CN107824057B - Hyperbranched polymer modified polymer film and preparation method and application thereof - Google Patents
Hyperbranched polymer modified polymer film and preparation method and application thereof Download PDFInfo
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- CN107824057B CN107824057B CN201710971148.3A CN201710971148A CN107824057B CN 107824057 B CN107824057 B CN 107824057B CN 201710971148 A CN201710971148 A CN 201710971148A CN 107824057 B CN107824057 B CN 107824057B
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- 229920000587 hyperbranched polymer Polymers 0.000 title claims abstract description 93
- 229920006254 polymer film Polymers 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000003999 initiator Substances 0.000 claims abstract description 59
- 150000008442 polyphenolic compounds Chemical class 0.000 claims abstract description 59
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 59
- 229920005597 polymer membrane Polymers 0.000 claims abstract description 56
- 239000012528 membrane Substances 0.000 claims description 155
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 149
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 115
- 239000011259 mixed solution Substances 0.000 claims description 107
- 239000007983 Tris buffer Substances 0.000 claims description 99
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 93
- 239000000243 solution Substances 0.000 claims description 81
- 238000003756 stirring Methods 0.000 claims description 77
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 55
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 54
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- 229910021641 deionized water Inorganic materials 0.000 claims description 53
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 44
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/46—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a hyperbranched polymer modified polymer membrane and a preparation method and application thereof, and belongs to the field of modified polymer membranes with anti-pollution performance. Aiming at the problems that the polymer membrane is easy to be polluted by protein, oil and the like to cause a series of temporary or permanent pollution and the like in the prior art due to the fact that the surface energy of the polymer membrane is low, the hyperbranched polymer with a special structure is prepared by starting from an initiator through benzyl protection and deprotection, and is grafted to the surface of the polymer membrane by utilizing plant polyphenol, so that the prepared hyperbranched polymer modified polymer membrane has remarkable pollution resistance, improved antibacterial property and hydrophilicity, and has a good application prospect in the field of sewage treatment. Meanwhile, the invention opens up an effective way with simple operation and strong universality for the modification of the polymer film under mild conditions.
Description
Technical Field
The invention relates to the field of modified polymer films with anti-pollution performance, in particular to a hyperbranched polymer modified polymer film and a preparation method and application thereof.
Background
The polymer film has excellent film forming property, chemical and thermal stability, oxidation resistance, corrosion resistance and acid and alkali resistance, and is one of the most common film materials. For example, the invention patent with the application number of 201310472682.1 discloses a method for preparing a polymer porous membrane for removing water pollutants, which is characterized in that cyclodextrin is blended with a membrane preparation material, and a cross-linking agent is added to fix the cyclodextrin in the membrane material, so that the problem that the cyclodextrin is lost from the polymer porous membrane after being used for many times, thereby losing the selective separation function of the polymer porous membrane and changing the hydrophilic performance and the like of the polymer porous membrane is avoided. The polymer porous membrane prepared by the invention has obvious adsorption and removal capacity on organic pollutants in water bodies of phenols and aromatic amines (aromatics), has good removal effect on heavy metal ions, has high separation efficiency, reduced pressure and convenient regeneration, is easy for large-scale production and application, and can be widely used in ecological protection water body purification treatment systems and water treatment systems.
Also as invented patent application No. 201280060321.X, "membrane, water treatment system and method of manufacture" is disclosed, characterized in that the membrane comprises a porous support and a polymer layer disposed on the porous support. The membrane further includes a plurality of substantially hydrophobic mesoporous nanoparticles disposed within the polymer layer. Water treatment systems and methods of making membranes are also provided.
The invention patent with application number 201110415045.1 discloses a permanent hydrophilic modification method for the surface of a porous membrane and the porous membrane obtained by the method, the method comprises the steps of soaking the porous membrane by using a solution of a polymer containing a vinyl alcohol chain segment, a first solvent and deionized water, evaporating to remove the solvent, adsorbing the hydrophilic polymer on the surface of the porous membrane and the surface of a membrane pore to form a thin layer, and then carrying out a crosslinking reaction by using a crosslinking agent and hydrophilic polymers adsorbed on the surface of the membrane to form a network-shaped hydrophilic polymer thin layer on the outer side of the porous membrane. The method can completely avoid the phenomenon of flux reduction caused by hole blocking, and the generated hydrophilic coating is firmer and has good hydrophilic treatment effect.
However, in the membrane separation process, the polymer membrane composed of these materials is generally liable to adsorb organic substances (such as proteins, colloids, microorganisms, etc.) in the raw material liquid, thereby causing membrane contamination; when contacting blood, nonspecific adsorption of proteins on the membrane surface also causes adverse effects such as coagulation, which deteriorates the performance and shortens the service life. In fact, the hydrophilicity, charge and charge density of the membrane surface all have important influence on the adsorption of organic pollutants.
For polymer porous membranes, although surface modification can change the above properties, increasing the thickness of the selective layer, decreasing or even plugging the pores of the membrane can cause additional mass transfer resistance, thereby affecting the permeability. In a continuous constant flux permeation process, the reduction of pore size and even pore blockage can cause the increase of local permeation flux and mass transfer resistance when liquid passes through the membrane pores. To maintain this flux, it is necessary to increase the transmembrane pressure during use, which also results in further accumulation of contaminants on the membrane surface and membrane pores. Such repeated vicious cycles shorten the life of the polymer membrane and increase the cost of the separation process. In order to improve the hydrophilicity of the polymer membrane, methods such as physical blending or surface grafting are often adopted, but the instability of physical blending and the complexity of surface grafting restrict the application of the polymer membrane in industry. Therefore, the technical scheme is necessary for providing a simple, convenient, efficient and high-universality technical scheme which can effectively adsorb impurities such as pollutants in water, efficiently treat water quality, keep the polymer membrane clean and recycle for many times.
Disclosure of Invention
In order to overcome the defects that a polymer membrane is easy to be polluted and the hydrophilic modification is uncontrollable in the using process, the invention aims to design a hydrophilic substance with a special structure, perform functional design on the surface of the membrane, construct a hydrophilic anti-pollution surface and prolong the service life of the membrane in the application process.
In order to achieve the above object, the present invention provides a method for preparing a hyperbranched polymer-modified polymer film, comprising the steps of:
(1) n, N-dibenzyl-2-aminopolyglycidyl ether (Bn)2-synthesis of TRIS-HbPG): initiator N, N-dibenzyl-2 amino-trihydroxymethyl methane (Bn)2-TRIS) is added into anhydrous benzene or toluene, cesium hydroxide monohydrate is added into the system after deoxygenation, a solid reactant is obtained after reaction, the solid reactant is added into diglyme, glycidol is added into the system drop by drop after deoxygenation to obtain a high-viscosity product, the high-viscosity product is dissolved and replaced by cation exchange resin to obtain a replacement solution, and the replacement solution is purified, precipitated and dried to obtain a product Bn2-TRIS-HbPG；
(2) Synthesis of amino-terminal hyperbranched polyglycidyl ether (NH)2-HbPG): b n is2Dissolving TRIS-HbPG in methanol solution, adding catalyst, and placing the system in a high-pressure hydrogen ringAfter reaction under the ambient condition, filtering, purifying and drying to obtain a product NH2-HbPG；
(3) Preparation of plant polyphenol modified polymer film: immersing the polymer film in TRIS buffer solution containing plant polyphenol and metal salt, and obtaining a plant polyphenol modified polymer film after reaction;
(4) hyperbranched Polymer graft-modified Polymer membranes (with M)HPG-PVDFRepresenting a hyperbranched polymer graft-modified polymer membrane); immersing the plant polyphenol modified polymer film in a solution containing NH2Reacting HbPG with NaCl in TRIS buffer solution, washing, and drying to obtain MHPG-PVDF；
Further, in the step (1), the initiator Bn2-synthesis of TRIS: adding TRIS (hydroxymethyl) aminomethane (TRIS) into a polar solvent, dissolving and mixing, adjusting the pH value of a system to 7-9, continuously stirring, adding benzyl bromide into the system, performing reflux reaction, distilling under reduced pressure, extracting with an organic solvent, washing, removing water, and recrystallizing to obtain an initiator Bn2-TRIS；
Further, the initiator Bn in the step (1)2The synthesis of the TRIS comprises the following steps of adding TRIS into a polar solvent, stirring for 1-2h at 40-60 ℃ to obtain a mixed solution A, wherein the ratio of the polar solvent to the TRIS is 100-200m L: 3-8g, adding strong base and weak acid salt into the mixed solution A, adjusting the pH value of the system to be 7-9, continuously stirring for 1-2h to obtain a mixed solution B, adding benzyl bromide into the mixed solution B, carrying out reflux reaction for 18-30h at the temperature of 120-160 ℃, cooling the reaction system to room temperature, filtering, removing strong base and weak acid salt solids to obtain a mixed solution C, wherein the mass ratio of the benzyl bromide to the TRIS is 14-20:3-8, placing the mixed solution C into a reduced pressure distillation device, and removing the polar solvent by the aid of a vacuum oven at the temperature of 80-90 ℃ to obtain Bn2-a crude TRIS product; dissolving Bn with chloroform2And (3) extracting the TRIS crude product to obtain a mixed solution D, repeatedly washing the mixed solution D with deionized water and a saturated sodium bicarbonate solution for 2-4 times, adding a water removing agent A into the mixed solution, stirring the mixed solution for 3-6 hours, removing residual water in the solution, filtering the mixed solution, removing a chloroform solvent in the system through rotary evaporation, adding ethyl acetate, and recrystallizing the mixed solution. Vacuum drying at 60-80 deg.C,obtaining a white solid initiator Bn2-TRIS。
Preferably, the strong base and weak acid salt is one of potassium carbonate, potassium bicarbonate, sodium carbonate and sodium bicarbonate.
Furthermore, the addition ratio of the TRIS, the chloroform, the water removing agent A and the ethyl acetate is 3-8 g: 200-400m L: 1-3 g: 20-30m L.
Further, the polar solvent in the step (1) is subjected to water removal treatment before the reaction with TRIS, and the specific method comprises the steps of adding a water removal agent B into the polar solvent, mixing, stirring for 6-12h at 60-80 ℃, and carrying out reduced pressure distillation to obtain the anhydrous polar solvent, wherein the ratio of the water removal agent B to the polar solvent is 1-3 g: 100-200m L.
