JP2009040959A - Method for production of propylene based polymer with improved melt property - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for effectively producing a propylene based polymer in a simple method which has excellent flow characteristics such as melt tension, melt viscoelastic properties, etc., excellent in molding process workability, allowing a high closed cell ratio in extrusion foaming molding, preferably used in blow molding or extrusion foaming molding. <P>SOLUTION: The method for producing the propylene based polymer comprises polymerization of propylene in the presence of a catalyst consisting of at least component [A]; at least two kinds of specific transition metal compounds of the fourth group of the periodic system, component [B]: at least a kind selected from the group consisting of aluminum oxy compounds, ionic compounds or Lewis acids, fine particle of a solid acid and ion exchanging layered silicates, and component [C]; organic aluminum compounds, wherein the propylene based polymer is characterized by having a degree (λmax) of strain hardening, measured by elongational viscosity, of 2.0 or more. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a propylene-based polymer, and more specifically, good flow characteristics such as melt tension and melt viscoelasticity, and accordingly, at the time of blow molding, because of a high swell ratio, the molding processability is excellent, The present invention relates to a method for efficiently producing a propylene polymer suitable for blow molding, extrusion foam molding and the like, which can increase the closed cell ratio because it exhibits strong strain-hardening properties during extrusion foam molding.

Conventionally, polypropylene has high mechanical strength such as rigidity, excellent balance of physical properties, chemically stable, excellent weather resistance, hardly affected by chemicals, etc., and has a high melting point, excellent heat resistance, and light weight. Since it has features such as being inexpensive, it is widely used in many fields. However, ordinary polypropylene has low melt tension and melt viscoelasticity, and has problems such as limited use in thermoforming, foam molding, blow molding and the like.
In order to solve these problems, as a method of adding a component for increasing the melt tension, a method of mixing a high-density polyethylene with a high melt tension produced by a chromium catalyst, a method of mixing a low-density polyethylene by a high-pressure radical polymerization method , Methods for polymerizing high molecular weight polyethylene in the pre-propylene polymerization stage are known, but in those methods, the modulus of elasticity, strength, lack of heat resistance, or fluidity reduction of the component that increases the melt tension, There is a drawback that the original characteristics of polypropylene are impaired.

Therefore, various methods have been devised to increase the melt tension by introducing cross-linking of polypropylene itself or long-chain branching. As a method of crosslinking, a method of irradiating an electron beam after polymerization (for example, refer to Patent Document 1), a method using a peroxide, a peroxide and a crosslinking aid (for example, refer to Patent Document 2), a long process. Examples of the method for introducing chain branching include a method of grafting a radically polymerizable monomer onto polypropylene (for example, see Non-Patent Document 1), a method of copolymerizing propylene and polyene (for example, see Patent Document 3), and the like. It is done.
However, in the method of cross-linking after polymerization, it is difficult to control the side reaction of high-order cross-linking, and the appearance of the gel and the mechanical properties are adversely affected by the generation of gel, and the moldability is arbitrarily controlled. However, there is a problem that the control range is narrow. On the other hand, in the method of grafting a radically polymerizable monomer, the chemical stability of polypropylene is impaired, and there is a problem in recyclability. Furthermore, in the method based on copolymerization with polyene, the effect of improving the melt tension is not always sufficient, and the formation of gel is also a concern, so it is difficult to control the physical properties. In addition, a process for separating and recovering the polyene is essential after the completion of the copolymerization, and there remains a problem in terms of production cost.

Recently, a macromer copolymerization method mainly using a metallocene catalyst has been proposed.
The metallocene catalyst is a transition metal compound having at least one conjugated five-membered ring ligand in a broad sense, and a ligand having a crosslinked structure is generally used for propylene polymerization. Initially found as complexes capable of producing isotactic polyolefin, ethylene bis (indenyl) zirconium dichloride and ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride (Japanese Patent Laid-Open No. 61-130314) ), Dimethylsilylene bis-substituted cyclopentadienyl zirconium dichloride having a silylene group as a bridging group (JP-A-1-301704), dimethylsilylenebis (indenyl) zirconium dichloride (JP-A-1-275609), cyclopentadi Dimethylsilylenebis (2-methylindenyl) zirconium dichloride (Japanese Patent Laid-Open No. 4-268307) whose stereoregularity and molecular weight are improved to some extent by attaching a substituent next to the bridging group of the enyl compound (2-position). further Dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride (Japanese Patent Laid-Open No. 6-1005209) and dimethylsilylene bis, which are further improved in activity, stereoregularity and molecular weight by introducing an aryl group at the position (2-Methyl-4-phenyl-4-hydroazurenyl) zirconium dichloride (Japanese Patent Laid-Open No. 10-226712), and more recently, dichloro (1,1) having a specific substituent introduced into a specific position of the 4-position aryl group 1'-dimethylsilylenebis (2-ethyl-4- (3-chloro-4-t-butylphenyl) -4H-azulenyl)) hafnium (Japanese Patent Laid-Open No. 2003-292518), bulky hetero substitution at position 2 JP-A 2002-194016, JP-T 2002-535339, JP-A 2004 2259, JP-2004-352707 Patent Publication discloses JP.
These are mainly for the purpose of improving the catalytic activity and the melting point and molecular weight of the resulting polypropylene, and there is no suggestion of the suitability for producing macromers or long-chain branched polypropylene.

As a macromer copolymerization method using a metallocene catalyst, for example, in the first stage of polymerization (hereinafter also referred to as a macromer synthesis step), a propylene macromer having a vinyl structure at the terminal is produced using a specific catalyst and specific polymerization conditions. Then, in the second stage of polymerization (hereinafter also referred to as a macromer copolymerization process), copolymerization with propylene under a specific catalyst and specific polymerization conditions eliminates higher-order crosslinking, and as a polypropylene There has been proposed a method (hereinafter also referred to as a macromer copolymerization method) in which the original chemical stability is not impaired, the recyclability is excellent, and there is no concern about the generation of a gel for improving the melt tension (hereinafter also referred to as a macromer copolymerization method). And Patent Documents 4 and 5).
However, in this method, it is necessary to perform polymerization at a relatively high temperature and low pressure in order to efficiently obtain the terminal vinyl structure required as a macromer in the previous stage. In the latter stage, the macromer and propylene obtained in the preceding stage are copolymerized, but the amount of macromer to be copolymerized is small relative to the charged amount of the macromer, so the molecular weight is not negligible in the product macromer copolymer. And macromers with low stereoregularity remain. In addition, a component having a low molecular weight and low regularity other than a vinyl group, for example, a saturated terminal component, which is by-produced in the macromer synthesis process, is contained without being copolymerized. As a result, mechanical properties such as rigidity and impact strength are lowered, stickiness problems occur, and control of fluidity and moldability becomes difficult.

A homopolymerization method (in situ macromer production method) in which a macromer synthesis step and a macromer copolymerization step are simultaneously performed has been proposed (for example, see Patent Document 6).
However, in the known technology, the amount of macromer produced and the amount of macromer copolymerization are not always sufficient, and there are many limitations and further improvements are necessary for industrial production.

On the other hand, a method for producing a propylene polymer having a wide molecular weight distribution and a wide stereoregularity distribution using two types of complexes is also known, for example, ethylene bisindenyl hafnium dichloride and a small amount of ethylene bisindenyl zirconium dichloride. Polypropylene having a molecular weight distribution of 4.8 to 6.3 has been reported to be obtained by a catalyst composed of a mixed complex and methylaluminoxane (see, for example, Patent Document 7), but a simple bimodal molecular weight distribution is reported. It is only obtained and the effect of improving the melt physical properties is not great.
Recently, two metallocene complexes, specifically rac-SiMe ₂ [2-Me-4-Ph-Ind] ₂ ZrCl ₂ and rac-SiMe ₂ [2-Me-4-Ph-Ind] ₂ using the complex such as HfCl _2, the catalyst in combination with the silica carrying the methylaluminoxane (MAO), in multi-stage polymerization, the resulting propylene polymer that exhibits a relatively high melt tension has been reported (For example, refer to Patent Document 8).
However, this method is a multistage polymerization in which a polymerization step at a low temperature or low pressure is essential, and therefore, a method for producing a propylene-based polymer capable of improving melt properties by a simple method under practical conditions. Development is highly desired.
Recently, a complex system having a high terminal vinyl selectivity with a C1-symmetric metallocene complex has been reported (for example, see Patent Documents 9 and 10).
US Pat. No. 5,541,236 WO99 / 27007 International Publication Pamphlet JP-A-5-194778 JP-T-2001-525460 JP 10-338717 A Special table 2002-523575 gazette JP-A-2-255812 JP 2001-64314 A JP 2005-336091 A JP 2005-336092 A T.A. C. Chung et al, Synthesis of Polypropylene-graft-poly (methyl methacrylate) Polymers by Borane Approach, Macromolecules, (1993), volume 26. 14, page 3467-3471

  The object of the present invention is to provide excellent flow characteristics such as melt tension and melt viscoelasticity in view of the above-mentioned problems of the prior art. An object of the present invention is to provide a method for efficiently producing a propylene-based polymer suitable for blow molding, extrusion foam molding and the like, which can increase the closed cell ratio because it exhibits strong strain hardening at the time of molding.

  As a result of intensive studies to solve the above problems, the present inventors conducted propylene polymerization by single-stage polymerization in the presence of a catalyst containing two specific types of metallocene catalyst components. It has been found that a strain hardening degree (λmax) in the measurement of 2.0 can be efficiently produced with a polymer having a characteristic of 2.0 or more, and accordingly improved flow characteristics such as melt tension and melt viscoelasticity. Based on these findings, the present invention has been completed.

