KR101703273B1 - Ansa-metallocene catalyst and preparation method of supported catalyst by using it - Google Patents

Abstract

The present invention relates to an anthra-metallocene compound having a novel structure capable of realizing excellent moldability for a polyolefin copolymer, a process for producing the same, and a process for producing a polyolefin using the anisole-metallocene compound.

Description

METHOD OF SUPPORTED CATALYST BY USING IT AND METHOD OF SUPPORTING CATALYST BY USING IT}

The present invention relates to an anisometallocene compound and a method for preparing a supported catalyst using the same.

The ansa-metallocene compound is an organometallic compound containing two ligands connected to each other by a bridge group, in which the rotation of the ligand is prevented by the bridge group, The structure is determined.

These anisometallocene compounds are used as catalysts in the production of olefinic homopolymers or copolymers. In particular, it is known that an anisometallocene compound containing a cyclopentadienyl-fluorenyl ligand can produce a high molecular weight polyethylene, thereby controlling the microstructure of the polypropylene have. It is also known that an anhydride-metallocene compound containing an indenyl ligand can produce a polyolefin having excellent activity and improved stereoregularity. Particularly, in recent years, excellent formability has been required in the production of products using polyolefins. In fact, when the polyolefin is applied and the moldability of the final product is poor, there is a problem that it is difficult to secure dimensions such as the desired product shape and thickness.

Therefore, it is necessary to develop a catalyst capable of producing a polyolefin that realizes better moldability. In this connection, various studies have been made on an anis-metallocene compound containing an indenyl ligand, It is still not enough.

The present invention is to provide an anisometallocene compound having a novel structure capable of realizing excellent moldability of an olefin-based polymer by ensuring a high swell ratio as a supported catalyst.

The present invention also provides a process for preparing the anthra-metallocene compound.

The present invention also provides a supported catalyst for olefin polymerization comprising the anisometallocene compound.

The present invention also provides a process for producing a polyolefin using the supported catalyst.

The present invention provides an anhydride-metallocene compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

M ¹ is a Group 3 transition metal, a Group 4 transition metal, a Group 5 transition metal, a lanthanide series transition metal or an ethanide series transition metal;

X is the same or different halogen;

A is a bridge group connecting an indenyl group as an element of Group 14;

R ¹ and R ² are the same as or different from each other, and are selected from the group consisting of alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, Alkoxy of 1 to 20 carbon atoms is substituted alkyl of 1 to 20 carbon atoms;

L ¹ and L ^{1 '} are the same or different alkylene of 1 to 20 carbon atoms;

R ³ , and R ^{3 '} are the same or different and are aryl or cycloalkyl having 6 to 20 carbon atoms;

n is an integer of 1 to 6;

The present invention also provides a process for preparing the anthra-metallocene compound.

The present invention also provides a supported catalyst for olefin polymerization comprising the anisometallocene compound.

The present invention also provides a process for producing a polyolefin using the supported catalyst.

Hereinafter, an anisma-metallocene compound according to a specific embodiment of the present invention, a process for producing the same, a catalyst for olefin polymerization comprising the catalyst, and a process for producing a polyolefin using the catalyst will be described in detail. It is to be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

In addition, throughout this specification, "comprising" or "containing ", unless specifically stated, refers to including any and all components (or components) Can not be interpreted as excluding.

The inventors of the present invention have made extensive studies on metallocene compounds and have found that, in the course of repeated studies on metallocene compounds, an indenyl group in which an alkylene group substituted with a specific aryl or cycloalkyl at position 3 is introduced as a ligand, An anthra-metallocene compound having a functional group capable of serving as a Lewis base was substituted for an oxygen-donor in a bridge group was prepared, and the above compound was used as a catalyst precursor to prepare a support It has been confirmed that a polyolefin having excellent moldability can be easily produced in the production of a polyolefin in the case of a supported catalyst, thereby completing the present invention.