Further, the polar solvent is one of N, N-Dimethylformamide (DMF), tetrahydrofuran, or N, N-dimethylacetamide.
Further, Bn of the step (1)2-the synthesis of TRIS-HbPG comprises the following steps: adding initiator Bn into anhydrous benzene or toluene2-TRIS, introducing nitrogen for 10-20 minutes to remove oxygen to obtain a suspension A, wherein the ratio of the initiator to anhydrous benzene or toluene is 0.5-5 g: 1-20m L, adding cesium hydroxide monohydrate to the suspension A, carrying out a stirring reaction at 50-70 ℃ for 1-2 hours, wherein the mass ratio of the cesium hydroxide monohydrate to the initiator is 0.2-2: 0.5-5, carrying out vacuum filtration at 70-80 ℃ for 1-2 hours to remove the solvent of the anhydrous benzene or toluene to obtain a mixture B, adding diglyme to the mixture B, heating the system to 90-100 ℃, continuously introducing nitrogen for 10-30 minutes, wherein the ratio of the diglyme to the initiator is 30-50m L: 1g, adding glycidol to the nitrogen-protected reaction system, dropwise adding the glycidol for not less than 8 hours, continuously carrying out a stirring reaction for 8-12 hours to obtain a high-viscosity product, wherein the ratio of the initiator to the glycidol is 1 g: 10m L-80m L, dissolving the product in methanol, carrying out a cation exchange resin, carrying out a dropwise addition, carrying out a filtration, carrying out a condensation reaction for 4-80 hours, and carrying out a condensation reaction under a vacuum exchange reaction for a final reaction under conditions of adding Bn, wherein the mass ratio of the initiator to obtain a precipitation is changed2-TRIS-HbPG。
Further, the glycidol and the diglyme in the step (1) need to be subjected to water removal treatment, and the specific method comprises the steps of adding a water removal agent B into the glycidol and the diglyme respectively, stirring for 6-12h, and carrying out reduced pressure distillation at the temperature of 60-80 ℃ to obtain anhydrous glycidol and anhydrous diglyme, wherein the ratio of the water removal agent B to the polar solvent is 1-3 g: 100-200m L.
Further, the water removing agent A is calcium hydride.
Further, the water removing agent B is one or more of anhydrous calcium chloride, anhydrous magnesium sulfate, activated alumina, anhydrous sodium sulfate, anhydrous calcium sulfate, calcium hydride and a 4A molecular sieve.
Further, the synthesis reaction in the step (1) is anion ring-opening polymerization, monomer glycidol is added into the system through a constant pressure dropping funnel or a constant speed injector, and the dropping process needs to be slowly carried out.
Further, NH of the step (2)2-synthesis of HbPG comprising the following steps: b n is2Adding TRIS-HbPG and 10% palladium-carbon in a mass ratio of 1-2:0.15-0.3 into a methanol solution, carrying out reduction reaction for 48-72h under a pressure of 50-80bar, filtering solid residues, precipitating by cold ether, and drying in vacuum at 60-80 ℃ for 6-8h until the mass is not changed. To obtain a synthetic product NH2-HbPG, said Bn2The ratio of-TRIS-HbPG to methanol was 1-2 g: 100-2The proportion of the addition of TRIS-HbPG was 100-200m L: 1-2 g.
Further, the preparation of the plant polyphenol modified polymer film in the step (3) comprises the following steps of (a) preparing a plant polyphenol mixed solution, namely adding TRIS and metal salt into deionized water, mixing, adjusting the pH to 7-10 to obtain a TRIS buffer solution, adding plant polyphenol into the TRIS buffer solution, and mixing to obtain a plant polyphenol mixed solution, wherein the adding proportion of the plant polyphenol to the plant polyphenol mixed solution is that the plant polyphenol to the metal salt to the water is 1-5.5g, the metal salt to the water is 1-6g, the metal salt to the water is 1-55g, and the plant polyphenol mixed solution is 1000m L;
(b) immersing the polymer film in the plant polyphenol mixed solution, and reacting in a constant-temperature water bath oscillator for 3-24h at the temperature of 20-30 ℃; and taking out the wet film, and repeatedly washing the wet film in deionized water for 10-20 minutes to obtain the plant polyphenol modified polymer film.
Further, in the step (3), the polymer membrane is one of a polyvinylidene fluoride membrane, a polytetrafluoroethylene membrane, a polysulfone membrane, a polyethersulfone membrane, a polypropylene membrane, a polyamide membrane or a regenerated cellulose membrane.
Further, in the step (3), the polymer film is pretreated by: immersing the polymer film in absolute ethyl alcohol for 0.5-1h, then immersing in deionized water for 0.5-1h, and repeating the steps for 2-4 times; after treatment, the polymer film was placed in deionized water for use.
Further, in the step (3), the plant polyphenol is one or more of tannic acid, caffeic acid, cinnamic acid, quinic acid, chlorogenic acid, kojic acid, tea polyphenol, grape seed polyphenol, agrimonine, sanguisorba officinalis, rose essence, anthocyanin, catechin, epicatechin, gerberrin, caesalpinia coriaria element, oenothera, prairitin, punicin, cornus officinalis, quercetin, gallic acid, ellagic acid or arbutin.
Further, the preparation of the hyperbranched polymer-modified polymer membrane of the step (4) comprises the following steps: (a) preparing a hyperbranched polymer mixed solution: adding TRIS and metal salt into deionized water, mixing, adjusting pH to 7-10 to obtain TRIS buffer solution, adding NH into TRIS buffer solution2Mixing and stirring HbPG to obtain a hyperbranched polymer mixed solution, wherein the hyperbranched polymer mixed solution comprises the following components in parts by weight: TRIS: metal salt: NH (NH)2-HbPG: 0.5-5 g: 5-50 g: 0.1-10 g: 1000m L;
(b)MHPG-PVDFthe preparation of (1): immersing the plant polyphenol modified polymer film into the hyperbranched polymer mixed solution, and slightly stirring the mixture at the temperature of between 20 and 30 ℃ to react for 6 to 12 hours; taking out the wet film, repeatedly rinsing in deionized water for 5-10 minutes, vacuum drying at 60-80 deg.C for 6-10h until the film quality does not change to obtain MHPG-PVDF。
It is another object of the present invention to provide a hyperbranched polymer-modified polymer film.
Another object of the present invention is to provide an application of the hyperbranched polymer-modified polymer membrane.
The hyperbranched polymer modified polymer membrane is applied to the protein pollution resistance.
Three water-protein-water solution circulating filtration experiments were performed under pressure in a cross-flow filtration mode. And (3) judging the pollution and cleaning performance of the membrane material by calculating the change of the membrane flux and the magnitude of the flux recovery rate. (pure water flux is often used as a basic index for evaluating membrane performance, and the change of flux reflects the degree of pollution of membrane materials to a certain extent.) the specific steps are as follows:
the membrane is cut into proper size, put into a filter element and connected with pure water. Firstly, prepressing for 15-30min under 0.05-0.4 MPa, reducing the pressure to 0.01-0.3 MPa, stabilizing the pressure, testing the quality of pure water passing once every 4-10min after the flux is stable, and calculating the pure water flux according to the following formula;
wherein V is the volume of the permeate; a is the effective area of the membrane; Δ t is the time required to permeate a volume V of filtrate.
Then, pure water is changed into Bovine Serum Albumin (BSA) solution of 1 g/L, the pressure is still maintained at 0.01 MPa-0.3 MPa, the change of the flux of the protein solution is tested every 4-10min, the testing time is 5-30min, finally, the membrane is taken out, the membrane is washed by phosphate buffer solution, after about 15-30min, the pure water is connected, the flux of the pure water is tested, and the above steps are repeated for three times, finally, stable pure water fluxes JW0, JW1, JW2 and JW3 are respectively obtained, JB1, JB2 and JB3 are obtained, and the pure water fluxes after each cleaning are marked as Jr1, Jr2 and Jr 3.
The Flux Recovery Ratio (FRR) is calculated as follows:
after water-protein circulation experiments, the hyperbranched polymer modified polymer membranes respectively reach more than 80 percent and are more than twice of the flux recovery rate of the pure polymer membranes, which shows that the introduction of the hyperbranched polymer leads the polymer membranes to form hydrophilic coatings, has good protein pollution resistance and lays a foundation for prolonging the service life of the membranes in the application process.
Advantageous effects
1. The modification method is simple, the operation is simple and convenient, the reaction is mild, and the modification process medium is water, so that the damage of the performance of the membrane body and the environmental pollution caused by an organic solvent are avoided. The invention has wide application range and has no limit to the appearance, the size, the membrane material and the like of the polymer membrane.
2. NH of the invention2The HPG can be effectively grafted to the surface of the polymer membrane, and the surface appearance and the integral structure of membrane pores of the surface of the polymer membrane are kept in the grafting process, so that the original excellent performance is kept. Meanwhile, the thickness of the functional layer of the modified membrane can be determined by measuring the particle size of the hyperbranched polymer, so that the purpose of controllably modifying the polymer membrane through hydrophilization is achieved.
3. The test results of the contact angle and the pure water permeability show that the hydrophilicity and the permeability of the polymer film modified by the hyperbranched polyglycidyl ether graft are obviously improved.
4. Compared with the pure polymer membrane, the hyperbranched polymer modified polymer membrane keeps higher flux in the whole circulating filtration process, and the initial water flux respectively reaches 249.02L/m2h、317.23L/m2h and 371.14L/m2h, much higher than 122.86L/m for a pure polymer film2h. After 3.5h of water-protein circulation experiment, the flux recovery rate of the pure polymer film is 41.25%, and the flux recovery rate of the modified polymer film is respectively 90.06%, 88.22% and 88.04%, which shows that the introduction of the hyperbranched polymer leads the polymer film to form a hydrophilic coating which has good protein pollution resistance and is used for prolonging the application processThe service life of the middle membrane lays a foundation.
