CN104610518B - Preparation method of PVDF-PAA (polyvinylidene fluoride-polyacrylic acid) block copolymer - Google Patents
Preparation method of PVDF-PAA (polyvinylidene fluoride-polyacrylic acid) block copolymer Download PDFInfo
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Abstract
The invention discloses a preparation method of a PVDF-PAA (polyvinylidene fluoride-polyacrylic acid) block copolymer. The method comprises steps as follows: firstly, preparing a PVDF seed emulsion through iodine transfer active free-radical miniemulsion polymerization, then adding acrylonitrile monomers to continue polymerization to obtain a PVDF-PAN (polyacrylonitrile) block copolymer, and finally, hydrolyzing the PVDF-PAN block copolymer under an alkaline condition to obtain the PVDF-PAA block copolymer. The method is simple in process, the molecular weight of PVDF and PAA blocks as well as components of the block copolymer are convenient to control, and the prepared PVDF-PAA block copolymer can be applied to preparation of porous PVDF membranes with excellent stain resistance and stable membrane flux for sewage treatment.
Description
Technical field
The invention belongs to Chemical Engineering and Technology field, more particularly to a kind of Kynoar-polyacrylic acid block copolymer
Preparation method.
Background technology
Kynoar (PVDF) is a kind of thermoplastic fluoropolymer, and its yield is only second to politef and occupies and contain
The second of fluoropolymer.PVDF fluorinated volumes are up to 59wt%, due to fluorine atom electronegativity by force, atomic radius less (1.32),
C-F keys bond energy is big (485KJ/mol), and fluorine atom symmetrically replaces distribution, PVDF to have hypocrystalline, heat-resisting, weather-proof and chemically-resistant
Corrosivity are excellent, and hydrophobic oleophobic, surface energy are low, the features such as dielectric constant is little.Therefore, PVDF is widely used in building, aviation boat
My god, electronics, chemical industry, environmental protection, the industry such as new forms of energy.
Membrane product is one of important application of PVDF, can obtain dense film and perforated membrane according to processing method difference, its
Middle perforated membrane is mainly used in various sewage disposals and desalinization etc., especially membrane bioreactor (MBR) sewage disposal device
In.MBR technology is a kind of Novel sewage treatment technology for organically combining membrane technology and biotechnology, and it is taken using membrane separation plant
For the second pond in conventional biochemical processing procedure, the activated sludge in biochemical reaction tank and larger molecular organicses are retained, is had
The advantages of contaminant removal efficiency height, stable effluent quality, convenient operation and management, little floor space, be most promising sewage
One for the treatment of technology.For the ultrafiltration of MBR, microfiltration membrane material through development in recent years, gradually realize from polyolefin film to
The transformation of pvdf membrane, PVDF are increasingly becoming the main flow membrane material of MBR, and define non-solvent inversion of phases, thermic inversion of phases and
Increase the membrane preparation method of support tube.Additionally, pvdf membrane isolation technics can also be used for conventional industries (such as oil, chemical industry, the energy
Deng) transform and new high-tech industry (such as desalinization, bio-pharmaceuticals and artificial organ etc.), play reducing energy consumption, propulsion correlation
The effect of industry progress.
Due to the hydrophobic property of PVDF so that non-modified pure PVDF membrane for water treatment is susceptible to micro- in use
Toxicity bioassay and pollution, cause being gradually lowered for membrane flux.Therefore, hydrophilic modifying is carried out to PVDF becomes production high-performance PVDF
The important content of water process perforated membrane.At present, hydrophilic modifying is carried out to PVDF mainly has two class methods：(1) blending method：Will
The hydrophilic such as PVDF and Polyethylene Glycol (PEG), polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyvinylpyrrolidone (PVP) is high
Molecule or hydrophilic inorganic nanoparticle physical blending, then prepare perforated membrane（Such as Chinese patent CN101091882,
CN101874992A；Materials and Manufacturing Processes 2010, 25 (9), 1018-1020）；
(2) graft copolymerization：Activation processing is carried out to pvdf membrane first, then by high-energy radiation free radical grafting copolymerization and living radical
Graft copolymerization (atom transferred free radical and reversible addion-fragmentation chain transfer graft copolymerization etc.) method, hydrophilic monomer is grafted to
PVDF surfaces are (such as the Chinese patent CN1469892 of MIT；Applied Surface Science 2012, 258 (7),
2856-2863；Journal of Polymer Research 2010,17 (1), 71-76 etc.).Method 1 belongs to physics and mixes
Close, PVDF and modified component often have compatibility difference, it is difficult to mix homogeneously, can cause the shakiness of PVDF porous film properties
It is fixed.On the other hand, hydrophilic macromolecule has certain solvability in water, with the increase of use time, gradually can dissolve
And migrate and depart from pvdf membrane, cause the hydrophilic ability of pvdf membrane to decline.Though method 2 can conquering method 1 shortcoming, technique ratio
It is more complicated, surface activation process (the such as processing means such as ozone, alkali, plasma or high-energy ray) generally first will be carried out to PVDF,
Corresponding functional group is introduced by surface chemical reaction again, hydrophilic list is realized finally by general radical or living radical copolymerization
Grafting of the body polymer on pvdf membrane.High-energy ray is higher to equipment and environmental requirement, and industrialization difficulty is big；Atom transfer and
The reaction condition of reversible addion-fragmentation chain transfer living free radical graft copolymerization is more harsh, complex process, it is difficult to which industrialization should
With.
