Hydrogenated polymer compositions comprising hydrogenated conjugated diene modified polymers with boron-containing functional groups and methods thereof.

Abstract

A method is provided for manufacturing a boron-functionalized hydrogenated conjugated diene modified polymer that is suitable for modifying various materials, such as polar materials or dispersing inorganic materials, in high yield; a hydrogenated polymer composition comprising the boron-functionalized hydrogenated conjugated diene modified polymer, which combines high reactivity to various polar functional groups and good dispersibility in thermoplastic polymers, typically in vinyl alcohol polymers; and a method for manufacturing a hydrogenated polymer composition comprising the boron-functionalized hydrogenated conjugated diene modified polymer.

Description

Technical Field

[0001] This invention relates to hydrogenated polymer compositions comprising hydrogenated conjugated diene modified polymers having boron-containing functional groups and methods for manufacturing the same. Prior Technology

[0002] Methods for synthesizing polymers with various functional groups at the ends by anionic polymerization have been studied. For example, methods for introducing boron-containing functional groups, such as boronic acid groups, into the polymer ends have been explored, and it has been found that polymers with boron-containing boronic acid groups or borinic acid groups at the ends are resin modifiers such as compatibilizers for thermoplastic resins with hydroxyl groups on the side chains, such as ethylene-vinyl alcohol copolymers (see Patent Document 1). [Previous Technical Documents] [Patent Literature]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 7-25918 Summary of the Invention

[0004] [The problem the invention aims to solve]

[0005] Specifically, Patent Document 1 explores a method for reacting the ends of an anionic polymer having structural units derived from conjugated dienes (hereinafter also referred to as "conjugated diene units") with trimethyl borate, followed by hydrogenation (hereinafter also referred to as "hydrogenation") of at least a portion of the carbon-carbon double bonds contained in the conjugated diene units, to obtain a hydrogenated conjugated diene modified polymer with borate groups at the ends. However, according to the inventors' investigation, while the manufacturing method of Patent Document 1 can yield a hydrogenated conjugated diene modified polymer with borate groups at the ends, the reactivity of the borate ester is insufficient, resulting in the presence of many unmodified polymers without borate groups. Therefore, even when using the polymer obtained in Patent Document 1 for resin modification, the proportion of polymers with borate groups is small, and there are many polymers that cannot react with polymers with groups that are reactive with borate groups. This results in problems such as insufficient grafting efficiency, insufficient dispersion in the resin, and increased overflow components.

[0006] The present invention is made in view of the above-mentioned facts, and aims to provide: a method for manufacturing a polymer that can obtain a hydrogenated conjugated diene modified polymer having boron functional groups in high yield, the hydrogenated conjugated diene modified polymer having boron functional groups being suitable for modifying various materials such as polar materials or dispersing inorganic materials; and a hydrogenated polymer composition comprising the hydrogenated conjugated diene modified polymer having boron functional groups, and having high reactivity to various polar functional groups and excellent dispersibility in thermoplastic polymers, typically in vinyl alcohol polymers. [Methods used to solve problems]

[0007] Through dedicated research, the inventors discovered that in the step of manufacturing a hydrogenated conjugated diene modified polymer having boron-containing functional groups, functional group modification is achieved by using a specified anionic polymeric active-terminated polymer containing conjugated diene units and a boric acid compound satisfying specified parameters, thereby hydrogenating at least a portion of the carbon-carbon double bonds contained in the conjugated diene units. This allows for the high-yield production of the desired hydrogenated conjugated diene modified polymer. Furthermore, it was discovered that specific hydrogenated polymer compositions containing the specified hydrogenated conjugated conjugated diene modified polymer containing boronite groups and the specified hydrogenated conjugated conjugated diene modified polymer containing hypoboronic acid groups exhibit reactivity to polar functional groups and excellent dispersibility in thermoplastic polymers, typically in vinyl alcohol-based polymers, thus completing the present invention.

[0008] That is, the present invention provides the following [1] to [5]. [1] A method for manufacturing a hydrogenated polymer composition comprising a hydrogenated conjugated diene modified polymer having a boron-containing functional group, comprising: step (1), wherein a monomer containing a conjugated diene is anionicly polymerized in the presence of an active metal or an active metal compound capable of anionic polymerization to produce an active end polymer (Z); step (2), wherein the active end polymer (Z) obtained in step (1) is reacted with a boric acid compound to obtain an unhydrogenated conjugated diene modified polymer having a boron-containing functional group, wherein the boric acid compound has at least two partial structures represented by the following formula (I), and at least one of the Rs bonded to the oxygen atoms contained in the partial structure has a Taft's steric parameter Es value of -0.30 or less; step (3), wherein at least a portion of the carbon-carbon double bonds contained in the conjugated diene unit contained in the unhydrogenated conjugated diene modified polymer obtained in step (2) is hydrogenated. BOR (I) (In formula (I), B represents a boron atom, O represents an oxygen atom, and R represents an organic group.) [2] The method for manufacturing hydrogenated polymer composition as described in [1] involves adding the aforementioned boric acid compound to the active end polymer (Z) after mixing the aforementioned polar compound with the boric acid compound in step (2) to allow it to react. [3] A hydrogenated polymer composition comprising 65-99% by mass of a borate-based hydrogenated conjugated diene modified polymer (A) and 1-35% by mass of a hypoboronic acid-based hydrogenated conjugated diene modified polymer (B), wherein the borate-based hydrogenated conjugated diene modified polymer (A) is selected from hydrogenated conjugated diene modified polymers containing borate groups as shown in formula (II), hydrogenated conjugated diene modified polymers containing borate ester groups as shown in formula (III), and hydrogenated conjugated diene modified polymers containing borate ester groups as shown in formula (IV). The hydrogenated conjugated diene modified polymer (B) is selected from at least one of the group consisting of hydrogenated conjugated diene modified polymers containing borate groups as shown in formula (V) or (VI), hydrogenated conjugated diene modified polymers containing borate ester groups as shown in formula (VII) or (VIII), and hydrogenated conjugated diene modified polymers containing borate groups as shown in formula (IX) or (X).

[0009] (In the above formula, P1, P2, and P3 represent polymer chains containing hydrogenated conjugated diene units; R1 and R2 each independently represent hydrogen atoms or alkyl groups having 1 to 12 carbon atoms; at least one of R1 and R2 is an alkyl group having 1 to 12 carbon atoms, or R1 and R2 are bonded to form an alkyl chain having 2 to 24 carbon atoms; R3, R4, and R5 each independently represent hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, or polymer chains containing hydrogenated conjugated diene units; at least one of R3, R4, and R5 is an alkyl group having 1 to 12 carbon atoms, or a polymer chain containing hydrogenated conjugated diene units; or R3 and R4, R3 and R5, or R4 and R5 can also be bonded to form an alkyl chain having 2 to 24 carbon atoms, and R3, R4, and R5 can also be bonded to form an alkyl chain having 2 to 24 carbon atoms.) Five bonds are formed to create a trivalent saturated hydrocarbon chain with 3 to 36 carbon atoms. M represents one alkali metal or half an alkaline earth metal.

[0010] (In the above formula, P4, P5, P6, P7, P8, P9, P10, P11, and P12 represent polymer chains containing hydrogenated conjugated diene units; R6, R7, R8, and R9 each independently represent alkyl groups having 1 to 12 carbon atoms; R10 and R11 each independently represent hydrogen atoms or alkyl groups having 1 to 12 carbon atoms; at least one of R10 and R11 is an alkyl group having 1 to 12 carbon atoms, or R10 and R11 are bonded to form an alkyl chain having 2 to 24 carbon atoms; R12 represents an alkyl group having 1 to 12 carbon atoms; R13 and R14 each independently represent hydrogen atoms or alkyl groups having 1 to 12 carbon atoms; at least one of R13 and R14 is an alkyl group having 1 to 12 carbon atoms, or R13 and R14 are bonded to form an alkyl chain having 2 to 24 carbon atoms.) (14 bonds form alkyl chains with 2 to 24 carbon atoms, where M represents one alkali metal or half an alkaline earth metal.) [4] A resin composition comprising a vinyl alcohol polymer and a hydrogenated polymer composition as described in [3]. [5] The resin composition described in [4] is an ethylene-vinyl alcohol copolymer. [Effects of the Invention]

[0011] According to the present invention, a hydrogenated polymer composition and a method for manufacturing the hydrogenated polymer composition are provided. The hydrogenated polymer composition contains a hydrogenated conjugated diene modified polymer containing borate ester groups and a hydrogenated conjugated diene polymer containing borate ester groups, and has high reactivity to polar functional groups and excellent dispersibility in thermoplastic polymers, typically in vinyl alcohol polymers. Simple Explanation of the Diagram

[0012] none. Implementation

[0013] [The form in which the invention is carried out]

[0014] The present invention will now be described in detail. The hydrogenated polymer composition of the present invention comprises 65-99% by mass of a borate-based hydrogenated conjugated diene modified polymer (A) and 1-35% by mass of a hypoboronic acid-based hydrogenated conjugated diene modified polymer (B). The borate-based hydrogenated conjugated diene modified polymer (A) is selected from hydrogenated conjugated diene modified polymers containing borate groups as shown in Formula (II), hydrogenated conjugated diene modified polymers containing borate ester groups as shown in Formula (III), and hydrogenated conjugated diene modified polymers containing borate ester groups as shown in Formula (IV). At least one of the group consisting of hydrogenated conjugated diene modified polymers containing borate groups, wherein the borate-based hydrogenated conjugated diene modified polymer (B) is selected from at least one of the group consisting of hydrogenated conjugated diene modified polymers containing borate groups as shown in formula (V) or (VI), hydrogenated conjugated diene modified polymers containing borate ester groups as shown in formula (VII) or (VIII), and hydrogenated conjugated diene modified polymers containing borate groups as shown in formula (IX) or (X).

[0015] The hydrogenated conjugated diene modified polymer containing borate groups in this invention refers to the product shown in formula (II) below.

[0016]

[0017] In formula (II), P1 represents a polymer chain containing hydrogenated conjugated diene units.

[0018] The hydrogenated conjugated diene modified polymer containing borate ester groups in this invention refers to the product shown in formula (III) below.

[0019]

[0020] In formula (III), P2 represents a polymer chain containing a hydrogenated conjugated diene unit, R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, at least one of R1 and R2 is an alkyl group having 1 to 12 carbon atoms, or R1 and R2 are bonded together to form an alkyl chain having 2 to 24 carbon atoms. Of R1 and R2, at least one preferably has a Taft stereoparameter Es value of -0.30 or less, more preferably -3.00 to -0.30, and even more preferably -1.55 to -0.39. Furthermore, a preferred state is that both R1 and R2 satisfy the above-mentioned Es values. Of R1 and R2, at least one preferably is n-propyl, isopropyl, n-butyl, dibutyl, isobutyl, or cyclohexyl, more preferably isopropyl or n-butyl, and even more preferably isopropyl. Furthermore, it is preferred that all of R1 and R2 are n-propyl, isopropyl, n-butyl, dibutyl, isobutyl, or cyclohexyl, more preferably isopropyl or n-butyl, and even more preferably isopropyl. Moreover, the Taft stereoparameter Es value will be explained below in step (2) of the preferred manufacturing method of the hydrogenated polymer composition.

