Mechanical hard sustainable plastic and green non-covalent production method thereof

Abstract

The present invention provides a complex comprising: an organic cation obtained by ionization of a compound having at least two amino groups or guanidino groups; and an oxygen-containing anion, in which the organic cation and the oxygen-containing anion are bonded to each other through an ionic bond and a hydrogen bond.

Description

Technical Field

[0001] The present invention relates to a mechanically robust sustainable plastic and a method for manufacturing the same. Background Art

[0002] In our daily lives, various plastics such as polyethylene terephthalate, polycarbonate, polymethacrylate, polyolefin, and polyurethane have been used. The amount of plastics produced since 1950 has exceeded 8.3 billion tons, and 6.3 billion tons of plastics have been disposed of as waste (Non-Patent Document 1). The impact of waste plastics on the environment, such as the ocean and soil, has become a problem.

[0003] Regulatory laws on plastics, such as the Basel law on the import and export of plastics in 2021 and the Plastic Resources Circulation Promotion Law in Japan, have been enforced both in Japan and abroad to promote plastic regulation. Plastics with a low environmental load need to be used.

[0004] Although the recycling of plastics has been promoted, even worldwide, the recycling rate is only about 9% of the production volume (Non-Patent Document 1), and most waste plastics are still incinerated. Although the recycling of polyethylene terephthalate has been relatively promoted, it is still difficult to degrade and recycle polyethylene terephthalate.

[0005] Various polymers that can be recycled with catalysts (Non-Patent Document 2) and biodegradable polymers (Non-Patent Document 3) have been developed. However, the recycling of plastics involves the following problems: recycling requires many steps, resulting in high costs; using catalysts such as precious metals in the recycling of plastics, resulting in high costs; and it is difficult to degrade plastics into monomers.

[0006] Meanwhile, in a supramolecular polymer in which monomers are bound to each other by non-covalent bonds, the monomers adhere to each other through weak reversible interactions. The polymer can be recycled because even when the monomers are separated from each other or the bonds between them are broken by external stimuli, the monomers will adhere to each other again through self-healing. Therefore, the polymer is expected to be a new material with low environmental load. For example, in Non-Patent Document 4, a photo-responsive supramolecular polymer glass formed by aggregation of 1,1,1-tris(hydroxymethyl)propane monomers having three ureido-4-pyrimidinone groups is disclosed, and the glass has high stiffness and satisfactory self-healing properties. In Non-Patent Document 5, a metal supramolecular copolymer formed by binding a monomer with Zn(NTf2)2 is disclosed, wherein the monomer is obtained by binding three 2,6-bis(1'-methylbenzimidazolyl)pyridine molecules to a 1,3,5-tris(alkyl)benzene nucleus, or by binding two 2,6-bis(1'-methylbenzimidazolyl)pyridine molecules to an ethylene-butene copolymer. However, the mechanical strength of the related art photo-responsive supramolecular polymer glass is poor.

[0007] Citation List

[0008] Non-Patent Literature (NPL)

[0009] NPL 1: Sci. Adv. 2017, 3, e1700782.

[0010] NPL 2: Science 2018, 360, 398 - 403.

[0011] NPL 3: Nature 2020, 590, 423 - 427.

[0012] NPL 4: Nature Commun. 2016, 7, 10995.

[0013] NPL 5: Nature Commun. 2022, 13, 356. Summary of the Invention

[0014] Technical Problem

[0015] The problem to be solved by the present invention is to provide a dynamically robust composite that can be green synthesized and molded with an aqueous solvent.

[0016] Solution

[0017] The present invention includes the following embodiments.

[0018] Item 1.

[0019] A composite, comprising:

[0020] An organic cation obtained by ionization of a compound having at least two amino groups or guanidyl groups; and

[0021] An oxyanion

[0022] wherein the organic cation and the oxyanion are bonded to each other by an ionic bond and a hydrogen bond.

[0023] Item 2.

[0024] The complex according to Item 1, wherein the organic cation and the oxyanion are bonded to each other by an ionic bond and a hydrogen bond represented by one or two or more of the following formulas (1) to (4):

[0025] [Chemical formula 1]

[0026]

[0027] In formulas (1) to (4), R represents an arbitrary monovalent organic group.

[0028] Item 3.

[0029] The complex according to Item 1, wherein the organic cation is an organic cation obtained by ionization of a guanidine compound represented by the following formula (6):

[0030] [Chemical formula 2]

[0031]

[0032] wherein R represents a substituted or unsubstituted hydrocarbon chain, and

[0033] when the hydrocarbon chain is substituted, partial methylenes of the hydrocarbon chain are each substituted with a group selected from the following: -NH-; -N(alkyl)-; -O-; -COO-; -O-COO-; -NHCO-; -S-; cycloalkane; cycloalkanone; benzene; a group represented by formula (7); and substituted or unsubstituted -N(guanidylalkylene)-, and when the -N(guanidylalkylene)- is substituted, partial methylenes of the guanidylalkylene are each substituted with the same group as the group substituting the partial methylenes of the hydrocarbon chain;

[0034] [Chemical formula 3]

[0035]

[0036] Wherein, R1 and R2 each independently represent an alkyl group having 1 to 6 carbon atoms, or phenyl, R3 and R4 each independently represent an alkyl group having 1 to 6 carbon atoms, or phenyl, "m" represents 1 to 6, "n" represents 1 to 6, "p" represents an integer from 0 to 20, and "q" represents an integer from 0 to 20, provided that p + q is an integer of 1 or greater.

[0037] Item 4.

[0038] The complex according to Item 3, wherein the guanidine compound contains the following compound (I), the following compound (II), or both of them:

[0039] (I) A compound represented by formula (6), wherein A represents a substituted or unsubstituted hydrocarbon chain. When the hydrocarbon chain is substituted, some of the methylene groups of the hydrocarbon chain are each substituted by a group selected from the following: -NH-; -N(alkyl)-; -O-; -COO-; -O-COO-; -NHCO-; -S-; cycloalkane; cycloalkanone; benzene; and substituted or unsubstituted -N(guanidinoalkyl)-, and when the -N(guanidinoalkyl)- is substituted, some of the methylene groups of the guanidinoalkyl are each substituted by the same group as the group substituting the methylene groups of the hydrocarbon chain, provided that a compound in which some of the methylene groups of the hydrocarbon chain are each substituted by a group represented by formula (7) is excluded; and

[0040] (II) A compound represented by formula (6), wherein A represents a substituted hydrocarbon chain, and some of the methylene groups of the hydrocarbon chain are each substituted by a group represented by formula (7).

[0041] Item 5.

[0042] The complex according to Item 1, wherein the oxyanion is an oxyanion of sulfur, phosphorus, silicon, or carbon.

[0043] Item 6.

[0044] The complex according to Item 5, wherein the oxyanion is a polyoxyanion.

[0045] Item 7.

[0046] 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), the anion of phytic acid, or the anion of a carboxylic acid:

[0047] [Chemical formula 4]

[0048]

[0049] Wherein, "n" represents 1 or 4;

[0050] [Chemical Formula 5]

[0051]

[0052] Among them, "n" represents an integer from 1 to 1000.

[0053] Item 8.

[0054] The complex according to Item 1 or 5, wherein the oxyanion is an oxyanion generated by ionizing and dissociating a polysaccharide having an anionic functional group.

[0055] Item 9.

[0056] The complex according to Item 1, wherein the complex is insoluble in organic solvents.

[0057] Item 10.

[0058] The complex according to Item 1, wherein the complex has processability in water at 20°C.

[0059] Item 11.

[0060] The complex according to Item 1, wherein the complex has self-healing properties.

[0061] Item 12.

[0062] The complex according to Item 1, wherein the light transmittance of the complex with a thickness of 0.5 mm is 90% or higher at 400 nm to 800 nm.

[0063] Item 13.

[0064] The complex according to Item 1, wherein the complex is a supramolecular plastic.

[0065] Item 14.

[0066] The complex according to Item 1, wherein the complex is a supramolecular polymer glass.

[0067] Item 15.

[0068] A composition comprising the complex according to any one of Items 1 to 14.

[0069] Item 16.

[0070] An article comprising the complex according to any one of Items 1 to 14.

[0071] Item 17.

[0072] A method for preparing a composite, the method comprising: mixing a compound having at least two amino groups or guanidine groups with a compound containing an oxyanion in water or an aqueous solution to prepare a composite, wherein an organic cation formed by ionization of the compound having at least two amino groups or guanidine groups and an oxyanion formed by ionization of the compound containing an oxyanion are bonded to each other by ionic bonds and hydrogen bonds.

[0073] Item 18.

[0074] Use of a compound having at least two amino groups or guanidine groups and a compound containing an oxyanion of sulfur, phosphorus, silicon, or carbon for preparing a supramolecular polymer composite.

[0075] Advantages of the invention

[0076] According to the present invention, a dynamically robust composite with a small or no environmental burden in its production and processing can be provided. Brief description of the drawings

[0077] Figure 1 It is a schematic diagram for explaining the polymer network of a supramolecular polymer glass (SPG).

[0078] Figure 2A It is a photograph showing liquid-liquid phase separation during the production of a supramolecular polymer glass (SPG).

[0079] Figure 2B It is a micrograph of micelles of a supramolecular polymer.

[0080] Figure 3 It is a graph showing the respective light transmittances of various plastics and the first-generation supramolecular polymer glass. The term "PMMA" represents polymethyl methacrylate, the term "PC" represents polycarbonate, the term "PET" represents polyethylene terephthalate, the term "PS" represents polystyrene, the term "glass" represents inorganic glass, and the term "SPG" represents supramolecular polymer glass.

[0081] Figure 4 It is a photograph showing the state of a heavy object loaded on the first-generation supramolecular polymer glass by thermocompression molding.

[0082] Figure 5 It is a graph showing the respective Young's moduli of various plastics and the first-generation supramolecular polymer glass. In the second bar from the right, the first-generation monomer Gu M Gen.I -(9-2) was used. In the rightmost bar, the first-generation monomer Gu M Gen.I-(9-4). The term "rubber" means rubber, the term "PVA" means polyvinyl acetate, the term "PTFE" means polytetrafluoroethylene, the term "PP" means polypropylene, the term "PET" means polyethylene terephthalate, the term "PS" means polystyrene, the term "PMMA" means polymethyl methacrylate, the term "PEEK" means aromatic polyether ketone, the term "nylon" means nylon, and the term "SPG" means supramolecular polymer glass.

