JP2014024885A - Method of manufacturing polymer composition and polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing polymer composition having excellent exothermic tendency and abrasion resistance.SOLUTION: A method of manufacturing polymer composition includes a step of forming a polymer component by polymerizing at least one kind of a conjugated diene compound and a non-conjugated olefin in the presence of the polymerization catalyst composition obtained by adding and reacting the first element which is a rare earth element-containing compound and includes a rare earth element compound or a reactant of the rare earth element compound and a Lewis base after aging and mixing the second element which includes a compound represented by the following formula (X) and the third element which contains silica, and the compounded amount of the silica is 6 pts.wt. or more based on the total amount of 100 pts.wt. of the added conjugated diene compound and/or non-conjugated olefin: YRRR(X), where Y is a metal selected from group I, group II, group XII and group XIII in a periodic table, Rand Rare a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, Ris a hydrocarbon group having 1 to 10 carbon atoms, R, Rand Rmay be same or different, and a is 1 and b and c are 0 when Y is the metal selected from group I, a and b are 1 and c is 0 when Y is the metal selected from group II and group XII, and a, b and c are 1 when y is the metal selected from group XIII.

Description

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

In recent years, there has been an increasing demand for fuel efficiency reduction of automobiles in connection with the global movement of regulation of carbon dioxide emissions due to increasing interest in environmental problems. In order to meet such demands, tires are required to reduce rolling resistance. As a technique for reducing the rolling resistance of the tire, a technique of applying a low heat-generating rubber composition to the tire can be mentioned.
As a conventionally known method, there is a method using a polymer having enhanced affinity with carbon black and silica (for example, Patent Document 1). According to Patent Document 1, the exothermic property of the rubber composition can be lowered by increasing the affinity between the filler and the rubber component. Thereby, a tire with low hysteresis loss can be obtained. However, as the fuel efficiency of automobiles has further improved, further improvements in low heat generation have been desired for tires. In addition, other methods are known in which the kneading time is increased, but there is a limit to the reduction in heat generation.
On the other hand, wear resistance is also required as a required characteristic of a tire along with low heat build-up, and establishment of a rubber composition that satisfies both of these has been required.

JP 2003-514079 A

  An object of the present invention is to provide a method for producing a polymer composition capable of obtaining a polymer composition having excellent low heat build-up and wear resistance. Another object of the present invention is to provide a polymer composition having excellent low heat buildup and wear resistance.

The method for producing a polymer composition of the present invention is a rare earth element-containing compound, and is represented by a first element including a rare earth element compound or a reaction product of a rare earth element compound and a Lewis base, and the following general formula (X): About the 2nd element containing a compound, and the 3rd element containing silica, after mixing and aging the 2nd element and the 3rd element, adding the 1st element and making it react, the polymerization catalyst composition obtained The total amount of the conjugated diene compound and / or the non-conjugated olefin to which the compounding amount of the silica is added includes the step of polymerizing at least one of the conjugated diene compound and the non-conjugated olefin in the presence of It is characterized by being 6 parts by weight or more with respect to parts by weight.
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 A hydrogen 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, 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)
By synthesizing a polymer using the above catalyst composition, silica can be dispersed in the polymer at a molecular level as compared with the conventional method, and silica is highly dispersed in the polymer. An excellent polymer can be obtained. Also, the abrasion resistance of the polymer composition can be improved by using the silica-containing polymer produced by the production method of the present invention as compared to the method of producing a polymer / silica composite by kneading. Became clear.
In this invention, the quantity of the silica mix | blended in the said polymerization catalyst composition shall be 6 weight part or more with respect to 100 weight part of total amounts of the conjugated diene compound and / or nonconjugated olefin to add. As a result, a crosslinked polymer composition having further improved heat build-up and wear resistance can be obtained.

  The moisture content of the third element is preferably 0.1% by weight or more. It has the effect that the polymerization reaction is further accelerated by the contained moisture.

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

In the method for producing a polymer composition of the present invention, the compound represented by the general formula (X) is preferably the following general formula (Xa):
AlR ¹ R ² R ³ (Xa)
(In the formula, ^{R 1} and ^{R 2} are a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms, ^{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.

