CN105037667B - A kind of amphipathic vinylidene group block copolymer and its application - Google Patents
A kind of amphipathic vinylidene group block copolymer and its application Download PDFInfo
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Abstract
The present invention relates to a kind of amphipathic vinylidene group block copolymer and its application.The amphipathic vinylidene group block copolymer is made up of Kynoar segment and polyvinyl alcohol segments, has molecular structure shown in formula (I)：
Description
Technical field
The present invention relates to a kind of amphipathic vinylidene group block copolymer and its application, belong to fluoropolymer technology
Field.
Background technology
Fluoropolymer material is high-performance organic material, has excellent combination property, is the good base of preparative separation film
Material.Kynoar (PVDF) resin turns into water process because its chemical stability, heat endurance and mechanical strength are all extremely prominent
Seperation film it is preferred.But PVDF has stronger hydrophobicity, and water flux is low after causing film forming, and absorption pollution is easily produced, sternly
Membrane separating property and service life are have impact on again, add running cost.Therefore, particularly heavy is seemed to pvdf membrane hydrophilic modification
Will.
At present, pvdf membrane hydrophilic modification method has surface to be modified and this modifies two major class.It is after film forming that surface, which is modified,
To membrane surface modification, such as surface coating, chemical surface treatment and graft modification.But existing surface modifying method is constantly present
The shortcomings that such or such, such as：The method equipment of surface initiation grafting is complicated, and running cost is high, and grafting is uneven；And high energy
Radiation treatment may destroy the body construction of film, reduce the separating property and mechanical strength of film.Originally it is modifies to refer to before film forming
Polymeric matrix be modified, mainly by being copolymerized and being blended realization.Modification by copolymerization technical process is complex, do not know because
Element is more, is unfavorable for industrialization development.Blending and modifying is mainly by the stronger material of hydrophily and PVDF physical blendings into polymer
Film is prepared again, has the advantages that technique is simple and convenient to operate, is modified thorough, more suitable for industrialized production.There is research poly- second
The linear water soluble polymers such as glycol as hydrophilic modifier and PVDF blending prepare hydrophilic film, but film forming procedure and
Easily soon being eluted in film application process, numerous researchs show that this kind of polymer is poor to the hydrophilic modifying effect of pvdf membrane,
Decay is fast, is nonideal hydrophilic modifying additive.To overcome the shortcomings of water-soluble modified dose, it is necessary to develop a kind of new structure
Modifying agent implement the hydrophilic modifying of pvdf membrane.
From MOLECULE DESIGN angle, design and prepare amphipathic block modified dose of one kind, it may be possible to which what is solved the above problems has
Effect method.Hydrophobic segment in amphipathic nature block polymer has good compatibility with film matrix material, and hydrophilic segment makes
Film has higher hydrophily.Having document report, (Wang Ting, PEG-PB-PEG triblock copolymer blending and modifying perforated membrane is ground
Study carefully, master thesis, Zhejiang University, 2012；Pang Dongxu etc., amphipathic three block copolymer PVP-b-PMMA-b-PVP conjunction
Into and its to pvdf membrane hydrophilic modifying effect, national macromolecule science free paper session thesis summary set in 2009, Tianjin,
In August, 2009), the amphipathic nature block polymer of polymethyl methacrylate base and polybutadiene-base, and it is used as pvdf membrane
Modifying agent, the resistance tocrocking of film and hydrophilic persistence be significantly improved, and shows preferable modified effect.But both change
Property agent hydrophobic section be hydrocarbon molecules, the carbon fluorine structure of itself and PVDF matrixes still has sizable difference, and its compatibility is bad, influences
To the persistence of hydrophilic modifying.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of amphipathic vinylidene group block copolymer and offer should
Application of the block copolymer as Pvdf Microporous Hollow Fiber Membrane permanent hydrophilic modifying agent.
