CN110317286A - A method of improving polyvinylidene fluoride resin degree of purity - Google Patents
A method of improving polyvinylidene fluoride resin degree of purity Download PDFInfo
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- CN110317286A CN110317286A CN201810295751.9A CN201810295751A CN110317286A CN 110317286 A CN110317286 A CN 110317286A CN 201810295751 A CN201810295751 A CN 201810295751A CN 110317286 A CN110317286 A CN 110317286A
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- fluorine
- cleaning agent
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- containing cleaning
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F114/18—Monomers containing fluorine
- C08F114/22—Vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/24—Treatment of polymer suspensions
Abstract
The present invention provides a kind of washing methods of polyvinylidene fluoride resin, washing realization is carried out to polyvinylidene fluoride resin by fluorine-containing cleaning agent, the fluorine-containing cleaning agent is selected from least one of hydrocarbon chlorofluoro-alkane, carbon hydrofluoroalkane, hydrocarbon fluorine cycloalkane, carbon fluothane hydrocarbon, carbon hydrofluoroether, the pure and mild hydrocarbon fluorine ketone of hydrocarbon fluorine and boiling point is greater than 30 DEG C.Method provided by the invention can remove initiator used in polymerization process, avoid forming Kynoar plasticizing material in washing kettle, to obtain the high polyvinylidene fluoride resin of degree of purity.
Description
Technical field
The invention belongs to polymer arts, are related to a kind of method for improving polymer degree of purity, mention more particularly, to one kind
The method of high polyvinylidene fluoride resin degree of purity.
Background technique
Kynoar (PVDF) has heat-resisting quantity, super-weathering resistance, corrosion resistance, pollution resistance, chemical inertness, extremely low
The characteristics such as surface energy, piezoelectricity, dielectricity, pyroelectricity, can not only be used for thermoplastic engineering plastic, also can be applied to petroleum
The fields such as work, electric, fluorocarbon coating and membrane material.
Industrially preparing the polymerization of Kynoar at present includes emulsion polymerization and suspension polymerisation, wherein suspension polymerisation
Method after the completion of reaction, generally removes the initiator contained in resin, decomposition of initiator product, dispersing agent by way of washing
With telogen etc..Water-washing method includes room temperature washing and hot water washing.Decomposition of initiator product is mainly lower alcohol, ketone, acid etc.,
There are preferable solubility, common telogen such as diethyl carbonate, ethyl acetate, diethyl malonate etc. in water, due to this
Body usage amount is few, although solubility is not satisfactory in water, also can remove major part using room temperature method for washing.Hot water wash
The solubility of decomposition product in water can be increased by washing, while destroy unreacted initiator, make its resolve into lower alcohol, ketone,
After acid etc., it is dissolved in water removing, therefore can be washed simultaneously using room temperature washing and hot water in water-washing process.
Although hot water washing can preferably remove unreacted initiator, after hot water washing is used for a long time, due to
The melting range of Kynoar is longer, and minimal amount of low melting point polyvinylidene fluoride resin is being washed after prolonged and repeated be heated in washing kettle
The plasticizing material for generating Kynoar in the kettle wall of kettle is washed, may be fallen off from kettle wall in washing process, into polyvinylidene fluoride
In alkene product, cause to be mixed into new impurity in Kynoar product, and so that by Kynoar products application in water
When process film and electrode of lithium cell binder occasion, there is insoluble matter in solution, influence properties of product.
For the washing methods for improving Kynoar, the prior art has made following effort:
(1) it is 70~90 DEG C, 4~8 points of wash time that Chinese patent CN102875711A, which reports the temperature of hot water washing,
Clock.This washing methods can not completely remove high decomposition temperature initiator peroxycarboxylic acid esters, and washing kettle makes in the long period
Kynoar plasticizing material is easy to appear after；
(2) Chinese patent CN105924554A reports the method washed using inorganic-organic compounding dispersing agent,
In Kynoar last handling process, the strong oxidizer relative to polyvinylidene fluoride resin wet feed weight 0.01~0.1% is added
Washed, described in strong oxidizer be selected from sodium peroxide, hydrogen peroxide, potassium permanganate, hypochlorous acid etc..Using strong in the method
Oxidant itself can introduce impurity, and partial oxidation agent such as sodium peroxide decomposition product alkalinity is too strong, will cause and gathers inclined fluorine
Vinyl decomposes, and potassium permanganate coloration ability is strong, and the aobvious pink of resin is difficult to be cleaned.
