JPH07188335A - Production of alpha-olefin polymer - Google Patents

Abstract

PURPOSE:To efficiently produce a polymer a high molecular weight without using any expensive catalyst component by bringing an olefin into contact with a catalyst comprising a specific transition metal compound and a reaction product from an alkyl borate and an organoaluminum compound. CONSTITUTION:The polymerization is carried out by bringing an olefin such as propylene into contact with a catalyst comprising (A) a compound of formula I {m is 1 to 3; M is a transition metal in group 4 to 6 in the periodic table; n is a number corresponding to the valency of M, 4 to 6; R<1> is formula II [R<3> is H, a 1 to 24C hydrocarbon, an Si-containing 1 to 24C hydrocarbon, plural R<3> may bond to each other to form a ring of 4 to 12 carbon atoms (including at least two carbon atoms in the conjugated heterocyclic ligands); R<2> is H, halogen, a 1 to 24C hydrocarbon, cyclopentadienyl} such as bis(phosphoryl) zirconium dichloride, and (B) a reaction product between a compound of formula III (R<4> is 1 to 10C hydrocarbon) such as ethyl borate and an organoaluminum compound such as trimethylaluminum.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION

FIELD OF THE INVENTION The present invention relates to a method for producing an α-olefin polymer. More specifically, the present invention relates to the use of a catalyst which, when polymerizing α-olefins, exhibits high activity without using expensive methylalumoxane and enables production of a high molecular weight polymer. Related to α
-It relates to a method for producing an olefin polymer.

[0002]

2. Description of the Related Art In recent years, as a catalyst capable of obtaining an olefin polymer with high activity, a polymerization catalyst composed of a metallocene compound of Group 4 of the periodic table and methylalumoxane has been developed. These are proposed in, for example, JP-A-58-19309 and JP-A-60-35007. However, the inventors of the present invention are aware that these techniques have a problem that it is necessary to use a large amount of expensive methylalumoxane and thus the catalyst cost is high.

On the other hand, as a technique which does not use expensive alumoxane, Japanese Patent Publication Nos. 1-501950 and 1-502.
036, JP-A-3-179005, JP-A-3-20
7703 and JP-A-3-207704 disclose organic boron compounds such as Lewis acids represented by tris (pentafluorophenyl) borane and anionic compounds represented by tetrakis (pentafluorophenyl) borate. It has been proposed to use a catalyst, or further to use a catalyst in which an organoboron compound and a trialkylaluminum coexist. However, since these catalyst systems do not seem to have sufficient polymerization activity, the cost reduction effect is low despite the absence of methylalumoxane.

Further, JP-A-6-49120 and JP-A-6-49
121 and 6-49123 each propose an olefin polymerization method using a compound having a heterocyclic ligand as an essential component. However, even with this method, it is difficult to obtain a satisfactory polymerization activity, and since the obtained polymer has a low molecular weight, there seems to be room for improvement when applied to the production of industrially useful materials. is there.

[0005]

[Outline of Invention]

[0006]

[Means for Solving the Problems]

<Summary> The present invention relates to the production of a high molecular weight olefin polymer by a catalyst system comprising a combination of a metal compound having a specific conjugated hetero five-membered ring ligand and a specific aluminum compound.

That is, the method for producing an olefin polymer according to the present invention comprises: contacting an olefin with a catalyst containing the following component (A) and component (B) to polymerize the catalyst:
It is characterized by.

<Component (A)> A compound represented by the following general formula (I).

[0009]

[Chemical 6] [In the formula (I), m represents 1, 2 or 3, and M represents a transition metal of Groups 4 to 6 of the periodic table. n is a number corresponding to the valence of M and represents 4, 5 or 6.

R ¹ represents the following conjugated heterocyclic ligand.

[0011]

[Chemical 7] R ^3'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. Further, the substituent R ³ is bonded to each other to form a ring to form a ring having 4 to 12 carbon atoms (including at least two carbon atoms constituting the conjugated heterocyclic ligand). Is also good.

When m is 2 or 3, R ¹ may be the same or different.

R ² is hydrogen, halogen, or having 1 to 24 carbon atoms.
Hydrocarbon group, a monovalent group containing 1 to 24 carbon atoms containing nitrogen, oxygen, sulfur, phosphorus or silicon, or a cyclopentadienyl or substituted cyclopentadienyl group. When there are a plurality of R ² 's, they may be the same or different. <Component (B)> (i) A compound represented by the following general formula (II)

[0014]

[Chemical 8] (ii) reaction product with an organoaluminum compound (where:
R ⁴ represents a hydrocarbon group having 1 to 10 carbon atoms). <Effect> According to the present invention, an olefin polymer can be efficiently produced without using expensive methylalumoxane and having a sufficiently high molecular weight as compared with existing catalyst systems. [Detailed Description of the Invention] <Component (A)> The component (A) is a compound represented by the following general formula (I).

