JP3280427B2 - Extruded body - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an extruded product comprising an olefin polymer composition formed by an extrusion method.

[0002]

BACKGROUND OF THE INVENTION Conventionally, high density polyethylene,
Olefin polymers typified by linear low-density polyethylene and polypropylene are excellent in transparency,
It has excellent mechanical strength such as rigidity and impact strength, and is used as sheets, films, and various parts. For example, film, sheet, pipe,
It is formed into hoses, electric wire coatings, monofilaments, etc.

[0003] By the way, such olefin polymers are:
Generally, since the melt tension (melt tension, MT) is low, it has been difficult to form a large molded body by, for example, an extrusion molding method. Also, generally, an olefin polymer having a high melt tension has a low melt flow rate, and thus an olefin polymer having a high melt tension suitable for producing a large molded article has a low melt flow rate. Molding conditions were limited, and it was difficult to mold at a particularly high speed.

Therefore, if an olefin polymer having a high melt tension appears, it is possible to extrude the olefin polymer into pipes, hoses, etc. at a high speed, and to obtain a large extruded product. Become. Further, in the case of a molded article that may be subjected to secondary processing such as a sheet, a molded article having excellent secondary processing properties can be obtained.

In view of the above prior art, the present inventors have conducted intensive studies to obtain an olefin polymer which can be extruded at a high speed and which can enlarge an extruded product. As a result, the olefin polymer composition containing the α-olefin / polyene copolymer-containing olefin polymer composed of the α-olefin / polyene copolymer and the olefin polymer has a high melt tension and is extruded at a high speed. The present inventors have found that it is possible to increase the size of the extruded product as well as to achieve the present invention.

[0006]

The object of the present invention is to enable high-speed extrusion,
Further, it is an object of the present invention to provide an extruded product comprising a specific olefin polymer composition capable of increasing the size of a product.

[0007]

According to the present invention, [I] [A] a transition metal compound catalyst component and [B] a periodic table
Organometallic compounds containing a selection Bareru metals from Group I-Group III
In and objects catalyst component, alpha-olefin and polyethylene emissions and copolymerization
A structural unit derived from an α-olefin
99 . From 999 to 50 mol%, from polyene compounds
The derived structural unit is contained in an amount of 0.001 to 50 mol%.
Α-olefin-polyene copolymer (i)
Olefin is polymerized using a prepolymerization catalyst having
Α obtained by forming the olefin polymer (ii) by copolymerizing
-An olefin / polyene copolymer-containing polymer: 0.00
An extruded product formed from an olefin polymer composition comprising 5 to 99% by weight and [II] olefin polymer: 1 to 99.995% by weight is provided.

The polymer [I] containing the α-olefin / polyene copolymer is, for example, [A] a transition metal compound catalyst component selected from Ti, Zr, Hf, Cr and V; [B] The organometallic compound catalyst component containing a metal selected from Groups I to III of the Periodic Table contains an α-olefin and a polyene compound in an amount of 0.01 to 2000 g per 1 g of the [A] transition metal compound catalyst component. A prepolymerized catalyst containing an α-olefin / polyene copolymer (i), which is polymerized or copolymerized with an olefin to form an olefin polymer (ii). it can.

[0009]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the extruded product comprising the olefin polymer composition according to the present invention will be specifically described. First, the olefin polymer composition constituting the extruded product will be described in detail.

The olefin polymer composition forming the extruded product according to the present invention comprises [I] a polymer containing an α-olefin / polyene copolymer and [II] an olefin polymer.

The α-olefin / polyene copolymer-containing polymer [I] comprises (i) an α-olefin / polyene copolymer and (ii) an olefin polymer.

Such a polymer [I] containing an α-olefin / polyene copolymer can be obtained, for example, by adding [A] a transition metal compound catalyst component and [B] an organometallic compound catalyst component to α.
-Α obtained by copolymerizing an olefin and a polyene compound
An olefin polymer (ii) is formed by polymerizing or copolymerizing an olefin with a prepolymerization catalyst containing the olefin-polyene copolymer (i).

The α-olefin and polyene compound used for forming the α-olefin / polyene copolymer (i) as described above will be described. Examples of the α-olefin used in the present invention include α-olefins having 2 to 20 carbon atoms, and specifically, ethylene, propylene, 1-
Butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, Examples include 1-hexadecene, 1-octadecene, and 1-eicosene. These may be used alone or in combination.

The α-olefin may be the same as or different from the α-olefin forming the olefin polymer (ii) described below. Of these, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 3-methyl
1-butene, 1-eicosene and the like are preferably used.

As the polyene compound, the following compounds are specifically mentioned. 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,
6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 6-methyl-1,6-nonadiene, 7-
Methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-
Ethyl-1,6-nonadiene, 6-methyl-1,6-decadiene, 7-
Methyl-1,6-decadiene, 6-methyl-1,6-undecadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-octadiene, 1,6-heptadiene, 1,7-octadiene, 1, 8-nonadiene, 1,9-decadiene, 1,13-tetradecadiene,
1,5,9-decatriene, butadiene, aliphatic polyene compounds such as isoprene, vinylcyclohexene, vinylnorbornene, ethylidene norbornene, dicyclopentadiene, cyclooctadiene, 2,5-norbornadiene,
1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,3-divinylcyclopentane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 1,4-
Diallylcyclohexane, 1-allyl-5-vinylcyclooctane, 1,5-diallylcyclooctane, 1-allyl-4-isopropenylcyclohexane, 1-isopropenyl-4-vinylcyclohexane, 1-isopropenyl-3-vinylcyclo Alicyclic polyene compounds such as pentane, and aromatic polyene compounds such as divinylbenzene and vinylisopropenylbenzene;

These are used alone or in combination. In the present invention, among the polyene compounds as described above, a polyene compound having 7 or more carbon atoms and having an olefinic double bond at both terminals is preferable, and further an aliphatic having an olefinic double bond at both terminals. Or an alicyclic polyene compound is more preferable.

Specifically, 1,6-heptadiene, 1,7-octadiene, 1,9-decadiene, 1,13-tetradecadiene,
1,5,9-decatriene, 1,4-divinylcyclohexane, 1,
Preferred examples include 3-divinylcyclopentane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, and 1,3,4-trivinylcyclohexane.

Of these, aliphatic polyene compounds having 8 or more carbon atoms, preferably 10 or more carbon atoms, are preferred, and linear aliphatic polyene compounds having 10 or more carbon atoms are particularly preferred.

In forming the α-olefin / polyene copolymer (i), among the α-olefin and polyene compounds as described above, ethylene / 1,7-octadiene, ethylene / 1,9-decadiene, ethylene / 1,13-tetradecadiene, ethylene / 1,5,9-decatriene, propylene /
1,7-octadiene, propylene / 1,9-decadiene, propylene / 1,13-tetradecadiene, propylene / 1,5,9-
Decatriene, butene / 1,9-decadiene, butene / 1,5,
9-decatriene, 4-methyl-1-pentene / 1,9-decadiene, 3-methyl-1-butene / 1,9-decadiene, 1-eicosene / 1,9-decadiene, propylene / 1,4-divinylcyclohexane , Butene / 1,4-divinylcyclohexane is preferred.

In such an α-olefin / polyene copolymer (i), the constitutional unit derived from the α-olefin is usually 99.999 to 50 mol%, preferably 99.9%.
99 to 70 mol%, more preferably 99.995 to 7
In an amount of 5 mol%, more preferably 99.99 to 80 mol%, particularly preferably 99.95 to 85 mol%, 0.001 to 50 mol%, preferably 0.1 to 50 mol% of the structural unit derived from the polyene compound. 001 to 30 mol%, more preferably 0.005 to 25 mol%, and still more preferably 0.01 to 25 mol%.
It is desirable that it be contained in an amount of 20 mol%, particularly preferably 0.05 to 15 mol%.

Α-olefin / polyene copolymer
(i) may contain a unit derived from another olefin described below as long as the object of the present invention is not impaired. In this case, the constituent unit derived from the olefin is usually contained in an amount of less than 30 mol%, preferably 20 mol% or less, particularly preferably 15 mol% or less.

The composition ratio of the α-olefin / polyene copolymer (i) as described above can be calculated by measuring the amounts of the α-olefin and the polyene compound consumed during the polymerization. Specifically, the structural unit [P mol%] derived from polyene is calculated as follows.

[0023]

(Equation 1)

(Where, [P ₀ ]: the number of moles of the polyene compound supplied at the time of polymerization [P _r ]: the number of moles of the unreacted polyene compound [α ₀ ]: the number of moles of the α-olefin supplied at the time of polymerization [Α _r ]: Number of moles of unreacted α-olefin) [α _r ] and [P _r ] are determined by measuring unreacted α-olefin and polyene compound remaining in the polymerization vessel by gas chromatography or the like. Is determined by

The olefin used for forming the olefin polymer (ii) forming the α-olefin / polyene copolymer-containing polymer is the above-mentioned olefin having 2 carbon atoms.
To 20 α-olefins.

Further, substituted styrenes such as styrene and dimethylstyrene, substituted allylbenzenes such as allylbenzene and allyltoluene, aromatic vinyl compounds such as vinylnaphthalene, substituted vinylnaphthalene, allylnaphthalene and substituted allylnaphthalene, vinylcyclohexane , Substituted vinylcyclohexanes, vinylcyclopentane, substituted vinylcyclopentanes, vinylcycloheptane, substituted vinylcycloheptanes, alicyclic vinyl compounds such as allylnorbornane, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, Tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,
Cyclic olefins such as 3,4,4a, 5,8,8a-octahydronaphthalene, allyltrimethylsilane, allyltriethylsilane, 4-trimethylsilyl-1-butene, 6-trimethylsilyl-1-hexene, 8-trimethylsilyl-1- Octen, 10
-Silane-based unsaturated compounds such as trimethylsilyl-1-decene and the above-mentioned polyene compounds.

These may be used alone or in combination. Of these, ethylene, propylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, vinylcyclohexane, dimethylstyrene, allyltrimethylsilane, allylnaphthalene, etc. It is preferably used.

