CN103387642A - Preparation method of high energy storage density and polyvinylidene fluoride group grafted modified polymer - Google Patents
Preparation method of high energy storage density and polyvinylidene fluoride group grafted modified polymer Download PDFInfo
- Publication number
- CN103387642A CN103387642A CN2013102944446A CN201310294444A CN103387642A CN 103387642 A CN103387642 A CN 103387642A CN 2013102944446 A CN2013102944446 A CN 2013102944446A CN 201310294444 A CN201310294444 A CN 201310294444A CN 103387642 A CN103387642 A CN 103387642A
- Authority
- CN
- China
- Prior art keywords
- polymkeric substance
- solvent
- catalyzer
- vdf
- ctfe
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 44
- 238000004146 energy storage Methods 0.000 title claims abstract description 23
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 21
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title abstract 2
- 239000002904 solvent Substances 0.000 claims abstract description 52
- 239000000178 monomer Substances 0.000 claims abstract description 27
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims abstract description 18
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 18
- 229940045803 cuprous chloride Drugs 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims description 92
- 238000006243 chemical reaction Methods 0.000 claims description 56
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 34
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 238000007865 diluting Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 230000002829 reductive effect Effects 0.000 claims description 19
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 17
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- 239000005357 flat glass Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 12
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- 238000006392 deoxygenation reaction Methods 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000010791 quenching Methods 0.000 claims description 8
- 230000003252 repetitive effect Effects 0.000 claims description 8
- 238000005201 scrubbing Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 230000004087 circulation Effects 0.000 claims description 6
- 229920002313 fluoropolymer Polymers 0.000 claims description 5
- 239000004811 fluoropolymer Substances 0.000 claims description 5
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 4
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 4
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 3
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- QATBRNFTOCXULG-UHFFFAOYSA-N n'-[2-(methylamino)ethyl]ethane-1,2-diamine Chemical compound CNCCNCCN QATBRNFTOCXULG-UHFFFAOYSA-N 0.000 claims description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 229920000131 polyvinylidene Polymers 0.000 abstract 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 6
- 239000004926 polymethyl methacrylate Substances 0.000 description 6
- 230000005311 nuclear magnetism Effects 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 230000005684 electric field Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
Images
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
A preparation method of high energy storage density and polyvinylidene fluoride group grafted modified polymer comprises following steps: adopting N-methyl 2 pyrrolidone as the solvent, taking cuprous chloride, 2,2-dipyridine and copper as the catalytic system, poly(vinylidene fluoride-trifluoroethylene-trifluorochloroethene) P(VDF-TrFE-CTFE) as the raw material, and polymethacrylate as the graft monomer to synthesize poly(vinylidene fluoride-trifluoroethylene-trifluorochloroethene) P(VDF-TrFE-CTFE) grafted polymethacrylate copolymer. The preparation method has the advantages of simple and controllable operation, low using amount of catalyst and easy purification of polymer.
Description
Technical field
The present invention relates to the modification of graft novel method of the basic fluoropolymer of a kind of polyvinylidene difluoride (PVDF) (PVDF), particularly the preparation method of high energy storage density polyvinylidene fluoride graft modification polymkeric substance.
Background technology
Polyvinylidene difluoride (PVDF) (PVDF) and binary/terpolymer thereof (P (VDF-TrFE) or P (VDF-CTFE) or (PVDF-TrFE-CTFE)) are posted great expectations and are used for the high energy storage capacitor dielectric materials of a new generation because having very high specific inductivity.Compare present commercial biaxial stretch-formed polypropylene (BOPP) polymeric film, the polyvinylidene fluoride fluoropolymer has very high electric field polarization value and quite high anti-breakdown electric field as a kind of polar polymer.But its typical ferroelectrics feature, make to have higher residual polarization value and then most stored charge can't effectively discharge.For this reason, the investigator introduces textural defect by the method for electron irradiation or copolymerization the 3rd monomer in P (VDF-TrFE), destroy its large size crystal grain, makes it change Relaxation Ferroelectrics into, promotes the stored energy release efficiency.At present, the energy density of P (VDF-CTFE) polymkeric substance can reach 25J/cm
3(650MV/m), but its energy waste still higher (approximately 40-60%).For this reason, how when keeping high-energy-density, effectively reduce its energy waste and be Research Challenges instantly.Recently, studies have reported that the method that adopts P (VDF-TrFE-CTFE) or P (VDF-CTFE) grafted polystyrene (PS) has significantly reduced the energy waste of polymkeric substance, but meanwhile the energy storage density of polymkeric substance is also significantly reducing, also the imperfect dielectric substance that meets high energy storage demand.
Summary of the invention
In order to overcome the defect of prior art, realize PVDF base fluoropolymer high energy storage density, low-yield drain performance, the object of the present invention is to provide a kind of preparation method of high energy storage density polyvinylidene fluoride graft modification polymkeric substance, by poly-(vinylidene-trifluoro-ethylene-trifluorochloroethylene) graft copolymerization methacrylic ester (comprising polymethylmethacrylate (PMMA), polyethyl methacrylate (PEMA) and poly-n-butyl methacrylate (PBMA)), when keeping polymkeric substance to have high energy storage density, significantly reduce energy waste.