Technical scheme is as follows：
A kind of amphipathic vinylidene group block copolymer, it is by Kynoar segment and polyvinyl alcohol segments group
Into having molecular structure shown in formula (I)：
In formula, a=12~1000, b=15~1000, and a/ (a+b)=0.15~0.40, b/ (a+b)=0.60~
0.85。
According to currently preferred, the number-average molecular weight of the amphipathic vinylidene group block copolymer for 2000~
100000, it is further preferred that the number-average molecular weight of the amphipathic vinylidene group block copolymer be 3500~
30000.The measure of molecular weight can use any known method, as gel permeation chromatography determines.
The preparation method of above-mentioned amphipathic vinylidene group block copolymer, comprises the following steps：
(1) by organic solvent, fluorinated olefin monomers, initiator, chain-transferring agent under the conditions of oxygen barrier, 50~90 DEG C of polymerizations are anti-
5~12h is answered, is purified, Kynoar active macromolecules are made；
The organic solvent, fluorinated olefin monomers, initiator, the mol ratio of chain-transferring agent are (3~15):(1~5):
(0.01~0.1):(0.01~1)；
Described fluorinated olefin monomers are vinylidene, and initiator is organic peroxide；
(2) addition vinylacetate, initiator into Kynoar active macromolecules made from step (1), 50~90
DEG C 4~8h of reaction, purifying, dries, PVDF-PVAc block copolymers is made；
The mol ratio of the vinylacetate, initiator and the organic solvent in step (1) is：(1~3):(0.005~
0.1):(2~10)；
Described initiator is azo-initiator；
(3) PVDF-PVAc block copolymers made from taking step (2), are dissolved in alcoholic solution, add acid solution, hydrolyze, system
Obtain amphipathic vinylidene group block copolymer.
According to currently preferred, purifying in the step (1) is reclaims unreacted vinylidene.
According to currently preferred, the chain-transferring agent in the step (1) is xanthate, the general molecular formula of xanthate
For：ZC=SSR, wherein, Z=OCH3Or OCH2CH3；R=C6H5, CH (CH3)COOCH3Or CH (CH3)COOCH3。
According to currently preferred, initiator is the peroxidating pivalic acid tert-butyl ester (TPBBI), peroxide in the step (1)
Change pivalic acid spy pentyl ester or the peroxidating carbonic acid -2- ethyl acid tert-butyl esters.
According to currently preferred, polymeric reaction temperature is 60~75 DEG C in the step (1).
According to currently preferred, organic solvent is DMF or N, N- dimethyl in the step (1)
Acetamide.
According to currently preferred, reaction temperature is 60~75 DEG C in the step (2).
According to currently preferred, in the step (2), initiator is azodiisobutyronitrile or AMBN.
According to currently preferred, in the step (2), purify dense to add mass percent into reacted system
Spend the methanol solution for 45~85%, the volume ratio of methanol solution and reaction system is (4~1):1, filtering, take precipitation.
According to currently preferred, in the step (3), alcoholic solution is methanol solution；It is further preferred that described first
The mass percent concentration of alcoholic solution is 10~15%.
According to currently preferred, the mass ratio of acid and PVDF-PVAc block copolymers is 1 in the step (3):(4~
20), the mass ratio of acid and water is 1:(1~5)；Preferably, the acid in the step (3) is hydrochloric acid or sulfuric acid.
According to currently preferred, 50~80 DEG C of hydrolysising reacting temperature in the step (3), hydrolysis time is 24~72 small
When.
Above-mentioned amphipathic vinylidene group block copolymer prepares poly- with durable hydrophilic property as hydrophilic modifier
Application in vinylidene hollow-fibre membrane.
Above-mentioned application, step are as follows：
(i) amphipathic vinylidene group block copolymer, the polyvinylidene fluoride resin of above-mentioned preparation are mixed with solvent,
10~15h, amphipathic vinylidene group block copolymer and polyvinylidene fluoride resin mixing quality are dissolved at 65~75 DEG C
Than for (1~25)：100,8~36 hours are stood, casting solution is made；
(ii) casting solution made from step (i) is prepared into durable hydrophilic property hollow-fibre membrane using conventional dry-wet processing,
Casting film 3.0~25.0mL/min of flow velocity, casting solution temperature are 30~80 DEG C, and coagulation bath temperature is 20~45 DEG C, doughnut
Film setting time is 1~8 minute.
