JPH06179722A - Unsaturated ethylenic copolymer and its production - Google Patents

Abstract

PURPOSE:To obtain an unsaturated ethylenic copolymer, having a high vulcanization rate, excellent in weather, heat and ozone resistance and useful as automotive parts, etc., by copolymerizing ethylene with a specific alpha-olefin and a specified polyene in a specific proportion in the presence of a specified catalyst. CONSTITUTION:(A) Ethylene is copolymerized with (B) a 3-20C alpha-olefin and (C) one or more polyenes of (i) formula I (n is 1-5; R<1> is l-8C alkyl; R<2> to R<12> are H or R<1>) or (ii) formula II (R<5> to R<16> are H or 1-8C alkyl; either of R<4> and R<4>' is H or 1-8C alkyl and the other is formula III) in the presence of a catalyst formed from a transition metallic compound and an organoaluminum compound to afford the objective copolymer, comprising 30-92mol% constituent unit of the component (A), 6-70mol% constituent unit of the component (B) and 0.1-30mol% constituent unit of the component (C) at (40/60) to (92/8) molar ratio of the components (A)/(B) and having structures of formulas IV and V and 0.05-10dl/g intrinsic viscosity [eta] measured in decalin at 35 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an unsaturated ethylene-based copolymer and a method for producing the same, and more specifically to a novel unsaturated ethylene excellent in weather resistance, heat resistance and ozone resistance and having a high vulcanization rate. A copolymer and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Unsaturated ethylene-based copolymers are
It is a vulcanizable polymer and has excellent weather resistance, heat resistance, and ozone resistance.
It is widely used as a rubber product such as electrical insulation materials, civil engineering materials, rubberized cloth, and as a material for blending plastics such as polypropylene and polystyrene.

Such unsaturated ethylene-based copolymers have hitherto been known as ethylene / propylene / 5-ethylidene-2-
Norbornene copolymer, ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / 1,4-
Hexadiene copolymers and the like are known. Among these, the ethylene / propylene / 5-ethylidene-2-norbornene copolymer has a faster vulcanization rate than other unsaturated ethylene-based copolymers and is particularly widely used.

However, it is a fact that further improvement of the vulcanization rate is desired for these conventional unsaturated ethylenic copolymers. That is, the unsaturated ethylene-based copolymer is, for example, ethylene / propylene / 5-ethylidene.
-2-Norbornene copolymers have slower vulcanization speed than diene rubbers such as natural rubber, styrene-butadiene rubber, isoprene rubber, butadiene rubber, nitrile rubber, and co-vulcanizability with diene rubbers. Was inferior to

Further, the unsaturated ethylenic copolymer has a slow vulcanization rate, so that the energy consumption during vulcanization is reduced by shortening the vulcanization time or lowering the vulcanization temperature. It was difficult to produce 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. However, 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, it has been desired to develop an unsaturated ethylenic copolymer having excellent weather resistance, heat resistance and ozone resistance, and having a high vulcanization rate. The present inventor, as a result of earnest research on unsaturated ethylene-based copolymers in view of the above-mentioned prior art, ethylene, an unsaturated ethylene-based copolymer consisting of α-olefin and a specific cyclic polyene,
The inventors have found that they have excellent weather resistance, heat resistance, ozone resistance, and high vulcanization rate, and have completed the present invention.

[0008]

SUMMARY OF THE INVENTION The present invention is intended to solve the above-mentioned problems in the prior art, and is an unsaturated ethylene type resin which is excellent in weather resistance, heat resistance and ozone resistance and has a high vulcanization rate. The purpose is to provide a copolymer.

[0009]

SUMMARY OF THE INVENTION 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) the following general formula [I ] Or [II], which is a random copolymer with at least one polyene,

[0010]

[Chemical 7]

(In the formula, n is an integer of 1 to 5, and R is¹Is
R is an alkyl group having 1 to 8 carbon atoms, ²~ R¹²Is that
Each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
It However, R²And R³Are simultaneously hydrogen atoms
There is no. ),

[0012]

[Chemical 8]

[0013] In the formula, R ⁵ to R ¹⁶ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁴ and R ^{4 'of} either the hydrogen atom or 1 to 8 carbon atoms It is an alkyl group and the other is the following group.

-(CH₂)_n-CR³= CR²CR¹ (N is an integer of 1 to 5 and R¹Is an al having 1 to 8 carbon atoms
R is a kill group²~ R ³Is a hydrogen atom or 1 to 1 carbon atoms
8 is an alkyl group. However, R²And R³At the same time
It is never a hydrogen atom. )], [B] (i) a structural unit derived from ethylene is 30 to 9
2 mol%, (ii) α-olefin having 3 or more carbon atoms
The structural unit derived from 6 to 70 mol%, (iii)
From the polyene represented by the above general formula [I] or [II]
With derived structural units being 0.1 to 30 mol%
And (i) the constitutional unit derived from ethylene / (ii) the number of carbons
The constitutional unit derived from 3 or more α-olefins is mol
The ratio is 40/60 to 92/8, and [C] is a polyester represented by the above general formula [I] or [II].
The structural unit derived from the formula is [I '] or [I
I '] has a structure represented by

[0015]

[Chemical 9]

[D] The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.05 to 10 dl / g. The method for producing an unsaturated ethylene-based 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] or [I].
[I] and at least one polyene are copolymerized in the presence of a catalyst formed from a transition metal compound and an organoaluminum compound to produce an unsaturated ethylenic copolymer as described above. It is characterized by that.

