JP3280426B2 - Olefin polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an olefin polymer composition, and more particularly to an olefin polymer composition containing a polymer containing an ethylene / polyene copolymer and having a high melt tension.

[0002]

BACKGROUND OF THE INVENTION Conventionally, high density polyethylene,
Olefin polymers typified by linear low-density polyethylene and polypropylene are excellent in transparency,
It has excellent mechanical strength such as rigidity and impact strength, and is formed into a film by an injection molding method, an extrusion molding method, or the like.

[0003] In general, such olefin polymers have low melt tension (melt tension, MT), and are therefore formed into, for example, large containers (bottles, etc.) by blow molding, and into linings of home appliances by vacuum forming. It was difficult to do. Due to such restrictions on molding, the obtained molded body is also limited, and at present, its use is limited despite having various excellent properties.

[0004] Further, when polypropylene or the like is formed into a film by an inflation molding method, draw-down occurs and molding conditions are limited due to low melt tension. For this reason, in the blow-molding of the conventional film, the bubble was stabilized by blending polypropylene with a high-pressure low-density polyethylene or the like and increasing the melt tension. However, such a method may cause a decrease in film strength and transparency.

Therefore, if olefin polymers such as polypropylene and linear low-density polyethylene having a high melt tension appear, large containers (bottles and the like) can be blow-molded using the olefin polymers, and home electric appliances. For example, it becomes possible to form a refrigerator lining or the like by a vacuum forming method, and the use of the olefin polymer is further expanded.

When an olefin polymer having a higher melt tension is formed into a film by an inflation molding method, bubbles can be stabilized and the molding speed can be increased.

[0007] The appearance of olefin polymers such as polypropylene, high-density polyethylene or linear low-density polyethylene having a high melt tension is desired.

The present inventors have conducted research with the aim of obtaining an olefin polymer having a high melt tension in order to meet the above requirements. As a result, an ethylene / polyene copolymer-containing polymer obtained by copolymerizing ethylene and a polyene compound with an olefin polymerization catalyst comprising a transition metal compound catalyst component and an organometallic compound catalyst component, and then polymerizing the olefin. Have a high melt tension. Further research based on this finding has revealed that, as described above, an ethylene / polyene copolymer-containing polymer obtained by copolymerizing ethylene and a polyene compound in the presence of an olefin polymerization catalyst, and then polymerizing the olefin. And a known olefin polymer, the olefin polymer composition has a high melt tension, has excellent moldability during inflation molding, and can be molded by a blow molding method, a vacuum molding method, or the like. The inventors have found that the present invention has been completed.

[0009]

The object of the present invention is to provide a blow molding method which is excellent in formability when inflation molding a film or the like.
It is an object of the present invention to provide an olefin polymer composition having a high melt tension that can be formed by a vacuum forming method or the like.

[0010]

SUMMARY OF THE INVENTION The olefin polymer composition according to the present invention comprises [I] [A] a transition metal compound catalyst component and [B] a period.
The organic metal containing at Table Group I - Group III or al metal selected
The compound catalyst component, ethylene, polyene of compound is copolycondensation
And ethylene containing a structural unit derived from ethylene in an amount of 99.999 to 50 mol% and a structural unit derived from a polyene compound in an amount of 0.001 to 50 mol%. An ethylene-polyene copolymer-containing polymer obtained by polymerizing or copolymerizing an olefin with a prepolymerization catalyst containing the polyene copolymer (i) to form an olefin polymer (ii): 0.005 II99% by weight and [II] olefin polymer: 1-99.995% by weight are blended.

Such an ethylene / polyene copolymer-containing polymer [I] contains, for example, [A] a transition metal compound catalyst component and [B] a metal selected from Groups I to III of the periodic table. In the organometallic compound catalyst component, ethylene and a polyene compound are the [A] transition metal compound catalyst component 1.
copolymerized in an amount of 0.01 to 2000 g per g,
The olefin polymer (ii) can be produced by polymerizing or copolymerizing an olefin with a prepolymerized catalyst containing the ethylene / polyene copolymer (i).

The olefin polymer composition comprising the ethylene / polyene copolymer-containing polymer [I] and the olefin polymer [II] has a high melt tension, and has high moldability during inflation molding. And can be formed into a large container or the like by a blow molding method or the like.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The olefin polymer composition according to the present invention will be specifically described below. In the present invention, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only a homopolymer but also a copolymer. Is sometimes used in a sense that also includes

The olefin polymer composition according to the present invention comprises:
[I] an ethylene / polyene copolymer-containing polymer,
I] an olefin polymer.

FIG. 1 is a graph showing the relationship between ethylene and ethylene used in the present invention.
The explanatory view of the preparation process of the polyene copolymer containing polymer [I] is shown. First, the ethylene-polyene copolymer-containing polymer [I] used in the present invention will be described.

The polymer [I] containing the ethylene / polyene copolymer used in the present invention is [A] a transition metal compound catalyst.
Component and [B] selected from Groups I to III of the Periodic Table
Metal and organometallic compound catalyst components containing
A structural unit derived from ethylene in an amount of 99.999 to 50 mol%, wherein the structural unit derived from ethylene is copolymerized with a liene compound;
An olefin polymer (ii) is formed by polymerizing or copolymerizing an olefin with a prepolymerized catalyst containing an ethylene / polyene copolymer (i) contained in an amount of 1 to 50 mol%. .

