CN105985495B - A kind of cationic functional fluoropolymer and preparation method thereof - Google Patents

A kind of cationic functional fluoropolymer and preparation method thereof Download PDF

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CN105985495B
CN105985495B CN201510058266.6A CN201510058266A CN105985495B CN 105985495 B CN105985495 B CN 105985495B CN 201510058266 A CN201510058266 A CN 201510058266A CN 105985495 B CN105985495 B CN 105985495B
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cationic functional
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functional fluoropolymer
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朱宝库
银雪
姚之侃
王纳川
方立峰
周名勇
崔月
许云秋
包永忠
朱利平
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Zhejiang University ZJU
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Abstract

The present invention discloses a kind of cationic functional fluoropolymer and preparation method thereof.The functionalization fluoropolymer is using fluorochemical monomer, can be grafted activated monomer and hydrophile function monomer as comonomer, the active precursor polymer that main chain contains atom transfer radical polymerization active lateral group is first aggregated into Aqueous dispersions system, then active lateral group is recycled to trigger cationic functional monomer to carry out interface atoms transferring free-radical polymerization in solid liquid interface, polymerization forms the cationic functional fluoropolymer containing cationic side chain.Cationic side chain contains quaternary ammonium salt and quaternary phosphonium salt class group, there is very strong lotus electropositive, make polymer that there is very strong anti-microbial property, hydrophilicity and anion exchange absorbing performance, it can be individually used for preparing or preparing high-hydrophilic antibiotic property with other resin alloys separating membrane product, gel electrolyte, adhesive, battery diaphragm, anion exchange absorbing material and antibiotic paint, the application range of vinyl chloride polymer is greatly widened, the good hydrophilic property compared with current material, antibacterial, application prospect are good.

Description

A kind of cationic functional fluoropolymer and preparation method thereof
Technical field
The invention belongs to the invention belongs to polymeric material field, more particularly to a kind of cationic functional fluoropolymer And preparation method thereof.
Background technology
Fluorine atom has the high bond energy (485.3kJ/mol) of strong electronegativity, hypopolarization rate, weak Van der Waals force and C-F keys, So that fluoropolymer has the heat-resisting of protrusion, solvent resistant, acid-alkali-corrosive-resisting, excellent weatherability, anti-flammability, and uniqueness Low-surface-energy etc..Fluoropolymer is broadly divided into fluoride containing polyolefins and acrylate containing fluorine polymer.
Kynoar (PVDF) is nontoxic odorless, and appearance is translucent or white powder or particle, and molecule contains firm Fluoro- carbonization is built jointly, has preferable chemical stability, heat resistance and a mechanical property, and uvioresistant irradiation and ageing-resistant etc. Performance；The molecule interchain arrangement of PVDF is close, and crystallinity is higher, and hydrophobicity is larger, to the poor resistance of alkali.Based on above-mentioned spy Point, PVDF are a kind of new materials of high comprehensive performance, are drawn in recent years in fluorocarbon coating, the field such as petrochemical industry and UF membrane The great interest of people is played.
Polytrifluorochloroethylene (PCTFE) crystallinity is high, has the spy that transparency is high, hardness is big, rigidity is strong, creep resistant is good Point.Because fluorine atom is more in molecular structure, product has non-hygroscopic and air impermeability, and intramolecular introduces chlorine atom, processability It can be improved, but heat resistance is poor.PCTFE is commonly used for corrosion-resistant, electronic instrument parts on chemical industry equipment and moisture-proof, anti- Adhesive coating layer.
Inert fluorine atom almost covers the surface of whole macromolecular chain, temperature tolerance and height in polytetrafluoroethylene (PTFE) (PTFE) Lubricity protrudes, and has fabulous chemical stability, and most of chemicals and solvent are shown with inertia, and it is strong to be resistant to strong acid Alkali, water and various organic solvents.Shortcoming is that PTFE has cold flow properties, non-stick and relatively low mechanical strength, be commonly used for rod, pipe, The making of the material such as plate, CABLE MATERIALS, raw material band, anti-stick coating.Fluorinated acrylate had both retained the hydrophobic oleophobic of fluoropolymer Property, and the bond properties with acrylic polymer, but because fluorinated acrylate inertia is larger, it is difficult to it is dissolved in water and one As solvent, usually by the monomer such as fluorinated acrylate and (methyl) acrylate, styrene carry out emulsion polymerization, obtain binary or Terpolymer, and extensive use and textile industry and coatings industry, assign ground excellent water and oil repellant effect.
At present, the research on fluorinated copolymer and preparation method thereof has been reported that both at home and abroad.Chinese patent (CN101692496A) disclose a kind of fluorine-containing alkene monomer containing functional group and carry out what cross-linking reaction obtained under certain condition Exchange membrane containing fluorine.Gained amberplex has higher proton conductivity and dimensional stability.Chinese patent (CN 1223271A) disclose the copolymerization of a kind of fluorinated olefins and maleic anhydride, maleic acid, dichloromaleic anhydride or dichloromaleic acid Thing, resulting polymers can be used as the adhesive or miscible agent of fluoropolymer, and available in coating.In existing fluorinated copolymer Rarer water solubility lotus positive electricity monomer is copolymerized with fluorochemical monomer, so existing fluorinated copolymer can not be specifically used to prepare antibacterial Property material.And the comonomer in existing fluorinated copolymer is mostly oil-soluble monomer (such as vinyl acetate, acrylate), Copolymerization content can reach 10~20wt%；Also a small amount of water-soluble monomer (such as maleic anhydride, acrylic acid), but due to polymerizeing Cheng Zhong, fluorochemical monomer is in oil phase, and comonomer, in water phase, two-phase can not dissolve each other, and cause water-soluble monomer in copolymer Constituent content is especially low, only below 5wt%, this causes existing fluorinated copolymer not possess good hydrophily.Copolymerization component Content is low and the missing of lotus positive electricity comonomer, significantly limit the application range of fluorinated polymer material.
The content of the invention
For overcome the deficiencies in the prior art, the technical problems to be solved by the invention are to provide one kind while have antibacterial Performance, super hydrophilicity, anion exchange absorbing performance and the adjustable cationic functional fluoropolymer of performance and its system Preparation Method.
The good cationic functional list of hydrophily is introduced in cationic functional fluoropolymer provided by the invention Body component, its content reach as high as 60wt%；Preferably, used cationic functional monomer can be selected from it is double bond containing Quaternary ammonium salt monomer, double bond containing quaternary phosphonium salt class monomer any one or it is any a variety of, this two classes monomer is respectively provided with well Anti-microbial property and anion exchange absorbing performance, and the water solubility due to monomer in itself, so excellent parent can also be provided Water-based energy so that there is the cationic functional fluoropolymer provided good anti-microbial property, anion exchange to inhale at the same time Attached performance and hydrophilicity.But since this two classes monomer is water-soluble monomer, the prior art can not realize its with it is oil-soluble The copolymerization of fluorine-containing hydrophobic monomer, and the present invention breaches this technology restriction, innovatively realizes a large amount of water miscible sun Ion functionalization monomer is grafted on oil-soluble fluorine-containing hydrophobic monomer, so as to prepare water-soluble cationic functionalization monomer group Point content very high (reaching as high as 60wt%) and water miscible cationic functional monomer component content it is adjustable (1~ Fluorinated copolymer 60wt%).The fluorine-containing hydrophobic monomer is selected from vinyl fluoride, vinylidene, trifluoro-ethylene, trifluoro chloroethene Alkene, tetrafluoroethene, hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, acrylic acid trifluoro ethyl ester, methacrylic acid trifluoro second Ester, perfluorobutyl ethylene, perfluorohexyl ethylene, perfluorooctyl ethylene, perfluor nonyl ethene, perfluorododecyl ethene, perfluor Myristyl ethene, perfluor hexadecyl vinyl, perfluoro butyl ethyl propylene acid esters, perfluoro hexyl ethyl propylene acid esters, perfluor Octyl group ethyl propylene acid esters, perfluor nonyl ethyl propylene acid esters, perfluorododecyl ethyl propylene acid esters, perfluor myristyl second Base acrylate, perfluor cetyl ethyl propylene acid esters, perfluoro butyl ethylmethyl acrylate, perfluoro hexyl ethyl-methyl Acrylate, perfluorooctylethyl group methacrylate, perfluor nonyl ethylmethyl acrylate, perfluorododecyl ethyl first Base acrylate, perfluor myristyl ethylmethyl acrylate, perfluor cetyl ethylmethyl acrylate, acrylic acid ten Any one or any a variety of, preferably vinylidene, chlorotrifluoroethylene, four of difluoro heptyl ester, dodecafluoroheptyl methacrylate Vinyl fluoride.
