CN102336854A - Preparation method for high heat resistance polyvinylidene fluoride - Google Patents
Preparation method for high heat resistance polyvinylidene fluoride Download PDFInfo
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Abstract
Provided is a preparation method for high heat resistance polyvinylidene fluoride, which belongs to the technical field of fluorochemical industry. The method is characterized by comprising the following steps: 1) blowing nitrogen into an enclosed polymerization kettle to remove oxygen and adding deionized water, magnesium hydroxide, diisopropyl peroxydicarbonate, diethyl malonate and vinylidene fluoride; 2) under the conditions that reaction pressure is 3.0 to 7.0 Mpa and reaction temperature is 45 to 120 DEG C, starting a stirring paddle, with a rotating speed being 350 to 750 r/min, and allowing an obtained mixture to react for 4 to 6 hours so as to prepare a polyvinylidene fluoride slurry; 3) rinsing the polyvinylidene fluoride slurry with deionized water until foams disappear, allowing the conductivity of rinsing liquid to decrease to less than 1 mu s/cm, and carrying out vacuum drying at a temperature of 90 to 100 DEG C for 15 to 20 hours so as to prepare a finished product. According to the invention, suspension polymerization is employed in the preparation method; a finally prepared polyvinylidene fluoride resin is loose and has greatly reduced possibility of adhering to the kettle and excellent high temperature resistance
Description
Technical field
The invention belongs to the fluorine chemical technical field, be specially the preparation method of high heat resistance pvdf.
Background technology
Pvdf (PVDF) is meant the homopolymer of vinylidene (VDF) or the multipolymer of vinylidene (VDF) and other a small amount of fluorine-containing vinyl monomers, and it is the thermoplastic engineering plastic of a kind of HMW, hemicrystalline, H.T..Usually, the relative molecular mass of PVDF is 40～600,000, fluorine content 59%, and percent crystallinity 60%～80%, its repeating unit is (CH
2-CF
2-)
nAlternately arranging of group.Because having the strongest electronegativity (4.0), fluorine atom makes that C-F is strong and becomes the maximum chemical bond (485KJ/mol) of bond energy in the covalent single bond in addition that fluorine atom has lower polarizability, the less model moral gas radius and the relatively symmetry that distributes.Therefore PVDF has high chemicalstability, highly insulativity, high light transmittance, high-wearing feature, high thermal resistance, radiation resistance, weathering resistance, low-refraction, low combustible, low pressure are electrical.The structure of comprehensive PVDF makes it have remarkable physical and chemical performance, has become the second largest kind that is only second to polytetrafluoroethylene (PTFE) in the fluoro-resin at present, is widely used in petrochemical industry, metallurgy; Pharmacy, building, food, environmental protection; Military project, fields such as aerospace, DEVELOPMENT PROSPECT is wide.The mode of production of PVDF mainly contains emulsion polymerization, suspension polymerization, solution polymerization process and supercritical polymerization method etc. at present, and is wherein general in industrial production with emulsion polymerization and suspension polymerization.
In the emulsion polymerization, the VDF monomer carries out polymerization in the presence of fluorine-containing salt tensio-active agent, and this system mainly is made up of monomer, initiator, emulsifying agent, chain-transfer agent, paraffin and deionized water.In polymerization process, add paraffin and can stablize the PVDF micella, after question response finished, filtration, cleaning, drying obtained particle diameter less than 1 micron powder.The advantage of this method is that (75-130 ℃) carries out polymerization under higher temperature, and polymerization velocity is very fast; Shortcoming is that emulsifying agent costs an arm and a leg, and emulsion needs postprocessing working procedures such as cohesion, washing, dehydration, drying, and production cost is higher, and the PVDF MWD broad of preparation, and thermostability is relatively poor.The patent that this respect can be mentioned has: US 4076929, and US 4025709.
The VDF monomer passes through dispersion agent in the suspension polymerization in water-soluble dispersion system, initiator, and the effect of chain-transfer agent (45～120 ℃) at a lower temperature is polymerized.The PVDF molecular chain of comparing suspension polymerization with letex polymerization is more regular, and side chain is few, and percent crystallinity is higher under the condition of identical weight-average molecular weight, and MWD is narrower, fusing point higher (>=3-5 ℃), and swelling capacity is littler in the chemical solvents; The suspended dispersed system can reduce the deposition of PVDF on reactor wall in addition, also need not condense this procedure in the last handling process, and production cost is lower.The dispersion agent that adsorbs on the granular resin is few, and product purity is high, can directly be used for granulation.
