Mechanically robust sustainable plastics and their green, non-covalent manufacturing methods

Abstract

A composite comprising an oxyanion and an organic cation obtained through ionization of a compound having at least two amino groups or guanidino groups, wherein the organic cation and the oxyanion are bound by an ionic bond and a hydrogen bond.

Description

[Technical Field]

[0001] This invention relates to a mechanically robust and sustainable plastic and a method for manufacturing the same. [Background technology]

[0002] Our daily lives involve the use of various plastics, including polyethylene terephthalate, polycarbonate, polymethacrylate, polyolefin, and polyurethane. Since 1950, over 8.3 billion tons of plastic have been produced, with 6.3 billion tons discarded as waste (Non-Patent Literature 1), and the impact of used plastics on the environment, such as oceans and soil, has become a serious problem.

[0003] With laws regulating plastics being enacted both domestically and internationally, such as the 2021 Basel Convention on the Import and Export of Plastics and Japan's "Act on Promotion of Resource Recycling Related to Plastics," regulations on plastics are progressing, and there is a growing demand for the use of environmentally friendly plastics.

[0004] Although plastic recycling is being promoted, the recycling rate is only about 9% of global production (Non-Patent Literature 1), and the majority of used plastics are still incinerated. While polyethylene terephthalate is relatively well recycled, it is difficult to decompose and recycle.

[0005] While various polymers that can be recycled using catalysts (Non-Patent Literature 2) and biodegradable polymers (Non-Patent Literature 3) have been developed, plastic recycling presents several problems, including the complexity and high cost of the recycling process, the cost associated with using catalysts such as precious metals for plastic regeneration, and the difficulty in decomposing plastics into monomers.

[0006] On the other hand, supramolecular polymers, in which monomers are bonded together by non-covalent bonds, are expected to be new materials with low environmental impact because they are recyclable, as the monomers adhere to each other through weak, reversible interactions, and can separate due to external stimuli or re-bond through self-repair even if bonding occurs. For example, Non-Patent Document 4 discloses a photoresponsive supramolecular polymer glass with high stiffness and good self-repairing properties, composed of an aggregate of 1,1,1-tris(hydroxymethyl)propane monomers having three ureido-4-pyrimidinone groups. Non-Patent Document 5 discloses a metal supramolecular copolymer composed of a monomer in which three 2,6-bis(1'-methylbenzimidazolyl)pyridines are bonded to a 1,3,5-tris(alkyl)benzene core, or a monomer in which two 2,6-bis(1'-methylbenzimidazolyl)pyridines are bonded to poly(ethylene-co-butylene) and combined with Zn(NTf2)2. However, conventional photoresponsive supramolecular polymer glasses have poor mechanical strength. [Prior art documents] [Non-patent literature]

[0007] [Non-Patent Document 1] Sci. Adv. 2017, 3, e1700782. [Non-Patent Document 2] Science 2018, 360, 398-403. [Non-Patent Document 3] Nature 2020, 590, 423-427. [Non-Patent Document 4] Nature Commun. 2016, 7, 10995. [Non-Patent Document 5] Nature Commun. 2022, 13, 356. [Overview of the project] [Problems that the invention aims to solve]

[0008] The problem that this invention aims to solve is to provide a mechanically robust composite that can be synthesized and molded using an aqueous solvent. [Means for solving the problem]

[0009] The present invention encompasses the embodiments described below. Section 1. An organic cation formed by the ionization of a compound having at least two amino groups or guanidino groups, It contains oxyanions, A composite in which the organic cation and the oxyanion are bonded together by ionic bonds and hydrogen bonds.

[0010] Section 2. The composite according to item 1, wherein the organic cation and the oxyanion are bonded by an ionic bond and a hydrogen bond represented by one or more of the following formulas (1) to (4).

[0011] [ka] (In each of equations (1) to (4), R is any monovalent organic group.)

[0012] Section 3. The composite according to item 1, wherein the organic cation is an organic cation obtained by ionizing a guanidine compound represented by the following formula (6).

[0013] [ka]

[0014] (In the formula, R is a substituted or unsubstituted hydrocarbon chain, When the hydrocarbon chain is substituted, a portion of the methylene groups in the hydrocarbon chain is substituted with a group selected from the group consisting of -NH-, -N(alkyl group)-, -O-, -COO-, -O-COO-, -NHCO-, -S-, cycloalkane, cycloalkanone, benzene, the group represented by formula (7), and substituted or unsubstituted -N(guanidylalkylene group)-. If the -N(guanidylalkylene group) is substituted, a portion of the methylene groups in the guazinylalkylene group is substituted with the same group that substituted a portion of the methylene groups in the hydrocarbon chain.

[0015] [ka]

[0016] (In the formula, R1 and R2 are each independently an alkyl group or phenyl group having 1 to 6 carbon atoms, R3 and R4 are each independently an alkyl group or phenyl group having 1 to 6 carbon atoms, m is 1 to 6, n is 1 to 6, p is an integer in the range of 0 to 20, q is an integer in the range of 0 to 20, where p+q is an integer of 1 or greater.) Section 4. The complex according to claim 3, wherein the guanidine compound comprises compound (I), compound (II), or both. (I) Compounds represented by formula (6), wherein A is a substituted or unsubstituted hydrocarbon chain, and if the hydrocarbon chain is substituted, a portion of the methylene groups of the hydrocarbon chain is substituted with a group selected from the group consisting of -NH-, -N(alkyl group)-, -O-, -COO-, -O-COO-, -NHCO-, -S-, cycloalkane, cycloalkanone, benzene, and substituted or unsubstituted -N(guanidylalkylene group)-, and if the -N(guanidylalkylene group) is substituted, a portion of the methylene groups of the guazinylalkylene group is substituted with the same group that substituted a portion of the methylene groups of the hydrocarbon chain, except for compounds in which a portion of the methylene groups of the hydrocarbon chain is substituted with a group represented by formula (7). (II) Compounds represented by formula (6), wherein A is substituted in a hydrocarbon chain, and a portion of the methylene groups in the hydrocarbon chain is substituted by a group represented by formula (7), Section 5. The composite according to item 1, wherein the oxyanion is an oxyanion of sulfur, phosphorus, silicon, or carbon. Section 6. The complex described in item 5, wherein the oxyanion is a polyoxyanion. Section 7. The complex according to item 5, wherein the oxyanion is a cyclic phosphate anion represented by the following formula (10), a linear phosphate anion represented by the following formula (11), a phytic acid anion, or a carboxylic acid anion.

[0017] [ka]

[0018] (In the formula, n is either 1 or 4)

[0019] [ka]

[0020] (In the formula, n is an integer from 1 to 1000) Section 8. The complex according to item 1 or 5, wherein the oxyanion is an oxyanion produced by the ionization of a polysaccharide having an anionic functional group. Section 9. The complex described in item 1, which is insoluble in organic solvents. Section 10. The composite according to item 1, which can be processed in water at 20°C. Section 11. The complex described in item 1, which has self-healing properties. Section 12. The composite according to item 1, wherein the composite with a thickness of 0.5 mm has a light transmittance of 90% or more in the 400-800 nm range. Section 13. The composite described in item 1 is a supramolecular plastic. Section 14. The composite described in item 1, which is a supramolecular polymer glass. Section 15. A composition comprising the complex described in any one of items 1 to 14. Section 16. Articles containing a composite as described in any one of paragraphs 1 to 14. Section 17. A method for producing a complex, comprising mixing a compound having at least two amino groups or guanidino groups with an oxyanion-containing compound in water or an aqueous solution, thereby generating a complex in which an organic cation formed by the ionization of the compound having at least two amino groups or guanidino groups and an oxyanion formed by the ionization of the oxyanion-containing compound are linked by ionic bonds and hydrogen bonds. Section 18. The use of a compound having at least two amino groups or guanidino groups and a compound containing an oxyanion of sulfur, phosphorus, silicon, or carbon for the production of a supramolecular polymer composite. [Effects of the Invention]

[0021] According to the present invention, it is possible to provide a mechanically robust composite that has little to no environmental impact during manufacturing and processing. [Brief explanation of the drawing]

