Sulfur-containing polymer compound and method for producing same, adhesive composition, adhesion method, molded body, and crosslinked polymer compound

Abstract

Provided are a novel sulfur-containing polymer compound having a carbon-carbon double bond site incorporated into a sulfur polymer, and a method for synthesizing the same. Also provided is a sulfur-containing polymer compound having excellent adhesive performance even in a high-temperature state.　The present invention is a sulfur-containing polymer compound which has a sulfur site represented by the general formula (1) -(S)n- (1) (in formula (1), n represents a number of 1 or more) and one or more multiple binding sites selected from the group consisting of carbon-carbon double bond sites and carbon-carbon triple bonds.

Description

Sulfur-containing polymer compounds and their manufacturing methods, adhesive compositions, adhesive methods, molded articles, and crosslinked polymer compounds

[0001] The present invention relates to sulfur-containing polymer compounds, methods for producing the same, adhesive compositions, adhesive methods, molded articles, and crosslinked polymer compounds.

[0002] Sulfur-containing polymers can be synthesized using sulfur, which is said to be discarded on the ground at a rate of 7 million tons per year, and possess superior properties not found in carbon polymers. Therefore, they are novel materials attracting attention from both an environmental and performance 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 because they decompose at room temperature, and are also insoluble in solvents and have poor processability. Therefore, there is an urgent need to develop efficient production methods for sulfur-containing polymers, along with improving their functionality. From this perspective, various sulfur-containing polymer compounds and methods for producing them have recently been proposed (for example, Patent Document 1, etc.).

[0004] Furthermore, Non-Patent Document 1 also discloses methods for producing sulfur-containing polymers, including a method for obtaining a sulfur-containing polymer compound by reacting a chlorous organic compound with a sulfur source, and a method for obtaining a sulfur-containing polymer compound by reacting a thiol compound with a sulfur source.

[0005] International Publication No. 2023 / 248625

[0006] Progress in Polymer Science 58 (2016) 90-125

[0007] Since sulfur-containing polymers are expected to exhibit new functions not found in conventional resins, the design of novel sulfur-containing polymers and the establishment of methods for synthesizing them are of paramount importance. From this perspective, the present invention aims to provide novel sulfur polymers (sulfur-containing polymer compounds). In particular, the present invention aims to provide novel sulfur-containing polymer compounds and methods for synthesizing the same, which incorporate carbon-carbon double bond sites or carbon-carbon triple bond sites into the sulfur polymer, and to provide sulfur-containing polymer compounds and methods for synthesizing the same that can easily form crosslinked structures. Furthermore, the present invention also aims to provide adhesive compositions, adhesive methods, and molded articles using sulfur-containing polymer compounds.

[0008] The inventors of this invention have diligently conducted research to achieve the above objectives and have succeeded in introducing sulfur moieties, carbon-carbon double bond moieties, and / or carbon-carbon triple bond moieties into structural units. They have found that this will achieve the above objectives, and have completed the present invention.

[0009] In other words, the present invention encompasses, for example, the subject matter described in the following sections: Section 1 A sulfur-containing polymer compound having the following general formula (1) - (S) ｎ - (1) (wherein formula (1), n ​​represents a number of 1 or more) A sulfur-containing polymer compound having a sulfur moiety represented by and one or more multiple bond moieties selected from the group consisting of carbon-carbon double bond moieties and carbon-carbon triple bond moieties. Item 2 The following general formula (2) - (S) ｎ -R １ - (2) (In formula (2), R １ The sulfur-containing polymer compound according to claim 1, comprising at least a structural unit represented by (where is an alkenylene group having at least one carbon-carbon double bond site). Claim 3 The following general formula (3) - (S) ｎ -R ２ - (3) (In formula (3), R ２(wherein it represents an alkylene group substituted with a group having at least one of the carbon-carbon double bond sites)), the sulfur-containing polymer compound according to item 1, containing at least a structural unit represented by the following. Item 4 The following general formula (3)-(S) ｎ -R ２ -(3) (In formula (3), R ２ represents an alkylene group substituted with a group having at least one of the carbon-carbon double bond sites)), the sulfur-containing polymer compound according to item 2, further containing a structural unit represented by the following. Item 5 The following general formula (2')-(S) ｎ -R ３ -(2') (In formula (2), R ３ represents an alkynylene group having at least one of the carbon-carbon triple bond sites)), the sulfur-containing polymer compound according to item 1, containing at least a structural unit represented by the following. Item 6 The following general formula (4)-(S) ｎ -R ４ -(4) (In formula (4), R ４ represents an alkylene group substituted with a group having at least one of the carbon-carbon triple bond sites)), the sulfur-containing polymer compound according to item 1, containing a structural unit represented by the following. Item 7 The following general formula (4)-(S) ｎ -R ４ -(4) (In formula (4), R ４A sulfur-containing polymer compound according to claim 5, further comprising a structural unit represented by (where is an alkylene group substituted with at least one carbon-carbon triple bond site). Claim 8 A method for producing a sulfur-containing polymer compound according to any one of claims 1 to 7, comprising the step of reacting a sulfur source or sulfur polymer with compound A, wherein compound A is at least one selected from the group consisting of compounds having a carbon-carbon double bond and at least two halogens in the molecule and compounds having a carbon-carbon triple bond and at least two halogens in the molecule. Claim 9 A method for producing a sulfur-containing polymer compound according to any one of claims 1 to 7, comprising the step of reacting a hydroxyl group-containing sulfur polymer with compound B, wherein compound B is at least one selected from the group consisting of compounds having a carbon-carbon double bond in the molecule and compounds having a carbon-carbon double bond in the molecule, and compound B further having a functional group that can react with a hydroxyl group through condensation or addition. Item 10: An adhesive composition comprising a sulfur-containing polymer compound as described in any one of items 1 to 7. Item 11: An adhesive method for bonding using a sulfur-containing polymer compound as described in any one of items 1 to 7. Item 12: A molded article comprising a sulfur-containing polymer compound as described in any one of items 1 to 7. Item 13: A crosslinked polymer compound having a self-crosslinked structure of a sulfur-containing polymer compound as described in any one of items 1 to 7.

[0010] The sulfur-containing polymer compound of the present invention is a novel polymer material having sulfur moieties and carbon-carbon double bond moieties and / or carbon-carbon triple bond moieties, which can easily form crosslinked structures and have excellent adhesive properties at high temperatures.

[0011] (a) is the reaction scheme carried out in Example 1a, and (b) is the reaction scheme carried out in Example 1b. (a) is the sulfur-containing polymer compound obtained in Example 1a and Example 1b. １(a) is the 1H-NMR measurement result, and (b) is the FT-IR spectrum measurement result. (a) is the reaction scheme carried out in Example 2a, and (b) is the reaction scheme carried out in Example 2b. (a) is the sulfur-containing polymer compound obtained in Example 2a and Example 2b. １ (a) is the 1H-NMR measurement result, and (b) is the FT-IR spectrum measurement result. This is the Raman spectroscopy spectrum measurement result of the sulfur-containing polymer compound obtained in Example 2b. (a) is the reaction scheme carried out in Example 3a, and (b) is the reaction scheme carried out in Example 3b. (a) is the sulfur-containing polymer compound obtained in Example 3a and Example 3b １ (b) is the 1H-NMR measurement result, and (b) is the FT-IR spectrum measurement result. This is the Raman spectroscopy spectrum measurement result of the sulfur-containing polymer compound obtained in Example 3b. This is a schematic diagram showing the procedure of the adhesion test. This is the reaction scheme carried out in Example 4a. (a) is the sulfur-containing polymer compound obtained in Example 4a １ (b) is the 1H-NMR measurement result, and (b) is the FT-IR spectrum measurement result. This is the reaction scheme carried out in Example 4b. (a) is the sulfur-containing polymer compound obtained in Example 4b. １ (b) is the 1H-NMR measurement result, and (b) is the FT-IR spectrum measurement result. This is the reaction scheme carried out in Example 4c. (a) is the sulfur-containing polymer compound obtained in Example 4c. １ (b) is the 1H-NMR measurement result, and (b) is the FT-IR spectrum measurement result. This is the reaction scheme carried out in Example 5. (a) is the sulfur-containing polymer compound obtained in Example 5. １ (a) shows the 1H-NMR measurement results, and (b) shows the FT-IR spectrum measurement results. (a) shows the results of the tensile test of the film obtained from the sulfur-containing polymer compound, and (b) shows the FT-IR spectrum results. (a) shows the reaction scheme carried out in Example 6, and (b) shows the results of the micro-Raman measurement of the sulfur-containing polymer compound obtained in Example 6. This is the reaction scheme carried out in Example 7. The sulfur-containing polymer compound obtained in Example 7 １ The H-NMR measurement results are shown.

[0012] Embodiments of the present invention will be described in detail below. In this specification, the expressions "containing" and "including" include the concepts of "containing," "including," "substantially consisting of," and "consisting only of."

[0013] In the numerical ranges described stepwise in this specification, the upper or lower limit of a numerical range in one step can be arbitrarily combined with the upper or lower limit of a numerical range in another step. In the numerical ranges described in this specification, the upper or lower limit of a numerical range may be replaced with values ​​shown in the examples or values ​​that can be uniquely derived from the examples. Furthermore, in this specification, numbers connected by "~" mean a numerical range that includes the numbers before and after "~" as the lower and upper limits.

[0014] 1. Sulfur-containing polymer compounds The sulfur-containing polymer compounds of the present invention are polymer compounds containing sulfur, and are of the following general formula (1) - (S) ｎ - (1) (wherein formula (1), n ​​represents a number of 1 or more) It has a sulfur moiety represented by and one or more multiple bond sites selected from the group consisting of carbon-carbon double bond sites and carbon-carbon triple bond sites. The sulfur moiety and the multiple bond sites are contained in the structural unit constituting the sulfur-containing polymer compound. For example, both the sulfur moiety and the multiple bond sites may be present in a single structural unit.

[0015] The sulfur-containing polymer compound of the present invention is a novel polymer material having sulfur moieties and the aforementioned multiple bonding moieties, and can easily form a crosslinked structure. Furthermore, the sulfur-containing polymer compound of the present invention can impart excellent adhesion, for example, it can bond various materials together even at high temperatures (e.g., in an atmosphere of 120°C), and the sulfur-containing polymer compound can exhibit adhesive function even when in a solid state (i.e., not dissolved or dispersed in a solvent, etc.). For this reason, the sulfur-containing polymer compound of the present invention can be suitably used as a component of an adhesive. When materials are bonded together by the sulfur-containing polymer compound of the present invention, they are difficult to peel off even in high-temperature environments (e.g., in an atmosphere of 120°C).

[0016] Furthermore, various molded articles can be manufactured using the sulfur-containing polymer compound of the present invention, and such molded articles may also have excellent mechanical properties.

[0017] The sulfur-containing polymer compound of the present invention may have a sulfur moiety represented by formula (1) in its structural unit.

[0018] In formula (1), n ​​is not particularly limited as long as it is a number of 1 or more. n may be 1 or a number greater than 1. In terms of improving the adhesion performance of sulfur-containing polymer compounds at high temperatures, n is preferably 1.5 or more, more preferably 2 or more, even more preferably 2.5 or more, and particularly preferably 3 or more. Furthermore, there is no particular upper limit to n; for example, it may be 10,000 or less, or 1,000 or less. In terms of improving adhesion performance, n may also be 10 or less, may be 8 or less, or may be 5 or less.

