JP3388075B2 - Ethylene / α-olefin / non-conjugated polyene random copolymer, rubber composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ethylene / α-olefin / non-conjugated polyene random copolymer and a method for producing the same. The present invention relates to a non-conjugated polyene random copolymer and a method for producing such a rubber. Further, the present invention relates to this ethylene / α-olefin
The present invention relates to a vulcanizable rubber composition containing a non-conjugated polyene random copolymer, having excellent mechanical strength, weather resistance and ozone resistance, and also having excellent processability.

[0002]

BACKGROUND OF THE INVENTION Conventionally, ethylene / propylene / polyene terpolymers (EPDM) and the like
α-olefin / non-conjugated polyene random copolymer (hereinafter also simply referred to as ethylene copolymer rubber) is excellent in weather resistance, ozone resistance, heat aging resistance, etc., and is used for automotive materials, electric wire materials, and civil engineering materials. Widely used as materials and industrial materials.

[0003] Ethylene / α used for such purposes
-It is desired that the olefin / non-conjugated polyene random copolymer has excellent moldability, a high vulcanization rate, and excellent vulcanization strength.

Among such ethylene copolymer rubbers, copolymer rubbers which can be vulcanized at high speed include, for example, ethylene propylene ethylidene norbornene (EN)
B) Copolymer rubber is known, but conventionally known ethylene / propylene / ENB copolymer rubber is inferior in extrusion moldability.

For example, ethylene-propylene-dicyclopentadiene copolymer rubber is known as an ethylene copolymer rubber having excellent extrusion moldability. The sulfur strength is not excellent.

[0006] For this reason, it is excellent in workability, the vulcanization speed is high,
Ethylene and α with excellent mechanical properties such as vulcanization strength
-The appearance of an olefin / non-conjugated polyene random copolymer, a rubber composition and a method for producing such a copolymer rubber is desired.

The present inventor has conducted intensive studies on the ethylene / α-olefin / non-conjugated polyene random copolymer, the rubber composition and the production method in view of the above prior art. Units derived from and (b)
40/60 to 95 with units derived from α-olefin
/ 5 [(a) / (b)], (ii) iodine value is 1 to 50, and (iii) intrinsic viscosity [η] is 0.1 to 8 dl.
/ G and (iv) ethylene having a gη ^* value of 0.2 to 0.9 or a g ′ value of 0.2 to 0.9 and having a long-chain branch in the molecule. The vulcanizable rubber composition containing the α-olefin / non-conjugated polyene random copolymer and the rubber has the above-mentioned properties,
The present inventors have found that this copolymer rubber can be efficiently obtained by using a catalyst containing a specific metallocene compound, and have completed the present invention.

[0008]

An object of the present invention is to provide an ethylene / α-olefin / non-olefin having excellent processability, high vulcanization rate, and excellent mechanical properties such as vulcanization strength which could not be obtained by the conventional production method. It is an object of the present invention to provide a conjugated polyene random copolymer and a method for producing the same, and a rubber composition containing the ethylene / α-olefin / non-conjugated polyene random copolymer.

[0009]

SUMMARY OF THE INVENTION The ethylene / α-olefin / non-conjugated polyene random copolymer of the present invention comprises (a) ethylene, (b) an α-olefin having 3 or more carbon atoms, and (c) carbon / carbon Among the heavy bonds, a carbon-carbon double bond polymerizable with a metallocene catalyst is a random copolymer consisting of only one non-conjugated polyene in one molecule, and has the following characteristics. are doing. (i) The molar ratio of (a) a unit derived from ethylene and (b) a unit derived from an α-olefin having 3 or more carbon atoms in a molar ratio of 40/60 to 95/5 [(a) / (b)]. (Ii) an iodine value of 1 to 50; (iii) intrinsic viscosity [η] measured in decalin at 135 ° C.
Is 0.1 to 8.0 dl / g, and (iv) the intrinsic viscosity [η] measured in the above (iii) is the same as the ethylene content having the same weight average molecular weight (by the light scattering method). Ratio of 70 mol% of linear ethylene / propylene copolymer to intrinsic viscosity [η] _blank gη ^* (= [η] /
[Η] _blank ) is 0.57 to 0.9.

The above-mentioned characteristic (iv) of the ethylene / α-olefin / non-conjugated polyene random copolymer according to the present invention.
May be specified by the following g ′ value instead of the g′η value. (iv) The intrinsic viscosity [η] measured in the above (iii) and the gel permeation chromatography (GP) of this ethylene / α-olefin / non-conjugated polyene random copolymer
C: 140 ° C., o-dichlorobenzene solvent), intrinsic viscosity [η] in terms of a linear ethylene-propylene copolymer having an ethylene content of 70 mol%, as determined by measuring the o-dichlorobenzene solvent).
_blank ' And the ratio g ′ (= [η] / [η] _blank ′) is 0.
It may be 61 to 0.9.

The ethylene / α-olefin of the present invention
The method for producing a non-conjugated polyene random copolymer comprises the above-mentioned ethylene / α-olefin / non-conjugated polyene random copolymer using a metallocene-based catalyst containing a metallocene compound represented by the following formula [I]. Is manufactured.

[0012]

Embedded image

Wherein M is a transition metal of Group IVB of the periodic table, R ¹ is a hydrocarbon group having 1 to 6 carbon atoms,
² , R ⁴ , R ⁵ , and R ⁶ may be the same or different, and each may be a hydrogen atom, a halogen atom, or
R ³ is an aryl group having 6 to 16 carbon atoms, and the aryl group may be substituted with a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an organic silyl group. Good.

X ¹ and X ² may be the same or different and include a hydrogen atom, a halogen atom, and a carbon atom having 1 to 2 carbon atoms.
0 is a hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group, and Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, Divalent halogenated hydrocarbon group, divalent silicon-containing group, divalent germanium-containing group, divalent tin-containing group, -O-, -C
O -, - S -, - SO -, - SO 2 -, - NR 7 -, -
^{P (R 7) -, -} P (O) (R 7) -, - BR 7 - or -AlR ⁷ - [proviso R ⁷ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, carbon atoms 1-20 halogenated hydrocarbon groups]. ).

The vulcanizable rubber composition according to the present invention is characterized by containing the above-mentioned ethylene / α-olefin / non-conjugated polyene random copolymer. The vulcanizable rubber composition according to the present invention can contain other components together with the ethylene / α-olefin / non-conjugated polyene random copolymer as described above, and specifically, ethylene / α-olefin -With respect to 100 parts by weight of the non-conjugated polyene random copolymer, a reinforcing agent and / or an inorganic filler can be contained in an amount of 10 to 200 parts by weight and a softening agent in an amount of 10 to 200 parts by weight. The vulcanized rubber according to the present invention is obtained from such a rubber composition.

[0016]

DETAILED DESCRIPTION OF THE INVENTION First, the ethylene / α-olefin / non-conjugated polyene random copolymer according to the present invention will be described.

Ethylene / α-olefin / non-conjugated polyether
Non-random copolymer The ethylene / α-olefin / non-conjugated polyene random copolymer according to the present invention comprises (a) ethylene and (b) 3 carbon atoms.
A non-conjugated polyene having only one α-olefin and one carbon-carbon double bond capable of being polymerized by a metallocene catalyst (c)
(c) also referred to as a non-conjugated polyene) and has the following properties.

The ethylene / α-olefin of the present invention
The non-conjugated polyene random copolymer (hereinafter also referred to as a random copolymer) is derived from (a) ethylene, (b) an α-olefin having 3 or more carbon atoms, and a specific (c) non-conjugated polyene.

This (b) has 3 or more carbon atoms, specifically 3 carbon atoms.
Examples of the α-olefin of -20 to 20 include propylene, 1-butene, 1-pentene, 1-hexene, and 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, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,
1-octadecene, 1-eicosene and combinations thereof.

Of these, α-olefins having 3 to 10 carbon atoms are preferable, and propylene, 1-butene, 1-hexene, 1-octene and the like are particularly preferably used.

Non-conjugated polyene (c) used in the present invention
Is a non-conjugated polyene in which only one carbon-carbon double bond polymerizable by a metallocene catalyst among carbon-carbon double bonds exists in one molecule. Such non-conjugated polyene
(c) does not include a chain polyene that is a vinyl group at both ends. When one of the two or more double bonds is a terminal vinyl group, the other double bond preferably has an internal olefin structure instead of the terminal vinyl group. Here vinyl groups refers to a -CH = CH ₂ structure. Specific examples of such a non-conjugated polyene (c) include, for example,
1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene,
4-ethyl-1,4-hexadiene, 3-methyl-1,4-hexadiene, 3,3-dimethyl-1,4-hexadiene, 5-methyl-1,4-
Heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-
1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 1,6-octadiene, 4-methyl-
1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene,
5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-
1,6-octadiene, 6-butyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl-1,4-nonadiene, 5-ethyl- 1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene, 6-methyl- 1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl- 1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1,5-decadiene, 6-methyl- 1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 6-ethyl-1,6-decadiene, 7-methyl- 1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-de Diene, 8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 6-methyl-1,6- And aliphatic polyenes such as undecadiene and 9-methyl-1,8-undecadiene.

As the alicyclic polyene, a polyene composed of an alicyclic portion having one unsaturated bond and a chain portion having an internal olefinic bond is preferable. For example, 5-ethylidene-2-norbornene , 5-isopropylidene
2-norbornene, 6-chloromethyl-5-isopropenyl-2
-Norbornene and the like.

Also, trienes such as 2,3-diisopropylidene-5-norbornene and 2-ethylidene-3-isopropylidene-5-norbornene can be mentioned. These can be used in combination of two or more.

In the present invention, among them, those having 7 carbon atoms
The non-conjugated polyene described above is preferable, and for example, 7-methyl-1,6-octadiene (MOD), 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene and the like are preferably used.

