US20060281845A1 - Aqueous process for making fluoropolymers - Google Patents

Aqueous process for making fluoropolymers Download PDF

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Publication number
US20060281845A1
US20060281845A1 US11/149,797 US14979705A US2006281845A1 US 20060281845 A1 US20060281845 A1 US 20060281845A1 US 14979705 A US14979705 A US 14979705A US 2006281845 A1 US2006281845 A1 US 2006281845A1
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United States
Prior art keywords
polyethylene glycol
fluoropolymer
emulsifier
polymerization
fluorinated
Prior art date
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Abandoned
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US11/149,797
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English (en)
Inventor
Ramin Amin-Sanayei
Christyn Olmstead
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Arkema Inc
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Arkema Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arkema Inc filed Critical Arkema Inc
Priority to US11/149,797 priority Critical patent/US20060281845A1/en
Assigned to ARKEMA INC. reassignment ARKEMA INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AMIN-SANAYEI, RAMIN, OLMSTEAD, CHRISTYN
Priority to EP06770939A priority patent/EP1891153B1/en
Priority to PCT/US2006/019894 priority patent/WO2006135543A2/en
Priority to KR1020087000767A priority patent/KR101298055B1/ko
Priority to CN2006800207481A priority patent/CN101223228B/zh
Priority to AT06770939T priority patent/ATE535553T1/de
Priority to ES06770939T priority patent/ES2376079T3/es
Priority to JP2008515733A priority patent/JP5112303B2/ja
Priority to US11/635,954 priority patent/US8080621B2/en
Priority to US11/635,873 priority patent/US8338518B2/en
Publication of US20060281845A1 publication Critical patent/US20060281845A1/en
Priority to US11/689,883 priority patent/US8158734B2/en
Priority to US13/297,884 priority patent/US8765890B2/en
Priority to US13/681,648 priority patent/US9068071B2/en
Abandoned legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • 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
    • C08F14/00—Homopolymers and 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
    • C08F14/18—Monomers containing fluorine
    • C08F14/22—Vinylidene fluoride
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • the invention relates to a process for making fluoropolymers using non-fluorinated, non-ionic emulsifiers.
  • the emulsifiers contain segments of polyethylene glycol and/or polypropylene glycol.
  • Fluoropolymers are generally made by an aqueous dispersion process, which provides a suitable heat sink for controlling the heat of polymerization and can produce a high yield and high molecular weight relative to polymerization conducted in an organic solvent.
  • a suitable surfactant or emulsifier In order to achieve stable dispersion or emulsion, a suitable surfactant or emulsifier must be employed. Fluorinated-surfactants are generally used because they can yield stable particle and high molecular weight fluoropolymers. However, the fluorinated-surfactants typically used in emulsion polymerization of fluoropolymers, such as the ammonium salt of perfluoro octanoic acid or salts of perfluoro sulfonic acids are expensive. They also present an environmental concern related to bio-persistence.
  • Emulsion polymerization of vinylidene fluoride at moderate pressures and temperatures using fluorinated surfactants, free radical initiators, and trichlorofluoromethane as chain transfer agent is taught in the U.S. Pat. No. 4,569,978 in which VF2 based polymers are produced with reduced tendency to generate cavity and greater resistance to discoloration at elevated temperatures.
  • the process was refined in the U.S. Pat. No. 6,734,264 wherein particularly ozone depleting agent (trichlorofluoromethane) was replace by propane which is environmentally friendly chemical. It is noteworthy that in both processes fluorinated surfactant was needed to produce stable emulsion.
  • perfluorocarboxylate salts was used to stabilize fluoropolymer emulsion polymerizations, with the most common example being ammonium perfluorooctanoate or ammonium perfluoronanoate.
  • the high degree of fluorination is thought to be necessary to prevent chain transfer reaction between a growing polymer chain and the surfactant which in turn may result in lowering molecular weight and/or inhibition of the polymerization.
  • Emulsifier-free aqueous emulsion polymerization process for making fluoropolymer such as TFE and/or VDF copolymers is described in U.S. Pat. No. 6,693,152.
  • emulsifier free emulsion polymerization first only inorganic ionic initiators such as persulfates or permangamates may work whereas organic peroxide initiators would not work.
  • the particle size of emulsifier free emulsion of fluoropolymers would be large; as a result, the shelf-life of latex would be very limited.
  • the solid content of emulsifier free latex is limited to low or moderate solids, where in fact a high solid latex is desirable in variety of commercial applications.
  • a fluoropolymer can be made by a process using non-fluorinated, non-ionic emulsifiers containing segments of polyethylene glycol and/or polypropylene glycol having varieties of different terminal groups and functions.
  • the fluoropolymer dispersions produced have good latex stability and shelf-life, and are coagulum and adhesion free.
  • the invention describes an aqueous fluoropolymer composition
  • aqueous fluoropolymer composition comprising