According to one embodiment of the present invention, there is provided an anhydride-metallocene compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

M ¹ is a Group 3 transition metal, a Group 4 transition metal, a Group 5 transition metal, a lanthanide series transition metal or an ethanide series transition metal;

X is the same or different halogen;

A is a bridge group connecting an indenyl group as an element of Group 14;

R ¹ and R ² are the same as or different from each other, and are selected from the group consisting of alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, Alkoxy of 1 to 20 carbon atoms is substituted alkyl of 1 to 20 carbon atoms;

L ¹ and L ^{1 '} are the same or different alkylene of 1 to 20 carbon atoms;

R ³ , and R ^{3 '} are the same or different and are aryl or cycloalkyl having 6 to 20 carbon atoms;

and n may be an integer of 1 to 6.

Preferably, one of R ¹ and R ² in Formula 1 is alkyl having 1 to 4 carbon atoms, and the remaining one of R ¹ and R ² is an alkoxy-substituted C 1 -C 20 alkyl group having 1 to 20 carbon atoms. 20 < / RTI > L ¹ , and L ^{1 '} are each alkylene having 1 to 6 carbon atoms; R ³ and R ^{3 '} are each aryl or cycloalkyl having 6 to 20 carbon atoms; A may be silicon (Si). More preferably, one of R < ¹ > and R < ² > in the formula (1) is methyl and the other is 6- (t-butoxy) hexyl; L ¹ , and L ^{1 '} are each methylene; R ³ and R ^{3 '} may each be phenyl or cyclohexyl.

In particular, the anisometallocene compound of the present invention may be represented by the following formula (2) or (3).

(2)

(3)

The anthese-metallocene compound according to the present invention comprises two indenyl groups as a ligand, and in particular, an oxygen-donor in a bridge group connecting the ligands to an Lewis base Functional group capable of acting as a substituent is substituted, thereby maximizing the activity as a catalyst. Accordingly, when the compound of Formula 1 is supported on its own or on a carrier and used as a catalyst in the production of polyolefins, a polyolefin having desired physical properties can be more easily produced.

According to another embodiment of the present invention, there is provided a process for preparing an anhydride-metallocene compound represented by the general formula (1).

The process for preparing an anisometallocene compound represented by the formula (1) according to the present invention may comprise the steps of: reacting a compound represented by the following formula (a) with a compound represented by the following formula (b) c < / RTI > And

(A)

[Formula b]

(C)

In the above formulas (a), (b) and (c)

A is an element of Group 14;

M 'is lithium, sodium, potassium, MgCl, MgBr or MgI;

R ¹ and R ² are the same as or different from each other, and are selected from the group consisting of alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, Alkoxy of 1 to 20 carbon atoms is substituted alkyl of 1 to 20 carbon atoms;

X is identical or different halogen;

L ¹ and L ^{1 '} are the same or different alkylene of 1 to 20 carbon atoms;

R ³ , and R ^{3 '} are the same or different and are aryl or cycloalkyl having 6 to 20 carbon atoms; And

And reacting the compound represented by the formula (c) with a compound represented by the following formula (d).

[Chemical formula d]

In the above formula (d)

M ¹ is a Group 3 transition metal, a Group 4 transition metal, a Group 5 transition metal, a lanthanide series transition metal or an ethanide series transition metal;

X is the same or different halogen;

n is an integer of 1 to 6;

According to an embodiment of the present invention, the step of preparing the compound of formula (c) may be carried out by first adding a solution of alkyllithium or the like to the compound of formula (b) and stirring at 10 to 50 ° C, preferably 20 to 40 ° C Can be performed. Thereafter, the compound of formula (c) can be prepared by dropwise adding the compound of formula (a) to the mixed solution at -150 ° C to 0 ° C, preferably -100 ° C to 0 ° C.

Thereafter, a solution such as alkyllithium is added to an organic solution containing the compound of Formula e at -150 ° C to 0 ° C, preferably -100 ° C to 0 ° C, and the compound of Formula d is added to the reaction product And then reacting the mixture.

Further, in addition to the above-mentioned steps, it is possible to further include steps which can be carried out conventionally in the technical field to which the present invention belongs before or after each of the above steps, so that the above- no.

According to another embodiment of the present invention, there is provided a catalyst for olefin polymerization comprising the anis-metallocene compound.

The anthese-metallocene compounds according to the invention can be used as catalysts for olefin polymerization, either alone or together with a cocatalyst as a catalyst precursor.

At this time, the catalyst for olefin polymerization may be a catalyst supported on a support.

