CN114044853A - Biomass-based EC-g-PSSA graft copolymer and preparation method and application thereof - Google Patents
Biomass-based EC-g-PSSA graft copolymer and preparation method and application thereof Download PDFInfo
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- CN114044853A CN114044853A CN202111348816.XA CN202111348816A CN114044853A CN 114044853 A CN114044853 A CN 114044853A CN 202111348816 A CN202111348816 A CN 202111348816A CN 114044853 A CN114044853 A CN 114044853A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
- C08F8/36—Sulfonation; Sulfation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
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Abstract
The invention relates to the technical field of high polymer materials, and particularly provides a biomass-based EC-g-PSSA graft copolymer, and a preparation method and application thereof, wherein the biomass-based EC-g-PSSA graft copolymer has the following structure:
wherein m is 2-800, n is 2-900, R is CH2CH3Or H. The invention synthesizes the biomass-based EC-g-PSSA graft copolymer by successively carrying out acylation reaction, ATRP reaction and sulfonation reaction, and obtains the graft copolymer with a certain thickness and a multi-stage ordered honeycomb micropore pattern thin layer by dripping to form a filmAnd (3) a membrane. The membrane has potential application value in the fields of fuel cell membranes, microfiltration separation, high-efficiency catalytic material preparation, microelectronics and the like.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a biomass-based EC-g-PSSA graft copolymer, and a preparation method and application thereof.
Background
The fuel cell membrane is a nano-channel material with ion transmission capability, and comprises an ion transmission functional layer and a mechanical support layer. The ion transmission functional layer can be prepared from charged or hydrolyzed ionized homopolymer, block polymer, graft polymer, random copolymer, alternating copolymer and the like. Early fuel cell membranes contained no solvent component and relied only on ions in the polar polymer network for electrical conduction. The ionizable grafting copolymer material which appears in recent years not only has high-efficiency conductivity, but also can form a rich ion channel structure with 5-100nm of highly ordered and controllable size, such as a spherical, columnar, bicontinuous, layered structure and the like through self-assembly. The Proton Exchange Membrane (PEM) material with strong proton transmission capability and mechanical property can be prepared by simultaneously combining an additive and a high-strength mechanical support body, conforms to the development trend of controllable proton transmission capability, light weight, safety, high efficiency and environmental protection of a chemical power supply, and becomes a hotspot for research and development of fuel cells at present.
However, a key issue in the design of graft copolymer-based PEM materials is addressing the balance between raw material source, environmental performance, and proton transport capability of the graft copolymer. Proton transport in such PEM materials is accomplished primarily within the graft copolymer region by peristaltic movement of the graft copolymer polymer segment across the energy barrier. Graft copolymer materials are generally expensive, have poor proton transport capabilities, and are not environmentally friendly. In 2021, the Martinelli group reported a high performance biomass-based cellulose and ionic liquid formed self-supporting proton exchange membrane material, which indicated that in addition to being inherently sustainable, biopolymers possess high thermo-mechanical stability and are widely used in fuel cell membranes. In addition, the Ulbricht topic group reviews the development prospect of advanced novel membrane materials on Journal of Membrane Science, and the Ubricht topic group indicates that the biomass-based graft copolymer fuel cell membrane becomes a research hotspot of people, namely, the purpose of simultaneously realizing the application of biomass-based environment-friendly materials and improving the ion transmission capability by modifying a modified or graft copolymer method is realized, so that the defects that the traditional fuel cell membrane has expensive raw materials, is not environment-friendly, has low proton transmission efficiency and cannot be put into practical use are overcome. However, existing biomass-based graft copolymer membranes, such as ethyl cellulose grafted polystyrene (EC-g-PS) ordered microporous membranes reported in liu wenyong theme group 2012, have only a small number of unreacted hydroxyl groups available for proton transport and low levels of ionizable anions; and the membrane pore structure is single, and the mass transfer resistance of a pore-free framework is large, so that efficient proton transmission cannot be realized.
Disclosure of Invention
The invention aims to provide a biomass-based EC-g-PSSA graft copolymer, and a preparation method and application thereof. In the project, a biomass-based material, namely cellulose derivative Ethyl Cellulose (EC) is selected as a main body part of a graft copolymer, and micromolecular acylation reaction and Atom Transfer Radical Polymerization (ATRP) reaction are adopted to realize the synthesis of the biomass-based EC-g-PS; secondly, sulfonating the PS chain segment part into polystyrene sulfonic acid (PSSA) to prepare an environment-friendly EC-g-PSSA raw material; and finally, preparing the multistage ordered microporous film material with strong proton transmission capacity by adopting a breathing pattern array self-assembly method. The EC-g-PSSA proton channel PEM with ordered height, adjustable appearance and adjustable size has a multistage ordered microporous structure, so that the EC-g-PSSA proton channel PEM has stronger proton transmission capability and stronger practicability in the field of fuel cells.
In order to achieve the above object, one of the technical solutions of the present invention is: a biomass-based EC-g-PSSA graft copolymer having the following structure:
wherein m is 2-800, n is 2-900, R is CH2CH3Or H.
The value of m in the invention is preferably 10-500, or 30-300, or 50-150, and the value of n is preferably 2-600, or 10-400, or 20-200.
In a preferred embodiment, m is 80, n is 21; or m-80, n-44; or m is 80, n is 60; or m is 110, n is 20; or m is 110, n is 40; or m is 110, n is 60; or m is 140, n is 20; or m is 140, n is 40; or m is 140 and n is 65.
In another preferred embodiment, m is 140 and n is 65.
