JP2001139620A - Catalyst for ethylene polymerization and method for producing polyethylene - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst system capable of producing a high-density polyethylene having a practically sufficient high molecular weight in an industrially practical temperature range of 70 ° C to 90 ° C in slurry polymerization. The zirconocene compound comprises an activator, and the zirconocene compound has an ethylene insertion reactivity parameter (ΔE _ins (kJ / mol)) and a polymer chain desorption reactivity parameter (ΔE _elm (kJ / mol)). And (E) preferably satisfy the condition of ΔE _ins ≦ 0.8 (ΔE _elm ) −13 (I) ΔE _ins ≦ 0.8 (ΔE _elm ) −25 (II) And a method for producing polyethylene using the catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an ethylene polymerization catalyst comprising a zirconocene compound and an activator capable of producing a high molecular weight polyethylene, and a method for producing a high molecular weight polyethylene using the catalyst.

[0002]

2. Description of the Related Art It has been found that a combination of a metallocene compound and methylaluminoxane (MAO) is a highly active olefin polymerization catalyst in homogeneous polymerization (Japanese Patent Application Laid-Open No. 58-19309). It is also known that a polyolefin having a high molecular weight can be polymerized to some extent by a non-crosslinked or monocrosslinked substituted metallocene compound and a cocatalyst such as methylaluminoxane (Japanese Patent Application Laid-Open No. 60-35007). However, 70 of these olefin polymerization catalysts used industrially
The polyolefin polymerized at a polymerization temperature of from 100 to 100 ° C. had a low molecular weight and was not practical.

In a catalyst comprising a zirconocene compound and an activator, it has been found that the molecular weight of polyethylene depends on the structure of a ligand containing a cyclopentadienyl skeleton in the zirconocene compound. The ligand containing the cyclopentadienyl skeleton is an indenyl group, and studies on the substituent at the 2-position of the indenyl group have been conducted (Kaminsky, Macromol. Chem. Phys.
197, 3907 (1996)), so far no catalyst for producing high molecular weight polyethylene has been obtained.

On the other hand, bis (cyclopentadienyl) zirconium dichloride / MAO system and bis (pentamethylcyclopentadienyl) zirconium dichloride / MAO
Attempts have been made to compare molecular orbital calculations using the density functional theory method with experimental results for system catalysts (K. Thorsha
ug, JA Stoveng, E. Rytter, M. Yestenes, Macromo
lecules, 31, 7149 (1998)). However, when these molecular orbital methods are used, the calculation is very time-consuming, and it is practically impossible to calculate for all existing zirconocenes only by applying to a specific ligand. It cannot be used as a means to obtain a catalyst for producing polyethylene. In addition, the molecular weight in ethylene polymerization decreases as the polymerization temperature increases, and it has been pointed out that the metallocene catalyst is unstable with respect to temperature (W. Kaminsky, W. Luker, Maclo).
mol. Chem., Rapid Commun., 10, 225 (1989)).

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a catalyst capable of producing a high-density polyethylene having a practically sufficient high molecular weight in an industrially practical temperature range of 70 ° C. to 90 ° C. in slurry polymerization. And a method for producing polyethylene using the catalyst.

[0006]

Means for Solving the Problems As a result of diligent studies to solve the above problems, the present inventors have found that in a catalyst comprising a zirconocene compound and an activator, the ethylene insertion reactivity parameter (ΔE _ins (kJ / mol) ) And the elimination reactivity parameter of the polymer chain (ΔE _elm (kJ / mol))
Is the formula (I)

(Equation 3) It has been found that a high molecular weight polyethylene can be obtained by a catalyst using a zirconocene compound that satisfies the above relationship, and the present invention has been completed.

Hereinafter, the present invention will be described in detail. In the present invention, the insertion reactivity parameter of ethylene (ΔE
_ins ) means the ease of taking the intermediate structure of the insertion reaction model (FIG. 4) when ethylene is inserted, and the insertion reaction model intermediate calculated by a computer described later when the zirconocene cation and the polymer chain are butyl groups. The difference between the total energy of the body and the total energy of the model zirconocene cation is represented by a value that minimizes the difference (FIG. 1).

In the present invention, the elimination reactivity parameter (ΔE _elm ) refers to the ease of taking out the elimination reaction model intermediate structure (FIG. 6) when the polymer chain is eliminated, as a zirconocene cation and a polymer chain. When a butyl group,
The difference between the total energy of the elimination reaction model intermediate and the total energy of the model zirconocene cation, which is determined by a computer described later, is represented by a value that minimizes the difference (FIG. 2).

In the present invention, the insertion reactivity parameter (ΔE _ins ) and the desorption reactivity parameter (ΔE _elm ) are:
Silicon Graphics Inc. (Silicon)
Graphics) Indigo 2 workstation, Cerius ² ver.3.8 as software, Force Field as a Force Field, Universal Force Fiel
Abbreviated as d, UFF. ) 1.02 was selected and determined as follows (for UUF, the following document (a)
Referenced to (c): (a) AK Rappe, CJ Casewit, KS Colwell,
WA Goddard-III, WM Skiff, J. Am. Chem. Soc.,
1992, 114, 10024, (b) LA Castongnay, AK R
appe, J. Am. Chem. Soc., 1992, 114, 5832, (c) A.
K. Rappe, KS Colwell, Inorg. Chem., 1993, 32,
3438-50.).

Other modules of Cerius ² include Minimizer, Conformer Search (C)
onformer Search), Dynamics Simulation, etc. were used. Further, the three-dimensional definition of the molecular structure used in this specification and the definition of words used in computer chemistry are based on the manual of Cerius ² (Ver. 3.8) unless otherwise specified.

The structure of the model zirconocene is described in Molecular Simulation I, USA.
nc.), generated in a computer using a visualizer, builder, etc. under the environment provided by the Cerius ² graphical user interface, and the total energy was calculated by molecular mechanics calculations. .

The intermediate of the insertion reaction model was defined as follows (see FIG. 3). First, the zirconium atom is located at the origin in the three-dimensional spatial coordinates, and the linear butyl group of the polymer chain model is bonded to the zirconium atom. Was located. Further, ethylene was positioned in the opposite direction to the α-agonistic hydrogen in η ² format such that the two carbons of ethylene and the four atoms of the α-carbon of the zirconium and butyl groups were coplanar. At this time, of the two carbon atoms of ethylene, the carbon spatially closer to the α-carbon was defined as C ² , and the carbon farther away was defined as C ^1, and this plane was defined as an XY plane. The relative positions of the two carbons of zirconium and ethylene, the α-carbon of the butyl group, and the α-hydrogen are arranged so as to be similar to the calculation result of the density functional theory by Tom Ziegler et al. Am. Chem. Soc., 1
17, 12793-12800 (1995)).

Furthermore, two zirconium atoms and ethylene
Carbon atom C of¹, C^TwoAnd butyl C ^αCarbon, alpha agoste
For a total of five elements of hydrogen, see Cerius^TwoOpen
Open Forcefield Restraint
Using conditions (Restraint), Zr-H^α(2.236Å),
C^α-H^α(1.140Å), Zr-C¹(2.480Å), Zr
-C^Two(2.480Å) and C^Two-C^α(2.700Å)
Force Constant 418,600
kJ / mol / Å^TwoSet to. Similarly, H^α-C
^α-Zr-C¹(180 °), C^α-Zr-C¹-C
^TwoForce Constant at each dihedral angle of (0.00 °)
418,600 kJ / mol / Rad^TwoSet to.

For the atoms whose structure has been restrained,
Table 1 shows the initial structure obtained by the Z-matrix method.
(The spatial coordinate representation of atoms by Z-matrix is Ce
rius ^TwoAccording to the method described in the manual. For reference,
Hirano, Tanabe, "Molecular Orbital MOPAC Guidebook" Umi
There is a temple. ). Not shown in Table 1 in FIG.
The atoms are not specifically restrained (Ceriu
s^TwoWas input according to the structural parameters of The binding style is
C¹-C^TwoIs a double line, except that
Gweed display system)
It is a union.

[0015]

[Table 1]

Furthermore, the following general formulas (1) and (2) or
The ligand represented by (3) is represented by Zr-C ^αBond, Zr-C¹
Bond and the center of the cyclopentadienyl ring of the ligand and Zr
Connecting η^FiveType bonds become tetrahedral around the Zr atom
And the center of the cyclopentadienyl ring and Zr
At a distance of 2.2 km. At this time, the ligand
In the case of the general formula (1), two ligands are used, and the ligand is generally
In the case of formula (2) or (3), one ligand was used. This
These were defined as insertion reaction model intermediates.
The case where the ligand of (1) is used is shown. ).

The total energy of the intermediate of the insertion reaction model was determined by selecting the Charge Equilibration method, using Qeq charged 1.1 as the parameter set, setting the charge so that it becomes +1 in the whole system, and calculating the molecular force field. . At this time, in the case of the ligand of the general formula (1), the ligand is rotated by the rotation of the bond connecting the center of the cyclopentadienyl ring and the Zr atom, and in the case of the ligand of the general formula (2) or (3), Depending on the symmetry of the ligand, there may be a plurality of intermediate structures of the insertion reaction model. In that case, molecular mechanics calculations were performed on the insertion reaction models of each structure for all of the structures, and the minimum value of the total energy obtained was taken as the total energy of the insertion reaction model intermediate.

As described above, the total energy of the model zirconocene cation is obtained by positioning the zirconium atom at the origin in the three-dimensional spatial coordinates, bonding the linear butyl group of the polymer chain model to the zirconium atom, The distance between the ligand represented by the general formula (1), (2) or (3) and the center of the cyclopentadienyl ring and Zr is
The model zirconocene cation was positioned so that the distance was 2.2 ° and the α-carbon of the linear butyl group and the center of the two cyclopentadienyl rings were positioned so as to be flush with zirconium. At this time, when the general formula (1) is a ligand, two ligands are used. When the general formula (2) or (3) is a ligand, one ligand is used. In addition, the coordinates of all atoms were optimized. The sum of the total energy of the generated zirconocene by molecular mechanics calculation and the total energy of the ethylene molecules obtained by the following method was defined as the total energy of the model zirconocene cation.

Structure of ethylene molecule [distance between carbons (double bond): 1.331 °, distance between carbon and hydrogen: 1.085 °, angle (hydrogen-carbon-hydrogen): 119.5 °, angle (hydrogen-carbon-carbon): 120.2 °, all elements are on the same plane. ] Was generated in a computer using 3D Sketcher, and a molecular force field calculation was performed under the same calculation environment as that for the calculation of the zirconocene compound to obtain the total energy of ethylene. That is, the insertion reactivity parameter in the present invention is determined from the difference between the total energy of the insertion reaction model intermediate and the total energy of the model zirconocene cation.

