CN103387642B - The preparation method of high energy storage density polyvinylidene fluoride graft modification polymer - Google Patents
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Abstract
The preparation method of high energy storage density polyvinylidene fluoride graft modification polymer, employing 1-METHYLPYRROLIDONE etc. is solvent, with stannous chloride, 2, 2-bipyridyl, copper etc. are catalyst system and catalyzing, to gather (vinylidene-trifluoro-ethylene-CTFE) P (VDF-TrFE-CTFE) as raw material, taking polymethacrylates as grafted monomers, synthetic poly-(vinylidene-trifluoro-ethylene-CTFE) P (VDF-CTFE-TrFE) grafting polymethacrylate copolymer, there is method easy control simple to operate, catalyst uses content low, be easy to the advantage of polymer purification.
Description
Technical field
The glycerol polymerization that the present invention relates to a kind of Kynoar (PVDF) base fluoropolymer polymer changesProperty new method, the particularly preparation of high energy storage density polyvinylidene fluoride graft modification polymerMethod.
Background technology
Kynoar (PVDF) and binary/terpolymer thereof (P (VDF-TrFE) orP (VDF-CTFE) or (PVDF-TrFE-CTFE)) posted because thering is very high dielectric constantGreat expectations is for the high energy-storage capacitor dielectric material of a new generation. Comparing current commercial twin shaft drawsStretched polypropylene (BOPP) thin polymer film, polyvinylidene fluoride fluoropolymer polymer is as a kind of utmost pointProperty polymer has very high electric field polarization value and quite high resistance to breakdown electric field. But its typical caseFerroelectric feature, make to have higher residual polarization value and then most stored charge withoutMethod effectively discharges. For this reason, researcher exists by the method for electron irradiation or copolymerization the 3rd monomerIn P (VDF-TrFE), introduce fault of construction, destroy its large scale crystal grain, make it change relaxation intoHenan Ferroelectric body, promotes stored energy release efficiency. At present, P (VDF-CTFE) polymerEnergy density can reach 25J/cm3(650MV/m), but its energy loss is still higher (approximately40-60%). For this reason, how, in keeping high-energy-density, effectively reduce its energy and damageConsumption is Research Challenges instantly. Recently, studies have reported that adopt P (VDF-TrFE-CTFE) orThe energy that the method for P (VDF-CTFE) grafted polystyrene (PS) has significantly reduced polymer damagesConsumption, but meanwhile the energy storage density of polymer is also significantly reducing, also imperfect satisfiedThe dielectric substance of high energy storage demand.
Summary of the invention
In order to overcome the defect of prior art, realize the energy storage of PVDF base fluoropolymer object height closeDegree, low-yield drain performance, the object of the present invention is to provide a kind of high energy storage density to gather inclined to one side fluorineThe preparation method that vinyl graft copolymer is polymer-modified, by poly-(vinylidene-trifluoro-ethylene-trifluoroVinyl chloride) graft copolymerization methacrylate (comprise polymethyl methacrylate (PMMA),Polyethyl methacrylate (PEMA) and polybutyl methacrylate (PBMA)), protectingWhen holding polymer and there is high energy storage density, significantly reduce energy loss.
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 polymer, comprisesFollowing steps:
Step 1, in there-necked flask, add polymer, add catalyst, part and reduction simultaneouslyAgent, after three circulations of vacuum nitrogen filling gas, adds the solvent of deoxygenation after mixing with syringe,The mass ratio of solvent and polymer is 15:1～30:1, fully stirs, and treats that polymer dissolves completelyAfter, reaction bulb is moved in oil bath, be warming up to 100 ° of C; Add grafted monomers with syringe,The mass ratio of grafted monomers and polymer is 1:1～5:1, and polymerisation is after 15 minutes-24 hoursStop.
Described polymer is poly-(vinylidene-trifluoro-ethylene-trifluoro chlorine of different component mol ratioEthene) P (VDF-TrFE-CTFE) polymer;
Described catalyst is stannous chloride (CuCl) or cuprous bromide (CuBr); Catalyst withCl atom in poly-(vinylidene-trifluoro-ethylene-CTFE) P (VDF-TrFE-CTFE)Mol ratio be 0.5:1～2:1;
Described part is 2,2-bipyridyl (BPy) or N, N, and N', N, ' N''-pentamethyl diethylideneTriamine (PMDETA) or three [(2-pyridine radicals) methyl] amine (TPMA) or hexamethyl triethyl groupTriamine (Me6TREN); The mol ratio of part and catalyst is 1:1～2:1;
Described reducing agent is copper powder simple substance (Cu); The mol ratio of reducing agent and catalystFor 0.5:1～2:1;
Described solvent is the good solvent of fluoropolymer polymer, comprise DMF (DMF),1-METHYLPYRROLIDONE (NMP) or dimethyl sulfoxide (DMSO) (DMSO);
Described reaction temperature is 100 ° of C;
Described grafted monomers comprises methyl methacrylate (MMA), EMAOr butyl methacrylate (BMA) (EMA).
