JP3029095B2 - Applications of higher α-olefin copolymers and vulcanizates thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel higher α-olefin copolymer, a method for producing the same, and a vulcanizate thereof.
More specifically, it has excellent characteristics such as dynamic fatigue resistance (bending fatigue resistance), weather resistance, ozone resistance, heat aging resistance, and low-temperature characteristics, and can be used for various rubber products and resin modifiers. The present invention relates to an olefin copolymer, a method for producing the same, and a vulcanized product thereof.

[0002]

BACKGROUND OF THE INVENTION Vulcanizates of ethylene-propylene-diene copolymers have good heat resistance and ozone resistance. Therefore, they are used in automobile industry parts, industrial rubber products, electrical insulation materials, and civil engineering construction materials. It is widely used as a material for plastic blending with articles, rubber products such as rubberized cloth, and polypropylene and polystyrene. However, this ethylene-propylene-diene copolymer is inferior in dynamic fatigue resistance and is therefore unsuitable for a specific application, for example, a vibration-proof rubber, a rubber roll, a belt, a tire, a cover material for a vibrating part, and the like. .

On the other hand, US Pat. No. 3,937,693 discloses that at least one monomer selected from 1-butene and an α-olefin having 5 to 12 carbon atoms, 5-methyl-1,4-hexadiene and 4-methyl-1 Copolymer of 1,4-hexadiene (with at least 15% of 5-methyl-1,4-hexadiene) with a coordination catalyst, sulfur-vulcanizable and low gel content copolymer disclosed are doing. U.S. Pat. No. 4,340,705 discloses a catalyst system comprising a transition metal compound and an organoaluminum compound to which hexaalkylphosphoric triamide or an organic phosphoric acid ester is added. Disclosed are high molecular weight, sulfur vulcanizable, low gel content copolymers of 8 to about 36 α, ω-polyenes.

[0004] The inventors of the present invention aimed at obtaining a polymer having excellent properties such as weather resistance, ozone resistance and heat aging resistance and capable of obtaining a vulcanizate having excellent dynamic properties such as flex resistance. After extensive research, a specific higher α-olefin was copolymerized with a specific non-conjugated diene in the presence of a specific olefin polymerization catalyst. The inventors have found that an olefin-based copolymer can be obtained, and have completed the present invention.

[0005]

Accordingly, the present invention provides a novel higher α-olefin / non-conjugated diene copolymer which is vulcanizable and substantially does not generate gel.

Further, the present invention provides a method for producing the above novel copolymer. Further, the present invention provides a novel additive having excellent weather resistance, ozone resistance, heat aging resistance, low temperature properties, vibration damping properties and dynamic labor resistance obtained from the above-mentioned novel higher α-olefin / non-conjugated diene copolymer. Provide sulphate.

[0007]

SUMMARY OF THE INVENTION According to the present invention, there is provided an anti-vibration rubber, a tire and the like.
Higher α-olefin copolymer for cover material of vibrating part
The copolymer is a copolymer comprising a higher α-olefin having 6 to 12 carbon atoms and a non-conjugated diene represented by the following general formula [I], wherein (a) the non-conjugated diene content is 0.01 to 30. in the range of mol%, it is higher α- olefin copolymer is in the range of (b) an intrinsic viscosity measured at decalin solvent 135 ° C. [eta] is 1.0~10.0dl / g It is characterized by:

[0008]

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Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² and R ³ are 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 vibration-proof rubber, tire and tire according to the present invention
The cover material of the vibrating part is
It is a vulcanizate of a polymer.

[0010]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the higher α-olefin copolymer according to the present invention, the method for producing the same, and the vulcanized product thereof will be described in detail.

The higher α-olefin copolymer according to the present invention comprises a higher α-olefin and a non-conjugated diene. The higher α-olefin used in the present invention is
Α-olefin having 6 to 12 carbon atoms, specifically, hexene-1, heptene-1, octene-1, nonene-1,
Decene-1, undecene-1, dodecene-1 and the like.

In the present invention, the higher α-
The olefin may be used alone or as a mixture of two or more. The non-conjugated diene used in the present invention is a non-conjugated diene represented by the following general formula [I].

[0013]

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Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² and R ³ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, provided that both R ² and R ³ are hydrogen atoms Specific examples of the non-conjugated diene as described above include 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-undecadiene, etc. Is mentioned.

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 particularly preferably used.

Further, in addition to the non-conjugated dienes as described above, other copolymerizable monomers such as ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1
May be used as long as the object of the present invention is not impaired.

