Hydrogel, use thereof, and production method therefor

Patent metadata

Field	Value
Publication number	US-11499018-B2
Application number	US-201816629087-A
Country	US
Kind code	B2
Filing date	May 18, 2018
Priority date	Aug 24, 2017
Publication date	Nov 15, 2022
Grant date	Nov 15, 2022

Abstract

A hydrogel has water, a polyvinylsulfonic acid-based polymer, and a polymer matrix containing the water and the polyvinylsulfonic acid-based polymer, in which the polymer matrix contains a copolymer of a monofunctional monomer having one ethylenically unsaturated group and a polyfunctional monomer having 2 to 6 ethylenically unsaturated groups, the copolymer has a hydrophilic group binding to its main chain, the polymer matrix is contained in an amount of 2 to 80 parts by mass in 100 parts by mass of the hydrogel, a polymer derived from the polyfunctional monomer is contained in a proportion of 0.1 to 5 parts by mass in 100 parts by mass of the copolymer, the polyvinylsulfonic acid-based polymer is contained in an amount of 0.1 to 150 parts by mass in 100 parts by mass of the polymer matrix, and the polyvinylsulfonic acid-based polymer has a weight average molecular weight of 200,000 to 3,000,000.

First claim

What is claimed is:

1. A hydrogel comprising water and a polyvinylsulfonic acid-based polymer in a polymer matrix,
wherein
said polymer matrix contains a copolymer of a monofunctional monomer having one ethylenically unsaturated group and a polyfunctional monomer having 2 to 6 ethylenically unsaturated groups,
said copolymer has a hydrophilic group binding to its main chain,
said polymer matrix is contained in an amount of 2 to 80 parts by mass in 100 parts by mass of said hydrogel,
a polymer derived from said polyfunctional monomer is contained in a proportion of 0.1 to 5 parts by mass in 100 parts by mass of said copolymer,
said polyvinylsulfonic acid-based polymer is contained in an amount of 0.1 to 150 parts by mass in 100 parts by mass of said polymer matrix, and
said polyvinylsulfonic acid-based polymer has a weight average molecular weight of 200,000 to 3,000,000.

2. The hydrogel according to claim 1 , wherein when a degree of swelling during immersion in a 7M aqueous potassium hydroxide solution for 1 week under a temperature of 25° C. is represented by B 25° C. [1 week] and a degree of swelling during immersion in a 7M aqueous potassium hydroxide solution for 1 week under a temperature of 60° C. is represented by B 60° C. [1 week] , said hydrogel has a degree of swelling of B 60° C. [1 week] and B 25° C. [1 week] being 550% or less.

3. The hydrogel according to claim 1 , wherein said hydrogel has a ratio of degree of swelling B 60° C. [1 week] /B 25° C. [1 week] (provided that B 60° C. [1 week] is a degree of swelling during immersion in a 7M aqueous potassium hydroxide solution for 1 week under a temperature of 60° C. and B 25° C. [1 week] is a degree of swelling during immersion in a 7M aqueous potassium hydroxide solution for 1 week under a temperature of 25° C.) of 0.5 to 1.5.

4. The hydrogel according to claim 1 , wherein when a piercing strength during immersion in a 7M aqueous potassium hydroxide solution for 1 week under a temperature of 25° C. is represented by F 25° C. [1 week] and a piercing strength during immersion in a 7M aqueous potassium hydroxide solution for 1 week under a temperature of 60° C. is represented by F 60° C. [1 week] , said hydrogel has a piercing strength of F 60° C. [1 week] and F 25° C.[1 week] being 0.25 N or more.

5. The hydrogel according to claim 1 , wherein said hydrogel has a piercing strength ratio (F 25° C. [1 week] −F 60° C. [1 week] )/F 25° C. [1 week] of 0.5 or less (provided that F 25° C. [1 week] is a piercing strength during immersion in a 7M aqueous potassium hydroxide solution for 1 week under a temperature of 25° C. and F 60° C. [1 week] is a piercing strength during immersion in a 7M aqueous potassium hydroxide solution for 1 week under a temperature of 60° C.).

6. The hydrogel according to claim 1 , wherein said monofunctional monomer is selected from (meth)acrylic acid, (meth)acrylamide, sodium (meth)acrylate, potassium (meth)acrylate, zinc (meth)acrylate, dimethyl(meth)acrylamide, vinyl sulfonic acid, sodium vinyl sulfonate, p-styrenesulfonic acid, sodium p-styrenesulfonate, allylsulfonic acid, sodium allylsulfonate, 2-(meth)acrylamido-2-methylpropanesulfonic acid, 3-((meth)acryloyloxy)-1-propanesulfonic acid, potassium 3-((meth)acryloyloxy)-1-propanesulfonate, 3-((meth)acryloyloxy)-2-methyl-1-propanesulfonic acid, potassium 3-((meth)acryloyloxy)-2-methyl-1-propanesulfonate, N-vinylacetamide, N-vinylformamide, allylamine, 2-vinylpyridine, and 4-vinylpyridine,
said polyfunctional monomer is selected from divinylbenzene, sodium divinylbenzenesulfonate, divinylbiphenyl, divinylsulfone, diethylene glycol divinyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, dimethyldiallylammonium chloride, N,N′-methylenebis(meth)acrylamide, ethylene glycol di(meth)acrylate, glycerin tri(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polyglycerin di(meth)acrylate, and
said polyvinylsulfonic acid-based polymer is selected from polystyrenesulfonic acid, sodium polystyrenesulfonate, potassium polystyrenesulfonate, calcium poly styrenesulfonate, polyvinylsulfonic acid, sodium polyvinylsulfonate, and potassium polyvinylsulfonate.

7. A gel-like electrolyte comprising the hydrogel according to claim 1 and an alkali component contained in said hydrogel.

8. The gel-like electrolyte according to claim 7 , wherein said alkali component is selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, and tetraethylammonium hydroxide.

9. A secondary battery including the hydrogel according to claim 1 .

10. A method for producing the hydrogel according to claim 1 , comprising:
preparing a hydrogel precursor containing water, a polyvinylsulfonic acid-based polymer, a monofunctional monomer having one ethylenically unsaturated group, a polyfunctional monomer having 2 to 6 ethylenically unsaturated groups, and a polymerization initiator; and
polymerizing said monofunctional monomer and the polyfunctional monomer to obtain the hydrogel.

11. A secondary battery including the gel-like electrolyte according to claim 7 .

Assignees

• Sekisui Plastics

Inventors

• Akuta Ryo
• Okamoto Koichiro

Classifications

• C08J3/075 Primary

  Macromolecular gels · CPC title

• C08L33/02

  Homopolymers or copolymers of acids; Metal or ammonium salts thereof · CPC title

• C08L41/00

  Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur; Compositions of derivatives of such polymers · CPC title

• C08J2325/06

  Polystyrene · CPC title

• H01B1/06

  mainly consisting of other non-metallic substances · CPC title