The elimination reaction model intermediate was defined as follows (see FIG. 5). Principles and Applications of Organometallic Chemistry (Principl
es and Applications of Organotransition Metal Chem
istry) (JP Collman, LS Hegedus, JR Norto
n, RG Finke, author), a zirconium atom is located at the origin in the three-dimensional spatial coordinates, and a linear butyl group of a polymer chain model is bonded to the zirconium atom. Position at the distance where the stick interacts. J. Am. Chem. So
c., 117, 12793-12800 (1995). Ethylene is converted to β-agonistic hydrogen so that two carbons of ethylene and the four carbon atoms of zirconium and α-carbon of the butyl group are coplanar. Position in ^two formats. At this time, of the two carbon atoms of ethylene, the carbon spatially closer to β-agonistic hydrogen is C ² , and the carbon farther away is C ¹ . This plane was defined as the XY plane. The relative positions of the two carbon atoms of zirconium and ethylene, the α-carbon of the butyl group, and the β-carbon and β-hydrogen are determined by Tom Zigler
egler) et al.

Further, a zirconium atom, two carbon atoms C ¹ and C ² of ethylene, and C ^α and C ^β carbons of a butyl group, β
For a total of six elements of agostic hydrogen, see Cerius
Using Restraint (constraint) of ^{2 Open Forcefield, Zr-C α (} 2.335Å), C α -C β (1.448Å),
^{C β -H β (1.179Å),} Zr-C 2 (2.614Å), Zr
Force Constant (constant of force) is 418,600k at each distance of -C ¹ (2.614Å) and C ¹ -C ² (1.351Å)
It was set in J / mol / Å ^2. Similarly, C ^β −C ^{α
-Zr-C 1 (0.00 °)} , H β -C β -C α -Zr (0.0
0 °) and C ^α -Zr-C ¹ -C ² (0.00 °), the Force Constant was 418,600 kJ /
It was set to mol / Rad ^2.

For the atoms whose structure has been restrained,
Table 2 shows the initial structures obtained by the Z-matrix method.
(The spatial coordinate representation of atoms by Z-matrix is Ce
rius ^TwoAccording to the method described in the manual, but as a reference
, Hirano, Tanabe, "Molecular Orbital Method MOPAC Guide Book
””, Which is described in Table 2 in FIG.
Atoms that do not have a particular restraint
Cerius^TwoWas input according to the structural parameters of Again
The combination style is C¹-C^TwoIs a solid line except that is a double bond
(Including flying wedge display method)
Is a single bond.

[0023]

[Table 2]

FIG. 5 shows a ligand containing a cyclopentadienyl skeleton as a Zr- ^Cα bond, and an η ⁵ type bond connecting the Zr-C ¹ bond to the center of the cyclopentadienyl ring of the ligand and Zr. Is tetrahedral around the Zr atom, and the distance between the center of the cyclopentadienyl ring and Zr is 2.
It was located at a distance of 2 mm and was used as an elimination reaction model intermediate.
FIG. 6 shows the case where the ligand is a cyclopentadienyl group.
The total energy of the elimination reaction model intermediate is
Select the Equilibration method and set the parameter set to Qeq
Using charged 1.1, the charge was set so that it would be +1 for the whole system, and the molecular force field calculation was performed. At this time, when the cyclopentadienyl group in the ligand is not cross-linked (general formula (1)), the center of the cyclopentadienyl ring and Z
When the cyclopentadienyl group is cross-linked (general formulas (2) and (3)) due to the rotation of the bond connecting r, the plurality of elimination reaction model intermediates exist due to the symmetry of the ligand. May be. In that case, a molecular force field calculation was performed for all the structures for the elimination reaction model of each structure, and the minimum value of the obtained total energy was defined as the total energy of the elimination reaction model intermediate.

The above values were used for the total energy of the model zirconocene cation. That is, the elimination reactivity parameter in the present invention is determined from the difference between the total energy of the elimination reaction model intermediate and the total energy of the model zirconocene cation.

The zirconocene compound of the present invention has two cyclopentadienyl skeletons coordinated to a zirconium atom in a coordination form of η ^{5 in} the molecule, and the above-mentioned ΔE
_ins (kJ / mol) and ΔE _elm (kJ / mol)
E is _ins ≦ 0.8 _{(ΔE elm)} zirconium compound is in the range -13.

Specifically, the general formula (1)

Embedded image Wherein, R ¹ to R ⁵ may be the same or different, mean respectively a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group having 1 to 10 carbon atoms,, R ¹ ~ R ⁵ may form a ring with the adjacent substituents. ],
General formula (2)

Embedded image Wherein, R ¹ to R ⁸ may be the same or different, mean respectively a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group having 1 to 10 carbon atoms,, R ¹ ~ R ⁸ may form a ring with a substituent adjacent to each other, and X ¹ which is a cross-linking group of a cyclopentadienyl ring is a dialkylsilylene group, a tetraalkyldisilenyl group, or a C 1 to C 3 It means an alkylene group, and the numerical value at the upper right of the parenthesis in the formula means a valence. Or general formula (3)

Embedded image Wherein, R ¹ to R ⁶ may be the same or different, mean respectively a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group having 1 to 10 carbon atoms,, R ¹ ~ R ⁶ may form a ring with a substituent adjacent to each other, and X ¹ and X ² which are a cross-linking group of a cyclopentadienyl ring may be the same or different from each other, and may be a dialkylsilylene group, It means an alkyldisilenyl group or an alkylene group having 1 to 3 carbon atoms. Is represented by 2 in the case of the general formula (1).
In the case of general formula (2) or (3), it is selected from among zirconocene compounds having one.

At this time, the substituent bonded to the zirconium atom other than the general formulas (1) to (3) may be any, and among these zirconocene compounds, ΔE
The relationship between _ins (kJ / mol) and ΔE _elm (kJ / mol) is _expressed by the formula (I).

(Equation 4) Preferably

(Equation 5) A zirconium compound satisfying the following condition is selected. Among these zirconocene compounds, compounds having a ligand represented by the general formula (2) or (3) are preferable.

In the case of the ligand represented by the general formula (1), two ligands which may be different from each other or the same are represented by "P
rinciples and Applications of Organotransition Met
al Chemistry ", (JP Collman, LS Hegedus, J.
R. Norton, an RG Finke, zirconium compounds bound to the zirconium atom centered coordination form of eta ⁵ defined by markedly). Similarly, the ligand represented by the general formula (2) or (3) is a zirconium compound in which the ligand is bonded to the central zirconium in a coordination form of η ⁵ .

For example, the oxidation number of a zirconium atom is +4
In the case of, other than the ligands represented by the two general formulas (1),-
A neutral zirconium compound in which two monovalent ligands are further bonded to zirconium is also a zirconocene compound of the present invention. Specifically, and zirconocene dichloride, zirconocene dimethyl, bis (eta ⁵ - indenyl) but such zirconium dibromide can be exemplified, but the invention is not limited thereto. More specifically, when the oxidation number of the zirconium atom is +4, a neutral compound in which one divalent ligand is further bonded to zirconium in addition to the two ligands represented by the general formula (1) Are also the zirconocene compounds of the present invention. Specifically, bis (η ⁵ -methylcyclopentadienyl) zirconium (2-butene-1,4-diyl) can be exemplified, but is not limited thereto.

For example, when the oxidation number of zirconium is +4, in addition to the two ligands represented by the general formula (1), one monovalent ligand is bonded to zirconium, and A cationic zirconium compound which is a salt with a cationic anion is also a zirconocene compound of the present invention. Specifically, bis [(eta ⁵ - ethyl cyclopentadienyl) zirconium methyl] ⁺ [tetrakis (pentafluorophenyl) borate] ^- the like can be exemplified, but not limited to.

For example, when the oxidation number of zirconium is +4, in addition to the two ligands represented by the general formula (1), one monovalent ligand is bonded to zirconium, and the neutral ligand is further neutralized. A cationic zirconium compound in which a ligand is coordinated to zirconium and is a salt with a non-coordinating anion is also a zirconocene compound of the present invention. Specifically, screw
[(Eta ⁵ - methylcyclopentadienyl) zirconium methyl (tetrahydrofuran)] ⁺ [tetrakis (pentafluorophenyl) borate] ^- the like can be exemplified, but not limited to.

Similar to the case of the ligand represented by the general formula (1), when the ligand is represented by the general formula (2) or (3), each of the zirconocene compounds of the present invention has η ⁵
Is a zirconium compound bonded to the central zirconium in a coordination form of

For example, when the oxidation number of zirconium is +4, a neutral zirconium compound in which two more monovalent ligands are bonded to zirconium in addition to the ligand represented by the general formula (2) is also used. The zirconocene compound of the invention. Specifically, it dimethylsilylenebis (eta ⁵ - cyclopentadienyl) zirconium dichloride, ethylenebis (eta ⁵ -
Examples thereof include (indenyl) zirconium dichloride, but are not limited thereto.

For example, when the oxidation number of zirconium is +4, one monovalent ligand other than the ligand represented by the general formula (3) is bonded to zirconium, and the neutral ligand is further neutralized. Is a zirconium compound of the present invention, which is a salt with a non-coordinating anion. Specifically, [bis (dimethylsilylene) bis {(eta ^{5-4-methylcyclopentadienyl)}} zirconium methyl (ethylene)] ⁺ [tetrakis (pentafluorophenyl) borate] ^- the like can be exemplified, which It is not limited to.

For example, when the oxidation number of zirconium is +3
Is a monovalent coordination other than the ligand represented by the general formula (2)
Neutral zirconium with one element bonded to zirconium
The compound is also a zirconocene compound of the present invention. Specifically
Is dimethylsilylenebis (η ^Five-Cyclopentadieni
F) zirconium methyl, etc.
Not determined.

Among the above zirconocene compounds, the compounds represented by the general formula (4) are preferred.

Embedded image

In the formula, M represents zirconium;¹~
R^FourMay be the same or different, and represent a hydrogen atom, carbon
A hydrocarbon group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms
Means a silsilyl group. R¹~ R^FourAre adjacent to each other
It may form a ring with a substituent. X is a halogen atom, hydrid
, An alkyl group having 1 to 10 carbon atoms and an alkyl group having 6 to 15 carbon atoms.
Reel base or OR⁹Group (in the group, R⁹Has 1 to 10 carbon atoms
An alkyl group, an aryl group having 6 to 15 carbon atoms, an aryl
A fluoroalkyl group or a fluoroaryl group. )
Means the alkoxy group to be formed. E¹And E^TwoIs German
Standing Si (R^Ten)_TwoOr C (R^Ten)_TwoAnd two R
^TenMay be the same or different, each having 1 carbon atom
10 to 10 alkyl groups, 6 to 15 carbon atoms of arylalkyl
Or a cycloalkyl group having 3 to 10 carbon atoms.
And n is 2.

Among the above zirconocene compounds, ΔE
_Ins and ΔE _elm are represented by ΔE _ins ≦ 0.8 (Δ
The following compounds can be exemplified as specific examples satisfying the condition of E _elm ) -13. Here, Me represents a methyl group, C ₁₃ H ₈ represents a fluorenyl group, and C ₉ H ₅ represents an indenyl group.

