JPH05194659A - Olefinic copolymer and its production - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer, having a high melt tension, excellent in moldability, transparency, rigidity and mechanical strength and useful as bottles, etc., by copolymerizing a specific alpha-olefin with a specified polyene compound in a specific proportion in the presence of a catalyst for polymerizing the olefin. CONSTITUTION:The objective copolymer is obtained by copolymerizing (A) preferably 50-99.99mol%, more preferably 70-99.99mol% 3-20C alpha-olefin such as propylene with (B) preferably 0.01-30mol% >=7C aliphatic and/or alicyclic polyene compound (e.g. 1,6-heptadiene) containing olefinic double bonds at both terminals in the presence of a catalyst composed of a transition metallic compound catalyst component such as a solid titanium catalyst component and an organometallic compound catalyst component such as an organoaluminum compound for polymerizing the olefin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention applies a blow molding method, an inflation molding method and the like to bottles, tanks, containers,
The present invention relates to an olefin-based copolymer having a high melt tension that can be formed into products such as films and tubes, and can be formed into large-sized products, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Conventionally, olefin polymers represented by polypropylene and the like are excellent in transparency and various characteristics such as rigidity and mechanical strength such as impact strength. It is used as a material for films formed by the molding method.

By the way, such an olefin polymer such as polypropylene generally has a low melt tension (melt tension, MT), and is molded into a large container such as a bottle or a lining of home electric appliances by blow molding or vacuum molding. Was difficult. Due to such limitations in molding, the molded articles to be obtained are also limited, and at present the use is limited despite having various excellent properties.

Further, when polypropylene or the like is formed into a film by an inflation molding method, there are problems that drawdown occurs and molding conditions are limited because of low melt tension. For this reason,
In conventional film inflation molding, polypropylene was compounded with high-pressure low-density polyethylene to increase melt tension and stabilize bubbles. However, such a method tends to cause a decrease in film strength and transparency.

Therefore, if an olefin polymer such as polypropylene having a high melt tension appears, a large container such as a bottle can be molded from this olefin polymer by a blow molding method, and an electric home appliance such as a refrigerator lining. And the like can be vacuum-formed, and the use of the olefin polymer is further expanded.

Furthermore, the olefin polymer having a high melt tension can stabilize the bubbles and can increase the molding speed when the film is formed by the inflation molding method.

The advent of olefin polymers such as polypropylene having such a high melt tension is desired. The present inventors have conducted research on an olefin-based copolymer having a high melt tension in order to meet the above requirements. As a result, α- having 3 to 20 carbon atoms
An olefin-based copolymer, which is a copolymer of an olefin and a specific polyene compound and contains a structural unit derived from an α-olefin having 3 to 20 carbon atoms in an amount of 50 to 99.99 mol% has a high melt tension. The inventors have found that they have the present invention and have completed the present invention.

[0008]

OBJECT OF THE INVENTION It is an object of the present invention to provide a novel olefin copolymer having a high melt tension and a method for producing the same.

[0009]

SUMMARY OF THE INVENTION The olefin copolymer according to the present invention is
Copolymerization of (i) an α-olefin having 3 to 20 carbon atoms and (ii) an aliphatic and / or alicyclic polyene compound having 7 or more carbon atoms and having olefinic double bonds at both ends 50 to 99.99 mol% of a structural unit derived from an α-olefin having 3 to 20 carbon atoms, which is a combination.
It is contained in the amount of.

The olefinic copolymer according to the present invention has a high melt tension. The method for producing an olefin-based copolymer according to the present invention comprises: (i) having 3 carbon atoms in the presence of an olefin polymerization catalyst comprising a [A] transition metal compound catalyst component and [B] an organometallic compound catalyst component. .About.20 .alpha.-olefin and (ii) an aliphatic and / or alicyclic polyene compound having 7 or more carbon atoms and having olefinic double bonds at both ends are copolymerized to obtain (i) Carbon number 3-20
A structural unit derived from the α-olefin of 50 to 9
It is characterized in that an olefin-based copolymer containing 9.99 mol% is obtained.

[0011]

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

In the present invention, the term "polymerization" may be used to include not only homopolymerization but also copolymerization, and the term "polymer" may refer to not only homopolymer but also copolymer. It may be used in a meaning including a polymer.

FIG. 1 is an explanatory view of the process for preparing the olefin copolymer according to the present invention. First, the olefin-based copolymer according to the present invention will be described. The olefin-based copolymer according to the present invention includes (i) an α-olefin having 3 to 20 carbon atoms, (ii) an aliphatic olefin having 7 or more carbon atoms, and having an olefinic double bond at both ends, and / Alternatively, it is a copolymer with an alicyclic polyene compound.

Here, (i) α having 3 to 20 carbon atoms used in forming the α-olefin copolymer according to the present invention.
-Olefin and specific (ii) polyene compounds are explained.

Specific examples of the (i) α-olefin having 3 to 20 carbon atoms used in the present invention include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene and 3-.
Methyl-1-pentene, 3-ethyl-1-pentene 4-methyl-1-
Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 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. Among these, especially propylene, butene, 4-
Methyl-1-pentene is preferred. Used in the present invention (i
i) The polyene compound has 7 or more carbon atoms and has olefinic double bonds at both ends, that is, α, ω-
Type of aliphatic and / or alicyclic polyene compounds.

Specific examples of the specific (ii) polyene compound include the following compounds. 1,6-
Heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,
Aliphatic polyene compounds such as 9-decadiene, 1,13-tetradecadiene, 1,5,9-decatriene, 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, 1,3,4-trivinylcyclohexane, Alicyclic polyene compounds such as 1-allyl-4-isopropenylcyclohexane, 1-isopropenyl-4-vinylcyclohexane and 1-isopropenyl-3-vinylcyclopentane.

These polyene compounds may be used alone or in combination. In the present invention, as described above
(ii) Of the polyene compounds, 1,7-octadiene, 1,9-decadiene, 1,13-tetradecadiene, 1,5,9-decatriene, 1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,5-divinylcyclooctane, 1-allyl-4-
Vinylcyclohexane, 1,4-diallylcyclohexane and the like are preferably used.

Among such polyene compounds having an olefinic double bond at both ends, aliphatic polyene compounds having 8 or more carbon atoms, particularly 10 or more carbon atoms are preferable, and linear aliphatic polyene compounds are particularly preferable.