Current; A lot of technology are arranged all in the thermotolerance of making great efforts to improve PVDF; But without exception be all to be that the combination of emulsifying agent (tensio-active agent), initiator and chain-transfer agent through selecting all kinds of qualities for use improves technology, and major part all is to adopt the mode of letex polymerization to produce PVDF.The preferential oil-soluble initiator that adopts is like benzoyl peroxide, ditertiary butyl peroxide, dialkyl peroxydicarbonates, peresters in the letex polymerization; The ionic surface active agent that organic acid or alkali derive out; Can not produce the chain-transfer agent of unsettled chain end group owing to thermal treatment.
Patent US4360652 discloses the emulsion polymerisation process of a kind of VDF, and it is chain-transfer agent that this method adopts Virahol.
Patent FR2259114 discloses the emulsion polymerisation process of a kind of VDF, and it is initiator that this method adopts peroxy dicarbonate salt, and acetone is chain-transfer agent.
Patent EP169328 discloses the emulsion polymerisation process of a kind of VDF, and this method adopts trichlorofluoromethane as chain-transfer agent.
Patent CN1532212A discloses the emulsion polymerisation process of a kind of VDF, and this method adopts HFA161 as chain-transfer agent.
Patent EP169328 discloses the emulsion polymerisation process of a kind of VDF, and this method adopts di-isopropyl peroxydicarbonate (IPP) as initiator.
Patent EP387938 discloses the emulsion polymerisation process of a kind of VDF, and this method adopts ammonium persulphate as initiator, and ETHYLE ACETATE is as chain-transfer agent.
Patent FR264446 discloses the emulsion polymerisation process of a kind of VDF, and this method adopts alkyl acetates as chain-transfer agent, does not use emulsifying agent.
Patent US5929152 discloses the emulsion polymerisation process of a kind of VDF, and this method adopts adds the thermostability that bismuth salt improves PVDF.
Patent FR1298572 discloses the emulsion polymerisation process of a kind of VDF, and this method adopts interpolation barium salt or strontium salt to improve the thermostability of PVDF.
Patent US3728303 discloses the emulsion polymerisation process of a kind of VDF, and this method adopts interpolation sodium-chlor, Repone K, VAL-DROP, Potcrate to improve the thermostability of PVDF.
Patent CN1526744A discloses the emulsion polymerisation process of a kind of VDF, and this method utilizes Potassium Persulphate in aqueous dispersions, to carry out polymerization as initiator, improves the thermostability of PVDF through the alkylsulphonic acid potassium that adds sodium acetate and choose wantonly.
Summary of the invention
In view of the problems referred to above that exist in the prior art, the objective of the invention is to design the preparing method's that a kind of high heat resistance pvdf is provided technical scheme, the pvdf that makes of method has excellent high temperature resistant tint permanence thus.
The preparation method of described high heat resistance pvdf is characterized in that may further comprise the steps:
1) in airtight polymerization reaction kettle, purges the nitrogen deoxygenation; Add deionized water, Marinco H, di-isopropyl peroxydicarbonate, ethyl malonate, vinylidene; The consumption of said deionized water is the 125-200% of vinylidene quality; The consumption of said Marinco H is the 0.05-0.18% of vinylidene quality, and the consumption of said di-isopropyl peroxydicarbonate is the 0.015-2.0% of vinylidene quality, and the consumption of said ethyl malonate is the 0.15-2.3% of vinylidene quality;
2) reaction pressure is 3.0 – 7.0Mpa, and temperature of reaction is 120 ℃ of 45 –, opens stirring rake, and rotating speed is 350 – 750r/min, finishes reaction after 4-6 hour, makes the pvdf slurry;
3) with the pvdf slurry with deionized water wash to lather collapse, the washings specific conductivity is reduced to below the 1 μ s/cm, and then at 90-100 ℃ of following vacuum-drying 15-20 hour, makes finished product.
The preparation method of described high heat resistance pvdf is characterized in that: vinylidene adds at twice, adds the 30-50% of predetermined dose during beginning; React after 1-1.5 hour, slowly add rest part, keep-up pressure, continue to finish reaction behind the insulation polyase 13-5 hour at 3.0 – 7.0Mpa.
