WO2016013887A1 - Procédé de polymérisation de monomères à base de fluor comprenant des émulsifiants à base de fluor, et polymères à base de fluor ainsi préparés - Google Patents

Procédé de polymérisation de monomères à base de fluor comprenant des émulsifiants à base de fluor, et polymères à base de fluor ainsi préparés Download PDF

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WO2016013887A1
WO2016013887A1 PCT/KR2015/007680 KR2015007680W WO2016013887A1 WO 2016013887 A1 WO2016013887 A1 WO 2016013887A1 KR 2015007680 W KR2015007680 W KR 2015007680W WO 2016013887 A1 WO2016013887 A1 WO 2016013887A1
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fluorine
monomer
emulsifier
polymerization
polymer
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PCT/KR2015/007680
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Korean (ko)
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하종욱
이수복
박인준
손은호
이광원
육신홍
이상구
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한국화학연구원
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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
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • 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
    • 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
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents

Definitions

  • the present invention relates to a polymerization method of a fluorinated monomer containing a fluorine-based emulsifier and a fluorine-based polymer prepared accordingly. More specifically, it is related with the method of manufacturing a fluorine-type polymer using the fluorine-type emulsifier containing a perfluoroalkyl group.
  • Fluorine-based polymers have been used in various industrial applications because they have good physical properties such as thermal stability, chemical resistance, weather resistance, UV stability, and the like.
  • the fluorine-based polymer may be prepared by various methods such as suspension polymerization, water dispersion emulsion polymerization, solution polymerization, supercritical CO 2 use polymerization, gas phase polymerization, and the like.
  • suspension polymerization water dispersion emulsion polymerization
  • solution polymerization solution polymerization
  • supercritical CO 2 use polymerization
  • gas phase polymerization gas phase polymerization, and the like.
  • the most commonly adopted polymerization methods are suspension polymerization and water dispersion emulsion polymerization.
  • the water dispersion emulsion polymerization is polymerized in the presence of a fluorine-based surfactant used for stabilizing the polymer particles formed, and conventionally perfluoroalkanoic acids or salts thereof (PFOA) as such a surfactant.
  • PFOA perfluoroalkanoic acids or salts thereof
  • fluorine-based surfactants of perfluoroalkanoic acid or salts thereof used in the related art accumulate in the human body, causing environmental problems, and have high price. Therefore, it is an urgent problem to develop a surfactant that can replace a fluorine-based surfactant such as a conventional perfluoroalkanoic acid or a salt thereof. In particular, there is a need for a new environmentally friendly surfactant that has low toxicity and no human accumulation.
  • US Pat. No. 5,804,650 discloses a technique in which a fluorine-based surfactant having a double bond is used as a reactive surfactant and a monomer serves as a surfactant.
  • a fluorine-based surfactant having a double bond is used as a reactive surfactant and a monomer serves as a surfactant.
  • aggregation of particles occurs.
  • An object of the present invention is a polymerization method of a fluorinated monomer including a fluorine-based emulsifier that has excellent chemical and thermal stability, has high polymerization rate, excellent dispersion stability and yield during emulsion polymerization, and is easy to control molecular weight and particle size of the fluorine-based polymer. And to provide a fluorine-based polymer prepared accordingly.
  • Another object of the present invention to solve the above problems is to provide a polymerization method of a fluorine-based monomer comprising a new environmentally friendly fluorine-based emulsifier having low toxicity in the manufacture of fluorine-based polymer and no human accumulation, and to provide a fluorine-based polymer prepared accordingly will be.
  • the present invention relates to a polymerization method of a fluorinated monomer containing a fluorine-based emulsifier and a fluorine-based polymer prepared accordingly.
