JPH05185490A - Blow molding - Google Patents

Abstract

PURPOSE:To provide a blow molding consisting of a specific olefin polymer, which is molded into a large-sized vessel such as bottles by a blow-molding method. CONSTITUTION:A blow molding is provided which consists of an olefin polymer containing an alpha-olefin.polyene copolymer comprising (i) an alpha-olefin.-polyene copolymer and (ii) an olefin polymer. Such polymer containing an alpha-olefin- polyene copolymer is manufactured, for example. such that an a olefin and a polyene compound are copolymerlzed in [A] a transition metal compound catalyst ingredient and [B] an organic metal compound catalyst ingredient containing metal selected from the first group-the third group of a periodic table at a quantity of 0.01-2000 g per l g of [A] a transition metal compound catalyst ingredient, and the olefin polymer (ii)is formed by polymerizing or copolymerizing olefin into a preliminary compound catalyst containing the alpha-olefin.polyene copolymer (i).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention relates to a blow molded product made of an olefin polymer molded by a blow molding method.

[0002]

BACKGROUND OF THE INVENTION Conventionally, high density polyethylene,
Olefin polymers represented by linear low-density polyethylene and polypropylene are excellent in transparency and
It has excellent mechanical strength such as rigidity and impact strength, and is used as various parts. For example, polypropylene is used as bumpers for automobiles and linings for refrigerators.

Since polypropylene has a low melt tension (melt tension, MT), it has been difficult to mold it into a large container such as a bottle by a blow molding method. Therefore, if an olefin polymer having a high melt tension appears, a large container such as a bottle can be manufactured from this olefin polymer by a blow molding method.

The present inventors have conducted research on an olefin polymer having a high melt tension in order to meet the above requirements. As a result, 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 a large container such as a bottle is manufactured by blow molding. The inventors have found that they can be achieved and have completed the present invention.

[0005]

OBJECT OF THE INVENTION It is an object of the present invention to provide a blow molded product made of a specific olefin polymer, which is molded into a large container such as a bottle by a blow molding method.

[0006]

SUMMARY OF THE INVENTION According to the present invention, (i) α-olefin
There is provided a blow-molded article made of an olefin polymer containing an α-olefin / polyene copolymer, which comprises a polyene copolymer and (ii) an olefin polymer.

Such an α-olefin / polyene copolymer-containing polymer is an organic compound containing, for example, a catalyst component [A] transition metal compound and a metal [B] selected from Group I to Group III of the periodic table. An α-olefin and a polyene compound are copolymerized with a metal compound catalyst component in an amount of 0.01 to 2000 g per 1 g of the [A] transition metal compound catalyst component, and an α-olefin / polyene copolymer (i) is obtained. An olefin polymer (ii) can be produced by polymerizing or copolymerizing an olefin with a prepolymerization catalyst containing

[0008]

DETAILED DESCRIPTION OF THE INVENTION The blow-molded article comprising the olefin polymer according to the present invention will be specifically described below. First, the α-olefin.
The polyene copolymer-containing olefin polymer (hereinafter sometimes simply referred to as olefin polymer) will be described in detail.

Such an α-olefin / polyene copolymer-containing polymer comprises (i) an α-olefin / polyene copolymer and (ii) an olefin polymer.

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

The α-olefin and polyene compound used for forming the above α-olefin / polyene copolymer (i) will be described. Examples of the α-olefin used in the present invention include α-olefins having 2 to 20 carbon atoms, 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, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned. 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 later. Of these, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 3-methyl
-1-Butene, 1-eicosene and the like are preferably used.

Specific examples of the polyene compound include the following compounds. 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,
Aliphatic polyene compounds such as 1,5,9-decatriene, butadiene and isoprene, vinylcyclohexene, vinylnorbornene, ethylidenenorbornene, 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, aromatic polyene compounds such as divinylbenzene and vinylisopropenylbenzene.

These may be used alone or in combination. In the present invention, among the above polyene compounds, polyene compounds having 7 or more carbon atoms and having olefinic double bonds at both ends are preferable, and aliphatic compounds having olefinic double bonds at both ends are preferable. Or an alicyclic polyene compound is more preferred.

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

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

In forming the α-olefin / polyene copolymer (i), ethylene / 1,7-octadiene, ethylene / 1,9-decadiene, ethylene are among the above α-olefin and polyene compounds. / 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 are preferably copolymerized.

In such an α-olefin / polyene copolymer (i), the constituent unit derived from the α-olefin is usually 99.999 to 50 mol%, preferably 99.
999-70 mol%, more preferably 99.995-7
5 mol%, more preferably 99.99-80 mol%,
Particularly preferably in an amount of 99.95 to 85 mol%, the structural unit derived from the polyene compound is 0.001 to 50 mol%, preferably 0.001 to 30 mol%, more preferably 0.005 to 25 mol%. %, More preferably 0.01
It is desirable that the content is ˜20 mol%, particularly preferably 0.05 to 15 mol%.

Further, α-olefin / polyene copolymer
(i) may contain units derived from other olefins described later, within a range that does not impair the object of the present invention. In this case, the structural 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 α-olefin and polyene compounds consumed during the polymerization. Specifically, the structural unit [P mol%] derived from polyene is calculated as follows.

[0021]

[Equation 1]

(Where [P ₀ ] is the number of moles of the polyene compound supplied during polymerization [P _r ] is the number of moles of the unreacted polyene compound [α ₀ ] is the number of moles of the α-olefin supplied during the polymerization. [Α _r ]: number of moles of unreacted α-olefin) The above [α _r ] and [P _r ] are the unreacted α-olefin and polyene compounds remaining in the polymerization vessel measured by gas chromatography or the like. It is determined by

As the olefin used for forming the olefin polymer (ii) forming the α-olefin / polyene copolymer-containing polymer, the above-mentioned olefin having 2 carbon atoms is used.
.About.20 .alpha.-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- Octene, 10
Examples include silane unsaturated compounds such as trimethylsilyl-1-decene, and the above-mentioned polyene compounds.

These may be used alone or in combination. Among 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 such an α-olefin / polyene copolymer-containing polymer [I], the α-olefin / polyene copolymer (i) is 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) was 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,
0.001 to α-olefin / polyene copolymer (i)
In an amount of 15% by weight, preferably 0.008-10% by weight,
Particularly preferred are those containing the olefin polymer (ii) in an amount of 99.999 to 85% by weight, preferably 99.992 to 90% by weight.

