KR100583822B1 - Unsymmetrical unbridged metallocene compounds and catalyst-compositions comprising the same - Google Patents

Abstract

The present invention relates to an asymmetric uncrosslinked metallocene compound and a catalyst composition comprising the same, wherein the general formula (Cp ^* R ¹ ) (CpR ² ) MX ₂ (where Cp ^* is a cyclopentadienyl radical substituted with cycloalkyl) And cycloalkyl substituted by cyclopentadienyl is one selected from a cyclohydrocarbyl radical having 3 to 11 carbon atoms, Cp is a radical having a cyclopentadienyl nucleus, and R ¹ and R ² are each Cp ^* and One or more substituents each substituted with Cp, these substituents may be the same or different from one another, hydrogen, phosphine, amino, alkyl having 1 to 20 carbon atoms, alkoxy, alkylamino, dialkylamino, alkoxy-alkyl, aryl, aryl Is an oxy-alkyl, alkenyl, alkylaryl, or arylalkyl radical, M is a transition metal of group 4B, 5B or 6B of the periodic table, X may be the same or different and is halogen, in carbon atoms Provides a metallocene compound of the 20-alkyl, aryl, alkenyl, alkylaryl, arylalkyl, alkoxy, and aryl is one member selected from the group consisting of hydroxy radicals.) Metal for olefin polymerization is represented by. The metallocene compound has excellent catalytic activity, and by using this, it is possible to polymerize a polyolefin having a large molecular weight.

Metallocene Catalyst, Aluminoxane, Olefin Polymerization, Cycloalkyl, Cyclopentadienyl

Description

Asymmetric unbridged metallocene compounds and catalyst-compositions comprising the same}

[Industrial use]

The present invention relates to a metallocene compound, and more particularly, to a metallocene compound used as a catalyst for olefin polymerization and a catalyst composition comprising the same.

[Prior art]

Catalysts containing transition metals are generally used for the polymerization of olefins. In particular, German Patent Nos. 2,608,933, 3,007,725 and the like are metals composed of a periodic table 4B transition metal such as zirconium, titanium and hafnium and a ligand of a cyclopentadiene-based structure. The use of a rosene compound with an active agent, such as methylaluminoxane, as a catalyst for olefin polymerization is disclosed. Examples of ligand compounds having a cyclopentadiene-based structure disclosed in these known patents include cyclopentadiene, indene, fluorene, substituted cyclopentadiene, substituted indene, substituted prue Oren.

Many types of cyclopentadiene-based metallocene compounds can be used in the catalyst system for olefin polymerization. The chemical structure change of cyclopentadiene-based metallocene has been known to have an important effect on the suitability of metallocene as a polymerization catalyst. . For example, the size and position of the substituents attached to the cyclopentadienyl ring have a great influence on the activity of the catalyst, stereospecificity of the catalyst, safety of the catalyst, and physical properties of the polymer that can be obtained by the polymerization reaction. Recently, it has been found that a catalytic system composed of substituted cyclopentadiene-based metallocenes and methylaluminoxanes containing zirconium as transition metals has high activity in olefin polymerization, which is described in European Patent Nos. 129,368, US Pat. No. 4,874,880, No. 5,324,800, Makromol. Chem. Rapid Commun., 4, 417 (1983), and the like.

Further, examples of metallocenes composed of zirconium and cyclopentadienyl ligands substituted with hydrocarbyl groups include bis (alkylcyclopentadienyl) zirconium dichloride, wherein alkyl is methyl, ethyl, isopropyl, tert-propyl Or trimethylsilyl) (J. Chem. Soc. Dalton Trans., 805 (1981)), bis (pentamethylcyclopentadienyl) zirconium dichloride (J. Amer. Chem. Soc., 100, 3078 (1978) ), (Pentamethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride (J. Amer. Chem. Soc., 106, 6355 (1984)), bis (di, tri, or tetra alkyl-cyclopentadiene Nil) zirconium dichloride (US Pat. No. 4,874,880) and the like are known, and most of these metallocene compounds are symmetric, non-crosslinked metallocenes comprising two identical cyclopentadienyl ligands.

On the other hand, asymmetric uncrosslinked metallocenes include (cyclopentadienyl) (indenyl) and (cyclopentadienyl) (fluorenyl) metallocene (US Pat. No. 5,541,272), (substituted indenyl) ( Metallocenes consisting of cyclopentadienyl (US Pat. Nos. 5,223,467 and 5,780,659) and the like are known. The asymmetric uncrosslinked (cyclopentadienyl) (indenyl) zirconium dichloride disclosed in U.S. Pat. It was found to be excellent.

