Polymer containing active hydrogen groups, poly(THIO)urethane resin, molded body, and method for producing polymer containing active hydrogen groups

Abstract

This polymer containing active hydrogen groups includes first constituent units (1) and second constituent units (2). The content of carbon atoms derived from aromatic hydrocarbon groups is 20 mass% or higher with respect to the mass of the whole compound containing active hydrogen groups. The proportion of the number n of the second constituent units to the sum of the number m of the first constituent units and the number n of the second constituent units exceeds 0 but is less than 0.09. (X represents -O-, -OC(=O)-, -C(=O)O-, -S-, -SC(=O)-, or -C(=O)S-, Y represents a hydrogen atom or a hydrocarbon group, R1 represents an aromatic hydrocarbon group, and R3 represents R2 or CY2R1CY2, and R2 represents a hydrocarbon group optionally containing a heteroatom.)

Description

Active hydrogen group-containing polymer, poly(thio)urethane resin, molded article, and method for producing an active hydrogen group-containing polymer.

[0001] The present invention relates to an active hydrogen group-containing polymer, a poly(thio)urethane resin, a molded article, and a method for producing an active hydrogen group-containing polymer.

[0002] Polymers containing active hydrogen groups are widely used in various industrial fields. As an example of a polymer containing active hydrogen groups, a crystalline polyether obtained by reacting 1,10-decanediol and p-xylylene glycol in the presence of sulfamic acid at 180°C has been proposed (see, for example, Patent Document 1 (Synthesis Example 3)).

[0003] Japanese Patent Publication No. 2012-255885

[0004] On the other hand, various industrial fields require polymers containing active hydrogen groups with relatively low viscosity.

[0005] Furthermore, the use of the above-mentioned active hydrogen group-containing polymer as a raw material for resins and molded articles is being considered. For example, the use of the active hydrogen group-containing polymer as a raw material for polyurethane resin and / or polythiourethane resin (hereinafter referred to as poly(thio)urethane resin) is being considered. In such cases, there is a need for an active hydrogen group-containing polymer that can produce molded articles with excellent mechanical properties.

[0006] The present invention relates to an activated hydrogen group-containing polymer that can be obtained to have resins and molded articles having relatively good handling properties and relatively good mechanical properties, a method for producing the same, and a poly(thio)urethane resin and molded article.

[0007] The present invention [1] is an active hydrogen group-containing polymer having aromatic hydrocarbon groups, comprising a first structural unit represented by formula (1) and a second structural unit represented by formula (2), wherein the content ratio of carbon atoms derived from the aromatic hydrocarbon groups to the total mass of the active hydrogen group-containing polymer is 20% by mass or more, and the ratio of the average number n of the second structural units contained in the active hydrogen group-containing polymer to the sum of the average number m of the first structural units contained in the active hydrogen group-containing polymer and the average number n of the second structural units contained in the active hydrogen group-containing polymer [n / (n+m)] is greater than 0 and less than 0.09.

[0008]

[0009]

[0010] (In formulas (1) and (2), X represents -O-, -OC(=O)-, -C(=O)O-, -S-, -SC(=O)-, or -C(=O)S-, Y represents a hydrogen atom or a hydrocarbon group, R １ R indicates an aromatic hydrocarbon group. ３ R ２ , or CY ２ R １ CY ２ R ２ (This indicates a hydrocarbon group that may contain heteroatoms.)

[0011] The present invention [2] is an active hydrogen group-containing polymer having aromatic hydrocarbon groups, comprising a first structural unit represented by formula (1) and a second structural unit represented by formula (2), wherein the content ratio of the aromatic hydrocarbon groups is 20% by mass or more with respect to the total mass of the active hydrogen group-containing polymer, and the decomposition composition by hydrogenation of the active hydrogen group-containing polymer comprises a first decomposition compound represented by formula (3) and a second decomposition compound represented by formula (4), wherein in the decomposition composition, the ratio of the number of moles N of the second decomposition compound to the sum of the number of moles M of the first decomposition compound and the number of moles N of the second decomposition compound [N / (M+N)] is greater than 0 and less than 0.09, wherein the active hydrogen group-containing polymer is included.

[0012]

[0013]

[0014] (In Formula (1) and Formula (2), X represents -O-, -OC(=O)-, -C(=O)O-, -S-, -SC(=O)-, or -C(=O)S-, Y represents a hydrogen atom or a hydrocarbon group, and R １ represents an aromatic hydrocarbon group, and R ３ is R ２ or CY ２ R １ CY ２ represents, and R ２ represents a hydrocarbon group which may contain a hetero atom.)

[0015]

[0016]

[0017] (In Formula (3) and Formula (4), Y and R １ are synonymous with Y and R １ in Formula (1).)

[0018] The present invention [3] contains the active hydrogen group-containing polymer according to [1] above, in which the ratio [n / (n + m)] of the average number n of the second constitutional units contained in the active hydrogen group-containing polymer to the total of the average number m of the first constitutional units contained in the active hydrogen group-containing polymer is more than 0 and 0.05 or less.

[0019] The present invention [4] contains the active hydrogen group-containing polymer according to any one of [1] to [3] above, in which the content ratio of carbon atoms derived from the aromatic hydrocarbon group is 20% by mass or more and 50% by mass or less with respect to the total mass of the active hydrogen group-containing polymer.

[0020] The present invention [5] contains the active hydrogen group-containing polymer according to any one of [1] to [4] above, in which in Formula (1) and Formula (2), R １ represents a phenylene group, and the phenylene group represents at least one selected from the group consisting of a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group.

[0021] The present invention [6] includes an active hydrogen group-containing polymer according to any one of the above claims [1] to [5], wherein the first structural unit represented by formula (1) contains a first a structural unit represented by formula (1a) and a first b structural unit represented by formula (1b).

[0022]

[0023]

[0024] (In equations (1a) and (1b), X, Y, R １ and R ２ These are X, Y, and R in equation (1). １ and R ２ (This is synonymous with...)

[0025] The present invention [7] relates to formula (1a), where R ２ However, it contains the active hydrogen group-containing polymer described in [6] above, which may contain heteroatoms as an aliphatic hydrocarbon group.

[0026] The present invention [8] relates to formula (1a), where R ２ However, it contains the active hydrogen group-containing polymer described in [6] above, which may contain heteroatoms in an alicyclic hydrocarbon group.

[0027] The present invention [9] includes an active hydrogen group-containing polymer according to any one of the above claims [1] to [9], wherein in formula (1) and formula (2), X represents -O-, and the active hydrogen group-containing polymer is a polyether polyol.

[0028] The present invention

[10] includes an active hydrogen group-containing polymer according to any one of the above claims [1] to [9], wherein in formulas (1) and (2), all Y represent hydrogen atoms.

[0029] The present invention

[11] includes an active hydrogen group-containing polymer according to any one of the above [1] to

[10] , having a number average molecular weight of 500 or more and 50,000 or less.

[0030] The present invention

[12] includes a poly(thio)urethane resin containing a reaction product of an active hydrogen component containing an active hydrogen group-containing polymer as described in any one of the above items [1] to

[11] and a polyisocyanate component.

[0031] The present invention

[13] includes a molded article containing the poly(thio)urethane resin described in

[12] above.

[0032] The present invention

[14] is a method for producing an active hydrogen group-containing polymer, comprising a preparation step of preparing a first raw material compound represented by formula (A) and a second raw material compound represented by formula (B), and a reaction step of reacting the first raw material compound and the second raw material compound at 60 to 140°C in the presence of an acid catalyst.

[0033]

[0034]

[0035] (In formulas (A) and (B), -XH represents -OH, -OC(=O)H, -C(=O)OH, -SH, -SC(=O)H, and / or -C(=O)SH, Y represents a hydrogen atom or a hydrocarbon group, and R １ R indicates an aromatic hydrocarbon group. ２ (This indicates a hydrocarbon group that may contain heteroatoms.)

[0036] The active hydrogen group-containing polymer of the present invention contains carbon atoms derived from aromatic hydrocarbon groups in a predetermined proportion, and the active hydrogen group-containing polymer of the present invention contains the constituent unit represented by formula (1) and the constituent unit represented by formula (2) in a predetermined proportion.

[0037] Therefore, the above-mentioned active hydrogen group-containing polymer has a relatively low viscosity and excellent handling properties. Furthermore, using the above-mentioned active hydrogen group-containing polymer, it is possible to obtain resins and molded articles with relatively excellent mechanical properties.

[0038] The poly(thio)urethane resin and molded articles of the present invention are obtained using the above-mentioned active hydrogen group-containing polymer. Therefore, the poly(thio)urethane resin and molded articles have excellent productivity. Furthermore, the poly(thio)urethane resin and molded articles have relatively excellent mechanical properties.

[0039] According to the method for producing an active hydrogen group-containing polymer of the present invention, the above-mentioned active hydrogen group-containing polymer can be produced efficiently.

[0040] Embodiments of the present disclosure are described below. These descriptions and examples are illustrative of embodiments and do not limit the scope of embodiments. In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. In the present disclosure, numerical ranges expressed using "~" mean a range that includes the numbers before and after "~" as lower and upper limits. In the present disclosure, the term "process" is included not only in the sense of an independent process, but also in the sense that the purpose of the process is achieved even if it cannot be clearly distinguished from other processes. In numerical ranges described in stages in the present disclosure, the upper or lower limit stated in one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. In numerical ranges described in the present disclosure, the upper or lower limit of that numerical range may be replaced with the value shown in the examples. In the present disclosure, each component may contain multiple types of the corresponding substance. When the amount of each component in the composition is referred to in the present disclosure, if there are multiple types of the substance corresponding to each component in the composition, it means the total amount of those multiple types of substances present in the composition unless otherwise specified. In this disclosure, "mass%" and "weight%" are synonymous, and "parts by mass" and "parts by weight" are synonymous. In this disclosure, "%" indicating the amount of a component is on a mass basis unless otherwise specified. In this disclosure, the term "layer" includes cases where the layer is formed throughout the entire region when the region in which the layer exists is observed, as well as cases where it is formed only on a part of the region. In the notation of groups (atomic groups) in this disclosure, notations that do not specify substitution or unsubstituted include both those with and without substituents.

[0041] 1. Active Hydrogen Group-Containing Polymers Active hydrogen group-containing polymers are high molecular weight compounds having active hydrogen groups, represented by -XH, at their molecular ends. In -XH, H represents a hydrogen atom, and X represents -O-, -OC(=O)-, -C(=O)O-, -S-, -SC(=O)-, or -C(=O)S-. That is, the active hydrogen group (-XH) represents a hydroxyl group (-OH), a formyloxy group (-OC(=O)H), a carboxyl group (-C(=O)OH), a mercapto group (-SH), a formylthio group (-SC(=O)H), and / or a thiocarboxyl group (-C(=O)SH). Preferably, the active hydrogen group is a hydroxyl group.

[0042] The active hydrogen group-containing polymer comprises a first structural unit represented by the following formula (1) and a second structural unit represented by the following formula (2).

[0043]

[0044]

[0045] (In formulas (1) and (2), X represents -O-, -OC(=O)-, -C(=O)O-, -S-, -SC(=O)-, or -C(=O)S-, Y represents a hydrogen atom or a hydrocarbon group, R １ R indicates an aromatic hydrocarbon group. ３ R ２ , or CY ２ R １ CY ２ R ２ (This indicates a hydrocarbon group that may contain heteroatoms.)

[0046] In formulas (1) and (2), X represents -O-, -OC(=O)-, -C(=O)O-, -S-, -SC(=O)-, or -C(=O)S-. In formulas (1) and (2), X preferably represents -O-.

[0047] In formulas (1) and (2), Y represents a hydrogen atom or a hydrocarbon group, either identical or distinct from each other. Examples of hydrocarbon groups include monovalent hydrocarbon groups, preferably alkyl groups. Examples of alkyl groups include C1 to C20 alkyl groups, preferably C1 to C10 alkyl groups, and more preferably C1 to C4 alkyl groups. Examples of C1 to C4 alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, and t-butyl groups. A preferred example of a C1 to C4 hydrocarbon group is the methyl group.

[0048] From the viewpoint of productivity and handling, in formulas (1) and (2), preferably, all Y represent hydrogen atoms. That is, preferably, R １ CH ２ Combine.

[0049] In equations (1) and (2), R １ This indicates an aromatic hydrocarbon group. That is, the active hydrogen group-containing polymer has an aromatic hydrocarbon group. Examples of aromatic hydrocarbon groups include divalent aromatic hydrocarbon groups, and more specifically, divalent aromatic hydrocarbon groups having 6 to 30 carbon atoms. Examples of divalent aromatic hydrocarbon groups having 6 to 30 carbon atoms include the phenylene group represented by formula (a-1) below, the naphthalenediyl group represented by formula (a-2) below, the phenanthrenediyl group represented by formula (a-3) below, and the anthracenediyl group represented by formula (a-4) below. These can be used individually or in combination of two or more types.

