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WO2009013214A1 - Procédé de préparation de dispersions de polymères - Google Patents

Procédé de préparation de dispersions de polymères Download PDF

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Publication number
WO2009013214A1
WO2009013214A1 PCT/EP2008/059367 EP2008059367W WO2009013214A1 WO 2009013214 A1 WO2009013214 A1 WO 2009013214A1 EP 2008059367 W EP2008059367 W EP 2008059367W WO 2009013214 A1 WO2009013214 A1 WO 2009013214A1
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process according
surfactants
dispersion
polymerization
fluohnated
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Inventor
Valeri Kapeliouchko
Tiziana Poggio
Stefana Musio
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Solvay Specialty Polymers Italy SpA
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Solvay Solexis SpA
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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
    • 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
    • C08F14/26—Tetrafluoroethene

Definitions

  • the present invention relates to a process for obtaining aqueous dispersions of TFE-based perfluoropolymers, which are totally free of fluohnated surfactants.
  • the TFE-based fluoropolymers of the dispersions of the present invention may be either thermoprocessable, for instance MFA (tetrafluoro- ethylene/perfluoromethyl vinyl ether copolymer) and PFA (tetrafluoro- ethylene/perfluoropropyl vinyl ether copolymer), or non-thermoprocessable, such as polytetrafluoroethylene (PTFE) homopolymer or modified.
  • MFA tetrafluoro- ethylene/perfluoromethyl vinyl ether copolymer
  • PFA tetrafluoro- ethylene/perfluoropropyl vinyl ether copolymer
  • non-thermoprocessable such as polytetrafluoroethylene (PTFE) homopolymer or modified.
  • fluoropolymer dispersions free of fluorinated surfactants means that the dispersion does not contain fluohnated surfactants to levels of 30 ppb (parts per billion) or less, relative to the weight of the fluoropolymer.
  • thermoprocessable polymers in particular thermoprocessable fluoropolymers, means polymers that are melt-processable by means of conventional extrusion devices (melt-extrusion and injection).
  • melt-extrusion and injection melt-extrusion and injection
  • viscosity of the melt ASTM D-1238-52T
  • thermoprocessable fluoropolymers at the process temperature is not greater than 10 7 poises.
  • non-thermoprocessable polymers in particular non-thermoprocessable fluoropolymers, means fluoropolymers that are not melt- processable via conventional techniques.
  • the viscosity of the melt determined by means of the same ASTM standard, for non-thermoprocessable fluoropolymers at the process temperature is greater than 10 7 poises, preferably from 10 7 to 10 13 poises and even more preferably from 10 9 to 10 12 poises.
  • thermoprocessable and non-thermoprocessable TFE-based fluoropolymers are used in many applications, for instance coating, manufactured products, impregnated fabrics, etc.
  • Thermoprocessable and non-thermoprocessable fluoropolymers are mainly produced via two different polymerization processes: suspension polymerization and emulsion polymerization.
  • the surfactant may be absent or used in small amounts.
  • the polymers obtained are in the form of particles of the order of millimetres in size.
  • the fluohnated monomers are dispersed in an aqueous phase in the presence of a surfactant capable of stabilizing the polymer latex that forms during the polymerization.
  • the polymerization is performed until a conversion equal to 15-35% by weight of fluoropolymer is obtained, and is performed in the presence of gentle stirring so as to prevent coagulation of the polymer.
  • the surfactants used must be non-telogenic so as to avoid chain transfer and thus obtain high molecular weight fluoropolymers therefore endowed with high mechanical properties. See patent US 2 559 752.
  • dispersions with higher concentrations, even up to about 75% by weight, of polymer may be obtained by using concentration processes known in the art. See, for example, US 3 037 953 and US 4 369 266.
