JPH11349617A - Catalyst component for polymerizing alpha-olefin, catalyst and preparation of alpha-olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst component for polymerizing α-olefin, which enables preparation in a high yield of an olefin polymer which has a sufficiently high melting point that a polymer obtained through extrusion molding or injection molding has a sufficient rigidity, tensile strength and heat resistance, a catalyst using the component and a preparation process of α-olefin polymers using the catalyst. SOLUTION: A catalyst component for polymerizing α-olefins is a catalyst component for (co)polymerization of α-olefins containing 3-20C α-olefins or copolymerization of 2-20C α-olefins and polyemes, wherein the energy difference ΔE (PrB-PrA) between the transition states of the insertion elementary reactions of monomers into polymers, each determined through a quantum chemical method, an IMOMM and then MM method, either at a coordination mode (PrA) of monomers giving isotactic polymers or a coordination mode (PrB) of monomers giving atactic bonds, is 11 kcal/mol or larger.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel organometallic compound and an isotactic α-α-organic compound comprising the organometallic compound.
The present invention relates to an olefin polymerization catalyst component, an isotactic α-olefin polymerization catalyst using the organometallic compound, and a method for producing an α-olefin polymer using the same. More specifically, the present invention relates to a polymerization catalyst component and a polymerization catalyst which enable the production of a high melting point α-olefin polymer, and a method for producing an α-olefin polymer using the catalyst.

[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 polyolefins with Kaminsky catalyst include ethylenebis (indenyl) zirconium dichloride and ethylenebis (4,5,
6,7-Tetrahydroindenyl) zirconium dichloride (for example, JP-A-61-130314) is known, but the stereoregularity of the produced polyolefin is not very high.

Further, dimethylsilylenebis-substituted cyclopentadienyl zirconium dichloride and the like are disclosed in
No. 301704, Polymer Preprin
ts, Japan Vol. 39, no. 6, p. 16
14-1616 (1990) and JP-A-3-12406, dimethylsilylenebis (indenyl) zirconium dichloride and the like are disclosed in JP-A-63-295007,
It has been proposed in each report of JP-A-1-275609, and it has become possible to obtain a polymer having a high stereoregularity and a high melting point by polymerization at a relatively low temperature. However, it seems that the stereoregularity and the melting point are remarkably reduced under high-temperature high-temperature polymerization conditions.

Further, there is known a compound in which a substituent is added to an indenyl group which is a part of a ligand to improve the isotacticity and molecular weight of polypropylene (for example, JP-A-4-268307). JP-A-6-157661, etc.). Further, a transition metal compound in which the sub-ring including two carbon atoms adjacent to the conjugated five-membered ring is a ring having a number of members other than the six-membered ring is also known (for example, JP-A-4-275294, JP-A-6-275294).
239914, JP-A-8-59724 and the like). However, there appears to be an inadequacy in performance under polymerization conditions at elevated polymerization temperatures, which are economically advantageous.

[0005] On the other hand, these catalyst systems are often soluble in the reaction medium, and the resulting polymer has very poor particle properties such as irregular particle shape, low bulk density, and many fine powders. When applied to slurry polymerization or gas phase polymerization, there are many problems in the production process, such as difficulty in continuous stable operation. On the other hand, in order to solve these problems, a method of polymerizing an olefin with a catalyst in which one or both of a transition metal compound and organoaluminum is supported on an inorganic oxide or an organic substance such as silica or alumina has been proposed ( JP-A-61-108610, JP-A-60-135408, JP-A-61-29600
No. 8, JP-A-3-74412 and JP-A-3-74412.
No. 74415).

However, the polymers obtained by these methods often contain fine powders and coarse particles, are often poor in particle properties such as low bulk density, and have low polymerization activity per solid component. In addition, there are also problems such as a decrease in molecular weight and stereoregularity as compared with a system using no support. In recent years, new research methods for providing useful knowledge for catalyst design using information on the structure and energy of elementary reactions using molecular science, especially quantum chemical calculations, have been remarkably advanced in recent years. Above all, the rapid progress of computers in recent years has made it possible to handle even large molecules by the ab initio molecular orbital method, and this progress has been remarkable. N. M.
van Leeuwen et al., edited book "Theo
"retical Aspects of Home"
neous Catalysis "(Kluwer)
See Dordrecht, 1995. However, almost all research is related to academic knowledge using modeled systems, and it must be said that there is still a distance in the industry.

Many quantum chemical studies have been reported for metallocene catalysts. Book "Ziegler Catalyst" edited by Fink et al. (Spr
Inger) Berlin, 1995, introduces many MM calculations and molecular orbital calculations. T. reported further later. Yoshida, N .; Koga, K .; Mor
okuma, Organometallics 15,7
66-777 (1996) is a study of the white eyebrows. However, even at this stage, the model skeleton obtained by the ab initio molecular orbital method is fixed, and the realistic ligand is evaluated by the MM method on the fixed base. At this stage, the reproducibility of existing measured data was still insufficient to estimate subtle substituent effects that are industrially problematic based on many experimental results. Therefore, in reality, the necessity of using a more advanced technique has been pressed, and the present invention has been produced by applying the more advanced techniques, namely, the IMOMM and the IMOMM then MM.

[0008]

DISCLOSURE OF THE INVENTION The present invention provides an olefin polymer which has a high melting point and has a high yield so that a polymer obtained by extrusion molding or injection molding has sufficient rigidity, tensile strength and heat resistance. It is an object of the present invention to provide an α-olefin polymerization catalyst component which makes it possible to obtain an α-olefin polymerization catalyst component. It is still another object of the present invention to provide an α-olefin polymerization catalyst using the catalyst component and a method for producing an α-olefin polymer using the same. Another object of the present invention is to provide a novel catalyst component which does not cause a decrease in performance when the catalyst component is supported on a carrier for use in improving process applicability.

[0009]

The present invention has been found as a result of intensive studies to solve the above problems. That is, the present invention is a catalyst that has been achieved as a result of designing a catalyst using quantum chemical calculation and performing experimental verification.
The essence lies in the results of new research that complements experiments with high-precision quantum chemistry calculations while spending a lot of calculation time.