[0015]

[Chemical 9] [In the formula (I), m represents 1, 2 or 3, and M represents a transition metal of Groups 4 to 6 of the periodic table. n is a number corresponding to the valence of M and represents 4, 5 or 6.

R ¹ represents the following conjugated heterocyclic ligand.

[0017]

[Chemical 10] R ^3'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. Further, the substituent R ³ is bonded to each other to form a ring to form a ring having 4 to 12 carbon atoms (including at least two carbon atoms constituting the conjugated heterocyclic ligand). Is also good.

When m is 2 or 3, R ¹ may be the same or different.

R ² is (a) hydrogen, (b) halogen,
(C) a hydrocarbon group having 1 to 24 carbon atoms, (D) a monovalent group having 1 to 24 carbon atoms containing nitrogen, oxygen, sulfur, phosphorus or silicon, or (V) cyclopentadienyl or substituted cyclo. Indicates a pentadienyl group.

A plurality of R ^2's may be the same or different. In the compound of formula (I), M is a transition metal of Group 4, 5 or 6 of the periodic table, that is, a Group 4 transition metal of titanium, zirconium or hafnium, a transition metal of Group 5 of vanadium, niobium or tantalum, chromium, molybdenum,
It is a Group 6 transition metal of tungsten. Preferred M is titanium, zirconium, or hafnium Group 4 transition metal,
More preferred M is zirconium.

R ¹ is a conjugated heterocyclic ligand having the above structure. R ^{3 in} this formula is (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 ^3's may be the same or different. Further, the substituent R ³ is bonded to each other to form a ring to form a ring having 4 to 12 carbon atoms (including at least two carbon atoms constituting the conjugated heterocyclic ligand). Is also good.

Preferred examples of the hydrocarbon group (b) include (i) methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group and s
-Butyl group, t-butyl group, amyl group, isoamyl group,
Hexyl group, heptyl group, octyl group, nonyl group, decyl group, cetyl group, alkyl group such as 2-ethylhexyl group, (ii) cyclopentyl group, cycloalkyl group such as cyclohexyl group, (iii) allyl group, vinyl group, etc. Alkenyl group, (iv) phenyl group, p-tolyl group, naphthyl group and other aryl groups, and (v) benzyl group, phenylethyl group, neophyll group and other aralkyl groups, and the like.
Of these, a methyl group, an ethyl group and a phenyl group are particularly preferable.

Further, preferred specific examples of the silicon-containing hydrocarbon group (c) include a trimethylsilyl group, a dimethylethylsilyl group, and a dimethylphenylsilyl group.

Particularly preferred among these R ³ are hydrogen, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group,
It is an alkyl group having 1 to 4 carbon atoms such as s-butyl group and t-butyl group. Among them, hydrogen, methyl group and ethyl group are particularly preferable.

Further, each of these R ^3's is bonded to form a ring and has 4 to 12 carbon atoms, preferably 6 to 8 carbon atoms (including at least two carbon atoms constituting the conjugated heterocyclic ligand). It may form a ring. Among the conjugated heterocyclic ligands in which R ³ is bonded to each other to form a ring, particularly preferable ones are R ³ bonded to a C atom in the conjugated heterocyclic ligand and R ³ bonded to the C atom. Another adjacent C
R ³ bonded to an atom is formed by bonding them to each other at their ω-ends, sharing the conjugated heterocyclic ligand and the above two C atoms in the role heterocyclic ligand. The above two R ³
Examples thereof include condensed rings with a 6-membered carbon ring derived from, that is, a phosphoindolyl group and a phosphoisoindolyl group.

R ² is (a) hydrogen, (b) halogen group,
(C) a hydrocarbon group having 1 to 24 carbon atoms, (D) a monovalent group containing 1 to 24 carbon atoms containing nitrogen, oxygen, sulfur, phosphorus or silicon, or (V) cyclopentadienyl, (F)
A substituted cyclopentadienyl group is shown.

Here, examples of the halogen group (b) include fluorine, chlorine and bromine. Further, as preferable specific examples of the hydrocarbon group (c), (i) methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group,
alkyl groups such as i-butyl group, s-butyl group, t-butyl group, amyl group, isoamyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, cetyl group, and 2-ethylhexyl group, (ii ) Cyclopentyl group, cyclohexyl group and other cycloalkyl groups, (iii) allyl group, vinyl group and other alkenyl groups, (iv) phenyl group, p-tolyl group, naphthyl group and other aryl groups, (v) benzyl group, phenyl Examples thereof include aralkyl groups such as ethyl group and neophyll group.

Preferred specific examples of the monovalent group (1) containing nitrogen, oxygen, sulfur, phosphorus or silicon of (d) include (i) dimethylamide group, diethylamide group, methylphenylamide group, Amido group such as diphenylamide group, (ii) methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group, phenoxy group, p-methylphenoxy group And alkoxy groups such as and aryloxy groups, (iii) sulfonyl groups such as trifluoromethanesulfonyl group, benzenesulfonyl group, and methanesulfonyl group, and (iv) trimethylsilyl group, dimethylethylsilyl group, dimethylphenylsilyl group, and the like.