The preparation method of described high heat resistance pvdf is characterized in that: ethyl malonate adds in batches, before polymerization begins, adds the 50-70% of predetermined dose; Rest part is after reaction 1-1.5 hour, and 40min divides 3 equivalent to add at interval, keep-ups pressure at 3.0 – 7.0Mpa, adds end continued insulation polymerization and finishes reaction after 1.5-3 hour.
The preparation method of described high heat resistance pvdf is characterized in that in the step 1): the consumption of said deionized water is the 130-180% of vinylidene quality, preferred 150-170%.
The preparation method of described high heat resistance pvdf is characterized in that in the step 1): the consumption of said Marinco H is the 0.08-0.15% of vinylidene quality, preferred 0.10-0.13%.
The preparation method of described high heat resistance pvdf is characterized in that in the step 1): the consumption of said di-isopropyl peroxydicarbonate is the 0.02-1.5% of vinylidene quality, preferred 0.5-1.2%, more preferably 0.75-1.0%.
The preparation method of described high heat resistance pvdf is characterized in that in the step 1): the consumption of said ethyl malonate is the 0.5-1.5% of vinylidene quality, preferred 0.8-1.2%.
The preparation method of described high heat resistance pvdf is characterized in that step 2) in: reaction pressure 3.5 – 6.5Mpa, preferred 4.0 – 6.0Mpa, more preferably 4.5 – 5.5Mpa.
The preparation method of described high heat resistance pvdf is characterized in that step 2) in: temperature of reaction is 100 ℃ of 50 –, 90 ℃ of preferred 55 –, and more preferably 60 – 80 ℃.
The preparation method of described high heat resistance pvdf is characterized in that step 2) in: rotating speed is 400 – 700r/min, preferred 500 – 650r/min, more preferably 550 – 600r/min.
The present invention selects the preparation method of suspension polymerization for use, and a kind of new dispersion agent-Marinco H is provided, and selects organic initiators and chain-transfer agent to the PVDF better heat stability for use, and then regulates dosage and the distribution of adding molecular weight in the time controlled polymerization process; Through the pattern of temperature and stir speed (S.S.) telomerized polymer, pass through post-processing technology at last with dispersion agent in addition, the content of chain-transfer agent is reduced to minimum.
Adopting the present invention to carry out the used dispersion agent of VDF homopolymerization is Marinco H, and this dispersion agent is stirred to dispose after with the 2:1 molar ratio reaction by sodium hydroxide solution and magnesium chloride solution and forms, and the pH value is between 11～12.Dispersant dosage has bigger influence to resin particle size, and consumption is too small, and resin particle is too thick, conglomeration easily, and chain-transfer agent is not easy stripping, brings considerable influence to aftertreatment; Consumption is excessive, and resin particle is too thin, self is not easy to be dissolved.
Adopting the present invention to carry out the used initiator of VDF homopolymerization is highly active organo-peroxide-di-isopropyl peroxydicarbonate (IPP).The PVDF thermostability that adopts this type initiator to prepare does not have organic initiators such as ammonium persulphate will be got well.The consumption of initiator is very big to the performance impact of the rate of polymerization of VDF and PVDF.Initiator amount is too small, and rate of polymerization is too slow, is unfavorable for suitability for industrialized production; Initiator amount is excessive, and rate of polymerization is too fast, and polyreaction is unstable, and molecular weight and productive rate all descend.
Adopting the present invention to carry out the used chain-transfer agent of VDF homopolymerization is ethyl malonate.Chain-transfer agent can be used to the molecular weight of controlling polymers, and the size of its consumption and joining day, the thermostability of MWD and PVDF all had profound influence to rate of polymerization.The chain-transfer agent consumption is excessive, and the radical termination chance increases, and it is fast to stop speed, and molecular weight reduces, and shows as melt mass flow rate and increases, and limiting viscosity reduces, and elongation at break improves.The little then molecular weight of chain-transfer agent consumption increases, and reaction is difficult to control, and productive rate is low.The adding mode of chain-transfer agent and joining day also can influence molecular weight and the distribution of PVDF.Suitable chain-transfer agent adding principle is that the molecular weight of controlling polymers effectively can not produce detrimentally affect to its rate of polymerization and thermostability again, and be added in the reaction kettle is optimal selection in batches.
Adopt the present invention to carry out the used deionized water specific conductivity of VDF homopolymerization and be generally less than 0.5 μ s/cm.The too high instability that causes suspension system easily of specific conductivity, and can influence performance and the color and luster of PVDF.
