Production method for sulfur-containing polymer compound and sulfur-containing polymer compound

Abstract

Provided are: a production method that makes it possible to produce a sulfur-containing polymer compound using a simple method; and a sulfur-containing polymer compound.　This production method for a sulfur-containing polymer compound comprises a step for reacting a sulfur compound with a brominated organic compound to obtain a sulfur-containing polymer compound, wherein the sulfur compound is at least one selected from the group consisting of chain sulfur polymers and metal sulfide compounds, and the brominated organic compound is a hydrocarbon compound having two or more bromo groups per molecule.

Description

Method for producing sulfur-containing polymer compound and sulfur-containing polymer compound

[0001] The present invention relates to a method for producing a sulfur-containing polymer compound and the sulfur-containing polymer compound.

[0002] Sulfur-containing polymers can be synthesized using sulfur, which is said to be disposed of on land at a rate of 7 million tons per year, as a raw material. Furthermore, they have high properties not found in carbon polymers, making them a new material that is attracting attention from both environmental and performance perspectives.

[0003] From this viewpoint, various methods for producing sulfur-containing polymers have been investigated in recent years. In particular, sulfur polymers (-(S) ｎ Since sulfur-containing polymers are unstable due to decomposition at room temperature and are insoluble in solvents and have poor processability, there is an urgent need to establish a technology for efficiently producing sulfur-containing polymers.

[0004] Non-Patent Document 1 discloses various methods for producing sulfur-containing polymers, such as a method for obtaining a sulfur-containing polymer compound by reacting a chlorinated organic compound with a sulfur source, and a method for obtaining a sulfur-containing polymer compound by reacting a thiol compound with a sulfur source.

[0005] Progress in Polymer Science 58 (2016) 90-125

[0006] However, the method for producing a sulfur-containing polymer compound as described in Non-Patent Document 1 requires the use of a large amount of an organic solvent and heating to a high temperature, which tends to make the process complicated and results in large energy consumption. From the perspective of the recent SDGs, there is a strong demand for a method for producing a sulfur-containing polymer compound more simply and with a small environmental impact.

[0007] The present invention has been made in view of the above, and an object of the present invention is to provide a production method that allows a sulfur-containing polymer compound to be produced in a simple manner, and the sulfur-containing polymer compound.

[0008] As a result of extensive research into achieving the above object, the present inventors have found that the above object can be achieved by reacting a specific sulfur compound with a specific brominated organic compound, thereby completing the present invention.

[0009] That is, the present invention encompasses, for example, the subject matter described in the following items. Item 1: A method for producing a sulfur-containing polymer compound, comprising a step of reacting a sulfur compound with a brominated organic compound to obtain a sulfur-containing polymer compound, wherein the sulfur compound is at least one selected from the group consisting of linear sulfur polymers and metal sulfide compounds, and the brominated organic compound is a hydrocarbon compound having two or more bromo groups in the molecule. Item 2: The linear sulfur polymer is a compound represented by the following formula (1): Y-(S) ｎ Item 3. The method for producing a sulfur-containing polymer compound according to Item 1, wherein the sulfur-containing polymer compound is a compound represented by the following formula (2a): Br—(CH ２ ) ｍ -Br (2a) (wherein m is a number of 1 or more), or a compound represented by the following formula (2b): Br-R １ -Br (2b) (In the above formula (2b), R １ represents an alkylene group having one or more bromo groups), and the following formula (2c): Br—R ２ -Br (2c), (in the above formula (2c), R ２ Item 5: The method for producing a sulfur-containing polymer compound according to any one of items 1 to 3, wherein the sulfur-containing polymer compound is one compound selected from the group consisting of compounds represented by the following formula (3): ｎ - (CH ２ ) ｋItem 6: The method for producing a sulfur-containing polymer compound according to any one of claims 1 to 3, which has a structural unit represented by the following formula (4)-(S): ｎ - (CH ２ ) ａ Item 7: A sulfur-containing polymer compound having a structural unit represented by the following formula (5)-(S): ｎ - (CH ２ ) ｂ - (5) (in the formula (5), n is a number of 1 or more, and b is a number of 1 or more), and a sulfur-containing polymer compound having a crosslinked structure.

[0010] The production method of the present invention makes it possible to produce a sulfur-containing polymer compound in a simple manner.

[0011] 1 shows a scheme of a synthesis reaction of a sulfur-containing polymer compound carried out in Example 1a, and the results of Raman measurement of the obtained sulfur-containing polymer compound. FIG. 2 shows a scheme of a synthesis reaction of a sulfur-containing polymer compound carried out in Example 2a, and the results of Raman measurement of the obtained sulfur-containing polymer compound. FIG. 3 shows a scheme of a synthesis reaction of a sulfur-containing polymer compound carried out in Example 2b, and the results of Raman measurement of the obtained sulfur-containing polymer compound. FIG. 4 shows a scheme of a synthesis reaction of a sulfur-containing polymer compound carried out in Example 2c, and the results of Raman measurement of the obtained sulfur-containing polymer compound. FIG. 5 shows a scheme of a synthesis reaction of a sulfur-containing polymer compound carried out in Example 2d, and the results of Raman measurement of the obtained sulfur-containing polymer compound. FIG. 6 shows a scheme of a synthesis reaction of a sulfur-containing polymer compound carried out in Example 3a. FIG. 7 shows a scheme of a synthesis reaction of a sulfur-containing polymer compound carried out in Example 4a, and the results of Raman measurement of the obtained sulfur-containing polymer compound. １ 1H-NMR spectrum measurement results. １1H-NMR spectrum measurement results. １ 1H-NMR spectrum measurement results. １ 1 shows the results of H-NMR spectrum measurement. １ 1H-NMR spectrum measurement results. １ 1H-NMR spectrum measurement results and an external photograph. １ 1H-NMR spectrum measurement results and an appearance photograph. １ 1H-NMR spectrum measurement results and an external appearance photograph. １ 1A and 1B show the results of H-NMR spectrum measurement and an external photograph. 1B shows a scheme of the synthesis reaction of a sulfur-containing polymer compound carried out in Example 7a. 1C shows a scheme of the synthesis reaction of a sulfur-containing polymer compound carried out in Example 8a. 1D shows a scheme of the synthesis reaction of a sulfur-containing polymer compound carried out in Example 9a, and the results of Raman measurement of the obtained sulfur-containing polymer compound. 1E shows a scheme of the synthesis reaction of a sulfur-containing polymer compound carried out in Example 10a, and the results of Raman measurement of the obtained sulfur-containing polymer compound. 1F shows a scheme of the synthesis reaction of a sulfur-containing polymer compound carried out in Example 11a, and the results of Raman measurement of the obtained sulfur-containing polymer compound. 1G shows a scheme of the synthesis reaction of a sulfur-containing polymer compound carried out in Example 12a, and the results of Raman measurement of the obtained sulfur-containing polymer compound. １1 shows a scheme of a synthesis reaction of a sulfur-containing polymer compound carried out in Example 13a, and a result of Raman spectroscopy of the obtained sulfur-containing polymer compound.

[0012]

[0023] In the present specification, the terms "contain" and "comprise" include the concepts of "contain," "comprise," "consist essentially of," and "consist only of."

[0013] 1. Method for Producing a Sulfur-Containing Polymer Compound The production method of the present invention is a method for producing a sulfur-containing polymer compound, and includes a step of reacting a sulfur compound with a brominated organic compound to obtain a sulfur-containing polymer compound. Hereinafter, this step will be referred to as "Step 1," and the sulfur-containing polymer compound obtained in Step 1 will be referred to as "sulfur-containing polymer compound A."

