JPH05247284A - Vulcanizable rubber composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. excellent in strengths, heat resistance, weatherability, vibration-damping properties, etc., by mixing a specific higher alpha-olefin copolymer with an ethylene-alpha-olefin copolymer in a specified wt. ratio. CONSTITUTION:A higher %a-olefin copolymer is produced by copolymerizing a 6-20C higher alpha-olefin (e.g. octene-1), an alpha,omega-diene of formula I (wherein n is 1-3; and R<1> and R<2> are each H or 1-8C alkyl)(e.g. 1,4-hexadiene).and a nonconjugated diene of formula II (wherein n is 1-5; R<3> is 1-4C alkyl; and R<4> and R<5> are each l H or 1-8C alkyl provided that they are not simultaneously H)(e.g. 4-methyl-1,4-hexadiene). The title compsn., suitable as a vibration-damping rubber, is prepd. by mixing the copolymer with an ethylene/3-6C alpha-olefin copolymer in a wt. ratio of (5:95)-(95:5).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a vulcanizable rubber composition having excellent strength properties, heat resistance, weather resistance, vibration damping property, vibration damping property and dynamic fatigue resistance (flexing fatigue resistance).

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Ethylene / α-olefin copolymers typified by ethylene / propylene / diene copolymers have excellent strength properties, heat resistance, weather resistance, etc.
Widely used for automobile parts, industrial rubber parts, electrical insulation materials, civil engineering building materials, etc. However, since ethylene / α-olefin copolymers are inferior in vibration damping property, vibration damping property and dynamic fatigue resistance (flexing fatigue resistance), they are used in specific applications such as vibration damping rubber, rubber rolls, belts and tires. There was still room for improvement to be used for such purposes.

On the other hand, although natural rubber is excellent in strength characteristics and dynamic fatigue resistance (flexing fatigue resistance), it has heat resistance,
It is inferior in weather resistance, and the vibration damping property and the vibration damping property are not sufficient, and improvements have been desired in practical use. The present inventors have earnestly studied to obtain a vulcanizable rubber composition having excellent strength characteristics, heat resistance, weather resistance, vibration damping property, vibration damping property and dynamic fatigue resistance (flexing fatigue resistance), A copolymer obtained by copolymerizing a specific higher α-olefin, a specific non-conjugated diene and a specific α, ω-diene in the presence of a specific olefin polymerization catalyst, and an ethylene / α-olefin copolymer It was found that a vulcanizable rubber composition excellent in the above-mentioned properties can be obtained by using a composition consisting of the above, and has completed the present invention.

[0004]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and provides strength characteristics, heat resistance, weather resistance, vibration damping, vibration damping and dynamic fatigue resistance. An object of the present invention is to provide a vulcanizable rubber composition having excellent (flexural fatigue resistance).

[0005]

SUMMARY OF THE INVENTION A vulcanizable rubber composition according to the present invention comprises:
A higher α-olefin copolymer comprising a higher α-olefin having 6 to 20 carbon atoms, an α, ω-diene represented by the following general formula [I], and a non-conjugated diene represented by the following general formula [II]. Ethylene / α composed of (1), ethylene and α-olefin having 3 to 6 carbon atoms
-The olefin copolymer (2), and the weight ratio of the higher α-olefin copolymer (1) and the ethylene / α-olefin copolymer (2) [(1) / (2 )]
Is 5/95 to 95/5.

[0006]

[Chemical 3]

In the formula [I], n is an integer of 1 to 3 and R
¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

[0008]

[Chemical 4]

In the formula [II], n is an integer of 1 to 5,
R ³ represents an alkyl group having 1 to 4 carbon atoms, R ⁴ and R ⁵ represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁴ and R ⁵ are both hydrogen atoms. Absent.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The vulcanizable rubber composition according to the present invention will be specifically described below. The vulcanizable rubber composition according to the present invention is composed of a specific higher α-olefin copolymer (1) and a specific ethylene / α-olefin copolymer (2).

[Higher α-Olefin Copolymer (1)]
The higher α-olefin copolymer used in the present invention is
It is a copolymer of a higher α-olefin having 6 to 20 carbon atoms, an α, ω-diene represented by the general formula [I], and a non-conjugated diene represented by the general formula [II]. Higher α-Olefin The higher α-olefin used in the present invention is a linear higher α-olefin having 6 to 20 carbon atoms, specifically, hexene-1, heptene-1, octene-1, Nonene-1, decene-1, undecene-1, dodecene-
1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, nonadecene-1, eicosene-1, 9-methyl-decene-1, 1
1-methyl-dodecene-1, 12-ethyl-tetradecene-1 and the like can be mentioned.

In the present invention, the above-mentioned higher α-
The olefin may be used alone or as a mixture of two or more kinds. Of the above-mentioned higher α-olefins, hexene-1, octene-1, and decene-1 are particularly preferably used. α, ω-Diene The α, ω-diene used in the present invention is represented by the following general formula [I].

[0013]

[Chemical 5]

In the formula [I], n is an integer of 1 to 3 and R
¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. In the above general formula [I], n is an integer of 1 to 3, R ¹ and R ² are each independently a hydrogen atom or a carbon atom of 1
Represents an alkyl group of ~ 8. Specific examples of the above α, ω-dienes include 1,4-hexadiene, 1,
5-hexadiene, 1,6-heptadiene, 3-methyl-1,4-hexadiene, 3-methyl-1,5-hexadiene, 3-methyl-1,6-heptadiene, 4-methyl-1,6-heptadiene, 3,3-dimethyl-1,4
-Hexadiene, 3,4-dimethyl-1,5-hexadiene, 4,4-dimethyl-1,6-heptadiene, 4-
Ethyl-1,6-heptadiene and the like can be mentioned.

In the higher α-olefin copolymer according to the present invention, when R ¹ and R ² are hydrogen atoms, the repeating unit derived from the α, ω-diene is usually [III] and / or formula [I
V] is considered to exist.

[0016]

[Chemical 6]

[0017]

[Chemical 7]

In the higher α-olefin copolymer, the repeating units described above form a substantially linear structure in which they are randomly arranged. The structure of each of these repeating units can be confirmed by ¹³ C-NMR. Here, the substantially linear structure may form a branched chain structure,
It means that it does not contain a network crosslinked structure. The fact that the higher α-olefin-based copolymer used in the present invention forms a substantially linear structure means that this copolymer is completely dissolved in decalin at 135 ° C. It can be confirmed by not containing.

Non-Conjugated Diene The non-conjugated diene used in the present invention is represented by the following general formula [I
I].

[0020]

[Chemical 8]

In the above general formula [II], n is an integer of 1 to 5, R ³ represents an alkyl group having 1 to 4 carbon atoms, and R ⁴ and R ⁵ are hydrogen atoms or carbon atoms. 1 to
8 represents an alkyl group, and R ⁴ and R ⁵ are not both hydrogen atoms. Specific examples of the non-conjugated diene as described above include 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-
1,4-hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl- 1,5-heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl- 1,5-octadiene, 6-methyl-1,5-octadiene, 5-
Ethyl-1,5-octadiene, 6-ethyl-1,5-
Octadiene, 6-methyl-1,6-octadiene, 7
-Methyl-1,6-octadiene, 6-ethyl-1,6
-Octadiene, 4-methyl-1,4-nonadiene, 5
-Methyl-1,4-nonadiene, 4-ethyl-1,4-
Nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5- Nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-
1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-
1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-
1,4-decadiene, 5-methyl-1,5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl-
1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 7-methyl-
1,6-decadiene, 6-ethyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-
1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-
1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-
Examples include 1,8-decadiene and 9-methyl-1,8-undecadiene.

