JP2002030109A - Catalyst composition for preparing olefin polymer having wide molecular weight distribution - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new catalyst composition useful for preparing an olefin polymer having a wide molecular weight distribution. SOLUTION: A catalyst composition comprising a carbon-bridged biscyclopentadienyl metallocene, a constrained geometry catalyst and an activation co-catalyst is used for polymerizing an olefin. An olefin polymer having a wide molecular weight distribution (Mw/Mn>=3) and in a single morphology, dual morphology or polymorphology is prepared.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a catalyst composition used for producing an olefin polymer, particularly to a monomodal polymer.
l), bimodal, or multimodal
The present invention relates to a catalyst composition used for producing an olefin polymer having a wide molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn ≧ 3).

[0002]

BACKGROUND OF THE INVENTION Metallocene catalysts activated by aluminoxanes are used to polymerize olefins to obtain polyolefins having a narrow molecular weight distribution (Mw / Mn = 2-3). However, thermoforming, extrusion,
In a variety of applications, such as blow molding, and in the formation of polyolefin foams and films, a broad bimorph molecular weight distribution is required for their excellent processability. Also, such polymers have a fast output under low energy, and the molten material (mo
lten material has a low perburbat
ion). For this reason, a highly efficient metallocene catalyst system that can be used for the production of polyolefins having a wide molecular weight distribution has been desired in related industries.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel catalyst composition capable of producing an olefin polymer having a broad molecular weight distribution in a monomorphic form, a dimorphic form or a polymorphic form.

[0004]

In order to achieve the above object, the catalyst composition of the present invention comprises (a) a bridged biscyclopentadienyl metallocene represented by the formula (B):
biscyclopentadienyl metallocene), (b) Formula (A)
1) or monocyclopentadienyl metallocene (mono) selected from the group consisting of compounds represented by formula (A2)
cyclopentadienyl metallocene), and (c)
Activated cocatalysts (R ¹¹ , R ¹²⁾ selected from (1) aluminoxane, (2) a mixture of AlR ¹¹ R ¹² R ¹³ and borate, or (3) a mixture of AlR ¹¹ R ¹² R ¹³ and aluminoxane , And R ¹³ are aliphatic groups having 1-20 carbon atoms, or aromatic groups having 6-10 carbon atoms).

[0005]

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In the formula (B), R ¹ is the same or different and is hydrogen, halogen, and an alkyl, alkenyl, aryl (eg, phenyl, alkylaryl) group having 1 to 20 carbon atoms, or A substituent selected from the group consisting of arylalkyl groups,
Or two adjacent R ^{1 s} are joined together to form a saturated or unsaturated ring having 4-20 carbon atoms, including the two carbon atoms to which each is attached. R ² are the same or different and are selected from the group consisting of hydrogen, halogen, and an alkyl, alkenyl, aryl (eg, phenyl, alkylaryl) or arylalkyl group having 1 to 20 carbon atoms. Is a substituent, or two adjacent R ¹ are bonded to each other;
It forms a saturated or unsaturated ring having 4 to 20 carbon atoms, including the two carbon atoms to which each is attached.

[0007] X is selected from the group consisting of carbon, silicon, germanium, and tin. n is 2-12. R
³ and R ⁴ are the same or different and are selected from the group consisting of hydrogen, halogen, and an alkyl, alkenyl, aryl (eg, phenyl, alkylaryl) or arylalkyl group having 1 to 12 carbon atoms. Is the substituent selected. M is a Group IVA transition metal having an oxidation state of +4. Y is the same or different and each is an anionic ligand having a valence of -1.

In the formula (A1) or (A2), M
¹ is a Group IVA transition metal having an oxidation state of +4. M ² is,
The oxidation state is selected from the group consisting of +3 Group IIIA transition metals, lanthanides, and titanium. Z is the same or different and is a Group IVB element. R ²¹ are the same or different,
A saturated or unsaturated divalent substituted or unsubstituted hydrocarbon group having 3 to 6 carbon atoms which forms a ring with Z; an alkyl group having 1 to 20 carbon atoms;
Alkenyl groups having 0 carbon atoms, aryl groups having 6 to 20 carbon atoms (for example, phenyl group, 7
And an alkylaryl group having from 20 to 20 carbon atoms), and a side chain selected from the group consisting of arylalkyl groups having from 7 to 20 carbon atoms.

