JP2016117876A - Catalyst for conjugated diene polymerization, manufacturing method of conjugated diene polymer, conjugated diene polymer, conjugated diene polymer composition, tire and rubber belt - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conjugated diene polymer having higher percentage content of cis-1,4 structure with higher activity than conventional ones by using a rare earth metal-based alkoxide compound.SOLUTION: The invention relates to a catalyst for conjugated diene polymerization containing a rare earth metal-based alkoxide compound (A) excluding a Sm-based alkoxide compound and a Yb-based alkoxide compound, an ionic compound consisting of non-coordinating anion and cation (B) and an organic metal compound of an element selected from II Group, XII group and VIII group in the periodic table (C).SELECTED DRAWING: None

Description

  The present invention relates to a conjugated diene polymerization catalyst using a rare earth metal alkoxide compound, a conjugated diene polymer production method, a conjugated diene polymer, a conjugated diene polymer composition, a tire, and a rubber belt.

  Many proposals have been made on the polymerization catalysts for conjugated dienes such as 1,3-butadiene and isoprene, some of which have been industrialized. For example, as a method for producing a conjugated diene polymer having a high cis-1,4 structure, a combination of a compound such as titanium, cobalt, nickel, or neodymium and organic aluminum is often used.

  The polymerization of conjugated dienes using Group 3 elements of the Periodic Table as a catalyst is known, and various polymerization methods have been proposed so far. For example, Patent Document 1 discloses a catalyst system comprising a rare earth metal alkoxide and organoaluminum. Patent Document 2 discloses a catalyst system comprising a rare earth metal salt, an organometallic compound of Group I to III elements of the periodic table, and a fluorine-containing organoboron compound. Patent Document 3 discloses a polymerization catalyst comprising a Group IIIB metal compound of the periodic table, an ionic compound of a non-coordinating anion and a cation, and an organometallic compound of Group I to III elements of the Periodic Table. Yes. Patent Document 4 lists organometallic compounds of elements selected from Groups 2, 12, and 13 of the periodic table. Patent Document 5 discloses a method for producing cis-1,4-polybutadiene using a compound of an element selected from the group consisting of scandium, yttrium, lanthanoid, and actinoid as a catalyst. Patent Documents 6 to 8 report conjugated diene polymerization using a metallocene gadolinium complex.

JP-A-7-70143 Japanese Patent Laid-Open No. 7-268013 Japanese Patent Laid-Open No. 11-80222 JP 2007-161921 A JP 2003-226721 A JP 2004-27179 A Japanese Patent Laid-Open No. 2004-238637 JP 2007-63240 A

However, the effects shown in the Examples as the catalysts described in Patent Documents 1 to 5 are limited to neodymium and praseodymium, and the catalytic activity is very low. Moreover, although the metallocene-type gadolinium catalyst is used for the catalyst of patent documents 6 thru | or 8, there exists a problem that a catalyst activity is low activity with 540 g / mmol-Gd / hr at maximum.
The present invention has been made in view of the above problems, and conjugated diene polymerization using a rare earth metal alkoxide compound capable of producing a conjugated diene polymer having a high cis-1,4 structure content with high activity. It is an object to provide a catalyst for use and a method for producing a conjugated diene polymer using the same.

  As a result of intensive studies to achieve the above object, the present inventors have used a rare earth metal-based alkoxide compound to produce a conjugated diene polymer having a higher cis-1,4 structure content than the conventional one. As a result, the present invention has been found.

1. Rare earth metal alkoxide compound (A) (except Sm alkoxide compound, Eu alkoxide compound and Yb alkoxide compound), ionic compound (B) comprising non-coordinating anion and cation, and periodic table A conjugated diene polymerization catalyst comprising: an organometallic compound (C) of an element selected from Group 2, 12, and 13.

2. Item 2. The conjugated diene polymerization catalyst according to Item 1, wherein the rare earth metal alkoxide compound (A) is an alkoxide compound represented by the following general formula (1).

（但し、Ｒは炭素数１〜６の置換基を表す。Ｏは酸素原子を表し、Ｌｎは希土類金属原子を表す（ただしＳｍ、Ｅｕ及びＹｂを除く）。）

(Wherein R represents a substituent having 1 to 6 carbon atoms, O represents an oxygen atom, and Ln represents a rare earth metal atom (except Sm, Eu and Yb).)

3. Item 3. The conjugated diene polymerization catalyst according to Item 1 or 2, wherein the organometallic compound (C) is organoaluminum.

4). Item 4. The conjugated diene polymerization catalyst according to any one of Items 1 to 3, wherein the ionic compound (B) is a boron-containing compound.

5. 5. A method for producing a conjugated diene polymer, comprising polymerizing a conjugated diene compound using the catalyst for conjugated diene polymerization according to any one of items 1 to 4.

6). 5. A conjugated diene polymer obtained by polymerizing a conjugated diene compound using the conjugated diene polymerization catalyst according to any one of items 1 to 4.

7). An ion comprising a rare earth metal alkoxide compound (A) represented by the following general formula (1) (excluding Sm alkoxide compounds, Eu alkoxide compounds and Yb alkoxide compounds), a non-coordinating anion and a cation Conjugated by polymerizing a conjugated diene compound using a conjugated diene polymerization catalyst having an organic compound (B) and an organometallic compound (C) of an element selected from Groups 2, 12 and 13 of the periodic table A conjugated diene polymer composition comprising a diene polymer (α), a diene polymer (β) other than (α), and a rubber reinforcing agent (γ).

（但し、Ｒ^１、Ｒ^２、Ｒ^３はそれぞれ水素、または炭素数１〜１２の置換基を表す。Ｌｎは希土類金属原子を表す（ただしＳｍ、Ｅｕ及びＹｂを除く）。）

(However, R ¹ , R ² and R ³ each represent hydrogen or a substituent having 1 to 12 carbon atoms. Ln represents a rare earth metal atom (except Sm, Eu and Yb).)

8). Item 8. The conjugated diene polymer composition according to Item 7, wherein the rubber reinforcing agent (γ) is carbon black and / or silica.

9. Item 7 or Item characterized in that the conjugated diene compound has a molecular weight adjusted by a compound selected from (1) hydrogen, (2) metal hydride compound, and (3) hydrogenated organometal compound. 9. The conjugated diene polymer composition according to 8.

10. Item 10. The conjugated diene polymer composition according to any one of Items 7 to 9, wherein the conjugated diene compound is 1,3-butadiene.

11. A tire using the conjugated diene polymer composition according to any one of Items 7 to 10.

12 A rubber belt using the conjugated diene polymer composition according to any one of Items 7 to 10.

  As described above, according to the present invention, a conjugated diene polymerization catalyst capable of producing a conjugated diene polymer having a high cis-1,4 structure content with high activity and production of a conjugated diene polymer using the same. A method can be provided.

  The rare earth metal alkoxide compound (A) used for the conjugated diene polymerization catalyst according to the present invention is a rare earth metal alkoxide compound represented by the following general formula (1).

（但し、Ｒは炭素数１〜６の置換基を表す。Ｏは酸素原子を表し、Ｌｎは希土類金属原子を表す。）

(However, R represents a C1-C6 substituent. O represents an oxygen atom and Ln represents a rare earth metal atom.)