[0022] [Figure 1] A schematic diagram showing the polymer network of supramolecular polymer glass (SPG). [Figure 2A] A photograph showing liquid-liquid phase separation during the manufacturing of supramolecular polymer glass (SPG). [Figure 2B] Microscopic image of a micelle of a supramolecular polymer. [Figure 3]A graph showing the light transmittance of various plastics and first-generation supramolecular polymer glass. PMMA: Polymethyl methacrylate, PC: Polycarbonate, PET: Polyethylene terephthalate, PS: Polystyrene, Glass: Inorganic glass, SPG: Supramolecular polymer glass. [Figure 4] A photograph showing a first-generation supramolecular polymer glass, formed by hot pressing, with a weight placed on top. [Figure 5] Graphs showing the Young's modulus of various plastics and first-generation supramolecular polymer glass. Second from the right: Uses first-generation monomer GuMGen.I-(9-2). Far right: Uses first-generation monomer GuMGen.I-(9-4). Rubber: Rubber, PVA: Polyvinyl acetate, PTFE: Polytetrafluoroethylene, PP: Polypropylene, PET: Polyethylene terephthalate, PS: Polystyrene, PMMA: Polymethyl methacrylate, PEEK: Aromatic polyether ketone, Nylon: Nylon, SPG: Supramolecular polymer glass [Figure 6] Graph showing the tensile strength of various plastics and first-generation supramolecular polymer glass. Second from the right: First-generation monomer GuMGen.I-(9-2) used. Far right: First-generation monomer GuMGen.I-(9-4) used. Rubber: Rubber, PVA: Polyvinyl acetate, PTFE: Polytetrafluoroethylene, PP: Polypropylene, PET: Polyethylene terephthalate, PS: Polystyrene, PMMA: Polymethyl methacrylate, PEEK: Aromatic polyether ketone, Nylon: Nylon, SPG: Supramolecular polymer glass [Figure 7] Young's modulus of first-generation supramolecular polymer glass (Gen.1SPG, far right), second-generation supramolecular polymer glass (Gen.2SPG, far left), and three third-generation supramolecular polymer glasses (Gen.2SPG and Gen.1SPG, the three bars in the center). The molar ratio of the guanidine compounds used in the production of each third-generation supramolecular polymer glass (denoted as M1 and M2, respectively) was varied. (From left to right: M1:M2 molar ratios are 4:1, 1:1, and 1:4). [Figure 8] (A)(B) Photographs showing the underwater processability of first-generation supramolecular polymer glass. (A) 10 seconds after immersion in water, (B) 2 hours after immersion in water. [Figure 9] Synthesis of supramolecular polymer glass using diamine and sodium hexametaphosphate. [Figure 10A] Measurement results of a compression experiment with SPG composed of GuMGen.II-1 and phytic acid. Force: force, Displacement: displacement. [Figure 10B] Measurement results of a compression experiment with SPG composed of GuMGen.I-2 and phytic acid. Force: force, Displacement: displacement. [Figure 11A] Measurement results from an indentation experiment of SPG composed of diamine and alginic acid. [Figure 11B] Measurement results from an indentation experiment of SPG composed of guanidine and alginate. [Figure 11C] Measurement results of an indentation experiment with SPG consisting of diamine / guanidine, alginic acid, and hexametaphosphate. [Figure 12] A photograph of a supramolecular polymer emulsion produced by mixing chondroitin sulfate and a first-generation monomer (GuMGen.I). [Figure 13] A photograph of the supramolecular polymer glass synthesized in Example 6. [Figure 14] A photograph of a supramolecular polymer emulsion produced by mixing sodium heparin sulfate with a first-generation monomer (GuMGen.I). [Figure 15] A photograph of the supramolecular polymer glass synthesized in Example 7. [Figure 16] A photograph of a supramolecular polymer emulsion produced by mixing dextran sulfate sodium with a first-generation monomer (GuMGen.I). [Figure 17] A photograph of the supramolecular polymer glass synthesized in Example 8. [Figure 18]A photograph of a supramolecular polymer emulsion produced by mixing β-cyclodextrin substituted with -SO3Na with a first-generation monomer (GuMGen.I). The inset on the left points to a glass tube containing the emulsion. [Figure 19] A photograph of the supramolecular polymer glass synthesized in Example 9. [Modes for carrying out the invention]

[0023] As used herein, "contains" and "include" also encompass the concept of "consist of."

[0024] In the numerical ranges described stepwise in this specification, the upper or lower limit of a numerical range in one step can be arbitrarily combined with the upper or lower limit of a numerical range in another step. Furthermore, in the numerical ranges described in this specification, the upper or lower limit of a numerical range may be replaced with values ​​shown in the examples or values ​​that can be uniquely derived from the examples. Moreover, in this specification, numbers connected by "~" mean a numerical range that includes the numbers before and after "~" as the lower and upper limits.

[0025] As used herein, "composite" refers to a material composed of two or more substances bonded together. Each substance constituting a composite may be referred to as a "monomer." A composite composed of two or more molecules bonded together may be referred to as a "molecular aggregate."

[0026] As used herein, "supramolecular polymer" refers to a polymer formed by the reversible interaction of two or more monomers. Examples of reversible interactions include hydrogen bonds, ionic bonds, hydrophobic interactions, electrostatic interactions, and / or non-covalent bonds such as van der Waals forces.

[0027] As used herein, "supramolecular plastic" refers to a polymer or composition containing a polymer formed by the reversible interaction of two or more monomers. "Supramolecular plastic" may be the same as "supramolecular polymer," or it may contain substances other than "supramolecular polymer." "Supramolecular plastic" may be a synthetic resin.

[0028] As used herein, "glass" refers to an amorphous solid material. Amorphous, also known as non-amorphous, refers to a material in which no clear diffraction phenomenon is observed by X-ray diffraction, and which exhibits a disordered atomic arrangement.

[0029] As used herein, “organic cation” means a cation having a structure that contains at least one carbon atom.

[0030] As used herein, "oxyanion" refers to an anion containing oxygen bonded to a nonmetal.

[0031] According to a first aspect of this disclosure, a composite is provided which contains an organic cation formed by ionizing a compound having at least two amino groups or guanidino groups, and an oxyanion, wherein the organic cation and the oxyanion are bonded by ionic bonds and hydrogen bonds.

[0032] To facilitate understanding of the invention, Figure 1 schematically shows an example of a composite made of a supramolecular polymer. The physical properties of the supramolecular polymer described below can be applied to the composite of the present invention.

[0033] In the supramolecular polymer (1), an organic cation (2), formed by the ionization of a compound having at least two amino groups or a compound having at least two guanidino groups, and an oxyanion (3) are bonded together by non-covalent bonds. Because the bonds between these monomers are strong, the mechanical strength of the supramolecular polymer is higher than that of conventional supramolecular polymers. Furthermore, compared to cases where monomers are covalently bonded, the separation of the organic cation and oxyanion is easier, resulting in superior recyclability. The organic cation and oxyanion can be separated, for example, by immersion in a polar medium such as water or an aqueous solution for a certain period of time. Note that compounds having at least two amino groups exclude compounds having at least two guanidino groups.

[0034] In some embodiments, the organic cation and the oxyanion are bonded by an ionic bond and a hydrogen bond represented by one or more of the following formulas (1) to (4).

[0035] [ka]

[0036] In each of formulas (1) to (4), R is any monovalent organic group. In this specification, an organic group means a group having one or more carbon atoms. If there are two or more Rs in a molecule, the Rs may be the same or different. As shown in formulas (1) and (2), hydrogen bonds are formed between the hydrogens derived from the two amino groups of the amine compound and the oxygen of the oxyanion, while an ionic bond is formed between the ammonium cation and the oxyanion. Alternatively, as shown in formulas (3) and (4), hydrogen bonds are formed between the hydrogens derived from the two guanidino groups of the guanidine compound and the oxygen of the oxyanion, while an ionic bond is formed between the guanidium cation and the oxyanion. This improves the mechanical strength of the supramolecular polymer. On the other hand, the bond between the organic cation and the oxyanion is easier to separate compared to a covalent bond.

[0037] In some embodiments, the compound having at least two amino groups is an amine compound represented by the following formula (5).

[0038] [ka]

[0039] (In the formula, R is a substituted or unsubstituted hydrocarbon chain. If the hydrocarbon chain is substituted, a portion of the methylene groups of the hydrocarbon chain is substituted with a group selected from the group consisting of -NH-, -N(alkyl group)-, -O-, -COO-, -O-COO-, -NHCO-, -S-, cycloalkane, cycloalkanone, benzene, the group represented by formula (7), and a substituted or unsubstituted -N(guanidylalkylene group)-. If the -N(guanidylalkylene group) is substituted, a portion of the methylene groups of the guazinylalkylene group is substituted with the same group that substitutes a portion of the methylene groups of the hydrocarbon chain.)

[0040] [ka]

[0041] (In the formula, R1 and R2 are each independently an alkyl group or phenyl group having 1 to 6 carbon atoms, R3 and R4 are each independently an alkyl group or phenyl group having 1 to 6 carbon atoms, m is 1 to 6, n is 1 to 6, p is an integer in the range of 0 to 20, q is an integer in the range of 0 to 20, where p+q is an integer of 1 or greater.)

[0042] The hydrocarbon chain of R may be an aliphatic hydrocarbon chain, an alicyclic hydrocarbon chain, an aromatic hydrocarbon chain, or a combination thereof. The aliphatic hydrocarbon chain may be a saturated straight aliphatic hydrocarbon chain or an unsaturated aliphatic hydrocarbon chain, and may be straight or branched. Preferably, the hydrocarbon chain is a straight or branched saturated hydrocarbon chain.

[0043] When some of the methylene groups in a hydrocarbon chain are substituted, the number of substituted methylene groups is not limited, but it is preferably 1 to 20, preferably 1 to 10, and more preferably 1 to 5.

[0044] In certain embodiments, the alkyl group of -N(alkyl group), which is a substituent on the methylene group of the hydrocarbon chain, is preferably a linear or branched alkyl group having 1 to 6 carbon atoms. In certain embodiments, the alkylene group of -N(guanidylalkylene group), which is a substituent on the methylene group of the hydrocarbon chain, is preferably a linear or branched alkylene having 1 to 6 carbon atoms.

[0045] In formula (7), the C1-C6 alkyl groups of R1 and R2 may be linear, branched, or cyclic. The C3 and R4 alkyl groups may be linear, branched, or cyclic. In a particular embodiment, the C1-C6 alkyl groups of R1, R2, R3, and R4 are each independently linear alkyl groups having C1-C6. In a particular embodiment, both p and q are integers in the range of 1 to 20. In a particular embodiment, one of p and q is an integer in the range of 1 to 20, and the other of p and q is 0.

[0046] A compound having at least two amino groups may have two, three, or four or more amino groups in a single molecule.

[0047] Amine compounds with three amino groups in a single molecule generally exhibit greater mechanical strength than those with two amino groups. Furthermore, when guanidine compounds have -NH- substituents on nitrogen in their hydrocarbon chain, their solubility in water improves, and they become more likely to form amorphous structures.

[0048] In some embodiments, the compound having at least two guanidino groups is a guanidine compound represented by the following formula (6).

[0049] [ka]

[0050] (In the formula, R is a substituted or unsubstituted hydrocarbon chain. If the hydrocarbon chain is substituted, a portion of the methylene groups of the hydrocarbon chain is substituted with a group selected from the group consisting of -NH-, -N(alkyl group)-, -O-, -COO-, -O-COO-, -NHCO-, -S-, cycloalkane, cycloalkanone, benzene, the group represented by formula (7), and a substituted or unsubstituted -N(guanidylalkylene group)-. If the -N(guanidylalkylene group) is substituted, a portion of the methylene groups of the guazinylalkylene group is substituted with the same group that substitutes a portion of the methylene groups of the hydrocarbon chain.)