That is, according to the first invention of the present invention, there is provided a method for producing a propylene polymer by polymerizing propylene in the presence of a catalyst containing at least the components shown in the following [A] to [C], The obtained propylene polymer has a characteristic that the degree of strain hardening (λmax) in the measurement of elongational viscosity is 2.0 or more, and a method for producing a propylene polymer is provided.
Component [A]: at least two transition metal compounds selected from the following components [A-1] and [A-2], which are group 4 transition metal compounds of the periodic table.
[A-1]: Compound represented by the general formula (1)

[In Formula (1), Q ¹ is a binding group that bridges two conjugated five-membered ring ligands, a divalent hydrocarbon group having 1 to 20 carbon atoms, and a hydrocarbon having 1 to 20 carbon atoms. A silylene group having a group or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms, Me ¹ represents zirconium or hafnium, and X ¹ and Y ¹ are each independently hydrogen, halogen group, carbon A hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms 20 silicon-containing hydrocarbon groups are shown. R ^{1 to} R ⁴ are each independently a hydrocarbon group having 1 to 12 carbon atoms, a halogenated hydrocarbon group, or a silicon-containing hydrocarbon group, and R ¹ and R ² and / or R ³ and R ^{4. May} be bonded to form a divalent group, and R ⁵ is a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. It is a halogenated hydrocarbon group, and R ⁶ is an aryl group having 6 to 30 carbon atoms which may contain halogen, silicon, or a plurality of hetero elements selected from these. ]
[A-2]: Compound represented by the general formula (2)

[In Formula (2), Q ² is a binding group that bridges two conjugated five-membered ring ligands, a divalent hydrocarbon group having 1 to 20 carbon atoms, and a hydrocarbon having 1 to 20 carbon atoms. shows a germylene group having a silylene group or a hydrocarbon group having 1 to 20 carbon atoms having a group, Me ² represents zirconium or hafnium, X ² and Y ² are each independently hydrogen, halogen, carbon A hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms 20 silicon-containing hydrocarbon groups are shown. R ⁷ and R ⁸ are each independently a hydrocarbon group having 1 to 6 carbon atoms. R ⁹ and R ¹⁰ are each independently an aryl group having 6 to 30 carbon atoms which may contain halogen, silicon, or a plurality of hetero elements selected from these. R ¹¹ and R ¹² are each independently an unsaturated divalent hydrocarbon group having 3 to 5 carbon atoms. R ¹³ and R ¹⁴ are each independently a hydrocarbon group having 1 to 6 carbon atoms, a halogenated hydrocarbon group, or a silicon-containing hydrocarbon group. m and n are each independently 0 or an integer less than or equal to twice the number of carbon atoms of R ¹³ and R ¹⁴ (provided that when m and n are 2 or more, R ¹³ and R ¹⁴ are each in an arbitrary position) And may be bonded to form a ring structure). ]
Component [B]: an aluminum oxy compound [B-1], an ionic compound or Lewis acid [B-2] that can be converted into a cation by reacting with the transition metal compound of component [A], solid acid fine particles [ B-3] and at least one selected from the group of compounds consisting of ion-exchangeable layered silicate [B-4].
Component [C]: Organoaluminum.

According to the second aspect of the present invention, in the first aspect, the ratio of the amount of [A-1] to the total amount of components [A-1] and [A-2] is 0.30 in terms of molar ratio. A method for producing a propylene-based polymer is provided.
According to the third invention of the present invention, in the first or second invention, the component [B] is an ionic layered silicate [B-4]. Is provided.
Furthermore, according to a fourth invention of the present invention, in any one of the first to third inventions, the ion-exchange layered silicate [B-4] is a smectite group. A manufacturing method is provided.

According to a fifth aspect of the present invention, there is provided the method for producing a propylene polymer according to any one of the first to fourth aspects, wherein Me ¹ of the component [A-1] is hafnium. The
According to a sixth aspect of the present invention, there is provided a process for producing a propylene polymer according to any one of the first to fifth aspects, wherein Me ² of the component [A-2] is hafnium. Provided.
Furthermore, according to the seventh invention of the present invention, in any one of the first to sixth inventions, R ⁵ of the component [A-1] is a hydrocarbon group having 3 to 6 carbon atoms having a branched structure. A method for producing a propylene-based polymer is provided.

As described above, the present invention relates to a method for producing a propylene-based polymer, and preferred embodiments thereof include the following.
(1) In the first invention, there is provided a method for producing a propylene-based polymer, wherein one of each of the components [A-1] and [A-2] is used as the component [A].
(2) Component [A-1] is dichloro {1,1′-dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2-isopropyl-4-phenyl-4H-azurenyl)} It is hafnium, and the component [A-2] is rac-dichloro (1,1′-dimethylsilylenebis (2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl)) hafnium. A method for producing the above propylene-based polymer is provided.
(3) Component [C] is a trialkylaluminum, preferably triisobutylaluminum (TiBA). The method for producing a propylene-based polymer is provided.

  According to the production method of the present invention, flow characteristics such as melt tension and melt viscoelasticity are good, and accordingly, blow molding is excellent in molding processability due to a high swell ratio, and strong extrusion hardening during extrusion foam molding. Therefore, a propylene-based polymer that can be used for blow molding, extrusion foam molding, and the like, which can increase the closed cell ratio to show the properties, can be efficiently produced by a simple technique. For this reason, the manufacturing method of the present invention has a great industrial significance.

The method for producing a propylene-based polymer of the present invention is a strain hardening in measurement of elongational viscosity by carrying out propylene polymerization by single-stage polymerization in the presence of a catalyst containing at least the components [A] to [C] described later. It is characterized in that a polymer having a characteristic (λmax) of 2.0 or more is obtained. And this polymer is a long-chain branched type propylene-based polymer, whose melt fluidity and melt tension are controlled by its properties, and which has an excellent balance between physical properties and processability.
Hereinafter, the production method of the propylene polymer, the catalyst used in the production method, the polymerization process, the characteristics of the propylene polymer, and the like will be described in detail for each item.

1. Catalyst It is essential that the catalyst used in the production method of the present invention contains the following components [A] to [C].
(1) Component [A]
As the component [A], at least two kinds of transition metal compounds selected from the following components [A-1] and [A-2] are used. At that time, one or more transition metal compounds belonging to the components [A-1] and [A-2] are used, or other metallocene compounds other than the components [A-1] and [A-2] are used in combination. However, it is usually preferable to use one each of components [A-1] and [A-2].

(1-1) Component [A-1]
Component [A-1] is a metallocene compound having the following structural formula (1).

In the above formula, Q ¹ is a binding group that bridges two conjugated five-membered ring ligands, and has a divalent hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms. A silylene group or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms, preferably a substituted silylene group or a substituted germylene group. The substituent bonded to silicon or germanium of the silylene group or germanylene group is preferably a hydrocarbon group having 1 to 12 carbon atoms, and two substituents may be linked.
Specific examples include methylene, dimethylmethylene, ethylene-1,2-diyl, dimethylsilylene, diethylsilylene, diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylsilylene, diethylsilylene, Examples thereof include diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylgermylene, diethylgermylene, diphenylgermylene, methylphenylgermylene and the like.

Me ¹ is zirconium or hafnium, preferably hafnium.
X ¹ and Y ¹ are auxiliary ligands that react with the cocatalyst of component [B] to produce an active metallocene having olefin polymerization ability. Therefore, as long as this purpose is achieved, X ¹ and Y ¹ are not limited to the type of ligand, and are independently hydrogen, halogen group, hydrocarbon group having 1 to 20 carbon atoms, carbon An alkoxy group having 1 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms is shown.

R ^{1 to} R ⁴ are each independently a hydrocarbon group, halogenated hydrocarbon group or silicon having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms. It is a contained hydrocarbon group.
Specific examples of the hydrocarbon group represented by R ^{1 to} R ⁴ include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n -In addition to alkyl groups such as hexyl, cyclopropyl, cyclopentyl and cyclohexyl, and alkenyl groups such as vinyl, propenyl and cyclohexenyl, phenyl groups and the like can be mentioned.
Specific examples of the silicon-containing hydrocarbon group represented by R ^{1 to} R ⁴ include trialkylsilyl groups such as trimethylsilyl, triethylsilyl, and t-butyldimethylsilyl.
The halogenated hydrocarbon group represented by R ^{1 to} R ⁴ is a group in which a halogen atom is substituted at an arbitrary position of the above hydrocarbon group, and the halogen atom is any one of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. It may be. Specific examples thereof include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-chlorophenyl, and 3,5-difluorophenyl. 2,6-difluorophenyl, 2,4-dichlorophenyl, 3,5-dichlorophenyl, 2,6-dichlorophenyl, 2,5-dichlorophenyl, 2,4,6-trifluorophenyl, pentafluorophenyl and the like.
As a preferred example, R ^{1 to} R ⁴ are all the same hydrocarbon group, and particularly preferably a methyl group.
When R ¹ and R ² and / or R ³ and R ⁴ combine to form a divalent group, the carbon number is usually 3 or more, preferably 4 or more, and usually 9 or less, preferably 6 or less. It is. As the kind of divalent group, a hydrocarbon group is preferable. Specific examples of the divalent hydrocarbon group include dimethylene, trimethylene, tetramethylene, heptamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, trimethylene, tetramethylene and heptamethylene are preferred, and tetramethylene is particularly preferred. preferable.
It is more preferable that each of them forms a divalent group than only ^one of R ¹ and R ² or R ³ and R ⁴ forms a divalent group.

R ⁵ is a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group having 1 to 10 carbon atoms, or a halogenated hydrocarbon group having 1 to 10 carbon atoms, preferably a carbon atom having 3 to 9 carbon atoms. A hydrogen group, a silicon-containing hydrocarbon group having 3 to 9 carbon atoms, and a halogenated hydrocarbon group having 3 to 9 carbon atoms, and more preferably a hydrocarbon group having 3 to 6 carbon atoms having a branched structure. Preferable specific examples include i-propyl, sec-butyl, iso-butyl, t-butyl, 2-pentyl, 3-methyl-2-butyl, 2-hexyl, 3-methyl-2-pentyl, 4- Examples thereof include methyl-2-pentyl, cyclohexyl, phenyl and the like, and i-propyl is particularly preferable.
R ⁶ is an aryl group having 6 to 30 carbon atoms, preferably 6 to 24 carbon atoms, which may contain halogen, silicon, or a plurality of hetero elements selected from these. Preferred examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4- (2-fluorobiphenylyl), 4- (2-chlorobiphenylyl), 1-naphthyl, 2-naphthyl, 3,5-dimethyl-4-tert-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, etc. Is mentioned.

Examples of the metallocene compound include, for example, the following compounds, but the present invention is not limited to these compounds.
(Abbreviation: OHFlu: 1,2,3,4,5,6,7,8-octahydro-9-fluorenyl. TMCp: 2,3,4,5-tetramethylcyclopentadienyl. Azu: 4H-1- Azulenyl. THAzu: 5,6,7,8-tetrahydro-4H-1-azurenyl.)