The α-olefin / polyene copolymer-containing polymer [I] 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 0.02-2000 g / 10 minutes,
It is particularly preferably 0.05 to 1000 g / 10 minutes.

The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.05 to 20 dl / g, preferably 0.
It is 1 to 15 dl / g, particularly preferably 0.2 to 13 dl / g.

Such an α-olefin / polyene copolymer-containing polymer has a high melt tension (melt tension,
MT). In the α-olefin / polyene copolymer-containing polymer 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 is an ethylene / polyene copolymer, and the olefin polymer (ii) is a polypropylene. In this case, the α-olefin / polyene copolymer-containing polymer has a log [MT] ≧ −0.8 log [MFR] +0.3, preferably a log [MT] ≧ −0.8 log [MFR] +. 0.5 More preferably, log [MT] ≧ −0.8log [MFR] +0.7, particularly preferably, the relational expression log [MT] ≧ −0.8log [MFR] +0.8 is satisfied. ..

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

Further, for example, the α-olefin / polyene copolymer-containing polymer 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 1g
/ 10 minutes, 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, further preferably 4.5 g or more, particularly preferably 5.0 g or more. Is.

The melt tension (M) of the polymer [I] containing the α-olefin / polyene copolymer used in the present invention is
T) satisfies the relational expression with the melt flow rate (MFR) as described above, and satisfies the following equation 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-containing polymer [I] forming the α-olefin / polyene copolymer (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] is preferably [log] [MT] ≧ 3.7 log [[η]] − 1.50. Satisfies the relationship represented by log [MT] ≧ 3.7log [[η]] − 1.45, particularly preferably log [MT] ≧ 3.7log [[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 the olefin polymer has a melt tension of 0.92 g / cm ³ and an intrinsic viscosity [η] of 1.8 dl / g, the melt tension of the olefin polymer is 2.5 g or more, preferably 3.5 g or more, and more preferably 4.0 g or more. , More preferably 4.5 g or more, particularly preferably 5.0 g or more.

The melt tension is measured as follows. Using an MT measuring device manufactured by Toyo Seiki Seisakusho, an orifice, a polymer 7 g, and a polymer were placed in a cylinder held at a polymer melting temperature (230 ° C. in the case of polypropylene).
Insert the pistons in that order. After 5 minutes, the piston is pushed down at a speed of 10 mm / min, and the molten polymer is pushed out through 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 wound up by a winding roller at a speed of 25 m / min. At this time,
The stress applied to the pulley is measured, and this value is taken as the melt tension of the polymer.

Next, the [A] transition metal compound catalyst component used when producing the above-mentioned polymer containing the α-olefin / polyene copolymer 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, preferably Ti, Zr, Hf, Nb, Ta,
Examples thereof include compounds containing at least one transition metal selected from Cr and V.

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

Such solid titanium catalyst component [A-1]
Details of the method for preparing are described in, for example, the following publications. Japanese Patent Publication 46-34
092, Japanese Patent Publication No. 53-46799, Japanese Patent Publication No. 60-3
No. 323, Japanese Examined Patent Publication No. 63-54289, JP-A 1-26.
1404, JP-A-1-261407, JP-B-47-
No. 41676, Japanese Patent Publication No. 47-46269, Japanese Patent Publication No. 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, and JP-A-58-20.
6613, JP-A-58-125706, JP-A-63.
-68606, JP-A 63-69806, JP-A 6-
0-81201, JP 61-40306, JP 51-281189, JP 50-126590,
JP-A-51-92885, JP-B-57-45244
No. 57-26613 / 61-5483
No. 5, JP-A-56-811, JP-B-60-37804
Japanese Patent Publication No. 59-50246, Japanese Patent Laid-Open No. 58-8300.
6, JP-A-48-16986, JP-A-49-659.
99, JP-A-49-86482, JP-B-56-39
No. 767, Japanese Patent Publication No. 56-32232, Japanese Patent Laid-Open No. 55-2.
9591, JP-A-53-146292, JP-A-57.
-63310, JP-A-57-63311, JP-A-5
7-63312, JP-A-62-273206, JP-A-63-69804, JP-A-61-21109, JP-A-63-264607, JP-A-60-23404.
JP-A-60-44507, JP-A-60-1582
04, JP-A-61-55104, JP-A-2-282.
01, JP-A-58-196210, JP-A-64-5
4005, JP-A-59-149905, JP-A-61.
-145206, JP-A-63-302, JP-A-63
-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-62-104813.

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

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 compounds represented by the following formula.

In the formula Ti (OR) _g X _4-g , 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 , 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 ) Br ₃ and other trihalogenated alkoxy titanium, Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti
_{(On-C 4 H 9)} 2 Cl 2, Ti (OC 2 H 5) dihalogenated dialkoxy titanium, such as _{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
Mono-halogenated trialkoxy titanium such as r, Ti (O
_{CH 3) 4, Ti (OC} 2 H 5) 4, Ti (On-C 4 H 9) 4, Ti
Examples thereof include tetraalkoxytitanium such as (O-iso-C ₄ H ₉ ) ₄ and Ti (O-2-ethylhexyl) ₄ .

Among these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds may be used alone or in combination of two or more. Alternatively, it may be diluted with a hydrocarbon or a halogenated hydrocarbon before use.

Titanium trichloride is used as the trivalent titanium compound. As such titanium trichloride,
For example, titanium trichloride obtained by bringing titanium tetrachloride into contact with hydrogen or a metal such as magnesium metal, aluminum metal, or titanium metal or an organometallic compound such as an organomagnesium compound, an organoaluminum compound, and an organozinc compound is preferable. Used.

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

Examples of the magnesium compound having a reducing ability include organomagnesium compounds represented by the following formula. X _n MgR _{2-n In the} formula, n is 0 ≦ n <2, and R is hydrogen or carbon number 1
To 20 alkyl groups, aryl groups or cycloalkyl groups, and when n is 0, two Rs may be the same or different, and X is halogen.

Specific examples of the organomagnesium compound having such a reducing ability include dimethyl magnesium, diethyl magnesium, dipropyl magnesium,
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 halides, butyl ethoxy magnesium, ethyl butoxy magnesium, and octyl butoxy magnesium, and butyl magnesium hydride.

