TW474953B

TW474953B - Process for hydrogenating conjugated diene polymer

Info

Publication number: TW474953B
Application number: TW086114780A
Authority: TW
Inventors: Koichi Miyamoto; Yuichi Kitagawa; Shigeru Sasaki
Original assignee: Asahi Chemical Ind
Priority date: 1996-04-16
Filing date: 1997-10-08
Publication date: 2002-02-01

Abstract

A process for hydrogenating a conjugated diene polymer, which process comprises the steps of: deactivating a conjugated diene polymer which is prepared by using an organic alkali metal compound as a polymerization initiator by adding a deactivator; and contacting the deactivated diene polymer with hydrogen in an inert hydrocarbon solvent to hydrogenate the double bond of the deactivated diene polymer, wherein the hydrogenation is carried out (i) in the presence of a catalyst selected from organometallic compounds represented by the following formula: wherein the symbols are defined in the specification and (ii) under a condition satisfying the following relationship: -6 < (M-Z+Al-Ti)/Ti < 2, wherein M represents the molar amount of the organic alkali metal compound; Z represents the molar amount of the deactivator; Al represents the molar amount of an organoaluminum compound; and Ti represents the molar amount of an organotitanium compound.

Description

474953 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明I ) 發明領域本發明有關一種氫化共軛二烯雙鍵之方法，其包括於惰性有機溶劑下使一種使炤有機鹼金屬化合物作爲聚合引發劑製備之共軛二烯聚合物與氫接觸。發明背景因不飽和雙鍵之故，具有烯烴不飽和雙鍵之聚合物有利於硫化，但是該雙鍵亦造成其對於熱與氧化之安定性差。此等聚合.物之不佳安定性可經由氫化去除聚合物中之不飽和雙鍵而明顯改善之。然而，與低分子量化合物相較，因該反應系統粘度、該聚合物鏈受阻因素之故，聚合物較不易氫化。此外，氫化完成之後，極難實質去除所使用之觸媒。完全分離該觸媒尤其不可能。因此，爲達成具有經濟優點之氫化作用，已迫切需要發展一種氫化用之觸媒，其於不需去除之低量下顯示充分活性，或者一種容易去除之觸媒。此外，假如氫化聚合物中殘留大量鹼金屬，該聚合物之耐候化變色特性會變差。本發明之發明者先前提出發現一種使用特定鈦五圜化合物與烷基鋰組合物氫化烯烴之方法（J P - A — 6 1 — 331 3 2與】卩一八一1一53851，本文所用之" JP - A -”一辭意指“未審査公告日本專利申請案”），一種使用金屬錯合物化合物、有機鋁化合物、鋅與鎂組合物氫化烯烴不飽和（共）聚合物之方法（J P — A - 6 1 -28507 與 JP-A - 62 — 209103)以及一種本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）訂 (請先閲讀背面之注意事項再填寫本頁)474953 Printed by A7 B7, Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs 5. Description of the Invention I) Field of the Invention The present invention relates to a method for hydrogenating a conjugated diene double bond, which comprises using an organic alkali metal compound in an inert organic solvent The conjugated diene polymer prepared as a polymerization initiator is contacted with hydrogen. BACKGROUND OF THE INVENTION Due to unsaturated double bonds, polymers having olefinically unsaturated double bonds are advantageous for vulcanization, but the double bonds also cause poor stability to heat and oxidation. The poor stability of these polymers can be significantly improved by hydrogenation to remove unsaturated double bonds in the polymer. However, compared to low molecular weight compounds, polymers are less prone to hydrogenation due to the viscosity of the reaction system and the hindered factors of the polymer chain. In addition, after the hydrogenation is completed, it is extremely difficult to substantially remove the catalyst used. It is particularly impossible to completely separate the catalyst. Therefore, in order to achieve hydrogenation with economic advantages, it has been urgently needed to develop a catalyst for hydrogenation, which exhibits sufficient activity at a low amount that does not need to be removed, or an easily removable catalyst. In addition, if a large amount of alkali metal remains in the hydrogenated polymer, the weatherability and discoloration characteristics of the polymer will be deteriorated. The inventor of the present invention previously proposed to find a method for hydrogenating olefins using a specific titanium pentafluorene compound and an alkyllithium composition (JP-A — 6 1 — 331 3 2 and] 八 181-153851, as used herein " JP-A-"means" Unexamined Japanese Patent Application Publication "), a method for hydrogenating olefin unsaturated (co) polymers using metal complex compounds, organoaluminum compounds, zinc and magnesium compositions ( JP — A-6 1 -28507 and JP-A-62 — 209103) and a paper size applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back before filling this page)

474953 經濟部中央標準局員工消費合作社印裝 A7 _____B7__五、發明説明j ) 使用特定鈦五圜化合物與烷基鋰組合物氫化含烯烴不飽和基之新鮮聚合物（living p〇lymer )之方法。然而，此等觸媒系統於高度活性時難以處理，而且長時間保存之貯存安定性不足。此外，此等系統需要還原劑（有機金屬）以將鈦五圜化合物還原成低價數化合物，該氫化活性視還原劑對該鈦五圜化合物之莫耳比率與接觸條件而定，此亦使該觸媒系統難以處理。使用於泰比（Tebbe’s )試劑（鈦五圜化合物與三甲基鋁之金屬環化合物）與烷基金屬化合物間之反應產物氫化含烯烴不飽和雙鍵聚合物之雙鍵係已知（美國專利5，2 44，980)。此方法中，其缺點係必須使用大量烷基鹼金屬化合物作爲共觸媒，以達到高氫化活性。此外，因爲此方法所使用觸媒之活性差，需要使用大量之觸媒。發明摘要本發明目的係提出用以氫化共軛二烯聚合物雙鍵之工業有利方法，其包括使共軛二烯聚合物與一種惰性有機溶劑接觸，該共軛二烯係使用一種有機鹼金屬化合物作爲聚合引發劑製備，該方法中，用以氫化之觸媒安定而易於處理，不需要鹼金屬化合物作爲共觸媒，所需之觸媒用量極少，而且該氫化作用定量進行，在廣泛溫度範圍內具有良好之結果重現性。由下列描述可明瞭本發明之其他目的與效果。已藉由提出· (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210Χ297公釐） -5 - 474953 A7 B7 五、發明説明3() (1 ) 一種氫化共軛二烯聚合物之方法，其包括步驟添加鈍化劑鈍化該共軛二烯聚合物，該聚合物係使用一種有機鹼金屬化合物作爲聚合引發劑製備；及於惰性烴溶劑中使該鈍化二烯聚合物與氫接觸，以氫化該經鈍化二烯聚合物之雙鍵，其中該氫化作用係於 (i )存在選自由下列化學式表示之有機金屬化合物觸媒： R5474953 Printing of A7 by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs _____B7__ V. Description of the invention j) Method for hydrogenating fresh polymers containing olefin unsaturated groups (living polymer) using specific titanium pentafluorene compounds and alkyl lithium compositions . However, these catalyst systems are difficult to handle when they are highly active and have insufficient storage stability for long periods of storage. In addition, these systems require a reducing agent (organic metal) to reduce the titanium pentafluoride compound to a low-value compound. The hydrogenation activity depends on the molar ratio of the reducing agent to the titanium pentafluorene compound and the contact conditions. This catalyst system is difficult to handle. The double bond system of hydrogenated olefin-containing unsaturated double bond polymers used in the reaction products of Tebbe's reagents (metal compounds of titanium pentafluorene and trimethylaluminum) and alkyl metal compounds is known (US patent 5, 2 44, 980). The disadvantage of this method is that a large amount of alkyl alkali metal compound must be used as a co-catalyst to achieve high hydrogenation activity. In addition, since the catalyst used for this method is poor in activity, it is necessary to use a large amount of catalyst. SUMMARY OF THE INVENTION The object of the present invention is to provide an industrially advantageous method for hydrogenating a double bond of a conjugated diene polymer, which comprises contacting the conjugated diene polymer with an inert organic solvent, the conjugated diene using an organic alkali metal The compound is prepared as a polymerization initiator. In this method, the catalyst used for hydrogenation is stable and easy to handle. No alkali metal compound is required as a co-catalyst, the amount of catalyst required is very small, and the hydrogenation is performed quantitatively, at a wide range of temperatures. Good results reproducibility within the range. Other objects and effects of the present invention will be apparent from the following description. It has been proposed that (Please read the precautions on the back before filling out this page) This paper size applies to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) -5-474953 A7 B7 V. Description of the invention 3 () (1 ) A method for hydrogenating a conjugated diene polymer, comprising the step of adding a passivating agent to passivate the conjugated diene polymer, the polymer being prepared using an organic alkali metal compound as a polymerization initiator; and using an inert hydrocarbon solvent The passivated diene polymer is contacted with hydrogen to hydrogenate the double bond of the passivated diene polymer, wherein the hydrogenation is based on (i) the presence of a catalyst selected from an organometallic compound represented by the following chemical formula: R5

C X· ，CH3C X ·, CH3

A I CH, 其中，R1、R2、R3、R4、r5、r6、r7r8、經濟部中央標準局員工消費合作社印製 R9與rig，可相同或不同，其各表示氫原子、具有 1 2個碳原子之烴基，或具有1至1 2個碳原子之烷基甲矽烷基；X表示鹵素原子或甲基； (i i )於滿足下列關係式： (M - A1 · Ti)/Ti < 2 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -6 - 474953 經濟部中央樣準局員工消費合作社印製 A7 B7__五、發明説明4() 其中Μ表示該有機鹼金屬化合物之莫耳量；Z表示該鈍化劑之莫耳量；A 1表示該有機鋁化合物之莫耳量；而T i 表示有機鈦化合物之莫耳量的條件下進行； (2 )根據上述（1 )之方法，其中該惰性烴溶劑實質上不含直鏈醚化合物； (3 )根據上述（1 )之方法，其中所添加之鈍化劑用量滿足關係式 -5 S (M - Z)/ Ti S 1 · 9; (4 )根據上述（1 )之方法，其中該氫化作用係於符合關係式-3 S (M - Z + Al - Ti)/Ti ^ 1之條件下進行； (5 )根據上述（1 )之方法，其中該觸媒係二鹵化鈦5圜與三甲基鋁之反應混合物；以及 (6)根據上述（1 )之方法，其中該氫化作用係於存在三級胺化合物下進行； .而達成本發明上述目的。本發明已發現下列事實。當於惰性有機溶劑下將使用有機鹼金屬化合物作爲聚合引發劑所製備之共軛二烯與氫接觸以氫化該共軛二烯之雙鍵時，於存在特定鈦五圜作爲組份（A )，並符合-6 < (Μ · Z + A1 · Ti)/Ti < 2 之下，不需使用鹼金屬化合物進行該反應即可使共軛二烯聚合物或共軛二烯/乙烯基芳族烴共聚物之烯烴不飽和雙鍵定量進行氫化作用。本發明者驚異地發現即使使用不需去除之極少量觸媒時，該氫化作用亦可定量進行，而且因爲該 (請先閲讀背面之注意事項再填寫本頁} 訂本紙張尺度適用中國國家標準（CNS ) A4規格（210X29*7公釐） A7 B7 474953 第86114780號專利申請案中文說明書修正頁五、發明説明（5 ) 觸媒系統於廣泛溫度範圍內顯示氫化活性，聚合作用之後不需控制氫化溫度之步驟。因此，該氫化作用可於溶液之粘度可能較低之高溫區進行，如此縮短氫化反應之時間。此外，不必於氫化作用期間添加有機鹼金屬化合物控制T i對於有機鹼金屬之比率，而且可安定地顯示具有極高結果重現性之觸媒活性。本發明係基於此等發現達成。亦即，本發明已經以該令人驚異之事實爲基礎完成，此事實係不需添加另外之有機鹼金屬化合物即可得到相當高之觸媒活性，該觸媒於廣泛溫度範圍中具有明顯之經改良耐熱性與高度活性，於共同存在特定添加劑下該觸媒之長期安定性明顯獲得改良。發明詳述作爲本發明聚合引發劑之有機鹼金屬化合物包括習知對於共軛二烯化合物具有陰離子聚合活性者，諸如脂族烴鹼金屬化合物、芳族烴鹼金屬化合物以及有機胺基鹼金屬化合物。該鹼金屬包括鋰、鈉與鉀。適用之有機鹼金屬化合物包括具有1至2 0個碳原子之脂族或芳族烴鋰化合物。此等鋰化合物可爲每個單一分子具有一個鋰原子之單鋰化合物，或每個單一分子具有多個鋰原子之二、三或四鋰化合物。該鋰化合物之特定實例係正丙基鋰、正丁基鋰、第二丁基鋰、第三丁基鋰、正戊基鋰、正己基鋰、卞基鋰、苯基鋰、甲苯基鋰、二異丙烯苯與第二丁基鋰之反應產物，以及二乙烯基苯、第二丁基鋰與小量1，3 - 丁二烯之反應本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） · _ 11---Γ---裝----„---訂------ (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印^ 474953 A7 ______B7__ 五、發明説明g ) 產物。本發明所使用之共軛二烯聚合物包括一種共軛二燒之均聚物、二或多種共軛二烯之共聚物，以及共軛二嫌與可與其共聚之單體之共聚物，該單體包括其中具有衍生自共軛二烯單體烯烴雙鍵之1，4 一、1，2 —或3 , 4 —聚合物。該共軛二烯包括具有4至2 0個碳原子者。其特定實例包括1 ，3 —丁二烯、異戊間二烯、2，3〜二甲基一 1，3 —丁二烯、1，3 —戊二烯、2 —甲基、：l，3 一戊二烯、1 ，3 —己二烯、4，5 -二乙基一 1，3 一經濟部中央標準局員工消費合作社印製辛二烯與3 — 丁基一 1，3 —辛二烯。就工業優點與製得具有優良物理性質之彈性產物而言，1，3 -丁：:：烯與異戊間二烯爲佳。其他可與該共軛二烯共聚之單體通常包括乙烯基芳族化合物。其特定實例包括苯乙烯、α〜甲基苯乙烯、間甲基苯乙烯、二乙烯基苯、1，1一二苯基乙烯、Ν，Ν —二甲基一間一胺基乙基苯乙烯與Ν，Ν —二乙基-間-胺基乙基苯乙烯。其中，以苯乙烯與α —甲基苯乙烯爲佳。包括此等單體之共軛二烯共聚物可爲無規或嵌段共聚物。本發明所使用之惰性烴溶劑係共軛二烯用之溶劑，其不會對該氫化作用造成負面影響。本發明中，於相同惰性烴溶劑中進行聚合作用，隨後進行氫化作用爲佳。適用溶劑之實例包括脂族烴類，諸如正丁烷、異丁烷、正戊烷、正己烷、正庚烷與正辛烷，以及脂環烴類，諸如環己烷、環庚烷與甲基環庚烷。可使用芳族烴類，諸如苯、甲苯、本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐）~" -9 - 474953 修正7 補充％^〇日 A7 _ ......—· 一· __B7_五、發明説明（7 ) 二甲苯與乙基苯’其僅限於芳族雙鍵在所使用之氫化條件下不會被氫化者。觸媒組份（A )係一種有機金屬化合物，其由下列化學式表示AI CH, where R1, R2, R3, R4, r5, r6, r7r8, R9 and rig printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs can be the same or different, each of which represents a hydrogen atom and has 12 carbon atoms A hydrocarbon group, or an alkylsilyl group having 1 to 12 carbon atoms; X represents a halogen atom or a methyl group; (ii) satisfying the following relationship: (M-A1 · Ti) / Ti < 2 sheets Standards are applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm) -6-474953 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7__V. Invention Description 4 () where M represents the organic alkali metal compound Ear amount; Z represents the mole amount of the passivating agent; A 1 represents the mole amount of the organoaluminum compound; and T i represents the mole amount of the organic titanium compound; (2) According to the above (1) Method, wherein the inert hydrocarbon solvent is substantially free of linear ether compounds; (3) the method according to (1) above, wherein the amount of the passivating agent added satisfies the relationship of -5 S (M-Z) / Ti S 1 · 9; (4) the method according to the above (1), wherein the hydrogenation is in accordance with the relational formula -3 S (M-Z + Al-Ti) / Ti ^ 1; (5) The method according to the above (1), wherein the catalyst is a reaction mixture of titanium dihalide 5 圜 and trimethylaluminum; and ( 6) The method according to the above (1), wherein the hydrogenation is performed in the presence of a tertiary amine compound; and the above-mentioned object of the invention is achieved. The present invention has discovered the following facts. When a conjugated diene prepared using an organic alkali metal compound as a polymerization initiator is contacted with hydrogen in an inert organic solvent to hydrogenate the double bond of the conjugated diene, a specific titanium pentafluorene is present as a component (A) And conforming to -6 < (Μ · Z + A1 · Ti) / Ti < 2 below, the conjugated diene polymer or conjugated diene / vinyl group can be made without using an alkali metal compound for the reaction. The olefinically unsaturated double bonds of the aromatic hydrocarbon copolymer are subjected to quantitative hydrogenation. The inventor was surprised to find that even when a very small amount of catalyst that does not need to be removed, the hydrogenation can be performed quantitatively, and because of this (please read the precautions on the back before filling this page) The paper size is applicable to Chinese national standards (CNS) A4 specification (210X29 * 7mm) A7 B7 474953 Patent Application No. 86114780 Chinese Specification Revised Page V. Description of the invention (5) The catalyst system shows hydrogenation activity in a wide temperature range, no control is required after polymerization Step of hydrogenation temperature. Therefore, the hydrogenation can be performed in a high temperature region where the viscosity of the solution may be low, thus shortening the time of the hydrogenation reaction. In addition, it is not necessary to add an organic alkali metal compound during the hydrogenation to control T i for the organic alkali metal. Ratio, and can stably show catalyst activity with extremely high reproducibility of results. The present invention is achieved based on these findings. That is, the present invention has been completed on the basis of this amazing fact, which is not required Addition of other organic alkali metal compounds can obtain a relatively high catalyst activity, the catalyst in a wide temperature range It has obvious improved heat resistance and high activity, and the long-term stability of the catalyst is obviously improved under the coexistence of specific additives. DETAILED DESCRIPTION OF THE INVENTION The organic alkali metal compounds used as the polymerization initiator of the present invention include the conventional conjugated diene. Compounds having anionic polymerization activity, such as aliphatic hydrocarbon alkali metal compounds, aromatic hydrocarbon alkali metal compounds, and organic amino alkali metal compounds. The alkali metals include lithium, sodium, and potassium. Suitable organic alkali metal compounds include those having 1 to 2 Aliphatic or aromatic hydrocarbon lithium compounds of 0 carbon atoms. These lithium compounds may be single lithium compounds having one lithium atom per single molecule, or two, three or four lithiums having multiple lithium atoms per single molecule. Compounds. Specific examples of this lithium compound are n-propyllithium, n-butyllithium, second butyllithium, third butyllithium, n-pentyllithium, n-hexyllithium, fluorenyllithium, phenyllithium, and tolyl. The reaction product of lithium, diisopropenebenzene and second butyl lithium, and the reaction of divinylbenzene, second butyl lithium and a small amount of 1,3-butadiene This paper is suitable for this paper National Standard (CNS) A4 specification (210X297 mm) · _ 11 --- Γ --- installation ---- „--- Order ------ (Please read the precautions on the back before filling in this Page) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ 474953 A7 ______B7__ 5. Description of the invention g) Product. The conjugated diene polymer used in the present invention includes a conjugated dialkyl homopolymer, two or more conjugate Copolymers of dienes, and copolymers of conjugated dienes and monomers copolymerizable therewith, the monomers including 1, 4 one, 1, 2, which have an olefin double bond derived from a conjugated diene monomer-or 3, 4-polymer. The conjugated diene includes those having 4 to 20 carbon atoms. Specific examples thereof include 1, 3-butadiene, isoprene, 2, 3 to dimethyl-1 , 3-butadiene, 1,3-pentadiene, 2-methyl ,: 1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-economic The Consumer Cooperative of the Central Bureau of Standards of the Ministry printed octadiene and 3-butyl-1,3-octadiene. In terms of industrial advantages and the production of elastic products with excellent physical properties, 1,3-butane ::: ene and isoprene are preferred. Other monomers copolymerizable with the conjugated diene usually include vinyl aromatic compounds. Specific examples thereof include styrene, α-methylstyrene, m-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-m-aminoaminoethylstyrene With N, N-diethyl-m-aminoethylstyrene. Of these, styrene and α-methylstyrene are preferred. The conjugated diene copolymer including these monomers may be a random or block copolymer. The inert hydrocarbon solvent used in the present invention is a solvent for a conjugated diene, which does not adversely affect the hydrogenation. In the present invention, it is preferable to perform polymerization in the same inert hydrocarbon solvent, followed by hydrogenation. Examples of suitable solvents include aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane and n-octane, and alicyclic hydrocarbons such as cyclohexane, cycloheptane and methyl Cycloheptane. Aromatic hydrocarbons can be used, such as benzene, toluene, etc. The size of this paper is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) ~ " -9-474953 amendment 7 supplementary% ^ 0 day A7 _..... --- I. __B7_V. Description of the invention (7) Xylene and ethylbenzene 'are limited to those whose aromatic double bonds will not be hydrogenated under the hydrogenation conditions used. The catalyst component (A) is an organometallic compound, which is represented by the following chemical formula

