JP2013194100A - Polymerization catalyst composition, and method for producing polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a polymer in which a conjugated diene except the conjugated diene or a non-conjugated olefin compound is added to the conjugated diene polymer to obtain a polymer material having a higher function than the conjugated diene polymer having a high cis-1,4-bond amount.SOLUTION: A polymerization catalyst composition is characterized by comprising a rare earth element-containing compound containing at least either of a rare earth element compound and a reaction product of a rare earth element compound with a Lewis base, at least one anion supply source selected from the group consisting of an ionic compound comprising a non-coordinating anion and a cation, aluminoxane and a halogen compound, and at least one monomer selected from the group consisting of conjugated dien monomers and non-conjugated olefins.

Description

  The present invention relates to a polymerization catalyst composition and a method for producing a polymer.

Conventionally, many proposals have been made on polymerization catalysts for conjugated dienes. Among these, particularly from the viewpoint of durability, a polymerization catalyst capable of obtaining a conjugated diene polymer having a high cis-1,4 bond amount has been desired and has been studied. For example, composite catalyst systems based on transition metal compounds such as nickel, cobalt and titanium are known, and some of them are already widely used industrially as polymerization catalysts for butadiene, isoprene and the like. (Non-patent document 1, Patent document 1, etc.). In addition, in order to achieve higher cis-1,4 bonds, composite catalyst systems composed of rare earth element compounds and Group 1 to 3 organometallic compounds have been researched and developed, and highly stereospecific polymerization has been studied. (Non-Patent Documents 2 to 6, Patent Document 2 and the like).
On the other hand, with the recent progress of industrial technology, the market demand for the function of polymer materials has become more and more advanced, and conjugated diene polymers having a high cis-1,4 bond amount can be further improved. It has been desired to develop a polymer material.

Japanese Patent Publication No. 37-8198 German patent application 2,848,964

End. Ing. Chem., 48, 784, 1956 Makromol. Chem. Suppl, 4, 61, 1981 J. Polym. Sci., Polym. Chem. Ed., 18, 3345, 1980 Sci. Sinica., 2/3, 734, 1980 Rubber Chem. Technol., 58, 117, 1985 Macromolecules, 15, 230, 1982; Makromol. Chem., 94, 119, 1981

  An object of the present invention is to obtain a polymer material obtained by further increasing the functionality of a conjugated diene polymer having a high cis-1,4 bond amount, and a conjugated diene other than the conjugated diene or a non-conjugated olefin. It is an object of the present invention to provide a catalyst composition capable of producing a polymer to which a polymer is added. Another object of the present invention is to provide a method for producing a polymer in which a conjugated diene other than the conjugated diene or a non-conjugated olefin is added to the conjugated diene polymer.

In order to solve the above problems, in the present invention, an ion comprising a rare earth element-containing compound containing at least one of a rare earth element compound and a reaction product of a rare earth element compound and a Lewis base, a non-coordinating anion, and a cation. And at least one anion source selected from the group consisting of a functional compound, an aluminoxane and a halogen compound, and at least one monomer selected from the group consisting of a conjugated diene monomer and a non-conjugated olefin. A polymerization catalyst composition is provided.
By using the polymerization catalyst composition, a conjugated diene other than the conjugated diene is added to the conjugated diene polymer in order to obtain a high-functional polymer material having a higher cis-1,4 bond conjugated diene polymer. Alternatively, it is possible to add non-conjugated olefins.

The polymerization catalyst composition of the present invention further includes 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 each a hydrocarbon group having 1 to 10 carbon atoms or hydrogen. An atom, R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ¹ , R ² and R ³ may be the same or different from each other, and Y is from Group 1 of the Periodic Table; When it is a selected metal, a is 1 and b and c are 0. 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 preferably 1).

As another form of the rare earth element-containing compound, the following general formula (V) or (VI):
M ¹¹ X ¹¹ ₂・ L ¹¹ w (V)
M ¹¹ X ¹¹ ₃ · L ¹¹ w (VI)
(In each formula, M ¹¹ represents a lanthanoid element, scandium or yttrium, and X ¹¹ 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. A residue, a carboxylic acid residue, a thiocarboxylic acid residue, a phosphorus compound residue, unsubstituted or substituted cyclopentadienyl, or unsubstituted or substituted indenyl; L ¹¹ represents a Lewis base; A compound represented by 0 to 3) can be preferably exemplified.
In addition, when using the rare earth element containing compound represented by the said general formula (V) or (VI) for a polymerization catalyst composition, addition of the compound represented by the said general formula (X) is required.

（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）：

（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、並びに下記一般式（ＩＩＩ）：

（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、無置換もしくは置換シクロペンタジエニル、インデニル又はフルオレニルを示し、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の整数を示し、［Ｂ］^-は、非配位性アニオンを示す）で表されるハーフメタロセンカチオン錯体からる群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。
なお、上記のメタロセン錯体、ハーフメタロセンカチオン錯体を重合触媒組成物に用いるにあたっては、上記一般式（Ｘ）で表される化合物の添加が必要となる。 The rare earth element-containing compound has 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), and the following general formula (III ):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^{R ′} represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxide group or 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, w represents an integer of 0 to 3, and [B] ⁻ represents a non-coordinating group. It preferably includes at least one complex selected from the group consisting of half-metallocene cation complexes represented by
In addition, when using said metallocene complex and a half metallocene cation complex for a polymerization catalyst composition, addition of the compound represented by the said general formula (X) is required.

  The rare earth element-containing compound represented by the general formula (V) or (VI) is preferably a compound having no bond between the rare earth element and carbon.

As still another form of the rare earth element-containing compound, the following general 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 Preferable examples include metallocene complexes represented by a hydrogen atom, wherein Y is coordinated to Q, and a and b are 2.

（式中、Ｍ¹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、Ｍ¹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錯体とすることが好ましい。 The rare earth element-containing compound of the general formula (A) is represented by 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. It is preferable to use a metallocene complex represented by

The compound represented by the general formula (X) is represented by the following general formula (Xa):
AlR ¹ R ² R ³ (Xa)
(In the formula, R ¹ and R ² are each 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 ¹ , R ² and R ³ Are preferably the same or different from each other).

  The ionic compound comprising the non-coordinating anion and cation is at least selected from the group consisting of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and triphenylcarbonium tetrakis (pentafluorophenyl) borate. Preferably one is included.

