JPH03174415A - Higher alpha-olefin copolymer and its production - Google Patents

Abstract

PURPOSE:To obtain the title copolymer excellent in dynamic fatigue resistance, weathering resistance, O3 resistance, etc., by specifying the molar ratio of the alpha-olefin to the 4-methylpentene-1, the iodine value, etc., of a copolymer comprising a specified linear higher alpha-olefin, a non-conjugated diene and 4- methylpentene-1. CONSTITUTION:A copolymer comprising a 6-20C linear higher alpha-olefin, 4- methylpentene-1 and a conjugated diene of the formula (wherein n is 1-5; R<1> is a 1-4C alkyl, and R<2> and R<3> are each H or a 1-8C alkyl group, provided that the case in which both are H atoms is excluded), wherein the molar ratio of the linear higher alpha-olefin to the 4-methylpentene-1 is 50/50-95/5, the iodine value is 2-40, the intrinsic viscosity as measured in decalin at 135 deg.C is 1.0-10.0dl/g, and the degree of crystallization is 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.
It has excellent properties such as bending fatigue resistance), weather resistance, ozone resistance, heat aging resistance, and low temperature properties, and is suitable for various rubber products and resin modification 44
This invention relates to a higher α-olefin copolymer that can be used for applications such as, and a method for producing the same.

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 key supplies, and rubber coatings.
It is widely used as a plastic blending material for rubber products such as 'li, 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. .

Furthermore, although natural rubber has excellent dynamic fatigue resistance, it has poor heat resistance and ozone resistance, which poses practical problems.

On the other hand, JP-A No. 63-150307 discloses a random copolymer consisting of hexene-i and 4-methylpentene-1. had to be vulcanized using peroxide. Therefore, when the above-mentioned vulcanization is carried out, vulcanization and molecular cleavage occur in parallel, resulting in the problem that the physical properties originally possessed by this copolymer cannot be sufficiently exhibited.

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. When a specific linear higher α-olefin, 4-methylpentene-1, and a specific non-conjugated diene were copolymerized in the presence of The present inventors have discovered that the present invention can be obtained, and have completed the present invention.

Purpose of the Invention The purpose of the present invention is to provide a high-grade α-olefin copolymer having excellent weather resistance, ozone resistance, heat aging resistance, and low-temperature properties as well as excellent dynamic fatigue resistance, and a method for producing the same. There is.

Summary of the Invention The higher α-olefin copolymer according to the present invention comprises a linear higher α-olefin having 6 to 20 carbon atoms, 4-methylpentene-1, and a nonconjugated copolymer represented by the following general formula [I1]. A copolymer consisting of a diene and (a) a linear higher α
- The molar ratio of olefin and 4-methylpentene-L (linear higher α-olefin/4-methylpentene-1) is within the range of 50/50 to 9515, and (b) iodine IdIi is 2 to 40 (c) The intrinsic viscosity [η] determined by 7]111 in a decalin solvent at 135°C is within the range of 1.0 to 10.0 dl/g, (d) As determined by X-ray diffraction method. It is characterized in that the measured crystallinity is within a range of 596 or less.

(In the formula, n is an integer of 1 to 5, and R1 has 1 to 4 carbon atoms.
The alkyl group, R2 and R3 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. However, R2 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 In the presence of an olefin polymerization catalyst formed from a catalyst component and [C] an electron donor catalyst component, a linear higher α-olefin having 6 to 20 carbon atoms, 4-methylpentene-l, and the following general By copolymerizing a non-conjugated diene represented by the formula [I1, (a) the molar ratio of linear higher α-olefin and 4-methylpentene (straight higher α-olefin/4-methylpentene- 1) is 5015
(b) has an iodine number in the range of 2 to 40, (c) has an intrinsic viscosity measured in decalin solvent at 135°C [
η] is 1.0 to 10. Od, l! (d) A higher α-olefin copolymer having a crystallinity determined by ApJ by X-ray diffraction 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. ) 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 is composed of a linear higher α-olefin, 4-methylpentene-1, and a nonconjugated diene.

The linear higher α-olefin used in the present invention is an α-olefin having 6 to 20 carbon atoms, and specifically includes hexene-11 heptene-1, octene-1, nonene-1
, decene-11 undecene-11 dodecene-1, tridecene-1, tetradecene-1, pentadecene-11 hexadecene-11 heptadecene-11 nonadecene-11 eicosene-1, and the like.

