WO2022239780A1

WO2022239780A1 - Sulfur-containing compound and high molecular weight material

Info

Publication number: WO2022239780A1
Application number: PCT/JP2022/019860
Authority: WO
Inventors: 裕一郎小林; 浩靖山口; 佑輝山岸; 顕義堀口; 大輝北野
Original assignee: 国立大学法人大阪大学
Priority date: 2021-05-10
Filing date: 2022-05-10
Publication date: 2022-11-17
Also published as: JPWO2022239780A1

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

Sulfur-containing compounds and polymeric materials

The present invention relates to sulfur-containing compounds and polymeric materials.

Since 7 million tons of sulfur are dumped on the ground every year, in recent years, there is a strong demand for effective utilization of that sulfur. Polymer materials using sulfur are attracting attention as one of the methods. When sulfur (S ₈ ) is heated, the 8-membered ring is cleaved to generate radicals, so that the polymerization reaction of sulfur can proceed only by heating. Therefore, although the polymerization of sulfur is very simple, the obtained sulfur polymer is a material with poor stability because depolymerization easily occurs at room temperature. Therefore, it is not easy to obtain high molecular weight sulfur polymers, and in addition, sulfur polymers are insoluble in common organic solvents, making them poorly processable materials.

From this point of view, methods for obtaining sulfur polymers are being actively investigated, and studies are also being widely conducted to improve the properties of sulfur polymers. For example, recently, various proposals have been made, such as a condensation polymerization method using a halogen compound, an insertion reaction method using a thiol compound, and a copolymerization method of a vinyl compound and sulfur.

Non-Patent Document 1 discloses a method for producing a sulfur polymer by copolymerization with a vinyl monomer or a dithiol monomer. Since the sulfur polymer obtained by such a method becomes soluble in general-purpose organic solvents such as chloroform and tetrahydrofuran, improvement in processability can be expected. In addition, Non-Patent Document 2 proposes an inverse vulcanization method including a step of copolymerizing a polyfunctional vinyl monomer and sulfur, which is expected to yield a more stable sulfur polymer.

Sulfur polymers are expected to be applied in various fields because they exhibit properties different from those of general-purpose resins. It can be said that the synthesis of sulfur polymers is indispensable for the development of the industrial world. However, since sulfur polymers undergo depolymerization when stored at room temperature, for example, they are poor in stability, and it has never been easy to obtain novel sulfur polymers that exist stably.

The present invention has been made in view of the above, and an object of the present invention is to provide a novel sulfur-containing compound with excellent stability and a polymer material containing the sulfur-containing compound.

As a result of intensive studies aimed at achieving the above object, the present inventors have found that the above object can be achieved by introducing a site containing a specific functional group into the sulfur segment, and have completed the present invention. .

That is, the present invention includes, for example, the subject matter described in the following sections.
Item 1
A sulfur-containing compound,
Formula (1) below in the molecule
- (S) _m - (1)
(In formula (1), m represents a number of 1 or more)
A first portion represented by
at least one second site containing a functional group F capable of interacting with other molecules and/or ions;
A sulfur-containing compound, wherein the second portion is covalently bonded to the sulfur of the first portion.
Item 2
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 coordinate bonds.
Item 3
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
Item 3. The sulfur-containing compound according to

Item

1 or 2, wherein the functional group F has hydrogen bonding properties.
Item 5
Item 5. The sulfur-containing compound according to any one of Items 1 to 4, which is a molecule having a structure in which the second portion is covalently bonded to one or both ends of the first portion.
Item 6
Item 5. The sulfur-containing compound according to any one of Items 1 to 4, which has a structure in which the second portion is covalently bonded to one end of the first portion as a repeating unit.
Item 7
The sulfur-containing compound according to any one of Items 1 to 6,
A sulfur-containing polymeric material in which at least two or more sulfur-containing compounds form an intermolecular interaction via the functional group F.

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

1 is an outline of the synthesis scheme of LS-bpy obtained in Example 1-1. (a) and (b) are the ¹ H-NMR spectrum and ¹³ C-NMR spectrum of LS-bpy obtained in Example 1-1, respectively. It is the MALDI-TOF MS spectrum of LS-bpy obtained in Example 1-1. 1 is the result of GPC measurement of the polymeric material obtained in Example 1-2. (a) and (b) are test results for confirming the formation of a coordinate bond between the bipyridine site (bpy site) in LS-bpy obtained in Example 1-2 and Cu. be. 1 is an outline of a synthesis scheme of a sulfur-UPy compound obtained in Example 2-1 or Example 2-2. ¹ H-NMR spectra of sulfur-UPy compounds obtained in Examples 2-1 and 2-2. Fig. 2 shows MALDI-TOF MS spectra of sulfur-UPy compounds obtained in Examples 2-1 and 2-2. (a) and (b) are FT-IR spectra and solid-state ¹ H-NMR spectra for confirming whether groups derived from Upy-NCO in sulfur-UPy form hydrogen bonds. 1 is an outline of the synthesis scheme of Poly(LS-bpy) obtained in Example 3. FIG. (a) and (b) are the results of ¹ H-NMR spectrum and ¹³ C-NMR spectrum of Poly(LS-bpy) obtained in Example 3, respectively. 4 is a MALDI-TOF MS spectrum of Poly(LS-bpy) obtained in Example 3. FIG. 2 shows the results of GPC measurement of Poly(LS-bpy) obtained in Example 3. FIG. 1 is an outline of the synthesis scheme of Poly(LS-BnNHCOS) obtained in Example 4. FIG. 4 is an FT-IR spectrum of Poly(LS-BnNHCOS) obtained in Example 4. FIG. 1 is the result of ¹ H-NMR spectrum of Poly(LS-BnNHCOS) obtained in Example 4. FIG. 4 shows the results of GPC measurement of Poly(LS-BnNHCOS) obtained in Example 4. FIG. 1 is an outline of the synthesis scheme of Poly(S-Upy) obtained in Example 5. FIG. 2 shows the results of GPC measurement of Poly(S-Upy) obtained in Example 5 in DMSO and chloroform.

Hereinafter, embodiments of the present invention will be described in detail. In this specification, the expressions "contain" and "include" include the concepts of "contain", "include", "substantially consist of" and "consist only of".

1. Sulfur-containing compound The sulfur-containing compound of the present invention has the following formula (1) in the molecule
- (S) _m - (1)
(In formula (1), m represents a number of 1 or more)
and at least one second site containing a functional group F capable of interacting with other molecules and/or ions, wherein the second site is the first site It is covalently bonded to the sulfur of the site. That is, the sulfur-containing compound of the present invention has a first site and a second site covalently bonded to the first site in the molecule.

Such a sulfur-containing compound has excellent stability and is a novel sulfur polymer. In particular, as will be described later, the sulfur-containing compound of the present invention can form a polymer material having a so-called supramolecular structure by directly or indirectly interacting between molecules. It is expected to exhibit functions not found in polymers. In addition, the sulfur-containing compound of the present invention can have a supramolecular structure, and thus can form a polymeric material that appears to have a high molecular weight.

(first part)
The sulfur-containing compound can have one or more first sites in the molecule. When the sulfur-containing compound has two or more first moieties, for example, the first moieties are repeating structural units of the sulfur-containing compound. The first site can be called a "sulfur segment" because it is represented by the above formula (1).

In the above formula (1), 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, still more preferably 4 or more, and particularly preferably 5 or more. Further, the upper limit of m is not particularly limited, for example, it can be 10000 or less, preferably 5000 or less, more preferably 3000 or less, further preferably 1000 or less, and 500 or less. It is particularly preferred to have m can also be 10 or less. The value of m can be calculated by MALDI-TOF MS spectrum.

(Second part)
The sulfur-containing compound can have one or more second moieties in the molecule. When the sulfur-containing compound has two or more second moieties, for example, the second moieties are repeating structural units of the sulfur-containing compound.

The second site includes a functional group F (hereinafter sometimes simply referred to as "functional group F") capable of interacting with other molecules and/or ions. "Other molecules" as used herein can mean, for example, the sulfur-containing compounds of the present invention. That is, the sulfur-containing compound of the present invention can form intermolecular interactions via the functional group F. On the other hand, "ion" here can mean an ion of metal M, which will be described later.

In addition, the "interaction" as used herein can include, for example, 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 hydrogen bond, hydrophobic interaction, electrostatic interaction, dipole interaction, ionic bond , π-electron interaction, host-guest interaction, and the like. Among them, the non-covalent bond is preferably a hydrogen bond from the viewpoint of facilitating molecular design.

In the second site, the functional group F is not particularly limited as long as it can form the interaction. At least one functional group F is present in the second site, and two or more may be present. When the second site has multiple functional groups F, the multiple functional groups F may all be the same, or some or all of them may be different. Moreover, when the second site has a plurality of functional groups F, the types of interactions caused by the functional groups F may all be the same, or some or all of them may be different.

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" includes, for example, a functional group based on a polydentate ligand. When the functional group F is a functional group based on a polydentate ligand, the functional group F is likely to form an interaction due to the coordinate bond described above. More specifically, when the functional group F is a functional group based on a polydentate ligand, the functional group F is likely to form a coordinate bond with ions.

When the functional group F is a functional group based on a polydentate ligand, examples of the polydentate ligand include known bidentate ligands, tridentate ligands, hexadentate ligands and hexadentate ligands. A wide range of polydentate ligands exceeding Specific 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, Tetra or higher carboxylic acid compounds or derivatives thereof, imidazole compounds or derivatives thereof, diimidazole compounds or derivatives thereof, triazole compounds or derivatives thereof, tetratriazole compounds or derivatives thereof can be mentioned.

From the viewpoint of easy production of sulfur-containing compounds and easy formation of coordinate bonds, when the functional group F is a functional group based on a multidentate ligand, the functional group F is a functional group based on bipyridine or a derivative thereof. is preferably

When the functional group F possessed by the second site is a functional group based on a polydentate ligand, the second site can be formed by, for example, the polydentate ligand B described later. That is, the second site can be a structural unit based on the polydentate ligand B.

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" is a group having the property of non-covalent bonding of various types described above. can also The groups having the property of non-covalent bonding of the functional group F exclude functional groups based on the aforementioned polydentate ligands.

When the "functional group F capable of interacting with other molecules and/or ions" is a group having the property of non-covalent bonding, the functional group F can be, for example, a group having hydrogen bonding properties. Hereinafter, the functional group F having hydrogen-bonding properties is referred to as "hydrogen-bonding functional group F".

The functional group F having hydrogen bonding properties is not particularly limited, and for example, a wide range of known functional groups having hydrogen bonding properties can be mentioned. Specific examples of the functional group F having hydrogen bonding properties include an amide group, an amino group, a carboxyl group, a hydroxyl group, an isocyanate group, a thioisocyanate group, a carbamide-derived group, a ureido-derived group, a pyrimidine ring-derived group, and the like. can be mentioned.

When the functional group F possessed by the second site is a hydrogen-bonding functional group F, the second site can be formed by, for example, a hydrogen-bonding compound C described later. That is, the second site can be a structural unit based on the hydrogen-bonding compound C.

In the sulfur-containing compound according to the present invention, the second site can be composed only of the functional group F, or can be composed of a group containing the functional group F. For example, when the functional group F is a functional group based on a polydentate ligand, the second site preferably consists of the functional group F only.

(Sulfur-containing compound)
The sulfur-containing compound has at least one first site and at least one second site in the molecule.

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

The main chain type supramolecular sulfur polymer has a structure in which the second site is covalently bonded to one end of the first site (hereinafter abbreviated as "structure a"), and both ends of the first site to which the second site is covalently bonded (hereinafter abbreviated as “structure b”). Thus, backbone-type supramolecular sulfur polymers have one primary site and one or two secondary sites in the molecule.

