JP2001081125A - Catalyst component for alpha-olefin-ethylene copolymerization, catalyst and method for producing alpha-olefin-ethylene copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject catalyst component with which a specific polymer having a high mol.wt. and capable of being extrusion-molded or the like can be produced in a high yield by including a specific organic metal compound. SOLUTION: This catalyst component for the copolymerization of a 3 to 20C α-olefin with ethylene comprises an organic ligand-containing metal complex compound having an energy index ΔEa of <=1.00 kcal/mol ΔEa=Ea(Me, Me)+Ea(H, H)-2*Ea(Me, H), [Ea(Me, Me), Ea(H, H), and Ea(Me, H) are the activation energies of reactions for converting the β-H of the terminal propylene unit of the polymer chain into propylene monomer, converting the β-H of the terminal ethylene unit of the polymer chain into ethylene monomer, and converting the β-H of the terminal propylene unit of the polymer chain into ethylene monomer, respectively]}. The energy index ΔEa is calculated on an activation energy obtained by a quantum chemical calculation method and the like with respect to a six central reaction for converting the β-H of the terminal propylene unit of the polymer chain into ethylene monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a catalyst component for α-olefin-ethylene copolymerization comprising a specific organometallic compound, a catalyst for α-olefin-ethylene copolymerization using the organometallic compound, and the use of the same. The present invention relates to a method for producing an α-olefin-ethylene copolymer having 3 to 20 carbon atoms. More specifically, a high molecular weight carbon number 3
The present invention relates to a polymerization catalyst component, a polymerization catalyst, and a method for producing an α-olefin-ethylene copolymer using the catalyst, which enables the production of α-olefin-ethylene copolymers of Nos. 1 to 20.

[0002]

2. Description of the Related Art As a homogeneous catalyst for olefin polymerization, a so-called Kaminski catalyst is well known. This catalyst is characterized by a very high polymerization activity and a polymer having a narrow molecular weight distribution. Transition metal compounds used for producing isotactic polypropylene by Kaminsky catalyst include ethylenebis (indenyl) zirconium dichloride and ethylenebis (4,5,5).
(6,7-Tetrahydroindenyl) zirconium dichloride (for example, JP-A-61-130314) is known. Further, a compound is known in which an isotacticity and a molecular weight of polypropylene are improved by adding a substituent to an indenyl group which is a part of a ligand (for example, JP-A-4-268307). JP-A-6-157661, etc.). Further, there are also reports on transition metal compounds in which the sub-ring including two adjacent carbon atoms of the conjugated five-membered ring is a ring having a number of members other than the six-membered ring (for example, JP-A-4-275294, JP-A-6-23).
No. 9914, JP-A-8-59724, etc.).

[0003] On the other hand, another characteristic of these catalyst systems is that they have a narrow composition distribution at the time of copolymerization and are excellent in random copolymerizability, so that high performance random copolymers which cannot be achieved with conventional olefin polymerization catalysts. Is expected to be obtained. However, when copolymerization of an α-olefin having 3 to 20 carbon atoms and ethylene is performed in these catalyst systems, the problem that the molecular weight of the produced polymer decreases with the introduction of ethylene is shown in the following report. (Pre
print of The Internationala
l Conference on Polyolefi
ns XI, P. 313 Houston, Febr
uary, 22-24, 1999, Science a
nd Technology in Catalysis
s 1994 p. 371) With conventional metallocene-type catalysts, it has been difficult to produce industrially valuable high molecular weight random copolymers used in the fields of extrusion molding and blow molding.

In recent years, new research methods for improving catalysts by calculating information on elementary reaction mechanisms and energies of catalytic reactions using molecular chemical calculations such as quantum chemical calculation or molecular force field calculation have been developed. . Numerous studies on metallocene catalysts have also been reported.
Book "Zieglar Catalog" edited by Fink et al.
lysis "(Springer) Berlin, 1
995 introduces many examples. In many cases where the catalytic reaction is calculated, it is necessary to perform quantum chemical calculation. However, it is difficult to handle the actual catalyst, and therefore, modeling such as simplification of the ligand is required. The method of determining the actual ligand by molecular force field calculation based on the model skeleton obtained in this way is effective in estimating the steric effect of the catalyst ligand, and the stereoregularity of polypropylene It is used for research. Studies using molecular science calculations on chain transfer reactions directly related to molecular weight have also been performed. For example, see C. W. Lohrenz, T .; K. Wo
o, T .; Zieglar, J .; Am. Chem. So
c. 117, 12973 (1995). However, at present, they are only at the stage where quantum chemical calculations are performed on simple ligands that model ligands that are industrially problematic.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a high-molecular-weight C3 to C2 compound which enables extrusion molding and blow molding.
It is an object of the present invention to provide a catalyst component for ethylene-α-olefin copolymerization, which makes it possible to obtain a copolymer of α-olefin and ethylene in a high yield. Another object of the present invention is to provide a catalyst for α-olefin-ethylene copolymer using the catalyst component and a method for producing an α-olefin-ethylene copolymer using the same. Particularly, under the same polymerization conditions (other than the monomers), a catalyst component for providing an α-olefin-ethylene copolymer having a molecular weight equal to or higher than that of an α-olefin homopolymer, and for use in an α-olefin-ethylene copolymer using this catalyst component An object of the present invention is to provide a catalyst and a method for producing an α-olefin-ethylene copolymer using the catalyst.

[0006]

The present invention has been found as a result of intensive studies to solve the above problems. That is, the present invention was created by applying the method of calculating the model skeleton by quantum chemical calculation, which was effective for stereoregularity, and treating the actual ligand by molecular force field calculation to the chain transfer reaction for copolymerization. This is the catalyst component that has been reached as a result of performing a catalyst design using the results and conducting experimental verification.

The present invention relates to a catalyst component for copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms, which is used for a six-center reaction in which the hydrogen at the β-position of the terminal propylene unit of the polymer is transferred to an ethylene monomer. Index ΔEa calculated based on (Equation 1) from the activation energy obtained using the calculation method and the molecular force field calculation method
Of an organic ligand-containing metal complex compound having a molecular weight of 1.00 kcal / mol or less. ΔEa = Ea (Me, Me) + Ea (H, H) −2 * Ea (Me, H) (Formula 1) Ea (Me, Me): Transfer of hydrogen at β-position of propylene unit at polymer chain terminal to propylene monomer The activation energy of the reaction. Ea (H, H): activation energy of the reaction of transferring the hydrogen at the β-position of the ethylene unit at the terminal of the polymer chain to the ethylene monomer. Ea (Me, H): activation energy of the reaction in which the hydrogen at the β-position of the propylene unit at the terminal of the polymer chain is transferred to an ethylene monomer.

