WO2023027057A1 - 高分子電解質、バイオプラスチック及び成形体 - Google Patents

高分子電解質、バイオプラスチック及び成形体 Download PDF

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WO2023027057A1
WO2023027057A1 PCT/JP2022/031675 JP2022031675W WO2023027057A1 WO 2023027057 A1 WO2023027057 A1 WO 2023027057A1 JP 2022031675 W JP2022031675 W JP 2022031675W WO 2023027057 A1 WO2023027057 A1 WO 2023027057A1
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polymer electrolyte
bioplastic
oxygen
fatty acid
substance
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French (fr)
Japanese (ja)
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岳志 今井
久明 三原
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Hyogo Prefectural Government
Ritsumeikan Trust
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Hyogo Prefectural Government
Ritsumeikan Trust
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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
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • 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
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/20—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
    • 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
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/22—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having three or more carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to polymers of unsaturated fatty acids, and particularly to polymers of polyunsaturated fatty acids.
  • Bioplastics are manufactured from raw materials including plant-based raw materials, and can be decomposed by microorganisms that exist in soil and water. In addition, since non-exhaustible resources are used, exhaustible resources such as petroleum can be saved during plastic production and global warming countermeasures can be taken.
  • Lipids such as fats and fatty acids are derived from natural products and are materials with low environmental impact. Lipids containing unsaturated fatty acids are known to oxidize and harden in the presence of catalysts. However, these gelate during the reaction, and the cured product has almost no thermoplasticity. Therefore, for example, it is difficult to use such cured lipids as raw materials for injection molded articles such as resin pellets.
  • lipids containing unsaturated fatty acids require oxygen for the curing reaction, it is difficult for air to reach the inside from the surface, and the polymerization reaction does not complete in the three-dimensional molded body. Therefore, the cured product of such a lipid cannot be used for anything other than coating.
  • the purpose of the present invention is to provide a novel polymer electrolyte, a bioplastic that can be molded into a tough three-dimensional object, and a molded article using these.
  • the present invention provides means for solving problems in the following aspects.
  • a bioplastic comprising a polyelectrolyte according to any one of aspects 1-7.
  • a molded article comprising the cured bioplastic material according to any one of aspects 8 to 10.
  • a method for producing a polymer electrolyte comprising:
  • a method for producing bioplastics comprising:
  • a method for producing a molded body comprising:
  • a novel polymer electrolyte, a bioplastic that can be molded into a tough three-dimensional object, and a molded body using these are provided.
  • the polymer electrolyte of the present invention has a structure in which some of the unsaturated groups of unsaturated fatty acids are bonded together. Accordingly, the polyelectrolyte of the present invention is a partial polymer of unsaturated fatty acids. In other words, the polymer electrolyte of the present invention still has unsaturated groups, which are further polymerized to exhibit curability.
  • the polymer electrolyte of the present invention has a structure in which some of the carboxyl groups derived from unsaturated fatty acids are converted into salts.
  • the polymer electrolyte exhibits electrical repulsion between the main chains, suppresses mutual entanglement, and exhibits thermoplasticity.
  • the polymer electrolyte of the present invention is produced using unsaturated fatty acids as raw materials.
  • Unsaturated fatty acids have double bonds and can be cured, for example, by polymerizing in the presence of oxygen in the air.
  • the unsaturated fatty acid has a carboxyl group, which can be converted into a salt by neutralizing it with a basic substance.
  • the unsaturated fatty acid for example, a fatty acid having 16 or more carbon atoms, 2 or more double bonds and a carboxyl group is used. Since the unsaturated fatty acid has two or more double bonds, it can form a crosslinked structure during the polymerization reaction, thereby improving the chemical resistance, heat resistance, or strength of the resulting molded product.
  • the number of double bonds in the unsaturated fatty acid is preferably 2-6, more preferably 2-4, still more preferably 2 or 3.
  • the unsaturated fatty acid preferably has 16 to 22 carbon atoms, more preferably 16 to 20 carbon atoms, and still more preferably 18 carbon atoms from the viewpoint of availability.
  • unsaturated fatty acids include oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid and docosahexaenoic acid.
  • unsaturated fatty acids are linoleic acid, linolenic acid and arachidonic acid.
