JPH02281011A - Higher alpha-olefin copolymer, its production and its vulcanized product - Google Patents

Abstract

PURPOSE:To obtain the subject novel copolymer free from generation of gel and giving a vulcanized product having excellent weather resistance, thermal aging resistance, etc., by copolymerizing a specific alpha-olefin and a specific non- conjugated diene in the presence of a specific catalyst. CONSTITUTION:The objective copolymer containing 0.01 to 30mol% of the non-conjugated diene of formula and having an intrinsic viscosity [eta] of 1 to 10dl/g measured in decalin solvent at 135 deg.C can be produced by copolymerizing a 6 to 12C higher alpha-olefin and a non-conjugated diene of formula (R<1> is 1 to 4C alkyl; R<2> and R<3> are H or R<1> provided that R<2> and R<3> are not H at the same time) (preferably 7-methyl-1,6-octadiene) in the presence of an olefin- polymerization catalyst consisting of (A) a solid titanium catalyst component containing Mg, Ti, a halogen and an electron donor as essential components (B) an organic Al compound catalyst component and (C) an electron donor catalyst component.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a novel higher α-olefin copolymer, a method for producing the same, and a vulcanizate thereof, and more particularly, dynamic fatigue resistance (flexural fatigue resistance). , has excellent properties such as weather resistance, ozone resistance, heat aging resistance, and low temperature properties, and is suitable for various rubber products,
The present invention relates to a higher α-olefin copolymer that can be used as a resin modifier, a method for producing the same, and a vulcanizate thereof.

Technical background of the invention The vulcanizate of ethylene-propylene-diene copolymer is
Due to its good heat resistance and ozone resistance, it is widely used as a plastic blending material for automobile industrial parts, industrial rubber products, electrical insulation materials, civil engineering and construction materials, rubber products such as rubberized cloth, polypropylene, polystyrene, etc. It is used. However, this ethylene-propylene diene copolymer has poor dynamic fatigue resistance, making it unsuitable for certain uses, such as anti-vibration rubber, rubber rolls, belts, tires, and covering materials for vibrating parts. .

On the other hand, U.S. Patent No. 3,933,769 discloses that at least one monomer selected from ■-butene and α-olefin having 5 to 12 carbon atoms, 5-methyl-1,4-hexadiene and 4-methyl-1,4 - copolymerizing a mixture of hexadiene (5-methyl-1,4-hexadiene is at least 15% or more) with a coordination catalyst,
A sulfur vulcanizable copolymer with low gel content is disclosed. Furthermore, U.S. Patent No. 4,340,705 discloses that a monoolefin having 4 to 12 carbon atoms and a non-conjugated monoolefin having 4 to 12 carbon atoms are combined with a catalyst system in which a hexaalkyl phosphoric triamide or an organic phosphoric acid ester is added to a transition metal compound and an organoaluminum compound. The present invention discloses high molecular weight, sulfur vulcanizable, low gel content copolymers copolymerized with α,ω-polyenes of from 8 to about 36.

The present inventors have conducted extensive research in order to obtain a polymer that can yield a vulcanizate that has excellent properties such as weather resistance, ozone resistance, and heat aging resistance, as well as excellent dynamic properties such as bending resistance. When a specific higher α-olefin and a specific non-conjugated diene were copolymerized in the presence of a specific olefin polymerization catalyst, a new higher α-olefin copolymer with excellent properties as described above and without gel formation was obtained. It was discovered that a polymer can be obtained, and the present invention was completed.

OBJECTS OF THE INVENTION The present invention thus provides a novel higher alpha-olefin/non-conjugated diene copolymer which is vulcanizable and substantially free of gel formation.

Furthermore, the present invention provides a method for producing the above novel copolymer.

Furthermore, the present invention also provides the above-mentioned novel higher α-olefin.
Provided is a new vulcanizate obtained from a non-conjugated diene copolymer that has excellent weather resistance, ozone resistance, heat aging resistance, low temperature properties, vibration damping properties, and dynamic fatigue resistance.

Summary of the Invention The higher α-olefin copolymer according to the present invention is a copolymer consisting of a higher α-olefin having 6 to 12 carbon atoms and a non-conjugated diene represented by the following general formula [I1], CB) The non-conjugated diene content is within the range of 0.01 to 30 mol%, (b) The intrinsic viscosity [η] determined by 11) I in a decalin solvent at 135°C is 1.0 to 10. It is characterized by being within the range of OdN/g.

(In the formula, R is an alkyl group having 1 to 4 carbon atoms, R2 and R
3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, R and R3 are never both hydrogen atoms. ) Further, the method for producing a higher α-olefin copolymer according to the present invention includes: [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] a higher α-olefin having 6 to 12 carbon atoms in the presence of an olefin polymerization catalyst formed from an electron donor catalyst component, and the following - general formula [I]
The non-conjugated diene content is within the range of 0.01 to 30 mol%, and 13
The intrinsic viscosity [η] measured in a decalin solvent at 5°C is 1.
0-10. Odd! It is characterized by obtaining a higher α-olefin copolymer within the range of /g.

(In the formula, R1 represents an alkyl group having 1 to 4 carbon atoms, and R2 and R3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, R and R3 are not both hydrogen atoms.) , the vulcanizate according to the present invention is a high grade α-
It is characterized by being a vulcanized product of an olefin copolymer.

DETAILED DESCRIPTION OF THE INVENTION The higher α-olefin copolymer, the method for producing the same, and the vulcanizate thereof according to the present invention will be specifically described below.

The higher α-olefin copolymer according to the present invention has a higher α-olefin copolymer.
- It is composed of an olefin and a non-conjugated diene.

The higher α-olefin used in the present invention has 6 carbon atoms.
-12 α-olefins, and specific examples include hexene-11hebutene-11octene-11nonene-11decene-11undecene-11dodecene-1.

In the present invention, the above-mentioned higher α-olefins may be used alone or as a mixture of two or more.

