Sulfur-containing compounds and polymer materials

Abstract

Provided are a new sulfur-containing compound having excellent stability and a high molecular weight material containing said sulfur-containing compound.　The sulfur-containing compound according to the present invention has, in the molecule, at least one each of a first portion represented by formula (1): -(S)n- (in formula (1), m represents a number equal to or more than 2) and a second portion including a functional group F capable of interacting with another molecule and / or ion. The second portion forms a covalent bond with sulfur in the first portion. The sulfur-containing compound according to the present invention is a new sulfur polymer that had not existed hitherto.

Description

[Technical Field]

[0001] This invention relates to sulfur-containing compounds and polymer materials.

[0002] With 7 million tons of sulfur being discarded on the ground annually, there has been a strong demand for its effective utilization in recent years. One method attracting attention is the use of sulfur-based polymer materials. Sulfur (S8) undergoes polymerization simply by heating, as heating causes the 8-membered ring to cleave and generate radicals. While this makes sulfur polymerization very easy, the resulting sulfur polymer is unstable because it is prone to depolymerization at room temperature. Consequently, obtaining high molecular weight sulfur polymers is not easy, and furthermore, sulfur polymers are insoluble in common organic solvents, resulting in poor processability.

[0003] From this perspective, methods for obtaining sulfur polymers are being actively investigated, and research into improving the properties of sulfur polymers is also being widely conducted. For example, various methods have recently been proposed, such as condensation polymerization using halogen compounds, insertion reaction methods using thiol compounds, and copolymerization methods of vinyl compounds and sulfur.

[0004] Non-patent document 1 discloses a method for producing sulfur polymers by copolymerization with vinyl monomers or dithiol monomers. Since the sulfur polymers obtained by this method are soluble in common organic solvents such as chloroform and tetrahydrofuran, improved processability can be expected. Furthermore, non-patent document 2 proposes a reverse vulcanization method that includes a step of copolymerizing a polyfunctional vinyl monomer with sulfur, and it is expected that a more stable sulfur polymer can be obtained. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] Jeffrey Pyun,et.al.Polym. Chem.2017,8,5167-5173 [Non-Patent Document 2] Chung,WJet.al.Nat.Chem.2013,35,518-524 [Overview of the project] [Problems that the invention aims to solve]

[0006] Because sulfur polymers exhibit properties different from general-purpose resins, they are expected to have applications in various fields. Combined with the aforementioned aspect of effective utilization of sulfur, their utility is extremely high, and synthesizing novel sulfur polymers is essential for the development of industry. However, sulfur polymers have poor stability, for example, because they depolymerize when stored at room temperature, making it far from easy to obtain novel sulfur polymers that exist stably.

[0007] The present invention has been made in view of the above, and aims to provide a novel sulfur-containing compound with excellent stability and a polymer material containing the sulfur-containing compound. [Means for solving the problem]

[0008] The inventors of this invention conducted extensive research to achieve the above objective and discovered that this objective can be achieved by introducing a specific functional group into the sulfur segment, thereby completing the present invention.

[0009] In other words, the present invention encompasses, for example, the subject matter described in the following sections. Item 1 A sulfur-containing compound, The molecule contains the following formula (1) -(S) m - (1) (In equation (1), m represents a number greater than or equal to 1.) The first part represented by, It has at least one second site containing a functional group F capable of interacting with other molecules and / or ions, The second site is a sulfur-containing compound that is covalently bonded to the sulfur of the first site. Item 2 The sulfur-containing compound according to item 1, wherein the interaction is at least one selected from the group consisting of non-covalent bonds and coordination bonds. Item 3 The sulfur-containing compound according to item 1 or 2, wherein the functional group F is a functional group based on a polydentate ligand. Item 4 The sulfur-containing compound according to item 1 or 2, wherein the functional group F has hydrogen bonding properties. Item 5 A molecule having a structure in which the second site is covalently bonded to one end or both ends of the first site, the sulfur-containing compound according to any one of items 1 to 4. Item 6 A sulfur-containing compound according to any one of items 1 to 4, having a structure in which the second site is covalently bonded to one end of the first site as a repeating unit. Item 7 Containing the sulfur-containing compound according to any one of items 1 to 6, A sulfur-containing polymer material in which at least two sulfur-containing compounds form an intermolecular interaction through the functional group F.

Advantages of the Invention

[0010] The sulfur-containing compound of the present invention is a novel sulfur compound or sulfur polymer with excellent stability.

Brief Description of the Drawings

[0011] [Figure 1] It is a schematic of the synthesis scheme of LS-bpy obtained in Example 1-1. [Figure 2] (a) and (b) are respectively the 1H-NMR spectrum and 13C-NMR spectrum of LS-bpy obtained in Example 1-1. [Figure 3] It is the MALDI-TOF MS spectrum of LS-bpy obtained in Example 1-1. [Figure 4]These are the GPC measurement results for the polymer materials obtained in Examples 1-2. [Figure 5] (a) and (b) are test results to confirm that a coordination bond is formed between the bipyridine moiety (bpy moiety) and Cu in the LS-bpy obtained in Example 1-2. [Figure 6] This is an outline of the synthesis scheme for the sulfur-UPy compound obtained in Example 2-1 or Example 2-2. [Figure 7] These are the 1H-NMR spectra of the sulfur-UPy compounds obtained in Examples 2-1 and 2-2. [Figure 8] These are the MALDI-TOF MS spectra of the sulfur-UPy compounds obtained in Examples 2-1 and 2-2. [Figure 9] (a) and (b) are FT-IR and solid-state 1H-NMR spectra, respectively, used to determine whether groups derived from Upy-NCO in sulfur-UPy form hydrogen bonds. [Figure 10] This is an outline of the synthesis scheme for Poly(LS-bpy) obtained in Example 3. [Figure 11] (a) and (b) are the 1H-NMR spectrum and 13C-NMR spectrum results of Poly(LS-bpy) obtained in Example 3, respectively. [Figure 12] This is the MALDI-TOF MS spectrum of Poly(LS-bpy) obtained in Example 3. [Figure 13] This shows the GPC measurement results for Poly(LS-bpy) obtained in Example 3. [Figure 14] This is an outline of the synthesis scheme for Poly(LS-BnNHCOS) obtained in Example 4. [Figure 15] This is the FT-IR spectrum of Poly(LS-BnNHCOS) obtained in Example 4. [Figure 16] This is the result of the 1H-NMR spectrum of Poly(LS-BnNHCOS) obtained in Example 4. [Figure 17] This shows the GPC measurement results for Poly(LS-BnNHCOS) obtained in Example 4. [Figure 18] This is an outline of the synthesis scheme for Poly(S-Upy) obtained in Example 5. [Figure 19] These are the GPC measurement results of Poly(S-Upy) obtained in Example 5 in DMSO and chloroform. [Modes for carrying out the invention]

[0012] Embodiments of the present invention will be described in detail below. In this specification, the expressions "containing" and "including" include the concepts of "containing," "including," "substantially consisting of," and "consisting only of."

[0013] 1. Sulfur-containing compounds The sulfur-containing compound of the present invention has the following formula (1) in its molecule -(S) m - (1) (In equation (1), m represents a number greater than or equal to 1.) The molecule has at least one first site represented by and at least one second site containing a functional group F that can interact with other molecules and / or ions, wherein the second site is covalently bonded to the sulfur of the first site. In other words, the sulfur-containing compound of the present invention has a first site and a second site covalently bonded to the first site within the molecule.

[0014] Such sulfur-containing compounds are highly stable and represent novel sulfur polymers. In particular, as will be described later, the sulfur-containing compounds of the present invention can form polymer materials with a so-called supramolecular structure through direct or indirect interactions between molecules, and are therefore expected to exhibit functions not found in conventional sulfur polymers. Furthermore, because the sulfur-containing compounds of the present invention can have a supramolecular structure, they can form polymer materials that appear to have a high molecular weight.

[0015] (First part) A sulfur-containing compound may have one or more of the first site in its molecule. If a sulfur-containing compound has two or more of the first site, for example, the first site is a repeating structural unit of the sulfur-containing compound. The first site can be called a "sulfur segment" because it is represented by formula (1) above.

[0016] In formula (1) above, m is not particularly limited as long as it is a number of 1 or more. m is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and particularly preferably 5 or more. Furthermore, there is no particular upper limit to m; for example, it can be 10000 or less, preferably 5000 or less, more preferably 3000 or less, even more preferably 1000 or less, and particularly preferably 500 or less. m can also be 10 or less. The value of m can be calculated by MALDI-TOF MS spectroscopy.

[0017] (Second part) Sulfur-containing compounds may have one or more second sites in their molecule. When a sulfur-containing compound has two or more second sites, for example, the second sites are repeating structural units of the sulfur-containing compound.

[0018] The second site contains a functional group F (hereinafter sometimes simply referred to as "functional group F") that can interact with other molecules and / or ions. "Other molecules" here can mean, for example, the sulfur-containing compounds of the present invention. That is, the sulfur-containing compounds of the present invention can form intermolecular interactions via the functional group F. On the other hand, "ions" here can mean ions of the metal M described later.

[0019] Furthermore, the term "interaction" as used here can refer to at least one selected from the group consisting of non-covalent bonds and coordinate bonds. The type of non-covalent bond is not particularly limited; for example, a wide range of known non-covalent bonds can be mentioned, specifically including hydrogen bonds, hydrophobic interactions, electrostatic interactions, dipole interactions, ionic bonds, π-electron interactions, host-guest interactions, etc. Among these, hydrogen bonds are preferred as they facilitate molecular design and other factors.

[0020] In the second site, the functional group F is not particularly limited as long as it can form the aforementioned interaction. The second site may have at least one functional group F, and may also have two or more. If the second site has multiple functional groups F, all of the functional groups F may be the same, or some or all of them may be different. Also, if the second site has multiple functional groups F, the types of interactions produced by each functional group F may all be the same, or some or all of them may be different.

[0021] In one embodiment of the sulfur-containing compound according to the present invention, the "functional group F capable of interacting with other molecules and / or ions" can be, for example, a functional group based on a polydentate ligand. When the functional group F is based on a polydentate ligand, the functional group F readily forms the aforementioned coordinate bond interactions. More specifically, when the functional group F is based on a polydentate ligand, the functional group F readily forms coordinate bonds with ions.

[0022] When functional group F is a functional group based on a polydentate ligand, examples of polydentate ligands include, for example, well-known bidentate ligands, tridentate ligands, hexadentate ligands, and polydentate ligands with more than six dentates. Specifically, examples of polydentate ligands include pyridine compounds or derivatives thereof, bipyridine compounds or derivatives thereof, terpyridine compounds or derivatives thereof, carboxylic acid compounds or derivatives thereof, dicarboxylic acid compounds or derivatives thereof, tricarboxylic acid compounds or derivatives thereof, carboxylic acid compounds or derivatives thereof with tetra or more tetravalent

[0023] From the viewpoint of ease of manufacturing sulfur-containing compounds and ease of forming coordinate bonds, when functional group F is a functional group based on a polydentate ligand, it is preferable that functional group F is a functional group based on bipyridine or a derivative thereof.

[0024] If the functional group F of the second site is a functional group based on a polydentate ligand, the second site can be formed, for example, by the polydentate ligand B described below. That is, the second site can be a structural unit based on the polydentate ligand B.

[0025] In another embodiment of the sulfur-containing compound according to the present invention, the "functional group F capable of interacting with other molecules and / or ions" can be any of the various non-covalent bonding groups described above. The non-covalent bonding group F excludes the functional groups based on the polydentate ligands described above.

[0026] If the "functional group F capable of interacting with other molecules and / or ions" is a group that has the property of forming non-covalent bonds, then the functional group F can be, for example, a group that has hydrogen bonding properties. Hereinafter, a functional group F that has hydrogen bonding properties will be referred to as a "hydrogen-bonding functional group F".

[0027] The hydrogen-bonding functional group F is not particularly limited, and for example, any known hydrogen-bonding functional group can be broadly listed. Specifically, examples of hydrogen-bonding functional groups F include amide groups, amino groups, carboxyl groups, hydroxyl groups, isocyanate groups, thioisocyanate groups, groups derived from carbamides, groups derived from ureids, and groups derived from pyrimidine rings.

[0028] If the functional group F of the second site is a hydrogen-bonding functional group F, the second site can be formed, for example, by a hydrogen-bonding compound C as described below. That is, the second site can be a structural unit based on a hydrogen-bonding compound C.

[0029] In the sulfur-containing compound according to the present invention, the second moiety may consist solely of a functional group F, or it may consist of a group containing the functional group F. For example, if the functional group F is a functional group based on a polydentate ligand, it is preferable that the second moiety consists solely of the functional group F.

[0030] (sulfur-containing compounds) A sulfur-containing compound has at least one first site and at least one second site in its molecule.

[0031] The sulfur-containing compound according to the present invention can be a molecule having a structure in which the second moiety is covalently bonded to one or both ends of the first moiety. Hereinafter, this embodiment of the sulfur-containing compound will be referred to as a "main-chain type supramolecular sulfur polymer".

[0032] Main-chain supramolecular sulfur polymers can be described as having a structure in which the second moiety is covalently bonded to one end of the first moiety (hereinafter abbreviated as "structure a"), and a structure in which the second moiety is covalently bonded to both ends of the first moiety (hereinafter abbreviated as "structure b"). Therefore, a main-chain supramolecular sulfur polymer has one first moiety and one or two second moieties in its molecule.

[0033] When a main-chain supramolecular sulfur polymer has the structure a, the group bonded to the end opposite to the end of the first site to which the second site is covalently bonded is not particularly limited, and examples include hydrogen atoms, alkali metal ions such as sodium, and the like.

[0034] When the main-chain supramolecular sulfur polymer has the structure a described above, the type of the second site is not particularly limited as long as it has the functional group F described above, and it is preferable that it has at least one selected from the group consisting of the multidentate ligand-based functional group F described above and the hydrogen-bonding functional group F.

[0035] When a main-chain supramolecular sulfur polymer has structure b, the second sites at both ends can be the same or different. It is preferable that the second sites at both ends are the same, as this facilitates manufacturing and makes it easier to form a supramolecular structure through interactions such as coordination bonds, as described later.

[0036] When the main-chain supramolecular sulfur polymer has the structure b, the type of the second site is not particularly limited as long as it has the functional group F, and it is preferable that it has at least one selected from the group consisting of the multidentate ligand-based functional group and the hydrogen-bonding functional group F.

[0037] Regardless of whether the main-chain supramolecular sulfur polymer has structure a or structure b, the second moiety is usually covalently bonded to the terminal sulfur atom of the first moiety.

[0038] When the sulfur-containing compound according to the present invention is a main-chain type supramolecular sulfur polymer, the weight-average molecular weight (Mw) is preferably 100 to 1,000,000, more preferably 500 to 100,000, and even more preferably 1,000 to 10,000. The weight-average molecular weight (Mw) as used herein is the value obtained by gel permeation chromatography (GPC).

[0039] The sulfur-containing compound according to the present invention may have a structure other than the main-chain type supramolecular sulfur polymer described above. Specifically, the sulfur-containing compound according to the present invention may have a repeating structure in which the second moiety is covalently bonded to one end of the first moiety. Hereinafter, this embodiment of the sulfur-containing compound will be referred to as a "side-chain type supramolecular sulfur polymer."

[0040] Side-chain supramolecular sulfur polymers are formed by repeating a structure in which a second site is bonded to a first site (one end of a sulfur segment). Therefore, if the first site is denoted as "M1" and the second site as "M2", the side-chain supramolecular sulfur polymer has a repeating (M1-M2) unit as its structural unit.

[0041] Since the side-chain type supramolecular sulfur polymer has the above (M1-M2) units as repeating structural units, the side-chain type supramolecular sulfur polymer molecule contains at least two of the first and second sites. The second site contained in the side-chain type supramolecular sulfur polymer molecule may be a single type or two or more different types.

[0042] In side-chain supramolecular sulfur polymers, the second site is typically covalently bonded to the terminal sulfur atom of the first site.

[0043] In a side-chain type supramolecular sulfur polymer, the type of the second site is not particularly limited as long as it has the functional group F, and it is preferable that it has at least one selected from the group consisting of the multidentate ligand-based functional group F and the hydrogen-bonding functional group F.

[0044] The side-chain supramolecular sulfur polymer can be formed from only two or more first sites and two or more second sites, or it may have structural units other than two or more first sites and two or more second sites, as long as the effects of the present invention are not hindered. The side-chain supramolecular sulfur polymer preferably contains 70 mol% or more of the first sites and second sites, more preferably 80 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more.

[0045] When the sulfur-containing compound according to the present invention is a side-chain type supramolecular sulfur polymer, the mass-average molecular weight (Mw) is preferably 100 to 1,000,000, more preferably 500 to 100,000, and even more preferably 1,000 to 10,000.

[0046] The sulfur-containing compounds according to the present invention, whether main-chain type supramolecular sulfur polymers or side-chain type supramolecular sulfur polymers, are usually linear compounds, but may have a branched structure if necessary.

[0047] 2. Method for producing sulfur-containing compounds The method for producing the sulfur-containing compound of the present invention is not particularly limited. For example, the sulfur-containing polymer material of the present invention may be produced by a production method comprising: step 1, obtaining a sulfur segment by a reaction between a sulfur source and a metal source; and step 2, obtaining a sulfur-containing compound by a reaction between the sulfur segment obtained in step 1 and a compound having a functional group F.

[0048] Step 1 is a process for generating sulfur segments through the reaction of a sulfur source with a metal source.

[0049] The sulfur source used in step 1 is a raw material that can provide a sulfur polymer. For example, the sulfur source is represented by the formula (1) above, "-(S) m -This is a raw material that can provide the "-" part. Therefore, the sulfur source may be elemental sulfur or a compound containing sulfur atoms. -(S) m - In terms of ease of application, it is preferable that the sulfur source contains elemental sulfur.

[0050] As an example of elemental sulfur, one can cite cyclic sulfur composed of sulfur atoms, and typically, an eight-membered sulfur ring can be used as a sulfur source. Such sulfur sources can be manufactured by known methods or obtained from commercially available products.

[0051] Furthermore, the sulfur source can be, for example, a sulfur polymer. Such sulfur polymers can be manufactured by known methods or obtained from commercially available products.

[0052] In step 1, examples of the metal source include alkali metals and alkali metal compounds. The alkali metal is not particularly limited and can be sodium, potassium, or lithium, with sodium being preferred. Examples of alkali metal compounds include alkali metal sulfides, with sodium sulfide being preferred. The alkali metal compound may also be a hydrate.

[0053] The metal source is preferably an alkali metal compound, more preferably an alkali metal sulfide, and particularly preferably sodium sulfide, because the reaction is simple and large-scale synthesis is possible.

[0054] In step 1, the method of reacting the sulfur source and the metal source is not particularly limited; for example, a method of mixing the sulfur source and the metal source in a solvent can be used. When a solvent is used in this reaction, the type of solvent is not particularly limited; in addition to water, various organic solvents can be used. When the metal source is an alkali metal compound, and especially when it is an alkali metal sulfide, it is preferable to use an aqueous solvent in the reaction of step 1, and especially water. Also, when the metal source is an alkali metal, it is preferable to use an organic solvent in the reaction of step 1, and especially polar solvents such as dimethylacetamide are preferred.

[0055] In step 1, the ratio of sulfur source to metal source used is not particularly limited. For example, the amount of metal source used per mole of sulfur source is preferably 0.1 to 20 moles, more preferably 1 to 3 moles.

[0056] In step 1, the reaction temperature when the sulfur source and the metal source are reacted is not particularly limited and can be, for example, 0 to 200°C, preferably 15 to 80°C. The reaction time between the sulfur source and the metal source is also not particularly limited and can be, for example, 10 minutes to 48 hours, preferably 30 minutes to 24 hours. The reaction can be carried out, for example, under an inert gas atmosphere such as nitrogen.

[0057] After the reaction in step 1, the resulting reactant can be used in step 2 without any purification treatment, or, if necessary, the reactant obtained in step 1 can be subjected to appropriate post-treatment before being used in step 2. The post-treatment is not particularly limited, and known purification and separation methods can be widely employed. For example, methods include purifying the reactant obtained in step 1 by filtration, or separating the solid content by removing the solvent from the reactant obtained in step 1 through drying.

[0058] The reactant obtained by step 1 above contains a sulfur segment. This sulfur segment is represented by formula (1) above as "-(S) m -(m is 1 or greater) is the component that constitutes the first site in the sulfur-containing compound of the present invention. Both ends of the sulfur segment are, for example, hydrogen atoms or metal salts (for example, sodium salts).

[0059] Step 2 is a step for obtaining a sulfur-containing compound by reacting the sulfur segment obtained in Step 1 with a compound having functional group F. The compound having functional group F may become a second site in the resulting sulfur-containing compound.

[0060] In compounds having a functional group F, the functional group F is the same as described above. Therefore, examples of functional group F include functional groups based on polydentate ligands and functional groups having hydrogen bonding properties.

[0061] Examples of compounds having a functional group F include various polydentate ligands. In this case, the resulting sulfur-containing compound will have a second site having a functional group F capable of coordination bonding.

[0062] Hereinafter, a polydentate ligand containing the functional group F will be referred to as "polydentate ligand B".

[0063] Examples of polydentate ligand B include a wide range of known bidentate ligands, tridentate ligands, hexadentate ligands, and polydentate ligands with more than six dentations. Examples include pyridine compounds or derivatives thereof, bipyridine compounds or derivatives thereof, terpyridine compounds or derivatives thereof, carboxylic acid compounds or derivatives thereof, dicarboxylic acid compounds or derivatives thereof, tricarboxylic acid compounds or derivatives thereof, carboxylic acid compounds or derivatives thereof with tetra or more tetravalent tetravalents, imidazole compounds or derivatives thereof, diimidazole compounds or derivatives thereof, triazole compounds or derivatives thereof, and tetratriazole compounds or derivatives thereof. Examples of bipyridine derivatives and terpyridine derivatives include structures in which at least one hydrogen atom is substituted with another substituent in one or more of the pyridine rings among a plurality of pyridine rings. The type of substituent is not particularly limited as long as the coordination bond is not inhibited, and specifically, examples include hydrocarbon groups (e.g., C1 to C10).

[0064] In particular, polydentate ligand B is preferably a compound that can react with the sulfur atom at the end of the sulfur segment. Preferred such compounds include compounds substituted with halogen atoms, compounds having an isocyanate group, compounds having an epoxy group, and compounds having a carbonyl chloride. Specific examples of polydentate ligand B include bipyridine or its derivatives having a halogen atom, and terpyridine or its derivatives having a halogen atom, with typical examples being 4-(Chloromethyl)-4'-methyl-2,2'-bipyridyl and 4,4'-Bis(chloromethyl)-2,2'-bipyridyl. The halogen atom may be something other than a chlorine atom, but it is preferably a chlorine atom from the viewpoint of reactivity.

[0065] Other specific examples of polydentate ligand B include the compounds represented by B-1 to B-34 below.

[0066] [ka]

[0067] If the polydentate ligand B is, for example, a bipyridine or derivative thereof having a halogen atom, or a terpyridine or derivative thereof having a halogen atom, then in the reaction in step 2, the halogen atom may be eliminated and bonded to the sulfur atom at the end of the sulfur segment. Therefore, when the polydentate ligand B has one halogen atom, the aforementioned main-chain type supramolecular sulfur polymer is produced, and such a main-chain type supramolecular sulfur polymer usually has structure b. Also, when the polydentate ligand B has two halogen atoms, the aforementioned side-chain type supramolecular sulfur polymer may be produced.

[0068] Besides the polydentate ligand B, other examples of compounds having a functional group F include compounds having a hydrogen-bonding functional group F. In this case, the resulting sulfur-containing compound will have a second site having, for example, a hydrogen-bonding functional group F.

[0069] Hereinafter, compounds containing a hydrogen-bonding functional group F will be referred to as "hydrogen-bonding compound C". Hydrogen-bonding compound C does not have functional groups based on polydentate ligands.

[0070] Examples of hydrogen-bonding compound C include a wide range of compounds having known hydrogen-bonding functional groups F. Specifically, examples of hydrogen-bonding functional groups F include amide groups, amino groups, carboxyl groups, hydroxyl groups, isocyanate groups, thioisocyanate groups, groups derived from carbamides, groups derived from ureids, and groups derived from pyrimidine rings.

[0071] Preferably, hydrogen-bonding compound C is a compound having a hydrogen-bonding functional group F, and the functional group F is capable of reacting with the terminal sulfur atom of the sulfur segment. Alternatively, hydrogen-bonding compound C may also be a compound having a hydrogen-bonding functional group F, and having a group other than the functional group F that can react with the terminal sulfur atom of the sulfur segment. Therefore, examples of hydrogen-bonding compound C include compounds having polycondensable groups and compounds having radically polymerizable double bonds.

[0072] When hydrogen-bonding compound C is a compound having a polycondensable group, such polycondensable groups can include amino groups, carboxyl groups, hydroxyl groups, and isocyanate groups, with isocyanate groups being preferred (i.e., hydrogen-bonding compound C is preferably a compound having an isocyanate group). These polycondensable groups can also function as hydrogen-bonding functional groups F after reacting with the sulfur segment. Of course, if hydrogen-bonding compound C has functional groups F other than polycondensable groups, these functional groups F can also function as hydrogen-bonding functional groups F. Therefore, when hydrogen-bonding compound C is a compound having a polycondensable group, the compound can have at least two or more hydrogen-bonding functional groups F in its molecule, preferably three or more, and can have 10 or fewer hydrogen-bonding functional groups F, preferably 8 or fewer, and more preferably 5 or fewer.

[0073] When hydrogen-bonding compound C is a compound having a polycondensation group, typical examples include compounds represented by the following formulas (C-1) and (C-2).

[0074] [ka]

[0075] If hydrogen-bonding compound C is a compound having a polycondensable group, the reaction in step 2 proceeds with polycondensation between the polycondensable group and the sulfur atom at the end of the sulfur segment. Therefore, if hydrogen-bonding compound C has one polycondensable group, the aforementioned main-chain type supramolecular sulfur polymer is produced, and such a main-chain type supramolecular sulfur polymer usually has structure a and / or structure b, preferably structure b. If hydrogen-bonding compound C has two polycondensable groups, the aforementioned side-chain type supramolecular sulfur polymer may be produced.

[0076] When hydrogen-bonding compound C is a compound having a radically polymerizable group, examples of such compounds include not only functional group F, but also radically polymerizable compounds such as allyl groups, acryloyl groups, methacryloyl groups, and styryl groups.

[0077] When hydrogen-bonding compound C is a compound having a radical polymerizable group, a typical example is the compound represented by the following formula (C-3).

[0078] [ka]

[0079] If hydrogen-bonding compound C is a compound having a radical polymerization group, the reaction in step 2 proceeds with a radical polymerization reaction between the radical polymerization group and the sulfur atom at the end of the sulfur segment. Therefore, if hydrogen-bonding compound C has one radical polymerization group, the aforementioned main-chain type supramolecular sulfur polymer is produced, and such a main-chain type supramolecular sulfur polymer usually has structure b. If hydrogen-bonding compound C has two radical polymerization groups, the aforementioned side-chain type supramolecular sulfur polymer may be produced.

[0080] In step 2, the method of reaction between the sulfur segment obtained in step 1 and the compound having the functional group F (i.e., polydentate ligand B or hydrogen bonding compound C) is not particularly limited. For example, one method is to mix the sulfur segment obtained in step 1 and the compound having the functional group F in a solvent.

[0081] For example, when the compound having the functional group F is a polydentate ligand B, it is preferable to employ an interfacial reaction. Specifically, one method is to add a solution of the polydentate ligand B dissolved in a solvent that phase-separates from water to water containing a sulfur segment, and react the compound having the functional group F and the polydentate ligand B at the interface of each solvent phase. Examples of solvents that phase-separate from water include various non-aqueous organic solvents, such as halogenated hydrocarbon solvents like chloroform.

[0082] Furthermore, if the compound having the functional group F is a hydrogen-bonding compound C, one method is to add the hydrogen-bonding compound C to an aqueous solvent containing a sulfur segment. Examples of aqueous solvents include water, C1-C3 alcohol compounds, and amide solvents.

[0083] In step 2, the ratio of the sulfur segment obtained in step 1 to the compound having functional group F is not particularly limited. For example, the amount of compound having functional group F used per mole of sulfur segment is preferably 0.1 to 20 moles, more preferably 2 to 3 moles. One or more compounds having functional group F can be used in step 2. For example, a combination of polydentate ligand B and hydrogen bonding compound C can be used.

[0084] In step 2, the temperature at which the sulfur segment reacts with the compound having functional group F is not particularly limited, and can be, for example, 0 to 200°C, preferably 10 to 170°C, and more preferably 15 to 80°C. The reaction time between the sulfur source and the metal source is also not particularly limited, and can be, for example, 10 minutes to 48 hours, preferably 30 minutes to 24 hours. The reaction can be carried out, for example, under an inert gas atmosphere such as nitrogen.

[0085] After the reaction in step 2, the desired sulfur-containing compound can be obtained by performing appropriate purification treatments as needed.

[0086] Furthermore, in the method for producing sulfur-containing compounds, the sulfur-containing compound produced in step 2 can also be reacted with a compound having a functional group F. Specifically, a new sulfur-containing compound can be produced by reacting the initially produced sulfur-containing compound with a compound having an additional functional group F. The compound having the additional functional group F can be a different type of compound from the first compound having a functional group F that is reacted.

[0087] 3. Sulfur-containing polymer materials The sulfur-containing polymer material of the present invention may contain the sulfur-containing compounds of the present invention described above. In particular, in the sulfur-containing polymer material of the present invention, at least two or more sulfur-containing compounds can form intermolecular interactions via the functional group F.

[0088] For example, if the functional group F at the second site of a sulfur-containing compound is a group based on a polydentate ligand, and the sulfur-containing polymer material contains a metal ion, the sulfur-containing compound can form intermolecular interactions through coordination bonds. Specifically, a polydentate ligand present in the sulfur-containing compound coordinates to the metal ion, and a polydentate ligand from another sulfur-containing compound coordinates to the metal ion. As a result, molecules of the sulfur-containing compound form aggregates via the metal ion, forming a so-called supramolecular polymer (see "Coordination-bonded main-chain supramolecular sulfur polymer" in Figure 1 or Figure 10 below). These aggregates can be easily decomposed by using a compound that breaks coordination bonds, such as EDTA.

[0089] The metal ions to which the polydentate ligands coordinate are not particularly limited as long as they are metals to which polydentate ligands can coordinate. For example, various transition metal ions can be cited, and typical examples include ions of Cu, Fe, Co, Mn, and Al, with divalent copper ions being particularly preferred.

[0090] Furthermore, if the functional group F at the second site of the sulfur-containing compound is a hydrogen-bonding functional group, hydrogen bonds are formed between one sulfur-containing compound and another sulfur-containing compound by the functional group F. This leads to the formation of aggregates of the sulfur-containing compounds, resulting in the formation of so-called supramolecular polymers.

[0091] For example, if the sulfur-containing polymer material of the present invention contains a sulfur-containing compound which is structure b in the main-chain type supramolecular sulfur polymer described above, the functional groups F at both ends of the sulfur-containing compound molecule and the functional groups F of other sulfur-containing compound molecules interact directly or indirectly via the metal ions to form aggregates. These aggregates then successively associate through interactions similar to those of other sulfur-containing compounds, thereby allowing the sulfur-containing polymer material to form a supramolecular structure. The sulfur-containing polymer material may contain structure a in addition to structure b, in which case sulfur-containing compounds of structure a are positioned at one or both ends of the supramolecular structure.

[0092] Furthermore, when the sulfur-containing polymer material of the present invention includes the aforementioned side-chain type supramolecular sulfur polymer, interactions occur directly or indirectly between the functional group F in the repeating structural unit of the sulfur-containing compound molecule and the functional group F in the repeating structural unit of other sulfur-containing compound molecules, thereby allowing the sulfur-containing polymer material to form a supramolecular structure (see "hydrogen-bonded side-chain type supramolecular sulfur polymer" in Figure 14 below).

[0093] As described above, the sulfur-containing polymer material of the present invention forms a supramolecular structure and can therefore be a material with an apparent high molecular weight. The apparent mass-average molecular weight of the sulfur-containing polymer material is preferably 200 to 1,000,000, more preferably 500 to 500,000, and even more preferably 1,000 to 100,000.

[0094] The sulfur-containing polymer material of the present invention is a novel sulfur polymer unlike any other, as aggregates of sulfur-containing compound molecules are easily formed. Furthermore, because aggregates of sulfur-containing compound molecules are formed, the sulfur-containing polymer material of the present invention is less prone to depolymerization, has excellent stability, and is easily able to achieve an apparent high molecular weight. Moreover, because aggregates of sulfur-containing compound molecules are formed, the characteristics of sulfur segments are more easily expressed compared to conventional sulfur polymers, resulting in improved various physical properties.

[0095] The sulfur-containing polymer material may also contain various additives, as long as the effects of the present invention are not hindered. Examples of additives include light stabilizers, antioxidants, preservatives, fillers such as inorganic particles, flame retardants, pigments, colorants, fungicides, and lubricants. One or more of these additives may be included in the water-absorbent resin dispersion.

[0096] The sulfur-containing polymer material may be in solid form, liquid form such as paste, solution, or dispersion. When the sulfur-containing polymer material is in solid form, its shape is not particularly limited and may be in the form of powder, granules, pellets, fibers, plates, films, blocks, sheets, rods, spheres, ellipsoids, or curved shapes.

[0097] The sulfur-containing polymer material of the present invention has excellent stability and processability, making it suitable for a variety of applications. For example, the sulfur-containing polymer material of the present invention can be suitably used in applications such as electronic components, battery materials, optical components, packaging materials, adhesive materials, and drug-carrying materials. [Examples]

[0098] The present invention will be described more specifically below with reference to examples, but the present invention is not limited to the embodiments of these examples.

[0099] (Example 1-1; Synthesis of LS-bpy) LS-bpy was synthesized by attaching a moiety (second moiety) having a bipyridine-based functional group F to both ends of a sulfur segment (first moiety) according to the reaction scheme shown in Figure 1. First, sulfur (300 mg, 1.17 mmol) and Na2S pentahydrate (295 mg, 1.76 mmol) were stirred in 2 mL of water at 25°C for 24 hours to obtain a reaction product, and this product was filtered to prepare a sulfur solution. To the obtained sulfur solution, a solution of bpyCl (4-(Chloromethyl)-4'-methyl-2,2'-bipyridyl, 847 mg, 3.87 mmol) dissolved in 2 mL of chloroform was added, and the mixture was stirred at room temperature (25°C) for 40 hours to allow the interfacial reaction to proceed. After that, the chloroform layer was collected, and magnesium sulfate was added to this chloroform layer, which was dried and purified by column chromatography to obtain LS-bpy.

[0100] Figures 2(a) and (b) show the LS-bpy obtained in Example 1-1, respectively. 1 H-NMR measurement and 13The results of the 1C-NMR measurement are shown. The upper spectrum of both NMR measurements is for comparison with bpy-Cl, and the lower spectrum is for LS-bpy obtained in Example 1-1. From both NMR spectra, it can be seen that the LS-bpy obtained in Example 1-1, compared to Bpy-Cl, has a high-field shift in the proton g or carbon k of the methylene chain linked to sulfur.

[0101] Figure 3 shows the MALDI-TOF MS spectrum of LS-bpy obtained in Example 1-1. The molecular weight of LS-bpy was detected in this spectrum. Elemental analysis of the sulfur content of LS-bpy confirmed that n=3.0 (i.e., the chain length m of the sulfur segment at the first site is 3).

[0102] Based on these results, it was confirmed that the target LS-bpy was successfully synthesized.

[0103] (Examples 1-2; Synthesis of LS-bpy) A polymer material (a main-chain supramolecular sulfur polymer with coordination bonds) was prepared using LS-bpy obtained in Example 1-1 according to the reaction scheme shown in Figure 1. Specifically, LS-bpy obtained in Example 1-1 (20 mg, 43 μmol) and Cu(NO3)2 trihydrate (26 mg, 108 μmol) were stirred in 900 μL of acetonitrile at room temperature (25°C) for 1 day, and then dried under reduced pressure to obtain the polymer material.

[0104] Figure 4 shows the GPC measurement results in CHCl3 for the polymer materials obtained in Example 1-2. The results show that the polymer materials obtained in Example 1-2 exhibited peaks on the higher molecular weight side compared to LS-bpy alone. The number-average molecular weight (Mn) was confirmed to be 3700, the mass-average molecular weight (Mw) 4600, and the PDI 1.26, all calculated as polyethylene glycol. This molecular weight was approximately equivalent to that of sulfur polymers reported to date (around 3000). Generally, supramolecules tend to exhibit a dissociation equilibrium under dilution conditions; therefore, it is expected that polymers with higher molecular weights than those observed in this study are formed under high-concentration conditions.

[0105] Figures 5(a) and (b) show the test results to confirm the formation of a coordination bond between the bipyridine moiety (bpy moiety) in LS-bpy and Cu, specifically the results of UV-Vis spectral measurements. In this measurement, a sample was prepared by adding an appropriate amount of 0.99 mM Cu(NO3)2·3H2O DMSO solution to a 23 μM LS-bpy DMSO solution, and the UV-Vis spectrum of this sample was measured. New peaks were observed at 302 nm and 510 nm in this UV-Vis spectrum, suggesting that LS-bpy has a structure linked by a coordination bond with Cu. To confirm whether this coordination bond formation occurs only at the bpy moiety, LS-Bn (see scheme in Figure 1) and Cu were mixed, but no new peaks were observed (see Figure (b)). This suggests that the polymer material obtained in Example 1-2 is linked by a coordination bond between the bpy moiety and Cu. In other words, it is presumed that a coordination bond is formed between the methylated bipyridine-derived group (functional group F) in the LS-bpy molecule and Cu, and that this Cu has a structure in which other methylated bipyridine-derived groups from other LS-bpy molecules are coordinated.

[0106] Since the polymer materials obtained in Examples 1-2 are formed by coordination bonds between the bpy moiety and Cu, it is expected that the polymer can be decomposed by dissociating these coordination bonds. Therefore, a sample was prepared by adding an excess amount of ethylenediaminetetraacetic acid (EDTA) to the polymer materials obtained in Examples 1-2 in DMSO and stirring, and this sample was subjected to GPC measurement. As a result, it was confirmed that the peak of the polymer material disappeared, indicating that the polymer materials obtained in Examples 1-2 can be easily decomposed by adding EDTA.

[0107] (Example 2-1; Synthesis of sulfur-UPy compounds) Sulfur-UPy compounds were synthesized by bonding a urea-derived group (second site) as a functional group F to both ends of a sulfur segment (first site) according to the reaction scheme shown in Figure 6. First, sulfur (375 mg, 1.47 mmol) was added to dry dimethylacetamide (30 mL), and Na (83 mg, 3.62 mmol) was added. The mixture was stirred at 70°C for 7 hours under a nitrogen atmosphere to obtain the reaction product. Ureidopyrimidinone (Upy-NCO, 944 mg) having an isocyanate group was added to this reaction product, and the mixture was stirred at 70°C for 12 hours under a nitrogen atmosphere. After returning to room temperature, the resulting precipitate was filtered off and dried under reduced pressure to obtain the sulfur-UPy compound.

[0108] (Example 2-2; Synthesis of sulfur-UPy compounds) Sulfur-UPy compounds were synthesized by bonding a urea-derived group (second site) as a functional group F to both ends of a sulfur segment (first site) according to the reaction scheme shown in Figure 6. First, a solution was prepared by dissolving sulfur (133 mg, 0.59 mmol) and Na2S pentahydrate (295 mg, 1.76 mmol) in 5 mL of water. To this solution, 40 mL of a chloroform solution of ureidopyrimidinone (Upy-NCO, 944 mg) having an isocyanate group was added, and the interfacial reaction was allowed to proceed by stirring at 40°C for 12 hours. During this reaction, insoluble matter was formed between the aqueous layer and the chloroform layer, so the insoluble matter was filtered off by suction filtration, and the sulfur-UPy compound was obtained by drying under reduced pressure.

[0109] Figure 7 shows the sulfur-UPy compounds obtained in Examples 2-1 and 2-2. 1 The results of the 1H-NMR measurements are shown. The upper spectrum of this NMR measurement is that of Upy-NCO for comparison, the middle spectrum is that of the sulfur-UPy compound obtained in Example 2-1, and the lower spectrum is that of the sulfur-UPy compound obtained in Example 2-2. From these NMR spectra, a low-field shift was observed in region A (protons of the methylene chain bonded to the NCO group) shown in the figure for both compounds, compared to UPy-NCO.

[0110] Figure 8 shows the MALDI-TOF MS spectra of the sulfur-UPy compounds obtained in Examples 2-1 and 2-2. The molecular weight of sulfur-UPy was detected in this spectrum. Elemental analysis of the sulfur content of sulfur-UPy confirmed that the number of sulfur atoms was 2.1 (i.e., the chain length m of the sulfur segment at the first site was approximately 2.1).

[0111] From the above results, it was confirmed that the target sulfur-UPy compound (hereinafter sometimes simply referred to as "sulfur-UPy") was successfully synthesized.

[0112] Figures 9(a) and (b) show the test results for confirming whether the groups derived from Upy-NCO in sulfur-UPy form hydrogen bonds. Specifically, (a) is the IR spectrum and (b) is the solid 1 1H-NMR spectrum. In the IR spectrum, peaks were observed at 3220 and 3145 cm -1 , and in the solid 1 1H-NMR spectrum, three peaks were observed at 10 - 14 ppm. These suggest that the groups derived from Upy-NCO form hydrogen bonds. Also, the sulfur-UPy obtained in Examples 2-1 and 2-2 was poorly soluble in chloroform but readily dissolved in chloroform containing trifluoroacetic acid, which is known to cleave hydrogen bonds.

[0113] From the above results, it was found that the sulfur-UPy obtained in Examples 2-1 and 2-2 forms a polymeric material composed of aggregates formed by intermolecular hydrogen bonds.

[0114] (Example 3; Synthesis of Poly(LS-bpy)) Poly(LS-bpy) was synthesized using repeating structural units formed by the bonding of a functional group F based on a bipyridine moiety (second moiety) to one end of a sulfur segment (first moiety). First, sulfur (300 mg, 1.17 mmol) and Na2S pentahydrate (295 mg, 1.76 mmol) were stirred in 2 mL of water at 25°C for 24 hours to obtain a reaction product, and this product was filtered to prepare a sulfur solution. To the obtained sulfur solution, a solution of bpy-diCl (4,4'-Bis(chloromethyl)-2,2'-bipyridyl(bpyCl), 979 mg, 3.87 mmol) dissolved in 2 mL of chloroform was added, and the mixture was stirred at room temperature (25°C) for 40 hours to allow the interfacial reaction to proceed. Subsequently, the chloroform layer was recovered, and after adding magnesium sulfate to this chloroform layer and drying, it was purified by column chromatography to obtain Poly(LS-bpy).

[0115] Figures 11(a) and (b) show the Poly(LS-bpy) obtained in Example 3, respectively. 1 H-NMR measurement and 13 The results of the 1C-NMR measurements are shown. The upper spectrum of both NMR measurements is for comparison with Bpy-diCl, and the lower spectrum is for Poly(LS-bpy) obtained in Example 3. 1 From the 1H-NMR spectrum, Poly(LS-bpy) obtained in Example 3 showed a high-field shift of proton d in the methylene chain linked to sulfur and broadening of all protons compared to Bpy-diCl. 13 From the 1C-NMR spectrum, a high-field shift of carbon f in the methylene chain linked to sulfur was confirmed. These results were similar to those obtained in Example 1-1, strongly suggesting the synthesis of the target Poly(LS-bpy).

[0116] Figure 12 shows the MALDI-TOF MS spectrum of Poly(LS-bpy) obtained in Example 3. In this spectrum, repeats corresponding to the molecular weights of bpy(183) and sulfur(32), which are repeating units in the polymer, were confirmed.

[0117] Figure 13 shows the GPC measurement results of Poly(LS-bpy) obtained in Example 3 in DMSO. From these results, it was confirmed that the molecular weight was 1900 in number average molecular weight, 2400 in mass average molecular weight, and 1.26 in terms of polyethylene glycol.

[0118] Based on these results, it was confirmed that the target Poly(LS-bpy) was successfully synthesized.

[0119] Furthermore, UV-Vis spectroscopy was performed to confirm the formation of a coordination bond between the bipyridine moiety (bpy moiety) in Poly(LS-bpy) and Cu. In this measurement, a sample was prepared by adding an appropriate amount of 1.16 mM Cu(NO3)2·3H2O DMSO solution to a 3.81 μM Poly(LS-bpy) DMSO solution, and the UV-Vis spectrum of this sample was measured. A new peak was observed at 470 nm in this UV-Vis spectrum, suggesting the formation of a polymer material having a structure in which the bpy moiety of Poly(LS-bpy) is linked to Cu by a coordination bond.

