JPH0446909A - Higher alpha-olefin copolymer and its production - Google Patents

Abstract

PURPOSE:To obtain a copolymer excellent in weathering resistance, ozone resistance, heat deterioration resistance, low-temperature properties and flex fatigue resistance by copolymerizing a higher alpha-olefin with butene-1 and a nonconjugated diene in the presence of a specified catalyst. CONSTITUTION:A 6-20C higher alpha-olefin is copolymerized with butene-1 and a nonconjugated diene of the formula in the presence of an olefin polymerization catalyst prepared from a solid titanium catalyst component essentially consisting of Mg, Ti, halogen and an electron donor, an organoaluminum compound catalyst component and an electron donor catalyst component to obtain a higher alpha-olefin copolymer having a molar ratio of the higher alpha-olefin to the butene-1 of 40/60 to 95/5, an iodine value of 2-40, an intrinsic viscosity [eta] as measured in decalin at 135 deg.C of 1.0-10.0dl/g and a degree of crystallinity as measured by X-ray diffractometry of 5% or below.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a novel higher α-olefin copolymer and a method for producing the same.
High-grade α-olefin copolymers with excellent properties such as bending fatigue resistance), weather resistance, ozone resistance, heat aging resistance, and low-temperature properties, and can be used for various rubber products, resin modifiers, etc., and their production. Regarding the method.

Technical Background of the Invention Ethylene-propylene-diene copolymers have good heat resistance and ozone resistance, so they are used in automobile industrial parts, industrial rubber products, electrical insulation materials, civil engineering and construction materials, rubberized fabrics, etc. It is widely used as a material for plastic blending in rubber products, polypropylene, polystyrene, etc. 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, although natural rubber has excellent dynamic fatigue resistance, it has poor heat resistance and ozone resistance, which poses practical problems.

The present inventors have conducted intensive research to obtain a polymer that has excellent properties such as weather resistance, ozone resistance, and heat aging resistance, as well as excellent dynamic properties such as bending resistance. In the presence, especially, a 2-specified higher α-olefin;
When butene-1 and a specific non-conjugated diene are copolymerized, it has been discovered that a higher α-olefin copolymer having the above-mentioned properties can be obtained, and the present invention has been completed.

Purpose of the Invention The present invention aims to solve the problems associated with the prior art as described above. The object of the present invention is to provide a high-grade α-olefin co-merger and a method for producing the same.

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 20 carbon atoms, 1 butene, and a nonconjugated diene represented by the following general formula [I]. (a) The molar ratio of higher α-olefin and butene-1 (higher α-olefin/butene-1) is 40/60 to 951.
(b) the iodine value is within the range of 2 to 40, (c) 13
The intrinsic viscosity [η] measured in a decalin solvent at 5°C is 1.
0-10. (d) crystallinity measured by X-ray diffraction method is within a range of 5% or less.

(In the formula, n is an integer of 1 to 5, and R1 has 1 to 4 carbon atoms.
alkyl group, R and R3 are hydrogen atoms or have 1 carbon number
~8 alkyl group. 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 [C] In the presence of an olefin polymerization catalyst formed from the electron donor catalyst component, a higher α-olefin having 6 to 20 carbon atoms, butene 1, and the following general formula [! ] by copolymerizing with a non-conjugated diene represented by (a) a molar ratio of higher α-olefin and butene-1 (higher α-olefin/butene-1) of 40/60 to 951.
(b) the iodine value is within the range of 2 to 40, (c) 13
The intrinsic viscosity [η] measured in a decalin solvent at 5°C is 1.
It is characterized by obtaining a higher α-olefin copolymer whose crystallinity is within the range of 0 to 10.0 dl/g and (d) whose crystallinity is within the range of 5% or less as measured by X-ray diffraction method. .

