JPH115818A - Ethylenic random copolymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a noncrystalline or low-crystalline ethylene random copolymer excellent in fluidity, crosslinking property by peroxide, heat aging characteristics and mechanical characteristics and useful for materials, etc., for automobiles by copolymerizing a specific ethylene with an α-olefin and a nonconjugated polyene. SOLUTION: (A) An ethylene is copolymerized with (B) a 3-20C α-olefin such as propylene and (C) a nonconjugated polyene having norbornene skeleton, e.g. 5-vinyl-2-norbornene so that the molar ratio of the component A to the component B is (40/60) to (95/5) and component C content is 0.5-50 (g/100 g) expressed by iodine value as a copolymer. In the copolymer, the effective network chain density υ is >=1.5×10<20> /cm<3> and the shear rate satisfies the formula 0.04×10<-19> <=log(γ2 /γ1 )/υ<=0.2×10<-19> and γ1 and γ2 are each a shear rate obtained when shearing stress is each 0.4×10<6> dyn/cm<2> and 2.4×10<6> dyn/cm<2> .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel structure of ethylene
More specifically, it relates to an α-olefin / non-conjugated polyene random copolymer and a method for producing the same. The present invention relates to a polyene random copolymer and a method for producing such an ethylene random copolymer.

[0002]

2. Description of the Related Art Conventionally, ethylene, α-olefin,
Ethylene and α such as polyene terpolymer (EPDM)
-Olefin / non-conjugated polyene random copolymer (hereinafter also simply referred to as ethylene copolymer rubber) has excellent weather resistance, ozone resistance, heat aging resistance, etc.,
It is widely used as a material for electric wires, building civil engineering materials, industrial materials and the like. In recent years, ethylene / α-olefin / non-conjugated polyene random copolymers used in such applications have been required to have even better heat aging resistance and high fluidity (high-speed moldability).

[0003] High fluidity (high-speed moldability) is higher than that of ethylene-propylene-ethylidene norbornene (ENB) copolymer rubber or ethylene-propylene-1,4-hexadiene copolymer rubber. It is known that copolymer rubber is superior.

[0004] On the other hand, as a method for obtaining excellent heat aging resistance, when heat is crosslinked using an organic peroxide in place of sulfur which is a commonly used vulcanizing agent, the heat aging resistance is greatly improved. Are known.

However, the price of organic peroxides is generally much higher than that of sulfur, and if the amount of organic peroxide used is reduced for the purpose of suppressing cost increase, ethylene-propylene-ethylidene norbornene (ENB) copolymer rubber Any of ethylene, propylene, 1,4-hexadiene copolymer rubber, ethylene propylene, and dicyclopentadiene (DCPD) copolymer rubber has a weak cross-linking and mechanical properties are impaired.

[0006]

Therefore, even if the amount of the organic peroxide used is reduced, excellent mechanical properties can be maintained, excellent heat aging resistance, and excellent flowability (high-speed moldability). The appearance of α-olefin / non-conjugated polyene random copolymer and such a production method is desired.

In view of the above prior art, the present inventors have conducted intensive studies on an ethylene / α-olefin / non-conjugated polyene random copolymer and a method for producing the same.・ Successfully produced non-conjugated polyene random copolymer. The present invention has a novel structure that could not be obtained by a conventional production method, and has excellent fluidity, excellent peroxide crosslinkability, heat aging resistance, and excellent mechanical properties.
An object of the present invention is to provide a non-conjugated polyene random copolymer and a method for producing the same.

[0008]

According to the present invention, ethylene (a), an α-olefin having 3 to 20 carbon atoms (b) and a non-conjugated polyene having a norbornene skeleton (satisfying the following requirements or more) are simultaneously satisfied. c) a non-crystalline or low-crystalline ethylene random copolymer, characterized by: a molar ratio of ethylene (a) to α-olefin (b) [(a) / (b)] Is in the range of 40/60 to 95/5, and the content of the non-conjugated polyene (c) is in the range of 0.5 to 50 (g / 100 g) in terms of the iodine value of the copolymer. On the other hand, dicumyl peroxide 0.
The effective network chain density ν when press-crosslinking at 170 ° C. for 10 minutes using 0.1 mol is 1.5 × 10 ²⁰ / cm ³ or more, and the shear stress 0.4 × obtained from the melt flow curve at 100 ° C. Shear speed γ when showing 10 ⁶ dyn / cm ²
₁ and the ratio γ ₂ / γ ₁ of shear rate γ ₂ when exhibiting shear stress 2.4 × 10 ⁶ dyn / cm ² and the effective network chain density ν are represented by the general formula [I] 0.04 × 10 ^-19 ≦ Log (γ ₂ / γ ₁ ) /ν≦0.2×10 ⁻¹⁹ [I], and the intrinsic viscosity [η] measured in decalin at 135 ° C.
It is provided that it is in the range of 0.5 to 10 dl / g.

In the ethylene random copolymer of the present invention, the non-conjugated polyene (c) has the following formula [II]

Embedded image Wherein n is an integer of 0 to 10, R ¹ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and / or Or the following formula [III]

Embedded image In the formula, R ³ is preferably a norbornene compound represented by the formula: hydrogen or an alkyl group having 1 to 10 carbon atoms.

According to the present invention, the copolymerization of ethylene (a), an α-olefin having 3 to 20 carbon atoms (b) and a non-conjugated polyene (c) having a norbornene skeleton is carried out by the following formula [IV] VO ( _{oR) n X 3-n ‥} [IV] wherein, R represents a hydrocarbon group, X is a halogen, 0 ≦ n ≦ 3, in the soluble vanadium compound and the following formula is represented ^{_{[V] R 4 m AlX 1}} 3- _m ‥ [V] In the formula, R ⁴ is a hydrocarbon group, X ¹ is a halogen, 0 <m <
3, a polymerization temperature of 30 to 60 ° C and a polymerization pressure of 4 to 12 kgf
/ Cm ² , the supply amount (molar ratio) of ethylene and non-conjugated polyene is in the range of 0.01 ≦ non-conjugated polyene / ethylene ≦ 0.2. Provided.

In the present invention, the organoaluminum compound has a molar ratio of Al (Et) ₂ Cl / Al (Et) _1.5 Cl _1.5 of １ ／ to 10/1, particularly １ ／ to 8/1.
(Et represents an ethyl group).

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The ethylene random copolymer of the present invention is derived from ethylene (a), an α-olefin having 3 to 20 carbon atoms (b) and a non-conjugated polyene (c) having a norbornene skeleton. However, it is characterized in that all of the above requirements are simultaneously satisfied.

The above-mentioned requirements define the composition ratio of ethylene (a) / α-olefin (b) in the copolymer. , Weather resistance and the like can be maintained at a satisfactory level.

The above requirement specifies the content of unsaturated bonds in the copolymer derived from the non-conjugated polyene (c) in terms of the iodine value. Is unfavorable, for example, and the permanent deformation rate increases (see Comparative Example 8 described later). On the other hand, if it is too large, it is not preferable because the resistance to environmental degradation deteriorates and the cost becomes disadvantageous.

The above-mentioned requirement indicates the ease of peroxide crosslinking of the copolymer or the degree of crosslinking obtained as an effective network chain density ν under a constant crosslinking condition (the measuring method will be described later). If this value is smaller than 1.5 × 10 ²⁰ pieces / cm ³ , the elongation becomes excessive and the permanent deformation rate increases, which is not preferable (see Comparative Examples 7 to 9 described later).

The above requirements show a balance between the shear stress dependence of the shear rate in the melt flow and the crosslinkability. The melt viscosity η is expressed by η = σ / γ, where γ is the shear rate and σ is the shear stress. The rate of increase in the shear rate per degree of increase is remarkably large. In the central term of the formula (I), the logarithmic value of the molecular shear rate ratio γ ₂ / γ ₁ is determined by The value is large when the shear stress dependence of the shear rate is large, and small when the shear stress dependence is small. On the other hand, the denominator ν represents the effective network chain density in the above requirements, and the ratio of the two characteristic values in the range of the formula (I) indicates that the processability and mechanical properties of the copolymer It is important to maintain the heat aging resistance at an excellent level while maintaining the properties at an excellent level. That is, when this ratio is less than 0.04, workability tends to decrease, while when it exceeds 0.2, strength tends to decrease, permanent set increases, and heat aging resistance tends to decrease. .

The above-mentioned requirement defines the molecular weight of the copolymer. If the intrinsic viscosity [η] is lower than the above range, physical properties such as mechanical properties are reduced. Workability and the like tend to decrease.

The above requirement specifies that the non-conjugated polyene used in the copolymer of the present invention is a norbornene compound having the chemical structure of the formulas [II] and [III]. Various types of cyclic non-conjugated polyenes, such as those having a norbornene skeleton and those having a dicyclopentadiene skeleton, are known. )
However, even if the iodine value of the copolymer falls within the range of the present invention, it is difficult to obtain a copolymer having an effective network chain density (ν) within the range defined by the above requirements. Such a copolymer has a large permanent set and is extremely poor in heat aging resistance (see Comparative Examples 1 to 5 described later).

