JP3444185B2 - Olefin (co) polymer composition and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin (co) polymer composition, and more particularly to an olefin (co) polymer composition having high melt tension and excellent moldability.

[0002]

2. Description of the Related Art Olefin (co) polymers such as polypropylene and polyethylene are widely used in various molding fields because they are excellent in mechanical properties, chemical resistance and the like and are extremely useful in balance with economic efficiency. Conventionally, these olefin (co) polymers mainly use a so-called Ziegler-Natta type catalyst in which titanium trichloride, titanium tetrachloride or a transition metal catalyst component in which these are supported on a carrier such as magnesium chloride and an organic aluminum compound are combined. Have been produced by (co) polymerizing olefins.

On the other hand, in recent years, an olefin (co) polymer is obtained by (co) polymerizing an olefin using a catalyst obtained by combining a metallocene and an aluminoxane different from the conventional catalyst system, and using the metallocene catalyst. The obtained olefin (co) polymer has a narrow molecular weight distribution, and in the case of the copolymer, since the comonomer is uniformly copolymerized, a more homogeneous olefin (co) polymer can be obtained than before. Are known. However, the olefin (co) polymers obtained by using these metallocene catalysts have a low melt tension as compared with the olefin (co) polymers obtained by using the conventional catalyst system, and depending on the application field, they may be used. May be restricted.

As a method of increasing the melt tension and crystallization temperature of polypropylene, a method of reacting polypropylene with an organic peroxide and a crosslinking aid in a molten state (Japanese Patent Laid-Open Nos. 59-93711 and 61-61). 15275
No. 4, etc.), a method of producing a polypropylene containing free-end long chain branches and containing no gel by reacting semi-crystalline polypropylene with a low decomposition temperature peroxide in the presence of oxygen (JP-A-2-298536). Gazette) is proposed.

As another method for improving melt viscoelasticity such as melt tension, there has been proposed a composition containing polyethylene or polypropylene having different intrinsic viscosities or molecular weights, and a method for producing such a composition by multi-step polymerization. ing.

For example, ultra high molecular weight polypropylene 2
A method in which 30 parts by weight is added to 100 parts by weight of ordinary polypropylene and extruded in a temperature range of melting point or more and 210 ° C. or less (Japanese Patent Publication No. 61-28694), and an intrinsic viscosity ratio obtained by a multistage polymerization method is 2 or more. Extruded sheet made of polypropylene with two different components (Japanese Patent Publication 1-1
No. 2770), a method for producing a polyethylene composition composed of three kinds of polyethylene having different viscosity average molecular weights, which contains 1 to 10% by weight of high viscosity average molecular weight polyethylene, by a melt-kneading method or a multistage polymerization method (Japanese Patent Publication No. Sho 62-62). No. 61057 gazette), an ultrahigh molecular weight polyethylene having an intrinsic viscosity of 20 dl / g or more was obtained by a multistage polymerization method using a highly active titanium / vanadium solid catalyst component.
To a method of polymerizing polyethylene to polymerize less than 1% by weight (Japanese Patent Publication No. 5-79383), a highly active titanium catalyst component prepolymerized with 1-butene or 4-methyl-1-pentene is used to obtain a special arrangement. There has been proposed a polyethylene polymerization method (Japanese Patent Publication No. 7-8890) in which 0.1 to 5% by weight of ultrahigh molecular weight polyethylene having an intrinsic viscosity of 15 dl / g or more is polymerized by a multistage polymerization method using a polymerization vessel.

Further, polypropylene having a high melt tension is produced by polymerizing propylene using a prepolymerized catalyst obtained by prepolymerizing ethylene and a polyene compound as a supported titanium-containing solid catalyst component and an organoaluminum compound catalyst component. Method (JP-A-5-22212)
No. 2) and a similar catalyst component, and prepolymerization is carried out by using ethylene alone to prepare a linear low density polyethylene (LLDPE) having a high melt tension using a prepolymerization catalyst containing polyethylene having an intrinsic viscosity of 20 dl / g or more. Has been proposed (Japanese Patent Laid-Open No. 4-55410).

As a study for improving the melt tension when a metallocene catalyst system is used, a silica carrier containing 1.0% by weight or more of water, a catalyst composed of metallocene, methylaluminoxane and triisobutylaluminum is used. Method (JP-A-5-140224, JP-A-5-140224), a method of using two kinds of metallocenes as catalyst components (JP-A-5-255436).
JP-A-5-255437, JP-A-6-2
No. 06939), and a method of using montmorillonite in a metallocene catalyst system (Japanese Patent Application Laid-Open No. 7-188317, Kaihei 7-188336) and the like.

[0009]

In the above-mentioned proposed various compositions and the production methods thereof in the conventional catalyst system, it is possible to improve the melt tension of the polyolefin to some extent at 190 ° C. under the measurement conditions. Although observed, there are still some points to be improved such as improvement of melt tension under use condition of 200 ° C. or higher, residual odor due to crosslinking aid, crystallization temperature, thermal stability of physical properties other than melt tension.

Further, although the above-mentioned proposed method for the metallocene catalyst system can improve the melt tension of the polyolefin to some extent at 190 ° C., the melt tension at 200 ° C. or higher is further improved. Is desired.

As is apparent from the above description, the present invention uses an olefin (co) polymer obtained by (co) polymerizing an olefin using a metallocene catalyst system, and has high melt tension to improve moldability. An object is to provide an excellent olefin (co) polymer composition. In particular, it is intended to improve the melt tension of the olefin (co) polymer obtained from metallocene and improve the moldability.

[0012]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the inventors of the present invention have found that a metallocene olefin (co) polymer and a catalyst for polyolefin production containing a small amount of the main (co) polymerization object Olefin (co) having high melt tension and excellent processability by blending olefin (co) polymer polymerized using polypropylene and polyethylene having a specific intrinsic viscosity and pre-activated catalyst It was found that a polymer composition can be obtained,
The present invention has been completed.

In order to achieve the above object, the olefin (co) polymer composition of the present invention comprises (I) the following compounds (A) and (B), or the following compounds (A), (B) and (C). The intrinsic viscosity [ηI] measured in tetralin at 135 ° C. obtained by (co) polymerizing an olefin using a catalyst consisting of 0.2 to 10 dl
/ G olefin (co) polymer (I) is 99-50
% By weight, compound (A): transition metal compound having at least one π-electron conjugated ligand (B): (B-1) aluminoxane, (B-2)
An ionic compound that reacts with the transition metal compound (A) to form an ionic complex, and (B-3) one or more compounds selected from a Lewis acid compound (C): organoaluminum compound (II) 1 to 50% by weight of the olefin (co) polymer (II) whose main component is 0.01 to 5 parts by weight of the component (II-1) of (II-1), and (II-1) ) A high molecular weight olefin (co) polymer having an intrinsic viscosity [ηE] measured with tetralin at 135 ° C. in the range of 15 to 100 dl / g , which is an ethylene homopolymer or
Ethylene containing 50% by weight or more of ethylene polymer units
Olefin Copolymer (II-2) The high molecular weight olefin (co) polymer (II-
Olefin (co) polymers other than 1) , which are propylene
50% by weight or less of homopolymer or propylene polymer unit
The propylene-olefin random copolymer also contained above
The main component is a composition comprising a propylene-olefin block copolymer .

[0014] In the prior SL compositions, the olefin (co)
The polymer (I) is preferably a propylene homopolymer or a propylene-olefin random copolymer or a propylene-olefin block copolymer containing 50% by weight or more of propylene polymer units. Further, in the above composition, the olefin (co) polymer composition has a melt tension (MS) at 230 ° C. of 21.18 N
Under load, between the melt flow index was measured have you to 230 ℃ (MFR), log ( MS)> - 1.28 × log (MFR) +0.
It is preferable to have a relationship represented by 44. In the composition, the compound (A) is preferably a transition metal compound represented by the following formula [1]. MLp ... [1] (where M is Zr, Ti, Hf, V, Nb,
A transition metal selected from Ta and Cr, p is the valence of the transition metal, L is a ligand that coordinates to the transition metal, and at least one L is a π-electron conjugated ligand. )

In the composition, the π-electron conjugated ligand is at least selected from η-cyclopentadienyl structure, η-benzene structure, η-cycloheptatrienyl structure and η-cyclooctatetraene structure. It is preferably one ligand. In the composition, the ligand having the η-cyclopentadienyl structure is
At least one ligand selected from cyclopentadienyl group, indenyl group, hydrogenated indenyl group and fluorenyl group (provided that these groups are hydrocarbon groups such as alkyl groups, aryl groups and aralkyl groups, trialkylsilyl groups). Group, such as a silicon-substituted hydrocarbon group, a halogen atom, an alkoxy group, an aryloxy group, a chain or cyclic alkylene group, and the like) are preferable.

In the above composition, when the transition metal compound represented by the general formula [1] contains two or more π-electron conjugated ligands, two of the π-electron conjugated ligands are Is an alkylene group, a substituted alkylene group, a cycloalkylene group, a substituted cycloalkylene group, a substituted alkylidene group, a phenylene group, a silylene group, a dimethylsilylene group, a diphenylsilylene group, a dialkylsilylyl group, a substituted dimethylsilylene group and a germyl group (Me. It is preferably crosslinked through at least one group selected from ₂ Ge). In the composition, L other than the π-electron conjugated ligand is a hydrocarbon group such as a halogen, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, a silicon-substituted hydrocarbon group, an alkoxy group or an aryloxy group. And a substituted sulfonato group is preferred.

Further, the above composition is preferably produced by blending the olefin (co) polymer composition described in any one of the above with the components optionally added by a mechanical mixing means. Further, in the above composition, the mechanical mixing means is preferably at least one mixing device selected from an extruder and a kneader.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION As used herein, the term "polypropylene" means a propylene homopolymer and a propylene-olefin random copolymer and a propylene-olefin block copolymer containing 50% by weight or more of propylene polymer units. The term "polyethylene" means an ethylene homopolymer and an ethylene-olefin random copolymer containing 50% by weight or more of ethylene polymer units.

The olefin (co) polymer composition of the present invention comprises 99 to 50% by weight of the olefin (co) polymer (I) and 1 to 50% by weight of the olefin (co) polymer (II). It is composed mainly of the following composition.

The olefin (co) polymer (I) constituting the olefin (co) polymer composition of the present invention has an intrinsic viscosity [η _I ] of 0.2 to ₁ measured in tetralin at 135 ° C.
It is an olefin (co) polymer of 0 dl / g and may be either a homopolymer or a copolymer of an olefin having 2 to 12 carbon atoms, but preferably 50 propylene homopolymers or propylene polymer units. Propylene-olefin random copolymer or propylene-olefin block copolymer containing at least wt%, more preferably propylene homopolymer, propylene-olefin random copolymer containing at least 90 wt% of propylene polymer units. Or the propylene polymer unit content is 70
It is a propylene-olefin block copolymer of not less than wt%. These (co) polymers may be not only one type but also a mixture of two or more types. From the viewpoint of mechanical properties and moldability of the finally obtained olefin (co) polymer composition,
The intrinsic viscosity [η _I ] of the olefin (co) polymer (I) is 0.2 to 10 dl / g, preferably 0.5 to 8 dl / g.
What is used.