Preferably, the biomass-based EC-g-PSSA graft copolymer has an EC repeating unit number of 2-800, preferably 50-150, and a PSSA volume content fPSSAIs 0.001-0.800, preferably 0.003-0.700.
The second technical scheme of the invention is as follows: a preparation method of a biomass-based EC-g-PSSA graft copolymer specifically comprises the following steps:
(1) using an acylation reagent and ethyl cellulose containing hydroxyl (hereinafter abbreviated as EC) as raw materials, adding an acid-binding agent, and carrying out micromolecule acylation reaction to obtain an EC macromolecular initiator;
(2) the EC macroinitiator, styrene, ligand and cuprous chloride are used as raw materials, and an atom transfer radical polymerization reaction is carried out to obtain a biomass-based EC-g-PS graft copolymer;
(3) and carrying out sulfonation reaction on the EC-g-PS graft copolymer and a sulfonation reagent serving as raw materials to obtain the EC-g-PSSA graft copolymer.
Further, in the step (1), the hydroxyl-containing EC has an ethyl substitution degree of 2.2 to 2.5 and a structural formula of:
preferably, in the step (1), the acylating reagent is selected from one of 2-bromoisobutyryl bromide, 2-chloroisobutyryl chloride, 2-chloroisobutyryl bromide, 2-bromoisobutyryl chloride and the like and hydroxyl-containing EC as raw materials, and an EC macroinitiator is obtained through a small molecule acylation reaction, preferably 2-bromoisobutyryl bromide; the acid-binding agent is one or a mixture of more of anhydrous triethylamine, anhydrous pyridine, anhydrous N, N-diisopropylethylamine and anhydrous 4-dimethylaminopyridine, and is preferably anhydrous triethylamine.
Preferably, in step (2), the ligand is selected from Pentamethyldiethylenetriamine (PMDETA), pentamethyldipropylenetriamine, tris (2-dimethylaminoethyl) amine (Me)6TREN), preferably PMDETA.
Preferably, in the step (3), the sulfonating agent is selected from one of more than 98 wt% concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, sulfur trioxide, acetyl sulfonate and the like, and is preferably more than 98 wt% concentrated sulfuric acid.
Preferably, in step (1), the solvent is selected from one or more of anhydrous tetrahydrofuran, anhydrous toluene, anhydrous dichloromethane and anhydrous chloroform.
According to the invention, anhydrous tetrahydrofuran is preferably selected as a solvent for synthesizing the EC macromolecular initiator, and the solvent can well dissolve all raw materials at room temperature, so that the reaction between hydroxyl on an EC macromolecular ring and acyl bromide is more thorough. Meanwhile, the acid-binding agent can keep high activity in the solvent, well adsorb hydrobromic acid obtained by the reaction, and is beneficial to the reaction to better proceed in the forward direction.
Preferably, step (2) is carried out in a solvent selected from one or a mixture of two of chlorobenzene and N, N-Dimethylformamide (DMF); in order to ensure the smooth reaction, the invention preferably selects one or a mixture of two of anhydrous chlorobenzene and anhydrous DMF, and more preferably selects anhydrous chlorobenzene; when 2 kinds of mixtures are used as the reaction solvent, the ratio of the amounts of the respective solvents is not particularly limited.
According to the invention, anhydrous chlorobenzene is preferably selected as a solvent for synthesizing the EC-g-PS graft copolymer, and the solvent can well dissolve the EC macroinitiator, the ligand, the styrene monomer and the like at room temperature, so that ATRP is polymerized into a homogeneous system, and the reaction is carried out more thoroughly. Meanwhile, the initiator can keep high activity in the solvent, and the EC-g-PS graft copolymer obtained by initiating monomer polymerization has small Polydispersity (PDI), thereby being beneficial to forming narrow-distribution EC-g-PSSA after sulfonation.
Preferably, step (3) is carried out in a solvent selected from a mixture of one or more of 1, 2-dichloroethane, cyclohexane, chloroform. Also in order to ensure the smooth progress of the reaction, the invention preferably uses an anhydrous solvent as the reaction solvent, i.e. preferably one or more of anhydrous 1, 2-dichloroethane, anhydrous cyclohexane and anhydrous chloroform, more preferably anhydrous 1, 2-dichloroethane; when 2 or more than 2 kinds of mixed solvents are selected, the amount of each solvent is not particularly limited.
According to the invention, anhydrous 1, 2-dichloroethane is preferably selected as a solvent for synthesizing the EC-g-PSSA graft copolymer, and the solvent can well dissolve the EC-g-PS graft copolymer, a sulfonation reagent and the like at room temperature, so that the sulfonation reaction is carried out more completely. Meanwhile, the sulfonation reagent can keep high activity in the solvent, which is beneficial to obtaining EC-g-PSSA graft copolymer with higher sulfonation rate and is more beneficial to forming multi-stage ordered uniform microporous membrane.
Preferably, in step (1), the hydroxyl group-containing EC: acylating reagent: acid-binding agent 1: (10-4000): (10-4000).
Preferably, in step (2), the EC macroinitiator: ligand: cuprous chloride: styrene ═ 1: (1-5): (1-5): (1-600).
Preferably, in step (3), the EC-g-PS graft copolymer: sulfonation reagent ═ 1: (1-1500).
Preferably, the reaction time of the step (1) is 16-48h, and more preferably 24 h; the reaction time of the step (2) is 10-24h, and the preferable time is 16 h; the reaction time of step (3) is 2 to 8 hours, and more preferably 3 hours.