[0017] Such an ethylene / polyene copolymer-containing polymer [I] is obtained, for example, by copolymerizing ethylene and a polyene compound with [A] a transition metal compound catalyst component and [B] an organometallic compound catalyst component. An olefin polymer (ii) is formed by polymerizing or copolymerizing an olefin with a prepolymerized catalyst containing the resulting ethylene / polyene copolymer (i).

An ethylene / polyene copolymer as described above
Specific examples of the polyene compound used in forming (i) 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-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,13-tetradeca Diene, 1,5,9-decatriene, butadiene, aliphatic polyene compounds such as isoprene, vinylcyclohexene, vinylnorbornene, ethylidene norbornene,
Dicyclopentadiene, cyclooctadiene, 2,5-norbornadiene, 1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,3-divinylcyclopentane,
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-
Alicyclic polyene compounds such as 3-vinylcyclopentane,
Aromatic polyene compounds such as divinylbenzene and vinylisopropenylbenzene;

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

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

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

Such an ethylene / polyene copolymer
In (i), the structural unit derived from ethylene is usually 9
9.999-50 mol%, preferably 99.999-70
The amount of the structural unit derived from the polyene compound is 0.1 mol%, more preferably 99.995 to 75 mol%, still more preferably 99.99 to 80 mol%, and particularly preferably 99.95 to 85 mol%. 001 to 50 mol%, preferably 0.001 to 30 mol%, more preferably 0.005 mol%.
To 25 mol%, more preferably 0.01 to 20 mol%, particularly preferably 0.05 to 15 mol%.

The ethylene / polyene copolymer (i) is
As long as the object of the present invention is not impaired, it may contain a unit derived from an olefin having 3 or more carbon atoms described later. In this case, the constituent unit derived from the olefin is usually contained in an amount of less than 30 mol%, preferably 20 mol% or less, particularly preferably 15 mol% or less.

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

[0025]

(Equation 1)

(Where, [P ₀ ]: the number of moles of the polyene compound supplied at the time of polymerization [P _r ]: the number of moles of the unreacted polyene compound [E ₀ ]: the number of moles of ethylene supplied at the time of polymerization [E _[r ]: mole number of unreacted ethylene) [ _Er ] and [ _Pr ] are determined by measuring unreacted ethylene and polyene compounds remaining in the polymerization vessel using gas chromatography or the like. .

The olefin used for forming the olefin polymer (ii) forming the ethylene-polyene copolymer-containing polymer [I] may have 2 to 20 carbon atoms.
Α-olefin.

Specific examples of such α-olefins include ethylene, propylene, 1-butene, 1-pentene,
1-hexene, 3-methyl-1-butene, 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.

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

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

In the ethylene-polyene copolymer-containing polymer [I], the ethylene-polyene copolymer (i)
Is 0.001 to 99% by weight, preferably 0.005 to 90% by weight.
Olefin polymer (ii) in an amount of from 99.999 to 1% by weight, preferably from 99.999 to 10% by weight, more preferably from 99.99 to 9% by weight, more preferably from 0.01 to 88% by weight. It is present in an amount of 12% by weight.

Of the ethylene-polyene copolymer-containing polymer [I], the ethylene-polyene copolymer (i) is 0.001 to 15% by weight, preferably 0.008%.
Olefin polymer (ii) in an amount of 99.9% by weight
Particularly preferred is one containing 99 to 15% by weight, preferably 99.992 to 90% by weight.

The ethylene-polyene copolymer-containing polymer [I] used in the present invention has a melt flow rate (MFR) of 5 in accordance with ASTM D1238E.
000 or less, preferably 0.01 to 3000 g / 10 min,
It is more preferably from 0.02 to 2000 g / 10 min, particularly preferably from 0.05 to 1000 g / 10 min.

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

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

For example, when the olefin polymer (ii) forming the ethylene / polyene copolymer-containing polymer [I] is polypropylene, log [MT] ≧ −0.8 log [MFR] +0.3 is preferable. Log [MT] ≧ −0.8 log [MFR] +0.5 More preferably, log [MT] ≧ −0.8 log [MFR] +0.7, particularly preferably log [MT] ≧ −0.8 log [ MFR] +0.8.

More specifically, for example, when the olefin polymer (ii) is polyethylene, the density of the ethylene-polyene copolymer-containing polymer [I] is about 0.92 g /
cm ³ and an MFR of 1 g / 10 min, the melt tension of the ethylene-polyene copolymer-containing polymer [I] is usually at least 2.5 g, preferably at least 3.5 g,
More preferably 4.0 g or more, still more preferably 4.5 g.
Above, particularly preferably 5.0 g or more.

Melt tension (MT) of the ethylene / polyene copolymer-containing polymer [I] used in the present invention
Satisfies the above-described relational expression with the melt flow rate (MFR), and also satisfies the following expression with the intrinsic viscosity ([η]).

For example, when the olefin polymer (ii) forming the ethylene-polyene copolymer-containing polymer [I] is polypropylene, the ethylene-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, the relationship represented by log [MT] ≧ 3.7 log [[η]]-1.0 is satisfied.

