CN104610518A - 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, particularly relate to the preparation method of a kind of polyvinylidene difluoride (PVDF)-polyacrylic acid segmented copolymer.
Background technology
Polyvinylidene difluoride (PVDF) (PVDF) is a kind of thermoplastic fluoropolymer, and its output is only second to tetrafluoroethylene and occupies the second of fluoropolymer.PVDF fluorine content is up to 59wt%, because fluorine atom electronegativity is strong, atomic radius less (1.32), C-F key bond energy large (485KJ/mol), and fluorine atom symmetry replaces distribution, PVDF has hypocrystalline, heat-resisting, weather-proof and chemical resistance is excellent, hydrophobic oleophobic, the features such as surface energy is low, and specific inductivity is little.Therefore, PVDF is widely used in the industries such as building, aerospace, electronics, chemical industry, environmental protection, new forms of energy.
Membrane product is one of important application of PVDF, can obtain dense film and porous-film according to working method difference, and wherein porous-film is mainly used in various sewage disposal and sea water desaltination etc., especially in membrane bioreactor (MBR) sewage disposal device.MBR technology is a kind of Novel sewage treatment technology organically combining membrane technique and biotechnology, it adopts the second pond in membrane separation plant replacement conventional biochemical treating processes, active sludge in biochemical reaction tank and larger molecular organics are retained, having the advantages such as contaminant removal efficiency is high, stable effluent quality, convenient operation and management, floor space are little, is one of the most promising sewage disposal technology.For the ultrafiltration of MBR, microfiltration membrane material through development in recent years, achieve by the transformation of polyolefin film to pvdf membrane gradually, PVDF becomes the main flow mould material of MBR gradually, and defines non-solvent inversion of phases, thermic inversion of phases and increase the membrane preparation method of supporting tube.In addition, pvdf membrane isolation technique also can be used for conventional industries (as oil, chemical industry, the energy etc.) transformation and new high-tech industry (as sea water desaltination, bio-pharmaceuticals and artificial organs etc.), plays the effect reducing energy consumption, advance relevant industries progress.
Due to the hydrophobic property of PVDF, make the pure PVDF membrane for water treatment of non-modified in use easily microorganism clogging and pollution occur, cause the reduction gradually of membrane flux.Therefore, the important content that hydrophilic modifying becomes production high-performance PVDF water treatment porous-film is carried out to PVDF.At present, hydrophilic modifying is carried out to PVDF and mainly contains two class methods: (1) blending method: by hydrophilic macromolecule or hydrophilic inorganic nanoparticle physical blendings such as PVDF and polyoxyethylene glycol (PEG), polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyvinylpyrrolidones (PVP), then porous-film is prepared (as Chinese patent CN101091882, CN101874992A; Materials and Manufacturing Processes 2010,25 (9), 1018-1020); (2) graft copolymerization: first activation treatment is carried out to pvdf membrane, again by high-energy radiation free radical grafting copolymerization and living free radical graft copolymerization (atom transferred free radical and reversible addion-fragmentation chain transfer graft copolymerization etc.) method, hydrophilic monomer is grafted to PVDF surface (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 physical mixed, and PVDF and modified component often exist consistency difference, is difficult to mix, and can cause the instability of PVDF porous-film performance.On the other hand, hydrophilic macromolecule has certain dissolving power in water, along with the increase of duration of service, can dissolve gradually and move disengaging pvdf membrane, causes the hydrophilic ability of pvdf membrane to decline.Though method 2 can the shortcoming of conquering method 1, but technics comparing is complicated, usually first surface activation process (as process means such as ozone, alkali, plasma or energetic rays) to be carried out to PVDF, introduce corresponding functional group by surface chemical reaction again, realize the grafting of polymerizable hydrophilic monomer thing on pvdf membrane finally by general radical or living radical copolymerization.Energetic ray to equipment and environmental requirement higher, industrialization difficulty is large; The reaction conditions of atom transfer and the copolymerization of reversible addion-fragmentation chain transfer living free radical graft is comparatively harsh, and complex process, is difficult to industrial applications.
Except above-mentioned two kinds of methods, it is also the important channel of carrying out hydrophilic modifying that PVDF and hydrophilic polymer form block copolymer structure, because hydrophilic polymer is connected with chemical bond with PVDF, therefore not easily run off in film use procedure, the long-acting pollution resistance of pvdf membrane and the stability of membrane flux can be kept.PVDF segmented copolymer is prepared mainly through substep active free radical polymerization, although the segmented copolymers such as PVDF and polystyrene, PVDF and poly-(methyl) esters of acrylic acid studies have reported that, but the segmented copolymer formed about PVDF and hydrophilic polymer is reported seldom, and the synthesis of PVDF and polyacrylic segmented copolymer and the application in the modification of PVDF porous-film thereof have not been reported.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of polyvinylidene difluoride (PVDF)-polyacrylic acid segmented copolymer.
