WO2023027057A1

WO2023027057A1 - Polyelectrolyte, bioplastic, and molded body

Info

Publication number: WO2023027057A1
Application number: PCT/JP2022/031675
Authority: WO
Inventors: 岳志今井; 久明三原
Original assignee: 兵庫県; 学校法人立命館
Priority date: 2021-08-24
Filing date: 2022-08-23
Publication date: 2023-03-02
Also published as: JPWO2023027057A1

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

Polymer electrolytes, bioplastics and moldings

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.

In addition, since 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.

[Aspect 1]
A polyelectrolyte having a partial polymer of a fatty acid having 16 or more carbon atoms, 2 or more double bonds and carboxyl groups, the carboxyl groups being partially neutralized with a basic substance polyelectrolytes, which have been converted to carboxylate anion groups.

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

[Aspect 3]
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.

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

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

[Aspect 6]
6. The polymer electrolyte according to any one of Embodiments 1 to 5, which has a polystyrene equivalent molecular weight of 10 ³ to 10 ⁹ .

[Aspect 7]
7. The polyelectrolyte according to any one of aspects 1 to 6, having a content of carboxylate anion groups of 1.3 to 96%.

[Aspect 8]
A bioplastic comprising a polyelectrolyte according to any one of aspects 1-7.

[Aspect 9]
A bioplastic according to aspect 8, comprising an oxygenator.

[Aspect 10]
10. A bioplastic according to aspect 9, wherein the oxygenator is present in an amount of 2.5-80% (w/w) based on the polyelectrolyte.

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

[Aspect 12]
partially polymerizing a fatty acid having 16 or more carbon atoms, two or more double bonds and a carboxyl group; and reacting a fatty acid partial polymer with a basic substance;
A method for producing a polymer electrolyte, comprising:

[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 an oxygen-introducing substance;
A method for producing bioplastics, comprising:

[Aspect 14]
plasticizing the bioplastic according to any one of aspects 8-10;
molding the plasticized bioplastic; and curing the resulting molded plastic;
A method for producing a molded body, comprising:

According to the present invention, a novel polymer electrolyte, a bioplastic that can be molded into a tough three-dimensional object, and a molded body using these are provided.

In the polymer electrolyte of the present invention, when the amount of sodium hydroxide added was increased, the C=O stretching vibration peak of the carboxyl group decreased, while the C=O stretching vibration peak of the carboxylate anion group increased. It is an infrared spectroscopy spectrum showing that. 1 is a differential molecular weight distribution curve obtained by HPLC analysis of a THF-soluble component of the polymer electrolyte of the present invention.

<Polymer electrolyte>
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.

In addition, 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 to carboxylate anion groups, 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.

As 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.

Specific examples of unsaturated fatty acids include oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid and docosahexaenoic acid. Among the preferred unsaturated fatty acids are linoleic acid, linolenic acid and arachidonic acid. From the viewpoint of reducing the environmental load, the unsaturated fatty acid is preferably derived from plants, more preferably linoleic acid, α-linolenic acid and γ-linolenic acid.

A single type of unsaturated fatty acid may be used, or a mixture of multiple types may be used. Moreover, as a raw material of the polymer electrolyte, even 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.

When the oxidation polymerization reaction is performed 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 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.

Conventionally known oxidation catalysts may be used as the catalyst used for the oxidation polymerization reaction. Specific examples of 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. , Rh, Ni, Zr, Al, Ag, B, Cr metal powders or their oxides, hydroxides, sulfates, nitrates, chlorides, acetates, naphthenates, or organic oxidizing agents. Examples include anthracene, methyl ethyl ketone peroxide, and benzoyl peroxide.

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. Therefore, 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. 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. There is Specific examples of 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%.

<Bioplastic>
The bioplastic of the present invention contains the polymer electrolyte. When 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. By including 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. On the other hand, 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. As 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. When 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. When a tangible material is used for the oxygen introducing substance, generally, the oxygen introducing substance is integrated by laminating, coating or impregnating the plasticized polymer electrolyte with the oxygen introducing substance.