[0019] In sulfur-containing polymer compounds, the value of n in formula (1) is the value of the sulfur-containing polymer compound １ It can be calculated based on the results of H-NMR spectroscopy and elemental analysis.

[0020] The sulfur-containing polymer compound of the present invention has one or more multiple bonding sites selected from the group consisting of carbon-carbon double bond sites and carbon-carbon triple bond sites. A carbon-carbon double bond site is, for example, a group having a carbon-carbon double bond. A carbon-carbon triple bond site is, for example, a group having a carbon-carbon triple bond. Hereinafter, these carbon-carbon double bond sites and carbon-carbon triple bond sites may be collectively abbreviated as "multiple bonding sites".

[0021] The carbon-carbon double bond site is not particularly limited in type, as long as it has a C=C bond; for example, CH ２ Examples include =CH-, -CH=CH-, CHR=CH- (where R is, for example, an alkyl group having 1 to 10 carbon atoms, more specifically a methyl group, etc.).

[0022] The carbon-carbon triple bond site is not particularly limited in type as long as it has a C≡C bond, and examples include CH≡CH-, -C≡C-, CR≡CH- (where R is, for example, an alkyl group having 1 to 10 carbon atoms, more specifically a methyl group, etc.).

[0023] Multiple bonding sites can be present in the main chain or side chain of the sulfur-containing polymer compound of the present invention. These multiple bonding sites can typically be directly or indirectly bonded to the main chain or side chain via chemical bonds (covalent bonds).

[0024] (Sulfur-containing polymer compounds having carbon-carbon double bond sites) The following describes sulfur-containing polymer compounds having carbon-carbon double bond sites. Such sulfur-containing polymer compounds include, for example, the following general formula (2) - (S) ｎ -R １ - It may contain at least the structural unit represented by (2). That is, the sulfur moiety and the multiple bond moiety (particularly the structural unit having a carbon-carbon double bond moiety) may mean the structural unit represented by the general formula (2). Therefore, as an example of an embodiment of the "sulfur-containing polymer compound having the sulfur moiety and the multiple bond moiety" of the present invention, a sulfur-containing polymer compound having the structural unit represented by formula (2) can be given.

[0025] Here, in equation (2), R １ This represents an alkenylene group having at least one carbon-carbon double bond site. An alkenylene group can mean a divalent linking group obtained by removing two hydrogen atoms from an alkene.

[0026] The alkenylene group may have only one carbon-carbon double bond site, or it may have two or more. The alkenylene group may have, for example, 10 or fewer carbon-carbon double bond sites, preferably 6 or fewer, more preferably 4 or fewer, and even more preferably 3 or fewer.

[0027] The number of carbon atoms in the alkenylene group is, for example, 3 to 20, preferably 16 or less, more preferably 12 or less, even more preferably 10 or less, even more preferably 8 or less, and particularly preferably 6 or less. The alkenylene group may be linear or branched. The alkenylene group may also have hydrogen atoms substituted with other substituents, for example. Examples of substituents include hydrocarbon groups, halo groups, nitro groups, cyano groups, oxo groups, thioxo groups, sulfo groups, sulfamoyl groups, sulfinamoyl groups, and sulfenamoyl groups. Hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, aralkyl groups, etc., and for example, have 1 to 10 carbon atoms.

[0028] In formula (2) above, a specific example of the alkenylene group (i.e., R １ Specific examples include -CH ２ -CH = CH - CH ２ Examples of groups represented by - (i.e., alkenylene groups derived from butadiene) can be cited. In this case, the sulfur-containing polymer compound of the present invention can become a sulfur polymer having a butadiene skeleton, which is known as a rubber material.

[0029] A sulfur-containing polymer compound having a carbon-carbon double bond site is, in another embodiment, the following general formula (3) - (S) ｎ -R ２ - It may contain at least the structural unit represented by (3). That is, the sulfur moiety and the multiple bond moiety (particularly the structural unit having a carbon-carbon double bond moiety) can mean the structural unit represented by the general formula (3). Therefore, as an example of an embodiment of the "sulfur-containing polymer compound having the sulfur moiety and the multiple bond moiety" of the present invention, a sulfur-containing polymer compound having the structural unit represented by formula (3) can also be cited.

[0030] Here, in equation (3), R ２ This represents an alkylene group substituted with at least one group having the carbon-carbon double bond moiety.

[0031] R in formula (3) ２ An example of an alkylene group (i.e., an alkylene group substituted with at least one carbon-carbon double bond site) is the following formula (3a) - (CH ２ ) ｍ - (CHR ２ａ ) ｋ - (CH ２ ) ｐ - A divalent group represented by (3a) can be listed.

[0032] Here, in formula (3a), m is an integer of 0 or greater than or equal to 1, k is an integer of 1 or greater, and p is an integer of 0 or greater than or equal to 1, R ２ａ This indicates a group having the carbon-carbon double bond site.

[0033] In formula (3a), m is preferably 1 or more, more preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. m may be 1. When m is 0, in formula (3a), "-(CH ２ ) ｍ This means that the part is missing.

[0034] In formula (3a), k is preferably 10 or less, more preferably 6 or less, even more preferably 4 or less, and particularly preferably 3 or less. k may also be 1.

[0035] In formula (3a), p is preferably 0 or greater, more preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. p may also be 0. Note that when p is 0, in formula (3a), "-(CH ２ ) ｐ This means that the part is missing.

[0036] In equation (3a), R ２ａ The type of R is not particularly limited as long as it is a group having the carbon-carbon double bond site. For example, R ２ａThe number of carbon atoms is preferably 2 or more, including the number of carbon atoms in the carbon-carbon double bond region, preferably 10 or less, more preferably 6 or less, even more preferably 4 or less, and particularly preferably 3 or less.

[0037] In equation (3a), R ２ａ Specifically, CH ２ = CH - ien CH ２ = CH - CH ２ Examples include -, CHR=CH- (where R is, for example, an alkyl group having 1 to 4 carbon atoms, more specifically a methyl group, etc.).

[0038] As an example of a divalent group represented by formula (3a), -CH ２ -CH (CH=CH ２ ) - are listed as examples.

[0039] R in formula (3) ２ Other examples include R ２ At least one hydrogen atom in the alkylene group (substituted with a group having at least one carbon-carbon double bond site) is "-OR ３ (However, R ３ Examples include alkylene groups having a structure substituted with (where represents a monovalent group having the carbon-carbon double bond moiety).

[0040] R ３ The type is not particularly limited as long as it has the carbon-carbon double bond site. For example, R ３ CH ２ = Groups containing CH-, CH ２ = CH - CH ２ Groups containing -, groups containing -CH=CH-, and groups containing (meth)acryloyl groups can be mentioned. Specifically, R ３Examples of addition-reactive functional groups include groups derived from compounds having an addition-reactive functional group and a (meth)acryloyl group, groups derived from vinyl compounds having an addition-reactive functional group and a C=C bond (excluding the (meth)acryloyl group), or groups derived from compounds having a condensation-reactive functional group and a (meth)acryloyl group. Examples of addition-reactive functional groups include isocyanate groups, carboxyl groups, amino groups, and hydroxyl groups. Examples of condensation-reactive functional groups include halogens (fluorine, chlorine, etc.), carboxyl groups, amino groups, and hydroxyl groups. Note that "(meth)acryloyl" means "acryloyl" or "methacryloyl," "(meth)acryl" means "acryl" or "methacrylic," "(meth)acrylate" means "acrylate" or "methacrylate," and "(meth)allyl" means "allyl" or "methallyl."

[0041] R ３ The number of carbon atoms is, for example, 3 to 20, preferably 3 to 16. ３ If the compound has heteroatoms, the number of heteroatoms is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 to 4. The heteroatoms are preferably nitrogen, oxygen, etc.

[0042] Examples of compounds having an addition-reactive functional group and a (meth)acryloyl group include compounds having an addition-reactive functional group such as an isocyanate group at the alkyl terminus of an alkyl (meth)acrylate. The number of carbon atoms in the alkyl group of the alkyl (meth)acrylate is, for example, 1 to 10, preferably 2 to 6. An example of a compound having an addition-reactive functional group such as an isocyanate group at the alkyl terminus of an alkyl (meth)acrylate is 2-isocyanate ethyl (meth)acrylate.

[0043] Examples of vinyl compounds having addition-reactive functional groups and C=C bonds (excluding (meth)acryloyl groups) include vinyl monomers having a structure in which an NCO group is bonded to a C=C bond via a hydrocarbon group. Examples of hydrocarbon groups in this case include linear or branched alkyl groups having 1 to 10 carbon atoms, aromatic groups having 5 to 12 carbon atoms, or groups having both. An example of such a vinyl monomer is 3-isopropenyl-α,α-dimethylbenzyl isocyanate.

[0044] Examples of compounds having a (meth)acryloyl group with a functional group capable of condensation include halogenated (meth)acryloyl, and specifically, acryloyl chloride.

[0045] R ３ If the group is derived from a compound having an addition-reactive functional group and a (meth)acryloyl group, the addition-reactive functional group reacts with the hydroxyl group as described below, resulting in the aforementioned "-OR ３ It is possible to form ". Also, R ３ If the group is derived from a compound having a (meth)acryloyl group that has a functional group capable of condensation reaction, then, as described below, the functional group capable of condensation reaction reacts with the hydroxyl group to produce the aforementioned "-OR ３ It is possible to form ".

[0046] R in formula (3) ２ However, at least one hydrogen atom is "-OR ３ In the case of an alkylene group having a structure substituted with ", the number of carbon atoms in the alkylene group can be 1 or more and 20 or less, preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, particularly preferably 5 or more, also preferably 18 or less, more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. ２ is, "-OR ３ It may have at least one of these, and preferably two. That is, R ２ This means that at least two hydrogen atoms are "-OR ３ It may also be an alkylene group having a structure substituted with ".

[0047] As described above, when a sulfur-containing polymer compound having a carbon-carbon double bond site contains the structural unit represented by formula (3), then R in formula (3) ２ This is a divalent group represented by formula (3a) above, or at least one hydrogen atom is "-OR ３ It can be an alkylene group having a structure substituted with ".

[0048] A sulfur-containing polymer compound having a carbon-carbon double bond site may have, for example, at least one of the structural unit represented by formula (2) and the structural unit represented by formula (3), or a sulfur-containing polymer compound having a carbon-carbon double bond site may have both the structural unit represented by formula (2) and the structural unit represented by formula (3).

[0049] With respect to all structural units constituting a sulfur-containing polymer compound having a carbon-carbon double bond site, the total content of the structural units represented by formula (2) and the structural units represented by formula (3) is preferably 50 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and particularly preferably 99 mol% or more.

[0050] When a sulfur-containing polymer compound having a carbon-carbon double bond site has both the structural unit represented by formula (2) and the structural unit represented by formula (3), the content ratio of the two structural units is not particularly limited, and can be, for example, 20:80 to 80:20 in molar ratio, preferably 40:60 to 60:40.

