JP5893937B2 - Anti-vibration rubber composition, crosslinked anti-vibration rubber composition and anti-vibration rubber - Google Patents

Description

  The present invention relates to an anti-vibration rubber composition, a cross-linked anti-vibration rubber composition and an anti-vibration rubber, in particular, an anti-vibration rubber composition excellent in stretch fatigue resistance, ozone resistance, low dynamic magnification, low temperature characteristics and processability, and cross-linking The present invention relates to an anti-vibration rubber composition and an anti-vibration rubber.

Conventionally, in various vehicles such as automobiles, in order to improve the comfort of passengers, various anti-vibration materials have been arranged at sites that are sources of vibration and noise to reduce the intrusion of vibration and noise into the room. Attempts have been made.
For example, for the engine that is the main source of vibration and noise, the vibration when the engine is driven is absorbed by using rubber as a component of vibration isolation devices such as torsional dampers, engine mounts, and muffler hangers. Vibration and noise intrusion and noise diffusion to the surrounding environment are reduced.

As a basic characteristic of such an anti-vibration rubber, a strength characteristic that supports a mass such as an engine and an anti-vibration performance that absorbs and suppresses the vibration are required. Furthermore, when used in a high-temperature environment such as an engine room, it has excellent strength characteristics, low dynamic magnification and excellent anti-vibration performance, as well as heat resistance, ozone resistance and compression set. It is also required to be excellent. In particular, in recent years, the engine room temperature tends to rise as the engine output is increased and the space in the engine room is reduced due to the expansion of the interior space. It has become more severe.
Since automobiles are also used in high latitude areas, in the case of automobile anti-vibration rubber, in addition to the above characteristics, improvement of spring characteristics (hereinafter referred to as “low temperature characteristics”) in a low temperature environment is also required. It is done.

  Thus, in order to give comprehensively excellent characteristics, development of blending a predetermined amount of a rubber component of an anti-vibration rubber, a crosslinking system and other additives has been actively conducted, and many patent applications have been filed. Among the numerous patent applications, there are those that positively employ bismaleimide compounds as an improvement of the crosslinking system.

For example, Patent Document 1 discloses a rubber composition excellent in heat resistance, low dynamic magnification, and the like by blending sulfur, bismaleimide, and specific carbon black with a rubber component.
Patent Document 2 discloses a rubber composition having excellent heat resistance, low dynamic magnification, and durability by using a bismaleimide compound and a thiazole vulcanization accelerator.

  However, the rubber compositions of Patent Document 1 and Patent Document 2 are excellent in heat resistance, low dynamic magnification, and the like, but are slightly inferior in terms of stretch fatigue properties, low dynamic magnification, and low temperature characteristics. Further, in order to maintain the spring characteristics that are strongly demanded of the vibration-proof rubber for a long period of time, it is necessary to suppress the modulus change rate as much as possible and to further improve the heat resistance.

  Therefore, in order to improve the elongation fatigue property, the low dynamic magnification, and the low temperature characteristics by containing sulfur, a specific sulfur compound, and a bismaleimide compound as a vulcanizing agent, An anti-vibration rubber composition containing 0.5 parts by mass or less of sulfur, 0.5 to 2 parts by mass of a sulfur-containing compound having a specific structure, and 0.5 to 3 parts by mass of a bismaleimide compound with respect to 100 parts by mass of rubber is disclosed. Has been.

JP-A-3-258840 JP 2005-194501 A JP 2010-254872 A

  However, although the anti-vibration rubber obtained by the technique of Patent Document 3 has certain stretch fatigue properties, low dynamic magnification, and low temperature characteristics, further improvement has been desired in terms of stretch fatigue properties and ozone resistance. .

  For this reason, the object of the present invention is to solve the above-mentioned problems. Specifically, by optimizing the content of the components, vibration isolation with excellent low dynamic magnification, low temperature characteristics, stretch fatigue characteristics and ozone resistance is achieved. An object of the present invention is to provide a rubber composition, a crosslinked vibration-proof rubber composition, a vibration-proof rubber composition excellent in low-temperature characteristics and processability, and a vibration-proof rubber using the crosslinked vibration-proof rubber composition.

  The inventors of the present invention have made extensive studies to solve the above-mentioned problems, and as a result, for the vibration-proof rubber composition, the bismaleimide compound as a vulcanizing agent, sulfur, and thiuram-based vulcanization acceleration (however, monosulfide only) ) And N-phenyl-N- (trichloromethylthio) benzenesulfonamide, and these synergistic effects result in low dynamic magnification, fracture characteristics, heat resistance and durability. As a result of the addition of a conjugated diene compound-nonconjugated olefin copolymer in the rubber component, it becomes possible to improve the elongation fatigue and ozone resistance, and as a result, the above-mentioned problems can be achieved, The present invention has been completed.

The present invention has been made based on such findings, and the gist thereof is as follows.
(1) a rubber component having a conjugated diene compound-nonconjugated olefin copolymer and a conjugated diene polymer;
A bismaleimide compound,
Sulfur and
Thiuram vulcanization accelerators (although,. Except those having a chemical structure of only monosulfide) and, viewed contains a N- phenyl -N- (trichloromethyl thio) benzenesulfonamide,
The content of the conjugated diene compound-nonconjugated olefin copolymer-derived moiety in the conjugated diene compound is 30 mol% or more,
The cis-1,4 bond content of the conjugated diene compound-derived moiety in the conjugated diene compound-nonconjugated olefin copolymer is more than 92%;
The content of the conjugated diene compound-nonconjugated olefin copolymer in 100 parts by mass of the rubber component is 10 to 90 parts by mass,
The non-conjugated olefin is an acyclic olefin,
An anti-vibration rubber composition characterized by that.

(2) The anti-vibration rubber composition according to the above (1), wherein the content of the thiuram vulcanization accelerator is 1.0 to 4.0 parts by mass with respect to 100 parts by mass of the rubber component. object.

(3) The anti-vibration rubber composition as described in (1) above, wherein the sulfur content is 0.4 to 1.0 part by mass with respect to 100 parts by mass of the rubber component.

(4) The anti-vibration rubber according to (1), wherein the conjugated diene compound-nonconjugated olefin copolymer has a cis-1,4 bond content of a conjugated diene compound-derived portion of 50% or more. Composition.

(5) The anti-vibration rubber composition according to (1) above, wherein the conjugated diene compound-nonconjugated olefin copolymer has a weight average molecular weight in terms of polystyrene of 10,000 to 10,000,000.

(6) The anti-vibration rubber composition as described in (1) above, wherein the conjugated diene compound-nonconjugated olefin copolymer has a molecular weight distribution (Mw / Mn) of 10 or less.

(7) The anti-vibration rubber composition according to (1) above, wherein the content of the conjugated diene compound-nonconjugated olefin copolymer is 10 to 90 parts by mass with respect to 100 parts by mass of the rubber component. object.

(8) The vibration-insulating rubber composition according to (1), wherein the non-conjugated olefin is an acyclic olefin.

(9) The vibration-insulating rubber composition according to (1), wherein the non-conjugated olefin has 2 to 10 carbon atoms.

(10) The anti-vibration rubber composition as described in (8) or (9) above, wherein the non-conjugated olefin is at least one selected from the group consisting of ethylene, propylene and 1-butene.

(11) The anti-vibration rubber composition as described in (10) above, wherein the non-conjugated olefin is ethylene.

(12) The anti-vibration rubber composition as described in (1) above, wherein the conjugated diene polymer is natural rubber.

(13) A crosslinked anti-vibration rubber composition obtained by crosslinking the anti-vibration rubber composition according to (1).

(14) An anti-vibration rubber using the anti-vibration rubber composition according to (1) or the crosslinked anti-vibration rubber composition according to (13).

  According to the present invention, an anti-vibration rubber composition and a crosslinked anti-vibration rubber composition excellent in low dynamic magnification, low temperature characteristics, stretch fatigue characteristics and ozone resistance, and anti-vibration rubber excellent in the low temperature characteristics and processability An anti-vibration rubber using the composition and the crosslinked anti-vibration rubber composition can be provided.

<Anti-Vibration Rubber Composition>
The anti-vibration rubber composition according to the present invention comprises a rubber component having a conjugated diene compound-nonconjugated olefin copolymer and a conjugated diene polymer, a vulcanizing agent having a bismaleimide compound, and N-phenyl-N-. And (trichloromethylthio) benzenesulfonamide.

(Rubber component)
The rubber component constituting the vibration-proof rubber composition of the present invention includes a conjugated diene compound-nonconjugated olefin copolymer and a conjugated diene compound.

Conjugated diene compound-nonconjugated olefin copolymer By having a conjugated diene compound-nonconjugated olefin copolymer in the rubber component, the action of the nonconjugated olefin component of the conjugated diene compound-nonconjugated olefin copolymer. Can realize excellent dynamic magnification and low temperature characteristics.

  Here, the conjugated diene compound-nonconjugated olefin copolymer is a copolymer of a conjugated diene compound and a nonconjugated olefin, and includes a nonconjugated olefin as a monomer unit component in the copolymer.

There is no restriction | limiting in particular as content of the conjugated diene compound origin part in the said conjugated diene compound-nonconjugated olefin copolymer, Although it can select suitably according to the objective, It is preferable that it is 30 mol%-80 mol%. .
When the content of the conjugated diene compound-derived portion in the conjugated diene compound-nonconjugated olefin copolymer is 30 mol% or more, the dynamic ratio can be improved. When the content is 80 mol% or less, the ratio of the nonconjugated olefin is This is because it increases and the stretch fatigue property is improved.

Moreover, there is no restriction | limiting in particular about content of the said nonconjugated olefin origin part in the said conjugated diene compound-nonconjugated olefin copolymer, According to the objective, it can select suitably.
For example, from the viewpoint of ensuring ozone resistance and crack growth resistance, the content of the non-conjugated olefin-derived portion is preferably in the range of 20 to 70 mol%. When the content of the non-conjugated olefin-derived portion in the conjugated diene compound-non-conjugated olefin copolymer is 20 mol% or more, the elongation fatigue property can be improved. When the content is 70 mol% or less, the dynamic magnification is improved. Is possible.

Further, the amount of cis-1,4 bonds in the conjugated diene compound-derived portion in the conjugated diene compound-nonconjugated olefin copolymer is not particularly limited and can be appropriately selected according to the purpose. % Or more is preferable.
If the amount of cis 1,4-bond in the conjugated diene compound-derived portion is 50% or more, a low glass transition point (Tg) can be maintained, whereby physical properties such as elongation fatigue resistance and wear resistance can be maintained. Is improved. Furthermore, by setting the cis 1,4-bond amount of the conjugated diene compound-derived portion to more than 92%, it becomes possible to improve dynamic magnification, elongation fatigue resistance, ozone resistance, heat resistance, and 95% or more. By doing so, it becomes possible to further improve dynamic magnification, stretch fatigue resistance, ozone resistance, and heat resistance.
The cis-1,4 bond amount is an amount in the conjugated diene compound-derived portion, and is not a ratio to the entire copolymer.

  On the other hand, in the conjugated diene compound-nonconjugated olefin copolymer, the nonconjugated olefin used as a monomer is a nonconjugated olefin other than the conjugated diene compound, and has excellent heat resistance and in the main chain of the copolymer. It is possible to increase the degree of freedom of design as an elastomer by reducing the proportion of double bonds occupied and reducing the crystallinity. Moreover, as a nonconjugated olefin, it is preferable that it is an acyclic olefin, and it is preferable that carbon number of this nonconjugated olefin is 2-10.

Accordingly, preferred examples of the non-conjugated olefin include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene. Among these, ethylene, propylene And 1-butene are preferred, with ethylene being particularly preferred. Here, the non-conjugated olefin does not contain styrene. Since the α-olefin has a double bond at the α-position of the olefin, copolymerization with a conjugated diene can be performed efficiently. These non-conjugated olefins may be used alone or in combination of two or more. In addition, an olefin refers to the compound which is an aliphatic unsaturated hydrocarbon and has one or more carbon-carbon double bonds.
In addition, when a block portion composed of a monomer unit of non-conjugated olefin is provided, it exhibits static crystallinity and is excellent in mechanical properties such as breaking strength.