When the main chain-type supramolecular sulfur polymer has the structure a, the group bonded to the end opposite to the end to which the second portion of the first portion is covalently bonded is not particularly limited, and a hydrogen atom , alkali metal ions such as sodium, and the like.

When the main-chain supramolecular sulfur polymer has the structure a, the type of the second site is not particularly limited as long as it has the functional group F. It is preferable to have at least one selected from the group consisting of binding functional groups F.

When the main chain-type supramolecular sulfur polymer has the structure b, the second sites at both ends can be the same, or can be of different types. The second sites at both ends are preferably the same from the viewpoint of ease of production and easy formation of a supramolecular structure due to interactions such as coordinate bonds, which will be described later.

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. It is preferable to have at least one selected from the group consisting of binding functional groups F.

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

When the sulfur-containing compound according to the present invention is a main chain type supramolecular sulfur polymer, the mass average molecular weight (Mw) is preferably 100 to 1,000,000, more preferably 500 to 100,000. It is preferably from 1,000 to 10,000. The weight average molecular weight (Mw) referred to in this specification is a value obtained by gel permeation chromatography (GPC) measurement.

The sulfur-containing compound according to the present invention can also have a structure other than the main chain type supramolecular sulfur polymer. Specifically, the sulfur-containing compound according to the present invention can also have, as a repeating unit, a structure in which the second portion is covalently bonded to one end of the first portion. Hereinafter, the sulfur-containing compound of this aspect is referred to as "side chain type supramolecular sulfur polymer".

A side chain type supramolecular sulfur polymer is formed by repeating a structure in which a first site (one end of a sulfur segment) is bonded to a second site. Therefore, when the first site is denoted as "M1" and the second site is denoted as "M2", the side chain type supramolecular sulfur polymer has (M1-M2) units as repeating structural units.

Since the side chain type supramolecular sulfur polymer has the (M1-M2) unit as a repeating structural unit, the side chain type supramolecular sulfur polymer molecule has at least the first site and the second site. Includes two or more. The second site contained in the side chain type supramolecular sulfur polymer molecule may be of one type alone, or may be of two or more different types.

The second site in the side chain type supramolecular sulfur polymer is usually present covalently bonded to the terminal sulfur atom of the first site.

In the 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. Among them, the functional group based on the above-mentioned multidentate ligand and the hydrogen-bonding functional group F It is preferable to have at least one selected from the group consisting of

The side chain type supramolecular sulfur polymer can be formed only with two or more first sites and two or more second sites, or two or more first sites unless the effects of the present invention are impaired. And it can also have structural units other than two or more second moieties. The side chain type supramolecular sulfur polymer preferably contains 70 mol% or more of the first site and the second site, more preferably 80 mol% or more, further preferably 90 mol% or more, and 95 mol % or more is particularly preferable.

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

The sulfur-containing compound according to the present invention, whether it is a main chain type supramolecular sulfur polymer or a side chain type supramolecular sulfur polymer, is usually a linear compound, and may have a branched structure as necessary. can.

2. Method for Producing Sulfur-Containing Compound 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 can be obtained by step 1 of obtaining sulfur segments by reacting a sulfur source and a metal source, and sulfur It can be produced by a production method comprising step 2 of obtaining a contained compound.

Step 1 is a step for producing a sulfur segment by reacting a sulfur source and a metal source.

The sulfur source used in step 1 is a raw material capable of giving a sulfur polymer. For example, the sulfur source is a raw material capable of providing the "-(S) _m -" site represented by the above formula (1). Therefore, the sulfur source may be sulfur alone or a compound containing a sulfur atom. The sulfur source preferably contains elemental sulfur in that it is easy to provide -(S) _m - sites.

Examples of simple sulfur include cyclic sulfur composed of sulfur atoms, and typically an eight-membered ring of sulfur can be used as a sulfur source. Such a sulfur source can be produced by a known method, or can be obtained from commercial products.

The sulfur source can also be, for example, a sulfur polymer. Such sulfur polymers can be produced by known methods, or can be obtained from commercial products.

In step 1, examples of metal sources include alkali metals and alkali metal compounds. The alkali metal is not particularly limited, and examples thereof include sodium, potassium, and lithium, with sodium being preferred. Examples of alkali metal compounds include sulfides of alkali metals, among which sodium sulfide is preferred. The alkali metal compound may be a hydrate.

The metal source is preferably an alkali metal compound, more preferably an alkali metal sulfide, and particularly preferably sodium sulfide, in that the reaction is simple and large-scale synthesis is possible.

In step 1, the method of reacting the sulfur source and the metal source is not particularly limited, and for example, a method of mixing the sulfur source and the metal source in a solvent can be mentioned. When a solvent is used in the reaction, its type is not particularly limited, and various organic solvents other than water can be used. When the metal source is an alkali metal compound, particularly an alkali metal sulfide, the reaction of step 1 preferably uses an aqueous solvent, particularly water. Further, when the metal source is an alkali metal, it is preferable to use an organic solvent in the reaction of step 1, and it is particularly preferable to use a polar solvent such as dimethylacetamide.

In step 1, the ratio of the sulfur source and the metal source used is not particularly limited. Mole.

The reaction temperature when reacting the sulfur source and the metal source in step 1 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 performed, for example, under an inert gas atmosphere such as nitrogen.

After the reaction in step 1, the reaction product obtained can be subjected to the next step 2 without purification treatment, etc., or the reaction product obtained in step 1 can be subjected to appropriate post-treatment as necessary. After performing, it can be subjected to the next step 2. Post-treatment is not particularly limited, and a wide range of known purification methods, separation methods, and the like can be employed. Examples thereof include a method of purifying the reaction product obtained in step 1 by filtration, and a method of separating the solid content by removing the solvent by drying treatment of the reaction product obtained in step 1.