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

(In the formula, R1 represents an alkyl group having 1 to 4 carbon atoms, and R2 and R3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, R and R3 are not both hydrogen atoms.) Specifically, the above-mentioned non-conjugated diene includes B-
Methyl-1,8-octadiene, 7-methyl-L, S-
Octadiene, B-ethyl-1,6-octadiene, 6
-broby-1.8-octadiene, 6-butyl-1.
8-octadiene, 6-methyl-1,6-nonadiene,
7-methyl-1,B-nonadiene, 6-ethyl-1,8
-nonadiene, 7-ethyl-1,6-nonadiene, 6-
Examples include methyl-[, 6-decadiene, 7-methyl-1,8-decadiene, 6-methyl-1,6-undecadiene, and the like.

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

Among the above-mentioned non-conjugated dienes, 7-methyl-1,8-octadiene is particularly preferably used.

Furthermore, in addition to the above-mentioned non-conjugated dienes, other copolymerizable heptenes such as ethylene, propylene, butene-1, pentene-1,4-methylpentene-1, etc. can be used for the purpose of the present invention. It may be used as long as it does not cause any damage.

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 '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 1.0 to 10
．． OdN/g, preferably in the range from 1.5 to 8 dII/l. This characteristic value is a measure of the molecular weight of the higher α-olefin copolymer of the present invention.

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 and a nonconjugated diene in the presence of an olefin polymerization catalyst.

The olefin polymerization catalyst used in the present invention is formed from a solid titanium catalyst component [A], an organoaluminum compound catalyst component [B], and an electron donor catalyst component [C].

FIG. 1 shows an example of a 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, norogen, and an electron donor as essential components.

Such a solid titanium catalyst component [A] is prepared by contacting a magnesium compound, a titanium compound, and an electron donor as described below.

In the present invention, the titanium compound used for preparing the solid titanium catalyst component (A) is, for example, Ti(OR).
Examples include tetravalent titanium compounds represented by X (R is a hydrocarbon group, X is)\4-g rogene atom, 0≦g≦4). More specifically, TI Cf
Tetrahalogenated titanium such as lTIBr, TiI4; TI(OCR)Cfl3, T1(QCH)Cfl3, TI(On-CH) Cfl3, Tl(OCR)Br3, TI(OIso CH ) Trihalogenated alkoxytitanium such as Br3; dihalogenated dialkoxytitanium such as Ti(OCR')CD2, TI(QCH)C1)2, TI(On-CH)Cfl2, TI(OCR)Br2 ; TI(OCH3,) 31! .

Monohalogenated trialkoxytitanium such as TI(OC2H5)3C1, TI(On-C4I9)3(1°Ti(OC2H5)3B"; Tl(OCHa)4, TI(QC2I5)4, Tt(On-C4Hta) ) 4 TI (Olso-C4H9) 4 TI (0-2 ethylhexyl) 4 and other tetraalkoxy titaniums.

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

In the present invention, the magnesium compound used in the preparation of the solid titanium catalyst component [A] includes a magnesium compound having reducibility and a magnesium compound not having reducibility.

Here, as a magnesium compound having reducing properties,
For example, magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond can be mentioned. Specific examples of magnesium compounds having such reducing properties include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, cyamylmagnesium, didecylmagnesium, didecylmagnesium, ethylmagnesium chloride, propylmagnesium chloride, Examples include butylmagnesium chloride, hexylmagnesium chloride, amylmagnesium chloride, butyl ethoxymagnesium, ethylbutylmagnesium, octylbutylmagnesium, and butylmagnesium halide. These magnesium compounds may be used alone or may form a complex compound with an organoaluminum compound described below. Moreover, these magnesium compounds may be liquid or solid.

Specific examples of non-reducing magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, and butoxychloride.・Alkoxymagnesium halides such as magnesium, octoxymagnesium chloride; Alkoxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride; ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium, 2-ethylhexoxymagnesium, etc. Alkoxymagnesium; Allyloxymagnesium such as phenoxymagnesium, dimethylphenoxymagnesium; Magnesium laurate,
Examples include magnesium carboxylates such as 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 can be derived from a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, etc. All you have to do is bring it into contact with a compound.

In addition, in the present invention, the magnesium compound includes not only the above-mentioned reducing magnesium compounds and non-reducing magnesium compounds, but also complex compounds, composite compounds, or other metal compounds of the above-mentioned magnesium compounds and other metals. It may be a mixture of. Furthermore, a mixture of two or more of the above compounds may be used.

In the present invention, among these, magnesium compounds that do not have reducing properties are preferred, and halogen-containing magnesium compounds are particularly preferred, and among these, magnesium chloride, alkoxymagnesium chloride,
Allyloxymagnesium chloride is preferably used.

In the present invention, the electron donor used in the preparation of the solid titanium catalyst component [A] includes organic carboxylic acid esters, preferably polyhydric carboxylic acid esters, and specifically, those having a skeleton represented by the following formula. Examples include compounds.

R'-C-COOR6 R3-C-COOR' R4- and -COOH5 In the above formula, R1 represents a substituted or unsubstituted hydrocarbon group, and R2R5R6 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group. , R3R4 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group. Note that at least one of RR' is preferably a substituted or unsubstituted hydrocarbon group. Further, R3 and R4 may be connected to each other to form a cyclic structure. Examples of the substituted hydrocarbon group include substituted hydrocarbon groups containing different atoms such as N, 0, and S, such as -C-0-C--COOR, -COOH.

Examples include substituted hydrocarbon groups having structures such as -OH, -5o3H, -C-N-C--NH2, and the like.

Among these, at least one of RR has 2 carbon atoms.
Diesters derived from dicarboxylic acids having the above alkyl groups are preferred.