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. Specific examples of 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. In addition, 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.

<Molded body>
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. In the process of plasticizing bioplastics, or when maintaining viscosity or plasticity from plasticization to completion of molding, bioplastics are plasticized and molded in an oxygen-free atmosphere. is preferred. On the other hand, for the reasons described above, when the simplicity of the work or equipment is emphasized, 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, α-linolenic acid and γ-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.
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples. The invention is not limited to these examples.

<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.

10 mL each of this linoleic acid was aliquoted and Sodium hydroxide was added in an amount to (w/w).

The polymer to which sodium hydroxide was added was heated with stirring at 100°C for 2 hours, after which the reactant was cooled. The 25% (w/w) sample soaped and was crushed to a certain size. Thereafter, 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.

In the spectrum of FIG. 1, as the amount of sodium hydroxide added increases, the peak at a wavelength of 1740 ^cm derived from the C=O stretching vibration of the carboxyl group decreases, and the C=O stretching vibration of the carboxylate anion group decreases. The peak at the wavelength 1557 cm ⁻¹ increases. From this, it can be seen that the carboxyl groups of the fatty acid polymer actually reacted with the basic substance and were converted to carboxylate anion groups.

<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%.

10 mg of this polymer electrolyte was taken, 1 mL of THF was added, and after shaking at 25°C for 1 hour, 20 µL of the supernatant was analyzed by HPLC using a GPC column (Shodex KF-805L, 40°C). The developing solvent was THF, the flow rate was 1 mL/min, and detection was performed with a differential refractometer (RI). Under these conditions, the polystyrene-equivalent molecular weight of the dissolved polymer electrolyte was calculated. As a result, a wide molecular weight distribution of 10 ³ to 10 ⁸ was observed. When this polymer electrolyte was heated to about 100° C., it showed fluidity and had 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 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.

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.

10 mg of this polymer electrolyte was taken, 1 mL of THF was added, and after shaking at 25°C for 1 hour, 20 µL of the supernatant was analyzed by HPLC using a GPC column (Shodex KF-805L, 40°C). The developing solvent was THF, the flow rate was 1 mL/min, and the detection was performed at RI. As a result, a differential molecular weight distribution curve as shown in FIG. 2 was obtained. The polymer electrolyte (LOW) obtained by polymerization for 1 hour exhibited fluidity even at room temperature of 25° C., and had thermoplasticity because its viscosity decreased when heated. 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.

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.

When the polymer electrolyte obtained by polymerization for 1 hour and the polymer electrolyte obtained by polymerization for 1 hour and 45 minutes were used as raw materials, molding was achieved, so a three-point bending test was performed with reference to JISK7171. As a result, the bending strength of the molding made from the polymer electrolyte obtained by polymerization for 1 hour was 19 MPa, and the bending elastic modulus was 385 MPa. The resulting molded product had a bending strength of 64 MPa and a bending elastic modulus of 1445 MPa. From these results, 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.

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.

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.

50% (w/w) of cellulose powder (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. "Cellulose, powder, 38um (400mesh) passing", or 50% (w/w) of carbon fiber fragments were added to the resulting polymer electrolyte. ("Carbon fiber chop 3 mm" manufactured by Yoshino Co., Ltd. was added, heated to 120°C to fluidize, and kneaded until they were uniformly dispersed.

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.

With reference to JISK7171, 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. Moreover, 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.

50% (w/w) of cellulose powder (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., "cellulose, powder, 38um (400mesh) passage") was added to the obtained polymer electrolyte, and heated to 120°C to fluidize and homogenize. It was kneaded until it was dispersed in For further foaming, water was added to about 20% (w/w) of the weight of the kneaded material and kneaded.

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.

