiltration/nanofiltration reversible conversion corrosion-resistant polyarylether separation membrane is characterized by being prepared by the following method:

(1) preparing a casting solution:

adding 16-30 parts by weight of corrosion-resistant polyarylether resin and 70-84 parts by weight of solvent into a dissolving kettle, stirring and dissolving at the temperature of 60-200 ℃, centrifuging and filtering after dissolving into a uniform polymer solution, removing solid impurities, defoaming in vacuum at the temperature of 40-100 ℃ for 10-48 hours, and sealing and storing for later use; wherein the corrosion-resistant polyarylether resin is the corrosion-resistant polyarylether resin of any one of claims 1 to 3 or prepared by the method of claim 4;

(2) preparing a polyarylether ultrafiltration membrane containing side chain tertiary amine: preparing a corresponding flat ultrafiltration membrane or hollow fiber ultrafiltration membrane by using the membrane casting solution obtained in the step (1);

(3) passivating a polyarylether ultrafiltration membrane containing side chain tertiary amine: immersing the ultrafiltration membrane obtained in the step (2) into 0.1-100 parts by weight of a thin film passivation treating agent, and carrying out passivation treatment at normal temperature for 0.5-48 h;

(4) purifying and hole-protecting post-treatment of the side-chain tertiary amine-containing polyarylether ultrafiltration membrane: washing and replacing the side chain-containing tertiary amine polyarylether ultrafiltration membrane prepared in the step (3) with water to remove residual solvent, and merging the solvent and recovering the solvent in a solvent recovery system; then immersing the purified separation membrane into a pore-protecting agent for pore-protecting treatment, and airing to obtain a corrosion-resistant polyarylether ultrafiltration membrane (a polyarylether passivation ultrafiltration membrane containing side chain tertiary amine);

(5) nanofiltration conversion of the side chain tertiary amine-containing polyarylether ultrafiltration membrane: immersing the corrosion-resistant polyarylether ultrafiltration membrane prepared in the step (4) into 5-200 parts by weight of an ultra/nanofiltration reversible conversion and nanofiltration conversion treating agent, and treating at 25-40 ℃ for 0.5-48 h to obtain a polyarylether passivation nanofiltration membrane containing side chain tertiary amine;

(6) ultrafiltration conversion of the ultrafiltration membrane containing the side chain tertiary amine polyarylether passivation: immersing the passivated nanofiltration membrane obtained in the step (5) into 5-200 parts by weight of an ultra/nanofiltration reversible conversion ultrafiltration treatment agent and 200-1000 parts by weight of an ultra/nanofiltration reversible conversion ultrafiltration conversion solvent, and treating at 25-40 ℃ for 2-48 h to obtain a polyarylether passivated ultrafiltration membrane containing side chain tertiary amine;

further, in the step (5), the ultra/nanofiltration reversible conversion nanofiltration conversion treatment agent is at least one of hydrochloric acid, dilute sulfuric acid, glacial acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, pivalic acid, caproic acid, caprylic acid and isooctanoic acid, a carboxyl-containing polymer solution comprising polyacrylic acid and a copolymer solution thereof, a carboxyl-containing phenolphthalein polyether sulfone solution, a carboxyl-containing phenolphthalein polyamide solution or a carboxyl-containing phenolphthalein polyarylate solution;

further, in the step (6), the ultra/nanofiltration reversible conversion ultrafiltration conversion treatment agent is at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, ammonium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, ammonia water, trimethylamine, triethylamine, tri-n-propylamine, tri-tert-butylamine, pyridine or piperazine;

further, in the step (6), the ultrafiltration/nanofiltration reversible conversion ultrafiltration conversion solvent is any one of water, methanol, ethanol, glycerol, isopropanol, acetone, tetrahydrofuran, dichloromethane, chloroform, carbon tetrachloride, petroleum ether, cyclohexane, n-hexane or dioxane.

9. A dihalogeno-monomer containing a tertiary amine in a side chain, characterized in that the dihalogeno-monomer containing a tertiary amine in a side chain is any one of compounds represented by the following structural formula:

10. a production method of a dihalo-monomer having a tertiary amine in a side chain according to claim 9, characterized by comprising the steps of:

(1) preparation of dihalogenated monomer containing tertiary amine at side chain

Sequentially adding 88-136 parts by weight of amine containing a tertiary amine structure, 40 parts by weight of alkali and 1-30 parts by weight of surfactant into 300-1500 parts by weight of deionized water, and dissolving at room temperature to obtain an amine solution containing a tertiary amine structure; uniformly mixing 176-209 parts by weight of 3, 5-dihalogenated formyl chloride and 500-3000 parts by weight of organic solvent, adding the mixture into a reaction vessel, dropwise adding the prepared tertiary amine structure-containing amine solution into the reaction vessel, and continuously reacting for 3-10 h at room temperature after dropwise adding the tertiary amine structure-containing amine solution to generate a side chain tertiary amine-containing dihalogenated monomer;

(2) purification of dihalogenated monomers having tertiary amine in side chain

Evaporating the organic solvent in the side chain tertiary amine-containing dihalogenated monomer, collecting heavy components, washing oily heavy components or solids for 3-6 times by using deionized water, removing water-soluble impurities, and performing water separation and drying to obtain the side chain tertiary amine-containing dihalogenated monomer;

further, the amine containing the tertiary amine structure is any one of N, N-dimethyl-p-phenylenediamine, N-dimethyl-ethylenediamine or N, N-dimethyl-propylenediamine;

further, the alkali is NaOH, KOH, LiOH, Na₂CO₃、K₂CO₃、Li₂CO₃Triethylamine or trimethylamine;

further, the surfactant is at least one of triethyl ammonium bromide, dodecyl triethyl ammonium chloride, hexadecyl dimethyl ammonium bromide, sodium sulfanilate, tetrabutyl ammonium bromide, benzyl triethyl ammonium chloride, dodecyl benzene sulfonate, sodium alginate or dodecyl sodium sulfonate and sodium stearate;

further, the organic solvent is any one of 1, 2-dichloroethane, dichloromethane, chloroform, chlorobenzene, m-dichlorobenzene, o-dichlorobenzene, cyclohexane, n-hexane, petroleum ether, or n-octane.

Technical Field

The invention relates to a corrosion-resistant polyarylether resin, a corrosion-resistant separation membrane and a preparation method thereof, belonging to the field of high polymer materials.