Such known metallocenes, however, are symmetric, uncrosslinked bis (cyclopentadienyl) based metallocenes, asymmetric uncrosslinked (substituted or unsubstituted indenyl) (unsubstituted cyclopentadienyl) metals Most of the rosenes are asymmetric, uncrosslinked (substituted cyclopentadienyl) (cyclopentadienyl) metallocenes, and the substituents of substituted cyclopentadienyls are bulky-cycloalkyl metallocenes. An example of did not appear. In addition, in terms of commercial applications, many of the non-crosslinkable metallocene catalyst compositions do not sufficiently exhibit the polymerization activity of olefins and have difficulty in polymerizing a large molecular weight polyolefin.

The present inventors use a metallocene compound comprising a cyclopentadienyl ligand having another bulky-cycloalkyl substituent, another cyclopentadienyl ligand, and a transition metal to form a catalyst system for olefin polymerization. The present invention has been accomplished by discovering that it can be manufactured efficiently.

It is therefore an object of the present invention to provide an asymmetric uncrosslinked metallocene compound comprising a cyclopentadienyl ligand with a bulky-cycloalkyl substituent. It is another object of the present invention to provide a metallocene compound capable of producing commercially useful high activity and high molecular weight polyolefins and a catalyst composition comprising the same. Still another object of the present invention is to provide an olefin polymerization method using the metallocene compound and the catalyst composition including the same.

In order to achieve the above object, the present invention provides a metallocene compound for olefin polymerization represented by the following formula (1).

[Formula 1]

(Cp ^* R ¹ ) (CpR ² ) MX ₂

Here, Cp ^* is a cyclopentadienyl radical substituted with cycloalkyl, cycloalkyl substituted with cyclopentadienyl is one selected from a cyclohydrocarbyl radical having 3 to 11 carbon atoms, and Cp is cyclopentadienyl A radical having a nucleus, and R ¹ and R ² are one or more substituents each substituted with Cp ^* and Cp, and these substituents may be the same or different from each other, hydrogen, phosphine, amino, alkyl having 1 to 20 carbon atoms, Alkoxy, alkylamino, dialkylamino, alkoxy-alkyl, aryl, aryloxy-alkyl, alkenyl, alkylaryl, or arylalkyl radicals, M is a transition metal of group 4B, 5B or 6B of the periodic table, and X is the same Or may be different and is one selected from the group consisting of halogen, alkyl having 1 to 20 carbon atoms, aryl, alkenyl, alkylaryl, arylalkyl, alkoxy and aryloxy radicals.

The present invention is also selected from the group consisting of a metallocene compound for olefin polymerization of Formula 1, and an aluminoxane of Formula 2 or Formula 3, an aromatic boron-based ionic compound substituted with fluorine, and a modified clay. It provides a metallocene catalyst composition comprising the above.

[Formula 2]

[Formula 3]

In Formulas 2 and 3, R 'is a hydrocarbon radical having 1 to 10 carbon atoms, x is an integer of 1 to 50, y is an integer of 3 to 50.

Hereinafter, the present invention will be described in detail.

The present invention provides a metallocene of Chemical Formula 1 including a cyclopentadienyl ligand (Cp ^* R ¹ ), a cyclopentadienyl ligand (CpR ² ), and a transition metal (M) to which the ligands are bonded, having a cycloalkyl substituent. It provides a compound and a metallocene catalyst composition comprising the same.

The metallocene compound of Chemical Formula 1 may be prepared according to a known asymmetric uncrosslinked metallocene compound manufacturing method, for example, an alkali metal salt of a cyclopentadienyl compound substituted with a cycloalkyl as shown in Scheme 1 below. It can be prepared by reacting (M ′ (Cp ^* R ¹ )) with an appropriate transition metal compound ((CpR ² ) MX ₃ ).

Scheme 1

M ′ (Cp ^* R ¹ ) + (CpR ² ) MX ₃ → (Cp ^* R ¹ ) (CpR ² ) MX ₂

It is preferable that cycloalkyl substituted by the said cyclopentadienyl compound is 1 type chosen from the C3-C11 cyclohydrocarbyl radical. The alkali metal salt (M ′ (Cp ^* R ¹ )) of the cyclopentadienyl compound substituted with the cycloalkyl may be prepared according to various known methods, and typically, a cyclopentadienyl compound substituted with a cycloalkyl is prepared. It may be prepared by reacting with a compound containing an alkali metal (M ′) such as lithium, sodium, potassium, or the like, for example, a metallization reagent such as butyllithium. In general, the conversion of the cyclopentadienyl compound substituted with cycloalkyl to the alkali metal compound is carried out for 2 to 40 hours at a temperature of −78 to 100 ° C. in the presence of a solvent and an inert atmosphere such as nitrogen. In this case, as the solvent, diethyl ether, diethylene glycol diethyl ether, tetrahydrofuran (THF), pentane, hexane, heptane, and the like may be used, and preferably diethyl ether, tetrahydrofuran (THF), pentane, or the like. Hexane is used. The alkali metal salt of the cyclopentadienyl compound substituted with the cycloalkyl obtained may be used directly in the reaction of the next step, or may be obtained as a metal compound in the form of a solid powder and then used in the next reaction.