[0014] The sulfur compound used in step 1 is at least one selected from the group consisting of linear sulfur polymers and metal sulfide compounds, and the brominated organic compound is a hydrocarbon compound having two or more bromo groups in the molecule.

[0015] The production method of the present invention can produce a sulfur-containing polymer compound in a simple manner. In particular, compared with conventional production methods for sulfur-containing polymer compounds, the production method of the present invention can produce a sulfur-containing polymer compound at a low temperature (e.g., room temperature) and does not necessarily require the use of an organic solvent, which reduces the environmental load, reduces energy consumption, and does not complicate the process.

[0016] Furthermore, in the production method of the present invention, the structure of the sulfur-containing polymer compound to be obtained is determined depending on the raw materials used, particularly the brominated organic compound, and therefore sulfur-containing polymer compounds having various molecular structures can be obtained.

[0017] (Sulfur Compound) The sulfur compound used in step 1 is a raw material for obtaining the sulfur-containing polymer compound A. In particular, in step 1, at least one sulfur compound selected from the group consisting of a linear sulfur polymer and a metal sulfide compound is used as the sulfur compound.

[0018] The linear sulfur polymer is a polymer composed of sulfur atoms (S) and has, for example, a linear structure.

[0019] The linear sulfur polymer may be, for example, a polymer represented by the following formula (1): Y-(S) ｎ A compound represented by —Y (1) is preferred.

[0020] In the formula (1), n ​​is a number of 1 or more, and two Ys may be the same or different and represent a hydrogen atom or an alkali metal.

[0021] In particular, in the linear sulfur polymer, both of the two Y's are preferably alkali metals, more preferably sodium, in view of excellent reactivity.

[0022] In the formula (1), n ​​is not particularly limited as long as it is a number of 1 or more. For example, n can be a number exceeding 1, and is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and particularly preferably 5 or more. The upper limit of n is not particularly limited, and can be, for example, 10,000 or less, preferably 5,000 or less, more preferably 3,000 or less, even more preferably 1,000 or less, and particularly preferably 500 or less. Furthermore, n may be 100 or less, 50 or less, or 10 or less. The value of n can be calculated by MALDI-TOF MS spectrum measurement of the linear sulfur polymer.

[0023] The linear sulfur polymer can be obtained by, for example, a known production method, for example, by reacting a sulfur source with a metal source.

[0024] The sulfur source may be, for example, elemental sulfur or a compound containing a sulfur atom. The sulfur source is preferably elemental sulfur, since it is easy to obtain a linear sulfur polymer. Examples of elemental sulfur include cyclic sulfur composed of sulfur atoms, and a representative example is an 8-membered sulfur ring (S ８Such sulfur sources can be produced by known methods or can be obtained commercially.

[0025] Examples of the metal source include alkali metals and alkali metal compounds. The alkali metal is not particularly limited, and examples include sodium, potassium, and lithium, with sodium being preferred. Examples of alkali metal compounds include alkali metal sulfides, with sodium sulfide being preferred. The alkali metal compound may be a hydrate. In terms of the ease of reaction and the possibility of mass synthesis, the metal source is preferably an alkali metal compound, more preferably an alkali metal sulfide, and particularly preferably sodium sulfide, from the viewpoint of the ease of reaction and the possibility of mass synthesis.

[0026] The method for reacting the sulfur source and the metal source is not particularly limited, and examples thereof include a method in which the sulfur source and the metal source are mixed in a solvent. When a solvent is used in the reaction, the type is not particularly limited, and various organic solvents, including water, can be used. When the metal source is an alkali metal compound, particularly an alkali metal sulfide, it is preferable to use an aqueous solvent, and water is particularly preferred. When the metal source is an alkali metal, it is preferable to use an organic solvent, and it is particularly preferred to use a polar solvent such as dimethylacetamide.

[0027] In the reaction of the sulfur source and the metal source, the ratio of the two to be used is not particularly limited. ｎ In terms of ease of controlling the chain length of the - moiety, i.e., the value of n, the amount of the metal source used per mole of the sulfur source is preferably 0.1 to 20 moles, more preferably 0.5 to 10 moles, even more preferably 0.8 to 8 moles, and particularly preferably 1 to 3 moles.

[0028] The reaction temperature when reacting the sulfur source with the metal source 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.

[0029] The sulfur compound used in step 1 may be the linear sulfur polymer or a metal sulfide compound as described above. As the metal sulfide compound, for example, a wide variety of known metal sulfide compounds can be used in the present invention.

[0030] Among these, sodium sulfide is preferred as the metal sulfide compound because of its high reactivity and easy availability.

[0031] The metal sulfide compound may be a hydrate. For example, sodium sulfide may be sodium sulfide pentahydrate (Na ２ S.5H ２ O) and the like.

[0032] The metal sulfide compound can be produced by a known method, or can be obtained from a commercial product.

[0033] (Brominated Organic Compound) The brominated organic compound used in step 1 is a hydrocarbon compound having at least two bromo groups in the molecule. The number of bromo groups in the brominated organic compound is preferably 5 or less, more preferably 4 or less, and may be 2 or 3. When the brominated organic compound has 2 bromo groups, the sulfur-containing polymer compound A obtained in step 1 can have a linear structure, and when the brominated organic compound has 3 or more bromo groups, the sulfur-containing polymer compound A obtained in step 1 can have a crosslinked structure (i.e., a three-dimensional network structure).

[0034] The brominated organic compound is not limited to a specific type as long as it is a hydrocarbon compound having at least two bromo groups in the molecule, and a wide variety of known bromo group-containing hydrocarbon compounds can be used. For example, a compound having two or more bromo groups in the molecule and an alkylene group can be used. In this case, it is preferable that the alkylene group has bromo groups attached to both ends.

[0035] In particular, the brominated organic compound is represented by the following formula (2a): Br—(CH ２ ) ｍ -Br (2a), a compound represented by the following formula (2b): Br-R １ —Br (2b), and the following formula (2c): Br—R ２ It is preferable that the compound is one compound selected from the group consisting of compounds represented by —Br (2c).

[0036] Here, in the formula (2a), m is a number of 1 or more.

[0037] In the formula (2b), R １ represents an alkylene group having one or more bromo groups.

[0038] In the formula (2c), R ２ represents a divalent group having an unsaturated ring which may contain a hetero atom.

[0039] In the formula (2a), the upper limit of m is not particularly limited, and taking into consideration ease of availability, for example, it is preferably 30 or less, more preferably 24 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 12 or less. m is preferably an integer.

[0040] Specific examples of the brominated organic compound represented by the formula (2a) include dibromomethane, 1,2-dibromoethane, 1,3-dibromopropane, 1,4-dibromobutane, 1,6-dibromohexane, 1,8-dibromooctane, 1,10-dibromodecane, and 1,12-dibromododecane.

[0041] In the formula (2b), R １That is, the alkylene group having one or more bromo groups preferably has 2 or more carbon atoms, more preferably 3 or more carbon atoms, and preferably 30 or less, more preferably 24 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 12 or less. １ That is, the alkylene group having one or more bromo groups may be linear, branched, or cyclic.

[0042] Specific examples of the brominated organic compound represented by formula (2b) include 1,2,3-tribromopropane, 1,1,2-tribromoethane, 1,1,2,2-tetrabromoethane, 1,2,3,4-tetrabromobutane, 1,2,5,6-tetrabromohexane, 1,2,5,6-tetrabromocyclooctane, and pentaerythrityl tetrabromide.