In addition it is different from existing fluorine-containing random copolymerization chain structure, cationic functional fluoropolymer provided by the invention In, lotus positive electricity segment is grafting segment, also, the quantity of grafting segment and length are adjustable, so that cationic functional The constituent content of monomer can be adjusted between 1~60wt%, so as to achieve the purpose that to adjust performance of copolymer.
Preparation method provided by the invention as shown in Figure 1, first using it is free-radical polymerized by fluorochemical monomer, activity can be grafted Monomer and a small amount of hydrophile function monomer copolymerization, have obtained certain hydrophilic and free containing atom transfer on main chain The active precursor polymer solid wet feed of base polymerization activity side base, then uses atom transfer radical polymerization in solid liquid interface Method (ATRP), cationic functional monomer is graft-polymerized to the active precursor polymer, finally obtain containing sun from Subtype side chain and cationic functional fluoropolymer that component is controllable.The free-radical polymerized middle addition of the first step it is hydrophilic Functionalization monomer and activated monomer can be grafted play the role of respectively different, the addition of hydrophile function monomer makes first step free radical The prepared active precursor polymer of copolymerization has certain hydrophily, in second step ATRP polymerization, water miscible cation work( Monomer can be changed can just fuse well with the hydrophilic active precursor polymer prepared by the first step, two reactants is in same In one phase, carry out providing possibility for copolyreaction；Before the addition of activated monomer can be grafted making the activity prepared by the first step Contain atom transfer radical polymerization active lateral group on the main chain of body polymer, itself and the low price added during second step ATRP polymerization Transition metal halide is together to form catalyst/initiator system with ATRP complexants, so as to fulfill being smoothed out for ATPR reactions. So hydrophile function monomer and the addition that can be grafted both monomers of activated monomer, are to realize cationic functional monomer with containing The important component of fluorine monomer copolymerization is indispensable.And ATRP reactions be can be by cationic functional monomer concentration and anti- Control between seasonable, contains cation functionalization monomer component in the cationic functional fluoropolymer that finally obtains to realize The control of amount.
Different from the prior art, cationic functional fluoropolymer provided by the invention and preparation method thereof, solves Some problems existing in the prior art：
(1) it is common when using oil-soluble comonomer (such as vinyl acetate, acrylate) in existing fluorinated copolymer During polycondensation monomer, copolymerization content can reach 10~20wt%；When using water-soluble monomer, can access fluorine-containing main chain at present only has Water-soluble carboxyl acids monomer (maleic anhydride, acrylic acid), and the amount of the water-soluble carboxyl acids monomer accessed only up to reach Below 5wt%.This is because fluorochemical monomer is in oil phase, and water-soluble carboxyl acids monomer, in water phase, two-phase can not dissolve each other, and lead Water-soluble monomer constituent content is especially low in cause fluorinated copolymer, its content can only achieve below 5wt%, in addition, molten to oil Property monomer and water-soluble monomer all do not have lotus positive electricity performance.And the technology of the present invention has widened the list with fluorochemical monomer copolymerization significantly The species of body, the cationic functional monomer employed in a kind of cationic functional fluoropolymer provided by the invention are optional From double bond containing quaternary ammonium salt monomer, double bond containing quaternary phosphonium salt class monomer any one or it is any a variety of；Preferably, it is described Double bond containing quaternary ammonium salt monomer is selected from trimethylallylammonium chloride, 2- MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, two Methyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac any one or it is any a variety of；Preferably, it is described Double bond containing quaternary phosphonium salt class monomer is selected from pi-allyl tributyl phosphonium chloride, pi-allyl triphenyl phosphine dichloride, pi-allyl triphen bromide Change phosphine any one or it is any a variety of.These monomers are respectively provided with very strong lotus positive electricity performance, therefore have extraordinary antibacterial Performance (as shown in Figure 2) and anion exchange absorbing performance.Further, cationic functional fluoropolymer provided by the invention Cation functionalization monomer component content may be up to 60wt% in thing, far above the comonomer group in existing fluorinated copolymer Divide content, have very strong lotus positive electricity performance, therefore there is extraordinary anti-microbial property (as shown in Figure 2) and anion exchange absorbing Performance, and cation functionalization monomer component can arbitrarily be adjusted between 1~60wt% in copolymer.
(2) existing prepare in fluorinated copolymer method is difficult to solve split-phase of the aqueous phase monomers with oil phase monomer when polymerizeing to ask Topic, so as to can not be copolymerized the water phase comonomer of the group containing functionalization and fluorochemical monomer, causes the functionalization of fluorinated copolymer It is single.And the method that the radical polymerization that the present invention uses is copolymerized successively with ATRP polymerization method, and it is equal with traditional ATRP Phase-polymerization is different, and the ATRP polymerization that the present invention uses is the solid liquid interface in active precursor polymer and cationic functional monomer Upper generation so that aqueous phase cation functionalization monomer has good intersolubility with oil phase fluorochemical monomer, so that having at the same time anti- It is prepared by the cationic functional fluoropolymer of bacterium performance, anion exchange absorbing performance and hydrophilicity.
For this reason, the present invention adopts the following technical scheme that：
A kind of cationic functional fluoropolymer, it is characterised in that the master of the cationic functional fluoropolymer Chain includes fluorine-containing chain link, activity grafting residue chain link and hydrophilic chain link, the side chain of the cationic functional fluoropolymer by Cation chain link forms, covalent for C-C between the cation chain link in activity grafting residue and the side chain in the main chain Key links, and the structural formula of the cationic functional fluoropolymer is as follows：
In formula：
The fluorine-containing chain link is polymerized by fluorochemical monomer A, and the structure of the fluorine-containing link units-A- is；
The activity grafting residue chain link is by that can be grafted after activated monomer B-X polymerize and cationic functional monomer F2Instead It should form, the activity grafting residue link unitsStructure be：
The hydrophilic chain link is by hydrophile function monomer F1It is polymerized, the hydrophilic link units-F1- structure For：
The cation chain link is by cationic functional monomer F2It is polymerized, the cation link units-F2- Structure be：
In formula：
R1Selected from H, CH3；
R2Selected from COOCH2CF2CHFCF3、COOCH2CF3、(CF2)mCF3、COOCH2CH2(CF2)mCF3、COOCH2CF (CF2CF3)(CH(CF3)2)；
M is 3,5,7,9,11,13,15；
R3Selected from H, F；
R4Selected from H, F；
R5Selected from H, F, Cl；
R6It is selected from
R7It is selected fromCN、COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH；
R8Selected from CH2N(CH3)3Cl、COOCH2CH2N(CH3)3Cl、CH2N(CH2=CHCH2)(CH3)2Cl、CH2P(C4H9)3Cl、CH2P(Ph)3Cl、CH2P(Ph)3Br、CH2CH2CH2P(Ph)3Br；
X is selected from Cl, Br, F, I；
A, b, c, d are the integer more than or equal to 1.