Further, for example, the ethylene / polyene copolymer-containing polymer [I] comprises the above-mentioned ethylene / polyene copolymer (i) and polyethylene (ii), and the olefin polymer has a density of 0.1%. When 92 g / cm ³ and intrinsic viscosity [η] are 1.8 dl / g, the melt tension of the olefin polymer is 2.5 g or more, preferably 3.5 g or more, more preferably 4.0 g or more. It is preferably at least 4.5 g, particularly preferably at least 5.0 g.

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

Next, the [A] transition metal compound catalyst component used for producing the above-mentioned ethylene-polyene copolymer-containing polymer [I] will be described. In the present invention, the [A] transition metal compound catalyst component includes a compound containing a transition metal selected from Groups III to VIII of the periodic table, and is preferably Ti, Zr, Hf, Nb, Ta,
Examples include compounds containing at least one transition metal selected from Cr and V.

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

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

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

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

[0047] During _{Ti (OR) g X 4-} g formulas, R is a hydrocarbon group, X is a halogen atom, a 0 ≦ g ≦ 4. Specific examples of such compounds include titanium tetrahalides such as TiCl ₄ , TiBr ₄ , and TiI ₄ , Ti (OCH ₃ ) Cl ₃ , and Ti (OC ₂ H ₅ ) Cl _3.
, Ti (On-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (O
-iso-C ₄ H ₉₎ trihalide, alkoxy titanium such as _{Br 3, Ti (OCH 3)} 2 Cl 2, Ti (OC 2 H 5) 2 Cl 2, Ti
Dialkoxytitanium dihalides such as (On-C ₄ H ₉ ) ₂ Cl ₂ and Ti (OC ₂ H ₅ ) ₂ Br ₂ , Ti (OCH ₃ ) ₃ Cl, Ti (O
_{C 2 H 5) 3 Cl,} Ti (On-C 4 H 9) 3 Cl, Ti (OC 2 H 5) 3 B
r and other monohalogenated trialkoxy titanium, Ti (O
CH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₄ H ₉ ) ₄ , Ti
Examples thereof include tetraalkoxy titanium such as (O-iso-C ₄ H ₉ ) ₄ and Ti (O-2-ethylhexyl) ₄ .

Preferred among these are titanium tetrahalides, and titanium tetrachloride is particularly preferred. These titanium compounds may be used alone or in combination of two or more. Alternatively, it may be used after being diluted with a hydrocarbon or a halogenated hydrocarbon. Titanium trichloride is used as the trivalent titanium compound.

As such titanium trichloride, for example, titanium tetrachloride is brought into contact with hydrogen or a metal such as metallic magnesium, metallic aluminum, metallic titanium or an organometallic compound such as an organic magnesium compound, an organic aluminum compound or an organic zinc compound. Titanium trichloride obtained by the reduction is preferably 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 an organic magnesium compound represented by the following formula. X _n MgR _{2-n In the} formula, n is 0 ≦ n <2, and R is hydrogen or carbon atom 1
20 to 20 alkyl groups, aryl groups or cycloalkyl groups. When n is 0, two Rs may be the same or different, and X is a halogen.

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

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

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

The magnesium compound having a reducing ability and the magnesium compound having no reducing ability include the organometallic compounds described later, for example, aluminum, zinc,
It may form a complex compound or complex compound with another metal such as boron, beryllium, sodium and potassium, or may be a mixture with another metal compound. Further, the magnesium compound may be used alone, or two or more of the above compounds may be used in combination. The magnesium compound may be used in a liquid state or a solid state. When the magnesium compound is a solid, the magnesium compound can be made into a liquid state by using an alcohol, a carboxylic acid, an aldehyde, an amine, a metal ester, or the like described later as the electron donor (a).

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, and the finally obtained solid titanium catalyst component [A-] In [1], it is preferable to take the form of a halogen-containing magnesium compound. Therefore, when a halogen-free magnesium compound is used, it is preferable to carry out a contact reaction with the halogen-containing compound during the preparation.

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

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

Preferred examples of the organic acid ester include a polycarboxylic acid ester having a skeleton represented by the following general formula.

[0060]

Embedded image

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

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

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

[0064]

Embedded image

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

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

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

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

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

Such a solid titanium catalyst component [A-1]
Is usually at -70 ° C to 200 ° C, preferably at -5 ° C.
It is performed at a temperature of 0 ° C to 150 ° C. The solid titanium catalyst component [A-1] thus obtained contains titanium, magnesium, halogen and preferably an electron donor (a).

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

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

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

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

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

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

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

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

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

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

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

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

[0083] In _{^{R 2 k R 3 l R 4}} m R 5 n M ( wherein, M is the transition metal, R ² is a group (ligand) having a cyclopentadienyl skeleton, R ^3, R ⁴ and R ⁵ are a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a trialkylsilyl group, an SO ₃ R group, a halogen atom or a hydrogen atom. And k is an integer of 1 or more and k + 1 + m + n = 4.) In the present invention, in the above formula R ² _k R ³ _l R ⁴ _m R ⁵ _n M, 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. These groups having a cyclopentadienyl skeleton are ethylene, alkylene groups such as propylene, isopropylidene, substituted alkylene groups such as diphenylmethylene, silylene group or dimethylsilylene, diphenylsilylene,
It may be bonded via a substituted silylene group such as a methylphenylsilylene group. R ⁴ and R ⁵ are a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a trialkylsilyl group, SO 4
₃ R is a halogen atom or a hydrogen atom.

