JP2013155301A - Vibration-proof rubber composition and vibration-proof rubber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a vibration-proof rubber composition that can improve ozone resistance (weatherability) and crack growth resistance of a vibration-proof rubber, and that can lower the dynamic-to-static modulus ratio; and the vibration-proof rubber.SOLUTION: A vibration-proof rubber composition includes, in a rubber component: a conjugated diene polymer; a conjugated diene compound-nonconjugated olefin copolymer; and a nonconjugated diene compound-nonconjugated olefin copolymer containing an ethylene-propylene-diene rubber.

Description

  The present invention relates to an anti-vibration rubber composition and an anti-vibration rubber, and in particular, an anti-vibration rubber composition capable of improving the ozone resistance (weather resistance) and crack growth resistance of the anti-vibration rubber and reducing the dynamic ratio. And vibration-proof rubber.

  Conventionally, in various vehicles such as automobiles, in order to improve the comfort of passengers, various anti-vibration materials have been arranged at sites that are sources of vibration and noise to reduce the intrusion of vibration and noise into the room. Attempts have been made. For example, for engines that are the main source of vibration and noise, vibrations during engine drive are absorbed by using anti-vibration rubber for components such as torsional dampers, engine mounts, and muffler hangers. Reduces the intrusion of vibration and noise and the spread of noise to the surrounding environment.

  As a basic characteristic of such an anti-vibration rubber, a strength characteristic that supports a heavy object such as an engine and an anti-vibration performance that absorbs and suppresses the vibration are required. Furthermore, when used in a high temperature environment such as an engine room, it is required to have high ozone resistance as well as excellent strength characteristics, low dynamic magnification, and excellent anti-vibration performance. Further, excellent crack growth resistance is also an important issue as one of the characteristics of the vibration-proof rubber.

  (I) natural rubber (NR), (ii) ethylene-propylene-diene rubber (EPDM), (iii) peroxide as vulcanizing agent, and (iv) zinc acrylate or methacrylic acid as co-crosslinking agent Studies have been undertaken to obtain anti-vibration rubbers with significantly improved creep resistance while maintaining heat resistance, tear resistance, high strength and low dynamic ratio by blending zinc with the anti-vibration rubber composition. (For example, see Patent Document 1).

  However, natural rubber (NR) and ethylene-propylene-diene rubber (EPDM) are incompatible polymers, and the island phase (ethylene-propylene-diene rubber (EPDM)) is uniform in the sea phase (natural rubber (NR)). In addition, it is difficult to disperse the polymer in an incompatible polymer, and there is little entanglement of polymer molecules between the incompatible polymers, and there is room for improvement in crack growth resistance and ozone resistance of the anti-vibration rubber. (Dynamic ratio) also had room for improvement.

  Therefore, (i) a study to improve the physical properties (particularly fatigue) of the vibration-proof rubber by controlling the morphology of natural rubber (NR) / ethylene-propylene-diene rubber (EPDM) (see, for example, Patent Document 2) ) And (ii) Zinc acrylate (ZA), Zinc methacrylate (ZMA), Fatty acid ester, Bismaleimide, Trimethylolpropane trimethacrylate, Dimethacrylic acid ethylene glycol, etc. are effectively cross-linked. Thus, studies have been made to improve the physical properties (particularly, crack growth resistance, dynamic magnification, creep resistance) of the anti-vibration rubber (see, for example, Patent Documents 3 to 5), Anti-vibration rubbers that improve the ozone resistance (weather resistance) and crack growth resistance of vibration-proof rubbers and can reduce dynamic magnification have not yet been developed. At present, the calling has been strongly desired.

JP 2011-144321 A JP 2010-260921 A JP 2009-298949 A JP 2011-46795 A JP 2011-132413 A

  Accordingly, an object of the present invention is to provide an anti-vibration rubber composition and an anti-vibration rubber that can improve the ozone resistance (weather resistance) and crack growth resistance of the anti-vibration rubber and reduce the dynamic magnification. is there.

  The present inventors blended a conjugated diene compound-nonconjugated olefin copolymer as a rubber component of the vibration-proof rubber composition, thereby conjugated diene polymer (for example, natural rubber) (island phase) / nonconjugated. The ozone resistance can be improved by controlling the morphology of the diene compound-nonconjugated olefin copolymer (for example, EPDM) (sea phase), and the conjugated diene in the conjugated diene compound-nonconjugated olefin copolymer can be improved. It has been found that the dynamic characteristics (dynamic magnification) can be improved by the influence of the compound components, and the present invention has been completed.

That is, the anti-vibration rubber composition of the present invention comprises a rubber component containing a conjugated diene polymer, a conjugated diene compound-non-conjugated olefin copolymer, and a non-conjugated diene compound-non-containing rubber containing ethylene-propylene-diene rubber. And a conjugated olefin copolymer.
The rubber component contains a conjugated diene polymer, a conjugated diene compound-nonconjugated olefin copolymer, and a nonconjugated diene compound-nonconjugated olefin copolymer containing ethylene-propylene-diene rubber. The ozone resistance (weather resistance) and crack growth resistance of the vibration rubber can be improved, and the dynamic magnification can be lowered.

The anti-vibration rubber composition of the present invention preferably further contains a vulcanizing agent in the rubber component.
If the rubber component further contains a vulcanizing agent, the heat resistance and durability (creep resistance at high temperature) of the vibration-proof rubber can be improved.

In the vibration-proof rubber composition of the present invention, the vulcanizing agent preferably contains a peroxide.
When the vulcanizing agent contains a peroxide, it is possible to further improve the heat resistance and durability (creep resistance at high temperature) of the vibration-proof rubber.

The vibration-proof rubber composition of the present invention preferably further contains a co-crosslinking agent in the rubber component.
If the rubber component further contains a co-crosslinking agent, the crack growth resistance of the vibration-proof rubber can be further improved.

In the vibration-proof rubber composition of the present invention, the co-crosslinking agent preferably contains zinc acrylate or zinc methacrylate.
When the co-crosslinking agent contains zinc acrylate or zinc methacrylate, the crack growth resistance of the vibration-proof rubber can be further improved.

In the vibration-proof rubber composition of the present invention, in the conjugated diene compound-nonconjugated olefin copolymer, the proportion of the conjugated diene compound-derived portion is preferably 30 mol% to 80 mol%.
In the conjugated diene compound-nonconjugated olefin copolymer, when the proportion of the conjugated diene compound-derived portion is 30 mol% to 80 mol%, the compatibility with the conjugated diene polymer is improved, and the workability and elastic modulus are increased. Can be sufficiently secured, and the weather resistance can be improved.

In the vibration-proof rubber composition of the present invention, in the conjugated diene compound-nonconjugated olefin copolymer, the cis-1,4 bond content of the conjugated diene compound-derived portion is preferably 50% or more.
In the conjugated diene compound-nonconjugated olefin copolymer, when the cis-1,4 bond content of the conjugated diene compound-derived portion is 50% or more, a low glass transition point (Tg) can be maintained. The physical properties such as crack growth resistance and wear resistance are improved.