Further, the olefin (co) polymer (I) of the present invention is prepared by converting an olefin by using the following compounds (A) and (B) or a catalyst comprising the following compounds (A), (B) and (C). Those obtained by (co) polymerization are used. Compound (A): transition metal compound having at least one π-electron conjugated ligand compound (B): (B-1) aluminoxane, (B-2)
Ionic compound that reacts with the transition metal compound (A) to form an ionic complex, and (B-3) one or more compounds selected from Lewis acids Compound (C): Organoaluminum compound The compound (A ) Is usually called metallocene, and is specifically a transition metal compound represented by the following formula [1]. MLp ... [1] In the formula, M is a transition metal selected from Zr, Ti, Hf, V, Nb, Ta and Cr, and p is the valence of the transition metal.

L is a ligand that coordinates to a transition metal,
At least one L is a π-electron conjugated ligand. Specific examples of the π-electron conjugated ligand include a ligand having an η-cyclopentadienyl structure, an η-benzene structure, an η-cycloheptatrienyl structure, or an η-cyclooctatetraene structure, Particularly preferred is a ligand having an η-cyclopentadienyl structure.

Examples of the ligand having an η-cyclopentadienyl structure include a cyclopentadienyl group, an indenyl group, a hydrogenated indenyl group, a fluorenyl group and the like. These groups include hydrocarbon groups such as alkyl groups, aryl groups and aralkyl groups, silicon-substituted hydrocarbon groups such as trialkylsilyl groups, halogen atoms, alkoxy groups, aryloxy groups, chain and cyclic alkylene groups, etc. May be replaced with.

When the transition metal compound represented by the above general formula [1] contains two or more π-electron conjugated ligands,
Two π-electron conjugated ligands among them are alkylene group, substituted alkylene group, cycloalkylene group, substituted cycloalkylene group, substituted alkylidene group, phenylene group,
Silylene group, dimethylsilylene group, diphenylsilylene group, dialkylsilylyl group, substituted dimethylsilylene group,
It may be crosslinked via a germyl group or the like.

L other than the π-electron conjugated ligand is halogen,
A hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group, a silicon-substituted hydrocarbon group, an alkoxy group, an aryloxy group, a substituted sulfonato group,
Further, a divalent group such as an amidosilylene group or an amidoalkylene group may be bonded to the π-electron conjugated ligand. In the above, halogen includes fluorine, chlorine, bromine and iodine, but chlorine is preferable.

The specific compounds are exemplified below, but the metallocene which is the compound (A) used in the present invention is not limited to the exemplified compounds. Examples of the metallocene having one π-electron conjugated ligand include (t-butylamido) (tetramethylcyclopentadienyl) -1,2-ethylenezirconium dimethyl, (t-butylamido) (tetramethylcyclopentadienyl)- 1,2-ethylenetitanium dimethyl, (methylamido) (tetramethylcyclopentadienyl) -1,2-ethylenezirconium dibenzyl, (methylamido) (tetramethylcyclopentadienyl) -1,2-ethylenetitanium dimethyl,
(Ethylamido) (tetramethylcyclopentadienyl) methylenetitanium dimethyl, (t-butylamido) dibenzyl (tetramethylcyclopentadienyl)
Silylene zirconium dibenzyl, (benzylamide)
Examples thereof include dimethyl (tetramethylcyclopentadienyl) silirenthanium diphenyl and (phenylphosphido) dimethyl (tetramethylcyclopentadienyl) silylenezirconium dibenzyl.

The metallocene having two π-electron conjugated ligands is a non-bridging metallocene of two π-conjugated ligands, and bis (cyclopentadienyl) when the transition metal is zirconium. Zirconium dichloride, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium methyl chloride, (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (methylcyclopenta) Dienyl) zirconium dimethyl, (cyclopentadienyl) (ethylcyclopentadienyl) zirconium dichloride,
(Cyclopentadienyl) (ethylcyclopentadienyl) zirconium dimethyl, (cyclopentadienyl)
(Dimethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (dimethylcyclopentadienyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dimethyl, bis ( Ethylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dimethyl, bis (propylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dimethyl, bis (butylcyclopentadienyl) Zirconium dichloride,
Bis (butylcyclopentadienyl) zirconium dimethyl, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dimethyl, bis (diethylcyclopentadienyl) zirconium dichloride, bis (diethylcyclopentadiene (Enyl) zirconium dimethyl, bis (methylethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadienyl) zirconium dimethyl, bis (trimethylcyclopentadienyl) zirconium dichloride, bis (trimethylcyclopentadienyl) zirconium dimethyl ,
Examples thereof include bis (triethylcyclopentadienyl) zirconium dichloride and bis (triethylcyclopentadienyl) zirconium dimethyl. Among these zirconium compounds, compounds in which zirconium is replaced with titanium, hafnium, vanadium, niobium, tantalum or chromium are also available. Can be mentioned.

In the above examples, the 2-substituted form of the cyclopentadienyl ring includes 1,2- and 1,3-substituted forms, and the 3-substituted form is 1,2,3- and 1,2. , 4-substituted. The alkyl group such as propyl and butyl includes isomers such as n-, i-, sec-, and tert-.

Examples of the metallocene in which two π-conjugated ligands are crosslinked are dimethylsilylene (3-t-butylcyclopentadienyl) (fluorenyl) zirconium dichloride and dimethylsilylene (3-t-butylcyclo). Pentadienyl) (fluorenyl) hafnium dichloride, rac-ethylenebis (indenyl) zirconium dimethyl, rac-ethylenebis (indenyl)
Zirconium dichloride, rac-dimethylsilylenebis (indenyl) zirconium dimethyl, rac-dimethylsilylenebis (indenyl) zirconium dichloride, rac-ethylenebis (tetrahydroindenyl) zirconium dimethyl, rac-ethylenebis (tetrahydroindenyl) zirconium dichloride, r
ac-dimethylsilylenebis (tetrahydroindenyl) zirconium dimethyl, rac-dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-)
4,5,6,7-Tetrahydroindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-
Methyl-4,5,6,7-tetrahydroindenyl) zirconium dimethyl, rac-ethylenebis (2-methyl-4,5,6,7-tetrahydroindenyl) hafnium dichloride, rac-dimethylsilylenebis (2
-Methyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dimethyl, r
ac-Dimethylsilylenebis (2-methyl-4-phenylindenyl) hafnium dichloride, rac-dimethylsilylenebis (2-methyl-4-naphthylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4-) Naphthylindenyl) zirconium dimethyl, rac-dimethylsilylenebis (2
-Methyl-4-naphthylindenyl) hafnium dichloride, rac-dimethylsilylenebis (2-methyl-)
4,5-benzoindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4,
5-benzoindenyl) zirconium dimethyl, rac
-Dimethylsilylenebis (2-methyl-4,5-benzoindenyl) hafnium dichloride, rac-dimethylsilylenebis (2-ethyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-ethyl-4) -Phenylindenyl) zirconium dimethyl, rac-dimethylsilylenebis (2
-Ethyl-4-phenylindenyl) hafnium dichloride, rac-dimethylsilylene bis (2-methyl-)
4,6-Diisopropylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4,6-diisopropylindenyl) zirconiumdimethyl, rac-dimethylsilylenebis (2-methyl-)
4,6-Diisopropylindenyl) hafnium dichloride, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylene (2,4-dimethylcyclopenta) Dienyl) (3 ', 5
′ -Dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) zirconium dimethyl, dimethylsilylene (2,4-dimethylcyclopenta) Dienyl) (3 ', 5
′ -Dimethylcyclopentadienyl) hafnium dichloride, dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) hafnium dimethyl, dimethylsilylene (2,
3,5-trimethylcyclopentadienyl) (2 ', 4
′, 5′-Trimethylcyclopentadienyl) titanium dichloride, dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ′, 4 ′, 5′-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (2,3,5-Trimethylcyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dimethyl, dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ' , 4 ', 5'-Trimethylcyclopentadienyl) hafnium dichloride, dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2
', 4', 5'-trimethylcyclopentadienyl) hafnium dimethyl.

These compounds (A) can be used as they are as the catalyst by directly combining with the compounds (B) or (B) and (C), but they can also be used by being supported on a fine particle carrier. is there. Such a fine particle carrier is an inorganic or organic compound having a particle diameter of 5 to 5.
Granular or spherical particulate solids of 300 μm, preferably 10-200 μm are used.

Among these, the inorganic compounds used for the carrier include SiO ₂ , Al ₂ O ₃ , MgO, TiO ₂ and Zn.
O or the like or a mixture thereof, for example, SiO ₂ —Al
₂ O ₃ , SiO ₂ —MgO, SiO ₂ —TiO ₂ , SiO
₂ -Al ₂ O ₃ -MgO and the like. Among these, those containing SiO ₂ or Al ₂ O ₃ as a main component are preferable.

As the organic compound used as the carrier, ethylene, propylene, 1-butene, 4-methyl-
Examples thereof include polymers or copolymers of α-olefins having 2 to 12 carbon atoms such as 1-pentene, and further polymers or copolymers of styrene or styrene derivatives.

Olefin (co) used in the composition of the present invention
The compound (B) combined with the compound (A) which is a metallocene as a catalyst component used in the production of the polymer (I) includes a compound (B-1) aluminoxane, and a compound (B-2) which reacts with the transition metal compound (A). And (B-3) one or more compounds selected from Lewis acids.

Of these, (B-1) aluminoxane is
An organoaluminum compound represented by the following general formula [Chemical formula 1] or [Chemical formula 2].

[Chemical 1]

[Chemical 2] Here, R ³ is a hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, isobutyl group, pentyl group, hexyl group, etc. Alkyl group, allyl group, 2-methylallyl group,
Examples thereof include an alkenyl group such as a propenyl group, an isopropenyl group, a 2-methyl-1-propenyl group, a butenyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cycloalkyl group such as a cyclohexyl group, and an aryl group. Of these, an alkyl group is particularly preferable, and each R ³ may be the same or different. Also, q is an integer of 4 to 30, preferably 6 to 30,
It is particularly preferably 8 to 30.

The above aluminoxane can be prepared under various known conditions. Specifically, the following method can be exemplified. (1) A method in which a trialkylaluminum is directly reacted with water using an organic solvent such as toluene or ether. (2) salts having trialkylaluminum and water of crystallization,
For example, a method of reacting with copper sulfate hydrate or aluminum sulfate hydrate. (3) A method of reacting trialkylaluminum with moisture impregnated in silica gel or the like. (4) A method in which trimethylaluminum and triisobutylaluminum are mixed and directly reacted with water using an organic solvent such as toluene or ether. (5) A method in which trimethylaluminum and triisobutylaluminum are mixed and reacted with salts having water of crystallization, such as copper sulfate hydrate and aluminum sulfate hydrate. (6) A method in which silica gel or the like is impregnated with water, triisobutylaluminum is reacted, and then trimethylaluminum is further reacted.

Further, (B-2) an ionic compound which reacts with the transition metal compound (A) to form an ionic complex (hereinafter sometimes referred to as "compound (B-2)"), and As (B-3) Lewis acid, Table 1
No. 501950, Japanese Patent Publication No. 1-502036, Japanese Patent Laid-Open No. 3-179005, Japanese Patent Laid-Open No. 3-179.
The ionic compounds and Lewis acids described in JP-A No. 006, JP-A-3-207703, JP-A-3-207704 and the like can be mentioned.