Therefore, it is necessary to make further technological improvement to the washing methods in Kynoar polymerization process.
Summary of the invention
The purpose of the present invention is to provide a kind of washing methods suitable for Kynoar polymerization, can remove and polymerize
Initiator used in journey avoids forming Kynoar plasticizing material in washing kettle, to obtain the high poly- inclined fluorine of degree of purity
Vinyl.
Present inventor's discovery has the fluorine-containing cleaning agent of good solubility to Kynoar initiator when using
When resin is washed, wherein it can will be transferred to fluorine-containing cleaning agent by unreacted initiator, then by fluorine-containing cleaning agent and gather inclined
Fluoroethylene resin is separated, to significantly improve the degree of purity of polyvinylidene fluoride resin.For what is contained in fluorine-containing cleaning agent
Initiator can also be removed by way of heating or alkali cleaning, realize the recycling to fluorine-containing cleaning agent.
The invention provides the following technical scheme:
A kind of washing methods of polyvinylidene fluoride resin, which comprises in polyvinylidene fluoride resin suspension polymerisation knot
Shu Hou washs polyvinylidene fluoride resin using fluorine-containing cleaning agent,
The fluorine-containing cleaning agent is selected from: hydrocarbon chlorofluoro-alkane (CxHyFzClw, 1≤x≤6, y+z+w=2x+2), hydrocarbon fluorine
Alkane (CxHyFz, 1≤x≤10, y+z=2x+2), hydrocarbon fluorine cycloalkane (CxHyFz, 5≤x≤12, y+z≤2x), carbon fluothane
Hydrocarbon (CxFy, 1≤x≤6, y=2x+2), carbon hydrofluoroether (CxHyFzOw, 2≤x≤12, y+z≤2x+2, w >=1), hydrocarbon fluorine alcohol
In (CxHyFzOw, 1≤x≤8, y+z=2x+2, w >=1) and hydrocarbon fluorine ketone (CxHyFzOw, 3≤x≤12, y+z=2x, w >=1)
At least one；
And the boiling point of the fluorine-containing cleaning agent is greater than 30 DEG C.
The fluorine-containing cleaning agent that the present invention uses need to have good solubility to initiator, and boiling point satisfaction makes it in washing process
In be liquid, and itself is less toxic or nontoxic, non-ignitable not quick-fried etc..
Suitable fluorine-containing cleaning agent is selected from: hydrocarbon chlorofluoro-alkane (CxHyFzClw, 1≤x≤6, y+z+w=2x+2), hydrocarbon
Fluothane hydrocarbon (CxHyFz, 1≤x≤10, y+z=2x+2), hydrocarbon fluorine cycloalkane (CxHyFz, 5≤x≤12, y+z≤2x), carbon fluorine
Alkane (CxFy, 1≤x≤6, y=2x+2), carbon hydrofluoroether (CxHyFzOw, 2≤x≤12, y+z≤2x+2, w >=1), hydrocarbon fluorine
Alcohol (CxHyFzOw, 1≤x≤8, y+z=2x+2, w >=1) and hydrocarbon fluorine ketone (CxHyFzOw, 3≤x≤12, y+z=2x, w >=1)
At least one of.
Preferably, the fluorine-containing cleaning agent is selected from carbon hydrofluoroalkane (CxHyFz, 1≤x≤10, y+z=2x+2) and carbon
At least one of hydrofluoroether (CxHyFzOw, 2≤x≤12, y+z=2x+2, w >=1).
The carbon hydrofluoroalkane, it is preferred that CxHyFz, 4≤x≤6, y+z=2x+2.It may further be preferable that described
Carbon hydrofluoroalkane is 2,3- dihydro Decafluoropentane (HFC-4310mee).
The carbon hydrofluoroether, it is preferred that CxHyFzOw, 4≤x≤7, y+z=2x+2, w >=1.It may further be preferable that
The carbon hydrofluoroether is selected from 1,1,1,2,3,3- hexafluoro propyl methyl ether (HFE-356mec), methyl nonafluorobutyl ether (HFE-
449s) and at least one of tetra- fluoro ethyl -2,2,2- trifluoroethyl ether (HFE-347pc-f) of 1,1,2,2-.