According to currently preferred, in the step (i), amphipathic vinylidene group block copolymer and polyvinylidene fluoride
The mixing quality ratio of olefine resin is (4~15)：100.
According to currently preferred, in the step (i), solvent is selected from DMA, N, N- dimethyl methyls
One of acid amides, 1-METHYLPYRROLIDONE or two or more mixing；Preferably, in the step (i), the addition of solvent is total
The 60~85% of reactant quality percentage composition.
Above-mentioned raw materials are ordinary commercial products unless otherwise specified.
Beneficial effect
1st, amphipathic vinylidene group block copolymer of the present invention, by Kynoar segment and polyvinyl alcohol
Segment composition, the ratio and molecular weight of different segments are can adjust by the addition and reaction time of monomer and chain-transferring agent；
2nd, amphipathic vinylidene group block copolymer of the present invention, can be applied to polyvinylidene fluoride hollow fiber
The hydrophilic modifying of film, it is in the advantage of polyvinylidene fluoride film hydrophilically modified aspect, and on the one hand its hydrophobic segment is same PVDF
Film matrix material structure identical PVDF segments, modifier molecules are good with matrix compatibility, mutually tangled between macromolecular chain, can be big
The big stability for improving modifying agent in film, on the other hand, its hydrophilic segment contains great amount of hydroxy group hydrophilic radical, in film-forming process
Middle hydrophilic segment can migrate to film surface and channel surfaces, so as to significantly improve film surface hydrophilicity and antifouling property, most
Improve to big degree film properties, and the hydrophilic section of amphiphilic Kynoar group block copolymer disclosed by the invention and hydrophobic
Length certain Duan Douyou, compared to the amphipathic nature polyalcohol with other structures form (the dressing structure formed such as grafting), it is more easy to
Distribution is migrated between PVDF matrix phases and water-wetted surface；
3rd, the polyvinylidene fluoride hollow fiber prepared using amphipathic vinylidene group block copolymer of the present invention
Film, good permanent hydrophilic modified effect can be shown, be remarkably improved the surface hydrophilicity and antifouling property of film.
Embodiment
Specific embodiment of the present invention is described by the following examples, but embodiment is not intended to limit the present invention's
Protection domain.
Detection method
Amphipathic vinylidene fluoride block copolymer amount in embodiment is by Waters-1525 type gel permeation chrommatographs
Tested, the instrument is mobile phase and solvent using tetrahydrofuran, and polystyrene resin is standard sample；Block copolymer
Kynoar and polyvinyl alcohol block molar ratio are by nuclear magnetic resonance hydrogen spectruming determining.
Detect hydrophilic persistence bibliography (Zhao, the YH of hydrophilic modifying film；Qian,YL；Zhu,BK；Xu,
YY.Journal of Membrane Science,2008,310(1-2):567；Wang Ting .PEG-PB-PEG triblock copolymers
The research of blending and modifying perforated membrane, Zhejiang University .2012.) report method, film is placed in 60 DEG C of waters bath with thermostatic control and continuously shaken
Different time (1 day, 7 days, 15 days and 30 days), observe the change of its water flux.After experimental result display vibration in (30 days) for a long time,
Modified Membrane still keeps higher water flux, shows that blend film still keeps preferable hydrophily, the i.e. inclined fluorine of amphipathic after vibration
Vinyl block copolymer can be effectively maintained in film, and there is the hydrophilic modifying lasting to pvdf membrane to act on.
Raw material described in embodiment is ordinary commercial products unless otherwise specified.