The following are specific examples of the transition metal compound in which M is zirconium. Bis (indenyl) zirconium dichloride, bis (indenyl)
Zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato) bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylene Bis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) zirconiumbis (methanesulfonato), ethylenebis ( Indenyl) zirconium bis (p-toluenesulfonate), ethylenebis (indenyl) zirconiumbis (trifluoromethanesulfonate), ethylenebis (4,5,6,7 -Tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (cyclopentadienyl) zirconium dichloride, Dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylene Bis (indenyl) zirconium bis (trifluoromethanesulfonate), dimethylsilicone Bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, methylphenylsilylenebis (indenyl) zirconium dichloride, bis (Cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl)
Methyl zirconium monochloride, bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride, bis (cyclopentadienyl)
Benzyl zirconium monochloride, bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) methyl zirconium monohydride, bis (cyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) diphenyl zirconium, Bis (cyclopentadienyl) dibenzyl zirconium, bis (cyclopentadienyl)
Zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxycyclolide, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato), bis (cyclo (Pentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl)
Zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxycyclolide, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadiyl) Enyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl)
Zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonato), bis (trimethylcyclopentadienyl) ) Zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride,
Bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl)
Zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride.

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

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

These compounds may be used alone or
Two or more kinds may be used in combination. 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 in which the central metal atom is zirconium and which has a ligand having at least two cyclopentadienyl skeletons is preferably used.

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

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

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

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

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

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

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

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

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

[0097] In R ^a _n AlY _3-n the above formulas, R ^a is as defined above, Y is -OR
^b group, -OSiR ^c ₃ group, -OAlR ^d ₂ group, -NR ^e ₂ group, -
A SiR ^f ₃ group or a —N (R ^g ) AlR ^h ₂ group, wherein n is 1
And R ^b , R ^c , R ^d and R ^h are methyl groups,
Ethyl, isopropyl, isobutyl, cyclohexyl, phenyl, etc., ^Re is hydrogen, methyl, ethyl, isopropyl, phenyl, trimethylsilyl, etc., and R ^f and R ^g are methyl, And an ethyl group.

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

[0099] As [B-1] organoaluminum compounds mentioned _{^{above, R a 3 Al, R a}} n Al (OR b) 3-n, R
an organoaluminum compound represented by _{^{a n Al (OAlR d 2)}} 3-n may be mentioned as preferred examples.

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

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

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

[0103]

Embedded image

(In the general formulas (1) and (2), R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group, and is preferably a methyl group, 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 And the same hydrocarbon group as R can be exemplified, and R ¹ and R ² represent different groups.]. In this case, aluminum formed from mixed alkyloxyaluminum units containing at least 30 mol%, preferably at least 50 mol%, particularly preferably at least 70 mol% of methyloxyaluminum units (OAl (CH ₃ )). 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. You may.

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

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

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

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

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

In the present invention, when [A] the transition metal compound catalyst component is [A-1] a solid titanium catalyst component or [A-2] a titanium trichloride catalyst component, [B] an organometallic catalyst component The compound catalyst component is preferably [B-1] an organoaluminum compound, and when [A] the transition metal compound catalyst component is [A-3] a metallocene compound, [B] the organometallic compound catalyst component is And [B-2] an organic aluminum oxy compound.

When preliminarily polymerizing ethylene and a polyene compound with the transition metal compound catalyst component (a) and the organometallic compound catalyst component (B), the electron donor (a) described above or the following An electron donor (b) such as described above may be used.

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

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

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

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

The above electron donors (b) can be used in combination of two or more. In the present invention, when forming the ethylene / polyene copolymer-containing polymer [I], first, the above-mentioned [A] transition metal compound catalyst component and [B]
Ethylene-polyene copolymer obtained by copolymerizing the above-mentioned ethylene and polyene compound with organometallic compound catalyst component
to form a prepolymerized catalyst containing (i).

In the present invention, when the transition metal compound catalyst component and the organometallic compound catalyst component [B] are prepolymerized with ethylene and a polyene compound, the polyene compound is usually added in an amount of 0.1 to 1 mol of ethylene. 0001-
It is preferably used in an amount of 10 mol, preferably 0.0005 to 5 mol, particularly preferably 0.001 to 2 mol.

In forming the prepolymerized catalyst, an α-olefin having 3 or more carbon atoms may be used as long as the object of the present invention is not impaired. This copolymerization of ethylene and the polyene compound can be carried out by any of a liquid phase polymerization method such as solution polymerization and suspension polymerization or a gas phase polymerization method. When the polymerization is carried out in a liquid phase, the polymerization can be carried out in the presence of an inert solvent described later. Further, the polymerization can be carried out using the olefin and / or polyene compound in a liquid state as a solvent or in a state substantially free of a solvent.

In the present invention, this preliminary copolymerization can be carried out in the presence of an inert solvent described later, and it is preferable to add the above-mentioned monomer and catalyst component to the inert solvent and carry out the reaction under relatively mild conditions. . At this time, the reaction may be carried out under a condition in which the produced prepolymer is dissolved in the polymerization medium, or may be carried out under a condition in which the prepolymer is not dissolved.