  The conjugated diene monomer preferably has 4 to 8 carbon atoms.

  The non-conjugated olefin is preferably an acyclic olefin having 2 to 10 carbon atoms.

The present invention also provides a rare earth element-containing compound containing at least one of a rare earth element compound and a reaction product of a rare earth element compound and a Lewis base, an ionic compound comprising a non-coordinating anion and a cation, an aluminoxane, and a halogen. Mixing and aging at least one anion source selected from the group consisting of compounds and at least one monomer selected from the group consisting of conjugated diene monomers and non-conjugated olefins, and then the monomers There is provided a method for producing a polymer, characterized in that a conjugated diene monomer different from the above is added and the added conjugated diene monomer is subjected to a polymerization reaction.
The polymer production method can produce a polymer in which a conjugated diene other than the conjugated diene or a non-conjugated olefin is added to the conjugated diene polymer.

  ADVANTAGE OF THE INVENTION According to this invention, the catalyst composition which can manufacture the polymer which added conjugated dienes other than this conjugated diene or nonconjugated olefins to the conjugated diene polymer can be provided. Moreover, according to this invention, the manufacturing method of the polymer which added conjugated dienes other than this conjugated diene or nonconjugated olefins to the conjugated diene polymer can be provided.

-Polymerization catalyst composition-
First, the polymerization catalyst composition according to the present invention will be exemplified and described in detail. In the polymerization catalyst composition of the present invention, a conjugated diene monomer is polymerized with a high 1,4-cis bond amount, and a conjugated diene monomer or a non-conjugated olefin different from the conjugated diene can be added. Is possible. Such a polymerization catalyst composition is preferably the following first polymerization catalyst composition, second catalyst composition, or third catalyst composition.

--First polymerization catalyst composition--
The first polymerization catalyst composition (hereinafter also referred to as “first polymerization catalyst composition”) will be described.
As the first polymerization catalyst composition,
(A) component: a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base, and preferably the rare earth element compound or reactant that does not have a bond between the rare earth element and carbon;
Component (B): Contains ionic compound (B-1) composed of non-coordinating anion and cation, aluminoxane (B-2), Lewis acid, complex compound of metal halide and Lewis base, and active halogen. At least one selected from the group consisting of at least one halogen compound (B-3) among organic compounds;
The polymerization catalyst composition containing is mentioned.
The polymerization catalyst composition further comprises:
(C) Component: 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 each a hydrocarbon group having 1 to 10 carbon atoms or R ³ is a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ¹ , R ² and R ³ may be the same or different from each other, and Y is group 1 of the periodic table 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 selected. 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).

Since the ionic compound (B-1) and the halogen compound (B-3) do not have a carbon atom to be supplied to the component (A), the carbon source for the component (A) is the above ( Component C) is required. In addition, even if it is a case where the said polymerization catalyst composition contains the said aluminoxane (B-2), this polymerization catalyst composition can contain the said (C) component. The first polymerization catalyst composition may contain other components, such as a promoter, contained in a normal rare earth element compound-based polymerization catalyst composition.
In the polymerization reaction system, the concentration of the component (A) contained in the first polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol / l.

The component (A) used in the first polymerization catalyst composition is a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base. Here, the reaction of the rare earth element compound and the rare earth element compound with the Lewis base is performed. It is preferable that the product does not have a bond between a rare earth element and carbon. When the rare earth element compound and the reactant 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. In addition, the said (A) component may be used individually by 1 type, and may be used in combination of 2 or more type.

The rare earth element compound is preferably a divalent or trivalent salt or complex compound of a rare earth metal, and one or more coordinations selected from a hydrogen atom, a halogen atom and an organic compound residue. More preferably, the rare earth element compound contains a child. Furthermore, the reaction product of the rare earth element compound or the rare earth element compound and a Lewis base is represented by the following general formula (V) or (VI):
M ¹¹ X ¹¹ ₂・ L ¹¹ w (V)
M ¹¹ X ¹¹ ₃ · L ¹¹ w (VI)
(In the formula, M ¹¹ represents a lanthanoid element, scandium or yttrium, and X ¹¹ 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 group, carboxylic acid residue, thiocarboxylic acid residue, phosphorus compound residue, unsubstituted or substituted cyclopentadienyl, or unsubstituted or substituted indenyl, L ¹¹ represents a Lewis base, w is 0 to 3).

  Specific examples of the group (ligand) bonded to the rare earth element of the rare earth element compound include a hydrogen atom; a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert- Aliphatic alkoxy groups 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, thio aliphatic thiolate groups such as sec-butoxy group and thio-tert-butoxy group; Noxy 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-butyl Arylamide groups such as ru-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.

In the component (A) used in the first polymerization catalyst composition, examples of the Lewis base that reacts with the rare earth element compound include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, Diolefins and the like. Here, when the rare earth element compound reacts with a plurality of Lewis bases (in the formulas (XI) and (XII), when w is 2 or 3), the Lewis base L ¹¹ is the same or different. It may be.

  The component (B) used in the first polymerization catalyst composition is at least one compound selected from the group consisting of an ionic compound (B-1), an aluminoxane (B-2), and a halogen compound (B-3). is there. In addition, it is preferable that content of the sum total of (B) component in said 1st polymerization catalyst composition is 0.1-50 times mole with respect to (A) component.

  The ionic compound represented by the above (B-1) is composed of a non-coordinating anion and a cation, and reacts with a reaction product of the rare earth element compound or its Lewis base as the component (A) to be cationic. Examples thereof include ionic compounds capable of generating a transition metal compound. Here, as the non-coordinating anion, for example, 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, tri Decahydride-7,8-dicarboundecaborate and the like can be mentioned. On the other hand, examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal. Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation and tri (substituted phenyl) carbonium cation, and more specifically, as tri (substituted phenyl) carbonyl cation, Examples include tri (methylphenyl) carbonium cation, tri (dimethylphenyl) carbonium cation, and the like. Specific examples of ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation (for example, tri (n-butyl) ammonium cation); N, N-dimethylanilinium N, N-dialkylanilinium cation such as cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation; dialkylammonium cation such as diisopropylammonium cation and dicyclohexylammonium cation Is mentioned. Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation. Accordingly, the ionic compound is preferably a compound selected and combined from the above-mentioned non-coordinating anions and cations, specifically, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbohydrate. Preferred is nitrotetrakis (pentafluorophenyl) borate. Moreover, these ionic compounds can be used individually by 1 type, or 2 or more types can be mixed and used for them. In addition, it is preferable that it is 0.1-10 times mol with respect to (A) component, and, as for content of the ionic compound in the said 1st polymerization catalyst composition, it is still more preferable that it is about 1 time mol.