The olefin copolymer according to the present invention is
(i) A structural unit derived from an α-olefin having 3 to 20 carbon atoms in an amount of 50 to 99.99 mol%, preferably 6
0-99.99 mol%, particularly preferably 70-9
In an amount of 9.99 mol%, the constituent unit derived from the (ii) polyene compound is 0.01 to 50 mol%, preferably 0.
It is contained in an amount of 01 to 40 mol%, more preferably 0.01 to 30 mol%.

Here, the structural unit (molar fraction) derived from (ii) α-olefin in the above copolymer is measured as follows. [Mole Fraction Measuring Method for Structural Units Derived from α-Olefin] 0.35 g of the copolymer is added to 2.0 ml of hexachlorobutadiene and thermally dissolved. After filtering this solution with a glass filter (G2), 0.5 ml of deuterated benzene is added to the filtrate, and the resulting solution is placed in an NMR tube having an inner diameter of 10 mm.

This is a GX-270 type N manufactured by JEOL Ltd.
Using an MR measuring device at 120 ° C ¹³C-NMR spectrum
Measure Torr. The total number of times is 20,000 or more
It Obtained as above¹³C-NMR spectrum
Is derived from an α-olefin having 3 to 20 carbon atoms
Peaks derived from structural units (hereinafter simply referred to as structural units)
Intensity and peak intensity derived from polyene compound constitutional unit
Alternatively, the sum of peak intensities is calculated and the carbon number is calculated from these.
Calculate the mole fraction of 3 to 20 α-olefin structural units
be able to.

Specifically, for example, the method of Bovey et al. (Ac
ademic Press P80 (1972)) and Ray et al.'s method (Macromole
cules, 10 , 773 (1977)) and so on, with 3 to 2 carbon atoms
The amount of constitutional units derived from 0 α-olefin can be determined.

When the olefin copolymer according to the present invention does not dissolve in hexachlorobutadiene as described above, the amount of α-olefin and polyene compound consumed during the polymerization is measured as described later. The structural unit of the copolymer can be calculated. Specifically, the mol% [α mol%] of the structural unit derived from α-olefin is calculated as follows.

[0025]

[Equation 1]

[Α ₀ ]: Number of moles of α-olefin supplied during polymerization [α _r ]: Number of moles of unreacted α-olefin [P ₀ ]: Number of moles of polyene compound supplied during polymerization [P _r ]: Number of moles of unreacted polyene compound The above [α _r ] and [P _r ] are determined by measuring the unreacted α-olefin and polyene compound remaining in the polymerization vessel by using gas chromatography or the like. It

Further, in the olefin copolymer according to the present invention, (i) an α-olefin having 3 to 20 carbon atoms and (ii)
Even if the constitutional unit derived from a copolymerizable monomer other than the specific polyene compound is contained in an amount of less than 50 mol%, preferably 40 mol% or less, more preferably 30 mol% or less. Good.

Examples of such other monomers include (iii) other olefins and (iv) other polyenes. Specifically, (iii) other olefins include styrene,
Aromatic vinyl compounds such as dimethylstyrenes, allylbenzene, allyltoluenes, vinylnaphthalenes, allylnaphthalenes, vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, alicyclic vinyl compounds such as allylnorbornane, cyclopentene, cycloheptene, Norbornene, 5-methyl-2-norbornene,
Tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,
Cyclic olefins such as 2,3,4,4a, 5,8,8a-octahydronaphthalene, allyltrimethylsilane, allyltriethylsilane, 4-trimethylsilyl-1-butene, 6-trimethylsilyl-1-hexene, 8-trimethylsilyl- 1-octene,
Examples include silane-based unsaturated compounds such as 10-trimethylsilyl-1-decene.

Further, (iv) other polyene compounds include 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-
Aliphatic polyene compounds such as 1,6-undecadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-octadiene, butadiene and isoprene, vinylcyclohexene, vinylnorbornene, ethylidenenorbornene, dicyclopentadiene, cyclooctadiene Alicyclic polyene compounds such as 2,5-norbornadiene and aromatic polyene compounds such as divinylbenzene and vinylisopropenylbenzene.

Such an olefin copolymer according to the present invention is a random copolymer or a block copolymer of (i) an α-olefin having 3 to 20 carbon atoms and (ii) a specific polyene compound. It may be either.

Preferred specific examples of the olefin copolymer according to the present invention include propylene / 1,9-decadiene copolymer, propylene / 1,13-tetradecadiene copolymer,
Propylene / 1,5,9-decatriene copolymer, propylene / 1,7-octadiene copolymer, butene / 1,9-decadiene copolymer, 4-methyl-1-pentene / 1,9-decadiene copolymer Examples include coalescing.

The olefin copolymer according to the present invention is
Melt flow rate (MFR) measured according to STM D1238E is 5000 g / 10 min or less, preferably 0.01 to 3000 g / 10 min, more preferably 0.0
2 to 2000 g / 10 minutes, particularly preferably 0.05 to 10
It is 00g / 10 minutes.

The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.05 to 20 dl / g, preferably 0.
1 to 15 dl / g, particularly preferably 0.2 to 13 dl / g. The olefin-based copolymer provided in the present invention has a higher melt tension (melt tension, MT) than conventional olefin polymers. It is generally known that the melt tension of an olefin polymer varies depending on the type of the olefin polymer and has a correlation with the melt flow rate (MFR) of the olefin polymer. Therefore, the melt tension (MT) of the olefin-based copolymer according to the present invention is difficult to unconditionally specify, but it satisfies the following formula with, for example, the melt flow rate (MFR).

For example, when the olefin-based copolymer is a propylene-based copolymer, log [MT] ≧ −0.8log [MFR] +0.3, preferably log [MT] ≧ −0.8log [ MFR] +0.4 More preferably, log [MT] ≧ −0.8log [MFR] +0.5, and most preferably log [MT] ≧ −0.8log [MFR] +0.6. Meets

The melt tension (MT) of the olefin copolymer according to the present invention satisfies the relational expression with the melt flow rate (MFR) as described above, and the following with the intrinsic viscosity ([η]): Meets the formula.