In the polymer [I] containing the α-olefin / polyene copolymer, the α-olefin / polyene copolymer (i) is used in an amount of usually 0.001 to 99% by weight, preferably 0.005 to 90% by weight. % By weight, particularly preferably 0.01 to
In an amount of 88% by weight, the olefin polymer (ii) is 99.9%
It is contained in an amount of 99 to 1% by weight, preferably 99.995 to 10% by weight, particularly preferably 99.99 to 12% by weight.

Among the α-olefin / polyene copolymer-containing polymers [I] used in the present invention,
α-olefin-polyene copolymer (i)
In an amount of 15% by weight, preferably 0.008 to 10% by weight,
Those containing the olefin polymer (ii) in an amount of 99.999 to 85% by weight, preferably 99.992 to 90% by weight, are particularly preferred.

The polymer [I] containing the α-olefin / polyene copolymer used in the present invention is ASTM D123
Melt flow rate (MF
R) is 5000 or less, preferably 0.01 to 3000 g
/ 10 minutes, more preferably 0.02 to 2000 g / 10 minutes,
Particularly preferred is 0.05 to 1000 g / 10 min.

The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.05 to 20 dl / g, preferably 0.1 to 20 dl / g.
It is 1 to 15 dl / g, particularly preferably 0.2 to 13 dl / g.

Such an α-olefin / polyene copolymer-containing polymer [I] has a high melt tension (melt tension, MT). In the polymer [I] containing the α-olefin / polyene copolymer used in the present invention, the melt tension (MT) expressed in relation to the melt flow rate (MFR) is specifically as follows.

For example, the α-olefin / polyene copolymer (i) forming the α-olefin / polyene copolymer-containing polymer [I] is an ethylene / polyene copolymer, and the olefin polymer (ii) is In the case of polypropylene, the α-olefin / polyene copolymer-containing polymer [I] has a log [MT] ≧ −0.8 log [MFR] +0.3, preferably a log [MT] ≧ −0. 0.8 log [MFR] +0.5 More preferably, log [MT] ≧ −0.8 log [MFR] +0.7, particularly preferably log [MT] ≧ −0.8 log [MFR] +0.8 The relational expression is satisfied.

The α-olefin / polyene copolymer (i) forming the α-olefin / polyene copolymer-containing polymer [I] is a copolymer of an α-olefin having 3 or more carbon atoms and a polyene. When the olefin polymer (ii) is polypropylene, the α-olefin / polyene copolymer-containing polymer [I] has a log [MT] ≧ −0.8 log [MFR] +0.30 Preferably, the formula of log [MT] ≧ −0.8 log [MFR] +0.35 is satisfied, more preferably log [MT] ≧ −0.8 log [MFR] +0.40.

Further, for example, the α-olefin / polyene copolymer-containing polymer [I] comprises the above-mentioned ethylene / polyene copolymer (i) and polyethylene (ii), and the density of this olefin polymer is about 0.92 g / cm ³ , MFR
Is 1 g / 10 minutes, the melt tension of the olefin polymer is at least 2.5 g, preferably at least 3.5 g, more preferably at least 4.0 g, and even more preferably at least 4.0 g.
It is at least 5 g, particularly preferably at least 5.0 g.

The α-olefin / polyene copolymer-containing polymer [I] used in the present invention has a melt tension (M
T) satisfies the above-mentioned relational expression with the melt flow rate (MFR) and also satisfies the following expression with the intrinsic viscosity ([η]).

For example, the α-olefin / polyene copolymer (i) forming the α-olefin / polyene copolymer-containing polymer [I] is an ethylene / polyene copolymer,
When the olefin polymer (ii) is polypropylene, the α-olefin / polyene copolymer-containing polymer [I] has a log [MT] ≧ 3.7 log [[η]]-1.5, preferably Log [MT] ≧ 3.7 log [[η]] − 1.3 More preferably, log [MT] ≧ 3.7 log [[η]]-1.1 Particularly preferably, log [MT] ≧ 3. 7log [[η]] − 1.0 is satisfied.

The α-olefin / polyene copolymer (i) forming the α-olefin / polyene copolymer-containing polymer [I] is a copolymer of an α-olefin having 3 or more carbon atoms and a polyene. When the olefin polymer (ii) is polypropylene, the α-olefin / polyene copolymer-containing polymer [I] has a log [MT] ≧ 3.7 log [[η]]-1.50. Satisfies the relationship expressed by log [MT] ≧ 3.7 log [[η]] − 1.45, particularly preferably log [MT] ≧ 3.7 log [[η]] − 1.40.

Further, for example, the α-olefin / polyene copolymer-containing polymer [I] comprises the above-mentioned ethylene / polyene copolymer (i) and polyethylene (ii), and the density of this olefin polymer is When 0.92 g / cm ³ and intrinsic viscosity [η] are 1.8 dl / g, the melt tension of the olefin polymer is 2.5 g or more, preferably 3.5 g or more, more preferably 4.0 g or more. And more preferably at least 4.5 g, particularly preferably at least 5.0 g.

The melt tension is measured as follows. Using an MT measuring device manufactured by Toyo Seiki Seisaku-Sho, an orifice, 7 g of polymer, and a cylinder held at a polymer melting temperature (230 ° C. for polypropylene)
Insert in piston order. After 5 minutes, the piston is pushed down at a speed of 10 mm / min, and the molten polymer is pushed out from the orifice at the bottom of the cylinder. The extruded strand is drawn into a filament, passed through a pulley of a load detector, and taken up by a take-up roller at a speed of 25 m / min. At this time,
The stress applied to the pulley is measured, and this value is used as the melt tension of the polymer.

Next, the [A] transition metal compound catalyst component used in producing the above-mentioned α-olefin / polyene copolymer-containing polymer [I] will be described. In the present invention, the [A] transition metal compound catalyst component includes a compound containing a transition metal selected from Groups III to VIII of the Periodic Table, and is preferably Ti, Zr, Hf, Nb, T
Compounds containing at least one transition metal selected from a, Cr and V are exemplified.

Examples of the [A] transition metal compound catalyst component include all known catalyst components, and specific examples include a solid titanium catalyst component containing titanium and halogen. More specifically, as an example of such a solid titanium catalyst component, titanium, magnesium, halogen and, if necessary, an electron donor (a)
And a solid titanium catalyst component [A-1].

Such a solid titanium catalyst component [A-1]
The method of preparing is described in detail in, for example, the following gazettes. 46-34
No.092, JP-B-53-46799, JP-B-60-3
No. 323, JP-B-63-54289, JP-A-1-26
1404, JP-A-1-261407, JP-B-47-
41676, JP-B-47-46269, JP-B-48
-19794, JP-A-60-262803, JP-A-59-147004, JP-A-59-149911,
JP-A-1-201308, JP-A-61-151211
JP-A-53-58495, JP-A-53-8799
No. 0, JP-A-59-206413, JP-A-58-20
No. 6613, JP-A-58-125706, JP-A-63
-68606, JP-A-63-69806, JP-A-63-69806
0-81210, JP-A-61-40306, JP-A-51-281189, JP-A-50-126590,
JP-A-51-92885, JP-B-57-45244.
No., JP-B-57-26613, JP-B-61-5483
No., JP-A-56-811, JP-B-60-37804.
No., JP-B-59-50246, JP-A-58-8300
6, JP-A-48-16986, JP-A-49-659
No. 99, JP-A-49-86482, JP-B-56-39
No. 767, JP-B-56-32222, JP-A-55-2.
9591, JP-A-53-146292 and JP-A-57-146292.
-63310, JP-A-57-63311, JP-A-5-6311
7-63312, JP-A-62-273206, JP-A-63-69804, JP-A-61-21109, JP-A-63-264607, JP-A-60-23404
No., JP-A-60-44507, JP-A-60-1582
04, JP-A-61-55104, JP-A-2-282
No. 01, JP-A-58-196210, JP-A-64-5
4005, JP-A-59-149905, JP-A-61-61905
-145206, JP-A-63-302, JP-A-63-302
-225605, JP-A-64-69610, JP-A-1-168707, JP-A-62-104810, JP-A-62-104811, and JP-A-62-104812.
And JP-A No. 62-104813.

The solid titanium catalyst component [A-1] is prepared by, for example, using a titanium compound, a magnesium compound and, if necessary, an electron donor (a) and bringing these compounds into contact.

Examples of the titanium compound used for preparing the solid titanium catalyst component [A-1] include a tetravalent titanium compound and a trivalent titanium compound. Examples of such a tetravalent titanium compound include a compound represented by the following formula.

Ti (OR) _g X _{4-g In the} formula, R is a hydrocarbon group, X is a halogen atom, and 0 ≦ g ≦ 4. Specific examples of such compounds include titanium tetrahalides such as TiCl ₄ , TiBr ₄ , and TiI ₄ , Ti (OCH ₃ ) Cl ₃ , and Ti (OC ₂ H ₅ ) Cl _3.
, Ti (On-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (O
-iso-C ₄ H ₉₎ trihalide, alkoxy titanium such as _{Br 3, Ti (OCH 3)} 2 Cl 2, Ti (OC 2 H 5) 2 Cl 2, Ti
Dialkoxytitanium dihalides such as (On-C ₄ H ₉ ) ₂ Cl ₂ and Ti (OC ₂ H ₅ ) ₂ Br ₂ , Ti (OCH ₃ ) ₃ Cl, Ti (O
_{C 2 H 5) 3 Cl,} Ti (On-C 4 H 9) 3 Cl, Ti (OC 2 H 5) 3 B
r and other monohalogenated trialkoxy titanium, Ti (O
CH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₄ H ₉ ) ₄ , Ti
Examples thereof include tetraalkoxy titanium such as (O-iso-C ₄ H ₉ ) ₄ and Ti (O-2-ethylhexyl) ₄ .

Of these, preferred are titanium tetrahalides, and particularly preferred is titanium tetrachloride. These titanium compounds may be used alone or in combination of two or more. Alternatively, it may be used after being diluted with a hydrocarbon or a halogenated hydrocarbon.

As the trivalent titanium compound, titanium trichloride is used. As such titanium trichloride,
For example, titanium trichloride obtained by contacting titanium tetrachloride with a metal such as hydrogen, metallic magnesium, metallic aluminum, or metallic titanium or an organometallic compound such as an organomagnesium compound, an organoaluminum compound, or an organozinc compound is preferably titanium trichloride. Used.

Examples of the magnesium compound used for preparing the solid titanium catalyst component [A-1] include a magnesium compound having a reducing ability and a magnesium compound having no reducing ability.

