Sulfur-containing high-molecular compound and preparation method thereof, polymer composition and sulfur-containing compound

Abstract

The invention provides a novel sulfur-containing polymer and a preparation method thereof, a composition containing the novel sulfur-containing polymer, and a sulfur-containing compound. This sulfur-containing polymer compound has, for example, a structural unit represented by general formula (1) (in formula (1), n represents a number of 1 or more, R represents an organic group, and R1 represents a divalent organic group derived from a polycondensable functional group. This method for producing a sulfur-containing polymer compound comprises a step for obtaining a sulfur-containing polymer compound by reacting a linear sulfur polymer with a compound (C) having two functional groups that can be polycondensed. -R1-R-R1-(S) n-(1) (In the formula,-R1-R-R1-(S) n

Description

Technical Field

[0001] The invention relates to a sulfur-containing macromolecular compound and a preparation method thereof, a polymer composition and a sulfur-containing compound. Background Art

[0002] Since high molecular compounds containing sulfur (sulfur-containing polymers) have properties that polymers composed of carbon atoms do not have, it is expected that they can be used in various fields. For example, since sulfur-containing polymers have high electrostatic capacitance and high transparency, their usefulness as positive electrode materials for various batteries is known, and their application in optical fields such as lenses can also be expected. In addition, since sulfur, which is a raw material of sulfur-containing polymers, is a surplus resource and inexpensive, sulfur-containing polymers are a material that has attracted attention from an economic point of view.

[0003] From this perspective, various methods for preparing sulfur-containing polymers have been studied in recent years. In particular, sulfur polymers (-(S) n -) decomposes at room temperature and is therefore unstable, and is insoluble in solvents and lacks processability, so it is urgent to establish a technology for efficiently preparing sulfur-containing polymers. For example, Non-Patent Document 1 discloses a method for preparing a sulfur-containing polymer having a cross-linked structure by reacting sulfur with a monomer having two or more vinyl groups (i.e., the so-called reverse vulcanization method). By adopting the reverse vulcanization method, it is possible to suppress the decomposition of raw materials during preparation, thereby obtaining a sulfur-containing polymer having a stable structure.

[0004] Prior art literature

[0005] Non-patent literature

[0006] Non-patent document 1: NATURE CHEMISTRY, VOL.5, 518-524 (2013) Summary of the invention

[0007] 1. Technical issues to be resolved

[0008] However, in the preparation method disclosed in non-patent document 1, the synthesis conditions are complicated, and since a cross-linked structure needs to be formed, the polymer structure is easily limited, and there is a problem of low degree of freedom in the design of the polymer. As with carbon-based polymer compounds, if, for example, a sulfur-containing polymer can be prepared by polycondensation, a sulfur-containing polymer can be obtained in a very simple manner, and a sulfur-containing polymer with various compositions and structures can be obtained, for example, it can also have performances (for example, physical properties, etc.) that were not previously available. From this perspective, a novel sulfur-containing polymer and a preparation method thereof are strongly sought to be developed.

[0009] The present invention has been made in view of the above circumstances, and its object is to provide a novel sulfur-containing polymer and a method for preparing the same. In addition, the present invention also aims to provide a composition and a sulfur-containing compound containing the novel sulfur-containing polymer.

[0010] (II) Technical solution

[0011] The inventors of the present application have conducted intensive studies to achieve the above-mentioned object and have found that the above-mentioned object can be achieved by introducing a functional group capable of condensation polymerization into the structure and by utilizing a condensation polymerization reaction, thereby completing the present invention.

[0012] That is, the present invention includes, for example, the subject matters described in the following items.

[0013] Item 1

[0014] A sulfur-containing polymer compound, wherein the sulfur-containing polymer compound has a structural unit represented by the following general formula (1), the following general formula (1') or the following general formula (1''),

[0015] -R 1 -RR 1 -(S) n - (1)

[0016] In formula (1), n ​​represents a number greater than 1, R represents an organic group, and two R 1 are the same or different and represent a divalent organic group derived from a functional group capable of condensation polymerization,

[0017] -R 1 -R-(S) n - (1')

[0018] In formula (1'), n, R and R 1 respectively with n, R and R in the formula (1) 1 Same meaning.

[0019] -CO-(S) n - (1'')

[0020] Item 2

[0021] The sulfur-containing polymer compound according to item 1, wherein R 1 It is -CH2-CH(OH)-, -CH2-CH2-CH(OH)-, -CO-, -COO- or -NHCO-.

[0022] Item 3

[0023] A method for producing a sulfur-containing polymer compound, comprising the step of obtaining the sulfur-containing polymer compound by reacting a linear sulfur polymer with a compound C having at least two functional groups capable of condensation polymerization.

[0024] Item 4

[0025] The method for preparing a sulfur-containing polymer compound according to item 3, wherein the compound C is a compound represented by the following general formula (2):

[0026] R 2 -RR 2 (2)

[0027] In formula (2), R is an organic group, and two R 2 The same or different functional groups are capable of condensation polymerization.

[0028] Item 5

[0029] The method for preparing a sulfur-containing polymer compound according to item 4, wherein the R 2 is an epoxy group, a halogen atom, a glycidyl group, -C(=O)X, -COOH or -NCO, wherein X of -C(=O)X is a halogen atom.

[0030] Item 6

[0031] A polymer composition, wherein the polymer composition comprises the sulfur-containing polymer compound described in item 1 or 2.

[0032] Item 7

[0033] A sulfur-containing compound having a structure in which organic groups derived from functional groups capable of condensation polymerization are bonded to both ends of a sulfur polymer represented by the following general formula (3),

[0034] -(S) n - (3)

[0035] In formula (3), n represents a number greater than or equal to 1.

[0036] (III) Beneficial effects

[0037] According to the present invention, a novel sulfur-containing polymer compound can be provided. In addition, according to the preparation method of the present invention, a novel sulfur-containing polymer compound can be obtained simply. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 is a diagram showing an overview of the reaction carried out in Example 1.

[0039] Figure 2 This is a diagram showing the overview of the reaction performed in Comparative Example 1.

[0040] Figure 3 is a diagram showing an overview of the reaction carried out in Example 8.

[0041] Figure 4 is the sulfur-containing polymer compound obtained in Example 1 1 H-NMR spectrum (the measurement solvent was DMSO-D6).

[0042] Figure 5 This is the result of elemental mapping of the sulfur-containing polymer compound obtained in Example 1.

[0043] Figure 6 is the comparative sample obtained in Comparative Example 1 1 H-NMR spectrum (the measurement solvent was DMSO-D6).

[0044] Figure 7 The following are the measurement results of the tensile test of the sulfur-containing polymer compound obtained in Example 1 and the comparative sample obtained in Comparative Example 1.

[0045] Figure 8 These are the results of tensile tests on the sulfur-containing polymer compounds obtained in the respective examples.

[0046] Fig. 9 is the sulfur-containing compound obtained in Example 8 1 H-NMR spectrum (the measurement solvent was DMSO-D6).

[0047] Fig.10 These are the measurement results of the tensile test of the sulfur-containing polymer compound obtained in Example 9.

[0048] Fig.11 The following are the measurement results of the tensile test of the sulfur-containing polymer compounds obtained in Examples 10 and 11 and Comparative Example 2.

[0049] Fig.12 (a) is the sulfur-containing polymer compound obtained in Example 12 1 H-NMR spectrum, Fig.12 (b) is the microscopic Raman spectrum of the sulfur-containing polymer compound obtained in Example 12. DETAILED DESCRIPTION

[0050] Hereinafter, embodiments of the present invention will be described in detail. In addition, in this specification, the expressions "comprising" and "including" include the concepts of "comprising", "including", "consisting essentially of", and "consisting only of".