  • the present invention relates to a polymerization method of a fluorine monomer comprising a fluorine emulsifier represented by the following formula (1).
  • R 1 is hydrogen or methyl
  • R 2 is straight or branched alkyl (C 1 -C 12 ), which may be further substituted with heterocycloalkyl or an amino group,
  • n is an integer from 1 to 5
  • x is 0.05 ⁇ in mole fraction ⁇ 0.99
  • y is the mole fraction of 0.01 ⁇ ⁇ 0.60
  • the present invention relates to a method for producing a fluorine-based polymer comprising the step of water-dispersion emulsion polymerization of at least one fluorine-based monomer using at least one fluorine-based emulsifier represented by the formula (1).
  • the present invention is to prepare a fluorine-based polymer using a fluorine-based emulsifier, the main component of the monomer containing a perfluorine group represented by the formula (1), has a fast polymerization rate, has excellent chemical, thermal stability, dispersion stability, It is characterized by being able to easily control molecular weight and particle size.
  • the solubility of the fluorine-based emulsifier provided in the present invention is easily adjusted according to the acidity (pH) of the aqueous solution, the fluorine-based emulsifier can be easily recovered from the aqueous solution from which the fluorine-based polymer is separated after the polymerization of the fluorine-based monomer. There is this.
  • the water dispersion emulsion polymerization of the fluorine-based monomer is disclosed in the presence of the fluorine-based emulsifier according to the present invention.
  • the fluorine-based emulsifier may be used by commercially available or synthesized by a method commonly used in the art.
  • the fluorine-based emulsifier according to the present invention may be a random copolymer or a block copolymer, and may be polymerized by any one of emulsion polymerization, suspension polymerization, bulk polymerization or solution polymerization, but may be polymerized by emulsion polymerization. It is preferable to prepare a polymer can be used as a polymer emulsifier dispersed in water as the polymer emulsifier, it is preferable for the reason that the additive is easily removed through drying and washing with water.
  • a fluorine-based polymer may be prepared including a fluorine-based monomer, a fluorine-based emulsifier represented by the following formula (1), a chain transfer agent and an initiator.
  • the fluorinated monomers polymerizable using the fluorine-based emulsifier according to the present invention include vinylidene fluoride, tetrafluoroethylene (TFE), hexafluoropropylene (TFP), chlorotrifluoroethylene (CTFE), and vinyl fluoride.
  • Trifluoroethylene Trifluoroethylene, hexafluoroisobutylene, perfluorobutylethylene, perfluoropropyl vinyl ether (PPVE), perfluoroethyl vinyl ether (PEVE), perfluoromethyl vinyl ether (PMVE), purple Any or two selected from the group consisting of urouro-2,2-dimethyl-1,3-dioxo (PDD) and perfluoro-2-methylene-4-methyl-1,3-dioxolane (PMD)
  • PDD urouro-2,2-dimethyl-1,3-dioxo
  • PMD perfluoro-2-methylene-4-methyl-1,3-dioxolane
  • the fluorine-based emulsifier may be represented by the following formula (1).
  • R 1 is hydrogen or methyl
  • R 2 is straight or branched alkyl (C 1 -C 12 ), which may be further substituted with heterocycloalkyl or an amino group,
  • n is an integer from 1 to 5
  • x is 0.05 ⁇ in mole fraction ⁇ 0.99
  • y is the mole fraction of 0.01 ⁇ ⁇ 0.60
  • the fluorine-based emulsifier represented by Chemical Formula 1 is a polymer of a hydrophilic monomer, a hydrophobic monomer, and a monomer including a perfluoroalkyl group.
  • acrylic acid or methacrylic acid may be used as the hydrophilic monomer, and the content thereof may be included in a molar fraction of 0.05 to 0.99, more preferably 0.20 to 0.80, based on the total polymer emulsifier.
  • hydrophobic monomer examples include methyl acrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, octadecyl methacrylate, lauryl methacrylate, dimethylaminoethyl methacrylate, ter Sherylbutylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 1-decyl acrylate, It can be selected from (meth) acrylate monomers containing linear or pulverized hydrocarbon alkyl groups such as 1-decyl methacrylate, lauryl acrylate or lauryl methacrylate, and also trifluoroethyl (meth Selected from (meth) acrylate monomers containing straight-