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

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

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

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

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

When an electron donor is used, the electron donor is used in an amount of 0.01 to 50 mol, preferably 0.05 to 50 mol, per 1 mol of 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 during the prepolymerization is usually about -20.
To + 100 ° C, preferably about -20 to + 80 ° C, and more preferably about -10 to + 40 ° C.
In the preliminary polymerization, a molecular weight regulator such as hydrogen may be used.

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

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

In the case where the above prepolymerized catalyst is used in a suspended state in the main polymerization step to be described later, for example, when [B] the organometallic compound catalyst component is sufficiently contained in the prepolymerized catalyst, [B] In some cases, it is not necessary to add the organometallic compound catalyst component.

In the present invention, the olefin can be preliminarily polymerized on the transition metal compound catalyst component [A] and the organometallic compound catalyst component before the preliminary copolymerization.

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

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

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

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

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

The polymerization conditions vary depending on the olefin used, but the polymerization temperature is usually -20 to 300 ° C, preferably about -20 to 150 ° C, and more preferably -10 to -1 ° C.
30 ° C., and the polymerization pressure is usually from normal pressure to 100 kg / cm.
² , preferably about ² to 50 kg / cm ² .

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

Next, the olefin polymer [II] contained in the olefin polymer composition according to the present invention will be described. As the olefin polymer [II] used in the present invention, conventionally known α-olefin polymers or copolymers having 2 to 20 carbon atoms can be widely used. Specifically, for example, high density 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 include various propylene-based block copolymers, propylene-based random copolymers, and mixtures thereof.

Among them, the olefin polymer [II] includes the ethylene / polyene copolymer-containing polymer [I].
The polymer of the same olefin as the olefin forming the olefin polymer (ii) contained in the above is preferably used.

The olefin polymer composition according to the present invention comprises:
The ethylene-polyene copolymer-containing polymer [I] was added to 0.1
The olefin polymer [I] in an amount of 005 to 99% by weight, preferably 0.01 to 90% by weight, more preferably 0.03 to 85% by weight, particularly preferably 0.05 to 80% by weight.
I] is 99.995-1% by weight, preferably 99.99%
10 to 10% by weight, more preferably 99.97 to 15% by weight, particularly preferably 99.95 to 20% by weight.

The olefin polymer composition according to the present invention comprises:
It is prepared by blending the above amount of the ethylene / polyene copolymer-containing polymer [I] and the olefin polymer [II]. Specifically, an ethylene / polyene copolymer-containing polymer [I] and an olefin polymer [II] are mixed at 100 to 350 ° C. using an apparatus generally used for kneading a polymer. Preferably 150
Knead at a temperature of ~ 300 ° C.

The olefin polymer composition according to the present invention comprises:
Conventionally known olefin polymers such as those described above [I
I] has a higher melt tension. In the olefin polymer composition according to the present invention, the relationship between the melt flow rate and the melt tension specifically satisfies the following expression.

When the olefin polymer [II] is polypropylene, the olefin polymer composition usually has a log [MT] ≧ −0.8 log [MFR] +0.28, preferably a log [MT] ≧ − 0.8 log [MFR] +0.30 More preferably, the relationship expressed by log [MT] ≧ −0.8 log [MFR] +0.33 is satisfied.

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

In addition, the following formula is usually satisfied with the intrinsic viscosity [η]. log [MT] ≒ 3.7 log [[η]]-1.6 The olefin polymer composition obtained in the present invention has a higher melt tension than the conventional olefin polymer as described above. Such an olefin polymer composition is excellent in moldability at the time of inflation molding, and can be molded into a film at a high yield and at a high speed, and can be applied to, for example, a blow molding method, a vacuum molding method and the like. Thus, the available applications are expanded.

In particular, the olefin polymer composition according to the present invention, which contains a high concentration of the ethylene / polyene copolymer-containing polymer [I] having a specific composition and melt tension, as described above, is preferably a masterbatch. It is preferably used as

When the olefin polymer composition according to the present invention is used particularly as a master batch, the olefin polymer composition contains a high concentration of the ethylene / polyene copolymer (i). An ethylene / polyene copolymer-containing polymer [I] is used. Specifically, in the ethylene / polyene copolymer-containing polymer [I], the ethylene / polyene copolymer (i) contains 15 to 99% by weight, preferably 20 to 90% by weight, and particularly preferably 22 to 90% by weight.
In an amount of ~ 88 wt%, the olefin polymer (ii) is
It is preferably present in an amount of 1% by weight, preferably 80 to 10% by weight, particularly preferably 78 to 12% by weight.

The ethylene-polyene copolymer-containing polymer [I] used in this case has a melt tension of at least 20 g, preferably 2 g, when the MFR is usually 2 g / 10 min.
5 g or more, more preferably 30 g or more. When measuring the melt tension of the olefin polymer composition for masterbatch described above, the measurement may not be possible due to thread breakage.

The olefin polymer composition used as such a masterbatch is prepared by adding the ethylene / polyene copolymer-containing polymer [I] having the specific composition as described above to 0.0%.
05-99% by weight, preferably 0.01-95% by weight,
More preferably, in an amount of 0.02 to 90% by weight, the olefin polymer [II] is used in an amount of 99.995 to 1% by weight, preferably 99.99 to 5% by weight, more preferably 99.9%.
It is contained in an amount of 8 to 10% by weight.