In the present invention, the above non-conjugated dienes may be used alone or as a mixture of two or more kinds. In addition to the non-conjugated dienes as described above, other copolymerizable monomers such as ethylene,
Propylene, butene-1, 4-methylpentene-1 and the like may be used as long as the object of the present invention is not impaired.

The molar ratio of the constituent unit derived from the higher α-olefin and the constituent unit derived from the α, ω-diene constituting the higher α-olefin copolymer of the present invention (higher α-olefin / α, ω -Diene) is 50 / 50-9
It is in the range of 5/5, preferably 60/40 to 90/10, and more preferably 65/35 to 90/10. High class α
The composition of the olefin-based copolymer can be measured by the ¹³ C-NMR method.

In the present invention, higher α-olefins have α, ω
-By copolymerizing a diene, the processability of a higher α-olefin copolymer can be improved. The content of the non-conjugated diene constituting the higher α-olefin copolymer of the present invention is 0.01 to 30 mol%, preferably 0.1.
To 20 mol%, particularly preferably 0.1 to 10 mol%, and the iodine value is 1 to 50, preferably 2 to 3
It is in the range of 0. This characteristic value is a reference value when the higher α-olefin copolymer of the present invention is vulcanized with sulfur or peroxide.

The intrinsic viscosity [η] of the higher α-olefin copolymer of the present invention measured in a decalin solvent at 135 ° C. is
1.0-10.0 dl / g, preferably 1.5-7 dl
/ G range. This characteristic value is a scale indicating the molecular weight of the higher α-olefin copolymer of the present invention, and by combining with other characteristic values, weather resistance, ozone resistance, heat aging resistance, low temperature characteristics, dynamic resistance It is useful in obtaining a copolymer having excellent properties such as fatigue resistance.

The vulcanizable rubber composition according to the present invention has improved vibration damping properties and also improved dynamic fatigue resistance. This is because the damping property is exhibited due to the peculiar relaxation behavior of the higher α-olefin copolymer (1), and the affinity between the higher α-olefin copolymer (1) and various fillers is high. Therefore, it is estimated that the dynamic fatigue resistance is improved. The higher α-olefin-based copolymer as described above can be produced by the following method.

The higher α-olefin copolymer used in the present invention comprises the higher α-olefin having 6 to 20 carbon atoms and the α represented by the above general formula [I] in the presence of an olefin polymerization catalyst. , Ω-diene and the above general formula [I
It is obtained by copolymerizing with a non-conjugated diene represented by [I]. The olefin polymerization catalyst used in the present invention is formed from a solid titanium catalyst component (a), an organoaluminum compound catalyst component (b), and an electron donor catalyst component (c).

FIG. 1 shows an example of a flow chart of a method for preparing an olefin polymerization catalyst component used in producing the higher α-olefin copolymer used in the present invention.
The solid titanium catalyst component (a) used in the present invention is a highly active catalyst component containing magnesium, titanium, halogen and an electron donor as essential components. Such a solid titanium catalyst component (a) is prepared by contacting the following magnesium compound, titanium compound and electron donor.

In the present invention, the titanium compound used for preparing the solid titanium catalyst component (a) is, for example, Ti (OR) _g X _4-g (R is a hydrocarbon group, X is a halogen atom, and 0≤g≤. The tetravalent titanium compound represented by 4) can be mentioned. More specifically, TiCl ₄ ,
Titanium tetrahalides such as TiBr ₄ and TiI ₄ ;
Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti
_{(O n -C 4 H 9)} Cl 3, Ti (OC 2 H 5) Br 3, Ti
_{(O-iso-C 4 H} 9) trihalide, alkoxy titanium such as _{Br 3; Ti (OCH 3)} 2 Cl 2, Ti (OC
_{2 H 5) 2 Cl 2,} Ti (O n -C 4 H 9) 2 Cl 2, Ti (O
C ₂ H ₅₎ dihalogenated dialkoxy titanium, such as _{2 Br 2; Ti (OCH 3} ) 3 Cl, Ti (OC 2 H 5) 3 Cl,
_{Ti (O n -C 4 H 9} ) 3 Cl, Ti (OC 2 H 5) 3 monohalogenated trialkoxy titanium such as Br; Ti (OC
_{H 3) 4, Ti (OC} 2 H 5) 4, Ti (O n -C 4 H 9) 4,
_{Ti (O-iso-C 4} H 9) 4, Ti (O-2- ethylhexyl) such as tetra-alkoxy titanium such as ₄ can be cited.

Of these, halogen-containing titanium compounds, particularly titanium tetrahalide, are preferred. Above all,
Titanium tetrachloride is particularly preferably used. These titanium compounds may be used alone or in combination of two or more. Furthermore, these titanium compounds are
It may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

Further, in the present invention, a trivalent titanium compound,
A tetravalent titanium compound is used, but a tetravalent titanium compound is particularly preferable. In the present invention, examples of the magnesium compound used for preparing the solid titanium catalyst component (a) include a reducing magnesium compound and a non-reducing magnesium compound.

Examples of the reducing magnesium compound include magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond. Specific examples of such a magnesium compound having a reducing property include dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl. Magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, octyl butyl magnesium,
Butyl magnesium halide and the like can be mentioned. These magnesium compounds may be used alone or may form a complex compound with an organic aluminum compound described later. Further, these magnesium compounds may be liquid or solid.

Specific examples of the magnesium compound having no reducing property include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; magnesium methoxy chloride, magnesium ethoxy chloride, and magnesium isopropoxy chloride. Alkoxy magnesium halides such as butoxy magnesium chloride and octoxy magnesium chloride; Alkoxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; Ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2-ethylhexoxy magnesium Alkoxy magnesium such as;
Examples thereof include allyloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium; and magnesium carboxylates such as magnesium laurate and magnesium stearate.

The non-reducing magnesium compound may be a compound derived from the above-mentioned reducing magnesium compound or a compound derived during preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducible magnesium compound, for example, a reducible magnesium compound may be prepared from polysiloxane compounds, halogen-containing silane compounds, halogen-containing aluminum compounds, esters, alcohols, etc. It may be brought into contact with the compound.

In the present invention, in addition to the above-mentioned reducing magnesium compound and non-reducing magnesium compound, the magnesium compound may be a complex compound, a complex compound or another compound of the above magnesium compound and another metal. It may be a mixture with a metal compound. Further, it may be a mixture of two or more of the above compounds.

In the present invention, among these, a magnesium compound having no reducing property is preferable, and a halogen-containing magnesium compound is particularly preferable, and among these, magnesium chloride, alkoxy magnesium chloride, and allyloxy magnesium chloride are preferably used. Be done. In the present invention, examples of the electron donor used for preparing the solid titanium catalyst component (a) include organic carboxylic acid esters and polyvalent carboxylic acid esters described below, and specifically, a skeleton represented by the following formula is used. The compound which has is mentioned.