Embodiment 1
A kind of preparation method of amphipathic vinylidene group block copolymer, comprises the following steps：
In 500ml reactors, DMF 300g, vinylidene 64.0g, peroxidating pivalic acid uncle are added
Butyl ester (TPBBI) 1.9540g, CH3CH2OC=SSC6H5Chain-transferring agent 3.0g, 0 DEG C is cooled to, is slowly introducing nitrogen 30 minutes,
Oxygen in exclusion system；It is warming up to 68 DEG C to start to polymerize, the room temperature that reaction time 12h is cooled to terminates to polymerize, and reclaims unreacted
VDF monomers, obtain Kynoar active macromolecules.129g vinylacetates, azodiisobutyronitrile are continuously added into kettle
1.5g, start stirring and be warming up to 70 DEG C and continue to stop after reacting 8h, add methanol/water (volume ratio 1:1) white precipitate is obtained,
Filtering vacuum is dried to obtain PVDF-PVAc block copolymers.
Take 20g PVDF-PVAc block copolymers to be dissolved in the solution for being configured to 12wt% in methanol, add the 2ml concentrated sulfuric acids,
5ml distilled water, hydrolyzed 24 hours in 70 DEG C of stirrings, obtain PVDF-PVA block copolymers.
The mol ratio of PVDF blocks and PVA blocks is 34 in nmr analysis block copolymer：66 (mol/mol), block gathers
The number-average molecular weight of compound is 3.5 ten thousand；Molecular structure is as follows：
In formula, a 234, b 454.
Embodiment 2
In 500ml reactors, DMF 300g, vinylidene 64.0g, peroxidating pivalic acid uncle are added
Butyl ester (TPBBI) 1.9540g, CH3CH2OC=SSC6H5Chain-transferring agent 3.0g, 0 DEG C is cooled to, is slowly introducing nitrogen 30 minutes,
Oxygen in exclusion system；68 DEG C are warming up to, starts to polymerize, reaction time 12h, room temperature is cooled to and terminates to polymerize, recovery is not anti-
VDF monomers are answered, obtain Kynoar active macromolecules.The addition 156g vinylacetates into kettle, azodiisobutyronitrile 1.5g,
Start stirring and be warming up to 70 DEG C and continue to stop after reacting 8h, add methanol/water (volume ratio 1:1) white precipitate is obtained, is filtered
Vacuum drying obtains PVDF-PVAc block copolymers.
Take 20g PVDF-b-PVAc block copolymers to be dissolved in the solution for being configured to 12wt% in methanol, add the dense sulphur of 2ml
Acid, 5ml distilled water, hydrolyzed 24 hours in 70 DEG C of stirrings, obtain PVDF-PVA block copolymers.
The mol ratio of PVDF blocks and PVA blocks is 26 in nmr analysis block copolymer：74 (mol/mol), block gathers
The number-average molecular weight of compound is 2.7 ten thousand；Molecular structure is as follows：
In formula, a 143, b 407.
Embodiment 3
In 500ml reactors, DMF 300g, vinylidene 64.0g, peroxidating pivalic acid spy are added
Pentyl ester 2.1151g, CH3CH2OC=SSC6H5Chain-transferring agent 4.5g, 0 DEG C is cooled to, is slowly introducing nitrogen 30 minutes, exclude system
In oxygen；65 DEG C are warming up to, starts to polymerize, reaction time 12h, room temperature is cooled to and terminates to polymerize, recovery unreacted VDF is mono-
Body, obtain Kynoar active macromolecules.129g vinylacetates are added into kettle, azodiisobutyronitrile 1.5g, starts and stirs
Mix and be warming up to 70 DEG C and continue to stop after reacting 8h, add methanol/water (volume ratio 1:1) white precipitate is obtained, filtering vacuum is done
It is dry to obtain PVDF-b-PVAc block copolymers.
Take 20g PVDF-b-PVAc block copolymers to be dissolved in the solution for being configured to 12wt% in methanol, add the dense sulphur of 2ml
Acid, 5ml distilled water, hydrolyzed 24 hours in 70 DEG C of stirrings, obtain PVDF-b-PVA block copolymers.