Add acetone diluted in step 2, the reaction solution that finally obtains in step 1 after, obtainDiluting reaction solution, acetone and reaction solution volume ratio are 1:5; Diluting reaction solution is poured into mixedClose in solution, mixed solution is acid water and methyl alcohol for pH=3 volume ratio 3:1, mixes moltenThe volume ratio of liquid and diluting reaction solution is not less than 5:1, stirs 1 hour, filters and separates out polymerizationThing; The mixed solution cyclic washing that resulting polymers water and methyl alcohol volume ratio are 3:1 repeatedly extremelyProduct is white in color; Resulting polymers Soxhlet extracting 24 hours in chloroform solvent; Not higher thanUnder 60 ° of C conditions, vacuum drying to constant weight obtains target product.
Step 3, the DMF for polymer (DMF) that step 2 is obtainedDissolve, the mass ratio of polymer and solvent DMF (DMF) is 3:100-6:100, after polymer fully dissolves, polymer solution is coated on clean glass plate, andPlace it on the heating plate of 50-100 ° of C, after solvent evaporates is complete, will be with polymerThe sheet glass of film is inserted constant temperature 4-24 hour in the baking oven of 150-200 ° of C, then soaks at onceEnter in 0 ° of C mixture of ice and water, obtain the thin polymer film of Quenching Treatment.
When the energy-storage property of test polymer film, with ion sputtering instrument at two of thin polymer filmIt is 0.069cm that face is sprayed area2, thickness is about the metal electrode of 80nm. Ferroelectric hysteresis loop is adoptedWith the ferroelectric test macro of the PremiereII of RadiantTechnologies company, test frequency is10Hz. Energy storage density is obtained by unidirectional electrical hysteresis curves integral and calculating, and formula is Ue=∫EdD，UeFor energy storage density, E is electric-field intensity, and D is dielectric displacement value.
The present invention adopts 1-METHYLPYRROLIDONE etc. for solvent, with stannous chloride, 2,2-bipyridyl,Copper etc. are catalyst system and catalyzing, to gather (vinylidene-trifluoro-ethylene-CTFE)P (VDF-TrFE-CTFE) is raw material, taking polymethacrylates as grafted monomers, synthetic poly-(vinylidene-trifluoro-ethylene-CTFE) P (VDF-CTFE-TrFE) grafting gathers methyl-propOlefin(e) acid ester copolymer, has method easy control simple to operate, and catalyst uses content low, is easy to gatherThe advantage of compound purifying.
Brief description of the drawings
Fig. 1 is graft copolymer1HNMR 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 energy storage density curve.
Detailed description of the invention
Embodiment mono-
The preparation method of high energy storage density polyvinylidene fluoride graft modification polymer, comprisesFollowing steps:
Step 1, in there-necked flask, add polymer raw material, add simultaneously catalyst, part andReducing agent, this mixture, after vacuum nitrogen filling gas three times circulation, adds deoxygenation with syringeSolvent, the mass ratio of solvent and polymer is 25:1; Fully stir, treat that polymer is completely moltenXie Hou, moves into reaction bulb in oil bath, is warming up to 100 ° of C of desired reaction temperature. Use syringeAdd monomer, the mass ratio of monomer and polymer is 1.5:1, and polymerisation stopped after 2 hours.
Described polymer raw material is poly-(vinylidene-trifluoro-ethylene-CTFE)P (VDF-TrFE-CTFE), mol ratio VDF/TrFE/CTFE=80/15/5.
Described catalyst is stannous chloride (CuCl).
In described catalyst agent and P (VDF-TrFE-CTFE), Cl atomic molar is than being 1:1.
Described part is 2,2-bipyridyl (BPy).
The mol ratio of described part and catalyst is 2:1.
Described reducing agent is copper powder simple substance (Cu).
