JPH11209426A - Process for polymerizing olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process polymerizing an olefin in the presence of a novel catalyst system having high polymerization activity at a temperatures as high as 50 deg.C or above and giving a polymer having a narrow molecular weight distribution and a high molecular weight. SOLUTION: An olefin is polymerized in the presence of a catalyst comprising (A) a reaction product of a compound of a divalent transition metal of group 10 in the periodic table with a compound represented by the formula and (B) at least one Lewis acid compound selected from the group consisting of organoaluminumoxy compounds, organoaluminum compounds, and organoboron compounds. In the formula, R<1> to R<8> , which are independent of each other, are each hydrogen, a halogen, a hydrocarbon group, a silyl-substituted hydrocarbon group, a hydrocarbon-group-substituted silyl, an alkyloxy, or a fluorohydrocarbon group; and Z is a divalent linking group selected from the group consisting of unsubstituted or hydrocarbon-group-substituted methylene groups. hydrocarbon-group-substituted silylene groups, and carbonyl groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for polymerizing olefins using a novel catalyst system.

[0002]

2. Description of the Related Art Hitherto, it has been known that a transition metal compound belonging to Group 10 of the periodic table, particularly a nickel compound, is a catalyst useful for synthesizing a low-molecular-weight olefin.
Organic Chemistry of Nick
el, 1975, Academic Press,
P. W. Jolly and G. Wilke). On the other hand, various attempts have been made to design and synthesize ligands for catalysts in order to obtain high molecular weight olefins. For example, as a catalyst system for ethylene polymerization, a method of performing polymerization with a nickel compound coordinated with ylide (Journal of
Molecular Catalysis, 1987
Year, vol. 41, p. 123, Angwante Chem
ie, International Edition
in English, 1987, 26, 63,
Journal of Chemical Society
y, Chemical Communication
s, 1994, p. 615, Journal of M
olecular Catalysis, 1994,
92, p. 21), a method of carrying out polymerization with a nickel compound to which aminobisiminophosphorane is coordinated (Angewa)
nt Chemie, International
Edition in English, 1981,
20, 116, 1985, 24, 1001, etc.). However, it is described that the polymer obtained by these methods is an oligomer or has a low polymerization activity even if it has a high molecular weight. As a proposal to solve this problem, a method in which polymerization is performed using a nickel or palladium compound coordinated with diimine (Journa)
l of American Chemical So
cityy, 1995, 117, 6414, WO
96/23010). This compound efficiently gives a high-molecular-weight olefin polymer at a low temperature of 0 ° C. to 50 ° C., but has a problem in industrial use because it rapidly loses its activity in a short time at a higher temperature.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for polymerizing olefins using a novel catalyst system, which has a high polymerization activity at a high temperature of 50 ° C. or more and gives a high molecular weight polymer. Aim.

[0004]

The present invention provides (A) a reaction product of a transition metal compound of Group 10 of the periodic table with a compound represented by the following general formula (1), and (B): This is a method of polymerizing an olefin in the presence of a catalyst comprising at least one Lewis acidic compound selected from the group consisting of an organic aluminum oxy compound, an organic aluminum compound and an organic boron compound.

[0005]

Embedded image

(Where R¹~ R⁸Are each independently hydrogen
Atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, charcoal
Silyl having 1 to 20 carbon atoms in which a part of the silicon is substituted with silicon
Substituted hydrocarbon group, substituted with C1-20 hydrocarbon group
A silyl group, an alkyloxy group having 1 to 20 carbon atoms,
Number of carbon atoms in which part or all of hydrogen has been replaced by fluorine groups
Represents 1 to 20 fluorohydrocarbon groups, Z is unsubstituted or
Is methylene substituted by a hydrocarbon group having 1 to 20 carbon atoms
Substituted with a hydrocarbon group having 1 to 20 carbon atoms
Divalent linking group selected from the group consisting of
And R¹And R ^Two, R^TwoAnd R^Three, R^ThreeAnd R^Four, R^FiveWhen
R⁶, R⁶And R⁷, R⁷And R⁸Are independent of each other
They may combine to form a condensed ring. The following describes the olefin polymerization catalyst according to the present invention and the olefin polymerization catalyst.
Detailed explanation of olefin polymerization method using catalyst
I do.