(In the formula, n is an integer of 1 to 5, and R1 has 1 to 4 carbon atoms.
alkyl group, R and R3 are hydrogen atoms or have 1 carbon number
~8 alkyl group. However, R and R3 are never both hydrogen atoms. ) Detailed Description of the Invention The higher α-olefin copolymer and the method for producing the same 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, butene-1, and a non-conjugated diene.

The higher α-olefin used in the present invention has 6 carbon atoms.
~20 α-olefins, specifically, published by Hexene, heptene-11 octane-1, nonene-1, decene-1, undecene-1, dodecene-1, tridecene-1
, Tetradecene-1, Published by Pentadecene, Hexadecene-
1, heptadecene-1, nonadecene-11 published by Eikosen, etc.

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

Among the above-mentioned higher α-olefins, hexene-1, octene-1, decene-11 and dodecene-1 are preferably used.

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

(In the formula, n is an integer of 1 to 5, and R1 has 1 to 4 carbon atoms.
alkyl group, R and R3 are hydrogen atoms or have 1 carbon number
~8 alkyl group. However, R and R3 are never both hydrogen atoms. ) Specifically, the above-mentioned non-conjugated dienes include 4-
Methyl-1,4-hexadiene, 5-methyl-14-hexadiene, 4-ethyl-1,4-hexadiene, 5-ethyl-1,4-hexadiene, 5-methyl-14-hebutadiene, 6-methyl-1 , 4-heptadiene, 5-ethyl-1,4-hebutadiene, 6-nityl-1,4-hebutadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-hebutadiene, 5-ethyl- 1,5-heptadiene, 6-nityl-1,5-hebutadiene, 6-methyl-14octadiene, 7-methyl, 4-octadiene, 6-ethyl-1,4-octadiene, 7-ethyl-1,4- Octadiene, 6-methyl-1,5-octadiene, 7-methyl-1,5-octadiene, 6-ethyl, 5-octadiene, 7-ethyl-1,5-octadiene, 6-methyl 1,6-octadiene, 7-Methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 7-ethyl-1,6-octadiene, 7-methyl-1,4-nonadiene, 8-methyl-1,4-nonadiene, 7 -ethyl-1,4-nonadiene, for 8-ethyl,
4-nonanene, 7-methyl, 5 nonadiene, 8-methyl-1,5-nonadiene, 7-ethyl-1,5-nonadiene, 8-ethyl-15-nonadiene, 7-methyl-
1,6-nonadiene, 8-methyl-16 nonadiene, 7
-ethyl-1,6-nonadiene, 8-ethyl-1,6-
Nonadiene, 7-methyl-1,7-nonadiene, tomethyl-1,7-nonadiene, 7-ethyl-1, founonadiene, toethyl-1,7-nonadiene, 8-methyl-1
, 4-decadiene, 9-methyl-1,4-decadiene,
8-ethyl-1,4-decadiene, 9-ethyl-1,4
-decadiene, 8-methyl-1,5-decadiene, 9-
Methyl 5-decadiene, 8-ethyl-1,5-decadiene, 9-ethyl-1,5-decadiene, 8-methyl-
1,6-decadiene, 9-methyl-1,6-decadiene, 8-ethyl 1,6-decadiene, 9-ethyl-1,6
-decadiene, 8-methyl-1,7-decadiene, 9-
Methyl-1,7-decadiene, 8-ethyl-1,7-decadiene, 9-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, tomethyl-1,8-decadiene, 8-ethyl- 1,8-decadiene, 9-ethyl-1
, 8-decadiene 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.

Furthermore, in addition to the non-conjugated dienes mentioned above, other copolymerizable monomers such as ethylene, propylene, 4-
Methylpentene-1 and the like may be used within a range that does not impair the purpose of the present invention.

The molar ratio of higher α-olefin and butene-1 (higher α-olefin/butene-1) constituting the higher α-olefin copolymer of the present invention is 40/60 to 9515, preferably 50150 to 9515, More preferably 501
It is within the range of 50 to 90/10.

The composition of the higher α-olefin copolymer is determined by 13CNMR.
It can be measured by the method.

In the present invention, it is extremely important to copolymerize butene-1. That is, copolymerization of butene improves strength properties. However, if the composition ratio of butene-1 is too high, the resulting rubber composition will lose its rubber elasticity and cannot be put to practical use.

The iodine value of the higher α-olefin copolymer of the present invention is:
It is in the range of 2-40, preferably 5-30. 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
．． 0 dl/g, preferably in the range of 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 by combining it with other characteristic values, it improves weather resistance, ozone resistance, heat aging resistance,
It is useful in obtaining copolymers with excellent properties such as low-temperature properties and dynamic fatigue resistance.

The degree of crystallinity of the higher α-olefin copolymer according to the present invention measured by X-ray diffraction is 5% or less, preferably 3%.
% or less. The degree of crystallinity was determined by performing X-ray diffraction measurement on the pressed sheet 20 hours after molding.

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, butene-1, 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 used in producing a 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.

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).
X (R is a hydrocarbon group, X is a halide atom, 0
Examples include tetravalent titanium compounds represented by ≦g≦4). More specifically, TiCJ, TiBr
, Ti14;
CH) B+ 3 and other trino-genide alkoxytitaniums; dino-10-genide dialkoxytitaniums such as Ti(OCH3)2C12, Ti(OC2H5)2C12, Ti(On-C4Hs)2C12, Ti(OC2H5)2B12; TI( OCH3)3 C1.

Ti(OC2H5)3C11 Ti(On-C4H9)3 C1.

Mono/% rogenated trialkoxytitaniums such as Ti(QCH)Br; Ti(OCHs)4, TI(QC2H5)4) Ti(oi-C4H9)4 Ti(Oiso-C4H,)4 Ti(0 Examples include tetraalkoxytitanium such as -2ethylhexyl)4.

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, butylmagnesium 11-hydride. These magnesium compounds may be used alone or may form a complex compound with an organoaluminum compound described below. In addition, these magnesium compounds are
It 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,
Alkoxymagnesium such as n-octoxymagnesium, 2-ethylhexoxymagnesium, allyloxymagnesium such as phenoxymagne S/Rum, 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.

In the above formula, R1 represents a substituted or unsubstituted hydrocarbon group, R and R5R' represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group, and R3R4 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group. represents. Note that at least one of R and R 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 a different atom such as N and OlS, such as -C-0-C--COOR, -COOH.

Examples include substituted hydrocarbon groups having structures such as OH, -3o3H, -C-N-C--NH2, and the like.

Among these, diesters derived from dicarboxylic acids in which at least one of RR2 is an alkyl group having 2 or more carbon atoms 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,
Isopropyl diethyl malonate, butyl diethyl malonate, phenyl diethyl malonate, diethyl malonate, allyl diethyl malonate, diisobutyl diethyl malonate, di-n-butyl diethyl malonate, dimethyl maleate, monooctyl maleate, diisooctyl maleate, maleic acid Fats such as diisobutyl acid, isobutyl butyl maleate, diethyl butyl maleate, diisopropyl β-methylglutarate, diallyl ethylsuccinate, di2-ethylhexyl fumarate, diethyl itaconate, diisobutyl itaconate, diisooctyl citraconate, dimethyl citraconate, etc. 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 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, benzylbutyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, dibutyl trimellitate Examples thereof include aromatic polycarboxylic acid esters such as Aromatic Polycarboxylic Acid 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 organosilicon 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, a solid compound may be pulverized. 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.

The solid titanium catalyst components listed in (1) to (8) above [AI
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.

Solid titanium catalyst component [The amount of each of the above-mentioned components used in preparing AI varies depending on the preparation method and cannot be unconditionally defined, but for example, the amount of electron donor per mole of magnesium compound is about 0.01 to In an amount of 5 mol, preferably 0.05 to 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 thus obtained [AI is
Contains magnesium, titanium, halogen and electron donor as essential components.