The preparation method of above-mentioned high heat resistance pvdf; Adopt the mode of suspension polymerization; Vinylidene fluoride monomers is under the effect of dispersion agent Marinco H; With the di-isopropyl peroxydicarbonate is initiator, and ethyl malonate is that chain-transfer agent generates the pvdf particle through radical polymerization in aqueous medium.The polyvinylidene fluoride resin that adopts the present invention finally to make is loose, and sticking still amount reduces significantly, has excellent high thermal resistance (xanthochromia index YI is far below currently available products scope " 28-40 ").
Embodiment
Followingly the present invention is described further through embodiment and corresponding test.
Embodiment 1
At capacity is to purge the nitrogen deoxygenation in the airtight polymerization reaction kettle of 20L, makes that oxygen level is lower than 50ppm in the still.Add the 12Kg vaal water, 3.9g Marinco H, 1.8g di-isopropyl peroxydicarbonate; The 50g ethyl malonate, the 2.5Kg vinylidene is warming up to 47 ℃; Open stirring rake, rotating speed is 700r/min, keeps after 1 hour; Slowly add the 4.5Kg vinylidene, pressure is remained on about 5.6MPa, 40min divides each 15g of interpolation ethyl malonate 3 times at interval simultaneously.Add end continued insulation polymerization and finish reaction after 2.5 hours.With the pvdf slurry with deionized water wash until lather collapse, the washings specific conductivity is reduced to below the 1 μ s/cm, and then 90 ℃ of following vacuum-dryings 15 hours, makes finished product.
Embodiment 2
At capacity is to purge the nitrogen deoxygenation in the airtight polymerization reaction kettle of 20L, makes that oxygen level is lower than 50ppm in the still.Add the 12Kg vaal water, 9.2g Marinco H, 145g di-isopropyl peroxydicarbonate; The 100g ethyl malonate, the 3.5Kg vinylidene is warming up to 60 ℃; Open stirring rake, rotating speed is 500r/min, keeps after 1.5 hours; Slowly add the 3.8Kg vinylidene, pressure is remained on about 6.6MPa, 40min divides each 15g of interpolation ethyl malonate 3 times at interval simultaneously.Add end continued insulation polymerization and finish reaction after 1.5 hours.With the pvdf slurry with deionized water wash until lather collapse, the washings specific conductivity is reduced to below the 1 μ s/cm, and then 96 ℃ of following vacuum-dryings 18 hours, makes finished product.
Embodiment 3
At capacity is to purge the nitrogen deoxygenation in the airtight polymerization reaction kettle of 20L, makes that oxygen level is lower than 50ppm in the still.Add the 12Kg vaal water, 10.5g Marinco H, 60g di-isopropyl peroxydicarbonate; The 30g ethyl malonate, the 3.2Kg vinylidene is warming up to 66 ℃; Open stirring rake, rotating speed is 620r/min, keeps after 1.1 hours; Slowly add the 4Kg vinylidene, pressure is remained on about 5.6MPa, 40min divides each 10g of interpolation ethyl malonate 3 times at interval simultaneously.Add end continued insulation polymerization and finish reaction after 2 hours.With the pvdf slurry with deionized water wash until lather collapse, the washings specific conductivity is reduced to below the 1 μ s/cm, and then 100 ℃ of following vacuum-dryings 20 hours, makes finished product.
Comparative example 1
Similar with embodiment 3, only difference is that the add-on of Marinco H is 30g.
Embodiment 4
At capacity is to purge the nitrogen deoxygenation in the airtight polymerization reaction kettle of 20L, makes that oxygen level is lower than 50ppm in the still.Add the 12Kg vaal water, 13.5g Marinco H, 145g di-isopropyl peroxydicarbonate; The 80g ethyl malonate, the 3.2Kg vinylidene is warming up to 70 ℃; Open stirring rake, rotating speed is 650r/min, keeps after 1 hour; Slowly add the 4.2Kg vinylidene, pressure is remained on about 6.0MPa, 40min divides each 25g of interpolation ethyl malonate 3 times at interval simultaneously.Add end continued insulation polymerization and finish reaction after 2.7 hours.With the pvdf slurry with deionized water wash until lather collapse, the washings specific conductivity is reduced to below the 1 μ s/cm, and then 100 ℃ of following vacuum-dryings 18 hours, makes finished product.
Comparative example 2
Similar with embodiment 4, only difference is that the add-on first of ethyl malonate is 100g, and 3 additional amounts of 40min are 40g at interval.
