Method for producing sulfur-containing polymer compound

Abstract

The present invention provides a method for producing a sulfur-containing polymer by a simple method without using an organic solvent.　A method for producing a sulfur-containing polymer compound according to the present invention comprises a step for obtaining a sulfur-containing polymer compound by reacting a linear sulfur polymer and a compound C having at least two sequentially polymerizable functional groups in the absence of an organic solvent, wherein the sulfur-containing polymer compound has a structural unit that is represented by general formula (1) : -R1-R-R1-(S)n- (in formula (1), n represents a number of 1 or more, R represents an organic group, and two R1 moieties are the same or different and each represent a divalent organic group derived from the polycondensable functional group), general formula (1'): -R1-R-(S)n- (in formula (1'), n, R, and R1 are the same as n, R, and R1 in formula (1), respectively), or general formula (1"): -CO-(S)n-.

Description

Method for producing sulfur-containing polymer compounds

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

[0002] Polymer compounds containing sulfur (sulfur-containing polymers) exhibit properties not found in polymers composed of carbon atoms, and are therefore expected to be applicable in various fields. For example, sulfur-containing polymers have high capacitance and high transparency, and are known to be useful as positive electrode materials for various batteries. They are also expected to be applied in the optical field, such as in lenses. Moreover, sulfur, which is the raw material for sulfur-containing polymers, is a surplus resource and is inexpensive, so sulfur-containing polymers are attracting attention from an economic perspective.

[0003] From this perspective, various methods for producing sulfur-containing polymers have been investigated in recent years. In particular, sulfur polymers (-(S)n-) are unstable due to decomposition at room temperature, and are insoluble in solvents and poor in processability. Therefore, there is an urgent need to establish a technology for efficiently producing sulfur-containing polymers. For example, Non-Patent Document 1 discloses a method for producing a sulfur-containing polymer having a crosslinked structure by reacting sulfur with a monomer having two or more vinyl groups (the so-called inverse vulcanization method). By employing such an inverse vulcanization method, it is possible to suppress decomposition of raw materials during production, and a sulfur-containing polymer having a stable structure can be obtained.

[0004] NATURE CHEMISTRY, VOL. 5, 518-524 (2013)

[0005] However, the production method disclosed in Non-Patent Document 1 has problems in that the synthesis conditions are complicated, and the polymer structure is easily restricted because a crosslinked structure must be formed, resulting in low flexibility in polymer design. Furthermore, from the viewpoint of reducing environmental impact in recent years, it is desirable to use organic solvents as much as possible during synthesis. From this viewpoint, there is a strong demand for the establishment of a technology for producing a sulfur-containing polymer in a simple manner that is easy to reduce environmental impact.

[0006] The present invention has been made in view of the above, and an object of the present invention is to provide a method for producing a sulfur-containing polymer by a simple method without using an organic solvent.

[0007] As a result of extensive research into achieving the above object, the present inventors have discovered that the above object can be achieved by utilizing step-growth polymerization (e.g., polycondensation reaction) of a predetermined compound in the absence of an organic solvent, and have thus completed the present invention.

[0008] That is, the present invention includes, for example, the subject matter described in the following items: Item 1: A method for producing a sulfur-containing polymer compound by reacting a linear sulfur polymer with a compound C having at least two sequentially polymerizable functional groups in the absence of an organic solvent, wherein the sulfur-containing polymer compound is represented by the following general formula (1) -R １ -R-R １ - (S) ｎ - (1) (In formula (1), n ​​represents a number of 1 or more, R represents an organic group, and two R １ are the same or different and represent a divalent organic group derived from the sequentially polymerizable functional group), １ -R-(S) ｎ - (1') (wherein n, R and R １ respectively represent n, R and R in the formula (1). １ or a compound represented by the following general formula (1") -CO-(S): ｎ Item 2. A method for producing a sulfur-containing polymer compound having a structural unit represented by the following general formula (2): R ２ -R-R ２ (2) (In formula (2), R is an organic group and has the same meaning as R in formula (1), and two R ２ Item 3: In the formula (2), R ２Item 4. The method for producing a sulfur-containing polymer compound according to Item 2, wherein R is an epoxy group, a halogen atom, a glycidyl group, —C(═O)X (X is a halogen atom), —COOH, or —NCO. １ is -CH ２ -CH(OH)-, -CH ２ -CH ２ Item 5. The method for producing a sulfur-containing polymer compound according to any one of Items 1 to 3, wherein the linear sulfur polymer is —CH(OH)—, —CO—, —COO—, or —NHCO—. Item 6. The method for producing a sulfur-containing polymer compound according to any one of Items 1 to 3, wherein the reaction of the linear sulfur polymer with the compound C is carried out in water. Item 7. The method for producing a sulfur-containing polymer compound according to any one of Items 1 to 3, wherein the reaction of the linear sulfur polymer with the compound C is carried out in the absence of a phase transfer catalyst.

[0009] According to the method for producing a sulfur-containing polymer compound of the present invention, a sulfur-containing polymer can be produced by a simple method without using an organic solvent.

