CN104725544A - Novel vinylidene fluoride copolymer with high cohesiveness - Google Patents
Novel vinylidene fluoride copolymer with high cohesiveness Download PDFInfo
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- vinylidene fluoride
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Abstract
The invention provides a novel vinylidene fluoride copolymer with high cohesiveness. The novel vinylidene fluoride copolymer is prepared via copolymerization of vinylidene fluoride monomer and at least one modified acrylic ester comonomer, and is suitable to be used as a lithium ion battery binder.
Description
Technical field
The present invention relates to a kind of high-adhesion vinylidene fluoride copolymers, especially relate to the high-adhesion vinylidene fluoride copolymers that a kind of energy is used as lithium ion cell electrode binding agent.
Background technology
PVDF is a kind of partially fluorinated, hemicrystalline polymkeric substance, has the excellent characteristic such as chemical resistant properties, thermomechanically performance, weathering resistance, also has solvent resistance, good molding processibility, good toughness that appropriateness is balanced simultaneously.There is good electrical property in addition, be therefore widely used in the fields such as mould material, coating, lithium electricity, tubing cable.
Lithium cell is the chargeable chemical cell that technology is the highest in the world at present, and nearest more than ten years development rapidly, is mainly used in mobile phone, electronic product and power tool.The active substance of lithium ion battery electrode assembly, conductive agent, remained in current collector by binding agent and use, and this has enough adhesive properties with regard to needing the binding agent used.
Because the adhesive property of PVDF homopolymer is limited, be difficult to the demand meeting high-capacity lithium battery, therefore need to carry out modification to improve its adhesive property to PVDF.Conventional polyvinylidene fluoride modified method has other method of modifying such as modification by copolymerization, blending and modifying and grafting, irradiation, modified with functional group.Prior art has following report for modification by copolymerization:
Japanese Patent Te Open 2003-155313 is open adds the adhesive property that 1wt%2-glycidyl methacrylate (2M-GMA) improves multipolymer in vinylidene.Embodiment data presentation uses the stripping strength of the electrode prepared compared with polyvinylidene fluoride homopolymer for the electrode of binding agent of this multipolymer to improve 5 times, and in propylene carbonate, to soak the stripping strength after 5 days high 14 times for high temperature.In actual polymerisation process, because the activity of 2M-GMA differs comparatively large with vinylidene, considerably reduce rate of polymerization after adding, emulsion polymerisation process cannot be taked to prepare, and the easy homopolymerization of 2M-GMA, cause battery life-time service stability to reduce.
The flat 9-161804 of Japanese Patent, flat 10-233217 and special Open 2001-22301 etc. disclose the multipolymer of vinylidene and TFE and perfluorovinyl sulfide ethers monomer, and the ratio control of vinylidene is between 60-80%.The introducing of TFE and perfluorovinyl sulfide ethers monomer, improves molecule chain flexibility and cohesive force.But perfluorovinyl sulfide ethers monomer is expensive.
Japanese Patent Te Open 2001-19896 discloses the multipolymer of the monomethyl maleate (MMM) of vinylidene and 1wt%, the electrode using this multipolymer to be binding agent comparatively polyvinylidene fluoride homopolymer stripping strength improves 4 times, after in the electrolytic solution of propylene carbonate/glycol dimethyl ether=1/1, high temperature soaks one week, stripping strength is homopolymerization object height 5 times comparatively.When this multipolymer is prepared with suspension polymerization, at 28 DEG C, need the reaction times of more than 40 hours; When preparing with emulsion polymerization, speed of reaction is extremely slow, easily causes breakdown of emulsion.
Chinese patent CN1714465A discloses the multipolymer of the monomer such as vinylidene and acrylate, maleic mono-ester, glycidyl allyl ether, to improve bounding force and the battery use safety of binding agent.
Chinese patent CN101188283A discloses the multipolymer of vinylidene and HFP, with other mineral binder bond acting in conjunction, suppresses the side reaction of positive electrode material and electrolytic solution.