Such a masterbatch is further blended with an olefin polymer at the time of use. As the olefin polymer to be blended with such a master batch, the same olefin polymer as the above-mentioned olefin polymer [II] is preferably used. When a masterbatch formed containing such an olefin polymer [II] is blended with the same olefin polymer as the olefin polymer [II], they have excellent compatibility with each other, and have an olefin having a desired composition at the time of molding. A polymer composition is easily obtained.

Further, the olefin polymer composition according to the present invention may contain various stabilizers, antistatic agents, antiblocking agents, lubricants, nucleating agents, pigments, dyes, inorganic or organic fillers and the like. .

It is preferable that the olefin polymer composition according to the present invention contains a phenolic stabilizer, since a molded article having excellent heat stability and transparency can be obtained. Particularly, a phenolic stabilizer and an organic phosphite are preferred. It is preferable to incorporate a system stabilizer since a film having particularly excellent heat stability and transparency can be obtained.

When the higher fatty acid metal salt is added to the composition relating to the olefin polymer according to the present invention, the thermal stability of the resin at the time of molding is improved, and further, rusting of the molding machine due to halogen gas caused by the catalyst. Further, troubles caused by corrosion can be suppressed. In particular, it is preferable to use a phenol stabilizer and / or an organic phosphite stabilizer together with a higher fatty acid metal salt.

As the phenol-based stabilizer, specifically, 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, 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), 2,2'-thiobis (4-methyl-6-t-
Butylphenol), 4,4'-methylenebis (2,6-di-t-
Butylphenol), 2,2′-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2,2′-ethylidenebis (4,6-di-t-butylphenol), 2,2′-butylidenebis ( 2-t-butyl-4-methylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, triethylene glycol-bis [3- (3-t- Butyl-5
-Methyl-4-hydroxyphenyl) propionate],
1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-
Hydroxyphenyl) propionate], 2,2'-thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis
(3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-tris (2,6-dimethyl -3-hydroxy-4-t-butylbenzyl) isocyanurate, 1,3,5-tris [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tris (4- t-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,
3,5-triazine, tetrakis [methylene-3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate] methane, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate) calcium, bis (3,5-di-t-butyl)
4-ethyl ethyl hydroxybenzylphosphonate) nickel,
Bis [3,3-bis (3-t-butyl-4-hydroxyphenyl)
Butyric acid] glycol ester, N, N'-bis [3
-(3,5-Di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, 2,2'-oxazamidebis [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;

As the 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 particularly preferably used.

In the molecule,

[0158]

Embedded image

A phenolic stabilizer having a structure represented by the following formula is 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 is 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.

[0160]

Embedded image

Of these, 2,6-di-tert-butyl-4-
Methylphenol, stearyl-β- (4-hydroxy-3,5
-Di-tert-butylphenol) propionate, 2,2'-
Ethylidenebis (4,6-di-tert-butylphenol) and tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane are preferred.

These phenolic stabilizers are used alone or as a mixture. Examples of the phosphite-based stabilizer include trioctyl phosphite, trilauryl phosphite, tristridecyl phosphite, tris isodecyl phosphite, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl Isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (butoxyethyl ) Phosphite, 4,4'-isopropylidene-diphenol alkyl phosphite (where alkyl has about 12 to 15 carbon atoms), 4,4'-isopropylidenebis (2-t-butylphenol) di (nonylphenyl) ) Phosphite, tris (biphenyl) phosphite, tetra (tridecyl) -1,1,3-tris (2-methyl -5-t
-Butyl-4-hydroxyphenyl) butanediphosphite, tris (3,5-di-t-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, bis (Octylphenyl)
・ Bis [4,4'-butylidenebis (3-methyl-6-t-butylphenol)] ・ 1,6-hexaneoldiphosphite, hexatridecyl-1,1,3-tris (2-methyl-4- Hydroxy
-5-t-butylphenol) diphosphite, tris [4,
4'-isopropylidenebis (2-t-butylphenol)] phosphite, tris (1,3-distearoyloxyisopropyl) phosphite, 9,10-dihydro-9-phosphaphenanthrene-10-oxide, tetrakis (2,4-di-t-
(Butylphenyl) -4,4'-biphenylenediphosphonite and the like.

Of these, tris (2,4-di-tert-
Butylphenyl) phosphite, tris (nonylphenyl) phosphite and tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphite are preferred, and tris (2,4-di-tert -Butylphenyl) phosphite is particularly preferred.

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

[0165]

Embedded image

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

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

Specifically, the saturated or unsaturated carboxylic acids 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 which forms a salt by reacting with these higher fatty acids, alkaline earth metal salts such as magnesium, calcium and barium, alkali metals such as sodium, potassium and lithium, And cadmium, zinc and lead.

Specific examples of higher fatty acid salts 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, and zinc montanate.

Among 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 are used alone or in combination.

When the above-mentioned stabilizer is incorporated, the phenolic stabilizer is usually contained in the olefin polymer composition in an amount of 0.01 to 1.0% by weight, preferably 0.02% by weight.
To 0.5% by weight, particularly preferably 0.03 to 0.2% by weight.

Similarly, the organic phosphite stabilizer is used in an amount of usually 0.01 to 1.0% by weight, preferably 0.02 to 0.1% by weight.
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 may be used in the same manner as above.
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.