[0010] 1 is a scheme showing an outline of the reaction carried out in Example 1. 2 is a Raman spectrum of the sulfur-containing polymer compounds obtained in Example 1 and Comparative Example 1. １ 1 shows a H-NMR spectrum; 2 shows an FT-IR spectrum of the sulfur-containing polymer compounds obtained in Example 1 and Comparative Example 1; 3 shows the measurement results of a tensile test of the sulfur-containing polymer compounds obtained in Example 1 and Comparative Example 1; and 4 shows the results of a tensile test of the sulfur-containing polymer compounds obtained in Examples 2a, 2b, 2c, and 2d. １ 1H-NMR spectrum of the sulfur-containing polymer compounds obtained in Example 3 and Comparative Example 3. １ 1H-NMR spectrum of the sulfur-containing polymer compounds obtained in Example 3 and Comparative Example 3. 1H-NMR spectrum of the sulfur-containing polymer compounds obtained in Example 4 and Comparative Example 4. １ 1H-NMR spectrum of the sulfur-containing polymer compounds obtained in Example 5 and Comparative Example 5. １1A-1H-NMR spectra of the sulfur-containing polymer compounds obtained in Examples 4 and 5. 1B-1H-NMR spectra of the sulfur-containing polymer compounds obtained in Examples 4 and 5. 1C-1H-NMR spectra of the sulfur-containing polymer compounds obtained in Examples 4 and 5. 1D-1H-NMR spectra of the sulfur-containing polymer compounds obtained in Examples 4 and 5.

[0011]

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

[0012] The method for producing a sulfur-containing polymer compound of the present invention includes a step of reacting a linear sulfur polymer with a compound C having at least two sequentially polymerizable functional groups in the absence of an organic solvent to obtain a sulfur-containing polymer compound. Hereinafter, this step will be referred to as "Step 1."

[0013] In step 1, a sulfur-containing polymer compound is obtained. Here, the sulfur-containing polymer compound is represented by the following general formula (1) -R １ -R-R １ - (S) ｎ - (1) (In formula (1), n ​​represents a number of 1 or more, R represents an organic group, and two R １ are the same or different and represent a divalent organic group derived from the sequentially polymerizable functional group), １ -R-(S) ｎ - (1') (wherein n, R and R １ respectively represent n, R and R in the formula (1). １ or a compound represented by the following general formula (1") -CO-(S): ｎ -(1") (wherein n has the same meaning as n in the formula (1)).

[0014] The method for producing a sulfur-containing polymer of the present invention (hereinafter referred to as the "production method of the present invention") allows for the production of a sulfur-containing polymer by a simple method without using an organic solvent. In particular, the production method of the present invention allows for the production of a sulfur-containing polymer in a higher yield than when an organic solvent is used, and also makes it easier to produce a sulfur-containing polymer having superior mechanical properties than when an organic solvent is used. Moreover, the production method of the present invention allows the reaction to proceed more rapidly than when an organic solvent is used, and the resulting sulfur-containing polymer has a larger molecular weight than a sulfur-containing polymer obtained using an organic solvent.

[0015] (Linear Sulfur Polymer) The linear sulfur polymer used in step 1 is, for example, a polymer represented by the following formula (4): Y-(S) ｎ -Y (4) (in formula (4), n represents a number of 1 or more, and two Ys are the same or different and represent a hydrogen atom, an alkali metal, or an organic base) can be used. In particular, from the viewpoint of excellent reactivity, it is preferable that both of the two Ys are alkali metals, and more preferably sodium. In formula (4), it is preferable that the two Ys are the same. When Y is an organic base, the type thereof is not particularly limited.

[0016] In the formula (4), n is not particularly limited as long as it is a number of 1 or more. n 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. n can also be 10 or less. The value of n can be calculated from a MALDI-TOF MS spectrum.

[0017] The linear sulfur polymer can be obtained, for example, by reacting a sulfur source with a metal source. The sulfur source may be, for example, elemental sulfur or a compound containing a sulfur atom. However, elemental sulfur is preferred because it is easy to obtain a linear sulfur polymer. Examples of elemental sulfur include cyclic sulfur composed of sulfur atoms, and typically, an eight-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 commercially available product.

[0018] 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.

[0019] 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.

[0020] In the reaction of the sulfur source and the metal source, the ratio of the two to be used is not particularly limited. ｎIn order to facilitate control of 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. 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 of the sulfur source with 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.

[0021] The linear sulfur polymer used in the production method of the present invention is obtained by the reaction of the sulfur source with the metal source.

[0022] (Compound C) A compound C having at least two sequentially polymerizable functional groups is used in step 1. Hereinafter, this may be simply referred to as "compound C."

[0023] In the compound C, the type of the sequentially polymerizable functional group is not particularly limited, and is preferably, for example, a functional group capable of polycondensation with the sulfur polymer represented by the formula (4). That is, in the present invention, the sequentially polymerizable functional group is preferably a functional group capable of polycondensation.

[0024] Specific examples of the polycondensable functional group include monovalent groups such as an epoxy group (a group obtained by removing one hydrogen atom from ethylene oxide), a halogen atom, a glycidyl group, -C(=O)X (X is a halogen atom such as chlorine or fluorine), -COOH, and -NCO. The halogen atom is a halo group, which is a chlorine atom, a fluorine atom, or a bromine atom.

[0025] The number of sequentially polymerizable functional groups possessed by compound C is preferably 6 or less, more preferably 5 or less. The number of sequentially polymerizable functional groups possessed by compound C may be 2 or 3, and it is particularly preferred that the number is 2.

[0026] The compound C is represented by the following general formula (2): ２ -R-R ２ (2) (In formula (2), R is an organic group, two R ２and are the same or different functional groups capable of successive polymerization. Such compounds are so-called bifunctional compounds.

[0027] In formula (2), R may be, for example, a divalent or higher organic group, preferably a divalent organic group. The divalent organic group is a group containing one or more carbon atoms, and means, for example, a group formed by removing two hydrogen atoms from an organic compound.

[0028] Examples of R in the formula (2) include an alkylene group (-C ｍ H ２ｍ - and m is an integer), an alkylene group which may have one or more substituents X and into which one or more ether bonds (-O-) may be inserted, an alkenylene group which may have one or more substituents X, an alkynylene group which may have one or more substituents X, a cycloalkylene group which may have one or more substituents X, a cycloalkenylene group which may have one or more substituents X, a cycloalkadienylene group which may have one or more substituents X, an arylene group which may have one or more substituents X, an aralkylene group which may have one or more substituents X, a non-aromatic heterocyclic group which may have one or more substituents X, and a heteroarylene group which may have one or more substituents X.