  The polymer composition of this invention is manufactured by the manufacturing method of one of said polymer compositions. As described above, in the polymer composition of the present invention, silica is highly dispersed in the polymer, and thereby, excellent low heat buildup and wear resistance can be achieved.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the polymer composition which can obtain the polymer composition which has the outstanding low heat generation property and abrasion resistance can be provided. Moreover, according to the present invention, a polymer composition having excellent low heat build-up and wear resistance can be provided.

Hereinafter, the method for producing the polymer composition of the present invention will be described by way of example based on the embodiment.
(Silica-containing polymer)
The silica-containing polymer constituting the polymer composition according to the method for producing a polymer composition of the present invention is a polymer of a conjugated diene compound alone or a polymer of a conjugated diene compound and a non-conjugated olefin. That is, it is a conjugated diene polymer or a copolymer of a conjugated diene compound and a non-conjugated olefin, and these are collectively referred to as a conjugated diene polymer.

  The conjugated diene compound used as the monomer preferably has 4 to 8 carbon atoms. Specific examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and among these, 1,3-butadiene and isoprene are preferable. Moreover, these conjugated diene compounds may be used independently and may be used in combination of 2 or more type.

  On the other hand, the non-conjugated olefin used as the monomer is an olefin other than the conjugated diene compound, and is preferably an acyclic olefin. Moreover, it is preferable that carbon number of this nonconjugated olefin is 2-8. Accordingly, preferred examples of the non-conjugated olefin include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and ethylene, propylene and 1-butene. Is more preferable, and ethylene is particularly preferable. These non-conjugated olefins may be used alone or in combination of two or more. In addition, an olefin refers to the compound which is an aliphatic unsaturated hydrocarbon and has one or more carbon-carbon double bonds.

  When the polymer is a copolymer, the copolymer may be any of alternating copolymer, periodic copolymer, random copolymer, block copolymer, graft copolymer, taper copolymer, etc. Although not particularly limited, block copolymers and taper copolymers are preferred.

The number average molecular weight (Mn) of the polymer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 100,000 to 400,000, more preferably 150,000 to 300,000. When the number average molecular weight (Mn) is 150,000 or more, it is possible to obtain a polymer composition with improved durability (breakage resistance and wear resistance). Moreover, it can prevent that workability falls that the said number average molecular weight (Mn) is 300,000 or less. On the other hand, when the number average molecular weight (Mn) is within the more preferable range, it is further advantageous in terms of both durability and workability.
Here, the number average molecular weight (Mn) is determined as a polystyrene-converted average molecular weight using polystyrene as a standard substance by gel permeation chromatography (GPC) at a measurement temperature of 140 ° C.

  The molecular weight distribution (Mw / Mn) represented by the ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer is not particularly limited and may be appropriately selected according to the purpose. 4.0 or less is preferable and 3.0 or less is more preferable. When the molecular weight distribution (Mw / Mn) is 4.0 or less, physical properties can be made uniform. On the other hand, if it is within the more preferable range, it is advantageous also in terms of low heat generation. Here, the molecular weight distribution (Mw / Mn) is a weight average molecular weight (Mw) and a number average molecular weight as a polystyrene-converted average molecular weight using polystyrene as a standard substance by gel permeation chromatography (GPC) at a measurement temperature of 140 ° C. (Mn) is calculated and calculated from the calculated weight average molecular weight (Mw) and number average molecular weight (Mn).

There is no restriction | limiting in particular as a gel fraction in the said polymer, Although it can select suitably according to the objective, 40% or less is preferable and 20% or less is more preferable.
When the gel fraction in the polymer is 40% or less, a polymer composition having improved durability (breakage resistance and wear resistance) can be obtained.
In addition, the polymer whose gel fraction in a polymer is 40% or less is low temperature (-50-100 degreeC) using the 1st, 2nd, or 3rd polymerization catalyst composition mentioned later, for example. , By polymerization for a predetermined time (30 minutes to 2 days).

