CN108530658A - Block polymer FPEG-CO-CA modified CA filter membranes and preparation method thereof - Google Patents
Block polymer FPEG-CO-CA modified CA filter membranes and preparation method thereof Download PDFInfo
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- C08J5/18—Manufacture of films or sheets
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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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
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Abstract
The present invention provides a kind of block polymer FPEG CO CA modified CA membrane preparation methods, it forms a film after using block polymer FPEG CO CA to be modified to CA as additive, block polymer FPEG CO CA modified CA filter membranes are made, wherein, esterification using simple free radical polymerization and room temperature obtains FPEG CO CA block polymers as the property-modifying additive of CA films, the operating procedure that this method is prepared compared to existing technology needed for block polymer additive is few, it is easy to operate, it is at low cost, it is easy to industrialized production；Block polymer FPEG CO CA obtained are blended with CA and prepare modified filter membranes, conventional immersion precipitation phase inversion process can be used to be prepared.Preparation process is simple, and modified condition requirement is low and easy to control, and membrane structure is controllable and uniform, and film has lasting stability.Using such novel block polymer modification CA seperation films, easy to operate, use scope is wider.
Description
Technical field
The present invention relates to macromolecular design and synthesis and technical field of membrane separation, more particularly to a kind of block polymer
FPEG-CO-CA modified CA filter membranes and preparation method thereof.
Background technology
As a kind of novel science and technology, membrane separation technique because its disengaging time is short, low energy consumption, it is efficient, need not make
The advantages that with additional chemical agent, non-secondary pollution and convenient operation and control, it is widely used in medical treatment, the energy, electronics
Equal fields, are also applied in the Practical Project of various wastewater treatments, and maximum resistance of the application of membrane in wastewater treatment
Hinder be film self-pollution problem.Cellulose acetate (CA) is because its filming performance is good, preparation process is simple, cheap, environment
The advantages that friendly by as history at most with widely applied material of preparing, but CA films because easily contaminated, not microbial corrosion resistance,
The shortcomings of easily being aoxidized greatly limits its further extensive use in UF membrane field.So technical staff
Physics, chemical modification are carried out to CA films by various methods, enhances its antifouling property, improves its separative efficiency, extend film
Service life.
In the method for modifying of film, blending and modifying is a kind of additive or second polymer to be added to matrix membrane material
In, the method that host material is modified by way of blending, it is advantageous that prepared film is with good uniform
Property, fenestra inside is almost the same with the chemical composition of film surface, and membrane separating effect is more preferable, is conducive to large-scale production and application.
In the prior art, Jayalakshmi etc. [Journal of Membrane Science.2014,465:117-
128] it has synthesized and has been grafted Methacrylamide (PIPA-g-MAA) on the poly- isophthaloyl amine of copolymer, film is blended with CA for it.When
When additive mass fraction is 10%, 20%, 30%, the water contact angle of blend film is respectively 38.2 °, 35.1 °, 31.4 ° it is low
In the water contact angle of CA films.CA：PIPA-g-MAA is 70:When 30, the attenuation rate of membrane filtration bovine serum albumin (BSA) is
76.7%, flux recovery rate is 92.4%, and irreversible membrane fouling 7.6%, film shows preferable antifouling property.The additive
PIPA-g-MAA is that a kind of combustibles benzoyl peroxide (BPO) has been used to be used as initiator, and graft polymerization MAA reacts on PIPA
The condition of strictly control anaerobic is needed come what is synthesized, in reaction process, the large dosage that this limits additive to a certain extent is raw
Production, hinders the industrial applications of Modified Membrane.
[the Journal of Membrane Science.2015,473 such as Mahdavi:256-266] use bis- (the hydroxyl first of 2,2-
Base) propionic acid and 1,1,1- trimethylolpropane has synthesized aliphatic hyper-branched polyester by melt condensation method, and itself and CA are mixed
Conjunction prepares Asymmetric Ultrafiltration Membrane.When the mixed proportion of CA and additive aliphatic hyper-branched polyester is 9:When 1, Modified Membrane is to albumen
The rejection of matter is up to 100%, and flux recovery rate is 85%, and the resistance tocrocking of this CA blend film is improved, but modification adds
Add agent to need under 140 DEG C of hot conditions, realize synthesis using p-methyl benzenesulfonic acid as dehydrating agent, reaction condition is also more
Harshness is very high to energy requirements.
Chinese patent CN 105396473A have invented temperature, the cellulose acetate preparation method of pH responses and the film
Using, week et al. is prepared for block polymer F127-b-PDMAEMA using regeneration activating Transfer Radical Polymerization, with
CA is prepared for blend film by immersion precipitation phase inversion process.The film has preferable hydrophily and resistance tocrocking, the water flux of film
It can change with temperature and pH value, that is, there is response.But the reaction for preparing block polymer is more harsh, such as needs to control
The condition of anaerobic processed has used more expensive metallic catalyst etc., and preparation method is relatively complicated.
Chinese patent CN 102500247A have invented a kind of preparation method of modified cellulose acetate ultrafiltration membrane, using poly-
Additive of the nano silicon dioxide that glycol monoethyl ether is modified as CA, prepares blend film, the experimental results showed that blend film
Hydrophily is improved, and film is to the rejection of oil emulsion up to 93.4%.Inorganic nano-particle used in the method for modifying
It is that poly glycol monomethyl ether is grafted on nano-silicon dioxide particle by polymerisation, it is harsh equally exists synthetic reaction
Defect；And inorganic nano silicon dioxide granule and the intermolecular forces of organic matter CA are weak, and there is dioxies after long-time service
The risk that SiClx particle falls off easily causes secondary pollution, while improving use cost.
As it can be seen that in existing organic film modifier, preparation method is realized by various polymerisations mostly, and is gathered
It is more demanding to experiment condition to close reaction, reaction condition, such as anhydrous and oxygen-free or high temperature have been must be strictly controlled in building-up process
Experiment condition, i.e. synthesis technology complexity are cumbersome.