[0043] In the formula (2c), R ２ When R is a divalent group having an unsaturated ring that does not have a heteroatom, the unsaturated ring may be a group in which two hydrogen atoms have been removed from an aromatic hydrocarbon ring, and a specific example thereof may be an arylene group. The arylene group may be a group in which one hydrogen atom has been removed from an aryl group. Examples of such aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl. Therefore, examples of the arylene group include a phenylene group and a naphthylene group, and among these, a phenylene group is preferred. ２ is a divalent group having an arylene group, the divalent group may consist of only the arylene group, or other substituents may be bonded to the arylene group. Examples of other substituents include -(CH ２ ) ｍ - (m is the same as in formula (2a)), or R defined in formula (2b). １ may be.

[0044] In the formula (2c), R ２When is a divalent group having an unsaturated ring with a heteroatom, such unsaturated ring can be a group in which two hydrogen atoms have been removed from an aromatic heterocycle, i.e., a heteroarylene group. The heteroarylene group can be a group in which one hydrogen atom has been removed from a heteroaryl group. Examples of such heteroaryl groups include monocyclic aromatic heterocyclic groups (e.g., 5- or 6-membered monocyclic aromatic heterocyclic groups).

[0045] Examples of the "5- or 6-membered monocyclic aromatic heterocyclic group" include pyrrolyl (e.g., 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl), furyl (e.g., 2-furyl, 3-furyl), thienyl (e.g., 2-thienyl, 3-thienyl), pyrazolyl (e.g., 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl), imidazolyl (e.g., 1-imidazolyl, 2-imidazolyl, 4-imidazolyl), isoxazolyl (e.g., 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl), oxazolyl (e.g., 2-oxazolyl, 4-oxazolyl, 5-oxazolyl), isothiazolyl (e.g., 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl), thiazolyl Examples of heteroarylene groups include aryl (e.g., 2-thiazolyl, 4-thiazolyl, 5-thiazolyl), triazolyl (e.g., 1,2,3-triazol-4-yl, 1,2,4-triazol-3-yl), oxadiazolyl (e.g., 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl), thiadiazolyl (e.g., 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl), tetrazolyl, pyridyl (e.g., 2-pyridyl, 3-pyridyl, 4-pyridyl), pyridazinyl (e.g., 3-pyridazinyl, 4-pyridazinyl), pyrimidinyl (e.g., 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl), pyrazinyl, and the like. Preferred examples of heteroarylene groups include groups in which one hydrogen atom has been removed from a pyridyl group.

[0046] R ２ is a divalent group having a heteroarylene group, the divalent group may consist of only the heteroarylene group, or other substituents may be bonded to the heteroarylene group. Examples of other substituents include -(CH２ ) ｍ - (m is the same as in formula (2a)), or R defined in formula (2b). １ may be.

[0047] The compound represented by the formula (2c) is α,α'-dibromo-p-xylene (i.e., R ２ Ga-CH ２ -C ６ H ４ -CH ２ - (two CH ２ is attached at the para position), and another example is 2,6-bis(bromomethyl)pyridine (i.e., R ２ At the 2nd and 6th positions of the pyridine, CH ２ and the like.

[0048] When the brominated organic compound represented by the formula (2a) is used, the sulfur-containing polymer compound A obtained in step 1 can have a linear structure, and when the brominated organic compound represented by the formula (2b) is used, the sulfur-containing polymer compound A obtained in step 1 can have a crosslinked structure (i.e., a three-dimensional network structure).

[0049] The brominated organic compound may be in a solid state such as a powder or in a liquid state at room temperature (e.g., 25°C), and is preferably in a liquid state in terms of facilitating the reaction of step 1. When the brominated organic compound is in a solid state such as a powder at room temperature (e.g., 25°C), it is preferably used in the form of a solution by dissolving it in a solvent or the like described below, or it is also preferably used as a solution in which the brominated organic compound in a solid state is dissolved in the brominated organic compound in a liquid state.

[0050] (Step 1) In step 1, the sulfur compound is reacted with the brominated organic compound to produce the target sulfur-containing polymer compound A.

[0051] The method for reacting the sulfur compound with the brominated organic compound is not particularly limited. For example, a method of reacting the sulfur compound with the brominated organic compound in a solvent can be employed. From the viewpoint of easily increasing the reactivity of the two, the reaction between the sulfur compound and the brominated organic compound is preferably carried out at an interface. Specifically, a solution 1 in which the sulfur compound is dissolved and a raw material containing the brominated organic compound are prepared, and the interface reaction can be carried out using these. Therefore, it is preferable that the solution 1 and the raw material containing the brominated organic compound are phase-separated from each other (are not dissolved in each other).

[0052] Examples of the solvent for preparing the solution 1 include water and aqueous solvents such as alcohol compounds, and also include polar solvents such as dimethylacetamide and acetonitrile. Of these, the solvent for preparing the solution 1 is preferably water.

[0053] The concentration of Solution 1 is not particularly limited and can be, for example, 0.1 to 500 g / L, preferably 0.5 to 300 g / L, more preferably 1 to 200 g / L, and even more preferably 2 to 100 g / L. The concentration of Solution 2 is not particularly limited and can be, for example, 0.1 to 500 g / L, more preferably 0.2 to 300 g / L, and even more preferably 0.5 to 200 g / L.

[0054] The raw material containing the brominated organic compound may not contain a solvent if the brominated organic compound is in a liquid state, or the raw material containing the brominated organic compound may contain a solvent regardless of whether the brominated organic compound is in a liquid state or not. Such a solvent is preferably an organic solvent that undergoes phase separation from the solvent in Solution 1, and examples thereof include hydrocarbon solvents such as benzene, toluene, xylene, and hexane; ketone solvents such as acetone, methyl ethyl ketone, and isophorone; alcohol solvents such as tert-butyl alcohol, benzyl alcohol, phenoxyethanol, and phenylpropylene glycol; halogenated hydrocarbon solvents such as methylene chloride and chloroform; ether solvents such as 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane, and anisole; ester solvents such as ethyl acetate, propyl acetate, ethyl carbitol acetate, and butyl carbitol acetate; amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide; and carbonate solvents such as dimethyl carbonate, diethyl carbonate, and propylene carbonate.

[0055] In the reaction between the sulfur compound and the brominated organic compound, the ratio of the two compounds to be used is not particularly limited. For example, 0.05 to 10 moles of the brominated organic compound can be used per mole of the sulfur compound. In the production method of the present invention, the brominated organic compound is preferably used in an amount of 0.1 to 8 moles, more preferably 0.2 to 5 moles, even more preferably 0.25 to 3 moles, and particularly preferably 0.3 to 2.5 moles, per mole of the sulfur compound. Therefore, even in the case of an interfacial reaction, the amount of the brominated organic compound used per mole of the sulfur compound can be within the above-mentioned range.

[0056] When an interfacial reaction is carried out, it can be carried out, for example, by a method similar to that of a known interfacial reaction. In this interfacial reaction, a catalyst can also be used as needed. As the catalyst, for example, a phase transfer catalyst conventionally used in interfacial reactions can be used, and examples thereof include ammonium salts having a long-chain alkyl group, such as hexadecyltrimethylammonium bromide. The amount of catalyst used is not particularly limited, and can be the same amount as in conventional interfacial reactions. Usually, a phase transfer catalyst can be used in a so-called catalytic amount.

[0057] The phase transfer catalyst may be contained in solution 1 or may be contained in the raw material containing the brominated organic compound.

[0058] The method for reacting the sulfur compound with the brominated organic compound may be a reaction form other than the interfacial reaction, and for example, a method in which the reaction between the sulfur compound and the brominated organic compound is carried out in solvent A. The type of solvent A is not particularly limited, and examples thereof include the same type of solvent as the solvent used to prepare solution 1, and also the same type of solvent as the solvent contained, if necessary, in the raw material containing the brominated organic compound.

