JP3224255B2 - Higher α-olefin copolymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel higher .alpha.-olefin copolymer and a method for producing the same, and more particularly, to dynamic fatigue resistance (bending fatigue resistance), weather resistance, ozone resistance, and heat aging. The present invention relates to a higher α-olefin-based copolymer having excellent properties and low-temperature properties as well as excellent processability, and which can be used for various rubber products and resin modifiers, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Ethylene-propylene-diene copolymers have good heat resistance and ozone resistance, so they can be used in automobile industrial parts, industrial rubber products, electrical insulating materials, civil engineering building materials, rubber coatings, etc. Rubber products such as cloth, polypropylene,
Widely used as a material for plastic blending with polystyrene and the like. However, this ethylene-propylene-diene copolymer is inferior in dynamic fatigue resistance, and is therefore used for specific applications, for example, as an anti-vibration rubber, a rubber roll, a belt, a tire, and a cover material for a vibrating part. Not.

On the other hand, natural rubber is excellent in dynamic fatigue resistance, but is inferior in heat resistance and ozone resistance, and has a problem in practical use. Regarding copolymers of higher α-olefins and non-conjugated dienes, U.S. Pat. Nos. 3,933,769, 4,064,335 and 4,340,705 disclose higher α-olefins. -Copolymers of olefins with methyl-1,4-hexadiene, α, ω-diene are disclosed. However, the above-mentioned methyl-1,4-hexadiene is 4-methyl-1,4-hexadiene and 5-methyl-
Since it is a mixture with 1,4-hexadiene, and the reaction rates of the respective monomers are different, it is difficult to recover and use the monomers when performing continuous polymerization. Is different between 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene, resulting in poor monomer conversion and poor efficiency. Further, when α, ω-diene was used, a gel was formed in the copolymer, which sometimes had a bad influence on the physical properties of the final product.

Further, in the process for producing a higher α-olefin copolymer disclosed in these specifications, a catalyst comprising titanium trichloride or a catalyst comprising titanium tetrachloride and organoaluminum is used. There was a disadvantage that the production cost was not high enough.

The present inventors have intensively studied to obtain a polymer which is excellent in dynamic fatigue resistance (bending fatigue resistance), weather resistance, ozone resistance, heat aging resistance, low-temperature characteristics, and processability. When a specific higher α-olefin, a specific non-conjugated diene, and a specific α, ω-diene were copolymerized 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.

[0006]

An object of the present invention is to solve the problems associated with the prior art as described above, and is intended to solve the problems of dynamic fatigue resistance (bending fatigue resistance), weather resistance, ozone resistance and heat aging resistance. ,
It is an object of the present invention to provide a higher α-olefin copolymer excellent in low-temperature properties and processability, and a method for efficiently producing such a higher α-olefin copolymer in high yield. I have.

[0007]

SUMMARY OF THE INVENTION A higher α-olefin copolymer according to the present invention comprises a higher α-olefin having 6 to 20 carbon atoms;
A copolymer of an α, ω-diene represented by the following general formula [I] and a non-conjugated diene represented by the following general formula [II], wherein (A) the higher α-olefin and α, ω- Molar ratio with diene [higher α-olefin / α, ω-diene]
Is 95/5 to 50/50, (B) the non-conjugated diene content is 0.01 to 30 mol%, and (C) 13
The intrinsic viscosity [η] measured in decalin at 5 ° C. is 1 to 10.
dl / g.

[0008]

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

[0010]

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In the above formula [II], n is an integer of 1 to 5, R ³ is an alkyl group having 1 to 4 carbon atoms,
R ⁴ and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, no R ⁴ and R ⁵ are both hydrogen atoms.

The method for producing a higher α-olefin copolymer according to the present invention comprises the steps of (a) adding magnesium, titanium,
In the presence of a solid titanium catalyst component containing a halogen and an electron donor as essential components, (b) an organoaluminum compound catalyst component, and (c) an olefin polymerization catalyst formed from the electron donor catalyst component, the number of carbon atoms is increased. 6-20
Is copolymerized with a higher α-olefin of the above formula, an α, ω-diene represented by the above general formula [I], and a non-conjugated diene represented by the above general formula [II].

[0013]

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

First, the higher α-olefin copolymer according to the present invention will be described. The higher α-olefin-based copolymer according to the present invention is characterized in that a specific linear higher α-olefin, a specific α, ω-diene and a specific non-conjugated diene are present in a specific ratio. Is a copolymer of

Higher α-Olefin Copolymer The higher α-olefin used in the present invention is a higher α-olefin having 6 to 20 carbon atoms, and specifically, hexene-1, heptene-1, octene and the like. -1, nonene-
1, decene-1, undecene-1, dodecene-1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, nonadecene-1,
Eicosene-1, 9-methyldecene-1, 11-methyldodecene-1, 12-ethyltetradecene-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. Of the higher α-olefins, hexene-1, octene-1 and decene-1 are particularly preferably used.