[0051] 1. Sulfur-containing polymer compounds

[0052] The sulfur-containing polymer compound of the present invention has a structural unit represented by the following general formula (1), the following general formula (1') or the following general formula (1''),

[0053] -R 1 -RR 1 -(S) n - (1)

[0054] In formula (1), n ​​represents a number greater than 1, R represents an organic group, and two R 1 are the same or different and represent a divalent organic group derived from a functional group capable of condensation polymerization,

[0055] -R 1 -R-(S) n - (1')

[0056] In formula (1'), n, R and R 1 respectively with n, R and R in the formula (1) 1 The same meaning,

[0057] -CO-(S) n - (1'')

[0058] In formula (1''), n has the same meaning as n in the above formula (1).

[0059] That is, the sulfur-containing polymer compound of the present invention is a polymer compound having a structure represented by formula (1) as a repeating unit, a polymer compound having a structure represented by formula (1') as a repeating unit, or a polymer compound having a structure represented by formula (1'') as a repeating unit.

[0060] The sulfur-containing polymer compound of the present invention is a novel compound, and it is expected to exhibit functions that conventional sulfur polymers do not have, and it is not easy to decompose. For example, the sulfur-containing polymer compound of the present invention has excellent physical properties. In addition, the sulfur-containing polymer compound of the present invention can also be obtained by a simple method.

[0061] In the formula (1), n ​​is not particularly limited as long as it is a number greater than 1. From the viewpoint of easily improving the physical properties of the sulfur-containing polymer compound, n is preferably greater than 2, more preferably greater than 3, further preferably greater than 4, and particularly preferably greater than 5. In addition, the upper limit of n is not particularly limited, and can be, for example, less than 10,000, preferably less than 5,000, more preferably less than 3,000, further preferably less than 1,000, and particularly preferably less than 500. n can also be less than 10. The value of n can be adjusted according to the type of the sulfur-containing polymer compound. 1 The calculations were performed based on the results of H-NMR spectroscopy and elemental analysis.

[0062] In the formula (1), R may be, for example, a divalent or higher valent organic group, preferably a divalent organic group. A divalent organic group is a group containing one or more carbon atoms, for example, a group formed by removing two hydrogen atoms from an organic compound.

[0063] Examples of R in the formula (1) include

[0064] The alkylene group (-C m H 2m -, m is an integer), an alkylene group which may have one or more substituents X and may have one or more ether bonds (-O-),

[0065] an alkenylene group which may have one or more substituents X,

[0066] an alkynylene group which may have one or more substituents X,

[0067] A cycloalkylene group which may have one or more substituents X,

[0068] a cycloalkenylene group which may have one or more substituents X,

[0069] A cycloalkadienyl group which may have one or more substituents X,

[0070] an arylene group which may have one or more substituents X,

[0071] an aralkylene group which may have one or more substituents X,

[0072] a non-aromatic heterocyclic group which may have one or more substituents X,

[0073] The heteroarylene group may have one or more substituents X.

[0074] The number of carbon atoms of 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 to 20, preferably 2 or more, preferably 15 or less, more preferably 10 or less, and further preferably 8 or less.

[0075] 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 preferably 15 or less, more preferably 10 or less, and further preferably 8 or less.

[0076] 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, preferably 15 or less, more preferably 10 or less, and further preferably 8 or less.

[0077] The number of carbon atoms in the cycloalkylene group, cycloalkenylene group and cyclodienylene group is not particularly limited, and can be, for example, 3 or more and 20 or less, preferably 4 or more, preferably 15 or less, more preferably 10 or less, and further preferably 8 or less.

[0078] The number of carbon atoms in the arylene group is not particularly limited, and can be, for example, 6 or more and 18 or less. The number of carbon atoms in the aralkylene group is not particularly limited, and can be, for example, 6 or more and 18 or less.

[0079] The non-aromatic heterocyclic group is monocyclic, bicyclic, tricyclic or tetracyclic, and can be, for example, a non-aromatic heterocyclic group containing 1 to 4 heteroatoms selected from oxygen atoms, sulfur atoms and nitrogen atoms as atoms constituting the ring, in addition to carbon atoms. The non-aromatic heterocyclic group is saturated or unsaturated.

[0080] Examples of the heteroarylene group include a monocyclic aromatic heterocyclic group (eg, a 5-membered or 6-membered monocyclic aromatic heterocyclic group) and an aromatic condensed heterocyclic group (eg, a 5- to 18-membered aromatic condensed heterocyclic group).

[0081] The type of the substituent X is not particularly limited, and examples thereof include hydrocarbon groups, halogen groups, nitro groups, cyano groups, oxy groups, sulfenyl groups, sulfo groups, sulfamoyl groups, sulfinamoyl groups, and sulfenamoyl groups. The hydrocarbon group is an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a cyclodienyl group, an aryl group, an aralkyl group, and the like, and the number of carbon atoms is, for example, 1 to 10.

[0082] The substituent X may be a polymer chain, specifically, -R 1 -(S) n -. That is, in the R of the formula (1), between the two -R 1 -(S) n - can be further bonded to -R 1 -(S) n -. At this time, the sulfur-containing polymer compound can form a three-dimensional network structure. When the substituent X is -R 1 -(S) n -, R 1 Bonded to R, -(S) n The terminal of the - site is hydrogen or an alkali metal as described below.

[0083] In formula (1), R is preferably an alkylene group which may have one or more substituents X, and preferably an arylene group which may have one or more substituents X. In this case, the preparation of the sulfur-containing polymer compound becomes easy, and the physical properties are also easy to improve. In formula (1), R is more preferably an alkylene group which may have one or more substituents X, and further preferably an alkylene group which does not have a substituent X. In this case, the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.

[0084] In the formula (1), R 1 There are no particular limitations as long as the divalent organic group is derived from a functional group capable of condensation polymerization. A divalent organic group is a group containing one or more carbon atoms, for example, a group formed by removing two hydrogen atoms from an organic compound. In formula (1), preferably two R 1 are the same as each other, and more preferably, -R 1 -RR 1 -The parts are symmetrical with R as the center.

[0085] The type of the polycondensable functional group is not particularly limited, but the polycondensable functional group is preferably a functional group that is polycondensable with the sulfur polymer represented by the following formula (4).

[0086] Y-(S) n -Y (4)

[0087] In formula (4), n represents a number of 1 or more, and two Ys are the same or different and represent a hydrogen atom or an alkali metal.

[0088] In formula (4), two Ys are preferably the same.

[0089] Examples of the functional group capable of condensation polymerization include monovalent groups such as epoxy groups (groups obtained by removing one hydrogen atom from ethylene oxide), glycidyl groups, -C(=O)X (X is a halogen atom such as chlorine or fluorine), -COOH, and -NCO. 1 It is noted that the polycondensable functional group is a functional group other than a halogen group (a fluorine group, a chlorine group, etc.).

[0090] When the functional group capable of condensation polymerization is an epoxy group, R in formula (1) 1 is -CH2-CHOH-. When R in formula (1) 1 In the case of -CH2-CHOH-, the carbon to which a hydroxyl group is not bonded may be bonded to R, and the carbon to which a hydroxyl group is bonded may be bonded to S, or vice versa. Furthermore, when two -CH2-CHOH- are bonded to R, the carbon to which a hydroxyl group is bonded may be bonded to S at one of them, and the carbon to which a hydroxyl group is bonded may be bonded to R at the other.