  • the invention also describes a process for preparing a fluoropolymer comprising polymerizing at least one fluoromonomer in an aqueous medium comprising at least one emulsifier consisting of a non-fluorinated, non-ionic emulsifier containing polyethylene glycol and/or polypropylene glycol segments with repeating units between 2 to 200.
  • fluoromonomer as used according to the invention means a fluorinated and olefinically unsaturated monomer capable of undergoing free radical polymerization reaction.
  • Suitable exemplary fluoromonomers for use according to the invention include, but are not limited to, vinylidene fluoride, vinyl fluoride, trifluoroethylene, tetrafluoroethylene (TFE), and hexafluoropropylene (HFP) and their respected copolymers.
  • fluoropolymer refers to polymers and copolymers (including polymers having two or more different monomers, including for example terpolymers) containing at least 50 mole percent of fluoromonomer units.
  • vinylidene fluoride polymer used herein includes both normally solid, high molecular weight homopolymers and copolymers within its meaning. Such copolymers include those containing at least 50 mole percent of vinylidene fluoride copolymerized with at least one comonomer selected from the group consisting of tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, hexafluoropropene, vinyl fluoride, pentafluoropropene, perfluoromethyl vinyl ether, perfluoropropyl vinyl ether and any other monomer that would readily copolymerize with vinylidene fluoride.
  • comonomer selected from the group consisting of tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, hexafluoropropene, vinyl fluoride, pentafluoropropene, perfluoromethyl vinyl ether, perfluoropropyl vinyl ether and any other
  • copolymers composed of from at least about 70 and up to 99 mole percent vinylidene fluoride, and correspondingly from 1 to 30 percent tetrafluoroethylene, such as disclosed in British Patent No. 827,308; and about 70 to 99 percent vinylidene fluoride and 1 to 30 percent hexafluoropropene (see for example U.S. Pat. No. 3,178,399); and about 70 to 99 mole percent vinylidene fluoride and 1 to 30 mole percent trifluoroethylene.
  • Terpolymers of vinylidene fluoride, hexafluoropropene and tetrafluoroethylene such as described in U.S. Pat. No.
  • 2,968,649 and terpolymers of vinylidene fluoride, trifluoroethylene and tetrafluoroethylene are also representatives of the class of vinylidene fluoride copolymers which can be prepared by the process embodied herein.
  • Emulsifiers suitable for use in this invention are non-fluorinated non-ionic emulsifiers containing segments of polyethylene glycol (PEG), polypropylene glycol (PPG) or a combination thereof, with repeating units between 2 to 200, preferably between 3 to 100, and more preferably 5 to 50.
  • the glycol-based emulsifiers used in this invention include, but are not limited to, polyethylene glycol acrylate (PEGA), polyethylene glycol (PEG), polyethylene glycol phenol oxide (Triton X-100), polypropylene glycol acrylate (PPGA), and polypropylene glycol (PPG).
  • the emulsifier may contain the same or different terminal groups on each end, such as hydroxyl, carboxylate, benzoate, sulfonic, phosphonic, acrylate, methacrylate, ether, hydrocarbon, phenol, functionalized phenol, ester, fatty ester, and the like.
  • the terminal group can contain halogen atoms like F, Cl, Br and I, and also other groups or functions such as amine, amid, cycle hydrocarbon, and others.
  • polyethylene glycol acrylate with Mn 375, polyethylene glycol with Mn 570, and polyethylene glycol with phenol oxide end group and many other example can be used in this invention to produce stable fluoropolymer latex with small particle size.
  • the chemical structure of the emulsifier of this invention could be altered so that PEG and/or PPG would not be the main backbone but the essential properties such as water solubility, chain transfer activities, and protective behaviors remains the same.
  • the emulsifier is used at a level of from 100 ppm to 2 percent, 100 ppm to 1 percent and 100 ppm to 1 ⁇ 2 percent, based on the total polymer solids of the fluoropolymer formed.
  • the emulsifier of this invention could be added all upfront prior to polymerization, fed continuously during the polymerization, fed partly before and then during polymerization, or fed after polymerization started and progressed for a while.
  • the reactor temperature is raised to the desired polymerization temperature, the predetermined amount of either vinylidene fluoride alone or a mixture of monomers such as vinylidene fluoride and hexafluoropropylene are fed to the reactor.
  • the temperature of the reaction can vary depending on the characteristics of the initiator used, but is typically from about 30° to 140° C., preferably from about 50° to 130° C.
  • an initiator solution made of either potassium persulfate, ammonium persulfate, or an emulsion of one or more organic peroxides such as propyl peroxidicarbonate, or dibutylperoxide in water, is charged to start the polymerization reaction.
  • the polymerization pressure may vary, but typically will be within the range of about 20 to 50 atmospheres.
  • the vinylidene fluoride or vinylidene/hexafluoropropylene mixture is continuously fed along with additional initiator to maintain the desired pressure.
  • the monomer feed(s) will be stopped, but initiator feed is continued to consume residual monomer(s).
  • a shot of vinylidene fluoride is added to bring the vinylidene fluoride concentration up. This step may be repeated more than one time depending on the hexafluoropropylene concentration in the reactor.
  • the initiator charge is stopped and after a delay time the reactor is cooled.
  • the unreacted monomer(s) are vented and the latex is recovered from the reactor.