The membrane dynamic protein pollution resistance circulating filtration experiment shows that NH along with hydrophilicity2The successful grafting of HPG improves the protein pollution resistance of the membrane surface, increases the flux recovery rate, and the polymer membrane modified by the hyperbranched polymer shows good protein pollution resistance. NH for modifying surface hydrophilicity of membrane2HPG can combine with water molecules to form a hydration layer, inhibit the adsorption and deposition of protein on the surface of the membrane and prevent the blockage of the membrane pores. In addition, a small amount of BSA adsorbed or deposited on the surface of the membrane is mostly physical pollution, and in addition, the existence of a hydration layer can easily be cleaned and removed, so that the membrane has high flux recovery rate and strong anti-pollution performance.
5. Compared with the traditional hyperbranched polyglycidyl ether, the hyperbranched polyglycidyl ether with monoamino has the advantages that n-1 hydroxyl groups around the hyperbranched polyglycidyl ether are reserved, one of the hydroxyl groups is changed into the amino group, and the structure is special. By changing the ratio of the monomer to the initiator in the synthesis process, the invention can synthesize hyperbranched polymers with different molecular weights, the range of the number average molecular weight is 500-6000g/mol, and the application of the hyperbranched polymers in the aspect of modifying polymer films is widened. The molecular weight and the grafting density of the hyperbranched polymer used in the invention have good controllability, and the relationship between hydrophilic modification and permeability can be balanced by selecting proper grafting chain length and grafting density.
The technical principle of the invention is as follows:
the hyperbranched polymer constructed by the invention is an ideal monodisperse macromolecule, has a highly branched three-dimensional space structure, and the tail end of the branched structure of the hyperbranched polymer contains a large number of functional groups. From the viewpoint of molecular structure, hyperbranched polymers are between linear polymers and dendrimers. Compared with linear polymers, the hyperbranched molecules have the characteristics of high solubility, low viscosity, large space volume, high reactivity and the like, so that the hyperbranched molecules have wide application in the fields of coatings, liquid crystals, drug release, polymer blending, water treatment and the like.
Hyperbranched polyglycidyl ether (HbPG) is a linear unit composition similar to polyethylene glycol, and contains a large amount of hydroxyl aroundThe polyether has excellent solubility and good biocompatibility. Based on the characteristic that tannic acid is easy to carry out secondary functionalization, the invention designs and synthesizes hyperbranched polyglycidyl ether (NH) with single amino terminal2HbPG), characterized by the preservation of n-1 hydroxyl groups around HbPG, starting from the initiator, so that each molecule contains a single amino function. When NH is present2After the Michael addition or Schiff base reaction of the amino groups of HbPG with the quinone groups of tannic acid, this hyperbranched polymer is anchored to the surface of a polymer film containing a tannic acid coating. Based on the characteristics of monoamino groups, the hyperbranched polymer is distributed on the surface of the membrane in a single layer and has a specific umbrella-shaped structure.
The invention provides a hyperbranched polyglycidyl ether with single amino terminal, which is prepared by introducing benzyl to protect amino of initiator trihydroxymethyl aminomethane, synthesizing and obtaining bis-benzyl protected hyperbranched polyglycidyl ether by an anion ring-opening polymerization method, and then hydrogenating and reducing benzyl to amino.
The invention takes plant polyphenol as a transition layer, and anchors the hyperbranched polymer with the special structure on the surface of a polymer film. Based on the characteristics of monoamino groups, the hyperbranched polymer is distributed on the surface of the polymer film in a single layer, so that the length and the density of grafted chains can be determined, and the hydrophilization performance of the polymer film can be improved.
It should be noted that the technical effect of the hyperbranched polymer modified polymer membrane prepared by the invention is the result of mutual synergy and interaction of all components, is not the simple superposition of raw material functions, and the generated effect far exceeds the superposition of the functions and effects of all single components, thus having better advancement and practicability.
Drawings
The invention will be further described with reference to the following drawings and specific embodiments:
FIG. 1: water contact Angle test (M) of PVDF membranes before and after modificationPVDF: a pure PVDF membrane; mTA-PVDFCoating a modified PVDF film with tannic acid; mHPG1-1-PVDF、MHPG1-2-PVDFAnd MHPG1-3-PVDF: hyperbranched polymer graft modified PVDF membranes with different molecular weights);
FIG. 2: PVDF membrane static anti-protein adsorption experiment before and after modification (M)PVDF: a pure PVDF membrane; mTA-PVDFCoating a modified PVDF film with tannic acid; mHPG1-1-PVDF、MHPG1-2-PVDFAnd MHPG1-3-PVDF: hyperbranched polymer graft modified PVDF membranes with different molecular weights);
FIG. 3: PVDF membrane static antibacterial adsorption experiment before and after modification (M)PVDF: a pure PVDF membrane; mTA-PVDFCoating a modified PVDF film with tannic acid; mHPG1-1-PVDF、MHPG1-2-PVDFAnd MHPG1-3-PVDF: hyperbranched polymer graft modified PVDF membranes with different molecular weights);
FIG. 4: dynamic protein contamination analysis (M) of PVDF membrane before and after modificationPVDF: unmodified PVDF membranes, MHPG1-1-PVDF、MHPG1-2-PVDFAnd MHPG1-3-PVDF: hyperbranched polymer graft-modified PVDF membranes of different molecular weights).
Detailed Description
The invention is described below by means of specific embodiments. Unless otherwise specified, the technical means used in the present invention are well known to those skilled in the art. In addition, the embodiments should be considered illustrative, and not restrictive, of the scope of the invention, which is defined solely by the claims. It will be apparent to those skilled in the art that various changes or modifications in the components and amounts of the materials used in these embodiments can be made without departing from the spirit and scope of the invention.
Example 1 preparation of hyperbranched Polymer modified Polymer membranes
The polymer membrane selected in this example was a polyvinylidene fluoride membrane.
(1) Initiator Bn2The synthesis of the-Tris comprises the steps of adding Tris into a polar solvent N, N-Dimethylformamide (DMF), stirring for 1.5 hours at 50 ℃ to obtain a mixed solution A, wherein the proportion of the DMF to the Tris is 150m L: 5g, adding sodium carbonate into the mixed solution A, adjusting the pH value of a system to 8, continuously stirring for 1.5 hours to obtain a mixed solution B, adding benzyl bromide into the mixed solution B, carrying out reflux reaction for 24 hours at 140 ℃, and obtaining a reactantCooling to room temperature, filtering, and removing sodium carbonate solids to obtain a mixed solution C, wherein the mass ratio of benzyl bromide to Tris is 17: 5.5; placing the mixed solution C in a reduced pressure distillation device, and removing the DMF solvent by the assistance of a vacuum oven at the temperature of 85 ℃ to obtain Bn2-Tris crude product; dissolving Bn with chloroform2Extracting a Tris crude product to obtain a mixed solution D, repeatedly washing the mixed solution D for 3 times by using deionized water and a saturated sodium bicarbonate solution, adding calcium hydride, stirring for 4 hours, removing residual water in the solution, filtering, removing a chloroform solvent in the system by rotary evaporation, adding ethyl acetate, and recrystallizing. Vacuum drying at 70 ℃ to obtain a white solid initiator Bn2-Tris。
Wherein the adding ratio of Tris, chloroform, calcium hydride and ethyl acetate is 5g to 300m L to 1.5g to 25m L.
The method comprises the specific steps of adding anhydrous calcium chloride into DMF, mixing, stirring for 9 hours at 70 ℃, and distilling under reduced pressure to obtain an anhydrous polar solvent, wherein the ratio of the anhydrous calcium chloride to the DMF is 2 g: 150m L.
(2)Bn2-the synthesis of Tris-HbPG comprises the following steps: adding initiator Bn into anhydrous benzene or toluene2Tris, introducing nitrogen for 15 minutes to remove oxygen to obtain a suspension A, adding cesium hydroxide monohydrate into the suspension A, stirring and reacting at 60 ℃ for 1.5 hours to obtain a suspension A, wherein the mass ratio of the cesium hydroxide monohydrate to the initiator is 1: 2.5, performing vacuum filtration at 75 ℃ for 1.5 hours to remove an anhydrous benzene or toluene solvent to obtain a mixture B, adding diglyme into the mixture B, heating the mixture B to 95 ℃, continuously introducing nitrogen for 20 minutes, wherein the ratio of the diglyme to the initiator is 40m L: 1g, dropwise adding glycidol into the nitrogen-protected reaction system for not less than 8 hours, continuously stirring and reacting for 10 hours to obtain a high-viscosity product, wherein the ratio of the initiator to the glycidol is 1 g: 45m L, dissolving the product into methanol, stirring and filtering by using a cation exchange resin to remove the cation exchange resin, concentrating, pouring the concentrated solution into cold diethyl ether for precipitation for several times, and vacuumizing at 75 ℃ to obtain a suspension A1.5h until the quality does not change any more, and the final reaction product Bn is obtained2The ratio of addition of the cold ether to the initiator was 150m L: 1.5 g.
The synthesis reaction in the step (2) is anion ring-opening polymerization, monomer glycidol is added into the system through a constant pressure dropping funnel or a constant speed injector, and the dropping process needs to be slowly carried out.
The method for removing water from the glycidol and the diglyme in the step (2) comprises the specific steps of adding anhydrous calcium chloride into the glycidol and the diglyme respectively, stirring for 9 hours, and distilling under reduced pressure at 70 ℃ to obtain the anhydrous glycidol and the anhydrous diglyme, wherein the ratio of the anhydrous calcium chloride to N, N-Dimethylformamide (DMF) is 2 g: 150m L.
(3)NH2-synthesis of HbPG comprising the following steps: b n is2Adding TRIS-HbPG and 10% palladium carbon in a mass ratio of 1.5:0.2 into a methanol solution, carrying out reduction reaction for 55h by using hydrogen under the pressure of 75bar, filtering solid residues, precipitating by using cold ether, and drying for 7h under vacuum at 70 ℃ until the mass is not changed. To obtain a synthetic product NH2-HbPG, said Bn2-TRIS-HbPG and methanol ratio 1.5 g: 150m L Cold diethyl ether and Bn2The proportion of added-TRIS-HbPG was 150m L: 1.5 g.