The content of the non-conjugated diene constituting the higher α-olefin copolymer of 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 is measured by ¹³ C-NMR method. This characteristic value is a standard value when the higher α-olefin copolymer of the present invention is vulcanized using 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 as follows:
1.0 to 10.0 dl / g, preferably 1.5 to 8 dl
/ G. This characteristic value corresponds to the high α-
It is a scale indicating the molecular weight of an olefin-based copolymer.

The higher α-olefin copolymer according to the present invention as described above can be produced by the following method.
The higher α-olefin copolymer according to the present invention is obtained by copolymerizing a higher α-olefin with a non-conjugated diene in the presence of an olefin polymerization catalyst.

The olefin polymerization catalyst used in the present invention comprises 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 according to 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] comprises:
It is prepared by contacting a magnesium compound, a titanium compound and an electron donor as described below. In the present invention, as the titanium compound used for preparing the solid titanium catalyst component [A], for example, Ti (OR) _g X
_4-g (R is a hydrocarbon group, X is a halogen atom, 0 ≦ g ≦
The tetravalent titanium compound represented by 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 (} Oiso-C 4 H 9) trihalide, alkoxy titanium such as _{Br 3; Ti (OCH 3)} 2 Cl 2, Ti (O
_{C 2 H 5) 2 Cl 2} , Ti (On-C 4 H 9) 2 Cl 2, Ti (OC 2
Dihalogenated dialkoxy titanium, such as H _{5) 2} Br _2; T
i (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Cl, Ti (On-C ₄
Monohalogenated trialkoxy titanium such as 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) 4, Ti (Oiso-C 4 H 9) 4,
Tetraalkoxytitanium such as Ti (O-2 ethylhexyl) ₄ can be used.

Of 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.

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.

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, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, didecylmagnesium, ethylmagnesium chloride, propylmagnesiumchloride, 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 or may form a complex compound with an organic aluminum compound described later. These magnesium compounds may be liquid or solid.

Specific examples of the non-reducing magnesium compound include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, and isopropoxy magnesium chloride. Alkoxy magnesium halides such as magnesium, butoxy magnesium chloride, octoxy magnesium chloride; alkoxy magnesium halides such as phenoxy magnesium chloride, methylphenoxy magnesium chloride; ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2-ethylhexoxy magnesium Alkoxymagnesium such as;
Allyloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium; magnesium carboxylate 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 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.

In the present invention, in addition to the above-mentioned magnesium compound having a reducing property and the magnesium compound having no reducing property, a magnesium compound is a complex compound, a double compound or another compound of the above-mentioned magnesium compound and another metal. It may be a mixture with a metal compound. Further, a mixture of two or more of the above compounds may be used.

In the present invention, among these, magnesium compounds having no reducing property are preferred, and halogen-containing magnesium compounds are particularly preferred. Of these, magnesium chloride, alkoxymagnesium chloride, and allyloxymagnesium chloride are preferably used. Can be

In the present invention, the electron donor used for preparing the solid titanium catalyst component [A] includes an organic carboxylic acid ester, preferably a polyvalent carboxylic acid ester, and is specifically represented by the following formula. Examples include compounds having a skeleton.

[0031]

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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. 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 a substituted hydrocarbon group containing a different atom such as N, O, and S. For example, -COC-,-
_{COOR, -COOH, -OH, -SO 3} H, -C-N
-C -, - and hydrocarbon group substituted with a structure such as NH _2.

Among them, 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,
Monooctyl maleate, diisooctyl maleate,
Diisobutyl maleate, diisobutyl butyl maleate, diethyl butyl maleate, diisopropyl β-methylglutarate, diallyl ethyl succinate, di-2-ethylhexyl fumarate, diethyl itaconate, diisobutyl itaconate, diisooctyl citrate, dimethyl citrate Aliphatic polycarboxylates, diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadicate, etc., aliphatic polycarboxylates, monoethyl phthalate, phthalic acid Dimethyl, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, mono-normal butyl phthalate, ethyl normal butyl phthalate, di-n-pro phthalate Diisopropyl phthalate, di-n-butyl phthalate, di-isobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, didecyl phthalate, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, Dibutyl naphthalene dicarboxylate, triethyl trimellitate,
Examples include aromatic polycarboxylic acid esters such as dibutyl trimellitate, and esters derived from heterocyclic polycarboxylic acids such as 3,4-furandicarboxylic acid.

