JP5836143B2 - Anti-vibration rubber composition and anti-vibration rubber - Google Patents

Description

  The present invention relates to an anti-vibration rubber composition and an anti-vibration rubber.

  Conventionally, in various types of vehicles such as automobiles, torsional dampers, engine mounts, mufflers are used to absorb vibrations when the engine is driven and to reduce the intrusion of vibrations and noise into the room and the spread of noise into the surrounding environment. Anti-vibration rubber is used as a constituent material such as hangers. Such an anti-vibration rubber is required to have excellent strength characteristics for supporting a heavy object, an anti-vibration function for absorbing and suppressing vibration of the heavy object to be supported, and excellent crack growth resistance. In addition, when the anti-vibration rubber is used in a high temperature environment such as an engine room, it is required to have excellent weather resistance such as ozone resistance in addition to heat resistance.

  As a rubber component of conventional anti-vibration rubber, natural rubber having excellent destructive properties was often used, but natural rubber has excellent destructive properties, but in addition to heat resistance, weather resistance such as ozone resistance However, the heat resistance and weather resistance were insufficient when used in a high temperature environment. On the other hand, it has been proposed to use natural rubber and ethylene-propylene-diene rubber in combination as a rubber component, but in this case, there is a problem in crack growth resistance and the weather resistance is sufficient. There wasn't.

  On the other hand, in Japanese Patent Application Laid-Open No. 2011-144321, natural rubber (NR) and ethylene-propylene-diene rubber (EPDM) are used as rubber components in a mass ratio (NR / EPDM) of 70/30 to 45/55. In addition, a vibration-insulating rubber composition containing a peroxide, zinc acrylate or zinc methacrylate, and diacrylic acid or lower alkylene glycols of dimethacrylic acid has been proposed. It is said that the creep resistance can be greatly improved while maintaining the properties, tear resistance, strength and low dynamic magnification.

JP 2011-144321 A

  However, as a result of investigation by the present inventor, the anti-vibration rubber composition disclosed in JP 2011-144321 A is composed of natural rubber (NR) and ethylene-propylene-diene rubber (EPDM) used as rubber components. It is incompatible, and it has been found that there is still room for improvement in crack growth resistance and weather resistance such as ozone resistance.

  Accordingly, an object of the present invention is to provide a vibration-insulating rubber composition that solves the above-mentioned problems of the prior art and has greatly improved crack growth resistance and weather resistance. Another object of the present invention is to provide a vibration-proof rubber using such a vibration-proof rubber composition and having excellent crack growth resistance and weather resistance.

  As a result of intensive studies to achieve the above object, the present inventor has found that a conjugated diene polymer, a conjugated diene-nonconjugated olefin copolymer, and a nonconjugated diene-nonconjugated olefin as rubber components of the rubber composition. A copolymer, and an ethylene-propylene-diene rubber as at least a part of the non-conjugated diene-non-conjugated olefin copolymer. Further, a peroxide is compounded as a crosslinking agent. As a crosslinking agent, it is found that the crack growth resistance and weather resistance of the rubber composition are greatly improved by blending zinc acrylate or zinc methacrylate and diacrylic acid or dialkylene methacrylate lower alkylene glycols, The present invention has been completed.

That is, the first vibration-proof rubber composition of the present invention is
The rubber component includes a conjugated diene polymer, a conjugated diene-nonconjugated olefin copolymer, and a nonconjugated diene-nonconjugated olefin copolymer,
The conjugated diene-nonconjugated olefin copolymer is an ethylene-butadiene block copolymer;
The non-conjugated diene-non-conjugated olefin copolymer contains an ethylene-propylene-diene rubber;
As a crosslinking agent, it contains a peroxide,
As a co-crosslinking agent, zinc acrylate or zinc methacrylate, and diacrylic acid or dimethacrylic acid lower alkylene glycols,
The number of carbon atoms of each lower alkylene moiety in the diacrylic acid or dimethacrylic acid lower alkylene glycol is 1-4.
Further, the second vibration-proof rubber composition of the present invention is
The rubber component includes a conjugated diene polymer, a conjugated diene-nonconjugated olefin copolymer, and a nonconjugated diene-nonconjugated olefin copolymer,
The conjugated diene-nonconjugated olefin copolymer is a block copolymer,
The conjugated diene-nonconjugated olefin copolymer has a cis-1,4 bond content of a conjugated diene moiety of 95% or more,
The non-conjugated diene-non-conjugated olefin copolymer contains an ethylene-propylene-diene rubber;
As a crosslinking agent, it contains a peroxide,
As a co-crosslinking agent, zinc acrylate or zinc methacrylate, and diacrylic acid or dimethacrylic acid lower alkylene glycols,
Carbon number of each lower alkylene moiety in the lower alkylene glycols of diacrylic acid or dimethacrylic acid is 1 to 4.
It is characterized by that.
Such anti-vibration rubber composition of the present invention has greatly improved crack growth resistance and weather resistance.

［式中、Ｒ¹は、それぞれ独立して水素又はメチル基であり、ＡＯは、それぞれ独立して、メチレンオキサイド、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であり、ｎは、１〜４の整数である］で表される。 In a preferred example of the vibration-proof rubber composition of the present invention, the diacrylic acid or the lower alkylene glycol of dimethacrylic acid is represented by the following general formula (I):

[Wherein, R ¹ is independently hydrogen or a methyl group, AO is independently methylene oxide, ethylene oxide, propylene oxide or butylene oxide, and n is an integer of 1 to 4. It is represented by.

In the first anti-vibration rubber composition of the present invention, the ethylene-butadiene block copolymer preferably has a cis-1,4 bond content of a butadiene portion of 50% or more.

  In the vibration-proof rubber composition of the present invention, the conjugated diene-nonconjugated olefin copolymer preferably has a polystyrene-equivalent weight average molecular weight (Mw) of 10,000 to 10,000,000.

  In the vibration-proof rubber composition of the present invention, the conjugated diene-nonconjugated olefin copolymer preferably has a molecular weight distribution (Mw / Mn) of 10 or less.

In another preferred embodiment of the second vibration-proof rubber composition of the present invention, the non-conjugated olefin is an acyclic olefin.

In the second vibration-proof rubber composition of the present invention, the non-conjugated olefin preferably has 2 to 10 carbon atoms.

In another preferable example of the second vibration-proof rubber composition of the present invention, the non-conjugated olefin is preferably at least one selected from the group consisting of ethylene, propylene and 1-butene, and is ethylene. It is particularly preferred.

  Moreover, the vibration-proof rubber of the present invention is characterized by using the above-mentioned vibration-proof rubber composition. Such an anti-vibration rubber of the present invention is excellent in crack growth resistance and weather resistance.

  According to the present invention, the rubber component includes a conjugated diene polymer, a conjugated diene-nonconjugated olefin copolymer, and a nonconjugated diene-nonconjugated olefin copolymer, and the nonconjugated diene-nonconjugated olefin copolymer. The polymer contains ethylene-propylene-diene rubber, and further contains a peroxide as a cross-linking agent, and as a co-cross-linking agent, zinc acrylate or zinc methacrylate, and diacrylic acid or dimethacrylic acid lower alkylene glycols. It is possible to provide an anti-vibration rubber composition having significantly improved crack growth resistance, weather resistance and loss characteristics. In addition, according to the present invention, it is possible to provide a vibration-proof rubber using such a vibration-proof rubber composition and having excellent crack growth resistance, weather resistance, and loss characteristics.

It is a figure which shows the ¹³ C-NMR spectrum chart of ethylene-butadiene copolymer rubber (EBR1). It is a figure which shows the DSC curve of ethylene-butadiene copolymer rubber (EBR1). It is a figure which shows the DSC curve of ethylene-butadiene copolymer rubber (EBR3).

<Anti-Vibration Rubber Composition>
Hereinafter, the present invention will be described in detail by illustrating its embodiments. The first vibration damping rubber composition of the present invention, as a rubber component, a conjugated diene polymer, a conjugated diene - and non-conjugated olefin copolymer, a non-conjugated diene - and a non-conjugated olefin copolymer, wherein The conjugated diene-nonconjugated olefin copolymer is an ethylene-butadiene block copolymer, the nonconjugated diene-nonconjugated olefin copolymer contains ethylene-propylene-diene rubber, and contains a peroxide as a crosslinking agent. In addition, as a co-crosslinking agent, zinc acrylate or zinc methacrylate and diacrylic acid or dimethacrylic acid lower alkylene glycols are included, and the second vibration-proof rubber composition of the present invention is a rubber component. A conjugated diene polymer, a conjugated diene-nonconjugated olefin copolymer, and a nonconjugated diene-nonconjugated olefin copolymer, The ene-nonconjugated olefin copolymer is a block copolymer, and the conjugated diene-nonconjugated olefin copolymer has a cis-1,4 bond content of the conjugated diene moiety of 95% or more, and the nonconjugated diene. -The non-conjugated olefin copolymer contains ethylene-propylene-diene rubber, contains a peroxide as a crosslinking agent, zinc acrylate or zinc methacrylate, and diacrylic acid or dimethacrylic acid lower alkylene glycol as a crosslinking agent Wherein each lower alkylene moiety in the diacrylic acid or dimethacrylic acid lower alkylene glycol has 1 to 4 carbon atoms , wherein the diacrylic acid or dimethacrylic acid lower alkylene glycol Carbon number of each lower alkylene part in it is 1-4.

  In general, conjugated diene polymers such as natural rubber (NR) and non-conjugated diene-nonconjugated olefin copolymers such as ethylene-propylene-diene rubber (EPDM) are incompatible with each other. It is difficult to disperse the island phase composed of one of the coalescence and the nonconjugated diene-nonconjugated olefin copolymer and the sea phase composed of the other. Therefore, a rubber composition using a conjugated diene polymer and a non-conjugated diene-non-conjugated olefin copolymer as a rubber component has room for improvement in crack resistance and weather resistance such as ozone resistance. It was. On the other hand, in the present invention, a conjugated diene-nonconjugated olefin copolymer is further used as the rubber component, and the conjugated diene-nonconjugated olefin copolymer acts as a compatibilizing agent. Controlling the morphology, disperse the island phase consisting of one of conjugated diene polymer and non-conjugated diene-nonconjugated olefin copolymer and the sea phase consisting of the other, resulting in weather resistance such as ozone resistance Can be improved.

  Further, in the present invention, the interface between the phase composed of the conjugated diene polymer and the phase composed of the non-conjugated diene-non-conjugated olefin copolymer is made of zinc acrylate or zinc methacrylate and diacrylate or dimethacrylate lower. Crack growth resistance is improved by co-crosslinking in combination with alkylene glycols. Furthermore, surprisingly, in the present invention, by using zinc acrylate or zinc methacrylate together with diacrylic acid or lower alkylene glycols of dimethacrylic acid, the hysteresis loss of the rubber composition is increased, and loss characteristics are increased. Has also improved.

<< Rubber component >>
The anti-vibration rubber composition of the present invention contains, as a rubber component, a conjugated diene polymer, a conjugated diene-nonconjugated olefin copolymer, and a nonconjugated diene-nonconjugated olefin copolymer. In addition, other rubber components may be included.

<<< Conjugated Diene Polymer >>>
The conjugated diene polymer means a polymer (polymer) containing as a main component a polymer obtained by polymerizing a conjugated diene monomer. The conjugated diene polymer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, natural rubber (NR), polybutadiene rubber (BR), synthetic polyisoprene rubber (IR), chloroprene rubber ( CR) and the like. These conjugated diene polymers may be used alone or in combination of two or more. Among these, natural rubber is preferable because it has good compatibility and can improve crack growth resistance.

  The content of the conjugated diene polymer in 100 parts by mass of the rubber component is preferably in the range of 45 to 70 parts by mass, and more preferably in the range of 60 to 70 parts by mass. If 45 to 70 parts by mass of 100 parts by mass of the rubber component is a conjugated diene polymer, the crack growth resistance of the vibration-insulating rubber composition can be sufficiently improved.

<<<< Conjugated diene-nonconjugated olefin copolymer >>>>
The conjugated diene-nonconjugated olefin copolymer is a copolymer of a conjugated diene and a nonconjugated olefin, and includes a conjugated diene and a nonconjugated olefin as monomer unit components in the copolymer. The conjugated diene-nonconjugated olefin copolymer can improve the compatibility between the conjugated diene polymer described above and the nonconjugated diene-nonconjugated olefin copolymer described below.

  The content of the conjugated diene-nonconjugated olefin copolymer in 100 parts by mass of the rubber component is preferably 5 parts by mass or more, and more preferably in the range of 10 to 20 parts by mass. If 5 parts by mass or more in 100 parts by mass of the rubber component is a conjugated diene-nonconjugated olefin copolymer, the crack growth resistance of the vibration-insulating rubber composition can be sufficiently improved.

  The content of the conjugated diene-derived moiety in the conjugated diene-nonconjugated olefin copolymer is preferably in the range of 20 mol% to 95 mol%, and more preferably in the range of 30 mol% to 80 mol%. It is particularly preferable that the content of the conjugated diene-derived portion in the conjugated diene-nonconjugated olefin copolymer is 30 mol% or more because processability can be sufficiently secured, and if it is 80 mol% or less, the ratio of nonconjugated olefin is large. And weather resistance is particularly improved.

  The content of the non-conjugated olefin-derived moiety in the conjugated diene-nonconjugated olefin copolymer is preferably in the range of 5 mol% to 80 mol%, and more preferably in the range of 20 mol% to 70 mol%. When the content of the non-conjugated olefin-derived portion in the conjugated diene-nonconjugated olefin copolymer is 20 mol% or more, the weather resistance can be greatly improved, and when it is 70 mol% or less, the conjugated diene-based weight The compatibility with the coalescence can be maintained and the weather resistance and crack growth resistance can be greatly improved.

  Further, the cis-1,4 bond content of the conjugated diene-derived portion in the conjugated diene-nonconjugated olefin copolymer is preferably 50% or more, particularly preferably more than 92%, and most preferably 95% or more. If the cis 1,4-bond amount of the conjugated diene-derived moiety is 50% or more, the crack growth resistance can be sufficiently improved. Further, by making the amount of cis 1,4-bond of the conjugated diene-derived portion more than 92%, the crack growth resistance can be further improved, and the amount of cis 1,4-bond of the conjugated diene-derived portion is 95%. By setting it as the above, it becomes possible to improve crack growth resistance further. The cis-1,4 bond amount is an amount in the conjugated diene-derived portion and is not a ratio to the entire copolymer.

  In the conjugated diene-nonconjugated olefin copolymer, the nonconjugated olefin used as a monomer is a nonconjugated olefin other than the conjugated diene, and has excellent heat resistance and a double bond in the main chain of the copolymer. It is possible to increase the degree of design freedom as an elastomer by controlling the crystallinity. The non-conjugated olefin is preferably an acyclic olefin, and the non-conjugated olefin preferably has 2 to 10 carbon atoms. Accordingly, preferred examples of the non-conjugated olefin include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene. Among these, ethylene, propylene And 1-butene are preferred, with ethylene being particularly preferred. Here, the non-conjugated olefin does not include styrene. Since the α-olefin has a double bond at the α-position of the olefin, it can be efficiently copolymerized with a conjugated diene. These non-conjugated olefins may be used alone or in combination of two or more. In addition, an olefin refers to the compound which is an aliphatic unsaturated hydrocarbon and has one or more carbon-carbon double bonds. In addition, when a block portion composed of a monomer unit of non-conjugated olefin is provided, it exhibits static crystallinity and is excellent in mechanical properties such as breaking strength.

  On the other hand, in the conjugated diene-nonconjugated olefin copolymer, the conjugated diene used as a monomer preferably has 4 to 12 carbon atoms. Specific examples of the conjugated diene include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and among these, 1,3-butadiene and isoprene are preferable. Moreover, these conjugated dienes may be used alone or in combination of two or more. Using any of the specific examples of the conjugated diene described above, the desired copolymer can be prepared by the same mechanism.

  The conjugated diene-nonconjugated olefin copolymer preferably has a polystyrene equivalent weight average molecular weight (Mw) of 10,000 to 10,000,000 from the viewpoint of application to a polymer structure material. More preferably, it is -1,000,000, and it is especially preferable that it is 50,000-600,000. If the Mw exceeds 10,000,000, the moldability may be deteriorated. Further, the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably 10 or less, and more preferably 6 or less. If the molecular weight distribution exceeds 10, the physical properties may not be uniform. Here, the average molecular weight and the molecular weight distribution can be determined using polystyrene as a standard substance by gel permeation chromatography (GPC).

