JPH0940586A - Norbornene compound containing chain polyene group and its production, unsaturated ethylenic copolymer using the same and its production, and rubber composition containing the same copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new norbornene compound containing a chain polyene group, excellent in weather resisting, heat resisting and ozone resisting properties, having a rapid vulcanization rate, and capable of suitably being used for the production of the unsaturated ethylenic copolymer useful for an automobile part such as a brake part, and a heat insulating material, etc. SOLUTION: This norbornene compound is a compound of formula I [R<1> is a 1-5C alkyl; R<2> , R<3> are each H or R<1> ; (n) is 1-5], e.g. 5-(2-ethylidene-6- methyl-5-heptenyl)-2-norbornene. The compound of the formula I is obtained by reacting (A) a compound of formula III obtained by reacting ethylene with a compound of formula II in the presence of a catalyst consisting of a transition metal compound and an organic aluminum compound, with (B) cyclopentadiene.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel chain polyene group-containing norbornene compound and a method for producing the same, and more specifically to a novel unsaturated compound having excellent weather resistance, heat resistance, ozone resistance and fast vulcanization rate. The present invention relates to a chain-like polyene group-containing norbornene compound that can be preferably used in the production of a water-soluble ethylene copolymer and a method for producing the same.

The present invention also relates to a novel unsaturated ethylenic copolymer having the above-mentioned characteristics, which uses the above-mentioned chain polyene group-containing norbornene compound, and a method for producing the same.

The present invention also relates to a rubber composition containing such an unsaturated ethylenic copolymer.

[0004]

BACKGROUND OF THE INVENTION Generally, a polyene compound is a compound (monomer) having two or more carbon-carbon double bonds in one molecule, and conventionally, 1,3-butadiene,
Many substances such as 1,3-pentadiene, 1,4-hexadiene, ethylidene-2-norbornene and dicyclopentadiene are known.

A vulcanizable unsaturated ethylenic copolymer can be obtained by copolymerizing such a polyene compound with an α-olefin such as ethylene or propylene. Such unsaturated ethylene-based copolymers are generally excellent in weather resistance, heat resistance and ozone resistance, and are used in automobile industrial parts, industrial rubber products, electrical insulation materials, civil engineering building materials, rubberized cloth, etc. Is widely used as a material for blending plastics such as polypropylene and polystyrene.

Conventionally, such unsaturated ethylene-based copolymers include ethylene / propylene / 5-ethylidene-2-norbornene copolymer and ethylene / propylene /
Dicyclopentadiene copolymer, ethylene / propylene / 1,4-hexadiene copolymer, etc. are used.
Of these, ethylene / propylene / 5-ethylidene
The -2-norbornene copolymer has a faster vulcanization rate than other unsaturated ethylenic copolymers and is widely used.

However, in these conventional unsaturated ethylene-based copolymers, it is a fact that further improvement of the vulcanization rate is desired. That is, the unsaturated ethylene copolymer is, for example, ethylene / propylene / 5-ethylidene.
-2- Even with norbornene copolymers, the vulcanization speed is slower than that of diene rubbers such as natural rubber, styrene / butadiene rubber, isoprene rubber, butadiene rubber, nitrile rubber, and covulcanization with diene rubbers. I was inferior in sex.

Further, the unsaturated ethylenic copolymer has a slower vulcanization rate than the above-mentioned diene rubber and the like, so that the vulcanization time can be shortened or the vulcanization temperature can be lowered. It has been difficult to reduce the energy consumption and manufacture vulcanized rubber with high productivity.

A large amount of a vulcanizing agent may be used to increase the vulcanization rate of the unsaturated ethylene copolymer, but if an attempt is made to vulcanize using a large amount of the vulcanizing agent, a vulcanized rubber obtained. The vulcanizing agent may bloom on the surface of the product, which is not hygienic.

Therefore, a novel polyene compound which is excellent in weather resistance, heat resistance and ozone resistance and which can produce an unsaturated ethylene copolymer having a high vulcanization rate, and an unsaturated property using the polyene compound The appearance of ethylene copolymers has been desired.

In view of the above-mentioned conventional techniques, the present inventor has conducted earnest research on a polyene compound and an unsaturated ethylene copolymer using the polyene compound, and as a result, found that a specific chain polyene group-containing norbornene compound was identified. The unsaturated ethylenic copolymer ethylene used, that is, α-
An unsaturated ethylenic copolymer having a structural unit derived from an olefin and a specific chain polyene group-containing norbornene compound, and having an unsaturated bond component is excellent in weather resistance, heat resistance and ozone resistance, Moreover, the inventors have found that the vulcanization rate is high and have completed the present invention.

Incidentally, Japanese Patent Publication No. 46-42365 discloses that ethylene, a general formula: RCH = CH ₂ (R: carbon number 1
At least one α-olefin having a hydrocarbon group having from 20 to 20 and a general formula:

[0013]

[Chemical 6]

(R ¹ and R ² are H and C 1-2, respectively.
A hydrocarbon group having 0, Q represents a hydrocarbon group having at least one internal double bond at a non-conjugated position and all double bonds being internal. 5-Polyenyl-2 having)
A method for producing an olefin copolymer in which a norbornene compound is brought into contact with a coordination catalyst is described.

However, the olefin copolymer obtained by the method described in the publication is desired to have excellent weather resistance, heat resistance and ozone resistance, and a good balance in vulcanization rate. From the point of view, it is not always enough.

[0016]

SUMMARY OF THE INVENTION The present invention is intended to solve the above problems associated with the prior art, and is an unsaturated ethylene having excellent weather resistance, heat resistance and ozone resistance and having a high vulcanization rate. An object of the present invention is to provide a chain-like polyene group-containing norbornene compound that can be suitably used in the production of a system copolymer and a method for producing the same.

Another object of the present invention is to provide an unsaturated ethylene copolymer having the above characteristics and a method for producing the same. Another object of the present invention is to provide a rubber composition containing such an unsaturated ethylene copolymer.

[0018]

SUMMARY OF THE INVENTION The chain polyene group-containing norbornene compound according to the present invention has the general formula [I]:

[0019]

[Chemical 7]

[In the formula [I], n is an integer of 1 to 5,
R ¹ is an alkyl group having 1 to 5 carbon atoms, and R ² and R ³
Is each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ]] Is represented.

In the method for producing a chain polyene group-containing norbornene compound according to the present invention, cyclopentadiene and general formula [III]:

[0022]

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[In the formula [III], n is an integer of 1 to 5, R ¹ is an alkyl group having 1 to 5 carbon atoms, and R ² and R ³ are each independently a hydrogen atom or 1 carbon atom. ~ 5 alkyl groups. ] The above-mentioned chain-like polyene group-containing norbornene compound is produced by reacting the above-mentioned chain-like polyene compound.

The unsaturated ethylenic copolymer according to the present invention comprises [A] (i) ethylene, (ii) an α-olefin having 3 to 20 carbon atoms, and (iii) the above general formula [I]. It is a random copolymer with at least one type of norbornene compound containing a chain polyene group represented by [B] (i) a constitutional unit derived from ethylene is 30 to 9
2 mol%, (ii) the constitutional unit derived from an α-olefin having 3 to 20 carbon atoms is 6 to 70 mol%, and (ii)
i) A structural unit derived from the chain polyene group-containing norbornene compound represented by the general formula [I] is 0.1 to 30.
Mol% and (iv) (i) a structural unit derived from ethylene / (ii) a structural unit derived from an α-olefin having 3 to 20 carbon atoms in a molar ratio of 40/60 to 92/8. [C] The structural unit derived from the chain polyene group-containing norbornene compound represented by the above general formula [I] has a structure represented by the following formula [II],

[0025]

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[In the formula [II], n is an integer of 1 to 5,
R ¹ is an alkyl group having 1 to 5 carbon atoms, and R ² and R ³
Is each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ] [D] Intrinsic viscosity [η] measured in decalin at 135 ° C
Is 0.05 to 10 dl / g.

In the method for producing an unsaturated ethylenic copolymer according to the present invention, (i) ethylene and (ii) carbon atoms of 3 to 20 are used.
And (iii) at least one chain polyene group-containing norbornene compound represented by the above general formula [I], a transition metal compound, an organoaluminum compound and / or an ionized ionic compound, The unsaturated ethylenic copolymer is produced by copolymerization in the presence of a catalyst formed from

In the unsaturated ethylene-based copolymer according to the present invention, in addition to the chain polyene group-containing norbornene compound [I] in the above [A] (iii), the following general formula [I-a ]:

[0029]

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(In the formula [Ia], n, R ¹ , R ² and R ³
Is the same as in the case of the above [I]. )) At least one norbornene compound containing chain polyene group [I-a] is present in a smaller amount than the above compound [I], preferably in a total of 100 mol% of [I] + [I-a]. May contain the compound [I-a] in an amount of less than 50 mol%, more preferably 40 mol% or less, and particularly preferably 35 mol% or less. In such a random copolymer, [B] (iii): Constitutional unit [II] derived from the norbornene compound containing a chain polyene group represented by the above general formula [I], and chain polyene group represented by the above general formula [Ia] The structural unit [II-a] described below derived from the norbornene compound has a total amount similar to that of the chain polyene group-containing norbornene compound [II] alone, that is, 0.1 to 30 mol%, The above structural unit [II] and the above structural unit The amount ratio between [II-a] is used were chain polyene group-containing norbornene compound [I] and [I-
a), the structural unit [II-a] is 50 mol% in 100 mol% in total of the structural units [II] and [II-a].
It is copolymerized in an amount of less than mol%, more preferably 40 mol% or less, particularly preferably 35 mol% or less.

Further, the above-mentioned [C]: the structural unit derived from the chain polyene group-containing norbornene compound represented by the above general formula [I] has a structure represented by the above formula [II], and The structural unit derived from the chain polyene group-containing norbornene compound represented by the general formula [Ia] is represented by the following formula [II-a]:

[0032]

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(In the formula [II-a], n, R ¹ , R ² and R
Each of ³ is the same as the case of the above [II]. ).

The unsaturated ethylenic copolymer according to the present invention comprises (i) ethylene, (ii) an α-olefin having 3 to 20 carbon atoms, and (iii) the above general formula [I]. At least one chain-like polyene group-containing norbornene compound represented, and a small amount of the above-mentioned general formula [I-a] as compared with the chain-like polyene group-containing norbornene compound [I]
Produced by copolymerizing at least one chain polyene group-containing norbornene compound represented by the formula (1) with a transition metal compound and an organoaluminum compound and / or an ionizable ionic compound in the presence of a catalyst. can do.

The rubber composition according to the present invention comprises any of the above unsaturated ethylenic copolymers and the following (a), (b) and (c):
And at least one component of the above are included. (a) Reinforcing agent in an amount of 300 parts by weight or less with respect to 100 parts by weight of the unsaturated ethylene copolymer, (b) 200 parts by weight or less with respect to 100 parts by weight of the unsaturated ethylene copolymer. Amount of softening agent, (c) vulcanizing agent.

The chain polyene group-containing norbornene compound according to the present invention as described above is excellent in weather resistance, heat resistance, ozone resistance and vulcanization rate by being copolymerized with α-olefins such as ethylene and propylene. It can be preferably used as a monomer when producing an unsaturated ethylenic copolymer having a high viscosity.

The unsaturated ethylenic copolymer according to the present invention as described above is excellent in weather resistance, heat resistance and ozone resistance and has a high vulcanization rate.

[0038]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a chain polyene group-containing norbornene compound according to the present invention, a method for producing the same, an unsaturated ethylene copolymer using the norbornene compound, a method for producing the same, and the unsaturated property The rubber composition containing the ethylene-based copolymer will be specifically described.

[Chain polyene group-containing norbornene compound
Product] The chain polyene group-containing norbornene compound [I ] according to the present invention is represented by the following general formula [I], as described above.

[0040]

[Chemical 12]

In the formula [I], n is an integer of 1 to 5 and R ¹
Is an alkyl group having 1 to 5 carbon atoms, and R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The numbers 1 to 7 and n + 3 indicate the carbon number (substituent position).

Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t -Butyl group, n-pentyl group, i-pentyl group and the like.

Specific examples of the chain polyene group-containing norbornene compound represented by the formula [I] (hereinafter, also referred to as chain polyene group-containing norbornene compound [I]) are as follows (1) to (24). And compounds (5), (6), (9) and (1
1), (14), (19) and (20) are used. (1): 5- (2-ethylidene-4-hexenyl) -2-norbornene, (2): 5- (2-ethylidene-5-methyl-4--
Hexenyl) -2-norbornene, (3): 5- (2-ethylidene-5-methyl-4-heptenyl) -2-norbornene,
(4): 5- (2-ethylidene-5-ethyl-heptenyl)-
2-norbornene, (5): 5- (2-ethylidene-4,5)
-Dimethyl-4-hexenyl) -2-norbornene,
(6): 5- (2-ethylidene-4,5-dimethyl-4-heptenyl) -2-norbornene, (7): 5- (2-ethylidene-4-octenyl) -2-norbornene, (8): 5-
(2-Ethylidene-5-methyl-4-octenyl) -2-norbornene, (9): 5- (2-ethylidene-4-propyl-
5-methyl-4-hexenyl) -2-norbornene, (1
0): 5- (2-ethylidene-5-heptenyl) -2-norbornene, (11): 5- (2-ethylidene-6-methyl-5-)
(Heptenyl) -2-norbornene, (12): 5- (2-ethylidene-6-nonenyl) -2-norbornene, (13):
5- (2-ethylidene-6-methyl-5-nonenyl) -2-norbornene, (14): 5- (2-ethylidene-5,6-dimethyl-5-heptenyl) -2-norbornene, (15): 5
-(2-Ethylidene-5,6-dimethyl-5-octenyl)-
2-norbornene, (16): 5- (2-ethylidene-5,5
6-dimethyl-5-nonenyl) -2-norbornene, (1
7): 5- (2-ethylidene-5-ethyl-6-methyl-5-
Nonenyl) -2-norbornene (18): 5- (2-ethylidene-5,6-diethyl-5-octenyl) -2-norbornene, (19): 5- (2-ethylidene-7-methyl-6-octenyl) ) -2-norbornene, (20): 5- (2-ethylidene-6,7-dimethyl-6-octenyl) -2-norbornene, (21): 5- (2-ethylidene-8-methyl-7-nonenyl) ) -2-Norbornene, (22): 5- (2-ethylidene-7,8-dimethyl-7-nonenyl) -2-norbornene,
(23): 5- (2-ethylidene-9-methyl-8-decenyl) -2-norbornene, (24): 5- (2-ethylidene)
-8,9-dimethyl-8-decenyl) -2-norbornene and the like.

The chemical formulas of the compounds (1) to (24) are summarized below.

[0045]

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[0046]

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[0047]

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Such a chain polyene group-containing norbornene compound [I] is preferably used as a monomer for producing an unsaturated ethylene-based copolymer described later, (i) ethylene, and (ii) a carbon number of 3 to 3. It is used together with 20 α-olefins, in which case the chain polyene group-containing norbornene compound [I] may be one of the stereoisomers, for example, the trans isomer alone or the cis isomer alone. It may be a mixture of isomers, for example a mixture of trans and cis isomers.

The chain polyene group-containing norbornene compound [I] as described above has a weather resistance, a heat resistance, a
It can be suitably used in the production of a novel unsaturated ethylene-based copolymer having excellent ozone resistance and high vulcanization rate.

Next, the method for producing the chain polyene group-containing norbornene compound [I] will be described in detail. [Production of norbornene compound [I] containing chain polyene group]
The method for producing the chain polyene group-containing norbornene compound [I] (and [I-a]) will be described in detail below.

The chain polyene group-containing norbornene compound [I] according to the present invention is produced as follows.