(1) Dichloro [dimethylsilylene (OHFlu) (2-i-propyl-4-phenyl-Azu)] hafnium (2) Dichloro [dimethylsilylene (OHFlu) (2-i-propyl-4- (4-chlorophenyl)- Azu)] hafnium (3) dichloro [dimethylsilylene (OHFlu) (2-i-propyl-4- (4-fluorophenyl) -Azu)] hafnium (4) dichloro [dimethylsilylene (OHFlu) (2-i-propyl) -4- (3-chlorophenyl) -Azu)] hafnium (5) dichloro [dimethylsilylene (OHFlu) (2-i-propyl-4- (3-fluorophenyl) -Azu)] hafnium (6) dichloro [dimethylsilylene (OHFlu) (2-i-propyl-4- (4-methylphenyl) -Azu)] Nium (7) dichloro [dimethylsilylene (OHFlu) (2-i-propyl-4- (4-i-propylphenyl) -Azu)] hafnium (8) dichloro [dimethylsilylene (OHFlu) (2-i-propyl- 4- (4-t-butylphenyl) -Azu)] hafnium (9) dichloro [dimethylsilylene (OHFlu) (2-i-propyl-4- (4-trimethylsilylphenyl) -Azu)] hafnium (10) dichloro [ Dimethylsilylene (OHFlu) (2-i-propyl-4- (4- (2-fluorobiphenylyl))-Azu)] hafnium (11) dichloro [dimethylsilylene (OHFlu) (2-i-propyl-4- ( 4- (2-chlorobiphenylyl))-Azu)] hafnium (12) dichloro [dimethylsilylene (O Flu) (2-i-propyl-4- (4- (2-chlorobiphenylyl))-Azu)] hafnium (13) dichloro [dimethylsilylene (OHFlu) (2-i-propyl-4- (1-naphthyl) ) -Azu)] hafnium (14) dichloro [dimethylsilylene (OHFlu) (2-i-propyl-4- (2-naphthyl) -Azu)] hafnium (15) dichloro [dimethylsilylene (OHFlu) (2-i- Propyl-4- (3,5-dimethyl-4-tert-butylphenyl) -Azu)] hafnium (16) dichloro [dimethylsilylene (OHFlu) (2-i-propyl-4- (3,5-dimethyl-4) -Trimethylsilylphenyl) -Azu)] hafnium (17) dichloro [dimethylsilylene (OHFlu) (2-sec-butyl-4-fur Nenyl-Azu)] hafnium (18) dichloro [dimethylsilylene (OHFlu) (2-sec-butyl-4- (4-chlorophenyl) -Azu)] hafnium (19) dichloro [dimethylsilylene (OHFlu) (2-sec- Butyl-4- (4-fluorophenyl) -Azu)] hafnium (20) dichloro [dimethylsilylene (OHFlu) (2-cyclohexyl-4-phenyl-Azu)] hafnium

(21) Dichloro [dimethylsilylene (OHFlu) (2-cyclohexyl-4- (4-chlorophenyl) -Azu)] hafnium (22) Dichloro [dimethylsilylene (OHFlu) (2-cyclohexyl-4- (4-fluorophenyl) -Azu)] hafnium (23) dichloro [dimethylsilylene (OHFlu) (2-phenyl-4-phenyl-Azu)] hafnium (24) dichloro [dimethylsilylene (OHFlu) (2-phenyl-4- (4-chlorophenyl)] -Azu)] hafnium (25) dichloro [dimethylsilylene (OHFlu) (2-phenyl-4- (4-fluorophenyl) -Azu)] hafnium (26) dichloro [dimethylsilylene (OHFlu) (2-sec-pentyl- 4- (4-Chlorophenyl) -Az )] Hafnium (27) dichloro [dimethylsilylene (OHFlu) (2-sec-butyl-4- (4-t-butylphenyl) -Azu)] hafnium (25) dichloro [dimethylsilylene (OHFlu) (2-sec-) Butyl-4- (4-trimethylsilylphenyl) -Azu)] hafnium (26) dichloro [dimethylsilylene (OHFlu) (2-sec-butyl-4- (4- (2-fluorobiphenylyl))-Azu)] hafnium (27) Dichloro [dimethylsilylene (2,7-di-t-butyl-OHFlu) (2-i-propyl-4- (4-chlorophenyl) -Azu)] hafnium (28) Dichloro [dimethylsilylene (2,7 -Di-t-butyl-OHFlu) (2-i-propyl-4-phenyl-Azu)] hafnium ( 9) Dichloro [dimethylsilylene (TMCp) (2-i-propyl-4-phenyl-Azu)] hafnium (29) Dichloro [dimethylsilylene (TMCp) (2-i-propyl-4- (4-chlorophenyl) -Azu )] Hafnium (30) dichloro [dimethylsilylene (TMCp) (2-i-propyl-4- (4-fluorophenyl) -Azu)] hafnium (31) dichloro [dimethylsilylene (TMCp) (2-i-propyl-) 4- (3-chlorophenyl) -Azu)] hafnium (32) dichloro [dimethylsilylene (TMCp) (2-i-propyl-4- (3-fluorophenyl) -Azu)] hafnium (33) dichloro [dimethylsilylene ( TMCp) (2-i-propyl-4- (4-methylphenyl) -Azu)] hafni Um (34) dichloro [dimethylsilylene (TMCp) (2-i-propyl-4- (4-i-propylphenyl) -Azu)] hafnium (35) dichloro [dimethylsilylene (TMCp) (2-i-propyl- 4- (4-t-butylphenyl) -Azu)] hafnium (36) dichloro [dimethylsilylene (TMCp) (2-i-propyl-4- (4-trimethylsilylphenyl) -Azu)] hafnium (37) dichloro [ Dimethylsilylene (TMCp) (2-i-propyl-4- (4- (2-fluorobiphenylyl))-Azu)] hafnium (38) dichloro [dimethylsilylene (TMCp) (2-i-propyl-4- ( 4- (2-chlorobiphenylyl))-Azu)] hafnium (39) dichloro [dimethylsilylene (TMCp) 2-i-propyl-4- (1-naphthyl) -Azu)] hafnium (40) dichloro [dimethylsilylene (TMCP) (2-i-propyl-4- (2-naphthyl) -Azu)] hafnium

(41) Dichloro [dimethylsilylene (TMCp) (2-i-propyl-4- (3,5-dimethyl-4-tert-butylphenyl) -Azu)] hafnium (42) Dichloro [dimethylsilylene (TMCp) (2 -I-propyl-4- (3,5-dimethyl-4-trimethylsilylphenyl) -Azu)] hafnium (43) dichloro [dimethylsilylene (TMCp) (2-sec-butyl-4-phenyl-Azu)] hafnium ( 44) Dichloro [dimethylsilylene (TMCp) (2-sec-butyl-4- (4-chlorophenyl) -Azu)] hafnium (45) Dichloro [dimethylsilylene (TMCp) (2-sec-butyl-4- (4- Fluorophenyl) -Azu)] hafnium (46) dichloro [dimethylsilylene (TMCp) (2- Chlohexyl-4-phenyl-Azu)] hafnium (47) dichloro [dimethylsilylene (TMCp) (2-cyclohexyl-4- (4-chlorophenyl) -Azu)] hafnium (48) dichloro [dimethylsilylene (TMCp) (2- Cyclohexyl-4- (4-fluorophenyl) -Azu)] hafnium (49) dichloro [dimethylsilylene (TMCp) (2-phenyl-4-phenyl-Azu)] hafnium (50) dichloro [dimethylsilylene (TMCp) (2 -Phenyl-4- (4-chlorophenyl) -Azu)] hafnium (51) dichloro [dimethylsilylene (TMCp) (2-phenyl-4- (4-fluorophenyl) -Azu)] hafnium (52) dichloro [dimethylsilylene (TMCp) (2-sec-pen Ru-4- (4-chlorophenyl) -Azu)] hafnium (53) dichloro [dimethylsilylene (TMCp) (2-sec-butyl-4- (4-t-butylphenyl) -Azu)] hafnium (54) dichloro [Dimethylsilylene (TMCp) (2-sec-butyl-4- (4-trimethylsilylphenyl) -Azu)] hafnium (55) dichloro [dimethylsilylene (TMCp) (2-sec-butyl-4- (4- (2 -Fluorobiphenylyl))-Azu)] hafnium (56) dichloro [dimethylmethylene (TMCp) (2-i-propyl-4-phenyl-Azu)] hafnium (57) dichloro [dimethylmethylene (TMCp) (2-i -Propyl-4- (4-chlorophenyl) -Azu)] hafnium (58) dichloro [diphe Nylsilylene (TMCp) (2-i-propyl-4-phenyl-Azu)] hafnium (59) dichloro [diphenylsilylene (TMCp) (2-i-propyl-4- (4-chlorophenyl) -Azu)] hafnium (60 ) Dichloro [diphenylsilylene (TMCp) (2-i-propyl-4-phenyl-Azu)] hafnium

(61) Dichloro [diphenylsilylene (TMCp) (2-i-propyl-4- (4-chlorophenyl) -Azu)] hafnium (62) Dichloro [dimethylgermylene (TMCp) (2-i-propyl-4-phenyl) -Azu)] hafnium (63) dichloro [dimethylgermylene (TMCp) (2-i-propyl-4- (4-chlorophenyl) -Azu)] hafnium (64) dichloro [dimethylgermylene (TMCp) (2-i -Propyl-4- (4-t-butylphenyl) -Azu)] hafnium

In order to use a transition metal compound having a C1 symmetry as the polymerization catalyst component as the component [A-1] according to the present invention, among the above-described transition metal compounds (1) to (64), dichloro [dimethylsilylene (TMCp ) (2-i-propyl-4-phenyl-Azu)] hafnium, dichloro [dimethylsilylene (TMCp) (2-i-propyl-4- (4-chlorophenyl) -Azu)] hafnium, dichloro [dimethylsilylene (TMCp) ) (2-i-propyl-4- (3-chlorophenyl) -Azu)] hafnium, dichloro [dimethylsilylene (TMCp) (2-i-propyl-4- (3-fluorophenyl) -Azu)] hafnium, dichloro [Dimethylsilylene (TMCp) (2-i-propyl-4- (4-t-butylphenyl) -Azu)] hafni Dichloro [dimethylsilylene (TMCp) (2-i-propyl-4- (4-trimethylsilylphenyl) -Azu)] hafnium, dichloro [dimethylsilylene (TMCp) (2-i-propyl-4- (4- ( 2-fluorobiphenylyl))-Azu)] hafnium, dichloro [dimethylsilylene (TMCp) (2-i-propyl-4- (3,5-dimethyl-4-tert-butylphenyl) -Azu)] hafnium, dichloro [Dimethylsilylene (TMCp) (2-i-propyl-4- (3,5-dimethyl-4-trimethylsilylphenyl) -Azu)] hafnium is preferred.
In addition, compounds in which the central metal M of the compounds represented by the formulas (1) to (64) exemplified above is replaced with zirconium instead of hafnium can also be used as the polymerization catalyst component.

(1-2) Component [A-2]
Component [A-2] is a metallocene compound having the following structural formula (2).