(4) The preparation method of the plant polyphenol modified polymer membrane comprises the following steps of (a) preparing a plant polyphenol mixed solution, namely adding Tris and metal salt into deionized water for mixing, adjusting the pH to 8.5 to obtain a Tris buffer solution, adding tannic acid into the Tris buffer solution for mixing to obtain a tannic acid mixed solution, wherein the addition ratio of the Tris to the tannic acid to the metal salt to the water is 3 g: 3.5 g: 20 g: 1000m L;
2) immersing the polymer film in the tannin mixed solution, and reacting for 9 hours in a constant-temperature water bath oscillator at the temperature of 25 ℃; and taking out the wet film, and repeatedly washing the wet film in deionized water to obtain the tannin modified polymer film.
In the step (4), the polymer film is pretreated: immersing the polymer film in absolute ethyl alcohol for 0.5-1h, then immersing in deionized water for 0.5-1h, and repeating the steps for 2-4 times; after treatment, the polymer film was placed in deionized water for use.
(5) The preparation of the hyperbranched polymer modified polymer membrane comprises the following steps: (a) preparing a hyperbranched polymer mixed solution: adding Tris and metal salt into deionized water, mixing, adjusting pH to 8.5 to obtain Tris buffer solution, adding NH into the Tris buffer solution2Mixing and stirring HbPG to obtain a hyperbranched polymer mixed solution, wherein the hyperbranched polymer mixed solution comprises the following components in parts by weight: TRIS: metal salt: NH (NH)2-HbPG: water 2 g: 15 g: 5 g: 1000m L;
(b)MHPG-PVDFthe preparation of (1): immersing the tannin modified polymer film into the hyperbranched polymer mixed solution, and slightly stirring and reacting for 9 hours at the temperature of 25 ℃; taking out the wet film, repeatedly rinsing in deionized water, vacuum drying at 70 deg.C for 8 hr until the film quality does not change to obtain MHPG-PVDF。
Example 2 preparation of hyperbranched Polymer modified Polymer membranes
The polymer membrane selected in this example was a polytetrafluoroethylene membrane.
(1) Initiator Bn2The synthesis of the Tris-phosphate comprises the following steps of adding Tris into a polar solvent, stirring for 2 hours at 40 ℃ to obtain a mixed solution A, adding sodium carbonate into the mixed solution A, adjusting the pH value of a system to 7, continuously stirring for 2 hours to obtain a mixed solution B, adding benzyl bromide into the mixed solution B, carrying out reflux reaction for 30 hours at 120 ℃, cooling the reaction system to room temperature, filtering to remove sodium carbonate solids to obtain a mixed solution C, wherein the mass ratio of the benzyl bromide to the Tris is 14:3, placing the mixed solution C into a reduced pressure distillation device, and removing a DMF solvent in a vacuum oven at 80 ℃ in an auxiliary manner to obtain Bn2-Tris crude product; dissolving Bn with chloroform2Extracting a Tris crude product to obtain a mixed solution D, repeatedly washing the mixed solution D with deionized water and a saturated sodium bicarbonate solution for 2-4 times, adding calcium hydride, stirring for 6 hours, removing residual water in the solution, filtering, removing a chloroform solvent in the system through rotary evaporation, adding ethyl acetate, and recrystallizing. At 60 deg.CVacuum drying to obtain white solid initiator Bn2-Tris。
The adding ratio of Tris, chloroform, calcium hydride and ethyl acetate is 3g to 200m L to 1g to 20m L.
The specific method comprises the steps of adding anhydrous magnesium sulfate into tetrahydrofuran serving as a polar solvent, mixing, stirring for 12 hours at the temperature of 60 ℃, and carrying out reduced pressure distillation to obtain anhydrous tetrahydrofuran, wherein the ratio of the anhydrous magnesium sulfate to the tetrahydrofuran is 1 g: 100m L.
(2)Bn2-the synthesis of Tris-HbPG comprises the following steps: adding initiator Bn into anhydrous benzene or toluene2Tris, introducing nitrogen for 10 minutes to remove oxygen to obtain a suspension A, adding cesium hydroxide monohydrate into the suspension A, stirring and reacting at 50 ℃ for 1 hour to obtain a suspension A, wherein the mass ratio of the cesium hydroxide monohydrate to the initiator is 0.2: 0.5, then carrying out vacuum filtration at 70 ℃ for 1 hour to remove the solvent of anhydrous benzene or toluene to obtain a mixture B, adding diethylene glycol dimethyl ether into the mixture B, heating the mixture B to 90 ℃, continuously introducing nitrogen for 10 minutes, wherein the mass ratio of the diethylene glycol dimethyl ether to the initiator is 30m L: 1g, dropwise adding glycidol into the nitrogen-protected reaction system for not less than 8 hours, continuously stirring and reacting for 12 hours to obtain a high-viscosity product, wherein the mass ratio of the initiator to the glycidol is 1 g: 10m L, dissolving the product into methanol, stirring and filtering to remove cation exchange resin, concentrating, pouring into cold ether for precipitation for several times, vacuumizing at 70 ℃ for 1 hour until the mass of the initiator does not change, and finally obtaining a product Bn2The ratio of addition of the cold ether to the initiator was 100m L: 1 g.
Further, the synthesis reaction in the step (2) is anion ring-opening polymerization, monomer glycidol is added into the system through a constant pressure dropping funnel or a constant speed injector, and the dropping process needs to be slowly carried out.
And (3) further, the glycidol and the diglyme in the step (2) need to be subjected to water removal treatment, and the specific method comprises the steps of adding anhydrous magnesium sulfate into the glycidol and the diglyme respectively, stirring for 6 hours, and carrying out reduced pressure distillation at the temperature of 60 ℃ to obtain the anhydrous glycidol and the anhydrous diglyme, wherein the ratio of the anhydrous magnesium sulfate to the tetrahydrofuran is 1 g: 100m L.
(3) NH of (2)2-synthesis of HbPG comprising the following steps: b n is2Adding TRIS-HbPG and 10% palladium carbon in a mass ratio of 1:0.15 into methanol solution, performing reduction reaction with hydrogen at a pressure of 50bar for 48h, filtering solid residue, precipitating with cold ether, and vacuum drying at 60 deg.C for 8h until the mass is unchanged. To obtain a synthetic product NH2-HbPG, said Bn2-TRIS-HbPG and methanol ratio is 1 g: 100m L cold ether and Bn2The proportion of added-TRIS-HbPG was 100m L: 1 g.
(4) Preparing a caffeic acid mixed solution, namely adding Tris and metal salt into deionized water, mixing, adjusting the pH value to 7 to obtain a Tris buffer solution, adding caffeic acid into the Tris buffer solution, and mixing to obtain the caffeic acid mixed solution, wherein the adding ratio of the caffeic acid to the metal salt to the water is 1 g: 1 g: 1 g: 1000m L;
(b) immersing the polymer film in the caffeic acid mixed solution, and reacting for 3 hours in a constant-temperature water bath oscillator at the temperature of 20 ℃; and taking out the wet film, and repeatedly washing in deionized water to obtain the caffeic acid modified polymer film.
Further, in the step (4), the polymer film is pretreated by: immersing the polymer film in absolute ethyl alcohol for 0.5h, and then immersing in deionized water for 0.5h, repeating the steps for 2-4 times; after treatment, the polymer film was placed in deionized water for use.
(5) The preparation of the hyperbranched polymer-modified polymer membrane of the step (5) comprises the following steps: (a) preparing a hyperbranched polymer mixed solution: adding Tris and metal salt into deionized water for mixing, adjusting the pH value to 7 to obtain Tris buffer solution, and adding NH into the Tris buffer solution2HbPG, mixing and stirring to obtain a hyperbranched polymer mixtureThe hyperbranched polymer mixed solution comprises the following components in proportion: TRIS: metal salt: NH (NH)20.5g of water (preferably: 5 g: 0.1 g: 1000m L;
(b)MHPG-PVDFthe preparation of (1): immersing the caffeic acid modified polymer membrane in the hyperbranched polymer mixed solution, and slightly stirring for reaction for 6 hours at the temperature of 20 ℃; taking out the wet film, repeatedly rinsing in deionized water, vacuum drying at 60 deg.C for 6 hr until the film quality does not change to obtain MHPG-PVDF。
Example 3 preparation of hyperbranched Polymer modified Polymer membranes
The polymer membrane selected in this example was a polysulfone membrane; the plant polyphenol is a mixture of tea polyphenol and grape seed polyphenol according to the mass ratio of 1: 1.
(1) Initiator Bn2The synthesis of the Tris comprises the following steps of adding Tris into a polar solvent, stirring for 1 hour at the temperature of 60 ℃ to obtain a mixed solution A, adding strong potassium bicarbonate into the mixed solution A, adjusting the pH value of a system to be 9, continuously stirring for 1 hour to obtain a mixed solution B, adding benzyl bromide into the mixed solution B, carrying out reflux reaction for 18 hours at the temperature of 160 ℃, cooling the reaction system to the room temperature, filtering to remove potassium bicarbonate solid to obtain a mixed solution C, wherein the mass ratio of the benzyl bromide to the Tris is 20:8, placing the mixed solution C into a reduced pressure distillation device, and removing a DMF solvent in a vacuum oven at the temperature of 90 ℃ to obtain Bn2-Tris crude product; dissolving Bn with chloroform2Extracting a Tris crude product to obtain a mixed solution D, repeatedly washing the mixed solution D with deionized water and a saturated sodium bicarbonate solution for 2-4 times, adding calcium hydride, stirring for 3 hours, removing residual water in the solution, filtering, removing a chloroform solvent in the system through rotary evaporation, adding ethyl acetate, and recrystallizing. Vacuum drying at 80 ℃ to obtain a white solid initiator Bn2-Tris。
The adding ratio of Tris, chloroform, calcium hydride and ethyl acetate is 8g to 400m L to 3g to 30m L.
The specific method comprises the steps of adding a water removing agent B, namely activated alumina into a polar solvent N, N-dimethylacetamide, mixing, stirring for 6 hours at 80 ℃, and distilling under reduced pressure to obtain the anhydrous polar solvent, wherein the ratio of the activated alumina to the polar solvent is 3g to 200m L.