Chinese patent CN101679563A discloses vinylidene and the copolymerization of (methyl) Acrylic Acid Monomer, and ensures that the polar monomer of 40% is uniformly distributed, and in order to keep mechanical property, the chemical stability of polyvinylidene difluoride (PVDF), improves cohesive force simultaneously.
PCT patent application WO01//57095 disclose a kind of method of fluoroolefins and non-fluorine polar monomer copolymerization, wherein fluoroolefins comprises tetrafluoroethylene, trifluorochloroethylene, trifluoro-ethylene, vinyl fluoride and vinylidene, and non-fluorine polar monomer comprises vinyl alcohol, vinylformic acid, acrylate, methacrylic ester.Supercritical polymerization process (carbonic acid gas makes reaction medium) is adopted to prepare multipolymer.
In sum, vinylidene and polar monomer copolymerization is made to be a more difficult job, monomer due to two types has different response features and poor compatibility, cause most polar monomer can not with vinylidene copolymerization, small portion polar monomer can with vinylidene copolymerization, but rate of polymerization comparatively vinylidene homopolymerization significantly decline.
Summary of the invention
The object of the present invention is to provide a kind of vinylidene fluoride copolymers, it has higher molecular-weight average, moderate molecular weight distribution, higher fusing point, good thermomechanical property and high-adhesion energy, and this vinylidene fluoride copolymers can be dissolved in the solvent of conventional polyvinylidene difluoride (PVDF) completely.
For reaching goal of the invention the technical solution used in the present invention be:
A kind of high-adhesion vinylidene fluoride copolymers, is selected from by vinylidene fluoride monomers and at least one the modification acrylate class comonomer that following general structural formula (I) represents and forms:
Wherein:
R
1, R
2and R
3independently selected from F, H, C
1-C
8alkyl, the C replaced by least one atom be selected from F, O, S and N
1-C
8alkyl;
R
4be selected from C
1-C
8alkyl, the C replaced by least one atom be selected from F, O, S and N
1-C
8alkyl;
Described modification acrylate class comonomer content is in the copolymer 0.1 ~ 10wt%.
Carry out copolymerization because acrylic ester monomer is more difficult with vinylidene, the present invention, by carrying out modification to acrylic ester monomer, makes its structure and polymerization activity and vinylidene similar, can more easily and vinylidene carry out copolymerization.
As preferred mode, in the modification acrylate class comonomer that said structure general formula (I) represents, substituting group: R
1, R
2and R
3independently selected from F, H, C
1-C
3alkyl, the C replaced by least one F atom
1-C
3. alkyl, more preferably R
1, R
2and R
3independently selected from F, H, methyl, ethyl, the methyl replaced by least one F atom or ethyl; R
4be selected from C
1-C
3alkyl, the C replaced by least one F atom
1-C
3alkyl, more preferably R
4be selected from methyl, ethyl, the methyl replaced by least one F atom or ethyl.The modification acrylate class comonomer that described general structure (I) represents is particularly preferably 2-trifluoroethyl methacrylate, 2-methacrylic acid trifluoro methyl esters, 1, the fluoro-2-methyl methacrylate of 1-bis-, 2-trifluoromethyl acrylate methyl esters, structural formula is as follows:
The consumption of the modification acrylate class comonomer that described general structure (I) represents, the content be preferably in the copolymer is 1 ~ 5wt%.
High-adhesion vinylidene fluoride copolymers of the present invention, further can contain the 3rd comonomer, the one of described 3rd comonomer preferably in vinyl fluoride, trifluoro-ethylene, tetrafluoroethylene, trifluorochloroethylene, tetrafluoroethylene, tetrafluoeopropene, five fluorine propylene, R 1216, perfluoro methyl vinyl ether and perfluoro propyl vinyl ether, more than two or three combination, more preferably R 1216.Described 3rd comonomer content is in the copolymer preferably 0.1 ~ 50wt%, and more preferably the 3rd comonomer content is in the copolymer 1 ~ 10%.