Specific examples of the magnesium compound having no reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride, and methoxy magnesium chloride.
Alkoxy magnesium halides such as ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride, allyloxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride, ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-oct Examples include alkoxymagnesium such as xymagnesium and 2-ethylhexoxymagnesium, allyloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium, and magnesium carboxylates such as magnesium laurate and magnesium stearate. In addition, magnesium metal and magnesium hydride can also be used.

The magnesium compound having no reducing ability may be a compound derived from the above-mentioned magnesium compound having reducing ability 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 used as a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, a halogen. It may be brought into 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
It may form an organometallic compound described later, for example, a complex compound with another metal such as aluminum, zinc, boron, beryllium, sodium and potassium, a double compound, or a mixture with another metal compound. Good. Further, the magnesium compound may be used alone, or two or more kinds of the above compounds may be combined, and may be used in a liquid state or a solid state. When the magnesium compound is a solid, alcohols, carboxylic acids, aldehydes, amines, metal acid esters, etc., which will be described later, can be used as the electron donor (a) to bring it into a liquid state.

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

Of these, a magnesium compound having no reducing ability is preferable, a halogen-containing magnesium compound is particularly preferable, and among these, magnesium chloride, alkoxy magnesium chloride, and aryloxy magnesium chloride are preferable.

An electron donor (a) is preferably used in the preparation of the solid titanium catalyst component [A-1]. Such electron donors (a) include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, organic acid or inorganic acid esters, ethers, diethers, acid amides. , Acid anhydrides, oxygen-containing electron donors such as alkoxysilanes, ammonia,
Examples thereof 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, isopropylbenzyl. C1-C18 alcohols such as alcohols, C1-C18 halogen-containing alcohols such as trichloromethanol, trichloroethanol and trichlorohexanol, phenol, cresol, xylenol, ethylphenol,
Propylenephenol, nonylphenol, cumylphenol, naphthol, and other phenols having 6 to 20 carbon atoms which may have a lower alkyl group, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone,
C3 to C15 ketones such as benzophenone and benzoquinone, acetaldehyde, propionaldehyde,
C2-C15 aldehydes such as octyl aldehyde, benzaldehyde, tolualdehyde, and naphthaldehyde, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, citrate. 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 ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethyl carbonate, etc. C2 to C18 organic acid esters, C2 to C15 acid halides such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride, 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,
Benzoic acid N, N-diethylamide, toluic acid N, N-dimethylamide and other acid amides, trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylethylenediamine and other amines, acetonitrile, benzonitrile, trinitrile and other nitriles 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 polyvalent carboxylic acid ester having a skeleton represented by the following general formula can be mentioned as a preferred example.

[0057]

[Chemical 1]

(In the formula, 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 hydrocarbon group. It is an unsubstituted hydrocarbon group, preferably at least one of which 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 includes a hetero atom such as N, O and S, and is, for example, C—O.
-C, COOR, COOH, OH, SO 3 H, -C-N
It has groups such as -C- and NH ₂ . ) As such a polyvalent carboxylic acid ester, specifically, an aliphatic polycarboxylic acid ester, an alicyclic polycarboxylic acid ester,
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 nadic acid, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-phthalate. Butyl, di-2-phthalate
Examples thereof include ethylhexyl and dibutyl 3,4-furandicarboxylate.

Examples of particularly preferable polycarboxylic acid esters include phthalic acid esters. Further, examples of the diether compound include compounds represented by the following general formula.

[0061]

[Chemical 2]

(In the formula, n is an integer of 2 ≦ n ≦ 10, and R ^{1 to} R ²⁶ are at least one selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon. It is a substituent having an element, and any R ¹ to
R ²⁶ , preferably R ^{1 to} R ²ⁿ may together form a ring other than a benzene ring, and the main chain may contain an atom other than carbon. ) As a preferred specific example, 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 can be exemplified.

The above electron donors (a) are used in combination of two or more kinds. The solid titanium catalyst component [A-1] used in the present invention is an organic compound containing silicon, phosphorus, aluminum, etc. used as a carrier compound and a reaction auxiliary agent in addition to the above-mentioned compounds at the time of preparation. Alternatively, an inorganic compound or the like may be contacted to prepare.

Examples of such carrier compounds include Al
₂ O ₃ , SiO ₂ , B ₂ O ₃ , MgO, CaO, TiO ₂ ,
Resins such as ZnO, SnO ₂ , BaO, ThO and styrene-divinylbenzene copolymer are used. Of these, 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 titanium compound, magnesium compound and preferably the electron donor (a).

The method of preparing the solid titanium catalyst component [A-1] using these compounds is not particularly limited, but in the case of using a tetravalent titanium compound, several examples of this method will be described below. Briefly. (1) A method in which a solution containing a magnesium compound, an electron donor (a) and a hydrocarbon solvent is contact-reacted with an organometallic compound to precipitate a solid, or while being precipitated, the titanium compound is contact-reacted. (2) A method in which a complex consisting of a magnesium compound and an electron donor (a) is reacted with an organometallic compound and then a titanium compound is subjected to a catalytic reaction. (3) A method of contacting a titanium compound with a contact product of an inorganic carrier and an organomagnesium compound. At this time, the contact product may be previously contact-reacted with the halogen-containing compound, the electron donor (a) and / or the organometallic compound. (4) Magnesium compound, electron donor (a), from a mixture of a solution optionally containing a hydrocarbon solvent and an inorganic or organic carrier, to obtain a magnesium compound-supported inorganic or organic carrier, then a titanium compound How to contact. (5) Magnesium compounds, titanium compounds, electron donors
(a) A method of obtaining a solid titanium catalyst component [A-1] carrying magnesium and titanium by contacting a solution optionally containing a hydrocarbon solvent with an inorganic or organic carrier. (6) A method of reacting an organomagnesium compound in a liquid state with a halogen-containing titanium compound by catalytic reaction. (7) A method in which a liquid organomagnesium compound is contact-reacted with a halogen-containing compound and then a titanium compound is contacted. (8) A method in which an alkoxy group-containing magnesium compound is catalytically reacted with a halogen-containing titanium compound. (9) A method in which a complex composed of an alkoxy group-containing magnesium compound and an electron donor (a) is catalytically reacted with a titanium compound. (10) A method in which a complex consisting of an alkoxy group-containing magnesium compound and an electron donor (a) is contacted with an organometallic compound and then contacted with a titanium compound. (11) A method of contacting and reacting a magnesium compound, an electron donor (a), and a titanium compound in any order. In this reaction, each component may be pretreated with an electron donor (a) and / or a reaction aid 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) as necessary to precipitate a solid magnesium-titanium complex. (13) A method of further reacting a titanium compound with the reaction product obtained in (12). (14) A method of further reacting the reaction product obtained in (11) or (12) with an electron donor (a) and a titanium compound. (15) A method of treating a solid material obtained by pulverizing a magnesium compound, a titanium compound, and optionally an electron donor (a) with halogen, a halogen compound or an aromatic hydrocarbon. This method may include a step of pulverizing only the magnesium compound, the complex compound composed of the magnesium compound and the electron donor (a), or the magnesium compound and the titanium compound. Further, after the pulverization, pretreatment with a reaction auxiliary agent and then treatment with halogen or the like may be performed. Examples of the reaction aid include organic metal compounds and halogen-containing silicon compounds. (16) A method of pulverizing a magnesium compound and then contacting and reacting with the titanium compound. At this time, an electron donor (a) or a reaction aid may be used during pulverization and / or contact / reaction. (17) A method of treating the compound obtained in (11) to (16) above with halogen or a halogen compound or an aromatic hydrocarbon. (18) A method of bringing a reaction product of a metal oxide, an organomagnesium and a halogen-containing compound into contact with a titanium compound and optionally an electron donor (a). (19) A method of reacting a magnesium compound such as a magnesium salt of an organic acid, alkoxy magnesium, or aryloxy magnesium with a titanium compound and / or a halogen-containing hydrocarbon and optionally an electron donor (a). (20) A method of bringing a hydrocarbon solution containing at least a magnesium compound and alkoxytitanium into contact 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) Solid magnesium obtained by reacting a liquid magnesium compound having no reducing ability with an organometallic compound.
A method in which a metal (aluminum) complex is deposited and then a titanium compound and, if necessary, an electron donor (a) are reacted.