  The aluminoxane represented by the above (B-2) is a compound obtained by bringing an organoaluminum compound and a condensing agent into contact with each other. For example, the repetition represented by the general formula: (—Al (R ′) O—) A chain aluminoxane or cyclic aluminoxane having a unit (wherein R ′ is a hydrocarbon group having 1 to 10 carbon atoms, and some of the hydrocarbon groups may be substituted with a halogen atom and / or an alkoxy group) The degree of polymerization of the unit is preferably 5 or more, and more preferably 10 or more. Here, specific examples of R ′ include a methyl group, an ethyl group, a propyl group, and an isobutyl group. Among these, a methyl group is preferable. Examples of the organoaluminum compound used as an aluminoxane raw material include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof, and trimethylaluminum is particularly preferable. For example, an aluminoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can be preferably used. The content of the aluminoxane in the first polymerization catalyst composition is such that the element ratio Al / M of the rare earth element M constituting the component (A) and the aluminum element Al of the aluminoxane is about 10 to 1000. It is preferable to do.

  The halogen compound represented by (B-3) is composed of at least one of a Lewis acid, a complex compound of a metal halide and a Lewis base, and an organic compound containing an active halogen, and is, for example, the component (A). By reacting with a rare earth element compound or a reaction product thereof with a Lewis base, a cationic transition metal compound, a halogenated transition metal compound, or a compound in which the transition metal center is deficient in charge can be generated. In addition, it is preferable that content of the sum total of the halogen compound in said 1st polymerization catalyst composition is 1-5 times mole with respect to (A) component.

As the Lewis acid, boron-containing halogen compounds such as B (C ₆ F ₅ ) ₃ and aluminum-containing halogen compounds such as Al (C ₆ F ₅ ) ₃ can be used. A halogen compound containing an element belonging to the group V, VI or VIII can also be used. Preferably, aluminum halide or organometallic halide is used. Moreover, as a halogen element, chlorine or bromine is preferable. Specific examples of the Lewis acid include methyl aluminum dibromide, methyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, diethyl aluminum bromide, diethyl Aluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquichloride, dibutyltin dichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, phosphorus trichloride , Pentachloride , Tin tetrachloride, titanium tetrachloride, tungsten hexachloride, etc., among which diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide, ethylaluminum dibromide preferable.

  The metal halide constituting the complex compound of the above metal halide and Lewis base includes beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, iodine. Calcium chloride, barium chloride, barium bromide, barium iodide, zinc chloride, zinc bromide, zinc iodide, cadmium chloride, cadmium bromide, cadmium iodide, mercury chloride, mercury bromide, mercury iodide, manganese chloride, Manganese bromide, manganese iodide, rhenium chloride, rhenium bromide, rhenium iodide, copper chloride, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, gold bromide, etc. Of these, magnesium chloride, calcium chloride, barium chloride, manganese chloride, zinc chloride, and copper chloride are preferred. , Magnesium chloride, manganese chloride, zinc chloride, copper chloride being particularly preferred.

  Moreover, as a Lewis base which comprises the complex compound of the said metal halide and a Lewis base, a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, alcohol, etc. are preferable. Specifically, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphinoethane, acetylacetone, benzoylacetone , Propionitrile acetone, valeryl acetone, ethyl acetylacetone, methyl acetoacetate, ethyl acetoacetate, phenyl acetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2-ethyl-hexanoic acid, olein Acid, stearic acid, benzoic acid, naphthenic acid, versatic acid, triethylamine, N, N-dimethylacetamide, tetrahydrofuran, diphenyl ether, 2-ethyl-hexyl alcohol Examples include oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, and lauryl alcohol. Among these, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2 -Ethylhexyl alcohol, 1-decanol and lauryl alcohol are preferred.

  The Lewis base is reacted at a ratio of 0.01 to 30 mol, preferably 0.5 to 10 mol, per 1 mol of the metal halide. When the reaction product with the Lewis base is used, the metal remaining in the polymer can be reduced.

  Examples of the organic compound containing the active halogen include benzyl chloride.

The component (C) used in the first polymerization catalyst composition is the above 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 each a hydrocarbon group having 1 to 10 carbon atoms or R ³ is a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ¹ , R ² and R ³ may be the same or different from each other, and Y is group 1 of the periodic table 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 selected. Is 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). General formula (Xa):
AlR ¹ R ² R ³ (Xa)
[Wherein R ¹ and R ² 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 ¹ , R ² and R ³ Are preferably the same or different from each other]. 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 component (C) described above can be used alone or in combination of two or more. In addition, it is preferable that it is 1-50 times mole with respect to (A) component, and, as for content of the organoaluminum compound in the said 1st polymerization catalyst composition, it is still more preferable that it is about 10 times mole.

  The first polymerization catalyst composition further contains a conjugated diene monomer and / or a non-conjugated olefin compound. As the conjugated diene monomer and / or non-conjugated olefin to be added here, a different type of monomer from the monomer constituting the main chain of the polymer which is the target of the polymerization reaction is used. The monomer previously blended as a polymerization catalyst composition (hereinafter also referred to as “blended monomer”) is not particularly limited as long as it is a conjugated diene monomer or a non-conjugated olefin. In the case of a monomer, the number of carbon atoms is preferably 4-8. Specific examples include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and among these, 1,3-butadiene and isoprene are preferable. In addition, these conjugated diene compounds may be used independently and may be used in combination of 2 or more type. In the case of a non-conjugated olefin, an acyclic olefin having 2 to 10 carbon atoms can be suitably used. Specific examples include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and styrene. Among these, ethylene, propylene, and 1-pentene are preferable. Butene and styrene are preferred. These non-conjugated olefins may be used alone or in combination of two or more.

  The blended monomer may or may not be polymerized in the catalyst composition. Moreover, when making it superpose | polymerize, although the product may be an oligomer or a polymer, it is preferable that the polymerization number of a mixing | blending monomer is 1-10. Moreover, it is preferable that the molecular weight per block which a compounding monomer comprises is 1000 or less. It is possible to adjust the polymerization degree of the compounded monomer by the amount of the compounded monomer added to the catalyst composition, the aging temperature, and the time.

