JP3483176B2 - Ethylene / α-olefin / non-conjugated polyene random copolymer and use of the copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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 method. Represents ethylene, α-olefin and non-conjugated polyene,
A method for producing an ethylene / α-olefin / non-conjugated polyene random copolymer which can be copolymerized with high activity, and with a high conversion of an α-olefin with 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, excellent flexibility at low temperatures, and excellent heat aging resistance.

[0002] The present invention also relates to the use of the above-mentioned ethylene / α-olefin / non-conjugated polyene random copolymer.

[0003]

BACKGROUND OF THE INVENTION Ethylene / propylene copolymer rubber (E) which is a random copolymer of ethylene and propylene
PM) or 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 molecular structure without heat and is superior in heat resistance and weather resistance compared to general-purpose conjugated diene rubber, so it is widely used for automotive parts, electric wire materials, building civil engineering materials, industrial material parts, etc. It's being used.

[0004] Such an ethylene / α-olefin rubber is usually used after vulcanization. However, the properties of the vulcanized rubber vary depending on the ethylene component content, molecular weight, iodine value and the like. Different values are used.

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

[0006] Among rubber applications, anti-vibration rubbers for brake parts, engine mounts, and the like are required to have particularly high heat resistance and low-temperature flexibility. However, with the conventionally known EPM or EPDM, it is possible to obtain a vulcanizate that satisfies both the heat resistance and the low-temperature flexibility required for the vibration damping rubber even when the ethylene component content, molecular weight, iodine value, etc. are changed. Is difficult, EPM or EPD
M was rarely used in such applications.

For this reason, the above-mentioned problems have been improved.
There has been a demand for 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, such ethylene / α-olefin / non-conjugated polyene copolymers, particularly ethylene / α-olefin / non-conjugated polyene copolymers having 4 or more carbon atoms, have been desired, although their appearance has been desired. As described above, it is difficult to manufacture, and it has not existed before.

The above-mentioned ethylene / propylene / non-conjugated diene random copolymer (EPDM) has been conventionally produced using a vanadium-based catalyst. However, in the presence of a known vanadium-based 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),
Even when an attempt is made to copolymerize with methyl-1,6-octadiene (hereinafter also referred to as MOD) or the like, 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 has been difficult to industrially produce non-conjugated polyene random copolymers.

Further, when ethylene, an α-olefin and the above-mentioned ENB or MOD are copolymerized using a solid titanium-based catalyst known as a catalyst for producing polyethylene and polypropylene, the composition distribution becomes wide, A copolymer having inferior vulcanization properties was obtained, and in the case of solution polymerization, components having a high ethylene content were precipitated, and it was difficult to carry out the polymerization in a uniform solution state.

Japanese Unexamined Patent Publication (Kokai) No. 2-51512 discloses an unsaturated ethylene / α-olefin random copolymer which can be vulcanized at a higher speed than a conventional unsaturated ethylene / α-olefin random copolymer. It is disclosed in
Japanese Patent Application No. -64111 describes a method for producing high-molecular-weight EPDM with low crystallinity by slurry polymerization using a catalyst comprising a metallocene compound of titanium, zirconium or hafnium and alumoxane.

However, in each of these publications, ethylene, an α-olefin having 4 or more carbon atoms, and a non-conjugated polyene are copolymerized with high activity, resulting in a narrow composition distribution, excellent mechanical strength, low-temperature flexibility and heat resistance. Ethylene with excellent aging properties
There is no indication that an α-olefin / non-conjugated polyene random copolymer is obtained.

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

Therefore, ethylene, α-olefin having 3 or more carbon atoms and non-conjugated polyene can be copolymerized with high activity, α-olefin with high conversion, and excellent random copolymerizability. In addition, the emergence of a production method capable of producing an ethylene / α-olefin / non-conjugated polyene random copolymer having a narrow composition distribution, a high molecular weight, and excellent flexibility at low temperatures and heat aging resistance. Is desired.

[0014]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has been made in consideration of ethylene and α-α having 3 or more carbon atoms.
Olefin and non-conjugated polyene are highly active, and α-olefins can be copolymerized with a high reaction rate and with excellent random copolymerizability, and a high molecular weight copolymer can be obtained. A method for producing an olefin / non-conjugated polyene random copolymer, and an ethylene / α-olefin / non-conjugated polyene random excellent in low-temperature flexibility and heat aging resistance having a narrow composition distribution and excellent mechanical strength obtained by the production method It is intended to provide a copolymer.

Further, the present invention relates to an ethylene
The purpose of the present invention is to provide applications of α-olefin / non-conjugated polyene random copolymers, especially containing such copolymers, and having excellent mechanical strength, weather resistance and ozone resistance, and also cold resistance (low temperature flexibility). It is another object of the present invention to provide a vulcanizable rubber composition having excellent heat resistance.

[0016]

SUMMARY OF THE INVENTION The ethylene / α-olefin / non-conjugated polyene random copolymer according to the present invention comprises: (i) a unit derived from (a) ethylene; and (b) an α-olefin having 4 to 10 carbon atoms. And (ii) the iodine value is 12 to 50, and (iii) measured in decalin at 135 ° C. The derived unit is contained in a molar ratio of 40/60 to 95/5 [(a) / (b)]. Limiting viscosity [η]
Is 1.6 to 6 dl / g, and (iv) T to Tαα in the ¹³ C-NMR spectrum.
αβ intensity ratio D (Tαβ / Tαα) is 0.5 or less; (v) 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 ]) (where [P _E ] is the content mole fraction of units derived from (a) ethylene in the random copolymer, [P _O ]
Is the mole fraction of 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.
(Vi) the glass transition temperature Tg determined by DSC is −50 ° C.
And the non-conjugated polyene is an alicyclic polyene or an aromatic polyene. Such an ethylene / α-olefin / non-conjugated polyene random copolymer of the present invention can be obtained by (a) in the presence of a metallocene-based catalyst containing a racemic metallocene compound represented by the following formula [I] or [II]: ) It is preferable to be obtained by random copolymerizing ethylene, (b) an α-olefin having 4 to 10 carbon atoms, and (c) a non-conjugated polyene.