[0083] Figure 6 is a graph showing the respective tensile strengths of various plastics and the first-generation supramolecular polymer glass. In the second bar from the right, the first-generation monomer Gu M Gen.I -(9-2). In the rightmost bar, the first-generation monomer Gu M Gen.I -(9-4). The term "rubber" means rubber, the term "PVA" means polyvinyl acetate, the term "PTFE" means polytetrafluoroethylene, the term "PP" means polypropylene, the term "PET" means polyethylene terephthalate, the term "PS" means polystyrene, the term "PMMA" means polymethyl methacrylate, the term "PEEK" means aromatic polyether ketone, the term "nylon" means nylon, and the term "SPG" means supramolecular polymer glass.

[0084] Figure 7 is the first-generation supramolecular polymer glass ( Gen.1 SPG, rightmost bar), the second-generation supramolecular polymer glass ( Gen.2 SPG, leftmost bar) and three third-generation supramolecular polymer glasses ( Gen.2 SPG and Gen.1 SPG, the three center bars). The mixing molar ratios between the guanidine compounds (referred to as "M1" and "M2") used to prepare each of the third-generation supramolecular polymer glasses were all changed (the molar ratios "M1:M2" arranged from left to right were 4:1, 1:1, and 1:4).

[0085] Figure 8 A and Figure 8 B are each photographs showing the underwater processability of the first-generation supramolecular polymer glass. Figure 8 A is a photograph showing the state 10 seconds after the glass was placed in water, Figure 8 B is a photograph showing the state 2 hours after being placed in water.

[0086] Figure 9 is a set of views and photographs of the synthesis of supramolecular polymer glass using diamine and sodium hexametaphosphate.

[0087] Figure 10A is a graph showing theGu M Gen.II -1 and phytic acid. The term "force" represents force, and the term "displacement" represents displacement.

[0088] Figure 10B is a graph showing the measurement results of the indentation experiment of SPG formed by Gu M Gen.I -2 and phytic acid. The term "force" represents force, and the term "displacement" represents displacement.

[0089] Figure 11A is a graph showing the measurement results of the indentation experiment of SPG formed by diamine and alginic acid.

[0090] Figure 11B is a graph showing the measurement results of the indentation experiment of SPG formed by guanidine and alginic acid.

[0091] Figure 11C is a graph showing the measurement results of the indentation experiment of SPG formed by diamine / guanidine, alginic acid and hexametaphosphate.

[0092] Figure 12 is a photograph of the supramolecular polymer emulsion produced by mixing chondroitin sulfate and the first-generation monomer ( Gu M Gen.I ).

[0093] Figure 13 is a photograph of the supramolecular polymer glass synthesized in Example 6.

[0094] Figure 14 is a photograph of the supramolecular polymer emulsion produced by mixing sodium heparin sulfate and the first-generation monomer ( Gu M Gen.I ).

[0095] Figure 15 is a photograph of the supramolecular polymer glass synthesized in Example 7.

[0096] Figure 16 is a photograph of the supramolecular polymer emulsion produced by mixing sodium dextran sulfate and the first-generation monomer ( Gu M Gen.I ).

[0097] Figure 17 is a photograph of the supramolecular polymer glass synthesized in Example 8.

[0098] Figure 18 is a photograph of the supramolecular polymer emulsion produced by mixing β-cyclodextrin substituted with -SO3Na and the first-generation monomer ( Gu M Gen.I ). The inserted photograph on the left shows a glass tube filled with the emulsion.

[0099] Figure 19 It is a photograph of the supramolecular polymer glass synthesized in Example 9. Detailed Description of the Invention

[0100] As used herein, the terms "comprising" and "including" both encompass the concept of "consisting of".

[0101] In the numerical ranges of the various stages described herein, the upper limit value or lower limit value of the numerical range of a certain stage can be freely combined with the upper limit value or lower limit value of the numerical range of any other stage. Additionally, in the numerical ranges described herein, the upper limit value or lower limit value of the numerical range can be replaced with the values described in the examples or the values that can be uniquely derived from the examples. Furthermore, in this specification, the numerical values related to each other by the term "to" refer to the numerical range including the numerical values before and after the term "to" as the lower limit value and the upper limit value.

[0102] As used herein, the term "complex" refers to a material formed by combining two or more substances. The corresponding substances used to form the complex are sometimes referred to as "monomers". A complex formed by combining two or more molecules is sometimes referred to as "molecular assembly".

[0103] As used herein, the term "supramolecular polymer" refers to a polymer obtained by combining two or more monomers through reversible interactions. Reversible interactions are, for example, non-covalent bonds such as hydrogen bonds, ionic bonds, hydrophobic interactions, electrostatic interactions, and / or van der Waals forces.

[0104] As used herein, the term "supramolecular plastic" refers to a polymer obtained by combining two or more monomers through reversible interactions or a composition containing the polymer. The "supramolecular plastic" may be the same as the "supramolecular polymer" or may contain substances other than the "supramolecular polymer". The "supramolecular plastic" may be a synthetic resin.

[0105] As used herein, the term "glass" refers to an amorphous solid material. The term "amorphous" is also referred to as "non-crystalline", meaning that no obvious diffraction phenomenon is observed by X-ray diffraction method, so the material has a disordered atomic arrangement.

[0106] As used herein, the term "organic cation" refers to a cation formed by a structure containing at least one carbon atom.

[0107] As used herein, the term "oxyanion" refers to an anion having oxygen bonded to a non-metal.

[0108] According to a first aspect of the present disclosure, there is provided a complex, comprising: an organic cation obtained by ionization of a compound having at least two amino groups or guanidine groups; and an oxyanion. The organic cation and the oxyanion are bonded to each other by an ionic bond and a hydrogen bond.

[0109] To facilitate understanding of the present invention, Figure 1 An example of the complex as a supramolecular polymer is schematically shown. The physical properties of the supramolecular polymer described below can be applied to the complex of the present invention.

[0110] In the supramolecular polymer (1), the organic cation (2) and the oxyanion (3) are bonded to each other by non-covalent bonds, wherein the organic cation (2) is obtained by ionization of a compound having at least two amino groups or a compound having at least two guanidine groups. Therefore, the bond between these monomers is strong, and thus the mechanical strength of the supramolecular polymer is higher than that of the supramolecular polymers of the prior art. In addition, compared with the case where monomers are covalently bonded to each other, since the organic cation and the oxyanion are easily separated from each other, the polymer has excellent recyclability. The organic cation and the oxyanion can be separated from each other, for example, by immersion in water or an aqueous solution as a polar medium for a period of time or longer. The compound having at least two amino groups does not include a compound having at least two guanidine groups.

[0111] In some embodiments, the organic cation and the oxyanion are bonded to each other by an ionic bond and a hydrogen bond represented by one or two or more of the following formulas (1) to (4):

[0112] [Chemical formula 6]

[0113]

[0114] In formulas (1) to (4), R represents an arbitrary monovalent organic group. The term "organic group" as used herein refers to a group having one or more carbon atoms. When there are two or more Rs in a molecule, the Rs may be the same or different from each other.

[0115] As shown in each of formulas (1) and (2), a hydrogen bond is formed between the hydrogen of each of the two amino groups from the amine compound and the oxygen of the oxyanion, and an ionic bond is formed between the ammonium cation and the oxyanion. Alternatively, as shown in each of formulas (3) and (4), a hydrogen bond is formed between the hydrogen of each of the two guanidine groups from the guanidine compound and the oxygen of the oxyanion, and an ionic bond is formed between the guanidinium cation and the oxyanion. Therefore, the mechanical strength of the supramolecular polymer is improved. At the same time, compared with a covalent bond, the bond between the organic cation and the oxyanion is easily separated.

[0116] In some embodiments, the compound having at least two amino groups is an amine compound represented by the following formula (5).

[0117] [Chemical formula 7]

[0118]

[0119] In the formula, R represents a substituted or unsubstituted hydrocarbon chain, and when the hydrocarbon chain is substituted, some of the methylene groups of the hydrocarbon chain are each substituted by a group selected from the following: -NH-; -N(alkyl)-; -O-; -COO-; -O-COO-; -NHCO-; -S-; cycloalkane; cycloalkanone; benzene; a group represented by formula (7); and substituted or unsubstituted -N(guanidinoalkyl)-, and when the -N(guanidinoalkyl)- is substituted, some of the methylene groups of the guanidinoalkyl are each substituted by the same group as the group substituting the methylene groups of the hydrocarbon chain;

[0120] [Chemical formula 8]

[0121]

[0122] In the formula, R1 and R2 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, R3 and R4 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, "m" represents 1 to 6, "n" represents 1 to 6, "p" represents an integer from 0 to 20, and "q" represents an integer from 0 to 20, provided that p + q is an integer of 1 or greater.

[0123] The hydrocarbon chain represented by R can be an aliphatic hydrocarbon chain, an alicyclic hydrocarbon chain, an aromatic hydrocarbon chain, or a combination thereof. The aliphatic hydrocarbon chain can be a saturated straight-chain aliphatic hydrocarbon chain or an unsaturated aliphatic hydrocarbon chain, and can be straight-chain or branched-chain. The hydrocarbon chain is preferably a straight-chain or branched-chain saturated hydrocarbon chain.

[0124] When some of the methylene groups of the hydrocarbon chain are substituted, the number of the substituted methylene groups is not limited. However, the number is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5.

[0125] In a specific embodiment, for -N(alkyl), as a substituent of the methylene group of the hydrocarbon chain, the alkyl is preferably a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms. In a specific embodiment, for -N(guanidinoalkyl)-, as a substituent of the methylene group of the hydrocarbon chain, the alkylidene is preferably a straight-chain or branched-chain alkylidene group having 1 to 6 carbon atoms.

[0126] In formula (7), the alkyl group having 1 to 6 carbon atoms represented by each of R1 and R2 can be linear, branched, or cyclic. The alkyl group having 1 to 6 carbon atoms represented by each of R3 and R4 can be linear, branched, or cyclic. In a specific embodiment, the alkyl groups having 1 to 6 carbon atoms represented by R1, R2, R3, and R4 are each independently a linear alkyl group having 1 to 6 carbon atoms. In a specific embodiment, "p" and "q" each represent an integer from 1 to 20. In a specific embodiment, one of "p" or "q" represents an integer in the range of 1 to 20, and the other of "p" or "q" represents 0.

[0127] The compound having at least two amino groups can have two, three, or four or more amino groups in its molecule.

[0128] In the case where the amine compound has three amino groups in its molecule, compared with the case where the compound has two amino groups in its molecule, the mechanical strength of the supramolecular polymer generally increases. In addition, when the guanidine compound has a substituent based on -NH- on the nitrogen in its hydrocarbon chain, the water solubility of the polymer is improved, and it easily has an amorphous shape.

[0129] In some embodiments, the compound having at least two guanidine groups is a guanidine compound represented by the following formula (6).

[0130] [Chemical formula 9]

[0131]

[0132] In the formula, R represents a substituted or unsubstituted hydrocarbon chain, and when the hydrocarbon chain is substituted, some of the methylene groups of the hydrocarbon chain are each substituted by a group selected from the following: -NH-; -N(alkyl)-; -O-; -COO-; -O-COO-; -NHCO-; -S-; cycloalkane; cycloalkanone; benzene; the group represented by formula (7); and substituted or unsubstituted -N(guanidinoalkyl)-, and when the -N(guanidinoalkyl)- is substituted, some of the methylene groups of the guanidinoalkyl are each substituted by the same group as the group substituting the methylene groups of the hydrocarbon chain;

[0133] [Chemical formula 10]

[0134]

[0135] In the formula, R1 and R2 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, R3 and R4 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, "m" represents 1 to 6, "n" represents 1 to 6, "p" represents an integer from 0 to 20, and "q" represents an integer from 0 to 20, provided that p + q is an integer of 1 or greater.

[0136] The hydrocarbon chain represented by R can be an aliphatic hydrocarbon chain, an alicyclic hydrocarbon chain, an aromatic hydrocarbon chain, or a combination thereof. The aliphatic hydrocarbon chain can be a saturated straight-chain aliphatic hydrocarbon chain or an unsaturated aliphatic hydrocarbon chain, and can be straight-chain or branched-chain. The hydrocarbon chain is preferably a straight-chain or branched-chain saturated hydrocarbon chain.

[0137] When a part of the methylene groups of the hydrocarbon chain is substituted, the number of the substituted methylene groups is not limited. However, the number is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5.

[0138] In a specific embodiment, -N(alkyl), as a substituent of the methylene group of the hydrocarbon chain, the alkyl is preferably a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms. In a specific embodiment, -N(guanidinoalkyl)-, as a substituent of the methylene group of the hydrocarbon chain, the alkyl group is preferably a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms.

[0139] In formula (7), the alkyl groups having 1 to 6 carbon atoms each represented by R1 and R2 can be straight-chain, branched-chain, or cyclic. The alkyl groups having 1 to 6 carbon atoms each represented by R3 and R4 can be straight-chain, branched-chain, or cyclic. In a specific embodiment, the alkyl groups each having 1 to 6 carbon atoms represented by R1, R2, R3, and R4 are each independently a straight-chain alkyl group having 1 to 6 carbon atoms. In a specific embodiment, "p" and "q" each represent an integer from 1 to 20. In a specific embodiment, one of "p" or "q" represents an integer in the range of 1 to 20, and the other of "p" or "q" represents 0.

[0140] The guanidine compound having at least two guanidine groups can have two, three, or four or more guanidine groups in its molecule.

[0141] In the case where the guanidine compound has three guanidine groups in its molecule, compared with the case where the compound has two guanidine groups in its molecule, the mechanical strength of the supramolecular polymer generally increases. In addition, when the guanidine compound has a -NH-based substituent on the nitrogen in its hydrocarbon chain, the water solubility of the polymer is improved, and it is likely to have an amorphous shape.

[0142] In some embodiments, the above-mentioned guanidine compounds are the following guanidine compounds (I) or the following guanidine compounds (II), or include both guanidine compound (I) and guanidine compound (II).

[0143] Guanidine compound (I):

[0144] A compound represented by formula (6), wherein A represents a substituted or unsubstituted hydrocarbon chain, and when the hydrocarbon chain is substituted, some of the methylene groups of the hydrocarbon chain are each substituted by a group selected from the following: -NH-, -N(alkyl)-, -O-, -COO-, -O-COO-, -NHCO-, -S-, cycloalkane, cycloalkanone, benzene, and substituted or unsubstituted -N(guanidinoalkyl)-, and when the -N(guanidinoalkyl)- is substituted, some of the methylene groups of the guanidinoalkyl are each substituted by the same group as the group substituting the methylene groups of the hydrocarbon chain, provided that a compound in which some of the methylene groups of the hydrocarbon chain are each substituted by a group represented by formula (7) is excluded.

[0145] Guanidine compound (II):

[0146] A compound represented by formula (6), wherein A represents a substituted hydrocarbon chain, and some of the methylene groups of the hydrocarbon chain are each substituted by a group represented by formula (7).

[0147] The supramolecular polymer produced by using the guanidine compound (I) has high mechanical strength but is easily soluble in water, and thus has high underwater processability.

[0148] Specific examples of the organic cations obtained by protonation of the guanidine compound (I) include the following organic cations.

[0149] Although the water solubility of the supramolecular polymer produced by using the guanidine compound (II) is lower than that of the supramolecular polymer produced by using the guanidine compound (I), its mechanical strength tends to be smaller.

[0150] Therefore, the supramolecular polymer produced by using both the guanidine compound (I) and the guanidine compound (II) can improve the mechanical strength of the supramolecular polymer produced by using the guanidine compound (II) while suppressing the water solubility of the supramolecular polymer produced by using the guanidine compound (I).

[0151] In the supramolecular polymers produced by using both the guanidine compound (I) and the guanidine compound (II), any combination of any guanidine compound (I) and any guanidine compound (II) disclosed herein can be used as the guanidine compound (I) and the guanidine compound (II). The types of each of the guanidine compound (I) and the guanidine compound (II) can be one or two or more.

[0152] Although the molar ratio of the guanidine compound (I) to the guanidine compound (II) for preparing the supramolecular polymer is not particularly limited, the ratio is preferably from 90:10 to 10:90, more preferably from 20:80 to 80:20.

[0153] Specific specific examples of the organic cation obtained by protonation of the guanidine compound (II) include the organic cations represented by the following formulas (9-1) to (9-10):

[0154] [Chemical formula 11]

[0155]

[0156] In the formulas (9-1) to (9-6), "n" represents an integer of 1 to 100;

[0157] In the formula (9-2), "m" represents an integer of 1 to 100.

[0158] Guanidine is a highly safe substance that exists even in living organisms. Each of the guanidine compounds can be synthesized by known methods or commercial products can be used.

[0159] The term "oxyanion" refers to an anion having a structure formed by a central element and oxygen bonded to the central element. The central element is not particularly limited and can be a metal element or a non-metal. However, from the aspects of safety or low environmental load, sulfur, phosphorus, silicon, or carbon is more preferred.

[0160] In some embodiments, the oxyanion is an oxyanion of sulfur, phosphorus, silicon, or carbon. The oxyanion is generated by electrolytic dissociation of a compound containing an oxyanion of sulfur, phosphorus, silicon, or carbon. The compound containing an oxyanion of sulfur, phosphorus, silicon, or carbon is, for example, but not limited to, salts selected from the following: sulfates; sulfites; sulfonates; protonated phosphates; phosphates; polyphosphates; metaphosphates; phosphites; pyrophosphates; silicates; carboxylates; carbonates; and combinations thereof. The salt is preferably a metal salt, and preferred examples of the metal used to form the metal salt include, but are not limited to, sodium, potassium, lithium, calcium, strontium, barium, and magnesium. One oxyanion can be incorporated into the supramolecular polymer, or two or more oxyanions can be incorporated therein. Alternatively, the compound containing an oxyanion of sulfur, phosphorus, silicon, or carbon is, for example, but not limited to, salts selected from the following: sulfates; phosphodiesters; silicates; carboxylates; and combinations thereof.

[0161] In some embodiments, the above oxyanion is a polyoxyanion having two or more central elements in its molecule. When the oxyanion is a divalent or higher-valent anion, the oxyanion can be bonded to the above organic cation as a counter molecule at two or more sites, and thus it is possible to form a network structure by the bonding of the above organic cation and the above oxyanion.

[0162] In some embodiments, the oxyanion is a cyclic phosphate anion represented by the following formula (10), a linear phosphate anion represented by the following formula (11), an anion of phytic acid, or an anion of a carboxylic acid.

[0163] [Chemical formula 12]

[0164]

[0165] In the formula, "n" represents an integer from 1 to 4.

[0166] [Chemical formula 13]

[0167]

[0168] In the formula, "n" represents an integer from 1 to 1000.

[0169] In the cyclic phosphate anion of formula (10), n preferably represents 1 or 4, and more preferably represents 4. When "n" represents 4, sodium hexametaphosphate as a raw material for the hexaphosphate ion is a compound approved by the US Food and Drug Administration (FDA), and thus has high safety. In addition, an oxyanion with n preferably representing 4 is more preferred because a supramolecular polymer with high mechanical strength can be obtained. The upper limit value of "n" is preferably 100.

[0170] In the linear phosphate anion represented by formula (11), "n" preferably represents 1 to 1000.

[0171] The oxygen-containing anion-containing compound of sulfur, phosphorus, silicon, or carbon can be synthesized by known methods or commercial products can be used.

[0172] The anion of phytic acid is an anion generated by deprotonation of phytic acid represented by formula (12).

[0173] [Chemical formula 14]

[0174]

[0175] The anion of the carboxylic acid is also called a "carbanion", and examples thereof include, but are not limited to, an anion generated by deprotonation of a carboxylic acid represented by formulas (13-1) and (13-2), and an anion of alginic acid represented by formula (14).

[0176] [Chemical formula 15]

[0177]

[0178] [Chemical formula 16]

[0179]

[0180] In some embodiments, the compound containing an oxyanion is a polysaccharide, and thus the above-mentioned oxyanion is an oxyanion generated by electrolytic dissociation of the polysaccharide. The polysaccharide is preferably a polysaccharide having an anionic functional group, more preferably an acidic polysaccharide having an anionic functional group. Examples of such anionic functional groups include acid groups, salts, acid esters, and combinations thereof. When the anionic functional group is a salt, the salt is, for example, but not limited to, salts selected from the following: sulfate; sulfite; sulfonate; protonated phosphate; phosphate; polyphosphate; metaphosphate; phosphite; pyrophosphate; silicate; carboxylate; carbonate; and combinations thereof. The salt is preferably a metal salt, and preferred examples of the metal used to form the metal salt include, but are not limited to, sodium, potassium, lithium, calcium, strontium, barium, and magnesium. Preferred examples of the anionic functional group include sulfate group, sulfate, sulfate ester, carboxyl group, carboxylate, carboxylate ester, sulfo group, sulfonate, sulfonate ester, phosphate group, phosphate, phosphate ester, phosphonic acid group, phosphonate, phosphonate ester, and combinations thereof. The polysaccharide is more preferably a polysaccharide having at least two anionic functional groups selected from: sulfate group; sulfate; sulfate ester salt; carboxyl group; carboxylate; carboxylate ester; sulfo group; sulfonate; sulfonate ester; phosphate group; phosphate; phosphate ester; phosphonic acid group; phosphonate; phosphonate ester; and phosphodiester. The types of the at least two anionic functional groups may be the same as or different from each other.

[0181] The polysaccharide having an anionic functional group preferably has one anionic functional group in each monomer unit that is a constituent unit of the polysaccharide. All monomer units of the polysaccharide may each have an anionic functional group, or some of the monomer units may each have an anionic functional group. At least two anionic functional groups may be directly bonded to a carbon-containing five-membered or six-membered ring of the monomer unit that is a constituent unit of the polysaccharide, or may each be bonded to the five-membered or six-membered ring through a substituted or unsubstituted hydrocarbon chain. The hydrocarbon chain is, for example, but not limited to, an alkylene group (e.g., methylene).

[0182] In the case of electrolytic dissociation of the at least two functional groups, each group is, for example, a sulfate ester group (-O-SO3 - ), a sulfonate ester group (-SO3 - ), a carboxylate ester group (-COO - ), a phosphate ester group (-O-PO3 2- ), or a phosphoryl group (-PO3 - ).

[0183] The polysaccharide having an anionic functional group can be a natural polysaccharide or a synthetic polysaccharide. The polysaccharide having an anionic functional group can be linear, branched, or cyclic. Examples of the polysaccharide include, but are not limited to, carboxymethyl cellulose, gellan gum, alginic acid, sulfated alginic acid, carrageenan, xanthan gum, chondroitin sulfate, heparin, hyaluronic acid, pectic acid, gum arabic, agar, tragacanth, sodium dextran sulfate, and sulfated sodium salt of cyclodextrin.

[0184] Although the number of monomer units of the polysaccharide that undergoes electrolytic dissociation to generate the oxyanion, particularly the number of the polysaccharide having an anionic functional group, is not particularly limited, the number is preferably from 2 to 100,000.

[0185] Although the molecular weight of the polysaccharide that undergoes electrolytic dissociation to generate the oxyanion, particularly the molecular weight of the polysaccharide having an anionic functional group, is not particularly limited, its weight-average molecular weight is preferably from 1,000 to 10,000,000, more preferably from 5,000 to 1,000,000. The weight-average molecular weight of the polysaccharide can be calculated by measurement using gel permeation chromatography (GPC).

[0186] The oxyanion generated from the above polysaccharide that undergoes electrolytic dissociation to generate an oxyanion, particularly the polysaccharide having an anionic functional group, can be bonded to an organic cation by an ionic bond and a hydrogen bond to form a complex, and the organic cation is obtained by ionization of any compound having at least two amino groups or guanidine groups described herein.

[0187] In some embodiments, the Young's modulus of the above supramolecular polymer measured under the following measurement conditions of the indentation experiment is 5 GPa or higher, preferably 10 GPa or higher, more preferably 15 GPa or higher, still more preferably 20 GPa or higher.

[0188] Measurement conditions: The supramolecular polymer is cut into a size of 1 cm in length, 1 cm in width, and 0.5 mm in thickness to produce a sample. At a measurement temperature of 20 °C, the Young's modulus of the sample is measured using an indentation hardness tester ENT-NEXUS (ELIONX Inc.). A diamond indenter tip is used in the indentation test. The test load is set to 50 mN, the loading time is set to 20,000 milliseconds, the holding time is set to 5,000 milliseconds, and the unloading time is set to 20,000 milliseconds.

[0189] Although the modulus of many known synthetic resins polymerized by covalent bonds (such as polytetrafluoroethylene, polypropylene, polyethylene terephthalate, polystyrene, polymethyl methacrylate, and aromatic polyether ketone) is 5 GPa or lower, the Young's modulus of the supramolecular polymer glass (SPG) can be greater than the modulus of such synthetic resins.

[0190] In some embodiments, the tensile strength of the above-mentioned supramolecular polymer measured under the following measurement conditions is preferably 5 MPa or higher and 50 MPa or lower. These values are comparable to the tensile strength of some known synthetic resins polymerized by covalent bonds, and thus can make the tensile strength of the supramolecular polymer glass (SPG) equal to or greater than that of such synthetic resins.

[0191] Measurement conditions: The supramolecular polymer is cut into a size of 2 mm in length, 35 mm in width, and 0.5 mm in thickness to prepare a sample. The test speed is set to 10 mm / s. The sensor indication of the tensile machine is 500 N. The measurement temperature is set to 20°C.

[0192] In some embodiments, the supramolecular polymer glass (SPG) can be processed in water at 20°C. In the supramolecular polymer glass (SPG), organic cations and oxygen-containing anions are bonded to each other by ionic bonds and hydrogen bonds. Therefore, when the glass is placed in water for a certain period of time, water will bond with its supramolecular polymer to swell and soften the polymer. Therefore, the glass can be processed by hand or machine. Adding an electrolyte such as sodium chloride to the water further promotes the dissociation of the polymer into monomers. In addition, the supramolecular polymer can be molded into any shape, such as a flat shape or a spherical shape, for example, by wetting with water. In addition, the drying of the molded supramolecular polymer can maintain the shape of the supramolecular polymer after the molding. 100% of the supramolecular polymer of this embodiment can be degraded in water, and the advantage of such a supramolecular polymer is its low environmental burden.

[0193] In some embodiments, the supramolecular polymer glass (SPG) can be molded into various shapes at a temperature above its glass transition temperature.

[0194] In some embodiments, the supramolecular polymer glass (SPG) has self-healing properties. For example, even when the supramolecular polymer glass breaks into two components, when its fracture surface is wetted with water and the two fracture surfaces are brought into contact with each other and held for a period of time, the two components can bond to each other.

[0195] In some embodiments, the Young's modulus of the above-mentioned supramolecular polymer is 5 GPa or higher at 20°C, preferably 10 GPa or higher, more preferably 15 GPa or higher, still more preferably 20 GPa or higher, and the tensile strength of the above-mentioned supramolecular polymer is 5 MPa or higher and 50 GPa or lower at 20°C. The supramolecular polymer having such a configuration has high rigidity and has a large mechanical strength to resist its tension.

[0196] In some embodiments, the supramolecular polymer glass (SPG) is insoluble in organic solvents. Examples of the organic solvents include dichloromethane, chloroform, methanol, ethanol, acetone, hexane, dimethylformamide, dimethyl sulfoxide, ethyl acetate, diethyl ether, and tetrahydrofuran.

[0197] In some embodiments, the light transmittance of the supramolecular polymer glass with a thickness of 0.5 mm is 95% or higher at 400 nm to 800 nm. The transparency of such a supramolecular polymer is excellent.

[0198] The supramolecular polymer as the complex of the first aspect of the present invention has one or more of the following advantages [1] to [8]. In a particularly preferred embodiment, the polymer has all the advantages except advantage [5], or has all the advantages [1] to [8].

[0199] [1] Quantitative green synthesis

[0200] An organic cation obtained by ionization of a compound having at least two amino groups or guanidine groups is non-covalently bonded to an oxygen-containing anion in a molar ratio of 1:1 to produce a supramolecular polymer. The supramolecular polymer can be synthesized without heating or pressurization. In addition, since the supramolecular polymer can be synthesized in water or an aqueous solvent, organic solvents are not required.

[0201] [2] Green molding

[0202] The supramolecular polymer can be processed in water. The processing does not require heating.

[0203] [3] Super strong

[0204] The Young's modulus of the supramolecular polymer is 5 GPa or higher at 20°C, and / or its tensile strength is 5 MPa or higher and 50 GPa or lower at 20°C.

[0205] [4] Self-healing

[0206] In the case where the supramolecular polymer breaks into two members, when its fracture surface is wetted with water, and the two fracture surfaces are brought into contact with each other and held, the two members can bond to each other.

[0207] [5] Water resistance

[0208] The water solubility of the supramolecular polymer produced by using the guanidine compound (II) is lower than the water solubility of the supramolecular polymer produced by using the guanidine compound (I).

[0209] [6] Organic solvent resistance

[0210] The supramolecular polymer is insoluble in organic solvents. Examples of the organic solvents include dichloromethane, chloroform, methanol, ethanol, acetone, hexane, dimethylformamide, dimethyl sulfoxide, ethyl acetate, diethyl ether, and tetrahydrofuran.

[0211] [7] Complete recycling

[0212] Different from the plastic polymers of the prior art, the recycling of the SPG according to this embodiment does not require any procedures that consume catalysts or energy. Immersing the SPG in an aqueous solution of ammonium chloride or an acid will disrupt the interaction of the salt bridge between the guanidyl group and the phosphodiester group, causing the SPG to completely return to its raw material monomers. The monomers can be recovered by purification methods such as ion exchange resins. The foregoing realizes resource recycling and thus realizes a microplastic-free ocean. The foregoing changes the common sense of plastics.

[0213] In some embodiments, the organic cation and the oxygen-containing anion in the complex according to the first aspect can be bonded to each other by other covalent bonds or non-covalent bonds in addition to ionic bonds and hydrogen bonds. Such other covalent bonds or non-covalent bonds can be formed by introducing functional groups into the above-mentioned organic cation and / or the above-mentioned oxygen-containing anion by known methods.

[0214] In some embodiments, the complex according to the first aspect is a supramolecular polymer. In some embodiments, the complex according to the first aspect is a supramolecular plastic. In some embodiments, the complex according to the first aspect is a supramolecular polymer glass. Preferably, the complex is a supramolecular polymer because the environmental burden during its production and processing becomes smaller or non-existent.

[0215] According to a second aspect of the present disclosure, there is provided a composition including the complex according to the first aspect. The composition may further include a polymer, such as a synthetic resin, an elastomer, or a rubber. In addition, the composition may further include additives other than the polymer. Examples of the additives include, but are not limited to, synthetic resins, elastomers, rubbers, surfactants, lubricants, dispersants, antioxidants, light stabilizers, UV absorbers, colorants, preservatives, and fragrances.

[0216] According to a third aspect of the present disclosure, there is provided an article including the complex according to the first aspect. The article may include components other than the complex according to the first aspect. Examples of the article include, but are not limited to, containers, packages, metal machine industrial products (industrial machines, electric motors, precision machines, and electric motors), household appliances, information devices (such as personal computers and mobile phones), kitchenware, cleaning appliances, stationery, toys, sports goods, furniture, clothes, detergents, pharmaceuticals, cosmetics, coatings, building materials, and vehicles (light vehicles and vehicles), as well as their components.

[0217] According to a fourth aspect of the present disclosure, there is provided a method for preparing a composite, the method comprising: mixing a compound having at least two amino groups or guanidine groups with a compound containing an oxyanion in water or an aqueous solution to prepare a composite, wherein an organic cation formed by ionization of the compound having at least two amino groups or guanidine groups and an oxyanion formed by ionization of the compound containing an oxyanion are bonded to each other by ionic bonds and hydrogen bonds. The composite material may be the composite described in the first aspect above. In some embodiments, the composite is a supramolecular polymer. In some embodiments, the composite is a supramolecular polymer glass.

[0218] The compound having at least two amino groups or guanidine groups, the compound containing an oxyanion, and the composite are as described for the composite in the first aspect. In particular, the supramolecular polymer, which is the composite described in the first aspect, can be produced in one stage.

[0219] When the compound having at least two amino groups or guanidine groups is mixed with the compound containing an oxyanion in water or an aqueous solution, the organic cation formed by ionization of the compound having at least two amino groups or guanidine groups and the oxyanion formed by ionization of the compound containing an oxyanion are ionically bonded and hydrogen-bonded to each other to form the supramolecular polymer. In addition, an anion generated by electrolytic dissociation of the compound having at least two amino groups or guanidine groups and an organic cation generated by electrolytic dissociation of the compound containing an oxyanion neutralize each other and dissolve in water. The supramolecular polymer can be easily separated or recovered from water or an aqueous solution by known methods such as centrifugation and recovery because the supramolecular polymer undergoes liquid-liquid phase separation with the solvent. Drying of the resulting supramolecular polymer provides a supramolecular polymer having high mechanical strength, although its monomer molecules are non-covalently bonded to each other. After being separated or recovered from water or an aqueous solution, the supramolecular polymer can be molded into any shape, such as a flat shape or a spherical shape. As the molding method, any molding method can be used, for example, compression molding, injection molding, or extrusion molding.

[0220] The method for preparing a composite according to this aspect can be carried out in an aqueous system and is environmentally friendly because the use of organic solvents can be avoided. In addition, neither heating nor pressurization is required, so the composite can be produced at a temperature of 5 °C to 40 °C and under an ambient atmosphere or at atmospheric pressure. Furthermore, the method saves costs because the use of expensive rare earth metal (rare metal) catalysts can be avoided.

[0221] According to a fifth aspect of the present disclosure, there is provided a use of a compound containing at least two amino or guanidine groups and an oxygen-containing anion-containing compound of sulfur, phosphorus, silicon, or carbon for preparing a supramolecular polymer complex. The compound having at least two amino or guanidine groups is as described in the complex of the oxygen-containing anion-containing compound of sulfur, phosphorus, silicon, or carbon in the first aspect.

[0222] The disclosures of all patent applications and documents cited herein are incorporated herein by reference in their entirety.

[0223] The present invention will be described more specifically below by way of examples. However, the present invention is not limited thereto.

[0224] Examples

[0225] Example 1 Synthesis of guanidine monomer ( Gu M)

[0226] 1. Synthesis of the first-generation monomer 1 ( Gu M Gen.I -1)

[0227] [Chemical formula 17]

[0228]

[0229] Diethyltriamine (54 mL, 0.5 mol) and S-methylisothiourea 0.5 H2SO4 (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 produce a white precipitate. The crude product was filtered and rinsed with ethanol, and then recrystallized in a mixture of water and isopropanol. Thus, Gu M Gen.I -1 (yield: 93%, based on diethyltriamine) was obtained. The product was identified by 1 H NMR and 13 C NMR. 1 H NMR (600 MHz, 298 K, D2O): δ 3.32 (t, 4H, NH-C H2 -CH2), 2.81 (t, 4H, C H2 -NH-CH2) ppm.

[0230] 13 C NMR (150 MHz, 298 K, D2O): δ 157.07 ( C =NH), 46.62 ( C H2-NH-CH2), 40.63 (NH- Cppm of H2-CH2

[0231] 3. Synthesis of the first-generation monomer 2 ( Gu M Gen.I -2)

[0232] [Chemical formula 18]

[0233]

[0234] In a 1-L three-necked round-bottom flask that had been dried in an oven, dissolve S-methylisothiourea 1 / 2 H2SO4 (250.5 g, 1.8 mol) in 700 mL of Milli-Q water. Add 70 mL of spermidine to the solution. Reflux the reaction mixture for 72 h. Cool the reaction mixture to room temperature. Place the flask in a refrigerator at 4 °C for 12 h to produce a white precipitate. Filter the crude product and wash it with ice water, and then recrystallize it with mL of Milli-Q water. Thus, Gu M Gen.I -2 (yield: 95%, based on spermidine) was obtained. Identify the product by 1 1H NMR and 13 13C NMR.

[0235] 1 1H NMR (600 MHz, 298 K, D2O): δ 2.04 (p, 4H; CH2C H2 CH2), 3.16 (t, 4H;C H2 -NH-C H2 ), 3.64 (t, 4H; NH-C H2 -CH2) ppm.

[0236] 13 13C 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.

[0237] 5. Synthesis of the first-generation monomer 3 ( Gu M Gen.I -3)

[0238] [Chemical formula 19]

[0239]

[0240] In a 100 mL three-necked round-bottom flask that had been 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 the solution. The reaction mixture was refluxed for 72 hours. The reaction mixture was cooled to room temperature. The crude residue was filtered and washed with ice water, and then recrystallized from a mixed solution of water and ethanol (v / v 1:1). Thereby, Gu M Gen.I -3 was obtained (yield: 53%, based on spermidine). The product was identified by 1 H NMR and 13 C NMR.

[0241] 1 H NMR (600 MHz, 298 K, D2O): δ 3.31 (t, 2H, NH-C H 2-(CH2)2-NH-CH2), 3.24 (t, 2H, NH-C H2 -(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 H2 -(CH2)2-NH-CH2) ppm. 13 C NMR (150 MHz, 298 K, 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- C H2-(CH2)2-NH-CH2), 24.95 (NH-CH2- CH2-CH2-NH), 22.83 (NH-(CH2)2- C H2-CH2-NH-CH2) ppm。

[0242] 4. Synthesis of the first-generation monomer 4 ( Gu M Gen.I -4)

[0243] [Chemical formula 20]

[0244]

[0245] In a 200 mL three-necked round-bottom flask that had been dried in an oven, S-methylisothiourea 0.5 H2SO4 (13.9 g, 0.1 mol) was dissolved in a mixed solution of water and ethanol (v / v 1:3). 16 mL of ethylenediamine was added to the solution. The reaction mixture was stirred for 24 hours to produce a white precipitate. The crude residue was washed with ethanol and recrystallized from a mixed solution of water and ethanol (v / v 1:1) to obtain Gu M Gen.I -4, as transparent crystals (yield: 96%, based on ethylenediamine). The product was identified by 1 1H NMR and 13 13C NMR.

[0246] 1 1H NMR (600 MHz, 298 K, D2O): δ 3.44 (s, 4H, C H2 -C H2 ). 13 13C NMR (150 MHz,298 K, D2O): δ 159.95 ( C =NH), 42.95 ( C H2- C H2).

[0247] 5. Synthesis of the first-generation monomer 5 ( Gu M Gen.I -5)

[0248] Gu M Gen.I -5 was synthesized through the following two steps.

[0249] [Chemical formula 21]

[0250]

[0251] Step I: In a 200 mL three-necked round-bottom flask that had been dried in an oven, S-methylisothiourea 0.5 H2SO4 (13.9 g, 0.1 mol) was dissolved in a mixed solution of 50 mL of water and ethanol (v / v 1:3). 10 mL of 1,3-propanediamine was added to the solution. After stirring the mixture for several minutes, the mixed solution of water and ethanol (v / v 1:3) was poured into the mixture and stirring was continued for 30 minutes. The crude residue was filtered, washed with water, and recrystallized to give the desired crystalline product (yield: 72%, based on 1,3-propanediamine). The product was identified by 1 NMR.

[0252] 1 H NMR (600 MHz, 298 K, D2O): δ 3.31 (t, 4H, CH2 -NH), 3.08 (p, 2H,C H2 -NH2), 1.98 (p, 2H, CH2-C H2 -CH2) ppm.

[0253] Step II: The product obtained in Step I (7.4 g) and S-methylisothiourea 0.5 H2SO4 (4.81 g, 34.5 mmol) was dissolved in 50 mL of water. 1.5 mL of aqueous sodium hydroxide solution (5 M) was added dropwise to the mixture and the whole was refluxed for 8 hours. The reaction mixture was cooled to room temperature. The flask was placed in a refrigerator at 4 °C for 12 hours to produce a white precipitate. The crude product was filtered, washed with water, and recrystallized to give Gu M Gen.I -5 (yield: 38%, based on 1,3-propanediamine). The product was identified by 1 H NMR and 13 C NMR.

[0254] 1 H NMR (600 MHz, 298 K, D2O): δ 3.28 (t, 4H, CH2 -NH), 1.89 (p, 2H,CH2-C H2 -CH2) ppm.

[0255] 13 C NMR (150 MHz, 298 K, D2O): δ 156.85 ( C =NH), 38.34 ( C H2-NH), 26.97(CH2- C H2-CH2) ppm.

[0256] 6. Synthesis of the first-generation monomers 6, 7, and 8 (Gu M Gen.I -6, Gu M Gen.I -7, and Gu M Gen.I -8)

[0257] [Chemical Formula 22]

[0258]

[0259] According to the same synthesis protocol as that for Gu M Gen.I -5, a series of guanidine monomers ( Gu M Gen.I -6 to Gu M Gen.I -8) were synthesized. In a flask, 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 refrigerator at 4 °C for 12 hours to produce a white precipitate. The crude product was filtered, washed with water, and recrystallized to afford each desired product ( Gu M Gen.I -6 to Gu M Gen.I -8). Each product was identified by 1 NMR and 13 C NMR.

[0260] Gu M Gen.I -6 (n = 3)

[0261] [Chemical Formula 23]

[0262]

[0263] 1 H NMR (600 MHz, 298 K, D2O): δ 3.22 (t, 4H, C H2 -NH), 1.56 (t, 4H, CH2-C H2 -C H2 -CH2) ppm.

[0264] Gu M Gen.I -7 (n = 4)

[0265] [Chemical Formula 24]

[0266]

[0267] 1 1H NMR (600 MHz, 298 K, D2O): δ 3.19 (t, 4H, C H2 -NH), 1.62 (t, 4H, CH2-C H2 -CH2-C H2 -CH2), 1.41 (p, 2H, CH2-CH2-C H2 -CH2-CH2) ppm. 13 13C NMR (150 MHz, 298K, D2O): δ 156.76 ( C =NH), 40.89 ( C H2-NH), 26.97 (CH2-C H2 -CH2-C H2 -CH2), 22.90 (CH2-CH2-C H2 -CH2-CH2) ppm.

[0268] Gu M Gen.I -8 (n = 5)

[0269] [Chemical Formula 25]

[0270]

[0271] 1 1H NMR (600 MHz, 298 K, D2O): δ 2.60 (t, 4H, C H2 -NH), 1.44 (t, H, NH-CH2-C H2 ), 1.33 (p, 6H, NH-CH2-CH2-C H2 -C H2 -C H2 ) ppm. 13 13C NMR (150 MHz, 298 K, 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.

[0272] 7. Synthesis of the first-generation monomer 9 ( Gu M Gen.I -9)

[0273] [Chemical formula 26]

[0274]

[0275] In a 200 mL three-necked round-bottom flask that had been 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 the solution. The reaction mixture was refluxed for 24 hours to produce a white precipitate. The crude residue was washed with ethanol and recrystallized with Milli-Q water to give Gu M Gen.I -9, as transparent crystals (yield: 96%, bis(2-aminoethyl)ethane-1,2-diamine). The product was identified by 1 1H NMR and 13 13C NMR.

[0276] 1 1H NMR (600 MHz, 298 K, D2O): δ 3.29 (t, 4H, C H2 -NH), 2.70 (t, 4H, N-C H2 -CH2) ppm.

[0277] 13 13C NMR (150 MHz, 298 K, D2O): δ 156.93 ( C =NH), 52.33 ( C H2-NH), 38.92 (N- C H2-CH2) ppm.

[0278] 8. Synthesis of the first-generation monomer 10 ( Gu M Gen.I -10)

[0279] [Chemical formula 27]

[0280]

[0281] In a 300 mL three-necked round-bottom flask that had been dried in an oven, S-methylisothiourea 0.5 H2SO4 (13.9 g, 0.1 mol) was dissolved in 80 mL of Milli-Q water. 30.6 mL of 2, 2’-thiobis(ethan-1-amine) (0.25 mol) was added to the solution. The mixture was refluxed for 3 days. The reaction mixture was cooled to room temperature to produce a white precipitate. The precipitate was suctioned off and recrystallized from water to afford Gu M Gen.I -10 as white crystals (yield: 72%, based on 2, 2’-thiobis(ethan-1-amine)). The product was characterized by 1 1H NMR and 13 13C NMR.

[0282] 1 1H NMR (600 MHz, 298 K, D2O): δ 3.43 (t, 4H; NH-C H2 ), 2.83 (t, 4H;C H2 -S) ppm. 13 13C NMR (150 MHz, 298 K, D2O): δ 156.90 ( C =N), 40.50 (NH- C CH2), 30.27( C CH2-S) ppm.

[0283] 9. Synthesis of the first-generation monomer 11 ( Gu M Gen.I -11)

[0284] [Chemical formula 28]

[0285]

[0286] In a 300 mL three-necked round-bottom flask that had been dried in an oven, S-methylisothiourea 0.5 H2SO4 (13.9 g, 0.1 mol) was dissolved in 80 mL of Milli-Q water. 40 mL of 2, 2’-dithiobis(diethylamine) (0.25 mol) was added to the solution. The mixture was refluxed for 24 hours. The reaction mixture was cooled to room temperature to produce a white precipitate. The precipitate was suctioned off and recrystallized from water to afford Gu M Gen.I -11 as white crystals (yield: 96%, based on 2, 2’-dithiobis(diethylamine)). The product was characterized by 1 1H NMR and 13 13C NMR.

[0287] 11H NMR (600 MHz, 298 K, D2O): δ 3.60 (t, 4H; NH-C H2 ), 3.38 (t, 4H; C H2 -S) ppm. 13 13C NMR (150 MHz, 298 K, D2O): δ 156.90 ( C =N), 39.77 (NH- C H2), 36.11 (NH-CH2- C H2) ppm.

[0288] 10. Synthesis of the first-generation monomer 12 ( Gu M Gen.I -12)

[0289] [Chemical formula 29]

[0290]

[0291] In a 300 mL three-necked round-bottom flask that had been dried in an oven, 2,2'-(ethane-1,2-diylbis(oxy))bis(ethan-1-amine) (38.5 mL, 0.25 mol) was added to a solution obtained by dissolving S-methylisothiourea 1 / 2 H2SO4 (13.9 g, 0.1 mol) in Milli-Q water. The mixture was refluxed for 24 hours. The refluxed product was concentrated using a small evaporator and then left to stand at 4 °C for 3 days. A transparent precipitate was formed and washed with cold ethanol. The washed product was recrystallized from a mixture of water and ethanol to give Gu M Gen.I -12 as transparent crystals (yield: 32%, based on 2,2'-(ethane-1,2-diylbis(oxy))bis(ethan-1-amine)). The product was identified by 1 1H NMR and 13 13C NMR.

[0292] 1 1H NMR (600 MHz, 298 K, D2O): δ 3.72 (t, 4H; NH-C H2 ), 3.70 (p, 4H; NH-CH2- C H2-O), 3.41 (t, 4H; O-C H2 -C H2 -O) ppm.

[0293] 1313C 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.

[0294] 11. Synthesis of the second-generation monomer 1 ( Gu M Gen.II -1)

[0295] [Chemical formula 30]

[0296]

[0297] In a 1000 mL three-necked round-bottom flask that had been dried in an oven, S-methylisothiourea 0.5 H2SO4 (40 g, 0.3 mol) was dissolved in 700 mL of Milli-Q water. 14 mL of 1,3-bis(3-aminopropyl)tetraethylsiloxane was added to the solution. The reaction mixture was refluxed for 24 hours. The reaction mixture was cooled to room temperature, and the crude residue was filtered and washed with cold water to afford Gu M Gen.II -1 (Yield: 53%, based on 1,3-bis(3-aminopropyl)tetraethylsiloxane). The product was identified by 1 1H NMR and 13 13C NMR.

[0298] 1 1H NMR (600 MHz, 298 K, D2O): δ 3.18 (t, 4H; NH-C H2 ), 1.62 (p, 4H; NH-CH2-C H2 ), 0.61 (t, 4H; C H2 -O-Si), 0.14 (s, 12H; Si-C H3 ) ppm. 13 13C 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.

[0299] 12. Synthesis of the second-generation monomer 2 ( Gu M Gen.II -2)

[0300] [Chemical formula 31]

[0301]

[0302] In a 100 mL three-necked round-bottom flask that had been dried in an oven, dissolve 3,3'-(1,1,3,3,5,5,7,7,9,9,11,11-dodecylhexasiloxane-1,11-diyl)bis(prop-1-amine) (5.4 mL, 10 mmol) in a solution of hydrochloric acid (1.5 mL, wt.% = 36.5%) in ethanol (20 mL). Add cyanamide (1.6 g, 0.04 mol) to the solution. Reflux the reaction mixture for 4 hours. Cool the reaction mixture to room temperature and then evaporate it under reduced pressure until the mixture is dry. A viscous liquid is thus obtained. Wash the resulting viscous liquid with warm water (70 °C, 100 mL × 3) to give Gu M Gen.II -2, as a liquid (yield: 12%, based on 3,3'-(1,1,3,3,5,5,7,7,9,9,11,11-dodecylhexasiloxane-1,11-diyl)bis(prop-1-amine)). Identify the product by 1 NMR.

[0303] 1 1H NMR (600 MHz, 298 K, MeOD): δ 2.92 (t, 4H; NH-C H2 ), 1.71 (p, 4H;NH-CH2-C H2 ), 0.64 (t, 4H; C H2 -O-Si), 0.12 (m, 36H; Si-C H3 ) ppm.

[0304] Example 2 Synthesis of supramolecular polymer glass (SPG)

[0305] 1. Synthesis of the first-generation supramolecular polymer glass ( Gen.I SPG)

[0306] The first-generation supramolecular polymer glasses were synthesized by using each of the first-generation monomers prepared in Example 1. The synthesis of the first-generation supramolecular polymer glasses can be carried out in an aqueous system, which involves neither any organic solvents nor any expensive rare-earth metal catalysts. In the following Examples 2 and 4 to 9, unless otherwise specified, the supramolecular polymer glasses were synthesized in a flask as described in Example 1.