  The total blending amount of the blended monomer in the polymerization catalyst composition is 0.1 to 10,000 mol equivalent, particularly 1 to 5000 mol equivalent, and further 10 to 3500 mol equivalent of the total blending amount of the rare earth element-containing compound. Is preferred. The compounding monomer may be polymerized or not polymerized depending on the desired function to be added to the target polymer. However, when the compounding amount of the compounding monomer exceeds 10,000 mol equivalent of the total compounding amount of the rare earth element-containing compound, the compounding monomer can be polymerized to form a relatively long chain polymer. If the polymer of the long chain compounding monomer is added to the main chain formed by polymerization later, the characteristics of the main chain may be impaired. On the other hand, if it is less than 0.1 mol equivalent of the total compounding amount of the rare earth element-containing compound, there is a possibility that the function is hardly added to the main chain.

（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）： --Second polymerization catalyst composition--
As the second polymerization catalyst composition (hereinafter also referred to as “second polymerization catalyst composition”), 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、並びに下記一般式（ＩＩＩ）：

(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), and the following general formula (III ):

（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、無置換もしくは置換シクロペンタジエニル、インデニル又はフルオレニルを示し、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の整数を示し、［Ｂ］^-は、非配位性アニオンを示す）で表されるハーフメタロセンカチオン錯体からる群より選択される少なくとも１種類の錯体を含む希土類元素含有化合物を含む重合触媒組成物が挙げられる。

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^{R ′} represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxide group or 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, w represents an integer of 0 to 3, and [B] ⁻ represents a non-coordinating group. And a polymerization catalyst composition containing a rare earth element-containing compound containing at least one complex selected from the group consisting of half metallocene cation complexes represented by

The second polymerization catalyst composition may further contain other components contained in the polymerization catalyst composition containing a normal metallocene complex, such as a promoter. 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 second 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.

In the half metallocene cation complex represented by the general formula (III), Cp ^{R ′} in the formula is unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and among these, unsubstituted or substituted indenyl It is preferable that Cp ^{R ′} having a cyclopentadienyl ring as a basic skeleton is represented by C ₅ H _5-X R _X. Here, X is an integer of 0-5. 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 Cp ^{R ′} having a cyclopentadienyl ring as a basic skeleton include the following.

（式中、Ｒは水素原子、メチル基又はエチル基を示す。）
一般式（ＩＩＩ）において、上記インデニル環を基本骨格とするＣｐ^R'は、一般式（Ｉ）のＣｐ^Rと同様に定義され、好ましい例も同様である。

(In the formula, R represents a hydrogen atom, a methyl group or an ethyl group.)
In the general formula (III), Cp ^{R ′} having the above indenyl ring as a basic skeleton is defined in the same manner as Cp ^{R in the} general formula (I), and preferred examples thereof are also the same.

In the general formula (III), Cp ^{R ′} having the 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, X is an integer of 0-9 or 0-17. 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.

  The central metal M in the general formulas (I), (II) and (III) 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 a group defined in the same manner as X in the general formula (III) described below, and preferred groups are also the same.

  In the general formula (III), X is a group 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. 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.

  In the general formula (III), the thiolate group represented by X includes a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thio n-butoxy group, a thioisobutoxy group, a thiosec-butoxy group, a thiotert-butoxy group and the like Group thiolate group; thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropyl Arylthiolate groups such as thiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, 2,4,6-triisopropylthiophenoxy group, etc. Among these, 2,4,6-triisopropylthiophenoxy group Preferred.

  In the general formula (III), examples of the amide group represented by X include aliphatic amide groups such as a dimethylamide group, a diethylamide group, and a diisopropylamide group; a phenylamide group, a 2,6-di-tert-butylphenylamide group, 2 , 6-diisopropylphenylamide group, 2,6-dineopentylphenylamide group, 2-tert-butyl-6-isopropylphenylamide group, 2-tert-butyl-6-neopentylphenylamide group, 2-isopropyl- Arylamide groups such as 6-neopentylphenylamide group and 2,4,6-tri-tert-butylphenylamide group; and bistrialkylsilylamide groups such as bistrimethylsilylamide group. Among these, bistrimethylsilylamide Groups are preferred.

  In the general formula (III), examples of the silyl group represented by X include trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropylsilyl (bistrimethylsilyl) silyl group, and the like. Among these, a tris (trimethylsilyl) silyl group is preferable.

  In the general formula (III), the halogen atom represented by X may be any of a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, but a chlorine atom or a bromine atom is preferred. Moreover, as a C1-C20 hydrocarbon group which X represents, specifically, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- Linear or branched aliphatic hydrocarbon groups such as butyl group, neopentyl group, hexyl group, octyl group; aromatic hydrocarbon groups such as phenyl group, tolyl group, naphthyl group; aralkyl groups such as benzyl group, etc. Others: Examples include hydrocarbon groups containing silicon atoms such as trimethylsilylmethyl group and bistrimethylsilylmethyl group. Among these, methyl group, ethyl group, isobutyl group, trimethylsilylmethyl group and the like are preferable.

  In the general formula (III), X is preferably a bistrimethylsilylamide group or a hydrocarbon group having 1 to 20 carbon atoms.

In the general formula (III), [B] ^- The non-coordinating anion represented by, for example, a tetravalent boron anion. Specific examples of the tetravalent boron anion 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, tri Decahydride-7,8-dicarbaoundecaborate and the like can be mentioned, and among these, tetrakis (pentafluorophenyl) borate is preferable.

  The metallocene complex represented by the general formulas (I) and (II) and the half metallocene cation complex represented by the general formula (III) are further 0 to 3, preferably 0 to 1 neutral. Contains Lewis base 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.

  Further, the metallocene complex represented by the general formula (I) and the formula (II) and the half metallocene cation complex represented by the general formula (III) may exist as a monomer, It may exist as a body or 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 half metallocene cation complex represented by the general formula (III) can be obtained, for example, by the following reaction.

Here, in the compound represented by the general formula (IV), M represents a lanthanoid element, scandium or yttrium, and Cp ^{R ′} independently represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl. , 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 0 to 3 Indicates an integer. In the ionic compound represented by the general formula [A] ⁺ [B] ⁻ , [A] ⁺ represents a cation, and [B] ⁻ represents a non-coordinating anion.

