CN106492660A - A kind of temperature-responsive PVDF semi-interpenetrating network polymer films and preparation method thereof - Google Patents
A kind of temperature-responsive PVDF semi-interpenetrating network polymer films and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of temperature-responsive PVDF semi-interpenetrating network polymer films and preparation method thereof, including following technique：(1) temperature-responsive monomer and PVDF are polymerized in DMF organic solvents, obtain semi-interpenetrating network polymer；(2) casting solution is obtained in organic solvent by dispersed to the semi-interpenetrating network polymer for obtaining and porogen；(3) the casting solution Glass rod for obtaining on the totally smooth glass plate striking into liquid film, then inversion of phases film forming in coagulating bath.Temperature-responsive PVDF semi-interpenetrating network polymer film good hydrophilic properties prepared by the present invention, membrane porosity are high；There is to temperature obvious dependency, flux varies with temperature scope for 200-2000L/m under 0.1MP2H, the premium properties to the rejection of bovine serum albumin up to more than 85%, with big flux and high retention.
Description
Technical field
The invention belongs to temperature responsive polymer film field, the more particularly to preparation method of semi-intercrossing network temperature responsive polymer film.
Background technology
Polymeric membrane for separation has that separation efficiency is high, energy consumption is low, simple operation and other advantages, become separating-purifying Main Means it
One.But the membrane separating process for developing rapidly proposes more new demands to the physics of membrane material, chemical property and functionalization etc.,
Causing to prepare new separation membrane with new technology and method becomes current research focus.
Kynoar (PVDF) is a kind of crystalline polymer, and ageing-resistant and anti-ultraviolet property is excellent, under room temperature by acid,
Alkali, strong oxidizer etc. corrode, and with good chemical stability, heat stability and mechanical performance, are a kind of comprehensive good
Separation membrane material, has been widely used in fields such as medical treatment, water process, petrochemical industry, food industry.But pure pvdf membrane does not have
Intelligent stalling characteristic, by its intelligent modification, gives the pole that the sensitivity characteristics such as its pH, temperature and ionic strength cause people
Big interest.
From in terms of current document report, the preparation of response pvdf membrane mainly has two kinds of method of modifying of blending and grafting.Blending and modifying
Function ingredients in prepared membrane material are easy to run off in separation process, and film properties can be caused to decline.Graft modification mainly has table
The methods such as face chemical modification, irradiation grafting modification, plasma modification.Surface chemical modification and irradiation grafting process are complicated, bar
Part is harsh, is difficult to accomplish scale production；Plasma-modified surfaces' treatment effeciency is relatively low, equipment is complicated and modified effect at any time
Between gradually decay.Therefore, the needs that simple, convenient, and reliable and inexpensive method of modifying becomes new are sought.
Semi-intercrossing network polymerization technique has preparation simple, easily realizes serialization commercial production, obtained semi-intercrossing network polymerization
Thing is to be interspersed in the network structure polymer formed in the polymer that another kind has been crosslinked by a kind of uncrosslinked linear polymer.
Blend is different from, two kinds of polymer yet suffers from respective phase in semi-interpenetrating network polymer structure；Also different from graft copolymerization
, in semi-interpenetrating network polymer structure, between two kinds of polymer, there are no chemical bonds in thing.The polymer with this structure is constituted
Homogeneous, it is not subject in use destroy, stable performance.The present invention is modified to PVDF using the technology, is prepared for
Temperature-responsive PVDF semi-interpenetrating network polymer films.The film has preferable hydrophilic, temperature sensitivity and stability, with height
Water flux and high protein interception capacity.
Content of the invention
The purpose of the present invention is using new method of modifying preparation temperature response pvdf membrane.The invention provides a kind of temperature-responsive
PVDF semi-interpenetrating network polymer films and preparation method thereof.Temperature-responsive high molecular crosslink polymer and line in film of the present invention
Property Kynoar (PVDF) formed half interpenetrating network structure, make film in use have lasting stability.This
Bright described membrane flux is big, rejection is high, and there is temperature-responsive；The film good hydrophilic property, can significantly improve antipollution simultaneously
Performance.