[0050]

[0051] From the viewpoint of productivity and ease of handling, a phenylene group represented by the above formula (a-1) is preferred as the aromatic hydrocarbon group.

[0052] Examples of phenylene groups include 1,2-phenylene, 1,3-phenylene, and 1,4-phenylene groups. These can be used individually or in combination of two or more. That is, the phenylene group represents at least one selected from the group consisting of 1,2-phenylene, 1,3-phenylene, and 1,4-phenylene groups.

[0053] From the viewpoint of the mechanical properties of the poly(thio)urethane resin (described later) and the molded product (described later), a 1,4-phenylene group is preferred as the phenylene group.

[0054] In equations (1) and (2), R ３ R ２ , or CY ２ R １ CY ２ This indicates.

[0055] R ２ R represents a hydrocarbon group which may contain heteroatoms. In other words, R ２ Examples include hydrocarbon groups containing heteroatoms and hydrocarbon groups not containing heteroatoms. From the viewpoint of the mechanical properties of the molded article (described later), hydrocarbon groups containing heteroatoms are preferred. ２ The number of carbon atoms contained in is, from the viewpoint of mechanical properties, for example, 1 or more, preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. Also, R ２ The number of carbon atoms contained in is, for example, 120 or less, preferably 60 or less, more preferably 30 or less, and even more preferably 12 or less. That is, R ２ The number of carbon atoms contained is, for example, 1 to 120, preferably 2 to 60, more preferably 3 to 30, and even more preferably 4 to 12.

[0056] Examples of hydrocarbon groups that may contain heteroatoms include aliphatic hydrocarbon groups that may contain heteroatoms, alicyclic hydrocarbon groups that may contain heteroatoms, aromatic hydrocarbon groups that may contain heteroatoms, and aromatic aliphatic hydrocarbon groups that may contain heteroatoms.

[0057] From the viewpoint of balancing the mechanical properties of the poly(thio)urethane resin (described later) and molded articles (described later) with the viscosity of the active hydrogen group-containing polymer, aliphatic hydrocarbon groups which may contain heteroatoms are preferred. Also, from the viewpoint of the mechanical properties of the poly(thio)urethane resin (described later) and molded articles (described later), alicyclic hydrocarbon groups which may contain heteroatoms are preferred.

[0058] Examples of aliphatic hydrocarbon groups that may contain heteroatoms include divalent aliphatic hydrocarbon groups that may contain heteroatoms, more specifically, divalent aliphatic hydrocarbon groups having 1 to 120 carbon atoms that may contain heteroatoms, preferably divalent aliphatic hydrocarbon groups having 2 to 60 carbon atoms that may contain heteroatoms, more preferably divalent aliphatic hydrocarbon groups having 3 to 30 carbon atoms that may contain heteroatoms, and even more preferably divalent aliphatic hydrocarbon groups having 4 to 12 carbon atoms that may contain heteroatoms.

[0059] Examples of alicyclic hydrocarbon groups that may contain heteroatoms include divalent alicyclic hydrocarbon groups that may contain heteroatoms, and more specifically, divalent alicyclic hydrocarbon groups having 3 to 30 carbon atoms that may contain heteroatoms.

[0060] Examples of heteroatoms include nitrogen, sulfur, oxygen, phosphorus, silicon, and boron atoms. These can be used individually or in combination of two or more. Preferably, sulfur and oxygen atoms are used, and more preferably, oxygen atoms are used.

[0061] Hydrocarbon groups, which may contain heteroatoms, may optionally have known substituents. Examples of substituents include hydroxyl groups, mercapto groups, halogeno groups, cyano groups, amino groups, carboxyl groups, sulfonyl groups, and alkoxy groups. These may be used individually or in combination of two or more. The number of substituents may be set appropriately depending on the purpose and application. The substitution positions may be set appropriately depending on the purpose and application.

[0062] More specifically, examples of hydrocarbon groups that may contain heteroatoms include the hydrocarbon groups represented by the following formulas (b-1) to (b-22).

[0063]

[0064]

[0065]

[0066] These can be used individually or in combination of two or more types. From the viewpoint of the mechanical properties of the poly(thio)urethane resin (described later) and the molded article (described later), hydrocarbon groups represented by the above formulas (b-1) to (b-9) are preferred.

[0067] From the viewpoint of balancing the mechanical properties of the poly(thio)urethane resin (described later) and molded articles (described later) with the viscosity of the active hydrogen group-containing polymer, more preferably, a divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms, which may contain heteroatoms, is used. More preferably, the hydrocarbon group represented by formulas (b-1) to (b-5) is used, and even more preferably, the hydrocarbon group represented by formulas (b-2) and (b-4) to (b-5) is used. From the viewpoint of availability and ease of handling, the hydrocarbon group represented by formula (b-1) is particularly preferred.

[0068] Furthermore, from the viewpoint of obtaining an active hydrogen group-containing polymer having excellent heat resistance, and in particular from the viewpoint of obtaining a poly(thio)urethane resin (described later) and molded articles (described later) having excellent mechanical properties, more preferably, a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, which may contain heteroatoms, is preferred, more preferably, a hydrocarbon group represented by formulas (b-6) to (b-9) is preferred, more preferably, a hydrocarbon group represented by formulas (b-6) to (b-8) is preferred, and particularly preferably, a hydrocarbon group represented by formula (b-7) is preferred.

[0069] Furthermore, from the viewpoint of balancing the mechanical properties of the poly(thio)urethane resin (described later) and molded articles (described later) with the viscosity of the active hydrogen group-containing polymer, a combination of the hydrocarbon group represented by formula (b-1) and the hydrocarbon groups represented by formulas (b-3) to (b-8) is more preferable.

[0070] When the hydrocarbon group represented by formula (b-1) and the hydrocarbon groups represented by formulas (b-3) to (b-7) are used in combination, the content ratio of the hydrocarbon group represented by formula (b-1) relative to the total amount of these is, for example, 10% by mass or more and 90% by mass or less, preferably 20% by mass or more and 80% by mass or less, and more preferably 30% by mass or more and 70% by mass or less.

[0071] CY ２ R １ CY ２ This is a divalent hydrocarbon group represented by the following formula (5).

[0072]

[0073] CY ２ R １ CY ２ In this, Y has the same meaning as Y above. That is, Y represents a hydrogen atom or a hydrocarbon group. Preferably, Y represents a hydrogen atom.

[0074] CY ２ R １ CY ２ In R １ The above R １ This is synonymous with R. １ R represents the aromatic hydrocarbon group described above. １ Preferably, it represents a phenylene group, more preferably a 1,3-phenylene group and / or a 1,4-phenylene group, and even more preferably a 1,4-phenylene group.

[0075] R １ If it represents a phenylene group, CY ２ R １ CY ２ This represents a xylylene group. Examples of xylylene groups include 1,2-xylylene, 1,3-xylylene, and 1,4-xylylene groups. These can be used individually or in combination of two or more types. That is, the xylylene group represents at least one selected from the group consisting of 1,2-xylylene, 1,3-xylylene, and 1,4-xylylene groups.

[0076] R １ If it represents a phenylene group, CY ２ R １ CY ２ Preferably, it represents a 1,3-xylylene group and / or a 1,4-xylylene group, and more preferably, it represents a 1,4-xylylene group.

[0077] The first constituent unit shown in formula (1) above is R ３ Accordingly, it can be divided into a first a component unit shown by the following formula (1a) and a first b component unit shown by the following formula (1b).

[0078] More specifically, in equation (1) above, R ３ R ２ In this case, the first constituent unit shown in formula (1) above is the first a constituent unit shown in formula (1a) below.

[0079]

[0080] (In equation (1a), X, Y, R １ and R ２ These are X, Y, and R in equation (1). １ and R ２ (This is synonymous with...)

[0081] In formula (1a), X has the same meaning as above. That is, X represents -O-, -OC(=O)-, -C(=O)O-, -S-, -SC(=O)-, or -C(=O)S-. Preferably, X represents -O-.

[0082] In formula (1a), Y has the same meaning as Y described above. That is, Y represents a hydrogen atom or a hydrocarbon group. Preferably, Y represents a hydrogen atom.

[0083] In equation (1a), R １ The above R １ This is synonymous with R. １ R represents the aromatic hydrocarbon group described above. １ Preferably, it represents a phenylene group, more preferably a 1,3-phenylene group and / or a 1,4-phenylene group, and even more preferably a 1,4-phenylene group.

[0084] In equation (1a), R ２ The above R ２ This is synonymous with R. ２ R represents a hydrocarbon group which may contain a heteroatom. ２ Preferably, this represents an aliphatic hydrocarbon group which may contain a heteroatom, or an alicyclic hydrocarbon group which may contain a heteroatom.

[0085] In the above formula (1), R ３ cy ２ R １ CY ２ In this case, the first constituent unit shown in formula (1) above is the first b constituent unit shown in formula (1b) below.

[0086]

[0087] (In equation (1b), X, Y, R １ and R ２ These are X, Y, and R in equation (1). １ and R ２ (This is synonymous with...)

[0088] In formula (1b), X has the same meaning as above. That is, X represents -O-, -OC(=O)-, -C(=O)O-, -S-, -SC(=O)-, or -C(=O)S-. Preferably, X represents -O-.

[0089] In formula (1b), Y has the same meaning as Y described above. That is, Y represents a hydrogen atom or a hydrocarbon group. Y preferably represents a hydrogen atom.

[0090] In formula (1b), R １ has the same meaning as R １ described above. That is, R １ represents the aromatic hydrocarbon group described above. R １ preferably represents a phenylene group, more preferably represents a 1,3-phenylene group and / or a 1,4-phenylene group, and even more preferably represents a 1,4-phenylene group.

[0091] The first structural unit represented by the above formula (1) preferably contains the first a-structural unit represented by the above formula (1a) and the first b-structural unit represented by the above formula (1b). That is, the active hydrogen group-containing polymer preferably contains both the first a-structural unit and the first b-structural unit.

[0092] Hereinafter, the average number of the first structural units contained in the active hydrogen group-containing polymer is denoted as m. The average number of the first a-structural units contained in the active hydrogen group-containing polymer is denoted as ma. The average number of the first b-structural units contained in the active hydrogen group-containing polymer is denoted as mb. The average number m of the first structural units contained in the active hydrogen group-containing polymer is the sum of the average number ma of the first a-structural units contained in the active hydrogen group-containing polymer and the average number mb of the first b-structural units contained in the active hydrogen group-containing polymer.

[0093] In an active hydrogen group-containing polymer, the ratio of the average number of first a-constituent units (ma / m) to the average number of first constituent units (m) is, for example, 0.50 or more, preferably 0.75 or more. Furthermore, in an active hydrogen group-containing polymer, the ratio of the average number of first a-constituent units (ma / m) to the average number of first constituent units (m) is, for example, 1.00 or less, preferably 0.95 or less. That is, in an active hydrogen group-containing polymer, the ratio of the average number of first a-constituent units (ma / m) to the average number of first constituent units (m) is, for example, 0.50 or more and 1.00 or less, preferably 0.75 or more and 0.95 or less. Note that in an active hydrogen group-containing polymer, the ratio of the average number of first a-constituent units (ma / m) to the average number of first constituent units (m) is, for example, １ It can be calculated based on H-NMR (described later), the mixing ratio of the first raw material compound (described later) and the second raw material compound (described later), and the hydroxyl value of the active hydrogen group-containing polymer.

[0094] In the active hydrogen group-containing polymer, the ratio of the average number of first b-constituent units (mb) to the average number of first b-constituent units (m) (mb / m) is, for example, 0.00 or more, preferably 0.05 or more. Furthermore, in the active hydrogen group-containing polymer, the ratio of the average number of first b-constituent units (mb) to the average number of first b-constituent units (mb / m) to the average number of first b-constituent units (m) (mb / m) is, for example, 0.50 or less, preferably 0.25 or less. That is, in the active hydrogen group-containing polymer, the ratio of the average number of first b-constituent units (mb) to the average number of first b-constituent units (mb / m) to the average number of first b-constituent units (m) (mb / m) is, for example, １ It can be calculated based on H-NMR (described later), the mixing ratio of the first raw material compound (described later) and the second raw material compound (described later), and the hydroxyl value of the active hydrogen group-containing polymer.

[0095] The second constituent unit shown in formula (2) above is R ３According to the situation, it is divided into a second a structural unit represented by the following formula (2a) and a second b structural unit represented by the following formula (2b).

[0096] More specifically, in the above formula (2), R ３ is R ２ When showing, the second structural unit represented by the above formula (2) is a second a structural unit represented by the following formula (2a).