Examples of the cation represented by [A] ⁺ 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 a triphenylcarbonium cation and a tri (substituted phenyl) carbonium cation. The tri (substituted phenyl) carbonyl cation is specifically exemplified by tri (methylphenyl). ) Carbonium cation and the like. Examples of amine cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N- N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation; dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation. Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation. Among these cations, N, N-dialkylanilinium cation or carbonium cation is preferable, and N, N-dialkylanilinium cation is particularly preferable.

The ionic compound represented by the general formula [A] ⁺ [B] ⁻ used for the above reaction is a compound selected and combined from the above non-coordinating anions and cations, which is N, N-dimethylaniline. Preference is given to nium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like. In addition, the ionic compound represented by the general formula [A] + [B]-is preferably added in an amount of 0.1 to 10 times mol, more preferably about 1 time mol based on the metallocene complex. When the half metallocene cation complex represented by the general formula (III) is used for the polymerization reaction, the half metallocene cation complex represented by the general formula (III) may be provided as it is in the polymerization reaction system, or the compound represented by the general formula (IV) and the general formula used in the reaction [a] ⁺ [B] ^- provides an ionic compound represented separately into the polymerization reaction system, the general formula in the reaction system (III You may form the half metallocene cation complex represented by this. Further, by using a combination of the metallocene complex represented by the general formula (I) or the formula (II) and the ionic compound represented by the general formula [A] ⁺ [B] ⁻ , A half metallocene cation complex represented by the formula (III) can also be formed.

  The structures of the metallocene complexes represented by the general formulas (I) and (II) and the half metallocene cation complex represented by the general formula (III) are preferably determined by X-ray structural analysis.

  The co-catalyst that can be used in the second polymerization catalyst composition can be arbitrarily selected from components used as a co-catalyst for a polymerization catalyst composition containing a normal metallocene complex. Suitable examples of the cocatalyst include aluminoxanes, organoaluminum compounds, and the above ionic compounds. These promoters may be used alone or in combination of two or more.

  The aluminoxane is preferably an alkylaminoxan, and examples thereof include methylaluminoxane (MAO) and modified methylaluminoxane. As the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem Co., Ltd.) and the like are preferable. The aluminoxane content in the second polymerization catalyst composition is such that the element ratio Al / M between the central metal 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 make it.

  On the other hand, as the organoaluminum compound, the general formula AlRR′R ″ (wherein R and R ′ are each independently a C1-C10 hydrocarbon group or a hydrogen atom, and R ″ is a C1-C10 An organoaluminum compound represented by (a hydrocarbon group) is preferable. Examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, and dialkylaluminum hydride. Among these, trialkylaluminum is preferable. Examples of the trialkylaluminum include triethylaluminum and triisobutylaluminum. In addition, it is preferable that it is 1-500 times mol with respect to a metallocene complex, and, as for content of the organoaluminum compound in the said polymerization catalyst composition, it is still more preferable that it is 10-150 times mol.

  Further, in the above polymerization catalyst composition, the metallocene complex represented by the general formula (I) and the formula (II) and the half metallocene cation complex represented by the above general formula (III) are each used as an appropriate promoter. By combining, the amount of cis-1,4 bonds and the molecular weight of the resulting polymer can be increased.

  The second polymerization catalyst composition further contains a conjugated diene monomer and / or a non-conjugated olefin compound. As the conjugated diene monomer and / or non-conjugated olefin to be added here, a different type of monomer from the monomer constituting the main chain of the polymer which is the target of the polymerization reaction is used. The monomer previously blended as a polymerization catalyst composition (hereinafter also referred to as “blended monomer”) is not particularly limited as long as it is a conjugated diene monomer or a non-conjugated olefin. In the case of a monomer, the number of carbon atoms is preferably 4-8. Specific examples include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and among these, 1,3-butadiene and isoprene are preferable. In addition, these conjugated diene compounds may be used independently and may be used in combination of 2 or more type. In the case of a non-conjugated olefin, an acyclic olefin having 2 to 10 carbon atoms can be suitably used. Specific examples include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and styrene. Among these, ethylene, propylene, and 1-pentene are preferable. Butene and styrene are preferred. These non-conjugated olefins may be used alone or in combination of two or more.

  The blended monomer may or may not be polymerized in the catalyst composition. Moreover, when making it superpose | polymerize, although the product may be an oligomer or a polymer, it is preferable that the polymerization number of a mixing | blending monomer is 1-10. Moreover, it is preferable that the molecular weight per block which a compounding monomer comprises is 1000 or less. It is possible to adjust the polymerization degree of the compounded monomer by the amount of the compounded monomer added to the catalyst composition, the aging temperature, and the time.

  The total blending amount of the blended monomer in the polymerization catalyst composition is 0.1 to 10,000 mol equivalent, particularly 1 to 5000 mol equivalent, and further 10 to 3500 mol equivalent of the total blending amount of the rare earth element-containing compound. Is preferred. The compounding monomer may be polymerized or not polymerized depending on the desired function to be added to the target polymer. However, when the compounding amount of the compounding monomer exceeds 10,000 mol equivalent of the total compounding amount of the rare earth element-containing compound, the compounding monomer can be polymerized to form a relatively long chain polymer. If the polymer of the long chain compounding monomer is added to the main chain formed by polymerization later, the characteristics of the main chain may be impaired. On the other hand, if it is less than 0.1 mol equivalent of the total compounding amount of the rare earth element-containing compound, there is a possibility that the function is hardly added to the main chain.

--Third polymerization catalyst composition--
Next, a third polymerization catalyst composition (hereinafter also referred to as “third polymerization catalyst composition”) will be described.
The third polymerization catalyst composition has the following formula (A) as a rare earth element-containing compound:
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.

（式中、Ｍ¹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、Ｍ¹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錯体が挙げられる。
上記メタロセン錯体を用いることで、重合体を製造することができる。また、上記メタロセン錯体、例えば予めアルミニウム触媒と複合させてなる錯体を用いることで、重合体合成時に使用されるアルキルアルミニウムの量を低減したり、無くしたりすることが可能となる。なお、従来の触媒系を用いると、重合体合成時に大量のアルキルアルミニウムを用いる必要がある。例えば、従来の触媒系では、金属触媒に対して１０当量以上のアルキルアルミニウムを用いる必要があるところ、上記メタロセン錯体であれば、５当量程度のアルキルアルミニウムを加えることで、優れた触媒作用が発揮される。 As a suitable example of the metallocene complex, 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 complexes represented by
A polymer can be produced by using the metallocene complex. In addition, by using the above metallocene complex, for example, a complex previously combined with an aluminum catalyst, it is possible to reduce or eliminate the amount of alkylaluminum used at the time of polymer synthesis. If a conventional catalyst system is used, it is necessary to use a large amount of alkylaluminum at the time of polymer synthesis. For example, in a conventional catalyst system, it is necessary to use 10 equivalents or more of alkylaluminum with respect to the metal catalyst. If the metallocene complex is used, excellent catalytic action is exhibited by adding about 5 equivalents of alkylaluminum. Is done.

