JP5769577B2 - Rubber composition for crawler and rubber crawler using the same - Google Patents

Description

  The present invention relates to a rubber composition for a crawler and a rubber crawler using the same, and in particular, the crack growth resistance (durability) of the rubber crawler without reducing the cut resistance (impact resistance) and tearing force of the rubber crawler. ), A rubber composition for a crawler capable of improving ozone resistance and abrasion resistance, and a rubber crawler using the same.

Rubber crawlers are mainly used in traveling parts such as agricultural machinery, construction machinery, and civil engineering machinery, and the performance required for the ground surface side (rug) rubber is tearing force, wear resistance, cut resistance, and crack growth resistance. And having a good balance between these properties and the resistance to ozone deterioration lead to a long life of the rubber crawler, particularly the lug rubber.
As a conventional rubber crawler, a rubber crawler obtained from a rubber composition containing NR or high styrene polymer (HSR) in SBR can be mentioned (for example, see Patent Document 1). Further, those obtained from a rubber composition in which styrene butadiene rubber (SBR) or butadiene rubber (BR) is contained in natural rubber (NR), or high cis butadiene rubber (high cis BR, cis-1,4) Those obtained from a rubber composition containing a binding content of 90% or more are also known (see, for example, Patent Documents 2 and 3). As described above, NR / SBR and NR / BR (or high cis BR) rubber compositions are usually used as rubber crawlers, and preferable performance can be obtained by changing the respective compounding ratios. It is the present situation that we are striving for.

However, the rubber composition described in Patent Document 1 has been required to have low crack growth resistance improvement due to the presence of SBR. In particular, agricultural crawlers in areas used in low-temperature environments and high-use Asian areas have a major issue of cracking due to ozone, cracking due to bending, and the rapid growth of cracks. In the NR / SBR blend formulation, the above problem may lead to an early life. Further, when blended with a SBR-based formulation that emphasizes cut resistance, further improvement in crack growth resistance has been demanded.
On the other hand, when the rubber composition described in Patent Document 2 or 3 is used, there is a risk that the crack growth resistance may be reduced due to the inclusion of SBR, as described above, while BR is contained without using SBR. In such a case, the problem of crack growth resistance is eliminated, but there is a risk of a decrease in cut resistance, and there is room for further improvement in any case. Patent Document 3 discloses an example using a high cis BR in which the cis-1,4 bond content in the 1,3-butadiene monomer unit is described as 90% or more. Even if this high-sis BR is used, the problem of significant reduction in cut resistance cannot be solved, and there is room for further improvement.
When BR or high cis BR is contained in a rubber composition, it is known that the wear resistance, ozone resistance and crack growth resistance are improved. Therefore, these BRs are preferably used. As described above, the cut resistance and tearing force (trauma property) decrease as the amount of these BR added increases. Therefore, the addition of a large amount to improve performance such as crack growth resistance, the rubber crawler There is a possibility of shortening the service life.

  In order to solve such a problem, by adding 5 to 40 parts by mass, particularly 10 to 30 parts by mass of a butadiene polymer (BR) to 100 parts by mass of the rubber composition, generation and growth of cracks are achieved. Has been studied to improve the wear resistance and ozone resistance and to suppress the deterioration of self-heating due to the low heat generation (see, for example, Patent Document 4).

  However, when a large amount of butadiene-based polymer (BR) is added to 100 parts by mass of the rubber composition with respect to the NR-based NR / SBR blend formulation, the life is not significantly extended.

  As described above, in the rubber crawler field, a rubber composition capable of improving crack growth resistance (durability), ozone resistance and wear resistance without reducing cut resistance (impact resistance) and tearing force. The product has not been developed yet, and the development is strongly desired.

JP 08-208890 A JP 11-139359 A JP 2001-026671 A JP 2009-298905 A

  Accordingly, an object of the present invention is to improve the crack growth resistance (durability), ozone resistance and wear resistance of a rubber crawler without reducing the cut resistance (impact resistance) and tearing force of the rubber crawler. An object of the present invention is to provide a rubber composition for a crawler and a rubber crawler using the same.

The present inventors provide a rubber composition for a crawler containing a conjugated diene polymer and a conjugated diene compound-nonconjugated olefin copolymer in a rubber component, and the rubber component is 100 parts by mass with respect to the rubber component. By including 10 to 30 parts by mass of the conjugated diene compound-nonconjugated olefin copolymer, the crack growth resistance of the rubber crawler is reduced without reducing the cut resistance (impact resistance) and tearing force of the rubber crawler ( Durability), ozone resistance and abrasion resistance can be improved, and the present invention has been completed.
In addition, the present inventors substituted the whole amount of butadiene rubber (BR) with a conjugated diene compound-nonconjugated olefin copolymer having higher crystallinity in a conventional blend of natural rubber (NR) / butadiene rubber (BR). By doing so, it has been found that the crystallization can significantly improve the suppression of crack growth of the rubber crawler and can greatly improve the wear resistance and ozone resistance of the rubber crawler. In addition, with regard to the cut resistance and tearing force of rubber crawlers, which have conventionally been a characteristic of concern, the butadiene rubber (BR) is completely replaced with a conjugated diene compound-nonconjugated olefin copolymer to suppress a significant decrease. I found that I can do it.

That is, the rubber composition for a crawler of the present invention is a rubber composition for a crawler containing a conjugated diene polymer and a conjugated diene compound-nonconjugated olefin copolymer in a rubber component, and the rubber component 100 to parts by weight, the conjugated diene compound - non-conjugated olefin copolymer seen containing 10 parts by mass to 30 parts by mass, the conjugated diene compound - the content of the non-conjugated olefin-derived moieties in the non-conjugated olefin copolymer, It is characterized by being 20 mol% to 70 mol% .

  In the rubber composition for a crawler according to the present invention, the proportion of the conjugated diene compound-derived portion in the copolymer is preferably 30 mol% to 80 mol%.

  In the rubber composition for a crawler of the present invention, it is preferable that the cis-1,4 bond content of the conjugated diene compound-derived portion in the copolymer is 50% or more.

  In the rubber composition for a crawler of the present invention, the conjugated diene polymer preferably contains at least one selected from the group consisting of natural rubber and styrene-butadiene copolymer rubber.

  In the rubber composition for a crawler of the present invention, the copolymer preferably has a polystyrene-equivalent weight average molecular weight of 10,000 to 10,000,000.

  The rubber composition for crawlers of the present invention preferably has a molecular weight distribution (Mw / Mn) of the copolymer of 10 or less.

  In the rubber composition for crawlers of the present invention, the non-conjugated olefin is preferably an acyclic olefin.

  In the rubber composition for a crawler of the present invention, the non-conjugated olefin preferably has 2 to 10 carbon atoms.

  In the rubber composition for a crawler of the present invention, the non-conjugated olefin is preferably at least one selected from the group consisting of ethylene, propylene, and 1-butene.

  In the rubber composition for a crawler according to the present invention, the non-conjugated olefin is preferably ethylene.

  In the rubber composition for a crawler of the present invention, the conjugated diene compound is preferably at least one selected from the group consisting of 1,3-butadiene and isoprene.

  The rubber composition for a crawler of the present invention preferably contains 60 to 80 parts by mass of the conjugated diene polymer with respect to 100 parts by mass of the rubber component.