Described former dose is 1:1 with the mol ratio of catalyst.
Described solvent is 1-METHYLPYRROLIDONE (NMP).
Described monomer is methyl methacrylate (MMA).
Add acetone diluted in step 2, the reaction solution that finally obtains in step 1 after, obtainDiluting reaction solution, acetone and reaction solution volume ratio are 1:5; Diluting reaction solution is poured into mixedClose in solution, mixed solution is acid water and methyl alcohol for pH=3 volume ratio 3:1, mixes moltenThe volume ratio of liquid and diluting reaction solution is not less than 5:1, stirs 1 hour, filters and separates out polymerizationThing; The mixed solution cyclic washing that resulting polymers water and methyl alcohol volume ratio are 3:1 repeatedly extremelyProduct is white in color. Resulting polymers Soxhlet extracting 24 hours in chloroform solvent. Not higher thanUnder 60 ° of C conditions, vacuum drying to constant weight obtains target product.
Nuclear-magnetism records the VDF/TrFE/CTFE that mole consists of of polymer/ MMA=80/15/5/25, amounting to PMMA mass percent is 27%. A curve in Fig. 1For P (VDF-TrFE-CTFE)-g-PMMA polymer1HNMR nuclear magnetic spectrogram.
Step 3, the DMF for polymer (DMF) that step 2 is obtainedDissolve, the mass ratio of polymer and solvent DMF (DMF) is 3:100-6:100, after polymer fully dissolves, polymer solution is coated on clean glass plate, andPlace it on the heating plate of 50-100 ° of C, after solvent evaporates is complete, will be with polymerThe sheet glass of film is inserted constant temperature 4-24 hour in the baking oven of 150-200 ° of C, then soaks at onceEnter in 0 ° of C mixture of ice and water, obtain the thin polymer film of Quenching Treatment.
Embodiment bis-
The preparation method of high energy storage density polyvinylidene fluoride graft modification polymer, comprisesFollowing steps:
Step 1, in there-necked flask, add polymer raw material, add simultaneously catalyst, part andReducing agent, this mixture, after vacuum nitrogen filling gas three times circulation, adds deoxygenation with syringeSolvent, the mass ratio of solvent and polymer is 25:1; Fully stir, treat that polymer is completely moltenXie Hou, moves into reaction bulb in oil bath, is warming up to 100 ° of C of desired reaction temperature; Use syringeAdd monomer, the mass ratio of monomer and polymer is 1.5:1, and polymerisation stopped after 2 hours.
Described polymer raw material is poly-(vinylidene-trifluoro-ethylene-CTFE)P (VDF-TrFE-CTFE), mol ratio VDF/TrFE/CTFE=80/15/5.
Described catalyst is stannous chloride (CuCl).
In described catalyst agent and P (VDF-TrFE-CTFE), Cl atomic molar is than being 1:1.
Described part is 2,2-bipyridyl (BPy).
The mol ratio of described part and catalyst is 2:1.
Described reducing agent is copper powder simple substance (Cu).
Described former dose is 1:1 with the mol ratio of catalyst.
Described solvent is 1-METHYLPYRROLIDONE (NMP).
Described monomer is EMA (EMA).
Add acetone diluted in step 2, the reaction solution that finally obtains in step 1 after, obtainDiluting reaction solution, acetone and reaction solution volume ratio are 1:5; Diluting reaction solution is poured into mixedClose in solution, mixed solution is acid water and methyl alcohol for pH=3 volume ratio 3:1, mixes moltenThe volume ratio of liquid and diluting reaction solution is not less than 5:1, stirs 1 hour, filters and separates out polymerizationThing; The mixed solution cyclic washing that resulting polymers water and methyl alcohol volume ratio are 3:1 repeatedly extremelyProduct is white in color. Resulting polymers Soxhlet extracting 24 hours in chloroform solvent. Not higher thanUnder 60 ° of C conditions, vacuum drying to constant weight obtains target product.
Nuclear-magnetism records the VDF/TrFE/CTFE that mole consists of of polymer/ EMA=80/15/5/25, amounting to PEMA mass percent is 30%. In Fig. 1, B curve isP (VDF-TrFE-CTFE)-g-PEMA polymer1HNMR nuclear magnetic spectrogram.