50% (w/w) of cellulose powder (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. "Cellulose, powder, 38 μm (400 mesh) passage") was added to each of the obtained polymer electrolytes. In the presence of oxygen, polymerization progressed further and kneading was likely to become difficult. Therefore, the entire container was covered with a heat-resistant autoclave bag, filled with nitrogen, and heated to 120°C under anaerobic conditions. and kneaded until each was uniformly dispersed.

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.

A three-point bending test was performed on the compact with reference to JISK7171. The flexural strength of the compact with cellulose powder was 80 MPa, and the flexural modulus was 3633 MPa. From this result, even if the polymer electrolyte has a low viscosity at the time of kneading, polymerization progresses, and by placing it under anaerobic conditions, the decrease in viscosity due to further polymerization is suppressed, and the final strength of the molded product is It was confirmed that it is possible to sufficiently knead to the extent that there is no effect on the

<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.

An equal amount (50% (w/w)) of the obtained polyelectrolyte raw material was applied to cotton gauze ("gauze handkerchief" manufactured by Suzuran Co., Ltd.) and sandwiched between Kimtowels (trade name, manufactured by Nippon Paper Crecia Co., Ltd.). A pressure of about 100 Pa was applied for 5 minutes to remove an excess amount of the polymer electrolyte raw material. After that, the gauze containing this polymer electrolyte was layered so as to have a thickness of about 3 mm, and heated at 140° C. for 1 hour and further at 180° C. for 1 hour.

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.

With reference to JISK7171, 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. In addition, it was confirmed that depending on the conditions, it can be used as a foam material, and that it can have the same strength as general polypropylene or polyethylene with about half the weight.

<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.

An equal amount (50% (w/w)) of the obtained polymer electrolyte raw material was impregnated into a cotton octopus thread (manufactured by Sanyu Sangyo Co., Ltd., "thickness 1 mm No. 6"), and Kimtowel (trade name, Nippon Paper Crecia Co., Ltd.) A pressure of about 100 Pa was applied to remove the surplus polymer electrolyte raw material. After that, it was heated at 140° C. for 1 hour and further at 180° C. for 1 hour.

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.

Claims

A polyelectrolyte having a partial polymer of a fatty acid having 16 or more carbon atoms, 2 or more double bonds and carboxyl groups, the carboxyl groups being partially neutralized with a basic substance polyelectrolytes, which have been converted to carboxylate anion groups.
The polymer electrolyte according to claim 1, which is a radical polymer.
The polymer electrolyte according to claim 1 or 2, wherein the basic substance is a substance containing an alkali metal or an alkaline earth metal.
The polymer electrolyte according to any one of claims 1 to 3, wherein the fatty acid is derived from a plant.
The polymer electrolyte according to any one of claims 1 to 4, wherein the fatty acid is linoleic acid or linolenic acid.
6. The polymer electrolyte according to any one of claims 1 to 5, which has a polystyrene equivalent molecular weight of 10 3 to 10 9 .
The polymer electrolyte according to any one of claims 1 to 6, which has a content of carboxylate anion groups of 1.3 to 96%.
A bioplastic containing the polymer electrolyte according to any one of claims 1 to 7.
The bioplastic according to claim 8, which contains an oxygen introducing substance.
The bioplastic according to claim 9, wherein the oxygen introducing substance is contained in an amount of 2.5 to 80% (w/w) based on the polyelectrolyte.
A molded body comprising the cured bioplastic according to any one of claims 8 to 10.
partially polymerizing a fatty acid having 16 or more carbon atoms, two or more double bonds and a carboxyl group; and reacting a fatty acid partial polymer with a basic substance;
A method for producing a polymer electrolyte, comprising:
a step of plasticizing the polymer electrolyte according to any one of claims 1 to 7; and a step of integrating the plasticized polymer electrolyte and an oxygen-introducing substance;
A method for producing bioplastics, comprising:
A step of plasticizing the bioplastic according to any one of claims 8-10;
molding the plasticized bioplastic; and curing the resulting molded plastic;
A method for producing a molded body, comprising: