CN106632922B - The method of the preparation method and its modified polyvinilidene fluoride microfiltration membranes of block polymer containing hydrophilic segment - Google Patents
The method of the preparation method and its modified polyvinilidene fluoride microfiltration membranes of block polymer containing hydrophilic segment Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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Abstract
The method for the block polymer modified polyvinilidene fluoride microfiltration membranes containing hydrophilic segment that the present invention provides a kind of comprising following steps: Step 1: polyvinylidene fluoride microporous filtering film is impregnated 1~100 minute in modifier solution；Step 2: the polyvinylidene fluoride microporous filtering film after immersion is irradiated 1~48 hour under ultraviolet light, washs to remove uncrosslinked block polymer, obtain the polyvinylidene fluoride microporous filtering film of hydrophilic modifying.The modifying process of hydrophilic modifying PVDF microfiltration membranes of the invention is easy to operate, and there is the Modified Membrane obtained good stability and good hydrophily and antifouling property therefore can be widely applied to the every field such as food industry, water process and environmental protection.
Description
Technical field
The invention belongs to polymeric film material fields, in particular to a kind of micro- by block polymer modified polyvinilidene fluoride
The method of filter membrane.
Background technique
Micro-filtration is also known as micro porous filtration, in the case where certain pressure pushes, is retained in solution using miillpore filter as filter medium
Some solid particles, drop or other biologic grains etc., and a large amount of solvents, small molecule and a small amount of macromolecular solute can penetrate
The separation process of film.In the subtractive process of water, micro-filter technology can remove bacterium and solid impurity, can be used for medicine, beverage
With the production of water.In the preparation of electronics industry ultrapure water, micro-filtration can be used for ultrafiltration and the pretreatment of reverse osmosis process and product
Terminal security personnel's filtering.Micro-filter technology also can be used for the filtering of the various drinks such as beer, yellow rice wine, to remove yeast therein, mould
With other microorganisms, product is clarified, and extends storage period.It includes oiliness sewage treatment that micro-filter technology, which can be used for sewage treatment,
Etc..Micro-filter technology is also widely used in fields such as drug degerming, biological detections.
The main component for realizing micro-filtration operation is membrane material.Wherein Kynoar (PVDF) is a kind of for UF membrane skill
The excellent polymeric film material of art, it has good chemical stability, heat resistance and mechanical stability.But the surface of PVDF
Can be very low, hydrophobicity is very strong, therefore is highly susceptible to pollute, and so as to cause membrane flux rapid decay, film reduced service life is simultaneously
And operating cost is increased, it is limited in the application in UF membrane field.And dirt can be reduced by improving membrane material surface hydrophilicity
Object is contaminated in the absorption of film surface, is a kind of important method for solving pvdf membrane pollution, is also become the research of researcher's recent years
Hot spot.Currently, the method to pvdf membrane hydrophilic modifying mainly has chemical method and physical method two major classes.Wherein, chemical method
Including direct surface processing and surface grafting etc..Physical method has physical blending and surface coating etc..
Direct surface processing is to be handled using strong acid, highly basic, strong oxidizer or plasma etc. film surface, in film
Surface generates the hydrophilic polars functional groups such as hydroxyl, carboxyl, amino and peroxy-radical, improves film to a certain extent to the affine of water
Property.Such as Chinese patent CN 102179189 A of 103831027 A and CN, using plasma technology is to polyvinylidene fluoride film
It is chemically modified and is modified, by increasing film surface hydrophilic radical number and optimizing the distribution of hydrophilic radical, to improve and change
The hydrophily of kind film surface, and then achieve the purpose that improve film antifouling property.But this method is hydrophilic in enhancing film
Meanwhile membrane body performance and membrane structure may be made to be destroyed to a certain extent, and the parent that this processing method illustrates
Water base group is smaller, is easy to migrate with polymer segment movement to membrane body, becomes modified effect slowly in use
Difference.
