JPH09124737A - Unsaturated olefinic random copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an α-olefin/cyclic nonconjugated diene random copolymer which can give a vulcanized rubber excellent in vibration-damping and mechanical properties and to provide a compsn. contg. the same. SOLUTION: A 6C or higher α-olefin/cyclic nonconjugated diene random copolymer is provided which has a cyclic nonconjugated diene content of 1-40mol%, a wt. average mol.wt. (Mw) in terms of polystyrene (by gel permeation chromatography) of 100,000-2,000,000, and a ratio of Mw/Mn (wherein Mn is the number average mol.wt. in terms of polystyrene) by gel permeation chromatography of 2-5. A compsn. is provided by compounding the random copolymer with a carbon black, a vulcanizing agent and/or a cross-linker, and if necessary a process oil.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin-based random copolymer containing an unsaturated group, and more specifically, a higher α-olefin / cyclic non-conjugated diene copolymer excellent in vibration damping property and mechanical properties, And its compositions.

[0002]

BACKGROUND OF THE INVENTION Unsaturated group-containing olefin-based random copolymers have excellent heat resistance and weather resistance, and are widely used as automobile parts, machine parts, civil engineering and construction materials, electric wire coating materials, electrical insulating materials, medical materials, etc. It is used and its variety is wide. In particular, an unsaturated group-containing olefin-based random copolymer using only olefins having 4 or more carbon atoms includes 1-butene / 1-hexene / 4 (or 5) -methyl-1,4-hexadiene copolymer Combined (see US Pat. Nos. 3,933,769 and 3,999,162), 1-hexene / 1,7-octadiene copolymer (US Pat. Nos. 3,933,769 and 399126).
No. 2, No. 4340705, No. 45515
No. 03 specification) and the like, and are used for cushion rubber for artificial joints and the like. However, the vulcanized rubber obtained from these copolymers has a drawback that the compression set is large. On the other hand, the inventors of the present invention, regarding the α-olefin / non-conjugated diene copolymer having 4 or more carbon atoms,
An unsaturated group-containing olefin-based random copolymer having a low impact resilience and excellent vibration damping property, which uses an α, ω-non-conjugated diene represented by 1,9-decadiene as a non-conjugated diene component (JP-A-2 No. 49008) and a non-conjugated diene having an unsaturated group at the terminal and the non-terminal represented by 7-methyl-1,6-octadiene as a non-conjugated diene component, low hardness and compression set. Unsaturated group-containing olefin-based random copolymer with small strain (Japanese Patent Application Laid-Open No. 2-12
3114). However, these copolymers have relatively low mechanical strength (for example, tensile strength) as a vulcanized rubber compared to other rubbers, and further improvement in mechanical strength has been desired.

[0003]

DISCLOSURE OF THE INVENTION The object of the present invention is that the vibration damping property and the compression set are equal to or more than those of the conventional unsaturated group-containing olefin random copolymer, and the mechanical strength is higher. It is to provide an excellent copolymer and a composition thereof.

[0004]

The gist of the present invention is as follows. Firstly, an α-olefin / cyclic non-conjugated diene random copolymer (C6 or more) having the characteristics shown in the following (1) to (3) ( Hereinafter, referred to as "first invention"). (1) Cyclic non-conjugated diene content is 1 to 40 mol%, (2)
The polystyrene reduced weight average molecular weight measured by gel permeation chromatography (GPC) is 100,000 to 2,000,000, and (3) the polystyrene reduced weight average molecular weight / number average molecular weight measured by gel permeation chromatography (GPC) is 2 ~ 5.

Secondly, the gist of the present invention is that, based on 100 parts by weight of the α-olefin / cyclic non-conjugated diene random copolymer having 6 or more carbon atoms of the first invention, carbon black 30 is used.
˜150 parts by weight, 0 to 100 parts by weight of process oil, and 0.3 to 10 parts by weight of a vulcanizing agent and / or a crosslinking agent (hereinafter referred to as “second invention”).