Further, the present invention provides a catalyst for α-olefin-ethylene copolymer using the catalyst component, and a catalyst having 3 to 3 carbon atoms.
It is another object of the present invention to provide a method for producing a copolymer of α-olefin and ethylene.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. <Calculation method> 1. Model reaction A reaction formula (Equation 2) that models a 6-center reaction in which the hydrogen at the β-position of the terminal monomer unit of the polymer is transferred to a monomer molecule.
Is calculated using. LM (CH ₂ CHPR ¹ ) (+) + CH ₂ CHR ² → LM (CH ₂ CH ₂ R ² ) (+) + CH ₂ CPR ¹ (Formula 2) L is a metal complex containing two chlorine atoms or an organic ligand. M represents an organic ligand, a π-bonding ligand portion (hereinafter referred to as L1) in the compound, or a biscyclopentadienyl ligand portion bridged at the 1-position in L1 (hereinafter referred to as L2). P represents a methyl group in quantum chemical calculation and CH ₂ CH in molecular force field calculation.
(CH ₃ ) CH ₂ CH (CH ₃ ) CH ₂ CH ₃ group. R ¹
Is a hydrogen atom or a methyl group R ² is a hydrogen atom or a methyl group (hereinafter, a hydrogen atom is represented by H and a methyl group is represented by Me) (+) is LM (CH ₂ CHPR ¹ ) and LM (CH ₂ CH ₂₎
R ² ) is a cation.

[0010] 2. Quantum Chemical Calculation (1) Model Reaction of Quantum Chemical Calculation Regarding the reaction represented by (Equation 2), the ligand L is two chlorine atoms, and the model substituent P of the polymer chain is a methyl group. M is a transition metal atom in the organic ligand-containing metal complex compound. Quantum chemical calculation is based on the pair of substituents R ¹ and R ² (R
¹ , R ² ) is (Me, Me), (H, H), (Me, H)
The calculation is performed for the case of.

(2) Software used For example, Gaussian Inc. Gaussi made by
an94 is used. (3) Quantum chemical calculation method Restrictive second-order mailer preset many-body perturbation method (RMP2
Method). A frozen core approximation is used that excludes the core electrons of each atom from the perturbation method. The basis set is Lanl2dz for M shown in (Equation 2), and the other atoms are 3
-21G is adopted. When the Gaussian 94 is used, both are built-in.

(4) Determination of Molecular Structure The six-center transition state structure of the reaction represented by (Equation 2) is determined by the energy gradient method. Further, LM (CH ₂ CHP)
The structure in which the monomer CH ₂ CH ₂ R ² is π-coordinated to M in R ¹ ) (+) is determined by the energy gradient method. (5) Determination of basic activation energy Using the total energy of the transition state structure and the π-coordination structure of the monomer obtained by performing the above calculation, the basic activation energy Eq (R ¹ , R ² ) Calculate.

Eq (R ¹ , R ² ) = E 1 (R ¹ , R ¹ ) −E 2 (R ¹ , R ² ) (Equation 3) E 1 (R ¹ , R ² ): transition state obtained from quantum chemical calculation total energy E2 structure (R ^1, R ^2): total energy wherein R ^1, R ² of the π coordination structure of the monomer obtained from quantum chemical calculations represent a substituent shown by equation (2).

3. Molecular force field calculation (6) Model reaction of molecular force field calculation Regarding the reaction represented by (Equation 2), P is CH ₂ CH (C
H ₃ ) CH ₂ CH (CH ₃ ) CH ₂ CH ₃ . The pair (R ¹ , R ² ) of the substituents R ¹ and R ² is (Me, Me), (H,
H), (Me, H). L is L1 and L2. (7) Software used For example, MSI (Molecular Simulat)
ions Inc. ) Is used.

(8) Method of calculating molecular force field A molecular force field CFF91 is used. However, M is treated as a dummy atom, and the force constant is 33.507 with minimizing 2.5872 ° between each carbon atom of the 5-membered ring portion of the ligand L.
A harmonic potential constraint of 9 kcal / mol * {*} is added. Here, Å means angstrom.

(9) Determination of transition state structure In the transition state structure obtained by the quantum chemical calculation, two chlorine atoms of L, all hydrogen atoms of the methyl group of P, and R ¹ and R ² are methyl groups. In such a case, the atomic coordinates of the partial structure from which all the hydrogen atoms have been removed are fixed and used in the molecular force field calculation. Using the energy gradient method, the structure in which the total energy has a minimum value is determined. The initial structure of the calculation is R ¹ , R ²
In such a way that the three-dimensional position of is the farthest distance from L. As the initial structure of the ligand L, if there is a molecular structure obtained by X-ray diffraction or the like of a complex containing a similar ligand, it will be used. If there is no corresponding molecular structure, a structure having the smallest energy among various energy minimum structures obtained as a result of performing the molecular force field calculation is adopted as the transition state structure.

(10) Determination of partial structure The LM partial structure is determined by the energy gradient method. The LM partial structure of the transition state molecular structure obtained when (R ¹ , R ² ) = (Me, H) in the above molecular force field calculation is calculated as an initial structure. (11) Determination of steric repulsion energy Using the total energies of the transition state structure and the partial structure obtained by performing the above molecular force field calculation, the steric repulsion energy Er (R ¹ , R ² ).

Er (R ¹ , R ² ) = Em (R ¹ , R ² ) −Eo (R ¹ , R ² ) + Em (0) −Eo (0) (Equation 4) Em (R ¹ , R ² ) : Total energy of transition state structure obtained by molecular force field calculation when ligand L is L1 Eo (R ¹ , R ² ): Total energy obtained by molecular force field calculation when ligand L is L2 Total energy of transition state structure Em (0): Total energy of LM substructure obtained by molecular force field calculation when ligand L is L1 Eo (0): Molecule when ligand L is L2 Total energy of LM partial structure obtained by force field calculation Here, R ¹ and R ² represent substituents represented by (Formula 2).

4. Calculation of energy index (12) Determination of activation energy Using the above calculation results, the activation energy Ea (R ¹ , R ¹ , R ² ) is determined. ^{Ea (R 1, R 2)} = Eq (R 1, R 2) -Er (R 1, R 2) ( Equation ^{5) Eq (R 1, R} 2) basic activation energy was determined according to: wherein 3) Er (R ¹ , R ² ): steric repulsion energy determined according to (Formula 4) Here, R ¹ and R ² represent substituents represented by (Formula 2).

(13) Determination of energy index Using the activation energy determined according to (Equation 5),
It is determined by the above (Equation 1). ΔEa = Ea (Me, Me) + Ea (H, H) −2 * Ea (Me, H) (Formula 1) Ea (Me, Me): Transfer of hydrogen at β-position of propylene unit at polymer chain terminal to propylene monomer The activation energy of the reaction. Ea (H, H): activation energy of the reaction of transferring the hydrogen at the β-position of the ethylene unit at the terminal of the polymer chain to the ethylene monomer. Ea (Me, H): activation energy of the reaction in which the hydrogen at the β-position of the propylene unit at the terminal of the polymer chain is transferred to an ethylene monomer.

[0021] R ¹ here notation Ea (R ^1, R ²⁾ in, R ²
Represents R ¹ and R ² shown in (Equation 2),
H represents a hydrogen atom, and Me represents a methyl group. The catalyst component used in the present invention has an energy index ΔEa calculated based on (Equation 1) of 1.00 kcal / mol or less,
The α-olefin / ethylene copolymerization catalyst component is preferably -1.6 kcal / mol or less. When ΔEa deviates from these values, the high molecular weight α-olefin-ethylene copolymer intended in the present invention cannot be obtained.

As a preferred catalyst component of the present invention, a transition metal compound represented by the following general formula (1) is used.