(I) (a) Ethylene / (b) α-olefin Component Ratio The ethylene / α-olefin / non-conjugated polyene random copolymer provided by the present invention comprises (a) a unit derived from ethylene, (b) a unit derived from an α-olefin having 3 or more carbon atoms (hereinafter sometimes simply referred to as (b) α-olefin) is 40/60 to 95/5, preferably 55/45.
９０90/10 [(a) / (b)].

(Ii) Iodine value The ethylene / α-olefin / non-conjugated polyene random copolymer has an iodine value of 1 to 50, preferably 2 to 40, more preferably 5 to 35, and particularly preferably 7 to 30.

The ethylene / α-olefin / non-conjugated polyene random copolymer having an iodine value as described above has a high vulcanization rate and can be vulcanized at high speed.

(Iii) Intrinsic viscosity [η] The intrinsic viscosity [η] of the ethylene / α-olefin / non-conjugated polyene random copolymer measured in decalin at 135 ° C. is preferably 0.1 to 8.0 dl / g. Is 0.2 to 6 dl
/ G.

(Iv) gη ^* value or g ′ value gη ^* value is the intrinsic viscosity [η] measured in the above (iii).
And the intrinsic viscosity [η] _blank of a linear ethylene-propylene copolymer having the same weight average molecular weight (by light scattering method) and an ethylene content of 70 mol% (gη ^* =
[Η] / [η] _blank ). ethylene·
g of α-olefin / non-conjugated polyene random copolymer
The η ^* value is between 0.2 and 0.9, preferably between 0.4 and 0.8. Note the [eta] _blank, for the ethylene-propylene-non-conjugated polyene copolymer, replacing the weight average molecular weight M _W determined by light scattering method to a viscosity-average molecular weight M _v, obtained by calculation from formula (I) . [Η] _blank = 7.2 × 10 ^-4 M _V ^0.667 (I)

The g 'value is determined by the intrinsic viscosity [η] measured in the above (iii) and the gel permeation chromatography (GPC: 140 ° C., of this ethylene / α-olefin / non-conjugated polyene random copolymer). o-dichlorobenzene solvent), a linear ethylene-propylene copolymer having an ethylene content of 70 mol% (E
PR) converted intrinsic viscosity [η] ratio to _blank '(g' =
[Η] / [η] _blank '). In the above [η] _blank ', first, a GPC measurement of an ethylene / α-olefin / non-conjugated polyene random copolymer is performed to obtain a polystyrene-equivalent molecular weight Mi _-PSt of each fraction.
Next, Mi _-PSt is _calculated using the formula [η] _i-PSt · Mi _-PSt = [η] _i-EPR · Mi _-EPR and [η] _i-PSt = 1.37 × 10 ^-4 M _{Using the} ^{equation of} _i-PSt ^0.686 , [η] _i-EPR = 7.2 × 10 ^-4 M _i-EPR ^0.667 , the molecular weight is converted to _EPR- converted molecular weight M _i-EPR . Next, the converted Mi _-EPR is _{calculated according} to the formula (II) to obtain [η]
_i-blank '. [Η] _i-blank '= 7.2 × 10 ⁻⁴ M _i-EPR ^0.667 (II) Here, the subscript i represents each fraction separated by GPC. Next, the transformed [η] _i-blank '
[Η] _blank 'is calculated by II). [Η] _blank '= Σω _i · [η] _i-blank ' / Σω _i (III) where ω represents a weight fraction. Thus, [η]
_Blank 'is calculated, and g' is determined from the ratio with [η]. The thus obtained ethylene / α-olefin / non-conjugated polyene random copolymer (g ′ = [η] /
[Η] _blank ') value is 0.2 to 0.9, preferably 0.4
-0.85, more preferably 0.4-0.8. The ethylene / α-olefin / non-conjugated polyene random copolymer obtained in the present invention has a gη ^* value or g ′ value considerably smaller than 1 as described above, and a long-chain branch is formed in the molecule. Is shown. Such a random copolymer rubber is excellent in processability.

The ethylene / α-olefin /
The non-conjugated polyene random copolymer may be modified with a polar monomer, and the modified product will be described later in detail.

In the present invention, the specific ethylene / α-olefin / non-conjugated polyene random copolymer as described above is obtained by reacting (a) ethylene with a metallocene catalyst.
It can be obtained by random copolymerizing (b) an α-olefin having 3 or more carbon atoms and (c) a non-conjugated polyene.

The metallocene catalyst used in the present invention is:
It is desirable to contain the following specific metallocene compound [A]. The metallocene-based catalyst suitably used in the present invention is not particularly limited except that it contains the metallocene compound [A]. For example, the metallocene compound [A] and the organic aluminum oxy compound [B] and / or [A] And a compound [C] which forms an ion pair by reacting with [A] and [B].
And / or an organic aluminum compound [D] together with [C].

The components will be described below. FIG. 1 shows an example of a process for preparing a metallocene catalyst used in the present invention and a process for producing an ethylene / α-olefin / non-conjugated polyene random copolymer.

[A] Metallocene Compound In the present invention, a compound represented by the following general formula [I] is preferably used as the metallocene compound [A].

[0036]

Embedded image

In the formula, M is a transition metal atom belonging to Group IVB of the periodic table, specifically, titanium, zirconium, or hafnium, particularly preferably zirconium. The substituent R ¹ R ¹ is a hydrocarbon group having 1 to 6 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n -Alkyl groups such as pentyl, neopentyl, n-hexyl and cyclohexyl, and alkenyl groups such as vinyl and propenyl. Among these, a primary alkyl group in which the carbon bonded to the indenyl group is preferred,
To 4 are preferred, and a methyl group and an ethyl group are particularly preferred.

The substituents R ² , R ⁴ , R ⁵ , R ⁶ R ² , R ⁴ , R ⁵ , and R ⁶ may be the same or different and each may be a hydrogen atom, a halogen atom or a carbon atom similar to R ^1. These are hydrocarbon groups of the formulas 1 to 6. Here, the halogen atom is fluorine, chlorine, bromine, or iodine.

The substituent R ³ R ³ is an aryl group having 6 to 16 carbon atoms. This aryl group may be substituted with a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an organic silyl group.

Examples of the aryl group include phenyl, α-naphthyl, β-naphthyl, anthracenyl, phenanthryl, pyrenyl, acenaphthyl, phenalenyl,
Aceanthrenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like. Of these, phenyl, naphthyl, anthracenyl and phenanthryl are preferred.

The hydrocarbon group having 1 to 20 carbon atoms which is a substituent of the aryl group includes, for example, methyl, ethyl, propyl, butyl, hexyl, cyclohexyl,
Octyl, nonyl, dodecyl, eicosyl, norbornyl, alkyl groups such as adamantyl, vinyl, propenyl, alkenyl groups such as cyclohexenyl, benzyl,
Examples include the arylalkyl groups such as phenylethyl and phenylpropyl, the aryl groups exemplified above, and the aryl groups such as tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, methylnaphthyl, and benzylphenyl. Examples of the organic silyl group include trimethylsilyl, triethylsilyl, triphenylsilyl and the like.

X ¹ and X ² X ¹ and X ² may be the same or different from each other, and represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen. , An oxygen-containing group or a sulfur-containing group. Specific examples include the same halogen atoms and hydrocarbon groups as described above.

Examples of the oxygen-containing group include a hydroxy group, an alkoxy group such as methoxy, ethoxy, propoxy and butoxy; an alloxy group such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; an arylalkoxy group such as phenylmethoxy and phenylethoxy; A trifluoroacetate group;

Examples of the sulfur-containing group include substituents obtained by substituting oxygen in the oxygen-containing group with sulfur, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate. , Trimethylbenzenesulfonate,
Sulfonate groups such as triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluorobenzenesulfonate, methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate, trimethylbenzene Sulfinate groups such as sulfinate and pentafluorobenzene sulfinate. Of these,
It is preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

[0045] Y Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, 1 to carbon atoms
20 divalent halogenated hydrocarbon groups, divalent silicon-containing groups, divalent germanium-containing groups, divalent tin-containing groups,-
O -, - CO -, - S -, - SO -, - SO 2 -, - N
R ^7- , -P (R ⁷ )-, -P (O) (R ⁷ )-, -B
R ⁷ — or —AlR ⁷ — (where R ⁷ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
20 halogenated hydrocarbon groups), specifically, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-
Alkylene groups such as 1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4-cyclohexylene, diphenylmethylene, diphenyl-1,2
-1 carbon atoms such as arylalkylene groups such as ethylene
To 20 divalent hydrocarbon groups, halogenated hydrocarbon groups obtained by halogenating the above divalent hydrocarbon groups having 1 to 20 carbon atoms such as chloromethylene, silylene, methylsilylene, dimethylsilylene, diethylsilylene, di ( Alkyl silylene such as n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene, and alkylarylsilylene , Arylsilylene group, tetramethyl-1,2-
Disilyl, alkylphenylsilyl such as tetraphenyl-1,2-disilyl, divalent silicon-containing groups such as alkylaryldisilyl and aryldisilyl groups, and the above divalent silicon-containing group in which silicon has been substituted with germanium or tin And divalent groups.

R ⁷ 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 these, Y is preferably a divalent silicon-containing group, a divalent germanium-containing group, more preferably a divalent silicon-containing group, and is an alkylsilylene, an alkylarylsilylene, or an arylsilylene. Is particularly preferred.

In the metallocene compound used in the present invention, the ligands having two cyclopentadienyl skeletons bonded via Y may be the same or different.