The carrier may be any of those generally used in the technical field to which the present invention belongs, so that it is not particularly limited, but preferably at least one carrier selected from the group consisting of silica, silica-alumina and silica-magnesia may be used. On the other hand, when supported on a support such as silica, since the silica carrier and the functional groups of the anisole-metallocene compound are chemically bonded and supported, there is almost no catalyst liberated from the surface in the olefin polymerization process and the polyolefin There is no fouling on the reactor wall surface or polymer particles when they are produced.

In addition, the polyolefin produced in the presence of such a silica carrier-containing catalyst is excellent in particle shape and apparent density of the polymer, and can be suitably used in conventional slurry or gas-phase polymerization processes.

Therefore, it is preferable to use a carrier which is dried at a high temperature and has a siloxane group having high reactivity on the surface. Specifically, silica, silica was dried at high temperature - can be used are alumina and the like, which are typically _{Na 2 O, K 2 CO 3} , BaSO 4, Mg (NO 3) an oxide of _2, such as carbonate, sulfate, nitrate component .

The catalyst for olefin polymerization may further include a promoter composed of alkylaluminoxane. When such a cocatalyst is used, it can be used as a catalyst in which the halogen group (X) bonded to the metal element (M ¹ ) of the metallocene compound is substituted with an alkyl group, for example, an alkyl group having 1 to 20 carbon atoms.

The above-mentioned cocatalyst is not particularly limited as it is customary in the technical field to which the present invention belongs, but one or more cocatalysts selected from the group consisting of silica, silica-alumina and organoaluminum compound may be used.

The anthra-metallocene compound catalyst of the present invention is basically a catalyst capable of producing a polyolefin having a high molecular weight. When hydrogen is added, a low molecular weight polyolefin can be effectively produced even with a small amount of hydrogenation, It has an advantage that the molecular weight range of the product can be widened.

According to another embodiment of the present invention, there is provided a process for producing a polyolefin comprising polymerizing at least one olefin monomer in the presence of the catalyst for olefin polymerization.

The olefin monomer may be selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, , 1-octadecene, 1-eicosene, and mixtures thereof.

Here, the polymerization of the polyolefin may be carried out by reacting at a temperature of 25 to 500 ° C and a pressure of 1 to 100 kgf / cm ² for 1 to 24 hours. At this time, the polymerization reaction temperature is preferably 25 to 200 ° C, more preferably 50 to 100 ° C. The polymerization reaction pressure is preferably 1 to 70 kgf / cm ² , more preferably 5 to 40 kgf / cm ² . The polymerization reaction time is preferably 1 to 5 hours.

The polyolefin prepared using the anisometallocene compound catalyst of the present invention may have a lower molecular weight than that of a conventional metallocene catalyst. For example, the polyolefin produced according to the present invention may have a weight average molecular weight (Mw) of 250,000 or less, or 30,000 to 250,000, preferably 200,000 or less, more preferably 150,000 or less.

The polyolefin thus prepared may have a molecular weight distribution (Mw / Mn) of 3.3 or less or 1 to 3.3, preferably 1.5 to 3.2, more preferably 2 to 3.

Further, the polyolefin may have a swell ratio of 1.8 or more, or 1.8 to 5.0, preferably 2.0 or more, more preferably 2.5 or more, measured according to American Society for Testing and Materials Standards Association ASTM D 1238. Here, the swell ratio of the polyolefin is preferably 1.8 or more in terms of securing excellent moldability in order to provide a uniform size and shape in the production of the final product.

In the present invention, matters other than those described above can be added or subtracted as required, and therefore, the present invention is not particularly limited thereto.

The anisometallocene compound according to the present invention can improve the moldability of the polyolefin when the polyolefin is prepared using the catalyst as a catalyst or a catalyst precursor. A product using a polyolefin having improved formability can be manufactured more easily, thereby contributing to an increase in product productivity.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

[Example 1]

Under the conditions shown in the following Table 1, the anisometallocene compound of Formula 2 and the supported catalyst for olefin polymerization containing the same were prepared as follows.

(2)

Preparation of metallocene compounds

Step 1: Preparation of (6-t-butoxyhexyl) dichloromethylsilane

100 mL of a solution of t-butoxyhexyl magnesium chloride (about 0.14 mol, ether) was added dropwise to 100 mL of a trichloromethylsilane solution (about 0.21 mol, hexane) at -100 ° C over 3 hours, And stirred for 3 hours.