Background

As a novel separation technology, membrane separation has very important research significance in material separation due to the advantages of low cost, low energy consumption, high efficiency, no pollution, capability of recovering useful materials and the like. The method is widely applied to the fields of food, medicine, biology, energy, water treatment, bionics and the like, has great influence on the production and life of human beings, and becomes one of the most important means in the separation science at present. It is well known that separation membranes are the core of membrane separation processes, and membrane materials are the basis for the development of separation membranes. From the aspects of separation mechanism and application range, the method can be divided into a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane, a reverse osmosis membrane, a pervaporation membrane and the like; the biggest factors influencing the use of the separation membrane are membrane separation efficiency, membrane pollution, membrane service life and the like,

the main polymer materials widely used for preparing the separation membrane at present comprise fluorine-containing resin such as polyvinylidene fluoride (PVDF), which has good film forming property and is generally used for preparing ultrafiltration and microfiltration membranes, but the hydrophobicity and the organic solvent corrosion resistance are poor; the sulfone-containing resin such as Polysulfone (PSU), polyether sulfone (PES) and the like has good temperature resistance and film forming property, is generally used for ultrafiltration and nanofiltration membranes, but has poor organic solvent corrosion resistance; polyvinyl chloride (PVC) which is low in cost and general in pore-forming property, but is poor in hydrophobicity, solvent corrosion resistance and temperature resistance; polyamide (PA) and Polyimide (PI) have poor pore forming property, are generally used for nanofiltration and reverse osmosis membranes, and have poor acid and alkali corrosion resistance; polypropylene (PP) is environment-friendly by adopting a thermoforming method, is suitable for a microfiltration membrane, and has poor hydrophobicity, solvent corrosion resistance and heat resistance. Therefore, how to prepare a separation membrane with high separation efficiency, corrosion resistance, pollution resistance and easy cleaning, regeneration or reversible function switching is very critical.

Disclosure of Invention

The invention aims to provide a corrosion-resistant polyarylether resin (polyarylether resin containing side chain tertiary amine) and a separation membrane prepared from the corrosion-resistant polyarylether resin, aiming at overcoming the defects of the prior art, and the obtained separation membrane has excellent separation efficiency, super corrosion resistance, pollution resistance, good mechanical property and extremely excellent reversible switching and membrane regeneration performance within a large-scale range of membrane pores, can be used for preparing a high-performance and multifunctional separation membrane, and has wide application prospect.

The technical scheme of the invention is as follows:

the first technical problem to be solved by the invention is to provide a corrosion-resistant polyarylether resin, which comprises the following raw materials:

wherein the side chain tertiary amine-containing dihalogenated monomer is any one of the compounds shown in the following structural formula:

further, the sulfur-containing or oxygen-containing monomer is any one of compounds shown in the following structural formula:

further, the dihalo-aromatic compound has a structural formula of Y-Ar-Y, Y ═ F or Cl,

wherein m is 2,4, 6, 8 or 10.

Further, the side chain tertiary amine-containing dihalogenated monomer is prepared by the following preparation method, and the preparation method comprises the following steps:

(1) preparation of dihalogenated monomer containing tertiary amine at side chain

Sequentially adding 88-136 parts by weight of amine containing a tertiary amine structure, 40 parts by weight of alkali and 1-30 parts by weight of surfactant into 300-1500 parts by weight of deionized water, and dissolving at room temperature to obtain an amine solution containing a tertiary amine structure; uniformly mixing 176-209 parts by weight of 3, 5-dihalogenated formyl chloride and 500-3000 parts by weight of organic solvent, adding the mixture into a reaction vessel, dropwise adding the prepared tertiary amine structure-containing amine solution into the reaction vessel, and continuously reacting for 3-10 h at room temperature after dropwise adding the tertiary amine structure-containing amine solution to generate a side chain tertiary amine-containing dihalogenated monomer;

(2) purification of dihalogenated monomers having tertiary amine in side chain

And evaporating the organic solvent in the side chain tertiary amine-containing dihalogenated monomer, collecting the heavy component, washing the oily heavy component or the solid for 3-6 times by using deionized water, removing water-soluble impurities, and performing water separation and drying to obtain the side chain tertiary amine-containing dihalogenated monomer.

Further, in the above method for producing a dihalogenated monomer having a side chain containing a tertiary amine, in step 1), the amine having a tertiary amine structure is any one of N, N-dimethyl-p-phenylenediamine, N-dimethylethylenediamine, and N, N-dimethylpropylenediamine.

Further, in the above-mentioned method for producing a dihalogenated monomer having a side chain containing a tertiary amine, in the step 1), the base is NaOH, KOH, LiOH or Na₂CO₃、K₂CO₃、Li₂CO₃Triethylamine or trimethylamine, and the like.

Further, in the preparation method of the dihalogenated monomer with the side chain containing the tertiary amine, in the step 1), the surfactant is at least one of triethylammonium bromide, dodecyltriethylammonium chloride, hexadecyl dimethyl ammonium bromide, sodium sulfanilate, tetrabutyl ammonium bromide, benzyl triethylammonium chloride, sodium dodecylbenzene sulfonate, sodium benzene sulfonate, sodium alginate or sodium dodecylsulfonate and sodium stearate.

Further, in the above method for producing a dihalogenated monomer having a side chain containing a tertiary amine, the organic solvent is any one of 1, 2-dichloroethane, dichloromethane, chloroform, chlorobenzene, m-dichlorobenzene, o-dichlorobenzene, cyclohexane, n-hexane, petroleum ether, and n-octane.

The second technical problem to be solved by the present invention is to provide a preparation method of the above corrosion-resistant polyarylether resin, wherein the preparation method comprises: taking a sulfur or oxygen-containing monomer, a dihalogenated monomer with a side chain containing tertiary amine and a dihalogenated aromatic compound as raw materials, and carrying out polymerization reaction under the protection of inert gas at 140-230 ℃ under the action of alkali, a catalyst, a solvent and a dehydrating agent to obtain a polyarylether resin crude product with the side chain containing tertiary amine; purifying the obtained crude product to obtain the corrosion-resistant polyarylether resin; wherein, the proportion of the sulfur or oxygen-containing monomer, the side chain tertiary amine-containing dihalogenated monomer and the dihalogenated aromatic compound is as follows: 56 to 400 parts by weight of a sulfur-or oxygen-containing monomer, 5 to 309 parts by weight of a dihalogenated monomer having a tertiary amine in a side chain, and 1 to 500 parts by weight of a dihalogenated aromatic compound.

Further, in the method, the crude product of the polyarylether resin containing the side chain tertiary amine is prepared by adopting the following method: adding 56-400 parts by weight of a sulfur or oxygen-containing monomer, 5-309 parts by weight of a side-chain tertiary amine-containing dihalogenated monomer, 1-500 parts by weight of a dihalogenated aromatic compound, 1-200 parts by weight of alkali, 1-100 parts by weight of a catalyst, 600-5000 parts by weight of a solvent and 0-100 parts by weight of a dehydrating agent into a reaction kettle, performing dehydration reaction for 0.5-3 h at 140-230 ℃ under the protection of inert gas (such as nitrogen), then performing reaction for 0.5-12 h at 150-230 ℃, and finally pouring the obtained polymer mixed solution into water while stirring to obtain a side-chain tertiary amine-containing polyarylether resin crude product.

Further, the solvent is dimethylacetamide, N-methylpropionamide, hexamethylphosphoric triamide, N-methylcaprolactam, N-dimethylpropyleneurea, N, any one of N ', N' -tetramethylurea, 1, 3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, N-cyclohexylpyrrolidone, 2-pyrrolidone quinoline, isoquinoline, diphenylsulfone, benzophenone, sulfolane, dimethylsulfone, dimethylsulfoxide, 2, 4-dimethylsulfolane, N-phenylmorpholine, dimethyl phthalate, diethyl phthalate, 1-methyl-3-propylimidazole bromide salt, 1-methyl-3-isopropylimidazole bromide salt, or 1, 3-dipropylimidazolium bromide salt.