Specific examples of the transition metal compound represented by the above general formula [I] are shown below. rac-dimethylsilylene-
Bis {1- (4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4-
Phenylindenyl) zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-methyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (β-naphthyl)
Indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (1-anthracenyl)
Indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (2-anthracenyl)
Indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (9-anthracenyl)
Indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (9-phenanthryl)
Indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (p-fluorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (Pentafluorophenyl) indenyl) zirconium dichloride, ra
c-dimethylsilylene-bis {1- (2-methyl-4- (p-chlorophenyl) indenyl)} zirconium dichloride, ra
c-dimethylsilylene-bis {1- (2-methyl-4- (m-chlorophenyl) indenyl)} zirconium dichloride, ra
c-dimethylsilylene-bis {1- (2-methyl-4- (o-chlorophenyl) indenyl)} zirconium dichloride, ra
c-dimethylsilylene-bis {1- (2-methyl-4- (o, p-dichlorophenyl) phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p -Bromophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (p-tolyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl -4- (m-
Tolyl) indenyl) zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-methyl-4- (o-tolyl)) indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (o, o'-dimethylphenyl) ) Indenyl) zirconium dichloride, ra
c-dimethylsilylene-bis {1- (2-methyl-4- (p-ethylphenyl) indenyl)} zirconium dichloride, ra
c-dimethylsilylene-bis {1- (2-methyl-4- (pi-propylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p-
Benzylphenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (p
-Biphenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (m-
Biphenyl) indenyl) zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-trimethylsilylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-
4- (m-trimethylsilylphenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis
(2-phenyl-4-phenyl) indenyl) デ zirconium dichloride, rac-diethylsilylene-bis ｛1- (2-methyl-4-phenyl) indenyl)｝ zirconium dichloride, rac-di- (i-propyl) silylene- Bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-di- (n-butyl) silylene-bis {1- (2-methyl)
-4-phenylindenyl)｝ zirconium dichloride,
rac-Dicyclohexylsilylene-bis {1- (2-methyl-4-
Phenylindenyl) zirconium dichloride, rac
-Methylphenylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-Diphenylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac- Di (p-tolyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis {1- (2-methyl-4-phenylindene) Nil) zirconium dichloride, rac-methylene-
Bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-ethylene-bis {1- (2-methyl-
4-phenylindenyl)｝ zirconium dichloride, r
ac-dimethylgermylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylstannylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dibromide, rac-dimethylsilylene-bis ｛1
-(2-methyl-4-phenylindenyl) zirconium dimethyl, rac-dimethylsilylene-bis ｛1- (2-methyl-
4-phenylindenyl)｝ zirconium methyl chloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4-phenylindenyl)｝ zirconium chloride SO ₂ M
e, rac-Dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride OSO ₂ M
e, rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium monochloride mono (trifluoromethanesulfonate), rac-dimethylsilylene-bis {1- (2-methyl-4) -Phenylindenyl) zirconium di (trifluoromethanesulfonate),
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium di (p-toluenesulfonate), rac-dimethylsilylene-bis {1- (2-methyl-
4-phenylindenyl)｝ zirconium di (methylsulfonate), rac-dimethylsilylene-bis ｛1- (2-methyl-4-phenylindenyl)｝ zirconiumdi (trifluoromethanesulfinate), rac-dimethyl Silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium di (trifluoroacetate), rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium monochloride (N-butoxide), r
ac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium di (n-butoxide), rac
-Dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium monochloride (phenoxide), rac-dimethylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride , Rac-dimethylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (β-naphthyl)
Indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (2-methyl-1-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl -4- (5-acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (9-anthracenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (9-phenanthryl) indenyl) デ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (o-methylphenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene -Bis {1- (2-ethyl-4- (m-methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (p-methylphenyl) Indenyl)} zirconium dichloride, rac- dimethylsilylene - bis {1- (2-ethyl-4- (2,3-dimethylphenyl) indenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-ethyl-4- (2,4-dimethylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,5-dimethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,
4,6-trimethylphenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl
-4- (o-chlorophenyl) indenyl) デ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl
-4- (m-chlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilyl-bis ｛1- (2-ethyl-4
-(P-chlorophenyl) indenyl) デ zirconium dichloride, rac-dimethylsilyl-bis ｛1- (2-ethyl-4-
(2,3-dichlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl
-4- (2,6-dichlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-ethyl-4- (3,5-dichlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene- Screw ｛1-
(2-ethyl-4- (2-bromophenyl) indenyl) デ zirconium dichloride, rac-dimethylsilylene-bis ｛1-
(2-ethyl-4- (3-bromophenyl) indenyl) デ zirconium dichloride, rac-dimethylsilylene-bis ｛1-
(2-ethyl-4- (4-bromophenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis-1-
(2-ethyl-4- (4-biphenylyl) indenyl) デ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-
Ethyl-4- (4-trimethylsilylphenyl) indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-n-propyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis ｛1
-(2-n-propyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1-
(2-n-propyl-4- (β-naphthyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis
(2-n-propyl-4- (2-methyl-1-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-n-propyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl-4- (9-anthracenyl) indenyl) ｝ Zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-propyl-4- (9-phenanthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-propyl-4 -Phenylindenyl) デ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-propyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2- i-propyl-4- (β-naphthyl) indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-i-propyl-4- (8-methyl-9-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-propyl-4- (5- Acenaphthyl)
Indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-propyl-4- (9-anthracenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-propyl -4- (9-phenanthryl) indenyl) zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-s-butyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl-4- (α-naphthyl) indenyl)} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-s-butyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl-4- (5- Acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s-butyl-4- (9-anthracenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-s -Butyl-4- (9-phenanthryl)
Indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-pentyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-n-pentyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-n-butyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis ｛1-
(2-n-butyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-
n-butyl-4- (β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-butyl-4- (2-methyl-1-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-
n-butyl-4- (5-acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-
n-butyl-4- (9-anthracenyl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1-
(2-n-butyl-4- (9-phenanthryl) indenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1
-(2-i-butyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-butyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethyl Silylene-bis ｛1- (2-i-butyl-4
-(Β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-butyl-4- (2
-Methyl-1-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-butyl-4)
-(5-acenaphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-butyl-4)
-(9-anthracenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-i-butyl
-4- (9-phenanthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-neopentyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2- Neopentyl
-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-n-hexyl-4
-Phenylindenyl) zirconium dichloride, rac
-Dimethylsilylene-bis {1- (2-n-hexyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-
Methylphenylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride , Rac-methylphenylsilylene-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, ra
c-methylphenylsilylene-bis {1- (2-ethyl-4- (9-
Phenanthryl) indenyl)｝ zirconium dichloride, rac-diphenylsilylene-bis ｛1- (2-ethyl-4-phenylindenyl)｝ zirconium dichloride, rac-diphenylsilylene-bis ｛1- (2-ethyl-4- (α -Naphthyl) indenyl)｝ zirconium dichloride, rac-diphenylsilylene-bis ｛1- (2-ethyl-4- (9-anthracenyl) indenyl)｝ zirconium dichloride, rac-diphenylsilylene-bis ｛1- (2-ethyl- 4- (9-phenanthryl) indenyl) zirconium dichloride, rac-
Diphenylsilylene-bis {1- (2-ethyl-4- (4-biphenylyl) indenyl)} zirconium dichloride, rac-
Methylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-methylene-bis} 1
-(2-ethyl-4- (α-naphthyl) indenyl) ニ ル zirconium dichloride, rac-ethylene-bis ｛1- (2-ethyl-4-
Phenylindenyl) zirconium dichloride, rac-
Ethylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-ethylene-bis {1- (2-n-propyl-4- (α-naphthyl) indenyl)}
Zirconium dichloride, rac-dimethylgermylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylgermylene-bis {1- (2-ethyl-4- (α-naphthyl) Indenyl)｝ zirconium dichloride, rac-dimethylgermylene-bis ｛1- (2-n-propyl-4-phenylindenyl)｝ zirconium dichloride and the like.

Further, compounds in which zirconium in the above compounds is replaced with titanium or hafnium can also be mentioned.

In the present invention, a racemate of the above metallocene compound is usually used as a catalyst component.
Molds can also be used.

In the present invention, two or more metallocene compounds as described above may be used in combination. Such a metallocene compound is disclosed in Journal of Organometallic Chem. 2
88 (1985), pp. 63-67, European Patent Application Publication No. 0,32.
It can be manufactured according to the specification of Japanese Patent No. 0,762.

[B] Organoaluminum oxy compound The organoaluminum oxy compound [B] used in the present invention may be a conventionally known aluminoxane, or as exemplified in JP-A-2-78687. Benzene-insoluble organic aluminum oxy compounds.

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 in 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. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered aluminoxane solution by distillation, and then redissolved in the solvent.

As the organoaluminum compound used in the production of aluminoxane, specifically, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trisec Trialkylalkyl such as -butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc., tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum, dimethylaluminum chloride, Such as diethylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride, etc. Alkylaluminum halides, diethylaluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride, dimethyl aluminum methoxide, dialkylaluminum alkoxides such as diethylaluminum ethoxide and dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide and the like.

Of these, trialkyl aluminum and tricycloalkyl aluminum are particularly preferred.
Further, as an organoaluminum compound used in the production of aluminoxane, a compound represented by the formula (i-C ₄ H ₉ ) _x Al _y (C ₅ H
₁₀ ) Isoprenyl aluminum represented by _z (where x, y, and z are positive numbers and z ≧ 2x) can 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, cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecane, and fats such as cyclopentane, cyclohexane, cyclooctane, methylcyclopentane Petroleum fractions such as cyclic hydrocarbons, gasoline, kerosene, and gas oil; and hydrocarbon solvents such as the above aromatic hydrocarbons, aliphatic hydrocarbons, halides of alicyclic hydrocarbons, especially chlorinated compounds, and brominated compounds. Can be

Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred. The above organoaluminum oxy compounds can be used in combination of two or more.