In the above formula, Q ² is a binding group that bridges two conjugated five-membered ring ligands, and has a divalent hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms. A germylene group having a silylene group or a hydrocarbon group having 1 to 20 carbon atoms, preferably a substituted silylene group or a substituted germylene group. The substituent bonded to silicon or germanium of the silylene group or germanylene group is preferably a hydrocarbon group having 1 to 12 carbon atoms, and two substituents may be linked. Specific examples include methylene, dimethylmethylene, ethylene-1,2-diyl, dimethylsilylene, diethylsilylene, diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylsilylene, diethylsilylene, Examples thereof include diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylgermylene, diethylgermylene, diphenylgermylene, methylphenylgermylene and the like.

Me ² is zirconium or hafnium, preferably hafnium.
X ² and Y ² are auxiliary ligands, and react with the cocatalyst of component [B] to produce an active metallocene having olefin polymerization ability. Therefore, as long as this purpose is achieved, X ² and Y ² are not limited to the type of ligand, and are independently hydrogen, halogen group, hydrocarbon group having 1 to 20 carbon atoms, carbon An alkoxy group having 1 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms is shown.

R ⁷ and R ⁸ are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, and preferably methyl. , Ethyl, n-propyl.
R ⁹ and R ¹⁰ may each independently contain a halogen having 6 to 30 carbon atoms, preferably 6 to 24 carbon atoms, silicon, or a plurality of hetero elements selected from these. A good aryl group. Preferred examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4- (2-fluorobiphenylyl), 4- (2-chlorobiphenylyl), 1-naphthyl, 2-naphthyl, 3,5-dimethyl-4-tert-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, etc. Is mentioned.
Further, R ¹¹ and R ¹² are each independently an unsaturated divalent hydrocarbon group having 3 to 5 carbon atoms, preferably 3, 4 and particularly preferably 4. Therefore, the condensed ring formed is a 6 to 8 membered ring, preferably a 6 or 7 membered ring, particularly preferably a 7 membered ring.

R ¹³ and R ¹⁴ are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, a halogenated hydrocarbon group, or a silicon-containing hydrocarbon group. It is not particularly necessary to use a bulky group, and preferred examples include methyl, ethyl, n-propyl and the like.
Further, m and n are each independently 0 or an integer of 2 or less times the number of carbon atoms of R ¹³ and R ¹⁴ (provided that when m and n are 2 or more, R ¹³ and R ¹⁴ are each an arbitrary number) It may be bonded at a position to form a ring structure.), Preferably 0.

  The compound of the general formula of component [A-2] in which the condensed ring is a 7-membered ring is a metallocene compound having the following structural formula (3), and is a complex of an azulene skeleton.

Examples of the metallocene compound include, for example, the following compounds, but the present invention is not limited to these compounds.
(1) Dichloro {1,1′-dimethylsilylenebis (2-methyl-4-phenyl-4-hydroazulenyl)} hafnium (2) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4 -Chlorophenyl) -4-hydroazurenyl}] hafnium (3) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-tert-butylphenyl) -4-hydroazurenyl}] hafnium (4) dichloro [ 1,1′-dimethylsilylenebis {2-methyl-4- (4-trimethylsilylphenyl) -4-hydroazulenyl}] hafnium (5) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3 -Chloro-4-t-butylphenyl) -4-hydroazurenyl}] hafnium (6) dichloro [1,1′-dimethylsilylenebis { -Methyl-4- (3-methyl-4-t-butylphenyl) -4-hydroazulenyl}] hafnium (7) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4) -Trimethylsilylphenyl) -4-hydroazurenyl}] hafnium (8) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium (9 ) Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (1-naphthyl) -4-hydroazurenyl}] hafnium (10) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-Naphthyl) -4-hydroazulenyl}] hafnium

(11) Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-fluoro-4-biphenyl) -4-hydroazulenyl}] hafnium (12) dichloro [1,1′-dimethylsilylenebis { 2-methyl-4- (2-chloro-4-biphenyl) -4-hydroazulenyl}] hafnium (13) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (9-phenanthryl) -4- Hydroazurenyl}] hafnium (14) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium (15) dichloro [1,1′- Dimethylsilylenebis {2-ethyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium (16) dichloro [1,1′-di Tylsilylenebis {2-n-propyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazulenyl}] hafnium (17) dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3- Chloro-4-t-butylphenyl) -4-hydroazurenyl}] hafnium (18) dichloro [1,1′-dimethylgermylenebis {2-methyl-4- (2-fluoro-4-biphenyl) -4-hydroazurenyl] }] Hafnium (19) dichloro [1,1′-dimethylgermylenebis {2-methyl-4- (4-tert-butylphenyl) -4-hydroazurenyl}] hafnium (20) dichloro [1,1 ′-( 9-silafluorene-9,9-diyl) bis {2-ethyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafniu

(21) Dichloro {1,1′-dimethylsilylenebis (2-methyl-4-phenylindenyl)} hafnium (22) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) ) Indenyl}] hafnium (23) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-t-butylphenyl) indenyl}] hafnium (24) dichloro [1,1′-dimethylsilylenebis] {2-Methyl-4- (4-trimethylsilylphenyl) indenyl}] hafnium (25) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3,5-di-t-butylphenyl) indenyl }] Hafnium (26) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3,5-dimethyl-4-tert-butylphenol) Nyl) indenyl}] hafnium (27) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-methyl-4-trimethylsilylphenyl) indenyl}] hafnium (28) dichloro [1,1′- Dimethylsilylenebis {2-methyl-4- (1-naphthyl) indenyl}] hafnium

  In the above-mentioned compounds, avoiding many complicated examples, only representative exemplary compounds are described, and compounds having a central metal of hafnium are described. However, similar zirconium compounds can be used, and various compounds can be used. Obviously, ligands, bridging groups or auxiliary ligands can be used arbitrarily.

(2) Component [B]
As the component [B], an aluminum oxy compound [B-1], an ionic compound that can be converted into a cation by reacting with the above transition metal compound or Lewis acid [B-2], solid acid fine particles [B- 3] and at least one selected from the group of compounds consisting of ion-exchangeable layered silicate [B-4].

(2-1) Component [B-1]
Specific examples of the aluminum oxy compound [B-1] include compounds represented by the following general formula (4), (5) or (6).

In each of the above general formulas, R ¹⁵ represents a hydrogen atom or a hydrocarbon residue, preferably a hydrocarbon residue having 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms. Further, a plurality of R ¹⁵ may each be the same or different. P represents an integer of 0 to 40, preferably 2 to 30.

The compounds represented by the general formulas (4) and (5) are also called alumoxanes. Among these, methylalumoxane or methylisobutylalumoxane is preferable.
The above alumoxane can be used in combination within a group and between groups. And said alumoxane can be prepared on well-known various conditions.

The compound represented by the general formula (6) is 10: 1 to 1: 1 of one type of trialkylaluminum or two or more types of trialkylaluminum and an alkylboronic acid represented by the following general formula (7). (Molar ratio) can be obtained by the reaction. In General Formulas (6) and (7), R ¹⁶ represents a hydrocarbon residue or halogenated hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.
R ¹⁶ B (OH) ₂ (7)

  Component [B-1] can also be used by being supported on a particulate carrier. The fine particle carrier will be described later.

(2-2) Component [B-2]
Component [B-2] is an ionic compound or a Lewis acid that can be converted into a cation by reacting with the above-described transition metal compound.
Specifically, examples of the ionic compound include a cation such as a carbonium cation and an ammonium cation, and an organic boron compound such as triphenylboron, tris (3,5-difluorophenyl) boron, and tris (pentafluorophenyl) boron. And a complex with a cation.

  Examples of the Lewis acid that can convert the component [A] into a cation include various organoboron compounds such as tris (pentafluorophenyl) boron. Alternatively, metal halogen compounds such as aluminum chloride and magnesium chloride are exemplified. In addition, a certain thing of said Lewis acid can also be grasped | ascertained as an ionic compound which can react with component [A] and can convert component [A] into a cation. Therefore, the compounds belonging to both the Lewis acid and the ionic compound belong to either one.

(2-3) Component [B-3]
Examples of the solid acid fine particles [B-3] include solid acids such as alumina and silica-alumina.
Here, the particulate carrier in [B-1] and [B-2] described above will be described.
In the present invention, the particulate carrier is not particularly limited with respect to its elemental composition and compound composition. For example, a particulate carrier made of an inorganic or organic compound can be exemplified. Examples of the inorganic carrier include silica, alumina, silica / alumina magnesium chloride, activated carbon, inorganic silicate, and the like. Alternatively, a mixture thereof may be used.

Examples of the organic carrier include polymers of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, and aromatic unsaturated hydrocarbons such as styrene and divinylbenzene. Examples thereof include a porous polymer fine particle carrier made of a polymer or the like. Alternatively, a mixture thereof may be used.
These fine particle carriers usually have an average particle diameter of 1 μm to 5 mm, preferably 5 μm to 1 mm, more preferably 10 μm to 200 μm.

(2-4) Component [B-4]
Component [B-4] is an ion-exchange layered silicate (hereinafter simply referred to as silicate). In the present invention, the silicate used as a raw material is a silicate compound having a crystal structure in which the surfaces constituted by ionic bonds and the like are stacked in parallel with each other and having exchangeable ions. Say. Most silicates are naturally produced mainly as the main component of clay minerals, and therefore often contain impurities (quartz, cristobalite, etc.) other than ion-exchanged layered silicates. But you can. Specific examples of the silicate include the following layered silicates described in Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1995).

  That is, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stemite and other smectites, vermiculite and other vermiculites, mica, illite, sericite and sea chlorite and other mica, attapulgite, sepiolite and palygorskite , Bentonite, pyrophyllite, talc, chlorite group, etc.

  The silicate used as a raw material in the present invention is preferably a silicate in which the main component silicate has a 2: 1 type structure, more preferably a smectite group, and particularly preferably montmorillonite. The type of interlayer cation is not particularly limited, but a silicate containing an alkali metal or an alkaline earth metal as a main component of the interlayer cation is preferable from the viewpoint of being relatively easy and inexpensive to obtain as an industrial raw material.

  Although the silicate used by this invention can be used as it is, without performing a process especially, it is preferable to give a chemical process. Here, as the chemical treatment, any of a surface treatment for removing impurities adhering to the surface and a treatment affecting the structure of the clay can be used. Specific examples of the chemical treatment in the present invention include a) acid treatment, b) salt treatment, c) alkali treatment, and d) organic matter treatment described below.

a) Acid treatment In addition to removing impurities on the surface, the acid treatment can elute some or all of cations such as Al, Fe, Mg, etc. having a crystal structure.
The acid used in the acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, and oxalic acid. Two or more acids may be used for the treatment. The treatment conditions with the acid are not particularly limited. Usually, the acid concentration is 0.1 to 50% by weight, the treatment temperature is room temperature to the boiling point, and the treatment time is 5 minutes to 24 hours. It is preferable to carry out the reaction under the condition that at least a part of the substance constituting at least one compound selected from the group consisting of ion-exchangeable layered silicates is eluted. The acid is generally used in an aqueous solution.

b) Salt treatment In the present invention, 40% or more, preferably 60% or more, of the exchangeable Group 1 metal cation contained in the ion-exchangeable layered silicate before being treated with salts is shown below. It is preferable to exchange ions with cations dissociated from salts.

