JP2758433B2 - Vulcanizable rubber composition - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a vulcanization excellent in properties such as strength properties, heat resistance, weather resistance, vibration damping properties, vibration damping properties and dynamic fatigue resistance (flex fatigue resistance). It relates to possible rubber compositions.

Technical Background of the Invention Ethylene / α-olefin copolymer rubber represented by ethylene / propylene / diene copolymer rubber is selected for its strength characteristics, heat resistance, weather resistance, etc. It is widely used for rubber products, electrical insulating materials, civil engineering materials, and other applications. However, this ethylene / α-olefin copolymer rubber has dynamic fatigue resistance,
Due to poor vibration damping properties and vibration damping properties, for specific applications, such as vibration damping rubber, rubber rolls, belts, tires, etc.,
There was room for improvement.

Natural rubber, on the other hand, has excellent strength properties and dynamic fatigue resistance, but is inferior in heat resistance and weather resistance, and cannot be said to have sufficient vibration damping and vibration damping properties. I was

Object of the Invention The present invention is intended to solve the problems associated with the prior art as described above, and has excellent strength properties, heat resistance, weather resistance, vibration damping properties, vibration damping properties and dynamic fatigue resistance. It is an object of the present invention to provide a vulcanizable rubber composition.

SUMMARY OF THE INVENTION The vulcanizable rubber composition according to the present invention has 6 to 12 carbon atoms.
And a non-conjugated diene represented by the following general formula [I] and having a higher α-olefin content in the range of 70 to 99.99 mol% (higher α-olefin-based copolymer rubber ( 1) ethylene and α-olefin having a molar ratio of ethylene to α-olefin (ethylene / α-olefin) of 50/50 to 95/5, which is composed of ethylene and α-olefin having 3 to 6 carbon atoms. Olefin copolymer rubber (2), and the weight ratio of the higher α-olefin copolymer rubber (1) to the ethylene / α-olefin copolymer rubber (2) [(1) / (2 )] Is 5/95 to 95/5.

(Wherein, R ¹ represents an alkyl group having 1 to 4 carbon atoms, R ² and R ³ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, provided that both R ² and R ³ are hydrogen atoms. There is no specific description of the invention. Hereinafter, the vulcanizable rubber composition according to the present invention will be specifically described.

The vulcanizable rubber composition according to the present invention comprises a higher α-olefin copolymer rubber (1) and an ethylene / α-olefin copolymer rubber (2).

Higher α-olefin copolymer rubber (1) The higher α-olefin copolymer rubber (1) used in the present invention is composed of a higher α-olefin and a non-conjugated diene.

The higher α-olefin used in the present invention is an α-olefin having 6 to 12 carbon atoms, and specifically, hexene-1, heptene-1, octene-1, nonene-1, decene-1, undecene and the like. -1, dodecene-1 and the like. In the present invention, the higher α-olefins described above may be used alone or as a mixture of two or more. Of the higher α-olefins, hexene-1, octene-1 and decene-1 are preferably used.

The content of the higher α-olefin constituting the higher α-olefin copolymer rubber (1) used in the present invention is 70 to 70%.
It is in the range of 99.99 mol%, preferably 80 to 99.9 mol%.

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

(Wherein, R ¹ represents an alkyl group having 1 to 4 carbon atoms, R ² and R ³ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, provided that both R ² and R ³ are hydrogen atoms. The non-conjugated diene as described above is specifically 6
-Methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 6 -Methyl-1,6-nonadiene, 7-methyl-1,6
-Nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-1,6 −
And undecadiene.

In the present invention, the above non-conjugated dienes may be used alone or as a mixture of two or more.

Among the non-conjugated dienes, 7-methyl-1,6-octadiene is preferably used.

The iodine value of the higher α-olefin copolymer rubber (1) used in the present invention is 1 to 50, preferably 2 to 30, and more preferably 4 to 20. Generally, when the iodine value of the higher α-olefin copolymer rubber (1) is too large, the resulting rubber composition tends to have a small elongation and tend to be brittle. On the other hand, when the iodine value of the higher α-olefin copolymer rubber (1) is too small, the vulcanization rate of the obtained rubber composition becomes too slow to be practically used.

The intrinsic viscosity [η] of the higher α-olefin copolymer rubber (1) used in the present invention measured in a decalin solvent at 135 ° C. is 1.0 to 10.0 dl / g, preferably 2.0 to 9.0 dl / g,
More preferably, it is 3.0 to 8.0 dl / g. When the intrinsic viscosity [η] exceeds 10 dl / g, processing of the obtained rubber composition tends to be difficult, while the intrinsic viscosity [η] is 1.0 dl / g.
When it is less than g, the strength properties of the obtained rubber composition tend to decrease.

In the vulcanizable rubber composition according to the present invention, the vibration damping property is improved, and the dynamic fatigue resistance is improved. The reason for this is
Although it is not clear yet, the specific α-olefin copolymer rubber (1) exhibits a damping property due to a specific relaxation behavior thereof,
In addition, since the affinity between the high-supply α-olefin copolymer rubber (1) and various fillers is high, it is estimated that dynamic fatigue resistance is improved.

The content of the non-conjugated diene constituting the higher α-olefin copolymer rubber (1) used in the present invention is in the range of 0.01 to 30 mol%, preferably 0.1 to 20 mol%.

The composition of the higher α-olefin copolymer rubber (1) is ¹³
It is measured by the C-NMR method.

The higher α-olefin copolymer rubber (1) used in the present invention can be produced, for example, by the following method.

The higher α-olefin-based copolymer rubber (1) used in the present invention is obtained by preparing a higher α-olefin copolymer rubber in the presence of an olefin polymerization catalyst.
-Obtained by copolymerizing an olefin and a non-conjugated diene.

The olefin polymerization catalyst used in the above copolymerization 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 flowchart of a method for preparing a catalyst component for olefin polymerization used in producing the higher α-olefin copolymer rubber (1) in the present invention.

The solid titanium catalyst component [A] 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 a magnesium compound, a titanium compound and an electron donor as described below.

