JP5851922B2 - Method for producing polymerization catalyst composition and polymerization catalyst composition - Google Patents

Description

The present invention relates to a method for producing a polymerization catalyst composition, and a polymerization catalyst composition produced by the production method.
In the present specification, “polymer” is a concept including not only “polymer” but also “oligomer”.

  Conventionally, as a polymerization catalyst composition for synthesizing a polymer, a catalyst composition using a rare earth metal is known. Examples thereof include (i) a rare earth element compound or a rare earth element-containing compound containing a reaction product of the rare earth element compound and a Lewis base described in Patent Document 1, (ii) an organoaluminum compound, and (iii) an ionic compound. Things are known. However, since the cost of the ionic compound (iii) is high in the catalyst composition, an alternative compound (iii) has been demanded. As an alternative compound, a method using silica is known (Non-Patent Document 1). However, since the method described in Non-Patent Document 1 requires firing the silica, it is also expensive. Had a point.

International Publication No. 2007/129670 Pamphlet

T. T. et al. J. et al. Woodman et al. Macromolecules (2005) 38, pp. 3060-3067

  The objective of this invention is providing the manufacturing method of a polymerization catalyst composition which can synthesize | combine a polymer composition, without using a high cost compound and without performing a special process. Another object of the present invention is to provide a polymerization catalyst in which silica is highly dispersed in a polymer, and the use of a kneading silica, a polymer, a coupling agent or a compatibilizer can be omitted or reduced. It is providing the manufacturing method of a composition, and this polymerization catalyst composition.

The method for producing a polymerization catalyst composition of the present invention includes a first element which is a rare earth element compound or a rare earth element-containing compound containing a reaction product of a rare earth element compound and a Lewis base, and a compound represented by the following formula (X): For the second element containing and the third element containing silica,
The second element and the third element are mixed and aged, and then the first element is added and reacted.
YR ¹ _a R ² _b R ³ _c (X)

(In the formula, Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. R ³ is a hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is a periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1)

  The moisture content of the third element is preferably 0.1% by weight or more. Since the silica having the moisture content can be used without going through steps such as baking and drying, it can be used easily. Moreover, it has the effect that a polymerization reaction is further accelerated | stimulated by the moisture contained.

  The blending amount of the third element is preferably more than 0 parts by weight and 100 parts by weight or less in terms of anhydride weight with respect to 100 parts by weight of the monomer constituting the polymer to be added later.

Other preferred examples of the rare earth element-containing compound include the following general formula (i) or (ii):
MX ₂ · L _w ... (i)
_{MX 3 · L w ··· (ii} )
(In the formula, M represents a lanthanoid element, scandium or yttrium, and each X independently represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, an aldehyde residue, a ketone residue, A carboxylic acid residue, a thiocarboxylic acid residue, a phosphorus compound residue, an unsubstituted or substituted cyclopentadienyl, or an unsubstituted or substituted indenyl; L represents a Lewis base; The complex represented by this is mentioned.
Preferably, the rare earth element-containing compound or the reaction product of the rare earth element compound and the Lewis base does not have a bond between the rare earth element and carbon.

In the catalyst composition of the present invention, the second element is preferably represented by the following general formula (Xa): AlR ¹ R ² R ³ (Xa)

(In the formula, R ¹ and R ² are the same or different, and are a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ is the above. R ¹ or R ² may be the same or different.

In the catalyst composition of the present invention, the third element is preferably a silicon-containing compound having a hydroxyl group in the molecule. More specifically, it preferably contains a hydroxide of silicon or a hydrate of a silicon compound.

  The catalyst composition of the present invention comprises a first element containing a rare earth element-containing compound, a second element containing a compound represented by the above formula (X), and a third element containing silica having a hydroxyl group in the molecule. A polymerization catalyst composition, which is produced by mixing and reacting the first element, the second element, and the third element.

  According to the method for producing a polymerization catalyst composition of the present invention, a polymer composition can be synthesized without using a high-cost compound and without performing a special treatment. Further, according to the method for producing the polymerization catalyst composition of the present invention and the polymerization catalyst composition produced by the production method, silica is highly dispersed in the polymer, and the kneading and coupling of the silica and the polymer are performed. The use of agents and compatibilizers can be omitted or reduced.

<< First Element >>
The first element constituting the polymerization catalyst composition according to the present invention contains a rare earth element-containing compound. A suitable first element includes a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base as the rare earth element-containing compound. Here, the rare earth element compound and the reaction product of the rare earth element compound and the Lewis base preferably do not have a bond between the rare earth element and carbon. When the rare earth element compound and the reaction product of the rare earth element compound and the Lewis base do not have a rare earth element-carbon bond, the compound is stable and easy to handle. Here, the rare earth element compound is a compound containing a lanthanoid element or scandium or yttrium composed of the elements of atomic numbers 57 to 71 in the periodic table. Specific examples of the lanthanoid element include lanthanium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. A 1st element may be used individually by 1 type, and may be used in combination of 2 or more type.
As the rare earth element-containing compound, the following rare earth element-containing compounds can be preferably used.

