JP2003268043A - Ethylene/alpha-olefin/nonconjugated polyene random copolymer and use of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ethylen/α-olefin/nonconjugated polyene random copolymer that has a specific composition, iodine value, intrinsic viscosity, strength ratio D (Tαβ/Tαα), B value and glass transition temperature Tg. <P>SOLUTION: The ethylene/α-olefin/nonconjugated polyene random copolymer has a narrow distribution of composition, excellent in mechanical strengths, flexibility at low temperature together with heat aging resistance, weather resistance and ozone resistance. A vulcanizable rubber composition containing the random copolymer of ethylene/α-olefin/nonconjugated polyene is excellent in mechanical strengths, weather resistance, ozone resistance, processability, cold resistance (flexibility at low temperature) and heat resistance. The rubber composition forms a molding of the vulcanized rubber or a vulcanized rubber foam excellent in those properties. <P>COPYRIGHT: (C)2003,JPO

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, an α-olefin and a 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 in automobile parts, electric wire materials, construction civil engineering materials, industrial material parts, etc. It's being used.

Such ethylene / α-olefin rubbers are usually used after being vulcanized. Since the properties of the vulcanized rubbers vary depending on the ethylene component content, the molecular weight, the iodine value, etc. Different values are used. For example, EP with high ethylene content
When M or EPDM is used, a vulcanized product with excellent heat resistance can be obtained, and EPM or EPDM with a low ethylene content is obtained.
It is known that vulcanizates excellent in low-temperature flexibility can be obtained by using.

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 if 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,
It has been desired to develop an ethylene / α-olefin / non-conjugated polyene copolymer excellent in heat resistance, heat aging resistance and low temperature flexibility, and a vulcanized product thereof. However, although such an ethylene / α-olefin / non-conjugated polyene copolymer, particularly an ethylene / α-olefin / non-conjugated polyene copolymer having 4 or more carbon atoms, has been desired to appear, 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 if an attempt is made to copolymerize with methyl-1,6-octadiene (hereinafter also referred to as MOD), the molecular weight does not increase as compared with 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 is 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.

Further, JP-A-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 for 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 a carbon number of 3 or more and a non-conjugated polyene are copolymerized by using a conventionally known catalyst as described above, an α-olefin having a carbon number of 3 or more is compared with ethylene. There is a problem that it is difficult to obtain an ethylene / α-olefin / non-conjugated polyene random copolymer having a low reaction rate (conversion rate) and a high content of an 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 production method capable of producing an ethylene / α-olefin / non-conjugated polyene random copolymer having 3 or more carbon atoms, which has a narrow composition distribution, a high molecular weight, and excellent low-temperature flexibility and heat aging resistance. Is desired.

[0012]

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 copolymer having a high molecular weight by copolymerizing an olefin and a non-conjugated polyene with high activity, and 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 excellent in low temperature flexibility and heat aging, which has a narrow composition distribution and excellent mechanical strength obtained by the production method The purpose is to provide a copolymer.

Further, the present invention is directed to ethylene.
The purpose of the invention is to provide a use of α-olefin / non-conjugated polyene random copolymer, and especially including the copolymer, it is excellent in 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.

[0014]

SUMMARY OF THE INVENTION An ethylene / α-olefin / non-conjugated polyene random copolymer according to the present invention comprises (i) (a) a unit derived from ethylene and (b) an α-olefin having 3 to 20 carbon atoms. Guided units are 40/60 to 95/5
It is contained in a molar ratio of [(a) / (b)] and (ii) has an iodine value of 1.
And (iii) the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.1 to 8.0 dl / g, and (iv) ¹³
The intensity ratio D (Tαβ / Tαα) of Tαβ to Tαα in the C-NMR spectrum 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, and [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), and (v
i) The glass transition temperature Tg determined by DSC is -50 ° C or less.

In the present invention, the α-olefin of (b) is preferably an α-olefin having 4 to 10 carbon atoms, and more preferably an α-olefin having 8 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 can 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. Alternatively, the inorganic filler may be contained in an amount of 10 to 200 parts by weight, and the softening agent may be contained in an amount of 10 to 200 parts by weight.