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

Among the above linear higher α-olefins, hexene-1,
Octene-1, decene-1, 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-1,4-
hexadiene, 4-ethyl-1,4-hexadiene, 5
-ethyl-1,4-hexadiene, 5-methyl-1,4
-hebutadiene, 6-methyl-1,4-heptadiene,
5-ethyl-1,4-hebutadiene, 6-nityl 1.
4-hebutadiene, 5-methyl-1,5-hebutadiene, 6-methyl-(,5-hebutadiene, 5-ethyl-1
, 5-hebutadiene, 6-ethyl-1,5-heptadiene, 6-methyl-1,4-octadiene, 7-methyl-
1,4-octadiene, 6-nityl-1,4-octadiene, 7-ethyl-1,4-octadiene, 6-methyl-1,5-octadiene, 7-methyl-1,5-octadiene, 6-nityl-1 .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, 8-ethyl-1,4-nonadiene, 7-methyl-1,5-nonadiene, 8-methyl-1,5-nonadiene, 7- Ethyl-1,5-nonadiene, 8-ethyl-
1,5-nonadiene, 7-methyl-1,6-nonadiene, 8-methyl-1,6-nonadiene, 7-nityl-t,
6-nonadiene, 8-ethyl-1,6-nonadiene, 7
-Methyl-1,7-nonadiene, 8-methyl-1,7-
nonadiene, 7-ethyl-1,funonadiene, 8-ethyl-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-1
, 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-thiru-t,e-decadiene, 8-me,thiru-1,7-zocadiene, 9-methyl-1,7-decadiene, 8-ethyl-1,7-decadiene, 9 -ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-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 singly or as a mixture of two or more.

Furthermore, in addition to the above-mentioned non-conjugated dienes, polymerizable monomers such as ethylene, propylene, butene-1, etc. may be used within the range that does not impair the object 1-1 of the present invention.

The molar ratio of linear higher α-olefin and 4-methylpentene-1 (linear higher α-olefin/4-methylpentene-1) constituting tM of the higher α-olefin copolymer of the present invention is , 50150-9515, preferably 55/
It is within the range of 45 to 90/10.

Higher α-olefin type (polymer composition is 13C-N
It can be measured by MR method.

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
．． 0dll/lr, preferably 1.5-7cN1)/g
is within the range of 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 can be used to improve weather resistance, ozone resistance, heat aging resistance, low temperature characteristics, and vibration resistance. It is useful in obtaining copolymers with excellent properties such as physical 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 is determined by performing X-ray diffraction δp+ constant on a pressed sheet 20 hours after molding.

The higher α-olefin type J (polymer) 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 can be obtained by copolymerizing a linear higher α-olefin, 4-methylpentene-1, and a nonconjugated diene in the presence of an olefin polymerization catalyst. can get.

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 13 (donor catalyst component [C]).

FIG. 1 shows an example of a flowchart of the "higher α-olefin system" method (preparation of catalyst component for olefin polymerization used in producing a polymer) 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 electron lj2 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).
It is possible to exclude tetravalent titanium compounds represented by More specifically, TiCg
% TiBrSTiI4, etc.; Ti(OCR)Cfla, Ti(OC2H5)CI13, TI(On-C4H9)(13, TI(OC2H5)Br3, T:(Oiso C4H9)Br3, etc. trihalogenated alkoxytitaniums such as Ti(OCH3)2Cg2, Ti(OC2H5)2CD2, TI(On-C4H9)2cg2, Ti(OC2H5)2B'2; dihalogenated dialkoxytitaniums such as Ti(OCH3)2C(1 .

”r+(OC2H5) 3tl, T i(On-C,s H9) 3C(1-Tl(O
Mono/halogenated trialkoxytitanium such as C2H5)38r; TI(OCH3)4, T1(OC2H5)4, Ti(On-C4H9)4Ti(O1So-C4H9)4 such as Ti(0-2ethylhexyl)4 Examples include tetraalkoxytitanium.

Among these, l.logen-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 can be used alone or
It may form a complex compound with an organoaluminum compound described later. Further, these magnesium compounds may be limbs or solids.

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, butquin magnesium,
Examples include alkoxymagnesiums such as n-octoxymagnesium and 2-ethylhexoxymagnesium; allyloxymagnesiums such as phenoxymagnesium and dimethylphenoxymagnesium; and magnesium carboxylates such as magnesium laurate and magnesium stearate.