[0174]

The olefin polymer composition according to the present invention has a higher melt tension than the conventional olefin polymer. Such an olefin polymer composition is excellent in moldability at the time of inflation molding, and can be molded into a film at a high yield and at a high speed, and can be applied to, for example, a blow molding method, a vacuum molding method and the like. Thus, the available applications are expanded.

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

[0176]

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 homogeneous solution. Phthalic anhydride in solution 21.
3 g was added, and the mixture was further 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.
Charged dropwise over time. After completion of the charging, the temperature of the mixed solution was raised to 110 ° C. over 4 hours, and when the temperature reached 110 ° C., diisobutyl phthalate (DIBP) 5.2 was obtained.
2 g was added, and the mixture was stirred and maintained at the same temperature for 2 hours.

After completion of the reaction, a solid portion was collected by hot filtration.
After resuspending this solid portion in 275 ml of titanium tetrachloride, the resulting suspension was heated again at 110 ° C. for 2 hours. After completion of the reaction, a solid portion was collected again by hot filtration, and
The solution was sufficiently washed with decane and hexane at 0 ° 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 was 2.4% by weight of titanium, 60% by weight of chlorine, 20% by weight of magnesium, and 13.0% by weight of DIBP.

[Preparation of Prepolymerized Solid Titanium Catalyst Component [B]] In a 400 ml four-neck glass reactor equipped with a stirrer, 200 ml of purified hexane, 6 mmol of triethylaluminum, and the above solid titanium catalyst component [ A] was added in an amount of 2.0 mmol in terms of titanium atoms, and then propylene was supplied to the reactor at a temperature of 20 ° C. at a rate of 6.4 liter / hour for 1 hour.

When the supply of propylene was completed, the inside of the reactor was replaced with nitrogen, and a washing operation including removal of the supernatant and addition of purified hexane was performed twice. The whole amount was transferred to obtain a prepolymerized solid titanium catalyst component [B].

[0181]Ethylene / polyene copolymer containing polymer
Production of [I] -1 "Copolymerization of ethylene and polyene" with 400ml stirrer
Purified hexane 3 in a four-neck glass reactor under a nitrogen atmosphere
34 ml, 1,9-decadiene 2 ml, diethylaluminum
10 mmol of chloride and the prepolymerized solid
1.0 mmol of the tan catalyst component [B] in terms of titanium atom
After the addition, ethylene is fed to the reactor at a temperature of 0 ° C.
did. When ethylene reacts 28 liters
Supply of gas was stopped.

When the supply of ethylene was completed, the inside of the reactor was replaced with nitrogen, and a washing operation including removal of the supernatant and addition of purified hexane was performed twice. The whole amount was transferred to obtain a prepolymerized catalyst [C] containing the ethylene / polyene copolymer (i).

With the prepolymerized catalyst [C] thus obtained, 15.3 / g of the transition metal compound catalyst component was used.
An ethylene / 1,9-decadiene copolymer was produced in an amount of g. "Polymerization of olefin" After charging 600 ml of purified hexane under a nitrogen atmosphere into a 1-liter five-necked glass reactor equipped with a stirrer, the temperature was raised to 60 ° C.
Mmol, cyclohexylmethyldimethoxysilane (C
MMS) 3 mmol and the prepolymerized catalyst [C]
After adding 0.6 mmol in terms of titanium atoms, propylene was supplied to this reactor at a flow rate of 150 liter / hour and hydrogen was supplied at a flow rate of 0.2 liter / hour, and polymerization was carried out for 60 minutes. The polymerization temperature was kept at 70 ° C.

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

After completion of the stirring, the slurry containing the produced solid was filtered to separate the polymer, followed by drying at 70 ° C. under reduced pressure to obtain 195.2 g of an ethylene / polyene copolymer-containing polymer [I] -1. Was. The MFR of the ethylene-polyene copolymer-containing polymer [I] -1 was 11.2 dg / min.

The composition of the ethylene-polyene copolymer-containing polymer [I] -1 thus obtained was as follows.
The polyene copolymer was 13.2% by weight, and the olefin polymer was 86.8% by weight.

Production of Polypropylene Composition 11.2 parts by weight of the ethylene / polyene copolymer-containing polymer [I] -1 obtained as described above, 1 part by weight of calcium stearate, 3,5-di-t -Butyl-4-hydroxytoluene 1 part by weight, tetrakis [methylene (3,5-di-t-butyl-4-hydroxy) hydrocinnamate] methane 1 part by weight, and propylene homopolymer [II] (MFR =
1.5 dg / min, [η] = 2.80 dl / g, boiling heptane extraction residual ratio 98.0%), and 1000 parts by weight.
It was granulated into pellets using an mmφ extruder.

The obtained polypropylene composition had a melt tension (MT) of 1.7 g and an MFR of 1.8 dg.
/ Min and [η] were 2.69 dl / g.

[0189]

Example 2 Preparation of Polymer [I] -2 Containing Ethylene / Polyene Copolymer
In a 1-liter five-neck glass reactor equipped with a stirrer, 600 ml of purified hexane was charged under a nitrogen atmosphere, and the temperature was raised to 60 ° C.
Mmol, cyclohexylmethyldimethoxysilane (C
MMS) 3 mmol and the prepolymerized catalyst [C]
After adding 0.6 mmol in terms of titanium atoms, propylene was supplied to this reactor at a flow rate of 150 liter / hour and hydrogen at a flow rate of 0.2 liter / hour, and polymerization was performed for 25 minutes. The polymerization temperature was kept at 70 ° C.