In conclusion the CA composite membranes that a kind of novel preparation process is simple and antipollution effect is good are urgently developed.
Invention content
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of easy methods, to solve
The hydrophobicity of conventional CA filter membranes (including plate membrane and hollow-fibre membrane) is strong, and water flux is low, in separation process easily by protein,
The problem of irreversible membrane fouling of the organic matters such as oils.
A further object of the invention be it is cumbersome in order to solve synthesis modification CA filter membranes method in the prior art, it is of high cost,
Operation requires high technical problem and partial reaction to be not easy to remove and be not easy industrialized technology using metal salt catalyst to ask
Topic.
A further object of the invention is using novel block polymer FPEG-CO-CA as blending and modifying additive, profit
It is made with simply oxidation and two step of esterification, preparation modified CA filter membrane reaction condition requirement is low, easy to control, and CA membrane materials
The hydrophily of material, the antifouling property for enhancing film are improved, and the service life of film is extended.
In order to achieve the above objects and other related objects, the present invention provides a kind of block polymer FPEG-CO-CA modified CAs
The preparation method of filter membrane forms a film after using block polymer FPEG-CO-CA to be modified to CA as additive, is made embedding
Section polymer FPEG-CO-CA modified CA filter membranes, wherein FPEG-CO-CA is synthesized by the following way route and is made：
Preferably, it is made by following steps：
1) perfluoroalkyl-polyethylene glycol (FPEG) is passed through and 2,2,6,6- tetramethyl piperidines nitrogen oxides (TEMPO) oxygen
Perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH) is obtained by the reaction in change；
2) cellulose acetate (CA) esterification is carried out with perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH) to synthesize
Block polymer FPEG-CO-CA；
3) cellulose acetate (CA), block polymer FPEG-CO-CA are placed in 60 DEG C of dryings in vacuum drying chamber respectively
12~36h is dried solvent n,N-dimethylacetamide (DMAc) using 4A types molecular sieve；By CA, FPEG- after drying
CO-CA is dissolved in by a certain percentage in the DMAc after drying, at a temperature of 40~80 DEG C, with the tachogenerator of 200~500r/min
Tool stirs 12~36h, forms casting solution；
4) casting solution is cooled to room temperature, under 6000~9000r/min rotating speeds, evacuation and centrifugal degassing 15min；
5) casting solution after deaeration is made to the hollow-fibre membrane of certain thickness plate membrane or certain wall thickness, in air
It after standing 5~20s, puts into coagulating bath, coagulating bath is pure water, and room temperature impregnates 2h moldings in coagulating bath；Molding film is changed
It is placed in pure water to impregnate to take out to be placed in 45% glycerine afterwards for 24 hours and impregnate for 24 hours；It finally takes out naturally dry, save backup, be made
Block polymer FPEG-CO-CA modified CA filter membranes.
Preferably, the mass ratio of CA and FPEG-CO-CA is 7:3~9:1.
Preferably, step 3) is to set cellulose acetate (CA), block polymer FPEG-CO-CA and pore-foaming agent respectively
60 DEG C of dry 12~36h in vacuum drying chamber carry out solvent n,N-dimethylacetamide (DMAc) using 4A types molecular sieve
It is dry；By after drying CA, FPEG-CO-CA and pore-foaming agent be dissolved in by a certain percentage it is dry after DMAc in, in 60 DEG C of temperature
Under, with rotating speed 12~36h of mechanical agitation of 200~500r/min, form casting solution.
Preferably, the pore-foaming agent is polyethylene glycol (PEG) or polyvinylpyrrolidone (PVP).
Preferably, CA, FPEG-CO-CA mass ratio are 7:3~9:1, pore-foaming agent additive amount is the casting solution gross mass
0.5~20wt%.
Preferably, the preparation method of perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH) is：By a certain amount of perfluor alkane
Base-polyethylene glycol (FPEG), 2,2,6,6- tetramethyl piperidines nitrogen oxides (TEMPO) and by sodium dihydrogen phosphate (NaH2PO4)/phosphorus
Sour disodium hydrogen (Na2HPO4) buffer solution that mixes pH=7 is respectively placed in round-bottomed flask, solvent acetonitrile is added
(CH3CN), sodium hypochlorite (NaClO) and sodium chlorite (NaClO is then added dropwise into round-bottomed flask simultaneously2) solution, it is added dropwise
Afterwards, 3~6h of mechanical agitation at a temperature of 25~50 DEG C；After reaction, reaction product is cooled to room temperature, be added suitable
Water adjusts pH to 8, and under 0 DEG C of ice-water bath, sodium thiosulfate (Na is added thereto2S2O3) after solution is quenched, add
Appropriate t-butyl methyl ether (MTBE) is simultaneously shaken, and after acquired solution layering, discards organic phase；Hydrochloric acid (HCl) is added into water phase
Solution adjusts pH to 3, then with more times of MTBE extractions, all organic phases generated in multiple extraction process is merged, after merging
Organic phase is dry with anhydrous magnesium sulfate (MgSO4), filtering, filtrate is obtained to weak yellow liquid FPEG- after rotary evaporation
COOH。
Preferably, the preparation method of block polymer FPEG-CO-CA is：By a certain amount of perfluoroalkyl-polyethylene glycol carboxylic
Sour (FPEG-COOH) is added to cellulose acetate (CA) in round-bottomed flask, and is added into round-bottomed flask a certain amount of by 4- bis-
The esterifying reagent and tetrahydrofuran (THF) solvent that picoline (DMAP), dicyclohexylcarbodiimide (DCC) are constituted, 25~
After reacting 1~3d at a temperature of 50 DEG C, reaction solution is obtained；Reaction solution is slowly added to be settled in a certain amount of deionized water,
Filter cake is collected after filtering, and filter cake is dissolved in a certain amount of tetrahydrofuran (THF), is poured slowly into deionized water and is sunk again
After drop, filtering for 24 hours by filtration product freeze-drying, faint yellow solid block polymer FPEG-CO-CA is obtained.