<Rare earth element-containing compound>
The rare earth element-containing compound may have the following structure. Preferably, the rare earth metal is a divalent or trivalent salt or complex compound, and the rare earth element-containing compound contains one or more ligands selected from a hydrogen atom, a halogen atom and an organic compound residue. More preferably. Furthermore, the reaction product of the rare earth element compound or the rare earth element compound and a Lewis base is preferably the following general formula (i) or (ii):
MX ₂ · Lw (i)
MX ₃ · Lw (ii)
(In the formula, M represents a lanthanoid element, scandium or yttrium, and each X independently represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, an aldehyde residue, a ketone residue, A carboxylic acid residue, a thiocarboxylic acid residue, a phosphorus compound residue, an unsubstituted or substituted cyclopentadienyl, or an unsubstituted or substituted indenyl; L represents a Lewis base; Can be represented by:

  Specific examples of the group (ligand) bonded to the rare earth element of the rare earth element-containing compound include a hydrogen atom; methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert -Aliphatic alkoxy group such as butoxy group; phenoxy group, 2,6-di-tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dineopentylphenoxy group, 2-tert-butyl-6 -Isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, 2-isopropyl-6-neopentylphenoxy group; thiomethoxy group, thioethoxy group, thiopropoxy group, thio n-butoxy group, thioisobutoxy group, Aliphatic thiolate groups such as thiosec-butoxy group and thiotert-butoxy group; Phenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropylthiophenoxy group, 2 Arylthiolate groups such as -tert-butyl-6-thioneopentylphenoxy, 2-isopropyl-6-thioneopentylphenoxy, 2,4,6-triisopropylthiophenoxy; dimethylamide, diethylamide, diisopropyl Aliphatic amide group such as amide group; phenylamide group, 2,6-di-tert-butylphenylamide group, 2,6-diisopropylphenylamide group, 2,6-dineopentylphenylamide group, 2-tert- Butyl-6-isopropylphenylamide group, 2-tert Arylamide groups such as butyl-6-neopentylphenylamide group, 2-isopropyl-6-neopentylphenylamide group, 2,4,6-tert-butylphenylamide group; bistrialkylsilylamides such as bistrimethylsilylamide group Groups: silyl groups such as trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropylsilyl (bistrimethylsilyl) silyl group; fluorine atom, chlorine atom, bromine atom, iodine And halogen atoms such as atoms. Furthermore, residues of aldehydes such as salicylaldehyde, 2-hydroxy-1-naphthaldehyde, 2-hydroxy-3-naphthaldehyde; 2′-hydroxyacetophenone, 2′-hydroxybutyrophenone, 2′-hydroxypropiophenone, etc. Hydroxyphenone residues of: acetylacetone, benzoylacetone, propionylacetone, isobutylacetone, valerylacetone, ethylacetylacetone, etc. diketone residues; isovaleric acid, caprylic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, Stearic acid, isostearic acid, oleic acid, linoleic acid, cyclopentanecarboxylic acid, naphthenic acid, ethylhexanoic acid, bivaric acid, versatic acid [trade name of Shell Chemical Co., Ltd., mixture of isomers of C10 monocarboxylic acid Synthetic acids comprised of, carboxylic acid residues such as phenylacetic acid, benzoic acid, 2-naphthoic acid, maleic acid, succinic acid; hexanethioic acid, 2,2-dimethylbutanethioic acid, decanethioic acid, thiobenzoic acid Thiocarboxylic acid residues such as dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, bis (2-ethylhexyl phosphate), bis (1-methylheptyl phosphate), dilauryl phosphate Dioleyl phosphate, diphenyl phosphate, bis (p-nonylphenyl) phosphate, bis (polyethylene glycol-p-nonylphenyl) phosphate, (butyl) phosphate (2-ethylhexyl), phosphoric acid (1-methylheptyl) ) (2-ethylhexyl), phosphoric acid esters such as phosphoric acid (2-ethylhexyl) (p-nonylphenyl) Residues; monobutyl 2-ethylhexylphosphonate, mono-2-ethylhexyl 2-ethylhexylphosphonate, mono-2-ethylhexyl phenylphosphonate, mono-p-nonylphenyl 2-ethylhexylphosphonate, mono-2-ethylhexyl phosphonate, Phosphonic acid ester residues such as mono-1-methylheptyl phosphonate, mono-p-nonylphenyl phosphonate, dibutylphosphinic acid, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, di Laurylphosphinic acid, dioleylphosphinic acid, diphenylphosphinic acid, bis (p-nonylphenyl) phosphinic acid, butyl (2-ethylhexyl) phosphinic acid, (2-ethylhexyl) (1-methylheptyl) phosphinic acid, (2-ethylhexyl) Phosphinic acids such as (p-nonylphenyl) phosphinic acid, butylphosphinic acid, 2-ethylhexylphosphinic acid, 1-methylheptylphosphinic acid, oleylphosphinic acid, laurylphosphinic acid, phenylphosphinic acid, p-nonylphenylphosphinic acid Can also be mentioned. In addition, these ligands may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the Lewis base that reacts with the rare earth element compound in the first element include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like. . Here, when the rare earth element compound reacts with a plurality of Lewis bases (in the formulas (I) and (II), when w is 2 or 3), the Lewis bases L are the same or different. May be.

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^a〜Ｒ^fは、それぞれ独立して炭素数１〜３のアルキル基又は水素原子を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体、及び下記一般式（ＩＩ）： <Preferred rare earth element-containing compound>
As the rare earth element-containing compound, the following general formula (I):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents unsubstituted or substituted indenyl, and R ^{a to} R ^f each independently represents an alkyl having 1 to 3 carbon atoms. A group or a hydrogen atom, L represents a neutral Lewis base, w represents an integer of 0 to 3), and the following general formula (II):

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｘ'は、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体より選択される少なくとも１種類の錯体を含むことが好ましい。

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and X ′ represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group. , A silyl group or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, and w represents an integer of 0 to 3). It is preferable that the complex is included.