The method of surface grafting is to introduce hydrophilic radical in film surface by way of Covalent bonding together.Generally first with table
The methods of face chemical treatment, corona treatment, gamma-ray irradiation or UV irradiation first introduce active reaction point in film surface, then
Hydrophilic radical is introduced by the method for grafting to improve the hydrophilicity of film.101293184 A of Chinese patent CN passes through gamma-rays
Radiation grafted method introduces acrylate copolymer in PVDF doughnut membrane aperture and film surface, makes the hydrophily and anti-pollution of film
Dye ability is significantly improved.Pvdf membrane is placed in plasma by 103831024 A of Chinese patent CN to be pre-processed,
Then the reaction of surface grafting acrylic acid is carried out, and it is molten that the modified pvdf membrane in polyacrylic acid surface is placed in polyanion electrolyte
It is adsorbed in liquid, polycation electrolyte solution or zwitterionic betaines quasi polymer solution, obtains that there is charged surface
And its outermost surface is the polyvinylidene fluoride porous film of electronegativity, electropositivity or electroneutral.Have obtained by final charged more
The polyvinylidene fluoride separation membrane on sample surface shows preferable antifouling property.103962011 A of Chinese patent CN will be dredged
Water PVDF seperation film is placed in progress plasma discharge processing in plasma processing apparatus, and film surface is made to generate hydroxyl isoreactivity
Group site recycles the orientation reaction of PEG and TMC high activity functional group, realizes the effective chemical graft of film surface.Final gained
The antifouling property of modified PVDF membrane significantly improves.Although hydrophilic radical can be passed through chemical method key by the method for surface grafting
It closes in film surface, but condition needed for grafting process is relative complex, generally requires multi step strategy.And grafting site may it is uneven or
Person's negligible amounts, to influence the performance of final Modified Membrane.
Physical blending can be completed in film-forming process, be a kind of method being easily achieved.Through frequently with inorganic nano-particle
Son, polyvinyl alcohol or amphipathic nature block polymer etc. and film base material blending and modifying, to improve the hydrophilicity of film and resist
Pollutant performance.102350232 A of Chinese patent CN is blended that preparation good hydrophilic property, resistance tocrocking are strong to be total to by polysulfones and with PVDF
Mixed micro-filtration flat sheet membrane, product good hydrophilic property, contamination resistance are strong.103127839 A of Chinese patent CN, by different nanoparticles
Son mixing is added in casting solution, prepares PVDF blend film using phase inversion.Pvdf membrane is significantly improved using the method
Contamination resistance.Film forming is blended in amphipathic copolymer and PVDF by 103007787 A of Chinese patent CN, preparation it is amphipathic total
Polymerized pvdf membrane product has the characteristics that permanent hydrophilic, antifouling property are excellent.104174304 A of Chinese patent CN
Film forming is blended with PVDF for chitosan and alkylated chitosan respectively with 104190267 A of CN, effectively increases PVDF seperation film
Hydrophily and antifouling property.104437121 A of Chinese patent CN is blended using block copolymer PEO-b-PMMA and PVDF
Film forming is blended film surface in PVDF and increases block copolymer PEO-b-PMMA, effectively raises the hydrophily of PVDF blend film,
The antifouling property for enhancing film solves tradition and the technical problem that the decline of membrane flux is fast, service life is short is blended.Although above-mentioned special
Modifying agent used in benefit and PVDF are blended the hydrophily and contamination resistance that can effectively improve polymer film, however additive and poly-
It is to have to the problem of facing that it is less, which to close the distribution of the compatibility and modifying agent of object matrix on surface,.
Surface coating be a kind of raising film surface hydrophily technology that comparison is easy, mainly by by modifying agent dispersion or it is molten
Solution is applied to film surface afterwards in a solvent to obtain the polymer film that surface has modifying agent coating.Modifying agent used can be height
Molecularly Imprinted Polymer is also possible to inorganic nano-particle.Chinese patent CN 102166485A uses TiO2Nano particle passes through physics
It is carried out dynamic membrane modifying coated on PVDF hollow fiber form micro-filtration film surface by effect, is declined so as to improve PVDF doughnut
The hydrophily and contamination resistance of filter membrane, the results showed that the Dynamic Membrane has lower fouling membrane rate of rise.But this method
It is faced with TiO2Nano particle is combined with the surface insecure, the problems such as being easy to fall off and modified effect is caused to fade away.
In conclusion the existing method for pvdf membrane hydrophilic modifying is unstable there are effect or duration is bad etc. asks
Topic.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of improvement PVDF microfiltration membranes are hydrophilic
Property method, by directly coating the modifying agent of Photocrosslinkable in PVDF micro-filtration film surface to form coating, then using ultraviolet
Light irradiation, crosslinks coating, and then fix its structure, to realize the hydrophilic modifying to PVDF microfiltration membranes.
It is a still further object of the present invention to provide a kind of for being modified the modifying agent of PVDF microfiltration membranes, the modifying agent be containing
The block polymer of hydrophilic segment, can be carried out photo-crosslinking.
It is a still further object of the present invention to provide a kind of preparation methods of block polymer containing hydrophilic segment.