  The rubber crawler of the present invention is characterized by using the rubber composition for a crawler of the present invention.

  According to the present invention, it is possible to improve the crack growth resistance (durability), ozone resistance and wear resistance of a rubber crawler without reducing the cut resistance (impact resistance) and tearing force of the rubber crawler. A rubber composition for a crawler and a rubber crawler using the same can be provided.

FIG. 1 is a schematic perspective view showing a rubber crawler according to the present invention. FIG. 2 is a schematic cross-sectional view along the line AA in FIG. FIG. 3 is a diagram showing a sheet chucking method in the measurement of crack growth resistance. FIG. 4 is a diagram showing a ¹³ C-NMR spectrum chart of copolymer A produced according to Preparation Example 1. FIG. 5 is a diagram showing a DSC curve of copolymer A produced according to Preparation Example 1. FIG. 6 is a diagram showing a DSC curve of copolymer C produced according to Preparation Example 3.

(Rubber composition for crawler)
The rubber composition for a crawler of the present invention comprises at least (i) a rubber component containing a conjugated diene polymer and a conjugated diene compound-nonconjugated olefin copolymer, and (ii) a cross-linking as necessary. An agent, (iii) a vulcanization accelerator, and (iv) other components.

<(I) Rubber component>
The rubber component includes at least a conjugated diene polymer and a conjugated diene compound-nonconjugated olefin copolymer, and further includes other rubber components as necessary.

-Conjugated diene polymer-
The conjugated diene polymer means a polymer (polymer) containing no non-conjugated olefin as a monomer unit component (part of copolymer). Styrene is not included in the non-conjugated olefin.
There is no restriction | limiting in particular as said conjugated diene polymer, According to the objective, it can select suitably, For example, natural rubber (NR), various polybutadiene rubber (BR) (for example, high cis-butadiene rubber), synthetic poly, etc. Isoprene rubber (IR), various styrene-butadiene copolymer rubber (SBR), ethylene-propylene rubber (EPR), styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene copolymer Examples thereof include rubber, acrylonitrile-butadiene copolymer rubber (NBR), and chloroprene rubber. These may be used individually by 1 type and may use 2 or more types together. Here, the high-cis butadiene rubber is a butadiene rubber or cis-1,4 bond having a cis-1,4 bond content of less than 90% in 1,3-butadiene monomer units as measured by FT-IR. High-cis butadiene rubber having a content of 90% or more and less than 98%.
Among these, styrene-butadiene copolymer and natural rubber are preferable from the viewpoint of the performance of the rubber crawler.
In addition, when the styrene-butadiene copolymer and natural rubber are used in combination, the weight ratio (styrene-butadiene copolymer: natural rubber) is not particularly limited and can be appropriately selected according to the purpose. 1: 3 to 3: 1 are preferred. When it is 1 or more: 3, a rubber compound advantageous for fatigue resistance can be obtained, and when it is 3 or less: 1, a rubber compound advantageous for cut resistance and tear strength can be obtained.

-Conjugated diene compound-Non-conjugated olefin copolymer-
The conjugated diene compound-nonconjugated olefin copolymer contains a nonconjugated olefin as a monomer unit component in the copolymer.

The cis-1,4 bond amount of the conjugated diene compound-derived portion in the conjugated diene compound-nonconjugated olefin copolymer is not particularly limited and may be appropriately selected depending on the intended purpose. Preferably, more than 92% is particularly preferable, and 95% or more is most preferable.
If the amount of cis 1,4-bond in the conjugated diene compound-derived portion is 50% or more, a low glass transition point (Tg) can be maintained, and thereby, such as crack growth resistance and wear resistance. Physical properties are improved.
On the other hand, the crack growth resistance, weather resistance, and heat resistance can be improved by setting the cis 1,4-bond amount of the conjugated diene compound-derived portion to more than 92%. Further, by making the cis 1,4-bond amount of the conjugated diene compound-derived portion 95% or more, the crack growth resistance, weather resistance, and heat resistance can be further improved.
The cis-1,4 bond amount is an amount in the conjugated diene compound-derived portion, and is not a ratio to the entire copolymer.

There is no restriction | limiting in particular as content of the said conjugated diene compound origin part in the said conjugated diene compound-nonconjugated olefin copolymer, Although it can select suitably according to the objective, 30 mol%-80 mol% are preferable.
When the content of the conjugated diene compound-derived portion in the conjugated diene compound-nonconjugated olefin copolymer is 30 mol% or more, the compatibility with the diene rubber is good, and the processability can be sufficiently secured. 80 mol% or less, the proportion of non-conjugated olefin is increased, a sufficient elastic modulus can be secured, and weather resistance is improved, which is preferable.

There is no restriction | limiting in particular as content of the said nonconjugated olefin origin part in the said conjugated diene compound-nonconjugated olefin copolymer, Although it can select suitably according to the objective, 20 mol%-70 mol% are preferable.
When the content of the non-conjugated olefin-derived portion in the conjugated diene compound-non-conjugated olefin copolymer is 20 mol% or more, a sufficient elastic modulus can be secured and weather resistance can be improved, and 70 mol% or less. When it is, compatibility with a conjugated diene polymer can be maintained, processability can be ensured, and weather resistance and crack growth resistance can be improved.

On the other hand, in the conjugated diene compound-nonconjugated olefin copolymer, the nonconjugated olefin used as a monomer is a nonconjugated olefin other than the conjugated diene compound, and has excellent heat resistance and in the main chain of the copolymer. It is possible to increase the degree of freedom of design as an elastomer by reducing the proportion of double bonds occupied and reducing the crystallinity. Moreover, as a nonconjugated olefin, it is preferable that it is an acyclic olefin, and it is preferable that carbon number of this nonconjugated olefin is 2-10. Accordingly, preferred examples of the non-conjugated olefin include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene. Among these, ethylene, propylene And 1-butene are preferred, with ethylene being particularly preferred. Here, the non-conjugated olefin does not contain styrene.
Since the α-olefin has a double bond at the α-position of the olefin, copolymerization with the conjugated diene can be performed efficiently. 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.
In addition, when a block portion composed of a monomer unit of non-conjugated olefin is provided, it exhibits static crystallinity and is excellent in mechanical properties such as breaking strength.

  In the conjugated diene compound-nonconjugated olefin copolymer, the conjugated diene compound used as a monomer preferably has 4 to 12 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.

  The copolymer of the present invention can be prepared by the same mechanism using any of the specific examples of the conjugated diene compound described above.

In the conjugated diene compound-nonconjugated olefin copolymer, the weight average molecular weight (Mw) is not particularly limited, and the weight average molecular weight (Mw) is not particularly limited. From the viewpoint of application to a molecular structure material, the polystyrene-converted weight average molecular weight (Mw) of the copolymer is preferably 10,000 to 10,000,000, more preferably 10,000 to 1,000,000, and 50 000 to 600,000 is particularly preferred. If the Mw exceeds 10,000,000, the moldability may be deteriorated.
Further, the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably 10 or less, more preferably 6 or less. This is because if the molecular weight distribution exceeds 10, the physical properties are not uniform. Here, the average molecular weight and the molecular weight distribution can be determined using polystyrene as a standard substance by gel permeation chromatography (GPC).