Specific examples of polyvalent carboxylic acid esters include diethyl succinate, dibutyl succinate, diethyl methylsuccinate,
Diisobutyl α-methylglutarate, dibutylmethyl malonate, diethyl malonate, diethyl ethyl malonate,
Diethyl isopropyl malonate, diethyl butyl malonate, diethyl phenyl malonate, diethyl diethyl malonate, diethyl allyl malonate, diethyl diisobutyl malonate, diethyl di-n-butyl malonate, dimethyl maleate, monooctyl maleate, diisooctyl maleate, maleic acid Aliphatic acids such as diisobutyl acid, diisobutyl butyl maleate, diethyl butyl maleate, diisopropyl β-methylglutarate, diallyl ethylsuccinate, di-2-ethylhexyl fumarate, diethyl itaconate, diisobutyl itaconate, diisooctyl citraconate, dimethyl citraconate, etc. Polycarboxylic acid esters, aliphatic polycarboxylic acid esters such as diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadic acid, monoethyl phthalate, dimethyl phthalate, Methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, mono-normal butyl phthalate,
Ethyl n-butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate,
Diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, didecyl phthalate, benzylbutyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, dibutyl trimellitate Examples thereof include aromatic polycarboxylic acid esters such as esters such as esters, and esters derived from heterocyclic polycarboxylic acids such as 3,4-furandicarboxylic acid.

Other examples of polyvalent carboxylic acid esters include long chain dicarboxylic acids such as diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, n-octyl sebacate, and di-2-ethylhexyl sebacate. Mention may be made of esters derived from.

Among these polyhydric carboxylic acid esters, compounds having a skeleton represented by the above-mentioned general formula are preferred, and compounds derived from phthalic acid, maleic acid, substituted malonic acid, etc. and an alcohol having 2 or more carbon atoms are more preferred. Preferred are esters, and particularly preferred are diesters obtained by the reaction of phthalic acid and an alcohol having 2 or more carbon atoms.

These polyvalent carboxylic acid esters do not necessarily need to be used as starting materials, and these polyvalent carboxylic acid esters can be derived in the process of preparing the solid titanium catalyst component [A]. A polyhydric carboxylic acid ester may be produced in the preparation step of the solid titanium catalyst component [A] using a compound that can be used.

In the present invention, electron donors other than polyhydric carboxylic acids that can be used when preparing the solid titanium catalyst [A] include alcohols, amines, amides, ethers, Ketones, nitriles, phosphines, stipines, arsines, phosphoramides, esters, thioethers, thioesters, acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy(aryloxy)silanes, etc. Examples include organic silicon compounds, organic acids, amides and salts of metals belonging to Groups 1 to 2 of the periodic table.

In the present invention, the solid titanium catalyst component [A] can be produced by bringing the above-described magnesium compound (or metal magnesium), electron donor, and titanium compound into contact with each other.

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. Note that the above components may be brought into contact with each other in the presence of other reaction agents such as silicon, phosphorus, and aluminum.

Several examples of methods for producing these solid titanium catalyst components [A] will be briefly described below.

(1) A method of reacting a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor with a titanium compound in a liquid phase. This reaction may be carried out in the presence of a grinding aid or the like.

Moreover, when reacting as described above, isomeric compounds may be ground. Furthermore, when reacting as described above, each component may be pretreated with an electron donor and/or a reaction aid such as an organoaluminum compound or a halogen-containing silicon compound. Note that in this method, the above electron donor is used at least once.

(2) a liquid magnesium compound that does not have reducing properties;
A method in which a solid titanium complex is precipitated by reacting a liquid titanium compound in the presence of an electron donor.

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

(4) The reaction product obtained in (1) or (2),
A method for further reacting an electron donor and a titanium compound.

(5) A solid material obtained by pulverizing a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor in the presence of a titanium compound is treated with either a halogen, a halogen compound, or an aromatic hydrocarbon. Method. In this method, a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor may be ground in the presence of a grinding aid or the like. Also,
A magnesium compound or a complex compound consisting of a magnesium compound and an electron donor may be ground in the presence of a titanium compound, then pretreated with a reaction aid, and then treated with a halogen or the like. Note that examples of the reaction aid include organoaluminum compounds and halogen-containing silicon compounds.

Note that in this method, an electron donor is used at least once.

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

(7) A method of contacting a contact reaction product of a metal oxide, dihydrocarbylmagnesium, and a halogen-containing alcohol with an electron donor and a titanium compound.

(8) A method of reacting a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or aryloxymagnesium with an electron donor, a titanium compound, and/or a halogen-containing hydrocarbon.

Solid titanium catalyst component [A] listed in (1) to (8) above
Among the preparation methods, a method using liquid titanium halide during catalyst preparation, a method using a titanium compound after use, or a method using a halogenated hydrocarbon when using a titanium compound are preferred.

The amount of each of the above-mentioned components used when preparing the solid titanium catalyst component [A] varies depending on the preparation method and cannot be unconditionally defined, but for example, the amount of electron donor per 1 mole of magnesium compound is about 0.01. In an amount of ~5 mol, preferably 0.05-2 mol, the titanium compound is about 0.0
It is used in an amount of 1 to 500 mol, preferably 0.05 to 300 mol.

The solid titanium catalyst component [A] thus obtained is:
Contains magnesium, titanium, halogen and electron donor as essential components.

In this solid titanium catalyst component [A], the halogen/titanium (atomic ratio) is about 4 to 200, preferably about 5 to 10.
0, and the electron donor/titanium (molar ratio) is about 0.
1 to 10, preferably about 0.2 to about 6, and the magnesium/titanium (atomic ratio) is preferably about 1 to 100, preferably about 2 to 50.

This solid titanium catalyst component [A] contains magnesium halide with a smaller crystal size than commercially available magnesium halide, and usually has a specific surface area of about 50rrr.
/g or more, preferably about 60 to 1000 rrr/g, more preferably about 100 to 800 rrr/g. and,
This solid titanium catalyst component [A] is substantially unchanged in composition by hexane washing, since the above-mentioned components are integrated to form the catalyst component.

Such a solid titanium catalyst component [A] can be used alone, but it can also be used 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, high catalytic activity is exhibited even if the specific surface area is smaller than the above-mentioned specific surface area.