The magnesium compound having a reducing ability includes, for example, an organic magnesium compound represented by the following formula. X _n MgR _{2-n In the} formula, n is 0 ≦ n <2, and R is hydrogen or carbon atom 1
20 to 20 alkyl groups, aryl groups or cycloalkyl groups. When n is 0, two Rs may be the same or different, and X is a halogen.

As the organomagnesium compound having such a reducing ability, specifically, dimethylmagnesium, diethylmagnesium, dipropylmagnesium,
Dialkyl magnesium compounds such as dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, octyl butyl magnesium, and ethyl butyl magnesium; alkyl magnesium such as ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, and amyl magnesium chloride Examples thereof include alkyl magnesium alkoxides such as halide, butyl ethoxy magnesium, ethyl butoxy magnesium and octyl butoxy magnesium, and other butyl magnesium hydrides.

Specific examples of magnesium compounds having no reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride, methoxymagnesium chloride, and the like.
Alkoxy magnesium halides such as ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride, etc., allyloxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride, ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octo And magnesium carboxylate such as magnesium magnesium laurate, magnesium stearate, etc .; alkoxymagnesium such as xoxymagnesium and 2-ethylhexoxymagnesium; allyloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium; In addition, magnesium metal and magnesium hydride can be used.

The magnesium compound having no reducing ability may be a compound derived from the magnesium compound having the reducing ability described above or a compound derived at the time of preparing the catalyst component. In order to derive a magnesium compound having no reducing ability from a magnesium compound having reducing ability, for example, a magnesium compound having reducing ability is converted into a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, and a halogen. What is necessary is just to contact with a containing compound or a compound having an OH group or an active carbon-oxygen bond.

The magnesium compound having a reducing ability and the magnesium compound having no reducing ability are as follows.
Organometallic compounds described below, for example, complex compounds with other metals such as aluminum, zinc, boron, beryllium, sodium and potassium, may form complex compounds, or may be mixtures with other metal compounds Good. Further, the magnesium compound may be alone,
Two or more of the above compounds may be used in combination, and may be used in a liquid state or a solid state. When the magnesium compound is a solid, an alcohol, a carboxylic acid, an aldehyde described below as the electron donor (a),
The liquid state can be obtained by using amines, metal acid esters and the like.

As the magnesium compound used for the preparation of the solid titanium catalyst component [A-1], many magnesium compounds can be used other than those described above, but the finally obtained solid titanium catalyst component [A-] In [1], it is preferable to take the form of a halogen-containing magnesium compound. Therefore, when a halogen-free magnesium compound is used, it is preferable to carry out a contact reaction with the halogen-containing compound during the preparation.

Of these, magnesium compounds having no reducing ability are preferred, and halogen-containing magnesium compounds are particularly preferred. Of these, magnesium chloride, alkoxymagnesium chloride and allyloxymagnesium chloride are preferred.

In the preparation of the solid titanium catalyst component [A-1], an electron donor (a) is preferably used. Such electron donors (a) include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, esters of organic or inorganic acids, ethers, diethers, acid amides , Acid anhydrides, oxygen-containing electron donors such as alkoxysilanes, ammonias,
Examples include nitrogen-containing electron donors such as amines, nitriles, pyridines, and isocyanates. More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropyl benzyl Alcohols having 1 to 18 carbon atoms such as alcohols and halogen-containing alcohols having 1 to 18 carbon atoms such as trichloromethanol and trichloroethanol and trichlorohexanol, phenol, cresol, xylenol, ethylphenol,
C6-20 phenols which may have a lower alkyl group such as propylphenol, nonylphenol, cumylphenol and naphthol, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone,
C3-C15 ketones such as benzophenone and benzoquinone, acetaldehyde, propionaldehyde,
C2 to C15 aldehydes such as octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, Ethyl herbate,
Methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoate Benzyl acid, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethyl carbonate, etc. C2 to C18 organic acid esters, acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, and other C2 to C15 acid halides, methyl ether, ethyl ether, isopropyl ether, butyl ether , Amyl ether, tetrahydrofuran, anisole, ethers having 2 to 20 carbon atoms, such as diphenyl ether, acetic acid N, N-dimethylamide,
Acid amides such as benzoic acid N, N-diethylamide and toluic acid N, N-dimethylamide; amines such as trimethylamine, triethylamine, tributylamine, tribenzylamine and tetramethylethylenediamine; nitriles such as acetonitrile, benzonitrile and trinitrile And pyridines such as pyridine, methylpyridine, ethylpyridine and dimethylpyridine, and acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride.

As the organic acid ester, a polycarboxylic acid ester having a skeleton represented by the following general formula can be mentioned as a preferred example.

[0059]

Embedded image

(Wherein, R ¹ is a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ , and R ⁶ are hydrogen or a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ are hydrogen or a substituted or unsubstituted It is an unsubstituted hydrocarbon group, preferably at least one is a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ may be linked to each other to form a cyclic structure. When the hydrogen groups R ^{1 to} R ⁶ are substituted, the substituent contains a different atom such as N, O, S, and, for example, C—O
-C, COOR, COOH, OH, SO 3 H, -C-N
-C-, having a group such as NH _2. Examples of such polyvalent carboxylic acid esters include aliphatic polycarboxylic acid esters, alicyclic polycarboxylic acid esters,
Examples thereof include aromatic polycarboxylic acid esters and heterocyclic polycarboxylic acid esters.

Preferred specific examples include n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadicate, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate. Butyl, 2-phthalic acid
Examples include ethylhexyl and dibutyl 3,4-furandicarboxylate.

Particularly preferred polyvalent carboxylic acid esters include phthalic acid esters. Further, as the polyether compound, a compound represented by the following general formula may be mentioned.

[0063]

Embedded image

(Wherein, n is an integer of 2 ≦ n ≦ 10, and R ^{1 to} R ²⁶ are at least one kind selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon) is a substituent having an element, any R ¹ ~
R ²⁶ , preferably R ^{1 to} R ^2n, may together form a ring other than a benzene ring, and the main chain may contain atoms other than carbon. ) Preferred examples include 2,2-
Diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3 -Dimethoxypropane and the like.

The electron donor (a) as described above can be used in combination of two or more. In addition, the solid titanium catalyst component [A-1] used in the present invention may be prepared by preparing an organic compound containing silicon, phosphorus, aluminum, or the like used as a carrier compound and a reaction aid, in addition to the compounds described above. And an inorganic compound or the like.

Examples of such a carrier compound include Al
₂ O ₃ , SiO ₂ , B ₂ O ₃ , MgO, CaO, TiO ₂ ,
_{ZnO, SnO 2, BaO, ThO} , styrene - like resins such as divinylbenzene copolymer. Among them, Al ₂ O ₃ , SiO ₂ and styrene-divinylbenzene copolymer are preferred.

The solid titanium catalyst component [A-1] used in the present invention is prepared by contacting the above-mentioned titanium compound, magnesium compound and preferably the electron donor (a).

The method for preparing the solid titanium catalyst component [A-1] using these compounds is not particularly limited. However, in the case of using a tetravalent titanium compound, several examples of this method are given below. Briefly described. (1) A method comprising contacting and reacting a solution comprising a magnesium compound, an electron donor (a) and a hydrocarbon solvent with an organometallic compound to precipitate a solid, or contacting and reacting with a titanium compound while precipitating. (2) A method in which a complex comprising a magnesium compound and an electron donor (a) is contact-reacted with an organometallic compound, followed by a contact reaction with a titanium compound. (3) A method in which a contact product of an inorganic carrier and an organic magnesium compound is contact-reacted with a titanium compound. At this time, the above-mentioned contact product may be brought into contact with a halogen-containing compound, an electron donor (a) and / or an organometallic compound in advance. (4) a magnesium compound, an electron donor (a), and optionally a mixture of a solution containing a hydrocarbon solvent and an inorganic or organic carrier, to obtain an inorganic or organic carrier on which a magnesium compound is supported, and then a titanium compound. How to make contact. (5) Magnesium compound, titanium compound, electron donor
(a) A method of obtaining a [A-1] solid titanium catalyst component carrying magnesium and titanium by optionally contacting a solution containing a hydrocarbon solvent with an inorganic or organic carrier. (6) A method of contacting a liquid state organomagnesium compound with a halogen-containing titanium compound. (7) A method in which a liquid state organomagnesium compound is brought into contact with a halogen-containing compound and then brought into contact with a titanium compound. (8) A method of contacting an alkoxy group-containing magnesium compound with a halogen-containing titanium compound. (9) A method of contacting a complex comprising an alkoxy group-containing magnesium compound and an electron donor (a) with a titanium compound. (10) A method comprising contacting a complex comprising an alkoxy group-containing magnesium compound and an electron donor (a) with an organometallic compound and then contacting the complex with a titanium compound. (11) A method of contacting and reacting a magnesium compound, an electron donor (a), and a titanium compound in an arbitrary order. In this reaction, each component may be pretreated with an electron donor (a) and / or a reaction auxiliary such as an organometallic compound or a halogen-containing silicon compound. (12) A method in which a liquid magnesium compound having no reducing ability is reacted with a liquid titanium compound in the presence of an electron donor (a), if necessary, to precipitate a solid magnesium / titanium composite. (13) A method in which a titanium compound is further reacted with the reaction product obtained in (12). (14) A method in which the reaction product obtained in (11) or (12) is further reacted with an electron donor (a) and a titanium compound. (15) A method in which a solid obtained by pulverizing a magnesium compound, a titanium compound and, if necessary, an electron donor (a) is treated with any of a halogen, a halogen compound and an aromatic hydrocarbon. This method may include a step of pulverizing only the magnesium compound, or a complex compound composed of the magnesium compound and the electron donor (a), or a magnesium compound and a titanium compound. Further, after the pulverization, a preliminary treatment with a reaction aid may be performed, followed by a treatment with a halogen or the like. Examples of the reaction aid include an organometallic compound and a halogen-containing silicon compound. (16) A method of pulverizing a magnesium compound and then contacting and reacting with a titanium compound. At this time, an electron donor (a) or a reaction aid may be used at the time of pulverization and / or contact / reaction. (17) A method of treating the compound obtained in the above (11) to (16) with a halogen, a halogen compound or an aromatic hydrocarbon. (18) A method of contacting a reaction product of a metal oxide, an organomagnesium and a halogen-containing compound with a titanium compound and, if necessary, an electron donor (a). (19) A method in which a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or aryloxymagnesium is reacted with a titanium compound and / or a halogen-containing hydrocarbon and, if necessary, an electron donor (a). (20) A method of contacting a hydrocarbon solution containing at least a magnesium compound and alkoxytitanium with a titanium compound and / or an electron donor (a). At this time, if necessary, a halogen-containing compound such as a halogen-containing silicon compound may be further contacted. (21) reacting a magnesium compound in a liquid state having no reducing ability with an organometallic compound to form a solid magnesium compound;
A method in which a metal (aluminum) complex is precipitated, and then a titanium compound and, if necessary, an electron donor (a) are reacted.