The content of 1,2 adducts (including 3,4 adducts) of the conjugated diene compound in the conjugated diene compound-derived part of the conjugated diene compound-nonconjugated olefin copolymer is not particularly limited and depends on the purpose. However, it is preferably 5% or less, more preferably 3% or less, and particularly preferably 2.5% or less.
When the content of 1,2 adducts (including 3,4 adducts) of the conjugated diene compound in the conjugated diene compound-derived part of the conjugated diene compound-nonconjugated olefin copolymer is 5% or less, The weather resistance and ozone resistance of the coalescence can be further improved.
On the other hand, the content of 1,2 adducts (including 3,4 adducts) of the conjugated diene compound in the conjugated diene compound-derived part of the conjugated diene compound-nonconjugated olefin copolymer is 2.5% or less. And the weather resistance and ozone resistance of the copolymer can be further improved.
The content of the 1,2-adduct portion (including the 3,4-adduct portion) is an amount in the portion derived from the conjugated diene compound, and is not a ratio to the whole copolymer.
The 1,2-adduct portion (including 3,4-adduct portion) content of the conjugated diene compound in the conjugated diene compound-derived portion has the same meaning as the 1,2-vinyl bond amount when the conjugated diene compound is butadiene. It is.

  The chain structure of the conjugated diene compound-nonconjugated olefin copolymer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a block copolymer, a random copolymer, a taper copolymer, An alternating copolymer etc. are mentioned.

--Block copolymer--
The block copolymer has a structure of (AB) _x , A- (BA) _x and B- (AB) _x (where A is a monomer unit of a non-conjugated olefin. It is a block part, B is a block part consisting of monomer units of a conjugated diene compound, and x is an integer of 1 or more. In addition, the block copolymer provided with two or more structures of (AB) or (BA) is called a multi-block copolymer.
When the conjugated diene compound-nonconjugated olefin copolymer is a block copolymer, the block portion composed of the monomer of the nonconjugated olefin exhibits static crystallinity, and thus has excellent mechanical properties such as breaking strength. The block portion showing crystallinity can suppress a decrease in storage elastic modulus (G ′).

--Random copolymer--
When the conjugated diene compound-nonconjugated olefin copolymer is a random copolymer, the arrangement of the monomer units of the nonconjugated olefin is irregular, so that the copolymer does not cause phase separation, and the block portion The crystallization temperature derived from is not observed. That is, since it becomes possible to introduce a non-conjugated olefin having properties such as heat resistance into the main chain of the copolymer, the heat resistance is improved.

--Tapered copolymer--
The taper copolymer is a copolymer in which a random copolymer and a block copolymer are mixed, a block portion composed of monomer units of a conjugated diene compound and a monomer unit of non-conjugated olefins. The block part is composed of at least one block part (also referred to as a block structure) and a random part (referred to as a random structure) in which monomer units of a conjugated diene compound and a nonconjugated olefin are irregularly arranged. It is a copolymer.
The structure of the taper copolymer indicates that the composition of the conjugated diene compound component and the non-conjugated olefin component is distributed continuously or discontinuously. Here, it is preferable that the chain structure of the non-conjugated olefin component does not contain many long-chain (high molecular weight) non-conjugated olefin block components but contains many short-chain (low molecular weight) non-conjugated olefin block components.

--Alternate copolymer--
The alternating copolymer has a structure in which a conjugated diene compound and a non-conjugated olefin are alternately arranged (a molecular chain structure of -ABABABAB-, where A is a non-conjugated olefin and B is a conjugated diene compound). It is a coalescence. In the case of an alternating copolymer, both flexibility and adhesiveness can be achieved.

  In the present invention, when the conjugated diene compound-nonconjugated olefin copolymer is a block copolymer, the block portion composed of the monomer of the nonconjugated olefin exhibits static crystallinity. In the case of an alternating copolymer, both flexibility and adhesiveness can be achieved. The copolymer is preferably at least one selected from a block copolymer and a tapered copolymer.

The content of the conjugated diene compound-nonconjugated olefin copolymer in 100 parts by mass of the rubber component is not particularly limited as long as it is 10 parts by mass to 30 parts by mass, and may be appropriately selected according to the purpose. Although it can do, 15 mass parts-20 mass parts are preferable.
When the content of the conjugated diene compound-nonconjugated olefin copolymer in 100 parts by mass of the rubber component is 10 parts by mass or more, wear resistance, crack growth resistance, and ozone resistance can be improved. If it is 30 parts by mass or less, it is possible to suppress a decrease in cut resistance and tearing force.
When the content of the conjugated diene compound-nonconjugated olefin copolymer in 100 parts by mass of the rubber component is less than 15 parts by mass, sufficient ozone resistance may not be obtained, and the content exceeds 20 parts by mass. When it exists, the fall as durability as a rubber compound will be caused, and the lifetime as a rubber crawler may become short.

--Conjugated diene compound-Method for producing non-conjugated olefin copolymer--
Next, a production method capable of producing the conjugated diene compound-nonconjugated olefin copolymer will be described in detail. However, the manufacturing method described in detail below is merely an example. The copolymer according to the present invention can polymerize a conjugated diene compound and a non-conjugated olefin in the presence of a polymerization catalyst or a polymerization catalyst composition.

  In the method for producing a conjugated diene compound-nonconjugated olefin copolymer, a polymerization by a normal coordination ion polymerization catalyst is used except that a polymerization catalyst described later, or first, second, and third polymerization catalyst compositions are used. A conjugated diene compound as a monomer and a non-conjugated olefin can be copolymerized in the same manner as in the production method of the coalescence. In the present invention, the polymerization catalyst or polymerization catalyst composition used will be described in detail later.

  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 method for producing a conjugated diene compound-nonconjugated olefin copolymer includes, for example, (1) a polymerization catalyst composition comprising a conjugated diene compound as a monomer and a non-conjugated olefin other than the conjugated diene compound. The components may be provided separately and used as a polymerization catalyst composition in the reaction system, or (2) a polymerization catalyst composition prepared in advance may be provided in the polymerization reaction system. Moreover, (2) includes providing a metallocene complex (active species) activated by a cocatalyst. In addition, the usage-amount of the metallocene complex contained in a polymerization catalyst composition has the preferable range of 0.0001-0.01 times mole with respect to the sum total of nonconjugated olefins other than a conjugated diene compound and this conjugated diene compound.

  Moreover, in the manufacturing method of the conjugated diene compound-nonconjugated olefin copolymer which concerns on this invention, you may stop superposition | polymerization using polymerization terminators, such as methanol, ethanol, and isopropanol.

  In the production method according to the present invention, the polymerization reaction of the conjugated diene compound and the non-conjugated olefin 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. Moreover, since the pressure of the said polymerization reaction fully takes in a conjugated diene compound and a nonconjugated olefin in a polymerization reaction system, the range of 0.1-10.0 MPa is preferable. Further, the reaction time of the above polymerization reaction is not particularly limited, and is preferably in the range of 1 second to 10 days, for example. it can.

  In the method for producing the copolymer, when the conjugated diene compound is polymerized with a non-conjugated olefin other than the conjugated diene compound, the pressure of the non-conjugated olefin is preferably 0.1 MPa to 10 MPa. When the pressure of the non-conjugated olefin is 0.1 MPa or more, the non-conjugated olefin can be efficiently introduced into the reaction mixture. Moreover, even if the pressure of the non-conjugated olefin is increased too much, the effect of efficiently introducing the non-conjugated olefin reaches a peak, and therefore the pressure of the non-conjugated olefin is preferably 10 MPa or less.