[0029] The number of carbon atoms in the alkylene group and the alkylene group into which one or more ether bonds (—O—) may be inserted is not particularly limited and can be, for example, 1 or more and 20 or less, preferably 2 or more, and preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

[0030] The number of carbon atoms in the alkenylene group is not particularly limited and can be, for example, 2 or more and 20 or less, preferably 3 or more, and more preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

[0031] The number of carbon atoms in the alkynylene group is not particularly limited and can be, for example, 2 or more and 20 or less, preferably 3 or more, and more preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

[0032] The number of carbon atoms in the cycloalkylene group, cycloalkenylene group, and cycloalkadienylene group is not particularly limited, and can be, for example, 3 or more and 20 or less, preferably 4 or more, and more preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

[0033] The number of carbon atoms in the arylene group is not particularly limited and may be, for example, 6 to 18. The number of carbon atoms in the aralkylene group is not particularly limited and may be, for example, 6 to 18.

[0034] The non-aromatic heterocyclic group may be monocyclic, bicyclic, tricyclic, or tetracyclic, and may contain, for example, carbon atoms and 1 to 4 heteroatoms selected from oxygen, sulfur, and nitrogen atoms as ring-constituting atoms. The non-aromatic heterocyclic group may be saturated or unsaturated.

[0035] Examples of the heteroarylene group include monocyclic aromatic heterocyclic groups (for example, 5- or 6-membered monocyclic aromatic heterocyclic groups) and aromatic fused heterocyclic groups (for example, 5- to 18-membered aromatic fused heterocyclic groups).

[0036] The type of the substituent X is not particularly limited, and examples thereof include a hydrocarbon group, a halo group, a nitro group, a cyano group, an oxo group, a thioxo group, a sulfo group, a sulfamoyl group, a sulfinamoyl group, and a sulfenamoyl group. The hydrocarbon group is an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkadienyl group, an aryl group, an aralkyl group, or the like, and has, for example, 1 to 10 carbon atoms.

[0037] The substituent X may be a polymer chain, specifically, -R １ - (S) ｎ That is, R in the formula (2) may have two -R １ - (S) ｎ - and then -R１ - (S) ｎ In this case, the sulfur-containing polymer compound can form a three-dimensional network structure. １ - (S) ｎ -, then R １ is bonded to R, and -(S) ｎ The terminal of the - moiety is hydrogen or an alkali metal as described below.

[0038] In formula (2), R is preferably an alkylene group optionally having one or more substituents X, or an arylene group optionally having one or more substituents X. In this case, production of the sulfur-containing polymer compound is facilitated, and mechanical properties are also likely to be improved. In formula (2), R is more preferably an alkylene group optionally having one or more substituents X, and even more preferably an alkylene group not having a substituent X. In these cases, the number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.

[0039] In the formula (2), two R ２ are preferably the same as each other, and the compound represented by the formula (2) more preferably has a symmetric structure with R as the center.

[0040] In the formula (2), R and R ２ Any combination of is possible as long as the above-mentioned conditions are satisfied. In the formula (2), examples of the functional group capable of successive polymerization include the above-mentioned functional groups capable of polycondensation.

[0041] In the case of producing a sulfur-containing polymer compound having a structural unit represented by the formula (1), one embodiment of the compound represented by the formula (2) is a compound in which R (a divalent organic group) is an alkylene group which may have one or more substituents X, two R ２ is an epoxy group (a group in which one hydrogen atom has been removed from ethylene oxide), —C(═O)X (X is a halogen atom such as chlorine or fluorine), —COOH, or —NCO.

[0042] In the case of producing a sulfur-containing polymer compound having a structural unit represented by the formula (1'), one embodiment of the compound represented by the formula (2) is a compound in which R (a divalent organic group) is an alkylene group which may have one or more substituents X, two R ２ One of the R groups can be exemplified by a monovalent group such as an epoxy group (a group obtained by removing one hydrogen atom from ethylene oxide), a glycidyl group, -C(=O)X (X is a halogen atom such as chlorine or fluorine), -COOH, and -NCO, and is not a halo group, and the other R ２ is a halo group. The halo group is, for example, a chlorine atom, a fluorine atom, or a bromine atom. ２ When one of the groups is an epoxy group (a group obtained by removing one hydrogen from ethylene oxide) and the other is a chlorine atom, the sulfur-containing polymer compound can be obtained in a higher yield.

[0043] Specific examples of the compound represented by formula (2) include compounds represented by the following formulas (2-1) to (2-7), which can be preferably used when producing a sulfur-containing polymer compound having a structural unit represented by formula (1).

[0044]

[0045] When a sulfur-containing polymer compound having a structural unit represented by the formula (1') is produced, a specific example of the compound represented by the formula (2) is epichlorohydrin.

[0046] When producing a sulfur-containing polymer compound having a structural unit represented by the formula (1"), specific examples of the compound C include COCl ２ Examples include:

[0047] The compound C may be a bifunctional compound represented by the formula (2) or a trifunctional or higher functional compound. For example, when the compound C is a trifunctional compound, for example, the compound represented by the formula (2) may further include another R ２ Specifically, the hydrogen atom of R in the compound represented by formula (2) can be further bonded to R ２ In this case, R２ is R in the formula (2) ２ and three R ２ are preferably all the same.

[0048] The compound C may be a bifunctional compound represented by the above formula (2) or a trifunctional or higher functional compound. Specific examples of such compounds include compounds represented by the following formulas (2-8) to (2-11).

