公开(公告)号：US12018106B2

公开(公告)日：2024-06-25

申请号：US17725459

申请日：2022-04-20

Applicant: AGC INC.

Inventor： Takeshi Hirai ,  Susumu Saito ,  Hiroyuki Watabe

IPC: H01M8/1004 ,  C08F216/14 ,  C08K3/04 ,  C08K3/08 ,  C08K3/22 ,  H01M8/1039 ,  H01M8/1072 ,  H01M8/10

CPC classification number: C08F216/1475 ,  C08K3/04 ,  C08K3/08 ,  C08K3/22 ,  H01M8/1004 ,  H01M8/1039 ,  H01M8/1072 ,  C08K2003/2244 ,  H01M2008/1095

Abstract: The present invention provides a fluoropolymer containing fluorosulfonyl groups capable of forming a polymer electrolyte membrane with high conductivity and hot water resistance, a method for its production, a fluoropolymer containing acid-form sulfonic acid groups and a method for its production, a polymer electrolyte membrane, a membrane-electrode assembly and a polymer electrolyte fuel cell. The method for producing a fluoropolymer containing fluorosulfonyl groups of the present invention comprises copolymerizing a monomer m1 (CF2═CFCF2O-Q1-SO2F) and TFE in a reactor at a temperature of from 150 to 200° C. in the presence of a radical polymerization initiator, wherein the radical polymerization initiator is continuously or sequentially added into the reactor so that the concentration of the radical polymerization initiator is kept to at most 2.5 mass ppm of the initial feed of the monomer m1 present in the reactor before initiation of the copolymerization during the copolymerization, and the molar ratio of the total feed of the monomer m1 to the total feed of tetrafluoroethylene is from 1.5 to 20.

公开(公告)号：US10975209B2

公开(公告)日：2021-04-13

申请号：US16716968

申请日：2019-12-17

Applicant: AGC Inc.

Inventor： Susumu Saito ,  Atsushi Watakabe

IPC: C08J5/22 ,  B01J39/04 ,  B01J47/00 ,  C08F216/14 ,  C08F214/24 ,  B01J39/20 ,  B01J39/05 ,  B01J47/012 ,  B01J39/07 ,  C25B1/46 ,  C25B13/08 ,  H01M8/1023 ,  H01M8/1039 ,  H01M8/1018

Abstract: To provide a method for producing a fluorinated polymer which enables stable production of a fluorinated polymer having a high molecular weight at a high polymerization rate with good productivity and reduced environmental burdens, a method for producing a fluorinated polymer having functional groups, and a method for producing an electrolyte membrane. A method for producing a fluorinated polymer, which comprises polymerizing a monomer mixture containing tetrafluoroethylene and a fluorinated monomer having a group convertible to a sulfonic acid group or a carboxylic acid group in a polymerization medium, wherein the polymerization medium contains as the main component a C4-10 cyclic hydrofluorocarbon. Further, a method for producing a fluorinated polymer having functional groups and a method for producing an electrolyte membrane, employing the production method.

公开(公告)号：US12040515B2

公开(公告)日：2024-07-16

申请号：US17472999

申请日：2021-09-13

Applicant: AGC Inc.

Inventor： Susumu Saito

IPC: H01M8/10 ,  H01M8/1004 ,  H01M8/1039 ,  H01M50/406 ,  H01M50/426 ,  H01M50/491 ,  H01M50/497

CPC classification number: H01M8/1004 ,  H01M8/1039 ,  H01M50/406 ,  H01M50/426 ,  H01M50/491 ,  H01M50/497 ,  H01M2300/0082 ,  H01M2300/0085

Abstract: To provide a membrane electrode assembly which can suppress cracking of the catalyst layers.
The membrane electrode assembly of the present invention is a membrane electrode assembly comprising an anode having a catalyst layer containing a proton-conductive polymer, a cathode having a catalyst layer containing a proton-conductive polymer, and a polymer electrolyte membrane disposed between the anode and the cathode, wherein the proton-conductive polymer contained in the catalyst layer of at least one of the anode and the cathode is a polymer (H) having units containing a cyclic ether structure and sulfonic acid-type functional groups, and the polymer electrolyte membrane contains a porous material containing a fluorinated polymer, and a fluorinated polymer (S) having sulfonic acid-type functional groups.

公开(公告)号：US11987656B2

公开(公告)日：2024-05-21

申请号：US17061703

申请日：2020-10-02

Applicant: AGC Inc.