  In the metallocene complex, 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. Preferred 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 can be represented by C ₉ H _7X R _X or C ₉ H _11X 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 ^B is 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、Ｍ²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、上記メタロセン錯体の構造は、¹Ｈ−ＮＭＲやＸ線構造解析により決定することが好ましい。 The metallocene complex is represented by, for example, the following formula (XVI) in a solvent:

(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 represents a group having 1 to 3 carbon atoms. an alkyl group or a hydrogen atom, L is a neutral Lewis base, w is, the metallocene complex represented by an integer of 0 to 3), an organoaluminum compound 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. The structure of the metallocene complex 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. Moreover, 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 catalyst can be easily synthesized. 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 for the production of the metallocene complex is represented by AlR ^K R ^L R ^M , where R ^K and R ^L are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. Alternatively, 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 R ^K or R ^L described above. 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. The amount of the organoaluminum compound used for the formation of the metallocene complex is preferably 1 to 50 times mol, and more preferably about 10 times mol to the metallocene complex.

  The third polymerization catalyst composition includes the metallocene complex and a boron anion, and further contains other components such as a cocatalyst contained in the polymerization catalyst composition containing a normal metallocene complex. It is preferable to include. The metallocene complex and boron anion are also referred to as a two-component catalyst. According to the third polymerization catalyst composition, since the boron anion is further contained in the same manner as the metallocene complex, it is possible to arbitrarily control the content of each monomer component in the polymer. .

  In the third polymerization catalyst composition, specific examples of the boron anion constituting the two-component catalyst include a tetravalent boron anion. For example, tetraphenylborate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethyl) Phenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tridecahydride-7,8-dicarboundecaborate Among these, tetrakis (pentafluorophenyl) borate is preferable.

  In addition, the said boron anion can be used as an ionic compound combined with the cation. Examples of the cation 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 a triphenylcarbonium cation and a tri (substituted phenyl) carbonium cation. The tri (substituted phenyl) carbonyl cation is specifically exemplified by tri (methylphenyl). ) Carbonium cation and the like. Examples of amine cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N- N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation; dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation. Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation. Among these cations, N, N-dialkylanilinium cation or carbonium cation is preferable, and N, N-dialkylanilinium cation is particularly preferable. Therefore, as the ionic compound, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like are preferable. In addition, it is preferable to add 0.1-10 times mol with respect to the said metallocene complex, and, as for the ionic compound which consists of a boron anion and a cation, it is still more preferable to add about 1 times mol.

  In the third polymerization catalyst composition, it is necessary to use the metallocene complex and the boron anion, but in the reaction system for reacting the metallocene complex represented by the formula (XVI) and the organoaluminum compound, If a boron anion is present, the metallocene complex of the above formula (XV) cannot be synthesized. Therefore, for the preparation of the third polymerization catalyst composition, it is necessary to synthesize the metallocene complex in advance, isolate and purify the metallocene complex, and then combine with the boron anion.

Examples of the third polymerization catalyst co-catalyst which can be used in the compositions, for example, other organic aluminum compound represented by AlR ^K R ^L R ^M described above, aluminoxane can be preferably used. The aluminoxane is preferably an alkylaminoxan, and examples thereof include methylaluminoxane (MAO) and modified methylaluminoxane. As the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem Co., Ltd.) and the like are preferable. These aluminoxanes may be used alone or in combination of two or more.

  The second polymerization catalyst composition further contains a conjugated diene monomer and / or a non-conjugated olefin compound. As the conjugated diene monomer and / or non-conjugated olefin to be added here, a different type of monomer from the monomer constituting the main chain of the polymer which is the target of the polymerization reaction is used. The monomer previously blended as a polymerization catalyst composition (hereinafter also referred to as “blended monomer”) is not particularly limited as long as it is a conjugated diene monomer or a non-conjugated olefin. In the case of a monomer, the number of carbon atoms is preferably 4-8. Specific examples include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and among these, 1,3-butadiene and isoprene are preferable. In addition, these conjugated diene compounds may be used independently and may be used in combination of 2 or more type. In the case of a non-conjugated olefin, an acyclic olefin having 2 to 10 carbon atoms can be suitably used. Specific examples include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and styrene. Among these, ethylene, propylene, and 1-pentene are preferable. Butene and styrene are preferred. These non-conjugated olefins may be used alone or in combination of two or more.

  The blended monomer may or may not be polymerized in the catalyst composition. Moreover, when making it superpose | polymerize, although the product may be an oligomer or a polymer, it is preferable that the polymerization number of a mixing | blending monomer is 1-10. Moreover, it is preferable that the molecular weight per block which a compounding monomer comprises is 1000 or less. It is possible to adjust the polymerization degree of the compounded monomer by the amount of the compounded monomer added to the catalyst composition, the aging temperature, and the time.

  The total blending amount of the blended monomer in the polymerization catalyst composition is 0.1 to 10,000 mol equivalent, particularly 1 to 5000 mol equivalent, and further 10 to 3500 mol equivalent of the total blending amount of the rare earth element-containing compound. Is preferred. The compounding monomer may be polymerized or not polymerized depending on the desired function to be added to the target polymer. However, when the compounding amount of the compounding monomer exceeds 10,000 mol equivalent of the total compounding amount of the rare earth element-containing compound, the compounding monomer can be polymerized to form a relatively long chain polymer. If the polymer of the long chain compounding monomer is added to the main chain formed by polymerization later, the characteristics of the main chain may be impaired. On the other hand, if it is less than 0.1 mol equivalent of the total compounding amount of the rare earth element-containing compound, there is a possibility that the function is hardly added to the main chain.

-Method for producing polymer-
Next, a method for producing a polymer using the second polymerization catalyst composition, the second catalyst composition, and the third catalyst composition will be described.