[0059] In step 1, the reaction temperature between the sulfur compound and the brominated organic compound is, for example, 60°C or lower, preferably 50°C or lower, more preferably 40°C or lower, even more preferably 35°C or lower, and particularly preferably 30°C or lower. The reaction temperature between the sulfur compound and the brominated organic compound may be room temperature (e.g., 25°C). The lower limit of the reaction temperature can be adjusted within a range in which the progress of the reaction is not inhibited, and is, for example, 0°C or higher, preferably 15°C or higher. The reaction time can be appropriately set depending on conditions such as concentration and temperature.

[0060] In step 1, after the reaction between the sulfur compound and the brominated organic compound is completed, the reaction product can be separated and obtained by an appropriate method. For example, after the reaction is completed, the reaction product can be separated and obtained by combining one or more appropriate means such as filtration, centrifugation, distillation, drying, etc. In the interfacial reaction as described above, insoluble matter is generated at the interface, and the reaction product can be obtained by treating this with the appropriate means.

[0061] The product obtained by the reaction in step 1 is the target sulfur-containing polymer compound A. The obtained sulfur-containing polymer compound A can be subjected to purification treatment or the like by an appropriate method.

[0062] The sulfur-containing polymer compound A obtained in step 1 is determined depending on the type of raw material used in the reaction in step 1. For example, the sulfur-containing polymer compound A obtained in step 1 has a structural unit represented by the following formula (3): -(S) ｎ - (CH ２ ) ｋ - (3)

[0063] In the formula (3), k is a number of 1 or more, and n has the same meaning as n in the formula (1). For example, when a compound represented by formula (2a) is used as the brominated organic compound in step 1, k is the same as m in the formula (2a). On the other hand, when a compound represented by formula (2b) is used as the brominated organic compound in step 1, k is the same as m in the formula (2b). １ The number of carbon atoms in the molecule is the same as that of the molecule itself.

[0064] One or more of the sulfur compounds and one or more of the brominated organic compounds can be used in step 1. For example, when two or more of the brominated organic compounds are used, the resulting sulfur-containing polymer compound A is a polymer containing two or more structural units represented by formula (3).

[0065] In the structural unit represented by the formula (3), -(S) ｎThe - moiety is, for example, a moiety introduced from the linear sulfur polymer. On the other hand, when the metal sulfide compound is used as the sulfur compound in the reaction of step 1, instead of the linear sulfur polymer, -(S) ｎ The - site is "-S-" (ie, n=1).

[0066] When the linear sulfur polymer is used as the sulfur compound in the reaction of step 1, n in formula (3) is, for example, a number exceeding 1, preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and particularly preferably 5 or more. The upper limit of n is not particularly limited, and can be, for example, 10,000 or less, preferably 5,000 or less, more preferably 3,000 or less, even more preferably 1,000 or less, and particularly preferably 500 or less. Furthermore, n may be 100 or less, 50 or less, or 10 or less.

[0067] The sulfur-containing polymer compound A may be a polymer having a linear structure or a polymer having a crosslinked structure. Specifically, when a compound represented by formula (2a) is used as the brominated organic compound in the reaction of step 1, the sulfur-containing polymer compound A can be a polymer having a linear structure. Furthermore, when a compound represented by formula (2b) is used as the brominated organic compound in the reaction of step 1, the sulfur-containing polymer compound A can be a polymer having a crosslinked structure.

[0068] In the reaction of step 1, the reaction between the sulfur compound and the brominated organic compound is a step-growth polymerization, an example of which is a polycondensation reaction. For example, the terminal sulfur of the sulfur compound reacts with the bromo group of the brominated organic compound to cause a polycondensation reaction, thereby producing the sulfur-containing polymer compound of the present invention.

[0069] Therefore, when the compound represented by the formula (2a) is used, since it has Br at both ends, chain elongation occurs at both ends, and a polymer having a linear structure is produced. On the other hand, when the compound represented by the formula (2b) is used, in addition to the Br at both ends, R １Since Br is also present in the sulfur-containing polymer compound A, chain elongation occurs repeatedly in at least three directions, resulting in the production of a polymer having a crosslinked structure (i.e., a polymer having a three-dimensional network structure). Whether the sulfur-containing polymer compound A has a linear structure or a crosslinked structure, it can have the structural unit represented by formula (3).

[0070] The polymer terminal of the sulfur-containing polymer compound A obtained in step 1 may be, for example, hydrogen, or may alternatively be an alkali metal, halogen, or hydroxyl group.

[0071] The production method of the present invention includes step 1, which allows for the simple production of a sulfur-containing polymer compound. In particular, compared to conventional methods for producing sulfur-containing polymer compounds, the sulfur-containing polymer compound can be produced at a lower temperature (e.g., room temperature). For example, while the production methods disclosed in Non-Patent Document 1 above all require high-temperature reactions, in step 1, the reaction can be carried out, for example, at around room temperature, as described above. Moreover, despite the reaction being carried out at a low temperature (e.g., room temperature), the production method of the present invention significantly improves the yield compared to reactions using chloro-group-containing compounds as disclosed in Non-Patent Document 1. Furthermore, the production method of the present invention does not necessarily require the use of an organic solvent.

[0072] Therefore, the manufacturing method of the present invention has a small environmental impact, consumes little energy, and is not prone to complicate the process.

[0073] Furthermore, in the production method of the present invention, the structure of the sulfur-containing polymer compound to be obtained is determined depending on the raw materials used, particularly the brominated organic compound, and therefore sulfur-containing polymer compounds having various molecular structures can be obtained. Therefore, the production method of the present invention is suitable as a method for producing a sulfur-containing polymer compound.

[0074] The number-average degree of polymerization of the sulfur-containing polymer compound obtained by the production method of the present invention is not particularly limited and is, for example, about 5 to 10000. The number-average degree of polymerization of the sulfur-containing polymer compound obtained by the production method of the present invention is preferably 10 or more, and is preferably 5000 or less, more preferably 1000 or less, even more preferably 500 or less, and particularly preferably 100 or less.

[0075] 2. Sulfur-Containing Polymer Compound The present invention also encompasses a sulfur-containing polymer compound. One embodiment of such a sulfur-containing polymer compound is a sulfur-containing polymer compound represented by the following formula (4)-(S): ｎ - (CH ２ ) ａ - (4) is a sulfur-containing polymer compound having a linear structure and a structural unit represented by the following formula:

[0076] In the formula (4), n is a number of 1 or more, and a is a number of 8 or more.

[0077] When a is 8 or more, the sulfur-containing polymer compound having the structural unit represented by formula (4) is obtained in a liquid state. Therefore, when such a sulfur-containing polymer compound is used, for example, as an additive, the liquid state provides better handling than a solid polymer and makes it easier to mix uniformly with the substance to which it is added. The upper limit of a is not particularly limited, and is, for example, preferably 30 or less, more preferably 24 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 12 or less. a may be 8 to 12, 8 to 10, or even 8. a is preferably an integer.

[0078] When a is less than 8, the sulfur-containing polymer compound is in a solid state.

[0079] In the formula (4), n is not particularly limited as long as it is a number of 1 or more. For example, n can be a number exceeding 1, preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and particularly preferably 5 or more. The upper limit of n is not particularly limited, and can be, for example, 10,000 or less, preferably 5,000 or less, more preferably 3,000 or less, even more preferably 1,000 or less, and particularly preferably 500 or less. Furthermore, n may be 100 or less, 50 or less, or 10 or less. The value of n can be calculated by MALDI-TOF MS spectrum measurement of the sulfur-containing polymer compound.