The substituent of the substituted cyclopentadienyl group (f) is typically an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. Therefore, typical examples of the substituted cyclopentadienyl group (f) include a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a dimethylcyclopentadienyl group,
There are a trimethylcyclopentadienyl group, a tetramethylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Further, the substituent R ² may have two substituents bonded to each other to share two carbon atoms in the cyclopentadienyl group to form a ring. A typical example of such a substituted cyclopentadienyl group is the indenyl group. In addition, a tetrahydroindenyl group, which is a hydrogenated product of this, is also an example of a substituted cyclopentadienyl group.
Can be mentioned.

Particularly preferred among such R ² groups are hydrogen, chlorine and methyl groups.

Therefore, non-limiting examples of the compound (I) forming the catalyst for the 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 (phosphoryl) zirconium monochloride monohydride, 8) Bis (dimethylphosphoryl) zirconium monochloride monohydride, 9) Bis (tetramethylphosphoryl) zirconium monohydrate Chloride monohydride, 10) Bis (n-butylphosphoryl) zirconium monochloride Monohydrate, 11) Bis (phosphoryl) zirconium monochloride Monomethyl 12) bis (dimethylphosphoryl) zirconium monochloride monomethyl, 13) bis (tetramethylphosphoryl) zirconium monochloride monomethyl, 14) bis (n-butylphosphoryl) zirconium monochloride monomethyl, 15) bis (tetramethylphosphoryl) zirconium dimethyl, 16) Bis (phosphoindolyl) zirconium dichloride, 17) Bis (phosphoindolyl) zirconium monochloride, 18) Bis (phosphoindolyl) zirconium dimethyl, 19) Bis (isophosphoindolyl) zirconium dichloride, 20) Bis (4,5,6,7-Tetrahydrophosphoindolyl) zirconium dichloride, 21) Bis (4,5,6,7-tetrahydrophosphoindolyl) zirconium dimethyl.

22) One or both of chlorides in these compounds 1) to 21) is hydrogen, halogen other than chloride, hydrocarbon group having 1 to 24 carbon atoms, nitrogen, oxygen,
A compound replacing a monovalent group containing 1 to 24 carbon atoms containing sulfur, phosphorus or silicon, or a cyclopentadienyl group or a substituted cyclopentadienyl group can also be exemplified.

Further, 23) compounds in which zirconium in these compounds 1) to 21) is replaced by titanium, hafnium, tantalum, niobium, vanadium, tungsten, molybdenum and the like can be exemplified.

The compound (I) can be synthesized by any method which is purposeful for forming a substituent or a bond. For example, F. Mathey, Chemical Reviews, Volume 88,
Phosphors and phosphoindoles, which can be synthesized by various methods described on pages 429 to 453 (1988), are metallized by a conventional method, and are reacted with a 4 to 6 group transition metal compound. You can name the route.

<Component (B)> The component (B) used in the present invention is (i) a compound represented by the following general formula (II):

[0037]

[Chemical 11] (ii) reaction product with an organoaluminum compound (where:
R ⁴ represents a hydrocarbon group having 1 to 10 carbon atoms).

Such component (B) can be regarded as a compound having the following structure (III).

[0039]

[Chemical 12] [However, R ⁴ is a hydrocarbon residue having 1 to 10 carbon atoms,
R ⁵ is hydrogen, halogen, siloxy group, lower alkyl-substituted siloxy group or a hydrocarbon residue having 1 to 10 carbon atoms, and four R ⁵ may be the same or different. ] Component (i) Component (i) has the general formula

[0040]

[Chemical 13] Is an alkylboronic acid represented by (R ⁴ represents a hydrocarbon residue having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms). Specific examples of such an alkylboronic acid include:
Methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, iso-
Examples include butylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid and 3,5-bis (trifluoromethyl) phenylboronic acid. It Of these, the preferred one is
Examples include methylboronic acid, iso-butylboronic acid, 3,5-difluorophenylboronic acid and pentafluorophenylboronic acid. More preferred is methylboronic acid. Component (ii) Component (ii) is an organoaluminum compound.