[0052]

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That is, the chain polyene group-containing norbornene compound [I] is described in Japanese Patent Application No. 6-154952 (filed on July 6, 1994) previously proposed by the applicant of the present application. As shown, first, ethylene and the formula [III-a]:

[0054]

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(In the formula [III-a], n is an integer of 1 to 5, R ¹ is an alkyl group having 1 to 5 carbon atoms, and R ² and R ³ are each independently a hydrogen atom or a carbon atom. Number 1-5
Is an alkyl group. Is reacted with a conjugated diene compound [III-a] represented by the formula (III):

[0056]

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(In the formula [III], n, R ¹ , R ² and R
³ shows the same thing as the case of the above [III-a]. )), And then disclosed in Japanese Patent Application No. 6-322099 (December 1994).
The above-mentioned norbornene compound [I] containing a chain polyene group is reacted by reacting this branched polyene compound [III] with cyclopentadiene (Diels-Alder reaction) as described in US Pat. can get.

Hereinafter, the chain polyene group-containing norbornene compound [I] will be sequentially described in more detail along with the above-mentioned production steps. [Production of Branched Polyene Compound [III]] The branched polyene compound [III] is a compound having a conjugated diene represented by the above formula [III-a] (hereinafter also referred to as a conjugated diene compound [III-a]). ) And ethylene.

In the above formula [III-a], examples of the alkyl group having 1 to 5 carbon atoms include those mentioned above.
Specific examples of such a conjugated diene compound represented by the formula [III-a] include the following compounds (1) to (24). (1): 3-methylene-1,5-heptadiene, (2): 6-methyl-3-methylene-1,5-heptadiene, (3): 6-methyl
-3-methylene-1,5-octadiene, (4): 6-ethyl-3-
Methylene-1,5-octadiene, (5): 5,6-dimethyl-3-
Methylene-1,5-heptadiene, (6): 5,6-dimethyl-3-
Methylene-1,5-octadiene, (7): 3-methylene-1,5-
Nonadiene, (8): 6-methyl-3-methylene-1,5-nonadiene, (9): 6-methyl-5-propyl-3-methylene-1,5-
Heptadiene, (10): 3-methylene-1,6-octadiene, (11): 7-methyl-3-methylene-1,6-octadiene, (12): 3-methylene-1,6-decadiene, (1
3): 7-methyl-3-methylene-1,6-decadiene, (1
4): 6,7-dimethyl-3-methylene-1,6-octadiene,
(15): 6,7-dimethyl-3-methylene-1,6-nonadiene,
(16): 6,7-dimethyl-3-methylene-1,6-decadiene,
(17): 7-methyl-6-ethyl-3-methylene-1,6-decadiene, (18): 6,7-diethyl-3-methylene-1,6-nonadiene, (19): 8-methyl- 3-methylene-1,7-nonadiene, (20): 7,8-dimethyl-3-methylene-1,7-nonadiene, (21): 9-methyl-3-methylene-1,8-decadiene,
(22): 8,9-dimethyl-3-methylene-1,8-decadiene,
(23): 10-methyl-3-methylene-1,9-undecadiene, (24): 9,10-dimethyl-3-methylene-1,9-undecadiene.

According to the above reaction, the branched polyene compound [III] is usually obtained as a mixture of trans isomer and cis isomer. Depending on the structure of the branched polyene compound [III], the trans form and the cis form can be separated by distillation.

Further, according to the above reaction, the following chain polyene compound represented by the general formula [III-b] may be produced as a by-product together with the branched chain polyene compound [III].

[0062]

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Specific examples of such by-products include:
For example, EMN is obtained by reacting 7-methyl-3-methylene-1,6-octadiene (β-myrcene) with ethylene.
5,9-dimethyl-1,4,8-decatriene which is by-produced when (4-ethylidene-8-methyl-1,7-nonadiene) is synthesized.

Such by-products can usually be separated by distillation. The reaction between the conjugated diene compound [III-a] and ethylene as described above is performed by the conjugated diene compound [I
II-a], usually 50-200 ° C
Preferably at a temperature of 70 to 150 ° C, ethylene pressure of 1 to 10
0 kg / cm ² preferably under a pressure of 10 to 70 kg / cm ^2,
Performed for 0.5 to 30 hours.

The reaction may be carried out in an atmosphere of an inert gas such as nitrogen or argon. The reaction can be performed without using a solvent. Can also.

This reaction is usually carried out in the presence of a catalyst. In particular, when the reaction is performed in the presence of a catalyst comprising a transition metal compound and an organoaluminum compound, a branched polyene compound [III] can be efficiently obtained.

Specific examples of such a transition metal compound include chlorides of transition metals selected from the iron group such as iron and ruthenium, the cobalt group such as cobalt, rhodium and iridium, and the nickel group such as nickel and palladium. Examples thereof include bromide, acetylacetonate salt, 1,1,1,5,5,5-hexafluoroacetylacetonate salt, and dipivaloylmethane salt. Of these, chlorides of cobalt, iron, nickel, rhodium and palladium are preferred, and chlorides of cobalt compounds are particularly preferred.

Such a transition metal compound (for example, a transition metal chloride) can be used in the reaction as it is, but it is preferably used as a transition metal complex in which an organic ligand is coordinated with the transition metal compound. That is, an organic compound (coordination compound) which can serve as a transition metal ligand coexists with the transition metal compound in the reaction system, or a transition metal complex is previously formed from the transition metal compound and the above coordination compound. It is preferable to use it.

Examples of the compound that can serve as such a ligand include bis (diphenylphosphino) methane,
1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, triethylphosphine, tributylphosphine, triphenylphosphine, cyclooctadiene, And cyclooctatetraene.

Further, as a complex in which an organic ligand is coordinated to a transition metal compound in advance, [1,2-bis (diphenylphosphino) ethane] cobalt (II) chloride, [1,2-bis (diphenylphosphine) Fino) ethane] nickel (II) chloride,
Bis (triphenylphosphine) nickel (II) chloride and the like are preferably used.

Examples of the organoaluminum compound include those used at the time of producing an unsaturated ethylene copolymer described later, and triethylaluminum is preferably used. The organoaluminum compound may be used as it is, or may be used as a toluene solution or a hexane solution.

In the reaction of the conjugated diene compound [III-a] with ethylene, the transition metal compound is preferably 0.001 to the conjugated diene compound [III-a].
In an amount of 10 mol%, particularly preferably 0.01 to 1 mol%
Used in amounts. Further, the coordination compound is preferably used in an amount of 0 to 20 times by mole, particularly preferably 0.1 to 5 times by mole, based on the transition metal compound.

The organoaluminum compound is preferably used in an amount of 1 to 200 mol times, and particularly preferably 3 to 100 mol times, of the transition metal compound.

In the present invention, after the transition metal compound (or transition metal complex) as described above and the organoaluminum compound are brought into contact with each other in advance, the reaction (conjugated diene compound [II
[Ia] with ethylene).

The conjugated diene compound [III-a] as described above
According to the reaction of ethylene with ethylene, the following branched polyene compound [III]:

[0076]

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(In the formula [III], n, R ¹ , R ² and R ³ have the same meanings as in the case of the formula [III-a]).

Such a branched polyene compound [II
Specific examples of [I] include compounds as exemplified in the following (1) to (24).
(6), (9), (11), (14), (19), (2)
0) is used. (1): 4-ethylidene-1,6-octadiene, (2): 7-
Methyl-4-ethylidene-1,6-octadiene, (3): 7-methyl-4-ethylidene-1,6-nonadiene, (4): 7-ethyl
--4-Ethylidene-1,6-nonadiene, (5): 6,7-Dimethyl-4-ethylidene-1,6-octadiene, (6): 6,7-Dimethyl-4-ethylidene-1,6- Nonadiene, (7): 4-ethylidene-1,6-decadiene, (8): 7-methyl-4-ethylidene
-1,6-decadiene, (9): 7-methyl-6-propyl-4-ethylidene-1,6-octadiene, (10): 4-ethylidene-
1,7-Nonadiene, (11): 8-methyl-4-ethylidene-1,
7-nonadiene (EMN), (12): 4-ethylidene-1,7
-Undecadiene, (13): 8-methyl-4-ethylidene-
1,7-Undecadiene, (14): 7,8-Dimethyl-4-ethylidene-1,7-nonadiene, (15): 7,8-Dimethyl-4-ethylidene-1,7-decadiene, (16): 7,8-dimethyl-4-
Ethylidene-1,7-undecadiene, (17): 8-methyl-
7-ethyl-4-ethylidene-1,7-undecadiene, (1
8): 7,8-diethyl-4-ethylidene-1,7-decadiene,
(19): 9-methyl-4-ethylidene-1,8-decadiene,
(20): 8,9-dimethyl-4-ethylidene-1,8-decadiene, (21): 10-methyl-4-ethylidene-1,9-undecadiene, (22): 9,10-dimethyl-4- Ethylidene-1,9-
Undecadiene, (23): 11-methyl-4-ethylidene-
1,10-dodecadien, (24): 10,11-dimethyl-4-ethylidene-1,10-dodecadien.

The chemical formulas of the above compounds (1) to (24) are summarized below.

[0080]

[Chemical 21]

[0081]

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[0082]

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[0083]

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These branched polyene compounds [III]
Are used alone or in combination of two or more when preparing the chain polyene group-containing norbornene compound [I]. The above-mentioned branched polyene compound [III] may be a mixture of a trans form and a cis form, or may be a trans form alone or a cis form alone.

[Chain polyene group-containing norbornene compound
[Production of [I]] In the present invention, then, the branched polyene compound (also referred to as “non-conjugated triene compound”) obtained as described above [III]:

[0086]

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By reacting (in the formula [III], n, R ¹ , R ² and R ³ have the same meanings as described above) with cyclopentadiene (Diels-Alder reaction),
Norbornene compound containing chain polyene group [I]:

[0088]

[Chemical formula 26]

(In the formula [I], n represents an integer of 1 to 5,
R ¹ represents an alkyl group having 1 to 5 carbon atoms, and R ² and R ³
Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ) Is obtained.

In the above general formula [I], when R ¹ , R ² or R ³ is an alkyl group having 1 to 5 carbon atoms, such an alkyl group includes, for example, a methyl group, an ethyl group,
n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n
-A pentyl group, an isopentyl group and the like.

In the branched polyene compound [III] used in the above reaction, R ¹ and R ² have 1 carbon atoms.
To 3 alkyl groups, particularly preferably a methyl group, and R ³ is preferably hydrogen.

Cyclopentadiene is usually obtained by pyrolytic distillation of its dimer, dicyclopentadiene, at 160 ° C. or higher. Therefore, in the present invention,
Cyclopentadiene and branched polyene compounds [III]
Depending on the reaction temperature employed, dicyclopentadiene is used in place of cyclopentadiene, and this dicyclopentadiene is thermally decomposed in the reaction system to generate cyclopentadiene. May be used for the reaction with the polyene compound [III].

The reaction between such a cyclopentadiene and the branched polyene compound [III] varies depending on the branched polyene compound [III] used, but is preferably an atmosphere of an inert gas such as nitrogen or argon. Below, 0.2 to 4 parts by weight, preferably 0.5 to 4 parts by weight of cyclopentadiene per 1 part by weight of the branched polyene compound [III].
3 parts by weight at 50 to 250 ° C., preferably 100 to 200 ° C.
It is carried out by heating and stirring at a temperature in the range of 1 ° C. under a pressure of 1 to 100 kg / cm ^2, preferably 5 to 70 kg / cm ² for about 0.5 to 30 hours.

The reaction may be carried out in the presence of a radical polymerization inhibitor such as hydroquinone, if necessary. In the reaction between the cyclopentadiene and the branched polyene compound [III], the reaction solvent need not be particularly used, but may be used.

When a reaction solvent is used, examples of the reaction solvent include hydrocarbon solvents such as hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, toluene and xylene, dichloromethane,
Halogen hydrocarbons such as dichloroethane and dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, methanol, ethanol, isopropanol, t
-An alcoholic solvent such as butanol can be used. Water can also be used as a reaction solvent.

The chain polyene group-containing norbornene compound [I] thus obtained is represented by the above formula [I],
Examples of the norbornene compound [I] containing a chain polyene group include those described above.

The chain-like polyene group-containing norbornene compound [I] thus obtained usually has a stereoisomeric structure (an endo-form and an exo-form and a chain-form polyene based on the bonding of the chain-form polyene to the norbornene skeleton). Trans and cis forms based on how to replace heavy bonds)
Having.

The structure of the chain polyene group-containing norbornene compound [I] can be determined by measuring mass spectrometry, infrared absorption spectrum, proton NMR spectrum and the like.

In the present invention, such a chain polyene group-containing norbornene compound [I] contains an unsaturated ethylene copolymer as described below, and the unsaturated ethylene copolymer. When used for producing a rubber composition, it may be a mixture of various norbornene compounds having the above-mentioned stereoisomeric structure as described above,
Any one of the stereoisomers may be used alone.

According to the above reaction, the chain polyene group-containing norbornene compound [I] is usually obtained as a mixture of an endo form and an exo form, and in some cases, can be separated by distillation.

In addition to the above branched polyene compound [III], the branched polyene compound [III] was synthesized as a raw material for the polyene compound used in the preparation of the chain polyene group-containing norbornene compound [I]. By-products generated in the process [III-b]:

[0102]

Embedded image

When this by-product [III-
b] and cyclopentadiene to form a norbornene compound containing chain polyene group [Ia]:

[0104]

Embedded image

(In the formula [Ia], R ¹ , R ² , R ³ and n are
This is the same as in the case of the formula [I]. ) Is by-produced. As will be described later, in the production of the unsaturated ethylene-based copolymer according to the present invention, a small amount of chain polyene group-containing norbornene compound [Ia] together with such chain polyene group-containing norbornene compound [I] is used. Containing norbornene compound containing chain polyene group containing (compounds [I] and [I
-A] can also be used.

As described above, in addition to the chain polyene group-containing norbornene compound [I], a by-product chain polyene group-containing norbornene compound [Ia] is also contained ([I] and [I- a)), as described below,
Unsaturated ethylene-based copolymer obtained when used as a chain polyene group-containing compound [A] (iii) in the reaction of ethylene (i) with α-olefin (ii) having 3 to 20 carbon atoms In addition to the structural unit [II] derived from the norbornene compound [I], a structural unit [II-a] derived from the norbornene compound [Ia] as a structural unit derived from a norbornene compound containing a chain polyene group You get the included ones.

For example, as the chain polyene group-containing norbornene compound, [I]: EMHN {: 5- (2-ethylidene-6-methyl-5-heptenyl) -2-norbornene}
In addition, a small amount of by-product [Ia]: (5- [3,7-
Dimethyl-2,6-octadienyl] -2-norbornene) -containing "EMHN-containing material" is used.
Structural unit derived from N [II ']:

[0108]

[Chemical 29]

In addition to the above, a structural unit [II-a ′] derived from the by-product [Ia]:

[0110]

Embedded image

Is obtained in the above amount (small amount). The chain polyene group-containing norbornene compound itself represented by the formula [Ia] is described in Japanese Patent Application No. 7-75288 (March 31, 1995).
It can also be obtained by the method described in (Japanese application).

That is, cyclopentadiene and general formula (a):

[0113]

[Chemical 31]

[In the formula (a), m and n each independently represent an integer of 1 to 5, and R ¹ , R ² , R ^{3 and} R ^a , R
^b represents hydrogen or an alkyl group having 1 to 5 carbon atoms as in the case of the formula [I]. Where R ¹ , R ² , R
³ is not simultaneously hydrogen. By reacting with a chain non-conjugated triene compound represented by the following formula (b):

[0115]

Embedded image

[In the formula (b), m, n, R ¹ , R ² , R ³ ,
R ^a and R ^b are the same as those in the case of the formula (a). And a chain polyene group-containing norbornene compound represented by the following formula:

Next, the unsaturated ethylene-based copolymer according to the present invention having the structural unit [II] derived from the chain polyene group-containing norbornene compound [I] as described above and the method for producing the same will be described.

[ Unsaturated Ethylene Copolymer] The unsaturated ethylene copolymer according to the present invention comprises [A] (i) ethylene, (ii) an α-olefin having 3 to 20 carbon atoms, and (iii) A random copolymer with a chain polyene group-containing norbornene compound [I].