In order to achieve the above object, technical scheme of the present invention is achieved in that
The preparation method of high energy storage density polyvinylidene fluoride graft modification polymkeric substance comprises the following steps:
Step 1, add polymkeric substance in there-necked flask, add simultaneously catalyzer, part and reductive agent, after mixing circulates for three times by vacuum nitrogen filling gas, the solvent that adds deoxygenation with syringe, the mass ratio of solvent and polymkeric substance is 15:1～30:1, fully stirs, after polymkeric substance dissolves fully, reaction flask is moved in oil bath, be warming up to 100 ° of C; Add grafted monomer with syringe, the mass ratio of grafted monomer and polymkeric substance is 1:1～5:1, and polyreaction stops after 15 minutes-24 hours.
Described polymkeric substance is poly-(vinylidene-trifluoro-ethylene-trifluorochloroethylene) P (VDF-TrFE-CTFE) polymkeric substance of different components mol ratio;
Described catalyzer is cuprous chloride (CuCl) or cuprous bromide (CuBr); Catalyzer is 0.5:1～2:1 with the mol ratio of the middle Cl atom of poly-(vinylidene-trifluoro-ethylene-trifluorochloroethylene) P (VDF-TrFE-CTFE);
Described part is 2,2-dipyridyl (BPy) or N, N, and N', N, ' N''-five methyl diethylentriamine (PMDETA) or three [(2-pyridyl) methyl] amine (TPMA) or hexamethyl triethyl triamine (Me
6TREN); The mol ratio of part and catalyzer is 1:1～2:1;
Described reductive agent is copper powder simple substance (Cu); The mol ratio of reductive agent and catalyzer is 0.5:1～2:1;
Described solvent is the good solvent of fluoropolymer, comprises DMF (DMF), N-Methyl pyrrolidone (NMP) or dimethyl sulfoxide (DMSO) (DMSO);
Described temperature of reaction is 100 ° of C;
Described grafted monomer comprises methyl methacrylate (MMA), β-dimethyl-aminoethylmethacrylate (EMA) or butyl methacrylate (BMA).
Obtain diluting reaction solution add acetone diluted in step 2, the reaction soln that obtains finally in step 1 after, acetone and reaction soln volume ratio are 1:5; Diluting reaction solution is poured in mixing solutions, and mixing solutions is that acidity is water and the methyl alcohol of pH=3 volume ratio 3:1, and the volume ratio of mixing solutions and diluting reaction solution is not less than 5:1, stirs 1 hour, filters and separates out polymkeric substance; Resulting polymers water and methyl alcohol volume ratio are that the mixing solutions repetitive scrubbing of 3:1 repeatedly is white in color to product; Resulting polymers Soxhlet extracting 24 hours in chloroform solvent; Vacuum-drying to constant weight obtains target product under not higher than 60 ° of C conditions.
During the energy-storage property of test polymer film, spraying area on the two sides of polymeric film with ion sputtering instrument is 0.069cm
2, thickness is about the metal electrode of 80nm.Ferroelectric hysteresis loop adopts the ferroelectric test macro of the Radiant Technologies Premiere II of company, and test frequency is 10Hz.Energy storage density is obtained by unidirectional electrical hysteresis curves integral and calculating, and formula is U
e=∫ EdD, U
eFor energy storage density, E is strength of electric field, and D is the electricdisplacement value.
The present invention adopts N-Methyl pyrrolidone etc. to be solvent, with cuprous chloride, 2,2-dipyridyl, copper etc. are catalyst system, take poly-(vinylidene-trifluoro-ethylene-trifluorochloroethylene) P (VDF-TrFE-CTFE) as raw material, take polymethacrylate as grafted monomer, synthetic poly-(vinylidene-trifluoro-ethylene-trifluorochloroethylene) P (VDF-CTFE-TrFE) grafting polymethacrylate copolymer, has method easy control simple to operate, catalyzer uses content low, is easy to the advantage of polymer purification.
Description of drawings
Fig. 1 is graft copolymer
1H NMR curve.
Fig. 2 be graft copolymer two-way ferroelectric hysteresis loop curve.
Fig. 3 be graft copolymer unidirectional electrical hysteresis curves curve.
Fig. 4 be graft copolymer the energy storage density curve.
Embodiment
Embodiment one
The preparation method of high energy storage density polyvinylidene fluoride graft modification polymkeric substance comprises the following steps:
Step 1, add polymer raw material in there-necked flask, add simultaneously catalyzer, part and reductive agent, this mixture after three circulations of vacuum nitrogen filling gas, adds the solvent of deoxygenation with syringe, and the mass ratio of solvent and polymkeric substance is 25:1; Fully stir, after polymkeric substance dissolves fully, reaction flask is moved in oil bath, be warming up to 100 ° of C of desired reaction temperature.Add monomer with syringe, the mass ratio of monomer and polymkeric substance is 1.5:1, and polyreaction stopped after 2 hours.