Hereinafter, the present invention will be described in detail. An α-olefin having 6 or more carbon atoms (hereinafter, referred to as “copolymer (A)”) used in the α-olefin having 6 or more carbon atoms / cyclic non-conjugated diene random copolymer in the first invention (hereinafter, “copolymer (A)”). "Higher α-olefin"), specifically, 1-hexene, 1-octene, 1-nonene, 1
Α-olefins having 20 or less carbon atoms such as -decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene, and preferably 1
-Hexene, 1-octene, 1-decene, 1-dodecene, more preferably 1-hexene and 1-octene are used. These higher α-olefins can be used alone or in admixture of two or more. Further, as the cyclic non-conjugated diene, specifically, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 2,5-norbornadiene, 1, 4-cyclohexadiene, 1,4-cyclooctadiene, 1,5-cyclooctadiene and the like are mentioned, preferably 5-ethylidene-2-norbornene and dicyclopentadiene, more preferably 5-ethylidene-2-norbornene. Used. These cyclic non-conjugated dienes can be used alone or in admixture of two or more. The cyclic non-conjugated diene content of the copolymer (A) is 1 to 40 mol%, preferably 2-35, and more preferably 4-30. In this case, if the cyclic non-conjugated diene content is less than 1 mol%, the vulcanization rate is lowered, and the co-vulcanizability with the conjugated diene rubber is impaired. Is extremely reduced and tear resistance is impaired, which is not preferable. Further, the polystyrene-converted weight average molecular weight (hereinafter referred to as “Mw”) of the copolymer (A) measured by gel permeation chromatography (GPC) is 1
0,000,000 to 2,000,000, preferably 150,000 to 1,500,000
More preferably, it is 250,000 to 1,000,000. in this case,
When the Mw is less than 100,000, the mechanical strength and compression set of the vulcanized rubber are inferior, which is not preferable, while when it exceeds 2 million, the roll processability of the rubber composition is deteriorated, which is not preferable. In addition, Mw / Mn measured by gel permeation chromatography (GPC) of the copolymer (A) (however,
Mn is a polystyrene reduced number average molecular weight. ) Is 2
It is -5, preferably 2.2-4.5, and more preferably 2.5-4. In this case, if Mw / Mn exceeds 5, mechanical properties of the vulcanizate may deteriorate, which is not preferable. A copolymer having Mw / Mn of less than 2 is generally difficult to produce.

The copolymer (A) is converted into a higher α-olefin by using, for example, a catalyst consisting of the following components (a) and (b) or a catalyst consisting of the following components (c) and (d). It can be produced by copolymerizing with a cyclic non-conjugated diene. Component (a) is a transition metal compound represented by the following general formula [I]. R ^″ _s (C ₅ R _m ) _p (R ^′ _n E) _q MQ _4-pq ... [I] In the formula, M is a Group 4 metal of the periodic table, and (C ₅ R _m ) is It is a cyclopentadienyl group or a substituted cyclopentadienyl group, and each R may be the same or different and is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, or 7 to 7 carbon atoms. 40 alkaryl group or 7 to 40 carbon aralkyl group, or two adjacent carbon atoms are combined to form a 4- to 8-membered carbon ring, and E is an atom having a non-bonded electron pair. And R'is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkaryl group having 7 to 40 carbon atoms, or 7 to 7 carbon atoms.
40 is an aralkyl group, R ^″ is an alkylene group having 1 to 20 carbon atoms, a dialkylsilicon or dialkylgermanium, and is a group that bonds two ligands,
Is 1 or 0, when s is 1, m is 4, n is a number smaller than the valence of E by 2, and when s is 0, m is 5,
n is one less than the valence of E, and when n ≧ 2, each R ′ may be the same or different, and each R ′ may be bonded to form a ring, and Q is a hydrogen atom. A halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkaryl group having 7 to 40 carbon atoms or an aralkyl group having 7 to 40 carbon atoms, and p and q are 0 to 4
Of 0 and satisfy the relation of 0 <p + q ≦ 4.