R ²² is the same or different and is hydrogen, 1-20
A linear, branched, or cyclic hydrocarbon group having two carbon atoms, or a silyl group, or two adjacent R ²² are bonded to each other to form two carbon atoms to be bonded to each other. Form a saturated or unsaturated ring having from 4 to 6 carbon atoms, including: X ²¹ is the same or different and is an anion ligand having a valence of −1 or −2, respectively. P is 2 or 1. Y ¹ and Y ² are a VB element or a VIB element. Q when Y ¹ is the VB element
Is 1. Q is 0 when Y ¹ is the VIB element. Y ²
Q is 2 when is a VB element. Q is 1 when Y ² is the VIB element. R ²³ are the same or different and are hydrogen or a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS <Catalyst composition> As described above, the catalyst composition of the present invention contains a bridged biscyclopentadienyl metallocene, a monocyclopentadienyl metallocene, and an activating cocatalyst.

<Bridged Biscyclopentadienyl Metallocene> The bridged biscyclopentadienyl metallocene used in the present invention can be represented by the formula (B). In formula (B), X (Group IVB element such as carbon, silicon, germanium, tin, etc.) is cross-linked by (R ³ R ⁴ C) _n . n is 2 to 12, preferably 3. R
³ and R ⁴ are hydrogen, halogen, and an alkyl group, alkenyl group, aryl group having 1 to 12 carbon atoms,
Or an arylalkyl group, preferably hydrogen.

In the formula (B), R ¹ and R ² are 1 to 2
When it is an alkyl group, alkenyl group, aryl group (for example, phenyl group, alkylaryl group) or arylalkyl group having 0 carbon atoms, 1 to 15
And preferably an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms (for example, a phenyl group , An alkylaryl group having 7 to 10 carbon atoms), and an arylalkyl group having 7 to 10 carbon atoms.

Representative examples of R ¹ and R ² include hydrogen, methyl, ethyl, propyl, butyl, isobutyl,
Examples include pentyl, isopentyl, hexyl, 2-ethylhexyl, heptyl, octyl, vinyl, allyl, isopropenyl, phenyl, and tolyl groups.

Two adjacent R ¹ (and / or R ² )
Combine with each other to form a saturated or unsaturated ring having from 4 to 20 carbon atoms, including the two carbon atoms to which each is attached, to form a ring having from 4 to 6 carbon atoms Is preferred. Two adjacent R ¹ (and / or R ² ) are bonded to each other to form a cyclopentadienyl moiet which is bonded to each other.
y) with a saturated or unsaturated polycyclic cyclopentadienyl ligand, for example a saturated or unsaturated polycyclic cyclopentadiene such as an indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl group Dienyl ligands can be formed.

Representative examples of such a ring include η ⁵ -cyclopentadienyl group, η ⁵ -methylcyclopentadienyl group, η ⁵ -ethylcyclopentadienyl group, η ⁵ -propylcyclopentadienyl group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - pentamethylcyclopentadienyl group, eta ^{5-n-butylcyclopentadienyl} group,
Examples include an indenyl group, a tetrahydroindenyl group, a fluorenyl group, and an octahydrofluorenyl group.

Y is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, a halogen, an aryl group having 6 to 20 carbon atoms (for example, phenyl group, alkyl having 7 to 20 carbon atoms) Aryl groups), arylalkyl groups having 7 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryloxy groups having 1 to 20 carbon atoms, NH ₂ , NHR ⁷ , NR ⁷ R ⁸ ,-
_{(C = O) NH 2,} - (C = O) NHR 9, - (C = O)
A ^{NR 9 R 10, R 7,} R 8, R 9, and it is preferred that R ^{1 0} is an alkyl group having 1 to 20 carbon atoms, respectively. Suitable Y includes methyl, ethyl, phenyl, chlorine, bromine, methoxy, ethoxy, -NH
_{2, -NH (CH 3),} - N (CH 3) 2, -N (C 2 H 5)
_2, and -N (C ₃ H ₇₎ include ₂ like.

<Monocyclopentadienyl metallocene>
The monocyclopentadienyl metallocene used in the present invention is a compound represented by the formula (A1) (compound (A1)) or a compound represented by the formula (A2) (compound (A2)), or a compound represented by the formula (A1) (A
It can be a combination with 2).