  • the fluorine-based emulsifier improves the stability of the particles and the yield of the fluorine-based polymer, the weight average molecular weight is preferably 5,000 to 500,000 g / mol to facilitate recovery from the reaction medium.
  • the fluorine-based emulsifier with a molecular weight too large it may not be economical because there is no additional advantage, it is preferable to use a fluorine-based emulsifier in the above range.
  • the content of the fluorinated emulsifier depends on the required physical properties such as the solid content and particle size of the prepared fluorine-based polymer, but the molecular weight, final reaction yield and particle size of the polymer polymer for excellent polymerization rate, dispersion stability and the purpose of the present invention For the control of 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight based on 100 parts by weight of the fluorine monomer.
  • an excessive amount of the fluorinated emulsifier it is preferable to use the above range because the size of the resulting fluorinated polymer particles becomes fine and the viscosity of the reaction medium becomes high, so that separation and recovery are not easy and additional advantages may not be economical. Do.
  • the fluorinated emulsifier may have a pH solubility in the reaction medium during the polymerization process, for example, the fluorine emulsifier may have a pH solubility in water used as the reaction medium during the polymerization of the fluorinated monomer. Can be.
  • the pH of the reaction medium is 5 to 10, so that the fluorine-based emulsifier is easily dissolved, and since the reaction is easily recovered from the reaction medium, the pH is preferably in the above range.
  • the pH of the reaction medium may be adjusted using, for example, sodium hydroxide, potassium hydroxide, ammonia water, but is not necessarily limited thereto.
  • Chain transfer agent of the present invention can be used for molecular weight control of the polymer produced in the water dispersion emulsion polymerization in the present invention.
  • esters such as diethylmalonate, ethers such as dimethyl ether, methyl t-butyl ether, alkanes such as ethane, n-pentane such as propane, carbon tetrachloride, chloroform, halogenated hydrocarbons such as dichloromethane, tetra
  • Any one or a mixture of two or more selected from carbon fluoride compounds such as fluoroethane, methyl acetate, ethyl acetate, propyl acetate and butyl acetate may be used, but is not necessarily limited thereto.
  • the content is preferably used 0.1 to 3 parts by weight based on 100 parts by weight of the fluorine monomer for molecular weight control.
  • the initiator of the present invention can be used to initiate free radical polymerization of the fluorine monomer.
  • Suitable initiators may include peroxides, azo compounds and redox based initiators.
  • the peroxide initiator include hydrogen peroxide, sodium or barium peroxide, diacetyl peroxide, disuccinyl peroxide, dipropionyl peroxide, dibutyryl peroxide, dibenzoyl peroxide, benzoylacetyl peroxide And diacyl peroxides such as diglutaric acid peroxide and dilauryl peroxide.
  • ammonium persulfate and alkali salt persulfate can be used.
  • Persulfate initiators such as ammonium persulfate may be used alone or in combination with other reducing agents.
  • Suitable reducing agents may include, but are not necessarily limited to, ammonium bisulfite or sodium metabisulfite, ammonium, potassium, sodium such as thiosulphate, hydrazine, and the like.
  • the content is preferably used in an amount of 0.001 to 1 parts by weight based on 100 parts by weight of the fluorine monomer in order to start free radical polymerization.
  • the water dispersion emulsion polymerization is easily carried out at a temperature of 20 to 110 °C and a pressure of 5 to 80 bar in the present invention to easily control the weight average molecular weight and particle size Preferred below, but not limited thereto.
  • the fluorine-based polymer prepared by the method for preparing a fluorine-based polymer according to the present invention may have physical properties of 10 to 35% solids, 50 to 500 nm in average diameter, and 50,000 to 800,000 g / mol in weight average molecular weight.
  • the polymer of the fluorinated monomer prepared by emulsion polymerization using the fluorine-based emulsifier of the present invention may be separated from the aqueous phase, which is a reaction medium, if necessary, and then used in the form of a powder or the like.
  • the pH of the aqueous phase may be adjusted to 4 or less, preferably pH 1 to 4, and hydrochloric acid to adjust the pH of the aqueous phase to the above range.
