WO2020044246A1 - Hydrogel et ses utilisations - Google Patents

Hydrogel et ses utilisations Download PDF

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Publication number
WO2020044246A1
WO2020044246A1 PCT/IB2019/057225 IB2019057225W WO2020044246A1 WO 2020044246 A1 WO2020044246 A1 WO 2020044246A1 IB 2019057225 W IB2019057225 W IB 2019057225W WO 2020044246 A1 WO2020044246 A1 WO 2020044246A1
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Prior art keywords
hydrogel
mass
parts
monomer
group
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PCT/IB2019/057225
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English (en)
Japanese (ja)
Inventor
▲芥▼諒
岡本光一朗
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積水化成品工業株式会社
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Priority claimed from JP2018163485A external-priority patent/JP6718489B2/ja
Priority claimed from JP2019038620A external-priority patent/JP6668530B2/ja
Application filed by 積水化成品工業株式会社 filed Critical 積水化成品工業株式会社
Priority to KR1020217002817A priority Critical patent/KR102489297B1/ko
Priority to US17/262,990 priority patent/US20210163694A1/en
Priority to CN201980051666.0A priority patent/CN112533997B/zh
Priority to EP19854865.3A priority patent/EP3845606A4/fr
Publication of WO2020044246A1 publication Critical patent/WO2020044246A1/fr

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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
    • 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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to hydrogels and uses thereof. More specifically, the present invention relates to a hydrogel capable of suppressing the growth of dendrite, a hydrogel usable even in a high-concentration aqueous electrolyte environment, a gel electrolyte using the same, a separator, and an alkaline battery.
  • the inventors of the present invention solve the second problem by introducing a certain amount of a strongly ionized functional group (for example, a sulfone group) into a skeleton of a polymer matrix constituting a hydrogel.
  • a strongly ionized functional group for example, a sulfone group
  • the hydrophilicity of the skeleton was sometimes increased by the introduction of a strongly ionized functional group. Since the increase in hydrophilicity affects the degree of swelling when immersed in the electrolytic solution and the mechanical strength of the hydrogel, there is room for improvement.
  • the hydrogel When the hydrogel is immersed in an aqueous solution containing 1.5 M LiOH and 10 M LiCl at a temperature of 25 ° C. for one week, it shows a piercing strength of 0.35 N or more. (6) When the hydrogel is immersed for one week in an aqueous solution containing 1.5 M LiOH and 10 M LiCl at a temperature of 25 ° C., the impedance at a frequency of 100 kHz shows a value of 20 ⁇ or less.
  • polyfunctional monomers include N, N '- ⁇ [(2-acrylamido-2-[(3-acrylamidopropoxy) methyl] propane-1,3-diyl) bis (oxy)] bis (propane- 1,3-diyl) diacrylamide (CAS No. 139329-90-2), N, N ', N "-triacryloyldiethylenetriamine (CAS No. 34330-10-4), N, N', N '',N'''-tetraacryloyltriethylenetetramine (CAS No. 158749-66-7) and the like.
  • the polyfunctional monomer may be only one kind or a mixture of plural kinds.
  • the copolymer includes units derived from a monofunctional monomer and a polyfunctional monomer, but the amount of each monomer used in the production of the copolymer, and the content of each unit in the copolymer, Almost the same.
  • the content of the unit derived from the polyfunctional monomer in the copolymer can be measured by pyrolysis GC and / or IR.
  • the hydrogel according to the first embodiment of the present invention may contain an additive, if necessary.
  • Additives include electrolytes, preservatives, bactericides, fungicides, rust inhibitors, antioxidants, defoamers, stabilizers, fragrances, surfactants, coloring agents, gel strength improvers (eg, cellulose nano Fiber).
  • the monofunctional monomer B is not particularly limited as long as it is a monomer having a carboxyl group and one ethylenically unsaturated group.
  • the carboxyl group includes the case where it is present in the monofunctional monomer B in the form of a salt.
  • the monofunctional monomer B may be a mixture of a monomer that is not in a salt form and a monomer in a salt form.
  • the monofunctional monomer B includes (meth) acrylic acid, sodium (meth) acrylate, potassium (meth) acrylate, lithium (meth) acrylate, vinyl benzoic acid, sodium vinyl benzoate, potassium vinyl benzoate, Examples thereof include lithium vinyl benzoate, vinyl acetic acid, sodium vinyl acetate, potassium potassium acetate, and lithium vinyl acetate.
  • (A-3) Content ratio of component derived from monofunctional monomer A and component derived from monofunctional monomer B When the copolymer contains a component derived from monofunctional monomer B, the monofunctional monomer A total of 100 mol% of the component derived from A and the component derived from the monofunctional monomer B, the component derived from the monofunctional monomer A is 30 mol% or more, and the component derived from the monofunctional monomer B is 70 mol. % Or less.