Further, the base is any one of lithium hydroxide, sodium hydroxide, calcium hydroxide, potassium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, barium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, calcium bicarbonate, barium bicarbonate, triethylamine, tripropylamine, or tri-t-butylamine.

Further, the catalyst is lithium oxalate, sodium oxalate, potassium oxalate, zinc oxalate, lithium malonate, sodium malonate, potassium malonate, zinc malonate, lithium succinate, sodium succinate, potassium succinate, zinc succinate adipate, sodium adipate, potassium adipate, zinc adipate, lithium terephthalate, sodium terephthalate, potassium terephthalate, zinc terephthalate, lithium formate, sodium formate, potassium formate, zinc formate, lithium acetate, sodium acetate, potassium acetate, zinc acetate, lithium benzoate, sodium benzoate, potassium benzoate, zinc benzoate, lithium ethylenediamine tetraacetate, sodium ethylenediamine tetraacetate, potassium ethylenediamine tetraacetate, zinc ethylenediamine tetraacetate, lithium ethylenediamine tetraacetate, trisodium ethylenediamine tetraacetate, tripotassium ethylenediamine tetraacetate, lithium chloride, lithium phosphate, sodium phosphate, potassium phosphate, lithium tartrate, lithium oxalate, sodium oxalate, potassium malonate, sodium malonate, potassium oxalate, sodium malonate, potassium oxalate, sodium oxalate, potassium oxalate, Sodium tartrate, potassium tartrate, zinc tartrate, sodium lactate, lithium sorbate, sodium sorbate, potassium sorbate, lithium lysinate, sodium lysinate, potassium lysinate, lithium cystinate, sodium cystinate, potassium cystinate, lithium citrate, sodium citrate, potassium citrate, zinc citrate, lithium 6-aminocaproate, sodium 6-aminocaproate, potassium 6-aminocaproate, zinc 6-aminocaproate, lithium nitrilotriacetate, sodium nitrilotriacetate, potassium nitrilotriacetate, zinc nitrilotriacetate, lithium hydroxyacetate, sodium hydroxyacetate, potassium hydroxyacetate, zinc hydroxyacetate, lithium gluconate, sodium gluconate, potassium gluconate, zinc gluconate, lithium diethylenetriaminepentacarboxylate, sodium diethylenetriaminepentacarboxylate, lithium heptonate, sodium heptonate, potassium heptonate, lithium glycocholate, sodium glycocholate, potassium glycolate, potassium glycocholate, potassium, At least one of zinc glycocholate, lithium dioctylsuccinate, sodium dioctylsuccinate, potassium dioctylsuccinate, lithium ethylenediamineterepthalate, sodium ethylenediamineterepthalate, potassium ethylenediamineterepthalate, lithium alginate, sodium alginate, potassium alginate, zinc alginate, lithium p-aminobenzenesulfonate, sodium p-aminobenzenesulfonate, potassium p-aminobenzenesulfonate, zinc p-aminobenzenesulfonate, lithium p-methylbenzenesulfonate, sodium p-methylbenzenesulfonate, potassium p-methylbenzenesulfonate, 15-crown-5, 18-crown-6, sodium stearate, potassium stearate, or zinc stearate.

Further, the dehydrating agent is toluene or xylene.

Further, in the above method, the purification method is: and (2) crushing the obtained polyarylether resin crude product containing the side chain tertiary amine, washing the crushed crude product with water and ethanol for 3-5 times, filtering, recovering and recycling the filtrate, and drying the collected filter cake at the temperature of 80-120 ℃ for 8-24 hours to obtain the corrosion-resistant polyarylether resin (namely the purified polyarylether resin containing the side chain tertiary amine).

The third technical problem to be solved by the invention is to indicate that the corrosion-resistant polyarylether resin can be used for preparing a corrosion-resistant polyarylether ultrafiltration membrane, a corrosion-resistant polyarylether nanofiltration membrane or a corrosion-resistant polyarylether separation membrane with reversible ultrafiltration/nanofiltration conversion.

The fourth technical problem to be solved by the invention is to provide a corrosion-resistant polyarylether ultrafiltration membrane, which is prepared by the following method:

(a) preparing a casting solution:

adding 16-30 parts by weight of corrosion-resistant polyarylether resin and 70-84 parts by weight of solvent into a dissolving kettle, stirring and dissolving at the temperature of 60-200 ℃, centrifuging and filtering after dissolving into a uniform polymer solution, removing solid impurities, defoaming in vacuum at the temperature of 40-100 ℃ for 10-48 hours, and sealing and storing for later use; wherein the corrosion-resistant polyarylether resin is the prepared polyarylether resin containing the side chain tertiary amine;

(b) preparing a polyarylether ultrafiltration membrane containing side chain tertiary amine: preparing a corresponding flat ultrafiltration membrane or hollow fiber ultrafiltration membrane by using the membrane casting solution obtained in the step (a);

(c) passivating a polyarylether ultrafiltration membrane containing side chain tertiary amine: immersing the ultrafiltration membrane obtained in the step (b) into 0.1-100 parts by weight of a thin film passivation treating agent, and carrying out passivation treatment at normal temperature for 0.5-48 h;

(d) purifying and hole-protecting post-treatment of the side-chain tertiary amine-containing polyarylether ultrafiltration membrane: washing and replacing the side chain-containing tertiary amine polyarylether ultrafiltration membrane prepared in the step (c) with water to remove residual solvent, and merging the solvent and recovering the solvent in a solvent recovery system; and then immersing the purified separation membrane into a pore-protecting agent for pore-protecting treatment, and airing to obtain the corrosion-resistant polyarylether ultrafiltration membrane (the polyarylether passivation ultrafiltration membrane containing side chain tertiary amine).

Further, in the step (a), the solvent is any one of 1, 3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, dimethyl sulfoxide, N-dimethylformamide or N, N-dimethylacetamide; in the step (d), the pore-protecting agent is any one of glycerol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600 or polyethylene glycol 800.

Further, in the step (c), the thin film passivation treating agent is at least one of concentrated sulfuric acid, concentrated nitric acid, dilute nitric acid, peroxyacetic acid, hypochlorous acid, sodium hypochlorite, potassium permanganate, manganese dioxide, potassium dichromate, potassium perchlorate, potassium chlorate, hydrogen peroxide, ferric sulfate or silver nitrate solution.

The fifth technical problem to be solved by the invention is to provide a corrosion-resistant polyarylether nanofiltration membrane, which is prepared by the following method: and (3) immersing the corrosion-resistant polyarylether ultrafiltration membrane into 5-200 parts by weight of an ultra/nanofiltration reversible conversion treatment agent, and treating at 25-40 ℃ for 0.5-48 h to obtain the corrosion-resistant polyarylether nanofiltration membrane (containing side chain tertiary amine polyarylether passivation nanofiltration membrane).

Further, the ultra/nanofiltration reversible conversion ultrafiltration conversion treatment agent is at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, ammonium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, ammonia water, trimethylamine, triethylamine, tri-n-propylamine, tri-tert-butylamine, pyridine or piperazine.

