CN106215727A - A kind of preparation method of polyamino acid modified polyphenyl thioether perforated membrane - Google Patents
A kind of preparation method of polyamino acid modified polyphenyl thioether perforated membrane Download PDFInfo
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- CN106215727A CN106215727A CN201610666063.XA CN201610666063A CN106215727A CN 106215727 A CN106215727 A CN 106215727A CN 201610666063 A CN201610666063 A CN 201610666063A CN 106215727 A CN106215727 A CN 106215727A
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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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
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- 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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
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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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- 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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
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Abstract
The invention discloses the preparation method of a kind of polyamino acid modified polyphenyl thioether perforated membrane.The method utilizes TIPS to prepare PPS perforated membrane, by nitrification reducing process in the surface ammonification of PPS perforated membrane, cause alpha amino acid N carboxyl inner-acid anhydride to react by amino, different types of aminoacid is grafted to PPS porous film surface as characteristic group, obtains polyamino acid MODIFIED PP S perforated membrane.This method utilizes the physical and chemical performance that PPS perforated membrane is excellent, to film modifying surface, does not destroy internal matrix structure and the pore passage structure of film, prepares a kind of perforated membrane with antipollution, biocompatibility.
Description
Technical field
The present invention relates to macromolecule member material preparation field, a kind of polyamino acid modified polyphenyl thioether perforated membrane
Preparation method.
Background technology
Polyphenylene sulfide (PPS) is a kind of novel thermoplastic resin, has high temperature resistant, the corruption of solvent resistant, acid and alkali-resistance of excellence
Erosion, radiation hardness, fire-retardant and good mechanical property and electric property, have widely at electronics, automobile, machinery and chemical field
Application, is described as the sixth-largest engineering plastics.PPS material can in acid, alkalescence and organic solvent long-time applied at elevated temperature, and its
Wearability, ageing-resistant the strongest.PPS can realize the direct process of organic solvent as membrane material, owing to PPS has excellent
Creep resistant, good stability of the dimension, elastic modelling quantity are high, can avoid the dissolving of membrane material and come off.Comprehensive described, PPS has
It is used as the potential quality of membrane material.
But due to the hydrophobicity of PPS, causing the PPS perforated membrane prepared by TIPS method is surface hydrophobicity, is particularly used for
To having the separation aspect of bioactive substance containing protein etc., easily cause flux low, and the adhesion of protein, easily make
The blocking of the pollution of film forming, even duct, directly affects the service life of film.And the hydrophilicity improving film can carry effectively
The antifouling property of high film;Surface-coated, grafting at film contain zwitterionic material, can be effectively improved the anti-protein of film
Pollutant performance, improves the biocompatibility of film.
Summary of the invention
For the deficiencies in the prior art, the technical problem that the present invention intends to solve is to provide a kind of polyamino acid modified polyphenyl
The preparation method of thioether perforated membrane.The method utilizes TIPS to prepare PPS perforated membrane, by nitrification reducing process at PPS perforated membrane
Surface ammonification, causes a-amino acid-N-carboxyl inner-acid anhydride to react, using different types of aminoacid as characteristic group by amino
It is grafted to PPS porous film surface, obtains polyamino acid MODIFIED PP S perforated membrane.
The present invention solves the technical scheme of described technical problem and is to provide a kind of polyamino acid modified polyphenyl thioether perforated membrane
Preparation method, it is characterised in that comprise the steps:
1) PPS perforated membrane prepared by TIPS method is put in salpeter solution, under the conditions of 30-80 DEG C, carry out nitration reaction
0.5-24h;Reaction washs PPS perforated membrane after terminating does not has NO to surface3 -, obtain nitrification PPS perforated membrane;
2) 0.01-1g catalyst is placed in 50-200ml reaction dissolvent dispersion 10-60min, then by 1-50g nitrification PPS
Perforated membrane is put into wherein, is warming up to 60-120 DEG C, adds 2-10g reducing agent, and after reaction 1-10h, washing is dried, and obtains ammonification
PPS perforated membrane;
Active component is loaded to make on carrier by described catalyst;Described active component is Pd, Ag, Au, Ru,
Cu, Ni or Fe;Described carrier is activated carbon, CNT, Graphene, lamellar graphite, SiC, ZrO2、TiO2、SiO2、SnO2、
Al2O3, ZSM-5, SBA-15, MCM-41, phosphate aluminium molecular sieve, montmorillonite, Y type molecular sieve or beta molecular sieve;
Described reaction dissolvent is alcohols solvent, halogenated hydrocarbon solvent, ether solvent, esters solvent, organic amine solvent, hydrocarbon
At least one in kind solvent or amide solvent;
Described reducing agent is hydrazine hydrate, metal hydride, Na2S, sulfur are for sodium sulfide or H2In at least one;
3) 0.02-1g a-amino acid-N-carboxyl inner-acid anhydride is dissolved in 50-200ml aprotic solvent, then by 1-50g
Ammonification PPS perforated membrane is put into wherein, 30-65 DEG C of reaction 1-48h, is put into by product in NaOH solution and soak after cleaning, and washing is dry
After dry, obtain polyamino acid MODIFIED PP S perforated membrane;
Described a-amino acid-N-carboxyl inner-acid anhydride is Pidolidone-γ-benzyl ester-N-carboxyl inner-acid anhydride, L-glycine-N-
In carboxyl inner-acid anhydride, alanine-N-carboxyl inner-acid anhydride, valine-N-carboxyl inner-acid anhydride or isoleucine-N-carboxyl inner-acid anhydride
At least one;
Described aprotic solvent is ether solvent, ketones solvent, nitrile solvents, halogenated hydrocarbon solvent, varsol, sulfone class
At least one in solvent or amide solvent.