In the vibration-proof rubber composition of the present invention, the conjugated diene compound-nonconjugated olefin copolymer preferably has a polystyrene-reduced weight average molecular weight of 10,000 to 10,000,000.
When the weight average molecular weight in terms of polystyrene of the conjugated diene compound-nonconjugated olefin copolymer is 10,000 to 10,000,000, deterioration of molding processability can be prevented.

In the vibration-proof rubber composition of the present invention, the molecular weight distribution (Mw / Mn) of the conjugated diene compound-nonconjugated olefin copolymer is preferably 10 or less.
When the molecular weight distribution (Mw / Mn) of the conjugated diene compound-nonconjugated olefin copolymer is 10 or less, the physical properties can be made uniform.

  In the vibration-proof rubber composition of the present invention, the non-conjugated olefin in the conjugated diene compound-non-conjugated olefin copolymer is preferably an acyclic olefin.

  In the vibration-proof rubber composition of the present invention, the nonconjugated olefin in the conjugated diene compound-nonconjugated olefin copolymer preferably has 2 to 10 carbon atoms.

  In the vibration-proof rubber composition of the present invention, the non-conjugated olefin in the conjugated diene compound-non-conjugated olefin copolymer is at least one selected from the group consisting of ethylene, propylene, and 1-butene. preferable.

  In the vibration-proof rubber composition of the present invention, the non-conjugated olefin in the conjugated diene compound-non-conjugated olefin copolymer is preferably ethylene.

  The vibration-proof rubber of the present invention is characterized by using the vibration-proof rubber composition of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the anti-vibration rubber composition and anti-vibration rubber which can improve the ozone resistance (weather resistance) and crack growth resistance of an anti-vibration rubber, and can make a dynamic magnification low can be provided.

FIG. 1 is a diagram showing a ¹³ C-NMR spectrum chart of copolymer A produced according to Preparation Example 1. FIG. 2 is a diagram showing a DSC curve of copolymer A produced according to Preparation Example 1. FIG. 3 is a diagram showing a DSC curve of copolymer C produced according to Preparation Example 3.

(Anti-vibration rubber)
The anti-vibration rubber of the present invention includes at least (i) a rubber component, and further includes (ii) a vulcanizing agent, (iii) a co-crosslinking agent, and (iv) other components as necessary. Become.

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

-Conjugated diene polymer (A)-
The conjugated diene polymer (A) means a polymer (polymer) containing no non-conjugated olefin as a monomer unit component (a part of the copolymer). Styrene is not included in the non-conjugated olefin.
The conjugated diene polymer (A) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include natural rubber (NR), various polybutadiene rubbers (BR), and synthetic polyisoprene rubber (IR). Various styrene-butadiene copolymer rubber (SBR), ethylene-propylene rubber (EPR), styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene copolymer rubber, acrylonitrile-butadiene Examples include copolymer rubber (NBR) and chloroprene rubber. These may be used individually by 1 type and may use 2 or more types together.
Among these, natural rubber (NR), synthetic polyisoprene rubber (IR), various polybutadiene rubbers (BR), and styrene-butadiene copolymer rubber (SBR) are non-conjugated containing ethylene-propylene-diene rubber described later. The compatibility with the diene compound-nonconjugated olefin copolymer (C) is good, and this is preferable in that the fracture resistance and crack growth resistance can be improved.

The content of the conjugated diene polymer (A) in 100 parts by mass of the rubber component is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 30 parts by mass to 65 parts by mass, 40 mass parts-60 mass parts are more preferable.
The content of the conjugated diene polymer (A) in 100 parts by mass of the rubber component is
When it is 30 parts by mass or more, it is possible to prevent deterioration of fracture resistance and workability,
It can prevent that a weather resistance deteriorates that it is 65 mass parts or less. Moreover, when content of the said conjugated diene polymer (A) in 100 mass parts of said rubber components exists in the said more preferable range, it is advantageous at the point of the balance of each performance.

-Conjugated diene compound-Non-conjugated olefin copolymer (B)-
The rubber composition of the present invention contains the conjugated diene compound-nonconjugated olefin copolymer (B), so that the conjugated diene portion of the conjugated diene compound-nonconjugated olefin copolymer (B) component is conjugated diene-based heavy. By improving the compatibility with the combined (A) component, and the non-conjugated olefin part of the (B) component improving the compatibility with the non-conjugated diene compound-non-conjugated olefin copolymer (C), fracture resistance And compatibility between the conjugated diene polymer (A) excellent in crack growth resistance and the nonconjugated diene compound-nonconjugated olefin copolymer (C) containing ethylene-propylene-diene rubber excellent in weather resistance. As a result of improvement, the weather resistance, fracture resistance and crack growth resistance of the rubber composition can be compatible at a high level. The conjugated diene compound-nonconjugated olefin copolymer (B) is a copolymer of a conjugated diene compound and a nonconjugated olefin, and 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.
Moreover, it becomes possible to improve crack growth resistance, a weather resistance, and heat resistance by making the amount of cis 1,4-bonds of the conjugated diene compound-derived portion 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.

  In the conjugated diene compound-nonconjugated olefin copolymer (B), the weight average molecular weight (Mw) does not cause a problem of lowering the molecular weight, and the weight average molecular weight (Mw) is not particularly limited. However, from the viewpoint of application to a polymer structural material, the polystyrene-equivalent weight average molecular weight (Mw) of the copolymer is preferably 10,000 to 10,000,000, more preferably 10,000 to 1,000,000. Preferably, 50,000-600,000 is more preferable. 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, and more preferably 6 or less. When the molecular weight distribution is 10 or less, the physical properties can be made 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).

In the conjugated diene compound-nonconjugated olefin copolymer (B), 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.
Using any of the specific examples of the conjugated diene compound described above, the block copolymer and the random copolymer can be prepared by the same mechanism.

  On the other hand, in the conjugated diene compound-nonconjugated olefin copolymer (B), the nonconjugated olefin used as a monomer is a nonconjugated olefin other than the conjugated diene compound, and has excellent heat resistance and the main chain of the copolymer. It is possible to increase the degree of design freedom as an elastomer by reducing the proportion of double bonds in the resin and reducing the crystallinity. As a kind of 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. 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 a non-conjugated olefin is provided, it exhibits excellent crystal properties such as breaking strength because it exhibits static crystallinity.

The content of the conjugated diene compound-containing non-conjugated olefin copolymer (B) in the conjugated diene compound-derived portion is not particularly limited as the content of the 1,2-adduct portion (including the 3,4-adduct portion) of the conjugated diene compound, Although it can select suitably according to the objective, 5% or less is preferable, 3% or less is more preferable, and 2.5% or less is especially preferable.
The conjugated diene compound-nonconjugated olefin copolymer (B) has a 1,2 adduct portion (including a 3,4 adduct portion) content of the conjugated diene compound in a portion derived from the conjugated diene compound of 5% or less. The weather resistance and ozone resistance of the copolymer can be further improved.
In addition, 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.