Here, the metallocene complex is a complex compound in which one or more cyclopentadienyl or a derivative thereof is bonded to a central metal, and in particular, one cyclopentadienyl or a derivative thereof bonded to the central metal. A certain metallocene complex may be called a half metallocene complex.
In the polymerization reaction system, the concentration of the complex contained in the polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol / L.

In the metallocene complexes represented by the above general formulas (I) and (II), Cp ^R in the formula is unsubstituted indenyl or substituted indenyl. 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, X is an integer of 0-7 or 0-11. In addition, each R is preferably independently a hydrocarbyl group or 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. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of the substituted indenyl include 2-phenylindenyl and 2-methylindenyl. Note that the two Cp ^Rs in the general formulas (I) and (II) may be the same as or different from each other.

  The central metal M in the general formulas (I) and (II) is a lanthanoid element, scandium or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferred examples of the central metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

The metallocene complex represented by the general formula (I) contains a silylamide ligand [—N (SiR ₃ ) ₂ ]. The R groups contained in the silylamide ligand (R ^{a to} R ^f in the general formula (I)) are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. Moreover, it is preferable that at least one of R ^{a to} R ^f is a hydrogen atom. By making at least one of R ^{a to} R ^f a hydrogen atom, the synthesis of the catalyst is facilitated, and the bulk height around silicon is reduced, so that non-conjugated olefin is easily introduced. From the same viewpoint, it is more preferable that at least one of R ^{a to} R ^c is a hydrogen atom and at least one of R ^{d to} R ^f is a hydrogen atom. Furthermore, a methyl group is preferable as the alkyl group.

The metallocene complex represented by the general formula (II) includes a silyl ligand [—SiX ′ ₃ ]. X ′ contained in the silyl ligand [—SiX ′ ₃ ] is selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, and a hydrocarbon group having 1 to 20 carbon atoms. It is a group. Here, examples of the alkoxide group include aliphatic alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group; a phenoxy group and 2,6-dioxy -Tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dinepentylphenoxy group, 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, Examples include aryloxide groups such as 2-isopropyl-6-neopentylphenoxy group, and among these, 2,6-di-tert-butylphenoxy group is preferable.

  The metallocene complex represented by the general formulas (I) and (II) further contains 0 to 3, preferably 0 to 1, neutral Lewis bases L. Here, examples of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like. Here, when the complex includes a plurality of neutral Lewis bases L, the neutral Lewis bases L may be the same or different.

  Moreover, the metallocene complex represented by the general formula (I) and the formula (II) may exist as a monomer, or may exist as a dimer or a higher multimer.

（式中、Ｘ''はハライドを示す。）
上記一般式（ＩＩ）で表されるメタロセン錯体は、例えば、溶媒中でランタノイドトリスハライド、スカンジウムトリスハライド又はイットリウムトリスハライドを、インデニルの塩（例えばカリウム塩やリチウム塩）及びシリルの塩（例えばカリウム塩やリチウム塩）と反応させることで得ることができる。なお、反応温度は室温程度にすればよいので、温和な条件で製造することができる。また、反応時間は任意であるが、数時間〜数十時間程度である。反応溶媒は特に限定されないが、原料及び生成物を溶解する溶媒であることが好ましく、例えばトルエンを用いればよい。以下に、一般式（ＩＩ）で表されるメタロセン錯体を得るための反応例を示す。 The metallocene complex represented by the general formula (I) includes, for example, a lanthanoid trishalide, scandium trishalide, or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt) and bis (trialkylsilyl). It can be obtained by reacting with an amide salt (for example, potassium salt or lithium salt). In addition, 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 metallocene complex represented by general formula (I) is shown.

(In the formula, X ″ represents a halide.)
The metallocene complex represented by the general formula (II) includes, for example, a lanthanoid trishalide, a scandium trishalide, or a yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt), and a silyl salt (for example, potassium). Salt or lithium salt). In addition, 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 metallocene complex represented by general formula (II) is shown.

（式中、Ｘ''はハライドを示す。）

(In the formula, X ″ represents a halide.)

  The structure of the metallocene complex represented by general formula (I) or formula (II) is preferably determined by X-ray structural analysis.

<Other suitable rare earth element-containing compounds>
The rare earth element-containing compound has the following formula (A):

R _a MX _b QY _b (A) (wherein R independently represents unsubstituted or substituted indenyl, R is coordinated to M, and M represents a lanthanoid element, scandium or yttrium) X is independently a hydrocarbon group having 1 to 20 carbon atoms, X is μ-coordinated to M and Q, Q is a Group 13 element of the Periodic Table, and Y is independently Or a metallocene compound represented by the formula (1): a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, wherein Y is coordinated to Q, and a and b are 2. Rare earth element-containing compounds).