For example, when the olefin-based copolymer is a propylene-based copolymer, log [MT] ≧ 3.7log [[η]]-1.5, preferably log [MT] ≧ 3.7log [ [Η]]-1.4 More preferably, log [MT] ≧ 3.7log [[η]]-1.3 Particularly preferably, log [MT] ≧ 3.7log [[η]]-1.2 Meets the relationship indicated by.

The melt tension is measured as follows. It is measured using an MT measuring device manufactured by Toyo Seiki Seisakusho. An orifice, a polymer 7 g, and a piston are inserted in this order in a cylinder maintained at a temperature higher than the melting temperature of the polymer (at 230 ° C. in the case of polypropylene). After 5 minutes, 10 mm
The piston is pushed down at a speed of / minute, and the molten polymer is pushed out through the orifice at the bottom of the cylinder. The extruded strand is drawn into a filament shape, 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.

In the olefin copolymer according to the present invention, the proportion of the insoluble component which is not extracted with hot xylene is 10% by weight or less, preferably 7% by weight or less, more preferably 5% by weight or less, and particularly preferably 3%. It is preferably not more than weight%.

Here, the thermal xylene insoluble component rate is measured as follows. [Measurement Method of Thermal Xylene Insoluble Component Ratio] About 1 g of an olefin-based copolymer is weighed (X gram), put in a 100 mesh wire mesh container, and then weighed again (Y gram). This is immersed under nitrogen in 500 ml of xylene (containing 50 mg of phenolic antioxidant) at 120 ° C. for 4 hours, and then a wire mesh container is taken out and dried. After drying, weigh (Z grams).

From these values, the thermal xylene insoluble component ratio is determined by the following formula.

[0041]

[Equation 2]

The olefin copolymer according to the present invention as described above has a higher melt tension than conventional olefin polymers. Further, the olefin-based copolymer according to the present invention has excellent rigidity, transparency, mechanical strength such as impact strength, and appearance.

Therefore, by using the olefin copolymer according to the present invention, it is possible to obtain a film having excellent appearance such as no fish eyes, excellent transparency, and high strength.

Further, the olefin-based copolymer having such characteristics has excellent moldability at the time of molding and can be molded into a film or the like with a high yield and at a high speed. Further, it becomes possible to apply a molding method, such as a blow molding method or a vacuum molding method, which could not be applied due to lack of melt tension in the related art, thereby expanding the usable applications.

Next, a method for producing the olefin copolymer according to the present invention will be described. The olefin-based copolymer according to the present invention is (i) having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst comprising a [A] transition metal compound catalyst component and a [B] organometallic compound catalyst component. It is obtained by copolymerizing an α-olefin with (ii) an aliphatic and / or alicyclic polyene compound having 7 or more carbon atoms and having olefinic double bonds at both ends.

First, the [A] transition metal compound catalyst component forming the olefin polymerization catalyst used in the present invention will be described. In the present invention, the [A] transition metal compound catalyst component may be a compound containing a transition metal selected from Groups III to VIII of the Periodic Table, preferably Ti or Z.
Examples thereof include compounds containing at least one transition metal selected from r, Hf, Nb, Ta, Cr and V.

Known catalyst components can be used as the [A] transition metal compound catalyst component, and specific examples thereof include a solid titanium catalyst component containing titanium and halogen. .. More specifically, as an example of the solid titanium catalyst component, titanium, magnesium, halogen and preferably an electron donor (a)
The 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 Laid-Open No. 51-28
1189, JP-A-50-126590, JP-A-51
-92885, JP-B 57-45244, JP-B 5
7-26613, JP-B-61-5483, JP-A-5
6-811, Japanese Patent Publication No. 60-37804, Japanese Patent Publication No. 59
-50246, JP-A-58-83006, JP-A-4
8-16986, JP-A-49-65999, JP-A-49-86482, JP-B-56-39767, JP-B-56-322322, JP-A-55-29591, JP-A-53-146292. JP-A-57-63310
JP-A-57-63311 and JP-A-57-6331.
2, JP-A-62-273206, JP-A-63-69.
804, JP-A-61-211109, JP-A-63-2
64607, JP-A-60-23404, JP-A-60
-44507, JP-A-60-158204, JP-A-61-55104, JP-A-2-28201, JP-A-58-196210, JP-A-64-54005, and JP-A-59-149905. No. JP-A-61-145206
No. 63-302605, 63-225605.
JP-A-64-69610, JP-A-1-16870
7, JP-A-62-104810, JP-A-62-10
4811, JP-A-62-104812, JP-A-62.
-104813, etc.

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

As such a tetravalent titanium compound,
The compound represented by the following formula can be mentioned. In the Ti (OR) _g X _4-g formula, R is a hydrocarbon group, X is a halogen atom, and 0 ≦ g ≦ 4.

Specific examples of such a compound include T
Tetrahalogenated titanium such as iCl ₄ , TiBr ₄ , 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 ) Trihalogenated alkoxy titanium such as Br ₃ , Ti (O
_{CH 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 ) ₂ Br ₂ and other dihalogenated dialkoxy titanium, Ti (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ C
1, monohalogenated trialkoxy titanium such as Ti (On-C ₄ H ₉ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Br, Ti (OCH ₃ ) ₄ ,
Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₄ H ₉ ) ₄ , Ti (O-iso-C ₄
Examples thereof include tetraalkoxytitanium such as H ₉ ) ₄ and Ti (O-2-ethylhexyl) ₄ .

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

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 dimethylmagnesium, diethylmagnesium, dipropylmagnesium,
Dialkyl magnesium compounds such as dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, octyl butyl magnesium, and ethyl butyl magnesium; alkyl magnesium such as ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, and amyl magnesium chloride. Examples thereof include halides, alkyl magnesium alkoxides such as butyl ethoxy magnesium, ethyl butoxy magnesium, and octyl butoxy magnesium, and butyl magnesium hydride.