The mol ratio of PVDF blocks and PVA blocks is 31 in nmr analysis block copolymer：69 (mol/mol), block gathers
The number-average molecular weight of compound is 2.2 ten thousand；Molecular structure is as follows：
In formula, a 136, b 302.
Embodiment 4
In 500ml reactors, DMF 300g, vinylidene 64.0g, peroxidating carbonic acid -2- are added
The ethyl acid tert-butyl ester 2.9341g, CH3CH2OC=SSC6H5Chain-transferring agent 3.0g, 0 DEG C is cooled to, is slowly introducing nitrogen 30 and divides
Clock, the oxygen in exclusion system；65 DEG C are warming up to, starts to polymerize, reaction time 6h, room temperature is cooled to and terminates to polymerize, recovery is not
VDF monomers are reacted, obtain Kynoar active macromolecules.129g vinylacetates, azodiisobutyronitrile are added into kettle
1.5g, start stirring and be warming up to 70 DEG C and continue to stop after reacting 8h, add methanol/water (volume ratio 1:1) white precipitate is obtained,
Filtering vacuum is dried to obtain PVDF-b-PVAc block copolymers.
Take 20g PVDF-b-PVAc block copolymers to be dissolved in the solution for being configured to 12wt% in methanol, add the dense sulphur of 2ml
Acid, 5ml distilled water, hydrolyzed 24 hours in 70 DEG C of stirrings, obtain PVDF-b-PVA block copolymers.
The mol ratio of PVDF blocks and PVA blocks is 19 in nmr analysis block copolymer：81 (mol/mol), block gathers
The number-average molecular weight of compound is 2.1 ten thousand；Molecular structure is as follows：
In formula, a 83, b 355.
Embodiment 5
In 500ml reactors, DMA 350g, vinylidene 64.0g, peroxidating pivalic acid uncle are added
Butyl ester (TPBBI) 1.9540g, CH3CH2OC=SSC6H5Chain-transferring agent 3.0g, 0 DEG C is cooled to, is slowly introducing nitrogen 30 minutes,
Oxygen in exclusion system；68 DEG C are warming up to, starts polymerization reaction time 12h, is cooled to room temperature and terminates to polymerize, reclaims unreacted
VDF monomers, obtain Kynoar active macromolecules.129g vinylacetates are added into kettle, azodiisobutyronitrile 1.5g, are opened
Move stirring and be warming up to 70 DEG C and continue to stop after reacting 5h, add methanol/water (volume ratio 1:1) white precipitate is obtained, filtering is true
Sky is dried to obtain PVDF-b-PVAc block copolymers.
Take 20g PVDF-b-PVAc block copolymers to be dissolved in the solution for being configured to 12wt% in methanol, add the dense sulphur of 2ml
Acid, 5ml distilled water, hydrolyzed 24 hours in 70 DEG C of stirrings, obtain PVDF-b-PVA block copolymers.
The mol ratio of PVDF blocks and PVA blocks is 38 in nmr analysis block copolymer：62 (mol/mol), block gathers
The number-average molecular weight of compound is 2.9 ten thousand；Molecular structure is as follows：
In formula, a 213, b 348.
Comparative example 1
In 500ml reactors, DMF 300g, vinylidene 21.0g, peroxidating pivalic acid uncle are added
Butyl ester (TPBBI) 1.9540g, CH3CH2OC=SSC6H5Chain-transferring agent 6.5g, 0 DEG C is cooled to, is slowly introducing nitrogen 30 minutes,
Oxygen in exclusion system；It is warming up to 68 DEG C to start to polymerize, the room temperature that reaction time 6h is cooled to terminates to polymerize, and reclaims unreacted
VDF monomers, obtain Kynoar active macromolecules.48g vinylacetates, azodiisobutyronitrile are continuously added into kettle
1.5g, start stirring and be warming up to 70 DEG C and continue to stop after reacting 8h, add methanol/water (volume ratio 1:1) white precipitate is obtained,
Filtering vacuum is dried to obtain PVDF-PVAc block copolymers.