  In the conjugated diene compound-nonconjugated olefin copolymer, the conjugated diene compound used as a monomer preferably has 4 to 12 carbon atoms. Specific examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and among these, 1,3-butadiene and isoprene are preferable. Moreover, these conjugated diene compounds may be used independently and may be used in combination of 2 or more type.

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

  In the conjugated diene compound-nonconjugated olefin copolymer, the weight average molecular weight (Mw) is not particularly limited, and the weight average molecular weight (Mw) is not particularly limited. From the viewpoint of application to a molecular structure material, the polystyrene-converted weight average molecular weight (Mw) of the copolymer is preferably 10,000 to 10,000,000, and is 10,000 to 1,000,000. It is more preferable, 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. This is because if the molecular weight distribution exceeds 10, the physical properties are not uniform. Here, the average molecular weight and the molecular weight distribution can be determined using polystyrene as a standard substance by gel permeation chromatography (GPC).

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

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

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

・ Random copolymer When the conjugated diene compound-nonconjugated olefin copolymer is a random copolymer, the arrangement of the monomer units of the nonconjugated olefin is irregular, and the copolymer causes phase separation. Without observing the crystallization temperature derived from the block portion. That is, since it becomes possible to introduce a non-conjugated olefin having properties such as heat resistance into the main chain of the copolymer, the heat resistance is improved.

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

-Alternating copolymer The alternating copolymer has a structure in which a conjugated diene compound and a non-conjugated olefin are alternately arranged (a molecular chain of -ABABABAB- where A is a non-conjugated olefin and B is a conjugated diene compound) A polymer having a structure).

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

The content of the conjugated diene compound-nonconjugated olefin copolymer in 100 parts by mass of the rubber component is preferably 10 to 90 parts by mass, and more preferably 10 to 60 parts by mass.
If the content of the conjugated diene compound-nonconjugated olefin copolymer is less than 10 parts by mass, the desired dynamic magnification and elongation fatigue properties may not be obtained. And cut resistance may be reduced.

-Manufacturing method of conjugated diene compound-nonconjugated olefin copolymer Next, the manufacturing method of said conjugated diene compound-nonconjugated olefin type copolymer is demonstrated in detail. However, the manufacturing method described in detail below is merely an example.
The process for producing a conjugated diene compound-nonconjugated olefin copolymer is carried out in the presence of a first polymerization catalyst composition, a second polymerization catalyst composition, or a third polymerization catalyst composition described below. It is preferable to include a step of polymerizing the conjugated diene compound. 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, hexane, cyclohexane, mixtures thereof etc. are mentioned.

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^a〜Ｒ^fは、それぞれ独立して炭素数１〜３のアルキル基又は水素原子を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体、及び下記一般式（ＩＩ）： First polymerization catalyst composition As the first polymerization catalyst composition (hereinafter also referred to as “first polymerization catalyst composition”), the following general formula (I):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents unsubstituted or substituted indenyl, and R ^{a to} R ^f each independently represents an alkyl having 1 to 3 carbon atoms. A group or a hydrogen atom, L represents a neutral Lewis base, w represents an integer of 0 to 3), and the following general formula (II):

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

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

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^R'は、無置換もしくは置換シクロペンタジエニル、インデニル又はフルオレニルを示し、Ｘは、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示し、［Ｂ］^-は、非配位性アニオンを示す）で表されるハーフメタロセンカチオン錯体からる群より選択される少なくとも１種類の錯体を含む重合触媒組成物が挙げられる。

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

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

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

In the half metallocene cation complex represented by the general formula (III), Cp ^{R ′} in the formula is unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and among these, unsubstituted or substituted indenyl It is preferable that Cp ^{R ′} having a cyclopentadienyl ring as a basic skeleton is represented by C ₅ H _5-X R _X. Here, X is an integer of 0-5. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of Cp ^{R ′} having a cyclopentadienyl ring as a basic skeleton include the following.

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

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

In the general formula (III), Cp ^{R ′} having the fluorenyl ring as a basic skeleton can be represented by C ₁₃ H _9-X R _X or C ₁₃ H _17-X R _X. Here, X is an integer of 0-9 or 0-17. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group.

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

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

The metallocene complex represented by the general formula (II) includes a silyl ligand [—SiX ′ ₃ ]. X ′ contained in the silyl ligand [—SiX ′ ₃ ] is a group defined in the same manner as X in the general formula (III) described below, and preferred groups are also the same.

  In the general formula (III), X is a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, and a hydrocarbon group having 1 to 20 carbon atoms. Here, examples of the alkoxide group include aliphatic alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group; a phenoxy group and 2,6-dioxy -Tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dinepentylphenoxy group, 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, Examples include aryloxide groups such as 2-isopropyl-6-neopentylphenoxy group, and among these, 2,6-di-tert-butylphenoxy group is preferable.

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

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

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

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

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

In the general formula (III), [B] ^- The non-coordinating anion represented by, for example, a tetravalent boron anion. Specific examples of the tetravalent boron anion include tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tri Decahydride-7,8-dicarbaoundecaborate and the like can be mentioned, and among these, tetrakis (pentafluorophenyl) borate is preferable.

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

  Further, the metallocene complex represented by the general formula (I) and the formula (II) and the half metallocene cation complex represented by the general formula (III) may exist as a monomer, It may exist as a body or higher multimer.

（式中、Ｘ''はハライドを示す。）
上記一般式（ＩＩ）で表されるメタロセン錯体は、例えば、溶媒中でランタノイドトリスハライド、スカンジウムトリスハライド又はイットリウムトリスハライドを、インデニルの塩（例えばカリウム塩やリチウム塩）及びシリルの塩（例えばカリウム塩やリチウム塩）と反応させることで得ることができる。なお、反応温度は室温程度にすればよいので、温和な条件で製造することができる。また、反応時間は任意であるが、数時間〜数十時間程度である。反応溶媒は特に限定されないが、原料及び生成物を溶解する溶媒であることが好ましく、例えばトルエンを用いればよい。以下に、一般式（ＩＩ）で表されるメタロセン錯体を得るための反応例を示す。 The metallocene complex represented by the general formula (I) includes, for example, a lanthanoid trishalide, scandium trishalide, or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt) and bis (trialkylsilyl). It can be obtained by reacting with an amide salt (for example, potassium salt or lithium salt). In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used. Below, the reaction example for obtaining the metallocene complex represented by general formula (I) is shown.