The salt used in the salt treatment for the purpose of ion exchange is a group consisting of a cation containing at least one atom selected from the group consisting of group 1 to 14 atoms, a halogen atom, an inorganic acid and an organic acid. A compound comprising at least one anion selected from the group consisting of at least one anion selected from the group consisting of group 2 to 14 atoms and Cl, Br, I, F, PO. ₄ , SO ₄ , NO ₃ , CO ₃ , C ₂ O ₄ , ClO ₄ , OOCCH ₃ , CH ₃ COCHCOCH ₃ , OCl ₂ , O (NO ₃ ) ₂ , O (ClO ₄ ) ₂ , O (SO ₄ ), At least one anion selected from the group consisting of OH, O ₂ Cl ₂ , OCl ₃ , OOCH, OOCCH ₂ CH ₃ , C ₂ H ₄ O ₄ and C ₅ H ₅ O ₇ Is a compound consisting of

_{Specifically, LiF, LiCl, LiBr, LiI} , Li 2 SO 4, Li (CH 3 COO), LiCO 3, Li (C 6 H 5 O 7), LiCHO 2, LiC 2 O 4, LiClO 4, Li ₃ PO ₄ , CaCl ₂ , CaSO ₄ , CaC ₂ O ₄ , Ca (NO ₃ ) ₂ , Ca ₃ (C ₆ H ₅ O ₇ ) ₂ , MgCl ₂ , MgBr ₂ , MgSO ₄ , Mg (PO ₄ ) ₂ , Mg (ClO ₄ ) ₂ , MgC ₂ O ₄ , Mg (NO ₃ ) ₂ , Mg (OOCCH ₃ ) ₂ , MgC ₄ H ₄ O ₄ , Ti (OOCCH ₃ ) ₄ , Ti (CO ₃ ) ₂ , Ti (NO ₃ ) ₄ , Ti (SO ₄ ) ₂ , TiF ₄ , TiCl ₄ , Zr (OOCCH ₃ ) ₄ , Zr (CO ₃ ) ₂ , Zr (NO ₃ ) ₄ , Zr (SO ₄ ) ₂ , Zr F ₄ , ZrCl ₄ , ZrOCl ₂ , ZrO (NO ₃ ) ₂ , ZrO (ClO ₄ ) ₂ , ZrO (SO ₄ ), HF (OOCCH ₃ ) ₄ , HF (CO ₃ ) ₂ , HF (NO ₃ ) ₄ , _{HF (SO 4) 2, HFOCl} 2, HFF 4, HFCl 4, V (CH 3 COCHCOCH 3) 3, VOSO 4, VOCl 3, VCl 3, VCl 4, VBr 3 , etc. _{and, Cr (CH 3 COCHCOCH 3)} 3 Cr (OOCCH ₃ ) ₂ OH, Cr (NO ₃ ) ₃ , Cr (ClO ₄ ) ₃ , CrPO ₄ , Cr ₂ (SO ₄ ) ₃ , CrO ₂ Cl ₂ , CrF ₃ , CrCl ₃ , CrBr ₃ , CrI _{3 , Mn (OOCCH 3) 2,} Mn (CH 3 COCHCOCH 3) 2, MnCO 3, Mn (NO 3) 2, MnO, Mn _{ClO 4) 2, MnF 2,} MnCl 2, Fe (OOCCH 3) 2, Fe (CH 3 COCHCOCH 3) 3, FeCO 3, Fe (NO 3) 3, Fe (ClO 4) 3, FePO 4, FeSO 4, Fe ₂ (SO ₄ ) ₃ , FeF ₃ , FeCl ₃ , FeC ₆ H ₅ O ₇ , Co (OOCCH ₃ ) ₂ , Co (CH ₃ COCHCOCH ₃ ) ₃ , CoCO ₃ , Co (NO ₃ ) ₂ , CoC ₂ O ₄ , Co (ClO ₄ ) ₂ , Co ₃ (PO ₄ ) ₂ , CoSO ₄ , CoF ₂ , CoCl ₂ , NiCO ₃ , Ni (NO ₃ ) ₂ , NiC ₂ O ₄ , Ni (ClO ₄ ) ₂ , NiSO ₄ , NiCl ₂ , NiBr _2, etc., Zn (OOCCH ₃ ) ₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ , ZnCO ₃ , Z n (NO ₃ ) ₂ , Zn (ClO ₄ ) ₂ , Zn ₃ (PO ₄ ) ₂ , ZnSO ₄ , ZnF ₂ , ZnCl ₂ , AlF ₃ , AlCl ₃ , AlBr ₃ , AlI ₃ , Al ₂ (SO ₄ ) ₃ Al ₂ (C ₂ O ₄ ) ₃ , Al (CH ₃ COCHCOCH ₃ ) ₃ , Al (NO ₃ ) ₃ , AlPO ₄ , GeCl ₄ , GeBr ₄ , GeI _{4 and the} like.
Moreover, 2 or more types of salts used for a process may be sufficient. The treatment conditions with salts are not particularly limited, but usually, the salt and acid concentrations are 0.1 to 50% by weight, the treatment temperature is room temperature to boiling point, and the treatment time is 5 minutes to 24 hours. be able to. In addition, salts and acids are generally used in an aqueous solution.

c) Alkali treatment Examples of the treating agent used in the alkali treatment include LiOH, NaOH, KOH, Mg (OH) 2, Ca (OH) 2, Sr (OH) ₂ , Ba (OH) ₂ .

d) Organic substance treatment Examples of the organic substance used for the organic substance treatment include trimethylammonium, triethylammonium, N, N-dimethylanilinium, triphenylphosphonium, and the like.
Examples of the anion constituting the organic treatment agent include hexafluorophosphate, tetrafluoroborate, tetraphenylborate and the like other than the anions exemplified as the anion constituting the salt treatment agent. It is not limited to these.
Among these acid treatment, salt treatment, alkali treatment, and organic matter treatment, preferred treatment methods are acid treatment and salt treatment. Any of these methods can be selected, and acid treatment, salt treatment, and treatment in which an acid and a salt coexist are generally performed once or more. Particularly preferably, an acid or an acid and a salt are used. This is a method of performing a salt treatment after the coexisting treatment.

These ion-exchange layered silicates usually contain adsorbed water and interlayer water. In the present invention, it is preferable to remove these adsorbed water and interlayer water and use them as component [B].
The heat treatment method of the ion-exchange layered silicate adsorbed water and interlayer water is not particularly limited, but it is necessary to select conditions so that interlayer water does not remain and structural destruction does not occur. The heating time is 0.5 hour or longer, preferably 1 hour or longer. At that time, the water content of the removed component [B] is 3% by weight or less, preferably 0% by weight when the water content is 0% by weight when dehydrated for 2 hours at a temperature of 200 ° C. and a pressure of 1 mmHg. Is preferably 1% by weight or less.

  As described above, in the present invention, as the component [B], an ion-exchange layered silicate having a water content of 3% by weight or less obtained by performing a salt treatment and / or an acid treatment is particularly preferable. It is.

  The ion-exchange layered silicate can be treated with the component [C] described later before being used as a catalyst or as a catalyst, which is preferable. Although there is no restriction | limiting in the usage-amount of component [C] with respect to 1g of ion-exchange layered silicate, Usually, 20 mmol or less, Preferably it is 0.5 mmol or more and 10 mmol or less. There is no limitation on the treatment temperature and time, the treatment temperature is usually 0 ° C. or more and 70 ° C. or less, and the treatment time is 10 minutes or more and 3 hours or less. It is also possible and preferable to wash after the treatment. As the solvent, the same hydrocarbon solvent as that used in the preliminary polymerization and slurry polymerization described later is used.

The component [B] is preferably spherical particles having an average particle diameter of 5 μm or more. If the particle shape is spherical, a natural product or a commercially available product may be used as it is, or a particle whose particle shape and particle size are controlled by granulation, sizing, fractionation, or the like may be used.
Examples of the granulation method used here include agitation granulation method and spray granulation method, but commercially available products can also be used.

Moreover, you may use organic substance, an inorganic solvent, inorganic salt, and various binders in the case of granulation.
The spherical particles obtained as described above desirably have a compressive fracture strength of 0.2 MPa or more, particularly preferably 0.5 MPa or more, in order to suppress crushing and generation of fine powder in the polymerization process. In the case of such particle strength, the effect of improving the particle properties is effectively exhibited especially when prepolymerization is performed.

Among the above-mentioned component [B], [B-4] ion exchange layered silicate is particularly preferable.
In the catalyst used in the production method of the present invention, [B-1] an aluminum oxy compound, [B-2] an ionic compound capable of reacting with component [A] to convert component [A] into a cation, or Lewis The acid, [B-3] solid acid fine particles, or [B-4] ion-exchange layered silicate fine particles are each used alone as component [B], and these four components are used in appropriate combination. be able to.

(3) Component [C]
As the component [C], an organoaluminum compound is used. In the present invention, an organoaluminum compound represented by the general formula: AlR ¹¹ _q Z _3-q is suitable.
In the present invention, it goes without saying that the compounds represented by this formula can be used alone, in combination of two or more, or in combination. In this formula, R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms, and Z represents a halogen, hydrogen, an alkoxy group, or an amino group. q is a number greater than 0 and up to 3. R ¹¹ is preferably an alkyl group, and Z is hydrogen, chlorine when it is halogen, chlorine when it is an alkoxy group, or alkoxy group having 1 to 8 carbon atoms when it is an amino group. A C1-C8 amino group is preferable.

Specific examples of preferred organoaluminum compounds include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethyl Examples thereof include aluminum sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, diisobutylaluminum chloride and the like. Of these, trialkylaluminum and dialkylaluminum hydrides with q = 3 are preferred. More preferably, R ¹¹ is a trialkylaluminum having 1 to 8 carbon atoms.

2. Formation of Catalyst / Preliminary Polymerization The catalyst according to the present invention can be formed by bringing the above-mentioned components into contact in the (preliminary) polymerization tank simultaneously or continuously, or once or several times. The contact of each component is usually carried out in an aliphatic hydrocarbon or aromatic hydrocarbon solvent. The contact temperature is not particularly limited, but is preferably between -20 ° C and 150 ° C.
As the contact order, any desired combination can be used, but particularly preferable ones for each component are as follows.
When component [C] is used, before contacting component [A] with component [B], component [A], or component [B], or both component [A] and component [B] The component [C] or the component [A] and the component [B] are contacted simultaneously with the component [C], or the component [A] and the component [B] are contacted with each other. It is possible to contact the component [C] after the contact, but it is preferable to contact the component [C] with the component [C] before contacting the component [A] with the component [B].
After contacting each component, it is possible to wash with an aliphatic hydrocarbon or an aromatic hydrocarbon solvent.

