Sulfur-containing polymer material and its manufacturing method

Abstract

To provide a sulfur-containing polymer material that is less susceptible to depolymerization and has high solubility in organic solvent and a method for producing the same.SOLUTION: A sulfur-containing polymer material contains a chain molecule, and at least one cyclic molecule. The chain molecule penetrates the at least one cyclic molecule in a skewering manner. The chain molecule contains at least a sulfur unit represented by the formula (1)-(S)-(1) as a constitutional unit. The sulfur-containing polymer material is less susceptible to depolymerization and has high solubility in organic solvent, so that it has excellent stability and processability.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a sulfur-containing polymeric material and a method for producing the same. [Background technology]

[0002] With 7 million tons of sulfur dumped on land annually, there has been a strong demand in recent years for the effective use of this sulfur. As one method, polymer materials using sulfur have attracted attention. When sulfur (S8) is heated, the 8-membered ring is cleaved to generate radicals, so the sulfur polymerization reaction proceeds simply by heating it. For this reason, sulfur polymerization is very simple, but the obtained sulfur polymer is a material with poor stability because it is prone to depolymerization at room temperature. Therefore, it is not easy to obtain a sulfur polymer with a high molecular weight, and in addition, sulfur polymers are insoluble in commonly used organic solvents, making them a material with poor processability.

[0003] From this viewpoint, methods for obtaining sulfur polymers have been actively studied, and methods for improving the properties of sulfur polymers have also been widely studied. For example, recently, various methods have been proposed, 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.

[0004] Non-Patent Document 1 discloses a method for producing a sulfur polymer by copolymerization with a vinyl monomer or a dithiol monomer. The sulfur polymer obtained by this method is soluble in general-purpose organic solvents such as chloroform and tetrahydrofuran, and is expected to have improved processability. Non-Patent Document 2 proposes an inverse vulcanization method including a step of copolymerizing a polyfunctional vinyl monomer with sulfur, and it is expected that a more stable sulfur polymer can be obtained. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] Jeffrey Pyun,et.al.Polym. Chem.2017,8,5167-5173 [Non-Patent Document 2] Chung,WJet.al.Nat.Chem.2013,35,518-524 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the sulfur polymer obtained by the technique disclosed in the above-mentioned Non-Patent Document 1 has good processability, but has a problem that it is poor in stability, for example, depolymerization occurs when left at room temperature, and it is difficult to obtain a high molecular weight sulfur polymer. On the other hand, the sulfur polymer obtained by the technique disclosed in the above-mentioned Non-Patent Document 2 has high stability because of the crosslinked structure, but the crosslinked structure makes it difficult to dissolve in a solvent, resulting in reduced processability. As such, in sulfur polymers, stability and processability are in a trade-off relationship, so there has been a strong demand for the development of a sulfur-containing polymer material in which both properties are improved.

[0007] The present invention has been made in view of the above, and an object of the present invention is to provide a sulfur-containing polymer material which is less susceptible to depolymerization and has high solubility in organic solvents, and a method for producing the same. [Means for solving the problem]

[0008] In order to achieve the above object, the present inventors have conducted extensive research from a perspective different from the conventional approach based on polymer chemistry of stabilizing sulfur-containing polymer materials by covalent bonds. As a result, they have found that the above object can be achieved by using a sulfur-containing chain molecule and at least one cyclic molecule, and have completed the present invention.

[0009] That is, the present invention includes, for example, the subject matter described in the following sections. Item 1 1. A sulfur-containing polymeric material, comprising: Contains a chain molecule and at least one cyclic molecule, the chain molecule pierces the at least one cyclic molecule in a skewered manner, The chain molecule is at least one represented by the following formula (1): -(S)- (1) A sulfur-containing polymer material containing a sulfur unit represented by the following formula (1): Section 2 The chain molecule has a structure represented by the following formula (1a) in the molecule. -(S) n - (1a) (where n is a number equal to or greater than 2) Item 2. The sulfur-containing polymer material according to item 1, having a moiety represented by the formula: Section 3 The chain molecule further contains a second constitutional unit, Item 3. The sulfur-containing polymer material according to item 1 or 2, wherein the second constitutional unit has a size such that it cannot penetrate through the ring of the cyclic molecule. Section 4 4. The sulfur-containing polymeric material according to any one of items 1 to 3, wherein the second constitutional unit is a vinyl constitutional unit. Section 5 the cyclic molecule comprises a cyclodextrin or a cyclodextrin derivative; Item 5. The sulfur-containing polymer material according to any one of items 1 to 4, wherein the cyclodextrin derivative has a structure in which hydrogen atoms of at least one or more hydroxyl groups of cyclodextrin are substituted with at least one group selected from the group consisting of a hydrocarbon group, an acyl group, and -CONHR (R is an alkyl group). Section 6 A method for producing the sulfur-containing polymeric material according to any one of claims 1 to 5, comprising the steps of: A production method comprising step A of mixing a sulfur source and a cyclic molecule. Section 7 Item 7. The method according to item 6, wherein in the step A, a product obtained by mixing the sulfur source and the cyclic molecule is polymerized with a vinyl polymerizable monomer. Effect of the Invention

[0010] The sulfur-containing polymer material according to the present invention is resistant to depolymerization and has high solubility in organic solvents, and therefore has excellent stability and processability. [Brief description of the drawings]

[0011] [Figure 1] FIG. 1 is a schematic diagram showing an example of an embodiment of a sulfur-containing polymer material of the present invention. [Diagram 2] 1 is a reaction scheme for producing the sulfur-containing polymer material of Example 1. [Diagram 3] 1 is a reaction scheme for producing a sulfur and styrene copolymer of Comparative Example 1. [Figure 4] 1 is a 1H-NMR spectrum of SPRx obtained in Example 1. [Diagram 5] 1 shows the results of GPC measurement of SPRx obtained in Example 1 and a copolymer of sulfur and styrene P(S / St) obtained in Comparative Example 1. [Figure 6] 1 shows the results of thermal analysis (TGA) of SPRx obtained in Example 1 and the sulfur and styrene copolymer P(S / St) obtained in Comparative Example 1. [Figure 7] 1 shows the change over time in weight average molecular weight (Mw) of SPRx obtained in Example 1 and P(S / St) obtained in Comparative Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Hereinafter, embodiments of the present invention will be described in detail. In this specification, the expressions "containing" and "comprise" include the concepts of "containing", "comprises", "consists essentially of" and "consists only of".

