阅读说明：本技术 一种高强度的磺基聚酰亚胺接枝丙烯酸基水凝胶吸附材料 (High-strength sulfopolyimide grafted acrylic acid-based hydrogel adsorption material ) 是由 冯程程 于 2020-08-24 设计创作，主要内容包括：本发明涉及吸附材料领域,且公开了一种高强度的磺基聚酰亚胺接枝丙烯酸基水凝胶吸附材料,含磺基的2,2’-双磺酸联苯胺、以及含酚羟基的2,2-双(3-氨基-4-羟基苯基)六氟丙烷作为二胺单体,与苝四甲酸二酐聚合得到含酚羟基的磺基聚酰亚胺,酚羟基与ATRP试剂2-溴异丁酰溴的酰溴原子进行亲核取代反应,得到2-溴异丁酯化的磺基聚酰亚胺,以其为大分子引发剂,引发甲基丙烯酸和丙烯酰胺原位交联聚合,通过共价键接枝,将磺基聚酰亚胺与聚丙烯酸水凝胶有机结合,丰富的磺基、羧基和氨基,对Cu<Sup>2+</Sup>等重金属离子具有优异的络合吸附性能,将力学性能优异聚酰亚胺的引入到聚丙烯酸水凝胶中,显著提高了材料的拉伸强度。(The invention relates to the field of adsorption materials and discloses a high-strength sulfopolyimide grafted acrylic acid based hydrogelThe method comprises the steps of using 2,2' -disulfonic acid benzidine containing sulfo groups and 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane containing phenolic hydroxyl groups as diamine monomers, polymerizing the diamine monomers with perylene tetracarboxylic acid dianhydride to obtain sulfo polyimide containing phenolic hydroxyl groups, carrying out nucleophilic substitution reaction on the phenolic hydroxyl groups and acyl bromide atoms of 2-bromoisobutyryl bromide of an ATRP reagent to obtain 2-bromoisobutyrated sulfo polyimide, using the sulfo polyimide as a macromolecular initiator to initiate methacrylic acid and acrylamide in-situ crosslinking polymerization, and organically combining the sulfo polyimide with polyacrylic acid hydrogel through covalent bond grafting, wherein the sulfo polyimide is rich in sulfo groups, carboxyl groups and amino groups and can be used for treating Cu 2+ The heavy metal ions have excellent complexing adsorption performance, and the polyimide with excellent mechanical property is introduced into the polyacrylic acid hydrogel, so that the tensile strength of the material is obviously improved.)

1. A high-strength sulfopolyimide grafted acrylic acid-based hydrogel adsorption material is characterized in that: the preparation method of the high-strength sulfopolyimide grafted acrylic acid-based hydrogel adsorption material comprises the following steps:

(1) adding triethylamine, benzoic acid, 2 '-disulfonic acid benzidine, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane and perylene tetracarboxylic dianhydride into a m-cresol solvent, placing the mixture into an oil bath reaction instrument, heating the mixture to 75-85 ℃, stirring the mixture for reaction for 3-6h, then heating the mixture to 190 ℃ for stirring the mixture for reaction for 18-36h, cooling the mixture to separate out precipitate and washing the precipitate to obtain sulfonic triethylamine polyimide;

(2) adding sulfonic triethylamine polyimide into a sulfuric acid solution, stirring to protonate the sulfonic triethylamine salt, filtering, washing and drying to prepare sulfopolyimide;

(3) adding sulfopolyimide and 2-bromoisobutyryl bromide into a pyridine solvent, reacting for 2-5h in an ice-water bath, then reacting for 10-20h at room temperature, precipitating, filtering, washing and drying to prepare 2-bromoisobutyrated sulfopolyimide;

(4) adding 2-bromine isobutyl sulfo polyimide, methacrylic acid, acrylamide, 4-dimethyl aminopyridine, cuprous chloride and copper chloride into an N, N-dimethylformamide solvent, heating to 50-80 ℃ in an argon atmosphere, stirring for reacting for 20-60min, adding N, N-methylene bisacrylamide, reacting for 10-20h, cooling, precipitating, washing, dialyzing and purifying to prepare the high-strength sulfo polyimide grafted acrylic acid based hydrogel adsorbing material.

