JP2012056949A - Yttrium compound and conjugated diene polymerization catalyst using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new yttrium compound having a bulky ligand; and to provide a conjugated diene polymerization catalyst using the compound, especially the polymerization catalyst capable of producing a conjugated diene polymer having a high content of cis-1,4 structure in high efficiency.SOLUTION: The conjugated diene polymerization catalyst comprises the new yttrium compound (A) having the bulky ligand, an ionic compound (B) comprising a non-coordinating anion and a cation, and an organometallic compound (C) of an element selected from group 2, 12 and 13 elements in the periodic table.

Description

  The present invention relates to a novel yttrium compound having a bulky ligand and a conjugated diene polymerization catalyst using the same.

  Many proposals have been made on 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.

  Polymerization of conjugated dienes using a Group 3 element of the periodic table as a catalyst is known, and various polymerization methods have been proposed so far. For example, Japanese Patent Laid-Open No. 7-268013 (Patent Document 1) 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. .

  JP-A-11-80222 (Patent Document 2) discloses a group IIIB metal compound of a periodic table, an ionic compound of a non-coordinating anion and a cation, and an organic metal of a group I to III element of the periodic table. A polymerization catalyst comprising a compound is disclosed.

  International Publication No. 2006/049016 (Patent Document 3) includes a yttrium compound having a bulky substituent, an ionic compound composed of a non-coordinating anion and a cation, and groups 2 and 12 of the periodic table. A catalyst system comprising an organometallic compound of an element selected from Group 13 elements is disclosed.

  Japanese Patent Application Laid-Open No. 2008-56584 (Patent Document 4) discloses an olefin or conjugated diene polymerization catalyst containing a scandium or yttrium cationic cyclopentadienyl complex. However, the activity is very low.

JP-A-7-70143 Japanese Patent Laid-Open No. 7-268013 International Publication No. 2006/049016 JP 2008-56584 A

  The present invention provides a novel yttrium compound having a bulky ligand and a conjugated diene polymerization catalyst using the same, and particularly, a conjugated diene polymer having a high cis-1,4 structure content is produced with high efficiency. An object of the present invention is to provide a polymerization catalyst that can be used.

（但し、Ｒ²、Ｒ³は水素、または炭素数１〜１２の置換基を表し、Ｏは酸素原子を表し、Ｙはイットリウム原子を表す。） The present invention is an yttrium compound having a bulky ligand represented by the following general formula (1).

(Wherein, R ^2, R ³ represents hydrogen, or a substituent having 1 to 12 carbon atoms, O represents an oxygen atom, Y represents yttrium atom.)

  The present invention also provides an yttrium compound (A) having the above-mentioned bulky ligand, an ionic compound (B) comprising a non-coordinating anion and a cation, groups 2, 12, and 13 in the periodic table. A process for producing a conjugated diene polymer, characterized by comprising a catalyst for conjugated diene polymerization comprising an organometallic compound (C) of an element selected from It is.

  By using the yttrium compound having a bulky ligand of the present invention, a polymerization catalyst capable of producing a conjugated diene polymer having a high cis-1,4 structure content with high activity can be provided.

（但し、Ｒ²、Ｒ³は水素、または炭素数１〜１２の置換基を表し、Ｏは酸素原子を表し、Ｙはイットリウム原子を表す。） The yttrium compound of the present invention is an yttrium compound having a bulky ligand represented by the following general formula (1).

(Wherein, R ^2, R ³ represents hydrogen, or a substituent having 1 to 12 carbon atoms, O represents an oxygen atom, Y represents yttrium atom.)

Specific examples of the substituent having 1 to 12 carbon atoms in R ² and R ³ 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 Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tricyclo [3.3.1.13.7. Saturated hydrocarbon groups such as dec-1-yl (adamantyl) group, unsaturated hydrocarbon groups such as vinyl group, 1-propenyl group and allyl group, alicyclic groups such as cyclohexyl group, methylcyclohexyl group and ethylcyclohexyl group Aromatic hydrocarbon groups such as hydrocarbon group, phenyl group, benzyl group, toluyl group, phenethyl group and the like can be mentioned. Further, 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. Among these, a saturated hydrocarbon group having 1 to 12 carbon atoms is preferable, and a saturated hydrocarbon group having 1 to 10 carbon atoms is particularly preferable.