[0017]

DETAILED DESCRIPTION OF THE INVENTION The unsaturated ethylene copolymer and the method for producing the same according to the present invention will be specifically described below.

The unsaturated ethylene copolymer according to the present invention is a random copolymer of [A] (i) ethylene, (ii) an α-olefin having 3 to 20 carbon atoms, and (iii) a cyclic polyene. It is united.

Specific examples of the (ii) α-olefin having 3 to 20 carbon atoms include propylene, 1-butene and 1-butene.
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-eikosen and the like. These may be used alone or in combination of two or more.

The above-mentioned (iii) polyene is a cyclic polyene having a norbornene skeleton and has the following general formula [I]:
Or represented by [II].

[0021]

[Chemical 10]

(In the formula, n is an integer of 1 to 5. Further, R is
¹ is an alkyl group having 1 to 8 carbon atoms, R ^{2 to} R ¹² are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ² and R ³ are hydrogen atoms at the same time. Absent. )

[0023]

[Chemical 11]

[0024] In the formula, R ⁵ to R ¹⁶ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁴ and R ^{4 'of} either the hydrogen atom or 1 to 8 carbon atoms It is an alkyl group and the other is the following group.

-(CH₂)_n-CR³= CR²CR¹ (N is an integer of 1 to 5 and R¹Is an al having 1 to 8 carbon atoms
R is a kill group²~ R ³Is a hydrogen atom or 1 to 1 carbon atoms
8 is an alkyl group. However, R²And R³At the same time
It is never a hydrogen atom. )], Carbon number as above
Specific examples of the alkyl group of 1 to 8 include a methyl group and an ether group.
Cyl group, propyl group, i-propyl group, n-butyl group, i-bu
Cyl group, t-butyl group, pentyl group, hexyl group, hepti
Group and octyl group.

The polyene having the norbornene skeleton represented by the formula (I) or [II] (iii) is as follows.
Specific examples include the following compounds.

[0027]

[Chemical 12]

[0028]

[Chemical 13]

[0029]

[Chemical 14]

[0030]

[Chemical 15]

[0031]

[Chemical 16]

[0032]

[Chemical 17]

[0033]

[Chemical 18]

[0034]

[Chemical 19]

[0035]

[Chemical 20]

[0036]

[Chemical 21]

[0037]

[Chemical formula 22]

These may be used alone or in combination of two or more. The polyene represented by the above formula [I] can be produced, for example, by condensing norbornadiene and polyenes having a conjugated diene by the Diels-Alder reaction as shown in the following formula.

[0039]

[Chemical formula 23]

The polyene represented by the above formula [II] is, for example, as shown in the following formula, 5-vinyl-norbornene (5-vinyl-bicyclo [2.2.1] hept-2-ene).
And a polyene having a conjugated diene can be condensed and produced.

[0041]

[Chemical formula 24]

According to the above reaction, the polyene having a norbornene skeleton is usually obtained as a stereoisomer mixture of endo and exo isomers. The unsaturated ethylenic copolymer according to the present invention has the above-mentioned (i) ethylene,
(ii) α-olefin and (iii) structural units derived from respective monomers of polyene are randomly arranged and bonded, and have a substantially linear structure which may have a branched structure. ing. The fact that this copolymer has a substantially linear structure and does not substantially contain a gelled crosslinked polymer means that the copolymer is soluble in an organic solvent and does not substantially contain an insoluble component. You can check. For example, when the intrinsic viscosity [η] is measured, it can be confirmed by completely dissolving the copolymer 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 0.1 to 30 mol%, preferably 0.1 to 30 mol% of the constitutional unit derived from (iii) polyene.
1 to 20 mol%, more preferably 0.2 to 10 mol%
It is contained in the amount of.

Particularly, in the unsaturated ethylene 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 / Fifty
It is present in an amount of ˜90 / 10, more preferably 50/88.

In the unsaturated ethylene copolymer according to the present invention, the constitutional unit derived from the polyene represented by the general formula [I] is substantially represented by the following formula [I ']. It has a structure.

[0046]

[Chemical 25]

The constitutional unit derived from the polyene represented by the general formula [II] has a structure substantially represented by the following formula [II '].

[0048]

[Chemical formula 26]

The fact that the structural unit derived from the cyclic polyene has the above structure means that the ¹³ C-
This can be confirmed by measuring the NMR spectrum.

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 5 dl / g.
More preferably, it is 0.2 to 3 dl / g.

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 ethylenic 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 polypropylene, polyethylene, polybutene, polystyrene, etc., impact resistance and stress crack resistance are dramatically improved. To do.

The unsaturated ethylene-based copolymer according to the present invention may be vulcanized alone and used, or may be co-vulcanized 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 vulcanizable with a diene rubber such as natural rubber, styrene-butadiene rubber, isoprene rubber, butadiene rubber, nitrile rubber, 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. The unsaturated ethylene-based copolymer according to the present invention comprises (i) ethylene and (ii) carbon atoms of 3 to
It is obtained by copolymerizing 20 α-olefins and (iii) the polyene represented by the above general formula in the presence of a catalyst.