  • the latex is coagulated to obtain fine powders, of the order of about 500 microns in size in the case of PTFE homopolymer.
  • the surfactants used with improved stabilizing efficacy are fluorinated surfactants, for example perfluorooctanoic acid or salts thereof.
  • the latter surfactant is the one most commonly used industrially and allows the production of dispersions of high molecular weight fluoropolymers.
  • the TFE-based fluoropolymer dispersions that may be obtained by emulsion polymerization in the presence of fluorinated anionic surfactants, for instance PFOA, have the following characteristics:
  • ⁇ mean particle diameter of from 10 nm to 400 nm
  • ⁇ amount of fluorinated anionic surfactants of from 800 ppm to 10,000 ppm and preferably from 1 ,200 ppm to 6,000 ppm, relative to the weight of the polymer.
  • Aqueous emulsion polymerization of fluorinated monomers to produce fluoropolymers in which fluorinated surfactants of PFOA type are neither used nor added during the polymerization are also known.
  • fluorinated surfactants are formed during the polymerization. See, for example, patent application US 2007/0 072 985, which describes a process for preparing fluoropolymers that comprises the aqueous emulsion polymerization of one or more fluorinated monomers, optionally in the presence of one or more fluorinated comonomers, the polymerization being initiated in the absence of fluorinated surfactants and no fluorinated surfactant is added during the polymerization.
  • the fluoropolymer is recovered from the dispersion, thus obtaining the fluoropolymer and effluent water, which is placed in contact with anion-exchange resin.
  • the aqueous fluoropolymer dispersions obtained may be placed in contact with anion-exchange resin and subsequently separated from the resin.
  • One subject of the present invention is a process for preparing dispersions of TFE-based perfluoropolymers with a high melt viscosity, which are thermoprocessable and non-thermoprocessable, comprising: a) aqueous-phase suspension polymerization of TFE, optionally in the presence of one or more ethylenically unsaturated fluorinated comonomers, in the presence of a radical initiator, without the initial addition of fluorinated surfactants, without the addition of fluorinated surfactants during the polymerization, and without any in situ formation of fluorinated surfactants.
  • the polymerization is performed by working at a temperature generally of between about 20 °C and about 120°C, preferably between 30 °C and 100°C and more preferably between 40 °C and 90 °C.
  • a temperature generally of between about 20 °C and about 120°C, preferably between 30 °C and 100°C and more preferably between 40 °C and 90 °C.
  • Non-fluohnated water- soluble initiators are used.
  • a redox couple, for instance APS and (NH 4 ) 2 Fe(SO 4 )2-6H 2 O (Mohr's salt) may also be used as initiator.
  • mixtures of salts of inorganic peracids and C 2 -C 4 , preferably C 4 , dicarboxylic acids may also be used: for example, mention may be made of the mixture of ammonium persulfate with succinic acid.
  • Peroxides may also be used, for instance disuccinic acid peroxide (DSAP).
  • step a fluorinated surfactants are not used at the start of the polymerization, nor are they added during the polymerization, and nor is there any in situ formation of fluorinated surfactants.
  • the pressure used is generally between 5 and 30 bar (0.5-3 MPa).
  • step a no chain-transfer agent is used.
  • the polymerization in step a) is stopped when the concentration of the polymer in the dispersion is such that it does not lead to coagulation of the polymer and/or the coagulate is present in an amount of less than 1 % and preferably less than 0.1 % relative to the weight of the polymer.
  • Stopping of the polymerization according to the methods described above constitutes the subsequent step b) of the process according to the preferred embodiment of the present invention.
  • the concentration of the fluoropolymer is between 0.2% and about 15%, preferably between 1 % and less than 10% and even more preferably 2-9.5%.
  • step b) is preferably stopped before coagulation of the system takes place.
