JPH0971617A - Production of ethylene/alpha-olefin/non-conjugated polyene random copolymer, ethylene/alpha-olefin/non-conjugated polyene random copolymer and use of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject copolymer having narrow compositional distribution, excellent flexibility at a low temperature and resistance to heat aging and useful for an automobile part material, etc., at high activity and high conversion ratio of olefin by using a specific metallocene-based catalyst and randomly copolymerizing ethylene with an α-olefin and a non-conjugated polyene. SOLUTION: (A) Ethylene is randomly copolymerized with (B) an α-olefin of >=3C and (C) a non-conjugated polyene in the presence of (D) a metallocene- based catalyst containing a compound of the formula [M is a transition metal of IV B-group in the periodic table; R<11> and R<12> are each H, a halogen, a 1-20C (halogenated) hydrocarbon group, an Si-containing group, an O-containing group, an S-containing group, an N-containing group or a P-containing group; R<13> and R<14> are each a 1-20C alkyl; X<1> and X<2> are each the same as R<11> excepting an N-containing group and a P-containing group; Y is a bifunctional 1-20C (halogenated) hydrocarbon group, a divalent Si-containing group, a divalent Ge-containing group, a divalent Sn-containing group, O, etc.], etc.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an ethylene / α-olefin / non-conjugated polyene random copolymer and an ethylene / α-olefin / non-conjugated polyene random copolymer obtained by the production method. Is ethylene, α-olefin and non-conjugated polyene,
A method for producing an ethylene / α-olefin / non-conjugated polyene random copolymer which is highly active and capable of copolymerizing an α-olefin with a high conversion rate and excellent random copolymerizability, and obtained by the method The present invention relates to an ethylene / α-olefin / non-conjugated polyene random copolymer having a narrow composition distribution, low temperature flexibility, and excellent heat aging resistance.

The present invention also relates to the use of the above ethylene / α-olefin / non-conjugated polyene random copolymer.

[0003]

TECHNICAL BACKGROUND OF THE INVENTION Ethylene / propylene copolymer rubber (E which is a random copolymer of ethylene and propylene)
PM) or a vulcanizable ethylene / α-olefin rubber such as ethylene / propylene / diene copolymer rubber (EPDM) containing a non-conjugated diene such as ethylidene norbornene as a diene component has an unsaturated bond in the polymer main chain. It has a unique molecular structure and is superior in heat resistance and weather resistance compared to general-purpose conjugated diene rubber, so it is widely used for automobile parts, electric wire materials, construction civil engineering materials, industrial material parts, etc. It's being used.

Such ethylene / α-olefin rubbers are usually vulcanized and used, but the properties of the vulcanized rubbers vary depending on the ethylene component content, molecular weight, iodine value, etc. Different values are used.

For example, when EPM or EPDM having a high ethylene content is used, a vulcanizate having excellent heat resistance is obtained, and when EPM or EPDM having a low ethylene content is used, a vulcanizate having excellent low-temperature flexibility is obtained. It is known to be obtained.

By the way, among rubber applications, anti-vibration rubbers for brake parts, engine mounts, etc. are required to have heat resistance and low temperature flexibility. However, with the conventionally known EPM or EPDM, it is possible to obtain a vulcanized product that satisfies both the heat resistance and low-temperature flexibility required for a vibration-proof rubber even when the ethylene component content, molecular weight, iodine value, etc. are changed. Is difficult, and EPM or EPD
M was rarely used in these applications.

Therefore, the above problems are improved,
The advent of ethylene / α-olefin / non-conjugated polyene copolymers and vulcanized products thereof, which are excellent in heat resistance, heat aging resistance and low temperature flexibility, has been desired. However, such an ethylene / α-olefin / non-conjugated polyene copolymer, in particular an ethylene / α-olefin / non-conjugated polyene copolymer having 4 or more carbon atoms, is It has been difficult to manufacture as shown in FIG.

The above ethylene / propylene / non-conjugated diene random copolymer (EPDM) has been conventionally produced using a vanadium catalyst. However, in the presence of a known vanadium catalyst, ethylene, an α-olefin having 4 or more carbon atoms, a non-conjugated polyene such as ethylidene norbornene (hereinafter also referred to as ENB), 7-
Even when trying to copolymerize with methyl-1,6-octadiene (hereinafter also referred to as MOD), the molecular weight does not increase compared to the case of producing EPDM, and the polymerization activity is extremely reduced. 4 or more α-olefins
It was difficult to industrially produce a non-conjugated polyene random copolymer.

When ethylene, α-olefin and the above ENB or MOD are copolymerized with a solid titanium-based catalyst known as a catalyst for producing polyethylene and polypropylene, the composition distribution becomes wide, A copolymer having inferior vulcanization properties was obtained, and it was difficult to carry out the solution polymerization in a uniform solution state because a component having a high ethylene content was precipitated.

Japanese Unexamined Patent Publication (Kokai) No. 2-51512 discloses an unsaturated ethylene / α-olefin random copolymer capable of high-speed vulcanization as compared with a conventional unsaturated ethylene / α-olefin random copolymer. Japanese Patent Application Laid-Open No. HEI-2
JP-A-64111 describes a method of producing a high molecular weight EPDM having a low crystallinity by slurry polymerization using a catalyst composed of a metallocene compound of titanium, zirconium or hafnium and an alumoxane.

However, in all of these publications, ethylene, an α-olefin having 4 or more carbon atoms and a non-conjugated polyene are copolymerized with high activity to have a narrow composition distribution, excellent mechanical strength, low temperature flexibility and heat resistance. Ethylene with excellent aging properties
It has not been shown to obtain α-olefin / non-conjugated polyene random copolymers.

When ethylene, an α-olefin having 3 or more carbon atoms and a non-conjugated polyene are copolymerized using the above-mentioned conventionally known catalyst, α having 3 or more carbon atoms is used as compared with ethylene. -There was a problem that the reaction rate (conversion rate) of olefin was low and it was difficult to obtain an ethylene / α-olefin / non-conjugated polyene random copolymer containing a high content of α-olefin component having 3 or more carbon atoms.

Therefore, ethylene, an α-olefin having 3 or more carbon atoms and a non-conjugated polyene can be copolymerized with high activity, and the α-olefin can be copolymerized with a high reaction rate and with excellent random copolymerizability, Moreover, the advent of a manufacturing method that enables the production of ethylene / α-olefin / non-conjugated polyene random copolymers with a narrow composition distribution, high molecular weight, and excellent low temperature flexibility and heat aging resistance Is desired.

[0014]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and is ethylene and α-containing 3 or more carbon atoms.
It is possible to obtain a high molecular weight copolymer by copolymerizing an olefin and a non-conjugated polyene with high activity, α-olefin with a high reaction rate and excellent random copolymerizability. Method for producing olefin / non-conjugated polyene random copolymer, and ethylene / α-olefin / non-conjugated polyene random having a narrow composition distribution and excellent mechanical strength, low temperature flexibility and heat aging resistance obtained by the production method The purpose is to provide a copolymer.

Further, the present invention is directed to ethylene.
The purpose of the present invention is to provide applications of α-olefin / non-conjugated polyene random copolymers. In particular, including the copolymer, it has excellent mechanical strength, weather resistance, ozone resistance, and cold resistance (low temperature flexibility). And it aims at providing the vulcanizable rubber composition excellent also in heat resistance.

[0016]

SUMMARY OF THE INVENTION A method for producing an ethylene / α-olefin / non-conjugated polyene random copolymer according to the present invention is carried out in the presence of a metallocene catalyst containing a metallocene compound represented by the following formula [I] or [II]. , (A) ethylene and (b)
The feature is that an α-olefin having 3 or more carbon atoms and (c) a non-conjugated polyene are randomly copolymerized.

The metallocene compound used in the present invention is represented by the following formula [I] or [II].

[0018]

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(In the formula, M is a transition metal of Group IVB of the Periodic Table, R ¹¹ and R ¹² may be the same or different from each other, and are a hydrogen atom, a halogen atom, or a carbon atom having 1 to 20 carbon atoms. A hydrogen group, a halogenated hydrocarbon group having 1 to 20 carbon atoms,
A silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, R ¹³ is an alkyl group having 1 to 20 carbon atoms, R ¹⁴ is an alkyl group having 1 to 20 carbon atoms, X ¹ and X ² may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group. A group or a sulfur-containing group, Y
Is a divalent hydrocarbon group having 1 to 20 carbon atoms, or 1 to 2 carbon atoms
0, a divalent halogenated hydrocarbon group, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group,
O -, - CO -, - S -, - SO -, - SO 2 -, - N
^{R 15 -, - P (R} 15) -, - P (O) (R 15) -, - B
R ¹⁵ - or -AlR ¹⁵ - (R ¹⁵ is 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) is. ),

[0020]

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(In the formula, M is a transition metal of Group IVB of the periodic table, X ³ and X ⁴ may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a carbon number. 1-10 alkoxy group, C6-C10 aryl group, C6-C10 aryloxy group, C2-1
0 alkenyl group, C7-40 arylalkyl group, C7-40 alkylaryl group, C8-
40 arylalkenyl group, OH group or halogen atom, R ²¹ may be the same or different from each other, and is a hydrogen atom, a halogen atom, an optionally halogenated alkyl group having 1 to 10 carbon atoms, or a carbon atom. number 6-10 aryl group or _{-NR 2, -SR, -OSiR 3,} -Si
R ₃ or —PR ₂ group (R is a halogen atom, having 1 to 1 carbon atoms)
An alkyl group of 0 or an aryl group having 6 to 10 carbon atoms), R ^{22 to} R ²⁸ are the same as those of R ²¹ above, or adjacent R ^{22 to} R ²⁸ together with the atom to which they are bonded, Aromatic- or may form an aliphatic ring,

[0022]

[Chemical 6]

= BR ²⁹ , = AlR ²⁹ , -Ge-, -Sn
-, - O -, - S -, = SO, = SO 2, = NR 29, =
CO, = PR ²⁹ or = P (O) R ²⁹ (where R
²⁹ and R ³⁰ may be the same or different from each other,
Hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, fluoroalkyl group having 1 to 10 carbon atoms, 6 to carbon atoms
An aryl group having 10 to 10 carbon atoms, a fluoroaryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms,
Arylalkenyl group having 8 to 40 carbon atoms or 7 carbon atoms
To 40 alkylaryl groups or R ²⁹ and R ³⁰
And each may form a ring together with the atom to which they are attached, and M ² is silicon, germanium or tin. ).