[0013] 1. Sulfur-containing polymer materials The sulfur-containing polymer material of the present invention comprises a chain molecule and at least one cyclic molecule, The chain molecule penetrates the at least one cyclic molecule in a skewered manner. The chain molecule is at least one of the following formula (1): -(S)- (1) The sulfur unit represented by the following formula (1) is contained as a constituent unit.

[0014] The sulfur-containing polymer material of the present invention is unlikely to undergo depolymerization and has high solubility in organic solvents, and therefore has excellent stability and processability. In the sulfur-containing polymer material of the present invention, cyclic molecules are included so as to be able to slide on the chain molecules (the so-called protective effect of the chain molecules by the cyclic molecules). Specifically, the cyclic molecules are able to slide on the chain molecules (particularly the sulfur polymer portion). This inhibits depolymerization of the chain molecules (particularly the sulfur polymer portion). As a result, the sulfur-containing polymer material has excellent stability.

[0015] The sulfur-containing polymer material of the present invention has a structure in which a chain molecule penetrates at least one cyclic molecule in a skewered manner, and thus has a so-called rotaxane structure. A rotaxane has a structure in which a cyclic molecule and a chain molecule are combined, and both ends of the chain molecule have blocking groups that prevent the cyclic molecule from being detached. On the other hand, when these blocking groups are not present, it is called a pseudorotaxane, and among them, a structure in which two or more cyclic molecules are skewered and fitted into a chain molecule is called a "pseudopolyrotaxane". In addition, a structure in which both ends of the chain molecule of such a pseudopolyrotaxane have blocking groups that prevent the cyclic molecule from being detached is called a "polyrotaxane".

[0016] For convenience, in this specification, pseudorotaxanes and pseudopolyrotaxanes are collectively referred to as “pseudopolyrotaxanes”, and rotaxanes and polyrotaxanes are collectively referred to as “polyrotaxanes”. Thus, in this specification, pseudopolyrotaxanes and polyrotaxanes have at least one or more cyclic molecules.

[0017] (cyclic molecule) In the sulfur-containing polymer material, the type of cyclic molecule is not particularly limited as long as the chain molecule can be threaded. For example, cyclic molecules conventionally used in polyrotaxanes can be widely applied.

[0018] Examples of the cyclic molecule include cyclodextrin compounds, specifically α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, dimethylcyclodextrin, glucosylcyclodextrin, etc., and other examples include cyclodextrin derivatives, etc. Other examples of the cyclic molecule include cyclic oligomers, artificial host molecules, etc. Examples of the cyclic oligomers include ethylene glycol oligomers, ethylene oxide oligomers, propylene glycol oligomers, polysaccharides, etc. Examples of artificial host molecules include calixarenes, crown ethers, cyclophanes, cucurbiturils, pillararenes, and derivatives thereof, more specifically, calix[6]arene sulfonic acid, calix[8]arene sulfonic acid, 12-crown-4, 18-crown-6, [6]paracyclophane, [2,2]paracyclophane, cucurbit[6]uril, cucurbit[7]uril, cucurbit[8]uril, pillar[5]arene, pillar[6]arene, pillar[7]arene, pillar[8]arene, pillar[9]arene, pillar

[10] arene, etc.

[0019] Here, the cyclodextrin derivative means, for example, a compound in which the hydrogen atom of at least one or more hydroxyl groups of cyclodextrin is substituted with another substituent A. The type of the substituent A is not particularly limited, and for example, at least one group selected from the group consisting of a hydrocarbon group, an acyl group, and -CONHR (R is an alkyl group) can be mentioned. Here, as a mere note for the sake of certainty, the expression "cyclodextrin" in this specification means at least one selected from the group consisting of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. Therefore, the cyclodextrin derivative is at least one selected from the group consisting of α-cyclodextrin derivatives, β-cyclodextrin derivatives, and γ-cyclodextrin derivatives.

[0020] In terms of ease of threading of chain molecules, the cyclodextrin derivative preferably has a structure in which the hydrogen atoms of 70% or more of the total number of hydroxyl groups present in one cyclodextrin molecule are substituted with the substituent A, more preferably has a structure in which the hydrogen atoms of 80% or more of the hydroxyl groups are substituted with the substituent A, even more preferably has a structure in which the hydrogen atoms of 90% or more of the hydroxyl groups are substituted with the substituent A, and particularly preferably has a structure in which the hydrogen atoms of all the hydroxyl groups are substituted with the substituent A.

[0021] When the substituent A is a hydrocarbon group, the type is not particularly limited. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. The number of carbon atoms in the hydrocarbon group is not particularly limited. In terms of ease of threading a chain molecule, the number of carbon atoms in the hydrocarbon group is preferably 1 to 4. Specific examples of the hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group. When the hydrocarbon group is a propyl group or a butyl group, it may be either a straight chain or a branched chain.

[0022] When the substituent A is an acyl group, its type is not particularly limited. Examples of the acyl group include an acetyl group, a propionyl group, and a formyl group. In terms of the ease of threading the chain molecule, the acyl group is preferably an acetyl group.

[0023] When the substituent A is -CONHR (R is a methyl group or an ethyl group), examples of the substituent A include a methyl carbamate group and an ethyl carbamate group. In terms of ease of threading a chain molecule, -CONHR is preferably an ethyl carbamate group.