[0021] The hydrogenated conjugated diene modified polymer containing borate groups in this invention refers to the product shown in formula (IV) below.

[0022]

[0023] In formula (IV), P3 represents a polymer chain containing a hydrogenated conjugated diene unit, and R3, R4 and R5 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a polymer chain containing a hydrogenated conjugated diene unit. At least one of R3, R4 and R5 is an alkyl group having 1 to 12 carbon atoms, or a polymer chain containing a hydrogenated conjugated diene unit. Alternatively, R3 and R4, R3 and R5, or R4 and R5 can be bonded to form an alkyl chain having 2 to 24 carbon atoms, and R3, R4 and R5 can also be bonded to form a trivalent saturated hydrocarbon chain having 3 to 36 carbon atoms. Of R3, R4, and R5, at least one preferably has a Taft stereoparameter Es value of -0.30 or less, more preferably -3.00 to -0.30, and even more preferably -1.55 to -0.39. Furthermore, a preferred morphology is that all of R3, R4, and R5 satisfy the aforementioned Es value. Of R3, R4, and R5, at least one is preferably n-propyl, isopropyl, n-butyl, dibutyl, isobutyl, or cyclohexyl, more preferably isopropyl or n-butyl, and even more preferably isopropyl. Furthermore, it is preferred that all of R3, R4, and R5 are n-propyl, isopropyl, n-butyl, dibutyl, isobutyl, or cyclohexyl, more preferably isopropyl or n-butyl, and even more preferably isopropyl. M represents one alkali metal or half an alkaline earth metal, preferably lithium, sodium, or potassium, and more preferably lithium. Furthermore, one alkali metal in formula (IV) means that, relative to the monovalent anionic group shown in parentheses, the cation of the alkali metal is monovalent, thus representing one alkali metal corresponding to the valence of that anionic group. Similarly, half an alkaline earth metal in formula (IV) means that, relative to the monovalent anionic group shown in parentheses, the cation of the alkaline earth metal is divalent, thus representing half an alkaline earth metal corresponding to the valence of that anionic group.

[0024] The hydrogenated conjugated diene modified polymer containing a hypoboronic acid group in this invention refers to the product shown in formula (V) or formula (VI).

[0025]

[0026] In formula (V), P4 and P5 represent polymer chains containing hydrogenated conjugated diene units.

[0027]

[0028] In formula (VI), P6 represents a polymer chain containing a hydrogenated conjugated diene unit, and R6 represents an alkyl group having 1 to 12 carbon atoms. Preferably, R6 is methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, isobutyl, or cyclohexyl; more preferably, isopropyl or n-butyl; and even more preferably, isopropyl.

[0029] The hydrogenated conjugated diene modified polymer containing a borate ester group in this invention refers to the product shown in formula (VII) or formula (VIII) below.

[0030]

[0031] In formula (VII), P7 and P8 represent polymer chains containing hydrogenated conjugated diene units, and R7 represents an alkyl group having 1 to 12 carbon atoms. Preferably, R7 has a Taft stereoparameter Es value of -0.30 or less, more preferably -3.00 to -0.30, and even more preferably -1.55 to -0.39. Preferably, R7 is n-propyl, isopropyl, n-butyl, dibutyl, isobutyl, or cyclohexyl, more preferably isopropyl or n-butyl, and even more preferably isopropyl.

[0032]

[0033] In formula (VIII), P9 represents a polymer chain containing a hydrogenated conjugated diene unit, R8 is an alkyl group having 1 to 12 carbon atoms, and R9 is an alkyl group having 1 to 12 carbon atoms. Preferably, R9 has a Taft stereoparameter Es value of -0.30 or less, more preferably -3.00 to -0.30, and even more preferably -1.55. -0.39. R 9 is preferably n-propyl, isopropyl, n-butyl, dibutyl, isobutyl, or cyclohexyl, more preferably isopropyl or n-butyl, and even more preferably isopropyl. The aforementioned R 8 is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, isobutyl, or cyclohexyl, more preferably isopropyl or n-butyl, and even more preferably isopropyl.

[0034] Modified polymers refer to those represented by formula (IX) or formula (X) below.

[0035]

[0036] In formula (IX), P10 and P11 represent polymer chains containing hydrogenated conjugated diene units, R10 and R11 are each independently hydrogen atoms or alkyl groups having 1 to 12 carbon atoms, at least one of R10 and R11 is an alkyl group having 1 to 12 carbon atoms, or R10 and R11 are bonded together to form an alkyl chain having 2 to 24 carbon atoms, and M represents one alkali metal or 1 / 2 alkaline earth metal. Of R10 and R11, at least one preferably has a Taft stereoparameter Es value of -0.30 or less, more preferably -3.00 to -0.30, and even more preferably -1.55 to -0.39. Furthermore, a preferred morphology is that all of R10 and R11 satisfy the aforementioned Es values. Of R10 and R11, at least one preferably is n-propyl, isopropyl, n-butyl, dibutyl, isobutyl, or cyclohexyl, more preferably isopropyl or n-butyl, and even more preferably isopropyl. Furthermore, it is preferred that all of R10 and R11 are n-propyl, isopropyl, n-butyl, dibutyl, isobutyl, or cyclohexyl, more preferably isopropyl or n-butyl, and even more preferably isopropyl. M is one alkali metal or half an alkaline earth metal, preferably lithium, sodium, or potassium, and even more preferably lithium.

[0037]

[0038] In formula (X), P12 represents a polymer chain containing a hydrogenated conjugated diene unit, R12 represents an alkyl group having 1 to 12 carbon atoms, R13 and R14 are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, at least one of R13 and R14 is an alkyl group having 1 to 12 carbon atoms, or R13 and R14 are bonded together to form an alkyl chain having 2 to 24 carbon atoms, and M represents one alkali metal or 1 / 2 alkaline earth metal. Of R13 and R14 mentioned above, at least one preferably has a Taft stereo parameter Es value of -0.30 or less, more preferably -3.00 to -0.30, and even more preferably -1.55 to -0.39. Furthermore, a preferred morphology is that all of R13 and R14 satisfy the aforementioned Es value. Of R13 and R14, at least one preferably is n-propyl, isopropyl, n-butyl, dibutyl, isobutyl, or cyclohexyl, more preferably isopropyl or n-butyl, and even more preferably isopropyl. Furthermore, it is preferred that all of R13 and R14 are n-propyl, isopropyl, n-butyl, dibutyl, isobutyl, or cyclohexyl, more preferably isopropyl or n-butyl, and even more preferably isopropyl. R 12 is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, isobutyl, or cyclohexyl, more preferably isopropyl or n-butyl, and even more preferably isopropyl. M is preferably lithium, sodium, or potassium, and more preferably lithium.

[0039] In the above formulas (II) to (X), as described above, there are polymer chains containing hydrogenated conjugated diene units represented by P1 to P12.

[0040] The hydrogenated conjugated diene units contained in P1 to P12 can be obtained by polymerizing conjugated dienes to obtain polymer chains containing conjugated diene units, followed by hydrogenation (hydrogenation) of the carbon-carbon double bonds of the conjugated diene units contained in the polymer chains. Examples of such conjugated dienes include butadiene, isoprene, 2,3-dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octtriene, laurylene, mycochlorobenzene, and chloroprene. Among these conjugated dienes, butadiene and isoprene are preferred, and butadiene is even more preferred. One of the above-mentioned conjugated dienes can be used alone, or two or more can be used in combination. Details regarding hydrogenation are described below in the manufacturing method section.

[0041] P1 to P12 may also include non-hydrogenated conjugated diene units other than hydrogenated conjugated diene units, and structural units derived from other monomers. A preferred form of structural unit derived from other monomers is a structural unit derived from aromatic vinyl compounds (hereinafter also referred to as "aromatic vinyl compound unit"). Examples of aromatic vinyl compounds that can be included as aromatic vinyl compound units in P1 to P12 include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-tributylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, vinyl anthracene, N,N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, and divinylbenzene. Among these aromatic vinyl compounds, styrene, α-methylstyrene, and 4-methylstyrene are preferred. One of the aromatic vinyl compounds that constitutes the above-mentioned aromatic vinyl compound units may be used alone, or two or more may be used in combination.

[0042] A preferred embodiment is that, of all monomer units constituting polymer chain P1 to P12, at least 30% by mass are unhydrogenated conjugated diene units derived from at least one conjugated diene selected from the group consisting of butadiene and isoprene, or hydrogenated conjugated diene units obtained by hydrogenating such conjugated diene units. The total content of conjugated diene units derived from at least one monomer selected from the group consisting of butadiene and isoprene, and the hydrogenated conjugated diene units of such conjugated diene, is preferably 30 to 100% by mass relative to all monomer units of polymer chain P1 to P12, more preferably 40 to 100% by mass, further preferably 50 to 100% by mass, even more preferably 60 to 100% by mass, and particularly preferably 70 to 100% by mass.

[0043] The content of monomer units other than unhydrogenated conjugated diene units and hydrogenated conjugated diene units of at least one conjugated diene selected from the group consisting of butadiene and isoprene, which constitutes polymer chain P1 to P12, is preferably 70% by mass or less, and more preferably 60% by mass or less.

[0044] Regarding polymer chains P1 to P12, examples include polymer chains formed by hydrogenating at least a portion of the carbon-carbon double bonds contained in the conjugated diene units of a single polymer chain or copolymer chain (random copolymer chain, block copolymer chain) of at least one conjugated diene or a copolymer chain (random copolymer chain, block copolymer chain) of a conjugated diene and a monomer other than the conjugated diene.

[0045] Preferably, the weight-average molecular weight (Mw) of polymer chains P1 to P12 is 1,000 to 1,000,000, more preferably 2,000 to 500,000, and even more preferably 3,000 to 100,000. Furthermore, the weight-average molecular weight (Mw) of the hydrogenated polymer composition of the present invention is also preferably within the above range. If the Mw of the polymer chains is within the aforementioned range, the manufacturing process has excellent permeability and tends to be economical. Moreover, in the present invention, unless otherwise specified, Mw is the weight-average molecular weight converted from standard polystyrene obtained by gel permeation chromatography (GPC).

[0046] The molecular weight distribution (Mw / Mn) of polymer chains P1 to P12 is preferably 1.0 to 20.0, more preferably 1.0 to 10.0, further preferably 1.0 to 5.0, even more preferably 1.0 to 2.0, particularly preferably 1.0 to 1.5, and even more preferably 1.0 to 1.2. Since the viscosity deviation of the obtained hydrogenated conjugated diene modified polymer is smaller when Mw / Mn is within the aforementioned range, it is preferable. Furthermore, the molecular weight distribution (Mw / Mn) of the hydrogenated polymer composition of the present invention is preferably within the above range, considering the point where the viscosity deviation is smaller. Moreover, in the present invention, Mn refers to the number average molecular weight, which is the number average molecular weight converted from standard polystyrene obtained by GPC measurement. Furthermore, molecular weight distribution (Mw / Mn) refers to the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of standard polystyrene obtained by GPC determination (Mw / Mn).