[0051] A sulfur-containing polymer compound having a carbon-carbon double bond moiety may consist only of the structural unit represented by formula (2), or it may consist only of the structural unit represented by formula (3). Furthermore, a sulfur-containing polymer compound having a carbon-carbon double bond moiety may consist only of the structural unit represented by formula (2) and the structural unit represented by formula (3).

[0052] (Sulfur-containing polymer compounds having carbon-carbon triple bond sites) The following describes sulfur-containing polymer compounds having carbon-carbon triple bond sites. Such sulfur-containing polymer compounds include, for example, the following general formula (2') - (S) ｎ -R ３ - It may contain at least one structural unit represented by (2'). That is, the sulfur moiety and the multiple bond moiety (particularly a structural unit having a carbon-carbon triple bond moiety) can mean the structural unit represented by the general formula (2'). Therefore, as an example of an embodiment of the "sulfur-containing polymer compound having the sulfur moiety and the multiple bond moiety" of the present invention, a sulfur-containing polymer compound having the structural unit represented by the formula (2') can be given.

[0053] Here, in equation (2'), R ３ This represents an alkynylene group having at least one carbon-carbon triple bond. An alkynylene group can mean a divalent linking group obtained by removing two hydrogen atoms from an alkyne.

[0054] The alkynylene group may have only one carbon-carbon triple bond site, or it may have two or more. The alkynylene group may have, for example, 10 or fewer carbon-carbon double bond sites, preferably 6 or fewer, more preferably 4 or fewer, and even more preferably 3 or fewer.

[0055] The number of carbon atoms in the alkynylene group is, for example, 3 or more and 20 or less, preferably 16 or less, more preferably 12 or less, even more preferably 10 or less, still more preferably 8 or less, and particularly preferably 6 or less. The alkynylene group may be linear or may have a branch. Further, the alkynylene group may be substituted with other substituents, for example, a hydrogen atom. Examples of the substituent 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, etc., and for example, the number of carbon atoms is 1 to 10.

[0056] In the formula (2'), specific examples of the alkynylene group (that is, specific examples of R ３ ) include a group represented by -CH ２ -C≡C-CH ２ - (that is, an alkynylene group derived from butyne).

[0057] The sulfur-containing polymer compound having a carbon-carbon triple bond site can, in another aspect, contain at least a structural unit represented by the following general formula (4) -(S) [[ID=I3]] ｎ -R ４ - (4). That is, the sulfur site and the multiple bond site (particularly, a structural unit having a carbon-carbon triple bond site) can mean a structural unit represented by the general formula (4). Therefore, as an example of an embodiment of the "sulfur-containing polymer compound having the sulfur site and the multiple bond site" of the present invention, a sulfur-containing polymer compound having a structural unit represented by the formula (4) can also be mentioned.

[0058] Here, in the formula (4), R ４ represents an alkylene group substituted with a group having at least one of the carbon-carbon triple bond sites.

[0059] R in the formula (4) ４(That is, an alkylene group substituted with a group having at least one of the carbon-carbon triple bond sites) As an example, the following formula (4a) - (CH ２ ) ｍ -(CHR ４ａ ) ｋ -(CH ２ ) ｐ - The divalent group represented by (4a) can be mentioned.

[0060] Here, in the formula (4a), m is an integer of 0 or 1 or more, k is an integer of 1 or more, p is an integer of 0 or 1 or more, and R ４ａ represents a group having the carbon-carbon triple bond site.

[0061] In the formula (4a), m is preferably 1 or more, preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. m may be 1. When m is 0, in the formula (4a), it means that there is no "- (CH ２ ) ｍ " site.

[0062] In the formula (4a), k is preferably 10 or less, more preferably 6 or less, even more preferably 4 or less, and particularly preferably 3 or less. k may be 1.

[0063] In the formula (4a), p is preferably 0 or more, preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. p may be 0. When p is 0, in the formula (4a), it means that there is no "- (CH ２ ) ｐ " site.

[0064] In the formula (4a), as long as R ４ａ is a group having the carbon-carbon triple bond site, its type is not particularly limited. For example, the number of carbon atoms of R ４ａ is preferably 2 or more including the number of carbon atoms of the carbon-carbon triple bond site, preferably 10 or less, more preferably 6 or less, even more preferably 4 or less, and particularly preferably 3 or less.

[0065] In equation (4a), R ４ａ Specifically, CH ２ = CH - ien CH ２ = CH - CH ２ Examples include -, CHR=CH- (where R is, for example, an alkyl group having 1 to 4 carbon atoms, more specifically a methyl group, etc.).

[0066] As an example of a divalent group represented by formula (4a), -CH ２ One example is -CH (C≡CH)-.

[0067] R in formula (4) ４ Other examples include R ４ At least one hydrogen atom in the alkylene group (substituted with a group having at least one carbon-carbon triple bond site) is "-OR ５ (However, R ５ Examples include alkylene groups having a structure substituted with (where represents a monovalent group having the carbon-carbon triple bond site).

[0068] R ５ The type is not particularly limited as long as it has the carbon-carbon triple bond site. For example, R ５ This is a group containing CH≡C−, CH≡C−CH ２ Examples include groups containing - and groups containing -CH≡C-. Specifically, R ５ Examples of functional groups that can undergo addition reactions include groups derived from compounds having C≡C bonds. Examples of functional groups that can undergo addition reactions include isocyanate groups, carboxyl groups, amino groups, and hydroxyl groups. Examples of functional groups that can undergo condensation reactions include halogens (fluorine, chlorine, etc.), carboxyl groups, amino groups, and hydroxyl groups.

[0069] R ５ The number of carbon atoms is, for example, 3 to 20, preferably 3 to 16. ３ If the compound has heteroatoms, the number of heteroatoms is preferably 1 to 10, more preferably 2 to 8, and even more preferably 2 to 6. The heteroatoms are preferably nitrogen, oxygen, etc.

[0070] Examples of compounds having an addition-reactive functional group and a C≡C bond include compounds having a structure in which a COOH group is bonded to a C≡C bond via a hydrocarbon group. Examples of hydrocarbon groups in this case include linear or branched alkyl groups having 1 to 10 carbon atoms, aromatic groups having 5 to 12 carbon atoms, or groups having both. Examples of compounds having an addition-reactive functional group and a C≡C bond include CH≡C-(CH ２ ) ３ -COOH is one example.

[0071] If a compound having an addition-reactive functional group and a C≡C bond is a "compound having a structure in which a COOH group is bonded to a C≡C bond via a hydrocarbon group," then, for example, the portion of the compound from which the OH group is removed from the COOH group is R ５ This corresponds to the aforementioned "-OR ５ It is possible to form "-OR ５ The oxygen atom in " and R ５ An ester bond is formed with the carbonyl group inside. For example, a compound having an addition-reactive functional group and a C≡C bond is CH≡C-(CH ２ ) ３ -COOH is the case, "-OR ５ " is "CH≡C-(CH ２ ) ３ "-COO-"

[0072] R in formula (4) ４ However, at least one hydrogen atom is "-OR ５ In the case of an alkylene group having a structure substituted with ", the number of carbon atoms in the alkylene group can be 1 or more and 20 or less, preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, particularly preferably 5 or more, also preferably 18 or less, more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. ４ is, "-OR ５ It may have at least one of these, and preferably two. That is, R ４ This means that at least two hydrogen atoms are "-OR ５It may also be an alkylene group having a structure substituted with ".

[0073] As described above, when a sulfur-containing polymer compound having a carbon-carbon triple bond site contains the structural unit represented by formula (4), then R in formula (4) ２ This is a divalent group represented by formula (4a) above, or at least one hydrogen atom is "-OR ５ It can be an alkylene group having a structure substituted with ".

[0074] A sulfur-containing polymer compound having a carbon-carbon triple bond site may have, for example, at least one of the structural unit represented by formula (2') and the structural unit represented by formula (4), or a sulfur-containing polymer compound having a carbon-carbon triple bond site may have both the structural unit represented by formula (2') and the structural unit represented by formula (4).

[0075] With respect to all structural units constituting a sulfur-containing polymer compound having a carbon-carbon triple bond site, the total content of the structural unit represented by formula (2') and the structural unit represented by formula (4) is preferably 50 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and particularly preferably 99 mol% or more.

[0076] When a sulfur-containing polymer compound having a carbon-carbon triple bond site has both the structural unit represented by formula (2') and the structural unit represented by formula (4), the content ratio of the two structural units is not particularly limited, and can be, for example, 20:80 to 80:20 in molar ratio, preferably 40:60 to 60:40.

[0077] A sulfur-containing polymer compound having a carbon-carbon triple bond site may consist only of the structural unit represented by formula (2') or only of the structural unit represented by formula (4). Furthermore, a sulfur-containing polymer compound having a carbon-carbon triple bond site may consist only of the structural unit represented by formula (2') and the structural unit represented by formula (4).

[0078] (Sulfur-containing polymer compounds of the present invention) Hereinafter, sulfur-containing polymer compounds having carbon-carbon double bond sites and sulfur-containing polymer compounds having carbon-carbon triple bond sites will be collectively referred to as "sulfur-containing polymer compounds of the present invention."

[0079] 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. Preferably, the weight-average molecular weight of the sulfur-containing polymer compound of the present invention is 4,000 or more, and preferably 20,000 or less. In this specification, the weight-average molecular weight (Mw) is the value obtained by gel permeation chromatography (GPC) measurement.

[0080] In the sulfur-containing polymer compound of the present invention, the content of S (element sulfur) is not particularly limited, but is preferably 30% by mass or more and 99% by mass, in that it tends to have excellent mechanical properties, a more preferable lower limit is 35% by mass, a more preferable upper limit is 80% by mass, an even more preferable upper limit is 70% by mass, and a particularly preferable upper limit is 50% by mass.

[0081] The sulfur-containing polymer compound of the present invention may also include structural units that do not have either a carbon-carbon double bond site or a carbon-carbon triple bond site. For example, the sulfur-containing polymer compound of the present invention may include structural units that have a sulfur site and do not have the aforementioned multiple bond. Such a structural unit may be, for example, the following formula (a) - (S) ｎ -R １０ - A structural unit represented by (a) can be listed. Here, "-(S) ｎ -" is the same as "-(S)" in formula (2) above. ｎ This is equivalent to "-". In equation (a), R １０ For example, this is a divalent alkylene group. The number of carbon atoms in the alkylene group can be 1 or more and 20 or less, preferably 2 or more, preferably 3, preferably 12 or less, more preferably 10 or less, even more preferably 8 or less, and particularly preferably 6 or less.

[0082] When the sulfur-containing polymer compound of the present invention has a structural unit represented by formula (2') and a structural unit represented by formula (a), the content ratio is not particularly limited. For example, the amount of the structural unit represented by formula (2') relative to the total amount of the structural units represented by formula (a) may be 80 mol% or less, 50 mol% or less, 30 mol% or less, 20 mol% or less, or 10 mol% or less. Alternatively, when the sulfur-containing polymer compound of the present invention has a structural unit represented by formula (2') and a structural unit represented by formula (a), the content ratio is not particularly limited. For example, the amount of the structural unit represented by formula (2') relative to the total amount of the structural units represented by formula (a) may exceed 90 mol%. In other words, when the sulfur-containing polymer compound of the present invention has a structural unit represented by formula (2') and a structural unit represented by formula (a), the content ratio of the two can be arbitrary.