In the present invention, the term "polymerization" is used to include not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymer but also copolymer. Used with the intent of including coalescence. In the present invention, the component (A) is a reaction product of a divalent transition metal belonging to Group 10 of the periodic table and a compound represented by the general formula [1].

The divalent transition metal compound of Group 10 of the periodic table is a nickel, palladium or platinum compound having an oxidation number of 2, and specific examples thereof include nickel (II) fluoride, nickel (II) chloride, and bromide. Nickel (II), nickel (II) iodide, dichloro (1,2-dimethoxyethane)
Nickel (II), dibromo (1,2-dimethoxyethane) nickel (II), dichlorotetrakisethanolnickel (II), dibromotetrakisethanolnickel (II), nickel acetate (II), palladium chloride (II), palladium bromide (II), palladium (II) iodide, dichloro (bisacetonitrile) palladium (II), dichloro (bisbenzonitrile) palladium (II), allylpalladium chloride (II),
Palladium acetate (II), palladium trifluoroacetate (II), platinum chloride (II), platinum bromide (II), platinum iodide (II) and the like can be mentioned.

Specific examples of the compound represented by the formula [1] include bis (2-pyridyl) methane, bis (6-fluoro-2-pyridyl) methane, bis (6-chloro-2-pyridyl) methane, Bis (5-chloro-2-pyridyl) methane, bis (3-chloro-2-pyridyl) methane, bis (3,5-dichloro-2-pyridyl) methane, bis (6
-Bromo-2-pyridyl) methane, bis (5-bromo-
2-pyridyl) methane, bis (6-methyl-2-pyridyl) methane, bis (5-methyl-2-pyridyl) methane, bis (6-ethyl-2-pyridyl) methane, bis (5-ethyl-2- Pyridyl) methane, bis (6-n-
Propyl-2-pyridyl) methane, bis (5-n-propyl-2-pyridyl) methane, bis (6-isopropyl-2-pyridyl) methane, bis (5-isopropyl-2)
-Pyridyl) methane, bis (6-n-butyl-2-pyridyl) methane, bis (5-n-butyl-2-pyridyl)
Methane, bis (6-isobutyl-2-pyridyl) methane, bis (5-isobutyl-2-pyridyl) methane, bis (6-trifluoromethyl-2-pyridyl) methane,
Bis (5-trifluoromethyl-2-pyridyl) methane, bis (3-chloro-5-trifluoromethyl-2-
Pyridyl) methane, bis (3-methoxy-2-pyridyl) methane, bis (3-methoxy-6-methyl-2-pyridyl) methane, bis (6-benzyl-2-pyridyl)
Methane, bis (5-benzyl-2-pyridyl) methane,
Bis (6-trimethylsilyl-2-pyridyl) methane,
Bis (5-trimethylsilyl-2-pyridyl) methane,
Bis (6-triethylsilyl-2-pyridyl) methane,
Bis (5-triethylsilyl-2-pyridyl) methane,
Bis (6-dimethyl-n-propylsilyl-2-pyridyl) methane, bis (5-dimethyl-n-propylsilyl-2-pyridyl) methane, bis (6-dimethylisopropylsilyl-2-pyridyl) methane, bis ( 5-dimethylisopropylsilyl-2-pyridyl) methane, bis (6-tert-butyldimethylsilyl-2-pyridyl) methane, bis (5-tert-butyldimethylsilyl-2-pyridyl) methane, bis (6-phenyldimethyl) Silyl-2-pyridyl) methane, bis (5-phenyldimethylsilyl-2-pyridyl) methane, bis (6-trimethylsilylmethyl-2-pyridyl) methane, bis (5-trimethylsilylmethyl-2-pyridyl) methane, bis ( 6-phenyldimethylsilylmethyl-2-pyridyl) methane, bis (5 Phenyldimethylsilylmethyl-2-pyridyl) methane, a group of compounds in which the linking group of the above group of compounds is replaced by a dimethylsilylene group from a methylene group; And a group of compounds substituted with a benzylidene group or the like.