The vulcanized rubber according to the present invention is obtained from the rubber composition as described above.

[0017]

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 properties. 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 Ethylene / α-olefin / non-conjugated polyene random copolymer (hereinafter also referred to as random copolymer) produced by the present invention comprises (a) ethylene and (b) 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 to 20 include propylene, 1-butene, 1-pentene, 1-hexene and 3-methyl-1-.
Butene, 3-methyl-1-pentene, 3-ethyl-1-pentene,
4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl
-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,
1-octadecene, 1-eicosene and combinations thereof.

Of these, α-olefins having 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 have excellent mechanical strength, and at the same time, the rubber has excellent mechanical strength. 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 of 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. .2-6dl
/ G range.

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 each (b) α- having 3 or more carbon atoms
It is a peak intensity of CH _{2 in} a unit derived from an olefin, and means two types of CH ₂ having different positions with respect to a tertiary carbon as shown below.

[0028]

[Chemical 1]

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)). Here, the strength ratio D will be described more specifically by taking an ethylene / 1-butene / 7-methyl-1,6-octadiene random copolymer as an example.

This ethylene 1-butene 7-methyl-1,6-
In the ¹³ C-NMR spectrum of the octadiene random copolymer, the peak appearing at 39 to 40 ppm is Tαα,
The peak appearing at 31 to 32 ppm is assigned to Tαβ. The intensity ratio D is calculated by the integrated value (area) ratio of each peak portion. The intensity ratio D thus obtained is generally 2,1 after the 1,2-addition reaction of 1-butene.
It is considered to be a measure of the rate at which the addition reaction occurs or the rate at which the 1,1 addition reaction of 1-butene is followed by the 1,2 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, the more (b)
This indicates that the bond direction of the α-olefin is regular, and 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 above 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 for 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, calculated 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 composition distribution of the random copolymer. Indicates that is narrow. The composition value distribution 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 having excellent 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, ethylene, 1-butene and ethylidene norbornene (ENB).
Is a random copolymer E of ethylene, propylene and ENB in which the composition ratio of ethylene, α-olefin and polyene is the same as that of the random copolymer E.
The glass transition temperature Tg is about 5 to 10 ° C. lower than that of PDM, and it has excellent low temperature characteristics.

(Vii) gη ^* value The gη ^* value is the intrinsic viscosity [η] measured in (iii) above.
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 ).

The above [η] _blank is calculated from the formula (I) by replacing the weight average molecular weight M _w of the ethylene / propylene non-conjugated polyene copolymer by the light scattering method with the viscosity average molecular weight M _v. Ask. [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 above-mentioned ethylene / α-olefin /
The non-conjugated polyene random copolymer may be modified with a polar monomer, and details of this modified product will be described later. Production Method In the present invention, using a specific metallocene-based catalyst as shown below, (a) ethylene, (b) an α-olefin having 3 or more carbon atoms, and (c) By random copolymerization with the conjugated polyene, the above ethylene / α-olefin / non-conjugated polyene random copolymer is obtained.

The metallocene catalyst used in the present invention is
It contains a specific [A] metallocene compound as described below. The metallocene catalyst used in the present invention is not particularly limited except that it contains the [A] metallocene compound, and for example, reacts with the metallocene compound [A] and the organoaluminum oxy compound [B] and / or [A]. And a compound [C] which 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].

[0044]

[Chemical 2]

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, arylalkyl groups such as benzyl, phenylethyl, 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 and iodine, or an organic silyl group such as trimethylsilyl, triethylsilyl and triphenylsilyl. As the silicon-containing group, monohydrocarbon-substituted silyl such as methylsilyl and phenylsilyl, dihydrocarbon-substituted silyl such as dimethylsilyl and diphenylsilyl, trimethylsilyl and triethylsilyl,
Trihydrocarbyl-substituted silyl such as tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl; silyl ether of hydrocarbon-substituted silyl such as trimethylsilyl ether; trimethylsilylmethyl, etc. And a silicon-substituted aryl group 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). As the oxygen-containing group,
Examples thereof 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.