The ethylene / α-olefin / non-conjugated polyene random copolymer produced by the present invention comprises (i) a unit derived from ethylene (a) and (b) a unit derived from α-olefin having 3 or more carbon atoms. 40/60
To 95/5 [(a) / (b)] in a molar ratio of (ii) iodine value of 1 to 50, and (iii) intrinsic viscosity [η] measured in 135 ° C. decalin.
Is 0.1 to 8.0 dl / g, and (iv) T relative to Tαα in the ¹³ C-NMR spectrum.
The intensity ratio D (Tαβ / Tαα) of αβ is 0.5 or less, and (v) the B value obtained from the ¹³ C-NMR spectrum and the following formula is 1.00 to 1.50; B value = [ P _OE ] / (2 · [P _E ] · [P _O ]) (wherein [P _E ] is the content mole fraction of units derived from (a) ethylene in the random copolymer, [P _O ]
Is the content mole fraction of the units derived from (b) α-olefin in the random copolymer, and [P _OE ] is α relative to the total number of dyad chains in the random copolymer.
-The ratio of the number of olefin / ethylene chains), (vi) the glass transition temperature Tg determined by DSC is -50 ° C.
And (vii) the intrinsic viscosity [η] measured in (iii) above and a linear ethylene / propylene copolymer having the same weight average molecular weight (by light scattering method) as the ethylene content of 70 mol%. It is desirable that the gη ^* value (= [η] / [η] _blank ) defined by the ratio of the intrinsic viscosity [η] _blank of the polymer is more than 0.9.

In the present invention, the above-mentioned (b) α-olefin is preferably an α-olefin having 4 to 10 carbon atoms.

The vulcanizable rubber composition according to the present invention is characterized by containing the above-mentioned ethylene / α-olefin / non-conjugated polyene random copolymer. This vulcanizable rubber composition may contain other components, and specifically, a reinforcing agent and / or a reinforcing agent and / or 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene random copolymer. Inorganic fillers can be included in amounts of 10 to 200 parts by weight and softeners in amounts of 10 to 200 parts by weight. The vulcanized rubber according to the present invention is obtained from the rubber composition as described above.

[0027]

DETAILED DESCRIPTION OF THE INVENTION In the method for producing an ethylene / α-olefin / non-conjugated polyene random copolymer according to the present invention, (a) ethylene and (a) ethylene are added in the presence of a specific metallocene catalyst as described below. b) An α-olefin having 3 or more carbon atoms and (c) a non-conjugated polyene are randomly copolymerized to produce an ethylene / α-olefin / non-conjugated polyene random copolymer having the following characteristics. be able to.

First, the ethylene / α produced by the present invention
-The olefin / non-conjugated polyene random copolymer will be described. Ethylene / α-olefin / non-conjugated polyene Random
Polymer An ethylene / α-olefin / non-conjugated polyene random copolymer (hereinafter also referred to as a random copolymer) produced by the present invention comprises (a) ethylene and (b) an α-olefin having 3 or more carbon atoms. , A specific (c) non-conjugated polyene.

(B) C3 or more, specifically C3
Examples of the α-olefin of -20 include propylene, 1-butene, 1-pentene, 1-hexene, 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 4 to 10 carbon atoms are preferable, and 1-butene, 1-hexene, 1-octene and the like are particularly preferable. Further, (c) the non-conjugated polyene, specifically, for example, 1,4-hexadiene,
1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,13-tetradecadiene, 1,5,9- Decatriene, 3-
Methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 3-methyl-1,5-hexadiene, 3, 3-dimethyl-1,
4-hexadiene, 3,4-dimethyl-1,5-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, 3- Methyl-1,6-heptadiene, 4-methyl-1,6-heptadiene, 4,4-dimethyl-1,6-heptadiene, 4-ethyl-1,6-heptadiene, 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-E Ru-1,7-decadiene, 8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 6- Aliphatic polyenes such as methyl-1,6-undecadiene and 9-methyl-1,8-undecadiene, vinylcyclohexene, vinylnorbornene, 5-ethylidene-2-norbornene, dicyclopentadiene, cyclooctadiene, 2,5-
Norbornadiene, 1,4-divinylcyclohexane, 1,3-
Divinylcyclohexane, 1,3-divinylcyclopentane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, 1,5-diallyl Cyclooctane, 1-allyl-4-isopropenylcyclohexane, 1-
Examples thereof include alicyclic polyenes such as isopropenyl-4-vinylcyclohexane and 1-isopropenyl-3-vinylcyclopentane, and aromatic polyenes such as divinylbenzene and vinylisopropenylbenzene.

These non-conjugated polyenes can be used in combination of two or more kinds. In the present invention, among these, non-conjugated polyenes having 7 or more carbon atoms are preferable,
For example, 7-methyl-1,6-octadiene (MOD), 5-ethylidene-2-norbornene (ENB), dicyclopentadiene (DCPD) 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 and (b) a unit derived from an α-olefin having 3 or more carbon atoms (hereinafter sometimes simply referred to as (b) α-olefin), 40/60 to 95/5, preferably 55/45
It is contained in a molar ratio of 90/10 [(a) / (b)].

When this random copolymer is used by blending it with a conjugated diene rubber, the above (a) /
(b) The molar ratio is preferably 65/35 to 80/20, and the random copolymer and the conjugated diene rubber having such a component ratio are excellent in mechanical strength and have a rubber composition even at a low temperature. A rubber composition capable of exhibiting properties can be obtained.

(Ii) Iodine Value The iodine value, which is an index of the amount of the non-conjugated polyene component in the ethylene / α-olefin / non-conjugated polyene random copolymer, is 1 to 50, preferably 5 to 40.

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

When this random copolymer is used by blending it with a conjugated diene rubber, the intrinsic viscosity [η]
Is particularly preferably 0.3 dl / g <[η] <5 dl / g. A random copolymer having such an intrinsic viscosity [η] is excellent in blendability (compatibility) with a conjugated diene rubber, and the random copolymer and the conjugated diene rubber have excellent mechanical strength characteristics. A vulcanizable rubber composition having excellent heat resistance and weather resistance can be obtained.

(Iv) Tαβ / Tαα The ethylene / α-olefin / non-conjugated polyene random copolymer has an intensity (area) ratio D (Tαβ / Tαα) of Tαβ to Tαα in the ¹³ C-NMR spectrum of 0.5 or less. Is. The strength ratio D value of this random copolymer varies depending on the type of the (b) α-olefin constituting the random copolymer, but is preferably 0.1 or less, more preferably 0.05 or less.

Here, T in the ¹³ C-NMR spectrum
αβ and Tαα are peak intensities of CH _{2 in} a unit derived from (b) an α-olefin having 3 or more carbon atoms, respectively. As shown below, two types of CH ₂ having different positions with respect to the tertiary carbon are I mean.

[0039]

[Chemical 7]

The strength ratio D of the random copolymer can be determined as follows. ¹³ C of random copolymer
-The NMR spectrum is, for example, JE manufactured by JEOL Ltd.
Hexachlorobutadiene / d ₆ -benzene = 2 with a sample concentration of 5% by weight using an OL-GX270 NMR measurement apparatus.
/ 1 (volume ratio) mixed solution, 67.8MHz, 25 ℃
At d ₆ -benzene (128 ppm).

Analysis of ¹³ C-NMR spectrum is basically carried out by Lindemann Adams (Analysis Chemistry 43,
p1245 (1971)), JCRandall (Review Macromolecular
Chemistry Physics, C29, 201 (1989)).

The above strength ratio D will be described more concretely by taking an ethylene / 1-butene / 7-methyl-1,6-octadiene random copolymer as an example. In the ¹³ C-NMR spectrum of this ethylene / 1-butene / 7-methyl-1,6-octadiene random copolymer, the peak appearing at 39-40 ppm was assigned to Tαα, and the peak appearing at 31-32 ppm was assigned to Tαβ. To be done.

The intensity ratio D is calculated by the integrated value (area) ratio of each peak portion. The intensity ratio D thus obtained is generally a ratio of 1,2-addition reaction of 1-butene followed by 2,1 addition reaction, or 1-butene 2,1
It is considered to be a scale showing the ratio of 1,2 addition reaction following the addition reaction. Therefore, the larger the strength ratio D value, the more irregular the bonding direction of the (b) α-olefin (1-butene). Conversely, the smaller the D value,
(b) This shows that the bonding direction of the α-olefin is regular. If the regularity is high, the molecular chains are likely to aggregate, and the random copolymer tends to have excellent strength and the like, which is preferable.

In the present invention, as described later,
By copolymerizing ethylene, an α-olefin having 3 or more carbon atoms and a non-conjugated polyene using a catalyst containing a Group IVB metallocene compound, a random copolymer having the strength ratio D of 0.5 or less is obtained. However, even if ethylene, 1-butene, and 7-methyl-1,6-octadiene are copolymerized in the presence of a Group VB metallocene catalyst such as vanadium, the strength ratio D is 0.5 or less. Ethylene 1-
Butene-7-methyl-1,6-octadiene random copolymer cannot be obtained. This means that α other than 1-butene
-The same applies to olefins.

(V) B value The ethylene / α-olefin / non-conjugated polyene random copolymer has a B value of 1.00 to 1.50, preferably 1.02, determined from the ¹³ C-NMR spectrum and the following formula.
˜1.50, more preferably 1.02 to 1.45, and most preferably 1.02 to 1.40.

B value = [P _OE ] / (2 · [P _E ] · [P _O ]) (In the formula, [P _E ] is a unit derived from (a) ethylene in the random copolymer. Is the mole fraction contained, [P _O ]
Is the content mole fraction of the units derived from (b) α-olefin in the random copolymer, and [P _OE ] is α relative to the total number of dyad chains in the random copolymer.
-The ratio of the number of olefin / ethylene chains), this B
The values are (a) ethylene and (b) in the random copolymer.
JC is an index showing the distribution state with α-olefin.
Randall (Macromolecules, 15, 353 (1982)), J.Ray (M
acromolecules, 10,773 (1977)) and others.

The larger the above B value, the shorter the block-like chain of (a) ethylene or (b) α-olefin, the more uniform the distribution of ethylene and α-olefin, and the compositional distribution of the random copolymer. Indicates that is narrow. The composition value of the random copolymer becomes wider as the B value becomes smaller than 1.00, and such a random copolymer has a smaller composition distribution than the random copolymer having a narrow composition distribution.
For example, when vulcanized, physical properties such as strength may not be sufficiently exhibited.