Other examples of polycarboxylic acid esters include diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, n-octyl sebacate, and di-2-ethylhexyl sebacate. 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 preferred are phthalic acid, maleic acid, substituted malonic acid and the like, and alcohols having 2 or more carbon atoms. Are preferred, and a diester obtained by reacting phthalic acid with an alcohol having 2 or more carbon atoms is 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 may be used during the preparation of the solid titanium catalyst component [A]. A polycarboxylic acid ester may be generated in the step of preparing the solid titanium catalyst component [A] using a compound capable of deriving an ester.

In the present invention, the solid titanium-based catalyst [A]
Examples of the electron donor other than the polyvalent carboxylic acid that can be used in preparing the compound include alcohols, amines, amides, ethers, ketones, nitriles, phosphines, and stippins as described below. , Arsines, phosphoramides, esters, thioethers, thioesters, acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy (aryloxy) silanes and other organic silicon compounds, organic acids and periodic table I of
Examples include amides and salts of metals belonging to groups IV to IV.

In the present invention, the solid titanium catalyst component [A] can be produced by contacting the above-mentioned magnesium compound (or metallic magnesium), 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 reaction product of 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.

In the method for preparing the solid titanium catalyst component [A] described in the above (1) to (8), a method using a liquid titanium halide at the time of preparing the catalyst, a method using a titanium compound, or a method using When using a compound, a method using a halogenated hydrocarbon is preferred.

The amount of each of the above-mentioned components used in preparing the solid titanium catalyst component [A] varies depending on the preparation method and cannot be specified unconditionally. 0.01-5
Moles, preferably 0.05 to 2 moles, and the titanium compound is present in an amount of about 0.01 to 500 moles, preferably 0.05 to 30 moles.
Used in an amount of 0 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], halogen / titanium (atomic ratio) is about 4 to 200, preferably about 5 to 100,
The electron donor / titanium (molar ratio) is about 0.1 to 10,
Preferably, it is about 0.2 to about 6, and the magnesium / titanium (atomic ratio) is about 1 to 100, preferably about 2 to 50.

The 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 to 800 m 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] comprises:
Although it can be used alone, it can also be used after being diluted with an inorganic or 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.

The method for preparing such a highly active titanium catalyst component is described in, for example, JP-A-50-108385,
No. 0-126590, No. 51-20297, No. 51-28189, No. 51-64586, No. 51-92885, No. 51-1366
No. 25, No. 52-87489, No. 52-100596, No. 5
No. 2-147688, No. 52-104593, No. 53-2580, No. 53-40093, No. 53-40094, No. 53-43094
No. 55-135102, No. 55-135103, No. 55
No. -152710, No. 56-811, No. 56-11908,
No. 56-18606, No. 58-83006, No. 58-138705, No. 58-138706, No. 58-138707, No. 58-1
No. 38708, No. 58-138709, No. 58-138710, No. 58-138715, No. 60-23404, No. 61-2110
No. 9, No. 61-37802, and No. 61-37803.

As the organoaluminum compound catalyst component [B], a compound having at least one Al-carbon bond in the molecule can be used. Such compounds include:
For example, (i) a general formula R ¹ _m Al (OR ² ) _n H _p X _q (wherein, R ¹ and R ² usually have 1 to 15 carbon atoms, preferably 1 to 15 carbon atoms.
These are four hydrocarbon groups, which may be the same or different from each other. X represents a halogen atom, and 0 <m ≦
3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q <3
A number, moreover m + n + p + q = a 3) an organoaluminum compound represented by, (ii) the general formula M ¹ AlR ¹ ₄ (wherein, M ¹ is Li, Na, K
And R ¹ is the same as defined 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 a number of 1.5 ≦ m ≦ 3), General formula R ¹ _m AlX _3-m (wherein, R ¹ is the same as above; X is halogen, m is preferably 0 <m <3); and a general formula R ¹ _m AlH _3-m (wherein, R ¹ is the same as described 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.

More specifically, the aluminum compounds belonging to (i) include trialkylaluminums such as triethylaluminum and tributylaluminum; trialkenylaluminums such as triisoprenylaluminum; diethylaluminum ethoxide and dibutylaluminum butoxide. Dialkylaluminum alkoxide; ethylaluminum sesquiethoxide,
Alkyl aluminum sesquialkoxides such as butyl aluminum sesquibutoxide, R ¹ _2.5 Al (OR ² )
Partially alkoxylated alkylaluminum having an average composition represented by _0.5 or the like; dialkylaluminum halide such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide; ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide Alkyl aluminum dihalides such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, and butyl aluminum dibromide; dialkyl aluminum hydrides such as diethyl aluminum hydride and dibutyl aluminum hydride; Ethyl aluminum dihydride, propyl aluminum Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as uranium dihydride; partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, and ethylaluminum ethoxybromide be able to.