[0091] When the functional group capable of condensation polymerization is a glycidyl group, R in formula (1) 1 is -CH2-CH2-CHOH-. When R in formula (1) 1 In the case of -CH2-CH2-CHOH-, the terminal carbon to which a hydroxyl group is not bonded may be bonded to R, and the carbon to which a hydroxyl group is bonded may be bonded to S, or vice versa. In addition, of the two -CH2-CH2-CHOH- bonded to R, the carbon to which a hydroxyl group is bonded may be bonded to S, and the carbon to which a hydroxyl group is bonded may be bonded to R.

[0092] When the functional group capable of condensation polymerization is -C(=O)X, R in formula (1) 1 It is -CO-.

[0093] When the functional group capable of condensation polymerization is -COOH, R in formula (1) 1 is -COO-. When R 1 In the case of -COO-, the ester carbons of the two -COO- are bonded to R, and the ester oxygen is bonded to S.

[0094] When the functional group capable of condensation polymerization is -NCO, R in formula (1) 1 is -NHCO-. When R 1 In the case of -NHCO-, the nitrogen atoms of the two -NHCO- atoms are bonded to R, and the oxygen atoms are bonded to S.

[0095] In the formula (1), R 1 Preferably, it is -CH2-CH(OH)-, -CH2-CH2-CHOH-, -CO-, -COO- or -NHCO-. In this case, it is easy to prepare the sulfur-containing polymer compound, and it is not easy to decompose, so the structure is stable and it is easy to have excellent physical properties. 1 More preferred is -CH2-CH(OH)-.

[0096] In the formula (1), R and R 1 All combinations are possible. As one embodiment, R is an alkylene group which may have one or more substituents X, and two R 1 It is a combination of -CH2-CH(OH)-, -CH2-CH2-CHOH-, -CO-, -COO- or -NHCO-.

[0097] In formula (1), -(S) n The terminal of the - site is hydrogen or an alkali metal as described below.

[0098] On the other hand, in formula (1'), as described above, n, R and R 1 respectively with n, R and R in the formula (1) 1The preferred forms of these groups are the same as those of n, R and R in the formula (1). 1 same.

[0099] The sulfur-containing polymer compound may also have -C(=O)-(S) as shown in the formula (1'') n - The structural unit represented.

[0100] The sulfur-containing polymer compound of the present invention may have other structural units as long as it has the structural unit represented by the formula (1), the structural unit represented by the formula (1'), or the structural unit represented by the formula (1''). Alternatively, the sulfur-containing polymer compound of the present invention may be composed only of the structural unit represented by the formula (1), the structural unit represented by the formula (1'), or the structural unit represented by the formula (1''). The sulfur-containing polymer compound of the present invention 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), the structural unit represented by the formula (1'), or the structural unit represented by the formula (1'').

[0101] The weight average molecular weight of the sulfur-containing polymer compound 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 4,000 or more and preferably 20,000 or less. In addition, the weight average molecular weight (Mw) described in this specification is a value obtained by gel permeation chromatography (GPC).

[0102] In the sulfur-containing polymer compound of the present invention, the content of S (sulfur element) is not particularly limited. For example, from the perspective of easily having excellent physical properties, the content of S (sulfur element) is 30% by mass or more, preferably 99% by mass, and a more preferred lower limit is 35% by mass. A more preferred upper limit is 80% by mass, a further preferred upper limit is 70% by mass, and a particularly preferred upper limit is 50% by mass.

[0103] The sulfur-containing polymer compound of the present invention is a novel compound. Since various structures can be introduced into the skeleton, molecular design can be performed according to the application. In particular, it has excellent physical properties while having the characteristics of sulfur-based polymers. For example, it has excellent tensile strength or physical properties when made into a film material. The physical properties of conventional sulfur-containing polymers are insufficient, which is a disadvantage when they are applied to various applications. In contrast, the sulfur-containing polymer compound of the present invention has excellent physical properties and is therefore easily applied to various applications. In addition, the sulfur-containing polymer compound of the present invention is also easy to control the refractive index.

[0104] In addition, the sulfur-containing polymer compound of the present invention can also exhibit a self-repairing function and further, can also have an adhesive property. Therefore, by shaping a material containing the sulfur-containing polymer compound of the present invention into a desired shape, it can be used as a self-repairing material or an adhesive material.

[0105] In addition, conventional sulfur polymers have a unique odor, but the sulfur-containing polymer compound of the present invention has a suppressed odor compared to conventional sulfur polymers.

[0106] Therefore, the sulfur-containing polymer compound of the present invention can be used in various applications and is suitable for battery materials, electronic materials, optical materials, packaging materials, agricultural materials, and adhesives.

[0107] The sulfur-containing polymer compound of the present invention can be made into a polymer composition alone, or can be combined with other compounds and / or additives to make a polymer composition. The polymer composition contains the sulfur-containing polymer compound, and thus can be applied to various uses such as those mentioned above, such as being suitable for use as various optical components such as lenses, and in addition, for example, being suitable for use as films, molding, self-repairing materials, bonding, etc.

[0108] The polymer composition can be used to form various materials, for example, various materials such as a film, a molded body, a powder material, a solution, a dispersion, and a paste.

[0109] The method for preparing the sulfur-containing polymer compound of the present invention is not particularly limited. For example, the sulfur-containing polymer compound of the present invention is preferably prepared by the method for preparing the sulfur-containing polymer compound of the present invention described below.

[0110] 2. Preparation method of sulfur-containing polymer compound

[0111] The method for producing a sulfur-containing polymer compound of the present invention (hereinafter referred to as "the production method of the present invention") comprises a step of obtaining a sulfur-containing polymer compound by reacting a linear sulfur polymer with a compound C having at least two functional groups capable of condensation polymerization. More specifically, the sulfur-containing polymer compound can be obtained by condensation polymerization of a linear sulfur polymer and a compound C having two functional groups capable of condensation polymerization.

[0112] As the linear sulfur polymer used in the production method of the present invention, for example, a sulfur polymer represented by the following formula (4) can be used.

[0113] Y-(S) n -Y (4)

[0114] In formula (4), n represents a number greater than or equal to 1, and two Ys are the same or different and represent a hydrogen atom or an alkali metal. In view of excellent reactivity, both Ys are preferably alkali metals, and more preferably sodium.

[0115] In the formula (4), n is not particularly limited as long as it is a number greater than 1. n is preferably greater than 2, more preferably greater than 3, further preferably greater than 4, and particularly preferably greater than 5. In addition, the upper limit of n is not particularly limited, and for example, it can be set to less than 10000, preferably less than 5000, more preferably less than 3000, further preferably less than 1000, and particularly preferably less than 500. n can also be set to less than 10. The value of n can be calculated by MALDI-TOF MS spectrum.

[0116] 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, a sulfur monomer or a compound containing a sulfur atom. From the perspective of easily obtaining a linear sulfur polymer, the sulfur source is preferably a sulfur monomer. Examples of the sulfur monomer include cyclic sulfur composed of sulfur atoms, and typically, an eight-membered ring of sulfur can be used as the sulfur source. The sulfur source can be prepared by a known method or can be obtained from a commercially available product.

[0117] As the metal source, for example, alkali metals and alkali metal compounds can be listed. There is no particular limitation on the alkali metal, and for example, sodium, potassium, and lithium can be listed, among which sodium is preferred. In addition, as the alkali metal compound, alkali metal sulfides can be listed, among which sodium sulfide is preferred. The alkali metal compound can be a hydrate. From the perspective of simple reaction and large-scale synthesis, the metal source is preferably an alkali metal compound, more preferably an alkali metal sulfide, and particularly preferably sodium sulfide.