[0097]

[0098] (In formula (2a), X, Y, R １ and R ２ are the same as X, Y, R １ and R ２ in formula (1).)

[0099] In formula (2a), X has the same meaning as the above X. That is, X represents -O-, -OC(=O)-, -C(=O)O-, -S-, -SC(=O)-, or -C(=O)S-. X preferably represents -O-.

[0100] In formula (2a), Y has the same meaning as the above Y. That is, Y represents a hydrogen atom or a hydrocarbon group. Y preferably represents a hydrogen atom.

[0101] In formula (2a), R １ has the same meaning as the above R １ . That is, R １ represents the above aromatic hydrocarbon group. R １ preferably represents a phenylene group, more preferably represents a 1,3-phenylene group and / or a 1,4-phenylene group, and even more preferably represents a 1,4-phenylene group.

[0102] In formula (2a), R ２ has the same meaning as the above R ２ . That is, R ２ represents a hydrocarbon group which may contain a hetero atom. R ２ preferably represents an aliphatic hydrocarbon group which may contain a hetero atom. Also, R ２ preferably represents a cycloaliphatic hydrocarbon group which may contain a hetero atom.

[0103] In the above equation (2), R ３ cy ２ R １ CY ２ In this case, the second constituent unit shown in formula (2) above is the second b constituent unit shown in formula (2b) below.

[0104]

[0105] (In equation (2b), X, Y, R １ and R ２ These are X, Y, and R in equation (2). １ and R ２ (This is synonymous with...)

[0106] In formula (2b), X has the same meaning as above. That is, X represents -O-, -OC(=O)-, -C(=O)O-, -S-, -SC(=O)-, or -C(=O)S-. Preferably, X represents -O-.

[0107] In formula (2b), Y has the same meaning as Y above. That is, Y represents a hydrogen atom or a hydrocarbon group. Preferably, Y represents a hydrogen atom.

[0108] In equation (2b), R １ The above R １ This is synonymous with R. １ R represents the aromatic hydrocarbon group described above. １ Preferably, it represents a phenylene group, more preferably a 1,3-phenylene group and / or a 1,4-phenylene group, and even more preferably a 1,4-phenylene group.

[0109] The second structural unit represented by formula (2) above preferably includes the second a structural unit represented by formula (2a) above and the second b structural unit represented by formula (2b) above.

[0110] In the following, the number of second constituent units contained in the active hydrogen group-containing polymer is denoted as n. The number of second a constituent units contained in the active hydrogen group-containing polymer is denoted as na. The number of second b constituent units contained in the active hydrogen group-containing polymer is denoted as nb. The average number n of second constituent units contained in the active hydrogen group-containing polymer is the sum of the average number na of second a constituent units contained in the active hydrogen group-containing polymer and the average number nb of second b constituent units contained in the active hydrogen group-containing polymer.

[0111] In the active hydrogen group-containing polymer, the ratio of the average number of second a-component units (na / n) to the average number of second-component units (n) is not particularly limited and is set appropriately according to the purpose and application. Furthermore, in the active hydrogen group-containing polymer, the ratio of the average number of second b-component units (nb / n) to the average number of second-component units (n) is not particularly limited and is set appropriately according to the purpose and application.

[0112] From the viewpoint of relatively reducing the viscosity of the active hydrogen group-containing polymer and obtaining a resin (described later) and molded article (described later) having excellent mechanical properties (particularly tensile properties), the active hydrogen group-containing polymer contains a first constituent unit and a second constituent unit in a predetermined ratio.

[0113] More specifically, from the viewpoint of adjusting the crystallinity of the active hydrogen group-containing polymer to a moderately high level and obtaining a resin (described later) and molded article (described later) having excellent mechanical properties (particularly tensile properties), the ratio of the average number of second constituent units in the active hydrogen group-containing polymer [n / (n+m)] to the sum of the average number of first constituent units m and the average number of second constituent units n in the active hydrogen group-containing polymer is greater than 0, preferably 0.01 or more.

[0114] Furthermore, from the viewpoint of adjusting the crystallinity of the active hydrogen group-containing polymer to a moderately low level and relatively reducing viscosity, the ratio of the average number of second constituent units n contained in the active hydrogen group-containing polymer to the sum of the average number of first constituent units m and the average number of second constituent units n contained in the active hydrogen group-containing polymer [n / (n+m)] is less than 0.09, preferably 0.05 or less, more preferably 0.03 or less, and even more preferably 0.02 or less.

[0115] In other words, from the viewpoint of relatively reducing the viscosity of the active hydrogen group-containing polymer and obtaining a resin (described later) and molded article (described later) having excellent mechanical properties (particularly tensile properties), the ratio of the average number n of the second constituent units contained in the active hydrogen group-containing polymer to the sum of the average number m of the first constituent units contained in the active hydrogen group-containing polymer and the average number n of the second constituent units contained in the active hydrogen group-containing polymer [n / (n+m)] is greater than 0 and less than 0.09, preferably greater than 0 and 0.05 or less, more preferably 0.01 or more and 0.05 or less, even more preferably 0.01 or more and 0.03 or less, and particularly preferably 0.01 or more and 0.02 or less.

[0116] In other words, the ratio of the average number of first constituent units m contained in the active hydrogen group-containing polymer to the sum of the average number of second constituent units n contained in the active hydrogen group-containing polymer [m / (n+m)] is greater than 0.91 and less than 1.00, preferably 0.95 or more and less than 1.00, more preferably 0.95 or more and 0.99 or less, even more preferably 0.97 or more and 0.99 or less, and particularly preferably 0.98 or more and 0.99 or less.

[0117] Furthermore, the above [n / (n+m)] and [m / (n+m)] are determined in accordance with the embodiments described later. １ It is measured by H-NMR.

[0118] Furthermore, the above-mentioned active hydrogen group-containing polymer is hydrogenated and decomposed by known methods. More specifically, for example, when the above-mentioned active hydrogen group-containing polymer is brought into contact with hydrogen in the presence of a known decomposition catalyst (e.g., a palladium catalyst), the first constituent unit is decomposed to obtain a first decomposition compound represented by formula (3) below, and the second constituent unit is decomposed to obtain a second decomposition compound represented by formula (4) below.

[0119]

[0120]

[0121] (In equations (3) and (4), Y and R １ These are Y and R in equation (1). １ (This is synonymous with...)

[0122] In other words, the hydrogenation-based decomposition composition of the above-mentioned active hydrogen group-containing polymer contains a first decomposition compound represented by formula (3) and a second decomposition compound represented by formula (4).

[0123] Examples of the first decomposition compound represented by formula (3) above include o-xylene, m-xylene, p-xylene, and 1,3-diisopropylbenzene. These can be used individually or in combination of two or more. Preferably, p-xylene is used as the first decomposition compound.

[0124] Examples of the second decomposition compound represented by formula (4) above include 1,4-dimethyl-2-(4-methylbenzyl)benzene, 2,4-diisopropyl-1-(4-methylbenzyl)benzene, and 2,4-diisopropyl-1-(2-(3-isopropylphenyl)propan-2-yl)benzene. These can be used individually or in combination of two or more. Preferably, the first decomposition compound is 1,4-dimethyl-2-(4-methylbenzyl)benzene.

[0125] In the decomposition composition, the ratio of the number of moles N of the second decomposition compound to the total number of moles M of the first decomposition compound (i.e., the molar ratio) [N / (M+N)] is greater than 0 and less than 0.09, preferably greater than 0 and 0.05 or less, more preferably 0.01 or more and 0.05 or less, even more preferably 0.01 or more and 0.03 or less, and particularly preferably 0.01 or more and 0.02 or less.

[0126] In other words, the ratio of the number of moles M of the first decomposition compound to the total number of moles N of the second decomposition compound (i.e., the molar ratio) [M / (M+N)] is greater than 0.91 and less than 1.00, preferably 0.95 or more and less than 1.00, more preferably 0.95 or more and 0.99 or less, even more preferably 0.97 or more and 0.99 or less, and particularly preferably 0.98 or more and 0.99 or less.

[0127] Furthermore, the above [N / (M+N)] and [M / (M+N)] can be calculated by performing gel permeation chromatography (GPC) analysis on the decomposed composition in accordance with the examples described later.

[0128] More specifically, for example, a decomposition composition is produced by contacting the above-mentioned active hydrogen group-containing polymer with hydrogen in a known manner in the presence of a known decomposition catalyst (e.g., a palladium catalyst) and decomposing it. Next, the decomposition composition is analyzed by gel permeation chromatography (GPC) at a detection wavelength of 254 nm, for example, to obtain a chromatogram of the decomposition composition. Then, in the chromatogram of the decomposition composition, the ratio of the peak area of ​​the peak derived from the second decomposition compound (S2) to the sum of the peak areas of the peak derived from the first decomposition compound (S1) and the peak area of ​​the peak derived from the second decomposition compound (S2) (i.e., the peak area ratio) [S2 / (S1+S2)] is calculated.

[0129] On the other hand, this method creates a calibration curve that shows the relationship between the molar ratio of the first decomposition compound and the second decomposition compound, and the ratio of the peak area of ​​the peak derived from the first decomposition compound to the peak area of ​​the peak derived from the second decomposition compound (peak area ratio).

[0130] In this method, the peak area ratio [S2 / (S1+S2)] is converted to the molar ratio [N / (M+N)] based on the calibration curve described above.

[0131] Similarly, in the chromatogram of the decomposition composition, the ratio of the peak area (S1) of the peak derived from the first decomposition compound to the sum of the peak areas (S2) of the peak derived from the second decomposition compound (i.e., the peak area ratio) [S1 / (S1+S2)] is calculated.

[0132] In this method, the peak area ratio [S1 / (S1+S2)] is converted to the molar ratio [M / (M+N)] based on the calibration curve described above.

[0133] Based on the above, the above molar ratios [N / (M+N)] and [M / (M+N)] can be calculated from the peak area ratio [S2 / (S1+S2)] and the peak area ratio [S1 / (S1+S2)].

[0134] The peak derived from the first decomposition compound is assigned by known methods based on the molecular structure and molecular weight of the first decomposition compound. Similarly, the peak derived from the second decomposition compound is assigned by known methods based on the molecular structure and molecular weight of the second decomposition compound.

[0135] Furthermore, from the viewpoint of obtaining resins (described later) and molded articles (described later) having excellent mechanical properties (particularly tensile properties), the active hydrogen group-containing polymer contains aromatic hydrocarbon groups (preferably the above R １ It contains carbon atoms derived from ) in a predetermined proportion.

[0136] More specifically, from the viewpoint of adjusting the crystallinity of the active hydrogen group-containing polymer to a moderately high level and obtaining a resin (described later) and molded article (described later) having excellent mechanical properties (particularly tensile properties), the amount of aromatic hydrocarbon groups (preferably the above R) relative to the total mass of the active hydrogen group-containing polymer is adjusted. １ The carbon content derived from ) is 20% by mass or more, preferably 25% by mass or more.

[0137] Furthermore, from the viewpoint of relatively reducing the viscosity of the active hydrogen group-containing polymer, it is preferable to use aromatic hydrocarbon groups (preferably the above R １ The proportion of carbon atoms derived from ) is adjusted.

[0138] More specifically, from the viewpoint of adjusting the crystallinity of the active hydrogen group-containing polymer to a moderately low level and relatively reducing viscosity, the amount of aromatic hydrocarbon groups (preferably the above R) relative to the total mass of the active hydrogen group-containing polymer is １ The carbon content derived from ) is, for example, 55% by mass or less, preferably 50% by mass or less, and more preferably 45% by mass or less.

[0139] In other words, from the viewpoint of relatively reducing the viscosity of the active hydrogen group-containing polymer and obtaining a resin (described later) and molded article (described later) having excellent mechanical properties (especially tensile properties), the amount of aromatic hydrocarbon groups (R of formula (1) above) relative to the total mass of the active hydrogen group-containing polymer is determined. １ The carbon content derived from the ) is, for example, 20% by mass or more and 55% by mass or less, preferably 25% by mass or more and 50% by mass or less, and more preferably 25% by mass or more and 45% by mass or less. The carbon content derived from the aromatic hydrocarbon group is calculated in accordance with the examples described later.

[0140] The number-average molecular weight (standard polystyrene equivalent molecular weight measured by GPC) of the active hydrogen group-containing polymer is, for example, 500 or more, preferably 800 or more, and more preferably 1000 or more. Furthermore, the number-average molecular weight (standard polystyrene equivalent molecular weight measured by GPC) of the active hydrogen group-containing polymer is, for example, 50000 or less, preferably 10000 or less, more preferably 5000 or less, even more preferably 3000 or less, and particularly preferably 2000 or less. That is, the number-average molecular weight (standard polystyrene equivalent molecular weight measured by GPC) of the active hydrogen group-containing polymer is, for example, 500 to 50000, preferably 800 to 10000, more preferably 1000 to 5000, even more preferably 1000 to 3000, and particularly preferably 1000 to 2000. The number-average molecular weight of the active hydrogen group-containing polymer is measured according to the examples described later.