  • the content of the component derived from the monofunctional monomer A can range from 30 mol% to less than 100 mol%, specifically, 30 mol%, 40 mol%, 50 mol%, 60 mol%, 70 mol%, 80 mol%, 90 mol%. , 99 mol%.
  • polyfunctional monomer is not particularly limited as long as it has 2 to 6 ethylenically unsaturated groups. From the viewpoint of alkali resistance, it is preferable not to have an ester bond.
  • polyfunctional monomers include divinylbenzene, sodium divinylbenzene sulfonate, divinyl biphenyl, divinyl sulfone, diethylene glycol divinyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, dimethyldiallylammonium chloride, N, N'- Methylenebis (meth) acrylamide, N, N'-ethylenebis (meth) acrylamide, N, N '- ⁇ [(2-acrylamido-2-[(3-acrylamidopropoxy) methyl] propane-1,3-diyl) bis (Oxy)] bis (propane-1,3-diyl) diacrylamide (CAS
  • the polyfunctional monomer preferably does not have an amide bond.
  • the polyfunctional monomer may be only one kind or a mixture of plural kinds.
  • the polymer derived from the polyfunctional monomer is preferably contained at a ratio of 0.1 to 5 parts by mass with respect to 100 parts by mass of the copolymer.
  • the proportion of the polymer derived from the polyfunctional monomer is less than 0.1 part by mass, the crosslinking density may be low. If the amount is more than 5 parts by mass, the polymer derived from the polyfunctional monomer may undergo phase separation, resulting in a hydrogel having a non-uniform crosslinked structure.
  • the ratio is more preferably from 0.2 to 4.5 parts by mass, and even more preferably from 0.4 to 4.0 parts by mass.
  • the copolymer is composed of components derived from monofunctional monomers and polyfunctional monomers, the amount of each monomer used in the production of the copolymer, the content of each component in the copolymer, Almost the same. Further, the content of the polymer derived from the polyfunctional monomer in the copolymer can be measured by pyrolysis GC and / or IR.
  • Examples of the carboxyl group-containing monomer include (meth) acrylic acid, vinylbenzoic acid, maleic acid, fumaric acid, itaconic acid, and alkali metal salts thereof.
  • Examples of the sulfonic acid monomer include vinyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfonic acid, (meth) acryl sulfonic acid, ethyl (meth) acrylate sulfonic acid, acrylamidohydroxypropane sulfonic acid, and (meth) acrylamidomethylpropane sulfonic acid.
  • the absorbance ratio is larger than 5.0, the ratio derived from the sulfonic acid group unit in the polymer becomes high, so that the cohesive force at the time of immersion in the high-concentration electrolyte solution becomes weak, and the strength reinforcing effect may not be obtained. If it is less than 0.001, the cohesive force becomes too strong, and the hydrogel is separated from water and may be cured.
  • the absorbance ratio is more preferably in the range of 0.001 to 4.5.
  • the range is more preferably from 0.005 to 4.0, further preferably from 0.01 to 3.5, further preferably from 0.025 to 3.0, and further preferably from 0.5 to 3.0.
  • the range is 0.1 to 3.0, more preferably, 0.2 to 2.0.
  • the average degree of polymerization is preferably from 3,000 to 1,800,000, and more preferably from 3,000 to 1,500,000.
  • the polyacrylic acid-based polymer is preferably contained in an amount of 0.5 to 19 parts by mass per 100 parts by mass of the hydrogel. If the content is less than 0.5 parts by mass, the effect of improving mechanical strength may not be obtained. If the amount is more than 19 parts by mass, the entanglement with the polymer network becomes too strong, and the water retention and flexibility of the hydrogel may decrease.
  • the content is preferably 0.5 to 15 parts by mass.
  • the component derived from the monofunctional monomer A and the polyacrylic acid-based polymer are present in the hydrogel in a mass ratio of 100: 2.5 to 90.
  • the water contained in the hydrogel according to the second aspect of the present invention is contained in 21 to 89.5 parts by mass per 100 parts by mass of the hydrogel.
  • the content is less than 21 parts by mass, the amount of the electrolyte component that can be contained becomes small, and when used as a gel electrolyte for a battery, the impedance is high and desired battery characteristics may not be obtained in some cases. If the amount is more than 89.5 parts by mass, the mechanical strength of the hydrogel may decrease.
  • the content is more preferably from 30 to 85 parts by mass, and still more preferably from 40 to 80 parts by mass.
  • the hydrogel according to the second aspect of the present invention may contain, as necessary, other components (a) a support material, (b) a protective film, and (c) an additive. Although it is good, it is the same as (a) the support material, (b) the protective film, and (c) the additive in the first embodiment described above, and thus the description is omitted.