Described polymer raw material is poly-(vinylidene-trifluoro-ethylene-trifluorochloroethylene) P (VDF-TrFE-CTFE), mol ratio VDF/TrFE/CTFE=80/15/5.
Described catalyzer is cuprous chloride (CuCl).
In described catalyzer agent and P (VDF-TrFE-CTFE), the Cl atomic molar is than being 1:1.
Described part is 2,2-dipyridyl (BPy).
The mol ratio of described part and catalyzer is 2:1.
Described reductive agent is copper powder simple substance (Cu).
The described former dose of mol ratio with catalyzer is 1:1.
Described solvent is N-Methyl pyrrolidone (NMP).
Described monomer is methyl methacrylate (MMA).
Obtain diluting reaction solution add acetone diluted in step 2, the reaction soln that obtains finally in step 1 after, acetone and reaction soln volume ratio are 1:5; Diluting reaction solution is poured in mixing solutions, and mixing solutions is that acidity is water and the methyl alcohol of pH=3 volume ratio 3:1, and the volume ratio of mixing solutions and diluting reaction solution is not less than 5:1, stirs 1 hour, filters and separates out polymkeric substance; Resulting polymers water and methyl alcohol volume ratio are that the mixing solutions repetitive scrubbing of 3:1 repeatedly is white in color to product.Resulting polymers Soxhlet extracting 24 hours in chloroform solvent.Vacuum-drying to constant weight obtains target product under not higher than 60 ° of C conditions.
What nuclear-magnetism recorded polymkeric substance mole consists of VDF/TrFE/CTFE/MMA=80/15/5/25, and amounting to the PMMA mass percent is 27%.In Fig. 1, the A curve is P (VDF-TrFE-CTFE)-g-PMMA polymkeric substance
1H NMR nuclear magnetic spectrogram.
Embodiment two
The preparation method of high energy storage density polyvinylidene fluoride graft modification polymkeric substance comprises the following steps:
Step 1, add polymer raw material in there-necked flask, add simultaneously catalyzer, part and reductive agent, this mixture after three circulations of vacuum nitrogen filling gas, adds the solvent of deoxygenation with syringe, and the mass ratio of solvent and polymkeric substance is 25:1; Fully stir, after polymkeric substance dissolves fully, reaction flask is moved in oil bath, be warming up to 100 ° of C of desired reaction temperature; Add monomer with syringe, the mass ratio of monomer and polymkeric substance is 1.5:1, and polyreaction stopped after 2 hours.
Described polymer raw material is poly-(vinylidene-trifluoro-ethylene-trifluorochloroethylene) P (VDF-TrFE-CTFE), mol ratio VDF/TrFE/CTFE=80/15/5.
Described catalyzer is cuprous chloride (CuCl).
In described catalyzer agent and P (VDF-TrFE-CTFE), the Cl atomic molar is than being 1:1.
Described part is 2,2-dipyridyl (BPy).
The mol ratio of described part and catalyzer is 2:1.
Described reductive agent is copper powder simple substance (Cu).
The described former dose of mol ratio with catalyzer is 1:1.
Described solvent is N-Methyl pyrrolidone (NMP).
Described monomer is β-dimethyl-aminoethylmethacrylate (EMA).
Obtain diluting reaction solution add acetone diluted in step 2, the reaction soln that obtains finally in step 1 after, acetone and reaction soln volume ratio are 1:5; Diluting reaction solution is poured in mixing solutions, and mixing solutions is that acidity is water and the methyl alcohol of pH=3 volume ratio 3:1, and the volume ratio of mixing solutions and diluting reaction solution is not less than 5:1, stirs 1 hour, filters and separates out polymkeric substance; Resulting polymers water and methyl alcohol volume ratio are that the mixing solutions repetitive scrubbing of 3:1 repeatedly is white in color to product.Resulting polymers Soxhlet extracting 24 hours in chloroform solvent.Vacuum-drying to constant weight obtains target product under not higher than 60 ° of C conditions.
What nuclear-magnetism recorded polymkeric substance mole consists of VDF/TrFE/CTFE/EMA=80/15/5/25, and amounting to the PEMA mass percent is 30%.In Fig. 1, the B curve is P (VDF-TrFE-CTFE)-g-PEMA polymkeric substance
1H NMR nuclear magnetic spectrogram.
Fig. 2 is the two-way ferroelectric hysteresis loop of resulting polymers; Fig. 3 is the unidirectional electrical hysteresis curves of resulting polymers; The energy storage density curve of Fig. 4 for by Fig. 3 curvilinear integral, being calculated.