Step 3, the DMF for polymer (DMF) that step 2 is obtainedDissolve, the mass ratio of polymer and solvent DMF (DMF) is 3:100-6:100, after polymer fully dissolves, polymer solution is coated on clean glass plate, andPlace it on the heating plate of 50-100 ° of C, after solvent evaporates is complete, will be with polymerThe sheet glass of film is inserted constant temperature 4-24 hour in the baking oven of 150-200 ° of C, then soaks at onceEnter in 0 ° of C mixture of ice and water, obtain the thin polymer film of Quenching Treatment.
Fig. 2 is the two-way ferroelectric hysteresis loop of resulting polymers; Fig. 3 is the unidirectional electrical of resulting polymersHysteresis curves; Fig. 4 is the energy storage density curve being calculated by Fig. 3 curvilinear integral.
Embodiment tri-
The preparation method of high energy storage density polyvinylidene fluoride graft modification polymer, comprisesFollowing steps:
Step 1, in there-necked flask, add polymer raw material, add simultaneously catalyst, part andReducing agent, this mixture, after vacuum nitrogen filling gas three times circulation, adds deoxygenation with syringeSolvent, the mass ratio of solvent and polymer is 25:1; Fully stir, treat that polymer is completely moltenXie Hou, moves into reaction bulb in oil bath, is warming up to 100 ° of C of desired reaction temperature. Use syringeAdd monomer, the mass ratio of monomer and polymer is 1.5:1, after the polymerisation regular hourStop.
Described polymer raw material is poly-(vinylidene-trifluoro-ethylene-CTFE)P (VDF-TrFE-CTFE), mol ratio VDF/TrFE/CTFE=80/15/5.
Described catalyst is stannous chloride (CuCl).
In described catalyst agent and P (VDF-TrFE-CTFE), Cl atomic molar is than being 1:1.
Described part is 2,2-bipyridyl (BPy).
The mol ratio of described part and catalyst is 2:1.
Described reducing agent is copper powder simple substance (Cu).
Described former dose is 1:1 with the mol ratio of catalyst.
Described solvent is 1-METHYLPYRROLIDONE (NMP).
Described monomer is butyl methacrylate (BMA).
The described reaction time is 2 hours.
Add acetone diluted in step 2, the reaction solution that finally obtains in step 1 after, obtainDiluting reaction solution, acetone and reaction solution volume ratio are 1:5; Diluting reaction solution is poured into mixedClose in solution, mixed solution is acid water and methyl alcohol for pH=3 volume ratio 3:1, mixes moltenThe volume ratio of liquid and diluting reaction solution is not less than 5:1, stirs 1 hour, filters and separates out polymerizationThing; The mixed solution cyclic washing that resulting polymers water and methyl alcohol volume ratio are 3:1 repeatedly extremelyProduct is white in color. Resulting polymers Soxhlet extracting 24 hours in chloroform solvent. Not higher thanUnder 60 ° of C conditions, vacuum drying to constant weight obtains target product.
Nuclear-magnetism records the VDF/TrFE/CTFE that mole consists of of polymer/ BMA=80/15/5/25, amounting to PBMA mass percent is 37%. In Fig. 1, C curve isP (VDF-TrFE-CTFE)-g-PBMA polymer1HNMR nuclear magnetic spectrogram.
Step 3, the DMF for polymer (DMF) that step 2 is obtainedDissolve, the mass ratio of polymer and solvent DMF (DMF) is 3:100-6:100, after polymer fully dissolves, polymer solution is coated on clean glass plate, andPlace it on the heating plate of 50-100 ° of C, after solvent evaporates is complete, will be with polymerThe sheet glass of film is inserted constant temperature 4-24 hour in the baking oven of 150-200 ° of C, then soaks at onceEnter in 0 ° of C mixture of ice and water, obtain the thin polymer film of Quenching Treatment.
Embodiment tetra-
The preparation method of high energy storage density polyvinylidene fluoride graft modification polymer, comprisesFollowing steps:
Step 1, in there-necked flask, add polymer raw material, add simultaneously catalyst, part andReducing agent, this mixture, after vacuum nitrogen filling gas three times circulation, adds deoxygenation with syringeSolvent, the mass ratio of solvent and polymer is 25:1; Fully stir, treat that polymer is completely moltenXie Hou, moves into reaction bulb in oil bath, is warming up to 100 ° of C of desired reaction temperature. Use syringeAdd monomer, the mass ratio of monomer and polymer is 1.5:1, after the polymerisation regular hourStop.