Compared with prior art, the present invention has the beneficial effects that: this method utilizes the physical chemistry that PPS perforated membrane is excellent
Can, to film modifying surface, do not destroy internal matrix structure and the pore passage structure of film, preparation one has antipollution, biology
The perforated membrane of the compatibility.By at PPS fenestra road outer surface grafting amino, it is achieved that hydrophobic film to the transformation of hydrophilic film,
Substantially increase the pure water flux of film;By a-amino acid-N-carboxyl inner-acid anhydride in ammonification PPS porous film surface ring-opening polymerisation,
Obtain polyamino acid MODIFIED PP S perforated membrane.This fenestra road narrowly distributing, mainly based on nanoscale duct, water contact angle is at 40-
Between 80 °, it is possible to achieve organic micromolecule compound or have the Selective Separation of bioactive material, this film has well
Contamination resistance, improve the service life of PPS perforated membrane.
Detailed description of the invention
The specific embodiment of the present invention is given below.Specific embodiment is only used for further describing the present invention, does not limits
The application scope of the claims processed.
The invention provides the preparation method of a kind of polyamino acid modified polyphenyl thioether perforated membrane, it is characterised in that include as
Lower step:
1) PPS perforated membrane prepared by TIPS method is put in salpeter solution, under the conditions of 30-80 DEG C, carry out nitration reaction
0.5-24h;Reaction washs PPS perforated membrane after terminating does not has NO to surface3 -, obtain nitrification PPS perforated membrane;
Described salpeter solution concentration is 10-60%;
2) 0.01-1g catalyst is placed in 50-200ml reaction dissolvent dispersion 10-60min, then by 1-50g nitrification PPS
Perforated membrane is put into wherein, is warming up to 60-120 DEG C, adds 2-10g reducing agent, and after reaction 1-10h, washing is dried, and obtains ammonification
PPS perforated membrane;
Active component is loaded to make on carrier by described catalyst;Described active component is Pd, Ag, Au, Ru,
Cu, Ni or Fe;Described carrier is activated carbon, CNT, Graphene, lamellar graphite, SiC, ZrO2、TiO2、SiO2、SnO2、
Al2O3, ZSM-5, SBA-15, MCM-41, phosphate aluminium molecular sieve, montmorillonite, Y type molecular sieve or beta molecular sieve;
Described reaction dissolvent is alcohols solvent, halogenated hydrocarbon solvent, ether solvent, esters solvent, organic amine solvent, hydrocarbon
At least one in kind solvent or amide solvent;Described alcohols solvent is propanol, isopropanol, butanol, isobutanol or benzyl alcohol
In at least one;Described halogenated hydrocarbon solvent is at least one in tetrachloromethane, 1,2-dichloroethanes or oxolane;Institute
Stating ether solvent is butyl ether;Described esters solvent is ethyl acetate, butyl acetate, ethyl benzoate, Ethyl formate, carbonic acid diformazan
At least one in ester, diethyl carbonate, dibutyl carbonate or dipropyl carbonate;Described organic amine solvent is aniline, propylamine
Or at least one in butylamine;Described varsol is at least one in hexamethylene, benzene or toluene;Described amide solvent N,
Dinethylformamide, N, at least one in N-diethyl acetamide;
Described reducing agent is hydrazine hydrate, metal hydride, Na2S, sulfur are for sodium sulfide or H2In at least one;Described metal
Hydride is NaAlH4Or NaBH4;
3) 0.02-1g a-amino acid-N-carboxyl inner-acid anhydride is dissolved in 50-200ml aprotic solvent, then by 1-50g
Ammonification PPS perforated membrane is put into wherein, 30-65 DEG C of reaction 1-48h, is put in 0.1-2mol/L NaOH solution by product after cleaning
Soaking 30min-24h, washing is dried, obtains polyamino acid MODIFIED PP S perforated membrane;
Described a-amino acid-N-carboxyl inner-acid anhydride is Pidolidone-γ-benzyl ester-N-carboxyl inner-acid anhydride, L-glycine-N-