The present invention solves the technical scheme of the product preparation method technical problem：Design a kind of Semi-IPN nets of temperature-responsive PVDF
The preparation method of network polymeric film, the preparation of synthesis and film including semi-intercrossing network shaped polymer, containing following steps：
(1) preparation of temperature-responsive PVDF semi-interpenetrating network polymers：By vinylidene (PVDF), temperature-responsive monomer, N, N- is sub-
Bisacrylamide (MBA), azodiisobutyronitrile (AIBN) are dissolved in organic solvent DMF, are carried out under nitrogen protective condition
Polymerization crosslinking, through being centrifuged, cleaning, be dried to obtain temperature-responsive PVDF semi-interpenetrating network polymers；Described temperature-responsive list
Body is NIPA (NIPAM) or the one kind in N,N-DMAA (PDMAAm).
(2) preparation of casting solution：The temperature-responsive PVDF semi-interpenetrating network polymers that step (1) is obtained are dispersed with porogen
In organic solvent, vacuum defoamation obtains casting solution；The organic solvent be DMF (DMF), N, N- diformazans
One kind in yl acetamide (DMAC), N-Methyl pyrrolidone (NMP).
(3) preparation of temperature-responsive PVDF semi-interpenetrating network polymers film：The casting solution Glass rod that step (2) is obtained is in clean
On smooth glass plate, into liquid film, inversion of phases film forming in coagulating bath, the coagulating bath are the ethanol of distilled water or 90-95% for striking
Aqueous solution.
The preparation method of the temperature-responsive PVDF semi-interpenetrating network polymer films of present invention design, using the friendship with temperature-responsive
Kynoar (PVDF) striking of linked polymer modification is formed.Its advantage one, temperature-responsive monomer is entered in the presence of PVDF
, so as to form half interpenetrating network structure, the method is compared with graft modification, simple to operate for row cross-linked polymeric, easily realizes continuous metaplasia
Produce；Compared with blending and modifying, temperature-responsive component is not easily runed off during film use, has lasting stability.Advantage two,
Fenestra can occur reversible swelling and contraction, effective control flux and retention.Advantage three, with good hydrophilic and resistance tocrocking
Energy.Advantage four, the film have big flux and high cutoff performance simultaneously, are a kind of new separation membranes.
The preparation technology and method of the present invention is simple, can be carried out under atmospheric pressure state, and agents useful for same is conventional reagent, and
Equipment is simple, it is easy to serialization commercial production.
Specific embodiment
The present invention relates to a kind of temperature-responsive PVDF semi-interpenetrating network polymer films and preparation method thereof.The film selects Kynoar
(PVDF) as the main material of film forming, will be obtained with polymerization crosslinking is carried out again after temperature-responsive monomer and PVDF physical blendings
Temperature-responsive PVDF semi-interpenetrating network polymers, finally adopt solution forming film with phase transformation method.Its design principle be by PVDF powder with
Temperature-responsive monomer is simultaneously dispensed in organic solvent DMF, adds the feelings that initiator, cross-linking agent promote monomer to exist in PVDF
Polymerization crosslinking is carried out under condition, forms semi-interpenetrating network polymer, then by its striking film forming.The preparation method of the present invention is made with temperature
Degree responsive polymer is not easily runed off during film use with PVDF, and membrane stability is good.
The method of the invention is applied to flat board film preparation, but can equally be well applied to the film of other forms, including hollow-fibre membrane,
Tubular membrane etc..
The preparation method of temperature-responsive PVDF semi-interpenetrating network polymer films of the present invention is made further below by embodiment
Narration.
Embodiment 1
5g PVDF are dispersed in 80mLDMF in there-necked flask at (1) 70 DEG C, add 5gN- isopropyl propylene
Amide (NIPAM), cross-linking agent MBA are respectively 0.08g and 0.13g (mass ratio of MBA and monomer is 1: 62.5 and 1: 40),
Stirring forms uniform mixed liquor, leads to nitrogen 30min；0.08g initiator A IBN are quickly adding in there-necked flask, nitrogen
Stirring reaction 6h under atmosphere.Reactant centrifugation, precipitate are vacuum dried 48h, grind into powder in 50 DEG C.
(2) step (1) products therefrom is added in a certain amount of DMF (DMF), keeps casting solution
Solid content is respectively 16%, 17%, 18%, 19%, 20%, stirs 2h at 60 DEG C so as to form homogeneous casting solution, and vacuum takes off
Bubble 30min.
(3) casting solution of step (2) gained is poured on clean glass plate, with Glass rod striking film forming, is immersed
Freezing film in 25 DEG C of distilled water, through, after the solvent that distilled water washes away remnants, obtaining described temperature-responsive film.