Preferably, the molecular weight of cellulose acetate (CA) is about 30000~50000, wherein acetyl content be 38~
40wt%, hydroxy radical content are 3~4wt%, and any commercial cellulose acetate can be used in cellulose acetate.
The present invention also provides a kind of block polymer FPEG-CO-CA modified CA filter membranes, are made by above-mentioned preparation method.
As described above, the present invention block polymer FPEG-CO-CA modified CA filter membranes and preparation method thereof have it is following
Advantageous effect：
1, the preparation of additive block polymer FPEG-CO-CA is anti-using simple free radical polymerization and the esterification of room temperature
Answer, this method compared to existing technology needed for operating procedure it is few, it is easy to operate, it is at low cost, be easy to industrialized production；Modified Membrane
It is prepared using using immersion precipitation phase inversion process, preparation process is simple, and reaction condition requires low and easy to control, membrane structure appearance
Easy to control and uniform, film has lasting stability；It combines both, easy to operate, use scope is wide；
2, the synthesis of block polymer FPEG-CO-CA is that polyethylene glycol (hydrophilic) and perfluor alkane are introduced into CA structures
Base (oleophobic) segment, is modified CA by way of blending, its hydrophily is enhanced on the basis of original CA basement membranes
And oleophobic property, and be conducive to reduce cost；
3, for compared to inorganic modifier, the organic modifiers block that synthesis contains similar functional groups with basal lamina material is poly-
Object FPEG-CO-CA is closed, is conducive to improve modifying agent and the compatibility of basal lamina material in the blending process, will not fall off secondary dirt
Dye problem, extends service life；
4, modified CA filter membrane all has preferable interception capacity to HA, BSA and oil (hexadecane), especially has excellent
Oil resistant contamination resistance；
5, prevent modified fenestra from caving in by being impregnated twice to keep fenestra shape in Modified Membrane preparation process 5 of the present invention
Shrinkage；
6, time chlorine is added dropwise into round-bottomed flask in the preparation process of perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH)
Sour sodium (NaClO) and sodium chlorite (NaClO2) solution, ensure that oxidation and reduction reaction occur simultaneously, promotes reaction rate.
Description of the drawings
Fig. 1 is the FT-IR infrared spectrograms of perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH)；
Fig. 2 is the FT-IR infrared spectrograms of block polymer FPEG-CO-CA；
Fig. 3 is perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH)1H-NMR nuclear magnetic spectrograms；
Fig. 4 is block polymer FPEG-CO-CA's1H-NMR nuclear magnetic spectrograms.
Specific implementation mode
Illustrate that embodiments of the present invention, those skilled in the art can be by this explanations by particular specific embodiment below
Content disclosed by book understands other advantages and effect of the present invention easily.
A kind of preparation method of block polymer FPEG-CO-CA modified CA filter membranes, uses block polymer FPEG-CO-
CA forms a film after being modified to CA as additive, block polymer FPEG-CO-CA modified CA filter membranes is made, wherein FPEG-
CO-CA is synthesized by the following way route and is made：
Embodiment 1：
Block polymer FPEG-CO-CA modified CAs filter membrane is made by following steps：
1) perfluoroalkyl-polyethylene glycol (FPEG) is passed through and 2,2,6,6- tetramethyl piperidines nitrogen oxides (TEMPO) oxygen
Perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH) is obtained by the reaction in change；
2) cellulose acetate (CA) esterification is carried out with perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH) to synthesize
Block polymer FPEG-CO-CA；
3) it is 7 by mass ratio:It is dry that 3 cellulose acetate (CA), block polymer FPEG-CO-CA are placed in vacuum respectively
60 DEG C of dry 12h in dry case are dried solvent n,N-dimethylacetamide (DMAc) using 4A types molecular sieve；After drying
CA, FPEG-CO-CA be dissolved in by a certain percentage it is dry after DMAc in, at a temperature of 40 DEG C, with the tachogenerator of 200r/min
Tool stirs 12~36h, forms casting solution；The molecular weight of cellulose acetate (CA) is about 30000, and wherein acetyl content is
38wt%, hydroxy radical content 3wt%；
4) casting solution is cooled to room temperature, under 6000r/min rotating speeds, evacuation and centrifugal degassing 15min；
5) casting solution after deaeration is made to the hollow-fibre membrane of certain thickness plate membrane or certain wall thickness, in air
It after standing 5s, puts into coagulating bath, coagulating bath is pure water, and room temperature impregnates 2h moldings in coagulating bath；By molding film it is hyperphoric in
It impregnates to take out to be placed in 45% glycerine afterwards for 24 hours in pure water and impregnate for 24 hours；It finally takes out naturally dry, save backup, block is made
Polymer FPEG-CO-CA modified CA filter membranes.
Embodiment 2：
Block polymer FPEG-CO-CA modified CAs filter membrane is made by following steps：
1) perfluoroalkyl-polyethylene glycol (FPEG) is passed through and 2,2,6,6- tetramethyl piperidines nitrogen oxides (TEMPO) oxygen
Perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH) is obtained by the reaction in change；
2) cellulose acetate (CA) esterification is carried out with perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH) to synthesize
Block polymer FPEG-CO-CA；
3) it is 9 by mass ratio:It is dry that 1 cellulose acetate (CA), block polymer FPEG-CO-CA are placed in vacuum respectively
60 DEG C of dry 36h in dry case are dried solvent n,N-dimethylacetamide (DMAc) using 4A types molecular sieve；After drying
CA, FPEG-CO-CA be dissolved in by a certain percentage it is dry after DMAc in, at a temperature of 80 DEG C, with the tachogenerator of 500r/min
Tool stirs 36h, forms casting solution；The molecular weight of cellulose acetate (CA) is about 50000, and wherein acetyl content is 40wt%,
Hydroxy radical content is 4wt%；
4) casting solution is cooled to room temperature, under 9000r/min rotating speeds, evacuation and centrifugal degassing 15min；
5) casting solution after deaeration is made to the hollow-fibre membrane of certain thickness plate membrane or certain wall thickness, in air
It after standing 20s, puts into coagulating bath, coagulating bath is pure water, and room temperature impregnates 2h moldings in coagulating bath；Molding film is hyperphoric
It impregnates to take out to be placed in 45% glycerine afterwards for 24 hours in pure water and impregnate for 24 hours；It finally takes out naturally dry, save backup, be made embedding
Section polymer FPEG-CO-CA modified CA filter membranes.