In carboxyl inner-acid anhydride, alanine-N-carboxyl inner-acid anhydride, valine-N-carboxyl inner-acid anhydride or isoleucine-N-carboxyl inner-acid anhydride
At least one;
Described aprotic solvent is ether solvent, ketones solvent, nitrile solvents, halogenated hydrocarbon solvent, varsol, sulfone class
At least one in solvent or amide solvent;Described ether solvent is at least one in oxolane, ether or methyl phenyl ethers anisole;
Described ketones solvent is at least one in acetone, butanone or 1-Phenylethanone.;Described nitrile solvents is acetonitrile or butyronitrile;Described halo
Varsol is at least one in carbon tetrachloride, chloroform or 1,2-dichloroethanes;Described varsol is benzene, toluene or hexamethylene
At least one in alkane;Described sulfone kind solvent is at least one in dimethyl sulfoxide, sulfolane or diphenyl sulphone (DPS);Described amide-type
Solvent is DMF, at least one in N-Methyl pyrrolidone or N,N-dimethylacetamide;
Embodiment 1
(1) PPS perforated membrane prepared by TIPS method being put into concentration is in 33% salpeter solution, and 50 DEG C seal immersion reaction
4h, reaction washs PPS porous film surface after terminating does not has NO3 -, obtain nitrification PPS perforated membrane;
(2) 0.06g Pd/C catalyst is disperseed in 30mL isobutanol 20min, then 10g nitrification PPS perforated membrane is put into
Wherein, being warming up to 80 DEG C, add 8mL hydrazine hydrate, after reaction 4h, washing is dried, and obtains ammonification PPS perforated membrane;
(3) 0.02g Pidolidone-γ-benzyl ester-N-carboxyl inner-acid anhydride is dissolved in 50ml anhydrous tetrahydro furan, then will
10g ammonification PPS perforated membrane is put into wherein, 40 DEG C of reaction 4h, and product is put into after cleaning immersion 2h in 2mol/L NaOH solution,
Washing is dried, obtains polyamino acid MODIFIED PP S perforated membrane.
Mercury injection method test membrane aperture is distributed as 0.1-1 micron, water contact angle 75 °, and the average water flux of film is 121L/m2H,
After film utilizes 48 days, water flux is held essentially constant, and finds no machine matter and pollutes.
Embodiment 2
(1) PPS perforated membrane prepared by TIPS method being put into concentration is in 33% salpeter solution, and 50 DEG C seal immersion reaction
4h, reaction washs PPS porous film surface after terminating does not has NO3 -, obtain nitrification PPS perforated membrane;
(2) by 0.06g Ni/SiO2Catalyst is in 30mL CCl4Middle dispersion 20min, then 10g nitrification PPS perforated membrane is put
Enter wherein, be warming up to 75 DEG C, add 8gH2, after reaction 4h, washing is dried, and obtains ammonification PPS perforated membrane;
(3) 0.02g isoleucine-N-carboxyl inner-acid anhydride is dissolved in the anhydrous butanone of 50ml, then by many for 10g ammonification PPS
Pore membrane is put into wherein, and 40 DEG C of reaction 4h, washing is dried, obtains polyamino acid MODIFIED PP S perforated membrane.
Mercury injection method test membrane aperture is distributed as 0.1-1.2 micron, water contact angle 71 °, and the average water flux of film is 125L/
m2h.After film utilizes 48 days, water flux is held essentially constant, and finds no machine matter and pollutes.
Embodiment 3
(1) PPS perforated membrane prepared by TIPS method being put into concentration is in 33% salpeter solution, and 50 DEG C seal immersion reaction
4h, reaction washs PPS porous film surface after terminating does not has NO3 -, obtain nitrification PPS perforated membrane;
(2) 0.06g Ru/SBA-15 catalyst is disperseed in 30mL oxolane 20min, then by many for 10g nitrification PPS
Pore membrane is put into wherein, is warming up to 60 DEG C, and addition 12g sulfur is for sodium sulfide, and after reaction 4h, washing is dried, and obtains ammonification PPS porous
Film;
(3) 0.05g L-glycine-N-carboxyl inner-acid anhydride is dissolved in 100ml anhydrous acetonitrile, then by 10g ammonification PPS
Perforated membrane is put into wherein, and 40 DEG C of reaction 4h, washing is dried, obtains polyamino acid MODIFIED PP S perforated membrane.