  • a person skilled in the art is readily capable of determining with little testing the extent of conversion of the system under these conditions.
  • What was surprising and unexpected with the process of the invention is that, by stopping the polymerization before coagulation, or when the coagulate is present is small amounts, generally less than 1 %, the sizes of the particles obtained are in the range 10-400 nm.
  • the dispersion is stable despite the fact that no fluorinated surfactant is present therein.
  • the dispersion is characterized as being shear-stable for the time sufficient to perform thereon stabilization by means of adding non-fluorinated surfactants.
  • the shear stability of the dispersion before adding the surfactant should be greater than 10 seconds and preferably greater than 20 seconds, via the test reported later.
  • the dispersions thus obtained contain fluoropolymer particles with a mean diameter of between 10 nm and 400 nm and preferably between 150 and 300 nm.
  • Gas-phase or liquid-phase (HPLC) chromatographic analysis did not reveal any presence of fluorinated surfactant.
  • the polymerization of the dispersion of the invention was performed in the absence of fluorinated surfactants, and furthermore no fluorinated surfactants were formed during the polymerization.
  • the polymerization of the present invention (step a)) is a suspension polymerization rather than an emulsion polymerization.
  • the amount of non-fluorinated surfactant (weight % relative to the polymer) is between 0.5% and 20%, more preferably between 1.0% and 15% and even more preferably between 2% and 10%.
  • non-fluorinated surfactants are nonionic, anionic and cationic surfactants; nonionic surfactants are preferably used.
  • Nonionic surfactants are known in the art. Mention may be made, for example, of the book “Nonionic Surfactants” Ed. M.J. Schick, Marcel Dekker 1967, pp. 76-85 and 103-141. Among the nonionic surfactants that are particularly preferred are polyethoxylated alcohols optionally containing one or more propylene oxide units. The following surfactants are even more preferred:
  • Tergitol ® TMN100x (Dow) having the formula: sec-Ci 2 H 2 5-(OCH 2 CH 2 ) 10 iOH;
  • Antarox ® 863 (Rhodia) having the formula: iso-Ci 3 H 27 -(OCH 2 CH 2 CH 2 )-(OCH 2 CH 2 ) 10 -OH;
  • Rhodasurf ® 870 (Rhodia) having the formula: iso-Ci 3 H 27 -(OCH 2 CH 2 ) 10 -OH ;
  • Genapol ® X080 (Clariant) having the formula: iso-C 13 H 27 -(OCH 2 CH 2 ) 8 -OH;
  • Genapol ® X090 (Clariant) having the formula: iso-C 13 H 27 -(OCH 2 CH 2 ) 9 -OH.
  • the non-fluohnated anionic surfactants are linear or branched, bearing one or more, preferably one, anionic group. They generally have an equivalent weight, defined as the molecular weight/number of anionic groups present in the surfactant, of greater than 350 and preferably greater than 600. Generally, the equivalent weight of the anionic surfactants that may be used in the process of the present invention is less than 5,000, preferably less than 3,000 and even more preferably less than 1 ,500. The molecular weight of the anionic surfactants is greater than 350, preferably greater than 400 and even more preferably greater than 600. See patent application EP 1 676 868 in the name of the Applicant.
  • anionic surfactants are preferred:
  • step d): concentration of the dispersion, may be performed.
  • the concentration of the dispersion is not greater than 70% and is preferably between 55% and 65%.
  • the concentration method also known as clouding, as described in US 3 037 953, US 3 301 807 and EP 1 526 142 in the name of the Applicant, may be used, for example.
  • Another concentration process which is also the preferred process, is that of ultrafiltration, described in US 4 369 266.
  • the non-fluorinated surfactant that is used may be recovered and reused.
  • the process of the present invention is performed continuously using a plant in which is used a continuous reactor of the plug flow type (plug flow reactor, PFR): see Fig. 1 in which the numbers correspond to the following parts of the plant:
  • the process represented in Fig. 1 is performed in the following manner.