（式中、Ｍ^１は、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Ｒは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^A及びＲ^Bは、それぞれ独立して炭素数１〜２０の炭化水素基を示し、該Ｒ^A及びＲ^Bは、Ｍ^１及びＡｌにμ配位しており、Ｒ^C及びＲ^Dは、それぞれ独立して炭素数１〜２０の炭化水素基又は水素原子を示す）で表されるメタロセン系化合物が挙げられる。 In a preferred example of the metallocene compound, the following formula (XV):

(In the formula, M ¹ represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents an unsubstituted or substituted indenyl group, and R ^A and R ^B each independently have 1 to 20 carbon atoms. R ^A and R ^B are μ-coordinated to M ¹ and Al, and R ^C and R ^D each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Metallocene compounds represented by

Hereinafter, the metallocene compound will be described in detail. The metallocene compound has a lanthanoid element, a rare earth element of scandium or yttrium, and a Group 13 element of the periodic table, and has the following formula (A):
R _a MX _b QY _b (A)
(In the formula, each R independently represents unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium, and each X independently represents 1 to 1 carbon atoms. 20 represents a hydrocarbon group, X is μ-coordinated to M and Q, Q represents a group 13 element of the periodic table, and Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or A hydrogen atom, wherein Y is coordinated to Q, and a and b are 2. The metallocene compound can reduce or eliminate the amount of alkylaluminum used at the time of copolymer synthesis, for example, by using a catalyst that is previously combined with an aluminum catalyst. If a conventional catalyst system is used, it is necessary to use a large amount of alkylaluminum at the time of copolymer synthesis. For example, in the conventional catalyst system, it is necessary to use 10 equivalents or more of alkylaluminum with respect to the metal catalyst. If the metallocene composite catalyst is used, an excellent catalytic action can be obtained by adding about 5 equivalents of alkylaluminum. Is demonstrated.

  In the metallocene compound, the metal M in the formula (A) is a lanthanoid element, scandium, or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferred examples of the metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

  In the formula (A), each R is independently an unsubstituted indenyl or a substituted indenyl, and the R is coordinated to the metal M. Specific examples of the substituted indenyl group include 1,2,3-trimethylindenyl group, heptamethylindenyl group, 1,2,4,5,6,7-hexamethylindenyl group, and the like. It is done.

  In the above formula (A), Q represents a group 13 element in the periodic table, and specific examples include boron, aluminum, gallium, indium, thallium and the like.

  In the above formula (A), each X independently represents a hydrocarbon group having 1 to 20 carbon atoms, and X is μ-coordinated to M and Q. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like. Note that the μ coordination is a coordination mode having a crosslinked structure.

  In the formula (A), each Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and the Y is coordinated to Q. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

In the above formula (XV), the metal M ¹ is a lanthanoid element, scandium or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferable examples of the metal M ¹ include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

In the above formula (XV), Cp ^R is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton may be represented by C ₉ H _7-X R _X or C ₉ H _11-X R _X. Here, X is an integer of 0-7 or 0-11. In addition, each R is preferably independently a hydrocarbyl group or 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. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of the substituted indenyl include 2-phenylindenyl and 2-methylindenyl. Incidentally, the two Cp ^R in the formula (XV) may each be the same or different from each other.

In the above formula (XV), ^{R A} and ^{R B} each independently represent a hydrocarbon group having 1 to 20 carbon atoms, said ^{R A} and R are coordinated μ to ^{M 1}及^{A l.} Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like. Note that the μ coordination is a coordination mode having a crosslinked structure.

In the above formula (XV), R ^C and R ^D are each independently a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

（式中、Ｍ^２は、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Ｒは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^Ｅ〜Ｒ^Ｊは、それぞれ独立して炭素数１〜３のアルキル基又は水素原子を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体を、ＡｌＲ^ＫＲ^ＬＲ^Ｍで表される有機アルミニウム化合物と反応させることで得られる。なお、反応温度は室温程度にすればよいので、温和な条件で製造することができる。また、反応時間は任意であるが、数時間〜数十時間程度である。反応溶媒は特に限定されないが、原料及び生成物を溶解する溶媒であることが好ましく、例えばトルエンやヘキサンを用いればよい。なお、上記メタロセン系化合物の構造は、^１Ｈ−ＮＭＲやＸ線構造解析により決定することが好ましい。 In addition, the said metallocene type compound is a following formula (XVI):

(In the formula, M ² represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and R ^{E to} R ^J each independently has 1 to 3 carbon atoms. An alkyl group or a hydrogen atom, L represents a neutral Lewis base, w represents an integer of 0 to 3, and a metallocene complex represented by AlR ^K R ^L R ^M It is obtained by reacting with. In addition, 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 or hexane may be used. Note that the structure of the metallocene compound is preferably determined by ¹ H-NMR or X-ray structural analysis.

In the metallocene complex represented by the above formula (XVI), Cp ^R is unsubstituted indenyl or substituted indenyl, and has the same meaning as Cp ^R in the above formula (XV). In the above formula (XVI), the metal M ² is a lanthanoid element, scandium or yttrium, and has the same meaning as the metal M ¹ in the above formula (XV).

The metallocene complex represented by the above formula (XVI) contains a silylamide ligand [—N (SiR ₃ ) ₂ ]. The R groups (R ^{E to} R ^J groups) contained in the silylamide ligand are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. In addition, it is preferable that at least one of R ^{E to} R ^J is a hydrogen atom. By making at least one of R ^{E to} R ^J a hydrogen atom, the synthesis of the catalyst becomes easy. Furthermore, a methyl group is preferable as the alkyl group.

  The metallocene complex represented by the above formula (XVI) further contains 0 to 3, preferably 0 to 1, neutral Lewis bases L. Here, examples of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like. Here, when the complex includes a plurality of neutral Lewis bases L, the neutral Lewis bases L may be the same or different.