The unsaturated ethylenic copolymer according to the present invention comprises [A] (i) ethylene, (ii) an α-olefin having 3 to 20 carbon atoms, and (iii) as described above. Chain polyene group-containing norbornene compound [I] and a small amount of the chain polyene group-containing norbornene compound [I-
It may be a random copolymer with a].

Specific examples of the (ii) C3-C20 α-olefin include propylene, 1-butene, and
1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4, 4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene,
3-Ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned, preferably propylene, 1-butene, 1- Hexene, 1-octene is used. These α-olefins are used alone or in combination of two or more.

The above-mentioned (iii) chain polyene group-containing norbornene compound [I] has the following general formula [I]:
It is represented by

[0122]

[Chemical 33]

In the formula [I], n is an integer of 1 to 5 and R ¹
Is an alkyl group having 1 to 5 carbon atoms, and R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The numbers 1 to 7 and n + 3 indicate the carbon number (substituent position).

Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-group. -Butyl group, n-pentyl group, i-pentyl group and the like.

Specific examples of the chain-like polyene group-containing norbornene compound (iii) represented by the formula [I] (chain-like polyene group-containing norbornene compound [I]) are as described above in (1) to (24). Examples include compounds such as
Preferably, (5), (6), (9), (11), (1
4), (19) and (20) are used.

These may be used alone or in combination of two or more. The chain polyene group-containing norbornene compound [I] used in the present invention may be one of the stereoisomers, for example, the trans isomer alone or the cis isomer alone, and a stereoisomer mixture such as the trans isomer and the cis isomer. It may be a mixture of bodies.

The unsaturated ethylene-based copolymer according to the present invention comprises the above-mentioned (i) ethylene, (ii) α-olefin and (iii) chain-like polyene group-containing norbornene compound [I] in a single amount. Constituent units derived from the body are randomly arranged and bound to each other, and (iii) has a branched structure derived from the chain-like polyene group-containing norbornene compound, and the main chain has a substantially linear structure. . The fact that the copolymer has a substantially linear structure and does not substantially contain a gel-like crosslinked polymer means that the copolymer is dissolved in an organic solvent and contains substantially no insoluble matter. Can be confirmed by For example, when the intrinsic viscosity [η] is measured, it can be confirmed by the fact that the copolymer is completely dissolved in decalin at 135 ° C.

The unsaturated ethylene-based copolymer according to the present invention comprises the structural unit derived from ethylene (i) above
To 92 mol%, preferably 40 to 90 mol%, more preferably 45 to 90 mol%, (ii) having 3 to 20 carbon atoms.
A structural unit derived from the α-olefin of 6 to 70
Mol%, preferably 8 to 60 mol%, more preferably 10 to 55 mol%, and (iii) 0.1 to 30 mol of the structural unit derived from the chain polyene group-containing norbornene compound [I]. %, Preferably 0.1-20 mol%,
More preferably, it is contained in an amount of 0.2 to 10 mol%.

Particularly in the unsaturated ethylene-based copolymer according to the present invention, the structural unit derived from (i) ethylene and
(ii) The structural unit derived from an α-olefin having 3 to 20 carbon atoms is a molar ratio ((i) ethylene / (ii) α-olefin) of 40/60 to 92/8, preferably 45 / 55
To 90/10, more preferably 50/50 to 88/1
Present in an amount of 2.

In the unsaturated ethylenic copolymer according to the present invention, the structural unit derived from the chain polyene group-containing norbornene compound [I] has a structure substantially represented by the following formula [II]: have.

[0131]

Embedded image

[In the formula [II], n is an integer of 1 to 5,
R ¹ is an alkyl group having 1 to 5 carbon atoms, and R ² and R ³
Is each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. It can be confirmed that the constitutional unit derived from the chain polyene group-containing norbornene compound has the above structure by measuring the ¹³ C-NMR spectrum of this copolymer.

The unsaturated ethylenic copolymer according to the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.05 to 10 dl / g, preferably 0.1 to 7 dl / g,
More preferably, it is 0.2 to 5 dl / g.

In the unsaturated ethylene-based copolymer according to the present invention, in addition to the chain polyene group-containing norbornene compound [I] in the above [A] (iii), the following general formula [I-a ]:

[0135]

Embedded image

(In the formula [Ia], n, R ¹ , R ² and R ³
Is the same as in the case of the above [I]. )) At least one chain polyene group-containing norbornene compound [Ia] is present in a small amount relative to the above compound [I], preferably in a total of 100 mol% of [I] + [Ia]. The compound [Ia] is less than 50 mol%, more preferably 4
It may be contained in an amount of 0 mol% or less, particularly preferably 35 mol% or less.

The chain polyene group-containing norbornene compound [Ia] is obtained as a by-product as described above when the chain polyene group-containing norbornene compound [I] is synthesized, for example.

In such a random copolymer, [B] (iii): the above structural unit [II] derived from the chain polyene group-containing norbornene compound represented by the above general formula [I], and the above general formula The total amount of the structural unit [II-a] derived from the chain polyene group-containing norbornene compound represented by [Ia] ([II] + [II]
-A]) is in the same range as the amount of the structural unit [II] derived from the chain polyene group-containing norbornene compound described above. That is, [II] + [II-a] = 0.
It is 1 to 30 mol%, preferably 0.1 to 20 mol%, and more preferably 0.2 to 10 mol%.

Further, the structural unit [II] and the structural unit [II-
The copolymerization ratio with a] is an amount corresponding to the molar ratio of the chain polyene group-containing norbornene compound [I] and [Ia] used. That is, the structural unit [II] and the structural unit [II
-A] in 100 mol% in total, the structural unit [II-a]
Is copolymerized at a component ratio of less than 50 mol%, preferably 40 mol% or less, more preferably 35 mol% or less.

In such a random copolymer,
[C]: the structural unit derived from the chain polyene group-containing norbornene compound represented by the general formula [I] has the structure represented by the formula [II] as described above,
The structural unit derived from the chain polyene group-containing norbornene compound represented by the above general formula [Ia] is represented by the following formula [II-a]:

[0141]

Embedded image

(In the formula [II-a], n, R ¹ , R ² and R
Each of ³ is the same as the case of the above [II]. ). Other points [Example: (i) Amount of ethylene constitutional units (mol%), (ii) Ethylene constitutional units /
α-olefin structural unit (molar ratio), intrinsic viscosity of copolymer, etc. ] Is the same as in the case of the above copolymer containing no structural unit [II-a].

[0143] In the present specification, unless otherwise specified, the "chain-like polyene group-containing norbornene compound" is simply referred to as "chain-like polyene group-containing norbornene compound [I] and chain-like polyene compound". The group-containing norbornene compound [Ia] is used to include both, and when the term "structural unit derived from the chain polyene group-containing norbornene compound" is used, the chain polyene group-containing norbornene compound [I] is used. Induced building blocks [II]
And a chain-like polyene group-containing norbornene compound [I-
a] is used to mean both structural units [II-a] derived from [a].

The unsaturated ethylenic copolymer according to the present invention as described above is excellent in weather resistance, heat resistance and ozone resistance and has a high vulcanization rate. The unsaturated ethylene copolymer according to the present invention may be used as it is unvulcanized, or may be vulcanized by a vulcanizing method as described below and used in a vulcanized state. When used in the sulphurized state, its properties are further exhibited.

Such an unsaturated ethylene-based copolymer is particularly preferably used as a resin modifier and various rubber products. Specifically, when the unsaturated ethylene copolymer according to the present invention is added as a resin modifier to, for example, polypropylene, polyethylene, polybutene, polystyrene, etc., its impact resistance and stress crack resistance are dramatically improved. improves.

The unsaturated ethylene copolymer according to the present invention may be vulcanized alone and used, or may be covulcanized with another rubber material before use. Since this unsaturated ethylene-based copolymer has a high vulcanization rate, it can be vulcanized in a shorter time or at a lower temperature than conventional unsaturated ethylene-based copolymers without using a large amount of vulcanizing agent. Therefore, the vulcanized rubber can be manufactured with high productivity.

The unsaturated ethylenic copolymer according to the present invention is particularly excellent in covulcanizability with diene rubbers such as natural rubber, styrene-butadiene rubber, isoprene rubber, butadiene rubber, nitrile rubber and chloroprene rubber. The co-vulcanized product of the unsaturated ethylene copolymer and the diene rubber is excellent and has the excellent mechanical properties, wear resistance, dynamic fatigue resistance, and oil resistance originally possessed by the diene rubber. It also has excellent weather resistance, ozone resistance, and heat aging resistance.

Specifically, for example, the co-vulcanized product of the unsaturated ethylene copolymer and the natural rubber according to the present invention is excellent in strength, weather resistance, ozone resistance and dynamic resistance. The co-vulcanized product of the unsaturated ethylene copolymer and the nitrile rubber according to the present invention is excellent in weather resistance, ozone resistance and oil resistance.

The co-vulcanized product of the unsaturated ethylene copolymer and butadiene rubber according to the present invention is excellent in weather resistance, ozone resistance and abrasion resistance. [ Production of Unsaturated Ethylene Copolymer ] The unsaturated ethylene copolymer according to the present invention as described above includes (i) ethylene, (ii) an α-olefin having 3 to 20 carbon atoms, and (iii)
A chain polyene group-containing norbornene compound represented by the above general formula [I] (and optionally a small amount of the above compound [Ia] relative to the amount of the compound [I]),
It is obtained by copolymerization in the presence of a catalyst.

As such a catalyst, a catalyst comprising a transition metal compound such as vanadium (V), zirconium (Zr) and titanium (Ti) and an organoaluminum compound (organoaluminumoxy compound) and / or an ionized ionic compound is used. In the present invention, among them, [a] a catalyst composed of a soluble vanadium compound and an organoaluminum compound, or [b] a metallocene compound of a transition metal selected from Group IVB of the periodic table,
A catalyst consisting of an organoaluminum oxy compound and / or an ionized ionic compound is particularly preferably used.

The soluble vanadium compound forming the catalyst [a] is specifically represented by the following general formula. VO (OR) _{a Xb} or V (OR) _c X _{d In the} formula, R is a hydrocarbon group, X is a halogen atom, and a, b, c, and d are respectively 0 ≦ a ≦ 3, 0 ≦ b ≦
3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ c
+ D ≦ 4 is satisfied.

Specific examples of the soluble vanadium compound represented by the above formula include VOCl ₃ and VO (OCH ₃ ) C.
l ₂ , VO (OC ₂ H ₅ ) Cl ₂ , VO (OC ₂ H ₅ ) _1.5 C
_{l 1.5, VO (OC 2 H} 5) 2 Cl, VO (O-n-C 3 H 7)
Cl ₂ , VO (O-iso-C ₃ H ₇ ) Cl ₂ , VO (O-n-C ₄
H ₉ ) Cl ₂ , VO (O-iso-C ₄ H ₉ ) Cl ₂ , VO (O-s
_{ec-C 4 H 9) Cl} 2, VO (O-t-C 4 H 9) Cl 2, VO
_{(OC 2 H 5) 3,} VOBr 2, VCl 4, VOCl 2 VO (O-n-C 4 H 9) 3, etc. VOCl ₃ · 2OC ₈ H ₁₇ OH and the like.

These may be used alone or in combination of two or more. The above-mentioned soluble vanadium compound can also be used as an electron donor adduct of these soluble vanadium compounds obtained by contacting an electron donor as shown below.

Examples of such electron donors include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, organic acid or inorganic acid esters, ethers, diethers and acid amides. , Acid anhydrides, oxygen-containing electron donors such as alkoxysilane, and nitrogen-containing electron donors such as ammonia, amines, nitriles, pyridines, and isocyanates.

More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol,
C1-C18 alcohols such as cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol; C1-C18 halogen-containing alcohols such as trichloromethanol, trichloroethanol and trichlorohexanol; phenol, cresol, xylenol, ethylphenol , Propylphenol,
Nonylphenol, cumylphenol, phenol having 6 to 20 carbon atoms which may have an alkyl group such as naphthol, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, ketones having 3 to 15 carbon atoms such as benzoquinone, Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate , Methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate,
Ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl Organic acid esters having 2 to 18 carbon atoms such as ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethyl carbonate, etc., acetyl chloride, benzoyl chloride C2-15 acid halides such as toluic acid chloride, anisic acid chloride, methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether and the like Ethers prime 2-20, acetic anhydride, phthalic acid anhydride, acid anhydrides such as benzoic acid,
Ethyl silicate, alkoxysilane such as diphenyldimethoxysilane, acetic acid N, N-dimethylamide, benzoic acid N, N-
Acid amides such as diethylamide and toluic acid N, N-dimethylamide; amines such as trimethylamine, triethylamine, tributylamine, tribenzylamine and tetramethylethylenediamine; nitriles such as acetonitrile, benzonitrile and tolunitrile; pyridine and methylpyridine And pyridines such as ethylpyridine and dimethylpyridine.

When preparing an electron donor adduct of a soluble vanadium compound, these electron donors can be used alone or in combination of two or more kinds. The organoaluminum compound used when forming the catalyst [a] in the present invention is represented by the following formula [III].

R ¹ _n AlX _3-n ... [III] In the formula, R ¹ is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1-3.

Examples of such a hydrocarbon group having 1 to 15 carbon atoms include an alkyl group, a cycloalkyl group and an aryl group. Specific examples include a methyl group, an ethyl group, an n-propyl group, Examples thereof include isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

Specific examples of such an organoaluminum compound include the following compounds. Trimethylaluminum, triethylaluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, trialkyl aluminum Nim and tri 2-ethylhexyl aluminum, the general formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z [In the formula, x, y, and z are positive numbers, and z ≧ 2x. ] Alkenyl aluminum such as isoprenyl aluminum, trialkenyl aluminum such as triisopropenyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, dialkyl aluminum halide such as dimethyl aluminum bromide, methyl aluminum sesqui Chloride, ethylaluminium sesquichloride,
Alkyl aluminum sesquihalides such as isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide, alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, ethyl aluminum dibromide, diethyl aluminum hydride, dibutyl aluminum Examples thereof include dialkyl aluminum hydrides such as hydride, ethyl aluminum dihydride, alkyl aluminum dihydrides such as propyl aluminum dihydride, and the like.

As the organoaluminum compound, a compound represented by the following formula [IV] can also be mentioned. R ¹ _n AlY _3-n ... [IV] wherein R ¹ is the same as in the above formula [III], and Y is -OR
¹⁰ group, -OSiR ¹¹ ₃ group, -OAlR ¹² ₂ group, -NR ¹³ ₂
Group, an -SiR ¹⁴ ₃ group or -N (R ¹⁵⁾ AlR ¹⁶ ₂ group. R ¹⁰ , R ¹¹ , R ¹² and R ¹⁶ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group and the like, and R ¹³ is hydrogen, a methyl group, an ethyl group, an isopropyl group, a phenyl group, R ¹⁴ and R ¹⁵ are a methyl group, an ethyl group and the like. n is 1-2.

Specific examples of the organoaluminum compound represented by the formula [IV] include the following compounds. However, Me is a methyl group, Et is an ethyl group, Bu is a butyl group, and R ¹ to ¹⁶ are the same as in [IV]. _{^{(1) R 1 n Al (}} OR 10) a compound represented by _3-n, e.g., dimethylaluminum methoxide, diethylaluminum ethoxide, dialkylaluminum alkoxides such as diisobutylaluminum methoxide, ethylaluminum sesquichloride ethoxide, butyl aluminum Partial alkoxy, such as sesquibutoxide and partially alkoxylated alkylaluminum, ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, and ethylaluminum ethoxybromide having an average composition represented by R ¹ _2.5 Al (OR ² ) _{0.5 and the} like. And halogenated alkyl aluminum. _{^{(2) R 1 n Al (}} OSi R 11 3) a compound represented by _3-n,
For example, such _{Et 2 Al (OSi Me 3)} (iso-Bu) 2 Al (OSi Me 3) (iso-Bu) 2 Al (OSi Et 3), (3) R 1 n Al (OAlR 12 2) 3- a compound represented by _n ,
For example, such _{Et 2 AlOAlEt 2 (iso-Bu} ) 2 AlOAl (iso-Bu) 2, (4) R 1 n Al (NR 13 2) a compound represented by _3-n, e.g., Me ₂ AlNEt ₂ Et ₂ such _{AlNHMe Me 2 AlNHEt Et 2 AlN (} Si Me 3) 2 (iso-Bu) 2 AlN (SiMe 3) 2, (5) R 1 n Al (Si R 14 3) a compound represented by _3-n, e.g. , (iso-Bu) _2, etc. _{AlSi Me 3, (6) R} 1 n Al [n (R 13) AlR 16 2] a compound represented by _3-n, e.g., _{Et 2 AlN (Me) AlEt 2} , (i
so-Bu) ₂ AlN (Et) Al (iso-Bu) ₂ etc.

