[go: up one dir, main page]

WO2011058016A1 - Procédé pour la fabrication de polymères greffés - Google Patents

Procédé pour la fabrication de polymères greffés Download PDF

Info

Publication number
WO2011058016A1
WO2011058016A1 PCT/EP2010/067133 EP2010067133W WO2011058016A1 WO 2011058016 A1 WO2011058016 A1 WO 2011058016A1 EP 2010067133 W EP2010067133 W EP 2010067133W WO 2011058016 A1 WO2011058016 A1 WO 2011058016A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
comonomer
liquid medium
moles
group
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/EP2010/067133
Other languages
English (en)
Inventor
Fabrizio Spada
Bradley Lane Kent
Shiow-Ching Lin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solvay Specialty Polymers Italy SpA
Original Assignee
Solvay Solexis SpA
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 Solvay Solexis SpA filed Critical Solvay Solexis SpA
Publication of WO2011058016A1 publication Critical patent/WO2011058016A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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

Definitions

  • This invention pertains to a process for manufacturing grafted polymers enabling maintaining native morphology of the parent polymer.
  • VDF polymers are fluoropolymers known to possess unique properties such as low surface energy, high chemical and thermal stability, and good mechanical properties. Such VDF polymers have been widely used for various applications including chemically resistant materials, filter membranes, electrical insulators, and the like. However, VDF polymers are normally highly hydrophobic and solvophobic, and present certain disadvantages, such as poor wettability, and miscibility. These problems might possibly limit their application in certain fields.
  • graft copolymers afforded a possibility to overcome many of the disadvantages discussed above. Indeed, properties such as wettability, amphiphilicity, biocompatibility, solubility, phase compatibility with other polymers, and adhesion to surfaces can be improved by graft copolymerization of co-monomers onto the backbone of VDF polymers. Depending on the nature of the co-monomer, graft copolymers may possess specific properties while retaining desirable properties of the parent VDF polymer.
  • graft copolymers are most commonly accomplished via free-radical reactions initiated by exposing the VDF polymer to ionizing radiation and/or a free-radical initiator in the presence of the comonomer.
  • Free radical syntheses in this manner can be an uncontrolled process. Numerous radicals are present not only on the polymer but also on the comonomer, which can undergo free-radical homopolymerization resulting in a mixture of homopolymers and graft copolymers.
  • a significant disadvantage of these free-radical techniques is that the product is typically a mixture of graft copolymer and homopolymer.
  • polymer backbone degradation and/or crosslinking can occur as a result of uncontrolled free-radical production, dramatically affecting properties of the parent VDF polymers.
  • ATRP atom transfer radical polymerization
  • document WO 02/22712 (MASSACHUSETTS INST TECHNOLOGY ) 21.03.2002 pertains to a method for grafting hydrophilic chains into polymers, including PVDF, by graft polymerization of vinyl monomers by ATRP.
  • PVDF grafted with methacrylic acid was thus obtained by solution-polymerizing PVDF and terbutylmethacrylate in NMP in the presence of an ATRP catalyst, precipitating the grafted polymer and hydrolizing the same with toluensulphonic acid.
  • p.3531 -3539 disclose a method for graft-polymerizing fluoropolymers comprising recurring units derived from chlorortrifluoroethylene (CFTE) with vinyl monomers, such as styrene, terbutylacrylate by ATRP
  • Grafting methods of the prior art cannot thus provide dispersions suitable for e.g. coating applications.
  • optical properties e.g. gloss
  • solvent resistance of coatings from hydrogenated resins and VDF polymers can be obtained by crosslinking
  • lack of cure site on VDF polymers might brought to 'disrupted' multiphase coatings, wherein the advantages of crosslinking are lost.
