Polymer electrolytes, bioplastics and molded articles

Abstract

The present invention addresses the problem of providing a novel polyelectrolyte, a bioplastic which can be molded into a tough three-dimensional object, and a molded body using same. The solution to the problem is a polyelectrolyte comprising a partial polymer of a fatty acid having at least 16 carbon atoms, at least 2 double bonds, and carboxyl groups, the carboxyl groups being partially neutralized with a basic substance and converted to carboxylate anion groups.

Description

[Technical Field]

[0001] This invention relates to polymers of unsaturated fatty acids, and more particularly to polymers of polyunsaturated fatty acids. [Background technology]

[0002] Bioplastics are manufactured from plant-based materials and can be decomposed by microorganisms present in soil and water. Furthermore, because they utilize non-depletable resources, they contribute to saving volatile resources such as petroleum during plastic manufacturing and help mitigate global warming.

[0003] Lipids, such as oils and fatty acids, are derived from natural sources and are materials with low environmental impact. It is well known that lipids containing unsaturated fatty acids oxidize and harden in the presence of a catalyst. However, these undergo gelation during the reaction, and the hardened product has almost no thermoplastic properties. Therefore, for example, such hardened lipids are difficult to use as raw materials for injection molded products such as resin pellets.

[0004] Furthermore, lipids containing unsaturated fatty acids require oxygen for the curing reaction, making it difficult for air to penetrate from the surface to the interior. As a result, the polymerization reaction does not complete in three-dimensional molded products. Therefore, cured products of such lipids are only suitable for coating applications. [Overview of the project] [Problems that the invention aims to solve]

[0005] The object of the present invention is to provide novel polymer electrolytes, bioplastics that can be molded into tough three-dimensional objects, and molded articles using these. [Means for solving the problem]

[0006] The present invention provides means for solving the following problems.

[0007] [Aspect 1] A polymer electrolyte comprising a partial polymer of a fatty acid having 16 or more carbon atoms, 2 or more double bonds, and a carboxyl group, wherein part of the carboxyl group is neutralized with a basic substance and converted into a carboxylate anion group.

[0008] [Aspect 2] The polymer electrolyte according to Aspect 1, which is a radical polymer.

[0009] [Aspect 3] The polymer electrolyte according to Aspect 1 or 2, wherein the basic substance is a substance containing an alkali metal or an alkaline earth metal.

[0010] [Aspect 4] The polymer electrolyte according to any one of Aspects 1 to 3, wherein the fatty acid is derived from a plant.

[0011] [Aspect 5] The polymer electrolyte according to any one of Aspects 1 to 4, wherein the fatty acid is linoleic acid or linolenic acid.

[0012] [Aspect 6] 10 3 to 10 9 The polymer electrolyte according to any one of Aspects 1 to 5, having a polystyrene-equivalent molecular weight of

[0013] [Aspect 7] The polymer electrolyte according to any one of Aspects 1 to 6, having a carboxylate anion group content of 1.3 to 96%.

[0014] [Aspect 8] A bioplastic comprising the polymer electrolyte according to any one of Aspects 1 to 7.

[0015] [Aspect 9] The bioplastic according to Aspect 8, comprising an oxygen-introducing substance.

[0016] [Aspect 10] The bioplastic according to aspect 9, wherein the oxygen-introducing substance is contained in an amount of 2.5 to 80% (w / w) based on the polymer electrolyte.

[0017] [Aspect 11] A molded article comprising a cured product of the bioplastic according to any one of aspects 8 to 10.

[0018] [Aspect 12] a step of partially polymerizing a fatty acid having 16 or more carbon atoms, 2 or more double bonds, and a carboxyl group; and a step of reacting a partial polymer of the fatty acid with a basic substance; A method for producing a polymer electrolyte, comprising the above steps.

[0019] [Aspect 13] a step of plasticizing the polymer electrolyte according to any one of aspects 1 to 7; and a step of integrating the plasticized polymer electrolyte and the oxygen-introducing substance; A method for producing a bioplastic, comprising the above steps.

[0020] [Aspect 14] a step of plasticizing the bioplastic according to any one of aspects 8 to 10; a step of molding the plasticized bioplastic; and a step of curing the obtained molded plastic; A method for producing a molded article, comprising the above steps. Effects of the Invention

[0021] According to the present invention, there are provided a novel polymer electrolyte, a bioplastic that can be molded into a tough three-dimensional article, and a molded article using these. Brief Description of the Drawings

[0022] [Figure 1]This infrared spectroscopic spectrum shows that when the amount of sodium hydroxide added to the polymer electrolyte of the present invention is increased, the C=O stretching vibration peak of the carboxyl group decreases, while the C=O stretching vibration peak of the carboxylate anionic group increases. [Figure 2] This is a differential molecular weight distribution curve obtained by HPLC analysis of the components of the polymer electrolyte of the present invention that dissolve in THF. [Modes for carrying out the invention]

[0023] <Polymer electrolyte> The polymer electrolyte of the present invention has a structure in which some of the unsaturated groups of an unsaturated fatty acid are bonded together. Therefore, the polymer electrolyte of the present invention is a partial polymer of an unsaturated fatty acid. In other words, the polymer electrolyte of the present invention still has unsaturated groups, and these can be further polymerized to exhibit curability.