In this solid titanium catalyst component [AI, 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 [AI contains magnesium halide with a smaller crystal size than commercially available magnesium halogenide, and its specific surface area is usually about 50rr.
f/g or more, preferably about 60 to 1000%/g, more preferably about 100 to 800 rrf/g. Since the solid titanium catalyst component [AI is composed of the above-mentioned components to form a catalyst component, its composition is not substantially changed by hexane washing.

Although such a solid titanium catalyst component [AI] can be used alone, 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, No. 51-20297, No. 5128189, No. 51-64586, No. 51-92885, No. 51-136625, No. 52-87489, No. 52-100596 Publication No. 52-147688, No. 52-1045
Publication No. 93, Publication No. 53-25H, Publication No. 534009
Publication No. 3, Publication No. 53-40094, Publication No. 53-430
Publication No. 94, Publication No. 55-135102, Publication No. 55-1
No. 35103, No. 55-15271G, No. 56-811, No. 5611908, No. 56
-18606 Publication, 5B-83006 Publication, 5
Publication No. 11-13117f15, 511-1:187
Publication No. 06, Publication No. 5g-138707, Publication No. 5B-
No. 138708, No. 58-138709, No. 58-138710, No. 58138715, No. 60-23404, No. 61-21109, No. 6l-37N2, No. 61-37803 , etc.

As the organoaluminum compound catalyst component [B], a compound having at least one AI-carbon bond in the molecule can be used. Such compounds include, for example, (wherein R and R2 are hydrocarbon groups containing usually 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and these may be the same or different from each other. X represents a halogen atom, Ohm≦3, n is 0≦n<3, p is 0≦p<3, q is a number of 0≦q<3, and m+n+p+q=3) Organoaluminum compounds, complex alkylated products of Group 1 metals and aluminum represented by (wherein M is Li, Ns, or K, and R1 is the same as above), and the like can be mentioned.

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

(In the formula, R1 and R2 are the same as above. m is preferably a number of 1.5≦m≦3), general formula R1111A1x
31 (wherein R1 is the same as above, X is halogen, m is preferably Q < m < 3), general formula R',
AI R3-1,l (in the formula, R1 is the same as above. m is preferably 2≦m<3), rogene, O<m≦3.0≦n<3.0≦q<3 , m+
n+q=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 having an average composition of 0.5 expressed as R' 2.5 AZ (OR); diethyl; Dialkylaluminum halides such as aluminum chloride, dibutylaluminum chloride, diethylaluminum bromide; Alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquipromide; Ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dichloride; Partially halogenated aluminum alkyls such as alkyl aluminum cybarides such as bromides.

Other partially hydrogenated alkylaluminums such as dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride, alkylaluminum dihydrites such as ethylaluminum dicdorite, probylaluminum dihydride: ethylaluminum ethoxy chloride, butyl Mention may be made of partially alkoxylated and halogenated alkyl aluminums such as aluminum butoxychloride, 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 (02H5)2AIOAI (C
2H5)2, (04H9)2AlOAl (04H9)
2, C21(5 methylaluminoxane, etc.).

Compounds belonging to the above (i) include L + A1 (C2Hs)4, t-I A I! (c 7 HI 5) 4, etc. can be mentioned.

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,
Diethyl phthalate, diisobutyl phthalate, di-1-butyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide,
Organic acid esters having 2 to 30 carbon atoms such as ethylene carbonate.

Acid halides with 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluyl chloride, and anisyl chloride; 2 to 15 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, and diphenyl ether 20 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 niacetonitrile, 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.