These non-reducing magnesium compounds may be compounds derived from the above-mentioned reducing magnesium compounds or compounds derived during the preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducing magnesium compound, for example, a reducing magnesium compound can be derived from a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, etc. It may be brought into contact with a compound such as.

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, 11! of the homogeneous titanium catalyst component [A]! J
Examples of the electron donor used in the production include organic carboxylic acid esters, preferably polyhydric carboxylic acid esters,
Specifically, compounds represented by the following formula having any skeleton may be mentioned.

R3-C-C0OR'R'-C-COOR"R' -C-COOR6 R3-C-COOR'R'-C-COOR" In the above formula, R1 represents a substituted or unsubstituted hydrocarbon group, R2R5R6 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, and 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 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, -3o H, -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,
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, di2-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 normal-butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, phthalate Diisobutyl acid, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, didecyl phthalate, benzylbutyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, dibutyl trimellitate, etc. Examples include aromatic polycarboxylic acid esters, esters derived from heterocyclic polycarboxylic acids such as 3,4-furandicarboxylic acid, and the like.

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 having 2 or more carbon atoms, and particularly preferred are diesters obtained by reacting phthalic acid with an alcohol having 2 or more carbon atoms.

As these polyvalent carboxylic acid esters, it is not necessarily necessary to use the polyvalent carboxylic acid esters as mentioned above as starting materials, and these polyvalent carboxylic acid esters are A polyhydric carboxylic acid ester may be generated in the preparation step of the solid titanium catalyst 1 [A] using a compound capable of inducing the following.

In the present invention, electrons 1j other than polyhydric carboxylic acids that can be used when preparing the solid titanium catalyst [A]
I-! 7. Examples include alcohols, amines, amides, ethers, ketones, nitriles, phosphine compounds, stibines, arsine, phosphoramides, esters, thioethers, thioesters, and acid anhydrides, as described below. organic silicon compounds such as acid halides, aldehydes, alcoholates, alkoxy(aryloxy)silanes, organic acids, and amides and salts of metals belonging to groups can be mentioned.

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 in which a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor is reacted with a titanium compound in a liquid (step 11). 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 is an electron! −j.

bodies and/or organoaluminum compounds and halogen a
Pretreatment with reaction aids such as l-7 silicon compounds may also be carried out. In addition, in this method, the above type 7-1j,
! =7. Use your body 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 wavy 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),
Electric j' fRF5. How to further react titanium compounds with titanium compounds.

(5) A solid substance obtained by pulverizing a magnesium compound or a complex compound consisting of a magnesium compound and an electron isomer in the presence of a titanium compound is treated with either a halogen, a halogen compound, or an aromatic hydrocarbon. How to process. In this method, a magnesium compound or a complex compound consisting of a magnesium compound and an electrolyte may be ground in the presence of a grinding aid or the like. A complex compound consisting of 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.As a reaction aid, an organoaluminum compound may be used. Alternatively, halogen-containing silicon compounds may be used.

In addition, in this method, at least all of the electron
Use j-body.

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

(7) Electron!
5. Methods of contact with the body and titanium compounds.

(8) Reaction of 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 methods for preparing the catalyst, a method using liquid titanium halide or a method using a titanium compound after preparing the catalyst, or a method using a halogenated hydrocarbon when using a titanium compound are particularly 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 specified, but for example, the amount of electron donor per 1 mole of magnesium compound is In an amount of about 0.01 to 5 mol, preferably 0.05 to 2 mol, the titanium compound
．． The amount preferably ranges from 0.01 to 500 mol, and preferably from 0.05 to 300 mol.

The solid titanium catalyst component [A] thus obtained contains magnesium, titanium, /% rogen, and an electron donor as essential components.

In this solid titanium catalyst component [A],
Titanium (atomic ratio) is approximately 4-200. Preferably around 5-1
00, and the electron donor/titanium (molar ratio) is approximately 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 halides, and usually has a specific surface area of about 501 Tl.
l/fr or more, preferably about 60 to 1000 rT'Il
It is more preferably about 100 to 800 i/g. The composition of this solid titanium catalyst component [A] is not substantially changed by hexane washing, since the above-mentioned components are integrated to form the catalyst I component.