After separating the transparent organic layer from the mixed solution, the separated transparent organic layer was vacuum dried to remove excess trichloromethylsilane. Thus, a transparent liquid (6-t-butoxyhexyl) dichloromethylsilane was obtained (yield: 84%).

^{1 H NMR (500 MHz, CDCl} 3, 7.24 ppm): 0.76 (3H, s), 1.11 (2H, t), 1.18 (9H, s), 1.32 ~ 1.55 (8H, m), 3.33 (2H, t)

Step 2: Preparation of (6-t-butoxyhexyl) (methyl) -bis (3-phenylmethylene-indenyl) silane

15.4 mL of n-butyllithium solution (2.5 M, hexane solvent) was slowly added dropwise to 77 mL of 3-phenylmethyleneindentene toluene / THF = 10/1 solution (34.9 mmol) at 0 ° C and 1 hour at 80 ° C Followed by stirring at room temperature for one day. Subsequently, 5 g of the (6-t-butoxyhexyl) dichloromethylsilane prepared previously was slowly added dropwise to the mixed solution at -78 ° C, and the mixture was stirred for about 10 minutes and then at 80 ° C for 1 hour. The organic layer was separated by adding water, purified by a silica column, and vacuum dried to obtain a sticky yellow oil in a yield of 78%.

^{1 H NMR (500 MHz, CDCl} 3, 7.24 ppm): -0.24 (3H, t), 0.17 ~ 1.53 (19H, m), 3.22 ~ 3.34 (3H, m), 3.45 ~ 3.49 (1H, m), 3.91 M), 3.97 (1H, d), 6.14 (1H, d), 7.13-7.45 (18H, m)

Step 3: Preparation of [(6-t-butoxyhexylmethylsilane-diyl) -bis (3-phenylmethylene-indenyl)] zirconium dichloride

To the 50 mL of the previously prepared (6-t-butoxyhexyl) (methyl) bis (3-phenylmethylene) indenylsilane ether / hexane = 1/1 solution (3.37 mmol) was added n-butyllithium solution (2.5 M in hexane ) Was slowly added dropwise at -78 ° C, stirred at room temperature for about 2 hours, and then vacuum-dried. Then, the salt was washed with hexane, followed by filtration and vacuum drying to obtain a yellow solid. The ligand salt synthesized in a glove box and bis (N, N'-diphenyl-1,3-propanediamido) dichlorozirconium bis (tetrahydrofuran) [Zr (C ₅ H ₆ NCH ₂ CH ₂ CH ₂ NC ₅ H ₆ ) Cl ₂ (C ₄ H ₈ O) ₂ ] was weighed in a Schlenk flask, ether was slowly added dropwise at -78 ° C., And stirred for one day. Thereafter, the red reaction solution was separated by filtration, 4 equivalents of an HCl ether solution (1M) was slowly added dropwise at -78 ° C, and the mixture was stirred at room temperature for 3 hours. It was then filtered and vacuum dried to obtain an orange-solid anisma-metallocene compound in a yield of 85%.

¹ H NMR (500 MHz, CDCl ₃ , 7.24 ppm): 0.80-1.86 (22H, m), 3.30-3.35 (2H, m), 4.13-4.29 (4H, m), 5.63 1H, < / RTI > d), 6.88-7.62 (18H, m)

Preparation of Supported Catalyst

10 g of silica was added to a pico reactor (buch) containing 100 mL of toluene, and 8 mmol / g SiO ₂ of methylaluminoxane (MAO) was added thereto, followed by reaction at 60 ° C. for 12 hours. After precipitation, the upper layer was removed and washed once with toluene. 1 mmol of the synthesized anthra-metallocene compound was dissolved in toluene and reacted at 40 ° C for 5 hours. After the completion of the reaction, the upper layer solution was removed, and the remaining reaction product was washed with toluene, washed again with hexane, and vacuum dried to obtain a silica-supported metallocene catalyst in the form of solid particles.

[Example 2]

Under the conditions shown in the following Table 1, an anisma-metallocene compound of Formula 3 and a catalyst for olefin polymerization comprising the same were prepared in the following manner.