  There is no restriction | limiting in particular as a chain structure of the said conjugated diene compound-nonconjugated olefin copolymer (B), According to the objective, it can select suitably, For example, a block copolymer, a random copolymer, a taper copolymer. A polymer, 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 (B) is a block copolymer, the block portion made of the monomer of the nonconjugated olefin exhibits static crystallinity, and therefore mechanical properties such as breaking strength. Excellent. The block portion showing crystallinity can suppress a decrease in storage elastic modulus (G ′).

--Random copolymer--
When the conjugated diene compound-nonconjugated olefin copolymer (B) 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. The crystallization temperature derived from the block part 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 the alternating copolymer, both flexibility and adhesiveness can be achieved.

  In the present invention, when the conjugated diene compound-nonconjugated olefin copolymer (B) is a block copolymer, the block portion composed of the monomer of the nonconjugated olefin exhibits static crystallinity. Therefore, the copolymer is preferably at least one selected from a block copolymer and a tapered copolymer.

Moreover, there is no restriction | limiting in particular as content of the said conjugated diene compound-nonconjugated olefin copolymer (B) in 100 mass parts of said rubber components, Although it can select suitably according to the objective, 5 mass parts -20 mass parts is preferable, and 10-15 mass parts is more preferable.
When the content of the conjugated diene compound-nonconjugated olefin copolymer (B) in 100 parts by mass of the rubber component is 5 parts by mass or more, the morphology can be improved and the weather resistance is prevented from deteriorating. When it is 20 parts by mass or less, it is possible to prevent deterioration of fracture resistance and workability.
Moreover, when the content of the conjugated diene compound-nonconjugated olefin copolymer (B) in 100 parts by mass of the rubber component is within the more preferable range, it is advantageous in terms of balance of performances.

--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 conjugated diene compound-nonconjugated olefin copolymer includes a step of polymerizing a conjugated diene compound and a nonconjugated olefin in the presence of the polymerization catalyst or polymerization catalyst composition shown below.
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.

  According to the above production method, except that the polymerization catalyst or the polymerization catalyst composition is used, the monomer conjugated diene compound and the non-conjugated olefin are produced in the same manner as in the production method of the polymer using the normal coordination ion polymerization catalyst. It 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）：

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Ｒは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｘ’は、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体、並びに下記一般式（ＩＩＩ）：

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Ｒ’は、無置換もしくは置換シクロペンタジエニル、インデニル又はフルオレニルを示し、Ｘは、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示し、［Ｂ］⁻は、非配位性アニオンを示す）で表されるハーフメタロセンカチオン錯体からな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、該重合触媒組成物は、更に、通常のメタロセン錯体を含む重合触媒組成物に含有される他の成分、例えば助触媒等を含んでいてもよい。ここで、メタロセン錯体は、一つ又は二つ以上のシクロペンタジエニル又はその誘導体が中心金属に結合した錯体化合物であり、特に、中心金属に結合したシクロペンタジエニル又はその誘導体が一つであるメタロセン錯体を、ハーフメタロセン錯体と称することがある。なお、重合反応系において、第一重合触媒組成物に含まれる錯体の濃度は０．１〜０．０００１ｍｏｌ／Ｌの範囲であることが好ましい。 <First polymerization catalyst composition>
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):

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

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R ′ represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxide group or a thiolate group. represents an amide group, a silyl group or a hydrocarbon group having a carbon number of 1 to 20, L is a neutral Lewis base, w is, an integer of 0 to 3, [B] ^- is a non-coordinating A polymerization catalyst composition (hereinafter also referred to as a first polymerization catalyst composition) comprising at least one complex selected from the group consisting of a half metallocene cation complex represented by The product 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 general formula (I) and formula (II), Cp ^R in the formula is an unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton may be represented by C ₉ H _7-X R _X or C ₉ H _11-X R _X. Here, X is an integer of 0-7 or 0-11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of the substituted indenyl include 2-phenylindenyl and 2-methylindenyl. Note that the two Cp ^Rs in the general formulas (I) and (II) may be the same as or different from each other.

（式中、Ｒは水素原子、メチル基又はエチル基を示す。） In the half metallocene cation complex represented by the above 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.

(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 the 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) includes a silylamide ligand [—N (SiR ₃ ) ₂ ]. The R groups (R ^{a to} R ^f in the general formula (I)) 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 ^{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 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.

  Moreover, 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, a dimer or It may be present as a higher multimer.

（式中、Ｘ’’はハライドを示す。） 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.)

（式中、Ｘ’’はハライドを示す。） 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.

(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.

[A] Examples of the cation represented by ⁺ 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, and is an 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 a metallocene complex represented by the general formula (I) or the formula (II) and an 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>
In addition, as the polymerization catalyst composition,
Component (a): 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): includes 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 Preferable examples include 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
When the second polymerization catalyst composition contains at least one of an ionic compound (b-1) and a 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 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 characterized by including.

The second polymerization catalyst composition used in the method for producing the copolymer needs to contain the component (a) and the component (b), where 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) have no 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 the said polymerization catalyst composition is a case where the said aluminoxane (b-2) is included, 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. Represents 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 names made by Shell Chemical Co., Ltd., a mixture of isomers of C10 monocarboxylic acid Synthetic acids composed of products], residues of carboxylic acids such as phenylacetic acid, benzoic acid, 2-naphthoic acid, maleic acid, succinic acid; hexanethioic acid, 2,2-dimethylbutanethioic acid, decanethioic acid, thiobenzoic acid Residues of thiocarboxylic acids such as acids, dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, phosphoric acid Dilauryl, dioleyl phosphate, diphenyl phosphate, bis (p-nonylphenyl) phosphate, bis (polyethylene glycol-p-nonylphenyl) phosphate, (butyl) phosphate (2-ethylhexyl), phosphate (1-methyl) Phosphoric acid ester such as heptyl) (2-ethylhexyl), phosphoric acid (2-ethylhexyl) (p-nonylphenyl) 2-ethylhexylphosphonate monobutyl, 2-ethylhexylphosphonate mono-2-ethylhexyl, phenylphosphonate mono-2-ethylhexyl, 2-ethylhexylphosphonate mono-p-nonylphenyl, phosphonate mono-2- Residues of phosphonates such as ethylhexyl, mono-1-methylheptyl phosphonate, mono-p-nonylphenyl phosphonate, dibutylphosphinic acid, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid , Dilaurylphosphinic acid, dioleylphosphinic acid, diphenylphosphinic acid, bis (p-nonylphenyl) phosphinic acid, butyl (2-ethylhexyl) phosphinic acid, (2-ethylhexyl) (1-methylheptyl) phosphinic acid, (2 -Ethylhe Xylyl) (p-nonylphenyl) phosphinic acid, butylphosphinic acid, 2-ethylhexylphosphinic acid, 1-methylheptylphosphinic acid, oleylphosphinic acid, laurylphosphinic acid, phenylphosphinic acid, p-nonylphenylphosphinic acid, etc. Can also be mentioned. These ligands may be used alone or in combination of two or more.

