JP5035864B2 - Metallocene complex and polymerization catalyst composition containing the same - Google Patents

Description

  The present invention relates to a metallocene complex, a polymerization catalyst composition containing the same, and a method for producing an addition polymer using the same.

  The metallocene complex is a compound that is used as one of catalyst components for various polymerization reactions, and is a complex compound in which one or two or more cyclopentadienyls or derivatives thereof are bonded to a central metal. In particular, a metallocene complex having one cyclopentadienyl or derivative thereof bonded to a central metal may be referred to as a half metallocene complex.

  As for the metallocene complex whose central metal is gadolinium Gd, bis (pentamethylcyclopentadienyl) gadolinium borate, dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadienyl) gadolinium, and the like are known. Is known to be used as a component of a polymerization catalyst composition (see, for example, Patent Document 1).

The lanthanoid metallocene complex having a bis (trimethylsilyl) amide ligand has a central metal of cerium Ce (see Non-Patent Document 1); a central metal of yttrium Y, lanthanum La, and cerium Ce (non-patent) There is known a material whose center metal is neodymium Nd, samarium Sm, or ytterbium Yb (see Non-Patent Document 3).
Any of these lanthanoid metallocene complexes having a bistrimethylsilylamide ligand has a tetramethylcyclopentadiene ligand.

On the other hand, many proposals have been made on polymerization catalysts for polymerization of conjugated dienes.
For example, it is known that a high cis 1,4-bond conjugated diene polymer can be obtained by using a composite catalyst system mainly composed of a neodymium compound and an organoaluminum compound, and some of these are butadiene polymerization catalysts. It is used industrially as a system (for example, see Non-Patent Documents 4 and 5).
It has also been reported that a high cis 1,4-bond conjugated diene polymer can be obtained using a catalyst system containing the aforementioned dimethylaluminum (μ-dimethyl) bis (cyclopentadienyl) gadolinium (Patent Document) 1).

However, there is a need for a more efficient method for producing a conjugated diene polymer having a high cis 1,4-structure content in the microstructure, a high molecular weight and a sharp molecular weight distribution, and development of a polymerization catalyst therefor is required. ing.
JP 2004-27179 A Orgnometallics 1989, 8, 2637-2646 Journal of Organometallic Chemistry, 364 (1989) 79-86. Inorg. Chem. 1981, 20, 3267-3270 Macromolecules, 15, 230, 1982. Makromol. Chem., 94, 119, 1981.

  An object of the present invention is to provide a new metallocene complex and to provide a new polymerization catalyst reaction using the same. In particular, it is an object to provide a catalyst composition for polymerizing a conjugated diene cis 1,4-selectively and in a high yield.

That is, the first of the present invention relates to the metallocene complex shown below.
[1] A metallocene complex represented by the following general formula (I).

(In general formula (I),
M represents gadolinium Gd;
Cp ^R each independently represents unsubstituted or substituted cyclopentadienyl,
R ^{a to} R ^f each independently represents an alkyl group having 1 to 3 carbon atoms,
L represents a neutral Lewis base;
w represents an integer of 0 to 3. )

[2] A metallocene complex represented by the following general formula (II).

(In general formula (II),
M represents gadolinium Gd;
Cp ^R represents unsubstituted or substituted cyclopentadienyl,
R ^{a to} R ^l each independently represent an alkyl group having 1 to 3 carbon atoms,
L represents a neutral Lewis base;
w represents an integer of 0 to 3. )

[3] A metallocene complex represented by the following general formula (III).

(In general formula (III),
M represents a lanthanoid element,
Cp represents cyclopentadienyl,
R ^{a to} R ^f each independently represents an alkyl group having 1 to 3 carbon atoms,
L represents a neutral Lewis base;
w represents an integer of 0 to 3. )

The second of the present invention relates to the polymerization catalyst composition shown below.
[4] A polymerization catalyst composition comprising the metallocene complex according to any one of [1] to [3].
[5] The polymerization catalyst composition according to [4], for polymerizing a conjugated diene.
[6] The polymerization catalyst composition according to [4] or [5], further comprising an aluminoxane.
[7] The polymerization catalyst composition according to [4] or [5], further comprising an organoaluminum compound and an ionic compound.

The third of the present invention relates to a method for producing an addition polymer shown below.
[8] A method for producing an addition polymer, comprising a step of polymerizing an addition polymerizable monomer in the presence of the polymerization catalyst composition according to any one of [4] to [7].
[9] The method according to [8], wherein the addition polymerizable monomer is a conjugated diene and the addition polymer is a conjugated diene polymer.
[10] The method according to [8], wherein the addition polymerizable monomer is 1,3-butadiene and the addition polymer is a butadiene polymer.