The amount of components [A], [B] and [C] used in the present invention is arbitrary. For example, the amount of component [A] used relative to component [B] is preferably in the range of 0.1 μmol to 1000 μmol, particularly preferably 0.5 μmol to 500 μmol, relative to 1 g of component [B]. The amount of the component [C] used relative to the component [B] is preferably such that the amount of Al is 0.01 to 1000 mmol, particularly preferably 0.05 to 500 mmol, relative to 1 g of the component [B]. Therefore, the amount of the component (C) relative to the component (A) is preferably in the range of 0.01 to 5 × 10 ⁶ , particularly preferably 0.1 to 100, in terms of the molar ratio of the transition metal.

  In the component [A-1] and the component [A-2] used in the present invention, the ratio of the amount of [A-1] to the total amount of each component [A-1] and [A-2] is propylene-based. Although it is arbitrary within the range satisfying the characteristics of the polymer, it is preferably 0.30 to 0.99 in terms of molar ratio. By changing this ratio, it is possible to adjust the balance between the melt properties and the catalyst activity, and particularly preferably for the production of propylene-based polymers for applications that require higher melt properties and high catalyst activity, It is in the range of 0.40 to 0.90, more preferably 0.5 to 0.8.

The catalyst according to the present invention is preferable because it can be subjected to a prepolymerization treatment consisting of a small amount of polymerization by bringing the olefin into contact therewith. The olefin to be used is not particularly limited, but propylene, ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene and the like. A propylene is preferable, and propylene is preferable.
The olefin feed method may be any method such as a feed method for maintaining the olefin at a constant speed or in a constant pressure state, a combination thereof, or a stepwise change.
The prepolymerization temperature and time are not particularly limited, but are preferably in the range of −20 ° C. to 100 ° C. and 5 minutes to 24 hours, respectively. Further, the amount of prepolymerization is such that the amount of prepolymerized polymer is in a weight ratio with respect to component [B], preferably 0.01 to 100, more preferably 0.1 to 50. Moreover, component [C] can also be added or added at the time of prepolymerization. It is also possible to wash after the prepolymerization.
A method of coexisting a polymer such as polyethylene or polypropylene or a solid of an inorganic oxide such as silica or titania at the time of contacting or after the contact of each of the above components is also possible.

3. Use of Catalyst / Propylene Polymerization As the polymerization mode, any mode can be adopted as long as the olefin polymerization catalyst including the component [A], the component [B], and the component [C] is in efficient contact with the monomer. Specifically, a slurry method using an inert solvent, a so-called bulk method, a solution polymerization method, or a substantially liquid solvent without using an inert solvent as a solvent. A gas phase method can be used. Further, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied. In addition to single-stage polymerization, it is possible to carry out multistage polymerization of two or more stages.

In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, toluene, or the like is used alone or as a polymerization solvent.
The polymerization temperature is 0 to 150 ° C., and hydrogen can be used supplementarily as a molecular weight regulator. The polymerization pressure is 0 to 200 MPa, preferably 0 to 5 MPa.

  In addition to the propylene monomer, copolymerization using an α-olefin having about 2 to 20 carbon atoms (excluding those used as a monomer) as a comonomer may be performed. The (total) comonomer content in the propylene-based polymer is in the range of 0 mol% or more and 20 mol% or less, and it is possible to use a plurality of the above-mentioned comonomers. Specifically, they are ethylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene. Further, in order to further improve the melt properties, a small amount of a linear diolefin, specifically 1,5-hexadiene, 1,9-decadiene, etc. may be copolymerized.

4). Analysis / property evaluation of propylene-based polymer The propylene-based polymer according to the present invention has improved melt physical properties compared to a normal propylene-based polymer.
In the present invention, the strain hardening degree (λmax) in the measurement of elongational viscosity defined as an index of melt physical properties is an index representing the strength at the time of melting. When this value is large, there is an effect of improving the melt tension. As a result, for example, uneven thickness hardly occurs during blow molding. Further, when foam molding is performed, there is an effect that the closed cell ratio can be increased. The strain hardening degree (λmax) in the measurement of the extensional viscosity of the propylene-based polymer according to the present invention is 2.0 or more, preferably 4.0 or more, particularly preferably 5.0 or more.

The degree of strain hardening is an index representing the nonlinearity of elongational viscosity, and it is usually said that this value increases as the molecular entanglement increases. Molecular entanglement is affected by the amount of branching and the length of the branched chain. Therefore, the greater the amount of branching and the length of branching, the greater the degree of strain hardening.
With respect to the method for measuring the strain hardening degree, any method can be used in principle as long as the uniaxial extensional viscosity can be measured. For example, the details of the measuring method and measuring instrument are described in the publicly known document Polymer 42 (2001) 8663. Are listed. In the measurement of the propylene-based polymer according to the present invention, preferable measurement methods and measuring instruments include the following.

Measuring method 1:
・ Device: Ales manufactured by Rheometrics
-Jig: EXTENSIONAL VISUALITY FIXTURE, manufactured by TA Instruments
・ Measurement temperature: 180 ℃
-Strain rate: 0.1 / sec
-Preparation of test piece: A sheet of 18 mm x 10 mm and a thickness of 0.7 mm is formed by press molding.

Measurement method 2:
・ Device: Toyo Seiki Co., Ltd., Melten Rheometer
・ Measurement temperature: 180 ℃
-Strain rate: 0.1 / sec
-Preparation of test piece: An extruded strand is prepared at a speed of 10 to 50 mm / min using an orifice with an inner diameter of 3 mm at 180 ° C. using a Capillograph manufactured by Toyo Seiki Co., Ltd.

Calculation method:
The elongational viscosity at a strain rate of 0.1 / sec is plotted as a log-log graph of time t (second) on the horizontal axis and elongational viscosity ηE (Pa · second) on the vertical axis. On the logarithmic graph, the viscosity immediately before strain hardening is approximated by a straight line, the maximum value (ηmax) of the extensional viscosity ηE until the amount of strain becomes 4.0 is obtained, and on the approximate straight line up to that time Let ηlin be the viscosity.
FIG. 2 is an example of a plot of elongational viscosity. ηmax / ηlin is defined as λmax and is used as an index of strain hardening degree.

  The elongational viscosity and strain hardening degree calculated from the measuring method 1 and the measuring method 2 are, in principle, measured for the inherent extensional viscosity and strain hardening degree of the substance, and show the same value. Therefore, either measurement method 1 or measurement method 2 may be used.

  However, the measurement method 2 has a measurement restriction that a measurement sample hangs down when the molecular weight is relatively low (that is, when MFR> 2), and the measurement accuracy is lowered. In the measurement method 1, when measuring a relatively high molecular weight (MFR> 1), the measurement sample is deformed in a non-uniform manner, and distortion occurs at the time of measurement. There is a problem of measurement accuracy that is averaged and the strain hardening degree is estimated to be small. Therefore, it is preferable for convenience to use the measuring method 1 for those having a low molecular weight and the measuring method 2 for those having a high molecular weight.

  In general, in order to show a high degree of strain hardening, it is said that the entanglement molecular weight of polypropylene is preferably 7,000 or more as the branch length, but in order to show the above degree of strain hardening, GPC It is thought that it is 15,000 or more in the value of the weight average molecular weight (Mw) measured by 1.

¹³ CNMR can be used as a method for measuring the branching amount of the propylene-based polymer. The characteristic peaks of propylene-based polymers containing long chain branches are 3 methylene carbons, one each at 44.0-44.1 ppm, 44.7-44.8 ppm and 44.8-44.9 ppm. And methine carbon is observed at 31.6 to 31.7 ppm. Three methylene carbons close to the branched methine carbon have multiple asymmetric carbons in the molecule and are not mirror images of each other (diastereotopic). (See Macromolecules, Vol. 35, NO. 10.2002, pages 3839-3842).
The calculation of the amount of branching is based on the total skeleton forming carbon (integral value of methylene carbon and methine carbon when 2,1 bond or 1,3 bond is added in addition to carbon in which propylene is regularly bonded). Calculated using the peak intensity of methine carbon observed at 31.6-31.7 ppm.

The reason why the long chain branching is generated in the propylene-based polymer according to the present invention is that the polymer one end generated from the active species derived from the component [A-1] mainly exhibits a propenyl structure, and a so-called macromer is generated. This macromer is presumed to be incorporated into the active species derived from the component [A-2] having a higher copolymerizability, and the macromer copolymer is proceeding.
The formation of the macromer is considered to be generated by a special chain transfer reaction generally called β-methyl elimination. Surprisingly, R ⁵ of the component [A-1] is carbonized in a branched structure such as i-propyl group. It was found that a complex having a hydrogen group is particularly susceptible to β-methyl elimination reaction.
On the other hand, since the component [A-2] has a high copolymerization property with respect to the macromer, even if the macromer production step and the macromer copolymerization step are simultaneously performed, the production of the target propylene-based polymer having high melt properties (that is, Single-stage polymerization is possible, and even when hydrogen is added, the molecular weight can be controlled without deteriorating the melt properties, and is considered an important advance as an industrial production technique.

The measurement conditions for ¹³ CNMR are as follows.
350-400 mg of a sample was completely dissolved in 2.5 ml of deuterated 1,1,2,2, -tetrachloroethane in an NMR sample tube (10φ), and then measured at 125 ° C. by a proton complete decoupling method. The chemical shift was set to 74.3 ppm at the center of the three deuterated 1,1,2,2-tetrachloroethane peaks, and the chemical shifts of the other carbon peaks were based on this.

Flip angle: 90 degrees Pulse interval: 10 seconds Resonance frequency: 100 MHz or more Integration frequency: 10,000 times or more Observation range: -20 ppm to 179 ppm
Number of data points: 32768

Furthermore, in the propylene polymer produced by the production method of the present invention, the mm fraction of the three propylene unit chains obtained by ¹³ C-NMR is preferably 90% or more, more preferably 92% or more.
The mm fraction is a ratio of three propylene unit chains in which the direction of methyl branching in each propylene unit is the same among arbitrary three propylene unit chains composed of head-to-tail bonds in the polymer chain. This mm fraction is a value indicating that the steric structure of the methyl group in the polypropylene molecular chain is controlled isotactically, and the higher the value, the higher the level.