The sixth technical problem to be solved by the invention is to provide an ultrafiltration/nanofiltration reversible conversion corrosion-resistant polyarylether separation membrane, which is prepared by adopting the following method:

(1) preparing a casting solution:

adding 16-30 parts by weight of corrosion-resistant polyarylether resin and 70-84 parts by weight of solvent into a dissolving kettle, stirring and dissolving at the temperature of 60-200 ℃, centrifuging and filtering after dissolving into a uniform polymer solution, removing solid impurities, defoaming in vacuum at the temperature of 40-100 ℃ for 10-48 hours, and sealing and storing for later use; wherein the corrosion-resistant polyarylether resin is the prepared polyarylether resin containing the side chain tertiary amine;

(2) preparing a polyarylether ultrafiltration membrane containing side chain tertiary amine: preparing a corresponding flat ultrafiltration membrane or hollow fiber ultrafiltration membrane by using the membrane casting solution obtained in the step (1);

(3) passivating a polyarylether ultrafiltration membrane containing side chain tertiary amine: immersing the ultrafiltration membrane obtained in the step (2) into 0.1-100 parts by weight of a thin film passivation treating agent, and carrying out passivation treatment at normal temperature for 0.5-48 h;

(4) purifying and hole-protecting post-treatment of the side-chain tertiary amine-containing polyarylether ultrafiltration membrane: washing and replacing the side chain-containing tertiary amine polyarylether ultrafiltration membrane prepared in the step (3) with water to remove residual solvent, and merging the solvent and recovering the solvent in a solvent recovery system; then immersing the purified separation membrane into a pore-protecting agent for pore-protecting treatment, and airing to obtain a corrosion-resistant polyarylether ultrafiltration membrane (a polyarylether passivation ultrafiltration membrane containing side chain tertiary amine);

(5) nanofiltration conversion of the side chain tertiary amine-containing polyarylether ultrafiltration membrane: immersing the corrosion-resistant polyarylether ultrafiltration membrane prepared in the step (4) into 5-200 parts by weight of an ultra/nanofiltration reversible conversion and nanofiltration conversion treating agent, and treating at 25-40 ℃ for 0.5-48 h to obtain a polyarylether passivation nanofiltration membrane containing side chain tertiary amine;

(6) ultrafiltration conversion of the ultrafiltration membrane containing the side chain tertiary amine polyarylether passivation: and (3) immersing the passivated nanofiltration membrane obtained in the step (5) into 5-200 parts by weight of an ultra/nanofiltration reversible conversion ultrafiltration treatment agent and 200-1000 parts by weight of an ultra/nanofiltration reversible conversion ultrafiltration conversion solvent, and treating at 25-40 ℃ for 2-48 h to obtain the polyarylether passivated ultrafiltration membrane containing side chain tertiary amine.

Further, in the step (5), the ultra/nanofiltration reversible conversion treatment agent is at least one of hydrochloric acid, dilute sulfuric acid, glacial acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, pivalic acid, caproic acid, caprylic acid, isooctanoic acid, a carboxyl group-containing polymer solution including polyacrylic acid and a copolymer solution thereof, a carboxyl group-containing phenolphthalein polyether sulfone solution, a carboxyl group-containing phenolphthalein polyamide solution, or a carboxyl group-containing phenolphthalein polyarylate solution.

Further, in the step (6), the ultrafiltration/nanofiltration reversible conversion ultrafiltration treatment agent is at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, ammonium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, ammonia, trimethylamine, triethylamine, tri-n-propylamine, tri-tert-butylamine, pyridine or piperazine.

Further, in the step (6), the ultrafiltration/nanofiltration reversible conversion ultrafiltration conversion solvent is any one of water, methanol, ethanol, glycerol, isopropanol, acetone, tetrahydrofuran, dichloromethane, chloroform, carbon tetrachloride, petroleum ether, cyclohexane, n-hexane or dioxane.

According to the invention, the separation membrane can be reversibly switched in a corresponding large-scale range of membrane pores according to application or membrane cleaning requirements, so that the adaptability, the separation efficiency and the service life of the separation membrane are greatly improved.

The seventh technical problem to be solved by the present invention is to provide a dihalogenated monomer containing tertiary amine in a side chain, wherein the dihalogenated monomer containing tertiary amine in a side chain is any one of compounds represented by the following structural formula:

an eighth technical problem to be solved by the present invention is to provide a method for producing the above dihalogenomonomer having a tertiary amine in a side chain, comprising the steps of:

(1) preparation of dihalogenated monomer containing tertiary amine at side chain

Sequentially adding 88-136 parts by weight of amine containing a tertiary amine structure, 40 parts by weight of alkali and 1-30 parts by weight of surfactant into 300-1500 parts by weight of deionized water, and dissolving at room temperature to obtain an amine solution containing a tertiary amine structure; uniformly mixing 176-209 parts by weight of 3, 5-dihalogenated formyl chloride and 500-3000 parts by weight of organic solvent, adding the mixture into a reaction vessel, dropwise adding the prepared tertiary amine structure-containing amine solution into the reaction vessel, and continuously reacting for 3-10 h at room temperature after dropwise adding the tertiary amine structure-containing amine solution to generate a side chain tertiary amine-containing dihalogenated monomer;

(2) purification of dihalogenated monomers having tertiary amine in side chain

And evaporating the organic solvent in the side chain tertiary amine-containing dihalogenated monomer, collecting the heavy component, washing the oily heavy component or the solid for 3-6 times by using deionized water, removing water-soluble impurities, and performing water separation and drying to obtain the side chain tertiary amine-containing dihalogenated monomer.

In the invention, the raw materials are in parts by weight except for special specifications.

The invention has the beneficial effects that:

1. the tertiary amine-containing dihalogenated monomer prepared by the invention adopts a one-step interfacial reaction preparation process, has short flow, mild reaction conditions, no need of heating, and high product yield and purity, and is beneficial to subsequent industrial amplification.

2. The preparation method adopts a normal pressure method to prepare the polyarylether resin (corrosion-resistant polyarylether resin) with the side chain containing the active tertiary amine structure, and has the advantages of mild reaction conditions, safety, reliability, strong repeatability, high resin yield and controllable cost; meanwhile, in the preparation process, except inorganic salt byproducts, no other three-waste pollution is generated, and the preparation method is green and environment-friendly; and the obtained resin has excellent comprehensive properties such as excellent film forming property, high mechanical strength, corrosion resistance and high temperature resistance.

3. The polyarylether separation membrane containing the side chain tertiary amine (corrosion-resistant polyarylether separation membrane) prepared by the method has super-strong corrosion resistance (can resist long-term corrosion of concentrated sulfuric acid, aqua regia, halogenated alkane such as chloroform and dichloromethane and strong polar organic solvents such as DMF, NMP and DMSO) after being subjected to simple passivation treatment by one step, can be used for separating organic media, and has excellent temperature resistance and mechanical properties.

4. According to the invention, the active alkalescent tertiary amine structure is introduced into the main chain of the polyarylether, and the separation membrane can be subjected to reversible cycle switching within a larger scale range through subsequent reversible regulation or after a carboxyl-containing polymer is introduced, so that the membrane is multipurpose, the separation efficiency and the service life of the separation membrane are greatly improved, meanwhile, the fixed investment of membrane equipment, components and site construction can be saved, and the production cost is greatly reduced;

drawings

FIG. 1 is a nuclear magnetic spectrum of 3, 5-difluorobenzoyl-N, N-dimethylethylenediamine (M228) in example 1.