As a better preparation method of the biomass-based EC-g-PSSA graft copolymer, raw materials used in the step (1) are hydroxyl-containing EC, 2-bromoisobutyryl bromide and anhydrous triethylamine, raw materials used in the step (2) are EC macroinitiator, PMDETA, styrene and cuprous chloride, raw materials used in the step (3) are concentrated sulfuric acid, and the rest of acylation reaction, ATPR operation and sulfonation reaction are the same as above.
More preferably, the preparation method of the invention comprises the following steps:
(1) and (3) synthesizing an EC macroinitiator: adding EC containing hydroxyl and a solvent into a single-neck flask, uniformly stirring, and then putting into an ice bath at 0 ℃ for stirring for 30 min; sucking a certain amount of acid binding agent by using an injector and quickly adding the acid binding agent into the system; slowly dripping 2-bromoisobutyryl bromide into the system by using a clean constant-pressure dropping funnel; after the dripping is finished, taking the constant-pressure dropping funnel away, plugging a cork, and continuously reacting at room temperature for 16-48h to obtain a crude product;
(2) synthesis of EC-g-PS graft copolymer: adding an EC macroinitiator, a ligand, styrene (St) and a solvent into a reaction vessel, freezing the reactor by liquid nitrogen, and adding cuprous chloride (CuCl); vacuumizing for 3-7min under the frozen state of liquid nitrogen, thawing under the condition of introducing nitrogen, stirring for 3-7min, repeating the vacuumizing and thawing operations for 2-5 times, and finally reacting for 10-24h at 90-120 ℃ under the vacuum state to obtain a crude product;
(3) synthesis of EC-g-PSSA graft copolymer: adding EC-g-PS and a solvent into a three-neck flask, uniformly stirring, and then putting into a water bath at 40 ℃ for stirring for 30 min; slowly dripping concentrated sulfuric acid into the system by using a clean constant-pressure dropping funnel, and reacting for 2-8h at 40 ℃ to obtain a crude product;
in order to ensure the quality of the product, the preparation method further comprises the step of carrying out post-treatment on the crude product (reaction liquid) obtained in the steps (1), (2) and (3):
work-up operations on the reaction of (1), namely: slowly dropping the reaction system into a large amount of deionized water, repeatedly precipitating, washing and filtering for more than three times to obtain a crude product;
the work-up operations for the reaction of (2), namely: quenching the reaction by using liquid nitrogen, removing copper salt, spin-drying the reaction solution, precipitating by using ether and alcohol solvents, and washing the product;
wherein the ether solvent is petroleum ether, diethyl ether or a mixture of the petroleum ether and the diethyl ether; preferably, cold ether solvent is adopted to precipitate and wash the product; the alcohol solvent is methanol, ethanol, propanol, etc.;
preferably, the copper salt is removed using a neutral alumina column. Further preferably, the reaction product is dissolved with dichloromethane before removing the copper salt;
the work-up operation for the reaction of (3), namely: washing the product with deionized water for more than three times, washing the product with absolute alcohol to be neutral, and then putting the product into an oven for low-temperature drying;
wherein the absolute alcohol solvent is methanol, ethanol or a mixture of the methanol and the ethanol; preferably, the product is washed by absolute ethyl alcohol solvent;
the invention also provides a biomass-based EC-g-PSSA graft copolymer prepared by any one of the methods.
The biomass-based EC-g-PSSA graft copolymer synthesized by the method is polymerized by one-step acylation reaction, one-step ATRP reaction and one-step sulfonation reaction in sequence, and further the effective synthesis of the biomass-based EC-g-PSSA graft copolymer is realized.
The third technical scheme of the invention is as follows: a biomass-based EC-g-PSSA graft copolymer multistage ordered honeycomb micropore pattern film is prepared from any biomass-based EC-g-PSSA graft copolymer or the biomass-based EC-g-PSSA graft copolymer prepared by any method.
Preferably, the biomass-based EC-g-PSSA graft copolymer multistage ordered honeycomb micropore pattern film is a pattern structure with macropores in ordered hexagonal arrangement and secondary micropores in random arrangement on a macroporous skeleton.
Preferably, the pore diameter of the macropores of the multilevel ordered honeycomb micropore pattern film is hundreds of nanometers to hundreds of micrometers, and the pore diameter of the secondary micropores is several nanometers to hundreds of nanometers.
The biomass-based EC-g-PSSA graft copolymer multistage ordered honeycomb micropore pattern film has a pattern structure that macropores are arranged in an ordered hexagon and secondary micropores are randomly arranged on a macropore framework, and the diameter of each macropore or the distance between the macropores can be adjusted; for example, the volume fraction f of PSSAPSSAThe EC-g-PSSA graft copolymer with different EC repeating unit values in the range of 0.001-0.800 can obtain the highly ordered hexagonal microporous film with the pore diameter of hundreds of nanometers to several micrometers or the highly ordered hexagonal microporous film with the pore spacing of hundreds of nanometers to several micrometers.
The fourth technical scheme of the invention is as follows: a preparation method of a biomass-based EC-g-PSSA graft copolymer multistage ordered honeycomb micropore pattern film specifically comprises the following steps: and (3) dropwise adding the prepared biomass-based EC-g-PSSA graft copolymer solution on a support to form a film with a certain thickness, and carrying out self-assembly on the film by using a breathing pattern array.
The biomass-based EC-g-PSSA graft copolymer is any one of the biomass-based EC-g-PSSA graft copolymers or is prepared by any one of the methods.
In order to ensure the effect of the dropping film, the support body is cleaned before the dropping film is carried out, the cleaning can adopt the conventional technical means in the field, and the preferred cleaning operation of the invention is as follows: the support body is respectively placed in acetone and ethanol for ultrasonic cleaning, and then nitrogen is used for blowing and drying.