In the method for producing the copolymer, when the conjugated diene compound is polymerized with a non-conjugated olefin other than the conjugated diene compound, the concentration of the conjugated diene compound at the start of polymerization (mol / l) and the concentration of the non-conjugated olefin (Mol / l) preferably satisfies the relationship of the following formula. By setting the value of the concentration of the non-conjugated olefin / the concentration of the conjugated diene compound to 1 or more, the non-conjugated olefin can be efficiently introduced into the reaction mixture.
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.0
More preferably, the relationship of the following formula is satisfied.
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.3
More preferably, the relationship of the following formula is satisfied.
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.7

  According to the production method of the present invention, a conjugated diene compound that is a monomer is used in the same manner as in the production method of a polymer using a normal coordination ion polymerization catalyst, except that the polymerization catalyst or the polymerization catalyst composition is used. And non-conjugated olefin can be copolymerized.

（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）： -First polymerization catalyst composition-
Next, the 1st polymerization catalyst composition used in the manufacturing method of the conjugated diene compound-nonconjugated olefin copolymer based on this invention is demonstrated.
The polymerization catalyst composition includes 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種類の錯体を含む重合触媒組成物（以下、第一重合触媒組成物ともいう）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. A polymerization catalyst composition (hereinafter also referred to as a first polymerization catalyst composition) containing at least one complex selected from the group consisting of half metallocene cation complexes represented by

The first 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 first 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. Further, the ionic compound represented by the general formula [A] + [B]-is preferably added in an amount of 0.1 to 10 times, more preferably about 1 time, with respect to 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 first 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 content of aluminoxane in the first 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 1-50 times mole 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 about 10 times mole.

  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 copolymer can be increased.

-Second polymerization catalyst composition-
Next, the second polymerization catalyst composition used in the method for producing a conjugated diene compound-nonconjugated olefin copolymer according to the present invention will be described.
In addition, as the polymerization catalyst composition,
(A) component: a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base, the rare earth element compound or the reaction product having no 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. A polymerization catalyst composition (hereinafter also referred to as a second polymerization catalyst composition) containing at least one selected from the group consisting of at least one halogen compound (B-3) among organic compounds can be preferably mentioned.
When the second polymerization catalyst composition contains at least one of the ionic compound (B-1) and the halogen compound (B-3), the polymerization catalyst composition further comprises:
(C) Component: The following general formula (X):
YR ¹ _a R ² _b R ³ _c (X)
[Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R1 and R2 are the same or different and have 1 to 10 carbon atoms. R ³ is a group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is 1 in the periodic table. When the metal is selected from the group, a is 1, and b and c are 0, and when Y is the metal selected from groups 2 and 12 of the periodic table, a and In the case where b is 1 and c is 0, and Y is a metal selected from Group 13 of the Periodic Table, a, b, and c are 1].

The second polymerization catalyst composition used in the method for producing the copolymer needs to contain the component (A) and the component (B), and the polymerization catalyst composition is the ionic compound (B). -1) and at least one of the above halogen compounds (B-3),
(C) Component: The following general formula (X):
YR ¹ _a R ² _b R ³ _c (X)
[Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. R ³ is a hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is a periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1]. It is necessary to include.
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 second 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 second polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol / l.

The component (A) used in the second 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 a Lewis base is performed. The object does not have a bond between 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 (XI) or (XII):
M ¹¹ X ¹¹ ₂ · L ¹¹ w (XI)
M ¹¹ X ¹¹ ₃ · L ¹¹ w (XII)
[Wherein, 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, a carboxylic acid residue, a thiocarboxylic acid residue or a phosphorus compound residue, L ¹¹ represents a Lewis base, and w represents 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 second 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 second 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 2nd 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 mole with respect to (A) component, and, as for content of the ionic compound in the said 2nd polymerization catalyst composition, it is still more preferable that it is about 1 time mole.

  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 aluminoxane content in the second 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 the said 2nd 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 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 second polymerization catalyst composition is represented by the following general formula (X):
YR ¹ _a R ² _b R ³ _c (X)
[Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. R ³ is a hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is a periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1]. Yes, the following general formula (Xa):
AlR ¹ R ² R ³ (Xa)
[Wherein, R ¹ and R ² are the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ represents the above It may be the same as or different from R ¹ or R ² ]. Examples of the organoaluminum compound of the formula (X) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, 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, diisohexyl hydride Aluminum, dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propyl aluminum Hydride, include isobutyl aluminum 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 2nd polymerization catalyst composition, it is still more preferable that it is about 10 times mole.

-Polymerization catalyst-
Next, the polymerization catalyst used in the method for producing a conjugated diene compound-nonconjugated olefin copolymer according to the present invention will be described.
As a polymerization catalyst, it is for superposition | polymerization with a conjugated diene compound and a nonconjugated olefin, and following formula (A):
R _a MX _b QY _b (A)
[In the formula, each R independently represents an unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium; 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系複合触媒が挙げられる。
上記メタロセン系重合触媒を用いることで、共役ジエン化合物−非共役オレフィン共重合体を製造することができる。また、上記メタロセン系複合触媒、例えば予めアルミニウム触媒と複合させてなる触媒を用いることで、共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、共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、上記メタロセン系複合触媒であれば、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。 In a preferred example of the metallocene composite catalyst, the following formula (XV):

[ ^Wherein , M ¹ represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents unsubstituted or substituted indenyl, 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 composite catalysts represented by
By using the metallocene polymerization catalyst, a conjugated diene compound-nonconjugated olefin copolymer can be produced. In addition, by using the metallocene composite catalyst, for example, a catalyst previously combined with an aluminum catalyst, the amount of alkylaluminum used at the time of copolymer synthesis can be reduced or eliminated. 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 composite catalyst, 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 _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 ^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、上記メタロセン系複合触媒の構造は、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 composite catalyst is, for example, in a solvent in 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 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 composite catalyst 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 composite catalyst is represented by AlR ^K R ^L R ^M , where R ^K and R ^L are each independently a monovalent carbon atom having 1 to 20 carbon atoms. R ^M is a hydrogen group or a hydrogen atom, and 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. In addition, the amount of the organoaluminum compound used for the production of the metallocene composite catalyst is preferably 1 to 50 times mole, more preferably about 10 times mole relative to the metallocene complex.

-Third polymerization catalyst composition-
The polymerization catalyst composition contains the metallocene composite catalyst and a boron anion, and further contains other components such as a cocatalyst contained in the polymerization catalyst composition containing a normal metallocene catalyst. Etc. are preferably included. The metallocene composite catalyst 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 composite catalyst, the content of each monomer component in the copolymer can be arbitrarily controlled. It becomes possible.

  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 mole with respect to the said metallocene type composite catalyst, and, as for the ionic compound which consists of a boron anion and a cation, it is still more preferable to add about 1 time mole.

  In the third polymerization catalyst composition, it is necessary to use the metallocene composite catalyst and the boron anion, but a reaction system for reacting the metallocene catalyst represented by the formula (XVI) with an organoaluminum compound. If a boron anion is present, the metallocene composite catalyst 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 composite catalyst in advance, isolate and purify the metallocene composite catalyst, 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.