Α, ω-Diene The α, ω-diene used in the present invention is represented by the following general formula [I].

[0018]

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In the above general formula [I], n is 1 to 3
Wherein R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
As the α, ω-diene as described above, specifically,
1,4-pentadiene, 1,5-hexadiene, 1,6
- heptadiene, 3-methyl-1,4-pentadiene,
3-methyl-1,5-hexadiene, 3-methyl-1,
6-heptadiene, 4-methyl-1,6-heptadiene, 3,3-dimethyl-1,4-hexadiene, 3,4
-Dimethyl-1,5-hexadiene, 4,4-dimethyl-1,6-heptadiene, 4-ethyl-1,6-heptadiene and the like.

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

[0021]

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[0022]

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In the higher α-olefin-based copolymer according to the present invention, the above-mentioned repeating units form a substantially linear structure in which the repeating units are randomly arranged. The structure of each of these repeating units can be confirmed by ¹³ C-NMR. Here, the term “substantially linear structure” means that a branched structure may be formed, but a network-like crosslinked structure is not included. The fact that the higher α-olefin-based copolymer according to the present invention forms a substantially linear structure means that this copolymer is completely dissolved in decalin at 135 ° C., and a gel-like cross-linked polymer is formed. It can be confirmed by not containing.

Non-conjugated diene The non-conjugated diene used in the present invention has the following general formula [I
I].

[0025]

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In the general formula [II], n is an integer of 1 to 5, R ³ is an alkyl group having 1 to 4 carbon atoms, and R ⁴ and R ⁵ are a hydrogen atom or a carbon atom. 1 to
And R ⁴ and R ⁵ are not both hydrogen atoms.

As the non-conjugated diene as described above, specifically, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 5- Methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-
Ethyl-1,5-heptadiene, 4-methyl-1,4-
Octadiene, 5-methyl-1,4-octadiene, 4
-Ethyl-1,4-octadiene, 5-ethyl-1,4
-Octadiene, 5-methyl-1,5-octadiene,
6-methyl-1,5-octadiene, 5-ethyl-1,
5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-
1,6-octadiene, 6-ethyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-
1,4-nonadiene, 4-ethyl-1,4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-
1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-
1,5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-
1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-
1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-
1,4-decadiene, 5-methyl-1,5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl-
1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 7-methyl-
1,6-decadiene, 6-ethyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-
1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-
1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-
Examples thereof include 1,8-decadiene and 9-methyl-1,8-undecadiene.

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

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

In the present invention, α, ω is added to the higher α-olefin.
-Processability of higher α-olefin copolymer can be improved by copolymerizing diene. The content of the non-conjugated diene constituting the higher α-olefin-based copolymer of the present invention is 0.01 to 30 mol%, preferably 0.1 to 30 mol%.
-20% by mole, particularly preferably in the range of 0.1-10% by mole, and the iodine value is 2-40, preferably 5-3%.
It is in the range of 0. 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 at 135 ° C. in a decalin solvent is as follows:
1.0 to 10.0 dl / g, preferably 1.5 to 7 dl
/ G. This characteristic value is a measure of the molecular weight of the higher α-olefin copolymer of the present invention, and is combined with other characteristic values to provide weather resistance, ozone resistance, heat aging resistance, low temperature characteristics, dynamic resistance. This is useful for obtaining a copolymer having excellent properties such as fatigue.

The higher α-olefin copolymer according to the present invention as described above can be produced by the following method. The higher α-olefin-based copolymer according to the present invention is prepared by adding a higher α-olefin having 6 to 20 carbon atoms to an α, ω-diene represented by the above general formula [I] in the presence of an olefin polymerization catalyst. And a non-conjugated diene represented by the above general formula [II].

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 used in producing the higher α-olefin copolymer 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.

The solid titanium catalyst component (a) is
It is prepared by contacting a magnesium compound, a titanium compound and an electron donor as described below. In the present invention, the titanium compound used for preparing the solid titanium catalyst component (a) includes, 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, TiCl ₄ , TiB
r ₄ , titanium tetrahalide such as TiI ₄ ; Ti
(OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (O
_{n -C 4 H 9) Cl 3} , Ti (OC 2 H 5) Br 3, Ti (O
-Iso-C ₄ H ₉₎ trihalide, alkoxy titanium such as _{Br 3; Ti (OCH 3)} 2 Cl 2, Ti (OC 2 H 5) 2 C
_{l 2, Ti (O n -C} 4 H 9) 2 Cl 2, Ti (OC 2 H 5) 2
Dihalogenated dialkoxytitanium such as Br ₂ ; Ti
(OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Cl, Ti (O
monohalogenated trialkoxy titanium such as _n- C ₄ H ₉ ) ₃ Cl and Ti (OC ₂ H ₅ ) ₃ Br; Ti (OCH ₃ ) ₄ ;
_{Ti (OC 2 H 5) 4} , Ti (O n -C 4 H 9) 4, Ti (O
-Iso-C ₄ H ₉₎ such as _4, Ti (tetraalkoxy titanium such as O-2-ethylhexyl) ₄ can be mentioned.