Inventor： Susumu Saito ,  Satoru Hommura ,  Hiroyuki Watabe

IPC: C08F216/38 ,  C08F214/18 ,  C08J5/22 ,  H01M8/1004 ,  H01M8/1039 ,  H01M8/1088 ,  H01M8/10

CPC classification number: C08F214/184 ,  C08F216/38 ,  C08J5/225 ,  H01M8/1004 ,  H01M8/1039 ,  H01M8/1088 ,  C08J2327/12 ,  H01M2008/1095

Abstract: To provide a method for producing a fluorinated polymer, in which it is possible to efficiently and easily control the molecular weight to be proper when polymerizing a perfluoromonomer having a dioxolane ring containing a polymerizable double bond in the ring skeleton, and in which the obtainable fluorinated polymer is less susceptible to a decrease in molecular weight even when contacted with a base. A method for producing a fluorinated polymer, comprising polymerizing a raw-material mixture which contains at least one of a monomer composition M11 which comprises a perfluoromonomer represented by the formula m11 and a fluorinated monomer m11H having at least some of fluorine atoms of said perfluoromonomer substituted by hydrogen atoms, and a monomer composition M12 which comprises a perfluoromonomer represented by formula m12 and a fluorinated monomer m12H having at least some of fluorine atoms of said perfluoromonomer substituted by hydrogen atoms, wherein the total amount of the fluorinated monomer mil H and the fluorinated monomer m12H is from 10 to 1,100 ppm to the total amount of the monomer composition M11 and the monomer composition M12.

公开(公告)号：US12261335B2

公开(公告)日：2025-03-25

申请号：US17333682

申请日：2021-05-28

Applicant: AGC Inc.

Inventor： Susumu Saito ,  Takumi Okuyama ,  Hiroyuki Watabe

IPC: H01M8/1039 ,  C08K3/22 ,  C08L27/12 ,  H01M8/1051 ,  H01M8/1067

Abstract: To provide a liquid composition capable of forming a polymer electrolyte membrane which is excellent in the initial power generation characteristics when made into a membrane electrode assembly, and which is excellent in durability and has few defects. This liquid composition comprises a liquid medium, a sulfonic acid group-containing fluorocarbon polymer and a hardly soluble cerium compound, wherein the ion exchange capacity of the sulfonic acid group-containing fluorocarbon polymer is from 1.36 to 2.50 meq/g dry resin, the average particle size of the hardly soluble cerium compound is from 1 nm to 3,000 nm, and the ratio of the total number of moles of cerium atoms in the hardly soluble cerium compound to the total number of moles of sulfonic acid groups in the sulfonic acid group-containing fluorocarbon polymer is from 0.001 to 0.3.

公开(公告)号：US11898018B2

公开(公告)日：2024-02-13

申请号：US17332145

申请日：2021-05-27

Applicant: AGC Inc.

Inventor： Takumi Okuyama ,  Takeshi Hirai ,  Susumu Saito ,  Chikaya Tamitsuji ,  Daisuke Jomuta

IPC: C08J5/22 ,  C08L29/10 ,  H01M8/10 ,  H01M8/1004 ,  H01M8/1039 ,  H01M8/1051

CPC classification number: C08J5/225 ,  C08L29/10 ,  H01M8/1004 ,  H01M8/1039 ,  H01M8/1051 ,  C08J2329/10 ,  H01M2008/1095 ,  H01M2300/0082

Abstract: To provide a liquid composition capable of forming a membrane excellent in durability against hydrogen peroxide or peroxide radicals and excellent in hydrogen gas barrier property; a polymer electrolyte membrane; a membrane electrode assembly; and a polymer electrolyte fuel cell.
Liquid composition comprising a liquid medium, an acid-type sulfonic acid group-containing fluorocarbon polymer of which the hydrogen gas permeation coefficient under the conditions of a temperature of 80° C. and a relative humidity of 10% is at most 2.5×10−9 cm3·cm/(s·cm2·cmHg), and cerium atoms; a polymer electrolyte membrane 15 comprising the acid-type sulfonic acid group-containing fluorocarbon polymer, and cerium atoms; and a membrane electrode assembly 10 comprising an anode 13 having a catalyst layer, a cathode 14 having a catalyst layer, and the polymer electrolyte membrane 15 disposed between the anode 13 and the cathode 14.

公开(公告)号：US11851508B2

公开(公告)日：2023-12-26

申请号：US17330788

申请日：2021-05-26

Applicant: AGC Inc.

Inventor： Takeshi Hirai ,  Susumu Saito ,  Hiroyuki Watabe ,  Chikaya Tamitsuji ,  Daisuke Jomuta

IPC: C08F16/30 ,  B01J39/05 ,  B01J39/20 ,  C08J5/22 ,  C25B1/04 ,  C25B13/08 ,  H01M8/1004 ,  H01M8/1023 ,  H01M8/1039 ,  H01M8/1067 ,  H01M8/10

CPC classification number: C08F16/30 ,  B01J39/05 ,  B01J39/20 ,  C08J5/2231 ,  C25B1/04 ,  C25B13/08 ,  H01M8/1004 ,  H01M8/1023 ,  H01M8/1039 ,  H01M8/1067 ,  C08J2329/10 ,  H01M2008/1095

Abstract: An acid-type sulfonic acid group-containing polymer containing perfluoromonomer units, no monomer units having a halogen atom other than a fluorine atom, and acid type sulfonic acid groups, whose hydrogen gas permeability coefficient under the conditions of a temperature of 80° C. and a relative humidity of 10% is at most 2.5×10−9 cm3·cm/(s·cm2·cmHg), and whose mass reduction rate when immersed in hot water at 120° C. for 24 hours is at most 15 mass %. Liquid composition, membrane electrode assembly, polymer electrolyte fuel cell, and ion exchange membrane utilizing the acid-type sulfonic acid group-containing polymer.