(2)Bn2-the synthesis of Tris-HbPG comprises the following steps: adding initiator Bn into anhydrous benzene or toluene2Tris, introducing nitrogen for 20 minutes to remove oxygen to obtain a suspension A, adding cesium hydroxide monohydrate into the suspension A, stirring and reacting at 70 ℃ for 1 hour to obtain a suspension A, wherein the mass ratio of the cesium hydroxide monohydrate to the initiator is 2: 5, then carrying out vacuum filtration at 80 ℃ for 1 hour to remove an anhydrous benzene or toluene solvent to obtain a mixture B, adding diethylene glycol dimethyl ether into the mixture B, heating the system to 100 ℃, continuously introducing nitrogen for 30 minutes, wherein the mass ratio of the diethylene glycol dimethyl ether to the initiator is 50m L: 1g, dropwise adding glycidol into the nitrogen-protected reaction system for not less than 8 hours, continuously stirring and reacting for 8 hours to obtain a high-viscosity product, wherein the mass ratio of the initiator to the glycidol is 1g to 80m L, dissolving the product in methanol, stirring and filtering to remove cation exchange resin, concentrating, pouring the product into cold ether for precipitation for several times, and carrying out vacuum at 80 ℃ for 1 hour until the mass does not change any more to obtain a final reaction product Bn2The ratio of addition of the cold ether to the initiator was 200m L: 2 g.
Wherein the synthesis reaction in the step (2) is anion ring-opening polymerization, monomer glycidol is added into the system through a constant-pressure dropping funnel or a constant-speed injector, and the dropping process needs to be slowly carried out.
The method comprises the specific steps of respectively adding activated alumina into the glycidol and the diglyme, stirring for 6 hours, and carrying out reduced pressure distillation at 80 ℃ to obtain anhydrous glycidol and anhydrous diglyme, wherein the ratio of the activated alumina to a polar solvent N, N-dimethylacetamide is 3 g: 200m L.
(3) NH of (2)2-synthesis of HbPG comprising the following steps: b n is2-TRIS-HbPG in mass with palladium on carbon at a concentration of 10%Adding into methanol solution at a ratio of 2:0.3, performing reduction reaction with hydrogen at 80bar pressure for 48h, filtering solid residue, precipitating with cold diethyl ether, and vacuum drying at 80 deg.C for 6h until the quality is unchanged. To obtain a synthetic product NH2-HbPG, said Bn2-TRIS-HbPG and methanol in a ratio of 2 g: 200m L Cold diethyl ether to Bn2The proportion of added-TRIS-HbPG was 200m L: 2 g.
(4) The preparation method of the plant polyphenol modified polymer membrane in the step (4) comprises the following steps of (a) preparing a plant polyphenol mixed solution, namely adding Tris and metal salt into deionized water for mixing, adjusting the pH value to 10 to obtain a Tris buffer solution, adding plant polyphenol into the Tris buffer solution, and mixing to obtain the plant polyphenol mixed solution, wherein the adding proportion of the plant polyphenol mixed solution is that Tris, plant polyphenol, metal salt and water is 5.5g, 6g, 55g, 1000m L;
(b) immersing the polymer film in the plant polyphenol mixed solution, and reacting for 24 hours in a constant-temperature water bath oscillator at the temperature of 30 ℃; and taking out the wet film, and repeatedly washing the wet film in deionized water to obtain the plant polyphenol modified polymer film.
Further, in the step (4), the polymer film is pretreated by: immersing the polymer film in absolute ethyl alcohol for 1h, and then immersing in deionized water for 1h, repeating the steps for 2-4 times; after treatment, the polymer film was placed in deionized water for use.
(5) The preparation of the hyperbranched polymer-modified polymer membrane of the step (5) comprises the following steps: (a) preparing a hyperbranched polymer mixed solution: adding Tris and metal salt into deionized water for mixing, adjusting the pH value to 10 to obtain Tris buffer solution, and adding NH into the Tris buffer solution2Mixing and stirring HbPG to obtain a hyperbranched polymer mixed solution, wherein the hyperbranched polymer mixed solution comprises the following components in parts by weight: TRIS: metal salt: NH (NH)2-HbPG: water 5 g: 50 g: 10 g: 1000m L;
(b)MHPG-PVDFthe preparation of (1): immersing the plant polyphenol modified polymer film into the hyperbranched polymer mixed solution, and slightly stirring the mixture at the temperature of 30 ℃ to react for 12 hours; taking out the wet film, and deionizingRepeatedly rinsing in water, vacuum drying at 80 deg.C for 6 hr until the membrane quality does not change to obtain MHPG-PVDF。
Example 4 preparation of hyperbranched Polymer modified Polymer membranes
The polymer film selected in this example is a polypropylene film, and the plant polyphenol is a mixture of tannic acid, Woodfordin, and punicin.
(1) The initiator Bn2-Tris synthesis method comprises the following steps of adding Tris into a polar solvent, stirring for 1-2 hours at 45-55 ℃ to obtain a mixed solution A, adjusting the proportion of the polar solvent to Tris to 140-160m L: 4-6g, adding sodium bicarbonate into the mixed solution A, adjusting the pH value of the system to 7-9, continuing stirring for 1-2 hours to obtain a mixed solution B, adding benzyl bromide into the mixed solution B, carrying out reflux reaction for 18-20 hours at the temperature of 135-145 ℃, cooling the reaction system to room temperature, filtering, removing solid sodium bicarbonate to obtain a mixed solution C, placing the mixed solution C in a reduced pressure distillation device, and removing DMF solvent in a vacuum oven at the temperature of 83-87 ℃ to obtain Bn2-Tris crude product; dissolving Bn with chloroform2And (3) extracting a Tris crude product to obtain a mixed solution D, repeatedly washing the mixed solution D with deionized water and a saturated sodium bicarbonate solution for 2-4 times, adding calcium hydride into the mixed solution, stirring the mixed solution for 3-6 hours, removing residual water in the solution, filtering the mixed solution, removing a chloroform solvent in the system through rotary evaporation, adding ethyl acetate into the mixed solution, and recrystallizing the mixed solution. Vacuum drying at 68-72 deg.C to obtain white solid initiator Bn2-Tris。
Wherein the adding proportion of Tris, chloroform, calcium hydride and ethyl acetate is 4-6 g: 260-320m L: 1-3 g: 24-26m L.
The method comprises the specific steps of adding anhydrous calcium sulfate into a polar solvent N, N-Dimethylformamide (DMF), mixing, stirring for 8-10h at 68-72 ℃, and distilling under reduced pressure to obtain the anhydrous polar solvent, wherein the ratio of the anhydrous calcium sulfate to the DMF is 1-3 g: 146-155m L.
(2)Bn2-the synthesis of Tris-HbPG comprises the following steps: adding initiator Bn into anhydrous benzene or toluene2Tris, deoxygenated by passing nitrogen through it for 14-16 minAdding cesium hydroxide monohydrate into the suspension A, stirring and reacting at 56-66 ℃ for 1-2 hours, wherein the mass ratio of the cesium hydroxide monohydrate to the initiator is 0.6-1.6: 2-3, performing vacuum filtration at 73-76 ℃ for 1-2 hours to remove anhydrous benzene or toluene solvent to obtain a mixture B, adding diglyme into the mixture B, heating the mixture B to 94-98 ℃, continuously introducing nitrogen for 20 minutes, wherein the ratio of the diglyme to the initiator is 38-42m L: 1g, dropwise adding glycidol into the reaction system protected by nitrogen for not less than 8 hours, continuously stirring and reacting for 8-12 hours to obtain a high-viscosity product, wherein the ratio of the initiator to the glycidol is 1g, 36m L-44 m L, dissolving the product in methanol, stirring and filtering to remove cation exchange resin, concentrating, precipitating in 74-76 hours, and performing vacuum filtration to obtain a high-viscosity product, and precipitating in 74-76 hours to obtain a high-viscosity product, wherein the quality of the high-viscosity product is changed under the condition that the reaction is not changed2TRIS-HbPG the cold diethyl ether and initiator are added in a ratio of 145-155m L: 1-2 g.
Wherein the synthesis reaction in the step (2) is anion ring-opening polymerization, monomer glycidol is added into the system through a constant-pressure dropping funnel or a constant-speed injector, and the dropping process needs to be slowly carried out.
The method comprises the specific steps of respectively adding anhydrous calcium sulfate into the glycidol and the diglyme, stirring for 8-10h, and carrying out reduced pressure distillation at 67-72 ℃ to obtain the anhydrous glycidol and the anhydrous diglyme, wherein the ratio of the anhydrous calcium sulfate to the DMF is 1-3 g: 145-155m L.
(3)NH2-synthesis of HbPG comprising the following steps: b n is2Adding TRIS-HbPG and 10% palladium-carbon in a mass ratio of 1-2:0.15-0.3 into a methanol solution, carrying out reduction reaction for 55-65h by using hydrogen under the pressure of 65-75bar, filtering solid residues, precipitating by using cold ether, and drying for 6-8h under vacuum at 65-75 ℃ until the mass is not changed. To obtain a synthetic product NH2-HbPG, said Bn2-the ratio of TRIS-HbPG to methanol is 1-2 g:145-155m L, the cold diethyl ether and Bn2The proportion of addition of TRIS-HbPG was 145-155m L: 1-2 g.
(4) The preparation method of the plant polyphenol modified polymer membrane in the step (4) comprises the following steps of (a) preparing a plant polyphenol mixed solution, namely adding Tris and metal salt into deionized water for mixing, adjusting the pH value to 7.5-8 to obtain a Tris buffer solution, adding plant polyphenol into the Tris buffer solution for mixing to obtain a plant polyphenol mixed solution, wherein the adding proportion of the plant polyphenol mixed solution is that Tris, the plant polyphenol, the metal salt and water is 2-4g, 3-4g, 20-30g, 1000m L;
(b) immersing the polymer film in the plant polyphenol mixed solution, and reacting for 7-12h in a constant-temperature water bath oscillator at the temperature of 24-28 ℃; and taking out the wet film, and repeatedly washing the wet film in deionized water to obtain the plant polyphenol modified polymer film.
In the step (4), the polymer film is pretreated: immersing the polymer film in absolute ethyl alcohol for 0.5-1h, then immersing in deionized water for 0.5-1h, and repeating the steps for 2-4 times; after treatment, the polymer film was placed in deionized water for use.