Regarding the preparation method of such a highly active titanium catalyst component, see, for example, JP-A-50-108385 and JP-A-50-108385.
-126590, 51-20297, 51-211189, 51-64586, 51-92885, 51-136625, 52-87489, 52- 10059
Publication No. 6, Publication No. 52-147688, Publication No. 52-10
No. 4593, No. 53-258C1, No. 53-
No. 40093, No. 53-40094, No. 53
-43094, 55-135102, 55-135103, 55-152710, 5B-811, 5B-11908, 5B-18606, 58- No. 83006, No. 58-138705, No. 58-13870
Publication No. 8, Publication No. 5g-138707, Publication No. 58-13
No. 8708, No. 58-138709, No. 58
-138710 publication, 58-138715 publication,
It is disclosed in 60-23404, 61-21109, 81-37802, 61-37803, and the like.

As the organoaluminum compound catalyst component [B], a compound having at least one Ag-carbon bond in the molecule can be used. Such compounds include, for example, (wherein R1 and R2 usually have 1 to 15 carbon atoms,
Preferably it is a hydrocarbon group containing 1 to 4, and these may be the same or different from each other. X represents a halogen atom, 0<m≦3, n is 0≦n<3, p is O≦p<3, q
is a number such that 0≦q<3, and m+ n+p+q=
(i) an organic aluminum compound represented by the general formula MIR14 (where M is Li, Na, and R1 is the same as above) and aluminum; Examples include complex alkylated products.

Examples of the organic aluminum compounds belonging to (i) above include the following compounds.

General formula R1,l (OR2) -m (wherein R and R2 are the same as above. m is preferably 1
．． 5≦m≦3), ■ General formula RAgX31 (In the formula, R1 is the same as above. X is halogen, and m is preferably Q<m<3), ■ General formula Rl! H31 ■ (Formula suspension, R1 is the same as above. m is preferably 2≦m<3
), (wherein R■ and R2 are the same as above. X is halogen,
O<m≦3.0≦n<3.0≦q<3, m+n+q−
Examples include compounds represented by 3).

More specifically, the aluminum compounds belonging to (i) include trialkylaluminum such as triethylaluminum and tributylaluminium; trialkenylaluminum such as triisoprenylaluminum; dialkylaluminum alkoxide such as diethylaluminum ethoxide and dibutylaluminum butoxide. : Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide, partially alkoxylated alkylaluminums with homogeneous composition; Dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide; Alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquipromide; partially halogenated alkyls such as alkylaluminum cybarides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide, etc. Aluminum; dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride; other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, probylaluminum dihydride; ethylaluminum ethoxy chloride, Mention may be made of partially alkoxylated and halogenated alkyl aluminums such as butylaluminum butoxy chloride, ethylaluminum ethoxybromide and the like.

Compounds similar to (i) include organoaluminum compounds in which two or more aluminum atoms are bonded via oxygen atoms or nitrogen atoms. Examples of such compounds include (C2H5)2AgOAg (C
2H5)2, (CH) AfIOAg (C4H9)
Examples include 2,2H5 methylaluminoxane.

Examples of compounds belonging to the above (i) include LIAg (C2H5)4, Lii (C7H15)4, and the like.

Among these, it is particularly preferable to use trialkylaluminum or alkylaluminum in which two or more of the above-mentioned aluminum compounds are combined.

As the electron donor catalyst component [C], oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, acid anhydrides, alkoxysilanes, etc. Nitrogen-containing electron donors such as , ammonia, amines, nitriles, isocyanates, or polyhydric carboxylic acid esters as described above can be used. More specifically, methanol, ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, cumyl alcohol, isopropylbenzyl alcohol Alcohols with 1 to 18 carbon atoms such as; phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol,
Phenols with 6 to 20 carbon atoms that may have a lower alkyl group such as cumylphenol and naphthol; Ketones with 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, and benzoquinone; acetaldehyde , propionaldehyde, octylaldehyde, benzaldehyde,
2-1 carbon atoms such as tolualdehyde and naphthaldehyde
Aldehydes of 5; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, croton ethyl acid, 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 ethylbenzoate, methyl anisate, n-butyl maleate , diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisopropyl tetrahydrophthalate,
Organic acid esters having 2 to 30 carbon atoms such as diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate; acetyl Acid halides with 2 to 15 carbon atoms such as chloride, benzoyl chloride, toluyl chloride, and anisyl chloride; 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, and diphenyl ether ethers; acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide; amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylenediamine; Nitriles such as acetonitrile, benzonitrile, and tolnitrile; 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 also be used.

R5l(OR') 4-n...
[I] [In the formula, R and R′ are hydrocarbon groups, and 0<n<4] As the organosilicon compound represented by the above general formula [I], specifically, trimethyl Methoxysilane, trimethylethoxysilane, dimethyldimethoxysilane,
Dimethyljethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyljethoxysilane, t-amylmethyljethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyljethoxysilane, bis p-tolyl Dimethoxysilane, bis-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-
Tolyldimethoxysilane, bisethyl phenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyljethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltrimethoxysilane Ethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-rolbrovirtrimethoxysilane, methyltoluethoxysilane,
Ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, l5O-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyl Triisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane,
2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxy(at Iyloxy)silane, vinyltris(β-
(methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, etc. are used.

Among these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane,
Vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis p-tolyldimethoxysilane, p-)lylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane silane,
Diphenyljethoxysilane is preferred.

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

SIRR(OR3) 1 3-1 ... [II] [wherein, R1
is a cyclopentyl group or a cyclopentyl group having an alkyl group, R2 is a group selected from the group consisting of an alkyl group, a cyclopentyl group, and a cyclopentyl group having an alkyl group, R3 is a hydrocarbon group, and m
is 0≦m≦2. ] In the above formula [I], R1 is a cyclopentyl group or a cyclopentyl group having an alkyl group, and as RL, in addition to the cyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group, 2,3 -Dimethylcyclopentyl group and other cyclopentyl groups having an alkyl group can be mentioned.

Further, in the formula [■], R2 is an alkyl group, a cyclopentyl group, or a cyclopentyl group having an alkyl group, and R2 is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, An alkyl group such as a hexyl group, or a cyclopentyl group exemplified as R1 and a cyclopentyl group having an alkyl group can be similarly mentioned.

Further, in formula [II], R3 is a hydrocarbon group,
Examples of i3 include hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups.