Embodiment 3：
Block polymer FPEG-CO-CA modified CAs filter membrane is made by following steps：
1) perfluoroalkyl-polyethylene glycol (FPEG) is passed through and 2,2,6,6- tetramethyl piperidines nitrogen oxides (TEMPO) oxygen
Perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH) is obtained by the reaction in change；
2) cellulose acetate (CA) esterification is carried out with perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH) to synthesize
Block polymer FPEG-CO-CA；
3) it is 5 by mass ratio:It is dry that 1 cellulose acetate (CA), block polymer FPEG-CO-CA are placed in vacuum respectively
60 DEG C of dry 50h in dry case are dried solvent n,N-dimethylacetamide (DMAc) using 4A types molecular sieve；After drying
CA, FPEG-CO-CA be dissolved in by a certain percentage it is dry after DMAc in, at a temperature of 60 DEG C, with the tachogenerator of 380r/min
Tool stirs 25h, forms casting solution；The molecular weight of cellulose acetate (CA) is about 40000, and wherein acetyl content is 39wt%,
Hydroxy radical content is 3.5wt%.
4) casting solution is cooled to room temperature, under 8000r/min rotating speeds, evacuation and centrifugal degassing 15min；
5) casting solution after deaeration is made to the hollow-fibre membrane of certain thickness plate membrane or certain wall thickness, in air
It after standing 13s, puts into coagulating bath, coagulating bath is pure water, and room temperature impregnates 2h moldings in coagulating bath；Molding film is hyperphoric
It impregnates to take out to be placed in 45% glycerine afterwards for 24 hours in pure water and impregnate for 24 hours；It finally takes out naturally dry, save backup, be made embedding
Section polymer FPEG-CO-CA modified CA filter membranes.
Embodiment 4：
Block polymer FPEG-CO-CA modified CAs filter membrane is made by following steps：
1) perfluoroalkyl-polyethylene glycol (FPEG) is passed through and 2,2,6,6- tetramethyl piperidines nitrogen oxides (TEMPO) oxygen
Perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH) is obtained by the reaction in change；
2) cellulose acetate (CA) esterification is carried out with perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH) to synthesize
Block polymer FPEG-CO-CA；
3) it is 7 by mass ratio:3 cellulose acetate (CA), block polymer FPEG-CO-CA and additive amount is the casting
The pore-foaming agent of the 0.5wt% of film liquid gross mass is placed in 60 DEG C of dry 36h in vacuum drying chamber respectively, uses 4A type molecular sieves pair
Solvent DMAC N,N' dimethyl acetamide (DMAc) is dried；By after drying CA, FPEG-CO-CA and pore-foaming agent by a certain percentage
It is dissolved in the DMAc after drying, at a temperature of 60 DEG C, with the rotating speed mechanical agitation 12h of 200r/min, forms casting solution；It is described
Pore-foaming agent is polyethylene glycol (PEG) or polyvinylpyrrolidone (PVP)；The molecular weight of cellulose acetate (CA) is about 30000,
Wherein acetyl content is 38wt%, hydroxy radical content 3wt%；
4) casting solution is cooled to room temperature, under 6000r/min rotating speeds, evacuation and centrifugal degassing 15min；
5) casting solution after deaeration is made to the hollow-fibre membrane of certain thickness plate membrane or certain wall thickness, in air
It after standing 5s, puts into coagulating bath, coagulating bath is pure water, and room temperature impregnates 2h moldings in coagulating bath；By molding film it is hyperphoric in
It impregnates to take out to be placed in 45% glycerine afterwards for 24 hours in pure water and impregnate for 24 hours；It finally takes out naturally dry, save backup, block is made
Polymer FPEG-CO-CA modified CA filter membranes.
Embodiment 5：
Block polymer FPEG-CO-CA modified CAs filter membrane is made by following steps：
1) perfluoroalkyl-polyethylene glycol (FPEG) is passed through and 2,2,6,6- tetramethyl piperidines nitrogen oxides (TEMPO) oxygen
Perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH) is obtained by the reaction in change；
2) cellulose acetate (CA) esterification is carried out with perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH) to synthesize
Block polymer FPEG-CO-CA；
3) it is 9 by mass ratio:1 cellulose acetate (CA), block polymer FPEG-CO-CA and additive amount is the casting
The pore-foaming agent of the 20wt% of film liquid gross mass is placed in 60 DEG C of dry 36h in vacuum drying chamber respectively, uses 4A type molecular sieves pair
Solvent DMAC N,N' dimethyl acetamide (DMAc) is dried；By after drying CA, FPEG-CO-CA and pore-foaming agent by a certain percentage
It is dissolved in the DMAc after drying, at a temperature of 60 DEG C, with the rotating speed mechanical agitation 36h of 500r/min, forms casting solution；It is described
Pore-foaming agent is polyethylene glycol (PEG) or polyvinylpyrrolidone (PVP)；The molecular weight of cellulose acetate (CA) is about 50000,
Wherein acetyl content is 40wt%, hydroxy radical content 3.5%；
4) casting solution is cooled to room temperature, under 9000r/min rotating speeds, evacuation and centrifugal degassing 15min；
5) casting solution after deaeration is made to the hollow-fibre membrane of certain thickness plate membrane or certain wall thickness, in air
It after standing 20s, puts into coagulating bath, coagulating bath is pure water, and room temperature impregnates 2h moldings in coagulating bath；Molding film is hyperphoric
It impregnates to take out to be placed in 45% glycerine afterwards for 24 hours in pure water and impregnate for 24 hours；It finally takes out naturally dry, save backup, be made embedding
Section polymer FPEG-CO-CA modified CA filter membranes.