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

[0018]

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

[0020]

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(Wherein M is a transition metal of Group IVB of the periodic table, X ³ and X ⁴ may be the same or different and each represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, An alkoxy group having 1 to 10, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, 2-1
0 alkenyl group, C 7-40 arylalkyl group, C 7-40 alkylaryl group, C 8-8
And R ²¹ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, an optionally halogenated alkyl group having 1 to 10 carbon atoms, a carbon atom Aryl groups of the formulas 6 to 10, or -NR ₂ , -SR, -OSiR ₃ , -Si
R ₃ or —PR ₂ groups (R is a halogen atom, having 1 to 1 carbon atoms)
R ^{22 to} R ²⁸ are the same as R ²¹ described above, or adjacent R ^{22 to} R ²⁸ together with the atoms to which they are bonded, May form an aromatic- or aliphatic ring,

[0022]

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= 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, C1-C10 alkyl group, C1-C10 fluoroalkyl group, C6-C6
An aryl group having 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,
An arylalkenyl group having 8 to 40 carbon atoms or 7 carbon atoms
An alkylaryl group of 基 40 or R ²⁹ and R ³⁰
And may each form a ring with the atoms to which they are attached, and M ² is silicon, germanium or tin. ).

[0024]

[0025]

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

[0027]

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

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

This (b) has 3 or more carbon atoms, specifically 3 carbon atoms.
Examples of the α-olefin of -20 to -20 include propylene, 1-butene, 1-pentene, 1-hexene, and 3-methyl-1-
Butene, 3-methyl-1-pentene, 3-ethyl-1-pentene,
4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl
-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,
Examples include 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 preferably used. As (c) 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-d 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 polyene such as methyl-1,6-undecadiene, 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. In the present invention, among these, a non-conjugated polyene having 7 or more carbon atoms is 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; (b) a unit derived from an α-olefin having 3 or more carbon atoms (hereinafter sometimes simply referred to as (b) α-olefin) is 40/60 to 95/5, preferably 55/45.
９０90/10 [(a) / (b)].

When this random copolymer is used by blending it with a conjugated diene rubber, the above (a) /
(b) The molar ratio is preferably from 65/35 to 80/20. From the random copolymer having such a component ratio and the conjugated diene rubber, the rubber has excellent mechanical strength, A rubber composition that can exhibit 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 at 135 ° C. in decalin of 0.1 to 8.0 dl / g. Preferably 0.2 to 6 dl
/ G.

When this random copolymer is used by blending with a conjugated diene rubber, the intrinsic viscosity [η]
Is particularly preferably 0.3 dl / g <[η] <5 dl / g. The random copolymer having such an intrinsic viscosity [η] is excellent in the blending property (compatibility) with the conjugated diene-based rubber, and has a mechanical strength characteristic from the random copolymer and the conjugated diene-based rubber. It is possible to obtain a vulcanizable rubber composition which is excellent in heat resistance and weather resistance.

(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 a ¹³ C-NMR spectrum of 0.5 or less. It is. The strength ratio D value of the random copolymer varies depending on the kind 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 (b) peak intensities of CH _{2 in} a unit derived from an α-olefin having 3 or more carbon atoms, and two types of CH ₂ having different positions with respect to the tertiary carbon as shown below. Means.

[0039]

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The strength ratio D of the random copolymer can be determined as follows. ¹³ C of random copolymer
-NMR spectrum is measured using, for example, JE
Using an OL-GX270 NMR measuring apparatus, hexachlorobutadiene / d ₆ -benzene = 2 at a sample concentration of 5% by weight was used.
/ 1 (volume ratio) mixed solution at 67.8 MHz, 25 ° C.
Is measured on the basis of d ₆ -benzene (128 ppm).

The analysis of the ¹³ C-NMR spectrum is basically based on the proposal of Lindemann Adams (Analysis Chemistry 43,
p1245 (1971)), JCRandall (Review Macromolecular
Chemistry Physics, C29, 201 (1989)).

Here, the above-mentioned strength ratio D will be described more specifically by taking an ethylene / 1-butene / 7-methyl-1,6-octadiene random copolymer as an example. In the ¹³ C-NMR spectrum of this ethylene / 1-butene / 7-methyl-1,6-octadiene random copolymer, peaks appearing at 39 to 40 ppm belong to Tαα, and peaks appearing at 31 to 32 ppm belong to Tαβ. Is done.

The intensity ratio D is calculated from the integrated value (area) ratio of each peak portion. The intensity ratio D thus determined is generally the ratio of the occurrence of the 1,1 addition reaction of 1-butene followed by the 2,1 addition reaction, or the ratio of 1-butene of 2,1 addition.
It is considered to be a scale indicating the rate at which 1,2 addition reactions occur after addition reactions. Therefore, it is shown that the larger the intensity ratio D value is, the more irregular the (b) the bonding direction of the α-olefin (1-butene) is. Conversely, the smaller the D value,
(b) It indicates that the bonding direction of the α-olefin is regular. If the regularity is high, the molecular chains are likely to assemble, and the random copolymer is preferable because the strength and the like tend to be excellent.

In the present invention, as will be 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 intensity 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, for example, the above intensity ratio D is 0.5 or less. Ethylene 1-
Butene-7-methyl-1,6-octadiene random copolymer cannot be obtained. This means that α other than 1-butene
-The same applies to olefins.

(V) B value The ethylene / α-olefin / non-conjugated polyene random copolymer has a ¹³ C-NMR spectrum and a B value obtained from the following formula of 1.0 to 1.5, preferably 1.02.
１1.50, more preferably 1.02 to 1.45, and particularly preferably 1.02 to 1.40.

B value = [P _OE ] / (2 · [P _E ] · [P _O ]) (where [P _E ] is the unit derived from (a) ethylene in the random copolymer) Content molar fraction, [P _O ]
Is the mole fraction of the unit 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)
Values are (a) ethylene and (b) in random copolymer
It is an index indicating the state of distribution with α-olefin, JC
Randall (Macromolecules, 15, 353 (1982)), J. Ray (M
acromolecules, 10,773 (1977)).

As the value B increases, the block chain of (a) ethylene or (b) α-olefin becomes shorter, the distribution of ethylene and α-olefin becomes more uniform, and the composition distribution of the random copolymer becomes larger. Is narrow. Note that the composition 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 will be described later,
By copolymerizing ethylene, an α-olefin having 3 or more carbon atoms and a non-conjugated polyene using a Group IVB metallocene compound, a random copolymer having the above B value of 1.0 to 1.50 is obtained. However, for example, even if ethylene, an α-olefin having 3 or more carbon atoms and a non-conjugated polyene are copolymerized in the presence of a titanium-based non-metallocene catalyst, ethylene / α-olefin / non- A conjugated polyene random copolymer cannot be obtained.

(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 less.