[0051] [ka]

[0052] (In the formula, R1 and R2 are each independently an alkyl group or phenyl group having 1 to 6 carbon atoms, R3 and R4 are each independently an alkyl group or phenyl group having 1 to 6 carbon atoms, m is 1 to 6, n is 1 to 6, p is an integer in the range of 0 to 20, q is an integer in the range of 0 to 20, where p+q is an integer of 1 or greater.) The hydrocarbon chain of R may be an aliphatic hydrocarbon chain, an alicyclic hydrocarbon chain, an aromatic hydrocarbon chain, or a combination thereof. The aliphatic hydrocarbon chain may be a saturated straight aliphatic hydrocarbon chain or an unsaturated aliphatic hydrocarbon chain, and may be straight or branched. Preferably, the hydrocarbon chain is a straight or branched saturated hydrocarbon chain.

[0053] When some of the methylene groups in a hydrocarbon chain are substituted, the number of substituted methylene groups is not limited, but it is preferably 1 to 20, preferably 1 to 10, and more preferably 1 to 5.

[0054] In certain embodiments, the alkyl group of -N(alkyl group), which is a substituent on the methylene group of the hydrocarbon chain, is preferably a linear or branched alkyl group having 1 to 6 carbon atoms. In certain embodiments, the alkylene group of -N(guanidylalkylene group), which is a substituent on the methylene group of the hydrocarbon chain, is preferably a linear or branched alkylene having 1 to 6 carbon atoms.

[0055] In formula (7), the C1-C6 alkyl groups of R1 and R2 may be linear, branched, or cyclic. The C3 and R4 alkyl groups may be linear, branched, or cyclic. In a particular embodiment, the C1-C6 alkyl groups of R1, R2, R3, and R4 are each independently linear alkyl groups having C1-C6. In a particular embodiment, both p and q are integers in the range of 1 to 20. In a particular embodiment, one of p and q is an integer in the range of 1 to 20, and the other of p and q is 0.

[0056] A guanidine compound having at least two guanidino groups may have two, three, or four or more guanidino groups in a single molecule.

[0057] Guanidine compounds with three guanidino groups in a single molecule generally exhibit greater mechanical strength than those with two guanidino groups. Furthermore, when guanidine compounds have -NH- substituents on nitrogen in their hydrocarbon chain, their solubility in water improves, and they become more likely to form amorphous structures.

[0058] In some embodiments, the guanidine compound is either the guanidine compound of (I) below, the guanidine compound of (II) below, or includes both the guanidine compound of (I) and the guanidine compound of (II).

[0059] (I) Guanidine compound: A compound represented by formula (6), wherein A is a substituted or unsubstituted hydrocarbon chain, and if the hydrocarbon chain is substituted, a portion of the methylene groups of the hydrocarbon chain is substituted with a group selected from the group consisting of -NH-, -N(alkyl group)-, -O-, -COO-, -O-COO-, -NHCO-, -S-, cycloalkane, cycloalkanone, benzene, and substituted or unsubstituted -N(guanidylalkylene group)-, and if the -N(guanidylalkylene group) is substituted, a portion of the methylene groups of the guazinylalkylene group is substituted with the same group that substituted a portion of the methylene groups of the hydrocarbon chain. However, this excludes compounds in which a portion of the methylene groups of the hydrocarbon chain is substituted with a group represented by formula (7).

[0060] (II) Guanidine compound: A compound represented by formula (6), wherein A is substituted in a hydrocarbon chain, and a portion of the methylene groups in the hydrocarbon chain are substituted by a group represented by formula (7).

[0061] The supramolecular polymer produced using the guanidine compound (I) has high mechanical strength, is easily soluble in water, and has high processability in water.

[0062] Specific examples of organic cations formed by the protonation of the guanidine compound (I) include the following organic cations:

[0063] Supramolecular polymers produced using guanidine compounds (II) tend to have lower solubility in water and lower mechanical strength compared to supramolecular polymers produced using guanidine compounds (I).

[0064] Therefore, a supramolecular polymer produced using both the guanidine compound (I) and the guanidine compound (II) can suppress the solubility in water of the supramolecular polymer produced using the guanidine compound (I) while improving the mechanical strength of the supramolecular polymer produced using the guanidine compound (II).

[0065] In a supramolecular polymer produced using both guanidine compound (I) and guanidine compound (II), each of guanidine compound (I) and guanidine compound (II) may be any combination of guanidine compound (I) and guanidine compound (II) disclosed herein. Each of guanidine compound (I) and guanidine compound (II) may be one type or two or more types.

[0066] The molar ratio of the guanidine compound (I) to the guanidine compound (II) for producing the supramolecular polymer is not particularly limited, but is preferably 90:10 to 10:90, and more preferably 20:80 to 80:20.

[0067] Specific examples of organic cations formed by the protonation of the guanidine compound (II) include the organic cations represented by the following formulas (9-1) to (9-10).

[0068] [ka]

[0069] (In each of equations (9-1) to (9-6), n is an integer between 1 and 100.)

[0070] In equation (9-2), m is an integer between 1 and 100.

[0071] Guanidine is a highly safe substance that is naturally present in living organisms. Guanidine compounds may be synthesized by known methods or commercially available products may be used.

[0072] An oxyanion refers to an anion having a structure consisting of a central element and oxygen bonded to that central element. The central element is not particularly limited and may be a metallic or nonmetallic element, but sulfur, phosphorus, silicon, or carbon are more preferred in terms of safety and low environmental impact.

[0073] In some embodiments, the oxyanion is a sulfur, phosphorus, silicon, or carbon oxyanion. The oxyanion is produced by the ionization of a sulfur, phosphorus, silicon, or carbon oxyanion-containing compound. Examples of sulfur, phosphorus, silicon, or carbon oxyanion-containing compounds include, but are not limited to, salts selected from the group consisting of sulfates, sulfites, sulfonates, protonated phosphates, phosphates, polyphosphates, metaphosphates, phosphoniates, oxyphosphates, silicates, carboxylates, carbonates, and combinations thereof. The salt is preferably a metal salt, and preferred metals constituting the metal salt include, but are not limited to, sodium, potassium, lithium, calcium, strontium, barium, and magnesium. The supramolecular polymer may contain one type of oxyanion or two or more types of oxyanions. Alternatively, examples of sulfur, phosphorus, silicon, or carbon oxyanion-containing compounds include, but are not limited to, salts selected from the group consisting of sulfate esters, phosphodiesters, silicate esters, and carboxylate esters, and combinations thereof.

[0074] In some embodiments, the oxyanion is a polyoxyanion having two or more central elements in a single molecule. Because the oxyanion is a divalent or higher anion, it can bond with the organic cation (the other molecule) at two or more locations, enabling the formation of a network structure through the bonding between the organic cation and the oxyanion.

[0075] In some embodiments, the oxyanion is a cyclic phosphate anion represented by formula (10), a linear phosphate anion represented by formula (11), a phytic acid anion, or a carboxylic acid anion.

[0076] [ka]

[0077] (In the formula, n is an integer between 1 and 4.)

[0078] [ka]

[0079] (In the formula, n is an integer from 1 to 1000)

[0080] In the cyclic phosphate anion of formula (10), n is preferably 1 or 4, and more preferably n is 4. Sodium hexametaphosphate, used as a raw material for the hexaphosphate ion when n is 4, is a compound approved by the U.S. Food and Drug Administration (FDA) and is highly safe. Furthermore, an oxyanion with n = 4 is more preferable in terms of obtaining a supramolecular polymer with high mechanical strength. The upper limit of n is preferably 100.

[0081] The linear phosphate anion n represented by formula (11) is preferably 1 to 1000.

[0082] Compounds containing sulfur, phosphorus, silicon, or carbon oxyanions may be synthesized by known methods or commercially available products may be used.

[0083] The anion of phytic acid is the anion produced when phytic acid, represented by formula (12), is deprotonated.

[0084] [ka]

[0085] Carboxylic acid anions, also called carbanions, include, but are not limited to, the anions produced by the deprotonation of carboxylic acids represented by formulas (13-1) and (13-2), and the alginic acid anion represented by formula (14).

[0086] [ka]

[0087] [ka]

[0088] In some embodiments, the oxyanion-containing compound is a polysaccharide, and the oxyanion is an oxyanion produced by the ionization of the polysaccharide. Preferably, the polysaccharide is a polysaccharide having an anionic functional group, and more preferably, an acidic polysaccharide having an anionic functional group. Examples of such anionic functional groups include acidic groups, salts, acid esters, or combinations thereof. When the anionic functional group is a salt, examples include, but are not limited to, salts selected from the group consisting of sulfates, sulfites, sulfonates, protonated phosphates, phosphates, polyphosphates, metaphosphates, phosphonites, oxyphosphates, silicates, carboxylates, carbonates, and combinations thereof. The salt is preferably a metal salt, and preferred metals constituting the metal salt include, but are not limited to, sodium, potassium, lithium, calcium, strontium, barium, and magnesium. Preferred anionic functional groups include, for example, sulfate groups, sulfate salts, sulfate esters, carboxyl groups, carboxylate salts, carboxylate esters, sulfo groups, sulfonates, sulfonic acid esters, phosphate groups, phosphate salts, phosphate esters, phosphonic acid groups, phosphonate salts, phosphonic acid esters, or combinations thereof. More preferably, the polysaccharide is a polysaccharide having at least two anionic functional groups selected from the group consisting of sulfate groups, sulfate salts, sulfate ester salts, carboxyl groups, carboxylate salts, carboxylate esters, sulfo groups, sulfonates, sulfonic acid esters, phosphate groups, phosphate salts, phosphate esters, phosphonic acid groups, phosphonate salts, phosphonic acid esters, and phosphodiesters. The at least two anionic functional groups may be of the same type or of different types. Polysaccharides having anionic functional groups preferably contain one anionic functional group per monomer unit, which is the constituent unit of the polysaccharide. The entire monomer unit may have an anionic functional group, or only a portion of the monomer unit may have an anionic functional group. At least two anionic functional groups may be directly bonded to a five-membered ring or six-membered ring containing carbon of the monomer unit, which is the constituent unit of the polysaccharide, or they may be bonded to the five-membered ring or six-membered ring via a substituted or unsubstituted hydrocarbon chain. Examples of hydrocarbon chains include, but are not limited to, alkylene groups (e.g., methylene groups). Examples of groups formed when the above-mentioned at least two functional groups are ionized include a sulfate ester group (-O-SO3 - ), sulfonic acid group (-SO3 - ), carboxylate group (-COO - ), phosphate group (-O-PO3 2- ), phosphoryl group (-PO3 2- ) are some examples. Polysaccharides having anionic functional groups may be natural polysaccharides or synthetic polysaccharides. Polysaccharides having anionic functional groups may be linear, branched, or cyclic. Examples of polysaccharides include, but are not limited to, carboxymethylcellulose, gellan gum, alginic acid, sulfated alginic acid, carrageenan, xanthan gum, chondroitin sulfate, heparin, hyaluronic acid, pectic acid, gum arabic, agar, tragacanth gum, sodium dextran sulfate, and sodium sulfated salts of cyclodextrin. The number of monomer units in polysaccharides that ionize to produce oxyanions, particularly polysaccharides having anionic functional groups, is not particularly limited, but is preferably between 2 and 100,000. The molecular weight of polysaccharides that ionize to produce oxyanions, particularly polysaccharides having anionic functional groups, is not particularly limited, but is preferably 1,000 to 10,000,000, and more preferably 5,000 to 1,000,000, by weight average molecular weight. The weight average molecular weight of polysaccharides can be calculated by gel permeation chromatography (GPC) measurement. The oxyanions produced from the above-mentioned polysaccharides that ionize to produce oxyanions, particularly polysaccharides having anionic functional groups, can form complexes by bonding through ionic and hydrogen bonds with organic cations formed by the ionization of any compound having at least two amino groups or guanidino groups as described herein. In some embodiments, the Young's modulus of the supramolecular polymer measured under the following indentation experiment conditions is 5 GPa or higher, preferably 10 GPa or higher, more preferably 15 GPa or higher, and more preferably 20 GPa or higher. Measurement conditions: Samples were prepared by cutting a supramolecular polymer into 1cm x 1cm sections with a thickness of 0.5mm. The Young's modulus of these samples was determined using an ENT-NEXUS (ELIONIX Inc.) indentation hardness tester at a measurement temperature of 20°C. A diamond indenter tip was used for indentation. The test load was 50mN, the loading time was 20,000msec, the holding time was 5,000msec, and the unloading time was 20,000msec.