[0024] Furthermore, 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. As a result of the conversion of the carboxyl groups into carboxylate anionic groups, the main chains repel each other electrically, suppressing entanglement and enabling the polymer electrolyte to exhibit thermoplasticity.

[0025] The polymer electrolyte of the present invention is manufactured using unsaturated fatty acids as raw materials. Unsaturated fatty acids have double bonds and can be cured by polymerization in the presence of oxygen in the air, for example. Furthermore, unsaturated fatty acids have carboxyl groups and can be converted into salts by neutralization with a basic substance.

[0026] As unsaturated fatty acids, for example, fatty acids having 16 or more carbon atoms, 2 or more double bonds, and carboxyl groups are used. Having 2 or more double bonds in unsaturated fatty acids allows them to form a cross-linked structure during polymerization reactions, improving the chemical resistance, heat resistance, or strength of the resulting molded article. The number of double bonds in the unsaturated fatty acid is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3. Furthermore, from the viewpoint of availability, the number of carbon atoms in the unsaturated fatty acid is preferably 16 to 22, more preferably 16 to 20, and even more preferably 18.

[0027] Specific examples of unsaturated fatty acids include oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, and docosahexaenoic acid. Among these, linoleic acid, linolenic acid, and arachidonic acid are preferred unsaturated fatty acids. From the viewpoint of reducing environmental impact, unsaturated fatty acids are preferably derived from plants, and more preferably linoleic acid, alpha-linolenic acid, and gamma-linolenic acid.

[0028] Unsaturated fatty acids may be used as a single type or as a mixture of multiple types. Furthermore, materials containing components other than fatty acids may be used as raw materials for the polymer electrolyte. Examples of such materials include waste oil, crude oil, semi-refined oil, or oilseed raw materials containing fatty acids.

[0029] Polymerization of unsaturated fatty acids is carried out by oxidative polymerization of unsaturated groups in the presence of oxygen. Oxidative polymerization can be carried out, for example, by stirring the unsaturated fatty acid in air or by blowing air into the unsaturated fatty acid and bringing it into contact with oxygen in the air. Heating or the use of a catalyst may be performed as needed to accelerate the oxidative polymerization reaction. The oxidative polymerization reaction is carried out so that the unsaturated fatty acid is partially polymerized to obtain a partial polymer.

[0030] When the oxidative polymerization reaction is carried out by heating, 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 lower than 100°C, the promotion of the oxidative polymerization reaction may be insufficient; if it exceeds 300°C, the volatilization amount of unsaturated fatty acids increases, which may reduce the yield of the polyelectrolyte.

[0031] As the catalyst used in the oxidative polymerization reaction, conventionally known oxidation catalysts may be used. Specific examples of usable catalysts include metal powders of Co, Mn, Pb, Ca, Zn, Cu, Zr, Ce, Fe, Pd, Pt, Sn, Mo, W, Ti, V, Rh, Ni, Zr, Al, Ag, B and Cr that are used as dryers for drying oils, as well as their oxides, hydroxides, sulfates, nitrates, chlorides, acetates and naphthenates; and organic oxidizing agents such as anthracene, methyl ethyl ketone peroxide and benzoyl peroxide.

[0032] The reaction time of the oxidative polymerization reaction varies depending on reaction conditions such as reaction temperature and the type of catalyst, and is preferably a time that allows obtaining a partial polymer that is solid at room temperature and exhibits thermoplasticity. Generally, it is appropriately adjusted within 30 minutes to 48 hours, preferably 1 to 24 hours. If the reaction time is too long, the polymer may irreversibly gel and pulverize, resulting in loss of thermoplasticity.

[0033] The polyelectrolyte of the present invention preferably has 10 3 to 10 9 in polystyrene-equivalent molecular weight. When eluted with tetrahydrofuran (THF), the polyelectrolyte has 10 4 or higher in polystyrene-equivalent molecular weight, if the polyelectrolyte does not meet this requirement, it may exhibit excessive fluidity at room temperature and lead to degraded handling properties; if the polyelectrolyte has a polystyrene-equivalent molecular weight exceeding 10 8 , insufficient thermoplasticity may occur. Therefore, the polystyrene-equivalent molecular weight of the polyelectrolyte when eluted with THF is preferably 10 3 to 10 9 , more preferably 10 4Containing the above polystyrene-equivalent molecular weight, 10 8 It exhibits a polystyrene-based molecular weight distribution that does not exceed [a certain value].

[0034] The resulting polymer is then reacted with a basic substance. This converts some of the carboxyl groups derived from the unsaturated fatty acid into carboxylate anionic groups. The basic substance can be any substance that is basic enough to convert carboxyl groups into carboxylate anionic groups, but typical examples include substances containing alkali metals or alkaline earth metals. Specific examples of basic substances that can be used include NaOH, KOH, Ca(OH)2, K(OH), Li(OH), Mg(OH)2, Ba(OH)2, Zn(OH)2, ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0035] The ratio of carboxylate anion groups to the number of carboxyl groups in a portion of the polymer before reaction with a basic substance (hereinafter referred to as "carboxylate anion group content") is preferably about 1.3 to 96%. If the carboxylate anion group content of the 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 may decrease. The carboxylate anion group content is more preferably 6 to 50%, and even more preferably 8 to 35%.

[0036] <Bioplastics> The bioplastic of the present invention contains the polymer electrolyte. When the bioplastic is used for a thin, planar molded body such as a coating, the surface of the polymer electrolyte comes into contact with oxygen in the air, causing an oxidative polymerization reaction and hardening, forming a tough coating film.

[0037] The bioplastic of the present invention preferably comprises the polymer electrolyte and an oxygen-introducing substance. The inclusion of the oxygen-introducing substance allows air to permeate from the surface to the interior of the polymer electrolyte, thereby introducing oxygen from the air and accelerating the curing process. This accelerated curing process within the molded body allows the bioplastic of the present invention to be molded into a tough, three-dimensional object.

[0038] The oxygen-introducing material is not limited in type, as long as it can coexist with polymer electrolytes and has a structure that allows air to pass through its interior. Preferably, the oxygen-introducing material is a particulate material with a diameter of 3 nm to 10 mm, or a fibrous material with a fiber width of 3 nm to 10 mm and an aspect ratio (fiber length / fiber width) of 5 or more, and more preferably a porous material of such dimensions. Specific examples of oxygen-introducing materials include pulp, cellulose, cellulose nanofibers, cotton, hemp cotton, silk floss, wool, rock wool, wood, wood powder, polishing powder, carbon powder, metal powder, glass powder, glass fiber, carbon fiber, boron fiber, aramid fiber, ultra-high molecular weight polyethylene fiber, poly(p-phenylenebenzobisoxazole) fiber, etc.

[0039] The oxygen-introducing material may be an amorphous material when viewed as a whole. On the other hand, the oxygen-introducing material may be a tangible material having a specific shape, such as a sheet or thread. The tangible material used as the oxygen-introducing material has a structure that allows air to pass through its interior and is flexible enough to be freely deformed. Examples of such materials include woven fabrics, nonwoven fabrics, gauze, and twisted yarns made from fibrous materials. The fibrous material is preferably one that has excellent breathability and flexibility, and for example, breathable natural fiber materials such as cotton, hemp cotton, silk floss, wool, and rock cotton may be used.

[0040] The oxygen-introducing agent is used in the amount necessary to sufficiently cure the entire molded plastic by allowing air to circulate within the bioplastic. The amount of oxygen-introducing agent used varies depending on its permeability, but is generally 2.5 to 80% (w / w), preferably 10 to 70% (w / w), and more preferably 20 to 60% (w / w) relative to the polymer electrolyte.

[0041] The oxygen-introducing substance is incorporated into the bioplastic by plasticizing the polymer electrolyte and integrating the plasticized polymer electrolyte with the oxygen-introducing substance. It is preferable to impart fluidity to the polymer electrolyte during plasticization, as this facilitates integration with the oxygen-introducing substance. Plasticization of the polymer electrolyte can be carried out, for example, by heating or dilution with a solvent.

[0042] The specific method for integrating the plasticized polymer electrolyte and the oxygen-introducing material differs depending on whether an amorphous material or a tangible material is used as the oxygen-introducing material. When an amorphous material is used as the oxygen-introducing material, integration is generally achieved by adding the oxygen-introducing material to the plasticized polymer electrolyte and mixing or kneading until uniformly dispersed. When a tangible material is used as the oxygen-introducing material, integration is generally achieved by laminating, coating, or impregnating the plasticized polymer electrolyte onto the oxygen-introducing material.

[0043] When polymer electrolytes come into contact with oxygen, an oxidative polymerization reaction occurs, increasing their viscosity, decreasing their plasticity, and ultimately solidifying them. Therefore, to maintain the viscosity or plasticity of a polymer electrolyte, it is preferable to perform plasticization or integration operations in an atmosphere where oxygen is absent. Specific examples of an atmosphere where oxygen is absent include an inert gas atmosphere, a vacuum, or a sealed state. Inert gases that can be used include nitrogen gas, argon, carbon dioxide, and helium.

[0044] The temperature at which the polymer electrolyte is plasticized or integrated is set appropriately considering the heat resistance of the polymer electrolyte and the work efficiency, but is generally 50 to 200°C, preferably 80 to 170°C, and more preferably 100 to 150°C.

[0045] Polymer electrolytes exhibit a relatively slow oxidative polymerization rate within their typical plasticization temperature range. Therefore, even when plasticized in an atmosphere with oxygen present, the rate of viscosity increase is gradual. Consequently, when ease of operation or equipment is a priority, plasticization or integration can be performed in an atmosphere containing air or ambient air.

[0046] The bioplastic of the present invention can be manufactured to become solid at room temperature. Furthermore, the bioplastic of the present invention can be manufactured in a form that is convenient for distribution as a raw material for injection molded articles such as resin pellets, or as a raw material for industrial products.