The present invention is directed to the (co) polymerization of α-olefins containing α-olefins having 3 to 20 carbon atoms or the polymerization of α-olefins having 2 to 20 carbon atoms.
Quantum chemistry in each of the coordination mode (PrA) of the monomer that gives the isotactic polymer and the coordination mode (PrB) of the monomer that gives the atactic bond in the catalyst component for copolymerizing the α-olefin and the polyene of No. 20 Energy difference ΔE (Ets (PrB) −Ets (Pr) in the transition state of the intercalation reaction of a monomer into a polymer measured by the IMOMM then MM method
(A)) is 11 kcal / mol or more, an α-olefin polymerization catalyst component, an α-olefin polymerization catalyst using the catalyst component, and an α-olefin polymerization catalyst.
An object of the present invention is to provide a method for producing an olefin polymer.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The catalyst component of the present invention is an organometallic compound capable of producing an olefin polymer having isotactic regularity. When the calculation is performed according to the provisions of the present invention, the energy difference ΔE (Ets (PrB) −Ets) of the transition state of the intercalation reaction of the monomer into the polymer is obtained.
(PrA)) is achieved by finding that an organometallic compound characterized by a certain numerical value or more can produce a polymer having high isotactic regularity.

The organometallic compound of the present invention is calculated on the assumption that a four-center structure is formed as a transition state in which an olefin causes an insertion reaction in a carbon-metal bond, but substantially forms a transition state. It doesn't mean that it is necessary. As a result of the calculation, all organometallic compounds are contained as long as the content is within a specific range. Α- having 3 to 20 carbon atoms
One of the important properties required for the polymer produced by copolymerizing olefin alone or α-olefin having 2 to 20 carbon atoms and polyene with at least two types is one that does not contain heterogeneous bonds. It is to be. In order to design a catalyst component that minimizes the formation of this heterogeneous bond as much as possible, academic studies for analyzing the mechanism of elementary reactions have recently been made based on quantum chemical techniques. As an example, Morokuma et al. Conducted research using metallocene model compounds.
ganometallics 1995, 15, 766. Although the gap between academic considerations and industrially useful realistic systems is large and often shows unexpected divergence, the present invention takes advantage of the known facts made in academic research to It was done through difficulties. The coordination mode of the monomer, which follows the designation used by Morokuma et al. In this report and gives an isotactic polymer, will be referred to as PrA: primary A. What is needed is a catalyst design in which only polymer growth from this mode occurs.

On the other hand, a coordination mode of a monomer that gives an unfavorable atactic bond will be referred to as PrB: primary B. Theoretically, the transition state energy of the elementary reaction of the insertion of the monomer into the polymer from PrA should be smaller than that from PrB and the difference should be greater, so that the isotactic regularity should be higher. Obtaining this absolute value for an industrially meaningful catalyst is nothing less than an extremely difficult task, but this evaluation can be made by using some reproducible approximate method.

The present invention provides a quantum chemical method I described below.
Using the MOMMthenMM method, the value of ΔE = Ets (PrB) −Ets (PrA) was obtained by calculation and evaluated. Where E
ts (PrB) represents the energy of the transition state in PrB, and Ets (PrA) represents the energy of the transition state in PrA. Making this ΔE as large as possible was used as a guideline for searching for a new catalyst, and as a result of repeating the synthesis of a new compound and the evaluation of polymerization based on it, ΔE was 11 kcal / mol or more, more preferably 12 kcal / mol.
It has been found that a catalyst component characterized by being at least 1 / mol significantly reduces atactic binding and produces the desired high melting point polymer.

[0015] The catalyst component of the present invention may be of any type as long as it achieves its effects. As the organometallic compound,
For example, JACS 119 (38) 8126 (1997)
Group 13 organometallic compounds disclosed in
Group 2 organometallic compounds R) ₂ or the like, 3-6 metallocene type
Group transition metal compounds, Organometallics
16-1810 (1997) and the like, non-metallocene transition metal compounds of Groups 3 to 6, JACS120 (16)
408 (1998) and the like are exemplified as the catalyst component of the present invention, such as a Group 8 to 10 transition metal compound.
However, it is needless to say that some are included as a result of the calculation and others are not included depending on the structure.

Although the effective range of the present invention is not limited to this system, it is needless to say that the following general formula [I] typically applied to the IMOMM then MM method, which is a method of the present invention using a metallocene type catalyst, is used here. ] Will be described in detail using a metallocene type catalyst represented by the following formula:

[0017]

Embedded image

Recently, the IMOMM method reported by Morokuma et al. (F. Masaeras, K. Morokuma, J. Mol.
Com. Chem. , 16, 1170 (1995)). First, a part involved in the reaction, that is, a five-membered ring part containing a central transition metal and a bridging part, SiH ₂ Cp ₂ , C ₂ H ₄ as a monomer part, and CH ₃ as a minimum unit nearest to the monomer of the polymer, an ab initio molecular orbital This is calculated by a general calculation, for example, a general-purpose program GAUSSIAN94.
On the other hand, a ligand part other than the above which is not directly involved in the formation and cleavage reaction of a chemical bond is calculated by the general-purpose program MM2, and the structure of the transition state is optimized while assigning the two parts to different calculation methods. . Details of the procedure are described in, for example, the document Int. J. Quantum. Che
m. , 60, 1101 (1996). However, the former basis set is a central metal LANL2DZ, SiH ₂ C
3-21G to p ₂ parts, the C ₂ H ₄ and CH ₃ parts D95
The calculations were performed at the RHF level using each V, and the rest was the 1985 version of the MM2 force field incorporated into the software Cerius2 from MSI.

Standard ligands that make full use of the IMOMM method
May be selected, but in the present invention, for example,
The azulene (2-Me, 4-Ph, Si) shown in (III)
Me _Two)_TwoSince an Hf compound was used, it will be explained using the compound.
You. Transition corresponding to PrA and PrB of this compound (III)
The transfer state is optimized by completely performing the IMOMM calculation.

[0020]

Embedded image

The energy difference thus obtained for (III) is ΔE. Thereafter, ΔE corresponding to the compound obtained by modification of many substituents is (III)
The part of the structure obtained by the ab initio molecular orbital method is fixed, and the part of the MM2 force field is optimized for each newly considered ligand structure, and the energy difference of the transition state obtained there is ΔE. . This method is called IMOMM then
Called MM. In this way, calculations were repeatedly performed for many ligands for the compounds of the system represented by the following general formula (IV).

[0022]

Embedded image

(R¹, R^Two, R^Four, R^Five, Q, M, X,
Y has the same meaning as described above. R⁹, R ^Ten, R¹¹, R¹²,
R¹³, R¹⁴, R^Fifteen, R¹⁶Are each independently a hydrogen source
, A hydrocarbon having 1 to 20 carbon atoms or a hydrocarbon having 1 to 20 carbon atoms
Shows a halogenated hydrocarbon group. And Ar¹, Ar^TwoIs
Each independently an aryl group having 8 to 20 carbon atoms,
8-20 halogen or halogenated hydrocarbon substituted ants
Represents a hydroxyl group. ) And based on the molecular design guidelines given by calculation,
While repeating the synthesis of the reference compound and the evaluation of polymerization using it
ΔE is 11 kcal / mol or more, more preferably 12 kcal / mol or more.
a catalyst component characterized by being at least kcal / mol
Has significantly reduced heterologous binding. The present invention
The preferred catalyst component is represented by the following formula [1]:
A transition metal compound of the general formula is used.

[0024]

Embedded image

Wherein A and A ′ are conjugated five-membered ring ligands (A and A ′ may be the same or different in the same compound), and Q is two conjugated five-membered ring ligands. Represents a bonding group that bridges the substituent at an arbitrary position, and M is
X and Y represent a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group. )

A and A 'are conjugated five-membered ring ligands,
As described above, these may be the same or different in the same compound. Specific examples of the conjugated five-membered ring ligand (A and A ') include a conjugated five-membered ring ligand, that is, a cyclopentadienyl group. Cyclopentadienyl group 4 hydrogen atoms (all binding sites except the bridge portion) having [C ₅ H ₄ -] may be, also, its derivatives, that is, some of its hydrogen atoms substituted May be substituted with a group. Examples of the substituent include a hydrocarbon group having 1 to 20, preferably 1 to 12 carbon atoms. Even if this hydrocarbon group is bonded to the cyclopentadienyl group as a monovalent group, when two or more of them are present, two of them are bonded at the other end (ω-end) to form cyclopentadienyl. A ring may be formed together with a part of the group. Examples of the latter are those in which two substituents are bonded at each ω-terminus and share a contiguous two carbon atoms in the cyclopentadienyl group to form a fused six-membered ring Ie, an indenyl group, a tetrahydroindenyl group or a fluorenyl group. Further, two substituents are each ω-
The two adjacent groups in the cyclopentadienyl group
And a condensed seven-membered ring formed by sharing two carbon atoms, that is, an azulenyl group and a tetrahydroazulenyl group.

That is, specific examples of the conjugated five-membered ring ligand represented by A and A 'include a substituted or unsubstituted cyclopentadienyl group, an indenyl group, a fluorenyl group, an azulenyl group and the like. Preferably, it is a substituted or unsubstituted azulenyl group. As the substituent on the cyclopentadienyl group or the like, in addition to the above-mentioned hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, a halogen atom group such as fluorine, chlorine, and bromine; An alkoxy group of
For example ^{-Si (R 1) (R 2} ) a silicon-containing hydrocarbon group having 1 to 24 carbon atoms represented by ^{(R 3), -P (R} 1) (R
² ) a phosphorus-containing hydrocarbon group having 1 to 18 carbon atoms represented by
^{-N (R 1) (R 2} ) nitrogen-containing hydrocarbon group having 1 to 18 carbon atoms represented by or -B (R ¹⁾ a boron-containing hydrocarbon group having 1 to 18 carbon atoms represented by (R ^2), Or a hydrocarbon group containing 1 to 20, preferably 1 to 12 carbon atoms containing halogen, oxygen, nitrogen, phosphorus, sulfur, boron and silicon. When there are a plurality of these substituents, each substituent may be the same or different. Also,
The above R ^{1 to} R ³ may be the same or different and represent a hydrogen atom, or an alkyl group, alkenyl group, aryl group or the like having 1 to 20 carbon atoms. Further, they may be linked to each other to form a cyclic substituent.

Q represents a linking group bridging at any position between the two conjugated five-membered ligands. As a specific example of Q,
(A) alkylene groups having 1 to 20 carbon atoms such as a methylene group, an ethylene group, an isopropylene group, a phenylmethylmethylene group, a diphenylmethylene group, and a cyclohexylene group;
(B) silylene group, dimethylsilylene group, phenylmethylsilylene group, diphenylsilylene group, disilylene group,
A silylene group such as a tetramethyldisilylene group, (c) a hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum, and more specifically, (CH ₃ ) ₂ G
e, (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.

M is a metal atom selected from Groups 3 to 6 of the periodic table, preferably a metal atom of Group 4 of the periodic table, specifically, titanium, zirconium, hafnium and the like. Particularly, zirconium and hafnium are preferable. X and Y
Are hydrogen, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an amino group, and 1 to 2 carbon atoms.
A nitrogen-containing hydrocarbon group containing 0, preferably 1 to 10, a phosphorus-containing hydrocarbon group having 1 to 20, preferably 1 to 12 carbon atoms such as a diphenylphosphine group, or a trimethylsilyl group, a bis (trimethylsilyl) methyl group, or the like. Is a silicon-containing hydrocarbon group having 1 to 20, preferably 1 to 12 carbon atoms. X and Y may be the same or different. Of these, a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, and a nitrogen-containing hydrocarbon group having 1 to 12 carbon atoms are preferable.

In the olefin polymerization catalyst component according to the present invention, among the compounds represented by the general formula [1] as component (A), those having the following substituents are preferred. A, A ′ = 2, 4, 5, trimethylcyclopentadienyl, 2-ethyl-4-isopropylcyclopentadienyl, 2-ethyl-4-phenyl-indenyl, 2-methyl-4-anthracenylindenyl, 2-ethyl 4, phenyl-tetrahydroindenyl, 2, methyl 4-naphthyl 4H azulenyl, 2-methyl-4-anthracenyl 4H azulenyl, 2-methyl-4- (2-naphthyl) azulenyl, 2-ethyl-4-naphthyl 4H azulenyl,
2-ethyl-4-anthracenyl 4H azulenyl, 2-
Methyl-4- (4-chlorophenyl) 4H azulenyl,
2-isopropyl-4-naphthyl azulenyl, 2-cyclopentyl-4-naphthyl azulenyl, Q = ethylene, dimethylsilylene, isopropylidene, M = transition metal of group 3 to 6, X, Y = chlorine, methyl, phenyl, benzyl And A, A '= 2-methyl, 4-naphthyl 4H azulenyl, 2-ethyl-4-naphthyl 4H azulenyl, 2-isopropyl-4-anthracenyl 4H azulenyl, 2-cyclopentyl-4-naphthyl 4H azulenyl, 2-cyclopentyl-4- (3,5-dimethylphenyl) 4H azulenyl, 2-isopropyl-4-anthracenyl 4H azulenyl, 2-isopropyl-4-
(4-chloro-3,5-dimethylphenyl) 4H azulenyl.

Specific examples of the compounds included in the present invention are as follows: (1) Dichlorodimethylsilylenebis (2-methyl,
-(1-naphthyl) 4H azulenyl) zirconium (2) dichlorodimethylsilylenebis (2-ethyl,
-(1-naphthyl) 4H azulenyl) zirconium (3) dichlorodimethylsilylenebis (2-methyl,
-(2-naphthyl) 4H azulenyl) zirconium (4) dichlorodimethylsilylenebis (2-ethyl,
-(2-naphthyl) 4H azulenyl) zirconium (5) dichlorodimethylsilylenebis (2-methyl,
-Anthracenyl 4H azulenyl) zirconium

(6) Dichlorodimethylsilylene bis (2
-Ethyl, 4-anthracenyl 4H azulenyl) zirconium (7) dichlorodimethylsilylene bis (2-cyclobutyl, 4-anthracenyl 4H azulenyl) zirconium (8) dichlorodimethylsilylene bis (2-cyclopentyl, 4-anthracenyl 4H azulenyl) zirconium (9 ) Dichlorodimethylsilylenebis (2-ethyl, 6
-Quinolyl, 4H azulenyl) zirconium (10) dichloroethylenebis (2-isopropyl,
-(9-anthryl) 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, hafnium, niobium, molybdenum, tungsten or the like can be used as the component (A). Among these, preferred are a zirconium compound, a hafnium compound and a titanium compound. More preferred are zirconium compounds and hafnium compounds. These (A) components may be used in combination of two or more. Also, at the end of the first stage of polymerization or before the start of the second stage polymerization,
The component (A) may be newly added.

In the present invention, the component (B) includes an aluminum oxy compound, an ionic compound capable of converting the component (A) into a cation by reacting with the component (A), and an ion other than Lewis acid and silicate. Exchangeable layered compound,
One or more substances selected from the group consisting of inorganic silicates are used. Certain types of Lewis acids include component (A)
Can be grasped as an ionic compound capable of converting the component (A) into a cation by reacting with the 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 aluminum oxy compound include compounds represented by the following general formulas [2], [3] or [4].

[0035]

Embedded image

In the above general formulas, R ¹ and R ² represent a hydrogen atom or a hydrocarbon residue, preferably a C 1-10, particularly preferably a C 1-6 hydrocarbon residue or a halogenated hydrocarbon. Shows a hydrogen group. A plurality of R ¹ may be the same or different. P 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 type of trialkylaluminum or two or more types of trialkylaluminum 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-mentioned aluminoxanes may 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 with two or more trialkylaluminums and (alkyl) boronic acid represented by the following general formula [5] in a ratio of 10: 1 to 1: 1. : 1 (molar ratio). In the general formula [5], R ² is hydrogen or carbon atom 1
And, preferably, a hydrocarbon residue having 1 to 6 carbon atoms or a halogenated hydrocarbon group.

[0038]

Embedded image R ² B- (OH) ₂ [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 the ionic compound capable of converting the component (A) into a cation by reacting with the component (A) include a compound represented by the general formula [6].

[0040]

[K] ^{e +} [Z] ^e- [6]

In the general formula [6], K is a cation component, for example, carbonium cation, tropylium cation, ammonium cation, oxonium cation,
Examples include 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 cations 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}
(B) tetraphenylaluminum, tetrakis (3,5-di (t-butyl) phenyl) boron, tetrakis (pentafluorophenyl) boron, etc.
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) Tetraphenyl antimony, tetrakis (pentafluorophenyl) antimony, etc. (g) Decaborate, undecaborate, carbado decaborate, decachloro decaborate, etc.

Examples of 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. Is mentioned. (A) Organic boron compounds such as triphenylboron, tris (3,5-difluorophenyl) boron, and tris (pentafluorophenyl) boron (b) Aluminum chloride, aluminum bromide, aluminum iodide, magnesium chloride, magnesium bromide Metal halide compounds such as, magnesium iodide, magnesium chlorobromide, magnesium chloroiodide, magnesium bromoiodide, magnesium hydride, magnesium hydride, magnesium hydride, magnesium alkoxide, magnesium alkoxide, etc. c) Solid acids such as alumina and silica-alumina

The ion-exchangeable layered compound except silicate is
A compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with weak bonding force to each other, and are compounds in which contained ions are exchangeable. Examples of the ion-exchange layered compound other than the silicate include an ionic crystalline compound having a layered crystal structure such as a hexagonal close-packed type, an antimony type, a CdCl ₂ type, and a CdI ₂ type. 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 (HA
sO ₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂ · H
₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ )
₂ , crystalline acidic salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

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, metahaloisite, halloysite group such as halloysite, chrysotile,
Razardite, anti-gorite, serpentinite, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, etc., smectite, vermiculite, etc. vermiculite minerals, illite, sericite, mica minerals, such as 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, NO
_Three, CO_Three, C_TwoO_Four, ClO_Four, OOCCH_Three, CH
_ThreeCOCHCOCH_Three, OCI_Two, O (NO_Three) _Two, O
(ClO_Four)_Two, O (SO_Four), OH, O_TwoCl_Two, O
Cl_Three, OOCH and OOCCH_TwoCH_ThreeA group of
Compound comprising at least one selected anion
It is. In addition, these salts use two or more kinds at the same time.
Is also good.