(3)

Preparation of metallocene compounds

Step 1: Preparation of (6-t-butoxyhexyl) dichloromethylsilane

(6-t-butoxyhexyl) dichloromethylsilane was prepared in the same manner as in Example 1.

Step 2: Preparation of (6-t-butoxyhexyl) (methyl) -bis (3-cyclohexylmethylene-indenyl) silane

15.4 mL of n-butyllithium solution (2.5 M, hexane solvent) was slowly added dropwise to 77 mL of 3-cyclohexylmethane indene toluene / THF = 10/1 solution (34.9 mmol) at 0 ° C, Followed by stirring at room temperature for one day. Subsequently, 5 g of the (6-t-butoxyhexyl) dichloromethylsilane prepared previously was slowly added dropwise to the mixed solution at -78 ° C, and the mixture was stirred for about 10 minutes and then at 80 ° C for 1 hour. The organic layer was separated by adding water, purified by a silica column, and vacuum dried to obtain a sticky yellow oil in a yield of 78%.

^{1 H NMR (500 MHz, CDCl} 3, 7.24 ppm): -0.5 (0.8H, s), -0.28 (1.2H, s), 0.06 (1H, s), 1.02 ~ 1.14 (2H, m), 1.18 ~ (2H, m), 1.83-1.96 (10H, m), 1.97-2.03 (4H, m), 1.31 (4H, m), 1.39-1.45 ), 2.05-2.10 (4H, m), 6.27-6.47 (2H, m), 7.36-7.40 (2H, m), 7.46-7.52

Step 3: Preparation of [(6-t-butoxyhexylmethylsilane-diyl) -bis (3-cyclohexylmethylene-indenyl)] zirconium dichloride

To the 50 mL of the previously prepared (6-t-butoxyhexyl) (methyl) bis (3-phenylmethylene) indenylsilane ether / hexane = 1/1 solution (3.37 mmol) was added n-butyllithium solution (2.5 M in hexane ) Was slowly added dropwise at -78 ° C, stirred at room temperature for about 2 hours, and then vacuum-dried. Then, the salt was washed with hexane, followed by filtration and vacuum drying to obtain a yellow solid. The ligand salt synthesized in a glove box and bis (N, N'-diphenyl-1,3-propanediamido) dichlorozirconium bis (tetrahydrofuran) [Zr (C ₅ H ₆ NCH ₂ CH ₂ CH ₂ NC ₅ H ₆ ) Cl ₂ (C ₄ H ₈ O) ₂ ] was weighed in a Schlenk flask, ether was slowly added dropwise at -78 ° C., And stirred for one day. Thereafter, the red reaction solution was separated by filtration, 4 equivalents of an HCl ether solution (1M) was slowly added dropwise at -78 ° C, and the mixture was stirred at room temperature for 3 hours. It was then filtered and vacuum dried to obtain an orange-solid anisma-metallocene compound in a yield of 85%.

¹ H NMR (500 MHz, CDCl ₃ , 7.24 ppm): -0.01 (3H, s), 1.02-1.33 (10H, m), 1.18-1.20 (9H, m), 1.38-1.49 (1H, m), 2.31 (2H, m), 2.51 (1H, m), 2.50 (2H, m), 6.86 (1H, m), 7.04 (1H, m), 7.16

Preparation of Supported Catalyst

Except that the anthra-metallocene compound [(6-t-butoxyhexylmethylsilane-diyl) -bis (3-cyclohexylmethylene-indenyl)] zirconium dichloride synthesized above was used, A silica-supported metallocene catalyst in the form of solid particles was prepared.

[Comparative Example 1]

Under the conditions shown in the following Table 1, an anisometallocene compound of Formula 4 and a catalyst for olefin polymerization comprising the same were prepared in the following manner.

[Chemical Formula 4]

Preparation of metallocene compounds

Step 1: Preparation of (6-t-butoxyhexyl) dichloromethylsilane

(6-t-butoxyhexyl) dichloromethylsilane was prepared in the same manner as in Example 1.