[0024] The cyclic molecules contained in the sulfur-containing polymer material may be of one type alone or of two or more different types in combination.

[0025] The cyclic molecule preferably contains cyclodextrin or a cyclodextrin derivative, in that the sulfur-containing polymer material can be easily produced and the stability can be easily improved. In that the chain molecules can easily penetrate, a cyclodextrin derivative is more preferable, and an α-cyclodextrin derivative is particularly preferable (note that cyclodextrin derivatives have fewer hydroxyl groups than cyclodextrin, and therefore a cage structure consisting of multiple molecules is less likely to be formed, and the chain molecules can more easily penetrate within the ring).

[0026] When the cyclic molecule is a cyclodextrin derivative, the cyclodextrin derivative preferably has a structure in which at least one hydrogen atom of a hydroxyl group in the cyclodextrin is substituted with at least one group selected from the group consisting of a hydrocarbon group, an acyl group, and -CONHR (R is an alkyl group), and among these, the cyclodextrin derivative preferably has a structure in which the hydrogen atom of at least one hydroxyl group in the cyclodextrin is substituted with the aforementioned hydrocarbon group having 1 to 4 carbon atoms. Therefore, the cyclic molecule preferably has a structure in which at least one hydrogen atom of a hydroxyl group in α-cyclodextrin is substituted with a hydrocarbon group having 1 to 4 carbon atoms.

[0027] When the number of cyclic molecules penetrating one chain molecule is two or more, all of them may be the same type, or some or all of them may be different types.

[0028] (chain molecule) In the sulfur-containing polymeric material, the chain molecule is a molecule that serves as the axis in the polyrotaxane.

[0029] The chain molecule pierces the at least one cyclic molecule in a skewered manner. In particular, the chain molecule is represented by the following formula (1): -(S)- (1) More specifically, the chain molecule has a moiety represented by formula (1) in its main chain. In particular, it is preferable that the main chain of the chain molecule has a repeating and continuous presence of the structural unit represented by formula (1), that is, has a sulfur oligomer or polymer moiety.

[0030] Therefore, the chain molecule has the following formula (1a) in the molecule: -(S) n - (1a) (where n is a number equal to or greater than 2) It is preferable that the chain molecule has a moiety represented by formula (1a) in its main chain. More specifically, it is preferable that the chain molecule has a moiety represented by formula (1a) in its main chain.

[0031] In formula (1a), n is not particularly limited as long as it is a number of 2 or more. n is more preferably 10 or more, even more preferably 30 or more, and particularly preferably 50 or more. The upper limit of n is not particularly limited, and is not particularly limited as long as it is a chain length that can be formed by polymerization. For example, the upper limit of n can be 10000 or less in consideration of processability, but is not limited thereto.

[0032] The chain molecule is, for example, "-(S)" represented by formula (1a). n -" alone or in the molecule. n It is possible for the chain molecule to have units other than -. n When only "-" is formed, the cyclic molecule can be dropped from the chain molecule, resulting in the pseudopolyrotaxane described above. n The "-" end is not particularly limited, and can be, for example, the same as that of known sulfur polymers, and can usually be hydrogen.

[0033] On the other hand, chain molecules are "-(S) nWhen the chain molecule has a structural unit other than "-", the type of the structural unit is not particularly limited, and a wide variety of structural units capable of bonding with sulfur can be used. In particular, such a structural unit is preferably a structural unit capable of preventing the cyclic molecule from falling off from the chain molecule. For example, when the chain molecule has a structural unit having a size that does not allow it to penetrate into the ring of the cyclic molecule, such a structural unit can act as a stopper (also called a blocking group) for the cyclic molecule and prevent the cyclic molecule from falling off from the chain molecule. Hereinafter, a structural unit having a size that does not allow it to penetrate into the ring of the cyclic molecule is referred to as a "second structural unit".

[0034] When the chain molecule further contains a second constituent unit and the second constituent unit has a size such that it cannot penetrate into the ring of the cyclic molecule, the cyclic molecule is prevented from falling off the chain molecule, and the protective effect of the cyclic molecule on the chain molecule is more easily exerted. As a result, the sulfur-containing polymer material is less susceptible to depolymerization and has improved stability.

[0035] The type of the second structural unit is not particularly limited, and can be appropriately selected according to the size of the opening of the cyclic molecule. A specific example of the second structural unit is a vinyl structural unit. The vinyl structural unit referred to here is a structural unit derived from a polymerizable vinyl compound. The structural unit derived from a polymerizable vinyl compound refers to a repeating structural unit formed when a vinyl compound is polymerized.

[0036] As the vinyl compound, for example, a wide variety of known radical polymerizable monomers can be used. Specific examples of the radical polymerizable monomer include styrene monomers, unsaturated ester monomers, unsaturated alcohol monomers, unsaturated carboxylic acid monomers, unsaturated carboxylate monomers, and unsaturated amide monomers.

[0037] Examples of styrene monomers include styrene, α-methylstyrene, β-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 2,4,6-trimethylstyrene, 4-methoxystyrene, 4-tert-butylstyrene, 4-chlorostyrene, 4-aminostyrene, 4-nitrostyrene, 4-vinylbenzoic acid, sodium 4-styrenesulfonate, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 4-(chloromethyl)styrene, β-chlorostyrene, 2-bromostyrene, 3-bromostyrene, 4-bromostyrene, 4-(bromomethyl)styrene, β-bromostyrene, 4-isopropenyltoluene, 2-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene, 4-(fluoromethyl)styrene, β-chlorostyrene, divinylbenzene, 1,4-diisopropenylbenzenetrivinylbenzene, 1-vinylnaphthalene, 9-vinylanthracene, and styryl cyanide.