[0141] Furthermore, the average number of functional groups (average number of active hydrogen groups) of the active hydrogen group-containing polymer is, for example, 1.8 or more, preferably 2.0 or more, and more preferably 2.1 or more. Also, the average number of functional groups (average number of active hydrogen groups) of the active hydrogen group-containing polymer is, for example, 4.0 or less, preferably 3.0 or less, and more preferably 2.5 or less. That is, the average number of functional groups (average number of active hydrogen groups) of the active hydrogen group-containing polymer is, for example, 1.8 or more and 4.0 or less, preferably 2.0 or more and 3.0 or less, and more preferably 2.1 or more and 2.5 or less. Note that the average number of functional groups (average number of active hydrogen groups) of the active hydrogen group-containing polymer is measured in accordance with the examples described later.

[0142] Furthermore, when the active hydrogen group-containing polymer has a hydroxyl group as the active hydrogen group, the hydroxyl value of the active hydrogen group-containing polymer is, for example, 50 mg KOH / g or more, preferably 80 mg KOH / g or more, and more preferably 100 mg KOH / g or more. Furthermore, when the active hydrogen group-containing polymer has a hydroxyl group as the active hydrogen group, the hydroxyl value of the active hydrogen group-containing polymer is, for example, 300 mg KOH / g or less, preferably 200 mg KOH / g or less, more preferably 150 mg KOH / g or less, and even more preferably 120 mg KOH / g or less. In other words, when the active hydrogen group-containing polymer has a hydroxyl group as the active hydrogen group, the hydroxyl value of the active hydrogen group-containing polymer is, for example, 50 mg KOH / g or more and 300 mg KOH / g or less, preferably 80 mg KOH / g or more and 200 mg KOH / g or less, more preferably 100 mg KOH / g or more and 150 mg KOH / g or less, and even more preferably 100 mg KOH / g or more and 120 mg KOH / g or less. The hydroxyl value of the active hydrogen group-containing polymer is measured according to the examples described later.

[0143] These active hydrogen group-containing polymers can be used individually or in combination of two or more types.

[0144] In active hydrogen group-containing polymers, preferably, X in formulas (1) and (2) represents -O- and / or -S-. That is, the active hydrogen group-containing polymer preferably has an ether bond (-O-) and / or a thioether bond (-S-) in its molecule. Furthermore, the active hydrogen group-containing polymer preferably has a hydroxyl group (-OH) and / or a mercapto group (-SH) at its molecular terminus.

[0145] In active hydrogen group-containing polymers, more preferably, X in formulas (1) and (2) represents -O-. That is, the active hydrogen group-containing polymer more preferably has an ether bond (-O-) in its molecule. Furthermore, the active hydrogen group-containing polymer preferably has a hydroxyl group (-OH) at its molecular terminus. In other words, polyether polyols are more preferably used as active hydrogen group-containing polymers.

[0146] Furthermore, in the active hydrogen group-containing polymer, preferably R of formula (1) and formula (2) １ This represents a phenylene group. In other words, the active hydrogen group-containing polymer is preferably a polybenzyl polyether polyol.

[0147] Furthermore, the above-mentioned active hydrogen group-containing polymer contains carbon atoms derived from aromatic hydrocarbon groups in a predetermined proportion, and the active hydrogen group-containing polymer of the present invention contains the structural unit represented by formula (1) and the structural unit represented by formula (2) in a predetermined proportion.

[0148] Therefore, the above-mentioned active hydrogen group-containing polymer has a relatively low viscosity and excellent handling properties. Furthermore, using the above-mentioned active hydrogen group-containing polymer, it is possible to obtain resins (described later) and molded articles (described later) with relatively excellent mechanical properties.

[0149] 2. Method for producing active hydrogen group-containing polymers The above-mentioned active hydrogen group-containing polymer can be obtained, for example, by the reaction of a first raw material compound represented by the following formula (A) and a second raw material compound represented by the following formula (B). That is, the active hydrogen group-containing polymer is, for example, a reaction product of a first raw material compound represented by the following formula (A) and a second raw material compound represented by the following formula (B).

[0150]

[0151]

[0152] (In formulas (A) and (B), -XH represents -OH, -OC(=O)H, -C(=O)OH, -SH, -SC(=O)H, and / or -C(=O)SH, Y represents a hydrogen atom or a hydrocarbon group, and R １ R indicates an aromatic hydrocarbon group. ２ (This indicates a hydrocarbon group that may contain heteroatoms.)

[0153] [First raw material compound] In the above formula (A), -XH represents a hydroxyl group (-OH), a formyloxy group (-OC(=O)H), a carboxyl group (-C(=O)OH), a mercapto group (-SH), a formylthio group (-SC(=O)H), and / or a thiocarboxyl group (-C(=O)SH), preferably a hydroxyl group (-OH).

[0154] In the above formula (A), Y has the same meaning as Y above. That is, Y represents a hydrogen atom or a hydrocarbon group. Preferably, Y represents a hydrogen atom.

[0155] In the above formula (A), R １ The above R １ This is synonymous with R. １ R represents the aromatic hydrocarbon group described above. １ Preferably, it represents a phenylene group, more preferably a 1,3-phenylene group and / or a 1,4-phenylene group, and even more preferably a 1,4-phenylene group.

[0156] More specifically, examples of the first starting material compound include aromatic aliphatic diols.

[0157] As an aromatic aliphatic diol, for example, all of Y in the above formula (A) represent hydrogen atoms, and R １ Examples include compounds exhibiting a 1,4-phenylene group, and more specifically, 1,4-benzenedimethanol represented by the following formula (A-1).

[0158]

[0159] Furthermore, as an aromatic aliphatic diol, for example, all Y in the above formula (A) are methyl groups, and R １ Examples include compounds exhibiting a 1,3-phenylene group, and more specifically, α,α'-dihydroxy-1,3-diisopropylbenzene represented by the following formula (A-2).

[0160]

[0161] [Second raw material compound] In the above formula (B), -XH represents a hydroxyl group (-OH), a carboxyl group (-C(=O)OH), a mercapto group (-SH), and / or a thiocarboxyl group (-C(=O)SH), preferably a hydroxyl group (-OH).

[0162] In the above formula (B), R ２ The above R ２ This is synonymous with R. ２ R represents a hydrocarbon group which may contain a heteroatom. ２ Preferably, this represents an aliphatic hydrocarbon group which may contain a heteroatom, or an alicyclic hydrocarbon group which may contain a heteroatom.

[0163] More specifically, examples of the second raw material compound include diols which may contain heteroatoms, polyols which may contain heteroatoms and have a valentity of 3 or more, and polyols which may contain heteroatoms and contain the above substituents (hereinafter referred to as substituent-containing polyols).

[0164] Examples of diols that may contain heteroatoms include diethylene glycol represented by formula (B-1) below, tetraethylene glycol represented by formula (B-2) below, dipropylene glycol represented by formula (B-3) below, 1,6-hexanediol represented by formula (B-4) below, 1,10-decanediol represented by formula (B-5) below, 1,4-cyclohexanedimethanol represented by formula (B-6) below, and tricyclo(5.2.1.0) represented by formula (B-7) below. ２，６Examples include decanedimethanol, ethylene glycol represented by formula (B-8), polyethylene glycol represented by formula (B-9), polypropylene glycol represented by formula (B-10), neopentyl glycol represented by formula (B-11), isosorbide represented by formula (B-12), and bisphenol A represented by formula (B-13). These can be used individually or in combination of two or more.

[0165]

[0166] Examples of polyols with a valency of 3 or higher that may contain heteroatoms include glycerin represented by formula (B-14), trimethylolpropane represented by formula (B-15), and pentaerythritol represented by formula (B-16). These can be used individually or in combination of two or more.

[0167]

[0168] Examples of substituent-containing polyols that may contain heteroatoms include dimethylolpropionic acid represented by formula (B-17), dihydroxyacetone represented by formula (B-18), 2-butene-1,4-diol represented by formula (B-19), 1,4-butynediol represented by formula (B-20), 2,2'-thiodiethanol represented by formula (B-21), and 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol represented by formula (B-22). These can be used individually or in combination of two or more.

[0169]

[0170] These can be used individually or in combination of two or more types. From the viewpoint of the mechanical properties of the poly(thio)urethane resin (described later) and molded articles (described later), preferred are diols which may contain heteroatoms, and more preferably are hydrocarbon groups represented by the above formulas (B-1) to (B-9).

[0171] From the viewpoint of balancing the mechanical properties of the poly(thio)urethane resin (described later) and molded articles (described later) with the viscosity of the active hydrogen group-containing polymer, more preferably, diols that do not contain a carbon ring are used, even more preferably, diols represented by formulas (B-1) to (B-5) above are used, even more preferably, diols represented by formulas (B-2) and (B-4) to (B-5) above are used, and particularly preferably, diols represented by formula (B-2) above are used.

[0172] Furthermore, from the viewpoint of obtaining an active hydrogen group-containing polymer having excellent heat resistance, and from the viewpoint of obtaining a poly(thio)urethane resin (described later) and molded articles (described later) having particularly excellent mechanical properties, a diol containing a carbon ring is more preferably, more preferably, a diol represented by the above formulas (B-6) to (B-7) is preferred, and particularly preferably, a diol represented by the above formula (B-7) is preferred.

[0173] Furthermore, from the viewpoint of balancing the mechanical properties of the poly(thio)urethane resin (described later) and molded product (described later) with the viscosity of the active hydrogen group-containing polymer, a combination of the diol represented by formula (B-1) and the diols represented by formulas (B-3) to (B-7) is more preferable.

[0174] When the diol represented by formula (B-1) and the diols represented by formulas (B-3) to (B-7) are used in combination, the content ratio of the diol represented by formula (B-1) relative to the total amount of these is, for example, 10% by mass or more and 90% by mass or less, preferably 20% by mass or more and 80% by mass or less, and more preferably 30% by mass or more and 70% by mass or less.

[0175] The method for reacting the first raw material compound and the second raw material compound is not particularly limited and can be appropriately selected depending on the types of the first and second raw material compounds.

[0176] For example, if the active hydrogen group (-XH) in the first raw material compound is a hydroxyl group (-OH), and the active hydrogen group (-XH) in the second raw material compound is a hydroxyl group (-OH), then, for example, an active hydrogen group-containing polymer can be obtained by condensing the first and second raw material compounds.

[0177] More specifically, in this method, first, the first raw material compound and the second raw material compound are prepared (preparation step). Next, in this method, the first raw material compound and the second raw material compound are reacted in the presence of an acid catalyst (reaction step).

[0178] In this method, the mixing ratio of the first raw material compound and the second raw material compound is adjusted, for example, so that the ratio of the average number of the first constituent units [m / (n+m)] to the sum of the average number of the first constituent units m and the average number of the second constituent units in the active hydrogen group-containing polymer falls within the above range.

[0179] Furthermore, in this method, the mixing ratio of the first raw material compound and the second raw material compound is adjusted, for example, so that in the above-mentioned decomposition composition, the ratio of the number of moles N of the second decomposition compound to the sum of the number of moles M of the first decomposition compound and the number of moles N of the second decomposition compound [N / (M+N)] falls within the above range.

[0180] Furthermore, in this method, the mixing ratio of the first raw material compound and the second raw material compound is adjusted, for example, so that the content of carbon atoms derived from aromatic hydrocarbon groups falls within the above range.

[0181] More specifically, the amount of the first raw material compound is, for example, 10% by mass or more, preferably 20% by mass or more, and more preferably 30% by mass or more, relative to the total mass of the first and second raw material compounds. Also, the amount of the first raw material compound is, for example, 90% by mass or less, preferably 80% by mass or less, and more preferably 70% by mass or less, relative to the total mass of the first and second raw material compounds. That is, the amount of the first raw material compound is, for example, 10% by mass or more and 90% by mass or less, preferably 20% by mass or more and 80% by mass or less, and more preferably 30% by mass or more and 70% by mass or less, relative to the total mass of the first and second raw material compounds.

[0182] Furthermore, the amount of the second raw material compound relative to the total amount of the first raw material compound and the second raw material compound is, for example, 10% by mass or more, preferably 20% by mass or more, and more preferably 30% by mass or more. Also, the amount of the second raw material compound relative to the total amount of the first raw material compound and the second raw material compound is, for example, 90% by mass or less, preferably 80% by mass or less, and more preferably 70% by mass or less. That is, the amount of the second raw material compound relative to the total amount of the first raw material compound and the second raw material compound is, for example, 10% by mass or more and 90% by mass or less, preferably 20% by mass or more and 80% by mass or less, and more preferably 30% by mass or more and 70% by mass or less.