Except above two method, it is also to carry out hydrophilic modifying that PVDF forms block copolymer structure with hydrophilic polymer
Important channel, as hydrophilic polymer and PVDF are bonded with chemistry, therefore not easily runs off during film use, can keep
The long-acting pollution resistance and the stability of membrane flux of pvdf membrane.PVDF block copolymers mainly pass through substep active free radical polymerization system
It is standby, it is although the block copolymer such as PVDF and polystyrene, PVDF and poly- (methyl) esters of acrylic acid studies have reported that, relevant
The block copolymer report of PVDF and hydrophilic polymer composition is little, and the synthesis of PVDF and polyacrylic block copolymer and
Its application in PVDF porous membrane modifyings has not been reported.
The content of the invention
It is an object of the invention to provide a kind of preparation method of Kynoar-polyacrylic acid block copolymer.
A kind of the step of preparation method of Kynoar-polyacrylic acid block copolymer is：
1) by the deionized water of 1000 mass parts, 2.5 ~ 5 mass parts emulsifying agents, 5 ~ 10 mass parts co-emulsifier, 7.5 ~ 30
The initiator of the chain-transferring agent and 1.5-6.5 mass parts of mass parts is added in reactor, and logical nitrogen deoxygenation is less than to oxygen content
5ppm, high-speed stirred fine crankshaft under room temperature；It is warmed up to 45 ~ 80oThe reaction design temperature of C, and vinylidene fluoride monomers are passed through to setting
3.0 MPa of constant-pressure, starts polymerization, after pressure drop 0.1MPa in kettle, supplements vinylidene fluoride monomers to pressure is set, repeatedly
Operation；When the pressure drop of accumulative monomer is 4.0 ~ 6.3MPa, stop supplementing vinylidene fluoride monomers, continue to be polymerized to pressure drop extremely
1.5MPa, is cooled to room temperature and terminates polymerization, exclude unreacted vinylidene fluoride monomers, obtain active Kynoar seed emulsion；
2) acrylonitrile monemer of 20 ~ 100 mass parts is added in active Kynoar seed emulsion, is stirred at normal temperatures
Dispersion, swelling 2 ~ 5h are mixed, 45 ~ 80 are warming up tooThe reaction design temperature of C continues 5 ~ 10h of polymerization, centrifugation, be dried to obtain it is poly-
Vinylidene-polyacrylonitrile block copolymer；
3) Kynoar-polyacrylonitrile block copolymer is dissolved inN,NQuality is obtained in-dimethyl acetylamide dense
Spend the solution for 10 ~ 15%, add relative toN,NNaOH water of the concentration of 2 ~ 10% mass of-dimethylacetamide solution for 50wt%
Solution, 50 ~ 75o2 ~ 8h is hydrolyzed under C, Kynoar-polyacrylic acid block copolymer is obtained.
Described emulsifying agent is perfluorooctanoic acid, cetyl trimethylammonium bromide or hexadecyltrimethylammonium chloride.
Described co-emulsifier is hexadecane or cetyl alcohol.Described chain-transferring agent is C4F9I、C6F13I、
ICF2CF2I or IC4F8I.Described initiator is azo dicyano valeric acid, 2,2'- azos [2- (2- imidazoline -2- bases) propane]
Dihydrochloride, Ammonium persulfate. or potassium peroxydisulfate.
Having the technical effect that using the inventive method：With water as reaction medium, using mini-emulsion polymerization method, can improve
Polymerization rate, obtains that molecular weight is controllable, the end-capping living PVDF of iodine of narrow molecular weight distribution, and can further regulate and control acrylonitrile
Polymerization, obtains constituting adjustable PVDF-PAN block copolymers；As acrylic monomerss are difficult to iodine transfer activity radical polymerization
PVDF-PAA block copolymers are obtained, and the present invention is embedding using PVDF-PAA being prepared indirectly by the hydrolysis of PVDF-PAN block copolymers
The method of section copolymer, process is simple；The polyacrylic acid hydrophilic segment that the present invention is obtained is with PVDF segments with Covalent bonding together, energy
The hydrophilic of long-acting improvement PVDF, improves the pollution resistance of PVDF perforated membranes.
Specific embodiment
The present invention prepares PVDF-PAN block copolymers using iodine transfer activity free radical mini-emulsion polymerization.Compare other work
Free love base be polymerized, iodine transfer activity radical polymerization be more suitable for fluorochemical monomer, especially vinylidene activity from
By base polymerization.The iodine transfer activity radical polymerization of vinylidene adopts alkyl iodide for chain-transferring agent, conventional alkyl iodide
Compound has C4F9I、C6F13I、ICF2CF2I and IC4F8I, can prepare the work containing single-ended base iodine using single iodine end alkyl iodide
Property PVDF, and the active PVDF of strand both-end base iodine can be prepared using the alkyl iodide containing two end group iodine, from single-ended base iodine
Active PVDF sets out and can prepare the PVDF block copolymers of diblock, and from both-end base iodine activity PVDF, can prepare three
The PVDF block copolymers of block.
The present invention adopt mini-emulsion polymerization method to carry out the active of VDF polymerizations and the acrylonitrile with PVDF as seed freely to gather
Close, mini-emulsion polymerization system is made up of water, primary emulsion and co-emulsifier, initiator, chain-transferring agent and monomer etc., water, main breast
First high-speed stirred forms homogenized liquid at low temperature for agent and co-emulsifier, chain-transferring agent, heats up after adding VDF monomers and initiator
Start polymerization, obtain stable polymer emulsion.According to the characteristic of VDF monomers, perfluorooctanoic acid, cetyl trimethyl are selected
Ammonium bromide and hexadecyltrimethylammonium chloride are primary emulsion；Hexadecane and cetyl alcohol is selected to be co-emulsifier.Main breast
The consumption of agent is 2.5 ~ 5 mass fraction/1000 mass fraction deionized waters, the consumption of co-emulsifier be 5 ~ 10 mass fractions/
1000 mass fraction deionized waters.