  The metallocene complexes of the present invention can be used, for example, as a polymerization catalyst, thereby providing a new polymerization reaction. Preferably, by using the metallocene complex of the present invention as a polymerization catalyst for a conjugated diene, a diene polymer having a high cis 1,4-content in the microstructure can be produced with high yield.

<The metallocene complex of the present invention>
The first of the metallocene complexes of the present invention is represented by the following formula (I), characterized in that the central metal M is gadolinium Gd, two cyclopentadienyl or its derivative ligand Cp ^R , and one bis (Trialkylsilyl) amide ligand [—N (SiR ₃ ) ₂ ].
The second metallocene complex of the present invention is represented by the following formula (II), characterized in that the central metal M is gadolinium Gd, one cyclopentadienyl or its derivative ligand Cp ^R , and two bis (Trialkylsilyl) amide ligand [—N (SiR ₃ ) ₂ ].
The second metallocene complex of the present invention is represented by the following formula (III), wherein the central metal M is a lanthanoid element, one cyclopentadienyl ligand Cp, and two bis (trialkylsilyl) amide coordinations. The child [-N (SiR ₃ ) ₂ ] is included.
Any of the metallocene complexes of the present invention may further contain a neutral ligand, for example, the Lewis base L.

Cp ^R in the general formulas (I) and (II) is an unsubstituted cyclopentadienyl or a substituted cyclopentadienyl. Examples of Cp ^R include 1) those having a cyclopentadienyl ring as a basic skeleton, and 2) those having a condensed ring containing cyclopentadienyl (such as an indenyl ring and a fluorenyl ring) as the basic skeleton.

Cp ^R having a cyclopentadienyl ring as a basic skeleton is represented by C ₅ H _5-X R _X. Here, X represents an integer of 0 to 5. Each R is preferably independently a hydrocarbyl group; a metalloid group.
The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Preferred specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group.
Examples of the metalloid-based metalloid include germyl Ge, stannyl Sn, and silyl Si. The metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the hydrocarbyl group described above. Specific examples of the metalloid group include a trimethylsilyl group.

Specific examples of Cp ^R having a cyclopentadienyl ring as a basic skeleton include the following.

Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7-X R _X or C ₉ H _11-X R _X. Here, R is the same as R of the cyclopentadienyl ring described above, and X is an integer of 0 to 7 or 0 to 11.
Cp ^R having a fluorenyl ring as a basic skeleton can be represented by C ₁₃ H _9-X R _X or C ₁₃ H _17-X R _X. Here, R is the same as R in the above-described cyclopentadienyl ring, and X is an integer of 0-9 or 0-17.

Two Cp ^R in the general formula (I) may be the same or different from each other.
In the general formula (III), Cp represents a cyclopentadienyl ligand C ₅ H ₅ .

  The central metal M in the general formula (I) or (II) is gadolinium Gd.

  The central metal M in the general formula (III) is a lanthanoid element. The lanthanoid elements include 15 elements having atomic numbers of 57 to 71, and are not particularly limited. Preferable examples of the central metal M include samarium Sm, neodymium Nd, praseodymium Pr, and gadolinium Gd.

The metallocene complex of the present invention represented by the general formula (I), (II) or (III) is characterized by containing a bistrialkylsilylamide [—N (SiR ₃ ) ₂ ] ligand. The alkyl R contained in the bistrialkylsilylamide (R ^{a to} R ^f in the general formula (I) or R ^{a to} R ^l in (II) or (III)) is independently an alkyl having 1 to 3 carbon atoms. And is preferably methyl.

  Furthermore, the metallocene complex of the present invention may contain 0 to 3 (preferably 0 to 1) neutral Lewis bases L. Examples of neutral Lewis bases include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride and the like. When a plurality of neutral Lewis bases L are included, each L may be the same or different.

  The metallocene complex of the present invention may exist as a monomer as shown by the general formula (I), (II) or (III), and exist as a dimer or a higher multimer. It does not matter.

The metallocene complex of this invention is manufactured by the procedure shown below, for example.
The complex represented by the general formula (I) is obtained by reacting bis (cyclopentadienyl derivative) gadolinium halide with a salt of bis (trialkylsilyl) amide (for example, potassium salt or lithium salt) in a solvent. Can do.
Since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used.
Below, the reaction example for obtaining the complex shown by general formula (I) is shown.