The peak based on the methyl group of the second unit in the third chain of propylene units represented by mm is based on the methyl group of the second unit in the three chain of propylene units represented by mr, less than 21.1 to 23.0 ppm. The peak is in the range of 20.5 to less than 21.1 ppm, and the peak based on the methyl group of the second unit in the three propylene unit chains represented by rr is in the range of 19.5 to less than 20.5 ppm. appear. Here, mm, mr, and rr are each represented by the following chemical structure.
The mm fraction was calculated from the spectral intensity of each structure of mm, mr, rr by the following formula.
mm fraction (%) = PPP [mm] / (PPP [mm] + PPP [mr] + PPP [rr]) × 100

  However, PPP [mm], PPP [mr], and PPP [rr] represent each structure of mm, mr, and rr in a propylene unit triple chain in which head-to-tail bonds are formed. The ratio was quantified from the area of the region attributed to each methyl carbon peak.

Here, PPP is not included in the methyl carbon peak intensity of the heterogeneous bond portion formed by the 2,1 bond (2,1 insertion) and the 1,3 bond (1,3 insertion) of the propylene monomer during polymerization. [Mm], PPP [mr], and PPP [rr] were each quantified.
In addition to the above-mentioned documents, spectrum assignment was carried out with reference to Macromolecules, (1975) 8 pp. 687 and Polymer, 30, vol. 1, 1350 (1989).
The proportion of the terminal propenyl structure was calculated by the same method as in JP-A-11-349634.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the summary is exceeded. In addition, the physical-property measurement, analysis, etc. in a following example follow the following method.

(1) Melt flow rate (MFR)
It was measured according to the melt flow rate (test conditions: 230 ° C., load 2.16 kgf) of the polypropylene test method of JIS K6758. The unit is g / 10 minutes.

(2) Molecular weight and molecular weight distribution (Mw, Mn, Q value)
The value of the weight average molecular weight (Mw) is obtained by gel permeation chromatography (GPC), and the details of the measuring method and measuring instrument are as follows.
Equipment: GPC manufactured by Waters (ALC / GPC, 150C)
Detector: MIRAN, 1A, IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: o-dichlorobenzene (ODCB)
Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection volume: 0.2 ml

The sample is prepared by preparing a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolving it at 140 ° C. for about 1 hour.
The baseline and section of the obtained chromatogram are performed as shown in FIG.
Further, the conversion from the retention capacity obtained by GPC measurement to the molecular weight is performed using a standard curve prepared in advance by standard polystyrene. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
Brand: F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
Inject 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL to create a calibration curve. The calibration curve uses a cubic equation obtained by approximation by the least square method.
The following numerical value is used for the viscosity formula: [η] = K × Mα used for conversion to molecular weight.
PS: K = 1.38 × 10 −4, α = 0.7
PP: K = 1.03 × 10−4, α = 0.78

(3) ME (memory effect):
Using a melt indexer manufactured by Takara Co., Ltd. at 190 ° C, an orifice diameter of 1.0 mm and a length of 8.0 mm were extruded under a load, and the extrusion speed was 0.1 g / min. At that time, the polymer extruded from the orifice was quenched in methanol, and the value of the strand diameter at that time was calculated as the value divided by the orifice diameter. This value correlates with MFR, and a large value indicates that the product appearance is improved when the swell is large and injection molding is performed.

(4) mm, long chain branching amount, terminal propenyl amount Using GSX-400, FT-NMR, manufactured by JEOL Ltd., and measured by the method described in the present specification. The unit is%.

(5) Elongation viscosity Measured by the method described in the present specification using a rheometer.

(6) Melting point (Tm)
Using a DSC6200 manufactured by Seiko Instruments Inc., the sample piece made into a sheet is packed in a 5 mg aluminum pan, heated from room temperature to 200 ° C. at a heating rate of 100 ° C./minute, held for 5 minutes, and then 10 ° C./minute. After the temperature was lowered to 20 ° C. for crystallization, the maximum melting peak temperature (° C.) when the temperature was raised to 200 ° C. at 10 ° C./min was obtained.

[Example 1]
(1) Component [A-1]: Dichloro {1,1′-dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2-isopropyl-4-phenyl-4H-azurenyl)} hafnium Synthesis of

(1-a) Synthesis of dimethyl (2,3,4,5-tetramethylcyclopentadienyl) (2-isopropyl-4-phenyl-1,4-dihydroazurenyl) silane 2-isopropylazulene (1.00 g , 5.9 mmol) was dissolved in hexane (30 mL), and a solution of phenyllithium in cyclohexane-diethyl ether (5.6 mL, 5.9 mmol, 1.04 N) was added dropwise at 0 ° C. After the dropwise addition, the mixture was warmed to room temperature and stirred for about 2 hours. The suspension was allowed to settle, the supernatant (20 mL) was removed, tetrahydrofuran (10 mL), hexane (10 mL) and N-methylimidazole (15 mL) were added, and chlorodimethyl (2,3,4,5-) was added at 0 ° C. Tetramethylcyclopentadienyl) silane (Aldrich, 1.3 mL, 5.9 mmol) was added dropwise. After dropping, the mixture was warmed to room temperature and stirred for 1.5 hours, and then distilled water was added to the reaction solution, followed by extraction with diethyl ether. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain dimethyl (2,3,4,5-tetramethylcyclopentadienyl) (2-isopropyl-4-phenyl-1,4-dihydroazule). Nyl) silane crude product (2.48 g) was obtained.

Synthesis of (1-b) dichloro {1,1′-dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2-isopropyl-4-phenyl-4H-azurenyl)} hafnium The crude ligand product (2.48 g) was dissolved in diethyl ether (15 mL), and an n-hexane solution of n-butyllithium (7.4 mL, 11.6 mmol, 1.58 N) was added dropwise at 0 ° C. After stirring at room temperature for 3 hours, toluene (70 mL) was added, cooled to −10 ° C., and hafnium tetrachloride (1.8 g, 5.8 mmol) was added. The temperature was raised slowly, and the mixture was stirred at room temperature for 3 hours.
The resulting reaction solution was concentrated to about ½, cooled and left overnight. The solution part was removed by decantation, and the precipitate was dried under reduced pressure to obtain a complex (2.9 g) containing an inorganic salt. Toluene (50 mL) was added thereto and heated to 70 ° C., and the insoluble matter was settled to separate the soluble matter. The obtained soluble component is concentrated to about ½, cooled to 0 ° C., and the precipitated product is filtered off and washed with hexane to obtain the desired dichloro {1,1′-dimethylsilylene (2,3,4). , 5-tetramethylcyclopentadienyl) (2-isopropyl-4-phenyl-4H-azurenyl)} hafnium (1.75 g) was obtained in a yield of 52%.
Proton nuclear magnetic resonance method of the obtained complex identified value according to ^{(1 H-NMR)} are shown below.

_{^{[1 H-NMR (CDCl 3}} ) Identification Results
¹ HNMR (400 MHz, CDCl ₃ )? 1.00 (s, 6 H, Me 2 Si), 1.01 (d, J = 8 Hz, 3 H, CH 3 CH ′ 3 CH), 1.06 (d, J = 8 Hz, 3 H, CH 3 CH '3CH), 2.01 (s, 3H, Me4Cp), 2.05 (s, 3H, Me4Cp), 2.11 (s, 3H, Me4Cp), 2.13 (s, 3H, Me4Cp), 3. 1 (m, 1H, CH), 5.2 (brs, 1H, 4-H), 5.76 (s, 1H, 3-H), 5.90-5.93 (m, 2H), 6 .09-6.11 (m, 1H), 6.75 (d, J = 11 Hz, 1H, 8-H), 7.2-7.45 (m, 5H, arom).

(2) Component [A-2]: Synthesis of rac-dichloro (1,1′-dimethylsilylenebis (2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl)) hafnium rac-dichloro (1,1 Synthesis of '-dimethylsilylenebis (2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl)) hafnium was carried out in the same manner as in Example 1 of JP-A-11-240909.

(3) Synthesis of Component [B-4]: Production and Preparation of Ion Exchangeable Layered Silicate (3-1) Chemical Treatment of Ion Exchangeable Layered Silicate 96% Sulfuric Acid (1044 g) in 3456 g of Distilled Water in a Separable Flask ) And then 600 g of montmorillonite (Mizusawa Chemical Benclay SL: average particle size 19 μm) was added as a layered silicate. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./minute, and reacted at 90 ° C. for 120 minutes. The reaction slurry was cooled to room temperature in 1 hour, added with 2400 g of distilled water and then filtered to obtain 1230 g of a cake-like solid.
Next, 648 g of lithium sulfate and 1800 g of distilled water were added to the separable flask to make a lithium sulfate aqueous solution, and the entire amount of the above solid on the cake was added, and 522 g of distilled water was further added. The slurry was heated to 90 ° C. over 1 hour at 0.5 ° C./minute, and reacted at 90 ° C. for 120 minutes. The reaction slurry was cooled to room temperature in 1 hour, filtered after adding 1980 g of distilled water, further washed with distilled water to pH 3, and filtered to obtain 1150 g of cake-like solid.
The obtained solid was preliminarily dried at 130 ° C. for 2 days under a nitrogen stream, and then coarse particles of 53 μm or more were removed, and further, rotary kiln drying was performed under a condition of 215 ° C. under a nitrogen stream for a residence time of 10 minutes. 340 g was obtained.
The composition of this chemically treated smectite is Al: 7.81 wt%, Si: 36.63 wt%, Mg: 1.27 wt%, Fe: 1.82 wt%, Li: 0.20 wt%, Al / Si = 0.222 [mol / mol].
Then, before using as a catalyst component, 200 degreeC vacuum drying was implemented for 5 hours, and it was used by the following catalyst preparation.

(4) Catalyst preparation The following operations were all performed under an inert gas. The solvent used was dehydrated and deoxygenated.
200 mg of the synthesized ion-exchange layered silicate was weighed into a 100 ml two-necked flask, 1.30 ml of n-heptane was added, and 0.70 ml of triisobutylaluminum (TiBA) -heptane solution (140 mg / ml) was added at room temperature. And stirred for reaction. After 1 hour, 50 ml of n-heptane was added and stirring was carried out for 5 minutes and allowed to stand. 50 ml of the supernatant was extracted with a siphon. This heptane addition was performed twice in total.
In parallel, dichloro {1,1′-dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2-isopropyl-4-phenyl-) synthesized in the above (1) and (2) was used. 4H-azurenyl)} hafnium and rac-dichloro (1,1′-dimethylsilylenebis (2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl)) hafnium are weighed and dissolved in toluene, and the component [A -1] was prepared at 0.5 mg / ml (0.590 micromol / ml), and component [A-2] was prepared at 0.3 mg / ml (0.369 micromol / ml).
To the previously prepared TiBA-treated ion-exchange layered silicate, component [A-1] dichloro {1,1′-dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2- 2.08 ml (1.20 μmol) of isopropyl-4-phenyl-4H-azulenyl)} hafnium solution was added and reacted, and after 5 minutes, rac-dichloro (1,1′-dimethylsilylenebis (2-methyl-) 4- (4-Chlorophenyl) -4-hydroazurenyl)) hafnium 0.81 ml (0.3 micromol) was added and reacted.