2. A high strength sulfopolyimide grafted acrylic-based hydrogel adsorbent material according to claim 1, wherein: the mass ratio of triethylamine, benzoic acid, 2' -disulfonic acid benzidine, bis (3-amino-4-hydroxyphenyl) hexafluoropropane and perylene tetracarboxylic dianhydride in the step (1) is 400-450:75-85:70-80:10-15: 100.

3. A high strength sulfopolyimide grafted acrylic-based hydrogel adsorbent material according to claim 1, wherein: the oil bath reaction instrument in the step (1) comprises a heating device, an oil bath pot is arranged above the heating device, a cover plate is arranged above the oil bath pot, a guide wheel is movably connected inside the cover plate, a moving screw rod is movably connected with the guide wheel, a clamping plate is fixedly connected with the moving screw rod, and a reaction bottle is movably connected with the clamping plate.

4. A high strength sulfopolyimide grafted acrylic-based hydrogel adsorbent material according to claim 1, wherein: the amount concentration of the sulfuric acid substance in the step (2) is 0.5-1 mol/L.

5. A high strength sulfopolyimide grafted acrylic-based hydrogel adsorbent material according to claim 1, wherein: the mass ratio of the sulfopolyimide to the 2-bromoisobutyryl bromide in the step (3) is 100: 180-220.

6. A high strength sulfopolyimide grafted acrylic-based hydrogel adsorbent material according to claim 1, wherein: the mass ratio of the 2-bromoisobutylated sulfopolyimide, the methacrylic acid, the acrylamide, the 4-dimethylaminopyridine, the cuprous chloride, the cupric chloride and the N, N-methylene bisacrylamide in the step (4) is 30-55:100:20-40:6-12:3.5-8:0.25-0.5: 0.3-0.8.

Technical Field

The invention relates to the field of adsorption materials, in particular to a high-strength sulfopolyimide grafted acrylic acid-based hydrogel adsorption material.

Background

At present, the problem of water pollution in China is increasingly severe, and water pollutants mainly comprise acid, alkali and salt, and inorganic pollutants such as copper, chromium, mercury and the like; organic contaminants such as halides and organic solvents; the method has the advantages that the method causes serious pollution to the water environment and has great harm to aquatic organisms and human health, and the existing treatment methods for water pollutants mainly comprise an adsorption method, a neutralization method, an oxidation-reduction method and the like, wherein the adsorption method is a simpler and more efficient treatment method.

The adsorbent mainly comprises an activated carbon material, silica gel, polyacrylamide and the like, the hydrogel is a three-dimensional gel and has excellent hydrophilicity and water absorbability, and the acrylic-based hydrogel is obtained by polymerizing monomers such as acrylic acid, acrylamide and the like, contains abundant hydroxyl, carboxyl and amino and is also rich in Cu²⁺、Cr²⁺The heavy metal ions have good complexing adsorption capacity and important application in the field of water treatment adsorption, but the traditional polyacrylic acid hydrogel has limited adsorption performance, and the mechanical properties such as tensile strength and the like of hydrogel adsorption treatment are poor, so that the polyacrylic acid hydrogel adsorption material is easy to crack and damage after being used in a complex water body environment for a long time, and further development and application of the polyacrylic acid hydrogel adsorption material are hindered.