Specific examples of the organoaluminum compound as the component (ii) include those represented by the general formula R ⁵ _3-p AlX _p or

[0042]

[Chemical 14] Or

[0043]

[Chemical 15] Some are represented by. (However, R ⁵ has 1 to 1 carbon atoms.
A hydrocarbon residue of 0, X is hydrogen or a halogen group, R is
⁶ represents hydrogen, halogen or a hydrocarbon residue having 1 to 10 carbon atoms, and p represents 0 ≦ p <3. ) Specifically, (a) trialuminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, tri-n-butylaluminum, tri-n-propylaluminum, triisoprenylaluminum, etc. Alkyl aluminum, (b) dimethyl aluminum chloride, diethyl aluminum monochloride, diisobutyl aluminum monochloride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, alkyl aluminum halides such as ethyl aluminum dichloride, (ha) dimethyl aluminum hydride, diethyl aluminum hydride, Alkyl Al such as Diisobutyl Aluminum Hydride Alkyl aluminum siloxides such as aluminum hydride, (d) dimethyl aluminum (trimethyl siloxide), dimethyl aluminum (trimethyl siloxide), and diethyl aluminum (trimethyl siloxide), tetra (e) tetraisobutyl alumoxane, tetraethyl alumoxane, etc. An alkyl alumoxane etc. are illustrated. It is also possible to use a mixture of a plurality of these.

Preferred among these organoaluminum compounds are derivatives of methylaluminum and isobutylaluminum such as trimethylaluminum, triisobutylaluminum, dimethylaluminum chloride, diisobutylaluminum chloride and diisobutylaluminum hydride. Even more preferred are trimethylaluminium, triisobutylaluminum, and mixtures thereof. The contact ratio between the component (i) and the component (ii) The component (i) and the use ratio in the case of reacting the component (ii) are arbitrary, but in order to efficiently produce the desired reaction product, the component It is preferable that the molar ratio of (i) to component (ii) is 1: 2. Also, the component (i) and the component
The reaction (ii) is usually carried out in an inert solvent under an inert gas atmosphere. Various contact methods can be used.
For example, (a) a method in which the component (i) is mixed in a toluene solvent, and then a toluene diluted solution of the component (ii) is added dropwise to react, and (b) the component (ii) is diluted in the hexane diluted solution. )
Examples thereof include a method of supplying and reacting as a solid, (c) a method of diluting the component (i) and the component (ii) in toluene and dropping each of them at a constant rate into another container to react. Component (i) and component
The reaction temperature and reaction time of (ii) are arbitrary, but in general, since a side reaction is likely to occur due to a rapid reaction, both components are kept at a low temperature, for example, -78 to 30 ° C, preferably -78 to 10 ° C.
The method of gradually raising the temperature, for example, -10 to 70 [deg.] C. after mixing in [1] is preferable. The reaction time is arbitrary as long as the desired product is obtained, but it is generally carried out in the range of 1 minute to 24 hours.

<Component (C)> In the method for producing an olefin polymer according to the present invention, the catalyst used is a catalyst containing the above-mentioned components (A) and (B). Here, "contains" also means that it contains a purposeful component other than the listed components, that is, the components (A) and (B). A typical example of such a purposeful component is the following component (C). The catalyst containing such components, (A), (B) and (C) constitutes one particularly preferred embodiment of the catalyst of the present invention.

The component (C) is a compound represented by the following general formula (IV).

R ⁷ R ⁸ R ⁹ Al (IV) [wherein R ^{7 to} R ⁹ are each independently a carbon number of 1
To 20, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. Specific preferred examples include trimethylaluminum, triethylaluminum, tri (n-propyl) aluminum, tri (i-butyl) aluminum, tri (n-hexyl) aluminum and the like. <Preparation of Catalyst> The catalyst used in the method of the present invention contains the respective catalyst components of the component (A) and the component (B), and the component (C) as an optional component.

Basically, such a catalyst can be formed by contacting these components in or out of the polymerization reactor at one time, stepwise, or divided into multiple times. it can.

As a preferred specific preparation method, for example, the component (A) and the component (B) are brought into contact with each other in advance, and this mixture is added to the polymerization reactor, or the component (A) and the component (B) are added. Can be separately added to the polymerization reactor.

A method for preparing a catalyst containing three components (A), (B) and (C) is, for example,
A method in which the component (A) and the component (B) are contacted in advance and the mixture and the component (C) are separately added to the polymerization reactor, or all of the components (A), (B) and (C) are added. Can be contacted in advance and this mixture can be added to the polymerization reactor.

The amount of each compound of the components (A) and (B) and the optional component (C) used in the present invention is arbitrary. For example, in the case of solvent polymerization, the amount of component (A) used is 10 ⁻⁷ to 10 ² mmol / liter, more preferably 10 ⁻⁴ to 1 mmol / liter as a transition metal atom.
Is preferred.

The amount of component (B) used is such that the atomic ratio of the aluminum atoms in component (B) to the transition metal in component (A) (A
1 / M), 0.01 to 100,000, preferably 1
The range is from 5,000 to 5,000.

When the component (C) is used, the amount used is the amount of aluminum atoms in the component (C) and the component (A).
The atomic ratio (Al / M) of the transition metal in the medium is 0.01 to 1
The range is 10,000, preferably 0.1 to 5,000, and more preferably 1 to 2,000. <Use of Catalyst / Production of α-Olefin Polymer> The catalyst of the present invention is of course applicable to solvent (solution and slurry) polymerization using a solvent, but is substantially free from a solvent in a liquid phase. It is also applied to solvent polymerization, gas phase polymerization, and bulk polymerization. Further, it is applicable to both continuous polymerization and batch polymerization.