[0038] Examples of the unsaturated ester monomer include monomers having a polymerizable double bond at an ester moiety, such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl cyclohexanecarboxylate, vinyl monochloroacetate, vinyl benzoate, isopropenyl acetate, and allyl acetate; esters of polymerizable carboxylic acid compounds, such as (meth)acrylic acid esters; and the like.

[0039] In this specification, "(meth)acrylic" means "acrylic" or "methacrylic", "(meth)acrylate" means "acrylate" or "methacrylate", and "(meth)allyl" means "allyl" or "methallyl".

[0040] Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, glycidyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, ethoxy-diethylene glycol acrylate, methoxy-triethylene glycol acrylate, and methoxy-polyethylene glycol acrylate.

[0041] Examples of the esters of polymerizable carboxylic acid compounds include, in addition to the (meth)acrylic acid esters, methyl crotonate, methyl angelate, methyl tiglate, methyl oleate, dimethyl maleate, and dimethyl fumarate.

[0042] Examples of the unsaturated alcohol monomer include allyl alcohol, β-methallyl alcohol, crotyl alcohol, 3-buten-1-ol, and oleyl alcohol.

[0043] Examples of the unsaturated carboxylic acid monomer include (meth)acrylic acid, crotonic acid, angelic acid, tiglic acid, oleic acid, maleic acid, maleic anhydride, and fumaric acid.

[0044] Examples of the unsaturated carboxylate monomer include sodium (meth)acrylate, zinc (meth)acrylate, ammonium (meth)acrylate, sodium crotonate, sodium oleate, sodium maleate, and sodium fumarate.

[0045] Examples of unsaturated amide monomers include (meth)acrylamide, N-methyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N,N-dimethylacrylamide, N,N-isopropylacrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxymethyl(meth)acrylate, 2-hydroxyethyl(meth)acrylamide, and N-vinylpyrrolidone.

[0046] Other examples of the vinyl compound include vinyl chloride, (meth)acrylonitrile, vinyl sulfonic acid, vinyl phosphonic acid, N-vinylpyrrolidone, 2-vinylpyridine, ethyl vinyl ether, vinyloxirane, methyl vinyl ketone, vinylene carbonate, and vinyl ethylene carbonate.

[0047] The second constitutional unit contained in the chain molecule may be of only one type, or may contain two or more types.

[0048] For example, when the cyclic molecule is cyclodextrin or a derivative of the cyclodextrin, the second constitutional unit is preferably a constitutional unit derived from a styrene monomer, a (meth)acrylic acid ester, an unsaturated amide monomer, etc., and more preferably a styrene monomer. In particular, when the cyclic molecule is α-cyclodextrin or an α-cyclodextrin derivative, the second constitutional unit is particularly preferably a constitutional unit derived from a styrene monomer, etc.

[0049] The content ratio of the second constitutional unit contained in the chain molecule is not particularly limited. For example, it is preferable that 2 to 1000 moles of the second constitutional unit are contained per mole of the chain molecule.

[0050] The second constitutional unit is preferably directly or indirectly bonded to -(S)- represented by the formula (1), and more preferably to "-(S)" represented by the formula (1a). n - is directly or indirectly attached to one or both ends of the

[0051] The chain molecule has in the molecule "-(S)" represented by the formula (1a). n It has two or more - sites and is marked "-(S) n It is particularly preferable that the second constitutional unit is provided at one or both ends of the "-" moiety. In this case, the sulfur-containing polymer material is less susceptible to depolymerization, has improved stability, and is highly soluble in organic solvents. In this case, both ends of the chain molecule are "-(S) n It may be a -" moiety or a second building block, and one end may be "-(S) n One or both ends of the chain molecule may be a "-(S)" moiety, and the other end may be a second building block. n It may be other than the - moiety and the second building block.

[0052] The terminus of the chain molecule is not particularly limited, and as described above, it is "-(S) n When the "-" site is at the end, the end of the chain molecule can be, for example, similar to known sulfur polymers, and can usually be hydrogen.

[0053] The chain molecule is "-(S) n When the chain molecule is formed by including a "-" moiety and a second constitutional unit, the content ratio of the two is not particularly limited. n The α-amino group can be formed only from the "-" moiety and the second building block.

[0054] The chain molecule may be either linear or branched, and is usually linear in that the cyclic molecules can easily thread through.

[0055] (Sulfur-containing polymer material) As described above, the sulfur-containing polymer material has a structure in which a chain molecule pierces at least one cyclic molecule in a skewered manner.

[0056] In the sulfur-containing polymer material, the number of cyclic molecules penetrating one chain molecule is not particularly limited and can vary depending on the chain length of the chain molecule, etc. Usually, the number of cyclic molecules penetrating one chain molecule is 1 or more, preferably 2 or more.

[0057] The chain molecule is "-(S) n When the compound is formed by including a -" moiety and a second building block, all of the "-(S) n It is preferred that at least one "-" moiety spans the cyclic molecule. In this case, each "-(S) n A circular molecule that penetrates the - site is called "-(S) n The second building blocks attached to both ends of the - site act as stoppers, forming the "-(S) n This prevents the cyclic molecule from falling off the - site. n Depolymerization of the - site is suppressed, improving the stability of sulfur-containing polymer materials.

[0058] In the sulfur-containing polymer material, the ratio of cyclic molecules to chain molecules is not particularly limited, and can be, for example, in the range of 1 to 100 moles of cyclic molecules per mole of chain molecules.

[0059] The weight average molecular weight (Mw) of the sulfur-containing polymer material is not particularly limited. Therefore, the sulfur-containing polymer material may be a low molecular weight polymer, so-called an oligomer, or may be an ultra-high molecular weight polymer. For example, the weight average molecular weight (Mw) of the sulfur-containing polymer material can be 500 or more. In this case, the sulfur-containing polymer material has high stability and high solubility in various solvents, so that it is excellent in processability, and also has excellent mechanical properties. The weight average molecular weight (Mw) referred to in this specification is a polystyrene equivalent value measured by gel permeation chromatography (GPC). The upper limit of the weight average molecular weight is not particularly limited, and is not particularly limited as long as it is a chain length that can be formed by polymerization. For example, the upper limit of the weight average molecular weight (Mw) can be 1,000,000 or less in consideration of processability, but is not limited thereto.