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

(Vii) gη ^* value The gη ^* value is the intrinsic viscosity [η] measured in the above (iii).
And the intrinsic viscosity [η] _blank of a linear ethylene-propylene copolymer having the same weight average molecular weight (by light scattering method) and an ethylene content of 70 mol% (gη ^* =
[Η] / [η] _blank ). The above [η]
_{The blank} is determined by replacing the weight average molecular weight _Mw of the ethylene / propylene non-conjugated polyene copolymer obtained by the light scattering method with the viscosity average molecular weight _Mv and calculating from the formula (I). _{[Η] blank = 7.2 × 10} -4 M v 0.667 ... (I)

The gη ^* value of the ethylene / α-olefin / non-conjugated polyene random copolymer desirably exceeds 0.9. The ethylene / α-olefin / non-conjugated polyene random copolymer as described above may be modified with a polar monomer. The modified product will be described later in detail.

[0053] In the manufacturing method of the present invention, by using a specific metallocene-based catalyst as shown below and (a) ethylene, and a (b) having 3 or more carbon α- olefin as described above, such as the ( c) A random copolymer of ethylene / α-olefin / non-conjugated polyene as described above is obtained by random copolymerization with a non-conjugated polyene.

The metallocene catalyst used in the present invention comprises:
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. For example, the metallocene compound [A] reacts with the organoaluminum oxy compound [B] and / or [A]. To form an ion pair with the compound [C] and further form [A], [B] and / or [C]
Together with the organoaluminum compound [D].

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

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

[0057]

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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 may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with halogen, a silicon-containing group,
An oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, or a phosphorus-containing group. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, propyl, n-butyl, isobutyl, sec-butyl, tert- Butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl, alkyl groups such as adamantyl, vinyl, propenyl, alkenyl groups such as cyclohexenyl, benzyl, phenylethyl, arylalkyl groups such as phenylpropyl, Phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, α- or β-naphthyl, methylnaphthyl, anthracenyl, phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, ace Ntorireniru, tetrahydronaphthyl, indanyl, and the like aryl groups such as biphenylyl.

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

Examples of the silicon-containing group include monohydrocarbon-substituted silyls such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl;
Trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, trinaphthylsilyl and other trihydrocarbon-substituted silyls, and hydrocarbon-substituted silyl and silyl such as trimethylsilyl ether Examples include a silicon-substituted alkyl group such as ether and trimethylsilylmethyl, and a silicon-substituted aryl group such as trimethylphenyl.

Further, as the silicon-containing group,-
SiR ₃ (where R is a halogen atom and carbon number 1 to 1)
An alkyl group having 10 or an aryl group having 6 to 10 carbon atoms).

Examples of the oxygen-containing group include a hydroxy group, an alkoxy group such as methoxy, ethoxy, propoxy and butoxy, an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy, and an arylalkoxy group such as phenylmethoxy and phenylethoxy. No.

Further, as the oxygen-containing group, -OSiR
₃ (where 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 has been replaced by sulfur, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, Trimethylbenzenesulfonate,
Sulfonate groups such as triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluorobenzenesulfonate, methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate, trimethylbenzene Sulfinate groups such as sulfinate and pentafluorobenzene sulfinate.

Further, as the sulfur-containing group,-
SR (where R is a halogen atom, having 1 to 10 carbon atoms)
An alkyl group or an aryl group having 6 to 10 carbon atoms)
And the group represented by

Examples of the nitrogen-containing group include an amino group, an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino, phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino. include an aryl amino group or alkylaryl amino groups, such as, -NR ₂ (but other than the as yet nitrogen-containing group, R represents a halogen atom, an alkyl group having 1 to 10 carbon atoms or carbon atoms, 6-10
An aryl group).

Examples of the phosphorus-containing group include dimethylphosphino, diphenylphosphino and the like. Further, as the phosphorus-containing group, other than the above, -PR ₂ (provided that R
Is 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).

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

R ¹³ and R ¹⁴ R ¹³ and R ^{14 each} have 1 to 2 carbon atoms as exemplified above.
0 alkyl groups, which 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, and each represents 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. group, a silicon-containing group, an oxygen-containing group or a sulfur-containing group, which specifically is 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.

[0071] Y Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, 1 to carbon atoms
20 divalent halogenated hydrocarbon groups, divalent silicon-containing groups, divalent germanium-containing groups, divalent tin-containing groups,-
O -, - CO -, - S -, - SO -, - SO 2 -, - N
R ^15- , -P (R ¹⁵ )-, -P (O) (R ¹⁵ )-, -B
R ¹⁵ — or —AlR ¹⁵ — (where R ¹⁵ is a hydrogen atom,
A halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen, or an alkoxy group).
Specifically, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-
Divalent hydrocarbon groups having 1 to 20 carbon atoms such as alkylene groups such as tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene, and arylalkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene , A halogenated hydrocarbon group obtained by halogenating a divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene, silylene, methylsilylene, dimethylsilylene, diethylsilylene, di (n-
Alkylsilylene groups such as propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene, and alkylarylsilylene groups , Arylsilylene group, tetramethyl-1,2-disilyl, tetraphenyl-1,2-
Examples thereof include a divalent silicon-containing group such as an alkyldisilyl group such as disilyl, an alkylaryldisilyl group, and an aryldisilyl group, and a divalent group in which silicon of the divalent silicon-containing group is substituted with germanium or tin.

Further, as the divalent silicon-containing group, the divalent germanium-containing group, and the divalent tin-containing group, the following formula [I
Examples of the group represented by Z in I] include a group containing any one of silicon, germanium, and tin.

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

Of these, divalent silicon-containing groups, 2
It is preferably a divalent germanium-containing group, more preferably a divalent silicon-containing group, and even more preferably an alkylsilylene, an alkylarylsilylene, or an arylsilylene.