Such a solid titanium catalyst component [A] can be used alone, but it can also be used with, for example, silicon compounds,
It can also be used after being diluted with an inorganic compound such as an aluminum compound or polyolefin, or an organic compound. Note that 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 publication, 51-20297 publication, 51-28189 publication, 51-64586 publication,
No. 51-92885, No. 5l-136Ff25, No. 52-87489, No. 52-10059
Publication No. 8, Publication No. 52-147688, Publication No. 52-10
Publication No. 4593, Publication No. 53-2580, Publication No. 53-4
No. 0093, No. 53-40094, No. 53-
No. 43094, No. 55-135102, No. 5
No. 5-135103, No. 55-152710, No. 5B-811, No. 5B-11908,
5B-18606, 58-83006, 5g-138705, 58-138708
No. 58-138707, No. 58-138
No. 708, No. 58-138709, No. 58-
No. 138710, No. 58-138715, No. 53-2580, No. 61-21109, No. 61-37802, No. 81-37803,
etc. are disclosed.

As the organoaluminum compound catalyst component [B], a compound having at least one Ag-carbon bond in the molecule can be used. Examples of 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 cumulative. X represents a halogen atom, 0<m≦3, n is 0≦n<3, p is O≦p<3, q is a number of 0≦q<3, and m+n+p+q=3. ), (i) a complex alkylated compound of Group 1 metal and aluminum represented by the general formula MiR14 (wherein Ml is Li, Na, and R1 is the same as above); can be mentioned.

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

(In the formula, R and R2 are the same as above. m is preferably 1
．． 5≦m53), general formula RADX3-I+1 (in the formula, R1 is the same as above, X is halogen, m is preferably 0<m<3), ■ general formula RApH3-m (in the formula , R1 is the same as above. m is preferably 2≦m<3
), (wherein R and R2 are the same as above.
<m≦3, O≦n<3, O≦q<3, m+n+q-3
Examples include compounds represented by

More specifically, aluminum compounds belonging to (i) include trialkylaluminum nitriisoprenylaluminum alkenylaluminum such as triethylaluminum and tributylaluminium; dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; ethylaluminum Sesquiethoxide, alkylaluminum sesquialkoxide such as butylaluminum sesquibutoxide, Hei 2,5 0.51'i expressed as R'l (OR)
Partially alkoxylated alkyl aluminum having the composition J; dialkyl aluminum halides such as diethylaluminum chloride, dibutyl aluminum chloride, diethylaluminum bromide; alkyl aluminum halides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquipromide Aluminum sesquihalides; Partially halogenated alkylaluminiums such as alkyl aluminum cybarides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide; Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride; ethylaluminum Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as dikudolide, probylaluminum dihydride; partially alkoxylated such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide and halogenated alkyl aluminums.

Compounds similar to (i) include organoaluminum compounds in which two or more pieces of aluminum are bonded together via an oxygen atom or a nitrogen atom. Examples of such monsters include (C2H5)2AJ70AD (
C2H5)2, (C4H9)2AgOAg (C4H9
)2, methylaluminoxane, etc.

As a compound belonging to the pre-historic period (i), LIAg
Examples include (C2H5)4, L i A,17 (CIH15)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. , ammonia, amines, nitriles, isocyanates, and the like, or polyhydric carboxylic acid esters such as those mentioned 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, etc. with 1 or more carbon atoms 18 Alcohols: Phenols with 6 to 20 carbon atoms that may have lower alkyl groups such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, naphthol, etc. Mi: acetone, methyl ethyl ketone, methyl isobutyl Ketones having 3 to 15 carbon atoms such as ketone, acetophenone, benzophenone, and benzoquinone; Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, nathaldehyde; methyl formate, methyl acetate, Ethyl acetate, vinyl acetate, propyl acetate, octyl acetate,
Cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate , octyl benzoate, cyclohexyl benzoate, phenyl benzoate,
Benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate,
Diethyl nazic acid, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di-2-ethylhexyl phthalate, γ
- Organic acid esters with 2 to 30 carbon atoms such as butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate; 2 to 1 carbon atoms such as acetyl chloride, benzoyl chloride, toluyl chloride, anisyl chloride, etc.
Acid halides of No. 5; methyl ether, ethyl ether,
Ethers having 2 to 20 carbon atoms such as isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether; acetate amide,
Acid amides such as benzoic acid amide and toluic acid amide;
Amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylenediamine; Nitriles such as acetonitrile, benzonitrile, tolnitrile; acetic anhydride, phthalic anhydride, benzoic anhydride Acid anhydrides such as acids 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 1, R and R′ are hydrocarbon groups, and Okn<
4] As the organosilicon compound represented by the above general formula [I], trimethylmethoxysilane, l
- Limethylethoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, diisopropyldimethoxysilane, L-butylmethyldimethoxysilane, L-butylmethyljethoxysilane, t-amylmethyljethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane , diphenyljethoxysilane,
Bis 0-tolyldimethoxysilane, bis m-tolyldimethoxysilane, bis I)-)lyldimethoxysilane, bis p-tolyljethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane,
Cyclohexylmethyldimethoxysilane, cyclohexylmethyljethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane Methoxysilane, γ-chloropropyltrimethoxysilane, methyltoluethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, 1so-butyltriethoxysilane, phenyltriethoxysilane Silane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriisopropoxysilane, vinyltriptoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxysilane, vinyltris(
β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, etc. are used.