High-adhesion vinylidene fluoride copolymers provided by the invention, its fusing point is 160 ~ 172 DEG C, thermal weight loss (400 DEG C) is for <1%(is according to its weightlessness stood in TGA analyzes of ISO11358 standard), limiting viscosity 0.7 ~ 4dl/g, weight-average molecular weight is 30 ~ 1,200,000 grams/mol, molecular weight distribution index is 1.6 ~ 5, molecular weight distribution curve is unimodal distribution, melt flow rate (MFR) is 0.02-10 gram/10 minutes (reference GB/T3682-2000, 230 DEG C, bear a heavy burden 5 kilograms), to be 1 ~ 10N/m(measure polymkeric substance preparation by ISO4624 standard (adhesive power pull-off test) to cohesive strength becomes the cohesive strength after electrode), wherein cohesive strength is further preferably 5 ~ 10N/m.
Originally the high-adhesion vinylidene fluoride copolymers provided, property indices illustrates, it is especially suitable for use as lithium ion battery binding agent.
High-adhesion vinylidene fluoride copolymers of the present invention can be prepared by emulsion polymerization or suspension polymerization.
When adopting emulsion polymerization, common preparation process is as follows:
A () provides vinylidene and the selected dispersion of one or more comonomers in water, described dispersion is optionally containing tensio-active agent;
B () adds a certain amount of water and dispersion agent to polymerization reaction kettle, add a certain amount of vinylidene fluoride monomers to polymeric kettle, be warming up to assigned temperature after closing still, adds chain-transfer agent and organic initiators with initiated polymerization;
C () adds organic initiators further, when reacting kettle inner pressure adds vinylidene fluoride monomers lower than during specified pressure;
D () adds the dispersion of the comonomer selected to reactor when vinylidene fluoride monomers add-on arrives certain value;
(e) when vinylidene add-on arrive designated value, and reacting kettle inner pressure lower than designated value time, stop add organic initiators;
F () carries out aftertreatment to products therefrom emulsion, obtain vinylidene fluoride copolymers.
When adopting emulsion polymerization way, in order to improve the stability of monomer dispersion liquid, also optionally in dispersion liquid, add stablizer.In a better example of the present invention, use paraffin as the stablizer of dispersion liquid.The add-on of stablizer is without particular limitation, mainly can stable dispersions.
When adopting emulsion polymerization way, the monomer feed mode being applicable to the inventive method is that vinylidene fluoride monomers and comonomer segmentation join in polymerization reaction kettle, vinylidene fluoride monomers is added to specified pressure when still internal pressure is less than 5.5 ~ 6.0MPa, when vinylidene fluoride monomers add-on is to certain value, at intervals comonomer dispersion is added to wherein by pressure measurement pump, until polyreaction terminates.Reaction pressure remains on generally and is greater than vinylidene fluoride monomers emergent pressure.
When adopting suspension polymerization, common preparation process is as follows:
A () provides vinylidene and one or more selected comonomers;
B () adds a certain amount of water and dispersion agent to polymerization reaction kettle, to close after still the disposable vinylidene fluoride monomers adding specified amount to polymeric kettle after, and by pressure measurement pump, comonomer is added to reactor, be warming up to assigned temperature, disposablely add chain-transfer agent and organic initiators with initiated polymerization by pressure measurement pump;
(c) when reacted between arrive certain value, and reacting kettle inner pressure lower than designated value time, stopped reaction;
D () carries out aftertreatment to products therefrom, obtain vinylidene fluoride copolymers.
In suspension polymerization, in order to improve the dispersiveness of monomer in water, optionally add dispersion agent to dispersion system.The add-on of dispersion agent is without particular limitation, mainly can improve the dispersiveness of monomer and can not produce adverse influence to the polymkeric substance of polyreaction subsequently or formation.The type of same dispersion agent is also without particular limitation, as long as it can improve the dispersiveness of monomer and can not have a negative impact to the polymkeric substance of polyreaction subsequently or formation.In a good example of the present invention, described dispersion agent generally adopts fluorochemical surfactant or Mierocrystalline cellulose, and its not limiting example has: XC
nf
2ncOOM, wherein X is fluorine atom or hydrogen atom, and n is the integer of 4 ~ 12, and M is hydrogen atom or alkalimetal ion or ammonium ion or substituted ammonium ion or polyether segment, as C
7f
15cOOH.In a better example of the present invention, by 100 weight parts monomers raw materials, dispersion agent add-on is 0.01 ~ 1 weight part.