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). Examples of the sulfur-containing group include a substituent in which oxygen of the oxygen-containing compound is substituted with sulfur, and methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate. Sulfonate groups such as phonate, triisobutylbenzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate, methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate , Trimethylbenzenesulfinate, pentafluorobenzenesulfinate, and other sulfinate groups.

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

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, or 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 and 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-
Propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene and other alkylsilylene groups, 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. Among these, a substituted silylene group such as a dimethylsilylene group, a diphenylsilylene group, and a methylphenylsilylene group is particularly preferable.

R ¹⁵ is the same halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms as described above. Of these, a divalent silicon-containing group and a divalent germanium-containing group are preferable,
A divalent silicon-containing group is preferable, and alkylsilylene, alkylarylsilylene, and 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. 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, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1 -(2,7-Dimethyl-4-
n-pentylindenyl)} zirconium dichloride, ra
c-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-phenyl) Ethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2,7-dimethyl-4-chloromethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-trimethylsilylmethylindenyl) } Zirconium dichloride,
rac-Dimethylsilylene-bis {1- (2,7-dimethyl-4-trimethylsiloxymethylindenyl)} zirconium dichloride, rac-diethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindene Nyl)} 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, r
ac-di (p-tolyl) silylene-bis {1- (2,7-dimethyl-4
-i-Propylindenyl)} zirconium dichloride, r
ac-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-chloro) Methylindenyl)} 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-diphenyl Silylene-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- Four-
i-Propylindenyl)} zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium dimethyl, ra
c-Dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium methyl chloride, rac-dimethylsilylene-bis {1- (2-methyl-4-i-
Propyl-7-methylindenyl)} 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 compounds 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 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 prepared by a known method from the indene derivative, for example, JP-A-4-26830.
It can be synthesized by the method described in JP-A-7. In the present invention, as the metallocene compound [A], E
The compounds represented by the following formula [II] described in P-549900 and Canada-2084017 can also be used.

[0060]

[Chemical 3]

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 each is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 carbon atom.
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. ,

[0062]

[Chemical 4]

= 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 halogen (halogenated) is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, in particular a fluorine atom or a chlorine atom.

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 as 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, and an alkoxy group having 1 to 10 carbon atoms, preferably 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 as 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.

[0066]

[Chemical 5]

= 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,
The residues R ²¹ are the same as each other and are an alkyl group having 1 to 4 carbon atoms, and R ^{22 to} R ²⁸ may be the same or different from each other, and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. , And Z is

[0069]

[Chemical 6]

(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. 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 Is a hydrogen atom, R ^{23 to} R ²⁷ may be the same or different, is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and Z is

[0072]

[Chemical 7]

(M ² is silicon, R ²⁹ and R ³⁰ may be the same or different from each other, and are 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 as follows: M is zirconium, X ³ and X ⁴ are chlorine atoms, the residue R ²¹ is a methyl group,
R ^{22 to} R ²⁸ are hydrogen atoms, and Z is

[0074]

[Chemical 8]

(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-acenaphthocyclopentadienyl) ) 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, and 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 directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran to recover it as 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. Further, the solvent or the unreacted organoaluminum compound may be removed by distillation from the recovered aluminoxane solution, 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 and triisobutylaluminum.
sec-Butyl aluminum, tri-tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum and other trialkyl aluminum, tricyclohexyl aluminum, tricyclooctyl aluminum and other tricycloalkyl aluminum, dimethyl aluminum chloride Dialkyl aluminum halides such as diethyl aluminum chloride, diethyl aluminum bromide and diisobutyl aluminum chloride, dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride, dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide, diethyl Examples thereof include dialkylaluminum aryloxides such as aluminum phenoxide.