[0089] While the Young's modulus of many known synthetic resins polymerized by covalent bonding, such as polytetrafluoroethylene, polypropylene, polyethylene tereflat, polystyrene, polymethyl methacrylate, and aromatic polyether ketones, is 5 GPa or less, the Young's modulus of supramolecular polymer glass (SPG) can be made greater than that of such synthetic resins.

[0090] In some embodiments, the tensile strength measured under the above-mentioned supramolecular polymer measurement conditions is preferably 5 MPa or more and 50 MPa or less. These values ​​are comparable to the tensile strength of some known synthetic resins polymerized covalently, and the tensile strength of supramolecular polymer glass (SPG) can be the same as or greater than that of such synthetic resins. Measurement conditions: Samples were prepared by cutting a supramolecular polymer into pieces measuring 2mm x 35mm in length and width, with a thickness of 0.5mm. The test speed was set to 10mm / s. The tensile strength sensor indicated 500N. The measurement temperature was 20°C.

[0091] In some embodiments, supramolecular polymer glass (SPG) can be processed in water at 20°C. Because the organic cation and the oxyanion in the supramolecular polymer glass (SPG) are bonded by ionic and hydrogen bonds, when placed in water for a certain period, water binds to the supramolecular polymer, causing it to swell, soften, and become processable by hand or machine. Adding an electrolyte such as sodium chloride to the water further promotes dissociation into monomers. Furthermore, the supramolecular polymer can be moistened with water and molded into any shape, such as a flat plate or a sphere. The molded supramolecular polymer can also be dried to maintain its shape after molding. The supramolecular polymer in this embodiment may be 100% biodegradable in water, and such a supramolecular polymer has the advantage of having a low environmental impact.

[0092] In some embodiments, supramolecular polymer glass (SPG) can be molded into various shapes at temperatures above its glass transition temperature.

[0093] In some embodiments, supramolecular polymer glass (SPG) is self-healing. For example, even if a supramolecular polymer is fractured into two pieces, the two pieces will bond together if the fracture surfaces are moistened with water and left in contact for a while.

[0094] In some embodiments, the Young's modulus of the supramolecular polymer at 20°C is 5 GPa or more, preferably 10 GPa or more, more preferably 15 GPa or more, and more preferably 20 GPa or more, and the tensile strength of the supramolecular polymer at 20°C is 5 MPa or more and 50 GPa or less. A supramolecular polymer with such a configuration has high rigidity and high tensile mechanical strength.

[0095] In some embodiments, supramolecular polymer glass (SPG) is insoluble in organic solvents. Examples of organic solvents include dichloromethane, chloroform, methanol, ethanol, acetone, hexane, dimethylformamide, dimethyl sulfoxide, ethyl acetate, diethyl ether, and tetrahydrofuran.

[0096] In some embodiments, a supramolecular polymer glass with a thickness of 0.5 mm exhibits a light transmittance of 95% or more in the 400-800 nm range. Such supramolecular polymers have excellent transparency.

[0097] A supramolecular polymer composite according to a first aspect of the present invention has one or more of the following advantages [1] to [8]. In a particularly preferred embodiment, it has all advantages except [5] or all of the advantages [1] to [8].

[0098] [1] Quantitative green synthesis An organic cation, formed by the ionization of a compound having at least two amino or guanidino groups, is non-covalently bonded to an oxyanion in a 1:1 molar ratio to produce a supramolecular polymer. This supramolecular polymer can be synthesized without heating or pressurizing. Furthermore, it can be synthesized in water or an aqueous solvent, and no organic solvent is required. [2] Green molding process Supramolecular polymers can be processed in water. Heating is not required for processing. [3] Super robust The Young's modulus of the supramolecular polymer at 20°C is 5 GPa or higher, and / or the tensile strength at 20°C is 5 MPa or higher and 50 GPa or lower. [4] Self-healing Even if a supramolecular polymer is fractured into two components, if the fracture surfaces are moistened with water and the two fracture surfaces are brought into contact, the two components will bond together. [5] Water resistance In the case of supramolecular polymers produced using guanidine compounds (II), the solubility in water is lower compared to supramolecular polymers produced using guanidine compounds (I). [6] Organic solvent tolerance Supramolecular polymers are insoluble in organic solvents. Examples of organic solvents include dichloromethane, chloroform, methanol, ethanol, acetone, hexane, dimethylformamide, dimethyl sulfoxide, ethyl acetate, diethyl ether, and tetrahydrofuran. [7] Fully recyclable Unlike conventional plastic polymers, the recycling of SPG in this embodiment does not require catalysts or energy-consuming procedures. By immersing SPG in an aqueous solution of ammonium chloride or acid, the salt crosslinking interaction between the guanidino group and the phosphodiester group is broken, allowing it to be completely returned to its raw material monomer. The monomer can then be recovered by purification methods such as ion exchange resins. This enables resource recycling and contributes to a microplastic-free ocean. This will change the conventional understanding of plastics.

[0099] In some embodiments, the organic cation oxyanion in the composite of the first embodiment may be bonded by further covalent or non-covalent bonds other than ionic and hydrogen bonds. Such further covalent or non-covalent bonds can be formed by introducing functional groups to the organic cation and / or oxyanion in known ways.

[0100] In some embodiments, the composite of the first embodiment is a supramolecular polymer. In some embodiments, the composite of the first embodiment is a supramolecular plastic. In some embodiments, the composite of the first embodiment is a supramolecular polymer glass. A supramolecular polymer composite is preferable because it results in less or no environmental impact during manufacturing and processing.

[0101] A second aspect of this disclosure provides a composition containing the composite of the first aspect described above. The composition may further contain polymers such as synthetic resins, elastomers, and rubbers. The composition may also further contain additives other than polymers. Examples of additives include, but are not limited to, synthetic resins, elastomers, rubbers, surfactants, lubricants, dispersants, antioxidants, light stabilizers, UV absorbers, colorants, preservatives, and fragrances.

[0102] A third aspect of this disclosure provides an article comprising the composite of the first aspect described above. The article may comprise components other than the composite of the first aspect. Examples of articles include, but are not limited to, containers, packaging, metal machinery industrial products (industrial machinery, electrical machinery, precision machinery, electrical machinery), home appliances, personal computers and mobile phones, kitchenware, cleaning supplies, stationery, toys, sporting goods, furniture, clothing, detergents, pharmaceuticals, cosmetics, coatings, building materials, vehicles (light vehicles, vehicles) and their parts.

[0103] A fourth aspect of this disclosure provides a method for producing a composite, comprising mixing a compound having at least two amino groups or guanidino groups with an oxyanion-containing compound in water or an aqueous solution, thereby generating a composite in which an organic cation formed by the ionization of the compound having at least two amino groups or guanidino groups and an oxyanion formed by the ionization of the oxyanion-containing compound are bonded by ionic bonds and hydrogen bonds. The composite may be the composite of the first aspect described above. In some embodiments, the composite is a supramolecular polymer. In some embodiments, the composite is a supramolecular polymer glass.

[0104] Compounds having at least two amino groups or guanidino groups, oxyanion-containing compounds, and complexes are as described with respect to the complexes of the first embodiment. In particular, the supramolecular polymer, which is a complex of the first embodiment, can be manufactured in a single step.

[0105] When a compound having at least two amino groups or guanidino groups is mixed with an oxyanion-containing compound in water or an aqueous solution, the organic cation formed by the ionization of the compound having at least two amino groups or guanidino groups and the oxyanion formed by the ionization of the oxyanion-containing compound form ionic and hydrogen bonds to form a supramolecular polymer. At the same time, the anion produced by the ionization of the compound having at least two amino groups or guanidino groups and the organic cation produced by the ionization of the oxyanion-containing compound neutralize each other and dissolve in water. Since the supramolecular polymer undergoes liquid-liquid phase separation with the solvent, it can be easily separated or recovered from water or an aqueous solution by known methods such as centrifugation and recovery. When the obtained supramolecular polymer is dried, a supramolecular polymer with high mechanical strength is obtained, even though the monomer molecules are bonded non-covalently. After separating or recovering the supramolecular polymer from water or an aqueous solution, it can be molded into any shape, such as a flat plate or a sphere. Any molding method can be used, such as press molding, injection molding, or extrusion molding.