The reactant obtained by step 1 above contains a sulfur segment. The sulfur segment is "-(S) _m - (m is 1 or more)" as represented by the above formula (1), and is a component that becomes the first site in the sulfur-containing compound of the present invention. be. Both ends of the sulfur segment are, for example, hydrogen atoms or metal salts (eg, sodium salts).

Step 2 is a step for obtaining a sulfur-containing compound by reacting the sulfur segment obtained in Step 1 with a compound having a functional group F. A compound having functional group F can be the second site in the resulting sulfur-containing compound.

In the compound having a functional group F, the functional group F is the same as described above. Therefore, as the functional group F, functional groups based on polydentate ligands and functional groups having hydrogen bonding properties can be mentioned.

Examples of compounds having a functional group F include various polydentate ligands. In this case, the resulting sulfur-containing compound is formed with, for example, a second site having a functional group F capable of coordinating.

The polydentate ligand as a compound having a functional group F is hereinafter referred to as "polydentate ligand B".

Examples of the multidentate ligand B include a wide range of known bidentate ligands, tridentate ligands, hexadentate ligands, and multidentate ligands exceeding hexadentate. pyridine compound or derivative thereof, bipyridine compound or derivative thereof, terpyridine compound or derivative thereof, carboxylic acid compound or derivative thereof, dicarboxylic acid compound or derivative thereof, tricarboxylic acid compound or derivative thereof, tetra- or higher carboxylic acid compound or derivative thereof, imidazole compounds or derivatives thereof, diimidazole compounds or derivatives thereof, triazole compounds or derivatives thereof, tetratriazole compounds or derivatives thereof. Bipyridine derivatives and terpyridine derivatives include, for example, structures in which at least one hydrogen atom in one or two or more pyridine rings out of a plurality of pyridine rings is substituted with another substituent. The type of the substituent is not particularly limited as long as it does not interfere with coordination bonding, and specific examples thereof include hydrocarbon groups (eg, having 1 to 10 carbon atoms).

Among them, the polydentate ligand B is preferably a compound capable of reacting with the terminal sulfur atom of the sulfur segment. As such a compound, a compound substituted with a halogen atom, a compound having an isocyanate group, a compound having an epoxy group, a compound having a carbonyl chloride, and the like are preferable. Specific examples of the polydentate ligand B include bipyridine having a halogen atom or a derivative thereof, terpyridine having a halogen atom or a derivative thereof, and typically 4-(Chloromethyl)-4'-methyl- 2,2'-bipyridyl, 4,4'-Bis(chloromethyl)-2,2'-bipyridyl and the like can be mentioned. Halogen atoms other than chlorine atoms may be used, but chlorine atoms are preferred from the viewpoint of reactivity.

In addition, specific examples of the polydentate ligand B include the compounds represented by B-1 to B-34 below.

When the multidentate ligand B is, for example, a bipyridine having a halogen atom or a derivative thereof, or a terpyridine having a halogen atom or a derivative thereof, in the reaction in step 2, the halogen atom is eliminated to form a sulfur atom at the end of the sulfur segment. can be bound to Therefore, when the multidentate ligand B has one halogen atom, the aforementioned backbone-type supramolecular sulfur polymer is produced, and such backbone-type supramolecular sulfur polymer usually has structure b. Moreover, when the polydentate ligand B has two halogen atoms, the aforementioned side chain type supramolecular sulfur polymer can be produced.

Examples of compounds having a functional group F include, in addition to the multidentate ligand B, compounds having a hydrogen-bonding functional group F. In this case, the resulting sulfur-containing compound is formed with, for example, a second site having a functional group F capable of hydrogen bonding.

A compound having a hydrogen-bonding functional group F is hereinafter referred to as a "hydrogen-bonding compound C". Hydrogen-bonding compound C does not have functional groups based on polydentate ligands.

As the hydrogen-bonding compound C, a wide range of known compounds having a functional group F having hydrogen-bonding properties can be cited. Specific examples of the functional group F having hydrogen bonding properties include an amide group, an amino group, a carboxyl group, a hydroxyl group, an isocyanate group, a thioisocyanate group, a carbamide-derived group, a ureido-derived group, a pyrimidine ring-derived group, and the like. can be mentioned.

The hydrogen-bonding compound C is preferably a compound that has a functional group F that has hydrogen-bonding properties, and that the functional group F can react with the terminal sulfur atom of the sulfur segment. Alternatively, the hydrogen-bonding compound C is a compound having a functional group F having hydrogen-bonding properties and having a group other than the functional group F capable of reacting with the terminal sulfur atom of the sulfur segment. is also preferred. Therefore, examples of the hydrogen-bonding compound C include compounds having a polycondensable group and compounds having a radically polymerizable double bond.

When the hydrogen-bonding compound C is a compound having a polycondensable group, examples of such polycondensable group include an amino group, a carboxyl group, a hydroxyl group, and an isocyanate group, among which an isocyanate group. (that is, the 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 sulfur segments. Of course, when the hydrogen-bonding compound C has a functional group F in addition to the polycondensable group, the functional group F can also function as the hydrogen-bonding functional group F. Therefore, when the hydrogen-bonding compound C is a compound having a polycondensable group, the compound may have at least two, preferably three or more hydrogen-bonding functional groups F in the molecule. may have 10 or less, preferably 8 or less, more preferably 5 or less functional groups F.

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

When the hydrogen-bonding compound C is a compound having a polycondensable group, in the reaction in step 2, the polycondensation reaction proceeds between the polycondensable group and the sulfur atom at the end of the sulfur segment. Therefore, when there is one polycondensable group in the hydrogen-bonding compound C, the aforementioned main-chain supramolecular sulfur polymer is produced, and such a main-chain supramolecular sulfur polymer usually has structures a and/or or has structure b, preferably structure b. Further, when the number of polycondensable groups in the hydrogen-bonding compound C is two, the aforementioned side chain type supramolecular sulfur polymer can be produced.