  • the unsaturated fatty acid is preferably derived from plants, more preferably linoleic acid, ⁇ -linolenic acid and ⁇ -linolenic acid.
  • a single type of unsaturated fatty acid may be used, or a mixture of multiple types may be used.
  • a material containing components other than the fatty acid can be used.
  • Such materials include, for example, waste oils containing fatty acids, crude oils, semi-refined oils, and oilseed materials.
  • Unsaturated fatty acids are polymerized by oxidative polymerization reaction between unsaturated groups in the presence of oxygen.
  • the oxidative polymerization reaction can be carried out, for example, by stirring the unsaturated fatty acid in the air or by blowing air into the unsaturated fatty acid to bring it into contact with oxygen in the air. In order to accelerate the oxidative polymerization reaction, heating or a catalyst may be used as necessary.
  • the oxidative polymerization reaction is carried out such that the unsaturated fatty acid is partially polymerized to obtain a partial polymer.
  • the reaction temperature is, for example, 100 to 350°C, preferably 150 to 300°C, more preferably 200 to 280°C. If the heating temperature is less than 100°C, the oxidative polymerization reaction may not be promoted sufficiently, and if it exceeds 300°C, the volatilization amount of the unsaturated fatty acid may increase and the yield of the polymer electrolyte may decrease.
  • oxidation catalysts may be used as the catalyst used for the oxidation polymerization reaction.
  • catalysts that can be used include Co, Mn, Pb, Ca, Zn, Cu, Zr, Ce, Fe, Pd, Pt, Sn, Mo, W, Ti, V, which are used as dryers for drying oils.
  • the reaction time of the oxidative polymerization reaction varies depending on the reaction conditions such as the reaction temperature and the type of catalyst, but is preferably the time at which a partial polymer that is solid at room temperature and exhibits thermoplasticity can be obtained. . Generally, it is adjusted appropriately between 30 minutes and 48 hours, preferably between 1 and 24 hours. If the reaction time is too long, the polymer may irreversibly gel, pulverize, and lose its thermoplastic properties.
  • the polymer electrolyte of the present invention preferably has a polystyrene equivalent molecular weight of 10 3 to 10 9 . If the polymer electrolyte when eluted with tetrahydrofuran (THF) does not have a polystyrene-equivalent molecular weight of 10 4 or more, it may exhibit excessive fluidity at room temperature, resulting in poor handling. Having a polystyrene equivalent molecular weight greater than 8 may result in insufficient thermoplasticity.
  • THF tetrahydrofuran
  • the polystyrene-equivalent molecular weight of the polymer electrolyte when eluted with THF is preferably 10 3 to 10 9 , more preferably contains a polystyrene-equivalent molecular weight of 10 4 or more, and exhibits a polystyrene-equivalent molecular weight distribution not exceeding 10 8 .
  • the resulting partial polymer is then reacted with a basic substance.
  • a basic substance As a result, some of the carboxyl groups derived from the unsaturated fatty acid are converted to carboxylate anion groups.
  • the type of basic substance is not limited as long as it has basicity to convert a carboxyl group into a carboxylate anion group, but typical examples include substances containing alkali metals or alkaline earth metals.
  • usable basic substances include NaOH, KOH, Ca(OH) 2 , K(OH), Li(OH), Mg(OH) 2 , Ba(OH) 2 , Zn(OH) 2 , Ammonia, monoethanolamine, diethanolamine, triethanolamine and the like can be mentioned.
  • the ratio of the number of carboxylate anion groups to the number of carboxyl groups in the partial polymer before reacting with the basic substance (hereinafter referred to as "content of carboxylate anion groups") is preferably about 1.3 to 96%. If the content of carboxylate anion groups in a portion of the polymer is less than 1.3%, the thermoplasticity of the polymer electrolyte may be insufficient, and if it exceeds 96%, the strength of the resulting molded article is reduced. may decrease.
  • the content of carboxylate anion groups is more preferably 6 to 50%, still more preferably 8 to 35%.
  • the bioplastic of the present invention contains the polymer electrolyte.
  • bioplastics are used for thin planar molded bodies such as coatings, when the surface of the polymer electrolyte comes into contact with oxygen in the air, an oxidative polymerization reaction occurs and hardens to form a tough coating film. be.
  • the bioplastic of the present invention preferably contains the polymer electrolyte and an oxygen introducing substance.