The step of the preparation method of a kind of polyvinylidene difluoride (PVDF)-polyacrylic acid segmented copolymer is:
1) deionized water of 1000 mass parts, 2.5 ~ 5 mass parts emulsifying agents, 5 ~ 10 mass parts assistant for emulsifying agents, the chain-transfer agent of 7.5 ~ 30 mass parts and the initiator of 1.5-6.5 mass parts are joined in reactor, logical nitrogen deoxygenation is less than 5ppm to oxygen level, high-speed stirring fine crankshaft under normal temperature; Be warmed up to 45 ~ 80
othe reaction design temperature of C, and pass into vinylidene fluoride monomers to setting pressure 3.0 MPa, start polymerization, when after still internal pressure decline 0.1MPa, supplement vinylidene fluoride monomers to setting pressure, repeatable operation; When accumulative monomer pressure drop is 4.0 ~ 6.3MPa, stops supplementing vinylidene fluoride monomers, continue to be polymerized to pressure drop to 1.5MPa, be cooled to normal temperature and terminate polymerization, get rid of unreacted vinylidene fluoride monomers, obtain active polyvinylidene difluoride (PVDF) seed emulsion;
2) in active polyvinylidene difluoride (PVDF) seed emulsion, add the acrylonitrile monemer of 20 ~ 100 mass parts, dispersed with stirring, swelling 2 ~ 5h, be warming up to 45 ~ 80 at normal temperatures
othe reaction design temperature of C continues polymerization 5 ~ 10h, and centrifugation, drying obtain polyvinylidene difluoride (PVDF)-polyacrylonitrile block multipolymer;
3) polyvinylidene difluoride (PVDF)-polyacrylonitrile block multipolymer is dissolved in
n,Nobtain the solution that mass concentration is 10 ~ 15% in-N,N-DIMETHYLACETAMIDE, add relative to
n,Nthe concentration of-dimethylacetamide solution 2 ~ 10% quality is the NaOH aqueous solution of 50wt%, 50 ~ 75
obe hydrolyzed 2 ~ 8h under C, obtain polyvinylidene difluoride (PVDF)-polyacrylic acid segmented copolymer.
Described emulsifying agent is ammonium perfluorocaprylate, cetyl trimethylammonium bromide or palmityl trimethyl ammonium chloride.
Described assistant for emulsifying agent is n-hexadecane or positive hexadecanol.Described chain-transfer agent is C
4f
9i, C
6f
13i, ICF
2cF
2i or IC
4f
8i.Described initiator is azo dicyano valeric acid, 2,2'-azos [2-(2-tetrahydroglyoxaline-2-base) propane] dihydrochloride, ammonium persulphate or Potassium Persulphate.
The technique effect of employing the inventive method is: take water as reaction medium, adopt mini-emulsion polymerization method, polymerization rate can be improved, obtain that molecular weight is controlled, the end-capping living PVDF of the iodine of narrow molecular weight distribution, and acrylonitrile polymerization can be regulated and controled further, obtain forming adjustable PVDF-PAN segmented copolymer; Obtain PVDF-PAA segmented copolymer because Acrylic Acid Monomer is difficult to the radical polymerization of iodine transfer activity, and the present invention adopts the method indirectly being prepared PVDF-PAA segmented copolymer by the hydrolysis of PVDF-PAN segmented copolymer, technique is simple; The polyacrylic acid hydrophilic segment that the present invention obtains and PVDF segment are with covalent bonds, and the wetting ability of energy long-acting improvement PVDF, improves the pollution resistance of PVDF porous-film.
Embodiment
The present invention adopts iodine transfer activity free radical mini-emulsion polymerization to prepare PVDF-PAN segmented copolymer.Compare other active free radical polymerization, the radical polymerization of iodine transfer activity is comparatively applicable to fluorochemical monomer, especially the active free radical polymerization method of vinylidene.The iodine transfer activity radical polymerization of vinylidene adopts alkyl iodide to be chain-transfer agent, and conventional alkyl iodide compounds has C
4f
9i, C
6f
13i, ICF
2cF
2i and IC
4f
8i, adopt single iodine end alkyl iodide can prepare active PVDF containing single-ended base iodine, and adopt the alkyl iodide containing two end group iodine can prepare the active PVDF of molecular chain both-end base iodine, the PVDF segmented copolymer of diblock can be prepared from the active PVDF of single-ended base iodine, and from the active PVDF of both-end base iodine, the PVDF segmented copolymer of three blocks can be prepared.
The present invention adopts mini-emulsion polymerization method to carry out VDF polymerization and take PVDF as the Active radical polymerization of vinyl cyanide of seed, mini-emulsion polymerization system is made up of water, primary emulsion and assistant for emulsifying agent, initiator, chain-transfer agent and monomer etc., water, primary emulsion and assistant for emulsifying agent, the first high-speed stirring at low temperatures of chain-transfer agent form homogenized liquid, heat up after adding VDF monomer and initiator and start polymerization, obtain stable polymer emulsion.According to the characteristic of VDF monomer, ammonium perfluorocaprylate, cetyl trimethylammonium bromide and palmityl trimethyl ammonium chloride is selected to be primary emulsion; N-hexadecane and positive hexadecanol is selected to be assistant for emulsifying agent.The consumption of primary emulsion is 2.5 ~ 5 mass fraction/1000 mass fraction deionized waters, and the consumption of assistant for emulsifying agent is 5 ~ 10 mass fraction/1000 mass fraction deionized waters.
Mini-emulsion polymerization both can be caused by water soluble starter, also can be caused by oil-soluble initiator, the present invention selects water soluble starter to cause VDF and AN polymerization, concrete kind is azo dicyano valeric acid (V-501), 2,2'-azo [2-(2-tetrahydroglyoxaline-2-base) propane] dihydrochloride (VA-044), ammonium persulphate (APS) and Potassium Persulphate (KPS), the consumption of initiator is the initiator of 1.5-6.5 mass fraction/1000 number.