Embodiment 5
At capacity is to purge the nitrogen deoxygenation in the airtight polymerization reaction kettle of 20L, makes that oxygen level is lower than 50ppm in the still.Add the 12Kg vaal water, 10.0g Marinco H, 65g di-isopropyl peroxydicarbonate; The 35g ethyl malonate, the 3.0Kg vinylidene is warming up to 62 ℃; Open stirring rake, rotating speed is 580r/min, keeps after 1.2 hours; Slowly add the 4Kg vinylidene, pressure is remained on about 5.0MPa, 40min divides each 10g of interpolation ethyl malonate 3 times at interval simultaneously.Add end continued insulation polymerization and finish reaction after 2.0 hours.With the pvdf slurry with deionized water wash until lather collapse, the washings specific conductivity is reduced to below the 1 μ s/cm, and then 100 ℃ of following vacuum-dryings 18 hours, makes finished product.
Comparative example 3
Similar with embodiment 5, only difference is that the add-on of Marinco H is 25g, and the add-on of di-isopropyl peroxydicarbonate is 145g, and ethyl malonate is disposable adding before the reaction beginning only, and add-on is 200g.
In any of the foregoing description, adhere to and block in the still that all do not induce reaction in polymerization process and after finishing.
In 265 ℃, the mensuration result of the xanthochromia property test of 1h is listed in the table below in 1 in the lump with the pvdf of the foregoing description and comparative example preparation.
Can find clearly that from the embodiment of above-mentioned table 1 and the result of comparative example high heat resistance pvdf provided by the invention has excellent high thermal resistance.
Claims (10)
1. the preparation method of high heat resistance pvdf is characterized in that may further comprise the steps:
1) in airtight polymerization reaction kettle, purges the nitrogen deoxygenation; Add deionized water, Marinco H, di-isopropyl peroxydicarbonate, ethyl malonate, vinylidene; The consumption of said deionized water is the 125-200% of vinylidene quality; The consumption of said Marinco H is the 0.05-0.18% of vinylidene quality, and the consumption of said di-isopropyl peroxydicarbonate is the 0.015-2.0% of vinylidene quality, and the consumption of said ethyl malonate is the 0.15-2.3% of vinylidene quality;
2) reaction pressure is 3.0 – 7.0Mpa, and temperature of reaction is 120 ℃ of 45 –, opens stirring rake, and rotating speed is 350 – 750r/min, finishes reaction after 4-6 hour, makes the pvdf slurry;
3) with the pvdf slurry with deionized water wash to lather collapse, the washings specific conductivity is reduced to below the 1 μ s/cm, and then at 90-100 ℃ of following vacuum-drying 15-20 hour, makes finished product.
2. the preparation method of high heat resistance pvdf as claimed in claim 1 is characterized in that: vinylidene adds at twice, adds the 30-50% of predetermined dose during beginning; React after 1-1.5 hour, slowly add rest part, keep-up pressure, continue to finish reaction behind the insulation polyase 13-5 hour at 3.0 – 7.0Mpa.
3. the preparation method of high heat resistance pvdf as claimed in claim 1 is characterized in that: ethyl malonate adds in batches, before polymerization begins, adds the 50-70% of predetermined dose; Rest part is after reaction 1-1.5 hour, and 40min divides 3 equivalent to add at interval, keep-ups pressure at 3.0 – 7.0Mpa, adds end continued insulation polymerization and finishes reaction after 1.5-3 hour.
4. the preparation method of high heat resistance pvdf as claimed in claim 1 is characterized in that in the step 1): the consumption of said deionized water is the 130-180% of vinylidene quality, preferred 150-170%.
5. the preparation method of high heat resistance pvdf as claimed in claim 1 is characterized in that in the step 1): the consumption of said Marinco H is the 0.08-0.15% of vinylidene quality, preferred 0.10-0.13%.
6. the preparation method of high heat resistance pvdf as claimed in claim 1 is characterized in that in the step 1): the consumption of said di-isopropyl peroxydicarbonate is the 0.02-1.5% of vinylidene quality, preferred 0.5-1.2%, more preferably 0.75-1.0%.
7. the preparation method of high heat resistance pvdf as claimed in claim 1 is characterized in that in the step 1): the consumption of said ethyl malonate is the 0.5-1.5% of vinylidene quality, preferred 0.8-1.2%.
8. the preparation method of high heat resistance pvdf as claimed in claim 1 is characterized in that step 2) in: reaction pressure 3.5 – 6.5Mpa, preferred 4.0 – 6.0Mpa, more preferably 4.5 – 5.5Mpa.