  In addition, the metallocene complex represented by the above formula (XVI) may exist as a monomer, or may exist as a dimer or a higher multimer.

On the other hand, the organoaluminum compound used to produce the metallocene compound is represented by AlR ^K R ^L R ^M , where R ^K and R ^L are each independently a monovalent hydrocarbon having 1 to 20 carbon atoms. A group or a hydrogen atom, R ^M is a monovalent hydrocarbon group having 1 to 20 carbon atoms, provided that R ^M may be the same as or different from the above R ^K or R ^L. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group and tetradecyl group. , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

  Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, Hexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride , Dioctylaluminum hydride, diisooctylaluminum hydride; ethylaluminum dihydride, n-propylaluminium Dihydride, isobutyl aluminum dihydride and the like. Among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. Moreover, these organoaluminum compounds can be used individually by 1 type, or 2 or more types can be mixed and used for them. In addition, the amount of the organoaluminum compound used for the production of the metallocene compound is preferably 1 to 50 times mol, more preferably about 10 times mol to the metallocene complex.

<< Second Element >>
The second element constituting the polymerization catalyst composition according to the present invention is represented by the following general formula (X)
YR ¹ _a R ² _b R ³ _c (X)
(In the formula, Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. R ³ is a hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is a periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1). is there.

In addition, the second element has the following general formula (Xa):
AlR ¹ R ² R ³ (Xa)
(In the formula, R ¹ and R ² are the same or different, and are a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ is the above. It is preferably an organoaluminum compound represented by the same or different from R ¹ or R ² . Examples of the organoaluminum compound represented by the general formula (X) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, and tripentylaluminum. , Trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diiso hydrogenated Hexyl aluminum, dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propyl aluminum Muzi hydride, isobutylaluminum dihydride and the like. Among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. The organoaluminum compound as the second element described above can be used singly or in combination of two or more. In addition, it is preferable that the compounding quantity of the 2nd element in a polymerization catalyst composition is 1-50 times mol with respect to the said 1st element, and it is still more preferable that it is about 10 times mol.

<< Third element >>
The third element constituting the polymerization catalyst composition according to the present invention contains silica, specifically, it does not indicate only silicon dioxide in a narrow sense (indicated by SiO ₂ in a general formula), but is filled with silicic acid. It means a material, and specifically includes silicates such as hydrous silicate, calcium silicate, and aluminum silicate in addition to anhydrous silicate. In addition, precipitation method silica, gel method silica, dry silica, colloidal silica and the like are included regardless of the aggregation state of silica. Moreover, the silica manufactured by any manufacturing method is included, and both a wet method and a dry method are included. Of these, wet silica having excellent wear resistance is preferred. The BET of silica is not particularly limited, and includes, for example, silica in the range of 10 to 1000 m ² / g. Examples of such silica include “Nip Seal AQ” manufactured by Tosoh Silica Co., Ltd. and BET 205 m ² / g.
In addition, although the silica used as a catalyst composition in a nonpatent literature 3 is baked and dehydrated, in the present invention, it is not necessary to burn the silica.
The blending amount of the third element in the polymerization catalyst composition is preferably more than 0 parts by weight and 100 parts by weight or less, based on 100 parts by weight of the monomer constituting the polymer to be added later, and 2 to 80 parts by weight. Particularly preferred is 5 to 60 parts by weight. By setting the blending amount of the third element within the above range, it is possible to effectively function as a catalyst and to effectively disperse silica in the polymer.

<< Polymerization catalyst composition >>
In the polymerization catalyst composition according to the present invention, the second element and the third element are mixed and aged, and then the first element is added and reacted. First, by mixing and aging the second element and the third element in a solvent, the moisture of the second element and the third element reacts to form a negatively charged complex (anionic complex). . This reaction is described in detail by S. Pasynkiewicz in Polyhedron, Vol. 9, pages 429-453 (1990), for example, that methylaluminoxane is produced by the reaction of alkylaluminum with water. It is supported from. As a result, it is assumed that the anion complex containing the second element is present in the vicinity of the silica of the third element as if a film is formed.
Under this circumstance, by adding the rare earth element-containing compound, which is the first element, to cause the reaction, the rare earth element cationic compound derived from the first element and the second element, and the reaction between the second element and the third element are derived. Thus, a silica-containing anion complex is produced in the reaction system.
The rare earth element of the rare earth element-containing compound of the first element according to the present invention is usually coordinated by three ligands, but depending on conditions, one or more of the ligands are separated in the presence of an anion to be cationized. It has the characteristic of being. Therefore, by reacting the anion complex formed by reacting the second element and the third element with the first element, the first element is cationized, and then the anion complex is bound to the generated cation. It is easy to be in a state.
Here, in the catalyst composition having a rare earth element cationic compound, when a metal such as aluminum (here, Y) is adjacent to the rare earth element, the active center of the catalyst is not the rare earth element, but the adjacent metal element Y (Y. Matsura et al., “Polymerization via the Insertion of Ethyl into the an Al-C Bond Catalyzed by Candom meth s” (See Abstracts, The Kinki Chemical Society, Japan, 2011). In the case of the polymerization catalyst composition, the active center of the polymerization reaction is transferred to the adjacent metal element Y instead of the rare earth element, and a polymer as the target product is produced in Y.
In the polymerization catalyst composition of the present invention, since the rare earth element is present in a state adjacent to the metal element Y existing in the form of a film on the silica particle, the active center can be transferred onto the silica particle. Thereby, the polymerization reaction is performed at the position of the metal element Y on the silica particles, and a polymer very close to the silica is generated. Some of the polymer enters the porous silica and may be integrated with the silica particles.
As described above, in the polymerization catalyst composition of the present invention, the metal element Y derived from the second element, the silica derived from the third element, and the polymer are close to or integrated with each other, and thus, in the produced polymer. Silica can be present in a highly dispersed state.