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

（式中、Ｘ''はハライドを示す。）

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

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

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

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

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

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

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

  The aluminoxane is preferably an alkylaminoxan, and examples thereof include methylaluminoxane (MAO) and modified methylaluminoxane. As the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem Co., Ltd.) and the like are preferable. The content of aluminoxane in the first polymerization catalyst composition is such that the element ratio Al / M between the central metal M of the metallocene complex and the aluminum element Al of the aluminoxane is about 10 to 1000, preferably about 100. It is preferable to make it.

  On the other hand, as the organoaluminum compound, the general formula AlRR′R ″ (wherein R and R ′ are each independently a C1-C10 hydrocarbon group or a hydrogen atom, and R ″ is a C1-C10 An organoaluminum compound represented by (a hydrocarbon group) is preferable. Examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, and dialkylaluminum hydride. Among these, trialkylaluminum is preferable. Examples of the trialkylaluminum include triethylaluminum and triisobutylaluminum. In addition, it is preferable that it is 1-50 times mole with respect to a metallocene complex, and, as for content of the organoaluminum compound in the said polymerization catalyst composition, it is still more preferable that it is about 10 times mole.

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

Second Polymerization Catalyst Composition Next, the second polymerization catalyst composition (hereinafter also referred to as “second polymerization catalyst composition”) 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. At least one selected from the group consisting of at least one halogen compound (B-3) among organic compounds;
The polymerization catalyst composition containing is mentioned.
When the second polymerization catalyst composition contains at least one of the ionic compound (B-1) and the halogen compound (B-3), the polymerization catalyst composition further comprises:
(C) Component: The following general formula (X):
YR ¹ _a R ² _b R ³ _c (X)
[Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R1 and R2 are the same or different and have 1 to 10 carbon atoms. R ³ is a group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is 1 in the periodic table. When the metal is selected from the group, a is 1, and b and c are 0, and when Y is the metal selected from groups 2 and 12 of the periodic table, a and In the case where b is 1 and c is 0, and Y is a metal selected from Group 13 of the Periodic Table, a, b, and c are 1].

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

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

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

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

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

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

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

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

  The halogen compound represented by (B-3) is composed of at least one of a Lewis acid, a complex compound of a metal halide and a Lewis base, and an organic compound containing an active halogen, and is, for example, the component (A). By reacting with a rare earth element compound or a reaction product thereof with a Lewis base, a cationic transition metal compound, a halogenated transition metal compound, or a compound in which the transition metal center is deficient in charge can be generated. In addition, it is preferable that content of the sum total of the halogen compound in the said 2nd polymerization catalyst composition is 1-5 times mole with respect to (A) component.

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

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

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

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

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

The component (C) used in the second polymerization catalyst composition is the general formula (X):
YR ¹ _a R ² _b R ³ _c (X)
(In the formula, Y is a metal selected from Group 1, Group 2, Group 12, and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. R ³ is a hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is a periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1). Yes, the following general formula (Xa):
AlR ¹ R ² R ³ (Xa)
[Wherein, R ¹ and R ² are the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ represents the above It may be the same as or different from R ¹ or R ² ]. Examples of the organoaluminum compound represented by the general formula (X) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, and tripentylaluminum. , Trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diiso hydrogenated Hexyl aluminum, dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propyl aluminum Muzi hydride, isobutylaluminum dihydride and the like. Among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. The organoaluminum compound as component (C) described above can be used alone or in combination of two or more. In addition, it is preferable that it is 1-50 times mole with respect to (A) component, and, as for content of the organoaluminum compound in the said 2nd polymerization catalyst composition, it is still more preferable that it is about 10 times mole.

Next, the structure and performance of the compound contained in the second catalyst composition as a polymerization catalyst will be described.
As a polymerization catalyst, it is for superposition | polymerization, and following formula (A):
R _a MX _b QY _b (A)
[In the formula, each R independently represents an unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium; 20 represents a hydrocarbon group, X is μ-coordinated to M and Q, Q represents a group 13 element of the periodic table, and Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or A hydrogen atom, wherein Y is coordinated to Q and a and b are 2].

（式中、Ｍ¹は、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^A及びＲ^Bは、それぞれ独立して炭素数１〜２０の炭化水素基を示し、該Ｒ^A及びＲ^Bは、Ｍ¹及びＡｌにμ配位しており、Ｒ^C及びＲ^Dは、それぞれ独立して炭素数１〜２０の炭化水素基又は水素原子を示す）で表されるメタロセン系複合触媒が挙げられる。
上記メタロセン系重合触媒を用いることで、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、重合体合成時に使用されるアルキルアルミニウムの量を低減したり、無くしたりすることが可能となる。なお、従来の触媒系を用いると、重合体合成時に大量のアルキルアルミニウムを用いる必要がある。例えば、従来の触媒系では、金属触媒に対して１０当量以上のアルキルアルミニウムを用いる必要があるところ、上記メタロセン系複合触媒であれば、５当量程度のアルキルアルミニウムを加えることで、優れた触媒作用が発揮される。 In a preferred example of the metallocene composite catalyst, the following formula (XV):

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

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

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

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

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

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

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

In the above formula (XV), Cp ^R is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7X R _X or C ₉ H _11X R _X. Here, X is an integer of 0-7 or 0-11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group.
Specific examples of the substituted indenyl include 2-phenylindenyl and 2-methylindenyl. Incidentally, the two Cp ^R in the formula (XV) may each be the same or different from each other.