The dosage satisfaction of mode of washing provided by the invention, the fluorine-containing cleaning agent used makes to remain in polyvinylidene fluoride resin
Initiator dissolution, in the fluorine-containing cleaning agent that is transferred to.
Preferably, the dosage of the fluorine-containing cleaning agent is 0.01~5 times of polyvinylidene fluoride resin dry weight.
It may further be preferable that the dosage of the fluorine-containing cleaning agent is 0.1~1 times of polyvinylidene fluoride resin dry weight.
Washing methods provided by the invention, after vinylidene suspension polymerisation, polyvinylidene fluoride resin enters washing
In kettle, dehydration is first passed through, then polyvinylidene fluoride resin is washed with the fluorine-containing cleaning agent, then is cleaned with deionized water
Polyvinylidene fluoride resin obtains polyvinylidene fluoride resin powder after dehydration, drying.
Washing methods provided by the invention, the washing times of fluorine-containing cleaning agent can be 1 time or repeatedly.It can select as needed
Select the washing times of fluorine-containing cleaning agent.
The present invention also provides a kind of recovery method of fluorine-containing cleaning agent, unreacted draw to be dissolved in fluorine-containing cleaning agent
Hair agent is handled, and so that it is resolved into the products such as water-soluble lower alcohol, ketone, ester, and then remove by water-washing method.It can make
Recovery method includes heating and alkali wash.
When recycling fluorine-containing cleaning agent using heating, after pvdf resin is reunited in the fluorine-containing cleaning agent washing,
The recovery method includes:
(1) by the half-life period of initiator used in vinylidene suspension polymerisation be 10 hours when corresponding temperature on the basis of temperature
Degree, is heated to 10~50 DEG C of fiducial temperature or more for the fluorine-containing cleaning agent of recycling；
(2) make that the fluorine-containing cleaning agent of extraction is washed with deionized.
When above-mentioned heating recycles fluorine-containing cleaning agent, consider from production efficiency and energy consumption angle, side as one preferred
Formula, in the step (1), corresponding temperature is base when the half-life period using initiator used in vinylidene suspension polymerisation is 10 hours
The fluorine-containing cleaning agent of recycling is heated to 20~40 DEG C of fiducial temperature or more by quasi- temperature.
The time of heating was generally advisable with 10~60 minutes.Consider from production efficiency and energy consumption angle, preferably 20~40
Minute.
When above-mentioned heating recycles fluorine-containing cleaning agent, in step (2) makes that fluorine-containing cleaning agent is washed with deionized, remove it
In the initiator and decomposition of initiator product that contain.Under normal circumstances, washing is repeated repeatedly, to remove initiator and initiator
Decomposition product.Preferably, make to be washed with deionized the fluorine-containing cleaning agent of extraction twice or more than twice.
When recycling fluorine-containing cleaning agent using alkali wash, after pvdf resin is reunited in the fluorine-containing cleaning agent washing,
The recovery method includes:
Fluorine-containing cleaning agent is extracted using the deionized water solution washing of highly basic.
When above-mentioned alkali wash recycles fluorine-containing cleaning agent, fluorine-containing cleaning agent, removal are washed using the deionized water solution of highly basic
The initiator and decomposition of initiator product wherein contained.Under normal circumstances, washing is repeated repeatedly, to remove initiator and initiation
Agent decomposition product.Preferably, fluorine-containing cleaning agent is extracted twice or more than twice using the deionized water solution washing of highly basic.
The highly basic is preferably selected from least one of sodium hydroxide, potassium hydroxide and ammonium hydroxide.
The concentration of the deionized water solution of highly basic meets the initiator and decomposition of initiator that can be removed in fluorine-containing cleaning agent
Product.