Vinylidene fluoride polymerization is the process of gas-liquid mass transferring/chemical reaction coupling, the VDF monomer concentration of reacting environment is relevant with solution-air rate of mass transfer with gaseous pressure, the present invention adopts polymerization to start first to be pressed in reactor the VDF monomer of 3.0MPa, and after polymeric kettle internal pressure decline 1.0MPa, supplement VDF monomer to setting pressure, and repeat above operation until reach certain accumulative monomer pressure drop (4.0 ~ 6.3MPa), stop supplementing VDF monomer, continue to be polymerized to pressure drop to 1.5MPa, terminate be polymerized and get rid of unreacted VDF monomer, obtain PVDF emulsion.
On obtained stable active PVDF emulsion basis, add AN monomer and fully swelling after, heat up polymerization, and iodine end-blocking PVDF can play Macromolecular chain transfer agent, and regulation and control polymerization generates PVDF-PAN segmented copolymer.
Cyano group in PVDF-PAN segmented copolymer is hydrolyzed in the basic conditions, can change carboxyl into, thus makes PAN-PAN segmented copolymer be converted into PAN-PAA segmented copolymer.Complete in order to ensure the conversion of cyano group, PVDF-PAN segmented copolymer is first dissolved in
n, N-in dimethylacetamide solvent, then add a small amount of containing NaOH aqueous hydrolysis.
The introducing of PAA block carries out simple evaluation to the hydrophilic effect of improving of PVDF by the water contact angle measuring polymeric film, and concrete testing method is: take a certain amount of PVDF or PVDF-PAA block copolymerization matter sample, be dissolved in
n,Nin-N,N-DIMETHYLACETAMIDE (DMAc), the solution of preparation 7wt%, gets appropriate solution and drips on glass substrate, 40 DEG C of standing film forming 48h.The OCA-20 video optics contact angle instrument etc. of German Dataphysics company is adopted to carry out the water contact angle measurement of polymeric film, 3.5 μ l water droplets are dripped with microsyringe, sample is upwards slowly also used camera recordings near drop from bottom, gets drips and carry out contact angle analysis to the sample surfaces image picture of the 2nd second.Wherein PVDF sample be polymerized by the first step obtain emulsion breaking, centrifugation, washing, vacuum-drying obtains.
The technique effect of employing the inventive method is: take water as reaction medium, adopt mini-emulsion polymerization method, polymerization rate can be improved, obtain that molecular weight is controlled, the end-capping living PVDF of the iodine of narrow molecular weight distribution, and AN polymerization can be regulated and controled further, obtain forming adjustable PVDF-PAN segmented copolymer; Obtain PVDF-PAA segmented copolymer because Acrylic Acid Monomer is difficult to the radical polymerization of iodine transfer activity, and the present invention adopts the method indirectly being prepared PVDF-PAA segmented copolymer by the hydrolysis of PVDF-PAN segmented copolymer, technique is simple; The polyacrylic acid hydrophilic segment that the present invention obtains and PVDF segment are with covalent bonds, and the wetting ability of energy long-acting improvement PVDF, improves the pollution resistance of PVDF porous-film.
embodiment 1
In 5L reactor, add the ICF of 2000 ml water, 5.0g ammonium perfluorocaprylate, the positive hexadecanol of 20.0g, 15.2g
2cF
2the VA-044 of I, 3.2g, passes into N
2row O
2to content lower than 5ppm, high-speed stirring 10min at 5 DEG C, obtains miniemulsion; Be warmed up to 45
oc, passing into VDF monomer to still internal pressure is 3.0 MPa, starts polymerization.When after still internal pressure decline 0.1MPa, supplementing VDF monomer to still internal pressure is 3.0MPa, repeatable operation.When accumulative monomer pressure drop reaches 4.0MPa, stop supplementing VDF monomer, continue to be polymerized to pressure drop to 1.5MPa, be cooled to room temperature and terminate polymerization, get rid of unreacted VDF monomer, obtain active PVDF seed emulsion.
In still, add 40g vinyl cyanide, stirred at ambient temperature disperses, swelling 2h.Stop after being warming up to 45 DEG C of continuation reaction 5h.Centrifugal settling, 50 DEG C of vacuum-dryings, obtain PVDF-PAN segmented copolymer.
Get 15g PVDF-PAN block polymer, be dissolved in DMAc the solution being configured to 15%wt, add the NaOH solution of 2g 50%wt, 50 DEG C are stirred hydrolysis 8h, obtain PVDF-PAA segmented copolymer.
The water contact angle of gained PVDF-PAA block copolymer film is 75 o, and the water contact angle of pure pvdf membrane is 120 o.
embodiment 2
In 5L reactor, add the C of 2000 ml water, 5.0g ammonium perfluorocaprylate, 10.0g n-hexadecane, 58g
6f1
3the VA-044 of I, 3.2g, passes into N
2row O
2to content lower than 5ppm, high-speed stirring 10min at 5 DEG C, obtains miniemulsion; Be warmed up to 50
oc, passing into VDF monomer to still internal pressure is 3.0 MPa, starts polymerization.When after still internal pressure decline 0.1MPa, supplementing VDF monomer to still internal pressure is 3.0MPa, repeatable operation.When accumulative monomer pressure drop reaches 6.3MPa, stop supplementing VDF monomer, continue to be polymerized to pressure drop to 1.5MPa, be cooled to room temperature and terminate polymerization, get rid of unreacted VDF monomer, obtain active PVDF seed emulsion.