  • thermosetting resins appropriate liquid viscosity, but also possessing increased compatibility towards hydrogenated polymers and/or crosslinking sites for taking part in crosslinking reactions in combination with thermosetting resins.
  • VDF vinylidene fluoride
  • coating compositions can be obtained combining easiness in
  • copolymer is intended to denote a copolymer obtained by covalently bonding a species to be grafted, referred to as a comonomer, to a parent polymer which provides the backbone in the graft copolymer.
  • the copolymer which comprises at least one comonomer (A) covalently attached to the parent polymer (F).
  • the graft copolymer comprises the same backbone as the parent polymer (F).
  • the graft copolymer generally differs from the parent polymer (F) in that the graft copolymer has a plurality of side chains protruding from the backbone. If reactive sites from which side chainsstem were present in the parent at regular intervals, the graft copolymer can result in side chains spaced at substantially regular intervals.
  • Such graft copolymers resemble a comb and are accordingly termed "comb polymers.”
  • the polymer (F) is typically a polymer comprising :
  • VDF vinylidene fluoride
  • (b') optionally from 0.1 to 15%, preferably from 0.1 to 12%, more preferably from 0.1 to 10% by moles of a fluorinated monomer different from VDF; said fluorinated monomer being preferably selected in the group consisting of vinylfluoride (VF-
  • vinylfluoride
  • CTFE chlorotrifluoroethylene
  • HFP hexafluoropropene
  • TFE tetrafluoroethylene
  • MVE perfluoromethylvinylether
  • TrFE trifluoroethylene
  • (c') optionally from 0.1 to 5 %, by moles, preferably 0.1 to 3 % by moles, more preferably 0.1 to 1 % by moles, based on the total amount of monomers (a') and (b'), of one or more hydrogenated comonomer(s).
  • the polymer (F) is preferably a polymer consisting essentially of :
  • VDF vinylidene fluoride
  • (b') optionally from 0.1 to 15%, preferably from 0.1 to 12%, more preferably from 0.1 to 10% by moles of a fluorinated monomer different from VDF; said fluorinated monomer being preferably selected in the group consisting of vinylfluoride (VF-
  • vinylfluoride
  • CTFE chlorotrifluoroethylene
  • HFP hexafluoropropene
  • TFE tetrafluoroethylene
  • MVE perfluoromethylvinylether
  • TrFE trifluoroethylene
  • Polymer (F) may still comprise other moieties such as defects,
  • the polymer (F) comprises recurring units containing at least one secondary halogen atom selected from CI, Br and I, preferably CI.
  • the polymer (F) comprises
  • CTFE chlorotrifluoroethylene
  • a particularly preferred polymer (F) is a copolymer of VDF and CTFE, possibly comprising recurring units derived from fluorinated monomer different from VDF and CTFE, as listed above under (b'), and generally in amounts as above defined.
  • Particles of polymer (F) to be used in the process of the invention are
  • Particles of polymer (F) are thus generally composed of agglomerates of primary particles having an average primary particle size of 10 to 500 nm, preferably of 50 to 450 nm, even more preferably of 150 to 350 nm.
  • liquid medium is intended to denote a medium which is available in liquid state at a temperature of 25°C.
  • dispersion is meant that the polymer (F) particles are stably dispersed in the liquid medium, so that neither solvation of the particles nor settlement into cake within time of use does occur.
  • substantially insoluble is understood to mean that the polymer (F) is optionally solubilised in the liquid medium at a concentration of less than 1 g/l, preferably of less than 0.5 g/l, more preferably of less than 0.1 g/l; most preferably the solubilised fraction is absent.
  • the liquid medium comprises at least one latent solvent for polymer (F).
  • a latent solvent for the polymer (F) is a solvent which does not dissolve or substantially swell polymer (F) at 25°C, which solvates polymer (F) at its boiling point, but on cooling, polymer (F) precipitates.