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 aluminoxane 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, and among these, a methyl group is preferable. Examples of the organoaluminum compound used as an aluminoxane raw material include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof, and trimethylaluminum is particularly preferable. For example, an aluminoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can be preferably used. The content of the aluminoxane in the 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. By reacting with a certain 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, as well as III, IV, 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 the component (c) described above can be used singly 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 said 2nd polymerization catalyst composition, it is still more preferable that it is about 10 times mole.

<Polymerization catalyst and third polymerization catalyst composition>
The polymerization catalyst is for polymerization of a conjugated diene compound and a non-conjugated olefin, and has the 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、Ｍ^１は、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Ｒは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^ａ及びＲ^ｂは、それぞれ独立して炭素数１〜２０の炭化水素基を示し、該Ｒ^ａ及びＲ^ｂは、Ｍ^１及びＡｌにμ配位しており、Ｒ^ｃ及びＲ^ｄは、それぞれ独立して炭素数１〜２０の炭化水素基又は水素原子を示す］で表されるメタロセン系複合触媒が挙げられる。 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 an unsubstituted or substituted indenyl group, and R ^a and R ^b each independently represent 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

  The third polymerization catalyst composition includes the metallocene composite catalyst and a boron anion.

<Metalocene composite catalyst>
Hereinafter, the metallocene composite catalyst will be described in detail. The metallocene composite catalyst includes a lanthanoid element, a rare earth element of scandium or yttrium, and a Group 13 element of the periodic table, and has the following formula (A):
R _a MX _b QY _b (A)
[In the formula, each R independently represents 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.] By using the metallocene polymerization catalyst, a copolymer of a conjugated diene compound and a non-conjugated olefin 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. Preferable examples of the metal M ¹ include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

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

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

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

（式中、Ｍ^２は、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Ｒは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^Ｅ〜Ｒ^Ｊは、それぞれ独立して炭素数１〜３のアルキル基又は水素原子を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体を、ＡｌＲ^ＫＲ^ＬＲ^Ｍで表される有機アルミニウム化合物と反応させることで得られる。なお、反応温度は室温程度にすればよいので、温和な条件で製造することができる。また、反応時間は任意であるが、数時間〜数十時間程度である。反応溶媒は特に限定されないが、原料及び生成物を溶解する溶媒であることが好ましく、例えばトルエンやヘキサンを用いればよい。なお、上記メタロセン系複合触媒の構造は、^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 has 1 to 3 carbon atoms. An alkyl group or a hydrogen atom, L represents a neutral Lewis base, w represents an integer of 0 to 3, and a metallocene complex represented by AlR ^K R ^L R ^M It is obtained by reacting with. In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene or hexane may be used. 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. In addition, it is preferable that at least one of R ^{E to} R ^J is a hydrogen atom. By making at least one of R ^{E to} R ^J a hydrogen atom, the synthesis of the catalyst becomes easy. Furthermore, a methyl group is preferable as the alkyl group.

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

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

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

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

  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. In addition, these aluminoxanes may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the method for producing a copolymer, as described above, polymerization is carried out in the same manner as in the method for producing a polymer using a normal coordination ion polymerization catalyst, except that the polymerization catalyst or the polymerization catalyst composition is used. be able to. Here, in the copolymer production method, for example, (1) a component of the polymerization catalyst composition is separately provided in a polymerization reaction system including a conjugated diene compound as a monomer and a non-conjugated olefin other than the conjugated diene compound. The polymerization catalyst composition may be used 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.

  In the method for producing a copolymer, the polymerization may be stopped using a polymerization terminator such as methanol, ethanol, or isopropanol.

  In the method for producing a copolymer, 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. The reaction time of the polymerization reaction is not particularly limited and is preferably in the range of 1 second to 10 days, for example, but can be appropriately selected depending on conditions such as the type of monomer to be polymerized, the type of catalyst, and the polymerization temperature.

  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) means the following formula:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.0
It is preferable to satisfy the relationship:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.3
And more preferably the following formula:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.7
Satisfy the relationship. 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.

  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.

<Non-conjugated diene compound-non-conjugated olefin copolymer (C)>
The rubber composition of the present invention contains a non-conjugated diene compound-non-conjugated olefin copolymer (C) containing ethylene-propylene-diene rubber (EPDM). Excellent weather resistance can be realized by EPDM contained in the non-conjugated diene compound-non-conjugated olefin copolymer (C).

  The non-conjugated diene compound-non-conjugated olefin copolymer (C) is a copolymer of a non-conjugated diene compound and a non-conjugated olefin, and includes a non-conjugated olefin as a monomer unit component in the copolymer. Furthermore, the diene content of the nonconjugated diene compound-nonconjugated olefin copolymer (C) is 10% or less.

  Here, regarding the EPDM contained in the non-conjugated diene compound-non-conjugated olefin copolymer (C), a small amount of the third component is added to the ethylene propylene rubber (EPM) which is a copolymer of ethylene and propylene. Introduced and provided with a double bond in the main chain. There are various synthetic rubbers depending on the type and amount of the third component, and typical third components include ethylidene norbornene (ENB), 1,4-hexadiene (1,4-HD), dicyclopentadiene (DCP). ) And the like. Regarding the properties of the EPDM, in addition to the above weather resistance, it is excellent in aging resistance, cold resistance, solvent resistance and the like.

  Moreover, it is preferable that content of EPDM in the said nonconjugated diene compound-nonconjugated olefin copolymer (C) is 10 mass% or more. This is because if the content is less than 10% by mass, the EPDM content is too small, and sufficient weather resistance may not be ensured.

In addition, about the other conditions (a conjugated diene compound, nonconjugated olefin copolymers other than EPDM, a manufacturing method, etc.) of the said nonconjugated diene compound-nonconjugated olefin copolymer (C), the said conjugated diene compound-nonconjugated. It is the same as that of the olefin copolymer (A).

There is no restriction | limiting in particular as content of the said nonconjugated diene compound-nonconjugated olefin copolymer (C) in 100 mass parts of said rubber components, Although it can select suitably according to the objective, 30 mass parts- 65 parts by mass is preferable, and 35 to 60 parts by mass is more preferable.
When the content of the non-conjugated diene compound-non-conjugated olefin copolymer (C) in 100 parts by mass of the rubber component is 30 parts by mass or more, sufficient weather resistance is obtained, which is 65 parts by mass or less. And sufficient crack growth resistance can be obtained.
Further, when the content of the non-conjugated diene-non-conjugated olefin copolymer (C) in 100 parts by mass of the rubber component is within the more preferable range, it is advantageous in terms of weather resistance.