Embodiment 2
5g PVDF are dispersed in 100mLDMF in there-necked flask at (1) 70 DEG C, add 7.5g N- isopropyls
Acrylamide (NIPAM), cross-linking agent MBA are respectively 0.12g and 0.19g (mass ratio of MBA and monomer is 1: 62.5 and 1: 40),
Stirring forms uniform mixed liquor, leads to nitrogen 30min；0.12g initiator A IBN are quickly adding in there-necked flask, nitrogen
Stirring reaction 6h under atmosphere.Reactant centrifugation, precipitate are vacuum dried 48h, grind into powder in 50 DEG C.
(2) step (1) products therefrom is added in a certain amount of N,N-dimethylacetamide (DMAC), keeps casting solution
Solid content is respectively 16%, 17%, 18%, 19%, 20%, stirs 2h at 60 DEG C so as to form homogeneous casting solution, and vacuum takes off
Bubble 40min.
(3) casting solution of step (2) gained is poured on clean glass plate, with Glass rod striking film forming, is immersed
Freezing film in 28 DEG C of 95% ethanol water, through, after the solvent that distilled water washes away remnants, obtaining described temperature-responsive film
Embodiment 3
5g PVDF are dispersed in 140mLDMF in there-necked flask at (1) 70 DEG C, add 11.7g N- isopropyls
Acrylamide (NIPAM), cross-linking agent MBA are respectively 0.19g and 0.3g (mass ratio of MBA and monomer is 1: 62.5 and 1: 40),
Stirring forms uniform mixed liquor, leads to nitrogen 30min；0.19g initiator A IBN are quickly adding in there-necked flask, nitrogen
Stirring reaction 6h under atmosphere.Reactant centrifugation, precipitate are vacuum dried 48h, grind into powder in 50 DEG C.
(2) step (1) products therefrom is added in a certain amount of N-Methyl pyrrolidone (NMP), keeps consolidating for casting solution
Content is respectively 16%, 17%, 18%, 19%, 20%, stirs 2h so as to form homogeneous casting solution, vacuum defoamation at 60 DEG C
50min.
(3) casting solution of step (2) gained is poured on clean glass plate, with Glass rod striking film forming, tool is immersed
Freezing film in 30 DEG C of 90% ethanol water, through, after the solvent that distilled water washes away remnants, obtaining described temperature-responsive film.
Embodiment 4
5g PVDF are dispersed in 200mLDMF in there-necked flask at (1) 75 DEG C, add 20g N- isopropyls third
Acrylamide (NIPAM), cross-linking agent MBA are respectively 0.32g and 0.5g (mass ratio of MBA and monomer is 1: 62.5 and 1: 40),
Logical nitrogen 30min；0.32g initiator A IBN are quickly adding in there-necked flask, stirring reaction 6h under nitrogen atmosphere.Will be anti-
Thing centrifugation, precipitate is answered to be vacuum dried 48h, grind into powder in 50 DEG C.
(2) with embodiment 1
(3) with embodiment 3
Embodiment 5
5g PVDF are dispersed in 80mLDMF in there-necked flask at (1) 75 DEG C, add 5g N, N- dimethyl propylenes
Acrylamide (PDMAAm), cross-linking agent MBA are respectively 0.08g and 0.13g (mass ratio of MBA and monomer is 1: 62.5 and 1: 40),
Stirring forms uniform mixed liquor, leads to nitrogen 30min；0.08g initiator A IBN are quickly adding in there-necked flask, nitrogen
Stirring reaction 6h under atmosphere.Reactant centrifugation, precipitate are vacuum dried 48h, grind into powder in 50 DEG C.
(2) with embodiment 1
(3) with embodiment 1
Embodiment 6
5g PVDF are dispersed in 100mLDMF in there-necked flask at (1) 75 DEG C, add 7.5gN, N- diformazans
Base acrylamide (PDMAAm), cross-linking agent MBA be respectively 0.12g and 0.19g (mass ratio of MBA and monomer for 1: 62.5 and
1: 40)), stirring forms uniform mixed liquor, leads to nitrogen 30min；0.12g initiator A IBN are quickly adding into there-necked flask
In, stirring reaction 6h under nitrogen atmosphere.Reactant centrifugation, precipitate are vacuum dried 48h, grind into powder in 50 DEG C.