Examples of the titanium compound used for preparing the solid titanium catalyst component (A) include Ti (OR) _g X _4-g (R is a hydrocarbon group, X is a halogen atom,
A tetravalent titanium compound represented by 0 ≦ g ≦ 4) can be exemplified. More specifically, titanium tetrahalides such as TiCl ₄ , TiBr ₄ , and TiI ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (OisoC ₄ H ₉ ) Br _3, etc .; trihalogenated alkoxytitanium; Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti ( _{On-C 4 H 9) 2} Cl 2, Ti (OC 2 H 5) 2 dihalogenated dialkoxy titanium, such as _{Br 2; Ti (OCH 3)} 3 Cl, Ti (OC 2 H 5) 3 Cl, Ti (On Monohalogenated trialkoxy titanium such as -C ₄ H ₉ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Br; Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₄ H) ₉₎ such as ₄ Ti (tetraalkoxy titanium such as _{Oiso-C 4 H 9) 4} Ti (O-2 _{-ethylhexyl) 4} can be mentioned.

Among these, a halogen-containing titanium compound, particularly a titanium tetrahalide, is preferable, and titanium tetrachloride is more preferably used. These titanium compounds may be used alone or in combination of two or more. Further, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

Examples of the magnesium compound used for preparing the solid titanium catalyst component [A] include a magnesium compound having a reducing property and a magnesium compound having no reducing property.

Here, examples of the magnesium compound having a reducing property include a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond. Specific examples of the magnesium compound having such a reducing property include dimethylmagnesium,
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 can be used alone,
A complex compound may be formed with an organic aluminum compound described below. 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 chloride, magnesium iodide, and magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, and butoxy magnesium chloride. And alkoxymagnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride; alkoxymagnesiums such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium and 2-ethylhexoxymagnesium. Allyloxymagne such as phenoxymagnesium and dimethylphenoxymagnesium Um; magnesium laurate, such as carboxylic acid salts of magnesium such as magnesium stearate and the like.

The non-reducing magnesium compound may be a compound derived from the above-described reducing magnesium compound or a compound derived during the preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducing magnesium compound, for example, a reducing magnesium compound is converted to a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, or the like. What is necessary is just to contact with a compound.

The magnesium compound is a complex compound, a complex compound of the above-mentioned magnesium compound and another metal, or a mixture of another metal compound, in addition to the above-mentioned magnesium compound having a reducing property and the magnesium compound having no reducing property. You may. Further, a mixture of two or more of the above compounds may be used.

Among these, a magnesium compound having no reducing property is preferable, and a halogen-containing magnesium compound is particularly preferable. Among these, magnesium chloride, alkoxymagnesium chloride, and allyloxymagnesium chloride are preferably used.

Examples of the electron donor used for preparing the solid titanium catalyst component [A] include organic carboxylic acid esters, preferably polyvalent carboxylic acid esters, and specifically, compounds having a skeleton represented by the following formula. Can be

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 represent a hydrogen atom Represents a substituted or unsubstituted hydrocarbon group. Preferably, at least one of R ³ and R ⁴ is a substituted or unsubstituted hydrocarbon group. R ³ and R ⁴ may be connected to each other to form a cyclic structure. Examples of the substituted hydrocarbon group include N,
Examples include substituted hydrocarbon groups containing a different atom such as O and S, and include, for example, —CO—C—, —COOR—, —COOH—, —OH, —SO ₃ H, —C—N—C—. include hydrocarbon groups substituted with a structure such as -NH _2.

Among these, a diester in which at least one of R ¹ and R ² is derived from a dicarboxylic acid having an alkyl group having 2 or more carbon atoms is preferable.

Specific examples of polyvalent carboxylic acid esters include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, dibutyl methyl malonate, diethyl malonate, diethyl ethyl malonate, diethyl isopropyl malonate, butyl Diethyl malonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl allylmalonate, diethyldiisobutylmalonate, diethyldinormalbutylmalonate, dimethylmaleate, monooctylmaleate, diisooctylmaleate, diisobutylmaleate, butylmaleic acid Diisobutyl, diethyl butyl maleate, β
-Aliphatic polycarboxylates such as diisopropyl methylglutarate, diallyl ethyl succinate, di-2-ethylhexyl fumarate, diethyl itaconate, diisobutyl itaconate, diisooctyl citraconic acid, dimethyl citraconic acid, 1,2-cyclohexanecarboxylic acid Aliphatic polycarboxylates such as diethyl, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadicate, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate , Ethyl isobutyl phthalate, mono-n-butyl phthalate,
Ethyl n-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 phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, trimellitic acid Examples include aromatic polycarboxylic acid esters such as dibutyl, and 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, and n-sebacate.
Octyl, di-2-ethylhexyl sebacate and the like,
Esters derived from long chain dicarboxylic acids can be mentioned.

Among these polycarboxylic acid esters, compounds having a skeleton represented by the aforementioned general formula are preferred, and more preferably phthalic acid, maleic acid, substituted malonic acid, and the like, and alcohols having 2 or more carbon atoms. Esters are preferred, and diesters obtained by reacting phthalic acid with alcohols having 2 or more carbon atoms are particularly preferred.

As these polycarboxylic acid esters, it is not always necessary to use the above-mentioned polycarboxylic acid esters as starting materials, and these polycarboxylic acid esters are derived during the preparation of the solid titanium catalyst component [A]. A polyvalent carboxylic acid ester may be formed in the step of preparing the solid titanium catalyst component [A] using a compound that can be used.

Examples of the electron donor other than the polyvalent carboxylic acid that can be used when preparing the solid titanium-based catalyst [A] include alcohols, amines, amides, ethers, ketones, and nitriles as described below. , Phosphines, stippins, arsines, phosphoramides, esters,
Organosilicon compounds such as thioethers, thioesters, acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy (aryloxy) silanes, organic acids, and members of Groups I to IV of the Periodic Table Examples thereof include metal amides and salts.

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

The method for producing the solid titanium catalyst component [A] will be briefly described below with several examples.

(1) A method of reacting a magnesium compound or a complex compound comprising a magnesium compound and an electron donor with a titanium compound in a liquid phase. This reaction may be performed in the presence of a grinding aid or the like. Further, when reacting as described above, the solid compound may be pulverized. Furthermore, when reacting as described above, each component may be pretreated with an electron donor and / or a reaction assistant 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 in which a liquid titanium compound is reacted in the presence of an electron donor to precipitate a solid titanium complex.

(3) A method in which a titanium compound is further reacted with the reaction product obtained in (2).

(4) The reaction product obtained in (1) or (2)
A method in which an electron donor and a titanium compound are further reacted.