The component (A) of the catalyst according to the present invention comprises the above-mentioned bivalent transition metal compound of Group 10 of the periodic table and a general formula [1]
By reacting the compound represented by with a suitable organic solvent in a nitrogen atmosphere in the range of -78 to 120 ° C. The compound represented by the formula [1] is used in a molar ratio of usually 1 to 10, preferably 1 to 2, with respect to the transition metal compound of Group 10 of the periodic table. Examples of the organic solvent used at this time include benzene, toluene, methanol, ethanol, acetonitrile, diethyl ether, tetrahydrofuran, dichloromethane and the like. The amount of the organic solvent used is not particularly limited as long as the transition metal compound and the compound of the formula [1] can be uniformly dissolved or dispersed.

In the present invention, the component (B) is at least one Lewis acidic compound selected from the group consisting of an organic aluminum oxy compound, an organic aluminum compound and an organic boron compound. The organic aluminum oxy compound is represented by the formula (—AlR ⁹ O—) _n (wherein R ⁹ represents a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, and 1 ≦ n ≦ 4
0. ) Is a linear or cyclic polymer. Specific examples of R ⁹ include a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, Examples include a nonyl group, a decyl group, and a mixture thereof, and a methyl group or a mixture of a methyl group and another group is particularly preferable. The number of repetitions n is preferably 2
To 40, more preferably 5 or more. Known methods for synthesizing this organoaluminum oxy compound include, for example, a method of dissolving an organoaluminum compound described below in a hydrocarbon solvent, gradually adding an equivalent amount of water to the organoaluminum compound, and hydrolyzing the hydrocarbon. A method in which copper sulfate hydrate or aluminum sulfate hydrate is suspended in a solvent, and an organic aluminum compound is brought into contact with 1 to 3 equivalents of the hydrate crystal water to slowly hydrolyze, or a hydrocarbon. It can be produced by, for example, a method in which 1 to 3 equivalents of an organoaluminum compound is brought into contact with water adsorbed on undehydrated silica gel suspended in a solvent and slowly hydrolyzed.

[0012] Organic aluminum compounds used in the present invention, wherein AlR ¹⁰ _m X _3-m (wherein, R ¹⁰ is 1 to 1 carbon atoms
0 represents a hydrocarbon group, X represents a halogen atom, and 0 ≦ m ≦ 3
It is. ). Specific examples include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, triphenylaluminum, trioctylaluminum, diisobutylaluminum chloride, diethylaluminum chloride and the like.

The organic boron compound used in the present invention includes a neutral type and an ion pair type. Neutral type organoboron compounds have the formula BR ¹¹
₃ (R ¹¹ represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, wherein the alkyl group includes a halogen-substituted alkyl group, and the aryl group includes a halogen-substituted aryl group and an alkyl-substituted aryl group. R ¹¹ may be the same or different from each other.) Specific examples of R ^11, include methyl group, ethyl group, propyl group, isobutyl group, amyl group, isoamyl group, octyl group, 2-ethylhexyl group, a pentafluorophenyl group, a tolyl group, a xylyl group, a benzyl group Can be

Specific examples of the neutral type organoboron compounds include triphenylborane, tris (pentafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane, tris (2,4, 6-trifluorophenyl) borane, tris (2,3-difluorophenyl) borane, tris (2-fluorophenyl) borane, tris [3,5-bis (trifluoromethyl) phenyl] borane, tris [4- (tri Fluoromethyl)
[Phenyl] borane, trimethylborane, triethylborane, tris (trifluoromethyl) borane, diphenylfluoroborane, bis (pentafluorophenyl) chloroborane, etc., and in particular, tris (pentafluorophenyl) borane is suitably used.

