CN103588922A - Vinylidene fluoride copolymer, and preparation method and application thereof - Google Patents
Vinylidene fluoride copolymer, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a vinylidene fluoride copolymer containing vinylidene fluoride monomers and at least one modified maleic acid ester monomer having a structure shown as a formula (I) (structural formula and substituent groups are specified in the descriptions), and the modified maleic ester accounts for more than 0-20% of the total copolymer monomer. The invention also provides a preparation method of the vinylidene fluoride copolymer. The vinylidene fluoride copolymer provided by the invention has high bonding strength, and is especially suitable for lithium ion battery.
Description
Technical field
The present invention relates to a kind of vinylidene fluoride copolymers.
Background technology
Polyvinylidene difluoride (PVDF) (PVDF) is the homopolymer of vinylidene (VDF), and it is a kind of thermoplastic engineering plastic of toughness.Polyvinylidene difluoride (PVDF) is except having the general characteristic of high thermal resistance, super-weathering resistance, erosion resistance, pollution resistance, unreactiveness and extremely low fluoropolymers such as surface energy, also there is the properties such as piezoelectricity, dielectricity, pyroelectricity, main pooled applications, in petrochemical complex, electric, fluorocarbon coating and the large field of mould material four, has vast potential for future development.
Lithium cell is the current the highest chargeable chemical cell of technology in the world, and more than ten years development recently rapidly, is mainly used in mobile phone, electronic product and power tool.Lithium-ions battery positive and negative electrode for the meeting of volume in charge and discharge process dilation, require binding agent can play certain shock absorption, the requirement that therefore must meet as lithium ion battery binding agent is: (1) has enough cohesive strengths, prevent that active substance from coming off from current collector, or cracking in battery assembling process; (2) binding agent can not be dissolved in for the organic solvent as electrolytic solution, but can be dissolved in the solvent of making current collector top coat; (3), at operating voltage range, binding agent can not be oxidated or reduced.
Because the surface of fluorine atom can be little, generally, the adhesive property of vinylidene fluoride homopolymer is limited, in order to prepare jumbo lithium cell, requires to improve the content of electrical conductor in unit volume.Because vinylidene fluoride homopolymer itself is non-conductive, this just need to guarantee that under the prerequisite of binding agent adhesive property, the least possible consumption of binder, therefore, need to carry out modification to polyvinylidene difluoride (PVDF) and improve its adhesive property.
At present the method for more common modified polyvinilidene fluoride mainly can be divided into three major types, i.e. other method of modifying such as blending and modifying, modification by copolymerization and grafting, irradiation, modified with functional group.Blending and modifying is easy and simple to handle, mainly common are at present the blend of polyvinylidene difluoride (PVDF) and polymethylmethacrylate, polyvinylidene difluoride (PVDF), the polymkeric substance that these add, itself has good cohesiveness, therefore relative and polyvinylidene difluoride (PVDF), such blend has better cohesiveness.But there is the factors leading to social instability such as thermotolerance declines, is separated.Modification by copolymerization is another kind of more common method of modifying, utilizes vinylidene and other monomer to form multipolymer, has following report in prior art:.
Japanese Patent Te Open 2003-155313 report, in vinylidene, add 1wt%2-glycidyl methacrylate (being called for short " 2M-GMA "), suspension copolymerization, this multipolymer is that the stripping strength of the electrode prepared compared with polyvinylidene fluoride homopolymer of the electrode of binding agent improves 5 times, and the stripping strength that in propylene carbonate, high temperature soaked after 5 days is high 14 times.But in actual polymerisation process, homopolymerization easily occurs 2M-GMA, reduced the stability of battery life-time service.
The flat 9-161804 of Japanese Patent, flat 10-233217 and special Open 2001-223011 patent research the copolymerization of vinylidene and TFE and perfluorovinyl sulfide ethers monomer, the ratio control of vinylidene is between 60-80%.TFE is introduced under the prerequisite that has guaranteed degree of crystallinity, has promoted Chain Flexibility, and perfluorovinyl sulfide ethers monomer not only promoted Chain Flexibility, more because it contains Sauerstoffatom, further promoted the cohesive force of molecular chain.But perfluorovinyl sulfide ethers monomer is expensive.