(5) A solid obtained by pulverizing a magnesium compound or a complex compound comprising a magnesium compound and an electron donor in the presence of a titanium compound is treated with any of a halogen, a halogen compound and an aromatic hydrocarbon. Method. In this method, a magnesium compound or a complex compound comprising a magnesium compound and an electron donor may be ground in the presence of a grinding aid or the like. Alternatively, a magnesium compound or a complex compound composed of a magnesium compound and an electron donor may be ground in the presence of a titanium compound, pre-treated with a reaction aid, and then treated with a halogen or the like. In addition, examples of the reaction assistant include an organic aluminum compound and a halogen-containing silicon compound. In this method, an electron donor is used at least once.

(6) A method of treating the compound obtained in the above (1) to (4) with a halogen, a halogen compound or an aromatic hydrocarbon.

(7) A method of contacting a catalyst reactant with a metal oxide, dihydrocarbylmagnesium and a halogen-containing alcohol 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, alkoxymagnesium, or aryloxymagnesium 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 the above (1) to (8), a method using a liquid titanium halide during the catalyst preparation, a method using a titanium compound, or a method using a titanium compound In this case, a method using a halogenated hydrocarbon is preferable.

The amount of each of the above components used in preparing the solid titanium catalyst component [A] varies depending on the preparation method and cannot be specified unconditionally. For example, the amount of the electron donor is about 0.01 to 5 per mole of the magnesium compound. Moles, preferably 0.05 to 2 moles, and the titanium compound is used in an amount of about 0.01 to 500 moles, preferably 0.05 to 300 moles.

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], halogen /
The titanium (atomic ratio) is about 4-200, preferably about 5-100, and the electron donor / titanium (molar ratio) is about 0.1-1.
0, preferably about 0.2 to about 6, and magnesium / titanium (atomic ratio) of about 1 to 100, preferably about 2 to 50.

This solid titanium catalyst component [A] contains a magnesium halide having a small crystal size as compared with a commercially available magnesium halide, and usually has a specific surface area of about 50 m ² / g or more, preferably about 60 to 1000 m ² / g, More preferably about 100
~800m is a ² / g. The solid titanium catalyst component [A] does not substantially change its composition by washing with hexane since the above components are integrated to form a catalyst component.

Such a solid titanium catalyst component [A] may be used alone, or may be used after being diluted with an inorganic compound or an organic compound such as a silicon compound, an aluminum compound, or a polyolefin. In addition, when a diluent is used, even if it is smaller than the above-mentioned specific surface area, it shows high catalytic activity.

For a method of preparing such a highly active titanium catalyst component, see, for example, JP-A-50-108385 and JP-A-50-126590.
No. 51-20297, No. 51-28189, No. 51
No. 64586, No. 51-92885, No. 51-136625, No. 52-87489, No. 52-1000596, No. 52-
No. 147688, No. 52-104593, No. 53-2580, No. 53-40093, No. 53-40094, No. 53-43
No. 094, No. 55-135102, No. 55-135103, No. 55-152710, No. 56-811, No. 56-119
No. 08, No. 56-18606, No. 58-83006,
JP-A-58-138705, JP-A-58-138706, JP-A-58-138707
JP-A-58-138708, JP-A-58-138709,
Nos. 58-138710, 58-138715, 60-23404
No. 61-21109, No. 61-37802, No. 61
-37803, and the like.

As the organoaluminum compound catalyst component [B], a compound having at least one Al-carbon bond in the molecule can be used. Examples of such a compound include: (i) a compound represented by the general formula R ¹ _m Al (OR ² ) _{n Hp} X _q (wherein R ¹ and R ² each usually have 1 to 15 carbon atoms, preferably 1 to X is a hydrocarbon group containing four, and may be the same or different from each other, and X represents a halogen atom;
0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0
≦ q <a number of 3, moreover organic aluminum compound represented by m + n + p + q = a 3), (ii) the general formula M ¹ Al R ¹ ₄ (wherein, M ¹ is a Li, Na, K, R ¹ is the same as described above) and a complex alkylated product of a Group 1 metal and aluminum.

As the organoaluminum compound belonging to the above (i), the following compounds can be exemplified.

General formula R ¹ _m Al (OR ² ) _3-m (wherein R ¹ and R ² are the same as above. M is preferably 1.
General formula R ¹ _m Al X _3-m (wherein R ¹ is the same as above; X is halogen, and m is preferably 0 <m <3); Formula R ¹ _m Al H _3-m (wherein R ¹ is the same as above. M is preferably 2 ≦ m <3
In a), the general formula _{^{R 1 m Al (OR 2)}} n X q ( wherein, R ¹ and R ² are the same .x said halogen, 0
<M ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3
And the like.

As the aluminum compound belonging to (i), more specifically, trialkylaluminum such as triethylaluminum and tributylaluminum; trialkenylaluminum such as triisoprenylaluminum; dialkylaluminum alkoxide such as diethylaluminum ethoxide and dibutylaluminum butoxide ; ethylaluminum sesquichloride ethoxide, alkyl aluminum sesqui alkoxides such as butyl sesquichloride _{^{butoxide, R 1 2.5 Al (OR 2}} ) 0.5 alkylaluminum partially alkoxylated with an average composition represented by like diethyl aluminum chloride, dibutyl Dialkylaluminum halides such as aluminum chloride and diethylaluminum bromide; ethylaluminum chloride Alkyl aluminum sesquihalides such as chloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; partially halogenated alkyl aluminum such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide; diethyl aluminum Dialkyl aluminum hydrides such as hydride and dibutyl aluminum hydride; other partially hydrogenated alkyl aluminums such as ethyl aluminum dihydride and alkyl aluminum dihydride such as propyl aluminum dihydride; ethyl aluminum ethoxycyclolide, butyl aluminum butoxycyclolide, ethyl Alcohol such as aluminum ethoxy bromide Shi reduction and halogenated alkylaluminum can be exemplified.

Examples of the compound similar to (i) include an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. Such compounds include, for _{example, (C 2 H 5) 2} Al O Al (C 2 H 5) 2, (C 4 H 9) 2 Al O Al (C 4 H 9) 2, Methyl aluminoxane and the like can be mentioned.

Examples of the compound belonging to (ii) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Among these, it is particularly preferable to use a trialkyl aluminum or an alkyl aluminum to which two or more of the above-mentioned aluminum compounds are bonded.