Among these, R1 is a cyclopentyl group, and R2
It is preferred to use organosilicon compounds in which R is an alkyl group or a cyclopentyl group and R3 is an alkyl group, especially a methyl group or an ethyl group.

Examples of such organosilicon compounds include trialkoxysilanes such as cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, and cyclopentyltriethoxysilane; dicyclopentyldimethoxysilane; Dialkoxysilanes such as silane, bis(2-methylcyclopentyl)dimethoxysilane, bis(2,3-dimethylcyclopentyl)dimethoxysilane, dicyclopentyljethoxysilane; tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxy Examples include monoalkoxysilanes such as silane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane. Among these electron donors, organic carboxylic acid esters or organic silicon compounds are preferred, and organic silicon compounds are particularly preferred.

The olefin polymerization catalyst used in the present invention is formed from the solid titanium catalyst component [A] as described above, the organoaluminum compound catalyst component CB], and the electron donor [C]. A higher α-olefin and a non-conjugated diene are polymerized using this olefin polymerization catalyst, but after prepolymerizing an α-olefin or a higher α-olefin using this olefin polymerization catalyst,
This catalyst can also be used to polymerize higher α-olefins and nonconjugated dienes (main polymerization). During pre-polymerization, α-olefin or higher α-olefin is prepolymerized in an amount of 0.1 to 500 g, preferably 0.3 to 300 g, particularly preferably 1 to 100 g, per 1 g of olefin polymerization catalyst.

In the prepolymerization, a catalyst can be used at a much higher concentration than the catalyst concentration in the system in the main polymerization.

The concentration of solid titanium catalyst component [A] in prepolymerization is:
Usually about 0.01 to 200 mmol, preferably about 0 mmol in terms of titanium atoms, per 1 g of the inert hydrocarbon medium described below.
．． A desirable range is 1 to 100 mmol, particularly preferably 1 to 50 mmol.

The amount of the organoaluminium catalyst component [B] is 0.1 to 500 g per 1 g of the solid titanium catalyst component [A1], preferably 0.1 to 500 g.
The amount may be such that 3 to 300 g of polymer is produced, and is usually about 0.1 to 100 mol, preferably about 0.5 to 5 mol, per 1 mol of titanium atoms in the solid titanium catalyst component [A].
An amount of 0 mol, particularly preferably 1 to 20 mol is desirable.

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

Prepolymerization is preferably carried out under mild conditions by adding the olefin or higher α-olefin and the above catalyst components to an inert hydrocarbon medium.

Examples of the inert hydrocarbon medium used at this time include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, etc. Examples include 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 preferred to use aliphatic hydrocarbons. Incidentally, the prepolymerization can be carried out using the olefin or higher α-olefin itself as a solvent, or the prepolymerization can be carried out substantially in the absence of a solvent.

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 prepolymerization is usually about -20 to +100°C.
, preferably about -20 to +80°C, more preferably O
It is desirable that the temperature is in the range of ~+40°C.

In addition, in the prepolymerization, a molecular weight regulator such as hydrogen can also be used. Such a molecular weight modifier is 1
The intrinsic viscosity [η] of the polymer obtained by prepolymerization measured in a decalin solvent at 35° C. is about 0.2 dj? It is desirable to use an amount of at least 0.5 dR/g, preferably about 0.5 to 10 dR/g.

The prepolymerization is carried out using the solid titanium catalyst component [A1
About 0.1-500g per gram, preferably about 0.3-3
It is desirable to carry out the reaction in such a way that 00 g, particularly preferably 1 to 100 g, of the polymer is produced. If the amount of prepolymerization is too large, the production efficiency of the olefin polymer may decrease.

Prepolymerization can be carried out batchwise or continuously.

It is formed from 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]. Copolymerization (main polymerization) of a higher α-olefin and a nonconjugated diene is performed in the presence of an olefin polymerization catalyst.

During copolymerization (main polymerization) of a higher α-olefin and a nonconjugated diene, in addition to the above-mentioned olefin polymerization catalyst, the organic aluminum compound used in producing the olefin polymerization catalyst is added as an organoaluminum compound catalyst component. The same components as the aluminum compound catalyst component [B] can be used.

In addition, 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 an electron donor catalyst component. Something similar can be used. In addition,
The organoaluminum compound and electron donor used in the copolymerization (main polymerization) of higher α-olefin and nonconjugated diene are not necessarily the organoaluminum compound and electron donor used in preparing the above-mentioned olefin polymerization catalyst. It does not have to be the same as the donor.

Copolymerization (main polymerization) of a higher α-olefin and a nonconjugated 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 nonconjugated diene, the solid titanium catalyst component [A] has a polymerization volume of 1
It is usually used in an amount of about 0.001 to about 1.0 mmol, preferably about 0.005 to 0.5 mmol, calculated as titanium atoms per g. In addition, in the organoaluminum compound catalyst component [B], the number of metal atoms in the organoaluminum compound catalyst component [B] is usually about 1 to 1 mole per mole of titanium atoms in the solid titanium catalyst component [A]. It is used in an amount of 2000 moles, preferably about 5 to 500 moles. Further, the electron donor catalyst component [C] is usually about 0.001 to 10 mol, preferably about 0.01 to 10 mol, per mol of metal atom in the organoaluminum compound catalyst component [B].
The amount used is such that it is 2 mol, particularly preferably about 0.05 to 1 mol.

By controlling the amount of hydrogen used during main polymerization, the molecular weight of the resulting polymer can be adjusted.

In the present invention, the polymerization temperature of higher α-olefin and nonconjugated diene is usually about 10 to 200°C, preferably about 30 to 100°C, and the pressure is usually normal pressure to 100 kg/
cJ, preferably set at normal pressure to 50 kg/cj.

In the copolymerization (main polymerization) of a higher α-olefin and a nonconjugated diene, the polymerization can be carried out in any of a batch method, a semi-continuous method, and a continuous method. Furthermore, 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, etc. In particular, when applied to resin modifiers and various rubber products, its properties are maximized.

As the resin modifier, for example, polypropylene, polyethylene, polystyrene, and the like can be used. When the higher α-olefin copolymer of the present invention is added to these resins, impact resistance and stress crack resistance can be dramatically improved.