[0183] Furthermore, the amount of the second raw material compound is, for example, 10 parts by mass or more, preferably 25 parts by mass or more, and more preferably 40 parts by mass or more, per 100 parts by mass of the first raw material compound. Also, the amount of the second raw material compound is, for example, 900 parts by mass or less, preferably 400 parts by mass or less, and more preferably 250 parts by mass or less, per 100 parts by mass of the first raw material compound. That is, the amount of the second raw material compound is, for example, 10 parts by mass or more and 900 parts by mass or less, preferably 25 parts by mass or more and 400 parts by mass or less, and more preferably 40 parts by mass or more and 250 parts by mass or less, per 100 parts by mass of the first raw material compound.

[0184] Furthermore, the amount of the first raw material compound relative to the total moles of the first and second raw material compounds is, for example, 20 mol% or more, preferably 30 mol% or more, and more preferably 40 mol% or more. Also, the amount of the first raw material compound relative to the total moles of the first and second raw material compounds is, for example, 90 mol% or less, preferably 70 mol% or less, and more preferably 55 mol% or less. That is, the amount of the first raw material compound relative to the total moles of the first and second raw material compounds is, for example, 20 mol% or more and 90 mol% or less, preferably 30 mol% or more and 70 mol% or less, and more preferably 40 mol% or more and 55 mol% or less.

[0185] Furthermore, the amount of the second raw material compound relative to the total moles of the first and second raw material compounds is, for example, 10 mol% or more, preferably 30 mol% or more, and more preferably 45 mol% or more. Also, the amount of the second raw material compound relative to the total moles of the first and second raw material compounds is, for example, 80 mol% or less, preferably 70 mol% or less, and more preferably 60 mol% or less. That is, the amount of the second raw material compound relative to the total moles of the first and second raw material compounds is, for example, 10 mol% or more and 80 mol% or less, preferably 30 mol% or more and 70 mol% or less, and more preferably 45 mol% or more and 60 mol% or less.

[0186] Furthermore, the amount of the second raw material compound per mole of the first raw material compound is, for example, 0.1 moles or more, preferably 0.4 moles or more, and more preferably 0.8 moles or more. Also, the amount of the second raw material compound per mole of the first raw material compound is, for example, 4 moles or less, preferably 2.5 moles or less, and more preferably 1.5 moles or less. That is, the amount of the second raw material compound per mole of the first raw material compound is, for example, 0.1 moles or more and 4 moles or less, preferably 0.4 moles or more and 2.5 moles or less, and more preferably 0.8 moles or more and 1.5 moles or less.

[0187] In the above reaction step, the type of acid catalyst is appropriately selected within the range that yields the above-mentioned active hydrogen group-containing polymer. For example, examples of acid catalysts include sulfuric acid, hydrochloric acid, phosphoric acid, boric acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, and solid acids. Examples of solid acids include Nafion and sulfated zirconia. These can be used individually or in combination of two or more. Sulfuric acid is preferably used as the acid catalyst.

[0188] In the above reaction step, the amount of acid catalyst is appropriately selected within the range in which the above-mentioned active hydrogen group-containing polymer can be obtained. For example, the blending ratio of the acid catalyst is, for example, 0.01 to 10 parts by mass, preferably 0.1 to 1 part by mass, per 100 parts by mass of the total amount of the first raw material compound and the second raw material compound.

[0189] In the above reaction step, the reaction temperature is, for example, 60°C to 150°C, preferably 80°C to 130°C, more preferably 90°C to 120°C, and even more preferably 90°C to 110°C, from the viewpoint of balancing the mechanical properties of the poly(thio)urethane resin (described later) and the molded product (described later) with the viscosity of the active hydrogen group-containing polymer.

[0190] The reaction time is, for example, 1 to 100 hours, preferably 20 to 50 hours, from the viewpoint of balancing the mechanical properties of the poly(thio)urethane resin (described later) and the molded product (described later) with the viscosity of the active hydrogen group-containing polymer.

[0191] Furthermore, in the above reaction process, water produced as a by-product is removed by distillation as needed. The method of removing the water is not particularly limited, and known methods can be employed.

[0192] Furthermore, in the above reaction step, the reaction is stopped by adding water and a neutralizing agent to neutralize the acid catalyst. Examples of neutralizing agents include well-known bases. Examples of bases include potassium hydroxide, sodium hydroxide, and potassium carbonate, with potassium hydroxide being preferred. The amount and timing of addition of the neutralizing agent are set appropriately according to the purpose and application.

[0193] In the above reaction step, an active hydrogen group-containing polymer is produced as a reaction product by the reaction of the first raw material compound and the second raw material compound.

[0194] More specifically, in the above reaction step, the active hydrogen group (preferably -OH) of the first raw material compound and the active hydrogen group (preferably -OH) of the second raw material compound undergo a condensation reaction to form the first a constituent unit represented by formula (1a).

[0195] Furthermore, in the above reaction step, the active hydrogen group (preferably -OH) of the first raw material compound and the active hydrogen group (preferably -OH) of the first raw material compound undergo a condensation reaction to form the first b constituent unit represented by formula (1b).

[0196] Furthermore, in the above reaction step, the R of the first constituent unit a １ The first starting compound undergoes a Friedel-Crafts reaction, and the first a-constituent unit R １ The alkyl group of the first raw material compound is added to it. In other words, the R of the first a constituent unit. １ The first raw material compound crosslinks against it. As a result, the second a structural unit represented by the above formula (2a) is formed.

[0197] Furthermore, in the above reaction step, the R of the first b constituent unit １ The first starting compound undergoes a Friedel-Crafts reaction, and the first b constituent unit R １ In some cases, an alkyl group of the first raw material compound may be added to it. In such cases, the R of the first b constituent unit is １ In some cases, the first raw material compound may crosslink. As a result, the second b structural unit represented by the above formula (2b) may be formed.

[0198] In other words, in the above reaction step, a first a-component unit represented by formula (1a), a first b-component unit represented by formula (1b), and a second a-component unit represented by formula (2a) are formed, and optionally, a second b-component unit represented by formula (2b) is also formed. To put it another way, the active hydrogen group-containing polymer obtained in the above reaction step comprises, for example, a first a-component unit represented by formula (1a), a first b-component unit represented by formula (1b), and a second a-component unit represented by formula (2a), and optionally, a second b-component unit represented by formula (2b).

[0199] Furthermore, the above-described method for producing the active hydrogen group-containing polymer allows for the efficient production of the active hydrogen group-containing polymer.

[0200] Furthermore, the active hydrogen group-containing polymer obtained by the above method contains carbon atoms derived from aromatic hydrocarbon groups in a predetermined proportion, and the active hydrogen group-containing polymer of the present invention contains the constituent unit represented by formula (1) and the constituent unit represented by formula (2) in a predetermined proportion.

[0201] Therefore, the activated hydrogen group-containing polymer obtained by the above method has a relatively low viscosity and excellent handling properties. Furthermore, the activated hydrogen group-containing polymer obtained by the above method can be used to obtain resins and molded articles with relatively excellent mechanical properties.

[0202] As a result, the above-described active hydrogen group-containing polymer and its production method are suitably used in the production of resins and molded articles.

[0203] Examples of resins include poly(thio)urethane resin and polyester resin, with poly(thio)urethane resin being preferred.

[0204] In other words, the above-described active hydrogen group-containing polymer and its production method are preferably used in the production of poly(thio)urethane resin and its molded articles.

[0205] 3. Poly(thio)urethane resin The poly(thio)urethane resin is a polyurethane resin and / or a polythiourethane resin. The poly(thio)urethane resin contains a reaction product of an active hydrogen component and a polyisocyanate component. Preferably, the poly(thio)urethane resin consists of a reaction product of an active hydrogen component and a polyisocyanate component.

[0206] The active hydrogen component contains the above-mentioned active hydrogen group-containing polymer as an essential component. The active hydrogen component may also contain other active hydrogen group-containing compounds as optional components. Examples of other active hydrogen group-containing compounds include polyol compounds and polyamine compounds.

[0207] Examples of polyol compounds include high molecular weight polyols and low molecular weight polyols.

[0208] High molecular weight polyols are polyols having a relatively high molecular weight. The number-average molecular weight (molecular weight equivalent to standard polystyrene as measured by GPC) of high molecular weight polyols is, for example, greater than 400 and 20,000 or less, preferably 500 to 10,000, and more preferably 1,000 to 5,000. Examples of high molecular weight polyols include polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, and vinyl monomer-modified polyols. These can be used individually or in combination of two or more types.

[0209] Low molecular weight polyols are polyols having a relatively low molecular weight. The number-average molecular weight of low molecular weight polyols is, for example, 40 to 400, preferably 50 to 300. Examples of low molecular weight polyols include dihydric alcohols, trihydric alcohols, and tetrahydric or higher alcohols. Examples of dihydric alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, and dipropylene glycol. Examples of trihydric alcohols include glycerin and trimethylolpropane. Examples of tetrahydric or higher alcohols include pentaerythritol and diglycerin. Furthermore, low molecular weight polyols can also be polymers obtained by addition polymerization of alkylene (C2-C3) oxides to dihydric or trihydric alcohols so that the number average molecular weight is 400 or less. These can be used individually or in combination of two or more types.

[0210] Examples of polyamine compounds include aromatic polyamines, aromatic aliphatic polyamines, alicyclic polyamines, aliphatic polyamines, amino alcohols, polyoxyethylene group-containing polyamines, alkoxysilyl compounds having a primary amino group, alkoxysilyl compounds having a primary and a secondary amino group, hydrazines, and hydrazine derivatives. These can be used individually or in combination of two or more types.

[0211] Other active hydrogen group-containing compounds can be used alone or in combination of two or more types.

[0212] In the active hydrogen component, the content ratio of other active hydrogen group-containing compounds is set appropriately according to the purpose and application. For example, the content ratio of other active hydrogen group-containing compounds is, for example, 50% by mass or less, preferably 30% by mass or less, more preferably 10% by mass or less, and particularly preferably 0% by mass, relative to the total amount of the active hydrogen component.

[0213] In other words, the content of the active hydrogen group-containing polymer is, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass, relative to the total amount of active hydrogen components. That is, the active hydrogen components preferably consist of the active hydrogen group-containing polymer.

[0214] The polyisocyanate component contains, for example, a polyisocyanate compound, and preferably consists of a polyisocyanate compound. Examples of polyisocyanate compounds include industrially common polyisocyanate compounds. Examples of polyisocyanate compounds include linear aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and aromatic aliphatic polyisocyanates. Examples of linear aliphatic polyisocyanates include pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), and their derivatives. Examples of alicyclic polyisocyanates include isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI), 4,4'-methylenebis(cyclohexyl isocyanate) (hydrogenated diphenylmethane diisocyanate, H １２ MDI), bis(isocyanatomethyl)cyclohexane(hydrogenated xylylene diisocyanate, H ６Examples of aromatic polyisocyanates include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and their derivatives. Examples of aromatic aliphatic polyisocyanates include xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), and their derivatives. Examples of derivatives include polymers, isocyanurate modified compounds, allophanate modified compounds, polyol modified compounds, biuret modified compounds, urea modified compounds, oxadiazinetrione modified compounds, and carbodiimide modified compounds. Furthermore, examples of aromatic polyisocyanate derivatives include polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI, polynuclear-containing diphenylmethane diisocyanate (p-MDI)). These can be used alone or in combination of two or more types.

[0215] Preferably, the polyisocyanate compound is an aromatic polyisocyanate and its derivatives, more preferably an aromatic polyisocyanate derivative, and even more preferably polymethylene polyphenyl polyisocyanate.

[0216] The reaction method between the active hydrogen component and the polyisocyanate component is not particularly limited, and known methods can be employed. Examples of reaction methods include bulk polymerization and solution polymerization.

[0217] In bulk polymerization, for example, a polyisocyanate component and an active hydrogen component are mixed and reacted under a nitrogen atmosphere. In solution polymerization, for example, a polyisocyanate component and an active hydrogen component are mixed and reacted in the presence of an organic solvent. Examples of organic solvents include ketones, nitriles, alkyl esters, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, ethers, glycol ether esters, halogenated aliphatic hydrocarbons, and polar aprotons.