In the present invention, as described later,
A random copolymer having a B value of 1.00 to 1.50 is obtained by copolymerizing ethylene, an α-olefin having 3 or more carbon atoms, and a non-conjugated polyene using a Group IVB metallocene compound. However, even if ethylene is copolymerized with an α-olefin having a carbon number of 3 or more and a non-conjugated polyene in the presence of a titanium-based nonmetallocene catalyst, for example, an ethylene / α-olefin / non-polymer having a B value in the above range is obtained. It is not possible to obtain a conjugated polyene random copolymer.

(Vi) Glass transition temperature Tg The glass transition temperature Tg of the ethylene / α-olefin / non-conjugated polyene random copolymer measured by DSC (differential scanning calorimeter) is -50 ° C or lower.

A vulcanizable rubber composition excellent in low-temperature flexibility can be obtained from a random copolymer having a glass transition temperature Tg of -50 ° C or lower. The random copolymer of the present invention, for example, a random copolymer of ethylene, 1-butene and ethylidene norbornene (ENB) is the same as the random copolymer having the same composition ratio of ethylene, α-olefin and polyene. Compared with the random copolymer EPDM of propylene and ENB, the glass transition temperature Tg is lower by about 5 to 10 ° C., and it is characterized by excellent low temperature characteristics.

(Vii) gη ^* value The 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 ). Above [η]
_Blank is obtained by replacing the weight average molecular weight M _w obtained by the light scattering method with the viscosity average molecular weight M _v of this ethylene / propylene non-conjugated polyene copolymer and calculating it from the formula (I). [Η] _blank = 7.2 × 10 ^-4 M _v ^0.667 (I)

The gη ^* value of the ethylene / α-olefin / non-conjugated polyene random copolymer is preferably more than 0.9. The ethylene / α-olefin / non-conjugated polyene random copolymer as described above may be modified with a polar monomer. Details of the modified product will be described later.

Production Method In the present invention, (a) ethylene and (b) an α-olefin having 3 or more carbon atoms as described above and the above ( c) An ethylene / α-olefin / non-conjugated polyene random copolymer as described above is obtained by random copolymerization with a non-conjugated polyene.

The metallocene catalyst used in the present invention is
It contains a specific [A] metallocene compound as described below. The metallocene-based catalyst used in the present invention is not particularly limited except that it contains the [A] metallocene compound. For example, the metallocene compound [A] reacts with the organoaluminum oxy compound [B] and / or [A]. And a compound [C] that forms an ion pair with each other, and further [A], [B] and / or [C]
It may be formed together with the organoaluminum compound [D].

Each of these components will be described below. FIG. 1 shows an example of a process for preparing the 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] or [II] is used as the metallocene compound [A].

[0057]

Embedded image

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

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

Examples of the silicon-containing group include monohydrocarbon-substituted silyl such as methylsilyl and phenylsilyl, dihydrocarbon-substituted silyl such as dimethylsilyl and diphenylsilyl,
Trihydrocarbyl-substituted silyl such as trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, trinaphthylsilyl, and hydrocarbyl-substituted silyl such as trimethylsilyl ether. Examples thereof include silicon-substituted alkyl groups such as ether and trimethylsilylmethyl, and silicon-substituted aryl groups such as trimethylphenyl.

Further, as the silicon-containing group, other than the above
SiR ₃ (where R is a halogen atom and has 1 to 1 carbon atoms)
And a group represented by an alkyl group having 10 or an aryl group having 6 to 10 carbon atoms).

Examples of the oxygen-containing group include a hydroxy group, an alkoxy group such as methoxy, ethoxy, propoxy and butoxy, an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy, and an arylalkoxy group such as phenylmethoxy and phenylethoxy. Can be mentioned.

Further, as the oxygen-containing group, -OSiR
₃ (wherein R is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms).

As the sulfur-containing group, a substituent in which oxygen of the oxygen-containing compound is replaced with sulfur, and methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, Trimethylbenzene sulfonate,
Sulfonate groups such as triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluorobenzenesulfonate, methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate, trimethylbenzene Sulfinate groups such as sulfinate and pentafluorobenzene sulfinate.

Further, as the sulfur-containing group, other than the above
SR (provided that R is a halogen atom and has 1 to 10 carbon atoms)
Alkyl group or aryl group having 6 to 10 carbon atoms)
And a group represented by.

Examples of the nitrogen-containing group include amino groups, alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and dicyclohexylamino, phenylamino, diphenylamino, ditolylamino, dinaphthylamino and methylphenylamino. And an arylamino group such as an alkylarylamino group and the like. Further, as the nitrogen-containing group, -NR ₂ (wherein R is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a carbon number having 1 to 10 carbon atoms) is used. 6-10
And the group represented by the aryl group).

Examples of the phosphorus-containing group include dimethylphosphino and diphenylphosphino. Further, as the phosphorus-containing group, -PR ₂ (provided that R
Is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms).

Of these, R ¹¹ is preferably a hydrocarbon group, and particularly preferably a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl or propyl. Also R
¹² is preferably a hydrogen atom or a hydrocarbon group, and particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl or propyl.

R ¹³ and R ¹⁴ R ¹³ and R ¹⁴ have 1 to 2 carbon atoms as exemplified above.
The alkyl groups are 0, and may be the same or different from each other. R ¹³ is preferably a secondary or tertiary alkyl group. R ¹⁴ may contain a double bond or a triple bond.

X ¹ and X ² X ¹ and X ² may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon having 1 to 20 carbon atoms. A group, a silicon-containing group, an oxygen-containing group or a sulfur-containing group, and these are specifically the same as the groups represented by R ¹¹ above. Of these, a halogen atom and a hydrocarbon group having 1 to 20 carbon atoms are preferable.

Y Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, 1 to 1 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 15 -, - P (R} 15) -, - P (O) (R 15) -, - B
R ¹⁵ - or -AlR ¹⁵ - (wherein R ¹⁵ is a hydrogen atom,
A halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with halogen, or an alkoxy group),
Specifically, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-
Divalent hydrocarbon group having 1 to 20 carbon atoms such as alkylene group such as tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene, arylalkylene group such as diphenylmethylene and diphenyl-1,2-ethylene , 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 (n-
Alkylsilylene groups such as propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene, alkylarylsilylene groups , Arylsilylene group, tetramethyl-1,2-disilyl, tetraphenyl-1,2-
Examples thereof include divalent silicon-containing groups such as alkyldisilyl such as disilyl, alkylaryldisilyl, and aryldisilyl groups, and divalent groups obtained by substituting germanium or tin for silicon in the above divalent silicon-containing groups.

Further, as the divalent silicon-containing group, the divalent germanium-containing group and the divalent tin-containing group, the following formula [I
Among the groups represented by Z in I], a group containing any one of silicon, germanium and tin can be mentioned.

Of these, substituted silylene groups such as dimethylsilylene group, diphenylsilylene group and methylphenylsilylene group are particularly preferable. R ¹⁵ is the same halogen atom as described above, a hydrocarbon group having 1 to 20 carbon atoms, or 1 carbon atom.
To 20 halogenated hydrocarbon groups.

Of these, divalent silicon-containing groups, 2
A divalent germanium-containing group is preferable, a divalent silicon-containing group is preferable, and an alkylsilylene, an alkylarylsilylene, and an arylsilylene are more preferable.

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

Specific examples of the metallocene compound represented by the above general formula [I] are shown below. rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1-
(2,7-dimethyl-4-n-propylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7
-Dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis { 1- (2,7-dimethyl-4-
sec-Butylindenyl)} zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-pentylindene) Nil)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-hexylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-cyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-methylcyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-phenylethylindenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2,7-dimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2,7-dimethyl-4-chloromethylindene) Nil)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-trimethylsilylmethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4) -Trimethylsiloxymethylindenyl)} zirconium dichloride, ra
c-Diethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (i-propyl) silylene-bis {1- (2,7-dimethyl-4) -i-
Propylindenyl) zirconium dichloride, rac-
Di (n-butyl) silylene-bis {1- (2,7-dimethyl-4-i-
Propylindenyl) zirconium dichloride, rac-
Di (cyclohexyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,7-dimethyl-4-i- Propylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,7 -Dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,7-dimethyl-
4-i-propylindenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride, rac-di (p-tolyl) silylene-bis {1- (2,7-dimethyl-4-i -Propylindenyl)} zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1 -(2-Methyl-4-i-propyl-7-ethylindenyl)} zirconium dibromide rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-
Ethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2, 3,7-Trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-butylindenyl)} zirconium dichloride, rac- Dimethylsilylene-bis {1- (2,3,7-trimethyl-4-sec-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-t- Butylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-n-pentylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-n-hexylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-cyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-methylcyclohexylindenyl)} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-trimethylsilylmethylindenyl)} zirconium dichloride,
rac-Dimethylsilylene-bis {1- (2,3,7-trimethyl-4-
Trimethylsiloxymethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-
Trimethyl-4-phenylethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,
3,7-Trimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-chloromethylindenyl)} zirconium dichloride, rac-diethylsilylene
-Bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (i-propyl)
Silylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (n-butyl) silylene-bis {1- (2,3,7-trimethyl- 4-i-Propylindenyl)} zirconium dichloride, rac-di (cyclohexyl) silylene-bis {1- (2,3,7-trimethyl-
4-i-propylindenyl)} zirconium dichloride,
rac-Methylphenylsilylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,3,7-
Trimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7-
Trimethyl-4-t-butylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7-
Trimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7
-Trimethyl-4-ethylindenyl)} zirconium dichloride, rac-di (p-tolyl) silylene-bis {1- (2,3,7
-Trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethyl silylene
-Bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium dimethyl, rac-dimethylsilylene
-Bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium methyl chloride, rac-dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-methyl Indenyl)} zirconium-bis (methanesulfonato), rac-dimethylsilylene-bis {1- (2-methyl-4-i-
Propyl-7-methylindenyl) zirconium-bis (p-phenylsulfinato), rac-dimethylsilylene-
Bis {1- (2-methyl-3-methyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4-i-propyl-7) -Methylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-phenyl-4-i-propyl-7-
Methylindenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-methyl-4-i-propyl-
7-Methylindenyl)} titanium dichloride, rac-
Dimethylsilylene-bis {1- (2-methyl-4-i-propyl-
7-methylindenyl)} hafnium dichloride, etc.

Further, a compound in which zirconium in the above compound is replaced by titanium or hafnium can also be mentioned. Of these, i-propyl and se are in 4th position
Those having a branched alkyl group such as a c-butyl or tert-butyl group are particularly preferable.

In the present invention, the racemic form of the metallocene compound is usually used as the catalyst component for olefin polymerization, but R type or S type can also be used. The metallocene compound as described above can be synthesized from the indene derivative by a known method, for example, the method described in JP-A-4-268307.