[0047] The vinyl content of polymer chains P1 to P12 is not particularly limited, but is 0.01 to 90 mol%, more preferably 0.1 to 80 mol%, and even more preferably 1 to 80 mol%. Furthermore, the vinyl content of the hydrogenated polymer composition of the present invention is also preferably within the above range. In the present invention, "vinyl content" means the total mol of conjugated diene units (other than 1,4-bonded and 1,13-bonded) of 100 mol% of the total conjugated diene units contained in the polymer chain or polymer before hydrogenation. The vinyl content was calculated using 1H-NMR by the ratio of the peak area of ​​the conjugated diene unit bonded by 1,2-, 3,4- (other than mycochloroene), and 3,13- (in the case of mycochloroene) to the peak area of ​​the conjugated diene unit bonded by 1,4- (other than mycochloroene) and 1,13- (in the case of mycochloroene).

[0048] The vinyl content of the polymer chains P1 to P12 can be designed according to the purpose. For example, if the vinyl content is less than 70 mol%, the glass transition temperature (Tg) of the polymer becomes lower, and the resulting hydrogenated polymer composition tends to have excellent flowability or low-temperature properties. In embodiments where the flowability and / or low-temperature properties of the resulting hydrogenated polymer composition are of particular importance, the vinyl content of the polymer chains P1 to P12 is preferably 1 to 60 mol%, more preferably 2 to 55 mol%, and even more preferably 3 to 50 mol%. Furthermore, the hydrogenated polymer composition of the present invention can be mixed with other polymers (β) other than the aforementioned hydrogenated polymer composition for use (details to follow), but in this case, the other polymer (β) is preferably a thermoplastic polymer (β1). As for the aforementioned (β1), for example in the case of a polymer containing vinyl alcohol and polypropylene, from the viewpoint of improving the dispersibility of the hydrogenated polymer composition with such thermoplastic polymers (β1), the vinyl content of the polymer chains P1 to P12 is preferably 45 to 90 mol%, more preferably 50 to 85 mol%, and even more preferably 55 to 80 mol.

[0049] Furthermore, the aforementioned vinyl content, for example in the case of manufacturing the hydrogenated polymer composition of the present invention by the method described later, can be made to the desired value by controlling the type of solvent used in step (1), the polar compound used as needed, the polymerization temperature, etc.

[0050] The glass transition temperature (Tg) of polymer chains P1 to P12 varies depending on the vinyl content of hydrogenated butadiene units, hydrogenated isoprene units, and hydrogenated conjugated diene units other than hydrogenated butadiene units and isoprene units, the type of hydrogenated conjugated diene units, and the content of structural units derived from monomers other than hydrogenated diene units, etc., but is preferably -150~50°C, more preferably -130~50°C, and even more preferably -130~30°C. If Tg is within the above range, for example, it is possible to suppress the increase in viscosity and make operation easier. Furthermore, the glass transition temperature (Tg) of the polymer composition of the present invention is preferably within the above range from the point of ease of operation. Moreover, in the present invention, Tg is the value of the peak of the DDSC (differential curve of DSC) obtained by differential scanning calorimetry (DSC).

[0051] The hydrogenated polymer composition of the present invention is characterized by comprising, relative to the total mass of all polymers contained in the composition, 65-99% by mass of a borate-based hydrogenated conjugated diene modified polymer (A) and 1-35% by mass of a hypoboronic acid-based hydrogenated conjugated diene modified polymer (B), wherein the borate-based hydrogenated conjugated diene modified polymer (A) is selected from hydrogenated conjugated diene modified polymers containing borate groups as shown in formula (II) above, and hydrogenated conjugated diene modified polymers containing borate ester groups as shown in formula (III) above. The hydrogenated conjugated diene modified polymer (B) is selected from at least one of the group consisting of hydrogenated conjugated diene modified polymers containing borate groups as shown in formula (V) or (VI), hydrogenated conjugated diene modified polymers containing borate ester groups as shown in formula (VII) or (VIII), and hydrogenated conjugated diene modified polymers containing borate groups as shown in formula (IX) or (X). The hydrogenated polymer composition of the present invention comprises, in the above proportions, a boronoid-based hydrogenated conjugated diene modified polymer (A) and a boronoid-based hydrogenated conjugated diene modified polymer (B), thereby improving the reactivity to polar functional groups and the dispersibility in thermoplastic polymers, typically in vinyl alcohol polymers.

[0052] Furthermore, the hydrogenated polymer composition of the present invention typically refers to a mixture of a polymer modified by a boron-containing functional group and an unmodified polymer that is not modified even if modified by this functional group. Therefore, a preferred form of the hydrogenated polymer composition of the present invention comprises only a mixture of a polymer modified by a boron-containing functional group and an unmodified polymer that is not modified even if modified by the functional group.

[0053] The contents of boronoid-based hydrogenated conjugated diene modified polymer (A) and boronoid-based hydrogenated conjugated diene modified polymer (B) in the hydrogenated polymer composition can be determined from the boron concentration and 11B-NMR spectrum of the hydrogenated polymer composition. The boron concentration can be determined by ICP atomic emission spectrometry, and the contents of (A) and (B) can be calculated from the area ratio of the signals in the 11B-NMR spectrum. Furthermore, in the case where the hydrogenated polymer composition is obtained using borate ester compounds, since the molecular weight of (B) becomes larger than that of (A), the contents of (A) and (B) can also be calculated from the area ratio of the GPC chart. In cases of low peak resolution, the peaks are separated, and the area ratio is calculated using a Gaussian peak distribution.

[0054] In thermoplastic polymers, typically, from the viewpoint of further improving the dispersibility in vinyl alcohol-based polymers, the preferred content ratio of the boronite-based hydrogenated conjugated diene modified polymer (A) and the hypoboronic acid-based hydrogenated conjugated diene modified polymer (B) in the hydrogenated polymer composition of the present invention is 65-99% by mass of the boronite-based hydrogenated conjugated diene modified polymer (A) and 1-35% by mass of the hypoboronic acid-based hydrogenated conjugated diene modified polymer (B), more preferably 80-99% by mass of the boronite-based hydrogenated conjugated diene modified polymer (A) and 1-20% by mass of the hypoboronic acid-based hydrogenated polymer (B).

[0055] The proportions of the borate-based hydrogenated conjugated diene modified polymer (A) and the borate-based hydrogenated conjugated diene modified polymer (B) in the hydrogenated polymer composition of the present invention can be controlled, for example, in the manufacturing method of the hydrogenated conjugated diene modified polymer described later, by means of Taft's stereoparameter Es value, reaction temperature, amount of polar compound, etc.

[0056] The Mw of the borate-based hydrogenated conjugated diene modified polymer (A) is preferably above 2,000 and below 200,000, and more preferably above 4,000 and below 100,000. The Mw of the hypoboronic acid-based hydrogenated conjugated diene modified polymer (B) is preferably 4,000 to 400,000, and more preferably 8,000 to 200,000.

[0057] Furthermore, the hydrogenated polymer composition of the present invention may, within the range that does not impair the reactivity of the hydrogenated polymer composition, further include at least one of the following: a boron crosslinked trimer (C) as shown in formula (XI) below, and an unmodified polymer (D) without boron-containing functional groups. Preferably, the content of (C) and (D) in the aforementioned hydrogenated polymer composition is 20% by mass or less for each.

[0058]

[0059] In the above formula (XI), P13, P14 and P15 represent polymer chains containing hydrogenated conjugated diene units in the same way as P1~P12.

[0060] The content of the hydrogenated polymer composition containing boron-functionalized hydrogenated conjugated diene modified polymer (typically, hydrogenated conjugated diene modified polymer with boron-functionalized groups at the ends) is preferably 60% by mass or more, more preferably 65% ​​by mass or more, relative to the total mass of the polymers contained in the composition.

[0061] The boron content in hydrogenated polymer compositions can be determined by quantitatively analyzing the boron content per unit weight of the hydrogenated polymer composition using ICP (Inductively Coupled Plasma) atomic emission spectrometry.

[0062] From the viewpoint of reactivity to polar functional groups and excellent dispersibility in thermoplastic polymers, typically in vinyl alcohol polymers, the boron content in the polymer composition is preferably 0.001 to 5% by mass, more preferably 0.003 to 2% by mass.

[0063] In the hydrogenated polymer composition of the present invention, at least a portion of the carbon-carbon double bonds contained in the conjugated diene units are hydrogenated, including the boron-based hydrogenated conjugated diene modified polymer (A) and the boron crosslinked trimer (C) of the above formula (XI) which may be included depending on the circumstances, and the unmodified polymer (D) which does not have boron atoms at the end. In the hydrogenated polymer compositions of the present invention, from the viewpoint of heat resistance and weather resistance, the hydrogenation rate (hydrogenation rate) of the carbon-carbon double bonds contained in the conjugated diene units of the polymer before hydrogenation (unhydrogenated) is preferably 50 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more. Furthermore, the hydrogenation rate is typically 100 mol% or less. Moreover, the hydrogenation rate can be substantially 100 mol% (i.e., substantially complete hydrogenation). Furthermore, the hydrogenation rate is a value obtained by calculating the content of carbon-carbon double bonds contained in the conjugated diene units of the polymer before and after hydrogenation using 1H-NMR, respectively.

[0064] Regarding the manufacturing method of the hydrogenated polymer composition of the present invention comprising a hydrogenated conjugated diene modified polymer having boron functional groups, it is preferred to include the manufacturing method comprising the following steps (1), (2) and (3).

[0065] Step (1): In the presence of an active metal or active metal compound capable of anionic polymerization, a monomer containing a conjugated diene is anionicly polymerized to produce an active-terminated polymer (hereinafter also referred to as active-terminated polymer (Z)).

[0066] The descriptions of specific examples and preferred forms of monomers that are structural units derived from the monomers constituting the active terminal polymer (Z), as well as the descriptions of specific examples and preferred forms of structural units derived from the monomers contained in the active terminal polymer (Z), are the same as the descriptions of polymer chains in the hydrogenated polymer composition above regarding the conjugated diene units represented by P1 to P12 that contain conjugated diene units for constituting hydrogenated conjugated diene units and, as needed, unhydrogenated conjugated diene units, aromatic vinyl compound units, and other structural units derived from monomers other than conjugated dienes.

[0067] Active-terminated polymers (Z) with anionic polymerizable active ends can be manufactured using known polymerization methods. For example, active-terminated polymers (Z) can be obtained by anionic polymerization of monomers in an inert solvent using an active metal or active metal compound capable of anionic polymerization as an initiator, in the presence of a polar compound as needed.

[0068] Regarding active metals or active metal compounds capable of anionic polymerization, organoalkali metal compounds are preferred, and organolithium compounds are even more preferred.

[0069] Among the aforementioned active metals capable of anionic polymerization, examples include alkali metals such as lithium, sodium, and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium, and barium; and lanthanide rare earth metals such as lanthanum and neodymium. Of these, alkali metals and alkaline earth metals are preferred, and alkali metals are even more preferred.

[0070] Examples of organoalkali metal compounds suitable for use as active metal compounds capable of anionic polymerization include, for example, monolithium compounds such as methyllithium, ethyllithium, n-butyllithium, dibutyllithium, tert-butyllithium, pentyllithium, hexyllithium, phenyllithium, and stilbene lithium; polyfunctional organolithium compounds such as dilithium methane, dinaphthalene, 1,4-dilithium butane, 1,4-dilithium-2-ethylcyclohexane, and 1,3,5-trilithiumbenzene; and sodium naphthene and potassium naphthene. Among these organoalkali metal compounds, organolithium compounds are preferred. Examples of such organolithium compounds include, for example, methyllithium, ethyllithium, n-butyllithium, dibutyllithium, tert-butyllithium, and pentyllithium.