When adopting suspension polymerization mode, the monomer feed mode being applicable to the inventive method is similarly vinylidene fluoride monomers segmentation and is added to reactor, comonomer after vinylidene fluoride monomers adds, still internal pressure is when being less than 5.5 ~ 6.0MPa, at intervals comonomer dispersion joined reactor by pressure measurement pump.Reaction pressure remains on generally and is greater than vinylidene fluoride monomers emergent pressure.In emulsion polymerization and suspension polymerization, the organic initiators of use is not particularly limited, and it can be the polymerization starter that this area is commonly used.Described initiator is generally organo-peroxide, and its example comprises: di-isopropyl peroxydicarbonate, peroxy dicarbonate diisobutyl ester, peroxy dicarbonate diethyl ester.In emulsion polymerization, general distribution adds organic initiators, by 100 weight part vinylidene fluoride monomers or copolymerization mix monomer, the consumption (i.e. the add-on of the middle initiator of step (b)) for the initiator of initial initiated polymerization can be 0.05 ~ 0.5 weight part.In suspension polymerization, generally disposablely add organic initiators.
In emulsion polymerization and suspension polymerization, also need to add chain-transfer agent, being applicable to chain-transfer agent of the present invention can be any compound that can continue vinylidene fluoride polymerization reaction, comprising: alcohols, as Virahol, propyl carbinol; Ketone, as acetone, butanone; Ester class, as ethyl acetate, diethyl carbonate, methylcarbonate; Containing halohydrocarbon, as chloroform, methylene dichloride; Aliphatic alkane, as normal hexane.By 100 weight part vinylidenes or copolymerization mix monomer, the consumption of chain-transfer agent is 0.01 ~ 0.2 weight part.
Vinylidene fluoride copolymers of the present invention can be dissolved in the solvent of conventional polyvinylidene difluoride (PVDF) completely, and the example of described solvent has N, N-dimethyl pyrrolidone (NMP), N,N-DIMETHYLACETAMIDE (DMAc), DMF (DMF) etc., preferred NMP.
High-adhesion vinylidene fluoride copolymers various performance parameters testing method of the present invention is as follows:
(1) measure polymkeric substance preparation by ISO4624 standard (adhesive power pull-off test) and become the cohesive strength after electrode, carry out under 25 DEG C and 50% relative humidity;
(2) by GB/T3682-2000 standard test melt flow rate (MFR) (MFR).Probe temperature is 230 DEG C, and loading is 5 kilograms;
(3) by ISO11358 standard, TGA analysis is carried out to sample.In a nitrogen atmosphere, carry out in a dynamic mode, record to obtain be respectively 0.5%, 0.75% and 1%wt polymkeric substance weightlessness needed for temperature, these temperature are higher, and the thermostability of polymkeric substance is higher;
(4) by ASTM D4591 standard test melting enthalpy.Heating schedule is: be warming up to 190 DEG C with the heat-up rate of 10 DEG C/min by 80 DEG C, 190 DEG C of insulations 10 minutes, be cooled to 80 DEG C with the cooling rate of 80 DEG C/min by 190 DEG C, in 80 DEG C, be incubated 2 minutes, be warming up to 190 DEG C with the heat-up rate of 10 DEG C/min by 80 DEG C.DSC spectrogram during the melting of record second time;
(5) solubility experiment uses NMP to be solvent.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, but does not limit the invention to these embodiments.One skilled in the art would recognize that all alternativess, improvement project and the equivalents that present invention encompasses and may comprise in Claims scope.