(請先閱讀背面之注意事 1# ，項再填· 裝—— :寫本頁) 訂 R9與R1。，可相同或不同，其各表示氫原子、具有1至 1 2個碳原子之烴基，或具有1至1 2個碳原子之烷基甲石夕院基；X表不鹵素原子或甲基。換言之，組份（A)包括泰比試劑與泰比型錯合物，即二鹵化鈦五圜與三甲基鋁之金屬環化合物，其與泰比試劑之結構相似。以 R1、R2、R3、R4、R5、R6、R7、r8、 R9與R1(D表示之具有1至1 2個碳原子之烴基包括直鏈烴基、分枝烴基、脂環烴基與芳族烴基。以R 1、R 2、 R3、R4、R5、R6、R7、R8、R9 與 R1。表示之烷基甲矽烷基係由RR{R“S i-或—SiRR’一（其中R、尺‘與！^ “分別表示具有1至1 2個碳原子之烷基）表示之。可由兩個選自R1、R2、R3、R4與R5或由兩個選本紙張尺度適用中國國家標準（CNS ) A4規格（21〇><297公釐） Φ. 經濟部智慧財產局員工消費合作社印製 -10- 474953 A7 B7 修正補充H轟經濟部智慧財產局員工消費合作社印製五、發明説明（8 ) 自R6、R7、R8、R9與R1。之基團形成環。此外，R 1、尺2、113、114與115之一可與116、117、118、119 與 R1Q 之一鍵結。Ri、R2、R3、R4、r5、r6、 R7、R8、R9與R1 ◦之特定實例包括氫原子與甲基、乙基、丙基、異丙基、正丁基、異丁基、第三丁基、第二丁基、正戊基、異戊基、1 一甲基丁基、2 -甲基丁基、 1 ，2 —二甲基丙基、新戊基、正己基、異己基、1—甲基戊基、2 —甲基戊基、3 —甲基戊基、1 ，1 一二甲基丁基、2 ’ 2 —二甲基丁基、3 ，3 —二甲基丁基、1 ， 2 —二甲基丁基、1 ，3 —二甲基丁基、1 ，1—乙基甲基丙基、1 -乙基丁基、2 -乙基丁基、環己基、正庚基、異庚基、4 一甲基己基、3 —甲基己基、2 —甲基己基、1—甲基己基、1 ，1 一二甲基戊基、2 ，2 —二甲基戊基、3，3_二甲基戊基、4，4 —二甲基戊基、1 ， 2 —二甲基戊基、1 ，3 —二甲基戊基、1 ，4 一二甲基戊基、1 一乙基戊基、1 一丙基丁基、2 -乙基戊基、3 一乙基戊基、1 ，1 一乙基甲基丁基、1 ，；[—二乙基丙基、2，3 -二甲基戊基、2，4 一二甲基戊基、3，4 一二甲基戊基、1—乙基—2 —甲基丁基、1—乙基一 3 一甲基丁基、4 一甲基環己基、3 —曱基環己基、環庚基、1 ，1 ，2 —三甲基丁基、1 ，1 ，3 —三甲基丁基、 2，2 ，1 —三甲基丁基、2, 2, 3-三甲基丁基、3，3 ，1_三甲基丁基、3 ，3 ，2 -三甲基丁基、1 ，1 ，2 ， 2 —四甲基丙基、正辛基、1 一甲基庚基、2 —甲基庚基 (請先閲讀背面之注意事 # 項再填· 裝---- :寫本頁) 訂—(Please read the note 1 # on the back, fill in the items and then install-: write this page) Order R9 and R1. , Which may be the same or different, and each represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or an alkylformyl group having 1 to 12 carbon atoms; X represents a halogen atom or a methyl group. In other words, component (A) includes a Taby reagent and a Taby complex, that is, a metal ring compound of titanium dihalide pentafluorene and trimethylaluminum, which has a similar structure to the Taby reagent. The hydrocarbon groups represented by R1, R2, R3, R4, R5, R6, R7, r8, R9 and R1 (D has 1 to 12 carbon atoms include straight chain hydrocarbon groups, branched hydrocarbon groups, alicyclic hydrocarbon groups and aromatic hydrocarbon groups The alkyl silyl group represented by R 1, R 2, R3, R4, R5, R6, R7, R8, R9 and R1 is represented by RR {R "S i- or -SiRR'- (where R, ruler 'And! ^ "Represents an alkyl group having 1 to 12 carbon atoms respectively). It can be selected from two selected from R1, R2, R3, R4 and R5, or from two selected paper sizes. The Chinese national standard (CNS ) A4 specification (21〇 < 297 mm) Φ. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -10- 953 953 A7 B7 Amends and supplements printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (8) The groups from R6, R7, R8, R9 and R1 form a ring. In addition, one of R 1, chi 2, 113, 114, and 115 may be bonded to one of 116, 117, 118, 119, and R1Q .Ri, R2, R3, R4, r5, r6, R7, R8, R9, and R1. Specific examples include a hydrogen atom and a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, Tributyl, second Base, n-pentyl, isopentyl, 1-methylbutyl, 2-methylbutyl, 1, 2-dimethylpropyl, neopentyl, n-hexyl, isohexyl, 1-methylpentyl , 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 2 '2-dimethylbutyl, 3, 3-dimethylbutyl, 1, 2-di Methylbutyl, 1,3-dimethylbutyl, 1,1-ethylmethylpropyl, 1-ethylbutyl, 2-ethylbutyl, cyclohexyl, n-heptyl, isoheptyl , 4-methylhexyl, 3-methylhexyl, 2-methylhexyl, 1-methylhexyl, 1,1-dimethylpentyl, 2,2-dimethylpentyl, 3,3-di Methylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 1-ethylpentyl Base, 1-propylbutyl, 2-ethylpentyl, 3-ethylpentyl, 1,1 monoethylmethylbutyl, 1; [-diethylpropyl, 2,3-di Methylpentyl, 2,4-dimethylpentyl, 3,4-dimethylpentyl, 1-ethyl-2-methylbutyl, 1-ethyl-3-methylbutyl 4 monomethylcyclohexyl, 3-fluorenylcyclohexyl, cycloheptyl, 1,1,2-trimethylbutyl, 1,1,3-trimethylbutyl, 2,2,1-trimethyl Butylbutyl, 2, 2, 3-trimethylbutyl, 3,3,1-trimethylbutyl, 3,3,2-trimethylbutyl, 1,1,2,2-tetramethyl Propylpropyl, n-octyl, 1-methylheptyl, 2-methylheptyl (please read the note on the back # item and fill in and install ----: write this page) Order —

