JPH07188319A - Catalyst component for polymerizing alpha-olefin and its use - Google Patents

Abstract

PURPOSE:To provide the highly active catalyst component containing a specific transition metal compound, and an Al oxy compound, a Lewis acid, an ionic compound t-eacting with the transition metal compound to convert the transition metal compound into a cation, etc., and capable of giving polyolefins in high yields. CONSTITUTION:An alpha-olefin is polymerized in the presence of a polymerization catalyst to obtain the corresponding polyolefin in a high yield. The polymerization catalyst is produced by carrying components comprising (A) a compound of for-mula I {m is 1-3; M is a IVB-VIB group transition metal; n is 4-6 which is a number corresponding to the atomic valency of M; R<1> is a conjugated heterocyclic ligand of formula II [R is H, (nitrogen-containing) 1-24C hydrocarbon group, but R<0> groups may be bound to each other to form a cyclic 4-12C ring (containing two or more carbon atoms composing the conjugated heterocyclic ligand); R<2> is H, halogen, 1-24C hydrocarbon group, cyclopentadlenyl, etc.,]} and (B) a compound such as an aluminum oxy compound, a Lewis acid or an ionic compound capable of reacting with the component A to convert the component A into a cation on (C) a fine particulate carrier.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION

The present invention relates to an α-comprising a transition metal compound of Group IVB to VIB having a specific conjugated heterocyclic ligand.
Olefin (in the present invention, "α-olefin" means
Includes ethylene. The same applies hereinafter. ) Novel polymerization catalyst component, an α-olefin polymerization catalyst comprising this catalyst component,
And a method for producing an α-olefin using the catalyst for polymerizing the α-olefin. According to the present invention, the corresponding polyolefin can be obtained in high yield.

[0002]

2. Description of the Related Art Conventionally, a metallocene compound having a Group IVB metal atom as a central metal is well known as a homogeneous catalyst for the polymerization of α-olefins. This catalyst has a very high polymerization activity and is characterized in that a polymer having a narrow molecular weight distribution can be obtained. These are disclosed, for example, in JP-A-58-1930.
No. 9 and Japanese Patent Laid-Open No. 60-35007.

On the other hand, a group IVB metal complex having a conjugated hetero 5-membered ring ligand having a phosphorus atom is known (Meunier
Et al., Journal of Organometallic Chemistry, 193 (1980) C.
13-C16, Nief et al., Organometallics, 1988, 7, p921-926).

However, it has not been found to the best of the knowledge of the present inventors that these compounds serve as a polymerization catalyst for α-olefins.

[0005]

[Outline of Invention]

[0006]

[Means for Solving the Problems]

<Summary> The present invention is based on the discovery of the fact that Group IVB to VIB transition metal compounds having a specific ligand have high polymerization activity for α-olefins.

Therefore, the catalyst component for α-olefin polymerization according to the present invention is characterized by comprising a compound represented by the following general formula (I).

[0008]

[Chemical 4] [In the formula (I), m represents 1, 2 or 3, and M represents
IVB to VIB transition metals are shown. n is a number corresponding to the valence of M and represents 4, 5 or 6. R ¹ represents the following conjugated heterocyclic ligand.

[0009]

[Chemical 5] R ^0's each independently represent hydrogen, a hydrocarbon group having 1 to 24 carbon atoms, or a hydrocarbon group having 1 to 24 carbon atoms containing silicon. In addition, the substituents R ⁰ may be bonded to each other to form a ring having a carbon number of 4 to 12 (including at least two carbon atoms constituting the conjugated heterocyclic ligand). m
When is 2 or 3, R ¹ may be the same or different.

R ² is hydrogen, a halogen group, or having 1 to 2 carbon atoms.
4 hydrocarbon groups, monovalent hydrocarbon groups having 1 to 24 carbon atoms containing nitrogen, oxygen, sulfur, phosphorus or silicon, or
A cyclopentadienyl group and a substituted cyclopentadienyl group are shown. R ² may be the same or different. The present invention also relates to an α-olefin polymerization catalyst containing the α-olefin polymerization catalyst component.

That is, the first catalyst for α-olefin polymerization according to the present invention is characterized by comprising the following components (A) and (B) in combination.

Component (A) A catalyst component for polymerization of α-olefin, which comprises a compound represented by the above formula (I). Component (B) A compound selected from the following (a), (b) and (c). (A) Aluminum oxy compound (b) Lewis acid (c) Ionic compound capable of reacting with compound (I) in component (A) and converting it to a cation

The second α-olefin polymerization catalyst according to the present invention is characterized in that the following component (A) and component (B) are supported on component (C). Component (A) A catalyst component for polymerization of α-olefin, which comprises a compound represented by the above formula (I). Component (B) A compound selected from the following (a), (b) and (c). (A) Aluminum oxy compound (b) Lewis acid (c) An ionic compound component (C) fine particle carrier capable of reacting with the compound (I) in the component (A) to convert it into a cation.

The present invention also relates to a method for producing an α-olefin polymer using a first α-olefin polymerization catalyst, and an α-olefin polymer using a second α-olefin polymerization catalyst. It relates to a manufacturing method.

That is, the first method for producing an α-olefin polymer according to the present invention comprises contacting an α-olefin with a catalyst obtained by combining the above-mentioned components (A) and (B) to polymerize the catalyst. It is a feature.

The second method for producing an α-olefin polymer according to the present invention is the same as the above-mentioned component (A) and component (B).
The α-olefin is brought into contact with a catalyst formed by supporting the above-mentioned component (C) to polymerize the catalyst.

<Effects> According to the present invention, it is possible to provide a novel catalyst component for polymerization of α-olefin having high activity, a catalyst for α-olefin polymerization, and a method for producing an α-olefin polymer. Further, the olefin polymer obtained by using the catalyst supported on the fine particle carrier of the present invention,
Since the molecular weight distribution is wide, the moldability becomes good. In addition, the properties of the produced polymer will be good.

[Detailed Description of the Invention] <Catalyst Component for α-Olefin Polymerization> Constituent / Compound (I) The catalyst component for α-olefin polymerization according to the present invention comprises a compound represented by the following general formula (I): It will be. Here, the term “consisting of” does not mean that the compound (I) is only the compound (I), and does not exclude the coexistence of other purposeful components. In addition, as mentioned above, "alpha-olefin" in the present invention includes ethylene.

[0019]

[Chemical 6] [In the formula (I), m represents 1, 2 or 3, and M represents
IVB to VIB transition metals are shown. n is a number corresponding to the valence of M and represents 4, 5 or 6. R ¹ represents the following conjugated heterocyclic ligand.

[0020]

[Chemical 7] R ^0's each independently represent hydrogen, a hydrocarbon group having 1 to 24 carbon atoms, or a hydrocarbon group having 1 to 24 carbon atoms containing silicon. In addition, the substituents R ⁰ may be bonded to each other to form a ring having a carbon number of 4 to 12 (including at least two carbon atoms constituting the conjugated heterocyclic ligand). m
When is 2 or 3, R ¹ may be the same or different.