Among these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane,
vinyltributoxysilane phenyldimethoxysilane,
Preferred are phenylmethyldimethoxysilane, bis-p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, and diphenyljethoxysilane.

Further, as the electron (codonor catalyst component [C]), an organosilicon compound represented by the following general formula [I1] can also be used.

[In the formula, 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 0≦m≦2. ] In the above formula [I1], R1 is a cyclopentyl group or a cyclopentyl group having an alkyl group, and R1
In addition to cyclopentyl, examples include cyclopentyl groups in which an alkyl group is hydrogenated, such as 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group, and 2,3-dimethylcyclopentyl group.

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.

Specifically, such organosilicon compounds include cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, and cyclopentyl!・Trialkoxysilanes such as ethoxysilane; Dialkoxysilanes such as dicyclopentyldimethoxysilane, bis(2-methylcyclopentyl)dimethoxysilane, bis(2,3-dimethylcyclopentyl)dimethoxysilane, dicyclopentyljethoxysilane; Monoalkoxysilanes such as tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, cyclopentyldimethylethoxysilane, etc. can be mentioned. Among these electron donors, organic carboxylic acid esters or organic silicon compounds are preferred, and H organosilicon 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 polymerize a higher α-olefin, 4-methylpentene-1, and a non-conjugated diene. After polymerization, higher α-olefin, 4-methylpentene-1, and non-conjugated diene can also be polymerized (main polymerization) using this catalyst. 0.1 to 500 g per 1 g of olefin polymerization catalyst during prepolymerization,
Preferably 0.3 to 300 g, especially 17' or 1
The α-olefin or higher α-olefin is prepolymerized in an amount of ˜100 g.

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 the solid titanium catalyst component [A] in the preliminary TJx reaction is usually about 0.01 to 200 mmol, preferably about 0.1 to 100 mmol, particularly about 0.1 to 100 mmol, in terms of titanium atoms, per 1 g of the inert hydrocarbon medium described below. Preferably, the amount is in the range of 1 to 50 mmol.

The amount of organoaluminum catalyst component [B] is 0.1 to 500 g per 1 g of solid titanium catalyst component [A1, preferably 0,
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 0.11 to 50 moles, preferably 0.5 to 30 moles, particularly preferably 1 to 10 moles, per mole 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.

Specific examples of the inert hydrocarbon medium used in this case include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene.

Examples include alicyclic hydrocarbons such as cyclopenkune, cyclohexane, and methylcyclopentane; 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 also be carried out using the olefin or higher α-olefin itself as a solvent.

The linear higher α-olefin used in the prefiit polymerization may be the same as or different from the linear higher α-olefin used in the main polymerization described later.

The reaction temperature during -3'-prepolymerization is usually about -2() to +
It is desirable that the temperature is 100°C, preferably about -20 to +80°C, more preferably 0 to +40°C.

In addition, in the prepolymerization, molecular weight such as hydrogen, ``1
,1. J moderation agents can also be used. Such a moderating agent having a molecular weight of 1 has an intrinsic specific viscosity [η] of the polymer obtained by prepolymerization measured in a decalin solvent at 135°C of about 0.
2dj7/g or more, preferably about 0. 5-1. Od
It is desirable to use an amount such that D/g.

T-EFH polymerization is carried out using a solid titanium catalyst component [about 0.1 to 500 g per 1 g of A, preferably about 0.0 g, as described above.
It is desirable to carry out the reaction in such a way that 3 to 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 is likely to decrease.