Embodiment 1
Adding in 5 liters of vertical polymerization reaction kettles in 2500 grams of deionized waters, 5 grams of ammonium perfluorocaprylates and homologous mixture thereof and 1 gram of melting range is the paraffin of about 60 DEG C.Merge reactor, vacuumize and use nitrogen replacement, until oxygen level is less than 5ppm in reactor, then adds a certain amount of vinylidene fluoride monomers and make still internal pressure to 2.0MPa.Then start to stir with the speed of 500rpm, reactor temperature is risen to 65 DEG C, continue to supplement vinylidene fluoride monomers and reach 6.0MPa to reacting kettle inner pressure.Add 0.5 gram of dibenzoyl peroxide (BPO), start polyreaction.Making reacting kettle inner pressure maintain 5.5 ~ 6.0MPa by adding vinylidene fluoride monomers, adding BPO with the speed of 0.1 gram/15 minutes, when the vinylidene fluoride monomers of total amount 1000g add complete and in still, reaction pressure is down to below 3.0MPa time stop adding BPO; Comonomer 2-trifluoroethyl methacrylate in vinylidene weight part 1% ratio feed intake and ethyl acetate 0.5g, when vinylidene fluoride monomers charged material weight reaches 30%, 45%, 60%, 70%, 80%, 95% of preset value, average segmentation joins polymeric kettle.Reaction terminates rear collection emulsion, filters, breakdown of emulsion, and washing is dry, obtains vinylidene fluoride copolymers toner.
Measure polymkeric substance preparation by ISO4624 standard (adhesive power pull-off test) and become the cohesive strength after electrode.The preparation process of electrode is as described below: under room temperature state, is dissolved in 50gNMP by aforementioned for the 1g vinylidene fluoride copolymers resin prepared under mechanical stirring.2g graphitized carbon black and 30g cobalt acid lithium (LiCoO is added under the state stirred
2), fully mixing ensures homogeneity.Then mixture is degassed under vacuo and spread on aluminium foil with scraper, finally the aluminium foil sprawling upper electrode material mixture is positioned over vacuum drying oven and is warming up to 60 DEG C of dryings 12 hours, finally prepare electrode slice.Puller system survey meter is used to measure the cohesive strength of electrode slice upper electrode material.Each value at least gets the mensuration mean value of 5 electrode slices, and test data is in table 1.
Embodiment 2
2500 grams of deionized waters, 5 grams of methylcellulose gum are added in 5 liters of vertical polymerization reaction kettles.Merge reactor, vacuumize and use nitrogen replacement, until oxygen level is less than 5ppm in reactor, adding the vinylidene fluoride monomers of 1500g, 5g2-trifluoroethyl methacrylate, 2g ethyl acetate.Then start to stir with the speed of 500rpm, reactor temperature is risen to 28 DEG C, add 2.5 grams of dibenzoyl peroxide (BPO), start polyreaction.React after 12 hours, Pressure Drop, to 3.0MPa, stops polyreaction.Reaction terminates rear collection material, washing, dry, obtains vinylidene fluoride copolymers toner.
After tested, the limiting viscosity of obtained vinylidene fluoride copolymers toner is 1.8dl/g.According to the method described in embodiment 1, the vinylidene fluoride copolymers toner of restraining 1 prepare electrode slice, test data is in table 1.
Embodiment 3
2500 grams of deionized waters, 5 grams of methylcellulose gum are added in 5 liters of vertical polymerization reaction kettles.Merge reactor, vacuumize and use nitrogen replacement, until oxygen level is less than 5ppm in reactor, adding the vinylidene fluoride monomers of 1500g, the fluoro-2-methyl methacrylate of 5g1,1-bis-, 2g ethyl acetate.Then start to stir with the speed of 500rpm, reactor temperature is risen to 28 DEG C, add 2.5 grams of dibenzoyl peroxide (BPO), start polyreaction.React after 12 hours, Pressure Drop, to 3.0MPa, stops polyreaction.Reaction terminates rear collection material, washing, dry, obtains vinylidene fluoride copolymers toner.
After tested, the limiting viscosity of obtained vinylidene fluoride copolymers toner is 1.9dl/g.According to the method described in embodiment 1, the vinylidene fluoride copolymers toner of restraining 1 prepare electrode slice, test data is in table 1.