Japanese Patent Te Open 2001-19896 report, the monomethyl maleate (being called for short " MMM ") that adds 1wt% in vinylidene, suspension copolymerization, this multipolymer is that the electrode of binding agent improves 4 times compared with polyvinylidene fluoride homopolymer stripping strength, in the electrolytic solution of propylene carbonate/glycol dimethyl ether=1/1, high temperature soaked after one week, and stripping strength is compared with 5 times of homopolymerization object heights.
In Chinese patent CN1714465A, mentioned the method for vinylidene with the monomer copolymerization that contains hydroxyl and carboxyl, enumerated the monomers such as acrylate, toxilic acid monoesters, glycidyl allyl ether, main purpose is to use safety for improving bounding force and the battery of binding agent.
Monomer mentioned in the comonomer of mentioning in Chinese patent CN1240053A and Japanese Patent Laid-Open 2001-223011 is basically identical, and adding of TFE improved swelling resistance performance, the adding in order to promote cohesive force of perfluorovinyl sulfide ethers monomer.
In Chinese patent CN101188283A, adopt the multipolymer of vinylidene and HFP, with other mineral binder bond acting in conjunction, suppress the side reaction of positive electrode material and electrolytic solution.
In Chinese patent CN101679563A, mention vinylidene and the copolymerization of (methyl) Acrylic Acid Monomer, and guarantee that 40% polar monomer is uniformly distributed, in order to keep mechanical property, the chemical stability of polyvinylidene difluoride (PVDF), improve cohesive force simultaneously.
PCT patent application WO01//57095 09.08.2001 discloses 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.Adopt supercritical polymerization process (carbonic acid gas is made reaction medium) to prepare multipolymer.This patent has also disclosed the difference due to non-fluorine polar monomer and Fluorine containing olefine consistency, polar monomer is more prone to autohemagglutination and forms a kind of block structure, according to change block length and the region of polymerizing condition, also change simultaneously, in this CO 2 supercritical polymerization, selected tensio-active agent can be adjusted the distributing homogeneity of Fluorine containing olefine in molecular chain.
In sum, making vinylidene and polar monomer copolymerization is a more difficult job, due to the monomer of two types there is different response features and consistency poor, the disclosed vinylidene fluoride copolymers of prior art is limited to improving the effect of polymer bonding performance.
Summary of the invention
The object of the present invention is to provide a kind of vinylidene fluoride copolymers, this multipolymer has higher molecular-weight average, moderate molecular weight distribution, higher fusing point and good thermomechanical property, the repeating unit of stochastic distribution polar monomer in molecular chain, thereby realize, improve adhesive property and to keep the balance between mechanical property that the finished product are higher, this vinylidene fluoride copolymers can be dissolved in the solvent of conventional polyvinylidene difluoride (PVDF) completely, and the time of required time of this multipolymer and production polyvinylidene fluoride homopolymer of producing is similar or slightly slow.
The inventor studies and finds that toxilic acid esters monomer can carry out copolymerization with vinylidene.The multipolymer of monomethyl maleate and vinylidene for example, its cohesiveness has obvious lifting compared with vinylidene fluoride homopolymer, but because its side chain lengths is shorter, the lifting of adhesive property still has Maximum Space.According to the ultimate principle of binding agent, when side chain atomicity is 4-10, have good Side Chain Flexibility, the nuclear power such as simultaneously more O, S, N, Cl and Br provide more cohesive action point, two aspect factor actings in conjunction, can significantly promote the adhesive property of polymkeric substance.