Take 20g PVDF-PVAc block copolymers to be dissolved in the solution for being configured to 12wt% in methanol, add the 2ml concentrated sulfuric acids,
5ml distilled water, hydrolyzed 24 hours in 70 DEG C of stirrings, obtain PVDF-PVA block copolymers.
The mol ratio of PVDF blocks and PVA blocks is 33 in nmr analysis block copolymer：67 (mol/mol), block gathers
The number-average molecular weight of compound is 0.15 ten thousand；Molecular structure is as follows：
In formula, a 9, b 20.
Comparative example 2
In 500ml reactors, DMF 300g, vinylidene 64.0g, peroxidating pivalic acid uncle are added
Butyl ester (TPBBI) 1.9540g, CH3CH2OC=SSC6H5Chain-transferring agent 3.0g, 0 DEG C is cooled to, is slowly introducing nitrogen 30 minutes,
Oxygen in exclusion system；It is warming up to 68 DEG C to start to polymerize, the room temperature that reaction time 12h is cooled to terminates to polymerize, and reclaims unreacted
VDF monomers, obtain Kynoar active macromolecules.21g vinylacetates, azodiisobutyronitrile are continuously added into kettle
1.5g, start stirring and be warming up to 70 DEG C and continue to stop after reacting 8h, add methanol/water (volume ratio 1:1) white precipitate is obtained,
Filtering vacuum is dried to obtain PVDF-PVAc block copolymers.
Take 20g PVDF-PVAc block copolymers to be dissolved in the solution for being configured to 12wt% in methanol, add the 2ml concentrated sulfuric acids,
5ml distilled water, hydrolyzed 24 hours in 70 DEG C of stirrings, obtain PVDF-PVA block copolymers.
The mol ratio of PVDF blocks and PVA blocks is 81 in nmr analysis block copolymer：19 (mol/mol), block gathers
The number-average molecular weight of compound is 2.6 ten thousand；Molecular structure is as follows：
In formula, a 350, b 82.
Embodiment 6
By embodiment 1~5 and comparative example 1~2-in-1 into amphipathic vinylidene group block copolymer respectively with it is poly- inclined
It is fluoride blended, using traditional dry-wet spinning technique (reference can be made to pertinent literature, such as Lv Xiaolong, Hu Chengsong, Hu Xinping are high
Performance polyvinylidene fluoride hollow fiber spins textile journals, 1999,20 (4):240~242.), prepare with permanent hydrophilic
The Pvdf Microporous Hollow Fiber Membrane of property, the antifouling property of polyvinylidene fluoride separation membrane can be improved.
1.6% ratio adds the amphipathic vinylidene fluoride block copolymerization of above-mentioned preparation by mass percentage successively
The ratio addition of thing, by mass percentage 20% ratio addition polyvinylidene fluoride resin, by mass percentage 78.4% (w/w)
DMA, then in 70 DEG C of stirring and dissolving 12h, it is stored at room temperature deaeration 12 hours, deviates from the bubble of remaining, is made
Casting solution.
Casting film flow velocity 10.0mL/min is controlled, casting solution temperature is 70 DEG C, and coagulation bath temperature is 40 DEG C, hollow-fibre membrane
Setting time is 3 minutes, and Hydrophilic hollow fiber membrane is prepared using traditional dry-wet spinning technique.
The hydrophilic persistence test result of hydrophilic modifying film is as shown in table 1.
The hydrophilic persistence test result of the hydrophilic modifying Pvdf Microporous Hollow Fiber Membrane of table 1
Interpretation of result
The polyvinylidene fluoride film that the Amphipathilic block polymer that it can be seen from the result of table 1 prepared by embodiment 1~5 is modified,
As duration of oscillation extends, water flux only has minimal amount of decline, illustrates that modifying agent keeps stable in matrix so that flux is protected
It is fixed to keep steady.Amphipathilic block polymer molecular weight prepared by comparative example 1 is too small, and molecular chain length is limited, with Kynoar tree
Winding when fat is blended between strand is lacked, it is difficult to keeps permanent in polyvinylidene fluoride resin matrix, majority, which can be lost in, to be caused
The flux of Modified Membrane declines seriously, and the hydrophilic persistence of film is bad.Block polymer hydrophilic segment prepared by comparative example 2 is short, parent
Water modified effect is limited, and membrane flux reduces with time lengthening is also gradually obvious.