Specific examples of the yttrium compound include tris (1,3-bis (1-adamantyl) -1,3-propanedionato) yttrium, tris (1- (1-adamantyl) -1,3-butanedionato) yttrium, and tris. (1- (1-adamantyl) -1,3-pentanedionato) yttrium, tris (1- (1-adamantyl) -4-methyl-1,3-pentandedionato) yttrium, tris (1- (1- Adamantyl) -4,4-dimethyl-1,3-pentanedionato) yttrium, tris (1- (1-adamantyl) -3-phenyl-1,3-propanedionato) yttrium, tris (1,3-bis (Adamantyl) -2-methyl-1,3-propanedionato) yttrium, tris (1- (1-adamantyl) -2,4,4- Rimechiru-1,3-pentanedionato), and the yttrium.

  The yttrium compound (A) having a bulky ligand is an ionic compound (B) composed of a non-coordinating anion and a cation, an element selected from Groups 2, 12, and 13 of the periodic table. By combining with the organometallic compound (C), it can be used as a conjugated diene polymerization catalyst.

  In the ionic compound comprising a non-coordinating anion and a cation as the component (B) of the catalyst system, examples of the non-coordinating anion include tetra (phenyl) borate and tetra (fluorophenyl) borane. , Tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (3,5-bistrifluoromethyl) Phenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (triyl) borate, tetra (xylyl) borate, triphenyl (pentafluorophenyl) borate, tris (pentafluorophenyl) (Phenyl) borate, tridecahydride-7,8- Cal Bowne deca borate - DOO, tetrafluoroborate - DOO, hexafluorophosphate - such DOO 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, those arbitrarily selected and combined from the non-coordinating anions and cations exemplified above can be preferably used.

  Among these, as ionic compounds, triphenylcarbonium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (fluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate. And 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate are preferred. An ionic compound 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 includes a chain aluminoxane represented by the general formula (—Al (R ′) O—) n or a cyclic aluminoxane. (R ′ is a hydrocarbon group having 1 to 10 carbon atoms, including those partially substituted with a halogen atom and / or an alkoxy group. 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 the organoaluminum compound used as an aluminoxane raw material include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof.

  Among these, alumoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can be suitably used.

  Moreover, as a condensing agent, water can be mentioned as a typical example, but in addition to this, an arbitrary one that the trialkylaluminum undergoes a condensation reaction, for example, adsorbed water such as an inorganic substance, a diol, and the like.

  Examples of organometallic compounds of Group 2, 12 and 13 of the periodic table that are the component (C) of the catalyst system include organic magnesium, organic zinc, and organic aluminum. Preferred among these compounds are dialkyl magnesium, alkyl magnesium chloride, alkyl magnesium bromide, dialkyl zinc, trialkyl aluminum, dialkyl aluminum chloride, dialkyl aluminum bromide, alkyl aluminum sesquichloride, alkyl aluminum sesquibromide, alkyl aluminum dichloride, Dialkylaluminum hydride and the like.

  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.

  In addition, 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.

  Although the conjugated diene can be polymerized using the above-mentioned catalyst, (1) hydrogen, (2) metal hydride compound, and (3) hydrogenated organometal as the molecular weight regulator of the resulting conjugated diene polymer. A compound selected from compounds can be used.

  Examples of the molecular weight regulator (2) metal hydride compound include lithium hydride, sodium hydride, potassium hydride, magnesium hydride, calcium hydride, borane, aluminum hydride, gallium hydride, silane, germane, Examples thereof include lithium borohydride, sodium borohydride, lithium aluminum hydride, sodium aluminum hydride, and the like.

  (3) Examples of hydrogenated organometallic compounds include alkylboranes such as methylborane, ethylborane, propylborane, butylborane, and phenylborane; dialkylboranes such as dimethylborane, diethylborane, dipropylborane, dibutylborane, and diphenylborane; methyl Alkyl aluminum dihydride such as aluminum dihydride, ethylaluminum dihydride, propylaluminum dihydride, butylaluminum dihydride, phenylaluminum dihydride, dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, dibutylaluminum hydride, diphenylaluminum hydride Dialkyl aluminum high dry Silanes such as methylsilane, ethylsilane, propylsilane, butylsilane, phenylsilane, dimethylsilane, diethylsilane, dipropylsilane, dibutylsilane, diphenylsilane, trimethylsilane, triethylsilane, tripropylsilane, tributylsilane, triphenylsilane, Germanium 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, triphenyl germane And the like.