Embodiment three
The preparation method of high energy storage density polyvinylidene fluoride graft modification polymkeric substance comprises the following steps:
Step 1, add polymer raw material in there-necked flask, add simultaneously catalyzer, part and reductive agent, this mixture after three circulations of vacuum nitrogen filling gas, adds the solvent of deoxygenation with syringe, and the mass ratio of solvent and polymkeric substance is 25:1; Fully stir, after polymkeric substance dissolves fully, reaction flask is moved in oil bath, be warming up to 100 ° of C of desired reaction temperature.Add monomer with syringe, the mass ratio of monomer and polymkeric substance is 1.5:1, and polyreaction stops after the regular hour.
Described polymer raw material is poly-(vinylidene-trifluoro-ethylene-trifluorochloroethylene) P (VDF-TrFE-CTFE), mol ratio VDF/TrFE/CTFE=80/15/5.
Described catalyzer is cuprous chloride (CuCl).
In described catalyzer agent and P (VDF-TrFE-CTFE), the Cl atomic molar is than being 1:1.
Described part is 2,2-dipyridyl (BPy).
The mol ratio of described part and catalyzer is 2:1.
Described reductive agent is copper powder simple substance (Cu).
The described former dose of mol ratio with catalyzer is 1:1.
Described solvent is N-Methyl pyrrolidone (NMP).
Described monomer is butyl methacrylate (BMA).
The described reaction times is 2 hours.
Obtain diluting reaction solution add acetone diluted in step 2, the reaction soln that obtains finally in step 1 after, acetone and reaction soln volume ratio are 1:5; Diluting reaction solution is poured in mixing solutions, and mixing solutions is that acidity is water and the methyl alcohol of pH=3 volume ratio 3:1, and the volume ratio of mixing solutions and diluting reaction solution is not less than 5:1, stirs 1 hour, filters and separates out polymkeric substance; Resulting polymers water and methyl alcohol volume ratio are that the mixing solutions repetitive scrubbing of 3:1 repeatedly is white in color to product.Resulting polymers Soxhlet extracting 24 hours in chloroform solvent.Vacuum-drying to constant weight obtains target product under not higher than 60 ° of C conditions.
What nuclear-magnetism recorded polymkeric substance mole consists of VDF/TrFE/CTFE/BMA=80/15/5/25, and amounting to the PBMA mass percent is 37%.In Fig. 1, C curve is P (VDF-TrFE-CTFE)-g-PBMA polymkeric substance
1H NMR nuclear magnetic spectrogram.
Embodiment four
The preparation method of high energy storage density polyvinylidene fluoride graft modification polymkeric substance comprises the following steps:
Step 1, add polymer raw material in there-necked flask, add simultaneously catalyzer, part and reductive agent, this mixture after three circulations of vacuum nitrogen filling gas, adds the solvent of deoxygenation with syringe, and the mass ratio of solvent and polymkeric substance is 25:1; Fully stir, after polymkeric substance dissolves fully, reaction flask is moved in oil bath, be warming up to 100 ° of C of desired reaction temperature.Add monomer with syringe, the mass ratio of monomer and polymkeric substance is 1.5:1, and polyreaction stops after the regular hour.
Described polymer raw material is poly-(vinylidene-trifluoro-ethylene-trifluorochloroethylene) P (VDF-TrFE-CTFE), mol ratio VDF/TrFE/CTFE=80/15/5.
Described catalyzer is cuprous chloride (CuCl).
In described catalyzer agent and P (VDF-TrFE-CTFE), the Cl atomic molar is than being 1:1.
Described part is 2,2-dipyridyl (BPy).
The mol ratio of described part and catalyzer is 2:1.
Described reductive agent is copper powder simple substance (Cu).
The described former dose of mol ratio with catalyzer is 1:1.
Described solvent is N-Methyl pyrrolidone (NMP).
Described monomer is methyl methacrylate (MMA).
The described reaction times is 15 minutes.
Obtain diluting reaction solution add acetone diluted in step 2, the reaction soln that obtains finally in step 1 after, acetone and reaction soln volume ratio are 1:5; Diluting reaction solution is poured in mixing solutions, and mixing solutions is that acidity is water and the methyl alcohol of pH=3 volume ratio 3:1, and the volume ratio of mixing solutions and diluting reaction solution is not less than 5:1, stirs 1 hour, filters and separates out polymkeric substance; Resulting polymers water and methyl alcohol volume ratio are that the mixing solutions repetitive scrubbing of 3:1 repeatedly is white in color to product.Resulting polymers Soxhlet extracting 24 hours in chloroform solvent.Vacuum-drying to constant weight obtains target product under not higher than 60 ° of C conditions.
What nuclear-magnetism recorded polymkeric substance mole consists of VDF/TrFE/CTFE/MMA=80/15/5/7, and amounting to the PMMA mass percent is 9%.