[0118] The method for reacting the sulfur source with the metal source is not particularly limited, and for example, a method of mixing the sulfur source with the metal source in a solvent can be cited. When a solvent is used in the reaction, its type is not particularly limited, and various organic solvents can be used in addition to water. When the metal source is an alkali metal compound, especially when it is an alkali metal sulfide, the solvent is preferably an aqueous solvent, and water is particularly preferably used. In addition, when the metal source is an alkali metal, the solvent is preferably an organic solvent, and a polar solvent such as dimethylacetamide is particularly preferably used.

[0119] In the reaction of the sulfur source and the metal source, the ratio of the two is not particularly limited. For example, it is easy to control - (S) n-From the perspective of the chain length of the part, that is, the value of n, the amount of the metal source is preferably 0.1 to 20 moles, more preferably 0.5 to 10 moles, further preferably 0.8 to 8 moles, and particularly preferably 1 to 3 moles relative to 1 mole of the sulfur source. The reaction temperature when the sulfur source and the metal source are reacted is not particularly limited, for example, it can be set to 0 to 200°C, preferably 15 to 80°C. The reaction time of the sulfur source and the metal source is also not particularly limited. For example, it can be set to 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.

[0120] The linear sulfur polymer used in the production method of the present invention can be obtained by the reaction of a sulfur source and a metal source.

[0121] In the compound C having at least two polycondensable functional groups used in the preparation method of the present invention, the polycondensable functional groups are the same as the polycondensable functional groups described above. Therefore, in the compound C, the polycondensable functional groups are preferably functional groups that can be polycondensed with the sulfur polymer represented by the formula (4).

[0122] That is, as functional groups capable of condensation polymerization, for example, monovalent groups such as epoxy groups (groups obtained by removing one hydrogen from ethylene oxide), glycidyl groups, -C(=O)X (X is a halogen atom such as chlorine or fluorine), -COOH and -NCO can be listed. In addition, when preparing a sulfur-containing polymer compound having a structural unit represented by the formula (1), the functional group capable of condensation polymerization is preferably a group other than a halogen group (fluorine group, chlorine group, etc.). In addition, when preparing a sulfur-containing polymer compound having a structural unit represented by the formula (1'), as functional groups capable of condensation polymerization, in addition to the above-mentioned monovalent groups, halogen atoms can be further listed. When preparing a sulfur-containing polymer compound having a structural unit represented by the formula (1''), two functional groups capable of condensation polymerization can be listed as halogen atoms.

[0123] The number of polycondensable functional groups possessed by compound C is preferably 6 or less, and more preferably 5 or less. The number of polycondensable functional groups possessed by compound C may be 2 or 3, and particularly preferably 2.

[0124] Examples of the compound C include compounds represented by the following general formula (2), which are so-called difunctional compounds.

[0125] R 2 -RR 2 (2)

[0126] In formula (2), R is an organic group, and two R 2 The same or different functional groups capable of condensation polymerization).

[0127] In formula (2), R has the same meaning as R in formula (1). Therefore, in formula (2), examples of R include an alkylene group (-C m H 2m -, m is an integer), an alkylene group which may have one or more substituents X and may have one or more ether bonds (-O-),

[0128] an alkenylene group which may have one or more substituents X,

[0129] an alkynylene group which may have one or more substituents X,

[0130] A cycloalkylene group which may have one or more substituents X,

[0131] a cycloalkenylene group which may have one or more substituents X,

[0132] a cyclodienylene group which may have one or more substituents X,

[0133] an arylene group which may have one or more substituents X,

[0134] an aralkylene group which may have one or more substituents X,

[0135] a non-aromatic heterocyclic group which may have one or more substituents X,

[0136] The heteroarylene group may have one or more substituents X.

[0137] The substituent X also has the same meaning as the substituent X that may be contained in the above formula (1) (however, when R in formula (2) has a substituent X, the substituent X preferably excludes the above polymer chain).

[0138] In formula (2), R is preferably an alkylene group which may have one or more substituents X, or an arylene group which may have one or more substituents X. In this case, polycondensation with the linear sulfur polymer is likely to occur, and the physical properties of the obtained sulfur-containing polymer compound are also likely to be improved. In formula (2), R (divalent organic group) is more preferably an alkylene group which may have one or more substituents X, and further preferably an alkylene group which does not have a substituent X. In these cases, the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.

[0139] In formula (2), R 2 is a functional group capable of condensation polymerization. 2Examples include epoxy groups (groups obtained by removing one hydrogen from ethylene oxide), halogen atoms, glycidyl groups, -C(=O)X (X is a halogen atom such as chlorine or fluorine), -COOH, and monovalent groups such as -NCO. Examples of compound C include 1,2,7,8-diepoxyoctane and adipoyl chloride.

[0140] When preparing a sulfur-containing polymer compound having a structural unit represented by formula (1), the two R 2 The two R 2 are not halogen groups at the same time. 2 For example, the fluorine group and the chlorine group are removed. On the other hand, when preparing a sulfur-containing polymer compound having a structural unit represented by the formula (1'), the two R 2 One of them can be exemplified by a monovalent group such as an epoxy group (a group obtained by removing one hydrogen 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 halogen group, and the other R 2 The halogen group in this case is, for example, a chlorine atom, a fluorine atom, or a bromine atom.

[0141] In the formula (2), R and R 2 When preparing a sulfur-containing polymer compound having a structural unit represented by the formula (1), as one form of the compound represented by the formula (2), R (divalent organic group) is an alkylene group which may have one or more substituents X, two R 2 is a combination of an epoxy group (a group obtained by removing one hydrogen from ethylene oxide), -C(=O)X (X is a halogen atom such as chlorine or fluorine), -COOH or -NCO. In addition, when preparing a sulfur-containing polymer compound having a structural unit represented by the formula (1'), as one form of the compound represented by the formula (2), R (a divalent organic group) is an alkylene group which may have one or more substituents X, and two R 2 A combination in which one of them is an epoxy group (a group obtained by removing one hydrogen from ethylene oxide), -C(=O)X (X is a halogen atom such as chlorine or fluorine), -COOH or -NCO, and the other is a chlorine atom.

[0142] When preparing a sulfur-containing polymer compound having a structural unit represented by the formula (1), specific examples of the compound represented by the formula (2) include compounds represented by the following formulas (2-1) to (2-7).

[0143] [Chemical formula 1]

[0144]

[0145] When a sulfur-containing polymer compound having a structural unit represented by the above formula (1') is prepared, epichlorohydrin is mentioned as a specific example of the compound represented by the above formula (2).

[0146] When preparing a sulfur-containing polymer compound having a structural unit represented by the above formula (1"), COCl2 can be cited as a specific example of compound C.

[0147] In addition to the difunctional compound represented by the above formula (2), the compound C may also be a trifunctional compound or higher. For example, when the compound C is a trifunctional compound, for example, another R is further bonded to R of the compound represented by the formula (2). 2 Specifically, the compound represented by the formula (2) may be a compound in which the hydrogen atom of R is further replaced by R 2 In this case, R 2 R of formula (2) 2 Same, and preferably 3 R 2 are the same.

[0148] In addition to the difunctional compound represented by the above formula (2), the compound C may be a trifunctional or higher compound. Specific examples of such compounds include compounds represented by the following formulae (2-8) to (2-11).