Mini-emulsion polymerization both can be caused by water soluble starter, also can be caused by oil-soluble initiator, and the present invention selects water
Soluble initiator causes VDF and AN polymerizations, and concrete kind is azo dicyano valeric acid (V-501), 2,2'- azos [2- (2- imidazoles
Quinoline -2- bases) propane] dihydrochloride (VA-044), Ammonium persulfate. (APS) and potassium peroxydisulfate (KPS), the consumption of initiator is 1.5-
The initiator of 6.5 mass fraction/1000 numbers.
Vinylidene fluoride polymerization is the process of gas-liquid mass transferring/chemical reaction coupling, the VDF monomer concentrations of reacting environment and gas
Phase pressure is relevant with solution-air mass transfer rate, and the present invention starts the VDF monomers of 3.0MPa are first pressed into into reactor using polymerization,
And after pressure drop 1.0MPa in polymeric kettle, supplement VDF monomers certain until reaching to more than pressure, and repetition operation is set
Accumulative monomer pressure drop (4.0 ~ 6.3MPa), stop supplementing VDF monomers, continue polymerization to pressure drop to 1.5MPa, terminate poly-
Merge and exclude unreacted VDF monomers, obtain PVDF emulsions.
On the basis of stable active PVDF emulsions are obtained, add AN monomers and it is fully swelling after, heat up polymerization, and iodine is blocked
PVDF can play Macromolecular chain transfer agent, and regulation and control polymerization generates PVDF-PAN block copolymers.
Cyano group in PVDF-PAN block copolymers is hydrolyzed in the basic conditions, can be changed into carboxyl, so that PAN-PAN
Block copolymer is converted into PAN-PAA block copolymers.In order to ensure cyano group conversion completely, PVDF-PAN block copolymers elder generation
It is dissolved inN,N-In dimethylacetamide solvent, a small amount of aqueous hydrolysis containing NaOH are added.
The introducing of PAA blocks can carry out letter by determining the water contact angle of polymeric film to the hydrophilic improvements of PVDF
Single to evaluate, concrete method of testing is：A certain amount of PVDF or PVDF-PAA block copolymers sample is weighed, is dissolved inN,N- dimethyl
The solution of 7wt% in acetamide (DMAc), being prepared, appropriate solution Deca being taken on glass substrate, 40 DEG C stand film forming 48h.Using
OCA-20 video optics contact angle instruments of German Dataphysics companies etc. carry out the water contact angle of polymeric film and survey
It is fixed, 3.5 μ l water droplets are dripped with microsyringe, near drop and use camera recordings by sample slow bottom-up, take drop
Dropping to the sample surfaces image picture of the 2nd second carries out contact angle analysis.Wherein PVDF samples obtain emulsion by first step polymerization
Breakdown of emulsion, centrifugation, washing, vacuum drying are obtained.
Having the technical effect that using the inventive method：With water as reaction medium, using mini-emulsion polymerization method, can improve
Polymerization rate, obtains that molecular weight is controllable, the end-capping living PVDF of iodine of narrow molecular weight distribution, and can further regulate and control AN and gather
Close, obtain constituting adjustable PVDF-PAN block copolymers；Obtain as acrylic monomerss are difficult to iodine transfer activity radical polymerization
To PVDF-PAA block copolymers, and the present invention prepares PVDF-PAA blocks indirectly using by the hydrolysis of PVDF-PAN block copolymers
The method of copolymer, process is simple；The polyacrylic acid hydrophilic segment that the present invention is obtained, can be grown with Covalent bonding together with PVDF segments
Effect improves the hydrophilic of PVDF, improves the pollution resistance of PVDF perforated membranes.
Embodiment 1
In 5L reactors, 2000 ml water, 5.0g perfluorooctanoic acids, 20.0g cetyl alcohol, 15.2g are added
ICF2CF2The VA-044 of I, 3.2g, is passed through N2Row O25ppm is less than to content, high-speed stirred 10min at 5 DEG C obtains thin breast
Liquid；It is warmed up to 45oC, it is 3.0 MPa to be passed through VDF monomers to pressure in kettle, starts polymerization.After pressure drop 0.1MPa in kettle,
Supplement VDF monomers to pressure in kettle be 3.0MPa, repeatable operation.When the pressure drop of accumulative monomer reaches 4.0MPa, stop supplementary VDF mono-
Body, continues polymerization to pressure drop to 1.5MPa, is cooled to room temperature and terminates polymerization, excludes unreacted VDF monomers, obtain activity
PVDF seed emulsions.
40g acrylonitrile, dispersed with stirring under room temperature, swelling 2h are added into kettle.It is warming up to 45 DEG C and continues stopping after reaction 5h.
Centrifugal sedimentation, 50 DEG C of vacuum drying, obtains PVDF-PAN block copolymers.
15g PVDF-PAN block polymers are taken, the solution of 15%wt in being dissolved in DMAc, is configured to, adds 2g 50%wt's
NaOH solution, 50 DEG C of stirring hydrolysis 8h, obtains PVDF-PAA block copolymers.