When the hydrogen-bonding compound C is a compound having a radically polymerizable group, the compound includes, in addition to the functional group F, radically polymerizable compounds such as an allyl group, an acryloyl group, a methacryloyl group, and a styryl group. .

When the hydrogen-bonding compound C is a compound having a radically polymerizable group, the compound represented by the following formula (C-3) can be typically mentioned.

When the hydrogen-bonding compound C is a compound having a radically polymerizable group, in the reaction in step 2, the radical polymerization reaction proceeds between the radically polymerizable group and the sulfur atom at the end of the sulfur segment. Therefore, when there is one radically polymerizable group in the hydrogen-bonding compound C, the main chain type supramolecular sulfur polymer described above is produced, and such main chain type supramolecular sulfur polymer usually has the structure b. . Moreover, when there are two radically polymerizable groups in the hydrogen-bonding compound C, the aforementioned side chain type supramolecular sulfur polymer can be produced.

In step 2, the method of reacting the sulfur segment obtained in step 1 with a compound having a functional group F (i.e., polydentate ligand B or hydrogen-bonding compound C) is not particularly limited. Among them, a method of mixing the sulfur segment obtained in step 1 and a compound having a functional group F can be mentioned.

For example, when the compound having a functional group F is a multidentate ligand B, it is preferable to employ an interfacial reaction. Specifically, a solution of multidentate ligand B dissolved in a solvent that phase separates from water is added to water in which sulfur segments are present, and a compound having a functional group F and multidentate ligand B are added. is reacted at the interface of each solvent phase. Examples of solvents that phase-separate from water include various non-aqueous organic solvents, such as halogen-based hydrocarbon solvents such as chloroform.

Further, when the compound having the functional group F is a hydrogen-bonding compound C, a method of adding the hydrogen-bonding compound C to an aqueous solvent in which sulfur segments are present can be used. Examples of aqueous solvents include water, alcohol compounds having 1 to 3 carbon atoms, amide solvents, and the like.

In step 2, the ratio of the compound having the functional group F to the sulfur segment obtained in step 1 is not particularly limited. For example, the amount of the compound having the functional group F is preferably used per 1 mol of the sulfur segment. is 0.1 to 20 mol, more preferably 2 to 3 mol. The compound having the functional group F used in step 2 can be one or two or more. For example, the polydentate ligand B and the hydrogen-bonding compound C can be used in combination.

In step 2, the temperature at which the sulfur segment and the compound having the functional group F are reacted is not particularly limited, and can be, for example, 0 to 200°C, preferably 10 to 170°C, 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 performed, for example, under an inert gas atmosphere such as nitrogen.

After the reaction in step 2, the target sulfur-containing compound can be obtained by performing appropriate purification treatment as necessary.

In addition, in the method for producing a sulfur-containing compound, the sulfur-containing compound produced in step 2 can be further reacted with a compound having a functional group F. Specifically, a new sulfur-containing compound can be generated by reacting the initially generated sulfur-containing compound with a compound having an additional functional group F. The compound with additional functional group F can be a different type of compound than the compound with functional group F to be reacted first.

3. Sulfur-Containing Polymeric Material The sulfur-containing polymeric material of the present invention can contain the sulfur-containing compounds of the present invention described above. In particular, in the sulfur-containing polymeric material of the present invention, at least two or more sulfur-containing compounds can form intermolecular interactions via the functional group F.

For example, if the functional group F in the second site of the sulfur-containing compound is a group based on a polydentate ligand, and the sulfur-containing polymeric material contains metal ions, the coordinate bond will cause the sulfur-containing compound can form intermolecular interactions. Specifically, a multidentate ligand present in a sulfur-containing compound coordinates to a metal ion, and the metal ion is coordinated to a multidentate ligand of another sulfur-containing compound. As a result, the molecules of the sulfur-containing compound form associations via the metal ions, forming a so-called supramolecular polymer (“coordination-bonded main chain-type supramolecular sulfur polymer” in FIG. 1 described later or in FIG. 10”) The aggregate can be easily disassembled by using a compound that breaks coordinate bonds, such as EDTA.

The metal ion to which the multidentate ligand coordinates is not particularly limited as long as it is a metal that can be coordinated by the multidentate ligand. Examples thereof include various transition metal ions. Ions of Cu, Fe, Co, Mn, Al, etc. Among them, divalent copper ions and the like are preferable.

Further, when the functional group F at the second site of the sulfur-containing compound is a functional group having hydrogen bonding properties, a hydrogen bond is generated by the functional group F between one sulfur-containing compound and another sulfur-containing compound, As a result, associations between molecules of the sulfur-containing compound are formed to form a so-called supramolecular polymer.

For example, when the sulfur-containing polymer material of the present invention contains a sulfur-containing compound having structure b in the main chain type supramolecular sulfur polymer described above, functional groups F at both ends of the sulfur-containing compound molecule and other sulfur-containing The functional group F of the compound molecule interacts directly or indirectly via the metal ion to form an aggregate. Then, the aggregates are successively associated with other sulfur-containing compounds through interactions similar to each other, whereby the sulfur-containing polymeric material can form a supramolecular structure. The sulfur-containing polymeric material can comprise structure a in addition to structure b, where sulfur-containing compounds of structure a are located at one or both ends of the supramolecular structure.

Further, when the sulfur-containing polymer material of the present invention contains the above-mentioned side chain type supramolecular sulfur polymer, the functional group F in the repeating structural unit of the sulfur-containing compound molecule and the repeating structural unit of another sulfur-containing compound molecule Direct or indirect interaction occurs between the functional groups F in the sulfur-containing polymeric material, whereby the sulfur-containing polymer material can form a supramolecular structure (“Hydrogen-bonded side chain-type supramolecular sulfur polymer ”).