[C] Reaction with metallocene compound [A]
Compound Forming Ion Pair The compound [C] that forms an ion pair by reacting with the metallocene compound [A] used in the present invention is described in
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 US Pat. No. 207704 and US Pat.

As the Lewis acid, a Lewis acid containing Mg, Al
And a B-containing Lewis acid. Of these, a B-containing Lewis acid is preferable. Specific examples of the Lewis acid containing a boron atom include compounds represented by the following general formula.

BR ¹¹ R ¹² R ¹³ (wherein R ¹¹ , R ¹² and R ¹³ are each independently
A fluorine atom, a phenyl group which may have a substituent such as a methyl group or a trifluoromethyl group, or a fluorine atom. Specific examples of the compound represented by the above general formula include trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, and 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], thereby stabilizing 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 those which are relatively bulky and stabilize transition metal cation species are preferable.
As cations, metal cations, organometallic cations,
Examples include a carbonium cation, a tripium cation, an oxonium cation, a sulfonium cation, a phosphonium cation, and an ammonium cation. More specifically, a triphenylcarbenium cation, a tributylammonium cation, an N, N-dimethylammonium cation, a ferrocenium cation, and the like.

Of these, ionic compounds containing a boron compound as an anion are preferred.
Examples of the trialkyl-substituted ammonium salt include 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, tributylammonium tetra (m, m-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron,
Tri (n-butyl) ammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (4-fluorophenyl) boron and the like are mentioned, and N, N-dialkylanilinium salts include -Dimethylaniliniumtetra (phenyl) boron, N, N-diethylaniliniumtetra (phenyl) boron, N, N-2,4,6-pentamethylaniliniumtetra (phenyl) boron and the like,
Examples of the dialkyl ammonium salt include di (n-propyl) ammonium tetra (pentafluorophenyl)
Boron, dicyclohexylammonium tetra (phenyl) boron and the like, and triarylphosphonium salts such as triphenylphosphonium tetra (phenyl) boron, tri (methylphenyl) phosphonium tetra (phenyl) boron, tri (dimethyl) Phenyl)
And phosphonium tetra (phenyl) boron.

In the present invention, as the ionic compound containing a boron atom, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) Phenyl) borate can also be mentioned.

The following compounds can also be exemplified.
(In the ionic compounds listed below, the counter ion is, but not limited to, tri (n-butyl) ammonium.) Salts of anions such as bis [tri (n-butyl) ammonium] nonaborate and bis [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 Examples thereof include -1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, and borane compounds and carborane compounds. These compounds are used as Lewis acids and ionic compounds.

Borane and carborane complex compounds and salts of carborane anions such as decaborane (14), 7,
8-dicarboundecaborane (13), 2,7-dicarboundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2, 7-dicarboundecaborane, bird (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 (1
2), tri (n-butyl) ammonium dodeca hydride-8-methyl 7,9-dicarboundecaborate, tri (n-butyl
Butyl) ammonium undecahydride-8-ethyl-
7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarboundecaborate, tri (n-butyl) ammoniumundecahydride-8-allyl-7, 9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7- Carboranes and salts of carboranes, such as carbaundecaborate, for example 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl -1,3-dicarbanonaborane, dodeca hydride-
The following compounds can also be exemplified, such as 1-methyl-1,3-dicarbanonaborane and undecahydride-1,3-dimethyl-1,3-dicarbanonaborane. (In the ionic compounds listed below, the counter ion is, but is not limited to, tri (n-butyl) ammonium.) Metal carborane salts and metal borane anions such as tri (n-butyl) ammonium bis (nona Hydride
1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) 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 (undecahydride-7,8- Dicarboundecaborate) cubate (cuprate) (III), 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) (II
I), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarboundecaborate)
Cobaltate (III), tri (n-butyl) ammonium bis (dodeca hydride dicarbadodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodeca hydride dodecaborate) nickelate (III), tris [Tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) Manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) cobaltate (II
I) and bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) nickelate (IV).

The compound [C] which forms an ion pair by reacting with the metallocene compound [A] as described above can be used in combination of two or more.

[D] Organoaluminum Compound The organoaluminum compound [D] used in the present invention is:
For example, it can be represented by the following general formula (a).

R ²¹ _n AlX _3-n (a) wherein R ²¹ 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 ²¹ is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group. , N-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl and tolyl groups.

Specific examples of such an organoaluminum compound include the following compounds. Trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum,
Trialkylaluminums such as trioctylaluminum and tri-2-ethylhexylaluminum, alkenylaluminums such as isoprenylaluminum, dimethylaluminum chloride, dialkylaluminum halides such as diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide, and methyl Alkyl aluminum sesquihalides such as aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide, methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, ethyl aluminum Alkylaluminum dihalides such as dibromide, diethyl aluminum hydride, alkyl aluminum hydride such as diisobutyl aluminum hydride.

Further, as the organoaluminum compound [D], a compound represented by the following formula (b) can also be used. R ²¹ nAlY _3-n (b) (wherein, R ²¹ is the same as above, Y is —OR ²² group,
-OSiR ²³ ₃ group, -OAlR ²⁴ ₂ group, -NR ²⁵ ₂ group,
-SiR ²⁶ ₃ group or -N (R ²⁷⁾ is AlR ²⁸ ₂ group, n is ^{1~2, R 22, R 23,} R 24 and R
²⁸ methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, R ²⁵
Is hydrogen, methyl, ethyl, isopropyl, phenyl, trimethylsilyl, etc., and R ²⁶ and R ²⁷
Represents a methyl group, an ethyl group or the like. Specific examples of such an organoaluminum compound include the following compounds.

(I) a compound represented by R ²¹ nAl (OR ²² ) _3-n , for example, dimethylaluminum methoxide
Diethylaluminum ethoxide, diisobutylaluminum methoxide and the like.

[0074] ^{(ii) R 21 nAl (OSiR} 23 3) a compound represented by _3-n, e.g., _{(C 2 H 5) 2 Al} (OSi (CH
₃ ) ₃ ), (iso-C ₄ H ₉ ) ₂ Al (OSi (CH ₃ ) ₃ ),
Such as _{(iso-C 4 H 9)} 2 Al (OSi (C 2 H 5) 3).

[0075] ^{(iii) R 21 nAl (OAlR} 24 2) Compounds represented by _3-n, e.g., _{(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..

[0076] ^{(iv) R 21 nAl (NR} 25 2) Compounds 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)), (C
H 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
Such as _{(CH 3) 3) 2]} .

[0077] ^{(v) R 16 nAl (SiR} 26 3) a compound represented by _3-n, e.g., _{(iso-C 4 H 9)} 2 Al (Si (CH
₃ ) ₃ ) etc. In the present invention, among these, R ²¹ ₃ Al and R ²¹ nAl
(OR ²²⁾ _3-n, can be mentioned organoaluminum compounds represented by _{^{R 21 nAl (OAlR 24 2)}} 3-n Suitable examples, R ⁵ is an isoalkyl group, compounds which are n = 2 is Particularly preferred. These organoaluminum compounds may be used in combination of two or more.

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

In the present invention, the metallocene compound [A]
Is generally used in an amount of about 0.0005 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 mol, preferably 10 to 10 mol of aluminum atom per 1 mol 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 10 mol, per mol of the transition metal atom. It is used in a molar amount.

Further, the organoaluminum compound [D] is
The amount is usually about 0 to 1000 mol, preferably about 0 to 500 mol, per 1 mol of the boron atom in the compound [C] forming an aluminum atom or an ion pair in the organic aluminum oxy compound [B]. It is used as needed in an amount.

Using the above metallocene catalyst,
(a) ethylene and (b) an α-olefin having 3 or more carbon atoms
(c) By copolymerizing with a non-conjugated polyene, an ethylene / α-olefin / non-conjugated polyene random copolymer can be obtained with excellent polymerization activity.

By using a group VB transition metal compound catalyst such as a vanadium catalyst, (a) ethylene, (b) α-olefin having 3 or more carbon atoms and (c) non-conjugated polyene are copolymerized. However, a copolymer rubber cannot be obtained with sufficient polymerization activity. Further, using a Group VB transition metal compound-based catalyst,
For example, when producing EPDM or the like, (c) the type of non-conjugated polyene is often limited to norbornene ring-containing polyenes such as ENB. On the other hand, as in the present invention,
When a group B metallocene catalyst is used, (c) the non-conjugated polyene is not limited to norbornene ring-containing polyenes, but also copolymerizes chain non-conjugated polyenes such as various polyenes such as MOD as described above. be able to.

In the present invention, when copolymerizing (a) ethylene, (b) an α-olefin having 3 or more carbon atoms, and (c) a non-conjugated polyene, the above metallocene compound constituting a metallocene catalyst [ A], the organoaluminum oxy compound [B], the compound [C] forming an ion pair, and the organoaluminum compound [D] may be separately supplied to the polymerization reactor, or the metallocene compound [A] may be supplied in advance.
May be subjected to a copolymerization reaction after preparing a metallocene-based catalyst.

In preparing the metallocene catalyst,
A hydrocarbon medium that is inert with the catalyst component can be used. Specific examples of the inert hydrocarbon medium include propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene. Hydrocarbons, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane, aromatic hydrocarbons such as benzene, toluene, and xylene, and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane can be used. These may be used in combination.

The above 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, the copolymerization of (a) ethylene, (b) an α-olefin having 3 or more carbon atoms, and (c) 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 particularly preferably atmospheric pressure to 50 kg / cm ² can be carried out under the conditions of atmospheric pressure 30 kg / cm ^2.

This 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.

The specific random copolymer as described above can be obtained by the present invention. The molecular weight of the random copolymer rubber can be adjusted by changing the polymerization conditions such as the polymerization temperature. It can also be controlled by controlling the amount of (molecular weight regulator) used.

The product immediately after polymerization is recovered from the polymerization solution by a conventionally known separation and recovery method and dried to obtain a solid random copolymer.