The ion pair type organic boron compound of the formula _{^{[On] + [BR 12 4}} ] - ([On] + is the Periodic Table 8
A cation of group 12 to 12 or an onium ion such as carbonium, sironium, oxonium, sulfonium, ammonium and phosphonium, [BR ¹²
_4] ^- are poor anion non-coordinating or coordinating, R ¹² is as defined above for R ^11. ). Specific examples include ferrocenium tetrakis (pentafluorophenyl) borate, silver (I) tetrakis (pentafluorophenyl) borate, copper (I) tetrakis (pentafluorophenyl) borate, and mercury (II) bis [tetrakis (pentafluorophenyl) Phenyl) borate],
Palladium (II) bis [tetrakis (pentafluorophenyl) borate], platinum (II) bis [tetrakis (pentafluorophenyl) borate], diphenylhydrocarboniumtetrakis (pentafluorophenyl) borate, triphenylcarboniumtetrakis (pentafluoro Phenyl) borate, triphenylsilonium tetrakis (pentafluorophenyl) borate, tricyclohexylcarbonium tetrakis (pentafluorophenyl) borate, triethyloxonium tetrakis (pentafluorophenyl) borate, triethylsulfonium tetrakis (pentafluorophenyl) borate, diethyl Anilinium tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (pen Fluorophenyl) borate,
Examples include tetrakis (pentafluorophenyl) borate salts such as triethylammonium tetrakis (pentafluorophenyl) borate, tetra-n-butylammonium tetrakis (pentafluorophenyl) borate, and triphenylphosphonium tetrakis (pentafluorophenyl) borate.

The catalyst according to the present invention comprises (A) a reaction product of a divalent transition metal compound of Group 10 of the periodic table with a compound represented by the general formula [1], (B) an organoaluminum oxy compound, It can be prepared by mixing a catalyst comprising at least one Lewis acidic compound selected from the group consisting of an organoaluminum compound and an organoboron compound in an inert hydrocarbon solvent or an olefin medium. The mixing order at this time is arbitrarily selected. Specific examples of the inert hydrocarbon solvent include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, and octadecane; and oils such as cyclopentane, methylcyclopentane, cyclohexane, and cyclooctane. Examples thereof include cyclic hydrocarbons, aromatic hydrocarbons such as benzene, toluene, and xylene, and petroleum fractions such as gasoline and light oil.

When the polymerization is carried out using the catalyst of the present invention, the concentration of each component varies depending on the polymerization method and various polymerization conditions and cannot be uniquely determined. Is usually used in the range of 10 ^-8 to 10 ^-1 mol / l, preferably 10 ^{-7 to} 5 × 10 ^-2 mol / l. On the other hand, when the organic aluminum oxy compound is used, the molar ratio of aluminum atom / transition metal atom of component A is usually 1 to 10 ⁶ , preferably 10 to 10 ⁴ when the organic aluminum oxy compound is used.
It is used in the range as follows. When an organoaluminum compound is used as the B component, aluminum atoms / A
The component is used in a molar ratio of transition metal atoms of usually 1 to 10 ⁵ , preferably 10 to 10 ³ . Further, when an organic boron compound is used as the component B, the molar ratio of boron atom / transition metal atom of the component A is usually 0.1 to 1
0, preferably in the range of 1-2.

The component (A) of the catalyst according to the present invention and / or
Or component (B) is silica, alumina, zirconia,
Alternatively, it can be used by being supported on a carrier such as a polymer. In the present invention, olefin polymerization is slurry polymerization,
It can be carried out in any polymerization method such as solution polymerization and gas phase polymerization. In the present invention, when performing the slurry polymerization, it is desirable that the polymerization temperature is usually in the range of -50 to 100C, preferably 20 to 90C. When performing solution polymerization, the polymerization temperature is usually 0 to 300 ° C,
Preferably, it is in the range of 100 to 250 ° C. When performing gas phase polymerization, the polymerization temperature is usually 0.
To 120 ° C, preferably 20 to 100 ° C.

The polymerization pressure is usually from normal pressure to 100 kg / c.
m ² , preferably from normal pressure to 50 kg / cm ² . The polymerization can be performed in any of a batch system, a non-continuous system, and a continuous system. Further, the polymerization can be performed in two or more stages having different reaction conditions. The molecular weight of the obtained olefin polymer can be adjusted by allowing a chain transfer agent such as hydrogen to be present in the polymerization system or by changing the polymerization temperature.