  Usually, in a polymerization catalyst composition containing a rare earth element compound, in order to increase the efficiency of the polymerization reaction, the amount of the rare earth element compound is increased. However, since the rare earth element compound is expensive, it is used in a large amount. There was a problem that it was difficult to do. However, when the polymerization catalyst composition of the present invention is used, the efficiency of the polymerization reaction depends on the blending amount of silica and metal element Y, not the rare earth element compound. It can be said that the increase in the manufacturing cost by increasing these compounding amounts is relatively low.

  In addition, although there exists a problem that a 1st element is easy to deactivate by presence of water, even if it coexists with the said anion complex, a 1st element is hard to deactivate. Therefore, the silica as the third element does not need to be anhydrous by calcination or the like. Since the steps such as firing can be omitted, the manufacturing cost can be reduced and the manufacturing process can be made more efficient. Rather, the third element preferably contains a certain amount or more of moisture, and a suitable moisture content is 0.1% or more, preferably 0.5% or more. Although there is no particular upper limit, it is preferably 60% by weight or less, more preferably 50% by weight or less, and still more preferably 40% by weight or less.

<< Polymer >>
The polymer that can be synthesized using the catalyst composition of the present invention is not particularly limited, and can be used for the synthesis of any polymer that requires addition of silica. In particular, it is preferably used for the synthesis of polybutadiene and polyisoprene.

<< Method for producing polybutadiene >>
The polymerization catalyst composition of the present invention can be used for the production of various polymers. In the present specification, the synthesis of polybutadiene using the polymerization catalyst composition of the present invention will be specifically described. However, the manufacturing method described in detail below is merely an example. The polybutadiene can be produced by polymerizing 1,3-butadiene as a monomer in the presence of the polymerization catalyst composition.

  The method for producing polybutadiene using the polymerization catalyst composition of the present invention includes at least a polymerization step, and further includes a coupling step, a washing step, and other steps, which are appropriately selected as necessary.

<Polymerization process>
The polymerization step is a step of polymerizing a butadiene monomer.
In the polymerization step, 1,3-butadiene, which is a monomer, is polymerized in the same manner as in the method for producing a polymer using a normal coordination ion polymerization catalyst, except that the polymerization catalyst composition according to the present invention is used. Can be made.

  As a polymerization method, 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 can be used. Moreover, when using a solvent for a polymerization reaction, the solvent used should just be inactive in a polymerization reaction, For example, toluene, cyclohexane, normal hexane, mixtures thereof etc. are mentioned.

  In the polymerization step, for example, (1) a component of the polymerization catalyst composition is separately provided in a polymerization reaction system containing 1,3-butadiene as a monomer, and the polymerization catalyst composition is formed in the reaction system. Alternatively, (2) a polymerization catalyst composition prepared in advance may be provided in the polymerization reaction system.

  Moreover, in the said polymerization process, you may stop superposition | polymerization using polymerization terminators, such as methanol, ethanol, and isopropanol.

  In the polymerization step, the polymerization reaction of 1,3-butadiene is preferably performed in an atmosphere of an inert gas, preferably nitrogen gas or argon gas. The polymerization temperature of the polymerization reaction is not particularly limited, but is preferably in the range of −100 to 200 ° C., for example, and can be about room temperature. If the polymerization temperature is raised, the cis-1,4 selectivity of the polymerization reaction may be lowered. Moreover, since the pressure of the said polymerization reaction takes in 1,3-butadiene fully in a polymerization reaction system, the range of 0.1-10.0 MPa is preferable. The reaction time of the polymerization reaction is not particularly limited, and is preferably in the range of 1 second to 10 days, for example, but can be appropriately selected depending on conditions such as the type of catalyst and polymerization temperature.

<Washing process>
The washing step is a step of washing the polybutadiene obtained in the polymerization step. The medium used for washing is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include methanol, ethanol, isopropanol and the like. When a catalyst derived from a Lewis acid is used as a polymerization catalyst. Can be used in particular by adding an acid (for example, hydrochloric acid, sulfuric acid, nitric acid) to these solvents. The amount of acid to be added is preferably 15 mol% or less with respect to the solvent. Above this, the acid remains in the polymer, which may adversely affect the reaction during kneading and vulcanization.
By this washing step, the amount of catalyst residue in the polybutadiene can be suitably reduced.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

(Example 1: Production method of polymer A)
In a glove box under a nitrogen atmosphere, 5.0 g of silica (trade name: Nipseal AQ, water content of 5.5% by weight calculated by weight reduction method, manufactured by Tosoh Silica Co., Ltd.) in a 1 L pressure-resistant glass reactor, toluene 40. 0 g, 10.0 mmol of trimethylaluminum (manufactured by Tosoh Finechem Co., Ltd.) and 10.0 mmol of triisobutylaluminum (manufactured by Tosoh Finechem Co., Ltd.) were charged and mixed and aged at room temperature for 30 minutes. Next, 68 mg (100 μmol) of bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] was charged and aged at room temperature for 30 minutes. Thereafter, the reactor was taken out from the glove box, and 530.0 g of a toluene solution containing 100.0 g (1.85 mol) of 1,3-butadiene was added, followed by polymerization at 50 ° C. for 180 minutes. After the polymerization, 2 mL of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass of isopropanol solution was added to stop the reaction, and the polymer was added with a large amount of methanol. Separation and vacuum drying at 70 ° C. gave Polymer A. The yield of the obtained polymer A was 88.0 g.