On the other hand, 5-methylene-2-norbornene (MND) and 5-vinyl-2-norbornene (V
When ND) is used, it is possible to produce a rubber having an effective network chain density of 2 × 10 ²⁰ / cm ³ when peroxide-crosslinked, and this rubber has a small permanent set and a remarkable heat aging resistance. Excellent (see Examples 1 to 7 described later). This means that even if the iodine value is the same, that is, even if the content of the unsaturated bond in the copolymer is the same, the copolymer derived from the norbornene compound having the chemical structure of the above formulas [II] and [III] This is because the rate of crosslinking by peroxide is high.

The following can be considered as a reason for this. That is, when a non-conjugated polyene is copolymerized, one ethylenic unsaturation participates in the copolymerization, and the remaining ethylenic unsaturation remains in the copolymer chain, but in the case of a cyclic non-conjugated polyene, There are cases where the remaining ethylenically unsaturated bond is in the ring and cases where it is outside the ring. It is considered that the ethylenically unsaturated bond outside the ring has a higher degree of freedom and is more reactive than the ethylenically unsaturated bond inside the ring. In the copolymer produced by the polymerization means of the present invention using the norbornene compounds having the chemical structures of the formulas [II] and [III], the proportion of ethylenically unsaturated bonds outside the ring is high, which is described above. Recognized as providing benefits.

The copolymer of the present invention is produced by copolymerizing ethylene (a), an α-olefin having 3 to 20 carbon atoms (b) and a non-conjugated polyene having a norbornene skeleton (c) in the above-mentioned quantitative ratio. In this case, the above formula [I
Using a catalyst comprising a soluble vanadium compound of the formula [V] and the organoaluminum compound of the formula [V], a polymerization temperature of 30 to 60 ° C., and a polymerization pressure of 4 to 12 kgf.
/ Cm ² and the supply amount (molar ratio) of ethylene and non-conjugated polyene in the range of 0.01 ≦ non-conjugated polyene / ethylene ≦ 0.2, thereby satisfying the above-mentioned requirements and above at the same time. Polymers can be produced.

In the present invention, the organoaluminum compound has a molar ratio of Al (Et) ₂ Cl / Al (Et) _1.5 Cl _1.5 of 1/5 to 10/1, particularly 1/2 to 8/1. Is preferred. Further, the soluble vanadium compound is preferably VOCl ₃ . Satisfying these conditions is advantageous because a polymer containing 1% or less xylene insolubles is obtained.

[Random Copolymer] The ethylene random copolymer of the present invention comprises ethylene (a) and 3 to 2 carbon atoms.
0-olefin (b) and a non-conjugated polyene (c) having a norbornene skeleton, and ethylene (a)
And the molar ratio of α-olefin (b) [(a) / (b)]
Is in the range of 40/60 to 95/5, and the content of the non-conjugated polyene (c) is 0.5 as an iodine value as a copolymer.
５０50 (g / 100 g).

In the random copolymer of the present invention, the α-olefin of (b) is an α-olefin having 3 to 20 carbon atoms.
Olefins, specifically, propylene, butene-
1,4-methylpentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, undecene-1, dodecene-1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene -1, heptadecene-1, nonadecene-1, eicosene-1, 9-methyl-decene-1, 11-methyl-dodecene-1, 12
-Ethyl-tetradecene-1 and the like.

These α-olefins may be used alone or in combination of two or more. Among them, α-olefins having 3 to 10 carbon atoms are preferable, and propylene, 1-butene, 1-hexene, 1-octene and the like are particularly preferably used.

The non-conjugated polyene (c) used in the present invention is
The polyene having a norbornene skeleton is preferably a norbornene compound represented by the general formula [II] or [III]. As the alkyl group for R ¹ in the general formula [II], specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, Examples include an n-pentyl group, an isopentyl group, a t-pentyl group, a neopentyl group, a hexyl group, an isohexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.

Further, specific examples of the R ² alkyl group in the general formula [II] include the alkyl groups having 1 to 5 carbon atoms in the specific examples of the above R ¹ .

Specific examples of the alkyl group of R ³ in the general formula [III] include the same alkyl groups as those described above for the alkyl group of R ¹ .

The above general formula [II] or the above general formula [II
I] Specifically, as the norbornene compound represented by
5-methylene-2-norbornene, 5-vinyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5-
(1-methyl-2-propenyl) -2-norbornene, 5
-(4-pentenyl) -2-norbornene, 5- (1-
Methyl-3-butenyl) -2-norbornene, 5- (5
-Hexenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, 5- (2,3
-Dimethyl-3-butenyl) -2-norbornene, 5-
(2-ethyl-3-butenyl) -2-norbornene, 5
-(6-heptenyl) -2-norbornene, 5- (3-
Methyl-5-hexenyl) -2-norbornene, 5-
(3,4-dimethyl-4-pentenyl) -2-norbornene, 5- (3-ethyl-4-pentenyl), 5- (7
-Octenyl) -2-norbornene, 5- (2-methyl-6-heptenyl) -2-norbornene, 5- (1,2
-Dimethyl-5-hexenyl) -2-norbornene, 5
-(5-ethyl-5-hexenyl) -2-norbornene, 5- (1,2,3-trimethyl-4-pentenyl)
-2-norbornene and the like.

Among them, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl)
-2-norbornene, 5- (4-pentenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5-
(7-octenyl) -2-norbornene is preferred.

In addition to 5-vinyl-2-norbornene, it can be used by mixing with the following non-conjugated polyene as long as the desired physical properties are not impaired. In particular,
1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-
Chain non-conjugated dienes such as hexadiene, 7-methyl-1,6-octadiene, methyltetrahydroindene, 5
-Ethylidene-2-norbornene, 5-methylene-2-
Cyclic non-conjugated dienes such as norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-
Trienes such as norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene can be exemplified.

(A) ethylene / (b) α-olefin component ratio: ethylene / α-olefin /
The non-conjugated polyene random copolymer is composed of (a) a unit derived from ethylene and (b) a unit derived from an α-olefin having 3 to 20 carbon atoms (hereinafter sometimes simply referred to as an α-olefin). 60 to 95/5, preferably 5
0 / 50-90 / 10, more preferably 55 / 45-
85/15, particularly preferably 60/40 to 80/20
[(A) / (b)] in molar ratio.

Iodine value: Ethylene used in the present invention
The iodine value of the α-olefin / non-conjugated polyene random copolymer is 0.5 to 50 (g / 100 g), preferably 0.8 to 40 (g / 100 g), and more preferably 1 to
30, particularly preferably 1.5 to 20. If this characteristic value is too small beyond the above range, the crosslinking efficiency is small,
If it is too large, the resistance to environmental degradation deteriorates and the cost becomes disadvantageous, which is not preferable.

Intrinsic viscosity: The intrinsic viscosity [η] of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber measured at 135 ° C. in decalin is 0.5 to 10 dl / g, preferably 0.88 dl / g. It is preferable to use a polymerized rubber in order to satisfy both physical properties and processability.

Molecular weight distribution: ethylene / α-olefin /
Molecular weight distribution of non-conjugated polyene random copolymer rubber (Mw
/ Mn) is 3 to 50, preferably 3.3 to 40,
More preferably, it is 3.5 to 30. Those having the above molecular weight range are excellent in a combination of physical properties and processability.

Crosslinking density: The ethylene / α-olefin / non-conjugated polyene random copolymer of the present invention gives a high crosslinking density by peroxide crosslinking. That is, 0.01 g of dicumyl peroxide was added to 100 g of the random copolymer.
and press-crosslinking at 170 ° C. for 10 minutes using a polymer having an effective network chain density ν of 1.5 × 10 ²⁰ / cm ³ or more, preferably 1.8 × 10 ²⁰ / c.
m ³ or more, more preferably 2.0 × 10 ²⁰ particles / cm ³
That is all.

Balance between crosslink density and melt flowability
(Γ ₂ / γ ₁ ) / ν: 0.4 × 10 ⁶ dyn / of ethylene / α-olefin / non-conjugated polyene random copolymer rubber obtained from a melt flow curve at 100 ° C.
Shear velocity γ ₁ when measuring cm ² and 2.4 × 10 ⁶ dy
n / cm ² the effective network chain density ν by the quotient of the shear rate gamma ₂ ratio γ ₂ / γ ₁ of the logarithm of the time indicating [Log (gamma ₂
/ Γ ₁ ) / ν] is 0.04 × 10 ^{−19 to} 0.2 × 10 ^−19.
And preferably 0.042 × 10 ^{−19 to} 0.19
× 10 ^-19 , more preferably 0.05 × 10
^{−19 to} 0.18 × 10 ⁻¹⁹ . The ethylene / α-olefin / non-conjugated polyene random copolymer as described above may be modified with a polar monomer. The modified product will be described later in detail.