  Among these, diisobutylaluminum hydride and diethylaluminum hydride are preferable, and diethylaluminum hydride is particularly preferable.

  The order of addition of the catalyst components is not particularly limited, but can be performed, for example, in the following order.

  (1) In an inert organic solvent, the component (C) is added in the presence or absence of the conjugated diene compound monomer to be polymerized, and the components (A) and (B) are added in any order.

  (2) In the inert organic solvent, the component (C) is added in the presence or absence of the conjugated diene compound monomer to be polymerized, the molecular weight regulator is added, and then the components (A) and (B ) Add ingredients in any order.

  (3) After adding the component (A) in the presence or absence of the conjugated diene compound monomer to be polymerized in an inert organic solvent, and adding the component (C) and the molecular weight regulator described above in any order. , (B) component is added.

  (4) After adding the component (B) in the presence or absence of the conjugated diene compound monomer to be polymerized in an inert organic solvent, and adding the component (C) and the molecular weight regulator described above in any order. , (A) component is added.

  (5) After adding component (C) in the presence or absence of a conjugated diene compound monomer to be polymerized in an inert organic solvent, and adding components (A) and (B) in any order Add the above-described molecular weight regulator.

  Moreover, you may age | cure and use each component previously. Especially, it is preferable to age | cure (A) component and (C) component.

  As aging conditions, the component (A) and the component (C) are mixed in an inert solvent in the presence or absence of the conjugated diene compound monomer to be polymerized. The aging temperature is -50 to 80 ° C, preferably -10 to 50 ° C, and the aging time is 0.01 to 24 hours, preferably 0.05 to 5 hours, particularly preferably 0.1 to 1 hour.

  In the present invention, each catalyst component may be supported on an inorganic compound or an organic polymer compound.

  Conjugated diene compound monomers include 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 these, a conjugated diene compound monomer mainly composed of 1,3-butadiene is preferable.

  These monomer components may be used singly or in combination of two or more.

  Here, the conjugated diene compound monomer to be polymerized may be the total amount or a part of the monomer. In the case of part of the monomer, the above contact mixture can be mixed with the remaining monomer or the remaining monomer solution. In addition to conjugated dienes, olefins such as ethylene, propylene, allene, 1-butene, 2-butene, 1,2-butadiene, pentene, cyclopentene, hexene, cyclohexene, octene, cyclooctadiene, cyclododecatriene, norbornene, norbornadiene, etc. A compound or the like may be contained.

  The polymerization method is not particularly limited, and bulk polymerization (bulk polymerization) using a conjugated diene compound monomer such as 1,3-butadiene itself as a polymerization solvent, or solution polymerization 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, and ethylbenzene, Examples thereof include olefinic hydrocarbons such as olefin compounds and cis-2-butene and trans-2-butene.

  Among these, benzene, toluene, cyclohexane, or a mixture of cis-2-butene and trans-2-butene is preferably used.

  The polymerization temperature is preferably in the range of -30 to 150 ° C, particularly preferably in the range of 30 to 100 ° C. The polymerization time is preferably in the range of 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-polybutadiene having a cis-1,4 structure of 90% or more, more preferably 92% or more, particularly preferably 96% or more. . [Η] of the conjugated diene polymer is preferably 0.1 to 10, more preferably 1 to 7, and particularly preferably 1.5 to 5.

Examples according to the present invention will be specifically described below. The polymerization conditions and polymerization results are summarized in Tables 1 and 2. Measuring methods for physical properties and the like are as follows.
1) NMR spectrum: Measured using a JNM / AL400 spectrum meter manufactured by JEOL.
2) Measurement of Y content: Measured by ICP emission spectrometry. For the measurement, Vista MPX type manufactured by Varian Japan was used.
3) Elemental analysis: The CHN coder MT-5 manufactured by Yanaco was used.
4) Microstructure: Performed by infrared absorption spectrum analysis. The microstructure was calculated from the absorption intensity ratio of cis 740 cm ⁻¹ , trans 967 cm ⁻¹ and vinyl 910 cm ⁻¹ .
5) Intrinsic viscosity ([η]): Measured at 30 ° C. using a toluene solution of the polymer.