[0047] <Molded body> The bioplastic of the present invention is thermoplastic and can be molded into a film, three-dimensional shape, or plate shape using, for example, heating to plasticize it and then melt molding methods such as coating and injection molding or heat and pressure molding methods such as hot pressing.

[0048] The heating temperature for plasticizing the bioplastic of the present invention is set appropriately depending on the molding method used, but is generally 50 to 200°C, preferably 80 to 170°C, and more preferably 100 to 150°C. When it is necessary to maintain viscosity or plasticity during the process of plasticizing the bioplastic, or from plasticization to the completion of molding, it is preferable to perform the plasticization and molding operations in an atmosphere where oxygen is absent. On the other hand, if simplicity of work or equipment is important for the reasons mentioned above, the plasticization and molding operations can be performed in an atmosphere containing air or ambient air.

[0049] The molded plastic is then heated to harden it internally. This creates a tough molded body. The molded body of the present invention formed in this way exhibits high strength, high elastic modulus, and high heat resistance, as well as high chemical resistance. The heating of the molded plastic is carried out in an environment where oxygen is present, such as in air or an oxygen atmosphere.

[0050] The heating temperature of molded plastics is adjusted as appropriate, taking into consideration the shape of the molded plastic, the manufacturing efficiency of the molded product, etc., but is generally 80 to 300°C, preferably 100 to 250°C, and more preferably 120 to 230°C. If the heating temperature is too high, the bioplastic may partially decompose and gasify.

[0051] The heating time for molded plastics is adjusted as appropriate, taking into account the shape of the molded plastic, the manufacturing efficiency of the molded product, etc., but is generally 30 minutes to 96 hours, preferably 1 to 46 hours, and more preferably 1 to 24 hours. If the added oxygen-introducing substance is sensitive to heat, the strength may decrease if the heating time is too long.

[0052] The molded article of the present invention may have a coating formed on its surface. By doing so, ventilation into the interior of the molded article is blocked, preventing deterioration and oxidation due to the absorption of moisture or oxygen from the air, thereby improving the water resistance, chemical resistance, and durability of the molded article.

[0053] The coating material formed on the surface of the molded body is preferably a paint that blocks air from entering the interior of the molded body and has excellent water resistance and chemical resistance. Specifically, unsaturated fatty acids are preferred coating materials. Since unsaturated fatty acids have a low environmental impact, they are suitable for the purpose of this invention and can react with oxygen in the air to form a water-resistant coating film. From the viewpoint of minimizing environmental impact, linoleic acid, α-linolenic acid, and γ-linolenic acid are more preferable as coating materials for the surface of the molded body. The coating material can be applied to the surface of the molded body using, for example, a spray application method, and then heated or cured as needed to form a film. The present invention will be described in more detail below with reference to examples. The present invention is not limited to these examples. [Examples]

[0054] <Example 1> Manufacturing of polymer electrolytes 50 ml of linoleic acid was placed in a 500 ml beaker, and 0.05% (w / w) FeCl3 was added as a radical initiator. The contents were heated to 200°C and reacted for approximately 1 hour while stirring to incorporate oxygen from the air. The linoleic acid turned brown.

[0055] Ten mL of this linoleic acid was taken, and sodium hydroxide was added in amounts to achieve concentrations of 0% (w / w), 1.0% (w / w), 2.5% (w / w), 5.0% (w / w), and 25% (w / w).

[0056] The polymer, to which sodium hydroxide was added, was heated at 100°C for 2 hours with stirring, and then the reaction mixture was cooled. The 25% (w / w) sample solidified into a soap-like substance, so it was crushed to a certain size. Then, 5 mg of each sample was placed on a glass slide and heated at 200°C for 30 minutes while being spread thinly to obtain a film-like polymer electrolyte. All experimental procedures were performed under an air atmosphere. Next, infrared spectroscopy analysis was performed on the obtained polymer electrolyte. The measured spectrum is shown in Figure 1.

[0057] In the spectrum of Figure 1, as the amount of sodium hydroxide added increases, the wavelength 1740 cm², which originates from the C=O stretching vibration of the carboxyl group, increases. -1 The peak decreases, and the wavelength 1557 cm is derived from the C=O stretching vibration of the carboxylate anionic group. -1 The peak is increasing. This indicates that the carboxyl groups of the fatty acid polymer actually reacted with a basic substance and were converted to carboxylate anionic groups.

[0058] <Example 2> Manufacturing of molded products (amorphous oxygen-introduced substances) 50 ml of linoleic acid was placed in a 500 ml beaker, and 0.05% (w / w) FeCl3 was added as a radical initiator. The mixture was heated to 280°C while stirring to incorporate oxygen from the air, and the reaction was allowed to proceed for approximately 1 hour and 30 minutes. The linoleic acid turned black and became viscous. 2.5% (w / w) sodium hydroxide was added, and the mixture was heated for another hour. The reaction was then cooled to obtain a solid polymer electrolyte at room temperature. The content of carboxylate anionic groups in the polymer electrolyte was calculated to be 15.9%.