The complex represented by the general formula (II) is obtained by reacting trihalogadolinium with one equivalent of a salt of a cyclopentadiene derivative (for example, sodium salt) and two equivalents of a salt of bis (trimethylsilyl) amide in a solvent. Can do. Here, trihalogadolinium is preferably reacted stepwise with a salt of a cyclopentadiene derivative and a salt of bis (trimethylsilyl) amide. For example, after reacting a salt of a cyclopentadiene derivative, a salt of bis (trimethylsilyl) amide can be reacted. However, it is not necessary to isolate the reaction product of trihalogadolinium and the salt of cyclopentadiene derivative as an intermediate, and the cyclopentadiene derivative salt and bis (trimethylsilyl) amide salt are continuously formed in the gadolinium complex in the reaction system. Can be reacted.
Since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction temperature is arbitrary, but it is about several hours to several tens of hours.
Below, the example of reaction for obtaining the complex shown by general formula (II) is shown.

  The complex represented by the general formula (III) can be produced by using trihalogadolinium as a trihalolanthanoid and a cyclopentadiene derivative salt as a cyclopentadiene salt in the production of the complex represented by the general formula (II). it can.

The structure of the metallocene complex of the present invention represented by the general formulas (I) and (II) is preferably determined by X-ray structural analysis. Since gadolinium complexes are paramagnetic compounds, they may not be identified by means other than X-ray structural analysis.
ORTEP diagram showing the result of X-ray crystal structure analysis of [(C ₅ Me ₅ ) ₂ GdN (SiMe ₃ ) ₂ ] and [(C ₅ Me ₅ ) Gd [N (SiMe ₃ ) ₂ ] ₂ ] (thf) ORTEP diagrams showing the results of X-ray crystal structure analysis are shown in FIGS. 1 and 2, respectively.
The structure of the metallocene complex of the present invention represented by the general formula (III) can be determined not only by X-ray structure analysis but also by ¹ H-NMR spectrum analysis, IR spectrum analysis, elemental analysis, and the like.

  The metallocene complex of the present invention can be applied to various fields. For example, it can be used as a component of a polymerization catalyst composition.

<Polymerization catalyst composition of the present invention>
The polymerization catalyst composition of the present invention is characterized by containing the above-mentioned metallocene complex (shown by the general formula (I), (II) or (III)), and further comprising a normal metallocene complex It is preferable to include other components contained in the composition, such as a promoter.

As described above, the polymerization catalyst composition of the present invention can contain any component other than the metallocene complex, and preferably contains a cocatalyst, for example. The cocatalyst can be arbitrarily selected from components used as a cocatalyst for a polymerization catalyst composition containing a normal metallocene complex.
Examples of preferred cocatalysts include 1) aluminoxane, and 2) a combination of an organoaluminum compound and an ionic compound.

  The aluminoxane is preferably an alkylaluminoxane, and examples of the alkylaluminoxane include methylaluminoxane (MAO), modified methylaluminoxane and the like. A preferred example of the modified methylaluminoxane includes MMAO-3A (manufactured by Tosoh Finechem).

  The content of the aluminoxane in the polymerization catalyst composition of the present invention is such that the element ratio Al / M of the central metal element M of the metallocene complex and the aluminum element Al of the aluminoxane is about 10 to 1000 (preferably about 100). It is preferable to do.

  On the other hand, examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, dialkylaluminum hydride and the like. Trialkylaluminum is preferred, and examples of trialkylaluminum include triethylaluminum and triisobutylaluminum.

The ionic compound that can be contained in the polymerization catalyst composition of the present invention preferably comprises a non-coordinating anion and a cation.
Examples of the non-coordinating anion that is a constituent component of the ionic compound include a tetravalent boron anion. Examples of tetravalent boron anions include tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) ) Borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tridecahydride- 7,8-dicarbaound decaborate and the like are included. Tetrakis (pentafluorophenyl) borate is preferable.

Examples of the cation that is a constituent component of the ionic compound include a carbonium cation, an oxonium cation, an amine cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal.
Examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation and tri (substituted phenyl) carbonium cation. Examples of the tri-substituted phenylcarbonium cation include a tri (methylphenyl) carbonium cation.
Examples of amine cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation and tributylammonium cation; N, N-dimethylammonium cation, N, N-diethylammonium cation, N, N- N, N-dialkylanilinium cations such as 2,4,6-pentamethylammonium cation; dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation are included.
Examples of phosphonium cations include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, tri (dimethylphenyl) phosphonium cation.
Of these cations, anilinium cation or carbonium cation is preferred, and anilinium cation is particularly preferred.