Embodiment 6：
Block polymer FPEG-CO-CA modified CAs filter membrane is made by following steps：
1) perfluoroalkyl-polyethylene glycol (FPEG) is passed through and 2,2,6,6- tetramethyl piperidines nitrogen oxides (TEMPO) oxygen
Perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH) is obtained by the reaction in change；
2) cellulose acetate (CA) esterification is carried out with perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH) to synthesize
Block polymer FPEG-CO-CA；
3) it is 5 by mass ratio:1 cellulose acetate (CA), block polymer FPEG-CO-CA and additive amount is the casting
The pore-foaming agent of the 11wt% of film liquid gross mass is placed in 60 DEG C of dry 25h in vacuum drying chamber respectively, uses 4A type molecular sieves pair
Solvent DMAC N,N' dimethyl acetamide (DMAc) is dried；By after drying CA, FPEG-CO-CA and pore-foaming agent by a certain percentage
It is dissolved in the DMAc after drying, at a temperature of 60 DEG C, with the rotating speed mechanical agitation 25h of 380r/min, forms casting solution；It is described
Pore-foaming agent is polyethylene glycol (PEG) or polyvinylpyrrolidone (PVP)；The molecular weight of cellulose acetate (CA) is about 40000,
Wherein acetyl content is 39wt%, hydroxy radical content 3.5wt%；
4) casting solution is cooled to room temperature, under 8000r/min rotating speeds, evacuation and centrifugal degassing 15min；
5) casting solution after deaeration is made to the hollow-fibre membrane of certain thickness plate membrane or certain wall thickness, in air
It after standing 13s, puts into coagulating bath, coagulating bath is pure water, and room temperature impregnates 2h moldings in coagulating bath；Molding film is hyperphoric
It impregnates to take out to be placed in 45% glycerine afterwards for 24 hours in pure water and impregnate for 24 hours；It finally takes out naturally dry, save backup, be made embedding
Section polymer FPEG-CO-CA modified CA filter membranes.
Embodiment 7：
Block polymer FPEG-CO-CA modified CAs filter membrane is made by following steps：
1) perfluoroalkyl-polyethylene glycol (FPEG) is passed through and 2,2,6,6- tetramethyl piperidines nitrogen oxides (TEMPO) oxygen
Perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH) is obtained by the reaction in change；
2) cellulose acetate (CA) esterification is carried out with perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH) to synthesize
Block polymer FPEG-CO-CA；
3) it is 9 by mass ratio:1 cellulose acetate (CA), block polymer FPEG-CO-CA and additive amount is the casting
The pore-foaming agent of the 1wt% of film liquid gross mass is placed in 60 DEG C of dry 25h in vacuum drying chamber respectively, using 4A type molecular sieves to molten
Agent DMAC N,N' dimethyl acetamide (DMAc) is dried；By after drying CA, FPEG-CO-CA and pore-foaming agent it is molten by a certain percentage
In DMAc after Xie Yu dryings, at a temperature of 60 DEG C, with the rotating speed mechanical agitation 25h of 380r/min, casting solution is formed；The cause
Hole agent is polyethylene glycol (PEG) or polyvinylpyrrolidone (PVP)；The molecular weight of cellulose acetate (CA) is about 40000,
Middle acetyl content is 39wt%, hydroxy radical content 3.5wt%；
4) casting solution is cooled to room temperature, under 8000r/min rotating speeds, evacuation and centrifugal degassing 15min；
5) casting solution after deaeration is made to the hollow-fibre membrane of certain thickness plate membrane or certain wall thickness, in air
It after standing 13s, puts into coagulating bath, coagulating bath is pure water, and room temperature impregnates 2h moldings in coagulating bath；Molding film is hyperphoric
It impregnates to take out to be placed in 45% glycerine afterwards for 24 hours in pure water and impregnate for 24 hours；It finally takes out naturally dry, save backup, be made embedding
Section polymer FPEG-CO-CA modified CA filter membranes.
Wherein, the preparation method of perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH) is in Examples 1 to 7：It will be certain
Perfluoroalkyl-polyethylene glycol (FPEG) of amount, 2,2,6,6- tetramethyl piperidines nitrogen oxides (TEMPO) and by sodium dihydrogen phosphate
(NaH2PO4)/disodium hydrogen phosphate (Na2HPO4) buffer solution that mixes pH=7 is respectively placed in round-bottomed flask, is added molten
Agent acetonitrile (CH3CN), sodium hypochlorite (NaClO) and sodium chlorite (NaClO is then added dropwise into round-bottomed flask simultaneously2) solution, drop
After adding, 3~6h of mechanical agitation at a temperature of 25~50 DEG C；After reaction, reaction product is cooled to room temperature, be added suitable
The water of amount adjusts pH to 8, and under 0 DEG C of ice-water bath, sodium thiosulfate (Na is added thereto2S2O3) after solution is quenched, then
Appropriate t-butyl methyl ether (MTBE) is added and shakes, after acquired solution layering, discards organic phase；Hydrochloric acid is added into water phase
(HCl) solution adjusts pH to 3, then will by all organic phases generated in multiple extraction process merging with more extractions of MTBE
Organic phase anhydrous magnesium sulfate (MgSO4) drying, filtering after merging, weak yellow liquid is obtained by filtrate after rotary evaporation
FPEG-COOH；
The preparation method of block polymer FPEG-CO-CA is：By a certain amount of perfluoroalkyl-polyethylene carboxylic acid
(FPEG-COOH) it is added in round-bottomed flask with cellulose acetate (CA), and is added into round-bottomed flask a certain amount of by 4- diformazans
The esterifying reagent and tetrahydrofuran (THF) solvent that yl pyridines (DMAP), dicyclohexylcarbodiimide (DCC) are constituted, 25~50
After reacting 1~3d at a temperature of DEG C, reaction solution is obtained；Reaction solution is slowly added to be settled in a certain amount of deionized water, mistake
Filter cake is collected after filter, and filter cake is dissolved in a certain amount of tetrahydrofuran (THF), is poured slowly into deionized water and is sunk again
After drop, filtering for 24 hours by filtration product freeze-drying, faint yellow solid block polymer FPEG-CO-CA is obtained.