<Microstructure of the conjugated diene compound-derived portion>
-Cis-1,4 binding amount-
The cis-1,4 bond amount of the conjugated diene compound-derived portion of the polymer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 90% or more, more preferably 95% or more, 98% or more is particularly preferable.
When the amount of cis-1,4 bonds is 90% or more, sufficient elongation crystallinity can be expressed.
On the other hand, when the amount of cis-1,4 bonds is within the more preferable range or the particularly preferable range, it is more advantageous in terms of improvement in durability due to stretched crystallinity.

-Trans-1,4 binding amount-
There is no restriction | limiting in particular as trans-1,4 bond amount of the conjugated diene compound origin part of the said polymer, Although it can select suitably according to the objective, 10% or less is preferable and 5% or less is more preferable.
When the amount of the trans-1,4 bond is 10% or less, sufficient elongation crystallinity can be expressed.
On the other hand, when the amount of the trans-1,4 bond is within the more preferable range, it is further advantageous in terms of improvement in durability due to stretched crystallinity.

−3,4-vinyl bond amount−
There is no restriction | limiting in particular as the 3, 4- vinyl bond amount of the conjugated diene compound origin part of the said polymer, Although it can select suitably according to the objective, 5% or less is preferable and 2% or less is more preferable.
When the 3,4-vinyl bond amount is 5% or less, sufficient elongation crystallinity can be expressed.
On the other hand, when the amount of 3,4-vinyl bond is within the more preferable range, it is further advantageous in terms of improvement in durability due to stretched crystallinity.

(Method for producing conjugated diene polymer)
Next, a production method capable of producing the conjugated diene polymer will be described in detail. However, the manufacturing method described in detail below is merely an example. The conjugated diene polymer can be produced by polymerizing a conjugated diene compound and / or a non-conjugated olefin in the presence of a polymerization catalyst composition.

<Polymerization catalyst composition>
The polymerization catalyst composition used in the above method for producing a conjugated diene polymer can be obtained by combining the following first element, second element and third element.

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

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

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

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

（式中、Ｍは、ランタノイド元素、スカンジウムまた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のアルキル基または水素原子を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体、及び下記一般式（ＩＩ）： <<< preferred rare earth element-containing compound >>>
As the rare earth element-containing compound, the following general formula (I):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents unsubstituted or substituted indenyl, and R ^{a to} R ^f each independently represents an alkyl having 1 to 3 carbon atoms. 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、スカンジウムまた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、シリル基または炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体より選択される少なくとも１種類の錯体を含むことが好ましい。

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

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

In the metallocene complexes represented by the above general formulas (I) and (II), Cp ^R in the formula is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7-X R _X or C ₉ H _11-X R _X. Here, X is an integer of 0-7 or 0-11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of the substituted indenyl include 2-phenylindenyl and 2-methylindenyl. Note that the two Cp ^Rs in the general formulas (I) and (II) may be the same as or different from each other.

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

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

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

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

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

（式中、Ｘ''はハライドを示す。）
上記一般式（ＩＩ）で表されるメタロセン錯体は、例えば、溶媒中でランタノイドトリスハライド、スカンジウムトリスハライドまた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, scandium trishalide or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt), and a silyl salt (for example, potassium). Salt or lithium salt). In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used. Below, the reaction example for obtaining the metallocene complex represented by general formula (II) is shown.

（式中、Ｘ''はハライドを示す。）

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

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

<<< other suitable rare earth element-containing compound >>>
The rare earth element-containing compound has 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 in 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) (third rare earth element-containing compound).

（式中、Ｍ^１は、ランタノイド元素、スカンジウムまたはイットリウムを示し、Ｃｐ^Ｒは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^Ａ及びＲ^Ｂは、それぞれ独立して炭素数１〜２０の炭化水素基を示し、該Ｒ^Ａ及びＲ^Ｂは、Ｍ^１及びＡｌにμ配位しており、Ｒ^Ｃ及びＲ^Ｄは、それぞれ独立して炭素数１〜２０の炭化水素基または水素原子を示す）で表されるメタロセン系化合物が挙げられる。 In a preferred example of the metallocene compound, the following general 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 represents a group having 1 to 20 carbon atoms. R ^A and R ^B are μ-coordinated to M ¹ and Al, and R ^C and R ^D each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Metallocene compounds represented by