Preferably, the concentration of the deionized water solution of the highly basic is 10-6To 10-2mol/L。
Vinylidene suspension polymerisation resin polymerization production method of the present invention can be according to method general in industry
Preparation, comprising:
(1) deionized water, dispersing agent, other auxiliary agents, vacuum nitrogen displacement are added into reactor；
(2) reaction temperature is risen into assigned temperature, it is disposable or be added portionwise vinylidene, initiator, chain-transferring agent and
Other polymerized monomers carry out polymerization reaction, can be changed to polymerization temperature in polymerization process；
(3) reaction pressure is down to specified pressure in kettle to be polymerized, and discharging, reaction terminates, and obtains Kynoar suspending resin
Crude product.
Initiator used in above-mentioned vinylidene suspension polymerisation resin polymerization production method, can be commonly used in the art
Polymerization initiator.The initiator is generally organic peroxide, and example includes: peroxy dicarbonate di-n-propyl ester, peroxide
Change two diisopropyl carbonates, dicetyl peroxydicarbonate diisobutyl ester, dicetyl peroxydicarbonate (2- ethylhexyl), the tertiary fourth of peroxidating two
Base, peroxidized t-butyl perbenzoate, lauroyl peroxide etc..It is anti-for initially causing polymerization based on 100 weight parts of polymer monomers
The dosage (i.e. the additional amount of initiator in step (2)) for the initiator answered can be 0.05~0.5 parts by weight.
Dispersing agent used in above-mentioned vinylidene suspension polymerisation resin polymerization production method, can be commonly used in the art
Dispersing agent, example include methylcellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl fibre
Tie up element, carboxymethyl cellulose, polyethylene glycol oxide, maleic acid modified polyethylene etc..It is appropriate based on 100 weight parts of polymer monomers
Dispersing agent additional amount be 0.01~1 parts by weight.
Chain-transferring agent suitable for the method for the present invention can be any compound that can continue vinylidene fluoride polymerization reaction,
Example includes: alcohols, such as methanol, isopropanol, n-butanol；Ketone, such as acetone, butanone；Esters, such as ethyl acetate, carbonic acid diethyl
Ester, dimethyl carbonate；Containing halogenated hydrocarbons, such as chloroform, methylene chloride；Aliphatic alkane, such as n-hexane, normal heptane.By 100 parts by weight
Polymerized monomer meter, the dosage of chain-transferring agent are 0.01~0.2 parts by weight.
The better suited polymerization temperature of the present invention is 20-140 DEG C, preferably 30-100 DEG C, more preferable 40-80 DEG C.
The better suited pressure of the present invention is 2.0-20.0MPa, preferably 4.0-15.0MPa, more preferable 6.0-12.0MPa.
Washing methods provided by the invention can remove the initiation in the polyvinylidene fluoride resin of suspension polymerization preparation
Agent.Initiator therein can be initiator used in suspension polymerization.As an example, the initiator includes organic peroxy
Compound, such as: peroxy dicarbonate di-n-propyl ester, di-isopropyl peroxydicarbonate, dicetyl peroxydicarbonate diisobutyl ester, peroxide
Change two carbonic acid (2- ethylhexyl), di-t-butyl peroxide, peroxidized t-butyl perbenzoate, lauroyl peroxide etc..
Washing methods provided by the invention is used not only for washing polyvinylidene fluoride polyamino alkenyl resin, additionally it is possible to for washing
Wash Kynoar copolymer resins.When the resin is Kynoar copolymer resins, the Kynoar copolymer resins
It can be vinylidene and be selected from vinyl fluoride, trifluoro-ethylene, tetrafluoroethene, chlorotrifluoroethylene, tetrafluoropropene, pentafluoropropene, six
Fluoropropene, perfluoro methyl vinyl ether, perfluoro propyl vinyl ether, acrylate, methacrylate, maleate, lemon health
At least one of acid esters, vinylacetate, vinylene carbonate and other monomers that can be copolymerized with vinylidene monomer is total to
Poly resin.
The present invention has effectively removed remaining initiator in polyvinylidene fluoride resin in such a way that fluorine-containing cleaning agent washs
And the decomposition product of initiator, the free radical for avoiding decomposition of initiator generation form double bond to resin chain structural damage, therefore
The degree of purity of polyvinylidene fluoride resin can be assessed by the way of Evaluation of Thermal Stability.