  • a solvent will be considered as not dissolving the polymer (F) when the polymer (F) cannot be solubilised in said solvent at a concentration exceeding 1 g/l, preferably exceeding 0.5 g/l, more preferably exceeding 0.1 g/l, even more preferably exceeding 0.01 g/l.
  • Latent solvent suitable for the process of the invention are notably methyl isobutyl ketone, n-butyl acetate, cyclohexanone, diacetone alcohol, diisobutyl ketone, ethyl acetoacetate, triethyl phosphate, propylene carbonate, triacetin (also known as 1 ,3-diacetyloxypropan-2-yl acetate), dimethyl phthalate, glycol ethers based on ethylene glycol, diethylene glycol and propylene glycol, and glycol ether acetates based on ethylene glycol, diethylene glycol and propylene glycol.
  • diethylene glycol and propylene glycol are notably ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol methyl ether, propylene glycol dimethyl ether, propylene glycol n-propyl ether.
  • Non limitative examples of glycol ether acetates based on ethylene glycol, diethylene glycol and propylene glycol are notably ethylene glycol methyl ether acetate, ethylene glycol monethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol methyl ether acetate.
  • a particularly preferred latent solvent is dimethyl phthalate.
  • the liquid medium can comprise additional solvents, provided that polymer (F) remains substantially insoluble at a temperature of 25°C in said liquid medium.
  • the liquid composition can thus further comprise at least one among
  • Mixtures of one or more than one latent solvent with one or more than one intermediate solvent and/or non-solvent can also be used.
  • An intermediate solvent for the polymer (F) is a solvent which does not dissolve or substantially swell the polymer (F) at 25°C, which solvates polymer (F) at its boiling point, and retains polymer (F) in solvated form, i.e. in solution, upon cooling.
  • a non-solvent for polymer (F) is a solvent which does not dissolve or
  • Non-solvents suitable for the process of the invention are notably methanol, hexane, toluene, ethanol and xylene.
  • Intermediate solvents suitable for the process of the invention are notably butyrolactone, isophorone and carbitol acetate.
  • liquid medium consist essentially of at least one latent solvent as above described. Minor amounts (less than 5 % wt, preferably less than 1 % wt) of other ingredients/impurities might be present, without properties of the liquid medium being affected.
  • Choice of the ethylenically unsaturated comonomer [comonomer (A)] is not particularly limited and will be done by the skilled in the art by reference to properties of polymer (F) to be modified.
  • Sequential use of two or more such comonomers (A) can provide block graft copolymers with corresponding side chains, properties and structure.
  • comonomer (A) suitable for the process of the invention mention can be made of styrene monomers, (meth)acrylic monomers, chlorinated monomers, functional fluoromonomers, and the like.
  • (meth)acrylic monomers mention can be made of acrylic acid and its ester derivatives, including functional derivatives, methacrylic acid and its ester derivatives, including functional derivatives, acrylonitrile, acrylamides, methacrylamides.
  • halogenated monomers mention can be made of vinyl halides such as vinyl chloride; of vinylidene halides such as vinylidene chloride.
  • CF2 CF(CF2) n SO2F wherein n is an integer between 0 and 6, preferably n is equal to 2 or 3 ;
  • m is an integer between 1 and 10, preferably between 1 and 6, more preferably between 2 and 4, even more preferably m equals 2;
  • CF 2 CF-(OCF2CF(RF 1 )) w -O-CF2(CF(RF2))ySO 2 F
  • w is an integer between 0 and 2
  • Ar is a C5-15 aromatic or heteroaromatic substituent.
  • the comonomer (A) is a
  • R'4 is a hydrogen atom or a C1 -C3 hydrocarbon group, optionally comprising one or more functional groups selected from -OH, -N(R'5)3, wherein each of R' 5, equal to or different from at each occurrence, is independently a hydrogen atom or a C-
  • the comonomer (A) is a