(Example 2: Production method of polymer B)
In a glove box under a nitrogen atmosphere, 5.0 g of silica (trade name: Nipseal AQ, water content of 5.5% by weight calculated by the weight reduction method, manufactured by Tosoh Silica Co., Ltd.) in a 1 L pressure-resistant glass reactor, normal hexane 55 0.0 g, 12.0 mmol of trimethylaluminum (manufactured by Tosoh Finechem Co., Ltd.) and 20.0 mmol of triisobutylaluminum (manufactured by Tosoh Finechem Co., Ltd.) were charged and mixed and aged at room temperature for 30 minutes. Next, 68 mg (100 μmol) of bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] was charged and aged at room temperature for 30 minutes. Thereafter, the reactor was taken out from the glove box, 350.0 g of a normal hexane solution containing 80.0 g (1.48 mol) of 1,3-butadiene was added, and polymerization was performed at 65 ° C. for 180 minutes. After the polymerization, 2 mL of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass of isopropanol solution was added to stop the reaction, and the polymer was added with a large amount of methanol. Separation and vacuum drying at 70 ° C. gave a polymer B. The yield of the obtained polymer B was 70.0 g.

(Example 3: Production method of polymer C)
In a glove box under a nitrogen atmosphere, 3.0 g of silica (trade name: Nipseal AQ, water content of 5.5% by weight calculated by weight reduction method, manufactured by Tosoh Silica Co., Ltd.) in a 1 L pressure glass reactor, normal hexane 25 0.0 g, trimethylaluminum 12.8 mmol (manufactured by Tosoh Finechem Co., Ltd.) and diisobutylaluminum hydride 3.2 mmol (manufactured by Tosoh Finechem Co., Ltd.) were charged and mixed and aged at room temperature for 30 minutes. Next, 43 mg (64 μmol) of bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] was charged and aged at room temperature for 30 minutes. Thereafter, the reactor was taken out from the glove box, 400.0 g of a normal hexane solution containing 80.0 g (1.48 mol) of 1,3-butadiene was added, and polymerization was performed at 65 ° C. for 300 minutes. After the polymerization, 2 mL of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass of isopropanol solution was added to stop the reaction, and the polymer was added with a large amount of methanol. Separation and vacuum drying at 70 ° C. gave Polymer C. The yield of the obtained polymer C was 77.0 g.

(Example 4: Production method of polymer D)
In a glove box under a nitrogen atmosphere, 5.0 g of silica (trade name: Nipseal AQ, water content 5.5% by weight calculated by weight reduction method, manufactured by Tosoh Silica Co., Ltd.) in a 1 L pressure-resistant glass reactor, normal hexane 60 0.0 g, trimethylaluminum 16.0 mmol (manufactured by Tosoh Finechem Co., Ltd.) and triisobutylaluminum 3.2 mmol (manufactured by Tosoh Finechem Co., Ltd.) were charged and mixed and aged at room temperature for 30 minutes. Next, 22 mg (32 μmol) of bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] was charged and aged at room temperature for 30 minutes. Then, after taking out the reactor from the glove box and adding 320.0 g of normal hexane solution containing 80.0 g (1.48 mol) of 1,3-butadiene, polymerization was performed at 80 ° C. for 90 minutes. After the polymerization, 2 mL of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass of isopropanol solution was added to stop the reaction, and the polymer was added with a large amount of methanol. Separation and vacuum drying at 70 ° C. gave a polymer D. The yield of the obtained polymer D was 26.5 g.

(Example 5: Production method of polymer E)
In a glove box under a nitrogen atmosphere, 8.0 g of silica (trade name: nip seal AQ, moisture content calculated by weight reduction method: 5.5% by mass, manufactured by Tosoh Silica Co., Ltd.) in a 1 L pressure-resistant glass reactor, normal hexane 80.0 g, 16.0 mmol of trimethylaluminum (manufactured by Tosoh Finechem Co., Ltd.) and 16.0 mmol of triisobutylaluminum (manufactured by Tosoh Finechem Co., Ltd.) were charged and mixed and aged at room temperature for 30 minutes. Next, 22 mg (32 μmol) of bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] was charged and aged at room temperature for 30 minutes. Thereafter, the reactor was taken out of the glove box, and after adding 320.0 g of a normal hexane solution containing 80.0 g (1.48 mol) of 1,3-butadiene, polymerization was performed at 80 ° C. for 240 minutes. After the polymerization, 2 mL of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass of isopropanol solution was added to stop the reaction, and the polymer was added with a large amount of methanol. Separation and vacuum drying at 70 ° C. gave a polymer E. The yield of the obtained polymer E was 78.5 g.