That is, the ionic compound contained in the catalyst composition of the present invention is a combination of those selected from the aforementioned non-coordinating anions and cations.
Preferably, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like are included.

The content of the organoaluminum compound in the polymerization catalyst composition of the present invention is preferably 1 to 50 times mol, more preferably about 10 times mol to the metallocene complex.
Moreover, it is preferable that it is 0.1-10 times mole with respect to a metallocene complex, and, as for content of the ionic compound in the polymerization catalyst composition of this invention, it is more preferable that it is about 1 time mole.

The polymerization catalyst composition of the present invention is provided for a polymerization reaction system of any monomer having addition polymerization property. For example, 1) a composition containing each component (such as a metallocene complex and a cocatalyst) may be provided in the polymerization reaction system, and 2) each component is separately provided in the polymerization reaction system. It is good also as a composition.
In the above 1), “providing a composition” includes providing a metallocene complex (active species) activated by a cocatalyst.

Examples of monomers polymerized using the polymerization catalyst composition of the present invention include olefin monomers, epoxy monomers, isocyanate monomers, lactone monomers, lactide monomers, cyclic carbonate monomers, alkyne monomers, etc. Is included.
Examples of the olefin monomer include α-olefin, styrene, ethylene, diene, cyclic olefin and the like. Further examples of dienes include 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethylbutadiene, 2-methylpentadiene, 4-methylpentadiene, and 2, Conjugated dienes such as 4-hexadiene are included. A more preferred conjugated diene is 1,3-butadiene.

  The metallocene complex (shown by the general formula (I), (II) or (III)) contained in the catalyst composition of the present invention is selected according to the use of the catalyst. For example, when used as a catalyst for conjugated diene polymerization, by using a metallocene complex whose central metal M is Gd, 1) the catalytic activity can be increased, and 2) the cis content of the resulting polydiene can be increased. Can do.

In addition, when used as a catalyst for conjugated diene polymerization, by adjusting the steric size of the substituent on the cyclopentadienyl derivative Cp ^R , 1) catalytic activity and 2) the resulting polydiene cis- The 1,4 content can be controlled. That is, when the substituent on Cp ^R is sterically reduced (for example, Cp ^R is unsubstituted cyclopentadienyl), the resulting polydiene tends to have a high cis 1,4-content. . On the other hand, when the substituent on Cp ^R is sterically enlarged (for example, Cp ^{R is changed} to tetramethylethylcyclopentadienyl), polydiene tends to be obtained with high yield in a short reaction time. .

  Further, when used as a catalyst for conjugated diene polymerization, 1) a polymerization catalyst composition by combining each of the metallocene complexes represented by the general formula (I), (II) or (III) with an appropriate promoter. 2) The cis content of the resulting polydiene can be increased. Hereinafter, the relationship between the metallocene complex represented by the general formula (I), (II) or (III) contained in the catalyst composition and the cocatalyst will be described.

<Catalyst composition containing a metallocene complex represented by the general formula (I)>
When the metallocene complex represented by the general formula (I) is used as a component of the conjugated diene polymerization catalyst composition, the number average molecular weight of the resulting polydiene tends to be increased by using an aluminoxane as the promoter.

<Catalyst composition containing a metallocene complex represented by the general formula (II) or (III)>
When the metallocene complex represented by the general formula (II) is used as a component of the conjugated diene polymerization catalyst composition, the number average molecular weight of the resulting polydiene tends to be increased by using an aluminoxane as the promoter. By using a combination of an organoaluminum compound and an ionic compound as a cocatalyst, the cis 1,4-content of the polydiene may be increased. In particular, when the central metal M is Gd and Cp ^R is unsubstituted cyclopentadienyl Cp, the resulting polydiene has a high cis 1,4-content.
However, these tendencies may not always apply due to differences in reaction conditions.

  The polymerization catalyst composition of the present invention is used not only as a homopolymerization reaction but also as a polymerization catalyst composition in a copolymerization reaction.

<Method for producing addition polymer of the present invention>
The method for producing an addition polymer of the present invention is characterized by including a step of subjecting any monomer having addition polymerizability to addition polymerization in the presence of the aforementioned catalyst composition. The production method of the present invention may be the same as the conventional production method of an addition polymer by an addition polymerization reaction using a coordination ion polymerization catalyst, except that the catalyst composition of the present invention is used as a polymerization catalyst. it can. That is, the method for producing the addition polymer of the present invention may be any method such as a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method. it can.
When using the solution polymerization method, the solvent used is not particularly limited as long as it is inert in the polymerization reaction and can dissolve the polymerization monomer and the catalyst composition. The amount of the solvent used is arbitrary, but is preferably an amount that makes the concentration of the complex contained in the polymerization catalyst 0.1 to 0.0001 mol / l.