Evaluation of Thermal Stability method are as follows:
The sheet material that appropriate polyvinylidene fluoride copolymer powder is pressed into 4mm thickness on compression molding instrument is weighed, is dried at 250 DEG C
Be heated 30min in case.It is measured and is tried with Hunter Lab CQX3576 yellowing afterwards, xanthochromia journey is characterized with yellow colour index (YID1925)
Degree, index is lower, and thermal stability is better.
Specific embodiment
Next combined with specific embodiments below invention is further explained, but does not limit the invention to these tools
Body embodiment.One skilled in the art would recognize that present invention encompasses may include in Claims scope
All alternatives, improvement project and equivalent scheme.
Embodiment 1: polyvinylidene fluoride resin preparation
2500 grams of deionized waters, 5 grams of hydroxyethyl celluloses are added in 5 liters of vertical polymerization reaction kettles.Merge reaction kettle, takes out
Vacuum is simultaneously replaced with nitrogen, until oxygen content is less than 10ppm in reaction kettle, adding a certain amount of vinylidene fluoride monomers makes kettle internal pressure
Power is to 2.0MPa.Then start to be stirred with the rate of 500rpm, reactor temperature is risen to 45 DEG C, continue to supplement inclined fluorine
Vinyl monomer to reacting kettle inner pressure reaches 5.0MPa.2.0 grams of di-isopropyl peroxydicarbonates and 2g diethyl carbonate are added,
Start polymerization reaction.Reacting kettle inner pressure is set to maintain 5.0MPa by adding vinylidene fluoride monomers.When the inclined fluorine of total amount 1000g
When vinyl monomer addition finishes and reaction pressure is down to 2.0MPa in kettle, reaction terminates, and discharges and collects resin.Above-mentioned experiment is total
Repeat 6 times, collects resin, and number consecutively sample 1, sample 2, sample 3, sample 4, sample 5, sample 6 respectively.
Embodiment 2: Kynoar suspending resin washing
Washing kettle is added in sample 1, methyl nonafluorobutyl ether (HFE-449s) 500g, deionized water is added in dehydration
5000g agitator treating 15 minutes, is removed and is recycled to obtain 486g methyl nonafluorobutyl ether (HFE-449s).Deionized water is added
5000g agitator treating 15 minutes, removes deionized water, is repeated 4 times.Drying, obtains Kynoar suspending resin 892g.
Embodiment 3: Kynoar suspending resin washing
Washing kettle is added in sample 2,2,3- dihydro Decafluoropentane (HFC-4310mee) 500g, deionized water is added in dehydration
5000g, agitator treating remove and recycle to obtain 479g2,3- dihydro Decafluoropentane (HFC-4310mee) after 15 minutes.Addition is gone
Ionized water agitator treating 15 minutes, removes deionized water, is repeated 4 times.Drying, obtains Kynoar suspending resin 901g.
Embodiment 4: Kynoar suspending resin washing
Washing kettle is added in sample 3,1,1,1,2,3,3- hexafluoro propyl methyl ether (HFE-356mec) is added in dehydration
500g, deionized water 5000g, agitator treating remove after 15 minutes and recycle to obtain 1,1,1,2,3,3- hexafluoro propyl first of 480g
Base ether (HFE-356mec).Deionized water is added, agitator treating 15 minutes, removes deionized water, is repeated 4 times.Drying, is gathered
Vinylidene suspending resin 901g.
Embodiment 5: the recycling and reusing of cleaning agent
Washing kettle is added in sample 4, methyl nonafluorobutyl ether (HFE-449s) 486g that embodiment 2 recycles is added in dehydration,
Fresh methyl nona-fluoro butyl group ether (HFE-449s) 14g, deionized water 5000g are supplemented, agitator treating was removed and recycled after 15 minutes
Obtain 479g methyl nonafluorobutyl ether (HFE-449s).Deionized water is added, agitator treating 15 minutes, removes deionized water, weight
It is 4 times multiple.Drying, obtains Kynoar suspending resin 902g.
Embodiment 6: the recycling and reusing of cleaning agent
2,3- dihydro Decafluoropentane (HFC-4310mee) 479g that embodiment 3 recycles, is heated to 70 in pressure vessel
DEG C, constant temperature 30 minutes.Deionized water is added to wash 3 times, each deionized water dosage is 500g.Obtain 465g methyl nona-fluoro butyl group
Ether (HFE-449s).