  • the polymer may then be isolated from the latex by standard methods, such as acid coagulation, freeze thaw or shear coagulation.
  • a paraffin antifoulant is an optional additive, and any long-chain, saturated, hydrocarbon wax or oil may be used for this purpose.
  • Reactor loadings of the paraffin typically are from 0.01 percent to 0.3 percent by weight on the total monomer weight used.
  • a chain transfer agent may be added all at once at the beginning of the reaction, or it may be added in portions, or continuously throughout the course of the reaction.
  • the amount of chain transfer agent added and its mode of addition depends on the desired molecular weight characteristics, but is normally used in an amount of from about 0.5 percent to about 5 percent based on total monomer weight used, preferably from about 0.5 percent to about 2 percent.
  • the initial monomer charge ratio and the incremental monomer feed ratio during polymerization can be adjusted according to apparent reactivity ratios to avoid compositional drift in the final copolymer product.
  • the reaction can be started and maintained by the addition of any suitable initiator known for the polymerization of fluorinated monomers including inorganic peroxides, “redox” combinations of oxidizing and reducing agents, and organic peroxides.
  • suitable initiator known for the polymerization of fluorinated monomers
  • inorganic peroxides include inorganic peroxides, “redox” combinations of oxidizing and reducing agents, and organic peroxides.
  • typical inorganic peroxides are the ammonium or alkali metal salts of persulfates, which have useful activity in the 65° C. to 105° C. temperature range.
  • Redox systems can operate at even lower temperatures and examples include combinations of oxidants such as hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, or persulfate, and reductants such as reduced metal salts, iron (II) salts being a particular example, optionally combined with activators such as sodium formaldehyde sulfoxylate, metabisulfite, or ascorbic acid.
  • oxidants such as hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, or persulfate
  • reductants such as reduced metal salts, iron (II) salts being a particular example, optionally combined with activators such as sodium formaldehyde sulfoxylate, metabisulfite, or ascorbic acid.
  • activators such as sodium formaldehyde sulfoxylate, metabisulfite, or ascorbic acid.
  • organic peroxides which can be used for the polymerization are the classes of dial
  • dialkyl peroxides is di-t-butyl peroxide, of peroxyesters are t-butyl peroxypivalate and t-amyl peroxypivalate, and of peroxydicarbonate, and di(n-propyl)peroxydicarbonate, diisopropyl peroxydicarbonate, di(sec-butyl)peroxydicarbonate, and di(2-ethylhexyl)peroxydicarbonate.
  • diisopropyl peroxydicarbonate for vinylidene fluoride polymerization and copolymerization with other fluorinated monomers is taught in U.S. Pat. No.
  • PEG and/or PPG emulsifier as the sole emulsifiers
  • co-emulsifiers or co-surfactants could also be present in the invention, including fluorinated or partially fluorinated emulsifiers.
  • the process of present invention is easy, convenient, cost effective, and more importantly is coagulum and adhesion free.
  • the resulting polymer dispersions have good latex stability and shelf-life, and a good quality of film formation. Additionally, the particle size of dispersion could be small ( ⁇ 100 nm) which in turn would be advantageous for many direct applications of fluoropolymer in a latex form. Furthermore, the fluoropolymer produced with the process of this invention, has a higher purity, with less extractable ions and less low molecular weight polymers.
  • the glycol-based emulsifiers used in this example include polyethylene glycol acrylate (PEGA), polyethylene glycol (PEG), and polyethylene glycol phenol oxide (Triton X-100), polypropylene glycol acrylate (PPGA), and polypropylene glycol (PPG). Inspection of results in the following table indicates that a with a low loading of the emulsifiers, emulsions of fluoropolymers having particle sizes of approximately 100 nm were produced. The solid level of these novel emulsions were as high as 42%.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US11/149,797 2005-06-10 2005-06-10 Aqueous process for making fluoropolymers Abandoned US20060281845A1 (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
US11/149,797 US20060281845A1 (en) 2005-06-10 2005-06-10 Aqueous process for making fluoropolymers
JP2008515733A JP5112303B2 (ja) 2005-06-10 2006-05-23 フルオロポリマーの水性製造方法
ES06770939T ES2376079T3 (es) 2005-06-10 2006-05-23 Procedimiento acuoso para la preparación de fluorpol�?meros.
PCT/US2006/019894 WO2006135543A2 (en) 2005-06-10 2006-05-23 Aqueous process for making fluoropolymers
KR1020087000767A KR101298055B1 (ko) 2005-06-10 2006-05-23 불소 중합체의 수성 제조방법
CN2006800207481A CN101223228B (zh) 2005-06-10 2006-05-23 制备含氟聚合物的水性方法
AT06770939T ATE535553T1 (de) 2005-06-10 2006-05-23 Wässriges verfahren zur herstellung von fluorpolymeren
EP06770939A EP1891153B1 (en) 2005-06-10 2006-05-23 Aqueous process for making fluoropolymers
US11/635,873 US8338518B2 (en) 2005-06-10 2006-12-08 Aqueous process for making a stable fluoropolymer dispersion
US11/635,954 US8080621B2 (en) 2005-06-10 2006-12-08 Aqueous process for making fluoropolymers
US11/689,883 US8158734B2 (en) 2005-06-10 2007-03-22 Aqueous process for making fluoropolymers
US13/297,884 US8765890B2 (en) 2005-06-10 2011-11-16 Aqueous process for making fluoropolymers
US13/681,648 US9068071B2 (en) 2005-06-10 2012-11-20 Aqueous process for making a stable fluoropolymer dispersion