Further, the corresponding monomers of fluorochemical monomer A are selected from vinyl fluoride, vinylidene, trifluoro-ethylene, trifluoro chlorine Ethene, tetrafluoroethene, hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, acrylic acid trifluoro ethyl ester, methacrylic acid trifluoro It is ethyl ester, perfluorobutyl ethylene, perfluorohexyl ethylene, perfluorooctyl ethylene, perfluor nonyl ethene, perfluorododecyl ethene, complete It is fluorine myristyl ethene, perfluor hexadecyl vinyl, perfluoro butyl ethyl propylene acid esters, perfluoro hexyl ethyl propylene acid esters, complete Fluorine octyl group ethyl propylene acid esters, perfluor nonyl ethyl propylene acid esters, perfluorododecyl ethyl propylene acid esters, perfluor myristyl Ethyl propylene acid esters, perfluor cetyl ethyl propylene acid esters, perfluoro butyl ethylmethyl acrylate, perfluoro hexyl ethyl first Base acrylate, perfluorooctylethyl group methacrylate, perfluor nonyl ethylmethyl acrylate, perfluorododecyl ethyl Methacrylate, perfluor myristyl ethylmethyl acrylate, perfluor cetyl ethylmethyl acrylate, acrylic acid Ten difluoro heptyl esters, dodecafluoroheptyl methacrylate any one or it is any a variety of, its structural formula is as follows：
In formula：
R1Selected from H, CH3；
R2Selected from COOCH2CF2CHFCF3、COOCH2CF3、(CF2)mCF3、COOCH2CH2(CF2)mCF3、COOCH2CF (CF2CF3)(CH(CF3)2)；
M is 3,5,7,9,11,13,15.
Further, the corresponding monomers of activated monomer B-X that are grafted are 2 bromo 2 methyl propionic acid allyl ester, 2- It is chloro-2-methyl allyl propionate, p-chloromethyl styrene, as follows to bromometllylstyrene, its structural formula：
In formula：
R9It is selected from
X is selected from Cl, Br, F, I.
Further, the hydrophile function monomer F1Corresponding monomer is vinyl pyrrolidone, acrylonitrile, methyl Hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, its structural formula are as follows：
In formula：
R1Selected from H, CH3；
R7It is selected fromCN、COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH；
Further, the cationic functional monomer F2Corresponding monomer is trimethylallylammonium chloride, 2- first Base acrylyl oxy-ethyl-trimethyl salmiac, dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, allyl Base tributyl phosphonium chloride, pi-allyl triphenyl phosphine dichloride, (2- methacrylics) triphenyl phosphine dichloride, pi-allyl triphenyl phosphonium bromide Phosphine, its structural formula are as follows：
In formula：
R1Selected from H, CH3；
R8Selected from CH2N(CH3)3Cl、COOCH2CH2N(CH3)3Cl、CH2N(CH2=CHCH2)(CH3)2Cl、CH2P(C4H9)3Cl、CH2P(Ph)3Cl、CH2P(Ph)3Br、CH2CH2CH2P(Ph)3Br。
Further, a/b=1000/1~1/2, preferably a/b=100/1~50/1；
A/c=100/1~2/1, preferably a/c=20/1~4/1；
A/d=100/1~1/2, preferably a/d=10/1~1/1.
Second object of the present invention is to provide the preparation method of the cationic functional fluoropolymer, including as follows Step：
1) the active precursor polymer that main chain contains atom transfer radical polymerization active lateral group is synthesized first；
2) and then using the active lateral group on the main chain of the active precursor polymer cationic functional monomer is triggered to exist Atom transfer radical polymerization is carried out in solid liquid interface, cationic functional fluoropolymer is made；
Wherein, the main chain of the active precursor polymer includes fluorine-containing chain link, activity grafting chain link and hydrophilic chain link, described Active precursor polymer backbone structure formula it is as follows：
In formula：
The fluorine-containing chain link is polymerized by fluorochemical monomer A, and the structure of the fluorine-containing link units-A- is；
The activity grafting chain link is polymerized by that can be grafted activated monomer B-X, the activity grafting link unitsStructure be：
The hydrophilic chain link is by hydrophile function monomer F1It is polymerized, the hydrophilic link units-F1- structure For：
In formula：
R1Selected from H, CH3；
R2Selected from COOCH2CF2CHFCF3、COOCH2CF3、(CF2)mCF3、COOCH2CH2(CF2)mCF3、COOCH2CF (CF2CF3)(CH(CF3)2)；
M is 3,5,7,9,11,13,15；
R3Selected from H, F；
R4Selected from H, F；
R5Selected from H, F, Cl；
R7It is selected fromCN、COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH；R9It is selected from
X is selected from Cl, Br, F, I；
A, b, c, d are the integer more than or equal to 1.
The main chain of the cationic functional fluoropolymer includes fluorine-containing chain link, activity grafting residue chain link and hydrophilic chain Section, the side chain of the polymer are made of cation chain link, the activity grafting residue in the main chain and the sun in the side chain It is C-C covalent linkages between ion chain link, the structural formula of the cationic functional fluoropolymer is as follows：
In formula：
The fluorine-containing chain link is polymerized by fluorochemical monomer A, and the structure of the fluorine-containing link units-A- is；
The activity grafting residue chain link is by that can be grafted after activated monomer B-X polymerize and cationic functional monomer F2Instead It should form, the activity grafting residue link unitsStructure be：
The hydrophilic chain link is by hydrophile function monomer F1It is polymerized, the hydrophilic link units-F1- structure For：
The cation chain link is by cationic functional monomer F2It is polymerized, the cation link units-F2- Structure be：
In formula：
R1Selected from H, CH3；
R2Selected from COOCH2CF2CHFCF3、COOCH2CF3、(CF2)mCF3、COOCH2CH2(CF2)mCF3、COOCH2CF (CF2CF3)(CH(CF3)2)；
M is 3,5,7,9,11,13,15；
R3Selected from H, F；
R4Selected from H, F；
R5Selected from H, F, Cl；
R6It is selected from
R7It is selected fromCN、COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH；
R8Selected from CH2N(CH3)3Cl、COOCH2CH2N(CH3)3Cl、CH2N(CH2=CHCH2)(CH3)2Cl、CH2P(C4H9)3Cl、CH2P(Ph)3Cl、CH2P(Ph)3Br、CH2CH2CH2P(Ph)3Br；
X is selected from Cl, Br, F, I；
A, b, c, d are the integer more than or equal to 1；
Further, step 1), 2) two-step reaction is completed in one pot.
Further, a/b=1000/1~1/2, preferably a/b=100/1~50/1；A/c=100/1~2/1, preferably a/ C=20/1~4/1；A/d=100/1~1/2, preferably a/d=10/1~1/1.
Further, the concrete operations of preparation method include the following steps：
(1) polymerization of active precursor polymer：Weigh fluorochemical monomer A, activated monomer B-X and hydrophile function list can be grafted Body F1Mix monomer is configured to, adds radical initiator, backbone polymerization reaction is carried out in Aqueous dispersions system, obtains main chain Active precursor polymer with atom transfer radical polymerization active lateral group；
(2) monomer and free radical on active precursor polymer are removed：After the polymerisation of step (1), removing is not The fluorochemical monomer A of reaction, and the free radical in system is inactivated, obtain active precursor polymer solid wet feed；
(3) atom transfer radical polymerization：Active precursor polymer solid wet feed is distributed to fluorine-containing list in step (1) On the basis of the weight of body A, cationic functional monomer F is added2In the water phase of catalyst/initiator system, in solid liquid interface, adopt With Transfer Radical Polymerization, trigger cationic functional using the active lateral group on the main chain of the active precursor polymer Change monomer F2, the graft polymerization of cationic monomer is carried out, cationic functional fluoropolymer is made.