[Production Method of Copolymer] In the present invention,
The specific ethylene / α-olefin / non-conjugated polyene random copolymer as described above includes ethylene (a), an α-olefin having 3 to 20 carbon atoms (b), and a non-conjugated polyene (c) having a norbornene skeleton. Ethylene (a) and α-
The molar ratio [(a) / (b)] with the olefin (b) is 40
/ 60 to 95/5, and the content of the non-conjugated polyene (c) is 0.5 to 5 in terms of iodine value as a copolymer.
The following formula [IV] VO (OR) _n X _3-n ‥ [IV] wherein R is a hydrocarbon group, X is a halogen, 0 ≦ n ≦ 3, so that the range is 0 (g / 100 g). Or a vanadium compound represented by VX ₄ , and the following formula [V] R ⁴ _m AlX ¹³ _3-m ‥ [V] In the formula, R ⁴ is a hydrocarbon group, X ¹ is a halogen, 0 <m <
Using a catalyst containing an organoaluminum compound represented by (3) as a main component, a polymerization temperature of 30 to 60 ° C, particularly 3
Under the conditions of 0 to 59 ° C. and a polymerization pressure of 4 to 12 kgf / cm ² , particularly 5 to 8 kgf / cm ² , and the supply amount (molar ratio) of ethylene and non-conjugated polyene is 0.01 ≦ non-conjugated polyene / ethylene ≦ It can be obtained by copolymerization within the range of 0.2. The polymerization is preferably carried out in a hydrocarbon medium.

In the copolymerization reaction, the soluble vanadium compound component used as a catalyst component is a vanadium compound component soluble in a hydrocarbon medium of a polymerization reaction system.
Specifically, the general formula VO (OR) _{n Xb} or V (OR) _c
X _d (where R is a hydrocarbon group, 0 ≦ n ≦ 3, 0 ≦ b ≦
3, 2 ≦ n + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ c
+ D.ltoreq.4), or an electron donor adduct thereof.

More specifically, VOCl ₃ , VO (OC
_{2 H 5) Cl 2, VO} (OC 2 H 5) 2 Cl, VO (O-i
_{so-C 3 H 7) Cl} 2, VO (O-n-C 4 H 9) Cl 2,
VO (OC ₂ H ₅ ) ₃ , VOBr ₃ , VCl ₄ , VO (O−
nC ₄ H ₉ ) ₃ and VCl ₃ .2OC ₆ H ₁₂ OH. Among them, VOCl ₃ is preferred.

The organoaluminum compound catalyst component used in the copolymerization reaction includes at least one A in the molecule.
Compounds having an l-carbon bond can be used. For example, (i) a compound represented by the general formula R ¹ _m Al (OR ² ) _n H _p X _q (where R ¹ and R ² each usually have 1 to 15 carbon atoms,
Preferably, the hydrocarbon group contains 1 to 4 and may be the same or different. X is halogen, m is 0 <m ≦
3, n is 0 ≦ n ≦ 3, p is 0 ≦ p ≦ 3, q is 0 ≦ q ≦ 3
(Ii) m + n + p + q = 3), (ii) a general formula M ¹ AlR ¹ (where M ¹ is Li, Na, K, and R ¹ is the same as above) And a co-alkylated product of a Group 1 metal and aluminum.

The following are examples of the organoaluminum compound belonging to the above (i). General formula R ¹ _m Al (OR ³ ) _3-m (where R ¹ and R ² are the same as above, m is preferably a number satisfying 1.5 ≦ m ≦ 3). General formula R ¹ _m AlX _3-m (where R ¹ is the same as above; X is halogen, m is preferably 0 <m <3). General formula R ¹ _m AlH _3-m (where R ¹ is the same as above. M is preferably 2 ≦ m <3
Is). General formula R ¹ _m Al (OR ² ) _{n Xq} (where R ¹ and R ² are the same as above; X is halogen, 0
<M ≦ 3, 0 ≦ nq <3, and m + n + q = 3)
Can be exemplified.

In the aluminum compounds belonging to (i), more specifically, trialkylaluminums such as triethylaluminum, tributylaluminum and triisopropylaluminum; dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; ethoxide, in addition to alkylaluminum sesqui alkoxides such as butyl sesquichloride _{^{butoxide, R 1 0.5 Al (OR 1}} ) partially alkoxylated alkyl aluminum having an average composition represented by like _0.5; diethylaluminum chloride, dibutyl aluminum Chloride, dialkylaluminum halides such as diethylaluminum bromide; ethylaluminum sesquichlore Partially halogenated alkylaluminums such as alkylaluminum sesquihalides such as butylaluminum sesquichloride, ethylaluminum sesquibromide, alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide A partially hydrogenated alkylaluminum of an alkylaluminum dihydride such as diethylaluminum hydride, dialkylaluminum hydride such as dibutylaluminum hydride, ethylaluminum dihydride, propylaluminum dihydride;
Partially alkoxylated and halogenated alkyl aluminums such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide and ethylaluminum ethoxybromide can be exemplified.

In the present invention, as the organoaluminum compound, a blend system of Al (Et) ₂ Cl / Al (Et) _1.5 Cl _1.5 is preferably used, and the molar ratio is 1/5 to 10/1, particularly 1: 1. / 2 to 8/1. When this blend system is used in combination with VOCl ₃ , a polymer having a xylene-insoluble content of 1% or less is obtained.

As a compound similar to (i), an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom may be used. As such a compound, for example, And the like.

Examples of the compounds belonging to the above (ii) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ . Among them, it is particularly preferable to use an alkyl aluminum halide, an alkyl aluminum dihalide or a mixture thereof.

The copolymerization reaction can be carried out in a hydrocarbon medium. Examples of the hydrocarbon medium include aliphatic hydrocarbons such as hexane, heptane, octane and kerosene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. Examples thereof include hydrocarbons, aromatic hydrocarbons such as benzene, toluene, and xylene, and the above-mentioned polymerizable unsaturated hydrocarbons. Even a mixed medium of two or more kinds may be used.

In the method for producing an ethylene-based random copolymer of the present invention, the copolymerization reaction is carried out by a continuous method. At this time, the concentration of the soluble vanadium compound supplied to the polymerization reaction system is 10 times or less, preferably 7 to 1 times, more preferably 5 to 1 times, and more preferably 3 to 1 times the concentration of the soluble vanadium compound in the polymerization reaction system. The range is one time.

The ratio (Al / V) of aluminum atoms to vanadium atoms in the polymerization reaction system is 2 or more, preferably 2 to 50, particularly preferably 3 to 20. The soluble vanadium compound and the organoaluminum compound are each usually supplied after being diluted with the hydrocarbon medium.

Here, the soluble vanadium compound is desirably diluted within the above concentration range, but the organoaluminum compound is adjusted to an arbitrary concentration of, for example, 50 times or less the concentration in the polymerization reaction system and supplied to the polymerization reaction system. The method is adopted.

In the copolymerization reaction, the concentration of the soluble vanadium compound in the copolymerization reaction system is usually in the range of 0.01 to 5 gram atoms / liter, preferably 0.05 to 3 gram atoms / liter as vanadium atoms. .

The copolymerization reaction is carried out at a temperature of 30 to 60 ° C., particularly 30 to 50 ° C. The copolymerization reaction is usually carried out by a continuous method. In that case, ethylene as a polymerization raw material,
α-olefin and norbornene-based polyene compound, soluble vanadium compound component of catalyst component, organoaluminum compound component and hydrocarbon medium are continuously supplied to the polymerization reaction system, and the polymerization reaction mixture is continuously released from the assembly reaction system. You.

The average residence time during the copolymerization reaction varies depending on the type of the polymerization raw material, the concentration of the catalyst component and the temperature.
Usually, it is in the range of 5 minutes to 5 hours, preferably 10 minutes to 3 hours.

The pressure during the copolymerization reaction is usually 4 to 12 k
gf / cm ² , especially 5 to 8 kg / cm ² , and optionally an inert gas such as nitrogen or argon. Further, in order to adjust the molecular weight of the copolymer, a molecular weight modifier such as hydrogen may be appropriately present.

The supply ratio of ethylene and α-olefin to be supplied to the copolymer varies depending on the polymerization conditions, but is usually about 20/80 to 80/20 in molar ratio.
The supply amount (molar ratio) of ethylene and non-conjugated polyene is preferably in the range of 0.01 ≦ non-conjugated polyene / ethylene ≦ 0.2. The supply and mixing of the starting olefin are controlled so that the proportion of each component in the generated ethylene-based random copolymer becomes the composition of the ethylene-based random copolymer of the present invention. The copolymerization reaction is carried out until the intrinsic viscosity of the resulting ethylene-based random copolymer reaches the intrinsic viscosity specified in the present invention.