Therefore the invention provides a kind of vinylidene fluoride copolymers, contain fluoride monomers and at least one modification toxilic acid esters monomer, modification toxilic acid esters monomer accounts for the quality proportioning of total comonomer for being greater than 0～20%, be in vinylidene comonomer, the content range of modification toxilic acid esters monomer is for being greater than 0 to being less than or equal to 20%, and described modification toxilic acid esters monomer has following structural formula (I):
（I）
Wherein:
R
1be selected from C
3-C
8alkyl, the C that contains optional at least one heteroatoms replacement in O, S, N, Cl and Br
1-C
8alkyl;
R
2, R
3independently selected from hydrogen atom, C
1-C
8alkyl, the C that contains optional at least one heteroatoms replacement in O, S, N, Cl and Br
1-C
8alkyl.
As preferred mode, in above-mentioned modification toxilic acid esters monomer, described R
1be preferably C
3-C
8alkyl or the C that contains optional at least one heteroatoms replacement in O, S, Cl and Br
1-C
8alkyl, more preferably contain that optional at least one heteroatoms in O and Cl replaces C
1-C
4alkyl; Described R
2and R
3be preferably hydrogen atom.
As preferred mode, the quality proportion optimization that above-mentioned modification toxilic acid esters monomer accounts for total comonomer is 0.1～10%, more preferably 1～5%.
Vinylidene fluoride copolymers of the present invention can also further contain the 3rd comonomer, described the 3rd comonomer be selected from vinyl fluoride, trifluoro-ethylene, tetrafluoroethylene, trifluorochloroethylene, tetrafluoroethylene, tetrafluoeopropene, five fluorine propylene, R 1216, perfluoro methyl vinyl ether, perfluoro propyl vinyl ether and other can with the Fluorine containing olefine of vinylidene copolymerization in a kind of, more than two or three combination, the quality proportioning that described the 3rd comonomer accounts for total comonomer is 0.1～50%.
The weight-average molecular weight of vinylidene fluoride copolymers of the present invention is preferably 30～1,200,000 grams/mol, molecular weight distribution coefficient is preferably 1.6～5, molecular weight distribution curve is preferably unimodal distribution, and melt flow rate (MFR) is preferably 0.02～10 gram/10 minutes, and limiting viscosity is preferably 0.5-4.0 * 10
2dl/g, fusing point is preferably greater than 150 ℃, is preferably being greater than the weightlessness that stands to be less than 1%wt at the temperature of 400 ℃.
The cohesive strength of vinylidene fluoride copolymers of the present invention is preferably more than 50N/m, is suitable as lithium ion battery binding agent.
The present invention also provides the polymerization process of above-mentioned vinylidene fluoride copolymers, comprises letex polymerization and suspension polymerization.Wherein emulsion polymerization comprises the following steps:
(1) to reactor, provide dispersion and the vinylidene fluoride monomers of at least one modification toxilic acid esters monomer claimed in claim 1 of part in water;
(2) to reactor, add emulsifying agent, chain-transfer agent and initiator, initiated polymerization under 70 ℃～120 ℃ temperature and 2.0～12.0MPa pressure;
(3) mode that adopts segmentation to feed intake adds dispersion and the vinylidene fluoride monomers of remaining at least one modification toxilic acid esters monomer claimed in claim 1 in water, and maintenance polymerization pressure is 3.0～12.0MPa, and adds initiator;
(4), when polymerization pressure drops to 2.0～11.0MPa, stop adding initiator, until reaction finishes;
In reaction process, the quality proportioning that the modification toxilic acid esters monomer total amount that control adds accounts for whole monomers is 0.1～20%.
As preferred mode, the vinylidene fluoride monomers amount adding in above-mentioned steps (1) accounts for 1～25% of total vinylidene fluoride monomers add-on.
The present invention is not particularly limited emulsifying agent, and it can be the conventional polymeric emulsifiers in this area, and its example comprises perfluorocarboxylic acid, perfluorocarboxylic acid salt, PFPE.Be preferably PFPE carboxylate salt, there is following structural formula (II)
CF
3CF
2CF
2O(CF(CF
3)CF
2O)
n-2CF(CF
3)COOM （II）
The integer of n=2～6 herein ,-COOM is an alkali metal salt, ammonium salt or rudimentary alkylamine salt.