Me_TwoSi (η^Five-C₁₃H₈)_TwoZrCl_Two, M
e_TwoSi (η^Five-C₁₃H₈)_TwoZrMe_Two, [Me_TwoSi (η^Five
-C₁₃H₈)_TwoZrMe]⁺ [B (C₆F_Five)_Four]^-, (N-C
_FourH₉)_TwoSi (η^Five-C₁₃H₈)_TwoZrCl_Two, (N-C_FourH₉)_Two
Si (η^Five-C₁₃H₈)_TwoZrMe_Two, [(N-C_FourH₉)_TwoSi
 (η^Five-C₁₃H₈)_TwoZrMe]⁺ [B (C₆F_Five)_Four]^-, Rac
-Me_TwoSi {η^Five-C₉H_Four-2- (CHMe_Two) -4-
Ph}_TwoZrCl_Two, Rac-Me_TwoSi {η^Five-C₉H_Four−
2- (CHMe_Two) -4-Ph}_TwoZrMe_Two, [Rac-
Me_TwoSi {η^Five-C₉H_Five-2- (CHMe_Two) -4-P
h}_TwoZrMe] ⁺ [B (C₆F_Five)_Four]^-, Rac-Me_TwoSi
{η^Five-C₉H_Five-2- (CHMe_Two)}_TwoZrCl_Two,

Rac-Me_TwoSi {η^Five-C₉H_Five-2-
(CHMe_Two)}_TwoZrMe_Two, [Rac-Me_TwoSi {η^Five−
C₉H_Five-2- (CHMe_Two)}_TwoZrMe]⁺ [B (C₆F_Five)
_Four]^-, Rac- (Me_TwoSi)_Two (η^Five-C_FiveH-4-Me)_Two
ZrCl_Two, Rac- (Me_TwoSi)_Two (η^Five-C_FiveH-4-
Me)_TwoZrMe_Two, [Rac- (Me_TwoSi)_Two (η^Five-C_Five
H-4-Me)_TwoZrMe]⁺ [B (C₆F_Five)_Four] ^-, Rac-
 (Me_TwoSi)_Two (η^Five-C_FiveH-3,5-Me_Two)_TwoZrCl
_Two, Rac- (Me_TwoSi)_Two (η^Five-C_FiveH-3,5-Me
_Two)_TwoZrMe_Two, [Rac- (Me_TwoSi)_Two (η^Five-C_FiveH-
3,5-Me_Two)_TwoZrMe]⁺ [B (C₆F_Five)_Four]^-, Rac
− (Me_TwoSi)_Two {η^Five-C_FiveH-3,5- (CHM
e_Two)_Two}_TwoZrCl_Two, Rac- (Me_TwoSi)_Two {η^Five-C_Five
H-3,5- (CHMe_Two)_Two}_TwoZrMe_Two,

[Rac- (Me_TwoSi)_Two {η^Five-C_FiveH-
3,5- (CHMe_Two)_Two}_TwoZrMe]⁺ [B (C
₆F_Five)_Four]^-, Rac- (Me_TwoSi)_Two {η^Five-C_FiveH-3,
5- (CMe_Three)_Two}_TwoZrCl_Two, Rac- (Me_TwoSi)_Two 
{η^Five-C_FiveH-3,5- (CMe_Three)_Two}_TwoZrMe_Two, [Ra
c- (Me_TwoSi)_Two {η^Five-C_FiveH-3,5- (CM
e_Three)_Two}_TwoZrMe]⁺ [B (C₆F_Five)_Four]^-, Rac- (Me_Two
Si)_Two {η^Five-C_FiveH-3- (CHMe_Two) -5-Me}_Two
ZrCl _Two, Rac- (Me_TwoSi)_Two {η^Five-C_FiveH-3-
 (CHMe_Two) -5-Me}_TwoZrMe _Two, [Rac− (M
e_TwoSi)_Two {η^Five-C_FiveH-3- (CHMe_Two) -5-M
e}_TwoZrMe]⁺ [B (C₆F_Five)_Four]^-, Rac- (Me_TwoS
i)_Two {η^Five-C_FiveH-3- (2-adamantyl) -5-M
e}_TwoZrCl_Two, Rac- (Me_TwoSi)_Two {η^Five-C_FiveH-
3- (2-adamantyl) -5-Me}_TwoZrMe_Two, [R
ac- (Me_TwoSi)_Two {η^Five-C_FiveH-3- (2-adama
N-yl) -5-Me} _TwoZrMe]⁺ [B (C₆F_Five)_Four]^-,

Rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-
3,5- (2-adamantyl) ₂ } ₂ ZrCl ₂ , rac-
(Me ₂ Si) ₂ {η ⁵ -C ₅ H-3,5- (2-adamantyl) ₂ } ₂ ZrMe ₂ , [rac- (Me ₂ Si) ₂ {η ⁵ -C ₅
H-3,5- (2- ^{_{adamantyl) 2} 2 ZrMe] + [}} B
(C ₆ F ₅ ) ₄ ] ^- , rac- (Me ₂ Si) ₂ (η ⁵ -C ₅ H-3
- cyclohexyl _{-5-Me} 2 ZrCl 2,} rac-
(Me ₂ Si) ₂ {η ⁵ -C ₅ H-3-cyclohexyl-5
Me} ₂ ZrMe ₂ , [rac− (Me ₂ Si) ₂ {η ⁵ −C ₅
H-3-cyclohexyl-5-Me} ₂ ZrMe] ⁺ [B
(C ₆ F ₅ ) ₄ ] ^- , rac- (Me ₂ Si) ₂ (η ⁵ -C ₅ H-3
_{- (CH 2 C 6 H 5} ) -5-Me} 2 ZrCl 2, rac-
(Me ₂ Si) ₂ {η ⁵ -C ₅ H-3- (CH ₂ C ₆ H ₅ ) -5
−Me} ₂ ZrMe ₂ , [rac− (Me ₂ Si) ₂ {η ⁵ −C
_{5 H-3- (CH 2 C} 6 H 5) -5-Me} 2 ZrMe 2] +
[B (C ₆ F ₅ ) ₄ ] ^- ,

Rac- (Me_TwoSi)_Two (η^Five-C_FiveH-
3,5-Me_Two)_TwoZrCl_Two, Rac- (Me_TwoSi)_Two 
(η^Five-C_FiveH-3,5-Me_Two)_TwoZrMe_Two, [Rac-
(Me_TwoSi)_Two (η^Five-C_FiveH-3,5-Me_Two)_TwoZrMe]
⁺ [B (C₆F_Five)_Four]^-, Rac- (Me_TwoSi)_Two {η^Five-C_Five
H-3,5- (CHMe_Two)_Two}_TwoZrCl_Two, Rac− (M
e_TwoSi)_Two {η^Five-C_FiveH-3,5- (CHMe_Two)_Two}_TwoZr
Me_Two, [Rac- (Me_TwoSi)_Two {η^Five-C_FiveH-3,5
− (CHMe_Two)_Two}_TwoZrMe]⁺ [B (C₆F_Five)_Four]^-, Ra
c- (Me_TwoSi)_Two {η^Five-C_FiveH-3- (CHMe_Two) −
5-Me}_TwoZrCl _Two, Rac- (Me_TwoSi)_Two {η^Five−
C_FiveH-3- (CHMe_Two) -5-Me}_TwoZrMe _Two, [R
ac- (Me_TwoSi)_Two {η^Five-C_FiveH-3- (CHMe_Two)
-5-Me}_TwoZrMe]⁺ [B (C₆F_Five)_Four]^-, Rac-
(Me_TwoSi)_Two {η^Five-C_FiveH-3- (2-adamantyl)
-5-Me}_TwoZrCl_Two, Rac- (Me_TwoSi)_Two {η^Five
-C_FiveH-3- (2-adamantyl) -5-Me}_TwoZr
Me_Two,.

The activator according to the present invention is a substance that exhibits ethylene polymerization activity when it comes into contact with a zirconocene compound. Specifically, chain or cyclic aluminoxanes represented by the general formulas (5) and (6) can be exemplified.

Embedded image

In the formula, R ²¹ represents a hydrocarbon group having 1 to 10 carbon atoms, preferably a methyl group, an ethyl group and an isobutyl group. n is an integer of 5 to 40, preferably 10 to 20. Preferably, as a single substance, methylaluminoxane, ethylaluminoxane, and modified methylaluminoxane can be exemplified.
Further, aluminoxanes having two or more alkyl side chains represented by the general formulas (7) and (8) can also be used.

Embedded image

In the formula, R ²¹ and R ²² represent different hydrocarbon groups having 1 to 10 carbon atoms, and are preferably a methyl group, an ethyl group or an isobutyl group. m and n are 1 to 4
It is an integer of 0, and m + n = 5 to 40. These can be used alone or as a mixture. Examples of the activator include borane and organic aluminum represented by the general formula (9).

Embedded image

In the formula, M represents a boron atom or an aluminum atom. When M is boron, the general formula (9) represents borane, and R ³¹ , R ³² and R ³³ may be the same or different and represent a hydrocarbon group having 1 to 10 carbon atoms or a halogenated hydrocarbon group. I do. Preferably, a phenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group are exemplified. Preferably, it is a pentafluorophenyl group.

When M is aluminum, the general formula (9) means an organoaluminum compound, and R ³¹ , R ³² and R ³³ may be the same or different, and have a hydrocarbon group of 1 to 10 carbon atoms, Means a hydrocarbon group. Preferably,
Examples thereof include a phenyl group, a pentafluorophenyl group, a 3,5-di (trifluoromethyl) phenyl group, a methyl group, an ethyl group, an isobutyl group, a halogen, a chlorine atom, and a hexyl group. Preferably, a pentafluorophenyl group,
It is an isobutyl group. Preferred specific examples include tris (pentafluorophenyl) borane and tris (3,5
-Di (trifluoromethyl) phenyl) borane.

Further, as the activator, an ionic compound can be exemplified. Representative ionic compounds include borates, preferably tetrakis (pentafluorophenyl) borate / dimethylanilinium salt, tetrakis (pentafluorophenyl) borate / triphenylcarbonium salt, and the like. A mixture containing these may be used.

These are basically substances that can be dissolved in an organic solvent such as toluene. However, solid substances obtained by physically or chemically supporting these soluble activators on silica or a polymer compound can be used. Activators are also used as activators in the present invention. Specific examples include silica supporting methylaluminoxane, silica supporting borate, and the like.

A preferred solid activator is WO 96/41808.
The ionic compound having a single-bonding functional group disclosed in the above publication is chemically bonded to a solid having a functional group. Here, a functional group is a covalent bond accompanied by a chemical reaction,
A group capable of forming an ionic bond, a metal bond, and a coordinate bond. Specific examples include a hydroxyl group, a carboxyl group, a halogen group, a silanyl group, and a halogenated silyl group.