In the present invention, the catalyst of the present invention may be preliminarily polymerized with an olefin during olefin polymerization. In this case, the olefin is the catalyst 1 of the present invention.
0.05-500 g per g, preferably 0.1-10
It is desirable to prepolymerize in an amount of 0 g. In the present invention, other components effective for olefin polymerization can be contained in addition to the above-mentioned components at the time of olefin polymerization.
It is also possible to use the catalyst of the present invention in combination for the purpose of multimodal polymerization or the like, or to use other catalyst components known in the art in combination with the catalyst of the present invention.

Examples of the olefin that can be polymerized by the olefin polymerization method of the present invention include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, and 4-olefin. Methyl-1-pentene, 1-octene, 1-decene, 1-
Tetradecene, 1-hexadecene, 1-octadecene,
1-eicosene, a cyclic olefin having 3 to 20 carbon atoms,
For example, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, 2-methyl-1,
4,5,8-Dimethano-1,2,3,4,4a, 5
8,8a-octahydronaphthalene and the like can be mentioned. Further, styrene, vinylcyclohexene, diene and the like can be used. Further, copolymerization can be carried out using two or more of these olefins. For example, ethylene / propylene, ethylene / 1-butene, ethylene / 1-hexene, ethylene / 1-octene and the like.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on embodiments. In producing the transition metal compound, a commercial product was used as a raw material. The catalyst activity in the examples indicates the amount of polymer produced (kilogram) per mole of catalyst metal and one hour of reaction time. The molecular weight and molecular weight distribution of the polymer were determined from the differential refractive index using 150 CV gel permeation chromatography manufactured by Waters using polystyrene as a standard substance.

[0023]

Synthesis Example 1 Synthesis of bis (6-methyl-2-pyridyl) dimethylsilane Organomet. Chem. , 56 p. 53
(1973), ibid., 104 p. 153 (1976),
Organometallics, 9 p. 347 (1
990) and the like. Under a nitrogen atmosphere, 10.0 g (42.2 m) of 2,6-dibromopyridine was placed in a glass reactor having an internal volume of 200 ml.
mol) and 80 ml of dry tetrahydrofuran,
Cooled to -90C. To this, 27.7 ml (44.3 mmol) of a hexane solution of n-butyllithium was added, and 15
After stirring for 6 minutes, 6.29 g of methyl iodide (44.3 mm
ol). Continue stirring at -90 ° C for 30 minutes,
After warming to room temperature, it was poured into water and the product was extracted with dichloromethane. After drying over anhydrous magnesium sulfate and concentration, the resulting oily product was distilled under reduced pressure to give 2-bromo-6-
Methylpyridine was obtained in a yield of 84.1%.

Next, 3.0 g (17.4 mmol) of this 2-bromo-6-methylpyridine and 40 ml of dry tetrahydrofuran were introduced into a 200 ml glass reactor under a nitrogen atmosphere, and cooled to -78 ° C. did. Where n
11.4 ml of a hexane solution of -butyllithium (18.
After adding 3 mmol) and stirring for 50 minutes, 1.19 g (9.2 mmol) of dimethyldichlorosilane was added. −
Stirring was continued for 30 minutes at 78 ° C., and after the temperature was raised to room temperature, the product was poured into water and the product was extracted with dichloromethane. An oily product obtained by drying over anhydrous magnesium sulfate and concentrating was distilled under reduced pressure to obtain bis (6-methyl-2-pyridyl).
Dimethylsilane was obtained as colorless crystals in a yield of 60.6%.