[0083] 2. Method for Producing Sulfur-Containing Polymer Compounds The method for producing the sulfur-containing polymer compound of the present invention is not particularly limited. For example, the sulfur-containing polymer compound of the present invention can be obtained by a production method comprising the following step 1. Step 1: A step of reacting a sulfur source or sulfur polymer with compound A described below.

[0084] Alternatively, the sulfur-containing polymer compound of the present invention can be obtained by a manufacturing method comprising the following step 2. Step 2: A step of reacting a hydroxyl group-containing sulfur polymer with compound B described below.

[0085] (Step 1) First, a method for producing the sulfur-containing polymer compound of the present invention by Step 1 will be described. In Step 1, a sulfur source or sulfur polymer is reacted with compound A.

[0086] The sulfur source used in step 1 may be elemental sulfur or a compound containing sulfur atoms. Examples of compounds containing sulfur atoms include metal sulfides. Examples of metals include alkali metals, among which sodium sulfide is particularly useful. When n in formulas (1), (2), or (3) is 1, a metal sulfide (preferably sodium sulfide) can be used in step 1.

[0087] The sulfur polymer used in step 1 is -(S) ｎ The polymer is represented by - (where n is synonymous with n in formula (1)), and can be obtained, for example, by the reaction of a sulfur source and a metal source. The sulfur source is the same as described above, and therefore may be elemental sulfur or a compound containing sulfur atoms, but it is preferable that the sulfur source be elemental sulfur because it is easier to obtain a sulfur polymer. Examples of elemental sulfur include cyclic sulfur composed of sulfur atoms, and typically, an eight-membered ring of sulfur can be used as the sulfur source. Such a sulfur source can be manufactured by known methods or can be obtained from commercially available products.

[0088] Examples of the metal source include alkali metals and alkali metal compounds. The alkali metal is not particularly limited and can be sodium, potassium, or lithium, with sodium being preferred. Examples of alkali metal compounds include alkali metal sulfides, with sodium sulfide being preferred. The alkali metal compound may also be a hydrate. The metal source is preferably an alkali metal compound, more preferably an alkali metal sulfide, and particularly preferably sodium sulfide, because the reaction is simple and large-scale synthesis is possible.

[0089] The method for reacting the sulfur source with the metal source is not particularly limited; for example, a method of mixing the sulfur source and the metal source in a solvent can be used. When a solvent is used in this reaction, the type of solvent is not particularly limited; in addition to water, various organic solvents can be used. When the metal source is an alkali metal compound, and especially when it is an alkali metal sulfide, it is preferable to use an aqueous solvent, and especially water. When the metal source is an alkali metal, it is preferable to use an organic solvent, and especially polar solvents such as dimethylacetamide.

[0090] In the reaction between the sulfur source and the metal source, the ratio of the two used is not particularly limited. For example, in terms of easily controlling the chain length of the -(S)n- moiety, i.e., the value of n, the amount of metal source used per mole of 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 and the metal source is not particularly limited, and can be, for example, 0 to 200°C, preferably 15 to 80°C. The reaction time between the sulfur source and the metal source is also not particularly limited, and can be, for example, 10 minutes to 48 hours, preferably 30 minutes to 24 hours. The reaction can be carried out, for example, under an inert gas atmosphere such as nitrogen.

[0091] The reaction between the sulfur source and the metal source described above produces the sulfur polymer "-(S)" used in step 1. ｎ "-" is obtained. - (S) ｎ - The terminal end of the part is hydrogen or an alkali metal as described below.

[0092] The sulfur polymer obtained by the reaction of the sulfur source and the metal source described above is, for example, linear. That is, the sulfur polymer used in step 1 may be a linear sulfur polymer. If the value of n in formula (1), (2), or (3) exceeds 1, a sulfur polymer can be used in step 1.

[0093] Compound A used in step 1 is at least one selected from the group consisting of compounds having a carbon-carbon double bond and at least two halogens in the molecule, and compounds having a carbon-carbon triple bond and at least two halogens in the molecule. In particular, when compound A is a compound having a carbon-carbon double bond and at least two halogens in the molecule, compound A is preferably an alkene compound having at least two halogens. When compound A is a compound having a carbon-carbon triple bond and at least two halogens in the molecule, compound A is preferably an alkyne compound having at least two halogens.

[0094] Examples of halogens in compound A include fluorine, chlorine, and bromine. The number of halogens in compound A is preferably five or less, and more preferably four or less. The number of halogens in compound A may be two or three.

[0095] If compound A is a compound having a carbon-carbon double bond and at least two halogens in its molecule, compound A may have only one carbon-carbon double bond site, or it may have two or more. Compound A may have, for example, 10 or fewer carbon-carbon double bonds, preferably 6 or fewer, more preferably 4 or fewer, and even more preferably 3 or fewer.

[0096] If compound A is a compound having a carbon-carbon triple bond and at least two halogens in its molecule, compound A may have only one carbon-carbon triple bond site, or it may have two or more. Compound A may have, for example, 10 or fewer carbon-carbon triple bonds, preferably 6 or fewer, more preferably 4 or fewer, and even more preferably 3 or fewer.

[0097] The number of carbon atoms in compound A is, for example, 2 or more and 20 or less, preferably 3 or more, preferably 16 or less, more preferably 12 or less, even more preferably 10 or less, even more preferably 8 or less, and particularly preferably 6 or less.

[0098] Compound A may be linear or branched. Furthermore, compound A may have hydrogen atoms substituted with other substituents. Examples of substituents include hydrocarbon groups, halo groups, nitro groups, cyano groups, oxo groups, thioxo groups, sulfo groups, sulfamoyl groups, sulfinamoyl groups, and sulfenamoyl groups. Hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, and aralkyl groups, and for example, have 1 to 10 carbon atoms.

[0099] Specific examples of compound A include compounds having a carbon-carbon double bond site, such as 3,4-dichloro-1-butene and 1,4-dichloro-2-butene; and compounds having a carbon-carbon triple bond site, such as 1,4-dichloro-2-butyne.

[0100] The compound A used in step 1 may be a single compound or two or more compounds. For example, when producing a sulfur-containing polymer compound having both the structural unit represented by formula (2) and the structural unit represented by formula (3), two different compounds A are used. Similarly, when producing a sulfur-containing polymer compound having both the structural unit represented by formula (2') and the structural unit represented by formula (4), two different compounds A are used.

[0101] In step 1, the method of reacting the sulfur source or sulfur polymer with compound A is not particularly limited, and known methods such as those disclosed in the aforementioned Patent Document 1 can be broadly employed in the present invention. For example, it is preferable to react the sulfur source or sulfur polymer with compound A at an interface. Specifically, a solution 1 in which the sulfur source or sulfur polymer is dissolved and compound A can be prepared, and the interfacial reaction can be carried out using these. Therefore, the solvent used to prepare the solution 1 is a solvent that undergoes phase separation with compound A (i.e., does not dissolve in each other).

[0102] The solvent for preparing the solution 1 may be water or an aqueous solvent such as an alcohol compound, or a polar solvent such as dimethylacetamide or acetonitrile. Among these, water is preferred as the solvent for preparing the solution 1.

[0103] The concentration of solution 1 is not particularly limited, and can be, for example, 0.1 to 500 g / L, preferably 0.5 to 300 g / L, more preferably 1 to 200 g / L, and even more preferably 2 to 100 g / L. Similarly, the concentration of solution 2 is not particularly limited, and can be, for example, 0.1 to 500 g / L, more preferably 0.2 to 300 g / L, and even more preferably 0.5 to 200 g / L.

[0104] In the reaction between the sulfur source or sulfur polymer and compound A, the ratio of the two used is not particularly limited. For example, 0.05 to 10 moles of compound A can be used per mole of sulfur source or sulfur polymer, 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.

[0105] Interfacial reactions can be carried out, for example, in the same manner as known interfacial reactions. In these interfacial reactions, catalysts may be used as needed. Examples of catalysts include conventional phase-transfer catalysts used in interfacial reactions, such as ammonium salts having long-chain alkyl groups, like hexadecyltrimethylammonium bromide. The amount of catalyst used is not particularly limited and can be the same as in conventional interfacial reactions; typically, a so-called catalytic amount of the phase-transfer catalyst can be used.

[0106] In the manufacturing method of the present invention, the reaction temperature is not particularly limited when reacting a sulfur source or sulfur polymer with compound A. For example, it can be 0 to 100°C, preferably 10 to 80°C.

[0107] The reaction between the sulfur polymer and compound A is a polycondensation reaction. Specifically, the sulfur at the ends of the linear sulfur polymer reacts with the polycondensable functional group (halogen) in compound A, and the polycondensation reaction proceeds to produce the sulfur-containing polymer compound of the present invention. After the reaction in step 1, the sulfur-containing polymer compound can be separated and obtained by an appropriate method.

[0108] In the manufacturing method including step 1, a sulfur-containing polymer compound containing the structural unit represented by formula (2) or a sulfur-containing polymer compound containing the structural unit represented by formula (2') can be easily produced. Furthermore, in the manufacturing method including step 1, in the sulfur-containing polymer compound containing the structural unit represented by formula (3), in particular R in formula (3) ２ A sulfur-containing polymer compound in which the divalent group represented by formula (3a) can be easily produced. Furthermore, in the production method including step 1, in the sulfur-containing polymer compound containing the structural unit represented by formula (4), in particular R in formula (4) ４ This allows for the easy production of a sulfur-containing polymer compound, which is represented by the divalent group in formula (4a).

[0109] (Step 2) Next, a method for producing the sulfur-containing polymer compound of the present invention will be described by Step 2. In Step 2, a hydroxyl group-containing sulfur polymer is reacted with compound B, which will be described later.

[0110] The hydroxyl group-containing sulfur polymer is a sulfur polymer and a compound represented by the following general formula (5) CR ２０ -R １０ -R ２０ (5) (In formula (5), R １０ is an organic group, two R ２０ It can be obtained by a polycondensation reaction with (which is a functional group that can polycondense, either identical or different). The conditions for such a polycondensation reaction can be found in the reaction described in Patent Document 1 mentioned above. Hereafter, the compound represented by formula (5) will be referred to as compound C.

[0111] R １０ As an example, an alkylene group (-C) which may have one or more substituents X. ｍ H ２ｍExamples of substituents include alkylene groups (where -, m is an integer) that may have one or more substituents X and may have one or more ether bonds (-O-) inserted, alkenylene groups that may have one or more substituents X, alkylene groups that may have one or more substituents X, cycloalkylene groups that may have one or more substituents X, cycloalkenylene groups that may have one or more substituents X, cycloalkadienylene groups that may have one or more substituents X, arylene groups that may have one or more substituents X, aralkylene groups that may have one or more substituents X, non-aromatic heterocyclic groups that may have one or more substituents X, and heteroarylene groups that may have one or more substituents X. Examples of substituents X include hydrocarbon groups, halo groups, nitro groups, cyano groups, oxo groups, thioxo groups, sulfo groups, sulfamoyl groups, sulfinamoyl groups, and sulfenamoyl groups. Hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, and aralkyl groups, for example, having 1 to 10 carbon atoms.