Active precursor polymer solid wet feed described in step (2) is the mixture of active precursor polymer and water.
In the step (3), the cationic functional monomer F of addition2With the material in catalyst/initiator system with step (1) On the basis of the weight of middle fluorochemical monomer A.
Preferably, the fluorochemical monomer A described in step (1) is selected from vinyl fluoride, vinylidene, trifluoro-ethylene, trifluoro chloroethene Alkene, tetrafluoroethene, hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, acrylic acid trifluoro ethyl ester, methacrylic acid trifluoro second Ester, perfluorobutyl ethylene, perfluorohexyl ethylene, perfluorooctyl ethylene, perfluor nonyl ethene, perfluorododecyl ethene, perfluor Myristyl ethene, perfluor hexadecyl vinyl, perfluoro butyl ethyl propylene acid esters, perfluoro hexyl ethyl propylene acid esters, perfluor Octyl group ethyl propylene acid esters, perfluor nonyl ethyl propylene acid esters, perfluorododecyl ethyl propylene acid esters, perfluor myristyl second Base acrylate, perfluor cetyl ethyl propylene acid esters, perfluoro butyl ethylmethyl acrylate, perfluoro hexyl ethyl-methyl Acrylate, perfluorooctylethyl group methacrylate, perfluor nonyl ethylmethyl acrylate, perfluorododecyl ethyl first Base acrylate, perfluor myristyl ethylmethyl acrylate, perfluor cetyl ethylmethyl acrylate, acrylic acid ten Difluoro heptyl ester, dodecafluoroheptyl methacrylate any one or it is any a variety of.
Preferably, the hydrophile function monomer F described in step (1)1Selected from vinyl pyrrolidone, acrylonitrile, methyl Hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate any one or it is any a variety of.
Preferably, the activated monomer B-X that is grafted described in step (1) is selected from 2 bromo 2 methyl propionic acid allyl ester, 2- Chloro-2-methyl allyl propionate, p-chloromethyl styrene, to bromometllylstyrene any one or it is any a variety of.
Preferably, the mix monomer preparation molar ratio described in step (1) is：Fluorochemical monomer/activated monomer can be grafted =1000/1~1/2；Fluorochemical monomer/hydrophile function monomer=100/1~2/1.It is furthermore preferred that fluorochemical monomer/work can be grafted Property monomer=100/1~50/1；Fluorochemical monomer/hydrophile function monomer=20/1~4/1.
Preferably, the polymerisation described in step (1) is selected from any one of suspension polymerization, emulsion polymerization.It is poly- Close reaction and use initiator, other additives, reaction temperature and reaction time known to radical polymerization field.It is furthermore preferred that The initiator is selected from dicetyl peroxydicarbonate two (2- ethyl hexyls) ester (EHP), azodiisobutyronitrile, dibenzoyl peroxide, mistake Potassium sulfate, ammonium persulfate any one or it is any a variety of, the additive is selected from polyvinyl alcohol (PVA), additive hydroxypropyl Methylcellulose (HPMC), methylcellulose, lauryl sodium sulfate, dodecyl sodium sulfate, nekal are appointed Anticipate a kind of or any a variety of, the reaction temperature is selected from 35~85 DEG C, the reaction time be selected from 1~20 it is small when.
Preferably, the method for the unreacted fluorochemical monomer A of removing described in step (2) is selected from decompression degassing method, air lift Any one of method, natural volatility process.It is furthermore preferred that the method choice of removing fluorochemical monomer A is carried out according to the boiling point of monomer Selection, when boiling point is higher than 20 DEG C, then preferably depressurizes degassing method, air- extraction any one；It is when boiling point is less than 20 DEG C, then excellent Any one of choosing decompression degassing method, air- extraction, natural volatility process.
Preferably, the method for inactivating the free radical in system described in step (2) is selected from plus terminator method, logical oxygen take off Any one of oxygen method.The terminator is selected from terminator known to radical polymerization field.In the logical oxygen deoxidation method Oxygenous gas is pure oxygen or air, and the method for removing oxygen is 1~60min of logical nitrogen or argon gas.
Preferably, the cationic functional monomer F described in step (3)2Selected from trimethylallylammonium chloride, 2- methyl Acrylyl oxy-ethyl-trimethyl salmiac, dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, pi-allyl Tributyl phosphonium chloride, pi-allyl triphenyl phosphine dichloride, (2- methacrylics) triphenyl phosphine dichloride, pi-allyl triphenyl phosphonium bromide Phosphine, (4- pentenyls) triphenylphosphinebromide any one or it is any a variety of.
Preferably, the cationic functional monomer F described in step (3)2The molar ratio of content is：Fluorochemical monomer/sun Ion functionalization monomer=100/1~1/2.It is furthermore preferred that fluorochemical monomer/cationic functional monomer=10/1~1/1.
Preferably, the catalyst/initiator system described in step (3) is low-valent transition metals halide and ATRP complexants Combination.It is furthermore preferred that low-valent transition metals halide of the present invention is selected from copper, stannous chloride, cuprous bromide, protochloride Iron, ferrous bromide any one or it is any a variety of, the ATRP complexants are selected from 2,2'- bipyridyls (bpy), 4,4'- bis- Nonyl -2,2'- bipyridyls (dNbpy), pentamethyl-diethylenetriamine (PMDETA), 1,1,4,7,10,10- hexamethyls triethylene four Amine (HMTETA), three (2- dimethylaminoethyls) amine (Me6TREN), three (2- pyridylmethyls) amine (TPMA) any one or It is any a variety of.
Preferably, the catalyst/initiator system middle or low price transition metal halide described in step (3) adds with ATRP complexants It is general addition known to ATRP polymerization field to enter amount.
Preferably, the Transfer Radical Polymerization (ATRP) described in step (3), reaction temperature are 0~80 DEG C；Instead 10 minutes~10 days between seasonable.It is furthermore preferred that reaction temperature is 10~60 DEG C；When reaction time 1 is small~24 it is small when.
Preferably, after the Transfer Radical Polymerization (ATRP) described in step (3), by filtering, washing, Cationic functional fluoropolymer is obtained after drying.
In step of the present invention, the hydrophile function monomer F of the free-radical polymerized middle addition of step (1)1It is active single with that can be grafted Body B-X plays the role of different, hydrophile function monomer F respectively1Addition have the active precursor polymer prepared by step (1) Certain hydrophily, in step (3) ATRP polymerization, water miscible cationic functional monomer F2Just can be with step (1) institute The hydrophilic active precursor polymer of preparation fuses well, two reactants is in same phase, is carried for copolyreaction Possibility is supplied；The addition of activated monomer B-X, which can be grafted, to be made to contain on the main chain of the active precursor polymer prepared by step (1) Atom transfer radical polymerization active lateral group, its low-valent transition metals halide added with step (3) are total to ATRP complexants With catalyst/initiator system is combined into, so as to fulfill being smoothed out for ATPR reactions.So hydrophile function monomer F1With can be grafted The addition of both monomers of activated monomer B-X, is to realize cationic functional monomer and the important component of fluorochemical monomer copolymerization, lacks One can not.And ATRP reaction be can be by the control to cationic functional monomer concentration and reaction time, to realize to most The control of cation functionalization monomer component content in the cationic functional fluoropolymer obtained eventually so that water miscible sun The ratio of ion functionalization monomer component can arbitrarily be adjusted between 1~60wt%.