In still, add 200g vinyl cyanide, stirred at ambient temperature disperses, swelling 5h.Stop after being warming up to 50 DEG C of continuation reaction 10h.Centrifugal settling, 50 DEG C of vacuum-dryings, obtain PVDF-PAN segmented copolymer.
Get 10g PVDF-PAN block polymer, be dissolved in DMAc the solution being configured to 10%wt, add the NaOH solution of 10g 50%wt, 70 DEG C are stirred hydrolysis 5h, obtain PVDF-PAA segmented copolymer.
The water contact angle of gained PVDF-PAA block copolymer film is 80 o, and the water contact angle of pure pvdf membrane is 120 o.
embodiment 3
In 5L reactor, add the C of 2000 ml water, 8.0g ammonium perfluorocaprylate, 15.0g n-hexadecane, 29.0g
4f
9the APS of I, 4.0g, passes into N
2row O
2to content lower than 5ppm, high-speed stirring 10min under 5 DEG C of conditions, obtains miniemulsion; Be warmed up to 80
oc, passing into VDF monomer to still internal pressure is 3.0 MPa, starts polymerization.When after still internal pressure decline 1.0MPa, supplementing VDF monomer to still internal pressure is 3.0MPa, repeatable operation.When accumulative monomer pressure drop reaches 5.8MPa, stop supplementing VDF monomer, continue to be polymerized to pressure drop to 1.5MPa, be cooled to room temperature and terminate polymerization, get rid of unreacted VDF monomer, obtain active PVDF seed emulsion.
In still, add 100g vinyl cyanide, stirred at ambient temperature disperses, swelling 2h.Stop after being warming up to 80 DEG C of continuation reaction 5h.Centrifugal settling, 50 DEG C of vacuum-dryings, obtain PVDF-PAN segmented copolymer.
Get 15g PVDF-PAN block polymer, be dissolved in DMAc the solution being configured to 15%wt, add the NaOH solution of 10g 50%wt, 75 DEG C are stirred hydrolysis 2h, obtain PVDF-PAA segmented copolymer.
The water contact angle of gained PVDF-PAA block copolymer film is 78 o, and the water contact angle of pure pvdf membrane is 120 o.
embodiment 4
In 5L reactor, add the C of 2000 ml water, 9.0g cetyl trimethylammonium bromide, 12.0g n-hexadecane, 16.0g
4f
9the APS of I, 4.0g, passes into N
2row O
2to content lower than 5ppm, high-speed stirring 10min under 5 DEG C of conditions, obtains miniemulsion; Be warmed up to 75
oc, passing into VDF monomer to still internal pressure is 3.0 MPa, starts polymerization.When after still internal pressure decline 1.0MPa, supplementing VDF monomer to still internal pressure is 3.0MPa, repeatable operation.When accumulative monomer pressure drop reaches 5.8MPa, stop supplementing VDF monomer, continue to be polymerized to pressure drop to 1.5MPa, be cooled to room temperature and terminate polymerization, get rid of unreacted VDF monomer, obtain active PVDF seed emulsion.
In still, add 100g vinyl cyanide, stirred at ambient temperature disperses, swelling 2h.Stop after being warming up to 75 DEG C of continuation reaction 5h.Centrifugal settling, 50 DEG C of vacuum-dryings, obtain PVDF-PAN segmented copolymer.
Get 15g PVDF-PAN block polymer, be dissolved in DMAc the solution being configured to 15%wt, add the NaOH solution of 8g 50%wt, 75 DEG C are stirred hydrolysis 2h, obtain PVDF-PAA segmented copolymer.
The water contact angle of gained PVDF-PAA block copolymer film is 73 o, and the water contact angle of pure pvdf membrane is 120 o.
embodiment 5
In 5L reactor, add the IC of 2000 ml water, 9.0g cetyl trimethylammonium bromide, 15.0g n-hexadecane, 20.0g
4f
8the KPS of I, 4.0g, passes into N
2row O
2to content lower than 5ppm, high-speed stirring 10min under 5 DEG C of conditions, obtains miniemulsion; Be warmed up to 75
oc, passing into VDF monomer to still internal pressure is 3.0 MPa, starts polymerization.When after still internal pressure decline 1.0MPa, supplementing VDF monomer to still internal pressure is 3.0MPa, repeatable operation.When accumulative monomer pressure drop reaches 5.0MPa, stop supplementing VDF monomer, continue to be polymerized to pressure drop to 1.5MPa, be cooled to room temperature and terminate polymerization, get rid of unreacted VDF monomer, obtain active PVDF seed emulsion.
In still, add 80g vinyl cyanide, stirred at ambient temperature disperses, swelling 2h.Stop after being warming up to 75 DEG C of continuation reaction 3h.Centrifugal settling, 50 DEG C of vacuum-dryings, obtain PVDF-PAN segmented copolymer.
Get 15g PVDF-PAN block polymer, be dissolved in DMAc the solution being configured to 15%wt, add the NaOH solution of 10g 50%wt, 65 DEG C are stirred hydrolysis 8h, obtain PVDF-PAA segmented copolymer.