The ionic compound having a carrier-binding functional group is a compound represented by the general formula (10). _{^{[M 2 (R 41) k}} (R 42) l (R 43) m (R 44 -L) n] - [D] + (10) wherein, M ² is an element of Group 13, R ⁴¹ , R ⁴² and R ⁴³ may be the same or different and each have 1 to 2 carbon atoms.
0 is a hydrocarbon group, a substituted hydrocarbon group, an alkoxide group or a halogen atom, and R ⁴⁴ is an alkylene group having 1 to 20 carbon atoms, a substituted alkylene group, a substituted phenylene group, a silanylene group, a substituted silanylene group, a silaalkylene group, A substituted silaalkylene group, an oxasilanylene group, a substituted oxasilanylene group, and an oxasilaalkylene group. k, l, m
Is an integer of 0 or 1 to 3, respectively, n is an integer of 1 to 4, and k + 1 + m + n = 4. R ⁴⁴ -L is such that L is R ⁴⁴
And L is a group represented by the following general formula (11) or (12).

-Si [(R ⁴⁵ ) (R ⁴⁶ ) (R ⁴⁷ )] (11) -Si [(R ⁵¹ ) (R ⁵² )]-Y-Si [(R ⁴⁸ ) (R ⁴⁹ ) (R ⁵⁰ ) )] (12)

In the formula, R ^{45 to} R ⁵² may be the same or different, and each represents a hydrocarbon group having 1 to 20 carbon atoms, a substituted hydrocarbon group, an alkoxide group, or a halogen atom. Is bound to At least one of R ⁴⁵ , R ⁴⁶ and R ⁴⁷ and at least one of R ⁴⁸ , R ⁴⁹ and R ⁵⁰ are a halogen atom. Y is -O-, an alkylene group having 1 to 20 carbon atoms, a substituted alkylene group, a phenylene group, or a substituted phenylene group. n
Is 2 or more, each R ⁴⁴ -L may be the same or different. D represents a monovalent cation selected from carbonium, anilinium, ammonium, ferrocenium, phosphonium, sodium, potassium and lithium.

Specific examples of such an ionic compound having a carrier-binding functional group include the following compounds in N, N-dimethylanilinium salt.
N, N-dimethylanilinium tris (pentafluorophenyl) p-trichlorosilyl tetrafluorophenyl borate, N, N-dimethylanilinium tris (pentafluorophenyl) p-methyldichlorosilyl tetrafluorophenyl borate, N, N-dimethyl Anilinium tris (pentafluorophenyl) p-dimethylchlorosilyltetrafluorophenyl borate, N, N
-Dimethylanilinium tris (pentafluorophenyl) p-trimethoxysilyltetrafluorophenyl borate, N, N-dimethylanilinium tris (pentafluorophenyl) p-dimethoxymethylsilyl tetrafluorophenyl borate,

N, N-dimethylanilinium tris (pentafluorophenyl) p-methoxydimethylsilyltetrafluorophenyl borate, N, N-dimethylanilinium tris (pentafluorophenyl) p-triethoxysilyl tetrafluorophenyl borate, N , N
-Dimethylanilinium tris (pentafluorophenyl) p-diethoxymethylsilyl tetrafluorophenyl borate, N, N-dimethylanilinium tris (pentafluorophenyl) p-ethoxydimethylsilyl tetrafluorophenyl borate, N, N-dimethylanily N-tris (pentafluorophenyl) p-trihydroxysilyltetrafluorophenyl borate, N,
N-dimethylanilinium tris (pentafluorophenyl) p-dihydroxymethylsilyl tetrafluorophenyl borate, N, N-dimethylanilinium tris (pentafluorophenyl) p-hydroxydimethylsilyl tetrafluorophenyl borate, triphenylcarbenium tris ( Pentafluorophenyl) p-trichlorosilyltetrafluorophenylborate, triphenylcarbenium tris (pentafluorophenyl)
p-methyldichlorosilyl tetrafluorophenyl borate, triphenylcarbenium tris (pentafluorophenyl) p-dimethylchlorosilyl tetrafluorophenyl borate,

Triphenylcarbenium tris (pentafluorophenyl) p-trimethoxysilyltetrafluorophenylborate, triphenylcarbenium tris (pentafluorophenyl) p-dimethoxymethylsilyltetrafluorophenylborate, triphenylcarbenium tris (pentane Fluorophenyl) p-methoxydimethylsilyl tetrafluorophenyl borate,
Triphenylcarbenium tris (pentafluorophenyl) p-triethoxysilyltetrafluorophenylborate, triphenylcarbenium tris (pentafluorophenyl) p-diethoxymethylsilyltetrafluorophenylborate, triphenylcarbenium tris (pentafluorophenyl) ) P-ethoxydimethylsilyl tetrafluorophenyl borate, triphenylcarbenium tris (pentafluorophenyl) p-trihydroxysilyl tetrafluorophenyl borate,
Triphenylcarbenium tris (pentafluorophenyl) p-dihydroxymethylsilyl tetrafluorophenyl borate, triphenylcarbenium tris (pentafluorophenyl) p-hydroxydimethylsilyl tetrafluorophenyl borate.

Among these ionic compounds, N, N
-Dimethylanilinium tris (pentafluorophenyl) 4- (trichlorosilyl) -2,3,5,6-tetrafluorophenyl borate, N, N-dimethylanilinium tris (pentafluorophenyl) 4- (methyldichlorosilyl) -2,3,5,6-tetrafluorophenyl borate and N, N-dimethylanilinium tris (pentafluorophenyl) 4- (dimethylchlorosilyl) -2,3,5,6-tetrafluorophenyl borate are preferred. .

The solid having a functional group refers to a surface capable of forming a chemical bond with a plurality of ionic compounds of the present invention and a functional group, and the surface has a plurality of active sites during polymerization reaction. Is a solid having an extent and properties to the extent that it can be formed, and is a solid having a functional group represented by the general formula (13). −OR ⁵³ (13)

In the formula, R ⁵³ is a hydrogen atom, a C1-20 alkyl group, an alkyl metal or an amine. Specific examples include inorganic oxides, inorganic chlorides, inorganic hydroxides, and organic polymer compounds, and specific examples thereof include inorganic compounds such as silica, alumina, silica-alumina, magnesia, titania, zirconia, and calcia. I can do it.

The solid having a functional group used in the present invention requires a large surface area, a fine pore diameter, and a functional group on the surface in order to be chemically modified with an ionic compound having a carrier-binding functional group on the surface. . In addition, the supported ionic compound forms a polymerization active species by forming an ion pair with the zirconocene compound. Therefore, a solid having a functional group requires a space capable of forming an ion pair.
Further, since the polymerization activity per catalyst increases as the amount of ion pairs formed on the solid having a functional group increases, the solid having a functional group preferably has a large surface area and a large average pore diameter.

In the present invention, the solid having a functional group has an average particle diameter of 5 to 200 μm and a specific surface area of 100 to 200 μm.
It is preferable to use fine particles having a diameter of 1000 m ² / g and an average pore diameter of 20 Å or more. The reaction between the solid having a functional group and the ionic compound having a functional group capable of binding to a carrier can be carried out by various methods. Generally, the reaction is performed in an organic solvent.

Specifically, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane and decane, alicyclic hydrocarbons such as methylcyclopentane, cyclopentane and cyclooctane, benzene, toluene, xylene, cumene, Use aromatic hydrocarbons such as cymene, aliphatic halogenated hydrocarbons such as chloroform and dichloromethane, aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, alcohols such as methanol and ethanol, and ethers such as diethyl ether and tetrahydrofuran. be able to.

The reaction between the solid having a functional group and the ionic compound having a functional group capable of binding to a carrier is optional as long as a desired bond is formed, but generally the following conditions are desirable.
The reaction temperature is generally -70C to 200C, preferably 0C to 150C. It is preferable that the reaction between the ionic compound having the carrier-binding function and the functional group on the solid surface having the functional group sufficiently proceed. Since the reaction time varies depending on conditions such as concentration and temperature, it cannot be specified unconditionally, but it is usually performed for 1 to 50 hours.

The concentration of the ionic compound in the reaction solvent is 1
The binding reaction can be performed at a concentration of about 10000 ppm and a solid having a functional group of about 1 to 50% (mass%, the same applies hereinafter). The reaction ratio of the ionic compound having a carrier-binding functional group to the solid having a functional group in the present invention is not particularly limited. When the number of functional groups on the solid surface is equal to or more than the equivalent of the carrier-binding functional group, the functional groups on the unreacted solid surface may react with the zirconocene compound and may not be able to form polymerization active species. By reacting the functional group with another compound, the compound can be prevented from reacting with the zirconocene compound.

For example, when the unreacted functional group is a hydroxyl group,
By treating the hydroxyl group with trimethylchlorosilane or the like, the reaction between the zirconocene compound and the unreacted functional group on the solid surface can be suppressed. An ethylene polymerization catalyst as a reaction product is separated from the reaction solution, and an unreacted ionic compound having a carrier-binding functional group is removed by washing.
The above-mentioned organic solvents can be used as the washing solvent. The washing temperature is from -30C to 120C, preferably from 0C to 100C. Washing is preferably performed until no ionic compound having a carrier-binding functional group is substantially detected in the washing solution. After the washing, the solid activator carrying the ionic compound can be used after drying or in the presence of an organic solvent.

The formation of a chemical bond between the ionic compound having a carrier-binding functional group and the solid having a functional group in the present invention is based on the determination of the amount of the functional group on the solid which decreases by the reaction, Can be confirmed by quantifying the compound generated as a result of the reaction between the functional group of the above and the carrier-binding functional group of the ionic compound. In addition, it can be confirmed by an IR absorption peak and an NMR peak of a new bond generated as a result of the reaction.

The catalyst in the present invention can be obtained by contacting a zirconocene compound with an activator. The production method is not particularly limited, but specific examples include the following methods.

(1) The catalyst can be obtained by dissolving both the activator and the zirconocene compound in an organic solvent capable of dissolving them and contacting them at a preferable concentration and temperature.
Examples of the activator at this time include methylaluminoxane, a preferable organic solvent is a hydrocarbon solvent, and a more preferable example is toluene. At this time, the contact concentration of the zirconocene compound is from 100 mol / L (L) to 0.001 mmol / L, preferably
mol / L to 0.1 mmol / L. The contact temperature at this time is from -78 ° C to 200 ° C, preferably-
The range is from 10 ° C to 50 ° C.

(2) When the activator is in a solid state that does not dissolve in the solvent, the solid activator is suspended in an organic solvent, and a zirconocene compound is brought into contact with the organic solvent at a preferable concentration and temperature to prepare a catalyst in a slurry state. Can be obtained. The obtained catalyst may be washed with an organic solvent as needed. In addition, the catalyst can be a solid catalyst by removing the organic solvent. Examples of the solid activator at this time include silica carrying methylaluminoxane and silica carrying borate. The organic solvent in which the solid activator is suspended is preferably a hydrocarbon solvent, more preferably an aromatic hydrocarbon solvent such as toluene. At this time, the slurry concentration of the suspension of the solid activator is 1 to 5
00 g / L, preferably 10 to 100 g / L. The concentration of the zirconocene compound at this time is 100
mol / L to 0.001 mmol / L, preferably 1 mol / L to 0.1 mmol / L. The contact temperature at this time is from -78 ° C to 200 ° C, preferably from -10 ° C to 50 ° C.