Of these, alkylaluminum halides, alkylaluminum dihalides and combinations thereof are particularly preferable. The organoaluminum compound used in the present invention may contain a small amount of an organic compound component of a metal other than aluminum.

Next, the catalyst composed of the metallocene compound [b] and the organoaluminumoxy compound or the ionized ionic compound used in the present invention will be described. Such a transition metal metallocene compound selected from Group IVB of the periodic table is specifically represented by the following formula [V].

MLx ... [V] In the formula [V], M is a transition metal selected from Group IVB of the periodic table, specifically zirconium, titanium or hafnium, and x is a valence of the transition metal. .

L is a ligand that coordinates to a transition metal, and at least one of these ligands L is a ligand having a cyclopentadienyl skeleton and has this cyclopentadienyl skeleton. The ligand may have a substituent.

Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n- or i-propylcyclopentadienyl group, n-,
i-, sec-, t-, butylcyclopentadienyl group, hexylcyclopentadienyl group, octylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group Group, pentamethylcyclopentadienyl group, methylethylcyclopentadienyl group, methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, methylhexylcyclopentadienyl group, methylbenzylcyclopentadienyl group, Alkyl- or cycloalkyl-substituted cyclopentadienyl groups such as ethylbutylcyclopentadienyl group, ethylhexylcyclopentadienyl group, methylcyclohexylcyclopentadienyl group, indenyl group, 4,5,6,7-tetrahydroindenyl group Group, fluores And the like.

These groups may be substituted with a halogen atom, a trialkylsilyl group or the like. Among these, an alkyl-substituted cyclopentadienyl group is particularly preferred.

When the compound represented by the formula [V] has two or more groups having a cyclopentadienyl skeleton as the ligand L, two of the groups having a cyclopentadienyl skeleton are ethylene groups. , An alkylene group such as propylene, a substituted alkylene group such as isopropylidene or diphenylmethylene, a silylene group or a dimethylsilylene group, a diphenylsilylene group, a substituted silylene group such as a methylphenylsilylene group, and the like.

Ligand having cyclopentadienyl skeleton
L other than is a hydrocarbon group having 1 to 12 carbon atoms,
Coxy group, aryloxy group, sulfonic acid-containing group (-SO
_Three R ^a ), A halogen atom or a hydrogen atom (where R^a 
Is an alkyl group, an alkyl group substituted with a halogen atom,
Substituted with aryl group, halogen atom or alkyl group
Aryl group. ).

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group, and more specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group. Groups, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, decyl group, alkyl groups such as dodecyl group, cyclopentyl group, cycloalkyl groups such as cyclohexyl group, Examples thereof include an aryl group such as a phenyl group and a tolyl group, and an aralkyl group such as a benzyl group and a neofil group.

As the alkoxy group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group,
Examples include an n-butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, a pentoxy group, a hexoxy group, and an octoxy group.

Examples of the aryloxy group include a phenoxy group, and examples of the sulfonic acid-containing group (-SO ₃ ^Ra ) include a methanesulfonato group, a p-toluenesulfonato group,
Examples include a trifluoromethanesulfonato group and a p-chlorobenzenesulfonato group.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. The metallocene compound represented by the above formula, for example, when the valence of the transition metal is 4,
More specifically, it is represented by the following formula [VI].

R ² _k R ³ _l R ⁴ _m R ⁵ _n M ... [VI] In the formula [VI], M is the above transition metal, and R ² is a group (ligand) having a cyclopentadienyl skeleton. And R ³ ,
R ⁴ and R ⁵ are independently the same as L except for a group having a cyclopentadienyl skeleton or a ligand having a cyclopentadienyl skeleton in the general formula [V]. k is an integer of 1 or more, and k + 1 + m + n = 4.

In the following, at least 2 ligands in which M is zirconium and have a cyclopentadienyl skeleton are used.
Metallocene compounds are exemplified. Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methyl zirconium monochloride, bis (cyclopentane Dienyl) zirconium phenoxymonochloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (n-propylcyclopentadienyl) zirconium dichloride, bis (isopropylcyclopentadienyl) )
Zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (sec-butylcyclopentadienyl) zirconium dichloride, bis (isobutylcyclopentadienyl) Zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (octylcyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (Indenyl) zirconium dibromide, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium methoxychloride, bis (cyclopentadienyl) di Ruconium ethoxycyclolide, bis (fluorenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato), bis (cyclopentadienyl) ) Zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (ethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (propylcyclopentadiene) Enyl) zirconium bis (trifluoromethanesulfonato), bis (butylcyclopentadienyl)
Zirconium bis (trifluoromethanesulfonate),
Bis (hexylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (1,3-dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (1-methyl-3-ethylcyclopentadi (Enyl) zirconium bis (trifluoromethanesulfonato), bis (1-methyl-3-propylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (1-methyl-3-butylcyclopentadienyl) zirconium bis (Trifluoromethanesulfonato), bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-ethylcyclopentadienyl) zirconium dichloride,
Bis (1-methyl-3-propylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-butylcyclopentadienyl) zirconium dichloride, bis (1-
Methyl-3-hexylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-octylcyclopentadienyl) zirconium dichloride, bis (1-ethyl
-3-butylcyclopentadienyl) zirconium dichloride, bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (methyl) Examples thereof include benzylcyclopentadienyl) zirconium dichloride, bis (ethylhexylcyclopentadienyl) zirconium dichloride, and bis (methylcyclohexylcyclopentadienyl) zirconium dichloride.

A compound obtained by substituting the 1,3-position-substituted cyclopentadienyl group with a 1,2-position-substituted cyclopentadienyl group can also be used in the present invention. Further, in the above formula [VI], at least two of R ² , R ³ , R ⁴ and R ⁵ , that is, R ² and R ³ are groups (ligands) having a cyclopentadienyl skeleton, and at least 2 of these groups are present. The group can also be exemplified by a bridge-type metallocene compound which is bonded via an alkylene group, a substituted alkylene group, a silylene group or a substituted silylene group. At this time, R ⁴ and R ⁵ are each independently the formula [V]
It is the same as L except for the ligand having a cyclopentadienyl skeleton described in the above.

Examples of such bridge-type metallocene compounds are ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium bis (trifluoromethanesulfonate), ethylenebis (indenyl) zirconium. Bis (methanesulfonato), ethylenebis (indenyl) zirconium bis (p-toluenesulfonato), ethylenebis (indenyl) zirconium bis (p-chlorobenzenesulfonato), ethylenebis (4,5,6,7-tetrahydro) Indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium Chloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) Zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconiumbis (trifluoromethanesulfonato), dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis ( Cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, Such as chill phenyl (indenyl) zirconium dichloride.

Furthermore, Japanese Patent Laid-Open No. Hei 4 (1994) represented by the following formula [A]
Metallocene compounds described in JP-A-268307. The metallocene has the formula [A]:

[0179]

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[In the formula [A], M ¹ is IV in the periodic table.
It is a metal of group b, Vb or VIb, and specific examples thereof include titanium, zirconium and hafnium.

R ¹ and R ² may be the same as or different from each other, and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, and 1 to 10 carbon atoms, preferably 1 carbon atom.
~ 3 alkoxy groups, 6-10 carbon atoms, preferably 6 carbon atoms
~ 8 aryl group, 6 to 10 carbon atoms, preferably 6 to
8 aryloxy groups, alkenyl groups having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms; arylalkyl groups having 7 to 40 carbon atoms, preferably 7 to 10 carbon atoms; alkyls having 7 to 40 carbon atoms, preferably 7 to 12 carbon atoms Aryl group, 8 carbon atoms
-40, preferably 8-12 arylalkenyl groups, or halogen atoms, preferably chlorine atoms.

R ³ and R ⁴ may be the same or different from each other, and are a hydrogen atom, a halogen atom, preferably a fluorine atom, a chlorine atom or a bromine atom, and an optionally halogenated carbon atom number of 1 to 10, preferably 1-4 alkyl group, an aryl group having 6 to 10 carbon atoms, preferably _{^{6~8, -NR 2 10, -SR 10}} , -OSiR 3 10, -SiR 3
Is ¹⁰ or -PR ₂ ¹⁰ radical, where R ¹⁰ is a halogen atom preferably a chlorine atom or an alkyl group having 1 to 10 preferably 1 to 3 carbon atoms, or carbon atoms, 6-1
0 is preferably a 6-8 aryl group.

R ³ and R ⁴ are particularly preferably hydrogen atoms. R ⁵ and R ⁶ may be the same or different and are preferably the same and have the same meaning as described for R ³ and R ^{4 with the} proviso that R ⁵ and R ⁶ are not hydrogen atoms. R ⁵ and R ⁶ are preferably an optionally halogenated alkyl group having 1 to 4 carbon atoms, specifically, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group. Alternatively, a trifluoromethyl group and the like can be mentioned, and a methyl group is preferable.

R ⁷ is the following:

[0185]

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= BR¹¹, = AlR¹¹, -Ge-, -Sn
-, -O-, -S-, = SO, = SO ₂, = NR¹¹, =
CO, = PR¹¹Or = P (O) R¹¹Where R
¹¹, R^{1 2}And R¹³May be the same or different
And preferably a hydrogen atom, a halogen atom, and a carbon number of 1 to 10.
Is an alkyl group of 1-4, more preferably a methyl group, carbon
A fluoroalkyl group having 1 to 10 atoms, preferably CF_Three
Group, aryl having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms
Group, preferably a fluoroaryl group having 6 to 10 carbon atoms
Is a pentafluorophenyl group, preferably having 1 to 10 carbon atoms.
Or 1-4 alkoxy groups, particularly preferably methoxy
Group, alkenyl having 2 to 10, preferably 2 to 4 carbon atoms
Group, aryl having 7 to 40 carbon atoms, preferably 7 to 10 carbon atoms
An alkyl group having 8 to 40 carbon atoms, preferably 8 to 12 carbon atoms;
An arylalkenyl group or a group having 7 to 40 carbon atoms
Preferably 7 to 12 alkylaryl groups, or
"R¹¹And R ¹²"Or" R¹¹And R¹³Is each
May form a ring with the atoms to which they bind
Yes.

M ² is silicon, germanium or tin, preferably silicon or germanium. R ⁷ is = CR
^{11 R 12, = SiR 11 R} 12, = GeR 11 R 12, -O -, -
S -, = SO, it is preferred that = PR ¹¹ or = P (O) R ^11.

R ⁸ and R ⁹ may be the same or different from each other and have the same meaning as described for R ¹¹ . m and n may be the same or different and are 0, 1 or 2, preferably 0 or 1, and m + n is 0, 1 or 2, preferably 0 or 1.

Particularly preferred metallocenes satisfying the above conditions are shown in (i) to (iii) below.

[0190]

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[In the above formulas (i), (ii) and (iii), M ¹ is Zr or Hf, R ¹ and R ² are methyl groups or chlorine atoms, and R ⁵ and R ⁶ are methyl groups. , Ethyl group or trifluoromethyl group, and R ⁸ , R ⁹ , R ¹⁰ and R ¹² have the above meanings. Among the compounds represented by the formulas (i), (ii) and (iii), the following compounds are particularly preferred.

Rac-ethylene (2-methyl-1-indenyl) ₂ -zirconium-dichloride, rac-dimethylsilylene (2-methyl-1-indenyl) ₂ -zirconium-dichloride, rac-dimethylsilylene (2-methyl-1) -
Indenyl) ₂ - Zirconium - dimethyl, rac- ethylene - (2-methyl-1-indenyl) ₂ - Zirconium - dimethyl, rac- phenyl (methyl) silylene - (2 Mechiru-1-indenyl) ₂ - Zirconium - dichloride, r
ac-diphenyl-silylene- (2-methyl-1-indenyl) ₂ -zirconium-dichloride, rac-methylethylene- (2-methyl-1-indenyl) ₂ -zirconium-dichloride, rac-dimethylsilylene- (2-ethyl-1)
-Indenyl) ₂ -zirconium-dichloride. Regarding the method for producing such a metallocene, it can be produced by a conventionally known method (for example, JP-A-4-2683).
No. 07 gazette).

In the present invention, a transition metal compound (metallocene compound) represented by the following formula [B] can also be used.

[0194]

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In the formula [B], M is IVa, Va, V of the periodic table.
It represents a transition metal atom of Group Ia, and specifically, titanium, zirconium, and hafnium. R ¹ and R ²
Are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group,
Represents a nitrogen-containing group or a phosphorus-containing group, specifically, a halogen atom such as fluorine, chlorine, bromine, or iodine; methyl,
Alkyl groups such as ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl and adamantyl, alkenyl groups such as vinyl, propenyl and cyclohexenyl, arylalkyl groups such as benzyl, phenylethyl and phenylpropyl, A hydrocarbon group having 1 to 20 carbon atoms such as an aryl group such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl, phenanthryl; and a halogen atom in the hydrocarbon group. Substituted halogenated hydrocarbon group; monohydrocarbon substituted silyl such as methylsilyl and phenylsilyl, dihydrocarbon substituted silyl such as dimethylsilyl and diphenylsilyl, trimethylsilyl, Triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, trinaphthylsilyl and other trihydrocarbon-substituted silyl, trimethylsilyl ether and other hydrocarbon-substituted silyl silyl ethers, trimethylsilyl Silicon-containing alkyl groups such as methyl, silicon-substituted aryl groups such as trimethylsilylphenyl, silicon-containing groups such as; hydroxy groups, alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, and allyoxy such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy. Group, an oxygen-containing group such as an arylalkoxy group such as phenylmethoxy or phenylethoxy; a substituent in which oxygen of the oxygen-containing group is replaced with sulfur Sulfur-containing groups; amino groups, alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino, arylamino such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino Groups or nitrogen-containing groups such as alkylarylamino groups;
And phosphorus-containing groups such as phosphino groups such as dimethylphosphino and diphenylphosphino.

Of these, R ¹ is preferably a hydrocarbon group, particularly methyl, ethyl and propyl having 1 carbon atoms.
It is preferably from 3 to 3 hydrocarbon groups. R ² is preferably hydrogen or a hydrocarbon group, particularly preferably hydrogen or a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl and propyl.

R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, Of these, hydrogen, a hydrocarbon group or a halogenated hydrocarbon group is preferable. R ³ and R ⁴ , R ⁴ and R ⁵ ,
At least one pair of R ⁵ and R ⁶ may form a monocyclic aromatic ring together with the carbon atom to which they are bonded.

When there are two or more kinds of hydrocarbon groups or halogenated hydrocarbon groups, the groups other than the group forming an aromatic ring may be bonded to each other to form a ring. When R ⁶ is a substituent other than an aromatic group, it is preferably a hydrogen atom.

Specific examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, and the halogenated hydrocarbon group having 1 to 20 carbon atoms include the same groups as the above R ¹ and R ² . Examples of the ligand coordinated to M, including a monocyclic aromatic ring formed by combining at least one of R ³ and R ⁴ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ , are as follows. Some examples are shown below.

[0200]

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Of these, those represented by the above formula (1) are preferable. The aromatic ring is a halogen atom, having 1 to 1 carbon atoms.
It may be substituted with 20 hydrocarbon groups or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

Examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, and the halogenated hydrocarbon group having 1 to 20 carbon atoms which substitute the aromatic ring include the same groups as R ¹ and R ^2. .

