JPH101516A - Vibrationproof rubber molding and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a vibrationproof rubber molding which is excellent in resistances to environmental aging and dynamic fatigue and has a long like by randomly copolymerizing ethylene, a specific α-olefin, and a nonconjugated polyene under specified conditions on the presence of a specific metallocene catalyst. SOLUTION: This molding contains ethylene units and 4-20C α-olefin units in a molar ratio of (40/60)-(85/15), has an iodine value of 1-50 and an intrinsic viscosity η (at 135 deg.C in decalin) of 2-10dl/g, and is obtd. by randomly copolymerizing ethylene, a 4-20C α-olefin, and a nonconjugated diene in the presence of a metallicence catalyst contg. a metallocene compd. such as one represented by the formula [wherein M is a transition metal of the group IVB; R<11> and R<12> are each H, halogen, a 1-20C hydrocarbon group, or a group contg. Si, O, S, N, or P; R<13> and R<14> are each 1-20C alkyl; X<1> and X<2> each H, halogen, a 1-20C hydrocarbon group, a halohydrocarbon group, or a group contg. O or S; and Y is a 1-20C divalent (halo)hydrocarbon group, a divalent Si- or Ge- contg. group, O, CO, S, SO2 , etc.].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anti-vibration rubber molded article and a method for producing the same, and more particularly to an anti-environmental aging resistance (heat aging resistance, weather resistance, ozone resistance) and a dynamic fatigue resistance ( The present invention relates to an anti-vibration rubber molded article having excellent bending fatigue resistance and a long life, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Vibration-proof rubber moldings are used to block or reduce the transmission of vibrations and are widely used in machinery, home appliances, civil engineering construction materials, automobiles, vehicles, and the like. Conventionally, natural rubber and SBR have been mainly used for these vibration-proof rubber molded articles.

[0003] However, in recent years, the use environment of vibration-proof rubber molded articles has become increasingly severe, and in addition to the demand for maintenance-free, longer life has been demanded.

[0004] Therefore, utilization of an ethylene-propylene-diene rubber (EPDM) excellent in heat aging resistance as a vibration-proof rubber molded article has been studied. However, this EPD
The vibration-proof rubber molded article using M has a problem that it is easily broken due to fatigue under so-called dynamic conditions where vibration is particularly severe.

[0005] Therefore, there has been a demand for a vibration-proof rubber molded article having excellent environmental aging resistance and excellent dynamic fatigue resistance (bending fatigue resistance) and a long life.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art as described above. The present invention is excellent in environmental aging resistance (heat aging resistance, weather resistance, ozone resistance), and is resistant to dynamic aging. It is an object of the present invention to provide an anti-vibration rubber molded article having excellent mechanical fatigue (bending fatigue resistance) and a long life, and a method for producing the same.

[0007]

SUMMARY OF THE INVENTION A vibration-proof rubber molded article according to the present invention is a rubber comprising an ethylene / α-olefin / non-conjugated polyene copolymer rubber comprising ethylene, an α-olefin having 4 to 20 carbon atoms and a non-conjugated polyene. A crosslinked rubber molded article comprising the composition, wherein the ethylene / α-olefin / non-conjugated polyene copolymer rubber contains ethylene and a C 4 to C 4 in the presence of a metallocene catalyst containing a metallocene compound.
(1) (a) a unit derived from ethylene, and (b) a carbon number of 4 to 4 obtained by randomly copolymerizing an α-olefin of 20 and a non-conjugated polyene.
The units derived from 20 α-olefins are 40/6
(2) iodine value is 1 to 50, (3) intrinsic viscosity [η] measured in decalin at 135 ° C.
Is 2 to 10 dl / g.

The metallocene compound includes a metallocene compound represented by the following general formula [I] or [II].

[0009]

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[Wherein, M is a transition metal of Group IVB of the periodic table, and R ¹¹ and R ¹² are a hydrogen atom, a halogen atom, or a carbon atom having 1 to 2 carbon atoms which may be substituted with halogen.
0 hydrocarbon group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group, R ¹³ and R ¹⁴ are each an alkyl group having 1 to 20 carbon atoms, and X ¹ And X ² are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group, and Y is a carbon atom A divalent hydrocarbon group of the formulas 1 to 20,
A divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, 2
Divalent silicon-containing group, divalent germanium-containing group, -O
-, - CO -, - S -, - SO -, - SO 2 -, - NR
^{7 -, - P (R 7} ) -, - P (O) (R 7) -, - BR
⁷ - or -AlR ⁷ - it is. (However, R ⁷ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.)]

[0011]

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[Wherein, M is a transition metal of Group IVB of the periodic table, R ²¹ may be the same or different, and may be a hydrogen atom, a halogen atom, a carbon atom which may be halogenated. An alkyl group having 1 to 10 carbon atoms and 6 to 10 carbon atoms
Aryl group, or -NR ₂ of 10, -SR, -OSi
R ₃ , —SiR ₃ or —PR ₂ (R is a halogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms), and R ^{22 to} R ²⁸ are as defined above. It is the same as R ²¹ , or adjacent R ^{22 to} R ²⁸ may form an aromatic ring or an aliphatic ring together with the atoms to which they are bonded, and X ³ and X ⁴ may be the same or different from each other. Hydrogen atom, halogen atom, O
H group, alkyl group having 1 to 10 carbon atoms, 1 carbon atom
Alkoxy group having 10 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, aryloxy group having 6 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, carbon atom An alkylaryl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms,

[0013]

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-Sn-, -O-, -S-, = SO, = S
O ₂ , ＮＲNR ²⁹ , ＣＯCO, ＰＲPR ²⁹ or ＰP (O) R
²⁹ . (However, R ²⁹ and R ³⁰ may be the same or different from each other, and include a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, and 6 carbon atoms. 10 to 10 aryl groups,
C6-C10 fluoroaryl group, C1-C10 alkoxy group, C2-C10 alkenyl group, C7-C40 arylalkyl group, C8-C40 aryl An alkenyl group or an alkylaryl group having 7 to 40 carbon atoms, or R
²⁹ and R ³⁰ may each form a ring with the atoms to which they are attached, and M ² is a silicon, germanium or tin atom. )] The above-mentioned ethylene / α-olefin / non-conjugated polyene copolymer rubber has, in addition to the above-mentioned properties (1) to (3), (4) ¹³ C-NMR spectrum and B obtained from the following formula. Preferably, the value is between 1.00 and 1.50.

B value = [P _OE ] / (2 · [P _E ] · [P _O ]) (where [P _E ] is a unit derived from (a) ethylene in the random copolymer rubber) Content mole fraction,
[P _O ] is the content mole fraction of units derived from (b) α-olefin in the random copolymer rubber, and [P _OE ]
Is the total dyad in random copolymer rubber
It is the ratio of the number of α-olefin / ethylene chains to the number of chains. Further, the method for producing a vibration-proof rubber molded article according to the present invention includes an ethylene / α-olefin / non-conjugated polyene copolymer rubber comprising ethylene, an α-olefin having 4 to 20 carbon atoms and a non-conjugated polyene. A method for producing a vibration-proof rubber molded article by crosslinking a rubber composition, comprising:
-The olefin / non-conjugated polyene copolymer rubber is prepared by reacting ethylene with an α-olefin having 4 to 20 carbon atoms in the presence of a metallocene catalyst containing a metallocene compound represented by the above formula [I] or [II]. , Obtained by random copolymerization with a non-conjugated polyene, (1) (a) a unit derived from ethylene and (b) 4 to 4 carbon atoms
The units derived from 20 α-olefins are 40/6
(2) iodine value is 1 to 50, (3) intrinsic viscosity [η] measured in decalin at 135 ° C.
Is 2 to 10 dl / g.

[0016]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a vibration-proof rubber molded product according to the present invention and a method for producing the same will be specifically described.

The vibration-proof rubber molded article according to the present invention is obtained by crosslinking (vulcanizing) a rubber composition containing a specific ethylene / α-olefin / non-conjugated polyene copolymer rubber. Ethylene / α-olefin / non-conjugated polyene copolymer
The ethylene / α-olefin / non-conjugated polyene copolymer rubber used in the present invention is prepared by adding ethylene and C 4 to C 2 in the presence of a specific metallocene catalyst as described below.
It can be obtained by random copolymerizing an α-olefin of 0 and a non-conjugated polyene.

Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene,
Undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-
Methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1
-Pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl -1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12
-Ethyl-1-tetradecene, and combinations thereof.

Of these, α-C 4-10
Olefins are preferred, further 1-butene, 1-hexene,
1-octene, 1-decene, especially 1-hexene, 1-octene,
1-decene and the like are preferably used.

Examples of the non-conjugated polyene include 5-ethylidene-2-norbornene, 5-propylidene-5-norbornene, dicyclopentadiene, 5-vinyl
Acyclic dienes such as -2-norbornene, 5-methyl-2-norbornene, 5-isopropylidene-2-norbornene, norbornadiene, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1 , 4-hexadiene, 5-methyl-1,5
-Non-conjugated chain diene such as heptadiene, 6-methyl-1,5-heptadiene, 6-methyl-1,7-octadiene, 7-methyl-1,6-octadiene, 2,3-diisopropylidene-5 -Trienes such as norbornene. Among them, 1,
4-hexadiene, dicyclopentadiene, 5-ethylidene
2-norbornene is preferably used.

These non-conjugated polyenes can be used alone or in combination of two or more. The ethylene / α-olefin / non-conjugated polyene copolymer rubber used in the present invention has the following properties. (1) Ethylene / α-olefin component ratio The ethylene / α-olefin / non-conjugated polyene copolymer rubber used in the present invention comprises (a) a unit derived from ethylene, and (b) a unit having 4 to 20 carbon atoms. a unit derived from an α-olefin (hereinafter sometimes simply referred to as α-olefin) is 40/60 to 85/15, preferably 40
/ 60-80 / 20, particularly preferably 50 / 50-75
/ 25 [(a) / (b)].

The ethylene / α-olefin / non-conjugated polyene copolymer rubber having such an ethylene component / α-olefin component ratio is excellent in both low-temperature flexibility and heat resistance. If the ethylene / α-olefin / non-conjugated polyene copolymer rubber has an ethylene / α-olefin component ratio of more than 85/15, it exhibits resin properties and low-temperature flexibility is reduced. If it is less than 40/60, the heat resistance tends to decrease. (2) Iodine value The iodine value which is one index of the non-conjugated polyene component amount of the ethylene / α-olefin / non-conjugated polyene copolymer rubber is
It is 1-50, preferably 5-40.

This characteristic value is a standard value when the ethylene / α-olefin / non-conjugated polyene copolymer rubber used in the present invention is crosslinked (vulcanized) with sulfur or an organic peroxide. . (3) Intrinsic viscosity [η] Intrinsic viscosity [η] of ethylene / α-olefin / non-conjugated polyene copolymer rubber measured at 135 ° C in decalin
Is 2 to 10 dl / g, preferably 2.5 to 7 dl / g.
g, more preferably 3 to 5 dl / g.

This characteristic value is a measure of the molecular weight of the ethylene / α-olefin / non-conjugated polyene copolymer rubber used in the present invention, and is combined with other characteristic values to provide mechanical strength and weather resistance. It is useful for obtaining a copolymer rubber having excellent properties such as ozone resistance, heat aging resistance and low-temperature properties.

Further, ethylene / α used in the present invention
-The olefin / non-conjugated polyene copolymer rubber preferably satisfies the following property (4). (4) B value The ethylene / α-olefin / non-conjugated polyene copolymer rubber desirably has a B value of 1.00 to 1.50 determined from the ¹³ C-NMR spectrum and the following formula.

B value = [P _OE ] / (2 · [P _E ] · [P _O ]) (where [P _E ] is the unit derived from (a) ethylene in the random copolymer rubber) Content mole fraction,
[P _O ] is the content mole fraction of units derived from (b) α-olefin in the random copolymer rubber, and [P _OE ]
Is the total dyad in random copolymer rubber
It is the ratio of the number of α-olefin / ethylene chains to the number of chains. The B value is an index indicating the distribution of ethylene and α-olefin in the copolymer rubber.
l (Macromolecules, 15, 353 (1982)), J. Ray (Macromolecules
olecules, 10,773 (1977)).

The larger the B value, the shorter the block chain of ethylene or α-olefin, the more uniform the distribution of ethylene and α-olefin, and the narrower the composition distribution of the copolymer rubber. I have. The composition distribution of the copolymer rubber becomes wider as the B value becomes smaller than 1.00, and such a copolymer rubber has a higher strength when crosslinked, for example, as compared with a copolymer rubber having a narrower composition distribution. Properties may not be fully exhibited.

In the present invention, as will be described later,
By copolymerizing ethylene, an α-olefin and a non-conjugated polyene using a Group IVB metallocene catalyst, a random copolymer rubber having a B value of 1.00 to 1.50 has been obtained. Even if ethylene, α-olefin and non-conjugated polyene are copolymerized in the presence of a titanium-based non-metallocene catalyst, an ethylene / α-olefin / non-conjugated polyene copolymer rubber having a B value in the above range can be obtained. It is not possible.

Ethylene α-having the above properties
From the olefin / non-conjugated polyene copolymer rubber, a vulcanizable rubber composition having excellent mechanical strength, weather resistance and ozone resistance, and also having excellent cold resistance (low temperature flexibility) and heat resistance, and A vulcanizate can be obtained.

The above-mentioned specific ethylene / α-olefin / non-conjugated polyene copolymer rubber can be prepared by adding ethylene and C 4-20 in the presence of a specific metallocene catalyst.
And a non-conjugated polyene are randomly copolymerized.

The metallocene catalyst used in the present invention is:
There is no particular limitation except that it contains the metallocene compound [A]. For example, a compound that forms an ion pair by reacting with the metallocene compound [A] and the organoaluminum oxy compound [B] and / or the metallocene compound [A] [ C]. Further, it may be formed from a metallocene compound [A], an organoaluminum oxy compound [B] and / or an organoaluminum compound [D] together with a compound [C] forming an ion pair.

Hereinafter, each component used in forming the metallocene catalyst in the present invention will be described. Metallocene compound [A] In the present invention, a compound represented by the following general formula [I] or [II] is used as the metallocene compound [A].

[0033]

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In the formula, M is a transition metal atom of Group IVB of the periodic table, and specifically, titanium, zirconium,
Hafnium, particularly preferably zirconium. R ¹¹ and R ¹² R ¹¹ and R ^{12 each} represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, Containing group or phosphorus-containing group, examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, a sec-butyl group,
tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, dodecyl group, eicosyl group, norbornyl group, alkyl group such as adamantyl group, vinyl group, propenyl group, cyclohexenyl group, etc. Alkenyl group, benzyl group, phenylethyl group, arylalkyl group such as phenylpropyl group,
Phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, α- or β-naphthyl, methylnaphthyl, anthracenyl, phenanthryl, benzylphenyl, pyrenyl, Examples include an aryl group such as an acenaphthyl group, a phenalenyl group, an aceanthrenyl group, a tetrahydronaphthyl group, an indanyl group, and a biphenylyl group.

These hydrocarbon groups include halogen atoms such as fluorine, chlorine, bromine and iodine, trimethylsilyl groups,
It may be substituted with an organic silyl group such as a triethylsilyl group and a triphenylsilyl group.

Specific examples of the oxygen-containing group include an alkoxy group such as a hydroxy group, a methoxy group, an ethoxy group, a propoxy group and a butoxy group, and an allyloxy group such as a phenoxy group, a methylphenoxy group, a dimethylphenoxy group and a naphthoxy group. And arylalkoxy groups such as phenylmethoxy group and phenylethoxy group.

As the sulfur-containing group, specifically, a substituent in which oxygen of the oxygen-containing group is replaced with sulfur, a methylsulfonate group, a trifluoromethanesulfonate group,
Phenylsulfonate, benzylsulfonate, p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluorobenzenesulfonate Sulfonate groups such as
Methyl sulfinate group, phenyl sulfinate group,
Examples include a benzenesulfinate group, a p-toluenesulfinate group, a trimethylbenzenesulfinate group, and a sulfinate group such as pentafluorobenzenesulfinate.

Examples of the nitrogen-containing group include an alkylamino group such as an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a dicyclohexylamino group, a phenylamino group, Examples thereof include an arylamino group such as a diphenylamino group, a ditolylamino group, a dinaphthylamino group, and a methylphenylamino group, and an alkylarylamino group.

Specific examples of the phosphorus-containing group include a dimethylphosphino group and a diphenylphosphino group. R ¹¹ is preferably a hydrocarbon group among them, and particularly preferably a hydrocarbon group having 1 to 3 carbon atoms such as a methyl group, an ethyl group and a propyl group.

R ¹² is preferably a hydrogen atom or a hydrocarbon group, particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group.

R ¹³ and R ¹⁴ R ¹³ and R ^{14 each} have 1 carbon atom as exemplified above.
-20 alkyl groups.

R ¹³ is preferably a secondary or tertiary alkyl group. R ¹⁴ may contain a double bond or a triple bond. X ¹ and X ² X ¹ and X ² represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group as exemplified above. Group or sulfur-containing group, a halogen atom,
It is preferably 20 hydrocarbon groups.

[0043] Y Y is a divalent hydrocarbon group, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group , -O-, -C
O -, - S -, - SO -, - SO 2 -, - NR 15 -, -
^{P (R 15) -, -} P (O) (R 15) -, - BR 15 - or -AlR ¹⁵ - [however, R ¹⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms , 1 carbon atom
To 20 halogenated hydrocarbon groups], and specifically,
Methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4- A divalent hydrocarbon group having 1 to 20 carbon atoms such as an alkylene group such as a cyclohexylene group, an arylalkylene group such as a diphenylmethylene group or a diphenyl-1,2-ethylene group; Halogenated hydrocarbon group obtained by halogenating a divalent hydrocarbon group of from 20 to 20; methylsilylene group, dimethylsilylene group, diethylsilylene group, di (n-propyl) silylene group, di (i-propyl) silylene group, Alkylsilylene groups such as (cyclohexyl) silylene group, methylphenylsilylene group, diphenylsilylene group, di (p-tolyl) silylene group, di (p-chlorophenyl) silylene, and alkylaryl Contains divalent silicon such as alkylsilyl group such as rusilylene group, arylsilylene group, tetramethyl-1,2-disilyl group, tetraphenyl-1,2-disilyl group, alkylaryldisilyl group, and aryldisilyl group Group: a divalent germanium-containing group in which silicon of the above-mentioned divalent silicon-containing group is substituted with germanium.

R ¹⁵ is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms as described above. Among them, Y is preferably a divalent silicon-containing group, a divalent germanium-containing group, more preferably a divalent silicon-containing group, and is preferably an alkylsilylene group, an alkylarylsilylene group, or an arylsilylene. Particularly preferred is a group.

Specific examples of the metallocene compound represented by the above general formula [I] are shown below. rac-dimethylsilylene-bis (2,7-dimethyl-4-ethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-n-propyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-
Dimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-n-butyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2, 7-dimethyl-4-sec
-Butyl-1-indenyl) zirconium dichloride, ra
c-dimethylsilylene-bis (2,7-dimethyl-4-t-butyl
-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-n-pentyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-n -Hexyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2,7-dimethyl-4-cyclohexyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2,7-dimethyl-4-methylcyclohexyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-phenylethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis (2,7-dimethyl-4-phenyldichloromethyl-1-
Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-chloromethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-trimethylsilylmethyl-1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-trimethylsiloxymethyl-1-indenyl) zirconium dichloride, rac-
Diethylsilylene-bis (2,7-dimethyl-4-i-propyl
-1-indenyl) zirconium dichloride, rac-di (i-
Propyl) silylene-bis (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-di (n-butyl) silylene-bis (2,7-dimethyl-4-i-propyl-1 -Indenyl) zirconium dichloride, rac-di (cyclohexyl) silylene-bis (2,7-dimethyl-4-i
-Propyl-1-indenyl) zirconium dichloride, r
ac-methylphenylsilylene-bis (2,7-dimethyl-4-i-
Propyl-1-indenyl) zirconium dichloride, r
ac-methylphenylsilylene-bis (2,7-dimethyl-4-t-
Butyl-1-indenyl) zirconium dichloride, rac
-Diphenylsilylene-bis (2,7-dimethyl-4-t-butyl-1-indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2,7-dimethyl-4-i-propyl-1)
-Indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2,7-dimethyl-4-ethyl-1-indenyl) zirconium dichloride, rac-di (p-tolyl) silylene-bis (2,7-dimethyl-4- i-propyl-1-indenyl) zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis (2,7-dimethyl-4-i-propyl-1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-ethyl-1
-Indenyl) zirconium dibromide rac-dimethylsilylene-bis (2,3,7-trimethyl-4-ethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis (2,3,7-trimethyl-4-n-propyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2,3,7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2,3,7-trimethyl-4-n-butyl-1-indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4-sec-butyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4-t- Butyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,
3,7-trimethyl-4-n-pentyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,
7-trimethyl-4-n-hexyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-
Trimethyl-4-cyclohexyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,
7-trimethyl-4-methylcyclohexyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2,3,7-trimethyl-4-trimethylsilylmethyl-1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4-trimethylsiloxymethyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,3,7-trimethyl-4-phenylethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4
-Phenyldichloromethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4-chloromethyl-1-indenyl) zirconium dichloride, rac-diethylsilylene-bis (2,3, 7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-di (i-propyl) silylene-bis (2,
3,7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-di (n-butyl) silylene-bis (2,3,7-trimethyl-4-i-propyl-1-indenyl) zirconium Dichloride, rac-di (cyclohexyl) silylene-bis (2,3,7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-methylphenylsilylene-bis (2,3,7-trimethyl-4 -i-propyl-1-
Indenyl) zirconium dichloride, rac-methylphenylsilylene-bis (2,3,7-trimethyl-4-t-butyl-1
-Indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2,3,7-trimethyl-4-t-butyl-1-
Indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2,3,7-trimethyl-4-i-propyl-1-
Indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2,3,7-trimethyl-4-ethyl-1-indenyl) zirconium dichloride, rac-di (p-tolyl)
Silylene-bis (2,3,7-trimethyl-4-i-propyl-1-
Indenyl) zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis (2,3,7-trimethyl-4-i-
Propyl-1-indenyl) zirconium dichloride, ra
c-dimethylsilylene-bis (2-methyl-4-i-propyl-7
-Methyl-1-indenyl) zirconium dimethyl, rac-
Dimethylsilylene-bis (2-methyl-4-i-propyl-7-
Methyl-1-indenyl) zirconium methyl chloride,
rac-dimethylsilylene-bis (2-methyl-4-i-propyl
-7-methyl-1-indenyl) zirconium-bis (methanesulfonato), rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium-bis (p-phenyl) Sulfinato), rac-dimethylsilylene-bis (2-methyl-3-methyl-4-i-propyl-7)
-Methyl-1-indenyl) zirconium dichloride, ra
c-Dimethylsilylene-bis (2-ethyl-4-i-propyl-7
-Methyl-1-indenyl) zirconium dichloride, ra
c-dimethylsilylene-bis (2-phenyl-4-i-propyl
-7-methyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-i-propyl
-7-methyl-1-indenyl) titanium dichloride, ra
c-dimethylsilylene-bis (2-methyl-4-i-propyl-7
-Methyl-1-indenyl) hafnium dichloride and the like.

Among these, i-propyl group at the 4-position, sec-
Compounds having a branched alkyl group such as a butyl group and a tert-butyl group are particularly preferred. In the present invention, a racemate of the transition metal compound is generally used as a catalyst component for olefin polymerization, but an R-type or S-type may also be used.

The transition metal compound as described above can be prepared from an indene derivative by a known method, for example, as described in JP-A-4-268307.
Can be synthesized by the method described in Japanese Patent Application Laid-Open No. H10-260, 1988. In the present invention, the metallocene compound [A] is EP
Compounds represented by the following formula [II] described in the specification of US Pat. No. 5,549,900 and Canadian 2084017 can also be used.

[0048]

Embedded image

In the formula, M is a transition metal atom belonging to Group IVB of the periodic table, and specifically, titanium, zirconium,
Hafnium, particularly preferably zirconium. R ²¹ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, preferably a fluorine atom or a chlorine atom, and an optionally halogenated carbon atom number of 1 to 1.
0, preferably 1-4 alkyl groups, 6-1 carbon atoms
0, preferably 6-8 aryl group, -NR _2, -S
R, —OSiR ₃ , —SiR _3, or —PR ₂ groups (where R is a halogen atom, preferably a chlorine atom, an alkyl group having 1 to 10, preferably 1 to 3 carbon atoms, or 6 to 10 carbon atoms; Preferably 6 to 8 aryl groups).

[0050] R ²² to R ²⁸ may be the same or different, have the same atom or group as R ^21, these R ²² to R
^At least two adjacent groups out of ²⁸ may form an aromatic ring or an aliphatic ring together with their bonding atoms.

X ³ and X ⁴ may be the same or different from each other, and include a hydrogen atom, a halogen atom, an OH group, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, and 1 to 10 carbon atoms. Preferably 1-3 alkoxy groups, 6-10 carbon atoms, preferably 6-8 aryl groups, 6-10 carbon atoms, preferably 6-8 aryloxy groups, 2-10 carbon atoms, Preferably, it has 2 to 4 alkenyl groups, 7 to 40 carbon atoms, preferably 7 to 10 arylalkyl groups, and 7 to 40 carbon atoms, preferably 7 to 10 carbon atoms.
A 12-alkylaryl group; and an arylalkenyl group having 8 to 40, preferably 8 to 12 carbon atoms.

[0052]

Embedded image

-Sn-, -O-, -S-, = SO, = S
O ₂ , ＮＲNR ²⁹ , ＣＯCO, ＰＲPR ²⁹ or ＰP (O) R
²⁹ . However, R ²⁹ and R ³⁰ may be the same or different from each other, and include a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, particularly preferably a methyl group and 1 carbon atom. 10 to 10 fluoroalkyl group, preferably CF ₃ group, 6 to 10 carbon atom, preferably 6 to 8 aryl group, 6 to 10 carbon atom fluoroaryl group, preferably pentafluorophenyl group, 1-10, preferably 1-4 alkoxy groups, particularly preferably methoxy group, 2-1 carbon atom
0, preferably 2 to 4 alkenyl groups, 7 to 7 carbon atoms
It is an arylalkyl group having 40, preferably 7 to 10 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, preferably 8 to 12 carbon atoms, and an arylalkyl group having 7 to 40 carbon atoms, preferably 7 to 12 carbon atoms.

R ²⁹ and R ³⁰ may form a ring together with the atoms to which they are bonded. M ² is silicon, germanium or tin.

The above-mentioned alkyl group is a linear or branched alkyl group, and the halogen (halogenated) is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, particularly preferably a fluorine atom or a chlorine atom. is there.

Among the compounds represented by the formula [II], M is zirconium or hafnium,
R ²¹ is the same as each other and is an alkyl group having 1 to 4 carbon atoms, and R ^{22 to} R ²⁸ may be the same or different from each other and is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X ³ and X ⁴ may be the same or different from each other, and are an alkyl group having 1 to 3 carbon atoms or a halogen atom;

[0057]

Embedded image

(M ² is silicon, R ²⁹ and R
³⁰ may be the same or different and are an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. ) Is preferable, and the substituents R ²² and R ²⁸ are a hydrogen atom, and R ^{23 to} R ²⁷ are more preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.

Further, M is zirconium, and R
²¹ is the same alkyl group having 1 to 4 carbon atoms from each other, R ²² and R ²⁸ are hydrogen atoms, R ²³ to R
²⁷ may be the same or different and has 1 to 4 carbon atoms
X ³ and X ^3
4 is a chlorine atom,

[0060]

Embedded image

(M ² is silicon, and R ²⁹ and R ³⁰
May be the same or different, and have 1 carbon atom
An alkyl group having 4 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Is preferred, and in particular, M is zirconium, R ²¹ is a methyl group, and R ^{22 to} R
²⁸ is a hydrogen atom, X ³ and X ⁴ are chlorine atoms,

[0062]

Embedded image

(M ² is silicon, and R ²⁹ and R ³⁰
May be the same or different and each is a methyl group or a phenyl group). Hereinafter, several examples of such a metallocene compound represented by the formula [II] will be shown.

Rac-dimethylsilylene-bis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4,5-
Acenaphthocyclopentadienyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3-6-trimethyl-4,5-benzoindenyl) zirconium dichloride, rac-methylphenylsilylene-bis -(2-methyl-4,5-benzoindenyl)｝ zirconium dichloride, rac-methylphenylsilylene-bis ｛1- (2-methyl
-4,5-acenaphthocyclopentadienyl) zirconium dichloride, rac-methylphenylsilylene-bis
(4,5-benzoindenyl) zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2,6-dimethyl)
-4,5-benzoindenyl) zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2,3-6-trimethyl-4,5-benzoindenyl)} zirconium dichloride.

Further, there may be mentioned compounds in which zirconium in the above compounds is replaced with titanium or hafnium. In the present invention, a racemic metallocene compound represented by the formula [I] or [II] is generally used as a catalyst component, but an R-type or S-type may also be used.

The above-mentioned metallocene compounds may be used in combination of two or more. Organoaluminum oxy compound [B] The organoaluminum oxy compound [B] used in the present invention may be a conventionally known aluminoxane or a benzene-insoluble compound as exemplified in JP-A-2-78687. May be an organic aluminum oxy compound.

A conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing water of adsorption or salts containing water of crystallization, such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of a hydrocarbon medium of Example 1 and reacting the suspension to recover a hydrocarbon solution. (2) A method in which water, ice or steam is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran to recover a hydrocarbon solution. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organic metal component. The solvent or unreacted organoaluminum compound may be removed from the recovered aluminoxane solution by distillation, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used in the production of aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec Trialkylaluminum such as -butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum; dimethylaluminum chloride; Diethylaluminum chloride,
Dialkylaluminum halides such as diethylaluminum bromide and diisobutylaluminum chloride; dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide; dialkylaluminum aryloxy such as diethylaluminum phenoxide And the like.

Of these, trialkyl aluminum and tricycloalkyl aluminum are particularly preferred.
As the organoaluminum compound used for preparing the aluminoxane formulas _{(i-C 4 H 9)} x Al y (C
₅ H ₁₀ ) _z (where x, y, and z are positive numbers, and z ≧
2x. ) Can also be used.

The above-mentioned organoaluminum compounds can be used in combination of two or more kinds. Solvents used in the production of aluminoxane include, for example, benzene,
Aromatic hydrocarbons such as toluene, xylene, cumene and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane, and fats such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane Petroleum fractions such as cyclic hydrocarbons, gasoline, kerosene, and gas oil; and hydrocarbon solvents such as the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons, and halides of alicyclic hydrocarbons, especially chlorinated compounds and brominated compounds. Can be

Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferred. Reacts with metallocene compound [A] to form an ion pair
Compound [C] Examples of the compound [C] which forms an ion pair by reacting with the metallocene compound [A] used in the present invention include:
JP-A-501950, JP-T1-5020236,
JP-A-3-179005, JP-A-3-179900
No. 6, JP-A-3-207703, JP-A-3-207703
Examples thereof include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in 207704 and US-5321106.

Examples of the Lewis acid include a Mg-containing Lewis acid, A
Examples thereof include l-containing Lewis acids and B-containing Lewis acids, and among them, B-containing Lewis acids are preferable. As the Lewis acid containing a boron atom, specifically, compounds represented by the following general formula can be exemplified.

BR ¹ R ² R ³ (wherein R ¹ R ² and R ³ are each independently a phenyl group which may have a substituent such as a fluorine atom, a methyl group and a trifluoromethyl group) Or a fluorine atom.) As the compound represented by the above general formula, specifically,
Trifluoroboron, triphenylboron, tris (4-
Fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl)
Boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron,
Tris (3,5-dimethylphenyl) boron and the like. Of these, tris (pentafluorophenyl) boron is particularly preferred.

The ionic compound used in the present invention is a salt comprising a cationic compound and an anionic compound. The anion functions to cationize the metallocene compound [A] by reacting with the metallocene compound [A] and to stabilize the transition metal cation species by forming an ion pair. Examples of such anions include an organic boron compound anion, an organic arsenic compound anion, and an organic aluminum compound anion, and an anion that is relatively bulky and stabilizes a transition metal cation species is preferable. Examples of the cation include a metal cation, an organic metal cation, a carbonium cation, a tripium cation, an oxonium cation, a sulfonium cation, a phosphonium cation, and an ammonium cation.
Specific examples include triphenylcarbenium cation, tributylammonium cation, N, N-dimethylammonium cation, ferrocenium cation, and the like.

In the present invention, an ionic compound having an organic boron compound anion is preferred. In particular,
Triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o-tolyl) boron, Tributylammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o,
p-dimethylphenyl) boron, tributylammoniumtetra (m, m-dimethylphenyl) boron, tributylammoniumtetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammoniumtetra (o-tolyl) boron, tri ( n-butyl) ammonium tetra (4-
Trialkyl-substituted ammonium salts such as fluorophenyl) boron, N, N-dimethylaniliniumtetra (phenyl) boron, N, N-diethylaniliniumtetra (phenyl) boron, N, N-2,4,6-pentamethyl N, N-dialkylanilinium salts such as anilinium tetra (phenyl) boron; dialkylammonium salts such as di (n-propyl) ammonium tetra (pentafluorophenyl) boron; dicyclohexylammonium tetra (phenyl) boron; triphenylphospho And triarylphosphonium salts such as ammonium tetra (phenyl) boron, tri (methylphenyl) phosphonium tetra (phenyl) boron, and tri (dimethylphenyl) phosphonium tetra (phenyl) boron.

In the present invention, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentane) are used as the ionic compound containing a boron atom. Fluorophenyl) borate can also be mentioned.

Further, the following ionic compounds containing a boron atom can also be exemplified. (Note that the counter ion in the ionic compounds listed below is, but not limited to, tri (n-butyl) ammonium.) Salts of anions such as bis [tri (n-butyl) ammonium] nonaborate, bis (tri-n-butyl) ammonium [Tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl)
Ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate, tri (n-butyl) ammonium-1-carbadecaborate, tri (n-butyl) ammonium-1-carboundecaborate , Tri (n-butyl) ammonium-1-carbadodecaborate, tri (n-butyl) ammonium-1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, etc. Include the following borane compounds and carborane compounds. These compounds are used as Lewis acids and ionic compounds.

Examples of the borane compound, the carborane complex compound and the salt of the carborane anion include decaborane (14), 7,8-dicarboundecaborane (13), 2,2
7-dicarboundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri (n-butyl ) Ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ammonium
7-carboundecaborate (13), tri (n-butyl)
Ammonium 7,8-dicarboundecaborate (12),
Tri (n-butyl) ammonium 2,9-dicarboundecaborate (12), tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarboundecaborate, tri (n-butyl) ammoniumundeca Hydride 8-ethyl-7,9-dicarboundecaborate, tri (n-
Butyl) ammonium undecahydride-8-butyl
-7,9-Dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-Dicarboundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7 , 8-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carboundecaborate, and the like.