The method that vinylidene fluoride copolymers is prepared in suspension polymerization comprises the following steps:
(1) to reactor, provide dispersion and the vinylidene fluoride monomers of at least one modification toxilic acid esters monomer claimed in claim 1 of part in water;
(2) add dispersion agent, chain-transfer agent and initiator, initiated polymerization under the condition of 20 ℃～60 ℃ temperature and 3.0～12.0MPa pressure;
(3) mode that adopts segmentation to feed intake adds dispersion and the vinylidene fluoride monomers of remaining at least one modification toxilic acid esters monomer claimed in claim 1 in water, and maintenance polymerization pressure is 3.0～12.0MPa.
(4), when polymerization pressure drops to 2.0～11.0MPa, reaction finishes;
In reaction process, the quality proportioning that the modification toxilic acid esters monomer total amount that control adds accounts for total comonomer is 0.1～20%.
As preferred mode, the vinylidene fluoride monomers amount adding in above-mentioned steps (1) accounts for 1～25% of total vinylidene fluoride monomers add-on.
The present invention has no special requirements to initiator, and it can be the conventional polymerization starter in this area.Described initiator is generally organo-peroxide, and its example comprises: di-isopropyl peroxydicarbonate, peroxy dicarbonate diisobutyl ester, peroxy dicarbonate diethyl ester.By 100 weight part polymerization single polymerization monomers, for the consumption (being the add-on of step (1) initiator) of the initiator of initial initiated polymerization, can be 0.05～0.5 weight part.
While adopting emulsion polymerization way, in reaction process, need further to add organic initiators.In the methods of the invention, the object of the organic initiators adding is subsequently to control to generate the instantaneous molecular weight of polymkeric substance and final molecular weight distribution, therefore need to control the variation of organic initiators concentration in reaction system.The method of controlling organic initiators change in concentration in reaction system is at the decomposition rate under specified temp, by certain time interval, to add initiator according to initiator.Disposablely while adopting suspension polymerization mode add all initiators to reactor.
The chain-transfer agent that is applicable to the inventive method can be any compound that can continue vinylidene polyreaction, and its example comprises: alcohols, as Virahol, propyl carbinol; Ketone, as acetone, butanone; Ester class, as ethyl acetate, diethyl carbonate, methylcarbonate; Containing halohydrocarbon, as chloroform, methylene dichloride; Aliphatics alkane, as normal hexane.By 100 weight part polymerization single polymerization monomers, the consumption of chain-transfer agent is 0.01～0.2 weight part.
When adopting suspension polymerization, for improving the dispersiveness of monomer in water, optionally to dispersion system, add dispersion agent.The add-on of dispersion agent is without particular limitation, mainly can improve the dispersed of monomer and can not produce adverse influence to polyreaction subsequently or the polymkeric substance of formation.The type of same dispersion agent is also without particular limitation, as long as it can improve the dispersed of monomer and can not have a negative impact to polyreaction subsequently or the polymkeric substance of formation.In a good example of the present invention, described dispersion agent generally adopts fluorochemical surfactant or Mierocrystalline cellulose, and its indefiniteness example has: XC
nf
2ncOOM, wherein X is fluorine atom or hydrogen atom, and n is 4～12 integer, 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 part polymerization single polymerization monomers, dispersion agent add-on is 0.01～1 weight part.
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.While adopting suspension polymerization mode without adding stablizer.
The reaction pressure that is applicable to the inventive method in whole operating process remains on a value that is greater than vinylidene fluoride monomers emergent pressure generally.
For used organic initiators, polyreaction of the present invention can adopt the polymerization temperature of the relative broad range that is greater than vinylidene fluoride monomers critical temperature.
Vinylidene fluoride copolymers prepared by 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),
n,
n-dimethyl formamide (DMF) etc., preferably NMP.