Embedded image (Wherein M is a transition metal selected from Group 4 transition metal elements, and two Ras may be the same or different, and are monovalent hydrocarbon groups having 1 to 20 carbon atoms, halogen atoms Group or halogen, silicon, boron, oxygen, nitrogen,
A phosphorus or sulfur-containing hydrocarbon group having 1 to 20 carbon atoms, 2
Rb may be the same or different and have 4 to 4 carbon atoms bonded to two adjacent carbon atoms of the five-membered ring ligand.
20 divalent hydrocarbon groups or 4 to 20 carbon atoms
Is a divalent hydrocarbon group containing halogen, silicon, germanium, boron, oxygen, nitrogen, phosphorus, or sulfur, and may have a substituent at any position.
Q represents a bonding group bridging the two ligands, and X and Y each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group. It represents a hydrogen group or a silicon-containing hydrocarbon group. )

M is a metal atom of Group 4 of the periodic table, specifically, titanium, zirconium, hafnium or the like. Particularly, zirconium and hafnium are preferable. The two Ras may be the same or different and contain a monovalent hydrocarbon group having 1 to 20 carbon atoms, a halogen atom group, or halogen, silicon, boron, oxygen, nitrogen, phosphorus, or sulfur. A hydrocarbon group having 1 to 20 carbon atoms. Preferably, it is a hydrocarbon group having 1 to 12 carbon atoms, a halogen atom group, a halogen atom, silicon, boron, oxygen, nitrogen, adjacent, or a hydrocarbon group having 1 to 12 carbon atoms containing sulfur. More specifically, Ra is a saturated hydrocarbon group such as alkyl and cycloalkyl, an unsaturated hydrocarbon group such as alkenyl and aryl, and a halogen atom group such as fluorine, chlorine and bromine;
A silicon-containing hydrocarbon group having 1 to 20 carbon atoms represented by SiRaRbRc, 1 to 20 carbon atoms represented by -BRaRb
Containing a boron-containing hydrocarbon group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms represented by -PRaRb, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms represented by -NRaRb, or containing halogen, oxygen, and sulfur. Examples thereof include a hydrocarbon group having 1 to 20 carbon atoms. Of these, alkyl groups such as methyl, ethyl and n-propyl are particularly preferred.

The two Rb's may be the same or different and are each a divalent hydrocarbon group having 4 to 20 carbon atoms bonded to two adjacent carbon atoms of the five-membered ring ligand. A divalent hydrocarbon group containing halogen, silicon, germanium, boron, oxygen, nitrogen, phosphorus, or sulfur represented by Formulas 4 to 20, and may have a substituent at any position.

More specifically, R ² is a saturated hydrocarbon group such as alkylene or cycloalkylene, or an unsaturated hydrocarbon group such as alkenylene, alkadienylene, or arylene, for example, a divalent carbon atom having 1 to 20 carbon atoms represented by -SiRaRbRc.
A silicon-containing hydrocarbon group, a divalent boron-containing hydrocarbon group having 1 to 20 carbon atoms represented by -BRaRb, -PRaR
b, a divalent phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, -NRaRb, a divalent nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, or divalent containing halogen, oxygen, and sulfur And a hydrocarbon group having 1 to 20 carbon atoms.

Particularly preferred among these are methyl,
It is an alkyl group such as ethyl and n-propyl. By the way, Rb may have a substituent at an arbitrary position. When two or more substituents are present, they may be the same or different, and the same substituent as the substituent represented by Ra can be used.

Among them, preferred are an alkyl group, an aryl group, a halogenated alkyl group and a halogenated aryl group. Specific examples of Rb include substituted or unsubstituted butylene, pentylene, 1,3-butadienylene,
Examples thereof include 3-pentadienylene and the like, and particularly preferred are 1,3-butadienylene and 1,3-pentadienylene having an aryl substituent or a halogenated aryl substituent.

Q represents a bonding group bridging the two ligands, and is a hydrocarbon group containing alkylene groups, alkylsilylene groups, germanium, phosphorus, nitrogen, boron or aluminum.

Specific examples of Q include (a) a methylene group,
C1-C20 alkylene groups such as ethylene group, isopropylene group, phenylmethylmethylene group, diphenylmethylene group, and cyclohexylene group;

(B) a silylene group, a dimethylsilylene group,
Silylene groups such as phenylmethylsilylene group, diphenylsilylene group, disilylene group, and tetramethyldisilylene group; and (c) hydrocarbon groups containing germanium, phosphorus, nitrogen, boron or aluminum. More specifically,
(CH ₃ ) ₂ Ge, (C ₆ H ₅ ) ₂ Ge, (CH ₃ ) P, (C
_{6 H 5) P, (C} 4 H 9) N, (C 6 H 5) N, (CH 3)
B, (C ₄ H ₉ ) B, (C ₆ H ₅ ) B, (C ₆ H ₅ ) Al,
And a group represented by (CH ₃ O) Al. Preferred are alkylene groups, silylene groups, and germylene groups.

X and Y each represent hydrogen, a halogen atom,
C1-C20, preferably C1-C10 hydrocarbon group, C1-C20, preferably C1-C10 alkoxy group, amino group, Nitrogen containing C1-C20, preferably C1-C10 A phosphorus-containing hydrocarbon group having 1 to 20, preferably 1 to 12 carbon atoms such as a hydrocarbon group and a diphenylphosphine group, or a carbon atom having 1 to 20, preferably 1 to 12 carbon atoms such as a trimethylsilyl group and a bis (trimethylsilyl) methyl group;
Is a silicon-containing hydrocarbon group. X and Y may be the same or different. Of these, halogen atoms and carbon numbers 1 to 1
A hydrocarbon group having 8 and a nitrogen-containing hydrocarbon group having 1 to 12 carbon atoms are preferred.

Specific examples of the compounds included in the present invention are as follows: (1) Dichlorodimethylsilylenebis (2-methyl-4
-(1-naphthyl) -4H-azulenyl) zirconium (2) dichlorodimethylsilylenebis (2-ethyl-4
-(1-naphthyl) -4H-azulenyl) zirconium (3) dichlorodimethylsilylenebis (2-n-propyl-4- (1-naphthyl) -4H-azulenyl) zirconium (4) dichlorodimethylsilylenebis (2-methyl -4
-Anthracenyl-4H-azulenyl) zirconium (5) dichlorodimethylsilylenebis (2-ethyl-4
-Anthracenyl-4H-azulenyl) zirconium (6) dichlorodimethylsilylenebis (2-n-propyl-4-anthracenyl-4H-azulenyl) zirconium (7) dichlorodimethylsilylenebis (2-methyl-4
-(9-phenanthryl) -4H-azulenyl) zirconium (8) dichlorodimethylsilylenebis (2-ethyl-4
-(9-phenanthryl) -4H-azulenyl) zirconium (9) dichlorodimethylsilylenebis (2-n-propyl-4- (9-phenanthryl) -4H-azulenyl)
zirconium

Further, those obtained by replacing chlorine in the above-mentioned compounds with bromine, iodine, hydride, methyl, phenyl and the like can also be used. Further, in the present invention, a compound in which the central metal of the zirconium compound exemplified above is replaced with titanium or hafnium can be used as the component (A).
Among these, preferred are zirconium compounds,
It is a hafnium compound. These (A) components may be used in combination of two or more. The component (A) may be newly added at the end of the first stage of the polymerization or before the start of the second stage of the polymerization.