[0106] The composite manufacturing method of this embodiment can be carried out in an aqueous system and is environmentally friendly as it reduces the use of organic solvents. Furthermore, it does not require heating or pressurization, and the composite can be manufactured at a temperature of 5 to 40°C under ambient atmosphere or atmospheric pressure. In addition, it is low-cost as it does not require the use of expensive rare earth metal catalysts.

[0107] According to a fifth aspect of this disclosure, the use of a compound having at least two amino groups or guanidino groups and a compound containing an oxyanion of sulfur, phosphorus, silicon, or carbon is provided for producing a supramolecular polymer composite. The compound having at least two amino groups or guanidino groups and the compound containing an oxyanion of sulfur, phosphorus, silicon, or carbon are as described with respect to the composite of the first aspect.

[0108] All patent applications and disclosures cited herein are incorporated herein by reference in their entirety.

[0109] The present invention is described more specifically below with reference to examples, but the present invention is not limited thereto. Examples

[0110] Example 1 Synthesis of guanidinium-based monomer ( Gu M) 1. Synthesis of first-generation monomer 1 ( Gu M Gen.I -1)

[0111] Chemical formula

[0112] Diethylenetriamine (54 mL, 0.5 mol) and S-methylisothiourea hemisulfate (139.2 g, 1 mol) were added to a mixed solution of water and ethanol (v / v 1:1, 500 mL). The reaction mixture was stirred at room temperature for 16 hours to yield a white precipitate. The crude product was filtered, rinsed with ethanol, and recrystallized in a mixture of water and isopropanol to obtain Gu M Gen.I -1 (yield: 93% based on diethylenetriamine). The product was identified by 1 ¹H NMR and 13 ¹³C NMR. 1 ¹H NMR (600 MHz, 298 K, D₂O): δ 3.32 (t, 4H, NH-C H H₂-CH₂), 2.81 (t, 4H, C H H₂-NH-CH₂) ppm. 13 ¹³C NMR (150 MHz, 298 K, D₂O): δ 157.07 ( C =NH), 46.62 ( C H₂-NH-CH₂), 40.63 (NH- C H₂-CH₂) ppm.

[0113] 2. Synthesis of first-generation monomer 2 ( Gu M Gen.I-2) Synthesis

[0114] [ka]

[0115] In a 1 L three-necked round-bottom flask dried in an oven, S-methylisothiourea·1 / 2 H2SO4 (250.5 g, 1.8 mol) was dissolved in 700 mL of Milli-Q water. 70 mL of norspermidine was added to this solution. The reaction mixture was refluxed for 72 hours. The reaction mixture was cooled to room temperature. The flask was placed in a freezer at 4°C for 12 hours to allow a white precipitate to form. The crude product was filtered, washed with ice water, and recrystallized in mL of Milli-Q water. Gu M Gen.I -2 was obtained. (Yield: 95% based on norspermidine). The product was 1 1H NMR and 13 It was identified by 13C NMR. 1 H NMR (600 MHz, 298 K, D2O): δ 2.04 (p, 4H; CH2C H 2CH2), 3.16 (t, 4H; C H 2-NH-C H 2), 3.64 (t, 4H; NH-C H 2-CH2) ppm. 13 C NMR (150 MHz, 298 K, D2O): δ 159.73 ( C =NH), 47.85 ( C H2-NH- C H2), 41.04 (NH- C H2-CH2), 27.83 (CH2- C H2-CH2) ppm.

[0116] 3. First-generation monomer 3( Gu M Gen.I -3) Synthesis

[0117] [ka]

[0118] In a 100 mL three-necked round-bottom flask dried in an oven, S-methylisothiourea·0.5 H₂SO₄ (12.53 g, 0.09 mol) was dissolved in 35 mL of Milli-Q water. 4 mL of spermidine was added to this solution. The reaction mixture was refluxed for 72 hours. The reaction mixture was cooled to room temperature. The crude residue was filtered, washed with ice water, and recrystallized in a mixture of water and ethanol (v / v 1:1). Gu M Gen.I -3 was obtained (yield: 53% based on spermidine). 1 1H NMR and 13 It was identified by 13C NMR. 1 H NMR (600 MHz, 298K, D2O): δ 3.31 (t, 2H, NH-C H 2-(CH2)2-NH-CH2), 3.24 (t, 2H, NH-C H 2-(CH2)3-NH-CH2), 3.12 (m, 2H, NH-(CH2)2-CH2-NH-CH2), 3.09 (m, 2H, NH-(CH2)3-C H 2-NH-CH2), 2.00 (tt, 2H, NH-CH2-C H 2-CH2-NH), 1.76 (m, 2H, NH-(CH2)2-C H 2-CH2-NH-CH2), 1.67 (m, 2H, NH-CH2-C H 2-(CH2)2-NH-CH2) ppm. 13 C NMR (150 MHz, 298K, D2O): δ 156.9 ( C =NH), 47.21 (NH-(CH2)3- C H2-NH-CH2), 44.83 (NH-(CH2)2- C H2-NH-CH2), 40.41 (NH- C H2-(CH2)3-NH-CH2), 38.19 (NH- C H2-(CH2)2-NH-CH2), 25.03 (NH-CH2- CH2-(CH2)2-NH-CH2), 24.95 (NH-CH2- C H2-CH2-NH), 22.83 (NH-(CH2)2- C H2-CH2-NH-CH2) ppm.

[0119] 4. First-generation monomer 4( Gu M Gen.I -4) Synthesis

[0120] [ka]

[0121] In a 200 mL three-necked round-bottom flask dried in an oven, S-methylisothiourea·0.5 H₂SO₄ (13.9 g, 0.1 mol) was dissolved in a mixture of water and ethanol (v / v 1:3). 16 mL of ethylenediamine was added to this solution. The reaction mixture was stirred for 24 hours to produce a white precipitate. The crude residue was washed with ethanol and recrystallized in a mixture of water and ethanol (v / v 1:1) to obtain clear crystals. Gu M Gen.I -4 was obtained (yield: 96% based on ethylenediamine). 1 1H NMR and 13 It was identified by 13C NMR. 1 H NMR (600 MHz, 298K, D2O): δ 3.44 (s, 4H, C H 2-C H 2). 13 CNMR (150 MHz, 298K, D2O): δ 159.95 ( C =NH), 42.95 ( C H2- C H2).

[0122] 5. First-generation monomer 5( Gu M Gen.I -5) Synthesis Gu M Gen.I -5 was synthesized through the following two steps:

[0123] [ka]

[0124] Step I: In a 200 mL three-necked round-bottom flask dried in an oven, S-methylisothiourea·0.5 H₂SO₄ (13.9 g, 0.1 mol) was dissolved in 50 mL of a water-ethanol mixture (v / v 1:3). 10 mL of 1,3-diaminopropane was added to this solution. After stirring for several minutes, the water-ethanol mixture (v / v 1:3) was added, and stirring was continued for a further 30 minutes. The crude residue was filtered, washed with water, and recrystallized to obtain the desired crystalline product (yield: 72% based on 1,3-diaminopropane). 1 It was identified by 1H NMR. 1 H NMR (600 MHz, 298K, D2O): δ 3.31 (t, 4H, CH 2-NH), 3.08 (p, 2H, C H 2-NH2), 1.98 (p, 2H, CH2-C H 2-CH2) ppm. Step II: The product obtained in Step I (7.4 g) and S-methylisothiourea · 0.5 H2SO4 (4.81 g, 34.5 mmol) were dissolved in 50 mL of water. 1.5 mL of aqueous sodium hydroxide solution (5 M) was added dropwise to this mixture, and the mixture was refluxed for 8 hours. The reaction mixture was cooled to room temperature. The flask was placed in a freezer at 4°C for 12 hours to allow a white precipitate to form. The crude product was filtered, washed with water, and recrystallized. Gu M Gen.I -5 was obtained (yield: 38% based on 1,3-diaminopropane). 1 1H NMR and 13 It was identified by 13C NMR. 1 H NMR (600 MHz, 298K, D2O): δ 3.28 (t, 4H, CH 2-NH), 1.89 (p, 2H, CH2-C H2-CH2) ppm. 13 C NMR (150 MHz, 298K, D2O): δ 156.85 ( C =NH), 38.34 ( C H2-NH), 26.97 (CH2- C H2-CH2) ppm.

[0125] 6. First-generation monomers 6, 7, and 8 ( Gu M Gen.I -6, Gu M Gen.I -7, and Gu M Gen.I -8) Synthesis

[0126] [ka]

[0127] This series of guanidium monomers. Gu M Gen.I -6 Gu M Gen.I (Up to -8) Gu M Gen.I The same synthesis protocol as in -5 was followed. An aliphatic diamine (0.5 mol) was added to a solution of S-methylisothiourea·0.5 H2SO4 (250.5 g, 1.8 mol), and the reaction mixture was stirred at 105°C for 3 days. The reaction mixture was cooled to room temperature. The flask was placed in a freezer at 4°C for 12 hours to produce a white precipitate. The crude product was filtered, washed with water, and recrystallized to obtain the desired product ( Gu M Gen.I -6 Gu M Gen.I We obtained up to -8. The product 1 1H NMR and 13 It was identified by 13C NMR. Gu M Gen.I -6 (n = 3)

[0128] [ka]

[0129] 1 H NMR (600 MHz, 298 K, D2O): δ 3.22 (t, 4H, C H 2-NH), 1.56 (t, 4H, CH2-C H 2-C H 2-CH2) ppm. Gu M Gen.I -7(n = 4)

[0130] [[Chemical]]

[0131] 1 H NMR (600 MHz, 298 K, D2O): δ 3.19 (t, 4H, C H 2-NH), 1.62 (t, 4H, CH2-C H 2-CH2-C H 2-CH2), 1.41 (p, 2H, CH2-CH2-C H 2-CH2-CH2) ppm. 13 13C NMR (150 MHz, 298 K, D2O): δ 156.76 ( C =NH), 40.89 ( C H2-NH), 26.97 (CH2-C H 2-CH2-C H 2-CH2), 22.90 (CH2-CH2-C H 2-CH2-CH2) ppm. Gu M Gen.I -8(n = 5)

[0132] [[Chemical]]

[0133] 1 H NMR (600 MHz, 298 K, D2O): δ 2.60 (t, 4H, C H 2-NH), 1.44 (t, 4H, NH-CH2-C H2), 1.33 (p, 6H, NH-CH2-CH2-C H 2-C H 2-C H 2) ppm. 13 CNMR (150 MHz, 298K, D2O): δ 156.73 ( C =NH), 41.20 ( C H2-NH), 27.82 (NH-CH2- C H2), 27.73 (NH-CH2-CH2- C H2), 25.63 (NH-CH2-CH2-CH2-CH2) ppm.