-Polymerization process-
The polymerization step referred to here refers to a polymerization step of a monomer constituting the main chain (hereinafter also referred to as “main chain monomer”), and is a single unit previously blended in the polymerization catalyst composition. It does not indicate a polymerization step into oligomers or polymers that can be produced during aging of the composition. A conjugated diene monomer is used as the main chain monomer. The main chain monomer is not particularly limited as long as it is of a different type from the monomer previously blended in the polymerization catalyst composition. Preferably, those having 4 to 8 carbon atoms are used. Specific examples include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and among these, 1,3-butadiene and isoprene are preferable. In addition, these conjugated diene compounds may be used independently and may be used in combination of 2 or more type.
In the main chain monomer-derived polymer portion, the cis 1,4-bond amount is preferably 80% or more, more preferably 90% or more, and 95% or more. Further preferred.

  In the polymerization step, the amount of the main chain monomer added to the reaction vessel in the presence of the polymerization catalyst composition is 9 times mol or more, particularly 10 to 1000 times mol, more preferably 20 to 500 times mol of the compounded monomer. It is preferable that Thereby, other characteristics can be imparted without impairing the characteristics of the original main chain.

  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 following description of each step, for convenience, the monomer pre-mixed in the polymerization catalyst composition is exemplified as styrene, and the monomer constituting the main chain of the target polymer is exemplified as isoprene. The monomers applicable to the present invention are not limited to these.

  In the polymerization step, an isoprene monomer is added to polymerize the isoprene monomer in the presence of the first, second, or third polymerization catalyst composition. The polymerization reaction 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 ° C. 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. The pressure of the polymerization reaction is preferably in the range of 0.1 to 10.0 MPa in order to sufficiently incorporate isoprene into the polymerization reaction system. 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.

  Prior to the above-described polymerization reaction of isoprene, in the polymerization catalyst composition, a certain amount or more of styrene blended in advance is in a state of being imparted to the active center of the catalyst in a monomer, oligomer or polymer state. In the polymerization step, a large amount of isoprene is added thereto, whereby styrene in a monomer, oligomer or polymer state is added to isoprene, and then a polymerization reaction between the isoprene occurs. As a result, a polymer having styrene added thereto with the isoprene polymer as the main chain is produced.

  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 of polymerization catalyst composition)
In a glove box under a nitrogen atmosphere, trisbistrimethylsilylamidogadolinium [Gd [N (SiMe3) 2] 3] 64 mg (100 μmol), bis (2-diphenylphosphinophenyl) amine 54 mg (100 μmol) in a 200 mL pressure glass reactor , Triisobutylaluminum 1.0 mmol (manufactured by Tosoh Finechem Co., Ltd.), triphenylcarbonium tetrakis (pentafluorophenyl) borate [Ph ₃ CB (C ₆ F ₅ ) ₄ ] 93 mg (100 μmol) (manufactured by Tosoh Finechem Co., Ltd.), toluene 20 mL was charged and aged at room temperature for 120 minutes. Thereafter, the reactor was taken out from the glove box, 1.1 g (10.0 mmol) of styrene was added, and the reaction was performed at 40 ° C. for 300 minutes. Thereafter, 1 ml of methanol was added to stop the reaction, followed by filtration. The filtration residue was vacuum-dried at 70 ° C. to obtain a product A. The yield of A obtained was 0.13 g. The number average molecular weight (Mn) measured by the method described later was 1,000, and the molecular weight distribution (Mw / Mn) was 1.5.
Since the product is considered to be a polymer of styrene, its yield is low, so that styrene moves in the state of monomer or low molecular weight oligomer or polymer to the filtrate side, that is, the catalyst composition side. I found out. This confirmed that styrene was imparted to the catalyst composition.

(Example 2: Production method of polymer B)
After carrying out the polymerization reaction in the same manner as in Example 1, the reactor was returned to room temperature, and then 20.0 g of isoprene was added, followed by reaction for 15 minutes. Thereafter, 1 ml of methanol was added to stop the reaction, followed by vacuum drying at 70 ° C. to obtain a product (polymer) B. The yield of B obtained was 18.5 g, the number average fraction medical (M) was 135,000, and the molecular weight distribution (Mw / Mn) was 4.0.
The obtained polymer B is considered to be polyisoprene, and since its yield is high, it was shown that the composition produced in the same manner as in Example 1 functions as a polymerization catalyst. .

(Example 3: Production method of polymer C)
Trisbistrimethylsilylamidogadolinium [Gd [N (SiMe3) 2] 3] 6.3 mg (9.4 μmol), bis (2-diphenylphosphinophenyl) amine 5.4 mg in a 1 L pressure glass reactor in a glove box under nitrogen atmosphere (9.4 μmol) and 1.0 g of toluene were aged for 30 minutes, and then 1.41 mmol of triisobutylaluminum and 5.0 g of toluene were added, followed by further aging for 30 minutes, and then triphenylcarbonium tetrakis (pentafluorophenyl) borate. 9.4 μmol of (Ph3CB (C6F5) 4) was added and aged for 15 minutes. Thereafter, the reactor was removed from the glove box, 3.4 g of styrene was added, and the mixture was stirred at 50 ° C. for 30 minutes. Thereafter, 161.4 g of cyclohexane and 65 g of isoprene were added, and polymerization was carried out at 50 ° C. for 2 hours. After the polymerization, 1 ml of 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) (NS-5) 5% by mass isopropanol solution was added to stop the reaction, and the polymer was separated with a large amount of methanol. The polymer C was obtained by vacuum drying at 70 ° C. The yield of the obtained polymer C was 62 g.
Thereby, it was shown that the production | generation of the polymerization catalyst composition of Example 1 and the polymerization reaction of a monomer can be continuously implemented by one pot.

(Comparative Example 1: Production method of polymer D)
Trisbistrimethylsilylamidogadolinium [Gd [N (SiMe3) 2] 3] 5.0 mg (7.4 μmol), bis (2-diphenylphosphinophenyl) amine 4.2 mg in a 1 L pressure glass reactor in a glove box under nitrogen atmosphere (7.4 μmol) and 1.0 g of toluene were aged for 30 minutes, and then 1.84 mmol of triisobutylaluminum and 5.0 g of toluene were added, followed by further aging for 30 minutes, and then triphenylcarbonium tetrakis (pentafluorophenyl) borate. 7.4 μmol of (Ph3CB (C6F5) 4) was added and aged for 15 minutes. Thereafter, the reactor was removed from the glove box, 164.7 g of cyclohexane and 65 g of isoprene were added, and polymerization was carried out at 50 ° C. for 2 hours. After the polymerization, 1 ml of 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) (NS-5) 5% by mass isopropanol solution was added to stop the reaction, and the polymer was separated with a large amount of methanol. The polymer D was obtained by vacuum drying at 70 ° C. The yield of the obtained polymer D was 65 g.