[0037]

[Chemical 9]

[0038]

[Chemical 10]

[0039]

[Chemical 11]

[0040]

[Chemical 12]

In the above formula, R ¹ represents a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ and R ⁶ represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ Represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
At least one of R ³ and R ⁴ is preferably a substituted or unsubstituted hydrocarbon group. R ³ and R ⁴ may be connected to each other to form a ring structure. Examples of the substituted hydrocarbon group include substituted hydrocarbon groups containing a heteroatom such as N, O and S, and for example, -C-O-C.
-, - COOR, -COOH, -OH , -SO 3 H, -
Substituted hydrocarbon groups having a structure such as C—N—C— and —NH ₂ are mentioned.

Of these, a diester derived from a dicarboxylic acid in which at least one of R ¹ and R ² is an alkyl group having 2 or more carbon atoms is preferable. Specific examples of the polyvalent carboxylic acid ester include diethyl succinate, dibutyl succinate, diethyl methyl succinate, α-
Diisobutyl methyl glutarate, dibutyl methyl malonate, diethyl malonate, diethyl ethyl malonate, isopropyl diethyl malonate, diethyl butyl malonate,
Diethyl phenylmalonate, diethyl diethylmalonate, diethyl allyl malonate, diethyl diisobutylmalonate, diethyl dinormal butylmalonate, dimethyl maleate, monooctyl maleate, diisooctyl maleate, diisobutyl maleate, diisobutyl butyl maleate, butyl maleate Fatty acid polycarboxylic acid ester such as diethyl acidate, diisopropyl β-methylglutarate, diallyl ethylsuccinate, di-2-ethylhexyl fumarate, diethyl itaconate, diisobutyl itaconate, diisooctyl citraconic acid, dimethyl citraconic acid; 1,2-cyclohexane Aliphatic polycarboxylic acids such as diethyl carboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadicate Carboxylic acid ester; monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate,
Monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, mononormal butyl phthalate, ethyl normal butyl phthalate, di-n-propyl phthalate,
Diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, didecyl phthalate, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, Examples include aromatic polycarboxylic acid esters such as dibutyl naphthalene dicarboxylate, triethyl trimellitate and dibutyl trimellitate; esters derived from heterocyclic polycarboxylic acids such as 3,4-furandicarboxylic acid.

Other examples of the polycarboxylic acid ester include diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, n-octyl sebacate, di-2-ethylhexyl sebacate and the like. The esters derived from the long-chain dicarboxylic acids of Among these polyvalent carboxylic acid esters, compounds having a skeleton represented by the general formula described above are preferred, and more preferably phthalic acid, maleic acid,
An ester derived from a substituted malonic acid or the like and an alcohol having 2 or more carbon atoms is preferable, and a diester obtained by reacting phthalic acid with an alcohol having 2 or more carbon atoms is particularly preferable.

As the polyvalent carboxylic acid ester, it is not always necessary to use the polyvalent carboxylic acid ester as described above as a starting material, and the polyvalent carboxylic acid ester may be used in the process of preparing the solid titanium catalyst component (a). A compound capable of inducing an ester may be used to form a polyvalent carboxylic acid ester in the step of preparing the solid titanium catalyst component (a).

In the present invention, electron donors other than polyvalent carboxylic acids that can be used when preparing the solid titanium catalyst component (a) include alcohols, amines, amides, as described below. Ethers, ketones, nitriles, phosphines, stipines, arsines, phosphoramides, esters, thioethers,
Thioesters, acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy (aryloxy) silanes and other organosilicon compounds, organic acids, and amides of metals belonging to Groups I to IV of the periodic table And salts.

In the present invention, the solid titanium catalyst component (a) can be produced by bringing the above-mentioned magnesium compound (or metallic magnesium), electron donor and titanium compound into contact with each other. In order to produce the solid titanium catalyst component (a), a known method of preparing a highly active titanium catalyst component from a magnesium compound, a titanium compound and an electron donor can be adopted. The above components may be contacted in the presence of other reaction agents such as silicon, phosphorus and aluminum.

The production method of these solid titanium catalyst components (a) will be briefly described below with some examples. (1) A method of reacting a magnesium compound or a complex compound composed of a magnesium compound and an electron donor with a titanium compound in a liquid phase. This reaction may be carried out in the presence of a grinding aid or the like. Further, when the reaction is performed as described above, the solid compound may be pulverized. Furthermore, when the reaction is carried out as described above, each component may be pretreated with an electron donor and / or a reaction aid such as an organoaluminum compound or a halogen-containing silicon compound. In this method, the electron donor is used at least once. (2) A liquid magnesium compound having no reducing property,
A method of reacting a liquid titanium compound in the presence of an electron donor to deposit a solid titanium composite agent. (3) A method of further reacting a titanium compound with the reaction product obtained in (2). (4) In the reaction product obtained in (1) or (2),
A method of further reacting an electron donor and a titanium compound. (5) A solid compound obtained by pulverizing a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor in the presence of a titanium compound is treated with any of halogen, a halogen compound and an aromatic hydrocarbon. Method. In this method, the magnesium compound or the complex compound consisting of the magnesium compound and the electron donor may be crushed in the presence of a crushing aid or the like. Alternatively, the magnesium compound or the complex compound consisting of the magnesium compound and the electron donor may be pulverized in the presence of the titanium compound, pretreated with a reaction aid, and then treated with halogen or the like. Examples of the reaction aid include organic aluminum compounds and halogen-containing silicon compounds. In this method, the electron donor is used at least once. (6) A method of treating the compound obtained in (1) to (4) with halogen, a halogen compound, or an aromatic hydrocarbon. (7) A method of bringing a reaction product of a metal acid compound, dihydrocarbyl magnesium and a halogen-containing alcohol into contact with an electron donor and a titanium compound. (8) A method in which a magnesium compound such as a magnesium salt of an organic acid, alkoxy magnesium, or aryloxy magnesium is reacted with an electron donor, a titanium compound, and / or a halogen-containing hydrocarbon.

Among the methods for preparing the solid titanium catalyst component (a) described in (1) to (8) above, a method using a liquid titanium halide during the catalyst preparation, a method using a titanium compound, or titanium is used. When using the compound, a method using a halogenated hydrocarbon is preferable. The amount of each of the above-mentioned components used when preparing the solid titanium catalyst component (a) differs depending on the preparation method and cannot be specified unconditionally, but for example, per mol of the magnesium compound,
The electron donor is about 0.01 to 5 mol, preferably 0.05.
In an amount of ˜2 mol, the titanium compound is used in an amount of about 0.01 to 500 mol, preferably 0.05 to 300 mol.

The solid titanium catalyst component (a) thus obtained contains magnesium, titanium, halogen and an electron donor as essential components. In this solid titanium catalyst component (a), the halogen / titanium (atomic ratio) is about 4 to 200, preferably about 5 to 100,
The electron donor / titanium (molar ratio) is about 0.1-10,
Desirably, it is about 0.2 to about 6, and the magnesium / titanium (atomic ratio) is desirably about 1 to 100, preferably about 2 to 50.

The solid titanium catalyst component (a) contains a magnesium halide having a smaller crystal size than that of a commercially available magnesium halide, and usually has a specific surface area of about 50 m ² / g or more, preferably about 60-1, 000m
² / g, more preferably about 100 to 800 m ² / g. Since the solid titanium catalyst component (a) forms the catalyst component by integrating the above components, the composition thereof is not substantially changed by washing with hexane.