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. As the solvent used in the production of aluminoxane, for example, benzene,
Aromatic hydrocarbons such as toluene, xylene, cumene and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane, and fats such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane Aromatic hydrocarbons, petroleum fractions such as gasoline, kerosene, and light oil, and halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, especially hydrocarbon solvents such as chlorinated compounds and brominated compounds. To be

Further, ethers such as ethyl ether and tetrahydrofuran can be used. Of these solvents, aromatic hydrocarbons are particularly preferable. You may use the said organoaluminum oxy compound [B] in combination of 2 or more types. [C] Reacts with metallocene compound [A] to form an ion pair
The compound [C] which forms an ion pair by reacting with the metallocene compound [A] used in the present invention is described in JP
501950 gazette, special table 1-502036 gazette,
JP-A-3-179005, JP-A-3-17900
No. 6, JP-A-3-207703, and 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 serves to stabilize the transition metal cation species by reacting with the metallocene compound [A] to cationize the metallocene compound [A] and to form 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) Mention may also be made of (phenyl) borate. Moreover, the following compounds can also be illustrated. (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, bis [tris] (N-Butyl) ammonium] decaborate, Bis [tri (n-butyl) ammonium] undecaborate, Bis [tri (n-butyl) ammonium] dodecaborate, Bis [tri (n-butyl) ammonium] decachlorodecaborate , Bis [tri (n-butyl) ammonium] dodecachlorododecaborate, tri (n-butyl)
Ammonium-1-carbadecaborate, tri (n-butyl) ammonium-1-carbaundecaborate, tri (n-)
-Butyl) ammonium-1-carbadodecaborate, tri (n-butyl) ammonium-1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo
-1-carbadodecaborate and the like; further borane compounds,
A carborane compound etc. can be mentioned. These compounds are used as Lewis acids and ionic compounds.

Borane and carborane complex compounds and salts of carborane anions, such as decaborane (14), 7,
8-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-carbaundecaborate (13), tri (n-butyl) ammonium
7,8-dicarbaundecaborate (12), tri (n-butyl) ammonium 2,9-dicarbaundecaborate (1)
2), tri (n-butyl) ammonium dodecahydride-8-methyl 7,9-dicarbaundecaborate, tri (n-
Butyl) ammonium undeca hydride-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- Carbalane and carborane salts, 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.) A salt of a metal carborane and a metal borane anion, for example, tri (n-butyl) ammonium bis (nona). Hydride
-1,3-Dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) ferrate (ferrate) (III), tri (n) -Butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate)
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 (dodeca hydride dicarbadodecaborate) Cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodeca hydride 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] and 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) (wherein 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,
Trioctylaluminum, trialkylaluminums such as 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.

As the organoaluminum compound [D], a compound represented by the following formula (b) can also be used. R ⁴⁰ _n AlY _3-n (b) (In the formula, R ⁴⁰ is the same as above, Y is an —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, etc., and R ⁴⁴ is a hydrogen atom, a methyl group, an ethyl group. 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 _n Al (OR ⁴¹ ) _3-n , such as dimethylaluminum methoxide,
Diethyl aluminum ethoxide, diisobutyl aluminum methoxide, etc. (ii) a compound represented by R ⁴⁰ _n Al (OSiR ⁴² ₃ ) _3-n , such as (C ₂ H ₅ ) ₂ Al (OSi (CH ₃ ) ₃ ),
(Iso-C ₄ H ₉ ) ₂ Al (OSi (CH ₃ ) ₃ ), (iso-C ₄
Etc. _{H 9) 2 Al (OSi (} C 2 H 5) 3).

(Iii) a compound represented by R ⁴⁰ _n Al (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 _n Al (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 )), (CH ₃ ) ₂
Al (NH (C ₂ H ₅ )), (C ₂ H ₅ ) ₂ Al [N (Si
_{(CH 3) 3) 2]} , (iso-C 4 H 9) 2 Al [N (Si (C
H ₃ ) ₃ ) ₂ ] etc.

(V) A compound represented by R ⁴⁰ _n Al (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 A
l, R ⁴⁰ _n Al (OR ⁴¹ ) _3-n , R ⁴⁰ _n Al (OAlR ⁴³
₂ ) An organoaluminum compound represented by _3-n can be mentioned as a preferable example, and a compound in which R ⁴⁰ is an isoalkyl group and n = 2 is particularly preferable. These organoaluminum compounds may 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 organoaluminum 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 used.
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. In the organoaluminum oxy compound [B], the aluminum atom is usually about 1 to 1 mol of the transition metal atom.
It can be used in an amount of 10,000 mol, preferably 10 to 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 usually added to 1 mol of the boron atom in the aluminum atom in the organoaluminum oxy compound [B] or in the compound [C] forming an ion pair.
It can be optionally used in an amount of about 0 to 1000 mol, preferably about 0 to 500 mol.

