CN110343212A - The manufacturing method of vinylidene fluoride copolymers - Google Patents
The manufacturing method of vinylidene fluoride copolymers Download PDFInfo
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- CN110343212A CN110343212A CN201811550858.XA CN201811550858A CN110343212A CN 110343212 A CN110343212 A CN 110343212A CN 201811550858 A CN201811550858 A CN 201811550858A CN 110343212 A CN110343212 A CN 110343212A
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- 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
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
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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
- C08F214/00—Copolymers 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
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
- C08F214/225—Vinylidene fluoride with non-fluorinated comonomers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The application realizes the method in a shorter time and more easily manufacturing vinylidene fluoride copolymers.In the manufacturing method of vinylidene fluoride copolymers, include: to the process for carrying out suspension polymerisation containing vinylidene fluoride monomers containing vinylidene and the other monomers that can be copolymerized with vinylidene, in the process, it is polymerize under the conditions of vinylidene becomes the temperature of supercriticality, it is described disposably to be put into containing vinylidene fluoride monomers.
Description
Technical field
The present invention relates to a kind of manufacturing methods of vinylidene fluoride copolymers.
Background technique
The general chemical-resistant of vinylidene fluoride copolymers, weatherability, stain resistance etc. are excellent, various films, moulding material,
It is utilized in the various uses such as coating and adhesive.
As the manufacturing method of vinylidene fluoride copolymers, for example, as it is known that having using the comonomer with carboxyl at 30 DEG C
The method of vinylidene fluoride copolymers is manufactured under neighbouring polymerization temperature (for example, referring to patent document 1).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 6-172452 bulletin (on June 21st, 1994 is open)
Summary of the invention
Problems to be solved by the invention
However, the polymerization time of manufacturing method documented by patent document 1 is long, from the viewpoint of productivity, still has and change
Kind leeway.
The purpose of a scheme of the invention is, realizes that manufacture vinylidene is copolymerized in a shorter time and more easily
The method of object.
Technical solution
The manufacturing method of the vinylidene fluoride copolymers of a scheme of the invention is characterized in that, includes: to contain inclined fluorine
The process that ethylene and the starting monomer for the other monomers that can be copolymerized with vinylidene carry out suspension polymerisation, in the process,
It is polymerize under the conditions of vinylidene becomes the temperature of critical state, the starting monomer is disposably put into.
Beneficial effect
According to the present invention, vinylidene fluoride copolymers can be manufactured in a shorter time and more easily.
Specific embodiment
Hereinafter, an embodiment of the invention is described in detail.
The manufacturing method of the vinylidene fluoride copolymers of present embodiment, which passes through, makes containing containing vinylidene and other monomers
Vinylidene fluoride monomers under conditions of vinylidene becomes supercriticality and carry out suspension polymerisation in water and manufacture inclined fluorine second
Alkene copolymer.
Vinylidene fluoride copolymers are will to contain vinylidene (critical temperature Tc=30.1 DEG C, critical pressure Pcr=
The copolymer of the other monomers that can polymerize 4.38MPa) and other than vinylidene being polymerized containing vinylidene fluoride monomers.Cause
This, vinylidene fluoride copolymers include the structural unit from vinylidene and the structure from the other monomers other than vinylidene
Unit.
In the example of other monomers, include: fluorochemical monomer is (for example, ethylene fluoride, trifluoro-ethylene, tetrafluoroethene, trifluoro
Vinyl chloride, hexafluoropropene, perfluoroalkyl vinyl ether), ethylene, unsaturated dibasic acid derivative (for example, monomethyl maleate,
Dimethyl maleate), vinyl acetate, (methyl) acrylamide, (methyl) dimethylacrylamide, allyl glycidol
Ether, (methyl) acrylic acid alkyl ester compound (for example, (methyl) methyl acrylate), ester compounds containing carboxy acrylic, (example
Such as, (methyl) acrylic acid, acrylic acid 2- carboxylic ethyl ester, succinic acid (methyl) acryloxy propyl ester, succinic acid (methyl) acryloyl
Oxygroup ethyl ester), acrylic acid 2- hydroxyl ethyl ester and hydroxypropyl acrylate.Wherein, it is preferably selected from by hexafluoropropene, maleic acid list first
Ester, (methyl) acrylic acid, acrylic acid 2- carboxylic ethyl ester, succinic acid (methyl) acryloxy propyl ester and succinic acid (methyl) third
One or more of the group that alkene acyloxy ethyl ester is constituted compound.Wherein, more preferable monomethyl maleate and hexafluoropropene.