In the present invention, the modified ethylene / α-olefin /
Non-conjugated polyene random copolymer (random copolymer)
May be graft-modified with a polar monomer.

Examples of the polar monomer include a hydroxyl group-containing ethylenically unsaturated compound, an amino group-containing ethylenically unsaturated compound, an epoxy group-containing ethylenically unsaturated compound, an aromatic vinyl compound, an unsaturated carboxylic acid or a derivative thereof, and a vinyl ester. Compounds, vinyl chloride and the like.

Examples of the hydroxyl group-containing ethylenically unsaturated compound include hydroxyethyl (meth) acrylate,
2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-3-
Phenoxy-propyl (meth) acrylate, 3-chloro
2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylolethane mono (meth) acrylate, butanediol mono (meth) acrylate (Meth) acrylates such as polyethylene glycol mono (meth) acrylate, 2- (6-hydroxyhexanoyloxy) ethyl acrylate, 10
-Undecen-1-ol, 1-octen-3-ol, 2-methanol norbornene, hydroxystyrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-methylolacrylamide, 2- (meth) acryloyloxyethyl acid phosphate, glycerin Monoallyl ether, allyl alcohol, allyloxyethanol, 2-butene-1,4-diol, glycerin monoalcohol and the like.

Examples of the amino group-containing ethylenically unsaturated compound include vinyl monomers having at least one kind of amino group or substituted amino group represented by the following formula.

[0097]

Embedded image

Wherein R ³¹ is a hydrogen atom, a methyl group or an ethyl group; R ³² is a hydrogen atom, having 1 to 12 carbon atoms;
Preferably an alkyl group having 1 to 8 carbon atoms, 6 to 1 carbon atoms
2, preferably 6 to 8 cycloalkyl groups. The above-mentioned alkyl group and cycloalkyl group may further have a substituent. )

Examples of such an amino group-containing ethylenically unsaturated compound include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, and methacrylic acid. Phenylaminoethyl acrylate, alkylester derivatives of acrylic acid or methacrylic acid such as cyclohexylaminoethyl methacrylate N-vinyldiethylamine, vinylamine derivatives such as N-acetylvinylamine allylamine, methacrylamine, N-methylacrylamine, Allylamine derivatives such as N, N-dimethylacrylamide and N, N-dimethylaminopropylacrylamide Acrylamide derivatives such as N-methylacrylamide Aminostyrene such as p-aminostyrene S 6-aminohexyl succinimide and 2-aminoethyl succinimide and the like.

As the epoxy group-containing ethylenically unsaturated compound, a monomer having at least one polymerizable unsaturated bond and at least one epoxy group in one molecule is used. Such epoxy group-containing ethylenically unsaturated compounds include, for example, glycidyl acrylate, glycidyl methacrylate, etc., mono- and diglycidyl esters of maleic acid, mono- and diglycidyl esters of fumaric acid, mono- and diglycidyl esters of crotonic acid, Mono- and diglycidyl esters of tetrahydrophthalic acid, mono- and glycidyl esters of itaconic acid,
Mono- and diglycidyl esters of butenetricarboxylic acid, mono- and diglycidyl esters of citraconic acid,
Mono- and diglycidyl esters of endo-cis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (Nadic acid ^™ ), endo-cis-bicyclo [2.2.1] hept-5-ene- 2-methyl-2,3-dicarboxylic acid (methylnadic acid ^TM)
Mono- and diglycidyl esters of dicarboxylic acids such as mono- and glycidyl esters of allyl succinic acid (alkyl groups having 1 to 12 carbon atoms in the case of monoglycidyl esters), alkyl glycidyl esters of p-styrene carboxylic acid, Allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxy-1-
Butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene,
5,6-epoxy-1-hexene, vinylcyclohexene monoxide and the like.

The aromatic vinyl compound is represented by the following formula.

[0102]

Embedded image

[0103] (wherein, R ¹ and R ² are each independently a hydrogen atom or an alkyl group such as methyl group having 1 to 3 carbon atoms, an ethyl group, a propyl group, .R ³ is 1 carbon atoms is isopropyl And a hydrocarbon group or a halogen atom, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a chlorine atom, a bromine atom or an iodine atom, and n is usually 0 to 5, preferably 1 It is an integer of ~ 5.)

As such an aromatic vinyl compound,
For example, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, p-chlorostyrene, m-chlorostyrene, p-chloromethylstyrene, 4-vinylpyridine, 2-vinylpyridine, 5 -Ethyl-2
-Vinylpyridine, 2-methyl-5-vinylpyridine, 2-isopropenylpyridine, 2-vinylquinoline, 3-vinylisoquinoline, N-vinylcarbazole, N-vinylpyrrolidone and the like.

Examples of the unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, and bicyclo [2,2,1 ] Unsaturated carboxylic acids such as hept-2-ene-5,6-dicarboxylic acid or derivatives thereof (eg, acid anhydrides, acid halides, amides, imides, esters, etc.)
Is mentioned.

Examples of the derivative include maleenyl chloride, malenimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6- Dicarboxylic anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citrate, dimethyl tetrahydrophthalate, bicyclo [2,2,1] hept-2-ene-5, Examples include dimethyl 6-dicarboxylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, aminoethyl methacrylate and aminopropyl methacrylate.

Among these, (meth) acrylic acid, maleic anhydride, hydroxyethyl (meth) acrylate, glycidyl methacrylate and aminopropyl methacrylate are preferred.

Examples of the vinyl ester compound include vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, and vinyl benzoate. , Pt-butyl vinyl benzoate, vinyl salicylate, vinyl cyclohexanecarboxylate and the like.

Preparation of Modified Random Copolymer The modified random copolymer can be obtained by graft-polymerizing a polar monomer to the above random copolymer.

When the above-mentioned polar monomer is graft-polymerized to the random copolymer, the polar monomer is
Usually 1 to 10 parts by weight based on 100 parts by weight of the random copolymer.
It is used in an amount of 0 parts by weight, preferably 5 to 80 parts by weight.

This graft polymerization is usually performed in the presence of a radical initiator. As the radical initiator, an organic peroxide or an azo compound can be used.

Examples of the organic peroxide include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, and 2,5-dimethylperoxide.
Dimethyl-2,5-bis (t-butylperoxy) hexyne-3,
1,3-bis (t-butylperoxyisopropyl) benzene,
1,1-bis (t-butylperoxy) bararate, benzoyl peroxide, t-butylperoxybenzoate, acetyl peroxide, isobutyryl peroxide,
Octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide and 2,4-dichlorobenzoyl peroxide, m-toluyl peroxide and the like can be mentioned.

Examples of the azo compound include azoisobutyronitrile and dimethylazoisobutyronitrile.

The radical initiator is selected from the random copolymer 10
It is desirable to use it in an amount of about 0.001 to 10 parts by weight with respect to 0 parts by weight. The radical initiator can be used as it is by mixing it with the random copolymer and the polar monomer, but can also be used after dissolving it in a small amount of an organic solvent. As the organic solvent, any organic solvent capable of dissolving a radical initiator can be used without any particular limitation. Examples thereof include aromatic hydrocarbon solvents such as benzene, toluene and xylene, pentane, hexane, heptane, and octane. , Aliphatic hydrocarbon solvents such as nonane and decane, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene, chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and Chlorinated hydrocarbons such as tetrachloroethylene, alcoholic solvents such as methanol, ethanol, n-propynol, iso-propanol, n-butanol, sec-butanol and tert-butanol, acetone, methyl ethyl ketone and methyl isobutyl ketone Ketone solvents such as down, ester solvents, dimethyl ether, diethyl ether, such as ethyl acetate and dimethyl phthalate, di -n- amyl ether, can be used ether solvents such as tetrahydrofuran and dioxy anisole.

When grafting a polar monomer to the random copolymer, a reducing substance may be used.
When a reducing substance is used, the graft amount of the polar monomer can be improved.

Examples of the reducing substance include iron (II) ion, chromium ion, cobalt ion, nickel ion, palladium ion, sulfite, hydroxylamine, hydrazine, -SH, SO ₃ H, -NHNH ₂ , -COC
Compounds containing groups such as H (OH)-are exemplified.

Specific examples of such a reducing substance include ferrous chloride, potassium dichromate, cobalt chloride, and the like.
Cobalt naphthenate, palladium chloride, ethanolamine, diethanolamine, N, N-dimethylaniline, hydrazine, ethylmercaptan, benzenesulfonic acid, p-
And toluene sulfonic acid.

In the present invention, the reducing substance can be used in an amount of usually 0.001 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the random copolymer. Graft modification of the random copolymer with a polar monomer can be performed by a conventionally known method. For example, a random copolymer is dissolved in an organic solvent, and then a polar monomer and a radical initiator are added to the solution.
At a temperature of 0 ° C, preferably 80-190 ° C, 0.5-1
The reaction can be carried out for 5 hours, preferably 1 to 10 hours.

The organic solvent is not particularly limited as long as it can dissolve the random copolymer. For example, aromatic hydrocarbon solvents such as benzene, toluene and xylene, and fatty solvents such as pentane, hexane and heptane A group hydrocarbon solvent or the like can be used.

The modified random copolymer can also be produced by reacting the random copolymer with a polar monomer without using a solvent using an extruder or the like.

This reaction is usually carried out at a temperature equal to or higher than the melting point of the random copolymer, specifically at a temperature of 120 to 250 ° C.
Desirably, it is performed for 5 to 10 minutes. The amount of modification (graft amount of polar monomer) of the modified random copolymer thus obtained is usually 0.1 to 50% by weight, preferably 0.2 to 30% by weight.

Vulcanizable Rubber Composition The vulcanizable rubber composition according to the present invention containing the above-mentioned ethylene / α-olefin / polyene random copolymer may be used in an unvulcanized state. However, when used as a vulcanizate, more excellent properties can be exhibited.