Present invention also offers a kind of polymeric material, it is characterised in that the polymeric material includes claim 1-6 any one of them cationic functional fluoropolymers.The antibacterial that the polymeric material is selected from high-hydrophilic separates Any one of membrane material, gel electrolyte, adhesive, battery diaphragm material, anion-exchange material, antibiotic paint.
Polymeric material provided by the invention is required according to usage, and polymeric material can also include other resinous woods Material or additive material.Other described resin materials can be polyvinyl chloride, polypropylene, polyethylene, Kynoar, poly- carbon Acid esters, nylon, polyether sulfone, the additive material can be common inorganic material, organic small molecule material, macromolecule material Material.
The beneficial effect of the present invention compared with prior art has：
Cation functionalization monomer component has at the same time in a kind of cationic functional fluoropolymer provided by the invention Anti-microbial property and hydrophilicity, its content may be up to 60wt%, it has anti-microbial property and hydrophilicity concurrently and is assigned for fluoropolymer New function is given.
Cation functionalization monomer component also has the moon in a kind of cationic functional fluoropolymer provided by the invention Ion exchange adsorbs performance, its content may be up to 60wt%, its anion exchange absorbing performance also imparts for fluoropolymer New function.
The ratio of cation functionalization monomer component can in a kind of cationic functional fluoropolymer provided by the invention Arbitrarily adjusted between 1~60wt% so that cationic functional fluoropolymer provided by the invention has very flexible Applicability.
The method that the radical polymerization that the present invention uses is copolymerized successively with ATRP polymerization method so that aqueous phase cation function Changing monomer and oil phase fluorochemical monomer has good intersolubility, greatly improves cation functionalization monomer component in polymer.
The method that the radical polymerization that the present invention uses is copolymerized successively with ATRP polymerization method causes cationic functional to contain Cation functionalization monomer component can be controlled easily by monomer addition and reaction time in fluoropolymer.
The method that the radical polymerization that this present invention uses is copolymerized successively with ATRP polymerization method, reaction process is short, equipment Simply, it is adapted to large-scale production.
Brief description of the drawings
Fig. 1 is that Transfer Radical Polymerization (ATRP) reacts schematic diagram in embodiment 1；
Fig. 2 is the antibacterial effect figure of cation functionalization fluoropolymer P1 films and poly- fluoropolymer membrane in embodiment 33.
Embodiment：
Below with specific embodiment the present invention will be described in detail cationic functional fluoropolymer preparation method.All implementations The implementation steps of example are identical with the implementation steps described in the content of the invention, and parameter is every implementation condition and is copolymerized in table The structure of thing.It should be noted that the embodiment is not construed as limiting the invention, those of ordinary skill in the art can be from All deformations that present disclosure is directly exported or associated, are considered as protection scope of the present invention.
Embodiment 1：
The synthesis of cationic functional fluoropolymer P1：
2000ml deionized waters, additives polyvinyl alcohol (PVA) 1.2g, additive hydroxypropyl are added in stainless steel cauldron Ylmethyl cellulose (HPMC) 0.4g, initiator dicetyl peroxydicarbonate two (2- ethyl hexyls) ester (EHP) 1g, vacuumize simultaneously inflated with nitrogen Vinylidene 1500g, hydroxy-ethyl acrylate 21.79g and 2 bromo 2 methyl propionic acid allyl ester 4.85g are added after 3 times repeatedly, Pre-dispersed stirring 30 minutes at room temperature.47 DEG C of polymerization temperatures are warming up to, carry out polymerisation.React 12 it is small when, when kettle internal drop Stop heating when reaching 0.2MPa, volatilize 15 minutes naturally, be passed through air 5 minutes, vacuumize simultaneously inflated with nitrogen repeatedly for three times after, add Enter trimethylallylammonium chloride 31.76g, copper 5g, stannous chloride 5g, 2,2'- bipyridyls (bpy) 16g, then 60 DEG C of temperature control, React 24 it is small when, (as shown in Figure 1).After question response, air is passed through into system and terminates reaction.Discharge, filter, washing, The cationic functional fluoropolymer (P1) just like lower structure is obtained after 50 DEG C of drying：
In formula：A/b=1000/1；A/c=100/1；A/d=100/1.
X=Br
R1=H；
R4=H；
R5=H；
R7=COOCH2CH2OH；
R8=CH2N(CH3)3Cl；
R10=F；
R11=F.
The characterizing method of P1 synthetic polymers structure and performance：
1st, structural characterization：Using1Its structure of H-NMR nuclear magnetic resoance spectrums map analysis.Obtained P1 is dissolved in deuterated In DMSO, nuclear-magnetism test is carried out.
2nd, performance characterization：Using gel permeation chromatography (GPC) analyzing molecules amount.Obtained P1 is dissolved in DMF, into Row GPC is tested.
Find out that the polymer prepared by above-mentioned preparation method is that structure above is characterized by polymer 1H-NMR characterizations Compound, cation functionalization monomer component content 1.01wt% in cationic functional fluoropolymer.Tested by GPC, Polymer number-average molecular weight Mn=52K prepared by the present embodiment；Molecular weight distribution PDI=1.4.
Embodiment 2：
The synthesis of cationic functional fluoropolymer P2：
P2 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P2 structures and performance characterization method are identical with described in embodiment 1.P2 structural formula general formulas are identical with P1, its formula of In parameter such as table 3；Cation functionalization monomer component content such as table 4 in P2 molecular weight, molecular weight distribution and polymer.
Embodiment 3：
The synthesis of cationic functional fluoropolymer P3：
P3 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P3 structures and performance characterization method are identical with described in embodiment 1.P3 structural formula general formulas are identical with P1, its formula of In parameter such as table 3；Cation functionalization monomer component content such as table 4 in P3 molecular weight, molecular weight distribution and polymer.
Embodiment 4：
The synthesis of cationic functional fluoropolymer P4：
P4 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P4 structures and performance characterization method are identical with described in embodiment 1.P4 structural formula general formulas are identical with P1, its formula of In parameter such as table 3；Cation functionalization monomer component content such as table 4 in P4 molecular weight, molecular weight distribution and polymer.
Embodiment 5：
The synthesis of cationic functional fluoropolymer P5：
P5 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P5 structures and performance characterization method are identical with described in embodiment 1.P5 structural formula general formulas are identical with P1, its formula of In parameter such as table 3；Cation functionalization monomer component content such as table 4 in P5 molecular weight, molecular weight distribution and polymer.
Embodiment 6：
The synthesis of cationic functional fluoropolymer P6：
P6 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P6 structures and performance characterization method are identical with described in embodiment 1.P6 structural formula general formulas are identical with P1, its formula of In parameter such as table 3；Cation functionalization monomer component content such as table 4 in P6 molecular weight, molecular weight distribution and polymer.
Embodiment 7：
The synthesis of cationic functional fluoropolymer P7：
P7 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P7 structures and performance characterization method are identical with described in embodiment 1.P7 structural formula general formulas are identical with P1, its formula of In parameter such as table 3；Cation functionalization monomer component content such as table 4 in P7 molecular weight, molecular weight distribution and polymer.
Embodiment 8：
The synthesis of cationic functional fluoropolymer P8：
P8 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P8 structures and performance characterization method are identical with described in embodiment 1.P8 structural formula general formulas are identical with P1, its formula of In parameter such as table 3；Cation functionalization monomer component content such as table 4 in P8 molecular weight, molecular weight distribution and polymer.