  • Various inorganic acids such as sulfuric acid can be used, but are not necessarily limited thereto.
  • the fluorinated emulsifier of the present invention satisfies all of the requirements as a fluorinated emulsifier that can replace the existing perfluoroalkanoic acid (PFOA) or salts thereof (APFO), and is used for the water dispersion emulsion polymerization of fluorinated monomers as well as fluorinated monomer mixtures. It can be usefully used.
  • PFOA perfluoroalkanoic acid
  • APFO salts thereof
  • the present invention has an excellent polymerization rate, dispersion stability and yield during emulsion polymerization using a fluorine-based emulsifier and at the same time it is easy to control the molecular weight and particle size of the polymer.
  • the fluorine-based polymer prepared in the present invention has a low toxicity, there is no human accumulation, there is an environment-friendly advantage.
  • the fluorine-based emulsifier used in the present invention can be easily recovered by adjusting the pH of the aqueous phase to 4 or less.
  • the weight average molecular weight and the molecular weight distribution index (PDI) of the fluorine-based polymer prepared by the polymer emulsifier and emulsion polymerization were measured by gel permeation chromatography (GPC, Waters 2690). Dimethylacetoamide (DMAc) was used as a mobile phase at room temperature, and measured using a RI detector. Molecular weight standard curves were prepared using monodisperse polystyrene.
  • the particle size of the fluorine-based polymer prepared by emulsion polymerization was measured by observing the dried particles with a scanning electron microscope (Tescan VEGA II LSU).
  • the chemical composition of the polymer emulsifier was measured by 1 H-NMR (Bruker DRX-300 FT-NMR) method using DMSO-d6 as a solvent.
  • the thermal properties of the dried samples were measured by melting point and crystallinity using a differential scanning calorimeter (TA Instruments. DSC2910).
  • 390 g of distilled water, 0.1 g of sodium bicarbonate, and 0.5 g of lauryl sulfate sodium salt were added to a 1 L reactor equipped with a stirrer and a condenser, and the temperature of the reactant was raised to 75 ° C. using a circulating thermostat.
  • 20 g of a monomer mixture composed of 40 g of methacrylic acid, 40 g of trifluoroethyl methacrylate, 20 g of tridecafluoroethyl methacrylate, and 0.3 g of 1-octanethiol was added thereto, and stirred at a stirring speed of 250 rpm for 20 minutes. It was.
  • the chemical composition of the fluorine-based emulsifier (FASP) was measured by 1 H-NMR and determined as 0.653 mole fraction of methacrylic acid, 0.306 mole fraction of trifluoroethyl methacrylate, and 0.041 mole fraction of tridecafluoroethyl methacrylate.
  • a high pressure reactor made of stainless steel with a magnetic drive was used for emulsion polymerization of the fluorine monomer.
  • the temperature in the reactor was controlled by supplying a heat medium to the reactor jacket using a circulation thermostat outside the reactor.
  • 300 g of distilled water, 0.5 g of fluorinated emulsifier (FASP), and 1 g of ethyl acetate (EA) were added to the reactor, followed by purging nitrogen several times to remove oxygen, and then 50 g of vinylidene fluoride (VDF) was added thereto.
  • the temperature of the mixture was increased to 82 ° C.
  • the reaction was started by adding 1 g of sodium persulfate dissolved in a small amount of distilled water, and 60 g of vinylidene fluoride was continuously added to maintain the pressure in the reactor at 20 atmospheres or more.
  • the reaction was terminated by further reacting for 30 minutes after the prescribed amount of monomer was added and discharging the unreacted monomer, and the results are shown in Table 1.
  • Sodium chloride was added to the aqueous dispersion of a certain amount of vinylidene fluoride polymer to induce agglomeration of the polymer particles, and the polymer was separated using a filtration device.
  • Hydrochloric acid aqueous solution was added to the transparent filtrate at this time to maintain a pH of 3 to obtain a white precipitate of a fluorine-based emulsifier, which was filtered and dried to measure the mass of the fluorinated emulsifier. It was.
  • Example 1 The experiment was conducted in the same manner as in Example 1, except that the amount of the monomer, the fluorine-based emulsifier, and ethyl acetate was changed in Example 1, and the results are shown in Table 1.