The amount containing the vinylidene in vinylidene fluoride monomers of present embodiment be vinylidene become principal component amount be
Can, such as can be 50 mass % or more.Content containing the vinylidene in vinylidene fluoride monomers can be inclined according to what is manufactured
Property required by fluoride copolymers suitably determines.Such as inclined fluorine is originated from from fully embodying in vinylidene fluoride copolymers
From the viewpoint of the structure of ethylene is played the role of, the content is preferably 80 mass % or more, further preferably 85 matter
% or more is measured, 90 mass % or more are particularly preferably contained.There is no limit for the upper limit of above-mentioned content, but in order to play as copolymer
Property, such as preferably 99.9 mass % are hereinafter, more preferably 99 mass % or less.
For the manufacturing method of present embodiment, other than temperature condition, list containing vinylidene can be made with passing through
Body is under conditions of vinylidene becomes supercriticality and carries out suspension polymerisation in water and manufactures vinylidene fluoride copolymers
Known method is similarly implemented.
In the manufacturing method of present embodiment, specific quantity is supplied containing vinylidene fluoride monomers and water to reactor,
Vinylidene carries out suspension polymerisation under conditions of becoming supercriticality.Here, containing vinylidene fluoride monomers disposably put into
Reactor.Input amount is not particularly limited.
In the manufacturing method of present embodiment, water can fully can implemented to contain inclined fluorine to the supply amount of reactor
It is suitably determined in the range of the suspension polymerisation of vinyl monomer.From the viewpoint, supply amount from water to reactor relative to
Containing vinylidene fluoride monomers to the supply amount of reactor, preferably 2 times or more, more preferably 2.2 times or more.In addition, from above-mentioned
Viewpoint considers that the supply amount of above-mentioned water is relative to the supply amount containing vinylidene fluoride monomers to reactor, and preferably 4 times hereinafter, more
Preferably 3.6 times or less.
In addition, polymerization temperature can be enough to make the vinylidene in reactor in the manufacturing method of present embodiment
It is suitably determined as within the temperature range of supercriticality.Within this range, if polymerization temperature is too low, the reaction of suspension polymerisation
Time is elongated, and the productivity of vinylidene fluoride copolymers is lower sometimes as a result, if polymerization temperature is excessively high, the reaction of suspension polymerisation
The pressure of system is got higher, it is sometimes desirable to the higher reactor of resistance to pressure.From the viewpoint for the productivity for improving vinylidene fluoride copolymers
Considering, polymerization temperature is preferably 35 DEG C or more, and more preferably 40 DEG C or more.In addition, from the surging of the pressure for inhibiting reaction system
From the viewpoint of, polymerization temperature is preferably 65 DEG C hereinafter, more preferably 60 DEG C or less.
The manufacturing method of present embodiment can further use other than above-mentioned water and containing vinylidene fluoride monomers
Other compositions.It include chain-transferring agent, polymerization initiator and suspending agent in the example of such other compositions.
Chain-transferring agent is used with adjusting the purpose of the molecular weight of obtained polymer.Chain-transferring agent can be one kind
It may be more than one.Chain-transferring agent can be from the known compound that can be used in adjusting the molecular weight containing vinylidene fluoride monomers
In suitably select.It include ethyl acetate, propyl acetate, acetone and diethyl carbonate in the example of chain-transferring agent.For example,
The amount of chain-transferring agent is relative to 100 mass parts containing vinylidene fluoride monomers, and for example, 5 below the mass.
Polymerization initiator can be for a kind of or more than one include that dicetyl peroxydicarbonate two is different in its example
Propyl ester, peroxy dicarbonate di-n-propyl ester and tert-Butyl peroxypivalate (perbutyl peroxypivalate).It is poly-
The amount of initiator is closed relative to 100 mass parts containing vinylidene fluoride monomers, for example, 0.001 mass parts~0.8 mass parts.
Suspending agent is used with improving the purpose of the dispersibility containing vinylidene fluoride monomers in water.Suspending agent can be one
Kind may be more than one.In the example of suspending agent, comprising methylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose,
Hydroxypropyl methyl cellulose, partly-hydrolysed polyvinyl acetate and acrylic acid series polymeric compounds.The amount of suspending agent is relative to containing inclined
100 mass parts of fluoride monomers, for example, 0.01 mass parts~2 mass parts.