The ionic compound (B-
2) is a salt of a cationic compound and an anionic compound. The anion reacts with the transition metal compound (A) to cationize the transition metal compound (A), and forms an ion pair to stabilize the transition metal cation species. Examples of such anions include organic boron compound anions and organic aluminum compound anions. Examples of cations include metal cations, organometallic cations, carbonium cations, trityl cations, oxonium cations, sulfonium cations, phosphonium cations and ammonium cations.

Of these, ionic compounds containing a boron atom as an anion are preferable, and specifically, triethylammonium tetrakis (pentafluorophenyl) borate and tetrakis (pentafluorophenyl) borate tri-
n-butylammonium, tetrakis (pentafluorophenyl) borate triphenylammonium, tetrakis (pentafluorophenyl) methylaninium tetrakis (pentafluorophenyl) borate dimethylaninium, tetrakis (pentafluorophenyl) borate trimethylanilium, etc. Can be mentioned.

As the (B-3) Lewis acid, a boron atom-containing Lewis acid is preferable, and a compound represented by the following general formula (Formula 3) can be used.

Embedded image BR ⁴ R ⁵ R ⁶ (In the formula, R ⁴ , R ⁵ and R ⁶ may each independently have a substituent such as a fluorine atom, a methyl group and a trifluorophenyl group. Indicates a phenyl group or a fluorine atom.)

Specific examples of the compound represented by the above general formula include tri (n-butyl) boron, triphenylboron and tris [3,5-bis (trifluoromethyl) phenyl].
Boron, tris [(4-fluoromethyl) phenyl] boron, tris (3,5-difluorophenyl) boron, tris (2,4,6-trifluorophenyl) boron, tris (pentafluorophenyl) boron and the like can be mentioned. , Tris (pentafluorophenyl) boron is particularly preferred.

Here, the ratio of the transition metal compound (A) to the compound (B) used is (B-1) as the compound (B).
When aluminoxane is used, 1 to 50,000 mol, preferably 10 to 30,000 mol, and particularly preferably 10 to 30,000 mol, of Al atom in (B-1) aluminoxane per 1 mol of transition metal atom in transition metal compound (A). Preferably 50-2
It is in the range of 10,000 mol.

As the compound (B), the compound (B-
When 2) or (B-3) Lewis acid is used, the compound (B-2) or (B-3) Lewis acid is added to 0.01 to 1 mol of the transition metal atom in the transition metal compound (A). Two
It is used in the range of 000 mol, preferably 0.1 to 500 mol.

It is possible to use one or more of any of the above-mentioned compounds (B).

Further, as the organoaluminum compound which is the compound (C) used as one component of the polymerization catalyst according to the present invention, the compound represented by the following general formula (Formula 4) can be used.

Embedded image AlR ⁷ _t R ⁸ _{t ′} X _{3- (t + t} ′ ₎ (In the formula, R ⁷ and R ⁸ are hydrocarbon groups such as an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, and an aryl group. Or an alkoxy group, X is a halogen atom, and t and t ′ are 0.
<T + t ′ ≦ 3 represents an arbitrary number. )

Specific examples of the compound represented by the above general formula include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-butylaluminum, dimethylaluminum chloride and dimethylaluminum. Bromide, diethyl aluminum chloride, dialkyl aluminum halides such as diisopropyl aluminum chloride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, ethyl aluminum sesquibromide,
Examples thereof include alkylaluminum sesquihalides such as isopropylaluminum sesquichloride, and it is possible to use one or more of them.

Here, the amount of the organoaluminum compound which is the compound (C) used is such that the Al atom in the organoaluminum compound (C) is 0 to 10, relative to 1 mol of the transition metal atom in the transition metal compound (A). 000 mol, preferably 0
It is in the range of 5,000 mol, particularly preferably 0 to 3,000 mol.

Compound (A) and compound (B) or compound (A) and compound (B) thus combined.
The olefin (co) polymer (I) used in the composition of the present invention can be obtained by (co) polymerizing an olefin using a specific catalyst comprising the compound (C) and the compound (C). Known as olefin (co)
Polymerization process can be used, butane, pentane, hexane, heptane, aliphatic hydrocarbons such as isooctane,
Aliphatic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane, aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, and olefins (co- ) Slurry polymerization method for polymerization, bulk polymerization using olefin itself as a solvent, and gas phase polymerization method for carrying out (co) polymerization of olefin in a gas phase, and a solution in which a polyolefin produced by (co) polymerization is liquid Polymerization or a combination of two or more of these processes can be used.

In the polymerization of olefin, the above-mentioned specific catalyst was prepared by mixing the compound (A) and the compound (B), or the compound (A), the compound (B) and the compound (C) in an inert solvent in advance. The compound may be supplied to the polymerization reaction system, or the compound (A) and the compound (B), or the compound (A), the compound (B) and the compound (C) may be separately supplied to the polymerization reaction system. Good. Furthermore,
Prior to the main polymerization of an olefin, a small amount of an olefin, specifically, a compound (A) and a compound (B) or a catalyst obtained by combining the compound (A), a compound (B) and a compound (C) in an inert solvent, specifically, Transition metal 1 in compound (A)
The obtained olefin (co) polymer (I) can also be obtained by carrying out a preliminary activation treatment for polymerizing an olefin in an amount of about 1 g to 500 kg per millimole and then carrying out a main polymerization of the olefin after the catalyst having been subjected to the preliminary activation treatment. Is effective within the scope of the present invention.

As the olefin that can be used in the above pre-activation treatment, α-olefin having 2 to 12 carbon atoms is preferably used, and specifically, ethylene, propylene, butene, pentene, hexene, octene and 4-methyl are used. -1-
Examples include pentene, and particularly ethylene, propylene, 4
-Methyl-1-pentene is preferably used.

The specific catalyst thus prepared for use in the present invention, or the specific catalyst which has been pre-activated is used for the (co) polymerization of an olefin by the above-mentioned polymerization method. As the polymerization conditions in (1), the same polymerization conditions as in olefin (co) polymerization using a known Ziegler type catalyst are adopted. That is, the polymerization temperature is −50 to 150 ° C., preferably −10 to 100 ° C., and the polymerization pressure is atmospheric pressure (0.1 MPa) to 7 MPa.
The pressure is preferably 0.2 MPa to 5 MPa, and the polymerization time is usually about 1 minute to 20 hours. The molecular weight of the obtained olefin (co) polymer (I) can be adjusted by selecting the above-mentioned polymerization conditions and introducing hydrogen, which is a molecular weight modifier, into the polymerization system.

After completion of the (co) polymerization of the olefin, if necessary, after undergoing known post-treatment steps such as a catalyst deactivation treatment step, a catalyst residue removal step and a drying step, the catalyst is used in the present invention.
The intrinsic viscosity [η _I ] measured in tetralin at 5 ° C. is 0.
2-10 dl / g olefin (co) polymer (I)
Is obtained.

The olefin (co) polymer (II) of the present invention contains 0.01 to 5 parts by weight of (II-1) and (II-2) 10 below.
It is composed mainly of 0 parts by weight.

(II-1) High molecular weight olefin (co) polymer having an intrinsic viscosity [η _E ] measured with tetralin at 135 ° C. of 15 to 100 dl / g (II-2) High molecular weight olefin (co) Polymer (II-
Olefin (co) polymers other than 1)

Polyethylene which is a typical example of the component (II-1) is a polyethylene having an intrinsic viscosity [η _E ] of 15 to 100 dl / g measured in tetralin at 135 ° C., which is an ethylene homopolymer or An ethylene-olefin copolymer containing 50% by weight or more of ethylene polymer units, preferably an ethylene homopolymer or an ethylene-olefin copolymer containing 70% by weight or more of ethylene polymer units, particularly preferably an ethylene homopolymer. Alternatively, an ethylene-olefin copolymer containing 90% by weight or more of ethylene polymer units is suitable.
The polymers may be used alone or in combination of two or more.

When the intrinsic viscosity [η _E ] of the component (II-1) polyethylene is less than 15 dl / g, the melt tension of the polypropylene composition (representative example) which is the olefin (co) polymer (II) obtained. Is insufficient, and the upper limit of the intrinsic viscosity [η _E ] is not particularly limited, but when the difference from the intrinsic viscosity [η _P ] of the polypropylene (representative example) of the component (II-2) is large, When used as a composition (II
The dispersion of the polyethylene of the component (II-1) into the polypropylene of the component-2) becomes poor, and as a result, the melt tension does not rise. Furthermore, from the viewpoint of manufacturing efficiency, the upper limit is 100.
It is preferably about dl / g. The intrinsic viscosity [η _E ] of the component (II-1) polyethylene is 1
It is in the range of 5 to 100 dl / g, preferably 17 to 50 dl / g. In addition, the polyethylene of the component (II-1) is 1
The intrinsic viscosity [η _E ] measured in tetralin at 35 ° C is 1
Since it is necessary to make the polymer have a high molecular weight of up to 5 dl / g, it is preferable that the ethylene polymerized units are 50% by weight or more from the viewpoint of efficiency of the high molecular weight.

The olefin other than ethylene which is copolymerized with ethylene constituting the polyethylene of the component (II-1) is not particularly limited, but an olefin having 3 to 12 carbon atoms is preferably used. Specifically, propylene, 1
-Butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, 3-methyl-1-pentene and the like are mentioned, and these olefins are not only one kind but also two kinds. It may be more than.

The density of polyethylene as the component (II-1) is not particularly limited, but specifically, it is 880 to 98.
It is preferably about 0 g / l.

As the olefin (co) polymer as the component (II-2), polypropylene will be described below as a typical example. Further, the olefin (co) polymer of the component (II) will also be described as a polypropylene composition.

The polypropylene as the component (II-2) is 13
The intrinsic viscosity [η _P ] measured in tetralin at 5 ° C. is 0.
2 to 10 dl / g of crystalline polypropylene, which is a propylene homopolymer or a propylene-olefin random copolymer or a propylene-olefin block copolymer containing 50% by weight or more of propylene polymer units, and preferably propylene homopolymer. Polymer, propylene containing 90% by weight or more of propylene polymer units
It is an olefin random copolymer or a propylene-olefin block copolymer having a propylene polymerization unit content of 70% by weight or more. These (co) polymers may be not only one type but also a mixture of two or more types.

The polypropylene (II-2) has an intrinsic viscosity [η _P ] of 0.2 to 10 dl / g, preferably 0.5.
The thing of -8 dl / g is used. When the intrinsic viscosity [η _P ] of the polypropylene as the component (II-2) is less than 0.2 dl / g, the mechanical properties of the resulting polypropylene composition (II) deteriorate, and when it exceeds 10 dl / g, it is obtained. Moldability of the polypropylene composition (II) deteriorates.

The olefin other than propylene which is copolymerized with propylene constituting the polypropylene as the component (II-2) is not particularly limited, but an olefin having 2 to 12 carbon atoms is preferably used. Specifically, ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, 3-
Methyl-1-pentene and the like can be mentioned, and these olefins may be not only one type but also two or more types.