[0071] Examples of solvents mentioned above include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; and aromatic hydrocarbons such as benzene, toluene, and xylene.

[0072] Polar compounds may also be added during the aforementioned anionic polymerization. Polar compounds in anionic polymerization generally do not deactivate the reaction but are used to adjust the microstructure (vinyl content) of the conjugated diene units. Examples of polar compounds include ether compounds such as dibutyl ether, tetrahydrofuran, and ethylene glycol diethyl ether; tertiary amines such as tetramethylethylenediamine and trimethylamine; alkali metal alkoxides, and phosphine compounds. Polar compounds are typically used in amounts of 0.01 to 1000 mol relative to 1 mol of an organoalkali metal compound.

[0073] The temperature range for the above-mentioned anionic polymerization is typically -80 to 150°C, preferably 0 to 100°C, and even more preferably 10 to 90°C. The polymerization process can be either batch or continuous.

[0074] Step (2): Reacting the aforementioned active terminal polymer (Z) with a boric acid compound to obtain a non-hydrogenated conjugated diene modified polymer having boron functional groups, wherein the boric acid compound has at least two partial structures represented by the following formula (I) (hereinafter, this structure is also referred to as partial structure (I)), and at least one of the R atoms bonded to the oxygen atoms contained in the partial structure (I) has a Taft stereoparameter Es value of -0.30 or less. BOR (I) (In formula (I), B represents a boron atom, O represents an oxygen atom, and R represents an organic group)

[0075] Here, the Taft stereoparameter Es value refers to the relative rate of esterification of substituted carboxylic acids under acidic conditions, based on the effect of methyl substituents, and is a general indicator of the stereobloat of the substituents. This invention includes the Es (Taft) values ​​listed in Table 1 of Tetrahedron, 1978, Vol. 34, pages 3553-3562, and values ​​measured according to the methods described in the aforementioned literature. For example, the value for hydrogen is 1.24, for methyl is 0.0, for ethyl is -0.08, for n-propyl is -0.36, for isopropyl is -0.47, for n-butyl is -0.39, for secondary butyl is -1.13, for isobutyl is -0.93, for tert-butyl is -1.54, and for cyclohexyl is -0.79.

[0076] The preferred Taft stereo parameter Es value is -3.00 to -0.30, and the more preferred value is -1.55 to -0.39.

[0077] For example, boric acid compounds containing at least one of the R atoms in partial structure (I) with a Taft stereoparameter Es value of -0.30 or less become difficult to form cluster structures composed of boric acid compounds due to steric hindrance. Therefore, they exhibit high electrophilicity, resulting in increased reactivity with active terminals, and ultimately yielding a polymer composition containing a high proportion of borate-based hydrogenated conjugated diene modified polymer (A). Furthermore, from the viewpoint of further improving the reactivity, a preferred morphology is one in which all R atoms bonded to the oxygen atoms in partial structure (I) satisfy the aforementioned Es value.

[0078] For R satisfying the above Es value, it is preferably n-propyl, isopropyl, n-butyl, dibutyl, isobutyl, or cyclohexyl, more preferably isopropyl or n-butyl, and even more preferably isopropyl.

[0079] The aforementioned boric acid compounds are boric acid compounds obtained by anionic polymerization that are reactive with the active ends of the active-terminal polymer (Z). Among these, boric acid esters represented by the following formula (XII) are preferred.

[0080]

[0081] In the above formula (XII), R16, R17 and R18 represent hydrocarbon groups with 1 to 12 carbon atoms. Of R16, R17, and R18, at least one preferably has a Taft stereoparameter Es value of -0.30 or less, more preferably -3.00 to -0.30, and even more preferably -1.55 to -0.39. Furthermore, a preferred state is that all of R16, R17, and R18 satisfy the aforementioned Es value. At least one of R16, R17, and R18 is preferably n-propyl, isopropyl, n-butyl, dibutyl, isobutyl, or cyclohexyl, more preferably isopropyl or n-butyl, and even more preferably isopropyl. Furthermore, it is preferred that all of R16, R17, and R18 are n-propyl, isopropyl, n-butyl, dibutyl, isobutyl, or cyclohexyl, more preferably isopropyl or n-butyl, and even more preferably isopropyl.

[0082] Examples of borate esters represented by formula (XII) above include tri-n-propyl borate, tri-n-butyl borate, triisopropyl borate, tri-dibutyl borate, triisobutyl borate, and tricyclohexyl borate. Among these, tri-n-propyl borate, tri-n-butyl borate, and triisopropyl borate are preferred.

[0083] In step (2), the boric acid compound is used in an amount of 0.5 to 10 mol, more preferably 1 to 5 mol, relative to 1 mol of the active end polymer (Z).

[0084] In step (2), it is preferable to mix the above-mentioned boric acid compound with a polar compound and then react the mixture with the above-mentioned active end polymer (Z).

[0085] Examples of the aforementioned polar compounds include ether compounds such as dibutyl ether, tetrahydrofuran, and ethylene glycol diethyl ether; tertiary amines such as tetramethylethylenediamine and trimethylamine; alkali metal alkoxides; and phosphine compounds. The polar compound is typically used in an amount of 0.01 to 1000 moles relative to the boric acid compound used in step (2). By adding the polar compound, the molecular association of the boric acid compound can be dissociated, thereby increasing its reactivity.

[0086] The reaction temperature of the active end polymer (Z) and boric acid compound in step (2) above is usually in the range of -80~150℃, preferably in the range of 0~100℃, and even more preferably in the range of 10~90℃.

[0087] Alternatively, the active-terminated polymer (Z) from step (2) can be reacted with a boric acid compound to obtain a non-hydrogenated conjugated diene modified polymer with boron functional groups, and then a polymerization terminator for the active-terminated polymer (Z) can be added. By adding a polymerization terminator in this way, side reactions originating from the active ends contained in the residual active-terminated polymer (Z) can be reliably suppressed after the reaction with the boric acid compound. Examples of polymerization terminators include alcohols such as methanol, ethanol, n-propanol, and isopropanol.

[0088] The reaction pattern in step (2) can be either batch or continuous.

[0089] Step (3): The step of hydrogenating (hydrogenating) at least a portion of the carbon-carbon double bonds contained in the conjugated diene units of the unhydrogenated conjugated diene modified polymer obtained in step (2).

[0090] Through this step (3), at least a portion of the carbon-carbon double bond contained in the conjugated diene unit will be added with hydrogen. There are no particular limitations on the method for hydrogenating the unhydrogenated conjugated diene modified polymer to obtain the hydrogenated polymer composition of the present invention; for example, known methods can be used. Steps (1) and (2) above, along with hydrogenation, can be performed continuously, or the composition obtained in step (2) containing the unhydrogenated conjugated diene modified polymer with boron functional groups can be isolated and then hydrogenated. The method for isolating the composition containing the unhydrogenated conjugated diene modified polymer is the same as the method for recovering the hydrogenated polymer composition of the reaction product obtained in step (3) described later.

[0091] Regarding the catalyst used in the hydrogenation reaction of step (2), a catalyst in which the carbon-carbon double bond contained in an olefin compound can be hydrogenated can be used. Examples of such catalysts include heterogeneous catalysts and homogeneous catalysts.

[0092] The aforementioned heterogeneous catalysts are not particularly limited, but specific examples include sponge metal catalysts such as sponge nickel, sponge cobalt, and sponge copper; and supported metal catalysts such as nickel silica, nickel aluminide, nickel zeolite, nickel diatomite, palladium silica, palladium aluminide, palladium zeolite, palladium diatomite, palladium carbon, palladium calcium carbonate, platinum silica, platinum aluminide, platinum zeolite, platinum diatomite, platinum carbon, platinum calcium carbonate, ruthenium silica, ruthenium aluminide, ruthenium zeolite, ruthenium diatomite, ruthenium carbon, ruthenium calcium carbonate, iridium silica, iridium aluminide, iridium zeolite, iridium diatomite, iridium carbon, iridium calcium carbonate, cobalt silica, cobalt aluminide, cobalt zeolite, cobalt diatomite, cobalt carbon, and cobalt calcium carbonate. These heterogeneous catalysts are designed to enhance activity, selectivity, and stability, and can also be modified with iron, molybdenum, magnesium, etc. Furthermore, these heterogeneous catalysts can be used alone or in combination with two or more types.

[0093] The homogeneous catalysts mentioned above are not particularly limited, but specific examples include Ziegler catalysts, such as those composed of transition metal compounds and catalysts composed of alkylaluminum or alkyllithium; and metallocene catalysts, such as those composed of bis(cyclopentadienyl) compounds of transition metals such as titanium, zirconium, and hafnium, and organometallic compounds of metals such as lithium, sodium, potassium, aluminum, zinc, or magnesium. Specific examples of transition metal compounds used in Ziegler-based catalysts include nickel salts such as nickel acetate, nickel octanoate, nickel neodecanoate, nickel naphthenate, and nickel acetoacetone; cobalt salts such as cobalt acetate, cobalt octanoate, cobalt neodecanoate, and cobalt acetoacetone; and titanium diacetene and zirconium diacetene. Specific examples of alkyl aluminum used in Ziegler catalysts include trimethylaluminum, triethylaluminum, triisobutylaluminum, and trioctylaluminum. Specific examples of alkyl lithiums used in Ziegler catalysts include methyl lithium, ethyl lithium, n-butyl lithium, secondary butyl lithium, and tertiary butyl lithium. These homogeneous catalysts can be used alone or in combination of two or more. Furthermore, it is also acceptable to use homogeneous and heterogeneous catalysts in combination.

[0094] From the perspective of reactivity, among these catalysts, homogeneous catalysts are preferred, Ziegler catalysts are more preferred, Ziegler catalysts composed of transition metal compounds and alkyl aluminum are even more preferred, and Ziegler catalysts composed of titanium dichlorocerocene and alkyl aluminum are particularly preferred. On the other hand, in the hydrogenation reaction of step (2), since the polymer is hydrogenated, the reactivity of low molecular weight compounds is usually reduced. Therefore, high temperature and high pressure conditions are generally preferred as reaction conditions. In this case, as the catalyst used in the hydrogenation reaction, in the case of thermal stability where catalyst activity is important, it is preferable to carry out the hydrogenation reaction with a heterogeneous catalyst with high thermal stability. From the perspective of hydrogenation activity, it is preferable to use nickel or palladium as the metal with hydrogenation activity. Furthermore, in order to suppress undesirable side reactions in the hydrogenation reaction, it is preferable to use calcium carbonate or a carbon support as the support, and it is even more preferable to use a carbon support.

[0095] Hydrogenation reactions are typically carried out in a solvent. The solvent is not particularly limited; for example, the solvent used in the anionic polymerization illustrated in step (1) above can be used.