  • an oxygen-introducing substance air is allowed to pass from the surface of the polymer electrolyte to the inside, so that oxygen in the air is introduced and curability is promoted.
  • the bioplastic of the present invention can be molded into a strong three-dimensional object by accelerating the curability of the interior of the molded body.
  • the type of oxygen-introducing substance is not limited as long as it can coexist with the polymer electrolyte and has a structure that allows air to pass through its interior.
  • the oxygen-introducing substance is preferably a particulate substance having a diameter of 3 nm to 10 mm, or a fibrous substance having a fiber width of 3 nm to 10 mm and an aspect ratio (fiber length/fiber width) of 5 or more, more preferably. is a porous material of such dimensions.
  • Specific examples of oxygen-introducing substances include pulp, cellulose, cellulose nanofiber, cotton, hemp cotton, floss, wool, rock wool, wood, wood powder, abrasive powder, carbon powder, metal powder, glass powder, glass fiber, and carbon fiber. , boron fiber, aramid fiber, ultra-high molecular weight polyethylene fiber, polyparaphenylenebenzobisoxazole fiber, and the like.
  • the oxygen-introducing substance may be an amorphous material when viewed as a whole material.
  • the oxygen-introducing substance may be a tangible material having a certain shape such as sheet-like and thread-like.
  • the tangible material used as the oxygen-introducing substance is a material that has a structure that allows air to pass through its interior and that is flexible enough to be freely deformed. Examples of such materials include woven fabrics, non-woven fabrics, gauze, twine, and the like formed from fibrous materials.
  • the fiber material one having excellent air permeability and flexibility is preferable. For example, natural fiber materials having air permeability such as cotton, linen, floss, wool and rock wool may be used.
  • the oxygen introducing substance is used in the amount necessary to fully cure the entire molded plastic by aerating the interior of the bioplastic.
  • the amount of the oxygen-introducing substance used varies depending on its gas permeability, but is generally 2.5 to 80% (w/w), preferably 10 to 70% (w/w), relative to the polymer electrolyte. , more preferably 20-60% (w/w).
  • the oxygen introducing substance is included in the bioplastic by plasticizing the polymer electrolyte and integrating the plasticized polymer electrolyte and the oxygen introducing substance.
  • the plasticization of the polymer electrolyte preferably imparts fluidity to the polymer electrolyte because it facilitates integration with the oxygen-introducing substance.
  • Plasticization of the polymer electrolyte can be performed, for example, by heating or diluting with a solvent.
  • the specific method for integrating the plasticized polymer electrolyte and the oxygen introduction substance differs between when an amorphous material is used as the oxygen introduction substance and when a tangible material is used.
  • an amorphous material is used as the oxygen introduction substance
  • the two are generally integrated by adding the oxygen introduction substance to the plasticized polymer electrolyte and mixing or kneading until they are uniformly dispersed.
  • a tangible material is used for the oxygen introducing substance
  • the oxygen introducing substance is integrated by laminating, coating or impregnating the plasticized polymer electrolyte with the oxygen introducing substance.
  • the polymer electrolyte When the polymer electrolyte comes into contact with oxygen, an oxidative polymerization reaction occurs, increasing its viscosity, reducing its plasticity, and finally solidifying it. Therefore, in order to maintain the viscosity or plasticity of the polymer electrolyte, the polymer electrolyte is preferably plasticized or integrated in an atmosphere free of oxygen.
  • the atmosphere in which no oxygen exists include an inert gas atmosphere, a vacuum state, or a closed state. Nitrogen gas, argon, carbon dioxide, helium, etc. can be used as the inert gas.
  • the temperature at which the polymer electrolyte is plasticized or the work such as integration is appropriately set in consideration of the heat resistance and work efficiency of the polymer electrolyte. °C, more preferably 100 to 150°C.
  • Polymer electrolytes have a relatively slow oxidative polymerization rate in the plasticizing temperature range that is normally used. Therefore, even when plasticized in an atmosphere in which oxygen is present in the surroundings, the speed at which the viscosity increases is moderate. Therefore, when the simplicity of work or equipment is emphasized, work such as plasticization or integration can be performed in the air or in an atmosphere containing air.
  • the bioplastic of the present invention can be produced so that it becomes solid under room temperature.