[0018]

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In the formula (A1), M ¹ is titanium (+
4), zirconium (+4), hafnium (+4), and the like are Group IVA transition metals having an oxidation state of +4. Z is a Group IVB element such as carbon, silicon, and germanium.

R ²¹ is a saturated or unsaturated divalent substituted or unsubstituted hydrocarbon group having 3 to 6 carbon atoms which forms a ring with Z, and has 1 to 20 carbon atoms. An alkyl group, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms (for example, a phenyl group, an alkylaryl group having 7 to 20 carbon atoms) or 7 to 20 And a side chain selected from the group consisting of arylalkyl groups having the following carbon atoms. Particularly, R ²¹ is preferably a saturated divalent substituted or unsubstituted hydrocarbon group having 3 to 6 carbon atoms. Representative examples of R ²¹ include trimethylene,
Includes tetramethylene, pentamethylene, hexamethylene and the like.

R ²² may be the same or different and may each be hydrogen, a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms, or a silyl group. The silyl group can be an alkylsilyl group, a dialkylsilyl group, a trialkylsilyl group, a cycloalkylsilyl group. Representative examples include a methylsilyl group, a dimethylsilyl group,
A trimethylsilyl group, a methylethylsilyl group and the like are included. On the other hand, two adjacent R ²² are bonded to each other, including the two carbon atoms, each of which binds 4-20
It may form a saturated or unsaturated ring having two carbon atoms.

Specifically, linear, branched or cyclic hydrocarbon groups having 1 to 20 carbon atoms are 1 to 20 carbon atoms.
Alkyl groups having 2 carbon atoms, alkenyl groups having 2-20 carbon atoms, aryl groups having 6-20 carbon atoms (e.g., phenyl groups, alkylaryl groups having 7-20 carbon atoms) ) Or 7-20
It can be an arylalkyl group having two carbon atoms.
Representative examples of R ²² include hydrogen, a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, a 2-ethylhexyl group, a heptyl group, an octyl group, a vinyl group, an allyl group , An isopropenyl group, a phenyl group, and a tolyl group.

[0023] Specifically, 4 including the two adjacent linked R ²² is in each other two carbon atoms, each of which binds
When forming a saturated or unsaturated ring having from 20 to 20 carbon atoms, R ²² represents a cyclopentadienyl group to which each is attached, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, or an octahydrofluorene group. Forming a saturated or unsaturated polycyclic cyclopentadienyl ligand such as a nyl group.

The cyclopentadienyl ligand C ₅ (R ²² ) ₄
A representative example, eta ⁵ - cyclopentadienyl group, eta ⁵ - methylcyclopentadienyl group, eta ⁵ - ethyl cyclopentadienyl group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - penta Methylcyclopentadienyl group, η ⁵
-N-butylcyclopentadienyl group, indenyl group,
Examples include a tetrahydroindenyl group, a fluorenyl group, and an octahydrofluorenyl group.

R ²³ is hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms (for example, phenyl group, Alkylaryl groups having 7 to 20 carbon atoms), and arylalkyl groups having 7 to 20 carbon atoms.

X ²¹ is an anion ligand having a valence of -1 or -2. P is 2 when X ²¹ is a valence-1 anion ligand. Representative examples of such X ^21,
Examples include hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, an alkoxide group, an aryloxide group, and an amide group. P is 1 when X ²¹ is a valence-2 anion ligand. Representative examples of such X ²¹ include dicarborane dianion (dicarborane dianion).
anion).

When Y ¹ is a Group VB element, q is 1. Representative examples of such Y ¹ include nitrogen, phosphorus, and arsenic. When Y ¹ is a Group VIB element, q
Is 0. Representative examples of such Y ¹ include oxygen, sulfur, and selenium. Representative examples of _{^{Y 1 (R 23) q,}} -NH -, - N (CH 3) -, - N (t- butyl)
-, - PH -, - P (CH 3) -, - P (t- butyl)
-, -O-, and -S- and the like.

Although the monocyclopentadienyl metallocene represented by the formula (A1) and the monocyclopentadienyl metallocene represented by the formula (A2) are structurally similar, M ² and Y in the formula (A2) are similar. The bond between ² and
It differs from the bond between M ¹ and Y ¹ in formula (A1). M ² in the formula (A2) is IIIA of which oxidation state is +3.
Group transition metal, lanthanide, or titanium.