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, ra
c-dimethylsilylene-bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-pentylindene) Nil)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-n-hexylindenyl)｝ zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-cyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-methylcyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-phenylethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-chloromethylindene) Nil)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-trimethylsilylmethylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4 -Trimethylsiloxymethylindenyl) zirconium dichloride, ra
c-Diethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (i-propyl) silylene-bis {1- (2,7-dimethyl-4) -i-
Propylindenyl) zirconium dichloride, rac-
Di (n-butyl) silylene-bis {1- (2,7-dimethyl-4-i-
Propylindenyl) zirconium dichloride, rac-
Di (cyclohexyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,7-dimethyl-4-i- Propylindenyl)｝ zirconium dichloride, rac-methylphenylsilylene-bis ｛1- (2,7-dimethyl-4-t-butylindenyl)｝ zirconium dichloride, rac-diphenylsilylene-bis ｛1- (2,7 -Dimethyl-4-t-butylindenyl) zirconium dichloride, rac-diphenylsilylene-bis {1- (2,7-dimethyl-
4-i-propylindenyl) zirconium dichloride,
rac-diphenylsilylene-bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride, rac-di (p-tolyl) silylene-bis {1- (2,7-dimethyl-4-i) -Propylindenyl)｝ zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis ｛1- (2,7-dimethyl-4-i-propylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1 -(2-methyl-4-i-propyl-7-ethylindenyl)｝ zirconium dibromide rac-dimethylsilylene-bis ｛1- (2,3,7-trimethyl-4-
Ethylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,3,7-trimethyl-4-n-propylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2, 3,7-trimethyl-4-i-propylindenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-butylindenyl) zirconium dichloride, rac- Dimethylsilylene-bis {1- (2,3,7-trimethyl-4-sec-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-t-) Butylindenyl) zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-n-pentylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-n-hexylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-cyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-methylcyclohexylindenyl)} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-trimethylsilylmethylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-
Trimethylsiloxymethylindenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3,7-
Trimethyl-4-phenylethylindenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2,
3,7-trimethyl-4-phenyldichloromethylindenyl) zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,3,7-trimethyl-4-chloromethylindenyl)} zirconium dichloride, rac-diethylsilylene
-Bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (i-propyl)
Silylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di (n-butyl) silylene-bis {1- (2,3,7-trimethyl- 4-i-propylindenyl)｝ zirconium dichloride, rac-di (cyclohexyl) silylene-bis ｛1- (2,3,7-trimethyl-
4-i-propylindenyl) zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2,3,7-
Trimethyl-4-t-butylindenyl) zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7-
Trimethyl-4-t-butylindenyl) zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7-
Trimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-diphenylsilylene-bis {1- (2,3,7)
-Trimethyl-4-ethylindenyl) zirconium dichloride, rac-di (p-tolyl) silylene-bis ｛1- (2,3,7
-Trimethyl-4-i-propylindenyl)｝ zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis ｛1- (2,3,7-trimethyl-4-i-propylindenyl)｝ zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium dimethyl, rac-dimethylsilylene
-Bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium methyl chloride, rac-dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-methyl) Indenyl)｝ zirconium-bis (methanesulfonato), rac-dimethylsilylene-bis ｛1- (2-methyl-4-i-
Propyl-7-methylindenyl) zirconium-bis (p-phenylsulfinato), rac-dimethylsilylene-
Bis {1- (2-methyl-3-methyl-4-i-propyl-7-methylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4-i-propyl-7) -Methylindenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-phenyl-4-i-propyl-7-)
Methylindenyl) zirconium dichloride, rac-
Dimethylsilylene-bis ｛1- (2-methyl-4-i-propyl-
7-methylindenyl) titanium dichloride, rac-
Dimethylsilylene-bis ｛1- (2-methyl-4-i-propyl-
7-methylindenyl)｝ hafnium dichloride.

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

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

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

[0080]

Embedded image

In the formula, M is a transition metal atom belonging to Group IVB of the periodic table, specifically, titanium, zirconium, or hafnium, particularly preferably zirconium.
X ³ and X ⁴ may be the same or different from each other, and include a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,
An alkoxy group having 10 to 10, 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,
C7-C40 alkylaryl group, C8-C40
R ²¹ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, an optionally halogenated alkyl group having 1 to 10 carbon atoms, 6 to 10 aryl groups or —NR ₂ , —SR, —OSiR ₃ , —SiR ₃ or —PR ₂ group (R is a halogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms) And R ^{22 to} R ²⁸ may be the same as R ²¹ described above, or the adjacent R ^{22 to} R ²⁸ may form an aromatic- or aliphatic ring together with the atoms to which they are bonded. ,

[0082]

Embedded image

= BR ²⁹ , = AlR ²⁹ , -Ge-, -Sn
-, - O -, - S -, = SO, = SO 2, = NR 29, =
CO, = PR ²⁹ or = P (O) R ²⁹ (where R
²⁹ and R ³⁰ may be the same or different from each other;
Hydrogen atom, halogen atom, C1-C10 alkyl group, C1-C10 fluoroalkyl group, C6-C6
An aryl group having 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,
An arylalkenyl group having 8 to 40 carbon atoms or 7 carbon atoms
An alkylaryl group of 基 40 or R ²⁹ and R ³⁰
And may each form a ring with the atoms to which they are attached, and M ² is silicon, germanium or tin. The alkyl groups are straight-chain or branched alkyl groups, and the halogens (halogenated) are fluorine, chlorine, bromine or iodine, especially fluorine or chlorine.

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

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

[0086]

Embedded image

= BR ²⁹ , = AlR ²⁹ , -Ge-, -Sn
-, - O -, - S -, = SO, = SO 2, = NR 29, =
CO, ＰＲPR ²⁹ or ＰP (O) R ²⁹ , wherein R ²⁹ and R ³⁰ may be the same or different from each other and include a hydrogen atom, a halogen atom, and an alkyl 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, C6-10 fluoroaryl group, preferably pentafluorophenyl group, C1
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,
An arylalkyl group having 40 carbon atoms, preferably an arylalkyl group having 7 to 10 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, preferably an arylalkenyl group having 8 to 12 carbon atoms, or an alkylaryl group having 7 to 40 carbon atoms, preferably carbon atoms It may be an alkylaryl group of the formulas 7 to 12, or R ²⁹ and R ³⁰ may form a ring together with their bonding atoms.

M ² is silicon, germanium or tin, especially silicon or germanium. In the compound of formula [II], M is zirconium or hafnium;
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 are the same or different from each other and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. And Z is

[0089]

Embedded image

Compounds wherein M ² is silicon and R ²⁹ and R ³⁰ may be the same or different and are an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms are particularly advantageous. It is.

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

[0092]

Embedded image

Compounds wherein M ² is silicon and R ²⁹ and R ³⁰ may be the same or different and are an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms are particularly advantageous. It is.

Among the compounds of the formula [II], particularly preferred compounds are those wherein M is zirconium, X ³ and X
⁴ is a chlorine atom, residue R ²¹ is a methyl group, R ²²
-R ²⁸ is a hydrogen atom, and Z is

[0095]

Embedded image

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

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

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

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

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

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

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

The above-mentioned organoaluminum compounds can be used in combination of two or more kinds.

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

Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferred. The above-mentioned organoaluminum oxy compound [B] may be used in combination of two or more kinds.

[C] Reaction with Metallocene Compound [A]
Compound forming 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-A-501950, JP-T1-5020236,
JP-A-3-179005, JP-A-3-179900
No. 6, JP-A-3-207703, JP-A-3-207703
Examples thereof include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in US Pat. No. 207704 and US Pat.