[0049]

[0050] (Step 1) In step 1, the linear sulfur polymer and compound C are reacted in the absence of an organic solvent. The sulfur-containing polymer compound can be obtained by the reaction carried out in step 1. More specifically, the sulfur-containing polymer compound can be obtained by polycondensation of the linear sulfur polymer and compound C.

[0051] In step 1, the reaction between the linear sulfur polymer and the compound C is carried out in the absence of an organic solvent. That is, no organic solvent is used as a solvent in the reaction in step 1. Generally, the reaction between the linear sulfur polymer and the compound C is considered to be carried out in an organic solvent. In particular, an interfacial reaction using an organic solvent and a non-organic solvent is considered to be preferable to increase the yield. However, in the present invention, no organic solvent is used. The present inventors have unexpectedly found that the reaction between the linear sulfur polymer and the compound C without the use of an organic solvent can actually increase the yield of the product, the sulfur-containing polymer compound.

[0052] In step 1, the reaction between the linear sulfur polymer and the compound C is preferably carried out in water. In this case, the sulfur-containing polymer can be produced in a higher yield, the reaction rate is likely to be improved, and the weight-average molecular weight of the obtained sulfur-containing polymer can be increased. Carrying out the reaction between the linear sulfur polymer and the compound C in water is also preferable in terms of further reducing environmental load.

[0053] When the reaction between the linear sulfur polymer and the compound C is carried out in water, the amount of water used is not particularly limited. For example, water can be used so that the concentration of the linear sulfur polymer is 0.1 to 500 g / L, and the concentration is preferably 0.5 to 300 g / L, more preferably 1 to 200 g / L, and even more preferably 2 to 100 g / L.

[0054] In step 1, the reaction between the linear sulfur polymer and compound C can be carried out in the presence or absence of a catalyst. In particular, in the present invention, the reaction can proceed without an interfacial reaction, so the reaction between the linear sulfur polymer and compound C in step 1 can also be carried out in the absence of a phase transfer catalyst.

[0055] In the reaction between the linear sulfur polymer and compound C, the ratio of the two is not particularly limited. For example, 0.05 to 10 moles of compound C can be used per mole of linear sulfur polymer. In the production method of the present invention, the amount of compound C used per mole of linear sulfur polymer is preferably 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. From another perspective, the amount of compound C used per mole of sulfur used in the synthesis of the linear sulfur polymer can be 0.1 moles or more and 10 moles or less, preferably 0.2 moles or more, more preferably 0.3 moles or more, even more preferably 0.4 moles or more, and particularly preferably 0.5 moles or more, and preferably 8 moles or less, more preferably 6 moles or less, even more preferably 4 moles or less, and particularly preferably 3 moles or less.

[0056] In step 1, the method for reacting the linear sulfur polymer with compound C is not particularly limited. For example, compound C may be added to water in which the linear sulfur polymer is dissolved or dispersed. Alternatively, the linear sulfur polymer and compound C can be reacted by mixing water containing the linear sulfur polymer with water containing compound C.

[0057] The reaction temperature is not particularly limited when reacting the linear sulfur polymer with compound C. In particular, in the production method of the present invention, the reaction between the linear sulfur polymer and compound C is a polycondensation reaction, and therefore the reaction temperature can be lower than that for conventional sulfur-containing polymer compounds, and can be, for example, 0 to 100°C, preferably 10 to 80°C. The reaction time can be appropriately set depending on conditions such as the concentration of the starting materials and the temperature.

[0058] After the reaction between the linear sulfur polymer and the compound C 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, and drying.

[0059] The resulting reaction product is the sulfur-containing polymer compound of the present invention, which is the target product. The resulting sulfur-containing polymer compound can be purified by an appropriate method.

[0060] The reaction between the linear sulfur polymer and compound C is a polycondensation reaction. Specifically, sulfur at the terminal of the linear sulfur polymer reacts with a sequentially polymerizable functional group (a polycondensable functional group) in compound C, causing a polycondensation reaction to proceed, thereby producing the target sulfur-containing polymer compound.

[0061] The production method of the present invention can produce a sulfur-containing polymer by a simple method without using an organic solvent, and in particular, the reaction proceeds more rapidly than when an organic solvent is used, and a sulfur-containing polymer compound can be obtained in a high yield. Furthermore, the obtained sulfur-containing polymer compound has a larger molecular weight and better mechanical properties than sulfur-containing polymer compounds obtained using an organic solvent.

[0062] Furthermore, the production method of the present invention is advantageous in that it allows the production of a sulfur-containing polymer compound by a simpler method than conventional production methods for sulfur-containing polymer compounds (for example, compared to production methods such as the inverse vulcanization method described above), and also allows the reaction temperature to be lower. In addition, the production method of the present invention uses linear sulfur polymers and compound C, which have little odor, as raw materials, making deodorization during production easy. Furthermore, for example, harmful hydrogen sulfide is less likely to be generated during production compared to production methods such as the inverse vulcanization method described above, and safety during the production of sulfur-containing polymer compounds is likely to be improved.

[0063] The production method of the present invention may consist of only step 1, or may be combined with other steps as necessary.

[0064] (Sulfur-Containing Polymer Compound) The sulfur-containing polymer compound obtained by the production method of the present invention (i.e., the sulfur-containing polymer compound produced in step 1) is a polymer compound having a structural unit represented by the general formula (1), the general formula (1'), or the general formula (1'').

[0065] In the formula (1), n ​​has the same meaning as n in the above formula (4). Therefore, in the formula (1), n ​​is not particularly limited as long as it is a number of 1 or more. In order to easily improve the mechanical properties of the sulfur-containing polymer compound, n is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and particularly preferably 5 or more. In addition, 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. n can also be 10 or less.