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.

When the above-mentioned salt treatment and / or acid treatment is performed, shape control may be performed 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 even when the component (A) and the optional component (C) described below come into contact with each other. 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 suitably used.

[0055]

Embedded image AlR _a P _3-a [7]

In the general formula [7], R represents a hydrocarbon group having 1 to 20 carbon atoms, P represents hydrogen, halogen, an alkoxy group or a siloxy group, and a 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. Of these, trialkylaluminum is preferred. Further, as the component (C), aluminoxanes such as methylaluminoxane can be used. (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 carried out 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.

When or after the above-mentioned components are contacted, solids of polymers such as polyethylene and polypropylene, and inorganic oxides such as silica and 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) used is
As the transition metal atom, usually 10 ^-7 ~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.

Further, as the component (B),
When an on-exchangeable layered compound or inorganic silicate is used,
The amount of component (A) is usually 10 g per minute (B).^-Four-10
mmol, preferably 10^-3~ 5 mmol, the components
(C) is usually 0.01 to 10^Fourmmol, preferably
0.1 to 100 mmol. In addition, component (A)
The atomic ratio between the transition metal and aluminum in component (C) is
Always 1: 0.01 to 10 ⁶, Preferably 1: 0.1 to 10
^FiveIt is. The catalyst thus prepared is washed after preparation.
It may be used without cleaning, or after cleaning
Is also good. Also, if necessary, combine component (C) newly.
They may be used together. That is, component (A) and / or
Alternatively, a catalyst is prepared using (B) and component (C).
In this case, component (C) is further reacted separately from this catalyst preparation.
It may be added to the reaction system. In this case, the component (C) used
In the component (C) with respect to the transition metal in the component (A).
In an atomic ratio of aluminum of 1: 0 to 10^FourSelected to be
Devour.

A fine particle carrier may coexist as an optional component (D). 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. Examples of the inorganic carrier include SiO ₂ , Al ₂ O ₃ , M
_{gO, ZrO, TiO 2, B} 2 O 3, oxides such as _{ZnO, SiO 2 -MgO, SiO 2} -Al 2 O 3, SiO
_{2 -TiO 2, SiO 2 -Cr 2} O 3, SiO 2 -Al
Complex oxides such as ₂ O ₃ —MgO are exemplified.

Examples of the above organic carrier include (co) polymers of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, styrene, divinylbenzene and the like. And a fine particle carrier of a porous polymer comprising a (co) polymer of an aromatic unsaturated hydrocarbon. These specific surface areas are usually 20 to
1000 m ² / g, preferably 50~700m ² / g, pore volume is usually 0.1 cm ² / g or more, preferably 0.3 cm ² / g, more preferably 0.8 cm ² /
g or more.

The olefin polymerization catalyst may be any component 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, the aluminum oxy compound of the component (B), the ionic compound capable of reacting with the component (A) to convert the component (A) into a cation, Lewis acid and silicate are excluded. One or more substances selected from the group consisting of ion-exchange layered compounds 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, but may be aluminum oxy compounds, It is preferable to include it in the olefin polymerization catalyst in combination with the hydrophilic compound or Lewis acid.

When the components (A), (B) and (C) are brought into contact in advance, a so-called prepolymerization in which a monomer to be polymerized is present to partially polymerize the α-olefin can 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. It is 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 α-olefin polymerized by the catalyst of the present invention, that is, the α-olefin (including ethylene) used in the polymerization reaction in the method of the present invention is an α-olefin having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms.
-An olefin. Specifically, for example, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1
-Hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. In addition, the catalyst of the present invention may be an α-carbon having 3 to 10 carbon atoms for stereoregular polymerization.
Preferred for the polymerization of olefins, especially preferred is propylene. These α-olefins can be used for polymerization by mixing two or more kinds.

The catalyst of the present invention can also copolymerize the above α-olefins. Further, other monomers copolymerizable with the α-olefin, for example, butadiene, 1,4-hexadiene, 7-methyl-1,6-octadiene, 1,8-nonadiene, 1,9-decadiene and the like. It is also effective for copolymerization with such conjugated and non-conjugated dienes or with cyclic olefins such as cyclopropene, cyclobutene, cyclopentene, norbornene, dicyclopentadiene and the like. In the polymerization, so-called multi-stage polymerization in which conditions are changed in multiple stages is also possible.

[0069]

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 distribution was determined by the ratio (Q value) between the weight average molecular weight (Mw) obtained by GPC and the number average molecular weight (Mn) (both in terms of polyethylene). This GP
The measurement of C was performed at a measurement temperature of 135 ° C. using a 150 CV type device manufactured by Waters, using ortho-dichlorobenzene as a solvent.

The melting point was measured by using a DuPont TA2000 type 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. The content of 2,1 bond and 1,3 bond in the polymer was determined by dissolving the polymer in 2 ml of ortho-dichlorobenzene using JNM EX270 manufactured by JEOL Ltd. and then adding 0.5 ml of deuterated benzene as a locking solvent. At 130 degrees. In order to improve the S / N, integration was performed 10,000 times. The analysis is described in J.A. C. Using the method already proposed by Randall (Junal of poly
merscience 12, 703, (1974)).

Example 1 Dichlorodimethylsilanediylbis (2-ethyl, 4-
Calculation of (2-naphthyl) 4H azulenyl) hafnium. The energy difference between the two transition states of PrA corresponding to the growth of an isotactic polymer chain and PrB corresponding to the growth of forming an atactic bond in the polymerization reaction of the complex was determined. A schematic diagram of these two transition states is shown below.

[0072]

Embedded image

(The dotted line indicates a hydrocarbon which may have a substituent and constitutes a ring having 6 to 20 carbon atoms together with the carbon atom on the five-membered ring to which it is bonded. may include a double bond.) first earlier standard compound shown (III) of the two one _of CH ₃ of Cl, and the other is substituted by CH ₂ = CH _2.
The parts handled in the ab initio molecular orbital calculation include the three carbon and seven hydrogen parts substituted for Cl, the central metal Hf, and Cp
—SiH ₂ —Cp. These are general purpose programs GA
Calculated by RHF method of USSIAN94 (version D3), the basis set is D95V for 3 carbons and 7 hydrogens, LANL2DZ for central metal, 3-21G for Cp-SiH ₂ -Cp
Were used.