Examples of the electron donor catalyst component [C] include alcohols,
Oxygen-containing electron donors such as phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, alkoxysilanes, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates Or a polycarboxylic acid ester such as those described above. More specifically, methanol, ethanol, propanol, pentanol,
Hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol,
C1-C18 alcohols such as isopropyl alcohol, cumyl alcohol and isopropylbenzyl alcohol; phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol,
Phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as cumylphenol and naphthol; acetone,
C3 to C15 ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone; C2 to C15 aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde; methyl formate , Methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate , Methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate Chill, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisopropyl tetrahydrophthalate, diethyl phthalate Organic acid esters having 2 to 30 carbon atoms, such as diisobutyl phthalate, di-n-butyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate; acetyl chloride, benzoyl C2 to C15 acid halides such as chloride, toluic acid chloride and anisic acid chloride; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether Ethers having 2 to 20 carbon atoms such as; acetamide, benzoic acid amide,
Acid amides such as toluic acid amide; methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzilamine, aniline, pyridine,
Amines such as picoline and tetramethylenediamine; nitriles such as acetonitrile, benzonitrile and tolunitrile; acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride are used.

Further, as the electron donor catalyst component [C], an organosilicon compound represented by the following general formula [I] can be used.

R _n Si (OR ′) _4-n [I] wherein R and R ′ are hydrocarbon groups, and 0 <n <4
Specific examples of the organosilicon compound represented by the above general formula [I] include trimethylmethoxysilane,
Trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethylmethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyl Diethoxysilane,
Bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, Ethyltrimethoxysilane,
Ethyltriethoxysilane, bityltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltoluethoxysilane , Ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane,
Wenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, bityltributoxysilane,
Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxy (allyloxy) Silane, vinyl tris (β-methoxyethoxy silane), vinyl triacetoxy silane, dimethyl tetraethoxy disiloxane and the like are used.

Among them, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-p-tolyldimethoxysilane Preferred are silane, 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 [II] can be used.

Si R ¹ R ² _m (OR ³ ) _3-m ... [II] [wherein, R ¹ is a cyclopentyl group or a cyclopentyl group having an alkyl group, and R ² is an alkyl group, a cyclopentyl group, and a cyclopentyl having an alkyl group. A group selected from the group consisting of groups, R ³ is a hydrocarbon group, and m is 0 ≦ m ≦ 2. In the formula [II], R ¹ is a cyclopentyl group or a cyclopentyl group having an alkyl group, and as R ¹ , in addition to the cyclopentyl group, a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 2-ethylcyclopentyl group And a cyclopentyl group having an alkyl group such as a 2,3-dimethylcyclopentyl group.

In the formula [II], R ² is any one of an alkyl group, a cyclopentyl group and a cyclopentyl group having an alkyl group, and R ² is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group. group, alkyl groups such as hexyl, or cyclopentyl group having an exemplified cyclopentyl group and an alkyl group as R ¹ can be exemplified similarly.

Further, in the equation [II], R ³ is a hydrocarbon group, R ³
Examples thereof include hydrocarbon groups such as an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

Among these, it is preferable to use an organosilicon compound in which R ¹ is a cyclopentyl group, R ² is an alkyl group or a cyclopentyl group, and R ³ is 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; dicyclopentyldimethoxy Dialkoxysilanes such as silane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane and dicyclopentyldiethoxysilane; tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxy Silane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldi Chill silane, mono-alkoxysilanes such as cyclopentyl dimethylethoxysilane, and the like.
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 production of the higher α-olefin copolymer rubber (1) includes a solid titanium catalyst component [A], an organoaluminum compound catalyst component [B], and an electron donor. In the present invention, the higher α-olefin and the non-conjugated diene are polymerized by using the olefin polymerization catalyst. In the present invention, the higher olefin polymerization catalyst is used to polymerize the α-olefin or higher olefin. After preliminarily polymerizing the α-olefin, a higher α-olefin and a non-conjugated diene can be polymerized (main polymerization) using this catalyst. In the prepolymerization, the α-olefin or higher α-olefin is prepolymerized in an amount of 0.1 to 500 g, preferably 0.3 to 300 g, particularly preferably 1 to 100 g per 1 g of the olefin polymerization catalyst.

In the prepolymerization, a catalyst having a considerably 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 usually about 0.01 to 200 mmol, preferably about 0.1 to 200 mmol, in terms of titanium atom, per inert hydrocarbon medium described later.
It is in the range of 100 mmol, particularly preferably 1 to 50 mmol.

The amount of the organoaluminum catalyst component [B] may be an amount such that 0.1 to 500 g, preferably 0.3 to 300 g of a polymer is produced per 1 g of the solid titanium catalyst component [A]. About 0.1 to 1 per mole of titanium atom
00 mol, preferably about 0.5-50 mol, particularly preferably 1 mol
In an amount of ~ 20 mol.

The electron donor catalyst component [C] is used in an amount of 0.1 to 50 mol, preferably 0.5 to 30 mol, particularly preferably 1 to 10 mol, per 1 mol of titanium atoms in the solid titanium catalyst component [A].

The prepolymerization is preferably performed under mild conditions by adding an olefin or a higher α-olefin and the above-mentioned catalyst component to an inert hydrocarbon medium.

As the inert hydrocarbon medium used at this time, specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, etc. Aliphatic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures thereof. Among these inert hydrocarbon media, it is particularly preferable to use an aliphatic hydrocarbon. The prepolymerization can be carried out using the olefin or higher α-olefin itself as a solvent, or the prepolymerization can be carried out 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 during the prepolymerization is usually about -20 to + 100 ° C,
Preferably about -20 to + 80 ° C, more preferably 0 to +40
It is in the range of ° C.

In the prepolymerization, a molecular weight regulator such as hydrogen can be used. Such molecular weight regulators are
It is desirable to use the polymer in an amount such that the intrinsic viscosity [η] of the polymer obtained by the prepolymerization measured in a decalin solvent at 135 ° C. is about 0.2 dl / g or more, preferably about 0.5 to 10 dl / g.

As described above, the prepolymerization is carried out so as to produce about 0.1 to 500 g, preferably about 0.3 to 300 g, particularly preferably 1 to 100 g of polymer per 1 g of the solid titanium catalyst component [A]. If the prepolymerization amount is too large, the production efficiency of the olefin polymer may decrease.

The prepolymerization can be performed in a batch system or a continuous system.