In the present invention, the component (B) includes
(I) an aluminum oxy compound, (ii) a Lewis acid,
(Iii) selected from the group consisting of ionic compounds capable of converting component (A) into cations by reacting with component (A), and (iv) ion-exchange layered compounds or inorganic silicates other than silicates. Use one or more substances. Certain Lewis acids can be understood as ionic compounds capable of reacting with the component (A) to convert the component (A) into a cation. Therefore, compounds belonging to both the above-mentioned Lewis acids and ionic compounds are understood to belong to either one.

Specific examples of the above (i) aluminum oxy compound include compounds represented by the following general formulas (2), (3) and (4).

[0036]

Embedded image

[0037]

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[0038]

Embedded image

In the above general formulas, Rc and Rd are each a hydrogen atom or a hydrocarbon residue, preferably a hydrocarbon residue having 1 to 10 carbon atoms, particularly preferably a hydrocarbon residue having 1 to 6 carbon atoms or a halogenated hydrocarbon group. Is shown. Further, a plurality of Rc may be the same or different. M represents an integer of 0 to 40, preferably 2 to 30.

The compounds represented by the general formulas (2) and (3) are compounds also called aluminoxanes, and are obtained by reacting one kind of trialkylaluminum or two or more kinds of trialkylaluminums with water. Specifically, (a) obtained from one kind of trialkylaluminum and water, methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, (b) obtained from two kinds of trialkylaluminum and water, Examples thereof include methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane and the like. Of these, methyl aluminoxane and methyl isobutyl aluminoxane are preferred.

The above aluminoxanes can be used in combination of two or more. And the above aluminoxane is
It can be prepared under various known conditions. The compound represented by the general formula (4) is obtained by mixing one or more trialkylaluminums or two or more trialkylaluminums with (alkyl) boronic acid represented by the following general formula (5) in the range of 10: 1 to 1 : 1 (molar ratio). In the general formula (5), Rd represents hydrogen or carbon atom 1
And, preferably, a hydrocarbon residue having 1 to 6 carbon atoms or a halogenated hydrocarbon group.

RdB- (OH) ₂ General formula (5)

Specifically, the following reaction products can be exemplified. (A) Trimethylaluminum and methylboronic acid 2:
(B) 2: 1 reaction product of triisobutylaluminum and methylboronic acid (c) 1: 1: 1 reaction product of trimethylaluminum, triisobutylaluminum and methylboronic acid (d) 2: 2 reaction of trimethylaluminum and methylboronic acid
1 Reactant (e) Triethylaluminum and butylboronic acid 2:
1 reactant

Examples of (ii) Lewis acids, especially Lewis acids capable of converting component (A) into cations, include various organic boron compounds, metal halide compounds, solid acids, and the like. The following compounds may be mentioned.

(A) triphenylboron, tris (3,
Organic boron compounds such as 5-difluorophenyl) boron and tris (pentafluorophenyl) boron (b) aluminum chloride, aluminum bromide, aluminum iodide, magnesium chloride, magnesium bromide, magnesium iodide, magnesium chloride bromide, chloride Metal halide compounds such as magnesium iodide, magnesium bromide iodide, magnesium chloride hydride, magnesium chloride hydroxide, magnesium bromide hydroxide, magnesium chloride alkoxide, magnesium bromide alkoxide, etc. (c) Solid acids such as alumina and silica-alumina

The (iii) ionic compound capable of converting the component (A) into a cation by reacting with the component (A) includes a compound represented by the general formula (6). [K] ^{e +} [Z] ^e- general formula (6)

In the general formula (10), K is a cation component, and examples thereof include a carbonium cation, a tropylium cation, an ammonium cation, an oxonium cation, a sulfonium cation, and a phosphonium cation. In addition, metal cations and organic metal cations that are easily reduced by themselves are also included.

Specific examples of the above cation include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, indenium, triethylammonium, tripropylammonium, tributylammonium, N, N-dimethylanilinium, dipropylammonium, Dicyclohexylammonium, triphenylphosphonium, trimethylphosphonium, tris (dimethylphenyl) phosphonium, tris (methylphenyl) phosphonium, triphenylsulfonium, triphenyloxonium, triethyloxonium, pyrylium, silver ion, gold ion, platinum ion, copper ion , Palladium ion, mercury ion, ferrocenium ion and the like.

In the above general formula (6), Z is an anion component, which is a component (generally a non-coordinating component) that becomes a counter anion to the converted cation species of component (A). As Z, for example, an organic boron compound anion,
Organic aluminum compound anion, organic gallium compound anion, organic phosphorus compound anion, organic arsenic compound anion, organic antimony compound anion, and the like,
Specific examples include the following compounds.

(A) Tetraphenylboron, tetrakis (3,4,5-trifluorophenyl) boron, tetrakis {3,5-bis (trifluoromethyl) phenyl}
Boron, tetrakis {3,5-di (t-butyl) phenyl} boron, tetrakis (pentafluorophenyl) boron, etc.

(B) Tetraphenylaluminum, tetrakis (3,4,5-trifluorophenyl) aluminum, tetrakis {3,5-bis (trifluoromethyl) phenyl} aluminum, tetrakis (3,5-di (t- Butyl) phenyl) aluminum, tetrakis (pentafluorophenyl) aluminum, etc.

(C) tetraphenylgallium, tetrakis (3,4,5-trifluorophenyl) gallium, tetrakis {3,5-bis (trifluoromethyl) phenyl} gallium, tetrakis (3,5-di (t- Butyl)
Phenyl) gallium, tetrakis (pentafluorophenyl) gallium, etc.

(D) Tetraphenyl phosphorus, tetrakis (pentafluorophenyl) phosphorus, etc. (e) Tetraphenyl arsenic, tetrakis (pentafluorophenyl) arsenic, etc. (f) Tetraphenylantimony, tetrakis (pentafluorophenyl) antimony, etc. (g ) Decaborate, undecaborate, carbado decaborate, decachloro decaborate, etc.

(Iv) The ion-exchangeable layered compound excluding silicate is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak bonding force, and the ions contained therein are exchangeable. Say things.

The ion-exchangeable layered compound except silicate is
Hexagonal close packing type, antimony type, CdCl ₂ type,
An ionic crystalline compound having a layered crystal structure such as CdI ₂ type can be exemplified. Specific examples of the ion-exchangeable layered compound having such a crystal structure include α-
Zr (HAsO ₄ ) ₂ · H ₂ O, α-Zr (HPO ₄ ) ₂ ,
α-Zr (KPO ₄ ) ₂ .3H ₂ O, α-Ti (HPO ₄ )
₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO
₄ ) ₂ · H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HP
Crystalline acidic salts of polyvalent metals such as O ₄ ) ₂ and γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O are mentioned.

Examples of the inorganic silicate include clay, clay mineral, zeolite, and diatomaceous earth. These may be a synthetic product or a naturally occurring mineral. Specific examples of clay and clay minerals include allophane group such as allophane, dickite, nacrite, kaolinite, kaolin group such as anoxite, metahalloysite, halloysite group such as halloysite, chrysotile,
Serpentites such as lizardite, antigolite, montmorillonite, sauconite, beidellite, nontronite, saponite, smectites such as hectorite, vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, chlorite, attapulgite, Sepiolite, Palygorskite, bentonite, Kibushi clay, Gairome clay, Hisingelite, pyrophyllite,
Ryokudei stone group and the like. These may form a mixed layer.