R ² is (a) hydrogen, (b) halogen group,
(C) Hydrocarbon group having 1 to 24 carbon atoms, (D) Monovalent hydrocarbon group having 1 to 24 carbon atoms containing nitrogen, oxygen, sulfur, phosphorus or silicon, or (V) cyclopentadienyl group Or (f) represents a substituted cyclopentadienyl group.

A plurality of R ^2's may be the same or different. ] In the compound of formula (I), M is IVB, VB or Periodic Table
VIB group transition metals, namely titanium, zirconium,
It is a group IVB transition metal of hafnium, a group VB transition metal of vanadium, niobium, and tantalum, and a group VIB transition metal of chromium, molybdenum, and tungsten. Preferred M is titanium,
Zirconium and hafnium Group IVB transition metals, more preferably M is zirconium.

R ¹ is a conjugated heterocyclic ligand having the above structure. R ^{0 in} this formula means (a) hydrogen,
(B) A hydrocarbon group having 1 to 24 carbon atoms or (c) a hydrocarbon group having 1 to 24 carbon atoms containing silicon. A plurality of R ^0's may be the same or different. Further, the substituents R ⁰ are bonded to each other to form a ring and have 4 to 4 carbon atoms.
It may form 12 rings (including at least two carbon atoms constituting the conjugated heterocyclic ligand), that is, a condensed ring with a conjugated heterocycle.

Examples of the hydrocarbon group (b) include, for example,
(I) methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group,
Alkyl groups such as amyl group, isoamyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, cetyl group, 2-ethylhexyl group, (ii) cyclohexyl group,
Cycloalkyl group such as cyclopentyl group, (iii) alkenyl group such as allyl group and vinyl group, (iv) aryl group such as phenyl group, tolyl group and naphthyl group, (v) aralkyl group such as benzyl group and phenylethyl group Etc.

Examples of the silicon-containing hydrocarbon group (c) include trimethylsilyl group, dimethylethylsilyl group and dimethylphenylsilyl group.

Among these R ⁰ , particularly preferable ones are hydrogen and those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, n-butyl group, i-butyl group and t-butyl group. Is an alkyl group.

Further, R ⁰ may be bonded to each other to form a ring having 4 to 12 carbon atoms, preferably 6 to 8 carbon atoms. A typical example of such a conjugated heterocyclic ligand in which R ⁰ is bonded to each other to form a ring is one in which a fused 6-membered ring is formed by sharing two adjacent carbon atoms in a phosphonyl group, That is, benzophosphonyl.

R ² is (a) hydrogen, (b) halogen group,
(C) a hydrocarbon group having 1 to 24 carbon atoms, (D) a monovalent hydrocarbon group having 1 to 24 carbon atoms containing nitrogen, oxygen, phosphorus or silicon, or (V) cyclopentadienyl group,
(F) shows a substituted cyclopentadienyl group. here,
Examples of the halogen group (b) include fluorine, chlorine and bromine.

As the hydrocarbon group (c),
(I) methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group,
Alkyl group such as amyl group, isoamyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, cetyl group, 2-ethylhexyl group, (ii) cyclopentyl group,
Examples include cycloalkyl groups such as cyclohexyl groups, (iii) allyl groups, alkenyl groups such as vinyl groups, (iv) aryl groups such as phenyl groups and tolyl groups, (v) benzyl groups, aralkyl groups such as neophyll groups, etc. .

The monovalent hydrocarbon group having 1 to 24 carbon atoms containing nitrogen, oxygen, sulfur, phosphorus or silicon of (d) includes (i) dimethylamide group, diethylamide group, methylphenylamide group, diphenylamide. Group, (ii) methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group, phenoxy group, methylphenoxy group, (iii) trifluoromethylsulfonyl Group, (iv) trimethylsilyl group, dimethylethylsilyl group, dimethylphenylsilyl group and the like.

The substituent of the substituted cyclopentadienyl group (f) is an alkyl group, preferably a lower one (having 1 carbon atom).
~ 4) alkyl groups are typical. Therefore,
Typical examples of the substituted cyclopentadienyl group (f) include a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group, and a tetramethylcyclopentadienyl group. Group, a pentamethylcyclopentadienyl group. In addition, the substituents may be bonded to each other to form a ring by sharing two carbon atoms in the cyclopentadienyl group. A typical example of such a substituted cyclopentadienyl group is a cyclopentadienyl group which shares two adjacent carbon atoms to form a fused 6-membered ring, that is, an indenyl group. Therefore, typical examples of the substituted cyclopentadienyl group in such a case include an indenyl group and a 4,5,6,7-tetrahydroindenyl group.

Therefore, non-limiting examples of the compound (I) forming the catalyst component for α-olefin polymerization according to the present invention include the following. 1) bis (phosphoryl) zirconium dichloride, 2) bis (methylphosphoryl) zirconium dichloride, 3) bis (dimethylphosphoryl) zirconium dichloride, 4) bis (trimethylphosphoryl) zirconium dichloride, 5) bis (tetramethylphosphoryl) zirconium dichloride, 6) bis (n-butylphosphoryl) zirconium dichloride, 7) bis (di-n-butylphosphoryl) zirconium dichloride, 8) bis (phosphoryl) zirconium monochloride monohydride, 10) bis (dimethylphosphoryl) zirconium monochloride monohydride , 11) Bis (trimethylphosphoryl) zirconium monochloride monohydride, 12) Bis (tetramethylphosphoryl) zirconium monochloride monohydra Id, 13) Bis (n-butylphosphoryl) zirconium monochloride monohydride, 14) Bis (di-n-butylphosphoryl) zirconium monochloride monohydride, 15) Bis (phosphoryl) zirconium monochloride monomethyl, 16) Bis (methyl) Phosphoryl) zirconium monochloride monomethyl, 17) Bis (dimethylphosphoryl) zirconium monochloride monomethyl, 18) Bis (trimethylphosphoryl) zirconium monochloride monomethyl, 19) Bis (tetramethylphosphoryl) zirconium monochloride monomethyl, 20) Bis (n- Butylphosphoryl) zirconium monochloride monomethyl, 21) Bis (di-n-butylphosphoryl) zirconium monochloride monomethyl, 22) Bis (benzophosphoryl) zirconium di Lolid, 23) Bis (2-methylbenzophosphoryl) zirconium dichloride, 24) Bis (2,3-dimethylbenzophosphoryl) zirconium dichloride, 25) Bis (4,5,6,7-tetrahydrobenzophosphoryl) zirconium dichloride, 26 ) Bis (2,3-dimethyl-4,5,6,7-tetrahydrobenzophosphoryl) zirconium dichloride, and one or both of the chlorides of these compounds are hydrogen, a halogen group other than chloride, and a carbon number of 1 to 24.
The hydrocarbon group, a monovalent hydrocarbon group having 1 to 24 carbon atoms containing nitrogen, oxygen, phosphorus or silicon, or a compound replacing the cyclopentadienyl group or the substituted cyclopentadienyl group can also be exemplified.