FIG. 2 is a nuclear magnetic spectrum of 3, 5-difluorobenzoyl-N, N-dimethylpropanediamine (M242) in example 2.

FIG. 3 is a nuclear magnetic spectrum of 3, 5-difluorobenzoyl-N, N-dimethyl-p-phenylenediamine (M276) in example 3.

FIG. 4 is an infrared spectrum of the polymer obtained in examples 1 to 3.

Detailed Description

The present invention is described in detail below by way of examples, it should be noted that the examples are only for the purpose of further illustration, and are not to be construed as limiting the scope of the present invention, and that those skilled in the art can make insubstantial modifications and adaptations of the present invention based on the teachings of the present invention described above.

Example 1

(1) Preparation of dihalogenated monomer containing tertiary amine at side chain (M228-10%)

Adding 88g of N, N-dimethylethylenediamine containing a tertiary amine structure, 40g of NaOH and 1g of surfactant triethylammonium bromide into 300g of deionized water in sequence, and dissolving at room temperature; uniformly mixing 176g of 3, 5-difluoro formyl chloride and 500g of organic solvent 1, 2-dichloroethane, adding the mixture into a three-neck flask, dropwise adding the prepared amine solution containing the tertiary amine structure into the three-neck flask, and continuously reacting for 3 hours at room temperature after the dropwise addition of the amine solution containing the tertiary amine structure is finished to generate 3, 5-difluoro benzoyl-N, N-dimethyl ethylenediamine (marked as M228) containing the tertiary amine difluoro monomer at the side chain;

(2) purification of dihalogenated monomers having tertiary amine in side chain

Evaporating the organic solvent in the side chain tertiary amine-containing dihalogenated monomer, collecting heavy components, washing oily heavy components or solids for 3 times by deionized water, removing water-soluble impurities, and drying by water separation to obtain a side chain tertiary amine-containing dihalogenated monomer M228, wherein a nuclear magnetic spectrum of the side chain tertiary amine-containing dihalogenated monomer is shown in figure 1, and each proton signal peak of the side chain tertiary amine-containing dihalogenated monomer is marked in the figure;

(3) preparation of polyarylether resin (corrosion-resistant polyarylether resin) containing side chain tertiary amine

Adding 186g of oxygen-containing monomer biphenyl diphenol, 1g of side-chain tertiary amine-containing dihalogenated monomer M22822.8g, 258.3g of 4, 4' -dichlorodiphenyl sulfone, 150g of sodium carbonate, 1g of lithium oxalate, 600g of hexamethylphosphoric triamide and 20g of dehydrating agent toluene into a reaction kettle, performing dehydration reaction for 0.5h at 230 ℃ under the protection of nitrogen, performing reaction for 1h at 230 ℃, and finally pouring the obtained polymer mixed solution into water while stirring to obtain a side-chain tertiary amine-containing polyarylether resin linear crude product;

(4) purification of polyarylether resins containing side chain tertiary amines

Crushing the polyarylether resin crude product containing the side chain tertiary amine obtained in the step (3), washing the crushed crude product with water and ethanol for 3 times, filtering, recovering and recycling the filtrate, and drying the collected filter cake at the temperature of 80 ℃ for 8 hours to obtain purified polyarylether resin containing the side chain tertiary amine; its infrared spectrum is shown in FIG. 4, in which 2960cm^-1is-CH₃Characteristic absorption peak of 1670cm^-1Is a characteristic absorption peak of-CONH-middle-CO-, 1320, 1150cm^-1is-SO₂Characteristic absorption peak of 1230cm^-1Characteristic absorption peak of tertiary amine group, 1110cm^-1A characteristic absorption peak of-O-;

(5) preparation of reversible cross-linking corrosion-resistant separation membrane with side chain containing tertiary amine

(a) Preparing a casting solution: adding 30g of side chain-containing tertiary amine polyarylether resin and 70g of solvent 1, 3-dimethyl-2-imidazolidinone into a dissolving kettle, stirring and dissolving at the temperature of 60 ℃, centrifuging and filtering after dissolving into uniform polymer solution, removing solid impurities, defoaming in vacuum at the temperature of 100 ℃ for 10 hours, and sealing and storing for later use;

(b) preparing a polyarylether ultrafiltration membrane containing side chain tertiary amine: preparing a corresponding flat ultrafiltration membrane or hollow fiber ultrafiltration membrane by using the membrane casting solution obtained in the step (a), and respectively detecting the flux and the corresponding retention rate;

(c) passivating a polyarylether ultrafiltration membrane containing side chain tertiary amine: immersing the ultrafiltration membrane obtained in the step (b) into 100g of a membrane passivation treating agent (concentrated sulfuric acid 10g +90g of hydrogen peroxide), passivating for 0.5h at normal temperature, detecting the corrosion resistance of the ultrafiltration membrane, and not dissolving the ultrafiltration membrane into common solvents such as dichloromethane, tetrahydrofuran, toluene, phosphoric acid and the like;

(d) purifying and hole-protecting post-treatment of the side-chain tertiary amine-containing polyarylether ultrafiltration membrane: washing and replacing the side chain-containing tertiary amine polyarylether ultrafiltration membrane prepared in the step (c) with water to remove residual solvent, and merging the solvent and recovering the solvent in a solvent recovery system; then immersing the purified separation membrane into glycerol serving as a pore-preserving agent for pore-preserving treatment, and airing to obtain a polyarylether passivated ultrafiltration membrane containing side chain tertiary amine for later use;

(e) nanofiltration conversion of the side chain tertiary amine-containing polyarylether ultrafiltration membrane: immersing the passivated ultrafiltration membrane obtained in the step (d) into 200g of ultra/nanofiltration reversible conversion nanofiltration conversion treatment agent (glacial acetic acid 180g and polyacrylic acid 20g), treating for 0.5h at 25 ℃ to obtain polyarylether passivated nanofiltration membrane containing side chain tertiary amine, and respectively detecting that the pure water flux of the polyarylether passivated nanofiltration membrane is 10-15Lm^-2h^-1bar^-1The retention rate of rhodamine B is more than or equal to 99.5 percent;

(f) ultrafiltration conversion of the ultrafiltration membrane containing the side chain tertiary amine polyarylether passivation: immersing the passivated nanofiltration membrane obtained in the step (e) into 200g of ultra/nanofiltration reversible conversion ultrafiltration treatment agent (lithium hydroxide 5g +195g of water), treating at 40 ℃ for 48h to obtain a polyarylether passivated ultrafiltration membrane containing side chain tertiary amine, and respectively detecting that the flux of the ultrafiltration membrane is 240 Lm-^-2h^-1bar^-1And the retention rate of rhodamine B is approximately equal to 50 percent.