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

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

Also preferably, the electron donor (a) is usually
The electron donor (a) / titanium (molar ratio) is 0.01 to 10
It is contained at a ratio of 0, preferably 0.05 to 50. In the present invention, the solid titanium catalyst component [A-1] as described above is used.
With regard to the above, an example using a titanium compound has been described, but in the above titanium compound, titanium may be replaced with zirconium, hafnium, vanadium, niobium, tantalum or chromium.

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

Details of the method for preparing such [A-2] titanium trichloride catalyst component are described in, for example, the following publications. JP 63-1
7274, JP-A-64-38409, JP-A-56-
34711, JP-A-61-287904, JP-A-6.
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
No. 1, JP-A 1-292901, JP-A 1-292901
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 a tetravalent titanium compound or after being brought into contact with them.

Further, in the present invention, [A-3] metallocene compound may be used as the [A] transition metal compound catalyst component. Details of the method for preparing such an [A-3] metallocene compound are described in, for example, the following publications.

JP-A-63-61010, JP-A-63-
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-1-259004, 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
-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. 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
179, JP-A-1-12407, JP-A-1-301
704, JP-A-1-319489, and JP-A-3-74.
412, JP-A-61-264010, JP-A 1-2.
75609, JP-A-63-251405, JP-A-6
4-74202, JP-A-2-41303, JP-A-2
-131488, JP-A-3-56508, JP-A-3
-70708, JP-A-3-70709 and the like.

Specific examples of the [A-3] metallocene compound include compounds represented by the following formula. 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 the ligand having a cyclopentadienyl skeleton has 1 to 1 carbon atoms.
2 hydrocarbon group, alkoxy group, aryloxy group, trialkylsilyl group, 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 Alternatively, it is a hydrogen atom, and x is the valence of the transition metal. Examples of the ligand having a cyclopentadienyl skeleton include, for example, 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 group Examples of alkyl-substituted cyclopentadienyl groups such as enyl group, methylbutylcyclopentadienyl group, hexylcyclopentadienyl group or indenyl group, 4,5,6,7-tetrahydroindenyl group, fluorenyl group, etc. You can These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

Of these ligands which coordinate to the transition metal, an alkyl-substituted cyclopentadienyl group is particularly preferable. When the compound represented by the above general formula contains two or more groups having a cyclopentadienyl skeleton, 2
Groups having two cyclopentadienyl skeletons are substituted with alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene, silylene groups or dimethylsilylene groups, diphenylsilylene groups, and methylphenylsilylene groups. It may be bound 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, the alkyl group includes 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., aralkyl group, benzyl group, neophyll group, etc. Are exemplified.

As the alkoxy group, a methoxy group,
Examples thereof include an ethoxy group and a butoxy group, examples of the aryloxy group include a phenoxy group, and examples of the halogen include fluorine, chlorine, bromine, iodine and the like.

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

R ² _k R ³ _l R ⁴ _m R ⁵ _n M (wherein M is the above transition metal, R ² is a group (ligand) having a cyclopentadienyl skeleton, and R ³ , R ⁴ and R ⁵ are groups having a cyclopentadienyl skeleton, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, trialkylsilyl groups, SO ₃ R groups, halogen atoms or hydrogen atoms. And k is an integer of 1 or more, and k + l + 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. Groups having these cyclopentadienyl skeletons include alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene, silylene groups or substituted silylene groups such as dimethylsilylene, diphenylsilylene and methylphenylsilylene groups. It may be bound via. R ⁴ and R ⁵ are groups having a cyclopentadienyl skeleton, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, trialkylsilyl groups, SO ₃
R, a halogen atom or a hydrogen atom.

Specific examples of the transition metal compound in which M is zirconium are shown below. 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, ethylene bis (indenyl) zirconium dichloride, ethylene Bis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) zirconium bis (methanesulfonate), ethylenebis ( Indenyl) zirconium bis (p-toluene sulfonate), ethylene bis (indenyl) zirconium bis (trifluoromethane sulfonate), ethylene bis (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 (trifluoromethane sulfonate),
Dimethyl silylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethyl silylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenyl silylene bis (indenyl) zirconium dichloride, methylphenyl silylene bis (indenyl) zirconium dichloride , Bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis (cyclopenta Dienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride, bis (cyclopentadienyl) benzyl Benzalkonium monochloride,
Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadiene) (Enyl) dibenzyl zirconium, bis (cyclopentadienyl) zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl)
Zirconium bis (p-toluene sulfonate), bis (cyclopentadienyl) zirconium bis (trifluoromethane sulfonate), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis ( Dimethylcyclopentadienyl) zirconium ethoxy chloride, 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, the di-substituted cyclopentadienyl ring includes 1,2- and 1,3-substituted compounds, and the tri-substituted compound is 1,2,3- and 1,2,4-substituted compounds. Including the body. Alkyl groups such as propyl and butyl are n-, i-, sec-, tert-
Including isomers such as.