As described above, the sulfur-containing polymer material of the present invention forms a supramolecular structure, so that it can appear to be a material with a high molecular weight. The apparent weight average molecular weight of the sulfur-containing polymeric material is preferably 200 to 1,000,000, more preferably 500 to 500,000, and preferably 1,000 to 100,000. More preferred.

The sulfur-containing polymer material of the present invention can be said to be a novel sulfur polymer that has never existed before, because associations between molecules of sulfur-containing compounds are easily formed. In addition, the sulfur-containing polymer material of the present invention is resistant to depolymerization due to the formation of associations between molecules of sulfur-containing compounds, is excellent in stability, and tends to have an apparent high molecular weight. Furthermore, the formation of aggregates between molecules of the sulfur-containing compound makes it easier for the sulfur segments to exhibit features compared to conventional sulfur polymers, improving various physical properties.

The sulfur-containing polymeric material can 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, antifungal agents, and lubricants. One or more of these additives may be contained in the water absorbent resin dispersion.

The sulfur-containing polymeric material may be, for example, solid, liquid such as paste, or a solution or dispersion. When the sulfur-containing polymeric material is solid, its shape is not particularly limited. It may have an ellipsoidal shape, a curved shape, or the like.

The sulfur-containing polymeric material of the present invention is excellent in stability and workability, so it can be used for various purposes. For example, the sulfur-containing polymeric material of the present invention can be suitably used for applications such as electronic members, battery materials, optical members, packaging materials, adhesive materials, and drug-carrying materials.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the embodiments of these examples.

(Example 1-1; Synthesis of LS-bpy)
According to the reaction scheme shown in FIG. 1, LS-bpy was synthesized by binding sites (second site) having functional groups F based on bipyridine sites to both ends of a sulfur segment (first site). First, sulfur (300 mg, 1.17 mmol) and Na ₂ S pentahydrate (295 mg, 1.76 mmol) were stirred in 2 mL of water at 25° C. for 24 hours to obtain a reactant, and then the reaction A sulfur solution was prepared by filtering the material. A solution of bpyCl (4-(Chloromethyl)-4'-methyl-2,2'-bipyridyl, 847 mg, 3.87 mmol) dissolved in 2 mL of chloroform was added to the resulting sulfur solution, and the mixture was stirred at room temperature (25°C). for 40 hours to allow the interfacial reaction to proceed. Then, after collecting and obtaining a chloroform layer, magnesium sulfate was added to the chloroform layer to dry it, followed by purification by column chromatography to obtain LS-bpy.

FIGS. 2(a) and (b) respectively show the results of ¹ H-NMR measurement and ¹³ C-NMR measurement of LS-bpy obtained in Example 1-1. The upper spectrum of both NMR measurements is bpy-Cl for comparison, and the lower spectrum is LS-bpy obtained in Example 1-1. From both NMR spectra, LS-bpy obtained in Example 1-1 shows that the proton g or carbon k of the methylene chain linked to sulfur is shifted upfield compared to Bpy-Cl. Recognize.

FIG. 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 n=3.0 (ie, the chain length m of the sulfur segment in the first site was 3).

From the above results, it was confirmed that the desired LS-bpy was synthesized.

(Example 1-2; Synthesis of LS-bpy)
According to the reaction scheme shown in FIG. 1, a polymeric material (a main-chain supramolecular sulfur polymer having coordinate bonds) was produced using LS-bpy obtained in Example 1-1. Specifically, LS-bpy (20 mg, 43 μmol) obtained in Example 1-1 and Cu(NO ₃ ) ₂ trihydrate (26 mg, 108 μmol) were mixed in 900 μL of acetonitrile at room temperature (25°C). After stirring for one day, the polymer material was obtained by drying under reduced pressure.

FIG. 4 shows the results of GPC measurement in CHCl ₃ of the polymer material obtained in Example 1-2. As a result, in the polymer material obtained in Example 1-2, a peak was observed on the higher molecular weight side than LS-bpy alone, the number average molecular weight (Mn) in terms of polyethylene glycol was 3700, and the weight average molecular weight (Mw ) was 4600 and the PDI was 1.26. This molecular weight was almost the same as the molecular weight of sulfur polymers reported so far (about 3000). In general, the equilibrium of supramolecules is biased toward dissociation under dilute conditions, so it is expected that polymers with molecular weights larger than those observed in this study are formed under high concentration conditions.

5(a) and (b) are test results for confirming that a coordination bond is formed between the bipyridine site (bpy site) in LS-bpy and Cu. -Vis spectrum measurement results. In this measurement, a sample was prepared by adding an appropriate amount of 0.99 mM Cu(NO ₃ ) _{2.3H 2} _O DMSO solution to a 23 μM LS-bpy DMSO solution, and the UV-Vis spectrum of this sample was measured. . In this UV-Vis spectrum, new peaks were observed at 302 nm and 510 nm, suggesting that LS-bpy has a structure in which LS-bpy and Cu are linked by coordinate bonds. We mixed LS-Bn (see scheme in FIG. 1) with Cu to see if this coordination bond formation occurred only at the bpy sites, but no new peaks were observed ((b ) see figure). This suggested that the polymer material obtained in Example 1-2 was linked by coordination bonds between the bpy sites and Cu. That is, a coordinate bond is formed between the methylated bipyridine-derived group (functional group F) in the LS-bpy molecule and Cu. It is presumed to have a structure in which groups derived from bipyridine are coordinated.

Since the polymer material obtained in Example 1-2 is formed by the coordinate bond between the bpy site and Cu, it is expected that the polymer can be decomposed by dissociating the coordinate bond. Therefore, a sample was prepared by adding an excessive amount of ethylenediaminetetraacetic acid (EDTA) to the polymeric material obtained in Example 1-2 in DMSO and stirring, and GPC measurement was performed on this sample. As a result, it was confirmed that the peak of the polymeric material disappeared, indicating that the polymeric material obtained in Example 1-2 could be easily decomposed by adding EDTA.

