KR102204962B1 - Supported hybrid metallocene catalyst and method for preparing of olefin based polymer using the same - Google Patents

Abstract

The present invention relates to a novel hybrid supported metallocene catalyst and a method for producing an olefin-based polymer using the same. The hybrid supported metallocene catalyst according to the present invention can be used when preparing an olefin-based polymer, has excellent processability, mechanical properties, and haze properties, and can prepare an olefin-based polymer having a narrow molecular weight distribution.

Description

A hybrid supported metallocene catalyst and a method for producing an olefin-based polymer using the same TECHNICAL FIELD [SUPPORTED HYBRID METALLOCENE CATALYST AND METHOD FOR PREPARING OF OLEFIN BASED POLYMER USING THE SAME}

The present invention relates to a novel hybrid supported metallocene catalyst and a method for producing an olefin-based polymer using the same.

The olefin polymerization catalyst system can be classified into a Ziegler Natta and a metallocene catalyst system, and these two highly active catalyst systems have been developed according to their respective characteristics. Ziegler Natta catalysts have been widely applied to conventional commercial processes since their invention in the 1950s, but since they are multi-site catalysts with multiple active points, they are characterized by a wide molecular weight distribution of polymers. There is a problem in that there is a limit to securing desired physical properties because the composition distribution of is not uniform.

Meanwhile, the metallocene catalyst is composed of a combination of a main catalyst composed of a transition metal compound and a cocatalyst composed of an organometallic compound composed mainly of aluminum. Such a metallocene catalyst is a homogeneous complex catalyst and is a single site catalyst. Therefore, a polymer having a narrow molecular weight distribution and a uniform composition distribution of the comonomer is obtained, and the stereoregularity, copolymerization characteristics, molecular weight, and crystallinity of the polymer can be changed according to the modification of the ligand structure of the catalyst and the change of polymerization conditions. It has characteristics.

U.S. Patent No. 5,914,289 describes a method of controlling the molecular weight and molecular weight distribution of a polymer using a metallocene catalyst supported on each carrier, but it takes a lot of time and the amount of solvent used to prepare the supported catalyst. In addition, there was a hassle of supporting each of the metallocene catalysts used on the carrier.

Korean Patent Application No. 2003-12308 discloses a method of controlling the molecular weight distribution by polymerizing while changing the combination of catalysts in the reactor by supporting a double-nuclear metallocene catalyst and a single-nuclear metallocene catalyst on a carrier together with an activator. have.

However, this method has a limitation in realizing the characteristics of each catalyst at the same time, and also has a disadvantage in that the metallocene catalyst portion is released from the carrier component of the completed catalyst, causing fouling in the reactor.

Therefore, in order to solve the above-described disadvantages, there is a continuing need for a method of preparing an olefin-based polymer having a desired physical property by simply preparing a mixed supported metallocene catalyst having excellent activity.

On the other hand, linear low-density polyethylene is a resin prepared by copolymerizing ethylene and alpha olefin at low pressure using a polymerization catalyst, and thus has a narrow molecular weight distribution, short chain branches of a constant length, and no long chain branches. Linear low-density polyethylene film has high breaking strength and elongation as well as the properties of general polyethylene, and has excellent tear strength and fall impact strength, so it is increasingly used for stretch films and overlap films, which are difficult to apply to existing low-density polyethylene or high-density polyethylene. have.

However, linear low-density polyethylene using 1-butene or 1-hexene as a comonomer is mostly produced in a single gas phase reactor or a single loop slurry reactor, and has higher productivity compared to the process using 1-octene comonomer, but these products are also used. Due to the limitations of catalyst technology and process technology, physical properties are significantly inferior to when using 1-octene comonomer, and the molecular weight distribution is narrow, resulting in poor processability.

Much effort has been made to improve this problem, and U.S. Patent No. 4,935,474 reports on a method for producing polyethylene having a broad molecular weight distribution by using two or more metallocene compounds. U.S. Patent No. 6,828,394 reports on a method for producing polyethylene having good processability and particularly suitable for films by mixing those having good comonomer binding properties and those not having good comonomer binding properties. In addition, U.S. Patent No. 6,841,631 and U.S. Patent No. 6,894,128 disclose a metallocene-based catalyst in which at least two kinds of metal compounds are used to prepare polyethylene having a bimodal or polymorphic molecular weight distribution, so that it is suitable for use in films, blow molding, pipes, etc. It is reported that it is applicable.