Example 2

(1) Preparation of dihalogenated monomer containing tertiary amine at side chain (M242-10%)

Adding 102g of N, N-dimethyl propane diamine containing a tertiary amine structure, 40g of NaOH and 5g of surfactant sodium dodecyl benzene sulfonate into 1500g of deionized water in sequence, and dissolving at room temperature; uniformly mixing 176g of 3, 5-difluoro formyl chloride and 2000g of organic solvent dichloromethane, adding the mixture into a three-neck flask, dropwise adding the prepared amine solution containing the tertiary amine structure into the three-neck flask, and continuously reacting for 10 hours at room temperature after the dropwise addition of the amine solution containing the tertiary amine structure is finished to generate 3, 5-difluoro benzoyl-N, N-dimethyl propylene diamine (marked as M242) containing the tertiary amine difluoro monomer on the side chain;

(2) purification of dihalogenated monomers having tertiary amine in side chain

Evaporating the organic solvent in the side chain tertiary amine-containing dihalogenated monomer, collecting heavy components, washing oily heavy components or solids for 4 times by deionized water, removing water-soluble impurities, and drying by water separation to obtain a side chain tertiary amine-containing dihalogenated monomer M242, wherein a nuclear magnetic spectrum of the side chain tertiary amine-containing dihalogenated monomer M242 is shown in figure 2, and each proton signal peak is marked in the figure;

(3) preparation of polyarylether resin containing side chain tertiary amine

Adding 186g of oxygen-containing monomer biphenyl diphenol, 24.2g of tertiary amine-containing dihalogenated monomer M24224.2 g on a side chain, 228.6g of 4, 4' -difluorodiphenyl sulfone, 180g of potassium carbonate, 50g of sodium gluconate, 2000g of N-methyl pyrrolidone and 100g of dehydrating agent xylene into a reaction kettle, performing dehydration reaction at 190 ℃ for 0.5h under the protection of nitrogen, then performing reaction at 200 ℃ for 12h, and finally pouring the obtained polymer mixed solution into water while stirring to obtain a side chain-containing tertiary amine polyarylether resin linear crude product;

(4) purification of polyarylether resins containing side chain tertiary amines

Crushing the polyarylether resin crude product containing the side chain tertiary amine obtained in the step (3), washing the crushed crude product with water and ethanol for 5 times, filtering, recovering and recycling the filtrate, and drying the collected filter cake at 120 ℃ for 10 hours to obtain purified polyarylether resin containing the side chain tertiary amine; its infrared spectrum is shown in FIG. 4, in which 2960cm^-1is-CH₃Characteristic absorption peak of 1680cm^-1Is a characteristic absorption peak of-CONH-medium-CO-, 1314, 1151cm^-1is-SO₂Characteristic absorption peak of (1), 1235cm^-1Characteristic absorption peak of tertiary amine group, 1107cm^-1A characteristic absorption peak of-O-;

(5) preparation of reversible cross-linking corrosion-resistant separation membrane with side chain containing tertiary amine

(a) Preparing a casting solution: adding 20g of side chain-containing tertiary amine polyarylether resin and 80g of solvent N-methyl pyrrolidone into a dissolving kettle, stirring and dissolving at 100 ℃, centrifuging and filtering after dissolving into uniform polymer solution, removing solid impurities, defoaming in vacuum at 80 ℃ for 48 hours, and sealing and storing for later use;

(b) preparing a polyarylether ultrafiltration membrane containing side chain tertiary amine: preparing a corresponding flat ultrafiltration membrane or hollow fiber ultrafiltration membrane by using the membrane casting solution obtained in the step (a), and respectively detecting the flux and the corresponding retention rate;

(c) passivating a polyarylether ultrafiltration membrane containing side chain tertiary amine: immersing the ultrafiltration membrane obtained in the step (b) into 60g of a thin film passivation treating agent (10 g of peroxyacetic acid and 50g of hydrogen peroxide), passivating for 1h at normal temperature, detecting the corrosion resistance of the ultrafiltration membrane, and not dissolving the ultrafiltration membrane into common solvents such as dichloromethane, tetrahydrofuran, toluene, phosphoric acid and the like;

(d) purifying and hole-protecting post-treatment of the side-chain tertiary amine-containing polyarylether ultrafiltration membrane: washing and replacing the side chain-containing tertiary amine polyarylether ultrafiltration membrane prepared in the step (c) with water to remove residual solvent, and merging the solvent and recovering the solvent in a solvent recovery system; then immersing the purified separation membrane into a pore-preserving agent polyethylene glycol 200 for pore-preserving treatment, and airing to obtain a polyarylether passivated ultrafiltration membrane containing side chain tertiary amine for later use;

(e) nanofiltration conversion of the side chain tertiary amine-containing polyarylether ultrafiltration membrane: immersing the passivated ultrafiltration membrane obtained in the step (d) into 100g of ultra/nanofiltration reversible conversion nanofiltration conversion treatment agent (100 g of propionic acid), treating for 6h at 40 ℃ to obtain polyarylether passivated nanofiltration membrane containing side chain tertiary amine, and respectively detecting that the pure water flux of the nanofiltration membrane is 20-25Lm^-2h^-1bar^-1The retention rate of rhodamine B is more than or equal to 99.2 percent;

(f) ultrafiltration conversion of the ultrafiltration membrane containing the side chain tertiary amine polyarylether passivation: immersing the passivated nanofiltration membrane obtained in the step (e) into 100g of ultra/nanofiltration reversible conversion ultrafiltration conversion treating agent (sodium hydroxide 3g +97g of water), treating for 24h at 40 ℃ to obtain a polyarylether passivated ultrafiltration membrane containing side chain tertiary amine, and respectively detecting the flux of the polyarylether passivated ultrafiltration membrane to be 400-^-2h^-1bar^-1And the retention rate of rhodamine B is approximately equal to 40 percent.

Example 3

(1) Preparation of dihalogenated monomer containing tertiary amine in side chain (M276-10%)

Sequentially adding 136g of N, N-dimethyl-p-phenylenediamine containing a tertiary amine structure, 40g of NaOH and 30g of sodium alginate serving as a surfactant into 1000g of deionized water, and dissolving at room temperature; uniformly mixing 176g of 3, 5-difluoro formyl chloride and 3000g of organic solvent chlorobenzene, adding the mixture into a three-neck flask, dropwise adding the prepared amine solution containing the tertiary amine structure into the three-neck flask, and continuously reacting for 10 hours at room temperature after the dropwise addition of the amine solution containing the tertiary amine structure is finished to generate a side chain difluoro monomer-3, 5-difluorobenzoyl-N, N-dimethyl p-phenylenediamine (marked as M276);

(2) purification of dihalogenated monomers having tertiary amine in side chain

Evaporating the organic solvent in the side chain tertiary amine-containing dihalogenated monomer, collecting heavy components, washing oily heavy components or solids for 5 times by using deionized water, removing water-soluble impurities, and drying by using water to obtain a side chain tertiary amine-containing dihalogenated monomer M276, wherein a nuclear magnetic spectrum of the side chain tertiary amine-containing dihalogenated monomer M276 is shown in figure 3, and each proton signal peak is marked in the figure;

(3) preparation of polyarylether resin containing side chain tertiary amine

Adding 186g of oxygen-containing monomer biphenyl diphenol, 50g of sodium gluconate dihalogenated monomer M27627.6 g of tertiary amine-containing side chain dihalogenated monomer, 228.6g of 4, 4' -difluorodiphenyl sulfone, 40g of sodium hydroxide, 3000g of N-cyclohexyl pyrrolidone and 20g of dehydrating agent xylene into a reaction kettle, performing dehydration reaction for 0.5h at 210 ℃ under the protection of nitrogen, performing reaction for 12h at 220 ℃, and finally pouring the obtained polymer mixed solution into water while stirring to obtain a crude polyarylether resin line product containing the tertiary amine at the side chain;