Specific examples of the component (a) include bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) zirconium dimethyl and bis (cyclopentadienyl). ) Zirconium diphenyl, dimethylsilylbis (cyclopentadienyl) zirconium dichloride, dimethylsilylbis (cyclopentadienyl) zirconium dimethyl, methylenebis (cyclopentadienyl) zirconium dichloride, ethylenebis (cyclopentadienyl) zirconium dichloride, bis (Indenyl) zirconium dichloride, bis (indenyl) zirconium dimethyl, dimethylsilylbis (indenyl) zirconium dichloride, methylenebis (indenyl) zirco Umujikurorido, bis (4,
5,6,7-tetrahydroindenyl) zirconium dichloride, bis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl, dimethylsilylbis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride , Dimethylsilylbis (4,5
6,7-tetrahydro-1-indenyl) zirconium dimethyl, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadiene) Enyl) zirconium dimethyl, dimethylsilyl bis (3-methyl-1-cyclopentadienyl) zirconium dichloride, methylene bis (3-methyl-1-cyclopentadienyl) zirconium dichloride, bis (tertiary butylcyclopentadienyl) Zirconium dichloride, dimethylsilylbis (3-tert-butyl-1-cyclopentadienyl) zirconium dichloride, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (2,4-di Chill-1-cyclopentadienyl) zirconium dichloride, bis (1,2,4-trimethyl cyclopentadienyl) zirconium dichloride, dimethyl silyl bis (2,3,5-trimethyl -1
-Cyclopentadienyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, dimethylsilylbis (fluorenyl) zirconium dichloride,
(Fluorenyl) (cyclopentadienyl) zirconium dichloride, dimethylsilyl (fluorenyl) (cyclopentadienyl) zirconium dichloride, (tertiary butylamide) (1,2,3,4,5-pentamethylcyclopentadienyl) Zirconium dichloride, dimethylsilyl (tertiary butylamide) (2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dichloride, methylene (tertiary butylamide) (2
3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dichloride, (phenoxy) (1,
2,3,4,5-pentamethylcyclopentadienyl)
Zirconium dichloride, dimethylsilyl (o-phenoxy) (2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dichloride, methylene (o
-Phenoxy) (2,3,4,5-tetramethyl-1-
Cyclopentadienyl) zirconium dichloride, ethylene (o-phenoxy) (2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dichloride, bis (dimethylamido) zirconium dichloride,
Bis (diethylamido) zirconium dichloride, bis (ditertiary butylamido) zirconium dichloride, dimethylsilylbis (methylamido) zirconium dichloride, dimethylsilylbis (tertiary butylamido) zirconium dichloride, and the like. Examples thereof include compounds substituted with hafnium, but are not limited to these. These transition metal compounds can be used alone or in combination of two or more kinds.

The component (b) is a linear aluminoxane compound represented by the following general formula [II] or the following general formula [I]
II] is a cyclic aluminoxane compound. During R ₂ Al-O-[Al (R) -O] _n -AlR ₂ ... [II] [Al (R) -0] _{n + 2} ... [III] wherein each R be the same or different May have 1 to 1 carbon atoms
An alkyl group of 20, an aryl group of 6 to 40 carbon atoms, an alkaryl group of 7 to 40 carbon atoms or an aralkyl group of 7 to 40 carbon atoms, preferably a methyl group, an ethyl group, particularly preferably a methyl group, n is 2 to 50, preferably 4
Is an integer of -30. These aluminoxane compounds can be used alone or in combination of two or more. The ratio of the component (a) and the component (b) used is usually 1: 1 in terms of the molar ratio of the transition metal and the aluminum atom.
˜1: 100,000, preferably 1: 5 to 1: 5000
It is in the range of 0.

Next, the component (c) is a transition metal alkyl compound represented by the following general formula [IV]. During ^{_{R '' s (C 5 R}} m) p (R 'n E) q MR''' 4-pq ... [IV] expression, M is the Group 4 metal of the periodic table, (C ₅ R _m ) is a cyclopentadienyl group or a substituted cyclopentadienyl group, and each R may be the same or different and is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a carbon atom. It is an alkaryl group having 7 to 40 carbon atoms or an aralkyl group having 7 to 40 carbon atoms, or two adjacent carbon atoms are bonded to form a 4- to 8-membered carbon ring, and E is a non-bonded electron pair. R ^′ is an atom having 1 to 20 carbon atoms, R ^′ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkaryl group having 7 to 40 carbon atoms, or 7 to
40 is an aralkyl group, R ^″ is an alkylene group having 1 to 20 carbon atoms, a dialkylsilicon or dialkylgermanium, and is a group that bonds two ligands,
Is 1 or 0, when s is 1, m is 4, n is a number smaller than the valence of E by 2, and when s is 0, m is 5,
n is a number less than the valence of E by one, and when n ≧ 2, each R ^′ may be the same or different, and each R ^′ may be bonded to form a ring ^; Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, and 7 to 7 carbon atoms
40 alkaryl group or C7-40 aralkyl group, p and q are integers of 0-3, and 0
<P + q ≦ 4.