The parts handled by MM2 are the upper and lower Cp of (III).
That replaces azulene and H in position 2 of Cp
CH ₃ , CH ₂ ＣC instead of H ₃ , H ₂ arriving at Si
CH _{3 in} which one H of H ₂ is substituted, and C ₈ H _{17 in} which one H of CH ₃ bonded to the central metal as a polymer is substituted. This CH ₂ C ₈ H ₁₇ results in 3
This corresponds to considering a series of molecules of propylene as the polymer portion. CH ₂ = but PrA of hydrogen CH ₂ is also PrB also position β replacing H of each as shown above and under the CH _3. When replacing the value calculated as H by the ab initio molecular orbital method with C, the bond length is CC when the H at Cp2 position is CH ₃ is 1.50.
6. Cp and azulene C at 1.505 (Cp and azulene 4-position C) and 1.342 (Cp C and azulene 8-position C), Si-C 1.895 and 1.892,
C-C of CH ₂ = CH ₂ and CH ₃ are 1.517, replaces one H of CH ₃ bonded to Hf in C ₈ H ₁₇ C-
C is 1.604 and the bond distance (all units are Δ) is fixed. However, the bond angle and the dihedral angle, which are the degrees of freedom of these bonds, are all optimized.

As described above, a large molecule is divided into a portion handled by ab initio molecular orbital and a portion handled by MM2, and both are recursively repeated to obtain the entire optimized structure. Thus Pr
An optimized structure for both A and PrB transition states is determined.
The procedure up to this point is described in F. Maseras K. et al. Morok
Uma's Journal of Computat
ionical Chemistry 16,1170-1
179 (1995). MM parameters are 1985 MM2 built into MSI's Cerius2 (version 3.0),
IMOMM used the program described in this document. Thus, PrA and P corresponding to the standard compound (III)
An optimized structure of two transition states of rB is obtained.

Thereafter, the 2-ethyl-substituted product of this example was used.
Is calculated as IMOMM then MM.
That is, for both transition states obtained above,
CH _ThreeIs replaced with an ethyl group, and the 4-position is replaced with a 2-naphthyl group.
After replacing, all of the MM part is optimized and this energy
The energy difference was determined to be 12.45 kcal / mol.

Example 2 As in the above example, first, the optimized structure (IMOM) of the transition state of PrA and SeA obtained for the standard compound (III) was used.
M), each of which is an ethyl group at the 2-position and 2-
The naphthyl group was substituted, and the optimized structure of the transition state and its energy were determined by MM2 calculation, and an energy difference of 3.01 kcal / mol was obtained.

Example 3 Similarly to the above example, first, the optimized structure (IMO) of the transition state of PrA and PrB obtained for the standard compound (III) was obtained.
Using MM), the optimized structure of the transition state and its energy were determined by MM2 calculation for several types described below, and the energy difference was calculated. Only the calculation results are described below. (2-ethyl, 4- (1-naphthyl) 4H azulenyl)
₂ Si (CH ₃ ) ₂ Hf 13.07 kcal / mol (2-ethyl, 4 (9-anthryl), 4H azulenyl) ₂ Si (CH ₃ ) ₂ Hf 14.15 kcal / mol (2-isopropyl, 4 (9- Anthryl), 4H azulenyl) ₂ Si (CH ₃ ) ₂ Hf 11.74 kcal / mol (2-benzo, 4- (2-naphthyl), 7-isopropyl 4H azulenyl) Si (isoPr) ₂ Hf 13.11 kcal / mol ( 2-phenyl, 4- (9-anthryl), 4H _{azulenyl) Si (CH 3) 2 Hf} 12.19kcal / mol

Example-4 (1) Dichlorodimethylsilylenebis (2-ethyl-4
Synthesis of-(2-naphthyl) -4H-azulenyl) hafnium: (a) Synthesis of a racemic-meso mixture; 2-bromonaphthalene (1.14 g, 5.5 mmol) was prepared by adding diethyl ether (10 mL) and hexane (10 mL). Dissolved in the mixed solvent, and a solution of t-butyllithium in pentane (6.7 mL,
11.0 mmol, 1.64 N) was added dropwise at -78 ° C. The mixture was stirred at -5 ° C for 1.5 hours. To this solution was added a solution of 2-ethylazulene (858 mg, 10.14 mmol) in diethyl ether (10 mL) and hexane (10 mL), and the mixture was stirred at room temperature for 1.5 hours. After cooling to 0 ° C., tetrahydrofuran (20 mL) was added. N-methylimidazole (10 μL) and dimethyldichlorosilane (0.
33 mL, 2.75 mmol) was added, the temperature was raised to room temperature, and the mixture was stirred at room temperature for 1.5 hours. Thereafter, dilute hydrochloric acid was added, and the mixture was separated. The organic phase was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to give dimethylsilylenebis (2-ethyl-4- (2-naphthyl) -1,4-dihydroazulene. ) Was obtained (1.81 g).

Next, the crude product obtained above was dissolved in diethyl ether (20 mL), and n-butyllithium in hexane (3.5 mL, 5.5 mmol) was added at −78 ° C.
(1.59 mol / L) was added dropwise, the temperature was gradually raised, and the mixture was stirred at room temperature overnight. The solvent was distilled off, and toluene (10 m
L) and diethyl ether (0.25 mL) were added. −
Cool to 78 ° C. and add hafnium tetrachloride (880 mg, 2.
75 mmol), and the mixture was gradually heated and stirred at room temperature for 4 hours. The obtained slurry solution was filtered using celite, and washed with toluene (2 mL × 2) and hexane (2 mL). The filtered product was extracted with dichloromethane (90 mL) to give a racemic / meso mixture of dichlorodimethylsilylenebis (2-ethyl-4- (2-naphthyl) -4H-azulenyl) hafnium (232 mg, 10% yield).
was gotten.