  In the method for producing an addition polymer of the present invention, the amount of the catalyst composition used relative to the amount of the monomer may be the same amount as that of a catalyst composition containing a normal metallocene complex.

  According to the method for producing an addition polymer of the present invention, not only a homopolymer but also a random copolymer, an alternating copolymer, a block copolymer, and other ordered copolymers can be produced.

Below, the example of the manufacture procedure of the polybutadiene from 1, 3- butadiene by the manufacturing method of this invention is shown.
(1) A metallocene complex of the present invention and, if necessary, a cocatalyst are added to a solvent. Here, the metallocene complex appears to change to an active form. To this, 1,3-butadiene is further added to obtain polybutadiene.
(2) The component of the catalyst composition is separately added to the solvent containing 1,3-butadiene, or the catalyst composition prepared and activated in advance is added to obtain polybutadiene.
Any procedure is preferably performed in an inert gas atmosphere. Examples of the inert gas include nitrogen gas and argon gas.

  In the production of polybutadiene, it is preferable to use a metallocene complex having a molar ratio of 1/10000 to 1/1000 times that of 1,3-butadiene.

The temperature of the polymerization reaction is not particularly limited and is, for example, in the range of −100 ° C. to 200 ° C., but can be about room temperature. Increasing the reaction temperature may decrease the cis 1,4-selectivity of the polymerization reaction.
The reaction time is not particularly limited and is, for example, in the range of 1 second to 10 days, and is appropriately selected depending on conditions such as the type of monomer to be polymerized, the type of catalyst used, and the reaction temperature.

By the method for producing an addition polymer of the present invention, a polydiene having a high cis 1,4-content can be produced from a conjugated diene compound. For example, the cis 1,4- content of polybutadiene produced by polymerizing butadiene by the method of the present invention is 90% or more, preferably 95% or more, more preferably 98% or more, and further preferably 99% or more. is there. The cis 1,4-content can be determined from the peak integration ratio of the spectrum charts of 1H-NMR and 13C-NMR, and a specific method thereof is described in JP-A-2004-27179.
Further, the number average molecular weight of the polybutadiene produced by the method of the present invention is not particularly limited, but is usually about several hundred thousand to millions, and Mw / Mn, which is an index of molecular weight distribution, is preferably 3 or less. Preferably it is 2 or less. The average molecular weight and molecular weight distribution Mw / Mn can be determined by GPC using polystyrene as a standard substance.

  When producing a polydiene from a conjugated diene compound by the method for producing an addition polymer of the present invention, the yield of polydiene obtained by appropriately selecting the type of metallocene complex or cocatalyst contained in the polymerization catalyst composition And the cis 1,4-content can be controlled. Specifically, it is as shown in the description of the polymerization catalyst composition.

Hereinafter, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited by these examples.
<Example 1>
Production of metallocene complex 1
In a nitrogen atmosphere, [(C ₅ Me ₅ ) ₂ GdCl ₂ Li (thf) ₂ ] (1.95 g, 3 mmol) in 40 ml of toluene solution was mixed with K [N (SiMe ₃ ) ₂ ] (0.60 g, 3 mmol) ( 15 ml of a toluene solution of Aldrich) was slowly added dropwise, and the resulting solution was stirred at room temperature for 16 hours.
After stirring, toluene was distilled off from the solution under reduced pressure, and 60 ml of hexane was added to the resulting residue, followed by stirring for 3 hours. The precipitate was removed by filtering through a filter. Hexane was distilled off from the obtained filtrate under reduced pressure to obtain [(C ₅ Me ₅ ) ₂ GdN (SiMe ₃ ) ₂ ] (1.10 g, yield 62%) as a yellow solid.
A single crystal obtained by recrystallization from toluene was subjected to X-ray crystal structure analysis to determine the structure.

In the same manner as in Example 1, [(C ₅ Me ₄ H) ₂ GdN (SiMe ₃ ) ₂ ] was obtained as a yellow-green solid (yield 65%), and [(C ₅ Me ₄ Et) ₂ GdN (SiMe ₃ ) ₂ ] as a yellow-green solid (yield 67%).