  Ln in the general formula (1) is a rare earth metal excluding Sm, Eu and Yb. The valence of the rare earth metal is usually trivalent, but rare earth metals such as Sm, Eu and Yb whose valence may be divalent did not function as a catalyst in the present invention.

  Among rare earth metals, scandium (Sc), yttrium (Y), lanthanum (La), praseodymium (Pr), neodymium (Nd), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (in particular) Ho), erbium (Er), and thulium (Tm) are preferably used. More preferred are scandium (Sc), lanthanum (La), praseodymium (Pr), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), and erbium (Er).

  Specific examples of the substituent having 1 to 6 carbon atoms in R in the general formula (1) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t -Butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, hexyl group Saturated hydrocarbon groups such as, unsaturated hydrocarbon groups such as vinyl group, 1-propenyl group, and allyl group, alicyclic hydrocarbon groups such as cyclohexyl group, methylcyclohexyl group, and ethylcyclohexyl group, and phenyl group, Examples thereof include aromatic hydrocarbon groups such as benzyl group, toluyl group, and phenethyl group. Furthermore, those in which a hydroxyl group, a carboxyl group, a carbomethoxy group, a carboethoxy group, an amide group, an amino group, an alkoxy group, a phenoxy group and the like are substituted at an arbitrary position are also included. Especially, a C1-C6 saturated hydrocarbon group is preferable.

Specific examples of the rare earth metal alkoxide compound (A) include trimethoxy scandium, triethoxy scandium, tri-n-propoxy scandium, triisopropoxy scandium, tributoxy scandium, tripentoxy scandium, trihexyloxy scandium,
Trimethoxy yttrium, triethoxy yttrium, tri-n-propoxy yttrium, triisopropoxy yttrium, tributoxy yttrium, tripentoxy yttrium, trihexyloxy yttrium,
Trimethoxy gadolinium, triethoxy gadolinium, tri n-propoxy gadolinium, triisopropoxy gadolinium, tributoxy gadolinium, tripentoxy gadolinium, trihexyloxy gadolinium,
Trimethoxyterbium, triethoxyterbium, tri-n-propoxyterbium, triisopropoxyterbium, tributoxyterbium, tripentoxyterbium, trihexyloxyterbium,
Trimethoxy dysprosium, triethoxy dysprosium, tri n-propoxy dysprosium, triisopropoxy dysprosium, tributoxy dysprosium, tripentoxy dysprosium, trihexyloxy dysprosium,
Trimethoxy lanthanum, triethoxy lanthanum, tri n-propoxylantan, triisopropoxylantan, tributoxylantan, tripentoxylantan, trihexyloxylantan,
Trimethoxy praseodymium, triethoxy praseodymium, tri-n-propoxy praseodymium, triisopropoxy praseodymium, tributoxy praseodymium, tripentoxy praseodymium, trihexyloxy praseodymium,
Trimethoxyneodymium, triethoxyneodymium, tri-n-propoxyneodymium, triisopropoxyneodymium, tributoxyneodymium, tripentoxyneodymium, trihexyloxyneodymium,
Trimethoxy holmium, triethoxy holmium, tri n-propoxy holmium, triisopropoxy holmium, tributoxy holmium, tripentoxy holmium, trihexyloxy holmium,
Trimethoxy erbium, triethoxy erbium, tri n-propoxy erbium, triisopropoxy erbium, tributoxy erbium, tripentoxy erbium, trihexyloxy erbium,
Examples include trimethoxy thulium, triethoxy thulium, tri n-propoxy thulium, triisopropoxy thulium, tributoxy thulium, tripentoxy thulium, trihexyloxy thulium, and the like.

  Of these, triisopropoxy scandium, triisopropoxy gadolinium, triisopropoxy terbium, and triisopropoxy dysprosium are preferable. The rare earth metal alkoxide compound (A) may be used alone or in combination of two or more.

  The rare earth metal alkoxide compound (A) includes an ionic compound (B) composed of a non-coordinating anion and a cation, and an organometallic compound of an element selected from Groups 2, 12, and 13 of the periodic table ( By combining with C), it can be used as a catalyst for conjugated diene polymerization.

  In the ionic compound comprising the non-coordinating anion and cation as the component (B), examples of the non-coordinating anion include tetra (phenyl) borate, tetra (fluorophenyl) borate, and tetrakis (difluorophenyl). Borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (3,5-bistrifluoromethylphenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra ( Triyl) borate, tetra (xylyl) borate, triphenyl (pentafluorophenyl) borate, tris (pentafluorophenyl) (phenyl) borate, tridecahydride-7,8-dicarba Ndekaboreto, tetrafluoroborate, hexafluorophosphate and the like.

  On the other hand, examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation.

  Specific examples of the carbonium cation include tri-substituted carbonium cations such as a triphenyl carbonium cation and a tri-substituted phenyl carbonium cation. Specific examples of the tri-substituted phenylcarbonium cation include tri (methylphenyl) carbonium cation and tri (dimethylphenyl) carbonium cation.

  Specific examples of ammonium cations include trialkylammonium cations, triethylammonium cations, tripropylammonium cations, tri (n-butyl) ammonium cations, tri (i-butyl) ammonium cations, and the like, N, N-dimethyl N, N-dialkylanilinium cations such as anilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation, di (i-propyl) ammonium cation, dicyclohexylammonium Mention may be made of dialkylammonium cations such as cations.

  Specific examples of phosphonium cations include triphenylphosphonium cation, tetraphenylphosphonium cation, tri (methylphenyl) phosphonium cation, tetra (methylphenyl) phosphonium cation, tri (dimethylphenyl) phosphonium cation, tetra (dimethylphenyl) phosphonium cation, etc. Of arylphosphonium cations.

  As the ionic compound (B), those arbitrarily selected and combined from the non-coordinating anions and cations exemplified above can be preferably used.

  Among them, as the ionic compound (B), a boron-containing compound is preferable, and among them, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (fluorophenyl) borate, N, N-dimethylaniline are particularly preferable. Nitrotetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate and the like are preferable. An ionic compound (B) may be used independently and may be used in combination of 2 or more type.

  In addition, alumoxane may be used in place of the ionic compound composed of the non-coordinating anion and cation as component (B). The alumoxane is obtained by bringing an organoaluminum compound and a condensing agent into contact with each other, and has a general formula (—Al (R ′) O—) n (R ′ is a hydrocarbon group having 1 to 10 carbon atoms). Including a partly substituted with a halogen atom and / or an alkoxy group, where n is the degree of polymerization and is 5 or more, preferably 10 or more). . Examples of R ′ include a methyl group, an ethyl group, a propyl group, and an isobutyl group, and a methyl group is preferable. Examples of organoaluminum compounds used as aluminoxane raw materials include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof. Among these, alumoxane using a mixture of trimethylaluminum and triisobutylaluminum as a raw material can be suitably used.