The stereoregularity of the polypropylene as the component (II-2) is not particularly limited, and any polypropylene that achieves the object of the present invention may be used as long as it is a crystalline polypropylene. Specifically, the isotactic pentad fraction (mmmm) measured by ¹³ C-NMR (nuclear magnetic resonance spectrum) is 0.80 to 0.99, preferably 0.85 to 0.99, and particularly preferably. 0.90
Polypropylene with a crystallinity of 0.99 is used.

Isotactic pentad fraction (mmm
m) is ¹³ C-NMR proposed by A. Zambelli and others (Macromolecules ⁶ , 925 (1973)).
It is the isotactic fraction in pentad units in the polypropylene molecular chain measured by
ambelli) and others (Macromolecules 8 , 687 (197
5)) It is decided according to the attribution. Specifically, a mixed solution of o-dichlorobenzene / benzene bromide = 8/2 weight ratio having a polymer concentration of 20 weight% was used and 67.20 MH was used.
z, determined at 130 ° C. As a measuring device, for example, JEOL-GX270NMR
A measuring device (made by JEOL Ltd.) is used.

The polypropylene composition (II) of the present invention contains 0.01 to 5 parts by weight, preferably 0.02 to 2 parts by weight, and particularly preferably 0.05 to 1 part by weight of the above-mentioned component (II-1) polyethylene. Parts by weight, and 100 parts by weight of polypropylene as the component (II-2). When the polyethylene of the component (II-1) is less than 0.01 parts by weight, the resulting polypropylene composition (II) has little effect of improving the melt tension,
Further, if it exceeds 5 parts by weight, the effect is saturated and the homogeneity of the obtained polypropylene composition (II) may be deteriorated, which is not preferable.

Component (II) Polyolefin Composition (II)
Melt tension of 1 and melt tension (MS) at 230 ℃
It is preferable that the intrinsic viscosity [η _II ] measured in tetralin at 35 ° C. has a relationship represented by log (MS)> 4.24 × log [η _II ] −1.05. The upper limit is not particularly limited, but since the moldability of the composition is deteriorated when the melt tension is too high, it is preferably 4.24 × lo.
g [η _II ] +0.50> log (MS)> 4.24 × log [η _II ] −1.05, more preferably 4.24 × log [η _II ] +0.24> log (MS)> 4.24
Xlog [[eta] _II ] -1.05, most preferably 4.24 * log [[eta] _II ]
+0.24> log (MS)> 4.24 × log [η _II ] −0.93.

Here, the melt tension at 230 ° C. (M
S) is a melt tension tester type 2 (manufactured by Toyo Seiki Seisakusho Co., Ltd.), which is used to heat the olefin (co) polymer composition to 230 ° C. in the apparatus to melt the olefin (co).
20 m of polymer composition from a 2.095 mm diameter nozzle
It is a value (unit: cN) obtained by measuring the tension of the filamentous polypropylene composition when the strand was extruded into the air at 23 ° C. at a speed of m / min to take it up at a speed of 3.14 m / min.

As the method for producing the polypropylene composition (II) of the present invention, any production method may be adopted as long as the melt tension of the composition is within the above range, but it will be described in detail below. It can be easily produced by adopting a method of subjecting (co) polymerizing propylene or propylene and another olefin in the presence of a catalyst preactivated by ethylene or ethylene and another olefin.

As used herein, the term "pre-activation" refers to the addition of a small amount (usually, prior to carrying out the (co) polymerization of propylene or propylene with other olefins using a catalyst for the production of polyolefins. , 5% by weight or less of the main (co) polymerization amount) means a process for (co) polymerizing an olefin. By the treatment, in the case of a homogeneous catalyst, a mixture of a small amount of an olefin (co) polymer and a homogeneous catalyst (a mixture slurry when the treatment is carried out in the presence of a solvent) is formed.
Further, in the case of a catalyst in which a transition metal compound catalyst component is supported on a carrier, the supported transition metal compound catalyst component (solid)
The olefin (co) polymer is coated (or carried) on the surface of the.

The pre-activating catalyst used for producing the polypropylene composition (II) of the present invention is the metallocene catalyst used for producing the olefin (co) polymer (I) of the present invention or the most industrially used catalyst. Although it is possible to produce from any of the transition metal compound catalyst components containing a titanium compound, a transition metal compound catalyst component containing a titanium compound as a typical example is used as a basic component, in addition to this, the following catalyst composition, ( 1) 0.0 per mol of transition metal atom
Periodic table of 1 to 1,000 mol (1991 version) Group 1 (eg Li, Na etc.), Group 2 (eg Mg etc.), Group 12 (eg Zn etc.) and Group 13 (eg Al etc.) An organometallic compound (AL1) of a metal selected from the group consisting of the metals belonging to, and (2) 0 to 1 mol of the transition metal atom.
A catalyst for producing a polyolefin, which comprises a combination of 500 mol of an electron donor (E1), and 0.01 to 100 g per 1 g of the transition metal compound component (3) supported on the catalyst.
Intrinsic viscosity [η _B ] measured in tetralin at 135 ° C
Of less than 15 dl / g Polypropylene (B) for (co) polymerization purpose, and (4) 1 g of transition metal compound catalyst component
Intrinsic viscosity [η _A ] measured in 0.01-5,000 g of tetralin at 135 ° C. is 15-100 dl / g
Which is polyethylene (A).

As the transition metal compound catalyst component in the above-mentioned pre-activated catalyst, any known catalyst component mainly composed of a transition metal compound catalyst component containing at least a titanium compound, which has been proposed for the production of polyolefin, is used. In particular, a titanium-containing solid catalyst is preferably used for industrial production.

As the titanium-containing solid catalyst component, a titanium-containing solid catalyst component containing a titanium trichloride composition as a main component (Japanese Patent Publication No. 56-3356 and Japanese Patent Publication No. 59-2857).
No. 3, JP-B-63-66323, etc.), a titanium-containing supported catalyst component containing titanium tetrachloride in a magnesium compound and containing titanium, magnesium, a halogen, and an electron donor as essential components (Japanese Patent Laid-Open Publication No. Sho 63-63). 62-10481
0, JP-A-62-104811, JP-A-6
2-104812, JP-A-57-63310, JP-A-57-63311, and JP-A-58-830.
No. 06, JP-A-58-138712, etc.) have been proposed, and any of these can be used.

As the organometallic compound (AL1), the periodic table (1991 version) Group 1, Group 2, Group 12 and Group 1
A compound having an organic group of a metal selected from the group consisting of metals belonging to Group 3, for example, an organolithium compound, an organosodium compound, an organomagnesium compound, an organozinc compound, an organoaluminum compound, etc. is used as the transition metal compound catalyst component. It can be used in combination with.

In particular, an organoaluminum compound having a general formula represented by the following formula (Formula 5) can be preferably used.

Embedded image AlR ¹ _p R ² _q X _{3- (p + q)} (In the formula, R ¹ and R ² are the same kind of a hydrocarbon group such as an alkyl group, a cycloalkyl group and an aryl group, and an alkoxy group. Or different types, X represents a halogen atom, and p and q represent a positive number of 0 <p + q ≦ 3).

Specific examples of the organoaluminum compound include trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-n-butyl aluminum, tri-i-butyl aluminum, tri-n-hexyl aluminum and tri-i-. Hexyl aluminum, trialkyl aluminum such as tri-n-octyl aluminum, diethyl aluminum chloride, di-n-propyl aluminum chloride, di-i
-Butyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide and other dialkyl aluminum monohalides, diethyl aluminum hydride and other dialkyl aluminum hydrides, ethyl aluminum sesquichloride and other alkyl aluminum sesquihalides, ethyl aluminum dichloride and other monoalkyl aluminum dihalides Other examples include alkoxyalkyl aluminum such as diethoxy monoethyl aluminum, and preferably trialkyl aluminum and dialkyl aluminum monohalide are used. These organoaluminum compounds may be used alone or in combination of two or more.

The electron donor (E1) is optionally used for the purpose of controlling the production rate and / or stereoregularity of the polyolefin. Electron donor (E1)
As, for example, ethers, alcohols, esters, aldehydes, fatty acids, ketones, nitriles, amines, amides, urea and thioureas, isocyanates, azo compounds, phosphines, phosphites, Phosphinites, hydrogen sulfide and thioethers, neoalcohols, silanols, and other organic compounds having an oxygen, nitrogen, sulfur, or phosphorus atom in the molecule, and organosilicons having a Si-O-C bond in the molecule A compound etc. are mentioned.

As the ethers, dimethyl ether,
Diethyl ether, di-n-propyl ether, di-n
-Butyl ether, di-i-amyl ether, di-n-
Pentyl ether, di-n-hexyl ether, di-i
-Hexyl ether, di-n octyl ether, di-i
-Octyl ether, di-n-dodecyl ether, diphenyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and the like, and alcohols such as methanol and
Ethanol, propanol, butanol, pentanol, hexanol, octanol, 2-ethylhexanol, allyl alcohol, benzyl alcohol, ethylene glycol, glycerin and the like, and phenols include phenol, cresol, xylenol, ethylphenol and naphthol. .

Examples of the esters include methyl methacrylate, methyl formate, methyl acetate, methyl butyrate, ethyl acetate, vinyl acetate, acetic acid-n-propyl acetate, acetic acid-i-propyl, butyl formate, amyl acetate, acetic acid-n-butyl acetate. , Octyl acetate, phenyl acetate, ethyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluate, ethyl toluate, methyl anisate, Monocarboxylic acid esters such as ethyl anisate, propyl anisate, phenyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate and ethyl phenylacetate , Diethyl succinate, diethyl malonate , Diethyl butylmalonate, dibutyl maleate, diethyl butylmaleate, etc., aliphatic polycarboxylic acid esters, monomethyl phthalate, dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, mono-phthalate n-butyl, di-n-butyl phthalate, di-i-butyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, i-diethyl phthalate, i-
Dipropyl phthalate, i-dibutyl phthalate, i-2-diethylhexyl phthalate, diethyl terephthalate,
Examples thereof include aromatic polyvalent carboxylic acid esters such as dipropyl terephthalate, dibutyl terephthalate, and di-i-butyl naphthalene dicarboxylate.

As the aldehydes, acetaldehyde, propionaldehyde, benzaldehyde and the like, and as the carboxylic acids, formic acid, acetic acid, propionic acid, butyric acid,
Oxalic acid, succinic acid, acrylic acid, maleic acid, valeric acid, monocarboxylic acids such as benzoic acid and acid anhydrides such as benzoic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride, ketones, acetone, methyl ethyl ketone,
Examples include methyl-i-butyl ketone and benzophenone.

Examples of the nitrogen-containing compound include nitriles such as acetonitrile and benzonitrile, methylamine, diethylamine, tributylamine, triethanolamine, β (N, N-dimethylamino) ethanol, pyridine, quinoline, α-picoline, 2 , 4,6-trimethylpyridine, 2,2,5,6-tetramethylpiperidine,
2,2,5,5, tetramethylpyrrolidine, N, N, N
′, N′-tetramethylethylenediamine, aniline,
Amine such as dimethylaniline, formamide, hexamethylphosphoric triamide, N, N, N ', N', N "
-Pentamethyl-N'-β-dimethylaminomethylphosphoric acid triamide, amides such as octamethylpyrophosphoramide, ureas such as N, N, N ', N'-tetramethylurea, phenyl isocyanate, toluyl isocyanate, etc. Examples thereof include isocyanates and azo compounds such as azobenzene.