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

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

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 may 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 magnesium compound having no reducing property 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 chloride, butoxy magnesium and octoxy magnesium chloride; Alkoxy magnesium halides such as magnesium phenoxy chloride and methyl phenoxy magnesium chloride; ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2-ethylhexoxy magnesium Alkoxymagnesium such as;
Alloxymagineium such as phenoxymagnesium and dimethylphenoxymagnesium; and magnesium carboxylate such as magnesium laurate and magnesium stearate.

These non-reducing magnesium compounds may be compounds derived from the above-mentioned reducing magnesium compounds or compounds 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 preferable, and halogen-containing magnesium compounds are particularly preferable. Among these, magnesium chloride, alkoxymagnesium chloride and allyloxymagnesium chloride are preferably used. Can be

In the present invention, examples of the electron donor used for preparing the solid titanium catalyst component (a) include an organic carboxylic acid ester and a polyvalent carboxylic acid ester described below. Compounds having the following skeleton.

[0045]

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[0046]

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[0047]

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[0048]

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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 , 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, -C-O-C
-, - COOR, -COOH, -OH , -SO 3 H, -
Substituted hydrocarbon groups having a structure such as C—N—C— and —NH ₂ are mentioned.

Of these, diesters 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 are preferred. Specific examples of the polycarboxylic acid ester include diethyl succinate, dibutyl succinate, diethyl methyl succinate, α-
Diisobutyl methyl glutarate, dibutyl methyl malonate, diethyl malonate, diethyl ethyl malonate, diethyl isopropyl malonate, diethyl butyl malonate,
Diethyl phenylmalonate, diethyl diethylmalonate, diethyl allylmalonate, diethyldiisobutylmalonate, diethyldinormalbutylmalonate, dimethylmaleate, monooctylmaleate, diisooctylmaleate, diisobutylmaleate, diisobutylbutylmaleate, butylmaleate Fatty acid polycarboxylic acid esters such as diethyl acrylate, diisopropyl β-methylglutarate, diallyl ethylsuccinate, di-2-ethylhexyl fumarate, diethyl itaconate, diisobutyl itaconate, diisooctyl citrate, and dimethyl citrate; 1,2-cyclohexane Aliphatic polymers such as diethyl carboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadicate Carboxylic acid ester; monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate,
Monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, mono-normal butyl phthalate, ethyl normal butyl phthalate, di-n-propyl phthalate,
Diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, didecyl phthalate, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, Aromatic polycarboxylic esters such as dibutyl naphthalene dicarboxylate, triethyl trimellitate and dibutyl trimellitate; esters derived from heterocyclic polycarboxylic acids such as 3,4-furandicarboxylic acid;

Other examples of the polycarboxylic acid ester include diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, n-octyl sebacate, di-2-ethylhexyl sebacate and the like. And esters derived from long-chain dicarboxylic acids.

Among these polycarboxylic acid esters,
Compounds having a skeleton represented by the aforementioned general formula are preferable, and more preferably esters derived from phthalic acid, maleic acid, substituted malonic acid and the like and alcohols having 2 or more carbon atoms, and phthalic acid and carbon atoms Number 2
Diesters obtained by the above reaction with alcohols 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 may be used during the preparation of the solid titanium catalyst component (a). A polycarboxylic acid ester may be formed in the step of preparing the solid titanium catalyst component (a) using a compound capable of deriving an ester.

In the present invention, examples of the electron donor other than the polyvalent carboxylic acid which can be used in preparing the solid titanium catalyst component (a) include alcohols, amines, amides and the like as described later. Ethers, ketones, nitriles, phosphines, stippins, arsines, phosphoramides, esters, thioethers,
Organosilicon compounds such as thioesters, acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy (aryloxy) silanes, organic acids, and amides of metals belonging to Groups I to IV of the Periodic Table And salts.

In the present invention, the solid titanium catalyst component (a) can be produced by 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 in which a magnesium compound or a complex compound comprising a magnesium compound and an electron donor is reacted 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 composite agent. (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 acid compound, 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 at the time of preparing the catalyst, a method using a titanium compound, 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 about 0.01 to 500 moles, preferably 0.05 to 3 moles, of the titanium compound.
It is used in an amount of 00 mol.

The solid titanium catalyst component (a) thus obtained contains magnesium, titanium, halogen and an electron donor as essential components. In this solid titanium catalyst component (a), the halogen / titanium (atomic ratio) is about 4-200, preferably about 5-100,
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 1, 000m
² / g, more preferably about 100 to 800 m ² / g. Since the solid titanium catalyst component (a) forms a catalyst component by integrating the above components, the composition is not substantially changed by hexane washing.

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.