[0080] The sulfur-containing polymer compound having the structural unit represented by the formula (4) can be produced, for example, by step 1 included in the production method of the present invention described above, or can also be produced by other production methods. For example, in step 1, the sulfur-containing polymer compound having the structural unit represented by the formula (4) can be obtained by using the linear sulfur polymer represented by the formula (1) or the metal sulfide and the compound represented by the formula (2a) in which m is 8 or more.

[0081] Another embodiment of the sulfur-containing polymer compound of the present invention is a compound represented by the following formula (5)-(S): ｎ - (CH ２ ) ｂ - (5) is a sulfur-containing polymer compound having a crosslinked structure and a structural unit represented by the following formula:

[0082] In the formula (5), n is a number equal to or greater than 1, and b is a number equal to or greater than 1. b is preferably 2 or greater, more preferably 3 or greater, and is preferably 30 or less, more preferably 24 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 12 or less.

[0083] In the formula (5), n is not particularly limited as long as it is a number of 1 or more. For example, n can be a number exceeding 1, preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and particularly preferably 5 or more. The upper limit of n is not particularly limited, and can be, for example, 10,000 or less, preferably 5,000 or less, more preferably 3,000 or less, even more preferably 1,000 or less, and particularly preferably 500 or less. Furthermore, n may be 100 or less, 50 or less, or 10 or less. The value of n can be calculated by MALDI-TOF MS spectrum measurement of the sulfur-containing polymer compound.

[0084] The sulfur-containing polymer compound having the structural unit represented by the formula (5) can be produced, for example, by step 1 included in the production method of the present invention described above, or can also be produced by other production methods. For example, by using the linear sulfur polymer represented by the formula (1) or the metal sulfide and the compound represented by the formula (2b) in step 1, a sulfur-containing polymer compound having the structural unit represented by the formula (5) and having a crosslinked structure can be obtained.

[0085] The sulfur-containing polymer compound having the structural unit represented by the formula (5) has a crosslinked structure, and therefore, when used as an additive, it can impart properties that linear polymers do not have.

[0086] The sulfur-containing polymer compound of the present invention can have one or more structural units represented by the formula (4) and can have one or more structural units represented by the formula (5).

[0087] The sulfur-containing polymer compound of the present invention according to each of the above embodiments can be used, for example, as various additives. For example, the sulfur-containing polymer compound of the present invention is useful as an additive for rubber, tires, etc., and can also be used as a raw material for coating agents, adhesives, pressure-sensitive adhesives, hoses, sealing materials, packaging materials, and films.

[0088] In specifying the inventions included in the present disclosure, the components (properties, structures, functions, etc.) described in each embodiment of the present disclosure may be combined in any manner. In other words, the present disclosure includes all subject matter consisting of all combinations of the components that can be combined as described in this specification.

[0089] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0090] (Example 1a) A sulfur-containing polymer compound (Product 1A) was synthesized according to the reaction scheme shown in FIG. 1(a). First, sodium sulfide pentahydrate (Na ２ S.5H ２29.7 g (0.177 mol) of sulfur-containing polymer (S-containing polymer) was dissolved in 170 mL of water. To this solution, 50.0 g (0.266 mol) of 1,2-dibromoethane (hereinafter abbreviated as DBE) and 0.05 mmol of hexadecyltrimethylammonium bromide as a phase transfer catalyst were added, and the mixture was stirred at room temperature (25°C) for one day to carry out an interfacial reaction (polycondensation reaction). Insoluble matter formed during the reaction, which was filtered off. The resulting solid was washed successively with water and chloroform, and then dried under reduced pressure to obtain the target sulfur-containing polymer in a 10% yield. Raman spectroscopy of the resulting sulfur-containing polymer revealed peaks for C-S bonds, as shown in Figure 1(b), but no S-S bonds were observed, confirming that product 1A shown in Figure 1(a) had been obtained. Considering the raw materials used and the reaction mechanism, product 1A was estimated to have m = approximately 15.

[0091] Table 1 shows the results of elemental analysis of the product 1A obtained in Example 1a, and it is clear that the product 1A is composed of elements close to the theoretical values.

[0092]

[0093] (Example 2a) A sulfur-containing polymer compound (Product 2A) was synthesized according to the reaction scheme shown in Figure 2(a). First, 5.69 g (0.022 mol) of sulfur and Na ２ S.5H ２ 29.7 g (0.177 mol) of O was dissolved in 280 mL of water and then filtered to obtain a solution of linear sulfur polymer (abbreviated as LS). ２ S.5H ２ O is the molar ratio (sulfur:Na ２ S.5H ２The sulfur-containing polymer was prepared by Raman spectroscopy using a 1:8 ratio of 0.266 mol of DBE and 0.05 mmol of hexadecyltrimethylammonium bromide as a phase transfer catalyst. To this solution, 50.0 g of DBE (0.266 mol) and 0.05 mmol of hexadecyltrimethylammonium bromide were added, and the mixture was stirred at room temperature (25°C) for one day to carry out an interfacial reaction (polycondensation reaction). Insoluble matter formed during the reaction, which was filtered off. The resulting solid was washed with water and chloroform, followed by drying under reduced pressure, yielding the target sulfur-containing polymer in a 17% yield. Raman spectroscopy of the resulting sulfur-containing polymer revealed both C-S bonds and S-S bonds, as shown in Figure 2(b), indicating that product 2A shown in Figure 2(a) had been obtained. Product 2A had n = 2.1, and considering the raw materials used and the reaction mechanism, it was estimated that m = approximately 15.

[0094] Table 2 shows the results of elemental analysis of Product 2A obtained in Example 2a, and it is found that Product 2A is composed of elements close to the theoretical values.

[0095]

[0096] (Example 2b) A sulfur-containing polymer compound (Product 2B) was synthesized according to the reaction scheme shown in FIG. ２ S.5H ２ O in a molar ratio (sulfur:Na ２ S.5H ２ A sulfur-containing polymer was obtained in a yield of 13% by the same method as in Example 2a, except that the sulfur-containing polymer was prepared by mixing the sulfur-containing polymer and the sulfur-containing polymer in an amount of 1:6. Raman spectroscopy of the obtained sulfur-containing polymer revealed both C-S bonds and S-S bonds, as shown in FIG. 3(b), indicating that product 2B shown in FIG. 3(a) was obtained. This product 2B had n = 2.5, and, taking into consideration the raw materials used and the reaction mechanism, it was estimated that m = approximately 15.

[0097] Table 3 shows the results of elemental analysis of Product 2B obtained in Example 2b, and it can be seen that Product 2B is composed of elements close to the theoretical values.

[0098]

[0099] (Example 2c) A sulfur-containing polymer compound (product 2C) was synthesized according to the reaction scheme shown in FIG. ２ S.5H ２ O in a molar ratio (sulfur:Na ２ S.5H ２ A sulfur-containing polymer was obtained in a 40% yield by the same method as in Example 2a, except that the sulfur-containing polymer (LS) was prepared by mixing the sulfur-containing polymer (LS) and sulfur-containing polymer (S—S) in a ratio of 1:3. Raman spectroscopy of the obtained sulfur-containing polymer revealed both C—S bonds and S—S bonds, as shown in FIG. 4(b), indicating that product 2C shown in FIG. 4(a) was obtained. Product 2C had n = 3.5, and, taking into consideration the raw materials used and the reaction mechanism, it was estimated that m was approximately 15.

[0100] Table 4 shows the results of elemental analysis of Product 2C obtained in Example 2c, and it is found that Product 2C is composed of elements close to the theoretical values.