<Example 2>
Production of metallocene complex 2
Under a nitrogen atmosphere, 1.59 ml of a THF solution of Na (C ₅ H ₅ ) (3.17 mmol) was slowly added dropwise to 10 ml of a THF solution of GdCl ₃ (0.84 g, 3.17 mmol). Stir at room temperature for 1 hour.
To the stirred solution, 15 ml of KN (SiMe ₃ ) ₂ (1.26 g, 6.34 mmol) in THF was added and stirred at room temperature for 14 hours.
To the residue obtained by evaporating THF from the solution under reduced pressure, 60 ml of hexane was added. The resulting solution was filtered with a filter to remove the precipitate. Hexane was distilled off from the filtrate under reduced pressure to obtain [(C ₅ H ₅ ) Gd [N (SiMe ₃ ) ₂ ] ₂ ] (thf) (1.14 g, 52%) as a white solid.
A single crystal obtained by recrystallization from hexane was subjected to X-ray crystal structure analysis to determine the structure.

In the same manner as in Example 2, [(C ₅ H ₅ ) Sm [N (SiMe ₃ ) ₂ ] ₂ ] (thf) was treated as a yellow solid (33%), [
(C ₅ H ₅ ) Nd [N (SiMe ₃ ) ₂ ] ₂ ] (thf) as a blue solid (45%), [(C ₅ H ₅ ) Pr [N (SiMe ₃ ) ₂ ] ₂ ] (thf) Were obtained as green solids (38%), respectively.

<Example 3>
In a glove box under a nitrogen atmosphere, bis (pentamethylcyclopentadienyl) gadolinium bis (trimethylsilylamide) [(C ₅ Me ₅ ) ₂ GdN (SiMe ₃ ) ₂ ] is placed in a well-dried 30 ml pressure-resistant glass bottle. 0.01 mmol was charged and dissolved in 6 ml of toluene.
Next, MMAO (toluene-soluble aluminoxane sold by Tosoh Finechem) was added so as to have an Al / Gd = 100 element ratio, and the bottle was stoppered.
Thereafter, the bottle was taken out from the glove box, charged with 1.35 g of 1,3-butadiene, and polymerized at 25 ° C. for 15 minutes.
After the polymerization, the reaction was stopped by adding 10 ml of a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol], and the polymer was separated with a large amount of methanol / hydrochloric acid mixed solvent. And vacuum dried at 60 ° C.
The yield of the obtained polymer was 100 wt%. The polymer microstructure had a cis 1,4-content of 97.52 mol%, a number average molecular weight of 1,027,400, and Mw / Mn of 2.05.

<Example 4>
In Example 3, instead of bis (pentamethylcyclopentadienyl) gadolinium bis (trimethylsilylamide), bis (tetramethylcyclopentadienyl) gadolinium bis (trimethylsilylamide) [(C ₅ Me ₄ H) ₂ GdN ( Polymerization was carried out in the same manner except that SiMe ₃ ) ₂ ] was used and the polymerization time was changed from 15 minutes to 90 minutes.
The yield of the obtained polymer was 100 wt%. The polymer microstructure had a cis 1,4-content of 98.69 mol%, a number average molecular weight of 535,500, and Mw / Mn of 1.96.

<Example 5>
In Example 3, instead of bis (pentamethylcyclopentadienyl) gadolinium bis (trimethylsilylamide), bis (tetramethylethylcyclopentadienyl) gadolinium bis (trimethylsilylamide) [(C ₅ Me ₄ Et) ₂ GdN Polymerization was carried out in the same manner except that (SiMe ₃ ) ₂ ] was used.
The yield of the obtained polymer was 100 wt%. The polymer microstructure had a cis 1,4-content of 98.03 mol%, a number average molecular weight of 490,300, and Mw / Mn of 2.38.

<Example 6>
In Example 3, instead of bis (pentamethylcyclopentadienyl) gadolinium bis (trimethylsilylamide), (cyclopentadienyl) gadolinium bis (bis (trimethylsilylamide)) (tetrahydrofuran) [(C ₅ H ₅ ) Gd Polymerization was carried out in the same manner except that [N (SiMe ₃ ) ₂ ] ₂ (thf)] was used.
The yield of the obtained polymer was 92 wt%. The polymer microstructure had a cis 1,4-content of 97.62 mol%, a number average molecular weight of 835,000, and Mw / Mn of 1.84.

<Example 7>
In Example 3, instead of bis (pentamethylcyclopentadienyl) gadolinium bis (trimethylsilylamide), (cyclopentadienyl) samarium bis (bis (trimethylsilylamide)) (tetrahydrofuran) [(C ₅ H ₅ ) Sm Polymerization was carried out in the same manner except that [N (SiMe ₃ ) ₂ ] ₂ (thf)] was used and the polymerization time was changed from 15 minutes to 20 hours.
The yield of the obtained polymer was 16 wt%. The cis 1,4-content of the polymer microstructure was 95.52 mol%, the number average molecular weight was 138,400, and Mw / Mn was 1.79.