[0025]

Synthesis Example 2 Synthesis of bis (6-trimethylsilyl-2-pyridyl) dimethylsilane Under a nitrogen atmosphere, 10.0 g (42.2 mmol) of 2,6-dibromopyridine was placed in a 200-ml glass reactor.
l) and 80 ml of dry tetrahydrofuran.
Cooled to 0 ° C. After adding 27.7 ml (44.3 mmol) of a hexane solution of n-butyllithium and stirring for 20 minutes, 4.81 g of trimethylchlorosilane (44.
3 mmol) was added. Stirring was continued for about 50 minutes at −90 ° C., and after the temperature was raised to room temperature, the product was poured into water and the product was extracted with dichloromethane. An oily product obtained by drying over anhydrous magnesium sulfate and concentrating was distilled under reduced pressure to obtain 2-bromo-6-trimethylsilylpyridine in a yield of 84.4%.

Next, 2.76 g (12.0 mmol) of this 2-bromo-6-trimethylsilylpyridine and 30 ml of dry tetrahydrofuran were added under nitrogen atmosphere to an internal volume of 20 ml.
It was introduced into a 0 ml glass reactor and cooled to -90 ° C. Here, 7.9 m of hexane solution of n-butyl lithium
1 (12.6 mmol) and stirred for about 20 minutes.
0.81 g (6.3 mmol) of dimethyldichlorosilane
Was added. Stirring was continued for 30 minutes at −90 ° C., and after the temperature was raised to room temperature, the product was poured into water and the product was extracted with dichloromethane. The oily product obtained by drying over anhydrous magnesium sulfate and concentrating was distilled under reduced pressure to obtain bis (6-trimethylsilyl-2-pyridyl) dimethylsilane as a colorless oil in a yield of 53.4%.

[0027]

[Synthesis Example 3] Synthesis of bis (2-pyridyl) dimethylsilane Under a nitrogen atmosphere, 4.74 g (30.0 mmol) of 2-bromopyridine and 60 ml of dry tetrahydrofuran were introduced into a 200 ml-volume glass reactor. Cooled to 90 ° C. Here, hexane solution of n-butyllithium 2
0.6 ml (33.0 mmol) was added over about 7 minutes, and immediately after the addition, 1.94 g of dimethyldichlorosilane was added.
(15.0 mmol) was added. Stirring was continued for about 1 hour at −90 ° C., and after the temperature was raised to room temperature, the product was poured into water and the product was extracted with dichloromethane. The oily product obtained by drying over anhydrous magnesium sulfate and concentrating was distilled under reduced pressure to obtain bis (2-pyridyl) dimethylsilane in a yield of 52.6% as a colorless oil.

[0028]

EXAMPLE 1 Under a nitrogen atmosphere, 0.463 g (1.5 mmol) of dibromo (1,2-dimethoxyethane) nickel (II) and bis (6) obtained in Synthesis Example 1 were placed in a glass reactor having an internal volume of 100 ml. 0.388 g (1.6 mmol) of -methyl-2-pyridyl) dimethylsilane was weighed, added with 20 ml of dry dichloromethane, and stirred at room temperature overnight.
The green precipitate formed was filtered off and dried under vacuum.

In a 1.6-liter autoclave purged with nitrogen, 600 ml of toluene and 5 μmo in terms of nickel were placed.
1 ml of a toluene solution of the above reaction product corresponding to 1 l, and 2.5 ml of a toluene solution of methylaluminoxane corresponding to 5 mmol in terms of aluminum are added, and ethylene is supplied at 80 ° C. and an ethylene pressure of 10 kg / cm ² G, and the total pressure is increased. The polymerization reaction was carried out for 1 hour while maintaining the temperature. After completion of the reaction, unreacted ethylene was removed, the reaction mixture was poured into hydrochloric acid-methanol, and the precipitate was separated by filtration and dried for 12 hours or more.
0.0 g of the polymer was obtained. The catalyst activity is 6000k
g / mol-Ni · hr, molecular weight Mw is 234000,
The molecular weight distribution Mw / Mn was 2.91.

[0030]

Example 2 Under a nitrogen atmosphere, 0.463 g (1.5 mmol) of dibromo (1,2-dimethoxyethane) nickel (II) and bis (6) obtained in Synthesis Example 2 were placed in a glass reactor having an inner volume of 100 ml. 0.574 g (1.6 mmol) of -trimethylsilyl-2-pyridyl) dimethylsilane was weighed, added with 20 ml of dry dichloromethane, and stirred at room temperature overnight. The green precipitate formed was filtered off and dried under vacuum.