Described polymer raw material is poly-(vinylidene-trifluoro-ethylene-CTFE)P (VDF-TrFE-CTFE), mol ratio VDF/TrFE/CTFE=80/15/5.
Described catalyst is stannous chloride (CuCl).
In described catalyst agent and P (VDF-TrFE-CTFE), Cl atomic molar is than being 1:1.
Described part is 2,2-bipyridyl (BPy).
The mol ratio of described part and catalyst is 2:1.
Described reducing agent is copper powder simple substance (Cu).
Described former dose is 1:1 with the mol ratio of catalyst.
Described solvent is 1-METHYLPYRROLIDONE (NMP).
Described monomer is methyl methacrylate (MMA).
The described reaction time is 15 minutes.
Add acetone diluted in step 2, the reaction solution that finally obtains in step 1 after, obtainDiluting reaction solution, acetone and reaction solution volume ratio are 1:5; Diluting reaction solution is poured into mixedClose in solution, mixed solution is acid water and methyl alcohol for pH=3 volume ratio 3:1, mixes moltenThe volume ratio of liquid and diluting reaction solution is not less than 5:1, stirs 1 hour, filters and separates out polymerizationThing; The mixed solution cyclic washing that resulting polymers water and methyl alcohol volume ratio are 3:1 repeatedly extremelyProduct is white in color. Resulting polymers Soxhlet extracting 24 hours in chloroform solvent. Not higher thanUnder 60 ° of C conditions, vacuum drying to constant weight obtains target product.
Nuclear-magnetism records the VDF/TrFE/CTFE that mole consists of of polymer/ MMA=80/15/5/7, amounting to PMMA mass percent is 9%.
Step 3, the DMF for polymer (DMF) that step 2 is obtainedDissolve, the mass ratio of polymer and solvent DMF (DMF) is 3:100-6:100, after polymer fully dissolves, polymer solution is coated on clean glass plate, andPlace it on the heating plate of 50-100 ° of C, after solvent evaporates is complete, will be with polymerThe sheet glass of film is inserted constant temperature 4-24 hour in the baking oven of 150-200 ° of C, then soaks at onceEnter in 0 ° of C mixture of ice and water, obtain the thin polymer film of Quenching Treatment.
Embodiment five
The preparation method of high energy storage density polyvinylidene fluoride graft modification polymer, comprisesFollowing steps:
Step 1, in there-necked flask, add polymer raw material, add simultaneously catalyst, part andReducing agent, this mixture, after vacuum nitrogen filling gas three times circulation, adds deoxygenation with syringeSolvent, the mass ratio of solvent and polymer is 25:1; Fully stir, treat that polymer is completely moltenXie Hou, moves into reaction bulb in oil bath, is warming up to 100 ° of C of desired reaction temperature. Use syringeAdd monomer, the mass ratio of monomer and polymer is 1.5:1, after the polymerisation regular hourStop.
Described polymer raw material is poly-(vinylidene-trifluoro-ethylene-CTFE)P (VDF-TrFE-CTFE), mol ratio VDF/TrFE/CTFE=80/12/8.
Described catalyst is stannous chloride (CuCl).
In described catalyst agent and P (VDF-TrFE-CTFE), Cl atomic molar is than being 1:1.
Described part is 2,2-bipyridyl (BPy).
The mol ratio of described part and catalyst is 2:1.
Described reducing agent is copper powder simple substance (Cu).
Described former dose is 0.5:1 with the mol ratio of catalyst.
Described solvent is 1-METHYLPYRROLIDONE (NMP).
Described monomer is methyl methacrylate (MMA).
The described reaction time is 2 hours.
Add acetone diluted in step 2, the reaction solution that finally obtains in step 1 after, obtainDiluting reaction solution, acetone and reaction solution volume ratio are 1:5; Diluting reaction solution is poured into mixedClose in solution, mixed solution is acid water and methyl alcohol for pH=3 volume ratio 3:1, mixes moltenThe volume ratio of liquid and diluting reaction solution is not less than 5:1, stirs 1 hour, filters and separates out polymerizationThing; The mixed solution cyclic washing that resulting polymers water and methyl alcohol volume ratio are 3:1 repeatedly extremelyProduct is white in color. Resulting polymers Soxhlet extracting 24 hours in chloroform solvent. Not higher thanUnder 60 ° of C conditions, vacuum drying to constant weight obtains target product.