(2) with embodiment 1
(3) with embodiment 3
Embodiment 7
5g PVDF are dispersed in 140mLDMF in there-necked flask at (1) 80 DEG C, add 11.7g N, N- diformazans
Base acrylamide (PDMAAm), cross-linking agent MBA be respectively 0.19g and 0.3g (mass ratio of MBA and monomer for 1: 62.5 and
1: 40), stirring forms uniform mixed liquor, leads to nitrogen 30min；0.19g initiator A IBN are quickly adding into there-necked flask
In, stirring reaction 6h under nitrogen atmosphere.Reactant centrifugation, precipitate are vacuum dried 48h, grind into powder in 50 DEG C.
(2) with embodiment 2
(3) with embodiment 3
Embodiment 8
5g PVDF are dispersed in 200mLDMF in there-necked flask at (1) 80 DEG C, add 20g N, N- dimethyl
Acrylamide (PDMAAm), cross-linking agent MBA are respectively 0.32g and 0.5g (mass ratio of MBA and monomer is 1: 62.5 and 1: 40),
Stirring forms uniform mixed liquor, leads to nitrogen 30min；0.32g initiator A IBN are quickly adding in there-necked flask, nitrogen
Stirring reaction 6h under atmosphere.Reactant centrifugation, precipitate are vacuum dried 48h, grind into powder in 50 DEG C.
(2) with embodiment 2
(3) with embodiment 3
Embodiment 9
(1) with embodiment 1
(2) step (1) products therefrom and mass percent (F127/ (F127+IPN)) are respectively 8%, 15%, 22% cause
Hole agent F127 is added in a certain amount of DMF (DMF), keeps the solid content of casting solution to be respectively 16%-20%,
2h is stirred under the conditions of 60 DEG C so as to form the homogeneous casting solution of clear, vacuum defoamation 30min.
(3) with embodiment 1
Embodiment 10
(1) with embodiment 2
(2) step (1) products therefrom and mass percent (F127/ (F127+IPN)) are respectively 8%, 15%, 22% cause
Hole agent F127 is added in a certain amount of N,N-dimethylacetamide (DMAC), and the solid content of casting solution is 16%-20%, 60 DEG C of bars
3h is stirred under part so as to form the homogeneous casting solution of clear, vacuum defoamation 30min.
(3) with embodiment 2
Embodiment 11
(1) with embodiment 5
(2) step (1) products therefrom and mass percent (F127/ (F127+IPN)) are respectively 8%, 15%, 22% cause
Hole agent F127 is added in a certain amount of N-Methyl pyrrolidone (NMP), and the solid content of casting solution is 16%-20%, 60 DEG C of conditions
Lower stirring 3h so as to form the homogeneous casting solution of clear, vacuum defoamation 30min.
(3) with embodiment 3
Embodiment 12
(1) with embodiment 6
(2) with embodiment 9
(3) with embodiment 1
Embodiment 13
(1) with embodiment 3
(2) step (1) products therefrom and mass percent (PEG/ (PEG+IPN)) are respectively 8%, 15%, 22% pore
Agent F127 is added in a certain amount of DMF (DMF), keeps the solid content of casting solution to be respectively 16%-20%,
2h is stirred under the conditions of 60 DEG C so as to form the homogeneous casting solution of clear, vacuum defoamation 30min.The molecular weight difference of PEG
For 6000,10000,20000.
(3) with embodiment 1
Embodiment 14
(1) with embodiment 4
(2) step (1) products therefrom and mass percent (PEG/ (PEG+IPN)) are respectively 8%, 15%, 22% pore
Agent F127 is added in a certain amount of N,N-dimethylacetamide (DMAC), and the solid content of casting solution is 16%-20%, 60 DEG C of conditions
Lower stirring 3h so as to form the homogeneous casting solution of clear, vacuum defoamation 30min.The molecular weight of PEG respectively 6000,
10000、20000.
(3) with embodiment 2
Embodiment 15
(1) with embodiment 7
(2) step (1) products therefrom and mass percent (PEG/ (PEG+IPN)) are respectively 8%, 15%, 22% pore
Agent F127 is added in a certain amount of N-Methyl pyrrolidone (NMP), and the solid content of casting solution is 16%-20%, under the conditions of 60 DEG C
Stirring 3h so as to form the homogeneous casting solution of clear, vacuum defoamation 30min.The molecular weight of PEG be respectively 6000,10000,
20000.