Embodiment 4
2500 grams of deionized waters, 5 grams of methylcellulose gum are added in 5 liters of vertical polymerization reaction kettles.Merge reactor, vacuumize and use nitrogen replacement, until oxygen level is less than 5ppm in reactor, adding the vinylidene fluoride monomers of 1500g, 5g2-trifluoromethyl acrylate methyl esters, 2g ethyl acetate.Then start to stir with the speed of 500rpm, reactor temperature is risen to 28 DEG C, add 2.5 grams of dibenzoyl peroxide (BPO), start polyreaction.React after 12 hours, Pressure Drop, to 3.0MPa, stops polyreaction.Reaction terminates rear collection material, washing, dry, obtains vinylidene fluoride copolymers toner.
After tested, the limiting viscosity of obtained vinylidene fluoride copolymers toner is 1.9dl/g.According to the method described in embodiment 1, the vinylidene fluoride copolymers toner of restraining 1 prepare electrode slice, test data is in table 1.
Comparing embodiment 1
2500 grams of deionized waters, 5 grams of methylcellulose gum are added in 5 liters of vertical polymerization reaction kettles.Merge reactor, vacuumize and use nitrogen replacement, until oxygen level is less than 5ppm in reactor, adding the vinylidene fluoride monomers of 1500g, 5g ethyl propenoate, 2g ethyl acetate.Then start to stir with the speed of 500rpm, reactor temperature is risen to 28 DEG C, add 2.5 grams of dibenzoyl peroxide (BPO), start polyreaction.Treat that Pressure Drop is to 3.0MPa, stop polyreaction.Reaction terminates rear collection material, washing, dry, obtains vinylidene fluoride copolymers toner.
After tested, the limiting viscosity of obtained vinylidene fluoride copolymers toner is 2.0dl/g.According to the method described in embodiment 1, the vinylidene fluoride copolymers toner of restraining 1 prepare electrode slice, test data is in table 1.
Comparing embodiment 2
According to the method described in embodiment 1, be that the KUREHA9200 vinylidene fluoride copolymers of 1.8dl/g prepares electrode slice by the limiting viscosity of 1 gram, test data is in table 1.
Comparing embodiment 3
According to the method described in embodiment 1, be that the SOLVAY5130 vinylidene fluoride copolymers of 2.3dl/g prepares electrode slice by the limiting viscosity of 1 gram, test data is in table 1.
Table 1
By the known vinylidene of the data of above-mentioned table 1 by after the modification acrylate class comonomer that represents with general structure (I), can obtain adhesive property and have the polyvinylidene fluoride copolymer significantly improved, and polymerization time more non-fluoro class polar monomer significantly reduces.
Claims (11)
1. a high-adhesion vinylidene fluoride copolymers, is characterized in that described vinylidene fluoride copolymers is selected from by vinylidene fluoride monomers and at least one the modification acrylate class comonomer that following general structural formula (I) represents and forms:
Wherein:
R
1, R
2and R
3independently selected from F, H, C
1-C
8alkyl, the C replaced by least one atom be selected from F, O, S and N
1-C
8alkyl;
R
4be selected from C
1-C
8alkyl, the C replaced by least one atom be selected from F, O, S and N
1-C
8alkyl;
Described modification acrylate class comonomer content is in the copolymer 0.1 ~ 10wt%.
2., according to high-adhesion vinylidene fluoride copolymers according to claim 1, it is characterized in that the R of described modification acrylate class comonomer
1, R
2and R
3independently selected from F, H, C
1-C
3alkyl, the C replaced by least one F atom
1-C
3. alkyl, R
4be selected from C
1-C
3alkyl, the C replaced by least one F atom
1-C
3alkyl, modification acrylate class comonomer content is in the copolymer 1 ~ 5wt%.
3., according to high-adhesion vinylidene fluoride copolymers according to claim 2, it is characterized in that the R of described modification acrylate class comonomer
1, R
2and R
3independently selected from F, H, methyl, ethyl, the methyl replaced by least one F atom or ethyl, R
4be selected from methyl, ethyl, the methyl replaced by least one F atom or ethyl.
4. according to high-adhesion vinylidene fluoride copolymers according to claim 3, it is characterized in that described modification acrylate class comonomer is 2-trifluoroethyl methacrylate, 2-methacrylic acid trifluoro methyl esters, 1,1-bis-fluoro-2-methyl methacrylate, 2-trifluoromethyl acrylate methyl esters.