(5) The preparation of the hyperbranched polymer-modified polymer membrane of the step (5) comprises the following steps: (a) preparing a hyperbranched polymer mixed solution: adding Tris and metal salt into deionized water, mixing, adjusting pH to 7.5-9 to obtain Tris buffer solution, adding NH into the Tris buffer solution2Mixing and stirring HbPG to obtain a hyperbranched polymer mixed solution, wherein the hyperbranched polymer mixed solution comprises the following components in parts by weight: TRIS: metal salt: NH (NH)2-HbPG: water 1.5-3 g: 10-20 g: 4-6 g: 1000m L;
(b)MHPG-PVDFthe preparation of (1): immersing the plant polyphenol modified polymer film into the hyperbranched polymer mixed solution, and slightly stirring the mixture at the temperature of between 24 and 28 ℃ to react for 8 to 10 hours; taking out the wet film, repeatedly rinsing in deionized water, vacuum drying at 64-68 deg.C for 6-10 hr until the film quality does not change to obtain MHPG-PVDF。
Example 5 preparation of hyperbranched Polymer modified Polymer membranes
The polymer membrane selected in this example was a polyvinylidene fluoride membrane.
1) The method comprises the steps of adding 5.5g of trihydroxymethylaminomethane and 150m L of anhydrous N, N-Dimethylformamide (DMF) into a round-bottom flask, stirring for 1h at 60 ℃, then adding 13.8g of potassium carbonate, continuously stirring for 1h, adding 17g of benzyl bromide, refluxing and reacting for 24h at 160 ℃, cooling the reaction system to room temperature, filtering, removing solid potassium carbonate, building a reduced pressure distillation device, removing DMF solvent in a vacuum oven at 80 ℃, adding 300m L of chloroform into the system, dissolving, repeatedly washing for 3 times by using a separating funnel, adding 2g of anhydrous magnesium sulfate, stirring for 6h, removing residual moisture in the solution, filtering, removing a chloroform solvent in the system by using a rotary evaporator, adding 20m L of ethyl acetate, recrystallizing, and drying in vacuum at 80 ℃ to obtain a white solid initiator Bn 2-TRIS.
2) Synthesis of bis-benzyl protected hyperbranched polyglycidyl ether (Bn2TRIS-HbPG) by adding 1.35g of initiator Bn2-TRIS into 3.3m L anhydrous benzene for suspension, introducing nitrogen for 10 minutes, adding 0.75g of cesium hydroxide monohydrate into the suspension, stirring at 60 ℃ for reaction for 1 hour, building a suction filtration system, vacuum-filtering at 80 ℃ for 2 hours to remove toluene solvent, adding diglyme into the system, heating the system to 100 ℃, continuously introducing nitrogen for 20 minutes, dropwise adding 15m L of glycidol into the nitrogen protected reaction system, dropwise adding for 12 hours, continuing to react for 12 hours to obtain a high-viscosity product, dissolving the product in 150m L of methanol, stirring with cation exchange resin for 30 minutes, filtering to remove the cation exchange resin, concentrating, pouring into 200m L of cold diethyl ether for precipitation for several times, vacuumizing at 80 ℃ for 2 hours until the mass does not change any more, and obtaining the final reaction product Bn 2-TRIS-ethyl ether2-TRIS-HbPG。
3) Synthesis of monoamino hyperbranched polyglycidyl ether (NH)2-HbPG); 1.5g Bn2Adding TRIS-HbPG into 150m L methanol solution, adding 300mg palladium carbon with concentration of 10%, reducing the system with hydrogen under 70bar pressure for 72h, filtering, precipitating with 200m L cold diethyl ether, and vacuum drying at 80 deg.C for 8h until the mass is unchanged to obtain the synthetic productNH2-HbPG。
4) Preparing a tannic acid modified polymer film, adding 2g of TRIS (hydroxymethyl) aminomethane (TRIS) into 1L deionized water, adjusting the pH to 8.5 by using a NaOH aqueous solution with the concentration of 0.1 mol/L to obtain a TRIS buffer solution, adding 2g of tannic acid and 16g of sodium chloride into 1L TRIS buffer solution, stirring for 5min to obtain a uniform tannic acid solution, soaking the polymer film in absolute ethyl alcohol and the deionized water for 30min respectively, repeating the soaking for two times, soaking in the deionized water for standby, wherein the soaking time is more than 6h, immersing the polymer film in a beaker filled with 200m L tannic acid solution, reacting for 6h in a constant-temperature water bath oscillator at the temperature of 30 ℃, taking out the modified polymer film from the beaker, and repeatedly rinsing the modified polymer film in the deionized water for 10 min.
5) Preparing the hyperbranched polymer graft modified polymer film, adding 2g of TRIS (hydroxymethyl) aminomethane (TRIS) into 1L deionized water, adjusting the pH to 8.5 by using 0.1 mol/L NaOH aqueous solution to obtain TRIS buffer solution, and adding 0.1-10g of NH2Adding HbPG and 16g of sodium chloride into 1L TRIS buffer solution, stirring for 5min to obtain uniform hyperbranched polymer solution, adding the tannic acid modified polymer film into a beaker filled with 200m of L hyperbranched polymer solution, slightly stirring at 25 ℃ to react for 12h, taking out the hyperbranched polymer modified polymer film, repeatedly rinsing in deionized water for 10min, and vacuum drying at 80 ℃ for 8h until the quality of the film is not changed.
Example 6 preparation of hyperbranched Polymer modified Polymer membranes
The polymer membrane selected in this example was a polyvinylidene fluoride membrane.
1) Synthesis of initiator bis (benzyltris) (Bn)2-TRIS), adding 5.5g of TRIS (hydroxymethyl) aminomethane and 150m L of anhydrous N, N-Dimethylformamide (DMF) into a round bottom flask, stirring for 1h at 60 ℃, then adding 13.8g of potassium carbonate, continuously stirring for 1h, adding 17g of benzyl bromide, refluxing and reacting for 24h at 160 ℃, cooling the reaction system to room temperature, filtering, removing potassium carbonate solid, building a reduced pressure distillation device, removing DMF solvent by a vacuum oven at 80 ℃, adding 300m L of chloroform into the system, dissolving, utilizing a separating funnel,repeatedly washing with 200m L deionized water and saturated sodium bicarbonate solution for 3 times, adding 2g anhydrous magnesium sulfate, stirring for 6h, removing residual water in the solution, filtering, removing chloroform solvent in the system by a rotary evaporator, adding 20m L ethyl acetate, recrystallizing, and drying in vacuum at 80 ℃ to obtain the white solid initiator Bn 2-TRIS.
2) Synthesis of double benzyl group protected hyperbranched polyglycidyl ether (Bn)2TRIS-HbPG) adding 1.35g of initiator Bn2-TRIS into 3.3m L of anhydrous benzene for suspension, introducing nitrogen for 10 minutes, adding 0.75g of cesium hydroxide monohydrate into the suspension, stirring and reacting for 1 hour at 60 ℃, building a suction filtration system, removing toluene solvent under vacuum for 2 hours at 80 ℃, adding diethylene glycol dimethyl ether, heating the system to 100 ℃, continuously introducing nitrogen for 20 minutes, dropwise adding 15-60m L glycidol into the nitrogen-protected reaction system, continuing to react for 12 hours to obtain a high-viscosity product, dissolving the product into 150m L of methanol, stirring for 30 minutes by using cation exchange resin, filtering to remove the cation exchange resin, concentrating, pouring into 200m L of cold ether for precipitation for several times, and vacuum for 2 hours at 80 ℃ until the mass does not change any more to obtain the final reaction product Bn2-TRIS2-TRIS-HbPG。
3) Synthesis of monoamino hyperbranched polyglycidyl ether (NH)2-HbPG); 1.5g Bn2Adding TRIS-HbPG into 150m L methanol solution, adding 300mg palladium carbon with concentration of 10%, reducing the system with hydrogen under 70bar pressure for 72h, filtering, precipitating with 200m L cold diethyl ether, and vacuum drying at 80 deg.C for 8h until the mass is unchanged to obtain synthetic product NH2-HbPG。
4) Preparing a tannic acid modified polymer film, adding 2g of TRIS (hydroxymethyl) aminomethane (TRIS) into 1L deionized water, adjusting the pH to 8.5 by using a NaOH aqueous solution with the concentration of 0.1 mol/L to obtain a TRIS buffer solution, adding 2g of tannic acid and 16g of sodium chloride into 1L TRIS buffer solution, stirring for 5min to obtain a uniform tannic acid solution, soaking the polymer film in absolute ethyl alcohol and the deionized water for 30min respectively, repeating the soaking for two times, soaking in the deionized water for standby, wherein the soaking time is more than 6h, immersing the polymer film in a beaker filled with 200m L tannic acid solution, reacting for 6h in a constant-temperature water bath oscillator at the temperature of 30 ℃, taking out the modified polymer film from the beaker, and repeatedly washing in the deionized water for 10 min.
5) Preparing the hyperbranched polymer graft modified polymer film, adding 2g of TRIS (hydroxymethyl) aminomethane (TRIS) into 1L deionized water, adjusting the pH to 8.5 by using 0.1 mol/L NaOH aqueous solution to obtain TRIS buffer solution, and adding 2g of NH2Adding HbPG and 16g of sodium chloride into 1L TRIS buffer solution, stirring for 5min to obtain uniform hyperbranched polymer solution, adding the tannic acid modified polymer film into a beaker filled with 200m of L hyperbranched polymer solution, slightly stirring at 25 ℃ to react for 12h, taking out the hyperbranched polymer modified polymer film, repeatedly washing in deionized water for 10min, and vacuum drying at 80 ℃ for 8h until the quality of the film is not changed.
Example 7 Experimental example Water contact Angle experiment of modified polymeric film
The water contact angle test of the membrane is a common method for representing the hydrophilic and hydrophobic performance of the membrane, and the smaller the water contact angle is, the better the hydrophilic performance of the membrane is. In the experiment, water contact angles of polymer films, namely polymer films modified by plant polyphenol and hyperbranched polymer modified polymer films with different molecular weights (namely different addition amounts of glycidol) are respectively tested.