[0060] Fig. 1 shows a schematic diagram of an embodiment of a sulfur-containing polymer material. In this embodiment of the sulfur-containing polymer material, a chain molecule 11 penetrates through the ring of a cyclic molecule 12, and a second constitutional unit 13 for preventing the cyclic molecule 12 from falling off is present in the chain molecule 11.

[0061] In FIG. 1, the chain molecule 11 is “-(S) n -" moieties, the cyclic molecule is n The - site is encapsulated in a sliding manner, and the stopper structural unit 13 prevents it from falling off from the chain molecule 11.

[0062] Generally, "-(S) n Sulfur polymer moieties such as "-" moieties are prone to depolymerization, specifically, they change into ring structures composed of multiple S atoms (e.g., eight-membered rings formed by eight sulfur atoms) upon depolymerization.

[0063] However, in the sulfur-containing polymer material according to the present invention, "-(S) n It is presumed that because sulfur polymer moieties such as "-" moieties are encapsulated in cyclic molecules, the formation of cyclic structures composed of multiple S atoms is suppressed, making depolymerization less likely to occur.

[0064] In addition, since the sulfur-containing polymer material according to the present invention has chain molecules penetrating cyclic molecules, it can be said that the material is more easily dissolved in various organic solvents than conventional crosslinked sulfur-based polymers. As a result, the sulfur-containing polymer material according to the present invention is a material with excellent processability.

[0065] The type of organic solvent is not limited, and examples thereof include chlorinated hydrocarbons such as chloroform and 1,2-dichloroethane; ether compounds such as diethyl ether and tetrahydrofuran; aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; ketone compounds such as acetone and methyl ethyl ketone; ester compounds such as vinyl acetate; alcohols such as methanol, ethanol, isopropyl alcohol and t-butanol; formamides such as N,N-dimethylformamide and N,N-dimethylacetamide; pyrrolidones such as 2-pyrrolidone and N-methylpyrrolidone; dimethyl sulfoxide, carbon disulfide, etc.

[0066] The sulfur-containing polymer material may contain various additives as long as the effects of the present invention are not impaired. Examples of the additives include light stabilizers, antioxidants, preservatives, fillers such as inorganic particles, flame retardants, pigments, colorants, mildew inhibitors, lubricants, etc. One or more of these additives may be contained in the water-absorbent resin dispersion.

[0067] The sulfur-containing polymer material may be, for example, a solid, a liquid such as a paste, or a solution or dispersion. When the sulfur-containing polymer material is a solid, its shape is not particularly limited, and it may have, for example, a powder, granule, pellet, fiber, plate, film, block, sheet, rod, sphere, oval sphere, distorted shape, or the like.

[0068] The sulfur-containing polymer material of the present invention is excellent in stability and processability, and therefore can be used in various applications. For example, the sulfur-containing polymer material of the present invention can be suitably used in applications such as electronic components, battery materials, optical components, packaging materials, adhesive materials, and drug-carrying materials.

[0069] The method for producing the sulfur-containing polymeric material of the present invention is not particularly limited, and various production methods can be adopted. In particular, it is preferable to produce the sulfur-containing polymeric material by the following production method.

[0070] 2. Manufacturing method of sulfur-containing polymer material The sulfur-containing polymer material of the present invention can be produced, for example, by a production method including a step of mixing a sulfur source and a cyclic molecule. Such a step will be referred to as "Step A" below.

[0071] The sulfur source used in step A is a raw material capable of giving a sulfur polymer. For example, the sulfur source may be a sulfur unit represented by the formula (1), preferably -(S) represented by the formula (1a). n - is a raw material that can provide a sulfur site. Therefore, the sulfur source may be elemental sulfur or a compound containing a sulfur atom. - (S) n The sulfur source preferably contains elemental sulfur in that it is easy to provide - sites.

[0072] Examples of sulfur include cyclic sulfur composed of sulfur atoms, and typically, an 8-membered sulfur ring can be used as the sulfur source. Such a sulfur source can be produced by a known method or can be obtained from a commercial product.

[0073] The sulfur source can also be, for example, a sulfur polymer, which can be produced by known methods or can be obtained commercially.

[0074] The cyclic molecule used in step A may be of the same type as the cyclic molecule contained in the sulfur-containing polymer material described above. Therefore, the cyclic molecule preferably contains cyclodextrin or a cyclodextrin derivative, and is more preferably a cyclodextrin derivative in that the chain molecule is easily threaded, and is particularly preferably an α-cyclodextrin derivative. The cyclodextrin derivative preferably has a structure in which at least one or more hydrogen atoms of hydroxyl groups in cyclodextrin are substituted with at least one group selected from the group consisting of a hydrocarbon group, an acyl group, and -CONHR (R is an alkyl group), and among them, the cyclodextrin derivative preferably has a structure in which the hydrogen atoms of at least one or more hydroxyl groups in cyclodextrin are substituted with a hydrocarbon group having 1 to 4 carbon atoms. In particular, the cyclic molecule preferably has a structure in which at least one or more hydrogen atoms of hydroxyl groups in α-cyclodextrin are substituted with a hydrocarbon group having 1 to 4 carbon atoms.

[0075] The cyclic molecule used in step A can be produced by a known method or can be obtained from a commercial product. When the cyclic molecule is a cyclodextrin derivative, it can be produced by a known method using cyclodextrin, for example.