5. according to high-adhesion vinylidene fluoride copolymers according to claim 1, it is characterized in that described vinylidene fluoride copolymers contains the 3rd comonomer, the one, more than two or three that described 3rd comonomer is selected from vinyl fluoride, trifluoro-ethylene, tetrafluoroethylene, trifluorochloroethylene, tetrafluoroethylene, tetrafluoeopropene, five fluorine propylene, R 1216, perfluoro methyl vinyl ether and perfluoro propyl vinyl ether combines, and described 3rd comonomer content is in the copolymer 0.1 ~ 50wt%.
6. according to high-adhesion vinylidene fluoride copolymers according to claim 5, it is characterized in that described 3rd comonomer is R 1216, described 3rd comonomer content is in the copolymer 1 ~ 10%.
7., according to high-adhesion vinylidene fluoride copolymers according to claim 1, it is characterized in that described vinylidene fluoride copolymers is prepared by emulsion polymerization or suspension polymerization.
8., according to high-adhesion vinylidene fluoride copolymers according to claim 7, it is characterized in that vinylidene fluoride monomers and the charging of modification acrylate class comonomer sectional type, add residual monomer when still internal pressure is less than 5.5 ~ 6.0MPa; Dispersion agent is XC
nf
2ncOOM, wherein X is fluorine atom or hydrogen atom, and n is the integer of 4 ~ 12, and M is hydrogen atom or alkalimetal ion or ammonium ion or substituted ammonium ion or polyether segment; Organic initiators is di-isopropyl peroxydicarbonate, peroxy dicarbonate diisobutyl ester, peroxy dicarbonate diethyl ester; Chain-transfer agent is Virahol, propyl carbinol, acetone, butanone, ethyl acetate, diethyl carbonate, methylcarbonate, chloroform, methylene dichloride, normal hexane.
9., according to the high-adhesion vinylidene fluoride copolymers one of claim 1-8 Suo Shu, it is characterized in that the fusing point of described vinylidene fluoride copolymers is 160 ~ 172 DEG C, cohesive strength is 1 ~ 10N/m, thermal weight loss (400 DEG C) is <1%, limiting viscosity 0.7 ~ 4dl/g.
10. according to high-adhesion vinylidene fluoride copolymers according to claim 8, it is characterized in that the weight-average molecular weight of described vinylidene fluoride copolymers is 30 ~ 1,200,000 grams/mol, molecular weight distribution index is 1.6 ~ 5, molecular weight distribution curve is unimodal distribution, melt flow rate (MFR) is 0.02 ~ 10 gram/10 minutes, cohesive strength is 5 ~ 10N/m, N can be dissolved in, N-dimethyl pyrrolidone, N,N-DIMETHYLACETAMIDE or DMF.
11. according to high-adhesion vinylidene fluoride copolymers according to claim 9, it is characterized in that described vinylidene fluoride copolymers is used as lithium ion battery binding agent.
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| CN111954657A (en) * | 2018-04-10 | 2020-11-17 | 阿科玛股份有限公司 | Functional fluoropolymers |
| EP3774714A4 (en) * | 2018-04-10 | 2021-12-22 | Arkema, Inc. | Functional fluoropolymers |
| WO2019239781A1 (en) | 2018-06-12 | 2019-12-19 | 株式会社クレハ | Binder composition, electrode mixture, electrode structure, method for manufacturing electrode structure, and secondary cell |
| CN112542588A (en) * | 2019-09-20 | 2021-03-23 | 浙江蓝天环保高科技股份有限公司 | Vinylidene fluoride copolymer, and preparation method and application thereof |
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Denomination of invention: A high adhesive vinylidene fluoride copolymer Effective date of registration: 20211011 Granted publication date: 20160817 Pledgee: Industrial and Commercial Bank of China Limited Hangzhou Zhaohui sub branch Pledgor: SINOCHEM LANTIAN Co.,Ltd. Registration number: Y2021330001830 |
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