[0096] The hydrogenation reaction described above can be carried out directly without special treatment of the solvent, for example, in the presence of the unhydrogenated conjugated diene modified polymer with boron functional groups in the solvent used in step (1). Alternatively, a portion of the solvent can be removed by distillation or other methods, and the reaction can be carried out in the remaining solvent. Furthermore, after step (1) is completed, once the composition containing the unhydrogenated conjugated diene modified polymer with boron functional groups is removed, this composition containing the unhydrogenated conjugated diene modified polymer can be placed in a solvent to carry out the hydrogenation reaction.

[0097] When hydrogenation is carried out in a solvent, the amount of solvent used is preferably between 1% and 30% by mass relative to the total concentration of the polymer containing the unhydrogenated conjugated diene-modified polymer in step (1) of the reaction solution. If the hydrogenation reaction is carried out at less than 1% by mass, there will be a significant decrease in productivity, and if it exceeds 30% by mass, the viscosity will increase significantly, resulting in a decrease in mixing efficiency.

[0098] The reaction pressure of the hydrogenation reaction can be set appropriately according to the catalyst used, etc., but in terms of total pressure, it is usually 0.1MPa~20MPa, preferably 0.5MPa~15MPa, and even more preferably 0.5MPa~5MPa.

[0099] Hydrogenation reactions are carried out in the presence of hydrogen gas, but they can also be carried out in the presence of a mixture of gases other than hydrogen that are inert to the hydrogenation reaction. Specific examples of gases inert to the hydrogenation reaction include nitrogen, helium, argon, and carbon dioxide. Furthermore, depending on the reaction conditions, there may be situations where the solvent used in the reaction is a gaseous component and has a significant partial pressure; however, this situation is generally not a problem as long as the hydrogenation reaction will proceed.

[0100] The reaction temperature for hydrogenation can be set appropriately according to the catalyst used, but it is usually 20℃~250℃, preferably 50℃~180℃, and even more preferably 60℃~180℃. Generally, heterogeneous catalysts are used where it is desirable to carry out the reaction at a higher temperature than homogeneous catalysts. The reaction time for hydrogenation can be appropriately set according to the type and amount of catalyst used and the reaction temperature, but it is usually 0.1 to 100 hours, preferably 1 to 50 hours. If the reaction time is too short, the expected hydrogenation rate may not be obtained. Conversely, if the reaction time is too long, undesirable side reactions will occur significantly, and the hydrogenated conjugated diene modified polymer composition containing the expected physical properties may not be obtained.

[0101] There are no particular restrictions on the reaction pattern of hydrogenation, as long as it is appropriately set according to the type of catalyst used in the reaction. Examples of reaction patterns include batch reaction, semi-continuous reaction (semi-batch reaction), and continuous reaction. Suitable continuous reaction patterns include plug flow (PFR) and continuous flow stirred (CSTR). When using heterogeneous catalysts, hydrogenation reactions can be carried out in a fixed-bed reactor. In the case of hydrogenation reaction under active mixing conditions, the mixing methods include mixing methods using stirring and mixing methods that circulate the reaction liquid through a loop. When a heterogeneous catalyst is used under mixed conditions, the reaction is a gas-liquid-solid reaction field, utilizing a suspended bed. Conversely, when a homogeneous catalyst is used under mixed conditions, the reaction field is a gas-liquid two-phase system. Alternatively, once the hydrogenation reaction in the reaction tank is complete, the reaction liquid can be extracted, and at least a portion of the extracted reaction liquid can be added to the same or different reaction tanks to carry out a further hydrogenation reaction. By carrying out the hydrogenation reaction in this manner, the localized heating associated with the hydrogenation reaction can be avoided, resulting in an increased hydrogenation rate. Hydrogenation can be carried out in a single reaction form or in combination of two or more of the same or different reaction forms. In cases where a higher hydrogenation rate is desired, there is a possibility that the hydrogenation reaction steps include steps that use a fixed-bed reactor to carry out the reaction in a plug flow manner.

[0102] The amount of catalyst used in the hydrogenation reaction can be appropriately set according to the type of catalyst used, the total concentration of the polymer containing the unhydrogenated conjugated diene modified polymer in step (1), the reaction mode, etc. However, when using a heterogeneous catalyst and carrying out the hydrogenation reaction in a suspended bed, the amount of catalyst used per 100 parts by mass of the reaction solution containing the unhydrogenated conjugated diene modified polymer in step (1) is usually 0.01 to 20 parts by mass, preferably 0.05 to 15 parts by mass, and even more preferably 0.1 to 10 parts by mass. If the amount of catalyst used is too small, the hydrogenation reaction will require a long time. If the amount of catalyst used is too large, more power will be needed to mix the heterogeneous catalyst. Furthermore, when carrying out the hydrogenation reaction in a fixed bed, it is difficult to specify the amount of catalyst used per unit of the reaction solution containing the unhydrogenated conjugated diene modified polymer in step (1). It can be appropriately set according to the type of reaction tank used, etc. When using Ziegler-based or metallocene-based catalysts as homogeneous catalysts, the concentration of transition metal compounds in the reaction solution containing the unhydrogenated conjugated diene modified polymer after step (1) is typically 0.001 mmol / L to 100 mmol / L, preferably 0.01 mmol / L to 10 mmol / L.

[0103] The catalyst used in the hydrogenation reaction can be separated from the liquid containing the hydrogenated conjugated diene modified polymer with boron functional groups, as needed, after the hydrogenation reaction is completed. There are no particular limitations on the separation method, as long as it can separate the catalyst. In the case of using a heterogeneous catalyst, the catalyst can be separated, for example, by continuous or batch filtration, centrifugation, sedimentation using settling, and decantation. In the case of using a homogeneous catalyst, the catalyst can be separated, for example, by coagulation precipitation, adsorption, washing, and aqueous phase extraction. Even when the used catalyst is separated using such separation methods, trace amounts of metal components originating from the catalyst may sometimes remain in the liquid containing the hydrogenated conjugated diene modified polymer with boron functional groups. Since this is also a case of metal components remaining in the liquid, as mentioned above, the residual metal components can be separated by separation methods such as coagulation precipitation, adsorption, washing, and aqueous phase extraction. The catalyst recovered through separation can be reused in hydrogenation reactions after some of it is removed or new catalyst is added as needed.

[0104] The hydrogenated polymer composition obtained by the manufacturing method of the present invention is recovered from the reaction product obtained in step (3) above. There are no particular limitations on the recovery method of the hydrogenated polymer composition, but if the reaction product is obtained in step (3) as a solution containing the hydrogenated polymer composition, it can be recovered, for example, by: injecting the obtained solution into a lean solvent such as methanol to precipitate the hydrogenated polymer composition; injecting the obtained solution together with steam into hot water to remove the solvent by azeotropic distillation (steam stripping); or washing the polymer solution with water, and drying it after separation to isolate the aforementioned polymer composition. In this case, the washing efficiency can be further improved by using an acidic aqueous solution for washing. Preferably, the acid used is a monovalent or polyvalent strong acid such as hydrochloric acid, nitric acid, or sulfuric acid; a monovalent or polyvalent carboxylic acid such as acetic acid, propionic acid, succinic acid, or citric acid; or a monovalent or polyvalent weak acid such as carbonic acid or phosphoric acid.

[0105] The resin composition of this invention is a hydrogenated polymer composition (hereinafter also referred to as hydrogenated polymer composition (α) comprising a boronite-based hydrogenated conjugated diene modified polymer (A) and a boronite-based hydrogenated conjugated diene modified polymer (B), and optionally a boron crosslinked trimer (C) and an unmodified polymer (D) without boron atoms at the ends. The resin composition of this invention may also contain other polymers (β) besides those contained in the hydrogenated polymer composition (α). These other polymers (β) may be thermoplastic polymers (β1) or curable polymers (β2).

[0106] Regarding the aforementioned thermoplastic polymers (β1), examples include acrylic resins such as polymethyl methacrylate and (meth)acrylate polymers or copolymers; olefin resins such as polyethylene, ethylene-vinyl acetate copolymer, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; ethylene-based ionomers; styrene resins such as polystyrene, styrene-maleic anhydride copolymer, impact-resistant polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, and MBS resin; styrene-methyl methacrylate copolymers; and styrene-methyl methacrylate-maleic anhydride copolymers. Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polylactic acid; polyamides such as Nylon 6, Nylon 66, and polyamide elastomers; polycarbonate; polyvinyl chloride; polyvinylidene chloride; polyvinyl acetate; vinyl alcohol polymers such as partially saponified polyvinyl alcohol, polyvinyl alcohol, and ethylene-vinyl alcohol copolymers; polyacetal; polyvinylidene fluoride; polyurethane; modified polyphenylene ether; polyphenylene sulfide; modified polysiloxane rubber resins; acrylic rubbers; polysiloxane rubbers; styrene-based thermoplastic elastomers such as SEPS, SEBS, and SIS; and olefin rubbers such as IR, EPR, and EPDM. From the perspective of superior dispersibility of the hydrogenated polymer composition (α) obtained by the present invention, vinyl alcohol polymers are preferred, more preferably partially saponified polyvinyl alcohol, polyvinyl alcohol, and ethylene-vinyl alcohol copolymers, and even more preferably ethylene-vinyl alcohol copolymers. Thermoplastic polymer (β1) can be used alone or in combination with two or more.

[0107] The aforementioned ethylene-vinyl alcohol copolymer is a saponified product of an ethylene-vinyl ester copolymer comprising structural units derived from ethylene (ethylene units) and structural units derived from ethylene esters (ethylene ester units). The content of ethylene units in the ethylene-vinyl alcohol copolymer is not particularly limited, but is typically in the range of 10-99 mol%, preferably 15-60 mol%, more preferably 20-60 mol%, and even more preferably 25-55 mol. Furthermore, there is no particular limitation on the saponification degree of the ethylene ester unit in the ethylene-vinyl alcohol copolymer, but it is generally in the range of 10 to 100 mol%, preferably 50 to 100 mol%, more preferably 80 to 100 mol%, further preferably 95 to 100 mol%, and most preferably 99 to 100 mol%. If the saponification degree is too low, the crystallinity will decrease, and the thermal stability during melt molding will deteriorate. Therefore, a higher saponification degree is preferred. Regarding ethylene esters, vinyl acetate can be cited as a representative example, but other examples include vinyl propionate, vinyl valerate, vinyl valerate, vinyl caprylate, and vinyl benzoate. These ethylene esters can also be used in combination, one or more of them. Alternatively, two or more different ethylene-vinyl alcohol copolymers can be mixed together as the aforementioned ethylene-vinyl alcohol copolymer.

[0108] To the extent that the purpose of this invention is not hindered, the ethylene-vinyl alcohol copolymer may also contain structural units derived from other monomers besides the aforementioned ethylene units, ethylene ester units, and saponified ethylene ester units. Examples of such other monomers include olefinic monomers such as propylene, 1-butene, and isobutene; acrylamide monomers such as acrylamide, N-methylacrylamide, N-ethylacrylamide, and N,N-dimethylacrylamide; methacrylamide monomers such as methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, and N,N-dimethylmethacrylamide; vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, tributyl vinyl ether, and dodecyl vinyl ether; allyl alcohol; vinyltrimethoxysilane; and N-vinyl-2-pyrrolidone.