—AT 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -11 - 474953 A7 B7 五、發明説明9() 、3 —甲基庚基、4 一甲基庚基、、1 一乙基己基、2 —乙基己基、基己基、1 ，1 一二甲基己基、2 ，3 —二甲基己基、4，4 一二甲基己基 5—甲基庚基、異辛基 3 —乙基己基、4 一乙 2 —二甲基己基、3 5 —二甲基己基、1 ，2 —二甲基己基、1 ，3 —二甲基己基、1 ，4 一二甲基己基、1 ，5—二甲基己基、2 ，3 —二甲基己基、2 ，4一二甲基己基、3，4 一二甲基己基、2 ，5 —二甲基己基、3，5 —二甲基己基、1 ，1 乙基戊基基戊基、一乙基一2—甲基戊基一乙基一 3 乙基一 1 一甲基一甲一乙基一 4 一甲基戊基、2 —乙基一 1 一甲基 3，3 —乙基甲基戊基、乙基一 4 一甲基戊基、3 戊基、2，2 —乙基甲基戊基、 2 —乙基一 3 —甲基戊基、2 — 一乙基一 4 一甲基戊基、3 —乙基一 2 —甲基戊基 1 一二乙基丁基、2，2 —二乙基丁基丁基、1 ， 1一甲基丙基丁基請先閱讀背面之注意事項再經濟部中央標準局員工消費合作社印製、3 —甲基一 1 一丙基丁基、4 環己基、3，4 一二甲基環己基基、1，1，3 —三甲基戊基、、2，2，1 一三甲基戊基、2 2，2，4一三甲基戊基、3, ，3，2—三甲基戊基、3，3 2，3—三甲基戊基、1，2, 2 —甲基一乙基環，4 一三甲基戊基、 4 一三甲基戊基、1 ，2，3 3 , 1 - ,4 一三 4 一三甲一三甲基 2，3 ，4 一三甲基戊基 1 ，2 —二乙基一 1 一丙基丁基己基、3 —乙基，2 -三甲基戊 4 一三甲基戊基一三甲基戊基、三甲基戊基、3 甲基戊基、1 ，基戊基、1，3 戊基、1，2，本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -12 - 474953 A7 B7 五、發明説明A ) ，2 —四甲基丁基、1，1，3，3—四甲基丁基、1 ， 1 ，2，3 —四甲基丁基、2，2，1 ，3 —四甲基丁基、1 一乙基一 1 ，2 —二甲基丁基、2—乙基一 1 ，2 — 二甲基丁基、1 一乙基一 2，3 —二甲基丁基、正壬基、異壬基、1 一甲基辛基、2 —甲基辛基、3 —甲基辛基、 4 一甲基辛基、5 —甲基辛基、6 —甲基辛基、1 一乙基庚基、2 —乙基庚基、3 —乙基庚基、4 一乙基庚基、5 一乙基庚基、1 ，1 一二甲基庚基、2，2 —二甲基庚基、3，3—二甲基庚基、4，4 一二甲基庚基、5，5 一二甲基庚基、6 ，6—二甲基庚基、1 ，2 —二甲基庚基、1 ，3 —二甲基庚基、1 ，4 一二甲基庚基、1 ，5 一二甲基庚基、1 ，6 —二甲基庚基、2，3 —二甲基庚基經濟部中央標準局員工消費合作社印製、2，4 一二甲基庚基、2，5 —二甲基庚基、2，6 一二甲基庚基、3，4 一二甲基庚基、3，5 —二甲基庚基、3，6 —二甲基庚基、4，5 —二甲基庚基、4，6 一二甲基庚基、5，6 —二甲基庚基、1 ，1 ，2 一三甲基己基、1 , 1 , 3 —三甲基己基、1 , 1 ，4 一二甲基己基、1 ，1 ，5 —三甲基己基、2，2，1 一三甲基己基、2 , 2，3 —三甲基己基、2，2，4 一三甲基己基、 2，2，5 —三甲基己基、3，3，1 一三甲基己基、4 ，4，1 一三甲基己基、4，4，2 —三甲基己基、4， 4，3 —三甲基己基、4，4，5 —三甲基己基、5，5 ，1 一三甲基己基、5，5，2 —三甲基己基、5，5， 3 —三甲基己基、5，5，4 一三甲基己基、1 ，2，3 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -13 - 474953 A7 B7 經濟部中央標準局員工消費合作社印製五、發明説明& ) 一甲基己基 2 f 3 9 4 一三甲基己基、 3 f 4 9 5 一甲基己基 1 f 3 t 4 — 三甲基己基 1 9 4 f 5 — 二甲基己基 2 4 5 — 三甲基己基 1 y 2 9 5 — 二甲基己基 1 > 2 j 4 一三甲基己基、 1 1 一乙基甲基己基 2 2 — 乙基甲基己基 3 f 3 一乙基甲基己基 4 > 4 一乙基甲基己基 5 9 5 一乙基甲基己基 1 一乙基 — 2 一甲基己基 1 — 乙基一 3 — 甲基己基 1 — 乙基 — 4 一甲基己基 1 — 乙基 — 5 一甲基己基 2 — 乙基 — 1 — 甲基己基 > 3 — 乙基 — 1 — 甲基己基 3 一乙基 — 2 一甲基己基 1 > 1 一二乙基戊基 2 2 一 — 二乙基戊基 3 3 一二乙基戊基 1 2 — 二乙基戊基 1 9 3 — 二乙基戊基 2 3 — 二乙基戊基 1 9 1 一甲基丙基戊基 2 » 2 — 甲基丙基戊基 1 一甲基一 2 — 丙基戊基正癸基、異癸基、 1 — 甲基壬基 2 一甲基壬基 3 — 甲基壬基 4 一甲基壬基 5 一甲基壬基 6 — 甲基壬基 λ 7 — 甲基壬基 1 — 乙基辛基 2 一乙基辛基 3 一乙基辛基 4 一乙基辛基 5 — 乙基辛基 6 一乙基辛基 1 1 一二甲基辛基 % 2 f 2 — 二甲基辛基 3 9 3 一二甲基辛基 \ 4 4 一二甲基辛基 5 赁 5 一二甲基辛基 6 j 6 一二甲基辛基 7 t 7 一一甲基辛基 1 9 2 — 一甲基辛基 1 3 一一甲基辛基 1 f 4 一二甲基辛基、 1 1 5 一二甲基辛基 1 f 6 — 一甲基辛基、 1 9 7 — 二甲基辛基 2 1 3 — 二甲基辛基 2 4 一二甲基辛基 2 > 5 一二甲基辛基 2 ， 6 一二甲基辛基 2 9 7 一二甲本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）請先閱讀背面之注意事項再 14 474953 A7 B7 修正補於曰五、發明説明（12 ) 基辛基、3，4 一，6 —二甲基辛基、3，7 — 基辛基、4，6 -二甲基辛基甲 3 ，5 —二甲基辛基、3 甲基辛基、4 ，5 —二甲 4，7 —二甲基辛基、5 6 —二甲基辛基 7 - 甲、正十一基、正十二基、三甲基甲矽烷基、三乙基甲矽烷基、三辛基甲矽院基與甲基二丁基甲矽烷基。該環與此等取代基所形成之鍵結基團實例包括芴基、茚基、四氫茚基、伸甲基、伸乙基、-C (CH3) 2 -、C (C2H5) 2 -、 —Si(CH3)2 —與一 Si (C2H5)2 一基。此等基團可單獨使用或以其二或多種於上述列舉者。該環戊二烯化合烷基甲矽烷基）數量自0至4爲此。爲獲得在該共軛二烯聚合物烴共聚物之共軛二烯部分上不飽確保廣泛溫度範圍之氫化位置之、R4、R5、R6、R7、R8 自氫原子，與曱基、乙基、丙基基、第三丁基、第二丁基、正戊之組合使用物之取代基佳，但是並或共軛二烯和雙鍵高度選擇性，R 、R 9 與 R 1 、異丙基、基、異戊基。該基團不限 (烴基及/或不特別受限於 /乙烯基芳族氫化活性，並 1、R 2、R 3 ^分別表示選正丁基、異丁 I I -7-7--.---裝----^---訂----- (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局S工消費合作社印製甲基丁基、2 -甲基丁基、1 ，2 —二甲基丙基、基、異己基、1 一甲基戊基、2 -甲基戊基基、1 ，1 一二甲基丁基、2 ，2 —二甲基丁基、3 一二甲基丁基、1，2 —二甲基丁基、1 ，基、1 ，1一乙基甲基丙基、1一乙基丁基、環己基、正庚基、異庚基、4 一甲基己基、3 戈基、正己 3 —甲基戊 3 3 —二甲基丁 2 —乙基丁基一甲基己基、本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -15- 474953 A7 B7 i修正I截m〇經濟部智慧財產局員工消費合作社印製五、發明説明（13) 2 —甲基己基、1 一曱基己基、1 ，1—二甲基戊基、2 ，2 —二甲基戊基、3 ，3 —二甲基戊基、4 ，4 —二甲基戊基、1 ，2 —二甲基戊基、1 ，3 —二甲基戊基、1 ，4 一二甲基戊基、1 一乙基戊基、1—丙基丁基、2_ 乙基戊基、3 —乙基戊基、1 ，1 一乙基甲基丁基、1 ， 1—二乙基丙基、2 ，3 —二甲基戊基、2 ，4 —二甲基戊基、3 ，4 一二甲基戊基、1—乙基一 2 —甲基丁基、 1 一乙基—3 —甲基丁基' 4 一甲基環己基、3 —甲基環己基、環庚基、1 ，1 ，2 -三甲基丁基、1 ，1 ，3_ 三甲基丁基、2，2，1—三甲基丁基、2，2，3 -三甲基丁基、3 ’ 3 ’ 1 一二甲基丁基、3 ，3 ，2 —三甲基丁基、1 ，1 ，2，2 -四甲基丙基與正辛基爲佳。對活性而言，特佳者係氫原子，與甲基、乙基、丙基、異丙基、正丁基、異丁基、第三丁基、第二丁基、正戊基、異戊基、1—甲基丁基、2 -甲基丁基、1 ，2 —二甲基丙基、新戊基、正己基、異己基、1 一甲基戊基、2 -甲基戊基、3 —甲基戊基、1 ，1—二甲基丁基、2，2 -二甲基丁基、3 ，3 —二甲基丁基、1 ，2 —二甲基丁基、 1 ，3 —二甲基丁基、1 ，1—乙基甲基丙基、1 一乙基丁基、2 -乙基丁基、環己基與正庚基。組份（A ) —般係由對應欽五圜之二鹵化物與三甲基鋁反應製備。組份（A )可由該反應混合物分離或以製成之反應混合物形式使用。以反應混合物形式使用可得到工業優點。單獨混合該二鹵化鈦五圜與三甲基鋁無法形成組 (請先閲讀背面之注意事項再填> :寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -16- 474953 A7 B7 五、發明説明& 經濟部中央標準局員工消費合作社印製份（A )。其必須完全反應。尤其是，該二鹵化鈦五圜分散或溶解於一種惰性溶劑中，於其中添加三甲基鋁，隨後於0至1 0 0 °C充分攪拌。反應溫度過低時，製造組份（ A )之時間太長。反應溫度過高時，易於發生副反應，所形成之組份（A)氫化活性降低。較佳反應溫度範圍自 1 0至5 0°C。該反應經由兩個階段進行，於開始階段時，該組份（A)尙未完全形成。於室溫時，該反應時間以一天或以上爲佳。因此，藉由例如NMR分析確認組份（ A )形成極爲重要。該錯合物之形成藉由泰比等人所提出之技術（J. Am. Chem. Soc·，第 100 卷，3611-361 3 ( 1 9 7 8 ))確認爲佳。已知在組份（A )之1 Η -NMR光譜中，該質子吸收係歸因於T i 一 A 1金屬環之伸甲基交聯特性，特別是顯現於磁場（7.8至8.3 p pm) —般T i錯合物與A 1化合物之質子吸收處。該尖峰與其他副產物尖峰之比較使其可確認組份（A )形成，並計算該產物比率。於惰性烴溶劑中使該共軛二烯聚合物與氫接觸進行氫化作用中，（M - Z + Al - Ti)/Ti (其中Μ表示該有機鹼金屬化合物之莫耳量；Ζ表示該鈍化劑之莫耳量；A 1表示該有機鋁化合物之莫耳量；T i表示該有機鈦金屬化合物之莫耳量）必須自大於一 6至小於2。該（ Μ · Z + A1 · Ti)/Ti自一 3至1爲佳。假如上述參數無法落於上述範圍內，無法藉由添加少量組份（A )而達到高氫化活性之優良效率。請_ 先閲讀^ Γ 之%， I ,fj 頁訂本紙張尺度適用中國國家標準（CNS ) A4規格（210X29*7公釐） -17- 五、發明説明（15) 該有機鹼金屬莫耳量Μ係作爲製造共軛二烯聚合物之聚合引發劑的有機鹼金屬化合物中所含之鹼金屬莫耳量。 (請先閱讀背面之注意事項再填寫本頁) 該鈍化劑係作爲鈍化該有機金屬化合物之化合物。本發明中，該鈍化劑係一種可以鈍化該作爲製造共軛二烯聚合物之聚合引發劑的有機鹼金屬化合物，並鈍化組份（A )之合成中所用之有機錦化合物。Z於單價鈍化劑實例中係指鈍化劑之莫耳量，於多價實例中係指該產物之莫耳量與其價數。有機鋁化合物之莫耳量A 1係添加於該氫化系統之有機鋁化合物之莫耳量。其係混入組份（A )之鋁、用以合成組份（A )之未反應有機鋁化合物以及合成期間有機鋁化合物之鋁的總莫耳量。有機鈦化合物之莫耳量T i係添加於該氫化系統之有機鈦化合物之莫耳量。其係混入組份（A )之鈦、用以合成組份（A )之未反應有機鈦化合物以及合成期間有機鈦化合物之鈦的總莫耳量。經濟部智慧財產局員工消費合作社印製該鈍化劑包括具有羥基、羧基、酯基、環氧基等之化合物，該基團與有機金屬化合物反應產生一種金屬烷氧化物與鹵素化合物，其與一種有機金屬化合物反應產生一種金屬鹵化物。視所需目的而定，可使酯類化合物、聚環氧化合物與聚鹵素化合物與該共軛二烯聚合物之鹼金屬末端反應，以提高該分子量或是形成分枝結構。適用之鈍化劑係甲醇、乙醇、正丙醇、正丁醇、第二丁醇、第三丁醇、 1—戊醇、2 —戊醇、3 —戊醇、1—己醇、2 —己醇、3 -18- 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 474953 Α7 Β7 經濟部中央標準局員工消費合作社印製五、發明説明乂 ) 一己醇、1 一庚醇、1—己醇、2 —己醇、3 -己醇、1 一庚醇、2 -庚醇、3 —庚醇、4 一庚醇、辛醇、壬醇、癸醇、十一醇、月桂基醇、烯丙基醇、環己醇、環戊醇以及芣基醇；酚類，諸如鄰甲苯酚、間甲苯酚、對甲苯酚、對烯丙基酚、2，6 —二一第三丁基一對一甲苯酚，以及二甲苯酚；有機羧酸，諸如醋酸、丙酸、丁酸、異醋酸、戊酸、己酸、庚酸、癸酸、肉豆蔻酸、硬脂酸、山窬酸以及苯酸；羧基化合物，諸如乙醛、丙酮、甲基乙基酮、二異丙基酮、乙醯丙酮、苯醛、二苯基酮與乙醯基苯；以及酯類，諸如醋酸乙酯，丙酸丁酯、己二酸二乙酯、苯酸甲酯、對酞酸二甲酯與苯均四酸三甲酯。亦可使用水或碳酸氣作爲鈍化劑，其先決條件係其莫耳比率可被工業控制。含鹵素之鈍化劑實例包括經鹵化烴類，諸如苯基氯、甲基氯、甲基溴、乙基氯、乙基溴、丙基氯、丙基溴、正丁基氯、正丁基溴與二溴乙烷；由通式R4-nS i Xn (其中R 表示具有自1至2 0個碳原子之烴基；X表示鹵素原子； η表示自1至4之整數）表示之鹵化矽化合物，諸如三甲基甲矽烷基氯、三甲基甲矽烷基溴、二乙基甲矽烷基二氯、甲基甲矽烷基三氯、第三丁基甲矽烷基化氯以及四氯矽烷；由通式R4-nS ηΧη (其中R表示具有自1至2 0個碳原子之烴基；X表示鹵素原子；η表示自1至4之整數 )表示之鹵化錫化合物，諸如三甲基錫化氯、三甲基錫化溴、二乙基錫化二氯、甲基錫化三氯、第三丁基錫化三氯以及四氯化錫。此等鈍化劑可單獨使用或將其二或多種組本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） (請先閲讀背面之注意事項再頁) 訂 -19 - 474953 A7 B7 五、發明説明; 合使用。添加於該聚合系統時，一級胺、二級胺、分子氫、乙炔化合物、丙二化合物等亦可鈍化該有機鹼金屬化合物。然而，因爲其與鈦五圜產生不當反應，所以最好與上述鈍化劑組合使用爲佳。此實例中，僅有上述鈍化劑之莫耳量以"Z ”表示。本發明中，鈍化劑對於使用有機鹼金屬化合物作爲聚合引發劑所製得共軛二烯聚合物之添加量符合關係式：請先閲讀背之注意事項再填1 寫1 頁 -5 Μ 一 Z ) / T i 此條件下，本發明特別令人即具高度氫化活性。，所以使用二鹵化鈦份（A )具有工業優鈦爲基準計算，該組，5 0%或以上特佳當使用二鹵化鈦份（A )時，該鈍化注目之特殊效應係以極少量氫化觸媒因爲使用工業可得化合物作爲原材料五圜與三甲基鋁之反應混合物作爲組點。此實例中，以二鹵化鈦五圜中之份（A )之產率必須爲2 0 %或以上訂經濟部中央標率局員工消費合作社印製五圜與三甲基鋁之反應混合物作爲組劑亦可添加於該反應混合物中。此實例中，反應混合物中所添加之鈍化劑用量符合關係式··- Ζ +—AT This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -11-474953 A7 B7 V. Description of the invention 9 (), 3-methylheptyl, 4-methylheptyl, 1- Ethylhexyl, 2-ethylhexyl, ylhexyl, 1,1-dimethylhexyl, 2,3-dimethylhexyl, 4,4-dimethylhexyl 5-methylheptyl, isooctyl 3 -Ethylhexyl, 4-ethyl2-dimethylhexyl, 3 5-dimethylhexyl, 1,2-dimethylhexyl, 1,3-dimethylhexyl, 1,4-dimethylhexyl, 1,5-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 3,4-dimethylhexyl, 2,5-dimethylhexyl, 3,5-di Methylhexyl, 1,1 ethylpentylpentyl, monoethyl-2 methylpentyl monoethyl 3 ethyl 1 methyl 1 methyl monoethyl 4 methyl pentyl, 2-ethyl-1 1-methyl 3,3-ethylmethylpentyl, ethyl-4 methyl-pentyl, 3-pentyl, 2,2-ethylmethylpentyl, 2-ethyl-1 3-methylpentyl, 2-monoethyl-4 methylol , 3-ethyl-2-methylpentyl 1-diethylbutyl, 2,2-diethylbutylbutyl, 1, 1-methylpropylbutyl Please read the precautions on the back first Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, 3-methyl-1,1-propylbutyl, 4-cyclohexyl, 3,4-dimethylcyclohexyl, 1,1,3-trimethylpentyl, , 2,2,1 trimethylpentyl, 2 2,2,4 trimethylpentyl, 3, 3,2-trimethylpentyl, 3,3 2,3-trimethylpentyl Group, 1,2,2-methyl monoethyl ring, 4-trimethylpentyl, 4-trimethylpentyl, 1,2,3 3, 1-, 4 one three four one three methyl one three Methyl 2,3,4-trimethylpentyl1,2-diethyl-1 monopropylbutylhexyl, 3-ethyl, 2-trimethylpent 4-trimethylpentyl-trimethyl Pentyl, trimethylpentyl, 3 methylpentyl, 1, pentyl, 1, 3 pentyl, 1,2, this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm)- 12-474953 A7 B7 V. Description of the invention A), 2-tetramethylbutyl, 1,1,3,3- Methylbutyl, 1,2,3-tetramethylbutyl, 2,2,1,3-tetramethylbutyl, 1-ethyl-1,2-dimethylbutyl, 2- Ethyl-1,2-dimethylbutyl, 1-ethyl-2,3-dimethylbutyl, n-nonyl, isononyl, 1-methyloctyl, 2-methyloctyl, 3-methyloctyl, 4-methyloctyl, 5-methyloctyl, 6-methyloctyl, 1-ethylheptyl, 2-ethylheptyl, 3-ethylheptyl, 4 Monoethylheptyl, 5-ethylheptyl, 1,1-dimethylheptyl, 2,2-dimethylheptyl, 3,3-dimethylheptyl, 4,4-dimethyl Heptyl, 5,5-dimethylheptyl, 6,6-dimethylheptyl, 1,2-dimethylheptyl, 1,3-dimethylheptyl, 1,4-dimethyl Heptyl, 1,5-dimethylheptyl, 1,6-dimethylheptyl, 2,3-dimethylheptyl Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, 2,4-dimethyl Heptyl, 2,5-dimethylheptyl, 2,6-dimethylheptyl, 3,4-dimethylheptyl, 3,5-dimethylheptyl, 3,6 — Methylheptyl, 4,5-dimethylheptyl, 4,6-dimethylheptyl, 5,6-dimethylheptyl, 1,1,2, trimethylhexyl, 1, 1, 3-trimethylhexyl, 1, 1, 4-dimethylhexyl, 1, 1, 5-trimethylhexyl, 2, 2, 1-trimethylhexyl, 2, 2, 3-trimethylhexyl , 2,2,4 trimethylhexyl, 2,2,5-trimethylhexyl, 3,3,1 trimethylhexyl, 4,4,1 trimethylhexyl, 4,4,2 -Trimethylhexyl, 4,4,3-trimethylhexyl, 4,4,5-trimethylhexyl, 5,5,1 trimethylhexyl, 5,5,2-trimethylhexyl, 5,5,3-Trimethylhexyl, 5,5,4 Trimethylhexyl, 1,2,3 This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -13-474953 A7 B7 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention &) Monomethylhexyl 2 f 3 9 4 trimethylhexyl, 3 f 4 9 5 monomethylhexyl 1 f 3 t 4 — trimethyl Hexyl 1 9 4 f 5 — dimethyl 2 2 5 5-trimethylhexyl 1 y 2 9 5-dimethylhexyl 1 > 2 j 4 monotrimethylhexyl, 1 1 monoethylmethylhexyl 2 2-ethylmethylhexyl 3 f 3 Monoethylmethylhexyl 4 > 4 monoethylmethylhexyl 5 9 5 monoethylmethylhexyl 1 monoethyl-2 monomethylhexyl 1-ethyl mono 3-methylhexyl 1-ethyl — 4 monomethylhexyl 1-ethyl-5 monomethylhexyl 2-ethyl-1-methylhexyl > 3-ethyl-1-methylhexyl 3 monoethyl-2-methylhexyl 1 > 1 diethylpentyl 2 2 di-diethylpentyl 3 3 diethylpentyl 1 2-diethylpentyl 1 9 3-diethylpentyl 2 3-diethylpentyl 1 9 1 monomethylpropylpentyl 2 »2-methylpropylpentyl 1 monomethyl 2-propylpropyl n-decyl, isodecyl, 1-methylnonyl 2 monomethylnonyl 3 — methyl nonyl 4 Monomethyl nonyl 5 Monomethyl nonyl 6 —methyl nonyl λ 7 — methyl nonyl 1 — ethyloctyl 2 monoethyloctyl 3 monoethyloctyl 4 monoethyloctyl 5 — Ethyl octyl 6 monoethyl octyl 1 1 dimethyl octyl% 2 f 2 — dimethyl octyl 3 9 3 dimethyl octyl \ 4 4 dimethyl octyl 5 Dimethyloctyl 6 j 6 Dimethyloctyl 7 t 7 Monomethyloctyl 1 9 2 — Monomethyloctyl 1 3 Monomethyloctyl 1 f 4 Dimethyloctyl, 1 1 5 dimethyloctyl 1 f 6 —monomethyloctyl, 1 9 7 —dimethyloctyl 2 1 3 —dimethyloctyl 2 4 dimethyloctyl 2 > 5 a Dimethyl octyl 2, 6 dimethyl octyl 2 9 7 dimethyl This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) Please read the precautions on the back before 14 474953 A7 B7 amendment Complementary to the fifth, description of the invention (12) Kissinki, 3, 4 a , 6-dimethyloctyl, 3,7-yloctyl, 4,6-dimethyloctylmethyl 3,5-dimethyloctyl, 3 methyloctyl, 4,5-dimethyl-4 , 7-dimethyloctyl, 5 6-dimethyloctyl 7-methyl, n-undecyl, n-dodecyl, trimethylsilyl, triethylsilyl, trioctylsilyl Home base with methyldibutylsilyl. Examples of the bonding group formed by the ring with these substituents include fluorenyl, indenyl, tetrahydroindenyl, methylen, ethyl, -C (CH3) 2-, C (C2H5) 2-, —Si (CH3) 2 —One group with Si (C2H5) 2. These groups may be used singly or in combination of two or more kinds thereof. The cyclopentadiene compound alkylsilyl) number is from 0 to 4 in this case. In order to obtain a hydrogenation position at a wide temperature range, which is not saturated on the conjugated diene portion of the conjugated diene polymer hydrocarbon copolymer, R4, R5, R6, R7, R8 self-hydrogen atoms, and fluorenyl, ethyl , Propyl, third butyl, second butyl, n-pentyl combination has good substituents, but the conjugated diene and double bonds are highly selective, R, R 9 and R 1, isopropyl Base, base, isoamyl. The group is not limited (hydrocarbon group and / or is not particularly limited to / vinyl aromatic hydrogenation activity, and 1, R 2, R 3 ^ respectively select n-butyl, isobutyl II -7-7 --.