As such a catalyst, a Ziegler type catalyst composed of a transition metal compound such as vanadium (V), zirconium (Zr) and titanium (Ti) and an organic aluminum compound (organic aluminum oxy compound) can be used. In the present invention, a catalyst comprising [a] a soluble vanadium compound and an organoaluminum compound, or [b] a catalyst comprising a metallocene compound of a transition metal selected from Group IVB of the periodic table and an organoaluminum oxy compound is particularly preferably used. To be

The soluble vanadium compound which forms the catalyst [a] is specifically represented by the following general formula. In the formula VO (OR) _a X _b or V (OR) _c X _d , R is a hydrocarbon group, and a, b, c and d are 0 ≦ a ≦ 3, 0 ≦ b ≦ 3 and 2 ≦ a + b, respectively. ≦ 3, 0 ≦ c ≦
4, 0 ≦ d ≦ 4, 3 ≦ c + d ≦ 4 are satisfied.

As the vanadium compound represented by the above formula, specifically, VOCl ₃ , VO (OCH ₃ ) Cl 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 (Ot-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 soluble vanadium compound can also be used as an electron donor adduct 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,
C1-C18 alcohols such as octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol, and C1-C18 alcohols such as trichloromethanol, trichloroethanol and trichlorohexanol Halogen-containing alcohols, phenol, cresol, xylenol,
C6-C20 phenols which may have a lower alkyl group such as ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol, carbon number such as acetone, methylethylketone, methylisobutylketone, acetophenone, benzophenone and benzoquinone 3 to 15 ketones, acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, and other aldehydes having 2 to 15 carbon atoms, 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 ethyl benzoate, methyl anisate, Organic acid esters having 2 to 18 carbon atoms such as ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide and ethyl carbonate, acetyl chloride, benzoyl chloride, toluyl chloride, Acid halides having 2 to 15 carbon atoms such as nissic acid chloride, ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether, acetic anhydride, phthalic anhydride Acids, acid anhydrides such as benzoic anhydride, ethyl silicate, alkoxysilanes such as diphenyldimethoxysilane, acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-dimethylamide and other acids Amides, trimethylamine, triethylamine, tributylamine, tribenzylamine, amines such as tetramethylethylenediamine, acetonitrile, benzonitrile, nitriles such as trinitrile, pyridine,
Pyridines such as methyl pyridine, ethyl pyridine, dimethyl pyridine and the like can be mentioned.

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 the 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 [Where x, y, z
Is a positive number and z ≧ 2x. ] Alkenyl aluminum such as isoprenyl aluminum represented by
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 sesquichloride, ethylaluminium sesquichloride, isopropyl aluminum sesquichloride. Alkyl aluminum sesquihalides such as butyl aluminum sesquichloride and ethyl aluminum sesquibromide, alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride and ethyl aluminum dibromide, diethyl aluminum hydride Dialkylaluminum hydride such as dibutyl aluminum hydride, ethyl aluminum dihydride, alkyl aluminum dihydride 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] In the formula, R ¹ is the same as the above formula [III], and Y is —OR.
¹⁰ groups, -OSiR ¹¹ ₃ groups, -OAlR ¹² ₂ groups, -NR ¹³ ₂ groups
Group, —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, A trimethylsilyl group and the like, and 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. (1) Compounds represented by R ¹ _n Al (OR ¹⁰ ) _3-n , for example, dialkyl aluminum alkoxides such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, ethyl aluminum sesquiethoxide, butyl aluminum Sesquibutoxide and partially alkoxylated alkylaluminum having an average composition represented by R ¹ _2.5 Al (OR ² ) _0.5 , ethylaluminum ethoxy chloride, butylaluminum butoxycyclolide, ethylaluminum ethoxy bromide and the like. And halogenated alkylaluminums. (2) a compound represented by R ¹ _n Al (OSi R ¹¹ ₃ ) _3-n ,
For example, Et ₂ Al (OSi Me ₃ ) (iso-Bu) ₂ Al (OSi Me ₃ ) (iso-Bu) ₂ Al (OSi Et ₃ ), etc. (3) R ¹ _n Al (OAlR ¹² ₂ ) _3- a compound represented by _n ,
For example, a compound represented by (4) R ¹ _n Al (NR ¹³ ₂ ) _3-n , such as Et ₂ AlOAlEt ₂ (iso-Bu) ₂ AlOAl (iso-Bu) ₂ , such as Me ₂ AlNEt ₂ Et ₂ AlNHMe Me ₂ AlNHET Et ₂ AlN (Si Me ₃ ) ₂ (iso-Bu) ₂ AlN (SiMe ₃ ) _{2 and} other compounds represented by (5) R ¹ _n Al (Si R ¹⁴ ₃ ) _3-n , for example, , (Iso-Bu) ₂ AlSi Me _3, etc., (6) compounds represented by R ¹ _n Al [N (R ¹³ ) AlR ¹⁶ ₂ ] _3-n , such as Et ₂ AlN (Me) AlEt ₂ , (iso -Bu) ₂ AlN (Et) Al (iso-Bu) _{2 and the} like.

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

Next, the catalyst composed of the metallocene compound [b] and the organoaluminum oxy compound used in the present invention will be described. A metallocene compound of a transition metal 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 the 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 Examples thereof include a nyl group.

These groups may be substituted with a halogen atom, a trialkylsilyl group or the like. L other than the ligand having a cyclopentadienyl skeleton has 1 to 1 carbon atoms.
2 hydrocarbon group, an alkoxy group, an aryloxy group, a sulfonic acid-containing group (-SO ₃ R ^a), a halogen atom or a hydrogen atom (wherein, R ^a is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group Or an aryl group substituted with a halogen atom or an alkyl 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, , Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-
Butyl, t-butyl, pentyl, hexyl, octyl, decyl, dodecyl, and other alkyl groups, cyclopentyl, cyclohexyl, and other cycloalkyl groups, phenyl, tolyl, and other aryl groups, and benzyl groups , An aralkyl group such as a neophyll group.