<Example 8>
In Example 3, instead of bis (pentamethylcyclopentadienyl) gadolinium bis (trimethylsilylamide), (cyclopentadienyl) neodymium bis (bis (trimethylsilylamide)) (tetrahydrofuran) [(C ₅ H ₅ ) Nd [ N (SiMe ₃ ) ₂ ] ₂ (thf)] was used, and the polymerization was carried out in the same manner except that the polymerization time was changed from 15 minutes to 180 minutes.
The yield of the obtained polymer was 76 wt%. The cis 1,4-content of the polymer microstructure was 95.28 mol%, the number average molecular weight was 352,700, and Mw / Mn was 1.86.

<Example 9>
In Example 3, instead of bis (pentamethylcyclopentadienyl) gadolinium bis (trimethylsilylamide), (cyclopentadienyl) praseodymium bis (bis (trimethylsilylamide)) (tetrahydrofuran) [(C ₅ H ₅ ) Pr Polymerization was carried out in the same manner except that [N (SiMe ₃ ) ₂ ] ₂ (thf)] was used and the polymerization time was changed from 15 minutes to 180 minutes.
The yield of the obtained polymer was 58 wt%. The polymer microstructure had a cis 1,4-content of 94.06 mol%, a number average molecular weight of 276,800, and Mw / Mn of 2.80.

<Example 10>
In Example 3, instead of bis (pentamethylcyclopentadienyl) gadolinium bis (trimethylsilylamide), (pentamethylcyclopentadienyl) gadolinium bis (bis (trimethylsilylamide)) [(C ₅ Me ₅ ) Gd [ Polymerization was conducted in the same manner except that N (SiMe ₃ ) ₂ ] ₂ ] was used and the polymerization time was changed from 15 minutes to 5 minutes.
The yield of the obtained polymer was 100 wt%. The polymer microstructure had a cis 1,4-content of 96.09 mol%, a number average molecular weight of 730,200, and Mw / Mn of 2.44.

<Example 11>
In a glove box under a nitrogen atmosphere, bis (pentamethylcyclopentadienyl) gadolinium bis (trimethylsilylamide) [(C ₅ Me ₅ ) ₂ GdN (SiMe ₃ ) ₂ ] is placed in a well-dried 30 ml pressure-resistant glass bottle. 0.01 mmol was charged and dissolved in 6 ml of toluene.
Next, 0.1 mmol of triisobutylaluminum and 0.01 mmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (Me ₂ NHPhB (C ₆ F ₅ ) ₄ ) were added, and the bottle was stoppered. Thereafter, the bottle was taken out from the glove box, charged with 1.35 g of 1,3-butadiene, and polymerized at 25 ° C. for 2 minutes.
After the polymerization, the reaction was stopped by adding 10 ml of a 10 wt% methanol solution of BHT [2,6-bis (t-butyl) -4-methylphenol], and the polymer was separated with a large amount of methanol / hydrochloric acid mixed solvent. And vacuum dried at 60 ° C.
The yield of the obtained polymer was 91 wt%. The polymer microstructure had a cis 1,4-content of 97.76 mol%, a number average molecular weight of 553,700, and Mw / Mn of 1.85.

<Example 12>
In Example 11, instead of bis (pentamethylcyclopentadienyl) gadolinium bis (trimethylsilylamide), bis (tetramethylcyclopentadienyl) gadolinium bis (trimethylsilylamide) [(C ₅ Me ₄ H) ₂ GdN ( SiMe ₃ ) ₂ ] and polymerization time of 2
Polymerization was conducted in the same manner except that the time was from 24 minutes to 24 minutes.
The yield of the obtained polymer was 10 wt%. The polymer microstructure had a cis 1,4-content of 98.23 mol%, a number average molecular weight of 240,200, and Mw / Mn of 2.29.

<Example 13>
In Example 11, instead of bis (pentamethylcyclopentadienyl) gadolinium bis (trimethylsilylamide), bis (tetramethylethylcyclopentadienyl) gadolinium bis (trimethylsilylamide) [(C ₅ Me ₄ Et) ₂ GdN Polymerization was carried out in the same manner except that (SiMe ₃ ) ₂ ] was used.
The yield of the obtained polymer was 100 wt%. The polymer microstructure had a cis 1,4-content of 97.22 mol%, a number average molecular weight of 346,600, and Mw / Mn of 1.98.