Embodiment 9：
The synthesis of cationic functional fluoropolymer P9：
P9 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P9 structures and performance characterization method are identical with described in embodiment 1.P9 structural formula general formulas are identical with P1, its formula of In parameter such as table 3；Cation functionalization monomer component content such as table 4 in P9 molecular weight, molecular weight distribution and polymer.
Embodiment 10：
The synthesis of cationic functional fluoropolymer P10：
P10 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P10 structures and performance characterization method are identical with described in embodiment 1.P10 structural formula general formulas are identical with P1, wherein logical Parameter such as table 3 in formula；Cation functionalization monomer component content such as table 4 in P10 molecular weight, molecular weight distribution and polymer.
Embodiment 11：
The synthesis of cationic functional fluoropolymer P11：
P11 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P11 structures and performance characterization method are identical with described in embodiment 1.P11 structural formula general formulas are identical with P1, wherein logical Parameter such as table 3 in formula；Cation functionalization monomer component content such as table 4 in P11 molecular weight, molecular weight distribution and polymer.
Embodiment 12：
The synthesis of cationic functional fluoropolymer P12：
P12 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P10 structures and performance characterization method are identical with described in embodiment 1.P12 structural formula general formulas are identical with P1, wherein logical Parameter such as table 3 in formula；Cation functionalization monomer component content such as table 4 in P12 molecular weight, molecular weight distribution and polymer.
Embodiment 13：
The synthesis of cationic functional fluoropolymer P13：
P13 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P13 structures and performance characterization method are identical with described in embodiment 1.P13 structural formula general formulas are identical with P1, wherein logical Parameter such as table 3 in formula；Cation functionalization monomer component content such as table 4 in P13 molecular weight, molecular weight distribution and polymer.
Embodiment 14：
The synthesis of cationic functional fluoropolymer P14：
P14 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P14 structures and performance characterization method are identical with described in embodiment 1.P14 structural formula general formulas are identical with P1, wherein logical Parameter such as table 3 in formula；Cation functionalization monomer component content such as table 4 in P14 molecular weight, molecular weight distribution and polymer.
Embodiment 15：
The synthesis of cationic functional fluoropolymer P15：
P15 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P15 structures and performance characterization method are identical with described in embodiment 1.P15 structural formula general formulas are identical with P1, wherein logical Parameter such as table 3 in formula；Cation functionalization monomer component content such as table 4 in P15 molecular weight, molecular weight distribution and polymer.
Embodiment 16：
The synthesis of cationic functional fluoropolymer P16：
P16 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P16 structures and performance characterization method are identical with described in embodiment 1.P16 structural formula general formulas are identical with P1, wherein logical Parameter such as table 3 in formula；Cation functionalization monomer component content such as table 4 in P16 molecular weight, molecular weight distribution and polymer.
Embodiment 17：
The synthesis of cationic functional fluoropolymer P17：
P17 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P17 structures and performance characterization method are identical with described in embodiment 1.P17 structural formula general formulas are identical with P1, wherein logical Parameter such as table 3 in formula；Cation functionalization monomer component content such as table 4 in P17 molecular weight, molecular weight distribution and polymer.
Embodiment 18：
The synthesis of cationic functional fluoropolymer P18：
P18 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P18 structures and performance characterization method are identical with described in embodiment 1.P18 structural formula general formulas are identical with P1, wherein logical Parameter such as table 3 in formula；Cation functionalization monomer component content such as table 4 in P18 molecular weight, molecular weight distribution and polymer.
Embodiment 19：
The synthesis of cationic functional fluoropolymer P19：
P19 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P19 structures and performance characterization method are identical with described in embodiment 1.P19 structural formula general formulas are identical with P1, wherein logical Parameter such as table 3 in formula；Cation functionalization monomer component content such as table 4 in P19 molecular weight, molecular weight distribution and polymer.
Embodiment 20：
The synthesis of cationic functional fluoropolymer P20：
P20 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P20 structures and performance characterization method are identical with described in embodiment 1.P20 structural formula general formulas are identical with P1, wherein logical Parameter such as table 3 in formula；Cation functionalization monomer component content such as table 4 in P20 molecular weight, molecular weight distribution and polymer.
Embodiment 21：
The synthesis of cationic functional fluoropolymer P21：
P21 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P21 structures and performance characterization method are identical with described in embodiment 1.P21 structural formula general formulas are identical with P1, wherein logical Parameter such as table 3 in formula；Cation functionalization monomer component content such as table 4 in P21 molecular weight, molecular weight distribution and polymer.
Embodiment 22：
The synthesis of cationic functional fluoropolymer P22：
P22 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P22 structures and performance characterization method are identical with described in embodiment 1.P22 structural formula general formulas are identical with P1, wherein logical Parameter such as table 3 in formula；Cation functionalization monomer component content such as table 4 in P22 molecular weight, molecular weight distribution and polymer.
Embodiment 23：
The synthesis of cationic functional fluoropolymer P23：
P23 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P23 structures and performance characterization method are identical with described in embodiment 1.P23 structural formula general formulas are identical with P1, wherein logical Parameter such as table 3 in formula；Cation functionalization monomer component content such as table 4 in P23 molecular weight, molecular weight distribution and polymer.
Embodiment 24：
The synthesis of cationic functional fluoropolymer P24：
P24 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P24 structures and performance characterization method are identical with described in embodiment 1.P24 structural formula general formulas are identical with P1, wherein logical Parameter such as table 3 in formula；Cation functionalization monomer component content such as table 4 in P24 molecular weight, molecular weight distribution and polymer.
Embodiment 25：
The synthesis of cationic functional fluoropolymer P25：
P25 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P25 structures and performance characterization method are identical with described in embodiment 1.P25 structural formula general formulas are identical with P1, wherein logical Parameter such as table 3 in formula；Cation functionalization monomer component content such as table 4 in P25 molecular weight, molecular weight distribution and polymer.
Embodiment 26：
The synthesis of cationic functional fluoropolymer P26：
P26 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P26 structures and performance characterization method are identical with described in embodiment 1.P26 structural formula general formulas are identical with P1, wherein logical Parameter such as table 3 in formula；Cation functionalization monomer component content such as table 4 in P26 molecular weight, molecular weight distribution and polymer.
Embodiment 27：
The synthesis of cationic functional fluoropolymer P27：
P27 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P27 structures and performance characterization method are identical with described in embodiment 1.P27 structural formula general formulas are identical with P1, wherein logical Parameter such as table 3 in formula；Cation functionalization monomer component content such as table 4 in P27 molecular weight, molecular weight distribution and polymer.
Embodiment 28：
The synthesis of cationic functional fluoropolymer P28：
P28 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P28 structures and performance characterization method are identical with described in embodiment 1.P28 structural formula general formulas are identical with P1, wherein logical Parameter such as table 3 in formula；Cation functionalization monomer component content such as table 4 in P28 molecular weight, molecular weight distribution and polymer.
Embodiment 29：
The synthesis of cationic functional fluoropolymer P29：
P29 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P29 structures and performance characterization method are identical with described in embodiment 1.P29 structural formula general formulas are identical with P1, wherein logical Parameter such as table 3 in formula；Cation functionalization monomer component content such as table 4 in P29 molecular weight, molecular weight distribution and polymer.
Embodiment 30：
The synthesis of cationic functional fluoropolymer P30：
P30 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P30 structures and performance characterization method are identical with described in embodiment 1.P30 structural formula general formulas are identical with P1, wherein logical Parameter such as table 3 in formula；Cation functionalization monomer component content such as table 4 in P30 molecular weight, molecular weight distribution and polymer.
Embodiment 31：
The synthesis of cationic functional fluoropolymer P31：
P31 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P31 structures and performance characterization method are identical with described in embodiment 1.P31 structural formula general formulas are identical with P1, wherein logical Parameter such as table 3 in formula；Cation functionalization monomer component content such as table 4 in P31 molecular weight, molecular weight distribution and polymer.