A method for preparing such a highly active titanium catalyst component is described in, for example, JP-A-50-108385.
No. 50-126590, No. 51-20297, No. 51-28189, No. 51-64586, No. 51-92885, No. 51-1366
No. 25, No. 52-87489, No. 52-100596,
No. 52-147688, No. 52-104593, No. 53-2580, No. 53-40093, No. 53-40094, No. 53-430
No. 94, No. 55-135102, No. 55-135103,
No. 55-152710, No. 56-811, No. 56-11908, No. 56-18606, No. 58-83006, No. 58-1387
No. 05, No. 58-138706, No. 58-138707,
No. 58-138708, No. 58-138709, No. 58-1387
No. 10, No. 58-138715, No. 60-23404, No.
These are disclosed in JP-A-61-21109, JP-A-61-37802, and JP-A-61-37803.

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

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

As the aluminum compound belonging to the above (i), more specifically, trialkylaluminums such as triethylaluminum and tributylaluminum; trialkenylaluminums such as triisoprenylaluminum; diethylaluminum ethoxide, dibutylaluminum butoxide and the like Dialkylaluminum alkoxides; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; (R ¹ ) _2.5 A
l (O (R ²⁾⁾ partially alkoxylated alkyl aluminum having an average composition represented by like _0.5;
Dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride and diethylaluminum bromide; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide Alkyl aluminum dihalides such as alkylaluminum dihalide; dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride Partially hydrogenated Kill aluminum; ethylaluminum ethoxy chloride, butyl aluminum butoxide cycloalkyl chloride, can be mentioned partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxy bromide.

Examples of the compound similar to the aluminum compound belonging to the above (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 AlOAl (C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ A
_{lOAl (C 4 H 9) 2} , (C 2 H 5) 2 AlN (C 2 H 5) A
l (C ₂ H ₅ ) ₂ and methylaminooxane.

Compounds belonging to the above (ii) include L
iAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ can be exemplified. 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, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, and oxygen-containing compounds such as alkoxysilanes. An electron donor, a nitrogen-containing electron donor such as ammonia, amine, nitrile, and isocyanate, or the above-mentioned polyvalent carboxylic acid ester can be used.

More specifically, carbon such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropyl benzyl alcohol, etc. Alcohols having 1 to 18 atoms; phenol, cresol, xylenol, ethylphenol, propylphenol,
C6-C20 which may have a lower alkyl group, such as nonylphenol, cumylphenol and naphthol.
Phenols; ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone;
Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, propionic acid Ethyl, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, Cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, n-butyl maleate, methylmalo Diisobutyl, cyclohexene carboxylic di -n- hexyl, nadic diethyl, tetrahydrophthalic acid diisopropyl, diethyl phthalate, diethyl phthalate, diisobutyl phthalate, di -
Organic acid esters having 2 to 30 carbon atoms, such as n-butyl, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate; acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid 2 to 1 carbon atoms such as chloride
5 acid halides; methyl ether, ethyl ether,
Ethers having 2 to 20 carbon atoms such as isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether; acid amides such as acetic acid amide, benzoic acid amide and toluic acid amide; methylamine, ethylamine, diethylamine and tributylamine Amines such as, for example, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylenediamine; nitriles such as acetonitrile, benzonitrile, tolunitrile; acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride; Can be

As the electron donor (c), an organosilicon compound represented by the following general formula [II] can also be used. R _n Si (OR ′) _4-n ... [1] (wherein R and R ′ are hydrocarbon groups, and n is 0 <n
<4. As the organosilicon compound represented by the general formula [1], specifically, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane,
Diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-ο-tolyldimethoxysilane,
Bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane , Ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n
-Propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltoluethoxysilane, ethyltriethoxysilane,
Vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-
Aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyl Dimethoxysilane,
Ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxy silane, vinyl tris (β-methoxyethoxy silane), vinyl triacetoxy silane, dimethyl tetraethoxy disiloxane and the like are used.

Of these, ethyltriethoxysilane, n-
Propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis
-p-Tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, and diphenyldiethoxysilane are preferred.

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

In the above formula [2], 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 allyl group such as an isopropyl group, a butyl group, and a hexyl group, or a cyclopentyl group having a cyclopentyl group and an alkyl group exemplified as R ¹ can be similarly mentioned.

In the above formula [2], R ³ is a hydrocarbon group, and examples of R ³ include hydrocarbon groups such as an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group.

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,
Monoallocoxysilanes such as dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, cyclopentyldimethylethoxysilane and the like can be mentioned. Among these electron donors, organic carboxylic acid esters or organic silicon compounds are preferable, and organic silicon compounds are particularly preferable.