The present invention also provides a kind of composition that forms electrode, comprises above-mentioned vinylidene fluoride copolymers, powder electrode material and gives the additive of electrical conductivity.In the composition of formation electrode of the present invention, each composition forms by following quality proportioning:
(1) vinylidene fluoride copolymers 1%～10%;
(2) as the carbon black that gives the additive of electrical conductivity, 2%～10%;
(3) powder electrode material 80%～97%, for by general formula LiMY
2the complex metal compound of representative, wherein M is selected from a kind of, more than two or three combination in Co, Ni, Fe, Mn, Cr and V, and Y is O or S.
The composition of formation electrode provided by the invention, is suitable as the electrode of lithium cell or electrical condenser.
Testing method of the present invention is as follows:
(1) by ISO4624 standard (adhesive power pull-off test), measuring polymkeric substance preparation becomes the cohesive strength after electrode, under 25 ℃ and 50% relative humidity, carries out.
(2) press GB/T 3682-2000 standard test melt flow rate (MFR) (MFR).Probe temperature is 230 ℃, and loading is 5 kilograms.
(3) by ISO11358 standard, sample is carried out to TGA analysis.Under nitrogen atmosphere, under dynamic mode, carry out, record is respectively 0.5%, 0.75% and the required temperature of weightlessness of the polymkeric substance of 1%wt to obtaining, and these temperature are higher, and the thermostability of polymkeric substance is higher.
(4) press ASTM D4591 standard test melting enthalpy.Heating schedule is: with the heat-up rates of 10 ℃/min, by 80 ℃, be warming up to 190 ℃, 190 ℃ of insulations 10 minutes, with the cooling rates of 80 ℃/min, by 190 ℃, be cooled to 80 ℃, in 80 ℃, be incubated 2 minutes, with the heat-up rates of 10 ℃/min, by 80 ℃, be warming up to 190 ℃.DSC spectrogram while recording melting for the second time.
(5) by ISO4624 standard (adhesive power pull-off test), measure polymkeric substance preparation and become the cohesive strength after electrode.
It is solvent that solubility experiment is used NMP, the results are shown in following table 1.
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 the present invention contained all alternativess, improvement project and the equivalents that within the scope of claims, may comprise.
embodiment 1
In 5 liters of vertical polymerization reaction kettles, adding in 2500 grams of deionized waters, 5 grams of ammonium perfluorocaprylates and homology mixture and 1 gram of melting range is the paraffin of 60 ℃ of left and right.Merge reactor, vacuumize and use nitrogen replacement, until oxygen level is less than 10ppm in reactor, then add a certain amount of vinylidene fluoride monomers to make still internal pressure to 2.0MPa.Then start to stir with the speed of 500rpm, reactor temperature is risen to 85 ℃, continue to supplement vinylidene fluoride monomers to reacting kettle inner pressure and reach 4.5MPa.Add 0.5 gram of di-isopropyl peroxydicarbonate (IPP), start polyreaction.By adding vinylidene fluoride monomers, make reacting kettle inner pressure maintain 4.5MPa, with the speed of 0.1 gram/15 minutes, add IPP, when the vinylidene fluoride monomers of total amount 1000g adds in complete and still reaction pressure to be down to 3.0MPa, stop adding IPP when following; The positive butyl ester of polar monomer toxilic acid list becomes 1% aqueous solution to feed intake and ethyl acetate 0.5g by 12% proportional arrangement of vinylidene weight part, vinylidene fluoride monomers feed intake weight reach preset value 50%, 60%, 70%, 80% time average segmentation join polymeric kettle.Reaction finishes rear collection emulsion, filters, and breakdown of emulsion, washing, dry, obtain polyvinylidene difluoride (PVDF) copolymer resin powder.