(Synthesis Example 1)
To a 500 ml eggplant-shaped two-necked flask were added 10.45 g (93.1 mmol) of t-butoxypotassium and 100 ml of dry DMF, and the mixture was stirred with a magnetic stirrer. Separately, a solution prepared by dissolving 12.06 g (62.1 mmol) of methyl 1-adamantanecarboxylate in 50 ml of dry DMF was prepared and dropped into a THF solution of t-butoxy potassium. Next, separately from this, a solution prepared by dissolving 13.28 g (74.5 mmol) of 1-adamantyl methyl ketone in 50 ml of dry DMF was prepared and dropped into the reaction solution. The reaction was carried out at 100 ° C. for 15 hours. After cooling to room temperature, 100 ml of 1N hydrochloric acid was added to stop the reaction. After DMF was distilled off, extraction was performed 3 times using 40 ml of ethyl acetate. After drying overnight with dry sodium sulfate, the mixture was filtered, and the filtrate was dried under reduced pressure to obtain a crude product. The obtained crude product was separated by column chromatography using silica gel to obtain 1,3-bis (1-adamantyl) -1,3-propanedione. Yield 5.03 g (14.8 mmol), yield 24%.
As a result of nuclear magnetic resonance spectrum (NMR) of the product, ¹ H-NMR δ (ppm): 5.7 (1H), 1.9 (18H), 1.6 (12H) However, the measurement solvent is C ₆ D ₆ was used.

(Synthesis Example 2)
To a 300 ml pear-shaped two-necked flask were added 0.99 g (3.71 mmol) of triisopropoxy yttrium manufactured by High Purity Chemical Laboratory and 40 ml of dehydrated toluene, and the mixture was stirred with a magnetic stirrer. Separately, a solution prepared by dissolving 4.02 g (11.5 mmol) of 1,3-bis (1-adamantyl) -1,3-propanedione in 80 ml of dehydrated toluene was dropped into a toluene solution of triisopropoxy yttrium. did. The reaction was performed for 22 hours under reflux of toluene, and the toluene was distilled off and dried under reduced pressure. 20 ml of dehydrated toluene was added to the obtained solid, and the mixture was heated to reflux for 1 hour. The solution was cooled to room temperature and the supernatant was removed. The resulting precipitate was dried under reduced pressure to obtain a toluene monohydrate of tris (1,3-bis ((1-adamantyl) propane-1,3 dionato) yttrium, yield 3.55 g (2.96 mmol). Yield 80%.
As a result of nuclear magnetic resonance spectrum (NMR) of the product, ¹ H-NMR δ (ppm): 7.3-7.0 (5H), 6.0 (3H), 2.1 (3H), 2.0 (54H) 1.7 (36H) However, C ₆ D ₆ was used as a measurement solvent.
The Y content of the product was 7.2%, the C content was 75.5%, and the H content was 8.6%.

(Synthesis Example 3)
Toluene monohydrate 123.4 mg (0.10 mmol) of the yttrium compound synthesized in Synthesis Example 2 was dried under reduced pressure at 160 ° C. for 30 minutes, and tris (1,3-bis ((1-adamantyl) propane-1 was obtained. , 3 Dionato) Yttrium was obtained.
As a result of nuclear magnetic resonance spectrum (NMR) of the product, ¹ H-NMR δ (ppm): 6.0 (3H), 2.0 (54H), 1.7 (36H) However, the measurement solvent is C ₆ D ₆ was used.
The Y content of the product was 7.2%, the C content was 74.8%, and the H content was 8.8%.

(Synthesis Example 4)
To a 500 ml eggplant-shaped two-necked flask, 6.77 g (60.4 mmol) of t-butoxypotassium and 80 ml of dry DMF were added and stirred with a magnetic stirrer. Separately, a solution prepared by dissolving 3.49 g (30.0 mmol) of methyl 2,2-dimethylpropionate (methyl pivalate) in 40 ml of dry DMF was added dropwise to a DMF solution of potassium t-butoxy. Next, separately from this, a solution prepared by dissolving 3.57 g (20.0 mmol) of 1-adamantyl methyl ketone in 40 ml of dry DMF was prepared and dropped into the reaction solution. After making it react at 80 degreeC for 5 hours, it heated up at 90 degreeC and reacted for 8 hours. After cooling to room temperature, 60 ml of 1N hydrochloric acid was added to stop the reaction. After DMF was distilled off, extraction was performed 3 times using 40 ml of ethyl acetate. After drying overnight with dry sodium sulfate, the mixture was filtered, and the filtrate was dried under reduced pressure to obtain a crude product. The obtained crude product was separated by column chromatography using silica gel to obtain 1- (1-adamantyl) -4,4-dimethyl-1,3-propanedione. Yield 1.79 g (6.82 mmol), yield 39%.
As a result of nuclear magnetic resonance spectrum (NMR) of the product, ¹ H-NMR δ (ppm): 17 (1H), 5.7 (1H), 1.8 (9H), 1.5 (6H), 1. 1 (9H) However, the measurement was used as a solvent C ₆ D _6.