[0101]

[0102] (Example 2d) A sulfur-containing polymer compound (product 2D) was synthesized according to the reaction scheme shown in FIG. ２ S.5H ２ O in a molar ratio (sulfur:Na ２ S.5H ２ A sulfur-containing polymer was obtained in a yield of 39% by the same method as in Example 2a, except that the sulfur-containing polymer (LS) and sulfur-containing polymer (S) were mixed in a 1:1 ratio to obtain a LS solution. Raman spectroscopy of the obtained sulfur-containing polymer revealed both C-S bonds and S-S bonds, as shown in FIG. 5(b), indicating that product 2D shown in FIG. 5(a) was obtained. This product 2D had n = 4.7, and, taking into consideration the raw materials used and the reaction mechanism, it was estimated that m was approximately 15.

[0103] Table 5 shows the results of elemental analysis of Product 2D obtained in Example 2d, and it is found that Product 2D is composed of elements close to the theoretical values.

[0104]

[0105] (Example 3a) A sulfur-containing polymer compound (Product 3A) was synthesized according to the reaction scheme shown in Figure 6. First, sodium sulfide pentahydrate (Na ２ S.5H ２ 22.1 g (0.131 mol) of sulfur-containing polymer (3A) was dissolved in 125 mL of water. To this solution, 40.0 g (0.174 mol) of 1,3-dibromopropane (hereinafter abbreviated as DBP) and 0.05 mmol of hexadecyltrimethylammonium bromide as a phase transfer catalyst were added, and the mixture was stirred at room temperature (25°C) for one day to carry out an interfacial reaction (polycondensation reaction). Insoluble matter formed during the reaction, which was filtered off. The resulting solid was washed successively with water and chloroform, and then dried under reduced pressure to obtain the target sulfur-containing polymer compound in a 4% yield. Considering the raw materials used and the reaction mechanism, it was estimated that m of this product 3A was approximately 15.

[0106] (Example 4a) A sulfur-containing polymer compound (Product 4A) was synthesized according to the reaction scheme shown in Figure 7(a). First, 4.27 g (0.017 mol) of sulfur and Na ２ S.5H ２ 22.3 g (0.132 mol) of O was dissolved in 210 mL of water and then filtered to obtain a solution of linear sulfur polymer (abbreviated as LS). ２ S.5H ２ O is the molar ratio (sulfur:Na ２ S.5H ２ To this solution, 40.0 g of DBP (0.174 mol) and 0.05 mmol of hexadecyltrimethylammonium bromide as a phase transfer catalyst were added, and the mixture was stirred at room temperature (25°C) for one day to carry out an interfacial reaction (polycondensation reaction). Insoluble matter was generated during the reaction, and this was filtered off. The obtained solid was washed with water and chloroform in that order, and then dried under reduced pressure to obtain the target sulfur-containing polymer compound in a yield of 19%. １When H-NMR measurement was performed, it was found that product 4A shown in Fig. 7(a) was obtained, as shown in the spectrum in Fig. 7(b) (the upper line is DBP, and the lower line is product 4A). From the results of elemental analysis, product 4A was estimated to have n = 2, and taking into consideration the raw materials used and the reaction mechanism, it was estimated to have m = 15 or so.

[0107] (Example 4b) A sulfur-containing polymer compound (Product 4B) was synthesized according to the reaction scheme shown in Figure 8(a). ２ SNa ２ S.5H ２ O5H ２ O in a molar ratio (sulfur:Na ２ SNa ２ S.5H ２ O5H ２ The sulfur-containing polymer was obtained in a yield of 18% by the same method as in Example 4a, except that the ratio of the sulfur-containing polymer to the sulfur-containing polymer was 1:6. １ H-NMR measurement revealed that product 4B shown in Fig. 8(a) was obtained, as shown in the spectrum in Fig. 8(b) (the upper line is DBP, and the lower line is product 4B). From the results of elemental analysis, product 4B was estimated to have n = 2.5, and taking into consideration the raw materials used and the reaction mechanism, it was estimated that m = approximately 15.

[0108] (Example 4c) A sulfur-containing polymer compound (Product 4C) was synthesized according to the reaction scheme shown in Figure 9(a). ２ S.5H ２ O in a molar ratio (sulfur:Na ２ S.5H ２ The sulfur-containing polymer was obtained in a yield of 28% by the same method as in Example 4a, except that the ratio of the sulfur-containing polymer to the sulfur-containing polymer was 1:3. １ 1H-NMR measurement revealed that product 4C shown in Fig. 9(a) was obtained, as shown in the spectrum in Fig. 9(b) (the upper line is DBP, and the lower line is product 4C). From the results of elemental analysis, product 4C was estimated to have n = 3.5, and taking into consideration the raw materials used and the reaction mechanism, it was estimated that m = approximately 15.

[0109] (Example 4d) A sulfur-containing polymer compound (product 4D) was synthesized according to the reaction scheme shown in FIG. ２ S.5H ２ O in a molar ratio (sulfur:Na ２ S.5H ２ The sulfur-containing polymer was obtained in a yield of 24% by the same method as in Example 4a, except that the sulfur-containing polymer was mixed in an amount of 1:1 to obtain a solution of LS. １ When H-NMR measurement was performed, it was found that product 4D shown in Fig. 10(a) was obtained, as shown in the spectrum in Fig. 10(b) (the upper line is DBP, and the lower line is product 4D). From the results of elemental analysis, product 4D was estimated to have n = 3.5, and taking into consideration the raw materials used and the reaction mechanism, it was estimated to have m = approximately 15.

[0110] (Example 5a) A sulfur-containing polymer compound (Product 5A) was synthesized according to the reaction scheme shown in FIG. 11(a). First, sodium sulfide pentahydrate (Na ２ S.5H ２ 706.7 mg (4.20 mmol) of sulfur-containing polymer (SbO) was dissolved in 5 mL of water. To this solution, 1.00 g (3.68 mmol) of 1,8-dibromooctane (hereinafter abbreviated as DBO) and 0.005 mmol of hexadecyltrimethylammonium bromide as a phase transfer catalyst were added, and the mixture was stirred at room temperature (25°C) for one day to carry out an interfacial reaction (polycondensation reaction). Insoluble matter was generated during the reaction, so this was filtered off, and the resulting solid was washed with water and chloroform in that order, and then dried under reduced pressure to obtain the target sulfur-containing polymer compound in a yield of 50%. １ When H-NMR measurement was performed, it was found that Product 5A shown in Fig. 11(a) was obtained, as shown in the spectrum in Fig. 11(b) (the upper part is DBO, and the lower part is Product 5A). Taking into consideration the raw materials used and the reaction mechanism, it was estimated that m of Product 5A was about 15.

[0111] (Example 6a) A sulfur-containing polymer compound (Product 6A) was synthesized according to the reaction scheme shown in Figure 12(a). First, 81.2 mg (0.317 mmol) of sulfur and Na ２ S.5H ２ 424.0 mg (2.52 mmol) of O was dissolved in 5 mL of water and then filtered to obtain a solution of linear sulfur polymer (abbreviated as LS). ２ S.5H ２ O is the molar ratio (sulfur:Na ２ S.5H ２ To this solution, 1.00 g of DBO (3.69 mmol) and 0.005 mmol of hexadecyltrimethylammonium bromide as a phase transfer catalyst were added, and the mixture was stirred at room temperature (25°C) for one day to carry out an interfacial reaction (polycondensation reaction). Insoluble matter was generated during the reaction, and this was filtered off. The obtained solid was washed with water and chloroform in that order, and then dried under reduced pressure to obtain the target sulfur-containing polymer compound in a yield of 47%. １ H-NMR measurement revealed that product 6A shown in Fig. 12(a) was obtained, as shown in the spectrum in Fig. 12(b) (the upper part is DBO, and the lower part is product 6A). From the results of elemental analysis, product 6A was estimated to have n = 2, and taking into consideration the raw materials used and the reaction mechanism, it was estimated that m = approximately 15.