As the solvent in the case of solvent polymerization, pentane, hexane, cyclohexane, heptane, 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 normal pressure to 50 kg / c.
It is in the range of m ² G.

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

The α-olefin (including ethylene in the present invention) used in the polymerization reaction according to the method of the present invention has 2 to 20 carbon atoms, preferably 2 to 1 carbon atoms.
0 is an α-olefin. Specific preferred α-olefins include, 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-eikosen etc. can be mentioned. Ethylene, propylene, 1-butene, 1-hexene, 1-octene and the like are preferable, and ethylene and propylene are particularly preferable. These α-olefins are
Two or more kinds can be mixed and used for polymerization.

Further, the polymerization method of the present invention is carried out by using another monomer copolymerizable with the above α-olefin, for example, butadiene,
Conjugated and non-conjugated dienes such as 1,4-hexadiene, 7-methyl-1,6-octadiene, 1,8-nonadiene, 1,9-decadiene, or cyclopropene, cyclobutene, cyclopentene, norbornadiene, diene It is also effective for binary or ternary copolymerization in which a cyclic olefin such as cyclopentadiene is used as a comonomer in an amount of 50 mol% or less, preferably 30 mol% or less, particularly preferably 10 mol% or less.

[0059]

The following examples further illustrate the present invention. The present invention, according to these examples,
It is not limited in any way.

The molecular weight of the polymer was measured by gel permeation chromatography (GPC) using o-dichlorobenzene as a solvent, and in the following examples,
Weight average molecular weight Mw and Q value showing the molecular weight distribution (Mw /
Mn). <Example 1 (Polymerization of ethylene)> Synthesis of component (A) (1) Synthesis of 1-phenyl-2,3,4,5-tetramethylphosphole 2-butyne (15 ml) in methylene chloride (150 ml)
The solution was added dropwise over 20 minutes to a suspension of aluminum chloride (13.6 g) in methylene chloride (150 ml) at 0 ° C. under a nitrogen atmosphere. After stirring at 0 ° C. for 30 minutes and further at room temperature for 30 minutes, the dark red reaction mixture was cooled to −60 ° C., to which dichlorophenylphosphine (19.9) was added.
g) diluted with methylene chloride (150 ml) was added to 2
It was added dropwise over 0 minutes. The reaction mixture was stirred at room temperature for 20 minutes and then cooled to -30 ° C. 35 ml of tri (n-butyl) phosphine was added dropwise to the reaction solution over 40 minutes to obtain a pale yellow solution. The solution was concentrated under reduced pressure and the product was extracted with hexane to give 1-phenyl-2,3,4,5-
Tetramethylphosphole (16.2 g) was obtained. The structure was confirmed by ¹ H- and ³¹ P-NMR. (2) Synthesis of bis (2,3,4,5-tetramethylphosphoryl) zirconium dichloride 1-phenyl-2,3,4,5 obtained in the above example
-2.9 g of tetramethylphosphole was dissolved in dry tetrahydrofuran (150 ml) and metallic lithium (0.37 g) was added thereto at room temperature. After 3 hours, excess lithium was filtered off. Aluminum chloride (0.60 g) was added to the dark red filtrate at 0 ° C., and the reaction solution was mixed with zirconium tetrachloride (1.48 g) in toluene (15 m).
l) The suspension was added dropwise at 0 ° C. over 15 minutes. The reaction was further carried out at room temperature for 30 minutes, and the solvent was distilled off under reduced pressure. The residue was extracted with dry diethyl ether (50 ml × 3), and the extract was dried. Furthermore, by extracting this with dry pentane (30 ml × 2), bis (2,2
1.24 g of 3,4,5-tetramethylphosphoryl) zirconium dichloride was obtained. (3) Synthesis of component (B) 500 m equipped with a stirrer and a reflux condenser with sufficient nitrogen substitution
100 ml of dehydrated and deoxygenated toluene in a 1-flask
1 was introduced. Then, 4.13 g (41 mmol) of (n-butyl) dihydroxyborane was introduced and the mixture was cooled to -60 ° C or lower. Then, a mixed solution of triisobutylaluminum (75.2 ml of a 160 mg / ml toluene solution) and triethylaluminum (14.4 ml of a 160 mg / ml toluene solution) was added to the above reactor 30 times.
It dripped over minutes. After the dropping was completed, the reaction temperature was slowly raised over 1 hour. Evolution of gas was observed in the range of -20 to 0 ° C. After the reaction temperature reached 20 ° C., the reaction was terminated by further stirring for 1 hour. Thus, the target component (B) was obtained. This solution contained 0.43 mmole / ml of aluminum atom. Less than,
This solution is referred to as a solution (No. 1). (4) Polymerization of ethylene 500 ml of toluene that had been thoroughly degassed with ethylene in the stirring autoclave having an internal volume of 1 liter and then degassed
And a solution of triisobutylaluminum in heptane (0.1
8 mM) 1.0 ml was introduced. Then, a toluene solution of bis (2,3,4,5-tetramethylphosphoryl) zirconium dichloride obtained in (2) of Example 1 (0.
96 mg / ml), 1.0 ml, and further, 4.7 ml of the solution (No. 1) of (3) of Example 1 was introduced, and 90 ° C.
The polymerization reaction was carried out at an ethylene pressure of 7 kg / cm ² for 1 hour. After the reaction, ethanol 500 was added to the obtained slurry.
ml was added and the polymer was isolated by filtration, which was then vacuum dried.