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

Examples of the aryloxy group include a phenoxy group and the like, and examples of the sulfonic acid-containing group (-SO ₃ ^Ra ) include a methanesulfonato group, a p-toluenesulfonato group,
Examples thereof 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]. As the catalyst composed of a Zr compound, 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 having a cyclopentadienyl skeleton. (Ligand), 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 above general formula [V]. k is an integer of 1 or more, and k + l + m + n = 4.

In the following, at least 2 ligands in which M is zirconium and have a cyclopentadienyl skeleton are used.
Examples of the metallocene compound containing one are shown. Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopenta 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 methoxy chloride, bis (cyclopentadienyl) di Ruconium ethoxy chloride, 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 (trifluoromethane sulfonate),
Bis (hexylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (1,3-dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (1-methyl-3-ethylcyclopentadiene) (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.

In the above formula (d), R ² , R ³ and R
^At least two of ⁴ and R ⁵ , ie R ² and R ³
Is a group (ligand) having a cyclopentadienyl skeleton, and these groups having two cyclopentadienyl skeletons are bonded to each other through an alkylene group, a substituted alkylene group, a silylene group or a substituted silylene group. It is also possible to exemplify a bridge-type metallocene compound. At this time, R ⁴ and R ⁵ are independently the same as L other than the ligand having the cyclopentadienyl skeleton described in the formula [V].

Examples of such bridge-type metallocene compounds include 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)
And so on.

Although a zirconocene compound has been exemplified as the metallocene compound in the above, a compound in which zirconium is replaced with titanium or hafnium can also be exemplified.

These compounds may be used alone,
You may use it in combination of 2 or more type. In the present invention, a zirconocene compound having a central metal atom of zirconium and having a ligand containing at least two cyclopentadienyl skeletons is preferably used as the metallocene compound.

These metallocene compounds may be diluted with hydrocarbon or halogenated hydrocarbon before use. The metallocene compound as described above can also be used together with the carrier compound by bringing it into contact with the particulate carrier compound.

Examples of the carrier compound include SiO ₂ , Al
₂ O ₃ , B ₂ O ₃ , MgO, Zr O ₂ , CaO, Ti
Inorganic carrier compounds such as O ₂ , ZnO, Zn ₂ O, SnO ₂ , BaO and ThO, polyethylene, polypropylene, poly-1
Resins such as -butene, poly-4-methyl-1-pentene, and styrene-divinylbenzene copolymer can be used.
These carrier compounds may be used in combination of two or more.

Next, the organoaluminum oxy compound used for forming the catalyst [b] in the present invention 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 conventionally known aluminoxane is specifically represented by the following general formula.

[0086]

[Chemical 27]

(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.) where the aluminoxane has the formula (OA
1 (R ¹ )) and an alkyloxyaluminum unit represented by the formula (OA1 (R ² )) [wherein R ¹ and R ² are the same hydrocarbon groups as R. And R ¹ and R ²
Represent different groups].

The 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 adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to an aromatic hydrocarbon solvent in which is suspended and reacted to recover a solution of the aromatic hydrocarbon solvent. (2) A method in which water (water, ice, or steam) is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran to recover it as a solution of an aromatic hydrocarbon solvent.

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 as described above, and specifically, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, and tri-n. -Butyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri te
rt-butyl aluminum, tripentyl aluminum,
Trihexylaluminum, trioctylaluminum, tridecyl aluminum, tricyclohexyl aluminum, trialkyl aluminum such as tri-cyclooctyl aluminum, the general formula _{(i-C 4 H 9)} x Al
_y (C ₅ H ₁₀ ) _z [where 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, diethyl aluminum hydride,
Examples thereof include dialkyl aluminum hydrides such as diisobutyl aluminum hydride, dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide, and dialkyl aluminum aryloxides such as diethyl aluminum phenoxide.

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.

[0092] 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 preferably in the range of to 0.07.

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

[0094]

[Chemical 28]

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

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.

[0097]

[Chemical 29]

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. Further, 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 an 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 organoaluminum oxy compound used in the present invention may contain a small amount of an organic compound component of a metal other than aluminum. The organoaluminum oxy compound can also be used by supporting it on the above-mentioned carrier compound.

When forming the catalyst [b], the aforementioned organoaluminum compound may be used together with the organoaluminum oxy compound. In the present invention, in the presence of the catalyst [a] or [b] as described above, (i) ethylene,
The (ii) α-olefin and (iii) polyene are usually copolymerized in the liquid phase. At this time, a hydrocarbon solvent can also be used.

Examples of such a hydrocarbon solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, and kerosene and halogen derivatives thereof, and alicyclic 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 polyene may be copolymerized by a batch method or a continuous method, but is preferably a continuous method. When carrying out the copolymerization by a continuous method,
The catalyst is used in the following concentrations.

When the catalyst [a] is used, the concentration of the soluble vanadium compound in the polymerization system is usually 0.01.
.About.5 mmol / liter (polymerization volume), preferably 0.1.
It is 05 to 3 mmol / liter. It is desirable that the soluble vanadium compound is supplied at a concentration of 10 times or less, preferably 1 to 7 times, and more preferably 1 to 5 times the concentration of the soluble vanadium compound present in the polymerization system. The organoaluminum compound has a ratio of aluminum atoms to vanadium atoms in the polymerization system (Al / V).
2 or more, preferably 2 to 50, more preferably 3
Supplied in an amount of ~ 20.