  • a thermal polymerization initiator or a photopolymerization initiator can be used.
  • a photopolymerization initiator which has little change in components before and after polymerization.
  • the photopolymerization initiator include 2-hydroxy-2-methyl-1-phenyl-propan-1-one (product name: Omnirad 1173, manufactured by BASF Japan), 1-hydroxy-cyclohexyl-phenyl-ketone ( Product name: Omnirad 184, manufactured by BASF Japan Ltd.), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-propan-1-one (product name: Omnirad 2959, BASF.
  • the polymerization initiator may be only one kind or a mixture of plural kinds.
  • the amount of the polymerization initiator to be used is preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of all the monomers (monofunctional monomer, polyfunctional monomer and optionally other monomer) in total. When the amount is less than 0.05 parts by mass, the polymerization reaction does not sufficiently proceed, and unpolymerized monomers may remain in the obtained hydrogel. If the amount is more than 5 parts by mass, a residue of the polymerization initiator after the polymerization reaction may give an odor, or physical properties may be reduced due to the influence of the residue.
  • the amount used is more preferably from 0.06 to 3 parts by mass, even more preferably from 0.07 to 1.5 parts by mass.
  • the hydrogel precursor is formed into a sheet by, for example, (i) a method of injecting the hydrogel precursor into a mold, (ii) pouring the hydrogel precursor between protective films, And (iii) a method of coating a hydrogel precursor on a protective film.
  • Method (i) has the advantage that a hydrogel of any shape can be obtained.
  • Methods (ii) and (iii) have the advantage that relatively thin hydrogels can be obtained.
  • the hydrogel containing the support is produced by method (i).
  • the hydrogel precursor may contain other monomers and additives described above.
  • a network structure can be obtained by polymerizing the monofunctional monomer and the polyfunctional monomer in the hydrogel precursor by applying heat or irradiating light.
  • the conditions of heat application and light irradiation are not particularly limited as long as a network structure can be obtained, and general conditions can be adopted.
  • the hydrogel can be used for an alkaline battery (eg, a gel electrolyte, a separator, etc.).
  • the alkaline battery here is a secondary battery that can use a hydrogel as an electrolyte layer and / or a separator between a positive electrode and a negative electrode.
  • Examples of such a secondary battery include a nickel-hydrogen secondary battery, a nickel-zinc secondary battery, a zinc-air battery, a lithium-air battery, an aluminum-air battery, a magnesium-air battery, a calcium-air battery, and a hydrogen-air battery.
  • these secondary batteries use an alkaline aqueous solution as an electrolytic solution, liquid leakage from the secondary batteries can be prevented by the hydrogel.
  • the configuration of the alkaline battery is not particularly limited, and any general configuration can be used.
  • nickel or a nickel alloy is used as a positive electrode of a nickel-hydrogen secondary battery
  • a hydrogen storage alloy is used as a negative electrode
  • nickel or a nickel alloy is used as a positive electrode of a nickel-zinc secondary battery
  • zinc or zinc oxide is used as a negative electrode.
  • the positive electrode and the negative electrode may be formed on a current collector made of nickel, aluminum, copper, or the like.
  • the hydrogel When the hydrogel is a separator, the hydrogel preferably includes a supporting material (intermediate base material).
  • the number of cycles at which the charge / discharge efficiency is 60% or less is preferably 65 cycles or more, more preferably 70 cycles or more, and even more preferably 75 cycles or more. And more preferably 80 cycles or more. A large number of cycles means that an internal short circuit due to dendrite generated on the negative electrode is suppressed.
  • the charge / discharge efficiency after 40 times of charge / discharge is preferably 70% or more, more preferably 75% or more, and further preferably 80%.
  • Applications other than the alkaline battery include uses such as a material for a capacitor, a material for an electric double layer capacitor, and a material for a concrete anticorrosion method.
  • the degree of swelling is defined as a value obtained by subtracting the mass of a blank from the mass of a tea bag containing a hydrogel swelled in a 4M KOH aqueous solution, with the mass of a tea bag containing no hydrogel immersed in a 4M KOH aqueous solution as a blank.
  • the swelling degree (%) was calculated by dividing by the mass of the hydrogel before swelling and multiplying by 100.
  • the degree of swelling after immersion at 25 ° C. for 14 days, after immersion for 21 days, and after immersion for 35 days was B 25 ° C. [14 days] , B 25 ° C.
  • the degree of swelling after dipping for 14 days, after dipping for 21 days, and after dipping for 35 days was B 60 ° C [14 days] , B 60 ° C [21 days] , and B 60 ° C [35 days] , respectively.