X ¹ and X ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group. Shown specifically, R ¹ and R
² the same halogen atom, hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen-containing groups can be exemplified.

Examples of the sulfur-containing group include the same groups as the above R ¹ and R ² , and methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate. Sulfonate groups such as phonate, triisobutylbenzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate, methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate , Trimethylbenzenesulfinate, pentafluorobenzenesulfinate, and other sulfinate groups.

Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, 2
Divalent silicon-containing group, divalent germanium-containing group, divalent tin-containing group, -O-, -CO-, -S-, -SO-,-
^{_{SO 2 -, - NR 7 -}} , - P (R 7) -, - P (O)
^{(R 7) -, - BR} 7 - or -AlR ⁷ - [However,
R ⁷ represents 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], specifically, methylene, dimethylmethylene, 1,2-ethylene, Dimethyl-1,2-ethylene, 1,3-trimethylene,
Divalent having 1 to 20 carbon atoms such as alkylene groups such as 1,4-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; methylsilylene, dimethylsilylene, diethylsilylene, di (n-
Alkyl silylenes such as propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene, alkylarylsilylene, aryl Silylene group,
Tetramethyl-1,2-disilylene, tetraphenyl-1,2-
A divalent silicon-containing group such as an alkyldisilylene such as disilylene, an alkylaryldisilirene, an aryldisilirene group; a divalent germanium-containing group obtained by substituting germanium for silicon in the divalent silicon-containing group; A divalent tin-containing group substituent obtained by substituting tin for silicon in the silicon-containing group, wherein R ⁷ is the same halogen atom as R ¹ and R ² described above, a hydrocarbon group having 1 to 20 carbon atoms, and a carbon number. 1 to 20 halogenated hydrocarbon groups.

Of these, a divalent silicon-containing group, a divalent germanium-containing group and a divalent tin-containing group are preferable, and a divalent silicon-containing group is more preferable,
Of these, alkylsilylene, alkylarylsilylene, and arylsilylene are particularly preferred.

Specific examples of the transition metal compound represented by the above formula [B] are shown below.

[0208]

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[0209]

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In the present invention, a transition metal compound in which zirconium metal in the above compounds is replaced by titanium metal or hafnium metal can be used. The transition metal compound is usually used as a catalyst component for olefin polymerization as a racemate, but may be an R-type or S-type.

The indene derivative ligand of such a novel transition metal compound can be synthesized, for example, according to the following reaction route and using a usual organic synthesis method.

[0212]

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The transition metal compound used in the present invention can be synthesized from these indene derivatives by a known method, for example, the method described in JP-A-4-268307.

In the present invention, a transition metal compound (metallocene compound) represented by the following formula [C] can also be used.

[0215]

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In the formula [C], M, R ¹ , R ² , R ³ ,
As R ⁴ , R ⁵ and R ⁶ , those similar to the case of the formula [B] can be mentioned. R ³ , R ⁴ , R ⁵ and R ⁶
Among them, two groups including R ³ are preferably alkyl groups, and R ³ and R ⁵ , or R ³ and R ⁶ are preferably alkyl groups. This alkyl group is preferably a secondary or tertiary alkyl group. The alkyl group may be substituted with a halogen atom or a silicon-containing group.
^And the substituents exemplified for R ² .

Of the groups represented by R ³ , R ⁴ , R ⁵ and R ⁶ , the groups other than the alkyl group are preferably hydrogen atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, A chain alkyl group and a cyclic alkyl group such as nonyl, dodecyl, eicosyl, norbornyl and adamantyl; an arylalkyl group such as benzyl, phenylethyl, phenylpropyl and tolylmethyl; and the like, including a double bond and a triple bond May be.

Two kinds of groups selected from R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a monocyclic or polycyclic ring other than the aromatic ring. As a halogen atom,
Specifically, the same groups as those for R ¹ and R ² can be exemplified.

Examples of X ¹ , X ² , Y and R ⁷ are the same as those in the case of the above formula [B]. The metallocene compound (transition metal compound) represented by the above formula [C] is shown below.
Here is a specific example.

Rac-Dimethylsilylene-bis (4,7-dimethyl)
-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,7-trimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,
4,6-trimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,5,6-trimethyl-1-
(Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,5,6-tetramethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,
4,5,6,7-pentamethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-n-
Propyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (4-i-propyl-7-
Methyl-1-indenyl) zirconium dichloride, rac-
Dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-i-propyl-6-methyl-1-indenyl) ) Zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-methyl-6-i-propyl
-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-i-propyl-5-methyl-1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4,6-di (i-propyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4,6- Di (i-propyl) -7-methyl-1-
Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-i-butyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-sec-butyl- 7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-methyl-4,6-di (sec-butyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-
Methyl-4-tert-butyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-cyclohexyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene- Screw (2-
Methyl-4-benzyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-phenylethyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-Methyl-4-phenyldichloromethyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-methyl-4-chloromethyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-methyl-4-trimethylsilylmethyl-7-methyl-
1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-trimethylsiloxymethyl
-7-methyl-1-indenyl) zirconium dichloride, r
ac-diethylsilylene-bis (2-methyl-4-i-propyl-7-
Methyl-1-indenyl) zirconium dichloride, rac-
Di (i-propyl) silylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride,
rac-di (n-butyl) silylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-di (cyclohexyl) silylene-bis (2-methyl-
4-i-Propyl-7-methyl-1-indenyl) zirconium dichloride, rac-methylphenylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-diphenylsilylene -Bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2-methyl-4-di (i-propyl) -1-indenyl) zirconium dichloride , Rac-di (p-tolyl) silylene-bis (2-methyl-
4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis
(2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-
Methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dibromide, rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dimethyl, rac- Dimethylsilylene-bis (2-methyl)
-4-i-Propyl-7-methyl-1-indenyl) zirconium methyl chloride, rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium-bis (methanesulfone Nato), rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium-bis (p-phenylsulfinato),
rac-Dimethylsilylene-bis (2-methyl-3-methyl-4-i-
Propyl-6-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-ethyl-4-i-propyl-6-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2- Phenyl-4-i-propyl-6-methyl-1-indenyl) zirconium dichloride.

In the present invention, a transition metal compound in which zirconium metal in the above compounds is replaced with titanium metal or hafnium metal can also be used. The transition metal compound is usually used as a racemic compound, but may be used in R-form or S-form.

The indene derivative ligand of such a transition metal compound can be synthesized, for example, by the same reaction route as described above and by a usual organic synthesis method. The transition metal compound (metallocene compound) represented by the above formula [C] can be synthesized from these indene derivatives by a known method, for example, a method described in JP-A-4-268307.

In the present invention, a transition metal compound (metallocene compound) represented by the following formula [D] can also be used.

[0224]

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In the formula [D], M, R ¹ , X ¹ , X ² and Y
Examples thereof include those similar to the formula [B] or the formula [C]. Among them, R ¹ is preferably a hydrocarbon group, particularly methyl, ethyl,
It is preferably a hydrocarbon group having 1 to 4 carbon atoms such as propyl and butyl.

Further, X ¹ and X ² are preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ² represents an aryl group having 6 to 16 carbon atoms, specifically, phenyl, α-naphthyl, β-naphthyl, anthracenyl, phenanthryl, pyrenyl, acenaphthyl,
Examples include phenalenyl and aceanthrylenyl. Of these, phenyl and naphthyl are preferred. These aryl groups may be substituted with the same halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms as in R ¹ .

Specific examples of the transition metal compound (metallocene compound) represented by the above formula [D] are shown below. rac-dimethylsilylene-bis (4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2
-Methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (α
-Naphthyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (β-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (1-anthracenyl)
1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (2-anthracenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (9- (Anthracenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-methyl-4- (9-phenanthryl) -1-indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p-fluorophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2
-Methyl-4- (pentafluorophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2
-Methyl-4- (p-chlorophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (m-chlorophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-
(o-chlorophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (o, p-
Dichlorophenyl) phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p-bromophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4 -
(p-tolyl) -1-indenyl) zirconium dichloride,
rac-Dimethylsilylene-bis (2-methyl-4- (m-tolyl)-
1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (o-tolyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (o, o '-Dimethylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-methyl-4- (p-ethylphenyl) -1-indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (pi-propylphenyl) -1-indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p-benzylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2
-Methyl-4- (p-biphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-
(m-biphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p-trimethylsilylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl -4- (m
-Trimethylsilylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-ethyl-
4-phenyl-1-indenyl) zirconium dichloride, r
ac-diphenylsilylene-bis (2-ethyl-4-phenyl-1-
(Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-phenyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-
n-propyl-4-phenyl-1-indenyl) zirconium dichloride, rac-diethylsilylene-bis (2-methyl-4-
(Phenyl-1-indenyl) zirconium dichloride, ra
c-di- (i-propyl) silylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-di-
(N-butyl) silylene-bis (2-methyl-4-phenyl-1-
(Indenyl) zirconium dichloride, rac-dicyclohexylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-methylphenylsilylene-bis (2-methyl-4-phenyl-1-indenyl)
Zirconium dichloride, rac-diphenylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-di (p-tolyl) silylene-bis (2-
Methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis (2
-Methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-methylene-bis (2-methyl-4-phenyl-1-
(Indenyl) zirconium dichloride, rac-ethylene-
Bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylgermyl-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethyltin-bis (2-methyl- 4-phenyl-1-
(Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dibromide, rac-dimethylsilylene-bis (2
-Methyl-4-phenyl-1-indenyl) zirconium dimethyl, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium methyl chloride, rac
-Dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium chloride SO ₂ Me, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium chloride OSO ₂ Me, and the like.

In the present invention, a transition metal compound in which zirconium metal in the above compounds is replaced with titanium metal or hafnium metal can be used. The transition metal compound represented by the formula [D] is described in Journa
l of Organometallic Chem. 288 (1985), pp. 63-67, EP-A-0,320,762 and examples, for example, as follows.

[0229]

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[0230]

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Such a transition metal compound [D] is usually used as a racemate, but an R isomer or an S isomer can also be used. In the present invention, a metallocene compound represented by the following formula [E-1] can also be used.

L ^a MX ₂ ... [E-1] (M is a group IV or lanthanide series metal of the periodic table, and L ^a is a derivative of a delocalized π-bonding group, (A metal M active site is provided with a constrained geometry, and X is independently hydrogen, halogen or a hydrocarbon group containing 20 or less carbon, silicon or germanium, a silyl group or a germanyl group.) Among the compounds represented by the formula [E-1],
Specifically, a compound represented by the following formula [E-2] is preferable.

[0233]

Embedded image

M is titanium, zirconium or hafnium, and X is the same as above. Cp is a substituted cyclopentadienyl group having a π bond to M and having a substituent Z or a derivative thereof.

Z is oxygen, sulfur, boron or an element of Group IVA of the periodic table, Y is a ligand containing nitrogen, phosphorus, oxygen or sulfur, and Z and Y form a condensed ring. Good.

Specific examples of the compound represented by the formula [E-2] include (dimethyl (t-butylamide))
(Tetramethyl-η ⁵ -cyclopentadienyl) silane)
Titanium dichloride, ((t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl) titanium dichloride, (dibenzyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) (Silane) titanium dichloride, (dimethyl (t-butylamide)
(Tetramethyl-η ⁵ -cyclopentadienyl) silane)
Dibenzyl titanium, (dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane) dimethyl titanium, ((t-butylamide) (tetramethyl-η ⁵
-(Cyclopentadienyl) -1,2-ethanediyl) dibenzyltitanium, ((methylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl) dineopentyltitanium, ((phenylphosphide ) (Tetramethyl
-η ⁵ -cyclopentadienyl) methylene) diphenyltitanium, (dibenzyl (t-butylamide) (tetramethyl
-η ⁵ -cyclopentadienyl) silane) dibenzyltitanium, (dimethyl (benzylamide) (η ⁵ -cyclopentadienyl) silane) di (trimethylsilyl) titanium,
(Dimethyl (phenyl phosphide)-(tetramethyl-
η ⁵ -cyclopentadienyl) silane) dibenzyltitanium, ((tetramethyl-η ⁵ -cyclopentadienyl) -1,
2-ethanediyl) dibenzyltitanium, (2-η ^5- (tetramethyl-cyclopentadienyl) -1-methyl-ethanolate (2-)) dibenzyltitanium, (2-η ^5- (tetramethyl-
Cyclopentadienyl) -1-methyl-ethanolate (2-))
Dimethyl titanium, (2-((4a, 4b, 8a, 9,9a-η) -9H-fluoren-9-yl) cyclohexanolate (2-)) dimethyl titanium, (2-((4a, 4b, 8a , 9,9a-η) -9H-Fluorene-9-
Il) cyclohexanolate (2-)) dibenzylzir titanium.

In the present invention, two or more kinds of the above metallocene compounds may be used in combination. In the above description, a titanium compound is exemplified as a metallocene compound, but a compound in which titanium is replaced with zirconium or hafnium can also be exemplified.

These compounds may be used alone,
Two or more kinds may be used in combination. In the present invention, the metallocene compounds [E-1] and [E-2] are preferably zirconocene compounds in which the central metal atom is zirconium and which has a ligand having at least two cyclopentadienyl skeletons. Used. In the metallocene compound [VI], the central metal atom is preferably titanium.

These metallocene compounds may be diluted with a hydrocarbon or a halogenated hydrocarbon before use. The metallocene compound as described above can be used in contact with a particulate carrier compound.

Examples of the carrier compound include SiO ₂ and Al ₂ O.
_{3, B 2 O 3, MgO} , ZrO 2, CaO, TiO 2, Zn
Use of inorganic carrier compounds such as O, Zn ₂ O, SnO ₂ , BaO, and ThO, and resins such as polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, and styrene-divinylbenzene copolymer Can be. These carrier compounds can be used in combination of two or more.

Next, according to the present invention, the catalyst [b] (IV of the periodic table)
The organic aluminum oxy compound and the ionized ionic compound used for forming the metallocene compound of the transition metal selected from the group III and the organic aluminum oxy compound or the ionized ionic compound) will be described.

The organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound.

Such a conventionally known aluminoxane is specifically represented by the following general formula.

[0244]

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(In the above general formula, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group or a butyl group, preferably a methyl group or an ethyl group, particularly preferably a methyl group, and m is 2 or more. , Preferably an integer of 5 to 40.) Here, the aluminoxane is an alkyloxyaluminum unit represented by the formula (OAl (R ¹ )) and an alkyloxyaluminum represented by the formula (OAl (R ² )). Even if it is formed of a mixed alkyloxyaluminum unit consisting of a unit [wherein R ¹ and R ² can represent the same hydrocarbon group as R, and R ¹ and R ² represent different groups] Good.

Conventionally known aluminoxane is produced, for example, by the following method, and is usually recovered as a solution of an aromatic hydrocarbon solvent. (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 an aromatic hydrocarbon solvent in which is suspended and reacting the resulting mixture to recover a solution of the aromatic hydrocarbon solvent. (2) A method in which water (water, ice or water vapor) is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran to recover the solution as an aromatic hydrocarbon solvent solution.

Of these methods, the method (1) is preferably adopted. Examples of the organoaluminum compound used when producing the solution of aluminoxane include the organoaluminum compounds described above, and specifically, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin -Butylaluminum, triisobutylaluminum, trisec-butylaluminum, trite
rt-butyl aluminum, tripentyl aluminum,
Trihexylaluminum, trioctylaluminum, tridecyl aluminum, tricyclohexyl aluminum, in trialkylaluminum, formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z [ expression such tricyclooctylammonium aluminum, x, y, and z are positive numbers, and z ≧ 2x. ] Alkenyl aluminum such as isoprenyl aluminum isoprenyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, dialkyl aluminum halides such as diisobutyl aluminum chloride, dialkyl aluminum hydride such as diethyl aluminum hydride, diisobutyl aluminum hydride, dimethyl Aluminum methoxide,
Dialkyl aluminum alkoxides such as diethyl aluminum ethoxide, dialkyl aluminum aryloxides such as diethyl aluminum phenoxide, and the like can be mentioned.