  • each of R1 , R2, R3, equal to or different from each other is independently a hydrogen atom or a C1-C3 hydrocarbon group, and ROH is a hydrogen or a C1 -C5 hydrocarbon moiety comprising at least one hydroxyl group.
  • hydrophilic (meth)acrylic monomers are notably acrylic acid, methacrylic acid, hydroxyethyl (meth)acrylate, hydroxypropyl(meth)acrylate; hydroxyethylhexyl(meth)acrylates.
  • the monomer (MA) is more preferably selected among:
  • HPA 2-hydroxypropyl acrylate
  • the ATRP catalyst comprises generally at least one transition metal and at least one ligand.
  • the ATRP catalyst can be provided to the process of the invention as pre-formed complex of comprising one or more transition metal(s) and one or more ligand(s) or can be formed in situ in the liquid medium by separate addition of one or more transition metal compound(s) and one or more ligand(s).
  • Transition metals comprised in the ATRP catalysts are generally selected in view of their redox chemistry, as they shall act advantageously as one electron oxidants/reductants.
  • Redox couples of transition metals which have been successfully applied in ATRP catalysts are notably Mo lv -Mo v , Mn M -Mn IM , Re v -Re vl , Fe M -Fe MI ,
  • the transition metal is thus preferably Copper or Ruthenium, more
  • Copper (I) salts are particularly suitable for being used as catalyst
  • said ATRP catalyst generally comprises at least one Copper (I) salt and at least one mono- or multi-dentate amine or nitrogenous ligand.
  • Copper (I) salt is generally a Copper (I) halide, preferably Copper (I)
  • the mono- or multi-dentate amine or nitrogenous ligand can be selected from 2,2'-bipyridine and 2,2'-bipyridines substituted at either one or both of the 4 and 4'-positions with one or more alkyl moieties, ethylenediamine, diethylenetriamine, and triethy lenetetramine, each of which can comprise at least one N-substituent independently selected from alkyl, cycloalkyl, and aryl substituents.
  • substituted bipyridine ligands examples include 4,4'-dimethyl-2,2'-bipyridine, 4,4'-di(5-nonyl)-2,2'-bipyridine and various other bipyridyl ligands comprising one or more such alkyl substituents.
  • Such multi-dentate amine ligands can include
  • ditertbutylethylenediamine 1 ,1 ,4,7,7-pentamethyldiethylenetriamine, 1 , 1 ,4,7,7- pentabutyldiethylenetriamine, and 1 ,1 ,4,7,10,10- hexamethyltriethylenetetramine.
  • Polymer (F) is reacted with an ATRP catalyst and with at least one
  • the temperature is higher than 40°C, preferably higher than 50°C, more preferably higher than 60°C.
  • Upper temperature limit is not particularly limited; it is nevertheless
  • the temperature will be selected as to remain below melting point of polymer (F). This temperature will be generally below 170°C, preferably below 150°C, more preferably below 130°C.
  • polymer (F) is at least partially swelled in the liquid medium.
  • the expression 'at least partially swelled' is understood to mean that the volume of the polymer (F) undergoes an increase, typically of at least 5 %, preferably of at least 10 %, more preferably of at least 15 %, with respect to the initial volume of the polymer (F) itself in dry form.
  • the liquid medium is finally cooled so as to obtain a dispersion of particles of grafted copolymer of polymer (F) and comonomer (A).
  • Cooling can be effected by any mean.
  • liquid medium is cooled under stirring, generally without using any external cooling mean, i.e. by simply letting the liquid medium coming naturally back to room
  • particles of grafted copolymer of polymer (F) and comonomer (A) can be separated from liquid medium by known techniques, like notably, filtration, sedimentation, and centrifugation.
  • the invention is further directed to a composition
  • a composition comprising particles of at least one grafted copolymer of polymer (F) and comonomer (A) in a liquid medium comprising at least one latent solvent, as above described, said particles being agglomerates of primary particles having an average primary particle size of 10 to 500 nm, preferably of 50 to 450 nm, even more preferably of 150 to 350 nm.