The olefin polymerization catalyst is preliminarily polymerized as described above, and is formed from the obtained solid titanium catalyst component [A], organoaluminum catalyst component [B], and electron donor catalyst component [C]. Copolymerization (main polymerization) of a higher α-olefin and a non-conjugated diene is performed in the presence of an olefin polymerization catalyst.

In the copolymerization (main polymerization) of a higher α-olefin and a non-conjugated diene, in addition to the olefin polymerization catalyst, the organic aluminum compound used as a catalyst component in the production of the olefin polymerization catalyst is used as a catalyst component. The same one as the aluminum compound catalyst component [B] can be used.
In the main polymerization of the higher α-olefin, the same electron donor catalyst component [C] used in producing the olefin polymerization catalyst can be used as the electron donor catalyst component. Note that the organoaluminum compound and the electron donor used in the copolymerization (main polymerization) of the higher α-olefin and the non-conjugated diene are not necessarily the organoaluminum compounds used in preparing the olefin polymerization catalyst. And need not be identical to the electron donor.

The copolymerization (main polymerization) of a higher α-olefin and a non-conjugated diene is usually performed in a liquid phase.

In the copolymerization (main polymerization) of a higher α-olefin and a non-conjugated diene, the solid titanium catalyst component [A] is usually used in an amount of about 0.001 to about 1.0 in terms of titanium atom per polymerization volume.
It is used in an amount of mmol, preferably about 0.005 to 0.1 mmol. Further, the organoaluminum compound catalyst component [B]
Is such that the metal atom in the organoaluminum compound catalyst component [B] is usually about 1 to 2000 mol, preferably about 5 to 500 mol per 1 mol of the titanium atom in the solid titanium catalyst component [A]. Used in quantity. Further, the electron donor catalyst component [C] is usually used in an amount of about 0.001 to 10 mol, preferably about 0.01 to 2 mol, particularly preferably about 0.05 to 2 mol per mol of metal atom in the organoaluminum compound catalyst component [B].
It is used in such an amount that it becomes １1 mol.

If hydrogen is used during the main polymerization, the molecular weight of the obtained polymer rubber can be adjusted.

The polymerization temperature of the higher α-olefin and the non-conjugated diene is
Usually about 20-200 ° C., preferably about 40-100 ° C., the pressure is usually normal pressure to 100 kg / cm ² , preferably normal pressure to 50 kg / cm
Set to ² . In the copolymerization (main polymerization) of a higher α-olefin and a non-conjugated diene, the polymerization 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 rubber (2) The ethylene / α-olefin copolymer rubber (2) used in the present invention is basically composed of ethylene and α-olefin. A component may be contained.

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. , Propylene and 1-butene are preferably used.

The ethylene / α-olefin copolymer rubber (2) used in the present invention has a molar ratio of ethylene / α-olefin (ethylene / α-olefin) of 50/50 to 95/50.
5, preferably 55/45 to 93/7, more preferably 60/40 to 9
1/9.

As the polyene component, a non-conjugated polyene is used. Specifically, 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene,
5-isopropenyl-2-norbornene, dicyclopentadiene and the like, among which 5-ethylidene-2
-Norbornene and dicyclopentadiene are preferably used.

The content of these non-conjugated polyene components is 1 to 50, preferably 4 to 40, more preferably 6 to 30 in iodine value.
0.1 to 10 mol%, preferably 0.5 to 0.5 mol%
-7 mol%, more preferably 1-5 mol%.

The intrinsic viscosity [η] of the ethylene / α-olefin copolymer rubber (2) used in the present invention measured at 135 ° C. in decalin solvent is 0.8 to 5 dl / g, preferably 0.9 to 4 dl / g, more preferably 1.0 to 3 dl / g. The intrinsic viscosity [η] is
If it exceeds 5 dl / g, the resulting rubber composition tends to be difficult to process, while if the intrinsic viscosity [η] is less than 0.8 dl / g, the strength properties of the obtained rubber composition tend to decrease. is there.

The vulcanizable rubber composition according to the present invention has high strength, which is presumed to be due to the long molecular chain of the ethylene / α-olefin copolymer rubber (2).

Higher α constituting the vulcanizable rubber composition according to the present invention
-The mixing ratio of the olefin copolymer rubber (1) and the ethylene / α-olefin copolymer rubber (2) is preferably 5/95 to 95/5 by weight ratio [(1) / (2)]. Is 10 / 90-9
0/10, more preferably 20/80 to 80/20.

The rubber composition according to the present invention, SRF, GPF, FEF, HAF,
Carbon blacks such as ISAF, SAF, FT, and MT, rubber reinforcing agents such as finely divided silica, and fillers such as light calcium carbonate, heavy calcium carbonate, talc, and clay may be blended. The types and amounts of these rubber reinforcing agents and fillers can be appropriately selected according to the intended use, but the amounts are usually selected from higher α-olefin copolymer rubber (1) and ethylene / α-olefin copolymer. Total amount with united rubber (2)
The maximum is 300 parts by weight, preferably 200 parts by weight, per 100 parts by weight.

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 exhibited most. That is, the higher α-olefin copolymer rubber (1) constituting the rubber composition according to the present invention has a function of improving the properties of the vulcanized product such as vibration damping properties and dynamic fatigue resistance. Since the ethylene / α-olefin copolymer rubber (2) has a function of improving properties such as strength properties of the vulcanized product, the rubber composition according to the present invention is used to obtain strength properties, vibration damping properties and dynamic resistance. A vulcanizate having excellent fatigue properties can be obtained.

When a vulcanizate is obtained from the rubber composition according to the present invention, a higher α-olefin copolymer rubber (1) and an ethylene / α-olefin copolymer rubber are used according to the intended use and performance of the vulcanizate. (2) In addition to the above, types and amounts of rubber reinforcing agents, fillers, and softeners, and vulcanizing agents, vulcanization accelerators,
The type and amount of the compound constituting the vulcanization system such as the vulcanization aid, the amount of the antioxidant and the type and the amount of the processing aid, and the process for producing the vulcanizate can be appropriately selected.

Higher α-olefin copolymer rubber (1) and ethylene / α-olefin copolymer rubber (2) in vulcanizate
Can be appropriately selected according to the intended performance and application of the vulcanized product, but is usually 20% by weight or more, preferably 25% by weight.
That is all.