  • the bioplastic of the present invention can be produced in a convenient form for distribution as a raw material for injection molded articles such as resin pellets, or as a raw material for industrial products.
  • the bioplastic of the present invention has thermoplasticity, for example, it is plasticized by heating, and is formed into a film, a three-dimensional shape, or a plate shape by using a melt molding method such as coating and injection molding or a hot pressure molding method such as hot press. can be molded into
  • the heating temperature for plasticizing the bioplastic of the present invention is appropriately set according to the molding method used, but is generally 50 to 200°C, preferably 80 to 170°C, more preferably 100 to 150°C. be.
  • bioplastics are plasticized and molded in an oxygen-free atmosphere. is preferred.
  • the work of plasticizing, molding, etc. can be carried out in the air or in an atmosphere containing air.
  • the molded plastic is then heated to harden to the inside. By doing so, a tough compact is formed.
  • the molded article of the present invention thus formed exhibits high strength, high elastic modulus and high heat resistance, and also exhibits high chemical resistance. Heating of the molded plastic is carried out in an environment in which oxygen is present in the environment, for example in air or in an oxygen atmosphere.
  • the heating temperature of the molded plastic is appropriately adjusted in consideration of the shape of the molded plastic, the production efficiency of the molded article, etc., but is generally 80 to 300°C, preferably 100 to 250°C, more preferably 120 to 230°C. be. If the heating temperature is too high, the bioplastic may partially decompose and gasify.
  • the heating time of the molded plastic is appropriately adjusted in consideration of the shape of the molded plastic, the production efficiency of the molded article, etc. Generally, it is 30 minutes to 96 hours, preferably 1 to 46 hours, more preferably 1 to 24 hours. is. If the added oxygen-introducing substance is heat-sensitive, the strength may decrease if the heating time is too long.
  • a coating may be formed on the surface of the molded article of the present invention. By doing so, ventilation to the inside of the molded body is blocked, deterioration and oxidation due to absorption of moisture or oxygen in the air are prevented, and water resistance, chemical resistance, durability, etc. of the molded body are improved.
  • the material of the coating formed on the surface of the molded body is preferably a paint that blocks air flow into the interior of the molded body and has excellent water resistance and chemical resistance.
  • Preferred coating materials specifically include unsaturated fatty acids. Since the unsaturated fatty acid is a material with low environmental load, it meets the object of the present invention and can react with oxygen in the air to form a water-resistant coating film. From the viewpoint of reducing the environmental load, the coating material formed on the surface of the molding is more preferably linoleic acid, ⁇ -linolenic acid and ⁇ -linolenic acid.
  • the material for the coating can be applied to the surface of the molded body using a coating method such as spraying, and heated or cured as necessary to form a film.
  • Example 1 Preparation of Polyelectrolyte A beaker with a capacity of 500 ml was charged with 50 ml of linoleic acid and 0.05% (w/w) FeCl 3 was added as a radical initiator. The content was heated to 200° C. while mixing oxygen in the air by stirring, and reacted for about 1 hour. Linoleic acid gave a brown color.
  • the polymer to which sodium hydroxide was added was heated with stirring at 100°C for 2 hours, after which the reactant was cooled.
  • 5 mg of each was placed on a slide glass and heated at 200° C. for 30 minutes while spreading thinly to obtain a polymer electrolyte cured in the form of a film. All experimental operations were performed in an air atmosphere. Then, the obtained polymer electrolyte was subjected to infrared spectroscopic analysis. The measured spectrum is shown in FIG.
  • Example 2 Manufacture of compacts (amorphous oxygen introduction material) A beaker with a capacity of 500 ml was charged with 50 ml of linoleic acid and 0.05% (w/w) FeCl 3 was added as a radical initiator. The content was heated to 280° C. while mixing oxygen in the air by stirring, and reacted for about 1 hour and 30 minutes. Linoleic acid colored black and became sticky. To this was added 2.5% (w/w) sodium hydroxide, followed by heating for 1 hour, after which the reaction was cooled to obtain a solid polymer electrolyte at ambient temperature. The calculated content of carboxylate anion groups in the polymer electrolyte is 15.9%.