Examples of the phosphorus-containing compound include ethylphosphine, triethylphosphine, di-n-octylphosphine, tri-n-octylphosphine, triphenylphosphine, triphenylphosphine oxide and other phosphines, dimethylphosphite, di-n-. Examples include phosphites such as octyl phosphite, triethyl phosphite, tri-n-butyl phosphite, and triphenyl phosphite.

In the pre-activated catalyst, polyethylene (A) has an intrinsic viscosity [η _A ] measured in tetralin at 135 ° C. of 15 to 100 dl / g, preferably 17 to 5
Ethylene homopolymers in the range of 0 dl / g or copolymers of ethylene and olefins having 3 to 12 carbon atoms with 50% by weight or more, preferably 70% by weight or more, and more preferably 90% by weight or more ethylene polymerization units. And finally constitutes the polyethylene of the component (II-1) in the polypropylene composition of the present invention. Therefore, (II-1)
The intrinsic viscosity of the polyethylene component [eta _E] and the intrinsic viscosity [eta _A] of the polyethylene (A), the relation of [eta _E] = [eta _A].

The amount of polyethylene (A) supported per 1 g of the transition metal compound catalyst component is 0.01 to 5,000 g, preferably 0.05 to 2,000 g, and more preferably 0.1 to 1,000 g. When the loading amount per 1 g of the transition metal compound catalyst component is less than 0.01 g, the effect of improving the melt tension of the polypropylene composition (II) finally obtained by the main (co) polymerization is insufficient, and 5,000 g When it exceeds the above range, not only the improvement of these effects is not remarkable but also the homogeneity of the finally obtained polypropylene composition (II) may be deteriorated, which is not preferable.

On the other hand, polypropylene (B) has an intrinsic viscosity [η _B ] of 15 dl / measured in tetralin at 135 ° C.
obtained by regular (co) polymerization less than g (II-2)
It is a polypropylene having the same composition as the component polypropylene, and finally (II-
2) Incorporated as part of the polypropylene component.
Polypropylene (B) is a component that imparts dispersibility to polyethylene (A) in the finally obtained polypropylene composition, and also in that sense, its intrinsic viscosity [η _B ] is the intrinsic viscosity of polyethylene (A). The intrinsic viscosity [η] of the polypropylene composition (II) finally obtained, which is smaller than the viscosity [η _A ]
_II ] is preferable.

On the other hand, the amount of polypropylene (B) supported per 1 g of the transition metal compound catalyst component is 0.01 to 100.
g, in other words, a range of 0.001 to 1% by weight based on the finally obtained polypropylene composition is preferable. When the carried amount of polypropylene (B) is small, the dispersibility of polyethylene (A) in the intended polypropylene composition becomes insufficient, and when it is too large, the dispersibility of polyethylene (A) in the polypropylene composition is saturated. Not only does this lead to a decrease in the production efficiency of the pre-activated catalyst.

In the present invention, the preactivating catalyst used for producing the polypropylene composition (II) is a transition metal compound catalyst component containing at least a titanium compound, an organometallic compound (AL1) and optionally an electron used. In the presence of a catalyst for producing a polyolefin, which comprises a combination of a donor (E1), propylene for the purpose of this (co) polymerization or propylene and other olefins are preliminarily (co) polymerized to produce polypropylene (B), and then ethylene. Alternatively, ethylene and other olefins are pre-activated (co) polymerized to produce polyethylene (A), and the transition metal compound catalyst component is supported by pre-activation treatment to support polypropylene (B) and polyethylene (A). .

In this preliminary activation treatment, a transition metal compound catalyst component containing a titanium compound, and 0.01 to 1,000 mols, preferably 0.05 to 500 mols, of organic metal relative to 1 mol of the transition metal in the catalyst component. The compound (AL1) and 0 to 500 mol, preferably 0 to 100 mol, of the electron donor (E1) per 1 mol of the transition metal in the catalyst component are used in combination as a catalyst for producing a polyolefin.

This catalyst for producing polyolefin is converted into the transition metal atom in the catalyst component in an amount of 0.001 to 5,000 mmol, preferably 0, per liter of (co) polymerization of ethylene or ethylene and other olefins. ．
0.01 to 500 g of propylene or a mixture of propylene and other olefins is supplied in the absence of a solvent or in a solvent of up to 100 liters per 1 g of a transition metal compound catalyst component. Preliminary (co) polymerized transition metal compound catalyst component 1
0.01 to 100 g of polypropylene (B) is produced per g and then 0.01 g to 10,000 of ethylene or a mixture of ethylene and ethylene and other olefins.
By supplying 0 g of the pre-activated (co) polymerization to produce 0.01 to 5,000 g of polyethylene (A) per 1 g of the transition metal compound catalyst component, polypropylene (B) is added to the transition metal compound catalyst component. And polyethylene (A) is coated and supported. In the present specification, the term "polymerization volume" means the volume of the liquid phase portion in the polymerization vessel in the case of liquid phase polymerization, and the volume of the gas phase portion in the polymerization vessel in the case of gas phase polymerization. To do.

The amount of the transition metal compound catalyst component used is preferably within the above range in order to maintain an efficient and controlled (co) polymerization reaction rate of propylene. Also,
If the amount of the organometallic compound (AL1) used is too small, the (co) polymerization reaction rate will be too slow, and even if it is increased, not only a corresponding increase in the (co) polymerization reaction rate can be expected, but finally it is obtained. This is not preferable because the amount of the organometallic compound (AL1) remaining in the resulting polypropylene composition is large. Furthermore, if the amount of the electron donor (E1) used is too large, the (co) polymerization reaction rate decreases. If the amount of the solvent used is too large, not only a large reaction vessel is required, but also it becomes difficult to control and maintain an efficient (co) polymerization reaction rate.

The preactivation treatment is carried out, for example, by an aliphatic hydrocarbon such as butane, pentane, hexane, heptane, octane, isooctane, decane and dodecane, an alicyclic hydrocarbon such as cyclopentane, cyclohexane and methylcyclohexane, toluene, Aromatic hydrocarbons such as xylene and ethylbenzene, as well as inert solvents such as gasoline fractions and hydrogenated diesel oil fractions, can be performed in the liquid phase using the olefin itself as a solvent, and can also be used without using a solvent. It is also possible to do it in phase.

The preliminary activation treatment may be carried out in the presence of hydrogen, but the intrinsic viscosity [η _A ] is 15 to 100 dl.
It is preferable not to use hydrogen in order to produce a high-molecular-weight polyethylene (A) of / g.

In the preliminary activation treatment, the preliminary (co) polymerization conditions of propylene or a mixture of propylene and other olefins are such that polypropylene (B) is produced in an amount of 0.01 to 100 g per 1 g of the transition metal compound catalyst component. What is necessary is just to carry out, and it is usually carried out at a temperature of −40 ° C. to 100 ° C. and a pressure of 0.1 MPa to 5 MPa for 1 minute to 24 hours. The pre-activation (co) polymerization conditions of ethylene or a mixture of ethylene and other olefins are as follows: polyethylene (A) is 0.01 to 5,000 g, preferably 0.05 to 2, per 1 g of the transition metal compound catalyst component. 0
There is no particular limitation so long as it is produced in an amount of 00 g, more preferably 0.1 to 1,000 g.
40 ° C to 40 ° C, preferably -40 ° C to 30 ° C, and more preferably -40 ° C to 20 ° C at a relatively low temperature,
0.1 MPa to 5 MPa, preferably 0.2 MPa to 5
Under a pressure of MPa, particularly preferably 0.3 MPa to 5 MPa, it is 1 minute to 24 hours, preferably 5 minutes to 18 hours, particularly preferably 10 minutes to 12 hours.

After the preliminary activation treatment, addition polymerization is carried out with propylene or a mixture of propylene and other olefins for the purpose of suppressing the reduction of the main (co) polymerization activity due to the preliminary activation treatment. ,
0.01 to 100 g per 1 g of transition metal compound catalyst component
Of polypropylene (C) may be produced. In this case, the organometallic compound (AL1), the electron donor (E
1), the solvent, and the amount of propylene or a mixture of propylene and other olefins used can be in the same range as in the preactivation polymerization with ethylene or a mixture of ethylene and another olefin, but the transition metal atom 1 0.005 to 10 mol per mol, preferably 0.1.
It is preferably carried out in the presence of 01 to 5 mol of electron donor. Regarding reaction conditions, the reaction is carried out at a temperature of −40 to 100 ° C. and a pressure of 0.1 to 5 MPa for 1 minute to 24 hours.

Organometallic compounds (A
Regarding L1), the electron donor (E1), and the type of solvent,
The same pre-activated polymerization with ethylene or a mixture of ethylene and other olefins can be used, and the same composition as the main (co) polymerization purpose is used for propylene or a mixture of propylene and other olefins. . The intrinsic viscosity [η _C ] of polypropylene produced by addition polymerization is in a range smaller than the intrinsic viscosity [η _A ] of polyethylene (A), and is finally incorporated as a part of polypropylene after the (co) polymerization. .

The preactivation catalyst may be the olefin main (co) polymerization catalyst as it is or may further contain an additional organometallic compound (AL2) and an electron donor (E2).
2 to 1 carbon atoms for obtaining the desired polypropylene composition
It can be used for the main (co) polymerization of two olefins.

The above-mentioned olefin main (co) polymerization catalyst is the above-mentioned pre-activated catalyst and the transition metal atom 1 in the pre-activated catalyst.
The total amount of the organometallic compound (AL2) and the organometallic compound (AL1) in the activated catalyst per mole (AL1 + AL2)
0.05-3,000 mol, preferably 0.1-1,
000 mol and 1 mol of the transition metal atom in the activated catalyst, the total of (E1 + E2) of the electron donor (E2) and the electron donor (E1) in the preactivated catalyst is 0 to 5,000 mol, preferably It consists of 0 to 3,000 mol.

Content of organometallic compound (AL1 + AL
If 2) is too small, the (co) polymerization reaction rate in the main (co) polymerization of propylene or propylene and other olefins is too slow, while if it is excessively large, the (co) polymerization reaction rate is as high as expected. Not only is there no increase, it is inefficient, and the residual amount of the organometallic compound remains in the finally obtained polypropylene composition, which is not preferable. Further, the content of the electron donor (E1 + E
If 2) is too large, the (co) polymerization reaction rate will be significantly reduced.

Olefin The kinds of the organometallic compound (AL2) and the electron donor (E2) additionally used as necessary in the catalyst for the main (co) polymerization are the above-mentioned organometallic compound (AL1) and the electron donor. The same thing as (E1) can be used. In addition, one kind may be used alone, or two or more kinds may be used in combination. Further, it may be the same as or different from the one used in the preliminary activation treatment.

Olefin The main (co) polymerization catalyst includes the solvent present in the pre-activated catalyst, unreacted olefin,
Organometallic compound (AL1) and electron donor (E1)
Etc. were removed by filtration or decantation to obtain a powder or a suspension obtained by adding a solvent to this powder, an additional organometallic compound (AL2) and optionally an electron donor (E2) May be combined, and the present solvent and unreacted olefin are removed by evaporation under reduced pressure or by evaporating with an inert gas flow, etc., or a suspension obtained by adding a solvent to the powder or granular material. If desired, the organometallic compound (AL2) and the electron donor (E2) may be combined.