The olefin polymerization catalyst used in the present invention is formed from the solid titanium catalyst component (a), the organoaluminum compound catalyst component (b), and the electron donor catalyst component (c) as described above. In the present invention, a higher α-olefin and α,
The ω-diene and the non-conjugated diene are polymerized. After preliminarily polymerizing the α-olefin or higher α-olefin using the catalyst for olefin polymerization, the higher α-olefin and α, The ω-diene and the non-conjugated diene can be polymerized (main polymerization). During the prepolymerization, 0.1 to 500 per gram of the olefin polymerization catalyst is used.
g, preferably 0.3 to 300 g, particularly preferably 1 to
The α-olefin or higher α-olefin is prepolymerized in an amount of 100 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 as follows:
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
0.1 to 500 g per 1 g of the solid titanium catalyst component (a),
The amount is preferably such that a polymer of 0.3 to 300 g is produced, and usually about 0.1 to 100 mol, preferably about 0.1 to 100 mol per mol of titanium atom in the solid titanium catalyst component (a). It is desirable that the amount is 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. Specific examples of the inert hydrogen medium used at this time include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, and the like. Alicyclic 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 olefin or higher α-olefin itself can be pre-polymerized in a solvent, or can be pre-polymerized 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 about 0.1 of a polymer obtained by prepolymerization, measured in a decalin solvent at 135 ° C.
It is desirable to use an amount of 2 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 solid titanium catalyst component (a) or the solid titanium catalyst component (a) obtained by prepolymerizing the olefin polymerization catalyst as described above, the organoaluminum catalyst component (b), and the electron donor catalyst component ( c) in the presence of an olefin polymerization catalyst formed from
-Copolymerization (main polymerization) of olefin, α, ω-diene and non-conjugated diene.

In the copolymerization (main polymerization) of a higher α-olefin, α, ω-diene and non-conjugated diene, the olefin polymerization catalyst is used as an organoaluminum compound catalyst component in addition to the olefin polymerization catalyst. The same components as the organoaluminum compound catalyst component (b) used in producing the catalyst for use can be used. In addition, in the copolymerization (main polymerization) of a higher α-olefin, α, ω-diene, and a non-conjugated diene, the electron donor catalyst component used for producing an olefin polymerization catalyst is used. Components similar to the donor catalyst component (c) can be used. The organoaluminum compound and the electron donor used in the copolymerization of the higher α-olefin, α, ω-diene and non-conjugated diene (main polymerization) are not necessarily prepared by preparing the above-mentioned olefin polymerization catalyst. It need not be the same as the organoaluminum compound and electron donor used in the reaction.

Copolymerization (main polymerization) of a higher α-olefin, α, ω-diene and non-conjugated diene is usually carried out in a liquid phase. As the reaction medium for the main polymerization, the above-mentioned inert hydrocarbon medium can be used, or an olefin liquid at the reaction temperature can be used.

In the copolymerization (main polymerization) of a higher α-olefin, α, ω-diene and non-conjugated diene, the solid titanium catalyst component (a) is converted into titanium atoms per liter of polymerization volume, Usually it is used in an amount of about 0.001 to about 1.0 mmol, preferably about 0.005 to 0.5 mmol. Further, the organic aluminum catalyst component (b)
The metal atom in the organoaluminum compound catalyst component (b) is usually about 1 to 2,000 moles, preferably about 5 to 5 moles per mole of titanium atom in the solid titanium catalyst component (a).
It is used in an amount of 500 moles. Further, the electron donor catalyst component (c) is usually added in an amount of about 0.00 per mole of metal atom in the organoaluminum compound catalyst component (b).
It is used in an amount of 1 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.05 to 1 mol.

When hydrogen is used at the time of the main polymerization, the molecular weight of the obtained polymer can be adjusted. In the present invention, the polymerization temperature of the higher α-olefin, α, ω-diene and non-conjugated diene is usually about 20 to 200 ° C, preferably about 40 to 100 ° C, and the pressure is usually normal pressure to normal pressure. 100
kg / cm ^2, preferably from normal pressure to 50 kg / cm ² . In the copolymerization (main polymerization) of a higher α-olefin, α, ω-diene and non-conjugated diene,
It can be carried out by any of batch, semi-continuous and continuous methods. 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 excellent in dynamic fatigue resistance (bending fatigue resistance), weather resistance, ozone resistance, heat aging resistance, low-temperature properties and processed. It is used as a polymer with excellent properties. Especially when applied to resin modifiers and various rubber products,
It demonstrates its characteristics to the maximum.

As the resin modifier, for example, it can be used as a modifier such as polypropylene, polyethylene, polybutene, polystyrene, ethylene / cyclic olefin copolymer and the like. When the higher α-olefin copolymer of the present invention is added to these resins, impact resistance and stress crack resistance can be drastically 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 as in the case of vulcanizing a general rubber, an unvulcanized compounded rubber is prepared once, and then It is manufactured by molding this compounded rubber into an intended shape and then performing 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 at the time of 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 0.1 to 10 parts by weight based on 100 parts by weight of the higher α-olefin copolymer of the present invention,
It is preferably used in an amount of 0.5 to 5 parts by weight.