- --Packing ---- ^ --- Order ----- (Please read the precautions on the back before filling out this page) M-butyl, 2-methyl Butyl, 1,2-dimethylpropyl, methyl, isohexyl, 1-methylpentyl, 2-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethyl Butyl, 3-dimethylbutyl, 1,2-dimethylbutyl, 1,1,1,1,1-ethylmethylpropyl, 1-ethylbutyl, cyclohexyl, n-heptyl, Iso-heptyl, 4-methylhexyl, 3-glycyl, n-hexyl 3-methylpent 3 3 -dimethylbutyl 2-ethylbutyl monomethylhexyl, this paper size applies Chinese National Standard (CNS) A4 Specifications (210X297 mm) -15- 474953 A7 B7 i Correction I Section m Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (13) 2-Methylhexyl, 1-Methylhexyl, 1, 1 -Dimethylpentyl, 2,2-dimethylpentyl, 3,3- Dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 1-ethyl Amyl, 1-propylbutyl, 2-ethylpentyl, 3-ethylpentyl, 1,1 monoethylmethylbutyl, 1, 1-diethylpropyl, 2, 3-dimethyl Pentyl, 2,4-dimethylpentyl, 3,4-dimethylpentyl, 1-ethyl-2-methylbutyl, 1-ethyl-3-methylbutyl '4 a Methylcyclohexyl, 3-methylcyclohexyl, cycloheptyl, 1,1,2-trimethylbutyl, 1,1,3-trimethylbutyl, 2,2,1-trimethylbutyl , 2,2,3-trimethylbutyl, 3 '3'1 dimethylbutyl, 3,3,2-trimethylbutyl, 1,1,2,2-tetramethylpropyl Preferred is n-octyl. For activity, particularly preferred is hydrogen atom, and methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, third butyl, second butyl , N-pentyl, isopentyl, 1-methylbutyl, 2-methylbutyl, 1, 2-dimethylpropyl, neopentyl, n-hexyl, isohexyl, 1-methyl Amyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1, 2 —Dimethylbutyl, 1,3-dimethylbutyl, 1,1-ethylmethylpropyl, 1-ethylbutyl, 2-ethylbutyl, cyclohexyl and n-heptyl. Part (A) is generally prepared by the reaction of the dihalide of the corresponding pentamidine with trimethylaluminum. Component (A) can be separated from the reaction mixture or used in the form of a prepared reaction mixture. Industrial advantages are obtained when used as a reaction mixture. Mixing the titanium dihalide pentafluorene and trimethylaluminum alone cannot form a group (please read the precautions on the reverse side and fill it up:> write this page) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -16- 474953 A7 B7 V. Description of Invention & Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (A). It must be fully reactive. In particular, the titanium dihalide pentafluoride is dispersed or dissolved in an inert solvent, and trimethylaluminum is added thereto, followed by sufficient stirring at 0 to 100 ° C. When the reaction temperature is too low, it takes too long to produce component (A). When the reaction temperature is too high, side reactions are liable to occur, and the hydrogenation activity of the formed component (A) is reduced. The preferred reaction temperature ranges from 10 to 50 ° C. The reaction proceeds through two stages. At the beginning stage, the component (A) 尙 is not completely formed. At room temperature, the reaction time is preferably one day or more. Therefore, it is extremely important to confirm the formation of the component (A) by, for example, NMR analysis. The formation of this complex was confirmed by the technique proposed by Tybee et al. (J. Am. Chem. Soc., Vol. 100, 3611-361 3 (1 9 7 8)). It is known that in the 1 Η-NMR spectrum of the component (A), the proton absorption is attributed to the extensional methyl cross-linking characteristic of the T i -A 1 metal ring, which appears particularly in a magnetic field (7.8 to 8.3 p pm) -Proton absorption of general T i complex and A 1 compound. The comparison of this spike with other by-product spikes makes it possible to confirm the formation of component (A) and calculate the product ratio. Contacting the conjugated diene polymer with hydrogen in an inert hydrocarbon solvent for hydrogenation, (M-Z + Al-Ti) / Ti (where M represents the molar amount of the organic alkali metal compound; Z represents the passivation The molar amount of the agent; A 1 represents the molar amount of the organoaluminum compound; T i represents the molar amount of the organotitanium metal compound) must be from greater than 6 to less than 2. The (M · Z + A1 · Ti) / Ti is preferably from 3 to 1. If the above parameters cannot fall within the above range, the excellent efficiency of high hydrogenation activity cannot be achieved by adding a small amount of component (A). Please read ^% of Γ, I, fj page size of paper is applicable to Chinese National Standard (CNS) A4 (210X29 * 7mm) -17- V. Description of the invention (15) Molar content of the organic alkali metal M is an amount of an alkali metal mole contained in an organic alkali metal compound as a polymerization initiator for producing a conjugated diene polymer. (Please read the precautions on the back before filling this page) The passivation agent is used as a compound to passivate the organometallic compound. In the present invention, the passivation agent is an organic alkali metal compound that can passivate the polymerization initiator used as a polymerization initiator for manufacturing a conjugated diene polymer, and passivates an organic bromide compound used in the synthesis of the component (A). Z in the example of the monovalent passivation agent refers to the molar amount of the passivation agent, and in the case of the multivalent example refers to the molar amount of the product and its valence. The molar amount of the organoaluminum compound A 1 is the molar amount of the organic aluminum compound added to the hydrogenation system. It is the total molar amount of aluminum mixed into component (A), unreacted organoaluminum compounds used to synthesize component (A), and the organoaluminum compounds during synthesis. The molar amount T i of the organic titanium compound is the molar amount of the organic titanium compound added to the hydrogenation system. It is the total molar amount of titanium mixed in component (A), unreacted organic titanium compound used to synthesize component (A), and titanium of the organic titanium compound during synthesis. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The passivating agent includes compounds having a hydroxyl group, a carboxyl group, an ester group, an epoxy group, and the like. The group reacts with an organometallic compound to produce a metal alkoxide and a halogen compound. The organometallic compound reacts to produce a metal halide. Depending on the desired purpose, ester compounds, polyepoxides and polyhalogen compounds can be reacted with the alkali metal ends of the conjugated diene polymer to increase the molecular weight or form a branched structure. Suitable passivation agents are methanol, ethanol, n-propanol, n-butanol, second butanol, third butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexane Alcohol, 3 -18- This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) 474953 Α7 Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of invention 发明) Hexanol, 1 hept Alcohol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, octanol, nonanol, decanol, undecanol, Lauryl alcohol, allyl alcohol, cyclohexanol, cyclopentyl alcohol, and fluorenyl alcohol; phenols, such as o-cresol, m-cresol, p-cresol, p-allylphenol, 2,6-biol Tributyl phenol, and xylenol; organic carboxylic acids such as acetic acid, propionic acid, butyric acid, isoacetic acid, valeric acid, hexanoic acid, heptanoic acid, capric acid, myristic acid, stearic acid, Behenic acid and benzoic acid; carboxy compounds such as acetaldehyde, acetone, methyl ethyl ketone, diisopropyl ketone, acetone acetone, benzoaldehyde, diphenyl ketone and acetophenone; And esters, such as ethyl acetate, butyl propionate, diethyl adipate, benzoic acid methyl ester, terephthalic acid dimethyl ester and pyromellitic acid trimethyl. Water or carbonic acid gas can also be used as a passivating agent. The prerequisite is that its molar ratio can be controlled by industry. Examples of halogen-containing passivation agents include halogenated hydrocarbons such as phenyl chloride, methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, propyl chloride, propyl bromide, n-butyl chloride, n-butyl bromide And dibromoethane; a silicon halide compound represented by the general formula R4-nS i Xn (where R represents a hydrocarbon group having from 1 to 20 carbon atoms; X represents a halogen atom; η represents an integer from 1 to 4), Such as trimethylsilyl chloride, trimethylsilyl bromide, diethylsilyl dichloride, methylsilyl trichloride, third butylsilyl chloride, and tetrachlorosilane; by the general formula R4 -nS ηχη (where R represents a hydrocarbon group having from 1 to 20 carbon atoms; X represents a halogen atom; η represents an integer from 1 to 4) a tin halide compound such as trimethyltin chloride, trimethyl Bromide tin, diethyltin chloride, methyltin chloride, third butyltin chloride, and tin tetrachloride. These passivation agents can be used alone or in combination of two or more of these paper sizes. Applicable to China National Standard (CNS) A4 size (210X297 mm) (please read the precautions on the back first) and then order -19-474953 A7 B7 5 Description of the invention; When added to the polymerization system, a primary amine, a secondary amine, molecular hydrogen, an acetylene compound, a propane compound, etc. can also passivate the organic alkali metal compound. However, since it reacts inappropriately with titanium pentafluorene, it is preferable to use it in combination with the above-mentioned passivating agent. In this example, only the molar amount of the above-mentioned passivation agent is represented by " Z ". In the present invention, the addition amount of the passivation agent to the conjugated diene polymer prepared by using an organic alkali metal compound as a polymerization initiator corresponds to the relationship Formula: Please read the precautions of the back first and then fill in 1 and write 1 page -5 Μ-Z) / T i Under these conditions, the present invention is particularly highly hydrogenated. Therefore, the use of titanium dihalide (A) has Industrial titanium is used as a benchmark. In this group, 50% or more is particularly good. When titanium dihalide (A) is used, the special effect of the passivation is that a small amount of hydrogenation catalyst is used because industrially available compounds are used as raw materials. The reaction mixture of thorium and trimethylaluminum is used as the assembly point. In this example, the yield (A) of titanium dihalide pentafluoride must be 20% or more. The reaction mixture of pentamidine and trimethylaluminum can also be added to the reaction mixture as a reagent. In this example, the amount of the passivating agent added to the reaction mixture conforms to the relationship ...