[0059] 10 mg of this polymer electrolyte was taken, 1 mL of THF was added, and the mixture was shaken at 25°C for 1 hour. The supernatant 20 μL was then analyzed by HPLC using a GPC column (Shodex KF-805L, 40°C). THF was used as the developing solvent, the flow rate was 1 mL / min, and detection was performed using a differential refractive index (RI) detector. The polystyrene-equivalent molecular weight of the dissolved polymer electrolyte was calculated under these conditions. As a result, 10 3 ~10 8 A wide distribution of molecular weight was observed. This polymer electrolyte exhibited fluidity and thermoplastic properties when heated to approximately 100°C.

[0060] 35% (w / w) pulp (unbleached Kimtowels, manufactured by Nippon Paper Crecia Co., Ltd., cut to a fiber length of approximately 3 mm in a mixer underwater and dried) was added to the obtained polymer electrolyte, heated to 120°C to fluidize, and kneaded until the pulp was uniformly dispersed.

[0061] The kneaded material was molded into a plate measuring 72 mm in length, 20 mm in width, and 2.8 mm in thickness. The molded body was heated at 140°C for 1 hour, and then at 160°C for 16 hours to complete the hardening process. All experimental procedures were performed under an air atmosphere.

[0062] A three-point bending test was performed on the molded article, referencing JIS K7171. The bending strength of the plate-shaped molded article was 35 MPa, and the bending modulus was 2125 MPa. Under these conditions, the molded article made from the polymer electrolyte of the present invention exhibited higher toughness than general polyester, confirming its superior toughness.

[0063] <Example 3> Manufacturing of molded products (amorphous oxygen-introduced substances) Seven 500ml beakers were each filled with 50ml of linoleic acid, and 0.05% (w / w) FeCl3 was added as a radical initiator. The contents were stirred to incorporate oxygen from the air, and the mixture was heated to 280°C and reacted for approximately 1 hour and 30 minutes in each beaker. To these, 0%, 0.2%, 0.5%, 1.0%, 2.0%, 15%, and 20% (w / w) sodium hydroxide were added, respectively, and the mixture was heated for another hour. The reaction mixture was then cooled to obtain a solid polymer electrolyte at room temperature.

[0064] 35% (w / w) pulp (unbleached Kimtowels, manufactured by Nippon Paper Crecia Co., Ltd., cut to a fiber length of approximately 3 mm in a mixer underwater and dried) was added to the obtained polymer electrolyte, heated to 120°C to fluidize, and kneaded until the pulp was uniformly dispersed.

[0065] The kneaded material was molded into a plate measuring 72 mm in length, 11 mm in width, and 2.0 mm in thickness. The molded body was heated at 140°C for 1 hour, and then at 160°C for 16 hours to complete the hardening process. All experimental procedures were performed under an air atmosphere.

[0066] A three-point bending test was performed on the molded articles, referring to JIS K7171. The bending strength of the plate-shaped molded articles is shown in Table 1. In the molded articles with 20% (w / w) sodium hydroxide added, the bending strength did not increase compared to the control molded article with 0% sodium hydroxide added. However, in the molded articles made from the polymer electrolyte of the present invention with other concentrations of sodium hydroxide added (0.2%, 0.5%, 1.0%, 2.0%, and 15% w / w), an increase in bending strength was observed compared to the control molded article with 0% sodium hydroxide added.

[0067] [Table 1]

[0068] <Example 4> Manufacturing of molded products (amorphous oxygen-introduced substances) Four 500ml beakers were filled with 50ml of linoleic acid, and 0.05% (w / w) FeCl3 was added as a radical initiator. Each beaker was then divided into two cases: one without heating, and the other heated at 280°C for 1 hour, 1 hour 45 minutes, and 2 hours 30 minutes while stirring to incorporate oxygen from the air. The mixture heated for 2 hours 30 minutes gelled and the mixture became powdered. 2.5% (w / w) sodium hydroxide was added to each beaker, and the mixture was heated for 1 hour while continuing to stir. The reaction mixture was then cooled to obtain a solid polymer electrolyte at room temperature.

[0069] 10 mg of this polymer electrolyte was taken, 1 mL of THF was added, and the mixture was shaken at 25°C for 1 hour. The supernatant 20 μL was then analyzed by HPLC using a GPC column (Shodex KF-805L, 40°C). THF was used as the developing solvent, the flow rate was 1 mL / min, and detection was performed using radioisotopes (RI). The polystyrene-equivalent molecular weight of the dissolved polymer electrolyte was calculated under these conditions. As a result, the differential molecular weight distribution curve shown in Figure 2 was obtained. The polymer electrolyte obtained after 1 hour of polymerization (LOW) showed fluidity even at room temperature (25°C) and its viscosity decreased upon heating, indicating thermoplasticity. The polymer electrolyte obtained after 1 hour and 45 minutes of polymerization (Middle) showed fluidity upon heating to approximately 150°C and also possessed thermoplasticity. The polymer electrolyte obtained after 2 hours and 30 minutes of polymerization (High) became more flexible upon heating to approximately 200°C, but lacked sufficient thermoplasticity.