The organic peroxide may be any one which is usually used for peroxide vulcanization of rubber. For example, dicumyl peroxide, di-t-butyl peroxide,
-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butyl hydroperoxide, t-butylcumyl peroxide, benzoyl peroxide,
2,5-dimethyl-2,5-di (t-butylperoxin) hexyne-3,2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,2
5-mono (t-butylperoxy) -hexane, α,
α'-bis (t-butylperoxy-m-isopropyl)
Benzene and the like can be mentioned. Among them, dicumyl peroxide, di-t-butyl peroxide and di-t-butylperoxy-3,3,5-trimethylcyclohexane are preferably used. One or more of these organic peroxides are used in an amount of 0.0003 to 0.05 mol, preferably 0.001 to 0.03 mol, per 100 g of the higher α-olefin copolymer. Used in
It is desirable to appropriately determine the optimum amount according to the required physical property values.

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-benzothiazol-sulfenamide, N-oxydiethylene-2-benzothiazol-sulfenamide, N, N-diisopropyl-2-benzothiazol-sulfenamide ,
2-mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,2
6-diethyl-4-morpholinothio) benzothiazole,
Thiazole compounds such as dibenzothiazyl disulfide; diphenylguanidine, triphenylguanidine,
Guanidine compounds such as diornitrile guanidine, orthonitrile biguanide, diphenylguanidine phthalate; aldehyde amines such as acetaldehyde-aniline reactant, butyraldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde ammonia and aldehyde-ammonia compounds Compounds: imidazoline compounds such as 2-mercaptoimidazoline; thiourea compounds such as thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea; tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram Thiuram compounds such as disulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide; Dithioacid salts such as zinc methyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate and tellurium dimethyldithiocarbamate Zantate compounds such as zinc dibutylxanthogenate; and compounds such as zinc white. These vulcanization accelerators are 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 higher α-olefin copolymer.

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

When an electron beam is used without using a vulcanizing agent as a vulcanizing method, a molded unvulcanized compounded rubber described below is added to a molded unvulcanized compounded rubber in an amount of 0.1 to 10 MeV (megaelectron volt), preferably 0.3 to 10 MeV. An electron having an energy of ~ 2 MeV, an absorbed dose of 0.5 to 35 Mrad (mega rad),
Irradiation is preferably performed so as to be 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 of the organic peroxide is 0 to 100 g of the higher α-olefin copolymer. 0.0001 to 0.1 mol, preferably 0.001 to 0.1
What is necessary is just to mix | blend in the ratio of 0.03 mol.

The unvulcanized compounded rubber is prepared by the following method. That is, after a higher α-olefin-based 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, the mixture is mixed with an open roll. After adding a vulcanizing agent and, if necessary, a vulcanization accelerator or a vulcanization aid, the mixture is kneaded at a roll temperature of 40 to 80 ° C. for 5 to 30 minutes, and then mixed. To prepare a ribbon or sheet compound rubber. As described above, the compounded rubber using the higher α-olefin-based copolymer of the present invention, that is, the vulcanizable rubber composition, is obtained by mixing the respective components with a roll, a Banbury, a kneader, etc. which are usually used in the rubber industry. Manufactured. Also,
Carbon black usually used in the rubber industry, reinforcing agents such as silica, fillers such as calcium carbonate and talc, triallyl isocyanurate, trimerol propane triacrylate, crosslinking aids such as m-phenylene bismaleimide, plasticizers, Various chemicals such as stabilizers, processing aids, and coloring agents can be appropriately mixed and used as needed.

The compounded rubber prepared as described above is
It is formed into an intended shape by an extruder, a calender roll or a press. Simultaneously with the molding or by introducing the molded product into a vulcanization tank and heating at a temperature of 150 to 270 ° C. for 1 to 30 minutes, or A vulcanized product is obtained by irradiating an electron beam according to 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 glass bead fluidized bed, 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 vulcanizates produced as described above can be used as such, such as anti-vibration rubber, automobile industrial parts such as cover materials for tire vibrating parts, industrial rubber products such as rubber rolls and belts, and electric rubber products. It can be used for applications such as insulating materials, civil engineering materials and rubberized fabrics. When a foaming agent is blended with the unvulcanized 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.

[0103]

The higher α-olefin copolymer according to the present invention contains a specific higher α-olefin, a specific α, ω-diene and a specific non-conjugated diene in a specific ratio, and Because it has viscosity [η], weather resistance, ozone resistance,
In addition to being excellent in heat aging resistance, low-temperature properties, vibration damping properties, and dynamic fatigue resistance, it has the effect of being excellent in workability, and the above-described properties can provide a more excellent vulcanizate.

Further, according to the method for producing a higher α-olefin copolymer according to the present invention, a higher α-olefin copolymer having the above-mentioned effects can be produced efficiently and in high yield. Can be.