In order to achieve the above objects and other related objects, the present invention provides a kind of block polymer containing hydrophilic segment and changes
The method of property polyvinylidene fluoride microporous filtering film comprising following steps:
Step 1: polyvinylidene fluoride microporous filtering film is impregnated 1~100 minute in modifier solution；
Step 2: the polyvinylidene fluoride microporous filtering film after immersion is irradiated 1~48 hour under ultraviolet light, wash to remove not
The block polymer of crosslinking obtains the polyvinylidene fluoride microporous filtering film of hydrophilic modifying；
Wherein, the modifying agent is by Formulas I structural unit and Formula II structural unit or Formulas I structural unit and formula III structure
The block polymer containing hydrophilic segment of unit composition:
Wherein, R1 is hydrogen atom or methyl, and R2 is the acylated acrylatoalkoxysilanes ester of cortex cinnamomi, and R3 is hydrogen atom or methyl,
R4 is the Arrcostab containing methoxyl group and ethyoxyl；N is integer in formula III structure.
Preferably, in step 1, the modifier solution solvent for use is tetrahydrofuran, dioxane, acetone, benzene first
One of ether, methylene chloride or chloroform, the mass concentration of the modifier solution are 1~25%；Tetrahydro is used in step 2
One of furans, dioxane, acetone, methyl phenyl ethers anisole, methylene chloride or chloroform wash polyvinylidene fluoride microporous filtering film to remove not
The block polymer of crosslinking.
Preferably, in step 2, the ultraviolet light is the ultraviolet light that commercial ultraviolet lamp issues, and the ultraviolet lamp power is 30
Watt~1000 watts.
Preferably, the polyvinylidene fluoride microporous filtering film aperture is 0.1~10 μm, with a thickness of 10~200 μm, porosity 10
~80%.
A kind of block polymer containing hydrophilic segment, structural formula are as follows:
The block polymer containing hydrophilic segment is by Formulas I structural unit and Formula II structural unit or Formulas I structure list
The block polymer of member and formula III structural unit composition；
Wherein, R1 is hydrogen atom or methyl, and R2 is the acylated acrylatoalkoxysilanes ester of cortex cinnamomi, and R3 is hydrogen atom or methyl,
R4 is the Arrcostab containing methoxyl group and ethyoxyl；The integer that n is 0~500 in formula III structure.
Preferably, in the Formulas I structural unit, R2 is the hydroxyethyl methacrylate that cortex cinnamomi is acylated or cortex cinnamomi is acylated third
One of olefin(e) acid hydroxyl ethyl ester.
Preferably, in the Formula II structural unit, R4 is 2- ihethoxyethyl methacrylate or 2- (2- methoxyl group second
One of oxygroup) ethylmethyl acrylate.
Preferably, the formula III structural unit be MPEG200, MPEG400, MPEG500, MPEG700, MPEG1000,
One of MPEG1500, MPEG2000, MPEG5000, MPEG10000 or MPEG20000.
Preferably, Formulas I and the number of Formula II structural unit are 1~500.
A kind of preparation method preparing the above-mentioned block polymer containing hydrophilic segment, it is poly- by atom transferred free radical
Conjunction method is prepared.
Specifically includes the following steps:
Step 1) prepares the brominated macromole evocating agent generated by Formula II structural unit or the polymerization of formula III structural unit；
Macromolecular initiation made from hydroxyethyl methacrylate, step 1) is added in step 2) in the round-bottomed flask of 100ml
Reaction system stirring and dissolving is led to argon gas Gu and steeped 30 minutes by agent and 2,2'- bipyridyl and solvent, then deoxygenation, then by reactant
System is transferred in the round-bottomed flask of the 100ml equipped with cuprous bromide, and in 50 DEG C of progress polymerization reaction 8h, reaction product is deposited in second
It in ether, is deposited in ether and is repeated twice again after methanol dissolution, be then dried in vacuo under the conditions of 40 DEG C for 24 hours to constant weight,
Obtain poly- Formula II structural unit-b- poly hydroxy ethyl acrylate block polymer or the poly- methyl-prop of poly- formula III structural unit-b-
Olefin(e) acid hydroxyl ethyl ester block polymer；
Block polymer, 50mL pyridine made from step 2) is added in step 3) in the round-bottomed flask of 100ml, stirs molten
Depolymerize object, and cinnamoyl chloride is added under condition of ice bath, is stirred to react at room temperature for 24 hours, and reaction product precipitates in methyl alcohol,
It precipitates in methyl alcohol and is repeated twice again after chloroform dissolution, be then dried in vacuo under the conditions of 40 DEG C for 24 hours to constant weight, obtain meat
The acylated poly- Formula II structural unit-b- poly hydroxy ethyl acrylate block polymer in osmanthus or the poly- first of poly- formula III structural unit-b-
Base hydroxy-ethyl acrylate block polymer.
The present invention, which uses to have, can be carried out photo-crosslinking and the block polymer containing hydrophilic segment for modifying agent, by it
It is directly coated on PVDF micro-filtration film surface and forms coating, then fix its knot using ultraviolet light crosslinked block polymer coating
Structure, to realize the hydrophilic modifying to PVDF microfiltration membranes.