Specific examples of the component (c) include bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diethyl, bis (cyclopentadienyl) zirconium diisobutyl, bis (cyclopentadienyl). Zirconium diphenyl, bis (cyclopentadienyl) zirconium di {bis (trimethylsilyl) methyl}, dimethylsilylbis (cyclopentadienyl) zirconium dimethyl, dimethylsilylbis (cyclopentadienyl) zirconium diisobutyl, methylenebis (cyclopentadienyl) ) Zirconium dimethyl, ethylene bis (cyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dimethyl, bis (indenyl) zirconium diisobutyl, dimethyl Rubis (indenyl) zirconium dimethyl, methylenebis (indenyl) zirconium dimethyl, ethylenebis (indenyl) zirconium dimethyl, bis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl, dimethylsilylbis (4,5,6,7 -Tetrahydro-1-indenyl) zirconium dimethyl, ethylenebis (4,5,6,7-
Tetrahydro-1-indenyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dimethyl, dimethylsilylbis (3-methyl-1-cyclopentadienyl) zirconium dimethyl, bis (third
Tert-butylcyclopentadienyl) zirconium dimethyl, dimethylsilylbis (3-tert-butyl-1-cyclopentadienyl) zirconium dimethyl, bis (1,
3-dimethylcyclopentadienyl) zirconium dimethyl, bis (1,3-dimethylcyclopentadienyl)
Zirconium diisobutyl, dimethylsilylbis (2,
4-dimethyl-1-cyclopentadienyl) zirconium dimethyl, methylenebis (2,4-dimethyl-1-cyclopentadienyl) zirconium dimethyl, ethylenebis (2,4-dimethyl-1-cyclopentadienyl)
Zirconium dimethyl, bis (1,2,4-trimethylcyclopentadienyl) zirconium dimethyl, dimethylsilylbis (2,3,5-trimethyl-1-cyclopentadienyl) zirconium dimethyl, bis (fluorenyl) zirconium dimethyl, dimethyl Silylbis (fluorenyl) zirconium dimethyl, (fluorenyl)
(Cyclopentadienyl) zirconium dimethyl, dimethylsilyl (fluorenyl) (cyclopentadienyl)
Zirconium dimethyl, (tertiary butyl amide) (1,
2,3,4,5-pentamethylcyclopentadienyl)
Zirconium dimethyl, dimethylsilyl (tertiary butylamide) (2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dimethyl, methylene (tertiary butylamide) (2,3,4,5-tetra Methyl-
1-cyclopentadienyl) zirconium dimethyl,
(Phenoxy) (1,2,3,4,5-pentamethylcyclopentadienyl) zirconium dimethyl, dimethylsilyl (o-phenoxy) (2,3,4,5-tetramethyl-1-cyclopentadienyl) Zirconium dimethyl, methylene (o-phenoxy) (2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dimethyl, bis (dimethylamido) zirconium dimethyl, bis (diethylamido) zirconium dimethyl, bis (di Examples include tertiary butylamido) zirconium dimethyl, dimethylsilylbis (methylamido) zirconium dimethyl, dimethylsilylbis (tertiary butylamido) zirconium dimethyl, and compounds in which zirconium in these compounds is replaced with titanium or hafnium. This The present invention is not limited to, et al. These transition metal alkyl compounds can be used alone or in combination of two or more kinds. The transition metal alkyl compound may be used after previously synthesized, also a transition metal halide was substituted for R ^'' in the general formula [IV] a halogen atom, trimethylaluminum, triethylaluminum, diethylaluminum monochloride , Triisobutylaluminum, methyllithium, butyllithium and the like may be formed by contacting them in the reaction system.

The component (d) is an ionic compound represented by the following general formula [V]. ([L] ^{k +} ) _p ([M'A ¹ A ² ... A ⁿ ] ^- ) _q ... [V] In the formula, [L] ^{k +} is a Bronsted acid or a Lewis acid, and M'is It is a group 13 to 15 element of the periodic table, and A ¹ to
^An is a hydrogen atom, a halogen atom, and a carbon number of 1 to 2, respectively.
0 alkyl group, C1-C30 dialkylamino group, C1-C20 alkoxy group, C6-C40 aryl group, C6-C40 aryloxy group, C7-C40 alka A reel group, an aralkyl group having 7 to 40 carbon atoms, a halogen-substituted hydrocarbon group having 1 to 40 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, or an organic metalloid group; Is an integer, p is an integer of 1 or more, and q = (k × p). Specific examples of the component (d) include trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, methyl (di-n-butyl) ammonium tetraphenylborate, and dimethylaniline tetraphenylborate. Aluminum, methylpyridinium tetraphenylborate, methyl tetraphenylborate (2-cyanopyridinium), methyl tetraphenylborate (4-cyanopyridinium), trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, Tri-n-butylammonium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate Di -n- butyl) ammonium tetrakis (pentafluorophenyl) borate dimethylanilinium tetrakis (pentafluorophenyl) borate methylpyridinium tetrakis (pentafluorophenyl) borate methyl (2-cyanopyridinium)
Methyl tetrakis (pentafluorophenylphenyl) borate (4-cyanopyridinium), dimethylanilinium tetrakis [bis (3,5-di-trifluoromethyl) phenyl] borate, ferrocenium tetraphenylborate, silver tetraphenylborate, tetrakis (penta Examples thereof include, but are not limited to, ferrocenium fluorophenyl) borate and the like. These ionic compounds can be used alone or in admixture of two or more. The ratio of the components (c) and (d) used is usually 1: 0.5 to 1: 2 in terms of molar ratio.
The range is 0, preferably 1: 0.8 to 1:10. At the time of producing the copolymer (A), at least a part of the catalyst component can be supported on a suitable carrier and used.
The type of such a carrier is not particularly limited, and any of inorganic oxide carriers, other inorganic carriers, and organic carriers can be used. Also, the supporting method is not particularly limited, and a known method may be appropriately used. Copolymer (A) obtained by using the above catalyst
Has good randomness and low crystallinity.
Furthermore, the molecular weight of the copolymer (A) can be adjusted by adding hydrogen during the polymerization. The polymerization temperature for producing the copolymer (A) is usually about 20 to 2
It is in the range of 00 ° C, preferably 30 to 100 ° C. The pressure during the polymerization is in the range of more than 0 and 100 Kg / cm ² , preferably more than 0 and 50 Kg / cm ² .

Next, the composition of the second invention is prepared by blending the above-mentioned copolymer (A) with carbon black, a vulcanizing agent and / or a crosslinking agent, and optionally a process oil. It will be. In the second invention, the blending amount of carbon black is in the range of 30 to 150 parts by weight, preferably 30 to 120 parts by weight, more preferably 30 to 100 parts by weight, relative to 100 parts by weight of the copolymer (A).
It is in the range of parts by weight. As the carbon black,
Commercially available rubber carbon black can be used, for example ISAF, SAF, HAF, FEF, S.
Grades such as RF and GPF are preferred. The blending amount of the process oil is in the range of 0 to 100 parts by weight, preferably 0 to 9 parts by weight, based on 100 parts by weight of the copolymer (A).
The amount is 0 parts by weight, more preferably 0 to 80 parts by weight. As the process oil, a commercially available rubber process oil can be used, and for example, paraffin type process oil and naphthene type process oil are preferable. Further, the compounding amount of the vulcanizing agent and / or the crosslinking agent is 0.3 to 1 with respect to 100 parts by weight of the copolymer (A).
0 parts by weight, preferably 0.5 to 8 parts by weight,
More preferably, it is in the range of 0.5 to 7 parts by weight. As the vulcanizing agent or crosslinking agent, a commercially available vulcanizing agent or crosslinking agent for rubber can be used.
The vulcanizing agent is preferably sulfur such as powdered sulfur and colloidal sulfur, and the crosslinking agent is preferably organic peroxide.