The manufacturing method of present embodiment can carry out in the following way: supplying water into reactor, contain inclined fluorine second
Temperature in reactor is heated to polymerization temperature, and maintains the temperature by alkene monomer and the other compositions being added as needed
Degree.The actual temperature in reactor at this time is generally remained in relative in the range of polymerization temperature ± 1 DEG C.
Reactor can be in the range of can be realized the condition of suspension polymerisation of present embodiment, from well known reactor
In suitably select.In the example of reactor, include autoclave (autoclave).
In the manufacturing method of present embodiment, the pressure in reactor rises to polymerization temperature by the temperature in reactor
The critical pressure (4.38MPa) of vinylidene is spent and sufficiently exceeds, usually the maximum value in the polymerization reaction.Contain as a result,
Vinylidene in vinylidene fluoride monomers is mainly used for polymerization reaction with the state of supercritical fluid.Pressure one in reaction system
As with containing vinylidene fluoride monomers be used for polymerize and reduce.
The hypertonia in reactor when if above-mentioned reaction system is heated to polymerization temperature, sometimes for resistance to pressure
High container, if above-mentioned hypotony, polymerization reaction time is elongated and reduce productivity sometimes.From the shortening reaction time
Viewpoint considers that the pressure in reactor when above-mentioned reaction system is heated to polymerization temperature is preferably 5MPa or more, more preferably
For 5.5MPa or more.In addition, above-mentioned pressure is preferably 10MPa hereinafter, more for example from the viewpoint of the cost for cutting down reactor
Preferably 9MPa or less.The pressure can be according to supply amount and the various principal elements such as polymerization temperature containing vinylidene fluoride monomers
To adjust.
In the manufacturing method of present embodiment, as needed, it can make to react to heating for multiple times is carried out in reaction system
Temperature in system repeatedly heats up.From inhibit along with the consumption of monomer the reduction of bring pressure and the drop of reaction speed
Low, from the viewpoint of improving reaction efficiency, above-mentioned heating for multiple times is preferred.
For the terminal of suspension polymerisation, the balance of the reduction of unreacted monomer amount and the long-time of polymerization time is considered
(i.e. the productivity of product polymer) suitably selects.For example, the terminal of suspension polymerisation other than the sampling of reaction product, is gone back
It can be judged according to the heating in reaction system and the variation for the pressure being accompanied by this.
In the manufacturing method of present embodiment, vinylidene fluoride copolymers are obtained with powder.The powder passes through outstanding
Polymer paste is dehydrated after floating polymerization, washes, dry to obtain.
Manufacturing method according to the present embodiment can be improved reaction efficiency, shorten polymerization time.Specifically, to
After reactor base feed, the polymerization time that reaching time point of polymerization temperature to polymerization terminates be, for example, about 30 hours with
It is interior, and then also can be set within 20 hours.
If the bulk density of the powder of partial fluorine ethylene polymer is too low, processing degree of difficulty when post-processing sometimes increases.
In addition, there are the tendencies that above-mentioned bulk density is got higher if the pressure of the reaction system of suspension polymerisation is excessively surging.As a result, from
Inhibit reaction system pressure it is excessive it is surging from the viewpoint of, bulk density is excessively high sometimes undesirable.From post-processing
From the viewpoint of treatability, above-mentioned bulk density is for example preferably 0.20g/cm3More than, more preferably 0.25g/cm3More than.Separately
Outside, from the viewpoint of the preferred scope for realizing the pressure in reaction system, above-mentioned bulk density is, for example, 0.80g/cm3With
Under.From the viewpoint of the powder for obtaining preferred shape of particle and inhibit the powder accident it is broken from the viewpoint of, volume is close
Degree is preferred in above-mentioned range.
By previous suspension polymerisation to manufacture vinylidene fluoride copolymers, for example, in manufacture vinylidene
In the case where the copolymer of the non-fluorine system monomer containing polar functional group, in particular, there are the following problems: polymerization generated
The bulk density of the powder of object is easily reduced, and the accident that the powder is easy to produce in postprocessing working procedures is broken.However, according to this
The manufacturing method of embodiment can easily control the powder for being made as generation product in the manufacture of vinylidene fluoride copolymers
Bulk density in desired range.Therefore, the generation of such problems can be prevented.