  • 35% (w/w) pulp (“Kimtowel (trade name) unbleached” manufactured by Nippon Paper Crecia Co., Ltd.) was cut in water with a mixer to a fiber length of about 3 mm, and dried. was added, heated to 120° C. to fluidize, and kneaded until the pulp was uniformly dispersed.
  • the kneaded product was molded into a plate having a length of 72 mm, a width of 20 mm and a thickness of 2.8 mm. All experimental operations were performed in an air atmosphere.
  • a three-point bending test was performed on the compact with reference to JISK7171.
  • the bending strength of the plate-like molding was 35 MPa, and the bending elastic modulus was 2125 MPa. It was confirmed that the molded article made from the polymer electrolyte of the present invention under these conditions has higher toughness than general polyester, and has high toughness.
  • Example 3 Manufacture of compacts (amorphous oxygen introduction material) 50 ml each of linoleic acid was placed in 7 beakers with a capacity of 500 ml, and 0.05% (w/w) FeCl 3 was added as a radical initiator. The content was heated to 280° C. while mixing oxygen in the air by stirring, and reacted for about 1 hour and 30 minutes each. To this is added 0%, 0.2%, 0.5%, 1.0%, 2.0%, 15%, 20% (w/w) sodium hydroxide respectively followed by heating for 1 hour, then , the reactants were cooled to obtain a solid polymer electrolyte at room temperature.
  • 35% (w/w) pulp (“Kimtowel (trade name) unbleached” manufactured by Nippon Paper Crecia Co., Ltd.) was cut in water with a mixer to a fiber length of about 3 mm, and dried. was added, heated to 120° C. to fluidize, and kneaded until the pulp was uniformly dispersed.
  • the kneaded product was molded into a plate with a length of 72 mm, a width of 11 mm and a thickness of 2.0 mm, and the molded body was heated at 140°C for 1 hour and then at 160°C for 16 hours to complete curing. All experimental operations were performed in an air atmosphere.
  • a three-point bending test was performed on the compact with reference to JISK7171.
  • the flexural strength of the plate-shaped compacts is shown in Table 1, and the flexural strength of the compacts to which 20% (w/w) sodium hydroxide was added compared to the 0% control compact to which no sodium hydroxide was added. 0.2%, 0.5%, 1.0%, 2.0%, 15% (w / w) sodium hydroxide at other concentrations without increasing the polymer electrolyte of the present invention increased flexural strength compared to the 0% non-additive control.
  • Example 4 Manufacture of compacts (amorphous oxygen introduction material) 50 mL of linoleic acid was placed in four 500 mL beakers, and 0.05% (w/w) FeCl 3 was added as a radical initiator. The contents were divided into non-heating and heating at 280° C. for 1 hour, 1 hour and 45 minutes, and 2 hours and 30 minutes while stirring the contents to mix oxygen in the air. Those heated for 2 hours 30 gelled and pulverized. Each 2.5% (w/w) sodium hydroxide was added and heated with continued stirring for 1 hour, after which the reaction was cooled to obtain a solid polyelectrolyte at ambient temperature.
  • the polymer electrolyte (middle) obtained by polymerization for 1 hour and 45 minutes showed fluidity and had thermoplasticity when heated at about 150°C.
  • the polymer electrolyte (High) obtained by polymerization for 2 hours and 30 minutes became more flexible when heated to about 200° C., but lacked thermoplasticity.
  • 35% (w/w) pulp (“Kimtowel (trade name) unbleached” manufactured by Nippon Paper Crecia Co., Ltd.) was cut in water with a mixer to a fiber length of about 3 mm, and dried. was added, heated to 120° C. to fluidize, and kneaded until the pulp was uniformly dispersed.
  • the kneaded product was molded into a plate having a length of 72 mm, a width of 11 mm and a thickness of 3.0 mm, and the molded body was heated at 140°C for 1 hour and then at 160°C for 16 hours to complete curing. All experimental operations were performed in an air atmosphere.
  • the unheated control sample and pulp moldings and the polyelectrolyte and pulp moldings obtained from polymerization for 2 hours and 30 minutes cracked during curing.
  • the polymer electrolyte of the present invention contains a polystyrene equivalent molecular weight of 10 4 or more when eluted with THF, and exhibits excellent moldability and toughness when the polystyrene equivalent molecular weight distribution does not exceed 10 8 . have understood.