[0066] In the formula (1), R has the same meaning as R in the formula (2). In the formula (1), R is preferably an alkylene group optionally having one or more substituents X, or an arylene group optionally having one or more substituents X. In this case, the production of the sulfur-containing polymer compound is facilitated, and the mechanical properties are also likely to be improved. In the formula (1), R is more preferably an alkylene group optionally having one or more substituents X, and even more preferably an alkylene group not having a substituent X. In these cases, the number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.

[0067] In the formula (1), R １ is a divalent organic group derived from a polycondensable functional group, and particularly R ２ is a divalent organic group derived from the formula: １ Examples of the alkyl group include groups derived from monovalent groups such as an epoxy group (a group obtained by removing one hydrogen atom from ethylene oxide), a halogen atom, a glycidyl group, -C(=O)X (X is a halogen atom such as chlorine or fluorine), -COOH, and -NCO.

[0068] R １ is a group derived from an epoxy group, -CH ２ -CH(OH)-. R in formula (1) １ Ga-CH ２ In the case of -CH(OH)-, the carbon atom not having a hydroxyl group can be bonded to R, and the carbon atom having a hydroxyl group can be bonded to S, or vice versa. ２ In —CH(OH)—, one carbon atom having a hydroxyl group bonded thereto can be bonded to S, and the other carbon atom having a hydroxyl group bonded thereto can be bonded to R.

[0069] R １ is a group derived from a glycidyl group, -CH ２ -CH ２ -CH(OH)-. R in formula (1) １ Ga-CH ２ -CH ２In the case of -CH(OH)-, the terminal carbon not having a hydroxyl group can be bonded to R, and the carbon having a hydroxyl group can be bonded to S, or vice versa. ２ -CH ２ In —CH(OH)—, one carbon atom having a hydroxyl group bonded thereto can be bonded to S, and the other carbon atom having a hydroxyl group bonded thereto can be bonded to R.

[0070] R １ is the aforementioned —C(═O)X, R in formula (1) １ is —CO—. １ is the aforementioned —COOH, R in formula (1) １ is —COO—. １ is -COO-, the ester carbon of each of the two -COO- is bonded to R, and the ester oxygen is bonded to S. １ is the aforementioned —NCO, in both of the two —NHCO—, the nitrogen is bonded to R and the oxygen is bonded to S.

[0071] In the formula (1), R １ is the aforementioned -CH ２ -CH(OH)-, -CH ２ -CH ２ Preferably, the sulfur-containing polymer is —CH(OH)—, —CO—, —COO—, or —NHCO—. In this case, the sulfur-containing polymer is easy to produce, the structure is stable because decomposition and the like are unlikely to occur, and the polymer tends to have excellent mechanical properties. １ is -CH ２ It is more preferably —CH(OH)—.

[0072] In the formula (1), R and R １ Any combination of R and R is possible. In one embodiment, R is an alkylene group which may have one or more substituents X; two R １ Ga-CH ２ -CH(OH)-, -CH ２ -CH ２ Examples of the combination include —CHOH—, —CO—, —COO—, and —NHCO—.

[0073] In formula (1), -(S) ｎ The terminal of the - moiety is hydrogen or an alkali metal as described below.

[0074] On the other hand, in formula (1′), n, R and R １ are, as described above, n, R and R in the formula (1), respectively. １ and preferred embodiments thereof are also the same as n, R and R in the formula (1). １ is the same as

[0075] The sulfur-containing polymer compound is represented by the formula (1"), which is -C(=O)-(S) ｎ It may also have a structural unit represented by the formula:

[0076] The sulfur-containing polymer compound may have other structural units as long as it has the structural unit represented by the formula (1), or the structural unit represented by the formula (1'), or the structural unit represented by the formula (1"), or the structural unit represented by the formula (1"). Alternatively, the sulfur-containing polymer compound may be formed only of the structural unit represented by the formula (1), or the structural unit represented by the formula (1'), or the structural unit represented by the formula (1"). The sulfur-containing polymer compound preferably contains 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more of the structural unit represented by the formula (1), or the structural unit represented by the formula (1'), or the structural unit represented by the formula (1").

[0077] The weight-average molecular weight of the sulfur-containing polymer compound obtained by the production method of the present invention is not particularly limited. For example, the weight-average molecular weight of the sulfur-containing polymer compound of the present invention is 1,000 or more and 100,000 or less. The weight-average molecular weight of the sulfur-containing polymer compound of the present invention is preferably 2,000 or more, more preferably 3,000 or more, even more preferably 4,000 or more, and preferably 20,000 or less. The weight-average molecular weight (Mw) referred to in this specification is a value measured by gel permeation chromatography (GPC).

[0078] In the sulfur-containing polymer compound, the content of S (elemental sulfur) is not particularly limited. For example, in terms of readily having excellent mechanical properties, it is preferably 30% by mass or more and 99% by mass, with a more preferred lower limit of 35% by mass, a more preferred upper limit of 80% by mass, a still more preferred upper limit of 70% by mass, and a particularly preferred upper limit of 50% by mass.

[0079] The sulfur-containing polymer compound obtained by the production method of the present invention can have various structures introduced into its backbone, allowing molecular design according to the application. In particular, it has excellent mechanical properties while retaining the properties of a sulfur-based polymer, and when made into a film material, for example, it has excellent tensile strength and mechanical properties. Conventional sulfur-containing polymer compounds have insufficient mechanical properties, which has been a drawback in applying them to various applications. In contrast, the sulfur-containing polymer compound obtained by the production method of the present invention has excellent mechanical properties and is therefore easily applicable to various applications. Furthermore, the refractive index of the sulfur-containing polymer compound of the present invention can be easily controlled.