Further, 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 methoxymagnesium 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 thereof 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 the organic metal compounds described below, such as aluminum and zinc,
It may form a complex compound or a double compound with another metal such as boron, beryllium, sodium or potassium, or may be a mixture with another metal compound. Further, the magnesium compound may be used alone, two or more kinds of the above compounds may be used in combination, and may be used in a liquid state or a solid state. When the magnesium compound is a solid, 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 described 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 allyloxy 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 and C1-C18 halogen-containing alcohols such as trichloromethanol, trichloroethanol and trichlorohexanol, phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol , Phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as naphthol, acetone,
Methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone and other ketones having 3 to 15 carbon atoms, acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde, naphthaldehyde and the like having 2 to 15 carbon atoms
Aldehydes, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, crotonic acid Ethyl, cyclohexanecarboxylate, methyl benzoate, ethyl benzoate,
Propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate,
Amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-
C2-C18 organic acid esters such as butyrolactone, δ-valerolactone, coumarin, phthalide, and ethyl carbonate, C2-C15 such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride
C2-20 ethers such as acid halides, methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide , Toluic acid
Acid amides such as N, N-dimethylamide, trimethylamine, triethylamine, tributylamine, tribenzylamine, amines such as tetramethylethylenediamine, nitriles such as acetonitrile, benzonitrile and trinitrile, pyridine, methylpyridine, ethylpyridine, Examples thereof include pyridines such as dimethylpyridine, 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.

[0062]

[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 . ) Specific examples of such polyvalent carboxylic acid ester include aliphatic polycarboxylic acid ester, alicyclic polycarboxylic acid ester, aromatic polycarboxylic acid ester, and heterocyclic polycarboxylic acid ester. ..

Preferred specific examples are 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 polyvalent carboxylic acid ester include phthalic acid esters.

Further, examples of the polyether compound include compounds represented by the following general formula.

[0066]

[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. ) Preferred specific examples include 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-
Dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl)-
Examples thereof include 1,3-dimethoxypropane.

The above electron donors (a) can be used alone or in combination of two or more kinds. The solid titanium catalyst component [A-1] used in the present invention is, in addition to the compound as described above, an organic compound containing silicon, phosphorus, aluminum, etc. used as a carrier compound and a reaction aid during preparation. It may be prepared by contacting with an inorganic compound or the like.

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 bringing the above-mentioned titanium compound, magnesium compound and preferably the electron donor (a) into contact with each other.

The method for preparing the solid titanium catalyst component [A-1] using these compounds is not particularly limited, but the method will be briefly described below with several examples. (1) A method in which a solution containing a magnesium compound, an electron donor and a hydrocarbon solvent is contact-reacted with an organometallic compound to precipitate a solid, or while being precipitated, a solution is contacted with a titanium compound. (2) A method in which a complex consisting of a magnesium compound and an electron donor (a) is subjected to a catalytic reaction with an organometallic compound and then a titanium compound is subjected to a catalytic reaction. (3) For the contact product between the inorganic carrier and the organic magnesium compound,
A method of catalytically reacting a titanium compound and preferably an electron donor (a). At this time, the contact product may be previously contact-reacted with the halogen-containing compound 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 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 in a 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 of reacting a complex of an alkoxy group-containing magnesium compound and an electron donor (a) with a titanium compound. (10) A method in which a complex comprising an alkoxy group-containing magnesium compound and an electron donor (a) is contacted with an organometallic compound and then reacted 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. In this method, it is preferable to use the electron donor (a) at least once. (12) A method of reacting a liquid magnesium compound having no reducing ability with a liquid titanium compound, preferably in the presence of an electron donor (a) 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) Magnesium compound and preferably electron donor (a)
And a titanium compound are pulverized to obtain a solid product, which is treated 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, it is preferable to use an electron donor (a) or a reaction aid 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 contact reaction product of a metal oxide, an organomagnesium and a halogen-containing compound into contact with the electron donor (a) and a titanium compound. (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 preferably 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, it is preferable to coexist with a halogen-containing compound such as a halogen-containing silicon compound. (21) Solid magnesium obtained by reacting a liquid magnesium compound having no reducing ability with an organometallic compound.
A method of depositing a metal (aluminum) complex and then reacting the electron donor (a) with a titanium compound.

Such a 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 respect 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-based 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. Like this [A-
2] The details of the method for preparing the titanium trichloride-based catalyst component are described in, for example, the following publications.

JP-A-56-34711, JP-A-61-
287904, JP-A-63-75007, JP-A-6-
3-83106, JP-A-59-13630, JP-A-63-108008, JP-A-63-27508, JP-A-57-70110, JP-A-58-219207.
JP-A-1-144405, JP-A-1-29201
1, JP-A-1-292011 and the like.

Specific examples of the titanium trichloride catalyst component [A-2] include titanium trichloride. As the titanium trichloride, for example, titanium tetrachloride is reduced by bringing it into contact with hydrogen or a metal such as metal magnesium, metal aluminum, metal titanium or an organometallic compound such as an organomagnesium compound, an organoaluminum compound or an organozinc compound. The titanium trichloride obtained is preferably used. Further, such titanium trichloride is used as the electron donor described above.
It can be used together with (a) and / or a tetravalent titanium compound or after being brought into contact with them.

Further, in the present invention, the [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-61-221207 and JP-A-62-121207
-121707, JP-A-63-66206, JP-A-2-22307, JP-A-2-173110, JP-A-2-302410, JP-A-1-129003, JP-A-1-210404, JP-A-3. -66710, JP-A-3-70710, JP-A-1-207248, JP-A-63-222177, JP-A-63-222178.
No. 63-222179, JP-A 1-1240
7, JP-A-1-301704, JP-A-1-3194
89, JP-A-3-74412, JP-A-61-264.
010, JP-A-1-275609 and JP-A-63-2.
51405, JP-A-64-74202, JP-A-2-
No. 41303, JP-A-2-131488, JP-A-3-
56508, JP-A-3-70708, JP-A-3-7
0709 etc.

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, and a tetramethylcyclopentadienyl group. , A pentamethylcyclopentadienyl group,
Ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclopentadienyl group, hexylcyclopentadienyl group Groups such as alkyl-substituted cyclopentadienyl group or indenyl group, 4,5,
Examples thereof include a 6,7-tetrahydroindenyl group and a fluorenyl group. These groups are halogen atoms,
It may be substituted with 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 bonded via a silylene group or the like to form a bridge structure.

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 such a ligand having 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, R ² ,
A metallocene compound in which at least two of 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 are ethylene, alkylene groups such as propylene, isopropylidene, substituted alkylene groups such as diphenylmethylene, silylene groups or dimethylsilylene, diphenylsilylene,
It may be bonded via a substituted silylene group such as a methylphenylsilylene group. 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.

In the present invention, a zirconocene compound having at least two cyclopentadienyl skeleton ligands and forming a bridge structure is preferably used.