In the method for producing a modified polypropylene composition according to the second aspect of the present invention, the amount of the pre-activated catalyst or the olefin main (co) polymerization catalyst used is such that the transition amount in the pre-activated catalyst is 1 liter of the polymerization volume. Converted to metal atoms,
0.001-1,000 mmol, preferably 0.00
Use 5-500 mmol. By setting the amount of the transition metal compound catalyst component used in the above range, an efficient and controlled (co) polymerization reaction rate of propylene or a mixture of propylene and a composition olefin can be maintained.

The (co) polymerization of propylene or a mixture of propylene and other olefins in the production of the polypropylene composition (II) using the above preactivated catalyst in the present invention is carried out by the olefin (co-polymerization) known as the polymerization process. ) Polymerization processes can be used, specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, isooctane, decane and dodecane, and alicyclic groups such as cyclopentane, cyclohexane and methylcyclohexane. Slurry polymerization method for carrying out (co) polymerization of olefins in hydrocarbons, aromatic hydrocarbons such as toluene, xylene, ethylbenzene, etc., as well as in inert solvents such as gasoline fractions and hydrogenated diesel oil fractions, olefins themselves Polymerization of olefin (co) polymerization in the gas phase Gas phase polymerization method in which in practice, further (co) polymerization process polyolefin produced by polymerization liquid phase polymerization is liquid, or a combination of two or more of these processes can be used.

When any of the above-mentioned polymerization processes is used, the polymerization temperature is 20 to 120 ° C., preferably 30 to 100 ° C., and particularly preferably 40 to 100 as polymerization conditions.
In the range of ℃, the polymerization pressure is 0.1 to 5 MPa, preferably 0.3 to 5 MPa, continuous, semi-continuous,
Alternatively, the polymerization time of 5 minutes to 24 hours is adopted batchwise. By employing the above-mentioned polymerization conditions, the polypropylene of the component (II-2) can be produced with high efficiency and controlled reaction rate.

In a more preferred embodiment of the method for producing the polypropylene composition (II) of the present invention, the intrinsic viscosity of the polypropylene of the component (II-2) produced in the (co) polymerization and the polypropylene composition finally obtained is [Η
_II ] is 0.2 to 10 dl / g, preferably 0.7 to 5 d
Polymerization conditions are selected such that the polypropylene composition (II) is in the range of 1 / g and the polyethylene (A) derived from the pre-activated catalyst used is in the range of 0.01 to 5% by weight. To do. Further, the molecular weight of the (co) polymer obtained by using hydrogen during the polymerization can be adjusted in the same manner as in the known olefin polymerization method.

After the completion of the main (co) polymerization, if necessary, known post-treatment steps such as a catalyst deactivation treatment step, a catalyst residue removal step, a drying step, etc. are carried out to obtain the desired high melt tension and high crystallization temperature. A polypropylene composition having is finally obtained.

In the method for producing the polypropylene composition (II) of the present invention, a method is used in which a high-molecular-weight polyethylene (A) is produced by a preliminary activation step and is uniformly dispersed in the finally obtained polypropylene composition. Therefore, it is possible to prepare the required amount of the pre-activated catalyst in a batch, while the main (co) polymerization of propylene or propylene and other olefins uses an existing process to carry out normal olefin (co) polymerization. So you can do
It is possible to maintain the same production amount as compared with usual polyolefin production.

By adopting the method for producing a polypropylene composition (II) using the pre-activated catalyst of the present invention, the above-mentioned melt tension (MS) at 230 ° C. and 13
A polypropylene composition satisfying the relationship with the intrinsic viscosity [η _II ] measured in tetralin at 5 ° C. can be easily obtained.

The olefin (co) polymer composition of the present invention is the olefin (co) polymer (I) thus obtained.
, 99 to 50% by weight, olefin (co) polymer (II)
Is 1 to 50% by weight.

The olefin (co) polymer composition of the present invention contains an antioxidant, an ultraviolet absorber, an antistatic agent, a nucleating agent, a lubricant, a flame retardant and an anti-blocking agent as long as the object of the present invention is not impaired. Various additives such as agents, colorants, inorganic or organic fillers, and various synthetic resins can be blended, and are usually melted and kneaded by heating, and various molded products in a pellet state cut into granules. To be used for manufacturing.

The olefin (co) polymer composition of the present invention can be produced by a known method, for example, the following method. (1) A method of mechanically blending the olefin (co) polymers (I) and (II), and optionally other components, using an extruder, a kneader or the like. (2) The olefin (co) polymers (I) and (II), and optionally other components are added to a suitable good solvent (eg, hexane, heptane, decane, cyclohexane, benzene, toluene, xylene, etc.). A hydrocarbon solvent) and then removing the solvent. (3) The olefin (co) polymers (I) and (II), and optionally other components, are separately dissolved in a suitable good solvent to prepare a solution, which is then mixed, and then the solvent is added. How to remove. (4) A method in which the above methods (1) to (3) are combined. (5) Polymerization is performed in two or more stages under different reaction conditions,
The olefin (co) polymer (I) is produced in at least one stage and the (II) is produced in another stage, or a plurality of polymerizers are used and one polymerizer (I) is used. And (II) are respectively produced in the other polymerization vessel.

The olefin (co) polymer composition of the present invention obtained as described above had a melt tension (MS) at 230 ° C. and a melt flow index (MFR) measured at 230 ° C. under a load of 21.18 N. , (Log (MS)> − 1.28 × log (MFR) +0.
Have 44 relationships.

The olefin (co) polymer composition of the present invention thus obtained from the metallocene catalyst system has a high melt tension and is excellent in moldability.

【Example】

The present invention will be described in more detail below with reference to examples and comparative examples. The definitions of the terms used in Examples and Comparative Examples and the measuring methods are as follows.

Intrinsic viscosity [η]: Intrinsic viscosity measured in tetralin at 135 ° C. by an Ostwald viscometer (manufactured by Mitsui Toatsu Chemicals, Inc.) (unit: dl /
g). Melt flow rate (MFR): JIS K72
The value (unit: g / 10) measured under the condition 14 of Table 1 (21.18N load, 230 ° C. condition) in accordance with
Minutes)

Melt tension (MS): value measured by melt tension tester type 2 (manufactured by Toyo Seiki Seisaku-sho, Ltd.) (unit: cN)

Melting point (Tm): Using an DSC7 differential scanning calorimeter (manufactured by Perkin Elmer), the olefin (co) polymer composition was heated from room temperature to 230 ° C. under a temperature rising condition of 30 ° C./min. Then, after holding at the same temperature for 10 minutes, -2
The temperature was lowered to −20 ° C. at 0 ° C./min, and the temperature was kept for 10 minutes at the same temperature, and then the temperature showing a peak during melting under the temperature rising condition of 20 ° C./min was taken as the melting point.

Crystallization temperature (Tc): Using an DSC7 differential scanning calorimeter (manufactured by Perkin-Elmer), the olefin (co) polymer composition was heated from room temperature to 230 ° C. under a temperature rising condition of 30 ° C./min. After raising the temperature and holding at the same temperature for 10 minutes,
The temperature is lowered to -20 ° C at -20 ° C / min, and 10 is kept at the same temperature.
After holding the temperature for 20 minutes, the temperature was raised to 230 ° C under a temperature rising condition of 20 ° C / minute, and after holding at the same temperature for 10 minutes, the temperature was lowered to 150 ° C at -80 ° C / minute. 5 ° C /
A value obtained by measuring the temperature showing the maximum peak during crystallization while lowering the temperature in minutes (unit: ° C).

Molecular weight distribution (Mw / Mn): Mw, Mn, M
Each w / Mn is calculated based on the measurement result of gel permeation chromatography (GPC) according to the following method. That is, when the polymer concentration is 0.05% by weight
-Using a dichlorobenzene solution, the column is a mixed polystyrene gel column (for example, PSKge manufactured by Tosoh Corporation)
1 GMH6-HT) and measured at 135 ° C. As the measuring device, for example, GPC-150C manufactured by Waters Co. is used.

[0117]

Example 1 (1) Production of Olefin (Co) polymer (I) (Propylene Polymerization) After replacing a stainless steel reactor equipped with a stirrer and having an internal volume of 100 dm ^{3 with} a stirrer with nitrogen gas, the reaction was carried out. Toluene 50dm ³ , toluene solution of methylaluminoxane in the container (manufactured by Tosoh Akzo Co., Ltd., trade name: MMAO, concentration: 2
(mol / dm ³ ) is ^2.3 mol in terms of Al atom and chiral dimethylsilylene (2,3,5) as metallocene.
-Trimethylcyclopentadienyl) (2 ', 4', 5 '
-Trimethylcyclopentadienyl) hafnium dichloride 2.1 × 10 ^-4 mol and meso-dimethylsilylene (2,3,5-trimethylcyclopentadienyl)
(2 ', 3', 5'-trimethylcyclopentadienyl)
A mixture of hafnium dichloride 0.2 × 10 ⁻⁴ mol was added at 20 ° C. with toluene 0.3 dm ³ . Subsequently, after introducing 0.08 mol of hydrogen, the temperature inside the polymerization vessel was set to 30 ° C., and under the condition of the polymerization temperature of 30 ° C., propylene was continuously added to 4 times while maintaining the gas phase pressure inside the polymerization vessel at 0.8 MPa. It was fed into the polymerization vessel for a period of time to carry out the main polymerization of propylene.

After completion of the polymerization, unreacted propylene was discharged from the inside of the polymerization reactor, 2-propanol ³ dm ³ was charged into the polymerization reactor, and the mixture was stirred for 10 minutes at 30 ° C. to deactivate the catalyst. Subsequently, hydrogen chloride aqueous solution (concentration: 12 mol / dm ³ )
It was added 0.2Dm ³ and methanol 8dm ^3, 60
It processed at 30 degreeC for 30 minutes. After the treatment, stirring was stopped and the aqueous phase portion was removed from the lower part of the polymerization reactor, and then the same amount of hydrogen chloride aqueous solution and methanol were added and the same operation was repeated. Then,
Aqueous sodium hydroxide solution (concentration: 5 mol / dm ³ )
0.02 dm ³ , water 2 dm ³ , and methanol 2 d
m ^{3 was} added, and the mixture was stirred at 30 ° C. for 10 minutes. After the treatment, stirring was stopped and the aqueous phase was removed from the bottom of the polymerization vessel,
After further adding 8 dm ³ of water and stirring for 10 minutes at 30 ° C,
After the operation of removing the water phase portion was repeated twice, the polymer slurry was taken out from the polymerization vessel, filtered and dried to have an MFR of 3.6 dg / min and an intrinsic viscosity [η _I ] of 1.92 dl.
3.2 kg of polypropylene composition (I), which is the olefin (co) polymer (I) of the present invention, was obtained.

(2) Production of olefin (co) polymer (II) (2-1) Preparation of transition metal compound catalyst component In a stainless reactor equipped with a stirrer, decane 0.
3 liters, 48 g of anhydrous magnesium chloride, 170 g of n-butyl orthotitanate and 195 g of 2-ethyl-1-hexanol were mixed, and the mixture was stirred at 130 ° C. for 1 hour.
It was heated and dissolved for a period of time to form a uniform solution. This homogeneous solution was heated to 70 ° C., 18 g of di-i-butyl phthalate was added with stirring, and after 1 hour, 520 g of silicon tetrachloride was added over 2.5 hours to precipitate a solid, and further 70 ° C.
It was heated and held for 1 hour. The solid was separated from the solution and washed with hexane to give a solid product.