[0080] Furthermore, the sulfur-containing polymer compound can exhibit a self-repairing function and also have adhesive properties, and therefore, by forming a material containing the sulfur-containing polymer compound into a desired shape, it can also be used as a self-repairing material or an adhesive material.

[0081] In addition, conventional sulfur polymers have a characteristic odor, but the sulfur-containing polymer compound obtained by the production method of the present invention has a reduced odor compared to conventional sulfur polymers.

[0082] The sulfur-containing polymer compound obtained by the production method of the present invention can be used in a variety of applications, and is suitable for use as a battery material, electronic material, optical material, packaging material, agricultural material, and adhesive.

[0083] 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.

[0084] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0085] Example 1 A sulfur-containing polymer compound was synthesized according to the reaction scheme shown in FIG. ２ S (pentahydrate, 3.28 g, 19.5 mmol, 2.0 eq.) was dissolved in 50.0 mL of water to obtain sulfur (S ８ , 2.50 g, 9.7 mmol, 1.0 eq.) was added and stirred for 24 hours. Subsequently, filtration was performed to obtain an aqueous solution of a linear sulfur polymer (abbreviated as LS) (LS aqueous solution). 1,7-octadiene diepoxide (abbreviated as OD, 4.72 g, 33.2 mmol) was added to this LS aqueous solution, and stirring was continued for 24 hours to carry out a polycondensation reaction (Step 1). Thereafter, the product precipitated at the interface was removed and washed with water, and then dried under reduced pressure to obtain the target sulfur-containing polymer compound. This was named "PolyOD-Sn." The yield of PolyOD-Sn was 5.41 g, and the yield that could be synthesized per 1 g of sulfur was 2.16 g.

[0086] (Comparative Example 1) Na ２ S (pentahydrate, 65.5 g, 390 mmol, 2.0 eq.) was dissolved in 1 L of water to obtain sulfur (S ８ , 50.0 g, 195 mmol, 1.0 eq) was added and stirred for 24 hours. Subsequently, filtration was performed to obtain an aqueous solution of a linear sulfur polymer (abbreviated as LS) (LS aqueous solution 1). Next, 1,2,7,8-diepoxyoctane (OD, 94.4 g, 664 mmol) was dissolved in 400 mL of chloroform to prepare solution 2. 24 mg of hexadecyltrimethylammonium bromide was further added to this solution 2 as a phase transfer catalyst. This solution 2 was then added to the LS aqueous solution 1, and stirring was continued for 23 hours to carry out an interfacial reaction (polycondensation reaction). During the interfacial reaction, insoluble matter formed between the water layer and the chloroform layer. This was filtered off, and the resulting solid was washed successively with water and chloroform, followed by drying under reduced pressure to obtain a sulfur-containing polymer compound. The yield of this sulfur-containing polymer compound was 62.4 g, and the yield that could be synthesized per gram of sulfur was 1.25 g.

[0087] Comparison of Example 1 and Comparative Example 1 Fig. 2 shows the results of measuring the Raman spectra of PolyOD-Sn and the sulfur-containing polymer compound obtained in Comparative Example 1. As shown in Fig. 2, －１ The peaks due to S—S bonds are observed at 630 to 790 cm －１ A peak derived from a C—S bond was confirmed.

[0088] FIG. 3 shows the results of the sulfur-containing polymer compound obtained in Comparative Example 1 and PolyOD-Sn. １ 1H-NMR spectrum (measurement solvent: DMSO-D6, measurement conditions: 500 MHz, 30°C, same below). As shown in FIG. 3, the appearance of a peak derived from an OH group and a peak shift and broadening derived from OD were observed.

[0089] 4 shows the FT-IR spectra of PolyOD-Sn and the sulfur-containing polymer compound obtained in Comparative Example 1. As shown in FIG. 4, peaks derived from OH groups were confirmed and observed.

[0090] 2 to 4, it was found that the target sulfur-containing polymer compound was obtained in Example 1.

[0091] GPC measurement of PolyOD-Sn showed that the number average molecular weight (Mn) was 4100 and Mw / Mn was 1.7. Elemental analysis of PolyOD-Sn revealed that the number of sulfur atoms (n) introduced into the polymer was 2.6 (C 40.45%, H 6.86%, N 0.00%, S 36.37%).

[0092] Furthermore, when comparing the yields that can be synthesized per gram of sulfur, it is clear that the reaction carried out in Example 1 gave a significantly higher yield of the sulfur-containing polymer compound than the reaction carried out in Comparative Example 1.

[0093] Furthermore, when comparing the time required for the orange color of LS to completely disappear during the reaction, it took about 3 days for the orange color of LS to completely disappear in Comparative Example 1, whereas it took about 24 hours in Example 1. This means that the reaction in Example 1 was about three times faster than the reaction in Comparative Example 1, and it was found that the reaction in Example 1 could significantly shorten the time required for the production of a sulfur-containing polymer compound.

[0094] FIG. 5 shows the results of tensile tests (n=4) for the sulfur-containing polymer compounds obtained in Example 1 and Comparative Example 1, and the comparative sample obtained in Comparative Example 1. In FIG. 5, the solid line indicates the measurement results for Example 1, and the dashed line indicates the measurement results for Comparative Example 1. The tensile test (stroke-test force curve) was evaluated by observing the break point of the sample using an "AUTOGRAPH" (model number: AGX-plus) manufactured by Shimadzu Corporation. This break point was defined as the end point, and the maximum stress up to the end point was defined as the breaking stress of the polymer material. This tensile test was performed using the up-type method, in which the lower end of the sheet-like polymer composite material was fixed and the upper end was moved at a tensile speed of 1 mm / sec. From this measurement, the Young's modulus and fracture energy of the polymer material were calculated. The sample was obtained by molding a dumbbell test piece (JIS K 6251, type 2 dumbbell test piece, thickness 0.2 mm).