The water contact angle of gained PVDF-PAA block copolymer films is 75, and the water contact angle of pure pvdf membrane is 120.
Embodiment 2
In 5L reactors, 2000 ml water, 5.0g perfluorooctanoic acids, 10.0g hexadecanes, the C of 58g are added6F13I、
The VA-044 of 3.2g, is passed through N2Row O25ppm is less than to content, high-speed stirred 10min at 5 DEG C obtains miniemulsion；It is warmed up to
50oC, it is 3.0 MPa to be passed through VDF monomers to pressure in kettle, starts polymerization.After pressure drop 0.1MPa in kettle, VDF is supplemented mono-
Body to pressure in kettle be 3.0MPa, repeatable operation.When the pressure drop of accumulative monomer reaches 6.3MPa, stop supplementing VDF monomers, continue poly-
Pressure drop is bonded to 1.5MPa, room temperature is cooled to and is terminated polymerization, exclude unreacted VDF monomers, obtain active PVDF seeds breast
Liquid.
200g acrylonitrile, dispersed with stirring under room temperature, swelling 5h are added into kettle.Stop after being warming up to 50 DEG C of continuation reaction 10h
Only.Centrifugal sedimentation, 50 DEG C of vacuum drying, obtains PVDF-PAN block copolymers.
10g PVDF-PAN block polymers are taken, the solution of 10%wt in being dissolved in DMAc, is configured to, adds 10g 50%wt's
NaOH solution, 70 DEG C of stirring hydrolysis 5h, obtains PVDF-PAA block copolymers.
The water contact angle of gained PVDF-PAA block copolymer films is 80, and the water contact angle of pure pvdf membrane is 120.
Embodiment 3
In 5L reactors, 2000 ml water, 8.0g perfluorooctanoic acids, 15.0g hexadecanes, the C of 29.0g are added4F9I、
The APS of 4.0g, is passed through N2Row O25ppm is less than to content, high-speed stirred 10min under the conditions of 5 DEG C obtains miniemulsion；It is warmed up to
80oC, it is 3.0 MPa to be passed through VDF monomers to pressure in kettle, starts polymerization.After pressure drop 1.0MPa in kettle, VDF is supplemented mono-
Body to pressure in kettle be 3.0MPa, repeatable operation.When the pressure drop of accumulative monomer reaches 5.8MPa, stop supplementing VDF monomers, continue poly-
Pressure drop is bonded to 1.5MPa, room temperature is cooled to and is terminated polymerization, exclude unreacted VDF monomers, obtain active PVDF seeds breast
Liquid.
100g acrylonitrile, dispersed with stirring under room temperature, swelling 2h are added into kettle.Stop after being warming up to 80 DEG C of continuation reaction 5h
Only.Centrifugal sedimentation, 50 DEG C of vacuum drying, obtains PVDF-PAN block copolymers.
15g PVDF-PAN block polymers are taken, the solution of 15%wt in being dissolved in DMAc, is configured to, adds 10g 50%wt's
NaOH solution, 75 DEG C of stirring hydrolysis 2h, obtains PVDF-PAA block copolymers.
The water contact angle of gained PVDF-PAA block copolymer films is 78, and the water contact angle of pure pvdf membrane is 120.
Embodiment 4
In 5L reactors, add 2000 ml water, 9.0g cetyl trimethylammonium bromide, 12.0g hexadecanes,
16.0g C4F9The APS of I, 4.0g, is passed through N2Row O25ppm is less than to content, high-speed stirred 10min under the conditions of 5 DEG C is obtained
Miniemulsion；It is warmed up to 75oC, it is 3.0 MPa to be passed through VDF monomers to pressure in kettle, starts polymerization.When pressure drop in kettle
After 1.0MPa, supplement VDF monomers to pressure in kettle be 3.0MPa, repeatable operation.When the pressure drop of accumulative monomer reaches 5.8MPa, stop
VDF monomers are supplemented, continue polymerization to pressure drop to 1.5MPa, be cooled to room temperature and terminate polymerization, exclude unreacted VDF monomers,
Obtain active PVDF seed emulsions.
100g acrylonitrile, dispersed with stirring under room temperature, swelling 2h are added into kettle.Stop after being warming up to 75 DEG C of continuation reaction 5h
Only.Centrifugal sedimentation, 50 DEG C of vacuum drying, obtains PVDF-PAN block copolymers.
15g PVDF-PAN block polymers are taken, the solution of 15%wt in being dissolved in DMAc, is configured to, adds 8g 50%wt's
NaOH solution, 75 DEG C of stirring hydrolysis 2h, obtains PVDF-PAA block copolymers.
The water contact angle of gained PVDF-PAA block copolymer films is 73, and the water contact angle of pure pvdf membrane is 120.
Embodiment 5
In 5L reactors, add 2000 ml water, 9.0g cetyl trimethylammonium bromide, 15.0g hexadecanes,
20.0g IC4F8The KPS of I, 4.0g, is passed through N2Row O25ppm is less than to content, high-speed stirred 10min under the conditions of 5 DEG C is obtained
Miniemulsion；It is warmed up to 75oC, it is 3.0 MPa to be passed through VDF monomers to pressure in kettle, starts polymerization.When pressure drop in kettle
After 1.0MPa, supplement VDF monomers to pressure in kettle be 3.0MPa, repeatable operation.When the pressure drop of accumulative monomer reaches 5.0MPa, stop
VDF monomers are supplemented, continue polymerization to pressure drop to 1.5MPa, be cooled to room temperature and terminate polymerization, exclude unreacted VDF monomers,
Obtain active PVDF seed emulsions.