[0112] In equation (5), R １０ Preferably, R is 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 mechanical properties of the resulting sulfur-containing polymer compound are also likely to be improved. In formula (5), R １０ The (divalent organic group) is more preferably an alkylene group which may have one or more substituents X, and even more preferably an alkylene group which does not have substituents 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.

[0113] In equation (5), R ２０ R is a polycondensable functional group. Therefore, ２０Examples of monovalent groups include epoxy groups (a group obtained by removing one hydrogen atom from ethylene oxide), halogen atoms, glycidyl groups, -C(=O)X (where X is a halogen atom such as chlorine or fluorine), -COOH, and -NCO, with epoxy groups or glycidyl groups being particularly preferred.

[0114] Compound C is, for example, an alkyl compound having 4 to 12 carbon atoms and epoxy groups at both ends, such as 1,2,7,8-diepoxyoctane.

[0115] The reaction between the sulfur polymer and compound C represented by formula (5) can be carried out using a wide range of known methods. For example, the reaction conditions described in the aforementioned Patent Document 1 can also be used in the present invention.

[0116] Compound B used in step 2 is at least one selected from the group consisting of compounds having a carbon-carbon double bond in the molecule and compounds having a carbon-carbon double bond in the molecule, and compound B may further have a functional group that can react with a hydroxyl group by condensation or addition. Examples of functional groups that can react with a hydroxyl group by condensation include halogens (fluorine, chlorine, etc.), carboxyl groups, amino groups, and hydroxyl groups. Examples of functional groups that can react with a hydroxyl group by addition include isocyanate groups, carboxyl groups, amino groups, and hydroxyl groups.

[0117] Specific examples of compound B used in step 2, which is a sulfur-containing polymer compound having a carbon-carbon double bond moiety, include compounds having an addition-reactive functional group such as an isocyanate group at the alkyl terminus of an alkyl (meth)acrylate. The number of carbon atoms in the alkyl group of the alkyl (meth)acrylate is, for example, 1 to 10, preferably 2 to 6. An example of a compound having an addition-reactive functional group such as an isocyanate group at the alkyl terminus of an alkyl (meth)acrylate is 2-isocyanate ethyl (meth)acrylate. Other examples of compound B other than (meth)acrylate include various vinyl monomers having an isocyanate group, for example, vinyl monomers having a structure in which an NCO group is bonded to a C=C bond via a hydrocarbon group. Examples of hydrocarbon groups in this case include, for example, a linear or branched alkyl group having 1 to 10 carbon atoms, an aromatic group having 5 to 12 carbon atoms, or a group having both. An example of such a vinyl monomer is 3-isopropenyl-α,α-dimethylbenzyl isocyanate.

[0118] Further examples of compound B used in step 2, which is a sulfur-containing polymer compound having a carbon-carbon double bond site, include compounds having a (meth)acryloyl group with a condensation-reactive functional group, such as halogenated (meth)acryloyl (compounds in which a halogen is bonded to the C=O carbon of the (meth)acryloyl group), such as acryloyl chloride.

[0119] Compound B used in step 2, which is a sulfur-containing polymer compound having a carbon-carbon triple bond site, is an example of compound B used to produce a sulfur-containing polymer compound. Examples of compound B include various compounds having a carboxyl group, for example, a compound having a structure in which a COOH group is bonded to a C≡C bond via a hydrocarbon group. Examples of hydrocarbon groups in this case include linear or branched alkyl groups having 1 to 10 carbon atoms, aromatic groups having 5 to 12 carbon atoms, or groups having both. An example of such a compound is CH≡C-(CH₂ ２ )ｎ Examples include -COOH. Here, n is a number between 1 and 10, preferably between 1 and 6.

[0120] In step 2, the reaction between the hydroxyl group-containing sulfur polymer and compound B can be carried out under conditions for known addition or condensation reactions, for example. In addition reactions, for example, known catalysts (such as dibutyltin dilaurate), polymerization inhibitors, solvents, etc., can be used. In condensation reactions, for example, known catalysts (such as triethylamine), polymerization inhibitors, solvents, etc., can be used. Solvents that can be used in addition or condensation reactions include chlorinated hydrocarbons such as chloroform and 1,2-dichloroethane; ether compounds such as diethyl ether and tetrahydrofuran; aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; ketone compounds such as acetone and methyl ethyl ketone; ester compounds such as vinyl acetate; alcohols such as methanol, ethanol, isopropyl alcohol, and t-butanol; formamides such as N,N-dimethylformamide and N,N-dimethylacetamide; pyrrolidones such as 2-pyrrolidone and N-methylpyrrolidone; and dimethyl sulfoxides.

[0121] In step 2, after reacting the hydroxyl group-containing sulfur polymer with compound B, the target sulfur-containing polymer compound can be obtained by purification treatment using an appropriate method.

[0122] In the reaction of step 2, the functional groups in compound B undergo a condensation or addition reaction with the hydroxyl groups in the hydroxyl group-containing sulfur polymer, thereby producing the sulfur-containing polymer compound of the present invention.

[0123] In the manufacturing method including step 2, the sulfur-containing polymer compound containing the structural unit represented by formula (3) is particularly R in formula (3). ２ However, at least one hydrogen atom is "-OR ３A sulfur-containing polymer compound (a sulfur-containing polymer compound having a carbon-carbon double bond site) having an alkylene group having a structure substituted with "" can be easily produced. Furthermore, in the production method including step 2, in the sulfur-containing polymer compound containing the structural unit represented by formula (4), in particular R in formula (4) ４ However, at least one hydrogen atom is "-OR ５ Sulfur-containing polymer compounds (sulfur-containing polymer compounds having a carbon-carbon triple bond site) having an alkylene group with a structure substituted with "" can be easily produced.

[0124] In the manufacturing method comprising step 1 or step 2 described above, a sulfur-containing polymer compound having the carbon-carbon double bond site or carbon-carbon triple bond site can be easily introduced into the sulfur polymer, that is, the sulfur-containing polymer compound of the present invention can be produced by a simple method.

[0125] 3. Crosslinked Polymer Compounds Crosslinked polymer compounds can be formed using the sulfur-containing polymer compound of the present invention. Specifically, since the sulfur-containing polymer compound of the present invention contains sulfur moieties and carbon-carbon double bond moieties or carbon-carbon triple bond moieties, sulfur radicals generated by external stimuli such as heating, for example, react with the C=C bonds or C≡C bonds in the sulfur-containing polymer compound (bond exchange) and form a crosslinked structure. This yields a crosslinked polymer compound. Therefore, such a crosslinked polymer compound has a structure in which the sulfur-containing polymer compound of the present invention has self-crosslinked.

[0126] External stimuli include, for example, heat and light such as active energy rays. When the external stimulus is heat, for example, the crosslinked polymer compound can be formed by heating the sulfur-containing polymer compound of the present invention. Specifically, the crosslinked polymer compound can be obtained by heating the sulfur-containing polymer compound of the present invention to, for example, 20 to 200°C, preferably 80 to 160°C.

[0127] In terms of easily forming a cross-linked structure, it is preferable that the number of sulfur atoms in the sulfur moiety of the sulfur-containing polymer compound of the present invention, i.e., the value of n in formula (1) above, be 2 or more. This is because S-S bonds are easily separated and reformed, and bond exchange (disulfide-ene reaction) with C=C bonds occurs particularly readily.

[0128] 4. Method of Use of Sulfur-Containing Polymer Compounds The sulfur-containing polymer compounds of the present invention can have excellent adhesive properties and can therefore be used as raw materials for adhesives, for example. That is, the sulfur-containing polymer compounds of the present invention can be used as components of adhesive compositions.

[0129] The above adhesive composition, by containing the sulfur-containing polymer compound of the present invention, can bond materials more strongly when bonded at high temperatures (e.g., 80 to 160°C). Furthermore, once materials are bonded together by the sulfur-containing polymer compound, they are less likely to peel off even after subsequent high-temperature treatment. Moreover, the sulfur-containing polymer compound of the present invention can bond materials together at temperatures above room temperature (e.g., 20°C or higher) even when in a solid state (film or powder). In this case as well, bonding at high temperatures (e.g., 80 to 160°C) results in a stronger bond between materials.

[0130] As described above, the bonding method using the sulfur-containing polymer compound of the present invention provides high adhesive performance in high-temperature environments, is resistant to peeling even after high-temperature treatment, and can exhibit adhesive function even in a solid state.

[0131] Methods for bonding using the sulfur-containing polymer compound of the present invention include, for example, the conventional method of using the sulfur-containing polymer compound in solution as an adhesive, as well as a method of attaching the sulfur-containing polymer compound in a solid state to the bonding area before bonding. When bonding by attaching the sulfur-containing polymer compound in a solid state to the bonding area, the bonding may be performed in an atmosphere of 80°C or lower, including room temperature, or by heating as necessary (for example, 80 to 160°C). In other words, by using the sulfur-containing polymer compound of the present invention, it is not necessary to adjust it to a solution or dispersion state, and it is possible to bond materials in a solid state (i.e., without using a solvent). The sulfur-containing polymer compound in a solid state may be, for example, in the form of a powder, film, etc.

[0132] The adhesive composition is not particularly limited in type, as long as it contains the sulfur-containing polymer compound of the present invention; for example, it may contain components found in known adhesives. The adhesive composition may consist solely of the sulfur-containing polymer compound of the present invention.

[0133] The type of material to be bonded by the adhesive composition is not particularly limited, and various substrates such as glass plates, PTFE (polytetrafluoroethylene) plates, and stainless steel plates can be used, with glass plates and stainless steel plates being preferred among them.

[0134] The sulfur-containing polymer compound of the present invention can also be used as a raw material for manufacturing various molded articles. For example, a resin composition can be prepared using the sulfur-containing polymer compound of the present invention, and a molded article can be manufactured using such a resin composition.

[0135] The above-mentioned molded article, by containing the sulfur-containing polymer compound of the present invention, will, for example, exhibit excellent mechanical strength.

[0136] The molded article is not particularly limited in type, as long as it contains the sulfur-containing polymer compound of the present invention, and may, for example, contain components found in known molded articles. The molded article may consist solely of the sulfur-containing polymer compound of the present invention. Examples of molded articles include films, sheets, thin films, plates, blocks, fibers, and the like.

[0137] In specifying the inventions contained herein, the components (properties, structures, functions, etc.) described in each embodiment of this disclosure may be combined in any way. That is, this disclosure encompasses all subject matter consisting of any combination of the combinatable components described herein.

[0138] The present invention will be described more specifically below with reference to examples, but the present invention is not limited to the embodiments of these examples.

[0139] (Example 1a) A sulfur-containing polymer compound was synthesized according to the reaction scheme shown in Figure 1(a). First, sodium sulfide pentahydrate (Na) was used as the sulfur source. ２ S・5H ２ Compound A (174.7 mg, 1.04 mmol) was dissolved in 5 mL of water. To the resulting solution, 3,4-dichloro-1-butene (193.3 mg, 1.56 mmol) as compound A and 0.05 mmol of hexadecyltrimethylammonium bromide as a phase transfer catalyst were added, and an interfacial reaction (polycondensation reaction) was carried out by stirring at room temperature (25°C) for 1 day. Since insoluble matter was produced during the reaction, a brown viscous substance was obtained by extraction by centrifugation. Subsequently, the target product, a sulfur-containing polymer compound, was obtained by drying under reduced pressure (yield 29.5 mg).