Further, instead of zirconium, compounds other than titanium, hafnium, tantalum, niobium, vanadium, tungsten, molybdenum, etc. can be exemplified. Preferred among the compounds of formula (I) are those in which each substituent is as follows. R ⁰ : hydrogen, a hydrocarbon group having 1 to 12 carbon atoms, or a hydrocarbon group having 1 to 12 carbon atoms containing silicon, and having adjacent substituents R ⁰ bonded to each other to have 4 to 8 carbon atoms (conjugated heterocyclic ring). (Including at least two carbon atoms constituting the ligand) may be formed. m: 1 or 2. M: IV Group _B transition metal. R ² : hydrogen, halogen, a hydrocarbon group having 1 to 12 carbon atoms,
1 carbon atom containing nitrogen, oxygen, sulfur, phosphorus or silicon
A hydrocarbon group of ~ 12, or a cyclopentadienyl group,
Substituted cyclopentadienyl group. A plurality of R ² may be the same or different.

Synthesis of Compound (I) The compound (I) of the present invention can be synthesized by any method suitable for forming a substituent or a bond. One representative synthetic route for bis (tetramethylphosphoryl) zirconium dichloride is as follows.

[0035]

[Chemical 8] [In the above, Me represents a methyl group and Ph represents a phenyl group. ]

<Catalyst for α-Olefin Polymerization (1)>
The first α-olefin polymerization catalyst according to the present invention is a combination of specific components (A) and (B). Here, the term "combined" does not exclude a combination with the other purposeful components in addition to the combination of the listed components (A) and (B) alone.

Component (A) Component (A) is a catalyst component for α-olefin polymerization, which comprises the compound represented by the above general formula (I). Details are as described above.

Component (B) Component (B) is a compound selected from the following (A), (B) and (C). (A) Aluminum oxy compound (b) Lewis acid (c) Ionic compound capable of reacting with compound (I) in component (A) and converting it to a cation

Some Lewis acids can be regarded as "ionic compounds capable of reacting with compound (I) and converting it into cations". Therefore, a compound belonging to both of the "Lewis acid" and the "ionic compound capable of reacting with the compound (I) to convert it into a cation" is understood to belong to either one.

As the aluminum oxy compound of (a), specifically, the following general formulas (II), (III) or (I
There is a compound represented by V).

[0041]

[Chemical 9] [Here, p is an integer of 0 to 40, preferably 2 to 30, and R ³ is hydrogen or a hydrocarbon residue, preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms. ,
Indicates. ]

The compounds of the general formulas (II) and (III) are compounds also called alumoxanes, which are products obtained by reacting one kind of trialkylaluminum or two or more kinds of trialkylaluminum with water. is there. Specifically, methylalumoxane obtained from one type of trialkylaluminum and water, for example, ethylalumoxane, propylalumoxane, butylalumoxane, isobutylalumoxane, methylethyl obtained from two types of trialkylaluminum and water. Alumoxanes such as methylbutyl alumoxane and methyl isobutyl alumoxane are exemplified. Particularly preferred among these are methylalumoxane and methylisobutylalumoxane.

A plurality of these alumoxanes can be used in combination in each group and between each group, and can also be used in combination with other alkylaluminum compounds such as tolmethylaluminum, triethylaluminum, triisobutylaluminum and dimethylaluminum chloride. It is also possible to do so. The combination can also be done intentionally,
It may be a case where the trialkylaluminum used excessively in the production method as described below remains as a result of residual use.

These alumoxanes can be prepared under various known conditions. Specifically, the following methods can be exemplified. Method of reacting trialkylaluminum directly with water using a suitable organic solvent such as benzene, toluene, ether, etc., Reacting with salt hydrate having trialkylaluminum and water of crystallization, for example, copper sulfate, aluminum sulfate hydrate Method, method of reacting trialkylaluminum and moisture impregnated in silica gel, etc., method of mixing trimethylaluminum and triisobutylaluminum, and reacting directly with water using a suitable organic solvent such as toluene, benzene, ether, Mixing trimethylaluminum and triisobutylaluminum, a salt hydrate having water of crystallization, such as copper sulfate,
Method of heating reaction with aluminum sulfate hydrate, method of impregnating silica gel with water, treatment with triisobutylaluminum, and further treatment with trimethylaluminum, trimethylalumoxane and isobutylalumoxane are synthesized by known methods. , A method of mixing a predetermined amount of these two components and heating the mixture, and adding a salt having water of crystallization such as copper sulfate pentahydrate to an aromatic hydrocarbon solvent such as benzene and toluene, and -40 to 40
A method of reacting trimethylaluminum under a temperature condition of about ℃. In this case, the amount of water used is usually 0.5 to 1.5 in molar ratio with respect to trimethylaluminum.
The methylalumoxane thus obtained is a linear or cyclic polymer of organoaluminum.

The compound represented by the general formula (IV) is composed of one kind of trialkylaluminum, or two or more kinds of trialkylaluminum.

[0046]

[Chemical 10] [Wherein R ⁴ has 1 to 10 carbon atoms, preferably 1 carbon atoms]
~ 6 hydrocarbon groups are shown. ] It can be obtained by the reaction of 10: 1 to 1: 1 (molar ratio) with an alkylboronic acid. Specifically, a 2: 1 reaction product of trimethylaluminum and methylboronic acid, a 2: 1 reaction product of triisobutylaluminum and methylboronic acid, and a 1: 1: 1 reaction product of trimethylaluminum, triisobutylaluminum and methylboronic acid. , A 2: 1 reaction product of trimethylaluminum and ethylboronic acid, a 2: 1 reaction product of triethylaluminum and butylboronic acid, and the like. These compounds of the general formula (IV) can be used in plural kinds, and alumoxane represented by the general formula (II) or (III), trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, etc. It is also possible to use in combination with the other alkylaluminum compound.

The compound (C) as the component (B), that is, the ionic compound capable of reacting with the compound (I) and converting it into a cation, has the general formula (V)
There is something represented by. [K] ^{e +} [Z] ^e- (V) Here, K is a cation component, and examples thereof include a carbonium cation, tripyrium cation, ammonium cation, oxonium cation, and sulfonium cation. In addition, metal cations and organic metal cations that are themselves easily reduced are also included. Specific examples of these cations include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, indenium, triethylammonium, tripropylammonium, tributylammonium, N, N-dimethylanilinium, dipropylammonium, dicyclohexylammonium, triphenylammonium. Phenylphosphonium, trimethylphosphonium, tri (dimethylphenyl) phosphonium, tri (methylphenyl) phosphonium, triphenylsulfonium, triphenyloxonium, triethyloxonium, pyrylium, and silver ion, gold ion, platinum ion, copper ion, palladium ion , Mercury ions, ferrocenium ions, etc.