M of (CpR ² ) MX ₃ is a transition metal of group 4B, 5B or 6B of the periodic table, preferably one selected from titanium, zirconium or hafnium of group 4B, and Cp is an organic group having a cyclopentadienyl nucleus. As (radical), preferably cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, fluorenyl radical, and the like, R ² is one or more substituted with Cp As substituents, these substituents may be the same or different from one another and include hydrogen, phosphine, amino, alkyl having 1 to 20 carbon atoms, alkoxy, alkylamino, dialkylamino, alkoxy-alkyl, aryl, aryloxy-alkyl, alkenyl, Alkylaryl, or an arylalkyl radical, X may be the same or different and is selected from the group consisting of halogen, alkyl having 1 to 20 carbon atoms, aryl, alkenyl, alkylaryl, arylalkyl, alkoxy and aryloxy radicals As, preferably Cl, B r or I.

The reaction of M '(Cp ^* R ¹ ) and (CpR ² ) MX _{3 in} the reaction scheme 1 is preferably carried out by dissolving the same chemical equivalents in a solvent and slowly mixing. The reaction is carried out in the presence of a solvent and at -78 to 100 ° C. for 1 hour to 3 days. As the solvent, diethyl ether, diethylene glycol diethyl ether, tetrahydrofuran (THF), dichloromethane and the like can be used. have. The reaction product produced by the above reaction is preferably used after purification by methods such as solvent removal, filtration, recrystallization and sublimation.

In the metallocene compound of Formula 1, X is halogen, in particular X is a chlorine atom, M is zirconium, or (Cp ^* R ¹ ) is (cyclopentyl cyclopentadienyl), (1-methyl-3 -Cyclopentyl cyclopentadienyl), (1-ethyl-3-cyclopentyl cyclopentadienyl), (1-butyl-3-cyclopentyl cyclopentadienyl), (cyclohexyl cyclopentadienyl), (1 -Methyl-3-cyclohexyl cyclopentadienyl), (1-ethyl-3-cyclohexyl cyclopentadienyl), (1-butyl-3-cyclohexyl cyclopentadienyl), (cyclohexylmethylenyl cyclopentayl) A radical selected from the group consisting of: dienyl), (cycloheptyl cyclopentadienyl), ((4-methylcyclohexyl) cyclopentadienyl), (cyclohexylethylenyl cyclopentadienyl) and analogs thereof, and (CpR ²⁾ a cyclo-pentadienyl La Knife or pentamethyl cyclo-pentadienyl radical and is preferably excellent in the activity of the catalyst, as a more preferred embodiment, illustrating when the metallocene compounds of zirconium include transition metal as follows.

(Cyclopentyl cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1-methyl-3-cyclopentyl cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1-ethyl-3-cyclo Pentyl cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1-butyl-3-cyclopentyl cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (cyclopentyl cyclopentadienyl) (penta Methylcyclopentadienyl) zirconium dichloride, (1-methyl-3-cyclopentyl cyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (1-ethyl-3-cyclopentyl cyclopentadienyl) (Pentamethylcyclopentadienyl) zirconium dichloride, (1-butyl-3-cyclopentyl cyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, Clohexyl cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1-methyl-3-cyclohexyl cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1-ethyl-3-cyclohexyl Cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1-butyl-3-cyclohexyl cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (cyclohexyl cyclopentadienyl) (pentamethyl Cyclopentadienyl) zirconium dichloride, (1-methyl-3-cyclohexyl cyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (1-ethyl-3-cyclohexyl cyclopentadienyl) ( Pentamethylcyclopentadienyl) zirconium dichloride, (1-butyl-3-cyclohexyl cyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (cycle Lohexylmethylenyl cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (cycloheptyl cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1-methyl-3-cycloheptyl cyclopentadienyl ) (Cyclopentadienyl) zirconium dichloride, (1-ethyl-3-cycloheptyl cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1-butyl-3-cycloheptyl cyclopentadienyl) ( Cyclopentadienyl) zirconium dichloride, (cyclohexylethylenyl cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, and similar compounds thereof.