80g acrylonitrile, dispersed with stirring under room temperature, swelling 2h are added into kettle.It is warming up to 75 DEG C and continues stopping after reaction 3h.
Centrifugal sedimentation, 50 DEG C of vacuum drying, obtains PVDF-PAN block copolymers.
15g PVDF-PAN block polymers are taken, the solution of 15%wt in being dissolved in DMAc, is configured to, adds 10g 50%wt's
NaOH solution, 65 DEG C of stirring hydrolysis 8h, obtains PVDF-PAA block copolymers.
The water contact angle of gained PVDF-PAA block copolymer films is 82, and the water contact angle of pure pvdf membrane is 120.
Embodiment 6
In 5L reactors, add 2000 ml water, 10.0g hexadecyltrimethylammonium chlorides, 10.0g hexadecanes,
25.0g IC4F9The APS of I, 4.0g, is passed through N2Row O25ppm is less than to content, high-speed stirred 10min under the conditions of 5 DEG C is obtained
Miniemulsion；It is warmed up to 78oC, it is 3.0 MPa to be passed through VDF monomers to pressure in kettle, starts polymerization.When pressure drop in kettle
After 1.0MPa, supplement VDF monomers to pressure in kettle be 3.0MPa, repeatable operation.When the pressure drop of accumulative monomer reaches 5.8MPa, stop
VDF monomers are supplemented, continue polymerization to pressure drop to 1.5MPa, be cooled to room temperature and terminate polymerization, exclude unreacted VDF monomers,
Obtain active DF seed emulsions.
100g acrylonitrile, dispersed with stirring under room temperature, swelling 2h are added into kettle.Stop after being warming up to 78 DEG C of continuation reaction 5h
Only.Centrifugal sedimentation, 50 DEG C of vacuum drying, obtains PVDF-PAN block copolymers.
15g PVDF-PAN block polymers are taken, the solution of 15%wt in being dissolved in DMAc, is configured to, adds 10g 50%wt's
NaOH solution, 75 DEG C of stirring hydrolysis 2h, obtains PVDF-PAA block copolymers.
The water contact angle of gained PVDF-PAA block copolymer films is 70, and the water contact angle of pure pvdf membrane is 120.
Embodiment 7
In 5L reactors, 2000 ml water, 10.0g perfluorooctanoic acids, 10.0g hexadecanes, 16.0g are added
ICF2CF2The APS of I, 4.0g, is passed through N2Row O25ppm is less than to content, high-speed stirred 10min under the conditions of 5 DEG C obtains thin breast
Liquid；It is warmed up to 75oC, it is 3.0 MPa to be passed through VDF monomers to pressure in kettle, starts polymerization.After pressure drop 1.0MPa in kettle,
Supplement VDF monomers to pressure in kettle be 3.0MPa, repeatable operation.When the pressure drop of accumulative monomer reaches 5.8MPa, stop supplementary VDF mono-
Body, continues polymerization to pressure drop to 1.5MPa, is cooled to room temperature and terminates polymerization, excludes unreacted VDF monomers, obtain activity
PVDF seed emulsions.
100g acrylonitrile, dispersed with stirring under room temperature, swelling 2h are added into kettle.Stop after being warming up to 75 DEG C of continuation reaction 5h
Only.Centrifugal sedimentation, 50 DEG C of vacuum drying, obtains PVDF-PAN block copolymers.
15g PVDF-PAN block polymers are taken, the solution of 15%wt in being dissolved in DMAc, is configured to, adds 2g 50%wt's
NaOH solution, 75 DEG C of stirring hydrolysis 8h, obtains PVDF-PAA block copolymers.
The water contact angle of gained PVDF-PAA block copolymer films is 74, and the water contact angle of pure pvdf membrane is 120.
Embodiment 8
In 5L reactors, 2000 ml water, 7.0g perfluorooctanoic acids, 10.0g hexadecanes, 25.0g are added
IC4F9The V-501 of I, 8.0g, is passed through N2Row O25ppm is less than to content, high-speed stirred 10min under the conditions of 5 DEG C obtains thin breast
Liquid；It is warmed up to 70oC, it is 3.0 MPa to be passed through VDF monomers to pressure in kettle, starts polymerization.After pressure drop 1.0MPa in kettle,
Supplement VDF monomers to pressure in kettle be 3.0MPa, repeatable operation.When the pressure drop of accumulative monomer reaches 5.5MPa, stop supplementary VDF mono-
Body, continues polymerization to pressure drop to 1.5MPa, is cooled to room temperature and terminates polymerization, excludes unreacted VDF monomers, obtain activity
PVDF seed emulsions.
100g acrylonitrile, dispersed with stirring under room temperature, swelling 5h are added into kettle.Stop after being warming up to 70 DEG C of continuation reaction 5h
Only.Centrifugal sedimentation, 50 DEG C of vacuum drying, obtains PVDF-PAN block copolymers.
15g PVDF-PAN block polymers are taken, the solution of 15%wt in being dissolved in DMAc, is configured to, adds 8g 50%wt's
NaOH solution, 75 DEG C of stirring hydrolysis 2h, obtains PVDF-PAA block copolymers.
The water contact angle of gained PVDF-PAA block copolymer films is 73, and the water contact angle of pure pvdf membrane is 120.