R5i(OR')4□...[I][
In the formula, R and Ro are hydrocarbon groups, and n<4] Specifically, as the organosilicon compound represented by the above general formula [I], trimethylmethoxysilane, trimethylethoxy Silane, dimethyldimethoxysilane,
Dimethyljethoxysilane, diisopropyldimethoxysilane, 1-butylmethyldimethoxysilane, 1-butylmethyljethoxysilane, 1-amylmethyljethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyljethoxysilane, bis o-tolyl diftquinsilane, bis m-1 lyldimethoxysilane, bis p-tolyl dimethoxysilane, bis p
- tolylshedoxinran, bisethyl phenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyljethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane,
Methyltrimethoxysilane, propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltoluethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, (-butyltriethoxysilane, award-butyltriethoxysilane, 1so-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxy (al171oB) Silane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, etc. are used.

Among these, ethyltriethoxysilane, l-propyltriethoxysilane, 1-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane,
Vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis p-)lyldimethoxysilane, p-tolylmethyldimethoxysilane, 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 [II] can also be used.

[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, and R3 is a hydrocarbon group, m is O≦m≦2. 1 In the above formula [n], R1 is a cyclopentyl group or a cyclopentyl group having an alkyl group, and R includes, in addition to the cyclopentyl group, a 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group, 2 , 3-dimethylcyclopentyl group and other alkyl group-containing cyclopentyl groups.

Further, in formula [I1], 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 [I1], R3 is a hydrocarbon group,
Examples of R3 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.

Dialkoxysilanes such as dicyclopentyldimethoxysilane, bis(2methylcyclopentyl)dimethoxysilane, bis(2,3-dimethylcyclopentyl)dimethoxysilane, dicyclopentyljethoxysilane, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclobenchi Examples include monoalkoxysilanes such as dimethylmethoxysilane, 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 a solid titanium catalyst component [A] as described above, an organoaluminum compound catalyst component [B], and an electron donor [C]. This olefin polymerization catalyst is used to copolymerize a higher α-olefin, butene-1, and a nonconjugated diene (main polymerization). After prepolymerizing, higher α-olefin, butene-1, and non-conjugated diene can be copolymerized (main polymerization) using this catalyst. 0.1 to 500 g, preferably 0.1 to 500 g per 1 g of olefin polymerization catalyst during prepolymerization.
α in an amount of 3 to 300 g, particularly preferably 1 to 100 g
- Prepolymerizing olefins or higher α-olefins.

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 in terms of titanium atoms, per inert hydrocarbon medium 11 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 atom 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.

Specifically, the inert hydrocarbon medium used at this time includes propane, butane, pentane, hexane, heptane, octane, decane, dodecane, aliphatic hydrocarbons such as kerosene, didiclopencune, 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. 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-+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 dl/g or more, preferably about 0.2 dl/g or more. It is desirable to use the amount such that the amount becomes 5~]Odl/g.

The prepolymerization is carried out using a solid titanium catalyst component [Al
1. About 0.1 to 500 g per g, preferably about 0.3 to 500 g
It is desirable to carry out the reaction in such a way that 300 g, particularly preferably 1 to 100 g, of polymer are 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.

Solid titanium catalyst component [A] obtained as above
Copolymerization of a higher α-olefin, a butene, and a nonconjugated diene in the presence of an olefin polymerization catalyst formed from an organoaluminum catalyst component [B] and an electron donor catalyst component [C]. (main polymerization).

High-grade α-olefin and butene! During copolymerization (main polymerization) with a non-conjugated diene, in addition to the above olefin polymerization catalyst, as an organoaluminum compound catalyst component,
The same organic aluminum compound catalyst component [B] used in producing the olefin polymerization catalyst can be used.

In addition, in the copolymerization (main polymerization) of higher α-olefin, butene-1, and non-conjugated diene, the electron donor used in producing the olefin polymerization catalyst is used as an electron donor catalyst component. The same catalyst component [C] can be used. Note that the organoaluminum compound and electron donor used in the copolymerization (main polymerization) of higher α-olefin, butene-1, and nonconjugated diene are not necessarily used in preparing the above-mentioned catalyst for olefin polymerization. The organoaluminum compound and electron donor used need not be the same.

