TW202134303A - Hydrogenated conjugated diene graft polymer and method for producing same - Google Patents

Hydrogenated conjugated diene graft polymer and method for producing same Download PDF

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TW202134303A
TW202134303A TW109146147A TW109146147A TW202134303A TW 202134303 A TW202134303 A TW 202134303A TW 109146147 A TW109146147 A TW 109146147A TW 109146147 A TW109146147 A TW 109146147A TW 202134303 A TW202134303 A TW 202134303A
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conjugated diene
polymer
graft polymer
hydrogenated conjugated
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神原浩
稻富敦
高井順矢
馬昭明
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日商可樂麗股份有限公司
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type

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Abstract

Provided is a hydrogenated conjugated diene graft polymer that has superior affinity to polar materials and is highly stable. This hydrogenated conjugated diene graft polymer comprises a side chain (b) which is formed from a polymer comprising a structural unit derived from at least one monomer selected from the group consisting of conjugated dienes and aromatic vinyl compounds, and which is bonded by a branch point, constituted by a single heteroatom having a valence of 3 or higher, to a main chain (a) formed from a polymer comprising a structural unit derived from a conjugated diene, at least some of the carbon-carbon double bonds included in the structural unit derived from the conjugated diene included in the graft polymer being hydrogenated.

Description

氫化共軛二烯系接枝聚合物、及其製造方法Hydrogenated conjugated diene graft polymer and its production method

本發明係關於一種具有與極性材料之優異親和性之同時還具有高安定性，且透明性、熱安定性優異的氫化共軛二烯系接枝聚合物、及其製造方法。The present invention relates to a hydrogenated conjugated diene graft polymer which has excellent affinity with polar materials and also has high stability, excellent transparency and thermal stability, and a method for producing the same.

歷來，已知與相同分子量之線狀聚合物相比，具有分支的聚合物流動性高，且加工性與力學特性的平衡優異。例如，已知：使利用氫矽化而接枝氯矽烷(silyl chloride)而成的聚丁二烯與具有活性陰離子聚合的活性末端的活性聚合物進行反應藉此形成共軛二烯系接枝聚合物的方法、藉由將該共軛二烯系接枝聚合物氫化而形成氫化共軛二烯系接枝聚合物的方法(參照非專利文獻1)。又，已知每1個矽原子與平均1個以上烷氧基及/或羥基結合而成的共軛二烯系星型聚合物具有優異的二氧化矽的分散性(參照專利文獻1)。 [先前技術文獻] [專利文獻]Traditionally, it has been known that, compared with linear polymers of the same molecular weight, a branched polymer has higher fluidity and an excellent balance between processability and mechanical properties. For example, it is known that a polybutadiene grafted with silyl chloride by hydrosilation is reacted with a living polymer having a living end of living anion polymerization to form a conjugated diene-based graft polymerization. A method of forming a hydrogenated conjugated diene-based graft polymer by hydrogenating the conjugated diene-based graft polymer (see Non-Patent Document 1). In addition, it is known that a conjugated diene star polymer formed by bonding an average of one or more alkoxy groups and/or hydroxyl groups per silicon atom has excellent dispersibility of silica (see Patent Document 1). [Prior Technical Literature] [Patent Literature]

[專利文獻1] 國際公開第2018/034195號 [專利文獻2] 日本專利公開2003-252927號公報 [非專利文獻][Patent Document 1] International Publication No. 2018/034195 [Patent Document 2] Japanese Patent Publication No. 2003-252927 [Non-Patent Literature]

[非專利文獻1] Macromolecules, 2001, 34, 7034[Non-Patent Document 1] Macromolecules, 2001, 34, 7034

[發明概要] [發明欲解決之課題][Summary of the invention] [The problem to be solved by the invention]

然而，非專利文獻1記載之共軛二烯系接枝聚合物或氫化共軛二烯系接枝聚合物，因不具有與極性材料具親和性之烷氧基矽基或矽醇基，故而於與玻璃、二氧化矽等之極性材料的親和性上有改善的空間。又，專利文獻1記載之共軛二烯系星型聚合物，因能引起縮合反應的烷氧基矽基及矽醇基之總含量高，故而有所謂聚合物之安定性低的問題。However, the conjugated diene-based graft polymer or hydrogenated conjugated diene-based graft polymer described in Non-Patent Document 1 does not have an alkoxysilyl group or a silanol group that has affinity for polar materials. There is room for improvement in the affinity with polar materials such as glass and silicon dioxide. In addition, the conjugated diene star polymer described in Patent Document 1 has a high total content of alkoxysilyl groups and silanol groups that can cause a condensation reaction, so there is a problem that the stability of the polymer is low.

又，非專利文獻1記載之共軛二烯系接枝聚合物於聚合物中含有為副生成物的鹵化物。鹵化物，因於燃燒時發生成為有害的生成物的原因等之環境上的問題，故而要求降低聚合物中的含量(參照專利文獻2)。又，已知鹵化物之含量多的非專利文獻1記載之共軛二烯系接枝聚合物於透明性、耐熱性有問題。於上述非專利文獻，對於降低聚合物中的鹵化物含量的手段並無任何檢討。In addition, the conjugated diene graft polymer described in Non-Patent Document 1 contains a halide as a by-product in the polymer. Halides are caused by environmental problems such as the cause of harmful products during combustion. Therefore, it is required to reduce the content in the polymer (refer to Patent Document 2). In addition, it is known that the conjugated diene-based graft polymer described in Non-Patent Document 1 having a high content of halide has problems in transparency and heat resistance. In the above-mentioned non-patent literature, there is no review on the means of reducing the halide content in the polymer.

本發明係鑑於上述之實情而作成，以提供具有與極性材料之親和性優異之同時還具有高安定性且透明性、熱安定性優異的氫化的共軛二烯系接枝聚合物、及該氫化共軛二烯系接枝聚合物之製造方法為目的。 [用以解決課題之手段]The present invention is made in view of the above facts to provide a hydrogenated conjugated diene graft polymer that has excellent affinity with polar materials and also has high stability, transparency, and thermal stability, and the The purpose is to produce a hydrogenated conjugated diene graft polymer. [Means to solve the problem]

本發明人等專心檢討的結果發現下述者而完成本發明：一種特定之氫化共軛二烯系接枝聚合物，其係連結鏈由包含共軛二烯所衍生的結構單元的聚合物所構成的主鏈，通過分支點，與側鏈結合，該側鏈係由包含選自包含共軛二烯及芳香族乙烯化合物的群組的至少1個單體所衍生的結構單元的聚合物所構成，該接枝聚合物所含的共軛二烯所衍生的結構單元中所含的碳-碳雙鍵之至少一部分經氫化；其中，該與前述分支點直接結合的選自包含烷氧基及羥基的群組的至少1個基之個數為一定之範圍內；該氫化共軛二烯系接枝聚合物具有與極性材料的親和性優異之同時還具有高安定性且透明性、熱安定性優異。As a result of intensive review, the inventors found the following to complete the present invention: a specific hydrogenated conjugated diene graft polymer, the linking chain of which is composed of a polymer containing structural units derived from a conjugated diene The main chain of the composition is bonded to a side chain through a branch point, and the side chain is composed of a polymer containing a structural unit derived from at least one monomer selected from the group consisting of a conjugated diene and an aromatic vinyl compound Structure, at least a part of the carbon-carbon double bond contained in the structural unit derived from the conjugated diene contained in the graft polymer is hydrogenated; wherein the directly bonded to the aforementioned branch point is selected from the group consisting of an alkoxy group The number of at least one group of the hydroxyl group is within a certain range; the hydrogenated conjugated diene-based graft polymer has excellent affinity with polar materials, and also has high stability, transparency, and thermal stability. Excellent stability.

即，本發明提供以下之[1]～[12]。 [1]一種氫化共軛二烯系接枝聚合物， 其係連結鏈由包含共軛二烯所衍生的結構單元的聚合物所構成的主鏈(a)，通過為分支點的價數為3以上之1個雜原子，與側鏈(b)結合，該側鏈(b)係由包含選自包含共軛二烯及芳香族乙烯化合物的群組的至少1個單體所衍生的結構單元的聚合物所構成；該接枝聚合物所含的共軛二烯所衍生的結構單元中所含的碳-碳雙鍵之至少一部分經氫化；其中， 前述主鏈(a)直接或通過連結鏈與分支點結合， 前述側鏈(b)直接與分支點結合， 前述雜原子為選自包含Si、Sn、Ge、Pb、P、B、及Al的群組的至少1者， 前述分支點之至少1者與選自包含烷氧基及羥基的群組的至少1個官能基(c)直接結合， 氫化共軛二烯系接枝聚合物每1分子之與前述分支點直接結合的官能基(c)的平均個數X與氫化共軛二烯系接枝聚合物每1分子之分支點的平均個數Y滿足下述式(2)之關係： 0＜(X/Y)＜1  (2)。 [2]如[1]記載之氫化共軛二烯系接枝聚合物，其中鹵素含量為1000ppm以下。 [3]如[1]或[2]記載之氫化共軛二烯系接枝聚合物，其中氫化共軛二烯系接枝聚合物每1分子之與前述分支點直接結合的官能基(c)的平均個數X滿足下述式(3)之關係： 0＜X≦10  (3)。 [4]如[1]～[3]中任一項記載之氫化共軛二烯系接枝聚合物，其中前述雜原子為Si。 [5]如[1]～[4]中任一項記載之氫化共軛二烯系接枝聚合物，其中氫化共軛二烯系接枝聚合物每1分子之與前述分支點直接結合的側鏈(b)之平均條數W與氫化共軛二烯系接枝聚合物每1分子之分支點的平均個數Y滿足下述式(4)之關係： 0.5≦(W/Y)  (4)。That is, the present invention provides the following [1] to [12]. [1] A hydrogenated conjugated diene graft polymer, The main chain (a) whose linking chain is composed of a polymer containing structural units derived from conjugated diene is bonded to the side chain (b) through a heteroatom with a valence of 3 or more as a branch point , The side chain (b) is composed of a polymer containing a structural unit derived from at least one monomer selected from the group consisting of a conjugated diene and an aromatic vinyl compound; At least a part of the carbon-carbon double bond contained in the structural unit derived from the conjugated diene is hydrogenated; wherein, The aforementioned main chain (a) is connected to the branch point directly or through a linking chain, The aforementioned side chain (b) directly binds to the branch point, The aforementioned heteroatom is at least one selected from the group consisting of Si, Sn, Ge, Pb, P, B, and Al, At least one of the aforementioned branch points is directly bonded to at least one functional group (c) selected from the group consisting of an alkoxy group and a hydroxyl group, The average number of functional groups (c) per molecule of the hydrogenated conjugated diene graft polymer directly bonded to the aforementioned branch point X and the average number of branch points per molecule of the hydrogenated conjugated diene graft polymer The number Y satisfies the relationship of the following formula (2): 0＜(X/Y)＜1 (2). [2] The hydrogenated conjugated diene graft polymer according to [1], wherein the halogen content is 1000 ppm or less. [3] The hydrogenated conjugated diene graft polymer as described in [1] or [2], wherein the functional group (c The average number X of) satisfies the relationship of the following formula (3): 0＜X≦10 (3). [4] The hydrogenated conjugated diene graft polymer according to any one of [1] to [3], wherein the heteroatom is Si. [5] The hydrogenated conjugated diene graft polymer according to any one of [1] to [4], wherein the hydrogenated conjugated diene graft polymer is directly bonded to the aforementioned branch point per molecule The average number W of side chains (b) and the average number Y of branch points per molecule of the hydrogenated conjugated diene graft polymer satisfy the relationship of the following formula (4): 0.5≦(W/Y) (4).

[6]一種如[1]～[5]中任一項記載之氫化共軛二烯系接枝聚合物之製造方法，其包含： (A-1)使下述式(I)所表示的活性末端聚合物(以下，將此聚合物稱為活性末端聚合物(I))、與具有包含下述式(II)所示的官能基的部分作為分支鏈的官能基改質共軛二烯系聚合物(以下，將此聚合物稱為官能基改質共軛二烯系聚合物(F))反應，而製作共軛二烯系接枝聚合物的步驟， P-X  (I) (式(I)中，P表示包含選自包含共軛二烯及芳香族乙烯化合物的群組的至少1個單體所衍生的結構單元的聚合物鏈，X表示陰離子聚合之活性末端。)[6] A method for producing a hydrogenated conjugated diene graft polymer as described in any one of [1] to [5], comprising: (A-1) A living terminal polymer represented by the following formula (I) (hereinafter, this polymer is referred to as living terminal polymer (I)), and a polymer having a function represented by the following formula (II) The functional group modified conjugated diene polymer (hereinafter, this polymer is referred to as the functional group modified conjugated diene polymer (F)) is reacted to produce a conjugated diene. Is the step of grafting polymer, P-X (I) (In formula (I), P represents a polymer chain containing a structural unit derived from at least one monomer selected from the group consisting of a conjugated diene and an aromatic vinyl compound, and X represents an anionic polymerization active end.)

Figure 02_image001
(式(II)中，V表示烷氧基或羥基，Z為Si、Sn、Ge、Pb、P、B、或Al，R1 表示碳數6～12之芳基、碳數1～12之烷基、或氫原子，N表示前述Z之價數，n為滿足下述式(5)的整數， 1≦n≦N-1  (5) n為2以上的情形，V可為相同亦可為相異，N-n為2以上的情形，R1 可為相同亦可為相異，對於主鏈，分支鏈含有複數個的情形，Z可為相同亦可為相異。)；及 (B)將上述共軛二烯系接枝聚合物所含的至少一部分之共軛二烯所衍生的結構單元中所含的碳-碳雙鍵進行氫化而形成氫化共軛二烯系接枝聚合物的步驟；及 (C)回收所獲得的氫化共軛二烯系接枝聚合物的步驟。 [7]如[6]或[7]記載之氫化共軛二烯系接枝聚合物之製造方法，其於步驟(A-1)之後且步驟(C)之前，進一步包含： (A-2)將前述共軛二烯系接枝聚合物或氫化共軛二烯系接枝聚合物中之選自包含烷氧基及羥基的群組的至少1個殘存的官能基之一部分進行不活性化的步驟。 [8]如[6]或[7]記載之氫化共軛二烯系接枝聚合物之製造方法，其中前述式(II)中之Z為Si。 [9]如[6]～[8]中任一項記載之氫化共軛二烯系接枝聚合物之製造方法，其中前述式(II)中之官能基V為烷氧基。 [10]如[1]～[5]中任一項記載之氫化共軛二烯系接枝聚合物，其係利用如[6]～[9]中任一項記載之製造方法而獲得。 [11]一種聚合物組成物，其含有如[1]～[5]及[10]中任一項記載之氫化共軛二烯系接枝聚合物。 [12]一種成形品，其係將如[11]記載之聚合物組成物成形而成。 [發明之效果]
Figure 02_image001
(In formula (II), V represents an alkoxy group or a hydroxyl group, Z represents Si, Sn, Ge, Pb, P, B, or Al, and R 1 represents an aryl group with 6 to 12 carbons, and a group with 1 to 12 carbons. Alkyl group or hydrogen atom, N represents the valence of the aforementioned Z, n is an integer satisfying the following formula (5), 1≦n≦N-1 (5) When n is 2 or more, V may be the same When Nn is 2 or more, R 1 may be the same or different. For the main chain and branch chains, Z may be the same or different.); and (B) Hydrogenating the carbon-carbon double bonds contained in the structural unit derived from at least a part of the conjugated diene contained in the above-mentioned conjugated diene graft polymer to form a hydrogenated conjugated diene graft polymer Step; and (C) the step of recovering the obtained hydrogenated conjugated diene graft polymer. [7] The method for producing a hydrogenated conjugated diene graft polymer as described in [6] or [7], after step (A-1) and before step (C), further comprising: (A-2 ) Inactivating a part of at least one remaining functional group selected from the group consisting of alkoxy and hydroxyl in the aforementioned conjugated diene graft polymer or hydrogenated conjugated diene graft polymer A step of. [8] The method for producing a hydrogenated conjugated diene graft polymer according to [6] or [7], wherein Z in the aforementioned formula (II) is Si. [9] The method for producing a hydrogenated conjugated diene graft polymer according to any one of [6] to [8], wherein the functional group V in the aforementioned formula (II) is an alkoxy group. [10] The hydrogenated conjugated diene graft polymer according to any one of [1] to [5], which is obtained by the production method according to any one of [6] to [9]. [11] A polymer composition comprising the hydrogenated conjugated diene graft polymer as described in any one of [1] to [5] and [10]. [12] A molded product formed by molding the polymer composition as described in [11]. [Effects of Invention]

依據本發明，可提供具有與極性材料之優異親和性之同時還具有高安定性且透明性、熱安定性優異的氫化共軛二烯系接枝聚合物、及其製造方法。According to the present invention, it is possible to provide a hydrogenated conjugated diene graft polymer that has excellent affinity with polar materials and also has high stability, transparency, and thermal stability, and a method for producing the same.

[用以實施發明的形態][Form to implement the invention]

以下，詳細地說明本發明。 本發明之氫化共軛二烯系接枝聚合物(以下，亦稱為氫化共軛二烯系接枝聚合物(G))係 具有下述結構：由包含共軛二烯所衍生的結構單元的聚合物所構成的主鏈(a)，通過為分支點的價數為3以上之1個雜原子，與側鏈(b)結合的結構，該側鏈(b)係由包含選自包含共軛二烯及芳香族乙烯化合物的群組的至少1個單體所衍生的結構單元的聚合物所構成； 該接枝聚合物所含的共軛二烯所衍生的結構單元中所含的碳-碳雙鍵之至少一部分經氫化； 前述主鏈(a)直接或通過連結鏈與分支點結合， 前述側鏈(b)直接與分支點結合； 前述雜原子為選自包含Si、Sn、Ge、Pb、P、B、及Al的群組的至少1者； 前述分支點之至少1者與選自包含烷氧基及羥基的群組的至少1個官能基(c)直接結合； 氫化共軛二烯系接枝聚合物(G)每1分子之與前述分支點直接結合的官能基(c)的平均個數X與氫化共軛二烯系接枝聚合物(G)每1分子之分支點的平均個數Y滿足下述式(2)之關係： 0＜(X/Y)＜1  (2)。 又，於本發明中，接枝聚合物係指具有作為幹的由高分子鏈所構成的主鏈及作為枝的由高分子鏈所構成的側鏈的聚合物，其構成主鏈的高分子鏈的單體所衍生的結構單元，與構成側鏈的高分子鏈的單體所衍生的結構單元，可為相同亦可為相異。又，於本發明中，氫化共軛二烯系接枝聚合物係指包含共軛二烯所衍生的結構單元的接枝聚合物，且為該共軛二烯所衍生的結構單元中所含的碳-碳雙鍵之至少一部分經氫化的接枝聚合物。Hereinafter, the present invention will be explained in detail. The hydrogenated conjugated diene graft polymer of the present invention (hereinafter also referred to as hydrogenated conjugated diene graft polymer (G)) is It has the following structure: a main chain (a) composed of a polymer containing a structural unit derived from a conjugated diene, a heteroatom having a valence of 3 or more through the branch point, and a side chain (b) In a bonded structure, the side chain (b) is composed of a polymer containing a structural unit derived from at least one monomer selected from the group consisting of a conjugated diene and an aromatic vinyl compound; At least a part of the carbon-carbon double bonds contained in the structural unit derived from the conjugated diene contained in the graft polymer is hydrogenated; The aforementioned main chain (a) is connected to the branch point directly or through a linking chain, The aforementioned side chain (b) directly binds to the branch point; The aforementioned heteroatom is at least one selected from the group consisting of Si, Sn, Ge, Pb, P, B, and Al; At least one of the aforementioned branch points is directly bonded to at least one functional group (c) selected from the group consisting of an alkoxy group and a hydroxyl group; The average number of functional groups (c) per molecule of the hydrogenated conjugated diene graft polymer (G) directly bonded to the aforementioned branch point X and the hydrogenated conjugated diene graft polymer (G) per 1 molecule The average number of branch points Y of the molecule satisfies the relationship of the following formula (2): 0＜(X/Y)＜1 (2). In addition, in the present invention, a graft polymer refers to a polymer having a main chain composed of a polymer chain as a stem and a side chain composed of a polymer chain as a branch, and the polymer constituting the main chain The structural unit derived from the monomer of the chain and the structural unit derived from the monomer of the polymer chain constituting the side chain may be the same or different. In addition, in the present invention, the hydrogenated conjugated diene-based graft polymer refers to a graft polymer containing a structural unit derived from a conjugated diene, and is contained in the structural unit derived from the conjugated diene A graft polymer in which at least a portion of the carbon-carbon double bond is hydrogenated.

＜主鏈(a)＞ 本發明之氫化共軛二烯系接枝聚合物(G)具有由包含共軛二烯所衍生的結構單元的聚合物所構成的主鏈(a)。又，本發明之氫化共軛二烯系接枝聚合物所含的主鏈係指包含構成主鏈的共軛二烯的全部單體所衍生的結構單元部分整體。例如，於利用本發明之製造方法製造氫化共軛二烯系接枝聚合物的情形，指為其製造所使用的官能基改質共軛二烯系聚合物(F)之先驅物的未改質之共軛二烯系聚合物(F')所衍生的部分整體。例如，該未改質之共軛二烯系聚合物(F')中包含經乙烯鍵結的丁二烯(1,3-丁二烯)所衍生的結構單元的情形，則包含到與聚合物骨架(-(C-C)n -)中之碳原子接合的-CH=CH2 部分(有加成改質的化合物的情形，則是成為-CH-CH2 -的部分)為止都稱為主鏈。<Main chain (a)> The hydrogenated conjugated diene-based graft polymer (G) of the present invention has a main chain (a) composed of a polymer containing a structural unit derived from a conjugated diene. In addition, the main chain contained in the hydrogenated conjugated diene-based graft polymer of the present invention refers to the whole part of the structural unit derived from all monomers including the conjugated diene constituting the main chain. For example, when the hydrogenated conjugated diene graft polymer is produced by the production method of the present invention, it means that the functional group used in its production is modified as the precursor of the conjugated diene polymer (F). The whole part derived from the conjugated diene polymer (F'). For example, when the unmodified conjugated diene polymer (F') contains a structural unit derived from ethylene-bonded butadiene (1,3-butadiene), it is included in the polymerization The -CH=CH 2 part where the carbon atoms in the structure (-(CC) n -) are joined (in the case of an addition-modified compound, the part that becomes -CH-CH 2 -) is called the main chain.

主鏈(a)係較佳為於其聚合物鏈骨架中不含有共軛二烯、芳香族乙烯化合物等之乙烯基單體所衍生的結構單元以外之單元(例如，具有偶合劑之殘渣所衍生的Si原子、N原子的單元)。主鏈骨架中含有前述乙烯基單體所衍生的結構單元以外之單元時，主鏈骨架會因為後述的為分支點的雜原子與碳的鍵結可被切斷的條件、或剪切或熱而開裂，故有物性容易降低的傾向。又，於主鏈的聚合物鏈末端可具有單體所衍生的結構單元以外之基。The main chain (a) is preferably a unit other than a structural unit derived from a vinyl monomer such as a conjugated diene or an aromatic vinyl compound in the polymer chain skeleton (for example, a residue with a coupling agent). Derivative Si atom, N atom unit). When the main chain skeleton contains units other than the structural units derived from the aforementioned vinyl monomers, the main chain skeleton may be cleaved due to the conditions under which the bonding between the heteroatoms at the branch point and the carbon can be cut, or shear or heat. And cracking, so the physical properties tend to decrease easily. In addition, the polymer chain end of the main chain may have a group other than the structural unit derived from the monomer.

主鏈(a)包含共軛二烯所衍生的結構單元作為構成該聚合物的單體所衍生的結構單元。就該共軛二烯而言，可列舉例如，丁二烯、異戊二烯；2,3-二甲基丁二烯、2-苯基丁二烯、1,3-戊二烯、2-甲基-1,3-戊二烯、1,3-己二烯、1,3-辛二烯、1,3-環己二烯、2-甲基-1,3-辛二烯、1,3,7-辛三烯、月桂油烯、菌綠烯、及氯丁二烯等之丁二烯及異戊二烯以外的共軛二烯。此等共軛二烯之中，以丁二烯及異戊二烯為較佳。成為上述共軛二烯所衍生的結構單元的共軛二烯係可使用單獨1種，亦可併用2種以上。The main chain (a) contains a structural unit derived from a conjugated diene as a structural unit derived from a monomer constituting the polymer. The conjugated dienes include, for example, 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, Butadiene such as 1,3,7-octatriene, myrcene, bacteriochloroprene, and chloroprene, and conjugated dienes other than isoprene. Among these conjugated dienes, butadiene and isoprene are preferred. The conjugated diene system which becomes the structural unit derived from the said conjugated diene may be used individually by 1 type, and may use 2 or more types together.

主鏈(a)，於構成其聚合物的全部單體所衍生的結構單元之中，50質量%以上為選自包含丁二烯及異戊二烯的群組的至少1個單體所衍生的結構單元為較佳的一態樣。丁二烯及異戊二烯所衍生的結構單元之合計含量，相對於主鏈(a)之全部單體所衍生的結構單元，較佳為60～100質量%，更佳為70～100質量%。Main chain (a), among the structural units derived from all monomers constituting the polymer, 50% by mass or more is derived from at least one monomer selected from the group including butadiene and isoprene The structural unit of is a preferred aspect. The total content of the structural units derived from butadiene and isoprene, relative to the structural units derived from all monomers of the main chain (a), is preferably 60-100% by mass, more preferably 70-100% by mass %.

就可含於主鏈(a)的丁二烯及異戊二烯所衍生的結構單元以外之其它單體所衍生的結構單元而言，可列舉前述的丁二烯及異戊二烯以外之共軛二烯所衍生的結構單元、芳香族乙烯化合物所衍生的結構單元等。Regarding the structural units derived from other monomers other than the butadiene and isoprene-derived structural units that can be contained in the main chain (a), examples include those other than the aforementioned butadiene and isoprene Structural units derived from conjugated dienes, structural units derived from aromatic vinyl compounds, etc.

就該芳香族乙烯化合物而言，可列舉例如，苯乙烯、α-甲基苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、4-丙基苯乙烯、4-三級丁基苯乙烯、4-環己基苯乙烯、4-十二基苯乙烯、2,4-二甲基苯乙烯、2,4-二異丙基苯乙烯、2,4,6-三甲基苯乙烯、2-乙基-4-苄基苯乙烯、4-(苯基丁基)苯乙烯、1-乙烯基萘、2-乙烯基萘、乙烯基蒽、N,N-二乙基-4-胺基乙基苯乙烯、乙烯基吡啶、4-甲氧基苯乙烯、單氯苯乙烯、二氯苯乙烯、及二乙烯基苯等。此等芳香族乙烯化合物之中，較佳為苯乙烯、α-甲基苯乙烯、及4-甲基苯乙烯。成為上述芳香族乙烯化合物所衍生的結構單元的芳香族乙烯化合物係可使用單獨1種，亦可併用2種以上。For the aromatic vinyl compound, for example, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene , 4-tertiary butylstyrene, 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, vinylanthracene, N,N -Diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, divinylbenzene, etc. Among these aromatic vinyl compounds, styrene, α-methylstyrene, and 4-methylstyrene are preferred. The aromatic vinyl compound system which becomes the structural unit derived from the said aromatic vinyl compound may be used individually by 1 type, and may use 2 or more types together.

主鏈(a)中之丁二烯及異戊二烯所衍生的結構單元以外的其它單體所衍生的結構單元之含量，較佳為50質量%以下，更佳為40質量%以下，進一步較佳為30質量%以下。例如，芳香族乙烯化合物所衍生的結構單元為上述範圍以下時，所獲得的氫化共軛二烯系接枝聚合物(G)之加工性有提升的傾向。又，利用本發明之製造方法製造氫化共軛二烯系接枝聚合物(G)的情形，藉由官能基將未改質共軛二烯系聚合物(F')改質之際，有反應性提升的傾向。The content of structural units derived from other monomers other than the structural units derived from butadiene and isoprene in the main chain (a) is preferably 50% by mass or less, more preferably 40% by mass or less, and further Preferably it is 30 mass% or less. For example, when the structural unit derived from the aromatic vinyl compound is below the above range, the processability of the obtained hydrogenated conjugated diene graft polymer (G) tends to be improved. In addition, when the hydrogenated conjugated diene-based graft polymer (G) is produced by the production method of the present invention, when the unmodified conjugated diene-based polymer (F') is modified by a functional group, there is The tendency to increase reactivity.

主鏈(a)之重量平均分子量(Mw)為1,000以上1,000,000以下者為較佳一態樣，2,000以上500,000以下為更佳，3,000以上100,000以下為進一步較佳。於本發明中，主鏈(a)之Mw，例如，於利用本發明之製造方法製造氫化共軛二烯系接枝聚合物(G)的情形，係意指後述的官能基改質共軛二烯系聚合物(F)、或未改質共軛二烯系聚合物(F')之氫化前之狀態的Mw。上述主鏈(a)之Mw為前述範圍內時，有製造時之製程通過性為優異、經濟性變良好的傾向。又，於本發明中，只要無特別說明，Mw為由凝膠滲透層析術(GPC)之測定所求得的標準聚苯乙烯換算之重量平均分子量。The weight average molecular weight (Mw) of the main chain (a) is preferably 1,000 or more and 1,000,000 or less, more preferably 2,000 or more and 500,000 or less, and more preferably 3,000 or more and 100,000 or less. In the present invention, the Mw of the main chain (a), for example, when the hydrogenated conjugated diene graft polymer (G) is produced by the production method of the present invention, means the functional group modified conjugate described later Mw in the state before hydrogenation of the diene polymer (F) or the unmodified conjugated diene polymer (F'). When the Mw of the main chain (a) is within the aforementioned range, the process passability at the time of manufacture tends to be excellent and the economic efficiency tends to be good. In addition, in the present invention, unless otherwise specified, Mw is a weight average molecular weight in terms of standard polystyrene obtained by the measurement of gel permeation chromatography (GPC).

主鏈(a)之乙烯基含量未被特別限制，90莫耳%以下為較佳一態樣，80莫耳%以下為更佳，70莫耳%以下為進一步較佳。主鏈(a)之乙烯基含量係0.5莫耳%以上為較佳，1莫耳%以上為更佳。於本發明中，「乙烯基含量」係意指氫化前之共軛二烯系接枝聚合物(以下，亦稱為共軛二烯系接枝聚合物(G'))中所含的共軛二烯所衍生的結構單元之合計100莫耳%中，以1,2-鍵結、3,4-鍵結(菌綠烯以外的情形)、及3,13-鍵結(菌綠烯的情形)進行鍵結的共軛二烯所衍生的結構單元(以1,4-鍵結(菌綠烯以外的情形)及1,13-鍵結(菌綠烯的情形)以外進行鍵結的共軛二烯所衍生的結構單元)之合計莫耳%。又，於本發明中，由氫化前之聚合物所含的共軛二烯所衍生的結構單元上的鍵結形態而求得的乙烯基含量，於氫化後之聚合物中，亦定義為該聚合物的乙烯基含量。於氫化前之聚合物中，使用1 H-NMR，從來自以1,2-鍵結、3,4-鍵結(菌綠烯以外的情形)、及3,13-鍵結(菌綠烯的情形)進行結合的共軛二烯所衍生的結構單元的峰、與來自以1,4-鍵結(菌綠烯以外的情形)及1,13-鍵結(菌綠烯的情形)進行結合的共軛二烯所衍生的結構單元的峰的面積比，而算出乙烯基含量。The vinyl content of the main chain (a) is not particularly limited, and it is preferably 90 mol% or less, more preferably 80 mol% or less, and even more preferably 70 mol% or less. The vinyl content of the main chain (a) is preferably 0.5 mol% or more, and more preferably 1 mol% or more. In the present invention, "vinyl content" means the copolymer contained in the conjugated diene graft polymer before hydrogenation (hereinafter, also referred to as conjugated diene graft polymer (G')) In the total 100 mol% of the structural units derived from conjugated diene, 1,2-bond, 3,4-bond (other than bacterene), and 3,13-bonded (bacterial In the case of) the structural unit derived from the bonded conjugated diene (in the case of 1,4-bonding (except for bacterene) and 1,13-bonding (in the case of bacterene) The total mole% of the structural unit derived from the conjugated diene). In addition, in the present invention, the vinyl content calculated from the bonding form on the structural unit derived from the conjugated diene contained in the polymer before hydrogenation is also defined as the content of the polymer after hydrogenation. The vinyl content of the polymer. In the polymer before hydrogenation, using 1 H-NMR, from 1,2-bond, 3,4-bond (except for bacterene), and 3,13-bond In the case of) the peak of the structural unit derived from the conjugated diene that is bound is combined with 1,4-bond (in the case of bacterolene) and 1,13-bond (in the case of bacterin) The vinyl content is calculated from the peak area ratio of the structural unit derived from the bonded conjugated diene.

主鏈(a)之乙烯基含量可因應目的而設計，例如，乙烯基含量小於50莫耳%時，後述的主鏈(a)之玻璃轉移溫度(Tg)變低，所獲得的氫化共軛二烯系接枝聚合物(G)之流動性、低溫特性有優異的傾向。又，為50莫耳%以上時，所獲得的氫化共軛二烯系接枝聚合物(G)之耐熱性有優異的傾向。又，主鏈(a)為僅由丁二烯所衍生的結構單元構成的情形，為了防止氫化後之結晶化所致的性能降低，將主鏈(a)之乙烯基含量作成25莫耳%以上為較佳。The vinyl content of the main chain (a) can be designed according to the purpose. For example, when the vinyl content is less than 50 mol%, the glass transition temperature (Tg) of the main chain (a) described later becomes lower, and the obtained hydrogenated conjugate The diene graft polymer (G) tends to be excellent in fluidity and low-temperature characteristics. In addition, when it is 50 mol% or more, the obtained hydrogenated conjugated diene graft polymer (G) tends to be excellent in heat resistance. In addition, when the main chain (a) is composed only of structural units derived from butadiene, in order to prevent performance degradation due to crystallization after hydrogenation, the vinyl content of the main chain (a) is set to 25 mol% The above is better.

又，於利用本發明之製造方法製造氫化共軛二烯系接枝聚合物(G)的情形，主鏈(a)之乙烯基含量，例如，可藉由控制於製造未改質共軛二烯系聚合物(F')之際所使用的溶劑之種類、因應必要使用的極性化合物、聚合溫度等，作成所冀望的值。In addition, in the case of producing the hydrogenated conjugated diene graft polymer (G) by the production method of the present invention, the vinyl content of the main chain (a) can be controlled by, for example, the production of unmodified conjugated diene The type of solvent used in the case of the olefin polymer (F'), the polar compound used as necessary, the polymerization temperature, etc., are made to the desired value.

主鏈(a)之玻璃轉移溫度(Tg)可依丁二烯、異戊二烯、及其它共軛二烯等之共軛二烯所衍生的結構單元的乙烯基含量、共軛二烯的種類、共軛二烯以外之單體所衍生的結構單元的含量等而變化，但-150～50℃為較佳，-130～50℃為更佳，-130～30℃為進一步較佳。Tg為上述範圍時，例如，可抑制黏度變高且處理變容易。又，於本發明中，Tg為由示差掃描熱量測定(DSC)測定而求得且為DDSC之峰頂之值。The glass transition temperature (Tg) of the main chain (a) can be based on the vinyl content of structural units derived from conjugated dienes such as butadiene, isoprene, and other conjugated dienes, and the content of conjugated dienes. The type, the content of the structural unit derived from the monomer other than the conjugated diene, etc. vary, but -150 to 50°C is preferable, -130 to 50°C is more preferable, and -130 to 30°C is even more preferable. When Tg is in the above range, for example, the viscosity can be suppressed from increasing and the handling can be facilitated. In the present invention, Tg is the value of the peak top of DDSC, which is obtained by differential scanning calorimetry (DSC) measurement.

＜側鏈(b)＞ 本發明之氫化共軛二烯系接枝聚合物(G)具有側鏈(b)，該側鏈(b)係由包含選自包含共軛二烯及芳香族乙烯化合物的群組的至少1個單體所衍生的結構單元的聚合物所構成。＜Side chain (b)＞ The hydrogenated conjugated diene graft polymer (G) of the present invention has a side chain (b) composed of at least 1 selected from the group consisting of conjugated dienes and aromatic vinyl compounds. It is composed of a polymer of structural units derived from each monomer.

側鏈(b)包含選自包含共軛二烯及芳香族乙烯化合物的群組的至少1個單體所衍生的結構單元作為構成該聚合物的單體所衍生的結構單元。The side chain (b) contains a structural unit derived from at least one monomer selected from the group consisting of a conjugated diene and an aromatic vinyl compound as a structural unit derived from the monomer constituting the polymer.

可構成側鏈(b)之單體所衍生的結構單元的共軛二烯之具體例，與構成主鏈(a)之單體所衍生的結構單元的共軛二烯之具體例相同。側鏈(b)所含的共軛二烯所衍生的結構單元的共軛二烯之中，丁二烯及異戊二烯為較佳。上述共軛二烯可使用單獨1種，亦可併用2種以上。The specific examples of the conjugated diene which can constitute the structural unit derived from the monomer of the side chain (b) are the same as the specific examples of the conjugated diene which constitutes the structural unit derived from the monomer of the main chain (a). Among the conjugated dienes of the structural unit derived from the conjugated diene contained in the side chain (b), butadiene and isoprene are preferred. The said conjugated diene may be used individually by 1 type, and may use 2 or more types together.

可構成側鏈(b)之單體所衍生的結構單元的芳香族乙烯化合物之具體例，與可構成主鏈(a)之單體所衍生的結構單元的芳香族乙烯化合物之具體例相同。此等芳香族乙烯化合物之中，較佳為苯乙烯、α-甲基苯乙烯、及4-甲基苯乙烯。成為上述芳香族乙烯化合物所衍生的結構單元的芳香族乙烯化合物係可使用單獨1種，亦可併用2種以上。The specific examples of the aromatic vinyl compound which can constitute the structural unit derived from the monomer of the side chain (b) are the same as the specific examples of the aromatic vinyl compound which can constitute the structural unit derived from the monomer of the main chain (a). Among these aromatic vinyl compounds, styrene, α-methylstyrene, and 4-methylstyrene are preferred. The aromatic vinyl compound system which becomes the structural unit derived from the said aromatic vinyl compound may be used individually by 1 type, and may use 2 or more types together.

側鏈(b)，其聚合物鏈的骨架可為：僅由1種共軛二烯或1種芳香族乙烯化合物所衍生的結構單元所構成的均聚物、由選自包含共軛二烯及芳香族乙烯化合物的群組的2種以上單體所衍生的結構單元所構成的共聚物、或由選自包含共軛二烯及芳族乙烯化合物的群組的1種以上單體與共軛二烯及芳族乙烯化合物以外的1種以上乙烯單體所衍生的結構單元所構成的共聚物。又，構成側鏈(b)的聚合物可為單獨1種，亦可為具有相異結構的2種以上。For the side chain (b), the polymer chain backbone may be: a homopolymer composed of structural units derived from only one conjugated diene or one aromatic vinyl compound, and one selected from the group consisting of conjugated diene A copolymer composed of structural units derived from two or more monomers in the group of aromatic vinyl compounds, or one or more monomers selected from the group consisting of conjugated dienes and aromatic vinyl compounds, and a copolymer A copolymer composed of structural units derived from one or more vinyl monomers other than conjugated dienes and aromatic vinyl compounds. In addition, the polymer constituting the side chain (b) may be one type alone, or two or more types having different structures.

可構成側鏈(b)的共軛二烯所衍生的結構單元之比率未被特別限制，可因應目的而設計，但50質量%以上為較佳，60質量%以上為更佳，70質量%以上為特佳，可為100質量%。共軛二烯所衍生的結構單元之比率為50質量%以上時，所獲得的氫化共軛二烯系接枝聚合物(G)之加工性有提升的傾向。The ratio of the structural unit derived from the conjugated diene that can constitute the side chain (b) is not particularly limited, and can be designed according to the purpose, but 50% by mass or more is preferred, 60% by mass or more is more preferably, 70% by mass The above is particularly preferable, and it may be 100% by mass. When the ratio of the structural unit derived from the conjugated diene is 50% by mass or more, the processability of the obtained hydrogenated conjugated diene-based graft polymer (G) tends to be improved.

可構成側鏈(b)的芳香族乙烯化合物所衍生的結構單元之比率未被特別限制，可因應目的而設計，但50質量%以上為較佳，60質量%以上為更佳，70質量%以上為特佳，可為100質量%。芳香族乙烯化合物所衍生的結構單元之比率為50質量%以上時，所獲得的氫化共軛二烯系接枝聚合物(G)之力學特性有提升的傾向。The ratio of the structural units derived from the aromatic vinyl compound that can constitute the side chain (b) is not particularly limited, and can be designed according to the purpose, but 50% by mass or more is preferred, 60% by mass or more is more preferred, and 70% by mass The above is particularly preferable, and it may be 100% by mass. When the ratio of the structural unit derived from the aromatic vinyl compound is 50% by mass or more, the mechanical properties of the obtained hydrogenated conjugated diene graft polymer (G) tend to be improved.

側鏈(b)係較佳為於其聚合物鏈骨架中不含有共軛二烯、芳香族乙烯化合物等之乙烯基單體所衍生的結構單元以外之單元(例如，具有偶合劑之殘渣所衍生的Si原子、N原子的單元)。側鏈(b)之聚合物鏈骨架中含有前述乙烯基單體所衍生的結構單元以外之單元時，主鏈骨架會因為後述的為分支點的雜原子與碳的結合可被切斷的條件、或剪切或熱而開裂，故有物性容易降低的傾向。又，於側鏈的聚合物鏈末端可具有單體所衍生的結構單元以外之基。The side chain (b) is preferably a unit other than a structural unit derived from a vinyl monomer such as a conjugated diene and an aromatic vinyl compound (for example, a residue with a coupling agent) in the polymer chain backbone. Derivative Si atom, N atom unit). When the polymer chain backbone of the side chain (b) contains units other than the structural units derived from the aforementioned vinyl monomers, the main chain backbone will be severable due to the conditions that the bonding of heteroatoms and carbons at the branch point described later , Or cracking due to shearing or heat, so the physical properties tend to decrease easily. In addition, the polymer chain end of the side chain may have a group other than the structural unit derived from the monomer.