The water contact angle of gained PVDF-PAA block copolymer film is 82 o, and the water contact angle of pure pvdf membrane is 120 o.
embodiment 6
In 5L reactor, add the IC of 2000 ml water, 10.0g palmityl trimethyl ammonium chloride, 10.0g n-hexadecane, 25.0g
4f
9the APS of I, 4.0g, passes into N
2row O
2to content lower than 5ppm, high-speed stirring 10min under 5 DEG C of conditions, obtains miniemulsion; Be warmed up to 78
oc, passing into VDF monomer to still internal pressure is 3.0 MPa, starts polymerization.When after still internal pressure decline 1.0MPa, supplementing VDF monomer to still internal pressure is 3.0MPa, repeatable operation.When accumulative monomer pressure drop reaches 5.8MPa, stop supplementing VDF monomer, continue to be polymerized to pressure drop to 1.5MPa, be cooled to room temperature and terminate polymerization, get rid of unreacted VDF monomer, obtain active DF seed emulsion.
In still, add 100g vinyl cyanide, stirred at ambient temperature disperses, swelling 2h.Stop after being warming up to 78 DEG C of continuation reaction 5h.Centrifugal settling, 50 DEG C of vacuum-dryings, obtain PVDF-PAN segmented copolymer.
Get 15g PVDF-PAN block polymer, be dissolved in DMAc the solution being configured to 15%wt, add the NaOH solution of 10g 50%wt, 75 DEG C are stirred hydrolysis 2h, obtain PVDF-PAA segmented copolymer.
The water contact angle of gained PVDF-PAA block copolymer film is 70 o, and the water contact angle of pure pvdf membrane is 120 o.
embodiment 7
In 5L reactor, add the ICF of 2000 ml water, 10.0g ammonium perfluorocaprylate, 10.0g n-hexadecane, 16.0g
2cF
2the APS of I, 4.0g, passes into N
2row O
2to content lower than 5ppm, high-speed stirring 10min under 5 DEG C of conditions, obtains miniemulsion; Be warmed up to 75
oc, passing into VDF monomer to still internal pressure is 3.0 MPa, starts polymerization.When after still internal pressure decline 1.0MPa, supplementing VDF monomer to still internal pressure is 3.0MPa, repeatable operation.When accumulative monomer pressure drop reaches 5.8MPa, stop supplementing VDF monomer, continue to be polymerized to pressure drop to 1.5MPa, be cooled to room temperature and terminate polymerization, get rid of unreacted VDF monomer, obtain active PVDF seed emulsion.
In still, add 100g vinyl cyanide, stirred at ambient temperature disperses, swelling 2h.Stop after being warming up to 75 DEG C of continuation reaction 5h.Centrifugal settling, 50 DEG C of vacuum-dryings, obtain PVDF-PAN segmented copolymer.
Get 15g PVDF-PAN block polymer, be dissolved in DMAc the solution being configured to 15%wt, add the NaOH solution of 2g 50%wt, 75 DEG C are stirred hydrolysis 8h, obtain PVDF-PAA segmented copolymer.
The water contact angle of gained PVDF-PAA block copolymer film is 74 o, and the water contact angle of pure pvdf membrane is 120 o.
embodiment 8
In 5L reactor, add the IC of 2000 ml water, 7.0g ammonium perfluorocaprylate, 10.0g n-hexadecane, 25.0g
4f
9the V-501 of I, 8.0g, passes into N
2row O
2to content lower than 5ppm, high-speed stirring 10min under 5 DEG C of conditions, obtains miniemulsion; Be warmed up to 70
oc, passing into VDF monomer to still internal pressure is 3.0 MPa, starts polymerization.When after still internal pressure decline 1.0MPa, supplementing VDF monomer to still internal pressure is 3.0MPa, repeatable operation.When accumulative monomer pressure drop reaches 5.5MPa, stop supplementing VDF monomer, continue to be polymerized to pressure drop to 1.5MPa, be cooled to room temperature and terminate polymerization, get rid of unreacted VDF monomer, obtain active PVDF seed emulsion.
In still, add 100g vinyl cyanide, stirred at ambient temperature disperses, swelling 5h.Stop after being warming up to 70 DEG C of continuation reaction 5h.Centrifugal settling, 50 DEG C of vacuum-dryings, obtain PVDF-PAN segmented copolymer.
Get 15g PVDF-PAN block polymer, be dissolved in DMAc the solution being configured to 15%wt, add the NaOH solution of 8g 50%wt, 75 DEG C are stirred hydrolysis 2h, obtain PVDF-PAA segmented copolymer.
The water contact angle of gained PVDF-PAA block copolymer film is 73 o, and the water contact angle of pure pvdf membrane is 120 o.
embodiment 9
In 5L reactor, add the ICF of 2000 ml water, 7.0g ammonium perfluorocaprylate, 10.0g n-hexadecane, 18.0g
2cF
2the VA-044 of I, 13.0g, passes into N
2row O
2to content lower than 5ppm, high-speed stirring 10min under 5 DEG C of conditions, obtains miniemulsion; Be warmed up to 50
oc, passing into VDF monomer to still internal pressure is 3.0 MPa, starts polymerization.When after still internal pressure decline 1.0MPa, supplementing VDF monomer to still internal pressure is 3.0MPa, repeatable operation.When accumulative monomer pressure drop reaches 5.5MPa, stop supplementing VDF monomer, continue to be polymerized to pressure drop to 1.5MPa, be cooled to room temperature and terminate polymerization, get rid of unreacted VDF monomer, obtain active PVDF seed emulsion.