Of these, trialkylaluminum is particularly preferable. The above organoaluminum compounds are used alone or in combination.

The benzene-insoluble organoaluminum oxy compound used in the present invention is, for example, a method of bringing a solution of aluminoxane into contact with water or an active hydrogen-containing compound, or an organoaluminum compound and water as described above. It can be obtained by a method of contacting.

[0250] In benzene-insoluble organoaluminum oxy-compound used in the present invention, the compound was analyzed by infrared spectroscopy (IR), the absorbance at around 1220 cm ^-1 and (D _1220), the absorbance at around 1260 cm ^-1 (D ₁₂₆₀₎ and the ratio of (D _{12 60} / D ₁₂₂₀₎ is 0.09
Or less, preferably 0.08 or less, particularly preferably 0.04.
It is desirably within the range of 0.07.

The above benzene-insoluble organoaluminum oxy compound is presumed to have an alkyloxy aluminum unit represented by the following formula.

[0252]

[Chemical 51]

In the formula, R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms. As such a hydrocarbon group, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-
Examples thereof include a butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a cyclohexyl group, and a cyclooctyl group. Of these, a methyl group and an ethyl group are preferred, and a methyl group is particularly preferred.

The benzene-insoluble organoaluminum oxy compound may contain an oxyaluminum unit represented by the following formula in addition to the alkyloxyaluminum unit represented by the above formula.

[0255]

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In the formula, R ⁸ is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a hydroxyl group, a halogen or a hydrogen atom. R ⁸ and R ⁷ in the above formula represent different groups.

When containing an oxyaluminum unit, an organoaluminum oxy having an alkyloxyaluminum unit containing the alkyloxyaluminum unit in a proportion of 30 mol% or more, preferably 50 mol% or more, particularly preferably 70 mol% or more. Compounds are desirable.

The organic aluminum oxy compound used in the present invention may contain a small amount of an organic compound component of a metal other than aluminum. Examples of ionized ionic compounds include Lewis acids, ionic compounds, borane compounds, and carborane compounds.

Examples of the Lewis acid include compounds represented by BR ₃ (R is a phenyl group which may have a substituent such as fluorine, a methyl group and a trifluoromethyl group, or fluorine.), For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p -Tolyl) boron, Tris (o-tolyl) boron, Tris (3,5-
Dimethylphenyl) boron and the like.

Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts and triarylphosphonium salts.

Specific examples of the trialkyl-substituted ammonium salt include, for example, 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, and the like.

As the N, N-dialkylanilinium salt,
For example, N, N-dimethylanilinium tetra (phenyl)
Boron, N, N-diethylanilinium tetra (phenyl)
Boron and N, N-2,4,6-pentamethylanilinium tetra (phenyl) boron.

Examples of the dialkyl ammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Further, as an ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl)
Other examples include borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and ferrocenium tetra (pentafluorophenyl) borate.

Further, as the borane compound, the following compounds may be mentioned. That is, specifically,
Examples of the borane compound include decaborane (14); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [ Salts of anions such as tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate; and tri (n Metal borane anion salts such as -butyl) ammonium bis (dodeca hydride dodecaborate) cobaltate (III) and bis [tri (n-butyl) ammonium] bis (dodeca hydride dodecaborate) nickelate (III) No.

Further, as carborane compounds, 4-carbanonaborane (14) and 1,3-dicarbanonaborane (1
3), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride -1,3-Dimethyl-1,3-dicarbanonaborane, 7,8-Dicarbaundecaborane (13), 2,7-Dicarbaundecaborane (13), Undecahydride-7,8
-Dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1- Carbaune decaborate,
Tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl
-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl)
Ammonium 6-carbadecaborate (14), tri (n-
Butyl) ammonium 6-carbadecaborate (12),
Tri (n-butyl) ammonium 7-carboundecaborate (13), tri (n-butyl) ammonium 7,8-dicarboundecaborate (12), tri (n-butyl) ammonium 2,9-dicarboundeca Borate (12), tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarboundecaborate, tri (n-butyl)
Ammonium undecahydride-8-ethyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium Decahydride-8-allyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-9-
Trimethylsilyl-7,8-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-4,6
Salts of anions such as -dibromo-7-carboundecaborate; and tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) Ammonium bis (undecahydride-7,8-dicarboundecaborate) 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-dicarbaundecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-Dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) ferrate (III), tri (N-Butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8 -Dicarbaundecaborate) cobaltate (II
I), 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 (III), Bis [tri (n-butyl) ammonium] bis (undecahydride-7-
Examples thereof include salts of metal carborane anions such as carbaundecaborate) nickelate (IV).

Ionized ionic compounds as described above are
Two or more kinds may be used in combination. In the present invention,
The organoaluminum oxy compound or the ionized ionic compound can be used by being supported on the above-described carrier compound.

When forming the catalyst [b], the aforementioned organoaluminum compound may be used together with the organoaluminum oxy compound or the ionized ionic compound.

In the present invention, the above-mentioned catalyst [a] (catalyst comprising a soluble vanadium compound and an organoaluminum compound) or catalyst [b] (a metallocene compound of a transition metal selected from Group IV of the periodic table and an organic compound) is used. (I) ethylene, (ii) α-olefin and (iii) chain polyene group-containing norbornene compound are usually copolymerized in a liquid phase in the presence of an aluminum oxy compound or an ionized ionic compound. At this time, a hydrocarbon solvent is generally used, but an α-olefin such as propylene may be used as a solvent.

Examples of such a hydrocarbon solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane and kerosene and halogen derivatives thereof, and cycloaliphatic hydrocarbons such as cyclohexane, methylcyclopentane and methylcyclohexane. Hydrogen and its halogen derivatives, aromatic hydrocarbons such as benzene, toluene and xylene, and halogen derivatives such as chlorobenzene are used. These solvents may be used in combination.

(I) ethylene and (ii) α-olefins and (ii
i) The chain polyene group-containing norbornene compound may be copolymerized by either a batch method or a continuous method. When the copolymerization is carried out by a continuous method, the above-mentioned catalyst is used in the following concentration.

In the present invention, when the above catalyst [a], that is, a catalyst comprising a soluble vanadium compound and an organoaluminum compound is used, the concentration of the soluble vanadium compound in the polymerization system is usually 0.01 to 5 mmol. / Liter (polymerization volume), preferably 0.05 to 3 mmol / liter. This soluble vanadium compound is desirably supplied at a concentration of 10 times or less, preferably 1 to 7 times, more preferably 1 to 5 times the concentration of the soluble vanadium compound present in the polymerization system. The organoaluminum compound is supplied in an amount of 2 or more, preferably 2 to 50, and more preferably 3 to 20 in terms of the ratio of aluminum atoms to vanadium atoms (Al / V) in the polymerization system.

The soluble vanadium compound and the organoaluminum compound [a] are usually supplied diluted with the above-mentioned hydrocarbon solvent and / or liquid (ii) α-olefin and (iii) chain-like polyene group-containing norbornene compound. It At this time, the soluble vanadium compound is desirably diluted to the above-mentioned concentration, but the organoaluminum compound is supplied to the polymerization system after being adjusted to an arbitrary concentration of, for example, 50 times or less the concentration in the polymerization system. Is desirable.

When a catalyst [b] comprising a metallocene compound and an organoaluminumoxy compound or an ionized ionic compound (also referred to as an ionic ionized compound or an ionic compound) is used, the metallocene compound in the polymerization system The concentration is usually 0.00005 to 0.1 mmol / liter (polymerization volume), preferably 0.000.
It is 1 to 0.05 mmol / liter. The organoaluminum oxy compound is a ratio of aluminum atom to metallocene compound in the polymerization system (Al / transition metal),
It is supplied in an amount of 1-10000, preferably 10-5000.

In the case of an ionized ionic compound, the molar ratio of the ionized ionic compound to the metallocene compound in the polymerization system (ionized ionic compound / metallocene compound) is 0.5 to 20, preferably 1 to 10. Supplied.

When an organoaluminum compound is used, it is usually used in an amount of about 0 to 5 mmol / liter (polymerization degree product), preferably about 0 to 2 mmol / liter.

In the present invention, (i) ethylene and (ii) α-
When an olefin and (iii) a chain polyene group-containing norbornene compound are copolymerized in the presence of a catalyst [a] composed of a soluble vanadium compound and an organoaluminum compound, the copolymerization reaction is usually carried out at a temperature of -50. ℃ ~ 100
° C, preferably -30 ° C to 80 ° C, more preferably-
At 20 ° C to 60 ° C, the pressure exceeds 0 to ~ 50 kg / cm ² ,
Preferably, it is carried out under a condition of exceeding 0 to 20 kg / cm ² .

Further, in the present invention, (i) ethylene and (ii)
When the α-olefin and (iii) the norbornene compound containing a chain polyene group are copolymerized in the presence of a catalyst [b] consisting of a metallocene compound and an organoaluminum oxy compound or an ionizable ionic compound, the copolymerization reaction is Usually, the temperature is -20 ° C to 150 ° C, preferably 0 ° C.
~ 120 ° C, more preferably 0 ° C to 100 ° C, and pressure above 0 to ~ 80 kg / cm ² , preferably above 0 ~
It is carried out under the condition of 50 kg / cm ² .

The reaction time (average residence time when the copolymerization is carried out by a continuous method) varies depending on the conditions such as catalyst concentration and polymerization temperature, but is usually 5 minutes to 5 hours, preferably 10 minutes. ~ 3 hours.

In the present invention, the (i) ethylene, (ii) α-olefin and (iii) the chain polyene group-containing norbornene compound are such that an unsaturated ethylenic copolymer having a specific composition as described above can be obtained. Is supplied to the polymerization system in various amounts. Further, upon copolymerization, a molecular weight regulator such as hydrogen may be used.

As described above, (i) ethylene, (ii) α-
When an olefin and (iii) a chain polyene group-containing norbornene compound are copolymerized, an unsaturated ethylene copolymer is usually obtained as a polymerization liquid containing the same. This polymerization liquid is treated by a conventional method to obtain an unsaturated ethylene copolymer.

[ Vulcanizable Rubber Composition ] The rubber composition according to the present invention containing the unsaturated ethylene copolymer as described above is a vulcanizable rubber composition (hereinafter, vulcanized). It is also possible to use the vulcanized rubber composition as it is, but it is possible to exhibit even more excellent properties when used as a vulcanized product.

The vulcanizable rubber composition according to the present invention can be vulcanized by heating using a vulcanizing agent or irradiating with an electron beam without using a vulcanizing agent.
The vulcanizable rubber composition according to the present invention can appropriately contain other components depending on the purpose together with the unsaturated ethylene-based copolymer, but the unsaturated ethylene-based copolymer,
It is desirable that the total rubber composition is contained in an amount of 20% by weight or more, preferably 25% by weight or more.

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

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

Specific examples of the inorganic filler include light calcium carbonate, heavy calcium carbonate, talc and clay. The rubber composition according to the present invention contains the reinforcing agent and / or the inorganic filler in an amount of usually 300 parts by weight or less, preferably 10 to 300 parts by weight, and more preferably 100 parts by weight of the unsaturated ethylene copolymer. Is 10 to 20
It can be contained in an amount of 0 parts by weight.

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

As the softening agent, the softening agents conventionally blended in rubber are widely used, and specifically, petroleum-based softening agents such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and petrolatum, Coal tar softeners such as coal tar and coal tar pitch, fatty oil softeners such as castor oil, linseed oil, rapeseed oil and coconut oil, waxes such as tall oil, sub, beeswax, carnauba wax and lanolin,
Ricinoleic acid, palmitic acid, barium stearate,
Fatty acids and fatty acid salts such as calcium stearate and zinc laurate, synthetic polymer substances such as petroleum resins, atactic polypropylene, and coumarone indene resins are used.

Of these, petroleum-based softeners are preferable, and process oil is particularly preferable. The rubber composition according to the present invention, the softening agent as described above, usually 200 parts by weight or less to 100 parts by weight of the unsaturated ethylene copolymer,
Preferably 10 to 200 parts by weight, more preferably 10
It can be contained in an amount of ˜150 parts by weight, particularly preferably 10 to 100 parts by weight.

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

Such an antioxidant can be appropriately used in an amount of 5 parts by weight or less, preferably 3 parts by weight or less, relative to 100 parts by weight of the unsaturated ethylene copolymer. Processing aids As processing aids, those generally compounded 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 can be appropriately used in an amount of 10 parts by weight or less, preferably 5 parts by weight or less, relative to 100 parts by weight of the unsaturated ethylene copolymer. When the vulcanizing agent or the rubber composition according to the present invention is vulcanized by heating, a compound constituting a vulcanizing system such as a vulcanizing agent, a vulcanization accelerator or a vulcanization aid is usually contained in the rubber composition. Mix.

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

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

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

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

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

When the vulcanizing agent is sulfur or a sulfur-based compound, it is used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the unsaturated ethylene copolymer. Can be used.

When the vulcanizing agent is an organic peroxide, 0.0003 to 0.05 mol, preferably 0.001 to 100 g of the unsaturated ethylene copolymer is used.
It can be used in an amount of 0.03 mol.

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

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

The vulcanization accelerator as described above is used in an amount of 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the unsaturated ethylene copolymer. desirable.

Vulcanization aid (polyfunctional monomer) When an organic peroxide is used as the vulcanizing agent, the vulcanization aid (polyfunctional monomer) is used in an amount of 0. It is preferable to use them in an amount of 5 to 2 moles, preferably approximately equimolar amounts.

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

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

As the foaming agent, a foaming agent generally used for foam-molding rubber can be widely used.
Specifically, inorganic blowing agents such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite, N, N'-dimethyl-N, N'-dinitrosoterephthalamide, N, N'-di Nitroso compounds such as nitrosopentamethylenetetramine, azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, azo compounds such as barium azodicarboxylate, benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p, p ' -Sulfonyl hydrazide compounds such as oxybis (benzenesulfonyl hydrazide) and diphenyl sulfone-3,3'-disulfonyl hydrazide, azide compounds such as calcium azide, 4,4-diphenyl disulfonyl azide and p-toluene sulfonyl azide To be

Of these, nitroso compounds, azo compounds and azide compounds are preferable. The foaming agent is 0.5 to 3 with respect to 100 parts by weight of the unsaturated ethylene copolymer.
It can be used in an amount of 0 parts by weight, preferably 1 to 20 parts by weight. From the rubber composition containing the foaming agent in such an amount, a foam having an apparent specific gravity of 0.03 to 0.8 g / cm ³ can be produced.

Further, a foaming aid can be used together with the foaming agent, and when the foaming aid is used in combination, the effects of lowering the decomposition temperature of the foaming agent, promoting decomposition, homogenizing bubbles, etc. Examples of such a foaming aid include organic acids such as salicylic acid, phthalic acid, stearic acid and oxalic acid, urea and derivatives thereof.

The foaming aid can be used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the unsaturated ethylene copolymer. Other rubbers The rubber composition according to the present invention can be used as a blend with other known rubbers within a range not impairing the object of the present invention.

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

Further, conventionally known ethylene / α-olefin copolymer rubbers can also be used. For example, ethylene / propylene random copolymer (EPR), ethylene / α-other than the unsaturated ethylene copolymers described above. An olefin / polyene copolymer such as EPDM can be used.

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

Vulcanized rubber The vulcanized product (vulcanized rubber) of the rubber composition according to the present invention is usually obtained by molding an unvulcanized rubber composition as described above into an extruder, calender roll, press or injection molding. Machine, transfer molding machine, etc., to obtain a desired shape by preforming, and simultaneously with molding or introducing the molded product into a vulcanization tank to heat or vulcanize it by irradiating it with an electron beam. be able to.

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

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

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

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

[0318]

EFFECTS OF THE INVENTION According to the present invention, it can be suitably used in the production of a novel unsaturated ethylene-based copolymer having excellent weather resistance, heat resistance, ozone resistance and fast vulcanization rate. A norbornene compound containing a chain polyene group is obtained. Further, according to the present invention, an unsaturated ethylene-based copolymer having the above properties in a well-balanced manner can be obtained.