[0070] 35% (w / w) pulp (unbleached Kimtowels, manufactured by Nippon Paper Crecia Co., Ltd., cut to a fiber length of approximately 3 mm in a mixer underwater and dried) was added to the obtained polymer electrolyte, heated to 120°C to fluidize, and kneaded until the pulp was uniformly dispersed.

[0071] The kneaded material was molded into a plate measuring 72 mm in length, 11 mm in width, and 3.0 mm in thickness. The molded body was heated at 140°C for 1 hour and then at 160°C for 16 hours to complete curing. All experimental procedures were performed under an air atmosphere. The molded body made from the unheated control sample and pulp, and the molded body made from the polymer electrolyte obtained by polymerization for 2 hours and 30 minutes and pulp, cracked during curing.

[0072] Since molding was achieved using polymer electrolytes obtained by polymerization for 1 hour and polymer electrolytes obtained by polymerization for 1 hour and 45 minutes as raw materials, a three-point bending test was performed in reference to JIS K7171. As a result, the bending strength of the molded article made from polymer electrolyte obtained by polymerization for 1 hour was 19 MPa and the bending modulus was 385 MPa, while the bending strength of the molded article made from polymer electrolyte obtained by polymerization for 1 hour and 45 minutes was 64 MPa and the bending modulus was 1445 MPa. From these results, it can be seen that the polymer electrolyte of the present invention exhibits 10% THF elution. 4 It contains the above polystyrene-equivalent molecular weight, and 10 8 It was found that the material exhibits excellent moldability and toughness when the polystyrene-equivalent molecular weight distribution does not exceed a certain value.

[0073] <Example 5> Manufacturing of molded products (amorphous oxygen-introduced substances) 50 ml of linolenic acid was placed in a 500 ml beaker, and 0.05% (w / w) FeCl3 was added as a radical initiator. The mixture was heated to 280°C while stirring to incorporate oxygen from the air, and the reaction was allowed to proceed for approximately 1 hour and 30 minutes. The linolenic acid turned black and became viscous. 2.5% (w / w) sodium hydroxide was added, and the mixture was heated for another hour. After that, the reaction was cooled to obtain a solid polymer electrolyte at room temperature.

[0074] 35% (w / w) pulp (unbleached Kimtowels, manufactured by Nippon Paper Crecia Co., Ltd., cut to a fiber length of approximately 3 mm in a mixer underwater and dried) was added to the obtained polymer electrolyte, heated to 120°C to fluidize, and kneaded until the pulp was uniformly dispersed.

[0075] The kneaded material was molded into a plate measuring 72 mm in length, 11 mm in width, and 2.8 mm in thickness. The molded body was heated at 140°C for 1 hour, and then at 160°C for 16 hours to complete the hardening process. All experimental procedures were performed under an air atmosphere.

[0076] A three-point bending test was performed on the molded body, referencing JIS K7171. The bending strength of the plate-shaped molded body was 22 MPa, and the bending modulus was 1290 MPa, confirming that it possesses a certain level of toughness similar to linoleic acid.

[0077] <Example 6> Manufacturing of molded products (amorphous oxygen-introduced substances) 50 ml of linoleic acid was placed in a 500 ml beaker, and 0.05% (w / w) FeCl3 was added as a radical initiator. The contents were stirred to incorporate oxygen from the air, and the mixture was heated to 280°C and reacted for approximately 1 hour and 30 minutes. 2.5% (w / w) sodium hydroxide was added, and the mixture was heated for another hour. The reaction was then cooled to obtain a solid polymer electrolyte at room temperature.

[0078] 35% (w / w) pulp (unbleached Kimtowels, manufactured by Nippon Paper Crecia Co., Ltd., cut to a fiber length of approximately 3 mm in a mixer underwater and dried) was added to the obtained polymer electrolyte, heated to 120°C to fluidize, and kneaded until the pulp was uniformly dispersed.

[0079] The kneaded material was shaped into a rod measuring 72 mm in length, 20 mm in width, and 20 mm in thickness. It was then heated at 140°C for 1 hour, followed by 160°C for 16 hours to complete the hardening process. All experimental procedures were performed under an air atmosphere. Subsequently, a plate measuring 72 mm in length, 10 mm in width, and 2.0 mm in thickness was cut from the center.

[0080] A three-point bending test was performed on the molded product, referencing JIS K7171. The bending strength of the plate-shaped molded product was 36 MPa, and the bending modulus was 3770 MPa, confirming that the inside of the molded product was sufficiently hardened.

[0081] <Example 7> Manufacturing of molded products (amorphous oxygen-introduced substances) 50 ml of linoleic acid was placed in two 500 ml beakers, and 0.05% (w / w) FeCl3 was added as a radical initiator. The contents were heated to 280°C while stirring to incorporate oxygen from the air, and the reaction was allowed to proceed for approximately 1 hour and 30 minutes. 2.5% (w / w) sodium hydroxide was then added, and the mixture was heated for another hour. After that, the reaction mixture was cooled to obtain a solid polymer electrolyte at room temperature.