In addition, an activator, a vulcanization accelerator, and a crosslinking aid can be used in the composition of the second invention. Specific examples of the activator include zinc white, active zinc white, and the like, and the compounding amount thereof is usually 30 parts by weight or less, preferably 2 to 15 parts with respect to 100 parts by weight of the copolymer (A). The range is parts by weight. Specific examples of the vulcanization accelerator include thiazole vulcanization accelerator, thiuram vulcanization accelerator, dithiocarbamic acid vulcanization accelerator, guanidine vulcanization accelerator, thiourea vulcanization accelerator and the like. , These may be used alone or in combination of two or more. The compounding amount of the vulcanization accelerator is usually 1 with respect to 100 parts by weight of the copolymer (A).
It is in the range of 0 parts by weight or less, preferably 2 to 8 parts by weight.
Specific examples of the crosslinking aid include oxime nitroso compounds such as p-benzoquinone dioxime and p, p'-dibenzoquinone dioxime; ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylpropane trimethacrylate, triallyl isocyanurate. And other polyfunctional monomers; sulfur compounds such as dipentamethylene thiuram tetrasulfide, and the like, and these may be used alone or in admixture of two or more. The amount of the crosslinking aid compounded is usually 0.5 to 5 parts by weight, preferably 1 to 3 parts by weight with respect to 100 parts by weight of the copolymer (A).
It is in the range of parts by weight. Further, the composition of the second invention comprises
In addition to carbon black, a white filler, a foaming agent, a processing aid for improving tackiness, and an antioxidant can be added. Examples of the white filler include silicates such as wet or dry silica, clay, talc and wollastonite; carbonates such as calcium carbonate, ground calcium carbonate and magnesium carbonate; zinc oxide, aluminum oxide, titanium oxide and the like. Metal oxides and the like, and fillers obtained by surface-treating these white fillers with coupling agents, fatty acids and the like are preferable, and these are used alone or in combination of two or more kinds. The blending amount of the white filler is 100% of the copolymer (A).
It is usually 100 parts by weight or less, preferably 10 to 80 parts by weight with respect to parts by weight. As the foaming agent,
Any commercially available foaming agent can be used, but in particular, p, p'-oxybis (benzenesulfonyl.
Hydrazide) is preferred, and the products thereof include Neocerbon N # 1000 (manufactured by Eiwa Chemical Co., Ltd.), Celmic S (manufactured by Sankyo Kasei Co., Ltd.), Celogen OT (manufactured by Uniroyal Chemical Co., Ltd.) and the like. When a foaming agent is used, the amount is usually 0.1 to 1 with respect to 100 parts by weight of the copolymer (A).
The amount is 0 parts by weight, preferably 2 to 7 parts by weight. Examples of the processing aid include paraffins, liquid paraffin, fatty acid esters, fatty acid amides and the like. Specific examples of such processing aids include polyethylene wax,
Polyethylene glycol, fatty acid amide, fatty acid ester, sub (factice), special compounding processing aid (trade name: Exton K-1, San-Aid HP, Yodoplast P, TE-80, Actiplast, Aflux 42,
Stractol WB-212 etc.) and the like, and these are used alone or in combination of two or more kinds. The blending amount of the processing aid is 100 parts by weight of the copolymer (A),
Usually, it is 10 parts by weight or less, preferably 5 parts by weight or less. Specific examples of the antioxidant include n-octadecyl-3- (4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate, tetrakis- {methylene-3- (3', 5). '-Di-tert-butyl-4'-hydroxyphenyl) propionate} methane and the like can be mentioned, and these can be used alone or in admixture of two or more. The blending amount of the antioxidant is usually 5 parts by weight or less, preferably 3 parts by weight or less with respect to 100 parts by weight of the copolymer (A). In addition, the composition of the second invention may be blended with other additives such as dehydrating agents such as calcium oxide, coloring agents, ultraviolet absorbers, flame retardants, mold release agents and the like which are commonly used in rubber compounding. . The method for preparing the composition of the second invention is not particularly limited, but, for example,
A closed type kneader such as a roll mill, a Banbury mixer, an intermixer, a pressure kneader, a continuous kneader, etc., containing the copolymer (A) and carbon black, a process oil, an activator, a processing aid, a release agent, etc. After kneading by using, a kneading agent, a vulcanization accelerator, a foaming agent, and a dehydrating agent are kneaded by a roll mill or a pressure kneader.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples. Parts and% in Examples and Comparative Examples are based on weight unless otherwise specified. Measurement of the properties of each copolymer and evaluation of each composition,
It carried out by the following method. The content of cyclic non-conjugated diene was measured by ¹³ C-NMR. Mw and Mw / Mn Using a 150C type high temperature GPC manufactured by Waters, measurement was performed at 135 ° C. using o-dichlorobenzene as a solvent. Tensile test Regarding vulcanized rubber obtained from each composition, JIS K630
It carried out based on 1. Hardness test According to JIS K6301, spring hardness (JIS
-A hardness) was measured. Compression set test Regarding vulcanized rubber obtained from each composition, JIS K630
In conformity with No. 1, it was carried out at a compression rate of 25% under the condition of 100 ° C. × 22 hours. Damping property (tan δ) The vulcanized rubber obtained from each composition was evaluated using a viscoelasticity spectrometer manufactured by Iwamoto Manufacturing Co., Ltd.