[0307] An aqueous solution of each guanidyl first-generation monomer ( Gu M Gen.I ) prepared in Example 1 was added to an aqueous solution of sodium hexametaphosphate (or sodium trimetaphosphate) such that the theoretical mixing molar ratio of the guanidine monomer to the phosphodiester became 1:1. Regardless of which first-generation monomer was used, the mixed aqueous solution immediately underwent liquid-liquid phase separation to produce a turbid supramolecular polymer emulsion ( Figure 2A and Figure 2B , in Fig. 2A, the aqueous layer 10 and the viscous liquid layer 11 formed by the supramolecular polymer glass underwent phase separation at the interface 12). The supramolecular polymer emulsion was centrifuged and concentrated to provide a viscous liquid. The liquid was rinsed with pure water and dried in vacuo to provide the first-generation supramolecular polymer glass ( Gen.I SPG) in a 98% yield.

[0308] 2. Synthesis of second-generation supramolecular polymer glasses ( Gen.II SPG)

[0309] The second-generation supramolecular polymer glasses were synthesized by using each of the second-generation monomers.

[0310] An aqueous solution of each guanidyl second-generation monomer ( Gu M Gen.II ) prepared in Example 1 was added to an aqueous solution of sodium hexametaphosphate (or sodium trimetaphosphate) such that the theoretical mixing molar ratio of the guanidine monomer to the phosphodiester became 1:1. Regardless of which second-generation monomer was used, the mixed aqueous solution immediately underwent liquid-liquid phase separation to produce a turbid supramolecular polymer emulsion. The supramolecular polymer emulsion was centrifuged and concentrated to provide a viscous liquid. The liquid was rinsed with pure water and dried in vacuo to provide the second-generation supramolecular polymer glass ( Gen.II SPG) in a 72% yield.

[0311] 3. Synthesis of third-generation supramolecular polymer glasses ( Gen.III SPG)

[0312] The third-generation supramolecular polymer glasses were synthesized by using both the first-generation monomers and the second-generation monomers.

[0313] The guanidyl first-generation monomers ( Gu M Gen.I), and a second-generation monomer ( Gu M Gen.II ), is added to an aqueous solution of sodium hexametaphosphate (or sodium metaphosphate) such that the theoretical mixing molar ratio of the guanidine monomer to the phosphodiester becomes 1:1. The mixed aqueous solution is immediately subjected to liquid-liquid phase separation to produce a turbid supramolecular polymer emulsion. The supramolecular polymer emulsion is centrifuged and concentrated to provide a viscous liquid. The liquid is rinsed with pure water and dried under vacuum to provide a third-generation supramolecular polymer glass ( Gen.III SPG) in 90% yield.

[0314] [Chemical formula 32]

[0315]

[0316] Example 3 Evaluation of the Physical Properties of Supramolecular Polymer Glass (SPG)

[0317] 1. Light transmittance of supramolecular polymer glass (SPG)

[0318] An SPG film with dimensions of 100 mm in length, 100 mm in width, and 0.5 mm in thickness is prepared, and the light transmittance of the SPG film is measured by the transmission mode of a UV-visible spectrometer.

[0319] (Results)

[0320] As a result, the optical transparency of the SPG film is in the range of 90% to 97%, although the optical transparency varies depending on the molecular structure of its monomers. Therefore, its light transmittance is comparable to that of commercially available transparent resin films (polymethyl methacrylate (PMMA)), polycarbonate (PC), polyethylene terephthalate (PET), polystyrene (PS), and inorganic glass (glass) ( Figure 3 ).

[0321] 2. Mechanical properties of supramolecular polymer glass (SPG)

[0322] An SPG film with dimensions of 100 mm in length, 100 mm in width, and 0.5 mm in thickness is prepared. The film is mounted on a metal plate, and its Young's modulus is measured using an indentation hardness tester ENT-NEXUS (ELIONX Inc.). A diamond indenter tip is used in the indentation test. The maximum load is set to 50 mN, the loading / unloading rate is set to 2.5 mN / s. The duration of the maximum load is set to 5 s. The Young's modulus and indentation hardness of the film are determined from the curve during unloading using the tester. The measurement temperature is 25 °C.

[0323] The tensile strength of the commercial material is the value described in Wikipedia and known literature. Samples with a length of 35 mm, a width of 2 mm, and a thickness of 0.5 mm were prepared, and their tensile strength was measured using a tensile machine at a test speed of 10 mm / s.

[0324] (Results)

[0325] As Figure 4 shown, even when a heavy object is loaded on the first-generation supramolecular polymer glass, the glass can maintain its shape and withstand the load.

[0326] As Figure 5 shown, unexpectedly, the Young's modulus of the second-generation supramolecular polymer glass is greater than 5 GPa, and the Young's modulus of the first-generation supramolecular polymer glass is greater than 15 GPa. Therefore, the Young's modulus of the SPG film is higher than that of the commercial resin film.

[0327] As Figure 6 shown, the tensile strength of the first-generation and second-generation supramolecular polymer glasses is in the range of 20 GPa to 50 GPa, and thus is not lower than that of the commercial resin film.

[0328] 3. Mechanical Properties of the Third-Generation Supramolecular Polymer Glass (SPG)

[0329] The Young's modulus of the third-generation SPG was also measured under the same conditions as in the above section "2. Mechanical Properties of Supramolecular Polymer Glass (SPG)". However, the measurement temperature was 30 °C.

[0330] (Results)

[0331] As Figure 7 shown, although the Young's modulus of the second-generation SPG ( Gen.2 SPG, the leftmost bar) is low, while the Young's modulus of the first-generation SPG ( Gen.1 SPG, the rightmost bar) is high, the mixture of the first-generation SPG and the second-generation SPG can adjust the Young's modulus.

[0332] 4. Processability of Supramolecular Polymer Glass (SPG)

[0333] The glass transition temperatures (Tg) of the first-generation SPG to the third-generation SPG prepared in Example 2 were 35 °C to 125 °C. Similar to synthetic resins such as PET in the related art, each SPG can be processed into various shapes or patterns by hot pressing at a temperature near its Tg.

[0334] 5. Self-Healing Property of Supramolecular Polymer Glass (SPG)

[0335] By applying pressure under environmental conditions (20 °C and 60% humidity), theGu M Gen.I The SPG with -2 groups is broken into two pieces and the SPG can completely self - heal. After self - healing, the mechanical properties of the SPG are not damaged. In addition, each SPG prepared in Example 2 can self - heal by means of water or humidity. Specifically, the first - generation supramolecular polymer glass can be pressed for 30 minutes under high - humidity (RH80%) conditions to self - heal, and the second - generation supramolecular polymer glass can be pressed for 20 minutes under water - spraying conditions to self - heal.

[0336] 6. Underwater processability of the first - generation supramolecular polymer glass ( Gen.I SPG)

[0337] When each of the first - generation supramolecular polymer glasses prepared in Example 2 is immersed in water, the glass gradually softens ( Figure 8 A), and becomes a viscous supramolecular polymer liquid within several hours ( Figure 8 B). When the viscous liquid is vacuum - dried at 80 °C for 6 hours in a Teflon (trademark) container, SPG with mechanical strength is obtained without monomer loss or mechanical property loss. Even by spraying water, Gen.I SPG will soften coordinately, so it can be molded into various structural products. Gen.I SPG

[0338] Example 4 Synthesis of supramolecular polymer glass using ammonium - based monomers

[0339] The ammonium group of the ammonium - based molecule interacts with an oxygen - containing anion (such as a carboxylate group or a phosphodiester group) to form a cross - linked supramolecular network, thereby producing SPG.

[0340] As a typical example, commercial low - molecular - weight materials with di / tri / tetra - amino groups can form supramolecular polymers with oxygen - containing anions through salt bridges.

[0341] As Figure 9 shown, 0.06 M of diamine monomer is dissolved in ethanol, and 0.2 M of sodium hexametaphosphate solution is added to the prepared diamine monomer solution. The solution immediately becomes turbid, and the liquid - liquid phase separation phenomenon is immediately observed. As a result of centrifuging at 12000 r / min for 10 minutes, as indicated by the dotted line in the lower - left photo, this clear liquid - liquid phase separation is observed. The lower - viscosity liquid is washed three times with 50 mL of deionized water. After the washed product is vacuum - dried at 80 °C for 3 hours, a transparent glass with a yield of about 98% is obtained. Figure 9 left - lower photo

[0342] Example 5 Synthesis of SPG using recyclable raw material monomers

[0343] Large amounts of water-soluble low-molecular-weight biomolecules or biopolymers are stored on Earth, and using our strategy, such molecules can form SPG. In this example, SPG is prepared by using the following two recyclable raw materials as the raw material monomers for oxyanions: phytic acid and alginic acid.

[0344] [Chemical formula 33]

[0345]

[0346] Phytic acid is the dihydrogen phosphate ester of inositol hexaphosphate and is the main storage form of phosphorus in grains, beans, oilseeds, and nuts. Alginic acid is a naturally occurring edible polysaccharide purified from brown algae and specific bacteria existing in nature. Alginic acid is rich in carboxyl groups and can thus form salt bridges with amino groups and guanidyl groups. In addition, alginic acid can be added as an additive for enhancing the mechanical properties of SPG to Gen.1 SPG or Gen.2 into SPG.

[0347] 1-1. Phytic acid-based SPG

[0348] An aqueous solution of the guanidyl monomer is added to an aqueous solution of phytic acid such that the stoichiometric molar ratio between the guanidyl group and the phosphate group (guanidinium ion and phosphate ion) becomes 1:1. The mixed aqueous solution immediately undergoes liquid-liquid phase separation to provide a turbid supramolecular polymer emulsion. The supramolecular polymer emulsion is centrifuged to be concentrated into a viscous liquid. When the viscous liquid is washed with Milli-Q water and then dried in vacuo, a supramolecular polymer glass (SPG) is obtained. The SPG can be processed into various shapes or patterns by hot pressing.