Examples of artificial synthetic products include synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite, and the like. Among these specific examples, preferably, kaolin group such as dickite, nacrite, kaolinite, anoxite, metahalloysite, halloysite group such as halloysite, chrysotile, lizardite, serpentine group such as antigolite, montmorillonite, sauconite, beidellite , Nontronite, saponite, smectites such as hectorite, vermiculite minerals such as vermiculite, illite, sericite, mica minerals such as chlorite, synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite, and particularly preferred. Are smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, vermiculite minerals such as vermiculite, synthetic mica, synthetic hectorite, synthetic saponite , Synthetic taeniolite. These may be used as they are without any particular treatment, or may be used after having been subjected to treatments such as ball milling and sieving. Also, even if used alone,
Two or more kinds may be used as a mixture.

The above-mentioned ion-exchange layered compound and inorganic silicate can change the acid strength of the solid by salt treatment and / or acid treatment. In the salt treatment, the surface area and the interlayer distance can be changed by forming an ion complex, a molecular complex, an organic derivative, and the like. That is, by using the ion exchange property and replacing the exchangeable ions between the layers with another large bulky ion, a layered material in which the layers are expanded can be obtained.

For compounds not subjected to the above pretreatment,
The exchangeable metal cations contained in the following salts
Exchange with cations dissociated from species and / or acids
Is preferred. Salts used for the above ion exchange
Is at least selected from the group consisting of atoms of groups 1 to 14
A compound containing a cation containing one type of atom.
Preferably, a small number selected from the group consisting of group 1-14 atoms
A cation containing at least one type of atom, a halogen atom,
At least one selected from the group consisting of mechanical acids and organic acids
Anions derived from species or groups of atoms
And more preferably a group 2-14 atom
A cation containing at least one atom selected from the group consisting of
Ions and Cl, Br, I, F, PO_Four, SO_Four, N
O_Three, CO_Three, C_TwoO_Four, ClO _Four, OOCCH_Three, CCH_Three
COCHCOCH_Three, OCI_Two, O (NO_Three)_Two, O (Cl
O_Four)_Two, O (SO_Four), OH, O_TwoCl_Two, OCI_Three, OO
CH and OOCCH_TwoCH_ThreeSelected from the group consisting of
It is a compound consisting of at least one kind of anion. Also,
Two or more of these salts may be used simultaneously.

The acid used for the above-mentioned ion exchange is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid, and two or more of them may be used simultaneously. As a method of combining the salt treatment and the acid treatment, a method of performing an acid treatment after performing the salt treatment, a method of performing the salt treatment after performing the acid treatment, a method of simultaneously performing the salt treatment and the acid treatment,
There is a method of performing salt treatment and acid treatment at the same time after performing salt treatment. In addition, the acid treatment has an effect of removing ions on the surface and ion exchange, and has a crystal structure of Al, Fe, M
It has the effect of eluting some cations such as g and Li.

The treatment conditions with salts and acids are not particularly limited. However, usually the salt and acid concentrations are at 0.
It is preferable that the treatment is carried out under conditions of 1 to 30% by weight, a treatment temperature of room temperature to the boiling point of the solvent used, a treatment time of 5 minutes to 24 hours, and elution of at least a part of the compound to be treated. In addition, salts and acids are generally used in an aqueous solution.

In the case of performing the salt treatment and / or the acid treatment, the shape may be controlled by pulverization or granulation before, during, or after the treatment. Further, another chemical treatment such as an alkali treatment or an organic substance treatment may be used in combination. As the component (B) thus obtained, the pore volume with a radius of 20 ° or more measured by a mercury porosimetry is preferably 0.1 cc / g or more, particularly preferably 0.3 to 5 cc / g. Clays and clay minerals usually contain adsorbed water and interlayer water. Here, the adsorbed water is water adsorbed on the surface of an ion-exchangeable layered compound or an inorganic silicate or a crystal fracture surface, and the interlayer water is water existing between crystal layers.

In the present invention, the clay or clay mineral is preferably used after removing the adsorbed water and interlayer water as described above. The dehydration method is not particularly limited, and a method such as heat dehydration, heat dehydration under gas flow, heat dehydration under reduced pressure, and azeotropic dehydration with an organic solvent is used. The heating temperature is in a temperature range in which adsorbed water and interlayer water do not remain, and is usually 100 ° C. or higher, preferably 150 ° C. or higher. However, high temperature conditions that cause structural destruction are not preferable.
The heating time is at least 0.5 hour, preferably at least 1 hour. At this time, the weight loss of the component (B) after dehydration and drying is preferably 3% by weight or less as a value when sucked for 2 hours at a temperature of 200 ° C. and a pressure of 1 mmHg. In the present invention, when the component (B) whose weight loss is adjusted to 3% by weight or less is used, the same weight loss is caused when the component (B) comes into contact with the essential component (A) and the optional component (C) described below. It is preferable to handle it as shown.

Next, an organoaluminum compound (component C)
Will be described. In the present invention, an organoaluminum compound represented by the general formula (7) is preferably used.

AlRe _m P _3-m General formula (7)

In the general formula (7), Re represents a hydrocarbon group having 1 to 20 carbon atoms, P represents hydrogen, a halogen, an alkoxy group or a siloxy group, and m represents a number greater than 0 and 3 or less. Specific examples of the organoaluminum compound represented by the general formula (7) include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum; halogens such as diethylaluminum monochloride and diethylaluminum monomethoxide. Or an alkoxy containing alkyl aluminum is mentioned. Of these, trialkylaluminum is preferred. In addition, component (C)
Examples thereof include aluminoxanes such as methylaluminoxane. (When component (B) is aluminoxane, aluminoxane is excluded as an example of component (C).)

The olefin polymerization catalyst is an essential component (A)
And (B) and optional component (C). The contact method is not particularly limited, but the following method can be exemplified. This contact is
It may be performed not only at the time of preparing the catalyst but also at the time of prepolymerization with olefin or at the time of polymerization of olefin. (1) The component (A) is brought into contact with the component (B). (2) The component (C) is added after the component (A) is brought into contact with the component (B). (3) The component (B) is added after the component (A) is brought into contact with the component (C). (4) The component (A) is added after the component (B) is brought into contact with the component (C). (5) The components (A), (B) and (C) are brought into contact simultaneously.

At the time of or after the contact of each of the above components, a solid such as a polymer such as polyethylene or polypropylene, or an inorganic oxide such as silica or alumina may coexist or may be brought into contact. The contact of each of the above components may be performed in an inert gas such as nitrogen or an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene and xylene. The contact is carried out at a temperature between -20 ° C and the boiling point of the solvent, particularly preferably at a temperature between room temperature and the boiling point of the solvent.

The amounts of components (A) and (B) used are arbitrary. For example, in the case of solvent polymerization, the amount of component (A), as a transition metal atom, usually 10 ^-7 to 10 ² mmol
/ L, preferably in the range of 10 ^{-4 to 1} mmol / L. In the case of an aluminum oxy compound, the molar ratio of Al / transition metal is usually 10 to 10 ⁵ , preferably 100 to 2
× 10 ^4, more preferably is in the range of 100 to 10 ^4. When an ionic compound or Lewis acid is used as the component (B), the molar ratio thereof to the transition metal is generally in the range of 0.1 to 1,000, preferably 0.5 to 100, and more preferably 1 to 50. It is said.