The soluble vanadium compound and the organoaluminum compound are usually supplied diluted with the above-mentioned hydrocarbon solvent and / or liquid (ii) α-olefin and (iii) polyene. At this time, the soluble vanadium compound is preferably diluted to the above-mentioned concentration, but the organoaluminum compound should be prepared at an arbitrary concentration of, for example, 50 times or less the concentration in the polymerization system and supplied to the polymerization system. Is desirable.

When the catalyst [b] consisting of a metallocene compound and an organoaluminumoxy compound is used, the concentration of the metallocene compound in the polymerization system is usually 0.
0.0005 to 0.1 mmol / liter (polymerization volume),
It is preferably 0.0001 to 0.05 mmol / liter. The organoaluminum oxy compound has a ratio of aluminum atom to metallocene compound in the polymerization system (Al / transition metal) of 1 to 10,000, preferably 1
Supplied in an amount of 0-5000. When an organoaluminum compound is used, it is usually about 0 based on 1 mol of aluminum atom in the organoaluminum oxy compound.
To 200 mol, preferably about 0 to 100 mol.

In the present invention, (i) ethylene and (ii) α-
When the olefin and (iii) polyene 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 ° C to 100 ° C, preferably Is -30 ° C to 80
℃, more preferably -20 ℃ ~ 60 ℃, the pressure is more than 0 ~ 50Kg / cm ² , preferably more than 0 ~ 20Kg
/ Cm ² conditions.

The copolymerization reaction carried out in the presence of the catalyst [b] consisting of the metallocene compound and the organoaluminum oxy compound is usually carried out at a temperature of -20 ° C to 150 ° C, preferably 0 ° C to 120 ° C, and more preferably Is 0 to 100
℃, the pressure is more than 0 ~ 80kg / cm ² , preferably 0
The carried out under conditions of ~50Kg / cm ² beyond.

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, (i) ethylene, (ii) α-olefin and (iii) polyene are added to the polymerization system in such amounts that an unsaturated ethylenic copolymer having a specific composition as described above can be obtained. Supplied. Further, in the copolymerization, a molecular weight modifier such as hydrogen can be used.

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

[0112] according to the vulcanization present invention unsaturated ethylene copolymer, its properties are exhibited more effectively when used in vulcanized state, as described above.

The unsaturated ethylene copolymer according to the present invention is vulcanized in the same manner as in the case of obtaining a general vulcanized rubber. That is, an unvulcanized compounded rubber (composition) is once prepared from this unsaturated ethylene copolymer, and then this compounded rubber is molded into a desired shape and then vulcanized.

Examples of the vulcanization method include a method of heating with a vulcanizing agent and a method of irradiating with an electron beam without using a vulcanizing agent. Specific examples of components to be added to such a compounded rubber (composition) include a reinforcing agent, a filler, a softening agent, a vulcanizing agent, a vulcanization aid, a plasticizer, a stabilizer, a processing aid, and a coloring. Examples include various agents such as agents, foaming agents, and other rubber compounding agents.

As the reinforcing agent, SRF, GPF, FE
Examples thereof include carbon black such as F, HAF, ISAF, SAF, FT and MT, and finely divided silicic acid. Examples of the filler include calcium carbonate, talc, clay, silica and the like.

Further, petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and petrolatum, coal tar-based softeners such as coal tar and coal tar pitch, castor oil, linseed oil, rapeseed oil, palm oil. Fatty oil softeners such as, tall oil, sub,
Examples thereof include waxes such as beeswax, carnauba wax and lanolin, and fatty acids and fatty acid salts such as stearic acid, ricinoleic acid, palmitic acid, barium stearate, calcium stearate and zinc laurate.

Examples of the vulcanizing agent include sulfur compounds and organic peroxides. Specific examples of the sulfur compound include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide,
Examples thereof include tetramethylthiuram disulfide and selenium dimethyldithiocarbamate. Of these, sulfur is preferred.

The sulfur compound is used in an amount of usually 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. As the organic peroxide, specifically, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylhydroperoxide, t-butylcumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxine) hexyne-3,2,5-dimethyl-
2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-mono (t-butylperoxy) -hexane, α,
Examples include α'-bis (t-butylperoxy-m-isopropyl) benzene and the like. Among these, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane and the like are preferable.

These organic peroxides are used alone or in combination of two or more, and usually 0.0003 to 0.05 mol, preferably 0.001 with respect to 100 mol of the unsaturated ethylene copolymer. It is used in an appropriate amount within the range of 0.03 mol.

When a sulfur compound is used as the vulcanizing agent, it is preferable to use a vulcanization accelerator together. Specific examples of vulcanization accelerators include N-cyclohexyl-2-benzothiazole sulfenamide and N-oxydiethylene-2-
Benzothiazole sulfenamide, N, N-diisopropyl-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl-4 -Thiazol compounds such as morpholinothio) benzothiazole and dibenzothiazyl disulfide, guanidine compounds such as diphenylguanidine, triphenylguanidine, diorsonitrile guanidine, orthonitrile biguanide and diphenylguanidine phthalate, acetaldehyde-aniline reaction products, butyl Aldehyde-aniline condensate, hexamethylenetetramine, aldehyde amines such as acetaldehyde ammonia and aldehyde-
Ammonia compounds, imidazoline compounds such as 2-mercaptoimidazoline, thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, thiourea compounds such as diorthotolylthiourea, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, Thiuram compounds such as tetraethylthiuram disulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate , Sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, dimethyldithiocarb Dithio acid salt-based compounds such as amine acid tellurium, xanthate-based compound such as dibutyl xanthate zinc, zinc flower and the like.