In the present invention, EP-549900 and Canada-208401 are used as the metallocene compound [A].
A compound represented by the following formula [II] described in No. 7 can also be used.

[0080]

Embedded image

In the formula, M is a transition metal atom of Group IVB of the periodic table, specifically titanium, zirconium or hafnium, particularly preferably zirconium.
X ³ and X ⁴ may be the same as or different from each other, and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a carbon number 1
An alkoxy group having 10 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms,
An aryloxy group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms,
Alkylaryl group having 7 to 40 carbon atoms, 8 to 40 carbon atoms
Is an arylalkenyl group, an OH group or a halogen atom, R ²¹ may be the same or different from each other, and is a hydrogen atom, a halogen atom, an optionally halogenated alkyl group having 1 to 10 carbon atoms, or a carbon number. aryl group, or -NR ₂ of 6 to 10, -SR, -OSiR _3, -SiR ₃ or -PR ₂ radical (R is a halogen atom, an alkyl group or an aryl group having 6 to 10 carbon atoms having 1 to 10 carbon atoms) And R ^{22 to} R ²⁸ are the same as R ²¹ described above, or adjacent R ^{22 to} R ²⁸ may form an aromatic ring or an aliphatic ring together with the atom to which they are bonded. ,

[0082]

Embedded image

= BR ²⁹ , = AlR ²⁹ , -Ge-, -Sn
-, - O -, - S -, = SO, = SO 2, = NR 29, =
CO, = PR ²⁹ or = P (O) R ²⁹ (where R
²⁹ and R ³⁰ may be the same or different from each other,
Hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, fluoroalkyl group having 1 to 10 carbon atoms, 6 to carbon atoms
An aryl group having 10 to 10 carbon atoms, a fluoroaryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms,
Arylalkenyl group having 8 to 40 carbon atoms or 7 carbon atoms
To 40 alkylaryl groups or R ²⁹ and R ³⁰
And each may form a ring together with the atom to which they are attached, and M ² is silicon, germanium or tin. ) Alkyl groups are straight-chain or branched alkyl groups and halogens (halogenated) are fluorine, chlorine, bromine or iodine atoms, in particular fluorine or chlorine atoms.

Substituents R ^{22 to} R of the two indenyl ligands
²⁸ may be the same or different (see the definition of R ²¹ ). X ³ and X ⁴ may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and preferably an alkoxy group having 1 to 3 carbon atoms. An aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms, 7 to 40 carbon atoms, preferably 7 to 10 carbon arylalkyl groups, 7 to 7 carbon atoms
40 preferably an alkylaryl group having 7 to 12 carbon atoms,
It is an arylalkenyl group having 8 to 40 carbon atoms, preferably 8 to 12 carbon atoms, an OH group or a halogen atom, preferably a chlorine atom.

The residues R ^{21 to} R ²⁸ may be the same or different from each other, and are a hydrogen atom, a halogen atom, preferably a fluorine atom, a chlorine atom or a bromine atom, and an optionally halogenated C 1-10 group. Alkyl group preferably having 1 carbon atom
To 4 alkyl group, an aryl group, or -NR ₂ aryl group is preferably 6 to 8 6 to 10 carbon atoms, -SR, -O
SiR ₃ , -SiR ₃ or -PR ₂ groups, where R
Is a halogen atom, preferably a chlorine atom, or a carbon number of 1 to
An alkyl group having 10 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, or an aryl group having 6 to 10 carbon atoms, preferably 6 to
8 is an aryl group.

[0086]

Embedded image

= BR ²⁹ , = AlR ²⁹ , -Ge-, -Sn
-, - O -, - S -, = SO, = SO 2, = NR 29, =
CO, = PR ²⁹ or = P (O) R ²⁹ , in which R ²⁹ and R ³⁰ may be the same or different from each other, and are a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms. Group preferably an alkyl group having 1 to 4 carbon atoms, particularly a methyl group, a fluoroalkyl group having 1 to 10 carbon atoms, preferably a CF ₃ group, an aryl group having 6 to 10 carbon atoms, preferably an aryl group having 6 to 8 carbon atoms, Fluoroaryl group having 6 to 10 carbon atoms, preferably pentafluorophenyl group, 1 carbon atom
Alkoxy group having 10 to 10 carbon atoms, preferably alkoxy group having 1 to 4 carbon atoms, particularly methoxy group, alkenyl group having 2 to 10 carbon atoms, preferably alkenyl group having 2 to 4 carbon atoms, 7 to 7 carbon atoms.
C 40 arylalkyl group, preferably C 7-10 arylalkyl group, C 8-40 arylalkenyl group, preferably C 8-12 arylalkenyl group, or C 7-40 alkylaryl group, preferably carbon It may be an alkylaryl group of the formulas 7 to 12, or R ²⁹ and R ³⁰ may form a ring together with the atom to which they are bonded.

M ² is silicon, germanium or tin, especially silicon or germanium. In the compound of formula [II], M is zirconium or hafnium, and X
³ and X ⁴ may be the same or different from each other,
An alkyl group having 1 to 3 carbon atoms or a halogen atom,
Residues R ²¹ are the same as each other and are an alkyl group having 1 to 4 carbon atoms, R ^{22 to} R ²⁸ may be the same or different from each other, and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. , And Z is

[0089]

[Chemical 12]

A compound which is (M ² is silicon, R ²⁹ and R ³⁰ may be the same or different from each other and is an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms) is particularly preferable. Is.

Further, compounds in which the substituents R ²² and R ²⁸ are hydrogen atoms and R ^{23 to} R ²⁷ are alkyl groups having 1 to 4 carbon atoms or hydrogen atoms are preferable. In particular, M is zirconium, X ³ and X ⁴ are both chlorine atoms, the residues R ²¹ are the same as each other and are alkyl groups having 1 to 4 carbon atoms, and R ²² and R ²⁸ are hydrogen atoms. And R ^{23 to} R ^{27, which} may be the same or different, are an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and Z is

[0092]

Embedded image

(M ² is silicon, R ²⁹ and R ³⁰ may be the same or different from each other and is an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms) are particularly preferable. Is.

Among the compounds represented by the formula [II], particularly preferable compounds are those in which M is zirconium, X ³ and X
⁴ is a chlorine atom, the residue R ²¹ is a methyl group, R ²²
~ R ²⁸ is a hydrogen atom, and Z is

[0095]

Embedded image

(M ² is silicon, R ²⁹ and R ³⁰ may be the same or different and each is a methyl group or a phenyl group). Some preferred examples of the compound represented by the formula [II] are shown below.

Rac-Dimethylsilylene-bis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4,5-acenaphthocyclo) Pentadienyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,6-trimethyl-4,5-benzoindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2- Methyl-
4,5-Benzoindenyl)} zirconium dichloride, ra
c-Methylphenylsilylene-bis {1- (2-methyl-4,5-acenaphthocyclopentadienyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (4,5-benzoindenyl)} Zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,6-dimethyl-4,5-benzoindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,3,6-trimethyl -4,5-benzoindenyl)} zirconium dichloride and the like.

In the present invention, the above metallocene compounds may be used in combination of two or more kinds. [B] Organoaluminum Oxy Compound The organoaluminum oxy compound [B] used in the present invention may be a conventionally known aluminoxane, or is insoluble in benzene as exemplified in JP-A-2-78687. The organoaluminum oxy compound of

The conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method of recovering a hydrocarbon solution by adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension and reacting the same. (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 organic metal component. The solvent or unreacted organoaluminum compound may be removed from the recovered aluminoxane solution by distillation, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used in the production of aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec. -Butyl aluminum, tri tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, trialkyl aluminum such as tridecyl aluminum, tricycloalkyl aluminum, tricycloalkyl aluminum such as tricyclooctyl aluminum, dimethyl aluminum chloride, Diethyl aluminum chloride, diethyl aluminum bromide, diisobutyl aluminum 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, trialkylaluminum and tricycloalkylaluminum are particularly preferable.
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 ) _{Isoprenylaluminum represented by z} (in the formula, x, y, and z are positive numbers and z ≧ 2x) can also be used.

The above organoaluminum compounds may be used in combination of two or more kinds.

Examples of the solvent used in the production of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, pentane,
Hexane, heptane, octane, decane, dodecane, hexadecane, octadecane and other aliphatic hydrocarbons, cyclopentane, cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclopentane, petroleum fractions such as gasoline, kerosene, and light oil, And the above aromatic hydrocarbons,
Examples thereof include halogenated hydrocarbons such as aliphatic hydrocarbons and alicyclic hydrocarbons, particularly hydrocarbon solvents such as chlorinated compounds and brominated compounds.

Further, ethers such as ethyl ether and tetrahydrofuran can be used. Of these solvents, aromatic hydrocarbons are particularly preferred. You may use the said organoaluminum oxy compound [B] in combination of 2 or more types.

[C] reacting with metallocene compound [A]
Compounds Forming Ion Pairs As the compound [C] which reacts with the metallocene compound [A] used in the present invention to form an ion pair, there are listed in Table 1-
501950 gazette, special table 1-502036 gazette,
JP-A-3-179005, JP-A-3-179900
No. 6, JP-A-3-207703, JP-A-3-207703
The Lewis acid, the ionic compound, the borane compound, and the carborane compound described in 207704, US-547718, etc. can be mentioned.

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

BR ³¹ R ³² R ³³ (wherein R ³¹ , R ³² and R ³³ are each independently
A phenyl group which may have a substituent such as a fluorine atom, a methyl group and a trifluoromethyl group, or a fluorine atom is shown. ) Specific examples of the compound represented by the above general formula include trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl). ) Boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like.
Of these, tris (pentafluorophenyl) boron is particularly preferable.

The ionic compound used in the present invention is a salt composed of a cationic compound and an anionic compound. The anion functions to cationize the metallocene compound [A] by reacting with the metallocene compound [A] and to stabilize the transition metal cation species by forming an ion pair. Examples of such anions include an organic boron compound anion, an organic arsenic compound anion, and an organic aluminum compound anion, and those which are relatively bulky and stabilize the transition metal cation species are preferable.
As the cation, a metal cation, an organometallic cation,
Examples thereof include carbonium cation, tripium cation, oxonium cation, sulfonium cation, phosphonium cation, and ammonium cation. More specifically, it includes a triphenylcarbenium cation, a tributylammonium cation, an N, N-dimethylammonium cation, and a ferrocenium cation.