[0349] 1-2. Properties of phytic acid-based SPG

[0350] Under the same measurement conditions as those described in Part 2 of Example 3, the mechanical properties of the SPG film prepared in Part 1-1 are determined by an indentation test using ENT-NEXUS (ELIONX Inc.). A diamond indenter tip with a Berkovich shape is used in the indentation experiment. In the case of the combination of phytic acid and Gu M Gen.II -1, the Young's modulus of the SPG is 5.5 GPa ( Figure 10A ). In addition, when SPG is prepared by using Gu M Gen.I -2 instead of Gu M Gen.II -1, the Young's modulus of the SPG increases to 10 GPa ( Figure 10B ).

[0351] 2-1. Alginic acid-based SPG

[0352] An amino or guanidine monomer is added to a dilute aqueous solution of alginic acid such that the stoichiometric molar ratio of guanidine / amino group to carboxyl group (guanidinium / ammonium ion and carboxylate ion) becomes 1:1. The mixed aqueous solution is immediately subjected to liquid-liquid phase separation to provide a turbid supramolecular polymer emulsion. The supramolecular polymer emulsion is centrifuged to concentrate it into a viscous liquid. When the viscous liquid is washed with Milli-Q water and then dried under vacuum, a supramolecular polymer glass is obtained.

[0353] 2-2. Alginate-reinforced SPG

[0354] An amino or guanidine monomer is added to a mixed aqueous solution of alginic acid and hexametaphosphoric acid such that the stoichiometric molar ratio of guanidine / amino group to carboxyl group (guanidinium / ammonium ion and carboxylate ion) becomes 1:1. The mixed aqueous solution is immediately subjected to liquid-liquid phase separation to provide a turbid supramolecular polymer emulsion. The supramolecular polymer emulsion is centrifuged to concentrate it into a viscous liquid. When the viscous liquid is washed with Milli-Q water and then dried under vacuum, a supramolecular polymer glass is obtained.

[0355] 2-3. Results

[0356] Under the same measurement conditions as in Part 2 of Example 3, the mechanical properties of the SPG film were determined by indentation testing using ENT-NEXUS (ELIONX Inc.). A diamond indenter tip with a Berkovich shape was used in the indentation experiment. The mechanical properties of alginate-based SPG and alginate-reinforced SPG are shown in Figures 11A to 11C .

[0357] In each sample, the Young's modulus of the SPG was greater than 10 GPa (12.21 GPa, 17.51 GPa, and 16.16 GPa in Figure 11A , Figure 11B , Figure 11C respectively).

[0358] Example 6 Synthesis of SPG using natural polysaccharides

[0359] An aqueous solution of chondroitin sulfate and an aqueous solution of each guanidine first-generation monomer ( Gu M Gen.I ) prepared in Example 1 were mixed such that the theoretical mixing molar ratio of guanidine monomer to anionic functional groups in chondroitin sulfate became 1:1. The mixed aqueous solution was subjected to liquid-liquid phase separation to produce a turbid supramolecular polymer emulsion ( Figure 12 ). The supramolecular polymer emulsion was centrifuged and concentrated to provide a viscous liquid. The liquid was rinsed with pure water and dried under vacuum to provide a supramolecular polymer glass in 95% yield ( Figure 13 ).

[0360] [Chemical Formula 34]

[0361]

[0362] Example 7: Synthesis of SPG using natural polysaccharide

[0363] An aqueous solution of heparin sulfate and an aqueous solution of each of the guanidyl first-generation monomers prepared in Example 1 ( Gu M Gen.I ) were mixed such that the theoretical mixing molar ratio of the guanidine monomer to the anionic functional groups in chondroitin sulfate became 1:1. The mixed aqueous solution was subjected to liquid-liquid phase separation to produce a turbid supramolecular polymer emulsion ( Figure 14 ). The supramolecular polymer emulsion was centrifuged and concentrated to provide a viscous liquid. The liquid was rinsed with pure water and dried in vacuo to provide a supramolecular polymer glass in 98% yield ( Figure 15 ).

[0364] [Chemical Formula 35]

[0365]

[0366] Example 8: Synthesis of SPG using synthetic polysaccharide

[0367] An aqueous solution of sodium dextran sulfate and an aqueous solution of each of the guanidyl first-generation monomers prepared in Example 1 ( Gu M Gen.I ) were mixed such that the theoretical mixing molar ratio of the guanidine monomer to the anionic functional groups in sodium dextran sulfate became 1:1. The mixed aqueous solution was subjected to liquid-liquid phase separation to produce a turbid supramolecular polymer emulsion ( Figure 16 ). The supramolecular polymer emulsion was centrifuged and concentrated to provide a viscous liquid. The liquid was rinsed with pure water and dried in vacuo to provide a supramolecular polymer glass in 100% yield ( Figure 17 ).

[0368] [Chemical Formula 36]

[0369]

[0370] Example 9: Synthesis of SPG using synthetic polysaccharide

[0371] An aqueous solution of β-cyclodextrin (product number: CAS 7585-39-9) in which a part of the hydrogen atoms of the hydroxyl groups were each replaced by -SO3Na and an aqueous solution of each of the guanidyl first-generation monomers prepared in Example 1 ( Gu M Gen.I)(aqueous solution) is mixed so that the theoretical mixing molar ratio of the guanidine monomer to the anionic functional group in β-cyclodextrin becomes 1:1. The mixed aqueous solution is subjected to liquid-liquid phase separation to produce a turbid supramolecular polymer emulsion ( Figure 18 ). The supramolecular polymer emulsion is centrifuged and concentrated to provide a viscous liquid. The liquid is rinsed with pure water and dried in vacuo to provide a supramolecular polymer glass in 98% yield ( Figure 19 ).

[0372] [Chemical Formula 37]

[0373]

[0374] The synthesis of each of the supramolecular polymer glasses in Example 2 and Examples 4 to 9 can be carried out at atmospheric pressure without heating or cooling the sample.

Claims

1. A complex, comprising: an organic cation obtained by ionization of a compound having at least two amino groups or guanidine groups; and an oxyanion, wherein the organic cation and the oxyanion are bonded to each other by an ionic bond and a hydrogen bond.

2. The composite according to claim 1, wherein The organic cation and the oxyanion are bonded to each other by an ionic bond and a hydrogen bond represented by one or two or more of the following formulas (1) to (4): [Chemical formula 1] ， In formulas (1) to (4), R represents an arbitrary monovalent organic group.

3. The composite according to claim 1, wherein, The organic cation is an organic cation obtained by ionization of a guanidine compound represented by the following formula (6): [Chemical formula 2] ， wherein R represents a substituted or unsubstituted hydrocarbon chain, and when the hydrocarbon chain is substituted, some of the methylene groups of the hydrocarbon chain are each substituted by a group selected from the following: -NH-; -N(alkyl)-; -O-; -COO-; -O-COO-; -NHCO-; -S-; cycloalkane; cycloalkanone; benzene; a group represented by formula (7); and substituted or unsubstituted -N(guanidinoalkyl)-, and when the -N(guanidinoalkyl)- is substituted, some of the methylene groups of the guanidinoalkyl are each substituted by the same group as the group substituting the methylene groups of the hydrocarbon chain; [Chemical formula 3] ， wherein R1 and R2 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, R3 and R4 each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, "m" represents 1 to 6, "n" represents 1 to 6, "p" represents an integer of 0 to 20, and "q" represents an integer of 0 to 20, provided that p + q is an integer of 1 or more.

4. The composite according to claim 3, wherein The guanidine compound contains the following compound (I), the following compound (II), or both of them: (I) A compound represented by formula (6), wherein A represents a substituted or unsubstituted hydrocarbon chain, and when the hydrocarbon chain is substituted, some of the methylene groups of the hydrocarbon chain are each substituted by a group selected from the following: -NH-, -N(alkyl)-, -O-, -COO-, -O-COO-, -NHCO-, -S-, cycloalkane, cycloalkanone, benzene, and substituted or unsubstituted -N(guanidinoalkyl)-, and when the -N(guanidinoalkyl)- is substituted, some of the methylene groups of the guanidinoalkyl are each substituted by the same group as the group substituting the methylene groups of the hydrocarbon chain, provided that a compound in which some of the methylene groups of the hydrocarbon chain are each substituted by a group represented by formula (7) is excluded; and (II) A compound represented by formula (6), wherein A represents a substituted hydrocarbon chain, and some of the methylene groups of the hydrocarbon chain are each substituted by a group represented by formula (7).

5. The composite according to claim 1, wherein, The oxyanion is an oxyanion of sulfur, phosphorus, silicon, or carbon.

6. The composite according to claim 5, wherein The oxyanion is a polyoxyanion.

7. The composite according to claim 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), an anion of phytic acid, or an anion of a carboxylic acid: [Chemical formula 4] ， wherein "n" represents 1 or 4; [Chemical formula 5] ， wherein "n" represents an integer of 1 to 1000.

8. The complex according to claim 1, wherein the oxyanion is an oxyanion generated by electrolytic dissociation of a polysaccharide having an anionic functional group.

9. The composite according to claim 1, wherein, The complex is insoluble in organic solvents.

10. The composite according to claim 1, wherein, The complex has processability in water at 20 °C.

11. The composite according to claim 1, wherein, The complex has self-healing properties.

12. The composite according to claim 1, wherein, The complex with a thickness of 0.5 mm has a light transmittance of 90% or higher at 400 nm to 800 nm.

13. The composite according to claim 1, wherein, The complex is a supramolecular plastic.

14. The composite according to claim 1, wherein, The complex is a supramolecular polymer glass.

15. A composition comprising the complex according to any one of claims 1 to 14.

16. An article comprising the complex according to any one of claims 1 to 14.

17. A method for preparing a composite, the method comprising: A complex is prepared by mixing a compound having at least two amino groups or guanidine groups with a compound containing an oxyanion in water or an aqueous solution, wherein an organic cation formed by ionization of the compound having at least two amino groups or guanidine groups and an oxyanion formed by ionization of the compound containing an oxyanion are bonded to each other by ionic bonds and hydrogen bonds.

18. Use of a compound having at least two amino groups or guanidine groups and a compound containing an oxyanion of sulfur, phosphorus, silicon, or carbon for preparing a supramolecular polymer complex.

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