When an ion-exchange layered compound other than silicate or an inorganic silicate is used as the component (B), the amount of the component (A) is usually 10 ^-4 to 10 per gram of the component (B).
mmol, preferably 10 ^{-3 to} 5 mmol, and the component (C) is usually 0.01 to 10 ⁴ mmol, preferably 0.1 to 100 mmol. The atomic ratio between the transition metal in the component (A) and the aluminum in the component (C) is usually 1: 0.01 to 10 ⁶ , preferably 1: 0.1 to 10 ^5.
It is. The catalyst thus prepared may be used without washing after preparation, or may be used after washing. Further, the component (C) may be used in combination as needed. That is, when the catalyst is prepared using the components (A) and / or (B) and the component (C), the component (C) may be added to the reaction system separately from the preparation of the catalyst. Good. At this time, the amount of the component (C) used is selected so that the atomic ratio of the aluminum in the component (C) to the transition metal in the component (A) is 1: 0 to 10 ⁴ .

Further, a fine particle carrier may coexist as an optional component. The fine particle carrier is a fine particle carrier composed of an inorganic or organic compound and having a particle size of usually 5 μm to 5 mm, preferably 10 μm to 2 mm. As the above-mentioned inorganic carrier, for example, SiO ₂ , Al ₂ O ₃ , Mg
Oxides such as O, ZrO, TiO ₂ , B ₂ O ₃ , ZnO, S
_{iO 2 -MgO, SiO 2 -Al 2} O 3, SiO 2 -Ti
Examples include composite oxides such as O ₂ , SiO ₂ Cr ₂ O ₃ , and SiO ₂ —Al ₂ O ₃ —MgO.

As the above organic carrier, for example, ethyl
Propylene, 1-butene, 4-methyl-1-pentene
(Co) polymerization of α-olefin having 2 to 14 carbon atoms such as olefin
, Aromatic unsaturated carbons such as styrene and divinylbenzene
Fine particles of porous polymer composed of (co) polymer of hydrogen
Subcarriers. These specific surface areas are usually 20 to
1000m^Two/ G, preferably 50-700 m^Two/ G
Pore volume is usually 0.1 cm^Two/ G or more, preferably
Is 0.3cm ^Two/ G, more preferably 0.8 cm^Two/ G or less
Above.

The catalyst for olefin polymerization includes, as optional components other than the fine particle carrier, for example, active hydrogen-containing compounds such as H ₂ O, methanol, ethanol and butanol, electron-donating compounds such as ethers, esters and amines, and phenyl borate. , Dimethylmethoxyaluminum, phenyl phosphite, tetraethoxysilane, diphenyldimethoxysilane and the like.

In the catalyst for olefin polymerization, component (B) (i) aluminum oxy compound, (ii)
A Lewis acid, (iii) an ionic compound capable of converting component (A) into a cation by reacting with component (A), (i.
v) One or more substances selected from the group consisting of ion-exchange layered compounds other than silicates and inorganic silicates can be used alone or in combination of these three components as appropriate.

One or more of the lower alkylaluminum, halogen-containing alkylaluminum, alkylaluminum hydride, alkoxy-containing alkylaluminum and aryloxy-containing alkylaluminum of component (C) are optional components, It is preferable to include the compound, ionic compound or Lewis acid in the olefin polymerization catalyst in combination.

When the components (A), (B) and (C) are brought into contact in advance, so-called prepolymerization in which a part of the α-olefin is polymerized in the presence of a monomer to be polymerized can also be carried out. That is, prior to polymerization, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-
Prepolymerization of an olefin such as butene, vinylcycloalkane, or styrene is performed, and if necessary, a prepolymerized product washed can be used as a catalyst. This pre-polymerization is preferably performed under mild conditions in an inert solvent,
It is preferable that the polymerization is carried out so as to generate usually 0.01 to 1000 g, preferably 0.1 to 100 g of polymer per 1 g of the solid catalyst.

<Use of Catalyst / Polymerization of Olefin> The catalyst of the present invention can be applied not only to solvent polymerization using a solvent, but also to liquid phase solventless polymerization and gas phase polymerization substantially using no solvent. It is also applied to melt polymerization. Further, it can be applied to continuous polymerization and batch polymerization. As the solvent in the case of solvent polymerization, an inert saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, and toluene may be used alone or as a mixture.

The polymerization temperature is about -78 to 250 ° C, preferably -20 to 100 ° C. The olefin pressure of the reaction system is not particularly limited, but is preferably normal pressure to 2000 kg.
· F / cm ² , more preferably from normal pressure to 50 kg / c
m ² · G. In the polymerization, the molecular weight can be adjusted by known means, for example, selection of temperature and pressure or introduction of hydrogen.

The monomers copolymerized with the catalyst of the present invention are α-olefin and ethylene. Here, the α-olefin used for the polymerization reaction in the method of the present invention is an α-olefin having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms. Specifically, for example, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-hexene
Octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. Of these, propylene is particularly preferred. These α-olefins can be used for polymerization by mixing two or more kinds.

The composition ratio of α-olefin to ethylene in the copolymer produced by the catalyst of the present invention is not particularly limited, provided that the proportion of α-olefin is greater than 0 mol% and less than 100 mol%. Is 0.1mo
1% to 50 mol%, more preferably 0.2 to 20 mol
1%.

The copolymer produced by the catalyst of the present invention has a composition ratio of α-olefin to ethylene of 0.2 to 20 mol% in terms of α-olefin.
When the polymerization is carried out under constant polymerization conditions other than the composition of the monomer gas used for the polymerization, the polymer has a property that the molecular weight of the polymer increases as the ethylene content in the polymer increases. A preferable value for this property is a value that satisfies (Equation 6).

RMw> HMw + HMw * [E] * 10 (Formula 6) RMw: Molecular weight of copolymer when ethylene content [E] HMw: Molecular weight when α-olefin homopolymerization [E]: Ethylene content in polymer (Mol%) In polymerization, so-called multi-stage polymerization in which polymerization conditions are changed in multiple stages is also possible.

[0083]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. The catalyst synthesis step and the polymerization step were all performed under a purified nitrogen atmosphere. The solvent used was dehydrated by MS-4A and then degassed by bubbling with purified nitrogen. The molecular weight is a weight average molecular weight (Mw) (polystyrene conversion value) obtained by GPC. The GPC was measured using a Waters 150CV type apparatus, ortho-dichlorobenzene as a solvent, and a measurement temperature. 1
Performed at 35 ° C.

The melting point was measured by using a DuPont TA2000 model at a rate of 10 ° C./min.
It was obtained by the measurement at the time of the second temperature rise after the number of times.

Calculation Examples Hereinafter, calculation examples used in the present invention will be described in detail. <Calculation method> 1. Model reaction A reaction formula (Equation 2) that models a 6-center reaction in which the hydrogen at the β-position of the terminal monomer unit of the polymer is transferred to a monomer molecule.
Is calculated using. 2. Quantum Chemical Calculation (1) Model Reaction of Quantum Chemical Calculation Regarding the reaction represented by (Equation 2), the ligand L is two chlorine atoms, and the model substituent P of the polymer chain is a methyl group. Quantum chemical calculations show that M is zirconium and hafnium, and that the pair (R ¹ , R ² ) of the substituents R ¹ and R ² is (Me, Me), (H, H), (Me, H). Calculations were performed on a case-by-case basis.