Embodiment five
The preparation method of high energy storage density polyvinylidene fluoride graft modification polymkeric substance comprises the following steps:
Step 1, add polymer raw material in there-necked flask, add simultaneously catalyzer, part and reductive agent, this mixture after three circulations of vacuum nitrogen filling gas, adds the solvent of deoxygenation with syringe, and the mass ratio of solvent and polymkeric substance is 25:1; Fully stir, after polymkeric substance dissolves fully, reaction flask is moved in oil bath, be warming up to 100 ° of C of desired reaction temperature.Add monomer with syringe, the mass ratio of monomer and polymkeric substance is 1.5:1, and polyreaction stops after the regular hour.
Described polymer raw material is poly-(vinylidene-trifluoro-ethylene-trifluorochloroethylene) P (VDF-TrFE-CTFE), mol ratio VDF/TrFE/CTFE=80/12/8.
Described catalyzer is cuprous chloride (CuCl).
In described catalyzer agent and P (VDF-TrFE-CTFE), the Cl atomic molar is than being 1:1.
Described part is 2,2-dipyridyl (BPy).
The mol ratio of described part and catalyzer is 2:1.
Described reductive agent is copper powder simple substance (Cu).
The described former dose of mol ratio with catalyzer is 0.5:1.
Described solvent is N-Methyl pyrrolidone (NMP).
Described monomer is methyl methacrylate (MMA).
The described reaction times is 2 hours.
Obtain diluting reaction solution add acetone diluted in step 2, the reaction soln that obtains finally in step 1 after, acetone and reaction soln volume ratio are 1:5; Diluting reaction solution is poured in mixing solutions, and mixing solutions is that acidity is water and the methyl alcohol of pH=3 volume ratio 3:1, and the volume ratio of mixing solutions and diluting reaction solution is not less than 5:1, stirs 1 hour, filters and separates out polymkeric substance; Resulting polymers water and methyl alcohol volume ratio are that the mixing solutions repetitive scrubbing of 3:1 repeatedly is white in color to product.Resulting polymers Soxhlet extracting 24 hours in chloroform solvent.Vacuum-drying to constant weight obtains target product under not higher than 60 ° of C conditions.
What nuclear-magnetism recorded polymkeric substance mole consists of VDF/TrFE/CTFE/MMA=80/12/8/25, and amounting to the PMMA mass percent is 30%.
Other non-limiting examples is as shown in the table:
Claims (2)
1. the preparation method of high energy storage density polyvinylidene fluoride graft modification polymkeric substance, is characterized in that, comprises the following steps:
Step 1, add polymer raw material in there-necked flask, add simultaneously catalyzer, part and reductive agent, after mixing circulates for three times by vacuum nitrogen filling gas, the solvent that adds deoxygenation with syringe, the mass ratio of solvent and polymkeric substance is 15:1～30:1, fully stirs, after polymkeric substance dissolves fully, reaction flask is moved in oil bath, be warming up to 100 ° of C; Add grafted monomer with syringe, the mass ratio of grafted monomer and polymkeric substance is 1:1～5:1, and polyreaction stops after 15 minutes-24 hours;
Described polymer raw material is poly-(vinylidene-trifluoro-ethylene-trifluorochloroethylene) P (VDF-TrFE-CTFE) polymkeric substance of different components mol ratio;
Described catalyzer is cuprous chloride CuCl or cuprous bromide CuBr; Catalyzer is 0.5:1～2:1 with the mol ratio of the middle Cl atom of poly-(vinylidene-trifluoro-ethylene-trifluorochloroethylene) P (VDF-TrFE-CTFE);
Described part is 2,2-dipyridyl (BPy) or N, N, and N', N, ' N''-five methyl diethylentriamine (PMDETA) or three [(2-pyridyl) methyl] amine (TPMA) or hexamethyl triethyl triamine (Me
6TREN); The mol ratio of part and catalyzer is 1:1～2:1;
Described reductive agent is copper powder simple substance Cu; The mol ratio of reductive agent and catalyzer is 0.5:1～2:1;
Described solvent is the good solvent of fluoropolymer, comprises DMF DMF, N-Methyl pyrrolidone NMP or dimethyl sulfoxide (DMSO) DMSO;
Described temperature of reaction is 100 ° of C;
Described grafted monomer comprises methyl methacrylate (MMA), β-dimethyl-aminoethylmethacrylate (EMA) or butyl methacrylate (BMA);
Obtain diluting reaction solution add acetone diluted in step 2, the reaction soln that obtains finally in step 1 after, acetone and reaction soln volume ratio are 1:5; Diluting reaction solution is poured in mixing solutions, and mixing solutions is that acidity is water and the methyl alcohol of pH=3 volume ratio 3:1, and the volume ratio of mixing solutions and diluting reaction solution is not less than 5:1, stirs 1 hour, filters and separates out polymkeric substance; Resulting polymers water and methyl alcohol volume ratio are that the mixing solutions repetitive scrubbing of 3:1 repeatedly is white in color to product; Resulting polymers Soxhlet extracting 24 hours in chloroform solvent.Vacuum-drying to constant weight obtains target product under not higher than 60 ° of C conditions;
Step 3, the polymkeric substance N that step 2 is obtained, dinethylformamide DMF dissolves, polymkeric substance and solvent N, the mass ratio of dinethylformamide DMF is 3:100-6:100, after polymkeric substance fully dissolves, polymers soln is coated on clean sheet glass, and place it on the hot-plate of 50-100 ° of C, after solvent evaporates is complete, to insert constant temperature 4-24 hour in the baking oven of 150-200 ° of C with the sheet glass of polymeric film, then immerse at once in 0 ° of C mixture of ice and water, obtain the polymeric film of quench treatment.