Examples of the carborane compound and the salt of carborane include 4-carbanonaborane (14), 1,3-
Dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-
Dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane and the like.

Further, the following compounds can be exemplified. (Note that the counter ion in the ionic compounds listed below is tri (n-butyl) ammonium,
It is not limited to this. Metal salt of carborane and metal borane anion such as tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (II
I), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) ferrate (ferrate) (III), tri (n-butyl) ammonium bis (undecahydride-7, 8-dicarboundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) nickelate (III), tri (n-butyl) ammonium bis (un) Decahydride-7,8-dicarboundecaborate) cubate (cuprate) (II
I), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) aurate (metal salt) (III), tri (n-butyl) ammonium bis (nonahydride-7,8- Dimethyl-7,8-dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) chromate (chromate) ( III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarboundecaborate) cobaltate (III), tri (n-butyl)
Ammonium bis (dodecahydride dicarbadodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III), tris [tri (n-butyl) ammonium] bis ( Undecahydride-7-carbaundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) manganate (I
V), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-cal) Bounce decaborate) nickelate (IV) and the like.

The above compound [C] can be used in combination of two or more kinds. Organoaluminum compound [D] The organoaluminum compound [D] used in the present invention is:
For example, it can be represented by the following general formula (a).

R ⁵ _n AlX _3-n (a) wherein R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to
3. In the above formula (a), R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group,
Examples include n-propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

Specific examples of such an organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum, and isoprenylaluminum. Alkenylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dialkylaluminum halide such as dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, etc. Ethyl aluminum Alkylaluminum sesquihalide such as Kiburomido, methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide, diethyl aluminum hydride, alkyl aluminum hydride such as diisobutylaluminum hydride and the like.

Further, as the organoaluminum compound [D], a compound represented by the following formula (b) can also be used. During ^{_{R 5 n AlY 3-n ···}} (b) ( wherein, R ⁵ is the same as R ⁵ in the formula (a), Y is -OR ⁶ group, -OSiR ⁷ ₃ group, -OAlR ⁸ ₂
Group, -NR ⁹ ₂ group, -SiR ¹⁰ ₃ group or -N (R ¹¹⁾
A AlR ¹² ₂ group, n is 1~2, R ^6, R ^7,
R ⁸ and R ¹² are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and R ⁹ is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, etc. And R ¹⁰ and R ¹¹ are a methyl group, an ethyl group or the like. Specific examples of such an organoaluminum compound include the following compounds.

(I) Compounds represented by R ⁵ _n Al (OR ⁶ ) _3-n , for example, dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide and the like.

[0087] _{^{(ii) R 5 n Al (}} OSiR 7 3) a compound represented by _3-n, e.g., _{(C 2 H 5) 2 Al} (OSi (C
H ₃ ) ₃ ), (iso-C ₄ H ₉ ) ₂ Al (OSi (C
_{H 3) 3), (iso} -C 4 H 9) 2 Al (OSi (C 2 H 5) 3)
Such.

[0088] _{^{(iii) R 5 n Al (}} OAlR 8 2) 3-n compound represented by, for example, _{(C 2 H 5) 2 Al} (OAl (C 2
_{H 5) 2), (iso} -C 4 H 9) 2 Al (OAl (iso-C
₄ H _{9) 2),} etc..

[0089] _{^{(iv) R 5 n Al (}} NR 9 2) a compound represented by _3-n, e.g., _{(CH 3) 2 Al (N} (C 2 H 5) 2),
(C ₂ H ₅ ) ₂ Al (NH (CH ₃ )), (CH ₃ ) ₂ Al
_{(NH (C 2 H 5)} ), (C 2 H 5) 2 Al [N (Si (CH
₃ ) ₃ ) ₂ ], (iso-C ₄ H ₉ ) ₂ Al [N (Si (C
Such as H _{3) 3) 2].}

(V) A compound represented by R ⁵ _n Al (SiR ¹⁰ ₃ ) _3-n , for example, (iso-C ₄ H ₉ ) ₂ Al (Si (C
H ₃ ) ₃ ). In the present invention, also R ⁵ ₃ A Of these
_{^{l, R 5 n Al (OR}} 6) 3-n, R 5 n Al (OAlR 8 2)
Preferred examples include an organoaluminum compound represented by _3-n , wherein R ⁵ is an isoalkyl group,
Compounds where n = 2 are particularly preferred. These organoaluminum compounds can be used in combination of two or more.

The specific metallocene-based catalyst used in the present invention contains the above-mentioned metallocene compound [A]. For example, as described above, the metallocene compound [A]
And an organic aluminum oxy compound [B]. It may be formed from a metallocene compound [A] and a compound [C] which reacts with the metallocene compound [A] to form an ion pair. Further, together with the metallocene compound [A], an organic aluminum oxy compound [B] is used. And a compound [C] which reacts with the metallocene compound [A] to form an ion pair. In these embodiments, it is particularly preferable to further use an organic aluminum compound [D] in combination.

In the present invention, the metallocene compound [A]
Is generally used in an amount of about 0.00005 to 0.1 mmol, preferably about 0.0001 to 0.05 mmol, in terms of transition metal atoms per liter of polymerization volume.

The organic aluminum oxy compound [B]
Is usually about 1 to 10,000 moles, preferably 10 to 10 moles of aluminum atoms per mole of transition metal atom.
It can be used in an amount of 5,000 mol.

The compound [C] which forms an ion pair by reacting with the metallocene compound [A] has a boron atom of usually about 0.5 to 20 mol, preferably 1 to 1 mol per mol of the transition metal atom. It is used in an amount to give 10 moles.

Further, the organoaluminum compound [D] is
It is usually about 0-1,000 mol, preferably about 0-500 mol, per 1 mol of boron atoms in the compound [C] forming an aluminum atom or an ion pair in the organic aluminum oxy compound [B]. Such amounts are used as needed.

Using the above metallocene catalyst,
Ethylene and an α-olefin having 4 to 20 carbon atoms;
When copolymerized with a non-conjugated polyene, an ethylene / α-olefin / non-conjugated polyene copolymer rubber can be obtained with excellent polymerization activity.

Even if ethylene, an α-olefin having 4 to 20 carbon atoms and a non-conjugated polyene are copolymerized using a Group VB transition metal compound-based catalyst such as a vanadium-based catalyst, sufficient polymerization can be achieved. Activity makes it impossible to obtain a copolymer rubber.

In the case of producing, for example, EPDM using a Group VB transition metal compound-based catalyst, the type of non-conjugated polyene is often limited to norbornene ring-containing polyenes such as ENB.

On the other hand, when a metallocene-based catalyst is used as in the present invention, the non-conjugated polyene is not limited to norbornene ring-containing polyenes, but various polyenes as described above, for example, 7-methyl-1,6- -Chain non-conjugated polyenes such as methyl octadiene (MOD) such as octadiene can also be copolymerized.

In the present invention, ethylene and C 4 -C 4
When the α-olefin of No. 20 and the non-conjugated polyene are copolymerized, the metallocene compound [A], the organoaluminum oxy compound [B], which constitute the metallocene catalyst,
The compound [C] forming the ion pair and the organoaluminum compound [D] may be separately supplied to the polymerization reactor, or a metallocene catalyst containing the metallocene compound [A] may be prepared in advance. May be subjected to a copolymerization reaction.

In preparing the metallocene catalyst,
A hydrocarbon solvent which is inert to the reaction with the catalyst component can be used. Specific examples of the inert hydrocarbon solvent include aliphatic solvents such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene. Hydrocarbon, cyclopentane, cyclohexane, alicyclic hydrocarbons such as methylcyclopentane, benzene, toluene, aromatic hydrocarbons such as xylene, ethylene chloride, chlorobenzene,
Halogenated hydrocarbons such as dichloromethane can be used. These hydrocarbon solvents can be used alone or in combination.

The above-mentioned metallocene compound [A], organic aluminum oxy compound [B], compound [C] forming an ion pair and organic aluminum compound [D] are usually
Mixing contact can be performed at 100 to 200 ° C, preferably -70 to 100 ° C.

In the present invention, ethylene and C 4 -C 4
The copolymerization of an α-olefin of 20 and a non-conjugated polyene is usually carried out at 40 to 200 ° C, preferably 50 to 150 ° C,
Particularly preferably, at 60 to 120 ° C. and at atmospheric pressure to 100 kg /
cm ^2, preferably atmospheric pressure to 50 kg / cm ^2, particularly preferably be carried out under the conditions of atmospheric pressure 30 kg / cm ^2.

The copolymerization reaction can be carried out by various polymerization methods, but is preferably carried out by solution polymerization. At this time, the above-mentioned hydrocarbon solvent can be used as the polymerization solvent.

The copolymerization can be carried out by any of a batch system, a semi-continuous system and a continuous system, but is preferably carried out by a continuous system. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

Further, the ethylene / α-
The olefin / non-conjugated polyene copolymer rubber can be obtained by the above-mentioned method, and the molecular weight of the copolymer rubber can be adjusted by changing polymerization conditions such as polymerization temperature, and hydrogen ( It can also be controlled by controlling the amount of the (molecular weight regulator) used.

The vibration- proof rubber molded product according to the present invention is composed of a vulcanized product of the above-mentioned ethylene / α-olefin / non-conjugated polyene copolymer rubber. Auxiliaries used, for example metal activators, compounds having an oxymethylene structure, scorch inhibitors may be included.

Further, a rubber reinforcing agent, a filler, a softening agent, an antioxidant, a processing aid,
When an additive such as a flame retardant is contained, the properties as a vibration-proof rubber molded article are further improved. Therefore, in the present invention, it is preferable to use the above-mentioned additives.

Manufacturing Method of Anti- Vibration Rubber Molding The anti-vibration rubber molding according to the present invention is preferably manufactured, for example, by the following method.

That is, by adding a vulcanizing agent to the above-mentioned ethylene / α-olefin / non-conjugated polyene copolymer rubber and performing vulcanization, the vibration-proof rubber molded article according to the present invention can be obtained. .

The vulcanization is performed by adding a vulcanizing agent to the ethylene / α-olefin / non-conjugated polyene copolymer rubber, and the vulcanizing agent is preferably added before molding. As a method for vulcanizing the ethylene / α-olefin / non-conjugated polyene copolymer rubber, sulfur vulcanization and organic peroxide vulcanization are effective.

Specific examples of the sulfur compound used in sulfur vulcanization include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dimethyldithiocarbamate. Can be Of these, sulfur is preferably used.

The sulfur compound is used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer rubber. .

When a sulfur compound is used as a vulcanizing agent, it is preferable to use a vulcanization accelerator in combination. Specific examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene
Sulfenamide compounds such as -2-benzothiazolesulfenamide and N, N-diisopropyl-2-benzothiazolesulfenamide; 2-mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, Thiazole compounds such as 2- (2,6-diethyl-4-morpholinothio) benzothiazole and dibenzothiazyldisulfide; diphenylguanidine, triphenylguanidine, diorthonitrileguanidine, orthonitrile biguanide, diphenylguanidine phthalate and the like Guanidine compounds; acetaldehyde-aniline reactants, butyraldehyde-aniline condensates, aldehyde amines such as hexamethylenetetramine, acetaldehyde ammonia or aldehyde-ammonia compounds; 2-
Imidazoline compounds such as mercaptoimidazoline; thiourea compounds such as thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea; tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutyl Thiuram compounds such as thiuram disulfide and pentamethylenethiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate,
Dithioacid salt compounds such as sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate and tellurium dimethyldithiocarbamate; xanthate compounds such as zinc dibutylxanthogenate; and compounds such as zinc white.

The vulcanization accelerator is used in an amount of 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer rubber.
Used in parts by weight.

The organic peroxide used in the vulcanization of an organic peroxide may be any compound which is usually used for vulcanization of a rubber. For example, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butyl hydroperoxide, t-butylcumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxin) hexyne-3, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5
-Mono (t-butylperoxy) -hexane, α, α'-
Bis (t-butylperoxy-m-isopropyl) benzene and the like can be mentioned. Among them, dicumyl peroxide, di-t-butyl peroxide and di-t-butylperoxy-3,3,5-trimethylcyclohexane are preferably used. These organic peroxides are used alone or in combination of two or more, and are used in an amount of 0.0003 to 0.000 to 100 g of the ethylene / α-olefin / non-conjugated polyene copolymer rubber.
It is used in an amount of 0.05 mol, preferably 0.001 to 0.03 mol, but it is desirable to determine an optimal amount appropriately according to the required physical property values.

When an organic peroxide is used as the vulcanizing agent, it is preferable to use a vulcanizing aid in combination. Specific examples of the vulcanization aid include sulfur; quinone dioxime compounds such as p-quinone dioxime; methacrylate compounds such as polyethylene glycol dimethacrylate; allyl compounds such as diallyl phthalate and triallyl cyanurate; Other maleimide compounds include divinylbenzene. Such a vulcanization aid is used in an amount of 0.5 to 2 mol, preferably about equimolar, based on 1 mol of the organic peroxide used.

In the production of the vibration-proof rubber molded article according to the present invention, it is preferable to further use a vulcanization aid such as a metal activator, a compound having an oxymethylene structure and an anti-scorch agent.

Specific examples of the metal activator include magnesium oxide, zinc white, zinc carbonate, higher fatty acid zinc, lead red, litharge, calcium oxide and the like. These metal activators are used in an amount of 3 to 1 based on 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer rubber.
It is used in an amount of 5 parts by weight, preferably 5 to 10 parts by weight.

To cope with various rubber processing steps, it is desirable to add a compound having an oxymethylene structure and a scorch inhibitor. Specific examples of the compound having an oxymethylene structure used in the present invention include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, and polypropylene glycol. Compounds having these oxymethylene structures are based on 100 parts by weight of ethylene / α-olefin / non-conjugated polyene copolymer rubber.
It is used in an amount of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight.

As the scorch inhibitor, known scorch inhibitors can be used, and specific examples thereof include maleic anhydride and salicylic acid. These scorch inhibitors are used in an amount of 0.2 to 5 parts by weight based on 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer rubber.
It is used in an amount of 0.3 parts by weight, preferably 0.3 to 3 parts by weight.

The rubber anti-vibration rubber article of the present invention has properties as a rubber anti-vibration article when additives such as a rubber reinforcing agent, a filler, a softening agent, an anti-aging agent and a processing aid are contained. Further improve. These additives may be appropriately mixed with the ethylene / α-olefin / non-conjugated polyene copolymer rubber before or after vulcanization.

Specific examples of the rubber reinforcing agent include SR
F, GPF, FEF, HAF, ISAF, SAF, F
Various carbon blacks such as T and MT, finely divided silicic acid, and various short fibers such as glass short fibers, cotton short fibers, polyester short fibers, nylon short fibers, and aramid short fibers.

Examples of the filler include light calcium carbonate, heavy calcium carbonate, talc, clay, silica and the like. The type and amount of these rubber reinforcing agents and fillers can be appropriately selected depending on the application, but the amount is usually up to 30 parts by weight based on 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer rubber.
0 parts by weight, preferably up to 200 parts by weight.

As the softening agent, a softening agent usually used for rubber can be used. Specifically, petroleum softening agents such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, petrolatum; coal tar softening agents such as coal tar and coal tar pitch; castor oil, linseed oil, rapeseed oil, Fatty oil-based softeners such as coconut oil;
Tall oil; sub; waxes such as beeswax, carnauba wax, and lanolin; fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate, zinc laurate; petroleum resins, atactic polypropylene, cumarone indene resins Synthetic plastics such as dioctyl phthalate, dioctyl agitate, dioctyl sebacate and the like. When a low molecular weight ethylene / α-olefin copolymer having an intrinsic viscosity [η] of 0.05 to 0.7 dl / g measured in decalin at 135 ° C. is used, not only a softener but also a roll processability can be improved. It has the effect of improving.

The amount of these softeners can be appropriately selected depending on the use of the vulcanizate. The amount of the softener is usually selected from ethylene / α-olefin / non-conjugated polyene copolymer rubber 100%.
Up to 150 parts by weight, preferably up to 1 part by weight
00 parts by weight.

As the antioxidant, an antioxidant which is usually used for rubber is added in an amount of 0.1 to 100 parts by weight of ethylene / α-olefin / non-conjugated polyene copolymer rubber.
It may be used in an amount of 1 to 5 parts by weight, preferably 0.5 to 3 parts by weight.

As the processing aid, a processing aid usually used for rubber is used in an amount of 10 parts by weight or less, preferably 1 to 5 parts by weight, based on 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer rubber. It may be used in parts by weight.

In the present invention, natural rubbers, diene rubbers such as SBR, IR, BR, etc., and EPDs may be incorporated into the composition for vibration-proof rubber moldings within a range not to impair the object of the present invention.
Other types of rubber such as M can also be compounded.

In the present invention, a flame retardant such as magnesium hydroxide, aluminum hydroxide, decabromodiphenyl oxide, antimony trioxide and the like can be blended.