  The number average molecular weight (Mn) and molecular weight distribution of the obtained product A and polymers B to D and commercially available isoprene rubber (IR2200, manufactured by JSR) were measured by the following methods. Moreover, about the polymers C and D and the commercially available isoprene rubber, the microstructure, the glass transition temperature (Tg), and (Tb) were analyzed by the method shown below. The analysis results of the polymers C and D and isoprene rubber are shown in Table 1.

(1) Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)
It was measured by gel permeation chromatography [GPC: manufactured by Tosoh Corporation, HLC-8020] using a refractometer as a detector, and was shown in terms of polystyrene using monodisperse polystyrene as a standard. The column is GMHXL [manufactured by Tosoh], the eluent is tetrahydrofuran, and the measurement temperature is 40 ° C.

(2) Microstructure (cis-1,4 bond amount)
Peaks obtained by ¹ H-NMR and ¹³ C-NMR [ ¹ H-NMR: δ 4.6-4.8 (3,4-vinyl unit = CH ₂ ), 5.0-5.2 (1, 4-unit -CH =), 13C-NMR: [δ 23.4 (1,4-cis unit), 15.9 (1,4-trans unit), 18.6 (3,4-unit)] Each was calculated from the integration ratio. The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were determined by polystyrene using polystyrene as a standard substance.

(3) Glass transition temperature (Tg)
After weighing 10 mg + 0.5 mg of sample, putting it in an aluminum measuring pan and covering it with a DSC device (TA Instruments) from room temperature to 50 ° C., and stabilizing for 10 minutes The glass transition point (Tg) was measured while cooling to −80 ° C. and stabilizing at −80 ° C. for 10 minutes, while increasing the temperature to 50 ° C. at a temperature increase rate of 10 ° C./min.

(4) Tensile strength (Tb (100 ° C)
The above polymers C, D and isoprene rubber were subjected to a tensile test at 100 ° C. in accordance with JIS K 6301-1995, and the tensile strength (Tb) of each polymer was measured. The side hand results are shown in Table 1.

  From the result of Table 1, since Tg of Example 3 is rising compared with the polymer D (polyisoprene) of the comparative example 1, styrene is added to the polymer C of Example 3. Was suggested. The polymer C had a high 1,4-cis bond amount similar to the polymer D, and showed very good results in the tensile strength test as compared with the polymer D and commercially available isoprene rubber.

  The polymerization catalyst composition of the present invention and the method for producing a polymer using the polymerization catalyst composition are suitable in all fields requiring functional rubber such as production of tire members (particularly, tire tread members). Is available.

Claims (12)

A rare earth element-containing compound containing at least one of a rare earth element compound and a reaction product of a rare earth element compound and a Lewis base;
At least one anion source selected from the group consisting of an ionic compound comprising a non-coordinating anion and a cation, an aluminoxane and a halogen compound;
A polymerization catalyst composition comprising: at least one monomer selected from the group consisting of a conjugated diene monomer and a non-conjugated olefin. Furthermore, 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 each a hydrocarbon group having 1 to 10 carbon atoms or hydrogen. An atom, R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ¹ , R ² and R ³ may be the same or different from each other, and Y is from Group 1 of the Periodic Table; When it is a selected metal, a is 1 and b and c are 0. 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 polymerization catalyst composition as described. The rare earth element-containing compound has the following general formula (V) or (VI):
M ¹¹ X ¹¹ ₂・ L ¹¹ w (V)
M ¹¹ X ¹¹ ₃ · L ¹¹ w (VI)
(In the formula, M ¹¹ represents a lanthanoid element, scandium or yttrium, and X ¹¹ 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. Group, carboxylic acid residue, thiocarboxylic acid residue, phosphorus compound residue, unsubstituted or substituted cyclopentadienyl, or unsubstituted or substituted indenyl, L ¹¹ represents a Lewis base, and w is 0 The polymerization catalyst composition of Claim 2 represented by -3. The rare earth element-containing compound has 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), and the following general formula (III ):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^{R ′} represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxide group or 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, w represents an integer of 0 to 3, and [B] ⁻ represents a non-coordinating group. The polymerization catalyst composition according to claim 2, comprising at least one complex selected from the group consisting of half metallocene cation complexes represented by   The polymerization catalyst composition according to claim 3, wherein the rare earth element-containing compound is a compound having no bond between a rare earth element and carbon. The rare earth element-containing compound 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 2. The polymerization catalyst composition according to claim 1, which is a metallocene complex represented by a hydrogen atom, wherein Y is coordinated to Q, and a and b are 2. The rare earth element-containing compound has 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. The polymerization catalyst composition of Claim 6 which is a metallocene complex represented by this. The compound represented by the general formula (X) is represented by the following general formula (Xa):
AlR ¹ R ² R ³ (Xa)
(In the formula, R ¹ and R ² are each 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 ¹ , R ² and R ³ The polymerization catalyst composition according to claim 2, wherein each may be the same or different from each other.   The ionic compound comprising the non-coordinating anion and cation is at least selected from the group consisting of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and triphenylcarbonium tetrakis (pentafluorophenyl) borate. The polymerization catalyst composition according to claim 1, comprising one.   The polymerization catalyst composition according to claim 1, wherein the conjugated diene monomer has 4 to 8 carbon atoms.   The polymerization catalyst composition according to claim 1, wherein the non-conjugated olefin is an acyclic olefin having 2 to 10 carbon atoms. A rare earth element-containing compound containing at least one of a rare earth element compound and a reaction product of a rare earth element compound and a Lewis base;
At least one anion source selected from the group consisting of an ionic compound comprising a non-coordinating anion and a cation, an aluminoxane and a halogen compound;
Mixing and aging at least one monomer selected from the group consisting of a conjugated diene monomer and a non-conjugated olefin,
Then, a conjugated diene monomer different from the monomer is added, and the added conjugated diene monomer is subjected to a polymerization reaction.