[0140] (Example 1b) A sulfur-containing polymer compound was synthesized according to the reaction scheme shown in Figure 1(b). First, sulfur (6.858 g, 0.027 mol) and Na ２ S・5H ２ O (8.976 g, 0.053 mmol) was dissolved in 100 mL of water, and then filtered to obtain a solution of linear sulfur polymer (abbreviated as LS). Note that sulfur and Na ２ S・5H ２ O is the molar ratio (sulfur:Na) ２ S・5H ２A solution was prepared in a 1:2 ratio using (O). To this solution, 3,4-dichloro-1-butene (10.0 g, 0.080 mol) as compound A and 0.05 mmol of hexadecyltrimethylammonium bromide as a phase transfer catalyst were added, and an interfacial reaction (polycondensation reaction) was carried out by stirring at room temperature (25°C) for 1 day. Since insoluble matter was produced during the reaction, it was filtered off, and the resulting solid was washed sequentially with water and chloroform, and then dried under reduced pressure to obtain the target sulfur-containing polymer compound (yield 4.31 g).

[0141] (Analysis of Example 1a) Figures 2(a) and 2(b) show the sulfur-containing polymer compounds obtained in Example 1a and Example 1b, respectively. １ Figure 2(a) shows the 1H-NMR measurement results, and Figure 2(b) shows the FT-IR spectrum measurement results. First, the NMR spectrum of the sulfur-containing polymer compound obtained in Example 1a (the middle spectrum shown in Figure 2(a)) showed a peak that was clearly different from that of the monomer (the upper spectrum shown in Figure 2(a)). Furthermore, when an aqueous solution of acidic potassium permanganate was added to the sulfur-containing polymer compound obtained in Example 1a, the reddish-purple color of the permanganate ion disappeared, and a peak that is thought to originate from a C=C bond was observed in the FT-IR measurement (the upper spectrum shown in Figure 2(b)), confirming the presence of a double bond in the sulfur-containing polymer compound obtained in Example 1a. From the above, it was found that the sulfur-containing polymer compound obtained in Example 1a yielded the product shown in the reaction scheme of Figure 1(a).

[0142] (Analysis of Example 1b) First, in the NMR spectrum of the sulfur-containing polymer compound obtained in Example 1b (the lower spectrum shown in Figure 2(a)), a shift in the integral value was observed, but a peak clearly different from that of the monomer (the upper spectrum shown in Figure 2(a)) was observed. Furthermore, when an aqueous solution of acidic potassium permanganate was added to the sulfur-containing polymer compound obtained in Example 1b, the reddish-purple color of the permanganate ion disappeared, and a peak thought to originate from a C=C bond was observed in the FT-IR measurement (the lower spectrum shown in Figure 2(b)), confirming the presence of a double bond in the sulfur-containing polymer compound obtained in Example 1b. From the above, it was found that the sulfur-containing polymer compound obtained in Example 1b yielded the product (n=4.4) shown in the reaction scheme of Figure 1(b).

[0143] (Example 2a) A sulfur-containing polymer compound was synthesized according to the reaction scheme shown in Figure 3(a). First, sodium sulfide pentahydrate (Na) was used as the sulfur source. ２ S・5H ２ Compound A (6.730 g, 0.0400 mol) was dissolved in 70 mL of water. To the resulting solution, 1,4-dichloro-2-butene (5.000 g, 0.0400 mol) as compound A and 0.05 mmol of hexadecyltrimethylammonium bromide as a phase transfer catalyst were added, and an interfacial reaction (polycondensation reaction) was carried out by stirring at room temperature (25°C) for 1 day. Since an insoluble substance was formed during the reaction, chloroform was added to it, and the organic layer was extracted. Chloroform was removed by evaporation, and a viscous substance was obtained. This viscous substance was dried under reduced pressure to obtain the target sulfur-containing polymer compound (yield 2.11 g).

[0144] (Example 2b) A sulfur-containing polymer compound was synthesized according to the reaction scheme shown in Figure 3(b). First, sulfur (3.428 g, 0.0134 mol) and Na ２ S・5H ２ 4.485 g, 0.0267 mol of O was dissolved in 50 mL of water, and then filtered to obtain the LS solution. ２ S・5H ２ O is the molar ratio (sulfur:Na) ２ S・5H２ A solution was prepared in a 1:2 ratio using O). To this solution, 1,4-dichloro-2-butene (5.006 g, 0.0400 mol) as compound A and 0.05 mmol of hexadecyltrimethylammonium bromide as a phase transfer catalyst were added, and an interfacial reaction (polycondensation reaction) was carried out by stirring at room temperature (25°C) for 1 day. Since insoluble matter was produced during the reaction, it was filtered off, and the obtained solid was washed sequentially with water and chloroform, and then dried under reduced pressure to obtain the target sulfur-containing polymer compound (yield 2.69 g).

[0145] (Analysis of Example 2a) Figures 4(a) and 4(b) show the sulfur-containing polymer compounds obtained in Example 2a and Example 2b, respectively. １ Figure 4(b) shows the results of 1H-NMR measurement (Figure 4(a)) and FT-IR spectral measurement (Figure 4(b)). First, the NMR spectrum of the sulfur-containing polymer compound obtained in Example 2a (the middle spectrum shown in Figure 4(a)) showed a peak that was clearly different from that of the monomer (the upper spectrum shown in Figure 4(a)). Furthermore, the FT-IR measurement of the sulfur-containing polymer compound obtained in Example 2a showed a peak that is thought to originate from a C=C bond (the upper spectrum shown in Figure 4(b)), confirming the presence of a double bond in the sulfur-containing polymer compound obtained in Example 2a. From the above, it was found that the sulfur-containing polymer compound obtained in Example 2a yielded the product shown in the reaction scheme of Figure 3(a).

[0146] (Analysis of Example 2b) First, the NMR spectrum of the sulfur-containing polymer compound obtained in Example 2b (lower spectrum shown in Figure 4(a)) showed peaks that were clearly different from those of the monomer (upper spectrum shown in Figure 4(a)). Since a peak thought to originate from a C=C bond was observed in the FT-IR measurement (lower spectrum shown in Figure 4(b)), the presence of a double bond was confirmed in the sulfur-containing polymer compound obtained in Example 2b. Furthermore, from the Raman spectrum of the sulfur-containing polymer compound obtained in Example 2b shown in Figure 5, the presence of C-S bonds and S-S bonds was confirmed in the sulfur-containing polymer compound obtained in Example 2b. From the above, it was found that the sulfur-containing polymer compound obtained in Example 2b yielded the product (n=5.2) shown in the reaction scheme of Figure 3(b).

[0147] (Example 3a) A sulfur-containing polymer compound was synthesized according to the reaction scheme shown in Figure 6(a). First, sodium sulfide pentahydrate (Na2S・5H) was used as the sulfur source. ２ Compound A (13.46 g, 0.0800 mol) was dissolved in 150 mL of water. To the resulting solution, 3,4-dichloro-1-butene (5.010 g, 0.0401 mol) and 1,4-dichloro-2-butene (5.000 g, 0.0400 mol) were added as compound A, and 0.05 mmol of hexadecyltrimethylammonium bromide was added as a phase transfer catalyst. The mixture was stirred at room temperature (25°C) for 1 day to carry out an interfacial reaction (polycondensation reaction). Insoluble matter was produced during the reaction, so chloroform was added to it to extract the organic layer, and the chloroform was removed by evaporation to obtain a viscous material. This viscous material was dried under reduced pressure to obtain the target sulfur-containing polymer compound (yield 1.79 g).

[0148] (Example 3b) A sulfur-containing polymer compound was synthesized according to the reaction scheme shown in Figure 6(b). First, sulfur (6.847 g, 0.0267 mol) and Na ２ S・5H ２ O (8.974 g, 0.0534 mol) was dissolved in 100 mL of water, and then filtered to obtain the LS solution. ２ S・5H ２O is the molar ratio (sulfur:Na) ２ S・5H ２ A solution was prepared in a 1:2 ratio using O). To this solution, 3,4-dichloro-1-butene (5.04 g, 0.0403 mol) and 1,4-dichloro-2-butene (5.01 g, 0.0401 mol) were added as compound A, and 0.05 mmol of hexadecyltrimethylammonium bromide was added as a phase transfer catalyst. The mixture was stirred at room temperature (25°C) for one day to carry out an interfacial reaction (polycondensation reaction). Insoluble matter was produced during the reaction, so this was filtered off, and the resulting solid was washed sequentially with water and chloroform, and then dried under reduced pressure to obtain the target sulfur-containing polymer compound (yield 5.32 g).

[0149] (Analysis of Example 3a) Figures 7(a) and 7(b) show the sulfur-containing polymer compounds obtained in Example 3a and Example 3b, respectively. １ Figure 7(b) shows the results of 1H-NMR measurement (Figure 7(a)) and FT-IR spectral measurement (Figure 7(b)). First, the NMR spectrum of the sulfur-containing polymer compound obtained in Example 3a (the third spectrum shown in Figure 7(a)) showed peaks that were clearly different from those of the monomer (the first and second spectra shown in Figure 7(a)). Furthermore, the FT-IR measurement of the sulfur-containing polymer compound obtained in Example 3a showed peaks that are thought to originate from C=C bonds (the upper spectrum shown in Figure 7(b)), confirming the presence of double bonds in the sulfur-containing polymer compound obtained in Example 3a. From the above, it was found that the sulfur-containing polymer compound obtained in Example 3a yielded the product shown in the reaction scheme in Figure 6(a).

[0150] (Analysis of Example 3b) First, the NMR spectrum of the sulfur-containing polymer compound obtained in Example 3b (the bottom spectrum shown in Figure 7(a)) showed peaks that were clearly different from those of the monomer (the first and second spectra shown in Figure 7(a)). Since a peak thought to originate from a C=C bond was observed in the FT-IR measurement (the bottom spectrum shown in Figure 7(b)), the presence of a double bond was confirmed in the sulfur-containing polymer compound obtained in Example 3b. Furthermore, from the Raman spectrum of the sulfur-containing polymer compound obtained in Example 3b shown in Figure 8, the presence of C-S bonds and S-S bonds was confirmed in the sulfur-containing polymer compound obtained in Example 3b. From the above, it was found that the sulfur-containing polymer compound obtained in Example 3b yielded the product (n=4.8) shown in the reaction scheme of Figure 6(b).

[0151] (Comparative Example 1a) A sulfur-containing polymer compound was obtained in the same manner as in Example 1a, except that compound A was changed to 1,2-dichloroethane.

[0152] (Comparative Example 1b) A sulfur-containing polymer compound was obtained in the same manner as in Example 1b, except that compound A was changed to 1,2-dichloroethane.