Polymer yield 21.5 g Mw 3.0 × 10 ⁵ Q value 3.4 <Example 2 (polymerization of ethylene)> (4) of Example 1 except that the polymerization temperature was 60 ° C. A polymer was obtained by exactly the same operation.

Polymer yield 11.8 g Mw 5.8 × 10 ⁵ Q value 3.3 <Comparative Example 1 (Polymerization of ethylene> Dry degassed toluene 5
00 ml, 2.2 ml of methylalumoxane manufactured by Tosoh Akzo (degree of polymerization: 16, toluene solution having a concentration of 2.0 mmole / ml as Al atom), and bis (2,3,4,5)
-Tetramethylphosphoryl) zirconium dichloride (0.96 mg) was introduced in this order, and the polymerization reaction was carried out at 90 ° C. and ethylene pressure of 7 kg / cm ² G for 1 hour. The post-treatment was carried out to obtain a polymer.

Polymer yield 21.5 g Mw 6.2 × 10 ⁴ Q value 5.6 <Comparative Example 2 (Ethylene polymerization)> Polymerization exactly the same as Comparative Example 1 except that the polymerization temperature was 60 ° C. A polymer was obtained by the operation.

Polymer yield 20.8 g Mw 3.2 × 10 ⁴ Q value 2.7 <Comparative Example 3 (Polymerization of ethylene)> Dry degassed toluene 500 ml, triethylaluminum heptane solution (0.60 M). 75 ml, screw (2,3,4,5-
Tetramethylphosphoryl) zirconium dichloride (0.96 mg), and dimethylanilinium tetrakis (pentafluorophenyl) borate (3.5 m
g) is introduced in this order, 90 ° C., ethylene pressure 7 kg
/ Cm ² G, the polymerization reaction was performed for 1 hour.

Polymer yield 26.0 g Mw 1.9 × 10 ⁵ Q value 3.1 <Example 3 (polymerization of propylene)> A stirring type autoclave having an internal volume of 1 liter was sufficiently replaced with propylene and then dried. Degassed toluene 500 ml and heptane solution of triisobutylaluminum (0.18 mM) 1.0 m
1 was introduced. Then, bis (2,3,4,5-tetramethylphosphoryl) zirconium dichloride (1.92)
mg) and 9.3 ml of the solution ((No. 1)) of (3) of Example 1 were introduced, and the propylene pressure was 7 kg / cm at 40 ° C.
^{At 2} , the polymerization reaction was performed for 1 hour. After the reaction was completed, the obtained slurry was concentrated to about 30 ml, 300 ml of ethanol was added thereto, the polymer was separated by filtration, and then this was dried under vacuum.

Polymer yield 0.75 g Mw 1.2 × 10 ⁴ Q value 1.4 <Comparative Example 4 (Polymerization of propylene)> 500 ml of dry degassed toluene, methylalumoxane manufactured by Tosoh Akzo (polymerization degree 16, As Al atom, concentration 2.0mmole / m
1 toluene solution), and bis (2,
3,4,5-Tetramethylphosphoryl) zirconium dichloride (1.92 mg) was introduced in this order, and the same polymerization operation as in Example 3 was performed.