It should be noted that the bulk density of the powder of polymer be for carried out it is antistatic after powder sample, and
The calculated value of measuring method of JIS K 6721-3.3 " bulk specific gravity " is based on about utensil and calculation method.
As the average grain diameter for the vinylidene fluoride copolymers that the manufacturing method by present embodiment obtains, preferably 80 μm
~300 μm, further preferably 130 μm~250 μm.If average grain diameter is too small, mobility reduces and becomes problem sometimes.
In addition, considering from the viewpoints such as physical property for various purposes are suitable for, obtained by the manufacturing method of present embodiment
The logarithmic viscosity number of vinylidene fluoride copolymers (makes 4g resin be dissolved to solution obtained by 1 liter of n,N-Dimethylformamide
Log viscosities at 30 DEG C) it is 0.5dL/g or more, particularly preferably it is set as the range of 0.8~4.0dL/g.
In the manufacturing method of present embodiment, without additional containing vinylidene fluoride monomers in the midway of suspension polymerisation.Therefore,
In the presence of the tendency that the composition of the monomer for suspension polymerisation is stable.As a result, from the viewpoint of the vinylidene fluoride copolymers of manufacture homogeneous
Consideration is preferred.
The vinylidene fluoride copolymers obtained by above-mentioned manufacturing method can be with the production higher than previous manufacturing method
Rate is manufactured, and various formed body formation material resins are preferably used as.
(summary)
As described above, the manufacturing method of vinylidene fluoride copolymers of the invention includes: to containing vinylidene and can be with
The process for carrying out suspension polymerisation containing vinylidene fluoride monomers of the other monomers of vinylidene copolymerization, in the process, in inclined fluorine
Ethylene includes the step disposably put into containing vinylidene fluoride monomers as being polymerize under the conditions of the temperature of supercriticality
Suddenly.
In an arrangement, it is preferred that the manufacturing method of vinylidene fluoride copolymers of the invention is at 35 DEG C~65 DEG C
It is polymerize in temperature range.
In an arrangement, it is preferred that in the manufacturing method of vinylidene fluoride copolymers of the invention, other described lists
Body is one or both of monomethyl maleate and hexafluoropropene.
In an arrangement, it is preferred that in the manufacturing method of vinylidene fluoride copolymers of the invention, in the process
Middle to use polymerization initiator, the amount of the polymerization initiator is 0.001 mass parts relative to 100 mass parts containing vinylidene fluoride monomers
~0.8 mass parts.
In an arrangement, it is preferred that in the manufacturing method of vinylidene fluoride copolymers of the invention, in the process
Obtained in vinylidene fluoride copolymers average grain diameter be 80 μm~300 μm.
Hereinafter, being illustrated by embodiment, comparative example to further progress of the present invention.
[embodiment]
The bulk density of vinylidene fluoride copolymers powder obtained in embodiment and comparative example by the following method into
Measurement is gone.
(bulk density)
The bulk density of vinylidene fluoride copolymers powder be based on JIS K 6721-3.3 " bulk specific gravity " measuring method into
Measurement is gone.Specifically, being directed to powder sample 100g, 5% ethanol solution 2mL of surfactant is added, spatula is used
(spatula) it after fully stirring, places 10 minutes.Powder sample 120mL of the progress after antistatic is put into ratio in bulk
After in the funnel inserted with baffle (damper) of weight measurement device, promptly extracts baffle out, sample is made to fall on receiver.Use glass
After glass stick scrapes the sample overflowed from receiver, the quality for being put into the receiver of sample is accurately weighed to 0.1g, is led to
It crosses following formula and calculates bulk density.
S=(C-A)/B
S: bulk density (g/cm3)
A: the quality (g) of receiver
B: the internal volume (cm of receiver3)
C: it is put into the quality (g) of the receiver of sample
(average grain diameter)
For the size distribution of vinylidene fluoride copolymers powder, uses (strain) flat work to make made Luo Taipu Formula II type and vibrate
Screen(ing) machine D type is determined according to JIS K 0069-3.1 by dry screen point-score.Calculating for average grain diameter is based on grain
The measurement result for spending distribution, is acquired by logarithm normal distribution method.For average grain diameter, use in granularity cumulative distribution
Indicate the partial size of 50% accumulated value (D50).