Wherein, control group MPVDF: an unmodified polyvinylidene fluoride membrane (PVDF membrane);
control group MTA-PVDF: coating the modified PVDF film with tannic acid prepared only according to the step (4) of example 5;
experimental groups: the modified PVDF membrane prepared in example 5, except that in step (2), the amount of glycidol added was varied, wherein M isHPG1-1-PVDFThe amount of glycidol added was 15M L, MHPG1-2-PVDFThe amount of glycidol added was 30M L MHPG1-3-PVDFThe amount of glycidol added was 45m L.
As can be seen from FIG. 1, the initial water contact angle of the pure PVDF membrane is as high as 93.2 +/-1.32 degrees, strong hydrophobicity is shown, the initial water contact angle is reduced to 71.2 +/-2.78 degrees after the pure PVDF membrane is modified by tannic acid, and the hydrophilicity improvement effect is not obvious. And the introduction of the hyperbranched polymer enables the contact angle to be reduced to 50.1 +/-1.78 degrees and 43.2 +/-1.43 degrees and 38.5 +/-4.32 degrees. The result shows that the hyperbranched polymer modified PVDF membrane has better hydrophilicity, and the water contact angle is gradually reduced and the hydrophilicity of the membrane is gradually improved along with the increase of the molecular weight. The terminal of the hyperbranched polymer with larger molecular weight has more hydroxyl, and the specific single active group enables the hyperbranched polymer to be distributed on the surface of PVDF in a single layer, thereby reducing the mutual embedding between the terminal hydroxyl. The introduction of the hyperbranched polymer enables a hydrated layer to be formed on the surface of the PVDF membrane, and the affinity between the PVDF membrane and water is remarkably enhanced along with the increase of the hydroxyl grafting amount on the surface of the PVDF membrane. The great improvement of the hydrophilic property of the modified PVDF membrane provides a foundation for the application of the modified PVDF membrane, and the purpose of controllable hydrophilic modification is achieved by changing the molecular weight of the hyperbranched polymer, namely the length of the grafted chain.
Example 8 Experimental example static anti-protein adsorption experiment of modified polymeric Membrane
The anti-adsorption capacity of the membrane surface to protein is an important index for measuring the anti-pollution capacity of the membrane. In this example, Bovine Serum Albumin (BSA) was used as a protein sample to examine the anti-protein adsorption capacity of the membrane.
Wherein, control group MPVDF: an unmodified polyvinylidene fluoride membrane (PVDF membrane);
control group MTA-PVDF: coating the modified PVDF film with tannic acid prepared only according to the step (4) of example 5;
experimental groups: the modified PVDF membrane prepared in example 5, except that in step (2), the amount of glycidol added was varied, wherein M isHPG1-1-PVDFThe amount of glycidol added was 15M L, MHPG1-2-PVDFThe amount of glycidol added was 30M L MHPG1-3-PVDFThe amount of glycidol added was 45m L.
As can be seen from FIG. 2, the BSA adsorption amounts of the pure PVDF membranes were 118.1. + -. 6.4. mu.g/cm2. The adsorption capacity of the PVDF membrane subjected to tannic acid coating modification is 100.5 +/-5.1 mu g/cm2, and is slightly smaller than that of a pure PVDF membrane. Although the introduction of tannic acid improves the hydrophilicity of the PVDF membrane, tannic acid is easy to combine with protein and attach to the surface of the membrane, and the permeation efficiency is influenced. Egg with PVDF membrane modified by hyperbranched polymerThe white adsorption capacity is far less than that of a pure PVDF membrane, and the white adsorption capacity is respectively 28.1 +/-4.1 mu g/cm2，25.0±2.9μg/cm2，21.5±2.3μg/cm2. And with the increase of the molecular weight of the hyperbranched polymer, the number of terminal hydroxyl groups in the molecule is gradually increased, the hydrophilicity is improved, and the protein adsorption quantity on the surface of the membrane is gradually reduced. Research shows that the adsorption performance of the membrane surface is closely related to the physicochemical properties of the membrane material. Due to the hydrophobic interaction between the membrane material and the protein, the protein is very easily adsorbed on the surface of the membrane, and the hyperbranched polymer enables the surface of the membrane to form a hydrophilic layer, so that the direct contact between the protein and the surface of the membrane can be effectively avoided, therefore, the surface of the modified membrane has a certain rejection effect on the protein, and the modified membrane shows good pollution resistance.
It should be noted that: the hyperbranched polymer modified polymer membranes prepared in the embodiments 1 to 4 and 6 of the invention have the experimental effects, and the differences between the embodiments and the experimental effects are not large.
Example 9 Experimental example static antibacterial adsorption experiment of modified polymeric Membrane
The microbial adhesion is an important factor influencing the service life of the polymer membrane, and in order to characterize the antibacterial adhesion performance of the PVDF membrane before and after modification, the antibacterial adhesion capacity of the PVDF membrane is evaluated by respectively adopting escherichia coli and staphylococcus aureus with both yin and yang properties in experiments.
Wherein, control group MPVDF: an unmodified polyvinylidene fluoride membrane (PVDF membrane);
control group MTA-PVDF: coating the modified PVDF film with tannic acid prepared only according to the step (4) of example 5;
experimental groups: the modified PVDF membrane prepared in example 5, except that in step (2), the amount of glycidol added was varied, wherein M isHPG1-1-PVDFThe amount of glycidol added was 15M L, MHPG1-2-PVDFThe amount of glycidol added was 30M L MHPG1-3-PVDFThe amount of glycidol added was 45m L.
As shown in FIG. 3, the results showed that the pure PVDF membrane and the tannin-modified PVDF membrane were easily contaminated with bacteria, and the adhesion percentages of the tannin-modified PVDF membrane to the two bacteria were as high as 100.9. + -. 5.4% and 95.3. + -. 5.5%, respectively, when the bacterial adhesion amounts of the pure PVDF membrane were used as the basis. And the adhesion amount of the PVDF membrane modified by the hyperbranched polymer to the two bacteria is less than 16 percent, and when the HPG-3 with the largest molecular weight is used as a modifier, the adhesion amount of the modified membrane to the two bacteria is as low as 8.5 +/-3.1 percent and 10.2 +/-2.3 percent. This also demonstrates that the increased molecular weight of the hyperbranched polymer increases the density of hydroxyl groups on the surface of the modified membrane and increases hydrophilicity. In general, the introduction of the hyperbranched polymer enables a hydration layer to be formed on the surface of the membrane, so that the nonspecific combination of bacteria and the surface of the membrane is effectively avoided, and the anti-pollution performance of the membrane is improved.
It should be noted that: the hyperbranched polymer modified polymer membranes prepared in the embodiments 1 to 4 and 6 of the invention have the experimental effects, and the differences between the embodiments and the experimental effects are not large.
Example 10 dynamic protein contamination resistance analysis of modified polymeric membranes
To further investigate the long-term protein contamination resistance of the membrane, a 3.5h three water-protein-water solution loop filtration experiment was performed.
Wherein, control group MPVDF: an unmodified polyvinylidene fluoride membrane (PVDF membrane).
Experimental groups: the modified PVDF membrane prepared in example 5, except that in step (2), the amount of glycidol added was varied, wherein M isHPG1-1-PVDFThe amount of glycidol added was 15M L, MHPG1-2-PVDFThe amount of glycidol added was 30M L MHPG1-3-PVDFThe amount of glycidol added was 45m L.
Three water-protein-water solution circulating filtration experiments were performed under pressure in a cross-flow filtration mode. And (3) judging the pollution and cleaning performance of the membrane material by calculating the change of the membrane flux and the magnitude of the flux recovery rate. (pure water flux is often used as a basic index for evaluating membrane performance, and the change of flux reflects the degree of pollution of membrane materials to a certain extent.) the specific steps are as follows:
the membrane is cut into proper size, put into a filter element and connected with pure water. Firstly, prepressing for 30min under 0.2MPa, reducing the pressure to 0.1MPa, stabilizing the pressure, testing the quality of pure water passing once every 5min after the flux is stable, and calculating the pure water flux according to the following formula;
wherein V is the volume of the permeate; a is the effective area of the membrane; Δ t is the time required to permeate a volume V of filtrate.
Then, pure water was changed to a Bovine Serum Albumin (BSA) solution of 1 g/L with the pressure maintained at 0.1MPa, and the change in the flux of the protein solution was measured every 5min (test 6 times), and finally, the membrane was taken out, washed with a phosphate buffer solution, and after about 20min, pure water was introduced and the flux of pure water was measured, which was repeated three times, to finally obtain stable pure water fluxes JW0, JW1, JW2, and JW3, and BSA fluxes JB1, JB2, and JB3, respectively, and the pure water fluxes after each washing were designated as Jr1, Jr2, and Jr 3.
The Flux Recovery Ratio (FRR) is calculated as follows:
FIG. 4 shows the flux change between pure PVDF membrane and different molecular weight PVDF membrane in the circular filtration experiment, when pure water is changed to protein solution, the PVDF membranes before and after modification are attenuated to different degrees and the attenuation rates of the fluxes are different, the initial flux of the pure PVDF membrane is the lowest and the attenuation is quicker, which also shows that the pure PVDF membrane is more easily polluted by protein due to the inherent hydrophobic property of the pure PVDF membrane, compared with the pure PVDF membrane, the PVDF membrane maintains higher flux in the whole circular filtration process, and the initial water fluxes respectively reach 249.02L/m2h、317.23L/m2h and 371.14L/m2h, 122.86L/m far higher than that of pure PVDF film2h. After 3.5h of water-protein cycle experiment, the flux recovery rate of the pure PVDF membrane is 41.25%, and the flux recovery rates of the modified PVDF membranes are respectively 90.06%, 88.22% and 88.04%, which shows that the introduction of the hyperbranched polymer leads the PVDF membrane to form hydrophilic coatingThe layer has good protein pollution resistance, and lays a foundation for prolonging the service life of the membrane in the application process.
It should be noted that: the hyperbranched polymer modified polymer membranes prepared in the embodiments 1 to 4 and 6 of the invention have the experimental effects, and the differences between the embodiments and the experimental effects are not large.