[0149] [Chemical formula 2]

[0150]

[0151] In the production method of the present invention, the method for reacting the linear sulfur polymer with the compound C is not particularly limited. For example, a method of reacting the linear sulfur polymer with the compound C in a solvent can be adopted. From the viewpoint of easily improving the reactivity of both, the reaction between the linear sulfur polymer and the compound C is preferably carried out at the interface. Specifically, a solution 1 in which the linear sulfur polymer is dissolved and a solution 2 in which the compound C is dissolved are prepared, and these two solutions can be used for the interfacial reaction. Therefore, a solvent used for preparing the solution 1 and a solvent that is phase-separated from (does not dissolve in each other) the solvent used for preparing the solution 1 are used separately.

[0152] In addition, as another aspect of the method for reacting the linear sulfur polymer with the compound C, there can be mentioned a method of reacting the linear sulfur polymer with the compound C in a solvent A. In this case, for example, the solvent used in the reaction for obtaining the linear sulfur polymer may be the same as or different from the solvent A used in the reaction of the linear sulfur polymer with the compound C, but is preferably the same from the viewpoint of simplicity. In addition, the reaction for obtaining the linear sulfur polymer is the reaction of sulfur with a metal source as described above.

[0153] Examples of the solvent used to prepare the solution 1 include water, an aqueous solvent such as an alcohol compound, and other polar solvents such as dimethylacetamide and acetonitrile. Among them, the solvent used to prepare the solution 1 is preferably water.

[0154] On the other hand, the solvent used to prepare the solution 2 is preferably an organic solvent that is phase-separated from the aqueous solvent. Examples of the organic solvent include hydrocarbon solvents such as benzene, toluene, xylene, and hexane; ketone solvents such as acetone, methyl ethyl ketone, and isophorone; alcohol solvents such as tert-butyl alcohol, benzyl alcohol, phenoxyethanol, and propylene glycol; halogenated hydrocarbon solvents such as dichloromethane and chloroform; ether solvents such as 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane, and anisole; ester solvents such as ethyl acetate, propyl acetate, ethyl carbitol acetate, and butyl carbitol acetate; amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide; carbonate solvents such as dimethyl carbonate, diethyl carbonate, and propylene carbonate. The solvent used to prepare the solution 2 is preferably a halogenated hydrocarbon solvent, and more preferably chloroform.

[0155] The concentration of the solution 1 is not particularly limited, and can be, for example, 0.1 to 500 g / L, preferably 0.5 to 300 g / L, more preferably 1 to 200 g / L, and further preferably 2 to 100 g / L. In addition, the concentration of the solution 2 is not particularly limited, and can be, for example, 0.1 to 500 g / L, more preferably 0.2 to 300 g / L, and further preferably 0.5 to 200 g / L.

[0156] The solvent A may be the same type of solvent as the solvent used to prepare the solution 1 or the solvent used to prepare the solution 2, and among them, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, etc. can be preferably used.

[0157] In the reaction of the linear sulfur polymer and the compound C, the ratio of the two is not particularly limited. For example, 0.05 to 10 mol of the compound C can be used per 1 mol of the linear sulfur polymer. In the production method of the present invention, 0.1 to 8 mol of the compound C is preferably used per 1 mol of the linear sulfur polymer, 0.2 to 5 mol is more preferably used, 0.25 to 3 mol is further preferably used, and 0.3 to 2.5 mol is particularly preferably used. Therefore, even when the interface reaction is performed using the solution 1 and the solution 2, the amount of the compound C used per 1 mol of the linear sulfur polymer can be set to the above range.

[0158] The interfacial reaction using the solution 1 and solution 2 can be carried out by the method identical with known interfacial reaction, for example. In this interfacial reaction, a catalyst can also be used as required. As catalyst, for example, the phase-transfer catalyst used in the interfacial reaction in the past can be used, and ammonium salts with long-chain alkyl groups such as hexadecyl trimethyl ammonium bromide can be illustrated. The usage amount of the catalyst is not particularly limited yet, and can be set to the amount identical with the interfacial reaction in the past, and can usually use a phase-transfer catalyst with a so-called catalyst amount.

[0159] In the production method of the present invention, when the linear sulfur polymer and the compound C are reacted, the reaction temperature is not particularly limited. In particular, in the production method of the present invention, since the reaction between the linear sulfur polymer and the compound C is a polycondensation reaction, the reaction temperature can be set to a lower temperature than that of conventional sulfur-containing polymers, for example, 0 to 100° C., preferably 10 to 80° C. When the above-mentioned interfacial reaction is adopted, the same temperature can also be set. The reaction time can be appropriately set according to conditions such as concentration and temperature.

[0160] After the reaction of the linear sulfur polymer and the compound C is completed, the reaction product can be separated by an appropriate method. For example, after the reaction is completed, the reaction product can be separated by combining one or more appropriate methods such as filtration, centrifugation, distillation, and drying. In the above-mentioned interfacial reaction, insoluble matter is generated at the interface, and the reaction product can be obtained by applying the above-mentioned appropriate method.

[0161] The obtained reaction product is the sulfur-containing polymer compound of the present invention as the target product. The obtained sulfur-containing polymer compound can be purified by an appropriate method.

[0162] In the preparation method of the present invention, the reaction between the linear sulfur polymer and compound C is a polycondensation reaction. Specifically, the terminal sulfur of the linear sulfur polymer reacts with the polycondensable functional group in compound C to produce the sulfur-containing polymer compound of the present invention.

[0163] By utilizing this polycondensation reaction, a sulfur-containing polymer compound can be prepared by a simple method compared to conventional methods for preparing sulfur-containing polymer compounds (for example, compared to the above-mentioned reverse sulfidation method and the like), and the reaction temperature can be set to a low temperature. In addition, in the preparation method of the present invention, since a linear sulfur polymer or compound C with little odor is used as a raw material, deodorization during preparation is easy. In addition, for example, compared to the above-mentioned reverse sulfidation method and the like, harmful hydrogen sulfide is not easily generated during preparation, and the safety during the preparation of the sulfur-containing polymer compound is easily improved.

[0164] Therefore, the production method of the present invention is suitable as a method for producing the above-mentioned sulfur-containing polymer compound of the present invention.

[0165] 3. Sulfur compounds

[0166] The present invention also includes a sulfur-containing compound having a structure in which organic groups derived from condensation-polymerizable functional groups are bonded to both ends of a sulfur polymer represented by the following general formula (3).

[0167] -(S) n - (3)

[0168] In formula (1), n ​​represents a number greater than or equal to 1.

[0169] In formula (3), n is not particularly limited as long as it is a number greater than 1. n is preferably greater than 2, more preferably greater than 3, further preferably greater than 4, and particularly preferably greater than 5. In addition, the upper limit of n is not particularly limited, and for example, it can be set to less than 10000, preferably less than 5000, more preferably less than 3000, further preferably less than 1000, and particularly preferably less than 500. n can also be set to less than 10. The value of n can be calculated by MALDI-TOF MS spectrum.

[0170] In the sulfur-containing compound, the organic group derived from the functional group capable of condensation polymerization includes R 3 -R 1 - represents a monovalent group. 1 R in the above formula (1) 1 have the same meaning. Therefore, R 3 -R 1 R 1 Examples thereof include -CH2-CH(OH)-, -CH2-CH2-CHOH-, -CO-, -COO- or -NHCO-.