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. It is sufficient to copolymerize (a) ethylene, (b) an α-olefin having 3 or more carbon atoms, and (c) a non-conjugated polyene using a Group VB transition metal compound catalyst such as a vanadium catalyst. A random copolymer cannot be obtained due to polymerization activity. Further, using a Group VB transition metal compound-based catalyst, for example, EB
When producing DM and the like, the type of the non-conjugated polyene (c) is often limited to norbornene ring-containing polyenes such as ENB. On the other hand, when the 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 those described above such as MOD Non-conjugated polyenes can also be copolymerized.

In the present invention, (a) ethylene, (b) an α-olefin having 3 or more carbon atoms, and (c) a non-conjugated polyene are copolymerized, and the above-mentioned IV which constitutes a 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. You may use these in combination.

The Group IVB metallocene compound [A], the organoaluminum oxy compound [B], the ion pair-forming compound [C] and the 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, (a)
Ethylene and (b) an α-olefin having 3 or more carbon atoms,
(c) The copolymerization with the non-conjugated polyene is usually 40 to 200 ° C.
It is preferably 50 to 150 ° C., particularly preferably 60 to 120.
At atmospheric pressure to 100 kg / cm ^2, preferably atmospheric pressure to 50
kg / cm ² and particularly preferably 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, as the polymerization solvent, the above-mentioned hydrocarbon solvent can be used. 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, the above specific random copolymer 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 can be adjusted. It can also be adjusted by controlling the amount of the (molecular weight modifier) used. The product immediately after the 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, a vinyl ester compound, and a chloride. Examples include vinyl.

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.

[0106]

[Chemical 9]

(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-mentioned 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, N-dimethylacrylamide, N, N-
Allylamine derivatives such as dimethylaminopropyl acrylamide Acrylamide derivatives such as N-methyl acrylamide Aminostyrenes such as p-aminostyrene 6-Aminohexyl succinimide, 2-
Examples include aminoethyl succinimide.

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, 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.

[0110]

[Chemical 10]

(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, and preferably 1 Is an integer of 5 to 5.) Examples of such an aromatic vinyl compound 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, n-vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate, pt- Examples thereof include vinyl butyl benzoate, vinyl salicylate, vinyl cyclohexanecarboxylate and the like.

Preparation of Modified Random Copolymer The modified random copolymer according to the present invention is obtained by graft-polymerizing a polar monomer onto the above random copolymer. When the polar copolymer as described above is graft-polymerized to the random copolymer, 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. As the organic peroxide, for example, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,
5-bis (t-butylperoxy) hexane, 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 Examples thereof include peroxide, 2,4-dichlorobenzoyl peroxide, m-toluyl peroxide and the like.

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. This 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, dimethyl ether, diethyl ether, such as ethyl acetate and dimethyl phthalate, di -n- amyl ether, can be used ether solvents such as tetrahydrofuran and dioxy anisole.

When 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. As a reducing substance, iron (II)
Ions, chromium ions, cobalt ions, nickel ions, palladium ions, sulfite, hydroxylamine, hydrazine, further -SH, SO ₃ H, -NHN
Examples thereof include compounds containing groups such as H ₂ and —COCH (OH) —.

Specific examples of such reducing substances include ferrous chloride, potassium dichromate, cobalt chloride,
Cobalt naphthenate, palladium chloride, ethanolamine, diethanolamine, N, N-dimethylaniline, hydrazine, ethyl mercaptan, benzenesulfonic acid, p-
Examples include toluene sulfonic acid. In the present invention, the reducing substance is based on 100 parts by weight of the random copolymer,
Usually, it can be used in an amount of 0.001 to 5 parts by weight, preferably 0.1 to 3 parts by weight.

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. 70
At a temperature of ~ 200 ° C, preferably 80-190 ° C.
The reaction can be carried out for 5 to 15 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. A modified random copolymer can also be produced by reacting a random copolymer with a polar monomer in the absence of solvent using an extruder or the like.