[0076] For example, known alkylation reactions can be widely adopted as a method for replacing the hydrogen atom of a hydroxyl group present in cyclodextrin with a hydrocarbon group. For example, known acylation reactions can be widely adopted as a method for replacing the hydrogen atom of a hydroxyl group present in cyclodextrin with an acyl group such as an acetyl group. Another example of a method for replacing the hydrogen atom of a hydroxyl group present in cyclodextrin with an acetyl group is an acetylation method using a solvent capable of trapping an acid such as pyridine in the presence of acetic anhydride or isopropyl acetate. For a method for replacing the hydrogen atom of a hydroxyl group present in cyclodextrin with -CONHR (R is a methyl group or an ethyl group), known alkyl carbamate reactions can be widely adopted.

[0077] In step A, by mixing a sulfur source with a cyclic molecule, for example, a pseudopolyrotaxane can be formed in which a sulfur polymer penetrates the ring of the cyclic molecule in a skewered manner. Specifically, a sulfur polymer derived from a sulfur source (for example, "-(S)" represented by the above formula (1a)) can be formed. n By inserting the cyclic amine group ("-site") into the ring of the cyclic molecule, a pseudopolyrotaxane can be formed.

[0078] The method for mixing the sulfur source and the cyclic molecules is not particularly limited, and for example, a mixture of the sulfur source and the cyclic molecules can be obtained by adding predetermined amounts of the sulfur source and the cyclic molecules to an appropriate container such as a reaction container in random order. When cyclic sulfur is used as the sulfur source, the cyclic sulfur is first opened to form a sulfur polymer, and then the sulfur polymer penetrates at least one cyclic molecule, thereby forming a pseudopolyrotaxane.

[0079] In step A, the mixture containing the sulfur source and the cyclic molecules can be held at a temperature equal to or higher than the temperature at which the sulfur polymer melts. In this case, the sulfur polymer derived from the sulfur source becomes liquid, and a mixture in which the cyclic molecules are dissolved or dispersed in this liquid sulfur (molten sulfur) is obtained. In terms of ease of melting the sulfur polymer and ease of forming pseudopolyrotaxane, the mixture in step A is preferably held at 130°C or higher, more preferably held at 140°C or higher, and even more preferably held at 155°C or higher. In terms of ease of forming pseudopolyrotaxane, the mixture is preferably held at 600°C or lower.

[0080] The time for which the mixture is kept at the above-mentioned predetermined temperature is not particularly limited and can be appropriately adjusted depending on the temperature. For example, the mixture in step A is preferably kept at a temperature of 160° C. or higher for 1 to 24 hours. In addition, in order to keep the mixture at the above-mentioned predetermined temperature, various containers such as known reactors and pressure-resistant containers can be widely used.

[0081] When the mixture is held in the container at a predetermined temperature for a predetermined time, the inside of the container can be filled with an inert gas atmosphere such as nitrogen.

[0082] By the above-mentioned step A, the sulfur polymer penetrates the ring of the cyclic molecule in a skewered manner, and thus a pseudopolyrotaxane can be formed. The sulfur polymer can be, for example, -(S) n The resulting pseudopolyrotaxane can be used as the sulfur-containing polymer material of the present invention.

[0083] Alternatively, if necessary, a compound capable of forming the above-mentioned second constitutional unit (hereinafter referred to as "compound 2") can be used in step A. In other words, a compound having a size that does not allow it to penetrate into the ring of the cyclic molecule can be used in step A.

[0084] The compound 2 may be the above-mentioned vinyl compound, that is, a known radical polymerizable monomer.

[0085] As described above, examples of the radical polymerizable monomer include styrene-based monomers, unsaturated ester-based monomers, unsaturated alcohol-based monomers, unsaturated carboxylic acid-based monomers, unsaturated carboxylate-based monomers, and unsaturated amide-based monomers, and are preferably styrene-based monomers, (meth)acrylic acid esters, and unsaturated amide-based monomers, and more preferably styrene-based monomers. In particular, when the cyclic molecule is α-cyclodextrin or an α-cyclodextrin derivative, it is particularly preferable that compound 2 is a styrene-based monomer.

[0086] When compound 2 is used in step A, the final sulfur-containing polymeric material can have a second building block as a stopper as shown in FIG. 1, for example, a cyclic molecule having the structure "-(S) n The "-" site is encapsulated in a sliding manner, and the second structural unit, which acts as a stopper, prevents the circular molecule from falling off the chain molecule.

[0087] When compound 2 is used in step A, compound 2 can be added to a mixture containing the sulfur source and the cyclic molecules, or compound 2 can be added to a product (pseudopolyrotaxane) obtained after holding a mixture containing the sulfur source and the cyclic molecules at a predetermined temperature for a predetermined time. In terms of easiness of obtaining a sulfur-containing polymer material as shown in FIG. 1, compound 2 is preferably added to a product (pseudopolyrotaxane) obtained after holding a mixture containing the sulfur source and the cyclic molecules at a predetermined temperature for a predetermined time. In any case, the addition of compound 2 advances a polymerization reaction between the sulfur terminal and compound 2, and a second constitutional unit can be introduced into the chain molecule. In particular, by adding compound 2 after the pseudopolyrotaxane is generated, the polymerization reaction between the sulfur terminal in the pseudopolyrotaxane and compound 2 advances, and thus the sulfur-containing polymer material shown in FIG. 1 is easily formed.

[0088] Therefore, the method for producing a sulfur-containing polymeric material preferably includes a step of polymerizing a product (i.e., pseudo-polyrotaxane) obtained by mixing the sulfur source and the cyclic molecule with a vinyl polymerizable monomer (such a step is referred to as "step A1"). In particular, the method for producing a sulfur-containing polymeric material preferably includes step A1 as the step A. By including step A1 in the method for producing a sulfur-containing polymeric material, a sulfur-containing polymeric material having excellent stability and processability can be easily obtained.