[0171] In addition, R 3 -R 1 R3 is a monovalent organic group to which one hydrogen atom is added to R in the above formula (1). 3 The following can be listed:

[0172] an alkyl group which may have one or more substituents X,

[0173] An alkyl group which may have one or more substituents X and may have one or more ether bonds (-O-) inserted therein,

[0174] an alkenyl group which may have one or more substituents X,

[0175] an alkynyl group which may have one or more substituents X,

[0176] A cycloalkyl group which may have one or more substituents X,

[0177] A cycloalkenyl group which may have one or more substituents X,

[0178] a cyclodienylene group which may have one or more substituents X,

[0179] The aryl group may have one or more substituents X.

[0180] In addition, R 3 -R 1 R 3 An alkyl group which may have one or more substituents X or an aryl group which may have one or more substituents X is preferred.

[0181] The sulfur-containing compound can be, for example, 3 -R 2 The reaction is obtained. Among them, R 2 R of formula (2) 2 have the same meaning, so R 2 It is a monovalent group such as an epoxy group (a group obtained by removing one hydrogen from ethylene oxide), a glycidyl group, -C(=O)X (X is a halogen atom such as chlorine or fluorine), -COOH, and -NCO.

[0182] For example, it is possible to react with R 3 -R 2 The interfacial reaction method can be the same as the method for preparing the sulfur-containing polymer compound of the present invention. 3 -R 2 For example, styrene oxide etc. are mentioned.

[0183] When specifying the invention included in the present disclosure, the various components (properties, structures, functions, etc.) described in the various embodiments of the present disclosure can be arbitrarily combined. That is, the present disclosure includes all the subject matter consisting of all combinations of the various components that can be combined as described in this specification.

[0184] Example

[0185] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the embodiments of these Examples.

[0186] (Example 1)

[0187] according to Figure 1 The sulfur-containing polymer compound was synthesized according to the reaction scheme shown in . First, sulfur (523 mg, 2.04 mmol) and Na2S (684 mg, 4.08 mmol, pentahydrate) were dissolved in 10 mL of water, and then, a solution 1 of a linear sulfur polymer (abbreviated as LS) was obtained by filtration. Next, a solution 2 was prepared by dissolving 1,2,7,8-diepoxyoctane (abbreviated as OctdiEpo, 239 μL, 2.04 mmol) in 10 mL of chloroform, and 0.005 mmol of hexadecyltrimethylammonium bromide as a phase transfer catalyst was further added to the solution 2. The solution 2 was added to the solution 1, and the mixture was stirred at room temperature (25°C) for 1 day to perform an interfacial reaction (polycondensation reaction). In addition, solutions 1 and 2 were prepared in such a way that the molar ratio of LS to OctdiEpo (LS: OctdiEpo) was 2:1. In the interfacial reaction, insoluble matter was generated between the water layer and the chloroform layer. Therefore, the insoluble matter was filtered out, and the obtained solid component was washed with water and chloroform in this order, and then dried under reduced pressure to obtain the target sulfur-containing polymer compound.

[0188] (Example 2)

[0189] A sulfur-containing polymer compound was obtained in the same manner as in Example 1 except that the solutions 1 and 2 were prepared so that the molar ratio of LS to OctdiEpo was 1.5:1.

[0190] (Example 3)

[0191] A sulfur-containing polymer compound was obtained in the same manner as in Example 1 except that the solutions 1 and 2 were prepared so that the molar ratio of LS to OctdiEpo was 3:1.

[0192] (Example 4)

[0193] A sulfur-containing polymer compound was obtained in the same manner as in Example 1 except that the solutions 1 and 2 were prepared so that the molar ratio of LS to OctdiEpo was 1:5.

[0194] (Example 5)

[0195] A sulfur-containing polymer compound was obtained in the same manner as in Example 1 except that the solutions 1 and 2 were prepared so that the molar ratio of LS to OctdiEpo was 1:2.

[0196] (Example 6)

[0197] A sulfur-containing polymer compound was obtained in the same manner as in Example 1 except that solution 1 and solution 2 were prepared so that the molar ratio of LS to OctdiEpo was 1:1.

[0198] (Example 7)

[0199] A sulfur-containing polymer compound was obtained in the same manner as in Example 1 except that the solutions 1 and 2 were prepared so that the molar ratio of LS to OctdiEpo was 5:1.

[0200] (Comparative Example 1)

[0201] according to Figure 2 According to the diagram shown in , a sulfoepoxy resin (Poly(S-OCtEpo-Bu)) with a small amount of sulfur atoms was synthesized as a comparative sample. First, 1,4-butanediol (316 mg, 3.52 mmol) and Na2S (591 mg, 3.52 mmol, pentahydrate) were dissolved in 5 mL of water, and chloroform (5.0 mL) in which OctdiEpo (500 mg, 3.52 mmol) was dissolved was added. Then, hexadecyltrimethylammonium bromide (7 mg, 19 μmol) was added as a phase transfer catalyst, and stirred at room temperature (25°C) for 2 days (interfacial reaction). In this interfacial reaction, insoluble matter was generated between the water layer and the chloroform layer, so the insoluble matter was filtered out, washed with water and chloroform, and then dried under reduced pressure. The sulfoepoxy resin (Poly(S-OCtEpo-Bu)) was obtained as a comparative sample.

[0202] (Example 8)

[0203] For reference, follow Figure 3The sulfur-containing compound was obtained as shown in the diagram. Sulfur (1.04 g, 4.08 mmol) and Na2S (1.37 g, 8.16 mmol, pentahydrate) were dissolved in water (30 mL) and filtered to obtain a solution 1 of a linear sulfur polymer (abbreviated as LS). Next, a solution 2 was prepared by dissolving styrene oxide (abbreviated as StEpo, 1.37 mL, 12.2 mmol) in 30 mL of chloroform, and 0.005 mmol of hexadecyltrimethylammonium bromide as a phase transfer catalyst was further added to the solution 2, and then the solution 2 was added to the solution 1, and the mixture was stirred at room temperature (25°C) for 18 hours to perform an interfacial reaction (polycondensation reaction). In addition, solutions 1 and 2 were prepared in such a way that the molar ratio of LS to StEpo was 1:1. After stirring, the chloroform layer was extracted, dried over sodium sulfate, and then filtered. The filtrate was evaporated and purified by column chromatography to obtain a sulfur-containing compound (LS-StEpo).

[0204] (Example 9)

[0205] The same method as in Example 1 (see below) was used except that epichlorohydrin was used instead of 1,2,7,8-diepoxyoctane. Fig.10 The sulfur-containing polymer compound is obtained by reaction (see reaction diagram in FIG. 1 ).

[0206] (Example 10)

[0207] A sulfur-containing polymer compound was obtained in the same manner as in Example 1 except that the amount of Na2S used was changed to 2.04 mmol.

[0208] (Example 11)

[0209] A sulfur-containing polymer compound was obtained in the same manner as in Example 1 except that the amount of Na2S used was changed to 12.24 mmol.

[0210] (Example 12)

[0211] A sulfur-containing polymer compound was obtained in the same manner as in Example 1 except that adipoyl chloride was used instead of 1,2,7,8-diepoxyoctane and the amount was changed to 11.7 mmol.

[0212] (Comparative Example 2)

[0213] A sulfur-containing polymer compound was obtained in the same manner as in Example 1 except that sulfur was not used.

[0214] Figure 4 is the sulfur-containing polymer compound obtained in Example 1 1H-NMR spectrum (the measurement solvent is DMSO-D6). Figure 4 The upper part of the spectrum is the raw material OctdiEpo 1 H-NMR spectrum, the lower part is the sulfur-containing polymer obtained in Example 1 1 H-NMR spectrum: From this spectrum, it can be observed that a peak derived from an OH group and a peak shift and broadening derived from OctdiEpo appear.