  • Example 5 Manufacture of compacts (amorphous oxygen introduction material) A beaker with a capacity of 500 ml was charged with 50 ml of linolenic acid and 0.05% (w/w) FeCl 3 was added as a radical initiator. The content was heated to 280° C. while mixing oxygen in the air by stirring, and reacted for about 1 hour and 30 minutes. The linolenic acid colored black and became sticky. To this was added 2.5% (w/w) sodium hydroxide, followed by heating for 1 hour, after which the reaction was cooled to obtain a solid polymer electrolyte at ambient temperature.
  • 35% (w/w) pulp (“Kimtowel (trade name) unbleached” manufactured by Nippon Paper Crecia Co., Ltd.) was cut in water with a mixer to a fiber length of about 3 mm, and dried. was added, heated to 120° C. to fluidize, and kneaded until the pulp was uniformly dispersed.
  • the kneaded product was molded into a plate with a length of 72 mm, a width of 11 mm and a thickness of 2.8 mm, and the molded body was heated at 140°C for 1 hour and then at 160°C for 16 hours to complete curing. All experimental operations were performed in an air atmosphere.
  • a three-point bending test was performed on the compact with reference to JISK7171.
  • the flexural strength of the plate-shaped molding was 22 MPa, and the flexural modulus was 1290 MPa, confirming that it has a certain toughness like linoleic acid.
  • Example 6 Manufacture of compacts (amorphous oxygen introduction material) A beaker with a capacity of 500 ml was charged with 50 ml of linoleic acid and 0.05% (w/w) FeCl 3 was added as a radical initiator. The content was heated to 280° C. while mixing oxygen in the air by stirring, and reacted for about 1 hour and 30 minutes. To this was added 2.5% (w/w) sodium hydroxide, followed by heating for 1 hour, after which the reaction was cooled to obtain a solid polymer electrolyte at ambient temperature.
  • 35% (w/w) pulp (“Kimtowel (trade name) unbleached” manufactured by Nippon Paper Crecia Co., Ltd.) was cut in water with a mixer to a fiber length of about 3 mm, and dried. was added, heated to 120° C. to fluidize, and kneaded until the pulp was uniformly dispersed.
  • the kneaded product was molded into a bar shape with a length of 72 mm, a width of 20 mm and a thickness of 20 mm, and heated at 140°C for 1 hour and then at 160°C for 16 hours to complete curing. All experimental operations were performed in an air atmosphere. After that, it was cut from the center into a plate shape of 72 mm long, 10 mm wide and 2.0 mm thick.
  • a three-point bending test was performed on the compact with reference to JISK7171.
  • the bending strength of the plate-shaped molding was 36 MPa, and the bending elastic modulus was 3770 MPa, confirming that the inside of the molding was sufficiently hardened.
  • Example 7 Manufacture of compacts (amorphous oxygen introduction material) Two 500 ml beakers were filled with 50 ml each of linoleic acid and 0.05% (w/w) FeCl 3 was added as a radical initiator. The content was heated to 280° C. while mixing oxygen in the air by stirring, and reacted for about 1 hour and 30 minutes. To this was added 2.5% (w/w) sodium hydroxide, followed by heating for 1 hour, after which the reaction was cooled to obtain a solid polymer electrolyte at ambient temperature.
  • the kneaded cellulose powder was molded into a plate with a length of 72 mm, a width of 10 mm and a thickness of 2.0 mm, and the carbon fiber fragment mixture was molded into a plate with a length of 72 mm, a width of 10 mm and a thickness of 1.5 mm.
  • Each compact was heated at 140° C. for 1 hour and then at 160° C. for 16 hours to complete curing. All experimental operations were performed in an air atmosphere.
  • a three-point bending test was performed on the compact.
  • the flexural strength of the compact with cellulose powder was 86 MPa, and the flexural modulus was 3860 MPa.
  • the bending strength of the molded body with the carbon fiber fragment was 96 MPa, and the bending elastic modulus was 1485 MPa. It was confirmed that the molded body with the cellulose powder and the molded body with the carbon fiber fragment under these conditions had densities of 0.7 cm 3 /g and 0.8 cm 3 /g, respectively, and had extremely light weight and high toughness.