Polymer yield 5.3 g Mw 7.1 × 10 ³ Q value 1.5 <Example 4 (polymerization of ethylene)> Synthesis of component (A) (1) 1-phenyl-2,3-dimethyl- 4, 5, 6,
Synthesis of 7-tetrahydrophosphoindole 2,8-decadiyne (4.23 g) and aluminum chloride (4.43 g) in methylene chloride (100 ml),
The reaction was carried out at 0 ° C, and phenyldichlorophosphine (6.20 g, -60 ° C) and tri (n-butyl) were successively added.
After reacting with phosphine (9.58 g, -65 ° C),
The same operation as in Example 1- (1) was performed and 4.27.
g of a pale yellow liquid was obtained. Based on ¹ H-NMR, this was assigned as 1-phenyl-2,3-dimethyl-4,5,6,7-tetrahydrophosphoindole. (2) Synthesis of bis (2,3-dimethyl-4,5,6,7-tetrahydrophosphoindolyl) zirconium dichloride 1-phenyl-2 obtained in (2) of Example 4 above
2.0 g of 3-dimethylphosphoindole was reacted with metallic lithium (0.23 g) in dry tetrahydrofuran at room temperature for 2 hours, excess lithium was filtered off, and the dark red filtrate was treated with aluminum chloride (0.37 g). did. After the reaction of the reaction solution thus obtained with a suspension of zirconium tetrachloride (0.96 g) in toluene (35 ml), 1.15 g of bis (2,3) was obtained by the same operation as in (2) of Example 1. -Dimethyl-4,5,6,7-tetrahydrophosphoindolyl) zirconium dichloride was obtained. (3) Polymerization of ethylene For 1.08 mg of bis (2,3-dimethyl-4,5,6,7-tetrahydrophosphoindolyl) zirconium dichloride obtained in (2) of Example 4 above as a zirconium compound Except for the above, the same polymerization operation as in (4) of Example 1 was performed.

Polymer yield 4.8 g Mw 3.8 × 10 ⁵ Q value 4.4 <Example 5 (polymerization of ethylene)> (3) of Example 4 except that the polymerization temperature was 60 ° C. A polymer was obtained by exactly the same operation.

Polymer yield 11.7 g Mw 9.4 × 10 ⁵ Q value 3.6 <Comparative example 5 (polymerization of ethylene)> 500 ml of dry and degassed toluene, methylalumoxane manufactured by Tosoh Akzo (polymerization degree 16, As an Al atom, 2.2 ml of a toluene solution having a concentration of 2.0 mmole / ml) and bis (2,3-dimethyl-4,5,6,7-tetrahydrophosphoindolyl) zirconium dichloride (1.08 mg) were prepared in this order. In the same manner as in Comparative Example 1, the polymerization and post-treatment operations were carried out.

Polymer yield 14.4 g Mw 1.2 × 10 ⁴ Q value 2.6 <Comparative Example 6 (Polymerization of ethylene)> Polymerization exactly the same as Comparative Example 5 except that the polymerization temperature was 60 ° C. A polymer was obtained by the operation.

Polymer yield 38.0 g Mw 6.8 × 10 ⁴ Q value 5.2 <Example 6 (polymerization of propylene)> As a zirconium compound, bis (2) obtained in (2) of Example 4 above was used. , 3-
The same polymerization reaction as in Example 3 was carried out except that 2.16 mg of dimethyl-4,5,6,7-tetrahydrophosphoindolyl) zirconium dichloride was used.

Polymer yield 0.70 g Mw 9.3 × 10 ³ Q value 1.2 <Comparative Example 7 (Polymerization of propylene)> As a zirconium compound, bis (2) obtained in (2) of Example 4 above was used. , 3-
A polymer was obtained by the same polymerization procedure as in Comparative Example 4 except that 2.16 mg of dimethyl-4,5,6,7-tetrahydrophosphoindolyl) zirconium dichloride was used.

Polymer yield 3.80 g Mw 5.5 × 10 ³ Q value 1.2 <Example 7 (polymerization of ethylene)> (1) Synthesis of component (B) Methyldihydroxyborane (1.0) as a boron compound.
g, 16.7 mmol) and triethylaluminum (23.7 ml of a 160 mg / ml toluene solution) as the trialkylaluminum were used, and the same operation as in (3) of Example 1 was carried out, A solution containing 0.32 mmole / ml of aluminum atom was obtained. This is a solution (No. 2). (2) Polymerization of ethylene Instead of the solution (No. 1), the solution (No. 2) 6.3m
An ethylene polymer was obtained by the same procedure as in (4) of Example 1 except that 1 was used.

Polymer yield 21.0 g Mw 3.1 × 10 ⁵ Q value 3.5 <Example 8 (polymerization of ethylene)> Instead of the solution (No. 1), the solution (No. 2) was added to 6. An ethylene polymer was obtained by the completely same operation as (3) of Example 4 except that 3 ml was used.

Polymer yield 4.2 g Mw 3.6 × 10 ⁵ Q value 4.5 <Example 9 (polymerization of ethylene)> (1) Synthesis of component (B) Methyldihydroxyborane (1.0) as a boron compound.
g, 16.7 mmol) as trialkylaluminum, triisobutylaluminum (160 mg / ml)
Toluene solution (31.0 ml) and triethylaluminum (160 mg / ml toluene solution 6.0 ml).
The target component (B) was obtained by the completely same operation as (3) of Example 1 except that the mixture of and was used. This solution contained 0.29 mmole / ml of aluminum atom. (2) Polymerization of ethylene Instead of the solution (No. 1), the solution (No. 3) is 7.1 m.
An ethylene polymer was obtained by the same procedure as in (4) of Example 1 except that 1 was used.