In the formula (A2), the bond between M ² and Y ² is not a covalent bond but a dative bond, and Y ² is M ²
To give two electrons. When Y ² is the VB element, q
Is 2. When Y ² is the VIB element, q is 1. Z, R ²¹ , R ²² , X ²¹ , and R ²³ have the same definition in both formulas (A1) and (A2).

In the formula (A2), Y^Two(R^{twenty three})_qRepresentative of
Examples include OH, OCH_Three, SH, SCH_Three, NH_Two, N
(CH_Three)_Two, NH (CH_Three), NH (C₆H₁₁), N (C
₆H₁₁)_Two, NH (tertiary butyl), PH_Two, P (C
H_Three)_Two, PH (CH_Three), PH (C₆H ₁₁), And P
(C₆H₁₁)_TwoAnd so on.

<Activating Cocatalyst> The activating cocatalyst applicable in the present invention includes (1) aluminoxane, (2) Al
A mixture of R ¹¹ R ¹² R ¹³ and a borate, or (3) Al
It is a mixture of R ¹¹ R ¹² R ¹³ and an aluminoxane.
R ¹¹ , R ¹² and R ¹³ are an aliphatic group having 1 to 20 carbon atoms or an aromatic group having 6 to 10 carbon atoms.

A common commercial aluminoxane is methylaluminoxane (MAO).

Representative examples of AlR ¹¹ R ¹² R ¹³ include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, and triisobutylaluminum (TIBA).

The borates applicable in the present invention include:
N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (N, N-dimethylanilinium tet)
rakis (pentafluorophenyl) borate), triphenyl carbenium tetrakis (pentafluorophenyl) borate
l) borate), trimethylammonium tetrakis (pentafluorophenyl) borate (trimethyl ammonium t
etrakis (pentafluorophenyl) borate), ferrocenium tetrakis (pentafluorophenyl) borate (ferr
ocenium tetrakis (pentafluorophenyl) borate), dimethyl ferrocenium tetrakis (pentafluorophenyl) borate
luorophenyl) borate), and silver tetrakis (pentafluorophenyl) borate
orophenyl) borate).

<Production of Olefin Polymer> By using the catalyst composition of the present invention, an olefin polymer can be produced successfully. In the presence of a catalytically effective amount of the catalyst composition of the present invention under polymerization conditions, olefins can be polymerized (homopolymerization), two or more olefins can be polymerized, and at least 1 One olefin can be polymerized with at least one other monomer (copolymerization).

The olefin monomer applicable to the present invention may be a cycloolefin or an acyclic olefin. The acyclic olefin can be ethylene or an α-olefin having 3 to 12 carbon atoms. Examples of α-olefins include 1-propylene, 1-butene, 1
-Pentene, 1-hexene, 1-octene and the like.

The catalyst composition of the present invention is preferably a linear low-density olefin polymer having a broad molecular weight distribution,
Particularly suitable for the production of polyethylene.

The catalyst composition of the present invention can be used under slurry reaction conditions, gas phase, and solution polymerization reaction conditions. The polymerization is generally carried out at a temperature of
The process is performed at a pressure of 0 psi or less.

US Pat. Nos. 4,530,914 and 56
96045 discloses a catalyst system for the polymerization of ethylene into polyethylene having a broad molecular weight distribution, which is bi- or polymorphic. However,
In these known techniques, the catalyst composition of the present invention is not described.

[0040]

EXAMPLES In order to further clarify the above-mentioned method and advantages of the present invention, preferred embodiments of the present invention will be described below in more detail, but this does not limit the present invention. Anyone skilled in the art can add various fluctuations and colors.

<Production of Metallocene> Example 1: Production of (C ₅ Me ₄ H) Li Tetramethylcyclopentadiene (C ₅ Me ₄ H ₂ )
(8.57 g, 70.2 mol) in diethyl ether 1
Placed in a Schlenk flask containing 50 ml. The flask was cooled to −78 ° C., and one equivalent of an n-butyllithium (n-BuLi) solution was injected with a syringe. Then
The mixture turned yellow and gradually faded in color. The mixture was warmed at room temperature and stirred overnight. Then, this was filtered and washed several times with pentane to obtain 4.83 g of a white solid (lithium salt).