A 佳，然後將該混合物添加於該聚合物溶液中進行氫化作用。該鈍化劑之添加量符合關係式：一0·5S(M -Z + A 1 一 Ti)/TiS2更佳。於此條件下，是爲本發明特別效應之高氫化活性可持續一段長時間，提供極大之工業優點。本紙張尺度適用中國國家標準（CNS ) Α4規格.（210Χ297公釐） 20 474953 A7 B7 五、發明説明4A is good, and then the mixture is added to the polymer solution for hydrogenation. The addition amount of the passivation agent conforms to the relational formula: -0.5S (M -Z + A 1 -Ti) / TiS2 is better. Under these conditions, the high hydrogenation activity of the special effect of the present invention can last for a long time, providing great industrial advantages. This paper size is applicable to China National Standard (CNS) A4. (210 × 297 mm) 20 474953 A7 B7 V. Description of Invention 4

請-先閱 -¾ : 背- 之注意/ I I i I 氫化作用可於實質上不含直鏈醚化合物之惰性烴溶劑中進行。該直鏈醚化合物包括二烷基醚與二烷基乙二醇，諸如二甲醚、二***、二一正一丙醚、二異丙醚、二一正一丁醚、乙二醇二甲醚、乙二醇二***、乙二醇二丙醚與乙二醇二丁醚。氫化系統中存在此種直鏈醚化合物會使觸媒之氫化活性降低，導致無法以少量該氫化觸媒達到高度氫化活性。本文中所使用之“實質上不含”一辭意指假如存在該直鏈醚化合物，其數量小到其效果不會顯現的程度。若每莫耳該觸媒有機鈦組份中存在〇·1莫耳或以上之直鏈醚化合物，該氫化觸媒之活性通常會降低。訂於存在三級胺化合物下進行氫化作用可以進一步加強以少量觸媒組份獲得之本發明高度氫化活性效果。本發明中可使用之三級胺係以通式：R11R12R13 經濟部中央標準局員工消費合作社印製 N (其中R11、R12與R13分別表示具有自1至2 0個碳原子之烴基，其可能含有一個三級胺基）表示。此等三級胺之實例包括三甲胺、三乙胺、三丁胺、Ν，Ν —二甲胺、Ν —乙基哌啶、Ν —甲基吡咯烷、Ν，Ν，Ν‘，Ν，一四甲基伸乙基二胺、Ν，Ν，Ν ‘，Ν，一四乙基伸乙基二胺、1 ，2 —二哌啶基乙烷、三甲基胺基乙基哌嗪、Ν , Ν ，Ν·，Ν “，Ν” 一五甲基伸乙基三胺以及Ν，Ν，—二辛基 -對一伸苯基二胺。亦可採用添加於聚合系統中以乙烯化該共軛二烯之三級胺。每莫耳鈦中，該三級胺化合物之存在量爲 0 · 0005至200莫耳爲佳，0 · 1至70莫耳特佳本紙張尺度適用中國國家標準（CNS ) A4規格（210X29*7公釐） -21 - 474953 A7 B7 五、發明説明（19 ) 使用有機鹼金屬化合物作聚合引發劑來均聚一 @ #車尼二烯或共聚一種共軛二烯與可共聚單體時，可於該系,統+ 添加一種三級胺化合物或醚化合物，以提高該共轭二燒之乙燒基結構（1 ’ 2 -鍵或3 ，4 一鍵）。其中以三級胺化合物爲佳。此處用以添加之三級胺化合物實例與上述者相同。直鍵醚化合物排除在可添加之醚化合物之外，因其會對上述氫化作用造成負面影響。適用之醚化合物實例包括環狀醚類，諸如四氫呋喃、2，5 -二甲基腭茂烷、2 ’ 2，5 ，5 —四甲基吗茂烷與2，2 -雙（2 -噚茂烷基）丙烷。於存在該有機鹼金屬化合物下之共軛二烯均聚或共聚作用可分批或連續進行。於本發明中可製得之經氫化共軛二烯（尤其是基於工業觀點考量）係經氫化嵌段共聚物，其包括一種共轭二烯聚合物嵌段（D)與乙烯基聚合物嵌段（S)，尤其是（Please read -¾: Note to the back- / I I i I Hydrogenation can be performed in an inert hydrocarbon solvent that is substantially free of linear ether compounds. The linear ether compounds include dialkyl ethers and dialkyl glycols, such as dimethyl ether, diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, and ethylene glycol dimethyl Ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, and ethylene glycol dibutyl ether. The presence of such linear ether compounds in the hydrogenation system will reduce the hydrogenation activity of the catalyst, resulting in the inability to achieve a high degree of hydrogenation activity with a small amount of the hydrogenation catalyst. The term "substantially free" as used herein means that if the linear ether compound is present, its amount is small to such an extent that its effect will not be exhibited. If 0.1 mol or more of a linear ether compound is present in the organic titanium component of the catalyst per mole, the activity of the hydrogenation catalyst will generally be reduced. The hydrogenation in the presence of a tertiary amine compound can further enhance the high hydrogenation activity effect of the present invention obtained with a small amount of a catalyst component. The tertiary amines that can be used in the present invention are printed by the general formula: R11R12R13 N printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (where R11, R12, and R13 represent hydrocarbon groups having from 1 to 20 carbon atoms, which may contain A tertiary amino group). Examples of such tertiary amines include trimethylamine, triethylamine, tributylamine, N, N-dimethylamine, N-ethylpiperidine, N-methylpyrrolidine, N, N, N ', N, Tetramethylethylenediamine, N, N, N ', N, Tetraethylethylenediamine, 1,2-Dipiperidinylethane, Trimethylaminoethylpiperazine, N , Ν, Ν ·, Ν ", Ν" pentamethylethylenetriamine and N, N, -dioctyl-p-phenylenediamine. A tertiary amine added to a polymerization system to ethylenize the conjugated diene may also be used. The amount of the tertiary amine compound per mole of titanium is preferably from 0. 0005 to 200 moles, and from 0. 1 to 70 moles. This paper is sized to the Chinese National Standard (CNS) A4 (210X29 * 7). (Mm) -21-474953 A7 B7 V. Description of the invention (19) When using an organic alkali metal compound as a polymerization initiator to homopolymerize one ## 车尼 diene or copolymerize a conjugated diene and a copolymerizable monomer, In this system, a + tertiary amine compound or an ether compound is added to improve the ethylenyl structure of the conjugated dioxane (1 ′ 2-bond or 3,4 one bond). Among them, tertiary amine compounds are preferred. Examples of the tertiary amine compound to be added here are the same as those described above. Straight-chain ether compounds are excluded from the range of ether compounds that can be added because they negatively affect the hydrogenation described above. Examples of suitable ether compounds include cyclic ethers, such as tetrahydrofuran, 2,5-dimethylphosphorane, 2'2,5,5-tetramethylmorphomones and 2,2-bis (2-fluorene Alkyl) propane. The homopolymerization or copolymerization of the conjugated diene in the presence of the organic alkali metal compound may be performed batchwise or continuously. The hydrogenated conjugated diene obtainable in the present invention (especially from an industrial point of view) is a hydrogenated block copolymer comprising a conjugated diene polymer block (D) and a vinyl polymer. Paragraph (S), especially (

D S)二嵌段共聚物、（S-D-S)三嵌段共聚物 aaiwM μβμιιμ (請先閲讀背面之注意事項再填寫本頁) —訂-----111^ 線' 經濟部智慧財產局員工消費合作社印製 (D — S — D - S)四嵌段共聚物 D )五嵌段共聚物、（c )DS) Diblock copolymer, (SDS) triblock copolymer aaiwM μβμιιμ (Please read the precautions on the back before filling out this page) —Order ----- 111 ^ Line 'Employees ’Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printed (D — S — D-S) tetrablock copolymer D) pentablock copolymer, (c)

(D - S D — S — D — S — η基團共聚物（其中c係偶合劑殘餘；η係自3至8之整數）及其混合物，該共軛二烯嵌段之雙鍵係經氫化。更特別的是包括苯乙烯聚合物嵌段與丁二烯聚合物嵌段，而且該丁二烯聚合物嵌段之雙鍵經氫化之經氫化嵌段共聚物就作爲橡膠組合物之原料橡膠、樹脂改良劑或膠粘劑之熱塑性彈性體而言極爲本纸張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 22- 474953 經濟部中央標準局員工消費合作社印裝 A7 ______ B7五、發明説明4 ) 重要。該氫化反應一般係以分子氫進行，其通常係以氣體狀態導入該共.範二烯聚合物中。該氫化作用係以攪拌進行，使所導入之氫與該聚合物迅速充分接觸。該反應可爲分批反應或連續反應。每100g該共軛二烯聚合物添加0 · 00 1至5 m m ο 1之組份即已充足。此用量足以充分氫化該共軛二烯聚合物之雙鍵，並且實質上不會氫化該共聚物中芳族環之雙鍵，如此實現極高度之氫化選擇性。該氫化作用可以超過20mm ο 1之用量進行，但是結果並不會較佳，因爲如此較不經濟，而且使反應後之觸媒去除作用複雜化。該觸媒之較佳用量係每100g該聚合物使用0.002 至lmmo 1觸媒，以〇 · 005至0 · 2mmo 1特佳〇組份（A )可於氫化作用開始前全部添加或分成二或多個部分添加。後者實例中，該反應開始前所添加之部分或該反應期間所添加之其餘部分可連續或間歇性進行。較佳之添加模式中，於開始反應之前添加5至9 9重量％部分，其餘部分係當該氫化作用以最終所達到之程度爲準之 3 0至9 5%時，分批添加或連續添加。根據此模式與於反應之前添加全部觸媒實例相較，組份（A )所需之用量減少。該氫化反應通常於自0°C至2 0 0 t溫度範圍內進行。假如該溫度低於0 °C，反應速率低而且增加組份（A ) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -23- 474953 A7 ______ B7 五、發明説明2(j ) 之所需量。因此，其不經濟。若以高於2 Ο 0 °C溫度進行 ’該反應系統容易產生副反應、分解或膠凝，而且該觸媒會不具活性，因此降低氫化活性。較佳之溫度係自2 0至 1 8 0 °C。較佳之氫化作用之氫壓力係0 · 1至lOMPa。於小於0 . IMP a氫壓力下，該反應速率過低，而且提高氫化作用之程度。假如壓力超過1 OMP a，候該高壓力之故，該氫化作用幾乎完全完成，其並無特殊意義而且引發不必要之副反應。更佳之氫壓力係0 · 2至3 Μ P a。最適之氫壓力視其與該觸媒用量等之關係而定。實際上，在上述適用範圍內，該觸媒用量遞減爲佳，所以選擇較高之氫壓力爲佳。依照所需之氫化程度自上述範圍內適當地選擇時間與壓力。經濟部中央標準局員工消費合作社印裝根據本發明，視所需之目的而定，該共軛二烯聚合物或共軛二烯/乙烯基芳族烴共聚物之雙鍵可氫化成任何所需程度。若情況需要，該氫化程度可穩定地高達9 5%或以上，甚至高達9 8 %或以上。以1 Η — N M R可輕易地測量所達到之氫化程度。當達到任何氫化程度（例如，3至9 5 %共軛二烯嵌段中之全部雙鍵被氫化時）時，可停止該氫化反應。其係於所述之氫化程度達成時，藉由控制氫之進料或鈍化該觸媒達成。若情況需要，可以在氫化後自該聚合物溶液去除觸媒殘餘，並自該溶液分離經氫化之聚合物。例如，藉由在反本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -24- 474953 經濟部智慧財產局員工消費合作社印製 A7 __B7卜五、發明説明（22 ) 應溶液中添加一種極性溶劑使該聚合物沉澱，其中該極性溶劑係該經氫化聚合物之不良溶劑，諸如丙酮或一種醇；將該反應溶液倒入熱水中並攪拌之，該聚合物與該溶劑一起蒸餾；或直接加熱該反應溶液以蒸發該溶劑，而分離該聚合物。本發明之氫化方法主要特徵係所使用之觸媒減量，而且不使用共觸媒。因此，即使該觸媒殘留在該經氫化聚合物中，其不會對該經氫化聚合物之物理特性造成不良影響。此外，大部分觸媒係於該聚合物分離過程中分解或與該分離。因此，不特別需要任何用以淸洗或去除該觸媒之特殊操作。此外，因爲不使用鹼金屬共觸媒，不需要觸媒組合之最適化。因此，可以經由極簡單而且結果重現性良好之方法完成該氫化作用。本發明方法之第二特徵係該觸媒於廣泛溫度範圍內對於烯烴具有高度氫化活性，此係其具有良好耐熱性之故，而且即使於相當低溫之下，其不易顯示氫化速率下降。參考下列實施例可以更詳細說明本發明，不過本發明並不受限於此。實施例1 於5 1具有攪拌器之經套管壓熱器中裝塡1 6 6 7 g 環己烷、12 · lmmo 1第二丁基鋰與4 . 5mmo 1 之N，N，N ‘，N，一四甲基伸乙基二胺，並於其中添加 2 5 0 g苯乙烯之3 0%環己烷溶液。於7 5 °C進行聚合作用。於該反應系統中添加1 1 6 7 g 1 ，3 —丁二烯之本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） .25^ (請先閱讀背面之注意事項再填寫本頁) -裝_(D-SD — S — D — S — η group copolymer (where c is the coupling agent residue; η is an integer from 3 to 8) and mixtures thereof, and the double bond system of the conjugated diene block is hydrogenated More specifically, it includes a styrene polymer block and a butadiene polymer block, and the hydrogenated block copolymer whose double bond of the butadiene polymer block is hydrogenated is used as the raw rubber of the rubber composition. For thermoplastic elastomers of resin modifiers or adhesives, this paper size is applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm) 22- 474953 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 ______ B7 V. Inventions Note 4) Important. The hydrogenation reaction is generally carried out with molecular hydrogen, which is usually introduced into the co-vanadiene polymer in a gaseous state. The hydrogenation is performed by stirring, so that the introduced hydrogen is brought into full and rapid contact with the polymer. This reaction may be a batch reaction or a continuous reaction. It is sufficient to add a component of 0.001 to 5 m m ο 1 per 100 g of the conjugated diene polymer. This amount is sufficient to sufficiently hydrogenate the double bond of the conjugated diene polymer, and substantially does not hydrogenate the double bond of the aromatic ring in the copolymer, thus achieving extremely high hydrogen selectivity. The hydrogenation can be performed in an amount exceeding 20 mm ο 1, but the result is not good because it is less economical and complicates the catalyst removal effect after the reaction. The preferred amount of the catalyst is 0.002 to lmmo 1 catalyst per 100 g of the polymer, and 0.005 to 0.2 mmo 1 is particularly preferred. Component (A) can be added or divided into two or two before hydrogenation begins. Multiple sections added. In the latter case, the part added before the reaction is started or the rest added during the reaction may be performed continuously or intermittently. In a preferred addition mode, 5 to 99% by weight is added before the reaction is started, and the rest is added in batches or continuously when the hydrogenation is 30 to 95% based on the degree finally achieved. According to this mode, the amount of component (A) required is reduced compared to the case where all catalyst examples are added before the reaction. The hydrogenation reaction is usually carried out at a temperature ranging from 0 ° C to 200 t. If the temperature is lower than 0 ° C, the reaction rate is low and the component (A) is increased. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -23- 474953 A7 ______ B7 V. Invention Description 2 (j ). Therefore, it is not economical. If it is carried out at a temperature higher than 200 ° C, the reaction system is liable to cause side reactions, decomposition or gelation, and the catalyst will be inactive, thus reducing hydrogenation activity. The preferred temperature is from 20 to 180 ° C. The preferred hydrogenation hydrogen pressure is from 0.1 to 10 MPa. At less than 0.1 IMP a hydrogen pressure, the reaction rate is too low, and the degree of hydrogenation is increased. If the pressure exceeds 1 OMP a, when the high pressure is reached, the hydrogenation is almost completely completed, which has no special meaning and causes unnecessary side reactions. A more preferred hydrogen pressure is from 0.2 to 3 MPa. The optimum hydrogen pressure depends on its relationship with the dosage of the catalyst. In fact, in the above range of application, the amount of catalyst used is gradually reduced, so it is better to choose a higher hydrogen pressure. The time and pressure are appropriately selected from the above ranges according to the required degree of hydrogenation. According to the present invention, the double bond of the conjugated diene polymer or conjugated diene / vinyl aromatic copolymer can be hydrogenated to any place according to the present invention, depending on the desired purpose. Need degree. If necessary, the degree of hydrogenation can be as high as 95% or more, or even 98% or more. The degree of hydrogenation achieved can be easily measured with 1 Η — N M R. When any degree of hydrogenation is reached (for example, when all double bonds in the 3 to 95% conjugated diene block are hydrogenated), the hydrogenation reaction can be stopped. It is achieved when the stated degree of hydrogenation is achieved by controlling the hydrogen feed or passivating the catalyst. If necessary, catalyst residues can be removed from the polymer solution after hydrogenation, and the hydrogenated polymer can be separated from the solution. For example, by applying the Chinese National Standard (CNS) A4 specification (210X297 mm) -24-474953 on the paper size of the paper, printed A7 __B7 by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Explanation of the invention (22) in solution Add a polar solvent to precipitate the polymer, where the polar solvent is a poor solvent for the hydrogenated polymer, such as acetone or an alcohol; pour the reaction solution into hot water and stir it, the polymer together with the solvent Distill; or directly heat the reaction solution to evaporate the solvent to isolate the polymer. The main feature of the hydrogenation method of the present invention is the reduction of the catalyst used without using a co-catalyst. Therefore, even if the catalyst remains in the hydrogenated polymer, it does not adversely affect the physical properties of the hydrogenated polymer. In addition, most catalysts are decomposed or separated from the polymer during the polymer separation process. Therefore, no special operation for washing or removing the catalyst is particularly required. In addition, because no alkali metal co-catalyst is used, no optimization of the catalyst combination is required. Therefore, the hydrogenation can be performed by a very simple method with good reproducible results. The second feature of the method of the present invention is that the catalyst has a high hydrogenation activity for olefins over a wide temperature range. This is because it has good heat resistance, and it is not easy to show a decrease in the hydrogenation rate even at a relatively low temperature. The present invention can be explained in more detail with reference to the following examples, but the present invention is not limited thereto. Example 1 A 166,7 g of cyclohexane, 12 · lmmo 1 second butyllithium and 4.5 mmmo 1 of N, N, N ', were placed in a sleeved autoclave with a stirrer. N, tetramethylethylene diamine, and a 30% cyclohexane solution of 250 g of styrene was added thereto. Polymerization was carried out at 7 5 ° C. Add 1 1 6 7 g 1, 3-butadiene to this reaction system. The paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm). 25 ^ (Please read the precautions on the back before (Fill in this page)-equipment_