[0095] 5. It is clear from FIG. 5 that the sulfur-containing polymer compound obtained in Example 1 has better mechanical properties than the sulfur-containing polymer compound obtained in Comparative Example 1.

[0096] (Example 2a) Na ２ S (pentahydrate, 10.4 g, 61.8 mmol, 2.0 eq.) was dissolved in 120 mL of water, and sulfur (7.92 g, 30.9 mmol, 1.0 eq.) was added and stirred for 23 hours. Subsequently, filtration was performed to obtain an aqueous solution of a linear sulfur polymer (abbreviated as LS) (LS aqueous solution). 25% by volume of this LS aqueous solution was collected, and 1,7-octadiene diepoxide (abbreviated as OD, 2.20 g, 15.5 mmol) was added to this, and stirring was continued for 24 hours to carry out a polycondensation reaction (Step 1). The product precipitated at the interface was then removed and washed with water, followed by drying under reduced pressure to obtain the target sulfur-containing polymer compound. The yield of the sulfur-containing polymer compound was 3.83 g, and the yield that could be synthesized per gram of sulfur was 1.93 g.

[0097] Example 2b A sulfur-containing polymer compound was obtained in the same manner as in Example 2a, except that the amount of OD used was changed to 19.3 mmol. The yield of the sulfur-containing polymer compound was 4.40 g, and the yield that could be synthesized per 1 g of sulfur was 2.22 g.

[0098] Example 2c A sulfur-containing polymer compound was obtained in the same manner as in Example 2a, except that the amount of OD used was changed to 23.2 mmol. The yield of the sulfur-containing polymer compound was 3.95 g, and the yield that could be synthesized per 1 g of sulfur was 1.99 g.

[0099] Example 2d A sulfur-containing polymer compound was obtained in the same manner as in Example 2a, except that the amount of OD used was changed to 26.3 mmol. The yield of the sulfur-containing polymer compound was 5.77 g, and the yield that could be synthesized per 1 g of sulfur was 2.91 g.

[0100] Table 1 shows the results of GPC measurement of the sulfur-containing polymer compounds obtained in Examples 2a to 2d.

[0101] FIG. 6 shows the results of the sulfur-containing polymer compounds obtained in Examples 2a to 2d. １ 6 shows the H-NMR spectrum of the sulfur-containing polymer compounds obtained in Examples 2a to 2d. It was confirmed from FIG.

[0102]

[0103] (Example 3) Na ２ S (pentahydrate, 10.4 g, 61.8 mmol, 2.0 eq.) was dissolved in 120 mL of water, and sulfur (7.92 g, 30.9 mmol, 1.0 eq.) was added and stirred for 24 hours. Subsequently, filtration was performed to obtain an aqueous solution of a linear sulfur polymer (abbreviated as LS) (LS aqueous solution). 25% by volume of this LS aqueous solution was sampled, and 1,4-butanediol diglycidyl ether (abbreviated as BDE, 8.75 g, 43.3 mmol) was added to this, and stirring was continued for 24 hours to carry out a polycondensation reaction (Step 1). The product precipitated at the interface was then removed and washed with water, and then dried under reduced pressure to obtain the target sulfur-containing polymer compound.

[0104] (Comparative Example 3) Na ２S (pentahydrate, 10.4 g, 61.8 mmol, 2.0 eq.) was dissolved in 120 mL of water, and sulfur (7.92 g, 30.9 mmol, 1.0 eq.) was added and stirred for 24 hours. Subsequently, an aqueous solution of linear sulfur polymer (abbreviated as LS) was obtained by filtration, and 25% by volume of this LS aqueous solution was collected and obtained as LS aqueous solution 3. 1,4-butanediol diglycidyl ether (abbreviated as BDE, 8.75 g, 43.3 mmol) was dissolved in 60 mL of chloroform to prepare solution 3. 14 mmg of hexadecyltrimethylammonium bromide was further added as a phase transfer catalyst to this solution 3. This solution 3 was added to the LS aqueous solution 3, and stirring was continued for 23 hours to carry out an interfacial reaction (polycondensation reaction). During the interfacial reaction, insoluble matter was generated between the water layer and the chloroform layer, and was filtered off. The resulting solid matter was washed with water and chloroform in that order, and then dried under reduced pressure to obtain a sulfur-containing polymer compound.

[0105] (Comparison between Example 3 and Comparative Example 3) Fig. 7 shows the results of measuring the Raman spectra of the sulfur-containing polymer compounds obtained in Example 3 and Comparative Example 3. As shown in Fig. 7, －１ The peaks due to S—S bonds are observed at 630 to 790 cm －１ A peak derived from a C—S bond was confirmed.

[0106] FIG. 8 shows the results of the sulfur-containing polymer compounds obtained in Example 3 and Comparative Example 3. １ 8 shows the H-NMR spectrum. As shown in Fig. 8, the appearance of a peak derived from OH groups and a peak shift and broadening derived from BDE were observed.

[0107] 9 shows the FT-IR spectra of the sulfur-containing polymer compounds obtained in Example 3 and Comparative Example 3. As shown in FIG. 9, peaks derived from OH groups were confirmed and observed.

[0108] From the results of FIGS. 7 to 9, it was found that the target sulfur-containing polymer compound was obtained in Example 3.

[0109] As a result of GPC measurement of the sulfur-containing polymer compound obtained in Example 3, the number average molecular weight (Mn) was 1,300 and Mw / Mn was 1.1.

[0110] Furthermore, as described above, when the reaction rate was examined based on the time until the orange color of LS during the reaction completely disappeared, it was found that in the reaction of Example 3, the time until the orange color of LS completely disappeared was 2 hours, and that the sulfur-containing polymer compound was rapidly produced.