As the softening agent, a softening agent usually used for rubber can be used, and specifically, a process oil, a lubricating oil,
Petroleum softeners such as paraffin, liquid paraffin, petroleum asphalt and petrolatum; coal tar softeners such as coal tar and coal tar pitch; fatty oil softeners such as castor oil, linseed oil, rapeseed oil and coconut oil; Oil; sub; waxes such as beeswax, carnauba wax, and lanolin; fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate, and zinc laurate; petroleum resins, atactic polypropylene, and cumarone indene resins The synthetic high molecular substance of the above can be mentioned. Among them, a petroleum softener is preferably used, and particularly, a process oil is preferably used.
The compounding amount of these softeners can be appropriately selected according to the use of the vulcanized product, but the compounding amount is usually higher α-olefin copolymer rubber (1) and ethylene / α-olefin copolymer rubber. It is at most 150 parts by weight, preferably 100 parts by weight, based on 100 parts by weight in total with (2).

To produce a vulcanizate from the rubber composition according to the present invention,
As in the case of vulcanizing a general rubber, an unvulcanized compounded rubber is once prepared by the method described later, and then the compounded rubber is molded into an intended shape and then vulcanized. As a vulcanization method, there are a method of heating using a vulcanizing agent and a method of irradiating an electron beam.

Examples of the vulcanizing agent used for vulcanization include a sulfur compound and an organic peroxide. Specific examples of the sulfur compound include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, selenium dimethyldithiocarbamate, and the like. Of these, sulfur is preferably used. The sulfur compound is a total of 10% of the higher α-olefin copolymer rubber (1) and the ethylene / α-olefin copolymer rubber (2).
It is used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 0 parts by weight. As the organic peroxide, specifically, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-
2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5- (tert-butylperoxy) hexyne-3,
Di-tert-butyl peroxide, di-tert-butyl peroxy-
3,3,5-trimethylcyclohexane, tert-butyl hydroperoxide and the like. Among them, dicumyl peroxide, di-tert-butyl peroxide and di-tert-butylperoxy-3,3,5-trimethylcyclohexane are preferably used. The organic peroxide is used in an amount of 3 × 10 ^{-4 to} 5 × 10 ^-2 per 100 g of the total of the higher α-olefin copolymer rubber (1) and the ethylene / α-olefin copolymer rubber (2).
Moles, preferably 1 × 10 ^{−3 to} 3 × 10 ⁻² moles.

When using a sulfur compound as a vulcanizing agent,
It is preferable to use a vulcanization accelerator in combination. Specific examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene-2
-Benzothiazolesulfenamide, N, N-diisopropyl-2-benzothiazolesulfenamide, 2-
Thiazole compounds such as mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole, dibenzothiazyldisulfide;
Guanidine compounds such as diphenyl guanidine, triphenyl guanidine, diortho tolyl guanidine, ortho toryl by guanide, diphenyl guanidine phthalate; aldehyde amines such as acetaldehyde-aniline compound, butyl aldehyde-aniline condensate, hexamethylene tetramine, acetaldehyde ammonia Or an aldehyde-ammonia compound; an imidazoline compound such as 2-mercaptoimidazoline; a thiourea compound such as thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, or diorthotolylthiourea; tetramethylthiuram monosulfide, tetramethyl Thiuram disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, pen Thiuram-based compounds such as methylenethiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethylthiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, dimethyldithiocarbamate Dithioate compounds such as selenium and tellurium diethyldithiocarbamate; xanthate compounds such as zinc dibutylxanthate; and compounds such as zinc white. These vulcanization accelerators are composed of higher α-olefin copolymer rubber (1) and ethylene • α.
-Used in an amount of 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the total amount of the olefin copolymer rubber (2).

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

When using an electron beam without using a vulcanizing agent as the vulcanization method, 0.1 to 1 to the molded unvulcanized compounded rubber described later
0 MeV (mega electron volts), preferably 0.3 to 2.0
Absorbed dose of 0.5 to 35 Mrad for electrons with MeV energy
(Megarad), preferably 0.5 to 10 Mrad. At this time, a vulcanization aid may be used in combination with an organic peroxide as a vulcanizing agent. The amount of the vulcanization aid depends on the higher α-olefin copolymer rubber (1) of the present invention and ethylene / α-olefin 1 × 10 ^-4 to 1 × 10 ^-1 mol, preferably 1 × 10 ^{-3 to} 3 mol per 100 g of the total amount with the copolymer rubber (2).
× 10 ^-2 mol.

Unvulcanized compounded rubber is prepared by the following method. That is, high-grade α-
After kneading the olefin copolymer, filler, and softener at a temperature of 80 to 170 ° C. for 3 to 10 minutes, use a roll such as an oven roll, and use a vulcanizing agent and, if necessary, vulcanization acceleration. And a vulcanizing aid, and mix at a roll temperature of 40-80 ° C.
After kneading for ~ 30 minutes, the mixture is dispensed to prepare a ribbon or sheet compound rubber.

The compounded rubber thus prepared is molded into a desired shape by an extruder, a calender roll, or a press, and simultaneously with molding or by introducing the molded product into a vulcanization tank,
A vulcanized product can be obtained by heating at a temperature of 0 to 270 ° C. for 1 to 30 minutes, or by irradiating with an electron beam by the method described above. In this vulcanization step, a mold may be used, or vulcanization may be performed without using a mold. When a mold is not used, the steps of molding and vulcanization are usually performed 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), and steam can be used.

Of course, when vulcanization is performed by electron beam irradiation, a compounded rubber containing no compounding agent is used.

The rubber vulcanizate produced as described above is itself used as an anti-vibration rubber, automobile parts such as a cover material for a tire vibrating part, industrial rubber products such as rubber rolls and belts, electric insulating materials, civil engineering building materials, It can be used for applications such as rubberized cloth. In particular, it can be suitably used for applications requiring vibration damping properties and dynamic fatigue resistance, for example, anti-vibration rubber, rubber rolls, belts, tires, wiper blades, and the like.

Furthermore, when producing a foam from the rubber composition according to the present invention, a foaming agent and, if necessary, a foaming aid can be blended.