Polyethylene produced by such a metallocene catalyst has improved processability, but the dispersion state for each molecular weight in the unit particle is not uniform, and thus the extrusion appearance is rough and physical properties are not stable even under relatively good extrusion conditions.

Against this background, there is a constant demand for production of better products with a balance between physical properties and processability, and further improvement is required.

The present invention is to provide a mixed supported metallocene catalyst capable of preparing an olefin-based polymer having excellent processability, improved transparency and mechanical properties, and a method for producing an olefin-based polymer using the same.

Therefore, the present invention,

A first metallocene compound represented by the following formula (1);

A second metallocene compound represented by the following formula (2);

Cocatalyst compounds; And

It provides a hybrid supported metallocene catalyst comprising a carrier.

[Formula 1]

[Formula 2]

In addition, the present invention provides a method for preparing an olefin-based polymer comprising polymerizing an olefin-based monomer in the presence of the hybrid supported metallocene catalyst.

The hybrid supported metallocene catalyst according to the present invention can be used in the production of an olefin-based polymer having a narrow molecular weight distribution and excellent processability. The olefin-based polymer prepared by using the hybrid supported metallocene catalyst has excellent processability, mechanical properties, and transparency, and thus can be usefully used for purposes such as blown films.

Hereinafter, the present invention will be described in more detail.

The hybrid supported metallocene catalyst according to the present invention includes a first metallocene compound represented by the following formula (1); A second metallocene compound represented by the following formula (2); Cocatalyst compounds; And a carrier.

[Formula 1]

In Formula 1,

M1 is a Group 4 transition metal;

X11 and X12 are the same as or different from each other, and each independently a halogen, a nitro group, an amido group, a sulfonate group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a silyl group, or an aryl group having 6 to 20 carbon atoms. ;

B1 is carbon (C), silicon (Si), or germanium (Ge);

Q11 and Q12 are the same as or different from each other, and each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms;

R1 to R14 are the same as or different from each other, and each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, a silyl group, a silylalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms;

[Formula 2]

In Chemical Formula 2,

M2 is a Group 4 transition metal;

X21 and X22 are the same as or different from each other, and each independently a halogen, a nitro group, an amido group, a sulfonate group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a silyl group, or an aryl group having 6 to 20 carbon atoms. ;

B2 is carbon (C), silicon (Si), or germanium (Ge);

Q21 and Q22 are the same as or different from each other, and each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, or are linked to each other to form an aliphatic ring having 4 to 10 ring atoms. Can be formed;

R21 to R31 are the same as or different from each other, and each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, a silyl group, a silylalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms;

n is the number of repeating alkylene units, and is an integer of 1 to 10;

R32 is hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.

In the metallocene compound according to the present invention, the substituents of Formulas 1 and 2 will be described in more detail as follows.

The alkyl group includes a linear or branched alkyl group, and specifically, a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, etc. It may be mentioned, but is not limited thereto.

The aryl group includes a monocyclic or condensed ring aryl group, and specifically, a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, a fluorenyl group, and the like, but are not limited thereto.

Examples of the Group 4 transition metal include titanium (Ti), zirconium (Zr), and hafnium (Hf), but are not limited thereto.

In the hybrid supported metallocene catalyst according to the present invention, R1 to R14 in Formula 1 are each independently hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group , A hexyl group, a heptyl group, an octyl group, or a phenyl group is more preferable, but is not limited thereto.

In the hybrid supported metallocene catalyst according to the present invention, M1 in Formula 1 is zirconium (Zr) or hafnium (Hf); X11 and X12 are the same as or different from each other, and each independently, more preferably chlorine (Cl) or bromine (Br), but is not limited thereto.

In the hybrid supported metallocene catalyst according to the present invention, B1 in Formula 1 is silicon (Si) or germanium (Ge); Q11 and Q12 are the same as or different from each other, and are each independently hydrogen, more preferably an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, but is not limited thereto.

Specifically, the metallocene compound of Formula 1 may be represented by the following structural formula.

In the hybrid supported metallocene catalyst according to the present invention, n in Formula 2 is an integer of 4 to 8; R32 may be hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, or tert-butyl, but is not limited thereto.

In the hybrid supported metallocene catalyst according to the present invention, M2 in Formula 2 is zirconium (Zr) or hafnium (Hf); X21 and X22 are the same as or different from each other, and each independently, more preferably chlorine (Cl) or bromine (Br), but is not limited thereto.