Z in the above general formula (V) is an ionic anion component, which is a component (generally non-coordinating) serving as a counter anion for the cation species converted by the compound (I). Examples thereof include organic boron compound anions, organic aluminum compound anions, organic gallium compound anions, organic phosphorus compound anions, organic arsenic compound anions, and organic antimony compound anions. Specifically, (i) tetraphenylboron, tetrakis (3,4,5-trifluorophenyl) boron, tetrakis (3,5-di (trifluoromethyl) phenyl) boron, tetrakis (3,5-di ( t-butyl) phenyl) boron, tetrakis (pentafluorophenyl) boron, (ii) tetraphenylaluminum, tetrakis (3,4,5-trifluorophenyl) aluminum, tetrakis (3,5-di (trifluoromethyl))
Phenyl) aluminum, tetrakis (3,5-di (t
-Butyl) phenyl) aluminum, tetrakis (pentafluorophenyl) aluminum, (iii) tetraphenylgallium, tetrakis (3,4,5-trifluorophenyl) gallium, tetrakis (3,5-di (trifluoromethyl) phenyl) Gallium, tetrakis (3
5-di (t-butyl) phenyl) gallium, tetrakis (pentafluorophenyl) gallium, (iv) tetraphenylphosphorus, tetrakis (pentafluorophenyl) phosphorus, (v) tetraphenylarsenic, tetrakis (pentafluorophenyl) arsenic, (Vi) Tetraphenyl antimony, tetrakis (pentafluorophenyl) antimony, (vii) decaborate, undecaborate, carbadodecaborate, decachlorodecaborate and the like.

Examples of the (b) Lewis acid as the component (B), particularly the Lewis acid capable of converting the compound (I) into a cation, include various organic boron compounds, metal halogen compounds, solid acids and the like. To be done. In particular,
(I) Organoboron compounds such as triphenylboron, tris (3,5-difluorophenyl) boron, tris (pentafluorophenyl) boron, (ii) aluminum chloride, aluminum bromide, aluminum iodide, magnesium chloride, bromide Magnesium, magnesium iodide,
Magnesium chloride bromide, magnesium chloride iodide, magnesium bromide iodide, magnesium chloride hydride,
Metal halide compounds such as magnesium chloride hydroxide, magnesium bromide hydroxide, magnesium chloride alkoxide, magnesium bromide alkoxide,
And (iii) solid acids such as silica-alumina, alumina.

These ionic compounds and Lewis acids can be used alone as the component (B) or can be used in combination with the aluminum oxy compound of the general formula (II), (III) or (IV). Further, tri-lower alkylaluminum, di-lower alkylaluminum monohalide, mono-lower alkylaluminum dihalide and lower-alkylaluminum sesquihalide, and those in which some of these lower-alkyl groups are replaced with phenoxy groups, such as trimethylaluminum and triethyl It is also possible to use together with an organic aluminum compound such as aluminum, triisobutylaluminum, diethylaluminum phenoxide, dimethylaluminum chloride.

<Component (C)> The component (C) is a fine particle carrier. The above-mentioned component (A) and component (B) can be preferably used by supporting them on the following component (C). Here, "support" includes impregnation.
The catalyst in which the components (A) and (B) are supported on the component (C) corresponds to the second α-olefin polymerization catalyst of the present invention.

The fine particle carrier as the component (C) may be either organic or inorganic. Specific examples of the organic compound carrier include (a) α-olefin polymers such as polyethylene, polypropylene, polybutene-1, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-hexane- 1 copolymer, propylene-
Butene-1 copolymer, propylene-hexene-1 copolymer, propylene-divinylbenzene copolymer, etc. (b)
Aromatic unsaturated hydrocarbon polymers such as polystyrene, styrene-divinylbenzene copolymers, etc., and (c) polar group-containing polymers such as polyacrylic acid esters, polymethacrylic acid esters, polyacrylonitrile, polyvinyl chloride, polyamides. , Polyphenylene ether, polyethylene terephthalate, polycarbonate and the like. Specific examples of the inorganic carrier include (a) inorganic oxides such as SiO ₂ , Al ₂ O ₃ , MgO, and Zr.
O ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO,
ThO ₂ , SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ ,
_{SiO 2 -TiO 2, SiO 2 -V} 2 O 5, SiO 2 -
_{Cr 2 O 3, SiO 2 -TiO} 2 -MgO , etc., (b) inorganic halides such as MgCl _2, AlCl _3, Mn
( ₂ ) Inorganic carbonates, sulfates, nitrates such as Cl ₂ such as Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgC
O ₃ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , M
g (NO ₃ ) ₂ etc., (d) Inorganic hydroxide, eg Mg
(OH) ₂ , Al (OH) ₃ , Ca (OH) _{2 and the} like are exemplified.

Among the fine particle carriers of the above component (C), the following are preferable. When an organic compound carrier is used, the carrier usually has a pore volume of 0.006 to 10 μm of 0.1 c.
C / g or more, preferably 0.3 cc / g or more, and more preferably 0.8 cc / g or more are used. Particularly, it is effective that the sum of the volume of the pores present in 0.05 to 2 μm is 50% or more of the total volume of the pores in the range of 0.006 to 10 μm. The particle size of the carrier is arbitrary, but generally 1 to 3000 μm,
Preferably 5 to 2000 μm, more preferably 10 μm
The range is from m to 1000 μm. Among them, preferably
Examples thereof include polyethylene powder, polypropylene powder and polystyrene powder. When an inorganic carrier is used, the carrier has an average particle size of 10 to 200 μm and a pore volume of 0.1 to 3
Those having a cc / g and a specific surface area of 100 to 500 m ² / g are effective. Among them, inorganic oxides are preferably used,
In particular, SiO ₂ and Al ₂ O ₃ are preferably used.

Also, the above-mentioned organic or inorganic carrier previously treated with water and an organoaluminum compound,
It is also possible to use it as a fine particle carrier. As the organoaluminum compound used in that case, trialkylaluminum is particularly preferable. By the treatment with water and the organoaluminum compound, alumoxane similar to the component (B) may be produced on the surface of particles of the component (C) or in the particles. Therefore, the component (C) previously treated with water and the organoaluminum compound can be regarded as carrying the component (B).

<Arbitrary Component> The catalyst of the present invention can be obtained by supporting the above-mentioned components (A) and (B) on the component (C), but any component may be added as long as the effect is not impaired. It is possible to use. Examples of the optional components that can be added include active hydrogen-containing compounds such as H ₂ O, methanol, ethanol, butanol, electron-donating compounds such as ethers, esters, amines, phenyl borate, dimethylmethoxyaluminum, and phosphorous acid. Alkoxy-containing compounds such as phenyl, tetraethoxysilane, diphenyldimethoxysilane, triethylborane, triphenylborane, tris (pentafluorophenyl)
Examples thereof include organic boron compounds such as borane and triphenylcarbyltetrakis (pentafluorophenyl) borane.