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

After completion of the stirring, the slurry containing the produced solid was filtered to separate the polymer, and dried at 70 ° C. under reduced pressure to obtain 98.3 g of an ethylene / polyene copolymer-containing polymer [I] -2. Was. The MFR of the ethylene / polyene copolymer-containing polymer [I] -2 was 8.0 dg / min.

The composition of the ethylene-polyene copolymer-containing polymer [I] -2 thus obtained was as follows.
The polyene copolymer was 25.7% by weight and the olefin polymer was 74.3% by weight.

Production of Composition for Masterbatch [M-1] 50 parts by weight of the ethylene / polyene copolymer-containing polymer [I] -2 obtained as described above, 1 part by weight of calcium stearate, 1 part by weight of 5-di-t-butyl-4-hydroxytoluene, tetrakis [methylene (3,5-di-t-butyl-
4-hydroxy) hydrocinnamate] methane 1 part by weight,
And propylene homopolymer [II] -2 (MFR = 7.
(0 dg / min, boiling heptane extraction residual ratio: 98.0%), 50 parts by weight were mixed and granulated into pellets with a 20 mmφ extruder to obtain a master batch composition [M-1].

Production of Polypropylene Composition The masterbatch composition [M-
1], 25 parts by weight, 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, and propylene homopolymer [II] (MFR = 1.5 dg / min, boiling heptane extraction residual ratio 98.0%)
The mixture was granulated into pellets using a 0 mmφ extruder.

The obtained polypropylene composition had a melt tension (MT) of 1.8 g and an MFR of 1.8 dg.
/ Min and [η] were 2.69 dl / g.

[0196]

Comparative Example 1 The MT of the propylene homopolymer [II] used in Examples 1 and 2 was 1.4 g.

[Brief description of the drawings]

FIG. 1 is a view showing a process for producing an ethylene / polyene copolymer-containing polymer [I] according to the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 3-204467 (32) Priority date August 14, 1991 (August 14, 1991) (33) Priority claim country Japan (JP) (56) References JP-A-62-32105 (JP, A) JP-A-59-56412 (JP, A) JP-A-2-311507 (JP, A) JP-A-4-159312 (JP, A) Unexamined Japanese Patent Publication No. 5-222122 (JP, A) U.S. Pat. No. 5,021,382 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/60-4/70 C08F 10/00-10/14 C08L 23/00-23/36 CA (STN) EPAT (QUESTEL) REGISTRY (STN) WPI / L (QUESTEL)

Claims (8)

(57) [Claims] [1] [I] [A] a transition metal compound catalyst component and
Beauty the [B] Periodic Table Group I - Group III or al metal selected
Includes organometallic compound catalyst components containing ethylene and polyene
And a structural unit derived from ethylene in an amount of 99.999 to 50 mol%, and a structural unit derived from the polyene compound in an amount of 0.001 to 50.
Ethylene / polyene copolymer contained in the amount of mol%
An ethylene / polyene copolymer-containing polymer obtained by polymerizing or copolymerizing an olefin with a prepolymerized catalyst containing (i) to form an olefin polymer (ii): 0.0
An olefin polymer composition obtained by blending from 0.5 to 99% by weight with [II] olefin polymer: 1 to 99.995% by weight. (I) The ethylene / polyene copolymer-containing polymer is (i) the ethylene / polyene copolymer in an amount of 0.001 to 15% by weight, and (ii) the olefin polymer is 99.999%. The olefin polymer composition according to claim 1, which is an ethylene / polyene copolymer-containing polymer contained in an amount of from about 85% by weight. 3. An organometallic compound comprising: [I] an ethylene / polyene copolymer-containing polymer comprising: [A] a catalyst component for a transition metal compound and [B] a metal selected from Groups I to III of the Periodic Table. A prepolymerized catalyst comprising an ethylene / polyene copolymer (i), wherein ethylene and a polyene compound are copolymerized in an amount of 0.01 to 2000 g per 1 g of the transition metal compound catalyst component; Polymerized or copolymerized with an olefin to form an olefin polymer
3. The olefin polymer composition according to claim 1, which is an ethylene / polyene copolymer-containing polymer obtained by forming (ii). 4. The olefin polymer composition according to claim 1, wherein the polyene compound is a polyene compound having olefinic double bonds at both ends. 5. The polyene compound is an aliphatic polyene compound and / or an alicyclic polyene compound having an olefinic double bond at both terminals and has 7 or more carbon atoms. 4. The olefin polymer composition according to 2 or 3. 6. The method according to claim 1, wherein the catalyst component (A) is Ti,
The olefin polymer composition according to claim 3, which is a compound containing at least one transition metal selected from Zr, Hf, Nb, Ta, Cr, and V. 7. The olefin polymer composition according to claim 3, wherein the catalyst component (A) is a solid titanium catalyst component containing titanium and halogen. 8. The olefin polymer composition according to claim 3, wherein the catalyst component (A) is a metallocene compound containing a ligand having a cyclopentadienyl skeleton.