Mercury injection method test membrane aperture is distributed as 0.1-1.35 micron, water contact angle 63 °, and the average water flux of film is 138L/
m2h.After film utilizes 48 days, water flux is held essentially constant, and finds no machine matter and pollutes.
Embodiment 4
(1) PPS perforated membrane prepared by TIPS method being put into concentration is in 33% salpeter solution, and 50 DEG C seal immersion reaction
4h, reaction washs PPS porous film surface after terminating does not has NO3 -, obtain nitrification PPS perforated membrane;
(2) 0.06g Fe/ZMS-5 catalyst is disperseed in 30mL dimethyl carbonate 20min, then by many for 10g nitrification PPS
Pore membrane is put into wherein, is warming up to 80 DEG C, adds 8g NaAlH4, after reaction 4h, washing is dried, and obtains ammonification PPS perforated membrane;
(3) 0.05g alanine-N-carboxyl inner-acid anhydride is dissolved in the anhydrous carbon tetrachloride of 60ml, then by 10g ammonification PPS
Perforated membrane is put into wherein, and 40 DEG C of reaction 4h, washing is dried, obtains polyamino acid MODIFIED PP S perforated membrane.
Mercury injection method test membrane aperture is distributed as 0.1-1.4 micron, water contact angle 68 °, and the average water flux of film is 147L/
m2h.After film utilizes 48 days, water flux is held essentially constant, and finds no machine matter and pollutes.
Embodiment 5
(1) PPS perforated membrane prepared by TIPS method being put into concentration is in 33% salpeter solution, and 50 DEG C seal immersion reaction
4h, reaction washs PPS porous film surface after terminating does not has NO3 -, obtain nitrification PPS perforated membrane;
(2) 0.06g Cu/SiC catalyst is disperseed in 30mL DMF 20min, then by 10g nitrification
PPS perforated membrane is put into wherein, is warming up to 80 DEG C, adds 8g NaBH4, after reaction 4h, washing is dried, and obtains ammonification PPS porous
Film;
(3) 0.1g valine-N-carboxyl inner-acid anhydride is dissolved in 100ml anhydrous dimethyl sulphoxide, then by 10g ammonification
PPS perforated membrane is put into wherein, and 40 DEG C of reaction 4h, washing is dried, obtains polyamino acid MODIFIED PP S perforated membrane.
Mercury injection method test membrane aperture is distributed as 0.1-1.4 micron, water contact angle 72 °, and the average water flux of film is 135L/
m2h.After film utilizes 48 days, water flux is held essentially constant, and finds no machine matter and pollutes.
The present invention does not addresses part and is applicable to prior art.
Claims (6)
1. the preparation method of a polyamino acid modified polyphenyl thioether perforated membrane, it is characterised in that comprise the steps:
1) PPS perforated membrane prepared by TIPS method is put in salpeter solution, under the conditions of 30-80 DEG C, carry out nitration reaction 0.5-
24h;Reaction washs PPS perforated membrane after terminating does not has NO to surface3 -, obtain nitrification PPS perforated membrane;
2) 0.01-1g catalyst is placed in 50-200ml reaction dissolvent dispersion 10-60min, then by 1-50g nitrification PPS porous
Film is put into wherein, is warming up to 60-120 DEG C, adds 2-10g reducing agent, and after reaction 1-10h, washing is dried, and obtains ammonification PPS many
Pore membrane;
Active component is loaded to make on carrier by described catalyst;Described active component is Pd, Ag, Au, Ru, Cu, Ni
Or Fe;Described carrier is activated carbon, CNT, Graphene, lamellar graphite, SiC, ZrO2、TiO2、SiO2、SnO2、Al2O3、
ZSM-5, SBA-15, MCM-41, phosphate aluminium molecular sieve, montmorillonite, Y type molecular sieve or beta molecular sieve;
Described reaction dissolvent is that alcohols solvent, halogenated hydrocarbon solvent, ether solvent, esters solvent, organic amine solvent, hydro carbons are molten
At least one in agent or amide solvent;
Described reducing agent is hydrazine hydrate, metal hydride, Na2S, sulfur are for sodium sulfide or H2In at least one;
3) 0.02-1g a-amino acid-N-carboxyl inner-acid anhydride is dissolved in 50-200ml aprotic solvent, then by 1-50g ammonification
PPS perforated membrane is put into wherein, 30-65 DEG C of reaction 1-48h, is put into by product in NaOH solution and soak after cleaning, and washing is dried,
Obtain polyamino acid MODIFIED PP S perforated membrane;
Described a-amino acid-N-carboxyl inner-acid anhydride is Pidolidone-γ-benzyl ester-N-carboxyl inner-acid anhydride, L-glycine-N-carboxyl
In inner-acid anhydride, alanine-N-carboxyl inner-acid anhydride, valine-N-carboxyl inner-acid anhydride or isoleucine-N-carboxyl inner-acid anhydride at least
A kind of;
Described aprotic solvent is ether solvent, ketones solvent, nitrile solvents, halogenated hydrocarbon solvent, varsol, sulfone kind solvent
Or at least one in amide solvent.