Example 2: (C ₅ Me ₄ H) (CH ₂ ) ₃ Si
Cl The lithium salt (4.8 g) obtained in Example 1 was dissolved in toluene / T
It was suspended in an HF mixed solution (2: 1 by volume). The slurry was cooled to -78 ° C and an excess of trimethylenesilyl dichloride was injected.
The mixture was warmed at room temperature and stirred overnight. This was stripped under vacuum to remove solvent and excess silyl dichloride. The residue is extracted with pentane, filtered and
The white LiCl salt was removed and stripped under vacuum to remove the solvent to give a pale yellow liquid (8.05 g).

Example 3 C ₅ Me ₄ H—Si (CH ₂ ) ₃ —
NHC (CH ₃ ) ₃ (C ₅ Me ₄ H) (CH ₂ ) ₃ SiCl (8
g) was dissolved in 30 ml of toluene. This solution was
After cooling to 8 ° C., excess t-butylamine (2.
1 eq.). The mixture was warmed at room temperature and stirred overnight. This thick slurry is filtered to remove white salts,
Stripped under vacuum to remove pentane solvent. This gave a faded yellow liquid (8.1 g).

Example 4: [C ₅ Me ₄ -Si (CH ₂ ) _3-
Preparation of NC (CH ₃ ) ₃ ] Li ₂ C ₅ Me ₄ H—Si (CH ₂ ) ₃ —NH obtained in Example 3
C (CH ₃ ) ₃ (8.1 g) was added to 60 ml of diethyl ether.
Dissolved in The solution was cooled to -78 C and 2 equivalents of n-BuLi were injected with a syringe. The mixture was warmed at room temperature and stirred overnight. This was filtered to obtain 7.5 g of a white solid.

Example 5: [C ₅ Me ₄ —Si (CH ₂ ) ₃ —
Preparation of NC (CH ₃ ) ₃ ] TiCl ₂ (Catalyst I) [C ₅ Me ₄ —Si (CH ₂ ) ₃ —NC (C
H ₃ ) ₃ ] Li ₂ and TiCl ₃ (thf) ₃ were suspended in 25 ml of tetrahydrofuran (THF), respectively.
Cooled to 30 ° C. The two solutions were mixed and stirred for 3 hours. Excess AgCl (2.1 g) was added to the mixture in the dark and stirred overnight. Then, Ag salts were removed by filtration. The filtrate was stripped under vacuum, extracted with toluene and recrystallized in toluene / pentane. A pale yellow solid product was obtained (80%).

Example 6: 1-cyclopentadienyl-1
Preparation of indenylcyclobutane Indene (5.8 g, 50 mmol) was added to 50 ml of THF.
Was placed in a 250 ml round bottom flask. This solution is placed in an ice bath and n-butyllithium (n-BuL
i) 40 ml (1.6 M, 64 mmol) were added. The mixture turned red-orange. The flask was then removed from the ice bath and the mixture was stirred for 3 hours. The reaction mixture was stripped under vacuum to remove the solvent, washed with 50 ml of pentane to remove excess n-BuLi,
The mixture was filtered to obtain a precipitate.

This precipitate was dissolved in 50 ml of THF,
The solution was placed in an ice bath and 6,6-trimethylenefulvene (5.9 g, 50 mmol) was added. After stirring for 24 hours, 1 ml of water was added to the mixture to terminate the reaction. The reaction mixture was stripped under vacuum to remove the solvent and hexane 100 ml.
And filtered to obtain a filtrate. Crude product (filtrate, etc.)
Was purified by column chromatography using 20 g of silica gel as packing and 100% hexane as eluent. The solution was concentrated under reduced pressure to obtain a faded yellow liquid (8.2 g, yield = 70).
%).

Example 7: cyclobutylidene (1-η ⁵
Preparation of -cyclopentadienyl)-(η ⁵ -indenyl) bis (dimethylamino) zirconium (catalyst II) 0.94 g (4 mmol) of 1-cyclopentadienyl-1-indenyl-cyclobutane obtained in Example 6 And Zr
(NMe ₂ ) ₄ was placed in a 100 ml round bottom flask. 20 ml of toluene was added and the reaction was carried out at room temperature for 15 hours. The reaction mixture was stripped under vacuum to remove any solvent. Then, 50 ml of pentane was added to dissolve the remaining solid. The mixture was filtered and the filtrate was concentrated to give a yellow solid product (1.45 g). The production rate was 95%.