Of these, ionic compounds containing a boron compound as an anion are preferable, and specifically,
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,
Examples thereof include tri (n-butyl) ammonium tetra (o-tolyl) boron and tri (n-butyl) ammonium tetra (4-fluorophenyl) boron. Examples of N, N-dialkylanilinium salts include N, N -Dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2,4,6-pentamethylanilinium tetra (phenyl) boron, and the like,
Examples of the dialkyl ammonium salt include di (n-propyl) ammonium tetra (pentafluorophenyl)
Examples thereof include boron and dicyclohexylammonium tetra (phenyl) boron, and triarylphosphonium salts such as triphenylphosphonium tetra (phenyl) boron, tri (methylphenyl) phosphonium tetra (phenyl) boron and tri (dimethyl). Phenyl)
Examples include phosphonium tetra (phenyl) boron.

In the present invention, as an ionic compound containing a boron atom, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluoro) is used. Mention may also be made of (phenyl) borate.

The following compounds can also be exemplified.
(Note that, in the ionic compounds listed below, the counter ion is, but not limited to, tri (n-butyl) ammonium.) Anion salts 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] dodecachloro dodecaborate,
Tri (n-butyl) ammonium-1-carbadecaborate, tri (n-butyl) ammonium-1-carbaundecaborate, tri (n-butyl) ammonium-1-carbadodecaborate, tri (n-butyl) ammonium -1-Trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, etc .; and borane compounds, carborane compounds and the like. These compounds are used as Lewis acids and ionic compounds.

Borane and carborane complex compounds and salts of carborane anions, eg decaborane (14), 7,
8-dicarbaundecaborane (13), 2,7-dicarbaundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane, dodecahydride-11-methyl-2, 7-Dicarbaundecaborane, tri (n-
Butyl) ammonium 6-carbadecaborate (14),
Tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ammonium 7-carboundecaborate (13), tri (n-butyl) ammonium
7,8-dicarboundecaborate (12), tri (n-butyl) ammonium 2,9-dicarboundecaborate (1
2), tri (n-butyl) ammonium dodecahydride-8-methyl 7,9-dicarbaundecaborate, tri (n-
Butyl) ammonium undecahydride-8-ethyl-
7,9-Dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7, 9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7- Carbaundecaborate, etc .; carborane and salts of carborane, such as 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl -1,3-Dicarbano Naborane, Dodeca Hydride-
The following compounds can also be exemplified, such as 1-methyl-1,3-dicarbanonaborane and undecahydride-1,3-dimethyl-1,3-dicarbanonaborane. (Note that the counter ion in the ionic compounds listed below is, but not limited to, tri (n-butyl) ammonium.) Salts of metal carboranes 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-dicarboundecaborate) ferrate (ferrate) (III), tri (n- Butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate)
Cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8- Dicarbaundecaborate) cubrate (cuprate) (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (metal salt) (III), tri (n-) Butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8- Dicarbaundecaborate) Chromate (Chromate) (II
I), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbaundecaborate)
Cobaltate (III), tri (n-butyl) ammonium bis (dodecahydride dicarbadodecaborate) Cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III), Tris [Tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) Manganate (IV), Bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) Cobaltate (II
I), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) nickelate (IV), and the like.

Two or more kinds of the compounds [C] which react with the metallocene compound [A] to form an ion pair can be used in combination.

[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 ⁴⁰ _n AlX _3-n (a) (In the formula, R ⁴⁰ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 1).
It is 3. In the above formula (a), R ⁴⁰ is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, n -Propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

Specific examples of such an organoaluminum compound include the following compounds. Trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum,
Trialkylaluminums such as trioctylaluminum and tri-2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dimethylaluminum chloride; diethylaluminum chloride; diisopropylaluminum chloride; diisobutylaluminum chloride; dialkylaluminum halides such as dimethylaluminum bromide; 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 ⁴⁰ nAlY _3-n (b) (In the formula, R ⁴⁰ is the same as above, Y is a —OR ⁴¹ group,
OSiR ⁴² ₃ groups, -OAlR ⁴³ ₂ groups, -NR ⁴⁴ ₂ groups,-
SiR ⁴⁵ ₃ group or —N (R ⁴⁶ ) AlR ⁴⁷ ₂ group,
n is 1 to 2, R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁷ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group and the like, and R ⁴⁴ is hydrogen, a methyl group, ethyl. Group, isopropyl group, phenyl group, trimethylsilyl group and the like, and R ⁴⁵ and R ⁴⁶ are methyl group, ethyl group and the like. ) Specific examples of such an organoaluminum compound include the following compounds.

(I) a compound represented by R ⁴⁰ nAl (OR ⁴¹ ) _3-n , such as dimethylaluminum methoxide,
Diethyl aluminum ethoxide, diisobutyl aluminum methoxide, etc.

(Ii) a compound represented by R ⁴⁰ nAl (OSiR ⁴² ₃ ) _3-n , for example, (C ₂ H ₅ ) ₂ Al (OSi (CH
_{3) 3), (iso-} C 4 H 9) 2 Al (OSi (CH 3) 3),
(Iso-C ₄ H ₉ ) ₂ Al (OSi (C ₂ H ₅ ) ₃ ) and the like.

(Iii) a compound represented by R ⁴⁰ nAl (OAlR ⁴³ ₂ ) _3-n , for example, (C ₂ H ₅ ) ₂ Al (OAl
_{(C 2 H 5) 2)} , (iso-C 4 H 9) 2 Al (OAl (iso-C
₄ H _{9) 2),} etc..

(Iv) A compound represented by R ⁴⁰ nAl (NR ⁴⁴ ₂ ) _3-n , such as (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
(CH ₃ ) ₃ ) ₂ ] etc.

(V) A compound represented by R ⁴⁰ nAl (SiR ⁴⁵ ₃ ) _3-n , for example (iso-C ₄ H ₉ ) ₂ Al (Si (CH
₃ ) ₃ ) etc. In the present invention, among these, R ⁴⁰ ₃ Al and R ⁴⁰ nAl
A preferable example is an organoaluminum compound represented by (OR ⁴¹ ) _3-n and R ⁴⁰ nAl (OAlR ⁴³ ₂ ) _3-n , and a compound in which R ⁴⁰ is an isoalkyl group and n = 2 is Particularly preferred. These organoaluminum compounds can be used in combination of two or more.

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

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

Organoaluminum oxy compound [B]
The aluminum atom is usually about 1 to 10,000 mol, preferably 10 to 1 mol of the transition metal atom.
It can be used in an amount such that it is 5,000 mol.

In the compound [C] which reacts with [A] to form an ion pair, the boron atom is usually used in an amount of about 0.5 to 20 mol, preferably 1 to 10 mol, based on 1 mol of the transition metal atom. It can be used in such an 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 aluminum atom in the organoaluminum oxy compound [B] or the boron atom in the compound [C] forming an ion pair. The amount can be used as needed.

Using the metallocene catalyst as described above,
(a) ethylene and (b) an α-olefin having 3 or more carbon atoms
(c) By copolymerizing with a non-conjugated polyene, the α-olefin can be copolymerized with excellent activity, high conversion, and excellent random copolymerizability.

Copolymerization of (a) ethylene with (b) an α-olefin having 3 or more carbon atoms and (c) a non-conjugated polyene is performed using a Group VB transition metal compound-based catalyst such as a vanadium catalyst. However, a random copolymer cannot be obtained with sufficient polymerization activity. Further, when producing EBDM or the like using a Group VB transition metal compound-based catalyst, the type of non-conjugated polyene (c) is often limited to norbornene ring-containing polyenes such as ENB. On the other hand, when a Group IVB metallocene catalyst is used as in the present invention, the non-conjugated polyene (c) is not limited to norbornene ring-containing polyenes, and various polyenes such as M
Chain-like non-conjugated polyenes such as OD can also be copolymerized.

In the present invention, (a) ethylene, (b) an α-olefin having a carbon number of 3 or more, and (c) a non-conjugated polyene are copolymerized, and the above-mentioned IV which constitutes the metallocene catalyst is used.
A group B metallocene compound [A], an organoaluminum oxy compound [B], a compound [C] that reacts with [A] to form an ion pair, and an organoaluminum compound [D] are separately supplied to a polymerization reactor. Alternatively, the catalyst containing the metallocene compound [A] may be prepared in advance and then subjected to the copolymerization reaction.

When preparing the metallocene catalyst,
A hydrocarbon medium which is reactive with the catalyst component can be used, and 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.

Group IVB metallocene compound [A], organoaluminum oxy compound [B], ion pair forming compound [C] and organoaluminum compound [D].
Is usually -100 to 200 ° C, preferably -70 to 10
It is possible to carry out mixed contact at 0 ° 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 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 solution polymerization is preferred. At this time, the above-mentioned hydrocarbon solvent can be used as the polymerization solvent.

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

Further, according to the present invention, a specific random copolymer as described above can be obtained. The molecular weight of this random copolymer can be adjusted by changing the polymerization conditions such as the polymerization temperature and the hydrogen content. It can also be adjusted by controlling the amount of the (molecular weight modifier) used.

The product immediately after polymerization is recovered from the polymerization solution and dried by a conventionally known separation / recovery method to obtain a solid random copolymer. Modified Random Copolymer In the present invention, ethylene / α-olefin /
The non-conjugated polyene random copolymer (hereinafter also simply referred to as a 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 its derivative, and a vinyl ester. Examples thereof include compounds and vinyl chloride.

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) acrylic acid esters 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-methylol acrylamide, 2- (meth) acryloyloxyethyl acid phosphate, glycerin Examples include monoallyl ether, allyl alcohol, allyloxyethanol, 2-butene-1,4-diol, and glycerin monoalcohol.

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

[0142]

[Chemical 15]

(In the formula, R ¹ is a hydrogen atom, a methyl group or an ethyl group, and R ² is a hydrogen atom, a carbon number of 1 to 12,
Preferably, an alkyl group having 1 to 8 carbon atoms, 6 to 1 carbon atoms
2, preferably 6 to 8 cycloalkyl groups. The above alkyl group and cycloalkyl group may further have a substituent. ) Such amino group-containing ethylenically unsaturated compounds include, for example, aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, phenyl methacrylate. Acrylic acid or methacrylic acid alkyl ester derivatives such as aminoethyl and cyclohexylaminoethyl methacrylate N-vinyldiethylamine, vinylamine derivatives such as N-acetylvinylamine Allylamine, methacrylamine, N-methylacrylamine, N, Allylamine derivatives such as N-dimethylacrylamide and N, N-dimethylaminopropylacrylamide Acrylamide derivatives such as acrylamide and N-methylacrylamide Aminostyrenes such as p-aminostyrene 6- Amino hexyl succinimide, such as 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. Examples of such an epoxy group-containing ethylenically unsaturated compound include glycidyl acrylate and glycidyl methacrylate, 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,
Endo-cis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (nadic acid ^TM ) mono and diglycidyl esters, endo-cis-bicyclo [2.2.1] hept-5-ene- 2-Methyl-2,3-dicarboxylic acid (methyl nadic acid ^TM )
Dicarboxylic acid mono and alkyl glycidyl esters such as allyl succinic acid mono and glycidyl esters (alkyl groups having 1 to 12 carbon atoms in the case of monoglycidyl ester), alkyl glycidyl esters of p-styrenecarboxylic 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,
Examples thereof include 5,6-epoxy-1-hexene and vinylcyclohexene monoxide.