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 AlO
Al (C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ AlOAl (C
₄ H _{9) 2,}

[0050]

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Methyl aluminoxane and the like can be mentioned. Compounds belonging to the above (ii) include Li A
1 (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Among these, it is particularly preferable to use trialkyl aluminum or 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, phenols, ketones, aldehydes, carboxylic acids,
Esters of organic or inorganic acids, ethers, acid amides,
Oxygen-containing electron donors such as acid anhydrides and alkoxysilanes,
A nitrogen-containing electron donor such as ammonia, an amine, a nitrile, and an isocyanate, or the above-mentioned polycarboxylic acid ester can be used. More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, cumyl alcohol, isopropyl benzyl alcohol, etc. Alcohols having 1 to 18 carbon atoms; phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, and naphthol; C3-C15 ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone; acetaldehyde, propyl Aldehydes having 2 to 15 carbon atoms such as aldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, butyric acid Methyl, 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, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadicate, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate C2-C30 organic acid esters such as di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate; acetyl chloride, benzoyl chloride, toluic acid chloride, anise C2 to C15 acid halides such as chloride; C2 to C20 ethers such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether; acetate amide, benzoic acid amide; Acid amides such as toluic acid amide; amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylenediamine; nitriles such as acetonitrile, benzonitrile, 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 ') in _4-n ... [I] [wherein, R and R' is a hydrocarbon group, 0 <n <4
Specific examples of the organosilicon compound represented by the above general formula [I] include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane,
Dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyl Dimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane,
Dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane Silane, 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-norbornanemethyldimethoxysilane,
Ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane and the like are used. Of these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-p-tolydimethoxysilane Silane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane,
Cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, diphenyldiethoxysilane are preferred.

Further, as the electron donor catalyst component [C],
An organosilicon compound represented by the following general formula [II] can also be used. SiR 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 group having an alkyl group Wherein 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 , other than a 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. Examples of R ² include a methyl group, an ethyl group, a propyl group and an isopropyl group. Groups, alkyl groups such as butyl group and hexyl group, or R
^The cyclopentyl group and the cyclopentyl group having an alkyl group exemplified as ¹ can be similarly mentioned.

In the formula [II], 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.

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; Dialkoxysilanes such as dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane and dicyclopentyldiethoxysilane; tricyclopentylmethoxysilane, tricyclopentylethoxysilane, Cyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyl Ethyl 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 present invention comprises a solid titanium catalyst component [A], an organoaluminum compound catalyst component [B], and an electron donor [C] as described above.
In the present invention, a higher α-olefin and a non-conjugated diene are polymerized using the olefin polymerization catalyst.
After pre-polymerization of the -olefin or the higher α-olefin, the higher α-olefin and the non-conjugated diene can be polymerized (main polymerization) using this catalyst. During prepolymerization, 0.1 to 500 g per 1 g of the olefin polymerization catalyst,
Preferably from 0.3 to 300 g, particularly preferably from 1 to 10
The α-olefin or higher α-olefin is prepolymerized in an amount of 0 g.

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 100 mmol, and particularly preferably 1 to 50 mmol, per liter of the inert hydrocarbon medium described below, in terms of titanium atoms.
Desirably, it is in the mmol range.

The amount of the organoaluminum catalyst component [B] is
The amount may be 0.1 to 500 g, preferably 0.3 to 300 g of polymer per 1 g of the solid titanium catalyst component [A]. It is usually desirable that the amount is about 0.1 to 100 mol, preferably about 0.5 to 50 mol, particularly preferably 1 to 20 mol.

The electron donor catalyst component [C] is used in an amount of 0.1 to 5 per mole 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.

The prepolymerization is preferably carried out 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; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene Hydrogen; 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. Preliminary polymerization can be carried out using olefin or higher α-olefin itself as a solvent,
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 -2.
It is desirable to be in the range of 0 to + 80 ° C, more preferably 0 to + 40 ° C.

In the prepolymerization, a molecular weight regulator such as hydrogen may 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. of about 0.2.
It is desirable to use an amount of dl / g or more, preferably about 0.5 to 10 dl / g.