Preferably, the support is one of a glass sheet, a silicon wafer, polyethylene terephthalate (PET), and an aluminum foil.
Preferably, the biomass-based EC-g-PSSA graft copolymer solution with the concentration of 2mg/mL-10mg/mL is prepared by using one or more of carbon disulfide, chloroform, dichloromethane and tetrahydrofuran as a solvent.
Preferably, the self-assembly conditions are: naturally volatilizing the solvent for 1-24h at the humidity of 20-90%; more preferably, the solvent is naturally volatilized for 16-24h under the humidity of 50% -90%.
The thickness of the self-assembled film of the biomass-based EC-g-PSSA graft copolymer multistage ordered honeycomb micropore pattern film prepared by the invention can reach 1-5 mu m, and the cross section of the self-assembled film can be clearly seen to be in a highly ordered honeycomb micropore structure.
The fifth technical scheme of the invention is as follows: the biomass-based EC-g-PSSA graft copolymer multistage ordered honeycomb microporous pattern film or the biomass-based EC-g-PSSA graft copolymer multistage ordered honeycomb microporous pattern film prepared by the method is applied to the fields of fuel cell diaphragms, microelectronics, microfiltration separation and the like; preferably in fuel cell membranes.
In the biomass-based graft copolymer, one graft section is a biomass-based cellulose derivative EC ring structure, and the biomass-based graft copolymer has the characteristics of environmental friendliness, low raw material cost, stable skeleton structure and strong rigidity; the other graft segment is polystyrene sulfonic acid (PSSA) which has the properties of strong hydrophilicity, high ion transmission capability, cross-linking and the like; the biomass-based EC-g-PSSA graft copolymer has larger mutual Haggins parameter value between two graft chain segments, and contains a stable and phase-separated annular EC chain segment and a PSSA chain segment with strong hydrophilicity and strong ion transmission capability, so that the preparation of the multistage ordered microporous film with high porosity, stable skeleton structure and high proton transmission efficiency is easily realized, and a potential copolymer material is provided for the preparation of fuel cell diaphragm materials, microelectronic template materials and microfiltration separation film materials.
The term "EC-g-PSSA", "EC-g-PSSA graft copolymer" and "biomass-based EC-g-PSSA graft copolymer" as used herein are intended to have the same meaning.
The raw materials or reagents involved in the present invention are commercially available.
On the basis of the common knowledge in the field, the above-mentioned preferred conditions can be combined with each other to obtain the preferred embodiments of the present invention.
Drawings
FIG. 1 is EC80Synthesized EC80Of macroinitiators, EC-g-PS graft copolymers and PS homopolymers1HNMR spectrogram comprising EC from top to bottom80、EC80Macroinitiators (EC)80 Macroinitiator)、EC80-g-PS21、EC80-g-PS44、EC140-g-PS65And PS200Of homopolymers1HNMR spectrogram;
FIG. 2 is a synthesized EC80-g-PSSA21、EC80-g-PSSA44And EC140-g-PSSA65Process for preparing graft copolymers1HNMR spectrogram;
FIG. 3 is a synthesized EC80Macroinitiator, EC80-g-PS44、EC80-g-PSSA21、EC80-g-PSSA44And EC140-g-PSSA65FTIR spectra of;
FIG. 4 is the EC prepared in example 480-g-PSSA44SEM image of the upper surface of the cellular microporous membrane;
FIG. 5 is the EC prepared in example 580-g-PSSA21SEM image of the upper surface of the cellular microporous membrane;
FIG. 6 is the EC prepared in example 6140-g-PSSA65SEM image of the upper surface of the cellular microporous membrane;
FIG. 7 is a multilevel ordered EC of about 1 μm thickness prepared in example 780-g-PSSA44A section SEM image of the cellular microporous film;
FIG. 8 is a multilevel ordered EC of about 5 μm thickness prepared in example 880-g-PSSA44Sectional SEM image of cellular microporous membrane.
Detailed Description
The following examples are presented to illustrate the present invention, but are not intended to limit the scope of the invention as claimed, and the operations involved in the following examples are conventional in the art unless otherwise specified.
Example 1
Biomass based EC80-g-PSSA44A process for preparing a graft copolymer comprising the steps of:
1)EC80and (3) synthesis of a macroinitiator:
into a 100mL round bottom flask was added 5.0g of hydroxyl group-containing EC80Powder (from Aladdin)And the cargo number: e110671-100g), then 50mL of Tetrahydrofuran (THF) is measured by a measuring cylinder and poured into the flask; placing the flask in an ice bath, and electromagnetically stirring for 30min to fully dissolve EC to form a transparent solution; then using an injector to suck 8.8mL of triethylamine, quickly adding the triethylamine into the system, and continuously stirring for 10min to uniformly mix the triethylamine and the triethylamine; simultaneously, sucking 14.0mL of 2-bromoisobutyryl bromide by using a syringe, diluting the solution by using 10mL of THF, adding the solution into a 25mL constant pressure drop funnel, screwing a polytetrafluoroethylene plug to control the flow rate of the solution, and dropwise adding the solution into a reaction system; after the addition was complete, the isopiestic dropping funnel was removed, the cork was stoppered, the ice-water bath was removed and the system allowed to continue to react at room temperature for 24 h. In which the EC contains hydroxyl80Powder: triethylamine: 2-bromo isobutyryl bromide ═ 1: 215: 385 (molar ratio).
After the reaction time is reached, slowly dropping the reaction system into a large amount of deionized water, repeatedly precipitating, washing and filtering for three times, and drying to obtain white EC80A macroinitiator solid. It is composed of1The H NMR is shown in FIG. 1, and the FTIR is shown in FIG. 3.