[0215] Furthermore, from the GPC measurement results of the sulfur-containing polymer compound obtained in Example 1, it was found that the number average molecular weight (Mn) of the sulfur-containing polymer compound obtained in Example 1 was 5700 (Mn / Mw=1.1).

[0216] Figure 5 This is the result of element distribution of the sulfur-containing polymer compound obtained in Example 1. It can be seen from SEM-EDX that sulfur is uniformly dispersed. It is thus confirmed that sulfur is uniformly introduced into the sulfur-containing polymer compound obtained in Example 1. In addition, when the S content in the sulfur-containing polymer compound is confirmed by elemental analysis, it is found that about 40 mass% (specifically, C is 37.01 mass%, hydrogen is 6.31 mass%, and S is 41.46 mass%) is present.

[0217] From the above, it can be seen that the sulfur-containing polymer compound obtained in Example 1 is a sulfur-containing thioepoxy resin, and the target product is obtained. In the sulfur-containing polymer compound, based on the results of NMR, elemental analysis, etc., it is estimated that n in formula (1) (i.e., the number of S per structural unit) is about 3. In addition, it is estimated that the value of n in the sulfur-containing polymer compound prepared in Example 10 is about 3, and the value of n in the sulfur-containing polymer compound prepared in Example 11 is about 2. In addition, the value of n in the sulfur-containing polymer compound prepared in Comparative Example 2 is about 1.

[0218] Table 1 shows the results of Mn, Mw, and S content of the sulfur-containing polymer compound obtained in each example.

[0219] [Table 1]

[0220]

[0221] Figure 6 is the comparative sample obtained in Comparative Example 1 1H-NMR spectrum (the measurement solvent is DMSO-D6). Through this spectrum, in addition to the peak of the newly appeared OH group, the peak from OctdiEpo or butanediol was also observed. In addition, when the sample obtained in Comparative Example 1 was measured by GPC, it was confirmed that the number average molecular weight (Mn) was 3100 (Mn / Mw=1.64).

[0222] The elemental analysis of the comparative sample obtained in Comparative Example 1 showed that the amount of sulfur present was about 11% by mass (C: 51.97% by mass, H: 8.83% by mass, S: 10.56% by mass), which was lower than the sulfur-containing polymer compound of Example 1 (S: 41.46% by mass). The reason why the comparative sample contained sulfur was that it came from the Na2S used in the reaction. The sulfur was not contained due to insufficient cleaning. The elemental distribution of SEM-EDX showed that the sulfur was uniformly dispersed in the range consistent with the SEM image, and it was confirmed that the sulfur was introduced into the material. From these results, it can be seen that the amount of sulfur in the comparative sample is small.

[0223] (Physical properties)

[0224] Figure 7 The following are the measurement results of the tensile test of the sulfur-containing polymer compound obtained in Example 1 and the comparative sample obtained in Comparative Example 1.

[0225] In addition, the tensile test (stroke-test force curve) is evaluated by observing the breaking point of the sample using "AUTOGRAPH" (model: AGX-pius) manufactured by SHIMADZU CORPORATION. The breaking point is taken as the end point, and the maximum stress until the end point is taken as the breaking stress of the polymer material. The tensile test is implemented by fixing the lower end of the sheet-like polymer composite material and moving the upper end upward at a tensile speed of 1mm / second. Through this measurement, the Young's modulus and fracture energy (fracture energy) of the polymer material are calculated. The sample is molded by a dumbbell test piece (JIS K 6251, No. 2 dumbbell test piece, thickness is 0.2mm).

[0226] according to Figure 7 The fracture stress of the comparative sample is 1.20MPa, the fracture strain is 29%, the Young's modulus is 3.04MPa, and the fracture energy is 0.181MJm -3 In contrast, the sulfur-containing polymer compound obtained in Example 1 has a fracture stress of 2.8 MPa, a fracture strain of 588%, a Young's modulus of 4.56 MPa, and a fracture energy of 10.3 MJm -3 , especially the fracture energy is 57 times higher than that of the comparison sample.

[0227] Figure 8 The results of the tensile test of the sulfur-containing polymer compound obtained in each example are shown. The physical strength increases with the increase of the amount of LS (linear sulfur polymer) and reaches the maximum at LS:OctdiEpo=2:1.

[0228] Interestingly, the physical strength of the sulfur-containing polymer obtained in Example 1 is comparable to that of the polysulfide (-(S) x -(CH2) y -) compared with the physical strength of the polysulfide obtained in Example 1, it can be seen that the fracture energy is more than 4.4 times higher (the fracture energy of the previous polysulfide is 1.37~2.32MPa). It is speculated that the sulfur-containing polymer compound obtained in Example 1 has a hydroxyl group in the molecule, which can form hydrogen bonds between polymers. Since the formation and dissociation of hydrogen bonds are reversible, when stress is applied to the material, the stress can be effectively dispersed. In addition, compared with the polymer made by the reverse vulcanization method, it can be seen that the sulfur-containing polymer compound obtained in Example 1 exhibits soft and tough physical properties that have not existed in sulfur polymers so far.

[0229] (Chemical stability)

[0230] The chemical stability of the sulfur-containing polymer compound obtained in Example 1 was evaluated using hydrogen sulfide test paper (ISIS Co., Ltd., model "MN90761"). As a result, no change was confirmed on the test paper. Therefore, no generation of hydrogen sulfide was confirmed in the sulfur-containing polymer compound obtained in Example 1, indicating that its chemical stability was high. In addition, the chemical stability using the hydrogen sulfide test paper was evaluated by setting the test tube size to 30 m / m and 200 m / m and placing about 0.5 g of the sample in the test tube together with the hydrogen sulfide test paper, and then evaluating whether the test paper was colored after 24 hours.

[0231] Fig. 9 is the sulfur-containing compound obtained in Example 8 1 H-NMR spectrum (the measurement solvent is DMSO-D6). The peak shift from StEpo and the new peak of OH group were observed in the spectrum. The sulfur-containing compound obtained in Example 8 was subjected to elemental analysis and measurement, and it was found that 35% by mass of sulfur (C: 52.35% by mass, H: 4.93% by mass, S: 34.6% by mass) was present.

[0232] (Self-healing)

[0233] The sulfur-containing polymer compound obtained in Example 1 was used to form a material having a rectangular shape (5 mm in length × 20 mm in width × 3 mm in thickness), and the material was cut using a utility knife. Then, when the cut pieces were brought into contact with each other at room temperature (25°C), they immediately adhered and could be picked up with tweezers. These results show that the sulfur-containing polymer compound obtained in Example 1 has a self-healing function.

[0234] (Adhesion)

[0235] A solution was prepared by dissolving 10 mg of the sulfur-containing polymer compound obtained in Example 1 in 10 μL of tetrahydrofuran. The solution was sandwiched between glass-glass, glass-stainless steel, glass-aluminum and polytetrafluoroethylene (PTFE)-PTFE, respectively, and dried at room temperature (25°C) to obtain a total of 4 laminates. When a 500 g weight was hung on a substrate on one side of each laminate and lifted, the weight was not dropped and lifted in all laminates. Therefore, it can be seen that the sulfur-containing polymer compound obtained in Example 1 has an adhesive function.

[0236] Particularly, although PTFE has high hydrophobic and oleophobic properties, it can still be bonded by sulfur-containing polymer compounds. In addition, different types of materials such as glass-stainless steel and glass-aluminum can also be bonded to each other, thus showing that the sulfur-containing polymer compounds obtained in Example 1 can be used as different types of bonding materials.