The aromatic vinyl compound is represented by the following formula.

[0146]

Embedded image

(In the formula, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group and an isopropyl group. R ³ is 1 carbon atom. To a hydrocarbon group or a halogen atom, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group and a chlorine atom, a bromine atom or an iodine atom, n is usually 0 to 5, preferably 1 Is an integer of 5 to 5.) Examples of such aromatic vinyl compounds include 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- Vinyl isoquinoline, N-
Examples thereof include vinylcarbazole and N-vinylpyrrolidone.

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

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

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

Preparation of Modified Random Copolymer The modified random copolymer according to the present invention can be obtained by graft-polymerizing a polar monomer onto the above random copolymer. When the random copolymer is graft-polymerized with the polar monomer as described above, the polar monomer is used in an amount of usually 1 to 100 parts by weight, preferably 5 to 80 parts by weight, based on 100 parts by weight of the random copolymer. Used in quantity.

This graft polymerization is usually carried out 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 peroxides include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane and 2,5-
Dimethyl-2,5-bis (t-butylperoxy) hexyne-3,
1,3-bis (t-butylperoxyisopropyl) benzene,
1,1-bis (t-butylperoxy) valerate, 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 a random copolymer 10
It is preferably used 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, or can be used after being dissolved in a small amount of an organic solvent. The organic solvent can be used without particular limitation as long as it is an organic solvent capable of dissolving a radical initiator, for example, aromatic hydrocarbon solvents such as benzene, toluene and xylene, pentane, hexane, heptane, 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 tetrachlorethylene, alcohol 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 such as ethyl acetate and dimethyl phthalate, dimethyl ether, diethyl ether, di -n
-Ether solvents such as amyl ether, tetrahydrofuran and dioxyanisole can be used.

When the polar copolymer is graft-polymerized with the random copolymer, a reducing substance may be used.
When a reducing substance is used, the amount of polar monomer grafted can be improved.

[0158] The reducing agent, iron (II) ions, chromium ions, cobalt ions, nickel ions, palladium ions, sulfite, hydroxylamine, hydrazine, further _{-SH, SO 3 H, -NHNH 2} , -COC
Examples include compounds containing groups such as H (OH)-.

Specific examples of such reducing substances include ferrous chloride, potassium dichromate, cobalt chloride,
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 carried out by a conventionally known method. For example, the random copolymer is dissolved in an organic solvent, and then the polar monomer and the radical initiator are added to the solution to 70 to 20.
0.5 to 1 at a temperature of 0 ° C., preferably 80 to 190 ° C.
The reaction can be performed for 5 hours, preferably 1 to 10 hours.

The above-mentioned organic solvent is not particularly limited as long as it is an organic solvent capable of dissolving the random copolymer. For example, aromatic hydrocarbon solvents such as benzene, toluene and xylene, and fats such as pentane, hexane and heptane. A group hydrocarbon solvent or the like can be used.

It is also possible to produce a modified random copolymer by reacting the random copolymer with the polar monomer in the absence of solvent using an extruder or the like. This reaction is usually at or above the melting point of the random copolymer, specifically 120 to 2
It is desirable to carry out at a temperature of 50 ° C. for usually 0.5 to 10 minutes.

The modified random copolymer thus obtained has a modification amount (amount of polar monomer grafted) of 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 / non-conjugated polyene random copolymer is used even in an unvulcanized state. However, when used as a vulcanized product, more excellent properties can be exhibited.

The vulcanizable rubber composition according to the present invention can be vulcanized by a method of heating with a vulcanizing agent or a method of irradiating with an electron beam without using a vulcanizing agent.
The vulcanizable rubber composition according to the present invention comprises ethylene / α-
Other components can be appropriately contained depending on the purpose together with the olefin / non-conjugated polyene random copolymer,
An ethylene / α-olefin / non-conjugated polyene random copolymer is contained in an amount of 20% by weight or more, preferably 2% by weight based on the total rubber composition.
It is desirable that the content is 5% by weight or more.

As other components, for example, a reinforcing agent,
Inorganic fillers, softeners, anti-aging agents (stabilizers), processing aids, and further foaming compounds such as foaming compounds, plasticizers, colorants, foaming agents, and other rubber compounding agents. Various drugs such as The other ingredients are
The type and content thereof are appropriately selected depending on the application, but among these, it is particularly preferable to use a reinforcing agent, an inorganic filler, a softening agent, etc., which will be described more specifically below.

Reinforcing Agent and Inorganic Filler As the reinforcing agent, specifically, SRF, GPF, FEF,
Examples include carbon blacks such as MAF, HAF, ISAF, SAF, FT, and MT; those obtained by surface-treating these carbon blacks with a silane coupling agent; silica; activated calcium carbonate; fine talc; fine silica;

Specific examples of the inorganic filler include light calcium carbonate, heavy calcium carbonate, talc and clay. The rubber composition according to the present invention contains a reinforcing agent and / or an inorganic filler as ethylene / α-olefin /
The non-conjugated polyene random copolymer may be contained in an amount of 10 to 300 parts by weight, preferably 10 to 200 parts by weight, based on 100 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-described 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, the softening agents conventionally blended in rubber are widely used. Specifically, petroleum-based softening agents such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and vaseline, Coal tar-based softeners such as coal tar and coal tar pitch, fatty oil-based softeners such as castor oil, linseed oil, rapeseed oil and coconut oil, waxes such as tall oil, sub, beeswax, carnauba wax and 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 resins, atactic polypropylene, and coumarone indene resins are used.

Of these, petroleum-based softeners are preferable, and process oil is particularly preferable. The rubber composition according to the present invention contains the above-mentioned softening agent in an amount of 10 to 200 parts by weight, preferably 10 to 150 parts by weight, particularly preferably 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene random copolymer. Can be contained in an amount of 10 to 100 parts by weight.

Anti-Aging Agent It is preferable that the rubber composition according to the present invention contains an anti-aging agent because the material life can be extended. As the antiaging agent, 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.

Such an antiaging agent is ethylene / α-
It can be appropriately used in an amount of 5 parts by weight or less, preferably 3 parts by weight or less, based on 100 parts by weight of the olefin / non-conjugated polyene random copolymer.

Processing aids As the processing aid, those generally compounded with rubber as the processing aid 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 appropriately used in an amount of 10 parts by weight or less, preferably 5 parts by weight or less, relative to 100 parts by weight of the non-conjugated polyene random copolymer.

[0176] When the vulcanization by heating a rubber composition according to the vulcanizing agent also present invention, the configuration typically vulcanizer in the rubber composition, vulcanization accelerator, a vulcanization system such as vulcanizing agent Compound is added.

As the vulcanizing agent, sulfur, sulfur compounds and organic peroxides 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, high molecular polysulfide, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide and selenium dimethyldithiocarbamate.

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-butylperoxin) hexyne-3, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-
Alkyl peroxides such as butylperoxy) -hexane, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, t-butylhydroperoxide,
t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxy vivarate, t-butyl peroxy maleic acid, t-butyl peroxy neodecanoate, t-butyl peroxybenzoate, di Examples thereof include peroxyesters such as -t-butylperoxyphthalate and ketone peroxides such as dicyclohexanone peroxide. These may be used in combination of two or more.

Of these, the one-minute half-life temperature is 13
Organic peroxides at 0 ° C to 200 ° C are preferable, and 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 preferable.

When the vulcanizing agent is sulfur or a sulfur-based compound, 0.1 to 1 is used with respect to 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene random copolymer.
It can be used in an amount of 0 parts by weight, preferably 0.5 to 5 parts by weight.

When the vulcanizing agent is an organic peroxide, it is 0.0003 to 0.05 mol, preferably 0.001 to 0.001 mol, per 100 g of the ethylene / α-olefin / non-conjugated polyene random copolymer. It can be used in an amount of 03 mol.

Vulcanization accelerator When sulfur or a sulfur compound is used as a vulcanizing agent, it is preferable to use a vulcanization accelerator together.

Specific examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazole sulfenamide (CB
S), sulfenamide compounds such as N-oxydiethylene-2-benzothiazolesulfenamide, N, N-diisopropyl-2-benzothiazolesulfenamide,
Mercaptobenzothiazole (MBT), 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-
Thiazole compounds such as diethyl-4-morpholinothio) benzothiazole and dibenzothiazyldisulfide;
Guanidine compounds such as diphenylguanidine, triphenylguanidine, diorsonitrile guanidine, orthonitrile biguanide, diphenylguanidine phthalate, acetaldehyde-aniline reactant, butyraldehyde-aniline condensate, hexamethylenetetramine, aldehyde amine such as acetaldehyde ammonia or Aldehyde-ammonia compounds, imidazoline compounds such as 2-mercaptoimidazoline, thiocarbanilide, diethylthiourea, dibutylthiourea,
Thiourea compounds such as trimethylthiourea and diortho tolyl thiourea, tetramethylthiuram monosulfide, tetramethylthiuram disulfide (TMT
D), thiuram-based compounds such as tetraethylthiuram disulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide, dipentamethylenethiuram tetrasulfide (DPTT), zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, di-n-butyldithiocarbamate Zinc salts such as zinc, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, and tellurium dimethyldithiocarbamate; xanthate compounds such as zinc dibutylxanthogenate; No.

The vulcanization accelerators as described above are ethylene / α
-Olefin / non-conjugated polyene random copolymer 100
With respect to parts by weight, 0.1 to 20 parts by weight, preferably 0.2 to
It is desirable to use in an amount of 10 parts by weight.

Vulcanization aid (polyfunctional monomer) When an organic peroxide is used as the vulcanizing agent, the vulcanization aid (polyfunctional monomer) is used in an amount of 0.1 mol per mol of the organic peroxide. It is preferable to use them in an amount of 5 to 2 moles, preferably approximately equimolar amounts.