[0109] The melt flow rate (hereinafter, sometimes simply referred to as "MFR") of the aforementioned ethylene-vinyl alcohol copolymer according to JIS K 7210:2014 (temperature 210°C, load 2160g) is preferably 0.1g / 10min or more, more preferably 0.5g / 10min or more, and even more preferably 1g / 10min or more. On the other hand, the MFR of the ethylene-vinyl alcohol copolymer is preferably 50g / 10min or less, more preferably 30g / 10min or less, and even more preferably 15g / 10min or less. By setting the MFR of the ethylene-vinyl alcohol copolymer to this range, melt formability is improved.

[0110] Examples of curable polymers (β2) include epoxy resins, unsaturated polyester resins, epoxy (meth)acrylate resins, ester (meth)acrylate resins, phenolic resins, urea resins, melamine resins, thermosetting carbamate resins, silicone resins, amide resins, furan resins, alkyd resins, allyl resins, and diallyl phthalate resins. From the viewpoints of accessibility and the basic physical properties of the cured product, as well as from the viewpoints of obtaining a superior resin composition due to bubble release and the resulting toughness of the cured product, epoxy resins, unsaturated polyester resins, and epoxy (meth)acrylate resins are preferred, with epoxy resins and unsaturated polyester resins being more preferred, and epoxy resins being even more preferred. One type of curable polymer (β2) may be used alone, or two or more may be used in combination.

[0111] When the resin composition of the present invention contains the above-mentioned polymer (β), the mass ratio (α) / (β) of the hydrogenated polymer composition (α) to other polymers (β) is preferably 50 / 50 to 1 / 99, more preferably 40 / 60 to 2 / 98, further preferably 30 / 70 to 3 / 97, even more preferably 20 / 80 to 3 / 97, and most preferably 15 / 85 to 3 / 97.

[0112] Furthermore, various additives can be added to the resin composition of the present invention without impairing its effects. For example, when the other polymer (β) is a thermoplastic polymer (β1), the additives can include reinforcing agents or fillers such as calcium carbonate, silica, carbon black, glass fiber, and clay, as well as plasticizers such as process oil, polyethylene glycol, glycerin, and phthalates. Other additives include heat stabilizers, antioxidants, ultraviolet absorbers, colorants, pigments, lubricants, and surfactants. Furthermore, foaming agents can be used as additives, and a foamed body can be produced from the polymer composition containing the foaming agent and the thermoplastic polymer (β1). For example, in cases where other polymers (β) are curing polymers (β2), the additives that can be mentioned include curing agents, curing accelerators, known rubbers, thermoplastic elastomers, impact modifiers such as core-shell particles, fillers (inorganic particles such as silica, talc, calcium carbonate, and aluminum hydroxide), flame retardants, defoamers, pigments, dyes, antioxidants, weathering agents, lubricants, and release agents.

[0113] The mixing method of other polymers (β) with the hydrogenated polymer composition (α) of the present invention can be adjusted by conventional polymer mixing methods according to the composition ratio of each component.

[0114] When other polymers (β) are thermoplastic polymers (β1), the resin composition of the present invention can be produced, for example, by using mixing apparatus such as extruders, mixing rollers, Banbury mixers, and kneaders. In particular, a preferred embodiment of the present invention is a melt-kneading method using such mixing apparatus.

[0115] In the case where other polymers (β) are curable polymers (β2), the resin composition of the present invention can be produced by thoroughly mixing with a stirrer or the like, then melting and kneading using a mixing roller machine, an extruder or the like, followed by cooling and pulverizing. [Example]

[0116] The present invention will be further described in detail below by way of examples, but the present invention is not limited to these examples. Furthermore, in the following examples and comparative examples, the physical properties of the hydrogenated polymer composition were evaluated by the following methods.

[0117] (1) Weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) The weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the polymer were obtained by gel permeation chromatography (GPC) with reference to standard polystyrene. Device: GPC device "HLC-8220" manufactured by Tosoh Corporation Separation column: "TSKgel SuperMultiporeHZ-M (column diameter = 4.6mm, column length = 15cm)" manufactured by Tosoh Corporation (used in series with 2 columns). Dissolution solution: Tetrahydrofuran Dissolution flow rate: 0.35 mL / min Column temperature: 40℃ Detection method: Differential refractive index (RI) Injection volume: 10μL Concentration: 1 mg / 1 mL (polymer / THF)

[0118] (2) Vinyl content, hydrogenation rate The vinyl content of the hydrogenated conjugated diene-modified polymer and the polymers produced at various stages were calculated using 1H-NMR. Furthermore, the vinyl content was calculated for the unhydrogenated polymer before hydrogenation, and was determined by the area ratio of the signal from the double bonds of the ethylene-derived conjugated diene units to the signal from the unethylene-derived conjugated diene units in the obtained spectrum. Since the signal from the double bonds of the conjugated diene units decreases before and after hydrogenation, the hydrogenation rate can be calculated by comparing the area ratio of the signal from the double bonds of the conjugated diene units in the unhydrogenated polymer to the same area ratio of appropriate signals that do not change with hydrogenation (signals from the aromatic ring of styrene, signals from the terminal methyl group of the initiator, etc.) with that of the hydrogenated polymer. Equipment: JEOL Ltd. manufactures the JNM-ECX400 nuclear magnetic resonance imaging (MRI) device. Solvent: deuterated chloroform Measurement temperature: 50℃ Integration count: 1024 times

[0119] (3) Boron-containing functional group introduction rate (mass %) The introduction rate of boron-containing functional groups to the polymer terminals (boron-containing functional group introduction rate) by the reaction of a boric acid compound and an active terminal polymer is calculated from the content ratio of boron atoms obtained by ICP (inductively coupled plasma) atomic emission spectrometry and the polymer components obtained by GPC measurement after decomposing the polymer composition obtained in the following examples, etc., by removing unreacted boric acid compounds by washing with water. The boron-containing functional group introduction rate can be obtained from the sum of the sub-boric acid-based hydrogenated conjugated diene-modified polymer (A) and the hypo-boric acid-based hydrogenated conjugated diene-modified polymer (B) by removing the mass of unmodified substances from the mass of the entire polymer composition obtained in each example, etc. <Microwave digestion> Device: ETHOS UP manufactured by MILESTONE Solvent: Nitric acid Decomposition temperature: 210 °C Decomposition time: 30 minutes <ICP atomic emission spectrometry> Device: iCAP7400 Duo manufactured by ThermoFisher

[0120] (4) Content (mass %) of sub-boric acid-based hydrogenated conjugated diene-modified polymer (A) and hypo-boric acid-based hydrogenated conjugated diene-modified polymer (B) in the polymer composition In the polymer composition obtained in each of the following examples, etc., the molecular weight of the hypo-boric acid-based hydrogenated conjugated diene-modified polymer (B) becomes larger than that of the sub-boric acid-based hydrogenated conjugated diene-modified polymer (A) and the unmodified polymer not modified by the boric acid compound. Also, the molecular weights of the sub-boric acid-based hydrogenated conjugated diene-modified polymer (A) and the unmodified polymer are the same. Due to these circumstances, first, the content (mass %) of the hypo-boric acid-based hydrogenated conjugated diene-modified polymer (B) in the polymer composition and the combined content (mass %) of the sub-boric acid-based hydrogenated conjugated diene-modified polymer (A) and the unmodified polymer are calculated from the area ratios obtained by GPC, respectively. Then, the content of the sub-boric acid-based hydrogenated conjugated diene-modified polymer (A) in the polymer composition is calculated as follows from the boron-containing functional group introduction rate obtained as described above and the content obtained from the results of the above GPC. (Content of boronite-based hydrogenated conjugated diene modified polymer (A) (mass %) = (Introduction rate of boron functional groups (mass %)) - (Content of boronite-based hydrogenated conjugated diene modified polymer (B) (mass %))

[0121] (5) Reactivity The reactivity of the boron-containing functional groups in the hydrogenated conjugated diene-modified polymers obtained in the Examples was evaluated based on the signal change when an equal amount of catechol from the polymer initiation terminal phase in step (1) of each Example or Comparative Example was added to the deuterated solvent solution of the polymer using 1H-NMR, and according to the following indicators. The amount of polymer initiation terminal phase was calculated from the integral ratio of the alkyl group from alkyllithium to the signal from the double bond of the conjugated diene unit in the polymer before hydrogenation using 1H-NMR. A: The catechol content of the signal displacement is over 70 mmol. B: The catechol content of the signal displacement is 50 mol% or more and less than 70 mol%. C: The catechol content of the signal displacement is above 25 mol% and less than 50 mol%. D: The amount of catechol in the signal displacement is less than 25 mol%.

[0122] (6) Dispersion The dispersibility of the polymers obtained in the examples in thermoplastic polymers was evaluated as follows. In the case of thermoplastic polymers, vinyl alcohol-based polymers were used. The dispersibility in vinyl alcohol-based polymers was determined by kneading 95 parts by mass of an ethylene-vinyl alcohol copolymer with an ethylene unit content of 32 mol% and a saponification degree of 99.9 mol%, and 5 parts by mass of a hydrogenated polymer composition, using a Labo Plastomill (device name 4M150, manufactured by Toyo Seiki Seisaku-sho, Ltd.) at 200°C for 10 minutes and 100 rpm to obtain a resin composition. The resulting resin composition was then pressurized at 200°C to form a 125 μm thick film. The dispersion diameter of the dispersed region in the cross-section was then confirmed using an optical microscope. Evaluation was performed according to the following indicators. A: In the dispersed regions of the cross-section, the largest one has a diameter of less than 3 μm. B: In the dispersed regions of the cross-section, the largest has a diameter greater than 3 μm and less than 5 μm. C: In the dispersed regions of the cross-section, the largest has a diameter greater than 5 μm and less than 7 μm. D: In the dispersed regions of the cross-section, the largest one has a diameter of 7 μm or more.

[0123] (7) Taft's solid parameter Es value The Taft stereo parameters Es values ​​of the organic groups bonded to oxygen atoms in the boric acid compounds used in the following examples and comparative examples were calculated by the method described in the embodiments of the invention described above.

[0124] [Example 1] (Step (1)) A thoroughly dried 5L autoclave was nitrogen-purged. 606g of cyclohexane, 4.51g of tetrahydrofuran, and 5.40g of secondary butyllithium (1.3M cyclohexane solution) were fed into the autoclave. The temperature was raised to 50°C, and under stirring, 140g of butadiene was added sequentially at a rate of 10mL / min while maintaining the polymerization temperature at 50°C. After the addition of butadiene, the polymerization was stopped by heating for 1 hour, yielding a polymer solution containing butadiene polymers with active ends.

[0125] (Step (2)) 1.69 g of triisopropyl borate was added to the polymerization solution obtained in step (1), and borate was introduced into the polymerization end of the butadiene polymer to obtain a liquid containing the polymer composition. The vinyl content of the obtained polymer composition was 47 mol%.