  Further, even if the first polymerization catalyst composition or the second polymerization catalyst composition is not used, that is, when a normal coordination ion polymerization catalyst is used, the monomer into the polymerization reaction system The copolymer can be produced by adjusting the charging method. That is, the second production method of the copolymer is characterized by controlling the chain structure of the copolymer by controlling the introduction of the conjugated diene compound in the presence of the non-conjugated olefin, The arrangement of the monomer units in the copolymer can be controlled. In addition, in this invention, a polymerization reaction system means the place where superposition | polymerization with a conjugated diene compound and a nonconjugated olefin is performed, A reaction container etc. are mentioned as a specific example.

  Here, the charging method of the conjugated diene compound may be either continuous charging or split charging, and further, continuous charging and split charging may be combined. Moreover, continuous injection means adding for a fixed time at a fixed addition rate, for example.

  Specifically, the concentration ratio of monomers in the polymerization reaction system can be controlled by dividing or continuously adding the conjugated diene compound to the polymerization reaction system for polymerizing the conjugated diene compound and the non-conjugated olefin. As a result, it is possible to characterize the chain structure (that is, the arrangement of monomer units) in the resulting copolymer. Further, when the conjugated diene compound is added, the presence of the non-conjugated olefin in the polymerization reaction system can suppress the formation of a conjugated diene compound homopolymer. The addition of the conjugated diene compound may be performed after the polymerization of the nonconjugated olefin is started.

  For example, when the copolymer is produced by the second production method, it is effective to continuously add a conjugated diene compound in the presence of the non-conjugated olefin to the polymerization reaction system in which the polymerization of the non-conjugated olefin has been started in advance. It becomes. In particular, when a multi-block copolymer is produced by the second production method, “a non-conjugated olefin is polymerized in a polymerization reaction system, and then the conjugated diene compound is reacted in the presence of the non-conjugated olefin. It is effective to repeat the operation of “continuous charging into the system” twice or more.

  The second production method is not particularly limited as described above, except that the method of charging the monomer into the polymerization reaction system as described above. For example, the solution polymerization method, the suspension polymerization method, the liquid phase bulk polymerization method, Any polymerization method such as an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. In addition, the second production method is the same as the first production method, except that the method of charging the monomer into the polymerization reaction system as described above, and the conjugated diene compound as a monomer Non-conjugated olefins can be copolymerized.

  In the second production method, it is necessary to control the input of the conjugated diene compound. Specifically, it is preferable to control the input amount of the conjugated diene compound and the input frequency of the conjugated diene compound. Examples of the method for controlling the introduction of the conjugated diene compound include a method of controlling by a program such as a computer and a method of controlling by analog using a timer or the like, but are not limited thereto. In addition, as described above, the method for charging the conjugated diene compound is not particularly limited, and examples thereof include continuous charging and divided charging. Here, when the conjugated diene compound is dividedly added, the number of times the conjugated diene compound is added is not particularly limited, but is preferably in the range of 1 to 5 times. If the conjugated diene compound is charged too many times, it may be difficult to distinguish between a block copolymer and a random copolymer.

  In the second production method, since it is necessary that the non-conjugated olefin is present in the polymerization reaction system when the conjugated diene compound is charged, the non-conjugated olefin is continuously supplied to the polymerization reaction system. Is preferred. Moreover, the supply method of a nonconjugated olefin is not specifically limited.

-Mass ratio of conjugated diene polymer and conjugated diene compound-non-conjugated olefin copolymer-
The mass ratio between the conjugated diene polymer and the conjugated diene compound-nonconjugated olefin copolymer is not particularly limited and may be appropriately selected depending on the intended purpose. Preferably, 85: 15-8: 2 is more preferable.
When the conjugated diene polymer exceeds the upper limit (the conjugated diene compound-non-conjugated olefin copolymer is less than the lower limit), the rubber crawler wear resistance, crack growth resistance, ozone degradation resistance and resistance. The effect of improving the cut property may be reduced, and if the conjugated diene polymer is less than the lower limit (the conjugated diene compound-nonconjugated olefin copolymer exceeds the upper limit), the cut resistance is reduced. The life of the rubber crawler may be reduced.

-Other rubber components-
There is no restriction | limiting in particular as said other rubber | gum, According to the use called a rubber crawler in the range which is not contrary to the objective of this invention, a small amount (For example, 10 mass parts or less with respect to 100 mass parts of rubber components) Other synthetic rubbers can be included.
There is no restriction | limiting in particular as said other synthetic rubber, According to the objective, it can select suitably, For example, polysulfide rubber, silicone rubber, fluororubber, urethane rubber etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

<(Ii) 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 Compound-based crosslinking agents, oxime-nitrosamine-based crosslinking agents, sulfur and the like can be mentioned. Among these, sulfur-based crosslinking agents are more preferable as rubber compositions for rubber crawlers.
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-10 mass parts are preferable with respect to 100 mass parts of rubber components.
If the content of the cross-linking agent is 0.1 parts by mass or more, the cross-linking can surely proceed, and if it is 10 parts by mass or less, the cross-linking has progressed during kneading with some cross-linking agents. It is possible to prevent the physical properties of the vulcanizate from being damaged.

-Sulfur-based crosslinking agent-
There is no restriction | limiting in particular as said sulfur type crosslinking agent, According to the objective, it can select suitably, For example, sulfur etc. are mentioned.
There is no restriction | limiting in particular as content of the said sulfur, Although it can select suitably according to the objective, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of rubber components, and 1 mass part-5 Part by mass is more preferable.
If the sulfur content is less than 0.1 parts by mass, a sufficient vulcanization effect may not be obtained, and the target performance may not be achieved. If it exceeds 10 parts by mass, the rubber becomes brittle, and the rubber The fatigue performance may be reduced.

<(Iii) Vulcanization accelerator>
There is no restriction | limiting in particular as said vulcanization accelerator, According to the objective, it can select suitably, For example, guanidine type | system | groups, such as DPG (diphenyl guanidine); Aldehyde-amine type; Aldehyde-ammonia type; M (2- Mercaptobenzothiazole), DM (dibenzothiazyl disulfide), thiazoles such as CZ (N-cyclohexyl-2-benzothiazylsulfenamide); N, N′-dicyclohexyl-2-benzothiazolylsulfenamide, etc. Compounds such as sulfenamides; thioureas; thiurams such as tetramethylthiuram disulfide; dithiocarbamates; xanthates;
There is no restriction | limiting in particular as said vulcanization accelerator, Although it can select suitably according to the objective, 0.1 mass part-5 mass parts are preferable with respect to 100 mass parts of said rubber components, 1 mass part- 5 parts by mass is more preferable.

<(Iv) Other components>
The other components are not particularly limited as long as the object of the present invention is not impaired. Examples thereof include reinforcing agents (for example, white fillers such as carbon black and silica), process oils, resins, and fatty acids. , Zinc oxide, anti-aging agent, wax, sulfur, vulcanization accelerator, vulcanization retarder (scorch inhibitor), silica coupling agent, peptizer, ozone crack inhibitor, antioxidant, clay, calcium carbonate, Etc., and commercially available products can be used.
There is no restriction | limiting in particular as addition amount of the said other component, Although those skilled in the art can select suitably in the range which does not impair the objective of this invention, 40 mass parts-80 mass parts are with respect to 100 mass parts of said rubber components. preferable.