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

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

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

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

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

The following compounds can also be exemplified.
(In the ionic compounds listed below, the counter ion is, but not limited to, tri (n-butyl) ammonium.) Salts of anions such as bis [tri (n-butyl) ammonium] nonaborate and bis [tri (N-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate , Bis [tri (n-
Butyl) ammonium] dodecachlorododecaborate,
Tri (n-butyl) ammonium-1-carbadecaborate, tri (n-butyl) ammonium-1-carboundecaborate, tri (n-butyl) ammonium-1-carbadodecaborate, tri (n-butyl) ammonium -1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate and the like; and borane compounds and carborane compounds. These compounds are used as Lewis acids and ionic compounds.

Borane and carborane complex compounds and salts of carborane anions such as decaborane (14), 7,
8-dicarboundecaborane (13), 2,7-dicarboundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2, 7-dicarboundecaborane, bird (n-
Butyl) ammonium 6-carbadecaborate (14),
Tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ammonium 7-carboundecaborate (13), tri (n-butyl) ammonium
7,8-dicarboundecaborate (12), tri (n-butyl) ammonium 2,9-dicarboundecaborate (1
2), tri (n-butyl) ammonium dodeca hydride-8-methyl 7,9-dicarboundecaborate, tri (n-butyl
Butyl) ammonium undecahydride-8-ethyl-
7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarboundecaborate, tri (n-butyl) ammoniumundecahydride-8-allyl-7, 9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7- Carborane caborate and the like; carborane and salts of carborane, such as 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl -1,3-dicarbanonaborane, dodeca hydride-
The following compounds can also be exemplified, such as 1-methyl-1,3-dicarbanonaborane and undecahydride-1,3-dimethyl-1,3-dicarbanonaborane. (In the ionic compounds listed below, the counter ion is, but not limited to, tri (n-butyl) ammonium.) Metal carborane salts and metal borane anions such as tri (n-butyl) ammonium bis (nona Hydride-
1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) ferrate (ferrate) (III), tri (n- Butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate)
Cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8- Dicarboundecaborate) cubate (cuprate) (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) aurate (metal salt) (III), tri (n- Butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8- Dicarboundecaborate) chromate (chromate) (II
I), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarboundecaborate)
Cobaltate (III), tri (n-butyl) ammonium bis (dodeca hydride dicarbadodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodeca hydride dodecaborate) nickelate (III), tris [Tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) Manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) cobaltate (II
I) and bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) nickelate (IV).

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

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

R 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
3. In the above formula (a), R ⁴⁰ is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group. -Propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group.

Specific examples of such an organoaluminum compound include the following compounds. Trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum,
Trialkyl aluminum such as trioctyl aluminum and tri-2-ethylhexyl aluminum, alkenyl aluminum such as isoprenyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, dialkyl aluminum halide such as dimethyl aluminum 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 nAlY _3-n (b) (wherein, R ⁴⁰ is the same as above, Y is —OR ⁴¹ group,
OSiR ⁴² ₃ group, -OAlR ⁴³ ₂ group, -NR ⁴⁴ ₂ group, -
SiR ⁴⁵ ₃ group or -N (R ⁴⁶⁾ is AlR ⁴⁷ ₂ group,
n is 1-2, 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, 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 nAl (OR ⁴¹ ) _3-n , for example, dimethyl aluminum methoxide
Diethylaluminum ethoxide, diisobutylaluminum methoxide and the like.

[0120] ^{(ii) R 40 nAl (OSiR} 42 3) a compound represented by _3-n, e.g., _{(C 2 H 5) 2 Al} (OSi (CH
₃ ) ₃ ), (iso-C ₄ H ₉ ) ₂ Al (OSi (CH ₃ ) ₃ ),
Such as _{(iso-C 4 H 9)} 2 Al (OSi (C 2 H 5) 3).

[0121] ^{(iii) R 40 nAl (OAlR} 43 2) Compounds represented by _3-n, e.g., _{(C 2 H 5) 2 Al} (OAl
(C ₂ H ₅ ) ₂ ), (iso-C ₄ H ₉ ) ₂ Al (OAl (iso-C
₄ H _{9) 2),} etc..

[0122] ^{(iv) R 40 nAl (NR} 44 2) Compounds represented by _3-n, e.g., _{(CH 3) 2 Al (N} (C
_{2 H 5) 2), (} C 2 H 5) 2 Al (NH (CH 3)), (C
_{H 3) 2 Al (NH (} C 2 H 5)), (C 2 H 5) 2 Al [N
(Si (CH ₃ ) ₃ ) ₂ ], (iso-C ₄ H ₉ ) ₂ Al [N (Si
Such as _{(CH 3) 3) 2]} .

[0123] ^{(v) R 40 nAl (SiR} 45 3) a compound represented by _3-n, e.g., _{(iso-C 4 H 9)} 2 Al (Si (CH
₃ ) ₃ ) etc. In the present invention, also R ⁴⁰ ₃ Al Of these, R ⁴⁰ nAl
(OR ⁴¹⁾ _3-n, it can be mentioned organoaluminum compounds represented by _{^{R 40 nAl (OAlR 43 2)}} 3-n Suitable examples, R ⁴⁰ is an isoalkyl group, compounds which are n = 2 is Particularly preferred. These organoaluminum compounds can be used in combination of two or more.

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

In the present invention, the metallocene compound [A]
Is usually used in an amount of about 0.0005 to 0.1 mmol, preferably about 0.0001 to 0.05 mmol, in terms of transition metal atoms per liter of polymerization volume.

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

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

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

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

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

In the present invention, when copolymerizing (a) ethylene, (b) an α-olefin having 3 or more carbon atoms, and (c) a non-conjugated polyene,
Group B metallocene compound [A], organic aluminum oxy compound [B], compound [C] reacting with [A] to form an ion pair, and organic aluminum compound [D] are separately supplied to the polymerization reactor. Alternatively, a catalyst containing the metallocene compound [A] may be prepared in advance and then subjected to the copolymerization reaction.

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

The Group IVB metallocene compound [A], the organoaluminum oxy compound [B], the compound [C] forming an ion pair and the organoaluminum compound [D]
Is usually -100 to 200C, preferably -70 to 10
Mixing contact can be performed at 0 ° C.

In the present invention, the copolymerization of (a) ethylene, (b) an α-olefin having 3 or more carbon atoms and (c) a non-conjugated polyene is usually carried out at 40 to 200 ° C., preferably 50 to 150 ° C.
Particularly preferably, at 60 to 120 ° C. and at atmospheric pressure to 100 kg /
cm ² preferably particularly preferably atmospheric pressure to 50 kg / cm ² can be carried out under the conditions of atmospheric pressure 30 kg / cm ^2.

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

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

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

The product immediately after polymerization is recovered from the polymerization solution and dried by a conventionally known separation and recovery method to obtain a solid random copolymer. In the present invention, the modified 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 a derivative thereof, and a vinyl ester. Compounds, vinyl chloride and the like.