  • the hydrogel used a nonwoven fabric or the like as the support material 0.3 g of the hydrogel was scraped off from the support material, and the swelling degree was calculated in the same manner as the above method using the sample as a measurement sample.
  • the degree of swelling was determined by setting the mass of a tea bag not containing a hydrogel immersed in an aqueous solution containing 1.5 M LiOH and 10 M LiCl as a blank, and adding a hydrogel swelled to an aqueous solution containing 1.5 M LiOH and 10 M LiCl.
  • the value obtained by subtracting the mass of the blank from the mass of the tea bag by the mass of the hydrogel before swelling was calculated as a swelling degree (%).
  • a swelling degree %.
  • the hydrogel used a nonwoven fabric or the like as the support material 0.3 g of the hydrogel was scraped off from the support material, and the swelling degree was calculated in the same manner as described above.
  • a piercing test was performed using XT Plus (manufactured by Eiko Seiki Co., Ltd.).
  • the hydrogel was placed on a table having a hole having a diameter of 7 mm, and adjusted to a position where a stainless steel jig having a diameter of 3 mm passed through the center of the hole of the table. Thereafter, the piercing was performed at a speed of 1.0 mm / sec, and the maximum stress until the tip of the jig penetrated was measured. This measurement was carried out for five test pieces, the maximum stress was calculated, and the average of these was defined as the piercing strength. At this time, the piercing strength after immersion at 25 ° C.
  • the piercing strength after immersion at 60 ° C. for 14 days, after immersion for 21 days, and after immersion for 35 days was F 60 ° C. [14 days] , F 60 ° C. [21 days] , and F 60 ° C. [35 days] .
  • the piercing strength after immersion at 60 ° C. for 14 days, after immersion for 21 days, and after immersion for 35 days was F 60 ° C. [14 days] , F 60 ° C. [21 days] , and F 60 ° C. [35 days] .
  • the thickness of the sheet was less than 2 mm, the sheets were laminated so that the thickness was adjusted to 2 mm.
  • a laminate of a zinc electrode plate and a hydrogel was produced by stacking two zinc electrode plates in a state where a hydrogel was interposed between opposed zinc electrode plates having a width of 15 mm, a length of 40 mm, and a thickness of 300 ⁇ m. . Further, the laminate was sandwiched and fixed between two 70 mm square acrylic plates to produce a cell for DC polarization measurement. Note that a sheet made of Teflon (registered trademark) having a width of 10 mm, a length of 30 mm, and a thickness of 800 ⁇ m is sandwiched between the acrylic plates at a position where the laminate of the zinc electrode plate and the hydrogel does not exist between the two acrylic plates.
  • Teflon registered trademark
  • This DC polarization measurement cell was immersed in a 4 M KOH aqueous solution in which zinc oxide was dissolved in saturation at 25 ° C. for 72 hours.
  • the cell for DC polarization measurement after immersion is placed in an acrylic solution containing a 4M aqueous solution of KOH in which zinc oxide is dissolved in saturation, and the zinc in the cell for DC polarization measurement is measured using a measuring device HJ1010SD8 (manufactured by Hokuto Denko KK).
  • a constant DC current of 1 mA / cm 2 was passed between the electrode plates, and a change in voltage over time was measured.
  • the energized state was determined, and the time during which the energized state was maintained from the start of the measurement was defined as the energized time.
  • the measured voltage was less than 0.014 V, a short-circuit state was set.
  • the obtained mixture was further mixed with a self-revolving mixer at 2,000 rpm for 20 minutes to prepare a negative electrode mixture.
  • the obtained negative electrode mixture was fixed to Celmet (manufactured by Sumitomo Electric Industries, Ltd.), dried at 150 ° C. for 5 hours or more, roll-pressed, and cut into 20 mm ⁇ 30 mm to obtain a negative electrode.
  • the thickness of the negative electrode was 700 ⁇ m on average, the negative electrode capacity per unit area was 25 mAh / cm 2 , and the capacity of the manufactured negative electrode was 150 mAh.
  • the battery was subjected to a charge / discharge cycle test in which the battery was charged at a 1 / 2C rate for 1 hour and charged and discharged at a 1 / 2C rate for 1 hour.
  • the number of times of charging and discharging was the number of times of charging and discharging at a 1 / 2C rate.
  • the charge / discharge cycle test was performed for 1 hour for charging and 1 hour for discharging, and the discharge cutoff voltage was 1.0 V.
  • the 1C rate is a current amount that can discharge or charge the entire capacity of the negative electrode in one hour. For example, when the capacity of the positive electrode is 128 mAh, the 1C rate is 128 mA, the 1 / 2C rate is 68 mA, and the 1 / 4C rate is 32 mA.
  • melting point The melting point of the polyfunctional monomer was calculated by differential scanning calorimetry (DSC measurement).