In addition, a similar list of metallocene compounds including titanium and hafnium transition metals can be made, and the metallocene compounds according to the present invention are not limited to the examples given in the above list, and other (cycloalkyl) not shown in the examples. Cyclopentadienyl) (cyclopentadienyl) zirconium dichloride with substituents, (cyclopentadienyl with cycloalkyl substituents) (cyclopentadienyl) titanium dichloride, (cyclopentadienyl with cycloalkyl substituents) (Cyclopentadienyl) hafnium dichloride and the like can also be included in the examples of the present invention.

The metallocene compound of the present invention may be used in combination of two or more kinds or alone, and may be used as a polymerization catalyst of an olefin monomer with a suitable cocatalyst. If necessary, the metallocene compound and / or the activator may be supported on a solid carrier and used as a solid supported catalyst. Examples of the active agent may include methyl aluminoxane (MAO), modified methyl aluminoxane (MMAO), and the like, and tri (butyl) ammonium tetra (pentafluorophenyl) boron, N, Aromatic boron-based ionic compounds substituted with fluorine such as N-dimethylanilinium tetra (pentafluorophenyl) boron, or N, N-dimethylanilinium montmorillonite (N, N-dimethylanilinium montmorillonite), N Modified clays such as N, N-dimethylanilinium hectorite and the like can also be used as the active agent.

As the methyl aluminoxane (MAO) or modified methyl aluminoxane (MMAO) activator any commercially available aluminoxane may be used, and an appropriate amount of water is added to trialkylaluminum, or a hydrocarbon compound or inorganic containing water. It can also be manufactured and used by a well-known method, such as making a hydrate salt and a trialkyl aluminum react. The aluminoxane is generally obtained in the form of a mixture of linear and circular aluminoxanes as shown in formulas (2) and (3), respectively. In the present invention, such linear or circular aluminoxanes may be used alone or in combination. Such aluminoxanes are commercially available in various forms of hydrocarbon solution. Among them, aromatic hydrocarbon solution aluminoxane is preferably used, and more preferably, aluminoxane solution dissolved in toluene.

[Formula 2]

[Formula 3]

In Formulas 2 and 3, R 'is a hydrocarbon radical, preferably a linear or branched alkyl radical of 1 to 10 carbon atoms, more preferably a majority of R' is a methyl group, x Is an integer of 1-50, Preferably it is an integer of 10-40, y is an integer of 3-50, Preferably it is an integer of 10-40.

The amount of the activator used with the metallocene compound of the present invention can be varied in a wide range, wherein the molar ratio of aluminum of aluminoxane to the transition metal of the metallocene compound ([aluminum]: [transition metal]) is 1 It may be selected in the range of 1: 1 to 100,000: 1, and more preferably used in a molar ratio of 5: 1 to 15,000: 1.

The catalyst composition of the present invention may be used for the polymerization of olefins in a solution state in which the metallocene compound and the activator are uniformly dissolved in a hydrocarbon solvent and the like, and the metallocene compound and / or the activator may be an inorganic oxide carrier (eg, silica, alumina, Silica-alumina mixtures, etc.) or insoluble particles thereof. Therefore, the catalyst composition for olefin polymerization composed of the metallocene compound and the active agent of the present invention can be applied to all of the solution, slurry or gas phase polymerization of olefin, and the respective polymerization reaction conditions are the type of metallocene compound used and the metallocene. It can be set in various ways depending on the state of the catalyst consisting of an active agent (uniform or heterogeneous phase (support type)), the polymerization method (solution polymerization, slurry polymerization, gas phase polymerization), the desired polymerization result or the type of polymer. .

The metallocene compound of the present invention can polymerize ethylene together with an aluminoxane activator in the presence of various other olefins. The other olefins include α-olefin hydrocarbons having 2 to 12 carbon atoms, preferably 3 to 10 carbon atoms, For example, propylene, butene-1, pentene-1, 3-methylbutene-1, hexene-1, 4-methylpentene-1, 3-methylpentene-1, heptene-1, octene-1, decene-1 ( decene-1), 4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene, 3,4-dimethyl-1-hexene, derivatives thereof, mixtures of these olefins, and the like.

The olefin polymerization is carried out in the presence of liquid or gaseous diluents, which must be non-reactive substances which do not adversely affect the catalyst system, for example propane, butane, isobutane, pentane, hexane, heptane, octane , Cyclohexane, methylcyclohexane, toluene, xylene, derivatives thereof, mixtures thereof and the like can be used, and the poisoning substances of the catalyst present in the reaction medium are preferably removed before the olefin is polymerized.

The olefin polymerization temperature may vary depending on the reactants, reaction conditions, and the like. A typical polymerization temperature is about 20 to 200 ° C., and a polymerization pressure is 10 to 7000 psig. The molecular weight of the polymer produced using the polymerization catalyst of the present invention can be controlled by changing the polymerization temperature or by injecting hydrogen into the reactor.