(5) Propylene polymerization Nitrogen was passed through a 3 L autoclave to dry it sufficiently, and after cooling, the inside of the tank was replaced with propylene. After cooling to 40 ° C. or lower, 2.86 mL (2.02 mmol) of a heptane solution of triisobutylaluminum (140 mg / mL) was added, and after introducing 750 g of liquid propylene, the temperature was raised to 75 ° C.
After the temperature was stabilized, the entire amount of the prepared catalyst was injected with argon, and propylene polymerization was started. After 1 hour, 5 ml of ethanol was added to stop the polymerization, the remaining propylene monomer was purged, and 283 g of propylene polymer was recovered.
The catalyst activity per solid catalyst was 1410 g / g-solid catalyst. Time, activity per metal complex is 220,000 g / g-complex. It was time.
The obtained polymer had a strain hardening (λmax) of 3.1, an MFR of 0.29 g / 10 min, a weight average molecular weight (Mw) of 558,000, and a molecular weight distribution (Mw / Mn) of 7. 98, and the melting point was 153.3 ° C. The results are summarized in Table 1.

[Comparative Example 1]
As component [A], dichloro {1,1′-dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2-isopropyl-4-phenyl-4H-azurenyl) of [A-1] } Performed in the same manner as in Example 1 except that 2.54 ml (1.5 μmol) of the hafnium solution was used and the polymerization temperature was 50 ° C.
As a result, 32 g of a propylene polymer was recovered. The catalytic activity per solid catalyst was 160 g / g. Time, activity per metal complex is 26,700 g / g-complex. It was time.
The obtained polymer was found to have a strain hardening (λmax) of 1.9, an MFR of 4.50 g / 10 min, a weight average molecular weight (Mw) of 28,000, and a molecular weight distribution (Mw / Mn) of 3. 30, ME was 1.64, and melting point was 152.2 ° C. The results are summarized in Table 1.

[Comparative Example 2]
As component [A], 2.44 ml of only rac-dichloro (1,1′-dimethylsilylenebis (2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl)) hafnium solution of [A-2] ( 1.5 micromole) was carried out in the same manner as in Example 1 except that it was used.
As a result, 340 g of a propylene polymer was recovered. The catalytic activity per solid catalyst was 1,700 g / g. Time, activity per metal complex is 279,000 g / g-complex. It was time.
The resulting polymer does not exhibit strain hardening in the measurement of elongational viscosity, MFR is 0.07 g / 10 min, weight average molecular weight (Mw) is 938,000, molecular weight distribution (Mw / Mn) is 3.11, and The melting point was 154.6 ° C. The results are summarized in Table 1.

[Reference Example 1]
It implemented similarly to the comparative example 1 except having implemented superposition | polymerization temperature at 75 degreeC. As a result, 98 g of propylene polymer was recovered.
The catalytic activity per solid catalyst was 490 g / g. Time, activity per metal complex is 81,700 g / g-complex. It was time. Since MFR was as high as 700 g / 10 min, the extensional viscosity and ME could not be measured. The weight average molecular weight (Mw) was 74,000, the molecular weight distribution (Mw / Mn) was 4.07, and the melting point was 143.7 ° C. The results are summarized in Table 1.
Moreover, when the terminal structure analysis was conducted by ¹³ CNMR, the proportion of the terminal propenyl structure was high, and the amount was converted to one propenyl per polymer chain when converted using the number average molecular weight (Mn) obtained from GPC as a standard. The end was found to be present. That is, almost 100% of the terminal ends are propenyl structures, indicating that the chain transfer reaction by β-methyl reaction occurs preferentially.

[Example 2]
The same procedure as in Example 1 was conducted except that 300 ml of hydrogen was added before propylene was introduced. As a result, 364 g of propylene polymer was recovered, and the catalyst activity per solid catalyst was 1,820 g / g. Time, activity per metal complex is 284,000 g / g-complex. It was time.
The obtained polymer had a strain hardening (λmax) of 6.35, an MFR of 0.93 g / 10 min, a weight average molecular weight (Mw) of 415,000, and a molecular weight distribution (Mw / Mn) of 6.35. 68, ME was 1.86, and melting point was 152.1 ° C. The results are summarized in Table 1.

[Example 3]
Amount of dichloro {1,1′-dimethylsilylene (2,3,4,5-tetramethylcyclopentadienyl) (2-isopropyl-4-phenyl-4H-azurenyl)} hafnium solution of component [A-1] From 2.08 ml (1.20 micromol) to 1.30 ml (0.75 micromol) to rac-dichloro (1,1′-dimethylsilylenebis (2-methyl-4- (4-chlorophenyl) -4 -Hydroazurenyl)) The amount of hafnium solution was changed from 0.81 ml (0.3 micromolar) to 2.03 ml (0.75 micromolar), with the exception that 450 ml of hydrogen were added before further propylene was introduced. 1 was carried out.
As a result, 450 g of propylene polymer was recovered, and the catalytic activity per solid catalyst was 2,250 g / g. Time, activity per metal complex is 357,000 g / g-complex. It was time.
The obtained polymer had a strain hardening (λmax) of 3.10, an MFR of 1.1 g / 10 min, a weight average molecular weight (Mw) of 398,000, and a molecular weight distribution (Mw / Mn) of 6.10. 31, ME was 1.79, and melting point was 152.9 ° C. The results are summarized in Table 1.

  As apparent from Table 1, the metallocene complex having a specific structure used in the production method of the present invention preferentially produces terminal propenyl, but when used alone, as in Comparative Examples 1 and 2, the melt properties Is insufficient performance as a catalyst for the production of an improved propylene polymer, but when used in combination with a specific complex for the macromer, the melt properties are improved as in Examples 1-3. Propylene polymers can be produced efficiently and with high activity. Further, in the production method of the present invention, as in Examples 2 and 3, even when hydrogen is added, the molecular weight can be controlled without deteriorating the melt properties.

  The production method of the propylene-based polymer of the present invention has good flow characteristics such as melt tension and melt viscoelasticity, and accordingly, at the time of blow molding, the swell ratio is high, so the molding processability is excellent, and at the time of extrusion foam molding, Since it has a strong strain hardening property, the closed cell ratio can be increased, and a propylene polymer suitable for blow molding, extrusion foam molding, etc. is efficiently produced by a simple method. It is highly available.

It is a figure explaining the baseline and section of the chromatogram in GPC. It is a plot figure which shows an example of the extensional viscosity measured with the uniaxial extensional viscometer.

Claims (7)

A method for producing a propylene polymer by polymerizing propylene in the presence of a catalyst containing at least the components shown in the following [A] to [C], wherein the obtained propylene polymer is measured for elongational viscosity. A method for producing a propylene-based polymer, wherein the strain hardening degree (λmax) in the resin has a characteristic of 2.0 or more.
Component [A]: at least two transition metal compounds selected from the following components [A-1] and [A-2], which are group 4 transition metal compounds of the periodic table.
[A-1]: Compound represented by the general formula (1)

[In Formula (1), Q ¹ is a binding group that bridges two conjugated five-membered ring ligands, a divalent hydrocarbon group having 1 to 20 carbon atoms, and a hydrocarbon having 1 to 20 carbon atoms. A silylene group having a group or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms, Me ¹ represents zirconium or hafnium, and X ¹ and Y ¹ are each independently hydrogen, halogen group, carbon A hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms 20 silicon-containing hydrocarbon groups are shown. R ^{1 to} R ⁴ are each independently a hydrocarbon group having 1 to 12 carbon atoms, a halogenated hydrocarbon group, or a silicon-containing hydrocarbon group, and R ¹ and R ² and / or R ³ and R ^{4. May} be bonded to form a divalent group, and R ⁵ is a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. It is a halogenated hydrocarbon group, and R ⁶ is an aryl group having 6 to 30 carbon atoms which may contain halogen, silicon, or a plurality of hetero elements selected from these. ]
[A-2]: Compound represented by the general formula (2)

[In Formula (2), Q ² is a binding group that bridges two conjugated five-membered ring ligands, a divalent hydrocarbon group having 1 to 20 carbon atoms, and a hydrocarbon having 1 to 20 carbon atoms. shows a germylene group having a silylene group or a hydrocarbon group having 1 to 20 carbon atoms having a group, Me ² represents zirconium or hafnium, X ² and Y ² are each independently hydrogen, halogen, carbon A hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms 20 silicon-containing hydrocarbon groups are shown. R ⁷ and R ⁸ are each independently a hydrocarbon group having 1 to 6 carbon atoms. R ⁹ and R ¹⁰ are each independently an aryl group having 6 to 30 carbon atoms which may contain halogen, silicon, or a plurality of hetero elements selected from these. R ¹¹ and R ¹² are each independently an unsaturated divalent hydrocarbon group having 3 to 5 carbon atoms. R ¹³ and R ¹⁴ are each independently a hydrocarbon group having 1 to 6 carbon atoms, a halogenated hydrocarbon group, or a silicon-containing hydrocarbon group. m and n are each independently 0 or an integer less than or equal to twice the number of carbon atoms of R ¹³ and R ¹⁴ (provided that when m and n are 2 or more, R ¹³ and R ¹⁴ are each in an arbitrary position) And may be bonded to form a ring structure). ]
Component [B]: an aluminum oxy compound [B-1], an ionic compound or Lewis acid [B-2] that can be converted into a cation by reacting with the transition metal compound of component [A], solid acid fine particles [ B-3] and at least one selected from the group of compounds consisting of ion-exchangeable layered silicate [B-4].
Component [C]: Organoaluminum.   The ratio of the amount of [A-1] to the total amount of components [A-1] and [A-2] is 0.30 to 0.99 in terms of molar ratio. A method for producing a propylene-based polymer.   The method for producing a propylene polymer according to claim 1 or 2, wherein the component [B] is an ionic layered silicate [B-4].   The method for producing a propylene-based polymer according to any one of claims 1 to 3, wherein the ion-exchangeable layered silicate [B-4] is a smectite group. The method for producing a propylene-based polymer according to any one of claims 1 to 4, wherein Me ^{1 of} component [A-1] is hafnium. The method for producing a propylene-based polymer according to any one of claims 1 to 5, wherein Me ^{2 of the} component [A-2] is hafnium. The production of the propylene-based polymer according to any one of claims 1 to 6, wherein R ^{5 of the} component [A-1] is a hydrocarbon group having 3 to 6 carbon atoms having a branched structure. Method.

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