側鏈(b)之重量平均分子量(Mw)為1,000以上200,000以下為較佳一態樣，2,000以上150,000以下為更佳，3,000以上100,000以下為進一步較佳。於本發明中，側鏈(b)之Mw，例如，於利用本發明之製造方法製造氫化共軛二烯系接枝聚合物(G)的情形，即為後述的活性末端聚合物(I)之氫化前之狀態的Mw。上述側鏈(b)之Mw為前述範圍內時，有製造時之製程通過性為優異、經濟性變良好的傾向。The weight average molecular weight (Mw) of the side chain (b) is preferably 1,000 or more and 200,000 or less, more preferably 2,000 or more and 150,000 or less, and more preferably 3,000 or more and 100,000 or less. In the present invention, the Mw of the side chain (b), for example, when the hydrogenated conjugated diene graft polymer (G) is produced by the production method of the present invention, is the living terminal polymer (I) described later The Mw of the state before hydrogenation. When the Mw of the side chain (b) is within the aforementioned range, the process passability at the time of manufacture tends to be excellent, and the economic efficiency tends to be improved.

側鏈(b)之乙烯基含量未被特別限制，但90莫耳%以下為較佳一態樣，80莫耳%以下為更佳，70莫耳%以下為進一步較佳。側鏈(b)之乙烯基含量係0.5莫耳%以上為較佳，1莫耳%以上為更佳。例如，於利用本發明之製造方法製造氫化共軛二烯系接枝聚合物(G)的情形，側鏈(b)之乙烯基含量，係藉由為後述的氫化前之活性末端聚合物(I)之1 H-NMR光譜，與為主鏈(a)的情形同樣地算出。The vinyl content of the side chain (b) is not particularly limited, but it is preferably 90 mol% or less, more preferably 80 mol% or less, and even more preferably 70 mol% or less. The vinyl content of the side chain (b) is preferably 0.5 mol% or more, and more preferably 1 mol% or more. For example, when the hydrogenated conjugated diene graft polymer (G) is produced by the production method of the present invention, the vinyl content of the side chain (b) is determined by the reactive terminal polymer before hydrogenation described later ( The 1 H-NMR spectrum of I) is calculated in the same manner as in the case of the main chain (a).

側鏈(b)之乙烯基含量可因應目的而設計，例如，乙烯基含量小於50莫耳%時，後述的側鏈(b)之玻璃轉移溫度(Tg)變低，所獲得的氫化共軛二烯系接枝聚合物(G)之流動性、低溫特性有優異的傾向。又，為50莫耳%以上時，所獲得的氫化共軛二烯系接枝聚合物(G)之耐熱性有優異的傾向。又，側鏈(b)為僅由丁二烯所衍生的結構單元構成的情形，為了防止氫化後之結晶化所致的性能降低，將側鏈(b)之乙烯基含量作成25莫耳%以上為較佳。The vinyl content of the side chain (b) can be designed according to the purpose. For example, when the vinyl content is less than 50 mol%, the glass transition temperature (Tg) of the side chain (b) described later becomes lower, and the obtained hydrogenated conjugate The diene graft polymer (G) tends to be excellent in fluidity and low-temperature characteristics. In addition, when it is 50 mol% or more, the obtained hydrogenated conjugated diene graft polymer (G) tends to be excellent in heat resistance. In addition, when the side chain (b) is composed of only structural units derived from butadiene, in order to prevent performance degradation due to crystallization after hydrogenation, the vinyl content of the side chain (b) is set to 25 mol% The above is better.

又，於利用本發明之製造方法製造氫化共軛二烯系接枝聚合物(G)的情形，側鏈(b)之乙烯基含量，例如，可藉由控制於製造側鏈(b)之構成要素的活性末端聚合物(I)之際所使用的溶劑之種類、因應必要使用的極性化合物、聚合溫度等，作成所冀望的值。In addition, when the hydrogenated conjugated diene graft polymer (G) is produced by the production method of the present invention, the vinyl content of the side chain (b) can be controlled, for example, by controlling the production of the side chain (b) The type of solvent used for the living terminal polymer (I) of the constituent element, the polar compound used as necessary, the polymerization temperature, etc., are made to the desired value.

側鏈(b)之玻璃轉移溫度(Tg)可依共軛二烯所衍生的結構單元之乙烯基含量、共軛二烯的種類、共軛二烯以外之單體所衍生的結構單元的含量等而變化，但-150～50℃為較佳，-130～50℃為更佳，-130～30℃為進一步較佳。Tg為上述範圍時，例如，可抑制黏度變高且處理變容易。The glass transition temperature (Tg) of the side chain (b) can be based on the vinyl content of the structural unit derived from the conjugated diene, the type of conjugated diene, and the content of the structural unit derived from the monomer other than the conjugated diene It may vary, but -150 to 50°C is preferred, -130 to 50°C is more preferred, and -130 to 30°C is even more preferred. When Tg is in the above range, for example, the viscosity can be suppressed from increasing and the handling can be facilitated.

＜氫化共軛二烯系接枝聚合物(G)＞ 本發明之氫化共軛二烯系接枝聚合物(G)係主鏈(a)通過為分支點的價數為3以上之1個雜原子與側鏈(b)結合，且前述分支點之至少1者與選自包含烷氧基及羥基的群組的至少1個官能基(c)結合的氫化共軛二烯系接枝聚合物(G)。<Hydrogenated conjugated diene graft polymer (G)> The hydrogenated conjugated diene graft polymer (G) of the present invention is based on the main chain (a) via a heteroatom having a valence of 3 or more as a branch point and is bonded to the side chain (b), and the aforementioned branch point Hydrogenated conjugated diene graft polymer (G) in which at least one is bonded to at least one functional group (c) selected from the group containing an alkoxy group and a hydroxyl group.

前述主鏈(a)直接或通過連結鏈與分支點結合，前述側鏈(b)直接與分支點結合，前述官能基(c)直接與分支點結合。此處，直接與分支點結合，係意指構成主鏈的單體所衍生的結構單元部分與分支點直接結合。通過連結鏈與分支點結合，係意指構成主鏈的單體所衍生的結構單元部分與連結鏈的一端的末端結合，該連結鏈的另一端的末端與分支點直接結合。例如，於經1,2-鍵結的丁二烯所衍生的結構單元與分支點結合的情形，下述式(III-1)所示的情形即為主鏈與分支點直接結合的情形，下述式(III-2)所示的情形即為主鏈通過連結鏈與分支點結合的情形。The main chain (a) is directly or through a linking chain and is directly bonded to the branch point, the side chain (b) is directly bonded to the branch point, and the functional group (c) is directly bonded to the branch point. Here, the direct bonding to the branch point means that the part of the structural unit derived from the monomer constituting the main chain is directly bonded to the branch point. By combining the linking chain with the branch point, it means that the structural unit part derived from the monomer constituting the main chain is bound to the end of one end of the linking chain, and the end of the other end of the linking chain is directly bound to the branch point. For example, in the case where a structural unit derived from 1,2-bonded butadiene is bonded to a branch point, the following formula (III-1) is the case where the main chain is directly bonded to the branch point. The case represented by the following formula (III-2) is a case where the main chain is connected to the branch point through the linking chain.

Figure 02_image003
Figure 02_image003

上述式(III-1)及(III-2)中，Z0 為成為分支點的雜原子，R2a 為連結鏈。R2a 為2價之有機基，但可具有雜原子的伸烷基為較佳。In the above formulas (III-1) and (III-2), Z 0 is a heteroatom that becomes a branch point, and R 2a is a linking chain. R 2a is a divalent organic group, but an alkylene group which may have a heteroatom is preferred.

將包含前述主鏈(a)與分支點的結合形態的自主鏈起之分支部分以化學式表示時，有如下述式(III-3)的包含分支點直接與主鏈(a)結合的形態的分支部分、如下述式(III-4)的包含通過連結鏈與分支點結合的形態的分支部分。於此等之分支部分之中，亦冀望如式(III-4)的包含通過連結鏈與分支點結合的形態的分支結構。When the branch portion from the main chain including the binding form of the main chain (a) and the branch point is represented by a chemical formula, it is like the form in which the branch point is directly bound to the main chain (a) in the following formula (III-3) The branch part is a branch part including a form in which a branch point is connected by a linking chain as shown in the following formula (III-4). Among these branch parts, it is also hoped that the branch structure of formula (III-4) includes a morphology that is combined with a branch point through a linking chain.

Figure 02_image005
Figure 02_image005

於上述式(III-3)及(III-4)，波浪線部分為主鏈(a)，V為官能基(c)，Z1 為分支點，P為側鏈(b)，R2b 為連結鏈。In the above formulas (III-3) and (III-4), the wavy line part is the main chain (a), V is the functional group (c), Z 1 is the branch point, P is the side chain (b), and R 2b is Link the chain.

式(III-3)及(III-4)中，V表示烷氧基或羥基，Z1 為Si、Sn、Ge、Pb、P、B、或Al，R2b 表示可具有雜原子的碳數1～12之伸烷基，R3 表示碳數6～12之芳基、碳數1～12之烷基、或氫原子，P表示包含選自包含共軛二烯及芳香族乙烯化合物的群組的至少1個單體所衍生的結構單元的聚合物鏈。N表示前述Z之價數，m及n各自獨立為滿足下述式(6)的整數； 0≦m≦N-1，0≦n≦N-1 (6) m為2以上的情形，P可為相同亦可為相異，n為2以上的情形，V可為相同亦可為相異，N-m-n為2以上的情形，R3 可為相同亦可為相異，分支點對主鏈為包含複數個的情形，Z1 可為相同或相異。惟，於滿足上述式(6)之關係的同時，本發明之氫化共軛二烯系接枝聚合物(G)必須含有V(官能基(c))及P(側鏈(b))。又，本發明之氫化共軛二烯系接枝聚合物(G)，因相對於1條主鏈，只要有1條以上的側鏈即可，故雖可包含未結合側鏈的Z1 (m為0的Z1 )，但此情形亦將Z1 定義為分支點。In formulas (III-3) and (III-4), V represents an alkoxy group or a hydroxyl group, Z 1 is Si, Sn, Ge, Pb, P, B, or Al, and R 2b represents the number of carbons that may have heteroatoms 1-12 alkylene, R 3 represents an aryl group with 6 to 12 carbons, an alkyl group with 1 to 12 carbons, or a hydrogen atom, and P represents a group selected from the group consisting of conjugated dienes and aromatic vinyl compounds A polymer chain of a structural unit derived from at least one monomer of the group. N represents the valence of the aforementioned Z, m and n are each independently an integer satisfying the following formula (6); 0≦m≦N-1, 0≦n≦N-1 (6) When m is 2 or more, P It can be the same or different. When n is 2 or more, V can be the same or different. When Nmn is 2 or more, R 3 can be the same or different. The branch point to the main chain is In the case of a plural number, Z 1 may be the same or different. However, while satisfying the relationship of the above formula (6), the hydrogenated conjugated diene graft polymer (G) of the present invention must contain V (functional group (c)) and P (side chain (b)). In addition, the hydrogenated conjugated diene graft polymer (G) of the present invention only needs to have one or more side chains with respect to one main chain. Therefore, although Z 1 ( Z 1 where m is 0), but in this case, Z 1 is also defined as a branch point.

上述分支點包含1個雜原子，該雜原子為價數3以上的雜原子。成為分支點的價數3以上之雜原子為選自包含Si、Sn、Ge、Pb、P、B、及Al的群組的至少1者。此等雜原子之中以Si、Sn、B為較佳，Si為更佳。The branch point includes one heteroatom, and the heteroatom is a heteroatom with a valence of 3 or more. The heteroatom having a valence of 3 or more used as a branch point is at least one member selected from the group consisting of Si, Sn, Ge, Pb, P, B, and Al. Among these heteroatoms, Si, Sn, and B are preferred, and Si is more preferred.

成為上述基V的官能基(c)為選自包含烷氧基及羥基的群組的至少1者。就烷氧基而言，可列舉例如，甲氧基、乙氧基、丙氧基等。上述官能基(c)之中，由與極性材料的親和性的觀點來看，甲氧基、乙氧基、及羥基為較佳。官能基(c)可為單獨1種之基，亦可為2種以上之複數個之基。The functional group (c) used as the group V is at least one member selected from the group consisting of an alkoxy group and a hydroxyl group. As for the alkoxy group, for example, a methoxy group, an ethoxy group, a propoxy group and the like can be mentioned. Among the above-mentioned functional groups (c), a methoxy group, an ethoxy group, and a hydroxyl group are preferable from the viewpoint of affinity with a polar material. The functional group (c) may be a single type of group, or may be a plurality of groups of two or more types.

上述式(III-3)及(III-4)中之R3 表示碳數6～12之芳基、碳數1～12之烷基、或氫原子。此等R3 之中，以碳數1～6之烷基為較佳，正丁基、二級丁基、正丙基、異丙基、乙基、甲基為更佳。R3 可為單獨1種之基，亦可為2種以上之複數個基。 R 3 in the above formulas (III-3) and (III-4) represents an aryl group having 6 to 12 carbons, an alkyl group having 1 to 12 carbons, or a hydrogen atom. Among these R 3 , an alkyl group having 1 to 6 carbon atoms is preferred, and n-butyl, di-butyl, n-propyl, isopropyl, ethyl, and methyl are more preferred. R 3 may be a single base or two or more bases.

就可成為R2b 的具有雜原子的碳數1～12之伸烷基而言，具有S的碳數1～12之伸烷基為較佳，SR2b' (R2b' 表示碳數1～12之伸烷基)為更佳。As for the alkylene group having a hetero atom and having a carbon number of 1 to 12 which can become R 2b , an alkylene group having 1 to 12 carbon atoms having S is preferred, and SR 2b' (R 2b' represents a carbon number of 1 to The alkylene of 12) is more preferred.

本發明之氫化共軛二烯系接枝聚合物(G)，著眼於該接枝聚合物所含的分支點的雜原子的情形，將該雜原子之價數設為N，將對1個之分支點直接結合的側鏈(b)之平均條數設為B，將與1個之分支點結合的前述官能基(c)的平均個數設為C的情形，成為滿足下述式(1)之關係者。藉由滿足此條件，分支點直接或通過連結鏈而與主鏈(a)結合，本發明之氫化共軛二烯系接枝聚合物(G)會成為至少包含側鏈(b)與官能基(c)。 N-1≧B＋C， B＞0， C＞0  (1)The hydrogenated conjugated diene graft polymer (G) of the present invention focuses on the heteroatom at the branch point contained in the graft polymer, and the valence of the heteroatom is set to N. When the average number of side chains (b) directly bonded to the branch point is set to B, and the average number of the aforementioned functional groups (c) bonded to one branch point is set to C, the following formula ( 1) The related person. By satisfying this condition, the branch point is bonded to the main chain (a) directly or through the linking chain, and the hydrogenated conjugated diene graft polymer (G) of the present invention becomes at least containing the side chain (b) and the functional group (c). N-1≧B＋C, B＞0, C＞0 (1)

本發明之氫化共軛二烯系接枝聚合物(G)，氫化共軛二烯系接枝聚合物(G)每1分子之與上述分支點直接結合的官能基(c)的平均個數X與氫化共軛二烯系接枝聚合物(G)每1分子之分支點之平均個數Y係滿足下述式(2)之關係。 0＜(X/Y)＜1  (2) 上述(X/Y)為0時，氫化共軛二烯系接枝聚合物(G)與極性材料的親和性有變差的傾向，上述(X/Y)為1以上時，氫化共軛二烯系接枝聚合物(G)之安定性有降低的傾向。The hydrogenated conjugated diene graft polymer (G) and the hydrogenated conjugated diene graft polymer (G) of the present invention have an average number of functional groups (c) directly bonded to the branch point per molecule The average number of branch points per molecule of X and the hydrogenated conjugated diene graft polymer (G) Y satisfies the relationship of the following formula (2). 0＜(X/Y)＜1 (2) When the above (X/Y) is 0, the affinity of the hydrogenated conjugated diene graft polymer (G) with the polar material tends to deteriorate. When the above (X/Y) is 1 or more, the hydrogenated conjugated diene The stability of the olefinic graft polymer (G) tends to decrease.

由與極性材料的親和性及安定性更優異的觀點來看，上述(X/Y)係0.01以上0.99以下之範圍為較佳，0.01以上0.9以下之範圍為更佳，0.01以上0.5以下之範圍為特佳。於本發明中，(X/Y)(氫化共軛二烯系接枝聚合物(G)所含的每1分支點之官能基(c)之平均個數)，例如，於Z為Si的情形，係由測定共軛二烯系接枝聚合物(G)之29 Si-NMR的結果而求得。具體而言，係將有1個官能基(c)結合的Si、有2個官能基(c)結合的Si等之積分值乘以官能基之個數而成者進行合計，藉由與積分值之單純合計進行比較而算出。Z為Si以外之雜原子的情形亦可同樣地求得(X/Y)。From the viewpoint of more excellent affinity and stability with polar materials, the above (X/Y) is preferably in the range of 0.01 or more and 0.99 or less, more preferably 0.01 or more and 0.9 or less, and 0.01 or more and 0.5 or less. It is especially good. In the present invention, (X/Y) (the average number of functional groups (c) per branch point contained in the hydrogenated conjugated diene graft polymer (G)), for example, when Z is Si The situation is determined from the result of 29 Si-NMR measurement of the conjugated diene graft polymer (G). Specifically, the integral value of Si with one functional group (c) bonded, Si with two functional groups (c) bonded, etc., is multiplied by the number of functional groups, and the total is calculated by adding It is calculated by comparing the simple total of the values. When Z is a heteroatom other than Si, (X/Y) can be obtained in the same manner.

又，氫化共軛二烯系接枝聚合物(G)每1分子之分支點的平均個數Y，使用利用電感耦合電漿質譜分析裝置(ICP-MS)所測定的氫化共軛二烯系接枝聚合物(G)中之特定的雜原子(Si、Sn、Ge、Pb、P、B、及Al)之含量(質量%)及標準聚苯乙烯換算的數量平均分子量(Mn)而由下述式(7)求得。 (氫化共軛二烯系接枝聚合物(G)每1分子之分支點的平均個數Y)=[(雜原子之含量(質量%))/100]×[(數量平均分子量Mn)/(苯乙烯所衍生的結構單元之分子量)×(共軛二烯及因應必要而包含的共軛二烯以外之其它單體所衍生的結構單元之平均分子量)]/(雜原子之原子量)  (7)In addition, the average number of branch points Y per molecule of the hydrogenated conjugated diene graft polymer (G) was measured using an inductively coupled plasma mass spectrometer (ICP-MS). The content (mass%) of the specific heteroatoms (Si, Sn, Ge, Pb, P, B, and Al) in the graft polymer (G) and the number average molecular weight (Mn) converted from standard polystyrene are determined by It is obtained by the following formula (7). (Hydrogenated conjugated diene graft polymer (G) average number of branch points per molecule Y)=((heteroatom content (mass%))/100)×((number average molecular weight Mn)/ (Molecular weight of structural unit derived from styrene)×(Average molecular weight of structural unit derived from conjugated diene and other monomers other than conjugated diene included if necessary))/(atomic weight of heteroatoms) ( 7)

本發明之氫化共軛二烯系接枝聚合物(G)，氫化共軛二烯系接枝聚合物(G)每1分子之與上述分支點直接結合的官能基(c)的平均個數X，滿足下述式(3)之關係為較佳。 0＜X≦10  (3) 官能基(c)的平均個數X係利用後述的方法而算出。上述X為0時，氫化共軛二烯系接枝聚合物(G)與極性材料的親和性有變差的傾向，上述X超過10時，氫化共軛二烯系接枝聚合物(G)之安定性有降低的傾向。The hydrogenated conjugated diene graft polymer (G) and the hydrogenated conjugated diene graft polymer (G) of the present invention have an average number of functional groups (c) directly bonded to the branch point per molecule X preferably satisfies the relationship of the following formula (3). 0＜X≦10 (3) The average number X of functional groups (c) is calculated by the method described later. When the above X is 0, the affinity of the hydrogenated conjugated diene graft polymer (G) with polar materials tends to deteriorate, and when the above X exceeds 10, the hydrogenated conjugated diene graft polymer (G) Its stability tends to decrease.

由與極性材料的親和性及安定性更優異的觀點來看，X為0.01以上9.9以下之範圍為較佳，0.02以上9以下之範圍為更佳，0.05以上5以下之範圍為特佳。於本發明中，氫化共軛二烯系接枝聚合物(G)每1分子之與上述分支點直接結合的官能基(c)的平均個數X，係使用上述氫化共軛二烯系接枝聚合物(G)所含的每1個分支點的官能基(c)的平均個數(X/Y)與上述氫化共軛二烯系接枝聚合物(G)每1分子之分支點的平均個數Y而求得。From the viewpoint of more excellent affinity and stability with the polar material, X is preferably in the range of 0.01 or more and 9.9 or less, more preferably in the range of 0.02 or more and 9 or less, and particularly preferably in the range of 0.05 or more and 5 or less. In the present invention, the average number X of functional groups (c) directly bonded to the branch point per molecule of the hydrogenated conjugated diene graft polymer (G) is based on the hydrogenated conjugated diene graft polymer (G). The average number (X/Y) of functional groups (c) per branch point contained in the branch polymer (G) is the same as the branch point per molecule of the above-mentioned hydrogenated conjugated diene-based graft polymer (G) The average number Y is obtained.

又，與上述分支點直接結合的側鏈(b)之條數及官能基(c)之個數，於利用本發明之製造方法製造氫化共軛二烯系接枝聚合物(G)的情形，可藉由例如，後述的步驟(A-1)中的活性末端聚合物(I)與官能基改質共軛二烯系聚合物(F)之進料量之莫耳比、為了將後述的步驟(A-2)中的選自包含烷氧基及羥基的群組的至少1個殘存的官能基(未反應而存在的官能基V)之一部分不活性化的試藥之使用量及反應時間、及因應必要所使用的極性化合物之種類及添加量，而調整至所冀望之範圍。In addition, the number of side chains (b) and the number of functional groups (c) directly bonded to the above-mentioned branch points are used when the hydrogenated conjugated diene graft polymer (G) is produced by the production method of the present invention , For example, the molar ratio of the feed amount of the living terminal polymer (I) and the functional group in the step (A-1) described later can be used to modify the conjugated diene polymer (F). In step (A-2), at least one remaining functional group selected from the group containing alkoxy and hydroxyl group (functional group V that is not reacted) is partially inactivated and the amount of reagent used and The reaction time and the type and amount of the polar compound used as necessary are adjusted to the desired range.

氫化共軛二烯系接枝聚合物(G)之安定性，可藉由例如於常溫、常壓下長期間保存之際的外觀變化及不溶分(膠化物)之生成而評價。又，亦可藉由將氫化共軛二烯系接枝聚合物(G)加熱、減壓，而促進烷氧基矽基或矽醇基之縮合反應的條件，來進行評價。The stability of the hydrogenated conjugated diene-based graft polymer (G) can be evaluated by, for example, the appearance change and the generation of insoluble matter (gelatinized product) during long-term storage at normal temperature and normal pressure. In addition, it is also possible to evaluate the conditions under which the hydrogenated conjugated diene graft polymer (G) is heated and reduced in pressure to promote the condensation reaction of the alkoxysilyl group or the silanol group.

與極性材料之親和性，可藉由例如，於玻璃基材上塗布氫化共軛二烯系接枝聚合物(G)、或含有共氫化共軛二烯系接枝聚合物(G)的聚合物組成物，進行一定時間加熱而硬化後，實施剝離強度之測定及方格試驗等而評價。又，藉由烷氧基矽基或矽醇基之縮合反應性，可評價與玻璃及矽石等之極性材料的反應性、及親和性。將包含氫化共軛二烯系接枝聚合物(G)的溶液，於酸性或鹼性條件下振盪之際，於縮合反應性為高的情形，因有不溶分(膠化物)生成，故以其之有無，可評價與玻璃及矽石等之極性材料的反應性。The affinity with polar materials can be achieved by, for example, coating a hydrogenated conjugated diene graft polymer (G) on a glass substrate, or polymerization containing a hydrogenated conjugated diene graft polymer (G) After the composition is heated and cured for a certain period of time, it is evaluated by measuring the peel strength and the checker test. In addition, by the condensation reactivity of alkoxysilyl groups or silanol groups, the reactivity and affinity with polar materials such as glass and silica can be evaluated. When the solution containing the hydrogenated conjugated diene graft polymer (G) is shaken under acidic or alkaline conditions, in the case where the condensation reactivity is high, insoluble components (colloids) are formed, so Whether it is available or not, the reactivity with polar materials such as glass and silica can be evaluated.

本發明之氫化共軛二烯系接枝聚合物(G)，將氫化共軛二烯系接枝聚合物(G)每1分子之與上述分支點直接結合的側鏈(b)之平均條數設為W，將氫化共軛二烯系接枝聚合物(G)每1分子之分支點的平均個數設為Y時，(W/Y)滿足下述式(4)之關係為較佳。 0.5≦(W/Y)  (4)The hydrogenated conjugated diene graft polymer (G) of the present invention has an average number of side chains (b) directly bonded to the branch point per molecule of the hydrogenated conjugated diene graft polymer (G) The number is set to W, and when the average number of branch points per molecule of the hydrogenated conjugated diene graft polymer (G) is set to Y, (W/Y) satisfies the relationship of the following formula (4). good. 0.5≦(W/Y) (4)

上述(W/Y)係0.6以上(0.6≦(W/Y))為更佳，0.8以上(0.8≦(W/Y))為進一步較佳。於本發明中，氫化共軛二烯系接枝聚合物(G)每1分子之與上述分支點直接結合的側鏈(b)之平均條數W，於利用本發明之製造方法製造氫化共軛二烯系接枝聚合物(G)的情形，係使用下述步驟(A-1)中的成為氫化共軛二烯系接枝聚合物(G)之側鏈(b)的活性末端聚合物(I)之每活性末端的進料量(莫耳數)與官能基改質共軛二烯系聚合物(F)之進料量(莫耳數)而由下述式(8)求得。 (氫化共軛二烯系接枝聚合物(G)每1分子之與上述分支點直接結合的側鏈(b)之平均條數W)=(側鏈(b)的活性末端聚合物(I)之每活性末端的進料量(莫耳數))/(官能基改質共軛二烯系聚合物(F)之進料量(莫耳數))  (8)The aforementioned (W/Y) is more preferably 0.6 or more (0.6≦(W/Y)), and more preferably 0.8 or more (0.8≦(W/Y)). In the present invention, the average number W of side chains (b) directly bonded to the above-mentioned branch points per molecule of the hydrogenated conjugated diene graft polymer (G) is used in the production of the hydrogenated copolymer by the production method of the present invention. In the case of the conjugated diene graft polymer (G), the living end polymerization of the side chain (b) of the hydrogenated conjugated diene graft polymer (G) in the following step (A-1) is used The feed amount (mole number) per active end of the substance (I) and the feed amount (mole number) of the functional group-modified conjugated diene polymer (F) are obtained by the following formula (8) have to. (The average number of side chains (b) per molecule of the hydrogenated conjugated diene graft polymer (G) directly bonded to the above-mentioned branch point W) = (side chain (b) living terminal polymer (I ) Feeding amount per active end (number of moles))/(Feeding amount of functional group-modified conjugated diene polymer (F) (number of moles)) (8)

又，氫化共軛二烯系接枝聚合物(G)每1分子之分支點的平均個數Y，係利用上述的方法而算出。上述(W/Y)為小於0.5時，氫化共軛二烯系接枝聚合物(G)之流動性降低，加工性與力學特性的平衡有變差的傾向。In addition, the average number Y of branch points per molecule of the hydrogenated conjugated diene graft polymer (G) is calculated by the method described above. When the aforementioned (W/Y) is less than 0.5, the fluidity of the hydrogenated conjugated diene graft polymer (G) decreases, and the balance between processability and mechanical properties tends to deteriorate.

氫化共軛二烯系接枝聚合物(G)之分支的程度，可由下列判斷：對於氫化共軛二烯系接枝聚合物(G)之利用絕對法而得的重量平均分子量(Mw)，將其迴轉半徑(R)進行雙對數作圖時的傾斜度(αs )、或對於氫化共軛二烯系接枝聚合物(G)之利用絕對法而得的重量平均分子量(Mw)，將其固有黏度(η)進行雙對數作圖時之傾斜度(αη)。通常之直鏈狀聚合物之無規則線圈鏈係αs 、αη之任一者皆表示0.6～0.8左右的值，小於0.6則暗示有分支鏈存在。本發明之氫化共軛二烯系接枝聚合物(G)之αs 或αη之值係小於0.6為較佳，0.55以下為更佳，0.50以下為進一步較佳。又，氫化共軛二烯系接枝聚合物(G)之利用絕對法而得的重量平均分子量(Mw)與旋轉半徑(R)或固有黏度(η)之雙對數作圖，可藉由例如SEC-MALS-VISCO法而取得。SEC-MALS-VISCO法為液體層析(SEC)的一種，其係利用分子大小(流體力學的體積)的不同而進行高分子鏈的分離，藉由組合示差折射率計(RI)、多角度光散射偵測器(MALS)、黏度偵測器(VISCO)，可算出經以SEC分別大小的高分子溶液之各分子量的旋轉半徑、固有黏度。本發明之氫化共軛二烯系接枝聚合物(G)之αs 或αη的值為上述之範圍時，氫化共軛二烯系接枝聚合物(G)之流動性提升，加工性與力學特性的平衡有優異的傾向。The degree of branching of the hydrogenated conjugated diene graft polymer (G) can be judged by the following: For the hydrogenated conjugated diene graft polymer (G), the weight average molecular weight (Mw) obtained by the absolute method, The inclination (α s ) when the radius of gyration (R) is plotted on a logarithmic basis, or the weight average molecular weight (Mw) obtained by the absolute method for the hydrogenated conjugated diene graft polymer (G), The slope (αη) when the inherent viscosity (η) is plotted on the logarithm. Any one of the random coil chain systems α s and α η of a normal linear polymer has a value of about 0.6 to 0.8, and a value of less than 0.6 indicates that there is a branched chain. The value of α s or α η of the hydrogenated conjugated diene graft polymer (G) of the present invention is preferably less than 0.6, more preferably 0.55 or less, and even more preferably 0.50 or less. In addition, the weight average molecular weight (Mw) of the hydrogenated conjugated diene graft polymer (G) obtained by the absolute method is plotted against the double logarithm of the radius of gyration (R) or the intrinsic viscosity (η), for example, Acquired by the SEC-MALS-VISCO method. The SEC-MALS-VISCO method is a type of liquid chromatography (SEC), which uses the difference in molecular size (hydrodynamic volume) to separate polymer chains. By combining differential refractive index (RI), multi-angle The light scattering detector (MALS) and the viscosity detector (VISCO) can calculate the radius of gyration and intrinsic viscosity of each molecular weight of the polymer solution of different sizes by SEC. When the value of α s or αη of the hydrogenated conjugated diene graft polymer (G) of the present invention is in the above-mentioned range, the fluidity of the hydrogenated conjugated diene graft polymer (G) is improved, and the processability is improved. The balance of mechanical properties tends to be excellent.

本發明之氫化共軛二烯系接枝聚合物(G)係之氫化共軛二烯系接枝聚合物(G)每1分子之與上述分支點直接結合的側鏈(b)之平均條數W較佳為1以上，2以上為更佳，3以上為進一步較佳。上述側鏈(b)之平均條數W係利用上述的方法而算出。上述側鏈(b)之平均條數W為小於1時，氫化共軛二烯系接枝聚合物(G)之流動性降低，加工性與力學特性的平衡有變差的傾向。The hydrogenated conjugated diene-based graft polymer (G) of the present invention is the hydrogenated conjugated diene-based graft polymer (G) per molecule of the average number of side chains (b) directly bonded to the above-mentioned branch point The number W is preferably 1 or more, more preferably 2 or more, and more preferably 3 or more. The average number W of the side chains (b) described above is calculated by the method described above. When the average number W of the side chains (b) is less than 1, the fluidity of the hydrogenated conjugated diene graft polymer (G) decreases, and the balance between processability and mechanical properties tends to deteriorate.

又，於利用本發明之製造方法製造氫化共軛二烯系接枝聚合物(G)的情形，上述側鏈(b)之平均條數W，可利用例如，後述的步驟(A-1)中的活性末端聚合物(I)與官能基改質共軛二烯系聚合物(F)之進料量之比，而調整為所冀望之範圍。例如，(活性末端聚合物(I)之進料量(莫耳數))/(官能基改質共軛二烯系聚合物(F)之進料量(莫耳數))=4/1的情形，側鏈(b)之平均條數W成為4條。惟，W之上限為官能基改質共軛二烯系聚合物(F)每1分子具有的官能基V之個數。In addition, when the hydrogenated conjugated diene graft polymer (G) is produced by the production method of the present invention, the average number W of the side chains (b) can be, for example, the step (A-1) described later The ratio of the feed amount of the living terminal polymer (I) to the functional group-modified conjugated diene polymer (F) in the slab is adjusted to the desired range. For example, (feeding amount of living end polymer (I) (number of moles))/(feeding amount of functional group-modified conjugated diene polymer (F) (number of moles))=4/1 In the case of, the average number W of side chains (b) becomes four. However, the upper limit of W is the number of functional groups V per molecule of the functional group-modified conjugated diene polymer (F).

氫化共軛二烯系接枝聚合物(G)所含的主鏈(a)的聚合物與側鏈(b)的聚合物之組合未特別限制，可相同亦可相異，可因應目的而設計。主鏈(a)的聚合物與側鏈(b)的聚合物不同，係意指選自包含下述(i)～(iv)的群組的至少1者不同。 (i)主鏈(a)的聚合物之分子量與側鏈(b)的聚合物之分子量不同。 (ii)主鏈(a)的聚合物之單體所衍生的結構單元之種類或種類的組合，與側鏈(b)的聚合物之單體所衍生的結構單元之種類或種類的組合不同。 (iii)主鏈(a)及側鏈(b)各自包含複數個之同一種單體所衍生的結構單元的情形，主鏈(a)的聚合物之單體所衍生的結構單元組成比，與側鏈(b)的聚合物之單體所衍生的結構單元組成比不同。 (iv)主鏈(a)及側鏈(b)各自包含共軛二烯所衍生的結構單元的情形，主鏈(a)的聚合物之共軛二烯所衍生的結構單元的乙烯基含量，與側鏈(b)的聚合物之共軛二烯所衍生的結構單元的乙烯基含量不同。The combination of the polymer of the main chain (a) and the polymer of the side chain (b) contained in the hydrogenated conjugated diene-based graft polymer (G) is not particularly limited, and may be the same or different, and may be used according to the purpose. design. The polymer of the main chain (a) is different from the polymer of the side chain (b), and it means that at least one selected from the group consisting of the following (i) to (iv) is different. (i) The molecular weight of the polymer of the main chain (a) is different from the molecular weight of the polymer of the side chain (b). (ii) The type or combination of structural units derived from the monomer of the polymer of the main chain (a) is different from the type or combination of structural units derived from the monomer of the polymer of the side chain (b) . (iii) When the main chain (a) and the side chain (b) each contain a plurality of structural units derived from the same monomer, the composition ratio of the structural units derived from the monomer of the polymer of the main chain (a), The composition ratio of the structural unit derived from the monomer of the polymer of the side chain (b) is different. (iv) When the main chain (a) and the side chain (b) each contain a structural unit derived from a conjugated diene, the vinyl content of the structural unit derived from the conjugated diene of the polymer of the main chain (a) , And the vinyl content of the structural unit derived from the conjugated diene polymer of the side chain (b) is different.

本發明之氫化共軛二烯系接枝聚合物(G)，於構成其聚合物的全部單體所衍生的結構單元之中，50質量%以上為選自包含丁二烯及異戊二烯的群組的至少1個單體所衍生的結構單元為較佳的一態樣。丁二烯及異戊二烯所衍生的結構單元之合計含量，相對於氫化共軛二烯系接枝聚合物(G)之全部單體所衍生的結構單元而言，60～100質量%為更佳，70～100質量%為進一步較佳。In the hydrogenated conjugated diene graft polymer (G) of the present invention, among the structural units derived from all monomers constituting the polymer, 50% by mass or more is selected from the group consisting of butadiene and isoprene A structural unit derived from at least one monomer in the group is a preferred aspect. The total content of the structural units derived from butadiene and isoprene is 60-100% by mass relative to the structural units derived from all monomers of the hydrogenated conjugated diene graft polymer (G) More preferably, 70 to 100% by mass is still more preferable.

本發明之氫化共軛二烯系接枝聚合物(G)中之丁二烯及異戊二烯以外之其它單體所衍生的結構單元之含量，50質量%以下為較佳，40質量%以下為更佳，30質量%以下為進一步較佳。例如，芳香族乙烯化合物所衍生的結構單元為上述範圍以下時，本發明之氫化共軛二烯系接枝聚合物(G)之加工性有提升的傾向。The content of structural units derived from monomers other than butadiene and isoprene in the hydrogenated conjugated diene graft polymer (G) of the present invention is preferably 50% by mass or less, and 40% by mass The following is more preferable, and 30% by mass or less is even more preferable. For example, when the structural unit derived from the aromatic vinyl compound is below the above range, the processability of the hydrogenated conjugated diene graft polymer (G) of the present invention tends to be improved.

本發明之氫化共軛二烯系接枝聚合物(G)，其接枝聚合物所含的共軛二烯所衍生的結構單元中所含的碳-碳雙鍵之至少一部分經氫化。本發明之氫化共軛二烯系接枝聚合物(G)，由耐熱性及耐候性之觀點來看，氫化前之共軛二烯系接枝聚合物(G')中之共軛二烯所衍生的結構單元中所含的碳-碳雙鍵係50莫耳%以上經氫化為較佳，80莫耳%以上經氫化為更佳，90莫耳%以上經氫化為進一步較佳。又氫化率通常為100莫耳%以下。再者，氫化率可為實質上100莫耳%(即實質上完全氫化)。又，氫化率係使用1 H-NMR，各自算出氫化之前後聚合物中之共軛二烯所衍生的結構單元所含的碳-碳雙鍵之含量，由此等含量而求得的值。In the hydrogenated conjugated diene graft polymer (G) of the present invention, at least a part of the carbon-carbon double bonds contained in the structural unit derived from the conjugated diene contained in the graft polymer is hydrogenated. The hydrogenated conjugated diene graft polymer (G) of the present invention is the conjugated diene in the conjugated diene graft polymer (G') before hydrogenation from the viewpoint of heat resistance and weather resistance The carbon-carbon double bonds contained in the derived structural units are preferably hydrogenated at 50 mol% or more, more preferably 80 mol% or more are hydrogenated, and more preferably 90 mol% or more are hydrogenated. The hydrogenation rate is usually 100 mol% or less. Furthermore, the hydrogenation rate may be substantially 100 mol% (that is, substantially completely hydrogenated). In addition, the hydrogenation rate is a value obtained by calculating the content of the carbon-carbon double bond contained in the structural unit derived from the conjugated diene in the polymer before and after the hydrogenation using 1 H-NMR.

本發明之氫化共軛二烯系接枝聚合物(G)之重量平均分子量(Mw)係5,000以上2,000,000以下者為較佳一態樣，30,000以上1,500,000以下為較佳，超過100,000且1,000,000以下為更佳。氫化共軛二烯系接枝聚合物(G)之Mw為前述範圍內時，有製造時之製程通過性優異、經濟性變良好的傾向。又，包含氫化共軛二烯系接枝聚合物(G)的聚合物組成物之加工性有提升的傾向。The hydrogenated conjugated diene graft polymer (G) of the present invention preferably has a weight average molecular weight (Mw) of 5,000 or more and 2,000,000 or less, preferably 30,000 or more and 1,500,000 or less, and more than 100,000 and 1,000,000 or less Better. When the Mw of the hydrogenated conjugated diene-based graft polymer (G) is within the aforementioned range, the process passability at the time of manufacture tends to be excellent and economical efficiency tends to be improved. In addition, the processability of the polymer composition containing the hydrogenated conjugated diene graft polymer (G) tends to be improved.

本發明之氫化共軛二烯系接枝聚合物(G)之分子量分布(Mw/Mn)係1.0～20.0為較佳，1.0～10.0為更佳，1.0～5.0為進一步較佳，1.0～2.0為特佳。Mw/Mn為前述範圍內時，氫化共軛二烯系接枝聚合物(G)之黏度的離差(dispersion)小，為更佳。又，於本發明中，Mn係意指數量平均分子量，Mn為由GPC之測定而求得的標準聚苯乙烯換算之數量平均分子量。又，分子量分布(Mw/Mn)係意指由GPC之測定所求得的標準聚苯乙烯換算之重量平均分子量(Mw)與數量平均分子量(Mn)之比。The molecular weight distribution (Mw/Mn) of the hydrogenated conjugated diene graft polymer (G) of the present invention is preferably 1.0 to 20.0, more preferably 1.0 to 10.0, more preferably 1.0 to 5.0, further preferably 1.0 to 2.0 It is especially good. When Mw/Mn is within the aforementioned range, the dispersion of the viscosity of the hydrogenated conjugated diene graft polymer (G) is small, which is more preferable. In addition, in the present invention, Mn means the number average molecular weight, and Mn is the number average molecular weight in terms of standard polystyrene obtained by GPC measurement. In addition, the molecular weight distribution (Mw/Mn) means the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in terms of standard polystyrene obtained by the measurement of GPC.

本發明之氫化共軛二烯系接枝聚合物(G)之乙烯基含量未被特別限制，但90莫耳%以下為較佳一態樣，80莫耳%以下為更佳，70莫耳%以下為進一步較佳。氫化共軛二烯系接枝聚合物(G)之乙烯基含量為0.5莫耳%以上為較佳，1莫耳%以上為更佳。本發明之氫化共軛二烯系接枝聚合物(G)之乙烯基含量為藉由氫化前之共軛二烯系接枝聚合物(G')之1 H-NMR光譜，與主鏈(a)的情形同樣地算出。The vinyl content of the hydrogenated conjugated diene graft polymer (G) of the present invention is not particularly limited, but it is preferably 90 mol% or less, more preferably 80 mol% or less, and 70 mol% or less. % Or less is more preferable. The vinyl content of the hydrogenated conjugated diene graft polymer (G) is preferably 0.5 mol% or more, and more preferably 1 mol% or more. The vinyl content of the hydrogenated conjugated diene graft polymer (G) of the present invention is determined by the 1 H-NMR spectrum of the conjugated diene graft polymer (G') before hydrogenation, and the main chain ( The case of a) is calculated in the same way.