  • the hydrogel was cut into a width of 20 mm and a length of 30 mm, and immersed in 100 mL of an aqueous solution containing 1.5 M LiOH and 10 M LiCl for one week. The hydrogel after immersion was bent until both ends on the long side were in contact. At this time, when the hydrogel was not cracked, it was evaluated as ⁇ , and when it was broken, it was evaluated as x.
  • the hydrogel was cut into a width of 20 mm ⁇ length of 20 mm ⁇ 2 mm and immersed in 100 mL of an aqueous solution containing 1.5 M LiOH and 10 M LiCl for one week to obtain a hydrogel after immersion in a high-concentration electrolyte.
  • the hydrogel after immersion in the high-concentration electrolyte was sandwiched between two Ni plates (width 20 mm, length 40 mm, thickness 1.0 mm) to obtain a test piece.
  • the AC amplitude of the test piece was measured by a two-terminal method with an AC amplitude of 10 mV (rms) and a measurement frequency range of 100 kHz to 100 Hz. From the obtained measurement results, the real component of the impedance at a frequency of 100 kHz (Z ′ / ⁇ ) was defined as the impedance at a frequency of 100 kHz, and the real component of the impedance at a frequency of 1 kHz (Z ′ / ⁇ ) was defined as the impedance at a frequency of 1 kHz.
  • the thickness of the test piece was less than 2 mm, the sheets were laminated, and the thickness of the laminated sheet was adjusted to 2 mm and measured.
  • the weight average molecular weight (Mw) was defined as pullulan-converted weight average molecular weight measured using gel permeation chromatography (GPC). Specifically, 50 mg of a sample was dissolved in 5 mL of a 0.2 M NaNO 3 aqueous solution (permeation time: 24 ⁇ 1 hr (complete dissolution)), and filtered through a 0.45 ⁇ m aqueous chromatodisk (13N) manufactured by GL. was measured using a chromatograph under the following measurement conditions, and the weight average molecular weight of the sample was determined from a standard pullulan calibration curve prepared in advance.
  • GPC gel permeation chromatography
  • the obtained absorbance [1040 ⁇ 20 cm ⁇ 1 ] is calculated using the straight line connecting the wave numbers of 1070 ⁇ 10 cm ⁇ 1 and 990 ⁇ 20 cm ⁇ 1 at the lowest absorbance position that does not intersect with the infrared absorption spectrum in the middle as the baseline.
  • the obtained absorbance [1650 ⁇ 130 cm ⁇ 1 ] is defined as a straight line connecting the wave number between 1770 ⁇ 40 cm ⁇ 1 and 1490 ⁇ 20 cm ⁇ 1 at the lowest absorbance position that does not intersect with the infrared absorption spectrum on the way.
  • a silicon frame having a thickness of 2 mm was placed on the peelable PET film, and the hydrogel precursor was poured into the frame. Then, the peelable PET film was placed on the hydrogel precursor. Then, using a small UV polymerization machine (manufactured by JATEC, J-cure 1500, metal halide lamp model name MJ-1500L), ultraviolet rays having an energy of 7,000 mJ / cm 2 were applied under the conditions of a conveyor speed of 0.4 m / min and a work-to-work distance of 150 mm. By performing the irradiation step three times, a sheet-shaped hydrogel having a thickness of 2 mm was produced.
  • a small UV polymerization machine manufactured by JATEC, J-cure 1500, metal halide lamp model name MJ-1500L
  • a piercing test after immersion in the prepared hydrogel with an alkaline solution was performed.
  • the hydrogel used for the DC polarization measurement and the charge / discharge test was prepared by the following procedure.
  • a polyolefin nonwoven fabric having a thickness of 103 ⁇ m and a basis weight of 45 g / m 2 (OA-1887P, manufactured by Nippon Vilene Co., Ltd.) was placed as a support between the two releasable PET films, and after pouring the above-mentioned hydrogel precursor, After adjusting to a thickness of 200 ⁇ m with a roller, irradiation with UV light of irradiation conditions of 65 mW / cm 2 and / 7,000 mJ / cm 2 was performed using a UV lamp system (product name: Light Hammer 10, manufactured by Heraeus). Thus, a hydrogel having a thickness of 200 ⁇ m was produced.
  • Example 2a The polyfunctional monomer was N, N ′- ⁇ [(2-acrylamido-2-[(3-acrylamidopropoxy) methyl] propane-1,3-diyl) bis (oxy)] bis (propane-1,3-diyl A) Hydrogel was obtained in the same manner as in Example 1a, except that diacrylamide (FAM401, manufactured by Fuji Film Co., melting point 107 ° C.) was changed to 0.66 parts by mass. The swelling characteristics of the obtained hydrogel were evaluated, a piercing test after immersion in an alkaline solution, a DC polarization test, a charge / discharge test, and an appearance evaluation after immersion in an electrolyte were performed.