The resulting copolymer solution obtained by the copolymerization reaction is a solution of an ethylene-based random copolymer in a hydrocarbon medium. The concentration of the ethylene random copolymer contained in the resulting copolymer solution is usually in the range of 2.0 to 20.0% by weight, preferably 2.0 to 10.0% by weight. The ethylene-based random copolymer of the present invention can be obtained by treating the resulting copolymer solution according to a conventional method.

[Modified Random Copolymer] In the present invention, the above-mentioned ethylene / α-olefin / non-conjugated polyene random copolymer may be graft-modified with a polar monomer. Examples of the polar monomer include a hydroxyl group-containing ethylenically unsaturated compound, an amino group-containing ethylenically unsaturated compound, an epoxy group-containing ethylenically unsaturated compound, an aromatic vinyl compound, an unsaturated carboxylic acid or a derivative thereof, a vinyl ester compound, and a chloride. Vinyl and the like.

Examples of the hydroxyl group-containing ethylenically unsaturated compound include hydroxyethyl (meth) acrylate,
2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxy-propyl (meth) acrylate,
3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylolethane mono (meth) acrylate, butanediol mono ( (Meth) acrylates such as meth) acrylate, polyethylene glycol mono (meth) acrylate, and 2- (6-hydroxyhexanoyloxy) ethyl acrylate; 10-undecene-1-ol; 1-octen-3-ol; -Methanol norbornene, hydroxystyrene, hydroxyethyl vinyl ether,
Hydroxybutyl vinyl ether, α-methylol acrylamide, 2- (meth) acryloyloxyethyl acid phosphate, glycerin monoallyl ether,
Allyl alcohol, allyloxyethanol, 2-butene-1,4-diol and glycerin monoalcohol.

The amino group-containing ethylenically unsaturated compound is represented by the following formula: (Wherein, R ³¹ is a hydrogen atom, a methyl group or an ethyl group, and R ³² is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and 6 to 12 carbon atoms, preferably And the above-mentioned alkyl group and cycloalkyl group may further have a substituent), or a vinyl-based monomer having at least one kind of substituted amino group. Mers.

Examples of such an amino group-containing ethylenically unsaturated compound include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate and methacrylic acid. Phenylaminoethyl acrylate, alkyl ester derivatives of acrylic acid or methacrylic acid such as cyclohexylaminoethyl methacrylate,
Vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine; allylamine derivatives such as allylamine, methacrylamine, N-methylacrylamine, N, N-dimethylacrylamide and N, N-dimethylaminopropylacrylamide; acrylamide And acrylamide derivatives such as N-methylacrylamide, aminostyrenes such as p-aminostyrene, 6-aminohexylsuccinimide, 2-aminoethylsuccinimide and the like.

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

The aromatic vinyl compound has the following formula (In the formula, Φ is a benzene ring or a heterocyclic ring, and R ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group.
² is a hydrocarbon group having 1 to 3 carbon atoms or a halogen atom, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a chlorine atom, a bromine atom and an iodine atom. n is an integer of usually 0 to 5, preferably 1 to 5. ).

As such an aromatic vinyl compound,
For example, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, p
-Chlorostyrene, m-chlorostyrene, p-chloromethylstyrene, 4-vinylpyridine, 2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5
-Vinylpyridine, 2-isopropenylpyridine, 2-
Vinyl quinoline, 3-vinyl isoquinoline, N-vinyl carbazole, and N-vinyl pyrrolidone.

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

The derivatives include, for example, maleenyl chloride, maleenyl imide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6- Dicarboxylic anhydride, dimethyl maleate, monomethyl maleate, ethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citrate, dimethyl tetrahydrophthalate, bicyclo [2,2,1] hept-2-
Dimethyl ene-5,6-dicarboxylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth)
Acrylates, glycidyl (meth) acrylate, aminoethyl methacrylate and aminopropyl methacrylate are included. Among these, (meth) acrylic acid, maleic anhydride, hydroxyethyl (meth) acrylate, glycidyl methacrylate, and aminopropyl methacrylate are preferred.

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

[Preparation of Modified Random Copolymer] The modified random copolymer can be obtained by graft-polymerizing a polar monomer to the above random copolymer.
When grafting the above-mentioned polar monomer to the random copolymer, the polar monomer is usually 1 to 100 parts by weight, preferably 5 to 80 parts by weight, based on 100 parts by weight of the random copolymer. Used in quantity.

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

Examples of the organic peroxide include dicumyl peroxide, di-t-butyl peroxide, 2,2
5-dimethyl-2,5-bis (t-butylperoxy)
Hexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) ) Balalate, benzoyl peroxide, t-butylperoxybenzoate, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide,
Examples include lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, and m-toluyl peroxide.

Examples of the azo compound include azoisobutyronitrile, dimethylazoisobutyronitrile and the like.

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

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

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

Specific examples of such reducing substances include ferrous chloride, potassium dichromate, cobalt chloride,
Cobalt naphthenate, palladium chloride, ethanolamine, diethanolamine, N, N-dimethylaniline,
Hydrazine, ethyl mercaptan, benzenesulfonic acid, p-toluenesulfonic acid and the like can be mentioned. In the present invention, the reducing substance is used in an amount of usually 0.001 to 5 parts by weight, preferably 0.1 to 100 parts by weight of the random copolymer.
It can be used in an amount of up to 3 parts by weight.

The graft modification of the random copolymer with a polar monomer can be carried out by a conventionally known method. For example, the random copolymer is dissolved in an organic solvent, and then the polar monomer and a radical initiator are added to the solution. 70
At a temperature of from 200 to 200 ° C, preferably from 80 to 190 ° C.
The reaction can be carried out for 5 to 15 hours, preferably 1 to 10 hours.

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

A modified random copolymer can also be produced by reacting a random copolymer with a polar monomer without using a solvent using an extruder or the like. This reaction is usually performed at a temperature equal to or higher than the melting point of the random copolymer, specifically, from 120 to 2
It is usually desirable to carry out at a temperature of 50 ° C. for usually 0.5 to 10 minutes. The amount of modification (graft amount of polar monomer) of the modified random copolymer thus obtained is usually from 0.1 to 50% by weight, preferably from 0.2 to 30% by weight.

[Vulcanizable Rubber Composition] The ethylene / α-olefin / polyene random copolymer of the present invention can be used as it is in an unvulcanized state. Characteristics can be exhibited.
The copolymer according to the present invention can be vulcanized by a method of heating using a vulcanizing agent or a method of irradiating an electron beam without using a vulcanizing agent.

The ethylene / α-olefin / polyene random copolymer of the present invention may optionally contain other components according to the purpose. The copolymer is
It is desirable that the content is 20% by weight or more, preferably 25% by weight or more in the whole rubber composition.

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

[Reinforcing Agent and Inorganic Filler] As the reinforcing agent, specifically, SRF, GPF, FEF, MAF, H
Examples thereof include carbon blacks such as AF, ISAF, SAF, FT, and MT, those obtained by subjecting these carbon blacks to surface treatment with a silane coupling agent, silica, activated calcium carbonate, fine talc, and fine silicates. Specific examples of the inorganic filler include light calcium carbonate, heavy calcium carbonate, talc, clay and the like.

The rubber composition contains 10 to 200 parts by weight, preferably 10 to 180 parts by weight, of a reinforcing agent and / or an inorganic filler based on 100 parts by weight of the ethylene / α-olefin / polyene copolymer (A). It can be contained in an amount.
From a rubber composition containing such an amount of a reinforcing agent, a vulcanized rubber having improved mechanical properties such as tensile strength, tear strength and abrasion resistance can be obtained. When the inorganic filler is blended in the above amount, the hardness can be increased without impairing other physical properties of the vulcanized rubber, and the cost can be reduced.

[Softeners] As softeners, softeners conventionally compounded in rubbers are widely used, and specific examples include petroleum softeners such as process oils, lubricating oils, paraffin, liquid paraffin, petroleum asphalt, and petrolatum. Agents, 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, lanolin , Ricinoleic acid, palmitic acid, barium stearate, calcium stearate,
Fatty acids and fatty acid salts such as zinc laurate, petroleum resins, synthetic high molecular substances such as atactic polypropylene and coumarone indene resin are used. Of these, petroleum softeners are preferred, and process oils are particularly preferred.

The rubber composition is prepared by adding the above softener to the ethylene / α-refin / polyene copolymer (A) 10
10 to 200 parts by weight, preferably 10 parts by weight per 0 parts by weight
To 150 parts by weight, particularly preferably 10 to 100 parts by weight.

[Antiaging Agent] The rubber or rubber composition exhibits excellent heat resistance and durability even without using an antiaging agent. Is possible as in the case of ordinary rubber. Antioxidants used in this case include:
Examples include amine antioxidants, phenol antioxidants, and sulfur antioxidants.