Copolymerization (main polymerization) of higher α-olefin, butene-1, and nonconjugated diene is usually carried out in a liquid phase.

As the reaction solvent for the main polymerization, the above-mentioned inert hydrocarbons can be used, or liquid olefins can be used in the wet carbon reaction.

In the copolymerization (main polymerization) of higher α-olefin, butene-1, and nonconjugated diene, the solid titanium catalyst component [A
] is usually about 0.001 to about 1.0 mmol, preferably about 0.0 mmol, in terms of titanium atoms per 11 polymerization volumes.
It is used in an amount of 0.05 to 0.5 mmol. In addition, the organoaluminum compound catalyst component [B] usually has about 1 to 2 metal atoms in the organoaluminum compound catalyst component [B] per 1 mole of titanium atoms in the solid titanium catalyst component [A].
000 mol, preferably about 5 to 500 mol. Furthermore, the electron donor catalyst component [C] is usually about 0.001 to 10 mol, preferably about 0.01 to 2 mol, particularly preferably about 0.001 to 2 mol, per mol of metal atom in the organoaluminum compound catalyst component [B]. is about 0.05 to 1
It is used in molar amounts.

If hydrogen is 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, butene-1, and nonconjugated diene is usually about 20 to 200
℃, preferably about 40 to 100 ℃, the pressure is usually normal pressure to 100 kg/cITr, preferably normal pressure to 50 kg
/cn. In the copolymerization (main polymerization) of higher α-olefins, butenes, and nonconjugated dienes, polymerization can be carried out in any of the batch, semi-continuous, and continuous methods. 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.

Examples of resin modifiers that can be used include polypropylene, polyethylene, polybutene, and polystyrene. To these resins, the high grade α-
Addition of an olefin copolymer can dramatically improve impact resistance and stress crack resistance.

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 as various rubber products, the vulcanizate is prepared by preparing an unvulcanized rubber compound in the same way as when general rubber is vulcanized, and then It is manufactured by molding this compounded rubber into an 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, 25-dimethyl-2,5
-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane,
Examples include 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, di-tert-butyl peroxide, di-tert-butyl peroxy-3,3,S-trimethylcyclohexane, and tert-butyl hydroperoxide. It will be done.

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' mol, preferably 1 x 10 to 5 x 10' mol, per 100 g of the higher α-olefin copolymer of the present invention.
It is used in an amount of 3 x 10' moles.

Further, when a sulfur compound is used as a vulcanizing agent, it is preferable to use a vulcanization accelerator together. Specific examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazole sulfenamide, leoxydiethylene-2-benzothiazole sulfenamide, and N,N-diisopropyl-2-benzothiazole sulfenamide. Amide, 2-mercaptobenzothiazole, 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-
Thiazole compounds such as ethyl-4-morpholinothio)benzothiazole and dibenzothiazyl disulfide; Guanidine compounds such as diphenylguanidine, triphenylguanidine, diorthotolylguanidine, orthotolyl pi guanide, and diphenylguanidine phthalate: acetaldehyde Aldehyde amine or aldehyde-ammonia compounds such as aniline reactants, butyraldehyde-aniline condensates, hexamethylenetetramine, acetaldehyde ammonia: imidacillin compounds such as 2-mercaptoimidacillin: thiocarbamic acid, diethylthiourea, dibutylthio Thiourea compounds such as urea, trimethylthiourea, diorthotolylthiourea; thiuram compounds such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide, dimethyldithiocarbamine Dithio acids such as zinc acid, zinc diethylthiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, and tellurium diethyldithiocarbamate. Examples include salt compounds; xanthate compounds such as zinc dibutylxanthate; and compounds such as zinc white. These vulcanization accelerators are used in amounts of 0.1 to 100 parts by weight of the high α-olefin copolymer.
It is used in an amount of 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 examples include maleimide compounds and divinylbenzene. 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
．． 3-2. Electrons having an energy of OMeV may be irradiated at an absorbed dose of 0.5 to 35 Mrid (megarad), preferably 0.5 to 1QMrsd. At this time, a vulcanization aid may be used in combination with the organic peroxide as a vulcanizing agent, and the amount thereof is 1 x 104 to 1 x 10-
1 mol, preferably 1X10' to 3X10-2 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
After kneading at 0° 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.