By ISO4624 standard (adhesive power pull-off test), measure polymkeric substance preparation and become the cohesive strength after electrode.The preparation process of electrode is as described below: under room temperature state, under mechanical stirring, the resin of producing in 1g example 1 is dissolved in 50gNMP.Under the state stirring, add 2g graphitized carbon black and 30g cobalt acid lithium (LiCoO2), fully mix and guarantee homogeneity.Then mixture is degassed and spread on aluminium foil with scraper under vacuum, finally the aluminium foil of sprawling upper electrode material mixture is positioned over vacuum drying oven be warming up to 60 ℃ dry 12 hours, finally prepare electrode slice.Use puller system survey meter to measure the cohesive strength of electrode slice upper electrode material.Each value is at least got the mensuration mean value of 5 electrode slices, and data are summarised in table 1.
embodiment 2
In 5 liters of vertical polymerization reaction kettles, add 2500 grams of deionized waters, 5 grams of methylcellulose gum.Merge reactor, vacuumize and use nitrogen replacement, until oxygen level is less than 10ppm in reactor, add the vinylidene fluoride monomers of 1000g, 5g toxilic acid mono carboxylic ethyl ester 1% aqueous solution, 2g ethyl acetate.Then start to stir with the speed of 500rpm, reactor temperature is risen to 28 ℃, add 2.5 grams of di-isopropyl peroxydicarbonates (IPP), polyreaction is after 40 hours, and Pressure Drop, to 2.0MPa, stops polyreaction.Reaction finishes rear collection material, and washing is dry, obtains polyvinylidene difluoride (PVDF) copolymer resin powder.
The multipolymer that the limiting viscosity of using 1 gram is 2.0dl/g is prepared electrode slice.Cohesive strength is measured and is summarised in table 1.
embodiment 3
In 5 liters of vertical polymerization reaction kettles, add 2500 grams of deionized waters, 8 grams of methylcellulose gum.Merge reactor, vacuumize and use nitrogen replacement, until oxygen level is less than 10ppm in reactor, add the vinylidene fluoride monomers of 1500g, 5g toxilic acid mono carboxylic ethyl ester 1% aqueous solution, 5g ethyl acetate.Then start to stir with the speed of 500rpm, reactor temperature is risen to 40 ℃, add 3 grams of di-isopropyl peroxydicarbonates (IPP), polyreaction is after 12 hours, and Pressure Drop, to 3.0MPa, stops polyreaction.Reaction finishes rear collection material, and washing is dry, obtains polyvinylidene difluoride (PVDF) copolymer resin powder.
The multipolymer that the limiting viscosity of using 1 gram is 2.0dl/g is prepared electrode slice.Cohesive strength is measured and is summarised in table 1.
embodiment 4
In 5 liters of vertical polymerization reaction kettles, add 2500 grams of deionized waters, 8 grams of methylcellulose gum.Merge reactor, vacuumize and use nitrogen replacement, until oxygen level is less than 10ppm in reactor, add the vinylidene fluoride monomers of 1000g, 3g toxilic acid mono carboxylic ethyl ester 1% aqueous solution, 3g ethyl acetate.Then start to stir with the speed of 500rpm, reactor temperature is risen to 40 ℃, add 3 grams of di-isopropyl peroxydicarbonates (IPP), until Pressure Drop, during to 4.5MPa, supplement 250g vinylidene fluoride monomers, 1g toxilic acid mono carboxylic ethyl ester, 1g ethyl acetate, repeat twice, treat that Pressure Drop, to 3.0MPa, stops polyreaction.Reaction finishes rear collection material, and washing is dry, obtains polyvinylidene difluoride (PVDF) copolymer resin powder.
The multipolymer that the limiting viscosity of using 1 gram is 2.0dl/g is prepared electrode slice.Cohesive strength is measured and is summarised in table 1.
comparative example 1
In 5 liters of vertical polymerization reaction kettles, add 2500 grams of deionized waters, 5 grams of methylcellulose gum.Merge reactor, vacuumize and use nitrogen replacement, until oxygen level is less than 10ppm in reactor, add the vinylidene fluoride monomers of 1000g, 5g monomethyl maleate, 2g ethyl acetate.Then start to stir with the speed of 500rpm, reactor temperature is risen to 28 ℃, add 2.5 grams of di-isopropyl peroxydicarbonates (IPP), polyreaction is after 40 hours, and Pressure Drop, to 3.0MPa, stops polyreaction.Reaction finishes rear collection material, and washing is dry, obtains polyvinylidene difluoride (PVDF) copolymer resin powder.