氫化共軛二烯系接枝聚合物(G)之乙烯基含量可因應目的而設計，例如，乙烯基含量小於50莫耳%時，氫化共軛二烯系接枝聚合物(G)之玻璃轉移溫度(Tg)變低，流動性、低溫特性為優異的傾向。又，50莫耳%以上時，氫化共軛二烯系接枝聚合物(G)之耐熱性有優異的傾向。又，就單體所衍生的結構單元而言，氫化共軛二烯系接枝聚合物(G)為僅由丁二烯所衍生的結構單元所構成的情形，為了防止氫化後的結晶化所致的性能降低，將氫化共軛二烯系接枝聚合物(G)之乙烯基含量作成25莫耳%以上為較佳。The vinyl content of the hydrogenated conjugated diene graft polymer (G) can be designed according to the purpose. For example, when the vinyl content is less than 50 mol%, the glass of the hydrogenated conjugated diene graft polymer (G) The transition temperature (Tg) becomes lower, and fluidity and low-temperature characteristics tend to be excellent. In addition, at 50 mol% or more, the hydrogenated conjugated diene graft polymer (G) tends to be excellent in heat resistance. In addition, with regard to the structural unit derived from the monomer, the hydrogenated conjugated diene graft polymer (G) is composed of only the structural unit derived from butadiene, in order to prevent crystallization after hydrogenation. It is preferable to make the vinyl content of the hydrogenated conjugated diene graft polymer (G) 25 mol% or more.

氫化共軛二烯系接枝聚合物(G)之玻璃轉移溫度(Tg)可依丁二烯、異戊二烯及其它之共軛二烯等之共軛二烯所衍生的結構單元的乙烯基含量、共軛二烯的種類、共軛二烯以外之單體所衍生的結構單元之含量等而變化，但-150～50℃為較佳，-130～50℃為更佳， -130～30℃為進一步較佳。Tg為上述範圍時，例如，可抑制黏度變高且處理變容易。The glass transition temperature (Tg) of the hydrogenated conjugated diene graft polymer (G) can be based on the ethylene of the structural unit derived from conjugated dienes such as butadiene, isoprene and other conjugated dienes. The content of the group, the type of the conjugated diene, the content of the structural unit derived from the monomer other than the conjugated diene, etc. vary, but -150 to 50°C is preferred, and -130 to 50°C is more preferred. -130 to 30°C is more preferable. When Tg is in the above range, for example, the viscosity can be suppressed from increasing and the handling can be facilitated.

本發明之氫化共軛二烯系接枝聚合物(G)中的主鏈(a)與側鏈(b)之質量比(a)/(b)係0.05/99.95～90/10之範圍為較佳，0.1/99.9～80/20之範圍為更佳，0.5/99.5～70/30之範圍為進一步較佳。主鏈與側鏈之質量比為上述範圍時，包含氫化共軛二烯系接枝聚合物(G)的聚合物組成物之加工性有提升的傾向。The mass ratio (a)/(b) of the main chain (a) to the side chain (b) in the hydrogenated conjugated diene graft polymer (G) of the present invention is in the range of 0.05/99.95 to 90/10 Preferably, the range of 0.1/99.9 to 80/20 is more preferable, and the range of 0.5/99.5 to 70/30 is even more preferable. When the mass ratio of the main chain to the side chain is in the above range, the processability of the polymer composition containing the hydrogenated conjugated diene graft polymer (G) tends to be improved.

本發明之氫化共軛二烯系接枝聚合物(G)，源自其製造所使用的聚合觸媒、氫化觸媒等的觸媒殘渣量的總量，以金屬換算，於0～500ppm之範圍為較佳。例如，作為用以製造氫化前之共軛二烯系接枝聚合物(G')之聚合觸媒，使用如後述的有機鋰化合物等之有機鹼金屬的情形，可包含鋰等之鹼金屬。又，於後述的共軛二烯系接枝聚合物(G')之氫化，使用齊格勒(Ziegler)系觸媒作為氫化觸媒的情形，可包含鎳、鋁。觸媒殘渣量的總量為上述範圍，加工等之際黏性不會降低，又本發明之氫化共軛二烯系接枝聚合物(G)之耐熱性會提升。氫化共軛二烯系接枝聚合物(G)之觸媒殘渣量的總量，以金屬換算，更佳為0～300ppm，進一步較佳為0～200ppm。又，觸媒殘渣量，例如可藉由使用電感耦合電漿質譜分析裝置(ICP-MS)、偏光的季曼原子吸收分光光度計(polarized Zeeman atomic absorption apectrophotometer)而測定。The hydrogenated conjugated diene graft polymer (G) of the present invention is derived from the total amount of catalyst residues of polymerization catalysts, hydrogenation catalysts, etc. used in its production, in terms of metal, within the range of 0 to 500 ppm The range is better. For example, when an organic alkali metal such as an organolithium compound described later is used as a polymerization catalyst for producing the conjugated diene graft polymer (G') before hydrogenation, it may contain an alkali metal such as lithium. In addition, in the hydrogenation of the conjugated diene-based graft polymer (G′) described later, when a Ziegler-based catalyst is used as the hydrogenation catalyst, nickel and aluminum may be included. The total amount of the catalyst residue is within the above range, the viscosity does not decrease during processing, etc., and the heat resistance of the hydrogenated conjugated diene-based graft polymer (G) of the present invention is improved. The total amount of catalyst residues of the hydrogenated conjugated diene graft polymer (G), in terms of metal, is more preferably 0 to 300 ppm, and still more preferably 0 to 200 ppm. In addition, the amount of catalyst residue can be measured, for example, by using an inductively coupled plasma mass spectrometer (ICP-MS) or a polarized Zeeman atomic absorption spectrophotometer (polarized Zeeman atomic absorption apectrophotometer).

就將氫化共軛二烯系接枝聚合物(G)之觸媒殘渣量設成此種特定量的方法而言，可列舉將氫化共軛二烯系接枝聚合物(G)純化，將觸媒殘渣充分去除的方法等。就純化的方法而言，利用水或溫水、酸性水溶液、或甲醇、丙酮等為代表的有機溶劑的洗淨、或利用超臨界流體二氧化碳的洗淨為較佳。於洗淨，藉由使用酸性水溶液，可提高洗淨效率。就使用的酸而言，例如，鹽酸、硝酸、硫酸等之一元或多元之強酸；乙酸、丙酸、琥珀酸、檸檬酸等之一元或多元羧酸；碳酸、磷酸等之一元或多元之弱酸為較佳。就洗淨次數而言，由經濟的觀點來看，1～20次為較佳，1～10次為更佳。又，就洗淨溫度而言，20～100℃為較佳，40～90℃為更佳。又藉由於聚合反應之前利用蒸餾或吸附劑去除阻礙聚合進行的雜質，而提高單體的純度然後再進行聚合，因減少所需的聚合觸媒量，而可減少觸媒殘渣量。The method of setting the amount of the catalyst residue of the hydrogenated conjugated diene graft polymer (G) to such a specific amount includes purifying the hydrogenated conjugated diene graft polymer (G), and Methods to fully remove catalyst residues, etc. As for the purification method, washing with water, warm water, acidic aqueous solution, or organic solvent represented by methanol, acetone, etc., or washing with supercritical fluid carbon dioxide is preferred. For cleaning, the cleaning efficiency can be improved by using an acidic aqueous solution. Regarding the acid used, for example, strong monobasic or polybasic acids such as hydrochloric acid, nitric acid, and sulfuric acid; monobasic or polybasic carboxylic acids such as acetic acid, propionic acid, succinic acid, and citric acid; monobasic or polybasic weak acids such as carbonic acid and phosphoric acid For better. In terms of the number of times of washing, from an economic point of view, 1 to 20 times is preferable, and 1 to 10 times is more preferable. Moreover, as for the washing temperature, 20 to 100°C is preferable, and 40 to 90°C is more preferable. In addition, by using distillation or adsorbent to remove impurities that hinder the polymerization before the polymerization reaction, the purity of the monomer is improved and then the polymerization is carried out. The amount of polymerization catalyst required is reduced, and the amount of catalyst residue can be reduced.

本發明之氫化共軛二烯系接枝聚合物(G)，鹵素含量為0～1,000ppm者為較佳。例如，作為用以製造氫化共軛二烯系接枝聚合物(G)的官能基改質共軛二烯系聚合物(F)，使用氯矽烷改質共軛二烯系聚合物的情形，成為基準的鹵素係氯。藉由鹵素含量於上述範圍，有透明性、耐熱性、耐候性變良好的傾向。就氫化共軛二烯系接枝聚合物(G)之鹵素含量而言，更佳為0～500ppm，進一步較佳為0～100ppm。又，鹵素含量，可藉由使用例如燃燒離子層析法而測定。The hydrogenated conjugated diene graft polymer (G) of the present invention preferably has a halogen content of 0 to 1,000 ppm. For example, as a functional group-modified conjugated diene-based polymer (F) used to produce the hydrogenated conjugated diene-based graft polymer (G), chlorosilane is used to modify the conjugated diene-based polymer, Standard halogen-based chlorine. When the halogen content is in the above range, transparency, heat resistance, and weather resistance tend to become better. The halogen content of the hydrogenated conjugated diene graft polymer (G) is more preferably 0 to 500 ppm, and still more preferably 0 to 100 ppm. In addition, the halogen content can be measured by using, for example, combustion ion chromatography.

就將氫化共軛二烯系接枝聚合物(G)之鹵素含量作成此種特定量的方法而言，可列舉使用不產生為副產物之鹵化物的烷氧基矽烷改質共軛二烯系聚合物作為用以製造氫化共軛二烯系接枝聚合物(G)之原料的官能基改質共軛二烯系聚合物(F)的方法。The method of making the halogen content of the hydrogenated conjugated diene graft polymer (G) into such a specific amount includes the use of alkoxysilanes that do not produce halide as a by-product to modify the conjugated diene A method for modifying the conjugated diene-based polymer (F) with functional groups as a raw material for the production of the hydrogenated conjugated diene-based graft polymer (G).

＜氫化共軛二烯系接枝聚合物(G)之製造方法＞ 本發明之氫化共軛二烯系接枝聚合物(G)之製造方法未被特別限制。 可列舉例如，(i)將包含選自包含共軛二烯及芳香族乙烯化合物的群組的至少1個單體所衍生的結構單元的巨單體(包含選自包含共軛二烯及芳香族乙烯化合物的群組的至少1個單體所衍生的結構單元的聚合物之活性末端，與具有聚合性官能基的化合物反應而獲得的巨單體)與包含共軛二烯的單體進行聚合，製作共軛二烯系接枝聚合物，將所獲得的共軛二烯系接枝聚合物進行氫化，而製造氫化共軛二烯系接枝聚合物的方法(由巨單體所含的聚合性官能基、及與巨單體反應的單體而獲得的聚合物鏈所衍生的部分為主鏈/包含巨單體所含的聚合性官能基的化合物所衍生的部分以外之聚合物鏈所衍生的部分為側鏈)； (ii)於四甲基乙二胺存在下，使包含共軛二烯所衍生的結構單元的聚合物與有機鹼金屬化合物反應，將該聚合物作成具有金屬活性部分的聚合物後，由該金屬活性部分聚合包含選自包含共軛二烯及芳香族乙烯化合物的群組的至少1個單體的單體，製作共軛二烯系接枝聚合物，將所獲得的共軛二烯系接枝聚合物氫化，而製造氫化共軛二烯系接枝聚合物的方法(與有機鹼金屬化合物反應的聚合物所含的聚合物鏈所衍生的部分為主鏈/由金屬活性部分聚合而獲得的聚合物鏈所衍生的部分為側鏈)； (iii)調製包含共軛二烯所衍生的結構單元且具有2個活性末端的聚合物、與包含選自包含共軛二烯及芳香族乙烯化合物的群組的至少1個單體所衍生的結構單元且具有1個活性末端的聚合物之混合物，於此混合物中添加具有3個以上之反應性部位的偶合劑而使其反應，製作共軛二烯系接枝聚合物，將所獲得的共軛二烯系接枝聚合物氫化，而製造氫化共軛二烯系接枝聚合物的方法(具有2個活性末端的聚合物所含的聚合物鏈所衍生的部分為主鏈/具有1個活性末端的聚合物所含的聚合物鏈所衍生的部分為側鏈)； (iv)將事先合成的包含共軛二烯所衍生的結構單元的聚合物以官能基改質而製作官能基改質聚合物，使該官能基改質聚合物所含的官能基，與包含選自包含共軛二烯及芳香族乙烯化合物的群組的至少1個單體的單體聚合而成的聚合物的活性末端反應，製作共軛二烯系接枝聚合物，將所獲得的共軛二烯系接枝聚合物進行氫化，而製造氫化共軛二烯系接枝聚合物的方法(官能基改質聚合物所含的聚合物鏈所衍生的部分為主鏈/具有活性末端的聚合物所含的聚合物鏈所衍生的部分為側鏈)等。<Method for producing hydrogenated conjugated diene graft polymer (G)> The method for producing the hydrogenated conjugated diene graft polymer (G) of the present invention is not particularly limited. For example, (i) a macromonomer containing a structural unit derived from at least one monomer selected from the group consisting of a conjugated diene and an aromatic vinyl compound (including a macromonomer selected from the group consisting of a conjugated diene and an aromatic vinyl compound). The active end of the polymer of the structural unit derived from at least one monomer of the group of vinyl compounds, the macromonomer obtained by reacting with a compound having a polymerizable functional group) is combined with a monomer containing a conjugated diene Polymerization to produce a conjugated diene-based graft polymer. The obtained conjugated diene-based graft polymer is hydrogenated to produce a hydrogenated conjugated diene-based graft polymer (contained by macromonomers). The polymer chain derived from the polymerizable functional group and the monomer that reacts with the macromonomer is the main chain/polymer other than the part derived from the compound containing the polymerizable functional group contained in the macromonomer The derived part of the chain is the side chain); (ii) In the presence of tetramethylethylenediamine, a polymer containing a structural unit derived from a conjugated diene is reacted with an organic alkali metal compound, and the polymer is made into a polymer with a metal active part. The metal active part polymerizes a monomer containing at least one monomer selected from the group consisting of a conjugated diene and an aromatic vinyl compound to produce a conjugated diene-based graft polymer, and the obtained conjugated diene-based graft polymer Hydrogenation of the graft polymer to produce a hydrogenated conjugated diene graft polymer The part derived from the obtained polymer chain is the side chain); (iii) Preparation of a polymer containing a structural unit derived from a conjugated diene and having two active ends, and a polymer derived from at least one monomer selected from the group consisting of a conjugated diene and an aromatic vinyl compound A mixture of polymers with structural units and one active end. A coupling agent with 3 or more reactive sites is added to this mixture to react to produce a conjugated diene graft polymer, and the obtained Hydrogenation of conjugated diene graft polymer to produce hydrogenated conjugated diene graft polymer The part derived from the polymer chain contained in the polymer of each active end is the side chain); (iv) Modification of a polymer containing a structural unit derived from a conjugated diene synthesized in advance with a functional group to prepare a functional group-modified polymer, the functional group-modified polymer containing the functional group, and The active end of a polymer polymerized by a monomer of at least one monomer selected from the group consisting of a conjugated diene and an aromatic vinyl compound is reacted to produce a conjugated diene-based graft polymer, and the obtained The conjugated diene-based graft polymer is hydrogenated to produce a hydrogenated conjugated diene-based graft polymer (the part derived from the polymer chain contained in the functional group-modified polymer is the main chain / has active The part derived from the polymer chain contained in the polymer is a side chain) and so on.

此等之製造方法之中，亦可自由控制氫化共軛二烯系接枝聚合物(G)之主鏈、及側鏈之重量平均分子量及乙烯基含量、側鏈的條數等，又，因可簡便地導入所冀望的官能基，而較佳為上述(iv)使包含共軛二烯所衍生的結構單元的官能基改質聚合物，與包含選自包含共軛二烯及芳香族乙烯化合物的群組的至少1個單體的單體聚合而成的聚合物的活性末端反應，製作共軛二烯系接枝聚合物，將所獲得的共軛二烯系接枝聚合物氫化，而製造氫化共軛二烯系接枝聚合物的方法。In these production methods, it is also possible to freely control the weight average molecular weight of the main chain and side chains of the hydrogenated conjugated diene graft polymer (G), the vinyl content, the number of side chains, etc., and, Since the desired functional group can be easily introduced, it is preferable that the above-mentioned (iv) a functional group-modified polymer containing a structural unit derived from a conjugated diene, and a polymer selected from the group consisting of conjugated diene and aromatic The active end of the polymer formed by polymerizing at least one monomer of the vinyl compound group is reacted to produce a conjugated diene graft polymer, and the obtained conjugated diene graft polymer is hydrogenated , And the method of producing hydrogenated conjugated diene graft polymer.

就本發明之氫化共軛二烯系接枝聚合物(G)之製造方法而言，包含下述步驟(A-1)、步驟(B)、及步驟(C)的製造方法為較佳。With regard to the production method of the hydrogenated conjugated diene graft polymer (G) of the present invention, a production method comprising the following steps (A-1), step (B), and step (C) is preferred.

(A-1)使下述式(I)所表示的活性末端聚合物(I)、與具有包含下述式(II)所示的官能基的部分作為分支鏈的官能基改質共軛二烯系聚合物(F)反應，而製作共軛二烯系接枝聚合物(G')的步驟(A-1) The living terminal polymer (I) represented by the following formula (I) is modified with a functional group containing a functional group represented by the following formula (II) as a branched chain. Step of making a conjugated diene graft polymer (G') by reacting the olefin polymer (F)

P-X  (I) (式(I)中，P表示包含選自包含共軛二烯及芳香族乙烯化合物的群組的至少1個單體所衍生的結構單元的聚合物鏈，X表示陰離子聚合之活性末端。)P-X (I) (In formula (I), P represents a polymer chain containing a structural unit derived from at least one monomer selected from the group consisting of a conjugated diene and an aromatic vinyl compound, and X represents an anionic polymerization active end.)

Figure 02_image007
(式(II)中，V表示烷氧基或羥基，Z為Si、Sn、Ge、Pb、P、B、或Al，R1 表示碳數6～12之芳基、碳數1～12之烷基、或氫原子，N表示前述Z之價數，n為滿足下述式(5)的整數； 1≦n≦N-1  (5) n為2以上的情形，V可為相同亦可為相異，N-n為2以上的情形，R1 可為相同亦可為相異，對於主鏈，分支鏈含有複數個的情形，Z可為相同亦可為相異。)；及 (B)將上述共軛二烯系接枝聚合物(G')所含的至少一部分之共軛二烯所衍生的結構單元中所含的碳-碳雙鍵進行氫化而形成氫化共軛二烯系接枝聚合物(G)的步驟；及 (C)回收所獲得的氫化共軛二烯系接枝聚合物(G)的步驟。
Figure 02_image007
(In formula (II), V represents an alkoxy group or a hydroxyl group, Z represents Si, Sn, Ge, Pb, P, B, or Al, and R 1 represents an aryl group with 6 to 12 carbons, and a group with 1 to 12 carbons. Alkyl group or hydrogen atom, N represents the valence of the aforementioned Z, n is an integer satisfying the following formula (5); 1≦n≦N-1 (5) When n is 2 or more, V may be the same When Nn is 2 or more, R 1 may be the same or different. For the main chain and branch chains, Z may be the same or different.); and (B) The carbon-carbon double bond contained in the structural unit derived from at least a part of the conjugated diene contained in the above-mentioned conjugated diene graft polymer (G') is hydrogenated to form a hydrogenated conjugated diene graft The step of grafting polymer (G); and (C) the step of recovering the obtained hydrogenated conjugated diene graft polymer (G).

又，官能基改質共軛二烯系聚合物(F)之分支鏈係意指官能基改質共軛二烯系聚合物(F)之主鏈以外的部分，此主鏈，係與共軛二烯系接枝聚合物中的主鏈(a)同樣地，指包含構成主鏈的共軛二烯的全部單體所衍生的結構單元部分整體。In addition, the branch chain of the functional group-modified conjugated diene polymer (F) means the part other than the main chain of the functional group-modified conjugated diene polymer (F). The main chain (a) in the conjugated diene-based graft polymer similarly refers to the whole of the structural unit part derived from all monomers including the conjugated diene constituting the main chain.

[步驟(A-1)] 上述步驟(A-1)所使用的活性末端聚合物(I)可使用周知之聚合方法而製造。例如，對於聚合末端，藉由於惰性溶劑中，將可陰離子聚合的活性金屬或活性金屬化合物作為起始劑，因應必要而於極性化合物之存在下，使單體進行陰離子聚合，可獲得活性末端聚合物(I)。此活性末端聚合物(I)之P成為上述共軛二烯系接枝聚合物(G')之側鏈(b')。[Step (A-1)] The living terminal polymer (I) used in the above step (A-1) can be produced using a known polymerization method. For example, for the polymerization terminal, by using an anionically polymerizable active metal or active metal compound as the initiator in an inert solvent, and if necessary, in the presence of a polar compound, anionic polymerization of the monomer can be obtained to obtain a living terminal polymerization.物(I). The P of the living terminal polymer (I) becomes the side chain (b') of the above-mentioned conjugated diene-based graft polymer (G').

成為構成活性末端聚合物(I)的單體所衍生的結構單元的單體之具體例、適合態樣等之說明、及活性末端聚合物(I)所含的單體所衍生的結構單元之具體例及適合態樣之說明，係與關於氫化共軛二烯系接枝聚合物(G)之側鏈(b)的說明相同。Specific examples and descriptions of suitable aspects, etc. of the monomers constituting the structural units derived from the monomers constituting the living terminal polymer (I), and among the structural units derived from the monomers contained in the living terminal polymer (I) The description of specific examples and suitable aspects is the same as the description of the side chain (b) of the hydrogenated conjugated diene graft polymer (G).

就可陰離子聚合的活性金屬或活性金屬化合物而言，有機鹼金屬化合物為較佳，有機鋰化合物為更佳。就上述有機鋰化合物而言，可列舉例如，甲基鋰、乙基鋰、正丁基鋰、二級丁基鋰、三級丁基鋰、戊基鋰等。As for the active metal or active metal compound that can be anionically polymerized, an organic alkali metal compound is preferable, and an organic lithium compound is more preferable. Examples of the above-mentioned organolithium compounds include methyl lithium, ethyl lithium, n-butyl lithium, secondary butyl lithium, tertiary butyl lithium, and pentyl lithium.

就上述溶劑而言，可列舉例如，正丁烷、正戊烷、異戊烷、正己烷、正庚烷、異辛烷等之脂肪族烴；環戊烷、環己烷、甲基環戊烷等之脂環式烴；苯、甲苯、二甲苯等之芳香族烴等。The above-mentioned solvents include, for example, aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, and isooctane; cyclopentane, cyclohexane, methylcyclopentane, etc. Alicyclic hydrocarbons such as alkanes; aromatic hydrocarbons such as benzene, toluene and xylene.

上述陰離子聚合之際，可添加極性化合物。極性化合物係於陰離子聚合中，通常，不使反應失活，而使用於用以調整共軛二烯部位之微結構(乙烯基含量)。就極性化合物而言，可列舉例如，二丁基醚、四氫呋喃、乙二醇二乙基醚等之醚化合物；四甲基乙二胺、三甲基胺等之3級胺；鹼金屬醇鹽(alkali metal alkoxide)、膦化合物等。極性化合物，相對於有機鹼金屬化合物1莫耳，通常以0.01～1000莫耳之量使用。During the above-mentioned anionic polymerization, a polar compound may be added. Polar compounds are used in anionic polymerization. Usually, they do not deactivate the reaction, but are used to adjust the microstructure (vinyl content) of the conjugated diene site. For polar compounds, for example, ether compounds such as dibutyl ether, tetrahydrofuran, and ethylene glycol diethyl ether; tertiary amines such as tetramethylethylenediamine and trimethylamine; alkali metal alkoxides (alkali metal alkoxide), phosphine compounds, etc. The polar compound is usually used in an amount of 0.01 to 1000 mol with respect to 1 mol of the organic alkali metal compound.

上述陰離子聚合之溫度，通常為-80～150℃之範圍，較佳為0～100℃之範圍，更佳為10～90℃之範圍。聚合樣式可為批次式或連續式之任一者。The temperature of the anionic polymerization is usually in the range of -80 to 150°C, preferably in the range of 0 to 100°C, more preferably in the range of 10 to 90°C. The aggregation mode can be either batch mode or continuous mode.

上述活性末端聚合物(I)之P經由後述的氫化步驟，最終地，成為本發明之氫化共軛二烯系接枝聚合物(G)之側鏈(b)。上述活性末端聚合物(I)之P之重量平均分子量(Mw)、乙烯基含量、Tg之適合態樣等的說明，係與關於本發明之氫化共軛二烯系接枝聚合物(G)之側鏈(b)者相同。The P of the above-mentioned living terminal polymer (I) undergoes the hydrogenation step described later, and finally becomes the side chain (b) of the hydrogenated conjugated diene-based graft polymer (G) of the present invention. The description of the weight average molecular weight (Mw), vinyl content, and Tg of P of the living terminal polymer (I) is related to the hydrogenated conjugated diene graft polymer (G) of the present invention. The side chain (b) is the same.

於上述步驟(A-1)，官能基改質共軛二烯系聚合物(F)，例如，可藉由將未改質共軛二烯系聚合物(F')於後述的改質步驟藉由官能基進行改質而獲得。前述未改質共軛二烯系聚合物(F')之製造方法未被特別限制，但較佳為例如，乳化聚合法、溶液聚合法，由所獲得的聚合物之分子量分布的觀點來看，更佳為溶液聚合法。官能基改質共軛二烯系聚合物(F)之官能基改質以外之部分成為上述共軛二烯系接枝聚合物(G')之主鏈(a')。In the above step (A-1), the functional group is modified to modify the conjugated diene polymer (F). For example, the unmodified conjugated diene polymer (F') can be modified in the following modification step Obtained by modifying functional groups. The method for producing the aforementioned unmodified conjugated diene polymer (F') is not particularly limited, but it is preferably, for example, an emulsion polymerization method and a solution polymerization method, from the viewpoint of the molecular weight distribution of the polymer obtained , More preferably a solution polymerization method. Functional group-modified conjugated diene-based polymer (F) The part other than functional group-modified becomes the main chain (a') of the above-mentioned conjugated diene-based graft polymer (G').

成為構成未改質共軛二烯系聚合物(F')的單體所衍生的結構單元的共軛二烯之具體例、適合例、及其適合含量、以及共軛二烯以外之其它單體(芳香族乙烯化合物)之具體例、適合例、適合含量等之說明，係與關於氫化共軛二烯系接枝聚合物(G)之主鏈(a)的說明相同。又，未改質共軛二烯系聚合物(F')之重量平均分子量(Mw)、乙烯基含量、Tg之適合態樣等之說明，係與關於氫化共軛二烯系接枝聚合物(G)之主鏈(a)的說明相同。Specific examples of conjugated dienes, suitable examples, suitable content, and monomers other than conjugated dienes, which become structural units derived from the monomers constituting the unmodified conjugated diene polymer (F') The description of specific examples, suitable examples, and suitable content of the compound (aromatic vinyl compound) is the same as the description of the main chain (a) of the hydrogenated conjugated diene graft polymer (G). In addition, the description of the weight average molecular weight (Mw), vinyl content, and Tg of the unmodified conjugated diene polymer (F') is related to the hydrogenated conjugated diene graft polymer The description of the main chain (a) of (G) is the same.

就為未改質共軛二烯系聚合物(F')之製造方法之一例的上述乳化聚合法而言，可適用周知或按照周知的方法。例如，將包含指定量之共軛二烯的單體於乳化劑之存在下，乳化分散於分散媒中，利用自由基聚合起始劑而乳化聚合。For the above-mentioned emulsion polymerization method, which is an example of a method for producing the unmodified conjugated diene polymer (F′), a well-known or a well-known method can be applied. For example, a monomer containing a specified amount of conjugated diene is emulsified and dispersed in a dispersing medium in the presence of an emulsifier, and then emulsified and polymerized by a radical polymerization initiator.

就乳化劑而言，可列舉例如碳數10以上之長鏈脂肪酸鹽及松香酸(rosin acid)鹽等。就長鏈脂肪酸鹽而言，可列舉例如，癸酸、月桂酸、肉豆蔻酸、棕櫚酸、油酸、硬脂酸等之脂肪酸的鉀鹽或鈉鹽等。As the emulsifier, for example, a long-chain fatty acid salt having a carbon number of 10 or more, a rosin acid salt, and the like can be cited. Examples of long-chain fatty acid salts include potassium or sodium salts of fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, and stearic acid.

就分散媒而言，通常使用水。於聚合時之安定性未被阻礙的範圍內，分散媒可包含甲醇、乙醇等之水溶性有機溶劑。As for the dispersion medium, water is usually used. As long as the stability during polymerization is not hindered, the dispersion medium may include water-soluble organic solvents such as methanol and ethanol.

就自由基聚合起始劑而言，可列舉例如過硫酸銨、過硫酸鉀的過硫酸鹽、有機過氧化物、過氧化氫等。Examples of radical polymerization initiators include persulfates of ammonium persulfate and potassium persulfate, organic peroxides, and hydrogen peroxide.

為了調整所獲得的未改質共軛二烯系聚合物(F')之分子量，可使用鏈轉移劑。就鏈轉移劑而言，可列舉例如，三級十二基硫醇、正十二基硫醇等之硫醇類；四氯化碳、硫乙醇酸、雙萜、萜品油烯(terpinolene)、γ-萜品烯、α-甲基苯乙烯二聚體等。In order to adjust the molecular weight of the obtained unmodified conjugated diene polymer (F'), a chain transfer agent can be used. For chain transfer agents, for example, mercaptans such as tertiary dodecyl mercaptan and n-dodecyl mercaptan; carbon tetrachloride, thioglycolic acid, diterpenes, terpinolene (terpinolene) , Γ-terpinene, α-methylstyrene dimer, etc.

乳化聚合之溫度可依使用的自由基聚合起始劑之種類等而適宜設定，但通常為0～100℃之範圍，較佳為0～60℃之範圍。聚合樣式可為連續聚合、批次聚合之任一者。The temperature of the emulsion polymerization can be appropriately set according to the kind of radical polymerization initiator used, etc., but it is usually in the range of 0-100°C, preferably in the range of 0-60°C. The polymerization style can be either continuous polymerization or batch polymerization.

聚合反應可藉由聚合停止劑之添加而停止。就聚合停止劑而言，可列舉例如，異丙基羥基胺、二乙基羥基胺、羥基胺等之胺化合物、氫醌及苯醌等之醌系化合物、亞硝酸鈉等。The polymerization reaction can be stopped by adding a polymerization stopper. The polymerization terminator includes, for example, amine compounds such as isopropylhydroxyamine, diethylhydroxyamine, and hydroxylamine, quinone compounds such as hydroquinone and benzoquinone, and sodium nitrite.

聚合反應停止後，因應必要可添加老化防止劑。聚合反應停止後，從所獲得的乳膠，因應必要去除未反應單體，接著，將氯化鈉、氯化鈣、氯化鉀等之鹽作為凝固劑，因應必要一邊添加硝酸、硫酸等之酸一邊將凝固系統之pH調整為指定的值，使上述未改質共軛二烯系聚合物(F')凝固後，藉由將分散媒分離而回收聚合物。接著水洗、及脫水後，藉由乾燥，可獲得上述未改質共軛二烯系聚合物(F')。又，於凝固之際，因應必要，預先將乳膠與油展於乳化分散液的油加以混合，可回收呈經油展的未改質共軛二烯系聚合物(F')。After the polymerization reaction is stopped, an anti-aging agent can be added as necessary. After the polymerization reaction is stopped, unreacted monomers are removed as necessary from the obtained latex. Then, sodium chloride, calcium chloride, potassium chloride and other salts are used as coagulants, and acids such as nitric acid and sulfuric acid are added as necessary. While adjusting the pH of the coagulation system to a predetermined value, the unmodified conjugated diene polymer (F') is coagulated, and then the dispersion medium is separated to recover the polymer. After washing with water, dehydrating, and drying, the above-mentioned unmodified conjugated diene polymer (F') can be obtained. In addition, at the time of coagulation, if necessary, the latex and the oil spread in the emulsified dispersion are mixed in advance to recover the unmodified conjugated diene polymer (F') in the form of oil spread.

就為未改質共軛二烯系聚合物(F')之製造方法之一例的上述溶液聚合法而言，可應用周知或按照周知的方法。例如，於溶劑中，使用齊格勒系觸媒、茂金屬系觸媒、或可陰離子聚合的活性金屬或活性金屬化合物作為起始劑，因應必要，於極性化合物之存在下，將包含共軛二烯的單體進行聚合。For the above-mentioned solution polymerization method, which is an example of a method for producing the unmodified conjugated diene polymer (F′), a well-known or a well-known method can be applied. For example, in the solvent, Ziegler-based catalysts, metallocene-based catalysts, or anionic polymerizable active metals or active metal compounds are used as initiators. If necessary, in the presence of polar compounds, conjugated Diene monomers are polymerized.

就溶劑而言，可列舉例如，正丁烷、正戊烷、異戊烷、正己烷、正庚烷、異辛烷等之脂肪族烴；環戊烷、環己烷、甲基環戊烷等之脂環式烴；苯、甲苯、二甲苯等之芳香族烴等。As for the solvent, for example, aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, and isooctane; cyclopentane, cyclohexane, methylcyclopentane Alicyclic hydrocarbons such as benzene, toluene, xylene, etc.;

就上述起始劑而言，可陰離子聚合的活性金屬或活性金屬化合物為較佳，可陰離子聚合的活性金屬化合物為更佳。With regard to the above-mentioned initiators, anionic polymerizable active metals or active metal compounds are preferred, and anionic polymerizable active metal compounds are more preferred.

就可陰離子聚合的活性金屬而言，可列舉例如，鋰、鈉、鉀等之鹼金屬；鈹、鎂、鈣、鍶、鋇等之鹼土金屬；鑭、釹等之鑭系元素系稀土類金屬等。此等之中以鹼金屬及鹼土金屬為較佳，鹼金屬為更佳。For anionic polymerizable active metals, for example, alkali metals such as lithium, sodium, and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium, and barium; and lanthanide-based rare earth metals such as lanthanum and neodymium Wait. Among these, alkali metals and alkaline earth metals are preferred, and alkali metals are more preferred.

就可陰離子聚合的活性金屬化合物而言，有機鹼金屬化合物為較佳。就有機鹼金屬化合物而言，可列舉例如，甲基鋰、乙基鋰、正丁基鋰、二級丁基鋰、三級丁基鋰、己基鋰、苯基鋰、二苯乙烯鋰等之有機單鋰化合物；二鋰代甲烷(dilithiomethane)、二鋰代萘、1,4-二鋰代丁烷、1,4-二鋰代-2-乙基環己烷、1,3,5-三鋰代苯等之多官能性有機鋰化合物；鈉萘、鉀萘等。此等有機鹼金屬化合物之中以有機鋰化合物為較佳，有機單鋰化合物為更佳。As for the anionic polymerizable active metal compound, an organic alkali metal compound is preferred. For organic alkali metal compounds, for example, methyl lithium, ethyl lithium, n-butyl lithium, secondary butyl lithium, tertiary butyl lithium, hexyl lithium, phenyl lithium, stilbene lithium, etc. Organic monolithium compounds; dilithiomethane, dilithium naphthalene, 1,4-dilithium butane, 1,4-dilithium-2-ethylcyclohexane, 1,3,5- Multifunctional organolithium compounds such as trilithium benzene; sodium naphthalene, potassium naphthalene, etc. Among these organic alkali metal compounds, organic lithium compounds are preferred, and organic monolithium compounds are more preferred.

上述起始劑之使用量，可因應未改質共軛二烯系聚合物(F')及官能基改質共軛二烯系聚合物(F)之融熔黏度、分子量等而適當設定，但相對於包含共軛二烯的全部單體100質量份，通常以0.01～3質量份之量使用。The usage amount of the above-mentioned initiator can be appropriately set according to the melting viscosity and molecular weight of the unmodified conjugated diene polymer (F') and the functional group modified conjugated diene polymer (F). However, it is usually used in an amount of 0.01 to 3 parts by mass relative to 100 parts by mass of all monomers containing conjugated diene.

將有機鹼金屬化合物作為起始劑使用的情形，上述有機鹼金屬化合物亦可使與二丁基胺、二己基胺、二苄基胺等之2級胺反應，而作為有機鹼金屬醯胺使用。When an organic alkali metal compound is used as an initiator, the organic alkali metal compound can also be used as an organic alkali metal amine by reacting with a secondary amine such as dibutylamine, dihexylamine, and dibenzylamine .

極性化合物係於陰離子聚合中，通常，不使反應失活，而使用於用以調整共軛二烯部位之微結構(乙烯基含量)。就極性化合物而言，可列舉例如，二丁基醚、四氫呋喃、乙二醇二乙基醚等之醚化合物；四甲基乙二胺、三甲基胺等之3級胺；鹼金屬醇鹽、膦化合物等。極性化合物相對於有機鹼金屬化合物1莫耳，通常以0.01～1000莫耳之量使用。Polar compounds are used in anionic polymerization. Usually, they do not deactivate the reaction, but are used to adjust the microstructure (vinyl content) of the conjugated diene site. For polar compounds, for example, ether compounds such as dibutyl ether, tetrahydrofuran, and ethylene glycol diethyl ether; tertiary amines such as tetramethylethylenediamine and trimethylamine; alkali metal alkoxides , Phosphine compounds, etc. The polar compound is usually used in an amount of 0.01 to 1000 mol with respect to 1 mol of the organic alkali metal compound.

溶液聚合之溫度，通常為-80～150℃之範圍，較佳為0～100℃之範圍，更佳為10～90℃之範圍。聚合樣式可為批次式或連續式之任一者。The temperature of the solution polymerization is usually in the range of -80 to 150°C, preferably in the range of 0 to 100°C, more preferably in the range of 10 to 90°C. The aggregation mode can be either batch mode or continuous mode.

上述溶液聚合之聚合反應可藉由聚合停止劑之添加而停止。就聚合停止劑而言，可列舉例如，甲醇、異丙醇等之醇。將所獲得的聚合反應液注入甲醇等之不良溶劑，使未改質共軛二烯系聚合物(F')析出；或者將聚合反應液以水洗淨，分離後，藉由乾燥可將上述未改質共軛二烯系聚合物(F')單離。The polymerization reaction of the above-mentioned solution polymerization can be stopped by the addition of a polymerization stopper. Examples of the polymerization terminator include alcohols such as methanol and isopropanol. Inject the obtained polymerization reaction liquid into a poor solvent such as methanol to precipitate the unmodified conjugated diene polymer (F'); or wash the polymerization reaction liquid with water, separate it, and dry it. The unmodified conjugated diene polymer (F') is isolated.

如此所獲得的未改質共軛二烯系聚合物(F')可以直接進行經由官能團的改質，但亦可於利用後述的氫化方法將該共軛二烯系聚合物中之共軛二烯所衍生的結構單元所含的碳-碳雙鍵之至少一部份氫化後，進行改質。The unmodified conjugated diene polymer (F') obtained in this way can be directly modified via functional groups, but the conjugated diene polymer in the conjugated diene polymer can also be modified by the hydrogenation method described later. After at least a part of the carbon-carbon double bond contained in the structural unit derived from the alkene is hydrogenated, it is modified.

藉由將上述未改質共軛二烯系聚合物(F')經由官能基進行改質，而製造具有包含上述式(II)所示的官能基的部分作為分支鏈的官能基改質共軛二烯系聚合物(F)的方法未被特別限制，但由導入較佳結構之官能基的觀點來看，可列舉例如，使未改質共軛二烯系聚合物(F')中所含的碳-碳雙鍵與具有巰基(-SH)的化合物進行自由基加成反應，藉此將烷氧基矽烷化合物所衍生的官能基導入的方法；將未改質共軛二烯系聚合物(F')中所含的碳-碳雙鍵，於含有鉑化合物的觸媒及因應必要使用的輔觸媒之存在下進行氫矽化，藉此將烷氧基矽烷化合物所衍生的官能基導入的方法等。此等之製造方法之中，由改質試藥、觸媒的取得性、製造成本的觀點來看，使具有巰基(-SH)的化合物進行自由基加成反應的方法為較佳，由所獲得的官能基改質共軛二烯系聚合物(F)之安定性的觀點來看，利用氫矽化將烷氧基矽烷化合物所衍生的官能基導入的方法為較佳。By modifying the above-mentioned unmodified conjugated diene polymer (F') through a functional group, a functional group-modified copolymer having a functional group represented by the above formula (II) as a branched chain is produced The method of the conjugated diene polymer (F) is not particularly limited, but from the viewpoint of introducing a functional group of a preferable structure, for example, the unmodified conjugated diene polymer (F') A method in which the contained carbon-carbon double bond undergoes a radical addition reaction with a compound having a mercapto group (-SH), whereby the functional group derived from the alkoxysilane compound is introduced; the unmodified conjugated diene system The carbon-carbon double bond contained in the polymer (F') undergoes hydrosilation in the presence of a platinum compound-containing catalyst and a co-catalyst as necessary, thereby converting the alkoxysilane compound derived function The method of base import, etc. Among these manufacturing methods, from the viewpoints of the availability of modified reagents and catalysts, and the manufacturing cost, the method of subjecting a compound having a sulfhydryl group (-SH) to a radical addition reaction is preferred. From the viewpoint of the stability of the obtained functional group-modified conjugated diene polymer (F), a method of introducing a functional group derived from an alkoxysilane compound by hydrosilation is preferred.

使上述未改質共軛二烯系聚合物(F')中所含的碳-碳雙鍵與具有巰基(-SH)的化合物進行自由基加成反應，藉此將烷氧基矽烷化合物所衍生的官能基導入的方法而言，較佳為使下述式(IV)所示的矽烷化合物(IV)進行自由基加成反應至未改質共軛二烯系聚合物(F')中所含的碳-碳雙鍵的方法。The carbon-carbon double bond contained in the unmodified conjugated diene polymer (F') is subjected to a radical addition reaction with a compound having a mercapto group (-SH), whereby the alkoxysilane compound is As for the method of introducing the derivatized functional group, it is preferable to subject the silane compound (IV) represented by the following formula (IV) to a radical addition reaction to the unmodified conjugated diene polymer (F') Method of containing carbon-carbon double bonds.