<Mass ratio of (A), (B) and (C)>
The mass ratio of the conjugated diene polymer (A), the conjugated diene compound-nonconjugated olefin copolymer (B), and the nonconjugated diene compound-nonconjugated olefin copolymer (C) is particularly limited. However, it is preferably 60:10:30 to 30:15:55 from the viewpoint that the weather resistance, fracture resistance, and workability can be exhibited in a balanced manner.
When the mass ratio of the conjugated diene compound-nonconjugated olefin copolymer (B) is less than 10%, the compatibilizing effect may not be sufficiently obtained, and the nonconjugated diene compound-nonconjugated olefin copolymer When the mass ratio of (C) is less than 30%, the effect of weather resistance may not be sufficiently obtained, and when the mass ratio of the non-conjugated diene compound-non-conjugated olefin copolymer (C) exceeds 55%. There is a possibility that the effect of crack growth resistance cannot be sufficiently obtained.

-Other rubber components-
There is no restriction | limiting in particular as said other rubber | gum, According to the objective, it can select suitably, For example, polysulfide rubber, silicone rubber, fluororubber, urethane rubber etc. are mentioned. About another rubber component, it may be used individually by 1 type and may use 2 or more types together.

<(Ii) Vulcanizing agent>
As the vulcanizing agent, it is preferable to use only a peroxide. By peroxide-crosslinking the rubber component using only the peroxide as a vulcanizing agent, it is superior in heat resistance and creep resistance at high temperatures compared to the case of crosslinking using sulfur. The heat resistance and durability of the vibration rubber can be increased.
There is no restriction | limiting in particular as a compounding quantity of the said vulcanizing agent, Although it can select suitably according to the objective, 1 mass part-10 mass parts are preferable with respect to 100 mass parts of said rubber components, 2 mass parts -8 mass parts is more preferable.
When the blending amount of the vulcanizing agent is 1 part by mass or more, it is possible to prevent a decrease in crosslinking density, a decrease in breaking strength, a deterioration in dynamic magnification, a deterioration in compression set, a decrease in durability, and the like. When the amount is 10 parts by mass or less, it is possible to prevent the rubber from being excessively cured and causing a decrease in elongation at break and a decrease in durability.

-Peroxide-
The peroxide is not particularly limited and may be appropriately selected depending on the intended purpose. For example, dicumyl peroxide, benzoyl peroxide, 1,1-bis (t-butylperoxy) -3,5 , 5-trimethylcyclohexane, diisobutyryl peroxide, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, 1,1,3 , 3-tetramethylbutylperoxyneodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneodecanoate, t -Butyl peroxyneodecanoate, t-butyl peroxy Neoheptanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, 1,1,3,3-tetra Methylbutylperoxy-2-ethylhexanoate, disuccinic acid peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexano , Di (4-methylbenzoyl) peroxide, t-butylperoxy-2-ethylhexanoate, di (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide, 1,1-di (t-butylperoxy) -2-methylcyclohexane, , 1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2, , 2-di (4,4-di- (t-butylperoxy) cyclohexyl) propane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5 , 5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-di-methyl -2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2 , 2-Di- (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl 4,4-di- (t-butylperoxy) valerate, di (2-t-butylperoxyisopropyl) Benzene, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroper Oxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide. These may be used individually by 1 type and may use 2 or more types together.
Among these, di (2-t-butylperoxyisopropyl) benzene and dicumyl peroxide are preferable.

<(Iii) Co-crosslinking agent>
The co-crosslinking agent is not an additive itself, but is an additive that causes a crosslinking reaction in rubber when used in combination with the peroxide.
The co-crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include zinc acrylate, zinc methacrylate, lower alkylene glycol diacrylate, lower alkylene glycol dimethacrylate, and the like. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together.

-Zinc acrylate, zinc methacrylate-
There is no restriction | limiting in particular as said zinc acrylate, According to the objective, it can select suitably, For example, zinc diacrylate (Zinc Diacrylate) etc. are mentioned.
There is no restriction | limiting in particular as said zinc methacrylate, According to the objective, it can select suitably, For example, zinc dimethacrylate (Zinc Dimethacrylate) etc. are mentioned.
There is no restriction | limiting in particular as a lower limit of the compounding quantity of the said zinc acrylate or the said zinc methacrylate, Although it can select suitably according to the objective, 1.5 mass parts or more with respect to 100 mass parts of said rubber components Is preferable, and 2.0 mass parts or more is more preferable.
Moreover, there is no restriction | limiting in particular as an upper limit of the compounding quantity of the said zinc acrylate or the said zinc methacrylate, Although it can select suitably according to the objective, It is 10 mass parts or less with respect to 100 mass parts of said rubber components. Is preferable, and 8 parts by mass or less is more preferable.
When the blending amount is less than or equal to the upper limit value, it is possible to prevent the rubber from being excessively cured and causing a decrease in elongation at break, and when it is greater than or equal to the lower limit value, the rubber is sufficiently crosslinked. It can be prevented that the breaking strength is lowered, the tear strength is lowered, the dynamic magnification is increased, and the compression set is increased.

In addition, fatty acid esters can be blended with rubber components together with zinc acrylate or zinc methacrylate, thereby improving the dispersibility of the zinc acrylate or zinc methacrylate with respect to the rubber component during kneading and vulcanization. The mechanical properties of the later rubber can be improved.
Both the fatty acid and alcohol constituting the fatty acid ester may have a linear structure or a branched structure, may be saturated or unsaturated, and the number of carbon atoms is not particularly limited. For example, as the fatty acid ester, a known fatty acid ester composed of a fatty acid having a chain length of 1 to 30 carbon atoms and an alcohol having a chain length of 1 to 30 carbon atoms can be used.
The fatty acid ester is not particularly limited and may be appropriately selected depending on the intended purpose. For example, stearic acid ethyl ester, stearic acid propyl ester, stearic acid butyl ester, palmitic acid ethyl ester, palmitic acid propyl ester, palmitic acid Acid butyl ester, and the like. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as a compounding quantity of the said fatty acid ester, Although it can select suitably according to the objective, 0.02 mass part-1.2 mass parts are preferable with respect to 100 mass parts of said rubber components, 0 .2 parts by mass to 0.6 parts by mass are more preferable. When the blending amount of the fatty acid ester is 1.2 parts by mass or less, it is possible to prevent rubber softening, deterioration of workability, deterioration of dynamic magnification, and the like, and 0.02 parts by mass or more. And the effect of improving dispersibility is obtained.

  This fatty acid ester exhibits the effect of improving dispersibility even when blended separately with the zinc acrylate or zinc methacrylate when kneaded with the rubber component. By premixing with zinc methacrylate, the dispersibility of zinc acrylate or zinc methacrylate in the rubber component can be further improved.

  As the co-crosslinking agent, dialkyl acrylate lower alkylene glycol or dimethacrylate acrylate can be used in combination with the zinc acrylate or zinc methacrylate.