  Hereinafter, the metallocene compound will be described in detail. The metallocene compound represented by the general formula (A) reduces or eliminates the amount of alkylaluminum used at the time of copolymer synthesis, for example, by using a catalyst that is previously combined with an aluminum catalyst. It becomes possible. If a conventional catalyst system is used, it is necessary to use a large amount of alkylaluminum at the time of copolymer synthesis. For example, in the conventional catalyst system, it is necessary to use 10 equivalents or more of alkylaluminum with respect to the metal catalyst. If the metallocene composite catalyst is used, an excellent catalytic action can be obtained by adding about 5 equivalents of alkylaluminum. Is demonstrated.

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

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

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

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

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

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

In the above formula (XV), Cp ^R is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton 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. Incidentally, the two Cp ^R in the formula (XV) may each be the same or different from each other.

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

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

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

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

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

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

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

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

On the other hand, the organoaluminum compound used to produce the metallocene compound is represented by AlR ^K R ^L R ^M , where R ^K and R ^L are each independently a monovalent hydrocarbon having 1 to 20 carbon atoms. A group or a hydrogen atom, R ^M is a monovalent hydrocarbon group having 1 to 20 carbon atoms, provided that R ^M may be the same as or different from 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 production of the metallocene compound is preferably 1 to 50 times mol, more preferably about 10 times mol to the metallocene complex.

<< Second Element >>
The second element constituting the polymerization catalyst composition is 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 A hydrogen 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, 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).

In addition, the second element has the following general formula (Xa):
AlR ¹ R ² R ³ (Xa)
(In the formula, ^{R 1} and ^{R 2} are a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms, ^{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 organic aluminum compound represented by the general formula (Xa) 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 Um dihydride, include isobutyl aluminum dihydride and the like, among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. The organoaluminum compound as the second element described above can be used singly or in combination of two or more. In addition, it is preferable that the compounding quantity of the 2nd element in a polymerization catalyst composition is 1-50 times mol with respect to the said 1st element, and it is still more preferable that it is about 10 times mol.

<< Third element >>
The third element constituting the polymerization catalyst composition according to the present invention includes silica, and the term “silica” specifically indicates only silicon dioxide in a narrow sense (indicated by SiO ₂ in the general formula). It means a silicic acid-based filler, and specifically includes silicates such as hydrous silicic acid, calcium silicate, and aluminum silicate in addition to anhydrous silicic acid. In addition, precipitation method silica, gel method silica, dry silica, colloidal silica and the like are included regardless of the aggregation state of silica. Moreover, the silica manufactured by any manufacturing method is included, and both a wet method and a dry method are included. Of these, wet silica having excellent wear resistance is preferred. The BET of silica is not particularly limited, and includes, for example, silica in the range of 10 to 1000 m ² / g. Examples of such silica include “Nip Seal AQ” manufactured by Tosoh Silica Co., Ltd. and BET 205 m ² / g.
In addition, although the silica used as a catalyst composition in a nonpatent literature 3 is baked and dehydrated, in the present invention, it is not necessary to burn the silica.
The blending amount of silica in the polymerization catalyst composition is 6 parts by weight or more with respect to 100 parts by weight of the conjugated diene compound and / or non-conjugated olefin to be added later, and is preferably 8 to 80 parts by weight. -50 parts by weight is preferable. By making the blending amount of the third element within the above range, it can function effectively as a catalyst, and silica can be efficiently dispersed in the polymer, thereby further reducing the heat buildup and wear resistance. It is possible to form an excellent polymer composition.

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

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

  In addition, although there exists a problem that a 1st element is easy to deactivate by presence of water, even if it coexists with the said anion complex, a 1st element is hard to deactivate. Therefore, the silica contained in the third element does not need to be anhydrous by calcination or the like. Since the steps such as firing can be omitted, the manufacturing cost can be reduced and the manufacturing process can be made more efficient. Rather, in order to accelerate the polymerization reaction, the third element preferably contains a certain amount or more of moisture, and a suitable moisture content is 0.1% by weight, and a particularly preferred moisture content is 0.1 to 20% by weight, more preferably the water content is 0.5 to 10% by weight.