[0112] (Example 6b) A sulfur-containing polymer compound (product 6B) was synthesized according to the reaction scheme shown in FIG. ２ S.5H ２ O in a molar ratio (sulfur:Na ２ S.5H ２ The sulfur-containing polymer was obtained in a yield of 56% by the same method as in Example 6a, except that the sulfur-containing polymer was mixed in an amount of 1:4 to obtain a solution of LS. １H-NMR measurement revealed that product 6B shown in Fig. 13(a) was obtained, as shown in the spectrum in Fig. 13(b) (the upper part is DBO, and the lower part is product 6B). Product 6B is presumed to have n = 3, and, taking into consideration the raw materials used and the reaction mechanism, it is presumed to have m = 15 or so.

[0113] (Example 6c) A sulfur-containing polymer compound (product 6C) was synthesized according to the reaction scheme shown in Figure 14(a). ２ S.5H ２ O in a molar ratio (sulfur:Na ２ S.5H ２ The sulfur-containing polymer was obtained in a yield of 59% by the same method as in Example 6a, except that the ratio of the sulfur-containing polymer to the sulfur-containing polymer was 1:3. １ H-NMR measurement revealed that product 6C shown in Fig. 14(a) was obtained, as shown in the spectrum in Fig. 14(b) (the upper line is DBO, and the lower line is product 6C). From the results of elemental analysis, product 6C was estimated to have n = 3.5, and taking into consideration the raw materials used and the reaction mechanism, it was estimated that m = approximately 15.

[0114] (Example 6d) A sulfur-containing polymer compound (product 6D) was synthesized according to the reaction scheme shown in FIG. ２ S.5H ２ O in a molar ratio (sulfur:Na ２ S.5H ２ The sulfur-containing polymer was obtained in a yield of 50% in the same manner as in Example 6a, except that the sulfur-containing polymer was mixed in an amount of 1:1 to obtain a solution of LS. １ 1H-NMR measurement revealed that product 6D shown in Fig. 15(a) was obtained, as shown in the spectrum in Fig. 15(b) (the upper line is DBO, and the lower line is product 6D). From the results of elemental analysis, product 6D was estimated to have n = 4.7, and taking into consideration the raw materials used, the reaction mechanism, etc., it was estimated that m = approximately 15.

[0115] (Example 7a) A sulfur-containing polymer compound (Product 7A) was synthesized according to the reaction scheme shown in Figure 16. First, sodium sulfide pentahydrate (Na ２ S.5H ２ 1.33 g (7.88 mmol) of sulfur-containing polymer (7A) was dissolved in 7.5 mL of water. To this solution, 2.00 g (7.14 mmol) of 1,2,3-tribromopropane (hereinafter abbreviated as TBP) and 0.005 mmol of hexadecyltrimethylammonium bromide as a phase transfer catalyst were added, and the mixture was stirred at room temperature (25°C) for one day to carry out an interfacial reaction (polycondensation reaction). Insoluble matter formed during the reaction, which was filtered off. The resulting solid was washed successively with water and chloroform, and then dried under reduced pressure to obtain the target sulfur-containing polymer compound in a 28% yield. Considering the raw materials used and the reaction mechanism, it was estimated that m of this product 7A was approximately 15.

[0116] (Example 8a) A sulfur-containing polymer compound (product 8A) was synthesized according to the reaction scheme shown in Figure 17. First, 152 mg (0.594 mmol) of sulfur and Na ２ S.5H ２ 795 mg (4.73 mmol) of O was dissolved in 7.5 mL of water, and then filtered to obtain a solution of linear sulfur polymer (abbreviated as LS). ２ S.5H ２ O is the molar ratio (sulfur:Na ２ S.5H ２ The sulfur-containing polymer was obtained in a yield of 41% by weight. From the results of elemental analysis, Product 8A was estimated to have an n=32 value. Furthermore, taking into consideration the raw materials used and the reaction mechanism, it was estimated to have an m=15 value.

[0117] (Example 8b) Sulfur and Na ２ S.5H２ O in a molar ratio (sulfur:Na ２ S.5H ２ A sulfur-containing polymer was obtained in a yield of 48% in the same manner as in Example 8a, except that the ratio of the sulfur-containing polymer to the sulfur-containing polymer was 1:4 to obtain a solution of LS.

[0118] (Example 8c) Sulfur and Na ２ S.5H ２ O in a molar ratio (sulfur:Na ２ S.5H ２ A sulfur-containing polymer was obtained in a yield of 39% in the same manner as in Example 8a, except that the ratio of LS to LS was 1:3.

[0119] (Example 8d) Sulfur and Na ２ S.5H ２ O in a molar ratio (sulfur:Na ２ S.5H ２ A sulfur-containing polymer was obtained in a yield of 40% in the same manner as in Example 8a, except that the sulfur-containing polymer and the sulfur-containing polymer were mixed in an amount of 1:1 to obtain a solution of LS.

[0120] Comparative Example 1a A sulfur-containing polymer compound was synthesized in the same manner as in Example 1a, except that 1,2-dichloroethane was used instead of 1,2-dibromoethane. However, the reaction did not proceed at room temperature (25°C), and the target compound could not be obtained.

[0121] Comparative Example 2a A sulfur-containing polymer compound was synthesized in the same manner as in Example 2a, except that 1,2-dichloroethane was used instead of 1,2-dibromoethane. However, the reaction did not proceed at room temperature (25°C), and the target compound could not be obtained.

[0122] Comparative Example 3a A sulfur-containing polymer compound was synthesized in the same manner as in Example 3a, except that 1,3-dichloropropane was used instead of 1,3-dibromopropane. However, the reaction did not proceed at room temperature (25°C), and the target compound could not be obtained.

[0123] Comparative Example 4a A sulfur-containing polymer compound was synthesized in the same manner as in Example 4a, except that 1,3-dichloropropane was used instead of 1,3-dibromopropane. However, the reaction did not proceed at room temperature (25°C), and the target compound could not be obtained.

[0124] (Example 9a) A sulfur-containing polymer compound (Product 9A) was synthesized according to the reaction scheme shown in Figure 18(a). First, 25.1 g (0.098 mol) of sulfur and Na ２ S.5H ２ 32.8 g (0.20 mol) of 0.1% methyl sulphur dioxide was dissolved in 350 mL of water and then filtered to obtain a solution of linear sulfur polymer (abbreviated as LS). ２ S.5H ２ O is the molar ratio (sulfur:Na ２ S.5H ２ The sulfur-containing polymer (Product 9A) was mixed in an amount of 1:2. To this solution, a solution of 6.07 g (0.016 mol) of powdered pentaerythritol tetrabromide dissolved in 49.1 g (0.26 mol) of DBE and 0.005 mmol of hexadecyltrimethylammonium bromide as a phase transfer catalyst were added, and the mixture was stirred at room temperature (25°C) for one day to carry out an interfacial reaction (polycondensation reaction). Insoluble matter formed during the reaction was filtered off, and the resulting solid was washed with water and chloroform, followed by drying under reduced pressure to obtain the target sulfur-containing polymer. Raman spectroscopy of the resulting sulfur-containing polymer (Product 9A) revealed C-S bonds and S-S bonds, as shown in Figure 18(b), confirming the synthesis of the sulfur-containing polymer (Product 9A) shown in Figure 18(a).

[0125] Table 6 shows the results of elemental analysis of Product 9A obtained in Example 9a. Judging from the sulfur content in the results, it was presumed that a crosslinked structure was formed.