In the zirconium compound as described above, 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,
You may use it in combination of 2 or more type. Further, it may be diluted with a hydrocarbon or a halogenated hydrocarbon before use.
In the present invention, as the metallocene compound [A-3], a zirconocene compound having a central metal atom of zirconium and having a ligand containing at least two cyclopentadienyl skeletons is preferably used.

The [A-3] metallocene compound as described above can also be used by supporting it on a carrier by bringing it into contact with a particulate carrier compound. As a carrier compound, SiO
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 kinds. Of these, SiO ₂ , Al
₂ O ₃ and MgO are preferably used. Next, a group I-group 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.

Such an organometallic compound catalyst component [B]
Are, for example, [B-1] organoaluminum compounds, complex alkyl compounds of Group I metal and aluminum,
Organometallic compounds of Group II metals and the like can be used.

As such an [B-1] organoaluminum compound, an organoaluminum compound represented by the following formula can be exemplified. R ^a _n AlX _3-n (In the formula, R ^a is a hydrocarbon group having 1 to 12 carbon atoms;
Is halogen or hydrogen, and n is 1 to 3. ) In the above formula, R ^a 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 isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group. As such an organoaluminum compound, the following compounds are specifically used.

Trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, tri 2-
Trialkylaluminum such as ethylhexylaluminum.

Alkenyl aluminum, such as isoprenyl aluminum. Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride and dimethyl aluminum bromide.

Alkyl aluminum sesquihalides 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. Further, as the [B-1] organoaluminum compound, a compound represented by the following formula can also be used.

R ^a _n AlY _{3-n In the} above formula, R ^a is the same as above, and Y is -OR.
^b group, -OSiR ^c ₃ group, -OAlR ^d ₂ group, -NR ^e ₂ group, -
SiR ^f ₃ group or —N (R ^g ) AlR ^h ₂ group, and n is 1
˜2, R ^b , R ^c , R ^d and R ^h are methyl groups,
An ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., R ^e is hydrogen, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, etc., and R ^f and R ^g are a methyl group, For example, an ethyl group.

As the [B-1] organoaluminum compound, the following compounds are specifically used. (i) R ^a _n Al (OR ^b ) _3-n dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, etc., (ii) R ^a _n Al (OSiR ^c ₃ ) _3-n Et ₂ Al (OSiMe ₃ ) (iso-Bu) ₂ Al (OSiMe ₃ ) (iso-Bu) ₂ Al (OSiEt ₃ ), etc. (iii) R ^a _n Al (OAlR ^d ₂ ) _3-n Et ₂ AlOAlEt ₂ (iso-Bu) ₂ AlOAl (iso-Bu) ₂ etc., (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 ₂ ] _3-n Et ₂ AlN (Me) -AlEt ₂ (iso-Bu) ₂ AlN (Et) Al (iso-Bu) _{2 and the} like.

Further, as the above [B-1] organoaluminum compound, R ^a ₃ Al, R ^a _n Al (OR ^b ) _3-n , R a
^A preferable example is an organoaluminum compound represented by ^a _n Al (OAlR ^d ₂ ) _3-n .

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 (provided that M ¹ is Li, Na, K, and R ^j has 1 carbon atom)
Specifically, LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄
And so on.

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

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 the general formulas (1) and (2).

[0100]

[Chemical 3]

(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
May be the same hydrocarbon group as R, and R ¹ and R ² represent different groups]. In that case, the methyloxyaluminum unit (OAl
(CH ₃ )) is 30 mol% or more, preferably 50 mol%
Above all, particularly preferably, an aluminoxane formed from mixed alkyloxyaluminum units contained in a proportion of 70 mol% or more is suitable.

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. May be.

As the method for producing such aluminoxane, the following method can be exemplified. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to the hydrocarbon medium suspension and reacted. (2) A method in which water is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran. (3) To an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene or toluene,
A method of reacting an organic tin compound such as dimethyltin oxide or dibutyltin oxide.

Among these methods, the method (1) is preferably adopted. It should be noted that the aluminoxane may contain a small amount of an organometallic component other than aluminum. Further, the solvent or the unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane and then redissolved in the solvent.

Specific examples of the organoaluminum compound used in the production of aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum and trialuminum.
n-butyl aluminum, triisobutyl aluminum,
Trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and other trialkylaluminums, tricyclohexylaluminum, tricyclooctylaluminum and other tricycloalkylaluminums, dimethylaluminum Dialkyl aluminum halides such as chloride, diethyl aluminum chloride, diethyl aluminum bromide and diisobutyl aluminum chloride, dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride, dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide, diethyl aluminum Examples thereof include dialkylaluminum aryloxides such as aluminum phenoxide.

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

The above organoaluminum compounds may be used alone or in combination. As the solvent used in the production of aluminoxane, aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, pentane, hexane, heptane, aliphatic hydrocarbons such as octane, decane, dodecane, hexadecane and octadecane. Of hydrocarbons, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons. Hydrocarbon solvents such as halides, especially chlorides and bromides, and ethers such as ethyl ether and tetrahydrofuran can be mentioned. Of these, aromatic hydrocarbons are particularly preferably used.

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

When preliminarily polymerizing the [A] transition metal compound catalyst component and the [B] organometallic compound catalyst component with an α-olefin and a polyene compound, the above-mentioned electron donor (a) is optionally used. 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 ′) _4-n (wherein R and R ′ are hydrocarbon groups, and 0 <n <4
Specific examples of the organosilicon compound represented by the above general formula include the following compounds.

Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysisilane, 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-norbornanemethylsilane Dimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane,
Methyltriallyloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane Silane, cyclopentyltriethoxysilane, dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, dicyclopentyldiethoxysilane, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, Dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, hexenyltrimethoxysilane, dicyclopentylmethylethoxysilane Orchid, 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 organosilicon compounds can be used in combination of two or more kinds. 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' Substituted methylenediamines such as N, N'-tetraethylmethylenediamine, nitrogen-containing electron donors such as 1,3-dibenzylimidazolidine, substituted methylenediamines such as 1,3-dibenzyl-2-phenylimidazolidine, triethylphos Phosphorus-containing electron donors such as phosphites such as phyto, tri-n-propyl phosphite, tri-isopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite and diethyl phenyl phosphite It is also possible to use oxygen-containing electron donors such as 2,2,6-substituted tetrahydropyrans and 2,5-substituted tetrahydropyrans.

The above electron donors (b) may be used alone or in combination of two or more. In the present invention,
In forming the α-olefin / polyene copolymer-containing polymer, first, the above-mentioned α-olefin and polyene compound are added to the above [A] transition metal compound catalyst component and [B] organometallic compound catalyst component. Polymerize α-
A prepolymerization catalyst containing an olefin / polyene copolymer (i) is formed.

In the present invention, when the [A] transition metal compound catalyst component and the [B] organometallic compound catalyst component are prepolymerized with an α-olefin and a polyene compound, the polyene compound is added to 1 mol of the α-olefin. Usually 0.0001 to 10 mol, preferably 0.0005 to 5 mol
It is preferably used in an amount of 0.001 to 2 mol, particularly preferably 0.001 to 2 mol.

The copolymerization of the α-olefin with the polyene compound can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. When the polymerization is carried out in the liquid phase, the polymerization can be carried out in the coexistence of an inert solvent described later. It is also possible to polymerize using the olefin and polyene compound itself used during the polymerization as a solvent, or to polymerize in a substantially solvent-free state.

In the present invention, this preliminary copolymerization can be carried out in the coexistence of an inert solvent which will be described later, and the above olefin, polyene compound and catalyst component are added to the inert solvent and the polymerization is carried out under relatively mild conditions. Preferably. At this time, it may be carried out under the condition that the produced prepolymer is dissolved in the polymerization medium, or it may be carried out under the condition of not dissolving it, but it is preferably carried out under the condition of not dissolving.

In the present invention, the prepolymerization catalyst as described above can be prepared more specifically as follows. i) In an inert solvent, the [A] transition metal compound catalyst component, the [B] organometallic compound catalyst component and optionally an electron donor are pre-contacted to form a prepolymerization catalyst,
A method of forming a prepolymerized catalyst by copolymerizing this catalyst with an α-olefin and the above polyene compound. ii) In the mixture of the α-olefin and the polyene compound, the catalyst is formed by previously contacting the [A] transition metal compound catalyst component, the [B] organometallic compound catalyst component and, if necessary, an electron donor. A method of forming a prepolymerized catalyst by copolymerizing this catalyst with an α-olefin and a polyene compound.

Specific examples of the above-mentioned 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. ..

Of these, it is particularly preferable to use an aliphatic hydrocarbon. The prepolymerization can be carried out in any of batch system, continuous system and semi-continuous system.

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

The organometallic compound catalyst component is 0.01 to 2000 g, preferably 0.03 to 1000 g, and more preferably 0.05 to 20 g, per 1 g 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 to 1000 mol, preferably about 0.5 to 500 mol, and particularly preferably, per mol of the 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 5 mol, per mol of the 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 in the prepolymerization is usually about -20.
It is desirable that the temperature is from about + 100 ° C, preferably about -20 to + 80 ° C, and more preferably about -10 to + 40 ° C.
In the prepolymerization, a molecular weight modifier such as hydrogen can be used.

The prepolymerization catalyst according to the present invention contains the above-mentioned [A] transition metal compound catalyst component and [B] organometallic compound catalyst component per 1 g of 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 prepolymerization catalyst containing the α-olefin / polyene copolymer (i) is usually obtained in a suspended state. Such a prepolymerization catalyst can be used in the suspension state in the polymerization in the next step, or can be used by separating the prepolymerization catalyst from the suspension.

The prepolymerized catalyst obtained in the above suspension state is
In the main polymerization step described below, it may be unnecessary to further add the organometallic compound catalyst component or the electron donor. In the present invention, prior to the above preliminary copolymerization,
Olefin can be preliminarily preliminarily polymerized with the transition metal compound catalyst component [A] and the organometallic compound catalyst component [B].

As the olefin, the above-mentioned olefins are used, but of these, α-olefins are preferable, and propylene is more preferable. Thus, when the olefin polymerization catalyst is preliminarily prepolymerized with the olefin prior to the precopolymerization, the following effects are specifically obtained. That is, as described above, when the olefin polymerization catalyst is preliminarily preliminarily polymerized with olefin prior to the preliminary copolymerization, a prepolymerization catalyst having an excellent particle shape such as particle size distribution and particle size distribution can be obtained.

In the present invention, the olefin polymer (ii) is then formed by polymerizing or copolymerizing the above-mentioned olefin with the prepolymerized catalyst obtained as described above. In forming the olefin polymer (ii), the prepolymerization catalyst is
The amount is usually about 0.001 to 100 mmol, preferably about 0.00, calculated as transition metal atoms per liter of polymerization volume.
Used in an amount of 05-20 mmol.

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

If 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 polymerization can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization or gas phase polymerization methods. Further, it can be carried out by any of batch method, semi-continuous method and continuous method.

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

Although the polymerization conditions vary depending on the olefin used during the polymerization, the polymerization temperature is usually -20 to 300.
C., preferably about −20 to 150 ° C., more preferably −10 to 130 ° C., and the polymerization pressure is usually atmospheric pressure to 10 ° C.
It is 0 kg / cm ² , preferably about ² to 50 kg / cm ² .

Further, the polymerization of this olefin 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 block copolymer composed of two or more olefins.

The α-olefin / polyene copolymer-containing olefin polymer as described above has a higher melt tension than conventional olefin polymers. The blow-molded article according to the present invention has the above-mentioned α-olefin.
It is molded by a blow molding method using a polyene copolymer-containing olefin polymer, but since this olefin polymer has a high melt tension, it is
It can be molded into large containers such as bottles.

Moreover, the blow-molded article according to the present invention has a high strength and can increase the molding rate during production. In order to produce the blow-molded article according to the present invention from the above-mentioned olefin polymer, a conventionally known blow-molding apparatus can be used. As the molding conditions, conventionally known conditions can be adopted.