2)EC80-g-PS44Synthesis of graft copolymer:
to a clean Schlenk bottle was added 0.5g of EC in sequence80Macroinitiator and 0.2g St monomer, and 6mL of dewatered chlorobenzene was pipetted with a clean rubber-tipped pipette and mixed well. Then, 12. mu.L of ligand PMDETA was pipetted into the reaction flask and mixed well. Then, the Schlenk bottle was frozen in liquid nitrogen for 5min, and 5.7mg of cuprous chloride (CuCl) catalyst was added under nitrogen atmosphere, and the top of the bottle was sealed with a rubber stopper. Wherein the feeding molar ratio is EC80Macroinitiator: st: ligand: 1, CuCl: 60: 2: 2. then vacuumizing for 5min under the condition of freezing by liquid nitrogen, unfreezing and stirring for 5min under the condition of introducing nitrogen, and circulating for 3 times. The high vacuum shut-off valve of the Schlenk bottle was then tightened with a vacuum applied by freezing, thawed and placed in a 110 ℃ oil bath and stirred for 16 hours.
After 16h of polymerization the reaction flask was taken out of the oil bath and quenched rapidly with liquid nitrogen, the rubber stopper was opened and the resulting product system was dissolved in dichloromethane and made neutralThe alumina column removes the copper salt, the filtrate is pipetted and settled three times in cold petroleum ether stirred at high speed to remove unreacted monomers and oligomers. And then, carrying out suction filtration on the settled suspension by using a sand core funnel, dissolving the solid obtained by suction filtration by using a small amount of dichloromethane, settling twice in methanol stirred at a high speed, and placing the light yellow solid obtained by suction filtration in a vacuum oven at 20 ℃ for drying for 16 hours. Finally, a pure dry white powder, 0.6g EC, is obtained80-g-PS44Graft copolymer of1The HNMR is shown in FIG. 1, and the FTIR is shown in FIG. 3.
3)EC80-g-PSSA44Synthesis of graft copolymer:
10mL of 1, 2-dichloroethane was added to a three-necked flask, and 0.2g of EC was weighed80-g-PS44The graft copolymer is dispersed in 1, 2-dichloroethane, heated to 40 ℃ in water bath and stirred for 30min to completely dissolve the copolymer, 0.7mL of 98 wt% concentrated sulfuric acid is put in a constant pressure dropping funnel, the 98 wt% concentrated sulfuric acid is slowly dropped into a three-neck flask, and the constant temperature reaction is carried out for 3 hours at 40 ℃. Wherein, EC80-g-PS44Graft copolymer: 98 wt% concentrated sulfuric acid 1: 1500 (molar ratio). Washing the reaction product with deionized water for three times, repeatedly washing with anhydrous ethanol to neutrality, and drying in oven at low temperature to obtain 0.15g gray sulfonated product EC80-g-PSSA44Which is1The H NMR is shown in FIG. 2, and the FTIR is shown in FIG. 3.
Example 2
EC80-g-PSSA21The graft copolymer was prepared as in example 1, except that:
in step 2), EC80Macroinitiator: st: ligand: catalyst 1: 40: 2: 2 (molar ratio). The dosage of each substance is respectively as follows: EC (EC)800.5g of macroinitiator, 12 mu L of ligand, 5.6mg of CuCl, 0.12g of St and 6.0mL of anhydrous chlorobenzene as reaction solvent. Finally, the EC with the number of PS chain segments of 21 is obtained80-g-PS210.5g of a graft copolymer1FIG. 1 shows H NMR;
in step 3), with EC80-g-PS21As raw material, chloroform isSolvent, chlorosulfonic acid is sulfonation reagent. EC (EC)80-g-PS21Graft copolymer: chlorosulfonic acid 1: 1200 (molar ratio), the dosage of each substance is respectively as follows: EC (EC)80-g-PS210.2g of raw material and 0.82mL of chlorosulfonic acid; the reaction solvent was chloroform (4 mL). To obtain a product EC80-g-PSSA21Is/are as follows1The H NMR is shown in FIG. 2, and the FTIR is shown in FIG. 3.
Example 3
EC140-g-PSSA65The graft copolymer was prepared as in example 1, except that:
in step 1), with an EC having a hydroxyl group140Powder (from Aladdin, product number: E110673-100g) as raw material, pyridine as acid-binding agent, 2-chloroisobutyryl chloride as acylation agent, and anhydrous dichloromethane as solvent. EC containing hydroxyl group140Powder: pyridine: 2-chloroisobutyryl chloride ═ 1: 420: 420 (molar ratio). The dosage of each substance is respectively as follows: EC with hydroxyl group1405.0g of powder, 5.7mL of pyridine, 8.3mL of 2-chloroisobutyryl chloride, and 50mL of anhydrous dichloromethane as a reaction solvent. Finally obtaining EC1407.0g of macroinitiator;
in step 2), EC140Macroinitiator: st: ligand: catalyst 1: 80: 3: 3 (molar ratio). The dosage of each substance is respectively as follows: EC (EC)1400.5g of macroinitiator, 11 mu L of ligand, 5.0mg of CuCl, 0.15g of St and 6.0mL of reaction solvent chlorobenzene. Finally, the EC with the PS chain segment number of 65 is obtained140-g-PS650.48g of a graft copolymer1FIG. 1 shows H NMR;
in step 3), with EC140-g-PS65Is used as raw material, 1, 2-dichloroethane as solvent and 98 wt% concentrated sulfuric acid as sulfonating agent. EC (EC)140-g-PS65Graft copolymer: 98 wt% concentrated sulfuric acid 1: 1000 (molar ratio), the dosage of each substance is respectively as follows: EC (EC)140-g-PS650.2g of raw material, and 0.30mL of 98 wt% concentrated sulfuric acid; 6mL of 1, 2-dichloroethane as a reaction solvent. To obtain a product EC140-g-PSSA65Is/are as follows1The HNMR is shown in FIG. 2, and the FTIR is shown in FIG. 3.