This reaction is usually carried out at a temperature not lower than the melting point of the random copolymer, specifically at a temperature of 120 to 250 ° C.
It is desirable to be performed for 5 to 10 minutes. The modified amount of the modified random copolymer thus obtained (the amount of the polar monomer grafted) is usually 0.1 to 50% by weight, preferably 0.2 to 30% by weight.

Vulcanizable Rubber Composition The vulcanizable rubber composition according to the present invention containing the ethylene / α-olefin / non-conjugated polyene random copolymer as described above is used even when it is unvulcanized. 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 using 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 may appropriately contain other components according to the purpose together with the ethylene / α-olefin / non-conjugated polyene random copolymer. It is desirable to contain the olefin / non-conjugated polyene random copolymer in an amount of 20% by weight or more, preferably 25% by weight or more, based on the total rubber composition.

As other components, for example, a reinforcing agent,
Inorganic fillers, softeners, antioxidants (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 thereof 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 silicate and the like.

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. Further, when the inorganic filler is blended in the above amount, the hardness can be increased without impairing other physical properties of the vulcanized rubber, and the cost can be reduced. As a softening agent, a softening agent that has been conventionally compounded in rubber is widely used. Specifically, a petroleum-based softening agent such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and petrolatum, coal tar, Coal tar type softeners such as coal tar pitch, fatty oil type softeners such as castor oil, linseed oil, rapeseed oil and coconut oil, tall oil, sub, beeswax, carnauba wax, lanolin and other waxes,
Ricinoleic acid, palmitic acid, barium stearate,
Fatty acids and fatty acid salts such as calcium stearate and zinc laurate, synthetic polymer substances such as petroleum resin, atactic polypropylene and coumarone indene resin are used.

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 life of the material 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 Phenol 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 stabilizers such as sulfides, benzimidazole stabilizers such as 2-mercaptobenzimidazole, dithiocarbamate stabilizers such as nickel dibutyldithiocarbamate, polymerization of 2,2,4-trimethyl-1,2-dihydroquinoline Examples include quinoline-based stabilizers for products. Two or more of these may be used in combination.

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 blended with rubber as the processing aid can be widely used. In particular,
Acids such as ricinoleic acid, stearic acid, palmitic acid, lauric acid and the like, salts of these higher fatty acids such as barium stearate, zinc stearate, calcium stearate or esters can be mentioned.

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. When the rubber composition according to the present invention is vulcanized by heating, a compound that constitutes a vulcanizing system such as a vulcanizing agent, a vulcanization accelerator, and a vulcanization aid is usually added to the rubber composition. Compound.

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. As sulfur compounds,
Specific examples thereof include sulfur chloride, sulfur dichloride, polymer 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-butylperoxine) 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. You may use these in combination of 2 or more types.

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 added 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 can be used in an amount of 0.0003 to 0.05 mol, preferably 0.001 to 0.03 mol, based on 100 g of the ethylene / α-olefin / non-conjugated polyene random copolymer.

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 (CBS), N-oxydiethylene-2-benzothiazole sulfenamide, N, N-diisopropyl-2-benzothiazole sulfoneamide. Sulfenamide compounds such as phenamide, 2-mercaptobenzothiazole (MBT), 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole, Thiazole compounds such as dibenzothiazyl disulfide, diphenylguanidine, triphenylguanidine, diorsonitrile guanidine, orthonitrile biguanide, guanidine compounds such as diphenylguanidine phthalate, acetaldehyde-aniline reaction product, butyraldehyde-aniline condensate, hexa Methylene tet Aldehyde amines or aldehydes such as lamin and acetaldehyde ammonia
Ammonia compounds, imidazoline compounds such as 2-mercaptoimidazoline, thiocarbanilide, diethyl thiourea, dibutyl thiourea, trimethyl thiourea, thiourea compounds such as diorsotolyl thiourea, tetramethyl thiuram monosulfide, tetramethyl thiuram disulfide ( TMTD), tetraethylthiuram disulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide, thiuram-based compound such as dipentamethylenethiuram tetrasulfide (DPTT), zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, di-n-butyldithiocarbamate Zinc, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, dimethyldithiocarbamine Sodium dimethyl dithiocarbamate selenium, dithio acid salt-based compounds such as dimethyl dithiocarbamate tellurium, xanthate-based compound such as dibutyl xanthate zinc, zinc flower and the like.