Nuclear-magnetism records the VDF/TrFE/CTFE that mole consists of of polymer/ MMA=80/12/8/25, amounting to PMMA mass percent is 30%.
Step 3, the DMF for polymer (DMF) that step 2 is obtainedDissolve, the mass ratio of polymer and solvent DMF (DMF) is 3:100-6:100, after polymer fully dissolves, polymer solution is coated on clean glass plate, andPlace it on the heating plate of 50-100 ° of C, after solvent evaporates is complete, will be with polymerThe sheet glass of film is inserted constant temperature 4-24 hour in the baking oven of 150-200 ° of C, then soaks at onceEnter in 0 ° of C mixture of ice and water, obtain the thin polymer film of Quenching Treatment.
Other non-limiting examples is as shown in the table:
Claims (1)
1. the preparation method of high energy storage density polyvinylidene fluoride graft modification polymer, is characterized in that, comprises the following steps:
Step 1, in there-necked flask, add polymer raw material, add catalyst, part and reducing agent simultaneously, after mixing after vacuum nitrogen filling gas three times circulation, add the solvent of deoxygenation with syringe, the mass ratio of solvent and polymer is 15:1～30:1, fully stirs, after polymer dissolves completely, reaction bulb is moved in oil bath, be warming up to 100 DEG C; Add grafted monomers with syringe, the mass ratio of grafted monomers and polymer is 1:1～5:1, and polymerisation stops after 15 minutes-24 hours;
Described polymer raw material is poly-(vinylidene-trifluoro-ethylene-CTFE) P (VDF-TrFE-CTFE) polymer of different component mol ratio;
Described catalyst is stannous chloride CuCl or cuprous bromide CuBr; Catalyst is 0.5:1～2:1 with the mol ratio of the middle Cl atom of poly-(vinylidene-trifluoro-ethylene-CTFE) P (VDF-TrFE-CTFE);
Described part is 2,2-bipyridyl (BPy) or N, N, and N', N, ' N "-five methyl diethylentriamine (PMDETA) or three [(2-pyridine radicals) methyl] amine (TPMA) or hexamethyl triethyl group triamine (Me6TREN); The mol ratio of part and catalyst is 1:1～2:1;
Described reducing agent is copper powder simple substance Cu; The mol ratio of reducing agent and catalyst is 0.5:1～2:1;
Described solvent is the good solvent of fluoropolymer polymer, comprises DMF DMF, 1-METHYLPYRROLIDONE NMP or dimethyl sulfoxide (DMSO) DMSO;
Described reaction temperature is 100 DEG C;
Described grafted monomers comprises methyl methacrylate (MMA), EMA (EMA) or butyl methacrylate (BMA);
Add acetone diluted in step 2, the reaction solution that finally obtains in step 1 after, obtain diluting reaction solution, acetone and reaction solution volume ratio are 1:5; Diluting reaction solution is poured in mixed solution, and mixed solution is acid water and methyl alcohol for pH=3 volume ratio 3:1, and the volume ratio of mixed solution and diluting reaction solution is not less than 5:1, stirs 1 hour, filters and separates out polymer; The mixed solution cyclic washing that resulting polymers water and methyl alcohol volume ratio are 3:1 is repeatedly 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 DEG C of conditions;
Step 3, the polymer N that step 2 is obtained, dinethylformamide DMF dissolves, polymer and solvent N, the mass ratio of dinethylformamide DMF is 3:100-6:100, after polymer fully dissolves, polymer solution is coated on clean glass plate, and place it on the heating plate of 50-100 DEG C, after solvent evaporates is complete, constant temperature 4-24 hour in the baking oven of 150-200 DEG C will be inserted with the sheet glass of thin polymer film, then immerse at once in 0 DEG C of mixture of ice and water, obtain the thin polymer film of Quenching Treatment.
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| 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 |
| 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 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6787238B2 (en) * | 1998-11-18 | 2004-09-07 | The Penn State Research Foundation | Terpolymer systems for electromechanical and dielectric applications |
-
2013
- 2013-07-12 CN CN201310294444.6A patent/CN103387642B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|
| High-field antiferroelectric behaviour and minimized energy loss in poly(vinylidene-co-trifluoroethylene)-graft- poly(ethyl methacrylate) for energy storage application;Junjie Li等;《Journal of Materials Chemistry》;20120922(第22期);第23468-23476页 * |
| 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》.2012,(第1期),第1111-1121页. * |
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| CN103387642A (en) | 2013-11-13 |
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