  • the water fed in at (1 ), the TFE fed in at (2) and the optional comonomers fed in at (3) are transferred into a stirred mixing reactor (4).
  • the aqueous phase exiting from (4) is mixed with the initiator or the mixture of initiators fed in at (5) and constitutes the mixture of reagents fed at (6) into the PFR (8).
  • An aqueous solution of a non-fluorinated surfactant is added at (1 1 ) to the polymer dispersion exiting from (8).
  • the aqueous dispersion containing the non-fluorinated surfactant is fed at (10) into the ultrafiltration apparatus (12), which has two outlets, respectively (13), from which is collected the concentrated polymer dispersion, and (14), from which is collected the permeate containing the non-fluorinated surfactant, which is conveyed to the reverse osmosis apparatus (15) for recovery of the non-fluorinated surfactant, a concentrated solution of recovered non-fluorinated surfactant being recovered at (16); the concentrated solution is mixed with a solution of fresh non-fluorinated surfactant originating from the tank (18) before being fed via (1 1 ) with the polymer dispersion leaving the reactor (8).
  • the throughput of the monomer or monomer mixture in the PFR (8) ranges from about 0.5 to about 600 kg/hour and preferably from about 5 to about 300 kg/hour.
  • the residence times in the PFR (8) range from about 1 minute to about 30 minutes, preferably between about 3 and about 20 minutes and even more preferably between about 5 and about 10 minutes. It is possible to arrange several ultrafiltration units in series.
  • thermoprocessable and non-thermoprocessable TFE-based perfluoropolymers that may be obtained via the process of the present invention are, for example, tetrafluoroethylene (TFE) homopolymers and copolymers of TFE with monomers bearing at least one unsaturation of ethylenic type.
  • TFE tetrafluoroethylene
  • the amount of comonomer is preferably less than 15% by weight, more preferably less than 10% and even more preferably less than 1 % to obtain non-thermoprocessable copolymers ("modified PTFE").
  • HFP hexafluoropropene
  • C 2 -C 6 chloro- and/or bromo- and/or iodo-fluoroolefins, such as chlorotrifluoroethylene (CTFE);
  • CTFE chlorotrifluoroethylene
  • CF 2 CFORf 0 , in which R f0 is a CrC 6 (per)fluoroalkyl, for example CF 3 , C 2 F 5 or C 3 F 7 ;
  • ⁇ (per)fluorooxyalkyl vinyl ethers CF 2 CFOX 0 , in which X 0 is a CrCi 2 alkyl or a CrCi 2 oxyalkyl, or a CrCi 2 (per)fluorooxyalkyl containing one or more ether groups, for example perfluoro-2-propoxypropyl;
  • fluorodioxoles preferably perfluorodioxoles.
  • thermoprocessable fluoropolymers examples include PFA and MFA.
  • Preferred fluoropolymers include PTFE homopolymer and modified PTFE.
  • the TFE-based fluoropolymer dispersions that may be obtained via the process of the invention are entirely free of fluorinated surfactants, in particular PFOA, since no fluorinated surfactant is used for the polymerization for their preparation in the process of the invention.
  • fluorinated surfactants in particular PFOA
  • no fluorinated or non-fluorinated surfactants are used during the polymerization of the invention. The reason for this is that it is well known that the latter surfactants would lead to a decrease in the molecular weight and thus to a reduction in the mechanical properties of the polymer.
  • hydrogenated surfactants act as chain transfer agents in the polymerization of TFE.
  • surfactants are relatively short molecules, containing a maximum of about 20 carbon atoms, preferably up to 14, which bear a terminal functional group, for example -COOH or -COO " , and have the capacity to reduce the surface tension of water.
  • fluoropolymer dispersions that may be obtained in steps a)-c) of the process of the present invention are characterized by the following combination of properties:
  • ⁇ shear stability determined according to the test described below, of greater than 10 seconds and preferably greater than 20 seconds
  • ⁇ mean particle diameter of between 10 nm and 400 nm and preferably between 150 and 300 nm
  • ⁇ amount of fluoropolymer expressed as a weight percentage relative to the total weight of the dispersion, of between 0.2% and about 15% and preferably between 1 % and less than 10%