Example 4
This embodiment providesMulti-stage ordered honeycomb EC80-g-PSSA44The preparation method of the graft copolymer microporous membrane comprises the following steps:
(1) compounding of EC80-g-PSSA44Copolymer solution:
taking 0.001g to 0.005g of EC from example 180-g-PSSA44And dissolved in 1mL of chloroform and stirred at room temperature for 2 hours to obtain a graft copolymer/CHCl concentration of 1 to 5mg/mL3And (3) solution.
(2) Treating a silicon wafer and dripping a film:
and (3) placing a 2 cm-2 cm monocrystalline silicon wafer in acetone for ultrasonic cleaning for 30min, and then placing in ethanol for ultrasonic cleaning for 30 min. Taking out the silicon wafer, and blowing the solvent on the surface of the silicon wafer by using nitrogen for standby. 2mg/mL of graft copolymer/CHCl was pipetted using a 1mL pipette30.5mL of the solution was dropped onto a clean silicon wafer, and the solvent was naturally volatilized at a humidity of 50% for 24 hours to form a film having a thickness of 1 μm.
The upper surface of the honeycomb-shaped film is subjected to scanning electron microscope picture, as shown in figure 4, macropores in the film are arranged in a hexagonal mode with the diameter of 1-5 mu m, and micropores are randomly arranged from a few nanometers to hundreds of nanometers.
Example 5
This example provides a multi-stage ordered cellular EC80-g-PSSA21The preparation method of the graft copolymer microporous membrane is the same as that of the embodiment 4, and the difference is only that: the graft polymer used is EC80-g-PSSA21. The top surface of the honeycomb film was subjected to scanning electron microscopy, see FIG. 5.
Example 6
This example provides a multi-stage ordered cellular EC140-g-PSSA65The preparation method of the graft copolymer microporous membrane is the same as that of the embodiment 4, and the difference is only that: the graft polymer used is EC140-g-PSSA65. The top surface of the honeycomb film was subjected to scanning electron microscopy, see FIG. 6.
Example 7
This example provides a multi-stage ordered cellular EC80-g-PSSA44The preparation method of the graft copolymer microporous film is the same as that of example 4, and only the difference is thatThe method comprises the following steps: the solvent for preparing the spin-coating liquid is a mixed solution of carbon disulfide, chloroform, tetrahydrofuran and dichloromethane in any proportion, the concentration of the mixed solution is 2mg/mL, the solvent is naturally volatilized for 24 hours under the humidity of 50 percent, and a film with the thickness of 1 mu m is formed. The cross section of the honeycomb film was subjected to scanning electron microscopy and is shown in FIG. 7.
Example 8
This example provides a process for the preparation of a multi-stage ordered cellular EC-g-PSSA graft copolymer microporous film with a thickness of a few microns, which differs from example 4 only in that: take 0.01g EC80-g-PSSA44The graft copolymer is prepared into a solution with the concentration of 10mg/mL, and the solvent is naturally volatilized for 24 hours under the humidity of 50 percent to form a film with the thickness of 5 mu m. The cross section of the honeycomb film was subjected to scanning electron microscopy, see FIG. 8.
Processing a film section scanning electron microscope sample: and (3) quenching the honeycomb-shaped film in liquid nitrogen, taking out the film after several seconds, cutting the film by using a glass cutter, and spraying gold to obtain a film section electron microscope sample which can be used for electron microscope detection.
As can be seen from fig. 4-8, the greater the polymer concentration, the thicker the resulting film; the multistage ordered microporous film material with adjustable hole diameter and spacing can be obtained by changing the number of the repeating units of EC and PSSA.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A biomass-based EC-g-PSSA graft copolymer, characterized by having the following structure:
wherein m is 2-800, n is 2-900, R is CH2CH3Or H, ethylThe degree of substitution is 2.2-2.5;
preferably m is from 10 to 500 or from 30 to 300 or from 50 to 150 and n is from 2 to 600 or from 10 to 400 or from 20 to 200;
more preferably m-80, n-21; or m-80, n-44; or m is 80, n is 60; or m is 110, n is 20; or m is 110, n is 40; or m is 110, n is 60; or m is 140, n is 20; or m is 140, n is 40; or m is 140 and n is 65.
2. The biomass-based EC-g-PSSA graft copolymer according to claim 1, wherein the EC-g-PSSA graft copolymer has an EC repeating unit number m of 2 to 800 and a PSSA volume content fPSSA0.001-0.800;
preferably, the EC-g-PSSA graft copolymer has an EC repeating unit number m of 50-150 and a PSSA volume content fPSSAIs 0.003-0.700.
3. The process for the preparation of biomass-based EC-g-PSSA graft copolymers according to any of claims 1 or 2, characterized in that it comprises in particular the following steps:
(1) using an acylation reagent, an acid-binding agent and Ethyl Cellulose (EC) containing hydroxyl as raw materials, and carrying out micromolecule acylation reaction to obtain an EC macromolecular initiator;
(2) the EC macromolecular initiator, cuprous chloride, styrene and ligand are used as raw materials, and an EC-g-PS graft copolymer is obtained through atom transfer radical polymerization reaction;
(3) the EC-g-PS graft copolymer and a sulfonation reagent are used as raw materials, and the EC-g-PS graft copolymer is obtained through sulfonation reaction.