As described above, the side of the block polymer modified polyvinilidene fluoride microfiltration membranes disclosed by the invention containing hydrophilic segment
Method has the advantages that
(1) block polymer containing hydrophilic segment used in the present invention can make coating stable after ultraviolet light cross-linking
Ground is attached to PVDF micro-filtration film surface, to increase the stability of coating, has gained hydrophilic modifying PVDF microfiltration membranes fine
Durability；
(2) block polymer of the invention containing hydrophilic segment can assign PVDF microfiltration membranes good hydrophilicity,
Since hydrophilic polymeric segment has the ability of anti-organic contamination, it is thus possible to improve the antifouling property of PVDF microfiltration membranes；
(3) modifying process of hydrophilic modifying PVDF microfiltration membranes of the invention is easy to operate, and the Modified Membrane obtained has very
Therefore good stability and good hydrophily and antifouling property can be widely applied to food industry, water process and environmental protection
Etc. every field.
Specific embodiment
Embodiments of the present invention are illustrated by particular specific embodiment below, those skilled in the art can be by this explanation
Content disclosed by book is understood other advantages and efficacy of the present invention easily.
Embodiment 1
A kind of preparation method can be carried out photo-crosslinking and the block polymer containing hydrophilic segment, including following step
It is rapid:
15.77g 2- ihethoxyethyl methacrylate, 0.268g2- bromine isobutyl are added in the round-bottomed flask of 100ml
Reaction system stirring and dissolving is led to argon gas Gu by sour mono methoxy glycol ester, 0.376g 2,2'- bipyridyl and 13ml methyl phenyl ethers anisole
Reaction system, is then transferred in the round-bottomed flask of the 100ml equipped with 0.172g cuprous bromide by bubble 30 minutes, then deoxygenation,
70 DEG C of progress polymerization reaction 5h, reaction product are crossed neutral alumina pillar and then are deposited in ether, four after being diluted with methyl phenyl ethers anisole
It is deposited in ether and is repeated twice again after the dissolution of hydrogen furans, be then dried in vacuo for 24 hours to constant weight, obtain under the conditions of 40 DEG C
The brominated poly- 2- ihethoxyethyl methacrylate macromole evocating agent in end, chain length is about 100.
The brominated poly- 2- methoxy in addition 7.82g hydroxyethyl methacrylate, the end 13.14g in the round-bottomed flask of 100ml
Base ethylmethyl acrylate macromole evocating agent, 0.313g 2,2'- bipyridyl and 20ml N, dinethylformamide, will be anti-
System stirring and dissolving is answered, leads to argon gas Gu and steeps 30 minutes, then deoxygenation, then reaction system is transferred to equipped with 0.143g cuprous bromide
100ml round-bottomed flask in, in 50 DEG C of progress polymerization reaction 8h, reaction product is deposited in ether, methanol dissolution after again
It is deposited in ether and is repeated twice, be then dried in vacuo under the conditions of 40 DEG C for 24 hours to constant weight, obtain poly- 2- methoxy ethyl first
Base acrylate-b- poly hydroxy ethyl acrylate block polymer, poly hydroxy ethyl acrylate chain length is about 50.
15.15g 2- ihethoxyethyl methacrylate-b- polymethylacrylic acid is added in the round-bottomed flask of 100ml
Methyl esters block polymer, 50mL pyridine, stirring and dissolving polymer 7.51g cinnamoyl chloride are added under condition of ice bath, in room temperature condition
Under be stirred to react for 24 hours, reaction product precipitates in methyl alcohol, precipitates in methyl alcohol and is repeated twice again after chloroform dissolution, then
It is dried in vacuo under the conditions of 40 DEG C for 24 hours to constant weight, obtains the acylated poly- first of poly- 2- ihethoxyethyl methacrylate-b- of cortex cinnamomi
Base hydroxy-ethyl acrylate block polymer.
A kind of method that PVDF micro-filtration is film hydrophilically modified, is realized by following steps:
The above-mentioned block polymer of 0.5g is dissolved in 20mL methyl phenyl ethers anisole.The PVDF micro-filtration for being 0.22 μm by aperture specification
Film impregnates 1 minute in copolymer solution.It drains to place it under 500 watts of ultraviolet lamps after solution and irradiate 1 hour.Then by spoke
According to treated, film removes uncrosslinked block polymer with methyl phenyl ethers anisole washing by soaking three times, and the PVDF of hydrophilic modifying can be obtained
Microfiltration membranes.