［但し、式（１），（２）中のＡＯは、それぞれ、エチレンオキサイド、プロピレンオキサイド又はブチレンオキサイドから選ばれる。また、式（１），（２）中のｎは、それぞれ１〜４の整数を表す。］
に示されるものが用いられる。
前記低級アルキレングリコールとしては、特に制限はなく、目的に応じて適宜選択することができ、例えば、モノエチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール等の（ポリ）エチレングリコール；モノプロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、ポリプロピレングリコール等の（ポリ）プロピレングリコール；１，２−プロパンジオール、１，３−プロパンジオール等の（ポリ）プロパンジオール；１，２−ブタンジオール、１，３−ブタンジオール、１，４−ブタンジオール等の（ポリ）ブタンジオール；などが挙げられる。これらは１種単独で用いてもよく、或いは２種以上が分子構造内に含まれていてもよい。
これらの中でも、エチレングリコールが好ましく、また、上記式（１）、（２）中のｎ＝１〜４のうち、ｎが１であることが好ましい。
この低級アルキレングリコールの炭素数が多くなると、圧縮永久歪みの悪化を招くおそれがある。また、ｎの値が多くなると、圧縮永久歪みの悪化を招くおそれがある。 Here, as the dialkylene glycol or dimethacrylic acid lower alkylene glycol, specifically, the following general formula (1) or (2)

[However, AO in the formulas (1) and (2) is selected from ethylene oxide, propylene oxide, or butylene oxide, respectively. Moreover, n in Formula (1), (2) represents the integer of 1-4, respectively. ]
The one shown in is used.
The lower alkylene glycol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include (poly) ethylene glycol such as monoethylene glycol, diethylene glycol, triethylene glycol and polyethylene glycol; monopropylene glycol, diethylene glycol (Poly) propylene glycol such as propylene glycol, tripropylene glycol and polypropylene glycol; (Poly) propanediol such as 1,2-propanediol and 1,3-propanediol; 1,2-butanediol, 1,3-butane (Poly) butanediol such as diol and 1,4-butanediol; These may be used individually by 1 type, or 2 or more types may be contained in the molecular structure.
Among these, ethylene glycol is preferable, and n is preferably 1 among n = 1 to 4 in the above formulas (1) and (2).
If the number of carbon atoms of the lower alkylene glycol is increased, the compression set may be deteriorated. Further, when the value of n increases, the compression set may be deteriorated.

  The lower limit of the amount of the diacrylic acid lower polyalkylene glycol or dimethacrylic acid lower polyalkylene glycol is not particularly limited and may be appropriately selected depending on the intended purpose. On the other hand, 0.4 mass part or more is preferable and 0.8 mass part or more is more preferable. The upper limit of the amount of the diacrylic acid lower polyalkylene glycol or dimethacrylic acid lower polyalkylene glycol is not particularly limited and may be appropriately selected depending on the intended purpose. On the other hand, it is preferably 3.2 parts by mass or less, and more preferably 2.8 parts by mass or less. When the blending amount is less than or equal to the upper limit value, tensile elongation, tensile strength, tearing, lowering of dynamic magnification, etc. can be prevented, and when it is greater than or equal to the lower limit value, compression set is deteriorated. Etc. can be prevented.

  Further, the blending amount of zinc acrylate or zinc methacrylate with respect to 100 parts by weight of the rubber component is X parts by weight, the blending amount of diacrylic acid or lower alkylene glycols with diacrylic acid is Y parts by weight, and the total weight part of the co-crosslinking agent is X + Y. = Z parts by mass, it is preferable to satisfy 3 ≦ Z ≦ 6, more preferably 4 ≦ Z ≦ 5 from the viewpoint of effectively exhibiting the effects of the present invention. Within this range, it can be prevented that the tensile elongation, the tensile strength, the tearability is lowered, the dynamic magnification is increased, the compression set is deteriorated, and the like.

<(Iv) Other components>
As the other components, a crosslinking aid, carbon black, silica, waxes (wax, amide compound), vulcanization accelerator, antioxidant, antioxidant, filler, as long as the object of the present invention is not impaired. Additives such as foaming agents, plasticizers, lubricants, tackifiers, ultraviolet absorbers, fatty acids, anti-aging agents, softeners, retarders, zinc oxide (zinc white (ZnO)) can be appropriately blended.

-Crosslinking aid-
There is no restriction | limiting in particular as said crosslinking adjuvant, According to the objective, it can select suitably, For example, sulfur etc. are mentioned.
There is no restriction | limiting in particular as a compounding quantity of the said crosslinking adjuvant, It is preferable to set it as the range of 0.1 mass part-0.5 mass part with respect to 100 mass parts of rubber components according to the objective.

-Carbon black-
There is no restriction | limiting in particular as said carbon black, According to the objective, it can select suitably, For example, FEF, GPF, SRF, HAF, N339, IISAF, ISAF, SAF etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
The carbon black nitrogen adsorption specific surface area: The _(N 2 SA, JIS K 6217-2 compliant 2001) is not particularly limited and may be appropriately selected depending on the ^purpose, 20m 2 / ^{g~100m 2} / g are ^preferred, 35m ² / ^g~80m 2 / g is more preferable. Wherein the carbon black nitrogen adsorption specific surface area (N 2 _SA) is less than 20 m 2 / ^g, low durability of the resulting rubber, may not sufficiently crack growth resistance is obtained, 100 m ² / When it exceeds g, low loss property falls and workability | operativity may be bad.
Incidentally, the nitrogen adsorption specific surface area _(N 2 SA), for example, JIS K 6217-2: can conform to 2001, measured.
There is no restriction | limiting in particular as content of carbon black with respect to 100 mass parts of said rubber components, Although it can select suitably according to the objective, 10 mass parts-70 mass parts are preferable, and 20 mass parts-60 mass parts are. More preferred. When the content of the carbon black is 10 parts by mass or more, it is possible to prevent the reinforcing property from being insufficient and deterioration of the fracture resistance, and when it is 70 parts by mass or less, workability and low loss property are prevented. Can be prevented from deteriorating. Moreover, when the content of the carbon black is within the more preferable range, it is advantageous in terms of balance of performances.

-Silica-
By using the silica in combination with the carbon black, an increase in elastic modulus can be suppressed while maintaining the fracture characteristics of rubber.
There is no restriction | limiting in particular as said silica, Although what is normally used in this field | area can be used, Hydrophobized silica is preferable.
As the hydrophobic treated silica is not particularly limited and may be appropriately selected depending on the purpose, the nitrogen adsorption specific surface area (BET method) is 150m ² / g~500m ² / g (preferably 150～350M ² / g with respect to wet silica 100 parts by weight in the range of), kinematic viscosity ^{10 -6 m 2 / s~1m 2 /} s silicone oil 0.1 part by weight to 50 parts by mass to surface treatment in the range of What is obtained is preferable.
When the specific surface area of the wet silica is less than 150 m ² / g, desired fracture characteristics may not be obtained, and when it exceeds 500 m ² / g, dispersibility in the rubber component may be reduced. In addition, there is no restriction | limiting in particular as DBP absorption amount of the said silica, Although it can select suitably according to the objective, 150 ml / 100g-350 ml / 100g are preferable.