These vulcanization accelerators are generally 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. When using an organic peroxide as a vulcanizing agent,
It is preferable to use a vulcanization aid together.

Specific examples of vulcanization aids include sulfur and p-
Quinonedioxime compounds such as quinonedioxime, (meth) acrylate compounds such as trimethylolpropane triacrylate, polyethylene glycol dimethacrylate, allyl compounds such as diallyl phthalate and triallyl cyanurate, m-phenylene bismaleimide, etc. Examples thereof include maleimide compounds and divinylbenzene.

Such a vulcanization aid is used in an amount of 0.5 to 2 mol, preferably about 1 mol, based on 1 mol of the organic peroxide used.
Used in molar amounts. The unvulcanized compounded rubber is prepared by the following method. That is, the unsaturated ethylene copolymer and the above-mentioned other components were mixed with a Banbury mixer to
After kneading at a temperature of 0 to 170 ° C. for 3 to 10 minutes, a vulcanizing agent, a vulcanization accelerator, a vulcanization aid, or the like is added as needed, and the roll temperature is set to 40 to 8 by an open roll or the like.
After kneading at 0 ° C for 5 to 30 minutes, the mixture is dispensed to obtain a ribbon-shaped or sheet-shaped compounded rubber.

The compounded rubber thus prepared is preformed into a desired shape by an extruder, a calender roll or a press, and at the same time as molding or by introducing the molded product into a vulcanization tank, a temperature of 150 to 270.degree. It is vulcanized by heating for 1 to 30 minutes or by irradiating with an electron beam.

When the above compounded rubber is vulcanized by heating, the vulcanization tank may be hot air, a fluidized bed of glass beads, UH.
A heating tank such as F (ultra-high frequency electromagnetic wave) or steam can be used.

When vulcanized by electron beam irradiation, an electron beam having an energy of 0.1 to 10 MeV, preferably 0.3 to 2 MeV is added to the preformed compounded rubber.
Absorbed dose is 0.5 to 35 Mrad, preferably 0.5 to
Irradiation may be performed at 10 Mrad.

A mold may or may not be used for molding / vulcanization. When a mold is not used, the compounded rubber is usually continuously molded and vulcanized. The rubber vulcanizate obtained by molding and vulcanizing as described above,
It can be used for applications such as automobile industrial parts, industrial rubber products such as rubber rolls and belts, electrical insulating materials, civil engineering building materials, rubberized cloth, and the like.

The 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.

[0129]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0130]

Example 1 4- (4′-methyl-3′-pentenyl) -tricyclo [6.2.1.
Synthesis of [ ^2,7 ] undecane- 4,9-diene (MPCTU) 136.2 g (1.0 mol) of myrcene, 92.0 g (1.0 mol) of norbornadiene and 72 of hydroquinone
After being placed in a stainless steel autoclave and sealed with nitrogen, the mixture was heated and stirred at 200 ° C. for 6 hours. After cooling to room temperature, the autoclave was opened and the precipitate was filtered off. The filtrate was distilled and purified under reduced pressure using a 5-stage Oldershaw to obtain the desired product, 4- (4'-methyl-3'-pentenyl) -tricyclo [6.2.1.0 ^2,7 ] undecane-4,9. -The Diene (MPC
TU) was isolated in the form of a mixture of endo isomer / exo isomer = 17/3 to obtain 66.0 g.

The MPCTU thus obtained had a purity of 94.0% as measured by gas chromatography, a boiling point of 107 to 114 ° C./0.1 mmHg, and a yield of 27%. .

Gas chromatography-mass spectrometry and infrared absorption spectrum of this MPCTU were measured. Gas chromatography-mass spectrometry: End body m / z 228 (M ⁺ ), 185, 162,
147, 93, 91 exo body m / z 228 (M ⁺ ), 185, 162,
147, 93, 91 infrared absorption spectrum (cm ^-1 , neat, mixture of endo and exo forms): 3060, 3030, 296
0, 2925, 2850, 1560, 1575, 146
5, 1450, 1380, 1330, 1105, 78
0, 760, 700 [Polymerization] Using a 2-liter polymerization vessel equipped with a stirring blade, a copolymerization reaction of ethylene, propylene and the above MPCTU was continuously carried out.

From the upper part of the polymerization reactor, a hexane solution of MPCTU was added at 0.5 liters per hour so that the concentration in the polymerization reactor was 2 ml / liter, and VO (OC ₂
A hexane solution of H ₅ ) Cl ₂ was added to the polymerization vessel at a concentration of vanadium of 0.2 mmol / liter per hour.
5 liters, ethyl aluminum sesquichloride (Al
A hexane solution of (C ₂ H ₅ ) _1.5 Cl _1.5 ) was added in an amount of 0.5 liter / hour and hexane was adjusted to 0.5 ml / hour so that the aluminum concentration in the polymerization vessel was 2.0 mmol / liter.
5 liters of each was continuously fed into the polymerization vessel,
On the other hand, the polymerization liquid in the polymerization vessel was continuously withdrawn from the upper portion of the polymerization vessel so that the polymerization liquid was always 1 liter.

Further, ethylene was supplied at a rate of 120 liters per hour, propylene was supplied at a rate of 180 liters per hour, and hydrogen was supplied at a rate of 5 liters per hour by 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 / MPCTU 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 polymer is heated at 100 ° C. for 2 hours.
It was dried under reduced pressure for 4 hours.