[0126] (Step (3)) In the liquid containing the polymer composition obtained in step (2), 0.0001 moles of μ-chloro-μ-methylene[bis(cyclopentadienyl)titanium]dimethylaluminum (Tebbe catalyst) was added as a hydrogenation catalyst relative to the carbon-carbon double bonds contained in the butadiene units of all polymers contained in the polymer composition. The hydrogenation reaction was carried out at 85°C and a hydrogen pressure of 1 MPa until the hydrogenation rate reached 96 moles. The resulting liquid containing the hydrogenated polymer composition was added to 5 times the amount of methanol to precipitate the polymer, which was then recovered and dried. The terminal functional group induction rate of the obtained hydrogenated polymer composition was 90% by mass. Furthermore, in the obtained hydrogenated polymer composition, the content of boronite-based hydrogenated conjugated diene modified polymer (A) is 86% by mass, while the content of boronite-based hydrogenated conjugated diene modified polymer (B) is 4% by mass. The weight average molecular weight of boronite-based hydrogenated conjugated diene modified polymer (A) is 30,000, and the Mw / Mn ratio is 1.05.

[0127] [Example 2] (Step (1)) A thoroughly dried 5L autoclave was nitrogen-purged. 606g of cyclohexane, 5.40g of secondary butyllithium (1.3M cyclohexane solution), and 0.65g of tetramethylethylenediamine (TMEDA) were fed into the autoclave. The temperature was raised to 40°C, and under stirring, 140g of butadiene was added sequentially at a rate of 10mL / min while maintaining the polymerization temperature at 40°C. The polymerization was terminated by heating for 1 hour after the addition of butadiene, yielding a polymer solution containing butadiene polymers with active ends.

[0128] (Step (2)) 1.69 g of triisopropyl borate was added to the polymerization solution obtained in step (1), and borate was introduced into the polymerization end of the butadiene polymer to obtain a liquid containing the polymer composition. The vinyl content of the obtained polymer composition was 75 mol%.

[0129] (Step (3)) In the liquid containing the polymer composition obtained in step (2), a 0.0001 mole% Tebbe catalyst was added as a hydrogenation catalyst relative to the carbon-carbon double bonds contained in the butadiene units of all polymers contained in the polymer composition. The hydrogenation reaction was carried out at 85°C and a hydrogen pressure of 1 MPa until the hydrogenation rate reached 96 moles. The resulting liquid containing the hydrogenated polymer composition was added to 5 times the amount of methanol to allow the polymer composition to separate, then recovered and dried. The terminal functional group introduction rate of the obtained hydrogenated polymer composition was 90% by mass. Furthermore, in the obtained hydrogenated polymer composition, the content of the boronite-based hydrogenated conjugated diene modified polymer (A) was 88% by mass, and the content of the boronite-based hydrogenated conjugated diene modified polymer (B) was 2% by mass. The weight average molecular weight of the boronite-based hydrogenated conjugated diene modified polymer (A) was 30,000, and the Mw / Mn ratio was 1.04.

[0130] [Example 3] (Step (1)) A thoroughly dried 5L autoclave was nitrogen-purged. 606g of cyclohexane, 5.40g of secondary butyllithium (1.3M cyclohexane solution), and 0.65g of tetramethylethylenediamine (TMEDA) were fed into the autoclave. The temperature was raised to 40°C, and under stirring, 140g of butadiene was added sequentially at a rate of 10mL / min while maintaining the polymerization temperature at 40°C. The polymerization was terminated by heating for 1 hour after the addition of butadiene, yielding a polymer solution containing butadiene polymers with active ends.

[0131] (Step (2)) A mixture of 0.65 g TMEDA and 1.69 g triisopropyl borate was added to the polymerization solution obtained in step (1), and borate was introduced into the polymerization end of the butadiene polymer to obtain a liquid containing the polymer composition. The vinyl content of the resulting polymer composition was 75 mol%.

[0132] (Step (3)) In the liquid containing the polymer composition obtained in step (2), a 0.0001 mole% Tebbe catalyst was added as a hydrogenation catalyst relative to the carbon-carbon double bonds contained in the butadiene units of all polymers contained in the polymer composition. The hydrogenation reaction was carried out at 85°C and a hydrogen pressure of 1 MPa until the hydrogenation rate reached 96 moles. The resulting liquid containing the hydrogenated polymer composition was added to 5 times the amount of methanol to precipitate the polymer components, which were then recovered and dried. The terminal functional group induction rate of the obtained hydrogenated polymer composition was 98% by mass. Furthermore, in the obtained hydrogenated polymer composition, the content of the boronite-based hydrogenated conjugated diene modified polymer (A) was 95% by mass, and the content of the boronite-based hydrogenated conjugated diene modified polymer (B) was 3% by mass. The weight average molecular weight of the boronite-based hydrogenated conjugated diene modified polymer (A) was 30,000, and the Mw / Mn ratio was 1.04.

[0133] [Example 4] Except for changing the types and amounts of compounds in each step as shown in Table 1, the process was carried out in the same manner as in Example 3 to obtain a hydrogenated polymer composition containing a hydrogenated conjugated diene modified polymer.

[0134] [Example 5] Except for changing the types and amounts of compounds in each step as shown in Table 1, the process was carried out in the same manner as in Example 1 to obtain a hydrogenated polymer composition containing a hydrogenated conjugated diene modified polymer.

[0135] [Example 6] (Step (1)) A thoroughly dried 5L autoclave was nitrogen-purged. 606g of cyclohexane and 4.19g of secondary butyllithium (1.3M cyclohexane solution) were fed into the autoclave. The temperature was raised to 50°C, and under stirring, 137g of isoprene was added sequentially at a rate of 10mL / min while maintaining the polymerization temperature at 50°C. After the addition of isoprene, the polymerization was stopped by heating for 1 hour, yielding a polymer solution containing isoprene polymers with active ends.

[0136] (Step (2)) 1.31 g of triisopropyl borate was added to the polymerization solution obtained in step (1), and borate was introduced into the polymerization end of the isoprene polymer to obtain a liquid containing the polymer composition. The vinyl content of the obtained polymer composition was 8 mol%.

[0137] (Step (3)) In the liquid containing the polymer composition obtained in step (2), a Ziegler-based hydrogenation catalyst, consisting of nickel octanoate and triethylaluminum, with a Ni content of 0.1 moles in the hydrogenation catalyst, was added relative to the carbon-carbon double bonds contained in the isoprene units of all polymers contained in the polymer composition. The hydrogenation reaction was carried out at 85°C and a hydrogen pressure of 1 MPa until the hydrogenation rate reached 96 moles. The resulting liquid containing the hydrogenated polymer composition was then added to 5 times the volume of methanol to allow the polymer composition to precipitate, followed by recovery and drying. The terminal functional group induction rate of the resulting hydrogenated polymer composition was 85% by mass. Furthermore, in the obtained hydrogenated polymer composition, the content of boronite-based hydrogenated conjugated diene modified polymer (A) is 73% by mass, while the content of boronite-based hydrogenated conjugated diene modified polymer (B) is 12% by mass. The weight average molecular weight of boronite-based hydrogenated conjugated diene modified polymer (A) is 30,000, and the Mw / Mn ratio is 1.05.

[0138] [Example 7] (Step (1)) A thoroughly dried 5L autoclave was nitrogen-purged. 606g of cyclohexane, 4.49g of secondary butyllithium (1.3M cyclohexane solution), and 0.54g of TMEDA were fed into the autoclave. The temperature was raised to 50°C, and under stirring, 93g of butadiene was added sequentially at a rate of 10mL / min while maintaining the polymerization temperature at 50°C. After the butadiene addition, the autoclave was heated for 1 hour, followed by the sequential addition of 30g of isoprene at a rate of 10mL / min. The polymerization was terminated by heating for 1 hour after the isoprene addition, yielding a polymer solution containing a block copolymer composed of butadiene polymer blocks with active ends and isoprene polymer blocks.

[0139] (Step (2)) A mixture of 0.54 g TMEDA and 1.41 g triisopropyl borate was added to the polymerization liquid obtained in step (1), and borate was introduced into the polymerization ends of the isoprene polymer blocks to obtain a liquid containing the polymer composition. The total vinyl content of the obtained polymer composition was 69 mol%.

[0140] (Step (3)) In the liquid containing the polymer composition obtained in step (2), a Ziegler-based hydrogenation catalyst, consisting of nickel octanoate and triethylaluminum, with a Ni content of 0.1 moles in the hydrogenation catalyst, was added as a hydrogenation catalyst relative to the carbon-carbon double bonds contained in the butadiene and isoprene units of all the polymers contained in the polymer composition. The hydrogenation reaction was carried out at 85°C and a hydrogen pressure of 1 MPa until the hydrogenation rate reached 96 moles. The resulting liquid containing the hydrogenated polymer composition was then added to 5 times the volume of methanol to allow the polymer composition to precipitate, followed by recovery and drying. The terminal functional group induction rate of the obtained hydrogenated polymer composition was 95% by mass. Furthermore, in the obtained hydrogenated polymer composition, the content of boronite-based hydrogenated conjugated diene modified polymer (A) is 83% by mass, while the content of boronite-based hydrogenated conjugated diene modified polymer (B) is 12% by mass. The weight average molecular weight of boronite-based hydrogenated conjugated diene modified polymer (A) is 30,000, and the Mw / Mn ratio is 1.05.

[0141] [Example 8] (Step (1)) A thoroughly dried 5L autoclave was nitrogen-purged. 606g of cyclohexane, 3.30g of secondary butyllithium (1.3M cyclohexane solution), and 0.39g of TMEDA were fed into the autoclave. The temperature was raised to 40°C, and under stirring, 47g of butadiene was added sequentially at a rate of 10mL / min while maintaining the polymerization temperature at 40°C. After adding butadiene, the autoclave was heated for 1 hour, followed by the sequential addition of 74g of styrene at a rate of 10mL / min. The polymerization was terminated by heating for 1 hour after adding styrene, yielding a polymer solution containing a block copolymer composed of butadiene polymer blocks with active ends and styrene polymer blocks.

[0142] (Step (2)) A mixture of 0.39 g TMEDA and 1.03 g triisopropyl borate was added to the polymerization solution obtained in step (1), and borate was introduced into the polymerization ends of the styrene polymer blocks. The resulting polymer composition had a vinyl content of 76 mol%.

[0143] (Step (3)) In the liquid containing the polymer composition obtained in step (2), a 0.0001 mole mol% Tebbe catalyst was added as a hydrogenation catalyst relative to the carbon-carbon double bonds contained in the butadiene units of all polymers contained in the polymer composition. The hydrogenation reaction was carried out at 85°C and a hydrogen pressure of 1 MPa until the hydrogenation rate reached 96 moles. The resulting liquid containing the hydrogenated polymer composition was then added to 5 times the volume of methanol to allow the polymer composition to precipitate, followed by recovery and drying. The terminal functional group induction rate of the resulting hydrogenated polymer composition was 95% by mass. Furthermore, in the obtained hydrogenated polymer composition, the content of boronite-based hydrogenated conjugated diene modified polymer (A) is 85% by mass, while the content of boronite-based hydrogenated conjugated diene modified polymer (B) is 10% by mass. The weight average molecular weight of boronite-based hydrogenated conjugated diene modified polymer (A) is 30,000, and the Mw / Mn ratio is 1.06.

[0144] [Comparative Example 1] Except for the addition of 0.93 g of trimethyl borate to replace triisopropyl borate in step (2) as described in Table 1, the process was carried out in the same manner as in Example 1 to obtain a hydrogenated polymer composition containing a hydrogenated conjugated diene modified polymer.