  Examples of organometallic compounds of Group 2, 12 and 13 of the periodic table that are the component (C) include organic magnesium, organic zinc, and organic aluminum. Among these compounds, preferred are dialkylmagnesium; alkylmagnesium halides such as alkylmagnesium chloride and alkylmagnesium bromide; dialkylzinc; trialkylaluminum; dialkylaluminum chloride, dialkylaluminum bromide; alkylaluminum sesquichloride, alkylaluminum sesquibromide Organic aluminum halogen compounds such as alkylaluminum dichloride; organoaluminum hydride compounds such as dialkylaluminum hydride.

  Specific compounds include alkyl magnesium halides such as methyl magnesium chloride, ethyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, octyl magnesium chloride, ethyl magnesium bromide, butyl magnesium bromide, butyl magnesium iodide, and hexyl magnesium iodide. Can be mentioned.

  Furthermore, dialkyl magnesium such as dimethylmagnesium, diethylmagnesium, dibutylmagnesium, dihexylmagnesium, dioctylmagnesium, ethylbutylmagnesium, and ethylhexylmagnesium can be exemplified.

  Furthermore, dialkyl zinc, such as dimethyl zinc, diethyl zinc, diisobutyl zinc, dihexyl zinc, dioctyl zinc, and didecyl zinc, can be mentioned.

  Furthermore, trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, and the like can be given.

  Furthermore, dialkylaluminum chlorides such as dimethylaluminum chloride and diethylaluminum chloride, organoaluminum halogen compounds such as ethylaluminum sesquichloride and ethylaluminum dichloride, and hydrogenated organoaluminum compounds such as diethylaluminum hydride, diisobutylaluminum hydride and ethylaluminum sesquihydride. Can be mentioned.

These organometallic compounds of Groups 2, 12, and 13 of the periodic table can be used alone or in combination of two or more.
Among them, group 13 elements are preferable, among which organic aluminum is preferable, and examples thereof include trimethylaluminum, triethylaluminum, and triisobutylaluminum. Particularly preferred is triethylaluminum.

  In the present invention, the conjugated diene can be polymerized using the catalyst provided with the components (A), (B) and (C) described above, but in the range not impeding the effects of the present invention other than the above, A condensing agent, a molecular weight regulator of the resulting conjugated diene polymer, and the like can be added.

  A typical example of the condensing agent is water, but in addition to this, an arbitrary one in which the trialkylaluminum undergoes a condensation reaction, for example, adsorbed water such as an inorganic substance, diol, and the like.

  Moreover, as a molecular weight regulator, the compound chosen from hydrogen, a metal hydride compound, and an organometallic compound can be used.

  Metal hydride compounds include lithium hydride, sodium hydride, potassium hydride, magnesium hydride, calcium hydride, borane, aluminum hydride, gallium hydride, silane, germane, lithium borohydride, sodium borohydride , Lithium aluminum hydride, sodium aluminum hydride and the like.

  Examples of the hydrogenated organometallic compound include alkylboranes such as methylborane, ethylborane, propylborane, butylborane and phenylborane, dialkylboranes such as dimethylborane, diethylborane, dipropylborane, dibutylborane and diphenylborane, and methylaluminum dihydride. Alkyl aluminum dihydride such as ethyl aluminum dihydride, propyl aluminum dihydride, butyl aluminum dihydride, phenyl aluminum dihydride, dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, dinormal butyl aluminum hydride, diisobutyl aluminum hydride, Diphenylaluminum high dry Dialkylaluminum hydride such as, methylsilane, ethylsilane, propylsilane, butylsilane, phenylsilane, dimethylsilane, diethylsilane, dipropylsilane, dibutylsilane, diphenylsilane, trimethylsilane, triethylsilane, tripropylsilane, tributylsilane, triphenylsilane Silanes such as, methyl germane, ethyl germane, propyl germane, butyl germane, phenyl germane, dimethyl germane, diethyl germane, dipropyl germane, dibutyl germane, diphenyl germane, trimethyl germane, triethyl germane, tripropyl germane, tributyl germane, tributyl germane Examples thereof include germanes such as phenyl germane.

  Among these, diisobutylaluminum hydride and diethylaluminum hydride are preferable.

  In the present invention, each catalyst component may be aged in advance. Especially, it is preferable to age | cure (A) component and (C) component.

  For aging, the component (A) and the component (C) are preferably mixed in an inert solvent in the presence or absence of the conjugated diene compound monomer. The aging temperature is −50 to 120 ° C., preferably −10 to 95 ° C., and the aging time is 0.005 to 24 hours, preferably 0.01 to 5 hours, and particularly preferably 0.02 to 1 hour.

  Furthermore, in the present invention, each catalyst component can be supported on an inorganic compound or an organic polymer compound.

  In the method for producing a conjugated diene polymer according to the present invention, the order of addition of the catalyst component is not particularly limited, and can be performed, for example, in the following order.

  (1) Add component (C) in the presence or absence of a conjugated diene compound monomer in an inert organic solvent, and add component (A) and component (B) in any order.

  (2) Add component (C) in the presence or absence of a conjugated diene compound monomer in an inert organic solvent, add the molecular weight regulator as described above, and then optionally add component (A) and component (B) Add in order.

  (3) In the inert organic solvent, the component (A) is added in the presence or absence of the conjugated diene compound monomer, the component (C) and the molecular weight regulator described above are added in any order, and (B) Add ingredients.

  (4) In the inert organic solvent, the component (B) is added in the presence or absence of the conjugated diene compound monomer, and the component (C) and the molecular weight regulator described above are added in any order, and then (A) Add ingredients.

  (5) In the inert organic solvent, the (C) component is added in the presence or absence of the conjugated diene compound monomer, the (A) component and the (B) component are added in any order, and then the molecular weight described above. Add modifier.

  The raw material conjugated diene compound monomer includes 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethylbutadiene, 2-methylpentadiene, 4-methylpentadiene. 2,4-hexadiene and the like. Among them, a conjugated diene compound monomer mainly composed of 1,3-butadiene is preferable. These monomer components may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, you may include the other thing of a conjugated diene by making a conjugated diene compound monomer into a part. Other conjugated dienes include ethylene, propylene, allene, 1-butene, 2-butene, 1,2-butadiene, pentene, cyclopentene, hexene, cyclohexene, octene, cyclooctadiene, cyclododecatriene, norbornene, norbornadiene. And olefin compounds.

  The polymerization method is not particularly limited, and bulk polymerization (bulk polymerization) or solution polymerization using a conjugated diene compound monomer such as 1,3-butadiene as a polymerization solvent can be applied. Solvents for solution polymerization include aliphatic hydrocarbons such as butane, pentane, hexane, and heptane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and cumene, Examples thereof include olefinic hydrocarbons such as olefin compounds and cis-2-butene and trans-2-butene. Among them, benzene, toluene, xylene, cyclohexane, or cis-2-butene and trans-2-butene. And the like are preferably used. These solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

  The polymerization temperature is preferably in the range of -30 to 150 ° C, particularly preferably in the range of 0 to 100 ° C. The polymerization time is preferably 1 minute to 12 hours, particularly preferably 5 minutes to 5 hours.

  After performing the polymerization for a predetermined time, the inside of the polymerization tank is released as necessary, and post-treatment such as washing and drying steps is performed.