Embodiment 32：
The synthesis of cationic functional fluoropolymer P32：
P32 building-up processes are with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
P32 structures and performance characterization method are identical with described in embodiment 1.P32 structural formula general formulas are identical with P1, wherein logical Parameter such as table 3 in formula；Cation functionalization monomer component content such as table 4 in P32 molecular weight, molecular weight distribution and polymer.
Embodiment 33：
The present embodiment is used to illustrate that cationic functional fluoropolymer has excellent parent compared to common fluoropolymer Water-based energy and anti-microbial property.Step is as follows：
(1) preparation of P1 films~P32 films：1~the P32 of copolymer p prepared in 20g embodiments 1-32 is dissolved in respectively In 100gN, N- dimethylacetylamide, preparation liquid is configured to；Preparation liquid is spread into liquid film on the glass sheet, and immerses 5~50 DEG C Water in film-forming, after washing 12h, P1 films~P32 films are made.
(2) preparation of PVDF1 films：20g Kynoar is dissolved in 100gN, in N- dimethylacetylamides, is configured to be film-made Liquid；Preparation liquid is spread into liquid film on the glass sheet, and immerses film-forming in 5~50 DEG C of water, PVDF1 is made after washing 12h Film.
(3) diaphragm obtained above is cleaned three times with deionized water and absolute ethyl alcohol, carries out contact angle experiments and antibacterial Property experiment.
Experimental result is as shown in table 5, (20~40 °) of the first contact angle starting for being much smaller than PVDF1 films of P1 films~P32 films Contact angle (89 °)；P1 films~P32 films are above 95% to the antibiotic rate of Escherichia coli, to the antibiotic rate of staphylococcus aureus 90% is above, and PVDF1 films are respectively 14.7% and 12.4% to the antibiotic rate of Escherichia coli and staphylococcus aureus.From It can be clearly seen that the clump count of P1 films is considerably less than the clump count of common PVDF1 films in Fig. 2, there is excellent antibiotic property Energy.
And from polymer from the point of view of the relation of cation functionalization monomer component content and antibiotic rate, contact angle, it contains Amount is higher, and antibiotic property is better, and hydrophily is also better.Can be poly- to adjust by cation functionalization monomer component content in polymer The anti-microbial property and hydrophilicity of compound.
The cationic functional fluoropolymer that the present embodiment is clearly demonstrated synthesized by the present invention can prepare have concurrently it is excellent The anti-biotic material of different hydrophilicity.
Embodiment 34：
The present embodiment is used to illustrate that cationic functional fluoropolymer has excellent the moon compared to common fluoropolymer Ion exchange adsorbs performance.Step is as follows：
(1) preparation of POH1 films~POH32 films：1~the P32 of copolymer p prepared in 20g embodiments 1-32 is dissolved in respectively In 100gN, N- dimethylacetylamide, preparation liquid is configured to；Preparation liquid is spread into liquid film on polyfluortetraethylene plate, and at 60 DEG C Vacuum drying oven in dry, wash 12h after, the film of gained is positioned in 1M KOH solutions, at 60 DEG C soak 24 it is small when, treat Br-or Cl-complete exchange remove remaining KOH with deionized water, respectively obtain OH- type anion-exchange membranes into after OH- POH1 films~POH32 films.
(2) preparation of PVDF2 films：20g Kynoar is dissolved in 100gN, in N- dimethylacetylamides, is configured to be film-made Liquid；Preparation liquid is spread into liquid film on polyfluortetraethylene plate, and is dried in 60 DEG C of vacuum drying oven, after washing 12h, is made PVDF2 films.
(3) ion exchange capacity (IEC) is carried out to test with electrical conductivity.
Ionic conductivity at IEC and 25 DEG C of experimental result anionic membrane is as shown in table 6, POH1 films~POH32 films IEC is 0.6~1.20mmol/g, hence it is evident that higher than the PVDF2 films for not possessing anion exchange performance；And at 25 DEG C, P1 films~ The ionic conductivity of P32 films is 9~20mS/cm, the same ionic conductivity for being far above PVDF2 films.
And from polymer cation functionalization monomer component content and IEC, ionic conductivity relation from the point of view of, it contains Amount is higher, and the value of IEC and ionic conductivity is higher, illustrates that the anion exchange absorbing performance of film is better.Can be by polymer Cationic functional monomer component content adjusts the anion exchange absorbing performance of polymer.
The cationic functional fluoropolymer that the present embodiment is clearly demonstrated synthesized by the present invention can be prepared with the moon Ion exchange adsorbs the high molecular material of performance.
Table 1
Table 2
Table 3
Table 4
Table 5：
Table 6：

Claims (19)

  1. A kind of 1. cationic functional fluoropolymer, it is characterised in that the main chain of the cationic functional fluoropolymer Including fluorine-containing chain link, activity grafting residue chain link and hydrophilic chain link, the side chain of the cationic functional fluoropolymer is by sun Ion chain link forms, and is C-C covalent bonds between the cation chain link in activity grafting residue and the side chain in the main chain Link, the structural formula of the cationic functional fluoropolymer are as follows：
    In formula：
    The fluorine-containing chain link is polymerized by fluorochemical monomer A, and the structure of the fluorine-containing link units-A- is；
    The activity grafting residue chain link is by that can be grafted after activated monomer B-X polymerize and cationic functional monomer F2Reaction and Into the activity grafting residue link unitsStructure be：
    The hydrophilic chain link is by hydrophile function monomer F1It is polymerized, the hydrophilic link units-F1- structure be：
    The cation chain link is by cationic functional monomer F2It is polymerized, the cation link units-F2- knot Structure is：
    In formula：
    R1Selected from H, CH3；
    R2Selected from COOCH2CF2CHFCF3 、COOCH2CF3、(CF2)mCF3、COOCH2CH2(CF2)mCF3、COOCH2CF(CF2CF3) (CH(CF3)2)；
    M is 3,5,7,9,11,13,15；
    R3Selected from H, F；
    R4Selected from H, F；
    R5Selected from H, F, Cl；
    R6It is selected from
    R7It is selected fromCN、COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH；
    R8Selected from CH2N(CH3)3Cl、COOCH2CH2N(CH3)3Cl、CH2N(CH2=CHCH2)(CH3)2Cl、CH2P(C4H9)3Cl、 CH2P(Ph)3Cl、CH2P(Ph)3Br、CH2CH2CH2P(Ph)3Br；
    X is selected from Cl, Br, F, I；
    A, b, c, d are the integer more than or equal to 1.
  2. 2. cationic functional fluoropolymer according to claim 1, it is characterised in that the fluorochemical monomer A's Structural formula is as follows：
    In formula：
    R1Selected from H, CH3；
    R2Selected from COOCH2CF2CHFCF3、COOCH2CF3、(CF2)mCF3、COOCH2CH2(CF2)mCF3、COOCH2CF(CF2CF3) (CH(CF3)2)；
    M is 3,5,7,9,11,13,15.
  3. 3. cationic functional fluoropolymer according to claim 1, it is characterised in that described being grafted is active single The structural formula of body B-X is as follows：
    In formula：
    R9It is selected from
    X is selected from Cl, Br, F, I.