The vulcanizable rubber composition according to the present invention can be vulcanized by heating using a vulcanizing agent or by irradiating an electron beam without using a vulcanizing agent.
The vulcanizable rubber composition according to the present invention is ethylene-α-
Other components can be appropriately contained according to the purpose together with the olefin / polyene copolymer).
-The olefin / polyene copolymer in the total rubber composition
It is desirable to contain it in an amount of 0% by weight or more, preferably 25% by weight or more.

Further, other components include, for example, a reinforcing agent,
Various compounds such as inorganic fillers, softeners, anti-aging agents (stabilizers), processing aids, and compounds constituting foaming systems such as foaming agents and foaming aids, plasticizers, coloring agents, and other rubber compounding agents. And the like. The type and content of the other components are appropriately selected depending on the application, and among these, it is particularly preferable to use a reinforcing agent, an inorganic filler, a softening agent, and the like, which will be more specifically described below.

Reinforcing Agent and Inorganic Filler Specific examples of the reinforcing agent include SRF, GPF, FEF,
Examples thereof include carbon blacks such as MAF, HAF, ISAF, SAF, FT, and MT, those obtained by subjecting these carbon blacks to surface treatment with a silane coupling agent, silica, activated calcium carbonate, fine talc, fine silicate, and the like.

Specific examples of the inorganic filler include light calcium carbonate, heavy calcium carbonate, talc, clay and the like. The rubber composition according to the present invention comprises a reinforcing agent and / or an inorganic filler containing ethylene / α-olefin /
10 to 3 with respect to 100 parts by weight of the polyene copolymer (A)
It can be contained in an amount of 00 parts by weight, preferably 10 to 200 parts by weight.

From the rubber composition containing such an amount of the reinforcing agent, a vulcanized rubber having improved mechanical properties such as tensile strength, tear strength and abrasion resistance can be obtained. When the inorganic filler is blended in the above amount, the hardness can be increased without impairing other physical properties of the vulcanized rubber, and the cost can be reduced.

As the softening agent, a softening agent conventionally compounded in rubber is widely used, and specific examples thereof include petroleum softening agents such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, petrolatum, and the like. Coal tar, coal tar softener such as coal tar pitch, castor oil, linseed oil, rapeseed oil, fatty oil softener such as coconut oil, tall oil, sub, beeswax, carnauba wax, waxes such as lanolin,
Ricinoleic acid, palmitic acid, barium stearate,
Fatty acids and fatty acid salts such as calcium stearate and zinc laurate, synthetic polymer substances such as petroleum resin, atactic polypropylene, and coumarone indene resin are used.

Among these, petroleum softeners are preferred, and process oils are particularly preferred. In the rubber composition according to the present invention, the softener as described above is used in an amount of 10 to 200 parts by weight, preferably 10 to 150 parts by weight, based on 100 parts by weight of the ethylene / α-olefin / polyene copolymer (A). Can be contained in an amount of 10 to 100 parts by weight.

Anti-aging agent The rubber composition according to the present invention preferably contains an anti-aging agent because the material life can be extended. As the antioxidant, specifically, phenylnaphthylamine,
Aromatic secondary amine stabilizers such as 4,4 '-(α, α-dimethylbenzyl) diphenylamine, N, N'-di-2-naphthyl-p-phenylenediamine, 2,6-di-t-butyl Phenolic stabilizers such as -4-methylphenol, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl]
Thioether stabilizer such as sulfide, benzimidazole stabilizer such as 2-mercaptobenzimidazole, dithiocarbamate stabilizer such as nickel dibutyldithiocarbamate, polymerization of 2,2,4-trimethyl-1,2-dihydroquinoline And quinoline-based stabilizers. These may be used in combination of two or more.

[0131] Such anti-aging agents include ethylene-α-
For 100 parts by weight of the olefin / polyene copolymer,
It can be appropriately used in an amount of 5 parts by weight or less, preferably 3 parts by weight or less.

Processing Aids As processing aids, those generally blended with rubber as processing aids can be widely used. In particular,
Acids such as ricinoleic acid, stearic acid, palmitic acid, and lauric acid, and salts of these higher fatty acids, such as barium stearate, zinc stearate, calcium stearate, and esters.

The processing aid is ethylene / α-olefin.
It can be suitably used in an amount of 10 parts by weight or less, preferably 5 parts by weight or less, based on 100 parts by weight of the polyene copolymer. When the vulcanizing agent or the rubber composition according to the present invention is vulcanized by heating, a compound constituting a vulcanizing system such as a vulcanizing agent, a vulcanization accelerator or a vulcanization aid is usually contained in the rubber composition. Mix.

As the vulcanizing agent, sulfur, sulfur compounds, organic peroxides and the like can be used. The form of sulfur is not particularly limited, and for example, powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur and the like can be used.

Specific examples of the sulfur compound include sulfur chloride, sulfur dichloride, polymer polysulfide, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, selenium dimethyldithiocarbamate and the like.

Further, as the organic peroxide, specifically,
Dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide, di-t-amyl peroxide, 2,5-dimethyl -2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butyl Alkyl peroxides such as peroxy) -hexane, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, t-butyl hydroperoxide, t-
Butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxyvivalate, t-butyl peroxymaleic acid, t-butyl peroxy neodecanoate, t-butyl peroxybenzoate, di-t Peroxyesters such as -butyl peroxyphthalate,
Ketone peroxides such as dicyclohexanone peroxide are exemplified. These may be used in combination of two or more.

Among them, the one-minute half-life temperature was 13
Organic peroxides at 0 ° C. to 200 ° C. are preferred, specifically, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butyl Cumyl peroxide, di-t-amyl peroxide, t-butyl hydroperoxide and the like are preferred.

When the vulcanizing agent is sulfur or a sulfur-based compound, 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the ethylene / α-olefin / polyene copolymer (A) is used. When it is an organic peroxide in an amount of parts by weight, it is 0.0003 to 0.05 mol, preferably 0.001 to 0.03 mol, per 100 g of the ethylene / α-olefin / polyene copolymer (A). Is desirably used in an appropriate amount.

Vulcanization Accelerator When sulfur or a sulfur compound is used as the 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-2-benzothiazolesulfenamide, N, N-diisopropyl-2-benzothiazolesulfuramide. Sulfenamide compounds such as phenamide, 2-mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole, dibenzothiazyl Thiazole compounds such as disulfide, 2- (4'-morpholinodithio) benzothiazole, diphenylguanidine, triphenylguanidine, diorsonitrile guanidine,
Guanidine compounds such as orthonitrile biguanide, diphenylguanidine phthalate, acetaldehyde-aniline reactant, butyraldehyde-aniline condensate, aldehyde amine or aldehyde-ammonia compounds such as hexamethylenetetramine, acetaldehyde ammonia, 2-mercaptoimidazoline (ethylenethione Urea) and other thiourea compounds such as imidazoline compounds such as thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea and diorthotolylthiourea, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide and tetrabutyl Thiuram-based compounds such as thiuram disulfide, pentamethylenethiuram tetrasulfide, Zinc methyl dithiocarbamate,
Dithioxanthate compounds such as zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, tellurium dimethyldithiocarbamate, dibutylxanthogen Xanthate compounds such as zinc acid, zinc white and the like can be mentioned.

[0141] The vulcanization accelerator as described above is ethylene • α.
-It is desirable to use 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the olefin / polyene copolymer (A).

[0142] When the organic peroxide is used as vulcanizing agent (polyfunctional monomer) The vulcanizing agent, vulcanization agent (polyfunctional monomer) with respect to the organic peroxide 1 mole 0. It is preferable to use 5 to 2 moles, preferably about equimolar amount.

As the vulcanization aid, specifically, sulfur,
quinone dioxime compounds such as p-quinone dioxime,
(Meth) acrylate compounds such as trimethylolpropane triacrylate and polyethylene glycol dimethacrylate; allyl compounds such as diallyl phthalate and triallyl cyanurate; maleimide compounds such as m-phenylenebismaleimide; and divinylbenzene.

In the present invention, among the above vulcanizing agents, it is preferable to use sulfur or a sulfur-based compound, especially sulfur, since the characteristics of the rubber composition according to the present invention can be exhibited.

Foaming Agent When the rubber composition according to the present invention contains a compound constituting a foaming system such as a foaming agent and a foaming aid, it can be foam-molded.

As the foaming agent, foaming agents generally used for foaming rubber can be widely used.
Specifically, inorganic foaming agents such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite, N, N'-dimethyl-N, N'-dinitrosoterephthalamide, N, N'-di Nitroso compounds such as nitrosopentamethylenetetramine, azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, azo compounds such as barium azodicarboxylate, benzenesulfonylhydrazide, toluenesulfonylhydrazide, p, p ' -Oxybis (benzenesulfonylhydrazide), sulfonylhydrazide compounds such as diphenylsulfone-3,3'-disulfonylhydrazide, and azide compounds such as calcium azide, 4,4-diphenyldisulfonylazide, and p-toluenesulfonylazide. Can be

Of these, nitroso compounds, azo compounds and azide compounds are preferred. The blowing agent can be used in an amount of 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the ethylene / α-olefin / polyene copolymer. From the rubber composition containing the foaming agent in such an amount, an apparent specific gravity of 0.03 to 0.8 g /
cm ³ foam can be produced.

A foaming aid can be used together with the foaming agent. When the foaming aid is used in combination, there are effects such as lowering the decomposition temperature of the foaming agent, accelerating the decomposition, and making the air bubbles uniform. Examples of such a foaming aid include organic acids such as salicylic acid, phthalic acid, stearic acid and oxalic acid, urea and derivatives thereof.

The foaming auxiliary is ethylene / α-olefin.
0.01 to 10 based on 100 parts by weight of the polyene copolymer
It can be used in an amount of preferably from 0.1 to 5 parts by weight.