Embodiment 2
A kind of preparation method can be carried out photo-crosslinking and the block polymer containing hydrophilic segment, including following step
It is rapid:
The dry PEG5000 of 20.1g is dispersed in 100ml anhydrous methylene chloride, 0.51g pyridine is added, in ice-water bath
Under the conditions of instill 1.09g 2- bromine isobutyl acylbromide.Then cancellation ice-water bath is warming up to naturally by reaction system reacts under room temperature
Then 4h is successively washed with 0.1mol/L sodium hydroxide, 0.1mol/L hydrochloric acid solution, saturated sodium-chloride water solution.It is organic
It is deposited in ether after being mutually concentrated, repeats washing of precipitate twice, vacuum drying obtains brominated PEG macromole evocating agent.
The brominated PEG macromolecular of 7.85g hydroxyethyl methacrylate, 5.01g is added in the round-bottomed flask of 100ml to cause
Reaction system stirring and dissolving is led to argon gas Gu and steeped 30 minutes by agent, 0.315g 2,2'- bipyridyl and 15ml methanol, then deoxygenation, so
Reaction system is transferred to afterwards in the round-bottomed flask of the 100ml equipped with 0.145g cuprous bromide, in 50 DEG C of progress polymerization reaction 8h,
Reaction product is deposited in ether, is deposited in ether and is repeated twice again after methanol dissolution, then true under the conditions of 40 DEG C
Sky is dry for 24 hours to constant weight, obtains PEG5000-b- poly hydroxy ethyl acrylate block polymer, poly hydroxy ethyl acrylate
Chain length is about 50.
10.15g 2- ihethoxyethyl methacrylate-b- polymethylacrylic acid is added in the round-bottomed flask of 100ml
Methyl esters block polymer, 50mL pyridine, stirring and dissolving polymer 7.35g cinnamoyl chloride are added under condition of ice bath, in room temperature condition
Under be stirred to react for 24 hours, reaction product precipitates in methyl alcohol, precipitates in methyl alcohol and is repeated twice again after chloroform dissolution, then
It is dried in vacuo under the conditions of 40 DEG C for 24 hours to constant weight, obtains the acylated PEG5000-b- poly hydroxy ethyl acrylate block of cortex cinnamomi
Polymer.
A kind of method that PVDF micro-filtration is film hydrophilically modified, is realized by following steps:
The above-mentioned prepared block polymer of 0.5g is dissolved in 20mL methyl phenyl ethers anisole.It is 0.22 μm by aperture specification
PVDF microfiltration membranes are impregnated 1 minute in copolymer solution.It drains to place it under 500 watts of ultraviolet lamps after solution and irradiate 1 hour.
Then the film after radiation treatment is removed into uncrosslinked block polymer with methyl phenyl ethers anisole washing by soaking three times, hydrophilic change can be obtained
The PVDF microfiltration membranes of property.
Embodiment 3
A kind of method that PVDF micro-filtration is film hydrophilically modified, is realized by following steps:
Block polymer prepared by 2g embodiment 1 is dissolved in 20mL methyl phenyl ethers anisole.It is 0.22 μm by aperture specification
PVDF microfiltration membranes are impregnated 1 minute in copolymer solution.It drains to place it under 500 watts of ultraviolet lamps after solution and irradiate 1 hour.
Then the film after radiation treatment is removed into uncrosslinked block polymer with methyl phenyl ethers anisole washing by soaking three times, hydrophilic change can be obtained
The PVDF microfiltration membranes of property.
Embodiment 4
A kind of method that PVDF micro-filtration is film hydrophilically modified, is realized by following steps:
Block polymer prepared by 5g embodiment 1 is dissolved in 20mL methyl phenyl ethers anisole.It is 0.22 μm by aperture specification
PVDF microfiltration membranes are impregnated 30 minutes in copolymer solution.Drain that irradiation 1 under 500 watts of ultraviolet lamps is placed it in after solution is small
When.Then the film after radiation treatment is removed into uncrosslinked block polymer with methyl phenyl ethers anisole washing by soaking three times, parent can be obtained
The modified PVDF microfiltration membranes of water.
Embodiment 5
A kind of method that PVDF micro-filtration is film hydrophilically modified, is realized by following steps:
Block polymer prepared by 1g embodiment 1 is dissolved in 20mL methyl phenyl ethers anisole.It is 0.22 μm by aperture specification
PVDF microfiltration membranes are impregnated 60 minutes in copolymer solution.Drain that irradiation 24 under 30 watts of ultraviolet lamps is placed it in after solution is small
When.Then the film after radiation treatment is removed into uncrosslinked block polymer with methyl phenyl ethers anisole washing by soaking three times, parent can be obtained
The modified PVDF microfiltration membranes of water.