As described above, the prepolymerization is carried out so that about 0.1 to 500 g, preferably about 0.3 to 300 g, and particularly preferably 1 to 100 g of polymer is produced per 1 g of the solid titanium catalyst component [A]. It is desirable to carry out. 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. 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 above-mentioned olefin polymerization catalyst, an organoaluminum compound catalyst component is used for producing an olefin polymerization catalyst. The same organic aluminum compound catalyst component [B] can be used. In the copolymerization (main polymerization) of a higher α-olefin and a non-conjugated diene, the electron donor catalyst component [C] used in producing the olefin polymerization catalyst is used as the electron donor catalyst component. Similar ones can be used. 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 carried out in a gas phase or 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 0.1 in terms of titanium atoms per liter of polymerization volume.
001 to about 1.0 mmol, preferably about 0.005 to
Used in an amount of 0.5 mmol. The organoaluminum compound catalyst component [B] has a metal atom in the organoaluminum compound catalyst component [B] of usually about 1 to 20 per mole of titanium atom in the solid titanium catalyst component [A].
It is used in an amount such that it amounts to 00 mol, preferably about 5 to 500 mol. Further, the electron donor catalyst component [C]
Metal atom 1 in organoaluminum compound catalyst component [B]
The amount is usually about 0.001 to 10 mol, preferably about 0.01 to 2 mol, particularly preferably about 0.05 to 1 mol, per mol.

During the main polymerization, the molecular weight of the obtained polymer can be controlled by controlling the amount of hydrogen used. In the present invention, the polymerization temperature of the higher α-olefin and the non-conjugated diene is usually about 10 to 200 ° C, preferably about 30 to 100 ° C, and the pressure is usually normal pressure to 100 kC.
g / cm ² , preferably from normal pressure to 50 kg / cm 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.

The higher α-olefin copolymer of the present invention obtained by the above polymerization is used as a polymer having excellent dynamic fatigue resistance, heat resistance, ozone resistance, low-temperature properties and the like. In particular, when applied to resin modifiers and various rubber products, they exhibit their characteristics to the fullest.

As the resin modifier, for example, a modifier such as polypropylene, polyethylene, or polystyrene can be used. These resins have a higher α-
When an olefin copolymer is added, impact resistance and stress crack resistance can be dramatically improved.

Various rubber products are generally used in a vulcanized state. If the higher α-olefin copolymer of the present invention is used in a vulcanized state, its properties are further exhibited. When the higher α-olefin-based copolymer of the present invention is used as various rubber products, the vulcanized product is prepared once as an unvulcanized compounded rubber, as in the case of vulcanizing a general rubber. It is produced by molding a compounded rubber into an intended shape followed by vulcanization.

As the vulcanization method, either a method of heating using a vulcanizing agent or a method of irradiating an electron beam may be employed. 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, and selenium dimethyldithiocarbamate. Of these, sulfur is preferably used.
The sulfur compound is used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the higher α-olefin copolymer of the present invention. Specific examples of the organic peroxide include dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, and 2,5-dimethylperoxide.
Dimethyl-2,5-di (benzoylperoxy) hexane,
2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, di-tert-butyl peroxide, di-tert-butylperoxy-3,3,5-trimethylcyclohexane, tert-butyl hydroperoxide, etc. Can be Among them, dicumyl peroxide, di-tert-butyl peroxide and di-tert-butylperoxy-3,3,5-trimethylcyclohexane are preferably used. The organic peroxide is 3 × 10 ^{-4 to} 5 × 1 per 100 g of the higher α-olefin copolymer of the present invention.
It is used in an amount of from 0 to ² mol, preferably from 1 × 10 ^{−3 to} 3 × 10 ⁻² mol.

When a sulfur compound is used 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-mercaptobenzothiazole, 2- (2,4-dinitrophenyl)
Thiazole compounds such as mercaptobenzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole, dibenzothiazyldisulfide; diphenylguanidine, triphenylguanidine, diorthotrilguanidine, orthotrile by guanide, diphenyl Guanidine compounds such as guanidine phthalate; aldehyde amine or aldehyde-ammonia compounds such as acetaldehyde-aniline reactant, butyraldehyde-aniline condensate, hexamethylenetetramine and acetaldehyde ammonia; imidazoline compounds such as 2-mercaptoimidazoline; thiocarbanilide Thiourea-based compounds, such as thiourea, diethylthiourea, dibutylthiourea, trimethylthiourea, and diorthotolylthiourea; Thiuram compounds such as ram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethylthiothiocarbamate, zinc di-n-butyldithiocarbamate, ethyl Dithioate compounds such as zinc phenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate and tellurium diethyldithiocarbamate; xanthate compounds such as zinc dibutylxanthate; compounds such as zinc white be able to.