Embodiment 9
In 5L reactors, 2000 ml water, 7.0g perfluorooctanoic acids, 10.0g hexadecanes, 18.0g are added
ICF2CF2The VA-044 of I, 13.0g, is passed through N2Row O25ppm is less than to content, high-speed stirred 10min under the conditions of 5 DEG C is obtained
Miniemulsion；It is warmed up to 50oC, it is 3.0 MPa to be passed through VDF monomers to pressure in kettle, starts polymerization.When pressure drop in kettle
After 1.0MPa, supplement VDF monomers to pressure in kettle be 3.0MPa, repeatable operation.When the pressure drop of accumulative monomer reaches 5.5MPa, stop
VDF monomers are supplemented, continue polymerization to pressure drop to 1.5MPa, be cooled to room temperature and terminate polymerization, exclude unreacted VDF monomers,
Obtain active PVDF seed emulsions.
100g acrylonitrile, dispersed with stirring under room temperature, swelling 5h are added into kettle.Stop after being warming up to 50 DEG C of continuation reaction 10h
Only.Centrifugal sedimentation, 50 DEG C of vacuum drying, obtains PVDF-PAN block copolymers.
15g PVDF-PAN block polymers are taken, the solution of 15%wt in being dissolved in DMAc, is configured to, adds 10g 50%wt's
NaOH solution, 65 DEG C of stirring hydrolysis 2h, obtains PVDF-PAA block copolymers.
The water contact angle of gained PVDF-PAA block copolymer films is 78, and the water contact angle of pure pvdf membrane is 120.
Embodiment 10
In 5L reactors, 2000 ml water, 7.0g perfluorooctanoic acids, 10.0g hexadecanes, 40.0g are added
IC4F9The V-501 of I, 10.0g, is passed through N2Row O25ppm is less than to content, high-speed stirred 10min under the conditions of 5 DEG C obtains thin breast
Liquid；It is warmed up to 70oC, it is 3.0 MPa to be passed through VDF monomers to pressure in kettle, starts polymerization.After pressure drop 1.0MPa in kettle,
Supplement VDF monomers to pressure in kettle be 3.0MPa, repeatable operation.When the pressure drop of accumulative monomer reaches 5.5MPa, stop supplementary VDF mono-
Body, continues polymerization to pressure drop to 1.5MPa, is cooled to room temperature and terminates polymerization, excludes unreacted VDF monomers, obtain activity
PVDF seed emulsions.
100g acrylonitrile, dispersed with stirring under room temperature, swelling 5h are added into kettle.Stop after being warming up to 70 DEG C of continuation reaction 10h
Only.Centrifugal sedimentation, 50 DEG C of vacuum drying, obtains PVDF-PAN block copolymers.
15g PVDF-PAN block polymers are taken, the solution of 15%wt in being dissolved in DMAc, is configured to, adds 2g 50%wt's
NaOH solution, 70 DEG C of stirring hydrolysis 8h, obtains PVDF-PAA block copolymers.
The water contact angle of gained PVDF-PAA block copolymer films is 83, and the water contact angle of pure pvdf membrane is 120.
Embodiment 11
In 5L reactors, 2000 ml water, 7.0g perfluorooctanoic acids, 10.0g hexadecanes, 58.0g are added
C6F13The V-501 of I, 10.0g, is passed through N2Row O25ppm is less than to content, high-speed stirred 10min under the conditions of 5 DEG C obtains thin breast
Liquid；It is warmed up to 70oC, it is 3.0 MPa to be passed through VDF monomers to pressure in kettle, starts polymerization.After pressure drop 1.0MPa in kettle,
Supplement VDF monomers to pressure in kettle be 3.0MPa, repeatable operation.When the pressure drop of accumulative monomer reaches 5.5MPa, stop supplementary VDF mono-
Body, continues polymerization to pressure drop to 1.5MPa, is cooled to room temperature and terminates polymerization, excludes unreacted VDF monomers, obtain activity
PVDF seed emulsions.
100g acrylonitrile, dispersed with stirring under room temperature, swelling 5h are added into kettle.Stop after being warming up to 70 DEG C of continuation reaction 10h
Only.Centrifugal sedimentation, 50 DEG C of vacuum drying, obtains PVDF-PAN block copolymers.
15g PVDF-PAN block polymers are taken, the solution of 15%wt in being dissolved in DMAc, is configured to, adds 10g 50%wt's
NaOH solution, 70 DEG C of stirring hydrolysis 5h, obtains PVDF-PAA block polymers.
The water contact angle of gained PVDF-PAA block copolymer films is 77, and the water contact angle of pure pvdf membrane is 120.
Embodiment 12
In 5L reactors, 2000 ml water, 10.0g perfluorooctanoic acids, 20.0g cetyl alcohol, the C of 58g are added6F13I、
The VA-044 of 13.0g, is passed through N2Row O25ppm is less than to content, high-speed stirred 10min under the conditions of 5 DEG C obtains miniemulsion；Rise
Temperature is to 50oC, it is 3.0 MPa to be passed through VDF monomers to pressure in kettle, starts polymerization.After pressure drop 1.0MPa in kettle, supplement
VDF monomers to pressure in kettle be 3.0MPa, repeatable operation.When the pressure drop of accumulative monomer reaches 6.3MPa, stop supplementing VDF monomers,
Continue polymerization to pressure drop to 1.5MPa, be cooled to room temperature and terminate polymerization, exclude unreacted VDF monomers, obtain active PVDF
Seed emulsion.
200g acrylonitrile, dispersed with stirring under room temperature, swelling 5h are added into kettle.Stop after being warming up to 50 DEG C of continuation reaction 10h
Only.Centrifugal sedimentation, 50 DEG C of vacuum drying, obtains PVDF-PAN block copolymers.