In the hybrid supported metallocene catalyst according to the present invention, B2 in Formula 2 is carbon (C) or silicon (Si); Q21 and Q22 are the same as or different from each other, and each independently, hydrogen or an alkyl group having 1 to 10 carbon atoms, or are linked to each other, more preferably to form an aliphatic ring having 4 to 10 ring atoms, but limited thereto. It is not.

Specifically, the metallocene compound of Formula 2 may be represented by the following structural formula.

The method for preparing the metallocene compound represented by Chemical Formulas 1 and 2 was described in detail in Examples to be described later.

The first metallocene compound represented by Chemical Formula 1 includes a cyclopentadienyl derivative and a tetrahydroindenyl derivative in different forms, and the two ligands are connected by a bridge group, and the cyclic ligand The electron cloud of is coordinated to the transition metal atom. When a transition metal compound having such a specific structure is activated by an appropriate method and used as a catalyst for the olefin polymerization reaction, an olefin-based polymer having high activity and excellent processability and mechanical properties can be prepared.

Specifically, as in Chemical Formula 1, a transition metal compound having a cyclopentadienyl ligand on one side and a tetrahydroindenyl ligand on the other side has relatively low electrons compared to other similar metallocene compound structures. Density and due to the steric hindrance effect by aliphatic rings, it has a relatively narrow molecular weight distribution It is effective in making olefin-based polymers.

Since the cyclopentadienyl ligand and the tetrahydroindenyl ligand are linked by a bridging group, they can have high structural stability, and can exhibit high polymerization activity even when supported on a carrier.

In addition, the second metallocene compound of Formula 2 has a structure in which a fluorene derivative and a cyclopentadienyl derivative are crosslinked by a bridge. In addition, when a substituent having a non-shared electron pair capable of acting as a Lewis base is introduced into the cyclopentadienyl group, and it is supported on the surface of a carrier having Lewis acid properties, not only the loading efficiency is increased, but also high polymerization activity can be exhibited. have.

In the case of the second metallocene compound represented by Formula 2, it may have a relatively high electron density due to the fluorene group, and the effect due to steric hindrance of the substituent is small, so that it has a relatively narrow molecular weight distribution and high molecular weight. It is advantageous for making active olefinic polymers.

The hybrid supported metallocene catalyst according to the present invention comprises at least one of the first metallocene compound represented by Formula 1 and at least one of the second metallocene compound selected from the compound represented by Formula 2 above. It is mixedly supported on a carrier together with a cocatalyst compound.

As described above, the first metallocene compound represented by Formula 1 of the hybrid supported metallocene catalyst mainly contributes to making a copolymer excellent in processability, and the second metallocene compound represented by Formula 2 is relatively It can contribute to making a high molecular weight, high activity copolymer.

Therefore, the olefin-based copolymer prepared using a mixed supported metallocene catalyst containing a heterogeneous metallocene compound including the metallocene compounds of Formulas 1 and 2, respectively, induces a narrow molecular weight distribution and thus has high transparency. While showing, processability and bubble stability may be improved.

In the hybrid supported metallocene catalyst according to the present invention, as an organometallic compound including a Group 13 metal, as a cocatalyst supported together on a carrier to activate the metallocene compound, an olefin is used under a general metallocene catalyst. It is not particularly limited as long as it can be used during polymerization.

Specifically, the cocatalyst compound may include one or more of the cocatalyst compounds represented by the following Chemical Formulas 3 to 6.

[Formula 3]

-[Al(R40)-O] _n-

In Chemical Formula 3,

R40 may be the same as or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a halogen-substituted C 1 to C 20 hydrocarbon;

n is an integer of 2 or more;

[Formula 4]

D(R50) ₃

In Chemical Formula 4,

R50 may be the same as or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a halogen-substituted C 1 to C 20 hydrocarbon;

D is aluminum or boron;

[Formula 5]

_{^{[LH] + [ZA 4]}} - or _{^{[L] + [ZA 4]}} -

In Chemical Formula 5,

L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a group 13 element; A may be the same as or different from each other, and each independently one or more hydrogen atoms is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy. .

Examples of the compound represented by Chemical Formula 3 include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like, and a more preferable compound is methylaluminoxane.

Examples of the compound represented by Formula 4 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl Boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, etc. are included, and more preferable compounds are selected from trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum.