(Example 2-1; synthesis of sulfur-UPy compound)
According to the reaction scheme shown in FIG. 6, a sulfur-UPy compound formed by binding a site (second site) having a urea-derived group as a functional group F to both ends of a sulfur segment (first site) is synthesized. did. First, sulfur (375 mg, 1.47 mmol) was added to dry dimethylacetamide (30 mL), to which Na (83 mg, 3.62 mmol) was added, and the reaction was stirred at 70° C. for 7 hours under nitrogen atmosphere. Obtained. A ureidopyrimidinone having an isocyanate group (Upy-NCO, 944 mg) was added to the reactant, stirred at 70°C for 12 hours under a nitrogen atmosphere, and then returned to room temperature. The resulting precipitate was filtered off and dried under reduced pressure. By doing so, a sulfur-UPy compound was obtained.

(Example 2-2; Synthesis of sulfur-UPy compound)
According to the reaction scheme shown in FIG. 6, a sulfur-UPy compound formed by binding a site (second site) having a urea-derived group as a functional group F to both ends of a sulfur segment (first site) is synthesized. did. First, a solution was prepared by dissolving sulfur (133 mg, 0.59 mmol) and Na ₂ S 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 mixture was stirred at 40° C. for 12 hours to allow interfacial reaction to proceed. During this reaction, insoluble matter was generated between the aqueous layer and the chloroform layer, so the insoluble matter was separated by suction filtration and dried under reduced pressure to obtain a sulfur-UPy compound.

FIG. 7 shows the results of ¹ H-NMR measurement of the sulfur-UPy compounds obtained in Examples 2-1 and 2-2. The upper spectrum of this NMR measurement is Upy-NCO for comparison, the middle spectrum is the sulfur-UPy compound obtained in Example 2-1, and the lower spectrum is the sulfur- obtained in Example 2-2. UPy compound. From this NMR spectrum, a downfield shift of the region A (protons of the methylene chain bound to the NCO group) shown in the figure was observed in both of them as compared with UPy-NCO.

FIG. 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 (ie, the chain length m of the sulfur segment in the first site was about 2.1).

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

9(a) and (b) are test results for confirming whether groups derived from Upy-NCO in sulfur-UPy form hydrogen bonds. Specifically, (a) is IR Spectra, (b) shows the solid-state ¹ H-NMR spectrum. Peaks were observed at 3220 and 3145 cm ⁻¹ in the IR spectrum, and three peaks were observed at 10-14 ppm in the solid state ¹ H-NMR spectrum. These suggest that groups derived from Upy-NCO form hydrogen bonds. In addition, the sulfur-UPy obtained in Examples 2-1 and 2-2 was poorly soluble in chloroform, but easily dissolved in chloroform containing trifluoroacetic acid, which is known to break hydrogen bonds. Dissolved.

From the above results, it was found that the sulfur-UPy obtained in Examples 2-1 and 2-2 formed a polymer material consisting of aggregates formed by intermolecular hydrogen bonds.

(Example 3; Synthesis of Poly(LS-bpy))
According to the reaction scheme shown in FIG. 10, a structural unit formed by binding a site (second site) having a functional group F based on a bipyridine site to one end of a sulfur segment (first site) is used as a repeating unit. Poly(LS-bpy) was synthesized. First, sulfur (300 mg, 1.17 mmol) and Na ₂ S pentahydrate (295 mg, 1.76 mmol) were stirred in 2 mL of water at 25° C. for 24 hours to obtain a reactant, and then the reaction A sulfur solution was prepared by filtering the material. 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 to the resulting sulfur solution, and the mixture was cooled to room temperature. The mixture was stirred at (25° C.) for 40 hours to allow the interfacial reaction to proceed. Then, after collecting and obtaining a chloroform layer, magnesium sulfate was added to the chloroform layer to dry it, followed by purification by column chromatography to obtain Poly(LS-bpy).

11(a) and (b) show the results of ¹ H-NMR measurement and ¹³ C-NMR measurement of Poly(LS-bpy) obtained in Example 3, respectively. The upper spectrum of both NMR measurements is Bpy-diCl for comparison, and the lower spectrum is Poly(LS-bpy) obtained in Example 3. From the ¹ H-NMR spectrum, Poly(LS-bpy) obtained in Example 3 exhibits an upfield shift of proton d of the sulfur-linked methylene chain and broadening of all protons compared to Bpy-diCl. conversion was confirmed. The ¹³ C-NMR spectrum confirmed the upfield shift of the sulfur-linked methylene chain carbon f. Since these results were similar to those of LS-bpy obtained in Example 1-1, synthesis of the desired Poly(LS-bpy) was strongly suggested.

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

FIG. 13 shows the results of GPC measurement in DMSO of Poly(LS-bpy) obtained in Example 3. From this result, the molecular weight is calculated as polyethylene glycol, the number average molecular weight is 1900, and the weight average molecular weight is 1,900. 2400, with a PDI of 1.26.

From the above results, it was confirmed that the desired Poly (LS-bpy) was synthesized.

In addition, UV-Vis spectroscopy was performed to confirm the formation of a coordinate bond between the bipyridine site (bpy site) in Poly(LS-bpy) and Cu. In this measurement, a sample was prepared by adding an appropriate amount of 1.16 mM Cu(NO ₃ ) ₂ .3H ₂ O DMSO solution to 3.81 μM Poly(LS-bpy) DMSO solution. Vis spectra were measured. In this UV-Vis spectrum, a new peak was observed at 470 nm, suggesting the formation of a polymeric material having a structure in which the bpy sites of Poly (LS-bpy) are linked to Cu via coordinate bonds. .