Various rubber products are generally used in a vulcanized state, but if the higher α-olefin copolymer of the present invention is also used in a vulcanized state, its properties will be further exhibited. When the high-grade α-olefin copolymer of the present invention is used in various rubber products, the vulcanizate is prepared by preparing an unvulcanized compounded rubber once, in the same way as when vulcanizing general rubber, and then using the vulcanized product. It is manufactured by molding compounded rubber into the intended shape and then vulcanizing it.

As the vulcanization method, either a method of heating using a vulcanizing agent or a method of irradiating with an electron beam may be adopted.

Examples of the vulcanizing agent used during vulcanization include sulfur compounds and organic peroxides. Examples of sulfur-based compounds include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide,
Examples include selenium dimethyldithiocarbamate.

Among them, 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. Specifically, the organic peroxides include dicumyl peroxide, 2,5-dimethyl-2,
5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane-3, di Examples include tert-butyl peroxide, di-tert-butyl peroxy-3,3,5-trimethylcyclohexane, and tert-butyl hydroperoxide. Among them, dicumyl peroxide, di-tert-butyl peroxide, and di-tert-butyl peroxide-3,3,5-trimethylcyclohexane are preferably used. The organic peroxide is used in an amount of 3 x 10 to 5 x 10-2 mol, preferably 1 x 1 mol, per 100 g of the higher α-olefin copolymer of the present invention.
It is used in amounts of 0 to 3×10 −2 moles.

=3 When using a sulfur compound as a vulcanizing agent, it is preferable to use a vulcanization accelerator together. Specifically, the vulcanization accelerator includes N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene-2-
Benzothiazolesulfenamide, N,N-diisopropyl-2-benzothiazolesulfenamide, 2-
Mercaptobenzothiazole, 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,
Thiazole compounds such as 8-diethyl-4-morpholinothio)benzothiazole and dibenzothiazyl disulfide; guanidine compounds such as diphenylguanidine, triphenylguanidine, diorthotolylguanidine, orthotolyl pi-guanide, and diphenylguanidine phthalate; Aldehyde amines or aldehyde-ammonia compounds such as acetaldehyde-aniline reactants, butyraldehyde-aniline condensates, hexamethylenetetramine, acetaldehyde ammonia; 2
- Imidacillin compounds such as mercaptoimidacillin; Thiourea compounds such as thiocarbamic acid, diethylthiourea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea; tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethyl Thiuram compounds such as thiuram disulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethylthiocarbamate, di-n
- Dithioate salt compounds such as zinc butyldithiocarbamate, zinc ethyl phenyl dithiocarbamate, zinc butylphenyl dithiocarbamate, sodium dimethyl dithiocarbamate, selenium dimethyl dithiocarbamate, tellurium diethyldithiocarbamate; xanthate compounds such as zinc dibutyl xanthate Compounds: Compounds such as zinc white can be mentioned. These vulcanization accelerators are used in an amount of 0 per 100 parts by weight of the higher α-olefin copolymer.
．． It is used in an amount of 1 to 20 parts by weight, preferably 0.2 to 10 parts by weight.

When using an organic peroxide as a vulcanizing agent, it is preferable to use a vulcanizing aid together. Examples of the vulcanization aid include sulfur, 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 and the like. Such a vulcanization aid is the organic peroxide used.
It is used in an amount of 1/2 to 2 moles, preferably about equimole.

When using an electron beam as the vulcanization method without using a vulcanizing agent, 0.1~
10 MeV (megaelectron volt), preferably 0
．． Electrons having an energy of 3 to 20 MeV may be irradiated at an absorbed dose of 0.5 to 35 Mrad (megarad), preferably 0.5 to 10 Mrad. At this time, a vulcanization aid may be used in combination with the organic peroxide as a vulcanizing agent, and the amount thereof is 1X10 to 1X1 per 100g of the higher α-olefin copolymer of the present invention.
0-' mol, preferably 1×10 to 3×10-2 mol.

Unvulcanized compounded rubber is prepared by the following method. That is, the high α-olefin copolymer, filler, and softener are mixed at 80 to 170°C using a mixer such as a Banbury mixer.
After kneading for 3 to 10 minutes at a temperature of 40 to 40 minutes, add and mix a vulcanizing agent and, if necessary, a vulcanization accelerator or vulcanization aid using rolls such as an oven roll.
After kneading at 80° C. for 5 to 30 minutes, the mixture is separated to prepare a ribbon-like or sheet-like compounded rubber.

The compounded rubber thus prepared is molded into the intended shape using an extruder, calendar roll, or press, and at the same time as the molding or the molded product is introduced into a vulcanization tank.
A vulcanizate can be obtained by heating at a temperature of 0 to 270°C for 1 to 30 minutes or by irradiating with an electron beam according to the method described above.

This vulcanization step may be carried out using a mold or without using a mold. When a mold is not used, the molding and vulcanization steps are usually carried out continuously. Heating methods in the vulcanization tank include hot air, glass beads fluidized bed, and UH.
A heating tank using F (ultra-high-frequency electromagnetic waves), steam, or the like can be used.

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

The rubber vulcanizate produced in the above manner can be used as an anti-vibration rubber, automatic industrial parts such as cover materials for tire vibrating parts, industrial rubber products such as rubber rolls and belts, electrical insulation materials, and civil engineering and construction materials. It can be used for applications such as rubber-coated fabrics. Further, by adding a foaming agent to the unvulcanized compounded rubber and foaming it by heating, a foamed material can be obtained, and this foamed material can be used for applications such as heat insulating materials, cushioning materials, and sealing materials. It can also be blended with resins such as polyolefins, polyamides, polyesters, and polycarbonates to improve the impact resistance of these resins.

Effects of the Invention The high-grade α-olefin copolymer of the present invention provides a vulcanizate with excellent weather resistance, ozone resistance, heat aging resistance, low-temperature properties, and vibration damping properties, as well as excellent dynamic fatigue resistance. Obtainable.