Specific examples of the transition metal compound in which M is zirconium are shown below. Ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) zirconium bis (Methanesulfonato), ethylenebis (indenyl) zirconium bis (p-toluenesulfonato), ethylenebis (indenyl) zirconium bis (trifluoromethanesulfonato), ethylenebis (4,5,6,7-tetrahydroindenyl) Zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) Zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadiene) Nil) zirconium dichloride, dimethylsilylene bis (cyclopentadienyl) zirconium dichloride, dimethylsilylene bis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (trimethylcyclopenta) Dienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium bis (trifluoromethanesulfonate), dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethyl Silylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylene bis (indenyl) zirconi Mudichloride, methylphenylsilylenebis (indenyl) zirconium dichloride, in the above example, the disubstituted cyclopentadienyl ring includes 1,2- and 1,3-substituted ones, and the trisubstituted one is 1,2,3 -And 1,2,4-substitutions are included. Alkyl groups such as propyl and butyl are n-, i-, sec-,
Includes isomers such as tert-.

It is also possible to use a compound in which zirconium is replaced with titanium, hafnium, vanadium, niobium, tantalum or chromium in the zirconium compound as described above.

In the present invention, a metallocene compound having a central metal atom of zirconium is preferably used as the metallocene compound [A-3]. These compounds may be used alone or in combination of two or more. It may be diluted with a hydrocarbon or a halogenated hydrocarbon before use.

The [A-3] metallocene compound as described above can also be used by supporting it on a carrier in 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 may be used in combination of two or more kinds. Of these, SiO ₂ , Al
₂ O ₃ and MgO are preferably used. Next, the organometallic compound catalyst component containing a metal selected from Group I to Group III of the periodic table used in the present invention 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 can be used.

Examples of such [B-1] organoaluminum compound include the organoaluminum compounds represented by the following formulas. 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 aluminums 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 dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum 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 and the} like, (iv) R ^a _n Al (NR ^e ₂ ) _3-n Me ₂ AlNEt ₂ Et ₂ AlNHMe Me ₂ AlNHEt Et ₂ AlN (Me ₃ Si) ₂ (iso-Bu) ₂ AlN etc. _{(Me 3 Si) 2, (} v) R a n Al etc. _{^{(SiR f 3) 3-n}} (iso-Bu) 2 AlSiMe 3, (vi) R a n Al [n (R ^g) -AlR ^h etc. _{2] 3-n Et 2 AlN (Me} ) -AlEt 2 (iso-Bu) 2 AlN (Et) Al (iso-Bu) 2.

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).

[0106]

[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 or an ethyl group, 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 are The same hydrocarbon group as R can be exemplified, and R ¹ and R ² represent different groups]. In that case, aluminum formed from mixed alkyloxyaluminum units containing methyloxyaluminum units (OAl (CH ₃ )) in a proportion of 30 mol% or more, preferably 50 mol% or more, particularly preferably 70 mol% or more. Nooxane is preferred.

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 a method for producing such an 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, cerium chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to the hydrocarbon medium suspension described in 1 above and reacted. (2) A method in which water is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran. (3) 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 and dibutyltin oxide.

Among these methods, the method (1) is preferably adopted. The aluminoxane may contain a small amount of an organometallic component other than aluminum. Further, the solvent or the unreacted organoaluminum compound may be distilled and removed 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 triisopropylaluminum.
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, benzene, toluene, xylene, cumene, aromatic hydrocarbons such as cymene, pentane, hexane, heptane, aliphatic such as octane, decane, dodecane, hexadecane, octadecane, etc. 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 the [A-1] solid titanium catalyst component or the [A-2] titanium trichloride catalyst component, the [B] organometallic compound catalyst component is , [B-1] organoaluminum compound is preferred, 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 preferably an organoaluminum oxy compound.

In the present invention, together with such a [A] transition metal compound catalyst component and [B] organometallic compound catalyst component, if necessary, the above-mentioned electron donor (a) or 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-norbornanemethyl 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 alone or in combination of two 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' , N'-Tetraethylmethylenediamine and other substituted methylenediamines, 1,3-dibenzylimidazolidine, 1,3-dibenzyl-2-phenylimidazoline and other substituted methylenediamines and other nitrogen-containing electron donors, triethylphos Fight, tri-n-propylphosphite, triisopropylphosphite, tri-n-butylphosphite, triisobutylphosphite, diethyl
Phosphorus-containing electron donors such as phosphites such as n-butylphosphite and diethylphenylphosphite, 2,
Mention may also be made of oxygen-containing electron donors such as 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, as described above, in the presence of the catalyst for olefin polymerization formed from the [A] transition metal compound catalyst component and the [B] organometallic compound catalyst component, (i) a C 3-20 α
-Production of an olefin-based copolymer by copolymerizing an olefin and (ii) an aliphatic and / or alicyclic polyene compound having 7 or more carbon atoms and having an olefinic double bond at both ends To do.

At this time, the olefin may be prepolymerized on the olefin polymerization catalyst prior to the main polymerization. Specific examples of the olefin used for the prepolymerization include ethylene and the above-mentioned (i) α-olefin having 3 to 20 carbon atoms, and the above-mentioned (iii) other olefins.

Such an olefin may be the same as or different from the olefin used in the main polymerization described later. In the prepolymerization, these above olefins can be homopolymerized or copolymerized.

In the present invention, propylene is preferably used among the above-mentioned olefins in the prepolymerization. In the prepolymerization, the electron donors (a) and (b) described above can be used together with the above catalyst components [A] and [B].

In the present invention, the prepolymerization can be carried out in the coexistence of an inert solvent described below, and the olefin and the catalyst component used in the prepolymerization are added to the inert solvent and the prepolymerization is carried out under relatively mild conditions. Is preferred. At this time, it may be carried out under the condition that the formed prepolymer is dissolved in the polymerization medium or may be dissolved therein, but preferably it is not dissolved.

Specific examples of such an inert solvent include propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and aliphatic hydrocarbons such as kerosene, cyclopentane, cyclohexane, methylcyclopentane, etc. Alicyclic hydrocarbons, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures thereof.