Step 2: Preparation of 6-t-butoxyhexyl-bisindenylmethylsilane

27.9 mL of n-butyllithium solution (2.5 M in hexane) was slowly added dropwise to 50 mL of an indene solution (77.55 mmol in ether) at 0 ° C, and then the mixed solution was stirred at room temperature for about 2 hours. Thereafter, 9.96 g of (6-t-butoxyhexyl) dichloromethylsilane prepared previously was slowly added dropwise to the mixed solution at -78 ° C, stirred for about 10 minutes, and then stirred at room temperature for about 3 hours. The reaction product was then filtered and vacuum dried to give 6-t-butoxyhexyl-bisindenylmethylsilane in the form of a sticky oil (yield 75%).

¹ H NMR (500 MHz, CDCl ₃ , 7.24 ppm): -0.45, -0.22, -0.07, 0.54 (total 3H, s), 0.87 (1H, m), 1.13 m), 3.25 (2H, m), 3.57 (1H, m), 6.75,6.85,6.90,77.11,7.12,7.19 (total 4H, m), 7.22-7.45 (4H, m), 7.48-7.51 , m)

Step 3: Preparation of [(6-t-butoxyhexylmethylsilane-diyl) -bis (indenyl)] zirconium dichloride

26 mL of n-butyllithium solution (2.5 M in hexane) was slowly added dropwise to 50 mL of the previously prepared (6-t-butoxyhexyl) -bisindenylmethylsilane solution (29 mmol, , Stirred at room temperature for about 2 hours, and vacuum dried. Thereafter, the salt was washed with hexane, followed by filtration and vacuum drying to obtain a white solid.

After dissolving it in toluene and dimethoxyethane, ZrCl ₄ toluene slurry was added thereto at -78 ° C, and the mixture was stirred at room temperature for about 3 hours. After drying in vacuo, hexane was added thereto, followed by filtration at a low temperature to obtain [(6-t-butoxyhexylmethylsilane-diyl) -bis (indenyl)] zirconium dichloride as an orange solid.

^{1 H NMR (500 MHz, CDCl} 3, 7.24 ppm): 1.09 (3H, s), 1.14 (9H, s), 1.60 (6H, m), 1.83 (4H, m), 3.33 (2H, m), 6.08 (2H, m), 6.91 (2H, m), 7.08 (2H, m), 7.35 (3H, m), 7.44

Preparation of Supported Catalyst

The same procedure as in Example 1 was carried out except that zirconium dichloride was used as the anthra-metallocene compound [(6-t-butoxyhexylmethylsilane-diyl) -bis (indenyl) Lt; / RTI >

Example 1 Example 2 Comparative Example 1 R1 CH3 CH3 CH3 R2 (t-Bu) OC6H8 (t-Bu) OC6H8 (t-Bu) OC6H8 M1 Zr Zr Zr X Cl Cl Cl N 2 2 2 L1, L1 ' CH2 CH2 - R3, R3 ' Ph C6H11 - Type of promoter compound MAO MAO MAO Reaction temperature (캜) 40 40 40 Reaction time (h) 5 5 5 Carrier type Silica Silica Silica Catalyst type powder powder powder

[ Manufacturing example  1 to 2 and Comparative Manufacturing Example  One]

Using the metallocene catalysts prepared in Examples 1 and 2 and Comparative Example 1, polyethylene polymers were prepared in the following manner, respectively.

Ethylene polymerization

First, a 600 mL stainless steel reactor was vacuum dried at 120 ° C., cooled, and 400 mL of hexane was added thereto at 50 ° C., 10 mmol of trimethylaluminum was added thereto, and the mixture was stirred for 5 minutes. After the internal solution was completely removed, 400 mL of hexane was added again, and 10 mg of the metallocene catalyst prepared in Examples 1 and 2 and Comparative Example 1 was added to the reactor. After the reactor temperature was gradually raised to 80 ° C, ethylene was fed at a pressure of 9 bar and polymerized for 1 hour. After the reaction was completed, the unreacted ethylene was vented.

The catalyst content, catalyst activity, and physical properties of the polymer were measured at this time, and are shown in Table 2 below.

≪ Measurement method of physical properties of polymer &

(1) Catalytic activity: Calculated as the ratio of the weight of polymer produced per kg of catalyst (gCat) (kg PE) based on unit time (h).