2. the preparation method of 1 high energy storage density polyvinylidene fluoride graft modification polymkeric substance according to claim 1, is characterized in that, comprises the following steps:
Step 1, add polymer raw material in there-necked flask, add simultaneously catalyzer, part and reductive agent, this mixture after three circulations of vacuum nitrogen filling gas, adds the solvent of deoxygenation with syringe, and the mass ratio of solvent and polymkeric substance is 25:1; Fully stir, after polymkeric substance dissolves fully, reaction flask is moved in oil bath, be warming up to 100 ° of C of desired reaction temperature.Add monomer with syringe, the mass ratio of monomer and polymkeric substance is 1.5:1, and polyreaction stopped after 2 hours;
Described polymer raw material is poly-(vinylidene-trifluoro-ethylene-trifluorochloroethylene) P (VDF-TrFE-CTFE), mol ratio VDF/TrFE/CTFE=80/15/5;
Described catalyzer is cuprous chloride (CuCl);
In described catalyzer agent and P (VDF-TrFE-CTFE), the Cl atomic molar is than being 1:1;
Described part is 2,2-dipyridyl (BPy);
The mol ratio of described part and catalyzer is 2:1;
Described reductive agent is copper powder simple substance (Cu);
The described former dose of mol ratio with catalyzer is 1:1;
Described solvent is N-Methyl pyrrolidone (NMP);
Described monomer is β-dimethyl-aminoethylmethacrylate (EMA);
Obtain diluting reaction solution add acetone diluted in step 2, the reaction soln that obtains finally in step 1 after, acetone and reaction soln volume ratio are 1:5; Diluting reaction solution is poured in mixing solutions, and mixing solutions is that acidity is water and the methyl alcohol of pH=3 volume ratio 3:1, and the volume ratio of mixing solutions and diluting reaction solution is not less than 5:1, stirs 1 hour, filters and separates out polymkeric substance; Resulting polymers water and methyl alcohol volume ratio are that the mixing solutions repetitive scrubbing of 3:1 repeatedly is white in color to product; Resulting polymers Soxhlet extracting 24 hours in chloroform solvent; Vacuum-drying to constant weight obtains target product under not higher than 60 ° of C conditions;
Step 3, the polymkeric substance N that step 2 is obtained, dinethylformamide (DMF) dissolves, polymkeric substance and solvent N, the mass ratio of dinethylformamide (DMF) is 3:100-6:100, after polymkeric substance fully dissolves, polymers soln is coated on clean sheet glass, and place it on the hot-plate of 50-100 ° of C, after solvent evaporates is complete, to insert constant temperature 4-24 hour in the baking oven of 150-200 ° of C with the sheet glass of polymeric film, then immerse at once in 0 ° of C mixture of ice and water, obtain the polymeric film of quench treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310294444.6A CN103387642B (en) | 2013-07-12 | 2013-07-12 | The preparation method of high energy storage density polyvinylidene fluoride graft modification polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310294444.6A CN103387642B (en) | 2013-07-12 | 2013-07-12 | The preparation method of high energy storage density polyvinylidene fluoride graft modification polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103387642A true CN103387642A (en) | 2013-11-13 |
| CN103387642B CN103387642B (en) | 2016-05-04 |
Family
ID=49532073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310294444.6A Active CN103387642B (en) | 2013-07-12 | 2013-07-12 | The preparation method of high energy storage density polyvinylidene fluoride graft modification polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103387642B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004218A (en) * | 2014-03-10 | 2014-08-27 | 江苏大学 | Artemisinin molecular imprinting film, preparation method and applications thereof |
| CN105153371A (en) * | 2015-07-24 | 2015-12-16 | 北京科技大学 | Manufacturing method for cationic polyelectrolyte and application of cationic polyelectrolyte in super capacitor |
| CN106206839A (en) * | 2016-06-30 | 2016-12-07 | 华侨大学 | A kind of solvent heat treatment method preparing perovskite solaode |
| CN106893039A (en) * | 2017-03-28 | 2017-06-27 | 南京工业大学 | A kind of method of photoinduction organic catalysis polymer modification |
| CN108395503A (en) * | 2018-03-14 | 2018-08-14 | 成都宏明电子股份有限公司 | It is a kind of antiferroelectric poly-（Vinylidene-trifluoro-ethylene-chlorotrifluoroethylene）The preparation method of graft polymers |
| CN110256642A (en) * | 2019-03-13 | 2019-09-20 | 南京航空航天大学 | A kind of ferroelectric polymers and preparation method thereof with allochromy |