Such a solid titanium catalyst component [A-1]
Is usually at -70 ° C to 200 ° C, preferably at -50 ° C.
It is carried out at a temperature of between 150C and 150C. The solid titanium catalyst component [A-1] thus obtained contains titanium, magnesium, halogen and preferably an electron donor (a).

In the solid titanium catalyst component [A-1], halogen / titanium (atomic ratio) is 2 to 200, preferably 4 to 90, and magnesium / titanium (atomic ratio) is 1 to 100, Preferably, it is 2 to 50.

Also preferably, the electron donor (a) is usually
When the electron donor (a) / titanium (molar ratio) is 0.01 to 10
0, preferably 0.05 to 50. In the present invention, the solid titanium catalyst component [A-1] as described above
Has been described above using a titanium compound. However, in the above-mentioned titanium compound, titanium may be replaced with zirconium, hafnium, vanadium, niobium, tantalum or chromium.

In the present invention, a conventionally known [A-2] titanium trichloride-based catalyst component can be used as another example of the solid titanium catalyst component exemplified as the transition metal compound catalyst component [A].

The method of preparing the [A-2] titanium trichloride-based catalyst component is described in detail in, for example, the following gazettes. JP-A-63-1
7274, JP-A-64-38409, JP-A-56-38
No. 34711, JP-A-61-287904, JP-A-6-287904
JP-A-3-75007, JP-A-63-83106, JP-A-59-13630, JP-A-63-108008, JP-A-63-27508, JP-A-57-70110,
JP-A-58-219207, JP-A-1-144405
JP-A-1-292011, JP-A-1-29201
No. 1, etc.

Examples of the [A-2] titanium trichloride-based catalyst component include the above-mentioned titanium trichloride. Further, such titanium trichloride can be used together with the above-mentioned electron donor (a) and / or tetravalent titanium compound or after being brought into contact therewith.

Furthermore, in the present invention, [A-3] a metallocene compound can be used as the catalyst component for the transition metal compound [A]. Details of such a method for preparing the [A-3] metallocene compound are described in, for example, the following gazettes.

JP-A-63-61010, JP-A-63-61010
No. 152608, JP-A-63-264606, JP-A-63-280703, JP-A-64-6003, JP-A-1-95110, JP-A-3-62806, JP-A-1-259004, JP-A-64-45406, JP-A-60-106808, JP-A-60-137911
JP-A-58-19309, JP-A-60-3500
6, JP-A-60-35007, JP-A-61-296
008, Patent Publication 63-501369, JP-A-61-61
JP-A-221207, JP-A-62-121707, JP-A-63-66206, JP-A-2-22307, JP-A-2-173110, JP-A-2-302410, JP-A-1-129003, JP-A-1-129003 No. 1-210404,
JP-A-3-66710, JP-A-3-70710, JP-A-1-207248, JP-A-63-222177
JP-A-63-222178, JP-A-63-222
No. 179, Japanese Patent Application Laid-Open No. 1-12407, Japanese Patent Application Laid-Open No. 1-301
704, JP-A-1-319489, JP-A-3-74
412, JP-A-61-264010, JP-A 1-2
No. 75609, JP-A-63-251405, JP-A-6-251405
4-74202, JP-A-2-41303, JP-A-2-42
JP-A-131488, JP-A-3-56508, JP-A-3-3508
-70708, JP-A-3-70709 and the like.

As such [A-3] metallocene compound, a compound represented by the following formula is specifically mentioned. ML _{x wherein} M is a transition metal selected from the group consisting of Zr, Ti, Hf, V, Nb, Ta and Cr, L is a ligand coordinated to the transition metal, and at least one L is a ligand having a cyclopentadienyl skeleton, and L other than a ligand having a cyclopentadienyl skeleton has 1 to 1 carbon atoms.
2, a hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, an SO ₃ R group (where R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen), a halogen atom Or a hydrogen atom, and x is the valence of the transition metal. Examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group, a methylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group,
Tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadiene Examples include alkyl-substituted cyclopentadienyl groups such as enyl group, methylbutylcyclopentadienyl group and hexylcyclopentadienyl group, or indenyl group, 4,5,6,7-tetrahydroindenyl group and fluorenyl group. Can be. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

Among the ligands which coordinate to these transition metals, an alkyl-substituted cyclopentadienyl group is particularly preferred. When the compound represented by the above general formula contains two or more groups having a cyclopentadienyl skeleton,
Groups having a cyclopentadienyl skeleton are substituted with an alkylene group such as ethylene and propylene, a substituted alkylene group such as isopropylidene and diphenylmethylene, a silylene group or a dimethylsilylene group, a diphenylsilylene group, and a methylphenylsilylene group. They may be bonded via a silylene group or the like.

Specific examples of the ligand L other than the ligand having a cyclopentadienyl skeleton include the following. Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Group, butyl group, etc., cycloalkyl group, cyclopentyl group, cyclohexyl group, etc., aryl group, phenyl group, tolyl group, etc., and aralkyl group, benzyl group, neophyl group, etc. And the like.

As the alkoxy group, a methoxy group,
An ethoxy group, a butoxy group and the like are exemplified. As the aryloxy group, a phenoxy group and the like are exemplified. As the halogen, fluorine, chlorine, bromine, iodine and the like are exemplified.

Examples of the ligand represented by SO ₃ R include a p-toluenesulfonato group, a methanesulfonato group, and a trifluoromethanesulfonato group. Including a ligand having such a cyclopentadienyl skeleton [A-3]
When the valence of the transition metal is 4, for example, the metallocene compound is more specifically represented by the following formula.

R ² _k R ³ _l R ⁴ _m R ⁵ _n M ( _where M is the above-mentioned transition metal, R ² is a group (ligand) having a cyclopentadienyl skeleton, and R ³ , R ⁴ and R ⁵ are a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a trialkylsilyl group, an SO ₃ R group, a halogen atom or a hydrogen atom. And k is an integer of 1 or more, and k + 1 + m + n = 4.) In the present invention, in the above formula R ² _k R ³ _l R ⁴ _m R ⁵ _n M,
A metallocene compound in which at least two of R ² , R ³ , R ⁴ and R ⁵ , that is, R ² and R ³ are groups (ligands) having a cyclopentadienyl skeleton is preferably used. These groups having a cyclopentadienyl skeleton include alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene, and silylene groups or substituted silylene groups such as dimethylsilylene, diphenylsilylene and methylphenylsilylene groups. May be connected via R ⁴ and R ⁵ are a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a trialkylsilyl group, SO ₃
R, a halogen atom or a hydrogen atom.

The following are specific examples of the transition metal compound in which M is zirconium. Bis (indenyl) zirconium dichloride, bis (indenyl)
Zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato) bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylene Bis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) zirconiumbis (methanesulfonato), ethylenebis ( Indenyl) zirconium bis (p-toluenesulfonato), ethylenebis (indenyl) zirconiumbis (trifluoromethanesulfonate), ethylenebis (4,5,6, 7-tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (cyclopentadienyl) zirconium dichloride Dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethyl Silylene bis (indenyl)
Zirconium bis (trifluoromethanesulfonate),
Dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, methylphenylsilylenebis (indenyl) zirconium dichloride , Bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis (cyclopentane Dienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride, bis (cyclopentadienyl) benzyl Benzalkonium monochloride,
Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) methyl zirconium monohydride, bis (cyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadiene) (Enyl) dibenzylzirconium, bis (cyclopentadienyl) zirconium methoxychloride, bis (cyclopentadienyl) zirconium ethoxycyclolide, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl)
Zirconium bis (p-toluenesulfonato), bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis ( Dimethylcyclopentadienyl) zirconium ethoxycyclolide, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadienyl) zirconium dichloride, Bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadiene) Le) zirconium dichloride, bis (methyl-butylcyclopentadienyl) zirconium dichloride, bis (methyl-butylcyclopentadienyl)
Zirconium bis (methanesulfonato), bis (trimethylcyclopentadienyl) zirconium dichloride,
Bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride.

In the above examples, disubstituted cyclopentadienyl ring includes 1,2- and 1,3-substituted, and tri-substituted cyclopentadienyl ring includes 1,2,3- and 1,2,4-substituted Including the body. Alkyl groups such as propyl and butyl are n-, i-, sec-, tert-
And isomers.

In the above zirconium compound, a compound in which zirconium is replaced with titanium, hafnium, vanadium, niobium, tantalum or chromium can also be used.

These compounds may be used alone,
Two or more kinds may be used in combination. It may be used after being diluted with a hydrocarbon or a halogenated hydrocarbon.
In the present invention, as the metallocene compound [A-3], a zirconocene compound in which the central metal atom is zirconium and which has a ligand having at least two cyclopentadienyl skeletons is preferably used.

The metallocene compound [A-3] as described above can be used by being brought into contact with a particulate carrier compound and carried on a carrier. As the carrier compound, SiO 2
₂ , Al ₂ O ₃ , B ₂ O ₃ , MgO, ZrO ₂ , CaO, Ti
Inorganic carrier compounds such as O ₂ , ZnO, SnO ₂ , BaO, and ThO, and resins such as polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, and styrene-divinylbenzene copolymer can be used. it can.

These carrier compounds can be used in combination of two or more. Of these, SiO ₂ , Al
₂ O ₃ and MgO are preferably used. Next, Group I to Periodic Table of the Periodic Table for forming the prepolymerized catalyst [I] according to the present invention.
The organometallic compound catalyst component [B] containing a metal selected from Group III will be described.