Figure 02_image009
(式(IV)中，R4 表示碳數1～6之2價之伸烷基，R5 、及R6 各自獨立表示碳數6～12之芳基、碳數1～12之烷基、或氫原子，n為1～3之整數，n為2以上的情形，R5 可為相同亦可為相異，3-n為2以上的情形，R6 可為相同亦可為相異。)
Figure 02_image009
(In formula (IV), R 4 represents a divalent alkylene group having 1 to 6 carbons, and R 5 and R 6 each independently represent an aryl group having 6 to 12 carbons, an alkyl group having 1 to 12 carbons, Or a hydrogen atom, n is an integer of 1 to 3, when n is 2 or more, R 5 may be the same or different, and when 3-n is 2 or more, R 6 may be the same or different. )

就上述矽烷化合物(IV)而言，可列舉例如，巰基亞甲基甲基二乙氧基矽烷、巰基亞甲基三乙氧基矽烷、2-巰基乙基三甲氧基矽烷、2-巰基乙基三乙氧基矽烷、2-巰基乙基甲氧基二甲基矽烷、2-巰基乙基乙氧基二甲基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷、3-巰基丙基二甲氧基甲基矽烷、3-巰基丙基二乙氧基甲基矽烷、3-巰基丙基二甲氧基乙基矽烷、3-巰基丙基二乙氧基乙基矽烷、3-巰基丙基甲氧基二甲基矽烷、3-巰基丙基乙氧基二甲基矽烷等。此等矽烷化合物可使用單獨1種，亦可併用2種以上。As for the above-mentioned silane compound (IV), for example, mercaptomethylenemethyldiethoxysilane, mercaptomethylenetriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyl Triethoxysilane, 2-mercaptoethylmethoxydimethylsilane, 2-mercaptoethylethoxydimethylsilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethyl Oxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyldiethoxymethylsilane, 3-mercaptopropyldimethoxyethylsilane, 3-mercaptopropyldiethyl Oxyethyl silane, 3-mercaptopropyl methoxy dimethyl silane, 3-mercaptopropyl ethoxy dimethyl silane, etc. These silane compounds may be used singly, or two or more of them may be used in combination.

藉由使上述矽烷化合物(IV)之巰基(-SH)，對未改質共軛二烯系聚合物(F')中所含的碳-碳雙鍵進行自由基加成反應，可獲得官能基改質共軛二烯系聚合物(F)，其具有矽烷化合物(IV)所衍生的官能基，具體而言，具有作為官能基之下述式(V)所示的部分結構。By subjecting the mercapto group (-SH) of the silane compound (IV) to a radical addition reaction to the carbon-carbon double bond contained in the unmodified conjugated diene polymer (F'), a functional The radical-modified conjugated diene polymer (F) has a functional group derived from the silane compound (IV), specifically, has a partial structure represented by the following formula (V) as a functional group.

Figure 02_image011
(式(V)中，R4 、R5 、R6 、及n之定義與式(IV)相同。)
Figure 02_image011
(In formula (V), the definitions of R 4 , R 5 , R 6 , and n are the same as those in formula (IV).)

使上述矽烷化合物(IV)加成至未改質共軛二烯系聚合物(F')的方法並未特別限定，例如，可採用於未改質共軛二烯系聚合物(F')中添加矽烷化合物(IV)，進一步因應必要添加自由基發生劑，於有機溶劑之存在下或非存在下進行加熱的方法。使用的自由基發生劑並未特別限制，通常可使用市售的有機過氧化物、偶氮系化合物、過氧化氫等。The method for adding the above-mentioned silane compound (IV) to the unmodified conjugated diene polymer (F') is not particularly limited. For example, it can be used for the unmodified conjugated diene polymer (F') It is a method of adding silane compound (IV), and further adding a free radical generator as necessary, and heating in the presence or absence of an organic solvent. The radical generator used is not particularly limited, and generally commercially available organic peroxides, azo compounds, hydrogen peroxide, etc. can be used.

就上述有機過氧化物而言，可列舉例如，甲基乙基酮過氧化物、環己酮過氧化物、3,3,5-三甲基環己酮過氧化物、甲基環己酮過氧化物、乙醯丙酮過氧化物、1,1-雙(三級丁基過氧基)-3,3,5-三甲基環己烷、1,1-雙(三級丁基過氧基)環己烷、1,1-雙(三級己基過氧基)環己烷、2,2-雙(三級丁基過氧基)丁烷、三級丁基氫過氧化物、異丙苯氫過氧化物、二異丙基苯氫過氧化物、對薄荷烷氫過氧化物、2,5-二甲基己烷2,5-二氫過氧化物、1,1,3,3-四甲基丁基氫過氧化物、二(三級丁基)過氧化物、三級丁基異丙苯基過氧化物、二異丙苯基過氧化物、雙(三級丁基過氧基異丙基)苯、2,5-二甲基-2,5-二(三級丁基過氧基)己烷、2,5-己醯基過氧化物、月桂醯基過氧化物、過氧琥珀酸、過氣化苯甲醯及其取代體、2,4-二氯苯甲醯基過氧化物、間甲苯甲醯基過氧化物、二異丙基過氧基二碳酸酯、三級丁基-2-乙基己酸酯、二-2-乙基己基過氧基二碳酸酯、二甲氧基異丙基過氧基碳酸酯、二(3-甲基-3-甲氧基丁基)過氧基二碳酸酯、三級丁基過氧基乙酸酯、過氧異丁酸三級丁酯、三級丁基過氧基新癸酸酯、三級丁基過氧基辛酸酯、三級丁基過氧基3,3,5-三甲基己酸酯、三級丁基過氧基月桂酸酯、三級丁基過氧基碳酸酯、三級丁基過氧基苯甲酸酯、三級丁基過氧基異丁酸酯等。For the above-mentioned organic peroxides, for example, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methyl cyclohexanone Peroxide, acetone peroxide, 1,1-bis(tertiary butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tertiary butylperoxy) Oxy)cyclohexane, 1,1-bis(tertiary hexylperoxy)cyclohexane, 2,2-bis(tertiary butylperoxy)butane, tertiary butyl hydroperoxide, Cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane 2,5-dihydroperoxide, 1,1,3 ,3-Tetramethylbutyl hydroperoxide, di(tertiary butyl) peroxide, tertiary butyl cumyl peroxide, dicumyl peroxide, bis(tertiary butyl) Peroxyisopropyl)benzene, 2,5-dimethyl-2,5-bis(tertiarybutylperoxy)hexane, 2,5-hexyl peroxide, lauryl peroxide Oxide, peroxysuccinic acid, peroxy benzyl peroxide and its substitutes, 2,4-dichlorobenzyl peroxide, m-tolyl peroxide, diisopropyl peroxy two Carbonate, tertiary butyl-2-ethylhexanoate, di-2-ethylhexyl peroxy dicarbonate, dimethoxy isopropyl peroxy carbonate, bis(3-methyl- 3-Methoxybutyl) peroxy dicarbonate, tertiary butyl peroxy acetate, tertiary butyl peroxyisobutyrate, tertiary butyl peroxy neodecanoate, tertiary Butyl peroxy octanoate, tertiary butyl peroxy 3,3,5-trimethyl hexanoate, tertiary butyl peroxy laurate, tertiary butyl peroxy carbonate, Tertiary butyl peroxy benzoate, tertiary butyl peroxy isobutyrate, etc.

就上述偶氮系化合物而言，可列舉例如，2,2'-偶氮雙異丁腈、1,1'-偶氮雙(環己烷-1-甲腈)、2,2'-偶氮雙(2-甲基丁腈)、2,2'-偶氮雙(2,4-二甲基戊腈)、2,2'-偶氮雙(2,4-二甲基-4-甲氧基戊腈)、2,2'-偶氮雙(2-(2-咪唑啉-2-基)丙烷)、2,2'-偶氮雙(2,4,4-三甲基戊烷)、2,2'-偶氮雙(2-甲基丙烷)、2,2'-偶氮雙(2-羥基甲基丙腈)、4,4'-偶氮雙(4-氰基戊酸)、二甲基2,2'-偶氮雙(2-甲基丙酸酯)、2-氰基-2-丙基偶氮甲醯胺、2-苯基偶氮-4-甲氧基-2,4-二甲基戊腈等。 上述自由基發生劑可使用單獨1種，亦可併用2種以上。The above-mentioned azo compounds include, for example, 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azo Azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4- Methoxyvaleronitrile), 2,2'-azobis(2-(2-imidazolin-2-yl)propane), 2,2'-azobis(2,4,4-trimethylpentane) Alkane), 2,2'-azobis(2-methylpropane), 2,2'-azobis(2-hydroxymethylpropionitrile), 4,4'-azobis(4-cyano Valeric acid), dimethyl 2,2'-azobis (2-methyl propionate), 2-cyano-2-propyl azomethamide, 2-phenylazo-4-methyl Oxy-2,4-dimethylvaleronitrile and the like. The said radical generator may be used individually by 1 type, and may use 2 or more types together.

就上述方法所使用的有機溶劑而言，一般可列舉烴系溶劑、鹵素化烴系溶劑。此等有機溶劑之中，以正丁烷、正己烷、正庚烷、環己烷、苯、甲苯、二甲苯等之烴系溶劑為較佳。 上述有機溶劑可使用單獨1種，亦可併用2種以上。The organic solvent used in the above-mentioned method generally includes a hydrocarbon-based solvent and a halogenated hydrocarbon-based solvent. Among these organic solvents, hydrocarbon solvents such as n-butane, n-hexane, n-heptane, cyclohexane, benzene, toluene, and xylene are preferred. The said organic solvent may be used individually by 1 type, and may use 2 or more types together.

再者，利用上述方法進行加成改質化合物的反應時，由抑制副反應的觀點等，可添加老化防止劑。 就此時所使用的較佳老化防止劑而言，可列舉例如，2,6-二(三級丁基)-4-甲基酚(BHT)、2,2'-亞甲基雙(4-甲基-6-三級丁基酚)、4,4'-硫雙(3-甲基-6-三級丁基酚)、4,4'-亞丁基雙(3-甲基-6-三級丁基酚)(AO-40)、3,9-雙[1,1-二甲基-2-[3-(3-三級丁基-4-羥基-5-甲基苯基)丙醯氧基]乙基]-2,4,8,10-四氧雜螺[5.5]十一烷(AO-80)、2,4-雙[(辛硫基)甲基]-6-甲基酚(Irganox1520L)、2,4-雙[(十二基硫基)甲基]-6-甲基酚(Irganox1726)、2-[1-(2-羥基-3,5-二-三級戊基苯基)乙基]-4,6-二-三級戊基苯基丙烯酸酯(SumilizerGS)、2-三級丁基-6-(3-三級丁基-2-羥基-5-甲基苄基)-4-甲基苯基丙烯酸酯(SumilizerGM)、6-三級丁基-4-[3-(2,4,8,10-四-三級丁基二苯并[d,f][1,3,2]二氧磷呯-6-基氧基)丙基]-2-甲基酚(SumilizerGP)、亞磷酸參(2,4-二三級丁基苯基)(Irgafos168)、二(十八基)3,3'-二硫雙丙酸酯、氫醌、對甲氧基酚、N-苯基-N'-(1,3-二甲基丁基)-對伸苯二胺(Nocrac 6C)、雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯(ADEKA LA-77Y)、N,N-二(十八基)羥基胺(IrgastabFS042)、雙(4-三級辛基苯基)胺(Irganox5057)等。 上述老化防止劑可使用單獨1種，亦可併用2種以上。In addition, when performing the reaction of the addition-modifying compound by the above-mentioned method, an anti-aging agent may be added from the viewpoint of suppressing side reactions and the like. As for the preferred anti-aging agent used at this time, for example, 2,6-bis(tertiarybutyl)-4-methylphenol (BHT), 2,2'-methylenebis(4- Methyl-6-tertiary butylphenol), 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 4,4'-butylene bis(3-methyl-6- Tertiary butyl phenol) (AO-40), 3,9-bis[1,1-dimethyl-2-[3-(3-tertiary butyl-4-hydroxy-5-methylphenyl) Propyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane (AO-80), 2,4-bis[(octylthio)methyl]-6- Methylphenol (Irganox1520L), 2,4-bis[(dodecylsulfanyl)methyl]-6-methylphenol (Irganox1726), 2-[1-(2-hydroxy-3,5-di-tri Grade pentyl phenyl) ethyl)-4,6-di-tertiary pentyl phenyl acrylate (SumilizerGS), 2-tertiary butyl-6-(3-tertiary butyl-2-hydroxy-5 -Methylbenzyl)-4-methylphenyl acrylate (SumilizerGM), 6-tertiary butyl-4-[3-(2,4,8,10-tetra-tertiary butyl dibenzo[ d,f][1,3,2]dioxphosphorane-6-yloxy)propyl]-2-methylphenol (SumilizerGP), ginseng phosphite (2,4-di-tertiary butylphenyl) ) (Irgafos168), two (octadecyl) 3,3'-dithiobispropionate, hydroquinone, p-methoxyphenol, N-phenyl-N'-(1,3-dimethylbutyl )-P-phenylenediamine (Nocrac 6C), bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (ADEKA LA-77Y), N,N-bis(ten Octyl) hydroxylamine (IrgastabFS042), bis(4-tertiary octylphenyl)amine (Irganox5057) and the like. The aforementioned anti-aging agent may be used alone or in combination of two or more kinds.

老化防止劑之添加量，相對於未改質共軛二烯系聚合物(F')100質量份，0～10質量份為較佳，0～5質量份為更佳。The amount of the anti-aging agent added is preferably 0-10 parts by mass, more preferably 0-5 parts by mass relative to 100 parts by mass of the unmodified conjugated diene polymer (F').

使上述矽烷化合物(IV)加成至未改質共軛二烯系聚合物(F')的反應中的溫度係10～200℃為較佳，50～180℃為更佳。又反應時間係1～200小時為較佳，1～100小時為更佳，1～50小時為進一步較佳。The temperature in the reaction for adding the silane compound (IV) to the unmodified conjugated diene polymer (F') is preferably 10 to 200°C, more preferably 50 to 180°C. Furthermore, the reaction time is preferably from 1 to 200 hours, more preferably from 1 to 100 hours, and even more preferably from 1 to 50 hours.

將未改質共軛二烯系聚合物(F')中所含的碳-碳雙鍵，於含有鉑化合物的觸媒及因應必要所使用的輔觸媒的存在下進行氫矽化，藉此將烷氧基矽烷化合物所衍生的官能基導入的方法而言，較佳為將未改質共軛二烯系聚合物(F')中所含的碳-碳雙鍵，於含有鉑化合物的觸媒之存在下(較佳為於含有鉑化合物的觸媒及輔觸媒之存在下)，利用下述式(VI)所示的矽烷化合物(VI)進行氫矽化的方法。The carbon-carbon double bond contained in the unmodified conjugated diene polymer (F') is hydrosilated in the presence of a catalyst containing a platinum compound and an auxiliary catalyst used as necessary. As for the method of introducing the functional group derived from the alkoxysilane compound, it is preferable to transfer the carbon-carbon double bond contained in the unmodified conjugated diene polymer (F') to the platinum compound-containing In the presence of a catalyst (preferably in the presence of a platinum compound-containing catalyst and an auxiliary catalyst), a method of hydrosilation using a silane compound (VI) represented by the following formula (VI).

Figure 02_image013
(式(VI)中，R7 、及R8 各自獨立表示碳數6～12之芳基、或碳數1～12之烷基，n為1～3之整數，n為2以上的情形，R7 可為相同亦可為相異，3-n為2以上的情形，R8 可為相同亦可為相異。)
Figure 02_image013
(In formula (VI), R 7 and R 8 each independently represent an aryl group having 6 to 12 carbons or an alkyl group having 1 to 12 carbons, n is an integer of 1 to 3, and n is 2 or more, R 7 may be the same or different, and when 3-n is 2 or more, R 8 may be the same or different.)

就上述矽烷化合物(VI)而言，可列舉例如，三甲氧基矽烷、甲基二甲氧基矽烷、二甲基甲氧基矽烷、三乙氧基矽烷、甲基二乙氧基矽烷、二甲基乙氧基矽烷等。此等矽烷化合物可使用單獨1種，亦可併用2種以上。As for the above-mentioned silane compound (VI), for example, trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, two Methyl ethoxysilane and so on. These silane compounds may be used singly, or two or more of them may be used in combination.

由上述矽烷化合物(VI)，藉由使未改質共軛二烯系聚合物(F')中所含的碳-碳雙鍵經氫矽化反應，可獲得官能基改質共軛二烯系聚合物(F)，其具有矽烷化合物(VI)所衍生的官能基，具體而言，具有作為官能基之下述式(VII)所示的部分結構。From the above-mentioned silane compound (VI), by subjecting the carbon-carbon double bond contained in the unmodified conjugated diene polymer (F') to a hydrosilation reaction, a functional group-modified conjugated diene can be obtained The polymer (F) has a functional group derived from the silane compound (VI), and specifically has a partial structure represented by the following formula (VII) as a functional group.

Figure 02_image015
(式(VII)中，R7 、R8 、及n之定義與式(VI)相同。)
Figure 02_image015
(In formula (VII), the definitions of R 7 , R 8 , and n are the same as those in formula (VI).)

就上述氫矽化反應所使用的含有鉑化合物的觸媒而言，未特別限定，但可列舉例如，氯化鉑酸、氯化鉑酸之醇溶液、鉑-1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物之甲苯或二甲苯溶液；肆三苯基膦鉑、二氯雙三苯基膦鉑、二氯雙乙腈鉑、二氯雙苯甲腈鉑、二氯環辛二烯鉑等、鉑-碳、鉑-氧化鋁、鉑-二氧化矽等之負載型觸媒等。 由進行氫矽化之際的選擇性的面向來看，0價之鉑錯合物為較佳，鉑-1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物之甲苯或二甲苯溶液為更佳。The platinum compound-containing catalyst used in the hydrosilation reaction is not particularly limited, but examples include chloroplatinic acid, an alcohol solution of chloroplatinic acid, and platinum-1,3-divinyl-1 ,1,3,3-Tetramethyldisiloxane complex in toluene or xylene solution; four triphenylphosphinoplatin, dichlorobistriphenylphosphinoplatin, dichlorobisacetonitrile platinum, dichlorobisbenzene Supported catalysts such as platinum nitrile, platinum dichlorocyclooctadiene, platinum-carbon, platinum-alumina, platinum-silica, etc. From the perspective of selectivity during hydrosilation, zero-valent platinum complexes are preferred, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane The toluene or xylene solution of the complex is more preferable.

含有鉑化合物的觸媒之使用量未被特別限定，但由反應性、生產性等的點來看，相對於上述矽烷化合物(VI)1莫耳，含有的鉑原子成為1×10-7 ～1×10-2 莫耳的量為較佳，1×10-7 ～1×10-3 莫耳的量為更佳。The use amount of the platinum compound-containing catalyst is not particularly limited, but from the viewpoints of reactivity, productivity, etc., the platinum atom contained is 1×10 -7 to 1 mol of the above-mentioned silane compound (VI). The amount of 1×10 -2 mol is preferable, and the amount of 1×10 -7 to 1×10 -3 mol is more preferable.

就上述反應中的輔觸媒而言，使用選自包含無機酸之銨鹽、醯胺化合物(acid amide compound)及羧酸的1種以上為較佳。As for the co-catalyst in the above reaction, it is preferable to use one or more selected from the group consisting of ammonium salts containing inorganic acids, acid amide compounds, and carboxylic acids.

就無機酸之銨鹽而言，可列舉例如，氯化銨、硫酸銨、胺基磺酸銨、硝酸銨、磷酸二氫一銨、磷酸氫二銨、磷酸三銨、二亞磷酸銨、碳酸銨、碳酸氫銨、硫化銨、硼酸銨、氟硼酸銨等。此等之中以pKa為2以上的無機酸之銨鹽為較佳，碳酸銨、碳酸氫銨為更佳。For ammonium salts of inorganic acids, for example, ammonium chloride, ammonium sulfate, ammonium sulfamate, ammonium nitrate, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium diphosphite, carbonic acid Ammonium, ammonium bicarbonate, ammonium sulfide, ammonium borate, ammonium fluoroborate, etc. Among these, ammonium salts of inorganic acids having a pKa of 2 or more are preferred, and ammonium carbonate and ammonium bicarbonate are more preferred.

就醯胺化合物而言，可列舉例如，甲醯銨、乙醯銨、N-甲基乙醯銨、N,N-二甲基乙醯銨、丙醯銨、丙烯醯銨、丙二醯胺、琥珀醯胺、苯甲醯胺、反丁烯二醯胺、苯甲醯胺、鄰苯二甲醯胺、棕櫚醯胺、硬脂醯胺等。As for the amide compound, for example, formamide, acetamide, N-methyl acetamide, N,N-dimethyl acetamide, propyl ammonium, acrylamide, malondiamide , Succinamide, benzamide, fumaramide, benzamide, phthalamide, palmitamide, stearylamine, etc.

就羧酸而言，可列舉例如，甲酸、乙酸、丙酸、酪酸、甲氧基乙酸、戊烷酸、己酸、庚烷酸、辛烷酸、乳酸、乙醇酸等。此等之中以甲酸、乙酸、乳酸為較佳，乙酸為更佳。Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, methoxyacetic acid, pentanoic acid, caproic acid, heptanoic acid, octanoic acid, lactic acid, glycolic acid, and the like. Among these, formic acid, acetic acid, and lactic acid are preferable, and acetic acid is more preferable.

輔觸媒之使用量未被特別限定，但由反應性、選擇性、成本等之觀點來看，相對於上述矽烷化合物(VI)1莫耳，1×10-5 ～1×10-1 莫耳為較佳，1×10-4 ～0.5×10-1 莫耳為更佳。The amount of co-catalyst used is not particularly limited, but from the viewpoints of reactivity, selectivity, cost, etc., relative to 1 mol of the above-mentioned silane compound (VI), 1×10 -5 to 1×10 -1 Ears are preferable, and 1×10 -4 to 0.5×10 -1 moles are more preferable.

又，上述氫矽化反應可於無溶劑進行，但亦可使用溶劑。就可使用的溶劑而言，可列舉例如，戊烷、己烷、環己烷、庚烷、異辛烷、苯、甲苯、二甲苯等之烴系溶劑；二乙基醚、四氫呋喃、二

Figure 109146147-A0304-12-0059-1
烷等之醚系溶劑；乙酸乙酯、乙酸丁酯等之酯系溶劑；N,N-二甲基甲醯銨等之非質子性極性溶劑；二氯甲烷、氯仿等之氯化烴系溶劑等。此等溶劑可使用單獨1種，亦可併用2種以上。。In addition, the above-mentioned hydrosilation reaction can be carried out without a solvent, but a solvent can also be used. The usable solvents include, for example, hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene, and xylene; diethyl ether, tetrahydrofuran, and diethyl ether;
Figure 109146147-A0304-12-0059-1
Ether solvents such as alkanes; ester solvents such as ethyl acetate and butyl acetate; aprotic polar solvents such as N,N-dimethyl ammonium carbamate; chlorinated hydrocarbon solvents such as dichloromethane and chloroform Wait. These solvents may be used individually by 1 type, and may use 2 or more types together. .

上述氫矽化反應中的反應溫度未被特別限定，通常為0℃以上之溫度，因應必要可於加熱條件下進行，但0～200℃為較佳。為了獲得適當的反應速度，使於加熱下反應為較佳，由此種觀點來看，反應溫度係40～110℃為更佳，40～90℃為進一步較佳。又，反應時間亦未被特別限定，通常1～60小時左右，但1～30小時為較佳，1～20小時為更佳。The reaction temperature in the above-mentioned hydrosilation reaction is not particularly limited. It is usually a temperature of 0°C or higher. It can be carried out under heating conditions if necessary, but 0 to 200°C is preferred. In order to obtain an appropriate reaction rate, it is preferable to make the reaction under heating. From this viewpoint, the reaction temperature is more preferably 40 to 110°C, and more preferably 40 to 90°C. In addition, the reaction time is also not particularly limited, and is usually about 1 to 60 hours, but preferably 1 to 30 hours, and more preferably 1 to 20 hours.

於上述官能基改質共軛二烯系聚合物(F)，具有上述式(V)或式(VII)所示的部分結構的官能基可含有單獨1種，亦可含有2種以上。因此，官能基改質共軛二烯系聚合物(F)可為由選自包含上述矽烷化合物(IV)及矽烷化合物(VI)的群組的1種之化合物所改質的二烯系聚合物，亦可為由2種以上之化合物所改質的二烯系聚合物。In the functional group-modified conjugated diene polymer (F), the functional group having the partial structure represented by the formula (V) or the formula (VII) may contain one type alone or two or more types. Therefore, the functional group-modified conjugated diene polymer (F) can be a diene polymer modified by a compound selected from the group consisting of the above-mentioned silane compound (IV) and silane compound (VI). The substance may also be a diene polymer modified by two or more compounds.

由所獲得的氫化共軛二烯系接枝聚合物(G)之與極性材料的親和性、安定性的觀點來看，上述式(II)中之Z係Si、Sn、B為較佳，Si為更佳。From the viewpoints of the affinity and stability of the obtained hydrogenated conjugated diene graft polymer (G) with polar materials, the Z-based Si, Sn, and B in the above formula (II) are preferable. Si is better.

由所獲得的氫化共軛二烯系接枝聚合物(G)之與極性材料的親和性、安定性、後述的偶合步驟中的反應性之觀點來看，就上述式(II)中之官能基V而言，烷氧基為較佳，碳數1～5之烷氧基為更佳，甲氧基、及乙氧基為特佳。From the viewpoints of the affinity and stability of the obtained hydrogenated conjugated diene graft polymer (G) with polar materials, and the reactivity in the coupling step described later, the function in the above formula (II) For the group V, an alkoxy group is preferable, an alkoxy group having 1 to 5 carbon atoms is more preferable, and a methoxy group and an ethoxy group are particularly preferable.

上述式(II)中之n為滿足上述式(5)的整數，由後述的偶合步驟中的反應性、與所獲得的氫化共軛二烯系接枝聚合物(G)之分支點結合的側鏈之條數的控制的觀點來看，2以上為較佳，3以上為更佳，與「Z之價數-1」相同者為特佳。N in the above formula (II) is an integer that satisfies the above formula (5), and is combined with the branch point of the hydrogenated conjugated diene graft polymer (G) obtained by the reactivity in the coupling step described later From the viewpoint of control of the number of side chains, 2 or more is preferable, 3 or more is more preferable, and the same as "valence of Z-1" is particularly preferable.

官能基改質共軛二烯系聚合物(F)每1分子之上述式(II)所示的部分的平均個數，1～50個為較佳，2～30個為更佳，3～20個為進一步較佳。The average number of moieties represented by the above formula (II) per molecule of the functional group-modified conjugated diene polymer (F) is preferably from 1 to 50, more preferably from 2 to 30, and from 3 to Twenty are more preferable.

官能基改質共軛二烯系聚合物(F)每1分子之上述式(II)中的官能基V的平均個數係2～150個為較佳，4～90個為更佳，6～60個為進一步較佳。The functional group-modified conjugated diene polymer (F) has an average number of functional groups V in the above formula (II) per molecule, preferably 2 to 150, more preferably 4 to 90, 6 ~60 is further preferred.

官能基改質共軛二烯系聚合物(F)每1分子之上述式(II)中之官能基V的平均個數，使用官能基改質共軛二烯系聚合物(F)所含的官能基V的官能基當量(g/eq)與標準聚苯乙烯換算之數量平均分子量(Mn)，由下述式(9)求得。 (官能基改質共軛二烯系聚合物(F)每1分子之上述式(II)中之官能基V的平均個數)=[(數量平均分子量Mn)/(苯乙烯所衍生的結構單元之分子量)×(共軛二烯及因應必要所含的共軛二烯以外之其它單體所衍生的結構單元之平均分子量)]/(官能基V之官能基當量)  (9)Functional group-modified conjugated diene-based polymer (F) The average number of functional groups V in the above formula (II) per molecule, and the functional group-modified conjugated diene-based polymer (F) contains The functional group equivalent (g/eq) of the functional group V and the number average molecular weight (Mn) in terms of standard polystyrene can be obtained from the following formula (9). (The average number of functional groups V in the above formula (II) per molecule of functional group-modified conjugated diene polymer (F))=((number average molecular weight Mn)/(structure derived from styrene) Molecular weight of unit)×(Average molecular weight of structural unit derived from conjugated diene and other monomers other than conjugated diene contained if necessary))/(functional group equivalent of functional group V) (9)

又，官能基改質共軛二烯系聚合物(F)所含的官能基V之官能基當量係意指官能基V每1個之共軛二烯及因應必要所含的共軛二烯以外之其它單體的質量。官能基之當量，使用1 H-NMR，由來自官能基V的峰與來自聚合物主鏈的峰的面積比而算出。又，來自官能基V的峰係指來自烷氧基及羥基的峰。In addition, the functional group equivalent of the functional group V contained in the functional group-modified conjugated diene polymer (F) means the conjugated diene per functional group V and the conjugated diene contained as necessary The quality of other monomers. The equivalent weight of the functional group was calculated from the area ratio of the peak derived from the functional group V to the peak derived from the polymer main chain using 1 H-NMR. In addition, the peak derived from the functional group V means the peak derived from an alkoxy group and a hydroxyl group.

未改質共軛二烯系聚合物(F')與上述矽烷化合物(IV)或矽烷化合物(VI)之混合比例，例如，只要適當設定成使官能基改質共軛二烯系聚合物(F)每1分子之式(II)所含的官能基V的平均個數成為所冀望的值即可，例如，只要混合成使未改質共軛二烯系聚合物(F')與上述矽烷化合物(IV)或矽烷化合物(VI)之質量比成為0.3～100即可。The mixing ratio of the unmodified conjugated diene polymer (F') and the above-mentioned silane compound (IV) or silane compound (VI), for example, should be appropriately set so that the functional group is modified to the conjugated diene polymer ( F) The average number of functional groups V contained in formula (II) per molecule can be the desired value. For example, it is only necessary to mix the unmodified conjugated diene polymer (F') with the above The mass ratio of the silane compound (IV) or the silane compound (VI) may be 0.3-100.

官能基改質共軛二烯系聚合物(F)之Mw及乙烯基含量之適合範圍係與未改質共軛二烯系聚合物(F')的情形相同。The suitable range of the Mw and vinyl content of the functional group-modified conjugated diene polymer (F) is the same as the case of the unmodified conjugated diene polymer (F').

上述官能基改質共軛二烯系聚合物(F)之於38℃測定的融熔黏度係0.1～2,000Pa・s為較佳，0.1～1500Pa・s為更佳，0.1～1000Pa・s為進一步較佳。官能基改質共軛二烯系聚合物(F)之融熔黏度為前述範圍內時，有製造時之製程通過性優異、經濟性變良好的傾向。The above-mentioned functional group-modified conjugated diene polymer (F) has a melt viscosity measured at 38°C of 0.1 to 2,000 Pa·s, preferably 0.1 to 1500 Pa·s, and more preferably 0.1 to 1000 Pa·s Further better. When the melt viscosity of the functional group-modified conjugated diene polymer (F) is within the aforementioned range, the process passability during manufacture tends to be excellent and the economic efficiency tends to be improved.

於步驟(A-1)，藉由使活性末端聚合物(I)與上述官能基改質共軛二烯系聚合物(F)反應，發生上述式(II)所示的部分中之官能基V與前述活性末端聚合物(I)之置換反應，形成了為分支點的雜原子Z與側鏈的前述活性末端聚合物(I)結合的共軛二烯系接枝聚合物(G')(以下，將本反應稱為偶合反應)。於該偶合反應、及後述的不活性化步驟中未反應的官能基V(選自包含烷氧基及羥基的群組的至少1個殘存的官能基)為直接殘存，或經水解，形成與氫化共軛二烯系接枝聚合物(G)之分支點結合的選自包含烷氧基及羥基的群組的至少1個官能基(c)。In step (A-1), by reacting the living terminal polymer (I) with the above-mentioned functional group-modified conjugated diene polymer (F), the functional group in the part represented by the above-mentioned formula (II) is generated The substitution reaction between V and the aforementioned living end polymer (I) forms a conjugated diene graft polymer (G') in which the heteroatom Z as a branch point is bonded to the aforementioned living end polymer (I) of the side chain (Hereinafter, this reaction is referred to as a coupling reaction). The unreacted functional group V (at least one remaining functional group selected from the group consisting of an alkoxy group and a hydroxyl group) remains unreacted in the coupling reaction and the inactivation step described later, or is formed by hydrolysis and At least one functional group (c) selected from the group containing an alkoxy group and a hydroxyl group to which the branch point of the hydrogenated conjugated diene graft polymer (G) is bonded.

氫化共軛二烯系接枝聚合物(G)每1分子之與上述分支點直接結合的側鏈(b)之平均條數W，可藉由上述偶合反應中的活性末端聚合物(I)與官能基改質共軛二烯系聚合物(F)之進料量的比，而調整至所冀望之範圍。例如，(活性末端聚合物(I)之進料量(莫耳數))/(官能基改質共軛二烯系聚合物(F)之進料量(莫耳數))=4/1的情形，側鏈(b)之平均條數W成為4條。惟，W之上限為官能基改質共軛二烯系聚合物(F)每1分子具有的官能基V之個數。The average number W of side chains (b) directly bonded to the above-mentioned branch points per molecule of the hydrogenated conjugated diene graft polymer (G) can be determined by the active terminal polymer (I) in the above-mentioned coupling reaction The ratio of the feed amount to the functional group-modified conjugated diene polymer (F) is adjusted to the desired range. For example, (feeding amount of living end polymer (I) (number of moles))/(feeding amount of functional group-modified conjugated diene polymer (F) (number of moles))=4/1 In the case of, the average number W of side chains (b) becomes four. However, the upper limit of W is the number of functional groups V per molecule of the functional group-modified conjugated diene polymer (F).

(活性末端聚合物(I)之進料量)/(官能基改質共軛二烯系聚合物(F)之進料量)之莫耳比，只要適當設定成使氫化共軛二烯系接枝聚合物(G)每1分子之與上述分支點直接結合的側鏈(b)之平均條數W成為所冀望的值即可，例如，1～200為較佳，2～100為更佳，3～50為進一步較佳。(活性末端聚合物(I)之進料量)/(官能基改質共軛二烯系聚合物(F)之進料量)之莫耳比小於1時，可導入的側鏈之條數變少，大於200時，後述的偶合率有降低的傾向。The molar ratio of (feeding amount of living terminal polymer (I))/(feeding amount of functional group-modified conjugated diene polymer (F)) can be appropriately set so that the hydrogenated conjugated diene The average number W of side chains (b) directly bonded to the above-mentioned branch points per molecule of the graft polymer (G) may be the desired value. For example, 1 to 200 is preferable, and 2 to 100 is more preferable. Preferably, 3-50 is more preferable. When the molar ratio of (feeding amount of living end polymer (I))/(feeding amount of functional group-modified conjugated diene polymer (F)) is less than 1, the number of side chains that can be introduced When it is smaller than 200, the coupling ratio described later tends to decrease.

上述偶合反應通常為0～100℃之溫度範圍，進行0.5～50小時。官能基改質共軛二烯系聚合物(F)可稀釋而使用，就稀釋溶劑而言，只要對活性末端為不活性，且對反應無不良影響即可，未特別限制，可列舉例如，己烷、環己烷、庚烷、辛烷、癸烷、甲苯、苯、二甲苯等之飽和脂肪族烴或芳香族烴。 又，於偶合反應之際，可添加鹼作為添加劑。就路易士鹼而言，可列舉例如，二甲基醚、二乙基醚、四氫呋喃等之醚類；乙二醇二甲基醚、二乙二醇二甲基醚等之二醇醚類；三乙基胺、N,N,N',N'-四甲基乙二胺、N-甲基

Figure 109146147-A0304-12-0020-6
啉等之胺類等。此等路易士鹼，可使用單獨1種，亦可併用2種以上。The above-mentioned coupling reaction is usually carried out in the temperature range of 0-100°C for 0.5-50 hours. The functional group-modified conjugated diene polymer (F) can be diluted and used. As far as the dilution solvent is concerned, as long as it is inactive to the active terminal and does not adversely affect the reaction, it is not particularly limited. For example, Saturated aliphatic or aromatic hydrocarbons such as hexane, cyclohexane, heptane, octane, decane, toluene, benzene, xylene, etc. In addition, at the time of the coupling reaction, a base may be added as an additive. For Lewis bases, for example, ethers such as dimethyl ether, diethyl ether, and tetrahydrofuran; glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; Triethylamine, N,N,N',N'-tetramethylethylenediamine, N-methyl
Figure 109146147-A0304-12-0020-6
Amines such as morpholino. These Lewis bases may be used singly, or two or more of them may be used in combination.

於上述偶合反應，可於合成上述活性末端聚合物(I)的反應容器中添加上述官能基改質共軛二烯系聚合物(F)，相反地，可對上述官能基改質共軛二烯系聚合物(F)添加上述活性末端聚合物(I)。又，如上述，上述活性末端聚合物(I)、上述官能基改質共軛二烯系聚合物(F)之任一者，因應必要可以溶劑進行稀釋而使用。又，上述活性末端聚合物(I)，可使用單獨1種，亦可併用2種以上，上述官能基改質共軛二烯系聚合物(F)，可使用單獨1種，亦可併用2種以上。In the above-mentioned coupling reaction, the above-mentioned functional group-modified conjugated diene polymer (F) can be added to the reaction vessel for synthesizing the above-mentioned living terminal polymer (I). Conversely, the above-mentioned functional group can be modified by the conjugated diene polymer (F). The olefin polymer (F) adds the above-mentioned living terminal polymer (I). In addition, as described above, any one of the living terminal polymer (I) and the functional group-modified conjugated diene polymer (F) can be used after being diluted with a solvent as necessary. In addition, the above-mentioned living terminal polymer (I) may be used alone or in combination of two or more. The functional group-modified conjugated diene polymer (F) may be used alone or in combination. More than species.

上述偶合反應中的偶合率係50%以上為較佳，60%以上為更佳，70%以上為進一步較佳。上述偶合率小於50%時，因所獲得的氫化共軛二烯系接枝聚合物(G)之力學特性降低而不佳。偶合率係使用GPC測定所獲得的偶合未反應之上述活性末端聚合物(I)所衍生的成分之峰面積與全部的峰面積之總和，由下述式(10)而求得。 (偶合率(%))=[｛(全部之峰面積的總和)-(活性末端聚合物(I)所衍生的成分之峰面積)｝/(全部之峰面積的總和)]×100  (10)The coupling ratio in the above-mentioned coupling reaction is preferably 50% or more, more preferably 60% or more, and even more preferably 70% or more. When the above-mentioned coupling ratio is less than 50%, the mechanical properties of the obtained hydrogenated conjugated diene graft polymer (G) are deteriorated, which is not good. The coupling rate is the sum of the peak area of the component derived from the coupled unreacted active terminal polymer (I) obtained by GPC measurement and the total peak area, and is calculated by the following formula (10). (Coupling rate (%))=[{(Sum of all peak areas)-(Peak area of components derived from active end polymer (I))}/(Sum of all peak areas)]×100 (10 )

偶合率可藉由提高官能基改質共軛二烯系聚合物(F)之添加量、提高路易士鹼之添加量、提高反應溫度、延長反應時間而調高。偶合反應可進行至偶合率成為所冀望之範圍為止。之後，藉由添加甲醇、異丙醇等之聚合停止劑，可停止偶合反應。The coupling rate can be adjusted by increasing the addition amount of the functional group-modified conjugated diene polymer (F), increasing the addition amount of Lewis base, increasing the reaction temperature, and prolonging the reaction time. The coupling reaction can proceed until the coupling rate becomes the desired range. After that, the coupling reaction can be stopped by adding a polymerization terminator such as methanol and isopropanol.

與上述分支點直接結合的官能基(c)之個數，可依上述偶合反應中的上述活性末端聚合物(I)與官能基改質共軛二烯系聚合物(F)之進料量的莫耳比、將後述選自包含烷氧基及羥基的群組的至少1個殘存的官能基(未反應之官能基V)之一部分不活性化的步驟中的試藥之使用量及反應時間、及因應必要所使用的極性化合物之種類及添加量，可調整至所冀望之範圍。 就將與上述分支點直接結合的官能基(c)之個數調整至所冀望之範圍的方法而言，可列舉例如，上述活性末端聚合物(I)與官能基改質共軛二烯系聚合物(F)之進料量以氫化共軛二烯系接枝聚合物(G)所含的每分支點之官能基(c)的平均個數(X/Y)成為1以上的方式的莫耳比進行偶合反應，之後，使(X/Y)成為小於1的方式將上述殘存的官能基(未反應之官能基V)之一部分不活性化的方法。The number of functional groups (c) directly bonded to the above-mentioned branch points can be modified according to the above-mentioned living terminal polymer (I) and functional groups in the above-mentioned coupling reaction to modify the feed amount of the conjugated diene polymer (F) The molar ratio of at least one remaining functional group (unreacted functional group V) selected from the group consisting of alkoxy and hydroxyl groups described below is partially inactivated. The amount of reagent used and the reaction The time, as well as the type and amount of polar compounds used as necessary, can be adjusted to the desired range. Regarding the method of adjusting the number of functional groups (c) directly bonded to the above-mentioned branch point to the desired range, for example, the above-mentioned living terminal polymer (I) and functional group-modified conjugated diene system The feed amount of the polymer (F) is such that the average number (X/Y) of the functional groups (c) per branch point contained in the hydrogenated conjugated diene graft polymer (G) becomes 1 or more A method in which a molar ratio undergoes a coupling reaction, and then a part of the remaining functional group (unreacted functional group V) is inactivated so that (X/Y) becomes less than 1.

[步驟(A-2)] 本發明之氫化共軛二烯系接枝聚合物(G)之製造方法，為了將與上述分支點直接結合的官能基(c)之個數調整為所冀望之範圍，於步驟(A-1)之後，包含下列者為較佳一態樣： (A-2)將前述共軛二烯系接枝聚合物(G')中、或經由後述的氫化步驟的氫化共軛二烯系接枝聚合物(G)中之選自包含烷氧基及羥基的群組的至少1個殘存的官能基(未反應而存在的官能基V)之一部分不活性化的步驟(以下，稱為不活性化步驟)。 認為藉由於回收步驟(C)添加的水或酸，所獲得的共軛二烯系接枝聚合物中所含的烷氧基反應而生成羥基，成為含有比較多的羥基時，此等多量之羥基彼此容易發生縮合反應，因而不活性化步驟(A-2)於回收步驟(C)之前進行為較佳。又，不活性化步驟(A-2)可於氫化步驟(B)之前後任一者中進行，但由官能基(c)之個數調整的容易性、及氫化步驟(B)中的反應性的觀點來看，氫化步驟(B)之前進行為較佳。[Step (A-2)] In the method for producing the hydrogenated conjugated diene graft polymer (G) of the present invention, in order to adjust the number of functional groups (c) directly bonded to the branch point to the desired range, step (A-1) After ), it is better to include the following: (A-2) Among the aforementioned conjugated diene graft polymer (G'), or the hydrogenated conjugated diene graft polymer (G) that has undergone the hydrogenation step described later, is selected from the group containing alkoxy groups A step of inactivating a part of at least one remaining functional group (functional group V that exists without reaction) of the group of hydroxyl groups (hereinafter referred to as an inactivation step). It is considered that the alkoxy groups contained in the obtained conjugated diene graft polymer react by the water or acid added in the recovery step (C) to generate hydroxyl groups, and when it contains a relatively large number of hydroxyl groups, such a large amount The hydroxyl groups are prone to condensation reaction with each other, and therefore the inactivation step (A-2) is preferably carried out before the recovery step (C). In addition, the inactivation step (A-2) can be performed before or after the hydrogenation step (B), but the ease of adjustment by the number of functional groups (c) and the reactivity in the hydrogenation step (B) From the viewpoint of, it is preferable to carry out the hydrogenation step (B) before.