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

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

[0142]

Embedded image

(Wherein, R ¹ is a hydrogen atom, a methyl group or an ethyl group, R ² is a hydrogen atom, having 1 to 12 carbon atoms,
Preferably an alkyl group having 1 to 8 carbon atoms, 6 to 1 carbon atoms
2, preferably 6 to 8 cycloalkyl groups. The above alkyl group and cycloalkyl group may further have a substituent. Examples of such an amino group-containing ethylenically unsaturated compound include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, and phenyl methacrylate. Aminoethyl, alkylester derivatives of acrylic acid or methacrylic acid such as cyclohexylaminoethyl methacrylate N-vinyldiethylamine, vinylamine derivatives such as N-acetylvinylamine allylamine, methacrylamine, N-methylacrylamine, N, Allylamine derivatives such as N-dimethylacrylamide and N, N-dimethylaminopropylacrylamide Acrylamide derivatives such as N-methylacrylamide Aminostyrenes such as p-aminostyrene 6-amido Hexyl succinimide, such as 2-aminoethyl succinimide and the like.

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

The aromatic vinyl compound is represented by the following formula.

[0146]

Embedded image

(Wherein, 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, or an isopropyl group. R ³ has 1 carbon atom. And a hydrocarbon atom or a halogen atom, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a chlorine atom, a bromine atom or an iodine atom, and n is usually 0 to 5, preferably 1 Examples of such an aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, p-chlorostyrene and m-methylstyrene.
Chlorostyrene, p-chloromethylstyrene, 4-vinylpyridine, 2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, 2-isopropenylpyridine, 2-vinylquinoline, 3-vinyl Vinyl isoquinoline, N-
Vinyl carbazole, N-vinyl pyrrolidone and the like.

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

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

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

Examples of the vinyl ester compound include vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, and vinyl benzoate. , Vinyl pt-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 to the above random copolymer. When the random copolymer is graft-polymerized with the polar monomer as described above, the polar monomer is usually 1 to 100 parts by weight, preferably 5 to 80 parts by weight, based on 100 parts by weight of the random copolymer. Used in quantity.

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

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

Examples of the azo compound include azoisobutyronitrile and dimethylazoisobutyronitrile. The radical initiator is a random copolymer 10
It is desirable to use it in an amount of about 0.001 to 10 parts by weight with respect to 0 parts by weight.

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

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

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

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

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

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

The modified random copolymer can also be produced by reacting the random copolymer with a polar monomer without using a solvent using an extruder or the like. This reaction is usually performed at a temperature equal to or higher than the melting point of the random copolymer, specifically, from 120 to 2
It is usually desirable to carry out at a temperature of 50 ° C. for 0.5 to 10 minutes.

The amount of modification (graft amount of polar monomer) of the modified random copolymer thus obtained is usually from 0.1 to 50% by weight, preferably from 0.2 to 30% by weight.

Vulcanizable Rubber Composition The vulcanizable rubber composition according to the present invention containing the above-mentioned ethylene / α-olefin / non-conjugated polyene random copolymer is used even if it is not vulcanized. However, when used as a vulcanizate, more excellent properties can be exhibited.

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

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

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

Specific examples of the inorganic filler include light calcium carbonate, heavy calcium carbonate, talc, clay and the like. The rubber composition according to the present invention comprises a reinforcing agent and / or an inorganic filler containing ethylene / α-olefin /
It can 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 of the non-conjugated polyene random copolymer.

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

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

Of these, petroleum softeners are preferred, and process oils are particularly preferred. The rubber composition according to the present invention is preferably a softener as described above, 10 to 200 parts by weight, preferably 10 to 150 parts by weight, based on 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 The rubber composition according to the present invention preferably contains an anti-aging agent because the material life can be extended. As the antioxidant, specifically, phenylnaphthylamine,
Aromatic secondary amine stabilizer such as 4,4 '-(α, α-dimethylbenzyl) diphenylamine, N, N'-di-2-naphthyl-p-phenylenediamine, 2,6-di-t-butyl Phenolic stabilizers such as -4-methylphenol, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl]
Thioether stabilizer such as sulfide, benzimidazole stabilizer such as 2-mercaptobenzimidazole, dithiocarbamate stabilizer such as nickel dibutyldithiocarbamate, polymerization of 2,2,4-trimethyl-1,2-dihydroquinoline And quinoline-based stabilizers. These may be used in combination of two or more.

[0173] Such anti-aging agents include 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 processing aids, those generally blended with rubber as processing aids can be widely used. In particular,
Acids such as ricinoleic acid, stearic acid, palmitic acid, and lauric acid, and salts of these higher fatty acids, such as barium stearate, zinc stearate, calcium stearate, and esters.

The processing aid is ethylene / α-olefin.
It can be appropriately used in an amount of 10 parts by weight or less, preferably 5 parts by weight or less based on 100 parts by weight of the non-conjugated polyene random copolymer.

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

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

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

As the organic peroxide, specifically,
Dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide, di-t-amyl peroxide, 2,5-dimethyl -2,5-di (t-butylperoxin) hexyne-3, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-
Alkyl peroxides such as butylperoxy) -hexane, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, t-butylhydroperoxide,
t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxyvivalate, t-butyl peroxymaleic acid, t-butyl peroxy neodecanoate, t-butyl peroxybenzoate, di- And peroxyesters such as -t-butylperoxyphthalate and ketone peroxides such as dicyclohexanone peroxide. These may be used in combination of two or more.

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

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

When the vulcanizing agent is an organic peroxide, it is 0.0003 to 0.05 mol, preferably 0.001 to 0.005 mol per 100 g of the ethylene / α-olefin / non-conjugated polyene random copolymer. It can be used in an amount of 03 mol.

Vulcanization Accelerator When sulfur or a sulfur compound is used as the vulcanizing agent, it is preferable to use a vulcanization accelerator in combination.

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

The vulcanization accelerator as described above is ethylene • α
-Olefin / non-conjugated polyene random copolymer 100
0.1 to 20 parts by weight, preferably 0.2 to 20 parts by weight,
Preferably, it is used in an amount of 10 parts by weight.

[0186] When the organic peroxide is used as vulcanizing agent (polyfunctional monomer) The vulcanizing agent, vulcanization agent (polyfunctional monomer) with respect to the organic peroxide 1 mole 0. It is preferable to use 5 to 2 moles, preferably about equimolar amount.