Examples of the amine-based antioxidants include naphthylamine-based antioxidants such as phenyl-α-naphthylamine and phenyl-β-naphthylamine;
(P-toluenesulfonylamide) -diphenylamine, 4,4- (α, α-dimethylbenzyl) diphenylamine, 4,4′-dioctyldiphenylamine, high-temperature reaction product of diphenylamine and acetone, low-temperature reaction of diphenylamine and acetone Reaction product, low-temperature reaction product of diphenylamine and aniline with acetone, reaction product of diphenylamine and diisobutylene, octylated diphenylamine, dioctylated diphenylamine,
diphenylamine-based antioxidants such as p, p'-dioctyldiphenylamine and alkylated diphenylamine;
N, N'-diphenyl-p-phenylenediamine, n-
Propyl-N′-phenyl-p-phenylenediamine,
N, N'-di-2-naphthyl-p-phenylenediamine, N-cyclohexyl-N'phenyl-p-phenylenediamine, N-phenyl-N '-(3-methacryloyloxy-2-hydroxypropyl) -p- Phenylenediamine, N, N'-bis (1-methylheptyl) -p
-Phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N'-
Bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N- (1,3-dimethylbutyl) -N '
And p-phenylenediamine-based antioxidants such as -phenyl-p-phenylenediamine.

Specific examples of the phenolic antioxidants include styrenated phenol, 2,6-di-t-butyl-4-methylphenol, and 2,6-di-t-butyl-p.
-Ethylphenol, 2,4,6-tri-t-butylphenol, butylhydroxyanisole, 1-hydroxy-3-methyl-4-isopropylbenzene, mono-t
-Butyl-p-cresol, mono-t-butyl-m-cresol, 2,4-dimethyl-6-t-butylphenol, butylated bisphenol A, 2,2'-methylene-
Bis- (4-methyl-6-t-butylphenol),
2,2 'methylene-bis- (4-ethyl-6-t-butylphenol), 2,2'-methylene-bis (4-methyl-6-t-nonylphenol), 2,2'-isobutylidene-bis- ( 4,6-dimethylphenol), 4,
4'-butylidene-bis- (3-methyl-6-t-butylphenol), 4,4'-methylene-bis- (2,6
-Di-t-butylphenol), 2,2-thio-bis-
(4-methyl-6-t-butylphenol), 4,4 '
-Thio-bis- (3-methyl-6-t-butylphenol), 4,4'-thio-bis- (2-methyl-6-butylphenol), 4,4'-thio-bis- (6-t- Butyl-3-methylphenol), bis (3-methyl-4)
-Hydroxy-5-t-butylbenzene) sulfide;
2,2-thio [diethyl-bis-3- (3,5-di-t
-Butyl-4-hydroxyphenol) propionate], bis [3,3-bis (4'-hydroxy-3'-
t-butylphenol) butyric acid] glycol ester, bis [2- (2-hydroxy-5-methyl-3-t-butylbenzene) -4-methyl-6-t-butylphenyl] terephthalate, 1,3 5-tris (3 ', 5'-di-tert-butyl-4'-hydroxybenzyl) isocyanurate, N, N'-hexamethylene-
Bis (3,5-di-t-butyl-4-hydroxy-hydroxyamide), N-octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butylphenol) propionate, tetrakis [methylene- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,1'-bis (4-hydroxyphenyl) cyclohexane, mono (α-methylbenzene) phenol, di (α-methyl Benzyl) phenol, tri (α-methylbenzyl) phenol, bis (2′-hydroxy-3′-t-butyl-5′-methylbenzyl) 4
-Methyl-phenol, 2,5-di-t-amylhydroquinone, 2,6-di-butyl-α-dimethylamino-
Examples include p-cresol, 2,5-di-t-butylhydroquinone, diethyl ester of 3,5-di-t-butyl-4-hydroxybenzylphosphoric acid, catechol, hydroquinone and the like.

Specific examples of the sulfur-based antioxidant include 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, zinc salt of 2-mercaptomethylbenzimidazole, Zinc salt of 2-mercaptomethylimidazole, dimyristylthiodipropionate, dilaurylthiodipropionate, disterialthiodipropionate, ditridecylthiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thio Propionate) and the like.

These antioxidants can be used alone or in combination of two or more. The amount of such an antioxidant is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A). It is desirable to use parts by weight.

[Processing Aid] As the processing aid, those generally blended with rubber as processing aids can be widely used. Specific examples include 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. Processing aids are ethylene, α-olefin,
It can be suitably used in an amount of 10 parts by weight or less, preferably 5 parts by weight or less, based on 100 parts by weight of the polyene copolymer.

[Vulcanizing Agent] When the rubber composition is vulcanized by heating, a vulcanizing system such as a vulcanizing agent, a vulcanization accelerator and a vulcanization aid is usually included in the rubber composition. Compound the compound. As the vulcanizing agent, sulfur, sulfur-based compounds, organic peroxides and the like can be used. Among these, an organic peroxide which is a vulcanizing agent having excellent heat aging resistance is preferable.
The form of the sulfur is not particularly limited, for example, powdered sulfur,
Precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur and the like can be used.

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

[0093] 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, t-butyl hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxin) hexyne-3,2,5-dimethyl-
2,5-di (benzoylperoxy) hexane, 2,5
-Dimethyl-2,5-mono (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy-m-
Dialkyl peroxides such as isopropyl) benzene; t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxybivalate, t-butylperoxymaleic acid, t-butylperoxyneodecano Ethate, t-butyl peroxybenzoate, di-t-butyl peroxyphthalate, 1,1
Peroxyesters such as -bis-t-butylperoxy-3,3,5-tri-methylcyclohexane; ketone peroxides such as dicyclohexanone peroxide; and mixtures thereof.

Among them, the temperature giving a half-life of 1 minute is 130
Organic peroxides in the range of from 200C to 200C are preferred, especially dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butyl. Cumyl peroxide, di-t-amyl peroxide, t-butyl hydroperoxide, 2,5-dimethyl-2,5-di (t-
Butylperoxin) hexyne-3,2,5-dimethyl-2,5-mono (t-butylperoxy) hexane,
Organic peroxides such as 1,1-bis-t-butylperoxy-3,3,5-tri-methylcyclohexane are preferably used.

When the vulcanizing agent is sulfur or a sulfur-based compound, 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the ethylene / α-olefin / polyene copolymer (A) is used. When it is an organic peroxide in an amount of parts by weight, it is 0.001 to 0.05 mol, preferably 0.002 to 0.02 mol, per 100 g of the ethylene / α-olefin / polyene copolymer (A). Is desirably used in an appropriate amount.

[Vulcanization Accelerator] When sulfur or a sulfur compound is used as the vulcanization agent, it is preferable to use a vulcanization accelerator in combination. As the vulcanization accelerator, specifically,
Sulfenamide compounds such as N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene-2-benzothiazolesulfenamide, N, N-diisopropyl-2-benzothiazolesulfenamide, 2-mercaptobenzo Thiazole, 2-
(2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl-4-morpholinothio)
Benzothiazole, dibenzothiazyl disulfide, 2
A thiazole compound such as-(4'-morpholinodithio) benzothiazole, a guanidine compound such as diphenylguanidine, triphenylguanidine, diorsonitrile guanidine, orthonitrile biguanide, diphenylguanidine phthalate, an acetaldehyde-aniline reactant, butyraldehyde -Aniline condensate, aldehyde amine or aldehyde-ammonia compound such as hexamethylenetetramine, acetaldehyde ammonia, imidazoline compound such as 2-mercaptoimidazoline (ethylenethiourea), thiocarbanilide,
Thiourea compounds such as diethylthiourea, dibutylthiourea, trimethylthiourea, and diorthotolylthiourea, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide,
Thiuram compounds such as pentamethylenethiuram tetrasulfide, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, dimethyldithiocarbamate Examples thereof include dithioate compounds such as selenium and tellurium dimethyldithiocarbamate, xanthate compounds such as zinc dibutylxanthate, and zinc white. Vulcanization accelerators such as those described above are ethylene / α-olefin /
0.1 parts by weight based on 100 parts by weight of the polyene copolymer (A)
It is desirable to use in an amount of from 20 to 20 parts by weight, preferably from 0.2 to 10 parts by weight.

[Vulcanization Aid (Polyfunctional Monomer)]
When an organic peroxide is used as the vulcanizing agent, the vulcanizing aid (polyfunctional monomer) is used in an amount of 0.5 to 2 mol, preferably approximately equimolar, to 1 mol of the organic peroxide. Is preferred. Specific examples of the vulcanization aid include sulfur, quinone dioxime compounds such as p-quinone dioxime, and (meth) acrylate compounds such as trimethylolpropane triacrylate, ethylene glycol dimethacrylate, and polyethylene glycol dimethacrylate. And allyl compounds such as diallyl phthalate and triallyl cyanurate; maleimide compounds such as m-phenylene bismaleimide; and divinylbenzene.