Such solid titanium catalyst component (a) is
It can be used alone, or can be diluted with an inorganic compound or an organic compound such as a silicon compound, an aluminum compound or a polyolefin. When a diluent is used, it exhibits high catalytic activity even if it has a specific surface area smaller than that described above. Regarding the method for preparing such a highly active titanium catalyst component, for example,
JP-A-50-108385, JP-A-50-126590, JP-A-51-2
0297 publication, 51-28189 publication, 51-64586 publication,
51-92885, 51-136625, 52-87489, 52-100596, 52-147688, 52-
No. 104593, No. 53-2580, No. 53-40093,
53-40094, 53-43094, 55-135102, 55-135103, 55-152710, 56.
-811, 56-11908, 56-18606, and
58-83006, 58-138705, 58-138706, 58-138707, 58-138708, 58
-138709 publication, 58-138710 publication, 58-138715 publication, 60-23404 publication, 61-21109 publication, 61-378 publication.
No. 02, No. 61-37803, etc.

As the organoaluminum compound catalyst component (b) used in the present invention, a compound having at least one Al-carbon bond in the molecule can be used. Examples of such compounds include (i) the general formula (R ¹ ) _m Al (O (R ² )) _n H _p X _q (wherein, R ¹ and R ² usually have 1 to 15 carbon atoms). ,
It is preferably a hydrocarbon group containing 1 to 4 groups, which may be the same or different from each other. X represents a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <
3 and q are numbers satisfying 0 ≦ q <3, and m +
an organic aluminum compound represented by the formula (n + p + q = 3), (ii) a general formula (M ¹ ) Al (R ¹ ) ₄ (in the formula, M ¹ is Li, Na, K, and R ¹ is the above (i). And a complex alkylated product of a Group I metal represented by R ¹ ) and aluminum.

Examples of the organoaluminum compound belonging to the above (i) include the following compounds. Formula _{^{(R 1) n Al (O}} (R2)) in _3-m (wherein, R ¹ R ¹ and R ² in the (i), R
Same as ² . m is a number preferably satisfying 1.5 ≦ m ≦ 3), the general formula ^{_{(R 1) m AlX 3-}} m ( wherein, R ¹ is the (i) the same .X is halogen and R ¹ in, m is a number preferably satisfying 0 <m <3), the general formula ^{_{(R 1) m AlH 3-}} m ( wherein, R ¹ is (i) above same .m preferably 2 ≦ a R ¹ in m <is a number satisfying 3), the general formula _{^{(R 1) m Al (oR}} 2) n X q ( wherein, R ¹ and R ² are the (i) R ¹ in, R
Same as ² . X is halogen, m is 0 <m ≦ 3, n is 0 ≦ n
<3, q is a number satisfying 0 ≦ q <3, and m + n + q
= 3) and the like.

Specific examples of the aluminum compound belonging to (i) above include trialkyl aluminum such as triethyl aluminum and tributyl aluminum; trialkenyl aluminum such as triisoprenyl aluminum; diethyl aluminum ethoxide and dibutyl aluminum butoxide. Dialkyl aluminum alkoxide; alkyl aluminum sesquialkoxide such as ethyl aluminum sesquiethoxide, butyl aluminum sesquibutoxide; (R ¹ ) _2.5 A
a partially alkoxylated alkylaluminum having an average composition such as 1 (O (R ² )) _0.5 ;
Dialkyl aluminum halides such as diethyl aluminum chloride, dibutyl aluminum chloride and diethyl aluminum bromide; alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide Partially halogenated alkyl aluminum such as alkyl aluminum dihalide; Dialkyl aluminum hydride such as diethyl aluminum hydride, dibutyl aluminum hydride; Alkyl aluminum dihydride such as ethyl aluminum dihydride, propyl aluminum dihydride Partially hydrogenated Kill aluminum; ethylaluminum ethoxy chloride, butyl aluminum butoxide cycloalkyl chloride, can be mentioned partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxy bromide.

As a compound similar to the aluminum compound belonging to the above (i), an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom can be mentioned. Such compounds include, for example, (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ ,
_{(C 4 H 9) 2 AlOAl} (C 4 H 9) 2, (C 2 H 5) 2 Al
Examples thereof include N (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ and methylaminooxane.

The compounds belonging to (ii) above include L
Examples thereof include iAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ . Among these, it is particularly preferable to use trialkylaluminum or alkylaluminum to which two or more kinds of aluminum compounds described above are bound. As the electron donor catalyst component (c), oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides and alkoxysilanes. Nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates, or polyvalent carboxylic acid esters as described above can be used.

More specifically, carbon such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol. Alcohols having 1 to 18 atoms; phenol, cresol, xylenol, ethylphenol, propylphenol,
6 to 20 carbon atoms which may have a lower alkyl group, such as nonylphenol, cumylphenol and naphthol
Phenols; acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone, and other ketones having 3 to 15 carbon atoms;
Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, propionic acid. Ethyl, 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, n-butyl maleate, methyl malo Diisobutyl, cyclohexene carboxylic di -n- hexyl, nadic diethyl, tetrahydrophthalic acid diisopropyl, diethyl phthalate, diethyl phthalate, diisobutyl phthalate, di -
Organic acid esters having 2 to 30 carbon atoms such as n-butyl, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate; acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid 2 to 1 carbon atoms such as chloride
Acid halides of 5; methyl ether, ethyl ether,
Ethers having 2 to 20 carbon atoms such as isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether; acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; methylamine, ethylamine, diethylamine, tributylamine , Amines such as piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylenediamine; nitriles such as acetonitrile, benzonitrile, tolunitrile; acid anhydrides such as acetic anhydride, phthalic anhydride, benzoic anhydride, etc. Be done.

Further, as the electron donor (c), an organosilicon compound represented by the following general formula [II] can be used. R _n Si (OR ′) _4-n ... [1] (In the formula, R and R ′ are hydrocarbon groups, and n is 0 <n.
It is a number that satisfies <4. ) Specific examples of the organosilicon compound represented by the above general formula [1] include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane,
Diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-ο-tolyldimethoxysilane,
Bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane , Ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n
-Propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltoluethoxysilane, ethyltriethoxysilane,
Vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-
Aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyl Dimethoxysilane,
Ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxy silane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane and the like are used.

Of these, ethyltriethoxysilane, n-
Propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis
Preference is given to -p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane and diphenyldiethoxysilane.

Further, as the electron donor catalyst component (c), an organosilicon compound represented by the following general formula [2] can be used. SiR ¹ R ² _m (OR ³ ) _3-m ... [2] (In the formula, R ¹ is a cyclopentyl group or a cyclopentyl group having an alkyl group, and R ² has an alkyl group, a cyclopentyl group and an alkyl group. A group selected from the group consisting of a cyclopentyl group, R ³ is a hydrocarbon group, and m is a number satisfying 0 ≦ m ≦ 2.) In the above formula [2], R ¹ is a cyclopentyl group or an alkyl group. And R ¹ is a cyclopentyl group having an alkyl group such as a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 2-ethylcyclopentyl group, a 2,3-dimethylcyclopentyl group, and the like. Can be mentioned.

In the above formula [2], R ² is any one of an alkyl group, a cyclopentyl group or a cyclopentyl group having an alkyl group, and R ² is, for example, a methyl group, an ethyl group, a propyl group, An allyl group such as an isopropyl group, a butyl group and a hexyl group, or a cyclopentyl group exemplified as R ¹ and a cyclopentyl group having an alkyl group can be mentioned in the same manner.

In the above formula [2], R ³ is a hydrocarbon group, and examples of R ³ include hydrocarbon groups such as an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group. Of these, R ¹
Is a cyclopentyl group, R ² is an alkyl group or a cyclopentyl group, and R ³ is preferably an alkyl group, particularly a methyl group or an ethyl group.