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

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

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

As the foaming agent, foaming agents generally used for foaming rubber can be widely used.
Specifically, inorganic blowing agents such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite, N, N'-dimethyl-N, N'-dinitrosoterephthalamide, N, N'-di Nitroso compounds such as nitrosopentamethylenetetramine, azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azo compounds such as azodiaminobenzene, barium azodicarboxylate, benzenesulfonylhydrazide, toluenesulfonylhydrazide, p, p ' Sulfonyl hydrazide compounds such as -oxybis (benzenesulfonyl hydrazide) and diphenylsulfone-3,3'-disulfonyl hydrazide; and azide compounds such as calcium azide, 4,4-diphenyldisulfonyl azide and p-toluenesulfonyl azide. Can be

Of these, nitroso compounds, azo compounds and azide compounds are preferred. 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 an amount of up to 20 parts by weight. From the rubber composition containing the foaming agent in such an amount, an apparent specific gravity of 0.
Foams of 03-0.8 g / cm ³ can be produced.

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

The foaming auxiliary is ethylene / α-olefin.
It 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 non-conjugated polyene random copolymer.

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

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

Further, conventionally known ethylene / α-olefin-based copolymer rubbers can also be used. Examples thereof include ethylene / propylene random copolymer (EPR) and ethylene / α-olefin / non-conjugated polyene random copolymer. Ethylene / α-olefin / non-conjugated polyene random copolymer such as EPDM can be used.

The vulcanizable rubber composition according to the present invention is prepared from an 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
-After kneading the olefin / non-conjugated polyene random copolymer and other components at a temperature of 80 to 170 ° C. for 3 to 10 minutes, a vulcanizing agent, a vulcanization accelerator or a vulcanization aid is added as necessary. In addition, using a roll such as an open roll or a kneader, a roll temperature of 40 to 80 ° C. and 5 to 3
It can be prepared by kneading for 0 minutes and then dispensing. In this way, a rubber composition (compounded rubber) usually in the form of a ribbon or sheet is obtained. When the kneading temperature in the above internal mixers is low, a vulcanizing agent,
A vulcanization accelerator, a foaming agent and the like can be simultaneously kneaded.

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

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

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

In molding and vulcanization, a mold may be used, or a mold may not be used. When a mold is not used, the rubber composition is usually continuously molded and vulcanized. The vulcanized rubber molded and vulcanized as described above is used for automotive parts such as weather strip, door glass run channel, window frame, radiator hose, brake parts, wiper blade, rubber roll, belt, packing, hose, etc. It can be used for applications such as rubber products, electric insulating materials such as anode caps and grommets, construction gaskets, civil engineering construction materials such as civil engineering sheets, and rubber cloth.

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

[0203]

According to the method for producing an ethylene / α-olefin / non-conjugated polyene random copolymer of the present invention, ethylene and α-olefin having 3 or more carbon atoms, which cannot be achieved by the conventional production method. An olefin and a non-conjugated polyene can be copolymerized with high activity, with a high conversion of α-olefin, and with excellent random copolymerizability, to obtain a high molecular weight copolymer. In addition, 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 can be efficiently produced. Can be manufactured.

Ethylene α-produced by the present invention
Olefin / non-conjugated polyene random copolymer has the above-mentioned properties, narrow composition distribution, excellent mechanical strength, excellent low-temperature flexibility and heat aging resistance, weather resistance, ozone resistance Excellent characteristics.

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

[0206]

EXAMPLES Next, the present invention will be described specifically 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 determined by a differential scanning calorimeter (DS).
C). This glass transition temperature Tg is an index of the low-temperature flexibility of the ethylene / α-olefin / non-conjugated polyene random copolymer.

Measurement of Tg by DSC A sample was taken from normal temperature (25 ° C) at a rate of 20 ° C / min.
Temperature, and kept at 180 ° C for 2 minutes, then -20 ° C
The mixture was cooled to -80 ° C at a rate of / min, kept at -80 ° C for 2 minutes, and then heated again at a rate of 20 ° C / min to determine Tg. The zirconium compounds used in the examples are shown below.

[0208]

Embedded image

[0209]

[Reference Example 1] Zirconium compound and methylalumoxane
With a predetermined amount of the zirconium compound A and a toluene solution of methylalumoxane (1.2 mg atom / aluminum atom)
) was mixed in a dark place by stirring at room temperature for 30 minutes to prepare a toluene solution in which zirconium compound A and methylalumoxane were dissolved. The Zr concentration of this toluene solution is 0.004 mmol / ml, and the methylalumoxane concentration is 1.2 mg atoms / ml in terms of aluminum atoms.

Next, hexane having a volume 5 times the volume of toluene was added to this toluene solution with stirring to prepare a catalyst solution having the following Zr concentration and methylalumoxane concentration. It was used as a catalyst. Zr concentration: 0.000067 mmol / ml (0.67 mmol / l) Methylalumoxane concentration (in terms of Al atom): 0.1
20 mmol / ml (200 mmol / liter)

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

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

Further, ethylene was fed from the upper part of the polymerization reactor at a rate of 20 hours / hour.
0 liter and 1-butene were continuously supplied at 155 liters per hour. The copolymerization reaction is performed at 90 ° C. and the average residence time is 1 hour (ie, a polymerization scale of 5 liters).
It was carried out so that

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

As described above, ethylene / 1-butene
A MOD random copolymer was obtained in an amount of 280 g per hour. The obtained random copolymer was obtained by converting a unit derived from ethylene and a unit derived from 1-butene into 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 gη ^* value was 1.05. Table 2 shows the results.

[0217]

[Examples 1 to 5, Reference Example 2-4] in Reference Example 1, participants
An ethylene / α-olefin / non-conjugated polyene random copolymer was produced in the same manner as in Reference 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. Table 2 shows the results.

[0218]

In Reference Example 5] Example 1, except for using propylene in place of 1-butene, in the same manner as in Example 1 to produce the ethylene-propylene-ethylidene norbornene (ENB) random copolymer. Table 2 shows the results.

[0219]

[Table 1]

[0220]

[Table 2]

[0221]

[Comparative Example 1] Using a 2 liter polymerization vessel equipped with a stirring blade, ethylene, 1-butene, 7-methyl-1,6-
Octadiene was copolymerized as follows.

From the top of the polymerization vessel, 7-methyl-1,6
-Octadiene (MOD) in hexane (concentration 36 g)
/ Liter) per hour, 0.5 liter per hour, VO as catalyst
Hexane solution of (OC ₂ H ₅ ) Cl ₂ (concentration 8 mmol /
Liter) per hour and a hexane solution of ethyl aluminum sesquichloride [Al (C ₂ H ₅ ) _1.5 Cl _1.5 ] (concentration 64 mmol / l) at a rate of 0.5 hour / hour.
Liter and then hexane were supplied at a rate of 0.5 liter per hour, while the polymerization solution in the reactor was continuously withdrawn from the lower part of the reactor so that the polymerization solution in the reactor was always 1 liter.

