JPH04285609A - Olefin polymerization catalyst and production of polyolefin using the same - Google Patents

Abstract

PURPOSE:To provide a process for the production of an olefin-polymerization catalyst having high activity and to provide a process for the production of a polyolefin using the above catalyst. CONSTITUTION:An olefin-polymerization catalyst is produced by contacting a metallocene compound, an organic magnesium compound and an organic aluminum halide compound. A polyolefin is produced by polymerizing an olefin in the presence of the above catalyst.

Description

[Detailed description of the invention]

0001

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst and a method for producing polyolefin using the same.

0002

[Prior Art] Since Japanese Patent Publication No. 39-12105 proposed a method of using a catalyst consisting of a supported transition metal, organoaluminium, and organic acid ester as a polymerization catalyst for α-olefin, many improved catalysts have been proposed. Both the catalytic activity and the stereoregularity of the resulting polymer have been significantly improved.

On the other hand, a catalyst system combining titanium trichloride containing no aluminum and an organic titanium compound is disclosed in US Pat. No. 2,992,212 and JP-A-5
No. 7-111307. Regarding this catalyst system that combines aluminum-free titanium trichloride and an organic titanium compound, instead of titanium trichloride, a catalyst system that combines a catalyst with a titanium compound supported on magnesium chloride and an organic titanium compound is used as a solid catalyst component. There are reports that α-olefin polymers with high activity per titanium content and high stereoregularity can be obtained (for example, Soga et al., Makromol. Chem.
．． Rapid Commun. , 1986, Volume 7, 719
page).

Furthermore, a highly active and highly stereoregular polymer can be obtained by polymerizing an α-olefin with a solid catalyst component containing magnesium, titanium, and halogen as essential components, an organic titanium compound, and an aluminoxane. has been proposed in Japanese Patent Application Laid-Open No. 1-217012.

On the other hand, a method for polymerizing olefins using methylaluminoxane obtained by the reaction of a metallocene compound having a group having conjugated π electrons, particularly cyclopentadiene and its derivatives as a ligand, trialkylaluminum, and water as a catalyst is known. ing. For example, JP-A-58-1
No. 9309 discloses a method for polymerizing olefins using biscyclopentadienylzirconium dichloride and methylaluminoxane as a catalyst. Also, JP-A-61-1
30314, JP-A-61-264010, JP-A-1
-301704 and JP-A-2-41303 disclose methods for producing isotactic poly-α-olefins or syndiotactic poly-α-olefins and polymerization catalysts for producing these stereoregular poly-α-olefins. has been done.

Recently, it has been reported that cationic metallocene compounds having cyclopentadiene and its derivatives as ligands can polymerize olefins without using methylaluminoxane. For example, R. F. J
ORDAN et al. Am. Chem. Soc. , 19
In 1986, Vol. 108, p. 7410, it is reported that a zirconium cation complex having tetraphenylborane as an anion and having biscyclopentadienyl group and methyl group as ligands has ethylene polymerization activity.

[0007] Also, Turner et al. Am. Che
m. Soc. , 1989, Vol. 111, p. 2728, and Japanese Patent Publication No. 1-501950 and Japanese Patent Application Publication No. 1-502036, it has been reported that ion pair type zirconium complexes have similar ethylene polymerization activity.

Furthermore, Zambelli et al.
olecules, 1989, vol. 22, 2186-21
On page 89, it is reported that isotactic polypropylene is polymerized by a combination of a zirconium compound having a cyclopentadiene derivative as a ligand, trimethylaluminum, and fluorodimethylaluminum.

[0009] Furthermore, it has been reported in J. D. that ethylene can be polymerized by using a catalyst in which an actinide metal pentamethylcyclopentadienylthorium dimethyl complex is supported on magnesium chloride. Am. Chem. Soc. , 1988
It is reported in Vol. 110, p. 1647. In this reaction, the methyl group is transferred onto the magnesium, suggesting the formation of a thorium cation complex.

0010

[Problems to be Solved by the Invention] However, the method of adding an organic acid ester during polymerization has problems such as leaving a characteristic ester odor in the polymer and causing coloring. desired.

On the other hand, a catalyst system that combines a catalyst in which a titanium compound is supported on magnesium chloride and an organic titanium compound does not use an organic acid ester, so there is no such problem, but the polymerization activity is insufficient and catalyst residue is generated. It is difficult to commercialize the catalyst without removing it at all, and it is desired to further improve the catalytic activity.