For example, in the case of extrusion blow molding, the resin temperature is 100 ° C to 300 ° C, preferably 170 ° C to 270 ° C.
With the die, a tubular parison is extruded in a molten state of the above olefin polymer, and then the parison is held in a mold having a shape to be imparted, and then air is blown into the parison.
C. to 300.degree. C., preferably 200.degree. C. to 270.degree. C., is attached to a mold to obtain a hollow molded article. Stretch ratio is 1.5 in the transverse direction
~ 5 times.

Resin temperature 100 ° C. for injection blow molding
The olefin polymer is injected into a mold at ˜300 ° C., preferably 170 ° C. to 270 ° C. to form a parison, and then the parison is held in a mold having a shape to be applied, and then air is blown into the mold to obtain a resin temperature of 120. C. to 300.degree. C., preferably 140.degree. C. to 270.degree. C., is attached to a mold to obtain a hollow molded article. The stretching ratio is 1.1 to 1.8 times in the machine direction and 1.3 to 2.5 times in the transverse direction.

In the case of injection blow molding, 100 ° C. to 350 ° C.
C., preferably 170.degree. C. to 300.degree. C., the above olefin polymer is injected into a mold to form a parison, which is pre-blown under predetermined conditions and then 80.degree. C. to 280.degree. C., preferably 100.degree. Stretch blow is carried out under the condition of 260 ° C. to obtain a hollow molded article. The draw ratio is 1.2 to 4.5 in the machine direction.
And 1.2 to 8.0 times in the lateral direction.

The olefin polymer forming the blow-molded article according to the present invention has at least one of a phenol stabilizer, an organic phosphite stabilizer, a thioether stabilizer, a hindered amine stabilizer and a higher fatty acid metal salt. It is preferable to contain one or more species.

Such a compound is the olefin polymer 1
0.005 to 5 parts by weight,
It is desirable to use it in an amount of preferably 0.01 to 0.5 part by weight.

As the phenol-based stabilizer, conventionally known ones can be used without any particular limitation, and 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-di
-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 Mixed cresol, dl-
α-tocophenol, t-butylhydroquinone, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4 '
-Butylidene bis (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'-ethylidene bis (4,6-di-t-butylphenol), 2,2'-butylidene bis (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
-Butyl-4-hydroxybenzylphosphonate ethyl) calcium, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) 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 Examples include β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester.

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

The following compounds are specifically used as the phosphite stabilizer. Trioctyl phosphite, trilauryl phosphite, tris tridecyl phosphite, tris isodecyl phosphite,
Phenyldiisooctylphosphite, phenyldiisodecylphosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenylisodecylphosphite, diphenyltridecylphosphite, triphenylphosphite, 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 (however, alkyl has about 12 to 15 carbon atoms), 4,4'-isopropylidene bis (2-t-butylphenol) di (nonylphenyl) phosphite, tris ( Biphenyl) phosphite, tetra (to) Decyl) -
1,1,3-tris (2-methyl-5-t-butyl-4-hydroxyphenyl) butanediphosphite, tris (3,5-di-t-butyl-4-hydroxyphenyl) phosphite, hydrogenation -4,4 '
-Isopropylidene diphenol polyphosphite, bis (octylphenyl) -bis [4,4'-butylidene bis (3-methyl-6-t-butylphenol)]-1,6-hexaneol diphosphite, 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'-biphenylene diphosphonite, distearyl pentaerythritol diphosphite, di (Nonylphenyl) pentaerythritol diphosphite, phenyl 4,4'-isopropylidene diphenol pentaerythritol 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 these, 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- t-Butylphenyl) phosphite is particularly preferred.

As the organic thioether stabilizer, it is preferable to use a polyhydric alcohol ester of dialkylthiodipropionate and alkylthiopropionic acid. The dialkylthiodipropionate used here is preferably a dialkylthiodipropionate having an alkyl group having 6 to 20 carbon atoms. Further, as the polyhydric alcohol ester of alkylthiopropionic acid,
A polyhydric alcohol ester of alkylthiopropionic acid having an alkyl group having 4 to 20 carbon atoms is preferable. 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 dialkylthiodipropionate include dilaurylthiodipropionate, dimyristylthiodipropionate and distearylthiodipropionate.

Examples of the polyhydric alcohol ester of alkylthiopropionic acid include glycerin tributyl thiopropionate, 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 Octyl thiopropionate, pentaerythritol tetralauryl thiopropionate and pentaerythritol tetrastearyl thiol 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-piperidyl benzoate, 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-butane tetracarboxylate, (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 (2,2,2
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 may be mentioned.

Of these hindered amine stabilizers, the following compounds are particularly preferable. Dimethyl succinate
-1- (2-hydroxyethyl) -4-hydroxy-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] 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-butane tetracarboxylate, (mixed 1,2,2,
6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,
4-butane tetracarboxylate, 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-Butane tetracarboxylate, mixed {1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ', β'-tetramethyl-3,9- [2, 4,8,1
0-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 condensation Object, 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],
A condensate of N, N'-bis (2,2,6,6-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 higher fatty acid metal salt 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 salt and barium salt, alkali metal salts such as cadmium salt, zinc salt, lead salt, sodium salt, potassium salt and lithium salt 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, etc.

The blow-molded article according to the present invention further comprises other heat resistance stabilizers, weather resistance stabilizers, antistatic agents, slip agents,
It may contain an antiblocking agent, an antifogging agent, a lubricant, a dye, a pigment, a natural oil, a synthetic oil, a wax and the like.

The blow-molded article according to the present invention contains silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, and hydroxide, as long as the object of the present invention is not impaired. Magnesium, basic magnesium carbonate, dolomite, calcium sulfate,
Potassium titanate, barium sulfate, calcium sulfite,
Talc, clay, mica, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, guf fight, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber, It may contain a filler such as polyamide fiber.

[0156]

According to the present invention, (i) α-olefin
There is provided a blow-molded article made of an olefin polymer containing an α-olefin / polyene copolymer, which comprises a polyene copolymer and (ii) an olefin polymer.