[0126]

[0127] (Example 10a) A sulfur-containing polymer compound (Product 10A) was synthesized according to the reaction scheme shown in Figure 19(a). First, 25.1 g (0.098 mol) of sulfur and Na２ S.5H ２ 32.8 g (0.20 mol) of 0.1% methyl sulphur dioxide was dissolved in 350 mL of water and then filtered to obtain a solution of linear sulfur polymer (abbreviated as LS). ２ S.5H ２ O is the molar ratio (sulfur:Na ２ S.5H ２ The sulfur-containing polymer (Product 10A) was mixed in an amount of 1:2. A solution of 5.86 g (0.016 mol) of powdered 1,2,3,4-tetrabromobutane in 49.1 g (0.26 mol) of DBE and 0.005 mmol of hexadecyltrimethylammonium bromide as a phase transfer catalyst were added to this solution, and the mixture was stirred at room temperature (25°C) for one day to carry out an interfacial reaction (polycondensation reaction). Insoluble matter formed during the reaction, which was filtered off. The resulting solid was washed with water and chloroform, followed by drying under reduced pressure to obtain the target sulfur-containing polymer. Raman spectroscopy of the resulting sulfur-containing polymer (Product 10A) revealed C-S bonds and S-S bonds, as shown in Figure 19(b), confirming the synthesis of the sulfur-containing polymer (Product 10A) shown in Figure 19(a).

[0128] Table 7 shows the results of elemental analysis of the product 10A obtained in Example 10a. Judging from the sulfur content in these results, it was presumed that a crosslinked structure had been formed.

[0129]

[0130] (Example 11a) A sulfur-containing polymer compound (Product 11A) was synthesized according to the reaction scheme shown in Figure 20(a). First, 25.1 g (0.098 mol) of sulfur and Na ２ S.5H ２ 32.8 g (0.20 mol) of 0.1% methyl sulphur dioxide was dissolved in 350 mL of water and then filtered to obtain a solution of linear sulfur polymer (abbreviated as LS). ２ S.5H ２ O is the molar ratio (sulfur:Na ２ S.5H ２The sulfur-containing polymer (Product 11A) was mixed in an amount of 1:2. A solution of 4.52 g (0.016 mol) of liquid 1,2,3-tribromopropane in 50.7 g (0.27 mol) of DBE and 0.005 mmol of hexadecyltrimethylammonium bromide as a phase transfer catalyst were added to this solution, and the mixture was stirred at room temperature (25°C) for one day to carry out an interfacial reaction (polycondensation reaction). Insoluble matter formed during the reaction, which was filtered off. The resulting solid was washed with water and chloroform, followed by drying under reduced pressure to obtain the target sulfur-containing polymer. Raman spectroscopy of the resulting sulfur-containing polymer (Product 11A) revealed C-S bonds and S-S bonds, as shown in Figure 20(b), confirming the synthesis of the sulfur-containing polymer (Product 11A) shown in Figure 20(a).

[0131] Table 8 shows the results of the elemental analysis of product 11A obtained in Example 11a.

[0132]

[0133] (Example 12a) A sulfur-containing polymer compound (product 12A) was synthesized according to the reaction scheme shown in Figure 21(a). First, 1.92 g (0.0075 mol) of sulfur and Na ２ S.5H ２ 2.52 g (0.015 mol) of 0.015 mol of sulfur dioxide was dissolved in 30 mL of water and then filtered to obtain a solution of linear sulfur polymer (abbreviated as LS). ２ S.5H ２ O is the molar ratio (sulfur:Na ２ S.5H ２O) were mixed in amounts such that the ratio was 1:2. To this solution, a solution of 4.77 g (0.018 mol) of powdered 2,6-bis(bromomethyl)pyridine in 30 mL of chloroform and 0.005 mmol of hexadecyltrimethylammonium bromide as a phase transfer catalyst were added, and the mixture was stirred at room temperature (25°C) for one day to carry out an interfacial reaction (polycondensation reaction). After the reaction, the solvent in the chloroform phase was distilled off, and the remaining dark red liquid was dissolved in 10 mL of chloroform and added dropwise to 200 mL of acetone to cause reprecipitation. This was centrifuged to obtain a dark red liquid. The mixture was then dried under reduced pressure to obtain the target sulfur-containing polymer compound. The obtained sulfur-containing polymer compound (Product 12A) １ When H-NMR measurement was performed, broadening of the peak of the obtained sulfur-containing polymer compound and splitting of the peak of the methylene group were observed, as shown in FIG. 21(b), which confirmed the synthesis of the sulfur-containing polymer (product 11A) shown in FIG. 21(a).

[0134] (Example 13a) A sulfur-containing polymer compound (Product 13A) was synthesized according to the reaction scheme shown in FIG. 22(a). First, 133 mg (0.519 mmol) of sulfur and Na ２ S.5H ２ 174 mg (1.04 mmol) of 0 was dissolved in 5 mL of water and then filtered to obtain a solution of linear sulfur polymer (abbreviated as LS). ２ S.5H ２ O is the molar ratio (sulfur:Na ２ S.5H ２The sulfur-containing polymer (Product 13A) was mixed in an amount of 1:2. To this solution, 411 mg (1.56 mmol) of α,α'-dibromo-p-xylene dissolved in 5 mL of chloroform and 0.005 mmol of hexadecyltrimethylammonium bromide as a phase transfer catalyst were added, and the mixture was stirred at room temperature (25°C) for one day to carry out an interfacial reaction (polycondensation reaction). Insoluble matter formed during the reaction, which was filtered off, and the resulting solid was washed successively with water and chloroform. The mixture was then dried under reduced pressure to obtain the target sulfur-containing polymer. Raman spectroscopy of the resulting sulfur-containing polymer (Product 13A) revealed C-S bonds and S-S bonds as shown in Figure 22(b), confirming the synthesis of the sulfur-containing polymer (Product 13A) shown in Figure 22(a).

Claims

1. A method for producing a sulfur-containing polymer compound, comprising the step of reacting a sulfur compound with a brominated organic compound to obtain a sulfur-containing polymer compound, wherein the sulfur compound is at least one selected from the group consisting of linear sulfur polymers and metal sulfide compounds, and the brominated organic compound is a hydrocarbon compound having two or more bromo groups in the molecule.

2. The linear sulfur polymer is represented by the following formula (1): Y-(S) ｎ 2. The method for producing a sulfur-containing polymer compound according to claim 1, wherein the sulfur-containing polymer compound is a compound represented by the formula (1):

3. The method for producing a sulfur-containing polymer compound according to claim 1, wherein the metal sulfide compound is sodium sulfide.

4. The brominated organic compound is represented by the following formula (2a): Br—(CH ２ ) ｍ -Br (2a) (in the formula (2a), m is a number of 1 or more), a compound represented by the following formula (2b): Br-R １ -Br (2b) (In the above formula (2b), R １ represents an alkylene group having one or more bromo groups), and the following formula (2c): Br-R ２ -Br (2c), (in the above formula (2c), R ２ The method for producing a sulfur-containing polymer compound according to any one of claims 1 to 3, wherein the sulfur-containing polymer compound is one compound selected from the group consisting of compounds represented by the formula:

5. The sulfur-containing polymer compound is represented by the following formula (3)-(S): ｎ - (CH ２ ) ｋ The method for producing a sulfur-containing polymer compound according to any one of claims 1 to 3, wherein the sulfur-containing polymer compound has a structural unit represented by the following formula (3):

6. The following formula (4) - (S) ｎ - (CH ２ ) ａ - (4) (in the formula (4), n is a number of 1 or more, and a is a number of 8 or more), and a sulfur-containing polymer compound having a linear structure.

7. The following formula (5) - (S) ｎ - (CH ２ ) ｂ - (5) (in the formula (5), n is a number of 1 or more, and b is a number of 1 or more), and a sulfur-containing polymer compound having a crosslinked structure.