、1T _線 474953 A7 B7 五、發明説明么 ) 經濟部中央標準局員工消費合作社印褽 3 0%環己烷溶液，並於其中添加2 5 0 g苯乙烯之3 0 %環己烷溶液繼續聚合製得一種S B S (苯乙烯一丁二嫌 -苯乙烯）三嵌段共聚物。以微量水鈍化二個百分比之零丁基鋰，留下11 · 9mmo 1之活性鋰。於所形成之新鮮聚合物（living polymer )溶液中添加12· 37 mm ο 1乙醇以鈍化該聚合物末端。分別於室溫下攪拌0 · 9 4mmo 1二氯化鈦五圜之環己烷溶液（Wako Pure Chemical Industries，Ltd·所製）與1 · 8 8mmo 1之三甲基鋁100小時。取出一半該產物，並蒸發之去除該揮發性物質。將其殘餘溶解於氚苯溶液中，並以iH — NMR分析。於7 · 15ΡΡΠ1由氚苯所致之尖峰作爲參考尖峰，每個尖峰與專業著作（】· Am. Chem. Soc·，第 100 卷，36 1 1 -36 1 3(1 978))中之泰比型 1 Η — N M R光譜比較以確認其一致性。亦可確認 (C Ρ ) 2 T i C 1 M e所致之尖峰。由該尖峰比率揭示泰比型錯合物與（CP) 2Ti C IMe之比率爲7 : 3 ° 將另一半該反應產物添加於上述製備之S B S聚合物溶液，於其中吹入氫使部分壓力爲0.7MPa ’於此條件下以8 0 t進行氫化作用。3 0分鐘之後’氫化程度到達 9 9 %。 Μ 係 1 1 . 9 m m ο 1 ，Z 係 1 2 · 3 7 m ιη ο 1 ’ A1 係〇.94mmol 而 Ti 係 0.47mmol ，其中（M — Ζ + A 1 一 Ti)/Ti 爲〇，（ Μ Ζ ) / Τ i 爲本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）請先閱讀背面之注意事項再、 1T _line 474953 A7 B7 V. What is the invention?) Employees of the Central Standards Bureau of the Ministry of Economy, Consumers ’Cooperative, printed 30% cyclohexane solution, and added 250 g of styrene 30% cyclohexane solution to continue. A SBS (styrene-butadiene-styrene) triblock copolymer was prepared by polymerization. Two percentages of zero butyl lithium were passivated with a trace of water, leaving 11.9 mmo 1 of active lithium. To the resulting living polymer solution was added 12.37 mm ο 1 ethanol to passivate the polymer ends. A cyclohexane solution (manufactured by Wako Pure Chemical Industries, Ltd.) of 0.94 mmo 1 of titanium dichloride and pentafluoride and trimethylaluminum of 1.8 8 mmo 1 were stirred at room temperature for 100 hours. Half of the product was removed and evaporated to remove the volatiles. The residue was dissolved in a toluene solution and analyzed by iH-NMR. In 7.15PPII1, the peaks caused by toluene are used as reference peaks. Each peak is related to the professional work (]. Am. Chem. Soc., Vol. 100, 36 1 1 -36 1 3 (1 978)). Type 1 Η — NMR spectra were compared to confirm their consistency. The peak caused by (C) 2 T i C 1 Me can also be confirmed. The peak ratio reveals that the ratio of the Tybee complex to (CP) 2Ti C IMe is 7: 3 °. The other half of the reaction product is added to the SBS polymer solution prepared above, and hydrogen is blown in to make part of the pressure 0.7MPa 'Under this condition, hydrogenation was performed at 80 t. After 30 minutes, the degree of hydrogenation reached 99%. Μ is 1 1. 9 mm ο 1, Z is 1 2 · 3 7 m ο 1 'A1 is 0.94 mmol and Ti is 0.47 mmol, where (M — Zn + A 1 -Ti) / Ti is 0, ( Μ) / Τ i is the standard of the paper. Applicable to China National Standard (CNS) A4 (210X297 mm). Please read the precautions on the back first.

訂 •26- 474953 A7 B7 五、發明説明& 實施例2 請先閱讀背面之注意事項再填寫本頁如實施例1之相同方法，使用一種有機鹼金屬化合物作爲聚合引發劑製備一種S B S三嵌段共聚物之新鮮聚合物溶液，並於其中添加13 · 78mmo 1乙醇以鈍化該聚合物末端。分別於室溫下攪拌0 · 9 4mmo 1之二氯化鈦五圜環己院溶液（Wako Pure Chemical Industries，Ltd.所製 )與2 · 82mmo 1之三甲基鋁72小時。取出一半該產物，並蒸發之去除該揮發性物質。將其殘餘溶解於氚苯溶液中，並以1H — NMR分析。於7 · 1 5p pm由氚苯所致之尖峰作爲參考尖峰，每個尖峰與專業著作（I. Am • Chem. Soc·，第 100 卷，36 11 ·361 3( 1 978))中之泰比型 1 Η — N M R光譜比較以確認其一致性。亦可確認 (CP) 2Τ i C IMe所致之尖峰。由該尖峰比率揭示泰比型錯合物與（CP) 2 丁 i C IMe之比率爲6 : 4。經濟部中央標準局員工消費合作社印製將另一半該反應產物添加於上述製備之S B S聚合物溶液，於其中吹入氫使部分壓力爲0.7MPa ，於此條件下以8 0 °C進行氫化作用。3 0分鐘之後，氫化程度到達 9 6 %。 Μ 係 11 · 9mmo 1，Z 係 13 · 78mmo 1， A1 係 1 · 41mmo 1 而 T i 係〇 · 4 7mmo 1 ，其中（M — Z + A1 — Ti)/Ti 爲一 2, (Μ 一 Z ) / Ti 爲一 4。本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 27- 474953 經濟部中央標準局員工消費合作社印裝 A7 ____ _B7五、發明説明“）實施例3 如實施例1之相同方法，使用一種有機鹼金屬化合物作爲聚合引發劑製備一種SBS三嵌段共聚物之新鮮聚合物溶液，並於其中添加11·66mmo1三甲基甲矽烷基化氯以鈍化該聚合物末端。分別於室溫下攪拌0 · 9 4mm ο 1之二氯化欽五圜環己院溶液（Wako Pure Chemical Industries，Ltd.所製）與2·82mmo1之三甲基鋁100小時。取出一半該產物，並蒸發之去除該揮發性物質。將其殘餘溶解於氚苯溶液中，並以iH—NMR分析。於7·15ppm由氚苯所致之尖峰作爲參考尖峰，每個尖峰與專業著作（Am. Chem· Soc·，第 100 卷，361 1 -361 3( 1978))中之泰比型1 Η -N M R光譜比較以確認其一致性。亦可確認 (CP) 2T i C IMe所致之尖峰。由該尖峰比率揭示泰比型錯合物與（CP) 2T i C IMe之比率爲7 : 3。將另一半該反應產物添加於上述製備之S B S聚合物溶液，於其中吹入氫使部分壓力爲0 . 7MP a，於此條件下以8 0 °C進行氫化作用。3 0分鐘之後，氫化程度到達 9 5 % 〇 1^係11.9111111〇1，冗係11.66111111〇1， A1 係〇 · 705mmo 1 而 T i 係〇 · 47mino 1 ，其中（Μ - Z + A 1 一 Ti)/Ti 爲 1， (Μ 一 Z ) / Ti 爲 0.5。本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -28- 474953 經濟部中央標準局員工消費合作社印装 • A7 _____B7 _五、發明説明“) 實施例4 、如實施例1之相同方法，使用一種有機鹼金屬化合物作爲聚合引發劑製備一種S B S三嵌段共聚物之新鮮聚合物溶液，並於其中添加1 1 · 9mmo 1三甲基甲矽烷基化氯以鈍化該聚合物末端。分別於室溫下攪拌0·Imo1之二氯化鈦五圜甲苯溶液（Wako Pure Chemical Industries，Ltd.所製）與〇·2m之三甲基鋁60小時。取出一半該產物，並蒸發之去除該揮發性物質，再結晶該殘餘物由甲苯中製得 1 4 g產物。再次由甲苯與含三甲基鋁之戊烷中再結晶該產物，製得9 · 5 g微紅之橙色晶體。將該晶體溶解於氚苯溶液中，並以iH — NMR分析。於7 · 15ppm由氚苯所致之尖峰作爲參考尖峰，每個尖峰與專業著作（Am • Chem· Soc·，第 100 卷，361 1-361 3(1978))中之泰比型1 Η - NMR光譜比較以確認其一致性。.其亦可確認不存在雜質〇將該晶體（0 · 2 0 m m ο 1 )之環己烷溶液添加於上述製備之S B S聚合物溶液，於其中吹入氫使部分壓力爲1 . 2 Μ P a ，於此條件下以1 〇 0 °C進行氫化作用。於氫化程度到達80%時，另外於其中添加0·11 mmo 1晶體之環己烷溶液，繼續進行該氫化作用。30 分鐘之後，氫化程度到達9 9 %。 Μ 係 11 ·9πΐΓηο1，Z 係 11 ·9πιιηο1，本紙張尺度適用中國國家標準(CNS ) Α4規格（210X297公釐） " " {請先閲讀背面之注意ί項再填寫本頁) 訂 -29- 474953 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明k ) A 1 (泰比錯合物中之A1)係0 .31m mol而Ti 係 0.31mmol，其中（Μ — Ζ + A 1 一 Ti)/Ti 爲〇，（M — Z)/ Ti 爲 0。實施例5 於51具有攪拌器之經套管壓熱器中裝塡I667g 環己烷、19.5111111〇1正丁基鋰與5.8111111〇1之 N，N，N‘，N，一四甲基伸乙基二胺，並於其中添加 2 5 0 g苯乙烯之3 0%環己烷溶液。於7 5 °C進行聚合作用。於該反應系統中添加1417gl，3 —丁二烯之 3 0%環己烷溶液，繼續聚合製得一種S B (苯乙烯一丁二烯）二嵌段共聚物。以微量水鈍化一個百分比.之正丁基鋰，留下19 · 3mmo 1之活性鋰。於所形成之新鮮聚合物（living polymer)溶液中添加2 · 9 mm ο 1四氯化錫使之偶合，形成Sn -（D — S) η基團嵌段聚合物。於該反應混合物中添加7 · 7 m m ο 1甲醇以鈍化該聚合物末端。於上述製備之SB聚合物溶液中添加0·50 mm ο 1與實施例4相同之泰比型錯合物環己烷溶液’並於其中吹入氫使部分壓力爲〇 · 7MP a，於此條件下以 8 0°C進行氫化作用。3 0分鐘之後，氫化程度到達9 8 % 〇 Μ 係 19 ·3πιιηο1，Z 係 2·9χ4 + 7 .7 =19 · 3mmol ，A1 (泰比錯合物中之A 1)係本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) Γ -30 - 474953 A7 B7 五、發明説明“） 0·50mmo1而Ti係〇·5〇mmo1 ，其中 Μ 一 Z + A 1 一 Μ - Z)/ Ti 爲〇•• 26- 474953 A7 B7 V. Description of the invention & Example 2 Please read the notes on the back before filling in this page as in Example 1, using an organic alkali metal compound as a polymerization initiator to prepare a SBS triple insert A fresh polymer solution of the block copolymer was added with 13.78 mmo 1 ethanol to passivate the polymer ends. At room temperature, 0.94 mmo 1 of titanium dichloride pentafluorene cyclopentane solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 2.82 mmo 1 of trimethylaluminum were stirred for 72 hours. Half of the product was removed and evaporated to remove the volatiles. The residue was dissolved in a toluene solution and analyzed by 1H-NMR. At 7 · 1 5p pm, the spikes caused by toluene were used as reference spikes, and each spike was related to professional works (I. Am • Chem. Soc ·, Vol. 100, 36 11 · 361 3 (1 978)) Type 1 Η — NMR spectra were compared to confirm their consistency. It is also possible to confirm the spike caused by (CP) 2T i C IMe. The peak ratio revealed that the ratio of the Tybee complex to (CP) 2 but i C IMe was 6: 4. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, adding the other half of the reaction product to the SBS polymer solution prepared above, blowing hydrogen into it to make part of the pressure 0.7MPa, under this condition hydrogenation at 80 ° C . After 30 minutes, the degree of hydrogenation reached 96%. Μ is 11 · 9mmo 1, Z is 13 · 78mmo 1, A1 is 1. · 41mmo 1 and T i is 0.4 · 7mmo 1, where (M — Z + A1 — Ti) / Ti is -2, (Μ-Z ) / Ti is a 4. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 27- 474953 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 ____ _B7 V. Description of the invention ") Example 3 The same method as in Example 1, A fresh polymer solution of an SBS triblock copolymer was prepared using an organic alkali metal compound as a polymerization initiator, and 11.66mmo1 trimethylsilyl chloride was added to passivate the polymer ends. At room temperature, respectively. Stir 0 · 9 4mm ο 1 bis chlorinated pentamidine hexacycline solution (made by Wako Pure Chemical Industries, Ltd.) and 2.82mmo1 trimethylaluminum for 100 hours. Remove half of this product and evaporate it. Remove this volatile substance. Dissolve the residue in toluene solution and analyze by iH-NMR. The peaks caused by toluene at 7.15ppm are used as reference peaks. Each peak is related to the professional work (Am. Chem · Soc). ·, Vol. 100, 361 1 -361 3 (1978)) The comparison of the Tabby 1 Η-NMR spectrum to confirm the consistency. The peak caused by (CP) 2T i C IMe can also be confirmed. From this peak Ratio reveals Tybee type error The ratio of the compound to (CP) 2T i C IMe was 7: 3. The other half of the reaction product was added to the SBS polymer solution prepared above, and hydrogen was blown into it to make part of the pressure 0.7 MPa, under these conditions The hydrogenation was carried out at 80 ° C. After 30 minutes, the degree of hydrogenation reached 95% 〇1 ^ system 11.9111111〇1, redundant system 11.66111111〇1, A1 system 0.705mmo 1 and T i system 0.447mino 1, Among them, (Μ-Z + A 1-Ti) / Ti is 1, and (Μ-Z) / Ti is 0.5. This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -28- 474953 Central Ministry of Economic Affairs Standard Bureau employee consumer cooperative printing • A7 _____B7 _V. Description of the invention ") Example 4, the same method as in Example 1, using an organic alkali metal compound as a polymerization initiator to prepare a fresh polymerization of an SBS triblock copolymer The polymer solution was added with 1 1.9 mmo 1 trimethylsilyl chloride to passivate the polymer terminal. A 0 · Imo1 solution of titanium dichloride pentaoxene in toluene (manufactured by Wako Pure Chemical Industries, Ltd.) and a trimethyl aluminum of 0.2 m were stirred at room temperature for 60 hours, respectively. One half of the product was taken out, and the volatile matter was removed by evaporation, and the residue was recrystallized to obtain 14 g of the product from toluene. The product was recrystallized from toluene and trimethylaluminum-containing pentane again to obtain 9.5 g of reddish orange crystals. The crystals were dissolved in a toluene solution and analyzed by iH-NMR. At 7.15ppm, the peaks caused by toluene are used as reference peaks. Each peak is related to the Taby type 1 in the professional work (Am • Chem · Soc ·, Vol. 100, 361 1-361 3 (1978))- NMR spectra were compared to confirm their consistency. It can also be confirmed that there are no impurities. A cyclohexane solution of the crystal (0. 20 mm ο 1) is added to the SBS polymer solution prepared above, and hydrogen is blown into it to make a partial pressure of 1.2 MPa. a, hydrogenation at 100 ° C under these conditions. When the degree of hydrogenation reached 80%, a cyclohexane solution of 0.11 mmo 1 crystals was added thereto, and the hydrogenation was continued. After 30 minutes, the degree of hydrogenation reached 99%. Μ series 11 · 9πΐΓηο1, Z series 11 · 9πιιηο1, this paper size applies Chinese National Standard (CNS) Α4 specification (210X297 mm) " " {Please read the note on the back first and then fill out this page) Order-29 -474953 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention k) A 1 (A1 in the Tybee complex) is 0.31 m mol and Ti is 0.31 mmol, where (M — Zn + A 1-Ti) / Ti is 0, and (M — Z) / Ti is 0. Example 5 In a sleeved autoclave with a stirrer, 1667 g of cyclohexane, 19.15111111〇1 n-butyllithium, and 5.8111111〇1 of N, N, N ', N, and tetramethyl ethylene glycol were charged. Diamine, and a 250% solution of styrene in 30% cyclohexane was added thereto. Polymerization was carried out at 7 5 ° C. 1417gl, a 30% cyclohexane solution of 3-butadiene was added to the reaction system, and polymerization was continued to obtain an SB (styrene-butadiene) diblock copolymer. A percentage of n-butyl lithium was passivated with a trace of water, leaving 19 · 3mmo 1 of active lithium. To the formed living polymer solution, 2 · 9 mm ο 1 tin tetrachloride was added to couple them to form a Sn- (D-S) η group block polymer. To the reaction mixture was added 7 · 7 m m ο 1 methanol to passivate the polymer terminal. To the SB polymer solution prepared above was added 0.50 mm ο 1 the same Thai ratio type complex cyclohexane solution 'as in Example 4 and hydrogen was blown into it to make a partial pressure of 0.7 MP a, here Hydrogenation was performed at 80 ° C under conditions. After 30 minutes, the degree of hydrogenation reached 98%. OM series 19 · 3πιιηο1, Z series 2.9χ4 + 7.7 = 19 · 3mmol, A1 (A1 in the Tybee complex) is a paper standard suitable for China. National Standard (CNS) A4 specification (210X297mm) (Please read the notes on the back before filling this page) Γ -30-474953 A7 B7 V. Description of the invention ") 0 · 50mmo1 and Ti series 0.5 · 50mmo1, Where M-Z + A 1-M-Z) / Ti is 〇