  The content of 1,2 adducts (including 3,4 adducts) of the conjugated diene in the conjugated diene-derived part of the conjugated diene-nonconjugated olefin copolymer is preferably 5% or less, more preferably 3% or less. 2.5% or less is particularly preferable. When the content of 1,2-adduct of conjugated diene (including 3,4-adduct) in the conjugated diene-derived portion of the conjugated diene-nonconjugated olefin copolymer is 5% or less, the crack growth resistance of the rubber composition When it is 2.5% or less, the crack growth resistance of the rubber composition can be further improved. The content of the 1,2-adduct portion (including the 3,4-adduct portion) is an amount in the conjugated diene-derived portion and is not a ratio to the whole copolymer. Moreover, the 1,2-adduct part content (including 3,4-adduct part) content of the conjugated diene in the conjugated diene-derived part has the same meaning as the 1,2-vinyl bond amount when the conjugated diene is butadiene.

The conjugated diene - nonconjugated olefin copolymer is a block copolymer.

The block copolymer has a structure of (AB) _x , A- (BA) _x and B- (AB) _x (where A is a block composed of monomer units of non-conjugated olefins). And B is a block part composed of monomer units of conjugated dienes, 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-nonconjugated olefin copolymer is a block copolymer, the block portion composed of the monomer of the nonconjugated olefin exhibits static crystallinity, and thus has excellent mechanical properties such as breaking strength.

  Next, the manufacturing method which can manufacture the said conjugated diene-nonconjugated olefin copolymer is demonstrated in detail. However, the production method described in detail below is merely an example, and the copolymer according to the present invention is obtained by polymerizing a conjugated diene and a non-conjugated olefin in the presence of a polymerization catalyst or a polymerization catalyst composition. It is done.

  In the method for producing the conjugated diene-nonconjugated olefin copolymer, the polymerization by the usual coordination ion polymerization catalyst is used except that the polymerization catalyst described later or the first, second and third polymerization catalyst compositions are used. In the same manner as in the method for producing a coalescence, a monomeric conjugated diene and a non-conjugated olefin can be copolymerized.

  As a polymerization method, any method such as a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. Moreover, when using a solvent for a polymerization reaction, the solvent used should just be inactive in a polymerization reaction, For example, toluene, cyclohexane, normal hexane, mixtures thereof etc. are mentioned.

  In the method for producing the conjugated diene-nonconjugated olefin copolymer, for example, (1) a component of the polymerization catalyst composition is separately provided in a polymerization reaction system containing a conjugated diene and a nonconjugated olefin as monomers. 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 a conjugated diene and a nonconjugated olefin.

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

  The polymerization reaction of the conjugated diene 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 and a nonconjugated olefin in a polymerization reaction system, the range of 0.1-10.0 MPa is preferable. Further, the reaction time of the above polymerization reaction is not particularly limited, and is preferably in the range of 1 second to 10 days, for example. it can.

  In the method for producing a copolymer, the pressure of the non-conjugated olefin is preferably 0.1 MPa to 10 MPa when the conjugated diene and the non-conjugated olefin are polymerized. 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 a copolymer, when polymerizing a conjugated diene and a non-conjugated olefin, the concentration (mol / l) of the conjugated diene at the start of polymerization and the concentration (mol / l) of the non-conjugated olefin are as follows: formula:
Non-conjugated olefin concentration / conjugated diene concentration ≧ 1.0
It is preferable to satisfy the relationship. By setting the non-conjugated olefin concentration / conjugated diene concentration value to 1 or more, the non-conjugated olefin can be efficiently introduced into the reaction mixture. Also, the following formula:
Non-conjugated olefin concentration / conjugated diene concentration ≧ 1.3
More preferably, the following relationship is satisfied:
Non-conjugated olefin concentration / conjugated diene concentration ≧ 1.7
It is even more preferable to satisfy this relationship.

（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（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、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（IV）：

（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）が挙げられる。 Next, the 1st polymerization catalyst composition used in the manufacturing method of the said conjugated diene-nonconjugated olefin copolymer is demonstrated. As the first polymerization catalyst composition, the following general formula (II):

(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 (III):

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

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^{R ′} represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxide group or a thiolate group. , An amide group, a silyl group, or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, w represents an integer of 0 to 3, and [B] ⁻ represents a non-coordinating group. A polymerization catalyst composition (hereinafter also referred to as a first polymerization catalyst composition) containing at least one complex selected from the group consisting of half metallocene cation complexes represented by

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

In the metallocene complexes represented by the above general formula (II) and formula (III), Cp ^R in the formula is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7-X R _X or C ₉ H _11-X R _X. Here, X is an integer of 0-7 or 0-11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of the substituted indenyl include 2-phenylindenyl and 2-methylindenyl. Incidentally, the two Cp ^R in the general formula (II) and formula (III) may each be the same 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）のものが例示される。一般式（IV）において、上記インデニル環を基本骨格とするＣｐ^R'は、一般式（II）のＣｐ^Rと同様に定義され、好ましい例も同様である。一般式（IV）において、上記フルオレニル環を基本骨格とするＣｐ^R'は、Ｃ₁₃Ｈ_9-XＲ_X又はＣ₁₃Ｈ_17-XＲ_Xで示され得る。ここで、Ｘは０〜９又は０〜１７の整数である。また、Ｒはそれぞれ独立してヒドロカルビル基又はメタロイド基であることが好ましい。ヒドロカルビル基の炭素数は１〜２０であることが好ましく、１〜１０であることが更に好ましく、１〜８であることが一層好ましい。該ヒドロカルビル基として、具体的には、メチル基、エチル基、フェニル基、ベンジル基等が好適に挙げられる。一方、メタロイド基のメタロイドの例としては、ゲルミルＧｅ、スタニルＳｎ、シリルＳｉが挙げられ、また、メタロイド基はヒドロカルビル基を有することが好ましく、メタロイド基が有するヒドロカルビル基は上記のヒドロカルビル基と同様である。該メタロイド基として、具体的には、トリメチルシリル基等が挙げられる。 In the half metallocene cation complex represented by the general formula (IV), 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. As Cp ^{R ′} having a cyclopentadienyl ring as a basic skeleton, specifically, the following:

(In the formula, R represents a hydrogen atom, a methyl group or an ethyl group). In the general formula (IV), Cp ^{R ′} having the above indenyl ring as a basic skeleton is defined in the same manner as Cp ^{R in the} general formula (II), and preferred examples thereof are also the same. In the general formula (IV), 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 formula (II), formula (III) and formula (IV) 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 (II) includes a silylamide ligand [—N (SiR ₃ ) ₂ ]. The R groups contained in the silylamide ligand (R ^{a to} R ^f in the general formula (II)) 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 (III) 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 (IV) described below, and preferred groups are also the same.

  In the general formula (IV), 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 (IV), 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. Of these, 2,4,6-triisopropylthiophenoxy group is preferred. Arbitrariness. In the general formula (IV), 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 (IV), 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 (IV), the halogen atom represented by X may be 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 general formula (IV), X is preferably a bistrimethylsilylamide group or a hydrocarbon group having 1 to 20 carbon atoms.

In formula (IV), [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 formula (II) and the formula (III) and the half metallocene cation complex represented by the general formula (IV) 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. In addition, the metallocene complex represented by the general formula (II) and the formula (III) and the half metallocene cation complex represented by the general formula (IV) may be present as a monomer. It may exist as a body or higher multimer.

（式中、Ｘ''はハライドを示す。） The metallocene complex represented by the general formula (II) includes, for example, a lanthanide 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 example of reaction for obtaining the metallocene complex represented by general formula (II) 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 (III) includes, for example, a lanthanoid trishalide, scandium trishalide, or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt), and a silyl salt (for example, potassium). Salt or lithium salt). In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used. The reaction example for obtaining the metallocene complex represented by the general formula (III) is shown below.

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

The half metallocene cation complex represented by the general formula (IV) can be obtained, for example, by the following reaction.

Here, in the compound represented by the general formula (V), M represents a lanthanoid element, scandium or yttrium, and Cp ^{R ′} independently represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl. , X represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, and w represents 0 to 3 Indicates an integer. In the ionic compound represented by the general formula [A] ⁺ [B] ⁻ , [A] ⁺ represents a cation, and [B] ⁻ represents a non-coordinating anion.

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

The ionic compound represented by the general formula [A] ⁺ [B] ⁻ used for the above reaction is a compound selected and combined from the above non-coordinating anions and cations, which is N, N-dimethylaniline. Preference is given to nium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like. In general formula [A] ⁺ [B] ^- ionic compounds represented by is preferably added from 0.1 to 10 mol per mol of the metallocene complex, more preferably it added about 1 molar. When the half metallocene cation complex represented by the general formula (IV) is used for the polymerization reaction, the half metallocene cation complex represented by the general formula (IV) may be provided as it is in the polymerization reaction system, or the compound represented by the general formula (V) 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 (IV 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 (II) or the formula (III) and an ionic compound represented by the general formula [A] ⁺ [B] ^- A half metallocene cation complex represented by the formula (IV) can also be formed.