(The following is a blank space) Effects of the Invention The higher α-olefin copolymer according to the present invention is composed of a specific higher α-olefin, butene-1, and a specific non-conjugated diene. -1 (higher α-olefin/butene-1) is within a specific range, has a specific iodine value, and has a specific intrinsic viscosity [η]
and has a specific degree of crystallinity, it has excellent weather resistance, ozone resistance, heat aging resistance, and low-temperature properties, as well as excellent dynamic fatigue resistance. Sulfur can be obtained.

Moreover, according to the production method according to the present invention, a higher α-olefin copolymer having the above-mentioned effects can be efficiently produced.
It can be produced with 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 were mixed into 13
After performing a heating reaction at 0°C for 2 hours to obtain a homogeneous solution, 21.3 g of phthalic anhydride was added to this solution, and further,
Stirring and mixing were performed at 130° C. for 1 hour to dissolve phthalic anhydride in this homogeneous solution. After the homogeneous solution thus obtained was cooled to room temperature, the entire amount of 75 ml of this homogeneous solution was dropped over 1 hour into 200 ml of titanium tetrachloride maintained at -20°C. After charging, the temperature of this mixed solution was raised to 110° C. over 4 hours, and when it reached 110° C., 5.22 g of diisobutyl phthalate was added, and the mixture was kept at the same temperature for 2 hours with stirring. After the 2-hour reaction, the solid portion was collected by hot filtration, and this solid portion was resuspended in 275 ml of titanium tetrachloride, and then suspended again in 1 ml of titanium tetrachloride.
A heating reaction was carried out at 10° 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. Solid titanium catalyst component [A] thus obtained
The composition was 2.5% by weight of titanium, 63.9% by weight of chlorine, 20.9% by weight of magnesium, and 12.7% by weight of diisobutyl phthalate.

(Polymerization) Using 41 glass polymerization vessels equipped with stirring blades, octene-1, butene-1, and 7-methyl-16-
A copolymerization reaction with octadiene was carried out.

That is, a decane solution of octene-1 and 7-methyl-1,6-octadiene was added from the top of the polymerization vessel, and the octene-1 concentration in the polymerization vessel was 1.07 g/l.
- A decane slurry solution of solid titanium catalyst component [8] was added as a catalyst at 1.4 m'/hour so that the concentration of octadiene in the polymerization vessel was 3.4 g/l, and the titanium concentration in the polymerization vessel was 0.03 0.41 mmol/l.
) A decane solution of isobutylaluminum was heated at 1.21% per hour so that the aluminum concentration in the polymerization vessel was 3.0 mmol/l. ) A solution of trimethylmethoxysilane in decane was added at 1 hourly so that the silane concentration in the polymerization vessel was 1.0 mmol/l. were continuously fed into the polymerization reactor at a rate of 100 ml. On the other hand, the polymerization solution in the polymerization vessel was continuously drawn out from the lower part of the polymerization vessel so that the concentration of the polymer solution was always 21. Also, from the top of the polymerization vessel, 151 butene-1 per hour and 2 I per hour of hydrogen were added.
, nitrogen was supplied at a rate of 1351/hr. 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 extracted from the lower part of the polymerization vessel to stop the copolymerization reaction, and the polymerization solution was immersed in a large amount of methanol to precipitate a copolymer. After thoroughly washing the copolymer with methanol, it was heated to 140°C.
After drying under reduced pressure all day and night, a butene-to-octane/7-methyl-16-octadiene copolymer was obtained at a rate of 190 g/hour.