Specific examples of such organosilicon compounds include trialkoxysilanes such as cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane and cyclopentyltriethoxysilane; Dialkoxysilanes such as dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, dicyclopentyldiethoxysilane; tricyclopentylmethoxysilane, tricyclopentylethoxysilane, di Cyclopentylmethylmethoxysilane,
Examples include monoalocoxysilanes such as dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane. Among these electron donors, organic carboxylic acid esters or organic silicon compounds are preferable, and organic silicon compounds are particularly preferable.

The olefin polymerization catalyst used in the present invention is formed from the solid titanium catalyst component (a) as described above, the organoaluminum compound catalyst component (b), and the electron donor catalyst component (c). In the present invention, the catalyst for olefin polymerization is used to produce higher α-olefins, α,
The ω-diene and the non-conjugated diene are polymerized. The olefin polymerization catalyst is used to prepolymerize α-olefins or higher α-olefins, and then the catalyst is used to The ω-diene and the non-conjugated diene can also be polymerized (main polymerization). During pre-polymerization, 0.1 to 500 per 1 g of olefin polymerization catalyst
g, preferably 0.3 to 300 g, particularly preferably 1 to
Prepolymerize α-olefins or higher α-olefins in an amount of 100 g.

In the prepolymerization, a catalyst having a much higher concentration than the catalyst concentration in the system in the main polymerization can be used.
The concentration of the solid titanium catalyst component (a) in the prepolymerization is
The amount is usually about 0.01 to 200 mmol, preferably about 0.1 to 100 mmol, and particularly preferably 1 to 50, in terms of titanium atom, per liter of an inert hydrocarbon medium described later.
It is desirable to set it in the millimolar range.

The amount of the organoaluminum catalyst component (b) is
0.1 to 500 g per 1 g of the solid titanium catalyst component (a),
The amount is preferably such that 0.3 to 300 g of a polymer is produced, and is usually about 0.1 to 100 mol, preferably about 0.1 per mol of titanium atom in the solid titanium catalyst component (a). An amount of 5 to 50 mol, particularly preferably 1 to 20 mol is desirable.

The electron donor catalyst component (c) is 0.1 to 5 per mol of titanium atom in the solid titanium catalyst component (a).
It is preferably used in an amount of 0 mol, preferably 0.5 to 30 mol, particularly preferably 1 to 10 mol. Prepolymerization is carried out by using an olefin or higher α
-It is preferable to add the olefin and the above-mentioned catalyst components and to carry out under mild conditions.

Examples of the inert hydrogen medium used in this case include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclo Examples thereof include alicyclic hydrocarbons such as pentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; and mixtures thereof. Of these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. In addition, olefin or higher α
-Olefin itself can be prepolymerized in a solvent, or can be prepolymerized in a substantially solvent-free state.

The higher α-olefin used in the prepolymerization may be the same as or different from the higher α-olefin used in the main polymerization described later. The reaction temperature in the prepolymerization is usually about −20 to + 100 ° C., preferably about −2.
It is desirable that the temperature is in the range of 0 to + 80 ° C, more preferably 0 to + 40 ° C. In the prepolymerization, a molecular weight modifier such as hydrogen can be used. Such a molecular weight modifier has an intrinsic viscosity [η] of a polymer obtained by prepolymerization measured in a decalin solvent at 135 ° C.
Is about 0.2 dl / g or more, preferably about 0.5 to 10
It is desirable to use it in such an amount that it becomes dl / g.

The prepolymerization is carried out so that about 0.1 to 500 g, preferably about 0.3 to 300 g, particularly preferably 1 to 100 g of a polymer is produced per 1 g of the solid titanium catalyst component (a), as described above. It is desirable to do this. If the prepolymerization amount is too large, the production efficiency of the olefin polymer may decrease. The prepolymerization can be carried out batchwise or continuously.

Solid titanium catalyst component (a) or a solid titanium catalyst component (a) obtained by prepolymerizing the olefin polymerization catalyst as described above, an organoaluminum catalyst component (b), and an electron donor. In the presence of the olefin polymerization catalyst formed from the catalyst component (c), the higher α-
Copolymerization (main polymerization) of olefins, α, ω-dienes and non-conjugated dienes.

In the copolymerization (main polymerization) of the higher α-olefin, the α, ω-diene and the non-conjugated diene, in addition to the above-mentioned olefin polymerization catalyst, olefin polymerization is performed as an organoaluminum compound catalyst component. The same component as the organoaluminum compound catalyst component (b) used in the production of the catalyst for use can be used. In the copolymerization (main polymerization) of higher α-olefins, α, ω-dienes and non-conjugated dienes, the electron donor catalyst component used in the production of the olefin polymerization catalyst was used. Components similar to the donor catalyst component (c) can be used. In addition, the organoaluminum compound and the electron donor used in the copolymer (main polymerization) of the higher α-olefin, the α, ω-diene, and the non-conjugated diene do not necessarily prepare the above olefin polymerization catalyst. It need not be the same as the organoaluminum compound and electron donor used in the process.

The copolymerization (main polymerization) of the higher α-olefin, the α, ω-diene and the non-conjugated diene is usually carried out in the liquid phase. As the reaction medium for the main polymerization, the above-mentioned inert hydrocarbon medium may be used, or an olefin which is liquid at the reaction temperature may be used. In the copolymerization (main polymerization) of a higher α-olefin, an α, ω-diene, and a non-conjugated diene, the solid titanium catalyst component (a) is usually about 10 0.001 to about 1.0 mmol, preferably about 0.00
Used in an amount of 5-0.5 mmol. The organoaluminum catalyst component (b) is a solid titanium catalyst component (a).
The metal atom in the organoaluminum compound catalyst component (b) is usually about 1 to 2,000 relative to 1 mol of the titanium atom therein.
It is used in an amount such that it is a mole, preferably about 5-500 moles. Further, the electron donor catalyst component (c) is usually about 0.001 to 10 mol, preferably 0.1 to 0.1 mol per mol of the metal atom in the organoaluminum compound catalyst component (b).
It is used in an amount of 01 to 2 mol, particularly preferably 0.05 to 1 mol.

If hydrogen is used during the main polymerization, the molecular weight of the resulting polymer can be adjusted. In the present invention, the polymerization temperature of the higher α-olefin, the α, ω-diene and the non-conjugated diene is usually about 20 to 200 ° C, preferably about 40 to 100 ° C, and the pressure is usually atmospheric pressure to 100
kg / cm ^{2 It is} preferably set to normal pressure to 50 kg / cm ² . In the copolymerization (main polymerization) of higher α-olefin, α, ω-diene, and non-conjugated diene, polymerization is
It can be carried out by any of a batch system, a semi-continuous system and a continuous system. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

[Ethylene / α-olefin Copolymer (2)] The ethylene / α-olefin copolymer (2) used in the present invention is basically composed of ethylene and α-olefin. You may contain a polyene component as a structural component. The α-olefin has 3 to 6 carbon atoms, and specific examples thereof include α-olefins such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene and 1-hexene. Among them, propylene and 1-butene are preferably used.