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. When an organic peroxide is used as a vulcanization aid (a polyfunctional monomer) or a vulcanization agent, the vulcanization aid (a polyfunctional monomer) is added in an amount of 0.5 to 2 with respect to 1 mol of the organic peroxide. It is preferable to use them in a molar amount, preferably in an approximately equimolar amount.

As the vulcanization aid, specifically, sulfur,
quinonedioxime compounds such as p-quinonedioxime,
(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, among 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 The rubber composition according to the present invention can be foam-molded when it contains a compound constituting a foaming system such as a foaming agent or a foaming auxiliary.

As the foaming agent, a foaming agent generally used in 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, azocyclohexyl nitrile, azo compounds such as azodiaminobenzene, 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 .

A foaming aid can be used together with the foaming agent. When the foaming aid is used in combination, the effects of lowering the decomposition temperature of the foaming agent, promoting decomposition, homogenizing bubbles, etc. Examples of such foaming aids include organic acids such as salicylic acid, phthalic acid, stearic acid, and oxalic acid, and urea or its derivatives. The foaming aid can 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 ethylene / α-olefin / 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. As such other rubber, natural rubber (N
R), isoprene rubber such as isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (N
Examples thereof include conjugated diene rubbers such as BR) and chloroprene rubber (CR).

Further, conventionally known ethylene / α-olefin copolymer rubbers can 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, etc. can also be kneaded simultaneously.

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 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 contains 0.1 to 10 MeV, preferably 0.3 to
The absorbed dose of an electron beam having an energy of 2 MeV is 0.5 to 35 Mrad, preferably 0.5 to 10 Mrad.
Irradiate so that

A mold may or may not be used in the 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.

[0151]

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 an α-olefin having 3 or more carbon atoms, which 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 is excellent in polymerization activity at high temperatures, so that an ethylene / α-olefin / non-conjugated polyene random copolymer is efficiently prepared. It can be manufactured.

Ethylene α-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 has mechanical strength,
Excellent weather resistance, ozone resistance, workability, etc., and also excellent cold resistance (low temperature flexibility) and heat resistance.

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

[0154]

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).
It was measured in C). The glass transition temperature Tg is an index of low temperature flexibility of the ethylene / α-olefin / non-conjugated polyene random copolymer.・ Measure Tg by DSC 180 from room temperature (25 ℃) to 20 ℃ / 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.

[0156]

[Chemical 11]

[0157]

Example 1 Zirconium compound and methylalumoxane
Preliminary contact with, 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) were placed in a dark place at room temperature for 30 minutes. Mixing was performed by stirring for a minute to prepare a toluene solution in which the zirconium compound A and methylalumoxane were dissolved. 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) overlap Using a 15-liter stainless steel polymerization vessel equipped with a stirring blade, ethylene, 1-butene and 7-methyl-1,6 were continuously added.
-Copolymerized with octadiene as follows.

First, from the top 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 upper part of the polymerization vessel, ethylene was added at the rate of 20 per hour.
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, and the copolymer was separated from the solvent by steam stripping treatment, and then at 100 ° C. under reduced pressure (100 mmHg). Then, 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. The results are shown in Table 2.

[0163]

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. The results are shown in Table 2.

[0164]

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. The results are shown in Table 2.

[0165]

[Table 1]

[0166]

[Table 2]

[0167]

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. 7-methyl-1,6-octadiene (MO
D) hexane solution (concentration 36 g / liter) 0.5 liter / hour, and VO (OC ₂ H ₅ ) Cl ₂ hexane solution (concentration 8 mmol / liter) 0.5 hour / hour as a catalyst.
5 liters, ethyl aluminum sesquichloride [Al
A solution of (C ₂ H ₅ ) _1.5 Cl _1.5 ] in hexane (concentration: 64 mmol / l) was supplied at a rate of 0.5 liter per hour, and hexane was further supplied at a rate of 0.5 liter per hour. The polymerization solution therein was continuously withdrawn so that the polymerization solution was always 1 liter.

In the 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. The 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, and the polymer was deposited at 100 ° C. for 24 hours. It was dried under reduced pressure.