15g PVDF-PAN block copolymers are taken, the solution of 15%wt in being dissolved in DMAc, is configured to, adds 8g 50%wt's
NaOH solution, 65 DEG C of stirring hydrolysis 2h, obtains PVDF-PAA block copolymers.
The water contact angle of gained PVDF-PAA block copolymer films is 65, and the water contact angle of pure pvdf membrane is 120.
Embodiment 13
In 5L reactors, 2000 ml water, 7.0g perfluorooctanoic acids, 15.0g cetyl alcohol, 15.2g are added
ICF2CF2The APS of I, 8.0g, is passed through N2Row O25ppm is less than to content, high-speed stirred 10min under the conditions of 5 DEG C obtains thin breast
Liquid；It is warmed up to 80oC, it is 3.0 MPa to be passed through VDF monomers to pressure in kettle, starts polymerization.After pressure drop 1.0MPa in kettle,
Supplement VDF monomers to pressure in kettle be 3.0MPa, repeatable operation.When the pressure drop of accumulative monomer reaches 4.0MPa, stop supplementary VDF mono-
Body, continues polymerization to pressure drop to 1.5MPa, is cooled to room temperature and terminates polymerization, excludes unreacted VDF monomers, obtain activity
PVDF seed emulsions.
40g acrylonitrile, dispersed with stirring under room temperature, swelling 5h are added into kettle.It is warming up to 80 DEG C and continues stopping after reaction 5h.
Centrifugal sedimentation, 50 DEG C of vacuum drying, obtains PVDF-PAN block copolymers.
15g PVDF-PAN block copolymers are taken, the solution of 15%wt in being dissolved in DMAc, is configured to, adds 5g 50%wt's
NaOH solution, 50 DEG C of stirring hydrolysis 2h, obtains PVDF-PAA block copolymers.
The water contact angle of gained PVDF-PAA block copolymer films is 70, and the water contact angle of pure pvdf membrane is 120.
Embodiment 14
In 5L reactors, add 2000 ml water, 10.0g hexadecyltrimethylammonium chlorides, 20.0g cetyl alcohol,
15.2g ICF2CF2The V-501 of I, 3.2g, is passed through N2Row O2To content be less than 5ppm, high-speed stirred 10min under the conditions of 5 DEG C,
Obtain miniemulsion；It is warmed up to 70oC, it is 3.0 MPa to be passed through VDF monomers to pressure in kettle, starts polymerization.When pressure drop in kettle
After 1.0MPa, supplement VDF monomers to pressure in kettle be 3.0MPa, repeatable operation.When the pressure drop of accumulative monomer reaches 5.0MPa, stop
VDF monomers are supplemented, continue polymerization to pressure drop to 1.5MPa, be cooled to room temperature and terminate polymerization, exclude unreacted VDF monomers,
Obtain active PVDF seed emulsions.
40g acrylonitrile, dispersed with stirring under room temperature, swelling 2h are added into kettle.It is warming up to 70 DEG C and continues stopping after reaction 5h.
Centrifugal sedimentation, 50 DEG C of vacuum drying, obtains PVDF-PAN block copolymers.
10g PVDF-PAN block copolymers are taken, the solution of 10%wt in being dissolved in DMAc, is configured to, adds 10g 50%wt's
NaOH solution, 70 DEG C of stirring hydrolysis 8h, obtains PVDF-PAA block copolymers.
The water contact angle of gained PVDF-PAA block copolymer films is 75, and the water contact angle of pure pvdf membrane is 120.
Embodiment 15
In 5L reactors, add 2000 ml water, 9.0g hexadecyltrimethylammonium chlorides, 10.0g hexadecanes,
25.0g IC4F9The VA-044 of I, 8.0g, is passed through N2Row O2To content be less than 5ppm, high-speed stirred 10min under the conditions of 5 DEG C,
Obtain miniemulsion；It is warmed up to 45oC, it is 3.0 MPa to be passed through VDF monomers to pressure in kettle, starts polymerization.When pressure drop in kettle
After 1.0MPa, supplement VDF monomers to pressure in kettle be 3.0MPa, repeatable operation.When the pressure drop of accumulative monomer reaches 5.0MPa, stop
VDF monomers are supplemented, continue polymerization to pressure drop to 1.5MPa, be cooled to room temperature and terminate polymerization, exclude unreacted VDF monomers,
Obtain active PVDF seed emulsions.
200g acrylonitrile, dispersed with stirring under room temperature, swelling 5h are added into kettle.Stop after being warming up to 45 DEG C of continuation reaction 5h
Only.Centrifugal sedimentation, 50 DEG C of vacuum drying, obtains PVDF-PAN block copolymers.
10g PVDF-PAN block copolymers are taken, the solution of 10%wt in being dissolved in DMAc, is configured to, adds 10g 50%wt's
NaOH solution, 75 DEG C of stirring hydrolysis 2h, obtains PVDF-PAA block copolymers.
The water contact angle of gained PVDF-PAA block copolymer films is 68, and the water contact angle of pure pvdf membrane is 120.