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

In the prepolymerization, a catalyst having a higher concentration than the catalyst concentration in the system in the main polymerization can be used. The concentration of the catalyst in the prepolymerization varies depending on the catalyst component used, but the concentration of the [A] transition metal compound catalyst component is usually about 0.01 to 5000 mmol, calculated as the transition metal atom, per liter of the polymerization volume. Preferably about 0.1-
The amount is 1000 mmol, particularly preferably 1 to 500 mmol.

[B] The organometallic compound catalyst component is [A]
0.01 to 1000 per 1 g of the transition metal compound catalyst component
g, preferably 0.03 to 1000 g, more preferably 0.05 to 200 g, is used in an amount such that a polymer is produced, and is usually about 1 mol per transition metal atom in the [A] transition metal compound catalyst component. It is used in an amount of 0.1 to 1000 mol, preferably about 0.5 to 500 mol, particularly preferably 1 to 100 mol.

In the case where the electron donors (a) and (b) are used, the electron donors (a) and (b) are usually added per mol of the transition metal atom in the catalyst component of the [A] transition metal compound. , 0.01
˜50 mol, more preferably 0.05 to 30 mol, particularly preferably 0.1 to 100 mol.

The reaction temperature in the prepolymerization is usually about -20.
It is desirable to be in the range of to + 100 ° C, preferably about -20 to + 80 ° C, more preferably -10 to + 40 ° C. A molecular weight modifier such as hydrogen may be used in the prepolymerization.

In the prepolymerization, usually 0.01 to 2000 g, and preferably 0.1 to 1 g of the transition metal compound catalyst component [A].
03-1000 g, particularly preferably 0.05-200 g
A prepolymerization catalyst is obtained by polymerizing the above olefin in an amount of.

The prepolymerized catalyst obtained as described above is usually obtained in a suspended state. Such a prepolymerized catalyst can be used as it is in a suspended state in the polymerization in the next step, or the prepolymerized catalyst produced from the suspension can be separated and used.

In the present invention, when the prepolymerization catalyst as described above is used in the main polymerization, it is preferred to further use the organometallic compound catalyst component [B] together with the prepolymerization catalyst. Further, when forming the olefin polymerization catalyst, the above-mentioned electron donor can be used as necessary.

In producing the olefinic copolymer according to the present invention, the above-mentioned (i) α-olefin having 3 to 20 carbon atoms and (ii) an aliphatic olefinic double bond at both ends and / Alternatively, it is copolymerized with an alicyclic polyene compound.

Furthermore, in the present invention, when (i) an α-olefin having 3 to 20 carbon atoms and (ii) a polyene compound are copolymerized, a copolymerizable monomer other than those mentioned above, that is, (iii) other The olefins of (4) and (iv) other polyenes can be copolymerized if necessary.

The amounts of (i) the α-olefin and (ii) the specific polyene compound used in the polymerization vary depending on the type of the polyene compound and the catalyst, the polymerization conditions, etc., and therefore cannot be generally stated. In the case of copolymerizing 9,9-decadiene, 1,9-decadiene is 0.0001 to 50 mol, preferably 0.001 to 1 mol of propylene.
It is desirable to use it in an amount of 0005 to 10 mol, more preferably 0.001 to 5 mol.

In the present invention, the above (i) α-olefin and
(ii) The copolymerization 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 reaction form of suspension polymerization, a liquid polyene compound or olefin at the reaction temperature and / or an inert solvent as described above can be used as a reaction solvent.

The catalyst used in the main polymerization varies depending on the kind, but is usually used in the following amount. The [A] transition metal compound catalyst component (including the prepolymerization catalyst) is usually converted to about 0.001 in terms of the transition metal atom in the [A] transition metal compound catalyst component or the prepolymerization catalyst per liter of the polymerization volume. ~ 100 mmol, preferably about 0.005
Used in an amount of ~ 20 mmol.

In the organometallic compound catalyst component [B], the metal atom in the catalyst component [B] is the transition metal atom 1 in the transition metal compound catalyst component [A] in the polymerization system or in the prepolymerization catalyst.
Usually about 1 to 2000 mol, preferably about 5 mol per mol.
It is used in an amount such that it is up to 500 mol.

Further, the electron donors (a) and (b) described above can be preferably used together with the above catalyst components [A] and [B]. When an electron donor is used, the amount of the electron donor is usually about 0.001 mol to 10 mol per 1 mol of the metal atom in the organometallic compound catalyst component [B].
It is used in a molar amount, preferably from 0.01 to 5 mol.

The olefin polymerization catalyst may contain other components useful for the polymerization of olefins, in addition to the above components. When hydrogen is used during the polymerization, the molecular weight of the obtained polymer can be adjusted, and a polymer having a high melt flow rate can be obtained.

The polymerization is usually carried out under the following conditions, although it depends on the polyene compound and olefin used. The polymerization temperature is about -40 to 300 ° C, preferably about -20 to 150 ° C, and the polymerization pressure is normal pressure to 10 ° C.
It is 0 kg / cm ² , preferably about ² to 50 kg / cm ² .

Such polymerization can be carried out in a batch system, a semi-continuous system,
It can be carried out by any of the continuous methods. Further, the polymerization can be carried out in two or more stages. At this time, the reaction conditions in each stage may be the same or different.

The olefinic copolymer according to the present invention as described above can be used as a blend with a conventionally known olefinic polymer. As such an olefin polymer, a conventionally known α-olefin fin polymer or copolymer having 2 to 20 carbon atoms can be widely used. Specifically, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, polybutene, poly (4-methyl-1-pentene), polypentene, ethylene / propylene copolymer, ethylene / butene copolymer , Propylene / butene copolymer, ethylene / propylene / butene copolymer, 4-methyl-1-pentene / olefin copolymer, ethylene / cyclic olefin copolymer, ethylene / propylene / polyene compound copolymer,
Examples thereof include various propylene block copolymers, propylene random copolymers, and mixtures thereof.

When the olefin copolymer according to the present invention is blended with a conventionally known olefin polymer, the olefin copolymer according to the present invention is usually 0.001-9.
Known olefin polymers are usually 99.999 to 5% by weight, preferably 99.995 to 20%, in an amount of 5% by weight, preferably 0.005 to 80% by weight, more preferably 0.01 to 50% by weight. % By weight, more preferably 99.9
Used in an amount of 9-50% by weight.