Formation of Catalyst (1) Among the catalysts of the present invention, the above-mentioned component (A) and component (B)
The catalyst obtained by combining the above can be obtained by contacting the above-mentioned component (A) and component (B) in the polymerization tank or outside the polymerization tank in the presence or absence of the monomer to be polymerized. it can.

The amounts of the component (A) and the component (B) used in the present invention are arbitrary. For example, in the case of solvent polymerization, the amount of the component (A) used is 10 ⁻⁷ as a transition metal atom.
It is preferably in the range of 10 ² mmol / liter, more preferably 10 ⁻⁴ to 1 mmol / liter. Ingredient (B) is (a)
In the case of an aluminum oxy compound, the Al / transition metal molar ratio is usually 10 or more and 100,000 or less, and further 10
0 or more and 20000 or less, particularly 100 or more and 10000
The following ranges are preferably used. On the other hand, when (iii) ionic compound or (ii) Lewis acid is used as the component (B), the molar ratio of the transition metal to the transition metal is 0.1 to 1000,
Preferably 0.5 to 100, more preferably 1 to 5
The range is 0.

The catalyst of the present invention comprises components (A) and (B).
Other than the above, it is possible to include other components as described above, but as the third component (optional component) that can be added to the components (A) and (B), for example, H ₂ O,
And lower alkanols, for example, active hydrogen-containing compounds such as methanol, ethanol, butanol, ethers,
Examples thereof include electron-donating compounds such as esters and amines, and alkoxy-containing compounds such as phenyl borate, dimethylmethoxyaluminum, phenyl phosphite, tetraethoxysilane, and diphenyldimethoxysilane.
These compounds fall into the category of those known as electron donors in Ziegler type or Ziegler / Natta type catalysts containing a halogen-containing titanium compound as a transition metal component.

When using these catalyst systems for the polymerization of olefins, components (A) and (B) may be introduced separately into the reaction vessel, or components (A) and (B) may have been contacted beforehand. You may introduce a thing into a reaction tank. When the components (A) and (B) are brought into contact with each other in advance, it is possible to carry out this in the presence of the monomer to be polymerized to partially polymerize the olefin (so-called prepolymerization).

Further, in the present invention, the olefin polymerization catalyst in the catalyst in which the component (A) and the component (B) are supported on the component (C) is the component (A), the component (B) and the component. It can be prepared by mixing (C), preferably in an inert hydrocarbon solvent. At this time, the mixing order is arbitrarily selected, but it is preferable that the component (B) and the component (C) are mixed and brought into contact with each other, and then the component (A) is mixed.
Are mixed or contacted, or component (A) and component (B) are mixed and contacted, and then component (C) is mixed and contacted.

When a fine particle carrier previously treated with water and an organoaluminum compound is used as the component (C), it can be prepared by mixing and contacting the components (A) and (C).

Specific examples of the inert hydrocarbon solvent used in the preparation of the olefin polymerization catalyst according to the present invention include (a) alicyclic hydrocarbons such as propane and butane,
Pentane, hexane, heptane, octane, decane, dodecane, cyclohexane, methylcyclopentane, etc.
(B) Aromatic hydrocarbons such as benzene, toluene and xylene; and (c) halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane and the like, and (d) mixtures thereof. When the components (A), (B) and (C) are mixed and brought into contact with each other, the component (A) is usually 10 ⁻⁷ to 10 ⁻³ mol, preferably 10 ⁻⁶ to 10 ⁻ per 1 g of the component (C). ⁴ moles,
Used in an amount of.

When the (a) aluminum oxy compound is used as the component (B), the atomic ratio of the aluminum of the component (B) to the transition metal in the component (A) (Al / transition metal).
Is usually 10 to 5000, preferably 20 to 2000,
Is.

As the component (B), when an ionic compound capable of reacting with (b) Lewis acid or (c) the compound (I) in the component (A) to convert it into a cation is used, The molar ratio of (B) and component (A) is usually 0.1.
˜1000, preferably 0.5 to 100.

When a fine particle carrier previously treated with water and an organoaluminum compound is used as the component (C),
The atomic ratio (Al / transition metal) of aluminum of the component (C) and the transition metal in the component (A) is usually 10 to 5,000,
It is preferably 20 to 2000.

Component (A), component (B) and component (C)
The contact temperature is usually -50 to 150 ° C, preferably -2.
It is 0 degreeC-120 degreeC.

The olefin polymerization catalyst of the present invention obtained as described above contains 10 ^-7 to 10 ^-3 per 1 g of the component (C).
Gram atoms, preferably 10 ^-6 to 10 ^-4 gram atoms, of the transition metal atom are supported, and when the component (B) is (a), 10 ^-6 to 10 ^-1 gram atoms, preferably 1
Aluminum of 0 ^-5 to 10 ^-2 g atom, (b),
In the case of (c), it is desirable that 10 ⁻⁷ to 10 ⁻³ mol, preferably 10 ⁻⁶ to 10 ⁻⁴ mol of the compound is supported.

In the present invention, the catalyst composed of each of the above components can be used as a prepolymerized olefin. The prepolymerization is carried out by the above component (A),
Component (B) and component (C) are mixed and contacted preferably in an inert hydrocarbon solvent, and olefin is introduced therein, or after removing the solvent, olefin is introduced and gas phase is conducted. You can When the prepolymerization is carried out in a solvent, the transition metal compound is used in an amount of 10 ^{-5 to} 1.0 mol / liter, preferably 10 ^-1 to 10 ^-3 mol / liter. The prepolymerization temperature is -20 ° C to 80 ° C, preferably 0 to 50 ° C, and the prepolymerization time is 0.
It is about 1 to 100 hours, preferably 0.2 to 50 hours.

The olefin used in the prepolymerization is selected from the olefins used in the polymerization, but is preferably one containing ethylene or propylene as the main component. Furthermore, it is desirable that the amount of the polymer produced by the prepolymerization is in the range of about 0.1 to 500 g, preferably 1 to 100 g per 1 g of the component (C). In addition, 10 ^-7 to 10 ^-3 g atom per 1 g of the component (C),
Preferably, 10 ⁻⁶ to 10 ⁻⁴ gram atom of a transition metal atom is supported, and when the component (B) is (a),
10 ^-6 to 10 ^-1 gram atom, preferably 10 ^-5 to 10
^-2 g atom, when aluminum is (b) or (c), it is 10 ^-7 to 10 ^-3 mol, preferably,
It is desirable that 10 ⁻⁶ to 10 ⁻⁴ mol of the compound is supported.

As the inert hydrocarbon catalyst used for preparing the olefin polymerization catalyst of the present invention, saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene are used alone or in a mixture. To be

Formation of Catalyst (No. 2) <Use of Catalyst / Production of α-Olefin Polymer> The catalyst of the present invention is of course applicable to solvent polymerization using a solvent, but substantially no solvent is used. Liquid phase solventless polymerization not used,
It is also applied to gas phase polymerization and melt polymerization. It is also applied to continuous polymerization and batch polymerization.