Prepolymerization can be carried out batchwise or continuously.

An olefin polymerization catalyst (solid titanium catalyst component [A] obtained by carrying out T-prepolymerization as described above),
7f of an olefin polymerization catalyst formed from an organoaluminum catalyst component [B] and an electron donor catalyst component [C]
Copolymerization (main polymerization) of a linear higher α-olefin, 4-methylpentene-1, and a non-J (functional diene) is carried out under the presence of the polymer.

Linear higher α-olefin and 4-methylpentene-1
During copolymerization (main polymerization) with a non-conjugated diene, in addition to the above olefin polymerization catalyst, the organoaluminum compound catalyst used in producing the olefin polymerization catalyst is added as an organoaluminum compound catalyst component. The same thing as component [B] can also be used. Also, linear high-grade α
- Used as an electron donor catalyst component in the copolymerization (main polymerization) of olefin, 4-methylpentene-l, and non-conjugated diene to produce an olefin polymerization catalyst)
The electron donor catalyst component [similar to C can be used. In addition, linear higher α-olefin and 4
-Copolymerization of methylpentene-1 and a non-)(functional diene)
The organoaluminum compound and electron donor used in the main polymerization are not necessarily the same as the organoaluminum compound and electron donor used in preparing the olefin polymerization catalyst described above.

Copolymerization (main polymerization) of a straight 111-shaped higher α-olefin, 4-methylpentene-1, and a nonconjugated diene is usually carried out by
It is done with liquid...

As the reaction solvent for the main polymerization, the above-mentioned inert hydrocarbon can be used, or an olefin in the shape of 1" at the reaction temperature can also be used.

Linear higher α-olefin and 4-methylpentene-1
In the copolymerization with non-conjugated diene (main polymerization), the solid titanium catalyst component [A] is usually about 0.001 to about 1.0 mmol in terms of titanium atoms per 12 polymerization volume,
Preferably, it is used in an amount of about 0.005 to 0.5 mmol.

In addition, the organoaluminum compound catalyst component [B] is χ4 per mole of titanium atoms in the solid titanium catalyst component [A],
The metal atoms in the aluminum compound catalyst component [B] are generally used in an amount of about 1 to 2000 mol, preferably about 5 to 500 mol. Furthermore, the electron donor catalyst component [C] is an organoaluminum compound catalyst component [8
Usually about 0.001 to 1 mole of metal source T-1
The amount used is such that it is 0 mol, preferably about 0.01 to 2 mol, particularly preferably about 0.05 to 1 mol.

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

In the present invention, the polymerization temperature of linear higher α-olefin, 4-methylpentene-1, and non-conjugated diene is usually about 20 to 200°C, preferably about 40 to 100°C, and the pressure is: Normal pressure is usually set to 100 kg/cJ, preferably normal pressure to 50 kg/cd. In the copolymerization (main polymerization) of a linear higher α-olefin, 4-methylpentene-1, and a nonconjugated diene, the polymerization can be carried out using a batch method, a semi-continuous method, or a continuous method. Furthermore, the polymerization can be carried out by changing the reaction conditions.
It can also be done in stages or more.

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. Especially when applied to resin modification and various rubber products, its properties are maximized.

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

Each rubber insert product is 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 desired 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 the higher α-olefin copolymer 100 of the present invention! lI
0.05 to 10 parts by weight, preferably 0.05 to 10 parts by weight, based on part f.
It is used in an amount of 1 to 5 parts by weight. 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)hexyne-3, di-tert-butyl peroxide, di-tert-butylperoxy-3,3,5-1-limethylcyclohexane, tert-butyl Examples include hydroperoxides. Among them, dicumyl peroxide, di-tert-butyl peroxide, di-tert-butyl peroxide-3,3,
5-h-limethylcyclohexane is preferably used.

The organic peroxide is used in an amount of 3 x 10 to 5 x 10 -2 mol, preferably 1 x 10 to 3 x 10 -2 mol, per 100 g of the higher α-olefin copolymer 4 of the present invention.