[0218] The ratio of the active hydrogen component to the polyisocyanate component is adjusted based on the equivalent ratio (NCO / active hydrogen group) of isocyanate groups in the polyisocyanate component to active hydrogen groups (preferably hydroxyl groups and / or mercapto groups) in the active hydrogen component. More specifically, the equivalent ratio (NCO / active hydrogen group) of isocyanate groups in the polyisocyanate component to active hydrogen groups (preferably hydroxyl groups and / or mercapto groups) in the active hydrogen component is, for example, 0.75 to 1.3, preferably 0.9 to 1.1.

[0219] Furthermore, when reacting active hydrogen components with polyisocyanate components industrially, a one-shot method is employed.

[0220] In the one-shot method, for example, the polyisocyanate component and the active hydrogen component are mixed together in the above proportions, reacted, and cured. The reaction temperature is, for example, 10 to 250°C, preferably 20 to 200°C. The reaction time is, for example, 5 minutes to 72 hours, preferably 4 to 24 hours. A poly(thio)urethane resin is obtained by the above reaction.

[0221] In the production of poly(thio)urethane resins, known (thio)urethane catalysts may be added as needed. Examples of (thio)urethane catalysts include amines and organometallic compounds (e.g., dibutyltin dilaurate (DBTDL)). These can be used individually or in combination of two or more. The blending ratio of the (thio)urethane catalysts is set appropriately according to the purpose and application.

[0222] Furthermore, in the manufacture of poly(thio)urethane resin, known additives may be added as needed. Examples of additives include plasticizers, anti-blocking agents, heat stabilizers, light stabilizers, antioxidants, mold release agents, pigments, dyes, lubricants, fillers, and hydrolysis inhibitors. These can be used individually or in combination of two or more. The amount and timing of additive addition are set appropriately according to the purpose and application. For example, additives may be added to the active hydrogen component in advance. Additives may also be added to the raw materials for the active hydrogen component. Additives may also be added together with the raw materials for the active hydrogen component during its manufacture. Additives may also be added during the purification of the active hydrogen component.

[0223] Furthermore, the above-mentioned poly(thio)urethane resin is obtained using the above-mentioned active hydrogen group-containing polymer. Therefore, the above-mentioned poly(thio)urethane resin has excellent productivity. Moreover, the above-mentioned poly(thio)urethane resin has relatively good mechanical properties.

[0224] 4. Molded article The molded article contains the above-mentioned poly(thio)urethane resin. Preferably, the molded article is made of the above-mentioned poly(thio)urethane resin.

[0225] The method for obtaining the molded article is not particularly limited, and known methods can be employed. Examples of methods for obtaining the molded article include casting, thermal compression molding, injection molding, extrusion molding, and spinning. Examples of shapes for the molded article include plate-like, fibrous, strand-like, film-like, sheet-like, pipe-like, bottle-like, hollow-like, box-like, and button-like shapes.

[0226] The molded article is preferably obtained by casting. Therefore, the molded article is preferably a cast polyurethane elastomer. A cast polyurethane elastomer is an article that has a predetermined shape according to its purpose and application.

[0227] The method for obtaining the molded body by casting is not particularly limited. For example, in the one-shot method, a mixture of a polyisocyanate component and an active hydrogen component is degassed, and then the resulting mixture is poured into a preheated mold and cured under the above conditions. As a result, a molded body containing poly(thio)urethane resin is obtained. After demolding, the molded body is aged as necessary.

[0228] The shape of the molded body is not particularly limited and includes, for example, pellet-like, plate-like, fibrous, strand-like, film-like, sheet-like, pipe-like, hollow, and box-like shapes.

[0229] The molded article is obtained using the above-mentioned active hydrogen group-containing polymer. Therefore, the molded article has excellent productivity. Furthermore, the molded article has relatively good mechanical properties.

[0230] Next, the present invention will be described based on synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples. Unless otherwise specified, "parts" and "%" are based on mass. Furthermore, specific numerical values ​​such as blending ratios (content), physical properties, and parameters used in the following description may be replaced with the corresponding upper limits (numerical values ​​defined as "less than or equal to" or "less than") or lower limits (numerical values ​​defined as "greater than or equal to" or "greater than") of the blending ratios (content), physical properties, and parameters described in the "Modes for Carrying Out the Invention" above.

[0231] [1] Measurement and Evaluation Methods Various physical properties were measured and evaluated by the following methods.

[0232] [1.1] Mass percentage of carbon atoms derived from aromatic hydrocarbon groups The mass percentage Y of carbon atoms derived from aromatic hydrocarbon groups was calculated using the following formula: Y (mass%) = (Mass of carbon atoms derived from aromatic hydrocarbon groups in the first and second raw material compounds × 100) / Mass of active hydrogen group-containing polymer

[0233] The mass of the active hydrogen group-containing polymer was calculated by subtracting the mass of the condensed water removed by distillation from the sum of the masses of the first raw material compound and the second raw material compound. However, in Comparative Example 3, the mass of the active hydrogen group-containing polymer was calculated by subtracting the mass of the hydrochloric acid removed by distillation from the mass of the potassium chloride produced.

[0234] [1.2] n / (n+m) of the active hydrogen group-containing polymer The n / (n+m) of the active hydrogen group-containing polymer is １ This was determined by 1H-NMR. １ The details of the H-NMR method are explained below.

[0235] <NMR Measurement> Under the following normal conditions, the active hydrogen group-containing polymer was measured. １ 1H-NMR measurements were performed. Apparatus: JNM-ECZ400S / L1 (400MHz), manufactured by JEOL Ltd. Solvent: Deuterated chloroform CDCl ３ (Sample concentration 4% by mass) Reference substances: Tetramethylsilane, chloroform

[0236] <Calculation Method> The peak observed at 4.0–4.1 ppm was assigned to originate from the methylene hydrogen in the diphenylmethane structure. The integral value of that peak was then calculated.

[0237] The peak observed in the 4.4–4.7 ppm range was attributed to the benzyl hydrogen of the benzyl ether and benzyl alcohol structures. The integral value of this peak was also calculated.

[0238] Then, [n / (n+m)] was calculated using the following formula: [n / (n+m)] = c / d

[0239] c: Integrated value of the peak originating from methylene hydrogen of the diphenylmethane structure observed at 4.0–4.1 ppm. d: Integrated value of the peak originating from benzyl hydrogen of the benzyl ether and benzyl alcohol structures observed at 4.4–4.7 ppm.

[0240] [1.3] N / (M+N) of decomposition compositions of active hydrogen group-containing polymers The N / (M+N) of decomposition compositions of active hydrogen group-containing polymers by hydrogenation was determined by GPC. The method for producing the decomposition composition and the method for calculating N / (M+N) by gel permeation chromatography (GPC) are described below.

[0241] <Method for producing the decomposition composition> In a 50 mL glass flask equipped with a three-way stopcock and a rotor, 5 g of an active hydrogen group-containing polymer, 0.5 g of palladium-supported carbon (product name: Pd / C, PE type (Pd 10% by mass), manufactured by NE Chemcat Co., Ltd.), and 5 g of ethanol (special grade (99.5%), manufactured by Junsei Chemical Co., Ltd.) were placed and mixed.

[0242] Next, a 2L balloon filled with hydrogen gas was connected to the three-way stopcock, creating a hydrogen atmosphere inside the flask. Then, the contents of the flask were stirred at room temperature for 24 hours to decompose the active hydrogen group-containing polymer with hydrogen, obtaining a decomposed composition.

[0243] Subsequently, the palladium-supported carbon was removed by filtration to obtain an ethanol solution of the decomposition composition.

[0244] <Method for Calculating N / (M+N) by GPC Method> The decomposed compositions were analyzed by gel permeation chromatography (GPC) under the following conditions, and chromatograms were obtained. Calibration curves for the first decomposed compound and the second decomposed compound were also created. Next, in the chromatogram, the ratio of the peak area of ​​the peak derived from the second decomposed compound (S2) to the sum of the peak areas of the peak derived from the first decomposed compound (S1) and the peak area of ​​the peak derived from the second decomposed compound (S2) [S2 / (S1+S2)] was calculated.

[0245] On the other hand, in the above GPC, a calibration curve was created showing the relationship between the molar ratio of the first decomposition compound and the second decomposition compound, and the ratio of the peak area of ​​the peak derived from the first decomposition compound to the peak area of ​​the peak derived from the second decomposition compound (peak area ratio).

[0246] The first decomposition compound and the second decomposition compound were identified by the following method. Specifically, in each example and comparative example, based on the molecular structure of the first raw material compound, R in formula (A) above was identified. １ And Y was identified. Next, R １ Based on Y, the molecular structure of the first decomposition compound represented by formula (3) and the molecular structure of the second decomposition compound represented by formula (4) were identified, respectively. Furthermore, the molecular weights of the first decomposition compound and the second decomposition compound were calculated based on their molecular structures.

[0247] Then, based on the calibration curve described above, the peak area ratio [S2 / (S1+S2)] was converted to the ratio of moles N of the second decomposition compound to the sum of moles M of the first decomposition compound and moles N of the second decomposition compound [N / (M+N)].

[0248] <GPC Measurement Conditions> THF Solvent Analyzer: HLC-8320GPC (Tosoh Corporation) Analysis Software: EcoSEC-WS (Tosoh Corporation) Column: TSKgel guardcolumn HXL-L + TSKgel G3000HXL + TSKgel G2000HXL + TSKgel G1000HXL (Tosoh Corporation) Solvent: THF (Tetrahydrofuran, Special Grade, Junsei Chemical Co., Ltd.) Flow Rate: 0.8 ml / min Standard Material: Polystyrene (TSKgel Standard Polystyrene, Tosoh Corporation) Measurement Temperature: 40℃

[0249] [1.4] Number-average molecular weight of active hydrogen group-containing polymers The number-average molecular weight of active hydrogen group-containing polymers was measured by gel permeation chromatography (GPC) under the following conditions. In this invention, the number-average molecular weight was determined by GPC measurement under the following measurement conditions and converted to standard polystyrene, with the highest frequency molecular weight being used.

[0250] THF solvent measuring instrument / analyzer: HLC-8320GPC (Tosoh Corporation) Analysis software: EcoSEC-WS (Tosoh Corporation) Column: TSKgel guardcolumn HXL-L + TSKgel G3000HXL + TSKgel G2000HXL + TSKgel G1000HXL (Tosoh Corporation) Solvent: THF (tetrahydrofuran, special grade, Junsei Chemical Co., Ltd.) Flow rate: 0.8 ml / min Standard substance: Polystyrene (TSKgel standard polystyrene, Tosoh Corporation) Measurement temperature: 40℃

[0251] [1.5] Hydroxyl value of active hydrogen group-containing polymers The hydroxyl value of active hydrogen group-containing polymers was determined by phthalation method in accordance with Method B of JIS K 1557-1 (2007).

[0252] [1.6] Average number of functional groups in active hydrogen group-containing polymers The average number of functional groups in active hydrogen group-containing polymers was calculated using the following formula: Average number of functional groups = Number average molecular weight × Hydroxyl value / (56.1 × 1000)

[0253] [1.7] Viscosity of Active Hydrogen Group-Containing Polymers The viscosity of active hydrogen group-containing polymers was measured using a cone-plate rotational viscometer in accordance with JIS K 1557-5 (2007).

[0254] [1.8] Pyrolysis Temperature The pyrolysis temperature of the active hydrogen group-containing polymer was measured using a differential thermogravimetric analyzer (product name: TG / DTA6200, autosampler: AST-2, manufactured by Seiko Instruments Corporation).

[0255] More specifically, 10.5 ± 0.5 mg of an active hydrogen group-containing polymer was filled into a platinum measuring container to obtain a measurement sample.

[0256] Next, the measurement sample was heated from 30°C to 400°C under conditions of an air gas flow rate of 200 mL / min and a heating rate of 10°C / min, and a TG / DTA curve was obtained.

[0257] Then, using the analysis software attached to the device, the temperature at which the active hydrogen group-containing polymer underwent a 10% weight reduction was calculated as the thermal decomposition temperature.

[0258] [1.9] Tensile Strength of Poly(thio)urethane In accordance with ISO 527, poly(thio)urethane was subjected to tensile testing, and stress / strain curves were obtained. The tensile strength was then determined based on the maximum stress observed first in the tensile test. The tensile elongation was also determined based on the maximum elongation. A JIS No. 3 dumbbell test specimen was used as the measurement sample.

[0259] [1.10] Balance Index 1 The balance between the tensile strength of the poly(thio)urethane and the viscosity of the active hydrogen group-containing polymer was evaluated based on the following Balance Index 1. A higher value of Balance Index 1 indicates that a relatively high tensile strength and a relatively low viscosity are achieved simultaneously.

[0260] Balance Index 1 [10 ９ [ / s] = Tensile strength of poly(thio)urethane (MPa) / Viscosity of active hydrogen group-containing polymer (mPa·s)

[0261] [1.11] Balance Index 2 The balance between the tensile elongation of the poly(thio)urethane and the viscosity of the active hydrogen group-containing polymer was evaluated based on the following Balance Index 2. A higher value of Balance Index 2 indicates that a relatively high tensile elongation and a relatively low viscosity are achieved simultaneously.