(Manufacturing process of conjugated diene polymer)
In describing the production process of the conjugated diene polymer, the production process of polybutadiene will be exemplified below. The production of polybutadiene using the polymerization catalyst composition includes at least a polymerization step, and further includes a coupling step, a washing step, and other steps that are appropriately selected as necessary.

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

  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.

  The said polymerization process is comprised by adding the monomer made to superpose | polymerize in the polymerization catalyst composition prepared previously.

  In the polymerization step, the polymerization may be stopped using a polymerization terminator such as methanol, ethanol, isopropanol or the like.

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

<Washing process>
The washing step is a step of washing the silica-containing polymer obtained in the polymerization step. In addition, there is no restriction | limiting in particular as a medium used for washing | cleaning, According to the objective, it can select suitably, For example, methanol, ethanol, isopropanol etc. are mentioned. Further, an acid (for example, hydrochloric acid, sulfuric acid, nitric acid) may be added to these solvents. The amount of the acid to be added is preferably 15 mol% or less with respect to the solvent. Above this, the acid remains in the silica-containing polymer, which may adversely affect the reaction during kneading and vulcanization.

(Polymer composition)
The polymer composition of the present invention includes at least the above-described polymer component, and further includes other polymer components, a filler, a crosslinking agent, and other components as necessary.

<Polymer>
The polymer contains at least one of the above-described conjugated diene polymers containing silica, and further contains other polymers as necessary. There is no restriction | limiting in particular as another polymer, According to the objective, it can select suitably, For example, butadiene (BR), styrene butadiene (SBR), acrylonitrile-butadiene (NBR), chloroprene rubber, ethylene-propylene rubber Examples thereof include rubber components such as (EPM), ethylene-propylene-nonconjugated diene rubber (EPDM), polysulfide rubber, silicone rubber, fluorine rubber, and urethane rubber. These may be used individually by 1 type and may use 2 or more types together.

<Filler>
The filler is not particularly limited except for silica contained in the polymerization catalyst composition, and can be appropriately selected according to the purpose. Examples thereof include carbon black and inorganic filler. At least one selected from black and inorganic fillers is preferred. Here, it is more preferable that the polymer composition contains carbon black. In addition, the said filler is mix | blended with a polymer composition in order to improve reinforcement property etc.

There is no restriction | limiting in particular as a compounding quantity (content) of the filler added after a polymerization reaction, Although it can select suitably according to the objective, 10 mass parts-100 mass parts are with respect to 100 mass parts of polymers. Preferably, 20 parts by weight to 80 parts by weight is more preferable, and 30 parts by weight to 60 parts by weight is particularly preferable.
When the blending amount of the filler is 10 parts by mass or more, an effect of adding the filler is seen, and when it is 100 parts by mass or less, the polymer can be sufficiently mixed with the filler. The performance as a thing can be improved.
On the other hand, when the blending amount of the filler is within the more preferable range or the particularly preferable range, it is more advantageous in terms of the balance between processability and low loss / durability.

<< carbon black >>
There is no restriction | limiting in particular as said carbon black, According to the objective, it can select suitably, For example, FEF, GPF, SRF, HAF, N339, IISAF, ISAF, SAF etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Nitrogen adsorption specific surface area of the carbon black: The _(N 2 SA, JIS K 6217-2 is measured according to 2001) is not particularly limited and may be appropriately selected depending on the intended purpose, ^{20 m} 2 / 150 m ² / g are ^preferred, 35m ² / ^g~145m 2 / g is more preferable.
When the nitrogen adsorption specific surface area (N ₂ SA) of the carbon black is 20 m ² / g or more, deterioration of the durability of the obtained polymer composition is prevented and sufficient crack growth resistance is obtained. If it is 100 m ² / g or less, the low-loss property can be improved, and the workability can be improved.
There is no restriction | limiting in particular as content of carbon black with respect to 100 mass parts of said polymers, Although it can select suitably according to the objective, 10 mass parts-100 mass parts are preferable, and 10 mass parts-70 mass parts are. More preferred is 20 to 60 parts by mass.
When the content of the carbon black is 10 parts by mass or more, it is possible to prevent deterioration of the fracture resistance due to insufficient reinforcement, and when it is 100 parts by mass or less, workability and low loss property Can be prevented from deteriorating.
On the other hand, when the content of the carbon black is within the more preferable range or the particularly preferable range, it is more advantageous in terms of balance of performances.