In a 1.6-liter autoclave purged with nitrogen, 600 ml of toluene and 5 μmo in terms of nickel were placed.
1 ml of a toluene solution of the above reaction product corresponding to 1 l, and 2.5 ml of a toluene solution of methylaluminoxane corresponding to 5 mmol in terms of aluminum are added, and ethylene is supplied at 80 ° C. and an ethylene pressure of 10 kg / cm ² G, and the total pressure is increased. The polymerization reaction was carried out for 1 hour while maintaining the temperature. After completion of the reaction, unreacted ethylene was removed, the reaction mixture was poured into hydrochloric acid-methanol, and the precipitate was separated by filtration and dried for 12 hours or more.
3.7 g of polymer were obtained. Catalyst activity is 2740k
g / mol-Ni · hr, molecular weight Mw is 583000,
The molecular weight distribution Mw / Mn was 2.44.

[0032]

Example 3 In a nitrogen atmosphere, 0.463 g (1.5 mmol) of dibromo (1,2-dimethoxyethane) nickel (II) and bis (2 -Pyridyl) dimethylsilane 0.3
43 g (1.6 mmol) was weighed, 15 ml of dry dichloromethane was added, and the mixture was stirred at room temperature overnight. The green precipitate formed was filtered off and dried under vacuum.

In a 1.6-liter autoclave purged with nitrogen, 600 ml of toluene and 5 μmo in terms of nickel were placed.
1 ml of a toluene solution of the above reaction product corresponding to 1 l, and 2.5 ml of a toluene solution of methylaluminoxane corresponding to 5 mmol in terms of aluminum are added, and ethylene is supplied at 80 ° C. and an ethylene pressure of 10 kg / cm ² G, and the total pressure is increased. The polymerization reaction was carried out for 1 hour while maintaining the temperature. After completion of the reaction, unreacted ethylene was removed, the reaction mixture was poured into hydrochloric acid-methanol, and the precipitate was separated by filtration and dried for 12 hours or more.
1.9 g of polymer were obtained. Catalyst activity is 4380k
g / mol-Ni · hr, molecular weight Mw is 325,000,
The molecular weight distribution Mw / Mn was 2.43.

[0034]

When olefin polymerization is carried out using the novel catalyst of the present invention, a high molecular weight olefin polymer having a narrow molecular weight distribution can be obtained without impairing the polymerization activity even at a high temperature of 50 ° C. or higher.

[Brief description of the drawings]

FIG. 1 is a flowchart showing a process for preparing an olefin polymerization catalyst of the present invention.

Claims (1)

[Claims] 1. A transition metal belonging to Group 10 of the bivalent periodic table
Reaction product between a compound and a compound represented by the following general formula [1]
Product, and (B) an organoaluminum oxy compound, having
Consisting of organic aluminum compounds and organic boron compounds
From at least one Lewis acidic compound selected from
Polymerizing an olefin in the presence of a catalyst. Embedded image(Where R¹~ R⁸Are each independently a hydrogen atom, halogen
Atoms, hydrocarbon groups having 1 to 20 carbon atoms, and
C1-C20 silyl group-substituted hydrocarbons substituted with iodine
Silyl substituted by a hydrocarbon group having 1 to 20 carbon atoms
Group, an alkyloxy group having 1 to 20 carbon atoms, and a part of hydrogen.
Or a fluorocarbon group having 1 to 20 carbon atoms, all of which are substituted with fluorine groups.
Represents a fluoro hydrocarbon group, and Z is unsubstituted or has 1 to 1 carbon atoms.
A methylene group substituted with a hydrocarbon group of 20;
A silylene group substituted with 20 hydrocarbon groups, carbonyl
A divalent linking group selected from the group consisting of¹When
R ^Two, R^TwoAnd R^Three, R^ThreeAnd R^Four, R^FiveAnd R⁶, R⁶And R
⁷, R⁷And R⁸Are each independently bonded to each other to form a fused ring
May be formed. )