The total amount of solid product is mixed with 1.5 liters of titanium tetrachloride dissolved in 1.5 liters of 1,2-dichloroethane, then 36 g of di-i-butyl phthalate are added and the mixture is stirred at 100 ° C. for 2 hours. After reacting for a period of time, the liquid phase portion was removed by decantation at the same temperature, 1.5 liters of 1,2-dichloroethane and 1.5 liters of titanium tetrachloride were added again, and the mixture was stirred and maintained at 100 ° C. for 2 hours, and hexane was added. 2.8% by weight titanium after washing with
A titanium-containing supported catalyst component (transition metal compound catalyst component) containing was obtained.

(2-2) Preparation of pre-activated catalyst After replacing a stainless steel reactor with an inclined blade with an internal volume of 5 liters with nitrogen gas, n-hexane 2.8 liters,
Triethylaluminum (organometallic compound (AL1))
4 gm and 9.0 g of the titanium-containing supported catalyst component prepared in the preceding paragraph (5.26 mmole in terms of titanium atom)
After the addition, 20 g of propylene was supplied, and prepolymerization was performed at -2 ° C for 10 minutes.

Separately, the polymer produced by the prepolymerization carried out under the same conditions was analyzed, and 2 g of propylene became polypropylene (B) per 1 g of the titanium-containing supported catalyst component. Intrinsic viscosity [η _B ] measured by 2.8 dl / g
Met.

After the reaction time was completed, unreacted propylene was discharged to the outside of the reactor, the gas phase part of the reactor was replaced with nitrogen once, and then the temperature in the reactor was kept at -1 ° C while Pre-activation was carried out by continuously supplying ethylene to the reactor for 2 hours so that the internal pressure was maintained at 0.59 MPa.

Separately, as a result of analyzing the polymer produced by the pre-activation polymerization carried out under the same conditions, 24 g of the polymer was present per 1 g of the titanium-containing supported catalyst component, and the measurement was carried out in tetralin at 135 ° C. of the polymer. The intrinsic viscosity [η _T2 ] was 31.4 dl / g.

The amount (W ₂ ) of polyethylene (A) per 1 g of the titanium-containing supported catalyst component produced by the preactivation polymerization with ethylene is the amount of the polymer produced per 1 g of the titanium-containing supported catalyst component after the preactivation treatment. The difference between (W _T2 ) and the production amount (W ₁ ) of polypropylene (B) per 1 g of the titanium-containing supported catalyst component after prepolymerization is obtained by the following formula. W ₂ = W _T2- W ₁

The intrinsic viscosity [ηA] of polyethylene (A) produced by pre-activation polymerization with ethylene is the intrinsic viscosity [η] of polypropylene (B) produced by pre-polymerization.
_B ] and the intrinsic viscosity [η _T2 ] of the polymer produced by the pre-activation treatment are calculated by the following equation. [Eta _A] = ([eta _T2] × W _T2 - [eta _B] × W ₁₎ / (W _T2
-W ₁ ) = [η _E ] The amount of polyethylene (A) produced by preactivation polymerization with ethylene according to the above formula was 22 g per 1 g of the titanium-containing supported catalyst component, and the intrinsic viscosity [η _A ] was 34.0 dl /
It was g.

After the reaction time was completed, unreacted ethylene was discharged to the outside of the reactor, the gas phase part of the reactor was replaced with nitrogen once, and then diisopropyldimethoxysilane (electron donor (E1)) was placed in the reactor. After 1.6 mmol was added, 20 g of propylene was supplied and maintained at 1 ° C. for 10 minutes to carry out addition polymerization after the preliminary activation treatment. Separately, the analysis result of the polymer produced by the addition polymerization carried out under the same conditions shows that 26 g of the polymer was present per 1 g of the titanium-containing supported catalyst component,
In addition, the intrinsic viscosity [η _T3 ] of the polymer measured in tetralin at 135 ° C. was 29.2 dl / g, and the production amount (W3) of polypropylene produced by the addition polymerization calculated in the same manner as described above was The amount of the type catalyst component was 2 g per 1 g, and the intrinsic viscosity [η _C ] was 2.8 dl / g.

After completion of the reaction time, unreacted propylene was discharged to the outside of the reactor, and the gas phase part of the reactor was replaced with nitrogen once,
A pre-activated catalyst slurry for the main (co) polymerization was prepared.

(2-3) Production of polypropylene composition (II) (main (co) polymerization of propylene) After a nitrogen substitution was carried out on a stainless steel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, n-hexane was added at 20 ° C. 24
0 liter, 780 mmol of triethylaluminum (organometallic compound (AL2)), 78 mmol of diisopropyldimethoxysilane (electron donor (E2)) and 1/2 volume of the preactivated catalyst slurry obtained above were charged into a polymerization vessel. did. Subsequently, 55 liters of hydrogen was introduced into the polymerization vessel, the temperature was raised to 70 ° C., and propylene was continuously added under the condition of the polymerization temperature of 70 ° C. while maintaining the gas phase pressure in the polymerization vessel at 0.79 MPa. Was fed into the polymerization vessel for 2 hours to carry out main polymerization of propylene.

After the lapse of the polymerization time, 1 liter of methanol was introduced into the polymerization vessel, the catalyst deactivation reaction was carried out at 70 ° C. for 15 minutes, the unreacted gas was continuously discharged, the solvent was separated, and the polymer was dried. , MFR is 5.8 dg / min. , Polymer having intrinsic viscosity [η _II ] of 1.81 dl / g 40.0 k
g was obtained. The obtained polymer had a polyethylene (A) content of 0.
25% by weight of the polypropylene composition (II),
-2) The intrinsic viscosity [η _P ] of the component polypropylene is 1.
It was 81 dl / g.

The polypropylene composition (II) thus obtained had a melt tension of 5.1 cN.

(3) Olefin (co) polymer (I), (I
Blend of I) 90 parts by weight of the polypropylene composition (I) prepared as above, 10 parts by weight of the polypropylene composition (II), 0.1 part by weight of 2,6-di-t-butyl-p-cresol. Parts and 0.1 part by weight of calcium stearate were mixed, and the mixture was granulated at 230 ° C. using an extruder having a screw diameter of 40 mm to form pellets. When the various physical properties of the pellet were evaluated and measured, the MFR was 3.9.
dg / min, melting point 164.3 ° C., crystallization temperature 12
The melt tension (MS) was 0.1 c and 0.8 cN. The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography was 2.1. Other physical properties are shown in Table 1.

[0133]

Example 2 80 parts by weight of the polypropylene composition (I) produced in Example 1, 20 parts by weight of the polypropylene composition (II), 0.1 parts of 2,6-di-t-butyl-p-cresol were used. Part by weight and 0.1 part by weight of calcium stearate were mixed, and the mixture was granulated at 230 ° C. using an extrusion granulator having a screw diameter of 40 mm to obtain pellets. Various physical properties of pellets were evaluated and measured, and MFR
Was 4.0 dg / min, the melting point was 164.5 ° C, the crystallization temperature was 119.7 ° C, and the melt tension (MS) was 1.0 cN. The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography was 2.0.
Other physical properties are shown in Table 1.

[0134]

Example 3 70 parts by weight of the polypropylene composition (I) produced in Example 1, 30 parts by weight of the polypropylene composition (II) and 0.1 part of 2,6-di-t-butyl-p-cresol. Part by weight and 0.1 part by weight of calcium stearate were mixed, and the mixture was granulated at 230 ° C. using an extrusion granulator having a screw diameter of 40 mm to obtain pellets. Various physical properties of pellets were evaluated and measured, and MFR
Was 4.1 dg / min, the melting point was 164.5 ° C, the crystallization temperature was 121.0 ° C, and the melt tension (MS) was 1.4 cN. The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography was 2.2.
Other physical properties are shown in Table 1.

[0135]

COMPARATIVE EXAMPLE 1 100 parts by weight of the polypropylene composition (I) prepared in Example 1, 2,6-di-t-butyl-p
-0.1 parts by weight of cresol and 0.1 parts by weight of calcium stearate are mixed and the mixture is screwed to a screw diameter of 40
Pelletized by granulating at 230 ° C. using a mm extrusion granulator. When various physical properties of the pellet were evaluated and measured, the MFR was 3.9 dg / min and the melting point was 164.6.
C., the crystallization temperature was 119.4 ° C., and the melt tension (MS) was 0.4 cN. The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography was 1.9. Other physical properties are shown in Table 1.

[0136]

[Table 1]

As is apparent from Table 1, it was confirmed that the olefin (co) polymers obtained from the metallocene catalyst system of the examples of the present invention had a high melt tension.

[0138]

Example 4 (1) Production of Olefin (Co) polymer (I) (Propylene Polymerization) [Preparation of Supported Catalyst] Sufficiently dried and N2 substituted 50
In a 0 ml flask, 0.52 g (0.9 mmol) of dimethylsilylenebis (2-methyl, 4,5-benzoindenyl) zirconium dichloride and a toluene diluted product of methylaluminoxane were converted to Al atoms at 267 mmo.
1 was added and reacted for 10 minutes. Then, at 800 ℃ 8
10 g of silica (Grace Davisson) that had been calcined for an hour was added and stirred for 10 minutes. Thereafter, a slight flow of N ₂ was added from the bottom while applying vacuum from the top of the vessel. The mixture was heated at 70 ° C. while evaporating the solvent for 9 hours. The dried solid was cooled overnight at room temperature. 250 ml of the solid catalyst thus obtained and isopentane were dried and dried in a 500 ml N ₂ -substituted flask, and the mixture was cooled to 0 ° C. Then, ethylene was continuously added at a flow rate of 80 ml / min for 4 hours to carry out prepolymerization. Then, the supernatant was decanted and further decanted and washed four times with 100 ml of isopentane. Further, it was vacuum dried at room temperature for 2 hours to prepare 35 g of a supported catalyst.

[Propylene Polymerization] A stainless steel reactor equipped with an inclined blade and having an internal volume of 100 dm ³ and equipped with a stirrer was replaced with nitrogen gas, and then 33 d of n-hexane was charged in the reactor.
17 mmol of m ³ and triethylaluminum were added and stirred for 5 minutes. Then, 3.6 g of the supported catalyst adjusted as described above was added while maintaining the temperature in the reactor at 50 ° C., immediately after which propylene monomer was started to be fed into the reactor, and the gas phase pressure in the polymerization reactor was adjusted to 1 While maintaining at 1 MPa, propylene was continuously fed into the polymerization vessel for 2 hours to carry out propylene polymerization at 50 ° C. The powder obtained is 2.6K
It was g. As a result of analyzing the obtained powder, MFR
The viscosity was 4.0 g / 10 min and the intrinsic viscosity was 1.88 dl / g.

(2) Production of polypropylene composition (II) A polypropylene composition (II) was produced in the same manner as in Example 1.