In still, add 100g vinyl cyanide, stirred at ambient temperature disperses, swelling 5h.Stop after being warming up to 50 DEG C of continuation reaction 10h.Centrifugal settling, 50 DEG C of vacuum-dryings, obtain PVDF-PAN segmented copolymer.
Get 15g PVDF-PAN block polymer, be dissolved in DMAc the solution being configured to 15%wt, add the NaOH solution of 10g 50%wt, 65 DEG C are stirred hydrolysis 2h, obtain PVDF-PAA segmented copolymer.
The water contact angle of gained PVDF-PAA block copolymer film is 78 o, and the water contact angle of pure pvdf membrane is 120 o.
embodiment 10
In 5L reactor, add the IC of 2000 ml water, 7.0g ammonium perfluorocaprylate, 10.0g n-hexadecane, 40.0g
4f
9the V-501 of I, 10.0g, passes into N
2row O
2to content lower than 5ppm, high-speed stirring 10min under 5 DEG C of conditions, obtains miniemulsion; Be warmed up to 70
oc, passing into VDF monomer to still internal pressure is 3.0 MPa, starts polymerization.When after still internal pressure decline 1.0MPa, supplementing VDF monomer to still internal pressure is 3.0MPa, repeatable operation.When accumulative monomer pressure drop reaches 5.5MPa, stop supplementing VDF monomer, continue to be polymerized to pressure drop to 1.5MPa, be cooled to room temperature and terminate polymerization, get rid of unreacted VDF monomer, obtain active PVDF seed emulsion.
In still, add 100g vinyl cyanide, stirred at ambient temperature disperses, swelling 5h.Stop after being warming up to 70 DEG C of continuation reaction 10h.Centrifugal settling, 50 DEG C of vacuum-dryings, obtain PVDF-PAN segmented copolymer.
Get 15g PVDF-PAN block polymer, be dissolved in DMAc the solution being configured to 15%wt, add the NaOH solution of 2g 50%wt, 70 DEG C are stirred hydrolysis 8h, obtain PVDF-PAA segmented copolymer.
The water contact angle of gained PVDF-PAA block copolymer film is 83 o, and the water contact angle of pure pvdf membrane is 120 o.
embodiment 11
In 5L reactor, add the C of 2000 ml water, 7.0g ammonium perfluorocaprylate, 10.0g n-hexadecane, 58.0g
6f
13the V-501 of I, 10.0g, passes into N
2row O
2to content lower than 5ppm, high-speed stirring 10min under 5 DEG C of conditions, obtains miniemulsion; Be warmed up to 70
oc, passing into VDF monomer to still internal pressure is 3.0 MPa, starts polymerization.When after still internal pressure decline 1.0MPa, supplementing VDF monomer to still internal pressure is 3.0MPa, repeatable operation.When accumulative monomer pressure drop reaches 5.5MPa, stop supplementing VDF monomer, continue to be polymerized to pressure drop to 1.5MPa, be cooled to room temperature and terminate polymerization, get rid of unreacted VDF monomer, obtain active PVDF seed emulsion.
In still, add 100g vinyl cyanide, stirred at ambient temperature disperses, swelling 5h.Stop after being warming up to 70 DEG C of continuation reaction 10h.Centrifugal settling, 50 DEG C of vacuum-dryings, obtain PVDF-PAN segmented copolymer.
Get 15g PVDF-PAN block polymer, be dissolved in DMAc the solution being configured to 15%wt, add the NaOH solution of 10g 50%wt, 70 DEG C are stirred hydrolysis 5h, obtain PVDF-PAA block polymer.
The water contact angle of gained PVDF-PAA block copolymer film is 77 o, and the water contact angle of pure pvdf membrane is 120 o.
embodiment 12
In 5L reactor, add the C of 2000 ml water, 10.0g ammonium perfluorocaprylate, the positive hexadecanol of 20.0g, 58g
6f
13the VA-044 of I, 13.0g, passes into N
2row O
2to content lower than 5ppm, high-speed stirring 10min under 5 DEG C of conditions, obtains miniemulsion; Be warmed up to 50
oc, passing into VDF monomer to still internal pressure is 3.0 MPa, starts polymerization.When after still internal pressure decline 1.0MPa, supplementing VDF monomer to still internal pressure is 3.0MPa, repeatable operation.When accumulative monomer pressure drop reaches 6.3MPa, stop supplementing VDF monomer, continue to be polymerized to pressure drop to 1.5MPa, be cooled to room temperature and terminate polymerization, get rid of unreacted VDF monomer, obtain active PVDF seed emulsion.
In still, add 200g vinyl cyanide, stirred at ambient temperature disperses, swelling 5h.Stop after being warming up to 50 DEG C of continuation reaction 10h.Centrifugal settling, 50 DEG C of vacuum-dryings, obtain PVDF-PAN segmented copolymer.
Get 15g PVDF-PAN segmented copolymer, be dissolved in DMAc the solution being configured to 15%wt, add the NaOH solution of 8g 50%wt, 65 DEG C are stirred hydrolysis 2h, obtain PVDF-PAA segmented copolymer.