The olefin copolymer according to the present invention includes
Various stabilizers can be incorporated. It is preferable that the olefin copolymer according to the present invention is blended with a phenolic stabilizer, since a molded product having excellent heat resistance stability and transparency can be obtained. Particularly, a phenolic stabilizer and an organic phosphite stabilizer are preferable. Is particularly preferable because a film excellent in heat stability and transparency can be obtained.

When the olefinic copolymer according to the present invention contains a higher fatty acid metal salt, the thermal stability of the resin at the time of molding is improved, and the halogen gas generated by the catalyst causes the molding machine to start. Trouble caused by rust and corrosion can be suppressed. Particularly, it is preferable to use a phenol-based stabilizer and / or an organic phosphite-based stabilizer in combination with a higher fatty acid metal salt.

Specific examples of the phenolic stabilizer include 2,6-di-t-butyl-4-methylphenol and 2,6-diphenol.
-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, styrenated mixed cresol, dl-α-tocophenol, t-butylhydroquinone, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6
-t-butylphenol), 4,4'-thiobis (3-methyl-6)
-t-butylphenol), 4,4'-thiobis (4-methyl-6)
-t-butylphenol), 4,4'-methylenebis (2,6-diphenol
-t-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2,2'-ethylidenebis (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, triethyleneglycol-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-4-4) Hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-4hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzimephosphonate- Diethyl ester, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-t-4butylbenzyl) 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-bi (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, β- (3,5-di
-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester and the like.

As the above-mentioned phenolic stabilizer, β- (3,5-di
When -t-butyl-4-hydroxyphenyl) propionic acid alkyl ester is used, an alkyl ester having 18 or less carbon atoms is preferably used.

In the molecule,

[0152]

[Chemical 4]

Phenolic stabilizers having the structure of are preferred. However, in the above formula, R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ¹ and R
² are each independently an alkyl group having 1 to 6 carbon atoms, and R ³ is an alkyl group having 1 to 6 carbon atoms or 1 to 6 carbon atoms.
6 is an alkoxy group. R ₄ is an alkyl group having 1 to 22 carbon atoms or a group having the following structure.

[0154]

[Chemical 5]

Among these, 2,6-di-tert-butyl-4-
Methyl-p-cresol, 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.

These phenolic stabilizers may be used alone or in combination. Examples of the phosphite stabilizer include trioctyl phosphite, trilauryl phosphite, tristridecyl phosphite, tris isodecyl phosphite, phenyldiisooctyl phosphite, phenyldiisodecyl phosphite, phenyldi (tridecyl) phosphite, diphenyl. Isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (butoxyethyl) ) Phosphite, tetratridecyl-
4,4'-butylidene bis (3-methyl-6-t-butylphenol) -diphosphite, 4,4'-isopropylidene-diphenolalkylphosphite (however, alkyl has about 12 to 15 carbon atoms), 4,4 ' -Isopropylidene bis (2-t
-Butylphenol) -di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-t-butyl-4-hydroxyphenyl) butanediphos Fight, tetra (tridecyl) -4,4'-butylidenebis (3-methyl-6-t-butylphenol) diphosphite, tris (3,5-di-t-butyl-4-hydroxyphenyl) phosphite, hydrogenated-
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,
Examples thereof include 9,10-dihydro-9-phosphaphenanthrene-10-oxide, tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenylenediphosphonite and the like.

Among these, tris (2,4-di-tert-
Butylphenyl) phosphite, tris (nonylphenyl) phosphite and tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphite are preferred, and tris (2,4-di-tert -Butylphenyl) phosphite is particularly preferred.

Further, a phosphite stabilizer derived from pentaerythritol represented by the following formula can also be used.

[0159]

[Chemical 6]

In the above formulas (1) and (2), R ¹
And R ² represents an alkyl group. Such organic phosphite stabilizers are used alone or in combination.

The higher fatty acid metal salt has 12 to 12 carbon atoms.
40 saturated or unsaturated carboxylic acid alkali metal salts,
Examples thereof include alkaline earth metal salts and other metal salts. The saturated or unsaturated carboxylic acid having 12 to 40 carbon atoms is
It may have a substituent such as a hydroxyl group.

Specific examples of the saturated or unsaturated carboxylic acid having 12 to 40 carbon atoms include stearic acid, oleic acid, lauric acid, capric acid, arachidonic acid, palmitic acid, behenic acid and 12-hydroxystearic acid.
Examples of higher fatty acids such as montanic acid, and as the metal that reacts with these higher fatty acids to form salts, alkaline earth metal salts such as magnesium, calcium and barium, alkali metals such as sodium, potassium and lithium, And cadmium, zinc, lead and the like.

Specific examples of the higher fatty acid salt include magnesium stearate, magnesium laurate, magnesium palmitate, calcium stearate, calcium oleate, calcium laurate, barium stearate, barium oleate, barium laurate,
Barium arachidonate, barium behenate, zinc stearate, zinc oleate, zinc laurate, lithium stearate, sodium stearate, sodium palmitate, sodium laurate, potassium stearate, potassium laurate and calcium 12-hydroxystearate, Examples thereof include sodium montanate, calcium montanate, zinc montanate and the like.

Of these higher fatty acid metal salts, zinc salts of saturated fatty acids having 12 to 35 carbon atoms are particularly preferably used. Such higher fatty acid metal salts may be used alone or in combination.

When the above stabilizer is blended, the amount of the phenolic stabilizer based on the olefin copolymer is usually 0.01 to 10% by weight, preferably 0.02.
Is used in an amount of .about.0.5% by weight, particularly preferably 0.03 to 0.2% by weight.

The organic phosphite stabilizer is also generally 0.01 to 1.0% by weight, preferably 0.02 to 0.
It is used in an amount of 5% by weight, particularly preferably 0.03 to 0.2% by weight.

The higher fatty acid metal salt is similarly 0.01 to
It is used in an amount of 1.0% by weight, preferably 0.02 to 0.5% by weight, particularly preferably 0.03 to 0.2% by weight.

[0168]

The olefin copolymer according to the present invention is
It has a high melt tension as compared with conventionally known olefin polymers. Therefore, this olefin-based copolymer can be formed into a film at a high yield at a high speed. Further, the present invention can be applied to a molding method which could not be applied due to the lack of melt tension in the related art, and the usage of the olefin polymer will be expanded.