The vibration-proof rubber molded article according to the present invention can be obtained, for example, by preparing and molding a rubber compound by the following method. That is, necessary additives such as an ethylene / α-olefin / non-conjugated polyene copolymer rubber, a reinforcing agent, a filler, and a softening agent are mixed by a mixer such as a Banbury mixer at a temperature of 80 to 170 ° C. for about 3 to 3 hours. 1
After kneading for 0 minutes, using a roll such as an open roll, a vulcanizing agent and, if necessary, a vulcanization accelerator or a vulcanization aid are additionally mixed, and a roll temperature of 40 to 80 ° C and 5 to 30 are used.
After kneading for a minute, the mixture is dispensed to prepare a ribbon-shaped or sheet-shaped compounded rubber.

The compounded rubber thus prepared is subjected to molding and vulcanization using a press molding machine, a transfer molding machine, an injection molding machine or the like to form a vibration-proof rubber molded body. The vibration-proof rubber molded product thus obtained is generally used in combination with iron. When it is necessary to bond iron and the vibration-proof rubber molded article according to the present invention, a sufficient adhesive force can be obtained even by using a commercially available adhesive. As such an adhesive, Chemlock 250, 253 manufactured by Lord Far East Co., etc. is preferably used.

The vibration-proof rubber molded article manufactured as described above has excellent environmental aging resistance (heat aging resistance, weather resistance, ozone resistance) and dynamic fatigue resistance (flex fatigue resistance).
Also shows excellent performance.

[0134]

According to the present invention, a vibration-proof rubber molded article according to the present invention is prepared by using a metallocene catalyst containing a specific metallocene compound, ethylene, an α-olefin having 4 to 20 carbon atoms, and a non-conjugated polyene. Is a random copolymer with
And a unit derived from ethylene and 4 to 20 carbon atoms
Having a molar ratio with a unit derived from an α-olefin, iodine value and intrinsic viscosity [η] of a specific range.
Since it is a cross-linked rubber molded article made of a rubber composition containing an α-olefin / non-conjugated polyene copolymer rubber, it has excellent effects of environmental aging resistance, excellent dynamic fatigue resistance, and long life.

Further, according to the production method of the present invention, it is possible to obtain an anti-vibration rubber molded article having the above effects. The anti-vibration rubber molded article according to the present invention is used for engine mounts, strut mounts, other mounts, bushings, torsional dampers, center supports, muffler hangers and other automobile anti-vibration rubbers, industrial anti-vibration rubbers, railway anti-vibration rubbers. It can be used for anti-vibration rubber such as anti-vibration rubber and marine anti-vibration rubber.

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples.

[0137]

[Production Example 1] Preliminary contact between zirconium compound and methylalumoxane
Preparation of catalyst solution

[0138]

Embedded image

A predetermined amount of the zirconium compound represented by the above formula and a toluene solution of methylalumoxane (1.2 mg atom / ml in terms of aluminum atom) are stirred at room temperature in a dark place for 30 minutes. To prepare a toluene solution in which the zirconium compound and methylalumoxane were dissolved. The Zr concentration of this toluene solution was 0.004 mmol / ml, and the methylalumoxane concentration was 1.10 in terms of aluminum atoms.
2 milligram atoms / ml.

Then, to this toluene solution, hexane, a 5-fold solution of toluene, was added with stirring to prepare a catalyst solution having the following Zr concentration and methylalumoxane concentration. Used as a reaction catalyst.

Zr concentration: 0.00067 mmol / ml
(= 0.67 mmol / l) Methylalumoxane concentration (in terms of Al atom): 0.
20 mmol / ml (= 200 mmol / l) using a stainless steel polymerization vessel 15 liters of capacity, equipped with Polymerization stirring blade, and continuously ethylene, 1-butene, 5-ethylidene-2-norbornene (hereinafter (Also referred to as ENB) in the presence of the above-mentioned polymerization reaction catalyst.

That is, first, 3.2 liters / hour of dehydrated and purified hexane, 0.005 liters / hour of the above-mentioned catalyst solution, and a hexane solution of triisobutylaluminum (concentration: 17 mmol / liter) were introduced into the polymerization vessel from the top of the polymerization vessel. , And a hexane solution of ENB (concentration: 0.025 liter / liter) was continuously supplied at 1.5 liters / hour.

Further, 200 l / h of ethylene and 200 l / h of 1-butene were continuously supplied from the upper part of the polymerization reactor into the polymerization reactor. This copolymerization reaction is 6
The reaction was carried out at 0 ° C. and the average residence time was 1 hour (that is, 5 liters of polymerization scale).

Next, a small amount of methanol was added to the polymerization solution withdrawn from the lower part of the polymerization vessel to stop the polymerization reaction.
After separating the copolymer from the solvent by steam stripping, under conditions of 100 ° C. and reduced pressure (100 mmHg),
Dry for 24 hours.

As described above, ethylene / 1-butene
ENB copolymer rubber [Copolymer rubber (A)] is 18 per hour
Obtained in an amount of 0 g. The resulting copolymer rubber has a molar ratio of units derived from ethylene to units derived from 1-butene (ethylene / 1-butene) of 72/28, and EN
The iodine value based on B was 22.

This copolymer rubber had an intrinsic viscosity [η] of 3.8 dl / g and a B value of 1.01 measured in decalin at 135 ° C. The results are shown in Table 1.

[0147]

Production Examples 2 to 4 An ethylene / α-olefin / non-conjugated polyene copolymer rubber [copolymer] was prepared in the same manner as in Production Example 1 except that the copolymerization reaction was carried out under different polymerization conditions. Rubbers (B) to (D)].

Table 1 shows the molar ratio, iodine value, intrinsic viscosity [η] and B value of the units derived from ethylene and the units derived from α-olefin of these copolymer rubbers.

[0149]

[Production Example 5] VOCl _3- (C ₂ H ₅ ) _1.5 Al as a catalyst
Using Cl _1.5 , ethylene-propylene-5
-Ethylidene-2-norbornene copolymer rubber [EPDM
(A)]. Table 1 shows the molar ratio, the iodine value, the intrinsic viscosity [η] and the B value of the units derived from ethylene and the units derived from propylene in the obtained copolymer rubber.

[0150]

[Table 1]

[0151]

Example 1 The copolymer (A) obtained in Production Example 1 was converted to a second
According to the table, blended and kneaded with a 2-liter capacity Banbury mixer [manufactured by Kobe Steel Ltd.] for 6 minutes, and further a pair of open rolls (surface temperature of front roll / surface temperature of rear roll: 50 ° C./50° C.) According to Table 3, a vulcanizing agent and a vulcanization accelerator were added and kneaded at a rotation speed of the front roll / rotation speed of the rear roll: 16 rpm / 18 rpm to obtain an unvulcanized compound rubber.

[0152]

[Table 2]

[0153]

[Table 3]

The compounded rubber obtained as described above was mixed with 1
Pressed at 60 ° C. for 20 minutes to prepare a vulcanized sheet having a thickness of 2 mm. The vulcanized sheet was subjected to a tensile test, a hardness test, a durability test, a compression set test, a dynamic viscoelasticity test and a Gehman low-temperature torsion test as follows. Was performed according to the method described in

Table 4 shows the results. <Test method> [1] Tensile test A vulcanized sheet was punched out and JIS K6301 (1989)
No. 3 dumbbell test piece described in
Using this test piece, a measurement temperature of 25 ° C. and a tensile speed of 500 m were applied in accordance with the method specified in JIS K6301 Paragraph 3.
A tensile test was conducted under the conditions of
_B and tensile elongation at break E _B was measured. [2] Hardness test The hardness test was performed in accordance with JIS K 6301 (1989), and the spring hardness H _S (JIS A hardness) was measured. [3] Durability test A vulcanized sheet was punched out to prepare a No. 1 dumbbell test piece described in JIS K 6301, and a 2 mm scratch was made at the center of the test piece. Of the 60 test pieces thus obtained, the elongation rate was set to 50% for 20 test pieces,
Elongation fatigue was performed under the conditions of a set temperature of 40 ° C. and a rotation speed of 300 rpm, and the average value of the number of times the dumbbell was cut was used as an index of durability. A durability test was also performed under the condition of an elongation of 100%.

Monsanto Fatigue Tester: Frequency 5 Hz, temperature 27 ° C. [4] Compression set test The compression set test is 12 in accordance with JIS K6301.
The compression set was measured in an atmosphere at a temperature of 0 ° C. for 22 hours, and the compression set was measured. The compression set was used as an index for evaluating sag resistance. [5] Dynamic Viscoelasticity Test The dynamic viscoelasticity test was performed on a vulcanized sheet having a thickness of 2 mm using a rheometric viscoelasticity tester (model RDS-2) at a measurement temperature of 27 ° C., a frequency of 10 Hz, and Distortion factor 1
%, And the loss tangent tan δ (index of vibration damping property) was determined by the following equation.

G _S = G ′ + ιG ″ [G _S : static elastic modulus, real part G ′: dynamic elastic modulus, imaginary part G ″: dynamic loss elastic modulus] tan δ = G ″ / G ′ [6] Gehman low temperature torsion test The Gehman low temperature torsion test is based on JIS K 6301 (19
1989), and T ₁₀ [unit: ° C.] was determined.