At the bottom of the GPC results shown in FIG. 13, the GPC measurement results of a polymer material having a structure in which the bpy sites of Poly(LS-bpy) are linked to Cu by coordination bonds are shown. Remarkably, the polymer material had a peak on the higher molecular weight side than Poly(LS-bpy) alone. The highest molecular weight peak had a number average molecular weight of 22,000, a weight average molecular weight of 46,000, and a PDI of 2.17 in terms of polyethylene glycol. These molecular weights are much higher than the molecular weights of sulfur polymers reported so far (about 3000), and by introducing the concept of supramolecules into sulfur polymers, we have achieved high molecular weight sulfur polymers. That is, a coordinate bond is formed between the methylated bipyridine-derived group (functional group F) in the Poly(LS-bpy) molecule and Cu, and this Cu has another Poly(LS-bpy) It is presumed to have a structure in which methylated bipyridine-derived groups in the molecule are coordinated.

(Example 4; Synthesis of Poly(LS-BnNHCOS))
According to the reaction scheme shown in FIG. 14, a structural unit formed by binding a site (second site) having an isocyanate-derived group as a functional group F to one end of a sulfur segment (first site) is used as a repeating unit. Poly(LS-BnNHCOS) was synthesized. First, sulfur (2.58 g, 10.1 mmol) and Na ₂ S pentahydrate (3.40 g, 20.2 mmol) were added to 60 mL of water at 25° C., stirred for 24 hours, filtered, The resulting filtrate was freeze-dried to obtain a solid (a polymer consisting of -(S) _m -segments). After dissolving this solid (524 mg, 3.01 mmol) in dehydrated DMF (60 mL), m-xylylene diisocyanate (BndiNCO, 472 μL, 3.01 mmol) was added, and the mixture was stirred at 25° C. for 20 hours under a nitrogen atmosphere. A reactant was obtained by stirring. After filtering the resulting reactant, DMF was distilled off to obtain a pale orange solid.

FIG. 15 shows the FT-IR spectrum of the resulting pale orange solid. In this FT-IR spectrum, the isocyanate-derived peak near 2250 cm ⁻¹ observed in the raw material BndiNCO disappeared, and −C═O at 1620 cm ⁻¹ , −NH at 3310 cm ⁻¹ , and C at 690 cm ⁻¹ . A peak derived from -S was observed. These results suggested that the monomer BndiNCO was consumed in the reaction and the reaction proceeded.

FIG. 16 shows the results of ¹ H-NMR measurement of the pale orange solid obtained in Example 4. 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. Broadening of all protons was observed from this NMR spectrum compared to BndiNCO. The results were similar for LS-bpy and Poly(LS-bpy). From the above, it was found that the desired Poly(LS-BnNHCOS) was synthesized.

FIG. 17 shows the results of GPC measurement of Poly(LS-BnNHCOS) in DMSO. In this GPC measurement, Poly(LS-BnNHCOS) has a peak on the higher molecular weight side than BndiNCO. , PDI was found to be 1.16. This molecular weight is much higher than the molecular weight of sulfur polymers reported so far (about 3000), and these results also indicate that BndiNCO reacts through polycondensation of —(S) _m — with BndiNCO. As a result, it was found that the desired Poly (LS-BnNHCOS) was synthesized.

The obtained Poly(LS-BnNHCOS) was poorly soluble in chloroform, but easily dissolved in chloroform containing trifluoroacetic acid. As described above, it was easily dissolved in chloroform in the presence of trifluoroacetic acid, so Poly(LS-BnNHCOS) has hydrogen bonds formed between side chains by thioisocyanate, and these hydrogen bonds are formed by trifluoroacetic acid. presumed to have been dissolved. That is, it was suggested that Poly(LS-BnNHCOS) is a hydrogen bond type side chain type supramolecular sulfur polymer.

(Example 5)
According to the reaction scheme of FIG. 18, Poly (Poly ( S-Upy) was synthesized. Poly(S -Upy).

FIG. 19 shows the results of GPC measurement of Poly(S-Upy) in DMSO and chloroform. As a result, a high molecular weight peak was confirmed in all measurement solvents, indicating that the desired Poly (S-Upy) was obtained. In this measurement, Poly(S-Upy) generated a large amount of insoluble matter in DMSO and chloroform. This indicates that hydrogen bonding was formed between the polymers, that is, Poly(S-Upy) forms a polymeric material with a supramolecular structure induced by hydrogen bonding. It was suggested.

(Method for measuring mass average molecular weight)
The mass average molecular weight (Mw) was measured using a gel permeation chromatograph (GPC) device under the following measurement conditions.
(Measurement condition)
・Measurement device name: Tosoh DP-8020 pump, CO-8020 column oven, UV-8020 ultraviolet detector, RI-8020 refractive-index detector
・Column: 2 TSKgel GMHHR-M ・Column temperature: 40°C
- Solvent _CHCl3 or DMSO
Flow rate: Po 1.0 mL/min when using CHCl ₃ as solvent, 3.0 mL/min when using DMSO
Standard samples: polystyrene standards when CHCl3 was used as solvent _, polyethylene glycol standards when DMSO was used

Claims

A sulfur-containing compound,
Formula (1) below in the molecule
- (S) m - (1)
(In formula (1), m represents a number of 1 or more)
A first portion represented by
at least one second site containing a functional group F capable of interacting with other molecules and/or ions;
A sulfur-containing compound, wherein the second portion is covalently bonded to the sulfur of the first portion.
2. The sulfur-containing compound according to claim 1, wherein said interaction is at least one selected from the group consisting of non-covalent bonds and coordinate bonds.
2. A sulfur-containing compound according to claim 1, wherein said functional group F is a functional group based on a polydentate ligand.
2. The sulfur-containing compound according to claim 1, wherein said functional group F has hydrogen bonding properties.
The sulfur-containing compound according to any one of claims 1 to 4, which is a molecule having a structure in which the second site is covalently bonded to one or both ends of the first site.
5. The sulfur-containing compound according to any one of claims 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.
comprising a sulfur-containing compound according to any one of claims 1 to 4,
A sulfur-containing polymeric material in which at least two or more sulfur-containing compounds form an intermolecular interaction via the functional group F.