Washing kettle is added in sample 5,2, the 3- dihydro Decafluoropentane (HFC- after deionized water is washed is added in dehydration
4310mee) 465g supplements fresh 2,3- dihydro Decafluoropentane (HFC-4310mee) 35g, deionized water 5000g, agitator treating
It is removed after 15 minutes and recycles to obtain 483g 2,3- dihydro Decafluoropentane (HFC-4310mee).Deionized water 5000g is added, stirs
Washing 15 minutes is mixed, deionized water is removed, is repeated 4 times.Drying, obtains Kynoar suspending resin 880g.
Embodiment 7: the recycling and reusing of cleaning agent
1,1,1,2,3,3- hexafluoro propyl methyl ether (HFE-356mec) 480g that embodiment 4 recycles, it is 10 that concentration, which is added,- 4The sodium hydroxide solution 500g of mol/L, washing extraction 3 times are added deionized water and wash 3 times, and each deionized water dosage is
500g.Obtain 469g methyl nonafluorobutyl ether (HFE-449s).
Washing kettle is added in sample 6,1,1,1,2,3, the 3- hexafluoro hydroxypropyl methyl after deionized water is washed is added in dehydration
Ether (HFE-356mec) 469g supplements fresh 1,1,1,2,3,3- hexafluoro propyl methyl ether (HFE-356mec) 31g, deionized water
5000g, agitator treating remove and recycle to obtain 483g1,1,1,2,3,3- hexafluoro propyl methyl ether (HFE- after 15 minutes
356mec).Deionized water 5000g is added, agitator treating 15 minutes, removes deionized water, is repeated 4 times.Drying, obtains gathering inclined fluorine
Ethylene suspending resin 880g.
Comparative example 1
With embodiment 1, resin discharges to washing kettle polymerization procedure, and deionized water 5000g is added, and agitator treating 15 divides
Clock removes deionized water, is repeated 6 times.Drying, obtains Kynoar suspending resin 892g.
Comparative example 2
With embodiment 1, resin discharges to washing kettle polymerization procedure, and 80 DEG C of deionized water 5000g are added, and stirs 30 points
Clock removes deionized water, is repeated twice.Deionized water 5000g is added, agitator treating 15 minutes, removes deionized water, repeats 4
It is secondary.Drying, obtains Kynoar suspending resin 892g.
Kynoar suspending resin thermal stability prepared by embodiment 2~7 and comparative example 1~2 is as shown in table 1.
Table 1
From the data in table 1, it can be seen that fluorine-containing cleaning agent cleaning step remains after effectively removing polymerization reaction in embodiment 2~7
Initiator, avoid decomposition of initiator generation free radical to resin chain structural damage formed double bond, the poly- inclined fluorine of preparation
Ethylene suspending resin impurity content is lower, and thermal stability is more preferable.
Claims (11)
1. a kind of washing methods of polyvinylidene fluoride resin, it is characterised in that the described method includes: outstanding in polyvinylidene fluoride resin
After floating polymerization, polyvinylidene fluoride resin is washed using fluorine-containing cleaning agent,
The fluorine-containing cleaning agent is selected from: hydrocarbon chlorofluoro-alkane (CxHyFzClw, 1≤x≤6, y+z+w=2x+2), carbon hydrofluoroalkane
(CxHyFz, 1≤x≤10, y+z=2x+2), hydrocarbon fluorine cycloalkane (CxHyFz, 5≤x≤12, y+z≤2x), carbon fluothane hydrocarbon
(CxFy, 1≤x≤6, y=2x+2), carbon hydrofluoroether (CxHyFzOw, 2≤x≤12, y+z≤2x+2, w >=1), hydrocarbon fluorine alcohol
In (CxHyFzOw, 1≤x≤8, y+z=2x+2, w >=1) and hydrocarbon fluorine ketone (CxHyFzOw, 3≤x≤12, y+z=2x, w >=1)
At least one；
And the boiling point of the fluorine-containing cleaning agent is greater than 30 DEG C.
2. the washing methods of polyvinylidene fluoride resin described in accordance with the claim 1, it is characterised in that the fluorine-containing cleaning agent choosing
From carbon hydrofluoroalkane (CxHyFz, 1≤x≤10, y+z=2x+2) and carbon hydrofluoroether (CxHyFzOw, 2≤x≤12, y+z=2x+
At least one of 2, w >=1).