(embodiment 1)
Into the autoclave of internal volume 2L, with ion exchange water 1040g, suspending agent (methylcellulose) 0.6g, chain tra nsfer
Agent (ethyl acetate) 3.2g and polymerization initiator (di-isopropyl peroxydicarbonate (IPP)) 1.8g together, are loaded as containing
The mixture of vinylidene (VDF) 396g and monomethyl maleate (MMM) 4g of vinylidene fluoride monomers are being warming up to as poly-
After 50 DEG C for closing temperature, maintains 15.7 hours, thus implement suspension polymerisation.
After polymerization, obtained polymer paste is dehydrated, is washed, and then drying 20 is small at 80 DEG C
When, obtain the copolymer powder 393g of vinylidene and monomethyl maleate.It is calculated according to supply amount containing vinylidene fluoride monomers
The yield of polymer out is 98.3%.In addition, the bulk density of the powder of obtained polymer is 0.31g/cm3, than dense
Log viscosities are 0.99dL/g.
(embodiment 2)
Into the autoclave of internal volume 2L, with ion exchange water 1040g, suspending agent (methylcellulose) 0.6g, chain tra nsfer
Agent (ethyl acetate) 4.8g and polymerization initiator (tert-Butyl peroxypivalate (PB-PV)) 2.0g together, are loaded as containing
The mixture of vinylidene (VDF) 396g and monomethyl maleate (MMM) 4g of vinylidene fluoride monomers are being warming up to as poly-
After 50 DEG C for closing temperature, maintains 24.0 hours, implement suspension polymerisation.
After polymerization, obtained polymer paste is dehydrated, is washed, and then drying 20 is small at 80 DEG C
When, obtain the copolymer powder 368g of vinylidene and monomethyl maleate.It is calculated according to supply amount containing vinylidene fluoride monomers
The yield of polymer out is 92.0%.In addition, the bulk density of the powder of obtained polymer is 0.30g/cm3, than dense
Log viscosities are 1.18dL/g.
(embodiment 3)
Other than being set as 1.2g by the amount of ethyl acetate, the time for being maintained at 50 DEG C is set as 7.8 hours, with embodiment
1 similarly implements suspension polymerisation.
After polymerization, obtained polymer paste is dehydrated, is washed, and then drying 20 is small at 80 DEG C
When, obtain the copolymer powder 366g of vinylidene and monomethyl maleate.It is calculated according to supply amount containing vinylidene fluoride monomers
The yield of polymer out is 91.5%.In addition, the bulk density of the powder of obtained polymer is 0.30g/cm3, than dense
Log viscosities are 1.25dL/g.
(embodiment 4)
Into the autoclave of internal volume 2L, with ion exchange water 1040g, suspending agent (methylcellulose) 0.6g, chain tra nsfer
Agent (diethyl carbonate) 2.0g and polymerization initiator (tert-Butyl peroxypivalate (PB-PV)) 1.4g together, are loaded as
The mixture of vinylidene (VDF) 396g and monomethyl maleate (MMM) 6g containing vinylidene fluoride monomers, are being warming up to conduct
After 60 DEG C of polymerization temperature, maintains 20.3 hours, thus implement suspension polymerisation.
After polymerization, obtained polymer paste is dehydrated, is washed, and then drying 20 is small at 80 DEG C
When, obtain the copolymer powder 344g of vinylidene and monomethyl maleate.It is calculated according to supply amount containing vinylidene fluoride monomers
The yield of polymer out is 84.8%.In addition, the bulk density of the powder of obtained polymer is 0.25g/cm3, than dense
Log viscosities are 1.21dL/g.
(embodiment 5)
Into the autoclave of internal volume 2L, with ion exchange water 1110g, suspending agent (methylcellulose) 0.6g, Yi Jiju
It closes initiator (di-isopropyl peroxydicarbonate (IPP)) 0.9g and together, is loaded as the vinylidene containing vinylidene fluoride monomers
(VDF) mixture of 398g, hexafluoropropene (HFP) 32g and monomethyl maleate (MMM) 6.5g, is being warming up to as polymerization
After 50 DEG C of temperature, maintains 20.3 hours, thus implement suspension polymerisation.