<Production of Polymer> Examples 8 to 10 and Comparative Examples 1-2: Production of Polyethylene The reactor was heated to 110 ° C. for 2 hours under vacuum and filled with high-purity nitrogen. The same procedure was repeated three to four times. Solvent having a water content of 10 ppm or less (toluene or isoper (Isop)
ar) E; 500 ml) was injected into the reactor by cannula. The reaction temperature was adjusted to the desired reaction temperature.
After the temperature was stabilized, an appropriate amount of co-catalyst (MAO) was added to the reactor with an injector and stirred well. Catalyst I obtained in Example 5
And the catalyst II obtained in Example 7 was dissolved in toluene and added to the reactor. After stirring for 3 minutes, constant pressure ethylene was introduced into the reactor. After reacting for 30 minutes, the reactor was cooled to room temperature, the pressure was reduced to normal pressure, and the product was discharged from the reactor. An excess amount of a mixed solvent (hydrochloric acid / methanol, v / v = 1/10) was added to the product to precipitate a polymer, and metal salts contained in the product were removed. The reaction mixture was filtered and washed several times with methanol. The resulting polymer was dried in a vacuum oven (65 ° C.) for 12 hours and subjected to various tests. Table 1 shows the results.

[0050]

[Table 1]

P _C2H4 = 150 psig, Al / metal (molar ratio) = 3000, temperature = 120 ° C., solvent = toluene, M
WD (Molecular weight distribution) = Mw / Mn From the results in Table 1, under the same reaction conditions for producing polyethylene, Catalyst II has higher polymer activity than Catalyst I, but the molecular weight of polyethylene obtained using Catalyst II Is lower than the molecular weight of polyethylene obtained using Catalyst I. When catalysis of the polymerization reaction is carried out using a mixed catalyst system in which the ratio of catalyst I and catalyst II is different, two peaks can be seen in the GPC diagram of the obtained polymer. This indicates that the obtained polymer is bimodal. The activity of the mixed catalyst system is in the range of the activity of the two single catalysts. As the amount of Catalyst II used increases, the activity of the mixed catalyst system increases and the molecular weight of the resulting polymer decreases.

Although the preferred embodiments of the present invention have been disclosed above, they are not intended to limit the present invention in any way, and any person skilled in the art can make various changes without departing from the spirit and scope of the present invention. , And the scope of protection of the present invention is based on the contents specified in the claims.

[0053]

According to the present invention, a wide molecular weight distribution (Mw
/ Mn ≧ 3) can be produced in mono-, bi-, or polymorphic olefin polymers.

Continued on front page F-term (reference) 4J028 AA02A AB01A AB02A AC01A AC09A AC27A AC45A AC49A BA00A BA01B BA02B BC15B BC25B CA39B EB01 EB02 EB04 EB05 EB07 EB08 EB09 EC01 EC02 FA02 GA06 GB07

Claims (34)