[0016]

【Example】

Example 1 (Production of Copolymer (A)) 2.5 liters of purified toluene and 550 ml of 1-hexene were placed in a 5 liter stainless steel autoclave which had been sufficiently replaced with nitrogen.
35 ml of 5-ethylidene-2-norbornene and 75 mmol of methylaluminoxane in terms of aluminum atoms dissolved in 60 ml of purified toluene were added, and the temperature was raised to 40 ° C. Then, purified toluene 20
15 μmol of bis (methylcyclopentadienyl) zirconium chloride dissolved in milliliter was added to initiate the polymerization reaction. During the reaction, the temperature was kept at 40 ° C. and polymerization was carried out for 60 minutes. After the reaction was completed, the obtained polymer solution was put into a large amount of methanol to precipitate a polymer, and the precipitated polymer was collected by filtration and dried under reduced pressure to obtain 83 g of a polymer. This polymer had a 1-octene content of 96.8 mol%, a 5-ethylidene-2-norbornene content of 3.2 mol%, Mw = 15,000, Mw /
It was a copolymer (A) with Mn = 2.5. This copolymer is referred to as a copolymer (A-1). (Preparation and evaluation of composition) Using the copolymer (A-1), Table-1
Compounds (i) were obtained by kneading each component excluding the vulcanizing agent component from the compounding recipe shown in (1) with a Labo Plastomill (internal volume 250 ml) at a rotor rotation speed of 60 rpm and 100 ° C. for 200 seconds. After that, a vulcanizing agent component was added, and the mixture was kneaded for 5 minutes with a 4-inch roll kept at 50 ° C. to obtain a compound (ii). Then, this compound (ii) was subjected to hot pressing at 170 ° C.,
It was heated under a pressing pressure of 150 kgf / cm ² for 15 minutes to prepare a vulcanized sheet of 120 × 120 × 2 mm and a sample for compression set test, and various evaluations were performed. Table 2 shows the evaluation results.

Example 2 (Production of Copolymer (A)) In the same manner as in Example 1 except that ethylene bis (fluorenyl) zirconium dichloride was used instead of bis (methylcyclopentadienyl) zirconium dichloride. 88 g of polymer was obtained. This polymer is a copolymer (A) having a 1-hexene content of 96.0 mol%, a 5-ethylidene-2-norbornene content of 4.0 mol%, Mw = 312,000 and Mw / Mn = 2.7. there were. This copolymer is referred to as copolymer (A-2). (Preparation and Evaluation of Composition) Compound (i) and compound (ii) were prepared and various evaluations were carried out in the same manner as in Example 1 except that the copolymer (A-2) was used. Table 2 shows the evaluation results.

Example 3 (Production of Copolymer (A)) In the same manner as in Example 2 except that the amount of 5-ethylidene-2-norbornene used was changed to 70 ml, 84.1 g of a polymer was obtained. . This polymer has a 1-hexene content of 89.2 mol%,
Ethylidene-2-norbornene content 10.8 mol%, M
Copolymer (A) with w = 356,000 and Mw / Mn = 2.8
Met. This copolymer is referred to as a copolymer (A-3). (Preparation and Evaluation of Composition) Compound (i) and compound (ii) were prepared and various evaluations were carried out in the same manner as in Example 1 except that the copolymer (A-3) was used. Table 2 shows the evaluation results.

Example 4 (Production of Copolymer (A)) In the same manner as in Example 2 except that the amount of 5-ethylidene-2-norbornene used was changed to 150 ml, 86.1 g of a polymer was obtained. .
This polymer has a 1-hexene content of 78.4 mol%, 5
-Ethylidene-2-norbornene content 21.6 mol%,
It was a copolymer (A) with Mw = 36.0 million and Mw / Mn = 2.7. This copolymer is referred to as a copolymer (A-4). (Preparation and Evaluation of Composition) Compound (i) and compound (ii) were prepared and various evaluations were carried out in the same manner as in Example 1 except that the copolymer (A-4) was used. Table 2 shows the evaluation results.