  The structures of the metallocene complexes represented by the general formulas (II) and (III) and the half metallocene cation complex represented by the general formula (IV) 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.

  Furthermore, in the above polymerization catalyst composition, the metallocene complex represented by the general formula (II) and the formula (III) and the half metallocene cation complex represented by the above general formula (IV), respectively, By combining, the amount of cis-1,4 bonds and the molecular weight of the resulting copolymer can be increased.

Next, the second polymerization catalyst composition used in the method for producing a conjugated diene-nonconjugated olefin copolymer according to the present invention will be described. As the second polymerization catalyst composition,
(A) component: a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base, the rare earth element compound or the reaction product having no bond between the rare earth element and carbon,
Component (B): Contains ionic compound (B-1) composed of non-coordinating anion and cation, aluminoxane (B-2), Lewis acid, complex compound of metal halide and Lewis base, and active halogen. A polymerization catalyst composition (hereinafter also referred to as a second polymerization catalyst composition) containing at least one selected from the group consisting of at least one halogen compound (B-3) among organic compounds can be preferably mentioned.

Further, when the second polymerization catalyst composition contains at least one of the ionic compound (B-1) and the halogen compound (B-3), the polymerization catalyst composition further comprises:
(C) Component: The following general formula (VI):
YR ¹ _a R ² _b R ³ _c (VI)
[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]. Including.

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

  The component (A) used in the second polymerization catalyst composition is a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base. Here, the reaction of the rare earth element compound and the rare earth element compound with a Lewis base is performed. The object does not have a bond between rare earth element and carbon. When the rare earth element compound and the reactant do not have a rare earth element-carbon bond, the compound is stable and easy to handle. Here, the rare earth element compound is a compound containing a lanthanoid element or scandium or yttrium composed of the elements of atomic numbers 57 to 71 in the periodic table. Specific examples of the lanthanoid element include lanthanium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. In addition, the said (A) component may be used individually by 1 type, and may be used in combination of 2 or more type.

The rare earth element compound is preferably a divalent or trivalent salt or complex compound of a rare earth metal, and one or more coordinations selected from a hydrogen atom, a halogen atom and an organic compound residue. More preferably, the rare earth element compound contains a child. Furthermore, the reaction product of the rare earth element compound or the rare earth element compound and a Lewis base is represented by the following general formula (VII) or (VIII):
M ¹¹ X ¹¹ ₂・ L ¹¹ w (VII)
M ¹¹ X ¹¹ ₃ · L ¹¹ w (VIII)
[Wherein, M ¹¹ represents a lanthanoid element, scandium or yttrium, and X ¹¹ independently represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, an aldehyde residue, a ketone residue. A group, a carboxylic acid residue, a thiocarboxylic acid residue or a phosphorus compound residue, L ¹¹ represents a Lewis base, and w represents 0 to 3].

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

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

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

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

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

The halogen compound represented by (B-3) is composed of at least one of a Lewis acid, a complex compound of a metal halide and a Lewis base, and an organic compound containing an active halogen, and is, for example, the component (A). By reacting with a rare earth element compound or a reaction product thereof with a Lewis base, a cationic transition metal compound, a halogenated transition metal compound, or a compound in which the transition metal center is deficient in charge can be generated. In addition, it is preferable that content of the sum total of the halogen compound in the said 2nd polymerization catalyst composition is 1-5 times mole with respect to (A) component. As the Lewis acid, boron-containing halogen compounds such as B (C ₆ F ₅ ) ₃ and aluminum-containing halogen compounds such as Al (C ₆ F ₅ ) ₃ can be used. A halogen compound containing an element belonging to the group V, VI or VIII can also be used. Preferably, aluminum halide or organometallic halide is used. Moreover, as a halogen element, chlorine or bromine is preferable. Specific examples of the Lewis acid include methyl aluminum dibromide, methyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, diethyl aluminum bromide, diethyl Aluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquichloride, dibutyltin dichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, phosphorus trichloride , Pentachloride , Tin tetrachloride, titanium tetrachloride, tungsten hexachloride, etc., among which diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide, ethylaluminum dibromide preferable. The metal halide constituting the complex compound of the above metal halide and Lewis base includes beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, iodine. Calcium chloride, barium chloride, barium bromide, barium iodide, zinc chloride, zinc bromide, zinc iodide, cadmium chloride, cadmium bromide, cadmium iodide, mercury chloride, mercury bromide, mercury iodide, manganese chloride, Manganese bromide, manganese iodide, rhenium chloride, rhenium bromide, rhenium iodide, copper chloride, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, gold bromide, etc. Of these, magnesium chloride, calcium chloride, barium chloride, manganese chloride, zinc chloride, and copper chloride are preferred. , Magnesium chloride, manganese chloride, zinc chloride, copper chloride being particularly preferred. Moreover, as a Lewis base which comprises the complex compound of the said metal halide and a Lewis base, a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, alcohol, etc. are preferable. Specifically, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphinoethane, acetylacetone, benzoylacetone , Propionitrile acetone, valeryl acetone, ethyl acetylacetone, methyl acetoacetate, ethyl acetoacetate, phenyl acetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2-ethyl-hexanoic acid, olein Acid, stearic acid, benzoic acid, naphthenic acid, versatic acid, triethylamine, N, N-dimethylacetamide, tetrahydrofuran, diphenyl ether, 2-ethyl-hexyl alcohol Examples include oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, and lauryl alcohol. Among these, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2 -Ethylhexyl alcohol, 1-decanol and lauryl alcohol are preferred. The Lewis base is reacted at a ratio of 0.01 to 30 mol, preferably 0.5 to 10 mol, per mol of the metal halide. When the reaction product with the Lewis base is used, the metal remaining in the polymer can be reduced. Examples of the organic compound containing the active halogen include benzyl chloride.

The component (C) used in the second polymerization catalyst composition is an organometallic compound represented by the above general formula (VI), and the following general formula (VI-a):
AlR ¹ R ² R ³ ... (VI-a)
[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 formula (VI-a) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, and tripentyl. Aluminum, 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, dihydrogen hydride Isohexyl aluminum, dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propyl aluminum Examples thereof include dihydride and isobutylaluminum dihydride. Among these, triethylaluminum, triisobutylaluminum, diethylaluminum hydride, and diisobutylaluminum hydride are preferable. The organoaluminum compound as component (C) described above can be used alone or in combination of two or more. In addition, it is preferable that it is 1-50 times mole with respect to (A) component, and, as for content of the organoaluminum compound in the said 2nd polymerization catalyst composition, it is still more preferable that it is about 10 times mole.

［式中、Ｍ¹は、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^A及びＲ^Bは、それぞれ独立して炭素数１〜２０の炭化水素基を示し、該Ｒ^A及びＲ^Bは、Ｍ¹及びＡｌにμ配位しており、Ｒ^C及びＲ^Dは、それぞれ独立して炭素数１〜２０の炭化水素基又は水素原子を示す］で表されるメタロセン系複合触媒が挙げられる。上記メタロセン系複合触媒を用いることで、共役ジエン−非共役オレフィン共重合体を製造することができる。また、上記メタロセン系複合触媒、例えば予めアルミニウム触媒と複合させてなる触媒を用いることで、共重合体合成時に使用されるアルキルアルミニウムの量を低減したり、無くしたりすることが可能となる。なお、従来の触媒系を用いると、共重合体合成時に大量のアルキルアルミニウムを用いる必要がある。例えば、従来の触媒系では、金属触媒に対して１０当量以上のアルキルアルミニウムを用いる必要があるところ、上記メタロセン系複合触媒であれば、５当量程度のアルキルアルミニウムを加えることで、優れた触媒作用が発揮される。 Next, the polymerization catalyst and the third polymerization catalyst composition used in the method for producing the conjugated diene-nonconjugated olefin copolymer will be described. The polymerization catalyst is for polymerization of conjugated dienes and non-conjugated olefins, and has the following formula (IX):
R _a MX _b QY _b (IX)
[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]. In a preferred example of the metallocene composite catalyst, the following formula (X):

[ ^Wherein , M ¹ represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents unsubstituted or substituted indenyl, and R ^A and R ^B each independently represents a group having 1 to 20 carbon atoms. R ^A and R ^B are μ-coordinated to M ¹ and Al, and R ^C and R ^D each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Metallocene composite catalysts represented by By using the metallocene composite catalyst, a conjugated diene-nonconjugated olefin copolymer can be produced. In addition, by using the metallocene composite catalyst, for example, a catalyst previously combined with an aluminum catalyst, the amount of alkylaluminum used at the time of copolymer synthesis can be reduced or eliminated. If a conventional catalyst system is used, it is necessary to use a large amount of alkylaluminum at the time of copolymer synthesis. For example, in the conventional catalyst system, it is necessary to use 10 equivalents or more of alkylaluminum with respect to the metal catalyst. If the metallocene composite catalyst is used, an excellent catalytic action can be obtained by adding about 5 equivalents of alkylaluminum. Is demonstrated.