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a high-strength sulfopolyimide grafted acrylic acid-based hydrogel adsorption material, and solves the problems that the traditional acrylic acid-based hydrogel adsorption material is limited in adsorption performance and poor in mechanical property of tensile strength.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: a high strength sulfopolyimide grafted acrylic-based hydrogel adsorption material: the preparation method of the high-strength sulfopolyimide grafted acrylic acid-based hydrogel adsorption material comprises the following steps:

(1) adding m-cresol solvent, triethylamine, benzoic acid, 2' -disulfonic acid benzidine, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and perylene tetracarboxylic dianhydride into a reaction bottle, placing the reaction bottle in an oil bath reaction instrument, heating to 75-85 ℃, uniformly stirring for reaction for 3-6h, then heating to 190 ℃ for 160-fold stirring, uniformly stirring for reaction for 18-36h, cooling to room temperature, adding acetone solvent to precipitate, and washing with acetone to obtain sulfonic triethylamine polyimide.

(2) Adding a sulfuric acid solution and sulfonic triethylamine polyimide into a reaction bottle, stirring at a constant speed to protonate the sulfonic triethylamine salt, filtering concentrated sulfuric acid, washing with distilled water and acetone, and drying to prepare the sulfopolyimide.

(3) Adding a pyridine solvent, sulfopolyimide and 2-bromoisobutyryl bromide into a reaction bottle, reacting for 2-5h in an ice-water bath, then reacting for 10-20h at room temperature, adding a methanol solvent to precipitate, filtering the solvent, washing with methanol and drying to prepare the 2-bromoisobutylated sulfopolyimide.

(4) Adding N, N-dimethylformamide solvent, 2-bromoisobutylated sulfopolyimide, methacrylic acid, acrylamide, 4-dimethylaminopyridine, cuprous chloride and copper chloride into a reaction bottle, heating to 50-80 ℃ in an argon atmosphere, stirring at a constant speed for reaction for 20-60min, adding N, N-methylene bisacrylamide, stirring at a constant speed for reaction for 10-20h, cooling to room temperature, adding distilled water to precipitate, washing with distilled water, dialyzing and purifying to prepare the high-strength sulfopolyimide grafted acrylic-based hydrogel adsorbing material.

Preferably, the mass ratio of triethylamine, benzoic acid, 2' -disulfonic acid benzidine, bis (3-amino-4-hydroxyphenyl) hexafluoropropane and perylene tetracarboxylic dianhydride in the step (1) is 400-450:75-85:70-80:10-15: 100.

Preferably, the oil bath reaction instrument in the step (1) comprises a heating device, an oil bath pot is arranged above the heating device, a cover plate is arranged above the oil bath pot, a guide wheel is movably connected inside the cover plate, the guide wheel is movably connected with a movable screw, a clamp plate is fixedly connected with the movable screw, and a reaction bottle is movably connected with the clamp plate.

Preferably, the amount concentration of the sulfuric acid substance in the step (2) is 0.5-1 mol/L.

Preferably, the mass ratio of the sulfopolyimide to the 2-bromoisobutyryl bromide in the step (3) is 100: 180-220.

Preferably, the mass ratio of the 2-bromoisobutylated sulfopolyimide, the methacrylic acid, the acrylamide, the 4-dimethylaminopyridine, the cuprous chloride, the cupric chloride and the N, N-methylenebisacrylamide in the step (4) is 30-55:100:20-40:6-12:3.5-8:0.25-0.5: 0.3-0.8.

(III) advantageous technical effects

Compared with the prior art, the invention has the following experimental principles and beneficial technical effects:

the high-strength sulfopolyimide grafted acrylic-based hydrogel adsorption material is prepared by polymerizing 2,2' -disulfonic acid benzidine containing sulfo groups and 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane containing phenolic hydroxyl groups as diamine monomers with perylenetetracarboxylic dianhydride to obtain sulfopolyimide containing phenolic hydroxyl groups in a main chain, carrying out nucleophilic substitution reaction on the phenolic hydroxyl groups and acyl bromide atoms of 2-bromoisobutyryl bromide of an ATRP reagent under the action of pyridine to obtain 2-bromoisobutyrated sulfopolyimide, using the sulfopolyimide as a macroinitiator to initiate in-situ crosslinking polymerization of methacrylic acid, acrylamide and N, N-methylenebisacrylamide on a sulfopolyimide molecular chain, grafting through covalent bonds, organically combining the sulfopolyimide with polyacrylic acid hydrogel, and grafting the sulfopolyimide grafted acrylic-based hydrogel containing abundant sulfo groups, Carboxyl and amino, p-Cu²⁺The heavy metal ions have excellent complexing adsorption performance, so that an excellent adsorption effect is achieved, and meanwhile, the polyimide with excellent mechanical properties is introduced into the branched chain of the polyacrylic acid hydrogel, so that the mechanical properties such as tensile strength of the hydrogel adsorption material are remarkably improved.

Drawings

FIG. 1 is a schematic front view of an oil bath reactor;

FIG. 2 is an enlarged schematic view of the movable screw;

fig. 3 is a schematic view of splint adjustment.

1-a heating device; 2-oil bath pan; 3-cover plate; 4-a guide wheel; 5-moving the screw; 6-clamping plate; 7-reaction flask.

Detailed Description

To achieve the above object, the present invention provides the following embodiments and examples: a high-strength sulfopolyimide grafted acrylic acid-based hydrogel adsorption material is prepared by the following steps:

(1) adding m-cresol solvent into a reaction bottle, placing triethylamine, benzoic acid, 2' -disulfonic acid benzidine, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and perylenetetracarboxylic dianhydride in a mass ratio of 400-450:75-85:70-80:10-15:100 into an oil bath reactor, wherein the oil bath reactor comprises a heating device, an oil bath pot is arranged above the heating device, a cover plate is arranged above the oil bath pot, a guide wheel is movably connected inside the cover plate, a moving screw is movably connected with the guide wheel, the moving screw is fixedly connected with a clamping plate, the clamping plate is movably connected with the reaction bottle, heating is carried out to 75-85 ℃, stirring and reacting at constant speed is carried out for 3-6h, heating is carried out to 190 ℃, stirring and reacting at constant speed is carried out for 18-36h, cooling is carried out to room temperature, adding acetone solvent to separate out precipitation, and washing with acetone to obtain sulfonic triethylamine polyimide.

(2) Adding a sulfuric acid solution with the substance amount concentration of 0.5-1mol/L and sulfotriethylamine polyimide into a reaction bottle, stirring at a constant speed to protonate the sulfotriethylamine salt, filtering concentrated sulfuric acid, washing with distilled water and acetone, and drying to prepare the sulfopolyimide.

(3) Adding a pyridine solvent, sulfopolyimide with the mass ratio of 100:180-220 and 2-bromine isobutyryl bromide into a reaction bottle, reacting for 2-5h in ice-water bath, then reacting for 10-20h at room temperature, adding a methanol solvent to precipitate, filtering the solvent, washing with methanol and drying to prepare the 2-bromine isobutyrated sulfopolyimide.

(4) Adding N, N-dimethylformamide solvent, 2-bromoisobutylated sulfopolyimide, methacrylic acid, acrylamide, 4-dimethylaminopyridine, cuprous chloride and copper chloride into a reaction bottle, heating to 50-80 ℃ in argon atmosphere, stirring at a constant speed for reaction for 20-60min, adding N, N-methylene bisacrylamide, wherein the mass ratio of the 2-bromoisobutylated sulfopolyimide, the methacrylic acid, the acrylamide, the 4-dimethylaminopyridine, the cuprous chloride, the copper chloride and the N, N-methylene bisacrylamide is 30-55:100:20-40:6-12:3.5-8:0.25-0.5:0.3-0.8, stirring at a constant speed for reaction for 10-20h, cooling to room temperature, adding distilled water to precipitate, washing with distilled water, dialyzing and purifying to prepare the high-strength sulfopolyimide grafted acrylic acid-based hydrogel adsorbing material.