  • Example 8 Manufacture of compacts (amorphous oxygen introduction material) A beaker with a capacity of 500 ml was charged with 50 ml of linoleic acid and 0.05% (w/w) FeCl 3 was added as a radical initiator. The content was heated to 280° C. while mixing oxygen in the air by stirring, and reacted for about 1 hour and 30 minutes. To this was added 2.5% (w/w) sodium hydroxide, followed by heating for 1 hour, after which the reaction was cooled to obtain a solid polymer electrolyte at ambient temperature.
  • the cellulose powder kneaded product was molded into a plate with a length of 72 mm, a width of 10 mm and a thickness of 2.0 mm, and the molded body was heated at 140°C for 1 hour and then at 160°C for 16 hours to complete foaming and curing. All experimental operations were performed in an air atmosphere.
  • This foam was subjected to a three-point bending test with reference to JISK7171.
  • the foam had a flexural strength of 6 MPa and a flexural modulus of 85 MPa. It was confirmed that the foam under these conditions had a density of 0.4 cm 3 /g, a light weight and a certain toughness.
  • Example 9 Manufacture of compacts (amorphous oxygen-introducing substances, plasticization under anaerobic conditions) Two 500 ml beakers were filled with 50 ml each of linoleic acid and 0.05% (w/w) FeCl 3 was added as a radical initiator. The content was heated to 280° C. while mixing oxygen in the air by stirring, and reacted for about 1 hour and 30 minutes. To this was added 2.5% (w/w) sodium hydroxide, followed by heating for 2 hours, after which the reaction was cooled to give a solid polyelectrolyte in the form of pellets, hard at ambient temperature.
  • the cellulose powder kneaded product was molded into a plate with a length of 72 mm, a width of 10 mm and a thickness of 2.0 mm. Each compact was heated at 140° C. for 1 hour and then at 180° C. for 1 hour to complete curing.
  • Example 10 Manufacture of compacts (tangible oxygen-introducing substances) A beaker with a capacity of 500 ml was charged with 50 ml of linoleic acid and 0.05% (w/w) FeCl 3 was added as a radical initiator. To the contents, 2.5% (w/w) sodium hydroxide was added and dissolved by heating and stirring at 200°C for 30 minutes.
  • the obtained spongy molded body which remained slightly thermoplastic, was divided into three equal parts, which were pressed at 250° C. for 10 minutes so as to have thicknesses of 3.0 mm, 1.5 mm, and 1.0 mm, respectively. Molded bodies with 0.13 cm 3 /g, 0.26 cm 3 /g, and 0.39 cm 3 /g having been cured were obtained. All experimental operations were performed in an air atmosphere.
  • a three-point bending test was performed on the compacts having densities of 0.13 cm 3 /g, 0.26 cm 3 /g and 0.39 cm 3 /g.
  • the flexural strengths are 0.4 MPa, 1.6 MPa, and 35.7 MPa, respectively, and the flexural moduli are 5 MPa, 95 MPa, and 3900 MPa, respectively. was confirmed.
  • Example 11 Manufacture of compacts (tangible oxygen-introducing substances) A beaker with a capacity of 500 ml was charged with 50 ml of linoleic acid and 0.05% (w/w) FeCl 3 was added as a radical initiator. To the contents, 2.5% (w/w) sodium hydroxide was added and dissolved by heating and stirring at 200°C for 30 minutes.
  • the resulting string which remains slightly thermoplastic, is folded back every 150 mm to bundle it with a radius of about 10 mm, and pressed at 250° C. for 10 minutes so as to have a thickness of 1.0 mm, and a density of 1.30 cm 3 /g.
  • a plate-like molded body that had been completely cured was obtained. All experimental operations were performed in an air atmosphere.
  • a three-point bending test was performed with reference to JISK7171.
  • the bending strength in the direction perpendicular to the string was 115.2 MPa, and the bending elastic modulus was 9635 MPa.

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WO2025057976A1 (ja) * 2023-09-13 2025-03-20 兵庫県 水系樹脂、及びその製造方法
WO2026048349A1 (ja) * 2024-08-27 2026-03-05 兵庫県 樹脂、樹脂の製造方法および硬化性樹脂組成物

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WO2026048349A1 (ja) * 2024-08-27 2026-03-05 兵庫県 樹脂、樹脂の製造方法および硬化性樹脂組成物

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