[Claims] (A) Formula (B)(R¹Are the same or different and are hydrogen, halogen, and 1
Alkyl groups having up to 20 carbon atoms, alkenyl
Group, aryl group, alkylaryl group, or aryl
A substituent selected from the group consisting of
Or two adjacent R¹Are connected to each other,
4 to 20 carbon atoms, including the two carbon atoms to which is attached
To form a saturated or unsaturated ring having^TwoIs the same
Alternatively, hydrogen, halogen, and 1-20 carbons
An alkyl group having an atom, an alkenyl group, an aryl group,
From an alkylaryl group or an arylalkyl group
A substituent selected from the group consisting of
R ¹Are bonded to each other, and two
Saturated or having 4 to 20 carbon atoms, including carbon atoms
Forms an unsaturated ring, X represents carbon, silicon, germanium
And tin are selected from the group consisting of
Yes, R^ThreeAnd R^FourAre the same or different, hydrogen, halogen
An alkyl group having 1 to 12 carbon atoms,
Alkenyl, aryl, alkylaryl, or
Is a substituent selected from the group consisting of arylalkyl groups
And M is a Group IVA transition metal having an oxidation state of +4;
Y is the same or different and each has an valence of -1;
Bridged biscyclopenta represented by the formula:
Dienyl metallocene, (b) Formula (A1) or Formula (A
2)(M¹Is a Group IVA transition metal with an oxidation state of +4,^Two
Is a lanthanide, a Group IIIA transition metal having an oxidation state of +3.
And Z are selected from the group consisting of
Is a different group IVB element, and R^{twenty one}Are the same or different
And saturated with 3 to 6 carbon atoms forming a ring with Z
Or an unsaturated divalent substituted or unsubstituted hydrocarbon group
An alkyl group having 1 to 20 carbon atoms,
Alkenyl groups having 20 carbon atoms, 6-20
Aryl groups having carbon atoms, 7 to 20 carbon atoms
Alkylaryl groups having from 7 to 20 carbon atoms
Selected from the group consisting of arylalkyl groups having
Can have a side chain;^{twenty two}Are the same or different, water
Elemental, linear, branched, having 1 to 20 carbon atoms
Or a cyclic hydrocarbon group or a silyl group;
Is two adjacent R ^{twenty two}Are connected to each other and
Having 4-20 carbon atoms, including the two carbon atoms
Forming a saturated or unsaturated ring,^{twenty one}Are the same or
Are different, each having a valence of -1 or -2.
P is 2 or 1, Y is¹And Y^Two
Is a group VB element or a group VIB element;¹Is the
When the element is a VB group element, q is 1;¹Is a Group VIB element
When q is 0, Y^TwoIs 2 if V is a group VB element
Yes, Y^TwoIs a group VIB element, q is 1;^{twenty three}Is
Same or different, hydrogen, or 1-20 carbon atoms
A linear, branched, or cyclic hydrocarbon group having
Selected from the group consisting of compounds represented by
Clopentadienyl metallocene and (c) (1)
Aluminoxane, (2) AlR¹¹R¹²R¹³And borate
Or (3) AlR¹¹R¹²R¹³And aluminoki
An activating cocatalyst selected from a mixture with sun (R¹¹,
R¹², And R¹³Is a fat having 1 to 20 carbon atoms
Aliphatic group or aromatic group having 6 to 10 carbon atoms
Olefin polymer characterized by containing
A catalyst composition for producing. 2. In the formula (B), R ¹ and R ² are hydrogen, an alkyl group having 10 to 10 carbon atoms, 2 to 1
An alkenyl group having 0 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 10 carbon atoms, and an arylalkyl group having 7 to 10 carbon atoms The catalyst composition according to claim 1, which is a substituent selected from each group. 3. R ¹ and R ² are hydrogen, methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, 2-ethylhexyl, heptyl, octyl, vinyl The catalyst composition according to claim 2, which is a substituent selected from the group consisting of a group, an allyl group, an isopropenyl group, a phenyl group, and a tolyl group. 4. In the formula (B), two adjacent R ¹
Are combined with each other to form a saturated or unsaturated ring having from 4 to 20 carbon atoms, including the two carbon atoms to which each is attached. 5. In the formula (B), two adjacent R ¹
5. The catalyst composition according to claim 4, wherein R 1 and R 2 are bonded to each other to form a saturated or unsaturated polycyclic cyclopentadienyl ligand with the cyclopentadienyl group bonded to each other. 6. The polycyclic cyclopentadienyl ligand is an indenyl group, a tetrahydroindenyl group, a fluorenyl group, or an octahydrofluorenyl group.
A catalyst composition as described. 7. In the formula (B), two adjacent R ²
7. The catalyst composition according to claim 4, 5 or 6, wherein R is bonded to each other to form a saturated or unsaturated ring having 4 to 12 carbon atoms including the two carbon atoms to which each is bonded. 8. In the formula (B), two adjacent R ²
Are bonded to each other to form a saturated or unsaturated polycyclic cyclopentadienyl ligand and a cyclopentadienyl group to which they are bonded. 9. The polycyclic cyclopentadienyl ligand is an indenyl group, a tetrahydroindenyl group, a fluorenyl group, or an octahydrofluorenyl group.