As described above, ethylene / propylene / M
PCTU copolymer was obtained in an amount of 32 g / h. The obtained copolymer had an ethylene constitutional unit of 63.5 mol% and a propylene constitutional unit of 35.7 mol%, and MP
It contained the CTU structural unit in an amount of 0.8 mol%, and the ratio of the ethylene structural unit / the propylene structural unit was 64/36 (molar ratio). The intrinsic viscosity [η] was 2.6 dl / g.

[0137]

Example 2 An ethylene / propylene / MPCTU copolymer was copolymerized in the same manner as in Example 1 except that MPCTU was supplied so that the concentration in the polymerization vessel was 4 ml / l. Was obtained in an amount of 31 g / h.

The resulting copolymer had an ethylene constitutional unit of 65.7 mol% and a propylene constitutional unit of 32.8.
The amount of the MPCTU structural unit was 1.5 mol% and the ratio of the ethylene structural unit / the propylene structural unit was 67/33 (molar ratio). The intrinsic viscosity [η] was 3.1 dl / g.

[0139]

Example 3 The composition shown in Table 1 containing the ethylene / propylene / MPCTU copolymer obtained in Example 2 was kneaded with a 6-inch open roll to obtain an unvulcanized compounded rubber.

The vulcanization rate of this compounded rubber was evaluated. The results are shown in Table 2.

[0141]

[Table 1]

[0142]

[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 per 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 are continuously fed into the polymerization vessel, respectively, while the polymerization liquid in the polymerization vessel is 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 in 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 the polymer, and then the temperature was raised to 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.

The vulcanization rate was evaluated in the same manner as in Example 2 by using the obtained copolymer. The results are shown in Table 2.

[0147]

[Table 2]

The vulcanization rate was measured by the JSR curlast meter.
-Type 3 (manufactured by Japan Synthetic Rubber Co., Ltd.)
Minimum torque value M obtained from the sulfur curve_LAnd the maximum value M_HDifference
To M _EAs 90% M_ETime to reach₉₀(Minutes)
It was

[0149]

Example 4 5- [1 ′-(4 ″ -methyl-3 ″ -pentenyl) -1′-cyclohex
Sen-4'-yl] -bicyclo [2.2.1] hept-2-ene (M
Synthesis of PCHNB) 115.6 g (0.85 mol) of myrcene, 204.3 g (1.7 mol) of 5-vinylnorbornene and 60 mg of hydroquinone were placed in a stainless steel autoclave and sealed with nitrogen. The mixture was heated and stirred for an hour. After cooling to room temperature, the autoclave was opened, and the resulting reaction solution was distilled and purified under reduced pressure using a 5-stage Oldershaw to obtain the desired product, 5- [1 '-(4''-methyl-3).'' -Pentenyl) -1'-cyclohexene-4'-yl] -bicyclo [2.
2.1] Hept-2-ene (MPCHNB) was isolated in the form of a mixture of four diastereomers to obtain 66.1 g.

MPCHNB thus obtained is
Purity measured by gas chromatography is 87.4%
The boiling point was 112 to 113 ° C./0.1 mmHg, and the yield was 26%.

For this MPCHNB, gas chromatography-mass spectrometry and infrared absorption spectrum were measured. Gas chromatography-mass spectrometry: m / z 256 (M ⁺ ), 21
3, 187, 145, 131, 91, 69 infrared absorption spectrum (cm ^-1 , neat, mixture of 4 diastereomers): 3080, 3030, 2930,
2850, 1640, 1455, 1380, 1105,
1000, 905 [Polymerization] Ethylene, propylene and MPCHNB obtained as described above were copolymerized using a 500 ml polymerization vessel equipped with a stirring blade and a gas blowing tube.

Under a nitrogen flow, 250 ml of dehydrated and dried toluene and 1.6 ml of MPCHNB were charged into the polymerization vessel. The temperature of this solution is kept at 30 ° C., and ethylene, propylene, and hydrogen are added at 120 liters / hour,
180 liters, 15 liters introduced continuously,
Ethyl aluminum sesquichloride (Al (C ₂ H ₅ ))
0.5 ml of a hexane solution of _1.5 Cl _1.5 ) (1 mmol / ml in terms of aluminum atom) was added. 0.5 ml of a hexane solution of VO (OC ₂ H ₅ ) Cl ₂ (0.1 mmol / ml) was added from a dropping funnel to start the copolymerization reaction.
The copolymerization reaction was carried out at 10 ° C. for 10 minutes, and a small amount of isobutyl alcohol was added to terminate the polymerization. The polymerization solution was washed with hydrochloric acid water and poured into a large amount of methanol to precipitate a copolymer. Then, the precipitated copolymer was recovered and
It was dried under reduced pressure overnight at 0 ° C.

As described above, ethylene / propylene / M
3.6 g of PCHNB copolymer was obtained. The resulting copolymer had an ethylene constitutional unit content of 65.4 mol%, a propylene constitutional unit content of 33.7 mol%, an MPCHNB constitutional unit content of 0.9 mol%, and an ethylene constitutional unit / propylene constitutional unit. Was 66/34 (molar ratio). The intrinsic viscosity [η] was 2.8 dl / g.

[0154]

Example 5 Using a 500 ml polymerization vessel equipped with a stirring blade and a gas blowing tube, ethylene, propylene and M
Copolymerized with PCTU.