The ratio of the zirconocene compound to the activator in the catalyst according to the present invention is not particularly limited, but when the activator is an aluminoxane, the aluminum atom in the aluminoxane is replaced with the aluminum atom in the zirconocene compound. It is used in a molar ratio of 1 to 10,000 times relative to zirconium. Preferably, the ratio is 10 to 3000 times.
In the case of borane, organic aluminum, and ionic compound, aluminum (or boron) is used at a ratio of 0.1 to 2000 times that of zirconium, preferably 1 to 500 times.

The catalyst in the present invention may contain components other than the zirconocene compound and the activator. For example, it may be mixed with a porous carrier such as silica or alumina or a layered clay compound such as montmorillonite. At that time, the content of the zirconocene compound is 0.01 to 80%, preferably 0.5 to 50%.

The catalyst of the present invention can be used together with the third component (co-catalyst component) in the polymerization of ethylene. An organoaluminum compound is exemplified as a promoter component. Particularly, triethylaluminum, triisobutylaluminum, diethylaluminum chloride and the like can be exemplified. The concentration of these promoter components in the reaction system is 0.1 to 100 mmol / L, preferably 0.1 to 10 mmol / L.

The catalyst of the present invention can be supplied to a reactor together with a scavenger component added during polymerization. An organolithium compound as a scavenger component,
Examples thereof include an organic aluminum compound and an organic magnesium compound. Specifically, normal butyl lithium, triisobutyl aluminum, butyl ethyl magnesium and the like can be exemplified. The concentration of these scavenger components in the reaction system is 0.1 to 100
mmol / L, preferably 0.1 to 10 mmol / L.

The polymerization temperature to which the catalyst of the present invention can be applied is not particularly limited, but a polymerization temperature range of 50 ° C. to 100 ° C. is particularly effective. The catalyst of the present invention shows a remarkable effect particularly in ethylene polymerization, and can produce high molecular weight polyethylene.
Pentene, 1-hexene, 1-octene, 1-decene,
1-undecene or the like can be copolymerized. The ethylene partial pressure used in the polymerization of ethylene is 0.1 to 3M.
Pa, preferably 1 to 2 MPa.

[0077]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. In the following examples, synthesis of a ligand and a zirconocene compound was performed under a nitrogen atmosphere. THF, the ligand, the solvent used in the synthesis of the zirconocene compound,
Toluene and hexane were dehydrated with an Na / K alloy, and dichloromethane was dehydrated with calcium hydride.

The structure of the model zirconocene is described in Molecular Simulation I, USA.
nc.), generated in a computer using a visualizer, builder, etc. under the environment provided by the Cerius ² graphical user interface, and the total energy was calculated by molecular mechanics calculations. . The hardware and software used for the actual calculations are shown below.

[Hardware] Silicon Graphics (Silicon Graphics)
Indigo 2 workstation [Software] Cerius ² Ver.3.8 A Universal Force Field (UFF) 1.02 was used as the Force Field. Modules included in Cerius ² include Minimizer, Conformer Search (Confo
rmer Search), dynamics simulation (D
dynamics Simulation).

The molecular weight (Mn) was determined by performing gel permeation chromatography (GPC) under the following conditions. Gel Permeation Chromatography Measurement Conditions: Apparatus: WATERS 150C model, Column: Shodex-HT806M, Solvent: 1,2,4-trichlorobenzene, Temperature: 135 ° C., Monodisperse polystyrene fraction was used to calculate the molecular weight. HLMFR was measured at 190 ° C. under a load of 21.6 kg according to the method described in JIS K6760.

Example 1 [Calculation of Insertion Reactivity Parameter and Desorption Reactivity Parameter] (1) Calculation of Total Energy of Insertion Reaction Model Intermediate As shown in the structure shown in FIG. 3, zirconium, ethylene,
A partial structure of zirconocene containing a butyl group was generated in a calculator. The coordinates of Zr, C ^α , H ^α , C ¹ , and C ² were determined as in the Z-matrix coordinates shown below. Ce
Rius ² of Open Forcefield of Restraint using ^{(constraint), Zr-H α (2.236Å} ), C α -H α (1.140
Å), Zr-C ¹ (2.480Å), Zr-C ² (2.480Å),
Force at each distance of C ² -C ^α (2.700Å)
Constant a (constant force) is set to 418,600kJ / mol / Å ^2. Similarly, H ^α -C ^α -Zr-C ¹ (18
0 °) and C ^α -Zr-C ¹ -C ² (0.00 °) at each dihedral angle of 418,600 kJ / force constant.
It was set to mol / Rad ^2.

[0082]

[Table 3]

The ligand of the zirconocene of Example 1 was {
(Me_TwoSi)_Two (C_FiveH-3,5-Me _Two)_Two}^2-Is
This ligand is represented by Zr-C^αBond, Zr-C¹Binding and distribution
Linking the center of the ligand cyclopentadienyl ring with Zr^Five
Type bonds become tetrahedral around Zr atoms
And the distance from the center of the cyclopentadienyl ring to Zr.
It was located at a distance of 2.2 mm. In this way the calculator
Within {(Me_TwoSi)_Two (C_FiveH-3,5-Me_Two)_Two}^2-Coordination
An insertion reaction model intermediate with offspring was generated. Charge meter
Select the Charge Equilibration method as the
The meter set used was Qeqcharged 1.1. This and
There is only one kind of insertion reaction model intermediate,
When the structure is optimized by Minimizer
Total energy (E^a1) Is at 712 kJ / mol
there were.

(2) Calculation of total energy of elimination reaction model intermediate As shown in FIG. 5, zirconium, ethylene,
Generate partial structure of zirconocene containing butyl group in computer
Alive. Like the Z-matrix coordinates shown below
, Zr, C^α, C^β, H^β, C¹, C^TwoCoordinates are determined
These atoms are Cerius^TwoOpen Forcefield Re
Using a straint (restriction condition), Zr-C ^α(2.335
Å), C^α-C^β(1.448Å), C^β-H^β(1.179
Å), Zr-C^Two(2.614Å), Zr-C¹(2.614Å),
C¹-C^Two(1.351Å) Force at each distance
Constant (force constant) of 418,600 kJ / mol / Å^TwoSet in
Specified. Similarly, C^β-C^α-Zr-C¹(0.00
°), H^β-C^β-C^α-Zr (0.00 °), C^α-Zr
-C¹-C^Two(0.00 °) at each dihedral angle
stant (constant of force) 418,600 kJ / mol / Rad^TwoTo
Set.

[0085]

[Table 4]

The ligand of the zirconocene of Example 1 was {
(Me_TwoSi)_Two (C_FiveH-3,5-Me _Two)_Two}^2-Is
This ligand is represented by Zr-C^αBond, Zr-C¹Binding and distribution
Linking the center of the ligand cyclopentadienyl ring with Zr^Five
Type bonds become tetrahedral around Zr atoms
And the distance from the center of the cyclopentadienyl ring to Zr.
It was located at a distance of 2.2 mm. In this way the calculator
Within {(Me_TwoSi)_Two (C_FiveH-3,5-Me_Two)_Two}^2-Coordination
An elimination model intermediate with offspring was generated. Charge meter
Select the Charge Equilibration method as the
The meter set used was Qeqcharged 1.1. This and
There is only one type of elimination reaction model intermediate,
When the structure is optimized by Minimizer
Total energy (E^b1) Is at 829 kJ / mol
there were.

(3) Calculation of Total Energy of Model Zirconocene Cation A zirconium atom is located at the origin in three-dimensional spatial coordinates, and a linear butyl group is bonded to the zirconium as a model of a polymer chain. {(Me ₂ Si) ₂ (C ₅ H−
3,5-Me ₂ ) ₂ } ^2- ligand so that the distance between the center of the cyclopentadienyl ring and Zr is 2.2 °, and the α carbon of the butyl group and the two The cyclopentadienyl center was positioned flush with the zirconium. The coordinates of all atoms were unconstrained. Select the Charge Equilibration method as the charge calculation method,
The parameter set used was Qeq charged 1.1. The zirconocene minimizer generated here (Minimize
r), the sum of the total energy of the ethylene molecule and the total energy of the ethylene molecule obtained separately (total energy E of the model zirconocene cation).
⁰ ) was 527 kJ / mol.

(4) Calculation of Insertion Reactivity Parameter ΔE _ins and Desorption Reactivity Parameter ΔE _{elm From} the above results, ΔE _ins and ΔE _elm were as follows, respectively. ΔE _ins = min (E ^a1 ) −E ⁰ = 712−527 = 18
5 kJ / mol ΔE _elm = min (E ^b1 ) −E ⁰ = 829−527 = 30
2kJ / mol

[(Me ₂ Si) ₂ (η ⁵ -C ₅ H-3,5-
Synthesis of Me ₂ ) ₂ ZrCl ₂ ] (1) Synthesis of Me ₂ Si (C ₅ H ₃ -Me ₂ ) ₂ 500 g of 12.3 g of 1,3-dimethylcyclopentadiene
l The mixture was placed in a three-necked flask and diluted with 150 ml of THF.
82.0 ml of n-BuLi / hexane solution (1.6 M) at 0 ° C
(131 mmol) was added and the mixture was stirred at room temperature for 2 hours. Further, dimethyldichlorosilane Me ₂ SiCl ₂ was added at 7.degree.
ml (65.1 mmol) and the mixture was stirred at room temperature overnight. Water 10
After 0 ml was added to quench the reaction, extraction was performed with hexane. The obtained organic phase was washed with saturated saline and dried over sodium sulfate. After removing sodium sulfate by filtration, the solvent was distilled off under reduced pressure, and the residue was distilled under reduced pressure. 13 g of a pale yellow liquid (94 ° C./40 Pa) was obtained.

(2) Synthesis of (Me ₂ Si) ₂ (C ₅ H ₂ —Me ₂ ) ₂ The obtained pale yellow liquid Me ₂ Si (C ₅ H ₄ —Me) ₂ (13
g, 54.7 mmol) was placed in a 300 ml two-necked flask, degassed under reduced pressure, and diluted with 100 ml of THF. This was added at 0 ° C. with n-BuLi / hexane solution (1.6M) 69.0 ml
(110 mmol) was added and the mixture was stirred at room temperature for 3 hours. Further, dimethyldichlorosilane Me ₂ SiCl ₂ was added at 0 ° C. for 6.70.
Then, the mixture was stirred overnight at room temperature. After quenching the reaction by adding 100 ml of water, extraction was performed with hexane. The obtained organic phase was washed with saturated saline and dried over sodium sulfate. After removing sodium sulfate by filtration, the solvent was distilled off under reduced pressure to obtain a yellow oily substance.

(3) (Me ₂ Si) ₂ (η ⁵ -C ₅ H-3,5-
Synthesis of Me ₂ ) ₂ ZrCl ₂ White crystals obtained (Me ₂ Si) ₂ (C ₅ H ₂ -Me ₂ ) ₂ (4
g, 13.6 mmol) in a 200 ml two-necked flask,
Dissolved in 50 ml of THF. N-BuLi at 0 ° C
17.0 ml (27.2 mmol) of a 1 / hexane solution (1.6 M) was added, and the mixture was stirred at room temperature for 1 hour, and THF was distilled off. 2.73 g (11.7 g) of zirconium tetrachloride (ZrCl ₄ ) was added to the dried residue.
mmol) in a 200 ml two-necked flask, and placed at −78 ° C.
Then, 50 ml of dichloromethane was added. After stirring at room temperature for 3 hours, the solvent was distilled off under reduced pressure, and 100 ml of toluene was added. The insolubles were filtered with a filter, and the filtrate was concentrated. When left overnight at room temperature, pale yellow crystals precipitated.