The multipolymer that the limiting viscosity of using 1 gram is 2.0dl/g is prepared electrode slice.Cohesive strength is measured and is summarised in table 1.
comparative example 2
KUREHA 9200 vinylidene fluoride copolymers that the limiting viscosity of using 1 gram is 1.8dl/g are prepared electrode slice.Cohesive strength is measured and is summarised in table 1.
comparative example 3
SOLVAY 5130 vinylidene fluoride copolymers that the limiting viscosity of using 1 gram is 2.3dl/g are prepared electrode slice.Cohesive strength is measured and is summarised in table 1.
Table 1
| Embodiment | Limiting viscosity | Comonomer | Melting index (g, 230 ° of C, 5kg/10min) | Fusing point (° C) | Cohesive strength (N/m) | Thermal weight loss (400 ℃) | Solution appearance |
| Embodiment 1 | 1.5 | The positive butyl ester of toxilic acid list | 0.47 | 168 | 123 | <1% | Clear |
| Embodiment 2 | 2.0 | Toxilic acid mono carboxylic ethyl ester | 0.23 | 170 | 102 | <1% | Clear |
| Embodiment 3 | 1.8 | Toxilic acid mono carboxylic ethyl ester | 0.31 | 169 | 81 | <1% | Clear |
| Embodiment 4 | 1.8 | Toxilic acid mono carboxylic ethyl ester | 0.35 | 169 | 92 | <1% | Clear |
| Comparative example 1 | 2.0 | Monomethyl maleate | 0.31 | 171 | 34 | <1% | Clear |
| Comparative example 2 | 1.8 | 0.56 | 171 | 23 | <1% | Clear | |
| Comparative example 3 | 3.0 | 0.12 | 166 | 56 | <1% | Clear |
The known vinylidene fluoride copolymers adhesive property provided by the invention of result by above-mentioned table 1 has significantly improvement.
Claims (13)
1. a vinylidene fluoride copolymers, it is characterized in that described vinylidene fluoride copolymers contains vinylidene fluoride monomers and at least one modification toxilic acid esters monomer, modification toxilic acid esters monomer accounts for the quality proportioning of total comonomer for being greater than 0～20%, and described modification toxilic acid esters monomer has following structural formula (I):
Wherein:
R
1be selected from C
3-C
8alkyl, the C that contains optional at least one heteroatoms replacement in O, S, N, Cl and Br
1-C
8alkyl;
R
2, R
3independently selected from hydrogen atom, C
1-C
8alkyl, the C that contains optional at least one heteroatoms replacement in O, S, N, Cl and Br
1-C
8alkyl.
2. according to vinylidene fluoride copolymers claimed in claim 1, it is characterized in that the quality proportioning that described modification toxilic acid esters monomer accounts for total comonomer is 0.1～10%, described R
1for C
3-C
8alkyl or the C that contains optional at least one heteroatoms replacement in O, S, Cl and Br
1-C
8alkyl, described R
2and R
3for hydrogen atom.
3. according to vinylidene fluoride copolymers claimed in claim 2, it is characterized in that the quality proportioning that described modification toxilic acid esters monomer accounts for total comonomer is 1～5%, described R
1for contain that optional at least one heteroatoms in O and Cl replaces C
1-C
4alkyl.
4. according to vinylidene fluoride copolymers claimed in claim 1, it is characterized in that described vinylidene fluoride copolymers contains the 3rd comonomer, described the 3rd comonomer be selected from vinyl fluoride, trifluoro-ethylene, tetrafluoroethylene, trifluorochloroethylene, tetrafluoroethylene, tetrafluoeopropene, five fluorine propylene, R 1216, perfluoro methyl vinyl ether, perfluoro propyl vinyl ether and other can with the Fluorine containing olefine of vinylidene copolymerization in a kind of, more than two or three combination, the quality proportioning that described the 3rd comonomer accounts for total comonomer is 0.1～50%.