The water contact angle of gained PVDF-PAA block copolymer film is 65 o, and the water contact angle of pure pvdf membrane is 120 o.
embodiment 13
In 5L reactor, add the ICF of 2000 ml water, 7.0g ammonium perfluorocaprylate, the positive hexadecanol of 15.0g, 15.2g
2cF
2the APS of I, 8.0g, passes into N
2row O
2to content lower than 5ppm, high-speed stirring 10min under 5 DEG C of conditions, obtains miniemulsion; Be warmed up to 80
oc, passing into VDF monomer to still internal pressure is 3.0 MPa, starts polymerization.When after still internal pressure decline 1.0MPa, supplementing VDF monomer to still internal pressure is 3.0MPa, repeatable operation.When accumulative monomer pressure drop reaches 4.0MPa, stop supplementing VDF monomer, continue to be polymerized to pressure drop to 1.5MPa, be cooled to room temperature and terminate polymerization, get rid of unreacted VDF monomer, obtain active PVDF seed emulsion.
In still, add 40g vinyl cyanide, stirred at ambient temperature disperses, swelling 5h.Stop after being warming up to 80 DEG C of continuation reaction 5h.Centrifugal settling, 50 DEG C of vacuum-dryings, obtain PVDF-PAN segmented copolymer.
Get 15g PVDF-PAN segmented copolymer, be dissolved in DMAc the solution being configured to 15%wt, add the NaOH solution of 5g 50%wt, 50 DEG C are stirred hydrolysis 2h, obtain PVDF-PAA segmented copolymer.
The water contact angle of gained PVDF-PAA block copolymer film is 70 o, and the water contact angle of pure pvdf membrane is 120 o.
embodiment 14
In 5L reactor, add the ICF of 2000 ml water, 10.0g palmityl trimethyl ammonium chloride, the positive hexadecanol of 20.0g, 15.2g
2cF
2the V-501 of I, 3.2g, passes into N
2row O
2to content lower than 5ppm, high-speed stirring 10min under 5 DEG C of conditions, obtains miniemulsion; Be warmed up to 70
oc, passing into VDF monomer to still internal pressure is 3.0 MPa, starts polymerization.When after still internal pressure decline 1.0MPa, supplementing VDF monomer to still internal pressure is 3.0MPa, repeatable operation.When accumulative monomer pressure drop reaches 5.0MPa, stop supplementing VDF monomer, continue to be polymerized to pressure drop to 1.5MPa, be cooled to room temperature and terminate polymerization, get rid of unreacted VDF monomer, obtain active PVDF seed emulsion.
In still, add 40g vinyl cyanide, stirred at ambient temperature disperses, swelling 2h.Stop after being warming up to 70 DEG C of continuation reaction 5h.Centrifugal settling, 50 DEG C of vacuum-dryings, obtain PVDF-PAN segmented copolymer.
Get 10g PVDF-PAN segmented copolymer, be dissolved in DMAc the solution being configured to 10%wt, add the NaOH solution of 10g 50%wt, 70 DEG C are stirred hydrolysis 8h, obtain PVDF-PAA segmented copolymer.
The water contact angle of gained PVDF-PAA block copolymer film is 75 o, and the water contact angle of pure pvdf membrane is 120 o.
embodiment 15
In 5L reactor, add the IC of 2000 ml water, 9.0g palmityl trimethyl ammonium chloride, 10.0g n-hexadecane, 25.0g
4f
9the VA-044 of I, 8.0g, passes into N
2row O
2to content lower than 5ppm, high-speed stirring 10min under 5 DEG C of conditions, obtains miniemulsion; Be warmed up to 45
oc, passing into VDF monomer to still internal pressure is 3.0 MPa, starts polymerization.When after still internal pressure decline 1.0MPa, supplementing VDF monomer to still internal pressure is 3.0MPa, repeatable operation.When accumulative monomer pressure drop reaches 5.0MPa, stop supplementing VDF monomer, continue to be polymerized to pressure drop to 1.5MPa, be cooled to room temperature and terminate polymerization, get rid of unreacted VDF monomer, obtain active PVDF seed emulsion.
In still, add 200g vinyl cyanide, stirred at ambient temperature disperses, swelling 5h.Stop after being warming up to 45 DEG C of continuation reaction 5h.Centrifugal settling, 50 DEG C of vacuum-dryings, obtain PVDF-PAN segmented copolymer.
Get 10g PVDF-PAN segmented copolymer, be dissolved in DMAc the solution being configured to 10%wt, add the NaOH solution of 10g 50%wt, 75 DEG C are stirred hydrolysis 2h, obtain PVDF-PAA segmented copolymer.
The water contact angle of gained PVDF-PAA block copolymer film is 68 o, and the water contact angle of pure pvdf membrane is 120 o.
embodiment 16
In 5L reactor, add the IC of 2000 ml water, 8.0g cetyl trimethylammonium bromide, 10.0g n-hexadecane, 20.0g
4f
9the VA-044 of I, 8.0g, passes into N
2row O
2to content lower than 5ppm, high-speed stirring 10min under 5 DEG C of conditions, obtains miniemulsion; Be warmed up to 50
oc, passing into VDF monomer to still internal pressure is 3.0 MPa, starts polymerization.When after still internal pressure decline 1.0MPa, supplementing VDF monomer to still internal pressure is 3.0MPa, repeatable operation.When accumulative monomer pressure drop reaches 4.0MPa, stop supplementing VDF monomer, continue to be polymerized to pressure drop to 1.5MPa, be cooled to room temperature and terminate polymerization, get rid of unreacted VDF monomer, obtain active PVDF seed emulsion.
In still, add 40g vinyl cyanide, stirred at ambient temperature disperses, swelling 5h.Stop after being warming up to 50 DEG C of continuation reaction 10h.Centrifugal settling, 50 DEG C of vacuum-dryings, obtain PVDF-PAN segmented copolymer.