These vulcanization accelerators are used in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the higher α-olefin copolymer.
Preferably it is used in an amount of 0.2 to 10 parts by weight. 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 sulfur and quinone dioxime compounds such as 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 an equimolar, based on 1 mol of the organic peroxide used. When an electron beam is used without using a vulcanizing agent as a vulcanization method, a molded unvulcanized compounded rubber, which will be described later, is used in an amount of 0.1 to 10 MeV (megaelectron volt), preferably 0.3 to 20 MeV. Irradiation may be performed so that the absorbed dose is 0.5 to 35 Mrad (mega rad), 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, and the amount thereof is 1 × 10 ^{−4 with} respect to 100 g of the higher α-olefin copolymer of the present invention.
１1 × 10 ^-1 mol, preferably 1 × 10 ^{-3 to} 3 × 10 ^-2
Mix moles.

The unvulcanized compounded rubber is prepared by the following method. That is, a higher α-olefin copolymer, a filler, and a softener are kneaded with a mixer such as a Banbury mixer at a temperature of 80 to 170 ° C. for 3 to 10 minutes, and then, using a roll such as an oven roll. , A vulcanizing agent, a vulcanization accelerator or a vulcanization aid as needed, and kneading at a roll temperature of 40 to 80 ° C for 5 to 30 minutes, then dispensing, ribbon-shaped or sheet-shaped compounded rubber. Prepare.

The compounded rubber thus prepared is molded into an intended shape by an extruder, a calender roll, or a press. The molded product is introduced at the same time as the molding or in a vulcanizing tank, and the temperature of 150 to 270 ° C. For 1 to 30 minutes, or by irradiating with an electron beam according to the method described above to obtain a vulcanized product. 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 the heating method in the vulcanizing tank, hot air, glass bead fluidized bed, UHF (ultra-high frequency electromagnetic wave),
A heating tank such as 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 vulcanizates produced as described above are used in the automotive industry as anti-vibration rubber, tires, and cover materials for vibrating parts.
It can be used for applications such as industrial rubber products such as parts , rubber rolls and belts, electrical insulating materials, civil engineering and construction materials, and rubber cloth. When a foaming agent is blended with the unvulcanized compounded rubber and foamed by heating, a foamed material can be obtained, and this foamed material can be used for applications such as a heat insulating material, a cushion material and a sealing material. Further, it can be blended with resins such as polyolefin, polyamide, polyester and polycarbonate to improve the impact resistance of these resins.

[0081]

According to the present invention, a vulcanized vulcanizate having excellent weather resistance, ozone resistance, heat aging resistance, low temperature properties, vibration damping properties and dynamic fatigue resistance can be obtained from the higher α-olefin copolymer of the present invention. You can get things.

Further, according to the production method of the present invention, a higher α-olefin copolymer having the above effects can be produced efficiently and in high yield. Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

[0083]

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 homogeneous solution. 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 thus obtained homogeneous solution to room temperature, 75 ml of this homogeneous solution was dropped into 200 ml of titanium tetrachloride kept at -20 ° C over 1 hour. After completion of the charging, the temperature of the mixed solution was raised to 110 ° C. over 4 hours. When the temperature reached 110 ° C., 5.22 g of diisobutyl phthalate 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, and the solid portion was resuspended in 275 ml of titanium tetrachloride, and then heated 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 [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 titanium 2.
2% by weight, 58.1% by weight of chlorine, 19.2% of magnesium
% By weight and 10.7% by weight of diisobutyl phthalate. (Polymerization) 142 ml of decane, 100 ml of octene-1 and 7-methyl-
8 ml of 1,6-octadiene were charged. The temperature of this solution was raised to 50 ° C., and hydrogen and nitrogen were each added at 1 hour / hour.
The solution was continuously introduced into the solution at a rate of 50 liters. After the temperature was raised to 50 ° C., 0.625 mmol of triisobutylaluminum, 0.21 mmol of trimethylethoxysilane and 0.0125 in terms of titanium atoms were converted.
The polymerization was started by charging mmol of the solid titanium catalyst component [A]. After polymerization at 50 ° 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. Next, after recovering the precipitated copolymer, 120
Dried under reduced pressure at ℃ for 24 hours and 12.4 g of octene-1 ·
A 7-methyl-1,6-octadiene copolymer was obtained. The intrinsic viscosity [η] of the obtained copolymer measured at 135 ° C. in decalin was 6.4 dl / g, and the content of 7-methyl-1,6-octadiene was 6.6 mol%.