The organometallic compound catalyst component [B]
Examples thereof include [B-1] an organoaluminum compound, a complex alkyl compound of a Group I metal and aluminum,
An organic metal compound of a Group II metal or the like can be used.

As the [B-1] organoaluminum compound, for example, an organoaluminum compound represented by the following formula can be exemplified. During R ^a _n AlX _3-n (wherein, R ^a is a hydrocarbon group having 1 to 12 carbon atoms, X
Is halogen or hydrogen, and n is 1-3. ) In the above formula, ^Ra is a hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Examples include an isobutyl group, a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, and a tolyl group. Specific examples of such an organoaluminum compound include the following compounds.

Trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri2-
Trialkyl aluminum such as ethylhexyl aluminum.

Alkenyl aluminums such as isoprenyl aluminum. Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide.

Alkyl aluminum sesquichlorides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide.

Alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride and ethyl aluminum dibromide.

Alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; [B-1] As the organoaluminum compound, a compound represented by the following formula can also be used.

[0096] In R ^a _n AlY _3-n the above formulas, R ^a is as defined above, Y is -OR
^b group, -OSiR ^c ₃ group, -OAlR ^d ₂ group, -NR ^e ₂ group, -
A SiR ^f ₃ group or a —N (R ^g ) AlR ^h ₂ group, wherein n is 1
And R ^b , R ^c , R ^d and R ^h are methyl groups,
Ethyl, isopropyl, isobutyl, cyclohexyl, phenyl, etc., ^Re is hydrogen, methyl, ethyl, isopropyl, phenyl, trimethylsilyl, etc., and R ^f and R ^g are methyl, And an ethyl group.

As the organic aluminum compound [B-1], the following compounds are specifically used. _{^{(i) R a n Al (}} OR b) 3-n dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum _{^{methoxide, (ii) R a n Al}} (OSiR c 3) 3-n Et 2 Al (OSiMe ₃₎ (such as _{iso-Bu) 2 Al (OSiMe} 3) (iso-Bu) 2 Al (OSiEt 3), (iii) R a n Al (OAlR d 2) 3-n Et 2 AlOAlEt 2 (iso-Bu) such as _{2 AlOAl (iso-Bu) 2} , (iv) R a n Al (NR e 2) 3-n Me 2 AlNEt 2 Et 2 AlNHMe Me 2 AlNHEt Et 2 AlN (Me 3 Si) 2 (iso-Bu) 2 AlN etc. _{(Me 3 Si) 2, (} v) R a n Al etc. ^{_{(SiR f 3) 3-n}} (iso-Bu) 2 AlSiMe 3, (vi) R a n Al [n (R ^g) -AlR ^h etc. _{2] 3-n Et 2 AlN (Me} ) -AlEt 2 (iso-Bu) 2 AlN (Et) Al (iso-Bu) 2.

As the above [B-1] organoaluminum compounds, R ^a3 Al, R ^a _n Al (OR ^b ) _3-n and R ^a ₃ Al
an organoaluminum compound represented by _{^{a n Al (OAlR d 2)}} 3-n may be mentioned as preferred examples.

Examples of the complex alkylated product of a Group I metal and aluminum include compounds represented by the following general formula. M ¹ AlR ^j ₄ (where M ¹ is Li, Na, K, and R ^j is C 1
To 15) More specifically, LiAl (C _{2
H 5) 4, LiAl (C} 7 H 15) 4 and the like.

Examples of the organometallic compounds of Group II metals include compounds represented by the following general formula. R ^k R ¹ M ² (where R ^k and R ¹ are a hydrocarbon group having 1 to 15 carbon atoms or halogen, and may be the same or different from each other, except when both are halogen. M ² Is M
g, Zn, and Cd). Specific examples include diethyl zinc, diethyl magnesium, butyl ethyl magnesium, ethyl magnesium chloride, and butyl magnesium chloride.

These compounds can be used in combination of two or more kinds. Specific examples of the [B-2] organoaluminum oxy compound include aluminoxanes represented by general formulas (1) and (2).

[0102]

Embedded image

(In the general formulas (1) and (2), R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group, preferably a methyl group, an ethyl group, and particularly preferably a methyl group. Yes, m is 2 or more, preferably 5
It is an integer of 40. Here, the aluminoxane is an alkyloxyaluminum unit represented by the formula (OAl (R ¹ )) and an alkyloxyaluminum unit represented by the formula (OAl (R ² )) wherein R ¹ and R ²
Can be exemplified by the same hydrocarbon groups as R, and R ¹ and R ² represent different groups.]. In that case, the methyloxyaluminum unit (OAl
(CH ₃ )) is at least 30 mol%, preferably at least 50 mol%
As described above, aluminoxane formed from a mixed alkyloxyaluminum unit containing at least 70 mol% is particularly preferable.

The [B-2] organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, or a benzene-insoluble organoaluminum oxy compound found by the present applicants. You may.

As a method for producing such an aluminoxane, for example, the following method can be exemplified. (1) Compounds containing water of adsorption or salts containing water of crystallization, such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as trialkylaluminum to a hydrocarbon medium suspension of the above to react. (2) A method in which water is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) Decane, benzene, organoaluminum compounds such as trialkylaluminum in a medium such as toluene,
A method of reacting an organotin compound such as dimethyltin oxide and dibutyltin oxide.

Among these methods, it is preferable to adopt the method (1). The aluminoxane may contain a small amount of an organic metal component other than aluminum. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered aluminoxane solution by distillation, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used in the production of aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum and triisopropylaluminum.
n-butyl aluminum, triisobutyl aluminum,
Trisec-butyl aluminum, tritert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, trialkyl aluminum such as tridecyl aluminum, tricyclohexyl aluminum, tricycloalkyl aluminum such as tricyclooctyl aluminum, dimethyl aluminum Dialkylaluminum halides such as chloride, diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride, dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride, dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide, diethylaluminum And dialkylaluminum aryloxides such as ammonium phenoxide.

Also, isoprenyl aluminum represented by the following general formula can be used. (I-C ₄ H ₉ ) x Aly (C ₅ H ₁₀ ) z (where x, y, and z are positive numbers and z ≧ 2x). Of these, trialkylaluminum is particularly preferred. .

The above-mentioned organoaluminum compounds are used alone or in combination. Solvents used in the production of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic solvents such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. Hydrocarbons, cyclopentane, cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclopentane, petroleum fractions such as gasoline, kerosene, gas oil, and the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons; Examples thereof include hydrocarbon solvents such as halides, especially chlorides and bromides, and ethers such as ethyl ether and tetrahydrofuran. Of these, aromatic hydrocarbons are particularly preferably used.

When the catalyst component [A] is a [A-1] solid titanium catalyst component or [A-2] a titanium trichloride catalyst component, [B] an organometallic compound catalyst component Is preferably [B-1] an organoaluminum compound, and when [A] the transition metal compound catalyst component is [A-3] a metallocene compound, [B] the organometallic compound catalyst component is [B-2]. ] It is preferable that it is an organic aluminum oxy compound.

In preliminarily polymerizing an α-olefin and a polyene compound with the [A] transition metal compound catalyst component and [B] organometallic compound catalyst component, the aforementioned electron donor (a) may be used, if necessary. Alternatively, the following electron donor (b) may be used.

As such an electron donor (b), an organosilicon compound represented by the following general formula can be used. R _n Si (OR ') in _4-n (wherein, R and R' is a hydrocarbon group, 0 <n <4
Specific examples of the organosilicon compound represented by the above general formula include the following compounds.

Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane,
t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane , Screw p-
Tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane,
Ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, Methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-
Aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyl Dimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane,
Methyl triaryloxy silane, vinyl tris (β-methoxyethoxy silane), vinyl triacetoxy silane, dimethyl tetraethoxy disiloxane, cyclopentyl trimethoxy silane, 2-methyl cyclopentyl trimethoxy silane, 2,3-dimethyl cyclopentyl trimethoxy Silane, cyclopentyltriethoxysilane, dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, dicyclopentyldiethoxysilane, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, Dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, hexenyltrimethoxysilane, dicyclopentylmethylethoxysilane Orchids, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, cyclopentyldimethylethoxysilane.

Of these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, Bis-p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane,
Cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, phenyltriethoxysilane, dicyclopentyldimethoxysilane, hexenyltrimethoxysilane, cyclopentyltriethoxysilane, tricyclopentylmethoxysilane, cyclopentyldimethylmethoxysilane, etc. It is preferably used.

These organic silicon compounds can be used in combination of two or more. Further, in the present invention, as the electron donor (b), 2,6-substituted piperidines, 2,5-substituted piperidines, N, N, N ', N'-tetramethylmethylenediamine, N, N, N' N-containing electron donors such as substituted methylenediamines such as N, N'-tetraethylmethylenediamine, substituted methylenediamines such as 1,3-dibenzylimidazolidine and 1,3-dibenzyl-2-phenylimidazolidine; Phosphorus-containing electron donors such as phosphites such as phytite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, tri-isobutyl phosphite, diethyl n-butyl phosphite and diethyl phenyl phosphite And oxygen-containing electron donors such as 2,6-substituted tetrahydropyrans and 2,5-substituted tetrahydropyrans.

The above-mentioned electron donors (b) are used alone or in combination of two or more. In the present invention,
In forming the α-olefin / polyene copolymer-containing polymer [I], the above-mentioned α-olefin and polyene compound are first added to the above-mentioned [A] transition metal compound catalyst component and [B] organometallic compound catalyst component. Are copolymerized to form a prepolymerized catalyst containing the α-olefin / polyene copolymer (i).

In the present invention, when the [A] transition metal compound catalyst component and [B] organometallic compound catalyst component are preliminarily polymerized with an α-olefin and a polyene compound, the polyene compound is added to 1 mol of the α-olefin per mole. Usually 0.0001 to 10 mol, preferably 0.0005 to 5 mol
It is preferred to use them in moles, particularly preferably in amounts of 0.001 to 2 moles.

The copolymerization of the α-olefin with the polyene compound can be carried out by any of a liquid phase polymerization method such as solution polymerization and suspension polymerization or a gas phase polymerization method. When the polymerization is carried out in a liquid phase, the polymerization can be carried out in the presence of an inert solvent described later. Further, the polymerization can be carried out using the olefin and the polyene compound used in the polymerization as a solvent or in a state substantially without a solvent.