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

[0106]

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. Thereafter, 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 to dissolve phthalic anhydride in the homogeneous solution. After cooling the homogeneous solution thus obtained to room temperature, 75 ml of titanium tetrachloride 2 was kept at -20 ° C.
The entire amount was dropped into 00 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 was added.
5.22 g was added thereto, 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 by hot filtration again,
The plate was washed sufficiently with decane and hexane at 10 ° C. until no free titanium compound was detected in the washing solution. The titanium catalyst component (a) prepared by the above operation was stored as a decane slurry, and a part thereof was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component (a) thus obtained was composed of 2.5% by weight of titanium,
5% by weight, 19% by weight of magnesium and 13.5% by weight of diisobutyl phthalate. [Polymerization] The copolymerization reaction of octene-1, 1,5-hexadiene and 7-methyl-1,6-octadiene was continuously performed using a 4-liter glass polymerization vessel equipped with stirring blades. Was.

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

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 give octene-1.
A 1,5-hexadiene / 7-methyl-1,6-octadiene copolymer was obtained at a rate of 90 g / h.

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

[0110]

Examples 2 to 6 In Example 1, copolymerization was carried out in the same manner as in Example 1 except that higher α-olefins and polymerization conditions were changed as shown in Table 1 to obtain copolymers as shown in Table 1. A coalescence was obtained.

In the copolymer obtained in Example 5, ¹³ C-
From the result of NMR analysis, the repeating unit derived from the 1,5-hexadiene component formed a ring structure represented by the following formula, and a trace of a peak due to a terminal double bond was observed. From the peak intensity, it was confirmed that 99% or more formed this ring structure.

[0112]

Embedded image

Hexene-1,1,5-hexadiene.7
- ¹³ C-NMR of methyl 1,6-octadiene copolymer
Each peak on the spectrum was as follows with deuterated benzene as a reference (128.0 ppm).

No. 11 Chemical shift [ppm] Chemical shift [ppm] 30.9-32.9 13. 38.4 2. 33.6-34.1 14. 35.3 3. 38.4 15. 29.3-29.4 4. 39.8-39.9 23.5 to 23.6 5. 40.1-41.0 17. 14.3 6. 42.5-42.7 18. 27.1 to 27.3 7. 44.3-44.4 19. 135.2 8. 40.5-44.4 20. 124.0-124.5 9. 40.5-43.0 21. 14.3 10. 33.7-35.1 22. 17.9 11. 36.3 23. 140 12. 37.0-37.1 24. 115 In the following formula, C represents a cis type, and T
Represents a trans type.

[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[Table 1]

[0126]

Example 7 Octene 1.1,1 produced in Example 1
According to Table 2, 5-hexadiene / 7-methyl-1,6-octadiene copolymer was kneaded with 8-inthio-pump roll to obtain an unvulcanized compound rubber. Workability at that time was evaluated, and the results are shown in Table 3.

[0127]

[Table 2] 1) Trade name: Asahi 80; manufactured by Asahi Carbon Co., Ltd. 2) Trade name: Sancera-M; manufactured by Sanshin Chemical Industry Co., Ltd. 3) Trade name: Sancera-TT; manufactured by Sanshin Chemical Industry Co., Ltd. Further, this compounded rubber was heated by a press heated to 160 ° C. for 20 minutes to produce a vulcanized sheet, and the following test was conducted. The test items are as follows. (Test items) Tensile test, hardness test, ozone resistance test, aging test, bending test, low temperature characteristics (Test method) Tensile test, hardness test, ozone resistance test, aging test, bending test are measured according to JIS K6301. did.

That is, the tensile test (T _B ) and the elongation (E _B ) in the tensile test, and the JISA hardness (H
_s ) was measured. The ozone resistance test is performed in an ozone test tank (ozone concentration: 50 pphm, elongation: 20%, temperature: 40 ° C., time: 200 hours, static test), and the state of surface deterioration (whether cracks are generated) is evaluated. did.

In the aging test, an air heating aging test was performed at 120 ° C. for 70 hours, and the retention ratios for physical properties before aging, that is, tensile strength retention ratio A _R (T _B ) and elongation retention ratio A _R (E _B )
I asked.

The flex test examined the resistance to crack growth in a dematcher tester. That is, the crack is 15mm
The number of times of bending until became. Low temperature characteristics are based on JIS
An impact embrittlement test was performed according to K6301, and the embrittlement temperature was determined.

Table 3 shows the results.

[0132]

[Embodiment 8] In Example 7, the octene of Example 1 was used.
Instead of the 1,1,5-hexadiene-7-methyl-1,6-octadiene copolymer, octene-1,1,5-hexadiene-7-methyl-1, produced in Example 2 was used.
Example 7 was repeated except that a 6-octadiene copolymer was used.

Table 3 shows the results.

[0134]

Ninth Embodiment In the seventh embodiment, the octene of the first embodiment is used.
Instead of the 1,1,5-hexadiene.7-methyl-1,6-octadiene copolymer, the hexene-1,1,5-hexadiene.7-methyl-1, produced in Example 3 was used.
Example 7 was repeated except that a 6-octadiene copolymer was used.

Table 3 shows the results.