Embodiment 16
In 5L reactors, add 2000 ml water, 8.0g cetyl trimethylammonium bromide, 10.0g hexadecanes,
20.0g IC4F9The VA-044 of I, 8.0g, is passed through N2Row O2To content be less than 5ppm, high-speed stirred 10min under the conditions of 5 DEG C,
Obtain miniemulsion；It is warmed up to 50oC, it is 3.0 MPa to be passed through VDF monomers to pressure in kettle, starts polymerization.When pressure drop in kettle
After 1.0MPa, supplement VDF monomers to pressure in kettle be 3.0MPa, repeatable operation.When the pressure drop of accumulative monomer reaches 4.0MPa, stop
VDF monomers are supplemented, continue polymerization to pressure drop to 1.5MPa, be cooled to room temperature and terminate polymerization, exclude unreacted VDF monomers,
Obtain active PVDF seed emulsions.
40g acrylonitrile, dispersed with stirring under room temperature, swelling 5h are added into kettle.Stop after being warming up to 50 DEG C of continuation reaction 10h
Only.Centrifugal sedimentation, 50 DEG C of vacuum drying, obtains PVDF-PAN block copolymers.
15g PVDF-PAN block copolymers are taken, the solution of 15%wt in being dissolved in DMAc, is configured to, adds 10g 50%wt's
NaOH solution, 50 DEG C of stirring hydrolysis 2h, obtains PVDF-PAA block copolymers.
The water contact angle of gained PVDF-PAA block copolymer films is 81, and the water contact angle of pure pvdf membrane is 120.
Claims (5)
1. the preparation method of a kind of Kynoar-polyacrylic acid block copolymer, it is characterised in that the step of method be：
1) by the deionized water of 1000 mass parts, 2.5 ~ 5 mass parts emulsifying agents, 5 ~ 10 mass parts co-emulsifier, 7.5 ~ 30 mass
The initiator of the chain-transferring agent and 1.5-6.5 mass parts of part is added in reactor, is led to nitrogen deoxygenation and is less than 5ppm to oxygen content,
High-speed stirred fine crankshaft under room temperature；It is warmed up to 45 ~ 80oThe reaction design temperature of C, and vinylidene fluoride monomers are passed through to setting pressure
3.0 MPa, start polymerization, after pressure drop 0.1MPa in kettle, supplement vinylidene fluoride monomers to setting pressure, repeatable operation；
When the pressure drop of accumulative monomer is 4.0 ~ 6.3MPa, stop supplementing vinylidene fluoride monomers, continue polymerization to pressure drop to 1.5MPa,
It is cooled to room temperature and terminates polymerization, excludes unreacted vinylidene fluoride monomers, obtain active Kynoar seed emulsion；
2) acrylonitrile monemer of 20 ~ 100 mass parts is added in active Kynoar seed emulsion, at normal temperatures stirring point
Scattered, swelling 2 ~ 5h, is warming up to 45 ~ 80oThe reaction design temperature of C continues 5 ~ 10h of polymerization, centrifugation, is dried to obtain poly- inclined fluorine
Ethylene-polypropylene nitrile block copolymer；
3) Kynoar-polyacrylonitrile block copolymer is dissolved inN,NMass concentration is obtained in-dimethyl acetylamide is
10 ~ 15% solution, add relative toN,NThe concentration of 2 ~ 10% mass of-dimethylacetamide solution is water-soluble for the NaOH of 50wt%
Liquid, 50 ~ 75o2 ~ 8h is hydrolyzed under C, Kynoar-polyacrylic acid block copolymer is obtained.
2. the preparation method of a kind of Kynoar-polyacrylic acid block copolymer according to claim 1, its feature exist
In described emulsifying agent be perfluorooctanoic acid, cetyl trimethylammonium bromide or hexadecyltrimethylammonium chloride.
3. the preparation method of a kind of Kynoar-polyacrylic acid block copolymer according to claim 1, its feature exist
In described co-emulsifier be hexadecane or cetyl alcohol.
4. the preparation method of a kind of Kynoar-polyacrylic acid block copolymer according to claim 1, its feature exist
In described chain-transferring agent be C4F9I、C6F13I、ICF2CF2I or IC4F8I。
5. the preparation method of a kind of Kynoar-polyacrylic acid block copolymer according to claim 1, its feature exist
In described initiator be azo dicyano valeric acid, 2,2'- azos [2- (2- imidazoline -2- bases) propane] dihydrochloride, over cure
Sour ammonium or potassium peroxydisulfate.
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| WO2019121494A1 (en) * | 2017-12-19 | 2019-06-27 | Solvay Specialty Polymers Italy S.P.A. | Fluorinated block copolymers and application thereof |
| CN109608569A (en) * | 2018-10-26 | 2019-04-12 | 中国石油化工股份有限公司 | A method of preparing ethylene-acrylic acid copolymer |
| CN109722190B (en) * | 2018-12-25 | 2021-01-19 | 浙江中科立德新材料有限公司 | Preparation method of lithium battery silicon-based negative electrode binder and binder thereof |
| 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 |
| CN117801297A (en) * | 2022-09-30 | 2024-04-02 | 宁德时代新能源科技股份有限公司 | BAB type block copolymer, preparation method, binder, positive electrode slurry, positive electrode plate, secondary battery and power utilization device |
| WO2024066210A1 (en) * | 2022-09-30 | 2024-04-04 | 宁德时代新能源科技股份有限公司 | Bab type block copolymer and preparation method therefor, binder, positive electrode sheet, secondary battery and electric device |
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| CN1403489A (en) * | 2001-07-16 | 2003-03-19 | 阿托菲纳公司 | Vinylidene polymer with non-transfer chain part and its producing process |
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| CN1403489A (en) * | 2001-07-16 | 2003-03-19 | 阿托菲纳公司 | Vinylidene polymer with non-transfer chain part and its producing process |
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