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

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

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

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

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

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

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

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

On the other hand, the organoaluminum compound used for the production of the metallocene composite catalyst is represented by AlR ^K R ^L R ^M , where R ^K and R ^L are each independently a monovalent carbon atom having 1 to 20 carbon atoms. R ^M is a hydrogen group or a hydrogen atom, and R ^M is a monovalent hydrocarbon group having 1 to 20 carbon atoms, provided that R ^M may be the same as or different from R ^K or R ^L described above. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group and tetradecyl group. , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

  Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, Hexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride , Dioctylaluminum hydride, diisooctylaluminum hydride; ethylaluminum dihydride, n-propylaluminium Dihydride, isobutyl aluminum dihydride and the like. Among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. Moreover, these organoaluminum compounds can be used individually by 1 type, or 2 or more types can be mixed and used for them. In addition, the amount of the organoaluminum compound used for the production of the metallocene composite catalyst is preferably 1 to 50 times mole, more preferably about 10 times mole relative to the metallocene complex.

Third polymerization catalyst composition The third polymerization catalyst composition (hereinafter also referred to as “third polymerization catalyst composition”) includes the metallocene composite catalyst and a boron anion. Furthermore, it is preferable that other components contained in the polymerization catalyst composition containing a normal metallocene catalyst, for example, a co-catalyst and the like are included. The metallocene composite catalyst and boron anion are also referred to as a two-component catalyst. According to the third polymerization catalyst composition, since the boron anion is further contained in the same manner as the metallocene composite catalyst, the content of each monomer component in the polymer can be arbitrarily controlled. It becomes.

  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, the metallocene composite catalyst and the boron anion need to be used. If a boron anion is present, the metallocene composite catalyst of the above formula (XV) cannot be synthesized. Therefore, for the preparation of the third polymerization catalyst composition, it is necessary to synthesize the metallocene composite catalyst in advance, isolate and purify the metallocene composite catalyst, and then combine with the boron anion.

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

-Polymerization process In the production of the non-conjugated olefin copolymer in the rubber composition according to the present invention, when the polymerization catalyst or the polymerization catalyst composition is used, for example, a polymer by a polymerization reaction using a conventional coordination ion polymerization catalyst. It can carry out similarly to the manufacturing method of. Here, when the method for producing a copolymer uses the above-described polymerization catalyst composition, for example, (1) the configuration of the polymerization catalyst composition in a polymerization reaction system containing a non-conjugated olefin and a conjugated diene compound as monomers. The components may be provided separately and the polymerization catalyst composition may be prepared in the reaction system, or (2) a previously prepared polymerization catalyst composition 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 nonconjugated olefin and a conjugated diene compound.

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

  The polymerization reaction is preferably performed in an atmosphere of an inert gas, preferably nitrogen gas or argon gas. The polymerization temperature of the polymerization reaction is not particularly limited, but is preferably in the range of −100 ° C. to 200 ° C., for example, and can be about room temperature. If the polymerization temperature is raised, the cis-1,4 selectivity of the polymerization reaction may be lowered. Further, the pressure of the polymerization reaction is preferably in the range of 0.1 to 10 MPa in order to sufficiently incorporate the non-conjugated olefin and the conjugated diene compound into the polymerization reaction system. 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.

Further, when the non-conjugated olefin and the conjugated diene compound are polymerized, the concentration of the conjugated diene compound (mol / l) and the concentration of the non-conjugated olefin (mol / l) at the start of polymerization are expressed by the following formula:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.0
It is preferable to satisfy the relationship:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.3
And more preferably the following formula:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.7
Satisfy the relationship. By setting the value of the concentration of the non-conjugated olefin / the concentration of the conjugated diene compound to 1 or more, the non-conjugated olefin can be efficiently introduced into the reaction mixture.

Conjugated Diene Polymer The conjugated diene polymer means a polymer (polymer) that does not contain a non-conjugated olefin as a monomer unit component (part of a copolymer). Styrene is not included in the non-conjugated olefin.

The type of the conjugated diene polymer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, natural rubber (NR), various polybutadiene rubbers (BR), synthetic polyisoprene rubber (IR), Various styrene-butadiene copolymer rubber (SBR), ethylene-propylene rubber (EPR), styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer Examples thereof include polymer rubber (NBR) and chloroprene rubber. These may be used individually by 1 type and may use 2 or more types together.
Among these, natural rubber (NR) is preferable in that it has high compatibility with the conjugated diene compound-nonconjugated olefin copolymer, and can further improve ozone resistance and crack growth resistance.

  Moreover, it is preferable that content of the said natural rubber is 10 mass parts or more with respect to 100 mass parts of rubber components. This is because excellent workability, dynamic magnification, and elongation fatigue properties can be obtained. When the amount is less than 10 parts by mass, the workability, dynamic magnification, and elongation fatigue properties may not be sufficiently obtained.

(Bismaleimide compound)
The anti-vibration rubber composition of the present invention contains a bismaleimide compound as a vulcanizing agent. By using in combination with N-phenyl-N- (trichloromethylthio) benzenesulfonamide and thiuram vulcanization accelerator, which will be described later, heat resistance, compression set, low dynamic ratio, tensile physical properties, low temperature properties are obtained through these synergistic effects. And there is an effect that all processability can be improved.

As the bismaleimide compound, known compounds can be used, and are not particularly limited. In the present invention, a bismaleimide compound represented by the following structural formula can be preferably used.

In the above formula, x and y each independently represent an integer of 0 to 20, more preferably an integer of 0 to 10. R ¹ represents an aromatic group having 5 to 18 carbon atoms or an aromatic group having 7 to 24 carbon atoms including an alkyl group, and specific examples thereof include aromatic groups having the following structures. In the following structure, two bonds are not described, but in the following structure, a divalent group is constituted by two bonds from two carbon atoms arbitrarily selected.

  Specific examples of the bismaleimide compound represented by the above structural formula include N, N′-o-phenylene bismaleimide, N, N′-m-phenylene bismaleimide, N, N′-p-phenylene bismaleimide, N , N ′-(4,4′-diphenylmethane) bismaleimide, 2,2-bis- [4- (4-maleimidophenoxy) phenyl] propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane Etc. can be illustrated. In the present invention, N, N′-m-phenylenebismaleimide and N, N ′-(4,4′-diphenylmethane) bismaleimide can be preferably used.

  In addition, the said bismaleimide compound can be used individually by 1 type or in combination of 2 or more types. About the content, it is preferable to set it as 0.2-5.0 mass parts with respect to 100 mass parts of said rubber components. If the content of the bismaleimide compound is less than 0.2 parts by mass, heat resistance and compression set may be deteriorated. On the other hand, if the content exceeds 5.0 parts by mass, tensile physical properties (elongation, strength) , Durability may be deteriorated.