  4. 4. cationic functional fluoropolymer according to claim 1, it is characterised in that the hydrophile function list Body F1Structural formula it is as follows：
    In formula：
    R1Selected from H, CH3；
    R7It is selected fromCN、COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH。
  5. 5. cationic functional fluoropolymer according to claim 1, it is characterised in that the cationic functional Monomer F2Structural formula it is as follows：
    In formula：
    R1Selected from H, CH3；
    R8Selected from CH2N(CH3)3Cl、COOCH2CH2N(CH3)3Cl、CH2N(CH2=CHCH2)(CH3)2Cl、CH2P(C4H9)3Cl、 CH2P(Ph)3Cl、CH2P(Ph)3Br、CH2CH2CH2P(Ph)3Br。
  6. 6. according to a kind of cationic functional fluoropolymer of claim 1-5 any one of them, it is characterised in that a/b= 1000/1~1/2, a/c=100/1~2/1, a/d=100/1~1/2.
  7. 7. according to a kind of cationic functional fluoropolymer of claim 1-5 any one of them, it is characterised in that a/b= 1000/1~1/2, a/c=20/1~4/1, a/d=100/1~1/2.
  8. 8. according to a kind of cationic functional fluoropolymer of claim 1-5 any one of them, it is characterised in that a/b= 1000/1~1/2, a/c=100/1~2/1, a/d=10/1~1/1.
  9. 9. according to a kind of cationic functional fluoropolymer of claim 1-5 any one of them, it is characterised in that a/b= 1000/1~1/2, a/c=20/1~4/1, a/d=10/1~1/1.
  10. 10. according to a kind of cationic functional fluoropolymer of claim 1-5 any one of them, it is characterised in that a/b= 100/1~50/1, a/c=100/1~2/1, a/d=100/1~1/2.
  11. 11. according to a kind of cationic functional fluoropolymer of claim 1-5 any one of them, it is characterised in that a/b= 100/1~50/1, a/c=100/1~2/1, a/d=10/1~1/1.
  12. 12. according to a kind of cationic functional fluoropolymer of claim 1-5 any one of them, it is characterised in that a/b= 100/1~50/1, a/c=20/1~4/1, a/d=100/1~1/2.
  13. 13. according to a kind of cationic functional fluoropolymer of claim 1-5 any one of them, it is characterised in that a/b= 100/1~50/1, a/c=20/1~4/1, a/d=10/1~1/1.
  14. 14. the preparation method of the cationic functional fluoropolymer described in claim 1, it is characterised in that the preparation side Method includes the following steps：
    1) the active precursor polymer that main chain contains atom transfer radical polymerization active lateral group is synthesized first；
    2) and then using the active lateral group on the main chain of the active precursor polymer cationic functional monomer F is triggered2In solid-liquid Atom transfer radical polymerization is carried out on interface, cationic functional fluoropolymer is made；
    Wherein, the main chain of the active precursor polymer includes fluorine-containing chain link, activity grafting chain link and hydrophilic chain link, the work The backbone structure formula of property precursor polymer is as follows：
    In formula：
    The fluorine-containing chain link is polymerized by fluorochemical monomer A, and the structure of the fluorine-containing link units-A- is；
    The activity grafting chain link is polymerized by that can be grafted activated monomer B-X, the activity grafting link unitsStructure be：
    The hydrophilic chain link is by hydrophile function monomer F1It is polymerized, the hydrophilic link units-F1- structure be：
    In formula：
    R1Selected from H, CH3；
    R2Selected from COOCH2CF2CHFCF3、COOCH2CF3、(CF2)mCF3、COOCH2CH2(CF2)mCF3、COOCH2CF(CF2CF3) (CH(CF3)2)；
    M is 3,5,7,9,11,13,15；
    R3Selected from H, F；
    R4Selected from H, F；
    R5Selected from H, F, Cl；
    R7It is selected fromCN、COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH；
    R9It is selected from
    X is selected from Cl, Br, F, I；
    A, b, c, d, n are the integer more than or equal to 1.
  15. 15. preparation method according to claim 14, it is characterised in that the preparation method includes the following steps：
    (1) polymerization of active precursor polymer：Weigh fluorochemical monomer A, activated monomer B-X can be grafted and hydrophile function monomer F1 Mix monomer is configured to, adds radical initiator, backbone polymerization reaction is carried out in Aqueous dispersions system, obtaining main chain has The active precursor polymer of atom transfer radical polymerization active lateral group；
    (2) monomer and free radical on active precursor polymer are removed：After the polymerisation of step (1), unreacted is removed Fluorochemical monomer A, and by system free radical inactivate, obtain active precursor polymer solid wet feed；
    (3) atom transfer radical polymerization：Active precursor polymer solid wet feed is distributed to and with the addition of cationic functional list Body F2In the water phase of catalyst/initiator system, the cationic functional monomer F of addition2With the material in catalyst/initiator system with step Suddenly in (1) on the basis of the weight of fluorochemical monomer A, in solid liquid interface, using Transfer Radical Polymerization, the work is utilized Property precursor polymer main chain on active lateral group trigger cationic functional monomer F2, the grafting for carrying out cationic monomer gathers Close, cationic functional fluoropolymer is made.
  16. 16. the preparation method according to claims 14 or 15, it is characterised in that the fluorochemical monomer A be selected from vinyl fluoride, Vinylidene, trifluoro-ethylene, chlorotrifluoroethylene, tetrafluoroethene, hexafluorobutyl acrylate, Hexafluorobutyl mathacrylate, propylene Sour trifluoro ethyl ester, trifluoroethyl methacrylate, perfluorobutyl ethylene, perfluorohexyl ethylene, perfluorooctyl ethylene, perfluoro decyl Ethene, perfluorododecyl ethene, perfluor myristyl ethene, perfluor hexadecyl vinyl, perfluoro butyl ethyl propylene acid esters, Perfluoro hexyl ethyl propylene acid esters, perfluorooctylethyl group acrylate, perfluoro decyl ethyl propylene acid esters, perfluorododecyl second Base acrylate, perfluor myristyl ethyl propylene acid esters, perfluor cetyl ethyl propylene acid esters, perfluoro butyl ethyl-methyl Acrylate, perfluoro hexyl ethylmethyl acrylate, perfluorooctylethyl group methacrylate, perfluoro decyl ethyl-methyl third Olefin(e) acid ester, perfluorododecyl ethylmethyl acrylate, perfluor myristyl ethylmethyl acrylate, perfluor cetyl Ethylmethyl acrylate, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate any one or it is any a variety of；Institute The activated monomer B-X that is grafted stated is selected from 2 bromo 2 methyl propionic acid allyl ester, 2- chloro-2-methyls allyl propionate, to chloromethyl Styrene, to bromometllylstyrene any one or it is any a variety of；The hydrophile function monomer F1Selected from vinylpyridine Pyrrolidone, acrylonitrile, hydroxyethyl methacrylate, hydroxy propyl methacrylate, hydroxy-ethyl acrylate, times of hydroxypropyl acrylate Anticipate a kind of or any a variety of.
  17. 17. the preparation method according to claims 14 or 15, it is characterised in that the cationic functional monomer F2Choosing From trimethylallylammonium chloride, 2- MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, dimethyl diallyl ammonium chloride, propylene Acyloxyethyl trimethyl ammonium chloride any one or it is any a variety of.
  18. 18. the preparation method according to claims 14 or 15, it is characterised in that the cationic functional monomer F2Choosing From pi-allyl tributyl phosphonium chloride, pi-allyl triphenyl phosphine dichloride, (2- methacrylics) triphenyl phosphine dichloride, pi-allyl triphen Base bromide phosphine, (4- pentenyls) triphenylphosphinebromide any one or it is any a variety of.
  19. 19. a kind of polymeric material, it is characterised in that the polymeric material includes claim 1-13 any one of them Cationic functional fluoropolymer.
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CN110894252B (en) * 2018-09-12 2021-04-30 浙江大学 Anionic fluorine-containing amphiphilic polymer and preparation method thereof
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