Furthermore, since organic titanium compounds are unstable and easily decomposed, organic zirconium compounds, organic hafnium,
It is desirable to use more stable organic transition metal compounds such as organic vanadium compounds, but when these transition metals are used as catalysts, the catalytic activity decreases, and in particular the stereoregularity decreases significantly, so it is not recommended to use these compounds. (For example, Soga et al., Makromol.C
hem. , 1989, Vol. 190, pp. 31-35).

[0013] The method disclosed in JP-A-1-217012 further uses aluminoxane to solve this problem, so that the activity is greatly improved. however,
In all of these conventional solid-type Ziegler-Natta catalysts, the titanium component contained in the solid catalyst exhibits polymerization activity, and the organic titanium component is not considered as an active species, so the titanium component contained in the solid catalyst is not considered to be an active species. Although the activity per titanium component used was high, the activity per organic titanium component used in large quantities was extremely low.

The method disclosed in JP-A-58-19303 is a unique method in that it has good activity per transition metal and can yield a polymer having a molecular weight distribution of about 2. However, although these methods using aluminoxane improve polymerization activity, they require the use of large amounts of expensive aluminoxane, which increases the cost of the resulting polymer. However, there was a problem in that it was difficult to remove aluminoxane from the resulting polymer after polymerization.

On the other hand, R. F. JORDAN et al., TURN
The method of ER et al. does not have the above problem because the cationic zirconium complex polymerizes ethylene without using aluminoxane, but the boron compound used as a cocatalyst in these catalysts is expensive and the polymerization activity is very low. Moreover, propylene either does not polymerize or can only be obtained with low stereoregularity.

The method of Zambelli et al. uses trimethylaluminum, dimethylaluminum fluoride, and a zirconium complex as a propylene polymerization catalyst to obtain isotactic polypropylene, and does not use expensive aluminoxane. However, there are problems in that it is necessary to use a special organometallic compound containing fluorine, and the polymerization activity is extremely low.

[0017]

[Means for Solving the Problems] The present inventors have conducted extensive studies on a method for solving the above-mentioned problems and producing highly active polyolefins with good productivity, and have completed the present invention.

That is, the present invention provides: a) the following general formula (5) or (6) (wherein A and B or A' and B' are the same or different, unsaturated hydrocarbons coordinated to the central atom); A residue, R is a divalent linear hydrocarbon residue which may have a side chain, or a residue whose linear carbon atom is substituted with a silicon atom, germanium atom or tin atom, (represents a hydrocarbon residue having 1 to 10 carbon atoms, M represents a metal atom selected from Groups 4 and 5 of the periodic table)
A transition metal compound represented by

[0019]

[C5]

[0020]

[C6]

b) Formula 7 of the following general formula (in the formula, R1 is a hydrocarbon residue having 1 to 20 carbon atoms, and R2 is a hydrocarbon residue having 1 to 20 carbon atoms)
~20 hydrocarbon residues or halogen atoms);

[0022]

[Chemical formula 7] MgR1 R2

c) Formula 8 of the following general formula (in the formula R4, R5
represents a hydrocarbon residue having 1 to 20 carbon atoms that are the same or different from each other, a halogen atom, an oxygen atom, a hydrogen atom, an alkoxy group, and X represents a halogen atom). This is an olefin polymerization catalyst.

[0024]

[Chemical formula 8] R4 R5 AlX

The present invention also provides a method for producing an olefin polymerization catalyst, characterized in that an organic magnesium compound b) and an organic aluminum halide compound c) are catalytically reacted in the presence of a transition metal compound a), Furthermore,
This is a method for producing a polyolefin, which is characterized by polymerizing or copolymerizing an olefin using the catalyst.

In the present invention, examples of the transition metal compound having a group having conjugated π electrons represented by the above general formula (5) or (6) as a ligand include the compounds described in the above-mentioned documents. Even if the structure is different, any transition metal compound having a group having conjugated π electrons as a ligand may be used, and compounds represented by the general formula 5 or 6 can be preferably used.