  • diacrylamide FAM401, manufactured by Fuji Film Co., melting point 107 ° C.
  • Example 3a Except that the polyfunctional monomer was changed to 0.47 parts by mass of N, N ′, N ′′, N ′ ′′-tetraacryloyltriethylenetetramine (FAM402, FAM402, melting point 110 ° C.) A hydrogel was obtained in the same manner as in 1a. The swelling characteristics of the obtained hydrogel were evaluated, a piercing test after immersion in an alkaline solution, a DC polarization test, a charge / discharge test, and an appearance evaluation after immersion in an electrolyte were performed.
  • FAM402 FAM402, melting point 110 ° C.
  • Example 4a A hydrogel was obtained in the same manner as in Example 1a, except that the monofunctional monomer was changed to 2-acrylamido-2-methylpropanesulfonic acid (AMPS, manufactured by MCC Unitech). The swelling characteristics of the obtained hydrogel were evaluated, a piercing test after immersion in an alkaline solution, a DC polarization test, a charge / discharge test, and an appearance evaluation after immersion in an electrolyte were performed.
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • Example 5a A hydrogel was obtained in the same manner as in Example 2a, except that the monofunctional monomer was changed to 2-acrylamido-2-methylpropanesulfonic acid. The swelling characteristics of the obtained hydrogel were evaluated, a piercing test after immersion in an alkaline solution, a DC polarization test, a charge / discharge test, and an appearance evaluation after immersion in an electrolyte were performed.
  • Example 1a A hydrogel was obtained in the same manner as in Example 1a, except that the polyfunctional monomer was changed to 0.3 parts by mass of sodium divinylbenzenesulfonate (DVBS, manufactured by Tosoh Organic Chemicals, Inc.). The swelling characteristics of the obtained hydrogel were evaluated, a piercing test after immersion in an alkaline solution, a DC polarization test, and a charge / discharge test were performed.
  • DVBS sodium divinylbenzenesulfonate
  • Example 2a A hydrogel was obtained in the same manner as in Example 1a, except that the polyfunctional monomer was changed to 0.6 parts by mass of sodium divinylbenzene sulfonate (manufactured by Tosoh Organic Chemicals, Inc.). The swelling characteristics of the obtained hydrogel were evaluated, a piercing test after immersion in an alkaline solution, a DC polarization test, and a charge / discharge test were performed.
  • Example 1a Example 1a except that the polyfunctional monomer was changed to 0.3 parts by mass of A-200 (polyethylene glycol # 200 diacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.) having two ethylenically unsaturated groups and an ester bond.
  • a hydrogel was obtained in the same manner as described above. Since the obtained hydrogel was liquefied when immersed in an alkaline solution, various physical properties could not be measured.
  • Example 1a Example 1a except that the polyfunctional monomer was changed to 0.4 parts by mass of A-400 (polyethylene glycol # 400 diacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.) having two ethylenically unsaturated groups and an ester bond.
  • a hydrogel was obtained in the same manner as described above. Since the obtained hydrogel was liquefied when immersed in an alkaline solution, various physical properties could not be measured.
  • Example 1a Example 1a except that the polyfunctional monomer was changed to 0.45 parts by mass of A-GLY-9EA having three ethylenically unsaturated groups and an ester bond (Ethoxylated glycerine triacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • a hydrogel was obtained in the same manner. Since the obtained hydrogel was liquefied when immersed in an alkaline solution, various physical properties could not be measured.
  • Example 6a Same as Example 1a except that the polyfunctional monomer was changed to 0.3 parts by mass of A-TMMT (pentaerythritol tetraacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.) having four ethylenically unsaturated groups and an ester bond. To obtain a hydrogel. Since the obtained hydrogel was liquefied when immersed in an alkaline solution, various physical properties could not be measured.
  • A-TMMT penentaerythritol tetraacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.
  • ⁇ Comparative Example 7a> According to the contents described in Japanese Patent Application Laid-Open No. 2015-95286, a polytetrafluoroethylene emulsion aqueous solution having a concentration of 60% by mass (Polyflon PTFE D made by Daikin Industries, Ltd.) is used for 2.5 g of hydrotalcite as a layered double hydroxide. -210C) 5 g, and 2.5 g of a 20% by mass aqueous solution of polyethyleneimine (EPOMIN SP200 manufactured by Nippon Shokubai Co., Ltd.) were kneaded and rolled to obtain a 200 ⁇ m sheet. The swelling characteristics of the obtained sheet were evaluated, a piercing test after immersion in an alkaline solution, a DC polarization test, and a charge / discharge test were performed.