(4) purification of polyarylether resins containing side chain tertiary amines

Crushing the polyarylether resin crude product containing the side chain tertiary amine obtained in the step (3), washing the crushed crude product with water and ethanol for 5 times, filtering, recovering and recycling the filtrate, and drying the collected filter cake at 100 ℃ for 10 hours to obtain purified polyarylether resin containing the side chain tertiary amine; its infrared spectrum is shown in FIG. 4, in which 2961cm^-1is-CH₃Characteristic absorption peak of 1673cm^-1Is a characteristic absorption peak of-CONH-medium-CO-, 1319, 1146cm^-1is-SO₂Characteristic absorption peak of (1), 1236cm^-1Is a characteristic absorption peak of the tertiary amine group, 1101cm^-1A characteristic absorption peak of-O-;

(5) preparation of reversible cross-linking corrosion-resistant separation membrane with side chain containing tertiary amine

(a) Preparing a casting solution: adding 25g of side chain-containing tertiary amine polyarylether resin and 80g of solvent N-methyl pyrrolidone into a dissolving kettle, stirring and dissolving at 100 ℃, centrifuging and filtering after dissolving into uniform polymer solution, removing solid impurities, defoaming in vacuum at 90 ℃ for 24 hours, and sealing and storing for later use;

(b) preparing a polyarylether ultrafiltration membrane containing side chain tertiary amine: preparing a corresponding flat ultrafiltration membrane or hollow fiber ultrafiltration membrane by using the membrane casting solution obtained in the step (a), and respectively detecting the flux and the corresponding retention rate;

(c) passivating a polyarylether ultrafiltration membrane containing side chain tertiary amine: immersing the ultrafiltration membrane obtained in the step (b) into 80g of a film passivation treating agent (potassium permanganate 10g +70g of hypochlorous acid), passivating for 2 hours at normal temperature, detecting the corrosion resistance of the ultrafiltration membrane, and not dissolving the ultrafiltration membrane into common solvents such as dichloromethane, tetrahydrofuran, toluene, phosphoric acid and the like;

(d) purifying and hole-protecting post-treatment of the side-chain tertiary amine-containing polyarylether ultrafiltration membrane: washing and replacing the side chain-containing tertiary amine polyarylether ultrafiltration membrane prepared in the step (c) with water to remove residual solvent, and merging the solvent and recovering the solvent in a solvent recovery system; then immersing the purified separation membrane into a pore-preserving agent polyethylene glycol 400 for pore-preserving treatment, and airing to obtain a polyarylether passivated ultrafiltration membrane containing side chain tertiary amine for later use;

(e) nanofiltration conversion of the side chain tertiary amine-containing polyarylether ultrafiltration membrane: immersing the passivated ultrafiltration membrane obtained in the step (d) into 150g of ultra/nanofiltration reversible conversion nanofiltration conversion treatment agent (butyric acid 150g), treating for 8h at 35 ℃ to obtain polyarylether passivated nanofiltration membrane containing side chain tertiary amine, and respectively detecting that the pure water flux of the nanofiltration membrane is 18-24Lm^-2h^-1bar^-1The retention rate of rhodamine B is more than or equal to 99.4 percent;

(f) ultrafiltration conversion of the ultrafiltration membrane containing the side chain tertiary amine polyarylether passivation: immersing the passivated nanofiltration membrane obtained in the step (e) into 150g of ultra/nanofiltration reversible conversion ultrafiltration treatment agent (potassium hydroxide 5g +145g of water), treating at 40 ℃ for 24h to obtain a polyarylether passivated ultrafiltration membrane containing side chain tertiary amine, and respectively detecting the flux of the polyarylether passivated ultrafiltration membrane to be 400-Lm and 420Lm^-2h^-1bar^-1The retention rate of rhodamine B is approximately equal to 45 percent.

Example 4

(1) Preparation of dihalogenated monomer containing tertiary amine in side chain (M261-20%)

Adding 88g of N, N-dimethylethylenediamine containing a tertiary amine structure, 40g of NaOH and 1g of surfactant triethylammonium bromide into 300g of deionized water in sequence, and dissolving at room temperature; uniformly mixing 209g of 3, 5-dichloroformyl chloride and 800g of organic solvent chloroform, adding the mixture into a three-neck flask, dropwise adding the prepared amine solution containing the tertiary amine structure into the three-neck flask, and continuously reacting for 3 hours at room temperature after the dropwise addition of the amine solution containing the tertiary amine structure is finished to generate side chain dichloromonomer-3, 5-dichlorobenzoyl-N, N-dimethylethylenediamine (marked as M261);

(2) purification of dihalogenated monomers having tertiary amine in side chain

Evaporating the organic solvent in the side chain tertiary amine-containing dihalogenated monomer, collecting heavy components, washing oily heavy components or solids for 4 times by deionized water, removing water-soluble impurities, and obtaining a side chain tertiary amine-containing dihalogenated monomer M261 after water separation and drying;

(3) preparation of polyarylether resin containing side chain tertiary amine

Adding 56g of sulfur-containing monomer sodium hydrosulfide, 52.2g of side-chain tertiary amine-containing dihalogenated monomer M26152.2 g, 172.2g of 4,4 '-dichlorodiphenyl sulfone, 45.6g of 4, 4' -difluorobenzophenone, 40g of sodium hydroxide, 10g of sodium sorbate, 1200g of N-phenylmorpholine and 20g of dehydrating agent toluene into a reaction kettle, carrying out dehydration reaction for 3h at the temperature of 170 ℃ under the protection of nitrogen, reacting for 6h at the temperature of 200 ℃, and finally pouring the obtained polymer mixed solution into water while stirring to obtain a side-chain tertiary amine-containing polyarylether resin linear crude product;

(4) purification of polyarylether resins containing side chain tertiary amines

Crushing the polyarylether resin crude product containing the side chain tertiary amine obtained in the step (3), washing the crushed crude product with water and ethanol for 4 times, filtering, recovering and recycling the filtrate, and drying the collected filter cake at 100 ℃ for 12h to obtain purified polyarylether resin containing the side chain tertiary amine;

(5) preparation of reversible cross-linking corrosion-resistant separation membrane with side chain containing tertiary amine

(a) Preparing a casting solution: adding 26g of side chain-containing tertiary amine polyarylether resin and 75g of solvent 1, 3-dimethyl-2-imidazolidinone into a dissolving kettle, stirring and dissolving at the temperature of 80 ℃, centrifuging and filtering after dissolving into uniform polymer solution, removing solid impurities, defoaming in vacuum at the temperature of 70 ℃ for 20 hours, and sealing and storing for later use;

(b) preparing a polyarylether ultrafiltration membrane containing side chain tertiary amine: preparing a corresponding flat ultrafiltration membrane or hollow fiber ultrafiltration membrane by using the membrane casting solution obtained in the step (a), and respectively detecting the flux and the corresponding retention rate;

(c) passivating a polyarylether ultrafiltration membrane containing side chain tertiary amine: immersing the ultrafiltration membrane obtained in the step (b) into 100g of a thin film passivation treating agent (diluted nitric acid 100g), passivating for 1h at normal temperature, detecting the corrosion resistance of the ultrafiltration membrane, and not dissolving the ultrafiltration membrane in common solvents such as NMP, concentrated sulfuric acid, dichloromethane, tetrahydrofuran, toluene, phosphoric acid and the like;