(sulfur)
The anti-vibration rubber composition of the present invention contains sulfur as a vulcanizing agent. As in the case of the bismaleimide compound, when used in combination with N-phenyl-N- (trichloromethylthio) benzenesulfonamide and a thiuram vulcanization accelerator, which will be described later, these synergistic effects result in heat resistance, compression set, low dynamics. There is an effect that the magnification, tensile physical properties, low temperature characteristics and workability can all be improved.

  The sulfur content is preferably 0.4 to 1.0 part by mass with respect to 100 parts by mass of the rubber component. If the sulfur content is less than 0.4 parts by mass, the low-temperature characteristics, dynamic magnification, and elongation fatigue characteristics may be deteriorated. On the other hand, if the content exceeds 1.0 parts by mass, the heat aging resistance and elongation are deteriorated. Fatigue properties may be deteriorated. In addition, it is more preferable that the total amount of sulfur is 0.6 to 1.0 part by mass from the viewpoint of improving the low temperature characteristics and dynamic magnification.

(Thiuram vulcanization accelerator)
The anti-vibration rubber composition of the present invention contains a vulcanization accelerator in order to promote the crosslinking reaction of each vulcanizing agent described above, and a thiuram vulcanization accelerator (but only monosulfide) as the vulcanization accelerator. Except those having the chemical structure of By using a thiuram vulcanization accelerator, low temperature properties, tensile properties, heat aging resistance, compression set properties, and dynamic physical properties of rubber can be improved.

  The thiuram vulcanization accelerator is not particularly limited as long as it excludes those having a chemical structure only of monosulfide, but, for example, those having the following chemical structure (A) or (B) are preferable. It is.

上記式中、ｘは２以上の正数、Ｒ₁、Ｒ₂、Ｒ₃及びＲ₄は、互いに同種又は異種であり、具体的には、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、２−メチルブチル基、１−メチルブチル基、ｎ−ヘキシル基、イソヘキシル基、３−メチルペンチル基、２−メチルペンチル基、１−メチルペンチル基、ヘプチル基、オクチル基、イソオクチル基、２−エチルヘキシル基等の鎖状アルキル基が挙げられる。

In the above formula, x is a positive number of 2 or more, and R ₁ , R ₂ , R ₃ and R ₄ are the same or different from each other, specifically, methyl group, ethyl group, n-propyl group, isopropyl group N-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl group, n-hexyl group, isohexyl group, 3-methylpentyl group And chain alkyl groups such as 2-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group and the like.

上記式中、ｙは２以上の正数であると共に、ｍ及びｎは２以上の正数である。上記式の具体例としては、ｍ，ｎ＝５であるジペンタメチレンチウラムテトラスルフィド（ＤＰＴＴ）を挙げることができる。

In the above formula, y is a positive number of 2 or more, and m and n are positive numbers of 2 or more. Specific examples of the above formula include dipentamethylene thiuram tetrasulfide (DPTT) in which m and n = 5.

  Examples of the thiuram vulcanization accelerator include tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, tetrakis (2-ethylhexyl) thiuram disulfide, dipentamethylene thiuram tetrasulfide and the like. As the commercial products, for example, trade names “Noxeller TT-P”, “Noxeller TET-G”, “Noxeller TBT”, “Noxeller TOT-N”, “Noxeller TRA” )) And the like.

  Moreover, it is preferable that content of the said thiuram type vulcanization accelerator is 0.5-5.0 mass parts with respect to 100 mass parts of rubber components. If the content of the thiuram vulcanization accelerator is less than 0.5 parts by mass, the degree of vulcanization will decrease, so low temperature characteristics, tensile properties (elongation, strength, etc.), heat resistance, compression set characteristics, and On the other hand, if the content exceeds 5.0 parts by mass, the vulcanization rate becomes too fast, which may lead to deterioration of workability and tensile properties (elongation, strength, etc.). The

(N-phenyl-N- (trichloromethylthio) benzenesulfonamide)
The anti-vibration rubber composition of the present invention contains N-phenyl-N- (trichloromethylthio) benzenesulfonamide, and the N-phenyl-N- (trichloromethylthio) benzenesulfonamide has the following chemical structure.
By including this component, due to the synergistic effect with the bismaleimide compound, the blending ratio of conventional sulfur and vulcanization accelerator, and the optimization of the vulcanization accelerator could not be improved, heat resistance It is possible to improve all aspects of compression set, dynamic magnification, low temperature characteristics and workability (scorch resistance).

  Specific examples of N-phenyl-N- (trichloromethylthio) benzenesulfonamide include “Vulkalent E / C” (manufactured by LANXESS).

  The content of N-phenyl-N- (trichloromethylthio) benzenesulfonamide is preferably 0.2 to 4 parts by mass with respect to 100 parts by mass of the rubber component. If the blending amount is deviated, a sufficient improvement effect may not be obtained in terms of heat resistance, compression set, dynamic magnification, low temperature characteristics, and workability (scorch resistance).

(Other ingredients)
In addition, the anti-vibration rubber composition of the present invention further includes a vulcanization accelerator, carbon black, silica, a vulcanization accelerator other than a thiuram, an anti-aging agent, an oil, etc., depending on various purposes. Can do.

  The anti-vibration rubber composition of the present invention may contain a vulcanization accelerator other than the thiuram vulcanization accelerator, and the type thereof is not particularly limited, but 2-mercaptobenzothiazole, Thiazoles such as dibenzothiazyl disulfide, N-cyclohexyl-2-benzothiazylsulfenamide, Nt-butyl-2-benzothiazylsulfenamide, Nt-butyl-2-benzothiazylsulfenamide Or sulfenamide vulcanization accelerators; guanidine vulcanization accelerators such as diphenylguanidine; dithiocarbamate vulcanization accelerators such as zinc dimethyldithiocarbamate; and other zinc dialkyldithiophosphates.

About the said vulcanization accelerator, 1 type (s) or 2 or more types, such as a sulfenamide type | system | group, a thiazole type | system | group, a guanidine type | system | group, a dithiocarbamate type | system | group, can be used together.
Moreover, the total content of the vulcanization accelerator is preferably 0.5 to 7 parts by mass with respect to 100 parts by mass of the rubber component.