Embodiment 6
A kind of method that PVDF micro-filtration is film hydrophilically modified, is realized by following steps:
Block polymer prepared by 2g embodiment 2 is dissolved in 20mL methyl phenyl ethers anisole.It is 0.22 μm by aperture specification
PVDF microfiltration membranes are impregnated 1 minute in copolymer solution.It drains to place it under 500 watts of ultraviolet lamps after solution and irradiate 1 hour.
Then the film after radiation treatment is removed into uncrosslinked block polymer with methyl phenyl ethers anisole washing by soaking three times, hydrophilic change can be obtained
The PVDF microfiltration membranes of property.
Embodiment 7
A kind of method that PVDF micro-filtration is film hydrophilically modified, is realized by following steps:
Block polymer prepared by 5g embodiment 2 is dissolved in 20mL methyl phenyl ethers anisole.It is 0.22 μm by aperture specification
PVDF microfiltration membranes are impregnated 30 minutes in copolymer solution.Drain that irradiation 1 under 500 watts of ultraviolet lamps is placed it in after solution is small
When.Then the film after radiation treatment is removed into uncrosslinked block polymer with methyl phenyl ethers anisole washing by soaking three times, parent can be obtained
The modified PVDF microfiltration membranes of water.
Embodiment 8
A kind of method that PVDF micro-filtration is film hydrophilically modified, is realized by following steps:
Block polymer prepared by 3g embodiment 2 is dissolved in 20mL methyl phenyl ethers anisole.It is 0.22 μm by aperture specification
PVDF microfiltration membranes are impregnated 10 minutes in copolymer solution.Drain that irradiation 24 under 30 watts of ultraviolet lamps is placed it in after solution is small
When.Then the film after radiation treatment is removed into uncrosslinked block polymer with methyl phenyl ethers anisole washing by soaking three times, parent can be obtained
The modified PVDF microfiltration membranes of water.
The hydrophilic modifying PVDF microfiltration membranes that embodiment is prepared are tested for the property below.Test method is as follows:
Membrane flux test:
Deionization is poured into ultrafiltration cup, the precompressed 30min under the pressurization of 0.1mpa nitrogen then calculates 100mL penetrating fluid
Time used calculates membrane flux.
Rejection test:
The BSA solution of 1000ppm is poured into ultrafiltration cup, then the precompressed 30min under the pressurization of 0.1mpa nitrogen is collected and seeped
Transparent liquid surveys its concentration with ultraviolet specrophotometer, calculates infiltration front and back concentration rejection.
Recovery rate test:
Film is polluted by bovine serum albumin, after then cleaning using sodium hypochlorite, calculates the recovery rate of membrane flux.
Water contact angle test:
Hydrolysis feeler is measured 10 points on a membrane sample using contact angle measurement and is averaged using drop method test of lying
The water contact angle of film surface after the method for value characterizes before modified.
Underwater oil contact angle test:
Film is immersed under water, oily contact angle is tested using underwater oil drop method, using contact angle measurement in a membrane sample
The water contact angle of film surface after the method that 10 points of surface measurements are averaged characterizes before modified.
The performance for the hydrophilic modifying PVDF microfiltration membranes that embodiment 1 to 8 is prepared is as shown in the table:
Table 1: the performance of the made PVDF microfiltration membranes of embodiment 1 to 8:
Above-described embodiment 1 to 8 is hydrophilic modifying PVDF microfiltration membranes, and comparative example is unmodified PVDF microfiltration membranes, can be seen
Out, hydrophilic modifying PVDF microfiltration membranes of the invention membrane flux and in terms of be substantially better than unmodified pvdf membrane.
In addition, PVDF microfiltration membranes service life obtained by embodiment 1 to 8 is considerably longer than comparative example under equal conditions.
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 all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.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 be covered by the claims of the present invention.
The invention belongs to polymeric film material fields, and in particular to one kind can be carried out photo-crosslinking and contain hydrophilic segment
Block polymer, and by the modified vinylidene microfiltration membranes of the block polymer to improve its hydrophilic and antifouling property side
Method.
The shortcomings that in order to overcome existing PVDF microfiltration membranes hydrophilic modification method and deficiency, the primary purpose of the present invention is that mentioning
It can be carried out photo-crosslinking and containing the block polymer of hydrophilic segment for a kind of.
It can be carried out photo-crosslinking and containing the block polymerization of hydrophilic segment another object of the present invention is to provide above-mentioned
The preparation method of object.
A further object of the present invention is to provide a kind of methods that PVDF micro-filtration is film hydrophilically modified, are handed over by the above-mentioned light that can be carried out
The connection reaction and block polymer coating containing hydrophilic segment in film surface and carries out photo-crosslinking and obtains.