[Foaming agent] When the rubber composition contains a compound constituting a foaming system such as a foaming agent and a foaming aid,
It can be foam molded. As the foaming agent, foaming agents generally used when foaming rubber can be widely used, and specifically, sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite and the like Inorganic blowing agent, N, N'-dimethyl-N, N'-dinitrosoterephthalamide, N, N '
A nitroso compound such as dinitrosopentamethylenetetramine, an azo compound such as azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate, benzenesulfonylhydrazide, toluenesulfonylhydrazide, p, p'-oxybis (benzenesulfonylhydrazide), diphenylsulfone-3,3'-
Sulfonyl hydrazide compounds such as disulfonyl hydrazide; and azide compounds such as calcium azide, 4,4-diphenyldisulfonyl azide, and p-toluenesulfonyl azide. Of these, nitroso compounds, azo compounds and azide compounds are preferred.

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

A foaming aid can be used together with the foaming agent. When the foaming aid is used in combination, there are effects such as lowering the decomposition temperature of the foaming agent, accelerating the decomposition, and homogenizing the bubbles. Examples of such a foaming aid include organic acids such as salicylic acid, phthalic acid, stearic acid and oxalic acid, urea and derivatives thereof. The foaming aid is used in an amount of 0.0 to 100 parts by weight of the ethylene / α-olefin / polyene copolymer.
It can be used in an amount of 1 to 10 parts by weight, preferably 0.1 to 5 parts by weight.

[Other Rubbers] The rubber composition according to the present invention comprises:
As long as the object of the present invention is not impaired, it can be used by blending with other known rubbers. 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), chloroprene rubber (CR)
Conjugated diene rubbers and silicone rubbers. Particularly in the case of organic peroxide crosslinking, BR, S
It is preferable to blend with a rubber having high crosslinking efficiency such as BR and silicone rubber.

Further, conventionally known ethylene / α-olefin-based copolymer rubbers can also be used. α-olefin / polyene copolymer, for example, EPD
M or the like can be used.

Also, when a styrene resin (PS) and an acrylonitrile / styrene resin (AS) are blended for the purpose of improving the impact resistance, the graft efficiency is higher than that of the existing EPT, and the grafting is easy. Also, T
Even when used as a raw material for PO, the efficiency of the organic peroxide is higher than that of the existing EPT, which is suitable.

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

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

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

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

In molding and vulcanization, a mold may be used, or a mold may not be used. When a mold is not used, the rubber composition is usually continuously molded and vulcanized.

The vulcanized rubber molded and vulcanized as described above is used for automobile industrial parts such as weather strips, door glass run channels, window frames, radiator hoses, brake parts, wiper blades, rubber rolls, belts,
It can be used for applications such as industrial rubber products such as packings and hoses, electric insulating materials such as anode caps and grommets, electric wire coating materials, construction gaskets, civil engineering building materials such as civil engineering sheets, and rubber cloth.

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

[0111]

EXAMPLES The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples. The measurement in the following examples was performed as follows. 1. Composition The composition of the copolymer was measured by ¹³ C-NMR method. 2. Iodine value It was determined by a titration method. 3. Intrinsic viscosity The intrinsic viscosity [η] was measured at 135 ° C. in decalin. 4. Molecular weight distribution Expressed as a ratio of weight average molecular weight Mw / number average molecular weight Mn determined by GPC. For GPC, Tosoh Corp.
GMH-HT or GMH-HTL manufactured by Orthodichlorobenzene was used as a solvent. 5. γ ₂ / γ ₁ A melt flow curve at 100 ° C. is determined, and a shear rate γ ₁ at a shear stress of 0.4 × 10 ⁶ dyn / cm ² is obtained.
And the shear rate γ ₂ when the shear stress was 2.4 × 10 ⁶ dyn / cm ² . 6. Effective network chain density According to JIS K 6258 (1993), the polymer was immersed in toluene at 37 ° C. for 72 hours, and Flory-Rehne
The effective network chain density was calculated from the equation of r. ν (pieces / cm ³ ) = [ν _R + ln (1-ν _R ) + μν _R ² ]
/ −V ₀ (ν _R ^1/3 −ν _R / 2) ν _R : Volume fraction of pure rubber relative to the volume of pure rubber in the swollen vulcanized rubber (volume of pure rubber + volume of absorbed solvent) μ: Rubber-solvent interaction constant (0.49) V ₀ : molecular volume of solvent ν (number / cm ³ ): effective network chain density. Number of effective mesh chains in 1 cm ^{3 of} pure rubber

The sample was prepared by using the random copolymer 10
0.01 g of dicumyl peroxide was added to 0 g, and kneading was carried out at 50 ° C. as follows. Kneading method: The test kneading roll machine is 150 × 330 mm specified in SRIS 2603 (standard kneading roll machine for rubber).
(6 × 13 type) A standard kneading roll for testing is used. Set the temperature of the roll machine to 50 ± 2 ° C and set the roll gap to 0.5m
m, the rubber is wound on the high-speed side, and 3/4 turn is performed once for each of the left and right sides. Time required 1.0 minute. Thereafter, 0.01 mol of dicumyl peroxide is added, and 3/4 switching is performed alternately left and right three times. What is 3/4 switching?
Cut by ／ of the roll width and make a cut with a knife until the pool on the roll is no longer visible. This operation is performed alternately on the left and right every 30 seconds. Required time 13.0
Minutes. Cut the batch from the roll and reduce the roll gap to about 0.
The rounding is performed six times while keeping the diameter at 5 mm. Time required 2.
0 minutes. Weigh the batch, and the change in mass is ±
Must be within 1%. The final thickness is about 2.2m
The sheet is taken out as a vulcanizing sheet so as to obtain a m. The obtained sample is press-vulcanized with a 100-ton press at 170 ° C. for 10 minutes to obtain a measurement sample.

7. Relationship between γ ₂ / γ ₁ and crosslink density Log (γ _{2 /} γ ₁ ) / ν was determined by calculation. 8. Xylene extraction residual ratio As a pretreatment, about 5 g of a sample is sandwiched between luminers and 160 ±
A sheet having a thickness of 0.5 mm is prepared using a 5 ° C hand press. Cut out 1 to 2 g and cut into 1 mm square or less. A stainless steel basket is weighed, and the weight at this time is defined as A. A sample of 1 ± 0.1 g is collected in a stainless steel basket and weighed (the weight at this time is B). Put 200 ml of zeolite and xylene into a 300 ml flat bottom flask. The cooling water for the condenser is passed and the nitrogen for sealing is passed. Mesh 32
Set the Soxhlet extractor with the filter of 5,
Start refluxing. Extraction is performed for 5 hours at a reflux rate of 4 to 6 minutes. After the completion of the reflux, the sample is taken out, replaced with n-heptane and acetone at room temperature, and dried under reduced pressure at 105 ° C. for 1 hour. After cooling for 1 hour, the sample is weighed, and the weight at this time is defined as C. The calculation is performed as follows. Xylene extraction calculation rate = (CB) × 100 / (BA)
(%) One digit after the decimal point is the measured value.

Example 1 A tertiary ethylene / propylene / 5-vinyl-2-norbornene copolymer was continuously prepared using a stainless steel polymerization vessel (stirring speed = 250 rpm) having a substantial internal volume of 100 liters equipped with stirring blades. Polymerization was performed. 60 l / h of hexane, 3.7 kg of ethylene, 8.8 kg of propylene, 320 g of 5-vinyl-2-norbornene, 40 g of hydrogen, 40 l of hydrogen, and a catalyst (a) 32 mmol of VOCl ₃ , (b) Al (E
t) ₂ Cl of 160 mmol, Al (Et) _1.5 Cl _1.5
Was continuously fed at a rate of 32 mmol. The copolymerization reaction was performed at 40 ° C.

When the copolymerization reaction was carried out under the conditions described above, an ethylene / propylene / 5-vinyl-2-norbornene copolymer was obtained in a uniform solution state. Then, a small amount of methanol was added to the polymerization solution continuously withdrawn from the lower part of the polymerization vessel to stop the polymerization reaction, and the polymer was separated from the solvent by steam stripping.
Vacuum drying was performed at 5 ° C. for 48 hours. The ethylene content of the copolymer (NO. 1) obtained as described above was 74 mol.
%, Intrinsic viscosity [η] is 1.89 dl / g, 5-vinyl-
The 2-norbornene content was 7.5 in iodine value. Γ ₂ / γ ₁ determined from the melt flow curve of this copolymer
Is 115.8, the effective network chain density ν is 29.7 × 10 ¹⁹ / cm ³ , and Log (γ ₂ / γ ₁ ) / ν is 0.069 × 10
^It took a value of ^-19 .

Examples 2 to 9 and Comparative Examples 1 to 8 In Example 1, copolymers having different properties were obtained by changing the polymerization conditions as shown in Table 3. The obtained copolymer was evaluated in the same manner as in Example 1. Table 3 shows the polymerization conditions and the copolymer.