[0134] 7. First-generation monomer 9( Gu M Gen.I -9) Synthesis

[0135] [ka]

[0136] In a 200 mL three-necked round-bottom flask dried in an oven, S-methylisothiourea·0.5 H₂SO₄ (13.9 g, 0.1 mol) was dissolved in Milli-Q water. 5 mL of bis(2-aminoethyl)ethane-1,2-diamine was added to this solution. The reaction mixture was refluxed for 24 hours to produce a white precipitate. The crude residue was washed with ethanol and recrystallized in Milli-Q water, yielding clear crystals. Gu M Gen.I -9 was obtained (yield: 96% bis(2-aminoethyl)ethane-1,2-diamine). 1 1H NMR and 13 It was identified by 13C NMR. 1 H NMR (600 MHz, 298K, D2O): δ 3.29 (t, 4H, C H 2-NH), 2.70 (t, 4H, NC H 2-CH2) ppm. 13 CNMR (150 MHz, 298K, D2O): δ 156.93 (C =NH), 52.33 ( C H2-NH), 38.92 (N- C H2-CH2) ppm.

[0137] 8. Synthesis of 1st Generation Monomer 10 ( Gu M Gen.I -10)

[0138]

Chemical Structure

[0139] S-methylisothiourea hemisulfate (13.9 g, 0.1 mol) was dissolved in 80 mL of Milli-Q water in an oven-dried 300 mL three-necked round-bottom flask. To this solution was added 30.6 mL of 2,2'-thiobis(ethane-1-amine) (0.25 mol). The mixture was refluxed for 3 days. The reaction mixture was cooled to room temperature to form a white precipitate. The precipitate was collected by suction filtration and recrystallized from water to obtain white crystalline Gu M Gen.I -10 (yield: 72%, based on 2,2'-thiobis(ethane-1-amine)). The product was identified by 1 1H NMR and 13 13C NMR spectroscopy. 1 1H NMR (600 MHz, 298 K, D2O): δ 3.43 (t, 4H; NH-C H 2), 2.83 (t, 4H; C H 2-S) ppm. 13 13C NMR (150 MHz, 298 K, D2O): δ 156.90 ( C =N), 40.50 (NH- C H2) 30.27 ( C H2-S) ppm.

[0140] 9. Synthesis of 1st Generation Monomer 11 ( Gu M Gen.I -11)

[0141] [ka]

[0142] In a 300 mL three-necked round-bottom flask dried in an oven, S-methylisothiourea·0.5H2SO4 (13.9 g, 0.1 mol) was dissolved in 80 mL of Milli-Q water. 40 mL of 2,2'-disulfanejyldiethaneamine (0.25 mol) was added to this solution. The mixture was refluxed for 24 hours. The reaction mixture was cooled to room temperature, and a white precipitate formed. The precipitate was aspirated and recrystallized from water, yielding white crystals. Gu M Gen.I -11 was obtained (yield: 96% based on 2,2'-disulfanejyldiethaneamine). 1 1H NMR and 13 It was identified by 13C NMR. 1 H NMR (600 MHz, 298 K, D2O): δ 3.60 (t, 4H; NH-C H 2), 3.38 (t, 4H; C H 2-S) ppm. 13 C NMR (150 MHz, 298 K, D2O): δ 156.90 ( C =N), 39.77 (NH- C H2), 36.11 (NH-CH2- C H2) ppm.

[0143] 10. First-generation monomer 12 ( Gu M Gen.I -12) Synthesis

[0144] [ka]

[0145] In a 300 mL three-necked round-bottom flask dried in an oven, 2,2'-(ethane-1,2-diylbis(oxy)bis(ethane-1-amine) (38.5 mL, 0.25 mol) was added to a solution of S-methylisothiourea hemisulfate (13.9 g, 0.1 mol) dissolved in Milli-Q water. The mixture was refluxed for 24 hours. After concentration using a small evaporator, the mixture was allowed to stand at 4°C for 3 days. A clear precipitate formed, which was washed with cold ethanol. Recrystallization from water / ethanol gave clear crystals of Gu M Gen.I -12 (yield: 32% based on 2,2'-(ethane-1,2-diylbis(oxy)bis(ethane-1-amine)). The product was 1 identified by ¹H NMR and 13 ¹³C NMR. 1 ¹H NMR (600 MHz, 298 K, D₂O): δ 3.72 (t, 4H; NH-C H ₂), 3.70 (p, 4H; NH-CH₂- C H₂-O), 3.41 (t, 4H; O-C H ₂-C H ₂-O) ppm. 13 ¹³C NMR (150 MHz, 298 K, D₂O): δ 157.30 ( C =N), 69.68 ( C H₂-O) 68.81 (O- C H₂- C H₂-O), 41.16 (NH- C H₂) ppm.

[0146] 11. Synthesis of second-generation monomer 1 ( Gu M Gen.II -1)

[0147]

Chemical Formula

[0148] In a 1000 mL three-necked round-bottom flask dried in an oven, S-methylisothiourea·0.5 H2SO4 (40 g, 0.3 mol) was dissolved in 700 mL of Milli-Q water. To this solution, 14 mL of 1,3-bis(3-aminopropyl)tetraethylsiloxane was added. The reaction mixture was refluxed for 24 hours. The reaction mixture was cooled to room temperature, the crude residue was filtered, and washed with cold water. Gu M Gen.II -1 was obtained (yield: 53% based on 1,3-bis(3-aminopropyl)tetraethylsiloxane). 1 1H NMR and 13 It was identified by 13C NMR. 1 H NMR (600 MHz, 298 K, D2O): δ 3.18 (t, 4H; NH-C H 2), 1.62 (p, 4H; NH-CH2-C H 2), 0.61 (t, 4H; C H 2-O-Si), 0.14 (s, 12H; Si-C H 3) ppm. 13 C NMR (150 MHz, 298 K, D2O): δ 156.67 ( C =N), 43.70 (NH- C H2), 22.14 (NH-CH2- C H2), 14.10 ( C H2-O-Si), 0.70 (Si- C H3) ppm.

[0149] 12. Second-generation monomer 2 ( Gu M Gen.II -2) Synthesis

[0150] [ka]

[0151] In a 100 mL three-necked round-bottom flask dried in an oven, 3,3'-(1,1,3,3,5,5,7,7,9,9,11,11-dodecamethylhexasiloxane-1,11-diyl)bis(propan-1-amine) (5.4 mL, 10 mmol) was dissolved in hydrochloric acid (1.5 mL, wt.% = 36.5%) in ethanol (20 mL). Cyanamide (1.6 g, 0.04 mol) was added to this solution. The reaction mixture was refluxed for 4 hours. After cooling the reaction mixture to room temperature, it was evaporated under reduced pressure until dry to obtain a viscous liquid. The obtained viscous liquid was rinsed with warm water (70 °C 100 mL × 3), and the liquid was... Gu M Gen.II -2 was obtained (yield: 12%) 3,3'-(1,1,3,3,5,5,7,7,9,9,11,11-dodecamethylhexasiloxane-1,11-diyl)bis(based on propan-1-amine). 1 It was identified by 1H NMR. 1 H NMR (600 MHz, 298 K, MeOD): δ 2.92 (t, 4H; NH-C H 2), 1.71 (p, 4H; NH-CH2-C H 2), 0.64 (t, 4H; C H 2-O-Si), 0.12 (m, 36H; Si-C H 3) ppm.

[0152] Example 2 Synthesis of supramolecular polymer glass (SPG) 1. First-generation supramolecular polymer glass ( Gen.I Synthesis of SPG The first-generation supramolecular polymer glass is synthesized using the first-generation monomers prepared in Example 1. This synthesis of the first-generation supramolecular polymer glass can be carried out in an aqueous system and does not involve any organic solvents or expensive rare-earth metal catalysts. In Examples 2, 4-9 below, unless otherwise specified, the supramolecular polymer glass was synthesized in a flask, similar to Example 1.

[0153] In an aqueous solution of sodium hexametaphosphate (or sodium trimetaphosphate), each guanidinium-based first-generation monomer prepared in Example 1 ( Gu M Gen.I An aqueous solution of ) was added to the guanidium monomer with a theoretical mixing molar ratio of 1:1 to the phosphate diester. In all cases using first-generation monomers, the mixed aqueous solution immediately underwent liquid-liquid phase separation, producing a turbid supramolecular polymer emulsion (Figures 2A, B; in Figure 2A, phase separation occurs at the interface 12 between the aqueous layer 10 and the viscous liquid 11 consisting of supramolecular polymer glass). The supramolecular polymer emulsion was concentrated by centrifugation to a viscous liquid, rinsed with pure water, and vacuum-dried to obtain first-generation supramolecular polymer glass in 98% yield. Gen.I I obtained SPG.

[0154] 2. Second-generation supramolecular polymer glass ( Gen.II Synthesis of SPG Second-generation supramolecular polymer glasses are synthesized using second-generation monomers.

[0155] In an aqueous solution of sodium hexametaphosphate (or sodium trimetaphosphate), each guanidinium-based second-generation monomer prepared in Example 1 ( Gu M Gen.II An aqueous solution of ) was added to the guanidium monomer phosphate diester in a theoretical mixing molar ratio of 1:1. In all cases where a second-generation monomer was used, the mixed aqueous solution immediately underwent liquid-liquid phase separation, producing a turbid supramolecular polymer emulsion. The emulsion was concentrated by centrifugation to a viscous liquid, rinsed with pure water, and vacuum-dried to obtain a second-generation supramolecular polymer glass in a yield of 72%. Gen.II I obtained SPG.