[0145] [Comparative Example 2] Except that the boric acid compound in step (2) was not added as described in Table 1, the process was carried out in the same manner as in Example 1 to obtain the hydrogenated polymer composition.

[0146] [Comparative Example 3] Except for the addition of 2.78 g of phenylboronic anhydride to replace triisopropyl borate in step (2) as described in Table 1, the process was carried out in the same manner as in Example 1 to obtain a hydrogenated polymer composition comprising a hydrogenated conjugated diene modified polymer with end-introduced hypoboronic acid.

[0147] [Table 1] Unit: g Example Comparative example 1 2 3 4 5 6 7 8 1 2 3 Conjugated diene polymers (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) Step (1) Cyclohexane 606 606 606 606 606 606 606 606 606 606 606 Secondary butyllithium 5.40 5.40 5.40 30.00 5.40 4.19 4.49 3.30 5.40 5.40 5.40 styrene - - - - - - - 74 - - - Tetramethylethylenediamine - 0.65 0.65 - - - 0.54 0.39 - - - Tetrahydrofuran 4.51 - - 4.76 4.51 - - - 4.51 4.51 4.51 butadiene 140 140 140 157 140 - 93 47 140 140 140 Isoprene - - - - - 137 30 - - - - Step (2) Triisopropyl borate 1.69 1.69 1.69 9.47 - 1.31 1.41 1.03 - - - Tributyl borate - - - - 2.07 - - - - - - Trimethyl borate - - - - - - - - 0.93 - - Benzeneboronic anhydride - - - - - - - - - - 2.78 Tetramethylethylenediamine - - 0.65 3.61 - - 0.54 0.39 - - -

[0148] Table 2 presents the physical properties of the hydrogenated polymer compositions containing hydrogenated conjugated diene polymers obtained in Examples 1-8 and Comparative Examples 1-3.

[0149] [Table 2] Example 1 Example 2 Example 3 Example 4 polymer composition 1 2 3 4 polymer (A) (B) (A) (B) (A) (B) (A) (B) monomer butadiene butadiene butadiene butadiene Weight average molecular weight 30,000 60,000 30,000 60,000 30,000 60,000 6,000 12,000 Mw / Mn 1.05 1.05 1.04 1.04 1.04 1.04 1.04 1.04 Vinyl content (mol%) 47 47 75 75 75 75 50 50 R Isopropyl Isopropyl Isopropyl Isopropyl Es (stereoparameters) -0.47 -0.47 -0.47 -0.47 Polymer (A) content (mass %) in polymer composition 86 - 88 - 95 - 92 - Polymer (B) content (mass %) in polymer composition - 4 - 2 - 3 - 3 Boron-containing functional group incorporation rate (mass%) 90 90 98 95 Reactivity A A A A Dispersion A A A A Example 5 Example 6 Example 7 Example 8 polymer composition 5 6 7 8 polymer (A) (B) (A) (B) (A) (B) (A) (B) monomer butadiene Isoprene Butadiene / isoprene Butadiene / styrene Weight average molecular weight 30,000 60,000 30,000 60,000 30,000 60,000 30,000 60,000 Mw / Mn 1.04 1.04 1.05 1.05 1.05 1.05 1.06 1.06 Vinyl content (mol%) 48 48 8 8 69 69 76 76 R n-Butyl Isopropyl Isopropyl Isopropyl Es (stereoparameters) -0.39 -0.47 -0.47 -0.47 Polymer (A) content (mass %) in polymer composition 73 - 73 - 83 - 85 - Polymer (B) content (mass %) in polymer composition - 5 - 12 - 12 - 10 Boron-containing functional group incorporation rate (mass%) 78 85 95 95 Reactivity A A A A Dispersion A A A A Comparative Example 1 Comparative Example 2 Comparative Example 3 polymer composition 9 10 11 polymer (A) (B) - (A) (B) monomer butadiene butadiene - butadiene Weight average molecular weight 30,000 60,000 30,000 - 30,000 Mw / Mn 1.06 1.06 1.05 - 1.05 Vinyl content (mol%) 47 47 48 - 50 R methyl - - - Es (stereoparameters) 0 - - - Polymer (A) content (mass %) in polymer composition 20 - 0 0 - Polymer (B) content (mass %) in polymer composition - 1 0 - 86 Boron-containing functional group incorporation rate (mass%) twenty one 0 86 Reactivity C D A Dispersion C D B

[0150] Furthermore, R in Table 2 refers to the organic group bonded to the oxygen atom of the boric acid compound used in step (1), which is R in formula (I).

[0151] As shown in Table 2, since the boric acid compounds with substituents having a Taft stereoparameter Es value of -0.30 or less were reacted as shown in Examples 1-8, hydrogenated diene polymers containing hydrogenated conjugated diene polymers with boron-containing functional groups can be obtained, exhibiting high terminal functional group introduction rates, excellent reactivity with polar functional groups, and excellent dispersibility in thermoplastic polymers (vinyl alcohol-based polymers). On the other hand, in Comparative Example 1, where boric acid compounds with substituents having a Taft stereoparameter Es value exceeding -0.30 were reacted, the terminal functional group introduction rate was low, and the reactivity and dispersibility in thermoplastic polymers (vinyl alcohol-based polymers) were poor. Furthermore, in Comparative Example 2, where no boric acid compound was reacted, it did not react with polar functional groups, and the dispersibility in thermoplastic polymers (vinyl alcohol-based polymers) was also poor. Furthermore, in Comparative Example 3, which contains only boric acid compounds, although the reactivity is excellent, the dispersibility in thermoplastic polymers (vinyl alcohol-based polymers) is poor, making it difficult to balance reactivity and dispersibility in thermoplastic polymers (vinyl alcohol-based polymers). [Potential for industrial application]

[0152] By means of the manufacturing method of the present invention, a boronite-based hydrogenated conjugated diene modified polymer (A) suitable for the modification of polar materials or the dispersion of inorganic materials can be obtained in high yield. Furthermore, the hydrogenated polymer composition obtained by the present invention, comprising a boronite-based hydrogenated conjugated diene modified polymer and a boronin-based hydrogenated conjugated diene modified polymer in a specific ratio, exhibits high reactivity to polar functional groups and excellent dispersibility in thermoplastic polymers, typically in vinyl alcohol polymers. Therefore, the hydrogenated polymer composition of the present invention and the resin composition comprising this polymer composition can be effectively used in a wide range of fields, including automotive interior and exterior parts, electrical / electronic components, packaging materials, sporting goods, daily necessities, laminated materials, stretch materials, various rubber products, medical supplies, various adhesives, and various coating primers.

[0153] none

Claims

1. A method for manufacturing a hydrogenated polymer composition comprising a hydrogenated conjugated diene modified polymer having boron functional groups, comprising: step (1), wherein a monomer comprising a conjugated diene is anionicly polymerized in the presence of an active metal or an active metal compound capable of anionic polymerization, thereby producing an active end polymer (Z); step (2), wherein the active end polymer (Z) obtained in step (1) is reacted with a boric acid compound represented by the following formula (XII) to obtain an unhydrogenated conjugated diene modified polymer having boron functional groups; step (3), wherein at least a portion of the carbon-carbon double bonds contained in the conjugated diene unit contained in the unhydrogenated conjugated diene modified polymer obtained in step (2) is hydrogenated; (in formula (XII), R16, R17 and R18 represent hydrocarbon groups having 1 to 12 carbon atoms, and at least one of R16, R17 and R18 has a Taft's stereoparameter.) (parameter) Es value below -0.30).

2. The method for manufacturing the hydrogenated polymer composition as claimed in claim 1, wherein in the aforementioned step (2), after mixing the aforementioned boric acid compound with a polar compound, it is added to the active end polymer (Z) to cause it to react.

3. A hydrogenated polymer composition comprising 65-99% by mass of a nitrite-based hydrogenated conjugated diene modified polymer (A) and 1-35% by mass of a hypoacid-based hydrogenated conjugated diene modified polymer (B), wherein the nitrite-based hydrogenated conjugated diene modified polymer (A) is selected from hydrogenated conjugated diene modified polymers containing nitrite groups as shown in formula (II), hydrogenated conjugated diene modified polymers containing ester groups as shown in formula (III), and hydrogenated conjugated diene modified polymers containing ester groups as shown in formula (IV). The diagram shows at least one hypoacid from the group consisting of hydrogenated conjugated diene modified polymers containing a hypoacid group, wherein the hypoacid-based hydrogenated conjugated diene modified polymer (B) is selected from at least one of the group consisting of hydrogenated conjugated diene modified polymers containing hypoacid group as shown in formula (V), hydrogenated conjugated diene modified polymers containing hypoacid ester group as shown in formula (VII) or (VIII), and hydrogenated conjugated diene modified polymers containing hypoacid ester group as shown in formula (IX) or (X). (In the above formula, P1, P2, and P3 represent polymer chains containing hydrogenated conjugated diene units; R1 and R2 each independently represent hydrogen atoms or alkyl groups having 1 to 12 carbon atoms; at least one of R1 and R2 is an alkyl group having 1 to 12 carbon atoms, or R1 and R2 are bonded to form an alkyl chain having 2 to 24 carbon atoms; R3, R4, and R5 each independently represent hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, or polymer chains containing hydrogenated conjugated diene units; R3, R4, and R5 are...) At least one of R5 is an alkyl group having 1 to 12 carbon atoms, or a polymer chain containing a hydrogenated conjugated diene unit; or R3 and R4, R3 and R5, or R4 and R5 can be bonded to form an alkyl group having 2 to 24 carbon atoms, and R3, R4, and R5 can also be bonded to form a trivalent saturated hydrocarbon chain having 3 to 36 carbon atoms; M represents one alkali metal or one / half an alkaline earth metal, and at least one of R1 and R2 has a Taft stereoparameter Es value of -0.30 or less, and at least one of R3, R4, and R5 has a Taft stereoparameter Es value of -0.30 or less. (In the above formula, P4, P5, P7, P8, P9, P10, P11, and P12 represent polymer chains containing hydrogenated conjugated diene units; R7, R8, and R9 each independently represent alkyl groups having 1 to 12 carbon atoms; R10 and R11 each independently represent hydrogen atoms or alkyl groups having 1 to 12 carbon atoms; at least one of R10 and R11 is an alkyl group having 1 to 12 carbon atoms, or R10 and R11 are bonded to form an alkyl group having 2 to 12 carbon atoms.) The alkyl chain of 24, where R12 represents an alkyl group having 1 to 12 carbon atoms, R13 and R14 are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, at least one of R13 and R14 is an alkyl group having 1 to 12 carbon atoms, or R13 and R14 are bonded together to form an alkyl chain having 2 to 24 carbon atoms, M represents one alkali metal or 1 / 2 alkaline earth metal, and the Taft stereoparameter Es value of R7 is less than -0.30, and the Taft stereoparameter Es value of R9 is -0.(For solids with a Taft solid parameter Es value of -0.30 or less, at least one of R10 and R11 has a Taft solid parameter Es value of -0.30 or less.) 4. A resin composition comprising a vinyl alcohol polymer and a hydrogenated polymer composition as claimed in claim 3.

5. The resin composition of claim 4, wherein the aforementioned vinyl alcohol polymer is an ethylene-vinyl alcohol copolymer.