The following presents a preferred embodiment to aid the understanding of the present invention. However, the following examples are provided to more easily understand the present invention, and do not limit the present invention.

In the following examples, the metallocene compound of the present invention was prepared under Schlenk technique in which air and moisture were completely blocked, and purified dried nitrogen was used as an inert gas. In addition, the solvent was mostly dried in the presence of sodium metal under an inert nitrogen atmosphere, and in the case of dichloromethane, dried in the presence of calcium hydride. Deuterated solvent for nuclear magnetic spectroscopic analysis was used by storing a molecular sieve.

Example 1 Preparation of (cyclopentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride

137 g (919 mmol) of cyclopentylbromide are dissolved in 300 mL of tetrahydrofuran solvent in a 2000 mL volumetric flask in a nitrogen atmosphere, and the mixture is cooled to 0 ° C with an ice water bath. To this was added 460 mL of sodium cyclopentadiene (2.0 M tetrahydrofuran solution) dropwise for 60 minutes, and then left to stand and stirred at room temperature overnight. The solvent was removed in vacuo, extracted with hexane, filtered, and analyzed by gas chromatography. As a result, 78% of cyclopentyl cyclopentadiene and two cyclopentyl added dicyclopentyl cyclopentadiene isomers were approximately 15%. 102 g were obtained, which was vacuum distilled to obtain 65 g of cyclopentyl cyclopentadiene (yield 52.7%).

The compound was added to a flask, dissolved in 400 mL of tetrahydrofuran, cooled to -78 ° C, and 296 mL of normal butyllithium (1.6 M hexane solution) was added dropwise for 1 hour, and then slowly warmed to room temperature, followed by stirring for 3 hours. In another flask, 124.3 g of CpZrCl ₃ was added, 300 mL of hexane was injected, cooled to −78 ° C., and then 200 mL of tetrahydrofuran was added while stirring, and the temperature was slowly raised to room temperature. The anion of the first flask was slowly transferred to the reaction of the second flask at 0 ° C. and stirred overnight. The solvent was removed in vacuo, extracted with 300 mL dichloromethane, filtered and the solvent removed again. 1000 mL of hexane was injected to slurry the reaction product, which was filtered, washed with 500 mL of hexane, and dried in vacuo to obtain 120 g of (cyclopentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride.

The 1 H NMR (CDCl ₃ , ppm) analysis of the obtained (cyclopentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride compound showed 6.46 (s, 5H), 6.25-6.33 (m, 4H), 3.20 ~ 3.14 (m, 1H) and 1.48-2.06 (m, 8H).

Example 2: Preparation of (1,2 / 1,3-methylcyclopentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride

8 g (99.85 mmol) of methylcyclopentadiene obtained through pyrolysis and distillation of methylcyclopentadiene dimer was placed in a flask, and 200 mL of tetrahydrofuran was injected, cooled to -78 ° C with stirring, and normal butyllithium (1.6 M hexane solution) 62.4 mL was slowly added dropwise, and then heated to room temperature and stirred for 2 hours. The reaction flask was cooled to 0 ° C. and 14.9 g of cyclopentylbromide was slowly added dropwise and stirred overnight. The solvent was removed in vacuo, extracted with hexane, filtered and the solvent was removed again to obtain 3.4 g (37.3%) of 1,2 / 1,3-methylcyclopentylcyclopentadiene through vacuum distillation. The compound was placed in a flask, and 60 mL of tetrahydrofuran was injected, cooled to −78 ° C. while stirring, 22.6 mL of normal butyllithium (1.6 M hexane solution) was added dropwise for 30 minutes, and then slowly warmed to room temperature, followed by stirring for 3 hours. In another flask, 9.5 g of CpZrCl ₃ was added, 30 mL of hexane was injected, cooled to −78 ° C., and 30 mL of tetrahydrofuran was added while stirring, and the temperature was slowly raised to room temperature. The anion of the first flask was slowly transferred to the reaction of the second flask at 0 ° C. and stirred overnight. The solvent was removed in vacuo, extracted with 30 mL dichloromethane, filtered and the solvent removed again. 150 mL of hexane was injected to slurry the reaction product, which was filtered, washed with 30 mL of hexane, washed with 30 mL, and dried in vacuo to give 10.5 g of (1,2 / 1,3-methylcyclopentylcyclopentadienyl) (cyclopentadienyl). Zirconium dichloride was obtained in a mixture of 1/1.

The 1 H NMR (CDCl ₃ , ppm) analysis of the obtained (1,2 / 1,3 cyclopentyl-cyclopentadienyl) (cyclopentadienyl) zirconium dichloride mixture showed 6.43 and 6.44 (s, 5H), 5.97 ˜6.28 (m, 3H), 3.07 (m, 1H), 2.23 and 2.17 (s, 3H), and 1.1-2.02 (m, 9H).