There is no restriction | limiting in particular as addition amount of the said silica, Although it can select suitably according to the objective, 1 mass part-10 mass parts are preferable with respect to 100 mass parts of rubber components, and 5 mass parts-10 masses. Part is more preferred.
If the amount of silica added exceeds 10 parts by mass, it may be difficult to obtain the desired shear modulus G, and if it is less than 1 part by mass, the effect on fracture characteristics may not be obtained.
In the present invention, when the silane is kneaded with the rubber component, a known silane coupling agent may be added as appropriate, thereby improving the dispersibility in the rubber component.

-Wax and amide compounds-
The wax and amide compound are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include waxes such as paraffin wax and microcrystalline wax; amides such as stearic acid amide, oleic acid amide and erucic acid amide. Compound; and the like. The said resin wax and an amide compound may be used individually by 1 type, and may be used in combination of 2 or more type.
Among these, microcrystalline wax and erucic acid amide are preferable in that the adhesiveness of the rubber sheet can be reduced and the molding workability can be improved.
The addition amount of the wax and amide compound is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.5 parts by mass to 2 parts by mass with respect to 100 parts by mass of the rubber component. 0.5 mass part-1 mass part are more preferable.
If the added amount of the wax or amide compound is less than 0.5 parts by mass, the desired processability improvement effect may not be obtained. If the amount exceeds 2 parts by mass, the appearance may be deteriorated. .

-Plasticizer-
The plasticizer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include process oils such as aromatic oils, naphthenic oils and paraffin oils; vegetable oils such as palm oils; synthesis of alkylbenzene oils and the like Oil; and the like.
Among these, process oil is preferable, and paraffin oil is particularly preferable.
There is no restriction | limiting in particular as addition amount of the said plasticizer, Although it can select suitably according to the objective, 20 mass parts-100 mass parts are preferable with respect to 100 mass parts of rubber components.

-Vulcanization accelerator-
The vulcanization accelerator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include CBS (N-cyclohexyl-2-benzothiazylsulfenamide) and TBBS (Nt-butyl- 2-benzothiazylsulfenamide), sulfenamide-based vulcanization accelerators such as TBSI (Nt-butyl-2-benzothiazylsulfenimide); guanidine-based additions such as DPG (diphenylguanidine) And sulfur accelerators; thiuram vulcanization accelerators such as tetraoctyl thiuram disulfide and tetrabenzyl thiuram disulfide; vulcanization accelerators such as zinc dialkyldithiophosphate; and the like.
There is no restriction | limiting in particular as addition amount of the said vulcanization accelerator, Although it can select suitably according to the objective, 1.5 mass parts-10 mass parts are preferable with respect to 100 mass parts of rubber components.

-Filler-
The filler is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include inorganic fillers such as white carbon, fine particle magnesium silicate, heavy calcium carbonate, magnesium carbonate, clay and talc, Examples thereof include organic fillers such as styrene resin, coumarone indene resin, phenol resin, lignin, modified melamine resin, and rosin derivative. There is no restriction | limiting in particular as addition amount of the said filler, Although it can select suitably according to the objective, 10 mass parts-50 mass parts are preferable with respect to 100 mass parts of rubber components.

-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.

-Softener-
There is no restriction | limiting in particular as said softener, According to the objective, it can select suitably, For example, hydrocarbon resins, such as an aromatic modified terpene hydrocarbon resin, etc. are mentioned.
There is no restriction | limiting in particular as content of the said softening agent, Although it can select suitably according to the objective, 1 mass part-15 mass parts are preferable with respect to 100 mass parts of rubber components.

-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.

-Retarder-
There is no restriction | limiting in particular as said retarder, According to the objective, it can select suitably, For example, N- (cyclohexylthio) phthalimide (PVI) etc. are mentioned.
There is no restriction | limiting in particular as content of the said retarder, Although it can select suitably according to the objective, 0.1 mass part-1.0 mass part are preferable with respect to 100 mass parts of rubber components.

-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-vibration rubber)
The vibration-proof rubber of the present invention is characterized by using the vibration-proof rubber composition of the present invention.
There is no restriction | limiting in particular as a shape, a structure, and a magnitude | size of the vibration-proof rubber of this invention, According to the objective, it can select suitably.

(Anti-Vibration Rubber Composition and Anti-Vibration Rubber Manufacturing Method)
The anti-vibration rubber composition of the present invention includes a conjugated diene polymer, a conjugated diene compound-nonconjugated olefin copolymer, and a rubber component containing at least a nonconjugated diene compound-nonconjugated olefin copolymer, and optionally necessary additives. And kneading. The kneading method may be in accordance with a method commonly practiced by those skilled in the art. For example, all components other than the vulcanizing agent, vulcanization accelerator, zinc oxide and vulcanization retarder are mixed with a Banbury mixer, Brabender, kneader, high shear. After kneading (kneading A) at 100 ° C. to 200 ° C. using a mold mixer or the like, a vulcanizing agent, a vulcanization accelerator, zinc oxide, a vulcanization retarder is added (B kneading), and the kneading roll machine or the like is used. What is necessary is just to knead | mix at ℃-130 degreeC. An anti-vibration rubber can be obtained by molding the obtained anti-vibration rubber composition with a heating mold.

  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.

(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, bis (2-phenylindenyl) gadolinium bis (dimethylsilyl) amide [(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, 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 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. A ¹³ C-NMR spectrum chart of copolymer A is shown in FIG. 1, and a DSC curve is shown in FIG.
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 (dimethylsilyl) amide [(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 three 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 the 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 (dimethylsilyl) amide [(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.

(Preparation Example 4)
<Preparation of ethylene-butadiene copolymer D (EBR4)>
Instead of using bis (2-phenylindenyl) gadolinium bis (dimethylsilyl) amide [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] in the production of the ethylene-butadiene copolymer C (EBR3). Except that bis (2-phenyl-1-methylindenyl) gadolinium bis (dimethylsilylamide) [(2-Ph-1-MeC ₉ H ₅ ) ₂ GdN (SiHMe ₂ ) ₂ ] is used. As a result of experiments, an ethylene-butadiene copolymer D (EBR4) (multi-block copolymer) was obtained. The yield of the obtained ethylene-butadiene copolymer D (EBR4) was 28.55 g.
About obtained ethylene-butadiene copolymer D (EBR4), ethylene content rate, a weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) were measured by said method.
As a result, the cis-1,4 bond content was 97% and the 1,2-vinyl bond content was 1.8% as the microstructure of the butadiene moiety in the ethylene-butadiene copolymer D (EBR4). The weight average molecular weight Mw was 221000, and the molecular weight distribution Mw / Mn was 3.13. The ethylene content was 45 mol% (butadiene content was 55 mol%).
The block polyethylene melting temperature (DSC peak temperature) was 122 ° C., and the chain structure was a block.

  A method for analyzing a conjugated diene compound-nonconjugated olefin copolymer is shown below. Table 1 shows the analysis results of the ethylene-butadiene copolymers AD.

<Method for analyzing copolymer>
(1) Microstructure of copolymer (1,2-vinyl bond content, cis-1,4 bond content)
The microstructure of the butadiene moiety in the copolymer (1,2-vinyl bond content) 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 ethylene-derived portion in the copolymer was determined 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.].