  In the metallocene composite catalyst, the metal M in the formula (IX) 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 (IX), 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 (IX), 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 (IX), 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 (IX), 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 (X), the metal M ¹ is a lanthanoid element, scandium or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferred examples of the metal M ¹ include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y. In the above formula (X), Cp ^R is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7-X R _X or C ₉ H _11-X R _X. Here, X is an integer of 0-7 or 0-11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of the substituted indenyl include 2-phenylindenyl and 2-methylindenyl. Note that the two Cp ^R 's in formula (X) may be the same as or different from each other. In the formula (X), R ^A and R ^B each independently represent a hydrocarbon group having 1 to 20 carbon atoms, said R ^A and R ^B is coordinated μ to M ¹及A ^l . Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like. Note that the μ coordination is a coordination mode having a crosslinked structure. In the above formula (X), R ^C and R ^D are each independently a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

（式中、Ｍ²は、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^E〜Ｒ^Jは、それぞれ独立して炭素数１〜３のアルキル基又は水素原子を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体を、ＡｌＲ^KＲ^LＲ^Mで表される有機アルミニウム化合物と反応させることで得られる。なお、反応温度は室温程度にすればよいので、温和な条件で製造することができる。また、反応時間は任意であるが、数時間〜数十時間程度である。反応溶媒は特に限定されないが、原料及び生成物を溶解する溶媒であることが好ましく、例えばトルエンやヘキサンを用いればよい。なお、上記メタロセン系複合触媒の構造は、¹Ｈ−ＮＭＲやＸ線構造解析により決定することが好ましい。 The metallocene composite catalyst is, for example, in a solvent, represented by the following formula (XI):

(In the formula, M ² represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and R ^{E to} R ^J each independently represents a group having 1 to 3 carbon atoms. an alkyl group or a hydrogen atom, L is a neutral Lewis base, w is, the metallocene complex represented by an integer of 0 to 3), an organoaluminum compound represented by AlR ^K R ^L R ^M It is obtained by reacting with. In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene or hexane may be used. The structure of the metallocene composite catalyst is preferably determined by ¹ H-NMR or X-ray structural analysis.

In the metallocene complex represented by the above formula (XI), Cp ^R is unsubstituted indenyl or substituted indenyl and has the same meaning as Cp ^R in the above formula (X). In the formula (XI), the metal M ² is a lanthanoid element, scandium or yttrium, and has the same meaning as the metal M ¹ in the formula (X). The metallocene complex represented by the above formula (XI) contains a silylamide ligand [—N (SiR ₃ ) ₂ ]. The R groups (R ^{E to} R ^J groups) contained in the silylamide ligand are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. Moreover, it is preferable that at least one of R ^{E to} R ^J is a hydrogen atom. By making at least one of R ^{E to} R ^J a hydrogen atom, the catalyst can be easily synthesized. Furthermore, a methyl group is preferable as the alkyl group. The metallocene complex represented by the above formula (XI) 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. Further, the metallocene complex represented by the above formula (XI) 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. R ^M is a hydrogen group or a hydrogen atom, and R ^M is a monovalent hydrocarbon group having 1 to 20 carbon atoms, provided that R ^M may be the same as or different from R ^K or R ^L described above. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group and tetradecyl group. , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like. Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, Hexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride , Dioctylaluminum hydride, diisooctylaluminum hydride; ethylaluminum dihydride, n-propylaluminium Dihydride, isobutyl aluminum dihydride and the like. Among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. Moreover, these organoaluminum compounds can be used individually by 1 type, or 2 or more types can be mixed and used for them. In addition, the amount of the organoaluminum compound used for the production of the metallocene composite catalyst is preferably 1 to 50 times mole, more preferably about 10 times mole relative to the metallocene complex.

  Further, the third polymerization catalyst composition is characterized in that it contains the metallocene composite catalyst and a boron anion, and further, other components contained in the polymerization catalyst composition containing a normal metallocene catalyst, For example, it preferably contains a cocatalyst and the like. The metallocene composite catalyst and boron anion are also referred to as a two-component catalyst. According to the third polymerization catalyst composition, since the boron anion is further contained in the same manner as the metallocene composite catalyst, the content of each monomer component in the copolymer can be arbitrarily controlled. It becomes possible.

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

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

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

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

  Further, even if the polymerization catalyst composition is not used, that is, even when a normal coordination ion polymerization catalyst is used, by adjusting how the monomer is charged into the polymerization reaction system, The copolymer can be produced. That is, the second method for producing the copolymer is characterized in that the chain structure of the copolymer is controlled by controlling the input of the conjugated diene in the presence of the non-conjugated olefin, thereby providing a copolymer. The arrangement of monomer units in the polymer can be controlled. In addition, in this invention, a polymerization reaction system means the place where superposition | polymerization with a conjugated diene and a nonconjugated olefin is performed, A reaction container etc. are mentioned as a specific example. Here, the conjugated diene charging method may be either continuous charging or split charging, and may be a combination of continuous charging and split charging. Moreover, continuous injection means adding for a fixed time at a fixed addition rate, for example. Specifically, it is possible to control the concentration ratio of the monomers in the polymerization reaction system by dividing or continuously charging the conjugated diene into the polymerization reaction system for polymerizing the conjugated diene 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 is added, the presence of the non-conjugated olefin in the polymerization reaction system can suppress the production of the conjugated diene homopolymer. The addition of the conjugated diene may be performed after the polymerization of the nonconjugated olefin is started.

<<<< Non-conjugated diene-non-conjugated olefin copolymer >>>>
The non-conjugated diene-non-conjugated olefin copolymer is a copolymer of a non-conjugated diene and a non-conjugated olefin. Here, examples of the non-conjugated diene include ethylidene norbornene (ENB), 1,4-hexadiene (1,4-HD), dicyclopentadiene (DCP), and the like. Examples of the non-conjugated olefin include ethylene, propylene, 1 Preferred are α-olefins such as -butene, 1-pentene, 1-hexene, 1-heptene, 1-octene.

  In the vibration-proof rubber composition of the present invention, the non-conjugated diene-non-conjugated olefin copolymer contains at least ethylene-propylene-diene rubber (EPDM), and the ethylene-propylene-diene rubber has excellent weather resistance. Realize. The ethylene-propylene-diene rubber is a synthetic rubber in which a small amount of a third component is introduced into ethylene propylene rubber (EPM), which is a copolymer of ethylene and propylene, and a double bond is provided 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.

  The content of the non-conjugated diene-non-conjugated olefin copolymer in 100 parts by mass of the rubber component is preferably 30 parts by mass or more, and more preferably in the range of 30 to 55 parts by mass. If 30 parts by mass or more of 100 parts by mass of the rubber component is a non-conjugated diene-non-conjugated olefin copolymer, the crack growth resistance of the vibration-proof rubber composition can be sufficiently improved. From the viewpoint of weather resistance, the content of ethylene-propylene-diene rubber (EPDM) in 100 parts by mass of the rubber component is preferably 30 parts by mass or more, more preferably in the range of 30 to 60 parts by mass, A range of 35 to 55 parts by mass is even more preferable.

<< Crosslinking agent >>
The anti-vibration rubber composition of the present invention contains a peroxide as a crosslinking agent. In the present invention, by using a peroxide as the crosslinking agent, the crack growth resistance and loss characteristics of the vibration-insulating rubber composition can be improved. Examples of the peroxide include dicumyl peroxide, benzoyl peroxide, 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, diisobutyryl peroxide, cumylperoxyneodeca Noate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, di (4 -T-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxyneohepta Noate, t-hexyl peroxypivalate t-butyl peroxypivalate, di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, disuccinic acid Acid peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, 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, 1,1-di (t-hexylperoxy) -3,3,5-tri Tylcyclohexane, 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-butylperoxylaurate, t- Butyl peroxyisopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-di-methyl-2,5-di (benzoylperoxy) hexane, t-butyl peroxy Acetate, 2,2-di- (t-butylperoxy) butane, t-butyl -Oxybenzoate, 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 hydroperoxide, 2,5-dimethyl-2,5-di (t-butyl) Peroxy) hexyne-3, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, and the like. Among these, di ( 2-t-Butylperoxyisopropyl) benzene and dicumyl peroxide are preferred. These peroxides may be used alone or in combination of two or more. The compounding quantity of the said peroxide is 1-10 mass parts normally with respect to 100 mass parts of said rubber components, Preferably it is 2-8 mass parts. When the amount of the peroxide is less than 1 part by mass, the crosslinking density is lowered, which may lead to a decrease in breaking strength, a deterioration in dynamic ratio, a deterioration in compression set and a decrease in durability. When it exceeds the part, the rubber is excessively cured, which may cause a decrease in elongation at break and a decrease in durability.