就用以將烷氧基及羥基不活性化所使用的試藥(以下，有時稱為不活性化試藥)而言，可列舉例如，甲基鋰、乙基鋰、正丙基鋰、異丙基鋰、正丁基鋰、二級丁基鋰、三級丁基鋰等之烷基鋰類；甲基鈉、乙基鈉、正丙基鈉、異丙基鈉、正丁基鈉、二級丁基鈉、三級丁基鈉等之烷基鈉類；甲基鉀、乙基鉀、正丙基鉀、異丙基鉀、正丁基鉀、二級丁基鉀、三級丁基鉀等之烷基鉀類；甲基鎂溴化物、乙基鎂溴化物、三級丁基鎂溴化物、三級丁基鎂氯化物、二級丁基鎂碘化物等之烷基鎂鹵化物類；二甲基銅鋰、二乙基銅鋰、甲基乙基銅鋰、甲基正丙基銅鋰、乙基正丁基銅鋰等之二烷基銅鋰類；鋰二異丙基醯胺、鋰二異乙基醯胺、鋰二(三級丁基)醯胺等之鋰醯胺類等之路易士鹼。此等之中，因期望加速不活性化反應進行而立體障礙小，正丁基鋰、二級丁基鋰、甲基鋰、甲基鎂溴化物、二甲基銅鋰為較佳。Examples of reagents used to inactivate alkoxy groups and hydroxyl groups (hereinafter, sometimes referred to as inactivation reagents) include methyl lithium, ethyl lithium, n-propyl lithium, Alkyl lithiums such as isopropyl lithium, n-butyl lithium, secondary butyl lithium, tertiary butyl lithium, etc.; methyl sodium, ethyl sodium, n-propyl sodium, isopropyl sodium, n-butyl sodium , Sodium secondary butyl sodium, tertiary butyl sodium, etc.; methyl potassium, ethyl potassium, n-propyl potassium, isopropyl potassium, n-butyl potassium, secondary butyl potassium, tertiary Alkyl potassium such as butyl potassium; Alkyl magnesium such as methyl magnesium bromide, ethyl magnesium bromide, tertiary butyl magnesium bromide, tertiary butyl magnesium chloride, secondary butyl magnesium iodide, etc. Halides; dimethyl copper lithium, diethyl copper lithium, methyl ethyl copper lithium, methyl n-propyl copper lithium, ethyl n-butyl copper lithium and other dialkyl copper lithiums; lithium diiso Lithium amides such as propyl amide, lithium diisoethyl amide, lithium bis(tertiary butyl) amide, etc. Among these, since it is desired to accelerate the progress of the inactivation reaction and the steric obstacle is small, n-butyl lithium, secondary butyl lithium, methyl lithium, methyl magnesium bromide, and dimethyl copper lithium are preferable.

步驟(A-2)中的不活性化試藥之使用量/步驟(A-1)所獲得的共軛二烯系接枝聚合物(G')中所含的官能基V所衍生的烷氧基及羥基之合計量的莫耳比為0.5以上為較佳，1.0以上為更佳，2.0以上為進一步較佳。又，100以下為較佳，50以下為更佳，20以下為進一步較佳。不活性化試藥之量為少的情形，無法將與上述分支點直接結合的官能基(c)之個數調整至所冀望之範圍，又，不活性化試藥之量為多的情形，經濟性有惡化的傾向。The amount of inactivation reagent used in step (A-2)/alkane derived from functional group V contained in the conjugated diene graft polymer (G') obtained in step (A-1) The molar ratio of the total amount of the oxy group and the hydroxy group is preferably 0.5 or more, more preferably 1.0 or more, and even more preferably 2.0 or more. Moreover, 100 or less is preferable, 50 or less is more preferable, and 20 or less is more preferable. When the amount of inactivation reagent is small, the number of functional groups (c) directly bonded to the branch point cannot be adjusted to the desired range, and when the amount of inactivation reagent is large, The economy tends to deteriorate.

上述步驟(A-2)之不活性化反應通常為0～100℃之溫度範圍，進行0.1～50小時。不活性化試藥可稀釋而使用，就稀釋溶劑而言，只要對不活性化試藥為不活性，且對反應無不良影響即可，未特別限制，可列舉例如，己烷、環己烷、庚烷、辛烷、癸烷、甲苯、苯、二甲苯等之飽和脂肪族烴或芳香族烴。又，上述不活性化反應之際可添加作為添加劑之路易士鹼，就路易士鹼而言，可列舉例如，二甲基醚、二乙基醚、四氫呋喃等之醚類；乙二醇二甲基醚、二乙二醇二甲基醚等之二醇醚類；三乙基胺、N,N,N',N'-四甲基乙二胺、N-甲基

Figure 109146147-A0304-12-0020-6
啉等之胺類等。此等路易士鹼可使用單獨1種，亦可併用2種以上。The inactivation reaction in the above step (A-2) is usually in the temperature range of 0-100°C and is carried out for 0.1-50 hours. The inactivation reagent can be diluted and used. As far as the dilution solvent is concerned, as long as it is inactive to the inactivation reagent and has no adverse effect on the reaction, it is not particularly limited. Examples include hexane and cyclohexane. , Heptane, octane, decane, toluene, benzene, xylene and other saturated aliphatic or aromatic hydrocarbons. In addition, at the time of the above-mentioned inactivation reaction, it is possible to add lysine as an additive. For Lewis’sine, for example, ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, etc.; ethylene glycol dimethyl ether Glycol ethers such as base ether and diethylene glycol dimethyl ether; triethylamine, N,N,N',N'-tetramethylethylenediamine, N-methyl
Figure 109146147-A0304-12-0020-6
Amines such as morpholino. These Lewis bases may be used singly, or two or more of them may be used in combination.

上述不活性化反應，可進行至與上述分支點直接結合的官能基(c)之個數成為所冀望之範圍為止。之後，藉由添加甲醇、異丙醇等之聚合停止劑，可使不活性化試藥失活。The above-mentioned inactivation reaction can proceed until the number of functional groups (c) directly bonded to the above-mentioned branch point becomes the desired range. After that, by adding a polymerization stopper such as methanol, isopropanol, etc., the inactivation reagent can be inactivated.

[步驟(B)] 本發明之氫化共軛二烯系接枝聚合物之製造方法包含： (B)將上述共軛二烯系接枝聚合物(G')氫化而形成氫化共軛二烯系接枝聚合物(G)的步驟。[Step (B)] The manufacturing method of the hydrogenated conjugated diene graft polymer of the present invention includes: (B) The step of hydrogenating the above-mentioned conjugated diene-based graft polymer (G′) to form a hydrogenated conjugated diene-based graft polymer (G).

藉由交付於將由前述方法所獲得的共軛二烯系接枝聚合物進行氫化的步驟，可獲得本發明之氫化共軛二烯系接枝聚合物。氫化的方法未特別限制，例如可使用周知之方法。可繼續進行上述步驟(A-1)(或步驟(A-2))與氫化，亦可自共軛二烯系接枝聚合物單離後進行氫化。將共軛二烯系接枝聚合物單離的方法，與後述的回收步驟(C)相同。The hydrogenated conjugated diene graft polymer of the present invention can be obtained by passing it to the step of hydrogenating the conjugated diene graft polymer obtained by the aforementioned method. The method of hydrogenation is not particularly limited, and, for example, a well-known method can be used. The above-mentioned step (A-1) (or step (A-2)) and hydrogenation can be continued, or the conjugated diene-based graft polymer can be isolated and then hydrogenated. The method for isolating the conjugated diene-based graft polymer is the same as the recovery step (C) described later.

就步驟(B)之氫化反應所使用的觸媒而言，能使用烯烴化合物等中所含的碳-碳雙鍵經氫化所獲得的觸媒。就此種觸媒而言，通常可列舉不均相觸媒、均相觸媒等。As the catalyst used in the hydrogenation reaction of the step (B), a catalyst obtained by hydrogenating carbon-carbon double bonds contained in an olefin compound or the like can be used. Regarding such catalysts, in general, heterogeneous catalysts, homogeneous catalysts, and the like can be cited.

上述不均相觸媒未特別被限定，但就其具體例而言，可列舉海綿鎳、海綿鈷、海綿銅等之海綿金屬觸媒；鎳二氧化矽、鎳氧化鋁、鎳沸石、鎳矽藻土、鈀二氧化矽、鈀氧化鋁、鈀沸石、鈀矽藻土、鈀碳、鈀碳酸鈣、鉑二氧化矽、鉑氧化鋁、鉑沸石、鉑矽藻土、鉑碳、鉑碳酸鈣、釕二氧化矽、釕氧化鋁、釕沸石、釕矽藻土、釕碳、釕碳酸鈣、銥二氧化矽、銥氧化鋁、銥沸石、銥矽藻土、銥碳、銥碳酸鈣、鈷二氧化矽、鈷氧化鋁、鈷沸石、鈷矽藻土、鈷碳、鈷碳酸鈣等之負載金屬觸媒。 此等不均相觸媒以活性提升、選擇性提升、安定性為目的，可藉由鐵、鉬、鎂等進行改質。又，此等不均相觸媒可單獨使用1種，亦可混合2種以上使用。The above heterogeneous catalyst is not particularly limited, but specific examples thereof include sponge metal catalysts such as sponge nickel, sponge cobalt, and sponge copper; nickel silica, nickel alumina, nickel zeolite, nickel silicon Algae earth, palladium silica, palladium alumina, palladium zeolite, palladium diatomaceous earth, palladium carbon, palladium calcium carbonate, platinum silica, platinum alumina, platinum zeolite, platinum diatomaceous earth, platinum carbon, platinum calcium carbonate , Ruthenium silica, ruthenium alumina, ruthenium zeolite, ruthenium diatomaceous earth, ruthenium carbon, ruthenium calcium carbonate, iridium silica, iridium alumina, iridium zeolite, iridium diatomaceous earth, iridium carbon, iridium calcium carbonate, cobalt Supported metal catalysts such as silica, cobalt alumina, cobalt zeolite, cobalt diatomaceous earth, cobalt carbon, cobalt calcium carbonate, etc. These heterogeneous catalysts aim at increasing activity, increasing selectivity, and stability, and can be modified by iron, molybdenum, magnesium, etc. Moreover, these heterogeneous catalysts may be used individually by 1 type, and may mix and use 2 or more types.

上述均相觸媒未特別被限定，但就其具體例而言，可列舉包含過渡金屬化合物、烷基鋁或烷基鋰的齊格勒系觸媒；茂金屬系觸媒。 就齊格勒系觸媒所使用的過渡金屬化合物之具體例而言，可列舉乙酸鎳、辛酸鎳、乙醯丙酮鎳等之鎳鹽；乙酸鈷、辛酸鈷、乙醯丙酮鈷等之鈷鹽；二氯化二茂鈦(titanocene dichloride)、二氯化二茂鋯(zirconocene dihydride)。 就齊格勒系觸媒所使用的烷基鋁之具體例而言，可列舉三甲基鋁、三乙基鋁、三異丁基鋁、三辛基鋁。 就齊格勒系觸媒所使用的烷基鋰之具體例而言，可列舉甲基鋰、乙基鋰、正丁基鋰、二級丁基鋰、三級丁基鋰。 此等均相觸媒可單獨使用1種，亦可混合2種以上使用。又，均相觸媒與不均相觸媒混合而使用亦無妨。The above-mentioned homogeneous catalyst is not particularly limited, but specific examples thereof include Ziegler-based catalysts containing transition metal compounds, aluminum alkyls, or lithium alkyls; metallocene-based catalysts. Specific examples of transition metal compounds used in Ziegler-based catalysts include nickel salts such as nickel acetate, nickel octoate, and nickel acetylacetonate; cobalt salts such as cobalt acetate, cobalt octoate, and cobalt acetylacetonate. ; Titanocene dichloride (titanocene dichloride), zirconocene dihydride (zirconocene dihydride). Specific examples of aluminum alkyls used in Ziegler-based catalysts include trimethylaluminum, triethylaluminum, triisobutylaluminum, and trioctylaluminum. Specific examples of alkyl lithium used in Ziegler-based 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. In addition, it does not matter if the homogeneous catalyst and the heterogeneous catalyst are mixed and used.

步驟(B)之氫化反應中，為了將聚合物氫化，相對於低分子化合物，反應活性一般較低。因此，作為反應條件，比較高溫、高壓條件為較佳情形為多的，以熱安定性高的不均相觸媒進行者為較佳。由氫化活性的面向來看，具有氫化活性且使用作為金屬之鎳或鈀者為較佳。又，為了抑制氫化反應中之不欲副反應，使用作為載體之碳酸鈣、碳載體為較佳，使用碳載體為進一步較佳。In the hydrogenation reaction of step (B), in order to hydrogenate the polymer, the reaction activity is generally lower than that of the low-molecular compound. Therefore, as the reaction conditions, there are many cases where relatively high temperature and high pressure conditions are better, and it is better to use heterogeneous catalysts with high thermal stability. From the aspect of hydrogenation activity, it is preferable to have hydrogenation activity and use nickel or palladium as the metal. In addition, in order to suppress unwanted side reactions in the hydrogenation reaction, it is preferable to use calcium carbonate or a carbon carrier as a carrier, and it is more preferable to use a carbon carrier.

氫化反應通常於有機溶劑中進行。該有機溶劑未被特別限定，例如可使用於上述步驟(A-1)中例示的陰離子聚合中使用的溶劑。The hydrogenation reaction is usually carried out in an organic solvent. The organic solvent is not particularly limited, and it can be used, for example, in the solvent used in the anionic polymerization exemplified in the above step (A-1).

上述氫化反應，例如，可於上述步驟(A-1)之際使用的溶劑中直接於共軛二烯系接枝聚合物(G’)存在的狀態，特別是未對有機溶劑施予處理而進行，亦可藉由將該溶劑之一部分蒸餾等之方法而去除後，於殘存的溶劑中進行，或可另外以有機溶劑稀釋後，於該溶劑中進行。又，上述步驟(A-1)(或步驟(A-2))結束後，一旦取出共軛二烯系接枝聚合物(G')，可將此共軛二烯系接枝聚合物(G')投入至有機溶劑中，於該溶劑中進行氫化反應。The above-mentioned hydrogenation reaction, for example, can be directly in the state where the conjugated diene-based graft polymer (G') exists in the solvent used in the above-mentioned step (A-1), especially if the organic solvent is not treated. It can also be carried out by a method such as distillation of a part of the solvent and then carried out in the remaining solvent, or it can be carried out in the solvent after being diluted with an organic solvent. In addition, after the above step (A-1) (or step (A-2)) is completed, once the conjugated diene-based graft polymer (G') is taken out, the conjugated diene-based graft polymer ( G') Put it into an organic solvent, and carry out a hydrogenation reaction in this solvent.

氫化反應於有機溶劑中進行的情形，有機溶劑之使用量，作為反應液中之共軛二烯系接枝聚合物(G')之濃度，成為1質量%以上、30質量%以下的量者為較佳。於小於1質量%進行時，有生產性顯著降低的情形，超過30質量%的情形，有黏度顯著變高，混合效率降低的情形。When the hydrogenation reaction is carried out in an organic solvent, the amount of the organic solvent used, as the concentration of the conjugated diene graft polymer (G') in the reaction solution, is 1% by mass or more and 30% by mass or less For better. When it is performed at less than 1% by mass, the productivity may be significantly reduced, and when it exceeds 30% by mass, the viscosity may increase significantly and the mixing efficiency may decrease.

氫化反應之反應壓力，因應使用的觸媒等而適當設定即可，作為全壓，通常為0.1MPa～20MPa，較佳為0.5MPa～15MPa，更佳為0.5MPa～5MPa。The reaction pressure of the hydrogenation reaction may be appropriately set according to the catalyst used, and the total pressure is usually 0.1 MPa to 20 MPa, preferably 0.5 MPa to 15 MPa, and more preferably 0.5 MPa to 5 MPa.

氫化反應係於氫氣存在下實施，但亦可於氫氣以外之對氫化反應不活性的氣體混合的氣體存在下實施。就對氫化反應不活性的氣體之具體例而言，可列舉氮、氦、氬、二氧化碳。又，依反應條件，反應中使用的溶劑可具有顯著比例之作為氣體成分的分壓的情形，但只要氫化反應進行，此種狀況通常無問題。The hydrogenation reaction is carried out in the presence of hydrogen, but it can also be carried out in the presence of a mixture of gases other than hydrogen that are inactive to the hydrogenation reaction. Specific examples of the gas inactive to the hydrogenation reaction include nitrogen, helium, argon, and carbon dioxide. In addition, depending on the reaction conditions, the solvent used in the reaction may have a significant proportion of the partial pressure of the gas component, but as long as the hydrogenation reaction proceeds, this situation is usually no problem.

氫化反應之反應溫度，因應使用的觸媒而適當設定即可，通常20℃～250℃，較佳為50℃～180℃，更佳為70℃～180℃。一般而言，不均相觸媒與均勻相相比，有希望於較高溫度下進行反應的情形。 氫化反應之反應時間，因應使用的觸媒種類、觸媒量、反應溫度而適當設定即可，通常為0.1～100小時，較佳為1～50小時。反應時間過短的情形，有無法獲得冀望的氫化率的情形。又，反應時間過長的情形，不希望的副反應的進行變顯著，有無法獲得所冀望的物性之氫化共軛二烯系接枝聚合物(G)的情形。The reaction temperature of the hydrogenation reaction may be appropriately set according to the catalyst used, and is usually 20°C to 250°C, preferably 50°C to 180°C, and more preferably 70°C to 180°C. Generally speaking, the heterogeneous phase catalyst is expected to react at a higher temperature than the homogeneous phase. The reaction time of the hydrogenation reaction may be appropriately set according to the type of catalyst used, the amount of catalyst, and the reaction temperature, and it is usually 0.1 to 100 hours, preferably 1 to 50 hours. When the reaction time is too short, there are cases where the desired hydrogenation rate cannot be obtained. In addition, when the reaction time is too long, the progress of undesirable side reactions becomes remarkable, and the hydrogenated conjugated diene-based graft polymer (G) of the desired physical properties may not be obtained in some cases.

氫化反應之反應形式未特別限制，因應反應使用的觸媒之種類等而適當設定即可。就此反應形式而言，可列舉例如，批次反應形式、半連續反應形式(半批次反應形式)、連續反應形式。就適合的連續反應形式而言，可列舉塞流(plug flow)形式(PFR)、連續流通攪拌形式(CSTR)等。 使用不均相觸媒的情形，可使用固定床反應槽而進行氫化反應。 於積極的混合條件下進行氫化反應的情形，作為此混合方法，可列舉利用攪拌的混合方法、以環路形式使反應液循環的混合方法。 於混合條件下使用不均相觸媒的情形，成為利用懸浮床的反應、或成為氣-液-固之反應場。又，於混合條件下使用均相觸媒的情形，成為氣-液2相系反應場。 一旦於反應器中之氫化反應結束，取出反應液，將該取出的反應液之至少一部分，投入相同或相異的反應器中，可以進一步進行氫化反應的反應形式下進行氫化反應。藉由於此種反應形式下進行氫化反應，可能迴避隨著氫化反應而發熱的局部化的情形、有氫化率提升的情形。 氫化反應能以單獨1種的反應形式進行，亦可組合相同或相異的2種以上之反應形式而進行。 以較高氫化率為目標的情形，有使用固定床反應槽，包含以塞流形式使反應的步驟的氫化反應步驟為冀望的情形。The reaction form of the hydrogenation reaction is not particularly limited, and may be appropriately set according to the type of catalyst used in the reaction, etc. Regarding this reaction format, for example, a batch reaction format, a semi-continuous reaction format (semi-batch reaction format), and a continuous reaction format can be cited. As for the suitable continuous reaction form, plug flow form (PFR), continuous flow stirring form (CSTR), etc. can be mentioned. When a heterogeneous catalyst is used, a fixed bed reaction tank can be used to perform the hydrogenation reaction. When the hydrogenation reaction is carried out under active mixing conditions, examples of this mixing method include a mixing method using stirring and a mixing method in which the reaction liquid is circulated in a loop. When a heterogeneous catalyst is used under mixed conditions, it becomes a reaction using a suspended bed or a gas-liquid-solid reaction field. In addition, when a homogeneous catalyst is used under mixed conditions, it becomes a gas-liquid two-phase reaction field. Once the hydrogenation reaction in the reactor is completed, the reaction liquid is taken out, and at least a part of the taken out reaction liquid is put into the same or different reactor, and the hydrogenation reaction can be carried out in a reaction mode in which the hydrogenation reaction can be further carried out. By carrying out the hydrogenation reaction in this type of reaction, it is possible to avoid the localization of heat generated by the hydrogenation reaction and the increase of the hydrogenation rate. The hydrogenation reaction can be carried out in a single reaction form, or in combination of two or more identical or different reaction forms. In the case where a higher hydrogenation rate is targeted, there is a case where a fixed bed reaction tank is used, and a hydrogenation reaction step including a step of reacting in the form of a plug flow is desirable.

氫化反應之觸媒使用量，因應使用的觸媒之種類、共軛二烯系接枝聚合物(G')之濃度、反應形式等而適當設定即可，利用使用不均相觸媒的懸浮床進行氫化反應的情形，包含共軛二烯系接枝聚合物(G')的反應液每100質量份的觸媒使用量，通常為0.01～20質量份，較佳為0.05～15質量份，更佳為0.1～10質量份。觸媒使用量過少的情形，氫化反應有成為需要長時間的情形，又，觸媒使用量過多的情形，有混合不均相觸媒的動力需要更多的情形。又，於固定床進行氫化反應的情形，規定每包含共軛二烯系接枝聚合物(G')的反應液之觸媒使用量為困難，因應使用的反應槽之種類等而適當設定即可。 作為均相觸媒之齊格勒系觸媒；使用茂金屬系觸媒的情形，就包含過渡金屬化合物之共軛二烯系接枝聚合物(G')的反應液中之濃度而言，通常為0.001毫莫耳/公升～100毫莫耳/公升，較佳為0.01毫莫耳/公升～10毫莫耳/公升。The amount of catalyst used in the hydrogenation reaction can be appropriately set according to the type of catalyst used, the concentration of the conjugated diene graft polymer (G'), the reaction form, etc., and the suspension using the heterogeneous catalyst can be used. In the case of bed hydrogenation reaction, the amount of catalyst used per 100 parts by mass of the reaction solution containing the conjugated diene graft polymer (G') is usually 0.01-20 parts by mass, preferably 0.05-15 parts by mass , More preferably 0.1-10 parts by mass. When the amount of catalyst used is too small, the hydrogenation reaction may take a long time, and when the amount of catalyst is too large, the power of mixing heterogeneous catalysts may require more. In addition, when the hydrogenation reaction is carried out in a fixed bed, it is difficult to specify the amount of catalyst used per reaction liquid containing the conjugated diene graft polymer (G'), and it is set appropriately according to the type of reaction tank used, etc. Can. Ziegler-based catalyst as a homogeneous catalyst; in the case of using a metallocene-based catalyst, in terms of the concentration in the reaction solution of the conjugated diene-based graft polymer (G') containing the transition metal compound, It is usually 0.001 millimole/liter to 100 millimole/liter, preferably 0.01 millimole/liter to 10 millimole/liter.

氫化反應使用的觸媒，於氫化反應結束後，因應必要，自包含氫化共軛二烯系接枝聚合物(G)的液中分離即可。分離的方法係只要可將觸媒分離即可，未特別限制。使用不均相觸媒的情形，例如，可利用連續式或批次式過濾、離心分離、利用靜置的沉降及藉由傾析，將前述觸媒分離。使用均相觸媒的情形，例如，可利用凝集沉澱、吸附、洗淨及水相萃取，將前述觸媒分離。 藉由此等之分離的方法，即使將使用後之觸媒分離，亦有源自觸媒的微量金屬成分殘留於包含氫化共軛二烯系接枝聚合物(G)的液中的情形。此情形亦由於金屬成分殘留於該液中，因而可通過如上所述的凝結沉澱、吸附、洗淨和水相萃取等分離方法分離殘留的金屬成分。 藉由分離而被回收的觸媒，因應必要，去除該一部分，或者追加新觸媒等後，可再次使用於氫化反應。The catalyst used in the hydrogenation reaction may be separated from the liquid containing the hydrogenated conjugated diene graft polymer (G) as necessary after the completion of the hydrogenation reaction. The method of separation is not particularly limited as long as the catalyst can be separated. In the case of using heterogeneous catalysts, for example, continuous or batch filtration, centrifugal separation, static sedimentation, and decantation can be used to separate the aforementioned catalysts. In the case of using a homogeneous catalyst, for example, the aforementioned catalyst can be separated by coagulation precipitation, adsorption, washing, and water phase extraction. With such a separation method, even if the catalyst after use is separated, trace metal components derived from the catalyst may remain in the liquid containing the hydrogenated conjugated diene-based graft polymer (G). In this case, since the metal components remain in the liquid, the remaining metal components can be separated by separation methods such as condensation precipitation, adsorption, washing, and aqueous phase extraction as described above. The catalyst recovered by separation can be reused in the hydrogenation reaction after removing the part or adding a new catalyst if necessary.

[步驟(C)] 本發明之氫化共軛二烯系接枝聚合物(G)之製造方法包含 (C)回收所獲得的氫化共軛二烯系接枝聚合物(G)的步驟。[Step (C)] The method for producing the hydrogenated conjugated diene graft polymer (G) of the present invention includes (C) A step of recovering the obtained hydrogenated conjugated diene graft polymer (G).

於步驟(C)，回收所獲得的本發明之氫化共軛二烯系接枝聚合物(G)。氫化共軛二烯系接枝聚合物(G)之回收方法未特別限制，但將包含氫化共軛二烯系接枝聚合物(G)的溶液於步驟(B)或步驟(A-2)中所獲得的情形，例如，將所獲得的溶液注入甲醇等之不良溶劑，使氫化共軛二烯系接枝聚合物(G)析出，或藉由將聚合反應液與蒸氣一起注入熱水中而藉由將溶劑共沸而去除(蒸汽汽提)後，使乾燥，或將聚合反應液以水洗淨，分離後，可藉由乾燥而將氫化共軛二烯系接枝聚合物(G)單離。In step (C), the obtained hydrogenated conjugated diene graft polymer (G) of the present invention is recovered. The recovery method of the hydrogenated conjugated diene graft polymer (G) is not particularly limited, but the solution containing the hydrogenated conjugated diene graft polymer (G) is used in step (B) or step (A-2) For example, by pouring the obtained solution into a poor solvent such as methanol to precipitate the hydrogenated conjugated diene graft polymer (G), or by pouring the polymerization reaction solution and steam into hot water After the solvent is removed by azeotropic boiling (steam stripping), it is dried or the polymerization reaction solution is washed with water. After separation, the hydrogenated conjugated diene graft polymer (G ) Single separation.

[聚合物組成物] 本發明之聚合物組成物包含本發明之氫化共軛二烯系接枝聚合物(G)。又上述聚合物組成物亦可另含有氫化共軛二烯系接枝聚合物(G)以外之其它聚合物(β)。其它聚合物(β)可為熱塑性聚合物(β1)，亦可為硬化性聚合物(β2)。[Polymer composition] The polymer composition of the present invention contains the hydrogenated conjugated diene graft polymer (G) of the present invention. In addition, the above-mentioned polymer composition may additionally contain other polymers (β) other than the hydrogenated conjugated diene graft polymer (G). The other polymer (β) may be a thermoplastic polymer (β1) or a curable polymer (β2).

就上述熱塑性聚合物(β1)而言，可列舉例如，聚甲基丙烯酸甲酯及(甲基)丙烯酸酯聚合物或共聚物等之丙烯酸系樹脂；聚乙烯、乙烯-乙酸乙烯基共聚物、聚丙烯、聚丁烯-1、聚-4-甲基戊烯-1、聚降莰烯等之烯烴系樹脂；乙烯系離子聚合物；聚苯乙烯、苯乙烯-順丁烯二酸酐共聚物、高衝擊聚苯乙烯、AS樹脂、ABS樹脂、AES樹脂、AAS樹脂、ACS樹脂、MBS樹脂等之苯乙烯系樹脂；苯乙烯-甲基丙烯酸甲酯共聚物；苯乙烯-甲基丙烯酸甲酯-順丁烯二酸酐共聚物；聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚乳酸等之聚酯樹脂；耐綸6、耐綸66、聚醯胺彈性體等之聚醯胺；聚碳酸酯；聚氯乙烯；聚偏二氯乙烯；聚乙烯基醇；乙烯-乙烯基醇共聚物；聚縮醛；聚偏二氟乙烯；聚胺基甲酸酯；改質聚苯醚；聚苯硫醚；矽氧橡膠改質樹脂；丙烯酸系橡膠；矽氧系橡膠；SEPS、SEBS、SIS等之苯乙烯系熱塑性彈性體；IR、EPR、EPDM等之烯烴系橡膠等。The above-mentioned thermoplastic polymer (β1) includes, for example, acrylic resins such as polymethyl methacrylate and (meth)acrylate polymers or copolymers; polyethylene, ethylene-vinyl acetate copolymers, Polypropylene, polybutene-1, poly-4-methylpentene-1, polynorbornene and other olefin resins; ethylene ionic polymer; polystyrene, styrene-maleic anhydride copolymer , High-impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin and other styrene resins; styrene-methyl methacrylate copolymer; styrene-methyl methacrylate -Maleic anhydride copolymer; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polylactic acid; among nylon 6, nylon 66, polyamide elastomers, etc. Polyamide; Polycarbonate; Polyvinyl Chloride; Polyvinylidene Chloride; Polyvinyl Alcohol; Ethylene-vinyl Alcohol Copolymer; Polyacetal; Polyvinylidene Fluoride; Polyurethane; Modification Polyphenylene ether; polyphenylene sulfide; silicone rubber modified resin; acrylic rubber; silicone rubber; styrene-based thermoplastic elastomers such as SEPS, SEBS, SIS, etc.; olefin-based rubbers such as IR, EPR, EPDM, etc. .

就硬化性聚合物(β2)而言，可列舉例如，環氧樹脂、不飽和聚酯樹脂、環氧基(甲基)丙烯酸酯樹脂、酯(甲基)丙烯酸酯樹脂、酚樹脂、尿素樹脂、三聚氰胺樹脂、熱硬化性胺甲酸酯樹脂、矽樹脂、醯亞胺樹脂樹脂、呋喃樹脂、醇酸樹脂、烯丙基樹脂、鄰苯二甲酸二烯丙酯樹脂。此等之中以取得性及硬化物之基本物性的觀點、又氣泡去除性、所獲得的硬化物的韌性更為優異的聚合物組成物等之觀點來看，環氧樹脂、不飽和聚酯樹脂及環氧基(甲基)丙烯酸酯樹脂為較佳，其中以環氧樹脂及不飽和聚酯樹脂為更佳，環氧樹脂為進一步較佳。硬化性聚合物(β2)可單獨使用1種，亦可併用2種以上。The curable polymer (β2) includes, for example, epoxy resin, unsaturated polyester resin, epoxy (meth)acrylate resin, ester (meth)acrylate resin, phenol resin, and urea resin. , Melamine resin, thermosetting urethane resin, silicone resin, imine resin resin, furan resin, alkyd resin, allyl resin, diallyl phthalate resin. Among these, from the viewpoints of accessibility and basic physical properties of the cured product, as well as from the viewpoints of the removal of bubbles, and the polymer composition that is more excellent in the toughness of the cured product, epoxy resins and unsaturated polyesters Resins and epoxy (meth)acrylate resins are preferred, among which epoxy resins and unsaturated polyester resins are more preferred, and epoxy resins are even more preferred. The curable polymer (β2) may be used singly, or two or more of them may be used in combination.

於上述聚合物組成物，含有氫化共軛二烯系接枝聚合物(G)及其它聚合物(β)的情形，氫化共軛二烯系接枝聚合物(G)與其它聚合物(β)的質量比(G)/(β)，係1/99～99/1為較佳。In the case where the above polymer composition contains the hydrogenated conjugated diene graft polymer (G) and other polymers (β), the hydrogenated conjugated diene graft polymer (G) and other polymers (β) The mass ratio (G)/(β) of) is preferably from 1/99 to 99/1.

又，於本發明之聚合物組成物，於無損本發明之效果的程度，可添加各種之添加劑。例如，其它聚合物(β)為熱塑性聚合物(β1)的情形，就該添加劑而言，可使用例如，碳酸鈣、二氧化矽、碳黑、玻璃纖維、黏土等之補強劑或填充劑、加工油(process oil)、聚乙二醇、甘油、鄰苯二甲酸酯等之可塑劑作為添加劑。又，就其它之添加劑而言，可列舉例如，熱安定劑、抗氧化劑、紫外線吸收劑、著色劑、顏料、潤滑劑、界面活性劑等。再者，作為該添加劑，可列舉發泡劑，由包含發泡劑與熱塑性聚合物(β1)的聚合物組成物製作發泡體為可能。 例如，其它聚合物(β)為硬化性聚合物(β2)的情形，就該添加劑而言，可列舉硬化劑、硬化促進劑、周知的橡膠、熱塑性彈性體、核-核粒子等之衝撃改質劑、填充劑(二氧化矽、滑石、碳酸鈣、氫氧化鋁等之無機粒子等)、難燃劑、消泡劑、顏料、染料、抗氧化劑、耐候劑、潤滑劑、離型劑等。In addition, various additives can be added to the polymer composition of the present invention to the extent that the effects of the present invention are not impaired. For example, when the other polymer (β) is a thermoplastic polymer (β1), for the additive, reinforcing agents or fillers such as calcium carbonate, silica, carbon black, glass fiber, clay, etc. can be used. Plasticizers such as process oil, polyethylene glycol, glycerin, and phthalate are used as additives. In addition, other additives include, for example, heat stabilizers, antioxidants, ultraviolet absorbers, colorants, pigments, lubricants, surfactants, and the like. Furthermore, as the additive, a foaming agent can be cited, and it is possible to produce a foam from a polymer composition containing a foaming agent and a thermoplastic polymer (β1). For example, when the other polymer (β) is a curable polymer (β2), the additives include hardeners, hardening accelerators, well-known rubbers, thermoplastic elastomers, core-core particles, etc. Substances, fillers (inorganic particles such as silica, talc, calcium carbonate, aluminum hydroxide, etc.), flame retardants, defoamers, pigments, dyes, antioxidants, weathering agents, lubricants, release agents, etc. .

本發明之聚合物組成物，因應氫化共軛二烯系接枝聚合物(G)與其它聚合物(β)等之各成分的組成比等，利用通常之高分子物質的混合方法可加以調製。The polymer composition of the present invention can be prepared by the usual mixing method of polymer materials in accordance with the composition ratio of each component of the hydrogenated conjugated diene graft polymer (G) and other polymers (β), etc. .

其它聚合物(β)為熱塑性聚合物(β1)的情形，例如，可利用擠出機、混合輥、班伯里混合機(Banbury mixer)、捏合機等之混合裝置而製作聚合物組成物。特別是於本發明中，使用此等混合裝置，進行熔融混練的方法為較佳一態樣。When the other polymer (β) is a thermoplastic polymer (β1), for example, a polymer composition can be produced using a mixing device such as an extruder, a mixing roll, a Banbury mixer, and a kneader. Particularly in the present invention, it is a preferable aspect to use such a mixing device to perform melt kneading.

其它聚合物(β)為硬化性聚合物(β2)的情形，例如藉由混合機等充分混合，接著藉由混合輥、擠出機等而熔融混練時，可藉由冷卻、粉卻的方法而製作聚合物組成物。When the other polymer (β) is a curable polymer (β2), for example, it is thoroughly mixed by a mixer, etc., and then melted and kneaded by a mixing roll, an extruder, etc., it can be cooled and powdered. And make a polymer composition.

本發明之聚合物組成物可由歷來已知的各種之成形法，作成成形品。The polymer composition of the present invention can be formed into a molded product by various conventionally known molding methods.

其它聚合物(β)為熱塑性聚合物(β1)的情形，可將聚合物組成物，藉由例如擠出成形、射出成形、中空成形、壓縮成形、真空成形、輪壓成形(calender molding)等進行成形，而製作成形品。藉由此等方法可獲得各種形狀之成形品、片材、薄膜等。又，藉由熔噴法(melt blow method)、跨接法(span bond method)等方法，亦可製作成為不織布、纖維狀物的成形品。When the other polymer (β) is a thermoplastic polymer (β1), the polymer composition can be formed by, for example, extrusion molding, injection molding, hollow molding, compression molding, vacuum molding, calender molding, etc. Molding is performed to produce a molded product. By this method, various shapes of molded products, sheets, films, etc. can be obtained. In addition, it is also possible to produce molded products into non-woven fabrics and fibrous materials by methods such as melt blow method and span bond method.

其它聚合物(β)為硬化性聚合物(β2)的情形，可將聚合物組成物，藉由例如，轉注成形法(transfer molding method)，藉由熱而硬化的成形品。就含有包含硬化性聚合物(β2)的聚合物組成物的情形之其它成形方法而言，可列舉例如，射出成型法、壓縮成形法。In the case where the other polymer (β) is a curable polymer (β2), the polymer composition can be a molded product hardened by heat by, for example, a transfer molding method. In the case of containing a polymer composition containing a curable polymer (β2), other molding methods include, for example, an injection molding method and a compression molding method.

其它聚合物(β)為熱塑性聚合物(β1)的情形，就由聚合物組成物所獲得的成形品之用途而言，可列舉例如，保險槓、儀表板等之汽車用內外用品、電視、立體聲、掃除機等之家電用之外殼材料、連接器等之電氣・電子構件、電線電纜用材料、肉類和鮮魚托盤、水果和蔬菜包裝、冷凍食品容器等之食品包裝材或食品容器、工業材料等之包裝材料，運動鞋材料等之運動用品、布或皮革製品、玩具、涼鞋等之日常雜貨、各種薄膜、片材、成形品的層壓材料、黏著劑/接著劑、用於尿布的彈性材料、軟管、管子、皮帶等之各種橡膠製品、醫療用品等。When the other polymer (β) is a thermoplastic polymer (β1), the use of the molded article obtained from the polymer composition includes, for example, automotive interior and exterior products such as bumpers and dashboards, televisions, Housing materials for home appliances such as stereos, sweepers, electrical and electronic components such as connectors, materials for wires and cables, meat and fresh fish trays, fruit and vegetable packaging, frozen food containers, and other food packaging materials or food containers, industrial materials Packaging materials such as sports shoes materials, sports goods such as cloth or leather products, toys, sandals, various films, sheets, laminated materials for molded products, adhesives/adhesives, elasticity for diapers Various rubber products such as materials, hoses, tubes, belts, etc., medical supplies, etc.

其它聚合物(β)為硬化性聚合物(β2)的情形，就聚合物組成物、其硬化物或成形品之用途而言，可列舉例如，纖維補強複合材用接著劑(混凝土纖維補強複合材料用接著劑、汽車・火車・飛機等運輸運送裝置用纖維補強複合材料用接著劑、各種運動用品用纖維補強複合材料用接著劑等)、組裝用接著劑(汽車・火車車量・飛機等運輸運送裝置中的零件組裝用接著劑等)等之各種接著劑；自來水及排放水用防蝕・防水塗料、金屬用防蝕塗料等之各種塗料；用於建築和土木工程的清漆底漆、汽車・火車車輛・飛機等運輸運送裝置用之清漆底漆等之各種清漆底漆；金屬用襯料、混凝土用襯料、儲罐類用襯料等之各種襯料；混凝土用龜裂補修材等之各種補修材；印刷電路基板、絕緣板、半導體密封劑、包裝材等之各種電氣電子構件等。 [實施例]When the other polymer (β) is a curable polymer (β2), the use of the polymer composition, its hardened product, or molded product includes, for example, an adhesive for fiber-reinforced composite materials (concrete fiber-reinforced composite Adhesives for materials, adhesives for fiber-reinforced composite materials for transportation equipment such as automobiles, trains, and airplanes, adhesives for fiber-reinforced composite materials for various sports goods, etc.), adhesives for assembly (cars, trains, airplanes, etc.) Various adhesives such as adhesives for assembling parts in transportation equipment, etc.; various coatings such as anti-corrosion and waterproof coatings for tap water and discharge water, and anti-corrosion coatings for metals; varnish primers for construction and civil engineering, automobiles, etc. Various varnish primers such as varnish primers used in transportation equipment such as trains and airplanes; various linings such as metal linings, concrete linings, storage tanks linings, etc.; concrete crack repair materials, etc. Various repair materials; various electrical and electronic components such as printed circuit boards, insulating boards, semiconductor sealants, packaging materials, etc. [Example]

以下，藉由實施例更詳細地說明本發明，但本發明並未被限定於此等之實施例。又，於以下之實施例及比較例，氫化共軛二烯系接枝聚合物之物性係藉由以下方法而評價。Hereinafter, the present invention will be explained in more detail through examples, but the present invention is not limited to these examples. In addition, in the following Examples and Comparative Examples, the physical properties of the hydrogenated conjugated diene graft polymer were evaluated by the following methods.