In the present invention, the preliminary copolymerization can be carried out in the presence of an inert solvent described later, and the above-mentioned olefin, polyene compound and catalyst component are added to the inert solvent, and the reaction is carried out under relatively mild conditions. Is preferred. At this time, the reaction may be carried out under a condition in which the produced prepolymer is dissolved in the polymerization medium, or may be carried out under a condition in which the prepolymer is not dissolved.

In the present invention, the above-mentioned prepolymerized catalyst can be prepared more specifically as follows. i) In an inert solvent, [A] a transition metal compound catalyst component, [B] an organometallic compound catalyst component and, if necessary, an electron donor are brought into contact in advance to form a prepolymerization catalyst,
A method in which an α-olefin and the polyene compound are copolymerized with the catalyst to form a prepolymerized catalyst. ii) in a mixture of an α-olefin and a polyene compound, [A] a transition metal compound catalyst component, [B] an organometallic compound catalyst component and, if necessary, an electron donor to previously contact to form a catalyst, A method in which an α-olefin and a polyene compound are copolymerized with the catalyst to form a prepolymerized catalyst.

Examples of the inert solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene.
Alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as α-olefin chloride and chlorobenzene; and mixtures thereof. .

Among them, it is particularly preferable to use an aliphatic hydrocarbon. The prepolymerization can be performed in any of a batch system, a continuous system, and a semi-continuous system.

Although the concentration of the catalyst component in the prepolymerization varies depending on the catalyst component used, the concentration of the transition metal compound catalyst component is usually about 0.001 to 5000 mmol, in terms of transition metal atoms, per liter of polymerization volume. , Preferably about 0.01 to 1000 mmol, particularly preferably 0.1 to 500 mmol.

The organometallic compound catalyst component is used in an amount of 0.01 to 2,000 g, preferably 0.03 to 1000 g, more preferably 0.05 to 20 g per gram of the transition metal compound catalyst component.
It is used in an amount such that 0 g of a polymer is produced, and is usually about 0.1-1000 mol, preferably about 0.5-500 mol, particularly preferably about 1 mol of transition metal atom in the transition metal compound catalyst component. It is used in an amount of 1 to 100 mol.

When an electron donor is used, the electron donor is used in an amount of 0.01 to 50 mol, preferably 0.05 to 50 mol, per 1 mol of transition metal atom in the transition metal compound catalyst component.
It is used in an amount of 30 mol, more preferably 0.1 to 10 mol.

The reaction temperature during the prepolymerization is usually about -20.
To + 100 ° C, preferably about -20 to + 80 ° C, and more preferably about -10 to + 40 ° C.
In the preliminary polymerization, a molecular weight regulator such as hydrogen may be used.

The prepolymerized catalyst according to the present invention comprises the above-mentioned [A] transition metal compound catalyst component and [B] organometallic compound catalyst component per 1 g of the transition metal compound catalyst component.
0.01 to 2000 g, preferably 0.03 to 1000 g,
More preferably, it is obtained by copolymerizing an α-olefin and a polyene compound in an amount of 0.05 to 200 g.

The prepolymerized catalyst containing the α-olefin / polyene copolymer (i) is usually obtained in a suspended state. Such a prepolymerized catalyst can be used as it is in a suspended state in the subsequent polymerization, or can be used by separating the prepolymerized catalyst from the suspension.

The prepolymerized catalyst obtained in the above suspension state was
In the main polymerization step described below, the organometallic compound catalyst component or the electron donor may not need to be further added. In the present invention, prior to the above preliminary copolymerization,
An olefin can be preliminarily polymerized on the [A] transition metal compound catalyst component and [B] the organometallic compound catalyst component.

As the olefin, the above-mentioned olefins are used. Of these, α-olefins are preferable, and propylene is more preferable. When the olefin is preliminarily polymerized in the olefin polymerization catalyst prior to the precopolymerization as described above, for example, the following effects can be specifically obtained. That is, when the olefin is preliminarily polymerized in the olefin polymerization catalyst prior to the precopolymerization as described above, a prepolymerized catalyst excellent in particle shape such as particle size distribution and particle size distribution can be obtained.

In the present invention, the above-mentioned olefin is polymerized or copolymerized with the prepolymerized catalyst obtained as described above to form an olefin polymer (ii). In forming the olefin polymer (ii), the prepolymerization catalyst is
Usually, about 0.001 to 100 mmol, preferably about 0.0100, in terms of transition metal atoms per liter of polymerization volume.
It is used in an amount of from 0.5 to 20 mmol.

At this time, if necessary, an organometallic compound catalyst component or an electron donor may be further used together with the prepolymerization catalyst. When the organometallic compound catalyst component [B] is used, the organometallic compound catalyst component [B] is
The metal atom in the catalyst component [B] is usually about 1 to 200 moles per 1 mole of the transition metal atom in the prepolymerization catalyst in the polymerization system.
It is used in an amount such that it is 0 mol, preferably about 2 to 500 mol. When an electron donor is used, the electron donor is generally used in an amount of about 0.001 mol to 10 mol, preferably 0.01 mol to 1 mol, per 1 mol of the metal atom in the organometallic compound catalyst component [B]. Used in an amount of 5 mol.

When hydrogen is used during the polymerization, the molecular weight of the obtained polymer can be adjusted, and a polymer having a high melt flow rate can be obtained. In the present invention, the olefin can be polymerized by any of a liquid phase polymerization method such as solution polymerization and suspension polymerization or a gas phase polymerization method. Further, it can be carried out by any of a batch system, a semi-continuous system and a continuous system.

When the polymerization takes a reaction form of slurry polymerization, the above-mentioned inert organic solvent or a liquid olefin at the reaction temperature can be used as the reaction solvent.

The polymerization conditions vary depending on the olefin used in the polymerization, but the polymerization temperature is usually from -20 to 300.
° C, preferably about -20 to 150 ° C, more preferably -10 to 130 ° C, and the polymerization pressure is usually normal pressure to 10
0 kg / cm ² , preferably about ² to 50 kg / cm ² .

Further, the olefin polymerization can be carried out in two or more stages. At this time, the reaction conditions in each stage may be the same or different. The olefin polymer (ii) thus formed is a homopolymer of olefin,
It may be a random copolymer or a block copolymer composed of two or more olefins.

Next, the olefin polymer [II] contained in the olefin polymer composition will be described. As the olefin polymer [II] used in the present invention, conventionally known α-olefin polymers or copolymers having 2 to 20 carbon atoms can be widely used. Specifically, for example, high-density poly-α-olefin, low-density poly-α-olefin, linear low-density poly-α-olefin, polypropylene, polybutene, poly (4-methyl-1-pentene), polypentene, α-olefin Olefin / propylene copolymer, α
-Olefin / butene copolymer, propylene / butene copolymer, α-olefin / propylene / butene copolymer, 4-methyl-1-pentene / olefin copolymer, α-
Examples include olefin / cyclic olefin copolymers, α-olefin / propylene / polyene compound copolymers, various propylene-based block copolymers, propylene-based random copolymers, and mixtures thereof.

Among them, the olefin polymer [II] is the same olefin polymer as the olefin forming the olefin polymer (ii) contained in the α-olefin / polyene copolymer-containing polymer [I]. It is preferably used.

The olefin polymer composition for forming the extruded product according to the present invention comprises the above-mentioned α-olefin / polyene copolymer-containing polymer [I] in an amount of 0.005 to 99%.
% By weight, preferably 0.01 to 90% by weight, more preferably 0.03 to 85% by weight, and particularly preferably 0.05 to 90% by weight.
In an amount of 80% by weight, the olefin polymer [I
I] is 99.995-1% by weight, preferably 99.9%
It is contained in an amount of 9 to 10% by weight, more preferably 99.97 to 15% by weight, particularly preferably 99.95 to 20% by weight.

The olefin polymer composition is prepared by blending the above amount of the α-olefin / polyene copolymer-containing polymer [I] and the olefin polymer [II]. Specifically, the α-olefin / polyene copolymer-containing polymer [I] and the olefin polymer [II] are mixed with each other by using an apparatus generally used for kneading a polymer in an amount of 100 to 350. ° C, preferably 1
Knead at a temperature of 50-300 ° C.

The olefin polymer composition forming the extruded product according to the present invention has a higher melt tension than the conventionally known olefin polymer [II] as described above, for example.

Specifically, in such an olefin polymer composition, the melt flow rate and the melt tension satisfy the following relational expression. When the olefin polymer [II] is polypropylene, the olefin polymer composition usually has a log [MT] ≧ −0.8 log [MFR] +0.28, preferably a log [MT] ≧ −0.8 log [MFR] +0.30 More preferably, the relationship represented by log [MT] ≧ −0.8 log [MFR] +0.33 is satisfied.

In the case of the polypropylene (olefin polymer [II]) alone, the melt flow rate and the melt tension usually satisfy the relationship represented by log [MT] = − 0.8 log [MFR] +0.24. ing.

The melt tension expressed in relation to the intrinsic viscosity [η] is usually represented by log [MT] = 3.7 log [η] -1.6.

The extruded product according to the present invention is molded by an extrusion method using the olefin polymer composition as described above. However, since this olefin polymer composition has a high melt tension, It can be molded at a high speed during extrusion molding, and a large product can be obtained.

The shape and product type of the extruded product according to the present invention are not particularly limited, but specific examples include sheets, films, pipes, hoses, wire coatings, and monofilaments.

In order to produce the extruded product according to the present invention from the olefin polymer composition as described above, a conventionally known extruder can be used. For example, a single screw extruder, a kneading extruder, a ram extruder, a gear extruder and the like are used. Further, an annular die or a T die may be attached to the extruder.

As the molding conditions, conventionally known conditions can be adopted. In the present invention, among such molding conditions, it is preferable to produce a molded body under the following conditions.

For example, using an extruder equipped with a T die,
Resin temperature 100-300 ° C, preferably 150-270
° C, T-die temperature 80 ° C to 270 ° C, preferably 130 ° C
A method of forming a sheet at a temperature of from 250C to 250C is exemplified.

Water is used for cooling the compact, and when a sheet is formed, there is a method using an air knife or a cooling roll. Further, at the time of molding, paper, cloth or the like can be fed onto a roll to produce artificial leather, waterproof cloth, and various laminated products.