  The conjugated diene polymer obtained in the present invention is preferably cis-1,4 having a cis-1,4 structure of 85.0% or more, more preferably 88.0% or more, and further preferably 89.5% or more. -Polybutadiene is mentioned. The intrinsic viscosity [η] of the conjugated diene polymer is preferably controlled to 0.1 to 10, more preferably 1.0 to 7.0, and particularly preferably 1.2 to 5.0. it can.

(Conjugated diene polymer composition)
The conjugated diene polymer composition of the present invention preferably contains the conjugated diene polymer (α) of the present invention, a diene polymer (β) other than (α), and a rubber reinforcing agent (γ). The method for producing a conjugated diene polymer composition of the present invention comprises a step of producing a conjugated diene polymer (α) by polymerizing a conjugated diene compound using the above-described conjugated diene polymerization catalyst of the present invention. It is what. In other words, the method for producing a conjugated diene polymer composition of the present invention comprises a step of producing a conjugated diene polymer (α) by the above-described method for producing a conjugated diene polymer of the present invention. It is.
Specifically, the conjugated diene polymer of the present invention is blended alone or blended with other synthetic rubber or natural rubber, and if necessary, oil-extended with process oil, and then a filler such as carbon black, Vulcanizers, vulcanization accelerators, and other normal compounding agents are added to vulcanize, and rubber applications that require mechanical properties, wear resistance, etc., such as tires, hoses, belts, crawlers, and other various industrial products Can be used for

  The conjugated diene polymer of the present invention is used as a modifier for plastic materials, for example, impact-resistant polystyrene, that is, impact-resistant polystyrene-based resin compositions and rubber-modified impact-resistant polystyrene-based resin compositions. It can also be manufactured.

  The mixing ratio of the conjugated diene polymer composition according to the present invention is preferably 90 to 5 parts by mass of the conjugated diene polymer (α) and 10 to 95 parts by mass of the diene polymer (β) other than (α). The rubber component (α) + (β) 100 parts by mass and the rubber reinforcing agent (γ) 20 to 120 parts by mass.

  The diene polymer (β) other than (α) contained in the conjugated diene polymer composition is preferably a vulcanizable rubber, specifically, natural rubber (NR), ethylene propylene diene rubber (EPDM), Nitrile rubber (NBR), butyl rubber (IIR), chloroprene rubber (CR), polyisoprene, high cis polybutadiene rubber, low cis polybutadiene rubber (BR), styrene-butadiene rubber (SBR), butyl rubber, chlorinated butyl rubber, brominated butyl rubber And acrylonitrile-butadiene rubber. Among these, NR and SBR are preferable. Further, in the case of SBR, although not particularly limited, solution polymerized styrene butadiene copolymer rubber (S-SBR) is particularly preferable. These rubbers may be used alone or in combination of two or more.

  Examples of the rubber reinforcing agent (γ) used in the present invention include various inorganic reinforcing agents such as carbon black, silica, activated calcium carbonate, and ultrafine magnesium silicate. Of these, carbon black and silica are usually preferred. These rubber reinforcing agents may be used alone or in combination of two or more.

Examples of the silica include silicon dioxide (shown by the general formula SiO ₂ ) and silicate fillers such as silicates such as anhydrous silicic acid, hydrous silicic acid, calcium silicate, and aluminum silicate. Further, there is no particular limitation on the aggregation state of silica such as dry silica, precipitation silica, gel silica, colloidal silica, and the production method such as wet method and dry method. These may be used alone or in combination of two or more. Preferably, wet silica having excellent wear resistance is used.

A silane coupling agent can also be used as an additive. The silane coupling agent used as an additive is an organosilicon compound represented by the general formula R ⁴ _n SiR ⁵ _4-n , where R ⁴ is a vinyl group, acyl group, allyl group, allyloxy group, amino group, epoxy group, It is a C1-C20 organic group having a reactive group selected from a mercapto group, a chloro group, an alkyl group, a phenyl group, hydrogen, a styryl group, a methacryl group, an acrylic group, a ureido group, etc., and R ⁵ is a chloro group. , An alkoxy group, an acetoxy group, an isopropenoxy group, an amino group, and the like, and n represents an integer of 1 to 3. The R ⁴ of the above silane coupling agent, those containing a vinyl group and / or a chloro group are preferable.

  As addition amount of the silane coupling agent of an additive, 0.2-20 mass parts is preferable with respect to 100 mass parts of fillers, such as a silica, 3-15 mass parts is more preferable, 5-15 mass parts is especially preferable. . If it is less than the above range, it may cause scorching. Moreover, when more than said range, it may become a cause of a deterioration of a tensile characteristic and elongation.

  The conjugated diene polymer composition according to the present invention can be obtained by kneading the above components using a conventional Banbury, open roll, kneader, biaxial kneader or the like.

  The conjugated diene polymer composition according to the present invention is usually used in the rubber industry as necessary, such as a vulcanizing agent, a vulcanization aid, an anti-aging agent, a filler, process oil, zinc white, and stearic acid. You may knead | mix a compounding agent.

  As the vulcanizing agent, known vulcanizing agents such as sulfur, organic peroxides, resin vulcanizing agents, metal oxides such as magnesium oxide, and the like can be used. The vulcanizing agent is preferably blended in an amount of about 0.5 to 3 parts by mass with respect to 100 parts by mass of the rubber component (α) + (β).

  As the vulcanization aid, known vulcanization aids such as aldehydes, ammonia, amines, guanidines, thioureas, thiazoles, thiurams, dithiocarbamates, xanthates and the like can be used.

  Examples of the anti-aging agent include amine / ketone series, imidazole series, amine series, phenol series, sulfur series and phosphorus series.

  Examples of the filler include inorganic fillers such as silica, calcium carbonate, basic magnesium carbonate, clay, Lissajous, and diatomaceous earth, and organic fillers such as carbon black, recycled rubber, and powder rubber.

  The process oil may be any of aromatic, naphthenic, and paraffinic.

  The conjugated diene polymer composition obtained by the present invention is used for various rubber applications such as industrial articles such as tires, anti-vibration rubbers, belts, hoses and seismic isolation rubbers, and footwear such as men's shoes, women's shoes, and sports shoes. can do. In that case, the rubber component is preferably blended so that at least 10% by weight or more of the conjugated diene polymer of the present invention such as the polybutadiene of the present invention is contained.

(Rubber composition for tire and rubber composition for rubber belt)
The conjugated diene polymer composition of the present invention comprises a rubber composition for a tire and a rubber composition for a rubber belt by adjusting the mixing ratio of the rubber component (α) + (β) and the rubber reinforcing agent (γ). Can be suitably used.
The tire of the present invention uses the conjugated diene polymer composition of the present invention. The method for producing a tire of the present invention is a method for producing a tire containing a conjugated diene polymer, and a conjugated diene polymer is produced by polymerizing a conjugated diene compound using the conjugated diene polymerization catalyst of the present invention described above. It has the process of manufacturing a conjugated diene polymer with the process, in other words, the manufacturing method of the conjugated diene polymer of this invention mentioned above.
The rubber belt of the present invention uses the conjugated diene polymer composition of the present invention. The method for producing a rubber belt of the present invention is a method for producing a rubber belt containing a conjugated diene polymer, and a conjugated diene compound is produced by polymerizing a conjugated diene compound using the above-described catalyst for conjugated diene polymerization of the present invention. It has the process of manufacturing a conjugated diene polymer with the process, in other words, the manufacturing method of the conjugated diene polymer of this invention mentioned above.