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 a high yield.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

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 at 1
After heating the reaction at 30'C for 2 hours to obtain a homogeneous solution, phthalic anhydride 21.3. was added and further stirred and mixed at 130° C. for 1 hour to dissolve phthalic anhydride in this homogeneous solution. After cooling the homogeneous solution obtained in this way to room temperature, 75 ml of this homogeneous solution
1 in 200 ml of titanium tetrachloride kept at -20°C.
The entire amount was added dropwise over a period of time. After charging, the temperature of this mixed liquid was raised to 110°C over 4 hours, and then the temperature was increased to 110°C.
When this temperature was reached, 5.22 g of diisobutyl phthalate was added, and the mixture was maintained at the same temperature for 2 hours with stirring. 2
After the completion of the reaction, the solid part was collected by hot filtration, and this solid part was resuspended in 275 ml of titanium tetrachloride.
The heating reaction was carried out again at 110° C. for 2 hours. After the reaction was completed, the solid portion was again collected by hot filtration and thoroughly washed with decane and hexane at 110° C. until no free titanium compound was detected in the washing liquid. The solid titanium catalyst component [A] prepared by the above procedure was stored as a decane slurry, and a portion of this was dried for the purpose of investigating the catalyst composition. The composition of the solid titanium catalyst component [A] thus obtained was 2.2% by weight of titanium, 58.1% by weight of chlorine, 19.2% by weight of magnesium, and 10.7% by weight of diisobutyl phthalate.

(Polymerization) Decane was added to a 500 ml polymerization vessel equipped with a stirring blade.
2m1. 100 ml of octene-1, 7-methyl-1
, 8-octadiene (8 ml) was charged. The temperature of this solution was raised to 50° C., and hydrogen and nitrogen were continuously introduced into the solution at a rate of ifI and 5CN per hour, respectively. After raising the temperature to 50°C, 0.625 mmol of triisobutylaluminum, 0.21 mmol of trimethylethoxysilane, and 0.0125 mmol of solid titanium catalyst component [A] in terms of titanium atoms were charged to start polymerization. did. After polymerization was carried out at 50° C. for 30 minutes, a small amount of isobutyl alcohol was added to stop the polymerization, and the polymerization solution was poured into a large amount of methanol to precipitate a copolymer. Next, the precipitated copolymer was collected and dried under reduced pressure at 120°C for one day to obtain 12.4g of octene-1.7.
-Methyl-1,6-octadiene copolymer was obtained.

The intrinsic viscosity [η] of the obtained copolymer measured in decalin at 135°C was 6.41! /g, 7-methyl-1
,6-octadiene content was 6.6 mol%.

Examples 2 to 6 In Example 1, the higher α-olefin and polymerization conditions were changed as shown in Table 1, and the same procedure as in Example 1 was carried out.
Copolymerization was carried out to obtain copolymers shown in Table 1.

Comparative Example 1 Titanium trichloride (manufactured by Toho Titanium Co., Ltd., TAC) was used as a catalyst.
Copolymerization was carried out in the same manner as in Example 1, except that 1.25 mmol and 2.5 mmol of 1.25 mmol and 2.5 mmol of diethylaluminum chloride and diethylaluminum chloride were used, respectively, to obtain the copolymers shown in Table 1. Activity per titanium is low, Example 1
It was only 0.7% of the total.

Example 7 A copolymerization reaction of octene-1 and 7-methyl-1,6-octadiene was continuously carried out using a 4 g glass polymerization vessel equipped with a stirring blade.

That is, a decane solution of octene-1 and 7-methyl-1,6-octadiene was poured from the top of the polymerization vessel until the octene-1 concentration in the polymerization vessel was 155 g/j! , 7-methyl-1
．． The concentration of 6-octadiene in the polymerization vessel is 14g/
The solid titanium catalyst component was added as 1 g of catalyst per hour, and the decane slurry solution of [A] was added at 0.1 g per hour so that the titanium concentration in the polymerization vessel was 0.05 mmol/g.
! , a decane solution of triisobutylaluminum was added every hour so that the aluminum concentration in the polymerization vessel was 2.5 mmol/g.

A decane solution of trimethylethoxysilane was added every hour so that the silane concentration in the polymerization vessel was 0.83 mmol/g.
．． Each was continuously fed into the polymerization vessel at a rate of 6 g. On the other hand, the polymerization liquid in the polymerization vessel is always 2fI from the bottom of the polymerization vessel.
It was extracted continuously so that Also, from the top of the polymerization vessel, 1g of hydrogen per hour and 50j of nitrogen per hour! was supplied at a rate of The copolymerization reaction was carried out at 50°C by circulating hot water through a jacket attached to the outside of 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 thoroughly washing the copolymer with methanol, it was heated to 140°C.
Dry under reduced pressure for a day and night to obtain octane-doermethyl-1,E.
l-Octadiene copolymer was obtained 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.

Example 8 Octene-doermethyl-1,6 produced in Example 1
- The octadiene copolymer was kneaded using an 8-inch oven roll according to Table 2 to obtain an unvulcanized compounded rubber.

Table product name: Asahi 70: Manufactured by Shio Carbon Co., Ltd. Product name: Sansen 4240: Manufactured by Nippon Sun Oil Co., Ltd. Product name: Sunceller M Manufactured by Nisan Shin Kagaku Co., Ltd. Product name: Suncella TT Manufactured by Nisan Shin Kagaku Co., Ltd. This compounded rubber was heated to 160°C. A vulcanized sheet was prepared by heating for 20 minutes using a press heated to
The following tests were conducted. The test items are as follows.

[Test items] Tensile test, hardness test, aging test, bending test, vibration damping, weather resistance, ozone resistance test, low temperature properties.

[Test method] JIS K for tensile test, hardness test, aging test, and bending test
6301. That is, tensile strength (T, ) and elongation (E, ) in the tensile test, and H8 in the hardness test.
The JIS A hardness was measured, and the aging test was conducted by air heating at 120° C. for 70 hours.

After the aging test, a tensile test was conducted to determine the retention of the physical properties before aging, that is, the tensile strength retention AR (T) and the elongation retention AR (EB). The bending test was performed using a dematcher testing machine to examine resistance to crack growth. That is, the number of bending times until the crack became 15 mm was measured.