(Synthesis Example 5)
To a 300 ml pear-shaped two-necked flask, 0.48 g (1.79 mmol) of triisopropoxy yttrium manufactured by High Purity Chemical Laboratory and 25 ml of dehydrated toluene were added and stirred with a magnetic stirrer. Separately, a solution prepared by dissolving 1.79 g (6.82 mmol) of 1-bis (1-adamantyl) -4,4-dimethyl-1,3-pentanedione in 60 ml of dehydrated toluene was prepared, and triisopropoxy yttrium It was dripped at the toluene solution. The reaction was performed for 22 hours under reflux of toluene, and the toluene was distilled off and dried under reduced pressure. 5 ml of dehydrated n-hexane was added to the obtained solid, and the mixture was heated to reflux for 1 hour. The solution was cooled with dry ice and the supernatant was removed. The resulting precipitate was dried under reduced pressure to obtain a toluene monohydrate of tris (1-((1-adamantyl) -4,4-dimethyl-pentane-1,3 dionato) yttrium. 1.10 mmol), 61% yield.
As a result of nuclear magnetic resonance spectrum (NMR) of the product, ¹ H-NMR δ (ppm): 5.9 (3H), 1.9 (27H), 1.6 (18H), 1.2 (27H) where The measurement solvent was C ₆ D ₆ .
The Y content of the product was 9.5%, the C content was 70.5%, and the H content was 8.6%.

Example 1
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 toluene and 140 ml of butadiene, the temperature of the solution was adjusted to 30 ° C., and 0.5 ml of a toluene solution of triethylaluminum (TEA) (2 mol / L) was added. The mixture was added and stirred at 500 rpm for 3 minutes. Next, 4 ml of a toluene solution (5 mmol / L) of tris (1,3-bis ((1-adamantyl) propane-1,3 diionato) yttrium was added and stirred for 4 minutes, and then the temperature was raised to 40 ° C. Polymerization was started by adding 0.1 ml of a toluene solution (0.43 mol / L) of triphenylcarbenium tetrakispentafluorophenylborate, and after polymerization for 25 minutes at 40 ° C., ethanol / heptane (1/1 1) 5 ml of the solution was added to stop the polymerization, and after releasing the pressure inside the autoclave, the polymerization solution was put into ethanol to recover the polybutadiene, and then the recovered polybutadiene was vacuum dried at 80 ° C. for 3 hours. The results are shown in Table 1.

(Example 2)
Polymerization was carried out in the same manner as in Example 1 except that the amount of triethylaluminum (TEA) added was 1 ml of a toluene solution (2 mol / L). The polymerization results are shown in Table 1.

Example 3
Polymerization was carried out in the same manner as in Example 1 except that the amount of triethylaluminum (TEA) added was 2 ml of a toluene solution (2 mol / L). The polymerization results are shown in Table 1.

Example 4
Polymerization was performed in the same manner as in Example 1 except that the amount of triethylaluminum (TEA) added was 3 ml of a toluene solution (2 mol / L). The polymerization results are shown in Table 1.

(Example 5)
The inside of the autoclave with an internal volume of 2 L was purged with nitrogen, charged with a solution consisting of 260 ml of toluene and 140 ml of butadiene, the temperature of the solution was adjusted to 30 ° C., and then 1 ml of a toluene solution of triethylaluminum (TEA) (2 mol / L) was added. The mixture was stirred at 500 rpm for 3 minutes. Next, 4 ml of a toluene solution (5 mmol / L) of tris (1,3-bis ((1-adamantyl) propane-1,3 diionato) yttrium was added and stirred at 40 ° C. for 30 minutes, and then triphenylcarbenium. Polymerization was started by adding 0.1 ml of a tetrakispentafluorophenylborate toluene solution (0.43 mol / L) After polymerization for 25 minutes at 40 ° C., 5 ml of an ethanol / heptane (1/1) solution containing an antioxidant. After the pressure inside the autoclave was released, the polymerization solution was put into ethanol and polybutadiene was recovered, and the recovered polybutadiene was then vacuum-dried at 80 ° C. for 3 hours. It was shown to.