  In the case of a tire rubber composition, the rubber composition comprises a rubber component (α) + (β comprising the conjugated diene polymer (α) of the present invention and a diene polymer (β) other than (α). ) And a rubber reinforcing agent (γ), and preferably 30 to 80 parts by mass of the rubber reinforcing agent (γ) with respect to 100 parts by mass of the rubber component (α) + (β).

  In the case of a rubber composition for rubber belts, the rubber composition comprises a rubber component (α) + comprising the conjugated diene polymer (α) of the present invention and a diene polymer (β) other than (α) +. It is preferable to contain 20 to 70 parts by mass of the rubber reinforcing agent (γ) with respect to 100 parts by mass of the rubber component (α) + (β), including (β) and a rubber reinforcing agent (γ).

The rubber composition for a tire and the rubber composition for a rubber belt according to the present invention include a diene polymer (β) other than the conjugated diene polymer (α), and is based on 90 to 5 parts by mass of the conjugated diene polymer (α). Thus, it is preferable to blend 10 to 95 parts by mass of a diene polymer (β) other than the conjugated diene polymer (α).
The diene polymer (β) blended in the tire rubber composition and rubber belt rubber composition according to the present invention is at least one of natural rubber, styrene-butadiene rubber (SBR), and polyisoprene. It is preferable.

  Examples of the rubber reinforcing agent (γ) blended in the tire rubber composition and the rubber composition for rubber belts according to the present invention include various carbon blacks, silica, activated calcium carbonate, ultrafine magnesium silicate, talc, mica and the like. Can be mentioned. Among these, at least one of carbon black and silica is preferable.

  Further, as the rubber reinforcing agent (γ) blended in the tire rubber composition and rubber belt rubber composition, fullerene as disclosed in JP-A-2006-131819 may be used. Examples of fullerenes include C60, C70, a mixture of C60 and C70, and derivatives thereof. Fullerene derivatives include PCBM (Phenyl C61-Butyric acid methyl ester), PCBNB (Phenyl C61-Butyric acid n-Butyl acid), PCBIB (Phenyl C61-Butyl acid 71), PCBIB (Phenyl C61-Butyl acid 71). ester) and the like. In addition, fullerene hydroxide, fullerene oxide, hydrogenated fullerene, and the like can also be used.

  Examples according to the present invention will be specifically described below. The polymerization conditions and polymerization results are summarized in Table 1. Measuring methods for physical properties and the like are as follows.

(Evaluation of polymer)
Catalytic activity: Polymer yield (g) per hour of polymerization time per 1 mmol of the central metal of the catalyst used in the polymerization reaction. For example, when the catalyst is a gadolinium compound, it is the polymer yield (g) per hour of polymerization time per 1 g of gadolinium metal of the gadolinium compound used in the polymerization reaction.

Microstructure: Performed by infrared absorption spectrum analysis. The microstructure was calculated from the absorption intensity ratio of cis 734 cm ⁻¹ , trans 967 cm ⁻¹ and vinyl 910 cm ⁻¹ .

  Number average molecular weight (Mn) and weight average molecular weight (Mw): Calibration performed from a molecular weight distribution curve obtained by GPC (manufactured by Shimadzu Corporation) at a temperature of 40 ° C. using polystyrene as a standard material and tetrahydrofuran as a solvent. The number average molecular weight and the weight average molecular weight were calculated using a line.

  Molecular weight distribution: Mw / Mn, which is the ratio of the weight average molecular weight Mw and the number average molecular weight Mn determined from GPC using polystyrene as a standard substance.

(Evaluation of composition)
Workability: According to JIS-K6300-1, using a Mooney viscometer manufactured by Shimadzu Corporation, the composition was preheated at 100 ° C. for 1 minute and then measured for 4 minutes to determine the Mooney viscosity (ML _{1 + 4} , 100 ° C.), and Comparative Example 3 described in Table 3 was taken as 100 and indicated as an index. The smaller Mooney viscosity is the better the processability. In addition, the index in Table 3 is described so as to increase as workability increases.

  Tensile stress: 50%, 100% and 300% tensile stress was measured in accordance with JIS-K6251 and each comparative example described in each table was indicated as an index. The higher the index, the better.

  Rebound resilience: According to JIS-K6255, the rebound resilience was measured at room temperature using a Dunlop trypometer, and each table indicated an index with each of the comparative examples described as 100. The higher the index, the better.

  Abrasion resistance: Lambourn abrasion resistance was measured at a slip ratio of 40% according to the measurement method defined in JIS-K6264, and the index was displayed with Comparative Example 3 described in Table 3 as 100. The higher the index, the better.

  Low exothermic property / permanent strain: The calorific value and permanent strain increased in 25 minutes at a measurement temperature of 100 ° C. using a flexometer according to JIS-K6265, and the comparative examples described in each table are 100 as each. The index was displayed. The calorific value and permanent set should be small. In addition, the index in each table is described so as to increase as the low heat build-up and permanent set increase.

  Filler dispersibility: Dispersibility of the filler in the composition due to strain dependency (Pain effect) of the storage elastic modulus (G ′), using a rubber processability analyzer RPA-2000 manufactured by Alpha Technology, 120 ° C., 1 Hz The dynamic strain analysis was performed under the condition of the frequency. For the Payne effect, the ratio of G ′ when the strain is 25% and G ′ when the strain is 0.5% (G′25% / G′0.5%) is set to 100 in Comparative Example 3 described in Table 3. The index was displayed. It shows that the dispersibility of a reinforcing agent is so favorable that an index | exponent is large.

  Wet grip performance (tan δ (0 ° C.)): Measured at a temperature range of −120 ° C. to 100 ° C., a frequency of 16 Hz, and a dynamic strain of 0.3% using a viscoelasticity measuring device (manufactured by GABO, EPLEXOR 100N). Was used as an index of wet grip performance. The index was displayed with Comparative Example 3 described in Table 3 as 100. The higher the index, the better.

  Low fuel consumption (tan δ (60 ° C.)): Measured at a temperature range of −120 ° C. to 100 ° C., a frequency of 16 Hz, and a dynamic strain of 0.3% using a viscoelasticity measuring device (manufactured by GABO, EPLEXOR 100N). Tan δ was used as an index of low fuel consumption. The index was displayed with Comparative Example 4 shown in Table 5 as 100. Low fuel consumption (tan δ) is better. In addition, the index in the table is described so as to increase as the fuel efficiency improves.

  Low temperature characteristics (−30 ° C. storage elastic modulus (E ′)): Using a viscoelasticity measuring device (manufactured by GABO, EPLEXOR 100N), temperature range −120 ° C. to 100 ° C., frequency 16 Hz, dynamic strain 0.3% The storage elastic modulus (E ′) at −30 ° C. was used. In each table, the comparative examples described were each represented as 100 as an index. The larger the index, the lower the elastic modulus at −30 ° C. and the better.