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, triallyl cyanurate and triallyl isocyanurate, maleimide compounds such as m-phenylene bismaleimide, divinylbenzene And so on.

In the present invention, of the above-mentioned vulcanizing agents, it is preferable to use sulfur or a sulfur-based compound, particularly sulfur, because 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 or a foaming auxiliary agent, it can be foam-molded.

As the foaming agent, a foaming agent generally used for foam-molding rubber can be widely used.
Specifically, inorganic blowing 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, benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p, p ' -Sulfonyl hydrazide compounds such as oxybis (benzenesulfonyl hydrazide) and diphenyl sulfone-3,3'-disulfonyl hydrazide, azide compounds such as calcium azide, 4,4-diphenyl disulfonyl azide and p-toluene sulfonyl azide To be

Of these, nitroso compounds, azo compounds and azide compounds are preferable. The blowing agent is ethylene / α-olefin / non-conjugated polyene random copolymer 1
0.5 to 30 parts by weight, preferably 1 to 100 parts by weight
It can be used in amounts of up to 20 parts by weight. From the rubber composition containing the foaming agent in such an amount, the apparent specific gravity is 0.
It is possible to produce foams of 03 to 0.8 g / cm ³ .

It is also possible to use a foaming auxiliary together with the foaming agent, and when the foaming auxiliary is used in combination, it is effective in lowering the decomposition temperature of the foaming agent, promoting decomposition, and homogenizing bubbles. 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 aid is ethylene / α-olefin /
It may be used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the non-conjugated polyene random copolymer.

Other Rubbers The rubber composition according to the present invention can be used as a blend with other known rubbers within a range not impairing the object of the present invention.

Examples of such other rubbers include natural rubber (NR), isoprene rubber such as 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 copolymer rubbers can also be used, for example, ethylene / propylene random copolymer (EPR), other than the above ethylene / α-olefin / non-conjugated polyene random copolymer. The ethylene / α-olefin / non-conjugated polyene random copolymer of, for example, EPDM can be used.

The vulcanizable rubber composition according to the present invention is prepared from ethylene / α-olefin / non-conjugated polyene random copolymer and other components as described above by a general method for preparing a rubber compound. can do. For example, using an internal mixer such as a Banbury mixer, a kneader, or an intermix, ethylene / α
-Olefin / non-conjugated polyene random copolymer and other components are kneaded at a temperature of 80 to 170 ° C for 3 to 10 minutes, and then, if necessary, a vulcanizing agent, a vulcanization accelerator or a vulcanization aid. In addition, using rolls such as an open roll or a kneader, the roll temperature is 40 to 80 ° C.
It can be prepared by kneading for 0 minutes and then dispensing. In this way, a ribbon-shaped or sheet-shaped rubber composition (blended rubber) is usually 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 vulcanized product (vulcanized rubber) of the rubber composition according to the present invention is usually obtained by molding an unvulcanized rubber composition as described above into an extruder, calender roll, press, injection molding. Machine, transfer molding machine, etc., to obtain a desired shape by preforming, and simultaneously with molding or introducing the molded product into a vulcanization tank to heat or vulcanize it by irradiating it with an electron beam. be able to.

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

When vulcanizing by electron beam irradiation without using a vulcanizing agent, the preformed rubber composition has 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.

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

The vulcanized foam obtained by heat-foaming a rubber compound containing a foaming agent can be used for heat insulating materials, cushioning materials, sealing materials and the like.

[0203]

EFFECTS OF THE INVENTION According to the method for producing an ethylene / α-olefin / non-conjugated polyene random copolymer according to the present invention, ethylene and α- having 3 or more carbon atoms cannot be achieved by the conventional production method. A high molecular weight copolymer can be obtained by copolymerizing an olefin and a non-conjugated polyene with high activity, α-olefin with a high conversion rate and excellent random copolymerizability. Further, the method for producing an ethylene / α-olefin / non-conjugated polyene random copolymer according to the present invention has excellent polymerization activity at high temperatures, so that an ethylene / α-olefin / non-conjugated polyene random copolymer can be efficiently prepared. It can be manufactured.

Ethylene .alpha.- produced by the present invention
The olefin / non-conjugated polyene random copolymer has the above-mentioned properties, and has a narrow composition distribution, excellent mechanical strength, low temperature flexibility, and heat aging resistance, weather resistance, and ozone resistance. It also has excellent characteristics.

A vulcanizable rubber composition containing such an ethylene / α-olefin / non-conjugated polyene random copolymer is excellent in mechanical strength, weather resistance, ozone resistance, processability and the like, and is resistant to cold. Excellent in heat resistance (low temperature flexibility) and heat resistance. The rubber composition according to the present invention can form a vulcanized rubber molded body or a vulcanized rubber foam which is particularly excellent in such properties.

[0206]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.
The glass transition temperature Tg of the ethylene / α-olefin / non-conjugated polyene random copolymer is measured by a differential scanning calorimeter (DS).
C). The glass transition temperature Tg is an index of low temperature flexibility of the ethylene / α-olefin / non-conjugated polyene random copolymer.

Measurement of Tg by DSC 180 ° C. from room temperature (25 ° C.) to 20 ° C./min
After raising the temperature to ℃ and keeping it at 180 ℃ for 2 minutes, -20 ℃
The Tg was determined by cooling to −80 ° C. at a rate of / min, holding at −80 ° C. for 2 minutes, and then raising the temperature again at a rate of 20 ° C./min. The zirconium compounds used in the examples are shown below.

[0208]

Embedded image

[0209]

Example 1 Pre-contact of zirconium compound and methylalumoxane
Touch, Preparation of Catalyst Solution A predetermined amount of the zirconium compound A and a toluene solution of methylalumoxane (1.2 mg atom / ml in terms of aluminum atom) are stirred for 30 minutes at room temperature in the dark. Thus, 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.
The concentration was 004 mmol / ml, and the methylalumoxane concentration was 1.2 mg / atom in terms of aluminum atom.
ml.

Next, to this toluene solution, hexane having a volume 5 times that of toluene was added with stirring to prepare a catalyst solution having the following Zr concentration and methylalumoxane concentration, which was subjected to a polymerization reaction. It was used as a catalyst. Zr concentration: 0.0067 mmol / ml (0.67 mmol / liter) Methylalumoxane concentration (converted to Al atom): 0.0
20 mmol / ml (200 mmol / liter)

[0211] using a stainless steel polymerization vessel 15 liter with a Polymerization stirring blade, and continuously ethylene, 1-butene, 7-methyl-1,6
-Copolymerized with octadiene as follows.

First, from the upper part of the polymerization vessel, into the polymerization vessel, dehydrated and purified hexane was 3.185 liters per hour, the catalyst solution obtained above was 0.015 liters per hour, and a hexane solution of triisobutyluminum (concentration: 17 mmol / hr). 0.3 liter / hr, 7-methyl-1,6-octadiene (hereinafter also referred to as MOD) hexane solution (concentration 0.15)
Liter / liter) was continuously fed at 1.5 liters per hour.

From the top of the polymerization vessel, ethylene was added at an hour of 20.
0 liter and 1-butene of 155 liter per hour were continuously supplied. The copolymerization reaction is 90 ° C., and the average residence time is 1 hour (that is, a polymerization scale of 5 liters).
It was done so that

On the other hand, a small amount of methanol was added to the polymerization solution extracted 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),
It was dried for 24 hours.

As described above, ethylene 1-butene
MOD random copolymer was obtained in an amount of 280 g / h. The obtained random copolymer had a unit derived from ethylene and a unit derived from 1-butene of 79/21.
(Molar ratio). It also contained units derived from 7-methyl-1,6-octadiene (MOD) in an amount of 2.3 mol%.

The iodine value of the random copolymer was 16, and the intrinsic viscosity [η] measured in decalin at 135 ° C.
Is 2.4 dl / g, the intensity ratio D of Tαβ to Tαα in the ¹³ C-NMR spectrum is less than 0.01, the B value is 1.08, and the glass transition temperature Tg is -58 ° C. And the g η ^* value was 1.05. Table 2 shows the results.

[0219]

Examples 2 to 9 In the same manner as in Example 1 except that the copolymerization reaction was carried out under the polymerization conditions shown in Table 1 instead of the polymerization conditions of Example 1, ethylene / α-olefin / A non-conjugated polyene random copolymer was prepared. Table 2 shows the results.

[0218]

Example 10 Ethylene propylene ethylidene norbornene (ENB) was obtained in the same manner as in Example 3 except that propylene was used instead of 1-butene.
A random copolymer was produced. Table 2 shows the results.

[0219]

[Table 1]

[0220]

[Table 2]

[0221]

Comparative Example 1 Using a 2-liter polymerization vessel equipped with a stirring blade, ethylene, 1-butene, and 7-methyl-1,6- were continuously added.
Copolymerized with octadiene as follows.

From the top of the polymerization vessel into the polymerization vessel, 7-methyl-1,6
-Hexane solution of octadiene (MOD) (concentration 36g
/ Liter) 0.5 liter / hour, VO as catalyst
Hexane solution of (OC ₂ H ₅ ) Cl ₂ (concentration 8 mmol /
0.5 liter / hour, and a hexane solution of ethylaluminum sesquichloride [Al (C ₂ H ₅ ) _1.5 Cl _1.5 ] (concentration 64 mmol / liter) 0.5 / hour.
Then, liter and hexane were each supplied in an amount of 0.5 liter per hour, and the polymerization solution in the polymerization vessel was continuously withdrawn from the lower portion of the polymerization vessel so that the polymerization solution was always 1 liter.

Further, in this polymerization vessel, ethylene was used at a rate of 130 liters per hour and 1-butene was charged at a rate of 20 per hour using a bubbling tube.
0 liter and hydrogen were supplied in an amount of 20 liter per hour.
The copolymerization reaction was carried out while maintaining the temperature at 20 ° C. by circulating a refrigerant in a jacket attached outside the polymerization vessel.

A polymerization solution of the ethylene / 1-butene / MOD random copolymer obtained by the above copolymerization reaction was decalcified with hydrochloric acid water, and then a large amount of methanol was added to precipitate the polymer to 100 ° C. And dried under reduced pressure for 24 hours.

Ethylene 1-butene
MOD random copolymer was obtained in an amount of 280 g / h. The obtained random copolymer (rubber) had a unit derived from ethylene and a unit derived from 1-butene of 7
The content was 4/26 (molar ratio). Also 7-methyl-1,6
It contained units derived from octadiene (MOD) in an amount of 2.1 mol%.