  As the carbon black, known ones can be used, and are not particularly limited. Examples thereof include carbon blacks such as SRF, GPF, FEF, FT, MT, and the like in the present invention. FEF can be preferably used. Moreover, these carbon blacks may be used individually by 1 type, and may use 2 or more types together. About the compounding quantity of carbon black, it is 15-60 mass parts normally with respect to 100 mass parts of rubber components, Preferably it is 20-50 mass parts. When the amount exceeds 100 parts by mass, workability may be deteriorated, and when it is less than 15 parts by mass, adhesion may be deteriorated.

  Further, it is recommended to blend silica as a filler, and the blending amount of silica used is preferably 10 to 80 parts by mass with respect to 100 parts by mass of the rubber component from the viewpoint of reducing the dynamic ratio. .

  About the said vulcanization | cure acceleration | stimulation adjuvant, it mix | blends from a viewpoint which accelerates | stimulates vulcanization | cure, and zinc white (ZnO), a fatty acid, etc. are used. The fatty acid may be any of 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 carbon atoms. ~ 30 fatty acids, more specifically, cyclohexane acid (cyclohexanecarboxylic acid), naphthenic acid such as anoalkylcyclopentane 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 and octadecanoic acid (stearic acid), unsaturated fatty acids such as methacrylic acid, oleic acid, linoleic acid and linolenic acid, resins such as rosin, tall oil acid and apietic acid An acid etc. are 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 vulcanization accelerators is preferably 1 to 15 parts by mass, more preferably 2 to 10 parts by mass with respect to 100 parts by mass of the rubber component.

  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 these anti-aging agents is usually 0.5 to 10 parts by mass, preferably 1 to 5 parts by mass with respect to 100 parts by mass of the rubber component.

  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, naphthenic oil can be suitably used. These can be used alone or in combination of two or more. The blending amount of these oils is not particularly limited, but can be approximately 2 to 80 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. In addition, when using an oil-extended rubber as 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.

  When obtaining the 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 one time. You may mix | blend and knead | mix. In the kneading, a kneader such as a roll, an internal mixer or a panbury rotor 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.

(Crosslinked anti-vibration rubber composition, anti-vibration rubber)
The crosslinked anti-vibration rubber composition of the present invention is obtained by crosslinking the above-described anti-vibration rubber composition.
For example, the anti-vibration rubber composition of the present invention can be produced by molding and then vulcanizing. Vulcanization conditions can be selected as appropriate, but are usually performed at a temperature of 135 ° C. to 180 ° C., preferably 150 to 170 ° C. for 10 minutes to 100 minutes.

  The anti-vibration rubber of the present invention is characterized by using the anti-vibration rubber composition or the cross-linked anti-vibration rubber composition described above, and has the effect of being excellent in extension fatigue resistance, ozone resistance, low dynamic magnification, low temperature characteristics and processability. Play. The member to which the vibration isolating rubber of the present invention is applied is not particularly limited, but is preferably used as a vibration isolating member for vehicles, particularly for automobiles, which have more severe performance requirements.

  Examples of anti-vibration members for automobiles include engine mounts, torsional dampers, rubber bushes, strut mounts, bound bumpers, helper rubbers, member mounts, stabilizer bushes, air springs, center supports, rubber-equipped propeller shafts, anti-vibration levers, companions Yon damper, damping rubber, idler arm bush, steering column bush, coupling rubber, body mount, muffler support, dynamic damper, piping rubber and the like. Among these, it is particularly suitable for engine mounting. Moreover, the anti-vibration rubber of the present invention has good ozone resistance, and is therefore suitably used for a center support that requires ozone resistance.

  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.

<Samples 1 to 13>
Each component of the blending ratio shown in Table 1 was kneaded to prepare a sample rubber composition.
About the preparation method of EBR1-4 shown in Table 1, it shows below.

(Preparation of ethylene-butadiene copolymer (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 a copolymer (EBR1, block copolymer). The yield of EBR1 obtained was 12.50 g.
For 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 analyzed by the methods described below. It was. The measurement results are shown in Table 2.

(Ethylene-butadiene copolymer (Preparation of 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, 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. , 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 a copolymer (EBR2, multi-block copolymer). The yield of EBR2 obtained was 14.00 g.
For 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 analyzed by the methods described below. It was. The measurement results are shown in Table 2.

(Preparation of ethylene-butadiene copolymer (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 was placed in a glass container. , Triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ ) 14.1 μmol and diisobutylaluminum hydride 0.87 mmol 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-dried at 70 ° C. to obtain a polymer (EBR3, multi-block copolymer). The yield of EBR3 obtained was 24.50 g.
For 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 analyzed by the methods described below. It was. The measurement results are shown in Table 2.

(Preparation of ethylene-butadiene copolymer (EBR4))
Instead of using bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] in the preparation of EBR3, bis (2-phenyl-1- An experiment was 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 a copolymer (EBR4 A multi-block copolymer). The yield of EBR4 obtained was 28.55 g.
For 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 analyzed by the methods described below. It was. The measurement results are shown in Table 2.

In addition, about the analysis method of each EBR1-4, it is as follows.
(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.].