(2) Polymer molecular weight distribution (PDI) and weight average molecular weight (Mw): The weight average molecular weight (Mw) and the number average molecular weight (Mw) of the polymer were measured by gel permeation chromatography (GPC) The molecular weight (Mn) was measured, and the molecular weight distribution (PDI) was calculated by dividing the weight average molecular weight by the number average molecular weight. At this time, the analysis temperature was 160 ° C, trichlorobenzene was used as a solvent, and the molecular weight was measured by standardizing with polystyrene.

(3) Swell ratio: Using a Dynisco MI (Melt Index) measuring device, a PE sample polymerized at 190 ° C was pushed out in a vertical direction for 10 minutes at a weight of 21.6 kg to prepare an orifice (Orifice, diameter: 2.09 mm (Reference: ASTM D1238), the diameter of the molten polymer injected was measured, and the swell ratio was measured according to the following equation (2).

[Equation 1]

Swell ratio = diameter of injected molten polymer / diameter of orifice

The polymerization process conditions of Production Examples 1 to 2 and Comparative Production Example 1 using the metallocene catalysts prepared in Examples 1 to 2 and Comparative Example 1 and the measurement results of physical properties of the resulting polypropylene are shown in Table 2 below .

Production Example 1 Production Example 2 Comparative Preparation Example 1 Catalyst type Example 1 Example 2 Comparative Example 1 Ethylene (bar) 9 9 9 The amount of catalyst (mg) 10 10 10 Polymerization method Bulk polymerization Bulk polymerization Bulk polymerization Polymerization temperature (캜) 80 80 80 Activity (kg / gCat · hr) 1.9 4.0 2.4 Mw 133,000 108,000 173,000 PDI 8.3 6.3 7.2 Swell ratio 2.3 2.2 1.7

As shown in Table 2, in the case of Production Examples 1 and 2 using the metallocene compounds of Examples 1 and 2 having specific substituents at the 3-position of the indenyl group according to the present invention as supported catalysts, It can be seen that a high swell ratio of 2.2 to 2.3 is ensured. Therefore, in Production Examples 1 and 2, excellent moldability can be obtained by achieving a high swell ratio in the development of polyethylene (PE) products.

On the other hand, in Comparative Preparation Example 1 using the metallocene compound of Comparative Example 1 having no such specific substituent as a catalyst, it can be seen that the resulting polyolefin has a swell ratio of 1.7, which is remarkably lowered. As described above, when the swell ratio is decreased, the moldability improving effect can not be obtained, and further optimization of the process and the like is required in order to secure a uniform size and shape in the final product.

Claims (11)

An anhydride-metallocene compound represented by the following general formula (2) or (3).
(2)

(3)

delete delete Reacting a compound represented by the formula (a) with a compound represented by the formula (b) to prepare a compound represented by the formula (c); And
(A)

[Formula b]

(C)

In the above formulas (a), (b) and (c)
A is silicon (Si);
M 'is lithium, sodium, potassium, MgCl, MgBr or MgI;
R ¹ is methyl and R ² is t-butoxyhexyl;
X is each Cl;
L ¹ and L ^{1 '} are each methylene;
R ³ and R ^{3 '} are each phenyl or cyclohexyl; And
(2) or (3), comprising the step of reacting a compound represented by the above formula (c) with a compound represented by the following formula (d): < EMI ID =
[Chemical formula d]

In the above formula (d)
M ¹ is Zr;
X is each Cl;
n is 2; A catalyst for olefin polymerization comprising an anhydride-metallocene compound according to claim 1. 6. The method of claim 5,
Wherein the anisole-metallocene compound is supported on at least one carrier selected from the group consisting of silica, silica-alumina and silica-magnesia. A process for the preparation of olefinic monomers comprising polymerizing at least one olefin monomer in the presence of a catalyst according to any one of claims 5 to 6 to obtain a polymer having a swell ratio of from 1.8 to 5.0 measured according to ASTM D 1238, To form a polyolefin. 8. The method of claim 7,
Wherein the polymerization of the polyolefin is carried out by reacting for 1 to 24 hours at a temperature of 25 to 500 DEG C and a pressure of 1 to 100 kgf / cm < ² >. 8. The method of claim 7,
The olefin monomer may be selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, , 1-octadecene, 1-eicosene, and mixtures thereof. 8. The method of claim 7,
Wherein the polyolefin has a weight average molecular weight (Mw) of 30,000 to 250,000. delete