  • a high pressure reactor made of stainless steel with a magnetic drive was used for emulsion polymerization of the fluorine monomer.
  • the temperature in the reactor was controlled by supplying a heat medium to the reactor jacket using a circulation thermostat outside the reactor.
  • an emulsifier ammonium salt of perfluoroalkanoic acid_ammonium pentadecafluorooctanoate: APFO
  • 0.01 g of ethyl acetate were added, followed by purging nitrogen several times to remove oxygen.
  • Sodium chloride was added to the aqueous dispersion of a certain amount of vinylidene fluoride polymer to induce agglomeration of the polymer particles, and the polymer was separated using a filtration device.
  • Hydrochloric acid aqueous solution was added to the transparent filtrate at this time to maintain a pH of 3, but it was impossible to obtain precipitation of the emulsifier.
  • a high pressure reactor made of stainless steel with a magnetic drive was used, and a heat medium was supplied to the reactor jacket using a circulating thermostat outside the reactor to control the temperature in the reactor.
  • a heat medium was supplied to the reactor jacket using a circulating thermostat outside the reactor to control the temperature in the reactor.
  • the reaction was started by adding 1 g of sodium persulfate dissolved in a small amount of distilled water, and 50 g of vinylidene fluoride was continuously added to maintain the pressure in the reactor at 20 atmospheres or more. After the predetermined amount of monomer was added, the reaction was further completed for 30 minutes and the reaction was terminated by discharging the unreacted monomer, and the results are shown in Table 3.
  • Sodium chloride was added to the aqueous dispersion of a certain amount of vinylidene fluoride polymer to induce agglomeration of the polymer particles, and the polymer was separated using a filtration device.
  • Hydrochloric acid aqueous solution was added to the transparent filtrate at this time to maintain a pH of 3, but it was impossible to obtain precipitation of the emulsifier.
  • the precipitate of emulsifier can be obtained by adding calcium aqueous solution, but it is not preferable because precipitation is incomplete and secondary water pollution occurs.
  • 390 g of distilled water, 0.1 g of sodium bicarbonate, and 0.5 g of lauryl sulfate sodium salt were added to a 1 L reactor equipped with a stirrer and a condenser, and the temperature of the reactant was raised to 75 ° C. using a circulating thermostat.
  • 20 g of a monomer mixture composed of 40 g of methacrylic acid, 40 g of methyl methacrylate, 20 g of butyl methacrylate, and 0.3 g of 1-octanethiol was added thereto, and stirred at a stirring speed of 250 rpm for 20 minutes.
  • the chemical composition of the hydrocarbon-based emulsifier (ASP) was measured by 1 H-NMR, and the result was confirmed by 0.284 mole fraction of methacrylic acid, 0.529 mole fraction of methyl methacrylate, and 0.187 mole fraction of butyl methacrylate.
  • a high pressure reactor made of stainless steel with a magnetic drive was used, and a heat medium was supplied to the reactor jacket using a circulating thermostat outside the reactor to control the temperature in the reactor.
  • 300 g of distilled water, 0.5 g of the hydrocarbon-based emulsifier (ASP) prepared above, and 0.1 g of ethyl acetate were added to the reactor and purged with nitrogen several times to remove oxygen, and then 50 g of vinylidene fluoride was added thereto. It heated up so that temperature reached 82 degreeC.
  • the reaction was started by adding 1 g of sodium persulfate dissolved in a small amount of distilled water, and 50 g of vinylidene fluoride was continuously added to maintain the pressure in the reactor at 20 atmospheres or more. After the predetermined amount of monomer was added, the reaction was further performed for 30 minutes, and the reaction was terminated by discharging unreacted monomer.
  • Sodium chloride was added to the aqueous dispersion of a certain amount of vinylidene fluoride polymer to induce agglomeration of the polymer particles, and the polymer was separated using a filtration device.
  • the hydrochloric acid solution was added to the transparent filtrate and the pH was maintained at 3 to obtain a white precipitate of the emulsifier. The precipitate was filtered and dried to measure the mass of the emulsifier, and the recovery rate of the emulsifier was measured.
  • APFO fluorine-based emulsifier including a perfluoroalkyl group in its molecular structure.