[0319]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. (1) In the following examples of polymer production, for example, EMHN {: 5- (2-ethylidene-6-methyl-5-heptenyl) -2-norbornene} is obtained in the following examples of monomer synthesis. In addition to EMHN (true EMHN), small amounts of by-products (5- [3,7-dimethyl-2,6
-Octadienyl] -2-norbornene), and unless otherwise contradicted, simply referred to as EMHN, etc., to be true EMN.
When a mixture of HN and a by-product (EMHN-containing material) is meant, and when it is referred to as an ethylene / propylene / EMHN copolymer or the like, the EMHN unit includes a true EMHN unit and a unit derived from the by-product. Containing (EMH
N-containing unit) in some cases. (2) Structural unit [II] derived from EMHN (I) as a main component
And the ratio of the structural unit [II-a] derived from the by-product [Ia] was determined by the following method. Apparatus and measurement conditions [apparatus] NMR: manufactured by JEOL Ltd., GSH-270 type, FT-N
MR [Main equipment conditions] ¹ H measurement Observation range: 5400 Hz (20 ppm) Pulse width: 7.3 μsec (45 °) Solvent: Hexachlorobutadiene Lock solvent: Deuterated benzene Measurement mode: Proton non-decoupling Measurement temperature: 120 ° C Concentration: 50 mg / 0.4 cc Cumulative number of times: 1000 to 3000 times [Calculation method] 5.07 to 5.17 ppm
Set to 1.

The area of the 5.17 to 5.35 ppm region is S
Assume 2. Structural unit [II] derived from the main component compound [I]
And the ratio (mol%) of the structural unit [II-a] derived from the by-product [I-a] can be obtained from the following equation.

[II]: [S2 × 2 / (S1 + S2)] × 100 [II-a]: [(S1-S2) / (S1 + S2)] × 100

[0322]

Embedded image

[0323]

[Reference Example 1] [Preparation of catalyst] Under an argon atmosphere, anhydrous cobalt (II) chloride 4 was placed in a 50 ml flask containing a stirrer stirrer.
3 mg (0.33 mmol), 263 mg (0.66 mmol) of 1,2-bis (diphenylphosphino) ethane and 23 ml of anhydrous decane were charged and stirred at 25 ° C. for 2 hours. Then, at this temperature (25 ° C.), the concentration of 1 mol / mol
Liter of triethylaluminum / toluene solution 17
The catalyst was prepared by adding 2 ml (17 mmol of triethylaluminum) and stirring for 2 hours.

[4-Ethylidene-8-methyl-1,7-nonadie
Synthesis of EMN]

[0325]

Embedded image

EMN represented by was synthesized as follows. 300ml stainless steel (SUS31
6) 7-methyl-3-methylene-1,6-octadiene (β-myrcene) 1 in an autoclave manufactured under argon atmosphere.
00 g (734 mmol) and the whole amount of the catalyst prepared as described above were added, and the mixture was sealed.

Next, an ethylene cylinder was connected (directly connected) to the autoclave so that the pressure inside the autoclave was 35 kg /
Ethylene was introduced until cm ² . Subsequently, the reaction was carried out by heating to 95 ° C. During this period, the consumed ethylene was intermittently replenished (added) five times, and the reaction was carried out for a total of 15 hours.

After completion of the reaction, the inside of the autoclave was cooled, the autoclave was opened, and the obtained reaction mixture was poured into 100 ml of water to separate an organic layer and an aqueous layer. Then, the separated organic layer was separated, and low-boiling substances were removed by an evaporator, followed by precision distillation under reduced pressure in 20 stages to obtain 83 g of the target EMN (yield: 69).
%, Β-myrcene conversion 90%).

As a reaction by-product, 5,9-dimethyl-1,
16 g of 4,8-decatriene was produced (13% yield).
The analysis results of 4-ethylidene-8-methyl-1,7-nonadiene (EMN) obtained above are shown below.

(1) Boiling point: 103 to 105 ° C./30 mmHg (2) GC-MS (gas chromatography-mass spectrometry):
m / z 164 (M ⁺ molecular ion peak), 149, 1
23, 95, 69, 41, 27 [Gas Chromatography Measurement Conditions: Column: J & W Scientific Co. Capillary Column DB-1701 (0.25 mm × 30)
m) Vaporization temperature: 250 ° C. Column temperature: After holding at 60 ° C. for 5 minutes, 10 up to 200 °
Temperature rise in ° C / min] (3) Infrared absorption spectrum (neat, cm ^-1 ) Absorption peak: 3080, 2975, 2925, 285
0, 1670, 1640, 1440, 1380, 123
5, 1110, 995, 910, 830. (4) ¹ H-NMR spectrum (solvent: CDCl ₃ ) The absorption peak is shown below.

[0331]

[Table 1]

[0332]

Example 1 {5- (2-ethylidene-6-methyl-5-heptenyl) -2-
Norbornene [: EMHN, chain polyene exemplified above
Synthesis of Group-Containing Norbornene Compound (11)] Reference Example 1
4-ethylidene-8-methyl-1,7-nonadiene (EMN) 240.7 g (1.156 mol) obtained in the above was placed in a 1-liter stainless steel autoclave and 2 kg
Of nitrogen and 153.0 g of cyclopentadiene (2.314 g) while heating and stirring at a temperature of 190 ° C. under a nitrogen pressure of / cm ^2.
Mol) was added over 5 hours.

After that, the mixture was further heated and stirred at a temperature of 190 ° C. for 1 hour, then cooled to room temperature, and the autoclave was opened. The reaction mixture thus obtained was distilled off under reduced pressure to remove low-boiling fractions. The residue was subjected to 40-stage precision vacuum distillation to obtain the desired EMH.
N ｛: 5- (2-ethylidene-6-methyl-5-heptenyl)
53.8 g of -2-norbornene was obtained. The yield was 20.2 based on 4-ethylidene-8-methyl-1,7-nonadiene.
%Met.

The by-product [5- (3,7-dimethyl-2,6-octadienyl)]-2-norbornene was obtained in an amount of 10.1 g. Therefore, the ratio of EMHN and by-product was 5.33 / 1.

The physicochemical data for EMHN are shown below. (1) Boiling point: 138 ° C./3 mmHg (2) Gas chromatography-mass spectrometry: m / z 23
0 (M ⁺ ), 215, 187, 123, 91, 69 Gas chromatography measurement conditions: Column: J & W Scientific, Capillary column D B-1701 (0.25 mm × 30 m) Vaporization temperature: 250 ° C. Column temperature: After holding at 40 ℃ for 5 minutes, 5 ℃ up to 200 ℃
(3) Infrared absorption spectrum (neat, cm ^-1 ) 3050, 2960, 2925, 2850, 1660,
1630, 1570, 1440, 1375, 1345,
1330, 1250, 1220, 1100, 980, 9
25, 900, 820, 780, 715. (4) Proton NMR spectrum (CDCl ₃ solvent) The absorption peak is shown below.

[0336]

[Table 2]

[0337]

Example 2 153.0 g of dicyclopentadiene (1.
157 mol) and 4-ethylidene-8-methyl-1,7-
240.7 g (1.156 mol) of nonadiene was placed in a 1-liter stainless steel autoclave and 2 kg /
The reaction was carried out by heating and stirring at 190 ° C. for 6 hours under a nitrogen pressure of cm ² .

After completion of the reaction, the autoclave was opened by cooling to room temperature. The reaction mixture thus obtained was distilled off under reduced pressure to remove low-boiling fractions, and the residue was subjected to 40-stage precision vacuum distillation to obtain the desired EM.
48.7 g of HN were obtained. The yield was 18.3% based on 4-ethylidene-8-methyl-1,7-nonadiene.

Further, 9.7 g of 5- [3,7-dimethyl-2,6-octadienyl] -2-norbornene, which is a by-product, was obtained. Thus, the ratio between EMHN and by-products was 5.02 / 1. <Reference> [5- (3,7-dimethyl-2,6-octadienyl)]
-2-norbornene : (1) Proton NMR spectrum (CDCl ₃ solvent): 0.55 (1H, multiplet) 1.0 to 2.3 (8H, multiplet) 1.60 (6H, singlet) 1.68 (3H) , Singlet) 2.7 (2H, multiplet) 5.1 (2H, multiplet) 5.9 to 6.2 (2H, multiplet) (2) Infrared absorption spectrum (neat, cm ^-1 ): 305
0, 2960, 2925, 2860, 1670, 164
0, 1450, 1380, 1340, 1250, 110
5,900,830,720

[0340]

[Example 3] Using a polymerization vessel equipped with a stirring blade and having a capacity of 2 liters, ethylene and propylene and the EMHN obtained in Example 1 above (: 5- (2-ethylidene-6-methyl-5-heptenyl)) were used. The terpolymerization reaction with the -2-norbornene} -containing material was continuously carried out.

This copolymerization reaction was carried out as follows. That is, a hexane solution of the EMHN-containing material was added from the upper part of the polymerization vessel at 0.5 liter / hour so that the concentration in the polymerization vessel was 15 mmol / liter, and VO (O
A hexane solution of C ₂ H ₅ ) Cl ₂ was added in an amount of 0.5 liter per hour so that the vanadium concentration in the polymerization vessel was 0.2 mmol / liter, ethylaluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 Cl _1.5 0.5 liter / hour and 0.5 liter / hour of hexane are continuously fed into the polymerization vessel so that the aluminum concentration in the polymerization vessel is 2.0 mmol / liter. On the other hand, the polymerization liquid in the polymerization vessel is always 1
It was continuously withdrawn so as to have a liter.

A bubbling tube was used for the polymerization system to supply ethylene at a rate of 140 liters / hour, propylene at a rate of 160 liters / hour, and hydrogen at a rate of 15 liters / hour. The copolymerization reaction was carried out at 30 ° C. by circulating a refrigerant in a jacket attached outside the polymerization vessel.

When the copolymerization reaction was carried out under the above conditions, a polymerization solution containing an ethylene / propylene / EMHN-containing copolymer was obtained. The obtained polymerization solution is decalcified with hydrochloric acid water, and then poured into a large amount of methanol to precipitate a polymer, and then the temperature is 100 ° C.
And dried under reduced pressure for 24 hours.

As described above, ethylene / propylene / E
An MHN-containing copolymer was obtained in an amount of 68 g per hour. The resulting copolymer had an ethylene constitutional unit amount of 67.2 mol% and a propylene constitutional unit amount of 31.6 mol%.
It contains the MHN-containing constituent structural unit in an amount of 1.2 mol%, and the ethylene structural unit / propylene structural unit is 68/3.
It was 2 (molar ratio). Intrinsic viscosity [η] is 2.5 dl / g
Met.

The EMHN-containing material structural unit 1.2
Mol% is 0.85 mol% of EMHN building units and 0.
35 mol% by-product {[5- (3,7-dimethyl-2,6
-Octadienyl)]-2-norbornene} structural unit.

Then, 100 parts by weight of the obtained ethylene / propylene / EMHN-containing copolymer was added to 1 part of zinc flower.
5 parts by weight, 1 part by weight of stearic acid, 80 parts by weight of N330 [Product name: Seast 3, Tokai Carbon Co., Ltd.], and 50 parts by weight of oil [Product name: Sansen 4240, Sunoil Co., Ltd.] And 1.0 part by weight of vulcanization accelerator A [trade name: Nox Cler TT, manufactured by Ouchi Shinko Chemical Co., Ltd.]
A composition shown in the following table containing 0.5 part by weight of a vulcanization accelerator B [trade name: NOXCELLER M, manufactured by Ouchi Shinko Kagaku Co., Ltd.] and 1.5 parts by weight of sulfur was placed on a 6-inch open roll. The mixture was kneaded to obtain an unvulcanized compounded rubber (unvulcanized rubber composition).

Table 3 also shows the unvulcanized compounded rubber composition. When the vulcanization rate of this compounded rubber was evaluated, T90
(Minutes) was 6.1. The results are shown in Table 4.

The vulcanization rate was measured by using JSR Curastometer Model 3 (manufactured by Japan Synthetic Rubber Co., Ltd.),
Minimum value ML and maximum value MH of torque obtained from vulcanization curve
When the difference of ME (MH-ML = ME) is taken and the time required to reach 90% ME: T90 (minutes) is evaluated, the result is 6.1.
It became.

Further, the unvulcanized compounded rubber obtained by compounding with the compounding composition shown in Table 3 was pressed at 160 ° C. under the condition of T90 (min) +2 min (that is, 6.8 + 2 = 8.8 min). After vulcanization, physical properties of vulcanized rubber were measured. Unvulcanized compound rubber T90
(Minutes) and the physical properties of the obtained vulcanized rubber were measured.

100% modulus (M100: kgf / cm ² ) as a physical property of vulcanized rubber is 35, 200% modulus (M200: kgf / cm ² ) is 85, 300
% Modulus (M300: kgf / cm ²⁾ is 125, tensile strength ^{_{(T B: kgf / cm 2}} ) is 195,
Elongation (E _B:%) is 460, the hardness (H _S: JIS
A) became 68.

The results are also shown in Table 4. In addition, all the measuring methods were based on JIS K6301.

[0352]

[Table 3]

[0353]

Example 4 The procedure of Example 3 was repeated except that the EMHN-containing material was fed so that the concentration in the polymerization vessel was 5.9 mmol / liter, ethylene was 130 liters per hour, and propylene was 170 liters per hour. Copolymerization was performed in the same manner as in 3 to obtain an ethylene / propylene / EMHN-containing material copolymer in an amount of 79 g / hr.

The obtained copolymer had an ethylene constitutional unit of 62.2 mol% and a propylene constitutional unit of 37.3.
It contained the EMHN-containing structural unit in an amount of 0.55% by mol, and the ratio of the ethylene structural unit / the propylene structural unit was 63/37 (molar ratio). The intrinsic viscosity [η] was 2.1 dl / g.

The EMHN-containing material constitutional unit 0.5
5 mol% is 0.38 mol% of EMHN constitutional unit,
0.17 mol% by-product {[5- (3,7-dimethyl-
2,6-octadienyl)]-2-norbornene} structural unit.

Then, an unvulcanized compounded rubber was obtained in the same manner as in Example 3 except that the above copolymer was used instead of the ethylene / propylene / EMHN-containing copolymer in Example 3. .

When the vulcanization rate of this compounded rubber was evaluated, the T90 (min) was 7.7. Moreover, in Example 3, except that the ethylene / propylene / EMHN-containing copolymer obtained as described above was used.
An unvulcanized compounded rubber was prepared in the same manner as in 1. and press-molded.

The physical properties of the vulcanized rubber are shown below. M100: 27, M200: 70, M300: 101, tensile strength (T _B ): 161, elongation (E _B ): 530, hardness (H _S ): 67.

The results are also shown in Table 4.

[0360]

[Comparative Example 1] Using a 2-liter polymerization vessel equipped with a stirring blade, ethylene, propylene and 5-ethylidene-2- were continuously added.
A copolymerization reaction with norbornene (ENB) was performed.

From the upper part of the polymerization vessel, a hexane solution of ENB (7.1 g / liter) was added at 0.5 liter / hour, and a hexane solution of VO (OC ₂ H ₅ ) Cl ₂ as a catalyst (0.8
0.5 liter / hour), ethyl aluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 C
1 _1.5 ) in hexane (8.0 mmol / l)
Of 0.5 liter / hour and hexane of 0.5 liter / hour were continuously fed into the polymerization vessel, respectively, while the polymerization liquid in the polymerization vessel was continuously fed from the upper portion of the polymerization vessel to 1 liter continuously. I pulled it out. In addition, ethylene was fed at a rate of 120 liters / hour, propylene was supplied at a rate of 180 liters / hour, and hydrogen was supplied at a rate of 5 liters / hour using a bubbling tube for the polymerization system. The copolymerization reaction was carried out at 30 ° C. by circulating a refrigerant in a jacket attached outside the polymerization vessel. When the copolymerization reaction was carried out under the above conditions, a polymerization solution containing an ethylene / propylene / ENB copolymer was obtained.