4. The method of claim 3, wherein the acylating agent is selected from one of 2-bromoisobutyryl bromide, 2-chloroisobutyryl chloride, 2-chloroisobutyryl bromide, 2-bromoisobutyryl chloride, preferably 2-bromoisobutyryl bromide; and/or:
the acid-binding agent is selected from one of anhydrous triethylamine, anhydrous pyridine, anhydrous N, N-diisopropylethylamine and anhydrous 4-dimethylaminopyridine, and is preferably anhydrous triethylamine; and/or;
the ligand is selected from one of pentamethyldiethylenetriamine, tri (2-dimethylaminoethyl) amine and pentamethyldipropylenetriamine, and is preferably pentamethyldiethylenetriamine; and/or;
the sulfonation reagent is selected from one of more than 98 wt% of concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, sulfur trioxide and acetyl sulfonate, and the more than 98 wt% of concentrated sulfuric acid is preferable; and/or;
step (1) is carried out in a solvent, wherein the solvent is one or a mixture of more of anhydrous tetrahydrofuran, anhydrous toluene, anhydrous dichloromethane and anhydrous trichloromethane, and is preferably anhydrous tetrahydrofuran; and/or;
the step (2) is carried out in a solvent, wherein the solvent is one or a mixture of two of chlorobenzene and N, N-dimethylformamide, preferably anhydrous chlorobenzene and one or a mixture of two of anhydrous N, N-dimethylformamide, and more preferably anhydrous chlorobenzene; and/or;
step (3) is carried out in a solvent selected from one or more of 1, 2-dichloroethane, cyclohexane and chloroform, preferably one or more of anhydrous 1, 2-dichloroethane, anhydrous cyclohexane and anhydrous chloroform, more preferably anhydrous 1, 2-dichloroethane.
5. The method for preparing biomass-based EC-g-PSSA graft copolymer according to any of claims 3 or 4, wherein the hydroxyl-containing EC in step (1): acylating reagent: acid-binding agent 1: (10-4000): (10-4000);
and/or, in step (2), the EC macroinitiator: ligand: cuprous chloride: styrene ═ 1: (1-5): (1-5): (1-600);
and/or, in step (3), the EC-g-PS graft copolymer: sulfonation reagent ═ 1: (1-1500).
6. The method of producing an EC-g-PSSA graft copolymer according to any of claims 3 to 5, further comprising a step of post-treating the reaction solution of steps (1) (2) (3),
the post-treatment in the step (1) is specifically as follows: dropping the reaction liquid into a large amount of deionized water, repeatedly precipitating, washing and filtering for more than three times;
the post-treatment in the step (2) is specifically as follows: quenching the reaction by using liquid nitrogen, removing copper salt, spin-drying the reaction solution, precipitating by using ether and alcohol solvents, and washing the product;
preferably, the ether solvent is petroleum ether, diethyl ether or a mixture of the petroleum ether and the diethyl ether;
preferably, a neutral alumina column is adopted to remove copper salt;
the post-treatment in the step (3) is specifically as follows: washing the product with deionized water for more than three times, washing the product with an anhydrous alcohol solvent to be neutral, and then putting the product into an oven for low-temperature drying;
preferably, the absolute alcohol solvent is absolute ethyl alcohol, absolute methyl alcohol or a mixture of the absolute ethyl alcohol and the absolute methyl alcohol.
7. A biomass-based EC-g-PSSA graft copolymer multistage microporous pattern film, characterized in that the film is prepared from the copolymer of any one of claims 1 or 2 or the graft copolymer prepared by the method of any one of claims 3 to 6.
8. The biomass-based EC-g-PSSA graft copolymer multistage microporous pattern film according to claim 7, wherein the multistage microporous pattern film is in a multistage ordered honeycomb microporous pattern structure;
preferably, the multi-stage microporous pattern film is a pattern structure with macropores arranged in an ordered hexagon, secondary micropores arranged randomly on a macroporous skeleton, the pore diameter of the macropores is hundreds of nanometers to hundreds of micrometers, and the pore diameter of the secondary micropores is several nanometers to hundreds of nanometers.
9. The method for preparing the biomass-based EC-g-PSSA graft copolymer multistage micropore pattern film as claimed in any one of claims 7 or 8, is characterized in that the prepared EC-g-PSSA graft copolymer solution is dripped on a support to form a film with a certain thickness, and the film is obtained after the solvent is naturally volatilized at different humidity;
preferably, the support body is one of a glass sheet, a silicon wafer, polyethylene terephthalate and an aluminum foil;
preferably, one or more of carbon disulfide, chloroform, dichloromethane and tetrahydrofuran are used as solvents to prepare the biomass-based EC-g-PSSA graft copolymer solution with the concentration of 2mg/mL-10 mg/mL;
preferably, the self-assembly conditions are: naturally volatilizing the solvent for 1-24h at the humidity of 20-90%; more preferably, the solvent is naturally volatilized for 16-24h under the humidity of 50% -90%.