(Example 6: Production method of polymer F)
In a glove box under a nitrogen atmosphere, 3.0 g of silica (trade name: Nipseal AQ, moisture content calculated by weight reduction method: 5.5% by mass, manufactured by Tosoh Silica Corporation) in a 1 L pressure glass reactor, normal hexane 80.0 g, trimethylaluminum 9.6 mmol (manufactured by Tosoh Finechem Co., Ltd.) and diisobutylaluminum hydride 3.2 mmol (manufactured by Tosoh Finechem Co., Ltd.) were charged and mixed and aged at room temperature for 30 minutes. Next, 21 mg (32 μmol) of trisbistrimethylsilylamid gadolinium [Gd [N (SiMe ₃ ) ₂ ] ₃ ] was charged and aged at room temperature for 30 minutes. Then, after taking out the reactor from the glove box and adding 320.0 g of normal hexane solution containing 80.0 g (1.48 mol) of 1,3-butadiene, polymerization was carried out at 80 ° C. for 480 minutes. After the polymerization, 2 mL of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass of isopropanol solution was added to stop the reaction, and the polymer was added with a large amount of methanol. Separation and vacuum drying at 70 ° C. gave a polymer F. The yield of the obtained polymer F was 66.0 g.

(Comparative Example 1)
Polymerization was carried out in the same manner as in Example 1 except that silica was not used, and no polymer was produced.

(Comparative Example 2)
In Example 1, except that silica (trade name: nip seal AQ, water content less than 0.1% by weight calculated by the weight reduction method, manufactured by Tosoh Silica Co., Ltd.) was used for 2 hours at 100 ° C. in air. When polymerization was carried out in the same manner, it was confirmed that almost no polymer was produced and silica was agglomerated.

  For the polymers A to G prepared as described above, the microstructure (cis-1,4 bond amount), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) were measured and evaluated by the following methods.

（式中、ａは、フーリエ変換赤外分光法（ＦＴ−ＩＲ）による透過率スペクトルの１１３０ｃｍ^−１付近の山ピーク値であり、ｂは、９６７ｃｍ^−１付近の谷ピーク値であり、ｃは、９１１ｃｍ^−１付近の谷ピーク値であり、ｄは、７３６ｃｍ^−１付近の谷ピーク値である）から導かれるｅ，ｆ，ｇの値を用い、下記式（ｉｉ）
（シス−１，４結合量の計算値＝ｅ／（ｅ＋ｆ＋ｇ）×１００ ・・・（ｉｉ）
にしたがって、シス１，４結合量の計算値を求めた。 <Analytical Method of Polymers A to F>
(1) Microstructure (cis-1,4 bond amount)
The microstructures (cis-1,4 bonds) of the polymers A to F were calculated by measuring the transmittance spectrum of Fourier transform infrared spectroscopy (FT-IR). Specifically, as a carbon disulfide blank in the same cell, a transmittance spectrum by FT-IR of a carbon disulfide solution of each polymer adjusted to a concentration of 5 mg / mL was measured, and the following determinant (i):

(In the formula, a is a peak peak value in the vicinity of 1130 cm ⁻¹ of the transmittance spectrum by Fourier transform infrared spectroscopy (FT-IR), b is a valley peak value in the vicinity of 967 cm ⁻¹ , and c is a valley peak value around 911 cm ^-1, d is, e derived from 736cm ^-1 is a valley peak value around), f, using the value of g, the following formula (ii)
(Calculated value of cis-1,4 bond amount = e / (e + f + g) × 100 (ii)
Thus, the calculated value of cis 1,4 bond amount was obtained.

(2) Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of polymers A to F
Gel permeation chromatography [GPC: Tosoh HLC-8220GPC, column: Tosoh GMH _XL- 2, detector: differential refractometer (RI)], based on monodisperse polystyrene, converted to polystyrene of synthetic polyisoprene The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were determined. The measurement temperature is 40 ° C. Tetrahydrofuran (THF) was used as an elution solvent.

  From the results in Table 1, it was confirmed that a polymer having a high cis-1,4 bond ratio can be synthesized using the polymerization catalyst composition of the present invention.

  The production method of the polymerization catalyst composition of the present invention and the polymerization catalyst composition produced by the production method are suitable for production of rubber products that require addition of silica, for example, tire members (particularly, tire tread members). Is available.

Claims (3)

A rare earth element-containing compound having the following general formula (I):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents unsubstituted or substituted indenyl, and R ^{a to} R ^f each independently represents an alkyl having 1 to 3 carbon atoms. A group or a hydrogen atom, L represents a neutral Lewis base, w represents an integer of 0 to 3), and the following general formula (II):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and X ′ represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group. , A silyl group or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, and w represents an integer of 0 to 3). A first element comprising a complex of
The following general formula (Xa):
AlR ¹ R ² R ³ (Xa)
(In the formula, R ¹ and R ² are the same or different, and are a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ is the above. A second element comprising a compound represented by the same or different from R ¹ or R ² ;
About the third element containing silica and having a water content of 0.1% by weight or more,
A polymerization catalyst composition , characterized in that the second element and the third element are mixed and aged and then the first element is added and reacted , and an ionic compound is not blended. Manufacturing method.   The polymerization according to claim 1, wherein the third element is blended so as to be more than 0 parts by weight and 100 parts by weight or less in terms of anhydride weight with respect to 100 parts by weight of the monomer constituting the polymer. A method for producing a catalyst composition. The method for producing a polymerization catalyst composition according to claim 1, wherein the complex does not have a bond between a rare earth element and carbon.