3. the washing methods of polyvinylidene fluoride resin according to claim 2, it is characterised in that the fluorine-containing cleaning agent choosing
From carbon hydrofluoroalkane (CxHyFz, 4≤x≤6, y+z=2x+2) and carbon hydrofluoroether (CxHyFzOw, 4≤x≤7, y+z=2x+2, w
At least one of >=1).
4. the washing methods of polyvinylidene fluoride resin described in accordance with the claim 3, it is characterised in that the fluorine-containing cleaning agent choosing
From 2,3- dihydro Decafluoropentane (HFC-4310mee), 1,1,1,2,3,3- hexafluoro propyl methyl ether (HFE-356mec), methyl nine
At least one in tetra- fluoro ethyl -2,2,2- trifluoroethyl ether (HFE-347pc-f) of fluorine butyl ether (HFE-449s) and 1,1,2,2-
Kind.
5. the washing methods of polyvinylidene fluoride resin described in accordance with the claim 1, it is characterised in that the fluorine-containing cleaning agent
Dosage is 0.01~5 times of polyvinylidene fluoride resin dry weight.
6. the washing methods of polyvinylidene fluoride resin according to claim 5, it is characterised in that the fluorine-containing cleaning agent
Dosage is 0.1~1 times of polyvinylidene fluoride resin dry weight.
7. the washing methods of polyvinylidene fluoride resin described in accordance with the claim 1, it is characterised in that the fluorine-containing cleaning agent exists
It is recycled after washing, recovery method includes:
(1) corresponding temperature, will as benchmark temperature when the half-life period of initiator used is 10 hours using in vinylidene suspension polymerisation
The fluorine-containing cleaning agent of recycling is heated to 10~50 DEG C of fiducial temperature or more；
(2) make that the fluorine-containing cleaning agent of extraction is washed with deionized.
8. the washing methods of polyvinylidene fluoride resin according to claim 7, it is characterised in that:
In the step (1), corresponding temperature is when the half-life period with initiator used in vinylidene suspension polymerisation is 10 hours
The fluorine-containing cleaning agent of recycling is heated to 20~40 DEG C of fiducial temperature or more by fiducial temperature；
In the step (2), make to be washed with deionized the fluorine-containing cleaning agent of extraction twice or more than twice.
9. the washing methods of polyvinylidene fluoride resin according to claim 7, it is characterised in that the fluorine-containing cleaning agent exists
It is recycled after washing, recovery method includes:
Fluorine-containing cleaning agent is extracted using the deionized water solution washing of highly basic.
10. the washing methods of polyvinylidene fluoride resin according to claim 7, it is characterised in that:
Fluorine-containing cleaning agent is extracted twice or more than twice using the deionized water solution washing of highly basic；
The highly basic is selected from least one of sodium hydroxide, potassium hydroxide and ammonium hydroxide；
The concentration of the deionized water solution of highly basic is 10-6To 10-2mol/L。
11. the washing methods of polyvinylidene fluoride resin described in accordance with the claim 1, it is characterised in that the Kynoar tree
Rouge is the copolymer resins of vinylidene and other monomers, and the other monomers are selected from vinyl fluoride, trifluoro-ethylene, tetrafluoroethene, three
Fluorine vinyl chloride, tetrafluoropropene, pentafluoropropene, hexafluoropropene, perfluoro methyl vinyl ether, perfluoro propyl vinyl ether, acrylic acid
Ester, methacrylate, maleate, citraconate, vinylacetate, vinylene carbonate and it is other can be total with vinylidene
At least one of poly- monomer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810295751.9A CN110317286A (en) | 2018-03-30 | 2018-03-30 | A method of improving polyvinylidene fluoride resin degree of purity |
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| CN111440255A (en) * | 2020-03-26 | 2020-07-24 | 东莞东阳光科研发有限公司 | Post-treatment method of fluorine-containing resin emulsion and fluorine-containing resin |
| WO2022045115A1 (en) * | 2020-08-31 | 2022-03-03 | ダイキン工業株式会社 | Composition containing fluorine oil |
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