(Reference Example 1)
The inside of the autoclave with an internal volume of 2 L was purged with nitrogen, charged with a solution consisting of 260 ml of toluene and 140 ml of butadiene, the temperature of the solution was adjusted to 30 ° C., and then 1 ml of a toluene solution of triethylaluminum (TEA) (2 mol / L) was added. The mixture was stirred at 500 rpm for 3 minutes. Next, 1 ml of a toluene solution (20 mmol / L) of yttrium (III) tris (2,2,6,6-tetramethyl-3,5-heptanedionate) was added and stirred for 4 minutes. The temperature was raised and 0.1 ml of a toluene solution (0.43 mol / L) of triphenylcarbenium tetrakispentafluorophenylborate was added to initiate polymerization. After polymerization at 40 ° C. for 30 minutes, 5 ml of an ethanol / heptane (1/1) solution containing an antiaging agent was added to terminate 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 6)
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 toluene and 140 ml of butadiene, the temperature of the solution was adjusted to 30 ° C., and then a toluene solution of diethylaluminum hydride (DEAH) (2 mol / L) 0.3 ml And stirred for 3 minutes at 500 rpm. Next, 4 ml of a toluene solution (5 mmol / L) of tris (1,3-bis ((1-adamantyl) propane-1,3 diionato) yttrium was added and stirred for 4 minutes, and then the temperature was raised to 40 ° C. Polymerization was initiated by adding 0.1 ml of a toluene solution (0.43 mol / L) of triphenylcarbenium tetrakispentafluorophenylborate, and after polymerization for 30 minutes at 40 ° C., ethanol / heptane (1/1 1) 5 ml of the solution was added to stop the polymerization, and after releasing the pressure inside the autoclave, the polymerization solution was put into ethanol to recover the polybutadiene, and then the recovered polybutadiene was vacuum dried at 80 ° C. for 3 hours. The results are shown in Table 2.

(Example 7)
Polymerization was performed in the same manner as in Example 6 except that the amount of diethylaluminum hydride (DEAH) added was 0.4 ml of a toluene solution (2 mol / L). The polymerization results are shown in Table 2.

(Example 8)
Polymerization was carried out in the same manner as in Example 6 except that the amount of diethylaluminum hydride (DEAH) added was 0.5 ml of a toluene solution (2 mol / L). The polymerization results are shown in Table 2.

Example 9
Polymerization was conducted in the same manner as in Example 6 except that the amount of diethylaluminum hydride (DEAH) added was 0.55 ml of a toluene solution (2 mol / L). The polymerization results are shown in Table 2.

(Example 10)
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 toluene and 140 ml of butadiene, the temperature of the solution was adjusted to 30 ° C., and then a toluene solution of diethylaluminum hydride (DEAH) (2 mol / L) 0.5 ml And stirred for 3 minutes at 500 rpm. Next, 4 ml of a toluene solution (5 mmol / L) of tris (1,3-bis ((1-adamantyl) propane-1,3 diionato) yttrium was added and stirred at 40 ° C. for 30 minutes, and then triphenylcarbenium. Polymerization was started by adding 0.1 ml of a tetrakispentafluorophenylborate toluene solution (0.43 mol / L), and after polymerization for 30 minutes at 40 ° C., 5 ml of an ethanol / heptane (1/1) solution containing an antioxidant. After the pressure inside the autoclave was released, the polymerization solution was poured into ethanol to recover polybutadiene, and the recovered polybutadiene was then vacuum dried at 80 ° C. for 3 hours. It was shown to.