[0111] (Example 4) Na ２ S (pentahydrate, 3.56 g, 21.2 mmol, 2.0 eq.) was dissolved in 100 mL of water, and sulfur (2.56 g, 9.98 mmol, 1.0 eq.) was added and stirred for 24 hours. Subsequently, filtration was performed to obtain an aqueous solution of a linear sulfur polymer (abbreviated as LS) (LS aqueous solution). 25% by volume of this LS aqueous solution was collected, and epichlorohydrin (abbreviated as EC, 785 mg, 8.48 mmol) was added thereto. Stirring was continued for 24 hours to carry out a polycondensation reaction (Step 1). The product precipitated at the interface was then removed and washed with water, and then dried under reduced pressure to obtain the target sulfur-containing polymer compound.

[0112] (Comparative Example 4) Na ２ S (pentahydrate, 3.56 g, 21.2 mmol, 2.0 eq.) was dissolved in 100 mL of water, and sulfur (2.56 g, 9.98 mmol, 1.0 eq.) was added and stirred for 24 hours. Next, an aqueous solution of linear sulfur polymer (abbreviated as LS) was obtained by filtration, and 25% by volume of this LS aqueous solution was collected and obtained as LS aqueous solution 4. Epichlorohydrin (EC, 785 mg, 8.48 mmol) was dissolved in 20 mL of chloroform to prepare solution 4. 12 mmg of hexadecyltrimethylammonium bromide was added as a phase transfer catalyst to this solution 4. This solution 4 was added to the LS aqueous solution 4, and stirring was continued for 23 hours to carry out an interfacial reaction (polycondensation reaction). During the interfacial reaction, insoluble matter was generated between the water layer and the chloroform layer, and was filtered off. The resulting solid matter was washed with water and chloroform in that order, and then dried under reduced pressure to obtain a sulfur-containing polymer compound.

[0113] Example 5 A sulfur-containing polymer compound was obtained in the same manner as in Example 4, except that EC was replaced with epibromohydrin (abbreviated as EB, 1.16 g, 8.48 mmol).

[0114] Comparative Example 5 A sulfur-containing polymer compound was obtained in the same manner as in Comparative Example 5, except that EC was changed to epibromohydrin (abbreviated as EB, 1.16 g, 8.48 mmol).

[0115] FIG. 10 shows the results of the sulfur-containing polymer compounds obtained in Example 4 and Comparative Example 4. １ 10 shows the H-NMR spectrum. As shown in Fig. 10, the appearance of a peak derived from an OH group and a peak shift and broadening derived from EC were observed.

[0116] FIG. 11 shows the results of the sulfur-containing polymer compounds obtained in Example 5 and Comparative Example 5. １ 11 is a H-NMR spectrum. As shown in Fig. 11, the appearance of a peak derived from an OH group and a peak shift and broadening derived from EC were observed.

[0117] 12 shows the results of measuring the Raman spectra of the sulfur-containing polymer compounds obtained in Examples 4 and 5. As shown in FIG. 12, the Raman spectra of the sulfur-containing polymer compounds obtained in Examples 4 and 5 are shown in FIG. －１ The peaks due to S—S bonds are observed at 630 to 790 cm －１ A peak derived from a C—S bond was confirmed.

[0118] Fig. 13 shows the FT-IR spectra of the sulfur-containing polymer compounds obtained in Examples 4 and 5. As shown in Fig. 13, peaks derived from OH groups were confirmed and observed.

[0119] 10 to 13, it was found that the target sulfur-containing polymer compounds were obtained in Examples 4 and 5.

[0120] Table 2 shows the results of GPC measurement of the sulfur-containing polymer compounds obtained in Examples 4 and 5 and Comparative Examples 4 and 5.

[0121]

[0122] Furthermore, as described above, when the reaction rate was examined based on the time until the orange color of LS during the reaction completely disappeared, it was found that in the reactions of Comparative Examples 4 and 5, it took more than three days for the orange color of LS to completely disappear, whereas in the reactions of Examples 4 and 5, it took only 10 minutes for the orange color of LS to completely disappear, indicating that a sulfur-containing polymer compound was rapidly produced.

Claims

1. A method for producing a sulfur-containing polymer compound, comprising the steps of: reacting a linear sulfur polymer with a compound C having at least two sequentially polymerizable functional groups in the absence of an organic solvent to obtain a sulfur-containing polymer compound; １ -R-R １ - (S) ｎ - (1) (In formula (1), n ​​represents a number of 1 or more, R represents an organic group, and two R １ are the same or different and represent a divalent organic group derived from the sequentially polymerizable functional group), １ -R-(S) ｎ - (1') (wherein n, R and R １ respectively represent n, R and R in the formula (1). １ or a compound represented by the following general formula (1") -CO-(S): ｎ - (1 ') (wherein n has the same meaning as n in formula (1)).

2. The compound C is represented by the following general formula (2): R ２ -R-R ２ (2) (In formula (2), R is an organic group and has the same meaning as R in formula (1), and two R ２ and are the same or different and are the sequentially polymerizable functional groups.

3. In the formula (2), R ２ is an epoxy group, a halogen atom, a glycidyl group, —C(═O)X (X is a halogen atom), —COOH, or —NCO.

4. In the formula (1), R １ is -CH ２ -CH(OH)-, -CH ２ -CH 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 -CH(OH)-, -CO-, -COO-, or -NHCO-.

5. The method for producing a sulfur-containing polymer compound according to any one of claims 1 to 3, wherein the reaction between the linear sulfur polymer and the compound C is carried out in water.

6. The method for producing a sulfur-containing polymer compound according to any one of claims 1 to 3, wherein the reaction between the linear sulfur polymer and the compound C is carried out in the absence of a phase transfer catalyst.

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