In order to illustrate the effect of the present invention, surveyed using film surface contact angle/surface tension apparatus (Ram é-Hart 500)
Examination CA membrane modifying front and rear surfaces static contact angles are measured and are measured using film chanical strength analysis instrument (Instron 5944)
The mechanical strength (elongation and tensile stress) of film, as shown in table 1：
Table 1：
It can be seen that from the test of the contact angle of film:The water contact angle of pure additive FPEG-CO-CA (film M1) is minimum
46.9 °, oily contact angle is up to 153.6 °, and compared with pure CA (film M0), hydrophilic and oleophobic property is significantly improved.After blending
Film water contact angle and oily contact angle among M0 and M1.With the addition of block polymer FPEG-CO-CA, modified CA
The water contact angle of film is gradually reduced, and oily contact angle gradually increases, i.e., the hydrophilic performance with oleophobic of modified CA films obtains simultaneously
Raising is arrived, this is mainly due to the feature functions containing FPEG in the structure for the block polymer FPEG-CO-CA being added
Group, i.e., caused by polyethylene glycol and perfluoroalkyl segments, wherein：Polyethylene glycol segment, which plays, can improve the hydrophilic of film surface
Effect, perfluoroalkyl segments can reduce the free energy of film surface, play the oleophobic performance of enhancing film surface.
It can be seen that from the mechanical strength (including tensile stress and tensile strength) of film：Block polymer FPEG-CO-CA with
After CA is mixed, the mechanical strength of Modified Membrane is reduced, this is because the compatibility in Blending Processes between CA and additive
Caused by variation.Experiment shows film M3 (9:1) than film M2 (7:3) bad mechanical strength, still, a small amount of additive, which is added, to be had
Conducive to the manufacturing cost of reduction film.Therefore, on the basis of film M3, consider that suitable pore-foaming agent PEG or PVP is added, as a result
Display：The mechanical strength of film M4 (PEG) and M5 (PVP) are promoted, and the hydrophily of film is also improved, this is because institute
The pore-foaming agent of addition all has certain hydrophily.
In addition, using ultrafiltration cup (MSC50,50mL), under the operating pressure of 0.1MPa, pure water flux survey is carried out to film
Examination, film MO, M1, M2 and M3 are not discharged under the operating pressure of 0.1MPa, i.e., pure water flux is 0.
By to humic acid (HA) solution (a concentration of 0.02g/L), bovine serum albumin (BSA) solution (a concentration of 1g/L) with
And hexadecane lotion (i.e. oil hydrosol, a concentration of 0.1g/L) is filtered experiment, tests the anti-pollution for preparing film M4 and M5
Metachromia energy, antifouling property is mainly by relative flux attenuation rate (RFD), relative flux recovery rate (RFR) and to pollutant
Rejection (R) these three indexs characterize, as shown in table 2：
Table 2：
Table 2 can be seen that modified CA film M4 and M5 in the filtration of demineralized water experiment of preceding 30min, the stabilized flux (J of film0)
All maintain about 33L/ (m2H) left and right；
Modified Membrane M4 and M5 couples three kinds different types of pollutant HA, BSA and hexadecane all have certain interception capacity,
Wherein, it is 54% or so that Modified Membrane M4 and M5 is then relatively small to the rejection of HA, and its RFD is maximum, is since HA is easier to richness
Collection causes film surface to block on film surface, and its RFR is then higher, up to 91.2% (M5)；
Modified Membrane M4 and M5 is medium to the stain resistance of BSA；
Modified Membrane M4 and M5 is minimum to the RFD of oily (hexadecane) lotion, and RFR is relatively high, illustrates in modified film surface
Oil (hexadecane) pollution it is most of be reversible membrane fouling, after being simply cleaned by ultrasonic, be enriched in the oil droplet of film surface compared with
Easily removal；Film M4, M5 are up to 92.5% and 90.1% respectively to the rejection R of oil, illustrate that modified CA film has excellent oil resistant
Pollution capacity, this is mainly related with the surface chemistry composition of Modified Membrane, because in the contact angle test of film, the equal tables of film M4 and M5
Reveal good hydrophilic and oleophobic characteristic.Therefore, block polymer FPEG-CO-CA, which is added in CA, greatly improves CA
The contamination resistance of film.
Polymer prepared by this experiment by Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy (1H-
NMR structural analysis characterization) is carried out, Fig. 1, Fig. 2 are infrared spectrogram；Fig. 3, Fig. 4 are nuclear-magnetism figure.