(1)重量平均分子量(Mw)、數量平均分子量(Mn)、分子量分布(Mw/Mn) 藉由凝膠滲透層析術(GPC)，以標準聚苯乙烯換算，求得氫化共軛二烯系接枝聚合物、及其製造之各階段中的聚合物之重量平均分子量(Mw)、數量平均分子量(Mn)、及分子量分布(Mw/Mn)。 裝置：Tosoh股份有限公司製 GPC裝置「HLC-8220」 分離管柱：Tosoh股份有限公司製 「TSKgel SuperMultiporeHZ-M(管柱徑=4.6mm、管柱長=15cm)」(串聯兩個使用) 溶離液：四氫呋喃 溶離液流量：0.35mL/分鐘 管柱溫度：40℃ 檢測方法：示差折射率(RI) 注入量：10μl 濃度：1mg/1cc(氫化共軛二烯系接枝聚合物/THF)(1) Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw/Mn) By gel permeation chromatography (GPC), the hydrogenated conjugated diene-based graft polymer and the weight average molecular weight (Mw) of the polymer in each stage of its production are calculated in terms of standard polystyrene. Number average molecular weight (Mn) and molecular weight distribution (Mw/Mn). Device: GPC device "HLC-8220" manufactured by Tosoh Co., Ltd. Separation column: "TSKgel SuperMultiporeHZ-M (tube column diameter=4.6mm, column length=15cm) manufactured by Tosoh Co., Ltd." (two in series) Eluent: Tetrahydrofuran Eluent flow rate: 0.35mL/min Column temperature: 40℃ Detection method: Differential refractive index (RI) Injection volume: 10μl Concentration: 1mg/1cc (hydrogenated conjugated diene graft polymer/THF)

(2)乙烯基含量、苯乙烯所衍生的結構單元含量、氫化率 藉由1 H-NMR，算出氫化共軛二烯系接枝聚合物、及其製造之各階段中的聚合物之乙烯基含量、及苯乙烯所衍生的結構單元含量、氫化率。由所獲得的光譜之來自經乙烯基化的共軛二烯所衍生的結構單元的雙鍵之峰、與來自非經乙烯基化的共軛二烯所衍生的結構單元的雙鍵之峰的面積比，算出乙烯基含量，由來自苯乙烯所衍生的結構單元的芳香環之峰，與來自共軛二烯所衍生的結構單元的雙鍵之峰的面積比，算出苯乙烯所衍生的結構單元含量。又，關於乙烯基含量、苯乙烯所衍生的結構單元含量，使用氫化前之共軛二烯系接枝聚合物之1 H-NMR而求得。又，關於氫化率，由氫化前之共軛二烯系接枝聚合物與氫化後之氫化共軛二烯系接枝聚合物之共軛二烯所衍生的結構單元的雙鍵之峰比而算出。 裝置：日本電子股份有限公司製核磁共振裝置「JNM-ECX400」 溶劑：氘代氯仿 測定溫度：50℃ 積算次數：1024次(2) Vinyl content, styrene-derived structural unit content, and hydrogenation rate. Calculate the hydrogenated conjugated diene graft polymer and the vinyl group of the polymer in each stage of its production by 1 H-NMR Content, content of structural units derived from styrene, and hydrogenation rate. The peak of the double bond derived from the structural unit derived from the vinylated conjugated diene and the peak derived from the double bond of the structural unit derived from the non-vinylated conjugated diene of the obtained spectrum Area ratio, calculate the vinyl content, and calculate the styrene-derived structure from the area ratio of the peak of the aromatic ring of the structural unit derived from styrene to the peak of the double bond of the structural unit derived from conjugated diene Unit content. In addition, the vinyl content and the content of the structural unit derived from styrene were determined using 1 H-NMR of the conjugated diene graft polymer before hydrogenation. In addition, the hydrogenation rate is based on the peak ratio of the double bond of the structural unit derived from the conjugated diene of the conjugated diene graft polymer before hydrogenation and the hydrogenated conjugated diene graft polymer after hydrogenation. Figure out. Apparatus: Nuclear Magnetic Resonance Device "JNM-ECX400" manufactured by JEOL Ltd. Solvent: Deuterated chloroform Measurement temperature: 50°C Total number of times: 1024 times

(3)聚合物每1分子之Si原子(分支點)的平均個數Y 氫化共軛二烯系接枝聚合物(G)、及官能基改質共軛二烯系聚合物(F)每1分子之Si原子(分支點)的平均個數Y，使用藉由電感耦合電漿質譜分析裝置(ICP-MS)測定的聚合物之Si含量(質量%)與標準聚苯乙烯換算之數量平均分子量(Mn)，由下式而求得。 (聚合物每1分子之Si原子之個數)=[(Si含量(質量%))/100]×[(數量平均分子量Mn)/(苯乙烯所衍生的結構單元之分子量)×(共軛二烯及而包含的共軛二烯以外之其它單體所衍生的結構單元之平均分子量)]/Si之原子量 關於實施例18，利用同樣的手法，求得聚合物每1分子之B原子(分支點)的平均個數Y。(3) The average number of Si atoms (branching points) per polymer molecule Y Hydrogenated conjugated diene graft polymer (G) and functional group-modified conjugated diene polymer (F) The average number of Si atoms (branching points) per molecule Y, using inductive coupling The Si content (mass %) of the polymer measured by the plasma mass spectrometer (ICP-MS) is calculated from the number average molecular weight (Mn) in terms of standard polystyrene by the following formula. (Number of Si atoms per molecule of polymer)=[(Si content (mass%))/100]×[(number average molecular weight Mn)/(molecular weight of structural unit derived from styrene)×(conjugated Diene and the average molecular weight of structural units derived from monomers other than conjugated diene)]/Si atomic weight Regarding Example 18, the average number Y of B atoms (branching points) per molecule of the polymer was obtained by the same method.

(4)氫化共軛二烯系接枝聚合物所含的每Si原子(分支點)的官能基(c)的平均個數(X/Y) 氫化共軛二烯系接枝聚合物所含的每Si原子(分支點)的官能基(c)(選自包含烷氧基及羥基的群組的至少1者)的平均個數(X/Y)，係由測定氫化共軛二烯系接枝聚合物之29 Si-NMR的結果而求得。具體而言，藉由將有官能基(c)1個結合的Si、有官能基(c)2個結合的Si等之積分值乘以官能基之個數者合計，與積分值之單純合計進行比較而算出。 關於實施例18，藉由測定11 B-NMR，利用同樣之手法，求得氫化共軛二烯系接枝聚合物所含的每B原子(分支點)的官能基(c)的平均個數(X/Y)。(4) The average number of functional groups (c) per Si atom (branch point) contained in the hydrogenated conjugated diene graft polymer (X/Y) The hydrogenated conjugated diene graft polymer contains The average number (X/Y) of functional groups (c) (at least one selected from the group consisting of alkoxy and hydroxyl groups) per Si atom (branching point) is determined by measuring the hydrogenated conjugated diene system Obtained from the result of 29 Si-NMR of the graft polymer. Specifically, by multiplying the integral value of Si with one functional group (c) bonded, Si with two functional groups (c), etc., multiplied by the number of functional groups, and the simple total of the integral value Calculate by comparing. Regarding Example 18, by measuring 11 B-NMR, the average number of functional groups (c) per B atom (branch point) contained in the hydrogenated conjugated diene graft polymer was obtained by the same method. (X/Y).

(5)氫化共軛二烯系接枝聚合物每1分子之官能基(c)的平均個數X 氫化共軛二烯系接枝聚合物每1分子之官能基(c)的平均個數X，使用氫化共軛二烯系接枝聚合物所含的每Si原子(分支點)的官能基(c)的平均個數(X/Y)與上述氫化共軛二烯系接枝聚合物每1分子之Si原子之平均個數Y，由下式而求得。 (氫化共軛二烯系接枝聚合物每1分子之官能基(c)的平均個數X)=(氫化共軛二烯系接枝聚合物所含的每Si原子(分支點)的官能基(c)的平均個數(X/Y))×(氫化共軛二烯系接枝聚合物每1分子之Si原子的平均個數Y) 關於實施例18，使用上述氫化共軛二烯系接枝聚合物所含的每B原子(分支點)的官能基(c)的平均個數與氫化共軛二烯系接枝聚合物每1分子之B原子的平均個數，求得氫化共軛二烯系接枝聚合物每1分子之官能基(c)的平均個數X。(5) The average number of functional groups (c) per molecule of hydrogenated conjugated diene graft polymer X The average number X of functional groups (c) per molecule of the hydrogenated conjugated diene graft polymer is the functional group per Si atom (branch point) contained in the hydrogenated conjugated diene graft polymer ( The average number (X/Y) of c) and the average number Y of Si atoms per molecule of the above-mentioned hydrogenated conjugated diene graft polymer can be obtained from the following formula. (The average number of functional groups (c) per molecule of the hydrogenated conjugated diene graft polymer X) = (functionality per Si atom (branch point) contained in the hydrogenated conjugated diene graft polymer The average number of groups (c) (X/Y))×(the average number of Si atoms per molecule Y of the hydrogenated conjugated diene graft polymer) Regarding Example 18, the average number of functional groups (c) per B atom (branch point) contained in the above-mentioned hydrogenated conjugated diene graft polymer and the number of functional groups (c) per 1 hydrogenated conjugated diene graft polymer were used. The average number of B atoms in the molecule is calculated, and the average number X of functional groups (c) per molecule of the hydrogenated conjugated diene graft polymer is obtained.

(6)氫化共軛二烯系接枝聚合物每1分子之側鏈(b)之平均條數W 氫化共軛二烯系接枝聚合物每1分子之側鏈(b)之平均條數W，使用上述偶合步驟中的氫化共軛二烯系接枝聚合物之側鏈(b)之成為構成要素的活性末端聚合物(I)之每活性末端的進料量(莫耳數)與官能基改質共軛二烯系聚合物(F)之進料量(莫耳數)，由下式而求得。 (氫化共軛二烯系接枝聚合物每1分子之側鏈(b)之平均條數W)=(側鏈(b)之構成要素的活性末端聚合物(I)之每活性末端的進料量(莫耳數))/(官能基改質共軛二烯系聚合物(F)之進料量(莫耳數))(6) The average number of side chains (b) per molecule of the hydrogenated conjugated diene graft polymer W The average number of side chains (b) W per molecule of the hydrogenated conjugated diene graft polymer is constituted by the side chain (b) of the hydrogenated conjugated diene graft polymer in the above coupling step The feed amount (number of moles) per active end of the active end polymer (I) and the feed amount (number of moles) of the functional group-modified conjugated diene polymer (F) are given by the following formula And get it. (The average number of side chains (b) per molecule of the hydrogenated conjugated diene graft polymer W) = (the side chain (b) component of the active end polymer (I) per active end) Feed amount (mole number))/(functional group-modified conjugated diene polymer (F) feed rate (mole number))

(7)氫化共軛二烯系接枝聚合物所含的每Si原子(分支點)的側鏈(b)之平均條數(W/Y) 氫化共軛二烯系接枝聚合物所含的每Si原子(分支點)的側鏈(b)之平均條數(W/Y)，使用上述氫化共軛二烯系接枝聚合物每1分子之側鏈(b)之平均條數W與上述氫化共軛二烯系接枝聚合物每1分子之Si原子的平均個數Y，由下式而求得。 (氫化共軛二烯系接枝聚合物所含的每Si原子的側鏈(b)之平均條數(W/Y))=(氫化共軛二烯系接枝聚合物每1分子之側鏈(b)之平均條數W)/(氫化共軛二烯系接枝聚合物每1分子之Si原子的平均個數Y) 關於實施例18，使用上述氫化共軛二烯系接枝聚合物每1分子之側鏈(b)之平均條數W與上述氫化共軛二烯系接枝聚合物每1分子之B原子的平均個數Y，而求得氫化共軛二烯系接枝聚合物所含的每B原子(分支點)的側鏈(b)之平均條數(W/Y)。(7) The average number of side chains (b) per Si atom (branching point) contained in the hydrogenated conjugated diene graft polymer (W/Y) The average number of side chains (b) per Si atom (branch point) contained in the hydrogenated conjugated diene graft polymer (W/Y), using the above-mentioned hydrogenated conjugated diene graft polymer per 1 The average number W of side chains (b) of the molecule and the average number Y of Si atoms per molecule of the above-mentioned hydrogenated conjugated diene graft polymer can be obtained from the following formula. (The average number of side chains (b) per Si atom contained in the hydrogenated conjugated diene graft polymer (W/Y)) = (Hydrogenated conjugated diene graft polymer per 1 molecule side The average number of chains (b) W)/(the average number of Si atoms per molecule Y of the hydrogenated conjugated diene graft polymer) Regarding Example 18, the average number W of side chains (b) per molecule of the hydrogenated conjugated diene graft polymer and the number of B atoms per molecule of the hydrogenated conjugated diene graft polymer were used. The average number Y is calculated to obtain the average number (W/Y) of side chains (b) per B atom (branching point) contained in the hydrogenated conjugated diene graft polymer.

(8)偶合率 氫化共軛二烯系接枝聚合物之偶合率，使用以上述GPC測定所獲得的偶合未反應之聚合物成分之峰面積與全部之峰面積的總和，由下式而求得。 (偶合率(%))=[｛((全部之峰面積的總和)-(活性末端聚合物(I)的成分之峰面積)｝/(全部之峰面積的總和)]×100(8) Coupling rate The coupling ratio of the hydrogenated conjugated diene-based graft polymer is determined by the following formula using the sum of the peak area of the coupled unreacted polymer component obtained by the above-mentioned GPC measurement and the total peak area. (Coupling rate (%))=[{((The sum of all peak areas)-(The peak area of the active end polymer (I) component)}/(The sum of all the peak areas)]×100

(9)氯的含量 藉由自動燃燒離子層析(combustion ion chromatography)，算出氫化共軛二烯系接枝聚合物所含的氯含量。 ＜燃燒裝置＞ ・裝置：Mitsubishi Chemical Analytech股份有限公司製自動試料燃燒裝置「AQF-2100H」 ・燃燒溫度：1000℃ ・吸收液：離子交換水 ＜離子層析＞ ・裝置：Thermo Fisher Scientific公司製 離子層析儀「ICS-2100」 ・分離管柱：Thermo Fisher Scientific公司製「IonPac AS20」 ・溶離液：KOH水溶液 ・管柱溫度：40℃(9) Chlorine content The chlorine content contained in the hydrogenated conjugated diene graft polymer was calculated by automatic combustion ion chromatography (combustion ion chromatography). ＜Combustion device＞ ・Device: Automatic sample combustion device "AQF-2100H" manufactured by Mitsubishi Chemical Analytech Co., Ltd. ・Combustion temperature: 1000℃ ・Absorbent liquid: ion exchange water ＜Ion Chromatography＞ ・Equipment: Ion chromatograph "ICS-2100" manufactured by Thermo Fisher Scientific ・Separation column: "IonPac AS20" manufactured by Thermo Fisher Scientific ・Eluent: KOH aqueous solution ・Column temperature: 40℃

(10)安定性 氫化共軛二烯系接枝聚合物的安定性，由將氫化共軛二烯系接枝聚合物的洗淨結束後之包含聚合物溶液進行乾燥的步驟(下述步驟(6))中的性狀變化，而進行評價。於70℃真空乾燥24小時的聚合物中添加100倍量之環己烷，於室溫振盪12h，藉由過濾將不溶分回收並乾燥。將飼入的聚合物的質量設為M1，將過濾、乾燥後的不溶分的質量設為M2，由下式算出不溶分的比率(凝膠分率)，以下列指標評價安定性。 (凝膠分率(%))=(M2/M1)×100 A：乾燥後之凝膠分率小於50質量% B：乾燥後之凝膠分率為50質量%以上(10) Stability The stability of the hydrogenated conjugated diene graft polymer is determined by the step of drying the polymer solution contained in the polymer solution after the washing of the hydrogenated conjugated diene graft polymer (the following step (6)) Changes in traits are evaluated. 100 times the amount of cyclohexane was added to the polymer dried in vacuum at 70°C for 24 hours, shaken at room temperature for 12 hours, and the insoluble matter was recovered by filtration and dried. The mass of the polymer fed is set to M1, and the mass of the insoluble matter after filtration and drying is set to M2, the ratio of insoluble matter (gel fraction) is calculated from the following formula, and the stability is evaluated by the following index. (Gel fraction (%))=(M2/M1)×100 A: The gel fraction after drying is less than 50% by mass B: The gel fraction after drying is more than 50% by mass

(11)縮合反應性 氫化共軛二烯系接枝聚合物之與極性材料的親和性，利用酸性條件中的烷氧基矽烷基之縮合反應性而進行評價。將氫化共軛二烯系接枝聚合物溶解於環己烷使固形分濃度成為10質量%，與1質量%乙酸水溶液以重量比1：1混合而於室溫振盪12h後，以目視確認是否有不溶分(凝膠)之生成，並以下列指標評價縮合反應性。有不溶分的情形者可謂縮合反應性高，與極性材料的親和性高。 A：有不溶分 B：無不溶分(11) Condensation reactivity The affinity of the hydrogenated conjugated diene graft polymer with polar materials was evaluated by the condensation reactivity of alkoxysilyl groups in acidic conditions. The hydrogenated conjugated diene graft polymer was dissolved in cyclohexane to make the solid content concentration 10% by weight, mixed with a 1% by weight acetic acid aqueous solution at a weight ratio of 1:1, and shaken at room temperature for 12 hours. Insoluble matter (gel) is formed, and the condensation reactivity is evaluated by the following indicators. Those with insoluble content can be said to have high condensation reactivity and high affinity with polar materials. A: There is insoluble content B: No insoluble matter

(12)透明性 氫化共軛二烯系接枝聚合物之透明性利用霧度(HAZE)加以評價。將氫化共軛二烯系接枝聚合物溶解於環己烷使聚合物的濃度成為30質量%，使用光路徑長10mm的液體用槽，使用日本電色工業股份有限公司製光譜霧度計(Spectral haze meter) 「SH7000」而測定霧度(HAZE)，以下列指標評價透明性。 A：霧度(HAZE)小於80% B：霧度(HAZE)為80%以上(12) Transparency The transparency of the hydrogenated conjugated diene graft polymer was evaluated by HAZE. The hydrogenated conjugated diene graft polymer was dissolved in cyclohexane so that the concentration of the polymer was 30% by mass, a liquid tank with an optical path length of 10 mm was used, and a spectral haze meter manufactured by Nippon Denshoku Kogyo Co., Ltd. was used ( Spectral haze meter) "SH7000" to measure the haze (HAZE), and evaluate the transparency with the following index. A: Haze (HAZE) is less than 80% B: Haze (HAZE) is above 80%

(13)耐熱性 氫化共軛二烯系接枝聚合物之耐熱性係利用目視的加熱時之外觀變化而評價。將氫化共軛二烯系接枝聚合物塗布於載玻片上，於大氣下120℃、或100℃加熱12h後的外觀，以下列指標評價耐熱性。 A：外觀無變化 B：凝膠化、或黃變(13) Heat resistance The heat resistance of the hydrogenated conjugated diene graft polymer was evaluated by visual observation of the appearance change during heating. The appearance of the hydrogenated conjugated diene graft polymer was coated on a glass slide and heated at 120°C or 100°C for 12 hours in the atmosphere, and the heat resistance was evaluated by the following indexes. A: No change in appearance B: Gelation, or yellowing

[實施例1] (步驟(1)) 將完全乾燥的5L高壓釜進行氮置換，飼入1370g環己烷和240g二級丁基鋰(10.5質量%環己烷溶液)，升溫至50℃後，攪拌條件下，一邊將聚合溫度控制於50℃，一邊逐次添加丁二烯1250g，並聚合1小時。之後添加甲醇14g而使聚合反應停止，獲得聚合物溶液。於所獲得的聚合物溶液中添加水而攪拌，以水將聚合物溶液洗淨。結束攪拌，確認聚合物溶液相與水相分離後，將水分離。藉由將洗淨結束後之聚合物溶液於70℃真空乾燥24小時，獲得未改質共軛二烯系聚合物(F'-1)。[Example 1] (step 1)) The completely dry 5L autoclave was replaced with nitrogen, fed with 1370g cyclohexane and 240g secondary butyllithium (10.5 mass% cyclohexane solution), heated to 50°C, while stirring, controlled the polymerization temperature at At 50°C, 1250 g of butadiene was added successively and polymerized for 1 hour. After that, 14 g of methanol was added to stop the polymerization reaction, and a polymer solution was obtained. Water is added to the obtained polymer solution and stirred, and the polymer solution is washed with water. After the stirring was completed and it was confirmed that the polymer solution phase was separated from the water phase, the water was separated. The polymer solution after washing was vacuum dried at 70°C for 24 hours to obtain an unmodified conjugated diene polymer (F'-1).

(步驟(2)) 接著，於容量1L的高壓釜中，飼入步驟(1)所獲得的未改質共軛二烯系聚合物(F'-1)460g，一邊於60℃攪拌3小時一邊進行氮脫氣。添加過氧異丁酸三級丁酯0.6g與3-巰基丙基三乙氧基矽烷290g，使於80℃反應8小時，獲得官能基改質共軛二烯系聚合物(F-1)。藉由所獲得的官能基改質共軛二烯系聚合物(F-1)之分析，可求得後述的共軛二烯系接枝聚合物(G-1)之主鏈(a)之重量平均分子量、乙烯基含量、苯乙烯所衍生的結構單元含量。所獲得的官能基改質共軛二烯系聚合物(F-1)之重量平均分子量為6,000，乙烯基含量為10莫耳%，苯乙烯所衍生的結構單元含量為0質量%，聚合物每1分子之Si原子的平均個數Y為8個。於所獲得的官能基改質共軛二烯系聚合物(F-1)中添加環己烷1750g，而稀釋為濃度30質量%，獲得於後述的偶合反應中使用的官能基改質共軛二烯系聚合物(F-1)之稀釋溶液。(Step (2)) Next, 460 g of the unmodified conjugated diene polymer (F'-1) obtained in step (1) was fed into an autoclave with a volume of 1 L, and nitrogen degassed while stirring at 60°C for 3 hours. Add 0.6 g of tertiary butyl peroxyisobutyrate and 290 g of 3-mercaptopropyl triethoxysilane, and react at 80°C for 8 hours to obtain a functional group-modified conjugated diene polymer (F-1) . By analyzing the obtained functional group-modified conjugated diene polymer (F-1), it is possible to determine the main chain (a) of the conjugated diene graft polymer (G-1) described later Weight average molecular weight, vinyl content, and styrene-derived structural unit content. The obtained functional group-modified conjugated diene polymer (F-1) has a weight average molecular weight of 6,000, a vinyl content of 10 mol%, and a styrene-derived structural unit content of 0% by mass. The average number Y of Si atoms per molecule is 8. To the obtained functional group-modified conjugated diene polymer (F-1), 1750 g of cyclohexane was added and diluted to a concentration of 30% by mass to obtain the functional group-modified conjugate used in the coupling reaction described later. A diluted solution of diene polymer (F-1).

(步驟(3)) 將完全乾燥的5L高壓釜進行氮置換，飼入2270g環己烷和8.7g二級丁基鋰(10.5質量%環己烷溶液)，升溫至50℃後，攪拌條件下，一邊將聚合溫度控制於50℃，一邊逐次添加異戊二烯570g，聚合1小時，獲得活性末端聚合物(I-1)。將步驟(3)中的聚合物溶液採樣而分析，可求得後述的氫化共軛二烯系接枝聚合物(G-1)之側鏈(b)之重量平均分子量、乙烯基含量、苯乙烯所衍生的結構單元含量。所獲得的活性末端聚合物(I-1)之重量平均分子量為60,000，乙烯基含量為10莫耳%，苯乙烯所衍生的結構單元含量為0質量%。(Step (3)) The completely dry 5L autoclave was replaced with nitrogen, 2270g cyclohexane and 8.7g secondary butyllithium (10.5 mass% cyclohexane solution) were fed, and after the temperature was raised to 50°C, the polymerization temperature was controlled while stirring. At 50°C, 570 g of isoprene was added successively and polymerized for 1 hour to obtain a living terminal polymer (I-1). By sampling and analyzing the polymer solution in step (3), the weight average molecular weight, vinyl content, and benzene of the side chain (b) of the hydrogenated conjugated diene graft polymer (G-1) described later can be determined. The content of structural units derived from ethylene. The weight average molecular weight of the obtained living terminal polymer (I-1) was 60,000, the vinyl content was 10 mol%, and the content of styrene-derived structural units was 0% by mass.

(步驟(4)) 接著，於包含步驟(3)所獲得的活性末端聚合物(I-1)的溶液中，添加四氫呋喃0.7g及步驟(2)所獲得的官能基改質共軛二烯系聚合物(F-1)之稀釋溶液20g，並於50℃使偶合反應2小時。之後，添加二級丁基鋰(10.5質量%環己烷溶液)26g，使反應6小時而將殘存的烷氧基之一部分封止。之後添加甲醇1.0g而使聚合反應停止，獲得含有氫化前之共軛二烯系接枝聚合物(G'-1)的溶液。(Step (4)) Next, to the solution containing the living terminal polymer (I-1) obtained in step (3), 0.7 g of tetrahydrofuran and the functional group-modified conjugated diene polymer (F-) obtained in step (2) were added. 1) 20g of the diluted solution, and the coupling reaction was carried out at 50°C for 2 hours. Then, 26 g of secondary butyl lithium (10.5 mass% cyclohexane solution) was added, and it was made to react for 6 hours, and a part of remaining alkoxy group was blocked. Then, 1.0 g of methanol was added to stop the polymerization reaction, and a solution containing the conjugated diene graft polymer (G'-1) before hydrogenation was obtained.

(步驟(5)) 於含所獲得的共軛二烯系接枝聚合物(G'-1)的溶液中，添加100mL之由辛酸鎳及三甲基鋁所形成的齊格勒系氫化觸媒(0.095mmol/L環己烷溶液)，於氫壓力1MPa、80℃之條件使反應5小時，而獲得含氫化共軛二烯系接枝聚合物(G-1)的溶液。(Step (5)) To the solution containing the obtained conjugated diene graft polymer (G'-1), add 100 mL of a Ziegler hydrogenation catalyst (0.095mmol/L) composed of nickel octoate and trimethylaluminum Cyclohexane solution), and reacted for 5 hours under the conditions of a hydrogen pressure of 1 MPa and 80°C to obtain a solution containing a hydrogenated conjugated diene graft polymer (G-1).

(步驟(6)) 藉由將含所獲得的氫化共軛二烯系接枝聚合物(G-1)的溶液水洗而去除上述觸媒，將洗淨結束後之聚合物溶液於70℃真空乾燥24小時，回收氫化共軛二烯系接枝聚合物(G-1)。所獲得的氫化共軛二烯系接枝聚合物(G-1)之重量平均分子量為486,000，Mw/Mn為1.5，苯乙烯所衍生的結構單元含量為0質量%，偶合率為95%，氫化率為99莫耳%，聚合物每1分子之Si原子(分支點)的平均個數為8個，聚合物每一分子的官能基(c)的平均個數為0.8個，每Si原子(分支點)的官能基(c)的平均個數為0.1個，聚合物每一分子的側鏈(b)之平均條數為8條，每Si原子(分支點)的側鏈(b)之平均條數為1條。將於實施例1使用的各試藥之種類、量示於表1，將所獲得的氫化共軛二烯系接枝聚合物(G-1)之分子規格、物性示於表3。(Step (6)) The catalyst is removed by washing the solution containing the obtained hydrogenated conjugated diene graft polymer (G-1) with water, and the polymer solution after washing is vacuum dried at 70°C for 24 hours, and the hydrogen is recovered Conjugated diene graft polymer (G-1). The weight average molecular weight of the obtained hydrogenated conjugated diene graft polymer (G-1) was 486,000, Mw/Mn was 1.5, the content of structural units derived from styrene was 0% by mass, and the coupling ratio was 95%. The hydrogenation rate is 99 mol%, the average number of Si atoms (branching points) per polymer molecule is 8, and the average number of functional groups (c) per polymer molecule is 0.8, per Si atom (Branch point) The average number of functional groups (c) is 0.1, the average number of side chains (b) per polymer molecule is 8, and the side chains (b) per Si atom (branch point) The average number of bars is 1. The types and amounts of the reagents used in Example 1 are shown in Table 1, and the molecular specifications and physical properties of the obtained hydrogenated conjugated diene graft polymer (G-1) are shown in Table 3.

[實施例2～15] 除了將步驟(1)～(6)中使用的各試藥之種類、量如表1及2記載的方式作變更以外，藉由與實施例1相同的方法，獲得氫化共軛二烯系接枝聚合物(G-2)～(G-15)。將所獲得的氫化共軛二烯系接枝聚合物(G-2)～(G-15)之分子規格、物性示於表3及4。[Examples 2-15] Except that the type and amount of each reagent used in steps (1) to (6) are changed as described in Tables 1 and 2, the same method as in Example 1 was used to obtain a hydrogenated conjugated diene-based Branch polymer (G-2) ~ (G-15). The molecular specifications and physical properties of the obtained hydrogenated conjugated diene graft polymers (G-2) to (G-15) are shown in Tables 3 and 4.

[實施例16] (步驟(1)) 將完全乾燥的5L高壓釜進行氮置換，飼入1370g環己烷和240g二級丁基鋰(10.5質量%環己烷溶液)，升溫至50℃後，攪拌條件下，一邊將聚合溫度控制於50℃，一邊逐次添加丁二烯1250g，並聚合1小時。之後添加甲醇14g而使聚合反應停止，獲得聚合物溶液。於所獲得的聚合物溶液中添加水而攪拌，以水將聚合物溶液洗淨。結束攪拌，確認聚合物溶液相與水相分離後，將水分離。藉由將洗淨結束後之聚合物溶液於70℃真空乾燥24小時，獲得未改質共軛二烯系聚合物(F'-16)。[Example 16] (step 1)) The completely dry 5L autoclave was replaced with nitrogen, fed with 1370g cyclohexane and 240g secondary butyllithium (10.5 mass% cyclohexane solution), heated to 50°C, while stirring, controlled the polymerization temperature at At 50°C, 1250 g of butadiene was added successively and polymerized for 1 hour. After that, 14 g of methanol was added to stop the polymerization reaction, and a polymer solution was obtained. Water is added to the obtained polymer solution and stirred, and the polymer solution is washed with water. After the stirring was completed and it was confirmed that the polymer solution phase was separated from the water phase, the water was separated. The unmodified conjugated diene polymer (F'-16) was obtained by vacuum drying the polymer solution after washing at 70°C for 24 hours.

(步驟(2)) 接著，於具備攪拌機、回流冷卻器、滴下漏斗及溫度計的5L分離式燒瓶中，飼入步驟(1)所獲得的未改質共軛二烯系聚合物(F'-16)530g、甲苯1400g、鉑-1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物之甲苯溶液(作為鉑原子，1.8×10-4 莫耳)、及乙酸1.1g。於其中，將三乙氧基矽烷220g於內溫75～85℃歷經2小時滴下後，於80℃攪拌1小時。攪拌結束後，減壓濃縮及過濾，獲得官能基改質共軛二烯系聚合物(F-16)。藉由所獲得的官能基改質共軛二烯系聚合物(F-16)之分析，可求得後述的共軛二烯系接枝聚合物(G-16)之主鏈(a)之重量平均分子量、乙烯基含量、苯乙烯所衍生的結構單元含量。所獲得的官能基改質共軛二烯系聚合物(F-16)之重量平均分子量為6,000，乙烯基含量為10莫耳%，苯乙烯所衍生的結構單元含量為0質量%，聚合物每1分子之Si原子之平均個數為8個。於所獲得的官能基改質共軛二烯系聚合物(F-16)中添加環己烷1750g，稀釋為濃度30質量%，獲得於後述之偶合反應中使用的官能基改質共軛二烯系聚合物(F-16)之稀釋溶液。(Step (2)) Next, the unmodified conjugated diene polymer (F'- 16) 530g, 1400g toluene, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in toluene solution (as platinum atom, 1.8×10 -4 mol ), and 1.1 g of acetic acid. Among them, 220 g of triethoxysilane was dropped at an internal temperature of 75 to 85°C for 2 hours, and then stirred at 80°C for 1 hour. After the stirring, it was concentrated under reduced pressure and filtered to obtain a functional group-modified conjugated diene polymer (F-16). By analyzing the obtained functional group-modified conjugated diene polymer (F-16), the main chain (a) of the conjugated diene graft polymer (G-16) described later can be determined Weight average molecular weight, vinyl content, and styrene-derived structural unit content. The obtained functional group-modified conjugated diene polymer (F-16) has a weight average molecular weight of 6,000, a vinyl content of 10 mol%, and a styrene-derived structural unit content of 0% by mass. The average number of Si atoms per molecule is 8. To the obtained functional group-modified conjugated diene polymer (F-16), 1750 g of cyclohexane was added and diluted to a concentration of 30% by mass to obtain the functional group-modified conjugated diene polymer used in the coupling reaction described later. Dilute solution of olefin polymer (F-16).

(步驟(3)) 將完全乾燥的5L高壓釜進行氮置換，飼入2270g環己烷和8.7g二級丁基鋰(10.5質量%環己烷溶液)，升溫至50℃後，攪拌條件下，一邊將聚合溫度控制於50℃，一邊逐次添加異戊二烯570g，聚合1小時，獲得活性末端聚合物(I-16)。將步驟(3)中的聚合物溶液採樣而分析，可求得後述的氫化共軛二烯系接枝聚合物(G-16)之側鏈(b)之重量平均分子量、乙烯基含量、苯乙烯所衍生的結構單元含量。所獲得的活性末端聚合物(I-16)之重量平均分子量為60,000，乙烯基含量為10莫耳%，苯乙烯所衍生的結構單元含量為0質量%。(Step (3)) The completely dry 5L autoclave was replaced with nitrogen, 2270g cyclohexane and 8.7g secondary butyllithium (10.5 mass% cyclohexane solution) were fed, and after the temperature was raised to 50°C, the polymerization temperature was controlled while stirring. At 50°C, 570 g of isoprene was added successively and polymerized for 1 hour to obtain a living terminal polymer (I-16). By sampling and analyzing the polymer solution in step (3), the weight average molecular weight, vinyl content, and benzene of the side chain (b) of the hydrogenated conjugated diene graft polymer (G-16) described later can be determined. The content of structural units derived from ethylene. The weight average molecular weight of the obtained living terminal polymer (I-16) was 60,000, the vinyl content was 10 mol%, and the content of styrene-derived structural units was 0% by mass.

(步驟(4)) 接著，於含有步驟(3)所獲得的活性末端聚合物(I-16)的溶液中，添加四氫呋喃0.7g及步驟(2)所獲得的官能基改質共軛二烯系聚合物(F-16)之稀釋溶液20g，於50℃使進行偶合反應2小時。之後，添加二級丁基鋰(10.5質量%環己烷溶液)26g，使反應6小時，而將殘存的烷氧基之一部分封止。之後添加甲醇1.0g而使聚合反應停止，獲得含有氫化前之共軛二烯系接枝聚合物(G'-16)的溶液。(Step (4)) Next, to the solution containing the living terminal polymer (I-16) obtained in step (3), 0.7 g of tetrahydrofuran and the functional group-modified conjugated diene polymer (F- 20g of the diluted solution of 16) was allowed to perform coupling reaction at 50°C for 2 hours. After that, 26 g of secondary butyllithium (10.5 mass% cyclohexane solution) was added and reacted for 6 hours, and a part of the remaining alkoxy group was blocked. Then, 1.0 g of methanol was added to stop the polymerization reaction, and a solution containing the conjugated diene graft polymer (G'-16) before hydrogenation was obtained.

(步驟(5)) 於含所獲得的共軛二烯系接枝聚合物(G'-16)的溶液中，添加100mL之由辛酸鎳及三甲基鋁所形成的齊格勒系氫化觸媒(0.095mmol/L環己烷溶液)，於氫壓力1MPa、80℃之條件使反應5小時，而獲得含氫化共軛二烯系接枝聚合物(G-16)的溶液。(Step (5)) To the solution containing the obtained conjugated diene graft polymer (G'-16), add 100 mL of a Ziegler hydrogenation catalyst (0.095mmol/L) composed of nickel octoate and trimethylaluminum Cyclohexane solution), and reacted for 5 hours under the conditions of a hydrogen pressure of 1 MPa and 80°C to obtain a solution containing a hydrogenated conjugated diene graft polymer (G-16).

(步驟(6)) 藉由將含所獲得的氫化共軛二烯系接枝聚合物(G-16)的溶液水洗而去除上述觸媒，將洗淨結束後之聚合物溶液於70℃真空乾燥24小時，回收氫化共軛二烯系接枝聚合物(G-16)。所獲得的氫化共軛二烯系接枝聚合物(G-16)之重量平均分子量為486,000，Mw/Mn為1.5，苯乙烯所衍生的結構單元含量為0質量%，偶合率為95%，氫化率為99莫耳%，聚合物每1分子之Si原子(分支點)的平均個數為8個，聚合物每一分子的官能基(c)的平均個數為0.8個，每Si原子(分支點)的官能基(c)的平均個數為0.1個，聚合物每一分子的側鏈(b)之平均條數為8條，每Si原子(分支點)的側鏈(b)之平均條數為1條。將所獲得的氫化共軛二烯系接枝聚合物(G-16)之分子規格示於表4。(Step (6)) The catalyst is removed by washing the solution containing the obtained hydrogenated conjugated diene graft polymer (G-16) with water, and the polymer solution after washing is vacuum dried at 70°C for 24 hours, and the hydrogen is recovered Conjugated diene graft polymer (G-16). The weight average molecular weight of the obtained hydrogenated conjugated diene graft polymer (G-16) was 486,000, Mw/Mn was 1.5, the content of structural units derived from styrene was 0% by mass, and the coupling ratio was 95%. The hydrogenation rate is 99 mol%, the average number of Si atoms (branching points) per polymer molecule is 8, and the average number of functional groups (c) per polymer molecule is 0.8, per Si atom (Branch point) The average number of functional groups (c) is 0.1, the average number of side chains (b) per polymer molecule is 8, and the side chains (b) per Si atom (branch point) The average number of bars is 1. Table 4 shows the molecular specifications of the obtained hydrogenated conjugated diene graft polymer (G-16).

[實施例17] (步驟(1)) 將完全乾燥的5L高壓釜進行氮置換，飼入1580g環己烷和56g二級丁基鋰(10.5質量%環己烷溶液)，升溫至50℃後，攪拌條件下，一邊將聚合溫度控制於50℃，一邊逐次添加四氫呋喃11g、丁二烯1250g，並聚合1小時。之後添加甲醇3.1g，而使聚合反應停止，獲得聚合物溶液。於所獲得的聚合物溶液中添加水而攪拌，以水將聚合物溶液洗淨。結束攪拌，確認聚合物溶液相與水相分離後，將水分離。藉由將洗淨結束後之聚合物溶液於70℃真空乾燥24小時，獲得未改質共軛二烯系聚合物(F'-17)。[Example 17] (step 1)) The completely dry 5L autoclave was replaced with nitrogen, 1580g cyclohexane and 56g secondary butyllithium (10.5 mass% cyclohexane solution) were fed, and the temperature was raised to 50°C, while stirring, the polymerization temperature was controlled at At 50°C, 11 g of tetrahydrofuran and 1,250 g of butadiene were added successively, and the polymerization was carried out for 1 hour. Then, 3.1 g of methanol was added to stop the polymerization reaction to obtain a polymer solution. Water is added to the obtained polymer solution and stirred, and the polymer solution is washed with water. After the stirring was completed and it was confirmed that the polymer solution phase was separated from the water phase, the water was separated. The unmodified conjugated diene polymer (F'-17) was obtained by vacuum drying the polymer solution after washing at 70°C for 24 hours.

(步驟(2)) 接著，於具備攪拌機、回流冷卻器、滴下漏斗及溫度計的5L分離式燒瓶中，飼入步驟(1)所獲得的未改質共軛二烯系聚合物(F'-17)700g、甲苯1400g、鉑-1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物之甲苯溶液(作為鉑原子，2.1×10-5 莫耳)、及乙酸0.12g。於其中，將三乙氧基矽烷34g於內溫75～85℃歷經2小時滴下後，於80℃攪拌1小時。攪拌結束後，減壓濃縮及過濾，獲得官能基改質共軛二烯系聚合物(F-17)。藉由所獲得的官能基改質共軛二烯系聚合物(F-17)之分析，可求得後述的共軛二烯系接枝聚合物(G-17)之主鏈(a)之重量平均分子量、乙烯基含量、苯乙烯所衍生的結構單元含量。所獲得的官能基改質共軛二烯系聚合物(F-17)之重量平均分子量為26,000，乙烯基含量為50莫耳%，苯乙烯所衍生的結構單元含量為0質量%，聚合物每1分子之Si原子之平均個數為4個。於所獲得的官能基改質共軛二烯系聚合物(F-17)中添加環己烷1710g，稀釋為濃度30質量%，獲得於後述之偶合反應中使用的官能基改質共軛二烯系聚合物(F-17)之稀釋溶液。(Step (2)) Next, the unmodified conjugated diene polymer (F'- 17) 700g, 1400g of toluene, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in toluene solution (as platinum atom, 2.1×10 -5 mol ), and 0.12g of acetic acid. Inside, 34 g of triethoxysilane was dropped at an internal temperature of 75 to 85°C over 2 hours, and then stirred at 80°C for 1 hour. After the stirring, it was concentrated under reduced pressure and filtered to obtain a functional group-modified conjugated diene polymer (F-17). According to the analysis of the obtained functional group-modified conjugated diene polymer (F-17), the main chain (a) of the conjugated diene graft polymer (G-17) described later can be determined Weight average molecular weight, vinyl content, and styrene-derived structural unit content. The obtained functional group-modified conjugated diene polymer (F-17) has a weight average molecular weight of 26,000, a vinyl content of 50 mol%, and a styrene-derived structural unit content of 0% by mass. The average number of Si atoms per molecule is 4. To the obtained functional group-modified conjugated diene polymer (F-17), 1710 g of cyclohexane was added and diluted to a concentration of 30% by mass to obtain the functional group-modified conjugated diene polymer used in the coupling reaction described later. Dilute solution of olefin polymer (F-17).

(步驟(3)) 將完全乾燥的5L高壓釜進行氮置換，飼入700g環己烷和78g二級丁基鋰(10.5質量%環己烷溶液)，升溫至50℃後，攪拌條件下，一邊將聚合溫度控制於50℃，一邊逐次添加四氫呋喃7.0g、及丁二烯340g，聚合1小時而獲得活性末端聚合物(I-17)。將步驟(3)中的聚合物溶液採樣而分析，可求得後述的氫化共軛二烯系接枝聚合物(G-17)之側鏈(b)之重量平均分子量、乙烯基含量、苯乙烯所衍生的結構單元含量。所獲得的活性末端聚合物(I-17)之重量平均分子量為5,000，乙烯基含量為50莫耳%，苯乙烯所衍生的結構單元含量為0質量%。(Step (3)) The completely dry 5L autoclave was replaced with nitrogen, and 700 g of cyclohexane and 78 g of secondary butyl lithium (10.5 mass% cyclohexane solution) were fed. After the temperature was raised to 50°C, the polymerization temperature was controlled under stirring conditions. At 50°C, 7.0 g of tetrahydrofuran and 340 g of butadiene were successively added, and polymerized for 1 hour to obtain a living terminal polymer (I-17). By sampling and analyzing the polymer solution in step (3), the weight average molecular weight, vinyl content, and benzene of the side chain (b) of the hydrogenated conjugated diene graft polymer (G-17) described later can be determined. The content of structural units derived from ethylene. The weight average molecular weight of the obtained living terminal polymer (I-17) was 5,000, the vinyl content was 50 mol%, and the content of styrene-derived structural units was 0% by mass.