(Example 11)
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 toluene and 140 ml of butadiene, the temperature of the solution was adjusted to 30 ° C., and then a toluene solution of diisobutylaluminum hydride (DIBAL-H) (1 mol / L) 1 0.5 ml was added and stirred for 3 minutes at 500 rpm. Next, 4 ml of a toluene solution (20 mmol / L) of tris (1-((1-adamantyl) -4,4-dimethyl-pentane-1,3 dionato) yttrium was added and stirred for 4 minutes. The temperature was raised and 0.4 ml of a toluene solution of triphenylcarbenium tetrakispentafluorophenylborate (0.43 mol / L) was added to initiate polymerization, and after polymerization at 40 ° C. for 30 minutes, Polymerization was stopped by adding 5 ml of heptane (1/1) solution, and after releasing the pressure in the autoclave, the polymerization solution was put into ethanol to recover polybutadiene, and then the recovered polybutadiene was vacuumed at 80 ° C. for 3 hours. The polymerization results are shown in Table 3.

(Example 12)
Polymerization was carried out in the same manner as in Example 11 except that the amount of diisobutylaluminum hydride (DIBAL-H) added was 2.4 ml of a toluene solution (1 mol / L). The polymerization results are shown in Table 3.

(Example 13)
Polymerization was conducted in the same manner as in Example 11 except that the amount of diisobutylaluminum hydride (DIBAL-H) added was 4.0 ml of a toluene solution (1 mol / L). The polymerization results are shown in Table 3.

(Example 14)
Polymerization was conducted in the same manner as in Example 11 except that the amount of diisobutylaluminum hydride (DIBAL-H) added was 5.6 ml of a toluene solution (1 mol / L). The polymerization results are shown in Table 3.

(Example 15)
The inside of the autoclave with an internal volume of 2 L was purged with nitrogen, charged with a solution consisting of 260 ml of toluene and 140 ml of butadiene, the temperature of the solution was adjusted to 30 ° C., and then a toluene solution of diisobutylaluminum hydride (DIBAL-H) (1 mol / L) 2 4 ml was added and stirred for 3 minutes at 500 rpm. After the temperature was raised to 40 ° C., 4 ml of a toluene solution (20 mmol / L) of tris (1-((1-adamantyl) -4,4-dimethyl-pentane-1,3 dionato) yttrium was added, and Polymerization was started by adding 0.4 ml of a toluene solution (0.43 mol / L) of phenylcarbenium tetrakispentafluorophenylborate, and after polymerization at 40 ° C. for 30 minutes, ethanol / heptane containing an anti-aging agent (1/1 The polymerization was stopped by adding 5 ml of the solution, and after releasing the pressure in the autoclave, the polymerization solution was put into ethanol to recover the polybutadiene, and then the recovered polybutadiene was vacuum dried at 80 ° C. for 3 hours. Are shown in Table 3.

(Example 16)
The inside of the autoclave with an internal volume of 2 L was purged with nitrogen, charged with a solution consisting of 260 ml of toluene and 140 ml of butadiene, the temperature of the solution was adjusted to 30 ° C., and then a toluene solution of diisobutylaluminum hydride (DIBAL-H) (1 mol / L) 2 4 ml was added and stirred for 3 minutes at 500 rpm. Next, 4 ml of a toluene solution (20 mmol / L) of tris (1-((1-adamantyl) -4,4-dimethyl-pentane-1,3 dionato) yttrium was added and stirred for 15 minutes. The temperature was raised and 0.4 ml of a toluene solution of triphenylcarbenium tetrakispentafluorophenylborate (0.43 mol / L) was added to initiate polymerization, and after polymerization at 40 ° C. for 30 minutes, Polymerization was stopped by adding 5 ml of heptane (1/1) solution, and after releasing the pressure in the autoclave, the polymerization solution was put into ethanol to recover polybutadiene, and then the recovered polybutadiene was vacuumed at 80 ° C. for 3 hours. The polymerization results are shown in Table 3.

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

Claims (5)

An yttrium compound having a bulky ligand represented by the following general formula (1).

^(Wherein, R 2, ^{R 3} represents hydrogen, or a substituent having 1 to 12 carbon atoms, O represents an oxygen atom, Y represents yttrium atom.) Tris (1,3-bis (1-adamantyl) -1,3-propanedionato) yttrium. Tris (1- (1-adamantyl) -4,4-dimethyl-1,3-pentandionato) yttrium. The yttrium compound (A) having a bulky ligand according to any one of claims 1 to 3, an ionic compound (B) comprising a non-coordinating anion and a cation, groups 2 and 12 of the periodic table A catalyst for conjugated diene polymerization, comprising an organometallic compound (C) of an element selected from Group 13. A method for producing a conjugated diene polymer, comprising polymerizing a conjugated diene compound using the conjugated diene polymerization catalyst according to claim 4.