<Example 14>
In Example 11, (cyclopentadienyl) gadolinium bis (bis (trimethylsilylamide)) (tetrahydrofuran) [(C ₅ H ₅ ) Gd instead of bis (pentamethylcyclopentadienyl) gadolinium bis (trimethylsilylamide) Polymerization was carried out in the same manner except that [N (SiMe ₃ ) ₂ ] ₂ (thf)] was used and the polymerization time was changed from 5 minutes to 60 minutes.
The yield of the obtained polymer was 60 wt%. The cis 1,4-content of the polymer microstructure was 99.28 mol%, the number average molecular weight was 571,500, and Mw / Mn was 2.15.

  The metallocene complexes of the present invention can be used, for example, as a component of a polymerization catalyst, thereby providing a new polymerization reaction, preferably providing a new polymer.

It is a ORTEP diagram showing a result of _{(C 5 Me 5) 2 GdN} (SiMe 3) 2 X-ray crystal structure analysis. (C ₅ H ₅₎ is a ORTEP diagram showing a result of X-ray crystal structure analysis of the _{Gd [N (SiMe 3) 2} ] 2 (OC 4 H 8). ^{1 is} a ¹ H-NMR spectrum chart of (C ₅ H ₅ ) Nd [N (SiMe ₃ ) ₂ ] ₂ (OC ₄ H ₈ ). 2 is a ¹ H-NMR spectrum chart and a ¹³ C-NMR spectrum chart of the polybutadiene obtained in Example 14. FIG. The peak (5.35 ppm) in the ¹ H-NMR spectrum chart is attributed to cis 1,4-unit olefin hydrogen. The peak (27.4 ppm) of the ¹³ C-NMR spectrum chart is attributed to 1,4 cis-units of methylene carbon.

Claims (10)

A metallocene complex represented by the following general formula (I).

(In general formula (I),
M represents gadolinium Gd;
Cp ^R is each independently C ₅ H _5-X R _X and X represents an integer of 0 to 5, or C ₉ H _7-X R _X and X represents an integer of 0 to 7, C ₉ H _11-X R _X and X represents an integer of 0 to ₁₁ , C ₁₃ H _9-X R _X and X represents an integer of 0 to 9, or C ₁₃ H _17-X R _X and X is 0
17 represents an integer of 17 and each of the substituents R is independently a hydrocarbyl group or a metalloid group having a hydrocarbyl group selected from germyl, stannyl, silyl ,
R ^{a to} R ^f each independently represents an alkyl group having 1 to 3 carbon atoms,
L represents a neutral Lewis base selected from tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, and lithium chloride;
w represents an integer of 0 to 3. ) A metallocene complex represented by the following general formula (II).

(In general formula (II),
M represents gadolinium Gd;
Cp ^R is C ₅ H _5-X R _X and X represents an integer of 0 to 5, or C ₉ H _7-X R _X and X is 0
Represents an integer of ˜7, is C ₉ H _11-X R _X and X represents an integer of 0 to 11, or is C ₁₃ H _9-X R _X and X represents an integer of 0 to 9, Or C ₁₃ H _17-X R _X , wherein X represents an integer of 0 to ₁₇ , and each substituent R is independently a hydrocarbyl group or a metalloid group having a hydrocarbyl group selected from germyl, stannyl, and silyl . ,
R ^{a to} R ^l each independently represent an alkyl group having 1 to 3 carbon atoms,
L represents a neutral Lewis base selected from tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, and lithium chloride;
w represents an integer of 0 to 3. ) A metallocene complex represented by the following general formula (III).

(In general formula (III),
M represents a lanthanoid element,
Cp represents cyclopentadienyl,
R ^{a to} R ^l each independently represent an alkyl group having 1 to 3 carbon atoms,
L represents a neutral Lewis base selected from tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, and lithium chloride;
w represents an integer of 0 to 3. )   The polymerization catalyst composition containing the metallocene complex as described in any one of Claims 1-3.   The polymerization catalyst composition according to claim 4 for polymerizing a conjugated diene.   The polymerization catalyst composition according to claim 4 or 5, further comprising an aluminoxane.   The polymerization catalyst composition according to claim 4 or 5, further comprising an organoaluminum compound and an ionic compound.   A method for producing an addition polymer, comprising polymerizing an addition polymerizable monomer in the presence of the polymerization catalyst composition according to any one of claims 4 to 7. The method according to claim 8, wherein the addition polymerizable monomer is a conjugated diene, and the addition polymer is a conjugated diene polymer.   The method according to claim 8, wherein the addition polymerizable monomer is 1,3-butadiene and the addition polymer is a butadiene polymer.

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