(步驟(4)) 接著，於包含步驟(3)所獲得的活性末端聚合物(I-17)的溶液中，添加步驟(2)所獲得的官能基改質共軛二烯系聚合物(F-17)之稀釋溶液1480g，於50℃使進行偶合反應2小時。之後，添加二級丁基鋰(10.5質量%環己烷溶液)190g，使反應6小時，而將殘存的烷氧基之一部分封止。之後添加甲醇21g而使聚合反應停止，獲得含氫化前之共軛二烯系接枝聚合物(G'-17)的溶液。(Step (4)) Next, to the solution containing the living terminal polymer (I-17) obtained in step (3), add the functional group obtained in step (2) to modify the dilution of the conjugated diene polymer (F-17) The solution was 1480 g, and the coupling reaction was carried out at 50°C for 2 hours. After that, 190 g of secondary butyllithium (10.5 mass% cyclohexane solution) was added and reacted for 6 hours, and a part of the remaining alkoxy group was blocked. Then, 21 g of methanol was added to stop the polymerization reaction, and a solution containing the conjugated diene graft polymer (G'-17) before hydrogenation was obtained.

(步驟(5)) 於含所獲得的共軛二烯系接枝聚合物(G'-17)的溶液中，添加100mL之由辛酸鎳及三甲基鋁所形成的齊格勒系氫化觸媒(0.095mmol/L環己烷溶液)，於氫壓力1MPa、80℃之條件使反應5小時，而獲得含氫化共軛二烯系接枝聚合物(G-17)的溶液。(Step (5)) To the solution containing the obtained conjugated diene graft polymer (G'-17), add 100 mL of a Ziegler hydrogenation catalyst (0.095mmol/L Cyclohexane solution), and reacted for 5 hours under the conditions of a hydrogen pressure of 1 MPa and 80°C to obtain a solution containing a hydrogenated conjugated diene graft polymer (G-17).

(步驟(6)) 藉由將含所獲得的氫化共軛二烯系接枝聚合物(G-17)的溶液水洗而去除上述觸媒，將洗淨結束後之聚合物溶液於70℃真空乾燥24小時，回收氫化共軛二烯系接枝聚合物(G-17)。所獲得的氫化共軛二烯系接枝聚合物(G-17)之重量平均分子量為46,000，Mw/Mn為1.5，苯乙烯所衍生的結構單元含量為0質量%，偶合率為95%，氫化率為99莫耳%，聚合物每1分子之Si原子(分支點)的平均個數為4個，聚合物每一分子的官能基(c)的平均個數為0.4個，每Si原子(分支點)的官能基(c)的平均個數為0.1個，聚合物每一分子的側鏈(b)之平均條數為4條，每Si原子(分支點)的側鏈(b)之平均條數為1條。將所獲得的氫化共軛二烯系接枝聚合物(G-17)之分子規格、物性示於表4。(Step (6)) The catalyst is removed by washing the solution containing the obtained hydrogenated conjugated diene graft polymer (G-17) with water, and the polymer solution after washing is vacuum dried at 70°C for 24 hours, and the hydrogen is recovered Conjugated diene graft polymer (G-17). The weight average molecular weight of the obtained hydrogenated conjugated diene graft polymer (G-17) was 46,000, Mw/Mn was 1.5, the content of styrene-derived structural units was 0% by mass, and the coupling ratio was 95%. The hydrogenation rate is 99 mol%, the average number of Si atoms (branching points) per polymer molecule is 4, and the average number of functional groups (c) per polymer molecule is 0.4 per Si atom (Branch point) The average number of functional groups (c) is 0.1, the average number of side chains (b) per polymer molecule is 4, and the side chains (b) per Si atom (branch point) The average number of bars is 1. Table 4 shows the molecular specifications and physical properties of the obtained hydrogenated conjugated diene graft polymer (G-17).

[實施例18] (步驟(1)) 將完全乾燥的5L高壓釜進行氮置換，飼入1580g環己烷和56g二級丁基鋰(10.5質量%環己烷溶液)，升溫至50℃後，攪拌條件下，一邊將聚合溫度控制於50℃，一邊逐次添加四氫呋喃11g、丁二烯1250g，並聚合1小時。之後添加甲醇3.1g，而使聚合反應停止，獲得聚合物溶液。於所獲得的聚合物溶液中添加水而攪拌，以水將聚合物溶液洗淨。結束攪拌，確認聚合物溶液相與水相分離後，將水分離。藉由將洗淨結束後之聚合物溶液於70℃真空乾燥24小時，獲得未改質共軛二烯系聚合物(F'-18)。[Example 18] (step 1)) The completely dry 5L autoclave was replaced with nitrogen, 1580g cyclohexane and 56g secondary butyllithium (10.5 mass% cyclohexane solution) were fed, and the temperature was raised to 50°C, while stirring, the polymerization temperature was controlled at At 50°C, 11 g of tetrahydrofuran and 1,250 g of butadiene were added successively, and the polymerization was carried out for 1 hour. Then, 3.1 g of methanol was added to stop the polymerization reaction to obtain a polymer solution. Water is added to the obtained polymer solution and stirred, and the polymer solution is washed with water. After the stirring was completed and it was confirmed that the polymer solution phase was separated from the water phase, the water was separated. The polymer solution after washing was vacuum dried at 70°C for 24 hours to obtain an unmodified conjugated diene polymer (F'-18).

(步驟(2)) 接著，於具備攪拌機、回流冷卻器、滴下漏斗及溫度計的5L分離式燒瓶中，飼入步驟(1)所獲得的未改質共軛二烯系聚合物(F'-18)700g、環己烷1400g，進行氮置換。於其中，添加硼酸三甲酯22g及三乙基胺硼烷1.8g，並於80℃進行10小時反應。反應結束後，減壓濃縮及過濾，獲得官能基改質共軛二烯系聚合物(F-18)。藉由所獲得的官能基改質共軛二烯系聚合物(F-18)之分析，可求得後述的共軛二烯系接枝聚合物(G-18)之主鏈(a)之重量平均分子量、乙烯基含量、苯乙烯所衍生的結構單元含量。所獲得的官能基改質共軛二烯系聚合物(F-18)之重量平均分子量為26,000，乙烯基含量為50莫耳%，苯乙烯所衍生的結構單元含量為0質量%，聚合物每1分子之B原子的平均個數為4個。於所獲得的官能基改質共軛二烯系聚合物(F-18)中添加環己烷1680g，稀釋為濃度30質量%，獲得於後述之偶合反應中使用的官能基改質共軛二烯系聚合物(F-18)之稀釋溶液。(Step (2)) Next, 700 g of the unmodified conjugated diene polymer (F'-18) obtained in step (1) and cyclohexanone were fed into a 5L separable flask equipped with a stirrer, a reflux cooler, a dropping funnel, and a thermometer. 1400 g of alkane was replaced with nitrogen. To this, 22 g of trimethyl borate and 1.8 g of triethylamine borane were added, and the reaction was carried out at 80°C for 10 hours. After completion of the reaction, it was concentrated under reduced pressure and filtered to obtain a functional group-modified conjugated diene polymer (F-18). Through the analysis of the obtained functional group-modified conjugated diene polymer (F-18), it can be determined that the main chain (a) of the conjugated diene graft polymer (G-18) described later Weight average molecular weight, vinyl content, and styrene-derived structural unit content. The obtained functional group-modified conjugated diene polymer (F-18) has a weight average molecular weight of 26,000, a vinyl content of 50 mol%, and a styrene-derived structural unit content of 0% by mass. The average number of B atoms per molecule is 4. To the obtained functional group-modified conjugated diene polymer (F-18), 1680 g of cyclohexane was added and diluted to a concentration of 30% by mass to obtain the functional group-modified conjugated diene polymer used in the coupling reaction described later. Dilute solution of olefin polymer (F-18).

(步驟(3)) 將完全乾燥的5L高壓釜進行氮置換，飼入700g環己烷和78g二級丁基鋰(10.5質量%環己烷溶液)，升溫至50℃後，攪拌條件下，一邊將聚合溫度控制於50℃，一邊逐次添加四氫呋喃7.0g、及丁二烯340g，聚合1小時而獲得活性末端聚合物(I-18)。將步驟(3)中的聚合物溶液採樣而分析，可求得後述的氫化共軛二烯系接枝聚合物(G-18)之側鏈(b)之重量平均分子量、乙烯基含量、苯乙烯所衍生的結構單元含量。所獲得的活性末端聚合物(I-18)之重量平均分子量為5,000，乙烯基含量為50莫耳%，苯乙烯所衍生的結構單元含量為0質量%。(Step (3)) The completely dry 5L autoclave was replaced with nitrogen, and 700 g of cyclohexane and 78 g of secondary butyl lithium (10.5 mass% cyclohexane solution) were fed. After the temperature was raised to 50°C, the polymerization temperature was controlled under stirring conditions. At 50°C, 7.0 g of tetrahydrofuran and 340 g of butadiene were sequentially added, and polymerized for 1 hour to obtain a living terminal polymer (I-18). By sampling and analyzing the polymer solution in step (3), the weight average molecular weight, vinyl content, and benzene of the side chain (b) of the hydrogenated conjugated diene graft polymer (G-18) described later can be determined. The content of structural units derived from ethylene. The weight average molecular weight of the obtained living terminal polymer (I-18) was 5,000, the vinyl content was 50 mol%, and the content of styrene-derived structural units was 0% by mass.

(步驟(4)) 接著，於包含步驟(3)所獲得的活性末端聚合物(I-18)的溶液中，添加步驟(2)所獲得的官能基改質共軛二烯系聚合物(F-18)之稀釋溶液1480g，於50℃使進行偶合反應2小時。之後，添加二級丁基鋰(10.5質量%環己烷溶液)190g，使反應6小時，而將殘存的烷氧基之一部分封止。之後添加甲醇21g而使聚合反應停止，獲得含氫化前之共軛二烯系接枝聚合物(G'-18)的溶液。(Step (4)) Next, to the solution containing the living terminal polymer (I-18) obtained in step (3), add the functional group obtained in step (2) to modify the dilution of the conjugated diene polymer (F-18) The solution was 1480 g, and the coupling reaction was carried out at 50°C for 2 hours. After that, 190 g of secondary butyllithium (10.5 mass% cyclohexane solution) was added and reacted for 6 hours, and a part of the remaining alkoxy group was blocked. Then, 21 g of methanol was added to stop the polymerization reaction, and a solution containing the conjugated diene graft polymer (G'-18) before hydrogenation was obtained.

(步驟(5)) 於含所獲得的共軛二烯系接枝聚合物(G'-18)的溶液中，添加100mL之由辛酸鎳及三甲基鋁所形成的齊格勒系氫化觸媒(0.095mmol/L環己烷溶液)，於氫壓力1MPa、80℃之條件使反應5小時，而獲得含氫化共軛二烯系接枝聚合物(G-18)的溶液。(Step (5)) To the solution containing the obtained conjugated diene graft polymer (G'-18), add 100 mL of a Ziegler hydrogenation catalyst (0.095mmol/L) composed of nickel octoate and trimethylaluminum Cyclohexane solution), and reacted for 5 hours under the conditions of a hydrogen pressure of 1 MPa and 80°C to obtain a solution containing a hydrogenated conjugated diene graft polymer (G-18).

(步驟(6)) 藉由將含所獲得的氫化共軛二烯系接枝聚合物(G-18)的溶液水洗而去除上述觸媒，將洗淨結束後之聚合物溶液於70℃真空乾燥24小時，回收氫化共軛二烯系接枝聚合物(G-18)。所獲得的氫化共軛二烯系接枝聚合物(G-18)之重量平均分子量為46,000，Mw/Mn為1.5，苯乙烯所衍生的結構單元含量為0質量%，偶合率為95%，氫化率為99莫耳%，聚合物每1分子B原子(分支點)的平均個數為4個，聚合物每一分子的官能基(c)的平均個數為0.4個，B原子(分支點)的官能基(c)的平均個數為0.1個，聚合物每一分子的側鏈(b)之平均條數為4條，B原子(分支點)的側鏈(b)之平均條數為1條。將所獲得的氫化共軛二烯系接枝聚合物(G-18)之分子規格、物性示於表4。(Step (6)) The catalyst is removed by washing the solution containing the obtained hydrogenated conjugated diene graft polymer (G-18) with water, and the polymer solution after washing is vacuum dried at 70°C for 24 hours, and the hydrogen is recovered Conjugated diene graft polymer (G-18). The weight average molecular weight of the obtained hydrogenated conjugated diene graft polymer (G-18) was 46,000, Mw/Mn was 1.5, the content of styrene-derived structural units was 0% by mass, and the coupling ratio was 95%. The hydrogenation rate is 99 mol%, the average number of B atoms (branching points) per polymer molecule is 4, the average number of functional groups (c) per polymer molecule is 0.4, and the average number of B atoms (branching points) is 0.4. The average number of functional groups (c) at point) is 0.1, the average number of side chains (b) per polymer molecule is 4, and the average number of side chains (b) at the B atom (branch point) is The number is 1. Table 4 shows the molecular specifications and physical properties of the obtained hydrogenated conjugated diene graft polymer (G-18).

[比較例1] (步驟(1)) 將完全乾燥的5L高壓釜進行氮置換，飼入1370g環己烷和240g二級丁基鋰(10.5質量%環己烷溶液)，升溫至50℃後，攪拌條件下，一邊將聚合溫度控制於50℃，一邊逐次添加丁二烯1250g，並聚合1小時。之後添加甲醇14g而使聚合反應停止，獲得聚合物溶液。於所獲得的聚合物溶液中添加水而攪拌，以水將聚合物溶液洗淨。結束攪拌，確認聚合物溶液相與水相分離後，將水分離。藉由將洗淨結束後之聚合物溶液於70℃真空乾燥24小時，獲得未改質共軛二烯系聚合物(F'-19)。[Comparative Example 1] (step 1)) The completely dry 5L autoclave was replaced with nitrogen, fed with 1370g cyclohexane and 240g secondary butyllithium (10.5 mass% cyclohexane solution), heated to 50°C, while stirring, controlled the polymerization temperature at At 50°C, 1250 g of butadiene was added successively and polymerized for 1 hour. After that, 14 g of methanol was added to stop the polymerization reaction, and a polymer solution was obtained. Water is added to the obtained polymer solution and stirred, and the polymer solution is washed with water. After the stirring was completed and it was confirmed that the polymer solution phase was separated from the water phase, the water was separated. The unmodified conjugated diene polymer (F'-19) was obtained by vacuum drying the polymer solution after washing at 70°C for 24 hours.

(步驟(2)) 接著，於具備攪拌機、回流冷卻器、滴下漏斗及溫度計的5L分離式燒瓶中，飼入步驟(1)所獲得的未改質共軛二烯系聚合物(F'-19)600g、環己烷1400g、鉑-1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物之2質量%二甲苯溶液(Petrarch System公司製「PC072」)5.6mL、三甲基氯矽烷120g，整夜攪拌此等。之後，於其中，滴加二甲基氯矽烷150g後，緩緩加熱至內溫成為70℃，將內溫直接保持於70℃並於回流下攪拌24小時。攪拌結束後，減壓濃縮及過濾，獲得官能基改質共軛二烯系聚合物(F-19)。藉由所獲得的官能基改質共軛二烯系聚合物(F-19)之分析，可求得後述的氫化共軛二烯系接枝聚合物(G-19)之主鏈(a)之重量平均分子量、乙烯基含量、苯乙烯所衍生的結構單元含量。所獲得的官能基改質共軛二烯系聚合物(F-19)之重量平均分子量為6,000，乙烯基含量為10莫耳%，苯乙烯所衍生的結構單元含量為0質量%，聚合物每1分子之Si原子的平均個數為8個。於所獲得的官能基改質共軛二烯系聚合物(F-19)中添加環己烷1750g，稀釋為濃度30質量%，獲得於後述之偶合反應中使用的官能基改質共軛二烯系聚合物(F-19)之稀釋溶液。(Step (2)) Next, in a 5L separable flask equipped with a stirrer, a reflux cooler, a dropping funnel, and a thermometer, 600 g of the unmodified conjugated diene polymer (F'-19) obtained in step (1), cyclohexanone 1400 g of alkane, 2% by mass xylene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex ("PC072" manufactured by Petrarch System) 5.6 mL, 120 g of trimethylchlorosilane, stirring this overnight. Thereafter, 150 g of dimethylchlorosilane was added dropwise, and the mixture was gradually heated until the internal temperature became 70°C, the internal temperature was directly maintained at 70°C, and the mixture was stirred under reflux for 24 hours. After the stirring, it was concentrated and filtered under reduced pressure to obtain a functional group-modified conjugated diene polymer (F-19). By analyzing the obtained functional group-modified conjugated diene polymer (F-19), the main chain (a) of the hydrogenated conjugated diene graft polymer (G-19) described later can be obtained The weight average molecular weight, vinyl content, and styrene-derived structural unit content. The obtained functional group-modified conjugated diene polymer (F-19) has a weight average molecular weight of 6,000, a vinyl content of 10 mol%, and a styrene-derived structural unit content of 0% by mass. The average number of Si atoms per molecule is 8. To the obtained functional group-modified conjugated diene polymer (F-19), 1750 g of cyclohexane was added and diluted to a concentration of 30% by mass to obtain the functional group-modified conjugated diene polymer used in the coupling reaction described later. Dilute solution of olefin polymer (F-19).

(步驟(3)) 將完全乾燥的5L高壓釜進行氮置換，飼入2270g環己烷和8.7g二級丁基鋰(10.5質量%環己烷溶液)，升溫至50℃後，攪拌條件下，一邊將聚合溫度控制於50℃，一邊逐次添加異戊二烯570g，聚合1小時，獲得活性末端聚合物(I-19)。將步驟(3)中的聚合物溶液採樣而分析，可求得後述的氫化共軛二烯系接枝聚合物(G-19)之側鏈(b)之重量平均分子量、乙烯基含量、苯乙烯所衍生的結構單元含量。所獲得的活性末端聚合物(I-19)之重量平均分子量為60,000，乙烯基含量為10莫耳%，苯乙烯所衍生的結構單元含量為0質量%。(Step (3)) The completely dry 5L autoclave was replaced with nitrogen, 2270g cyclohexane and 8.7g secondary butyllithium (10.5 mass% cyclohexane solution) were fed, and after the temperature was raised to 50°C, the polymerization temperature was controlled while stirring. At 50°C, 570 g of isoprene was added successively, and polymerized for 1 hour to obtain a living terminal polymer (I-19). By sampling and analyzing the polymer solution in step (3), the weight average molecular weight, vinyl content, and benzene of the side chain (b) of the hydrogenated conjugated diene graft polymer (G-19) described later can be determined. The content of structural units derived from ethylene. The weight average molecular weight of the obtained living terminal polymer (I-19) was 60,000, the vinyl content was 10 mol%, and the content of styrene-derived structural units was 0% by mass.

(步驟(4)) 接著，於含有步驟(3)所獲得的活性末端聚合物(I-19)的溶液中，添加四氫呋喃0.7g及步驟(2)所獲得的官能基改質共軛二烯系聚合物(F-19)之稀釋溶液20g，於50℃使進行偶合反應2小時。之後，添加二級丁基鋰(10.5質量%環己烷溶液)26g，使反應6小時，而將殘存的烷氧基之一部分封止。之後添加甲醇1.0g而使聚合反應停止，獲得含有氫化前之共軛二烯系接枝聚合物(G'-19)的溶液。(Step (4)) Next, to the solution containing the living terminal polymer (I-19) obtained in step (3), 0.7 g of tetrahydrofuran and the functional group-modified conjugated diene polymer (F-) obtained in step (2) were added. 20 g of the diluted solution of 19) was subjected to coupling reaction at 50°C for 2 hours. After that, 26 g of secondary butyllithium (10.5 mass% cyclohexane solution) was added and reacted for 6 hours, and a part of the remaining alkoxy group was blocked. Then, 1.0 g of methanol was added to stop the polymerization reaction, and a solution containing the conjugated diene graft polymer (G'-19) before hydrogenation was obtained.

(步驟(5)) 於含所獲得的共軛二烯系接枝聚合物(G'-19)的溶液中，添加100mL之由辛酸鎳及三甲基鋁所形成的齊格勒系氫化觸媒(0.095mmol/L環己烷溶液)，於氫壓力1MPa、80℃之條件使反應5小時，而獲得含氫化共軛二烯系接枝聚合物(G-19)的溶液。(Step (5)) To the solution containing the obtained conjugated diene graft polymer (G'-19), add 100 mL of a Ziegler hydrogenation catalyst (0.095mmol/L) composed of nickel octoate and trimethylaluminum Cyclohexane solution), and reacted for 5 hours under the conditions of a hydrogen pressure of 1 MPa and 80°C to obtain a solution containing a hydrogenated conjugated diene-based graft polymer (G-19).

(步驟(6)) 藉由將含所獲得的氫化共軛二烯系接枝聚合物(G-19)的溶液水洗而去除上述觸媒，將洗淨結束後之聚合物溶液於70℃真空乾燥24小時，回收氫化共軛二烯系接枝聚合物(G-19)。所獲得的氫化共軛二烯系接枝聚合物(G-19)之重量平均分子量為486,000，Mw/Mn為1.5，苯乙烯所衍生的結構單元含量為0質量%，偶合率為95%，氫化率為99莫耳%，聚合物每1分子之Si原子(分支點)的平均個數為8個，聚合物每一分子的官能基(c)的平均個數為0個，每Si原子(分支點)的官能基(c)的平均個數為0個，聚合物每一分子的側鏈(b)之平均條數為8條，每Si原子(分支點)的側鏈(b)之平均條數為1條。將所獲得的氫化共軛二烯系接枝聚合物(G-19)之分子規格、物性示於表4。(Step (6)) The catalyst is removed by washing the solution containing the obtained hydrogenated conjugated diene graft polymer (G-19) with water, and the polymer solution after washing is vacuum dried at 70°C for 24 hours, and the hydrogen is recovered Conjugated diene graft polymer (G-19). The weight average molecular weight of the obtained hydrogenated conjugated diene graft polymer (G-19) was 486,000, Mw/Mn was 1.5, the content of styrene-derived structural units was 0% by mass, and the coupling ratio was 95%. The hydrogenation rate is 99 mol%, the average number of Si atoms (branching points) per polymer molecule is 8, and the average number of functional groups (c) per polymer molecule is 0, per Si atom (Branch point) The average number of functional groups (c) is 0, the average number of side chains (b) per polymer molecule is 8, and the side chains (b) per Si atom (branch point) The average number of bars is 1. Table 4 shows the molecular specifications and physical properties of the obtained hydrogenated conjugated diene graft polymer (G-19).

[比較例2] (步驟(1)) 將完全乾燥的5L高壓釜進行氮置換，飼入1580g環己烷和56g二級丁基鋰(10.5質量%環己烷溶液)，升溫至50℃後，攪拌條件下，一邊將聚合溫度控制於50℃，一邊逐次添加四氫呋喃11g、丁二烯1250g，並聚合1小時。之後添加甲醇3.1g，而使聚合反應停止，獲得聚合物溶液。於所獲得的聚合物溶液中添加水而攪拌，以水將聚合物溶液洗淨。結束攪拌，確認聚合物溶液相與水相分離後，將水分離。藉由將洗淨結束後之聚合物溶液於70℃真空乾燥24小時，獲得未改質共軛二烯系聚合物(F'-20)。[Comparative Example 2] (step 1)) The completely dry 5L autoclave was replaced with nitrogen, 1580g cyclohexane and 56g secondary butyllithium (10.5 mass% cyclohexane solution) were fed, and the temperature was raised to 50°C, while stirring, the polymerization temperature was controlled at At 50°C, 11 g of tetrahydrofuran and 1,250 g of butadiene were added successively, and the polymerization was carried out for 1 hour. Then, 3.1 g of methanol was added to stop the polymerization reaction to obtain a polymer solution. Water is added to the obtained polymer solution and stirred, and the polymer solution is washed with water. After the stirring was completed and it was confirmed that the polymer solution phase was separated from the water phase, the water was separated. The unmodified conjugated diene polymer (F'-20) was obtained by vacuum drying the polymer solution after washing at 70°C for 24 hours.

(步驟(2)) 接著，於具備攪拌機、回流冷卻器、滴下漏斗及溫度計的5L分離式燒瓶中，飼入步驟(1)所獲得的未改質共軛二烯系聚合物(F'-20)700g、環己烷1400g、鉑-1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物之2質量%二甲苯溶液(Petrarch System公司製「PC072」)5.6mL、三甲基氯矽烷120g，整夜攪拌此等。之後，於其中，滴加二甲基氯矽烷20g後，緩緩加熱至內溫成為70℃，將內溫直接保持於70℃並於回流下攪拌24小時。攪拌結束後，減壓濃縮及過濾，獲得官能基改質共軛二烯系聚合物(F-20)。藉由所獲得的官能基改質共軛二烯系聚合物(F-20)之分析，可求得後述的氫化共軛二烯系接枝聚合物(G-20)之主鏈(a)之重量平均分子量、乙烯基含量、苯乙烯所衍生的結構單元含量。所獲得的官能基改質共軛二烯系聚合物(F-20)之重量平均分子量為26,000，乙烯基含量為50莫耳%，苯乙烯所衍生的結構單元含量為0質量%，聚合物每1分子之Si原子之平均個數為4個。於所獲得的官能基改質共軛二烯系聚合物(F-20)中添加環己烷1680g，稀釋為濃度30質量%，獲得於後述之偶合反應中使用的官能基改質共軛二烯系聚合物(F-20)之稀釋溶液。(Step (2)) Next, in a 5L separable flask equipped with a stirrer, a reflux cooler, a dropping funnel, and a thermometer, 700 g of the unmodified conjugated diene polymer (F'-20) obtained in step (1), cyclohexanone 1400 g of alkane, 2% by mass xylene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex ("PC072" manufactured by Petrarch System) 5.6 mL, 120 g of trimethylchlorosilane, stirring this overnight. Thereafter, 20 g of dimethylchlorosilane was added dropwise, and the mixture was gradually heated until the internal temperature became 70°C, the internal temperature was directly maintained at 70°C, and the mixture was stirred under reflux for 24 hours. After the stirring, it was concentrated under reduced pressure and filtered to obtain a functional group-modified conjugated diene polymer (F-20). By analyzing the obtained functional group-modified conjugated diene polymer (F-20), the main chain (a) of the hydrogenated conjugated diene graft polymer (G-20) described later can be determined The weight average molecular weight, vinyl content, and styrene-derived structural unit content. The obtained functional group-modified conjugated diene polymer (F-20) has a weight average molecular weight of 26,000, a vinyl content of 50 mol%, and a styrene-derived structural unit content of 0% by mass. The average number of Si atoms per molecule is 4. To the obtained functional group-modified conjugated diene polymer (F-20), 1680 g of cyclohexane was added and diluted to a concentration of 30% by mass to obtain the functional group-modified conjugated diene polymer used in the coupling reaction described later. Dilute solution of olefin polymer (F-20).

(步驟(3)) 將完全乾燥的5L高壓釜進行氮置換，飼入700g環己烷和78g二級丁基鋰(10.5質量%環己烷溶液)，升溫至50℃後，攪拌條件下，逐次添加四氫呋喃7.0g、及丁二烯340g，而將聚合溫度控制於50℃，聚合1小時而獲得活性末端聚合物(I-20)。將步驟(3)中的聚合物溶液採樣而分析，可求得後述的氫化共軛二烯系接枝聚合物(G-20)之側鏈(b)之重量平均分子量、乙烯基含量、苯乙烯所衍生的結構單元含量。所獲得的活性末端聚合物(I-20)之重量平均分子量為5,000，乙烯基含量為50莫耳%，苯乙烯所衍生的結構單元含量為0質量%。(Step (3)) The completely dry 5L autoclave was replaced with nitrogen, and 700g of cyclohexane and 78g of secondary butyllithium (10.5 mass% cyclohexane solution) were fed. After the temperature was raised to 50°C, under stirring, 7.0g of tetrahydrofuran, And 340 g of butadiene, while controlling the polymerization temperature to 50°C, polymerizing for 1 hour to obtain a living terminal polymer (I-20). By sampling and analyzing the polymer solution in step (3), the weight average molecular weight, vinyl content, and benzene of the side chain (b) of the hydrogenated conjugated diene graft polymer (G-20) described later can be determined. The content of structural units derived from ethylene. The weight average molecular weight of the obtained living terminal polymer (I-20) was 5,000, the vinyl content was 50 mol%, and the content of styrene-derived structural units was 0% by mass.

(步驟(4)) 接著，於包含步驟(3)所獲得的活性末端聚合物(I-20)的溶液中，添加步驟(2)所獲得的官能基改質共軛二烯系聚合物(F-20)之稀釋溶液1480g，於50℃使進行偶合反應2小時。之後，添加二級丁基鋰(10.5質量%環己烷溶液)190g，使反應6小時，而將殘存的烷氧基之一部分封止。之後添加甲醇21g而使聚合反應停止，獲得含氫化前之共軛二烯系接枝聚合物(G'-20)的溶液。(Step (4)) Next, to the solution containing the living terminal polymer (I-20) obtained in step (3), add the functional group obtained in step (2) to modify the dilution of the conjugated diene polymer (F-20) The solution was 1480 g, and the coupling reaction was carried out at 50°C for 2 hours. After that, 190 g of secondary butyllithium (10.5 mass% cyclohexane solution) was added and reacted for 6 hours, and a part of the remaining alkoxy group was blocked. Then, 21 g of methanol was added to stop the polymerization reaction, and a solution containing the conjugated diene graft polymer (G'-20) before hydrogenation was obtained.

(步驟(5)) 於含所獲得的共軛二烯系接枝聚合物(G'-20)的溶液中，添加100mL之由辛酸鎳及三甲基鋁所形成的齊格勒系氫化觸媒(0.095mmol/L環己烷溶液)，於氫壓力1MPa、80℃之條件使反應5小時，而獲得含氫化共軛二烯系接枝聚合物(G-20)的溶液。(Step (5)) To the solution containing the obtained conjugated diene graft polymer (G'-20), add 100 mL of a Ziegler hydrogenation catalyst (0.095mmol/L Cyclohexane solution), and reacted for 5 hours under the conditions of a hydrogen pressure of 1 MPa and 80°C to obtain a solution containing a hydrogenated conjugated diene graft polymer (G-20).

(步驟(6)) 藉由將含所獲得的氫化共軛二烯系接枝聚合物(G-20)的溶液水洗而去除上述觸媒，將洗淨結束後之聚合物溶液於70℃真空乾燥24小時，回收氫化共軛二烯系接枝聚合物(G-20)。所獲得的氫化共軛二烯系接枝聚合物(G-20)之重量平均分子量為46,000，Mw/Mn為1.5，苯乙烯所衍生的結構單元含量為0質量%，偶合率為95%，氫化率為99莫耳%，聚合物每1分子之Si原子(分支點)的平均個數為4個，聚合物每一分子的官能基(c)的平均個數為0個，每Si原子(分支點)的官能基(c)的平均個數為0個，聚合物每一分子的側鏈(b)之平均條數為4條，每Si原子(分支點)的側鏈(b)之平均條數為1條。將所獲得的氫化共軛二烯系接枝聚合物(G-20)之分子規格、物性示於表4。(Step (6)) The catalyst is removed by washing the solution containing the obtained hydrogenated conjugated diene graft polymer (G-20) with water, and the polymer solution after washing is vacuum dried at 70°C for 24 hours, and the hydrogen is recovered Conjugated diene graft polymer (G-20). The weight average molecular weight of the obtained hydrogenated conjugated diene graft polymer (G-20) was 46,000, Mw/Mn was 1.5, the content of styrene-derived structural units was 0% by mass, and the coupling ratio was 95%. The hydrogenation rate is 99 mol%, the average number of Si atoms (branching points) per polymer molecule is 4, and the average number of functional groups (c) per polymer molecule is 0, per Si atom (Branch point) The average number of functional groups (c) is 0, the average number of side chains (b) per polymer molecule is 4, and the side chains (b) per Si atom (branch point) The average number of bars is 1. Table 4 shows the molecular specifications and physical properties of the obtained hydrogenated conjugated diene graft polymer (G-20).

[比較例3] (步驟(1)) 將完全乾燥的5L高壓釜進行氮置換，飼入1370g環己烷和240g二級丁基鋰(10.5質量%環己烷溶液)，升溫至50℃後，攪拌條件下，一邊將聚合溫度控制於50℃，一邊逐次添加丁二烯1250g，並聚合1小時。之後添加甲醇14g而使聚合反應停止，獲得聚合物溶液。於所獲得的聚合物溶液中添加水而攪拌，以水將聚合物溶液洗淨。結束攪拌，確認聚合物溶液相與水相分離後，將水分離。藉由將洗淨結束後之聚合物溶液於70℃真空乾燥24小時，獲得未改質共軛二烯系聚合物(F'-21)。[Comparative Example 3] (step 1)) The completely dry 5L autoclave was replaced with nitrogen, fed with 1370g cyclohexane and 240g secondary butyllithium (10.5 mass% cyclohexane solution), heated to 50°C, while stirring, controlled the polymerization temperature at At 50°C, 1250 g of butadiene was added successively and polymerized for 1 hour. After that, 14 g of methanol was added to stop the polymerization reaction, and a polymer solution was obtained. Water is added to the obtained polymer solution and stirred, and the polymer solution is washed with water. After the stirring was completed and it was confirmed that the polymer solution phase was separated from the water phase, the water was separated. The unmodified conjugated diene polymer (F'-21) was obtained by vacuum drying the polymer solution after washing at 70°C for 24 hours.

(步驟(2)) 接著，於容量1L的高壓釜中，飼入步驟(1)所獲得的未改質共軛二烯系聚合物(F'-21)460g，一邊於60℃攪拌3小時一邊進行氮脫氣。添加過氧異丁酸三級丁酯0.6g與3-巰基丙基三乙氧基矽烷290g，使於80℃反應8小時，獲得官能基改質共軛二烯系聚合物(F-21)。藉由所獲得的官能基改質共軛二烯系聚合物(F-21)之分析，可求得後述的氫化共軛二烯系接枝聚合物(G-21)之主鏈(a)之重量平均分子量、乙烯基含量、苯乙烯所衍生的結構單元含量。所獲得的官能基改質共軛二烯系聚合物(F-21)之重量平均分子量為6,000，乙烯基含量為10莫耳%，苯乙烯所衍生的結構單元含量為0質量%，聚合物每1分子之Si原子的平均個數為8個。於所獲得的官能基改質共軛二烯系聚合物(F-21)中添加環己烷1750g，稀釋為濃度30質量%，獲得於後述之偶合反應中使用的官能基改質共軛二烯系聚合物(F-21)之稀釋溶液。(Step (2)) Next, 460 g of the unmodified conjugated diene-based polymer (F'-21) obtained in step (1) was fed into an autoclave with a volume of 1 L, and nitrogen was degassed while stirring at 60°C for 3 hours. Add 0.6 g of tertiary butyl peroxyisobutyrate and 290 g of 3-mercaptopropyl triethoxysilane, and react at 80°C for 8 hours to obtain a functional group-modified conjugated diene polymer (F-21) . By analyzing the obtained functional group-modified conjugated diene polymer (F-21), the main chain (a) of the hydrogenated conjugated diene graft polymer (G-21) described later can be determined The weight average molecular weight, vinyl content, and styrene-derived structural unit content. The obtained functional group-modified conjugated diene polymer (F-21) has a weight average molecular weight of 6,000, a vinyl content of 10 mol%, and a styrene-derived structural unit content of 0% by mass. The average number of Si atoms per molecule is 8. To the obtained functional group-modified conjugated diene polymer (F-21), 1750 g of cyclohexane was added and diluted to a concentration of 30% by mass to obtain the functional group-modified conjugated diene polymer used in the coupling reaction described later. Dilute solution of olefin polymer (F-21).

(步驟(3)) 將完全乾燥的5L高壓釜進行氮置換，飼入2270g環己烷和8.7g二級丁基鋰(10.5質量%環己烷溶液)，升溫至50℃後，攪拌條件下，一邊將聚合溫度控制於50℃，一邊逐次添加異戊二烯570g，聚合1小時，獲得活性末端聚合物(I-21)。將步驟(3)中的聚合物溶液採樣而分析，可求得後述的氫化共軛二烯系接枝聚合物(G-21)之側鏈(b)之重量平均分子量、乙烯基含量、苯乙烯所衍生的結構單元含量。所獲得的活性末端聚合物(I-21)之重量平均分子量為60,000，乙烯基含量為10莫耳%，苯乙烯所衍生的結構單元含量為0質量%。(Step (3)) The completely dry 5L autoclave was replaced with nitrogen, 2270g cyclohexane and 8.7g secondary butyllithium (10.5 mass% cyclohexane solution) were fed, and after the temperature was raised to 50°C, the polymerization temperature was controlled while stirring. At 50°C, 570 g of isoprene was added successively and polymerized for 1 hour to obtain a living terminal polymer (I-21). By sampling and analyzing the polymer solution in step (3), the weight average molecular weight, vinyl content, and benzene of the side chain (b) of the hydrogenated conjugated diene graft polymer (G-21) described later can be determined. The content of structural units derived from ethylene. The weight average molecular weight of the obtained living terminal polymer (I-21) was 60,000, the vinyl content was 10 mol%, and the content of styrene-derived structural units was 0% by mass.

(步驟(4)) 接著，於含有步驟(3)所獲得的活性末端聚合物(I-21)的溶液中，添加四氫呋喃0.7g及步驟(2)所獲得的官能基改質共軛二烯系聚合物(F-21)之稀釋溶液20g，於50℃使進行偶合反應2小時。之後添加甲醇1.0g而使聚合反應停止，獲得含有氫化前之共軛二烯系接枝聚合物(G'-21)的溶液。(Step (4)) Next, to the solution containing the living terminal polymer (I-21) obtained in step (3), 0.7 g of tetrahydrofuran and the functional group-modified conjugated diene polymer (F- 20g of the diluted solution of 21) was subjected to coupling reaction at 50°C for 2 hours. Then, 1.0 g of methanol was added to stop the polymerization reaction, and a solution containing the conjugated diene graft polymer (G'-21) before hydrogenation was obtained.

(步驟(5)) 於含所獲得的共軛二烯系接枝聚合物(G'-21)的溶液中，添加100mL之由辛酸鎳及三甲基鋁所形成的齊格勒系氫化觸媒(0.095mmol/L環己烷溶液)，於氫壓力1MPa、80℃之條件使反應5小時，而獲得含氫化共軛二烯系接枝聚合物(G-21)的溶液。(Step (5)) To the solution containing the obtained conjugated diene graft polymer (G'-21), add 100 mL of a Ziegler hydrogenation catalyst (0.095mmol/L Cyclohexane solution), and reacted for 5 hours under the conditions of a hydrogen pressure of 1 MPa and 80°C to obtain a solution containing a hydrogenated conjugated diene graft polymer (G-21).

(步驟(6)) 藉由將含所獲得的氫化共軛二烯系接枝聚合物(G-21)的溶液水洗而去除上述觸媒，將洗淨結束後之聚合物溶液於70℃真空乾燥24小時後，氫化共軛二烯系接枝聚合物(G-21)為不溶化，凝膠分率為80質量%以上。所獲得的氫化共軛二烯系接枝聚合物(G-21)之重量平均分子量為486,000，Mw/Mn為1.5，苯乙烯所衍生的結構單元含量為0質量%，偶合率為95%，氫化率為99莫耳%，聚合物每1分子之Si原子(分支點)的平均個數為8個，聚合物每一分子的官能基(c)的平均個數為16個，每Si原子(分支點)的官能基(c)的平均個數為2個，聚合物每一分子的側鏈(b)之平均條數為8條，每Si原子(分支點)的側鏈(b)之平均條數為1條(重量平均分子量、Mw/Mn、乙烯基含量、苯乙烯單元含量、聚合物每1分子之Si原子(分支點)的平均個數、聚合物每一分子的官能基(c)的平均個數、每Si原子(分支點)的平均個數，係測定步驟(4)或步驟(5)所獲得的聚合物溶液於常溫、常壓下進行乾燥而獲得的聚合物的值)。將所獲得的氫化共軛二烯系接枝聚合物(G-21)之分子規格、物性示於表4。(Step (6)) The catalyst is removed by washing the solution containing the obtained hydrogenated conjugated diene graft polymer (G-21) with water, and the polymer solution after washing is vacuum dried at 70°C for 24 hours, and then hydrogenated The conjugated diene-based graft polymer (G-21) is insolubilized and has a gel fraction of 80% by mass or more. The weight average molecular weight of the obtained hydrogenated conjugated diene graft polymer (G-21) was 486,000, Mw/Mn was 1.5, the content of styrene-derived structural units was 0% by mass, and the coupling ratio was 95%. The hydrogenation rate is 99 mol%, the average number of Si atoms (branching points) per polymer molecule is 8, and the average number of functional groups (c) per polymer molecule is 16, per Si atom (Branch point) The average number of functional groups (c) is 2, and the average number of side chains (b) per polymer molecule is 8, and the side chains (b) per Si atom (branch point) The average number is 1 (weight average molecular weight, Mw/Mn, vinyl content, styrene unit content, average number of Si atoms (branching points) per polymer molecule, functional groups per polymer molecule The average number of (c) and the average number per Si atom (branch point) are the polymer obtained by drying the polymer solution obtained in step (4) or step (5) at room temperature and pressure Value). Table 4 shows the molecular specifications and physical properties of the obtained hydrogenated conjugated diene graft polymer (G-21).

[比較例4] (步驟(1)) 將完全乾燥的5L高壓釜進行氮置換，飼入1580g環己烷和56g二級丁基鋰(10.5質量%環己烷溶液)，升溫至50℃後，攪拌條件下，一邊將聚合溫度控制於50℃，一邊逐次添加四氫呋喃11g、丁二烯1250g，並聚合1小時。之後添加甲醇3.1g，而使聚合反應停止，獲得聚合物溶液。於所獲得的聚合物溶液中添加水而攪拌，以水將聚合物溶液洗淨。結束攪拌，確認聚合物溶液相與水相分離後，將水分離。藉由將洗淨結束後之聚合物溶液於70℃真空乾燥24小時，獲得未改質共軛二烯系聚合物(F'-22)。[Comparative Example 4] (step 1)) The completely dry 5L autoclave was replaced with nitrogen, 1580g cyclohexane and 56g secondary butyllithium (10.5 mass% cyclohexane solution) were fed, and the temperature was raised to 50°C, while stirring, the polymerization temperature was controlled at At 50°C, 11 g of tetrahydrofuran and 1,250 g of butadiene were added successively, and the polymerization was carried out for 1 hour. Then, 3.1 g of methanol was added to stop the polymerization reaction to obtain a polymer solution. Water is added to the obtained polymer solution and stirred, and the polymer solution is washed with water. After the stirring was completed and it was confirmed that the polymer solution phase was separated from the water phase, the water was separated. The unmodified conjugated diene polymer (F'-22) was obtained by vacuum drying the polymer solution after washing at 70°C for 24 hours.