<< Inorganic filler >>
The inorganic filler is not particularly limited except for silica contained in the polymerization catalyst composition, and can be appropriately selected according to the purpose. For example, aluminum hydroxide, clay, alumina, talc, mica, kaolin, Examples thereof include glass balloons, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium carbonate, magnesium oxide, titanium oxide, potassium titanate, and barium sulfate. These may be used individually by 1 type and may use 2 or more types together.
In addition, when using said inorganic filler, you may use a silane coupling agent suitably.

<Crosslinking agent>
There is no restriction | limiting in particular as said crosslinking agent, According to the objective, it can select suitably, For example, a sulfur type crosslinking agent, an organic peroxide type crosslinking agent, an inorganic crosslinking agent, a polyamine crosslinking agent, a resin crosslinking agent, sulfur A compound type crosslinking agent, an oxime-nitrosamine type crosslinking agent, etc. are mentioned, Among these, a sulfur type crosslinking agent is more preferable.

  There is no restriction | limiting in particular as content of the said crosslinking agent, Although it can select suitably according to the objective, 0.1 mass part-20 mass parts are preferable with respect to 100 mass parts of polymers. When the content of the crosslinking agent is 0.1 parts by mass or more, crosslinking can proceed, and when the content is 20 parts by mass or less, a part of the crosslinking agent prevents crosslinking from proceeding during kneading. Or the physical properties of the vulcanizate can be prevented from being impaired.

<< Other ingredients >>
In addition, it is also possible to use a vulcanization accelerator in combination, and examples of the vulcanization accelerator include guanidine, aldehyde-amine, aldehyde-ammonia, thiazole, sulfenamide, thiourea, thiuram, Dithiocarbamate and xanthate compounds can be used.
If necessary, softeners, vulcanization aids, colorants, flame retardants, lubricants, foaming agents, plasticizers, processing aids, antioxidants, anti-aging agents, scorch inhibitors, UV inhibitors, antistatic agents Known agents such as a colorant, an anti-coloring agent, and other compounding agents can be used depending on the purpose of use.

(Crosslinked polymer composition)
The polymer composition of the present invention may be cross-linked and used as a cross-linked polymer composition.
The cross-linked polymer composition is not particularly limited as long as it is obtained by cross-linking the polymer composition of the present invention, and can be appropriately selected according to the purpose.
The crosslinking conditions are not particularly limited and may be appropriately selected depending on the intended purpose. However, a temperature of 120 ° C. to 200 ° C. and a heating time of 1 minute to 900 minutes are preferable.

  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: Method for producing silica-containing polymer A)
(Example 1: Method for producing silica-containing polymer A)
In a glove box under a nitrogen atmosphere, 5.0 g of silica (trade name: Nipseal AQ, water content of 5.5% by weight calculated by weight reduction method, manufactured by Tosoh Silica Co., Ltd.) in a 1 L pressure glass reactor, normal hexane 50 0.0 g, 20.0 mmol of trimethylaluminum (manufactured by Tosoh Finechem Co., Ltd.) and 20.0 mmol of triisobutylaluminum (manufactured by Tosoh Finechem Co., Ltd.) were charged and mixed and aged at room temperature for 30 minutes. Next, 68 mg (100 μmol) of bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] was charged and aged at room temperature for 60 minutes. Thereafter, the reactor was taken out from the glove box, and after adding 470.0 g of a normal hexane solution containing 100.0 g (1.85 mol) of 1,3-butadiene, polymerization was carried out at 65 ° C. for 250 minutes. After the polymerization, 1 mL of a 5% by weight isopropanol solution of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) was added to stop the reaction. The coalescence was separated and vacuum dried at 70 ° C. to obtain a silica-containing polymer A. The yield of the resulting silica-containing polymer A was 88.0 g.