Further, when using a sulfur compound as a vulcanizing agent, it is preferable to use a vulcanization accelerator. 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-(2,6
-diethyl-4-morpholinothio)benzothiazole,
Thiazole compounds such as dibenzothiazyl disulfide; diphenylguanidine, triphenylguanidine,
Guanidine compounds such as diorthotolyl guanidine, orthotolyl pi guanide, diphenylguanidine phthalate; acetaldehyde-aniline reaction products;
Aldehyde amine or aldehyde-ammonia compounds such as butyraldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde ammonia; 2-
imidacillin compounds such as mercaptoimidacillin;
Thiourea-based compounds such as thiocarbamic acid, diethylthiourea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea; tetramethylthiuram monosulfide, tetramethylthiuram disulfide,
Thiuram compounds such as tetraethylthiuram 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 include compounds such as zinc white. These vulcanization accelerators are used in an amount of 0.00 parts by weight per 100 parts by weight of the higher α-olefin copolymer.
It is used in amounts 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 1 x 10-4 to 100 g of the higher α-olefin copolymer of the present invention. 1×
10-1 mol, preferably 1 x 10 to 3 x 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
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 performed using a mold or may be carried out without using a mold. When a mold is not used, the molding and vulcanization steps are usually carried out continuously. As a heating method in the vulcanization tank, a heating tank using hot air, glass beads fluidized bed, UHF (ultra high frequency electromagnetic waves), steam, etc. 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 blending a foaming agent into 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 comprises a specific linear higher α-olefin and 4-methylpentene-1
and a specific non-conjugated diene, forming a linear higher α-
The molar ratio of olefin and 4-methylpentene-1 (linear higher α-olefin/4-methylpentene-1) is within a specific range, the specific iodine number, the specific intrinsic viscosity [
η] and 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. A better vulcanizate can be obtained.

Further, according to the production method according to the present invention, a higher α-olefin copolymer having the above-mentioned effects can be produced in a high yield in young cows.

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

Example 1 (Preparation of homogeneous titanium catalyst component [A]) Anhydrous magnesium chloride 95.2. , Decane 442 ml
and 2-ethylhexyl alcohol 390. After heating and reacting fzr at 130°C for 2 hours to make a homogeneous solution, 21.3 g of phthalic anhydride was added to this solution, and stirring and mixing was further performed at 130°C for 1 hour to dissolve the phthalic anhydride. Dissolved in a homogeneous solution. After cooling the homogeneous solution obtained in this way to room temperature, 75 ml of this homogeneous solution was added.
1 in 200 ml of titanium tetrachloride kept at -20°C.
The entire amount was dropped and charged over a period of time. After charging, the temperature of this mixed liquid was raised to 110°C over 4 hours, and 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 reaction was completed, the solid portion was collected by hot filtration, and after resuspending the solid portion in 275 ml of titanium tetrachloride, the reaction was heated 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 titanium compound of a-isolated 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 2.5% by weight of titanium, 63.9% by weight of chlorine, 20.9mHkg6 of magnesium, and 12.7% by weight of diisobutyl phthalate.

(Polymerization) Stir r1! A 500 ml polymerization vessel equipped with wings was charged with 200 ml of decane, 30 ml of octene-1, 20 ml of 1,4-methylpentene-1, and 1 ml of 1,7-methyl-1,B-octadiene. The temperature of this solution was set to 50”C.
and hydrogen and nitrogen at 3R and 5R per hour, respectively.
0.047 into the solution continuously. After raising the temperature to 50'C, 0.625 mmol of triisobutylaluminum, 0.21 mmol of trimethylethoxysilane, and 0.013 mmol of solid titanium catalyst component [A] in terms of titanium atoms were charged to initiate polymerization. It started. 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 100°C overnight to give 12.3g of 4-methylbentene-
A too-octento 7-methyl-1,6-octadiene copolymer was obtained. The molar ratio of octene-1 and 4-methylpentene-1 (octene-1) forming the groove bottom of the obtained copolymer is
174-methylpentene-1) has a ratio of 73/27, an iodine number of 6.2, an intrinsic viscosity [η] measured in decalin at 135°C of 4.7 dfl/g, and an X-ray diffraction method. The measured crystallinity was 0%.

Examples 2 to 5 Copolymerization was carried out in the same manner as in Example 1 except that the monomers and polymerization conditions were changed as shown in Table 1 to obtain the copolymers shown in Table 1.

Implementation row 6 Stir J'l! Using a 4g glass polymerization vessel equipped with wings,
A copolymerization reaction of octene-1, 4-methylpentene-1, and 7-methyl-1,6-octadiene was continuously carried out.