Example 3: Preparation of (cyclohexylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride

8 g of cyclohexyl cyclopentadiene was obtained using 13.4 g of cyclohexyl bromide instead of the cyclopentyl bromide of Example 1, and reacted with CpZrCl ₃ as in Example 1 to 9.5 g of (cyclohexyl cyclopentadienyl) (cyclo Pentadienyl) zirconium dichloride was obtained. The result of 1 H NMR (CDCl ₃ , ppm) analysis of the obtained (cyclopentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride compound was 6.46 (s, 5H), 6.23-6.31 (m, 4H), 2.82 ~ 2.75 (m, 1H) and 1.01-2.10 (m, 10H).

Example 4: Preparation of (cycloheptylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride

14 g of cycloheptyl bromide was used instead of the cyclopentyl bromide of Example 1 to obtain 10.1 g of cycloheptylcyclopentadiene, which was reacted with CpZrCl ₃ as in Example 1 to 11.5 g of (cyclohexyl cyclopentadienyl) (cyclo Pentadienyl) zirconium dichloride was obtained. The result of 1 H NMR (CDCl ₃ , ppm) analysis of the obtained (cyclopentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride compound was 6.41 (s, 5H), 6.20-6.32 (m, 4H), 2.95∼ 3.01 (m, 1H) and 1.32-2.13 (m, 12H).

Example 5: (Cyclopentylcyclopentadienyl) (Cyclopentadienyl) Preparation of a Supported Catalyst of Zirconium Dichloride

15 mg of MAO (10% toluene solution, Al 4.64 wt%) was injected into 74 mg of the compound prepared in Example 1, and ultrasonic wave was injected for 1 hour (sonication through an oil bath), and silica (Grace D-948 grade) was added thereto. 4 g was added and the ultrasound was injected for 1 hour. The solution was discarded, 40 mL of hexane was injected, shaken for 5 minutes, and the filtrate was discarded again five times, followed by drying in vacuo to prepare a supported catalyst. The contents of Zr and Al components of the supported catalyst were 0.31 and 10.2 weight percent, respectively, as confirmed by ICP-MS.

Example 6. Preparation of a Supported Catalyst of (1,2 / 1,3-Methylcyclopentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride

The title supported catalyst was prepared in the same manner as in Example 5, except that 77 mg of the compound prepared in Example 2 was used. The contents of Zr and Al components of the supported catalyst were 0.3 and 10.1 weight percent, respectively, as confirmed by ICP-MS.

Example 7. (Cyclopentylcyclopentadienyl) (Cyclopentadienyl) Preparation of a Complex Supported Catalyst of Zirconium Dichloride

15 mg of MAO (10% toluene solution, Al 4.64 wt%) was injected into 74 mg of the compound prepared in Example 1, and ultrasonic wave was injected for 1 hour (sonication through an oil bath), and silica (Grace D-948 grade) was added thereto. 4 g was added and the ultrasound was injected for 1 hour. 5 mL of MAO (10% toluene solution, Al 4.64wt%) was injected into 28 mg of ethylenebis (indenyl) zirconium dichloride, and ultrasonic waves were injected for 1 hour, and then transferred to the previous reaction, and ultrasonic waves were injected for 1 hour. The solution was discarded, 40 mL of hexane was injected, shaken for 5 minutes, and the filtrate was discarded again five times, followed by drying in vacuo to prepare a supported catalyst. The contents of Zr and Al components of the supported catalyst were 0.36 and 12.5 weight percent, respectively, as confirmed by ICP-MS.

Example 8. Preparation of Complex Supported Catalyst of (1,2 / 1,3-Methylcyclopentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride

The title supported catalyst was prepared in the same manner as in Example 7, except that 77 mg of the compound prepared in Example 2 was used. The contents of Zr and Al components of the supported catalyst were 0.38 and 12.0 weight percent, respectively, as confirmed by ICP-MS.

Example 9. Ethylene Polymerization

In a glove box, the metallocenes prepared in Examples 1-4 and bis (cyclopentadienyl) zirconium dichloride and bis (indenyl) zirconium dichloride, respectively, were placed in flasks and dissolved in 30 mL of toluene. After taking 6.0 μmol of metallocene solution, put it in another flask, add Methyl aluminoxane solution (MAO solution) (Albemarle Co .; 10 wt% MAO in toluene) so that the Al / Zr molar ratio was 2,500. Agitated to prepare a catalyst solution.