(B) Purification of the racemic form: The racemic-meso mixture (226 mg) obtained above was treated with dichloromethane (2
0 mL), and suspended with a high-pressure mercury lamp (100 W).
Irradiation was performed with 0 spectrum. The solvent was distilled off from this solution under reduced pressure. Toluene (3 mL) was added to the obtained solid to suspend it, followed by filtration. After washing with toluene (1 mL × 2) and hexane (2 mL) and drying under reduced pressure, the racemate (126 mg, 56 mg
%)was gotten. ¹ H NMR (300 MHz, CDCl ₃ ) δ 0.96
(S, 6H, SiMe ₂ ), 0.96 (t, J = 9H
_{z, 6H, CH 3 CH 2} ), 2.44 (m, 2H),
2.63 (m, 2H), 5.08 (br s, 2H, 4
-H), 5.8-6.05 (m, 8H), 6.75.
(D, J = 11 Hz, 2H), 7.40-7.52
(M, 6H, arom), 7.7-7.8 (m, 8H,
arom).

(2) Polymerization of propylene using methylalumoxane as a co-catalyst: In a 2-liter stirred autoclave, methylalumoxane (MMA manufactured by Tosoh Akzo Co., Ltd.) was used.
O ") 4 mmol (in terms of Al atom) was introduced. on the other hand,
0.3 mg of the above racemate in a catalyst feeder with a rupture disk
Was diluted with toluene and introduced. Then, after introducing 1500 ml of propylene into the autoclave, the rupture plate was cut at room temperature, the temperature was raised to 70 ° C., and the polymerization operation was performed for 1 hour to obtain 7 g of polypropylene. Complex activity is 1.0 × 1
04. Tm of polypropylene is 158.8 ° C,
MFR was 0.01.

Example-5 <Polymerization of α-olefin using clay mineral as co-catalyst> (1) Chemical treatment of clay mineral: 10 g of sulfuric acid and 90 m of deionized water
Then, 10 g of montmorillonite ("Kunipia F", manufactured by Kunimine Kogyo Co., Ltd.) was dispersed in the diluted sulfuric acid, and the mixture was heated to the boiling point and stirred for 6 hours. After that, the collected montmorillonite was sufficiently washed with demineralized water, and pre-dried.
It was dried at 00 ° C. for 2 hours to obtain a chemically treated clay mineral. 200 mg of this chemically treated montmorillonite
Then, 0.8 ml of a toluene solution of triethylaluminum having a concentration of 0.5 mol / l was added thereto, followed by stirring at room temperature for 1 hour. Then, it was washed with toluene to obtain a montmorillonite-toluene slurry of 33 mg / ml.

(2) Polymerization: 0.25 mmol (in terms of Al atom) of triisobutylaluminum (manufactured by Tosoh Akzo) was introduced into a 1 L stirred autoclave. On the other hand, Example 3 (1) was applied to a catalyst feeder with a rupture disk.
1.31 mg of the racemate obtained in the above was diluted and introduced with toluene, and the slurry containing 50 mg of montmorillonite and 0.015 mmol of triisobutylaluminum were further added.
1 (in terms of Al atom) was introduced. Thereafter, 700 ml of propylene was introduced into the autoclave, the rupture plate was cut at room temperature, the temperature was raised to 80 ° C., and polymerization was carried out for 1 hour to obtain 85.3 g of polypropylene. The catalyst activity was 1700, and the complex activity was 6.5 × 104. The Tm of polypropylene is 154.5 ° C., the MFR is 0.4, and the Mw is 5.3 × 10 5
, Q was 2.9.

Comparative Example 1 Dimethylsilylenebis (2-methyl-4-phenyl-4)
Calculation result of (H-azulenyl) hafnium: Calculated in the same manner as in Example-1. As a result, 10.63 Kcal / mol
Met. Comparative Example-2 (1) Dichlorodimethylsilylenebis (2-methyl-4
Synthesis of -phenyl-4H-azulenyl) hafnium: (a) Synthesis of racemic-meso mixture; 2-methylazulene (3.22 g) was dissolved in hexane (30 mL), and a solution of phenyllithium in cyclohexane-diethyl ether (21 mL) was added. It was added in small portions at 0 ° C. After stirring this solution at room temperature for 1.5 hours, it was cooled to -78 ° C and tetrahydrofuran (30 mL) was added. To this solution was added 1-methylimidazole (0.05 mmol) and dimethyldichlorosilane (1.37 mL), and the mixture was heated to room temperature and reacted for 1 hour. Thereafter, an aqueous solution of ammonium chloride was added, and the mixture was separated. The organic phase was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. As a result, 5.84 g of a crude product of dimethylsilylenebis (2-methyl-4-phenyl-1,4-dihydroazulene) was obtained.

The dimethylsilylenebis (2) obtained above
-Methyl-4-phenyl-1,4-dihydroazulene)
Was dissolved in diethyl ether (30 mL), and a solution of n-butyllithium in hexane (14.2 mL,
(1.64N) was added dropwise, and the temperature was gradually raised, followed by stirring at room temperature for 12 hours. After evaporating the solvent under reduced pressure, the obtained solid was washed with hexane and dried under reduced pressure. To this was added toluene / diethyl ether (40: 1) (80 mL), 3.3 g of hafnium tetrachloride was added at −60 ° C., and the mixture was gradually heated and stirred at room temperature for 15 hours. The obtained solution is concentrated under reduced pressure, and the obtained solid is washed with toluene, extracted with dichloroethane, and 1.74 g of a racemic / meso mixture of dichlorodimethylsilylenebis (2-methyl-4-phenyl-4H-azulenyl) hafnium. )was gotten.

(B) Purification of racemic form: 1.74 g of the racemic-meso mixture obtained above was treated with dichloromethane (30 m
L) and subjected to 40 spectral irradiations using a high-pressure mercury lamp (100 W). The solvent was distilled off from this solution under reduced pressure. Toluene (8 mL) was added to the obtained solid to suspend it, followed by filtration. After washing with hexane (4 mL) and drying under reduced pressure, a racemic form (917 mg) was obtained.