That is, a decane solution of octene-1,4-methylpentene-1 and 7-methyl-1,6-octadiene was poured into the upper part of the polymerization vessel until the octene-■ concentration in the polymerization vessel was 69 g.
/ff, so that the concentration of 4-methylpentene-1 in the polymerization vessel is 16 g/47.7-methyl-1,8-octadiene in the polymerization vessel is 5.3 g/(l). every nl
2 g, a decane slurry solution of solid titanium catalyst component [A'] was used as a catalyst until the titanium concentration in the polymerization vessel was 0.0.
A solution of triisobutylaluminum in decane was added at 0.4 g per hour so that the aluminum concentration in the polymerization vessel was 3.5 mmol/g.
A decane solution of 8/N, l-limethylmethoxysilane was continuously fed into each polymerization vessel at a rate of 0.8fI/hour so that the silane concentration in the polymerization vessel was 0.7 mmol/ρ. . On the other hand, the polymer solution in the polymerization vessel was continuously drawn out from the lower part of the polymerization vessel so that the amount of the polymer solution remained at 2 g at all times.

Additionally, from the top of the polymerization vessel, 3 g of hydrogen per hour and 5 O of nitrogen per hour are added.
It was fed at a rate of N. The copolymerization reaction is carried out at 50% by circulating hot water through a jacket attached to the outside of the polymerization vessel.
It was carried out at ℃.

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.
After drying under reduced pressure for a day and a night, a 4-methylpentene-1/octane-1,7-methyl-1,6-octadiene copolymer was obtained at a rate of 124 g/hour.

The molar ratio of octane-1 and 4-methylpentene-1 (octene-1/4-methylpentene-1) constituting the obtained copolymer was 76/24, and the iodine value was 12.
4, and the intrinsic viscosity [η
] was 3.7, and the crystallinity measured by X-ray diffraction was 0%.

Example 7 The 4-methylpentene-to-octenate 7-methyl-1,6-octadiene copolymer produced in Example 1 is shown in Table 2.
Accordingly, the mixture was kneaded using an 8-inch oven roll to obtain an unvulcanized compounded rubber.

Table 2 1) Product name: Asahi 80: Manufactured by Asahi Carbon Co., Ltd. 2) Product name: Suncera-M Manufactured by Nisan Shin Kagaku Co., Ltd. 3) Product name: Suncera-
This compounded rubber manufactured by TT Nisan Shin Kagaku Co., Ltd. was heated for 20 minutes in a press heated to 160°C to produce a vulcanized sheet.
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] The tensile test, hardness test, ozone resistance test, aging test, and bending test were measured according to JIS K 8301. That is, the tensile strength (TB) and elongation (E) were determined in the tensile test, and the H8 JISA hardness was determined in the hardness test. The ozone resistance test was carried out in an ozone test tank, and the conditions were that the ozone concentration was 50 pphn, the elongation rate was 20%, and the static test was conducted at 40° C. for 200 hours.

The surface condition was evaluated according to JIS K 6301 standards. The aging test was conducted by air heating at 120° C. for 70 hours. After the aging test, a tensile test is performed to determine the retention rate of the physical properties before aging, that is, the tensile strength retention rate A.
(TB) and elongation retention A(E)RR13 were determined. The bending test was performed using a dematcher testing machine to examine resistance to crack growth. That is, the number of times the sample was bent until the crack opened 15 times was measured.

The results are shown in Table 3.

Table 3

[Brief explanation of the drawing]

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) a linear higher α-olefin having 6 to 20 carbon atoms;
A copolymer consisting of -methylpentene-1 and a non-conjugated diene represented by the following general formula [I], the copolymer comprising (a)
The molar ratio of linear higher α-olefin and 4-methylpentene-1 (linear higher α-olefin/4-methylpentene-1) is within the range of 50/50 to 95/5, (
b) the iodine value 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 5.
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 linear higher α-olefin having 6 to 20 carbon atoms, 4-methylpentene-1, and a nonconjugated diene represented by the following general formula [I] are copolymerized in the presence of a catalyst for a) The molar ratio of linear higher α-olefin and 4-methylpentene-1 (linear higher α-olefin/4-methylpentene-1) is within the range of 50/50 to 95/5; (b) the iodine value 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: ▲Mathematical formulas, chemical formulas, tables, etc.▼… [I] (In the formula, n is an integer from 1 to 5, and R^1 is carbon Number 1~
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. )