As shown in Fig. 1 (FT-IR), FPEG-COOH is in wavelength 1744cm-1There is typical carbonyl peak in place, in λ
3496cm-1Place is the hydroxyl peak in carboxylic acid, illustrates the generation of oxidation product carboxylic acid, wavelength 1116,1147 and 1211,1243cm-1
Peak be polyethylene group C-O keys stretching vibration peak；
In conjunction with Fig. 3 (1H-NMR), the peak of active hydrogen (- OH) can be found at chemical shift δ 12.49ppm, it was demonstrated that product carboxylic
In acid-presence of COOH group, it was confirmed that the correctness of FPEG-COOH structures；
It is 1747cm in wavelength as shown in Fig. 2 (FT-IR)-1There is carbonyl peak, peak heights herein are apparently higher than FPEG-
Carbonyl peak (Fig. 1,1744cm in COOH-1), absorbance increases about 4 times, illustrates that-the OH in FPEG-COOH and CA occurs
The generation of esterification, and due to also containing ester carbonyl group in CA structures, the introducing of CA structural units can also enhance the strong of ester carbonyl group
Degree；In wavelength 1053cm-1The stretching vibration peak of C-O keys in the CA being predominantly introduced into；
Meanwhile from Fig. 4 (1H-NMR it can be seen that in)：The peak of active hydrogen near at chemical shift δ 12.49ppm is complete
It totally disappeared mistake, it was demonstrated that-the OH in-COOH and CA in polymer FPEG-COOH occurs esterification and generates product FPEG-CO-
CA。
Block polymer FPEG-CO-CA modified CAs filter membrane includes mainly following two step：
1, the synthesis of block polymer perfluoroalkyl-polyethylene glycol carboxylic-vinegar acid cellulose (FPEG-CO-CA)：
The molecular weight of cellulose acetate CA used in experiment is about 40000, acetyl content 39.8wt%, hydroxyl
Content is 3.5wt%, and the synthetic route of polymer FPEG-CO-CA is：It first will be in perfluoroalkyl-polyethylene glycol (FPEG)
Alcoholic extract hydroxyl group obtains perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH) through peroxidating；Recycle the hydroxyl and FPEG- in CA
Simple esterification synthesizing new polymer blocks polymer FPEG-CO-CA is carried out between carboxylic acid in COOH；
FPEG or polyethylene glycol (PEG) are often used directly to chemically react because containing hydroxyl (- OH) in its structure, such as with
Esterification occurs for carboxylic acid (- COOH), and then synthesizes the compound containing FPEG or PEG group, this research is then first by FPEG
In-OH be converted into-COOH, oxidation reaction is simple to operation, then esterification occurs between-the OH in CA to prepare block poly-
Close object additive；
Because containing a large amount of acetyl group and a small amount of hydroxyl in CA, mostly most of research is to utilize the acetyl in structure
Such as acquisition carboxylic acid first is hydrolyzed to acetyl group in base, and carboxylic acid group is recycled to carry out next step chemical reaction.And in this research
In, without carrying out any chemical treatment to CA directly using the hydroxyl in structure, enormously simplify synthetic method.
Wherein, the synthesis of perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH)：Perfluoroalkyl-polyethylene carboxylic acid
(FPEG-COOH) by perfluoralkyl surfactant (FPEG) (FSN-100) through 2,2,6,6- tetramethyl piperidine nitrogen oxygen
Compound (TEMPO) oxidation is prepared, and specific synthetic method is as follows：By a certain amount of FPEG, TEMPO and buffer solution (pH=
7) it is respectively placed in round-bottomed flask, acetonitrile (CH is added3CN it) is used as solvent, sodium hypochlorite is then added dropwise into round-bottomed flask simultaneously
(NaClO) and sodium chlorite (NaClO2) solution, after being added dropwise, by reaction system, mechanical agitation 4h, reaction are tied at 35 DEG C
Shu Hou is cooled to room temperature, suitable water is added into reaction solution, and the pH of solution is adjusted to 8, under ice-water bath, uses thiosulfuric acid
Sodium (Na2S2O3) after reaction solution is quenched in solution, appropriate t-butyl methyl ether (MTBE) is added and shakes, after solution layering,
Discard organic phase.Hydrochloric acid (HCl) solution is added into water phase, adjusts the pH to 3 of solution.It is extracted, is associated with by several times with MTBE again
Machine phase, with anhydrous magnesium sulfate (MgSO4) dry, filtering, it is weak yellow liquid FPEG- that filtrate obtains product after rotary evaporation
COOH；
The synthesis of block polymer FPEG-CO-CA：By a certain amount of FPEG-COOH and CA be added in round-bottomed flask into
Row esterification：A certain amount of 4- lutidines (DMAP) is added into round-bottomed flask and dicyclohexylcarbodiimide (DCC) is made
For esterifying reagent, tetrahydrofuran (THF) is used as solvent, reaction solution to react 3d at 25 DEG C, after reaction, reaction solution is slowly added
Enter and settled in a certain amount of deionized water, filter cake is collected after filtering, and filter cake is dissolved in a certain amount of THF, slowly
It pours into deionized water and settles again, product is obtained after filtering and be freeze-dried for 24 hours, obtain faint yellow solid, i.e. block polymerization
Object FPEG-CO-CA.
2, antipollution CA films synthesize：
Plate membrane is prepared using immersion precipitation phase inversion process (L-S methods)：First by polymer CA, block polymer FPEG-CO-
CA, pore-foaming agent etc. is placed in 60 DEG C of dryings in vacuum drying chamber, and for 24 hours, solvent n,N-dimethylacetamide (DMAc) uses 4A types point
Son sieve be dried, by after drying CA, FPEG-CO-CA and pore-foaming agent be dissolved in DMAc by a certain percentage, in 60 DEG C of temperature
Under, when rotating speed is 350r/min, mechanical agitation for 24 hours, after casting solution is cooled to room temperature, under 9000r/min rotating speeds, centrifugation is de-
15min is steeped, the casting solution after deaeration is uniformly poured on the glass plate of cleaning, drying of knifing machine, is scraped and is made centainly with scraper
The plate membrane of thickness is put into 2h in coagulating bath after standing 10s in air；Then it is impregnated in pure water molding film is hyperphoric
After for 24 hours；It takes out and is soaked in 45% glycerine and impregnate for 24 hours；It further takes out to be soaked in n-hexane and impregnate for 24 hours, finally take out certainly
It so dries, preserves for use.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology can all carry out modifications and changes to above-described embodiment without violating the spirit and scope of the present invention.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should by the present invention claim be covered.