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Abstract

La présente invention concerne un procédé de polymérisation de monomères à base de fluor comprenant des émulsifiants à base de fluor et les polymères à base de fluor préparés par ce procédé. Plus précisément, la présente invention concerne un procédé de préparation de polymères à base de fluor par polymérisation de monomères à base de fluor, et en particulier, un procédé de polymérisation d'émulsion dispersible dans l'eau à l'aide d'émulsifiants à base de fluor représentés par la formule chimique 1
PCT/KR2015/007680 2014-07-25 2015-07-23 Procédé de polymérisation de monomères à base de fluor comprenant des émulsifiants à base de fluor, et polymères à base de fluor ainsi préparés WO2016013887A1 (fr)

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KR1020140094489A KR101596277B1 (ko) 2014-07-25 2014-07-25 불소계 유화제를 포함하는 불소계 단량체의 중합방법 및 이에 따라 제조되는 불소계 고분자
KR10-2014-0094489 2014-07-25

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110872363A (zh) * 2018-08-31 2020-03-10 浙江大学 可交联含氟大分子乳化剂、含所述乳化剂的含氟乳液、其制备及使用方法

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KR20040024528A (ko) * 2000-09-22 2004-03-20 듀폰 다우 엘라스토마스 엘. 엘. 씨. 불화 엘라스토머의 제조 방법
US20090053462A1 (en) * 2005-04-22 2009-02-26 Ji Guo Perfluoroalkyl (meth)acrylate polymers and their use as surfactant and substrate treating reagents
WO2010113950A1 (fr) * 2009-03-30 2010-10-07 ダイキン工業株式会社 Polytétrafluoroéthylène et son procédé de fabrication
KR20110027718A (ko) * 2008-06-02 2011-03-16 솔베이 솔렉시스 에스.피.에이. 비닐리덴 플루오라이드 및 트리플루오로에틸렌을 함유한 중합체

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Publication number Priority date Publication date Assignee Title
KR20010083176A (ko) * 2000-02-22 2001-08-31 오틸리오 마세롤리; 카를로 코그리아티 플루오르화 중합체들의 수용성분산액의 제조방법
KR20040024528A (ko) * 2000-09-22 2004-03-20 듀폰 다우 엘라스토마스 엘. 엘. 씨. 불화 엘라스토머의 제조 방법
US20090053462A1 (en) * 2005-04-22 2009-02-26 Ji Guo Perfluoroalkyl (meth)acrylate polymers and their use as surfactant and substrate treating reagents
KR20110027718A (ko) * 2008-06-02 2011-03-16 솔베이 솔렉시스 에스.피.에이. 비닐리덴 플루오라이드 및 트리플루오로에틸렌을 함유한 중합체
WO2010113950A1 (fr) * 2009-03-30 2010-10-07 ダイキン工業株式会社 Polytétrafluoroéthylène et son procédé de fabrication

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110872363A (zh) * 2018-08-31 2020-03-10 浙江大学 可交联含氟大分子乳化剂、含所述乳化剂的含氟乳液、其制备及使用方法

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