(Example 2: Method for producing silica-containing polymer B)
In a glove box under a nitrogen atmosphere, 8.0 g of silica (trade name: Nipseal AQ, water content of 5.5% by weight calculated by the weight reduction method, manufactured by Tosoh Silica Co., Ltd.) in a 1 L pressure glass reactor, normal hexane 80 0.06 g, trimethylaluminum 16.8 mmol (manufactured by Tosoh Finechem Co., Ltd.) and triisobutylaluminum 16.8 mmol (manufactured by Tosoh Finechem Co., Ltd.) were charged and mixed and aged at room temperature for 30 minutes. Next, 22 mg (32 μmol) of bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] was charged and aged at room temperature for 60 minutes. Thereafter, the reactor was taken out of the glove box, and after adding 320.0 g of a normal hexane solution containing 80.0 g (1.48 mol) of 1,3-butadiene, polymerization was performed at 80 ° C. for 240 minutes. After the polymerization, 1 mL of a 5% by weight isopropanol solution of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) was added to stop the reaction. The coalescence was separated and vacuum dried at 70 ° C. to obtain silica-containing polymer B. The yield of the obtained silica-containing polymer B was 83.0 g.

(Example 3: Production method of silica-containing polymer C)
In a glove box under a nitrogen atmosphere, 8.0 g of silica (trade name: Nipseal AQ, water content of 5.5% by weight calculated by the weight reduction method, manufactured by Tosoh Silica Co., Ltd.) in a 1 L pressure glass reactor, normal hexane 80 0.0 g, 19.2 mmol of trimethylaluminum (manufactured by Tosoh Finechem Co., Ltd.) and 19.2 mmol of triisobutylaluminum (manufactured by Tosoh Finechem Co., Ltd.) were charged and mixed and aged at room temperature for 30 minutes. Next, 22 mg (32 μmol) of bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] was charged and aged at room temperature for 60 minutes. Then, after taking out the reactor from the glove box and adding 320.0 g of normal hexane solution containing 80.0 g (1.48 mol) of 1,3-butadiene, polymerization was performed at 80 ° C. for 200 minutes. After the polymerization, 1 mL of a 5% by weight isopropanol solution of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) was added to stop the reaction. The coalescence was separated and vacuum dried at 70 ° C. to obtain a silica-containing polymer C. The yield of the obtained silica-containing polymer C was 68.0 g.

(Example 4: Production method of silica-containing polymer D)
In a glove box in a nitrogen atmosphere, 5.0 g of silica (trade name: Nipseal AQ, water content 5.5% by weight calculated by weight reduction method, manufactured by Tosoh Silica Co., Ltd.) in a 1 L pressure-resistant glass reactor, normal hexane 65 0.0 g, trimethylaluminum 16.0 mmol (manufactured by Tosoh Finechem Co., Ltd.) and triisobutylaluminum 3.2 mmol (manufactured by Tosoh Finechem Co., Ltd.) were charged and mixed and aged at room temperature for 30 minutes. Next, 22 mg (32 μmol) of bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] was charged and aged at room temperature for 60 minutes. Thereafter, the reactor was taken out from the glove box, and 340.0 g of a normal hexane solution containing 80.0 g (1.48 mol) of 1,3-butadiene was added, followed by polymerization at 80 ° C. for 90 minutes. After the polymerization, 1 mL of a 5% by weight isopropanol solution of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) was added to stop the reaction. The coalescence was separated and vacuum dried at 70 ° C. to obtain silica-containing polymer D. The yield of the obtained silica-containing polymer D was 27.0 g.

(Comparative Example 1: Polymer E)
As Comparative Example 1, polybutadiene rubber (UBEPOL BR 150, hereinafter referred to as “150 L butadiene”) manufactured by Ube Industries, Ltd. was used.