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US11/149,797 US20060281845A1 (en) 2005-06-10 2005-06-10 Aqueous process for making fluoropolymers

Related Child Applications (3)

Application Number Title Priority Date Filing Date
US11/635,954 Continuation-In-Part US8080621B2 (en) 2005-06-10 2006-12-08 Aqueous process for making fluoropolymers
US11/635,873 Continuation-In-Part US8338518B2 (en) 2005-06-10 2006-12-08 Aqueous process for making a stable fluoropolymer dispersion
US11/689,883 Division US8158734B2 (en) 2005-06-10 2007-03-22 Aqueous process for making fluoropolymers

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US11/149,797 Abandoned US20060281845A1 (en) 2005-06-10 2005-06-10 Aqueous process for making fluoropolymers
US11/689,883 Active 2027-12-08 US8158734B2 (en) 2005-06-10 2007-03-22 Aqueous process for making fluoropolymers

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EP (1) EP1891153B1 (enrdf_load_stackoverflow)
JP (1) JP5112303B2 (enrdf_load_stackoverflow)
KR (1) KR101298055B1 (enrdf_load_stackoverflow)
CN (1) CN101223228B (enrdf_load_stackoverflow)
AT (1) ATE535553T1 (enrdf_load_stackoverflow)
ES (1) ES2376079T3 (enrdf_load_stackoverflow)
WO (1) WO2006135543A2 (enrdf_load_stackoverflow)