| CN113906065A (en) * | 2019-08-08 | 2022-01-07 | 株式会社Lg新能源 | Copolymer for polymer electrolyte, and gel polymer electrolyte and lithium secondary battery comprising the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020146567A1 (en) * | 1998-11-18 | 2002-10-10 | The Penn State Research Foundation | Terpolymer systems for electromechanical and dielectric applications |
| CN1616564A (en) * | 2003-08-01 | 2005-05-18 | 阿托菲纳公司 | PVDF-based PTC paints and their applications for self-regulated heating systems |
| CN101691412A (en) * | 2009-09-30 | 2010-04-07 | 西安交通大学 | Method for preparing poly(VDF-CTFE-TrFE) or poly(VDF-TrFE) by using poly(VDF-CTFE) |
| CN101955619A (en) * | 2009-07-15 | 2011-01-26 | 北京化工大学 | All-organic nanometer composite film with high energy storage density and preparation method thereof |
| CN102603986A (en) * | 2012-02-24 | 2012-07-25 | 常州大学 | Surface solid phase graft modified PVDF (Polyvinylidene Fluoride) and preparation method thereof |
-
2013
- 2013-07-12 CN CN201310294444.6A patent/CN103387642B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020146567A1 (en) * | 1998-11-18 | 2002-10-10 | The Penn State Research Foundation | Terpolymer systems for electromechanical and dielectric applications |
| CN1616564A (en) * | 2003-08-01 | 2005-05-18 | 阿托菲纳公司 | PVDF-based PTC paints and their applications for self-regulated heating systems |
| CN101955619A (en) * | 2009-07-15 | 2011-01-26 | 北京化工大学 | All-organic nanometer composite film with high energy storage density and preparation method thereof |
| CN101691412A (en) * | 2009-09-30 | 2010-04-07 | 西安交通大学 | Method for preparing poly(VDF-CTFE-TrFE) or poly(VDF-TrFE) by using poly(VDF-CTFE) |
| CN102603986A (en) * | 2012-02-24 | 2012-07-25 | 常州大学 | Surface solid phase graft modified PVDF (Polyvinylidene Fluoride) and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JUNJIE LI等: "High-field antiferroelectric behaviour and minimized energy loss in poly(vinylidene-co-trifluoroethylene)-graft- poly(ethyl methacrylate) for energy storage application", 《JOURNAL OF MATERIALS CHEMISTRY》, no. 22, 22 September 2012 (2012-09-22), pages 23468 - 23476 * |
| JUNJIE LI等: "Tuning phase transition and ferroelectric properties of poly(vinylidene fluoride-co- trifluoroethylene) via grafting with desired poly(methacrylic ester)s as side chains", 《JOURNAL OF MATERIALS CHEMISTRY C》, no. 1, 29 November 2012 (2012-11-29), pages 1111 - 1121 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004218A (en) * | 2014-03-10 | 2014-08-27 | 江苏大学 | Artemisinin molecular imprinting film, preparation method and applications thereof |
| CN104004218B (en) * | 2014-03-10 | 2016-08-31 | 江苏大学 | A kind of preparation method and applications of artemisinin molecularly imprinted film |
| CN105153371A (en) * | 2015-07-24 | 2015-12-16 | 北京科技大学 | Manufacturing method for cationic polyelectrolyte and application of cationic polyelectrolyte in super capacitor |
| CN105153371B (en) * | 2015-07-24 | 2018-02-27 | 北京科技大学 | A kind of manufacture method of cationic polyelectrolyte and the application in ultracapacitor |
| CN106206839A (en) * | 2016-06-30 | 2016-12-07 | 华侨大学 | A kind of solvent heat treatment method preparing perovskite solaode |
| CN106893039A (en) * | 2017-03-28 | 2017-06-27 | 南京工业大学 | A kind of method of photoinduction organic catalysis polymer modification |
| CN108395503A (en) * | 2018-03-14 | 2018-08-14 | 成都宏明电子股份有限公司 | It is a kind of antiferroelectric poly-（Vinylidene-trifluoro-ethylene-chlorotrifluoroethylene）The preparation method of graft polymers |
| CN108395503B (en) * | 2018-03-14 | 2021-07-20 | 成都宏明电子股份有限公司 | Preparation method of anti-ferroelectric poly (vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene) graft polymer |
| CN110256642A (en) * | 2019-03-13 | 2019-09-20 | 南京航空航天大学 | A kind of ferroelectric polymers and preparation method thereof with allochromy |
| CN110256642B (en) * | 2019-03-13 | 2021-07-30 | 南京航空航天大学 | Ferroelectric polymer with phosphorescence effect and preparation method thereof |
| CN113906065A (en) * | 2019-08-08 | 2022-01-07 | 株式会社Lg新能源 | Copolymer for polymer electrolyte, and gel polymer electrolyte and lithium secondary battery comprising the same |
| EP3961784A4 (en) * | 2019-08-08 | 2022-06-29 | LG Energy Solution, Ltd. | Copolymer for polymer electrolyte, gel polymer electrolyte comprising same, and lithium secondary battery |
| JP2022534952A (en) * | 2019-08-08 | 2022-08-04 | エルジー エナジー ソリューション リミテッド | Copolymer for polymer electrolyte, gel polymer electrolyte containing the same, and lithium secondary battery |