Specific examples of the blowing agent include inorganic foaming agents such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, and ammonium nitrite; N, N'-dimethyl N, N'-dinitroso terephthalamide, N , N′−
Nitroso compounds such as dinitrosopentamethylenetetramine; azo compounds such as azodicarboxamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, barium / azodicarboxylate; benzenesulfonylhydrazide, toluenesulfonylhydrazide, P Sulfonyl hydrazide compounds such as, P'-oxybis (benzenesulfonyl hydrazide) and diphenylsulfone-3,3'-disulfonyl hydrazide;
Azide compounds such as calcium azide, 4,4'-diphenyldisulfonyl azide, p-toluenesulfonyl azide and the like can be mentioned. Among them, nitroso compounds, azo compounds and azide compounds are preferably used. Such a foaming agent comprises a total amount of the higher α-olefin copolymer rubber (1) and the ethylene / α-olefin copolymer rubber (2).
By mixing at a ratio of 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight with respect to 100 parts by weight, the apparent specific gravity is 0.03 to 0.3.
7 foams can be manufactured. The foaming aid is an additive that functions to lower the decomposition temperature of the foaming agent, promote the decomposition, and make the cells uniform. Specific examples of the foaming aid include organic acids such as salicylic acid, phthalic acid and stearic acid; urea and derivatives thereof.

The foam produced from the rubber composition according to the present invention can be used for applications such as a heat insulating material, a floating material, a cushion material, and a soundproofing material.

Effect of the Invention The vulcanizable rubber composition according to the present invention has a specific higher α
-Since it contains the olefin copolymer rubber (1) and the ethylene / α-olefin copolymer rubber (2) in a specific ratio, strength properties, heat resistance, weather resistance, vibration damping properties, vibration damping properties And a vulcanizate having the above-mentioned effects can be provided.

Since the vulcanizate obtained from the vulcanizable rubber composition according to the present invention has the above-described effects, it is itself used as a vibration-isolating rubber, an automobile part such as a cover material for a tire vibrating part,
It can be used for applications such as industrial rubber products such as rubber rolls and belts, electrical insulating materials, civil engineering building materials, and rubberized cloth. In particular, it can be suitably used for applications requiring vibration damping properties and dynamic fatigue resistance, for example, anti-vibration rubber, rubber rolls, belts, tires, wiper blades, and the like.

The foam produced from the rubber composition according to the present invention can be used for applications such as a heat insulating material, a floating material, a cushion material, and a soundproofing material.

Hereinafter, the present invention will be described with reference to examples, the present invention,
It is not limited to these examples.

Example 1 (Preparation of solid titanium catalyst component) 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 2-
After 390.6 g of ethylhexyl alcohol was heated and reacted at 130 ° C. for 2 hours to form a homogeneous solution, 21.3 g of phthalic anhydride was added to the solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour. Was dissolved in this homogeneous solution. After cooling the homogeneous solution thus obtained to room temperature, 75 ml of this homogeneous solution was maintained at -20 ° C.
The whole amount was dropped in 200 ml over 1 hour. After completion of the charging, the temperature of the mixture was raised to 110 ° C. over 4 hours, and when the temperature reached 110 ° C., diisobutyl phthalate 5.2
2 g was added, and the mixture was kept under stirring at the same temperature for 2 hours. After completion of the reaction for 2 hours, a solid portion was collected by hot filtration,
After this solid portion was resuspended in 275 ml of titanium tetrachloride, a heating reaction was performed again at 110 ° C. for 2 hours. After the completion of the reaction, the solid portion was collected again by hot filtration, and sufficiently washed with decane and hexane at 110 ° C. until no free titanium compound was detected in the washing solution. The solid titanium catalyst component prepared by the above operation was held 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 thus obtained was 2.2% by weight of titanium, 58.1% by weight of chlorine and 19.
2% by weight and 10.7% by weight of diisobutyl phthalate.

(Polymerization) 142 ml of decane, 100 ml of octene-1 and 8 m of 7-methyl-1,6-octadiene in a 500 ml polymerization vessel equipped with a stirring blade.
l Charged. The temperature of the solution was raised to 50 ° C., and hydrogen and nitrogen were continuously introduced into the solution at a rate of 6, 50 per hour, respectively. After the temperature was raised to 50 ° C., 0.625 mol of triisobutylaluminum, 0.21 mmol of trimethylethoxysilane, and 0.0125 mmol of a solid titanium catalyst component in terms of titanium atoms were charged to initiate polymerization. 50
After polymerization at 30 ° C. for 30 minutes, a small amount of isobutyl alcohol was added to terminate the polymerization, and then the polymerization solution was poured into a large amount of methanol to precipitate a copolymer. Then
After recovering the precipitated copolymer, it was dried under reduced pressure at 120 ° C for 24 hours to obtain 14.3 g of octene-1.7-methyl-1,6-octadiene copolymer. The intrinsic viscosity [η] of the obtained copolymer measured at 135 ° C. in decalin was 4.5 dl / g, the iodine value (IV) was 10, and octene-1 and 7-
Mole ratio with methyl-1,6-octadiene (octene-1 / 7
-Methyl-1,6-octadiene) was 96/4.

 Table 1 shows the above polymerization conditions.

(Production of vulcanized rubber) 50.0 parts by weight of the octene-1.7-methyl-1,6-octadiene copolymer rubber (1-a) as the higher α-olefin copolymer rubber (1), As the ethylene / α-olefin copolymer rubber (2), the molar ratio of ethylene and propylene (ethylene / propylene) is 70/30, and the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C.
2.5 dl / g, 50 parts by weight of ethylene-propylene / 5-ethylidene-2-norbornene copolymer rubber (2-a) having an iodine value of 5-ethylidene-2-norbornene of 15; [Manufactured by Sakai Chemical Industry Co., Ltd.] 5.0 parts by weight, stearic acid 1.0 part by weight, FEF carbon (trade name: Seast SO, manufactured by Tokai Carbon Co., Ltd.) 50.0 parts by weight, naphthenic oil [trade name: Sansen 4240 10.0 parts by weight of sulfur, 1.0 part by weight of sulfur, and 0.5 parts by weight of 2-mercaptobenzothiazole [trade name: Suncellar M, manufactured by Sanshin Chemical Industry Co., Ltd.] Methylthiuram disulfide [Product name Suncellar T
T, manufactured by Sanshin Chemical Industry Co., Ltd.] and 1.5 parts by weight.

Upon compounding, first, the above copolymer rubber (1-a),
Copolymer rubber (2-a), stearic acid, zinc white, FEF
Carbon and naphthenic oils were kneaded for 6 minutes with 4.3 Banbury mixer (manufactured by Kobe Steel Ltd.), and then allowed to stand at room temperature for 1 day.

The vulcanization accelerator and sulfur were added to the kneaded material obtained in this manner with a 14-inch open roll, and the mixing time with the open roll was 4 minutes. 70 ℃, rotation speed is 16rp with front roll
m, and mixed by a rear roll at 18 rpm.