Claims (21)
1. a kind of amphipathic vinylidene group block copolymer, is made up of Kynoar segment and polyvinyl alcohol segments,
Characterized in that, there is formula（I）Shown molecular structure：
In formula, the ＜ b ＜ 1000 of 12 ＜ a ＜ 1000,15, and 0.15 ＜ a/ (a+b) ＜ 0.40,0.60 ＜ b/ (a+b) ＜ 0.85；
The number-average molecular weight of the amphipathic vinylidene group block copolymer is more than or equal to 21000 and less than 100000.
2. amphipathic vinylidene group block copolymer as claimed in claim 1, it is characterised in that the amphipathic is inclined
The number-average molecular weight of fluoride-based block copolymer is more than or equal to 21000 and less than 30000.
3. the preparation method of amphipathic vinylidene group block copolymer described in claim 1, it is characterised in that including as follows
Step：
（1）By organic solvent, fluorinated olefin monomers, initiator, chain-transferring agent under the conditions of oxygen barrier, 50~90 DEG C of polymerisations 5
~12 h, purifying, Kynoar active macromolecules are made；
The organic solvent, fluorinated olefin monomers, initiator, the mol ratio of chain-transferring agent are（3~15）:（1~5）:（0.01~
0.1）:（0.01~1）；
Described fluorinated olefin monomers are vinylidene, and initiator is organic peroxide；
（2）To step（1）Vinylacetate, initiator are added in obtained Kynoar active macromolecules, 50~90 DEG C anti-
4~8h is answered, purifying, is dried, PVDF-PVAc block copolymers are made；
The vinylacetate, initiator and step（1）In the mol ratio of organic solvent be：（1~3）:（0.005~0.1）:
（2~10）；
Described initiator is azo-initiator；
（3）Take step（2）Obtained PVDF-PVAc block copolymers, are dissolved in alcoholic solution, add acid solution, hydrolysis, are made two
Parent's property Kynoar group block copolymer.
4. preparation method as claimed in claim 3, it is characterised in that the step（1）In purifying for reclaim it is unreacted
Vinylidene.
5. preparation method as claimed in claim 3, it is characterised in that the step（1）In chain-transferring agent be xanthate,
The general molecular formula of xanthate is：ZC=SSR, wherein, Z=OCH3Or OCH2CH3；R=C6H5, CH (CH3)COOCH3。
6. preparation method as claimed in claim 3, it is characterised in that the step（1）Middle initiator is peroxidating pivalic acid
The tert-butyl ester or peroxidating pivalic acid spy's pentyl ester.
7. preparation method as claimed in claim 3, it is characterised in that the step（1）Middle polymeric reaction temperature is 60~75
℃。
8. preparation method as claimed in claim 3, it is characterised in that the step（1）Middle organic solvent is N, N- dimethyl
Formamide or DMAC N,N' dimethyl acetamide.
9. preparation method as claimed in claim 3, it is characterised in that the step（2）Middle reaction temperature is 60~75 DEG C.
10. preparation method as claimed in claim 3, it is characterised in that the step（2）In, initiator is the isobutyl of azo two
Nitrile or AMBN.
11. preparation method as claimed in claim 3, it is characterised in that the step（2）In, purify as to reacted body
Mass percent concentration is added in system as 45~85% methanol solution, the volume ratio of methanol solution and reaction system is（4~1）:
1, filtering, take precipitation.
12. preparation method as claimed in claim 3, it is characterised in that the step（3）In, alcoholic solution is methanol solution.
13. preparation method as claimed in claim 12, it is characterised in that the mass percent concentration of described methanol solution is
10~15%.