A 1L stainless autoclave reactor equipped with a jacket for supplying external cooling water to control the polymerization temperature was washed once with propane and 5 times ethylene at about 85 ℃ before polymerization to completely remove impurities and return to room temperature. Lowered the temperature. After adding 300 mL of hexane dried at room temperature and 0.5 mmol of triisobutylaluminum (TIBAL) as an impurity remover, and then raising the temperature to 70 ° C., the prepared catalyst solution was added directly to the reactor and ethylene (10 psig pressure) was added. After the reaction was raised to 14 psig, the polymerization was carried out for 1 hour, and the reaction mixture was discharged and cooled to terminate the polymerization. A solution containing about 5% hydrogen chloride (HCl) in 300 mL methanol was added to the reaction mixture and stirred for about 2 hours to neutralize the MAO component and active catalyst component remaining in the polymer. The slurry containing the polymer was filtered and washed with 2 liters of water to remove the hydrogen chloride component, and the polymer obtained by drying in a dryer at a temperature of 60 ° C. was obtained. The results for polymerization yield, activity of catalyst, molecular weight and molecular weight distribution of the polymer are shown in Table 1 below.

Catalytic system Yield (g) activation Average molecular weight Molecular Weight Distribution (Mw / Mn) Compound of Example 1 34.0 5,600 69,800 3.1 Compound of Example 2 33.5 5,580 64,500 4.7 Compound of Example 3 22.3 3,720 65,000 3.6 Compound of Example 4 17.8 2,960 63,700 3.4 Comparative Example 1: (Cp) ₂ ZrCl ₂ 10 1,660 26,000 2.8 Comparative Example 2: (Ind) ₂ ZrCl ₂ 15 2,450 54,000 4.8

     In Table 1, the activity indicates the weight of the polyethylene polymerized per unit catalyst, kgPE / mol Zr. Hours at ethylene pressure of 10 psig, 70 ° C, and the average molecular weight (Mw) is in units of g / mol. As shown in Table 1, the metallocene catalyst system consisting of cyclopentadienyl ligand and cyclopentadienyl ligand having a cycloalkyl substituent is excellent in terms of activity, and in particular, cyclopentadier having a cyclopentyl substituent The metallocene catalyst system composed of the nil and cyclopentadienyl ligands shows excellent activity and can produce polymers of higher molecular weight, so that a polymer having a wider molecular weight control range can be obtained by a molecular weight modifier such as hydrogen. It can be seen.

Example 10 Ethylene / Hexene Copolymerization of Supported Catalysts

A 1L stainless autoclave reactor equipped with a jacket for supplying external cooling water to control the polymerization temperature was washed once with propane and 5 times ethylene at about 85 ℃ before polymerization to completely remove impurities and return to room temperature. Lowered the temperature. 400 mL of propane and 1.0 mmol of triisobutylaluminum were added to the 1 L high-pressure reactor, and the mixture was stirred at 70 ° C. Then, 100 mL of propane and a predetermined amount of the supported catalyst prepared in Examples 5-8 were added to the reactor, so that the ethylene partial pressure was 120 psig. Ethylene and 37 ml of 1-hexene were added and polymerization was carried out for 60 minutes at 70 ° C. maintaining the reactor total pressure at 490 psig. After completion of the polymerization reaction, 1-hexene and propane remaining without reaction were discharged, and the reactor was easily opened to recover a free-flowing polymer, and no fouling phenomenon was observed. The physical properties of the polymer thus prepared were measured and shown in Table 2.

Catalytic system Catalyst usage (mg) Yield (g) activation Oil Index (g / 10min) Polymer density (g / cc) Supported catalyst of Example 5 32 86.0 2.69 0.31 0.9188 Supported catalyst of Example 6 33 69.4 2.10 0.28 0.9167 Supported catalyst of Example 7 20 128.8 6.44 0.1 0.9029 Supported catalyst of Example 8 25 118.2 4.73 0.12 0.9162

    In Table 2, the activity represents the ethylene pressure 120psig, the unit time at 70 ℃, the weight of the polymerized polyolefin per kg catalyst (kgPolymer / g catalyst. Time), the melt index is ASTM D1238, polymer density is ASTM D1505 test method Measured accordingly.

When a novel asymmetric non-crosslinked metallocene compound composed of a cyclopentadienyl and cyclopentadienyl ligand having a cycloalkyl substituent of the present invention and a transition metal (titanium, zirconium, hafnium, etc.) is used as a catalyst for olefin polymerization, Polyolefin can be manufactured by polymerization activity. In particular, by changing the type and structure of cyclopentadienyl radicals substituted with cycloalkyl of the metallocene compound of the present invention, not only polyolefins of various physical properties can be prepared, but also prepared as supported catalysts, slurry And it can be applied to gas phase polymerization to prepare a spherical particulate polyolefin.