(2) Software used Gaussian Inc. Gaussian9 made by
4 was used. Calculation conditions used default values unless otherwise specified below. (3) Quantum chemical calculation method Restrictive second-order mailer preset many-body perturbation method (RMP2
Method). A frozen core approximation was used that excludes the core electrons of each atom from the perturbation method. The basis set is zirconium,
Hafnium atom is Lanl2dz, other atoms are 3
-21G was adopted, and both used numerical values built in Gaussin 94.

(4) Determination of Molecular Structure The six-center transition state structure of the reaction represented by (Equation 2) was determined by the energy gradient method. Further, LM (CH ₂ CHP)
The structure in which the monomer CH ₂ CHR ² was π-coordinated to M in R ¹ ) (+) was determined by the energy gradient method. (5) Determination of basic activation energy Using the total energy of the transition state structure and the π-coordination structure of the monomer obtained by performing the above calculation, the basic activation energy Eq (R ¹ , R ² ) calculated.

3. Molecular force field calculation (6) Model reaction of molecular force field calculation Regarding the reaction represented by (Equation 2), P is CH ₂ CHMe
CH ₂ CHMeCH ₂ CH ₃ . The pair (R ¹ , R ² ) of the substituents R ¹ and R ² is (Me, Me), (H, H), (M
e, H). L is L1 and L2. In the case of the two organic ligand-containing metal complex compounds used this time, L2 is a dimethylsilylenebiscyclopentadienyl ligand.

(7) Software used The Discover3 made by MSI was used. Calculation conditions used default values unless otherwise specified below. (8) Method of calculating molecular force field The molecular force field CFF91 built in Discover3 was used. However, M is treated as a dummy atom, and the force constant is 33.5079 kcal / mol * Å with a minimum of 2.5872Å between each carbon atom of the 5-membered ring portion of the ligand L.
* Harmonic potential constraint is added. here,
Å means Angstrom.

(9) Determination of Transition State Structure The transition state structure was determined according to the following procedure. From the transition state structure obtained by the quantum chemical calculation, two chlorine atoms of L, all hydrogen atoms of a methyl group used as P, and all hydrogen atoms of a methyl group used as R ¹ and R ² were removed. Consider partial structure A. Based on the partial structure A obtained above, L is L1 and L2, and P is CH ₂ CHMeCH ₂ CHMeCH ₂ CH ₃ . In the case of a methyl group, the R ¹ and R ² parts are restored by adding a hydrogen atom. This is designated as structure B. Using the energy gradient method, a structure in which the total energy of the structure B has a minimum value is determined. At this time, the atomic coordinates of the partial structure A are fixed and not moved.

(10) Determination of partial structure The LM partial structure was determined by the energy gradient method. (11) Determination of steric repulsion energy Using the total energy of the transition state structure and the partial structure obtained by performing the molecular force field calculation, the steric repulsion energy Er (R ¹ , R ² ) were calculated. The combination of (R ¹ , R ² ) is (Me, Me),
Since there are three types (H, H) and (Me, H), Em (R
¹ , R ² ) and Eo (R ¹ , R ² )
In total, eight calculations were performed, one for Em (0) and one for Eo (0).

[0092] 4. Calculation of energy index (12) Determination of activation energy Using the above calculation results, the activation energy Ea (R ¹ , R ¹ , R ² ) was determined. Again, the combination of (R ¹ , R ² ) is (Me, Me),
Since there are three types (H, H) and (Me, H), Ea (R
¹ , R ² ) are calculated three times, and Ea (Me, Me),
The values of Ea (Me, H) and Ea (H, H) were calculated. (13) Determination of energy index Using the activation energy determined according to (Equation 5),
It was determined by (Equation 1).

Example-1 (1) Dichlorodimethylsilylenebis (2-methyl-4)
Calculation of the energy index of-(1-naphthyl) -4H-azulenyl) hafnium According to the calculation method described above, calculation is performed on dimethylsilylenebis {2-ethyl-4- (1-naphthyl) -1,4-dihydroazulene} hafnium. The energy index ΔEa obtained was -1.72 Kcal / mol. (2) dichlorodimethylsilylenebis (2-methyl-4
Synthesis of-(1-naphthyl) -4H-azulenyl) hafnium:

(Synthesis of Meso-Racemic Mixture) 1-bromonaphthalene (2.5 g, 12 mmol) was dissolved in a mixed solvent of diethyl ether (18 mL) and hexane (18 mL), and a solution of t-butyllithium in pentane (16.3) was obtained.
mL, 24 mmol, 1.48 M) was added dropwise at -78 ° C. After slowly raising the temperature and stirring at -5 ° C for 1 hour, 2-methylazulene (1.88 g, 12 mmol) was added to the solution.
l) was added. The temperature was immediately raised to room temperature and stirred for 1 hour. Tetrahydrofuran (18 mL) was added, the mixture was cooled to 0 ° C., N-methylimidazole (20 μL) and dimethyldichlorosilane (0.73 mL, 6.0 mmol) were added, and the mixture was stirred at room temperature for 2 hours. Thereafter, 1N hydrochloric acid (50 m
L) was added, and the mixture was separated. The organic phase was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure.

The crude product obtained was purified by column chromatography (silica gel, Merck Co., methylene chloride / n-hexane) to give dimethylsilylenebis {2-methyl-
4- (1-naphthyl) -1,4-dihydroazulene}
(2.8 g, yield 75%) was obtained. Next, the reaction product (2.8 g, 4.5 mmol) obtained above was dissolved in diethyl ether (30 mL), and n-
Butyllithium n-hexane solution (5.9 mL, 9.
(0 mmol, 1.53 M) was added dropwise, the temperature was gradually raised, and the mixture was stirred at room temperature for 1 hour.

The solvent was distilled off, and toluene (80 mL) and diethyl ether (2 mL) were added. Cool to -70 ° C and hafnium tetrachloride (1.44 g, 4.5 mmol)
, And the mixture was gradually heated and stirred at room temperature overnight. The obtained slurry solution was filtered using celite, washed with toluene, and the filtrate was concentrated.

After the crude product was washed five times with diethyl ether, extraction was repeated three times with a mixed solvent of dichloromethane and hexane 2: 1. After further washing with diethyl ether, dichlorodimethylsilylenebis {2-methyl-4- (1-
A racemic meso mixture of (naphthyl) -4H-azulenyl @ hafnium (4: 1) was obtained.

(Purification of Racemic Form) The racemic / meso mixture (226 mg) obtained above was mixed with a mixed solvent of dichloromethane and hexane, dichloromethane / hexane (20 mL).
, And the soluble matter was extracted into the solvent, followed by filtration. This operation was repeated five times, and then the same operation was repeated twice except that the solvent was changed to diethyl ether (20 mL).

Further, a series of steps using the mixed solvent of dichloromethane and hexane and diethyl ether was repeated once. Here, toluene (3 mL) was added to the obtained solid.
Was added and suspended, followed by filtration. Toluene (1 mL x 2),
After washing with hexane (2 mL) and drying under reduced pressure, a racemate (34 mg, 15%) was obtained.