¹ H-NMR (CDCl ₃ ): δ (ppm) 0.58
(s, 6H, SiMe), 0.81 (s, 6H, SiMe), 2.20 (s, 12H, Cp
Me), 6.06 (s, 2H, CpH). ¹³ C-NMR (CDCl ₃ ): δ (ppm) 1.73 (SiMe), 5.11 (S
iMe), 16.67 (Cp-Me), 110.64, 123.17, 151.38 (Cp).

[Catalyst preparation] (M
e ₂ Si) ₂ (η ⁵ -C ₅ H-3,5-Me ₂ ) ₂ ZrCl
₂ 101 mg of (DMM) was added and dissolved in 5.0 ml of toluene. 14 ml of a MAO / toluene solution (3.37M) was added thereto, followed by stirring at room temperature for 10 minutes. 10 prepared separately
Silica (Crossfield E)
S-70) 2.50 g was added to a slurry of 15.0 ml of toluene. After stirring at room temperature for 1 hour, toluene was distilled off to obtain a white powder.

[Polymerization] Butyl ethylmagnesium (BEM) was added to a dried 1.5 L stainless steel autoclave.
8 mmol was added. After 800 ml of isobutane was injected into this reactor, the temperature was raised to 70 ° C. while stirring at 300 rpm. At this temperature, an ethylene pressure of 1 MPa was applied.
80 mg of the silica-supported catalyst prepared above was mixed with 5 ml of hexane.
As a slurry of the above, press-in polymerization was started into the reactor at 4 MPa of nitrogen. After 60 minutes, ethylene and isobutane were purged to terminate the polymerization. The polymer yield after vacuum drying is 10
It was 0 g. The polyethylene molecular weight (Mn) obtained is
It was 440000.

[0095]Example 2 [Calculation of insertion reactivity parameter and desorption reactivity parameter
(1) Calculation of total energy of insertion reaction model intermediate As shown in FIG. 3, zirconium, ethylene,
Generate partial structure of zirconocene containing butyl group in computer
Alive. Like the Z-matrix coordinates shown below
, Zr, C^α, H^α, C¹, C^TwoCoordinates were determined. Ce
rius^TwoOpen Forcefield Restraint
Using Zr-H^α(2.236Å), C^α-H ^α(1.140
Å), Zr-C¹(2.480Å), Zr-C^Two(2.480Å),
C^Two-C^αForce at each distance of (2.700 デ ィ)
 Constant (force constant) of 418,600 kJ / mol / Å^TwoTo
Set. Similarly, H^α-C^α-Zr-C¹(18
0 °), C^α-Zr-C¹-C^Two(0.00 °) dihedral angle
At 418,600 kJ /
mol / Rad^TwoSet to.

[0096]

[Table 5]

The ligand of the zirconocene of Example 2 is [r
_{ac- (Me 2 Si) 2 {} C 5 H-3-Me-5- (CHM
e ₂ )} ₂ ] ^2- , this ligand is represented by a Zr— ^Cα bond,
The η ⁵ type bond connecting the Zr—C ¹ bond and the center of the cyclopentadienyl ring of the ligand to the Zr is tetrahedral around the Zr atom, and the distance from the center of the cyclopentadienyl ring to the Zr. Was placed at a distance of 2.2 km. Thus, {(Me ₂ Si) ₂ (C ₅ H ₂ -4-M
e) An insertion reaction model intermediate having a ₂ } ^2- ligand was generated. The Charge Equilibration method was selected as the charge calculation method, and Qeq charged 1.1 was used as the parameter set. At this time, there are two types of insertion reaction model intermediates, and the total energy (E ^a1 and E ^a2 ) when this structure is optimized by a minimizer is 7
28 and 736 kJ / mol.

(2) Calculation of total energy of elimination reaction model intermediate As shown in FIG. 5, zirconium, ethylene,
Generate partial structure of zirconocene containing butyl group in computer
Alive. Like the Z-matrix coordinates shown below
, Zr, C^α, C^β, H^β, C¹, C^TwoCoordinates are determined
These atoms are Cerius^TwoOpen Forcefield Re
Using a straint (restriction condition), Zr-C ^α(2.335
Å), C^α-C^β(1.448Å), C^β-H^β(1.179
Å), Zr-C^Two(2.614Å), Zr-C¹(2.614Å),
C¹-C^Two(1.351Å) Force at each distance
Constant (force constant) of 418,600 kJ / mol / Å^TwoSet in
Specified. Similarly, C^β-C^α-Zr-C¹(0.00
°), H^β-C^β-C^α-Zr (0.00 °), C^α-Zr
-C¹-C^Two(0.00 °) at each dihedral angle
stant (constant of force) 418,600 kJ / mol / Rad^TwoTo
Set.

[0099]

[Table 6]

The ligand of the zirconocene of Example 2 is [r
_{ac- (Me 2 Si) 2 {} C 5 H-3-Me-5- (CHM
e ₂ )} ₂ ] ^2- , this ligand is represented by a Zr— ^Cα bond,
The η ⁵ type bond connecting the Zr—C ¹ bond and the center of the cyclopentadienyl ring of the ligand to the Zr is tetrahedral around the Zr atom, and the distance from the center of the cyclopentadienyl ring to the Zr. Was placed at a distance of 2.2 km. In this way, [rac− (Me ₂ Si) ₂ {C ₅ H
-3-Me-5- (CHMe ₂ )} ₂ ] An elimination reaction model intermediate having a ^2- ligand was generated. Ch as charge calculation method
The arge Equilibration method was selected, and the parameter set used was Qeq charged 1.1. At this time, there were two types of elimination reaction model intermediates, and the total energies E ^b1 and E ^b2 when this structure was optimized with a minimizer were both 837 kJ / mol.

(3) Model zirconocene cation tota
Calculating the energy of the zirconium atom in the three-dimensional spatial coordinates
The zirconium as a model of the polymer chain
Attach linear butyl groups. [rac- (Me _TwoSi)_Two 
{C_FiveH-3-Me-5 (CHMe_Two)}_Two]^2-Ligand
The distance between the center of the clopentadienyl ring and Zr is 2.2Å
And the α-carbon of the butyl group,
Two cyclopentadienyl centers identical to zirconium
It was positioned to be flat. All atom coordinates are constrained
Not in a state. Charge Equil as charge calculation method
Select the ibration method and set the parameter set to Qeq char
ged 1.1 was used. The zirconocene produced
Obtained by molecular mechanics calculation using Minimizer
Total energy and total energy of ethylene molecules
Sum of Lugie (total energy of model zirconocene cation)
Nergie E⁰) Was 548 kJ / mol.

(4) Calculation of Insertion Reactivity Parameter ΔE _ins and Desorption Reactivity Parameter ΔE _{elm From} the above results, ΔE _ins and ΔE _elm were as follows, respectively. ΔE _ins = min (E ^a1 , E ^a2 ) −E ⁰ = 728−548
= 180 kJ / mol ΔE _elm = min (E ^b1 , E ^b2 ) −E ⁰ = 837-548
= 289 kJ / mol

[Rac- (Me ₂ Si) ₂ {η ⁵ -C ₅ H-
_{3-Me-5- (CHMe 2} )} of ₂ ZrCl ₂ Synthesis] S. M
iyake, L. Henling, JE Bercaw, Organometallics,
1998, 17, 5528. ¹ H-NMR (benzne-d ₆ ): δ (ppm) 0.46 (s, 6H, SiM
e), 0.56, 6H, SiMe), 0.96 (d, 6H, -CHMe ₂₎ , 1.35 (d,
6H, -CHMe ₂₎ , 2.21 (s, 6H, -CpMe), 2.85 (h, 2H, -C
HM _e2 ), 6.16 (s, 2H, CpH).

[Preparation of catalyst] (M)
^{_{e 2 Si) 2 {η 5}} -C 5 H-3-Me-5- (CHMe 2)
} ₂ ZrCl ₂ , 122 mg of (DMP) and toluene 5.
Dissolved in 0 ml. Add MAO / toluene solution (3.37
M) 12.8 ml was added and the mixture was stirred at room temperature for 10 minutes. Into a separately prepared 100 ml two-necked flask, 2.50 g of silica (ES-70 manufactured by Crossfield) was added, and toluene 15.0 m
of the slurry. After stirring at room temperature for 1 hour, toluene was distilled off to obtain a white powder.

[Polymerization] Butyl ethyl magnesium (BEM) was added to a dried 1.5 L stainless steel autoclave.
8 mmol was added. After 800 ml of isobutane was injected into this reactor, the temperature was raised to 70 ° C. while stirring at 300 rpm. At this temperature, an ethylene pressure of 1 MPa was applied.
90 mg of the silica-supported catalyst prepared above was mixed with 5 ml of hexane.
As a slurry of the above, press-in polymerization was started into the reactor at 4 MPa of nitrogen. After 60 minutes, ethylene and isobutane were purged to terminate the polymerization. The polymer yield after vacuum drying was 13
It was 0 g. The polyethylene molecular weight (Mn) obtained is
It was 510000.

[0106] Example 3 [Insert reactivity parameters, elimination reactivity calculation parameters] a ligand _{rac- [(Me 2 Si) {} C 9 H 5 -2-
(CHMe ₂ )} ₂ ] The procedure of Example 1 was repeated except for using ^2- . (1) calculate the insertion reaction model intermediates total energy of insertion reaction model intermediates are 2 kinds, the total energy when optimized with this structure minimizer (Minimizer) (E ^a1 and E ^a2) is 808 And 816kJ / mo
l.

(2) Calculation of total energy of elimination reaction model intermediates There are two types of elimination reaction model intermediates, and the total energies E ^b1 and E ^b2 when this structure is optimized by a minimizer (Minimizer) Are 900 kJ / mol and 904
kJ / mol.

(3) Model zirconocene cation tota
Calculation of the energy of the model zirconocene cation obtained in the same manner as in Example 1.
Total energy E ⁰Is 628 kJ / mol.
Was.

(4) Calculation of Insertion Reactivity Parameter ΔE _ins and Desorption Reactivity Parameter ΔE _{elm From} the above results, ΔE _ins and ΔE _elm were respectively as follows. ΔE _ins = min (E ^a1 , E ^a2 ) −E ⁰ = 808-628
= 180 kJ / mol ΔE _elm = min (E ^b1 , E ^b2 ) −E ⁰ = 900−628
= 272 kJ / mol

[0110] _{[rac- (Me 2 Si) {} C 9 H 5 -2-
(CHMe ₂ )} ₂ Synthesis of ZrCl ₂ (2IIZ)] W. Spal
eck, F. Kuber, A. Winter, J. Rohrmann, B. Bochman
n, M. Antberg, V. Dolle, EF Pauls, Organometalli
cs, 1994, 13, 945.