  • dispersions having the same characteristics as those described above are obtained, except that the amount of fluoropolymer, as stated, may also reach high concentrations, of not greater than 70%, preferably between 55% and 65%.
  • the dispersions of the invention contain as fluoropolymers TFE homopolymers or TFE copolymers modified with one or more comonomers up to 1 % by weight, these fluoropolymers have a specific weight SSG (ASTM D 4895) of between 2.00 and 2.29 g/cm 3 and preferably from 2.12 to 2.25 g/cm 3 .
  • the analysis to determine in the dispersions of the present invention the absence of PFOA at ppb levels is performed using HPLC apparatus equipped with an Alltima C18 3 mm x 50 mm x 4.6 mm column, with a mass detector.
  • the test for determining the shear stability of the polymerization latex is as follows. A volume of latex equal to 150 ml is introduced into a container equipped with two breakwaters and is subjected to mechanical stirring at a speed of 843 rpm. The stability of the dispersion is evaluated by determining the time interval, in seconds, between the start of stirring and the moment at which it is observed that the dispersion begins to gel, i.e. assumes the consistency of a gel.
  • thermoprocessable fluoropolymers of the invention generally have a melt viscosity (ASTM D-1238-52T) at the process temperature of greater than 10 2 poises and less than 10 7 poises.
  • the non-thermoprocessable fluoropolymers generally have a melt viscosity (ASTM D-1238-52T) of greater than 10 7 poises, preferably from 10 7 to 10 13 poises and even more preferably from 10 9 to 10 12 poises.
  • the dispersions of TFE-based fluoropolymers of the invention preferably after the concentration step d), may be used in the typically applications of fluoropolymers, for example for producing coatings.
  • the methods for obtaining coatings are known in the art. Mention may be made of the following: spin coating, casting, deep coating.
  • the surfaces of the said manufactured products may be constituted of organic or inorganic polymers, glass, ceramic, metals, etc.
  • 500 g of dispersion are filtered through a nylon gauze of known weight with a mesh size equal to 50 ⁇ m. After filtration, 500 ml of water are passed through the gauze to remove the excess dispersion. The gauze with the residue, if any, is dried in an oven at 105°C for one hour and then weighed. The amount of coagulate is determined by difference relative to the initial weight of the gauze. By dividing the difference by the amount of polymer contained in 500 g of dispersion and multiplying by 100, the percentage of coagulate in the polymer is obtained.
  • the sensitivity limit of the method is 0.005% by weight relative to the polymer. Determination of the mean particle diameter
  • the mean particle diameter is determined on the basis of the method according to ISO standard 13321.
  • the diameter is measured using an instrument based on laser light scattering, in particular on photon correlation spectroscopy, equipped with a model 2030 At Brookhaven correlator and an argon laser light source with a wavelength of 514.5 nm from the company Spectra-Physics.
  • the samples of latex to be subjected to measurement are diluted with water filtered at 0.2 ⁇ m through a Millipore filter.
  • the scattering measurement is performed at room temperature at an angle of 90°.
  • the latex particle diameter is obtained via the cumulative method. Determination of the fluoropolymer content of the latex
  • the polymer content of the latex removed from the reactor and of the supernatant obtained by ultracentrifugation is determined after drying at 150°C for 1 hour. About 20 grams of latex are weighed in a glass beaker and placed in a drying oven for 1 hour at 150°C. The dry content of the latex is obtained by means of the formula:
  • the sample for analysis is prepared by adding 1 gram of latex to 2 grams of acetone, with stirring. The supernatant organic phase (acetone) is separated out and filtered to obtain about 1 g of filtrate. 3 grams of water are added, the mixture is stirred briefly to homogenize and 0.1 ml of the final solution is injected into the liquid chromatograph. The analysis time is about 12 minutes. The sensitivity limit of the method is 30 ppb. Shear stability of the polymerization latex