[0237] (Breathability)

[0238] A film of the sulfur-containing polymer compound obtained in Example 1 with a thickness of 300 μm was prepared, and the gas permeation was measured for four gases, CO2, O2, N2, and H2O, using "GTR-10XACT" of GTR TEC Corporation. As a result, the permeation amount was N2, O2, and H2O in descending order, while CO2 did not permeate at all. From these results, it can be seen that the film of the sulfur-containing polymer compound obtained in Example 1 does not permeate CO2.

[0239] (Material Recycling Test)

[0240] After hot pressing the sample (i.e., the broken sample) after the tensile test of the sulfur-containing polymer compound obtained in Example 1 at 80°C, it was stamped and reshaped into a dumbbell-shaped test piece. The same tensile test (re-tensile test) was performed again on the reshaped sample. As a result, the SS curve of the re-tensile test was completely consistent with the SS curve of the tensile test of the sulfur-containing polymer compound (original) before reshaping, and it was found that they had the same fracture stress and fracture strain. These results show that the sulfur-containing polymer compound obtained in Example 1 can be recycled.

[0241] (Determination of hydrogen sulfide generation)

[0242] The amount of hydrogen sulfide (H2S) gas generated during the polycondensation reaction performed in Example 1 was measured. In the conventional reverse sulfidation method, 850 mass ppm of hydrogen sulfide was generated. In contrast, in Example 1, the generation of hydrogen sulfide was so small that the generation of hydrogen sulfide was not detected, so it was confirmed that the preparation of the sulfur-containing polymer compound was carried out more safely. In addition, the reverse sulfidation method is as follows. That is, sulfur (1.00 g, 3.90 mmol, 50 wt%) was heated to 160 ° C under a nitrogen atmosphere to melt it, and 1,3-diisopropenylbenzene (DIB1.00 g, 6.30 mmol, 50 wt%) was added thereto, stirred for 24 hours, and the reverse sulfidation method was implemented.

[0243] (Odor measurement)

[0244] The odor measurement was performed according to the following procedure.

[0245] 1) Cut off a corner of a 5L sampling bag (hereinafter referred to as a 5L bag), insert 2g of sample into the 5L bag, and plug the cut portion.

[0246] 2) Degas the 5L bag using a vacuum pump, inject 2L of high-purity nitrogen into the 5L bag using a cumulative flow meter, and leave it at room temperature for 1 day.

[0247] 3) Use a silicone tube to connect the cannulas of the 5L bag and the 2L sampling bag (hereinafter referred to as the 2L bag) to transfer approximately 2L of nitrogen in the 5L bag to the 2L bag.

[0248] 4) The nitrogen in the 2L bag is analyzed using a gas sensor array and the accompanying analysis software is used to calculate the similarity, odor contribution value, and odor index equivalent value.

[0249] As a result of the odor measurement, the odor index equivalent value of the sulfur-containing polymer compound obtained in Example 1 was 8.6, whereas that of the sample prepared by the above-mentioned reverse vulcanization method was 35. These results indicate that the sulfur-containing polymer compound obtained in Example 1 is nearly odorless.

[0250] Fig.10 The results of the tensile test of the sulfur-containing polymer compound obtained in Example 9 are shown in FIG. Fig.10 The diagram of the preparation of the sulfur-containing polymer compound obtained in Example 9 is shown in FIG. Fig.10 It can be seen that the sulfur-containing polymer compound obtained in Example 9 has a breaking stress of 0.81 MPa and a breaking strain of 89%, and has excellent physical properties.

[0251] Fig.11These are the measurement results of the tensile test of the sulfur-containing polymer compounds obtained in Examples 10, 11 and Comparative Example 2. The physical strength (fracture stress of 5.0 MPa, fracture strain of 350%) of the sulfur-containing polymer compound (n=2) obtained in Example 11 is higher than the physical strength (fracture stress of 1.0 MPa, fracture strain of 20%) of the sulfur-containing polymer compound (n=1) obtained in Comparative Example 2. This is considered to be due to the introduction of disulfide bonds as sacrificial bonds, so that the stress is dispersed and the material becomes tough. Interestingly, the physical strength of the sulfur-containing polymer compound (n=3) obtained in Example 11 (fracture stress of 2.3 MPa, fracture strain of 600%, fracture energy of 10 MJ / m 3 ) is even higher than Example 11. This is considered to be because the SS bond is inherently deformable and soft compared to the CC bond, and the movable area of ​​the bond angle is wide, so it has the property of being easier to stretch when a force is applied. In addition, it can be considered that the polymers are entangled with each other, and by stretching, the entanglement between each other is reduced, and while stretching occurs, the energy applied is used to cause crystallization, and through these synergistic effects, the physical strength is increased. These results show that the polymer can be made tough by increasing the sulfur content (increasing the chain length).

[0252] Fig.12 (a) shows the sulfur-containing polymer compound obtained in Example 12. 1 H-NMR general, Fig.12 (b) shows the micro Raman spectrum of the sulfur-containing polymer compound obtained in Example 12. Fig.12 (a) 1 The upper part of the H-NMR spectrum is the spectrum of adipoyl chloride, and the lower part is the spectrum of the sulfur-containing polymer compound obtained in Example 12. 1 H-NMR spectrum.

[0253] exist Fig.12 (a) 1 In the H-NMR spectrum, it was confirmed that the peak of the proton "a" observed in the spectrum of adipoyl chloride was shifted and expanded in the spectrum of the sulfur-containing polymer compound. Fig.12 This is also confirmed by the observation of peaks from CS bonds and SS bonds in the micro-Raman spectrum of (b). Regarding molecular weight, the highest molecular weight was shown when it was produced in a double-layer system. Based on these results, it was confirmed that polythioesters using sulfur as a raw material can be synthesized.

Claims

1. A sulfur-containing polymer compound having a structural unit represented by the following general formula (1), the following general formula (1') or the following general formula (1''), -R 1 -R-R 1 -(S) n - (1) In formula (1), n ​​represents a number greater than 1, R represents an organic group, and two R 1 are the same or different and represent a divalent organic group derived from a functional group capable of condensation polymerization, -R 1 -R-(S) n - (1’) In formula (1'), n, R and R 1 respectively with n, R and R in the formula (1) 1 The same meaning, -SOMETHING) n - (1'')。 2. The sulfur-containing polymer compound according to claim 1, wherein The R 1 It is -CH2-CH(OH)-, -CH2-CH2-CH(OH)-, -CO-, -COO- or -NHCO-.

3. A method for producing a sulfur-containing polymer compound, comprising the step of obtaining the sulfur-containing polymer compound by reacting a linear sulfur polymer with a compound C having at least two functional groups capable of condensation polymerization.

4. The method for preparing a sulfur-containing polymer compound according to claim 3, wherein: The compound C is a compound represented by the following general formula (2): R 2 -R-R 2 (2) In formula (2), R is an organic group, and two R 2 The same or different functional groups are capable of condensation polymerization.

5. The method for preparing a sulfur-containing polymer compound according to claim 4, wherein: The R 2 is an epoxy group, a halogen atom, a glycidyl group, -C(=O)X, -COOH or -NCO, wherein X in -C(=O)X is a halogen atom.

6. A polymer composition comprising the sulfur-containing polymer compound according to claim 1 or 2.

7. A sulfur-containing compound having a structure in which organic groups derived from condensation-polymerizable functional groups are bonded to both ends of a sulfur polymer represented by the following general formula (3), -(S) n - (3) In formula (3), n represents a number greater than or equal to 1.

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