-Carbon black-
The carbon black is not particularly limited and may be appropriately selected depending on the purpose. For example, standard types such as SAF, ISAF, HAF, FEF, GPF, SRF (rubber furnace for rubber), MT carbon black ( Pyrolytic carbon), and the like.
There is no restriction | limiting in particular as content of the said carbon black, Although it can select suitably according to the objective, 20 mass parts-90 mass parts are preferable with respect to 100 mass parts of said rubber components, 40 mass parts-80 Part by mass is more preferable.
There is no restriction | limiting in particular as an iodine adsorption amount by the measuring method according to JISK1474 of the said carbon black, Although it can select suitably according to the objective, 50 g / kg or more is preferable.

-Process oil-
There is no restriction | limiting in particular as said process oil, According to the objective, it can select suitably, For example, process oils, such as a paraffin type, a naphthene type, and an aromatic type, can be mentioned.

-Resin-
The resin is not particularly limited and may be appropriately selected depending on the purpose. For example, polyester polyol resin, dicyclopentadiene resin, rosin resin, phenol resin, xylene resin, aliphatic / alicyclic C5 petroleum resin C5 / C9 petroleum resin, C9 petroleum resin, terpene resin, and copolymers and modified products thereof.
There is no restriction | limiting in particular as content of the said resin, Although it can select suitably according to the objective, 0.5 mass part-20 mass parts are preferable with respect to 100 mass parts of rubber components, and 1 mass part- 10 parts by mass is more preferable.

-Fatty acid-
There is no restriction | limiting in particular as said fatty acid, According to the objective, it can select suitably, For example, a stearic acid etc. are mentioned.
There is no restriction | limiting in particular as content of the said fatty acid, Although it can select suitably according to the objective, 0.5 mass part-10 mass parts are preferable with respect to 100 mass parts of rubber components, and 1 mass part- 5 parts by mass is more preferable.

-Zinc oxide-
There is no restriction | limiting in particular as content of the said zinc oxide, Although it can select suitably according to the objective, 0.5 mass part-10 mass parts are preferable with respect to 100 mass parts of rubber components, 1 mass part -5 mass parts is more preferable.

-Anti-aging agent-
There is no restriction | limiting in particular as said anti-aging agent, According to the objective, it can select suitably, For example, N-phenyl-N '-(1,3-dimethylbutyl) -p-phenylenediamine (6C), N Known amine-based or phenol-based anti-aging agents such as -phenyl-N'-isopropyl-p-phenylenediamine (3C) and 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD) Can be mentioned.
There is no restriction | limiting in particular as content of the said anti-aging agent, Although it can select suitably according to the objective, 0.5 mass part-10 mass parts are preferable with respect to 100 mass parts of rubber components, and 1 mass. Part to 10 parts by mass is more preferable.

-Wax-
There is no restriction | limiting in particular as said wax, According to the objective, it can select suitably, For example, paraffin wax etc. are mentioned.
There is no restriction | limiting in particular as content of the said wax, Although it can select suitably according to the objective, 0.5 mass part-10 mass parts are preferable with respect to 100 mass parts of rubber components, and 1 mass part- 10 mass parts is more preferable, and 1 mass part-5 mass parts is especially preferable.

<Method for Producing Crawler Rubber Composition>
The rubber composition for a crawler of the present invention can be obtained by kneading a rubber component containing at least a conjugated diene polymer and a conjugated diene compound-nonconjugated olefin copolymer with appropriate additives. The kneading method may be according to a method usually carried out by those skilled in the art. For example, all components other than sulfur, a vulcanization accelerator, zinc oxide, and a vulcanization retarder are mixed with a Banbury mixer, Brabender, kneader, high shear type mixer. Kneading (kneading A) at 100 ° C. to 200 ° C., etc., and then adding sulfur, vulcanization accelerator, zinc oxide, vulcanization retarder (B kneading) and 60 ° C. to 130 ° C. with a kneading roll machine or the like. And kneading. By molding the obtained rubber composition for a crawler using a heating mold, a rubber crawler or a rubber crawler lug rubber can be obtained.

(Rubber crawler)
The rubber crawler of the present invention is characterized by using the rubber composition for a crawler of the present invention.
The rubber crawler of the present invention includes, for example, a tread rubber layer 1, an intermediate rubber layer 2, a galvanized steel cord 3, and a cored bar 4 as shown in FIGS.

  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.

  A method for analyzing a conjugated diene compound-nonconjugated olefin copolymer and a method for evaluating a resin composition are shown below.

<Method for analyzing copolymer>
(1) Microstructure of copolymer (1,2-vinyl bond content, cis-1,4 bond content)
The microstructure (1,2-vinyl bond amount) of the butadiene moiety in the copolymer was determined by ¹ H-NMR spectrum (100 ° C., d-tetrachloroethane standard: 6 ppm) according to the 1,2-vinyl bond component (5.0 -5.1 ppm) and the integral ratio of the entire butadiene bond component (5-5.6 ppm). Further, the microstructure (cis-1,4 bond amount) of the butadiene moiety in the copolymer is determined based on the ¹³ C-NMR spectrum (100 ° C., d-tetrachloroethane standard: 73.8 ppm). (26.5-27.5 ppm) and the total butadiene bond component (26.5-27.5 ppm + 31.5-32.5 ppm) were obtained from the integral ratio.

(2) Content of ethylene-derived portion of copolymer The content (mol%) of the ethylene-derived portion in the copolymer is the whole by ¹³ C-NMR spectrum (100 ° C., d-tetrachloroethane standard: 73.8 ppm). The integration ratio of the ethylene bond component (28.5-30.0 ppm) and the total butadiene bond component (26.5-27.5 ppm + 31.5-32.5 ppm).

(3) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the copolymer
Gel permeation chromatography [GPC: Tosoh HLC-8121GPC / HT, column: Tosoh GMH _HR- H (S) HT × 2, detector: differential refractometer (RI)] on the basis of monodisperse polystyrene The polystyrene equivalent weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer were determined. The measurement temperature is 140 ° C.

(4) Block polyethylene melting temperature of copolymer (DSC peak temperature)
Differential scanning calorimetry (DSC) was performed in accordance with JIS K7121-1987, a DSC curve was drawn, and a block polyethylene melting temperature (DSC peak temperature) was measured. In order to avoid the influence of impurities such as single polymer and catalyst residue, the measurement was performed by immersing the copolymer in a large amount of tetrahydrofuran for 48 hours, removing all components dissolved in tetrahydrofuran, and then using the dried rubber component as a sample. did.

(5) Identification of copolymer The chain distribution was analyzed by applying the ozonolysis-GPC method in the literature ("Proceedings of the Society of Polymer Science, Vol. 42, No. 4, Page 1347"). The gel permeation chromatography was measured based on [GPC: Tosoh HLC-8121GPC / HT, column: Showa Denko GPC HT-803 × 2, detector: differential refractometer (RI), monodisperse polystyrene as a reference. The temperature was measured using 140 ° C.].