  • a volume of 150 ml of latex is introduced into an open container equipped with two breakwaters and subject to mechanical stirring with a twin-impeller stirrer at a speed of 843 rpm.
  • the stability of the dispersion is expressed by means of the time interval, in seconds, between the start of stirring and the moment at which gelling of the dispersion begins. Determination of the absolute specific weight (SSG)
  • the absolute specific weight is determined according to ASTM standard D 4895-04. Determination of the molecular weight
  • the molecular weight is calculated from the SSG value by applying the following formula, described by R. C. Doban et al. in the document "Formula from molecular weight of Polytetrafluoroethylene", American Chemical Society Meeting, Atlantic City, N.J., September 1956:
  • MWn 0.597[log ] ⁇ x l ⁇ 6 .
  • the COO " group is detected at a frequency of 1670 cm “1 , the COF group at a frequency of 1884 cm “1 , the extinction coefficient being 215/mol cm.
  • the sensitivity limit of the method is 0.05 mmol/kg of polymer for each end group. Determination of the content of fluorinated surfactants by GC
  • the mixture is stirred and left to stand.
  • the 2 phases are separated, and 1 ⁇ l of the lower fluorinated phase containing the ester of the surfactant is taken.
  • the peak area is related to the amount of surfactant present by means of the calibration curve.
  • the sensitivity limit of the determination method in the case of PFOA is 10 ppm.
  • TFE is begun by means of a compressor so as to maintain a constant pressure of 20 bar inside the reactor.
  • the internal temperature of the reactor is raised to 80°C.
  • the introduction of TFE is stopped when 1 % by weight of PTFE is reached in the latex produced, which is obtained after 10 minutes, during which time 500 grams of TFE are reacted; the reactor is then depressuhzed, emptied and cooled.
  • the primary particle diameter of the polymer measured by laser light scattering (LLS) is equal to 260 nm.
  • the shear stability is greater than 10 seconds. This stability is sufficient to perform the subsequent concentration step.
  • the latex removed from the reactor has a coagulant content of less than 0.01 % by weight relative to the polymer.
  • the latex is concentrated via the clouding concentration method as described below.
  • the latex is then filtered through a 200 ⁇ m filter.
  • the latex is placed under stirring and heating is commenced.
  • 5% by weight of nonionic surfactant (Triton ® ) and 0.05% of ammonium sulfate are added to the dispersion (2,200 g of latex).
  • Triton ® nonionic surfactant
  • ammonium sulfate ammonium sulfate
  • the concentrated polymer phase which corresponds to the lower phase, is removed and filtered through a filter with a mesh size of 100 ⁇ m.
  • the titre of the concentrated latex is 1 1.6% PTFE, and the pH is 3.17. This operation is repeated to obtain a dispersion containing 65% by weight of fluoropolymer.
  • the absolute specific weight is 2.159 g/cm 3 .
  • the calculated molecular weight MWn is 2.09 x 10 7 .
  • the introduction of TFE is begun at a temperature of 22°C so as to maintain a constant pressure of 16 bar inside the reactor.
  • the introduction of TFE is stopped after 6 minutes, when an amount of PTFE equal to 0.3% by weight is formed in the latex. During this interval, 7 kg of TFE are reacted; the reactor is then depressurized, emptied and cooled.
  • the primary particle diameter of the polymer measured is 292 nm, and the absolute specific weight is 2.156 g/cm 3 .
  • the calculated molecular weight MWn is 3.01 x 10 7 .
  • the PFOA content is below the analytical limit, i.e. less than 30 ppb.
  • the shear stability is greater than 20 seconds.
  • the dispersion is concentrated to 65% by weight of fluoropolymer via ultrafiltration using six Koch membranes in series, each with a surface area of 0.1 m 2 .
  • the average yield under the conditions used in the example was good and was 200 litres/(h m 2 ).