Example 10 First, the ingredients shown in Table 1 were mixed at a temperature of 140 to 150 ° C. using a 1.7 liter Banbury mixer.
The mixture was kneaded for minutes to obtain a blend (1).

[Table 1] * 1: Copolymer obtained in Example 1: ethylene / propylene / 5-vinyl-2-norbornene copolymer (NO.
1) Ethylene / propylene (molar ratio) = 74/26 Intrinsic viscosity [η] measured in 135 ° C decalin = 1.8
9 dl / g, iodine value = 7.5 * 2: manufactured by Sakai Chemical Industry Co., Ltd. * 3: manufactured by NOF Corporation, camellia (trademark) * 4: manufactured by Asahi Carbon Co., Ltd., Asahi # 70 (trademark) * 5: Diana Process Oil PW3 manufactured by Idemitsu Kosan Co., Ltd.
80 (trademark) * 6: polyethylene glycol, molecular weight = 4000 * 7: Ciba-Geigy Co., Ltd., Irganox 1010 (trademark) * 8: Nouchik MB (trademark) manufactured by Ouchi Shinko Chemical Industry Co., Ltd.

Next, the compound (1) was wound around an 8-inch open roll [manufactured by Nippon Roll Co., Ltd.], and a compounding agent was added on the open roll so as to have a compounding formula shown in Table 2, After kneading for 3 minutes, take out the sheet and thickness 3mm
Sheet was obtained. At this time, the roll surface temperature was 50 ° C. for the front roll and 60 ° C. for the rear roll.

[Table 2] The mixture (2) obtained as described above was heated at a mold temperature of 170 ° C. for 20 minutes using a press molding machine (manufactured by Kotaki Seiki Co., Ltd.) to obtain a vulcanized sheet having a thickness of 2 mm and a modulus of 2 mm. , Tensile properties, Crosslink density, Compression set Aging properties Moldability was measured.

[0119] These measuring methods are as follows. (1) Modulus According to JIS K 6301, a tensile test was performed under the conditions of a measurement temperature of 25 ° C. and a tensile speed of 500 mm / min, and a modulus M ₅₀ when the vulcanized sheet was stretched by 50% was measured. (2) in accordance Tensile properties JIS K 6301, measurement temperature 25 ° C., subjected to tensile test at a tensile rate of 500 mm / min condition was measured elongation E _B and strength T _B and hardness H _A at break of the vulcanized sheet. (3) Effective network chain density (index of crosslinking density) According to JIS K 6301, the vulcanized sheet was immersed in toluene at 37 ° C, and the effective network chain density was calculated from the following equation. ν (pieces / cm ³ ) = [ν _R + In (1-ν _R ) + μν _R ² ]
/ −V ₀ (ν _R ^1/3 −ν _R / 2) where ν _{R is} the volume fraction of the pure rubber relative to the volume of the swollen pure rubber in the swollen vulcanized rubber (the volume of the pure rubber + the volume of the solvent absorbed). μ: interaction constant between rubber and solvent (0.49) V ₀ : molecular volume of solvent ν (pieces / cm ³ ): effective network chain concentration. Pure rubber number of effective network chains in 1 cc (4) conforms to the compression set JIS, to determine the compression set C _S. Incidentally, 17
Using a sample vulcanized at 0 ° C. for 25 minutes, it was determined under the conditions of a 100-ton electric press. (5) Aging properties According to JIS K 6301, the vulcanized sheet was placed in an oven at 175 ° C. for 168 hours for aging, and then subjected to a tensile test at a measurement temperature of 25 ° C. and a tensile speed of 500 mm / min. The elongation and strength at break were measured, and the tensile strength retention A _R (T _B ) and the elongation retention A _R (E _B ) were calculated. Further, a change A _{H in} hardness was also determined. (6) Formability (a) Rollability The kneaded material kneaded by the above method was left at room temperature for 24 hours. Using an 8-inch open roll, 1.5 kg of the kneaded material was maintained at a roll temperature of 50 ° C. and a roll gap of 5 mm, the state of winding around the roll was observed, and the roll workability was evaluated on a 5-point scale. [Five-level evaluation] 5: The rubber band is completely adhered to the roll, and the band is rotating smoothly. 4: The band sometimes separates from the roll surface from the top of the roll to the bank. 3: The band separates from the roll surface from the top of the roll to between the banks. 2: The band does not adhere to the roll surface and cannot be rolled without hand. 1: The band hangs down without any close contact with the roll surface,
Roll processing is not possible without help.

(B) Extrudability The kneaded product kneaded by the above method was left at room temperature for 24 hours. The kneaded product was extruded using a 50 mm extruder under the following conditions, and the extruded skin was evaluated on a 5-point scale as an index of extrudability. [Extrusion conditions] L / D = 14,50 mm extruder, using a modifier / garbage die Extrusion temperature: after cylinder / before cylinder / head = 60
° C / 70 ° C / 80 ° C [Five-grade evaluation] 5: No surface irregularities at all, good gloss 4: Almost no surface irregularities, no luster 3: Slight surface irregularities, no luster 2: Surface irregularities No gloss 1... There are large irregularities on the surface and no gloss at all.

Example 11 In Example 10, the ethylene / propylene / 5-vinyl-2-norbornene copolymer (NO. 1) of Example 1 was used.
Instead of the following copolymer obtained in Example 2 (NO.
Except using 2), it carried out similarly to Example 10. Ethylene propylene 5-vinyl obtained in Example 2
2-norbornene copolymer (NO.2): ethylene / propylene (molar ratio) = 75/25 Intrinsic viscosity [η] measured in 135 ° C decalin = 1.8
3dl / g Iodine value = 10.9 The results are shown in Table 4.

Example 12 In Example 10, the copolymer (N) obtained in Example 1 was used.
O. Example 10 was carried out in the same manner as in Example 10 except that the copolymer (NO. 3) obtained in Example 3 below was used instead of 1). The ethylene-propylene / 5-vinyl-2-norbornene copolymer (N) of the copolymer obtained in Example 3
O. 3): Ethylene / propylene (molar ratio) = 74/26 Intrinsic viscosity [η] measured in 135 ° C decalin = 1.7
5dl / g Iodine value = 18.4 The results are shown in Table 4.

Example 13 In Example 10, the copolymer (N) obtained in Example 1 was used.
O. Example 10 was carried out in the same manner as in Example 10 except that the copolymer (NO. 4) obtained in Example 4 below was used instead of 1). Ethylene / 1-butene / 5 obtained in Example 4
-Vinyl-2-norbornene copolymer (NO.4): ethylene / 1-butene (molar ratio) = 81/19 Intrinsic viscosity [η] measured at 135 ° C in decalin = 2.6
2 dl / g iodine value = 5.4 The results are shown in Table 4.

Example 14 In Example 10, the copolymer rubber of Example 1 (NO.
Example 10 was repeated except that the copolymer (NO.5) obtained in Example 5 below was used instead of 1). Ethylene propylene 5- obtained in Example 5
Vinyl-2-norbornene copolymer (NO.5): ethylene / propylene (molar ratio) = 75/25 Intrinsic viscosity [η] measured at 135 ° C. in decalin = 2.0
1 dl / g iodine value = 8.0 The results are shown in Table 4.

Example 15 In Example 10, the copolymer rubber of Example 1 (NO.
Example 10 was carried out in the same manner as in Example 10 except that the copolymer (NO. 6) obtained in Example 6 below was used instead of 1). Ethylene propylene 5- obtained in Example 6
Vinyl-2-norbornene copolymer (NO.6): Ethylene / propylene (molar ratio) = 75/25 Intrinsic viscosity [η] measured in 135 ° C. decalin = 2.8
1 dl / g Iodine value = 8.5 The results are shown in Table 4.

Example 16 In Example 10, the copolymer rubber of Example 1 (NO.
Example 10 was carried out in the same manner as in Example 10 except that the copolymer rubber (NO.7) obtained in Example 7 below was used instead of 1). Ethylene / propylene / 5 obtained in Example 7
-Methylene-2-norbornene copolymer (NO.7): ethylene / propylene (molar ratio) = 74/26 Intrinsic viscosity [η] measured in decalin at 135 ° C. = 1.9
5dl / g Iodine value = 7.8 The results are shown in Table 4.

Comparative Example 9 In Example 10, the copolymer of Example 1 (No. 1) was used.
Was carried out in the same manner as in Example 10 except that the copolymer (H-1) obtained in Comparative Example 1 below was used instead of Ethylene / propylene / DCPD copolymer (H-1) obtained in Comparative Example 1: ethylene / propylene (molar ratio) = 66/34 Intrinsic viscosity [η] measured in decalin at 135 ° C. = 1.8
5dl / g Iodine value = 12.0 The results are shown in Table 4.