[0084]

Examples 2 to 6 Copolymerization was carried out in the same manner as in Example 1 except that the higher α-olefin and the polymerization conditions were changed as shown in Table 1, and the copolymer shown in Table 1 was obtained. I got

[0085]

Comparative Example 1 The procedure of Example 1 was repeated except that 1.25 mmol and 2.5 mmol of titanium trichloride (TAC-131, manufactured by Toho Titanium Co., Ltd.) and diethylaluminum chloride were used as catalysts, respectively. Table 1
Was obtained. The activity per titanium was low, only 0.7% of Example 1.

[0086]

[Table 1]

[0087]

Example 7 Using a 4 liter glass polymerization vessel equipped with a stirring blade, octene-1 and 7-methyl-1,6-octadiene were continuously copolymerized.

That is, a decane solution of octene-1 and 7-methyl-1,6-octadiene was supplied from the upper part of the polymerization vessel to an octene-1 concentration of 155 g / liter and 7-methyl
One liter per hour so that the concentration of -1,6-octadiene in the polymerization vessel becomes 14 g / liter, and a decane slurry solution of the solid titanium catalyst component [A] as a catalyst is used to adjust the titanium concentration in the polymerization vessel to 0.05. A decane solution of triisobutylaluminum is polymerized at a rate of 0.4 liter / hour to give a mmol / L and a decane solution of trimethylethoxysilane is prepared at a rate of 1 liter / hour so that the aluminum concentration in the polymerization vessel becomes 2.5 mmol / L. 1. Hourly so that the silane concentration in the vessel is 0.83 mmol / l.
Each was continuously fed into the polymerization vessel at a rate of 6 liters. On the other hand, the polymerization liquid in the polymerization vessel always reaches 2 from the bottom of the polymerization vessel.
It was continuously withdrawn to liters. From the top of the polymerization vessel, hydrogen was supplied at a rate of 1 liter / hour and nitrogen was supplied at a rate of 50 liters / hour. The copolymerization reaction is carried out by circulating warm water through a jacket attached to the outside of the polymerization vessel.
Performed at 0 ° C.

Next, a small amount of methanol was added to the polymerization solution taken out 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 a copolymer. After sufficiently washing the copolymer with methanol, it was dried under reduced pressure at 140 ° C. for 24 hours to obtain an octane-1,7-methyl-1,6-octadiene copolymer at a rate of 225 g / h.

The content of 7-methyl-1,6-octadiene in the obtained copolymer was 7.2 mol%, and the intrinsic viscosity [η] measured in decalin at 135 ° C. was 5.2. .

[0091]

Example 8 The octene-1,7-methyl-1,6-octadiene copolymer produced in Example 1 was kneaded with an 8-inch open roll according to Table 2 to obtain an unvulcanized compound rubber. .

[0092]

[Table 2]

1) Trade name: Asahi 70: manufactured by Asahi Carbon Co., Ltd. 2) Trade name: Sansen 4240: manufactured by Nippon Sun Oil Co., Ltd. 3) Trade name: Suncellar M: manufactured by Sanshin Chemical Co. 4) Trade name: Suncellar TT: San This compound rubber is manufactured by Shin Chemical Co., Ltd.
After heating for 5 minutes, a vulcanized sheet was prepared and the following test was conducted. The test items are as follows. [Test items] Tensile test, hardness test, aging test, bending test, vibration damping property, weather resistance, ozone resistance test, low-temperature characteristics. [Test Methods] Tensile tests, hardness tests, aging tests, and bending tests were measured according to JIS K 6301. That is, in the tensile test, the tensile strength (T _B ) and the elongation (E _B ), and in the hardness test, H _S
The JISA hardness was measured, and the aging test was performed by air aging at 120 ° C. for 70 hours.

After the aging test, a tensile test was carried out, and the retention of physical properties before aging, that is, the tensile strength retention A
_R (T _B ) and elongation retention A _R (E _B ) were determined. 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 at 25 ° C. and 100 rad / sec using a dynamic spectrometer manufactured by Rheometrics as an index of the damping property. Next, the weather resistance was examined using a sunshine weather meter. The conditions of the sunshine weather meter were such that the black panel temperature was 63 ° C., the carbon arc was turned on, and water was sprayed for 18 minutes in a 120-minute cycle. This cycle is 2
After the test was performed for 00 hours, a tensile test was performed to determine the strength and elongation retention before the test.

The ozone resistance test was performed according to JIS K6301. The test conditions were an ozone concentration of 50 pphm, a test atmosphere temperature of 40 ° C., and an elongation of 30%. Low temperature characteristics
According to JIS K 6301, an impact embrittlement test was performed to determine the embrittlement temperature.

Table 3 shows the results.