(Examples 1-12 and Comparative Examples 1-2)
Anti-vibration rubber compositions were prepared by kneading the components in the blending ratios shown in Tables 2-3.

Brands such as polymers used in the compositions of Tables 2 to 3 are shown below.
NR ^{* 1} : Natural rubber “RSS # ¹ ”
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
EBR4: ethylene-butadiene copolymer D prepared in Preparation Example 4
EPDM ^{* 2} : “EP96” manufactured by JSR (diene content: 5.8 wt%)
Carbon black ^{* 3} : FEF grade carbon black; "Asahi # 65" manufactured by Asahi Carbon Co., Ltd.
Stearic acid: PALMAC1600 (trade name), manufactured by ACIDCHEM Zinc oxide: “Ginren (registered trademark) SR” (trade name), Toho Zinc Co., Ltd. anti-aging agent ^{* 4} : 2,2,4-trimethyl-1,2 -Dihydroquinoline polymer, "NOCRACK (registered trademark) 224" manufactured by Ouchi Shinsei Chemical Co., Ltd.
Wax ^{* 5} : Trade name “SUNITE S” (manufactured by Seiko Chemical Co., Ltd.)
Peroxide ^{* 6} : Di (2-t-butylperoxyisopropyl) benzene, “NOVA CO., LTD.” “Peroximon F-40”
Zinc diacrylate ^{* 7} : “SR633” manufactured by Sartomer
Zinc Dimethacrylate ^{* 8} : “SR634” manufactured by Sartomer

<Characteristic evaluation of vulcanized rubber>
Each sample of the rubber composition was vulcanized at 165 ° C. for 30 minutes and then evaluated by the following test method.

(1) Crack growth resistance (constant strain)
About the vulcanized rubber samples obtained in each Example and Comparative Example, a 0.5 mm crack was put in the center of the JIS No. 3 test piece, and fatigue was given repeatedly at 35 ° C. with a constant strain of 0 to 100%. The number of times until cutting was measured and evaluated. The results are shown in Tables 2 and 3 above.
About evaluation, it displays by the index when the frequency | count of the comparative example 1 is set to 100, and it shows that crack growth resistance (constant strain) is so favorable that an index value is large.

(2) Ozone resistance A dynamic ozone test was performed in accordance with JIS K6259. The test piece was attached to a testing machine without any tensile strain, and adjusted so that a tensile strain of 20% was applied by a predetermined reciprocating motion (0.5 Hz). The ambient temperature of the test was 40 ° C., and the ozone concentration was 40 pphm. The evaluation results are obtained by indexing the time until ozone cracking occurs.

(3) Dynamic magnification (low loss)
In accordance with JIS K 6385, the static spring constant Ks is applied three times with a deflection in the range of 0 mm to +4.5 mm at a displacement speed of 20 mm / min in the direction perpendicular to the axis of the test piece in the bi-directional load method of the static characteristic test. Then, the load-deflection relationship in the third loading process was measured, and using this relationship, the deflection range was calculated in the range of 1.5 to 3.0 mm by the calculation method described in the same standard.
The dynamic spring constant Kd is determined in accordance with JIS K 6385, in a non-resonant method of a dynamic property measurement test, under a load of 10% (3 mm), with a vibration frequency of 100 Hz and an amplitude of ±± Measurement was performed under the condition of 0.05 mm.
And as dynamic magnification, Kd / Ks was computed based on K6385. The results are shown in Tables 2 and 3 above.
About evaluation, it displays by the index when the dynamic magnification of the comparative example 1 is set to 100, and it shows that a result is so favorable that it is a small index value (it is a low dynamic magnification).

  As is apparent from Tables 2 and 3, the vulcanized rubbers obtained from the anti-vibration rubber compositions of Examples 1 to 12 contained a conjugated diene polymer (natural rubber) and a conjugated diene compound in the rubber component. Comparative example 1 which does not contain a conjugated diene compound-nonconjugated olefin copolymer (EBR) by including a nonconjugated olefin copolymer (EBR) and a nonconjugated diene compound-nonconjugated olefin copolymer (EPDM). It can be seen that the crack growth resistance and the ozone resistance can be improved and the dynamic magnification can be lowered as compared with.

  As is apparent from Table 3, the rubber compositions of Examples 5 to 12 contain Examples 1 to 4 that do not contain zinc acrylate or zinc methacrylate by including zinc acrylate or zinc methacrylate in the rubber component. It can be seen that the crack growth resistance can be further improved as compared with FIG.

  The anti-vibration rubber using the anti-vibration rubber composition of the present invention is suitably used as a constituent material for torsional dampers, engine mounts, muffler hangers and the like.

Claims (14)

  The rubber component contains a conjugated diene polymer, a conjugated diene compound-nonconjugated olefin copolymer, and a nonconjugated diene compound-nonconjugated olefin copolymer containing ethylene-propylene-diene rubber. Anti-vibration rubber composition.   The anti-vibration rubber composition according to claim 1, further comprising a vulcanizing agent in the rubber component.   The anti-vibration rubber composition according to claim 2, wherein the vulcanizing agent contains a peroxide.   The anti-vibration rubber composition according to claim 1, further comprising a co-crosslinking agent in the rubber component.   The anti-vibration rubber composition according to claim 4, wherein the co-crosslinking agent contains zinc acrylate or zinc methacrylate.   2. The vibration-insulating rubber composition according to claim 1, wherein in the conjugated diene compound-nonconjugated olefin copolymer, a ratio of the conjugated diene compound-derived portion is 30 mol% to 80 mol%.   The anti-vibration rubber composition according to claim 1, wherein the conjugated diene compound-nonconjugated olefin copolymer has a cis-1,4 bond content of the conjugated diene compound-derived portion of 50% or more.   The anti-vibration rubber composition according to claim 1, wherein the conjugated diene compound-nonconjugated olefin copolymer has a polystyrene-reduced weight average molecular weight of 10,000 to 10,000,000.   The anti-vibration rubber composition according to claim 1, wherein a molecular weight distribution (Mw / Mn) of the conjugated diene compound-nonconjugated olefin copolymer is 10 or less.   The anti-vibration rubber composition according to claim 1, wherein the non-conjugated olefin in the conjugated diene compound-non-conjugated olefin copolymer is an acyclic olefin.   The anti-vibration rubber composition according to claim 1, wherein the non-conjugated olefin in the conjugated diene compound-non-conjugated olefin copolymer has 2 to 10 carbon atoms.   The non-conjugated olefin in the conjugated diene compound-non-conjugated olefin copolymer is at least one selected from the group consisting of ethylene, propylene, and 1-butene. Anti-vibration rubber composition according to claim 1.   The anti-vibration rubber composition according to claim 12, wherein the non-conjugated olefin in the conjugated diene compound-non-conjugated olefin copolymer is ethylene.   An anti-vibration rubber comprising the anti-vibration rubber composition according to claim 1.

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