After polymerization, obtained polymer paste is dehydrated, is washed, and then drying 20 is small at 80 DEG C
When, obtain the copolymer powder 404g of vinylidene Yu hexafluoropropene and monomethyl maleate.According to containing vinylidene fluoride monomers
The yield of the calculated polymer of supply amount is 92.5%.In addition, the bulk density of the powder of obtained polymer is
0.32g/cm3, logarithmic viscosity number 2.82dL/g.(comparative example 1)
Into the autoclave of internal volume 2L, with ion exchange water 1040g, suspending agent (methylcellulose) 0.8g, chain tra nsfer
Agent (ethyl acetate) 2.0g and polymerization initiator (di-isopropyl peroxydicarbonate (IPP)) 4.0g together, are loaded as containing
The mixture of vinylidene (VDF) 400g and monomethyl maleate (MMM) 4g of vinylidene fluoride monomers are being warming up to as poly-
After 26 DEG C for closing temperature, maintains 41.7 hours, thus implement suspension polymerisation.
After polymerization, obtained polymer paste is dehydrated, is washed, and then drying 20 is small at 80 DEG C
When, obtain the copolymer powder 364g of vinylidene and monomethyl maleate.It is calculated according to supply amount containing vinylidene fluoride monomers
The yield of polymer out is 90.9%.In addition, the bulk density of the powder of obtained polymer is 0.45g/cm3, than dense
Log viscosities are 1.19dL/g.
By the polymerizing condition of above-described embodiment and comparative example, the yield and volume of obtained vinylidene fluoride copolymers
Density is shown in table 1.
[table 1]
Claims (5)
1. a kind of manufacturing method of vinylidene fluoride copolymers, which is characterized in that
Include: suspending to the vinylidene fluoride monomers that contain containing vinylidene and the other monomers that can be copolymerized with vinylidene
The process of polymerization,
In the process, it is polymerize under the conditions of vinylidene becomes the temperature of supercriticality,
It is described disposably to be put into containing vinylidene fluoride monomers.
2. the manufacturing method of vinylidene fluoride copolymers according to claim 1, which is characterized in that
In 35 DEG C~65 DEG C of temperature
It is polymerize in range.
3. the manufacturing method of vinylidene fluoride copolymers according to claim 1 or 2, which is characterized in that
The other monomers are one or both of monomethyl maleate and hexafluoropropene.
4. the manufacturing method of vinylidene fluoride copolymers according to any one of claim 1 to 3, which is characterized in that in institute
It states using polymerization initiator in process, the amount of the polymerization initiator is 0.001 relative to 100 mass parts of vinylidene fluoride monomers are contained
Mass parts~0.8 mass parts.
5. the manufacturing method of vinylidene fluoride copolymers according to any one of claim 1 to 4, which is characterized in that
The average grain diameter of the vinylidene fluoride copolymers obtained in the process is 80 μm~300 μm.
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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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| WO2002010233A1 (en) * | 2000-07-31 | 2002-02-07 | Solvay (Societe Anonyme) | Vinylidene fluoride polymers, process for manufacturing them and use thereof |
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| JP3371001B2 (en) * | 1991-08-01 | 2003-01-27 | 呉羽化学工業株式会社 | Vinylidene fluoride polymer and method for producing the same |
| JP3121943B2 (en) * | 1992-12-02 | 2001-01-09 | 呉羽化学工業株式会社 | Vinylidene fluoride copolymer |
| US20130090439A1 (en) | 2011-10-05 | 2013-04-11 | Honeywell International Inc. | Polymerization Of 2,3,3,3-Tetrafluoropropene And Polymers Formed From 2,3,3,3-Tetrafluoropropene |
| CN103988121B (en) | 2011-12-06 | 2017-03-15 | 株式会社Lg化学 | Liquid crystal cells |
| CN104272502B (en) | 2012-06-28 | 2016-12-21 | 株式会社吴羽 | The manufacture method of rechargeable nonaqueous electrolytic battery resin molding and rechargeable nonaqueous electrolytic battery resin molding |
| US9850394B2 (en) | 2012-06-28 | 2017-12-26 | Kureha Corporation | Resin composition, filler-containing resin film for non-aqueous electrolyte secondary battery, and method for producing filler-containing resin film for non-aqueous electrolyte secondary battery |
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| CN112375169A (en) * | 2020-07-31 | 2021-02-19 | 万向一二三股份公司 | Novel binder synthesis method |
| CN112375169B (en) * | 2020-07-31 | 2022-08-02 | 万向一二三股份公司 | Method for synthesizing binder |
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