  • composition can be suitable itself for coating or can be further formulated to yielding proper coating composition.
  • composition of the invention can additionally comprise at least one
  • Polymer (M) typically comprises recurring units selected from the group of formulae j, jj, jjj:
  • R4, R5, R6, R7, equal to or different from each other are independently H or C-i-20 alkyl group
  • RQ is H, alkyl, cycloalkyl, alkaryl, aryl, heterocyclic C-i-36 group.
  • Optionally polymer (M) can comprise additional recurring units different from I, j, jj, jjj, typically derived from ethylenically unsaturated monomers, such as notably olefins, preferably ethylene, propylene, 1 -butene, styrene monomers, such as styrene, alpha-methyl-styrene and the like.
  • polymer (M) is a polymer comprising recurring units derived from one or more than one alkyl (meth)acrylate.
  • a polymer (M) which gave particularly good result within the context of the present invention is a copolymer of methyl methacrylate and ethyl acrylate. This polymer (M) is notably commercially available under trade name PARALOIDTM B-44.
  • the composition can also comprise, either in addition to polymer (M) or in alternative to polymer (M), one or more thermoset resin, said thermoset resin can advantageously undergo crosslinking with the grafted copolymer of polymer (F) and comonomer (A).
  • thermoset resins which can be advantageously used in the composition of the invention are notably:
  • thermosetting - polyamides with amino end groups which can be crosslinked with grafted copolymers containing epoxy groups to form thermosetting
  • Example 1 Manufacture of a graft copolymer of P(VDF-co-CTFE) and 2-hydroxyethyl methacrylate
  • the polymer was transferred to a separatory funnel and washed 4 times with 500ml_ of 50:50 (v/v) Dl watenmethanol, 500 ml_ of 25:75 (v/v) Dl water: methanol, 500 ml_ of methanol, and 500 ml_ of Dl water.
  • Figure 1 is a sketch comprising 9 F-NMR traces recorded from a
  • Figure 2 is a 2D-NMR spectrum by FH-HOESY, which confirms that the CF group having signals in the -170 ppm region indeed interact both with -CH3 group of HEMA and -CH2- groups of the adjacent VDF recurring unit and HEMA.
  • Example 2 Crosslinking of the P(VDF-coCTFE)-£-HEMA copolymer of example 1 with melamine
  • the so-obtained solution was cast onto a glass plate and oven-cured at 120°C for 30 minutes. Upon cooling, a self-standing film was gently detached from the glass support. Said film was tested for its solvent resistance by contacting the same with acetone; no significant swelling nor weight gain or loss was observed when contacting the sample with acetone for 24 hours and separating the same from liquid phase.
  • grafted and melamine crosslinked materials exhibit increased resistance towards acetone, well known as a good solvent for PVDF polymers.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention porte sur un procédé pour la fabrication d'une dispersion d'un copolymère greffé, ledit procédé consistant à : se procurer une dispersion de particules d'au moins un polymère de fluorure de vinylidène (VDF) [polymère (F)] dans un milieu liquide comprenant au moins un solvant latent pour le polymère (F), ledit polymère (F) étant pratiquement insoluble à une température de 25°C dans ledit milieu liquide ; faire réagir dans ledit milieu liquide ledit polymère (F) avec un catalyseur d'ATRP comprenant au moins un sel de métal de transition et au moins un ligand et avec un comonomère à insaturation éthylénique [comonomère (A)] à une température supérieure à 25°C, ledit polymère (F) étant au moins partiellement gonflé dans ledit milieu liquide ; refroidir ledit milieu liquide afin d'obtenir une dispersion de particules de copolymère greffé de polymère (F) et de comonomère (A).
PCT/EP2010/067133 2009-11-13 2010-11-09 Procédé pour la fabrication de polymères greffés Ceased WO2011058016A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US26118509P 2009-11-13 2009-11-13
US61/261,185 2009-11-13