¹ H-NMR (300 MHz, CDCl ₃ )
δ 0.94 (t, J = 7 Hz, 6H, 2CH ₂ C
_{H 3), 1.04 (s,} 6H, Si (CH 3) 2),
2.23 (s, 6H, 2- CH 3), 5.70~6.0
5 (m, 10H), 6.80 (d, J = 8 Hz, 2
H), 7.16-8.01 (m, 14H, arom)

(2) Polymerization of propylene using methylalumoxane as a cocatalyst: After sufficiently replacing the inside of a 3 L stirred autoclave with propylene, 1.5 liters of heptane sufficiently dehydrated and deoxygenated were introduced. , Internal temperature 70
C. was maintained. Then, methylalumoxane (Tosoh
200 mg of "MMAO" manufactured by Akzo Co., Ltd. were introduced, and dichlorodimethylsilylenebis (2-methyl-4-
5 mg of racemic (1-naphthyl) -4H-azulenyl) hafnium was diluted with toluene and introduced. afterwards,
The temperature was raised to 75 ° C, and propylene was added to 5.5 kg / cm ² · G.
And polymerization was started, and a polymerization operation was performed for 1 hour. As a result, Mw (weight average molecular weight) was 1.81.
207 g of × 10 ⁵ polypropylene was obtained.

Example 2 Example 1 was repeated except that the monomer to be introduced was changed to a mixed gas of propylene and ethylene (propylene / ethylene = 98/2: mol ratio) which had been adjusted in another autoclave in advance.
Polymerization was carried out in the same manner as described above. As a result, propylene having an ethylene content of 2.4 mol% and an Mw of 2.66 × 10 ⁵ was obtained.
180 g of an ethylene copolymer was obtained.

Example 3 Example 1 was repeated except that the monomer to be introduced was changed to a mixed gas of propylene and ethylene (propylene / ethylene = 95/5: mol ratio) which was previously adjusted in another autoclave.
Polymerization was carried out in the same manner as described above. As a result, propylene having an ethylene content of 4.3 mol% and an Mw of 2.98 × 10 ⁵ was obtained.
180 g of an ethylene copolymer was obtained.

Comparative Example-1 (1) Calculation of Energy Index of Dichlorodimethylsilylenebis (2-methylbenzoindenyl) zirconium According to the above-mentioned calculation method, calculation was performed for dichlorodimethylsilylenebis (2-methylbenzoindenyl) zirconium. The energy index ΔEa obtained is 2.34 k
cal / mol.

(2) Dichlorodimethylsilylene bis (2
Synthesis of Racemic Form of (-Methylbenzoindenyl) zirconium Organometallics 1994, 13,
P. Synthesized according to the method described in 964 reference.

(3) Methylalumoxane as cocatalyst
Polymerization of propylene: Stirring autoclave with 3L internal volume
After thoroughly replacing the inside with propylene, sufficiently dehydrate and dehydrate
1.5 liters of oxygenated heptane was introduced and the internal temperature was reduced to 70
C. was maintained. Next, methylalumoxane (Tosoh
Introduce 100mg of Akzo “MMAO”)
In addition, dichlorodimethylsilylene bis (2-methylbenzo
0.75 mg of racemic indenyl) zirconium
Diluted with Ruen and introduced. Then, the temperature was raised to 75 ° C,
5.5 kg / cm of propylene^Two・ Introduction to GG
The polymerization was started and the polymerization operation was performed for 1 hour. That
As a result, Mw 1.65 × 10 ^Five255g of polypropylene
I got

Comparative Example 2 Comparative Example 1 except that the monomer to be introduced was changed to a mixed gas of propylene and ethylene (propylene / ethylene = 96/4: mol ratio) which was previously adjusted in another autoclave.
Polymerization was carried out in the same manner as described above. As a result, propylene having an ethylene content of 5.0 mol% and an Mw of 1.22 × 10 ⁵ was obtained.
240 g of an ethylene copolymer was obtained.

[0108]

According to the present invention, when a novel organometallic compound which satisfies the above-mentioned requirements of the present invention is provided, the resulting polymer has a high stereoregularity and a high molecular weight α-C 3 -C 20.
It becomes possible to obtain a copolymer of olefin and ethylene in high yield.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Takao Tatano 1 Tohocho, Yokkaichi-shi, Mie Japan Process Development Center (72) Inventor Toshihiko Sugano 1 Tohocho, Yokkaichi-shi, Mie Japan Nippon Polychem Inside Process Development Center Co., Ltd. BC25B CA30B EA01 EB04 EB05 EB07 EB09 EB10 EC02 FA01 FA02 FA04 4J100 AA02Q AA03P AA04P AA15P AA16P AA17P AA19P AA21P CA04 CA27 DA01 DA24 FA10 FA43

Claims (5)

[Claims] In a catalyst component for copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms, quantum chemical calculation is performed on a 6-center reaction in which hydrogen at the β-position of a terminal propylene unit of a polymer is transferred to an ethylene monomer. Activation energy obtained by the method of calculation and molecular force field calculation (Equation 1)
Energy index ΔEa calculated on the basis of 1.00k
A catalyst component for α-olefin-ethylene copolymerization comprising an organic ligand-containing metal complex compound having a cal / mol or less. ΔEa = Ea (Me, Me) + Ea (H, H) −2 * Ea (Me, H) (Formula 1) Ea (Me, Me): Transfer of hydrogen at β-position of propylene unit at polymer chain terminal to propylene monomer The activation energy of the reaction. Ea (H, H): activation energy of the reaction of transferring the hydrogen at the β-position of the ethylene unit at the terminal of the polymer chain to the ethylene monomer. Ea (Me, H): activation energy of the reaction in which the hydrogen at the β-position of the propylene unit at the terminal of the polymer chain is transferred to an ethylene monomer. 2. The α-olefin-ethylene copolymerization catalyst component according to claim 1, wherein the catalyst component is a Group 4 transition metal compound represented by the following general formula (2). Embedded image (Wherein M is a transition metal selected from Group 4 transition metal elements, and two Ras may be the same or different, and are monovalent hydrocarbon groups having 1 to 20 carbon atoms, halogen atoms Group, halogen, silicon, boron, oxygen, nitrogen, phosphorus,
Or a hydrocarbon group having 1 to 20 carbon atoms containing sulfur,
The two Rb's may be the same or different, and have four carbon atoms bonded to two adjacent carbon atoms of the five-membered ring ligand.
-20 divalent hydrocarbon groups or 4-2 carbon atoms
0 is a divalent hydrocarbon group containing halogen, silicon, germanium, boron, oxygen, nitrogen, phosphorus, or sulfur, and may have a substituent at any position.
Q represents a binding group bridging the two ligands, and X and Y each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon. Shows a hydrogen group or a silicon-containing hydrocarbon group. ) 3. The following component (A) and component (B):
A catalyst for α-olefin-ethylene copolymerization, which comprises optionally combining an optional component (C). Component (A) The catalyst component for α-olefin-ethylene copolymerization according to any one of claims 1 and 2, Component (B) (i) an aluminum oxy compound, (ii) a Lewis acid,
(Iii) selected from the group consisting of an ionic compound capable of converting component (A) into a cation by reacting with component (A), and (iv) an ion-exchange layered compound other than silicate or an inorganic silicate. One or more compounds Component (C) organoaluminum compound 4. The component (A) or the component (B) according to claim 3.
And an α-olefin having 3 to 20 carbon atoms and ethylene being brought into contact with a catalyst obtained by combining an optional component (C) as required, and copolymerizing the mixture.
A method for producing an ethylene copolymer. 5. The method for producing an α-olefin-ethylene copolymer according to claim 4, wherein the α-olefin having 3 to 20 carbon atoms is propylene.