Example 1
The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 245 ml of cyclohexane solvent and 250 ml of butadiene was charged. Then, 1.0 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, after adding 0.6 ml of a toluene solution (0.005 mol / L) of gadolinium (III) triisopropoxide (Gd (OiPr) ₃ ), a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate 1.5 ml (0.004 mol / L) was added. After polymerization at 60 ° C. for 25 minutes, 3 ml of an ethanol solution containing an antioxidant was added to stop the polymerization. After releasing the pressure inside the autoclave, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

(Example 2)
The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 245 ml of cyclohexane solvent and 250 ml of butadiene was charged. Then, 1.0 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, after adding 0.4 ml of a toluene solution (0.005 mol / L) of gadolinium (III) triisopropoxide (Gd (OiPr) ₃ ), a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate 1.0 ml (0.004 mol / L) was added. After polymerization at 60 ° C. for 25 minutes, 3 ml of an ethanol solution containing an antioxidant was added to stop the polymerization. After releasing the pressure inside the autoclave, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

(Example 3)
The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 245 ml of cyclohexane solvent and 250 ml of butadiene was charged. Then, 1.0 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, after adding 0.4 ml of a toluene solution (0.005 mol / L) of gadolinium (III) triisopropoxide (Gd (OiPr) ₃ ), a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate 1.0 ml (0.004 mol / L) was added. After polymerization at 50 ° C. for 25 minutes, 3 ml of an ethanol solution containing an antioxidant was added to stop the polymerization. After releasing the pressure inside the autoclave, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

Example 4
The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 245 ml of cyclohexane solvent and 250 ml of butadiene was charged. Then, 1.0 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, after adding 0.8 ml of a toluene solution (0.005 mol / L) of gadolinium (III) triisopropoxide (Gd (OiPr) ₃ ), a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate 2.0 ml (0.004 mol / L) was added. After polymerization at 50 ° C. for 25 minutes, 3 ml of an ethanol solution containing an antioxidant was added to stop the polymerization. After releasing the pressure inside the autoclave, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

(Example 5)
The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 245 ml of cyclohexane solvent and 250 ml of butadiene was charged. Then, 1.0 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, after adding 0.6 ml of a toluene solution (0.005 mol / L) of gadolinium (III) triisopropoxide (Gd (OiPr) ₃ ), a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate 1.5 ml (0.004 mol / L) was added. After polymerization at 50 ° C. for 25 minutes, 3 ml of an ethanol solution containing an antioxidant was added to stop the polymerization. After releasing the pressure inside the autoclave, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

(Example 6)
The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 245 ml of cyclohexane solvent and 250 ml of butadiene was charged. Then, 1.25 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, after adding 0.6 ml of a toluene solution (0.005 mol / L) of gadolinium (III) triisopropoxide (Gd (OiPr) ₃ ), a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate 1.5 ml (0.004 mol / L) was added. After polymerization at 50 ° C. for 25 minutes, 3 ml of an ethanol solution containing an antioxidant was added to stop the polymerization. After releasing the pressure inside the autoclave, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

(Example 7)
The inside of the 1.5 L autoclave was purged with nitrogen, and a solution consisting of 495 ml of cyclohexane solvent and 500 ml of butadiene was charged. Then, 3.0 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, after adding 1.2 ml of a toluene solution (0.005 mol / L) of gadolinium (III) triisopropoxide (Gd (OiPr) ₃ ), a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate 3.0 ml (0.004 mol / L) was added. After polymerization at 50 ° C. for 25 minutes, 5 ml of an ethanol solution containing an antioxidant was added to terminate the polymerization. After releasing the pressure inside the autoclave, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

(Example 8)
The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 245 ml of cyclohexane solvent and 250 ml of butadiene was charged. Then, 1.0 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, after adding 0.4 ml of a toluene solution (0.005 mol / L) of praseodymium (III) triisopropoxide (Pr (OiPr) ₃ ), a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate 1.0 ml (0.004 mol / L) was added. After polymerization at 50 ° C. for 25 minutes, 3 ml of an ethanol solution containing an antioxidant was added to stop the polymerization. After releasing the pressure inside the autoclave, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

Example 9
The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 245 ml of cyclohexane solvent and 250 ml of butadiene was charged. Then, 1.0 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, after adding 0.4 ml of a toluene solution (0.005 mol / L) of dysprosium (III) triisopropoxide (Dy (OiPr) ₃ ), a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate 1.0 ml (0.004 mol / L) was added. After polymerization at 50 ° C. for 25 minutes, 3 ml of an ethanol solution containing an antioxidant was added to stop the polymerization. After releasing the pressure inside the autoclave, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

(Example 10)
The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 245 ml of cyclohexane solvent and 250 ml of butadiene was charged. Then, 1.0 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, after adding 0.4 ml of a toluene solution (0.005 mol / L) of lanthanum (III) triisopropoxide (La (OiPr) ₃ ), a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate 1.0 ml (0.004 mol / L) was added. After polymerization at 50 ° C. for 25 minutes, 3 ml of an ethanol solution containing an antioxidant was added to stop the polymerization. After releasing the pressure inside the autoclave, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

(Example 11)
The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 245 ml of cyclohexane solvent and 250 ml of butadiene was charged. Then, 1.0 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, after adding 0.4 ml of a toluene solution (0.005 mol / L) of neodymium (III) triisopropoxide (Nd (OiPr) ₃ ), a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate 1.0 ml (0.004 mol / L) was added. After polymerization at 50 ° C. for 25 minutes, 3 ml of an ethanol solution containing an antioxidant was added to stop the polymerization. After releasing the pressure inside the autoclave, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

(Example 12)
The inside of the autoclave having an internal volume of 2 L was purged with nitrogen, charged with a solution consisting of 260 ml of cyclohexane and 140 ml of butadiene, and 0.9 ml of a toluene solution of triethylaluminum (TEAL) (2 mol / L) was added. Next, 0.15 ml of scandium (III) triisopropoxide in toluene (0.04 mol / L) and 3.2 ml of triphenylcarbenium tetrakis (pentafluorophenyl) borate in toluene (0.0038 mol / L) were added. Then, polymerization was started. After polymerization at 40 ° C. for 25 minutes, 4 ml of an ethanol solution containing an antioxidant was added to stop the polymerization. After releasing the pressure inside the autoclave, the polymerization solution was put into ethanol to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

(Example 13)
The inside of the autoclave having an internal volume of 2 L was purged with nitrogen, a solution consisting of 260 ml of cyclohexane and 140 ml of butadiene was charged, and 1.5 ml of a toluene solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, 0.15 ml of scandium (III) triisopropoxide in toluene (0.04 mol / L) and 3.2 ml of triphenylcarbenium tetrakis (pentafluorophenyl) borate in toluene (0.0038 mol / L) were added. Then, polymerization was started. After polymerization at 40 ° C. for 25 minutes, 4 ml of an ethanol solution containing an antioxidant was added to stop the polymerization. After releasing the pressure inside the autoclave, the polymerization solution was put into ethanol to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