The purpose of the invention is achieved by the following technical solution:
It is a kind of to can be carried out photo-crosslinking and the block polymer containing hydrophilic segment, it is by Formulas I and Formula II structural unit
The block polymer of block polymer or Formulas I structural unit and the formula III composition of composition；Wherein, Formulas I and Formula II structural unit
Number be 1-500；The number of Formula II structural unit is 1-500；The numerical value of n is 0-500 in formula III structure；
In Formulas I, R1 is hydrogen atom or methyl, and R2 is the acylated acrylatoalkoxysilanes ester of cortex cinnamomi, the acylated acyloxy of cortex cinnamomi
Alkoxy ester can make to be crosslinked between polymer molecule under ultraviolet light；
Preferably, Formulas I structural unit is the acylated hydroxyethyl methacrylate of cortex cinnamomi, the acylated hydroxy-ethyl acrylate of cortex cinnamomi
One of；
In Formula II, R3 is hydrogen atom or methyl, and R4 is the Arrcostab containing methoxyl group and ethyoxyl, can assign polymer
Hydrophilicity；
Preferably, Formula II structural unit is 2- ihethoxyethyl methacrylate, 2- (2- methoxy ethoxy) ethyl
One of methacrylate；
Formula III is mono methoxy polyethylene glycol quasi polymer (MPEG), has excellent hydrophilicity；
Preferably, formula III MPEG200, MPEG400, MPEG500, MPEG700, MPEG1000, MPEG1500,
One of MPEG2000, MPEG5000, MPEG10000, MPEG20000.
It is above-mentioned to can be carried out photo-crosslinking and block polymer containing hydrophilic segment be by atom transfer freedom
Base polymerization is prepared.
A kind of method that PVDF micro-filtration is film hydrophilically modified can be carried out photo-crosslinking and containing the embedding of hydrophilic segment by above-mentioned
Section polymer is realized by following steps:
(1) PVDF microfiltration membranes are impregnated 1-100 minutes in copolymer solution；
(2) the PVDF microfiltration membranes after immersion are irradiated 1-48 hours under ultraviolet light, removes uncrosslinked block polymer
The PVDF microfiltration membranes of hydrophilic modifying are obtained afterwards；
PVDF micro-filtration membrane aperture described in step (1) is 0.1-10 μm, with a thickness of 10-200 μm, porosity 10-80%；
The mass concentration of the polymer solution is 1-25%, and solvent is tetrahydrofuran, dioxane, acetone, benzene first
One of ether, methylene chloride, chloroform；
Step (2) described ultraviolet light can use the ultraviolet light that commercial ultraviolet lamp issues, and the power of ultraviolet lamp tube can be
30 watts -1000 watts；
It is described remove uncrosslinked block polymer be using the method for solvent washing, solvent used be tetrahydrofuran,
One of dioxane, acetone, methyl phenyl ethers anisole, methylene chloride, chloroform；
The principle of the present invention is: using with can be carried out photo-crosslinking and block polymer containing hydrophilic segment to change
Property agent form coating in PVDF micro-filtration film surface using the method directly coated, it is then poly- using ultraviolet light crosslinked block
It closes object coating and fixes its structure, to realize the hydrophilic modifying to PVDF microfiltration membranes.
Since hydrophilic polymeric segment has the ability of anti-organic contamination, it is thus possible to improve the anti-pollution of PVDF microfiltration membranes
Metachromia energy.And crosslinkable polymer block is attached to PVDF microfiltration membranes table with can making coating stable after ultraviolet light cross-linking
Face, to increase the stability and durability of coating.
The present invention has the following advantages and effects with respect to the prior art:
(1) block polymer used in the present invention had not only contained hydrophilic segment but also can carry out photo-crosslinking, to guarantee
Gained hydrophilic modifying PVDF microfiltration membranes have good durability.
(2) block polymer of the invention can assign PVDF microfiltration membranes good hydrophilicity, so as to improve it
Antifouling property.
(3) modifying process of hydrophilic modifying PVDF microfiltration membranes of the invention is very simple, and the Modified Membrane obtained has very
Good stability and good hydrophilicity and antifouling property, therefore, can be widely used in food industry, water process,
The every field such as environmental protection.
Claims (9)
1. a kind of method of the block polymer modified polyvinilidene fluoride microfiltration membranes containing hydrophilic segment, which is characterized in that including
Following steps:
Step 1: polyvinylidene fluoride microporous filtering film is impregnated 1~100 minute in modifier solution；
Step 2: the polyvinylidene fluoride microporous filtering film after immersion is irradiated 1~48 hour under ultraviolet light, wash uncrosslinked to remove
Block polymer, obtain the polyvinylidene fluoride microporous filtering film of hydrophilic modifying；
Wherein, the modifying agent is by Formulas I structural unit and Formula II structural unit or Formulas I structural unit and formula III structural unit
The block polymer containing hydrophilic segment of composition:
Wherein, R1 is hydrogen atom or methyl, and R2 is the acylated acrylatoalkoxysilanes ester of cortex cinnamomi, and R3 is hydrogen atom or methyl, and R4 is
Arrcostab containing methoxyl group and ethyoxyl；N is integer in formula III structure；In the Formula II structural unit, R4 is 2- methoxyl group
One of ethylmethyl acrylate or 2- (2- methoxy ethoxy) ethylmethyl acrylate.