[Catalyst preparation] Ra was placed in a 30 ml two-necked flask.
c- (Me_TwoSi) {C₉H_Five-2- (CHMe_Two)} _TwoZr
Cl_Two(2IIZ) Add 102mg to toluene 5.0ml
Dissolved. Add MAO / toluene solution (3.37M) 12.8
Then, the mixture was stirred at room temperature for 10 minutes. Prepare this separately
Silica (Crossfield)
ES-70) 2.50 g and toluene 15.0 ml slurry
Lee and added to what was. After stirring for 1 hour at room temperature,
Ruene was distilled off to obtain a white powder.

[Polymerization] Butyl ethyl magnesium (BEM) was added to a dried 1.5 L stainless steel autoclave.
8 mmol was added. After 800 ml of isobutane was injected into this reactor, the temperature was raised to 70 ° C. while stirring at 300 rpm. At this temperature, an ethylene pressure of 1 MPa was applied.
100 mg of the silica-supported catalyst prepared above was treated with 5 m of hexane.
Injection polymerization was started into the reactor at 4 MPa of nitrogen as 1 slurry. After 60 minutes, ethylene and isobutane were purged to terminate the polymerization. The polymer yield after vacuum drying was 8
It was 0 g. The polyethylene molecular weight (Mn) obtained is
It was 610000.

Example 4 [Dimethylanilinium 4-dimethylchlorosilyl-
Production of 2,3,5,6-tetrafluorophenyltris (pentafluorophenyl) borate] 1,2,4,5
7.5 g (50 mmol) of tetrafluorobenzene were dissolved in 50 ml of diethyl ether and cooled in dry ice / denatured alcohol. To this solution, 31.3 ml of a 1.6 mol / L hexane solution of n-butyllithium was added dropwise, and 30
Stirred for minutes. The obtained solution was 883 m of a 2.9% solution of tris (pentafluorophenyl) borane in isoparaffin.
1 (50 mmol) and stirred at 25 ° C. for 30 minutes. At this time, the product (C) was deposited. The solution layer was removed, washed with hexane and dried under vacuum. The obtained product (C) was recrystallized from diethyl ether (yield 34.5).
g). 8.44 g (9.5 mmol) of the product (C) was dissolved in 30 ml of tetrahydrofuran and cooled in a dry ice / denatured alcohol bath. 6.25 ml of a 1.6 mol / L hexane solution of n-butyllithium was added dropwise to this solution,
After stirring for 12 minutes, 12 ml of dimethyldichlorosilane (1
0 mmol) was added to 50 ml of the dissolved tetrahydrofuran, and the mixture was stirred at 25 ° C for 30 minutes. After stirring, 100 ml of heptane was added, and tetrahydrofuran was distilled off.
The heptane layer was removed, washed with hexane, and dried under vacuum. The obtained product was dissolved in 30 ml of dichloromethane, and N,
20 ml of a dichloromethane solution of 2.99 g (19.0 mmol) of N-dimethylaniline hydrochloride was added, and the mixture was stirred for 30 minutes to remove lithium chloride deposited and dried under vacuum. Dimethylanilinium 4-dimethylchlorosilyl-2,3,
1.6 g of 5,6-tetrafluorophenyltris (pentafluorophenyl) borate was obtained. From NMR measurement data (a part of which is shown below), the structure was confirmed. ¹ H-NMR (CD ₂ Cl ₂ ): δ 0.77 (6H), 3.23 (6H), 7.50
(2H), 7.57 (3H), 11.5 (1H); ¹⁹ F-NMR (CD ₂ C
l ₂ ): δ-128.6, -129.1, -130.0, -159.8, -163.6.

Example 5 [Preparation of solid activator]
0.5 g of silica dried at 50 ° C. and 66.7 Pa for 4 hours was added, and a dichloromethane solution of 56 μmol / ml of the ionic compound having a carrier-binding functional group obtained in Example 4 was added.
ml was added with stirring and refluxed for 2 hours. 40 ℃
Was washed three times with 20 ml of dichloromethane and dried under vacuum.
As a result of measuring the boron content of the obtained olefin polymerization catalyst component by inductively coupled high frequency plasma (ICP) spectroscopy, 0.25 mmol of the ionic compound of Example 4 was supported per 1 g of the catalyst component. Was confirmed. In addition, the amount of hydroxyl groups on the silica surface after loading,
It was quantified by measuring the amount of ethane generated as a result of the reaction between the hydroxyl groups on the silica surface and triethylaluminum. As a result, it was confirmed that the hydroxyl groups in the silica were reduced by about 0.25 mmol / g. From this result, it can be seen that substantially all of the ionic compound supported on the silica has reacted with the hydroxyl group on the silica surface. After the gas phase of dichloromethane used as the reaction solvent was brought into contact with water, the solution was neutralized with sodium carbonate, and titrated with an aqueous solution of silver nitrate using potassium chromate as an indicator, thereby reacting the ionic compound with silica. At times, it was confirmed that hydrogen chloride was generated. The solid activator component obtained in this way was washed three times with boiling dichloromethane, but the amount of the ionic compound carried hardly changed, and the bond between the ionic compound and the carrier was sufficiently strong. It was confirmed that there was.

Example 6 [Catalyst preparation] (Me ₂ Si) ₂ (η ⁵ -C ₅ H-3,5-Me
₂ ) ₂ ZrMe ₂ 2 ml of 0.57 mmol / L toluene solution was prepared. Separately, the solid activator 2 obtained in Example 5
70 mg was suspended in 5 ml of toluene. A total of the above zirconocene dimethyl solution was added to a toluene suspension of the solid activator at room temperature and stirred for 2 minutes to form a catalyst suspension.

[Polymerization] 1.6 m of a 0.5 mol / L hexane solution of butylethylmagnesium was placed in a 1.5 L autoclave.
and 800 ml of isobutane were charged, and the temperature was raised to 70 ° C. Under an ethylene pressure of 1 MPa, 3 ml of the above-mentioned catalyst suspension solution dispersed uniformly was injected into the autoclave with nitrogen. The polymerization reaction was continued at 70 ° C. for 60 minutes. Thereafter, the reaction was stopped with ethyl alcohol. The pressure of the reaction gas was released, and the polyethylene was taken out of the reactor and dried under reduced pressure. There was no adhesion of the polymer to the vessel wall. 240g yield
Met. The HLMFR of the resulting polyethylene is no.
It was a flow.

[0117] Example 7 [Catalyst _{preparation] rac- (Me 2 Si) 2} {η 5 -C 5 H-3
_{- (CH 2 C 6 H 5} ) -5-Me} 2 ZrMe 2 0.6mmol
/ L toluene solution (2 ml) was prepared. Separately, 260 mg of the solid activator obtained in Example 5 was suspended in 5 ml of toluene. A total of the above zirconocene dimethyl solution was added to a toluene suspension of the solid activator at room temperature and stirred for 2 minutes to form a catalyst suspension.

[Copolymerization of 1-hexene] A 1.5 L autoclave was charged with 1.6 ml of a 0.5 mol / L hexane solution of butylethylmagnesium, 800 ml of isobutane and 15 g of 1-hexene, and the temperature was raised to 70 ° C. Ethylene pressure 1
With the MPa applied, 3 ml of the above-mentioned catalyst suspension solution uniformly dispersed was injected into an autoclave with nitrogen. 60
The polymerization reaction was continued at 70 ° C. for minutes. Thereafter, the reaction was stopped with ethyl alcohol. The pressure of the reaction gas was released, and the polyethylene was taken out of the reactor and dried under reduced pressure. There was no adhesion of the polymer to the vessel wall. The yield was 280 g. The HLMFR of the resulting polyethylene was no flow.
From the measurement of ¹³ C-NMR of the obtained copolymer, it was found that hexene was incorporated in the main chain. Melting point is 11
8 ° C.

Comparative Example 1 [Calculation of Insertion Reactivity Parameter and Desorption Reactivity Parameter] The same procedure as in Example 1 was carried out except that two [Cp] ⁻ were used as ligands. (1) Calculation of Total Energy of Insertion Reaction Model Intermediate There was one type of insertion reaction model intermediate, and the total energy E ^a1 when this structure was optimized by a Minimizer was 938 kJ / mol. .

(2) Calculation of total energy of elimination reaction model intermediate There is one kind of elimination reaction model intermediate, and the total energy E ^b1 when this structure is optimized by a minimizer is 954 kJ. / Mol.

(3) Model Total Zirconocene Cation
Calculation of the energy of the model zirconocene cation obtained in the same manner as in Example 1.
Total energy E ⁰Is 800 kJ / mol
Was.

(4) Calculation of Insertion Reactivity Parameter ΔE _ins and Desorption Reactivity Parameter ΔE _{elm From} the above results, ΔE _ins and ΔE _elm were as follows, respectively. ΔE _ins = min (E ^a1 ) −E ⁰ = 938−800 = 13
8 kJ / mol ΔE _elm = min (E ^b1 ) −E ⁰ = 954-800 = 15
4 kJ / mol

[Preparation of catalyst] A catalyst was prepared in the same manner as in Example 1 except that the commercially available bis (cyclopentadienyl) zirconium dichloride was used as the zirconocene compound.

[Polymerization] Butyl ethyl magnesium (BEM) was added to a dried 1.5 L stainless steel autoclave.
8 mmol was added. After 800 ml of isobutane was injected into this reactor, the temperature was raised to 70 ° C. while stirring at 300 rpm. At this temperature, an ethylene pressure of 1 MPa was applied.
200 mg of the silica-supported catalyst prepared above was mixed with 5 m of hexane.
Injection polymerization was started into the reactor at 4 MPa of nitrogen as 1 slurry. After 60 minutes, ethylene and isobutane were purged to terminate the polymerization. The polymer yield after vacuum drying was 4
It was 0 g. The polyethylene molecular weight (Mn) obtained is
46000.

[0125] Comparative Example 2 [Insert reactive parameters and calculation of the elimination reactivity Parameters ligand into two [n-Bu-Cp] ^- but using a ligand, in the same manner as in Example 1 Done. (1) Calculating the total energy of the insertion reaction model intermediate There are many elimination reaction model intermediates due to differences in the cyclopentadienyl ring conformation. Of these, the structure is optimized using a minimizer. The minimum total energy when converted is 963 kJ / mo
l.

(2) Calculation of Total Energy of Elimination Reaction Model Intermediate There are many elimination reaction model intermediates due to differences in cyclopentadienyl ring conformation. Minimizer), the minimum total energy is 980 kJ / mo
l.