5. according to vinylidene fluoride copolymers claimed in claim 1, the weight-average molecular weight that it is characterized in that described vinylidene fluoride copolymers is 30～1,200,000 grams/mol, molecular weight distribution coefficient is 1.6～5, molecular weight distribution curve is unimodal distribution, melt flow rate (MFR) is 0.02～10 gram/10 minutes, and limiting viscosity is 0.5-4.0 * 10
2dl/g, fusing point is greater than 150 ℃, is being greater than the weightlessness that stands to be less than 1%wt at the temperature of 400 ℃.
6. according to the vinylidene fluoride copolymers one of claim 1 to 5 Suo Shu, it is characterized in that the cohesive strength of described vinylidene fluoride copolymers is greater than 50N/m, as lithium ion battery binding agent.
7. according to a preparation method for vinylidene co-polymer claimed in claim 1, it is characterized in that adopting letex polymerization, comprise the following steps:
(1) to reactor, provide dispersion and the vinylidene fluoride monomers of at least one modification toxilic acid esters monomer claimed in claim 1 of part in water;
(2) to reactor, add emulsifying agent, chain-transfer agent and initiator, initiated polymerization under 70 ℃～120 ℃ temperature and 2.0～12.0MPa pressure;
(3) mode that adopts segmentation to feed intake adds dispersion and the vinylidene fluoride monomers of remaining at least one modification toxilic acid esters monomer claimed in claim 1 in water, and maintenance polymerization pressure is 3.0～12.0MPa, and adds initiator;
(4), when polymerization pressure drops to 2.0～11.0MPa, stop adding initiator, until reaction finishes;
In reaction process, the quality proportioning that the modification toxilic acid esters monomer total amount that control adds accounts for whole monomers is 0.1～20%.
8. according to the preparation method of vinylidene co-polymer claimed in claim 7, it is characterized in that described emulsifying agent is PFPE carboxylate salt, there is following structural formula (II):
CF
3CF
2CF
2O(CF(CF
3)CF
2O)
n-2CF(CF
3)COOM （II）
Wherein: the integer of n=2～6 ,-COOM is an alkali metal salt, ammonium salt or rudimentary alkylamine salt.
9. according to a preparation method for vinylidene fluoride copolymers claimed in claim 1, it is characterized in that adopting suspension polymerization, comprise the following steps:
(1) to reactor, provide dispersion and the vinylidene fluoride monomers of at least one modification toxilic acid esters monomer claimed in claim 1 of part in water;
(2) add dispersion agent, chain-transfer agent and initiator, initiated polymerization under the condition of 20 ℃～60 ℃ temperature and 3.0～12.0MPa pressure;
(3) mode that adopts segmentation to feed intake adds dispersion and the vinylidene fluoride monomers of remaining at least one modification toxilic acid esters monomer claimed in claim 1 in water, and maintenance polymerization pressure is 3.0～12.0Mpa;
(4), when polymerization pressure drops to 2.0～11.0MPa, reaction finishes;
In reaction process, the quality proportioning that the modification toxilic acid esters monomer total amount that control adds accounts for total comonomer is 0.1～20%.
10. according to the preparation method of the vinylidene co-polymer described in claim 7 or 9, it is characterized in that the vinylidene fluoride monomers amount adding in described step (1) accounts for 1～25% of total vinylidene fluoride monomers add-on.
11. 1 kinds of compositions that form electrode, is characterized in that comprising according to the vinylidene fluoride copolymers described in claim 6, powder electrode material and give the additive of electrical conductivity.
12. according to the composition of the formation electrode described in claim 11, it is characterized in that in described composition, each composition forms by following quality proportioning:
(1) vinylidene fluoride copolymers 1%～10%;
(2) as the carbon black that gives the additive of electrical conductivity, 2%～10%;
(3) powder electrode material 80%～97%, for by general formula LiMY
2the complex metal compound of representative, wherein M is selected from a kind of, more than two or three combination in Co, Ni, Fe, Mn, Cr and V, and Y is O or S.
13. according to the composition of the formation electrode described in claim 11, it is characterized in that the electrode as lithium cell or electrical condenser.
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