[0158]

Example 2 In Example 1, the copolymer (B) obtained in Production Example 2 was used in place of the copolymer rubber (A).
The procedure was performed in the same manner as in Example 1 except that the blending amounts of EF-HS carbon black and oil were changed to 65 parts by weight and 55 parts by weight, respectively.

The results are shown in Table 4.

[0160]

Example 3 Example 1 was repeated except that the copolymer rubber (C) obtained in Production Example 3 was used instead of the copolymer rubber (A).

Table 4 shows the results.

[0162]

Example 4 The procedure of Example 1 was repeated, except that the copolymer rubber (D) obtained in Production Example 4 was used instead of the copolymer rubber (A).

Table 4 shows the results.

[0164]

Comparative Example 1 The procedure of Example 1 was repeated, except that the EPDM (A) obtained in Production Example 5 was used instead of the copolymer rubber (A).

Table 4 shows the results.

[0166]

[Table 4]

Claims (5)

[Claims] 1. A cross-linked rubber molded article comprising a rubber composition containing an ethylene / α-olefin / non-conjugated polyene copolymer rubber comprising ethylene, an α-olefin having 4 to 20 carbon atoms and a non-conjugated polyene. The ethylene / α-olefin / non-conjugated polyene copolymer rubber, in the presence of a metallocene-based catalyst containing a metallocene compound,
Ethylene and an α-olefin having 4 to 20 carbon atoms;
(1) (a) a unit derived from ethylene and (b) a carbon number of 4 to
The units derived from 20 α-olefins are 40/6
(2) iodine value is 1 to 50, (3) intrinsic viscosity [η] measured in decalin at 135 ° C.
Is 2 to 10 dl / g. 2. The metallocene compound represented by the following general formula [I] or [II]: [In the formula, M is a transition metal of Group IVB of the periodic table, and R ¹¹ and R ¹² are a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by halogen. , A silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, R ¹³ and R ¹⁴ are each an alkyl group having 1 to 20 carbon atoms, and X ¹ and X ² are A hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group; Divalent hydrocarbon group, divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, divalent silicon-containing group, divalent germanium-containing group, -O-, -C
O -, - S -, - SO -, - SO 2 -, - NR 7 -, -
^{P (R 7) -, -} P (O) (R 7) -, - BR 7 - or -AlR ⁷ - a. (However, R ⁷ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.)], [Wherein, M is a transition metal of Group IVB of the periodic table, and R ^{21 s} may be the same or different from each other, and may be a hydrogen atom, a halogen atom, or an optionally halogenated carbon atom having 1 to 1 carbon atoms. 10 alkyl groups, aryl groups having 6 to 10 carbon atoms, or -NR ₂ , -SR, -OSiR ₃ , -SiR
₃ or —PR ₂ groups (R is a halogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms), and R ^{22 to} R ²⁸ are the same as defined above for R ²¹ . And R ^{22 to} R ^{28 which} are present or adjacent to each other may form an aromatic ring or an aliphatic ring together with the atoms to which they are bonded, X ³ and X ⁴ may be the same or different from each other; Hydrogen atom, halogen atom, OH group, 1 to 1 carbon atoms
10 alkyl groups, 1 to 10 carbon atom alkoxy groups, 6 to 10 carbon atom aryl groups, 6 to 6 carbon atoms
10 aryloxy groups, alkenyl groups having 2 to 10 carbon atoms, arylalkyl groups having 7 to 40 carbon atoms, alkylaryl groups having 7 to 40 carbon atoms, 8 carbon atoms
~ 40 arylalkenyl groups; -Sn -, - O -, - S -, = SO, = SO 2, = NR
²⁹ , = CO, = PR ²⁹ or = P (O) R ²⁹ .
(However, R ²⁹ and R ³⁰ may be the same or different from each other, and include a hydrogen atom, a halogen atom,
10 alkyl groups, fluoroalkyl group having 1 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, fluoroaryl group having 6 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, carbon number An alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, and 8 carbon atoms
-40 arylalkenyl groups or 7-4 carbon atoms
0 may be an alkylaryl group, or R ²⁹ and R ³⁰ may each form a ring with the atoms to which they are attached, and M ² is a silicon, germanium or tin atom. 2. The vibration-proof rubber molded article according to claim 1, which is a metallocene compound represented by the following formula: 3. The ethylene / α-olefin / non-conjugated polyene copolymer rubber according to (4), wherein the B value obtained from the ¹³ C-NMR spectrum and the following formula is 1.00 to 1.50. B value = [P _OE ] / (2 · [P _E ] · [P _O ]), wherein [P _E ] is a random number. [ _Po ] is the mole fraction of the unit derived from (b) α-olefin in the random copolymer rubber, which is the mole fraction of the unit derived from ethylene in the copolymer rubber. And [P _OE ] is the ratio of the number of α-olefin / ethylene chains to the total number of dyad chains in the random copolymer rubber). 4. A vibration-proof rubber molded article obtained by crosslinking a rubber composition containing an ethylene / α-olefin / non-conjugated polyene copolymer rubber comprising ethylene, an α-olefin having 4 to 20 carbon atoms and a non-conjugated polyene. Wherein the ethylene / α-olefin / non-conjugated polyene copolymer rubber comprises ethylene and ethylene in the presence of a metallocene catalyst containing a metallocene compound represented by the following formula [I] or [II]. Obtained by random copolymerization of an α-olefin having 4 to 20 carbon atoms and a non-conjugated polyene, (1) (a) a unit derived from ethylene, and (b) a carbon atom having 4 to 20 carbon atoms.
The units derived from 20 α-olefins are 40/6
(2) iodine value is 1 to 50, (3) intrinsic viscosity [η] measured in decalin at 135 ° C.
Is 2 to 10 dl / g, a process for producing a vibration-proof rubber molded product; [In the formula, M is a transition metal of Group IVB of the periodic table, and R ¹¹ and R ¹² are a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by halogen. , A silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, R ¹³ and R ¹⁴ are each an alkyl group having 1 to 20 carbon atoms, and X ¹ and X ² are A hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group; Divalent hydrocarbon group, divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, divalent silicon-containing group, divalent germanium-containing group, -O-, -C
O -, - S -, - SO -, - SO 2 -, - NR 7 -, -
^{P (R 7) -, -} P (O) (R 7) -, - BR 7 - or -AlR ⁷ - a. (However, R ⁷ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.)], [Wherein, M is a transition metal of Group IVB of the periodic table, and R ^{21 s} may be the same or different from each other, and may be a hydrogen atom, a halogen atom, or an optionally halogenated carbon atom having 1 to 1 carbon atoms. 10 alkyl groups, aryl groups having 6 to 10 carbon atoms, or -NR ₂ , -SR, -OSiR ₃ , -SiR
₃ or —PR ₂ groups (R is a halogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms), and R ^{22 to} R ²⁸ are the same as defined above for R ²¹ . And R ^{22 to} R ^{28 which} are present or adjacent to each other may form an aromatic ring or an aliphatic ring together with the atoms to which they are bonded, X ³ and X ⁴ may be the same or different from each other; Hydrogen atom, halogen atom, OH group, 1 to 1 carbon atoms
10 alkyl groups, 1 to 10 carbon atom alkoxy groups, 6 to 10 carbon atom aryl groups, 6 to 6 carbon atoms
10 aryloxy groups, alkenyl groups having 2 to 10 carbon atoms, arylalkyl groups having 7 to 40 carbon atoms, alkylaryl groups having 7 to 40 carbon atoms, 8 carbon atoms
~ 40 arylalkenyl groups; -Sn -, - O -, - S -, = SO, = SO 2, = NR
²⁹ , = CO, = PR ²⁹ or = P (O) R ²⁹ .
(However, R ²⁹ and R ³⁰ may be the same or different from each other, and include a hydrogen atom, a halogen atom,
10 alkyl groups, fluoroalkyl group having 1 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, fluoroaryl group having 6 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, carbon number An alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, and 8 carbon atoms
-40 arylalkenyl groups or 7-4 carbon atoms
0 may be an alkylaryl group, or R ²⁹ and R ³⁰ may each form a ring with the atoms to which they are attached, and M ² is a silicon, germanium or tin atom. )]. 5. The ethylene / α-olefin / non-conjugated polyene copolymer rubber according to (4), wherein the B value determined from the ¹³ C-NMR spectrum and the following formula is 1.00 to 1.50. B value = [P _OE ] / (2 · [P _E ] · [P _O ]) (wherein [P _E ] is: The molar fraction of the units derived from (a) ethylene in the random copolymer rubber, and [P _O ] is the molar fraction of the units derived from the (b) α-olefin in the random copolymer rubber. [P _OE ] is the ratio of the number of α-olefin / ethylene chains to the total number of dyad chains in the random copolymer rubber).