[0262] Balance Index 2 [10 / Pa·s] = Tensile elongation of poly(thio)urethane (%) / Viscosity of active hydrogen group-containing polymer (mPa·s)

[0263] [1.12] Tear strength of poly(thio)urethane The tear strength of poly(thio)urethane was measured in accordance with JIS K 7312 (1996). An angle-shaped test piece with a thickness of 2 mm was used as the measurement sample.

[0264] [1.13] Balance Index 3 The balance between the tear strength of the poly(thio)urethane and the viscosity of the activated hydrogen group-containing polymer was evaluated based on the following Balance Index 3. A higher value of Balance Index 3 indicates that a relatively high tear strength and a relatively low viscosity are achieved simultaneously.

[0265] Balance Index 3 [10 ５* m / s = Tear strength of poly(thio)urethane (N / cm) / Viscosity of active hydrogen group-containing polymer (mPa·s)

[0266] [2] Raw materials [2.1] First raw material compound (A-1) 1,4-benzenedimethanol, Tokyo Chemical Industry Co., Ltd.: Purity 99.0% or higher, in the above formula (A), R １ R represents a 1,4-phenylene group, -XH represents an -OH group, and Y represents a hydrogen atom. (A-2) α,α'-dihydroxy-1,3-diisopropylbenzene, Tokyo Chemical Industry Co., Ltd.: Purity 98.0% or higher, In the above formula (A), R １ R represents a 1,3-phenylene group, -XH represents an -OH group, and Y represents a methyl group. (A-3) Dichloroparaxylene, Tokyo Chemical Industry Co., Ltd.: Purity 98.0% or higher, In the above formula (A), R １ -XH represents a 1,4-phenylene group, -XH represents -Cl, and Y represents a hydrogen atom.

[0267] [2.2] Second raw material compound (B-1) Diethylene glycol, Fujifilm Wako Pure Chemical Industries, Ltd.: Wako Special Grade, in the above formula (B), R ２ R is the above formula (b-1), and -XH represents -OH. (B-2) Tetraethylene glycol, Fujifilm Wako Pure Chemical Industries: Wako Special Grade, in the above formula (B), R ２ R is the above formula (b-2), and -XH represents -OH. (B-3) Dipropylene glycol, ADEKA Corporation: Dipropylene glycol, in the above formula (B), ２ R is the above formula (b-3), and -XH represents -OH. (B-4) 1,6-Hexanediol, Fujifilm Wako Pure Chemical Industries: Wako Special Grade, In the above formula (B), R ２ R is shown in the above formula (b-4), and -XH represents -OH. (B-5) 1,10-decanediol, Tokyo Chemical Industry Co., Ltd.: Wako Special Grade, In the above formula (B), R ２ In the above formula (b-5), -XH represents -OH. (B-6) 1,4-cyclohexanedimethanol, Tokyo Chemical Industry Co., Ltd.: cis-,trans- mixture, purity 99.0% or higher, in the above formula (B), R ２ The above formula (b-6) is shown, and -XH represents -OH. (B-7) Tricyclo(5.2.1.0 ２，６) Decandimethanol, Tokyo Chemical Industry Co., Ltd.: Purity 90.0% or higher, in the above formula (B), R ２ R is the above formula (b-7), and -XH represents -OH. (B-8) Ethylene glycol, Fujifilm Wako Pure Chemical Industries: Reagent grade, In the above formula (B), R ２ R is the above formula (b-8), and -XH represents -OH. (B-9) Polyethylene glycol (PEG400), Fujifilm Wako Pure Chemical Industries: Wako Grade 1, In the above formula (B), R ２ The above formula (b-9) is where -XH represents -OH.

[0268] [3] Active hydrogen group-containing polymer [3.1] Production of active hydrogen group-containing polymer [3.1.1] Example 1 (Active hydrogen group-containing polymer 1) Active hydrogen group-containing polymer 1 was obtained by dehydration condensation reaction of the first raw material compound and the second raw material compound in the mass ratio shown in Table 1.

[0269] More specifically, 253.4 g of diethylene glycol (second starting compound, 2.39 mol), 300.0 g of 1,4-benzenedimethanol (first starting compound, 2.17 mol), and 4.15 g of sulfuric acid (catalyst, 0.04 mol) were charged into a 500 ml glass round-bottom separable flask equipped with a rectification column, stirrer, thermometer, and nitrogen inlet tube.

[0270] Next, the contents of the flask were heated and stirred at a reaction temperature of 110°C, and a dehydration condensation reaction was carried out for 40 hours under atmospheric pressure and a nitrogen stream, while distilling off the water. During the dehydration condensation reaction, 74 g of condensation water was distilled off.

[0271] Next, 14.4 g (0.80 mol) of water and 4.6 g (0.08 mol) of potassium hydroxide were added to the flask to neutralize the sulfuric acid catalyst and stop the reaction.

[0272] Next, the contents of the flask were heated and stirred at 110°C, and dehydrated under reduced pressure using a vacuum pump. Then, the neutralized salt was removed from the contents of the flask by filtration. As a result, diethylene glycol / 1,4-benzenedimethanol copolymer (hereinafter referred to as polybenzyl polyether polyol) was obtained as the active hydrogen group-containing polymer 1. The polybenzyl polyether polyol was a yellow, transparent liquid at room temperature.

[0273] [3.1.2] Example 2 (Active Hydrogen Group-Containing Polymer 2) The reaction temperature was changed to 80°C and the reaction time was changed to 300 hours. Except as above, the same method as in Example 1 was used to obtain diethylene glycol / 1,4-benzenedimethanol copolymer (hereinafter referred to as polybenzyl polyether polyol) as Active Hydrogen Group-Containing Polymer 2. In the dehydration condensation reaction, 74 g of condensation water was removed by distillation. The polybenzyl polyether polyol was a yellow, transparent liquid at room temperature.

[0274] [3.1.3] Example 3 (Active Hydrogen Group-Containing Polymer 3) The reaction temperature was changed to 130°C. Except as above, the same method as in Example 1 was used to obtain diethylene glycol / 1,4-benzenedimethanol copolymer (hereinafter referred to as polybenzyl polyol) as the active hydrogen group-containing polymer 3. In the dehydration condensation reaction, 74 g of condensation water was removed by distillation. The polybenzyl polyether polyol was a brown transparent liquid at room temperature.

[0275] [3.1.4] Example 4 (Active Hydrogen Group-Containing Polymer 4) 253.4 g (2.39 mol) of diethylene glycol was replaced with 330.1 g (1.70 mol) of tetraethylene glycol. The amount of 1,4-benzenedimethanol was also changed to 198.0 g (1.43 mol). Except as above, the same method as in Example 1 was used to obtain tetraethylene glycol / 1,4-benzenedimethanol copolymer (hereinafter referred to as polybenzyl polyether polyol) as active hydrogen group-containing polymer 4. In the dehydration condensation reaction, 48 g of condensation water was removed by distillation. The polybenzyl polyether polyol was a yellow, transparent liquid at room temperature.

[0276] [3.1.5] Example 5 (Active Hydrogen Group-Containing Polymer 5) The amount of diethylene glycol was changed to 247.5 g (2.33 mol). Also, 300.0 g (2.17 mol) of 1,4-benzenedimethanol was changed to 269.8 g (1.95 mol) of 1,4-benzenedimethanol and 42.2 g (0.22 mol) of α,α'-dihydroxy-1,3-diisopropylbenzene. Except as above, the same method as in Example 1 was used to obtain diethylene glycol / 1,4-benzenedimethanol / α,α'-dihydroxy-1,3-diisopropylbenzene copolymer (hereinafter referred to as polybenzyl polyether polyol) as the active hydrogen group-containing polymer 5. In the dehydration condensation reaction, 74 g of condensation water was removed by distillation. The polybenzyl polyether polyol was an orange transparent liquid at room temperature.

[0277] [3.1.6] Example 6 (Active Hydrogen Group-Containing Polymer 6) 253.4 g (2.39 mol) of diethylene glycol was replaced with 135.3 g (1.28 mol) of diethylene glycol and 135.3 g (1.01 mol) of dipropylene glycol. The reaction time was also changed to 70 hours. Except as above, the same method as in Example 1 was used to obtain diethylene glycol / dipropylene glycol / 1,4-benzenedimethanol copolymer (hereinafter referred to as polybenzyl polyether polyol) as active hydrogen group-containing polymer 6. In the dehydration condensation reaction, 71 g of condensation water was removed by distillation. The polybenzyl polyether polyol was a yellow transparent liquid at room temperature.

[0278] [3.1.7] Example 7 (Active Hydrogen Group-Containing Polymer 7) 253.4 g (2.39 mol) of diethylene glycol was replaced with 127.5 g (1.20 mol) of diethylene glycol and 127.5 g (1.08 mol) of 1,6-hexanediol. Except as above, the same method as in Example 1 was used to obtain diethylene glycol / 1,6-hexanediol / 1,4-benzenedimethanol copolymer (hereinafter referred to as polybenzyl polyether polyol) as the active hydrogen group-containing polymer 7. In the dehydration condensation reaction, 71 g of condensation water was removed by distillation. The polybenzyl polyether polyol was a yellowish-white turbid liquid at room temperature and a yellow transparent liquid at 80°C.

[0279] [3.1.8] Example 8 (Active Hydrogen Group-Containing Polymer 8) 253.4 g (2.39 mol) of diethylene glycol was replaced with 142.0 g (1.34 mol) of diethylene glycol and 142.0 g (0.81 mol) of 1,10-decanediol. The amount of 1,4-benzenedimethanol was also changed to 270.0 g (1.95 mol). Except as above, the same method as in Example 1 was used to obtain diethylene glycol / 1,10-decanediol / 1,4-benzenedimethanol copolymer (hereinafter referred to as polybenzyl polyether polyol) as the active hydrogen group-containing polymer 8. In the dehydration condensation reaction, 65 g of condensation water was removed by distillation. The polybenzyl polyether polyol was a yellowish-white turbid liquid at room temperature and a yellowish transparent liquid at 80°C.

[0280] [3.1.9] Example 9 (Active Hydrogen Group-Containing Polymer 9) 253.4 g (2.39 mol) of diethylene glycol was replaced with 131.0 g (1.23 mol) of diethylene glycol and 131.0 g (0.91 mol) of 1,4-cyclohexanedimethanol. The amount of 1,4-benzenedimethanol was also changed to 282.0 g (2.04 mol). Except as above, the same method as in Example 1 was used to obtain diethylene glycol / 1,4-cyclohexanedimethanol / 1,4-benzenedimethanol copolymer (hereinafter referred to as polybenzyl polyether polyol) as the active hydrogen group-containing polymer 9. In the dehydration condensation reaction, 68 g of condensation water was removed by distillation. The polybenzyl polyether polyol was a yellowish-white solid at room temperature and a yellow transparent liquid at 80°C.

[0281] [3.1.10] Example 10 (Active hydrogen group-containing polymer 10) 253.4 g (2.39 mol) of diethylene glycol was mixed with 145.8 g (1.37 mol) of diethylene glycol and tricyclo(5.2.1.0 ２，６The amount of decanedimethanol was changed to 145.8 g (0.74 mol). In addition, the amount of 1,4-benzenedimethanol was changed to 264.0 g (1.91 mol). Except as above, the same method as in Example 1 was used to obtain diethylene glycol / 1,4-cyclohexanedimethanol / 1,4-benzenedimethanol copolymer (hereinafter referred to as polybenzyl polyether polyol) as the active hydrogen group-containing polymer 10. In the dehydration condensation reaction, 64 g of condensation water was removed by distillation. The polybenzyl polyether polyol was a yellow, transparent liquid at room temperature.

[0282] [3.1.11] Example 11 (Active Hydrogen Group-Containing Polymer 11) Diethylene glycol 253.4 g (2.39 mol) was changed to ethylene glycol 199.3 g (3.21 mol). Also, the amount of 1,4-benzenedimethanol was changed to 360.0 g (2.61 mol). Except as above, the same method as in Example 1 was used to obtain ethylene glycol / 1,4-benzenedimethanol copolymer (hereinafter referred to as polybenzyl polyether polyol) as the active hydrogen group-containing polymer 11. In the dehydration condensation reaction, 88 g of condensation water was removed by distillation. The polybenzyl polyether polyol was a yellow transparent liquid at room temperature.