Other Rubbers The rubber composition according to the present invention can be used by blending with other known rubbers as long as the object of the present invention is not impaired.

Examples of such other rubbers include isoprene-based rubbers such as natural rubber (NR) and isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR) And conjugated diene rubbers such as chloroprene rubber (CR).

Further, conventionally known ethylene / α-olefin-based copolymer rubbers can also be used, for example, ethylene / propylene random copolymer (EPR) and ethylene / α-olefin / polyene copolymers other than the above-mentioned ethylene / α-olefin / polyene copolymers. α-olefin / polyene copolymer, for example, EPD
M or the like can be used.

The vulcanizable rubber composition according to the present invention can be prepared from an ethylene / α-olefin / polyene copolymer and other components as described above by a general method for preparing a rubber compound. it can. For example, using an internal mixer such as a Banbury mixer, a kneader or an intermix, ethylene / α-olefin /
After kneading the polyene copolymer and other components at a temperature of 80 to 170 ° C. for 3 to 10 minutes, if necessary, a vulcanizing agent,
It is prepared by adding a vulcanization accelerator or a vulcanization aid, kneading the mixture with a roll such as an open roll or a kneader at a roll temperature of 40 to 80 ° C. for 5 to 30 minutes, and then dispensing. be able to. In this way, a rubber composition (compounded rubber) usually in the form of a ribbon or sheet is obtained. When the kneading temperature in the above internal mixers is low, a vulcanizing agent, a vulcanization accelerator, a foaming agent and the like can be kneaded at the same time.

Vulcanized Rubber The vulcanizate (vulcanized rubber) of the rubber composition according to the present invention is obtained by subjecting the unvulcanized rubber composition as described above to an extrusion molding machine, a calender roll, a press, and an injection molding. Preforming into a desired shape by various molding methods such as a molding machine, a transfer molding machine, and heating at the same time as molding or by introducing a molded product into a vulcanization tank, or vulcanizing by irradiating an electron beam. be able to.

When the above rubber composition is vulcanized by heating, a heating tank of a heating form such as hot air, a fluidized bed of glass beads, UHF (ultra-high frequency electromagnetic wave), steam, and LCM (hot molten salt tank) is used. At a temperature of 150 to 270 ° C.
Heating for 30 minutes is preferred.

When vulcanization is performed by electron beam irradiation without using a vulcanizing agent, the preformed rubber composition is added to the vulcanizate in an amount of 0.1%.
An electron beam having an energy of from 10 to 10 MeV, preferably from 0.3 to 2 MeV, is irradiated with an absorbed dose of 0.5 to 35 Mra.
d, preferably 0.5 to 10 Mrad.

For molding and vulcanization, a mold may be used, or a mold may not be used. When a mold is not used, the rubber composition is usually continuously molded and vulcanized. The vulcanized rubber molded and vulcanized as described above is used for automotive parts such as weather strips, door glass run channels, window frames, radiator hoses, brake parts, wiper blades, rubber rolls, belts, packings, hoses, etc. It can be used for applications such as rubber products, electric insulation materials such as anode caps and grommets, construction gaskets, civil engineering construction materials such as civil engineering sheets, and rubberized fabrics.

A vulcanized foam obtained by heating and foaming a rubber compound containing a foaming agent can be used for applications such as a heat insulating material, a cushion material and a sealing material.

[0159]

The ethylene / α-olefin / non-conjugated polyene random copolymer according to the present invention is excellent in weather resistance and ozone resistance, excellent in processability, and excellent in mechanical properties such as vulcanization strength. ing.

The ethylene / α-olefin of the present invention
According to the method for producing a non-conjugated polyene random copolymer,
It is possible to produce an ethylene / α-olefin / non-conjugated polyene random copolymer excellent in processability that cannot be obtained by such a conventional production method and excellent in mechanical properties such as vulcanization strength. The ethylene of the present invention
The method for producing an α-olefin / non-conjugated polyene random copolymer has excellent polymerization activity at high temperatures,
An α-olefin / non-conjugated polyene random copolymer can be efficiently produced.

The vulcanizable rubber composition according to the present invention containing the specific ethylene / α-olefin / non-conjugated polyene copolymer as described above has improved mechanical strength, weather resistance, ozone resistance and the like. Excellent, and also excellent in workability.

The rubber composition according to the present invention can form a vulcanized rubber molded product or a vulcanized rubber foam having particularly excellent properties.

[0163]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.
In the following examples, the following metallocene compounds were used.

[0164]

Embedded image

[0165]

Example 1 Pre-contact between zirconium compound and methylalumoxane
And preparation of a catalyst solution A predetermined amount of the above zirconium compound A and a toluene solution of methylalumoxane (1.2 mg atom / ml in terms of aluminum atom) are stirred in a dark place at room temperature for 30 minutes. By mixing, a toluene solution in which the zirconium compound A and methylalumoxane were dissolved was prepared. The Zr concentration of this toluene solution is 0.1.
002 mmol / ml, and the methylalumoxane concentration was 1.2 mg atom /
ml.

Next, hexane having a volume 5 times the volume of toluene was added to this toluene solution with stirring to prepare a catalyst solution having the following Zr concentration and methylalumoxane concentration, and the following catalyst solution was prepared. It was used as a polymerization reaction catalyst. Zr concentration: 0.00133 mmol / ml = 0.33 mmol / l Methylalumoxane concentration (converted to Al atom): 0.3
20 mmol / ml = 200 mmol / liter

[0167] using a stainless steel polymerization vessel 15 liter with a Polymerization stirring blade, and continuously ethylene, propylene, 7-methyl -
Copolymerization with 1,6-octadiene was performed. That is, first, 3.17 liters / hour of dehydrated and purified hexane and 0.03 liters / hour of the above mixed solution of zirconium compound A and methylalumoxane were introduced into the polymerization vessel from the top of the polymerization vessel.
Hexane solution of triisobutylaluminum (concentration 17
(Mmol / l), 0.3 l / h, 7-methyl-
1,6-octadiene (abbreviated as MOD) in hexane (concentration: 0.15 liter / liter), 1.5 liter / hour,
Each was fed continuously.

Further, 200 liters / hour of ethylene and 200 liters / hour of propylene were continuously supplied from the upper part of the polymerization vessel into the polymerization vessel. This copolymerization reaction is 6
The reaction was performed 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.

By the above operation, ethylene / propylene / 7-
Methyl-1,6-octadiene random copolymer is 33 per hour
Obtained in an amount of 0 g. The obtained random copolymer had a molar ratio of units derived from ethylene to units derived from propylene (ethylene / propylene) of 70/30, and an iodine value of 22 (g-iodine / 100 g-polymer). ), And the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. was 2.6 dl / g. The glass transition temperature was -61 ° C. The value of gη ^* was 0.63, and the value of g ′ was 0.70. When calculating the g ′ value, GPC was performed using Waters ALC / GPC 150C, and GMH-HT and GMH-HTL were used as columns.
(Manufactured by Tosoh Corporation). Table 1 shows the results.

[0171]

Examples 2 to 7 In the same manner as in Example 1, except that the copolymerization reaction was carried out under the polymerization conditions shown in Table 1 in place of the polymerization conditions of Example 1, ethylene / α was used. −
An olefin / non-conjugated polyene random copolymer (copolymer rubber) was obtained. Table 1 shows the properties of the obtained copolymer rubber.

[0172]

[Table 1]

[0173]

[Table 2]

[0174]

COMPARATIVE EXAMPLE 1 A copolymerization reaction of ethylene, propylene and ethylidene norbornene (ENB) was continuously performed using a 2-liter polymerization vessel equipped with a stirring blade.

That is, EN was introduced into the polymerization vessel from the top of the polymerization vessel.
A hexane solution (concentration: 36 g / liter) of B was added at a rate of 0.1 hour
5 l, 0.5 l / h of a hexane solution of VO (OC ₂ H ₅ ) Cl ₂ as a catalyst (concentration: 8 mmol / l), ethyl aluminum sesquichloride [Al (C
₂ H ₅ ) _1.5 Cl _1.5 ] in a hexane solution (concentration: 64 mmol / L) was supplied at a rate of 0.5 L / h, and hexane was further supplied at a rate of 0.5 L / h. Was continuously withdrawn so that the polymerization liquid of 1 was always 1 liter.

In this polymerization vessel, ethylene was supplied at 130 liters / hour and propylene was supplied at a rate of 1 hour using a bubbling tube.
70 liters and hydrogen were supplied at a rate of 40 liters per hour. The copolymerization reaction was carried out at a temperature of 20 ° C. by circulating a refrigerant through a jacket attached to the outside of the polymerization vessel.

When a copolymerization reaction was carried out under the above conditions,
A polymerization solution containing the ethylene / propylene / ethylidene norbornene copolymer was obtained. Next, the resulting polymerization solution was demineralized with hydrochloric acid, and then a large amount of methanol was added to precipitate a polymer, followed by drying under reduced pressure at 100 ° C. for 24 hours.

An ethylene / propylene / ethylidene norbornene copolymer (rubber) was obtained in an amount of 53 g / h.

The copolymer obtained had a molar ratio of units derived from ethylene to units derived from propylene (ethylene / propylene) of 72/28 and an iodine value of 2
1 (g-iodine / 100 g-polymer) and 135
The intrinsic viscosity [η] measured in decalin solvent is 2.1 dl
/ G. Furthermore, the gη ^* value is 0.98,
The g 'value was 0.99.

As described above, when the vanadium catalyst system was used, gη ^* and g ′ were close to 1, indicating that no long-chain branch was formed. Table 2 shows the results.