As the solvent in the case of solvent polymerization, hexane, heptane, pentane, cyclohexane, benzene,
Saturated aliphatic or aromatic hydrocarbons such as toluene may be used alone or as a mixture.

The polymerization temperature is about -78 to 200 ° C, preferably -20 to 100 ° C. The olefin pressure of the reaction system is not particularly limited, but is preferably atmospheric pressure to 50 Kg / c.
The range is m ² · G.

In the polymerization, the molecular weight can be controlled by known means such as selection of temperature and pressure or introduction of hydrogen.

Α-Olefin polymerized by the catalyst of the present invention, that is, α-olefin used in the polymerization reaction in the method of the present invention.
-The olefin includes ethylene and is an α-olefin having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms. 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. Preferred are ethylene, propylene, 1-hexene, 1-octene and the like, and particularly preferred are ethylene, propylene and the like. These α-olefins can be mixed for use in polymerization.

Further, the catalyst of the present invention comprises another monomer copolymerizable with the above α-olefin such as butadiene, 1,
Conjugated and non-conjugated dienes such as 4-hexadiene, 7-methyl-1,6-octadiene, 1,8-nonadiene, 1,9-decadiene, or cyclopropene, cyclobutene, cyclopentene, norbornene, dicyclopentadiene It is also effective for the copolymerization of cyclic olefins such as

[0077]

The following examples serve to explain the present invention more specifically, and the present invention is not limited to these examples. Synthesis Example 1 1-Phenyl-2,3,4,5-tetramethylphosphor
Synthesis of 1-phenyltetramethylphosphole shown below was synthesized as follows.

[0078]

[Chemical 11]

Aluminum chloride 13.6 in a nitrogen atmosphere
g was suspended in 150 ml of methylene chloride. 150 ml of methylene chloride containing 15 ml of 2-butyne
ml was added dropwise in an ice bath in 20 minutes, and the mixture was stirred as it was for 30 minutes. Further, the mixture was reacted at room temperature for 30 minutes to obtain a dark red solution. This was cooled to −60 ° C., and 150 m of methylene chloride containing 19.9 g of dichlorophenylphosphine.
1 was added dropwise in 20 minutes. The mixture was returned to room temperature with stirring to obtain a dark purple solution. 150m methylene chloride here
35 ml of tri-n-butylphosphine dissolved in 1-
It was added dropwise at 30 ° C. in 10 minutes. The solution became pale yellow.
The solvent was removed under reduced pressure to obtain a yellowish brown viscous solid.

It was extracted with 700 ml of hexane, and the extract was washed with 200 ml of an aqueous sodium hydrogen carbonate solution (5% by weight) and 400 ml of pure water. 30 g of anhydrous magnesium sulfate was added as a drying agent, and the mixture was left standing overnight. Anhydrous magnesium sulfate was filtered off and the hexane solvent was removed. In this way, pale yellow oily 1-phenyl-2,3,4,5-tetramethylphosphole was obtained with a yield of 80%. Identification is ¹ H
-NMR and ³¹ P-NMR were performed.

Example 1 Bis (2,3,4,5-tetramethylphosphoryl) dil
Synthesis of Conium Dichloride 2.89 g (13.4 mmol) of 1-phenyl-2,3,4,5-tetramethylphosphole obtained by synthesizing according to Synthesis Example 1 in an atmosphere of argon gas was dried with 50 ml of tetrahydrofuran. Melted into When 0.37 g of granular metallic lithium was added thereto at room temperature, the solution gradually changed to deep red. The reaction was continued while stirring for 3 hours. After the reaction, the dark red solution part was separated from the lithium reaction residue, and 0.60 g (4.50 g) of anhydrous aluminum chloride was added in an ice bath to deactivate the contained phenyllithium.
mmol) was added over 10 minutes, and the reaction was further performed for 3 hours.
This is designated as solution A.

In a nitrogen gas atmosphere, 1.48 g (6.35 mmol) of zirconium tetrachloride was suspended in 15 ml of toluene and placed in an ice bath. The above-mentioned liquid A was dropped into this in 15 minutes,
It was further reacted for 30 minutes. After returning to room temperature, the solvent was removed under reduced pressure, and the residue was dried. This dried solid was extracted with 130 ml of dry diethyl ether, the solvent was removed, and the mixture was dried to 60 ml of dry n-pentane, and the same operation was performed.
1.24 g of 3,4,5-tetramethylphosphoryl) zirconium dichloride (yield 44% based on zirconium tetrachloride) was obtained. Identification was carried out by ¹ H-NMR and ³¹ P
-It was performed by NMR.

[0083]

[Chemical 12]

Polymerization of ethylene After the inside of a stirring autoclave having an internal volume of 1 liter was sufficiently replaced with ethylene, 400 ml of toluene that had been thoroughly dehydrated and deoxygenated, and methylalumoxane (average degree of polymerization: 16) manufactured by Toso Akzo Co., Ltd. were converted into Al atoms. At 4 mmol (0.
23 g) was introduced and the bis (2,3,4,5) synthesized above was introduced.
-Tetramethylphosphoryl) zirconium dichloride (0.90 mg, 2 μmol) and hydrogen gas (200 ml) were introduced, the temperature was raised to 90 ° C., and the polymerization was carried out at an ethylene pressure of 7 Kg / cm ² G for 1 hour.

After completion of the polymerization, 500 ml of ethanol was added to the obtained polymer slurry, the polymer was separated by filtration, and then the polymer was dried by heating under reduced pressure. Catalytic activity: 181000 g / g-Zr Mn: 8700 Mw: 36000 Mw / Mn: 4.14 Here, the catalytic activity (unit [g / g-Zr]) is the production per weight of zirconium contained in the catalyst used. The polymer weight is shown. In addition, the number average molecular weight (denoted as Mn), the weight average molecular weight (denoted as Mw), and the molecular weight distribution (Mw / Mn)
Is a polystyrene-equivalent value obtained by gel permeation chromatography (hereinafter the same in each example).

Example 2 Polymerization of ethylene After thoroughly replacing the inside of a stirring autoclave with an internal volume of 1 liter with ethylene, 400 ml of toluene that had been thoroughly dehydrated and deoxygenated and a heptane solution of triethylaluminum (concentration: 68 mg / ml) were added. 74 ml was introduced, 0.96 mg of bis (tetramethylphosphoryl) zirconium dichloride synthesized in Example 1 above, and a toluene solution of dimethylanilium tetrakis (pentafluorophenyl) borate (concentration: 1.0 mg / ml) 3 .5
ml, hydrogen gas 200 ml, and heated to 90 ° C.,
Polymerization was carried out at an ethylene pressure of 7 kg / cm ² G for 1 hour.