(Comparative example 2: Production method of silica-containing polymer F)
In a glove box under nitrogen atmosphere, 3.0 g of silica (trade name: Nipseal AQ, water content of 5.5% by weight calculated by weight reduction method, manufactured by Tosoh Silica Co., Ltd.) in a 1 L pressure-resistant glass reactor, normal hexane 80 0.0 g, trimethylaluminum 9.6 mmol (manufactured by Tosoh Finechem Co., Ltd.) and triisobutylaluminum 3.2 mmol (manufactured by Tosoh Finechem Co., Ltd.) were charged and mixed and aged at room temperature for 30 minutes. Next, 22 mg (32 μmol) of bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] was charged and aged at room temperature for 60 minutes. Then, after taking out the reactor from the glove box and adding 320.0 g of normal hexane solution containing 80.0 g (1.48 mol) of 1,3-butadiene, polymerization was performed at 65 ° C. for 180 minutes. After the polymerization, 1 mL of a 5% by weight isopropanol solution of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) was added to stop the reaction. The coalescence was separated and vacuum dried at 70 ° C. to obtain silica-containing polymer F. The yield of the obtained silica-containing polymer F was 55.0 g.

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

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

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

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

<Physical property test of polymer composition>
For the polymers A to F, a polymer composition having the formulation shown in Table 2 was prepared, and vulcanized polymer composition obtained by vulcanization at 145 ° C. for 33 minutes, according to the following method. (1) Loss tangent (tan δ) and (2) wear resistance were measured. The measurement results are shown in Table 1.

(1) Loss tangent (tan δ)
A test piece was prepared from each vulcanized polymer composition, and tan δ was used under the conditions of an initial load of 160 g, a dynamic strain of 2%, a frequency of 52 Hz, and a temperature of 25 ° C. using a viscoelastic spectrometer manufactured by Toyo Seiki Co., Ltd. Was measured. The smaller the value of tan δ, the better the low exothermic property.

(2) Abrasion resistance (index)
The amount of wear was measured at a slip rate of 60% at room temperature using a Lambourn type wear tester, and displayed as an index with the reciprocal of Comparative Example 1 being 100. The higher the value, the better the wear resistance.

* 1: Polymers A to F
* 2: Tosoh Silica Corporation: Nip Seal AQ
* 3: Product name “A / O Mix” (Process Oil), manufactured by Sankyo Oil Chemical Co., Ltd.
* 4: Product name “Si75” manufactured by Degussa
* 5: N- (1,3-dimethylbutyl) -N′-p-phenylenediamine, manufactured by Ouchi Shinsei Chemical Co., Ltd., knock rack 6C
* 6: Ouchi Shinsei Chemical Co., Ltd .: Noxeller MZ
* 7: Ouchi Shinsei Chemical Co., Ltd .: Noxeller NS

  From the results in Table 1, it was confirmed that in the method for producing a polymer composition of the present invention, a polymer composition excellent in wear resistance and low heat build-up can be synthesized.

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

Claims (6)

A first element comprising a rare earth element-containing compound or a reaction product of a rare earth element compound or a rare earth element compound and a Lewis base;
A second element comprising a compound represented by the following general formula (X);
For the third element containing silica,
After mixing and aging the second element and the third element, the first element is added and reacted, and in the presence of the resulting polymerization catalyst composition,
Comprising polymerizing at least one of a conjugated diene compound and a non-conjugated olefin to form a polymer component,
6. A method for producing a polymer composition, comprising adding 6 parts by weight or more with respect to 100 parts by weight of the total amount of conjugated diene compound and / or non-conjugated olefin to which the compounding amount of silica is added.
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 A hydrogen 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, 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 method for producing a polymer composition according to claim 1, wherein the water content of the third element is 0.1 wt% or more. The first element is represented by the following general formula (i) or (ii):
MX ₂ · Lw (i)
MX ₃ · Lw (ii)
(In each formula, M represents a lanthanoid element, scandium or yttrium, and X is independently a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, an aldehyde residue, or a ketone residue. , Carboxylic acid residue, thiocarboxylic acid residue, phosphorus compound residue, unsubstituted or substituted cyclopentadienyl, or unsubstituted or substituted indenyl, L represents a Lewis base, and w represents 0 to 3 The manufacturing method of the polymer composition of Claim 1 containing the complex represented by this.   The method for producing a polymer composition according to claim 1, wherein the rare earth element compound and a reaction product of the rare earth element compound and a Lewis base do not have a bond between the rare earth element and carbon. 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 a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms, ^{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). The method for producing a polymer composition according to claim 1.   A polymer composition produced using the method for producing a polymer composition according to any one of claims 1 to 5.