The preparation method of polyamino acid modified polyphenyl thioether perforated membrane the most according to claim 1, it is characterised in that described
Step 1) in salpeter solution concentration be 10-60%.
The preparation method of polyamino acid modified polyphenyl thioether perforated membrane the most according to claim 1, it is characterised in that step
2) metal hydride described in is NaAlH4Or NaBH4。
The preparation method of polyamino acid modified polyphenyl thioether perforated membrane the most according to claim 1, it is characterised in that step
2) alcohols solvent described in is at least one in propanol, isopropanol, butanol, isobutanol or benzyl alcohol;Described halogenated hydrocarbon is molten
Agent is at least one in tetrachloromethane, 1,2-dichloroethanes or oxolane;Described ether solvent is butyl ether;Described esters is molten
Agent be ethyl acetate, butyl acetate, ethyl benzoate, Ethyl formate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate or
At least one in dipropyl carbonate;Described organic amine solvent is at least one in aniline, propylamine or butylamine;Described hydro carbons
Solvent is at least one in hexamethylene, benzene or toluene;Described amide solvent is N,N-dimethylformamide or N, N-diethyl
Yl acetamide.
The preparation method of polyamino acid modified polyphenyl thioether perforated membrane the most according to claim 1, it is characterised in that described
Step 3) in time of soaking in NaOH solution of product be 30min-24h, the concentration of NaOH solution is 0.1-2mol/L.
The preparation method of polyamino acid modified polyphenyl thioether perforated membrane the most according to claim 1, it is characterised in that described
Step 3) described ether solvent is at least one in oxolane, ether or methyl phenyl ethers anisole;Described ketones solvent is acetone, butanone
Or at least one in 1-Phenylethanone.;Described nitrile solvents is acetonitrile or butyronitrile;Described halogenated hydrocarbon solvent is carbon tetrachloride, chloroform
Or at least one in 1,2-dichloroethanes;Described varsol is at least one in benzene, toluene or hexamethylene;Described sulfone class
Solvent is at least one in dimethyl sulfoxide, sulfolane or diphenyl sulphone (DPS);Described amide solvent is DMF,
At least one in N-Methyl pyrrolidone or DMAC N,N' dimethyl acetamide.
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CN109248711A (en) * | 2018-10-15 | 2019-01-22 | 天津工业大学 | A kind of load TiO2PPS photocatalysis membrana preparation method |
CN112252022A (en) * | 2020-10-25 | 2021-01-22 | 天津工业大学 | Preparation method of super-hydrophilic PPS composite fiber membrane |
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CN112626639A (en) * | 2020-12-16 | 2021-04-09 | 四川大学 | Active carbon-loaded polyphenylene sulfide porous fiber and preparation method and application thereof |
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CN112252022A (en) * | 2020-10-25 | 2021-01-22 | 天津工业大学 | Preparation method of super-hydrophilic PPS composite fiber membrane |
CN112626639A (en) * | 2020-12-16 | 2021-04-09 | 四川大学 | Active carbon-loaded polyphenylene sulfide porous fiber and preparation method and application thereof |
CN112626639B (en) * | 2020-12-16 | 2021-12-17 | 四川大学 | Active carbon-loaded polyphenylene sulfide porous fiber and preparation method and application thereof |
CN117117270A (en) * | 2023-10-23 | 2023-11-24 | 国家电投集团氢能科技发展有限公司 | Modified porous membrane, ion exchange membrane, preparation method and application of modified porous membrane and ion exchange membrane, and fuel cell |
CN117117270B (en) * | 2023-10-23 | 2024-02-09 | 国家电投集团氢能科技发展有限公司 | Modified porous membrane, ion exchange membrane, preparation method and application of modified porous membrane and ion exchange membrane, and fuel cell |
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