* 1 Natural rubber: “RSS # 1”
* 2 Carbon black: FEF grade carbon black (iodine adsorption amount = 43 g / kg, DBP oil absorption amount = 121 ml / 100 g, N ₂ SA (nitrogen adsorption specific surface area) = 42 m ² / g), “Asahi” manufactured by Asahi Carbon Co., Ltd. # 65 "
* 3 Stearic acid: “Stearic acid 50S” manufactured by Shin Nippon Chemical Co., Ltd.
* 4 Zinc flower: “No. 3 Zinc flower” manufactured by Hakusui Tech Co., Ltd.
* 5 WAX: Product name "Santight S" (manufactured by Seiko Chemical Co., Ltd.)
* 6 Anti-aging agent A: 2,2,4-trimethyl-1,2-dihydroquinoline polymer, “NOCRACK 224” manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 7 Anti-aging agent B: N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine, “NOCRACK NS-6” manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 8 Anti-aging agent C: 2-mercaptobenzimidazole, “NOCRACK MB” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
* 9 Naphthenic oil: SUN REFING AND MARKETING COMPANY “Sunthene 4240”
* 10 N, N'-m-phenylene dimaleimide: "Banorenock PM" manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 11 Vulcanization accelerator A: Tetramethylthiuram monosulfide, “Noxeller TS” manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 12 Vulcanization accelerator B: Tetramethylthiuram disulfide, “Noxeller TT-P” manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 13 Vulcanization accelerator C: N-cyclohexyl-2-benzothiazolylsulfenamide, “Noxeller CZ-G” manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 15 Vulcanization accelerator E: Tetrabutylthiuram disulfide, “Noxeller TBT” manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 16 Vulcanization accelerator F: Tetraethylthiuram disulfide, “Noxeller TET-G” manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 17 Vulcanization accelerator G: Tetrakis (2-ethylhexyl) thiuram disulfide, “Noxeller TOT-N” manufactured by Ouchi Shinsei Chemical Co., Ltd.

<Characteristic evaluation of vulcanized rubber>
For each sample of the rubber composition, after vulcanization and curing at 165 ° C. for 20 minutes, a sheet molded product having a length of 120 mm × width of 120 mm × thickness of 2 mm was prepared, and this molded sheet was evaluated for the vibration-proof rubber of the present invention. The body. Each obtained molded sheet was evaluated by the following test method.

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

(2) For each sample of the low temperature characteristic rubber composition, after vulcanization, a cylindrical rubber molded product having a diameter of 30 mm and a height of 30 mm is prepared, and the dynamic spring constant Kd is 40 Hz in accordance with JIS K 6385. Measured (this is the initial Kd). Thereafter, after exposure at −35 ° C. for 10 days, Kd was rapidly measured under the same conditions as above (this is referred to as Kd after low temperature exposure). Kd after low temperature exposure / initial Kd was calculated as an index of low temperature characteristics.
The evaluation was performed according to the following criteria. The evaluation results are shown in Table 3.
○: Kd after low temperature exposure / initial Kd is 10 times Δ: Kd after low temperature exposure / initial Kd is more than 10 times and less than 20 times ×: Kd after low temperature exposure / initial Kd is 20 times or more

(3) Tensile fatigue resistance Each sample of the example and the comparative example was subjected to a test with a dumbbell specimen in accordance with JIS K6270 at a test strain of 100%, a test frequency of 5 Hz, and the number of repetitions until breaking. Was measured.
About evaluation, it displays as an index value when the frequency | count until it fractures in the sample 1 is set to 100, and it shows that there are many times until it fractures, so that a numerical value is large, and an elongation fatigue property is favorable. The evaluation results are shown in Table 3.

(4) Ozone resistance Each sample of the examples and comparative examples was subjected to a dynamic ozone test in accordance with JIS K6259. The test piece was attached to a testing machine without any tensile strain, and adjusted so that a tensile strain of 20% was applied by a predetermined reciprocating motion (0.5 Hz). The atmospheric temperature of the test was 40 ° C., and the ozone concentration was 50 pphm.
In addition, an evaluation result is displayed as an index value when the time until the occurrence of ozone cracking is set to 100 as the value of sample 1, and the larger the value, the better the result.

  From Table 3, it was found that the samples of the examples showed good results for all of dynamic magnification, low temperature characteristics, stretch fatigue resistance, and ozone resistance. On the other hand, it was found that the sample of the comparative example showed a result in which at least one of the evaluation items was inferior to the sample of the example.

  ADVANTAGE OF THE INVENTION According to this invention, the anti-vibration rubber composition and crosslinked anti-vibration rubber composition which were excellent in the low dynamic magnification, the low-temperature characteristic, the elongation fatigue property, ozone resistance, and workability can be provided. The anti-vibration rubber using the anti-vibration rubber composition or the crosslinked anti-vibration rubber composition is suitably used as a constituent material for a torsional damper, an engine mount, a muffler hanger, and the like.

Claims (11)

A rubber component having a conjugated diene compound-nonconjugated olefin copolymer and a conjugated diene polymer;
A bismaleimide compound,
Sulfur and
A thiuram vulcanization accelerator (except those having a chemical structure of monosulfide only),
And N- phenyl -N- (trichloromethyl thio) benzenesulfonamide seen including,
The content of the conjugated diene compound-nonconjugated olefin copolymer-derived moiety in the conjugated diene compound is 30 mol% or more,
The cis-1,4 bond content of the conjugated diene compound-derived moiety in the conjugated diene compound-nonconjugated olefin copolymer is more than 92%;
The content of the conjugated diene compound-nonconjugated olefin copolymer in 100 parts by mass of the rubber component is 10 to 90 parts by mass,
The non-conjugated olefin is an acyclic olefin,
An anti-vibration rubber composition characterized by that.   The anti-vibration rubber composition according to claim 1, wherein a content of the thiuram vulcanization accelerator is 0.5 to 5.0 parts by mass with respect to 100 parts by mass of the rubber component.   The anti-vibration rubber composition according to claim 1 or 2, wherein the sulfur content is 0.4 to 1.0 part by mass with respect to 100 parts by mass of the rubber component.   The anti-vibration rubber composition according to claim 1, wherein the conjugated diene compound-nonconjugated olefin copolymer has a polystyrene-reduced weight average molecular weight of 10,000 to 10,000,000.   The anti-vibration rubber composition according to claim 1, wherein a molecular weight distribution (Mw / Mn) of the conjugated diene compound-nonconjugated olefin copolymer is 10 or less. The anti-vibration rubber composition according to claim 1, wherein the non-conjugated olefin has 2 to 10 carbon atoms. The vibration-insulating rubber composition according to claim 5 or 6 , 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 7 , wherein the non-conjugated olefin is ethylene.   The vibration-insulating rubber composition according to claim 1, wherein the conjugated diene polymer is natural rubber. Crosslinked vibration damping rubber composition characterized in that cross-linking the vibration damping rubber composition according to claim 1. An anti-vibration rubber produced using the anti-vibration rubber composition according to claim 1 or the crosslinked anti-vibration rubber composition according to claim 10 .