[0120] The bottom row of the GPC results shown in Figure 13 displays the GPC measurement results for a polymer material having a structure in which the bpy portion of Poly(LS-bpy) is linked to Cu by a coordination bond. Notably, this polymer material showed peaks on the higher molecular weight side compared to Poly(LS-bpy) alone. The highest molecular weight peak had a number average molecular weight of 22,000, a mass average molecular weight of 46,000, and a PDI of 2.17 in terms of polyethylene glycol. These molecular weights are far higher than the molecular weights of sulfur polymers reported to date (approximately 3,000), demonstrating that high molecular weight sulfur polymers were achieved by introducing the concept of supramolecules to sulfur polymers. In other words, it is inferred that a coordination bond is formed between the methylated bipyridine-derived group (functional group F) in the Poly(LS-bpy) molecule and Cu, and that this Cu has a structure in which the methylated bipyridine-derived group in other Poly(LS-bpy) molecules is coordinated.

[0121] (Example 4; Synthesis of Poly(LS-BnNHCOS)) Poly(LS-BnNHCOS) was synthesized using repeating structural units formed by the bonding of a sulfur segment (first site) to one end of a site (second site) having a functional group F derived from an isocyanate (LS-BnNHCOS). First, sulfur (2.58 g, 10.1 mmol) and Na2S pentahydrate (3.40 g, 20.2 mmol) were added to 60 mL of water at 25°C, stirred for 24 hours, filtered, and the resulting filtrate was freeze-dried to obtain a solid (-(S)). m -A polymer consisting of segmentes was obtained. This solid (524 mg, 3.01 mmol) was dissolved in anhydrous DMF (60 mL), and then m-xylylene diisocyanate (BndiNCO), 472 μL, 3.01 mmol) was added. The mixture was stirred under a nitrogen atmosphere at 25°C for 20 hours to obtain the reaction product. After filtering the obtained reaction product, the DMF was removed by distillation to obtain a pale orange solid.

[0122] Figure 15 shows the FT-IR spectrum of the obtained pale orange solid. In this FT-IR spectrum, 2250 cm⁻¹ is observed in the raw material, BndiNCO. -1 The peaks derived from isocyanates in the vicinity have disappeared, and the peak at 1620 cm is -1 -C=O, 3310cm -1 ni-NH, 690cm -1 A peak originating from CS was observed. These results suggest that the monomer BndiNCO was consumed in the reaction, allowing the reaction to proceed.

[0123] Figure 16 shows the pale orange solid obtained in Example 4. 1The results of the 1H-NMR measurement are shown. The lower spectrum of this NMR measurement is that of BndiNCO for comparison, and the upper spectrum is that of the pale orange solid obtained in Example 4. From this NMR spectrum, broadening of all protons was observed compared to BndiNCO. This result was similar to that of LS-bpy and Poly(LS-bpy). From the above, it was found that the target Poly(LS-BnNHCOS) had been synthesized.

[0124] Figure 17 shows the GPC measurement results for Poly(LS-BnNHCOS) in DMSO. In this GPC measurement, Poly(LS-BnNHCOS) showed a peak on the higher molecular weight side compared to BndiNCO. The molecular weight of Poly(LS-BnNHCOS) was confirmed to be 7000 (number average molecular weight), 8100 (mass average molecular weight), and 1.16 (PDI) in terms of polyethylene glycol. This molecular weight is significantly higher than the molecular weight of sulfur polymers reported to date (approximately 3000), suggesting that -(S) m It was found that the polycondensation of - with BndiNCO caused BndiNCO to react, resulting in the synthesis of the desired Poly(LS-BnNHCOS).

[0125] The obtained Poly(LS-BnNHCOS) was poorly soluble in chloroform, but readily soluble in chloroform containing trifluoroacetic acid. As described above, since it readily soluble in chloroform in the presence of trifluoroacetic acid, it is presumed that hydrogen bonds are formed between the side chains of Poly(LS-BnNHCOS) by thioisocyanates, and these hydrogen bonds are dissolved by trifluoroacetic acid. In other words, it is suggested that Poly(LS-BnNHCOS) is a hydrogen-bonded side-chain type supramolecular sulfur polymer.

[0126] (Example 5) Poly(S-Upy) was synthesized using repeating structural units formed by the bonding of a hydrogen-bonding functional group F (second site) to one end of a sulfur segment (first site). Poly(S-Upy) was obtained by stirring sulfur (1.01 g, 3.89 mmol) and UPy-HDI-HEMA (165.3 mg, 0.389 mmol) synthesized by a known method at 160°C for 24 hours under a nitrogen atmosphere.

[0127] Figure 19 shows the GPC measurement results of Poly(S-Upy) in DMSO and chloroform. The results showed peaks of high molecular weight molecules in both measurement solvents, indicating that the desired Poly(S-Upy) was obtained. Furthermore, in this measurement, Poly(S-Upy) generated a large amount of insoluble matter in both DMSO and chloroform. This indicates the formation of hydrogen bonds between polymers, suggesting that Poly(S-Upy) forms a polymer material with a supramolecular structure induced by hydrogen bonding.

[0128] (Method for measuring mass-average molecular weight) The mass-average molecular weight (Mw) was measured using a gel permeation chromatography (GPC) instrument under the following measurement conditions. (Measurement conditions) • Measurement equipment names: Tosoh DP-8020 pump, CO-8020 column oven, UV-8020 ultraviolet detector, RI-8020 refractive index detector • Column: Two TSKgel GMHHR-M columns were used. Column temperature: 40°C • Solvent: CHCl3 or DMSO • Flow rate: 1.0 mL / min when using CHCl3 as the solvent, 3.0 mL / min when using DMSO. • Standard sample: Polystyrene standard when CHCl3 is used as the solvent, polyethylene glycol standard when DMSO is used.

Claims

1. A sulfur-containing compound, The molecule contains the following formula (1) -(S) ｍ - (1) (In equation (1), m represents a number greater than or equal to 1.) The first part represented by, It has at least one second site containing a functional group F capable of interacting with other molecules and / or ions, The second site is a functional group based on a bipyridine site, or The second site is a site based on a compound represented by the following formula (C-1), a compound represented by the following formula (C-2), or a compound represented by the following formula (C-3), 【Chemistry 1】 【Chemistry 2】 The second portion is covalently bonded to the sulfur of the first portion. A sulfur-containing compound comprising only the first and second portions.

2. The sulfur-containing compound according to claim 1, wherein the molecule has a structure in which the second portion is covalently bonded to one or both ends of the first portion.

3. The sulfur-containing compound according to claim 1, having a repeating unit structure in which the second portion is covalently bonded to one end of the first portion.

4. The sulfur-containing compound is described in any one of claims 1 to 3, A sulfur-containing polymer material in which at least two or more sulfur-containing compounds form intermolecular interactions via the functional group F.

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