(3) with embodiment 3
Embodiment 16
(1) with embodiment 8
(2) step (1) products therefrom and mass percent (PEG/ (PEG+IPN)) are respectively 8%, 15%, 22% pore
Agent F127 is added to a certain amount of DMF (DMF)) in, the solid content of casting solution is 16%-20%, 60 DEG C of conditions
Lower stirring 4h so as to form the homogeneous casting solution of clear, vacuum defoamation 30min.The molecular weight of PEG respectively 6000,
10000、20000.
(3) with embodiment 3
After testing, the temperature-responsive PVDF semi-interpenetrating network polymer films prepared by the present invention, temperature-responsive polymer and PVDF
Mass ratio be 1: 1-1: 4；With the increase of temperature-responsive amount of monomer, fenestra quantity is more, and flux increases, hydrophilic
Significantly improve；With the increase of pore dosage, fenestra increasing number, aperture increases, contact angle can be reduced to 0 ° from 80 °,
Membrane aperture size is adjustable between 100-1000nm.Temperature-responsive PVDF semi-interpenetrating network polymers film has significantly to temperature
Dependency, under 0.1MP, variations of flux scope is in 200-2000L/m2Between h, and to the rejection of bovine serum albumin up to 85%
More than.
The preparation method of temperature-responsive PVDF semi-interpenetrating network polymer films proposed by the present invention, is retouched by embodiment
State, content as herein described is modified in without departing from present invention, spirit and scope or suitably change comes in fact with combining
The existing present invention.Specifically thing, all similar replacements and change are apparent for a person skilled in the art
's.They are considered as being included in the spirit of the present invention, scope, content.
Claims (8)
1. a kind of temperature-responsive PVDF semi-interpenetrating network polymer films, it is characterised in that the film be by a kind of temperature-responsive polymer with
Kynoar (PVDF) is Semi-IPN to be formed, and Kynoar is 1: 1-1: 4 with the mass ratio of the temperature-responsive polymer.
2. a kind of temperature-responsive PVDF semi-interpenetrating network polymer films according to claim 1, is characterized in that fenestra size can be led to
Cross ambient temperature to adjust and change, under 0.1MP, flux magnitude is in 200-1800L/m2Adjustable between h, to Ox blood serum egg
White rejection is more than 85%.
3. a kind of temperature-responsive PVDF semi-interpenetrating network polymer films according to claim 1, is characterized in that described temperature is rung
Answering property polymer is poly-N-isopropyl acrylamide or poly- N,N-DMAA.
4. a kind of preparation method step of temperature-responsive PVDF semi-interpenetrating network polymer films is as follows：
(1) preparation of temperature-responsive PVDF semi-interpenetrating network polymers：A certain amount of PVDF is dissolved in organic solvent DMF, so
Temperature-responsive monomer added afterwards, cross-linking agent N,N methylene bis acrylamide and initiator azodiisobutyronitrile, radical polymerization,
Obtain temperature-responsive PVDF semi-interpenetrating network polymers；
(2) preparation of casting solution：The temperature-responsive PVDF semi-interpenetrating network polymers that step (1) is obtained are dispersed with porogen
In organic solvent, vacuum defoamation 30-50min, obtains casting solution；
(3) preparation of temperature-responsive PVDF semi-interpenetrating network polymers film：The casting solution Glass rod that step (2) is obtained is in clean
On smooth glass plate, striking is into liquid film, inversion of phases film forming in coagulating bath.
5. the preparation method of a kind of temperature-responsive PVDF semi-interpenetrating network polymer films according to claim 4, it is characterised in that
The temperature-responsive monomer is NIPA or N,N-DMAA.
6. the preparation method of a kind of temperature-responsive PVDF semi-interpenetrating network polymer films according to claim 4, it is characterised in that
The organic solvent is DMF (DMF) or N,N-dimethylacetamide (DMAC) or N-Methyl pyrrolidone (NMP)
In one kind.
7. the preparation method of a kind of temperature-responsive PVDF semi-interpenetrating network polymer films according to claim 4, it is characterised in that
Described porogen is F127 or PEG.
8. the preparation method of a kind of temperature-responsive PVDF semi-interpenetrating network polymer films according to claims 4, it is characterised in that
The coagulating bath is the ethanol water of distilled water or 90-95%.
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| CN110684150A (en) * | 2019-09-06 | 2020-01-14 | 南方医科大学 | Amino acid nano hydrogel and preparation method and application thereof |
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