The ethylene / α-olefin copolymer (2) used in the present invention has a molar ratio of ethylene and α-olefin (ethylene / α-olefin) of 50 /
It is 50 to 95/5, preferably 55/45 to 93/7, and more preferably 60/40 to 91/9. As the polyene component, a non-conjugated polyene is used, and specifically, 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, diene Examples thereof include cyclopentadiene, and among them, 5-ethylidene-2-norbornene and dicyclopentadiene are preferably used.

The content of these non-conjugated polyene components is
The iodine value is 1 to 50, preferably 4 to 40, more preferably 6 to 30, and the mol% is 0.1 to 0.1.
It is 10 mol%, preferably 0.5 to 7 mol%, more preferably 1 to 5 mol%. The intrinsic viscosity [η] of the ethylene / α-olefin copolymer (2) of the present invention measured in a 135 ° C decalin solvent is 0.8 to 5 dl / g, preferably 0.9 to 4 dl / g, and more preferably Is 1.0 to 3
dl / g. When the intrinsic viscosity [η] exceeds 5 dl / g, the obtained rubber composition tends to be difficult to process. On the other hand, when the intrinsic viscosity [η] is less than 0.8 dl / g, the strength and physical properties of the obtained rubber composition tend to deteriorate.

In the vulcanizable rubber composition according to the present invention,
Although the strength is high, it is presumed that the reason is that the ethylene / α-olefin copolymer (2) has a long molecular chain length. The compounding ratio of the higher α-olefin copolymer (1) and the ethylene / α-olefin copolymer (2) constituting the vulcanizable rubber composition according to the present invention is such that the weight ratio [(1) / (2)] is 5/95 to 95/5, preferably 10/90 to 90/10, more preferably 20/80.
~ 80/20.

The rubber composition according to the present invention contains SRF, G
PF, FEF, HAF, ISAF, SAF, FT, MT
Carbon black such as, rubber reinforcing agents such as finely divided silicic acid, and light calcium carbonate, heavy calcium carbonate,
Fillers such as talc, clay and silica may be added. The types and blending amounts of these rubber reinforcing agents and fillers can be appropriately selected depending on the application, but the blending amounts are usually higher α-olefin copolymer (1) and ethylene.
The maximum amount is 300 parts by weight, preferably the maximum amount is 200 parts by weight, relative to the total amount of 100 parts by weight with the α-olefin copolymer (2).

The rubber composition according to the present invention can be used as it is in an unvulcanized state, but when it is used as a vulcanized product, its properties can be most exerted. That is, the higher α-olefin copolymer (1) constituting the rubber composition according to the present invention has a function of improving properties such as vibration damping and dynamic fatigue resistance of the vulcanized product, and ethylene -The α-olefin copolymer (2) has a function of improving properties such as strength of the vulcanized product, and therefore, the rubber composition according to the present invention has excellent strength properties, vibration damping properties and dynamic fatigue resistance. A vulcanized product can be obtained.

When a vulcanized product is obtained from the rubber composition according to the present invention, a high-grade α-is used depending on the intended use and performance of the vulcanized product.
In addition to the olefin-based copolymer (1) and the ethylene / α-olefin copolymer (2), the types and blending amounts of rubber reinforcing agents, fillers, softening agents, vulcanizing agents, vulcanization accelerators, The type and compounding amount of a compound constituting a vulcanization system such as a sulfurization aid, the type and compounding amount of an antioxidant and a processing aid, and the step of producing a vulcanized product can be appropriately selected.

The total amount of the higher α-olefin copolymer (1) and the ethylene / α-olefin copolymer (2) in the vulcanizate is appropriately determined depending on the intended performance and use of the vulcanizate. Although it can be selected, it is usually 20% by weight or more, preferably 25% by weight or more. As the softening agent, a softening agent usually used for rubber can be used. Specifically, petroleum-based softening agents such as process oils, lubricating oils, paraffins, liquid paraffin, petroleum asphalt, and petrolatum; co-roller-based softening agents such as coulters and coulter pitches; castor. Fat oil softeners such as oils, linseed oil, rapeseed oil and coconut oil; tol oil; sub; waxes such as beeswax, carnauba wax and lanolin; ricinoleic acid, palmitic acid, barium stearate, calcium stearate , Fatty acids and fatty acid salts such as zinc laurate;
Examples include synthetic polymer substances such as petroleum resin, atactic polypropylene, and coumarone indene resin.
Of these, petroleum-based softeners are preferably used, and process oils are particularly preferably used. The blending amount of these softening agents can be appropriately selected depending on the use of the vulcanized product, but the blending amount is usually higher α-olefin copolymer (1) and ethylene / α-olefin copolymer (2). With respect to the total amount of 100 parts by weight, a maximum of 150 parts by weight, preferably a maximum of 100 parts by weight
Parts by weight.

In order to produce a vulcanized product from the rubber composition according to the present invention, an unvulcanized compounded rubber is prepared once and then this compounded rubber is prepared in the same manner as in the case of vulcanizing a general rubber. Vulcanization may be performed after molding into the intended shape. As a vulcanization method, either a method of heating using a vulcanizing agent or a method of irradiating with an electron beam may be adopted.

Examples of the vulcanizing agent used during vulcanization include sulfur compounds and organic peroxides. In particular, when a sulfur compound is used, the performance of the rubber composition according to the present invention can be best exhibited. Specific examples of sulfur compounds include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dimethyldithiocarbamate. Of these, sulfur is preferably used. The sulfur compound is 100 in total of the higher α-olefin copolymer (1) and the ethylene / α-olefin copolymer (2) of the present invention.
0.1 to 10 parts by weight, preferably 0.5
Used in amounts of up to 5 parts by weight.

When a sulfur compound is used as a vulcanizing agent, it is preferable to use a vulcanization accelerator together. Specific examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazolsulfenamide, N-oxydiethylene-2-benzothiazolsulfenamide, N, N-diisopropyl-2-benzothiazolsulfenamide. ,
2-mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,2
6-diethyl-4-morpholinothio) benzothiazole,
Thiazol compounds such as dibenzothiazyl disulfide; diphenylguanidine, triphenylguanidine,
Guanidine compounds such as diorsonitrile guanidine, orthonitrile biguanide, diphenylguanidine phthalate; acetaldehyde-aniline reaction products, butyraldehyde-aniline condensates, hexamethylenetetramine, aldehyde amines such as acetaldehyde ammonia, or aldehyde-ammonia systems. Compounds; 2-Mercaptoimidazoline and other imidazoline compounds; Thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, diorsotolylthiourea and other thiourea compounds; tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram Thiuram-based compounds such as disulfide, tetrabutylthiuram disulfide, pentamethylene thiuram tetrasulfide; Dithioates such as zinc methyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, and tellurium dimethyldithiocarbamate. Examples thereof include zanthate compounds such as zinc dibutylxanthate; compounds such as zinc white. These vulcanization accelerators are 0.1 to 20 parts by weight, preferably 0 to 100 parts by weight of the total amount of the higher α-olefin copolymer (1) and the ethylene / α-olefin copolymer (2). .2 to 10 parts by weight.

The organic peroxide may be any of those usually used for peroxide vulcanization of rubber. For example, 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,
α'-bis (t-butylperoxy-m-isopropyl)
Examples include benzene. Among them, dicumyl peroxide, di-t-butylperoxide and di-t-butylperoxy-3,3,5-trimethylcyclohexane are preferably used. These organic peroxides are used alone or in combination of two or more, and the total amount of the higher α-olefin copolymer (1) of the present invention (1) and the ethylene / α-olefin copolymer (2) is 100 g. 0.0003-0.0
It is used in an amount of 5 mol, preferably 0.001 to 0.03 mol, but it is desirable to appropriately determine the optimum amount according to the required physical properties.