14. preparation method as claimed in claim 3, it is characterised in that the step（3）Middle acid is total to PVDF-PVAc blocks
The mass ratio of polymers is 1:（4~20）, sour and water mass ratio is 1:（1~5）.
15. preparation method as claimed in claim 3, it is characterised in that the step（3）In acid be hydrochloric acid or sulfuric acid.
16. preparation method as claimed in claim 3, it is characterised in that the step（3）Middle hydrolysising reacting temperature 50~80
DEG C, hydrolysis time is 24~72 hours.
17. amphipathic vinylidene group block copolymer described in claim 1 is prepared as hydrophilic modifier has persistently parent
Application in water-based Pvdf Microporous Hollow Fiber Membrane.
18. application as claimed in claim 17, it is characterised in that step is as follows：
（i）The amphipathic vinylidene group block copolymer, polyvinylidene fluoride resin are mixed with solvent, at 65~75 DEG C
10~15h is dissolved, the mixing quality ratio of amphipathic vinylidene group block copolymer and polyvinylidene fluoride resin is（1~
25）：100,8~36 hours are stood, casting solution is made；
（ii）By step（i）Obtained casting solution prepares durable hydrophilic property hollow-fibre membrane, casting film using conventional dry-wet processing
The mL/min of flow velocity 3.0~25.0, casting solution temperature are 30~80 DEG C, and coagulation bath temperature is 20~45 DEG C, and hollow-fibre membrane coagulates
Gu the time is 1~8 minute.
19. application as claimed in claim 18, it is characterised in that the step（i）In, amphipathic vinylidene fluoride block
The mixing quality of copolymer and polyvinylidene fluoride resin ratio is（4~15）：100.
20. application as claimed in claim 18, it is characterised in that the step（i）In, solvent is selected from N, N- dimethylacetamides
One of amine, N,N-dimethylformamide, 1-METHYLPYRROLIDONE or two or more mixing.
21. application as claimed in claim 18, the step（i）In, the addition of solvent contains for total reactant quality percentage
The 60~85% of amount.
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| CN105709618B (en) * | 2016-04-19 | 2019-08-09 | 贵阳学院 | By the Pvdf Microporous Hollow Fiber Membrane of amphipathic three block copolymer blending and modifying |
| CN106432585B (en) * | 2016-09-20 | 2020-06-30 | 广州中国科学院先进技术研究所 | Fluorine-containing polymer and preparation method and application thereof |
| WO2018209121A1 (en) * | 2017-05-12 | 2018-11-15 | Terapore Technologies, Inc. | Chemically resistant fluorinated multiblock polymer structures, methods of manufacturing and use |
| FR3071500B1 (en) * | 2017-09-27 | 2020-05-15 | Arkema France | SYNTHESIS OF POLY LATEX (VINYLIDENE FLUORIDE) WITHOUT SURFACTANT BY RAFT EMULSION POLYMERIZATION |
| CN109021186A (en) * | 2018-06-21 | 2018-12-18 | 济南大学 | A kind of amphiphilic star-like multi-arm polyvinylidene fluoride alkene block copolymer and preparation method thereof |
| CN109096453B (en) * | 2018-06-21 | 2020-11-06 | 济南大学 | Comb-shaped amphiphilic polyvinylidene fluoride-based block copolymer and application thereof |
| CN108976369B (en) * | 2018-06-21 | 2020-07-07 | 济南大学 | Amphiphilic star-shaped three-arm polyvinylidene fluoride block copolymer |
| CN110124540B (en) * | 2019-05-27 | 2020-04-17 | 济南大学 | Preparation method of super-hydrophilic polyvinylidene fluoride membrane |
| CN112029057B (en) * | 2020-07-14 | 2022-04-19 | 乳源东阳光氟树脂有限公司 | Hydrophilic modified polyvinylidene fluoride block copolymer, water treatment membrane, preparation method and application thereof |
| CN114752025B (en) * | 2022-05-24 | 2024-02-23 | 阳光储能技术有限公司 | Modified polyvinylidene fluoride, preparation method thereof, diaphragm and lithium ion battery |
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