  The anti-vibration rubber composition of the present invention may contain sulfur as a crosslinking agent in addition to the above-described peroxide, and the amount of sulfur is 0 to 100 parts by mass of the rubber component. A range of 0.5 parts by mass is preferable, and a range of 0.1 to 0.5 parts by mass is more preferable.

<< Co-crosslinking agent >>
The anti-vibration rubber composition of the present invention contains zinc acrylate or zinc methacrylate as a co-crosslinking agent and dialkyl acid or dialkyl methacrylate lower alkylene glycols, wherein the diacrylic acid or dimethacrylate lower alkylene Carbon number of each lower alkylene part in glycols is 1-4. The co-crosslinking agent is not an ability to generate a crosslinking point by itself, but is an additive that causes a crosslinking reaction in rubber when used in combination with the peroxide.

  The zinc acrylate or zinc methacrylate is a salt of zinc and acrylic acid or methacrylic acid, and is usually zinc diacrylate or zinc dimethacrylate. The blending amount of the zinc acrylate or zinc methacrylate is preferably in the range of 1.5 to 4.0 parts by weight, more preferably in the range of 2.0 to 3.8 parts by weight with respect to 100 parts by weight of the rubber component. . If the blending amount of zinc acrylate or zinc methacrylate exceeds the above range, the rubber may be hardened too much, leading to a decrease in elongation at break or the like, and if it is below the above range, the rubber is not sufficiently crosslinked. Further, there is a risk of causing a decrease in breaking strength, a decrease in tear strength, an increase in dynamic magnification, an increase in compression set, and the like.

On the other hand, as said diacrylic acid or dimethacrylic acid lower alkylene glycol, the compound represented by the said general formula (I) is preferable. In general formula (I), R < ¹ > is respectively independently hydrogen or a methyl group. In general formula (I), AO is each independently methylene oxide, ethylene oxide, propylene oxide, or butylene oxide, preferably ethylene oxide (C ₂ H ₄ O). Moreover, in general formula (I), n is an integer of 1-4 and it is preferable that it is 1. When the value of n increases, the number of carbon atoms of the lower alkylene glycol increases, which may cause deterioration of compression set.

Specific examples of the diacrylic acid or dimethacrylic acid lower alkylene glycols represented by the above general formula (I) are represented by the above general formula (I), R ¹ is a methyl group, and AO is ethylene oxide (C in ₂ H ₄ O), ethylene glycol dimethacrylate n is 1, represented by the general formula (I), in which R ¹ is a methyl group, with AO is ethylene oxide _{(C 2 H 4 O),} n is 2 to 4 polyethylene glycol dimethacrylate, represented by the above general formula (I), R ¹ is a methyl group, AO is propylene oxide (C ₃ H ₆ O), and n is 1 Glycol, dimethacrylic acid polypropylene glycol represented by the above general formula (I), R ¹ is a methyl group, AO is propylene oxide (C ₃ H ₆ O), and n is 2 to 4, and the above general formula (I ) , In which R ¹ is a methyl group, AO is butylene oxide _{(C 4 H 8 O),} n is represented by di methacrylate tetramethylene glycol is 1, the general formula (I), R ¹ is a methyl group, AO is butylene oxide (C ₄ H ₈ O), and n is 2 to 4 polytetramethylene glycol dimethacrylate, represented by the above general formula (I), R ¹ is hydrogen, AO is ethylene oxide (C in ₂ H ₄ O), n is ethylene glycol diacrylate is 1, represented by the general formula (I), in which R ¹ is hydrogen, with AO is ethylene oxide _{(C 2 H 4 O),} n is 2 4, polyethylene glycol diacrylate and the like.

  With respect to the lower alkylene glycols of diacrylic acid or dimethacrylic acid, examples of the lower alkylene glycol include (poly) ethylene glycol such as monoethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol, monopropylene glycol, dipropylene glycol, and triethylene glycol. (Poly) propylene glycol such as propylene glycol and polypropylene glycol, (poly) propanediol such as 1,2-propanediol and 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1, Examples include (poly) butanediol such as 4-butanediol, and among these, ethylene glycol is preferable.

  The amount of the diacrylic acid or dimethacrylic acid lower alkylene glycol is preferably in the range of 0.4 to 3.2 parts by mass, and in the range of 0.8 to 2.8 parts by mass, with respect to 100 parts by mass of the rubber component. Is more preferable. If the blending amount exceeds the above range, the tensile elongation, the tensile strength, the tearability may decrease, the dynamic magnification may increase, and if the blending amount is less than the above range, the compression set may deteriorate. .

  The total amount of the blending amount of the zinc acrylate or zinc methacrylate and the blending amount of the diacrylic acid or the lower alkylene glycol of dimethacrylate is 4.0 to 6.0 parts by weight with respect to 100 parts by weight of the rubber component. The range is preferable, and the range of 4.5 to 5.5 parts by mass is more preferable. If it deviates from this range, the tensile elongation, the tensile strength, the tearability may be lowered, the dynamic magnification may be increased, and the compression set may be deteriorated.

<< Other ingredients >>
The anti-vibration rubber composition of the present invention may further contain a fatty acid ester. By adding a fatty acid ester to the vibration-proof rubber composition of the present invention, the dispersibility of the zinc acrylate or zinc methacrylate in the rubber component during kneading is improved, and the mechanical properties of the rubber after crosslinking are improved. Can do. Here, the fatty acid and the alcohol constituting the fatty acid ester may both have a linear structure or a branched structure, may be either saturated or unsaturated, and the carbon number is not particularly limited. In the present invention, 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. May be ethyl stearate, propyl stearate, butyl stearate, ethyl palmitate, propyl palmitate, butyl palmitate and the like. These fatty acid esters may be used alone or in combination of two or more. The blending amount of the fatty acid ester is preferably in the range of 0.02 to 1.2 parts by mass, more preferably in the range of 0.2 to 0.6 parts by mass with respect to 100 parts by mass of the rubber component. If the blending amount is less than 0.02 parts by mass, the effect of improving dispersibility may not be obtained. On the other hand, if it exceeds 1.2 parts by mass, rubber softening, workability deterioration, dynamic magnification deterioration, etc. There is a risk of inviting. The fatty acid ester exhibits the effect of improving dispersibility even when blended separately with the zinc acrylate or zinc methacrylate at the time of kneading 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.

  Further, in the vibration-proof rubber composition of the present invention, the above rubber component, as long as it does not impair the effects of the present invention, a cross-linking agent, a cross-linking accelerator, an aging usually used in the rubber industry. Inhibitor, carbon black, silica, zinc white (ZnO), wax, antioxidant, foaming agent, plasticizer, oil, lubricant, tackifier, petroleum resin, ultraviolet absorber, dispersant, compatibilizer, Additives such as a homogenizing agent can be appropriately blended.

  As the oil, known oils can be used, and are not particularly limited. Specifically, process oils such as aromatic oils, naphthenic oils, paraffin oils, vegetable oils such as palm oil, alkylbenzene oils, etc. Synthetic oil, castor oil, and the like can be used. In the present invention, paraffin oil can be preferably used. These oils may be used alone or in combination of two or more. The blending amount of the oil is preferably in the range of 15 to 45 parts by mass with respect to 100 parts by mass of the rubber component. If the blending amount deviates from the above range, the kneading workability may be deteriorated. When oil-extended rubber is used for the rubber component, the total amount of oil contained in the rubber and oil added separately during mixing may be adjusted within the above range.

  The carbon black may be a known one, and is not particularly limited. Examples thereof include carbon black of grades such as SRF, GPF, FEF, HAF, ISAF, SAF, FT, and MT. In the present invention, FT or FEF can be preferably used. Moreover, these carbon blacks may be used alone or in combination of two or more. The compounding amount of the carbon black is preferably in the range of 15 to 100 parts by mass, more preferably in the range of 20 to 50 parts by mass with respect to 100 parts by mass of the rubber component. If the blending amount is less than 15 parts by mass, the adhesiveness may be deteriorated. On the other hand, if it exceeds 100 parts by mass, the workability may be deteriorated.