T / T i 爲〇實施例6T / T i is 〇 Example 6

以同實施例1相同方式，於室溫下攪拌0·94 mmo 1二氯化鈦五圜之環己烷溶液與1 · 88mni〇 1 之三甲基鋁1 0 0小時。以1 H — NMR分析一半該反應產物，以確認泰比型錯合物形成。於另一半中添加 0 · 24mmo 1乙醇，並以25°C保存該產物30天。如實施例1之相同方法，使用一種有機鹼金屬化合物作爲聚合引發劑製備一種S B S三嵌段共聚物之新鮮聚合物溶液，並於其中添加11.9mmo1乙醇以鈍化該聚合物末端。於該S B S聚合物溶液中添加該含有泰比型錯合物之經保存反應產物，並於其中吹入氫使其部分壓力爲 0 · 7 Μ P a ，於此條件下以8 0 °C進行氫化作用。3 0 分鐘之後，氫化程度到達9 9 %。經濟部中央標準局員工消费合作社印製係 1 1 · 9 m m ο 1，Z 係 1 1 · 9 + 0 · 2 4 = 12· 14mmol ，A1 係〇.94mmol 而 Ti 係 0.47mmol，其中（Μ — Ζ + A 1 — T i ) / T i 爲 0 · 5。實施例7 如實施例1之相同方法，使用一種有機鹼金屬化合物本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） • 31 - 474953 A7 B7 經濟部中央標準局員工消費合作社印裝五、發明説明“) 作爲聚合引發劑製備一種S B S三嵌段共聚物之新鮮聚合物溶液，並於其中添加11 · 9mmo乙醇以鈍化該聚合物末端。分別於室溫下將0 · lmo 1之雙（甲基環戊二烯基 )二氯化鈦五圜（由 Nippon Fine Chemical Co· Ltd·所製）與0 · 3m ο 1之三甲基鋁之己烷溶液混合並攪拌7 0小時。蒸發該反應混合物以去除揮發性物質，再結晶該殘餘物。以實施例4中分析泰比試劑之相同方式以1 Η - N M R 分析該晶體。於7 . 1 5 p p m由氚苯所致之尖峰作爲參考尖峰，每個尖峰與專業著作（J. Am. Chem. Soc.，第100 卷，36Π-3613(1978))中之泰比型1 Η - NMR光譜比較。結果，於7 · 9 4ppm處觀察到泰比型錯合物特有之伸甲基交聯尖峰，得似確認上述化合物已形成。將該晶體（0 . 2 0 m m ο 1 )之環己烷溶液添加於上述製備之S B S聚合物溶液，於其中吹入氫使部分壓力爲1 · 2MPa ，於此條件下以90°C進行氫化作用。於氫化程度到達8 0%時，另外於其中添加0 . 2 0 mmo 1晶體之環己烷溶液，繼續進行該氫化作用。3 0 分鐘之後，氫化程度到達9 9 %。 Μ係 1 1 · 9mmo 1，Z 係 1 1 · 9mmo 1， A1 (泰比錯合物中之A1)係0.40mmol而Ti 係 0.40mmol，其中（Μ — Z + A 1 一 T i ) / T i 爲 0。 (請先閱讀背面之注意事項再填寫本頁) Γ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 32 474953 經濟部中央標準局員工消費合作社印裝 A7 B7五、發明説明心) 實施例8 如實施例1之相同方法，使用一種有機鹼金屬化合物作爲聚合引發劑製備一種S B S三嵌段共聚物之新鮮聚合物溶液，並於其中添加1 1 · 9mmo 1乙醇以鈍化該聚合物末端。分別於室溫下將0 · lmo 1之雙（正丁基環戊二烯基）二氯化欽五圜（由 Nippon Fine Chemical Co· Ltd.所製 )與0 · 3m ο 1之三甲基鋁己烷溶液混合並攪拌7 0小時。蒸發該反應混合物以去除揮發性物質，再結晶該殘餘物。以實施例4中分析泰比試劑之相同方式以1 Η - N M R 分析該晶體。於7 · 1 5 p p m由氚苯所致之尖峰作爲參考尖峰，每個尖峰與專業著作（J. Am. Chem· Soc·，第100卷，36 1 1 -36 1 3( 1 978))中之泰比型1H-NMR光譜比較。結果，於7 · 9 4 p pm處觀察到泰比型錯合物特有之伸甲基交聯尖峰，得以確認上述化合物已形成。將該晶體（0 · 20mmo 1 )之環己烷溶液添加於上述製備之S B S聚合物溶液，於其中吹入氫使部分壓力爲1 . 2 Μ P a，於此條件下以9 0 °C進行氫化作用。於氫化程度到達8 0%時，另外於其中添加0 . 2 0 mmo 1晶體之環己烷溶液，繼續進行該氫化作用。30 分鐘之後，氫化程度到達9 9 %。 Μ係 1 1 · 9mmo 1，Z 係 11 · 9mmo 1 ， A 1 (泰比錯合物中之A 1.)係0 · 4〇mmo 1而丁 i 係 0.40mmol，其中（Μ — Z + A 1 一本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） •33· 474953 ,m^2；o - A7 - ' __ B7 _ 五、發明説明（刈） T i ) / T i 爲〇。 (請先閲讀背面之注意事項再填寫本頁) 對照實例1 如實施例1之相同方法，使用一種有機鹼金屬化合物作爲聚合引發劑製備一種S B S三嵌段共聚物之新鮮聚合物溶液，並於其中添加1 1 . 9 m m ο 1乙醇以鈍化該聚合物末端。於該溶液中添加4.7mmo1第二丁基鋰，並另外添加0 . 4 7 m m ο 1由Aldrich製之泰比試劑。於其中吹入氫使部分壓力爲〇 . 7 Μ P a，於此條件下以 8 0 °C進行氫化作用。3 0分鐘之後，氫化程度到達3 3 % 〇In the same manner as in Example 1, a 0.994 mmo 1 solution of titanium dichloride pentafluorene in cyclohexane and 1.88 mni 3 of trimethylaluminum were stirred at room temperature for 100 hours. One half of the reaction product was analyzed by 1 H-NMR to confirm the formation of a Tybee type complex. 0. 24mmo 1 ethanol was added to the other half, and the product was stored at 25 ° C for 30 days. In the same manner as in Example 1, a fresh polymer solution of an S B S triblock copolymer was prepared using an organic alkali metal compound as a polymerization initiator, and 11.9 mm of ethanol was added thereto to passivate the polymer end. The preserved reaction product containing the Tybee complex was added to the SBS polymer solution, and hydrogen was blown into the SBS polymer solution so that part of the pressure was 0. 7 MPa. Under this condition, it was performed at 80 ° C. Hydrogenation. After 30 minutes, the degree of hydrogenation reached 99%. The printing department of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 1 · 9 mm ο 1, Z is 1 · 9 + 0 · 2 4 = 12.14 mmol, A1 is 0.94 mmol and Ti is 0.47 mmol, of which (M — Z + A 1 — T i) / T i is 0 · 5. Example 7 The same method as in Example 1, using an organic alkali metal compound. The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) • 31-474953 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Description of the invention ") As a polymerization initiator, a fresh polymer solution of SBS triblock copolymer was prepared, and 11.9 mmo ethanol was added to passivate the polymer ends. 0 · lmo 1 of Bis (methylcyclopentadienyl) titanium dichloride pentafluorene (manufactured by Nippon Fine Chemical Co. Ltd.) was mixed with a hexane solution of 0.3 m of 1 trimethylaluminum and stirred for 70 hours. The reaction mixture was evaporated to remove volatile materials, and the residue was recrystallized. The crystals were analyzed by 1 Η-NMR in the same manner as the Tybee reagent in Example 4. At 7.15 ppm, a peak caused by toluene As reference spikes, each spike was compared with a Tabby-type 1 Η-NMR spectrum in a professional work (J. Am. Chem. Soc., Vol. 100, 36Π-3613 (1978)). As a result, at 7.4 ppm Tybee complex There is a peak of methyl extension crosslinking, which seems to confirm that the above compound has formed. A cyclohexane solution of this crystal (0.20 mm ο 1) is added to the SBS polymer solution prepared above, and hydrogen is blown into it to make Partial pressure is 1 · 2 MPa. Under this condition, the hydrogenation is performed at 90 ° C. When the degree of hydrogenation reaches 80%, another 0.20 mmo 1 crystal of cyclohexane solution is added thereto, and the hydrogenation is continued. After 30 minutes, the degree of hydrogenation reached 99%. M is 1 1 · 9mmo 1, Z is 1 1 · 9mmo 1, A1 (A1 in the Tybee complex) is 0.40mmol and Ti is 0.40mmol, of which (M — Z + A 1-T i) / T i is 0. (Please read the precautions on the back before filling this page) Γ This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 32 474953 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description) Example 8 The same method as in Example 1, using an organic alkali metal compound as a polymerization initiator to prepare a fresh polymerization of an SBS triblock copolymer Solution, and add 1 1 · 9mmo to it 1 ethanol was used to passivate the polymer end. 0 · lmo 1 bis (n-butylcyclopentadienyl) dichloropentachloride (manufactured by Nippon Fine Chemical Co. Ltd.) and 0 · 3m ο 1 trimethylaluminum hexane solution was mixed and stirred for 70 hours. The reaction mixture was evaporated to remove volatiles and the residue was recrystallized. The crystal was analyzed at 1 Η-N M R in the same manner as in the analysis of the Tybee reagent in Example 4. At 7.15 ppm, the peaks caused by toluene are used as reference peaks. Each peak is associated with a professional work (J. Am. Chem · Soc ·, Vol. 100, 36 1 1 -36 1 3 (1 978)). Comparison of Taby 1H-NMR spectra. As a result, a peak of cross-linking of methyl group peculiar to the Tybee complex was observed at 7.94 p pm, and it was confirmed that the above compound was formed. A cyclohexane solution of this crystal (0.20mmo 1) was added to the SBS polymer solution prepared above, and hydrogen was blown thereinto to make a partial pressure of 1.2 MPa, and under this condition, it was performed at 90 ° C. Hydrogenation. When the degree of hydrogenation reached 80%, a cyclohexane solution of 0.20 mmo 1 crystals was added thereto, and the hydrogenation was continued. After 30 minutes, the degree of hydrogenation reached 99%. Μ is 1 1 · 9mmo 1, Z is 11.9mmo 1, A 1 (A 1. in the Taby complex) is 0 · 4〇mmo 1 and Dingi is 0.40mmol, where (M — Z + A 1 A paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) • 33474474, m ^ 2; o-A7-'__ B7 _ 5. Description of the invention (刈) T i) / T i is 〇. (Please read the precautions on the back before filling this page) Comparative Example 1 The same method as in Example 1 was used to prepare a fresh polymer solution of an SBS triblock copolymer using an organic alkali metal compound as a polymerization initiator. 1 1. 9 mm ο 1 ethanol was added to passivate the polymer end. To this solution was added 4.7 mmo1 of second butyllithium, and 0.47 m m of 1 Taby reagent made by Aldrich was additionally added. Hydrogen was blown thereinto to make a partial pressure of 0.7 MPa, and hydrogenation was performed at 80 ° C under these conditions. After 30 minutes, the degree of hydrogenation reached 33%.

Μ 係 11. 9 + 4.7 = 16.6mmol，Z 係 1 1. 9mmo 1 ，A 1 係〇 . 47mmol 而 T i 係 0.47mmol，其中（Μ - Ζ + A 1 - T i ) / T i 爲 1 〇。對照實例2 經濟部智慧財產局員工消費合作社印製如實施例1之相同方法，使用一種有機鹼金屬化合物作爲聚合引發劑製備一種S B S三嵌段共聚物之新鮮聚合物溶液，並於其中添加1 1 · 9 m m ο 1乙醇以鈍化該聚合物末端。於該溶液中添加1.9mmo1第二丁基鋰，並另外添加〇 · 47mmo 1由A1 dr i ch製之泰比 I式劑。於其中吹入氫使部分壓力爲〇 . 7 Μ P a ，於此條件下以8 0 °C進行氫化作用。3 0分鐘之後，氫化程度到達 6 3 %。本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 474953 A7 B7 經濟部中央標準局員工消費合作社印袈五、發明説明) Μ 係 11.9 + 1· 9 = l3.8mm〇l，Z 係 11.9mmol ，A1 係〇.47mmol 而 Ti 係 0.47mmol，其中（Μ - Ζ + A 1 — Τ i ) / Τ i 爲 4 〇對照實例3 如實施例1之相同方法，使用一種有機鹼金屬化合物作爲聚合引發劑製備一種S B S三嵌段共聚物之新鮮聚合物溶液，並於其中添加15 . 66mmo 1乙醇以鈍化該聚合物末端。於該溶液中添加〇 . 47mmo 1由Aldrich 製之泰比試劑。於其中吹入氫使部分壓力爲〇·7MPa ，於此條件下以8 0 °C進行氫化作用。3 0分鐘.之後，氫化程度到達3 5 %。 ]^係11.9111111〇1，2係15.66111111〇1， A1 係〇.47mmol 而 Ti 係〇.47mmol ，其中（M — Z + A 1 一 Ti)/Ti 爲一 8。對照實例4 如實施例1之相同方法，使用一種有機鹼金屬化合物作爲聚合引發劑製備一種S B S三嵌段共聚物之新鮮聚合物溶液，並於其中添加11.9mmo1乙醇以鈍化該聚合物末牺。分別於室溫下攪拌0.94mmo1之二氯化鈦五圜甲苯溶液（Wako Pure Chemical Industries，Ltd·所製）與請先閲讀背面之注意事項再填寫本頁)Μ is 11. 9 + 4.7 = 16.6 mmol, Z is 11.9 mmo 1, A 1 is 0.47 mmol and T i is 0.47 mmol, where (M-Zn + A 1-T i) / T i is 1 〇 . Comparative Example 2 The same method as in Example 1 was printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, using an organic alkali metal compound as a polymerization initiator to prepare a fresh polymer solution of an SBS triblock copolymer, and adding 1 to it 1 · 9 mm ο 1 ethanol to passivate the polymer end. To this solution was added 1.9 mmo1 of second butyllithium, and 0.47 mmo 1 of Tybee I made by A1 dr ich. Hydrogen was blown thereinto to a partial pressure of 0.7 MPa, and hydrogenation was performed at 80 ° C under this condition. After 30 minutes, the degree of hydrogenation reached 63%. The size of this paper applies to China National Standard (CNS) A4 (210X297 mm) 474953 A7 B7 Employee Consumer Cooperative Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs of the People's Republic of China 5. Description of the invention) Μ is 11.9 + 1. 9 = l3.8mm〇l, Z 11.9 mmol, A1 0.47 mmol and Ti 0.47 mmol, where (M-Zn + A 1-Τ i) / Τ i is 4 〇 Comparative Example 3 In the same manner as in Example 1, an organic alkali metal compound was used A fresh polymer solution of an SBS triblock copolymer was prepared as a polymerization initiator, and 15.66 mmo 1 ethanol was added thereto to passivate the polymer end. To this solution was added 0.47 mmol 1 of Tybee reagent made by Aldrich. Hydrogen was blown thereinto to make a partial pressure of 0.7 MPa, and hydrogenation was performed at 80 ° C under these conditions. After 30 minutes, the degree of hydrogenation reached 35%. ^ Series 11.9111111〇1, 2 series 15.66111111〇1, A1 series 0.47mmol and Ti series 0.47mmol, in which (M — Z + A 1 -Ti) / Ti is -8. Comparative Example 4 In the same manner as in Example 1, a fresh polymer solution of an S B S triblock copolymer was prepared using an organic alkali metal compound as a polymerization initiator, and 11.9 mmo1 of ethanol was added thereto to passivate the polymer. Stir 0.94mmo1 of titanium dichloride pentafluorene toluene solution (made by Wako Pure Chemical Industries, Ltd.) at room temperature and read the precautions on the back before filling this page)