(d) purifying and hole-protecting post-treatment of the side-chain tertiary amine-containing polyarylether ultrafiltration membrane: washing and replacing the side chain-containing tertiary amine polyarylether ultrafiltration membrane prepared in the step (c) with water to remove residual solvent, and merging the solvent and recovering the solvent in a solvent recovery system; then immersing the purified separation membrane into glycerol serving as a pore-preserving agent for pore-preserving treatment, and airing to obtain a polyarylether passivated ultrafiltration membrane containing side chain tertiary amine for later use;

(e) nanofiltration conversion of the side chain tertiary amine-containing polyarylether ultrafiltration membrane: immersing the passivated ultrafiltration membrane obtained in the step (d) into 150g of ultra/nanofiltration reversible conversion nanofiltration conversion treatment agent (130 g of propionic acid and 20g of carboxyl-containing phenolphthalein polyether sulfone solution), treating at 35 ℃ for 2h to obtain a polyarylether passivated nanofiltration membrane containing side chain tertiary amine, and respectively detecting that the pure water flux of the nanofiltration membrane is 20-30Lm^-2h^-1bar^-1The retention rate of methylene blue is more than or equal to 99.0 percent;

(f) ultrafiltration conversion of the ultrafiltration membrane containing the side chain tertiary amine polyarylether passivation: immersing the passivated nanofiltration membrane obtained in the step (e) into 200g of ultra/nanofiltration reversible conversion ultrafiltration treatment agent (potassium hydroxide 10g +190g of water), treating at 40 ℃ for 48h to obtain a polyarylether passivated ultrafiltration membrane containing side chain tertiary amine, and respectively detecting that the flux of the ultrafiltration membrane is 320-380Lm^-2h^-1bar^-1The retention rate of methylene blue is approximately equal to 20 percent.

Example 5

(1) Preparation of dihalogenated monomer containing tertiary amine in side chain (M275-10%)

Adding 102g of N, N-dimethyl propane diamine containing a tertiary amine structure, 40g of NaOH and 8g of surfactant benzyltriethylammonium chloride into 600g of deionized water in sequence, and dissolving at room temperature; uniformly mixing 209g of 3, 5-dichloroformyl chloride and 2000g of organic solvent chlorobenzene, adding the mixture into a three-necked flask, dropwise adding the prepared amine solution containing the tertiary amine structure into the three-necked flask, and continuously reacting for 3 hours at room temperature after the dropwise addition of the amine solution containing the tertiary amine structure is finished to generate a side chain dichloromonomer-3, 5-dichlorobenzoyl-N, N-dimethylpropylenediamine (marked as M275);

(2) purification of dihalogenated monomers having tertiary amine in side chain

Evaporating the organic solvent in the side chain tertiary amine-containing dihalogenated monomer, collecting heavy components, washing oily heavy components or solids for 5 times by deionized water, removing water-soluble impurities, and drying by water separation to obtain a side chain tertiary amine-containing dihalogenated monomer M275;

(3) preparation of polyarylether resin containing side chain tertiary amine

Adding 78g of sulfur-containing monomer sodium sulfide, 45.6g of tertiary amine-containing dihalogenated monomer M27527.5g of side chain, 352.1g of bi (4-chlorobenzenesulfone), 45.6g of 4, 4' -difluorobenzophenone, 2g of sodium hydroxide, 20g of sodium succinate, 1500g of N-methylpyrrolidone and 10g of dehydrating agent toluene into a reaction kettle, dehydrating at 190 ℃ for 1h under the protection of nitrogen, reacting at 200 ℃ for 8h, and finally pouring the obtained polymer mixed solution into water while stirring to obtain a side chain-containing tertiary amine polyarylether resin linear crude product;

(4) purification of polyarylether resins containing side chain tertiary amines

Crushing the polyarylether resin crude product containing the side chain tertiary amine obtained in the step (3), washing the crushed crude product with water and ethanol for 4 times, filtering, recovering and recycling the filtrate, and drying the collected filter cake at 100 ℃ for 12h to obtain purified polyarylether resin containing the side chain tertiary amine;

(5) preparation of reversible cross-linking corrosion-resistant separation membrane with side chain containing tertiary amine

(a) Preparing a casting solution: adding 22g of side chain-containing tertiary amine polyarylether resin and 70g of solvent N-methylpyrrolidone into a dissolving kettle, stirring and dissolving at 90 ℃, centrifuging and filtering after dissolving into uniform polymer solution, removing solid impurities, defoaming in vacuum at 80 ℃ for 24 hours, and sealing and storing for later use;

(b) preparing a polyarylether ultrafiltration membrane containing side chain tertiary amine: preparing a corresponding flat ultrafiltration membrane or hollow fiber ultrafiltration membrane by using the membrane casting solution obtained in the step (a), and respectively detecting the flux and the corresponding retention rate;

(c) passivating a polyarylether ultrafiltration membrane containing side chain tertiary amine: immersing the ultrafiltration membrane obtained in the step (b) into 100g of membrane passivation treating agent (100 g of peroxyacetic acid), passivating for 2h at normal temperature, detecting the corrosion resistance of the ultrafiltration membrane, and not dissolving the ultrafiltration membrane in common solvents such as NMP, concentrated sulfuric acid, dichloromethane, tetrahydrofuran, toluene, phosphoric acid and the like;

(d) purifying and hole-protecting post-treatment of the side-chain tertiary amine-containing polyarylether ultrafiltration membrane: washing and replacing the side chain-containing tertiary amine polyarylether ultrafiltration membrane prepared in the step (c) with water to remove residual solvent, and merging the solvent and recovering the solvent in a solvent recovery system; then immersing the purified separation membrane into a pore-preserving agent polyethylene glycol 600 for pore-preserving treatment, and airing to obtain a polyarylether passivated ultrafiltration membrane containing side chain tertiary amine for later use;

(e) nanofiltration conversion of the side chain tertiary amine-containing polyarylether ultrafiltration membrane: immersing the passivated ultrafiltration membrane obtained in the step (d) into 120g of ultra/nanofiltration reversible conversion nanofiltration conversion treatment agent (glacial acetic acid 100g + carboxyl-containing phenolphthalein polyamide solution 20g), treating at 32 ℃ for 20h to obtain polyarylether passivated nanofiltration membrane containing side chain tertiary amine, and respectively detecting that the pure water flux of the nanofiltration membrane is 30-45Lm^-2h^-1bar^-1The retention rate of methylene blue is more than or equal to 98 percent;

(f) ultrafiltration conversion of the ultrafiltration membrane containing the side chain tertiary amine polyarylether passivation: immersing the passivated nanofiltration membrane obtained in the step (e) into 200g of ultra/nanofiltration reversible conversion ultrafiltration conversion treating agent (100 g of tri-tert-butylamine and 100g of acetone), treating for 48h at 30 ℃ to obtain a polyarylether passivated ultrafiltration membrane containing side chain tertiary amine, and respectively detecting the flux of the ultrafiltration membrane to be 310-370 Lm-^-2h^-1bar^-1The retention rate of methylene blue is approximately equal to 25 percent.