公开(公告)号：US11274168B2

公开(公告)日：2022-03-15

申请号：US16282377

申请日：2019-02-22

Applicant: AGC Inc.

Inventor： Susumu Saito ,  Wakako Hashimoto

IPC: C08F14/18 ,  C08F34/02 ,  H01M8/1032 ,  H01M8/1004 ,  H01M4/90 ,  H01M8/1027 ,  H01M8/10 ,  C08F214/26 ,  C08F216/14 ,  C08F234/02 ,  C08F134/02 ,  C08F214/18 ,  C08F114/18

Abstract: To provide a monomer composition in which the solubility of the polymerization inhibitor in the cyclic monomer is good, the stability of the cyclic monomer during storage is good, and the cyclic monomer and the polymerization inhibitor are easily separated by distillation; and a method for producing a high molecular weight fluorinated polymer from the monomer composition.
A monomer composition which comprises a specific cyclic monomer and a polymerization inhibitor, wherein the polymerization inhibitor is a polymerization inhibitor which satisfies (a) it is a 6-membered unsaturated cyclic hydrocarbon having from 1 to 4 substituents, (b) it has, as the substituent, at least one type selected from the group consisting of a t-butyl group, a methyl group, an isopropenyl group, an oxo group and a hydroxy group, (c) in a case where it has an oxo group as one type of the substituent, it has, as the substituent other than the oxo group, either one or both of a t-butyl group and a methyl group, and (d) in a case where it has a hydroxy group as the substituent, the number of the hydroxy group is only one.

公开(公告)号：US20190221874A1

公开(公告)日：2019-07-18

申请号：US16363746

申请日：2019-03-25

Applicant: AGC Inc.

Inventor： Susumu Saito ,  Hiroyuki Watabe ,  Takumi Okuyama

IPC: H01M8/1039 ,  H01M8/1023 ,  H01M8/1004 ,  C08F216/14

CPC classification number: H01M8/1039 ,  C08F8/12 ,  C08F216/1466 ,  C08F216/16 ,  C08F2216/1475 ,  C08J5/22 ,  H01B1/06 ,  H01M8/02 ,  H01M8/10 ,  H01M8/1004 ,  H01M8/1023 ,  H01M2008/1095

Abstract: To provide a polymer capable of forming a polymer electrolyte membrane that is resistant to breakage even when being repeatedly subjected to humidification and drying or a catalyst layer that is resistant to formation of cracks; a polymer electrolyte membrane employing said polymer; and a membrane/electrode assembly for a polymer electrolyte fuel cell. A polymer comprising units (u1) having two ion-exchange groups and units (u2) of e.g. a perfluoro(alkyl vinyl ether), wherein the molar ratio (u2)/((u1)+(u2)) is more than 0.30 and at most 0.70. A membrane/electrode assembly 10 comprising an anode 13 having a catalyst layer 11 and a gas diffusion layer 12, a cathode 14 having a catalyst layer 11 and a gas diffusion layer 12, and a polymer electrolyte membrane 15 disposed between the anode 13 and the cathode 14 in a state of being contact with the catalyst layers 11, wherein either one or each of the catalyst layers 11 and the polymer electrolyte membrane 15 contains the aforementioned polymer.

公开(公告)号：US10214619B2

公开(公告)日：2019-02-26

申请号：US15176408

申请日：2016-06-08

Applicant: AGC Inc.

Inventor： Norihide Sugiyama ,  Ryujiro Yamasaki ,  Susumu Saito ,  Akihiko Asakawa ,  Masahiro Ohkura ,  Shinji Wada

IPC: C08J3/24 ,  C08F214/18 ,  C08J3/28 ,  H01L33/56

Abstract: To provide a process for producing a fluorinated crosslinked product which is excellent in stability and produces less HF.A process for producing a fluorinated crosslinked product, which comprises irradiating a fluorinated polymer having a unit represented by the following formula (1), with active energy rays having a wavelength of from 150 to 300 nm: wherein X1 and X2 are each independently a hydrogen atom or a fluorine atom, Rf1 is a fluoroalkylene group or a fluoroalkylene group having at least two carbon atoms and an etheric oxygen atom between carbon-carbon atoms, Q1 is a single bond or an etheric oxygen atom, and Z1 is OH, OR1 or NR2R3, wherein R1 is an alkyl group, and R2 and R3 are each independently a hydrogen atom or an alkyl group.