(Example 14)
The inside of the autoclave having an internal volume of 2 L was purged with nitrogen, a solution consisting of 260 ml of toluene and 140 ml of butadiene was charged, and 5 ml of a toluene solution of triethylaluminum (TEAL) (3 mol / L) was added. Next, 0.06 ml of a scandium (III) triisopropoxide solution in toluene (0.04 mol / L) and 2 ml of a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (0.0024 mol / L) were added. Polymerization was started. After polymerization at 40 ° C. for 30 minutes, 4 ml of an ethanol solution containing an antioxidant was added to terminate the polymerization. After releasing the pressure inside the autoclave, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

(Example 15)
The inside of the autoclave having an internal volume of 2 L was purged with nitrogen, a solution consisting of 260 ml of toluene and 140 ml of butadiene was charged, and 6.8 ml of a toluene solution of triethylaluminum (TEAL) (3 mol / L) was added. Next, 0.06 ml of a scandium (III) triisopropoxide solution in toluene (0.04 mol / L) and 2 ml of a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (0.0024 mol / L) were added. Polymerization was started. After polymerization at 40 ° C. for 30 minutes, 4 ml of an ethanol solution containing an antioxidant was added to terminate the polymerization. After releasing the pressure inside the autoclave, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

(Example 16)
The inside of the autoclave having an internal volume of 2 L was purged with nitrogen, a solution consisting of 260 ml of toluene and 140 ml of butadiene was charged, and 5 ml of a toluene solution of triethylaluminum (TEAL) (3 mol / L) was added. Next, 0.06 ml of a scandium (III) triisopropoxide solution in toluene (0.04 mol / L) and 2 ml of a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (0.0024 mol / L) were added. Polymerization was started. After polymerization at 40 ° C. for 30 minutes, 4 ml of an ethanol solution containing an antioxidant was added to terminate the polymerization. After releasing the pressure inside the autoclave, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

(Example 17)
The inside of the autoclave having an internal volume of 2 L was purged with nitrogen, a solution consisting of 260 ml of toluene and 140 ml of butadiene was charged, and 5 ml of a toluene solution of triethylaluminum (TEAL) (3 mol / L) was added. Next, 0.06 ml of a scandium (III) triisopropoxide solution in toluene (0.04 mol / L) and 2 ml of a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (0.0024 mol / L) were added. Polymerization was started. After 30 minutes of polymerization at 30 ° C., 4 ml of an ethanol solution containing an antioxidant was added to stop the polymerization. After releasing the pressure inside the autoclave, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

(Example 18)
The inside of the autoclave having an internal volume of 2 L was purged with nitrogen, a solution consisting of 260 ml of toluene and 140 ml of butadiene was charged, and 5 ml of a toluene solution of triethylaluminum (TEAL) (3 mol / L) was added. Next, 0.06 ml of a scandium (III) triisopropoxide solution in toluene (0.04 mol / L) and 2 ml of a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (0.0024 mol / L) were added. Polymerization was started. After polymerization at 50 ° C. for 30 minutes, 4 ml of an ethanol solution containing an antioxidant was added to terminate the polymerization. After releasing the pressure inside the autoclave, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

(Example 19)
The inside of the autoclave having an internal volume of 2 L was purged with nitrogen, a solution consisting of 260 ml of toluene and 140 ml of butadiene was charged, and 6.7 ml of a toluene solution (1.8 mol / L) of triisobutylaluminum (TIBA) was added. Next, 0.2 ml of a scandium (III) triisopropoxide solution in toluene (0.04 mol / L) and 4 ml of a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (0.004 mol / L) were added. Polymerization was started. After polymerization at 40 ° C. for 30 minutes, 4 ml of an ethanol solution containing an antioxidant was added to terminate the polymerization. After releasing the pressure inside the autoclave, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

(Example 20)
The inside of the autoclave having an internal volume of 2 L was purged with nitrogen, a solution consisting of 260 ml of toluene and 140 ml of butadiene was charged, and 6.7 ml of a toluene solution (1.8 mol / L) of triisobutylaluminum (TIBA) was added. Next, 0.2 ml of a scandium (III) triisopropoxide solution in toluene (0.04 mol / L) and 4 ml of a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (0.004 mol / L) were added. Polymerization was started. After polymerization at 40 ° C. for 30 minutes, 4 ml of an ethanol / heptane (1/1) solution containing an antioxidant was added to stop the polymerization. After releasing the pressure inside the autoclave, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

(Example 21)
The interior of the autoclave having an internal volume of 2 L was purged with nitrogen, charged with a solution consisting of 240 ml of cyclohexane and 260 ml of butadiene, and 4.0 ml of a toluene solution of triethylaluminum (TEAL) (2 mol / L) was added. Next, 0.38 ml of a toluene solution (0.04 mol / L) of scandium (III) triisopropoxide was added, and then a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate (0.004 mol / L) 7 .6 ml was added to initiate the polymerization. After polymerization at 60 ° C. for 30 minutes, 4 ml of an ethanol solution containing an antioxidant was added to stop the polymerization. After releasing the pressure inside the autoclave, ethanol was added to the polymerization solution to recover polybutadiene. The recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. The polymerization results are shown in Table 1.

(Comparative Example 1)
The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 245 ml of cyclohexane solvent and 250 ml of butadiene was charged. Then, 1.0 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, after adding 0.4 ml of toluene solution (0.005 mol / L) of samarium (III) triisopropoxide (Sm (OiPr) ₃ ), toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate 1.0 ml (0.004 mol / L) was added. After polymerization at 50 ° C. for 25 minutes, 3 ml of an ethanol solution containing an antioxidant was added to stop the polymerization. After releasing the pressure inside the autoclave and then adding ethanol to the polymerization solution, no polybutadiene was produced and the yield was 0.0 g. The polymerization results are shown in Table 1.

(Comparative Example 2)
The inside of an autoclave having an internal volume of 1.5 L was purged with nitrogen, and a solution consisting of 245 ml of cyclohexane solvent and 250 ml of butadiene was charged. Then, 1.0 ml of a cyclohexane solution (2 mol / L) of triethylaluminum (TEAL) was added. Next, after adding 0.4 ml of a toluene solution (0.005 mol / L) of ytterbium (III) triisopropoxide (Yb (OiPr) ₃ ), a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate 1.0 ml (0.004 mol / L) was added. After polymerization at 50 ° C. for 25 minutes, 3 ml of an ethanol solution containing an antioxidant was added to stop the polymerization. After releasing the pressure inside the autoclave and then adding ethanol to the polymerization solution, no polybutadiene was produced and the yield was 0.0 g. The polymerization results are shown in Table 1.

(Reference Example 1)
Table 1 shows the results of calculating the yield and the catalytic activity of Example 11 described in JP-A-7-70143 (Patent Document 1).

(Reference Example 2)
Table 1 shows the results of calculating the yield and catalytic activity of Example 23 described in JP-A-7-70143 (Patent Document 1).

  As described above, a conjugated diene polymer having a high cis-1,4 structure content can be produced with high activity by using the conjugated diene polymerization catalyst containing the rare earth metal alkoxide compound of the present invention.