  • Polyflon PTFE D made by Daikin Industries, Ltd.
  • the obtained hydrogel was cut into a 30 mm square.
  • the cut hydrogel was immersed in 100 mL of a 4 M aqueous KOH solution at a temperature of 25 ° C. for 3 days.
  • the distance between adjacent vertices of the hydrogel after immersion was measured, and the distance D between vertices was determined.
  • the distance D between the vertices was divided by 30 mm and the value was less than 0.75, it means that the hydrogel after immersion in the electrolytic solution was warped or wound, and was evaluated as x.
  • the value was 0.75 or more, it means that the hydrogel sheet did not change in shape after immersion in the electrolytic solution, and was evaluated as ⁇ .
  • Example 1b 20 parts by mass of 2-acrylamide-2-methylpropanesulfonic acid (product name: TBAS, manufactured by MCC Unitech), 0.3 parts by mass of sodium divinylbenzenesulfonate (product name: DVBS, manufactured by Tosoh Organic Chemicals), ion exchange 54.6 parts by mass of water was put in a container and stirred. Further, 25 parts by mass of a 20% by mass aqueous solution of Julimer AC-10LP (manufactured by Toagosei Co., Ltd., polyacrylic acid, weight average molecular weight: 20,000) was added and stirred.
  • Julimer AC-10LP manufactured by Toagosei Co., Ltd., polyacrylic acid, weight average molecular weight: 20,000
  • a sheet-shaped hydrogel having a thickness of 2 mm was produced.
  • the prepared hydrogel was subjected to swelling degree measurement, immersion in electrolyte solution, bending test, piercing test, and AC impedance measurement.
  • Example 1b A 2 mm-thick sheet-like hydrogel was prepared in the same manner as in Example 1b except that this hydrogel precursor was used.
  • the prepared hydrogel was subjected to swelling degree measurement, immersion in electrolyte solution, bending test, piercing test, and AC impedance measurement.
  • Example 1b A 2 mm-thick sheet-like hydrogel was prepared in the same manner as in Example 1b except that this hydrogel precursor was used.
  • the prepared hydrogel was subjected to swelling degree measurement, immersion in electrolyte solution, bending test, piercing test, and AC impedance measurement.
  • Example 5b 20 parts by mass of 2-acrylamide-2-methylpropanesulfonic acid (product name: TBAS, manufactured by MCC Unitech), 0.3 parts by mass of sodium divinylbenzenesulfonate (product name: DVBS, manufactured by Tosoh Organic Chemicals), polyacryl 80 parts by mass of a 5% by mass aqueous solution of an acid (manufactured by Wako Pure Chemical Industries, polyacrylic acid, weight average molecular weight: 1,000,000) was added and stirred. 0.10 parts by mass of Omnirad 1173 (manufactured by BASF Japan) as a polymerization initiator was added to this solution, and the mixture was stirred to prepare a hydrogel precursor.
  • TBAS 2-acrylamide-2-methylpropanesulfonic acid
  • DVBS sodium divinylbenzenesulfonate
  • polyacryl 80 parts by mass of a 5% by mass aqueous solution of an acid manufactured by Wako Pure Chemical Industries, polyacrylic acid, weight average molecular
  • Example 9b 20 parts by mass of 2-acrylamide-2-methylpropanesulfonic acid (product name: TBAS, manufactured by MCC Unitech), 0.3 parts by mass of sodium divinylbenzenesulfonate (product name: DVBS, manufactured by Tosoh Organic Chemicals), ion exchange 54.6 parts by mass of water was put in a container and stirred. Further, 25 parts by mass of a 20% by mass aqueous solution of Aqualic DL453 (manufactured by Nippon Shokubai Co., Ltd., sodium polyacrylate, weight average molecular weight: 50,000) was added and stirred.
  • Aqualic DL453 manufactured by Nippon Shokubai Co., Ltd., sodium polyacrylate, weight average molecular weight: 50,000
  • ⁇ Comparative Example 2b 20 parts by mass of acrylic acid (manufactured by Nippon Shokubai Co., Ltd.), 0.3 parts by mass of sodium divinylbenzenesulfonate (product name: DVBS, manufactured by Tosoh Organic Chemicals), and 79.5 parts by mass of ion-exchanged water were put in a container and stirred. To this solution was added 0.20 parts by mass of Omnirad 1173 (manufactured by BASF Japan) as a polymerization initiator, and the mixture was stirred to prepare a hydrogel precursor. A 2 mm-thick sheet-like hydrogel was prepared in the same manner as in Example 1b except that this hydrogel precursor was used. The prepared hydrogel was subjected to swelling degree measurement, immersion in electrolyte solution, bending test, piercing test, and AC impedance measurement.