[0089] In step A1, the method for obtaining a product (i.e., the method for forming a pseudo-polyrotaxane) is the same as in the above-mentioned step A. In step A1, the method for mixing the pseudo-polyrotaxane and the compound 2 is not particularly limited, and for example, a predetermined amount of the pseudo-polyrotaxane and the compound 2 can be added in any order to an appropriate container such as a reaction vessel. In particular, the pseudo-polyrotaxane is formed from a sulfur source and a cyclic molecule, and then, for example, the compound 2 is added directly to the pseudo-polyrotaxane in a molten state, thereby obtaining a sulfur-containing polymer material (polyrotaxane).

[0090] In step A1, the mixture containing the pseudopolyrotaxane and compound 2 is preferably kept at 130° C. or higher, more preferably at 140° C. or higher, and even more preferably at 155° C. or higher, from the viewpoint of facilitating the polymerization reaction. In step A1, the mixture is preferably kept at 600° C. or lower, from the viewpoint of facilitating the polymerization reaction.

[0091] In step A1, the time for which the mixture is held at the above-mentioned predetermined temperature is not particularly limited and can be appropriately adjusted depending on the temperature. For example, the mixture in step A1 is preferably held at a temperature of 160° C. or higher for 1 to 24 hours. In addition, in order to hold the mixture at the above-mentioned predetermined temperature, for example, various types of containers such as known reactors and pressure-resistant containers can be widely used.

[0092] In step A1, when the mixture is held in a container at a predetermined temperature for a predetermined time, the inside of the container can be filled with an inert gas atmosphere such as nitrogen.

[0093] The polymer obtained by step A1 is the desired sulfur-containing polymer material. After the polymerization reaction, it can be purified as necessary, for example, a purification treatment using a known column or the like can be performed. The type of solvent used for purification is also not particularly limited.

[0094] In step A or step A1, the ratio of the sulfur source to the cyclic molecule is not particularly limited. For example, the amount of the cyclic molecule used per mole of the sulfur source can be 0.01 to 1000 moles.

[0095] In step A1, there is no particular limitation on the ratio of the pseudopolyrotaxane to the compound 2. For example, the amount of the compound 2 used per mole of the sulfur source used to obtain the pseudopolyrotaxane can be 0.01 to 1,000 moles. EXAMPLES

[0096] 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.

[0097] Example 1 A sulfur-containing polymeric material was produced according to the reaction scheme shown in Figure 2. First, an α-cyclodextrin derivative having a structure in which all hydrogen atoms of the hydroxyl groups of α-cyclodextrin are replaced with methyl groups was produced as a cyclic molecule by a known method. This cyclic molecule was named "TMαCD". 48 mg (39 × 10 -3 A mixture containing 1.0 g (3.9 mmol) of sulfur (S8) was prepared. The mixture was stirred in a container at 160°C for 6 hours under a nitrogen atmosphere to obtain a melt containing pseudopolyrotaxane. Next, while maintaining the melt at 160°C, 2.0 g of styrene (20 mmol) was added as a vinyl polymerizable monomer to the melt, and the mixture was stirred at 160°C for 3 hours under a nitrogen atmosphere to perform a polymerization reaction and obtain a polymer. The obtained solid polymer was purified by column chromatography using ethyl acetate / hexane (volume ratio 1:1) as an extraction solvent to obtain the desired sulfur-containing polymer material. Such a sulfur-containing polymer material was designated as "SPRx".

[0098] Comparative Example 1 According to the reaction scheme shown in FIG. 3, sulfur and styrene copolymer P(S / St) was produced. 1.0 g (3.9 mmol) of sulfur (S8) was placed in a vessel and stirred under a nitrogen atmosphere at 160°C for 6 hours to obtain a melt. 2.0 g of styrene (20 mmol) was added to this melt, and the polymerization reaction was carried out by stirring under a nitrogen atmosphere at 160°C for 3 hours to obtain a polymer. The obtained polymer was dissolved in chloroform to prepare a solution, and methanol was added to this solution to cause reprecipitation. The precipitate was washed with methanol and dried to obtain a sulfur and styrene copolymer P(S / St).

[0099] (Measurement of weight average molecular weight Mw) The weight average molecular weight (Mw) was measured using gel permeation chromatography (GPC). The measuring instruments used were "UV-8020" and "RI-8020" manufactured by Tosoh Corporation. The measured weight average molecular weight was the weight average molecular weight converted into polystyrene (PS). First, 10 ml of tetrahydrofuran (THF) was dissolved in 50 mg of sample, and the resulting solution was filtered through a 0.45 μm non-aqueous chromatographic disk. The filtrate was analyzed under the following conditions, and the PS-converted weight average molecular weight was measured. Column: Two columns of "TSKgel GMHHRM-M" manufactured by Tosoh Corporation were used. Column temperature: 40℃ Carrier gas: Tetrahydrofuran (THF) Detector: RI (Differential Refractive Index Detector) Standard polystyrene for calibration curve: "Standard polystyrene kit PStQuick" manufactured by Tosoh Corporation

[0100] (Heating loss analysis (TGA)) The heat loss analysis was carried out using "STA6000" manufactured by PerkinElmer, Inc. The heating conditions were heating from 20°C to 500°C in a nitrogen atmosphere, and the heating rate was 10°C / min.

[0101] (Evaluation Results) A dissolution test was carried out on the SPRx obtained in Example 1, and it was found that SPRx was soluble in any of the organic solvents, chloroform, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, benzene, toluene, and acetone. The dissolution test was carried out by mixing 100 parts by mass of the organic solvent and 1 part by mass of SPRx for 1 hour in an environment of 25°C, and it was determined that the SPRx was soluble in the organic solvent if no residual solvent was visible.

[0102] FIG. 4 shows the SPRx obtained in Example 1. 1 1 shows the H-NMR spectrum. Specifically, in the spectrum of FIG. 1, (A) shows the H-NMR spectrum of the mixture of P(S / St) and TMαCD obtained in Comparative Example 1 at a mass ratio of 40:1. 1H-NMR spectrum, (B) of TMαCD 1 H-NMR spectrum, (C) is the SPRx spectrum obtained in Example 1. 1 1H-NMR spectrum.