Examples of the compound represented by Formula 5 include triethyl ammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium tetra (p-tolyl) Boron, trimethylammonium tetra (o,p-dimethylphenyl) boron, tributyl ammonium tetra (p-trifluoromethylphenyl) boron, trimethyl ammonium tetra (p-trifluoromethylphenyl) boron, tributyl ammonium tetra Pentafluorophenyl boron, N,N-diethylanilinium tetraphenyl boron, N,N-diethylanilinium tetrapentafluorophenyl boron, diethylammonium tetrapentafluorophenyl boron, triphenylphosphonium Tetraphenyl boron, trimethylphosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra (p-tolyl ) Aluminum, tripropyl ammonium tetra (p-tolyl) aluminum, triethyl ammonium tetra (o,p-dimethylphenyl) aluminum, tributyl ammonium tetra (p-trifluoromethylphenyl) aluminum, trimethyl ammonium tetra ( p-trifluoromethylphenyl)aluminum, tributylammonium tetrapentafluorophenylaluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylanilinium tetrapentafluorophenylaluminum, di Ethyl ammonium tetrapenta tetraphenyl aluminum, triphenyl phosphonium tetraphenyl aluminum, trimethyl phosphonium tetraphenyl aluminum, tripropyl ammonium tetra (p-tolyl) boron, triethyl ammonium tetra (o,p-dimethylphenyl) boron , Tributylammonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetrapentafluorophenyl boron, and the like.

In the hybrid supported metallocene catalyst according to the present invention, the mass ratio of the transition metal to the carrier of the first and second metallocene compounds is preferably 1:1 to 1:1,000. When the carrier and the metallocene compound are included in the mass ratio, it may exhibit an appropriate supported catalytic activity, which may be advantageous in terms of maintaining the activity of the catalyst and economical efficiency.

In addition, the mass ratio of the cocatalyst compound of Formula 3 or 5 to the carrier is preferably 1:20 to 20:1, and the mass ratio of the cocatalyst compound of Formula 5 to the carrier is preferably 1:10 to 100:1.

In addition, it is preferable that the mass ratio of the first metallocene compound to the second metallocene compound is 1:100 to 100:1. When the cocatalyst and the metallocene compound are included in the mass ratio, it may exhibit an appropriate catalytic activity, which may be advantageous in terms of maintaining the activity of the catalyst and economical efficiency.

In the hybrid supported metallocene catalyst according to the present invention, a carrier containing a hydroxy group on the surface may be used as the carrier, and preferably, a highly reactive hydroxy group and a siloxane group are dried to remove moisture from the surface. You can use your own carrier.

For example, silica dried at high temperature, silica-alumina, and silica-magnesia may be used, and these are usually oxides, carbonates, such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg(NO ₃ ) ₂ , It may contain sulfate and nitrate components.

The drying temperature of the carrier is preferably 100 to 800. When the drying temperature of the carrier is less than 100, there is too much moisture so that the moisture on the surface and the cocatalyst react, and when it exceeds 800, the pores on the surface of the carrier are combined and the surface area decreases, and a lot of hydroxyl groups on the surface disappear. It is not preferable because only the siloxane group remains and the reaction site with the cocatalyst decreases.

The amount of hydroxy groups on the surface of the carrier is preferably 0.1 to 10 mmol/g, and more preferably 0.2 to 5 mmol/g. The amount of hydroxy groups on the surface of the carrier can be controlled by a method and conditions for preparing the carrier or drying conditions such as temperature, time, vacuum or spray drying.

If the amount of the hydroxyl group is less than 0.1 mmol/g, the reaction site with the cocatalyst is small, and if it exceeds 10 mmol/g, it is not preferable because it may be due to moisture other than the hydroxyl group present on the surface of the carrier particle. not.

In the hybrid supported metallocene catalyst according to the present invention, the steps of supporting a cocatalyst compound on a carrier, supporting the first metallocene compound on the carrier, and supporting the second metallocene compound on the carrier Can be prepared in steps. In the method for preparing the hybrid supported metallocene catalyst, the order of the steps of supporting the first and second metallocene compounds may be changed as necessary. That is, a first metallocene compound is first supported on a carrier, and then a second metallocene compound is additionally supported to prepare a hybrid supported metallocene catalyst, or a second metallocene compound is first supported on the carrier. Thereafter, the first metallocene compound may be supported. Alternatively, the first and second metallocene compounds may be simultaneously added and supported.