2. the method for the block polymer modified polyvinilidene fluoride microfiltration membranes according to claim 1 containing hydrophilic segment,
It is characterized by: the modifier solution solvent for use is tetrahydrofuran, dioxane, acetone, methyl phenyl ethers anisole, two in step 1
One of chloromethanes or chloroform, the mass concentration of the modifier solution are 1~25%；In step 2 using tetrahydrofuran,
It is uncrosslinked to remove that one of dioxane, acetone, methyl phenyl ethers anisole, methylene chloride or chloroform wash polyvinylidene fluoride microporous filtering film
Block polymer.
3. the method for the block polymer modified polyvinilidene fluoride microfiltration membranes according to claim 1 containing hydrophilic segment,
It is characterized by: in step 2, the ultraviolet light is the ultraviolet light that commercial ultraviolet lamp issues, the ultraviolet lamp power is 30 watts~
1000 watts.
4. micro- to the block polymer modified polyvinilidene fluoride described in 3 any one containing hydrophilic segment according to claim 1
The method of filter membrane, it is characterised in that: the polyvinylidene fluoride microporous filtering film aperture is 0.1~10 μm, with a thickness of 10~200 μm, hole
Gap rate is 10~80%.
5. a kind of block polymer containing hydrophilic segment, which is characterized in that its structural formula are as follows:
The block polymer containing hydrophilic segment be by Formulas I structural unit and Formula II structural unit or Formulas I structural unit with
The block polymer of formula III structural unit composition；
Wherein, R1 is hydrogen atom or methyl, and R2 is the acylated acrylatoalkoxysilanes ester of cortex cinnamomi, and R3 is hydrogen atom or methyl, and R4 is
Arrcostab containing methoxyl group and ethyoxyl；The integer that n is 0~500 in formula III structure；In the Formula II structural unit, R4 is
One of 2- ihethoxyethyl methacrylate or 2- (2- methoxy ethoxy) ethylmethyl acrylate.
6. the block polymer according to claim 5 containing hydrophilic segment, it is characterised in that: the Formulas I structural unit
In, R2 is the acylated hydroxyethyl methacrylate of cortex cinnamomi or one of the hydroxy-ethyl acrylate that cortex cinnamomi is acylated.
7. the block polymer according to claim 5 containing hydrophilic segment, it is characterised in that: the formula III structure list
Member be MPEG200, MPEG400, MPEG500, MPEG700, MPEG1000, MPEG1500, MPEG2000, MPEG5000,
One of MPEG10000 or MPEG20000.
8. the block polymer according to any one of claims 5 to 7 containing hydrophilic segment, it is characterised in that: Formulas I and
The number of Formula II structural unit is 1~500.
9. a kind of preparation method for preparing the block polymer according to any one of claims 8 containing hydrophilic segment, it is characterised in that: logical
It crosses atom transfer radical polymerization method and the block polymer, structural formula is prepared are as follows:
The block polymer containing hydrophilic segment be by Formulas I structural unit and Formula II structural unit or Formulas I structural unit with
The block polymer of formula III structural unit composition；Wherein, R1 is hydrogen atom or methyl, and R2 is the acylated acyloxy alcoxyl of cortex cinnamomi
Base ester, R3 are hydrogen atom or methyl, and R4 is 2- ihethoxyethyl methacrylate or 2- (2- methoxy ethoxy) ethyl first
One of base acrylate；The integer that n is 0~500 in formula III structure.
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| EP3838388A1 (en) * | 2019-12-19 | 2021-06-23 | Solvay SA | Polymer additive comprising zwitterionic moieties for vinylidene fluoride polymer based membranes |
| CN111467970A (en) * | 2020-04-30 | 2020-07-31 | 郑州轻工业大学 | Preparation method based on novel charged loose nanofiltration membrane |
| CN114525674B (en) * | 2022-01-19 | 2024-03-22 | 河北钢铁集团矿业有限公司 | High-performance anti-scaling modified filter cloth for vacuum filter and preparation method thereof |
| CN114522546B (en) * | 2022-02-24 | 2022-11-29 | 泰州南潇新材料科技有限公司 | High-hydrophilicity polysulfone ultrafiltration membrane and preparation method thereof |
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