<Evaluation method>
(1) Crack growth resistance As shown in FIG. 3, a sheet of “width 100 mm × length 30 mm × thickness 2 mm” was chucked in full width leaving a length of 10 mm, and 0 mm at a room temperature of 10 mm in length. Repetitive fatigue was given at a strain of% to 100%, and the growth rate (da / dN: crack growth length with respect to the number of repeated fatigue) of a 20 mm crack placed in one end was measured in advance. The value at each strain was determined, and the average value was used, and the index was displayed with Comparative Example 1 or 5 as 100. It shows that it is excellent in crack growth resistance, so that an index value is large.
(2) Abrasion resistance The amount of abrasion was measured at room temperature using a Ramborn type abrasion tester, the reciprocal of the amount of abrasion was calculated, and Comparative Example 1 or 5 was taken as 100 and indicated as an index. It shows that it is excellent in abrasion resistance, so that an index value is large.
(3) Cut resistance A rubber block measuring 60 mm long x 70 mm wide x 30 mm high was vulcanized to produce a sample. At room temperature, a sharp blade with an angle of 60 degrees with a weight of 15 kg was dropped from a height of 70 cm away from the sample, the crack depth (mm) produced was measured, the reciprocal was calculated, and Comparative Example 1 Or, 5 was set as 100 and displayed as an index. It shows that it is excellent in cut resistance, so that an index value is large.
(4) Tear force Based on a trouser-type tear test [JIS K6252 (1993)], the vulcanized rubber composition was cut into a 2 mm thick trouser-type test piece, and the tear force was measured. Comparative Example 1 or 5 Is shown as an index with 100 being 100. It shows that it is excellent in tearing power, so that an index value is large.
(5) Ozone-resistant (deterioration) resistance According to JIS K6301 (1975) [JIS K6259 (2004)], the surface of the rubber composition after being exposed to ozone for 120 hours was observed, and its ozone-deterioration resistance Evaluated. In the table, A to C indicate the number of occurrences of scratches, and A <B <C. Moreover, the numerical value described in the right side of A-C shows the magnitude | size of a crack, and has a relationship of 1 <2 <3. Specifically, A-1 cannot be confirmed with the naked eye, but indicates that there are a small number of cracks that can be confirmed with a 10x magnifier, and A-2 indicates that there are a small number of cracks that can be confirmed with the naked eye, B-2 indicates that there are many cracks that can be confirmed with the naked eye, B-3 indicates that there are many deep and relatively large cracks (less than 1 mm), and C-3 indicates that there are many deep and relatively large cracks. (Less than 1 mm) is innumerable. “No Crack” indicates that no visible scratches and no visible scratches with a 10 × magnifier occurred.

(Preparation Example 1)
<Preparation of ethylene-butadiene copolymer A (EBR1)>
After adding 160 mL of toluene solution to a sufficiently dry 400 mL pressure-resistant glass reactor, ethylene was introduced at 0.8 MPa. On the other hand, in a glove box under a nitrogen atmosphere, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 28.5 μmol in a glass container. And 34.2 μmol of dimethylanilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] and 1.43 mmol of diisobutylaluminum hydride were dissolved in 8 mL of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, an amount of 28.2 μmol in terms of gadolinium was added to the monomer solution, and polymerization was performed at room temperature for 5 minutes. Thereafter, 100 mL of a toluene solution containing 15.23 g (0.28 mol) of 1,3-butadiene was added while lowering the ethylene introduction pressure at a rate of 0.2 MPa / min, and polymerization was further performed for 90 minutes. After the polymerization, 1 mL of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass of isopropanol solution was added to stop the reaction, and a copolymer with a large amount of methanol was added. Was separated and vacuum dried at 70 ° C. to obtain a copolymer A (block copolymer). The yield of the obtained copolymer A was 12.50 g.
For the obtained copolymer A, the microstructure, ethylene content, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), block polyethylene melting temperature (DSC peak temperature) and chain structure were measured by the above methods. evaluated. FIG. 4 shows a ¹³ C-NMR spectrum chart of copolymer A, and FIG. 5 shows a DSC curve.
As the microstructure of the butadiene portion in the copolymer A, the cis-1,4-bond amount was 98%, and the 1,2-vinyl bond amount was 1.2%.
The weight average molecular weight Mw was 350,000, and the molecular weight distribution Mw / Mn was 2.2.
The ethylene content was 7 mol% (butadiene content was 93 mol%).
The block polyethylene melting temperature (DSC peak temperature) was 121 ° C., and the chain structure was a block.

(Preparation Example 2)
<Preparation of ethylene-butadiene copolymer B (EBR2)>
After adding 100 ml of toluene solution to a sufficiently dried 400 ml pressure-resistant glass reactor, ethylene was introduced at 0.8 MPa. On the other hand, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 28.5 μmol in a glass container in a glove box under a nitrogen atmosphere. , 34.2 μmol of dimethylanilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] and 1.43 mmol of diisobutylaluminum hydride were dissolved in 8 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, an amount of 28.2 μmol in terms of gadolinium was added to the monomer solution, and polymerization was performed at room temperature for 5 minutes. Thereafter, 30 ml of a toluene solution containing 4.57 g (0.085 mol) of 1,3-butadiene was added while lowering the ethylene introduction pressure at a rate of 0.2 MPa / min, and polymerization was further performed for 60 minutes. Next, “the ethylene introduction pressure was returned to 0.8 MPa, polymerization was performed for 5 minutes, and then the ethylene introduction pressure was decreased at a rate of 0.2 MPa / min, while 4.57 g of 1,3-butadiene (0.085 mol). The operation of “addition of 30 ml of a toluene solution containing) followed by further polymerization for 60 minutes” was repeated a total of 3 times. After the polymerization, 1 ml of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass of isopropanol solution was added to stop the reaction, and a copolymer with a large amount of methanol was added. Was separated and dried under vacuum at 70 ° C. to obtain a copolymer B (multi-block copolymer). The yield of the obtained copolymer B was 14.00 g.
For the obtained copolymer B, the microstructure, ethylene content, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), block polyethylene melting temperature (DSC peak temperature) and chain structure were measured by the above methods. evaluated.
As a microstructure of the butadiene portion in the copolymer B, the cis-1,4-bond amount was 97% and the 1,2-vinyl bond amount was 1.2%.
The weight average molecular weight Mw was 283000, and the molecular weight distribution Mw / Mn was 2.8.
The ethylene content was 13 mol% (butadiene content was 87 mol%).
The block polyethylene melting temperature (DSC peak temperature) was 121 ° C., and the chain structure was a block.