(3) Model Total Zirconocene Cation
Calculation of the energy of the model zirconocene cation obtained in the same manner as in Example 1.
Total energy E ⁰Is 808 kJ / mol
Was. (4) Insertion reactivity parameter ΔE_insAnd elimination reactive parameters
Data ΔE_elmFrom the above results, ΔE_ins, ΔE_elmAre as follows
became. ΔE_ins= Min (E^a1, E^a2, ...)-E⁰= 963-80
8 = 155 kJ / mol ΔE_elm= Min (E^b1, E^b2, ...)-E⁰= 980-80
8 = 172 kJ / mol

[Preparation of Catalyst] A catalyst was prepared in the same manner as in Example 1 except that the commercially available bis (n-butylcyclopentadienyl) zirconium dichloride was used as the zirconocene compound.

[Polymerization] Butyl ethyl magnesium (BEM) was added to a dried 1.5 L stainless steel autoclave.
8 mmol was added. After 800 ml of isobutane was injected into this reactor, the temperature was raised to 70 ° C. while stirring at 300 rpm. At this temperature, an ethylene pressure of 1 MPa was applied.
100 mg of the silica-supported catalyst prepared above was treated with 5 m of hexane.
Injection polymerization was started into the reactor at 4 MPa of nitrogen as 1 slurry. After 60 minutes, ethylene and isobutane were purged to terminate the polymerization. The polymer yield after vacuum drying was 6
It was 0 g. The polyethylene molecular weight (Mn) obtained is
70000.

Comparative Example 3 [Calculation of Insertion Reactivity Parameter and Desorption Reactivity Parameter] The same procedure as in Example 1 was carried out except that rac- [Et (Ind)] ^- was used as the ligand. (1) Calculation of Total Energy of Insertion Reaction Model Intermediate There are two types of insertion reaction model intermediates. The total energies E ^a1 and E ^a2 when this structure is optimized by a minimizer are 1000 and 975 kJ. / Mol.

(2) Calculation of total energy of elimination reaction model intermediates There are two types of elimination reaction model intermediates, and the total energies E ^b1 and E ^b2 when this structure is optimized with a minimizer (Minimizer) Were 1026 and 1021 kJ / mol.

(3) Model Total Zirconocene Cation
Calculation of the energy of the model zirconocene cation obtained in the same manner as in Example 1.
Total energy E ⁰Is 816 kJ / mol
Was.

(4) Calculation of Insertion Reactivity Parameter ΔE _ins and Desorption Reactivity Parameter ΔE _{elm From} the above results, ΔE _ins and ΔE _elm were as follows, respectively. ΔE _ins = min (E ^a1 ) −E ⁰ = 975-816 = 15
9 kJ / mol ΔE _elm = min (E ^b1 ) −E ⁰ = 1021-816 = 2
05kJ / mol

[Catalyst preparation] The zirconocene compound was converted to rac
A catalyst was prepared in the same manner as in Example 1 except that ethylenebis (indenyl) zirconium dichloride was used.

[Polymerization] Butyl ethyl magnesium (BEM) was added to a dried 1.5 L stainless steel autoclave.
8 mmol was added. After 800 ml of isobutane was injected into this reactor, the temperature was raised to 70 ° C. while stirring at 300 rpm. At this temperature, an ethylene pressure of 1 MPa was applied.
150 mg of the silica-supported catalyst prepared above was mixed with 5 m of hexane.
Injection polymerization was started into the reactor at 4 MPa of nitrogen as 1 slurry. After 60 minutes, ethylene and isobutane were purged to terminate the polymerization. The polymer yield after vacuum drying was 6
It was 0 g. The polyethylene molecular weight (Mn) obtained is
86000.

Comparative Example 4 [Calculation of Insertion Reactivity Parameter and Desorption Reactivity Parameter] rac- [Me ₂ Si (C ₅ H ₂ -2,4-
Me _{2) 2]} ^- except for using it was carried out in the same manner as in Example 1.

(1) Calculation of Total Energy of Insertion Reaction Model Intermediate There are two types of insertion reaction model intermediates, and the total energies E ^a1 and E ^a2 when this structure is optimized by a minimizer are: 637 and 653 kJ / mol.

(2) Calculation of total energy of elimination reaction model intermediates There are two types of elimination reaction model intermediates, and the total energies E ^b1 and E ^b2 when this structure is optimized by a minimizer Was 678 and 657 kJ / mol.

(3) Model zirconocene cation tota
Calculation of the energy of the model zirconocene cation obtained in the same manner as in Example 1.
Total energy E ⁰Is 494 kJ / mol
Was.

(4) Calculation of Insertion Reactivity Parameter ΔE _ins and Desorption Reactivity Parameter ΔE _{elm From} the above results, ΔE _ins and ΔE _elm were as follows, respectively. ΔE _ins = min (E ^a1 , E ^a2 ) −E ⁰ = 637-494
= 143 kJ / mol ΔE _elm = min (E ^b1 , E ^b2 ) −E ⁰ = 657-494
= 163 kJ / mol

[Preparation of catalyst] The zirconocene compound was converted to rac
-Me_TwoSi (C_FiveH_Two−2,4-Me_Two)_TwoZrCl _Twoage
A catalyst was prepared in the same manner as in Example 1 except for the above.

[Polymerization] Butyl ethyl magnesium (BEM) was added to a dried 1.5 L stainless steel autoclave.
8 mmol was added. After 800 ml of isobutane was injected into this reactor, the temperature was raised to 70 ° C. while stirring at 300 rpm. At this temperature, an ethylene pressure of 1 MPa was applied.
200 mg of the silica-supported catalyst prepared above was mixed with 5 m of hexane.
Injection polymerization was started into the reactor at 4 MPa of nitrogen as 1 slurry. After 60 minutes, ethylene and isobutane were purged to terminate the polymerization. The polymer yield after vacuum drying is 7
It was 0 g. The polyethylene molecular weight (Mn) obtained is
77,000.

Table 7 summarizes the results of Examples 1 to 3, 6, and 7 and Comparative Examples 1 to 4.

[Table 7]

[0144]

According to the present invention, the HLMFR having a number average molecular weight (Mn) of 250,000 or more estimated by GPC in ethylene polymerization at a practical polymerization temperature of 70 ° C. or more,
(Method described in JIS K6760: 190 ° C, 21.6 kg
The present invention provides a catalyst capable of obtaining polyethylene having a high load (no load) with high activity.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of the difference between the total energy of an insertion reaction model intermediate and the total energy of a model zirconocene cation when the polymer chain is a butyl group in the zirconocene cation.

FIG. 2 is an explanatory diagram of the difference between the total energy of the elimination reaction model intermediate and the total energy of the model zirconocene cation when the polymer chain is a butyl group in the zirconocene cation.

FIG. 3 is an explanatory diagram of an insertion reaction model intermediate.

FIG. 4. Ethylene insertion reactivity parameter (Δ
The intermediate structure of an insertion reaction model when ethylene is inserted in obtaining E _ins ) is shown.

FIG. 5 is an explanatory diagram of an elimination reaction model intermediate.

FIG. 6: Desorption reactivity parameter of ethylene (Δ
The elimination reaction model intermediate structure when ethylene is eliminated in obtaining E _elm ) is shown.

Continuation of the front page (72) Inventor Masaki Fushimi 1-5-12 Nakajima Nishi, Oita City, Oita Prefecture Green Hill Nakajima 801 F-term (Reference) 4J028 AA01A AB00A AC26A AC27A AC28A BA00B BA01A BA01B BA02A BA02B BA03A BA04A BB00A BB01B BB01B BB01B BC01B BC04B BC12A BC13A BC14B BC15A BC15B BC16B BC25A CA25A CA27A CA28A CA29A CA30A CB02A CB04A CB12A CB14A CB23A CB27A CB47A DB04A DB05A EA01 EB02 EB05 EB07 A04A01A01A01A02A

Claims (8)

[Claims] 1. A zirconocene compound and an activator, wherein the zirconocene compound has an ethylene insertion reactivity parameter (ΔE _ins (kJ / mol)) and a polymer chain desorption reactivity parameter (ΔE _elm (kJ / mol)). ) Is given by the formula (I): A catalyst for ethylene polymerization characterized by satisfying the following conditions: 2. A zirconocene compound represented by the general formula (1): Wherein, R ¹ to R ⁵ may be the same or different, mean respectively a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group having 1 to 10 carbon atoms,, R ¹ ~ R ⁵ may form a ring with the adjacent substituents. ],
General formula (2) Wherein, R ¹ to R ⁸ may be the same or different, mean respectively a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group having 1 to 10 carbon atoms,, R ¹ ~ R ⁸ may form a ring with a substituent adjacent to each other, and X ¹ which is a cross-linking group of a cyclopentadienyl ring is a dialkylsilylene group, a tetraalkyldisilenyl group, or a C 1 to C 3 It means an alkylene group, and the numerical value at the upper right of the parenthesis in the formula means a valence. Or the general formula (3) Wherein, R ¹ to R ⁶ may be the same or different, mean respectively a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group having 1 to 10 carbon atoms,, R ¹ ~ R ⁶ may form a ring with a substituent adjacent to each other, and X ¹ and X ² which are a cross-linking group of a cyclopentadienyl ring may be the same or different from each other, and may be a dialkylsilylene group, It means an alkyldisilenyl group or an alkylene group having 1 to 3 carbon atoms. The catalyst for ethylene polymerization according to claim 1, which has a ligand represented by the formula: 3. The method of claim 1, wherein ΔE _elm (kJ / mol) and ΔE _ins (k
J / mol) is given by the formula (II): The catalyst for ethylene polymerization according to claim 1, which satisfies the following condition: 4. The catalyst for ethylene polymerization according to claim 1, wherein the relationship between ΔE _elm and ΔE _ins satisfies the condition of the formula (I), and ΔE _elm is 251 kJ / mol or more. 5. The ethylene polymerization catalyst according to claim 3, wherein the relationship between ΔE _elm and ΔE _ins satisfies the condition of the formula (II), and ΔE _elm is 251 kJ / mol or more. 6. The zirconocene compound represented by the general formula (4): [Wherein, M represents zirconium, and R ^{1 to} R ⁴ may be the same or different and each represent a hydrogen atom, a carbon number of 1 to 1;
0 represents a hydrocarbon group or an alkylsilyl group having 1 to 10 carbon atoms, R ^{1 to} R ⁴ may form a ring with a substituent adjacent to each other, and X represents a halogen atom, a hydride, or a carbon atom having 1 carbon atom. An alkyl group having 10 to 10, an aryl group having 6 to 15 carbon atoms,
Or an alkoxy group represented by an OR ⁹ group (wherein R ⁹ is an alkyl group having 1 to 10 carbon atoms, an aryl group, an arylalkyl group or a fluoroaryl group having 6 to 15 carbon atoms), E ¹ and E ² are each independently Si
(R ¹⁰ ) ₂ or C (R ¹⁰ ) ₂ , wherein two R ^{10 s} may be the same or different and each have an alkyl group having 1 to 10 carbon atoms, an arylalkyl group having 6 to 15 carbon atoms, or It means a cycloalkyl group having 3 to 10 carbon atoms, and n is 2. The catalyst for ethylene polymerization according to claim 1 or 2, wherein the activator is a solid activator. 7. A method for producing polyethylene, comprising using the catalyst according to claim 1. Description: 8. The method according to claim 7, wherein an organometallic compound is used as the third component during the polymerization.