In Embodiment 3 (2), Embodiment 3 (1)
0.26mg of the above racemate instead of the racemate obtained in
The procedure of Example 3 (2) was repeated, except that was used, to obtain 27.8 g of polypropylene. Complex activity is 1.07x
10 ⁵ . Tm of polypropylene is 154.4
° C, MFR was 0.08, Mw was 8.4 × 10 ⁵ , and Q was 3.8.

Comparative Example 3 <Polymerization of α-olefin Using Clay Mineral as Cocatalyst> In Example 4, the racemic product obtained in Example 3 (1) was used instead of the racemic product obtained in Comparative Example 2 (1). The same operation as in Example 4 was performed except that 0.98 mg of the racemate was used, to obtain 204.9 g of polypropylene. The catalyst activity was 4,100, and the complex activity was 2.1 × 10 ⁵ . Tm of polypropylene is 152.7 ° C., MFR is 0.8, and Mw is 4.1 × 1.
0 ⁵ and Q were 2.6.

[0090]

According to the present invention, when a novel organometallic compound which satisfies the requirements of the present invention is provided, an olefin polymer having a high stereoregularity and a high melting point can be produced, which can be produced by extrusion molding or injection molding. An olefin polymer having high heat resistance and high rigidity can be obtained by molding.

[Brief description of the drawings]

FIG. 1 is a flowchart for helping an understanding of the present invention.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Toshihiko Kanno 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsubishi Chemical Research Institute (72) Inventor Nao Iwama 1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Mitsubishi Chemical Research Institute Yokohama Research Laboratory

Claims (10)

[Claims] (1) a (co) polymerization of an α-olefin containing an α-olefin having 3 to 20 carbon atoms or an α-olefin having 2 to 20 carbon atoms;
In a catalyst component for copolymerizing an olefin and a polyene, a quantum chemical technique IMOMM in each of a coordination mode (PrA) of a monomer providing an isotactic polymer and a coordination mode (PrB) of a monomer providing an atactic bond is used. The energy difference ΔE (Ets (PrB) −Ets (PrA)) of the transition state of the intercalation reaction of the monomer into the polymer measured by the then MM method is 11
A catalyst component for α-olefin polymerization, wherein the catalyst component is at least kcal / mol. 2. The α-olefin polymerization catalyst component according to claim 1, wherein the catalyst component is a transition metal compound. 3. The α-olefin polymerization catalyst component according to claim 2, wherein the catalyst component is a Group 3-6 transition metal compound represented by the following general formula [I]. Embedded image (Wherein, A is a conjugated five-membered ring ligand, and A ′ is a divalent 15, 16 or conjugated group which may have a conjugated five-membered ring ligand or a hydrocarbon group.
A group-bonding group (in the case of a conjugated five-membered ring ligand, it may be the same as or different from A), Q is a bonding group bridging the two ligands at any positions, and M is X represents a metal atom selected from Groups 3 to 6 of the periodic table, X and Y represent a hydrogen atom,
Halogen atom, hydrocarbon group, alkoxy group, amino group,
It represents a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group. ) 4. The α-olefin polymerization catalyst component according to claim 3, wherein M is a Group 4 transition metal. 5. The α-olefin polymerization catalyst component according to claim 1, wherein the α-olefin polymerization catalyst component is a transition metal compound represented by the following general formula [II]. General formula [II]: ^{(Wherein, R 1, R 2, R} 4, R 5 are each independently a hydrogen atom or a hydrocarbon group or a silicon-containing hydrocarbon group having 1 to 18 carbon atoms having 1 to 10 carbon atoms, R ^3, R ⁶ each independently represents a divalent saturated or unsaturated hydrocarbon group having 3 to 10 carbon atoms which forms a condensed ring with the five-membered ring to which R ⁶ is bonded, provided that at least one of R ³ and R ⁶ Has 5 to 10 carbon atoms, and R ⁷ and R ⁸ are each independently a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, and a phosphorus-containing hydrocarbon. A hydrogen group, a nitrogen-containing hydrocarbon group, or a silicon-containing hydrocarbon group, m and n each independently represent an integer of 0 to 20. Q represents a carbon atom having 1 to 20 carbon atoms, which bonds two 5-membered rings. A hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms,
An oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, or an alkylene group having a silicon-containing hydrocarbon group, or a hydrocarbon group having 1 to 20 carbon atoms,
A silylene group having a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a silicon-containing hydrocarbon group, or a carbon number of 1 to 20;
And a germylene group having a hydrocarbon group of 0, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, or a silicon-containing hydrocarbon group. X and Y each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, It represents a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, and M represents a transition metal of Groups III to VIB of the periodic table. ) 6. An α-olefin polymerization catalyst comprising a combination of the following components (A) and (B) and, if necessary, an optional component (C). Component (A) The catalyst component for α-olefin polymerization according to any one of claims 1 to 5 Component (B) (a) Reaction with (b) Lewis acid or (c) component (A) One or more compounds selected from the group consisting of ionic compounds capable of converting component (A) into cations, (d) ion-exchange layered compounds other than silicates, and inorganic silicates Component (C) organoaluminum compounds 7. An α-olefin polymerization catalyst comprising a combination of the following component (A), component (B), optional component (C) and component (D). Component (A) The catalyst component for α-olefin polymerization according to any one of claims 1 to 5 Component (B) (a) Reaction with (b) Lewis acid or (c) component (A) Ionic compounds capable of converting component (A) into cations (d) One or more compounds selected from ion-exchange layered compounds other than silicates or inorganic silicates Component (C) Organoaluminum compound Component (D) ) Fine particle carrier 8. An α-olefin having 3 to 20 carbon atoms or an α-olefin having 2 to 20 carbon atoms and a polyene are polymerized or copolymerized by using the catalyst component for α-olefin polymerization according to any one of claims 1 to 5. A method for producing an α-olefin polymer, comprising polymerizing. 9. The component (A) or the component (B) according to claim 6.
And optionally a combination of an optional component (C)
-A method for producing an α-olefin polymer, which comprises bringing an α-olefin into contact with an olefin polymerization catalyst to carry out polymerization or copolymerization. 10. An α-olefin is brought into contact with an α-olefin polymerization catalyst obtained by combining component (A), component (B), optional component (C) and component (D) according to claim 7 to polymerize or Characterized by copolymerization,
A method for producing an α-olefin polymer.