10. Use of the biomass-based EC-g-PSSA graft copolymer multi-stage microporous pattern film of any of claims 7 or 8 or prepared by the method of claim 9 in the fields of fuel cell membranes, microelectronics, microfiltration separations, etc.; preferably in fuel cell membranes.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002009781A2 (en) * | 2000-07-28 | 2002-02-07 | The Dow Chemical Company | Sulfonated substantially random interpolymer-based absorbent materials |
| CN1341283A (en) * | 1999-02-26 | 2002-03-20 | 瑞威殴公司 | Solid gel membrane |
| CN102675543A (en) * | 2012-05-23 | 2012-09-19 | 湖南工业大学 | Ordered mesoporous material based on ethyecellulose grafted polrvinyl benzene copolymer and preparation method thereof |
| CN104194018A (en) * | 2014-08-29 | 2014-12-10 | 扬州大学 | Method for constructing functional ordered porous membrane by taking honeycomb-shaped porous membrane as template |
| CN104716353A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Porous membrane used for liquid flow cell and preparation and application thereof |
| CN104804715A (en) * | 2015-03-18 | 2015-07-29 | 西南石油大学 | Modified hydroxyethyl cellulose tackifier for well drilling and preparation method thereof |
| WO2016185009A1 (en) * | 2015-05-20 | 2016-11-24 | Danmarks Tekniske Universitet | Partially fluorinated electrospun proton exchange membranes |
| CN107236075A (en) * | 2017-05-31 | 2017-10-10 | 浙江理工大学 | Pressure-sensitive polymer composite foam with hierarchical porous structure and preparation method thereof |
| CN108359055A (en) * | 2018-01-10 | 2018-08-03 | 湖南工业大学 | A kind of cellulose acetate graft copolymer ordered porous membrane material and preparation method thereof |
| CN111217962A (en) * | 2019-07-08 | 2020-06-02 | 湖南工业大学 | Ethyl cellulose-based photoresponse ordered porous membrane material and preparation method thereof |
| WO2020165803A1 (en) * | 2019-02-13 | 2020-08-20 | King Abdullah University Of Science And Technology | Isoporous polymer membranes |
| CN111971114A (en) * | 2018-03-12 | 2020-11-20 | 特拉波雷技术有限公司 | Self-supporting pleatable block copolymer material and method of making the same |
| CN112979877A (en) * | 2021-02-22 | 2021-06-18 | 文水县是大高分子材料有限公司 | Cellulose-based dispersing agent, preparation method and application thereof, and coal water slurry |
-
2021
- 2021-11-15 CN CN202111348816.XA patent/CN114044853B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1341283A (en) * | 1999-02-26 | 2002-03-20 | 瑞威殴公司 | Solid gel membrane |
| WO2002009781A2 (en) * | 2000-07-28 | 2002-02-07 | The Dow Chemical Company | Sulfonated substantially random interpolymer-based absorbent materials |
| CN102675543A (en) * | 2012-05-23 | 2012-09-19 | 湖南工业大学 | Ordered mesoporous material based on ethyecellulose grafted polrvinyl benzene copolymer and preparation method thereof |
| CN104716353A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Porous membrane used for liquid flow cell and preparation and application thereof |
| CN104194018A (en) * | 2014-08-29 | 2014-12-10 | 扬州大学 | Method for constructing functional ordered porous membrane by taking honeycomb-shaped porous membrane as template |
| CN104804715A (en) * | 2015-03-18 | 2015-07-29 | 西南石油大学 | Modified hydroxyethyl cellulose tackifier for well drilling and preparation method thereof |
| WO2016185009A1 (en) * | 2015-05-20 | 2016-11-24 | Danmarks Tekniske Universitet | Partially fluorinated electrospun proton exchange membranes |
| CN107236075A (en) * | 2017-05-31 | 2017-10-10 | 浙江理工大学 | Pressure-sensitive polymer composite foam with hierarchical porous structure and preparation method thereof |
| CN108359055A (en) * | 2018-01-10 | 2018-08-03 | 湖南工业大学 | A kind of cellulose acetate graft copolymer ordered porous membrane material and preparation method thereof |
| CN111971114A (en) * | 2018-03-12 | 2020-11-20 | 特拉波雷技术有限公司 | Self-supporting pleatable block copolymer material and method of making the same |
| WO2020165803A1 (en) * | 2019-02-13 | 2020-08-20 | King Abdullah University Of Science And Technology | Isoporous polymer membranes |
| CN111217962A (en) * | 2019-07-08 | 2020-06-02 | 湖南工业大学 | Ethyl cellulose-based photoresponse ordered porous membrane material and preparation method thereof |
| CN112979877A (en) * | 2021-02-22 | 2021-06-18 | 文水县是大高分子材料有限公司 | Cellulose-based dispersing agent, preparation method and application thereof, and coal water slurry |
Non-Patent Citations (4)
| Title |
|---|
| ASMAA ATTYA SHALABY ET AL.: "Development of novel cellulose acetate-g-poly(sodium 4-styrenesulfonate) proton conducting polyelectrolyte polymer", 《JOURNAL OF SAUDI CHEMICAL SOCIETY》 * |
| ASMAA ATTYA SHALABY ET AL.: "Development of novel cellulose acetate-g-poly(sodium 4-styrenesulfonate) proton conducting polyelectrolyte polymer", 《JOURNAL OF SAUDI CHEMICAL SOCIETY》, vol. 25, 14 August 2021 (2021-08-14), pages 1 - 13, XP086806477, DOI: 10.1016/j.jscs.2021.101327 * |
| SENBIN CHEN ET AL.: "Synthesis of amphiphilic diblock copolymers derived from renewable dextran by nitroxide mediated polymerization: towards hierarchically structured honeycomb porous films", 《POLYM. CHEM.》 * |
| SENBIN CHEN ET AL.: "Synthesis of amphiphilic diblock copolymers derived from renewable dextran by nitroxide mediated polymerization: towards hierarchically structured honeycomb porous films", 《POLYM. CHEM.》, vol. 5, 12 May 2014 (2014-05-12), pages 5310 - 5319 * |
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