(Compound evaluation)
(Example 22)
Using polybutadiene synthesized according to Example 7, natural rubber, carbon black (ISAF), zinc oxide, stearic acid, anti-aging agent (Antigen 6C manufactured by Sumitomo Chemical Co., Ltd.), oil ( Implemented primary blending by adding naphthenic oil from Japan Energy Co., Ltd., followed by secondary blending with vulcanization accelerator (Noxeller NS, manufactured by Ouchi Shinsei Chemical Co., Ltd.) and sulfur. Thus, a compounded rubber was produced. Furthermore, the physical properties of the vulcanized product obtained by molding this compounded rubber according to the desired physical properties and press vulcanizing at 150 ° C. were measured. Table 3 shows the measurement results of various compound physical properties.

(Comparative Example 3)
Using UBEPOL BR150L (conjugated diene polymer polymerized using a Co-based catalyst) manufactured by Ube Industries, Ltd., in accordance with the formulation shown in Table 2, natural rubber, carbon black (ISAF), zinc oxide, stearic acid according to the formulation shown in Table 2 , Anti-aging agent (Antigen 6C manufactured by Sumitomo Chemical Co., Ltd.) and oil (naphthenic oil manufactured by Japan Energy Co., Ltd.) were added and kneaded, followed by a vulcanization accelerator (Ouchi Shinsei Chemical Industry) on a roll. Noxeller NS) manufactured by Co., Ltd., and a secondary compounding with sulfur was carried out to produce a compounded rubber. Furthermore, the physical properties of the vulcanized product obtained by molding this compounded rubber according to the desired physical properties and press vulcanizing at 150 ° C. were measured. Table 3 shows the measurement results of various compound physical properties.

  Table 2 shows the formulation.

  Table 3 shows the evaluation results of the obtained blend.

  The numerical values in Table 3 are Ube Industries, Ltd., UBEPOL BR150L (a conjugated diene polymer polymerized using a Co-based catalyst), with each characteristic value of Comparative Example 3 as a reference (100). Each item is displayed as an index. The larger the value, the better the characteristics.

  As shown in Table 3, the composition of Example 22 using polybutadiene obtained in Example 7 is more workable, tensile strength, rebound resilience, abrasion resistance than the composition of Comparative Example 3 using UBEPOL BR150L. Excellent exothermic property, permanent strain, filler dispersibility (Pain effect), wet grip performance (tan δ (0 ° C.)), and low temperature characteristics (low temperature storage modulus).

(Example 23)
Using polybutadiene synthesized according to Example 21, according to the formulation shown in Table 4, natural rubber, carbon black (ISAF), zinc oxide, stearic acid, anti-aging agent (Antigen 6C manufactured by Sumitomo Chemical Co., Ltd.), oil ( Implemented primary blending by adding naphthenic oil from Japan Energy Co., Ltd., followed by secondary blending with vulcanization accelerator (Noxeller NS, manufactured by Ouchi Shinsei Chemical Co., Ltd.) and sulfur. Thus, a compounded rubber was produced. Furthermore, the physical properties of the vulcanized product obtained by molding this compounded rubber according to the desired physical properties and press vulcanizing at 150 ° C. were measured. Table 5 shows the measurement results of various compound physical properties.

(Comparative Example 4)
Using UBEPOL BR150L (conjugated diene polymer polymerized using a Co-based catalyst) manufactured by Ube Industries, Ltd., according to the formulation shown in Table 4, natural rubber, carbon black (ISAF), zinc oxide, stearic acid according to the formulation shown in Table 4 , Anti-aging agent (Antigen 6C manufactured by Sumitomo Chemical Co., Ltd.) and oil (naphthenic oil manufactured by Japan Energy Co., Ltd.) were added and kneaded, followed by a vulcanization accelerator (Ouchi Shinsei Chemical Industry) on a roll. Noxeller NS) manufactured by Co., Ltd., and a secondary compounding with sulfur was carried out to produce a compounded rubber. Furthermore, the physical properties of the vulcanized product obtained by molding this compounded rubber according to the desired physical properties and press vulcanizing at 150 ° C. were measured. Table 5 shows the measurement results of various compound physical properties.

  Table 4 shows the formulation.

  Table 5 shows the evaluation results of the obtained blend.

  The numerical values in Table 5 are Ube Industries, Ltd., UBEPOL BR150L (a conjugated diene polymer polymerized using a Co-based catalyst), each characteristic value of Comparative Example 4 as a reference (100), Each item is displayed as an index. The larger the value, the better the characteristics.

  As shown in Table 5, the composition of Example 23 using the polybutadiene obtained in Example 21 is higher in tensile strength, rebound resilience, low heat build-up, permanent set than the composition of Comparative Example 4 using UBEPOL BR150L. Excellent low temperature characteristics (low temperature storage modulus) and low fuel consumption (tan δ (60 ° C.)).

Claims (12)

  Rare earth metal alkoxide compound (A) (except Sm alkoxide compound, Eu alkoxide compound and Yb alkoxide compound), ionic compound (B) comprising non-coordinating anion and cation, and periodic table A conjugated diene polymerization catalyst comprising: an organometallic compound (C) of an element selected from Group 2, 12, and 13. The conjugated diene polymerization catalyst according to claim 1, wherein the rare earth metal alkoxide compound (A) is an alkoxide compound represented by the following general formula (1).

(Wherein R represents a substituent having 1 to 6 carbon atoms, O represents an oxygen atom, and Ln represents a rare earth metal atom (except Sm, Eu and Yb).)   The catalyst for conjugated diene polymerization according to claim 1 or 2, wherein the organometallic compound (C) is organoaluminum.   The catalyst for conjugated diene polymerization according to any one of claims 1 to 3, wherein the ionic compound (B) is a boron-containing compound.   A method for producing a conjugated diene polymer, comprising polymerizing a conjugated diene compound using the conjugated diene polymerization catalyst according to claim 1.   A conjugated diene polymer obtained by polymerizing a conjugated diene compound using the conjugated diene polymerization catalyst according to claim 1. An ion comprising a rare earth metal alkoxide compound (A) represented by the following general formula (1) (excluding Sm alkoxide compounds, Eu alkoxide compounds and Yb alkoxide compounds), a non-coordinating anion and a cation Conjugated by polymerizing a conjugated diene compound using a conjugated diene polymerization catalyst having an organic compound (B) and an organometallic compound (C) of an element selected from Groups 2, 12 and 13 of the periodic table A conjugated diene polymer composition comprising a diene polymer (α), a diene polymer (β) other than (α), and a rubber reinforcing agent (γ).

(However, R ¹ , R ² and R ³ each represent hydrogen or a substituent having 1 to 12 carbon atoms. Ln represents a rare earth metal atom (except Sm, Eu and Yb).)   The conjugated diene polymer composition according to claim 7, wherein the rubber reinforcing agent (γ) is carbon black and / or silica.   The molecular weight of the conjugated diene compound is adjusted with a compound selected from (1) hydrogen, (2) a metal hydride compound, and (3) a hydrogenated organometal compound. 9. The conjugated diene polymer composition according to 8.   The conjugated diene polymer composition according to any one of claims 7 to 9, wherein the conjugated diene compound is 1,3-butadiene.   A tire using the conjugated diene polymer composition according to any one of claims 7 to 10.   A rubber belt using the conjugated diene polymer composition according to any one of claims 7 to 10.