[0283] [3.1.12] Example 12 (Active Hydrogen Group-Containing Polymer 12) Diethylene glycol 253.4 g (2.39 mol) was changed to ethylene glycol 168.1 g (2.71 mol). Also, the amount of 1,4-benzenedimethanol was changed to 360.0 g (2.61 mol). Except as above, the same method as in Example 1 was used to obtain ethylene glycol / 1,4-benzenedimethanol copolymer (hereinafter referred to as polybenzyl polyether polyol) as the active hydrogen group-containing polymer 12. In the dehydration condensation reaction, the polybenzyl polyether polyol from which 87 g of condensation water was distilled off was a yellowish-white solid at room temperature and a yellow transparent liquid at 80°C.

[0284] [3.1.13] Example 13 (Active Hydrogen Group-Containing Polymer 13) 253.4 g (2.39 mol) of diethylene glycol was replaced with 301.7 g (1.55 mol) of tetraethylene glycol. The amount of 1,4-benzenedimethanol was also changed to 210.0 g (1.52 mol). Except as above, the same method as in Example 1 was used to obtain tetraethylene glycol / 1,4-benzenedimethanol copolymer (hereinafter referred to as polybenzyl polyether polyol) as the active hydrogen group-containing polymer 13. In the dehydration condensation reaction, 51 g of condensation water was removed by distillation. The polybenzyl polyether polyol was an orange transparent liquid at room temperature.

[0285] [3.1.14] Comparative Example 1 (Active Hydrogen Group-Containing Polymer 14) The reaction temperature was changed to 180°C. Except as above, diethylene glycol and 1,4-benzenedimethanol were reacted in the same manner as in Example 1 to obtain a diethylene glycol / 1,4-benzenedimethanol copolymer (hereinafter referred to as polybenzyl polyether polyol) as the active hydrogen group-containing polymer 14. However, at a reaction time of 2 hours, the viscosity of the polybenzyl polyether polyol increased significantly and gelled. Therefore, the reaction was stopped at a reaction time of 2 hours. In the dehydration condensation reaction, 74 g of condensation water was removed by distillation. Since this polybenzyl polyether polyol gelled, various analyses of the polybenzyl polyether polyol were not performed.

[0286] [3.1.15] Comparative Example 2 (Active Hydrogen Group-Containing Polymer 15) 253.4 g (2.39 mol) of diethylene glycol was replaced with 382.1 g (0.96 mol) of PEG-400 (polyethylene glycol, number average molecular weight 400). The amount of 1,4-benzenedimethanol was also changed to 120.0 g (0.87 mol). Except as above, the same method as in Example 1 was used to obtain PEG-400 / 1,4-benzenedimethanol copolymer (hereinafter referred to as polybenzyl polyether polyol) as the active hydrogen group-containing polymer 15. In the dehydration condensation reaction, 28 g of condensation water was removed by distillation. The polybenzyl polyether polyol was a yellow transparent liquid at room temperature.

[0287] [3.1.16] Comparative Example 3 (Active Hydrogen Group-Containing Polymer 16) Active hydrogen group-containing polymer 16 was obtained by the Williamson synthesis method.

[0288] Specifically, 134.0 g (1.26 mol) of diethylene glycol and 71.0 g (1.27 mol) of potassium hydroxide were charged into a 500 ml glass round-bottom separable flask equipped with a rectification column, stirrer, and thermometer. The contents of the flask were then stirred while being heated at a reaction temperature of 110°C, and dehydration was carried out under reduced pressure using a vacuum pump. In this way, the diethylene glycol was alcoholized (first time).

[0289] Next, 100 mL of tetrahydrofuran and 100 mL of toluene were added to the flask as solvents, and then 67 g (0.38 mol) of α,α'-dichloro-p-xylene was added. The contents of the flask were then heated and stirred at a reaction temperature of 80°C and reacted for 4 hours. The contents of the flask were then filtered to remove 56.0 g (0.75 mol) of potassium chloride salt as a by-product. The filtrate was then returned to the flask (first time), and then 35.5 g (0.63 mol) of potassium hydroxide was added to the flask.

[0290] Next, the contents of the flask were stirred while being heated at a reaction temperature of 110°C, and dehydrated under reduced pressure using a vacuum pump. This process further alkoxideized the diethylene glycol (for the second time).

[0291] Next, 100 mL of tetrahydrofuran and 100 mL of toluene were added to the flask as solvents, and then 67 g (0.38 mol) of α,α'-dichloro-p-xylene was added. The contents of the flask were then heated and stirred at a reaction temperature of 80°C and reacted for 4 hours. The contents of the flask were then filtered to remove 54.0 g (0.72 mol) of potassium chloride salt as a by-product. The filtrate was then returned to the flask (second time), and then 35.5 g (0.63 mol) of potassium hydroxide was added to the flask.

[0292] Next, the contents of the flask were stirred while being heated at a reaction temperature of 110°C, and dehydrated under reduced pressure using a vacuum pump. This process further alkoxideized the diethylene glycol (for the third time).

[0293] Next, 100 mL of tetrahydrofuran and 100 mL of toluene were added to the flask, and then 67 g (0.38 mol) of α,α'-dichloro-p-xylene was added. The contents of the flask were then heated and stirred at a reaction temperature of 80°C and reacted for 4 hours. The contents of the flask were then filtered to remove 54.0 g (0.72 mol) of potassium chloride salt as a by-product. The filtrate was then returned to the flask (third time).

[0294] Next, 1.3 g of adsorbent (product name KW-700, aluminum silicate, manufactured by Kyowa Chemical Industry Co., Ltd.) was added to the flask. Then, the contents of the flask were stirred while being heated at a reaction temperature of 110°C, and dehydration was carried out under reduced pressure using a vacuum pump. The solvent was then removed by distillation.

[0295] Next, the contents of the flask were filtered to remove the adsorbent. As described above, diethylene glycol and α,α'-dichloro-p-xylene were reacted using the Williamson synthesis method.

[0296] As a result, a reaction product of diethylene glycol and α,α'-dichloro-p-xylene (hereinafter referred to as polybenzyl polyether polyol) was obtained as the active hydrogen group-containing polymer 16. The polybenzyl polyether polyol was a slightly cloudy yellow liquid at room temperature.

[0297] [4] Polyurethane resin [4.1] Examples 14-26 and Comparative Examples 4-6 In accordance with the description in Table 2, 0.19 g (0.35 mmol) of an antioxidant (trade name Irganox 1076, manufactured by BASF Japan) was added to the active hydrogen group-containing polymers (i.e., polybenzyl polyether polyols) of Examples 1-13 and Comparative Examples 1-3 to obtain the active hydrogen component. In Comparative Example 1, the active hydrogen group-containing polymer gelled, and in Comparative Example 4, the active hydrogen component could not be obtained.

[0298] As the polyisocyanate component, we prepared Cosmonate M-200 (manufactured by Kinko Mitsui Chemicals, polyphenylmethane polyisocyanate, isocyanate group content = 31.2% by mass) as a polyisocyanate.

[0299] In the formulations shown in Table 2, the active hydrogen component, polyisocyanate component, and dibutyltin dilaurate (urethane catalyst, DBTDL, manufactured by Tokyo Chemical Industry Co., Ltd.) of each example and comparative example were placed in a 500 mL reaction vessel and mixed with a stirring blade for 1 minute.

[0300] Next, the contents of the reaction vessel were degassed under vacuum for 3 minutes. Then, the contents of the reaction vessel were poured into a mold measuring 2 mm x 120 mm x 320 mm and cured in an 80°C oven for 22 hours to obtain a 2 mm thick molded polyurethane resin product.

[0301]

[0302]

[0303] The above invention is provided as an illustrative embodiment of the present invention, but this is merely illustrative and should not be interpreted restrictively. Modifications of the present invention that are obvious to those skilled in the art are included in the claims described below.

[0304] The active hydrogen group-containing polymer of the present invention is suitably used in various industrial fields where active hydrogen groups are required.

Claims

1. An active hydrogen group-containing polymer having aromatic hydrocarbon groups, comprising a first structural unit represented by formula (1) and a second structural unit represented by formula (2), wherein the content ratio of carbon atoms derived from the aromatic hydrocarbon groups to the total mass of the active hydrogen group-containing polymer is 20% by mass or more, and the ratio of the average number n of the second structural units contained in the active hydrogen group-containing polymer to the sum of the average number m of the first structural units contained in the active hydrogen group-containing polymer and the average number n of the second structural units contained in the active hydrogen group-containing polymer [n / (n+m)] is greater than 0 and less than 0.

09. (In formulas (1) and (2), X represents -O-, -OC(=O)-, -C(=O)O-, -S-, -SC(=O)-, or -C(=O)S-, Y represents a hydrogen atom or a hydrocarbon group, R １ R indicates an aromatic hydrocarbon group. ３ R ２ , or CY ２ R １ CY ２ R ２ (This indicates a hydrocarbon group that may contain heteroatoms.) 2. An active hydrogen group-containing polymer having an aromatic hydrocarbon group, comprising a first structural unit represented by the formula (1) and a second structural unit represented by the formula (2), wherein the content ratio of the aromatic hydrocarbon group is 20% by mass or more based on the total mass of the active hydrogen group-containing polymer, and the decomposition composition obtained by hydrogenating the active hydrogen group-containing polymer comprises a first decomposition compound represented by the formula (3) and a second decomposition compound represented by the formula (4), and in the decomposition composition, the ratio [N / (M + N)] of the number of moles N of the second decomposition compound to the total of the number of moles M of the first decomposition compound and the number of moles N of the second decomposition compound is more than 0 and less than 0.

09. An active hydrogen group-containing polymer. (In the formula (1) and the formula (2), X represents -O-, -OC(=O)-, -C(=O)O-, -S-, -SC(=O)-, or -C(=O)S-, Y represents a hydrogen atom or a hydrocarbon group, and R １ represents an aromatic hydrocarbon group, and R ３ represents R ２ or CY ２ R １ CY ２ and R ２ represents a hydrocarbon group which may contain a hetero atom.) (In the formula (3) and the formula (4), Y and R １ have the same meanings as Y and R １ in the formula (1).) 3. The active hydrogen group-containing polymer according to claim 1, wherein the ratio of the average number of second constituent units n contained in the active hydrogen group-containing polymer to the sum of the average number of first constituent units m contained in the active hydrogen group-containing polymer and the average number of second constituent units n contained in the active hydrogen group-containing polymer [n / (n+m)] is greater than 0 and 0.05 or less.

4. The active hydrogen group-containing polymer according to claim 1 or 2, wherein the content ratio of carbon atoms derived from the aromatic hydrocarbon group is 20% by mass or more and 50% by mass or less with respect to the total mass of the active hydrogen group-containing polymer.

5. In equations (1) and (2), R １ The active hydrogen group-containing polymer according to claim 1 or 2, wherein the polymer exhibits a phenylene group, and the phenylene group exhibits at least one selected from the group consisting of a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group.

6. The active hydrogen group-containing polymer according to claim 1 or 2, wherein the first structural unit represented by formula (1) contains the first a structural unit represented by formula (1a) and the first b structural unit represented by formula (1b). (In equations (1a) and (1b), X, Y, R １ and R ２ These are X, Y, and R in equation (1). １ and R ２ (This is synonymous with...) 7. In equation (1a), R ２ The active hydrogen group-containing polymer according to claim 6, wherein the polymer exhibits an aliphatic hydrocarbon group which may contain a heteroatom.

8. In equation (1a), R ２ The active hydrogen group-containing polymer according to claim 6, wherein the polymer exhibits an alicyclic hydrocarbon group which may contain heteroatoms.

9. The active hydrogen group-containing polymer according to claim 1 or 2, wherein in formulas (1) and (2), X represents -O-, and the active hydrogen group-containing polymer is a polyether polyol.

10. The active hydrogen group-containing polymer according to claim 1 or 2, wherein in formulas (1) and (2), all Y represent hydrogen atoms.

11. The active hydrogen group-containing polymer according to claim 1 or 2, wherein the number average molecular weight is 500 or more and 50,000 or less.

12. A poly(thio)urethane resin containing a reaction product of an active hydrogen component containing an active hydrogen group-containing polymer according to claim 1 or 2 and a polyisocyanate component.

13. A molded article containing the poly(thio)urethane resin described in claim 12.

14. A method for producing an active hydrogen group-containing polymer, comprising: a preparation step of preparing a first raw material compound represented by formula (A) and a second raw material compound represented by formula (B); and a reaction step of reacting the first raw material compound and the second raw material compound at 60 to 140°C in the presence of an acid catalyst. (In formulas (A) and (B), -XH represents -OH, -OC(=O)H, -C(=O)OH, -SH, -SC(=O)H, and / or -C(=O)SH, Y represents a hydrogen atom or a hydrocarbon group, R １ R indicates an aromatic hydrocarbon group. ２ (This indicates a hydrocarbon group that may contain heteroatoms.)

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