The iodine value of the random copolymer was 14, the intrinsic viscosity [η] measured in decalin at 135 ° C. was 0.13 dl / g, and the intensity ratio D of Tαβ to Tαα in the ¹³ C-NMR spectrum was D. Is 1.54,
The gη ^* value was 1.03.

As described above, it was found that when the vanadium catalyst system was used, the molecular weight of the product (random copolymer) was extremely low, and the random copolymer could not be used as a rubber.

[0228]

Example 11 Using a 15-liter stainless steel polymerization vessel equipped with a combined stirring blade, ethylene, 1-butene, and ethylidene norbornene (hereinafter, also referred to as ENB) were continuously copolymerized as follows. Let

First, from the upper part of the polymerization vessel, into the polymerization vessel, dehydrated and purified hexane was 3.185 liters / hr, and the catalyst solution containing the zirconium compound A and methylalumoxane prepared in Example 1 was 0.015 liters / hr. Hexane solution of triisobutylaluminum (concentration 17 mmol /
0.3 liter / hr and a hexane solution of ENB (concentration 0.02 liter / liter) were continuously fed at 1.5 liter / hr.

From the top of the polymerization reactor, ethylene was added at an hour of 20.
0 liter and 1-butene of 155 liter per hour were continuously supplied. The copolymerization reaction is carried out at 80 ° C. and the average residence time is 1 hour (that is, a polymerization scale of 5 liters).
I went to.

On the other hand, a small amount of methanol was added to the polymerization solution extracted 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),
It was dried for 24 hours.

As described above, ethylene 1-butene
ENB copolymer was obtained in an amount of 250 g / h. The obtained copolymer contained units derived from ethylene and units derived from 1-butene in a ratio of 80/20 (molar ratio). The iodine value based on ENB was 15.

The intrinsic viscosity [η] of the copolymer measured in decalin at 135 ° C. was 2.7 dl / g, and ¹³ C-NM
Intensity ratio D of Tαβ to Tαα in the R spectrum
Was less than 0.01, the B value was 1.1, the glass transition temperature Tg was −56 ° C., and the gη ^* value was 1.05. The results are shown in Table 3.

[0234]

Examples 12 to 16 Ethylene / α-olefin, non-conjugated polyene random copolymers were produced in the same manner as in Example 11 except that the copolymerization reaction was carried out by changing the polymerization conditions. The results are shown in Table 3.

[0235]

[Table 3]

[0236]

Examples 17 to 22 Compounded rubbers prepared by using the ethylene / α-olefin / non-conjugated polyene random copolymers produced in Examples 11 to 16 and other components in the compounding amounts shown in Table 4 ( A crosslinked product of the rubber composition) was obtained. That is, ethylene / α-olefin / non-conjugated polyene random copolymer, stearic acid, zinc white, paraffin oil and carbon were kneaded for 10 minutes using a 1.7 liter Banbury mixer (Kobe Steel). Further, using a 6-inch roll (F / B = 50/50 ° C.), a vulcanizing agent and a vulcanization accelerator were added and kneaded.

Next, this compounded rubber was vulcanized by pressing at 160 ° C. for 10 minutes to obtain a crosslinked sheet having a thickness of 2 mm. The test piece for compression set (CS) measurement has a thickness of 1
A right cylindrical test piece with a diameter of 2.7 mm and a diameter of 29 mm is
Obtained by vulcanizing at 0 ° C. for 15 minutes.

The rubber composition and the vulcanized product (crosslinked sheet) obtained above were evaluated by the following methods.
The composition of the unvulcanized rubber composition is shown in Table 4, and the test result of the vulcanized product is shown in Table 5.

(1) Tensile test (T _B and E _B ) A vulcanized rubber sheet was punched out to produce a No. 3 type dumbbell test piece described in JIS K 6301, and the test piece was used. According to the method specified in the third paragraph, a tensile test was conducted under the conditions of a measuring temperature of 25 ° C. and a tensile speed of 500 mm / min, and the tensile breaking stress T _B and the tensile breaking elongation E _B were measured.

(2) Hardness test (Hs hardness) In the hardness test, the spring hardness Hs (JISA hardness) was measured according to JIS K6301.

(3) Aging test (AR (T _B ), AR
(E _B) and A _H) aging test is carried out for 70 hours air heating aging test at 125 ° C., retention for the physical properties before aging, i.e. tensile strength retention AR (T _B), elongation retention ratio AR (E _B ), The change in hardness A _H (JIS A) was determined.

(4) Compression set test (CS) The compression set test is based on JIS K 6301.
The low temperature compression set (CS) after 22 hours at -40 ° C was determined. The smaller the low temperature compression set, the better the low temperature flexibility.

[0243]

[Table 4]

[0244]

[Table 5]

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing an example of a process for preparing a Group IVB transition metal compound catalyst used in the method for producing an ethylene / α-olefin / non-conjugated polyene random copolymer according to the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, Toshihiro Aine, No. 6, 1-2, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture, Mitsui Petrochemical Industry Co., Ltd. (72) Toshiyuki Tsutsui, Kuga-gun, Yamaguchi Prefecture 6-1-2 Waki, Waki Mitsui Petrochemical Co., Ltd. (72) Inventor Hide Hide Nakahama 3 Chikusaigan, Ichihara, Chiba Mitsui Sekiyu Kagaku Kogyo Co., Ltd.

Claims (8)

[Claims] 1. In the presence of a metallocene catalyst containing a metallocene compound represented by the following formula [I] or [II], (a)
Ethylene, (b) an α-olefin having 3 or more carbon atoms, (c)
A method for producing an ethylene / α-olefin / non-conjugated polyene random copolymer, characterized by random copolymerizing with a non-conjugated polyene; (In the formula, M is a transition metal of Group IVB of the periodic table, R ¹¹ and R ¹² may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, A halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, R ¹³ is an alkyl group having 1 to 20 carbon atoms, R ¹⁴ Is an alkyl group having 1 to 20 carbon atoms, X ¹ and X ² may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon atom having 1 to 20 carbon atoms. It is a halogenated hydrocarbon group, a silicon-containing group, an oxygen-containing group or a sulfur-containing group, 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 15 -, - P (R} 15) -, - P (O) (R 15) -, - B
R ¹⁵ - or -AlR ¹⁵ - (R ¹⁵ is 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) is. ), Embedded image (In the formula, M is a transition metal of Group IVB of the periodic table, X ³ and X ⁴ may be the same or different from each other,
Hydrogen atom, C1-C10 alkyl group, C1-C1
0 alkoxy group, C 6-10 aryl group, C 6-10 aryloxy group, C 2-10 alkenyl group, C 7-40 arylalkyl group, C 7-40 alkyl It is an aryl group, an arylalkenyl group having 8 to 40 carbon atoms, an OH group or a halogen atom, and R ²¹ may be the same or different from each other, and is a hydrogen atom, a halogen atom or an optionally halogenated C 1 10 alkyl group, aryl group, or -NR ₂ of 6 to 10 carbon atoms, -SR, -OSiR _3, -SiR ₃ or -PR ₂ radical (R is a halogen atom, an alkyl group or a C 1 to 10 carbon atoms a number of 6 to 10 aryl group), R ²² to R ²⁸ are either the same as the above R ^21, or adjacent R ²² to R ^28, together with the atoms connecting them, an aromatic - or cycloaliphatic It may form a family ring, ## STR3 ## = BR ²⁹ , = AlR ²⁹ , -Ge-, -Sn-, -O-,
-S -, = SO, = SO 2, = NR 29, = CO, = PR
²⁹ or = P (O) R ²⁹ (wherein R ²⁹ and R ³⁰
May be the same as or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and 1 to 1 carbon atoms.
Fluoroalkyl group having 10 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, fluoroaryl group having 6 to 10 carbon atoms, 1 to carbon atoms
An alkoxy group having 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms,
Arylalkyl group having 7 to 40 carbon atoms, 8 to 40 carbon atoms
Or an arylaryl group having 7 to 40 carbon atoms, or R ²⁹ and R ³⁰ each may form a ring together with the atom to which they are bonded, M ²
Is silicon, germanium or tin. ). 2. The (b) α-olefin has 4 to 1 carbon atoms.
The method for producing an ethylene / α-olefin / non-conjugated polyene random copolymer according to claim 1, wherein the α-olefin is 0. 3. The ethylene according to claim 1 or 2.
The unit obtained from the method for producing an α-olefin / non-conjugated polyene random copolymer is (i) (a) a unit derived from ethylene, and (b) a unit derived from an α-olefin having 3 or more carbon atoms. / 60 to 95/5 [(a) / (b)] in a molar ratio, (ii) iodine value is 1 to 50, (iii) intrinsic viscosity [η] measured in 135 ° C decalin
Is 0.1 to 8.0 dl / g, and (iv) T relative to Tαα in the ¹³ C-NMR spectrum.
The intensity ratio D (Tαβ / Tαα) of αβ is 0.5 or less, and (v) the B value obtained from the ¹³ C-NMR spectrum and the following formula is 1.00 to 1.50; B value = [ P _OE ] / (2 · [P _E ] · [P _O ]) (wherein [P _E ] is the content mole fraction of units derived from (a) ethylene in the random copolymer, [P _O ] is the mole fraction of the units derived from the (b) α-olefin in the random copolymer, and [P _OE ] is the total dyad (dy) in the random copolymer.
ad) is the ratio of α-olefin / ethylene chain number to the chain number), (vi) the glass transition temperature Tg determined by DSC is -50 ° C.
And (vii) the intrinsic viscosity [η] measured in (iii) above and a linear ethylene / propylene copolymer having the same weight average molecular weight (by light scattering method) as the ethylene content of 70 mol%. The gη ^* value (= [η] / [η] _blank ) defined by the ratio of the intrinsic viscosity [η] _blank of the polymer is more than 0.9, ethylene / α-olefin / non Conjugated polyene random copolymer. 4. The (b) α-olefin has 4 to 1 carbon atoms.
4. The ethylene / α-olefin / non-conjugated polyene random copolymer according to claim 3, wherein the α-olefin is 0. 5. The ethylene / α- according to claim 3 or 4.
A vulcanizable rubber composition comprising an olefin / non-conjugated polyene random copolymer. 6. A reinforcing agent and / or an inorganic filler is contained in an amount of 10 to 200 parts by weight with respect to 100 parts by weight of an ethylene / α-olefin / non-conjugated polyene random copolymer. Item 6. A rubber composition according to item 5. 7. 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 5, wherein the rubber composition is contained in an amount of 0 to 200 parts by weight. 8. A vulcanized rubber obtained from the vulcanizable rubber composition according to claim 5.