Next, a sheet of the compounded rubber thus obtained was prepared, and a vulcanized sheet was prepared by pressing at 150 ° C. for 30 minutes.
The following tests were performed.

 The test items are as follows.

[Test items] Tensile test, hardness test, aging test, bending test, vibration damping property.

[Test method] JIS K 63 for tensile test, hardness test, aging test and flex test
Measured according to 01. That is, in the tensile test, the tensile strength (T _B ) and elongation (E _B ) were measured, and in the hardness test, the spring hardness (H _S , JIS A hardness) was measured. Aging test is 70 at 120 ° C
A time air heat aging test was performed. After the aging test, a tensile test was performed to determine a retention rate for physical properties before aging, that is, a tensile strength retention rate A _R (T _B ) and an elongation retention rate A _R (E _B ). The bending test examined the resistance to crack growth with a dematcher tester. That is, the number of times of bending until the crack became 15 mm was measured.

The loss tangent (tan δ) was measured using a rheometric dynamic spectrometer as an index of damping.
The temperature was measured at 100 rad / sec.

 Table 2 shows the results.

Example 2 In the same manner as in Example 1, except that the blending amounts of the copolymer rubber (1-a) and the copolymer rubber (2-a) were 80 parts by weight and 20 parts by weight, respectively. To obtain a vulcanized sheet, and the above test was conducted.

 Table 2 shows the results.

Example 3 The same as Example 1 except that the blending amounts of the copolymer rubber (1-a) and the copolymer rubber (2-a) were changed to 20 parts by weight and 80 parts by weight, respectively. To obtain a vulcanized sheet, and the above test was conducted.

 Table 2 shows the results.

Comparative Example 1 In Example 1, copolymer rubber (1-a) was used instead of copolymer rubber (1-a) and copolymer rubber (2-a).
A vulcanized sheet was obtained and subjected to the above test in the same manner as in Example 1 except that 100 parts by weight was used alone.

 Table 2 shows the results.

Comparative Example 2 In Example 1, copolymer rubber (2-a) was used instead of copolymer rubber (1-a) and copolymer rubber (2-a).
A vulcanized sheet was obtained and subjected to the above test in the same manner as in Example 1 except that 100 parts by weight was used alone.

 Table 2 shows the results.

Example 4 The procedure of Example 1 was repeated, except that the copolymer rubber (1-a) was replaced with higher α-olefins and the polymerization conditions as shown in Table 1 above. Example 1 except that the hexene-1.7-methyl-1,6-octadiene copolymer rubber (1-b) obtained by the above was used.
A vulcanized sheet was obtained in the same manner as described above, and the above test was conducted.

The properties of the hexene-1.7-methyl-1,6-octadiene copolymer rubber are as follows.

Monomer ratio (molar ratio): hexene-1 / 7-methyl-1,6
-Octadiene = 96/4 intrinsic viscosity [η] (135 ° C., decalin): 5.1 dl / g iodine value (IV): 12 The results are shown in Table 2.

Example 5 The procedure of Example 1 was repeated, except that the copolymer rubber (1-a) was replaced with higher α-olefins and the polymerization conditions as shown in Table 1 above. A vulcanized sheet was obtained in exactly the same manner as in Example 1 except that the decene-1.7-methyl-1,6-octadiene copolymer rubber (1-c) obtained by the above was used. Was performed.

The properties of the above decene-1.7-methyl-1,6-octadiene copolymer rubber are as follows.

Monomer ratio (molar ratio): decene-1 / 7-methyl-1,6-
Octadineene = 95/5 Intrinsic viscosity [η] (135 ° C., decalin): 4.0 dl / g Iodine value (IV): 10 The results are shown in Table 2.

Example 6 The procedure of Example 1 was repeated except that, instead of the copolymer rubber (2-a), an ethylene / 1-butene / 5-ethylidene-2-norbornene copolymer rubber (2-b) was used. A vulcanized sheet was obtained in exactly the same manner as in Example 1, and the above test was conducted.

The properties of the ethylene / 1-butene / 5-ethylidene-2-norbornene copolymer rubber are as follows.

 Ethylene / 1-butene (molar ratio): 90/10 Intrinsic viscosity [η] (135 ° C., decalin): 2.8 dl / g Iodine value (IV): 10.0 The results are shown in Table 2.

[Brief description of the drawings]

FIG. 1 is a flow chart showing a process for preparing an olefin polymerization catalyst used in producing the higher α-olefin copolymer rubber (1) in the present invention.

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Shuji Minami 6-1, 1-2 Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Industries, Ltd. (58) Field surveyed (Int. Cl. ⁶ , DB name) ) C08L 23/18 C08L 23/08

Claims (6)

(57) [Claims] (1) a higher α-olefin having 6 to 12 carbon atoms and a non-conjugated diene represented by the following general formula [I], wherein the content of the higher α-olefin is 70 to 99.99 mol%.
, A higher α-olefin-based copolymer rubber (1) having a molar ratio of ethylene / α-olefin (ethylene / α-olefin) comprising ethylene and α-olefin having 3 to 6 carbon atoms. (Α / olefin) is 50/50 to 95/5, the ethylene / α-olefin copolymer rubber (2), and the higher α-olefin copolymer rubber (1) and the ethylene / α-olefin copolymer A vulcanizable rubber composition, wherein the weight ratio [(1) / (2)] to the rubber (2) is 5/95 to 95/5; (Wherein, R ¹ represents an alkyl group having 1 to 4 carbon atoms, R ² and R ³ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, provided that both R ² and R ³ are hydrogen atoms. Is not.) 2. The intrinsic viscosity [η] of the higher α-olefin copolymer rubber (1) measured in a decalin solvent at 135 ° C. is in the range of 1.0 to 10.0 dl / g. The rubber composition according to claim 1. 3. The rubber composition according to claim 1, wherein the higher α-olefin copolymer rubber (1) has an iodine value of 1 to 50. 4. The method according to claim 1, wherein the α-olefin constituting the ethylene / α-olefin copolymer rubber (2) is propylene or 1-butene. 3. The rubber composition according to item 1. 5. The intrinsic viscosity [η] of the ethylene / α-olefin copolymer rubber (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 4. 6. The method according to claim 1, wherein said ethylene / α-olefin copolymer rubber (2) contains 0.1 to 5 mol% of a non-conjugated polyene. The rubber composition as described in the above.