The molar ratio of octane and butene-1 (octene-1/butene) constituting the obtained copolymer was 78/22, and the iodine value was 5.3, measured in decalin at 135°C. The intrinsic viscosity [η] is 5.1 dl/g), and
The degree of crystallinity measured by line diffraction was 0.

Examples 2 to 6 In Example 1, copolymerization was carried out in the same manner as in Example 1 by changing the monomers and polymerization conditions to obtain the copolymers shown in Table 1. .

\ \ Example 7 The butene-octenate 7-methyl-16-octadiene copolymer produced in Example 1 was kneaded using an 8-inch open roll according to Table 2 to obtain an unvulcanized compounded rubber.

Table 2 1) Product name, Asahi 80: Manufactured by Asahi Carbon ■2) Product name, Suncellar support; Manufactured by Sanshin Kagaku Kogyo ■3) Product name
Suncellar TT - Manufactured by Sanshin Kagaku Kogyo ■ This compounded rubber was heated for 20 minutes in a press heated to 160°C to produce a vulcanized sheet, and the following tests were conducted. The test items are as follows.

[Test items] Tensile test, hardness test, ozone resistance test, aging test, bending test.

[Test Method] Tensile test, hardness test, ozone resistance test, aging test, and bending test were measured according to Monthly S K 6301. That is,
In the tensile test, tensile strength (T), elongation (E),
In the hardness test, H8Its^ hardness was measured. The ozone resistance test was conducted in an ozone test tank, and the conditions were that the ozone concentration was 5.
0 pphm, elongation rate 20%, static test was conducted at 40°C atmosphere. Evaluation is based on the surface condition of its K 6301
This was done in accordance with the standards. As for the aging test, an air heating aging test was conducted at 120° C. for 70 hours. After the aging test, a tensile test was conducted to determine the retention rate of the physical properties before aging, that is, the tensile strength retention rate A.

(T), elongation retention A, and (E,) were determined.

The bending test was performed using a dematcher testing machine to examine resistance to crack growth.

That is, 1 crack 5m5 The number of times it was bent was measured.

The results are shown in Table 3.

table

[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.

Claims (1)

[Scope of Claims] 1) Higher α-olefin having 6 to 20 carbon atoms and butene-
1 and a nonconjugated diene represented by the following general formula [I], comprising (a) molar ratio of higher α-olefin to butene-1 (higher α-olefin/butene-1); is 40/60~95/
(b) the iodine number is within the range of 2 to 40, (c) the intrinsic viscosity measured in decalin solvent at 135°C [
η] is within the range of 1.0 to 10.0 dl/g, and (d) the degree of crystallinity measured by X-ray diffraction is within the range of 5% or less. Copolymer; ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] (In the formula, n is an integer from 1 to 5, and R^1 is a carbon number of 1 to
The alkyl group of 4, R^2 and R^3 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. However, R^2 and R^3 are never both hydrogen atoms. ) 2) Olefin polymerization formed 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 (a) A higher α-olefin is obtained by copolymerizing a higher α-olefin having 6 to 20 carbon atoms, butene-1, and a non-conjugated diene represented by the following general formula [I] in the presence of a catalyst for and butene-1 (higher α-olefin/butene-1) is 40/60 to 95/
(b) the iodine number is within the range of 2 to 40, (c) the intrinsic viscosity measured in decalin solvent at 135°C [
η] is within the range of 1.0 to 10.0 dl/g, and (d) obtain a higher α-olefin copolymer whose crystallinity as measured by X-ray diffraction is within the range of 5% or less. A method for producing a high-grade α-olefin copolymer characterized by; ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] (In the formula, n is an integer from 1 to 5, and R^1 has 1 or more carbon atoms
The alkyl group of 4, R^2 and R^3 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. However, R^2 and R^3 are never both hydrogen atoms. )