When an organic peroxide is used as a vulcanizing agent, it is preferable to use a vulcanizing auxiliary together. Specific examples of the vulcanization aid include sulfur; quinone dioxime compounds such as p-quinone dioxime; methacrylate compounds such as polyethylene glycol dimethacrylate; diallyl phthalate and triallyl cyanurate. And other allyl compounds; other maleimide compounds; divinylbenzene and the like. Such a vulcanization aid is used in an amount of 0.5 to 2 mol, preferably about equimolar, relative to 1 mol of the organic peroxide used.

When an electron beam is used as a vulcanizing method without using a vulcanizing agent, 0.1 to 10 MeV (megaelectron volt), preferably 0.3, is added to a molded unvulcanized compounded rubber described later. An electron with an energy of ˜2 MeV and an absorbed dose of 0.5 to 35 Mrad,
Irradiation may be performed preferably at 0.5 to 10 Mrad.

The unvulcanized compounded rubber is prepared, for example, by the following method. That is, a higher α-olefin copolymer (1), an ethylene / α-olefin copolymer (2), a filler, and a softening agent are mixed with a mixer such as a Banbury mixer at a temperature of 80 to 170 ° C. After kneading for 10 minutes, a vulcanizing agent and optionally a vulcanization accelerator or vulcanization aid are additionally mixed using a roll such as an open roll, and the roll temperature is set. After kneading at 40 to 80 ° C. for 5 to 30 minutes, the mixture is dispensed to prepare a ribbon-shaped or sheet-shaped compounded rubber.

The unvulcanized compounded rubber thus prepared is molded into an intended shape by an extruder, a calendar roll, or a press, and the molded product is placed at the same time as molding or in a vulcanization tank. Introduced, at a temperature of 150-270 ° C.
A vulcanized product is obtained by heating for 30 minutes or by irradiating with an electron beam by the above-mentioned method. A mold may be used for this vulcanization step, or vulcanization may be carried out without using a mold. When a mold is not used, the molding and vulcanization steps are usually carried out continuously. As a heating method in the vulcanization tank, a heating tank such as hot air, a fluidized bed of glass beads, UHF (ultra high frequency electromagnetic wave) or a steam can be used. Of course, when vulcanization is performed by electron beam irradiation, compounded rubber containing no vulcanizing agent is used.

The rubber vulcanizates produced as described above are anti-vibration rubbers, automobile parts such as cover materials for tire vibrating parts, industrial rubber products such as rubber rolls and belts, electrical insulating materials, and civil engineering materials. It can be used for applications such as building materials and rubberized cloth. In particular, it can be suitably used for applications where vibration damping and dynamic fatigue resistance are required, such as anti-vibration rubber, rubber rolls, belts, tires, wiper blades and the like.

Furthermore, in the case of producing a foam from the rubber composition according to the present invention, a foaming agent usually used for rubber and a foaming auxiliary agent can be blended if necessary, and the obtained foaming material can be added. Can be used for heat insulating materials, cushioning materials, sealing materials and the like. These foaming agents are composed of the higher α-olefin copolymer (1) of the present invention and ethylene.
Used in an amount of 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the total amount of the α-olefin copolymer (2), and having an apparent specific gravity of 0.03 to 0.7. The body can be manufactured.

[0093]

The vulcanizable rubber composition according to the present invention is
Since it contains the specific higher α-olefin copolymer (1) and the ethylene / α-olefin copolymer (2) in a specific ratio, it has strength properties, heat resistance, weather resistance, vibration damping, and anti-vibration properties. It is possible to provide a vulcanized product that has the effect of being excellent in vibration resistance and dynamic fatigue resistance and that has such an effect.

Since the vulcanized product obtained from the vulcanizable rubber composition according to the present invention has the above-mentioned effects, it is used as an anti-vibration rubber, an automobile part such as a cover material for a tire vibrating part, and a rubber roll. Widely used for industrial rubber products such as belts, electrical insulating materials, civil engineering materials, rubberized cloth, etc. Above all, applications in which vibration damping and dynamic fatigue resistance are required, such as anti-vibration rubber, rubber rolls, belts, tires, wipers.
It can be suitably used for blades and the like.

The foam produced from the rubber composition according to the present invention can be used for heat insulating materials, cushioning materials, sealing materials and the like. Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

[0096]

Example 1 [Preparation of solid titanium catalyst component (a)] 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol were heated and reacted at 130 ° C. for 2 hours to form a uniform solution. Thereafter, 21.3 g of phthalic anhydride was added to this solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride in this homogeneous solution. After cooling the homogeneous solution thus obtained to room temperature, 75 ml of titanium tetrachloride 2 kept at -20 ° C
The entire amount was added dropwise to 00 ml over 1 hour. After the completion of charging, the temperature of this mixed solution was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., diisobutylphthalate was added.
(5.22 g) was added and the mixture was kept at the same temperature for 2 hours with stirring. After the completion of the reaction for 2 hours, the solid portion was collected by hot filtration, and the solid portion was resuspended in 275 ml of titanium tetrachloride, and then heated and reacted again at 110 ° C for 2 hours. After completion of the reaction, hot filtration is performed again to collect a solid portion, and 1
It was sufficiently washed with 10 ° C. decane and hexane until no free titanium compound was detected in the washing liquid. The titanium catalyst component (a) prepared by the above operation was stored as a decane slurry, and a part of this was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component (a) thus obtained was 2.5% by weight of titanium and 6% of chlorine.
5% by weight, 19% by weight of magnesium and 13.5% by weight of diisobutyl phthalate. [Polymerization] A 4-liter glass polymerization vessel equipped with a stirring blade was used to continuously carry out the copolymerization reaction of octene-1, 1,5-hexadiene, and 7-methyl-1,6-octadiene. It was

That is, from the top of the polymerization vessel, octene-1,
A hexane solution of 1,5-hexadiene and 7-methyl-1,6-octadiene was added in the polymerization vessel at an octene-1 concentration of 200 g / liter and a 1,5-hexadiene concentration of 3
9 g / liter, 2.1 liter / hour, so that the concentration of 7-methyl-1,6-octadiene was 10 g / liter, hexane slurry solution of solid titanium catalyst component (a) was used as a catalyst in the polymerization vessel 0.4 liter / hour so that the concentration becomes 0.045 mmol / liter, and 1 liter / hour of trimethylmethoxysilane is added to the hexane solution of triisobutylaluminum so that the aluminum concentration in the polymerization vessel becomes 8 mmol / liter. Hexane solution of silane concentration of 2.6 mmol /
It was continuously fed into each of the polymerization vessels at a rate of 0.5 liter per hour so as to be 1 liter. On the other hand, the polymerization solution in the polymerization vessel was continuously withdrawn from the lower portion of the polymerization vessel so as to always have a volume of 2 liters. Further, from the upper part of the polymerization vessel, hydrogen was supplied at 1 liter / hour and nitrogen was supplied at 50 liter / hour. The copolymerization reaction was carried out at 50 ° C. by circulating warm water in a jacket attached outside the polymerization vessel.

Next, a small amount of methanol was added to the polymerization solution extracted from the lower part of the polymerization vessel to stop the copolymerization reaction, and this polymerization solution was poured into a large amount of methanol to precipitate the copolymer. . After the copolymer was thoroughly washed with methanol, it was dried under reduced pressure at 140 ° C for a whole day and night.
A 1,5-hexadiene / 7-methyl-1,6-octadiene copolymer was obtained at a rate of 90 g / h.