[0136]

Example 10 In Example 7, the octene of Example 1 was used.
-Instead of the 1,1,5-hexadiene-7-methyl-1,6-octadiene copolymer, the hexene-1,1,5-hexadiene-7-methyl- produced in Example 4 was used.
Example 7 was repeated except that a 1,6-octadiene copolymer was used.

Table 3 shows the results.

[0138]

Example 11 In Example 7, the octene of Example 1 was used.
-Instead of the 1,1,5-hexadiene-7-methyl-1,6-octadiene copolymer, the hexene-1,1,5-hexadiene-7-methyl- produced in Example 5 was used.
Example 7 was repeated except that a 1,6-octadiene copolymer was used.

Table 3 shows the results.

[0140]

Example 12 In Example 7, the octene of Example 1 was used.
-Instead of the 1,1,5-hexadiene / 7-methyl-1,6-octadiene copolymer, the decene-1,1,6-heptadiene / 7-methyl-1, produced in Example 6
Example 7 was repeated except that a 6-octadiene copolymer was used.

Table 3 shows the results.

[0142]

Comparative Example 1 In Example 1, copolymerization was carried out in the same manner as in Example 1 except that 1,5-hexadiene was not used, and under the polymerization conditions shown in Table 1, to give octene-1,7-methyl-1,6-
An octadiene copolymer was obtained.

Next, in Example 7, the octene-1,1,5-hexadiene / 7-methyl-1,1 of Example 1 was used.
Example 7 was repeated, except that the octene-1.7-methyl-1,6-octadiene copolymer obtained as described above was used instead of the 6-octadiene copolymer.

Table 3 shows the results.

[0145]

[Table 3]

[0146]

Example 13 80 parts by weight of polypropylene (manufactured by Mitsui Petrochemical Industry Co., Ltd., product number J700) and 80 parts by weight of octene-1,1,5-hexadiene-7- produced in Example 1
20 parts by weight of a methyl-1,6-octadiene copolymer,
0.1 part by weight of 2,6-di-t-butyl-4-methylphenol was kneaded with a Banbury mixer at 190 ° C. for 3 minutes and then sheeted out with an open roll. The resulting sheet was pelletized with a square pelletizer.

Next, the pellets obtained as described above were subjected to injection molding to obtain a pellet having a size of 150 mm × 120 mm × 2 mm.
Was formed. The injection molding conditions are as follows. (Injection molding conditions) Primary injection pressure: 1000 kg / cm ² , cycle 5 seconds Secondary injection pressure: 800 kg / cm ² , cycle 5 seconds Injection speed: 40 mm / sec Resin temperature: 230 ° C. JIS K using this sheet The yield point stress (Y _S ) and the elongation at break (E _L ) were measured by the method specified in 6758.
Further, Izod impact strength was measured in an atmosphere at 23 ° C. according to ASTM D256.

Table 4 shows the results.

[0149]

Comparative Example 2 The procedure of Example 13 was repeated, except that the higher α-olefin-based copolymer was not used, and the polypropylene was directly used for injection molding.

Table 4 shows the results.

[0151]

[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.

──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Keiji Okada 3rd Chikusa Beach, Ichihara-shi, Chiba Mitsui Oil Chemical Industry Co., Ltd. No. 1-2 in Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A-2-123114 (JP, A) JP-A-2-49008 (JP, A) JP-A-3-131164 (JP, A) ( 58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 210/00-210/18 C08F 4/00-4/82 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A higher α-olefin having 6 to 20 carbon atoms, an α, ω-diene represented by the following general formula [I],
A copolymer of a non-conjugated diene represented by the following general formula [II]: (A) a molar ratio of the higher α-olefin to α, ω-diene [higher α-olefin / α, ω-diene] ] Is 95/5
(B) the non-conjugated diene content is 0.01 to 30 mol%, and (C) the intrinsic viscosity [η] measured in decalin at 135 ° C.
Is higher than 1 to 10 dl / g, a higher α-olefin copolymer; Wherein n is an integer of 1 to 3, and R ¹ and R ² are
Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms], [In the formula, n is an integer of 1 to 5, and R ³ has 1 carbon atom.
Represents to 4 alkyl groups, R ⁴ and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁴
And R ⁵ cannot both be hydrogen atoms]. 2. A catalyst comprising: (a) a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components; (b) an organoaluminum compound catalyst component; and (c) an electron donor catalyst component. In the presence of an olefin polymerization catalyst, a higher α-olefin having 6 to 20 carbon atoms, an α, ω-diene represented by the following general formula [I], and a non-conjugated diene represented by the following general formula [II] And a method for producing a higher α-olefin copolymer, characterized by copolymerizing Wherein n is an integer of 1 to 3, and R ¹ and R ² are
Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms], [In the formula, n is an integer of 1 to 5, and R ³ has 1 carbon atom.
Represents to 4 alkyl groups, R ⁴ and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁴
And R ⁵ cannot both be hydrogen atoms].