The olefin polymer composition forming the extruded product according to the present invention comprises a phenol-based stabilizer, an organic phosphite-based stabilizer, a thioether-based stabilizer, a hindered amine-based stabilizer, and a higher fatty acid metal salt. It is preferable to include at least one or more.

These compounds are used in an amount of preferably 0.005 to 5 parts by weight, preferably 0.01 to 0.5 parts by weight, based on 100 parts by weight of the olefin polymer composition.

As the phenolic stabilizer, conventionally known phenolic stabilizers can be used without any particular limitation. Specifically, the following compounds are used. 2,6-di-t-butyl
-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-diphenol
-t-Amyl-4-methylphenol, 2,6-di-t-octyl
-4-n-propylphenol, 2,6-dicyclohexyl-4-n
-Octylphenol, 2-isopropyl-4-methyl-6-t
-Butylphenol, 2-t-butyl-2-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-5-t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, styrene Cresol, dl-
α-tocophenol, t-butylhydroquinone, 2,2′-methylenebis (4-methyl-6-t-butylphenol), 4,4 ′
-Butylidenebis (3-methyl-6-t-butylphenol)
, 4,4'-thiobis (3-methyl-6-t-butylphenol)
, 2,2'-thiobis (4-methyl-6-t-butylphenol)
, 4,4'-methylenebis (2,6-di-t-butylphenol)
, 2,2'-methylenebis [6- (1-methylcyclohexyl) -p
-Cresol], 2,2'-ethylidenebis (4,6-di-t-butylphenol), 2,2'-butylidenebis (2-t-butyl
-4-methylphenol), 1,1,3-tris (2-methyl-4-
(Hydroxy-5-t-butylphenyl) butane, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2'-thiodiethylenebis [3-
(3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di -t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4
-t-butylbenzyl) isocyanurate, 1,3,5-tris
[(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tris (4-t-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 2,4- Bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, tetrakis [methylene-3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate] methane, bis (3,5-di-t
-Ethyl butyl-4-hydroxybenzylphosphonate) calcium, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate) nickel, bis [3,3-bis (3-t
-Butyl-4-hydroxyphenyl) butyric acid]
Glycol ester, N, N'-bis [3- (3,5-di-t-butyl
-4-hydroxyphenyl) propionyl] hydrazine,
2,2'-Ogizamide bis [ethyl-3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate], bis [2-t-
Butyl-4-methyl-6- (3-t-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 1,3,5-trimethyl-2,4,6-tris (3,5-di- t-butyl-4-hydroxybenzyl) benzene, 3,9-bis [1,1-dimethyl-2- (β
-(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2,2-bis [4- ( 2- (3,5-di-t-butyl-4-hydroxyhydrocinnamoyloxy)) ethoxyphenyl] propane and stearyl-β- (4-hydroxy-3,5-di-tert-butylphenol) propionate β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester and the like.

Among them, 2,6-di-tert-butyl-4-
Methylphenol, stearyl-β- (4-hydroxy-
3,5-di-tert-butylphenol) propionate, 2,2 '
-Ethylidenebis (4,6-di-tert-butylphenol),
Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane is preferred.

As the phosphite-based stabilizer, specifically, the following compounds are used. Trioctyl phosphite, trilauryl phosphite, tristridecyl phosphite, tris isodecyl phosphite,
Phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, Tris (2,4-di-t-butylphenyl) phosphite, tris (butoxyethyl) phosphite, tetratridecyl-4,4'-butylidenebis (3-methyl-6-t-butylphenol) -diphosphite, 4, 4'-isopropylidene-diphenol alkyl phosphite (where alkyl is about 12 to 15 carbon atoms), 4,4'-isopropylidenebis (2-t-butylphenol) di (nonylphenyl) phosphite, tris ( Biphenyl) phosphite, tetra (g Decyl) -
1,1,3-tris (2-methyl-5-t-butyl-4-hydroxyphenyl) butane diphosphite, tris (3,5-di-t-butyl-4-hydroxyphenyl) phosphite, hydrogenated -4,4 '
-Isopropylidene diphenol polyphosphite, bis (octylphenyl) bis [4,4'-butylidenebis (3-methyl-6-t-butylphenol)]-1,6-hexaneoldiphosphite, hexatridecyl- 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenol) diphosphite, tris [4,4′-isopropylidenebis (2
-t-butylphenol)] phosphite, tris (1,3-
Distearoyloxyisopropyl) phosphite, 9,
10-dihydro-9-phosphaphenanthrene-10-oxide, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite, distearylpentaerythritol diphosphite, (Nonylphenyl) pentaerythritol diphosphite, phenyl-4,4'-isopropylidenediphenolpentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite and phenylbisphenol-A-pentaerythritol diphosphite.

Among them, tris (2,4-di-tert-
Butylphenyl) phosphite, tris (nonylphenyl) phosphite and tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite are preferred, and tris (2,4-di- Particularly preferred is (t-butylphenyl) phosphite.

As the organic thioether-based stabilizer, it is preferable to use dialkylthiodipropionates and polyhydric alcohol esters of alkylthiopropionic acids. As the dialkylthiodipropionate used here, a dialkylthiodipropionate having an alkyl group having 6 to 20 carbon atoms is preferable. Further, as the polyhydric alcohol ester of alkylthiopropionic acid,
Polyhydric alcohol esters of alkylthiopropionic acid having an alkyl group having 4 to 20 carbon atoms are preferred. In this case, examples of the polyhydric alcohol constituting the polyhydric alcohol ester include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and trishydroxyethyl isocyanurate.

Specific examples of such a dialkylthiodipropionate include dilaurylthiodipropionate, dimyristylthiodipropionate and distearylthiodipropionate.

Examples of the polyhydric alcohol ester of alkylthiopropionic acid include glycerin tributylthiopropionate, glycerin trioctyl thiopropionate, glycerin trilauryl thiopropionate and glycerin tristearyl thiopropionate; Methylol ethane tributyl thiopropionate, trimethylol ethane trioctyl thiopropionate, trimethylol ethane trilauryl thiopropionate and trimethylol ethane tristearyl thiopropionate; pentaerythritol tetrabutyl thiopropionate, pentaerythritol tetra Octylthiopropionate, pentaerythritol tetralaurylthiopropionate and pentaerythritol tetrastearylthione Propionate can be mentioned.

Of these, dilauryl thiodipropionate, distearyl thiodipropionate and pentaerythritol tetralauryl thiopropionate are preferably used.

The following compounds are specifically used as the hindered amine stabilizer. Screw (2,2,
6,6-tetramethyl-4-piperidyl) sebacate, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-succinate
2,2,6,6-tetramethylpiperidine polycondensate, poly [[6
-(1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexa Methylene [(2,2,6,6-tetramethyl-4-piperidyl) imino], tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxy Rate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis- (1,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-tert-butyl-4 -Hydroxybenzyl) -2-n-butylmalonate, bis- (N-methyl-2,2,
6,6-tetramethyl-4-piperidyl) sebacate, 1,1'-
(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), (mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3 , 4-butanetetracarboxylate, (mixed 1,2,2,6,6-pentamethyl-4-
Piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mixed {2,2,6,6-tetramethyl-4-
Piperidyl / β, β, β ', β'-tetramethyl-3,9- [2,4,
8,10-Tetraoxaspiro (5,5) undecane] diethyl {-1,2,3,4-butanetetracarboxylate, mixed {1,2,2,6,6-pentamethyl-4-piperidyl / β , β,
β ', β'-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,
6,6-pentamethyl-4-piperidyl) amino] -6-chloro-
1,3,5-triazine condensate, poly [6-N-morpholyl-1,3,5
-Triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4
-Piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imide], N, N'-bis (2,2,
Condensation product of 6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane, [N- (2,2,6,6-
Tetramethyl-4-piperidyl) -2-methyl-2- (2,2,6,6-
Tetramethyl-4-piperidyl) imino] propionamide. Among these hindered amine stabilizers, the following compounds are particularly preferred.

Dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [6- (1,1,3,3-tetramethyl Butyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,
2,6,6-tetramethyl-4-piperidyl) imino], tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-
Butanetetracarboxylate, bis- (1,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-tert-butyl-4-
Hydroxybenzyl) -2-n-butylmalonate, 1,1'-
(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), (mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3 , 4-butanetetracarboxylate, (mixed 1,2,2,6,6-pentamethyl-4-
Piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mixed {2,2,6,6-tetramethyl-4-
Piperidyl / β, β, β ', β'-tetramethyl-3,9- [2,4,
8,10-Tetraoxaspiro (5,5) undecane] diethyl {-1,2,3,4-butanetetracarboxylate, mixed {1,2,2,6,6-pentamethyl-4-piperidyl / β , β,
β ', β'-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,
6,6-pentamethyl-4-piperidyl) amino] -6-chloro-
1,3,5-triazine condensate, poly [6-N-morpholyl-1,3,5
-Triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4
-Piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imide], N, N'-bis (2,2,
Condensation product of 6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane, [N- (2,2,6,6-
Tetramethyl-4-piperidyl) -2-methyl-2- (2,2,6,6-
Tetramethyl-4-piperidyl) imino] propionamide.

Examples of the metal salts of higher fatty acids include magnesium salts of higher fatty acids such as stearic acid, oleic acid, lauric acid, capric acid, arachidic acid, palmitic acid, behenic acid, 12-hydroxystearic acid, ricinoleic acid and montanic acid. Alkaline earth metal salts such as calcium salts and barium salts, cadmium salts, zinc salts, lead salts, alkali metal salts such as sodium salts, potassium salts and lithium salts are used. Specifically, the following compounds are used.

Magnesium stearate, magnesium laurate, magnesium palmitate, calcium stearate, calcium oleate, calcium laurate, barium stearate, barium oleate, barium laurate, barium arachidate, barium behenate, zinc stearate, olein Zinc acid, zinc laurate, lithium stearate, sodium stearate, sodium palmitate, sodium laurate, potassium stearate, potassium laurate, 12-
Calcium hydroxystearate, calcium montanate and the like.

The extruded product according to the present invention may further comprise other heat stabilizers, weather stabilizers, antistatic agents, slip agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils , Wax and the like.