[0153] (Test Example 1) Following the adhesive test procedure schematically shown in Figure 9, the adhesive performance of the sulfur-containing polymer compounds prepared in each example and comparative example was evaluated as follows. First, 10 mg of film-like (solid) sulfur-containing polymer compound was placed on one of a pair of substrates, and the other substrate was placed on top of it, thereby creating a laminate in which the sulfur-containing polymer compound was sandwiched between the pair of substrates. A 1 kg weight was placed on this laminate and left to stand for 24 hours in an atmosphere at room temperature (20°C) or 120°C to confirm whether the pair of substrates adhered to each other. Glass plates, PTFE plates (Teflon®) or stainless steel plates were used as substrates. The adhesive performance of whether the pair of substrates adhered to each other was evaluated according to the following criteria. <Criteria> ○: When a 500 g weight was suspended from one of the substrates of the laminate and lifted, the weight was lifted without falling. △: When a 500g weight was attached to one side of the laminated substrate and lifted, there was a slight wobble in the adhesive area, but the weight did not fall off. ×: When a 500g weight was attached to one side of the laminated substrate and lifted, the adhesive area completely detached and the weight fell off.

[0154] Table 1 shows the results of the adhesive performance evaluation test for Test Example 1. From Table 1, it can be seen that the sulfur-containing polymer compound obtained in the example has high adhesive performance even at high temperatures.

[0155]

[0156] Table 2 shows the results of testing whether the pair of substrates separated after heating the laminate obtained in Test Example 1 (however, the laminate had a glass substrate) at 120°C for 24 hours.

[0157]

[0158] For comparison, a sulfur-containing polymer compound obtained in Example 1 described in Patent Document 1 was separately manufactured, and the same test as in Test Example 1 was performed using this sulfur-containing polymer compound. However, it was not possible to bond the pair of substrates at either room temperature (20°C) or 120°C.

[0159] From the above results, it was demonstrated that the sulfur-containing polymer compounds obtained in the examples have excellent adhesive properties even in a solid state, and in particular, they can bond materials together more strongly when bonded at high temperatures. Furthermore, when materials were bonded together using the sulfur-containing polymer compounds obtained in the examples, they were difficult to peel off even after high-temperature treatment. This is presumed to be because the sulfur-containing polymer compounds formed a cross-linked structure through self-crosslinking when treated at high temperatures, i.e., curing was accelerated. When sulfur-containing polymer compounds are heated, the S-S bonds in the sulfur-containing polymer compounds cleave and sulfur radicals are generated. These radicals react with the C=C bonds in the sulfur-containing polymer compounds, causing so-called bond exchange. In other words, it is presumed that the sulfur-containing polymer compounds exhibit excellent adhesive properties at high temperatures because they self-crosslink and harden when heated.

[0160] (Manufacturing Example 1) Sulfur (523 mg, 2.04 mmol) and Na ２ Solution 1 of the linear sulfur polymer (abbreviated as LS) was obtained by dissolving S (684 mg, 4.08 mmol, pentahydrate) in 10 mL of water and then filtering the solution. Next, 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 was added to Solution 2 as a phase transfer catalyst. Solution 2 was added to Solution 1, and an interfacial reaction (polycondensation reaction) was carried out by stirring at room temperature (25°C) for 1 day. Solutions 1 and 2 were prepared so that the molar ratio of LS to OctdiEpo (LS:OctdiEpo) was 2:1. Since an insoluble substance was formed between the aqueous layer and the chloroform layer during the aforementioned interfacial reaction, this was filtered off, and the resulting solid was sequentially washed with water and chloroform, and then dried under reduced pressure to obtain the target product, a hydroxyl group-containing sulfur polymer "PolyOD-S ３．４ " was obtained. Such PolyOD-S ３．４ Mn = 7.8 × 10 ３ , Mw=13.0×10 ３ The ratio Mw / Mn was 1.6.

[0161] (Manufacturing Example 2) Following the manufacturing procedure of Manufacturing Example 1, the hydroxyl group-containing sulfur polymer "PolyOD-S ３．５ " was obtained. Such PolyOD-S ３．５ Mn = 2.3 × 10 ３ Mw = 7.2 × 10 ３ The ratio of Mw / Mn was 7.1.

[0162] (Example 4a) A sulfur-containing polymer compound was synthesized according to the reaction scheme shown in Figure 10. First, the hydroxyl group-containing sulfur polymer (PolyOD-S) obtained in Production Example 1 was synthesized. ３．４ 489 mg (assumed amount of hydroxyl groups: 3.88 mmol, 1.0 eq.) of compound B was dissolved in 10 mL of anhydrous DMF. To the resulting solution, 2-isocyanate ethyl acrylate (EA-NCO, 821 mg, 5.82 mmol, 1.5 eq. relative to the assumed amount of hydroxyl groups) was added as compound B, and dibutyltin dilaurate (DBTDL, 21 mg, 0.033 mmol, 20 μL, 0.0086 eq.) was added as a catalyst. The reaction was carried out at room temperature (20°C) for 18 hours under a nitrogen atmosphere, shielded from light with aluminum foil. The solution changed from yellow to brown, and after stirring was continued at 50°C for 3 hours, no further color change was observed in the solution. The solvent was then removed by evaporation, yielding a viscous liquid. The viscous liquid was washed three times with diethyl ether and acetone, respectively, and then dried under reduced pressure at 60°C to obtain a yellow resin yield of 662 mg.

[0163] (Analysis of Example 4a) Figure 11 shows the yellow resin obtained in Example 4a. １The results of 1H-NMR and FT-IR spectroscopy are shown. First, in the NMR spectrum of the yellow resin obtained in Example 4a (the lower spectrum shown in Figure 11(a)), the disappearance of peaks originating from the raw material hydroxyl group-containing sulfur polymer and compound B (the upper and middle spectra shown in Figure 11(a), respectively), and the appearance of peaks originating from C=C bonds and NH bonds were observed, and the integral value was in agreement with the assumed structure. In the FT-IR measurement of the yellow resin (the lower spectrum shown in Figure 11(b)), in addition to the observation of peaks originating from C=C bonds, C=O bonds and C-N-H bonds, the peak originating from the OH group shifted, and the formation of NH groups was observed. From the above, the yellow resin obtained in Example 4a is a sulfur-containing polymer compound (PolyOD-S) whose product is shown in the reaction scheme of Figure 10. ３．４ It was found that the result was named EA, i.e., obtained as n = 3.4.

[0164] (Example 4b) A sulfur-containing polymer compound was synthesized according to the reaction scheme shown in Figure 12. First, the hydroxyl group-containing sulfur polymer (PolyOD-S) obtained in Production Example 1 was synthesized. ３．４ 634 mg (assumed amount of hydroxyl groups: 5.04 mmol, 1.0 eq.) of compound B was dissolved in 10 mL of anhydrous DMF. To the resulting solution, 2-isocyanate methyl acrylate (EMA-NCO, 1170 mg, 7.55 mmol, 1.5 eq. relative to the assumed amount of hydroxyl groups) was added as compound B, and dibutyltin dilaurate (DBTDL, 21 mg, 0.033 mmol, 20 μL, 0.0086 eq.) was added as a catalyst. The reaction was carried out at room temperature (20°C) for 22 hours under a nitrogen atmosphere, shielded from light with aluminum foil. As a result, the solution changed from yellow to light brown, and the solvent was removed by evaporation to obtain a viscous liquid. This viscous liquid was washed three times each with acetone and ethyl acetate, and then dried under reduced pressure at 80°C to obtain an orange resin in a yield of 408 mg.

[0165] (Analysis of Example 4b) Figures 13(a) and (b) show the orange resin obtained in Example 4b, respectively. １Figure 13(a) shows the 1H-NMR measurement results and Figure 13(b) shows the FT-IR spectrum measurement results. First, in the NMR spectrum of the orange resin obtained in Example 4b (the lower spectrum shown in Figure 13(a)), the disappearance of peaks originating from the raw material hydroxyl group-containing sulfur polymer and compound B (the upper and middle spectra shown in Figure 13(a), respectively) and the appearance of peaks originating from C=C bonds and NH bonds were observed. In the FT-IR measurement of the orange resin (the lower spectrum shown in Figure 13(b)), in addition to the observation of peaks originating from C=C bonds, C=O bonds and C-N-H bonds, the peak originating from the OH group shifted, and the formation of NH groups was observed. From the above, the orange resin obtained in Example 4b is a sulfur-containing polymer compound (PolyOD-S) as shown in the reaction scheme of Figure 12. ３．４ It was found that it was obtained as (named EMA).

[0166] (Example 4c) A sulfur-containing polymer compound was synthesized according to the reaction scheme shown in Figure 14. First, the hydroxyl group-containing sulfur polymer (PolyOD-S) obtained in Production Example 1 was synthesized. ３．４ 655 mg (assumed amount of hydroxyl groups: 5.2 mmol, 1.0 eq.) was dissolved in 10 mL of anhydrous DMF. To the resulting solution, 3-isopropenyl-α,α-dimethylbenzyl isocyanate (IPDMB-NCO, 1570 mg, 7.80 mmol, 1.5 eq. relative to the assumed amount of OH) was added as compound B, and dibutyltin dilaurate (DBTDL, 21 mg, 0.033 mmol, 20 μL, 0.0086 eq.) was added as a catalyst. The reaction was carried out at room temperature (20°C) for 22 hours under a nitrogen atmosphere, shielded from light with aluminum foil. As a result, the solution changed from yellow to dark brown, and the solvent was removed by evaporation to obtain a viscous liquid. This viscous liquid was washed three times each with acetone and ethyl acetate, and then dried under reduced pressure at 80°C to obtain a brownish-white resin in a yield of 138 mg.

[0167] (Analysis of Example 4c) Figures 15(a) and (b) show the brownish-white resin obtained in Example 4c, respectively. １Figure 15(b) shows the results of 1H-NMR measurement (Figure 15(a)) and FT-IR spectral measurement (Figure 15(b)). First, in the NMR spectrum of the brownish-white resin obtained in Example 4c (lower spectrum shown in Figure 15(a)), the disappearance of peaks originating from the raw material hydroxyl group-containing sulfur polymer and compound B (upper and middle spectra shown in Figure 15(a), respectively) and the appearance of peaks originating from C=C bonds and NH bonds were observed. In the FT-IR measurement of the brownish-white resin (lower spectrum shown in Figure 15(b)), in addition to the observation of peaks originating from C=C bonds, C=O bonds and C-N-H bonds, the peak originating from the OH group shifted, and the formation of NH groups was observed. From the above, the brownish-white resin obtained in Example 4c is a sulfur-containing polymer compound (PolyOD-S) as shown in the reaction scheme of Figure 14. ３．４ It was found that it was obtained as (named IPDMB).

[0168] (Example 5) A sulfur-containing polymer compound was synthesized according to the reaction scheme shown in Figure 16. First, the hydroxyl group-containing sulfur polymer (PolyOD-S) obtained in Production Example 1 was synthesized. ３．４ 398 mg (assumed amount of hydroxyl groups: 3.16 mmol, 1.0 eq.) was dissolved in 5 mL of anhydrous DMF. To the resulting solution, acryloyl chloride (AC, 572 mg, 6.31 mmol, 1.5 eq. relative to the assumed amount of OH) was added as compound B, and triethylamine (TEA, 640 mg, 6.32 mmol, 877 μL, 2.0 eq.) was added as a catalyst. The reaction was carried out under a nitrogen atmosphere at room temperature (20°C) for 4 hours. The reaction was stopped by adding the resulting reaction solution to 100 mL of water, and the solvent was removed by evaporation. The mixture was then washed three times with water and methanol, and subsequently dried under reduced pressure at 70°C to obtain a yellow resin yield of 50.4 mg.