  In the present invention, from the viewpoint of accelerating crosslinking, a crosslinking accelerating aid such as zinc white (ZnO) or a fatty acid can be blended. The fatty acid may be a saturated, unsaturated, linear or branched fatty acid, and is not particularly limited as the carbon number of the fatty acid. For example, the fatty acid has 1 to 30 carbon atoms, preferably 15 to 15 carbon atoms. 30 fatty acids, more specifically naphthenic acid such as cyclohexane acid (cyclohexanecarboxylic acid), alkylcyclopentane having a side chain, hexanoic acid, octanoic acid, decanoic acid (including branched carboxylic acid such as neodecanoic acid), Saturated fatty acids such as dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid (stearic acid), unsaturated fatty acids such as methacrylic acid, oleic acid, linoleic acid, linolenic acid, resin acids such as rosin, tall oil acid, abietic acid, etc. Is mentioned. These may be used alone or in combination of two or more. In the present invention, zinc white and stearic acid can be preferably used. The blending amount of these crosslinking accelerating aids is preferably in the range of 1 to 10 parts by mass, more preferably in the range of 2 to 7 parts by mass with respect to 100 parts by mass of the rubber component. When the blending amount is less than 1 part by mass, there is a risk of crosslinking delay or the like. On the other hand, when it exceeds 10 parts by mass, workability and dynamic ratio may be degraded.

  As the anti-aging agent, known ones can be used, and are not particularly limited, and examples thereof include phenol-based anti-aging agents, imidazole-based anti-aging agents, and amine-based anti-aging agents. The blending amount of the anti-aging agent is preferably in the range of 2 to 10 parts by mass, more preferably in the range of 3 to 7 parts by mass with respect to 100 parts by mass of the rubber component.

<< Production Method of Anti-Vibration Rubber Composition >>
When obtaining the anti-vibration rubber composition of the present invention, there is no particular limitation on the blending method of each of the above components, and all the component raw materials may be blended and kneaded at once, or divided into two or three stages. You may mix and knead | mix a component. In the kneading, a kneader such as a roll, an internal mixer, a Banbury rotor or the like can be used. Furthermore, when forming into a sheet shape or a belt shape, a known molding machine such as an extrusion molding machine or a press machine may be used.

  The crosslinking conditions for curing the vibration-insulating rubber composition of the present invention are not particularly limited, but it is usually possible to employ crosslinking conditions at 140 to 180 ° C. for 5 to 120 minutes.

<Anti-vibration rubber>
Moreover, the vibration-proof rubber of the present invention is characterized by using the above-mentioned vibration-proof rubber composition. Such an anti-vibration rubber of the present invention is excellent in crack growth resistance and weather resistance. The anti-vibration rubber of the present invention is excellent in crack growth resistance and weather resistance, and can be used for an anti-vibration member. Although there is no restriction | limiting in particular in the said vibration-proof member, It uses preferably as a vibration-proof member for vehicles with especially severe performance requirements, especially for motor vehicles. Examples of the vibration isolator for an automobile include an engine mount, a torsional damper, a rubber bush, a strut mount, a bound bumper, a helper rubber, a member mount, a stabilizer bush, an air spring, a center support, a rubber propeller shaft, a vibration isolating lever, Examples include companion dampers, damping rubbers, idler arm bushes, steering column bushes, coupling rubbers, body mounts, muffler supports, dynamic dampers, and piping rubbers. Among these, it is particularly suitable for engine mounting.

  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.

<Synthesis of ethylene-butadiene copolymer rubber (EBR1)>
After adding 160 mL of toluene solution to a sufficiently dry 400 mL pressure-resistant glass reactor, ethylene was introduced at 0.8 MPa. On the other hand, in a glove box under a nitrogen atmosphere, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 28.5 μmol in a glass container. And 34.2 μmol of dimethylanilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] and 1.43 mmol of diisobutylaluminum hydride were dissolved in 8 mL of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, an amount of 28.2 μmol in terms of gadolinium was added to the monomer solution, and polymerization was performed at room temperature for 5 minutes. Thereafter, 100 mL of a toluene solution containing 15.23 g (0.28 mol) of 1,3-butadiene was added while lowering the ethylene introduction pressure at a rate of 0.2 MPa / min, and polymerization was further performed for 90 minutes. After the polymerization, 1 mL of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass 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 an ethylene-butadiene copolymer (EBR1). The yield of EBR1 obtained was 12.50 g.

About the obtained EBR1, 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 and evaluated by the following methods. A ¹³ C-NMR spectrum chart of EBR1 is shown in FIG. 1, and a DSC curve is shown in FIG.

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

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

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

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

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

  As a result of the analysis, as the microstructure of the butadiene portion in the obtained EBR1, the cis-1,4-bond amount was 98% and the 1,2-vinyl bond amount was 1.2%. Moreover, the weight average molecular weight (Mw) was 350,000, and molecular weight distribution (Mw / Mn) was 2.2. The ethylene content was 7 mol% (butadiene content was 93 mol%). Furthermore, the block polyethylene melting temperature (DSC peak temperature) was 121 ° C., and the chain structure was a block. These results are listed in Table 1.

<Synthesis of ethylene-butadiene copolymer rubber (EBR2)>
After adding 100 ml of toluene solution to a sufficiently dried 400 ml pressure-resistant glass reactor, ethylene was introduced at 0.8 MPa. On the other hand, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 28.5 μmol in a glass container in a glove box under a nitrogen atmosphere. , 34.2 μmol of dimethylanilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] and 1.43 mmol of diisobutylaluminum hydride were dissolved in 8 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, an amount of 28.2 μmol in terms of gadolinium was added to the monomer solution, and polymerization was performed at room temperature for 5 minutes. Thereafter, 30 ml of a toluene solution containing 4.57 g (0.085 mol) of 1,3-butadiene was added while lowering the ethylene introduction pressure at a rate of 0.2 MPa / min, and polymerization was further performed for 60 minutes. Next, “the ethylene introduction pressure was returned to 0.8 MPa, polymerization was performed for 5 minutes, and then the ethylene introduction pressure was decreased at a rate of 0.2 MPa / min, while 4.57 g of 1,3-butadiene (0.085 mol). The operation of “addition of 30 ml of a toluene solution containing) followed by further polymerization for 60 minutes” was repeated a total of 3 times. After the polymerization, 1 ml of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass of isopropanol solution was added to stop the reaction, and a copolymer with a large amount of methanol was added. Was separated and vacuum dried at 70 ° C. to obtain an ethylene-butadiene copolymer (EBR2). The yield of EBR2 obtained was 14.00 g.

  With respect to the obtained EBR2, 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 and evaluated by the above methods. As a result, as the microstructure of the butadiene portion in the obtained EBR2, the cis-1,4-bond amount was 97% and the 1,2-vinyl bond amount was 1.2%. Moreover, the weight average molecular weight (Mw) was 283,000, and molecular weight distribution (Mw / Mn) was 2.8. The ethylene content was 13 mol% (butadiene content was 87 mol%). Furthermore, the block polyethylene melting temperature (DSC peak temperature) was 121 ° C., and the chain structure was a block. These results are listed in Table 1.

<Synthesis of ethylene-butadiene copolymer rubber (EBR3)>
After adding 150 ml of toluene to a sufficiently dry 2 L stainless steel reactor, ethylene was introduced at 0.8 MPa. On the other hand, in a glove box under a nitrogen atmosphere, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 14.5 μmol in a glass container. Then, 14.1 μmol of triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ ) and 0.87 mmol of diisobutylaluminum hydride were charged and dissolved in 5 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, an amount of 14.1 μmol in terms of gadolinium was added to the monomer solution, and polymerization was carried out at 50 ° C. for 5 minutes. Thereafter, 20 ml of a toluene solution containing 3.05 g (0.056 mol) of 1,3-butadiene was added while lowering the ethylene introduction pressure at a rate of 0.2 MPa / min, and polymerization was further performed for 15 minutes. Next, “the ethylene introduction pressure was returned to 0.8 MPa, polymerization was performed for 5 minutes, and then the ethylene introduction pressure was reduced at a rate of 0.2 MPa / min, while 6.09 g (0. The operation of adding 40 ml of a toluene solution containing 113 mol) and then performing polymerization for another 30 minutes was repeated a total of 3 times. After the polymerization, 1 ml of 2,2′-methylene-bis (4-ethyl-6-t-butylphenol) (NS-5) 5% by mass isopropanol solution was added to stop the reaction, and the copolymer was separated with a large amount of methanol. And vacuum drying at 70 ° C. to obtain an ethylene-butadiene copolymer (EBR3). The yield of EBR3 obtained was 24.50 g.