Claims (10)
1. a kind of preparation method of block polymer FPEG-CO-CA modified CA filter membranes, which is characterized in that use block polymer
FPEG-CO-CA forms a film after being modified to CA as additive, and block polymer FPEG-CO-CA modified CA filter membranes are made,
In, FPEG-CO-CA is synthesized by the following way route and is made：
2. the preparation method of block polymer FPEG-CO-CA modified CA filter membranes according to claim 1, which is characterized in that
It is made by following steps：
1) perfluoroalkyl-polyethylene glycol (FPEG) is anti-by being aoxidized with 2,2,6,6- tetramethyl piperidines nitrogen oxides (TEMPO)
It should obtain perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH)；
2) cellulose acetate (CA) is subjected to esterification with perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH) and synthesizes block
Polymer FPEG-CO-CA；
3) by cellulose acetate (CA), block polymer FPEG-CO-CA be placed in respectively 60 DEG C of dryings 12 in vacuum drying chamber~
36h is dried solvent n,N-dimethylacetamide (DMAc) using 4A types molecular sieve；By CA, FPEG-CO- after drying
CA is dissolved in by a certain percentage in the DMAc after drying, at a temperature of 40~80 DEG C, is stirred with the rotating speed machinery of 200~500r/min
12~36h is mixed, casting solution is formed；
4) casting solution is cooled to room temperature, under 6000~9000r/min rotating speeds, evacuation and centrifugal degassing 15min；
5) casting solution after deaeration is made to the hollow-fibre membrane of certain thickness plate membrane or certain wall thickness, is stood in air
It after 5~20s, puts into coagulating bath, coagulating bath is pure water, and room temperature impregnates 2h moldings in coagulating bath；By molding film it is hyperphoric in
It impregnates to take out to be placed in 45% glycerine afterwards for 24 hours in pure water and impregnate for 24 hours；It finally takes out naturally dry, save backup, block is made
Polymer FPEG-CO-CA modified CA filter membranes.
3. the preparation method of block polymer FPEG-CO-CA modified CA filter membranes according to claim 2, which is characterized in that
The mass ratio of CA and FPEG-CO-CA is 7:3~9:1.
4. the preparation method of block polymer FPEG-CO-CA modified CA filter membranes according to claim 2, which is characterized in that
Step 3) is that cellulose acetate (CA), block polymer FPEG-CO-CA and pore-foaming agent are placed in respectively 60 in vacuum drying chamber
DEG C dry 12~36h, is dried solvent n,N-dimethylacetamide (DMAc) using 4A types molecular sieve；After drying
CA, FPEG-CO-CA and pore-foaming agent are dissolved in by a certain percentage in the DMAc after drying, at a temperature of 60 DEG C, with 200~500r/
Rotating speed 12~36h of mechanical agitation of min forms casting solution.
5. the preparation method of block polymer FPEG-CO-CA modified CA filter membranes according to claim 4, which is characterized in that
The pore-foaming agent is polyethylene glycol (PEG) or polyvinylpyrrolidone (PVP).
6. the preparation method of block polymer FPEG-CO-CA modified CA filter membranes according to claim 5, which is characterized in that
CA, FPEG-CO-CA mass ratio are 7:3~9:1, pore-foaming agent additive amount is 0.5~20wt% of the casting solution gross mass.
7. according to the preparation method of claim 1~6 any one of them block polymer FPEG-CO-CA modified CA filter membranes,
It is characterized in that, the preparation method of perfluoroalkyl-polyethylene carboxylic acid (FPEG-COOH) is：By the poly- second of a certain amount of perfluoroalkyl-
Glycol (FPEG), 2,2,6,6- tetramethyl piperidines nitrogen oxides (TEMPO) and by sodium dihydrogen phosphate (NaH2PO4)/disodium hydrogen phosphate
(Na2HPO4) buffer solution that mixes pH=7 is respectively placed in round-bottomed flask, solvent acetonitrile (CH is added3CN), then together
When sodium hypochlorite (NaClO) and sodium chlorite (NaClO is added dropwise into round-bottomed flask2) solution, after being added dropwise, at 25~50 DEG C
At a temperature of 3~6h of mechanical agitation；After reaction, reaction product is cooled to room temperature, suitable water is added, adjust pH to 8,
Under 0 DEG C of ice-water bath, sodium thiosulfate (Na is added thereto2S2O3) after solution is quenched, add appropriate t-butyl methyl ether
(MTBE) it and shakes, after acquired solution layering, discards organic phase；Hydrochloric acid (HCl) solution is added into water phase, adjusts pH to 3,
Again with more times of MTBE extractions, all organic phases generated in multiple extraction process are merged, by the organic phase after merging with anhydrous
Magnesium sulfate (MgSO4) dry, filtering, filtrate is obtained to weak yellow liquid FPEG-COOH after rotary evaporation.
8. block polymer FPEG-CO-CA modified CA filter membranes according to claim 7 and preparation method thereof, feature
It is, the preparation method of block polymer FPEG-CO-CA is：By a certain amount of perfluoroalkyl-polyethylene carboxylic acid (FPEG-
COOH it) is added in round-bottomed flask with cellulose acetate (CA), and is added into round-bottomed flask a certain amount of by 4- lutidines
(DMAP), the esterifying reagent and tetrahydrofuran (THF) solvent that dicyclohexylcarbodiimide (DCC) is constituted, in 25~50 DEG C of temperature
After 1~3d of lower reaction, reaction solution is obtained；Reaction solution is slowly added to be settled in a certain amount of deionized water, filter after receive
Collect filter cake, and filter cake is dissolved in a certain amount of tetrahydrofuran (THF), is poured slowly into deionized water and settles, filter again
Afterwards for 24 hours by filtration product freeze-drying, faint yellow solid block polymer FPEG-CO-CA is obtained.
9. according to claim 1~6, the preparation method of 8 any one of them block polymer FPEG-CO-CA modified CA filter membranes,
It is characterized in that, the molecular weight 30000~50000 of cellulose acetate (CA), wherein acetyl content are 38~40wt%, hydroxyl
Content is 3~4wt%.
10. a kind of block polymer FPEG-CO-CA modified CA filter membranes, which is characterized in that pass through any one of claim 1~9
The preparation method is made.
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| CN115155335B (en) * | 2022-06-09 | 2023-12-15 | 苏州科技大学 | FPEOAA/UiO-66-NH 2 MOF (metal oxide fiber) film of PEI (polyethylene terephthalate) modified PVDF (polyvinylidene fluoride) and preparation method thereof |
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