Claims (11)

An asymmetric uncrosslinked metallocene compound of formula (Cp ^* R ¹ ) (CpR ² ) MX ₂ , wherein Cp ^* is a cyclopentadienyl radical substituted with one radical selected from cycloalkyl radicals having 3 to 11 carbon atoms and, Cp is cyclo pentadienyl a radical with a carbonyl nucleus, R ¹ and R ² is one or more substituents, each substituted on Cp ^* and Cp, these substituents may be the same or different from each other, hydrogen, phosphine, amino, Alkyl, alkoxy, alkylamino, dialkylamino, alkoxy-alkyl, aryl, aryloxy-alkyl, alkenyl, alkylaryl, or arylalkyl radical of 1 to 20 carbon atoms, M is a group of 4B, 5B or 6B of the periodic table Is a transition metal, X may be the same or different and is selected from the group consisting of halogen, hydrogen, alkyl having 1 to 20 carbon atoms, aryl, alkenyl, alkylaryl, arylalkyl, alkoxy and aryloxy radicals.) . The metallocene compound of claim 1, wherein X is halogen. The metallocene compound according to claim 2, wherein X is a chlorine atom. The metallocene compound according to claim 1, wherein M is zirconium. The method according to claim 4, wherein (Cp ^* R ¹ ) is (cyclopentyl cyclopentadienyl), (1-methyl-3-cyclopentyl cyclopentadienyl), (1-ethyl-3-cyclopentyl cyclopentadiene Yl), (1-butyl-3-cyclopentyl cyclopentadienyl), (cyclohexyl cyclopentadienyl), (1-methyl-3-cyclohexyl cyclopentadienyl), (1-ethyl-3-cyclo Hexyl cyclopentadienyl), (1-butyl-3-cyclohexyl cyclopentadienyl), (cyclohexylmethylenyl cyclopentadienyl), (cycloheptyl cyclopentadienyl), and (cyclohexylethylenyl cyclopentayl) Metallocene compound which is a radical selected from the group which consists of dienyl). The metallocene compound of claim 4, wherein (CpR ² ) is a cyclopentadienyl radical or a pentamethylcyclopentadienyl radical. a) at least ^one asymmetric non-crosslinked metallocene compound of formula (Cp ^* R ¹ ) (CpR ² ) MX ₂ , wherein Cp ^* is substituted with one radical selected from cycloalkyl radicals having 3 to 11 carbon atoms A cyclopentadienyl radical , Cp is a radical having a cyclopentadienyl nucleus, and R ¹ and R ² are one or more substituents each substituted with Cp ^* and Cp, and these substituents may be the same or different from each other, hydrogen, Phosphine, amino, alkyl having 1 to 20 carbon atoms, alkoxy, alkylamino, dialkylamino, alkoxy-alkyl, aryl, aryloxy-alkyl, alkenyl, alkylaryl, or arylalkyl radicals, M being 4B of the periodic table, Transition metal of group 5B or 6B, X may be the same or different and is selected from the group consisting of halogen, hydrogen, alkyl having 1 to 20 carbon atoms, aryl, alkenyl, alkylaryl, arylalkyl, alkoxy and aryloxy radicals 1 paper .); And b) a metallocene catalyst composition comprising at least one member selected from the group consisting of aluminoxanes represented by the following Chemical Formulas 2 or 3, aromatic fluorine-based ionic compounds substituted with fluorine, and modified clays. [Formula 2]

[Formula 3]

In Formula 2 or 3, R 'is a hydrocarbon radical having 1 to 10 carbon atoms, x is an integer of 1 to 50, y is an integer of 3 to 50. 8. The metallocene catalyst composition of claim 7, wherein M is zirconium and X is a chlorine atom. The method according to claim 7, wherein (Cp ^* R ¹ ) is (cyclopentyl cyclopentadienyl), (1-methyl-3-cyclopentyl cyclopentadienyl), (1-butyl-3-cyclopentyl cyclopentadiene Yl), (cyclohexyl cyclopentadienyl), (1-methyl-3-cyclohexyl cyclopentadienyl), (1-butyl-3-cyclohexyl cyclopentadienyl), (cyclohexylmethylenyl cyclopentadiene Metallocene catalyst composition which is a radical selected from the group consisting of (Nyl), (cycloheptyl cyclopentadienyl), and (cyclohexylethylenyl cyclopentadienyl). The method of claim 7, wherein the fluorine-substituted aromatic boron-based ionic compound is tri (butyl) ammonium tetra (pentafluorophenyl) boron or N, N-dimethylanilinium tetra (pentafluorophenyl) boron Metallocene catalyst composition.        8. The metallocene catalyst composition of claim 7, wherein the modified clay is N, N-dimethylanilinium montmorillonite or N, N-dimethylanilinium hectorite.