(3) Olefin (co) polymer (I),
Blend of (II) 90 parts by weight of the polypropylene composition (I) produced as described above, 10 parts by weight of the polypropylene composition (II), 2,6-di-t-butyl-p-cresol 0.1. 1 part by weight and 0.1 part by weight of calcium stearate are mixed, and the mixture is screw diameter 40 mm.
The pelletizer was used to granulate at 230 ° C. using When various physical properties of the pellet were evaluated and measured, the MFR was 4.0 dg / min and the melt tension (MS) was 0.8 cN. The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography was 2.0.

[0142]

Example 5 80 parts by weight of the polypropylene composition (I) produced in Example 4, 20 parts by weight of the polypropylene composition (II), and 01 parts by weight of 2,6-di-t-butyl-p-cresol. , And 0.1 part by weight of calcium stearate were mixed, and the mixture was granulated at 230 ° C. using an extruder having a screw diameter of 40 mm to form pellets. When various physical properties of the pellet were evaluated and measured, the MFR was 4.1 dg / min and the melt tension (MS) was 1.1 cN. The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography was 2.1.

[0143]

Example 6 70 parts by weight of the polypropylene composition (〓) produced in Example 4, 30 parts by weight of the polypropylene composition (〓) and 01 parts by weight of 2,6-di-t-butyl-p-cresol , And 0.1 part by weight of calcium stearate were mixed, and the mixture was granulated at 230 ° C. using an extruder having a screw diameter of 40 mm to form pellets. When various physical properties of the pellet were evaluated and measured, the MFR was 4.0 dg / min and the melt tension (MS) was 1.4 cN. The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography was 2.1.

[0144]

COMPARATIVE EXAMPLE 2 100 parts by weight of the polypropylene composition (I) prepared in Example 4, 2,6-di-t-butyl-p
-01 parts by weight of cresol and 0.1 part by weight of calcium stearate are mixed, and the mixture is mixed with a screw diameter of 40 m.
Granulation was carried out at 230 ° C. by using an extrusion granulator of m. When various physical properties of the pellet were evaluated and measured, the MFR was 4.0 dg / min and the melt tension (MS) was 0.4 cN. The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography was 1.9. Table 2 shows the conditions and results of Examples 4 to 6 and Comparative Example 2 described above.

[0145]

[Table 2]

As is apparent from Table 2, it was confirmed that the olefin (co) polymers obtained from the metallocene catalyst system of the examples of the present invention had a high melt tension.

[0147]

Example 7 (1) Production of Olefin (Co) polymer (I) (Propylene Polymerization) [Preparation of Supported Catalyst] Sufficiently dried and N ₂ substituted 50
In a 0 ml flask, 0.57 g (0.9 mmol) of dimethylsilylenebis (2-methyl, 4, phenyl-indenyl) zirconium dichloride and a toluene diluted product of methylaluminoxane were converted to Al atoms at 267 mmo.
1 was added and reacted for 10 minutes. Then, at 800 ℃ 8
10 g of silica (Grace Davisson) that had been calcined for an hour was added and stirred for 10 minutes. Thereafter, a slight flow of N ₂ was added from the bottom while applying vacuum from the top of the vessel. The mixture was heated at 70 ° C. while evaporating the solvent for 9 hours. The dried solid was cooled overnight at room temperature. 250 ml of the solid catalyst thus obtained and isopentane were dried and dried in a 500 ml N ₂ -substituted flask, and the mixture was cooled to 0 ° C. Then, ethylene was continuously added at a flow rate of 80 ml / min for 4 hours to carry out prepolymerization. Then, the supernatant was decanted and further decanted and washed four times with 100 ml of isopentane. Further, it was vacuum dried at room temperature for 2 hours to prepare 37 g of a supported catalyst.

[Propylene Polymerization] A stainless steel reactor equipped with a stirrer and having an inner volume of 100 dm ³ and equipped with a stirrer was replaced with nitrogen gas, and then 50 d of n-hexane was charged in the reactor.
Add 100 mmol of m ³ and triethylaluminum 5
Stir for minutes. Then, while maintaining the reactor internal temperature at 70 ° C., 3.8 g of the supported catalyst prepared above was added,
Immediately start supplying propylene monomer into the reactor, and while maintaining the gas phase pressure in the polymerization vessel at 1.1 MPa, continuously supply propylene for 2 hours into the polymerization vessel and carry out propylene polymerization at 70 ° C. did. The powder obtained is 7.4.
It was Kg. As a result of analyzing the obtained powder, MF
R4.1g / 10min, intrinsic viscosity 1.78dl / g
Met.

(2) Production of polypropylene composition (II) A polypropylene composition (II) was produced in the same manner as in Example 1.

(3) Olefin (co) polymer (I),
Blend of (II) 90 parts by weight of the polypropylene composition (I) produced as described above, 10 parts by weight of the polypropylene composition (II), 2,6-di-t-butyl-p-cresol 0.1. Part by weight and 0.1 part by weight of calcium stearate were mixed, and the mixture was granulated at 230 ° C. using an extrusion granulator having a screw diameter of 40 mm to obtain pellets. When the various physical properties of the pellet were evaluated and measured, the MFR was 3.9.
The dg / min and melt tension (MS) were 0.9 cN. The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography was 2.0.

[0151]

Example 8 80 parts by weight of the polypropylene composition (I) produced in Example 7, 20 parts by weight of the polypropylene composition (II), and 01 parts by weight of 2,6-di-t-butyl-p-cresol. , And 0.1 part by weight of calcium stearate were mixed, and the mixture was granulated at 230 ° C. using an extruder having a screw diameter of 40 mm to form pellets. When various physical properties of the pellet were evaluated and measured, the MFR was 4.0 dg / min and the melt tension (MS) was 1.0 cN. The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography was 2.0.

[0152]

Example 9 70 parts by weight of the polypropylene composition (I) produced in Example 7, 30 parts by weight of the polypropylene composition (II), and 01 parts by weight of 2,6-di-t-butyl-p-cresol. , And 0.1 part by weight of calcium stearate were mixed, and the mixture was granulated at 230 ° C. using an extruder having a screw diameter of 40 mm to form pellets. When various physical properties of the pellet were evaluated and measured, the MFR was 4.0 dg / min and the melt tension (MS) was 1.5 cN. The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography was 2.0.

[0153]

COMPARATIVE EXAMPLE 3 100 parts by weight of the polypropylene composition (I) prepared in Example 7, 2,6-di-t-butyl-p
-01 parts by weight of cresol and 0.1 part by weight of calcium stearate are mixed, and the mixture is mixed with a screw diameter of 40 m.
Granulation was carried out at 230 ° C. by using an extrusion granulator of m. When various physical properties of the pellet were evaluated and measured, the MFR was 4.1 dg / min and the melt tension (MS) was 0.4 cN. The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography was 2.0. Table 3 shows conditions and results of Examples 7 to 9 and Comparative Example 3 described above.

[0154]

[Table 3]

As is apparent from Table 3, it was confirmed that the olefin (co) polymers obtained from the metallocene catalyst system of the examples of the present invention had a high melt tension.

[0156]

The olefin (co) polymer obtained from the metallocene catalyst system of the present invention has a high melt tension and is excellent in moldability.

[Brief description of drawings]

FIG. 1 is a flow sheet of a method for producing a polypropylene composition according to an embodiment of the present invention.

Continuation of the front page (56) References International publication 98/035997 (WO, A1) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 23/02-23/36 C08F 4/64-4 / 69 C08F 10/00-10/14 C08F 110/00-110/14 C08F 210/00-210/18 C08F 297/08

Claims (10)

(57) [Claims] 1. (I) The following compounds (A) and (B):
Alternatively, 1 obtained by (co) polymerizing an olefin using a catalyst consisting of the following compounds (A), (B) and (C):
99-50% by weight of an olefin (co) polymer (I) having an intrinsic viscosity [ηI] of 0.2-10 dl / g measured in tetralin at 35 ° C., Compound (A): π-electron conjugated ligand Transition metal compound compound (B) having at least one: (B-1) aluminoxane, (B-2)
An ionic compound that reacts with the transition metal compound (A) to form an ionic complex, and (B-3) one or more compounds selected from a Lewis acid compound (C): organoaluminum compound (II) 1 to 50% by weight of the olefin (co) polymer (II) whose main component is 0.01 to 5 parts by weight of the component (II-1) of (II-1), and (II-1) ) A high molecular weight olefin (co) polymer having an intrinsic viscosity [ηE] measured with tetralin at 135 ° C. in the range of 15 to 100 dl / g , which is an ethylene homopolymer or
Ethylene containing 50% by weight or more of ethylene polymer units
Olefin Copolymer (II-2) The high molecular weight olefin (co) polymer (II-
Olefin (co) polymers other than 1) , which are propylene
50% by weight or less of homopolymer or propylene polymer unit
The propylene-olefin random copolymer also contained above
More specifically , an olefin (co) polymer composition containing a composition comprising a propylene-olefin block copolymer as a main component. 2. The olefin (co) polymer (I) is a propylene homopolymer or a propylene-olefin random copolymer or a propylene-olefin block copolymer containing 50% by weight or more of propylene polymer units. The composition according to 1. Wherein the olefin (co) polymer composition, the melt tension (MS) at the 230 ° C., under 21.18N load, between the melt flow index (MFR) as measured have you to 230 ° C., log (MS)> − 1.28 × log (MFR) +0.
The composition of claim 1 having a relationship represented by 44. 4. The composition according to claim 1, wherein the compound (A) is a transition metal compound represented by the following formula [1]. MLp ... [1] (where M is Zr, Ti, Hf, V, Nb,
A transition metal selected from Ta and Cr, p is the valence of the transition metal, L is a ligand that coordinates to the transition metal, and at least one L is a π-electron conjugated ligand. ) 5. The π-electron conjugated ligand is at least one ligand selected from η-cyclopentadienyl structure, η-benzene structure, η-cycloheptatrienyl structure and η-cyclooctatetraene structure. The composition according to claim 4 , which is 6. A ligand having an η-cyclopentadienyl structure is at least one ligand selected from a cyclopentadienyl group, an indenyl group, a hydrogenated indenyl group and a fluorenyl group (provided that these groups are Substituted with hydrocarbon groups such as alkyl groups, aryl groups and aralkyl groups, silicon-substituted hydrocarbon groups such as trialkylsilyl groups, halogen atoms, alkoxy groups, aryloxy groups, chain and cyclic alkylene groups, etc. The composition according to claim 5 , wherein 7. When the transition metal compound represented by the general formula [1] contains two or more π-electron conjugated ligands, two π-electron conjugated ligands among them are alkylene groups, Substituted alkylene group, cycloalkylene group, substituted cycloalkylene group, substituted alkylidene group, phenylene group, silylene group, dimethylsilylene group, diphenylsilylene group, dialkylsilylyl group, substituted dimethylsilylene group and germyl group (Me ₂ Ge) A composition according to claim 4 , which is crosslinked via at least one group which is 8. L other than the π-electron conjugated ligand is a hydrocarbon group such as a halogen, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, a silicon-substituted hydrocarbon group,
The composition according to claim 4 , which is an alkoxy group, an aryloxy group or a substituted sulfonato group. 9. The method according to claim 6, which is produced by blending the olefin (co) polymer composition according to any one of claims 1 to 8 and optionally added components by mechanical mixing means. Composition. 10. The mechanical mixing means is at least one mixing device selected from an extruder and a kneader.
9. The composition according to 9 .