Under a nitrogen flow, 250 ml of dehydrated and dried toluene and 2.4 ml of MPCTU were placed in this polymerization vessel. The temperature of this solution was maintained at 20 ° C., and ethylene and propylene were continuously introduced in the amounts of 80 liter and 120 liter per hour, respectively. 3.5 ml of a toluene solution of methylalumoxane (0.72 mmol / ml in terms of aluminum atom) and a hexane solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (0.005 mmol / ml) ) Was charged to start the polymerization. 20
After carrying out the polymerization at 30 ° C. for 30 minutes, a small amount of isobutyl alcohol was added to terminate the polymerization. The polymerization solution was washed with hydrochloric acid water and poured into a large amount of methanol to precipitate a copolymer. Then, the precipitated copolymer was recovered and dried under reduced pressure at 100 ° C. for 24 hours.

As described above, ethylene / propylene / M
8.6 g of PCTU copolymer was obtained. The resulting copolymer had an ethylene constitutional unit of 67.5 mol%, a propylene constitutional unit of 31.7 mol% and an MPCTU constitutional unit of 0.8.
It was contained in an amount of mol%, and the ratio of the ethylene structural unit / the propylene structural unit was 68/32 (molar ratio). The intrinsic viscosity [η] was 2.7 dl / g.

Front page continued (72) Inventor Hideshi Matsuoka Climbing No. 1-2, Waki, Waki-cho, Kuma-gun, Yamaguchi Prefecture Mitsui Petrochemical Industries, Ltd. Address Mitsui Sekiyu Kagaku Kogyo Co., Ltd.

Claims (2)

[Claims] 1. [A] (i) ethylene and (ii) carbon number 3 to 2
An α-olefin of 0, and (iii) the following general formula [I] or
Rand with at least one polyene represented by [II]
Is a copolymer of(In the formula, n is an integer of 1 to 5, and R¹Has 1 to 8 carbon atoms
Is an alkyl group of R²~ R¹²Are each independently hydrogen
An atom or an alkyl group having 1 to 8 carbon atoms. However, R
²And R³Are not hydrogen atoms at the same time. ), [Chemical formula 2][In the formula, R^Five~ R¹⁶Are each independently a hydrogen atom or charcoal
R is an alkyl group having a prime number of 1 to 8,^FourAnd R^Four'Nozu
One of them is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
And the other is the following groups: -(CH₂)_n-CR³= CR²CR¹ (N is an integer of 1 to 5 and R¹Is an al having 1 to 8 carbon atoms
R is a kill group²~ R ³Is a hydrogen atom or 1 to 1 carbon atoms
8 is an alkyl group. However, R²And R³At the same time
It is never a hydrogen atom. )], [B] (i) a structural unit derived from ethylene is 30 to 9
2 mol%, (ii) α-olefin having 3 or more carbon atoms
The structural unit derived from 6 to 70 mol%, (iii)
From the polyene represented by the above general formula [I] or [II]
The derived constitutional unit is 0.1 to 30 mol%, and
(i) Structural units derived from ethylene / (ii) C3 or more
The structural units derived from the above α-olefin are in molar ratio
40/60 to 92/8, and [C] the polyester represented by the above general formula [I] or [II].
The structural unit derived from the formula is [I '] or [I
I '] has a structure represented by:[D] Intrinsic viscosity [η] measured in decalin at 135 ° C
Is characterized by a value of 0.05 to 10 dl / g
Ethylene-based copolymer. 2. (i) Ethylene and (ii) α having 3 to 20 carbon atoms.
-Olefin, and (iii) the following general formula [I] or [II]
With at least one polyene represented by
Formed from organic compounds and organoaluminum compounds
Copolymerized in the presence of(In the formula, n is an integer of 1 to 5, and R¹Has 1 to 8 carbon atoms
Is an alkyl group of R²~ R¹²Are each independently hydrogen
An atom or an alkyl group having 1 to 8 carbon atoms. However, R
²And R³Are not hydrogen atoms at the same time. ), [Chemical 5][In the formula, R^Five~ R¹⁶Are each independently a hydrogen atom or charcoal
R is an alkyl group having a prime number of 1 to 8,^FourAnd R^Four'Nozu
One of them is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
And the other is the following groups: -(CH₂)_n-CR³= CR²CR¹ (N is an integer of 1 to 5 and R¹Is an al having 1 to 8 carbon atoms
R is a kill group²~ R ³Is a hydrogen atom or 1 to 1 carbon atoms
8 is an alkyl group. However, R²And R³At the same time
It is never a hydrogen atom. )], [A] (i) ethylene, and (ii) α-ole having 3 to 20 carbon atoms.
A fin and (iii) represented by the above general formula [I] or [II]
A random copolymer with at least one polyene
Yes, [B] (i) 30 to 9 constitutional units derived from ethylene
2 mol%, (ii) α-olefin having 3 or more carbon atoms
The structural unit derived from 6 to 70 mol%, (iii)
From the polyene represented by the above general formula [I] or [II]
The derived constitutional unit is 0.1 to 30 mol%, and
(i) Structural units derived from ethylene / (ii) C3 or more
The structural units derived from the above α-olefin are in molar ratio
40/60 to 92/8, and [C] the polyester represented by the above general formula [I] or [II].
The structural unit derived from the formula is [I '] or [I
I '] has a structure represented by:[D] Intrinsic viscosity [η] measured in decalin at 135 ° C
Of unsaturated ethylenic copolymer with a value of 0.05 to 10 dl / g
Unsaturated ethylene-based copolymers characterized by obtaining a coalescence
Body manufacturing method.