The loss tangent (tan δ) was measured using a Rheometric dynamic spectrometer as an index of damping performance.
The lungs were incubated at 100 rad/see at 100°C.

Next, weather resistance was examined using a sunshine weather meter. The conditions of the sunshine weather meter were: black panel temperature 63℃, carbon arc turned on, 12℃
Water was sprayed for 18 minutes on a 0 minute cycle. After performing this cycle for 200 hours, a tensile test was conducted to determine the retention of strength and elongation compared to before the test.

The ozone resistance test was conducted according to JIS K 8301.

The test conditions were an ozone concentration of 50 pphm, a test atmosphere temperature of 40° C., and an elongation rate of 30%, and the test was conducted after 200 hours to determine the embrittlement temperature.

The results are shown in Table 3.

Example 9 In Example 8, a vulcanized sheet was obtained in exactly the same manner as in Example 8, except that the copolymer produced in Example 2 was used, and the above tests were conducted.

The results are shown in Table 3.

Example 10 In Example 8, a vulcanized sheet was obtained and the above tests were conducted in exactly the same manner as in Example 8, except that the copolymer produced in Example 4 was used.

The results are shown in Table 3.

Example 11 In Example 8, a vulcanized sheet was obtained in exactly the same manner as in Example 8, except that the copolymer produced in Example 5 was used, and the above tests were conducted.

The results are shown in Table 3.

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

The results are shown in Table 3.

Example 12 Polypropylene (Mitsui Petrochemical Highball J700
), 20 parts by weight of the higher α-olefin copolymer produced in Example 1, and 0.1 part by weight of 2.6-sitashary-butyl-4-methylphenol at 190°C.
After kneading for a minute using a B-type Banbury mixer (manufactured by Kobe Steel, Ltd.), the mixture was rolled out into a sheet using an oven roll. This was pelletized using a square pelletizer (manufactured by Horai Tekko Co., Ltd.) and subjected to injection molding to form a sheet with a size of 150 cm x 120 m x 2 m. The injection molding conditions are as follows.

Injection - Next pressure: 1000 kg/aJ, held for 5 seconds in a cycle Secondary pressure: 800 kg/aJ, 5 seconds in a cycle Injection speed: 4Cb Resin temperature: 230℃ From this sheet, the yield point stress (YS) and breakage point elongation were determined by the method specified in JIS K 8758. (EL) was measured, and Izod impact strength was also measured in an atmosphere at 23° C. according to STM D 25B.

The results are shown in Table 4.

Comparative Example 3 The same procedure as in Example 12 was conducted except that the higher α-olefin copolymer was not used and the polypropylene was used as it was for injection molding.

The results are shown in Table 4.

Table 4

[Brief explanation of drawings]

FIG. 1 is a flowchart showing the steps for preparing an olefin polymerization catalyst used in producing a higher α-olefin copolymer according to the present invention. Agent Patent Attorney Shun Suzuki Indication of Partial Procedural Amendment Case 1999 Patent Application No. 103,679 1999
Patent Department filed on April 24th (3) 2゜ Title of the invention: Higher α-olefin copolymer, its manufacturing method, and its vulcanizate 3゜ Relationship with the case of person making an amendment Patent applicant address: Tokyo Chiyoda-ku Kasumigaseki 3-chome [I2-5 name
Name Mitsui Petrochemical Industries Co., Ltd. Representative Takebayashi Yoriai 4, Agent Address (zip code 141) 3rd floor, Araku Building, 2-19-2 Nishigotanda, Tokyo Parts Ward [Telephone: 03 (491) 31B1] 6゜7゜Contents of the amendment in the column “3. Detailed description of the invention” of the specification subject to the amendment As shown in the attached sheet (no changes to the content other than the matters stated in the column subject to the amendment) Contents of the amendment (1) Specification No. In page 51, line 15, rO,3~
20MeVJ and Arno are corrected as r 0 , 3~2, 0MeVJ. (2) On page 57, line 7 of the same document, the phrase "manufactured by Toho Titanium Co., Ltd." is amended to read "manufactured by Toho Titanium ■." (3) In the 7th line from the bottom of page 61 of the same book, the phrase “manufactured by Asahi Carbon Co., Ltd.” is corrected to “J made by Asahi Carbon ■.” (4) In the 6th line from the bottom of page 61 of the same book, , "manufactured by Nippon Sun Oil Co., Ltd." is corrected to "manufactured by Nippon Sun Oil Kanko Co., Ltd." (5) In the fourth and fifth lines from the bottom of page 61 of the same book, the phrase "manufactured by Sanshin Kagaku Co., Ltd." is amended to read "manufactured by Sanshin Kagaku Kogyo ■." (6) In the second line of page 66 of the same document, "manufactured by Mitsui Petrochemicals Co., Ltd." is amended to "manufactured by Mitsui Petrochemicals Co., Ltd.". (7) In the 7th line of page 66 of the same document, "(Kobe Steel Shinsei)" is amended to read "(-Kobe Steel Shinsei)". (8) In the 9th line of page 66 of the same document, the phrase "(made by Horai Tekko Co., Ltd.)" is amended to read "(■Made by Horai Tekko Co., Ltd.)". Below

Claims (1)

[Scope of Claims] 1) A copolymer consisting of 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 (b) Intrinsic viscosity measured in decalin solvent at 135°C [
η] is within the range of 1.0 to 10.0 dl/g; ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] , R^1 represents an alkyl group having 1 to 4 carbon atoms, and R^2 and R^3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.However, when R^2 and R^3 are both hydrogen atoms, 2) From [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 the olefin polymerization catalyst to be formed, a higher α-olefin having 6 to 12 carbon atoms and the following general formula [I
] A method for producing a higher α-olefin copolymer according to claim 1, which comprises copolymerizing with a non-conjugated diene represented by; ] (In the formula, R^1 represents an alkyl group having 1 to 4 carbon atoms, and R^2 and R^3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, if R^2 and R^3 are 3) A vulcanizate of the higher α-olefin copolymer according to claim 1.