A catalyst composition as described. 10. The catalyst composition according to claim 1, wherein in the formula (B), X is carbon. 11. In the formula (B), n is 3, and R
³ and R ⁴ are hydrogen 10. A catalyst composition according. 12. In the formula (B), Y is hydrogen, 1 to
Hydrocarbon groups having 20 carbon atoms, halogens, 6 to
Aryl groups having 20 carbon atoms, alkylaryl groups having 7-20 carbon atoms, arylalkyl groups having 7-20 carbon atoms, alkoxy groups having 1-20 carbon atoms, 1- an aryloxy group having 20 carbon ^{_{atoms, NH 2, NHR 7, NR}} 7 R 8, -
_{(C = O) NH 2,} - (C = O) NHR 9, - (C = O)
A ^{NR 9 R 10, R 7,} R 8, R 9, and catalyst composition of claim 1 wherein the alkyl group R ¹⁰ has from 1 to 20 carbon atoms, respectively. 13. The method according to claim 12, wherein Y is —N (CH ₃ ) _2.
A catalyst composition as described. 14. In the formulas (A1) and (A2),
The catalyst composition according to claim 1, wherein R ²¹ is a divalent substituted or unsubstituted hydrocarbon group. 15. The method according to claim 14, wherein R ²¹ is trimethylene.
A catalyst composition as described. 16. In the formulas (A1) and (A2),
2. The catalyst composition according to claim 1, wherein Z is silicon. 17. In the formulas (A1) and (A2),
R ²² is hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, 6 to
A substituent selected from the group consisting of an aryl group having 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and a silyl group. The catalyst composition according to claim 1. 18. R ²² is hydrogen, a methyl group, an ethyl group,
Propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, 2-ethylhexyl, heptyl, octyl, vinyl, allyl, isopropenyl, phenyl, and tolyl groups 18. The catalyst composition according to claim 17, which is a substituent selected. 19. The catalyst composition according to claim 17, wherein R ²² is a substituent selected from the group consisting of a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, and a methylethylsilyl group. 20. In the formulas (A1) and (A2),
Two adjacent bonded R ²² is mutually catalyst composition of each saturated or claim 1 wherein the forming an unsaturated ring having from 4 to 20 carbon atoms including two carbon atoms are bonded object. 21. R ²² are bonded to each other, and cyclopentadienyl group, each of which binds claim 20 to form a polycyclic cyclopentadienyl ligand saturated or unsaturated
A catalyst composition as described. 22. The polycyclic cyclopentadienyl ligand,
22. The catalyst composition according to claim 21, which is an indenyl group, a tetrahydroindenyl group, a fluorenyl group, or an octahydrofluorenyl group. 23. In the formulas (A1) and (A2),
p is 2 and X ²¹ has a valence of −1 selected from the group consisting of hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, an alkoxide group, an aryloxide group, and an amide group. The catalyst composition according to claim 1, which is an anionic ligand. 24. In the formula (A1), q is 1;
The catalyst composition according to claim 1, wherein Y ¹ is a Group VB element. 25. In the formula (A1), q is 0,
The catalyst composition according to claim 1, wherein Y ¹ is a Group VIB element. 26. In the formula (A2), q is 2;
The catalyst composition of claim 1 wherein Y ² is a group VB element. 27. In the formula (A2), q is 1;
The catalyst composition of claim 1 wherein Y ² is a group VIB element. 28. In the formulas (A1) and (A2),
R ²³ is hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, 6 to
2. A substituent selected from the group consisting of an aryl group having 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms. Catalyst composition. 29. The catalyst composition according to claim 1, wherein AlR ¹¹ R ¹² R ¹³ is selected from the group consisting of trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, and triisobutylaluminum. 30. The borate according to claim 1, wherein the borate is N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, or trimethylammonium tetrakis (pentafluorophenyl). Claims are selected from the group consisting of borate, ferrocenium tetrakis (pentafluorophenyl) borate, dimethylferrocenium tetrakis (pentafluorophenyl) borate, and silver tetrakis (pentafluorophenyl) borate. A catalyst composition according to claim 1. 31. The catalyst composition according to claim 1, wherein said activating catalyst is methylaluminoxane. 32. The activating cocatalysts is AlR ¹¹ R ¹² R ¹³
The catalyst composition according to claim 1, wherein the catalyst composition is a mixture of and borate. 33. An olefin monomer, or (b) at least one olefin monomer and at least one other monomer, in the presence of a catalytically effective amount of the catalyst composition of claim 1 under polymerization conditions. A process for producing an olefin polymer, comprising the step of polymerizing 34. The method according to claim 33, wherein the olefin monomer is ethylene.