In the formula, A and B or A' and B' are the same or different monovalent or divalent unsaturated hydrocarbon residues, and R is a divalent straight chain which may have a side chain. A hydrocarbon residue or a residue in which some or all of its straight chain carbon atoms are substituted with a silicon atom, germanium atom or tin atom, X is a hydrocarbon residue having 1 to 10 carbon atoms, M
represents a metal atom selected from Groups 4 and 5 of the periodic table.

The unsaturated hydrocarbon residue represented by A, B, A' or B' is a monocyclic ring having 5 to 50 carbon atoms;
Alternatively, a polycyclic group having conjugated π electrons can be exemplified, and specifically, cyclopetadienyl or a part or all of its hydrogen is substituted with a hydrocarbon residue having 1 to 10 carbon atoms (herein, The hydrogen residue may have a structure in which its terminal end is bonded to the cyclopentadiene ring again.)
or polycyclic aromatic hydrocarbon residues such as indenyl and fluorenyl, or those in which part or all of the hydrogen atoms thereof are replaced with hydrocarbon residues having 1 to 10 carbon atoms.

The divalent group represented by R is a methylene group represented by the following general formula 9, or a part or all of the carbon atoms of the methylene group are silicon atoms, germanium atoms,
Alternatively, examples include a silylene group, germylene group, or stanylene group substituted with a tin atom.

[0030]

[Chemical formula 9]-(R'2C)n-(R'2Si)m-(R
'2Ge)p-(R'2Sn)q- (in the formula, R' represents a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms, and the two R's may be the same or different, and n, m , p
, q are integers from 0 to 4 and represent integers that satisfy the above formula. ).

Examples of X include alkyl groups such as methyl, ethyl, propyl and butyl groups, and aryl groups such as phenyl, benzyl and cyclopentadienyl groups.

The organomagnesium compounds represented by the above general formula (7) used in the present invention include dimethylmagnesium, diethylmagnesium, dibutylmagnesium, n-butylethylmagnesium, methylmagnesium chloride, ethylmagnesium chloride,
Examples include magnesium compounds having at least one hydrocarbon residue, such as ethylmagnesium ethoxide and ethylmagnesium isopropoxide.

In general formula 7, in order to make these organomagnesium compounds easily soluble in hydrocarbon solvents,
Alternatively, a small amount of aluminum compound may be added to form a complex to facilitate synthesis.
It is also possible to use complexes with such aluminum compounds.

The ratio of the organomagnesium compound to the above-mentioned transition metal compound is 1 to 100,000 times by mole, usually 1 to 5,000 times by mole.

In addition, the above general formula 8 used in the present invention
The organic aluminum halide compound represented by has a residue such as a halogen atom, an oxygen atom, a hydrogen atom, an alkyl group, an alkoxy group, or an aryl group as a ligand, and each of these ligands may be the same or , may be different, but at least one has a halogen group. For example, an alkyl aluminum halide, an alkoxy metal halide, etc. in which 1 to 3 halogen atoms having 1 to 12 carbon atoms are bonded can be used. Among them, alkyl aluminum halide compounds are preferably used, such as dimethyl aluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride,
Examples include isopropyl aluminum dichloride.

The ratio of organic aluminum halide compound to the above transition metal compound is 1 to 1000.
00 mol times, usually 1 to 5000 mol times.

The catalyst of the present invention is produced by contacting an organic magnesium compound and an organic aluminum halide compound in the presence of a transition metal compound. When these are brought into contact, usually an organomagnesium compound or an organic aluminum halide compound is added to the transition metal compound, and then an organomagnesium compound or an organic aluminum halide compound is added. It does not matter which of the compounds is added first.

Examples of the solvent used in the preparation, polymerization, or treatment of the catalyst using the catalyst component in the present invention include saturated hydrocarbons such as propane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane, and cyclohexane. Aromatic hydrocarbon compounds such as benzene, toluene, and xylene, and halogenated hydrocarbon compounds such as methylene chloride and chlorobenzene can also be used. Further, ether, nitrile, ester compounds, etc. can also be used as long as the solvent itself does not bind or strongly coordinate with the generated transition metal cation compound to inactivate the polymerization activity.

There are no particular limitations on the conditions for polymerizing olefins using this catalyst component, and solvent polymerization using an inert medium, bulk polymerization in the absence of substantially an inert medium, and gas phase polymerization can also be used.