Example 5 (Production of Copolymer (A)) 87.3 g of a polymer was obtained in the same manner as in Example 2 except that the amount of 5-ethylidene-2-norbornene used was changed to 250 ml. .
This polymer has a 1-hexene content of 65.4 mol%, 5
-Ethylidene-2-norbornene content 34.6 mol%,
It was a copolymer (A) with Mw = 331,000 and Mw / Mn = 2.8. This copolymer is referred to as a copolymer (A-5). (Preparation and Evaluation of Composition) Compound (i) and compound (ii) were prepared and various evaluations were carried out in the same manner as in Example 1 except that the copolymer (A-5) was used. Table 2 shows the evaluation results.

Example 6 (Production of Copolymer (A)) 1- Instead of 1-Hexene
In the same manner as in Example 3 except that octene was used, 80.
7 g of polymer was obtained. This polymer had a 1-octene content of 88.6 mol%, a 5-ethylidene-2-norbornene content of 11.4 mol%, Mw = 392,000, and Mw / Mn.
It was a copolymer (A) of = 2.6. This copolymer is referred to as a copolymer (A-6). (Preparation and Evaluation of Composition) Compound (i) and compound (ii) were prepared and various evaluations were carried out in the same manner as in Example 1 except that the copolymer (A-6) was used. Table 2 shows the evaluation results.

Example 7 (Production of Copolymer (A)) 75.6 g of a polymer was obtained in the same manner as in Example 6 except that dicyclopentadiene was used instead of 5-ethylidene-2-norbornene. .
This polymer had a 1-octene content of 90.1 mol%, a dicyclopentadiene content of 9.9 mol%, and Mw = 41.4.
The copolymer (A) had Mw / Mn = 3.0. This copolymer is referred to as a copolymer (A-7). (Preparation and Evaluation of Composition) Compound (i) and compound (ii) were prepared and various evaluations were carried out in the same manner as in Example 1 except that the copolymer (A-7) was used. Table 2 shows the evaluation results.

Example 8 (Production of Copolymer (A)) 1- Instead of 1-Hexene
79.5 except that decene was used.
g of polymer were obtained. This polymer had a 1-decene content of 87.7 mol%, a 5-ethylidene-2-norbornene content of 12.3 mol%, Mw = 363,000 and Mw / Mn =
It was a copolymer (A) of 2.8. This copolymer is referred to as a copolymer (A-8). (Preparation and Evaluation of Composition) Compound (i) and compound (ii) were prepared and various evaluations were carried out in the same manner as in Example 1 except that the copolymer (A-8) was used. Table 2 shows the evaluation results.

Comparative Example 1 A copolymer prepared in the same manner as in Example 4 of JP-A-2-123114 (hereinafter referred to as "copolymer (B-1)") was used. In the same manner as in Example 1, the compound (i) and the compound (ii) were prepared and various evaluations were performed. Table 3 shows the evaluation results.

[0025]

[Table 1]

[0026]

[Table 2]

[0027]

[Table 3]

As is apparent from Table 2, the composition of the second invention exhibited excellent vibration damping properties and also excellent mechanical properties such as tensile strength, elongation at break, and compression set.

[0029]

EFFECT OF THE INVENTION The α-olefin / cyclic non-conjugated diene random copolymer having 6 or more carbon atoms of the present invention can provide a vulcanized rubber having excellent vibration damping properties and mechanical properties, It is extremely useful for a wide range of applications such as anti-vibration rubber, automobile parts, machine parts, civil engineering and construction materials, electric wire coating materials, electrical insulating materials, medical materials and the like.

Claims (2)

[Claims] 1. An α-olefin / cyclic non-conjugated diene random copolymer having 6 or more carbon atoms, which has the following characteristics (1) to (3). (1) Cyclic non-conjugated diene content is 1 to 40 mol%, (2)
The polystyrene reduced weight average molecular weight measured by gel permeation chromatography (GPC) is 100,000 to 2,000,000, and (3) the polystyrene reduced weight average molecular weight / number average molecular weight measured by gel permeation chromatography (GPC) is 2 ~ 5. 2. To 100 parts by weight of the α-olefin / cyclic non-conjugated diene random copolymer having 6 or more carbon atoms according to claim 1, 30 to 150 parts by weight of carbon black, 0 to 100 parts by weight of process oil, and A composition comprising 0.3 to 10 parts by weight of a vulcanizing agent and / or a crosslinking agent.