Polymer yield 12.1 g Mw 3.0 × 10 ⁵ Q value 3.4

[0077]

According to the present invention, the olefin polymer is
"Summary of the invention" means that it can be efficiently produced without using expensive methylalumoxane and has a sufficiently high molecular weight as compared with existing catalyst systems.
This is as described above in the section.

Front page continued (72) Inventor Tomohiko Takahama 1 Toho-cho, Yokkaichi-shi, Mie Prefecture Yokkaichi Research Institute, Mitsubishi Petrochemical Co., Ltd. (72) Hideki Kurokawa 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Oil Chemical Company Yokkaichi Research Institute

Claims (5)

[Claims] 1. A process for producing an olefin polymer, which comprises contacting an olefin with a catalyst containing the following component (A) and component (B) to polymerize the catalyst. <Component (A)> A compound represented by the following general formula (I). [Chemical 1] [In the formula (I), m represents 1, 2 or 3, and M represents a transition metal of Groups 4 to 6 of the periodic table. 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 ^3'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. Further, the substituent R ³ is bonded to each other to form a ring to form a ring having 4 to 12 carbon atoms (including at least two carbon atoms constituting the conjugated heterocyclic ligand). Is also good. When m is 2 or 3, R ¹ may be the same or different. R ² is hydrogen, halogen, carbon number 1
~ 24 hydrocarbon groups, C 1-24 monovalent groups containing nitrogen, oxygen, sulfur, phosphorus or silicon, or cyclopentadienyl or substituted cyclopentadienyl groups. When there are a plurality of R ² 's, they may be the same or different. <Component (B)> (i) A compound represented by the following general formula (II) and (ii) reaction product with an organoaluminum compound (where:
R ⁴ represents a hydrocarbon group having 1 to 10 carbon atoms). 2. The method for producing an olefin polymer according to claim 1, wherein the catalyst comprises the following component (C). <Component C> R ⁷ R ⁸ R ⁹ Al [wherein R ^{7 to} R ⁹ are each independently a carbon number of 1]
~ 20 hydrocarbon groups are shown] 3. The process for producing an olefin polymer according to claim 1, wherein the component (A) is a compound selected from 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 (phosphoryl) zirconium monochloride monohydride, 8) Bis (dimethylphosphoryl) zirconium monochloride monohydride, 9) Bis (tetramethylphosphoryl) zirconium monochloride monohydride , 10) Bis (n-butylphosphoryl) zirconium monochloride monohydride, 11) Bis (phosphoryl) zirconium monochloride monomethyl, 12) Bis ( Methylphosphoryl) zirconium monochloride monomethyl, 13) bis (tetramethylphosphoryl) zirconium monochloride monomethyl, 14) bis (n-butylphosphoryl) zirconium monochloride monomethyl, 15) bis (tetramethylphosphoryl) zirconium dimethyl, 16) bis ( Phosphoindolyl) zirconium dichloride, 17) Bis (phosphoindolyl) zirconium monochloride, 18) Bis (phosphoindolyl) zirconium dimethyl, 19) Bis (isophosphoindolyl) zirconium dichloride, 20) Bis (4,5) , 6,7-Tetrahydrophosphoindolyl) zirconium dichloride, 21) Bis (4,5,6,7-tetrahydrophosphoindolyl) zirconium dimethyl. 22) One or both of the chlorides in these compounds 1) to 21) is hydrogen, halogen other than chloride, and carbon number 1
To a hydrocarbon group of 1 to 24, a monovalent group containing 1 to 24 carbon atoms containing nitrogen, oxygen, sulfur, phosphorus or silicon, or a compound substituted for the cyclopentadienyl or the substituted cyclopentadienyl group, 23) these Compounds in which zirconium in Compounds 1) to 22) is replaced with titanium, hafnium, tantalum, niobium, vanadium, tungsten, molybdenum and the like. 4. The method for producing an olefin polymer according to claim 1, 2 or 3, wherein the component (ii) is a compound selected from the following. R ⁵ _3-p AlX _p [Chemical 5] [Here, R ⁵ represents a hydrocarbon residue having 1 to 10 carbon atoms,
X is hydrogen or a halogen group, R ⁶ is hydrogen, a halogen or a hydrocarbon residue having 1 to 10 carbon atoms, and p is 0 ≦ p <
3 are shown respectively] 5. The method for producing an olefin polymer according to claim 4, wherein the component (ii) is a compound selected from the following. (A) Trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, tri n-butyl aluminum, tri n-propyl aluminum, triisoprenyl aluminum, (b) dimethyl aluminum chloride, diethyl Aluminum monochloride, diisobutyl aluminum monochloride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, (c) dimethyl aluminum hydride, diethyl aluminum hydride, diisobutyl aluminum hydride, (d) dimethyl aluminum (trimethylsiloxide), dimethyl Aluminum (trimethylsiloxide , Diethylaluminum (trimethyl siloxide), (e) tetra isobutyl alumoxane, tetraethyl alumoxane.