Comparative Example 10 In Example 10, the copolymer of Example 1 (No. 1) was used.
In place of the copolymer (H-) obtained in Comparative Example 2 below.
Except using 2), it carried out similarly to Example 10. Ethylene / propylene / ENB copolymer (H-2) obtained in Comparative Example 2: ethylene / propylene (molar ratio) = 66/34 Intrinsic viscosity [η] measured at 135 ° C. in decalin = 1.9
8dl / g iodine value = 13.0 The results are shown in Table 4.

Comparative Example 11 In Example 10, the copolymer of Example 1 (No. 1) was used.
In place of the copolymer (H-) obtained in Comparative Example 3 below.
The procedure was performed in the same manner as in Example 10 except that 3) was used. Ethylene / propylene / DCPD copolymer (H-3) obtained in Comparative Example 3: ethylene / 1-butene (molar ratio) = 89/11 intrinsic viscosity [η] measured in decalin at 135 ° C. = 1.2
dl / g Iodine value = 10.0 The results are shown in Table 4.

Comparative Example 12 In Example 10, the copolymer of Example 1 (No. 1) was used.
In place of the copolymer (H-) obtained in Comparative Example 4 below.
The procedure was performed in the same manner as in Example 10 except that 4) was used. Ethylene / propylene / 5-ethylidene-2-norbornene copolymer (H-4) obtained in Comparative Example 4: ethylene / propylene (molar ratio) = 66/34 Intrinsic viscosity [η] measured in decalin at 135 ° C. = 2.7
3dl / g Iodine value = 22.0 The results are shown in Table 4.

Comparative Example 13 In Example 10, the copolymer of Example 1 (No. 1) was used.
In place of the copolymer (H-) obtained in Comparative Example 5 below.
The procedure was performed in the same manner as in Example 10 except that 5) was used. Ethylene / propylene / DCPD copolymer rubber (H-5) obtained in Comparative Example 5: ethylene / propylene (molar ratio) = 67/33 Intrinsic viscosity [η] measured in decalin at 135 ° C. = 2.0
2dl / g Iodine value = 10.0 The results are shown in Table 4.

Comparative Example 14 In Example 10, the copolymer of Example 1 (No. 1) was used.
In place of the copolymer (H-) obtained in Comparative Example 6 below.
The procedure was performed in the same manner as in Example 10 except that 6) was used. Ethylene / propylene / 5-ethylidene-2-norbornene copolymer (H-6) obtained in Comparative Example 6: ethylene / propylene (molar ratio) = 79/21 Intrinsic viscosity [η] measured in decalin at 135 ° C. = 2.6
2dl / g iodine value = 11.2 The results are shown in Table 4.

Comparative Example 15 In Example 10, the copolymer of Example 1 (No. 1) was used.
In place of the copolymer (H-) obtained in Comparative Example 7 below.
The procedure was performed in the same manner as in Example 10 except that 7) was used. Ethylene propylene 5-vinyl obtained in Comparative Example 7
2-norbornene copolymer (H-7): ethylene / propylene (molar ratio) = 59/41 intrinsic viscosity [η] measured in 135 ° C decalin = 2.6
4 dl / g Iodine value = 2.6 The results are shown in Table 4.

Comparative Example 16 In Example 10, the copolymer of Example 1 (No. 1) was used.
In place of the copolymer (H-) obtained in Comparative Example 8 below.
Except using 8), it carried out similarly to Example 10. Ethylene propylene 5-vinyl obtained in Comparative Example 8
2-norbornene copolymer (H-8): ethylene / propylene (molar ratio) = 74/26 Intrinsic viscosity [η] measured in 135 ° C decalin = 2.2
6dl / g Iodine value = 0.3 The results are shown in Table 4.

Example 17 In Example 10, the copolymer of Example 1 (No. 1) was used.
In place of the copolymer (N) obtained in Example 8 below.
O. Except using 8), it carried out similarly to Example 10. Ethylene / propylene / 5-vinyl-2-norbornene copolymer (No. 8) obtained in Example 8: ethylene / propylene (molar ratio) = 74/26 Intrinsic viscosity [η] measured in decalin at 135 ° C. = 1.9
7 dl / g Iodine value = 3.1 The results are shown in Table 4.

Example 18 The procedure of Example 10 was repeated except that the copolymer of Example 1 (No. 1) was used.
Is replaced by the copolymer (N) obtained in Example 9 below.
O. Except using 9), it carried out similarly to Example 10. Ethylene / propylene / 5-vinyl-2-norbornene copolymer (NO.9) obtained in Example 9: ethylene / propylene (molar ratio) = 75/25 Intrinsic viscosity [η] measured in decalin at 135 ° C. = 1.8
6dl / g Iodine value = 3.8 The results are shown in Table 4.

[0137]

[Table 3]

[0138]

[Table 4]

[0139]

[Table 5]

[0140]

[Table 6]

[0141]

According to the process for producing an ethylene / α-olefin / norbornene-based non-conjugated polyene random copolymer according to the present invention, it has excellent peroxide crosslinking properties, excellent fluidity and excellent heat aging resistance. In addition, an ethylene / α-olefin / non-conjugated polyene random copolymer having excellent mechanical properties can be produced.

Further, the method for producing an ethylene / α-olefin / norbornene-based non-conjugated polyene random copolymer according to the present invention is to efficiently produce an ethylene / α-olefin / norbornene-based non-conjugated polyene random copolymer. Can be.

The ethylene / α-olefin / norbornene-based non-conjugated polyene random copolymer of the present invention comprises:
It is excellent in crosslinkability and can form crosslinks effectively with a small amount of peroxide and the like, and the crosslinked rubber composition obtained by using this is heat aging resistance, mechanical strength, weather resistance, ozone resistance. Excellent in nature.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masaaki Kawasaki 3 Chigusa Coast, Ichihara City, Chiba Prefecture Inside Mitsui Oil Chemicals Co., Ltd.

Claims (6)

[Claims] 1. It is derived from ethylene (a), an α-olefin having 3 to 20 carbon atoms (b), and a non-conjugated polyene having a norbornene skeleton (c), which simultaneously satisfy the following requirements. Non-crystalline or low-crystalline ethylene random copolymer: The molar ratio [(a) / (b)] of ethylene (a) to α-olefin (b) is in the range of 40/60 to 95/5. The content of the non-conjugated polyene (c) is in the range of 0.5 to 50 (g / 100 g) in terms of an iodine value of the copolymer, and 0.1 g of dicumyl peroxide is added to 100 g of the copolymer.
The effective network chain density ν when press-crosslinking at 170 ° C. for 10 minutes using 0.1 mol is 1.5 × 10 ²⁰ / cm ³ or more, and the shear stress 0.4 × obtained from the melt flow curve at 100 ° C. Shear speed γ when showing 10 ⁶ dyn / cm ²
₁ and the ratio γ ₂ / γ ₁ of shear rate γ ₂ when exhibiting shear stress 2.4 × 10 ⁶ dyn / cm ² and the effective network chain density ν are represented by the general formula [I] 0.04 × 10 ^-19 ≦ Log (γ ₂ / γ ₁ ) /ν≦0.2×10 ⁻¹⁹ [I], and the intrinsic viscosity [η] measured in decalin at 135 ° C.
0.5 to 10 dl / g. 2. The non-conjugated polyene (c) has the following formula [I
I] Wherein n is an integer of 0 to 10, R ¹ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and / or Or the following formula [III]: Wherein, R ³ is ethylene random copolymer according to claim 1 is hydrogen or an alkyl group having 1 to 10 carbon atoms, in a norbornene compound represented. 3. Ethylene (a), α- having 3 to 20 carbon atoms
The copolymerization of the olefin (b) and the non-conjugated polyene (c) having a norbornene skeleton is carried out by the following formula [IV] VO (OR) _n X _3-n ‥ [IV] where R is a hydrocarbon group and X is a halogen , 0 ≦ n ≦ 3, and a soluble vanadium compound represented by the following formula [V] R ⁴ _m AlX ¹³ _-m ‥ [V] wherein R ⁴ is a hydrocarbon group, X ¹ is halogen, and 0 <m <
3, a polymerization temperature of 30 to 60 ° C and a polymerization pressure of 4 to 12 kgf
/ Cm ^2, the supply amount of ethylene and non-conjugated polyene ethylenically described (molar ratio) in claim 1, characterized in that in a range of 0.01 ≦ nonconjugated polyene / ethylene ≦ 0.2 random copolymer Method for producing polymer. 4. The method according to claim 3, wherein the organoaluminum compound comprises a blend having a molar ratio of Al (Et) ₂ Cl / Al (Et) _1.5 Cl _1.5 of 1/5 to 10/1. 5. The method according to claim 3, wherein the organoaluminum compound comprises a blend having a molar ratio of Al (Et) ₂ Cl / Al (Et) _1.5 Cl _1.5 of 乃至 to 8/1. 6. The method according to claim 6, wherein the soluble vanadium compound is VOCl ₃
The method according to claim 4 or 5, wherein