As described above, 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.

[0171]

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 hourly rate 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, and the copolymer was separated from the solvent by steam stripping treatment, and then at 100 ° C. under reduced pressure (100 mmHg). Then, 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.

[0176]

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.

[0177]

[Table 3]

[0178]

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 ) The aging test was carried out by air heating aging test at 125 ° C. for 70 hours, and the retention rate to the physical properties before aging, that is, the tensile strength retention rate AR (T _B ), elongation retention AR (E _B ), and hardness change A _H (JIS A) were determined.

(4) Compression set test (CS) The compression set test was conducted in accordance with 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.

[0183]

[Table 4]

[0184]

[Table 5]

[Brief description of drawings]

FIG. 1 is an explanatory view 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.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Tetsuo Tojo             3 Chikusaigan, Ichihara, Chiba Prefecture Mitsui Chemicals Stock Association             In-house (72) Inventor Toshihiro Aine             Mitsui 6-1-2 Waki, Waki Town, Kuga District, Yamaguchi Prefecture             Inside Chemical Co., Ltd. (72) Inventor Toshiyuki Tsutsui             Mitsui 6-1-2 Waki, Waki Town, Kuga District, Yamaguchi Prefecture             Inside Chemical Co., Ltd. (72) Inventor Hidenori Nakahama             3 Chikusaigan, Ichihara, Chiba Prefecture Mitsui Chemicals Stock Association             In-house F-term (reference) 4J002 AE05X AG00X BA01X BB05W                       BB14W BB15W BB17W BB19W                       DA036 DE047 DE236 DJ006                       DJ016 DJ046 EF057 EG037                       FB096 FD016 FD027 GL00                       GM00 GN00 GQ01                 4J100 AA02P AA02R AA03Q AA04Q                       AA07Q AA09Q AA15Q AA16Q                       AA17Q AA18Q AA19Q AA21Q                       AB16Q AR16R AR22R AS11R                       AS13Q AS15Q CA05 DA09                       DA24 DA31 DA36 DA47 DA48                       DA51 JA28 JA44 JA67

Claims (7)

[Claims] 1. A unit derived from (i) (a) ethylene and (b) a unit derived from an α-olefin having 3 to 20 carbon atoms are 40/60 to 95/5 [(a) / ( b)] in a molar ratio of (ii) iodine value of 1 to 50, and (iii) 135 ° C.
The intrinsic viscosity [η] measured in decalin is 0.1 to 8.
A 0DL / g, obtained from (iv) ¹³ C-NMR intensity ratio of Tiarufabeta for Tiarufaarufa in the spectrum D (Tαβ / Tαα) is 0.5 or less, (v) ¹³ C-NMR spectrum and the following formula B value is from 1.00 to 1.50; B value = [P _OE ] / (2 · [P _E ] · [P _O ]) (where [P _E ] is in the random copolymer) (A) is the molar fraction of the units derived from ethylene, [P _O ] is the molar fraction of the units derived from the (b) α-olefin in the random copolymer, [P _OE ] Is the total dyad (dy
ad) is the ratio of α-olefin / ethylene chain number to the chain number), and (vi) the glass transition temperature Tg determined by DSC is -50 ° C or less, ethylene / α-olefin / non Conjugated polyene random copolymer. 2. The (b) α-olefin has 4 to 1 carbon atoms.
The ethylene / α-olefin / non-conjugated polyene random copolymer according to claim 1, wherein the random copolymer is 0-α-olefin. 3. The (b) α-olefin is an α-olefin having 8 carbon atoms.
An ethylene / α-olefin / non-conjugated polyene random copolymer according to claim 1, which is an olefin. 4. A vulcanizable rubber composition comprising the ethylene / α-olefin / non-conjugated polyene random copolymer according to any one of claims 1 to 3. 5. 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 the ethylene / α-olefin / non-conjugated polyene random copolymer. The rubber composition according to claim 4. 6. The softening agent is contained in an amount of 10 to 200 parts by weight, based on 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene random copolymer, according to claim 4 or 5. The rubber composition described. 7. A vulcanized rubber obtained from the vulcanizable rubber composition according to any one of claims 4 to 6.