After completion of the polymerization, 500 ml of Echinene was added to the obtained polymer slurry, the polymer was separated by filtration, and then the polymer was dried by heating. Catalytic activity: 99000 g / g-Zr Mn: 71000 Mw: 205000 Mw / Mn: 2.88

Example 3 Polymerization of Propylene After the inside of a stirring autoclave having an internal volume of 1 liter was sufficiently replaced with propylene, 400 ml of sufficiently dehydrated and deoxygenated toluene and 2 mmol of Toma Akzo MMAO in terms of Al atom were introduced. , Bis (tetramethylphosphoryl) zirconium dichloride synthesized above was added to 0.96
Introducing mg, raising the temperature to 40 ° C., and propylene pressure 7 Kg /
Polymerization was carried out at cm ² G for 1 hour. After completion of the polymerization, toluene was removed from the reaction solution, the polymer was separated, and then the polymer was dried by heating. Catalytic activity: 23000 g / g-Zr Mn: 6000 Mw: 10000 Mw / Mn: 1.65

Example 4 Preparation of Supported Catalyst 4.8 g of methylalumoxane-supported silica (methylalumoxane content 48% by weight, manufactured by Witco) was placed in a 300 ml flask which was sufficiently purged with nitrogen and suspended in 30 ml of toluene. Then, the same screws (2, 3, 3) as in Example 1
3.7 ml of a toluene solution of 4,5-tetramethylphosphoryl) zirconium dichloride (solution concentration 1.0 mg zirconium / ml toluene) was introduced, and the mixture was stirred at room temperature for 10 minutes. Then, the toluene was distilled off to obtain a supported catalyst 4.8.
g was obtained.

Polymerization of ethylene After the inside of a stirring autoclave having an internal volume of 1.5 liters was sufficiently replaced with nitrogen, 150 g of sodium chloride was added, and the mixture was stirred at 90 ° C. for 20 minutes while purging with nitrogen. Then, 1 ml of a toluene solution of triisobutylaluminum (160 mg triisobutylaluminum / ml toluene) and 0.65 g (corresponding to 0.5 mg Zr) of the supported catalyst prepared above were used.
cc was added. Then, the temperature was raised to 70 ° C and the ethylene pressure was adjusted to 7
Polymerization was performed for 2 hours at kg / cm ² G. After completion of the polymerization, sodium chloride was removed by washing with water, and water was removed with acetone to separate the polymer. Subsequently, the polymer was dried by heating under reduced pressure to obtain 4.8 g of the polymer (Zr
Y 9250g polymer, Mw = 220,000, Q value
16).

Example 5 Preparation of prepolymerization catalyst 4.8 g of methylalumoxane-supported silica (manufactured by Witco: methylalumoxane content 48% by weight) was placed in a 300 ml flask which had been sufficiently replaced with nitrogen, and 100 m of heptane was added.
It was suspended in 1 l. Then prepared as in Example 1,
Toluene solution of bis (2,3,4,5-tetramethylphosphoryl) zirconium dichloride (solution concentration 1.0m
(3.7 g of zirconium / ml toluene),
Stir at room temperature for 10 minutes. Then, ethylene gas was allowed to flow under normal pressure, and prepolymerization was carried out in the flask at 20 ° C./1 hour. Then, the heptane was distilled off, and the prepolymerization catalyst 12.
95 g were obtained. Polymerization of ethylene In the polymerization of ethylene in Example 4, the polymerization operation was performed in the same manner as in Example 4 except that 1.75 g of the prepolymerized catalyst prepared above was used instead of the supported catalyst to obtain 4.9 g of a polymer. Obtained (ZrY 9800 g polymer, Mw =
287,000, Q value 29).

Example 6 Polymerization of ethylene After the inside of a stirring autoclave having an internal volume of 1.5 liters was sufficiently replaced with ethylene, 500 ml of heptane was added. Thereafter, 1 ml of a toluene solution of triisobutylaluminum (concentration: 160 mg triisobutylaluminum / ml toluene), 1 ml of a heptane slurry of the supported catalyst prepared in Example 4 (concentration: 0.65 g, supported catalyst / ml).
Heptane) and 50 cc of hydrogen were added. Then 70 ° C
The temperature was raised to 7 kg, and the polymerization was carried out at an ethylene pressure of 7 kg / cm ² G for 2 hours to obtain 4.7 g of a polymer (ZrY
9400g polymer, Mw = 503000, Q value 3
2).

Example 7 Polymerization of ethylene In the polymerization of ethylene in Example 6, instead of using the supported catalyst prepared in Example 4, 5 ml of a heptane slurry liquid of the prepolymerized catalyst prepared in Example 5 (0.35 g solid (Catalyst / ml heptane) and 50 cc of hydrogen were added. Then, the temperature was raised to 70 ° C. and the ethylene pressure was 7 kg / cm ² G
Polymerization was carried out for 2 hours to obtain 4.3 g of polymer (ZrY 8600 g polymer, Mw = 32300).
0, Q value 28).

Example 8 Synthesis 1 Synthesis of 1 -phenyl-2,3-dimethyl-4,5,6,7-tetrahydrophosphoindole

[0095]

[Chemical 13]

All operations were performed under a nitrogen atmosphere. Anhydrous aluminum chloride (4.43 g) was suspended in dry dichloromethane (50 ml) and magnetically stirred at 0 ° C. A solution of 2,8-decadiyne (4.23 g) in dry dichloromethane (50 ml) was added dropwise to this suspension over 30 minutes. After the addition was complete, the reaction mixture was cooled in a dry ice-acetone bath, at which temperature phenyldichlorophosphine (4.7 ml) was added to dry dichloromethane (10 m).
The solution diluted with l) was added dropwise over 5 minutes. Then, the reaction temperature was returned to room temperature and further stirred for 1 hour.
The reactor was cooled again in a dry ice-acetone bath, and a solution of tri (n-butyl) phosphine (11.8 ml) diluted with dry dichloromethane (40 ml) was added dropwise over 20 minutes. The reaction solution was returned to room temperature and stirred for 1 hour, and then the solvent was distilled off under reduced pressure to obtain a yellow residue. The residue was extracted with 30 ml of pentane and the extract was concentrated to obtain 4.27 g (56% yield) of a pale yellow viscous liquid. ^The product was identified as 1-phenyl-2,3-dimethyl-4,5,6,7-tetrahydrophosphoindole by ¹ H-NMR.

Synthesis 2 Synthesis of bis (2,3-dimethyl-4,5,6,7-tetrahydrophosphoindolyl) zirconium dichloride

[0098]

[Chemical 14]

All the following operations were performed under a nitrogen atmosphere. Lithium metal (0.23g) was added to dry THF (20m
1-phenyl-obtained in Synthesis 1 above by suspending in 1)
Dry THF (10 ml) of 2,3-dimethyl-4,5,6,7-tetrahydrophosphoindole (2.00 g)
The solution was added at room temperature. The reaction mixture was stirred at room temperature for 2 hours. Then, the reaction solution was cooled in an ice bath, and 0.37 g of anhydrous aluminum chloride was added. The reaction mixture is further added at 0 ° C for 1
After stirring for 30 minutes at room temperature and then at room temperature, the solution in which excess metallic lithium was decanted off (designated as solution A) was used in the next step.