[0098]

Example 9 A vulcanized sheet was obtained in the same manner as in Example 8, except that the copolymer prepared in Example 2 was used as the copolymer, and the above test was conducted.

Table 3 shows the results.

[0100]

Example 10 A vulcanized sheet was obtained in the same manner as in Example 8 except that the copolymer prepared in Example 4 was used, and the above test was conducted.

Table 3 shows the results.

[0102]

Example 11 A vulcanized sheet was obtained in the same manner as in Example 8, except that the copolymer produced in Example 5 was used, and the above test was conducted.

Table 3 shows the results.

[0104]

Comparative Example 2 In Example 8, a commercially available ethylene-propylene-diene copolymer (Mitsui EPT 3070, manufactured by Mitsui Petrochemical Industries, Ltd.) was used without using the copolymer according to the present invention.
A vulcanized sheet was obtained and subjected to the above-described test in exactly the same manner as in Example 8 except for using.

Table 3 shows the results.

[0106]

[Table 3]

[0107]

Example 12 80 parts by weight of polypropylene (Hypol J700 manufactured by Mitsui Petrochemical Co., Ltd.), 20 parts by weight of the higher α-olefin copolymer produced in Example 1, and 2,6-di-tert-butyl-4-methyl 0.1 parts by weight of phenol
After kneading at 0 ° C. for 3 minutes with a B-type Banbury mixer (manufactured by Kobe Steel), sheets were taken out with an open roll.
This was pelletized by a square pelletizer (produced by Horai Iron & Steel Co., Ltd.), subjected to injection molding, and sized to 150 mm × 120 mm ×
A 2 mm sheet was formed. The injection molding conditions are as follows.

Injection primary pressure 1000 kg / cm ² , cycle 5 seconds Holding secondary pressure 800 kg / cm ² , cycle 5 seconds Injection speed 40 mm / sec Resin temperature 230 ° C. Yield point stress from this sheet according to the method specified in JIS K 6758 ( YS) and elongation at break (EL) were measured.
The Izod impact strength was measured in an atmosphere at 23 ° C. according to 256.

Table 4 shows the results.

[0110]

Comparative Example 3 The procedure of Example 12 was repeated, except that the higher α-olefin copolymer was not used and the polypropylene was directly used for injection molding.

Table 4 shows the results.

[0112]

[Table 4]

[Brief description of the drawings]

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

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08F 236: 20) (72) Inventor Keiji Okada 3rd Chigusa Coast, Ichihara-shi, Chiba Mitsui Oil Chemical Industry Co., Ltd. (56) References JP-A-2-123114 (JP, A) JP-A-4-46909 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 210/14 C08L 23/18 B60C 1 / 00 E04H 9/02

Claims (6)

(57) [Claims] (1) a higher α-olefin having 6 to 12 carbon atoms,
A copolymer comprising a non-conjugated diene represented by the following general formula [I], wherein (a) the non-conjugated diene content is in the range of 0.01 to 30 mol%, and (b) decalin at 135 ° C. The intrinsic viscosity [η] measured in a solvent is in the range of 1.0 to 10.0 dl / g ,
Higher α-olefin copolymer for vibration damping rubber ; (Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² and R
³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, R ² and R ³ are not both hydrogen atoms. ) 2. An anti-vibration rubber obtained by vulcanizing the higher α-olefin copolymer according to claim 1 . 3. A higher α-olefin having 6 to 12 carbon atoms,
A copolymer comprising a non-conjugated diene represented by the following general formula [I], wherein (a) the non-conjugated diene content is in the range of 0.01 to 30 mol%, and (b) decalin at 135 ° C. The intrinsic viscosity [η] measured in a solvent is in the range of 1.0 to 10.0 dl / g ,
Higher α-olefin copolymer for ear use ; (Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² and R
³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, R ² and R ³ are not both hydrogen atoms. ) 4. A tire obtained by vulcanizing the higher α-olefin copolymer according to claim 3 . 5. A higher α-olefin having 6 to 12 carbon atoms,
A copolymer comprising a non-conjugated diene represented by the following general formula [I], wherein (a) the non-conjugated diene content is in the range of 0.01 to 30 mol%, and (b) decalin at 135 ° C. The intrinsic viscosity [η] measured in a solvent is in the range of 1.0 to 10.0 dl / g ,
Higher α-olefin copolymer for cover material of moving part ; (Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² and R
³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, R ² and R ³ are not both hydrogen atoms. ) 6. A cover material for a vibrating portion obtained by vulcanizing the higher α-olefin copolymer according to claim 5 .