The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

[0170]

Example 1 “Preparation of solid titanium catalyst component [A]” 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol were heated at 130 ° C. for 2 hours to form a uniform solution. Phthalic anhydride in solution 21.
3 g was added, and the mixture was stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride. After cooling the homogeneous solution thus obtained to room temperature, 75 ml of this homogeneous solution was added to 200 ml of titanium tetrachloride kept at -20 ° C.
Dropwise charged over time. After the completion of charging, the temperature of this mixed solution was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., diisobutyl phthalate (DIBP) 5.2 was added.
2 g was added, and the mixture was kept stirring 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 275 ml 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 thoroughly washed with decane and hexane at 110 ° C. until no free titanium compound was detected in the solution. The solid titanium catalyst component [A] prepared by the above operation was stored as a decane slurry, and a part of this was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component [A] thus obtained is as follows: titanium 2.4% by weight, chlorine 60% by weight, magnesium 20% by weight, DIBP 13.0% by weight.
Met. "Preliminary Polymerization of Solid Titanium Catalyst Component [A]" In a 400 ml four-necked glass reactor equipped with a stirrer, 200 ml of purified hexane under nitrogen atmosphere, 6 mmol of triethylaluminum and the above solid titanium catalyst component [A] were converted into titanium atoms. Propylene was fed to the reactor for 1 hour at a temperature of 20 ° C. and a rate of 6.4 liters / hour.

When the supply of propylene was completed, the inside of the reactor was replaced with nitrogen, and the washing operation consisting of removal of the supernatant and addition of purified hexane was carried out twice, and then resuspended in purified hexane to prepare a catalyst bottle. The whole amount was transferred to obtain a prepolymerized catalyst [B]. "Copolymerization" Purified into an autoclave with an internal volume of 2 liters n-
Insert 750 ml of hexane and 10 ml of 1,9-decadiene, and
Triethylaluminum (0.75 mmol), cyclohexylmethyldimethoxysilane (CMMS) (0.75 mmol) and prepolymerization catalyst [B] (0.015 mmol) in terms of titanium atom were charged at 0 ° C. in a propylene atmosphere.

200 ml of hydrogen was introduced and the temperature was raised to 70.degree.
After the propylene was fed over 2 hours, propylene and 1,
Copolymerization of 9-decadiene was performed. Pressure during polymerization is 7 kg
/cm ²I kept it at G. Slurry containing solids produced after polymerization
Was filtered and separated into a white powder and a liquid phase part. White after drying
Yield of colored powdery polymer is 227.0 g, insoluble in hot xylene
The solution component ratio is 0%, and the extraction residual ratio by boiling heptane is 98.
32%, MFR 2.05 dg / min, apparent bulk specific gravity
0.40 g / ml, [η] is 2.62 dl / g, melt ten
The amount was 2.95 g. On the other hand, by concentrating the liquid phase,
Thus, 0.9 g of a solvent-soluble polymer was obtained. Therefore,
The property is 15,200 g-pp / mM-Ti, and the total I
I (t-I.I.) Was 97.9%.

The results are shown in Table 1.

[0175]

[Example 2] "Copolymerization" Copolymerization was carried out in the same manner as in Example 1 except that 20 ml of 1,9-decadiene was used. The thermal xylene insoluble component ratio was 0%.

The results are shown in Table 1.

[0177]

Comparative Example 1 "Copolymerization" Propylene was polymerized in the same manner as in Example 1 except that 1,9-decadiene was not used.

The results are shown in Table 1.

[0179]

[Table 1]

[0180]

[Example 3] "Copolymerization of propylene / 1,9-decadiene" In a 400 ml four-necked glass reactor equipped with a stirrer, under a nitrogen atmosphere, 334 ml of purified hexane, 2 ml of 1,9-decadiene, 10 mmol of triethylaluminum, After adding 2 mmol of cyclohexylmethyldimethoxysilane (CMMS) and 1.0 mmol of the above solid titanium catalyst component [A] in terms of titanium atom, propylene was supplied to this reactor at a temperature of 20 ° C. When 16 liters of propylene had reacted, the supply of propylene was stopped.

When the supply of propylene was completed, the inside of the reactor was replaced with nitrogen, a large amount of isobutyl alcohol containing a small amount of hydrochloric acid was added to stop the reaction, and stirring was continued at 60 ° C. for 30 minutes to remove the catalyst residue. .. After the stirring is completed, the polymer containing the resulting solid is separated by filtering the slurry,
It was dried under reduced pressure at 0 ° C. to obtain 30.5 g of a propylene / 1,9-decadiene copolymer.

The obtained polymer contained 0.8 mol% of 1,9-decadiene constitutional unit. "Production of polypropylene composition" 1.6 parts by weight of the above propylene / 1,9-decadiene copolymer, 1 part by weight of calcium stearate, 1 part by weight of 3,5-di-t-butyl-4-hydroxytoluene, 1 part by weight of tetrakis [methylene (3,5-di-t-butyl-4-hydroxy) hydrocinnamate] methane, a homopolymer of propylene (MT = 1.4 g, MFR = 1.5 dg / min, [η] =
2.80 dl / g, boiling heptane extraction residual rate 98.0%) 1
000 parts by weight were mixed and granulated into pellets with a 20 mmφ extruder.

The polypropylene composition obtained had a melt tension (MT) of 1.6 g and an MFR of 1.5 dg.
/ Min, [η] was 2.80 dl / g.

[Brief description of drawings]

FIG. 1 is a diagram showing a process for preparing an olefin-based copolymer according to the present invention.

Claims (2)

[Claims] 1. An aliphatic and / or alicyclic polyene having (i) an α-olefin having 3 to 20 carbon atoms and (ii) having 7 or more carbon atoms and having olefinic double bonds at both ends. A copolymer with a compound, wherein (i) the carbon number is 3 to 2
50 to 9 constitutional units derived from 0 α-olefin
An olefin-based copolymer, characterized in that it is contained in an amount of 9.99 mol%. 2. In the presence of an olefin polymerization catalyst comprising a transition metal compound catalyst component [A] and an organometallic compound catalyst component [B], (i) an α-olefin having 3 to 20 carbon atoms; ii) Copolymerizing with an aliphatic and / or alicyclic polyene compound having 7 or more carbon atoms and having olefinic double bonds at both ends,
(i) A method for producing an olefin-based copolymer containing a structural unit derived from an α-olefin having 3 to 20 carbon atoms in an amount of 50 to 99.99 mol%.