Publications (1)

Publication Number Publication Date
WO2011058016A1 true WO2011058016A1 (fr) 2011-05-19

Family

ID=43302860

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2010/067133 Ceased WO2011058016A1 (fr) 2009-11-13 2010-11-09 Procédé pour la fabrication de polymères greffés

Country Status (1)

Country Link
WO (1) WO2011058016A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015106564A (ja) * 2013-12-02 2015-06-08 三星エスディアイ株式会社Ｓａｍｓｕｎｇ ＳＤＩ Ｃｏ．，Ｌｔｄ． 電池用セパレータ、該電池、及びバインダ用グラフト共重合体の製造方法
WO2015128339A1 (fr) * 2014-02-28 2015-09-03 Solvay Specialty Polymers Italy S.P.A. Fluoropolymères réticulables
CN110734514A (zh) * 2018-07-18 2020-01-31 西南科技大学 一种透明阻燃型聚不饱和磷酸酯及其制备方法
CN111095654A (zh) * 2017-09-14 2020-05-01 株式会社Lg化学 二次电池固体电解质组合物和由其制备的固体电解质
CN113260643A (zh) * 2018-12-21 2021-08-13 索尔维特殊聚合物意大利有限公司 高柔性vdf聚合物

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1019864A (en) * 1963-06-28 1966-02-09 Du Pont Hydrofluorocarbon polymer film-forming composition
GB1049088A (en) * 1964-10-23 1966-11-23 Pennsalt Chemicals Corp Polymer dispersions
GB1049089A (en) * 1964-10-30 1966-11-23 Pennsalt Chemicals Corp Pigmented polymer composition
GB1411577A (en) * 1971-12-21 1975-10-29 Hoechst Ag Coating compositions
EP0341716A2 (fr) * 1988-05-13 1989-11-15 Asahi Glass Company Ltd. Procédé pour fabriquer une dispersion aqueuse, dispersion aqueuse et composition de revêtement aqueux
US4988771A (en) * 1986-07-01 1991-01-29 Soken Kagaku Kabushiki Kaisha Graft copolymer having dispersion stabilizing effect, a process for producing the same, and a process of emulsion polymerization using the same
WO2002022712A2 (fr) 2000-09-11 2002-03-21 Massachusetts Institute Of Technology Copolymeres greffes, procedes servant a greffer des chaines hydrophiles sur des polymeres hydrophobes et articles
US20040192828A1 (en) * 2001-06-28 2004-09-30 Nobuo Mitsuhata Aqueous emulsion resin compositions
WO2007117493A2 (fr) 2006-04-05 2007-10-18 University Of Massachusetts Copolymères greffés et procédés d'élaboration connexes

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1019864A (en) * 1963-06-28 1966-02-09 Du Pont Hydrofluorocarbon polymer film-forming composition
GB1049088A (en) * 1964-10-23 1966-11-23 Pennsalt Chemicals Corp Polymer dispersions
GB1049089A (en) * 1964-10-30 1966-11-23 Pennsalt Chemicals Corp Pigmented polymer composition
GB1411577A (en) * 1971-12-21 1975-10-29 Hoechst Ag Coating compositions
US4988771A (en) * 1986-07-01 1991-01-29 Soken Kagaku Kabushiki Kaisha Graft copolymer having dispersion stabilizing effect, a process for producing the same, and a process of emulsion polymerization using the same
EP0341716A2 (fr) * 1988-05-13 1989-11-15 Asahi Glass Company Ltd. Procédé pour fabriquer une dispersion aqueuse, dispersion aqueuse et composition de revêtement aqueux
WO2002022712A2 (fr) 2000-09-11 2002-03-21 Massachusetts Institute Of Technology Copolymeres greffes, procedes servant a greffer des chaines hydrophiles sur des polymeres hydrophobes et articles
US20040192828A1 (en) * 2001-06-28 2004-09-30 Nobuo Mitsuhata Aqueous emulsion resin compositions
WO2007117493A2 (fr) 2006-04-05 2007-10-18 University Of Massachusetts Copolymères greffés et procédés d'élaboration connexes

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
POLYM. ADV. TECHNOL., 2009
ZHAI M ET AL: "Synthesis of fluorinated polymer electrolyte membranes by radiation grafting and atom transfer radical polymerization techniques", POLYMER, ELSEVIER SCIENCE PUBLISHERS B.V, GB, vol. 50, no. 5, 23 February 2009 (2009-02-23), pages 1159 - 1165, XP025952348, ISSN: 0032-3861, [retrieved on 20090114], DOI: DOI:10.1016/J.POLYMER.2009.01.014 *
ZHANG, MINGFU ET AL.: "Graft Copolymers from Poly(vinylidene fluoride-co-chlorotrifluoroethylene) via Atom Transfer radical Polymerization", MACROMOLECULES, vol. 39, no. 10, 2006, pages 3531 - 3539