[0181]

Example 8 using a stainless steel polymerization vessel 15 liter with a Polymerization stirring blade, and continuously ethylene, propylene, the copolymerization of 5-ethylidene-2-norbornene (hereinafter referred to as ENB) went. That is, first, 3.17 liters of dehydrated and purified hexane was poured into the polymerization vessel from the top of the polymerization vessel at a rate of
0.03 l / h of a mixed solution of zirconium compound A and methylalumoxane prepared in the above, 0.3 l / h of a hexane solution of triisobutylaluminum (concentration 17 mmol / l), and a hexane solution of ENB (concentration 0.015 l) Per liter) was continuously supplied at 1.5 liters per hour.

Further, 200 l / h of propylene and 200 l / h of propylene 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.

In the above operation, ethylene / propylene / E
The NB copolymer was obtained in an amount of 70 g per hour. The resulting copolymer had a molar ratio (ethylene / propylene) of a unit derived from ethylene to a unit derived from propylene of 70/30, and an iodine value of 22 (g-iodine / 10).
0 g-polymer), and the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. was 2.3 dl / g. The gη ^* value was 0.65, and the g ′ value was 0.70.
Table 2 shows the results.

[0185]

Examples 9 to 11 An ethylene / α-olefin / polyene copolymer was produced in the same manner as in Example 8, except that the copolymerization reaction was carried out under different polymerization conditions. Table 2 shows the results.

[0186]

[Table 3]

The evaluation test methods for the ethylene / α-olefin / non-conjugated polyene copolymer composition and the vulcanized rubber in the following Examples and Comparative Examples are as follows. [1] Physical Properties Test of Unvulcanized Rubber The physical properties of the unvulcanized rubber were measured according to JIS K 6300. [2] Tensile test The upper part of the vulcanized tubular sponge was JIS lengthwise.
A test piece was obtained by punching out with a No. 3 type dumbbell described in K6301 (1989). According to the method defined in the JIS K 6301 Paragraph 3 by using the test piece, measuring temperature 25 ° C., a tensile subjected to tensile test at a rate of 500 mm / min conditions, elongation at break and tensile tensile stress at break T _B the E _B was measured. [3] Specific gravity measurement 20 mm × 20 from the top of the vulcanized tubular sponge
mm test piece is punched out, and dirt on the surface is wiped off with alcohol. The test piece was attached to an automatic hydrometer (M-1 type, manufactured by Toyo Seiki Seisaku-sho, Ltd.) in an atmosphere of 25 ° C., and the specific gravity was measured from the difference in mass between the air and pure water. [4] Compression set test The vulcanized tubular sponge is cut into 30 mm and attached to a compression set measuring die. Compress so that the height of the test piece is の of the height before applying the load,
Heat treated in a gear oven at 200C for 200 hours. After cooling for 30 minutes, the height of the test piece was measured, and the compression set was calculated by the following formula.

[0188]

(Equation 1)

[5] Measurement of Shape Retention The ratio of the height to the width of the cross-section of the vulcanized tubular sponge was measured and defined as the shape retention.

[0190]

(Equation 2)

[6] Measurement of Surface Roughness The surface roughness of the sponge rubber was represented by numerically expressing the irregularities on the upper surface of the sponge rubber using a stylus type surface roughness measuring instrument.
Actually, the tube-shaped sponge rubber obtained as described above is cut into a length of 50 mm, and from the sum of the heights (h ₁ ) of the highest to the tenth convex parts among the extracted parts, the tenth to the tenth lowest. The value calculated by dividing the value (h ₁ −h ₂ ) obtained by subtracting the sum of the heights of the concave portions (h ₂ ) from the above by 10 was defined as the surface roughness of the sponge rubber.

[0192]

Example 12 Ethylene propylene produced in Example 8 above was used.
A compounded rubber (rubber composition) was prepared using the α-olefin / non-conjugated polyene copolymer and other components in the amounts shown in Table 3. That is, an ethylene / α-olefin / non-conjugated polyene copolymer, paraffinic oil, carbon black, stearic acid, dimethyl distearyl ammonium chloride, and activated zinc white were mixed with a 1.7-liter Banbury mixer (Kobe Steel, Ltd.) For 10 minutes. Further, a vulcanizing agent and other components were added and kneaded using a 14-inch open roll (F / B = 50/50 ° C.) to obtain a rubber compound.

Next, the rubber compound was subjected to a die temperature of 80 ° C. and a cylinder temperature of 60 ° C. by using a 50 mm extruder equipped with a tubular die (inner diameter: 10 mm, wall thickness: 1 mm).
And extruded into a tube. This molded body was vulcanized in a hot air vulcanization tank at 220 ° C. for 6 minutes to obtain a sponge rubber. Table 4 shows the results.

[0194]

Examples 13 to 15 In Example 12, ethylene
α-olefin / non-conjugated polyene random copolymer
A compounded rubber (rubber composition) was prepared in the same manner as in Example 12 except that the ethylene / α-olefin / non-conjugated polyene random copolymer produced in Examples 9 to 11 was used. Obtained. Table 4 shows the results.

[0195]

Comparative Example 2 The same procedure as in Example 12 was repeated except that the ethylene / α-olefin / non-conjugated polyene random copolymer was used.
A rubber compound (rubber composition) was prepared in the same manner as in Example 12, except that the ethylene / α-olefin / polyene random copolymer produced in the above was used, and then a sponge rubber was obtained. Table 4 shows the results.

[0196]

[Table 4]

[0197]

[Table 5]

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing an example of a preparation process of a metallocene-based catalyst used in a method for producing an ethylene / α-olefin / non-conjugated polyene random copolymer according to the present invention.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toshihiro Aine 1-2-1, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Toshiyuki Tsutsui Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Industry Co., Ltd. (72) Inside of Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Tatsuya Tanizaki 6-1, Waki Town, Waki-machi, Kuga-gun, Yamaguchi Prefecture References JP-A-58-191705 (JP, A) JP-A-6-100579 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 10/00-10/14 C08F 110 / 00-110/14 C08F 210/00-210/18 C08F 4/60-4/70 C08L 1/00-101/16

Claims (7)

(57) [Claims] (1) Ethylene and (b) α-carbon having 3 or more carbon atoms.
A run consisting of only an olefin and (c) a non-conjugated polyene having only one carbon-carbon double bond polymerizable with a metallocene catalyst among carbon-carbon double bonds in one molecule. A dam copolymer, comprising: (i) (a) a unit derived from ethylene, and (b) a unit derived from an α-olefin having 3 or more carbon atoms, wherein 40/60 to 95/5 [(a) / (B)], (ii) an iodine value of 1 to 50, and (iii) intrinsic viscosity [η] measured in decalin at 135 ° C.
Is 0.1 to 8.0 dl / g, and (iv) the intrinsic viscosity [η] measured in the above (iii) is the same as the ethylene content having the same weight average molecular weight (by the light scattering method). Ratio of 70 mol% of linear ethylene / propylene copolymer to intrinsic viscosity [η] _blank gη ^* (= [η] /
[Η] _blank ) is 0.57 to 0.9, wherein the ethylene / α-olefin / non-conjugated polyene random copolymer is used. 2. A method according to claim 2, wherein (a) ethylene and (b) α-
A run consisting of only an olefin and (c) a non-conjugated polyene having only one carbon-carbon double bond polymerizable with a metallocene catalyst among carbon-carbon double bonds in one molecule. A dam copolymer, comprising: (i) (a) a unit derived from ethylene, and (b) a unit derived from an α-olefin having 3 or more carbon atoms, wherein 40/60 to 95/5 [(a) / (B)], (ii) an iodine value of 1 to 50, and (iii) intrinsic viscosity [η] measured in decalin at 135 ° C.
Is 0.1 to 8.0 dl / g, and (iv) the intrinsic viscosity [η] measured in the above (iii) and the gel permeation of the ethylene / α-olefin / non-conjugated polyene random copolymer. Amination chromatography (G
PC: 140 ° C., o-dichlorobenzene solvent), intrinsic viscosity [η] calculated as a straight-chain ethylene / propylene copolymer having an ethylene content of 70 mol%.
'ratio g _{of' blank (= [η] /} [η] blank ') is 0.
Ethylene-alpha-olefin-nonconjugated polyene random copolymer which is a 6 1 to 0.9. 3. An ethylene / α-olefin / non-conjugated polyene random copolymer according to claim 1 or 2, wherein a metallocene-based catalyst containing a metallocene compound represented by the following formula [I] is used. Ethylene-α-
Method for producing olefin / non-conjugated polyene random copolymer; (Wherein, M is a transition metal of Group IVB of the periodic table, R ¹ is a hydrocarbon group having 1 to 6 carbon atoms, and R ² , R ⁴ , R ⁵ , and R ⁶ are the same or different from each other.) May be different, and may be a hydrogen atom, a halogen atom or a carbon atom
R ³ is an aryl group having 6 to 16 carbon atoms, and the aryl group is substituted with a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an organic silyl group. Is also good. X ¹ and X ² may be the same or different from each other and include 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. Y is a divalent hydrocarbon group having 1 to 20 carbon atoms,
20 divalent halogenated hydrocarbon group, 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
-[Where R ⁷ is a hydrogen atom, a halogen atom,
20 hydrocarbon groups and halogenated hydrocarbon groups having 1 to 20 carbon atoms]. ). 4. The ethylene • α- according to claim 1 or 2
A vulcanizable rubber composition comprising an olefin / non-conjugated polyene random copolymer. 5. The ethylene • α- according to claim 1 or 2
The reinforcing agent and / or the inorganic filler is added to 10 parts by weight of the olefin / non-conjugated polyene random copolymer.
The rubber composition according to claim 4, wherein the rubber composition is contained in an amount of from 200 to 200 parts by weight. 6. A softening agent is added to 100 parts by weight of an ethylene / α-olefin / non-conjugated polyene random copolymer.
The rubber composition according to claim 4, which is contained in an amount of 0 to 200 parts by weight. 7. A vulcanized rubber obtained from the vulcanizable rubber composition according to claim 4.