[0103] As shown in FIG. 4, the SPRx obtained in Example 1 1 In the H-NMR spectrum (C), peaks due to TMαCD and polystyrene were observed. From this result, it was found that TMαCD and polystyrene were present in the SPRx obtained in Example 1. 13 A similar phenomenon was observed in the C-NMR spectrum.

[0104] In addition, as shown in Figure 4 1 In the H-NMR spectrum, a shift in the peak position due to TMαCD was not observed in comparison between (A) and (B), whereas a shift in the peak position due to TMαCD (indicated as "Peak shift" in Figure 4) was observed in (C). In light of the fact that it is generally known that a peak shift due to cyclodextrin occurs when a compound is included in the cavity of cyclodextrin, the results in Figure 4 indicate that the SPRx obtained in Example 1 has a structure in which a chain molecule penetrates the ring of a cyclic molecule. Since no shift in the peak due to polystyrene occurred, it is also evident that the SPRx obtained in Example 1 has a sulfur polymer moiety (-(S) n It can be determined that the compound has a rotaxane structure in which TMαCD encapsulates the α-site.

[0105] 5 shows the results of GPC measurement of SPRx obtained in Example 1 and the sulfur-styrene copolymer P(S / St) obtained in Comparative Example 1. It was found that the weight average molecular weight Mw of SPRx obtained in Example 1 was about 5000, which was larger than the weight average molecular weight Mw (about 1300) of P(S / St) obtained in Comparative Example 1. This result shows that the polyrotaxane structure leads to a high molecular weight.

[0106] FIG. 6 shows the results of thermal analysis (TGA) of SPRx obtained in Example 1, sulfur-styrene copolymer P(S / St) obtained in Comparative Example 1, and a mixture (P(S / St)+TMαCD) obtained in Comparative Example 1 in which P(S / St) and TMαCD were mixed in a mass ratio of 40:1. The mass of P(S / St) in Comparative Example 1 gradually decreased with increasing temperature, and a rapid mass decrease was observed near 215°C. In contrast, the mass of SPRx obtained in Example 1 did not decrease rapidly near 215°C, and a rapid mass decrease was observed only at temperatures exceeding 255°C on the higher temperature side. From this result, it was found that the decomposition temperature of SPRx is 50°C higher than that of P(S / St). Such an effect of increasing the decomposition temperature was not observed in P(S / St)+TMαCD, which is a system in which TMαCD was added only to P(S / St). Therefore, the sulfur polymer moiety (-(S) n It is presumed that the inclusion of the sulfur polymer moiety (- moiety) with TMαCD suppresses depolymerization of the sulfur polymer moiety, resulting in improved thermal stability.

[0107] FIG. 7 shows the results of GPC of SPRx obtained in Example 1 and P(S / St) obtained in Comparative Example 1, and shows the change over time in weight average molecular weight Mw.

[0108] From the PGC results shown in Figure 7, it was found that the Mw of P(S / St) of Comparative Example 1 had decreased when it was measured again after being left stationary for about 2 weeks in an environment at 25°C from the first measurement (P(P / St)(2 weeks) in the figure), whereas the Mw of SPRx obtained in Example 1 did not decrease even after being left stationary for 6 months in an environment at 25°C from the first measurement (SPRx(6 mounths) in the figure). In the observation of the appearance of the sample, P(S / St) of Comparative Example 1 changed from deep orange to yellow, whereas the appearance of SPRx obtained in Example 1 did not change.

[0109] Therefore, the results in Figure 7 show that the sulfur polymer site (-(S) nThis indicates that the inclusion of the sulfur polymer moiety (- moiety) with TMαCD suppresses depolymerization of the sulfur polymer moiety, resulting in improved thermal stability. It was also found that the environmental stability of the SPRx obtained in Example 1 is significantly improved.

[0110] From the above, it was found that the SPRx (sulfur-containing polymer material) obtained in Example 1 is a material excellent in stability and processability because it is difficult for depolymerization to occur and has high solubility in organic solvents.

Claims

1. 1. A sulfur-containing polymeric material, comprising: Contains a chain molecule and at least one cyclic molecule, the chain molecule pierces the at least one cyclic molecule in a skewered manner, The chain molecule is at least one represented by the following formula (1a): -(S) ｎ - (1a) (Here, n is a number equal to or greater than 2, except for n=2.) The moiety is represented by the cyclic molecule comprises a cyclodextrin or a cyclodextrin derivative; The cyclodextrin derivative is a sulfur-containing polymer material having a structure in which a hydrogen atom of at least one hydroxyl group of cyclodextrin is substituted with at least one group selected from the group consisting of a hydrocarbon group, an acyl group, and -CONHR (R is an alkyl group).

2. 2. The sulfur-containing polymeric material according to claim 1, wherein n is a number of 10 or more.

3. The chain molecule further contains a second constitutional unit, The sulfur-containing polymer material according to claim 1 or 2, wherein the second constitutional unit has a size such that the second constitutional unit cannot penetrate into the ring of the cyclic molecule.

4. The sulfur-containing polymer material according to claim 3 , wherein the second structural unit is a vinyl-based structural unit.

5. The sulfur-containing polymer material described in claim 4, wherein the vinyl-based constituent unit is a styrene-based monomer.

6. A method for producing the sulfur-containing polymeric material according to any one of claims 1 to 5, comprising the steps of: A method for producing a sulfur-containing polymer, comprising: a step A of mixing a sulfur source and a cyclic molecule.

7. The method according to claim 6 , wherein in the step A, a product obtained by mixing the sulfur source and the cyclic molecule is polymerized with a vinyl polymerizable monomer.

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