[0082] To the obtained polymer electrolytes, 50% (w / w) cellulose powder (Fujifilm Wako Pure Chemical Industries, Ltd. "Cellulose, Powder, 38um (400mesh) permeable") or 50% (w / w) carbon fiber fragments (Yoshino Corporation "Carbon Fiber Chop 3mm") were added, heated to 120°C to fluidize, and kneaded until uniformly dispersed.

[0083] Cellulose powder mixture was molded into plates measuring 72 mm in length, 10 mm in width, and 2.0 mm in thickness, and carbon fiber fragment mixture was molded into plates measuring 72 mm in length, 10 mm in width, and 1.5 mm in thickness. Each molded body was heated at 140°C for 1 hour and then at 160°C for 16 hours to complete curing. All experimental procedures were performed under an air atmosphere.

[0084] A three-point bending test was performed on the molded bodies in accordance with JIS K7171. The bending strength of the molded body with cellulose powder was 86 MPa and the bending modulus was 3860 MPa. The bending strength of the molded body with carbon fiber fragments was 96 MPa and the bending modulus was 1485 MPa. Under these conditions, the density of the molded bodies with cellulose powder and the molded bodies with carbon fiber fragments was 0.7 cm³. 3 / g, 0.8cm 3 It was confirmed to be extremely lightweight and highly tough at [amount] / g.

[0085] <Example 8> Manufacturing of molded products (amorphous oxygen-introduced substances) 50 ml of linoleic acid was placed in a 500 ml beaker, and 0.05% (w / w) FeCl3 was added as a radical initiator. The contents were stirred to incorporate oxygen from the air, and the mixture was heated to 280°C and reacted for approximately 1 hour and 30 minutes. 2.5% (w / w) sodium hydroxide was added, and the mixture was heated for another hour. The reaction was then cooled to obtain a solid polymer electrolyte at room temperature.

[0086] 50% (w / w) of cellulose powder (Fujifilm Wako Pure Chemical Industries, Ltd. "Cellulose, Powder, 38um (400mesh) permeable") was added to the obtained polymer electrolyte, heated to 120°C to fluidize, and kneaded until uniformly dispersed. Further kneading was performed by adding water at a rate of approximately 20% (w / w) of the weight of the mixture to induce foaming.

[0087] Cellulose powder mixture was molded into a plate measuring 72 mm in length, 10 mm in width, and 2.0 mm in thickness. The molded body was heated at 140°C for 1 hour, and then at 160°C for 16 hours to complete foaming and hardening. All experimental procedures were performed under an air atmosphere.

[0088] A three-point bending test was performed on this foam, referencing JIS K7171. The bending strength of the foam was 6 MPa, and the bending modulus was 85 MPa. Under these conditions, the density of the foam was 0.4 cm³. 3 It was confirmed that it is lightweight and possesses a certain degree of toughness at a weight of / g.

[0089] <Example 9> Manufacturing of molded products (amorphous oxygen-introduced material, plasticization under anaerobic conditions) 50 ml of linoleic acid was placed in two 500 ml beakers, and 0.05% (w / w) FeCl3 was added as a radical initiator. The contents were heated to 280°C while stirring to incorporate oxygen from the air, and the reaction was allowed to proceed for approximately 1 hour and 30 minutes. 2.5% (w / w) sodium hydroxide was then added, and the mixture was heated for another 2 hours. After that, the reaction mixture was cooled to obtain a hard, pellet-shaped solid polymer electrolyte at room temperature.

[0090] To each of the obtained polymer electrolytes, 50% (w / w) cellulose powder (Fujifilm Wako Pure Chemical Industries, Ltd. "Cellulose, Powder, 38um (400 mesh) passable") was added. The obtained polymer electrolytes had low viscosity, and further polymerization would proceed in the presence of oxygen, potentially making mixing difficult. Therefore, the containers were covered with a heat-resistant autoclave bag, nitrogen was sealed inside, and the mixture was heated to 120°C under anaerobic conditions to fluidize it, and then mixed until each was uniformly dispersed.

[0091] Cellulose powder mixture was molded into plates measuring 72 mm in length, 10 mm in width, and 2.0 mm in thickness. Each molded plate was heated at 140°C for 1 hour, and then at 180°C for 1 hour to complete the curing process.

[0092] A three-point bending test of the molded article was conducted based on JIS K7171. The bending strength of the molded article with cellulose powder was 80 MPa, and the bending modulus was 3633 MPa. From these results, it was confirmed that even with the polymer electrolyte in question, which has a low viscosity during mixing due to advanced polymerization, further polymerization and viscosity reduction can be suppressed by placing it under anaerobic conditions, and it is possible to mix it sufficiently without affecting the strength of the final molded article.

[0093] <Example 10> Manufacturing of molded products (tangible oxygen-introduced materials) 50 ml of linoleic acid was placed in a 500 ml beaker, and 0.05% (w / w) FeCl3 was added as a radical initiator. 2.5% (w / w) sodium hydroxide was added to the contents and dissolved by heating and stirring at 200°C for 30 minutes.