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Abstract

L'invention porte sur un procédé de préparation de dispersions aqueuses de polymères comprenant : a) la polymérisation en suspension en phase aqueuse de TFE, facultativement en présence d'un ou plusieurs comonomères à insaturation éthylénique, en présence d'un amorceur de radicaux libres, sans l'addition initiale de tensio-actifs fluorés, sans l'addition de tensio-actifs fluorés pendant la polymérisation et sans une quelconque formation in situ d'agents tensio-actifs fluorés.
PCT/EP2008/059367 2007-07-20 2008-07-17 Procédé de préparation de dispersions de polymères Ceased WO2009013214A1 (fr)

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EP07425449 2007-07-20
EP07425449.1 2007-07-20

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Cited By (5)

* Cited by examiner, † Cited by third party
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US20120116015A1 (en) * 2010-11-09 2012-05-10 E. I. Du Pont De Nemours And Company Reducing the Telogenic Behavior of Hydrocarbon-Containing Surfactants in Aqueous Dispersion Fluoromonomer Polymerization
US20120116003A1 (en) * 2010-11-09 2012-05-10 E. I. Du Pont De Nemours And Company Aqueous Polymerization of Perfluoromonomer Using Hydrocarbon Surfactant
WO2012064846A1 (fr) 2010-11-09 2012-05-18 E. I. Du Pont De Nemours And Company Nucléation en polymérisation en milieu aqueux de fluoromonomère
US9676929B2 (en) 2013-11-26 2017-06-13 The Chemours Company Fc, Llc Employing polyalkylene oxides for nucleation in aqueous polymerization of fluoromonomer
CN113728015A (zh) * 2019-04-26 2021-11-30 大金工业株式会社 氟聚合物水性分散液的制造方法和氟聚合物水性分散液

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US20070072985A1 (en) * 2005-09-27 2007-03-29 3M Innovative Properties Company Method of making a fluoropolymer

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070072985A1 (en) * 2005-09-27 2007-03-29 3M Innovative Properties Company Method of making a fluoropolymer

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US9371405B2 (en) 2010-11-09 2016-06-21 The Chemours Company Fc, Llc Nucleation in aqueous polymerization of fluoromonomer
US9518170B2 (en) 2010-11-09 2016-12-13 The Chemours Company Fc, Llc Aqueous polymerization of perfluoromonomer using hydrocarbon surfactant
WO2012064858A1 (fr) 2010-11-09 2012-05-18 E. I. Du Pont De Nemours And Company Réduction du comportement télogène d'agents tensioactifs contenant des hydrocarbures lors de la polymérisation de fluoromonomère en dispersion aqueuse
WO2012064846A1 (fr) 2010-11-09 2012-05-18 E. I. Du Pont De Nemours And Company Nucléation en polymérisation en milieu aqueux de fluoromonomère
US8563670B2 (en) 2010-11-09 2013-10-22 E I Du Pont De Nemours And Company Nucleation in aqueous polymerization of fluoromonomer
US9074025B2 (en) 2010-11-09 2015-07-07 The Chemours Company Fc, Llc Reducing the telogenic behavior of hydrocarbon-containing surfactants in aqueous dispersion fluoromonomer polymerization
US9255164B2 (en) 2010-11-09 2016-02-09 The Chemours Company Fc, Llc Aqueous polymerization of perfluoromonomer using hydrocarbon surfactant
US20160122509A1 (en) * 2010-11-09 2016-05-05 The Chemours Company Fc, Llc Aqueous polymerization of perfluoromonomer using hydrocarbon surfactant
US20120116003A1 (en) * 2010-11-09 2012-05-10 E. I. Du Pont De Nemours And Company Aqueous Polymerization of Perfluoromonomer Using Hydrocarbon Surfactant
US20170073435A1 (en) * 2010-11-09 2017-03-16 The Chemours Company Fc, Llc Aqueous polymerization of perfluoromonomer using hydrocarbon surfactant
US20120116015A1 (en) * 2010-11-09 2012-05-10 E. I. Du Pont De Nemours And Company Reducing the Telogenic Behavior of Hydrocarbon-Containing Surfactants in Aqueous Dispersion Fluoromonomer Polymerization
US11655312B2 (en) 2010-11-09 2023-05-23 The Chemours Company Fc, Llc Aqueous polymerization of perfluoromonomer using hydrocarbon surfactant
EP3533811A1 (fr) 2010-11-09 2019-09-04 The Chemours Company FC, LLC Nucléation dans la polymérisation aqueuse de monomères fluorés
US10703829B2 (en) 2010-11-09 2020-07-07 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
CN113728015A (zh) * 2019-04-26 2021-11-30 大金工业株式会社 氟聚合物水性分散液的制造方法和氟聚合物水性分散液
EP3960777A4 (fr) * 2019-04-26 2023-01-18 Daikin Industries, Ltd. Procédé de production d'une dispersion aqueuse de fluoropolymère et dispersion aqueuse de fluoropolymère

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