Octene-1 constituting the obtained copolymer
And 1,5-hexadiene molar ratio (octene-1 /
The 1,5-hexadiene) was 68/32, and the iodine value was 7.7. The intrinsic viscosity [η] measured in decalin at 135 ° C was 4.8 dl / g. The above polymerization conditions are shown in Table 1.

[0100]

[Table 1]

[Production of Vulcanized Rubber] Octene produced by the above method as the higher α-olefin copolymer (1)
As the ethylene / α-olefin copolymer (2), the molar ratio of ethylene and propylene (ethylene-1,5-hexadiene / 7-methyl-1,6-octadiene copolymer (1-a) / Propylene) is 70/30, the intrinsic viscosity [η] measured in decalin at 135 ° C. is 2.5 dl / g, and the iodine value is 15 ethylene / propylene / 5-ethylidene-2-norbornene co-weight Compound (2-a) was compounded according to Table 2 to obtain an unvulcanized compounded rubber.

Upon blending, the above-mentioned higher α-olefin copolymer (1-a), ethylene / α-olefin copolymer (2-a), zinc white, stearic acid, FEF carbon and naphthene oil. Was kneaded with a 4.3-liter Banbury mixer [manufactured by Kobe Steel, Ltd.] for 6 minutes, and then allowed to stand at room temperature for 1 day. To the kneaded material thus obtained, a vulcanization accelerator and sulfur were added to open a roll (front roll / back roll: 50/60 ° C., 16/18 rp).
m) was kneaded to obtain a compounded rubber.

[0103]

[Table 2]

The compounded rubber obtained as described above was added to 15
The vulcanized sheet was heated for 30 minutes with a press heated to 0 ° C.
Were prepared and the following tests were conducted. The test items are as follows. (Test item) Tensile test, hardness test, aging test, bending test, vibration damping test (Test method) Tensile test, hardness test, aging test, and bending test were measured according to JIS K6301.

That is, in the tensile test, the tensile strength (T
_B), elongation (E _B), JIS A hardness in the hardness test (H
_s ) was measured. The aging test was carried out by air heating aging test at 120 ° C. for 70 hours, and the retention ratio to the physical properties before aging,
That tensile strength retention A _R (T _B), elongation retention ratio A
_R (E _B ) was determined.

The bending test examined the resistance to crack growth on a dematcher tester. That is, the number of times of bending until a crack became 15 mm was measured and used as an index of dynamic fatigue resistance. Loss tangent (tan δ) was measured as an index of vibration damping property by using a dynamic spectrometer of Rheometric Co. under the condition of 25 ° C. and 100 rad / sec. The results are shown in Table 3.

[0107]

Example 2 In Example 1, the blending amounts of the copolymer (1-a) and the copolymer (2-a) were 80 parts by weight and 2 respectively.
The same procedure as in Example 1 was carried out except that the amount was 0 part by weight. The results are shown in Table 3.

[0108]

Example 3 In Example 1, the blending amounts of the copolymer (1-a) and the copolymer (2-a) were 20 parts by weight and 8 parts by weight, respectively.
The same procedure as in Example 1 was carried out except that the amount was 0 part by weight. The results are shown in Table 3.

[0109]

COMPARATIVE EXAMPLE 1 The procedure of Example 1 was repeated, except that the copolymer (2-a) was not used and 100 parts by weight of the copolymer (1-a) was used alone. . The third result
Shown in the table.

[0110]

COMPARATIVE EXAMPLE 2 The procedure of Example 1 was repeated, except that the copolymer (1-a) was not used and 100 parts by weight of the copolymer (2-a) was used alone. .. The third result
Shown in the table.

[0111]

Example 4 In the same manner as in Example 1, except that the copolymer (1-a) was replaced by a higher α-olefin and the polymerization conditions were changed as shown in Table 1 above, copolymerization was carried out in the same manner as in Example 1. Hexene-1,1,5-hexadiene
7-methyl-1,6-octadiene copolymer (1-b)
The same procedure as in Example 1 was performed except that was used.

The results are shown in Table 3.

[0113]

Example 5 In the same manner as in Example 1, except that instead of the copolymer (1-a), higher α-olefin and polymerization conditions were changed as shown in Table 1, copolymerization was carried out in the same manner as in Example 1. Decene obtained by the following procedure: 1,1,6-Heptadiene-7-
The procedure of Example 1 was repeated except that the methyl-1,6-octadiene copolymer (1-c) was used.

The results are shown in Table 3.

[0115]

[Example 6] In Example 1, instead of the copolymer (2-a), ethylene / 1-butene / 5-ethylidene-2-
Norbornene copolymer (2-b) [ethylene / 1-butene (molar ratio); 90/10, [η] measured in decalin at 135 ° C; η]; 2.8 dl / g, iodine value except 10) Was performed in the same manner as in Example 1.

The results are shown in Table 3.

[0117]

[Table 3]

[Brief description of drawings]

FIG. 1 is a flowchart showing a process for preparing an olefin polymerization catalyst used in the production of a higher α-olefin copolymer according to the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masaaki Kawasaki Akira 6-1-2 Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Industries, Ltd. 6-1-2 Waki, Waki Town Mitsui Petrochemical Industry Co., Ltd.

Claims (7)

[Claims] 1. A higher α-comprising a higher α-olefin having 6 to 20 carbon atoms, an α, ω-diene represented by the following general formula [I], and a non-conjugated diene represented by the following general formula [II]. An olefin copolymer (1) and an ethylene / α-olefin copolymer (2) composed of ethylene and an α-olefin having 3 to 6 carbon atoms, and the higher α-olefin copolymer Polymer (1) and the ethylene
Weight ratio with α-olefin copolymer (2) [(1) /
(2)] is 5/95 to 95/5, which is a vulcanizable rubber composition; [In the formula, n is an integer of 1 to 3, and R ¹ and R ² are
Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms], [In the formula, n is an integer of 1 to 5 and R ³ is 1 carbon atom.
Represents to 4 alkyl groups, R ⁴ and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁴
Neither R ⁵ nor R ⁵ is a hydrogen atom]. 2. The higher α-olefin copolymer (1)
Molar ratio [higher α-olefin / α, ω-diene] of higher α-olefin to α, ω-diene of 95/5 to 50
The rubber composition according to claim 1, wherein the rubber composition is / 50. 3. The higher α-olefin copolymer (1)
Intrinsic Viscosity [η] measured in decalin solvent at 135 ℃
Is in the range of 1.0 to 10.0 dl / g. 3. The rubber composition according to claim 1, wherein 4. The higher α-olefin copolymer (1)
The iodine value of 1 to 50 is 1 to 50.
The rubber composition according to any one of 3 above. 5. The rubber composition according to claim 1, wherein the α-olefin constituting the ethylene / α-olefin copolymer (2) is propylene or 1-butene. object. 6. The intrinsic viscosity [η] of the ethylene / α-olefin copolymer (2) measured in a decalin solvent at 135 ° C. is in the range of 0.8 to 5.0 dl / g. The rubber composition according to any one of claims 1 to 5. 7. The rubber according to claim 1, wherein the ethylene / α-olefin copolymer (2) contains a non-conjugated polyene in an amount of 0.1 to 5 mol%. Composition.