[0169] (Analysis of Example 5) Figures 17(a) and (b) show the yellow resin obtained in Example 5, respectively. １Figure 17(b) shows the results of 1H-NMR measurement (Figure 17(a)) and FT-IR spectral measurement (Figure 17(b)). First, in the NMR spectrum of the yellow resin obtained in Example 5 (lower spectrum shown in Figure 17(a)), the disappearance of the peak originating from the hydroxyl group-containing sulfur polymer of the raw material (upper spectrum shown in Figure 17(a)) and the appearance of C=C bonds were observed. In the FT-IR measurement of the yellow resin (lower spectrum shown in Figure 17(b)), peaks originating from C=C bonds and C=O bonds were observed. From the above, the yellow resin obtained in Example 5 is a sulfur-containing polymer compound (PolyOD-S) as the product shown in the reaction scheme of Figure 16. ３．４ It was found that it was obtained as (named AC).

[0170] (Test Example 2) Sulfur-containing polymer compound obtained in Example 4a (PolyOD-S ３．４ Tensile tests were performed on two films: Film 1, which was formed from -EA) at 80°C with a molding pressure of 2kN, and Film 2, which was formed at 160°C with a molding pressure of 2kN and then held at 160°C for 1 hour.

[0171] Figure 18(a) shows the results of tensile tests on film 1 (dashed line) and film 2 (solid line).

[0172] Figure 18(a) shows that although the elongation of film 2 was about 1 / 10 that of film 1, the breaking stress was 58.4 MPa, which was about 58 times that of film 1, indicating a significant increase in mechanical strength. This is presumed to be because, during the manufacturing process of film 2, holding it at 160°C for one hour caused the S-S bonds in the sulfur-containing polymer compound contained in the film to break, generating sulfur radicals. These radicals then reacted with the C=C bonds in the sulfur-containing polymer compound, causing what is known as bond exchange. In other words, it is presumed that the heating of film 2 caused the sulfur-containing polymer compound to self-crosslink, resulting in a significant improvement in its mechanical properties. The fact that film 1 (before bond exchange) dissolved in DMSO, while film 2 (after bond exchange) did not, also supports the formation of a crosslinked structure in film 2 due to self-crosslinking.

[0173] Figure 18(b) shows the FT-IR spectra of film 1 (dashed line) and film 2 (solid line). In film 2, the intensity peak originating from the C=C bond was reduced, which also supports the conclusion that the aforementioned bond exchange occurred.

[0174] (Test Example 3) The adhesive performance of the sulfur-containing polymer compound was evaluated using the same procedure as in Test Example 1 described above. First, the film-like (solid state) sulfur-containing polymer compound (PolyOD-S) obtained in Example 4a was evaluated. ３．４ -EA) 10 mg was placed on one of a pair of glass plates, and the other glass plate was placed on top of it to create a laminate in which the sulfur-containing polymer compound was sandwiched between the pair of glass plates. A 1 kg weight was placed on this laminate and left to stand for 24 hours in an atmosphere of 120°C to evaluate whether the pair of glass plates adhered together.

[0175] When a 500g weight was attached to one side of the substrate of the resulting laminate and lifted, the weight was lifted without falling. Therefore, PolyOD-S ３．４ -EA has excellent adhesive properties, and it has been demonstrated that it can bond materials together even more strongly when bonded at high temperatures. This is PolyOD-S ３．４ - It is presumed that the aforementioned bond exchange occurred when EA was heated, leading to the formation of crosslinks.

[0176] (Example 6) A sulfur-containing polymer compound was synthesized according to the reaction scheme shown in Figure 19(a). First, sulfur (3821.5 mg, 14.87 mmol, 1.0 eq.) and Na ２ S・5H ２ 4997 mg, 29.74 mmol, 2.0 eq. of O was dissolved in 50 mL of water, and then filtered to obtain the LS solution. ２ S・5H ２ O is the molar ratio (sulfur:Na) ２ S・5H ２A solution was prepared in a 1:2 ratio using (O). To this solution, 3,4-dichloro-1-butyne (379 mg, 2.974 mmol, 0.2 eq.) and 1,4-dibromoethane (5029 mg, 26.77 mmol, 1.8 eq.) were added as compound A, and the mixture was stirred at room temperature for 24 hours to obtain the target sulfur-containing polymer compound (yield 4801 mg). The obtained sulfur-containing polymer compound was insoluble in the main solvent. Micro-Raman analysis of the sulfur-containing polymer compound (Figure 19(b)) showed peaks originating from C-S bonds and S-S bonds within the polymer, confirming that the reaction was proceeding.

[0177] A film was prepared by molding the sulfur-containing polymer compound having a triple bond obtained in Example 6 above at 80°C. This film was left to stand for 1 hour at 160°C under a pressure of 2 kN. Observation of the appearance of the film after standing revealed a clear change in color and shape compared to before standing. This suggests that so-called bond exchange occurred when the film was placed at 160°C under a pressure of 2 kN, meaning that the sulfur-containing polymer compound obtained in Example 6 has the property of hardening upon heating.

[0178] (Example 7) A sulfur-containing polymer compound was synthesized according to the reaction scheme shown in Figure 20. First, the hydroxyl group-containing sulfur polymer (PolyOD-S) obtained in Production Example 2 was synthesized. ３．５489 mg (1002 mg, assumed amount of OH 7.80 mmol, 1.0 eq.) was dissolved in 20 mL of anhydrous DMF. To the resulting solution, 5-hexynoic Acid (HXA-COOH, 848 mg, 8.58 mmol, 1.1 eq. relative to the assumed amount of OH) was added as compound B, and 4-Dimethylaminopyridine (DMAP, 95 mg, 0.780 mmol, 0.1 eq. relative to the assumed amount of OH) was added as a catalyst. To the resulting solution, a solution of 1-(3-Dimethylaminopropyl)-3-ethylcarbonidiumide Hydrochloride (EDC, 2393 mg, 12.48 mmol, 1.6 eq. relative to the assumed amount of OH) dissolved in 35 ml of anhydrous DMF was added under ice cooling to initiate the reaction. After stirring at room temperature for 24 hours, the solution changed from yellow to black. The solvent was then removed by evaporation, yielding a viscous liquid which was washed three times with methanol and water, followed by drying under reduced pressure at 80°C. The resulting product was a brown resin (yield: 408 mg). １ HNMR measurements revealed the disappearance of peaks originating from the raw polymer and low-molecular-weight compounds, and the appearance of peaks originating from C≡C bonds, as shown in Figure 21. FT-IR measurements showed peaks originating from C≡C and C=O bonds. Based on these results, PolyOD-S shown in Figure 20 was identified. ３．５ - The synthesis of HXA was confirmed. In Figure 21, the top row of the NMR spectrum shows HXA-COOH, and the second row shows a hydroxyl group-containing sulfur polymer (PolyOD-S ３．５ ) The third row is PolyOD-S ３．５ -HXA (reprecipitation treatment with diethyl ether), the fourth step is PolyOD-S ３．５ -HXA (reprecipitation treatment with methanol), the 5th stage is PolyOD-S ３．５ -HXA (reprecipitation treatment with water) is shown. Also, in Figure 21, the top row of the IR spectrum is hydroxyl group-containing sulfur polymer (PolyOD-S ３．５ The second stage is HXA-COOH, and the third stage is PolyOD-S ３．５ -HXA (reprecipitation treatment with diethyl ether), the fourth step is PolyOD-S ３．５- Indicates HXA (reprecipitation treatment with water).

[0179] A film was prepared by molding the sulfur-containing polymer compound having a triple bond obtained in Example 7 above at 80°C. This film was left to stand for 1 hour at 160°C under a pressure of 2 kN. Observation of the appearance of the film after standing revealed a clear change in color and shape compared to before standing. This suggests that so-called bond exchange occurred when the film was placed at 160°C under a pressure of 2 kN, meaning that the sulfur-containing polymer compound obtained in Example 7 has the property of hardening upon heating.

Claims

1. A sulfur-containing polymer compound having the following general formula (1) - (S) ｎ - A sulfur-containing polymer compound having a sulfur moiety represented by formula (1) (wherein n is a number of 1 or more) and one or more multiple bond moieties selected from the group consisting of carbon-carbon double bond moieties and carbon-carbon triple bond moieties.

2. The following general formula (2) - (S) ｎ -R １ - (2) (In formula (2), R １ The sulfur-containing polymer compound according to claim 1, comprising at least a structural unit represented by (where (represents an alkenylene group having at least one carbon-carbon double bond site).

3. The following general formula (3) - (S) ｎ -R ２ - (3) (In formula (3), R ２ The sulfur-containing polymer compound according to claim 1, comprising at least a structural unit represented by (where represents an alkylene group substituted with at least one of the carbon-carbon double bond sites).

4. The following general formula (3)-(S) ｎ -R ２ - (3) (In formula (3), R ２ represents an alkylene group substituted with a group having at least one of the carbon-carbon double bond sites), and further contains a structural unit represented by the sulfur-containing polymer compound according to claim 2.

5. The following general formula (2') - (S) ｎ -R ３ - (2') (In formula (2), R ３ The sulfur-containing polymer compound according to claim 1, comprising at least a structural unit represented by (where (representing an alkylylene group having at least one carbon-carbon triple bond site).

6. The following general formula (4) - (S) ｎ -R ４ - (4) (In formula (4), R ４ The sulfur-containing polymer compound according to claim 1, comprising a structural unit represented by (where represents an alkylene group substituted with at least one of the carbon-carbon triple bond sites).

7. The following general formula (4) - (S) ｎ -R ４ - (4) (In formula (4), R ４ The sulfur-containing polymer compound according to claim 5, further comprising a structural unit represented by (where represents an alkylene group substituted with at least one of the carbon-carbon triple bond sites).

8. A method for producing a sulfur-containing polymer compound according to any one of claims 1 to 7, comprising the step of reacting a sulfur source or a sulfur polymer with compound A, wherein compound A is at least one selected from the group consisting of compounds having a carbon-carbon double bond and at least two halogens in the molecule, and compounds having a carbon-carbon triple bond and at least two halogens in the molecule.

9. A method for producing a sulfur-containing polymer compound according to any one of claims 1 to 7, comprising the step of reacting a hydroxyl group-containing sulfur polymer with compound B, wherein compound B is at least one selected from the group consisting of compounds having a carbon-carbon double bond in the molecule and compounds having a carbon-carbon double bond in the molecule, and compound B further has a functional group that can react with a hydroxyl group through condensation or addition.

10. An adhesive composition comprising a sulfur-containing polymer compound according to any one of claims 1 to 7.

11. A bonding method comprising bonding using a sulfur-containing polymer compound as described in any one of claims 1 to 7.

12. A molded article comprising a sulfur-containing polymer compound according to any one of claims 1 to 7.

13. A crosslinked polymer compound having a structure in which the sulfur-containing polymer compound described in any one of claims 1 to 7 is self-crosslinked.

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