(步驟(2)) 接著，於容量1L的高壓釜中，飼入步驟(1)所獲得的未改質共軛二烯系聚合物(F'-22)700g，一邊於60℃攪拌3小時一邊進行氮脫氣。添加過氧異丁酸三級丁酯0.6g與3-巰基丙基三乙氧基矽烷51g，使於80℃反應8小時，獲得官能基改質共軛二烯系聚合物(F-22)。藉由所獲得的官能基改質共軛二烯系聚合物(F-22)之分析，可求得後述的氫化共軛二烯系接枝聚合物(G-22)之主鏈(a)之重量平均分子量、乙烯基含量、苯乙烯単位含量。所獲得的官能基改質共軛二烯系聚合物(F-22)之重量平均分子量為26,000，乙烯基含量為50莫耳%，苯乙烯單元含量為0質量%，聚合物每1分子之Si原子的平均個數為4個。於所獲得的官能基改質共軛二烯系聚合物(F-21)中添加環己烷1750g，稀釋為濃度30質量%，獲得於後述之偶合反應中使用的官能基改質共軛二烯系聚合物(F-22)之稀釋溶液。(Step (2)) Next, 700 g of the unmodified conjugated diene-based polymer (F'-22) obtained in step (1) was fed into an autoclave with a volume of 1 L, and nitrogen degassed while stirring at 60°C for 3 hours. Add 0.6 g of tertiary butyl peroxyisobutyrate and 51 g of 3-mercaptopropyl triethoxysilane, and react at 80°C for 8 hours to obtain a functional group-modified conjugated diene polymer (F-22) . By analyzing the obtained functional group-modified conjugated diene polymer (F-22), the main chain (a) of the hydrogenated conjugated diene graft polymer (G-22) described later can be determined The weight average molecular weight, vinyl content, styrene unit content. The obtained functional group-modified conjugated diene polymer (F-22) has a weight average molecular weight of 26,000, a vinyl content of 50 mol%, a styrene unit content of 0% by mass, and a polymer per molecule of The average number of Si atoms is four. To the obtained functional group-modified conjugated diene polymer (F-21), 1750 g of cyclohexane was added and diluted to a concentration of 30% by mass to obtain the functional group-modified conjugated diene polymer used in the coupling reaction described later. Dilute solution of olefin polymer (F-22).

(步驟(3)) 將完全乾燥的5L高壓釜進行氮置換，飼入700g環己烷和78g二級丁基鋰(10.5質量%環己烷溶液)，升溫至50℃後，攪拌條件下，逐次添加四氫呋喃7.0g、及丁二烯340g，而控制聚合溫度成為50℃，聚合1小時並獲得活性末端聚合物(I-22)。將步驟(3)中的聚合物溶液採樣而分析，可求得後述的氫化共軛二烯系接枝聚合物(G-22)之側鏈(b)之重量平均分子量、乙烯基含量、苯乙烯所衍生的結構單元含量。所獲得的活性末端聚合物(I-22)之重量平均分子量為5,000，乙烯基含量為50莫耳%，苯乙烯所衍生的結構單元含量為0質量%。(Step (3)) The completely dry 5L autoclave was replaced with nitrogen, and 700g of cyclohexane and 78g of secondary butyllithium (10.5 mass% cyclohexane solution) were fed. After the temperature was raised to 50°C, under stirring, 7.0g of tetrahydrofuran, And 340 g of butadiene, while controlling the polymerization temperature to 50°C, the polymerization was carried out for 1 hour to obtain a living terminal polymer (I-22). By sampling and analyzing the polymer solution in step (3), the weight average molecular weight, vinyl content, and benzene of the side chain (b) of the hydrogenated conjugated diene graft polymer (G-22) described later can be determined. The content of structural units derived from ethylene. The weight average molecular weight of the obtained living terminal polymer (I-22) was 5,000, the vinyl content was 50 mol%, and the content of styrene-derived structural units was 0% by mass.

(步驟(4)) 接著，於包含步驟(3)所獲得的活性末端聚合物(I-22)的溶液中，添加步驟(2)所獲得的官能基改質共軛二烯系聚合物(F-22)之稀釋溶液1480g，於50℃使進行偶合反應2小時。之後，添加甲醇20g而使聚合反應停止，獲得含氫化前之共軛二烯系接枝聚合物(G'-22)的溶液。(Step (4)) Next, to the solution containing the living terminal polymer (I-22) obtained in step (3), add the functional group obtained in step (2) to modify the dilution of the conjugated diene polymer (F-22) The solution was 1480 g, and the coupling reaction was carried out at 50°C for 2 hours. After that, 20 g of methanol was added to stop the polymerization reaction, and a solution containing the conjugated diene graft polymer (G'-22) before hydrogenation was obtained.

(步驟(5)) 於含所獲得的共軛二烯系接枝聚合物(G'-22)的溶液中，添加20mL之由辛酸鎳及三甲基鋁所形成的齊格勒系氫化觸媒(0.095mmol/L環己烷溶液)，於氫壓力1MPa、80℃之條件使反應5小時，而獲得含氫化共軛二烯系接枝聚合物(G-22)的溶液。(Step (5)) To the solution containing the obtained conjugated diene graft polymer (G'-22), add 20 mL of a Ziegler hydrogenation catalyst (0.095mmol/L Cyclohexane solution), and reacted for 5 hours under the conditions of a hydrogen pressure of 1 MPa and 80°C to obtain a solution containing a hydrogenated conjugated diene graft polymer (G-22).

(步驟(6)) 藉由將含所獲得的氫化共軛二烯系接枝聚合物(G-22)的溶液水洗而去除上述觸媒，將洗淨結束後之聚合物溶液於70℃真空乾燥24小時後，氫化共軛二烯系接枝聚合物(G-22)為不溶化，凝膠分率為80質量%以上。所獲得的氫化共軛二烯系接枝聚合物(G-22)之重量平均分子量為46,000，Mw/Mn為1.5，苯乙烯所衍生的結構單元含量為0質量%，偶合率為95%，氫化率為99莫耳%，聚合物每1分子之Si原子(分支點)的平均個數為4個，聚合物每一分子的官能基(c)的平均個數為8個，每Si原子(分支點)的官能基(c)的平均個數為2個，聚合物每一分子的側鏈(b)之平均條數為4條，每Si原子(分支點)的側鏈(b)之平均條數為1條(重量平均分子量、Mw/Mn、乙烯基含量、苯乙烯單元含量、聚合物每1分子之Si原子(分支點)的平均個數、聚合物每一分子的官能基(c)的平均個數、每Si原子(分支點)的平均個數，係測定步驟(4)或步驟(5)所獲得的聚合物溶液於常溫、常壓下進行乾燥而獲得的聚合物的值)。將所獲得的氫化共軛二烯系接枝聚合物(G-22)之分子規格、物性示於表4。(Step (6)) The catalyst is removed by washing the solution containing the obtained hydrogenated conjugated diene graft polymer (G-22) with water, and the polymer solution after washing is vacuum dried at 70°C for 24 hours, and then hydrogenated The conjugated diene-based graft polymer (G-22) is insolubilized and has a gel fraction of 80% by mass or more. The weight average molecular weight of the obtained hydrogenated conjugated diene graft polymer (G-22) was 46,000, Mw/Mn was 1.5, the content of styrene-derived structural units was 0% by mass, and the coupling ratio was 95%. The hydrogenation rate is 99 mol%, the average number of Si atoms (branching points) per polymer molecule is 4, and the average number of functional groups (c) per polymer molecule is 8, per Si atom (Branch point) The average number of functional groups (c) is 2, and the average number of side chains (b) per polymer molecule is 4, and the side chains (b) per Si atom (branch point) The average number is 1 (weight average molecular weight, Mw/Mn, vinyl content, styrene unit content, average number of Si atoms (branching points) per polymer molecule, functional groups per polymer molecule The average number of (c) and the average number per Si atom (branch point) are the polymer obtained by drying the polymer solution obtained in step (4) or step (5) at room temperature and pressure Value). Table 4 shows the molecular specifications and physical properties of the obtained hydrogenated conjugated diene graft polymer (G-22).

將於實施例1～15中的步驟(1)～(6)使用的各試藥之種類、量、反應時間示於以下之表1及2，將實施例1～18及比較例1～4所獲得的氫化共軛二烯系接枝聚合物的物性示於表3及4。The types, amounts, and reaction times of the reagents used in steps (1) to (6) in Examples 1 to 15 are shown in Tables 1 and 2 below. Examples 1 to 18 and Comparative Examples 1 to 4 The physical properties of the obtained hydrogenated conjugated diene graft polymer are shown in Tables 3 and 4.

[表1]   實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 步驟(1) 溶劑 環己烷 g 1370 1370 1580 1580 1580 1580 1580 1580 陰離子起始劑 SBL g 240 240 56 56 56 56 18 56 極性化合物 THF g 0 0 11 2.9 11 11 11 11 單體   Bd Bd Bd Bd Bd Bd Bd Bd g 1250 1250 1250 1250 1250 1250 1220 1250 停止劑 甲醇 g 14 14 3.3 3.3 3.3 3.3 1.1 3.3 未改質共軛二烯系聚合物   (F'-1) (F'-2) (F'-3) (F'-4) (F'-5) (F'-6) (F'-7) (F'-8) 步驟(2) 未改質共軛二烯系聚合物   (F'-1) (F'-2) (F'-3) (F'-4) (F'-5) (F'-6) (F'-7) (F'-8) g 460 460 700 700 700 700 700 700 自由基發生劑 t-BPOP g 0.6 0.6 0.9 0.9 0.9 0.9 0.9 0.9 矽烷化合物   MPTES MPTES MPTES MPTES MPTES MPTES MPTES MPTES g 290 290 51 51 51 51 17 51 官能基改質共軛二烯系聚合物   (F-1) (F-2) (F-3) (F-4) (F-5) (F-6) (F-7) (F-8) 稀釋溶劑 環己烷 g 1750 1750 1750 1750 1750 1750 1670 1750 步驟(3) 溶劑 環己烷 g 2270 2330 700 700 700 700 340 1060 陰離子起始劑 SBL g 8.7 8.7 78 78 78 78 37 55 極性化合物 THF g 0 0 7.0 7.0 4.3 7.0 3.4 10 單體   Ip Bd/Ip =50/50 (質量) Bd Bd Bd Bd Bd Bd g 570 500 340 340 340 340 340 480 活性末端聚合物   (I-1) (I-2) (I-3) (I-4) (I-5) (I-6) (I-7) (I-8) 步驟(4) 路易士鹼 THF g 0.7 0.7 0 0 0 0 0 0 官能基改質共軛二烯系聚合物之 稀釋溶液   (F-1) (F-2) (F-3) (F-4) (F-5) (F-6) (F-7) (F-8) g 20 20 1480 1480 1480 1480 1970 1060 不活性化試藥 SBL g 26 26 190 190 190 65 94 140 停止劑 甲醇 g 1.0 1.0 21 21 21 7.0 10 15 步驟(5) 氫化觸媒 mL 100 100 100 100 100 100 100 100 反應時間 h 5 5 5 5 5 5 5 5 步驟(6) 氫化共軛二烯系接枝聚合物   (G-1) (G-2) (G-3) (G-4) (G-5) (G-6) (G-7) (G-8) [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 step 1) Solvent Cyclohexane g 1370 1370 1580 1580 1580 1580 1580 1580 Anionic initiator SBL g 240 240 56 56 56 56 18 56 Polar compound THF g 0 0 11 2.9 11 11 11 11 monomer Bd Bd Bd Bd Bd Bd Bd Bd g 1250 1250 1250 1250 1250 1250 1220 1250 Stopping agent Methanol g 14 14 3.3 3.3 3.3 3.3 1.1 3.3 Unmodified conjugated diene polymer (F'-1) (F'-2) (F'-3) (F'-4) (F'-5) (F'-6) (F'-7) (F'-8) Step (2) Unmodified conjugated diene polymer (F'-1) (F'-2) (F'-3) (F'-4) (F'-5) (F'-6) (F'-7) (F'-8) g 460 460 700 700 700 700 700 700 Free radical generator t-BPOP g 0.6 0.6 0.9 0.9 0.9 0.9 0.9 0.9 Silane compounds MPTES MPTES MPTES MPTES MPTES MPTES MPTES MPTES g 290 290 51 51 51 51 17 51 Functional group modified conjugated diene polymer (F-1) (F-2) (F-3) (F-4) (F-5) (F-6) (F-7) (F-8) Dilution solvent Cyclohexane g 1750 1750 1750 1750 1750 1750 1670 1750 Step (3) Solvent Cyclohexane g 2270 2330 700 700 700 700 340 1060 Anionic initiator SBL g 8.7 8.7 78 78 78 78 37 55 Polar compound THF g 0 0 7.0 7.0 4.3 7.0 3.4 10 monomer Ip Bd/Ip =50/50 (quality) Bd Bd Bd Bd Bd Bd g 570 500 340 340 340 340 340 480 Living end polymer (I-1) (I-2) (I-3) (I-4) (I-5) (I-6) (I-7) (I-8) Step (4) Lewisine THF g 0.7 0.7 0 0 0 0 0 0 Functional group modified dilute solution of conjugated diene polymer (F-1) (F-2) (F-3) (F-4) (F-5) (F-6) (F-7) (F-8) g 20 20 1480 1480 1480 1480 1970 1060 Inactivation reagent SBL g 26 26 190 190 190 65 94 140 Stopping agent Methanol g 1.0 1.0 twenty one twenty one twenty one 7.0 10 15 Step (5) Hydrogenation catalyst mL 100 100 100 100 100 100 100 100 Reaction time h 5 5 5 5 5 5 5 5 Step (6) Hydrogenated conjugated diene graft polymer (G-1) (G-2) (G-3) (G-4) (G-5) (G-6) (G-7) (G-8)

[表2]   實施例9 實施例10 實施例11 實施例12 實施例13 實施例14 實施例15 步驟(1) 溶劑 環己烷 g 1580 1580 1580 1580 1580 1580 1580 陰離子起始劑 SBL g 56 56 56 56 56 56 56 極性化合物 THF g 11 11 11 11 11 11 11 單體   Bd Bd Bd Bd/Ip =50/50 (質量) Bd Bd Bd g 1250 1250 1250 1410 1250 1250 1250 停止劑 甲醇 g 3.3 3.3 3.3 3.3 3.3 3.3 3.3 未改質共軛二烯系聚合物   (F'-9) (F'-10) (F'-11) (F'-12) (F'-13) (F'-14) (F'-15) 步驟(2) 未改質共軛二烯系聚合物   (F'-9) (F'-10) (F'-11) (F'-12) (F'-13) (F'-14) (F'-15) g 700 700 700 700 700 700 700 自由基發生劑 t-BPOP g 0.9 0.9 0.9 0.9 0.9 0.9 0.9 矽烷化合物   MPTES MPTES MPTES MPTES MPTES MPTES MPTMS g 51 100 51 51 51 51 42 官能基改質共軛二烯系聚合物   (F-9) (F-10) (F-11) (F-12) (F-13) (F-14) (F-15) 稀釋溶劑 環己烷 g 1750 1870 1750 1750 1750 1750 1750 步驟(3) 溶劑 環己烷 g 1350 990 700 700 700 700 700 陰離子起始劑 SBL g 34 110 78 78 78 78 78 極性化合物 THF g 12 9.8 7.0 7.0 7.0 7.0 7.0 單體   Bd Bd Bd Bd Bd/Ip =50/50 (質量) Bd/St =50/50 (質量) Bd g 600 470 340 340 380 450 340 活性末端聚合物   (I-9) (I-10) (I-11) (I-12) (I-13) (I-14) (I-15) 步驟(4) 路易士鹼 THF g 0 0 0 0 0 0 0 官能基改質共軛二烯系聚合物之 稀釋溶液   (F-9) (F-10) (F-11) (F-12) (F-13) (F-14) (F-15) g 660 1040 1480 1480 1480 1480 1480 不活性化試藥 SBL g 86 140 190 190 190 190 190 停止劑 甲醇 g 9.2 15 21 21 21 21 21 步驟(5) 氫化觸媒 mL 100 100 100 100 100 100 100 反應時間 h 5 5 2 5 5 5 5 步驟(6) 氫化共軛二烯系接枝聚合物   (G-9) (G-10) (G-11) (G-12) (G-13) (G-14) (G-15) [Table 2] Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 step 1) Solvent Cyclohexane g 1580 1580 1580 1580 1580 1580 1580 Anionic initiator SBL g 56 56 56 56 56 56 56 Polar compound THF g 11 11 11 11 11 11 11 monomer Bd Bd Bd Bd/Ip =50/50 (quality) Bd Bd Bd g 1250 1250 1250 1410 1250 1250 1250 Stopping agent Methanol g 3.3 3.3 3.3 3.3 3.3 3.3 3.3 Unmodified conjugated diene polymer (F'-9) (F'-10) (F'-11) (F'-12) (F'-13) (F'-14) (F'-15) Step (2) Unmodified conjugated diene polymer (F'-9) (F'-10) (F'-11) (F'-12) (F'-13) (F'-14) (F'-15) g 700 700 700 700 700 700 700 Free radical generator t-BPOP g 0.9 0.9 0.9 0.9 0.9 0.9 0.9 Silane compounds MPTES MPTES MPTES MPTES MPTES MPTES MPTMS g 51 100 51 51 51 51 42 Functional group modified conjugated diene polymer (F-9) (F-10) (F-11) (F-12) (F-13) (F-14) (F-15) Dilution solvent Cyclohexane g 1750 1870 1750 1750 1750 1750 1750 Step (3) Solvent Cyclohexane g 1350 990 700 700 700 700 700 Anionic initiator SBL g 34 110 78 78 78 78 78 Polar compound THF g 12 9.8 7.0 7.0 7.0 7.0 7.0 monomer Bd Bd Bd Bd Bd/Ip =50/50 (quality) Bd/St =50/50 (quality) Bd g 600 470 340 340 380 450 340 Living end polymer (I-9) (I-10) (I-11) (I-12) (I-13) (I-14) (I-15) Step (4) Lewisine THF g 0 0 0 0 0 0 0 Functional group modified dilute solution of conjugated diene polymer (F-9) (F-10) (F-11) (F-12) (F-13) (F-14) (F-15) g 660 1040 1480 1480 1480 1480 1480 Inactivation reagent SBL g 86 140 190 190 190 190 190 Stopping agent Methanol g 9.2 15 twenty one twenty one twenty one twenty one twenty one Step (5) Hydrogenation catalyst mL 100 100 100 100 100 100 100 Reaction time h 5 5 2 5 5 5 5 Step (6) Hydrogenated conjugated diene graft polymer (G-9) (G-10) (G-11) (G-12) (G-13) (G-14) (G-15)

表1及2中，縮寫各自表示下述 SBL：二級丁基鋰 THF：四氫呋喃 t-BPOP：過氧異丁酸三級丁酯 Bd：丁二烯 Ip：異戊二烯 St：苯乙烯 MPTES：(3-巰基丙基)三乙氧基矽烷 MPTMS：(3-巰基丙基)三甲氧基矽烷In Tables 1 and 2, the abbreviations respectively indicate the following SBL: Secondary Butyl Lithium THF: Tetrahydrofuran t-BPOP: tertiary butyl peroxyisobutyrate Bd: Butadiene Ip: isoprene St: Styrene MPTES: (3-mercaptopropyl) triethoxysilane MPTMS: (3-mercaptopropyl) trimethoxysilane

[表3]     實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例10 實施例11 氫化共軛二烯系接枝聚合物(G)   G-1 G-2 G-3 G-4 G-5 G-6 G-7 G-8 G-9 G-10 G-11 偶合 條件 官能基改質共軛二烯系聚合物(F)   F-1 F-2 F-3 F-4 F-5 F-6 F-7 F-8 F-9 F-10 F-11 官能基(c)   乙氧基矽基 乙氧基矽基 乙氧基矽基 乙氧基矽基 乙氧基矽基 乙氧基矽基 乙氧基矽基 乙氧基矽基 乙氧基矽基 乙氧基矽基 乙氧基矽基 活性末端聚合物(I)/官能基改質 共軛二烯系聚合物(F) 莫耳比 8 8 4 4 4 4 4 4 4 8 4 結構 主鏈(a) 組成   Bd Bd Bd Bd Bd Bd Bd Bd Bd Bd Bd 重量平均分子量(Mw)   6,000 6,000 26,000 26,000 26,000 26,000 78,000 26,000 26,000 26,000 26,000 乙烯基含量 莫耳% 10 10 50 30 50 50 50 50 50 50 50 側鏈(b) 組成   Ip Bd/Ip Bd Bd Bd Bd Bd Bd Bd Bd Bd 重量平均分子量(Mw)   60,000 60,000 5,000 5,000 5,000 5,000 5,000 10,000 20,000 5,000 5,000 乙烯基含量 莫耳% 10 10 50 50 30 50 50 50 50 50 50 氫化共軛二烯系 接枝聚合物(G) 重量平均分子量(Mw)   486,000 486,000 46,000 46,000 46,000 46,000 98,000 66,000 106,000 66,000 46,000 Mw/Mn   1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 苯乙烯所衍生的 結構單元之含量 質量% 0 0 0 0 0 0 0 0 0 0 0 偶合率 % 95 95 95 95 95 95 95 95 95 95 95 氫化率 莫耳% 99 99 99 99 99 99 99 99 99 99 60 為分支點的雜原子   Si Si Si Si Si Si Si Si Si Si Si 聚合物每1分子之 分支點的平均個數(Y)   8 8 4 4 4 4 4 4 4 8 4 聚合物每1分子之 官能基(c)的平均個數(X)   0.8 0.8 0.4 0.4 0.4 2 0.4 0.4 0.4 0.8 0.4 每分支點的 官能基(c)的平均個數(X/Y)   0.1 0.1 0.1 0.1 0.1 0.5 0.1 0.1 0.1 0.1 0.1 聚合物每1分子之 側鏈(b)之平均條數(W)   8 8 4 4 4 4 4 4 4 8 4 每分支點的 側鏈(b)之平均條數(W/Y)   1 1 1 1 1 1 1 1 1 1 1 氯的含量 ppm 3 - - - - - - - - - - 物性 安定性   A A A A A A A A A A A 縮合反應性   A A A A A A A A A A A 透明性   A A A A A A A A A A A 耐熱性 100℃、12h   A A A A A A A A A A A 120℃、12h   A A A A A A A A A A A [table 3] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Hydrogenated conjugated diene graft polymer (G) G-1 G-2 G-3 G-4 G-5 G-6 G-7 G-8 G-9 G-10 G-11 Coupling conditions Functional group modified conjugated diene polymer (F) F-1 F-2 F-3 F-4 F-5 F-6 F-7 F-8 F-9 F-10 F-11 Functional group (c) Ethoxysilyl Ethoxysilyl Ethoxysilyl Ethoxysilyl Ethoxysilyl Ethoxysilyl Ethoxysilyl Ethoxysilyl Ethoxysilyl Ethoxysilyl Ethoxysilyl Living terminal polymer (I)/functional group-modified conjugated diene polymer (F) Molby 8 8 4 4 4 4 4 4 4 8 4 structure Main chain (a) composition Bd Bd Bd Bd Bd Bd Bd Bd Bd Bd Bd Weight average molecular weight (Mw) 6,000 6,000 26,000 26,000 26,000 26,000 78,000 26,000 26,000 26,000 26,000 Vinyl content Mole% 10 10 50 30 50 50 50 50 50 50 50 Side chain (b) composition Ip Bd/Ip Bd Bd Bd Bd Bd Bd Bd Bd Bd Weight average molecular weight (Mw) 60,000 60,000 5,000 5,000 5,000 5,000 5,000 10,000 20,000 5,000 5,000 Vinyl content Mole% 10 10 50 50 30 50 50 50 50 50 50 Hydrogenated conjugated diene graft polymer (G) Weight average molecular weight (Mw) 486,000 486,000 46,000 46,000 46,000 46,000 98,000 66,000 106,000 66,000 46,000 Mw/Mn 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 The content of structural units derived from styrene quality% 0 0 0 0 0 0 0 0 0 0 0 Coupling rate % 95 95 95 95 95 95 95 95 95 95 95 Hydrogenation rate Mole% 99 99 99 99 99 99 99 99 99 99 60 Heteroatom Si Si Si Si Si Si Si Si Si Si Si Average number of branch points per molecule of polymer (Y) 8 8 4 4 4 4 4 4 4 8 4 Average number of functional groups (c) per molecule of polymer (X) 0.8 0.8 0.4 0.4 0.4 2 0.4 0.4 0.4 0.8 0.4 Average number of functional groups (c) per branch point (X/Y) 0.1 0.1 0.1 0.1 0.1 0.5 0.1 0.1 0.1 0.1 0.1 Average number of side chains (b) per molecule of polymer (W) 8 8 4 4 4 4 4 4 4 8 4 Average number of side chains (b) per branch point (W/Y) 1 1 1 1 1 1 1 1 1 1 1 Chlorine content ppm 3 - - - - - - - - - - Physical properties Stability A A A A A A A A A A A Condensation reactivity A A A A A A A A A A A Transparency A A A A A A A A A A A Heat resistance 100°C, 12h A A A A A A A A A A A 120°C, 12h A A A A A A A A A A A

[表4]     實施例12 實施例13 實施例14 實施例15 實施例16 實施例17 實施例18 比較例1 比較例2 比較例3 比較例4 氫化共軛二烯系接枝聚合物(G)   G-12 G-13 G-14 G-15 G-16 G-17 G-18 G-19 G-20 G-21 G-22 偶合 條件 官能基改質共軛二烯系聚合物(F)   F-12 F-13 F-14 F-15 F-16 F-17 F-18 F-19 F-20 F-21 F-22 官能基(c)   乙氧基矽基 乙氧基矽基 乙氧基矽基 甲氧基矽基 乙氧基矽基 乙氧基矽基 硼酸酯基 矽氯基 矽氯基 乙氧基矽基 乙氧基矽基 活性末端聚合物(I)/官能基改質 共軛二烯系聚合物(F) 莫耳比 4 4 4 4 8 4 4 8 4 8 4 結構 主鏈(a) 組成   Bd/Ip Bd Bd Bd Bd Bd Bd Bd Bd Bd Bd 重量平均分子量(Mw)   26,000 26,000 26,000 26,000 6,000 26,000 26,000 6,000 26,000 6,000 26,000 乙烯基含量 莫耳% 50 50 50 50 10 50 50 10 50 10 50 側鏈(b) 組成   Bd Bd/Ip Bd/St Bd Ip Bd Bd Ip Bd Ip Bd 重量平均分子量(Mw)   5,000 5,000 5,000 5,000 60,000 5,000 5,000 60,000 5,000 60,000 5,000 乙烯基含量 莫耳% 50 50 50 50 10 50 50 10 50 10 50 氫化共軛二烯系 接枝聚合物(G) 重量平均分子量(Mw)   46,000 46,000 46,000 46,000 486,000 46,000 46,000 486,000 46,000 486,000 46,000 Mw/Mn   1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 苯乙烯所衍生的 結構單元之含量 質量% 0 0 25 0 0 0 0 0 0 0 0 偶合率 % 95 95 95 95 95 95 95 95 95 95 95 氫化率 莫耳% 99 99 99 99 99 99 99 99 99 99 99 為分支點的雜原子   Si Si Si Si Si Si B Si Si Si Si 聚合物每1分子之 分支點的平均個數(Y)   4 4 4 4 8 4 4 8 4 8 4 聚合物每1分子之 官能基(c)的平均個數(X)   0.4 0.4 0.4 0.4 0.8 0.4 0.4 0 0 16 8 每分支點的 官能基(c)的平均個數(X/Y)   0.1 0.1 0.1 0.1 0.1 0.1 0.1 0 0 2 2 聚合物每1分子之 側鏈(b)之平均條數(W)   4 4 4 4 8 4 4 8 4 8 4 每分支點的 側鏈(b)之平均條數(W/Y)   1 1 1 1 1 1 1 1 1 1 1 氯的含量 ppm - - - - - - - 500 9000 - - 物性 安定性   A A A A A A A A A B B 縮合反應性   A A A A A A A B B 無法評價 無法評價 透明性   A A A A A A A A B 無法評價 無法評價 耐熱性 100℃、12h   A A A A A A A A B 無法評價 無法評價 120℃、12h   A A A A A A A A B 無法評價 無法評價 [Table 4] Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Hydrogenated conjugated diene graft polymer (G) G-12 G-13 G-14 G-15 G-16 G-17 G-18 G-19 G-20 G-21 G-22 Coupling conditions Functional group modified conjugated diene polymer (F) F-12 F-13 F-14 F-15 F-16 F-17 F-18 F-19 F-20 F-21 F-22 Functional group (c) Ethoxysilyl Ethoxysilyl Ethoxysilyl Methoxysilyl Ethoxysilyl Ethoxysilyl Boronate group Silyl Chloride Silyl Chloride Ethoxysilyl Ethoxysilyl Living terminal polymer (I)/functional group-modified conjugated diene polymer (F) Molby 4 4 4 4 8 4 4 8 4 8 4 structure Main chain (a) composition Bd/Ip Bd Bd Bd Bd Bd Bd Bd Bd Bd Bd Weight average molecular weight (Mw) 26,000 26,000 26,000 26,000 6,000 26,000 26,000 6,000 26,000 6,000 26,000 Vinyl content Mole% 50 50 50 50 10 50 50 10 50 10 50 Side chain (b) composition Bd Bd/Ip Bd/St Bd Ip Bd Bd Ip Bd Ip Bd Weight average molecular weight (Mw) 5,000 5,000 5,000 5,000 60,000 5,000 5,000 60,000 5,000 60,000 5,000 Vinyl content Mole% 50 50 50 50 10 50 50 10 50 10 50 Hydrogenated conjugated diene graft polymer (G) Weight average molecular weight (Mw) 46,000 46,000 46,000 46,000 486,000 46,000 46,000 486,000 46,000 486,000 46,000 Mw/Mn 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 The content of structural units derived from styrene quality% 0 0 25 0 0 0 0 0 0 0 0 Coupling rate % 95 95 95 95 95 95 95 95 95 95 95 Hydrogenation rate Mole% 99 99 99 99 99 99 99 99 99 99 99 Heteroatom Si Si Si Si Si Si B Si Si Si Si Average number of branch points per molecule of polymer (Y) 4 4 4 4 8 4 4 8 4 8 4 Average number of functional groups (c) per molecule of polymer (X) 0.4 0.4 0.4 0.4 0.8 0.4 0.4 0 0 16 8 Average number of functional groups (c) per branch point (X/Y) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0 0 2 2 Average number of side chains (b) per molecule of polymer (W) 4 4 4 4 8 4 4 8 4 8 4 Average number of side chains (b) per branch point (W/Y) 1 1 1 1 1 1 1 1 1 1 1 Chlorine content ppm - - - - - - - 500 9000 - - Physical properties Stability A A A A A A A A A B B Condensation reactivity A A A A A A A B B Can't evaluate Can't evaluate Transparency A A A A A A A A B Can't evaluate Can't evaluate Heat resistance 100°C, 12h A A A A A A A A B Can't evaluate Can't evaluate 120°C, 12h A A A A A A A A B Can't evaluate Can't evaluate

由表3及4可知，每Si原子(分支點)的官能基(c)的平均個數(X/Y)為0＜(X/Y)＜1之範圍的實施例1～18之氫化共軛二烯系接枝聚合物，因縮合反應性高，與極性材料的親和性優異。再者，得知於將包含氫化共軛二烯系接枝聚合物的洗淨結束後之聚合物溶液進行乾燥的步驟中，因不溶分的比率小，具有高安定性。 另一方面，每Si原子(分支點)的官能基(c)的平均個數(X/Y)為0的比較例1及比較例2之氫化共軛二烯系接枝聚合物，因縮合反應性低，與極性材料的親和性差。又，每Si原子(分支點)的官能基(c)的平均個數(X/Y)大於1(1＜(X/Y))範圍的比較例3及比較例4之氫化共軛二烯系接枝聚合物，於將聚合物溶液乾燥的步驟中不溶分的比率高且取出有困難。 [產業上利用之可能性]It can be seen from Tables 3 and 4 that the average number (X/Y) of functional groups (c) per Si atom (branch point) is in the range of 0<(X/Y)<1 for the hydrogenation of Examples 1-18 The conjugated diene graft polymer has high condensation reactivity and excellent affinity with polar materials. Furthermore, it is known that in the step of drying the polymer solution containing the hydrogenated conjugated diene graft polymer after washing, the ratio of insoluble matter is small and the stability is high. On the other hand, the hydrogenated conjugated diene graft polymer of Comparative Example 1 and Comparative Example 2 in which the average number (X/Y) of functional groups (c) per Si atom (branch point) is 0, due to condensation Low reactivity, poor affinity with polar materials. In addition, the hydrogenated conjugated diene of Comparative Example 3 and Comparative Example 4 in which the average number (X/Y) of functional groups (c) per Si atom (branch point) is greater than 1 (1<(X/Y)) The graft polymer has a high ratio of insolubles in the step of drying the polymer solution and it is difficult to take out. [Possibility of Industrial Use]

本發明之氫化共軛二烯系接枝聚合物，因與極性材料的親和性優異的同時，具有高安定性，可有效使用於汽車用內外配件砸電氣・電子構件、包裝材料、運動用品、日用雜貨、層壓材料、伸縮材料、各種橡膠製品、醫療用品、各種接著劑、各種塗裝底漆等廣泛領域。The hydrogenated conjugated diene-based graft polymer of the present invention has excellent affinity with polar materials and high stability. It can be effectively used for automotive interior and exterior parts to smash electrical and electronic components, packaging materials, sports goods, Daily miscellaneous goods, laminated materials, stretch materials, various rubber products, medical supplies, various adhesives, various coating primers, and other broad fields.

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Claims (12)

一種氫化共軛二烯系接枝聚合物， 其係如下氫化共軛二烯系接枝聚合物： 由包含共軛二烯所衍生的結構單元的聚合物所構成的主鏈(a)，通過為分支點的價數為3以上之1個雜原子，與側鏈(b)結合，該側鏈(b)係由包含選自包含共軛二烯及芳香族乙烯化合物的群組的至少1個單體所衍生的結構單元的聚合物所構成；該接枝聚合物所含的共軛二烯所衍生的結構單元中所含的碳-碳雙鍵之至少一部分經氫化；其中， 該主鏈(a)直接或通過連結鏈與分支點結合， 該側鏈(b)直接與分支點結合， 該雜原子為選自包含Si、Sn、Ge、Pb、P、B、及Al的群組的至少1者， 該分支點之至少1者與選自包含烷氧基及羥基的群組的至少1個官能基(c)直接結合， 氫化共軛二烯系接枝聚合物每1分子之與該分支點直接結合的官能基(c)的平均個數X與氫化共軛二烯系接枝聚合物每1分子之分支點的平均個數Y滿足下述式(2)之關係： 0＜(X/Y)＜1  (2)。A hydrogenated conjugated diene graft polymer, It is the following hydrogenated conjugated diene graft polymer: The main chain (a) composed of a polymer containing a structural unit derived from a conjugated diene is bonded to the side chain (b) through a heteroatom with a valence of 3 or more as a branch point, and the side chain (b) It is composed of a polymer containing a structural unit derived from at least one monomer selected from the group consisting of a conjugated diene and an aromatic vinyl compound; the conjugated diene contained in the graft polymer At least a part of the carbon-carbon double bond contained in the derived structural unit is hydrogenated; wherein, The main chain (a) is connected to the branch point directly or through a linking chain, The side chain (b) is directly combined with the branch point, The heteroatom is at least one member selected from the group consisting of Si, Sn, Ge, Pb, P, B, and Al, At least one of the branch points is directly bonded to at least one functional group (c) selected from the group containing an alkoxy group and a hydroxyl group, The average number of functional groups (c) per molecule of the hydrogenated conjugated diene graft polymer directly bonded to the branch point X and the average number of branch points per molecule of the hydrogenated conjugated diene graft polymer The number Y satisfies the relationship of the following formula (2): 0＜(X/Y)＜1 (2). 如請求項1之氫化共軛二烯系接枝聚合物，其中鹵素含量為1000ppm以下。The hydrogenated conjugated diene graft polymer of claim 1, wherein the halogen content is 1000 ppm or less. 如請求項1或2之氫化共軛二烯系接枝聚合物，其中氫化共軛二烯系接枝聚合物每1分子之與該分支點直接結合的官能基(c)的平均個數X滿足下述式(3)之關係： 0＜X≦10  (3)。The hydrogenated conjugated diene graft polymer of claim 1 or 2, wherein the average number of functional groups (c) directly bonded to the branch point per molecule of the hydrogenated conjugated diene graft polymer X Satisfy the relationship of the following formula (3): 0＜X≦10 (3). 如請求項1至3中任一項之氫化共軛二烯系接枝聚合物，其中該雜原子為Si。The hydrogenated conjugated diene graft polymer according to any one of claims 1 to 3, wherein the heteroatom is Si. 如請求項1至4中任一項之氫化共軛二烯系接枝聚合物，其中氫化共軛二烯系接枝聚合物每1分子之與該分支點直接結合的側鏈(b)之平均條數W與氫化共軛二烯系接枝聚合物每1分子之分支點的平均個數Y滿足下述式(4)之關係： 0.5≦(W/Y)  (4)。The hydrogenated conjugated diene graft polymer according to any one of claims 1 to 4, wherein per molecule of the hydrogenated conjugated diene graft polymer is one molecule of the side chain (b) directly bonded to the branch point The average number W and the average number Y of branch points per molecule of the hydrogenated conjugated diene graft polymer satisfy the relationship of the following formula (4): 0.5≦(W/Y) (4). 一種如請求項1至5中任一項之氫化共軛二烯系接枝聚合物之製造方法，其包含： (A-1)使下述式(I)所表示的活性末端聚合物、與具有包含下述式(II)所示的官能基的部分作為分支鏈的官能基改質共軛二烯系聚合物反應，而製作共軛二烯系接枝聚合物的步驟， P-X  (I) (式(I)中，P表示包含選自包含共軛二烯及芳香族乙烯化合物的群組的至少1個單體所衍生的結構單元的聚合物鏈，X表示陰離子聚合之活性末端)，
Figure 03_image017
(式(II)中，V表示烷氧基或羥基，Z為Si、Sn、Ge、Pb、P、B、或Al，R1 表示碳數6～12之芳基、碳數1～12之烷基、或氫原子，N表示該Z之價數，n為滿足下述式(5)的整數， 1≦n≦N-1  (5) n為2以上的情形，V可為相同亦可為相異，N-n為2以上的情形，R1 可為相同亦可為相異，對於主鏈，分支鏈含有複數個的情形，Z可為相同亦可為相異)；及 (B)將上述共軛二烯系接枝聚合物所含的至少一部分之共軛二烯所衍生的結構單元中所含的碳-碳雙鍵進行氫化而形成氫化共軛二烯系接枝聚合物的步驟；及 (C)回收所獲得的氫化共軛二烯系接枝聚合物的步驟。A method for producing a hydrogenated conjugated diene graft polymer according to any one of claims 1 to 5, which comprises: (A-1) a living terminal polymer represented by the following formula (I), and A step of modifying a conjugated diene-based polymer by reacting with a functional group containing a functional group represented by the following formula (II) as a branched functional group to produce a conjugated diene-based graft polymer, PX (I) (In formula (I), P represents a polymer chain containing a structural unit derived from at least one monomer selected from the group consisting of a conjugated diene and an aromatic vinyl compound, and X represents an anionic polymerization active end),
Figure 03_image017
(In formula (II), V represents an alkoxy group or a hydroxyl group, Z represents Si, Sn, Ge, Pb, P, B, or Al, and R 1 represents an aryl group with 6 to 12 carbons, and a group with 1 to 12 carbons. Alkyl group or hydrogen atom, N represents the valence of the Z, n is an integer satisfying the following formula (5), 1≦n≦N-1 (5) When n is 2 or more, V may be the same Is different, when Nn is 2 or more, R 1 may be the same or different, for the main chain, the branch chain contains a plurality of cases, Z may be the same or different); and (B) The step of hydrogenating the carbon-carbon double bonds contained in the structural unit derived from at least a part of the conjugated diene contained in the above-mentioned conjugated diene graft polymer to form a hydrogenated conjugated diene graft polymer And (C) the step of recovering the obtained hydrogenated conjugated diene graft polymer. 如請求項6之氫化共軛二烯系接枝聚合物之製造方法，其於步驟(A-1)之後且於步驟(C)之前，進一步包含： (A-2)將該共軛二烯系接枝聚合物或氫化共軛二烯系接枝聚合物中之選自包含烷氧基及羥基的群組的至少1個殘存的官能基之一部分進行不活性化的步驟。The method for producing a hydrogenated conjugated diene graft polymer according to claim 6, after step (A-1) and before step (C), further comprises: (A-2) Part of at least one remaining functional group selected from the group consisting of an alkoxy group and a hydroxyl group in the conjugated diene graft polymer or hydrogenated conjugated diene graft polymer Perform the inactivation step. 如請求項6或7之氫化共軛二烯系接枝聚合物之製造方法，其中該式(II)中之Z為Si。The method for producing a hydrogenated conjugated diene graft polymer according to claim 6 or 7, wherein Z in the formula (II) is Si. 如請求項6至8中任一項之氫化共軛二烯系接枝聚合物之製造方法，其中該式(II)中之官能基V為烷氧基。The method for producing a hydrogenated conjugated diene graft polymer according to any one of claims 6 to 8, wherein the functional group V in the formula (II) is an alkoxy group. 如請求項1至5中任一項之氫化共軛二烯系接枝聚合物，其係利用如請求項6至9中任一項之製造方法而獲得。The hydrogenated conjugated diene graft polymer according to any one of claims 1 to 5 is obtained by the production method according to any one of claims 6 to 9. 一種聚合物組成物，其含有如請求項1至5及10中任一項之氫化共軛二烯系接枝聚合物。A polymer composition containing the hydrogenated conjugated diene graft polymer according to any one of claims 1 to 5 and 10. 一種成形品，其係將如請求項11之聚合物組成物成形而成。A molded product formed by molding the polymer composition of claim 11.
TW109146147A 2019-12-26 2020-12-25 Hydrogenated conjugated diene graft polymer and method for producing same TW202134303A (en)

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