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015106564A (ja) * 2013-12-02 2015-06-08 三星エスディアイ株式会社Ｓａｍｓｕｎｇ ＳＤＩ Ｃｏ．，Ｌｔｄ． 電池用セパレータ、該電池、及びバインダ用グラフト共重合体の製造方法
JP2019178332A (ja) * 2013-12-02 2019-10-17 三星エスディアイ株式会社Samsung SDI Co., Ltd. 電池用セパレータ、該電池、及びバインダ用グラフト共重合体の製造方法
WO2015128339A1 (fr) * 2014-02-28 2015-09-03 Solvay Specialty Polymers Italy S.P.A. Fluoropolymères réticulables
US10696768B2 (en) 2014-02-28 2020-06-30 Solvay Speciality Polymers Italy S.P.A. Crosslinkable fluoropolymers
CN111095654A (zh) * 2017-09-14 2020-05-01 株式会社Lg化学 二次电池固体电解质组合物和由其制备的固体电解质
EP3664210A4 (fr) * 2017-09-14 2020-11-11 LG Chem, Ltd. Composition d'électrolyte solide de batterie secondaire et électrolyte solide préparé à partir de celle-ci
JP2020533762A (ja) * 2017-09-14 2020-11-19 エルジー・ケム・リミテッド 二次電池用固体電解質組成物及びこれより製造された固体電解質
US11417909B2 (en) 2017-09-14 2022-08-16 Lg Energy Solution, Ltd. Secondary battery solid electrolyte composition and solid electrolyte prepared therefrom
CN111095654B (zh) * 2017-09-14 2023-05-23 株式会社Lg新能源 二次电池固体电解质组合物和由其制备的固体电解质
CN110734514A (zh) * 2018-07-18 2020-01-31 西南科技大学 一种透明阻燃型聚不饱和磷酸酯及其制备方法
CN113260643A (zh) * 2018-12-21 2021-08-13 索尔维特殊聚合物意大利有限公司 高柔性vdf聚合物
CN113260643B (zh) * 2018-12-21 2024-01-09 索尔维特殊聚合物意大利有限公司 高柔性vdf聚合物

Similar Documents

Publication Publication Date Title
Guerre et al. Deeper insight into the MADIX polymerization of vinylidene fluoride
CN111040058B (zh) 聚四氟乙烯水性分散液的制造方法
US8337725B2 (en) Vinylidene fluoride copolymers
US20070244262A1 (en) Graft copolymers and related methods of preparation
WO2011058016A1 (fr) Procédé pour la fabrication de polymères greffés
CN105985495B (zh) 一种阳离子功能化含氟聚合物及其制备方法
JP5223435B2 (ja) 含フッ素ブロック共重合体
CN110156999B (zh) 一种点击化学合成两亲性含氟嵌段共聚物的制备方法
CN104725545A (zh) 一种新型高粘结性偏氟乙烯共聚物
JP2015507072A (ja) スチレン系フルオロポリマーの調製のための方法
WO2020196779A1 (fr) Procédé de production d'un polymère fluoré, liquide de dispersion aqueuse, et composition de polymère fluoré
CN103588922A (zh) 一种偏氟乙烯共聚物、其制备方法及应用
RU2503689C2 (ru) Способ получения частиц фторполимера
JP7225655B2 (ja) 含フッ素脂肪族環構造を含むフッ素樹脂粒子の製造方法
CN102597033B (zh) 交联的含氟聚合物网络
JP6241929B2 (ja) 異種複合金属ナノ粒子の調製方法
CN110343211B (zh) 一种聚偏氟乙烯共聚物树脂及其制备方法
CN106414512A (zh) 含氟聚合物水性分散液的制造方法
CN110894252B (zh) 一种阴离子型含氟两亲聚合物及其制备方法
Mocny et al. Selective and controlled grafting from PVDF-based materials by oxygen-tolerant green-light-mediated ATRP
CN105985494B (zh) 一种非离子功能化含氟聚合物及其制备方法
JP3824331B2 (ja) ポリフッ化ビニリデンブレンドと高光沢塗料組成のための用途
CN115087677B (zh) 含氟聚合物和其制造方法
CN110894250B (zh) 一种阴离子型含氯两亲聚合物及其制备方法
JP2010037548A (ja) 環構造含有重合体組成物及びその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10773641

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10773641

Country of ref document: EP

Kind code of ref document: A1