| JP7317432B2 (en) | 2019-08-08 | 2023-07-31 | エルジー エナジー ソリューション リミテッド | Copolymer for polymer electrolyte, gel polymer electrolyte containing the same, and lithium secondary battery |
| CN113906065B (en) * | 2019-08-08 | 2024-05-28 | 株式会社Lg新能源 | Copolymer for polymer electrolyte, gel polymer electrolyte including the same, and lithium secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103387642B (en) | 2016-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103387642A (en) | Preparation method of high energy storage density and polyvinylidene fluoride group grafted modified polymer | |
| Liu et al. | A novel porous gel polymer electrolyte based on poly (acrylonitrile-polyhedral oligomeric silsesquioxane) with high performances for lithium-ion batteries | |
| Voet et al. | Block copolymer route towards poly (vinylidene fluoride)/poly (methacrylic acid)/nickel nanocomposites | |
| Sui et al. | Antifouling PVDF ultrafiltration membranes incorporating PVDF-g-PHEMA additive via atom transfer radical graft polymerizations | |
| Voet et al. | Poly (vinylidene fluoride)/nickel nanocomposites from semicrystalline block copolymer precursors | |
| Lu et al. | Advanced semi-interpenetrating polymer network gel electrolyte for rechargeable lithium batteries | |
| CN105860375B (en) | Caustic resistant film | |
| Hsu et al. | High thermal and electrochemical stability of PVDF-graft-PAN copolymer hybrid PEO membrane for safety reinforced lithium-ion battery | |
| Fang et al. | Facile introduction of polyether chains onto polypropylene separators and its application in lithium ion batteries | |
| Zhou et al. | Preparation and performances of porous polyacrylonitrile–methyl methacrylate membrane for lithium-ion batteries | |
| Prasanna et al. | Effect of SiO2 coating on polyethylene separator with different stretching ratios for application in lithium ion batteries | |
| Wei et al. | Cross-linked porous polymer separator using vinyl-modified aluminum oxide nanoparticles as cross-linker for lithium-ion batteries | |
| CN103387682B (en) | Preparation method for crosslinkable high voltage-resistant high-energy density polyvinylidene fluoride (PVDF) plastic film | |
| He et al. | Enhanced ionic conductivity and electrochemical capacity of lithium ion battery based on PVDF-HFP/HDPE membrane | |
| EP2349523A1 (en) | Water flux polymer membranes | |
| Jamalpour et al. | Improved performance of lithium ion battery by the incorporation of novel synthesized organic-inorganic hybrid nanoparticles SiO2-poly (methyl methacrylate-co-ureidopyrimidinone) in gel polymer electrolyte based on poly (vinylidene fluoride) | |
| CN108395503B (en) | Preparation method of anti-ferroelectric poly (vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene) graft polymer | |
| Ren et al. | A novel PVFM based membranes prepared via phase inversion method and its application in GPE | |
| Li et al. | PVDF/PMMA brushes membrane for lithium‐ion rechargeable batteries prepared via preirradiation grafting technique | |
| Saikia et al. | Study of Li3+ ion irradiation effects in P (VDF–HFP) based gel polymer electrolytes for application in Li-ion battery | |
| JP2020061312A (en) | Trace metallic bridge separator | |
| EP2604332A1 (en) | Method for preparing a functionalized nanoporous track-etched PVDF membrane with RAFT polymerization | |
| TWI511352B (en) | Ion polymer film material and its preparation method and lithium secondary battery | |
| KR101519278B1 (en) | Manufacturing method of uv-curable type mesoporous gel polymer for lithium battery | |
| CN112510318B (en) | Crosslinked resin dispersion separator |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200114 Address after: 214437 West 3rd Floor, Block B, Chuangzhi Industrial Park, 201 Jinshan Road, Jiangyin City, Wuxi City, Jiangsu Province Patentee after: Wuxi Xinju Electronic Technology Co.,Ltd. Address before: 710049 Xianning Road, Shaanxi, China, No. 28, No. Patentee before: Xi'an Jiaotong University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240425 Address after: Institute of Chemistry, Chinese Academy of Sciences, No. 2 North 1st Street, Zhongguancun, Haidian District, Beijing, 100089 Patentee after: Zhang Zhicheng Country or region after: China Address before: 214437 West, 3rd floor, Cyberport B, Chuangzhi Industrial Park, 201 Jinshan Road, Jiangyin City, Wuxi City, Jiangsu Province Patentee before: Wuxi Xinju Electronic Technology Co.,Ltd. Country or region before: China |