The obtained polymerization solution was decalcified with hydrochloric acid water, and then poured into a large amount of methanol to precipitate a polymer, and then 100 ° C.
And dried under reduced pressure for 24 hours. As described above, an ethylene / propylene / ENB copolymer was obtained in an amount of 64.8 g per hour.

The obtained copolymer had an ethylene structural unit content of 66.8 mol% and a propylene structural unit content of 31.
4 mol%, ENB constitutional unit content is 1.8 mol%,
68/32 ethylene constitutional units / propylene constitutional units
(Molar ratio). The intrinsic viscosity [η] was 2.2 dl / g.

When the vulcanization rate of this compounded rubber was evaluated, T90 (min) was 11.2. Example 3
In, the unvulcanized compounded rubber was prepared and press-molded in the same manner as in Example 3 except that the copolymer obtained as described above was used.

The physical properties of the vulcanized rubber are shown below. M100: 30, M200: 74, M300: 117, tensile strength (T _B): 168, elongation (E _B): 400, hardness (H _S): 68.

The results are also shown in Table 4.

[0367]

Example 5 A heptane (900 ml) and the EMHN-containing material (15 ml) obtained in Example 1 were charged into a stainless steel autoclave having an internal volume of 2 liters, which had been sufficiently replaced with nitrogen, and the pressure in the system was 80 ° C. 3.5 kg / cm ²
Propylene was introduced so as to be -G.

Then, ethylene was introduced until it reached 8 kg / cm ² -G. Thereafter, 1 mmol of triisobutylaluminum, 0.005 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate and [dimethyl (t-butylamido) (tetramethylcyclopentadienyl) silane] titanium dichloride: 0.001 mmol. Polymerization was started by press-fitting with nitrogen.

Then, the total pressure was kept at 8 kg / cm ² -G by continuously supplying only ethylene, and polymerization was carried out at 80 ° C. for 20 minutes. After the polymerization was stopped by adding a small amount of ethanol to the system, unreacted monomers were purged.

The polymer was deposited by pouring the obtained polymer solution into a large excess of methanol. The polymer was recovered by filtration and the stabilizer [Irganox1
010 (manufactured by Ciba Geigy): 30 mg and Mark3
29k (manufactured by Asahi Denka Co., Ltd .: 60 mg), and then 120
Dry overnight under reduced pressure at ° C.

As a result, the ethylene unit content was 64.9 mol%.
In the amount of 33.7 mol% of propylene units,
HN content unit is contained in an amount of 1.4 mol%,
Ethylene / propylene / EMHN having a molar ratio of ethylene units and propylene units (ethylene units / propylene units) of 65.8 / 34.2 (molar ratio) and an intrinsic viscosity [η] of 3.01 dl / g. Inclusion copolymer 6
0.1 g was obtained.

Also, this EMHN-containing material structural unit 1.4
Mol% is equal to 1.0 mol% of EMHN building blocks and 0.4
It consisted of mol% of the by-product {[5- (3,7-dimethyl-2,6-octadienyl)]-2-norbornene} building block.

When the vulcanization rate of this compounded rubber was evaluated, T90 (min) was 5.4. Further, an unvulcanized compounded rubber was prepared and press-molded in the same manner as in Example 3, except that the copolymer obtained as described above was used.

The physical properties of the vulcanized rubber are shown below. M100: 45, M200: 93, M300: 135, tensile strength (T _B): 170, elongation (E _B): 420, hardness (H _S): 69.

The results are shown in Table 4 together.

[0376]

Example 6 In Example 5, the amount of heptane used was changed to 9
1 ml of 1-octene instead of propylene
Polymerization was carried out in the same manner as in Example 5 except that 00 ml was introduced and the polymerization time was 15 minutes. As a result, ethylene units were contained in an amount of 78.6 mol%, 1-octene units were contained in an amount of 19.7 mol%, and EMHN-containing units were contained in an amount of 1.7 mol%. The molar ratio with the 1-octene unit (ethylene unit / 1-octene unit) was 80.
It is 0 / 20.0 (molar ratio) and the intrinsic viscosity [η] is 2.
21 dl / g of ethylene / 1-octene / EMHN
48 g of a content copolymer was obtained.

Also, this EMHN-containing material constitutional unit 1.7 was used.
Mol% is 1.2 mol% of EMHN building blocks and 0.5
It consisted of mol% of the by-product {[5- (3,7-dimethyl-2,6-octadienyl)]-2-norbornene} building block.

When the vulcanization rate of this compounded rubber was evaluated, T90 (min) was 5.9. Further, an unvulcanized compounded rubber was prepared and press-molded in the same manner as in Example 3, except that the copolymer obtained as described above was used.

The physical properties of the vulcanized rubber are shown below. M100: 38, M200: 90, M300: 132, tensile strength (T _B): 150, elongation (E _B): 380, hardness (H _S): 67.

The results are also shown in Table 4.

[0381]

Example 7 Example 5 was repeated except that 1-butene was introduced in place of propylene at 80 ° C. so as to be 3.7 kg / cm ² -G, and the polymerization time was 30 minutes. Polymerization was performed in the same manner.

As a result, the ethylene unit content was 68.0 mol%.
Of 1-butene units in an amount of 30.6 mol%, EM
HN content unit is contained in an amount of 1.4 mol%,
The ethylene unit and the 1-butene unit have a molar ratio (ethylene unit / 1-butene unit) of 69.0 / 31.0 (molar ratio) and an intrinsic viscosity [η] of 2.51 dl / g. -54-containing 1-butene-EMHN-containing copolymer
g was obtained.

Also, this EMHN-containing material structural unit 1.4
Mol% is 0.98 mol% EMHN building blocks and 0.
42 mol% by-product {[5- (3,7-dimethyl-2,6
-Octadienyl)]-2-norbornene} structural unit.

When the vulcanization rate of this compounded rubber was evaluated, T90 (min) was 6.0. Further, an unvulcanized compounded rubber was prepared and press-molded in the same manner as in Example 3, except that the copolymer obtained as described above was used.

The physical properties of the vulcanized rubber are shown below. M100: 33, M200: 82, M300: 120, tensile strength (T _B): 185, elongation (E _B): 470, hardness (H _S): 66.

The results are also shown in Table 4.

[0387]

Example 8 [5- (2-Ethylidene-6-methyl-5-heptenyl]
Synthesis of (2-)-norbornene (EMHN) (4-ethylidene-8-methyl 1, obtained in Example 2 )
316 g of 7-nonadiene (EMN) (purity 95%, 1.
83 mol) and dicyclopentadiene (DCPD) 2
4.2 g (0.183 mol) was placed in a stainless steel autoclave having a volume of 1 liter and reacted at 220 ° C. for 2 hours under a nitrogen pressure of ² kg / cm ² . After cooling to room temperature, the autoclave was opened. As a result of analysis under the same gas chromatography measurement conditions as those described in Reference Example, DC
The conversion rate of PD was 96%, and the target EMHN selectivity (based on cyclopentadiene) was 57%. The EMN remaining in the reaction mixture was removed by simple distillation under reduced pressure, and the resulting residue was subjected to 40-stage precision vacuum distillation to obtain 43 g of EMHN-containing product, which was the target EMH.
40.9 g of N was obtained (isolated yield 48%, based on cyclopentadiene).

As a by-product (by-product), [5-
(3,7-Dimethyl-2,6-octadienyl)]-2
2.1 g of norbornene were obtained. Therefore, EMHN
And the by-product ratio (EMHN / by-product) is 19.5 /
It was one.

The physicochemical data for EMHN are shown below. Boiling point: 138 ° C / 3 mmHg Gas chromatography-mass spectrometry: m / z 230
(M ⁺ ), 215, 187, 123, 91, 69 Gas chromatography measurement conditions: the same as in Reference Example 1 infrared absorption spectrum (neat, cm ⁻¹ ) 3050, 2960, 2925, 2850, 1660,
1630, 1570, 1440, 1375, 1345,
1330, 1250, 1220, 1100, 980, 9
25, 900, 820, 780, 715 Proton NMR spectrum (CDCl ₃ solution, 500M
Hz NMR) 0.55 (1H, multiplet) 1.1 to 2.3 (10H, multiplet) 1.55 (3H, doublet, J = 7Hz) 1.60 (3H, singlet) 1.67 (3H, singlet) 2.7 (2H, multiplet) 5.10 (1H, multiplet) 5.20 (1H, quartet, J = 7Hz) 5.9 to 6.2 (2H, multiplet)

[0390]

Example 9 Copolymerization was performed in the same manner as in Example 3 except that the EMHN-containing material having a purity of 95% was used to obtain an ethylene / propylene / EMHN-containing material copolymer in an amount of 65 g / hr.

The obtained copolymer had an ethylene constitutional unit of 67.9 mol% and a propylene constitutional unit of 30.9 mol%.
It contained the EMHN-containing structural unit in an amount of 1.2 mol% in an amount of mol%, and the ratio of the ethylene structural unit / the propylene structural unit was 69/31 (molar ratio). Intrinsic viscosity [η]
Was 2.6 dl / g.

Further, 1.2 mol% of the EMHN-containing unit is 1.0 mol% of the EMHN constituent unit and 0.2 mol% of a by-product {[5- (3,7-dimethyl-2,2 6-octadienyl)]-2-norbornene} -derived constitutional unit.

The vulcanization rate T ₉₀ (minutes) of the compounded rubber prepared by compounding the ethylene / propylene / EMHN-containing copolymer in the same manner as in Example 3 was 6.2.
Further, an unvulcanized compounded rubber was prepared and press-molded in the same manner as in Example 3, except that the copolymer obtained as described above was used.

The physical properties of the vulcanized rubber are shown below. M100: 36, M200: 87, M300: 128, tensile strength (T _B): 196, elongation (E _B): 470, hardness (H _S): 68.

The results are also shown in Table 4.

[0396]

[Table 4]

(Note) In Table 4, "M100, M200, M300"
Are 100% tensile modulus (unit: kgf / cm ² ), 200% tensile modulus (unit: kgf / cm ² ), 300% tensile modulus (unit: kgf / c) as vulcanized rubber physical properties, respectively.
m ² ) is shown. "TB" is the tensile strength (unit: kgf / cm ²⁾ indicates, "E _B" extends (unit:%) indicates, "HS"
Indicates hardness (measurement method: JIS A compliant). "T
_“90 (minutes)” indicates the vulcanization rate (minutes) measured at 160 ° C.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nori Kihara Akira 6-1-2 Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Industries Ltd. (72) Toshiyuki Tsutsui, Kuga-gun, Yamaguchi Prefecture Waki Town Waki 6-1-2 Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Toshihiro Aine 3-5-2 Kasumigaseki, Kasumigaseki, Chiyoda-ku, Tokyo Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Masaaki Kawasaki 3 Chikusaigan, Ichihara, Chiba Mitsui Sekiyu Kagaku Kogyo Co., Ltd. (72) Inventor Hidehide Nakahama 3 Chikusaigan, Ichihara, Chiba Mitsui Sekiyu Kagaku Kogyo Co., Ltd. (54) [Invention] Name: Norbornene compound containing chain polyene group, process for producing the same, unsaturated ethylene copolymer using the norbornene compound, and process for producing the same Method and rubber composition containing the unsaturated ethylene copolymer

Claims (7)

[Claims] 1. General formula [I]: [In the formula [I], n is an integer of 1 to 5, and R ¹ has ¹ carbon atom.
And R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ] The norbornene compound containing a chain polyene group represented by 2. Cyclopentadiene and the general formula [III]: [In the formula [III], n is an integer of 1 to 5, R ¹ is an alkyl group having 1 to 5 carbon atoms, and R ² and R ³ are each independently a hydrogen atom or a 1 to 5 carbon atom. It is an alkyl group. ] The branched polyene compound represented by these is reacted, The manufacturing method of the norbornene compound containing a chain polyene group of Claim 1 characterized by the above-mentioned. 3. [A] (i) ethylene and (ii) carbon atoms of 3 to 2
Is a random copolymer of α-olefin of 0 and (iii) at least one norbornene compound containing a chain polyene group represented by the above general formula [I], and is derived from [B] (i) ethylene. 30 to 9 units
2 mol%, (ii) the constitutional unit derived from an α-olefin having 3 to 20 carbon atoms is 6 to 70 mol%, and (ii)
i) A structural unit derived from the chain polyene group-containing norbornene compound represented by the general formula [I] is 0.1 to 30.
Mol% and (iv) (i) a structural unit derived from ethylene / (ii) a structural unit derived from an α-olefin having 3 to 20 carbon atoms in a molar ratio of 40/60 to 92/8. [C] The structural unit derived from the norbornene compound containing a chain polyene group represented by the above general formula [I] has a structure represented by the following formula [II]: [In the formula [II], n is an integer of 1 to 5, R ¹ is an alkyl group having 1 to 5 carbon atoms, and R ² and R ³ are each independently a hydrogen atom or a carbon atom having 1 to 5 carbon atoms. It is an alkyl group. ] [D] Intrinsic viscosity [η] measured in decalin at 135 ° C
Is from 0.05 to 10 dl / g, an unsaturated ethylene copolymer. 4. (i) Ethylene and (ii) α having 3 to 20 carbon atoms.
-Forming an olefin and (iii) at least one chain polyene group-containing norbornene compound represented by the above general formula [I] from a transition metal compound, an organoaluminum compound and / or an ionizable ionic compound The method for producing an unsaturated ethylene copolymer according to claim 3, wherein the copolymerization is carried out in the presence of a catalyst. 5. [A] (i) ethylene and (ii) carbon number 3 to 2
0-α-olefin, and (iii) a small amount of at least one chain polyene group-containing norbornene compound represented by the above general formula [I] and a small amount of the chain polyene group-containing norbornene compound [I]. It is a random copolymer with at least one chain-like polyene group-containing norbornene compound represented by the following general formula [Ia]: [In the formula [Ia], n, R ¹ , R ² and R ³ are respectively the same as in the case of the formula [I]. ] [B] (i) The structural unit derived from ethylene is 30 to 9
2 mol%, (ii) the constitutional unit derived from an α-olefin having 3 to 20 carbon atoms is 6 to 70 mol%, and (ii)
i) A constitutional unit derived from the chain polyene group-containing norbornene compound represented by the general formula [I] and a small amount of the general formula [I- a] and a structural unit derived from the chain polyene group-containing norbornene compound represented by a.
1 to 30 mol%, and (iv) (i) a structural unit derived from ethylene / (ii) a structural unit derived from an α-olefin having 3 to 20 carbon atoms in a molar ratio of 40/60 to 92
/ 8, [C] the structural unit derived from the chain polyene group-containing norbornene compound represented by the above general formula [I] has a structure represented by the above formula [II], and The constitutional unit derived from the chain polyene group-containing norbornene compound represented by the above general formula [Ia] has a structure represented by the following formula [II-a]: [In the formula [II-a], n, R ¹ , R ² and R ³ are the same as in the case of the formula [II]. ] [D] Intrinsic viscosity [η] measured in decalin at 135 ° C
Is from 0.05 to 10 dl / g, an unsaturated ethylene copolymer. 6. (i) ethylene and (ii) α having 3 to 20 carbon atoms
An olefin, and (iii) at least one chain polyene group-containing norbornene compound represented by the general formula [I],
And at least one chain-like polyene group-containing norbornene compound represented by the above general formula [Ia], a catalyst formed from a transition metal compound and an organoaluminum compound and / or an ionizable ionic compound. The method for producing an unsaturated ethylenic copolymer according to claim 5, wherein the copolymerization is carried out in the presence. 7. The unsaturated ethylenic copolymer according to claim 3 or 5, and at least one component selected from the following (a), (b) and (c): A rubber composition comprising: (a) a reinforcing agent in an amount of 300 parts by weight or less based on 100 parts by weight of the unsaturated ethylene copolymer, and (b) the unsaturated ethylene copolymer. Softening agent in an amount of 200 parts by weight or less based on 100 parts by weight of the polymer, (c) a vulcanizing agent.