Claims (10)
1. A preparation method of a hyperbranched polymer modified polymer film is characterized by comprising the following steps: the method comprises the following steps: (1) synthesis of N, N-dibenzyl-2 amino polyglycidyl ether: adding an initiator N, N-dibenzyl-2 amino-trihydroxymethyl methane into anhydrous benzene or toluene, deoxidizing, adding cesium hydroxide monohydrate into a system, reacting to obtain a solid reactant, adding the solid reactant into diglyme, deoxidizing, dropwise adding glycidol into the system to obtain a high-viscosity product, dissolving the high-viscosity product, replacing by cation exchange resin to obtain a replacement solution, purifying, precipitating and drying the replacement solution to obtain a product N, N-dibenzyl-2 amino polyglycidyl ether;
(2) synthesis of amino-terminal hyperbranched polyglycidyl ether: dissolving N, N-dibenzyl-2 amino polyglycidyl ether into a methanol solution, adding a catalyst, reacting the system in a high-pressure hydrogen environment, and filtering, purifying and drying to obtain a product of amino-terminal hyperbranched polyglycidyl ether;
(3) preparation of plant polyphenol modified polymer film: immersing the polymer film in TRIS buffer solution containing plant polyphenol and metal salt, and obtaining a plant polyphenol modified polymer film after reaction;
(4) preparing a hyperbranched polymer graft modified polymer membrane; and immersing the plant polyphenol modified polymer film into a TRIS buffer solution containing amino-terminal hyperbranched polyglycidyl ether and NaCl for reaction, washing and drying to obtain the hyperbranched polymer grafted modified polymer film.
2. The method of claim 1, wherein the hyperbranched polymer-modified polymer film comprises: in the step (1), the initiator N, N-dibenzyl-2 amino-trimethylolmethane is synthesized by the following steps: adding trihydroxymethyl aminomethane (TRIS) into a polar solvent, dissolving and mixing, adjusting the pH value of the system to 7-9, continuously stirring, adding benzyl bromide into the system, and performing reflux reaction, reduced pressure distillation, organic solvent extraction, washing, water removal and recrystallization to obtain the initiator N, N-dibenzyl-2 amino-trihydroxymethyl methane.
3. The method of claim 1, wherein the hyperbranched polymer-modified polymer film comprises: the synthesis of the initiator N, N-dibenzyl-2-amino-trimethylolmethane in the step (1) comprises the following steps: adding TRIS into a polar solvent, and stirring for 1-2h at 40-60 ℃ to obtain a mixed solution A, wherein the ratio of the polar solvent to the TRIS is 100-: 3-8 g; adding strong base and weak acid salt into the mixed solution A, adjusting the pH value of the system to 7-9, and continuously stirring for 1-2h to obtain mixed solution B; adding benzyl bromide into the mixed solution B, carrying out reflux reaction for 18-30h at the temperature of 120-160 ℃, cooling the reaction system to room temperature, filtering, and removing strong base and weak acid salt solids to obtain a mixed solution C, wherein the mass ratio of the benzyl bromide to the TRIS is 14-20: 3-8; placing the mixed solution C in a reduced pressure distillation device, and removing the polar solvent in a vacuum oven at the temperature of 80-90 ℃ in an auxiliary manner to obtain a crude product of the N, N-dibenzyl-2-amino-trimethylolpropane; dissolving the crude product of the N, N-dibenzyl-2-amino-trimethylolpropane methane by using chloroform, extracting to obtain a mixed solution D, repeatedly washing the mixed solution D by using deionized water and a saturated sodium bicarbonate solution for 2 to 4 times, adding a water removing agent A into the mixed solution, stirring the mixed solution for 3 to 6 hours, removing residual water in the solution, filtering the mixed solution, removing a chloroform solvent in a system by rotary evaporation, adding ethyl acetate, and recrystallizing the mixed solution; vacuum drying at 60-80 deg.C to obtain white solid initiator N, N-dibenzyl-2 amino-trihydroxymethyl methane; the addition proportions of the TRIS, the chloroform, the water removing agent A and the ethyl acetate are as follows: 3-8 g: 200-400 ml: 1-3 g: 20-30 ml.
4. The method of claim 1, wherein the hyperbranched polymer-modified polymer film comprises: the synthesis of the N, N-dibenzyl-2 amino polyglycidyl ether in the step (1) comprises the following steps: adding an initiator N, N-dibenzyl-2 amino-trihydroxymethyl methane into anhydrous benzene or toluene, introducing nitrogen for 10-20 minutes to remove oxygen to obtain a suspension A, wherein the ratio of the initiator to the anhydrous benzene or toluene is 0.5-5 g: 1-20 ml; adding cesium hydroxide monohydrate into the suspension A, and reacting for 1-2 hours at 50-70 ℃ with stirring, wherein the mass ratio of the cesium hydroxide monohydrate to the initiator is 0.2-2: 0.5 to 5; then, carrying out vacuum filtration for 1-2h at 70-80 ℃, and removing an anhydrous benzene or toluene solvent to obtain a mixture B; adding diglyme into the mixture B, heating the system to 90-100 ℃, and continuously introducing nitrogen for 10-30 minutes, wherein the proportion of the diglyme to the initiator is 30-50 ml: 1g of a compound; dropwise adding glycidol into a reaction system protected by nitrogen, wherein the dropwise adding time is not less than 8h, continuously stirring for reacting for 8-12h to obtain a high-viscosity product, wherein the ratio of the initiator to the glycidol is 1 g: 10ml to 80 ml; dissolving the product in methanol, stirring by using cation exchange resin, filtering to remove the cation exchange resin, concentrating, pouring into cold diethyl ether for precipitation for several times, and vacuumizing for 1-3h at 70-80 ℃ until the quality does not change any more, thereby obtaining the final reaction product N, N-dibenzyl-2 amino polyglycidyl ether.
5. The method of claim 2, wherein the hyperbranched polymer-modified polymer film comprises: the polar solvent in the step (1) is subjected to water removal treatment before the reaction with TRIS, and the specific method comprises the following steps: adding a water removing agent B into the polar solvent, mixing, stirring for 6-12h at 60-80 ℃, and distilling under reduced pressure to obtain an anhydrous polar solvent; the proportion of the water remover B to the polar solvent is 1-3 g: 100-; the glycidol and the diglyme in the step (1) need to be subjected to water removal treatment, and the specific method comprises the following steps: adding a water removing agent B into the glycidol and the diglyme respectively, stirring for 6-12h, and carrying out reduced pressure distillation at the temperature of 60-80 ℃ to obtain anhydrous glycidol and anhydrous diglyme; the proportion of the water remover B to the polar solvent is 1-3 g: 100-.
6. The method of claim 1, wherein the hyperbranched polymer-modified polymer film comprises: the synthesis of the amino-terminal hyperbranched polyglycidyl ether of the step (2) comprises the following steps: adding N, N-dibenzyl-2 amino polyglycidyl ether and palladium carbon with the concentration of 10% into a methanol solution according to the mass ratio of 1-2:0.15-0.3, carrying out reduction reaction for 48-72h by using hydrogen under the pressure of 50-80bar, filtering solid residues, precipitating by using cold ethyl ether, and carrying out vacuum drying for 6-8h at the temperature of 60-80 ℃ until the mass is not changed to obtain a synthetic product, namely the amino-terminal hyperbranched polyglycidyl ether, wherein the ratio of the N, N-dibenzyl-2 amino polyglycidyl ether to the methanol is 1-2 g: 100-; the adding proportion of the cold ethyl ether to the N, N-dibenzyl-2 amino polyglycidyl ether is as follows: 100-200 ml: 1-2 g.
7. The preparation method of the hyperbranched polymer modified polymer film as claimed in claim 1, wherein the preparation of the plant polyphenol modified polymer film in the step (3) comprises the steps of (a) preparing a plant polyphenol mixed solution, namely adding TRIS and metal salt into deionized water for mixing, adjusting the pH to 7-10 to obtain a TRIS buffer solution, adding plant polyphenol into the TRIS buffer solution for mixing to obtain a plant polyphenol mixed solution, wherein the adding proportion of the plant polyphenol to the plant polyphenol mixed solution is that TRIS, the plant polyphenol to the metal salt to water is 1-5.5g, 1-6g, 1-55g, 1000m L;
(b) immersing the polymer film in the plant polyphenol mixed solution, and reacting in a constant-temperature water bath oscillator for 3-24h at the temperature of 20-30 ℃; and taking out the wet film, and repeatedly washing the wet film in deionized water for 10-20 minutes to obtain the plant polyphenol modified polymer film.
8. The preparation method of the hyperbranched polymer modified polymer film according to claim 1, wherein the preparation method of the hyperbranched polymer modified polymer film in the step (4) comprises the steps of (a) preparing a hyperbranched polymer mixed solution, namely adding TRIS and a metal salt into deionized water for mixing, adjusting the pH value to 7-10 to obtain a TRIS buffer solution, adding amino-terminal hyperbranched polyglycidyl ether into the TRIS buffer solution, and mixing and stirring to obtain a hyperbranched polymer mixed solution, wherein the hyperbranched polymer mixed solution comprises the following components in proportion of TRIS, metal salt, amino-terminal hyperbranched polyglycidyl ether, water and the like, and the proportion is 0.5-5g, 5-50g, 0.1-10g, and 1000m L;
(b) preparation of hyperbranched polymer graft modified polymer membrane: immersing the plant polyphenol modified polymer film into the hyperbranched polymer mixed solution, and slightly stirring the mixture at the temperature of between 20 and 30 ℃ to react for 6 to 12 hours; taking out the wet film, and repeatedly rinsing the wet film in deionized water for 5-10 minutes; vacuum drying for 6-10h at 60-80 ℃ until the quality of the membrane is not changed, and obtaining the hyperbranched polymer grafted and modified polymer membrane.
9. The hyperbranched polymer-modified polymer film obtained by the production method according to any one of claims 1 to 8.
10. Use of a hyperbranched polymer-modified polymer membrane according to claim 9.
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Application publication date: 20180323 Assignee: Oushangyuan Intelligent Equipment Co.,Ltd. Assignor: TIANJIN POLYTECHNIC University Contract record no.: X2024980001938 Denomination of invention: A hyperbranched polymer modified polymer film and its preparation method and application Granted publication date: 20200728 License type: Common License Record date: 20240206 |