Get 15g PVDF-PAN segmented copolymer, be dissolved in DMAc the solution being configured to 15%wt, add the NaOH solution of 10g 50%wt, 50 DEG C are stirred hydrolysis 2h, obtain PVDF-PAA segmented copolymer.
The water contact angle of gained PVDF-PAA block copolymer film is 81 o, and the water contact angle of pure pvdf membrane is 120 o.
Claims (5)
1. a preparation method for polyvinylidene difluoride (PVDF)-polyacrylic acid segmented copolymer, is characterized in that the step of method is:
1) deionized water of 1000 mass parts, 2.5 ~ 5 mass parts emulsifying agents, 5 ~ 10 mass parts assistant for emulsifying agents, the chain-transfer agent of 7.5 ~ 30 mass parts and the initiator of 1.5-6.5 mass parts are joined in reactor, logical nitrogen deoxygenation is less than 5ppm to oxygen level, high-speed stirring fine crankshaft under normal temperature; Be warmed up to 45 ~ 80
othe reaction design temperature of C, and pass into vinylidene fluoride monomers to setting pressure 3.0 MPa, start polymerization, when after still internal pressure decline 0.1MPa, supplement vinylidene fluoride monomers to setting pressure, repeatable operation; When accumulative monomer pressure drop is 4.0 ~ 6.3MPa, stops supplementing vinylidene fluoride monomers, continue to be polymerized to pressure drop to 1.5MPa, be cooled to normal temperature and terminate polymerization, get rid of unreacted vinylidene fluoride monomers, obtain active polyvinylidene difluoride (PVDF) seed emulsion;
2) in active polyvinylidene difluoride (PVDF) seed emulsion, add the acrylonitrile monemer of 20 ~ 100 mass parts, dispersed with stirring, swelling 2 ~ 5h, be warming up to 45 ~ 80 at normal temperatures
othe reaction design temperature of C continues polymerization 5 ~ 10h, and centrifugation, drying obtain polyvinylidene difluoride (PVDF)-polyacrylonitrile block multipolymer;
3) polyvinylidene difluoride (PVDF)-polyacrylonitrile block multipolymer is dissolved in
n,Nobtain the solution that mass concentration is 10 ~ 15% in-N,N-DIMETHYLACETAMIDE, add relative to
n,Nthe concentration of-dimethylacetamide solution 2 ~ 10% quality is the NaOH aqueous solution of 50wt%, 50 ~ 75
obe hydrolyzed 2 ~ 8h under C, obtain polyvinylidene difluoride (PVDF)-polyacrylic acid segmented copolymer.
2. the preparation method of a kind of polyvinylidene difluoride (PVDF)-polyacrylic acid segmented copolymer according to right 1, is characterized in that described emulsifying agent is ammonium perfluorocaprylate, cetyl trimethylammonium bromide or palmityl trimethyl ammonium chloride.
3. the preparation method of a kind of polyvinylidene difluoride (PVDF)-polyacrylic acid segmented copolymer according to right 1, is characterized in that described assistant for emulsifying agent is n-hexadecane or positive hexadecanol.
4. the preparation method of a kind of polyvinylidene difluoride (PVDF)-polyacrylic acid segmented copolymer according to right 1, is characterized in that described chain-transfer agent is C
4f
9i, C
6f
13i, ICF
2cF
2i or IC
4f
8i.
5. the preparation method of a kind of polyvinylidene difluoride (PVDF)-polyacrylic acid segmented copolymer according to right 1, it is characterized in that described initiator is azo dicyano valeric acid, 2,2'-azos [2-(2-tetrahydroglyoxaline-2-base) propane] dihydrochloride, ammonium persulphate or Potassium Persulphate.
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| CN106543388A (en) * | 2016-10-22 | 2017-03-29 | 宁波大学 | A kind of environment-friendly preparation method thereof of anionic PVDF membrane material |
| 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 |
| CN109722190A (en) * | 2018-12-25 | 2019-05-07 | 浙江中科立德新材料有限公司 | A kind of preparation method and its binder of lithium battery silicon-based anode binder |
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| CN112029057A (en) * | 2020-07-14 | 2020-12-04 | 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 |
| CN115286805A (en) * | 2022-09-30 | 2022-11-04 | 宁德时代新能源科技股份有限公司 | BAB type block copolymer, preparation method, binder, positive pole piece, secondary battery and electric device |
| WO2024066507A1 (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, preparation method, binder, positive pole piece, secondary battery, and electrical apparatus |
| 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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| CN106543388B (en) * | 2016-10-22 | 2018-09-04 | 宁波大学 | A kind of environment-friendly preparation method thereof of anionic PVDF membrane material |
| WO2019121494A1 (en) * | 2017-12-19 | 2019-06-27 | Solvay Specialty Polymers Italy S.P.A. | Fluorinated block copolymers and application thereof |
| CN111511787A (en) * | 2017-12-19 | 2020-08-07 | 索尔维特殊聚合物意大利有限公司 | Fluorinated block copolymers and uses thereof |
| US11655325B2 (en) | 2017-12-19 | 2023-05-23 | Solvay Specialty Polymers Italy S.P.A. | Fluorinated block copolymers and application thereof |
| CN111511787B (en) * | 2017-12-19 | 2023-11-03 | 索尔维特殊聚合物意大利有限公司 | Fluorinated block copolymers and their use |
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