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WO2011014715A2 (en) 2009-07-31 2011-02-03 3M Innovative Properties Company Fluoropolymer compositions containing a polyol compound and methods of making them
US20110034632A1 (en) * 2008-04-07 2011-02-10 Arkema Inc, Polymerization of fluoropolymers using polycaprolactone
EP2284200A1 (en) 2009-07-31 2011-02-16 3M Innovative Properties Company Aqueous fluoropolymer dispersions containing a polyol comprising at least one long chain residue and method for producing them
WO2012064858A1 (en) 2010-11-09 2012-05-18 E. I. Du Pont De Nemours And Company Reducing the telogenic behavior of hydrocarbon-containing surfactants in aqueous dispersion fluoromonomer polymerization
US8563670B2 (en) 2010-11-09 2013-10-22 E I Du Pont De Nemours And Company Nucleation in aqueous polymerization of fluoromonomer
US8735520B2 (en) 2010-11-09 2014-05-27 E.I. Du Pont De Nemours And Company Vinyl fluoride polymerization and aqueous dispersion of vinyl fluoride polymer
US9255164B2 (en) 2010-11-09 2016-02-09 The Chemours Company Fc, Llc Aqueous polymerization of perfluoromonomer using hydrocarbon surfactant
US9676929B2 (en) 2013-11-26 2017-06-13 The Chemours Company Fc, Llc Employing polyalkylene oxides for nucleation in aqueous polymerization of fluoromonomer
CN110709466A (zh) * 2017-06-06 2020-01-17 阿科玛法国公司 含氟聚合物热塑性弹性体
CN111148772A (zh) * 2017-09-27 2020-05-12 阿科玛法国公司 通过raft乳液聚合合成不含表面活性剂的聚(偏二氟乙烯)胶乳
EP3765530A4 (en) * 2018-03-16 2022-01-12 Arkema Inc. SURFACTANT-FREE HIGH SOLIDS FLUOROPOLYMER
EP4378966A4 (en) * 2021-06-11 2025-08-06 Zhonghao Chenguang Res Institute Of Chemical Industry Company Limited POLYETHER DIACID OR POLYETHER DIACID SALT SURFACTANT, AND USE THEREOF

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US8338518B2 (en) * 2005-06-10 2012-12-25 Arkema Inc. Aqueous process for making a stable fluoropolymer dispersion
US20080015304A1 (en) 2006-07-13 2008-01-17 Klaus Hintzer Aqueous emulsion polymerization process for producing fluoropolymers
US7728087B2 (en) * 2005-12-23 2010-06-01 3M Innovative Properties Company Fluoropolymer dispersion and method for making the same
US9000069B1 (en) 2010-07-02 2015-04-07 The Sherwin-Williams Company Self-stratifying coatings
US11111612B2 (en) 2014-05-19 2021-09-07 Arkema Inc. High melt flow fluoropolymer composition
EP3194457B1 (en) * 2014-09-17 2018-11-21 Solvay Specialty Polymers Italy S.p.A. Vinylidene fluoride polymers
EP3059265B1 (en) 2015-02-23 2020-10-07 3M Innovative Properties Company Peroxide curable fluoropolymers obtainable by polymerization with non-fluorinated emulsifiers
US10633468B2 (en) 2016-04-01 2020-04-28 Arkema Inc. 3-D printed fluoropolymer structures
US11629249B2 (en) * 2016-10-05 2023-04-18 Solvay Specialty Polymers Italy S.P.A. Vinylidene fluoride and trifluoroethylene containing polymers latexes
KR102120447B1 (ko) * 2017-11-22 2020-06-09 한국화학연구원 폴리에틸렌글리콜을 이용한 폴리비닐리덴 플루오라이드 나노 입자의 제조방법 및 이에 따라 제조되는 폴리비닐리덴 플루오라이드 나노 입자
JP6768176B2 (ja) 2018-05-31 2020-10-14 株式会社クレハ 非水電解質二次電池用樹脂組成物、ならびにこれを用いた非水電解質二次電池用セパレータ、電極合剤層用樹脂組成物、非水電解質二次電池用電極、および非水電解質二次電池
WO2020101963A2 (en) 2018-11-12 2020-05-22 Arkema Inc. Process for making a fluoropolymer dispersion
JP2022512330A (ja) 2018-12-06 2022-02-03 アーケマ・インコーポレイテッド フッ素－熱可塑性エラストマーブレンド
US12054605B2 (en) 2019-03-29 2024-08-06 Kureha Corporation Vinylidene fluoride-based polymer composition obtained using non-fluorinated surfactant and production method therefor
CN116075527B (zh) 2020-08-06 2025-06-24 阿科玛股份有限公司 可加工的四氟乙烯共聚物
JPWO2022071232A1 (enrdf_load_stackoverflow) * 2020-09-30 2022-04-07
US20240002553A1 (en) 2020-10-01 2024-01-04 The Chemours Company Fc, Llc Employing low reactivity hydrocarbon dispersing agent in aqueous polymerization of fluoropolymers
EP4438632A1 (en) 2023-03-29 2024-10-02 Arkema France Polyvinylidene fluoride for high purity water supply applications
EP4458869A1 (en) 2023-05-03 2024-11-06 Arkema, Inc. Process for the production of polyvinylidene fluoride copolymers

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