,aT 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） •35- 474953 A7 B7 經濟部中央標準局員工消费合作社印製五、發明説明“） 6 · 2mmo 1之三異丁基鋁2 0分鐘。取出一半該產物，並蒸發之去除該揮發性物質。將其殘餘溶解於氚苯溶液中，並以實施例1之同方式以1 Η — NMR分析之。該光譜並未顯示T i 一 A 1金屬環特有之伸甲基交聯之質子吸收，表示尙未形成泰比型錯合物。將另一半該反應產物添加於上述製備之S B S聚合物溶液，於其中吹入氫使部分壓力爲0·7MPa ，於此條件下以8 0 °C進行氫化作用。3 0分鐘之後，氫化程度到達 2 5 %。對照實例5 如實施例1之相同方法，使用一種有機鹼金.屬化合物作爲聚合引發劑製備一種S B S三嵌段共聚物之新鮮聚合物溶液，並於其中添加1 1 · 9 m m ο 1乙醇以鈍化該聚合物末端。分別於室溫下攪拌0 · 9 4mmo 1之二氯化鈦五圜甲苯溶液（Wako Pure Chemical Industries，Ltd·所製）與 6 · 2mmo 1之三異丁基鋁100小時。取出一半該產物，並蒸發之去除該揮發性物質。將其殘餘溶解於氚苯溶液中，並以實施例1之同方式以1 Η — NMR分析之。該光譜並未顯示T i 一 A 1金屬環特有之伸甲基交聯之質子吸收，表示尙未形成泰比型錯合物。將另一半該反應產物添加於上述製備之S B S聚合物溶液，於其中吹入氫使部分壓力爲〇·7MPa ，於此條 (請先閲讀背面之注意事項再填寫本頁), aT This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) • 35- 474953 A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention ") 6 · 2mmo 1 triisobutyl Aluminum for 20 minutes. Half of the product was taken out and evaporated to remove the volatile matter. The residue was dissolved in the toluene solution and analyzed in the same manner as in Example 1 by 1 Η—NMR. The spectrum is not shown The proton absorption of the methylated cross-linking peculiar to Ti-A1 metal ring indicates that thallium does not form a Taby complex. The other half of the reaction product is added to the SBS polymer solution prepared above, and hydrogen is blown into it. Partial pressure was 0 · 7MPa, under this condition at 80 ° C for hydrogenation. After 30 minutes, the degree of hydrogenation reached 25%. Comparative Example 5 As in Example 1, the same method, using an organic alkali gold. Metal compounds as polymerization initiators to prepare a fresh polymer solution of SBS triblock copolymer, and add 1 1 · 9 mm ο 1 ethanol to passivate the polymer ends. Stir 0 · 9 4mmo 1 at room temperature respectively Of Titanium chloride pentaoxene toluene solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 6.2mmo 1 triisobutylaluminum for 100 hours. Half of the product was taken out and evaporated to remove the volatile matter. The residue was dissolved In a toluene solution, it was analyzed by 1 Η — NMR in the same manner as in Example 1. The spectrum did not show the proton absorption of the methylated cross-linking peculiar to the T i -A 1 metal ring, indicating that 尙 did not form benzene. The other half of the reaction product is added to the SBS polymer solution prepared above, and hydrogen is blown into it to make part of the pressure 0.7MPa. Please read the notes on the back before filling this page )

T 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -36 - 474953 A7 B7 經濟部中央標準局員工消費合作社印裝五、發明説明“）件下以8 0 °C進行氫化作用。3 0分鐘之後，氫化程度到達 4 5 % 〇對照實例6 如實施例1之相同方法，使用一種有機鹼金屬化合物作爲聚合引發劑製備一種S B S三嵌段共聚物之新鮮聚合物溶液，並於其中添加11·9mmo1乙醇以鈍化該聚合物末端。分別於室溫下攪拌0 . 9 4mmo 1之二氯化鈦五圜甲苯溶液（Wako Pure Chemical Industries，Ltd·所製）與6 · 2mmo 1之三異丁基鋁20分鐘。取出一半該產物，並蒸發之去除該揮發性物質。將其殘餘溶解於氚苯溶液中，並以實施例1之同方式以1 Η — NMR分析之。該光譜並未顯示T i 一 A 1金屬環特有之伸甲基交聯之質子吸收，表示尙未形成泰比型錯合物。將另一半該反應產物添加於上述製備之S B S聚合物溶液，於其中吹入氫使部分壓力爲0·7MPa ，於此條件下以8 0 °C進行氫化作用。3 0分鐘之後，氫化程度到達 1 5 %。對照實例7 如實施例1之相同方法，使用一種有機鹼金屬化合物作爲聚合引發劑製備一種S B S三嵌段共聚物之新鮮聚合物溶液，並於其中添加11·9mmo1乙醇以鈍化該聚 (請先閲讀背面之注意事項再填寫本頁) 訂本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公嫠） -37- 474953 經濟部中央標準局員工消費合作社印裝 A7 B7 五、發明説明“) 合物末端。於該溶液中添加0.94mmo1之三甲基鋁，然後添加0 · 47mmol由Aldrich製之泰比試劑。於其中吹入氫使部分壓力爲0 · 7MP a，於此條件下以 8 0 °C進行氫化作用。3 0分鐘之後，氫化程度到達4 8 %。對照實例8 如實施例1之相同方法，使用一種有機鹼金屬化合物作爲聚合引發劑製備一種S B S三嵌段共聚物之新鮮聚合物溶液，並於其中添加1 1 · 9mmo 1乙醇以鈍化該聚合物末端。分別於室溫下攪拌0 · 9 4mmo 1之二氯.化鈦五圜甲苯溶液（Wako Pure Chemical Industries，Ltd.所製）與 1 · 88mmo 1之三異丁基鋁20分鐘。取出一半該產物，並蒸發之去除該揮發性物質。將其殘餘溶解於氚苯溶液中，並以實施例1之同方式以1 H -NMR分析之。該光譜並未顯示T i - A 1金屬環特有之伸甲基交聯之質子吸收，表示尙未形成泰比型錯合物。以實施例1之相同方式，將另一半該反應產物添加於上述製備之S B S聚合物溶液，於其中吹入氫使部分壓力爲0 · 7 Μ P a，於此條件下以8 〇 °C進行氫化作用。 3 0分鐘之後，氫化程度到達5 5%。如上述，本發明方法提供一種用以氫化共軛二烯聚合物雙鍵之工業有利方法，其包括使共軛二烯聚合物與一種本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁)T This paper size is in accordance with Chinese National Standard (CNS) A4 (210X 297 mm) -36-474953 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention ") Hydrogenated at 80 ° C under the conditions After 30 minutes, the degree of hydrogenation reached 45%. Comparative Example 6 In the same manner as in Example 1, a fresh polymer solution of an SBS triblock copolymer was prepared using an organic alkali metal compound as a polymerization initiator, and To this was added 11.9 mmo1 of ethanol to passivate the polymer ends. The 0.94 mmo 1 titanium chloride pentaoxene solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 6.2 mmo 1 were stirred at room temperature, respectively. Triisobutyl aluminum for 20 minutes. Take out half of the product and evaporate to remove the volatiles. Dissolve the residue in the toluene solution and analyze it by 1 方式 -NMR in the same manner as in Example 1. The The spectrum does not show the proton absorption of the methylated cross-linking peculiar to the T i -A 1 metal ring, indicating that thallium does not form a Taby complex. The other half of the reaction product is added to the SBS polymer prepared above. Hydrogen solution was blown into it to make part of the pressure 0 · 7 MPa, and hydrogenation was performed at 80 ° C under this condition. After 30 minutes, the degree of hydrogenation reached 15%. Comparative Example 7 Same as Example 1 Method, using an organic alkali metal compound as a polymerization initiator to prepare a fresh polymer solution of SBS triblock copolymer, and adding 11.9mmo1 ethanol to passivate the poly (Please read the precautions on the back before filling this page ) The size of the paper is applicable to Chinese National Standards (CNS) A4 specifications (210X297 gong) -37- 474953 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. To this solution, 0.94 mmo1 of trimethylaluminum was added, and then 0.47 mmol of Tybee reagent manufactured by Aldrich was added. Hydrogen was blown in to make part of the pressure at 0.7 MPa, and hydrogenation was performed at 80 ° C under these conditions. After 30 minutes, the degree of hydrogenation reached 48%. Comparative Example 8 A fresh polymer solution of an SBS triblock copolymer was prepared using the same method as in Example 1 using an organic alkali metal compound as a polymerization initiator, and 1 1 · 9mmo 1 ethanol was added to passivate the polymer. End. A 0. 94 mmo 1 dichloride, titanium pentamidine toluene solution (manufactured by Wako Pure Chemical Industries, Ltd.) and a 1.88 mmo triisobutylaluminum were stirred at room temperature for 20 minutes, respectively. Take out half of the product and evaporate to remove the volatiles. The residue was dissolved in a toluene solution and analyzed by 1 H-NMR in the same manner as in Example 1. This spectrum does not show the absorption of protons, which are peculiar to the extension of methyl groups of T i-A 1 metal rings, indicating that thorium type complexes are not formed. In the same manner as in Example 1, the other half of the reaction product was added to the above-prepared SBS polymer solution, and hydrogen was blown into it to make part of the pressure 0. 7 MPa. Under this condition, it was performed at 80 ° C. Hydrogenation. After 30 minutes, the degree of hydrogenation reached 55%. As mentioned above, the method of the present invention provides an industrially advantageous method for hydrogenating a double bond of a conjugated diene polymer, which includes adapting the conjugated diene polymer and a paper size to the Chinese National Standard (CNS) A4 specification (210X297). Li) (Please read the notes on the back before filling in this page)

T -38 · 474953 A7 ____ Β7五、發明説明“) 惰性有機溶劑接觸，該共軛二烯係使用一種有機鹼金屬化合物作爲聚合引發劑製備，該方法中，用以氫化之觸媒安定而易於處理，不需要鹼金屬化合物作爲共觸媒，所需之觸媒用量極少，而且該氫化作用在廣泛溫度範圍内定量進行。雖然本發明已經詳細說明並參照其特定實例，在不違背其精神與範疇之下，熟知本技藝者可由此明瞭各種改變與改良0 (請先閲讀背面之注意事項再填寫本頁) - 訂經濟部中央標準局員工消費合作杜印製本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐〉 -39 -T -38 · 474953 A7 ____ B7 V. Description of the invention ") Contact with an inert organic solvent. The conjugated diene is prepared using an organic alkali metal compound as a polymerization initiator. In this method, the catalyst used for hydrogenation is stable and easy to use. The treatment does not require an alkali metal compound as a co-catalyst, the amount of catalyst required is extremely small, and the hydrogenation is performed quantitatively over a wide temperature range. Although the present invention has been described in detail and referenced to specific examples, it does not violate its spirit and Under the scope, those skilled in the art can understand various changes and improvements. (Please read the precautions on the back before filling out this page)-Order the consumer cooperation of the Central Standards Bureau of the Ministry of Economic Affairs, and print this paper to apply Chinese national standards ( CNS) Α4 size (210X297 mm> -39-

Claims

474953 A8 B8 C8 D8 附件二A :第861 14780號專利申請案474953 A8 B8 C8 D8 Annex II A: Patent Application No. 861 14780

合物，該聚合物係使用發劑來製備，該有機鹼且該鈍化劑爲具有經基其可與有機金麝反應產合物，其可與有機金屬烯聚合物與氫接觸，以該惰性烴溶劑爲脂族烴在氫化條件下不會被·氫 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製申請專利範圍添加鈍化劑鈍化該共軛二烯聚一種有機鹼金屬化合物作爲聚合引金屬化合物脂族烴鹼金屬化合物，、羧基、酯基或環氧基之化合物，生一種金屬烷氧化物，或爲鹵素化化合物反應產生一種金屬鹵化物；及於惰性烴溶劑中使該鈍化二氫化該經鈍化二烯聚合物之雙鍵，或芳族烴，其中芳族烴之芳族雙鍵化，其中該氫化作用係於： (i )存在選自由下列北學式表示之有機金屬化合物觸媒 R5 R4The polymer is prepared by using a hair-agent, the organic base and the passivation agent have a base which can react with an organometallic compound, which can be contacted with an organometallic polymer and hydrogen to make the inert Hydrocarbon solvents are aliphatic hydrocarbons that will not be hydrogenated under hydrogenation conditions (please read the precautions on the back before filling this page) Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to apply for a patent to add a passivating agent to passivate the conjugated diene Polymerizing an organic alkali metal compound as a polymer metal-inducing compound, an aliphatic hydrocarbon alkali metal compound, a compound of a carboxyl group, an ester group, or an epoxy group, generating a metal alkoxide, or reacting a halogenated compound to produce a metal halide; and The passivated dihydrogenated double bond of the passivated diene polymer, or an aromatic hydrocarbon in which an aromatic double bond is aromaticized in an inert hydrocarbon solvent, wherein the hydrogenation is due to: (i) the presence of Organic metal compound catalyst R5 R4

H： C X〆 ,C H3 A CH, ' 本紙張尺度適用中國國家梂準（CNS ) A4規格（210X；297公釐） 474953 A8 B8 C8 _______ D8 六、申請專利範圍 (請先閱讀背面之注意事項再填寫本頁) R9與R1Q ’可相同或不同，其各表示氫原子、具有1至 1 2個碳原子之烴基，或具有1至1 2個碳原子之烷基甲矽烷基；X表示鹵素原子或甲基； (i i )於滿足下列關係式： -6 < (M - z + A1 - Ti)/Ti < 2 其中Μ表示該有機鹼金屬化合物之莫耳量；z表示該鈍化劑之莫耳量；A 1表示該有機鋁化合物之莫耳量；而τ i 表示有機鈦化合物之莫耳量的條件下進行。 2 · 如申請專利範圍第1項之方法，其中該惰性烴溶劑實質上不含直鏈醚化合物。 3 · 如申請專利範圍第1項之方法，其中鈍化劑之添加量符合關係式一 5 ^ ( Μ — Ζ)/ Τ i $1.9。經濟部智慧財產局3(工消費合作社印製 4 _如申I靑專利範圍第i項之方法，其中該氫化作用係於符合關係式—3 ^ ( Μ — Z + A 1 一 T i ) / T i ^ 1之條件下進行。 5 ·如申請專利範圍第1項之方法，其中該觸媒係二鹵化鈦五圜與三甲基鋁之反應混合物。 6 ·如申請專利範圍第1項之方法，其中該氫化作用係於存在一種三級胺化合物下進行。本紙張尺度逋用中國國家標準（CNS ) A4規格（210><297公釐）H: CX〆, C H3 A CH, 'This paper size applies to China National Standards (CNS) A4 specifications (210X; 297 mm) 474953 A8 B8 C8 _______ D8 6. Scope of patent application (please read the precautions on the back first) Fill out this page again) R9 and R1Q 'may be the same or different, and each represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or an alkylsilyl group having 1 to 12 carbon atoms; X represents halogen Atom or methyl group; (ii) satisfying the following relationship: -6 < (M-z + A1-Ti) / Ti < 2 where M represents the molar amount of the organic alkali metal compound; z represents the passivation agent Molar amount; A 1 represents the molar amount of the organoaluminum compound; and τ i represents the molar amount of the organic titanium compound. 2. The method of claim 1 in which the inert hydrocarbon solvent is substantially free of linear ether compounds. 3. The method of item 1 in the scope of patent application, in which the addition amount of the passivation agent conforms to the relational expression 5 ^ (Μ—Z) / Τi $ 1.9. Bureau of Intellectual Property, Ministry of Economic Affairs 3 (Printed by Industry and Consumer Cooperatives 4 _ Rushen I 靑 Method of Patent Scope Item i, where the hydrogenation is in accordance with the relationship — 3 ^ (Μ — Z + A 1-T i) / Performed under the conditions of T i ^ 1. 5 · The method according to item 1 of the scope of patent application, wherein the catalyst is a reaction mixture of titanium dihalide pentafluorene and trimethyl aluminum. 6 · The method according to item 1 of the scope of patent application Method, in which the hydrogenation is carried out in the presence of a tertiary amine compound. This paper uses the Chinese National Standard (CNS) A4 specification (210 > < 297 mm)