This blow molded product has high strength and can be manufactured efficiently at high speed. Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

[0158]

[Example 1] "Preparation of solid titanium catalyst component [A]" In a 4.5 m ³ reactor, 240 kg of anhydrous magnesium chloride and 11 decane
00 liters and 2-ethylhexyl alcohol 990
After charging Kg and heating at 130 ° C. to make a uniform solution, 54 kg of phthalic anhydride was added to this solution, and further 13
The mixture was stirred at 0 ° C to dissolve phthalic anhydride. After cooling the homogeneous solution thus obtained to room temperature, -25 ° C
This all-homogeneous solution was added dropwise to 6.7 m ^{3 of} titanium tetrachloride held in the above vessel while stirring. The temperature after charging is approx.-
It was 20 ° C. The temperature of this mixture is 11 for 4 hours.
The temperature was raised to 0 ° C., and when it 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, the solid portion was collected by hot filtration,
The solid portion was resuspended in 7.3 m ³ of titanium tetrachloride, and then heated again at 110 ° C for 2 hours. After completion of the reaction, the solid part was collected again by hot filtration and washed sufficiently 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, 19% by weight of magnesium and 12.7% by weight of DIBP.

"Preliminary Polymerization of Solid Titanium Catalyst Component [A]" In a reactor equipped with a stirrer of 80 liters, 40 liters of purified hexane and 0.
After adding 9 mol and 0.3 mol of the above solid titanium catalyst component [A] in terms of titanium atom, propylene was fed to a 1.66 kg reactor at a temperature of 20 ° C. and prepolymerized for 2 hours.

After completion of the reaction, the inside of the reactor was replaced with nitrogen, and a washing operation consisting of removal of the supernatant and addition of purified hexane was carried out 3 times to obtain a prepolymerized catalyst [B]. Then 0 ℃
68.4 liters of purified hexane, 1,9-decadiene 1.
After the addition of 6 liters, 2.1 mol of diethylaluminium chloride, ethylene was fed to the reactor. The temperature was kept at 0 ° C. during the polymerization reaction, and the ethylene supply was stopped when 4650 liters of ethylene had reacted.

When the supply of ethylene was completed, the inside of the reactor was replaced with nitrogen, and a washing operation consisting of removal of the supernatant and addition of purified hexane was carried out 5 times to carry out the prepolymerization catalyst [C].
Got The prepolymerized catalyst [C] was resuspended in purified hexane and stored.

In the prepolymerized catalyst [C] thus obtained, 10.2 per 1 g of the transition metal compound catalyst component was used.
g of ethylene / 1,9-decadiene copolymer was formed. "Polymerization" Insert 450 liters of purified n-hexane into a reactor equipped with a stirrer and having an internal volume of 1000 liters, and add 400 mol of triethylaluminum in a propylene atmosphere at 60 ° C.
Cyclohexylmethyldimethoxysilane (CMMS) 8
0 mol and 8 of the prepolymerized catalyst [C] in terms of titanium atom
Molar Ti charge.

45 liters of hydrogen was introduced, the temperature was raised to 70 ° C., and this was held for 3.2 hours to carry out propylene polymerization. The pressure during the polymerization was kept at 6 kg / cm ² G. After the polymerization was completed, the pressure was released, the slurry containing the produced solid was centrifuged, and dried by a dryer to obtain 200 kg of a white powdery polymer.
Got

Table 1 shows the results of measuring or calculating the boiling heptane extraction residual ratio, MFR, [η], apparent bulk specific gravity, melt tension, concentration of liquid phase portion, etc. of the obtained polymer.
Shown in.

[Blow molding of polypropylene] A heat-resistant stabilizer (calcium stearate, 3,5-di-t-
Butyl-4-hydroxytoluene and tetrakis [methylene (3,5-di-t-butyl-4-hydroxy) hydrocinnamate] methane were added each at 0.1% by weight of the polymer, and melted at 220 ° C. Blow molding machine (NB made by Japan Steel Works
-20 type) was used to extrude the parison from the die head at a speed of 12 cm / sec. Immediately after that, the mold was closed, and then 6 kgf / cm ² of compressed air was blown into the parison for 1
A 0 liter canister was molded.

No drawdown occurred on the way and the moldability was good.

[0169]

Example 2 "Polymerization" Polymerization was carried out in the same manner as in Example 1 except that 130 liters of hydrogen were used.

The results are shown in Table 1. "Blow molding of polypropylene" The above polymer was manufactured from Sumitomo Bechrome's SE91 / HBV121 type hollow molding machine (D =
90 mm, L / D = 20) was used to mold a 500 ml bottle in the same manner as in Example 1 except that compressed air of 5 kgf / cm ² was blown.

No drawdown occurred on the way and the moldability was good.

[0172]

Comparative Example 1 Example 1 except that the "polymerization" prepolymerization catalyst [B] was used.
Polymerization of propylene was carried out in the same manner as in.

The results are shown in Table 1. "Blow Molding of Polypropylene" An attempt was made to mold a 10 liter canister with the same procedure as in Example 1 except that the above polymer was used, but drawdown occurred and the canister could not be obtained.

[0174]

Comparative Example 2 Example 2 except that the "polymerization" prepolymerization catalyst [B] was used.
Polymerization of propylene was carried out in the same manner as in.

The results are shown in Table 1. "Polypropylene blow molding" An attempt was made to mold a 500 ml bottle in the same manner as in Example 2 except that the above polymer was used, but drawdown occurred and the bottle could not be obtained.

[0176]

[Table 1]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (31) Priority claim number Japanese patent application No. 3-204467 (32) Priority date Hei 3 (1991) August 14 (33) Priority claim country Japan (JP) (72) Inventor Ki-oka Mamoru 6-1-2, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Industry Co., Ltd.

Claims (6)

[Claims] 1. A blow molding product comprising an α-olefin / polyene copolymer-containing olefin polymer comprising (i) an α-olefin / polyene copolymer and (ii) an olefin polymer. 2. The α-olefin / polyene copolymer-containing olefin polymer is (i) an α-olefin / polyene copolymer of 0.001 to 0.001.
The blow-molded product according to claim 1, wherein the olefin polymer (ii) is contained in an amount of 15 wt% in an amount of 99.999 to 85 wt%. 3. An α-olefin / polyene copolymer-containing olefin polymer, wherein the [A] transition metal compound catalyst component and [B] a metal selected from Group I to Group III of the periodic table. An α-olefin / polyene copolymer is obtained by copolymerizing a compound catalyst component with 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.
An olefin polymer 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).
The blow-molded article described in 1. 4. The blow molded product according to claim 1, 2 or 3, 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 olefinic double bonds at both ends and has a carbon number of 7 or more. The blow-molded article according to item 2 or 3. 6. The olefin polymer (ii) is polypropylene or polyethylene.
The blow-molded article according to 2 or 3.