[0156] 3. Third type of supramolecular polymer glass ( Gen.III Synthesis of SPG Third-generation supramolecular polymer glasses are synthesized using both first-generation and second-generation monomers.

[0157] In an aqueous solution of sodium hexametaphosphate (or sodium trimetaphosphate), the guanidinium-based first-generation monomer prepared in Example 1 ( Gu M Gen.I ) and each second-generation monomer ( Gu M Gen.II An aqueous solution of the following was added to the guanidium monomer phosphate diester in a theoretical mixing molar ratio of 1:1. The mixed aqueous solution immediately underwent liquid-liquid phase separation, producing a turbid supramolecular polymer emulsion. The emulsion was concentrated by centrifugation to a viscous liquid, rinsed with pure water, and vacuum-dried to obtain third-generation supramolecular polymer glass in 90% yield. Gen.III I obtained SPG.

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[0159] Example 3: Evaluation of the physical properties of supramolecular polymer glass (SPG) 1. Light transmittance of supramolecular polymer glass (SPG) SPG films with dimensions of 100 mm in length, 100 mm in width, and 0.5 mm in thickness were manufactured, and the light transmittance of the SPG films was measured using the transmission mode of a UV-Vis spectrometer. (result) As a result, the optical transmittance of the SPG film ranged from 90% to 97%, depending on the molecular structure of the monomer, and was comparable to the light transmittance of commercially available transparent resin films (polymethyl methacrylate (PMMA)), polycarbonate (PC), polyethylene terephthalate (PET), polystyrene (PS), and inorganic glass (Glass) (Figure 3).

[0160] 2. Mechanical properties of supramolecular polymer glass (SPG) SPG film with dimensions of 100 mm in length, 100 mm in width, and 0.5 mm in thickness was manufactured. This film was placed on a metal plate, and its Young's modulus was determined using an ENT-NEXUS (ELIONIX Inc.) indentation hardness tester. A diamond indenter tip was used for the indentation test. The maximum load was 50 mN, and the load / unload speed was 2.5 mN / s. The duration of the maximum load was 5 seconds. Young's modulus and indentation hardness were determined from the unloaded curve using the tester. The measurement temperature was 25°C.

[0161] The tensile strength of commercially available materials is based on values ​​found on Wikipedia and other publicly available literature. The tensile strength was measured using a tensile machine at a test speed of 10 mm / s on a sample measuring 35 mm in length, 2 mm in width, and 0.5 mm in thickness. (result) As shown in Figure 4, the first-generation supramolecular polymer glass maintains its shape and can withstand loads even when weights are placed on top of it.

[0162] As shown in Figure 5, unexpectedly, the Young's modulus of the SPG film exceeded 5 Gpa for second-generation supramolecular polymer glass and 15 Gpa for first-generation supramolecular polymer glass, which was higher than that of commercially available resin films.

[0163] As shown in Figure 6, the tensile strength of the first and second generation supramolecular polymer glasses was in the range of 20 to 50 Gpa, which was comparable to that of commercially available resin films.

[0164] 3. Mechanical properties of third-generation supramolecular polymer glass (SPG) For the third-generation SPG, the Young's modulus was measured under the same conditions as described in "2. Mechanical Properties of Supramolecular Polymer Glass (SPG)" above. However, the measurement temperature was 30°C. (result) As shown in Figure 7, the Young's modulus is the second generation SPG ( Gen.2 SPG (far left) is low, and the first generation SPG ( Gen.1Although SPG (far right) has a high value, the Young's modulus could be adjusted by mixing first-generation and second-generation SPG.

[0165] 4. Processability of supramolecular polymer glass (SPG) The glass transition temperatures (Tg) of the first to third generation SPGs produced in Example 2 ranged from 35°C to 125°C. Each SPG, like conventional synthetic resins such as PET, exhibited the same T g Hot pressing at ambient temperatures allowed for processing into various shapes or patterns.

[0166] 5. Self-healing properties of supramolecular polymer glass (SPG) The product manufactured in Example 2 Gu M Gen.I The SPG based on -2 was able to completely self-repair after being broken into two fragments by applying pressure under ambient conditions (20°C, 60% humidity). The mechanical properties of the SPG were not impaired after self-repair. Furthermore, all SPGs produced in Example 2 can self-repair with the assistance of water or moisture. Specifically, first-generation supramolecular polymer glass. Gen.I SPG can self-repair by pressing it for 30 minutes under high humidity (RH80%) conditions, and is a second-generation supramolecular polymer glass. Gen.II SPG was able to self-repair by being pressed for 20 minutes under a spray of water.

[0167] 6. First-generation supramolecular polymer glass ( Gen.I SPG) underwater machinability Each first-generation supramolecular polymer glass manufactured in Example 2 Gen.I When SPG was immersed in water, it gradually softened (Figure 8(A)), and after several hours it became a viscous supramolecular polymer liquid (Figure 8(B))). When this viscous liquid was vacuum-dried in a Teflon® container at 80°C for 6 hours, there was no loss of monomers or mechanical properties, and the mechanical strength remained intact. Gen.I SPG was obtained. Gen.I SPG can be softened and molded into various structures by spraying it with water, making it viscous.

[0168] Example 4 Synthesis of supramolecular polymer glass using ammonium-based monomers The ammonium group in ammonium molecules interacts with oxyanions such as carboxylate groups and phosphodiester groups to form a cross-linked supramolecular network, generating SPGs.

[0169] As a typical example, commercially available low molecular weight molecules having di / tri / tetraamino groups can form supramolecular polymers with oxyanions via salt bridges.

[0170] As shown in Figure 9, the diamine monomer was dissolved in ethanol at 0.06 M, and a 0.2 M sodium hexametaphosphate solution was added to the prepared diamine monomer solution. The solution immediately became turbid, and a liquid-liquid phase separation phenomenon was observed instantaneously. After centrifugation at 12000 r / min for 10 minutes, a clear liquid-liquid phase separation was observed as shown by the dotted line in the lower left photograph of Figure 9. The viscous liquid at the bottom was washed three times with 50 mL of deionized water. After vacuum drying at 80°C for 3 hours, clear glass was obtained in a yield of approximately 98%.

[0171] Example 5 Synthesis of SPG using renewable raw material monomers Water-soluble low-molecular-weight biomolecules or biopolymers are abundantly stored on Earth, and these can also be used to form SPGs using our strategy. In this example, SPGs were prepared using two renewable raw materials, phytic acid and alginic acid, as oxoanion monomers.

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[0173] Phytic acid is a hexaploid dihydrogen phosphate ester of inositol and is the main storage form of phosphorus in cereals, legumes, oilseeds, and nuts. Alginic acid is a naturally occurring edible polysaccharide refined from brown algae and certain bacterial genera found in nature. It is rich in carboxyl groups and can form salt bridges with ammonium and guanidium groups. Alginic acid is also used as an additive to enhance the mechanical properties of SPG. Gen.1 SPG and Gen.2 It can also be integrated into SPG.

[0174] 1-1. Phytic acid-based SPG An aqueous solution of guanidinium monomer was added to an aqueous solution of phytic acid in such a stoichiometric molar ratio of guanidino group to phosphate group (guanidinium ion and phosphate ion) that it was 1:1. This mixed aqueous solution underwent instantaneous liquid-liquid phase separation, yielding a turbid supramolecular polymer emulsion. This supramolecular polymer emulsion was concentrated into a viscous liquid by centrifugation, washed with Milli-Q water, and then vacuum-dried to obtain supramolecular polymer glass (SPG). The SPG could be processed into various shapes and patterns by hot pressing.

[0175] 1-2. Characteristics of phytic acid-based SPGs The mechanical properties of the SPG film manufactured in 1-1 were determined by an indenter test using ENT-NEXUS (ELIONIX Inc.) under the same measurement conditions as in Example 3, Section 2. A Berkovich-shaped diamond indenter tip was used for the indentation experiment. Phytic acid and Gu M Gen.II In the case of combination -1, the Young's modulus of SPG was 5.5 GPa (Figure 10A). Also, Gu M Gen.II Instead of -1 Gu M Gen.I When SPG was fabricated using -2, the Young's modulus of the SPG increased to 10 GPa (Figure 10B).

[0176] 2-1. Alginate-based SPG Amine-based or guanidine-based monomer was added to a diluted aqueous solution of alginic acid in a stoichiometric molar ratio of guanidino group / amino group and carboxyl group (guanidinium ion / ammonium ion and carboxylate ion) of 1:1. This mixed aqueous solution underwent instantaneous liquid-liquid separation, yielding a turbid supramolecular polymer emulsion. This supramolecular polymer emulsion was concentrated into a viscous liquid by centrifugation, washed with Milli-Q water, and then dried under vacuum to obtain supramolecular polymer glass.

[0177] 2-2. Alginate-enhanced SPG Amine-based or guanidine-based monomer was added to an aqueous mixture of alginic acid and hexametaphosphate in such a stoichiometric molar ratio of guanidino group / amino group to carboxyl group (guanidinium ion / ammonium ion to carboxylate ion) of 1:1. This aqueous mixture underwent instantaneous liquid-liquid separation, yielding a turbid supramolecular polymer emulsion. This supramolecular polymer emulsion was concentrated into a viscous liquid by centrifugation, washed with Milli-Q water, and then dried under vacuum to obtain supramolecular polymer glass.

[0178] 2-3.Results The mechanical properties of the SPG film were determined by indenter testing using ENT-NEXUS (ELIONIX Inc.) under the same measurement conditions as in Example 3, Section 2. A Berkovich-shaped diamond indenter tip was used for the indentation experiment. The mechanical properties of alginate-based SPG and alginate-reinforced SPG are shown in Figures 11A-C.

[0179] In all samples, the Young's modulus of the SPG was high, exceeding 10 GPa (12.21 GPa, 17.51 ​​GPa, and 16.16 GPa in Figures 11A, B, and C, respectively).