Examples of olefins used in polymerization include olefins having 2 to 25 carbon atoms, specifically ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, Nonen-1,
In addition to linear α-olefins such as decene-1, undecene-1, dodecene-1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, and octadecene-1, 3-methylbutene-1,4-methyl Penten
Examples include branched α-olefins such as 1,4,4-dimethylpentene-1, and cyclic olefins such as cyclopentene, cyclooctene, and norbornene. Can be used for copolymerization.

[0041] As the polymerization temperature and pressure, general conditions used in known methods are used, and the polymerization temperature is usually -20 to 150°C, and the polymerization pressure is normal pressure to 50°C.
Kg/cm2.

[0042]

[Examples] The present invention will be further explained by showing examples below.

Example 1 Isopropylcyclopentadienyl-1-fluorenyl-1-fluorene synthesized according to a conventional method is lithiated, reacted with zirconium tetrachloride, and recrystallized to produce isopropyl(cyclopentadienyl-1-fluorenyl)zirconium dichloride. Obtained.

Isopropyl (cyclopentadienyl-1-
Dissolve 40 mg of fluorenyl) zirconium dimethyl in 20 ml of toluene, and dissolve 2 n-butylethylmagnesium
．． An n-heptane solution containing 32g (trade name MAGALA
19.5 ml of BEM (manufactured by Tosoh Akzo Co., Ltd.) was added.

Next, the above mixture was charged under a nitrogen stream into an autoclave having an internal volume of 5 liters which had been thoroughly dried and purged with nitrogen, and then 1.5 kg of liquid propylene was added.
Further, 34.9 ml of a toluene solution containing 5.06 g of diethylaluminium chloride was added, and the mixture was heated to 60° C. and polymerization was continued for 2 hours. Unreacted propylene was purged and the contents were taken out and dried at 60° C. and 70 mmHg for 8 hours to obtain 110 g of white powdery polypropylene. The intrinsic viscosity (hereinafter referred to as η) of this polypropylene measured in a tetralin solution at 135 °C is 0.65, and the
The ratio of the weight average molecular weight to the number average molecular weight (hereinafter referred to as MW/MN) measured with 4-trichlorobenzene is 2.
．． It was 2. According to 13C-NMR, the syndiotactic pentad fraction was 0.77.

Example 2 The same procedure as in Example 1 was carried out except that dimethylsilylbis(2,4-dimethylcyclopentadienyl)zirconium dimethyl was used instead of isopropyl(cyclopentadienyl-1-fluorenyl) zirconium dimethyl. However, 16 g of polypropylene was obtained. Polymer η is 0
．． 25, MW/MN was 2.3. Moreover, the isotactic pentad fraction was 0.86.

[0047]

Effects of the Invention By carrying out the method of the present invention, it is possible to economically obtain a polyolefin with high activity per catalyst using an inexpensive catalyst, which is extremely valuable industrially.

[Brief explanation of the drawing]

FIG. 1 is a flow diagram to aid in understanding the present invention.

Claims (3)

[Claims] Claim 1: a) Formula 1 or Formula 2 of the following general formula (wherein A and B or A' and B' are the same or different, and represent an unsaturated hydrocarbon residue coordinated to the central atom) , R is a divalent linear hydrocarbon residue which may have a side chain or a residue in which the carbon atom of the linear chain is substituted with a silicon atom, germanium atom or tin atom, and X is a carbon atom (1 to 10 hydrocarbon residues, M represents a metal atom selected from Groups 4 and 5 of the periodic table) and a transition metal compound represented by [Chemical formula 1] [Chemical formula 2] b) The following Chemical formula 3 (in the formula, R1 has 1 to 2 carbon atoms)
0 hydrocarbon residue, R2 represents a hydrocarbon residue having 1 to 20 carbon atoms or a halogen atom); In the formula, R4 and R5 are the same or different from each other and represent a hydrocarbon residue having 1 to 20 carbon atoms, a halogen atom, an oxygen atom, a hydrogen atom, an alkoxy group, and X represents a halogen atom). An olefin polymerization catalyst consisting of an aluminum chloride compound. [Chemical formula 4] R4 R5 AlX 2. A method for producing an olefin polymerization catalyst, which comprises carrying out a catalytic reaction between an organomagnesium compound b) and an organohalogenated aluminum compound c) in the presence of the transition metal compound a) according to claim 1. 3. A method for producing a polyolefin, which comprises polymerizing or copolymerizing an olefin using the catalyst according to claim 1 or 2.