(Preparation Example 3)
<Preparation of ethylene-butadiene copolymer C (EBR3)>
After adding 150 ml of toluene to a sufficiently dry 2 L stainless steel reactor, ethylene was introduced at 0.8 MPa. On the other hand, in a glove box under a nitrogen atmosphere, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 14.5 μmol in a glass container. Then, 14.1 μmol of triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ ) and 0.87 mmol of diisobutylaluminum hydride were charged and dissolved in 5 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, an amount of 14.1 μmol in terms of gadolinium was added to the monomer solution, and polymerization was carried out at 50 ° C. for 5 minutes. Thereafter, 20 ml of a toluene solution containing 3.05 g (0.056 mol) of 1,3-butadiene was added while lowering the ethylene introduction pressure at a rate of 0.2 MPa / min, and polymerization was further performed for 15 minutes. Next, “the ethylene introduction pressure was returned to 0.8 MPa, polymerization was performed for 5 minutes, and then the ethylene introduction pressure was reduced at a rate of 0.2 MPa / min, while 6.09 g (0. The operation of adding 40 ml of a toluene solution containing 113 mol) and then performing polymerization for another 30 minutes was repeated a total of 3 times. 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 copolymer was separated with a large amount of methanol. And dried in vacuo at 70 ° C. to obtain a polymer C (multi-block copolymer). The yield of the obtained copolymer C was 24.50 g.
For the obtained copolymer C, the microstructure, ethylene content, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), block polyethylene melting temperature (DSC peak temperature) and chain structure were measured by the above methods. evaluated. The DSC curve of copolymer C is shown in FIG.
As the microstructure of the butadiene portion in the copolymer C, the cis-1,4-bond amount was 97% and the 1,2-vinyl bond amount was 1.4%.
The weight average molecular weight Mw was 205000, and the molecular weight distribution Mw / Mn was 9.15.
The ethylene content was 34 mol% (butadiene content was 66 mol%).
The block polyethylene melting temperature (DSC peak temperature) was 121 ° C., and the chain structure was a block.

Brands such as polymers used in the compositions of Tables 2 to 3 are described below.
NR ^{* 1} : Natural rubber grade RSS # 4
SBR ^{* 2} : Styrene butadiene rubber grade 1500 JSR high cis BR ^{* 3} : butadiene rubber grade BR01 (trade name) JSR EBR1: ethylene-butadiene copolymer A prepared in Preparation Example 1
EBR2: ethylene-butadiene copolymer B prepared in Preparation Example 2
EBR3: ethylene-butadiene copolymer C prepared in Preparation Example 3
Carbon black (HAF): Asahi # 70 (trade name), manufactured by Asahi Carbon Co., Ltd. Process oil: “Komolex (registered trademark) NH-60T” (trade name), manufactured by Shin Nippon Oil Co., Ltd. Stearic acid: PALMAC 1600 (product) Name), zinc oxide manufactured by ACIDCHEM: “Ginbae (registered trademark) SR” (product name), anti-aging agent manufactured by Toho Zinc Co., Ltd. TMDQ: “NOCRACK (registered trademark) 224” (product name), Ouchi Shinsei Chemical Industry Aging inhibitor 6C: “ANTIGENE (registered trademark) 6C” (trade name), manufactured by Sumitomo Chemical Co., Ltd. Paraffin wax: paraffin wax 135 (trade name), manufactured by Nippon Seiki Co., Ltd. Sulfur: Sulfax 5 (trade name) Tsurumi Chemical Co., Ltd. vulcanization accelerator DPG: “Noxeller (registered trademark) D” (trade name), 1,3-Dif Niruguanidine, a vulcanization accelerator manufactured by Ouchi Shinsei Chemical Co., Ltd. CBS: “Noxeller (registered trademark) CZ-G” (trade name), N-cyclohexyl-2-benzothiazolylsulfenamide, Ouchi Shinsei Chemical Industry Resin: Quinton (registered trademark) 1920 dicyclopentadiene resin, Nippon Zeon Co., Ltd. Vulcanization accelerator MBTS: "Noxeller (registered trademark) DM-T" (trade name), dibenzothiazyl disulfide, Ouchi Eshin Vulcanization accelerator manufactured by Chemical Industry Co., Ltd. BBS: “Noxeller (registered trademark) NS-F” (trade name), N-tert-butylbenzoylsulfenamide, manufactured by Ouchi Shinsei Chemical Co., Ltd.

As is clear from Table 2, the rubber compositions of Reference Examples 1 to 3, 5 and 6 and Examples 4 and 7 were a conjugated diene polymer and a conjugated diene compound-nonconjugated olefin copolymer in the rubber component. A rubber composition for crawlers, comprising 10 parts by mass to 30 parts by mass of the conjugated diene compound-nonconjugated olefin copolymer with respect to 100 parts by mass of the rubber component. In comparison, it was possible to achieve improvement in crack growth resistance (durability), ozone resistance and wear resistance without reducing cut resistance (impact resistance) and tearing force.

As is clear from Table 3, the rubber compositions of Reference Examples 8 to 10, 12 and 13 and Examples 11 and 14 were a conjugated diene polymer and a conjugated diene compound-nonconjugated olefin copolymer in the rubber component. The rubber composition for crawlers containing 10 parts by weight to 30 parts by weight of the conjugated diene compound-nonconjugated olefin copolymer with respect to 100 parts by weight of the rubber component. In comparison, it was possible to achieve improvement in crack growth resistance (durability), ozone resistance and wear resistance without reducing cut resistance (impact resistance) and tearing force.

  The rubber composition for crawlers of the present invention can be used for rubber crawlers and rubber crawler lug rubber applications. Such a rubber crawler or a rubber crawler provided with a lug rubber can be used for agricultural machinery, construction machinery, or civil engineering machinery.

1 Tread rubber layer 2 Intermediate rubber layer 3 Galvanized steel cord 4 Core metal 11 Testing machine 12 Sheet sandwiched between the upper and lower sides of the testing machine

Claims (13)

A rubber composition for a crawler containing a conjugated diene polymer and a conjugated diene compound-nonconjugated olefin copolymer in a rubber component,
The rubber relative to 100 parts by weight of the component, the conjugated diene compound - non-conjugated olefin copolymer seen containing 10 parts by mass to 30 parts by mass,
The content of the non-conjugated olefin-derived portion in the conjugated diene compound-non-conjugated olefin copolymer is 20 mol% to 70 mol%.
A rubber composition for a crawler characterized by the above.   2. The rubber composition for a crawler according to claim 1, wherein a ratio of the conjugated diene compound-derived portion in the copolymer is from 30 mol% to 80 mol%.   The rubber composition for a crawler according to claim 1 or 2, wherein the copolymer has a cis-1,4 bond content of the portion derived from the conjugated diene compound of 50% or more.   The rubber composition for a crawler according to any one of claims 1 to 3, wherein the conjugated diene polymer contains at least one selected from the group consisting of natural rubber and styrene-butadiene copolymer rubber. object.   The rubber composition for a crawler according to any one of claims 1 to 4, wherein the copolymer has a polystyrene-reduced weight average molecular weight of 10,000 to 10,000,000.   6. The rubber composition for a crawler according to claim 1, wherein the copolymer has a molecular weight distribution (Mw / Mn) of 10 or less.   The rubber composition for a crawler according to any one of claims 1 to 6, wherein the non-conjugated olefin is an acyclic olefin.   The rubber composition for a crawler according to any one of claims 1 to 7, wherein the non-conjugated olefin has 2 to 10 carbon atoms.   The rubber composition for a crawler according to any one of claims 1 to 8, wherein the non-conjugated olefin is at least one selected from the group consisting of ethylene, propylene, and 1-butene.   The rubber composition for a crawler according to claim 9, wherein the non-conjugated olefin is ethylene.   The rubber composition for a crawler according to any one of claims 1 to 10, wherein the conjugated diene compound is at least one selected from the group consisting of 1,3-butadiene and isoprene.   The rubber composition for a crawler according to any one of claims 1 to 11, comprising 60 to 80 parts by mass of the conjugated diene polymer with respect to 100 parts by mass of the rubber component.   A rubber crawler comprising the crawler rubber composition according to claim 1.

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