  About the obtained EBR3, 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 and evaluated by the above methods. The DSC curve of copolymer C is shown in FIG. As a result, as the microstructure of the butadiene portion in the obtained EBR3, the cis-1,4-bond amount was 97% and the 1,2-vinyl bond amount was 1.4%. Moreover, the weight average molecular weight (Mw) was 205,000 and molecular weight distribution (Mw / Mn) was 9.15. Moreover, ethylene content rate was 34 mol% (butadiene content rate was 66 mol%). Furthermore, the block polyethylene melting temperature (DSC peak temperature) was 121 ° C., and the chain structure was a block. These results are listed in Table 1.

<Synthesis of ethylene-butadiene copolymer rubber (EBR4)>
In the synthesis of EBR3, instead of using bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ], bis (2-phenyl-1- Experiments were conducted in the same manner except that methylindenyl) gadolinium bis (dimethylsilylamide) [(2-Ph-1-MeC ₉ H ₅ ) ₂ GdN (SiHMe ₂ ) ₂ ] was used, and ethylene-butadiene co A polymer (EBR4) was obtained. The yield of EBR4 obtained was 28.55 g.

  With respect to the obtained EBR4, 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 and evaluated by the above methods. As a result, as the microstructure of the butadiene portion in the obtained EBR4, the cis-1,4-bond amount was 97% and the 1,2-vinyl bond amount was 1.8%. Moreover, the weight average molecular weight (Mw) was 221,000, and molecular weight distribution (Mw / Mn) was 3.13. The ethylene content was 45 mol% (butadiene content was 55 mol%). Furthermore, the block polyethylene melting temperature (DSC peak temperature) was 122 ° C., and the chain structure was a block. These results are listed in Table 1.

(Examples 1-8 and Comparative Examples 1-3)
A rubber composition having a formulation shown in Table 2 was prepared by kneading and crosslinking to prepare a rubber sheet having a length of 120 mm, a width of 120 mm, and a thickness of 2 mm. The resulting rubber sheet was evaluated and measured for crack growth resistance, ozone resistance, and tan δ by the following methods. The results are shown in Table 2.

(6) Crack growth resistance About the sample obtained by each Example and the comparative example, a 0.5 mm crack was put in the center part of a JIS3 test piece, and repeated fatigue was given at a constant strain of 0 to 100% at 35 ° C. The number of times until the sample was cut was measured, and indexed with Comparative Example 1 as 100. The larger the index value, the greater the number of times until cutting and the better the crack growth resistance.

(7) Ozone resistance A dynamic ozone test was performed according to JIS K 6259. 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). Test atmosphere temperature: 40 ° C., ozone concentration: 50 pphm. The evaluation results are obtained by indexing the time until the occurrence of ozone cracking with Comparative Example 1 as 100. The larger the index value, the longer the time until ozone cracking occurs, indicating better ozone resistance.

(8) tan δ
In accordance with JIS K 6385, tan δ is a non-resonant method of a dynamic property measurement test. A sample having a height of 30 mm × φ30 mm is subjected to a deflection of 10% (3 mm), and the frequency is 15 Hz in the direction perpendicular to the axis of the test piece. The measurement was performed under the condition of amplitude ± 0.5 mm, and the index was displayed with Comparative Example 1 as 100. The larger the index value, the larger the hysteresis loss and the better the loss characteristic.

* 1 NR: Natural rubber, “RSS # 1”
* 2 EPDM: “EP96” manufactured by JSR, ENB content = 6.0% by mass, ethylene content = 66% by mass (15 parts by mass of oil component per 30 parts by mass of rubber component)
* 3 Anti-aging agent: 2,2,4-trimethyl-1,2-dihydroquinoline polymer, “NOCRACK 224” manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 4 Carbon Black: FT grade, Asahi Thermal “Asahi Thermal”
* 5 Wax: Trade name “Suntite S” (manufactured by Seiko Chemical Co., Ltd.)
* 6 Peroxide: Di (2-t-butylperoxyisopropyl) benzene, NOF "Peroximon F-40"
* 7 Zinc diacrylate: “SR633” manufactured by Sartomer
* 8 Ethylene glycol dimethacrylate (n = 1): Sanshin Chemical Co., Ltd., trade name “Sunester EG”, represented by the above general formula (I), R ¹ is a methyl group, AO is ethylene oxide (C ₂ H ₄ O) and n is 1 compound * 9 Diethylene glycol dimethacrylate (n = 2): manufactured by NOF Corporation, trade name “Blemmer PDE-100”, represented by the above general formula (I), R ¹ Is a methyl group, AO is ethylene oxide (C ₂ H ₄ O), and n is 2

  From the results shown in Table 2, a conjugated diene polymer, a conjugated diene-nonconjugated olefin copolymer, and an ethylene-propylene-diene rubber are used as the rubber component of the rubber composition. By blending an oxide and zinc diacrylate and a lower alkylene glycol dimethacrylate as a co-crosslinking agent, the crack growth resistance and ozone resistance of the rubber composition are greatly improved. You can see that the loss also increases.

  Moreover, from the results of Examples 1 to 4 and Examples 5 to 8, crack growth resistance and ozone resistance were improved as the ethylene content in the blended ethylene-butadiene copolymer rubber (EBR) increased. It can be seen that the hysteresis loss increases.

Claims (12)

The rubber component includes a conjugated diene polymer, a conjugated diene-nonconjugated olefin copolymer, and a nonconjugated diene-nonconjugated olefin copolymer,
The conjugated diene-nonconjugated olefin copolymer is an ethylene-butadiene block copolymer;
The non-conjugated diene-non-conjugated olefin copolymer contains an ethylene-propylene-diene rubber;
As a crosslinking agent, it contains a peroxide,
As a co-crosslinking agent, zinc acrylate or zinc methacrylate, and diacrylic acid or dimethacrylic acid lower alkylene glycols,
The anti-vibration rubber composition, wherein each lower alkylene moiety in the diacrylic acid or dimethacrylic acid lower alkylene glycol has 1 to 4 carbon atoms. The rubber component includes a conjugated diene polymer, a conjugated diene-nonconjugated olefin copolymer, and a nonconjugated diene-nonconjugated olefin copolymer,
The conjugated diene-nonconjugated olefin copolymer is a block copolymer,
The conjugated diene-nonconjugated olefin copolymer has a cis-1,4 bond content of a conjugated diene moiety of 95% or more,
The non-conjugated diene-non-conjugated olefin copolymer contains an ethylene-propylene-diene rubber;
As a crosslinking agent, it contains a peroxide,
As a co-crosslinking agent, zinc acrylate or zinc methacrylate, and diacrylic acid or dimethacrylic acid lower alkylene glycols,
Carbon number of each lower alkylene moiety in the lower alkylene glycols of diacrylic acid or dimethacrylic acid is 1 to 4.
An anti-vibration rubber composition characterized by that. The anti-vibration rubber composition according to claim 1 or 2, wherein the conjugated diene-nonconjugated olefin copolymer has a conjugated diene-derived content of 55 mol% to 95 mol%. The diacrylic acid or dialkyl methacrylate lower alkylene glycol is represented by the following general formula (I):

[Wherein, R ¹ is independently hydrogen or a methyl group, AO is independently methylene oxide, ethylene oxide, propylene oxide or butylene oxide, and n is an integer of 1 to 4. The anti-vibration rubber composition according to claim 1 or 2 , wherein 2. The vibration-proof rubber composition according to claim 1, wherein the ethylene-butadiene block copolymer has a cis-1,4 bond content of a butadiene portion of 50% or more. The vibration-insulating rubber composition according to claim 1 or 2 , wherein the conjugated diene-nonconjugated olefin copolymer has a polystyrene-equivalent weight average molecular weight (Mw) of 10,000 to 10,000,000. object. The vibration-insulating rubber composition according to claim 1 or 2 , wherein the conjugated diene-nonconjugated olefin copolymer has a molecular weight distribution (Mw / Mn) of 10 or less. The vibration-insulating rubber composition according to claim 2 , wherein the non-conjugated olefin is an acyclic olefin. The vibration-insulating rubber composition according to claim 2 or 8 , wherein the non-conjugated olefin has 2 to 10 carbon atoms. The vibration-insulating rubber composition according to claim 8 or 9 , wherein the non-conjugated olefin is at least one selected from the group consisting of ethylene, propylene, and 1-butene. The vibration-insulating rubber composition according to claim 10 , wherein the non-conjugated olefin is ethylene. An anti-vibration rubber using the anti-vibration rubber composition according to claim 1 .

Images