  • a 2 mm-thick sheet-like hydrogel was prepared in the same manner as in Example 1b except that this hydrogel precursor was used.
  • the prepared hydrogel was subjected to swelling degree measurement, immersion in electrolyte solution, bending test, piercing test, and AC impedance measurement.
  • ⁇ Comparative Example 5b 10 parts by mass of 2-acrylamide-2-methylpropanesulfonic acid (product name: TBAS, manufactured by MCC Unitech), 0.3 parts by mass of sodium divinylbenzenesulfonate (product name: DVBS, manufactured by Tosoh Organic Chemicals), ion exchange 54.6 parts by mass of water was put in a container and stirred.
  • 2-acrylamide-2-methylpropanesulfonic acid product name: TBAS, manufactured by MCC Unitech
  • sodium divinylbenzenesulfonate product name: DVBS, manufactured by Tosoh Organic Chemicals
  • Table 7 shows the absorbance and the absorbance ratio of the polyacrylic acid polymers used in Examples 1b to 13b.

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Abstract

La présente invention concerne un hydrogel et ses utilisations. L'invention concerne spécifiquement un hydrogel contenant de l'eau et une matrice macromoléculaire et des utilisations dudit hydrogel, l'hydrogel étant caractérisé en ce que : la matrice macromoléculaire comprend un copolymère d'un monomère monofonctionnel possédant un groupe hydrophile et un groupe à insaturation éthylénique et d'un monomère polyfonctionnel possédant un groupe amide et trois à six groupes à insaturation éthylénique mais ne comportant pas de liaison ester; 40 à 95 parties en masse d'eau et 5 à 60 parties en masse de la matrice macromoléculaire sont incluses pour 100 parties en masse de l'hydrogel; et lorsque l'hydrogel a été immergé dans une solution aqueuse de KOH 4M à une température de 25 °C pendant 14 jours, le degré de gonflement de l'hydrogel n'est pas supérieur à 650 %.
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CN201980051666.0A CN112533997B (zh) 2018-08-31 2019-08-28 水凝胶和其用途
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WO2017051734A1 (fr) 2015-09-25 2017-03-30 積水化成品工業株式会社 Hydrogel et son procédé de production
JP2017068933A (ja) 2015-09-28 2017-04-06 ニッポン高度紙工業株式会社 電池用セパレータ及び該セパレータを備えた二次電池
JP2017183204A (ja) 2016-03-31 2017-10-05 積水化成品工業株式会社 アルカリ亜鉛蓄電池
JP2018163485A (ja) 2017-03-24 2018-10-18 富士ゼロックス株式会社 データ送信システムおよびプログラム
JP2018168757A (ja) 2017-03-30 2018-11-01 株式会社豊田自動織機 スクロール型圧縮機
JP2019038620A (ja) 2017-08-22 2019-03-14 キヤノン株式会社 画像形成装置、温度制御方法

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JP2005322635A (ja) 2004-04-09 2005-11-17 Dainichiseika Color & Chem Mfg Co Ltd アルカリ電池用高分子ヒドロゲル電解質およびその製造方法
JP2012033490A (ja) 2010-07-28 2012-02-16 Samsung Electronics Co Ltd リチウム空気電池
JP2013185119A (ja) * 2012-03-09 2013-09-19 Sekisui Plastics Co Ltd 粘着性ハイドロゲル及びその用途
JP2015095286A (ja) 2013-11-08 2015-05-18 株式会社日本触媒 アニオン伝導膜及び電池
WO2015146840A1 (fr) * 2014-03-28 2015-10-01 積水化成品工業株式会社 Gel adhérent riche en eau, composition pour la fabrication d'un gel adhérent riche en eau, et plot d'électrode
WO2016031709A1 (fr) * 2014-08-29 2016-03-03 富士フイルム株式会社 Produit cosmétique pour ongles, ongle artificiel, et trousse de décoration d'ongles
WO2017051734A1 (fr) 2015-09-25 2017-03-30 積水化成品工業株式会社 Hydrogel et son procédé de production
JP2017068933A (ja) 2015-09-28 2017-04-06 ニッポン高度紙工業株式会社 電池用セパレータ及び該セパレータを備えた二次電池
JP2017183204A (ja) 2016-03-31 2017-10-05 積水化成品工業株式会社 アルカリ亜鉛蓄電池
JP2018163485A (ja) 2017-03-24 2018-10-18 富士ゼロックス株式会社 データ送信システムおよびプログラム
JP2018168757A (ja) 2017-03-30 2018-11-01 株式会社豊田自動織機 スクロール型圧縮機
JP2019038620A (ja) 2017-08-22 2019-03-14 キヤノン株式会社 画像形成装置、温度制御方法

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