In this polymerization vessel, 130 l / h of ethylene and 1-butene were fed at a rate of 20 h / h using a bubbling tube.
0 liters and hydrogen were supplied at a rate of 20 liters per hour.
The copolymerization reaction was performed while maintaining the temperature at 20 ° C. by circulating a refrigerant through a jacket attached to the outside of the polymerization vessel.

The polymerization solution of the ethylene / 1-butene / MOD random copolymer obtained by the above copolymerization reaction was deashed with hydrochloric acid water, and a large amount of methanol was added to precipitate the polymer. For 24 hours under reduced pressure.

As described above, ethylene / 1-butene
A MOD random copolymer was obtained in an amount of 280 g per hour. The obtained random copolymer (rubber) is composed of a unit derived from ethylene and a unit derived from 1-butene as 7
4/26 (molar ratio). 7-methyl-1,6
It contained units derived from -octadiene (MOD) in an amount of 2.1 mol%.

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

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

[0228]

Example 6 using a stainless steel polymerization vessel 15 liter with a Polymerization stirring blade (hereinafter also referred to as ENB) and continuously ethylene, 1-butene, ethylidenenorbornene
Were copolymerized as follows.

First, 3.185 liters / hour of dehydrated and purified hexane and 0.015 liters / hour of the catalyst solution containing zirconium compound A and methylalumoxane prepared in Reference Example 1 were introduced into the polymerization vessel from the top of the polymerization vessel. Hexane solution of triisobutylaluminum (concentration 17 mmol /
Liter), and a hexane solution of ENB (concentration: 0.02 liter / liter) was continuously supplied at 1.5 liter / hour.

Also, ethylene was fed from the upper part of the polymerization reactor at a rate of 20 hours / hour.
0 liter and 1-butene were continuously supplied at 155 liters per hour. The copolymerization reaction is carried out at 80 ° C. and the average residence time is 1 hour (ie, a polymerization scale of 5 liters).
I went to become.

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

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

The intrinsic viscosity [η] of the copolymer measured at 135 ° C. in decalin was 2.7 dl / g, and ¹³ C-NM
Intensity ratio D of Tαβ to Tαα in 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. Table 3 shows the results.

[0234]

EXAMPLES 7-11 In Examples 6, except performing the copolymerization reaction by changing polymerization conditions, to produce the ethylene · alpha-olefin, non-conjugated polyene random copolymer in the same manner as in Example 6. Table 3 shows the results.

[0235]

[Table 3]

[0236]

Examples 12-17 Compounded rubbers containing the ethylene / α-olefin / non-conjugated polyene random copolymer prepared in Examples 6-11 and other components in the amounts shown in Table 4 were used. Rubber composition) was obtained. That is, ethylene / α-olefin / non-conjugated polyene random copolymer, stearic acid, zinc white, paraffin oil,
The carbon was kneaded for 10 minutes using a 1.7 liter Banbury mixer (manufactured by Kobe Steel). Using a 6-inch roll (F / B = 50/50 ° C.), a vulcanizing agent and a vulcanization accelerator were added and kneaded.

Next, the 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 measuring compression set (CS) has a thickness of 1
A 2.7 mm, 29 mm diameter right cylindrical test piece was
It was obtained by vulcanizing at 0 ° C. for 15 minutes.

The rubber composition obtained above and its vulcanizate (crosslinked sheet) were evaluated and tested by the following methods.
Table 4 shows the composition of the unvulcanized rubber composition, and Table 5 shows the test results of the vulcanized product.

(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 JIS K 6301 was used by using the test piece. according to the method defined in Section 3, measurement temperature 25 ° C., subjected to tensile test at a tensile rate of 500 mm / min condition, the tensile stress at break T _B and tensile elongation at break E _B were measured.

(2) Hardness test (Hs hardness) In the hardness test, a 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 performed by performing an air heating aging test at 125 ° C. for 70 hours, and the retention ratios for physical properties before aging, that is, the tensile strength retention AR (T _B ) and the elongation retention AR (E _B) ) And hardness change A _H (JIS A) were determined.

(4) Compression set test (CS) The compression set test is based on JIS K6301,
The low temperature compression set (CS) after 22 hours at -40 ° C was determined. The lower the low-temperature compression set, the better the low-temperature flexibility.

[0243]

[Table 4]

[0244]

[Table 5]

[Brief description of the drawings]

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

Continued on the front page. (72) Inventor: Toshihiro Aine 1-2-1, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industry Co., Ltd. No. 6 1-2 Ki, Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Hidenari Nakahama 3 Chigusa Coast, Ichihara-shi, Chiba Prefecture Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A-6-80713 ( JP, A) JP-A-62-121711 (JP, A) JP-A-60-35007 (JP, A) JP-A-5-262827 (JP, A) JP-A-7-165813 (JP, A) JP Hei 6-345809 (JP, A) JP-A-58-191705 (JP, A) WO 93/025591 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/60 -4/70 C08F 10/00-10/14 C08F 110/00-110/14 C08F 210/00-210/18

Claims (5)

(57) [Claims] (1) a unit derived from (a) ethylene and (b) a unit derived from an α-olefin having 4 to 10 carbon atoms, wherein 40/60 to 95/5 [(a) / ( b)], (ii) an iodine value of 12 to 50, and (iii) intrinsic viscosity [η] measured at 135 ° C. in decalin.
There is 1.6~ 6 dl / g, (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 B value obtained from the following formula is 1.00 to 1.50; B value = [P _OE ] / (2 · [P _E ] · [P _O ]) (where [P _E ] is Is the mole fraction of (a) units derived from ethylene in the random copolymer, and [P _O ] is the mole fraction of units (b) in the random copolymer derived from α-olefin. [P _OE ] is the total dyad (dy) in the random copolymer.
ad) the ratio of the number of α-olefin / ethylene chains to the number of chains), (vi) the glass transition temperature Tg determined by DSC is −50 ° C.
An ethylene / α-olefin / non-conjugated polyene random copolymer, wherein the non-conjugated polyene is an alicyclic polyene or an aromatic polyene. 2. A vulcanizable rubber composition comprising the ethylene / α-olefin / non-conjugated polyene random copolymer according to claim 1 . 3. A method according to claim 1, wherein a reinforcing agent and / or an inorganic filler 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. The rubber composition according to claim 2 . Relative wherein said ethylene-alpha-olefin-nonconjugated polyene random copolymer 100 parts by weight, according to claim 2, characterized in that it contains a softening agent in an amount of 10 to 200 parts by weight Rubber composition. 5. A vulcanized rubber obtained from the vulcanizable rubber composition according to any one of claims 2 to 4 .