9. the preparation method of high heat resistance pvdf as claimed in claim 1 is characterized in that step 2) in: temperature of reaction is 100 ℃ of 50 –, 90 ℃ of preferred 55 –, and more preferably 60 – 80 ℃.
10. the preparation method of high heat resistance pvdf as claimed in claim 1 is characterized in that step 2) in: rotating speed is 400 – 700r/min, preferred 500 – 650r/min, more preferably 550 – 600r/min.
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| CN102875711A (en) * | 2012-09-20 | 2013-01-16 | 中昊晨光化工研究院有限公司 | Condensing washing method of polyvinylidene fluoride emulsion |
| CN103524647A (en) * | 2013-08-16 | 2014-01-22 | 巨化集团技术中心 | Method for preparing polyvinylidene fluoride resin |
| CN103626900A (en) * | 2012-08-22 | 2014-03-12 | 株式会社吴羽 | Manufacturing method of vinylidene fluoride system polymer |
| CN104497190A (en) * | 2014-12-29 | 2015-04-08 | 浙江孚诺林化工新材料有限公司 | Preparation method of vinylidene fluoride polymer of lithium ion battery electrode material binder |
| CN104710550A (en) * | 2013-12-11 | 2015-06-17 | 浙江蓝天环保高科技股份有限公司 | High molecular weight polyvinylidene fluoride resin and preparation method thereof |
| CN105461837A (en) * | 2015-12-18 | 2016-04-06 | 常熟三爱富振氟新材料有限公司 | Preparation method of polyvinylidene fluoride ultrafiltration membrane |
| CN105924554A (en) * | 2016-06-12 | 2016-09-07 | 巨化集团技术中心 | Preparation method of polyvinylidene fluoride resin |
| CN110317286A (en) * | 2018-03-30 | 2019-10-11 | 浙江蓝天环保高科技股份有限公司 | A method of improving polyvinylidene fluoride resin degree of purity |
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| CN116375915A (en) * | 2023-04-03 | 2023-07-04 | 乳源东阳光氟树脂有限公司 | Method for preparing ultra-high molecular weight PVDF resin by supercritical polymerization process |
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| CN103626900A (en) * | 2012-08-22 | 2014-03-12 | 株式会社吴羽 | Manufacturing method of vinylidene fluoride system polymer |
| CN103626900B (en) * | 2012-08-22 | 2016-01-06 | 株式会社吴羽 | The manufacture method of vinylidene based polymer |
| CN102875711B (en) * | 2012-09-20 | 2014-05-14 | 中昊晨光化工研究院有限公司 | Condensing washing method of polyvinylidene fluoride emulsion |
| CN102875711A (en) * | 2012-09-20 | 2013-01-16 | 中昊晨光化工研究院有限公司 | Condensing washing method of polyvinylidene fluoride emulsion |
| CN103524647A (en) * | 2013-08-16 | 2014-01-22 | 巨化集团技术中心 | Method for preparing polyvinylidene fluoride resin |
| CN104710550A (en) * | 2013-12-11 | 2015-06-17 | 浙江蓝天环保高科技股份有限公司 | High molecular weight polyvinylidene fluoride resin and preparation method thereof |
| CN104497190A (en) * | 2014-12-29 | 2015-04-08 | 浙江孚诺林化工新材料有限公司 | Preparation method of vinylidene fluoride polymer of lithium ion battery electrode material binder |
| CN104497190B (en) * | 2014-12-29 | 2016-09-21 | 浙江孚诺林化工新材料有限公司 | A kind of preparation method of the partial fluorine ethylene polymer for lithium ion battery electrode material binding agent |
| CN105461837A (en) * | 2015-12-18 | 2016-04-06 | 常熟三爱富振氟新材料有限公司 | Preparation method of polyvinylidene fluoride ultrafiltration membrane |
| CN105924554A (en) * | 2016-06-12 | 2016-09-07 | 巨化集团技术中心 | Preparation method of polyvinylidene fluoride resin |
| CN105924554B (en) * | 2016-06-12 | 2018-12-25 | 巨化集团技术中心 | A kind of preparation method of polyvinylidene fluoride resin |
| CN110317286A (en) * | 2018-03-30 | 2019-10-11 | 浙江蓝天环保高科技股份有限公司 | A method of improving polyvinylidene fluoride resin degree of purity |
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| CN102336854B (en) | 2013-05-29 |
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