[0180] Example 6 Synthesis of SPG using natural polysaccharides An aqueous solution of chondroitin sulfate and each of the guanidinium-based first-generation monomers prepared in Example 1 ( Gu M Gen.IAn aqueous solution of ) was mixed with the guanidium monomer to achieve a theoretical molar ratio of 1:1 for the anionic functional groups in chondroitin sulfate. The mixed aqueous solution underwent liquid-liquid phase separation, yielding a turbid supramolecular polymer emulsion (Figure 12). The emulsion was concentrated by centrifugation to a viscous liquid, rinsed with pure water, and vacuum-dried to obtain supramolecular polymer glass in 95% yield (Figure 13).

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[0182] Example 7 Synthesis of SPG using natural polysaccharides An aqueous solution of sodium heparin sulfate and each of the guanidinium-based first-generation monomers prepared in Example 1 ( Gu M Gen.I An aqueous solution of ) was mixed with the guanidium monomer in such a theoretical molar ratio of 1:1 to the anionic functional groups in sodium heparin sulfate. The mixed aqueous solution underwent liquid-liquid phase separation, yielding a turbid supramolecular polymer emulsion (Figure 14). The emulsion was concentrated by centrifugation to a viscous liquid, rinsed with pure water, and vacuum-dried to obtain supramolecular polymer glass in 98% yield (Figure 15).

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[0184] Example 8 Synthesis of SPG using synthetic polysaccharides An aqueous solution of dextran sulfate sodium and each of the guanidinium-based first-generation monomers prepared in Example 1 ( Gu M Gen.IAn aqueous solution of ) was mixed with the guanidium monomer in such a theoretical molar ratio of 1:1 to the anionic functional groups in dextran sulfate sodium. The mixed aqueous solution underwent liquid-liquid phase separation, yielding a turbid supramolecular polymer emulsion (Figure 16). The emulsion was concentrated by centrifugation to a viscous liquid, rinsed with pure water, and vacuum-dried to obtain supramolecular polymer glass in 100% yield (Figure 17).

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[0186] Example 9 Synthesis of SPG using synthetic polysaccharides An aqueous solution of β-cyclodextrin (product number CAS7585-39-9) in which some of the hydrogen atoms of the hydroxyl group are substituted with -SO3Na, and each of the guanidinium-based first-generation monomers prepared in Example 1 ( Gu M Gen.I An aqueous solution of ) was mixed with the guanidium monomer in such a theoretical molar ratio of 1:1 to the anionic functional groups in the β-cyclodextrin. The mixed aqueous solution underwent liquid-liquid phase separation, yielding a turbid supramolecular polymer emulsion (Figure 18). The emulsion was concentrated by centrifugation to a viscous liquid, rinsed with pure water, and vacuum-dried to obtain supramolecular polymer glass in 98% yield (Figure 19).

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[0188] The synthesis of the supramolecular polymer glasses in Examples 2, 4-9 could be carried out under atmospheric pressure without requiring heating or cooling of the sample.

Claims

1. It contains an organic cation formed by the ionization of a compound having at least two guanidino groups, and an oxyanion. The organic cation and the oxyanion are bonded together by ionic bonds and hydrogen bonds. It is a complex, The aforementioned organic cation is an organic cation obtained by ionizing a guanidine compound represented by the following formula (6), 【Chemistry 1】 (In the formula, R is a substituted or unsubstituted hydrocarbon chain, When the hydrocarbon chain is substituted, a portion of the methylene groups of the hydrocarbon chain is substituted with a group selected from the group consisting of -NH-, -N(alkyl group)-, -O-, -COO-, -O-COO-, -NHCO-, -S-, cycloalkane, cycloalkanone, benzene, the group represented by formula (7), and substituted or unsubstituted -N(guanidylalkylene group)-. If the -N(guanidylalkylene group) is substituted, a portion of the methylene groups of the guazinylalkylene group is substituted with the same group that substituted a portion of the methylene groups of the hydrocarbon chain. 【Chemistry 2】 (In the formula, R 1 , R 2 Each of these is independently an alkyl group or phenyl group having 1 to 6 carbon atoms, and R 3 , R 4 Each of these is independently an alkyl group or phenyl group having 1 to 6 carbon atoms, m is 1 to 6, n is 1 to 6, p is an integer in the range of 0 to 20, and q is an integer in the range of 0 to 20, where p + q is an integer of 1 or greater. The oxyanion comprises a sulfur, phosphorus, or carbon polyoxyanion. A composite in which the carbon polyoxyanion is a supramolecular polymer containing an oxyanion produced by the ionization of a polysaccharide.

2. The composite according to claim 1, wherein the guanidine compound comprises compound (I), compound (II), or both. (I) Compounds represented by formula (6), wherein R is a substituted or unsubstituted hydrocarbon chain, and if the hydrocarbon chain is substituted, a portion of the methylene groups of the hydrocarbon chain is substituted with a group selected from the group consisting of -NH-, -N(alkyl group)-, -O-, -COO-, -O-COO-, -NHCO-, -S-, cycloalkane, cycloalkanone, benzene, and substituted or unsubstituted -N(guanidylalkylene group)-, and if the -N(guanidylalkylene group) is substituted, a portion of the methylene groups of the guazinylalkylene group is substituted with the same group that substituted a portion of the methylene groups of the hydrocarbon chain, except for compounds in which a portion of the methylene groups of the hydrocarbon chain is substituted with a group represented by formula (7). (II) A compound represented by formula (6), wherein the R is substituted hydrocarbon chain, and a portion of the methylene groups of the hydrocarbon chain is substituted by a group represented by formula (7),

3. The composite according to claim 1, wherein the oxyanion is a cyclic phosphate anion represented by the following formula (10), a linear phosphate anion represented by the following formula (11), or a phytic acid anion. 【Transformation 3】 (In the formula, n is either 1 or 4) 【Chemistry 4】 (In the formula, n is an integer between 2 and 1000.)

4. The complex according to claim 1, wherein the polysaccharide comprises carboxymethylcellulose, gellan gum, alginic acid, sulfated alginic acid, carrageenan, xanthan gum, chondroitin sulfate, heparin, hyaluronic acid, pectic acid, gum arabic, agar, tragacanth gum, sodium dextran sulfate, or a sodium sulfated salt of cyclodextrin.

5. The composite according to claim 1, which is insoluble in organic solvents.

6. The composite according to claim 1, which can be processed in water at 20°C.

7. The composite according to claim 1, having self-healing properties.

8. The composite according to claim 1, wherein the composite, having a thickness of 0.5 mm, has a light transmittance of 90% or more in the 400 to 800 nm range.

9. The composite according to claim 1, which is a supramolecular plastic.

10. The composite according to claim 1, which is a supramolecular polymer glass.

11. A composition comprising the complex according to any one of claims 1 to 10.

12. An article comprising the composite according to any one of claims 1 to 10.

13. A method for producing a supramolecular polymer composite, comprising mixing a compound having at least two guanidino groups and an oxyanion-containing compound in water or an aqueous solution, thereby generating a composite in which an organic cation formed by the ionization of the compound having at least two guanidino groups and an oxyanion formed by the ionization of the oxyanion-containing compound are bonded by ionic bonds and hydrogen bonds, The aforementioned organic cation is an organic cation obtained by ionizing a guanidine compound represented by the following formula (6), 【Transformation 5】 (In the formula, R is a substituted or unsubstituted hydrocarbon chain, When the hydrocarbon chain is substituted, a portion of the methylene groups of the hydrocarbon chain is substituted with a group selected from the group consisting of -NH-, -N(alkyl group)-, -O-, -COO-, -O-COO-, -NHCO-, -S-, cycloalkane, cycloalkanone, benzene, the group represented by formula (7), and substituted or unsubstituted -N(guanidylalkylene group)-. If the -N(guanidylalkylene group) is substituted, a portion of the methylene groups of the guazinylalkylene group is substituted with the same group that substituted a portion of the methylene groups of the hydrocarbon chain. 【Transformation 6】 (In the formula, R 1 , R 2 Each of these is independently an alkyl group or phenyl group having 1 to 6 carbon atoms, and R 3 , R 4 Each of these is independently an alkyl group or phenyl group having 1 to 6 carbon atoms, m is 1 to 6, n is 1 to 6, p is an integer in the range of 0 to 20, and q is an integer in the range of 0 to 20, where p + q is an integer of 1 or greater. The oxyanion comprises a sulfur, phosphorus, or carbon polyoxyanion. A method wherein the carbon polyoxyanion contains an oxyanion produced by the ionization of a polysaccharide, and the resulting complex is a supramolecular polymer.

14. The use of a compound having at least two guanidino groups and a compound containing a sulfur, phosphorus, or carbon oxyanion for the production of a supramolecular polymer composite, The supramolecular polymer composite is a composite comprising an organic cation formed by the ionization of a compound having at least two guanidino groups, and an oxyanion, wherein the organic cation and the oxyanion are bonded together by ionic bonds and hydrogen bonds. The aforementioned organic cation is an organic cation obtained by ionizing a guanidine compound represented by the following formula (6), 【Transformation 7】 (In the formula, R is a substituted or unsubstituted hydrocarbon chain, When the hydrocarbon chain is substituted, a portion of the methylene groups of the hydrocarbon chain is substituted with a group selected from the group consisting of -NH-, -N(alkyl group)-, -O-, -COO-, -O-COO-, -NHCO-, -S-, cycloalkane, cycloalkanone, benzene, the group represented by formula (7), and substituted or unsubstituted -N(guanidylalkylene group)-. If the -N(guanidylalkylene group) is substituted, a portion of the methylene groups of the guazinylalkylene group is substituted with the same group that substituted a portion of the methylene groups of the hydrocarbon chain. 【Transformation 8】 (wherein R 1 , R 2 are each independently an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R 3 , R 4 are each independently an alkyl group having 1 to 6 carbon atoms or a phenyl group, m is 1 to 6, n is 1 to 6, p is an integer in the range of 0 to 20, q is an integer in the range of 0 to 20, with the proviso that p+q is an integer of 1 or more.) The oxyanion comprises a sulfur, phosphorus, or carbon polyoxyanion. The aforementioned carbon polyoxyanion includes oxyanions produced by the ionization of polysaccharides.

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