[0094] The obtained polymer electrolyte material was applied to an equal amount (50% w / w) of cotton gauze (Suzuran Co., Ltd.'s "Gauze Handkerchief"), and the gauze was sandwiched between Kimtowels (product name, Nippon Paper Crecia Co., Ltd.) and subjected to a pressure of approximately 100 Pa for 5 minutes to remove the excess polymer electrolyte material. After that, the gauze containing the polymer electrolyte was layered to a thickness of approximately 3 mm and heated at 140°C for 1 hour, and then at 180°C for another 1 hour.

[0095] The resulting slightly thermoplastic sponge-like molded body was divided into three equal parts, and each was pressed at 250°C for 10 minutes to achieve thicknesses of 3.0 mm, 1.5 mm, and 1.0 mm respectively, with a density of 0.13 cm³. 3 / g, 0.26cm 3 / g, 0.39cm 3 A molded body with complete curing at / g was obtained. All experimental procedures were performed under an air atmosphere.

[0096] Based on JIS K7171, the obtained densities were 0.13 cm³ each. 3 / g, 0.26cm 3 / g, 0.39cm 3 Three-point bending tests were performed on molded bodies weighing / g. The bending strengths were 0.4 MPa, 1.6 MPa, and 35.7 MPa, respectively, and the bending moduli were 5 MPa, 95 MPa, and 3900 MPa, respectively. This confirmed that molded bodies with arbitrary densities and strengths can be produced by changing the press pressure. Furthermore, it was confirmed that under certain conditions, it can be used as a foam material and that it can achieve a similar level of strength to general polypropylene or polyethylene at about half the weight.

[0097] <Example 11> Manufacturing of molded products (tangible oxygen-introduced materials) 50 ml of linoleic acid was placed in a 500 ml beaker, and 0.05% (w / w) FeCl3 was added as a radical initiator. 2.5% (w / w) sodium hydroxide was added to the contents and dissolved by heating and stirring at 200°C for 30 minutes.

[0098] The obtained polymer electrolyte material was impregnated with an equal amount (50% w / w) of cotton twine (1mm thickness, No. 6, manufactured by Sanyo Sangyo Co., Ltd.), sandwiched between Kimtowels (product name, manufactured by Nippon Paper Crecia Co., Ltd.), and pressure of approximately 100 Pa was applied to remove the excess polymer electrolyte material. After that, it was heated at 140°C for 1 hour, and then at 180°C for 1 hour.

[0099] The resulting slightly thermoplastic cord is folded every 150 mm to form bundles with a radius of approximately 10 mm, and then pressed at 250°C for 10 minutes to a thickness of 1.0 mm, resulting in a density of 1.30 cm².3 A plate-shaped molded body with complete curing at / g was obtained. All experimental procedures were performed under an air atmosphere.

[0100] A three-point bending test was conducted based on JIS K7171. The bending strength perpendicular to the string was 115.2 MPa, and the bending modulus was 9635 MPa, confirming that a molded body with sufficient strength can be produced from the string-like raw material.

Claims

1. A polymer electrolyte having a partial polymer of a fatty acid having 16 or more carbon atoms, 2 or more double bonds, and carboxyl groups, wherein a portion of the carboxyl groups are neutralized with a basic substance and converted into carboxylate anionic groups, It has a content of 1.3 to 96% carboxylic acid anionic groups, A polymer electrolyte that is solid at room temperature.

2. The polymer electrolyte according to claim 1, which is a radical polymer.

3. The polymer electrolyte according to claim 1, wherein the basic substance is a substance containing an alkali metal or an alkaline earth metal.

4. The polymer electrolyte according to claim 1, wherein the fatty acid is derived from a plant.

5. The polymer electrolyte according to claim 1, wherein the fatty acid is linoleic acid or linolenic acid.

6. 10 ３ ~10 ９ The polymer electrolyte according to claim 1, having a polystyrene-equivalent molecular weight.

7. A bioplastic comprising a polymer electrolyte according to any one of claims 1 to 6.

8. The bioplastic according to claim 7, comprising an oxygen-introducing substance.

9. The bioplastic according to claim 8, wherein the oxygen-introducing substance is contained in an amount of 2.5 to 80% (w / w) based on the polymer electrolyte.

10. A molded article comprising a cured bioplastic according to claim 9.

11. A step of partially polymerizing a fatty acid having 16 or more carbon atoms, 2 or more double bonds, and a carboxyl group; and A step of reacting a partial polymer of fatty acids with a basic substance; and A step to adjust the content of carboxylate anionic groups to 1.3 to 96%; A method for producing a polymer electrolyte that is solid at room temperature and contains [a specific component].

12. A step of plasticizing a polymer electrolyte according to any one of claims 1 to 6; and A process of integrating a plasticized polymer electrolyte with an oxygen-introducing material; A method for producing bioplastics, including

13. A step of plasticizing a bioplastic according to claim 7; A process for molding plasticized bioplastics; and A process for curing the resulting molded plastic; A method for manufacturing a molded article, including the following:

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