The extruded product according to the present invention can be used as long as the object of the present invention is not impaired, such as silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, and hydroxide. Magnesium, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, guffite, Aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber,
A filler such as polyethylene fiber, polypropylene fiber, polyester fiber, and polyamide fiber may be included.

[0167]

The extruded product according to the present invention comprises a specific olefin polymer composition and can be molded at high speed.
The size can be increased.

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

[0169]

EXAMPLE 1 The reactor of the "solid titanium catalyst component [A] Preparation of" 4.5 m ^3, anhydrous magnesium chloride 240 Kg, decane 11
00 liter and 2-ethylhexyl alcohol 990
After charging Kg and heating at 130 ° C. to make a homogeneous solution, 54 Kg of phthalic anhydride was added to this solution,
The mixture was stirred at 0 ° C. to dissolve phthalic anhydride. After cooling the homogeneous solution thus obtained to room temperature,
The whole homogeneous solution was dripped into 6.7 m ^{3 of} titanium tetrachloride held in the flask while stirring. Temperature after charging is approx.
20 ° C. The temperature of the mixture was raised to 11 over 4 hours.
The temperature was raised to 0 ° C., and when the temperature reached 110 ° C., 13 kg of diisobutyl phthalate (DIBP) was added, and the mixture was stirred and maintained at the same temperature for 2 hours.

After completion of the reaction, a solid portion was collected by hot filtration.
This solid portion was resuspended in 7.3 m ³ of titanium tetrachloride and then heated again at 110 ° C. for 2 hours. After the completion of the reaction, the solid portion was collected again by hot filtration, and sufficiently washed with decane and hexane at 110 ° C. until no free titanium compound was detected in the solution.

By the above operation, a solid titanium catalyst component [A] was obtained. The composition of the solid titanium catalyst component [A] thus obtained was 2.2% by weight of titanium and 61% of chlorine.
% By weight, magnesium by 19% by weight, and DIBP by 12.7% by weight. "Preliminary polymerization of solid titanium catalyst component [A]" Purified hexane 40 in a 80-liter reactor equipped with a stirrer under nitrogen atmosphere
Liter, 0.9 mol of triethylaluminum and the solid titanium catalyst component [A] in an amount of 0.1% in terms of titanium atom.
After adding 3 moles, 1.66 propylene was added at a temperature of 20 ° C.
The mixture was supplied to a Kg reactor and prepolymerized for 2 hours.

After the completion of the reaction, the inside of the reactor was replaced with nitrogen, and a washing operation including removal of a supernatant and addition of purified hexane was performed three times to obtain a prepolymerized catalyst [B]. Then, at 0 ° C
68.4 liters of hexane, 1,9-decadiene 1.
After adding 6 liters and 2.1 moles of diethylaluminum ethoxide, ethylene was fed to the reactor. During the polymerization reaction, the temperature was kept at 0 ° C, and when 4650 liters of ethylene had reacted, the supply of ethylene was stopped.

When the supply of ethylene was completed, the inside of the reactor was replaced with nitrogen, and a washing operation including removal of the supernatant and addition of purified hexane was performed five times, and the prepolymerized catalyst [C]
I got The prepolymerized catalyst [C] was resuspended in purified hexane and stored.

With the prepolymerized catalyst [C] thus obtained, 10.2 g / g of the transition metal compound catalyst component was used.
g of ethylene / 1,9-decadiene copolymer was produced. "Polymerization" After charging 50 liters of purified hexane under a nitrogen atmosphere into a reactor with a stirrer of 80 liters, the temperature was raised to 60 ° C, and 5 mol of triethylaluminum, 1 mol of cyclohexylmethyldimethoxysilane (CMMS) and the above prepolymerized catalyst component [C] is 0.1 mol in terms of titanium atom,
After adding 0.3 liter of hydrogen, propylene was supplied to the reactor and polymerization was performed for 2 hours. The polymerization temperature was kept at 70 ° C. and the pressure was kept at ² kg / cm ² .

The polymerization reaction was stopped by adding a large amount of isobutyl alcohol to which a small amount of hydrochloric acid was added, and the gas to be supplied was switched to nitrogen.
Stirring was continued for minutes.

After the completion of the stirring, the slurry containing the produced solid was filtered to separate the polymer, and dried under reduced pressure at 70 ° C. to obtain 20.3 kg of a polyene / olefin copolymer-containing composition [C]. The polyolefin / olefin copolymer-containing composition [C] has an MFR of 8.0 dg / min. And [η] of 1.
85 dl / g, polyene / olefin copolymer content is 1
It was 4.5% by weight. "Production of polypropylene composition" 30 parts by weight of a polyene / olefin copolymer-containing composition [C], 1 part by weight of calcium stearate, 1 part by weight of 3,5-di-t-butyl-4-hydroxytoluene, tetrakis [ Methylene (3,5-di-t-butyl-4-hydroxy) hydrocinnamate] methane 1 part by weight, polypropylene [II] (homopolymer) (MFR =
3.0 dg / min., [Η] is 2.42 dl / g, boiling heptane extraction residual ratio 98.0%), and 1000 parts by weight are mixed.
It was granulated into pellets using an mmφ extruder. The resulting polypropylene composition had a melt tension (MT) of 5.3 g, an MFR of 3.1 dg / min., And [η] of 2.40 dl /
g, polyene-olefin copolymer content was 0.46% by weight. "Extrusion molding of polypropylene composition" The above-mentioned polypropylene composition was mixed with an FS-65 type pipe molding machine (D
= 65 mmφ, L / D = 25), resin temperature 220 ° C
Thus, a pipe having a thickness of 1 mm and a diameter of 10 cm was formed. Drawdown did not occur on the way, and the moldability was good.

[0177]

[Comparative Example 1] "Extrusion molding of polypropylene" A pipe was molded in the same manner as in Example 1 except that the commercially available polypropylene of Example 1 was used. However, drawdown occurred halfway, and molding was not possible.

[0178]

Example 2 "Production of polypropylene composition" 25 parts by weight of a polyene / olefin copolymer-containing composition [C], 1 part by weight of calcium stearate, 3,5-di-t-butyl-4-hydroxytoluene 1 Parts by weight, tetrakis [methylene (3,5-di-t-butyl-4-hydroxy) hydrocinnamate] methane 1 part by weight, polypropylene [II] (homopolymer) (MFR =
0.5 dg / min., [Η] = 3.54 dl / g, boiling heptane extraction residual ratio 98.5%), and 1000 parts by weight.
It was granulated into pellets using an mmφ extruder. The resulting polypropylene composition had a melt tension (MT) of 18.5 g, an MFR of 0.6 dg / min., And [η] of 2.40 dl / min.
g, polyene-olefin copolymer content was 0.40% by weight. "Extrusion molding of polypropylene composition" A pipe having a thickness of 1.8 mm and a diameter of 70 cm was molded in the same manner as in Example 1 except that the above-mentioned polypropylene composition was used. Drawdown did not occur on the way, and the moldability was good.

[0179]

[Comparative Example 2] "Extrusion molding of polypropylene" A pipe was molded in the same manner as in Example 1 except that the commercially available polypropylene of Example 2 was used. However, drawdown occurred halfway and molding was not possible.

[0180]

Example 3 "Extrusion molding of polypropylene composition" The polypropylene composition produced in Example 1 was used in combination with GS-65 manufactured by Ikegai Iron Works.
Using a mold sheet forming machine (D = 65 mmφ, L / D = 25), a sheet having a resin temperature of 220 ° C. and a thickness of 2 mm was formed.
Drawdown did not occur on the way, and the moldability was good.

──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 3-204467 (32) Priority date August 14, 1991 (August 14, 1991) (33) Priority claim country Japan (JP) (72) Inventor: Mamoru Kioka 1-2-1, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A-62-32105 (JP, A) 56412 (JP, A) JP-A-2-311507 (JP, A) JP-A-4-159312 (JP, A) JP-A-5-202238 (JP, A) US Pat. No. 5,021,382 (US, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 4/60-4/70 C08F 10/00-10/14 C08L 23/00-23/36 CA (STN) EPAT (QUESTEL) REGISTRY (STN) WPI / L (QUESTEL)

Claims (6)

(57) [Claims] [1] [I] [A] a transition metal compound catalyst component
[B] Periodic Table Group I - including the selection Bareru metal from Group III
Α-olefins and poly
And a d emissions formed by copolymerization, is derived from α- olefin
99 . In an amount of 999-50 mol%, poly
0.001 to 50 of the structural unit derived from the ene compound
Α-olefins and polyenes
Using a prepolymerized catalyst containing polymer (i),
Polymerize or copolymerize the olefin polymer (ii) to form
Α-olefin / polyene copolymer-containing polymer obtained by synthesis: 0.005 to 99% by weight, and [II] olefin polymer: 1 to 99.995% by weight. An extruded body characterized in that it is made. 2. The α-olefin / polyene copolymer-containing olefin polymer [I] comprises: (i) an α-olefin / polyene copolymer in an amount of 0.001 to 0.001;
The extrudate according to claim 1, characterized in that it comprises (ii) an olefin polymer in an amount of 99.999 to 85% by weight in an amount of 15% by weight. 3. The catalyst component for a transition metal compound, wherein the α-olefin / polyene copolymer-containing olefin polymer [I] is [A] selected from Ti, Zr, Hf, Cr and V ; B] The organometallic compound catalyst component containing a metal selected from Groups I to III of the Periodic Table includes an α-olefin and a polyene compound in an amount of 0.01 to 2000 g per 1 g of the [A] transition metal compound catalyst component. Α-olefin / polyene copolymer
An olefin polymer is obtained by polymerizing or copolymerizing an olefin with a prepolymerization catalyst containing (i).
3. An α-olefin / polyene copolymer-containing polymer obtained by forming (ii).
An extruded product according to the above. 4. The extruded product according to claim 1, wherein the polyene compound is a polyene compound having olefinic double bonds at both ends. 5. The polyene compound is an aliphatic polyene compound and / or an alicyclic polyene compound having an olefinic double bond at both terminals and has 7 or more carbon atoms. 4. The extruded product according to 2 or 3. 6. The method according to claim 1, wherein the olefin polymer (ii) is polypropylene or polyethylene.
4. The extruded product according to 2 or 3.