1.56 g of zirconium tetrachloride / THF complex compound (containing 2 mol of THF molecule per gram atom of zirconium) was suspended in dry toluene (20 ml), and this suspension was cooled in an ice bath. . Next, the above solution A was added dropwise over 25 minutes, and after the addition was completed, the reaction mixture was stirred at room temperature for another 30 minutes, and then the solvent was distilled off under reduced pressure to obtain a viscous residue. The residue was extracted with dry diethyl ether (50 ml x 1 and 20 ml x 3),
A red viscous product was obtained. Add this to dry pentane (2
0 ml × 5), the extract was concentrated, and the residue was recrystallized from a mixed solvent of toluene / pentane,
1.15 g (yield 56%) of orange crystals were obtained. ¹ H-N
Based on MR, this product was identified as bis (2,3-dimethyl-4,5,6,7-tetrahydrophosphoindolyl) zirconium dichloride.

Polymerization of ethylene In Example 4, instead of using the toluene solution of bis (2,3,4,5-tetramethylphosphoryl) zirconium dichloride, the bis (2,3-dimethyl-4,5 prepared above was synthesized. , 6,7-Tetrahydrophosphoindolyl) zirconium dichloride in 1 ml of toluene solution (solution concentration 0.2 mg zirconium / ml toluene) was subjected to the same polymerization procedure as in Example 4 to obtain 38 g of a polymer ( ZrY 190000g Polymer, M
w83200 Q value 5.2).

Example 9 Preparation of Supported Catalyst 4.8 g of methylalumoxane-supported silica (manufactured by witco: methylalumoxane content 48% by weight) was placed in a 300 ml flask which was sufficiently replaced with nitrogen, and 30 ml of toluene was added.
Suspended in. Then bis (2,3) prepared in Example 8
-Dimethyl-4,5,6,7-tetrahydrophosphoindolyl) zirconium dichloride in toluene solution (solution concentration 1.0 mg zirconium / ml toluene) 3.7
ml was introduced, and the mixture was stirred at room temperature for 10 minutes. Then, toluene was distilled off to obtain 4.8 g of a supported catalyst.

Polymerization of ethylene After the inside of a stirring autoclave having an internal volume of 1.5 liters was sufficiently replaced with ethylene, 500 ml of heptane was added.
Then 1m of toluene solution of triisobutylaluminum
l (concentration 160 mg triisobutylaluminum / ml
Toluene), 1 ml of the supported catalyst heptane slurry prepared above (concentration 0.65 g supported catalyst / ml heptane),
50 cc of hydrogen was added. After that, the temperature was raised to 70 ° C., and the polymerization operation was performed at an ethylene pressure of 7 kg / cm ² G for 2 hours,
2.1 g of polymer was obtained (ZrY 4200 g polymer Mw = 527000 Q value 14).

[0104]

[Table 1]

[0105]

Industrial Applicability According to the present invention, it is possible to provide a novel catalyst component for polymerization of α-olefin having a high activity, a catalyst for α-olefin polymerization, and a method for producing an α-olefin polymer.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tomohiko Takahama 1 Toho-cho, Yokkaichi-shi, Mie Prefecture Yokkaichi Research Institute, Mitsubishi Petrochemical Co., Ltd. (72) Inventor Kazuhiro Yamamoto 1 Toho-cho, Yokkaichi-shi, Mie Address Mitsubishi Petrochemical Co., Ltd. Yokkaichi Research Institute

Claims (8)

[Claims] 1. A catalyst component for α-olefin polymerization, comprising a compound represented by the following general formula (I). [Chemical 1] [In the formula (I), m represents 1, 2 or 3, and M represents
IVB to VIB transition metals are shown. n is a number corresponding to the valence of M and represents 4, 5 or 6. R ¹ represents the following conjugated heterocyclic ligand. [Chemical 2] R ^0's each independently represent hydrogen, a hydrocarbon group having 1 to 24 carbon atoms, or a hydrocarbon group having 1 to 24 carbon atoms containing silicon. In addition, the substituents R ⁰ may be bonded to each other to form a ring having a carbon number of 4 to 12 (including at least two carbon atoms constituting the conjugated heterocyclic ligand). m
When is 2 or 3, R ¹ may be the same or different. R ² is hydrogen, a halogen group, a hydrocarbon group having 1 to 24 carbon atoms, a monovalent hydrocarbon group having 1 to 24 carbon atoms containing nitrogen, oxygen, sulfur, phosphorus or silicon, or a cyclopentadienyl group. Represents a substituted cyclopentadienyl group.
R ² may be the same or different. ] 2. An α-olefin polymerization catalyst comprising a combination of the following components (A) and (B). Component (A) The catalyst component for polymerization of α-olefin according to claim 1. Component (B) A compound selected from the following (a), (b) and (c). (A) Aluminum oxy compound (b) Lewis acid (c) Ionic compound capable of reacting with compound (I) in component (A) and converting it to a cation 3. A catalyst for α-olefin polymerization, which comprises the following component (A) and component (B) supported on component (C). Component (A) The catalyst component for α-olefin polymerization according to claim 1. Component (B) A compound selected from the following (a), (b) and (c). (A) Aluminum oxy compound (b) Lewis acid (c) An ionic compound component (C) fine particle carrier capable of reacting with the compound (I) in the component (A) to convert it into a cation. 4. The catalyst for α-olefin polymerization according to claim 2, wherein the aluminum oxy compound (a) is a compound represented by the formula [II], [III] or [IV]. [Chemical 3] (Here, p is a number from 0 to 40, and R ³ represents hydrogen or a hydrocarbon residue.) 5. The ionic compound (C) capable of reacting with the compound (I) in the component (A) and converting it into a cation is a compound represented by the formula [V]. The catalyst for polymerization of α-olefin according to 2 or 3. [K] ^{e +} [Z] ^e- [V] (wherein K is an ionic cation component, and is a carbonium cation, tripyrium cation, ammonium cation, oxonium cation, sulfonium cation, or a reduction itself. Z is an ionic anion component that is a counter anion for the cation species converted by the compound (I), and is an organic boron compound. Anions, organic aluminum compound anions, organic gallium compound anions, organic phosphorus compound anions, organic arsenic compound anions, organic antimony compound anions.) 6. The fine particle carrier of component (C) has 2 to 1 carbon atoms.
The catalyst for α-olefin polymerization according to claim 3 or 4, which comprises 0-α-olefin polymer. 7. A catalyst comprising a combination of the component (A) and the component (B) according to any one of claims 2, 4, and 5, wherein an α-olefin is brought into contact with the catalyst for polymerization. A method for producing an α-olefin polymer. 8. A catalyst comprising an ingredient (A) and an ingredient (B) according to any one of claims 3, 4, 5 and 6 supported on an ingredient (C), the α-olefin being brought into contact with the catalyst. A method for producing an α-olefin polymer, which comprises polymerizing.