When preparing the hybrid supported metallocene catalyst, a hydrocarbon solvent such as pentane, hexane, or heptane, or an aromatic solvent such as benzene or toluene may be used as a reaction solvent. In addition, the metallocene compound and the cocatalyst compound may be used in a form supported on silica or alumina.

In addition, another aspect of the present invention provides a method for producing an olefin-based polymer comprising polymerizing an olefin-based monomer in the presence of the hybrid supported metallocene catalyst.

In the method for producing an olefin-based polymer according to the present invention, specific examples of the olefin-based monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1 -There are octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, etc., and two or more of them may be mixed and copolymerized.

The olefin-based polymer is more preferably an ethylene/alpha olefin copolymer, but is not limited thereto.

In the case where the olefin-based polymer is an ethylene/alpha-olefin copolymer, the content of the alpha-olefin, which is the comonomer, is not particularly limited, and may be appropriately selected according to the use and purpose of the olefin-based polymer. More specifically, it may be greater than 0 and not more than 99 mol%.

The polymerization reaction may be performed by homopolymerization with one olefinic monomer or copolymerization with two or more monomers using one continuous slurry polymerization reactor, loop slurry reactor, gas phase reactor, or solution reactor.

The mixed supported metallocene catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, such as pentane, hexane, heptane, nonane, decane, and isomers thereof, and aromatic hydrocarbon solvents such as toluene and benzene, dichloromethane, chlorobenzene, and It can be dissolved or diluted in a hydrocarbon solvent substituted with the same chlorine atom and injected. The solvent used here is preferably used after removing a small amount of water or air acting as a catalyst poison by treating a small amount of alkyl aluminum, and it is also possible to further use a cocatalyst.

The first metallocene compound represented by Formula 1 of the hybrid supported metallocene catalyst mainly contributes to making a copolymer with excellent processability, and the second metallocene compound represented by Formula 2 has a relatively high molecular weight and high activity. Can contribute to making a copolymer of.

Therefore, the olefin-based copolymer prepared using a mixed supported metallocene catalyst containing a heterogeneous metallocene compound including the metallocene compounds of Formulas 1 and 2, respectively, induces a narrow molecular weight distribution and thus has high transparency. While showing, processability, bubble stability (melt strength), and strength may be improved.

Using the hybrid supported metallocene catalyst of the present invention, the polymerization temperature may be about 25 to about 500, preferably about 25 to about 200, more preferably about 50 to about 150. In addition, the polymerization pressure may be about 1 to about 100kgf/cm ² , preferably about 1 to about 70kgf/cm ² , more preferably about 5 to about 50kgf/cm ² .

The olefin-based polymer according to the present invention can be obtained by homopolymerization of ethylene or copolymerization of ethylene and alpha olefin by using the hybrid supported metallocene compound as a catalyst.

The hybrid supported metallocene catalyst of the present invention exhibits excellent activity, and the olefin-based polymer prepared using the hybrid supported metallocene catalyst of the present invention has excellent mechanical properties such as strength, optical properties such as transparency, and workability.

For example, the olefin-based polymer prepared by the production method of the present invention exhibits a narrow molecular weight distribution (Mw/Mn, PDI) of about 2.0 to about 4.0, preferably about 2.3 to about 3.5, showing an effect of improving transparency. I can.

In the present invention, the weight average molecular weight (Mw) of the olefin-based polymer may be about 50,000 to about 500,000 g/mol, preferably about 80,000 to about 200,000 g/mol, but is not limited thereto.

Therefore, the olefin-based polymer prepared by the production method of the present invention has mechanical properties such as impact strength, tensile strength, and tear strength, and in particular, the fall impact strength value measured by a method such as ASTM D 1709 [Method A] is about 500 g Above, preferably, from about 500g to about 700g, it is very excellent, has excellent optical properties such as haze, and at the same time has excellent processability. Thus, the olefin-based polymer prepared by the production method of the present invention can be used in various applications requiring such physical properties, and in particular, can be preferably used in applications such as blown films requiring excellent strength and transparency.

Hereinafter, a preferred embodiment is presented to aid the understanding of the present invention. However, the following examples are provided for easier understanding of the present invention, and the content of the present invention is not limited thereby.

< Example >

< Metallocene Preparation of compound>

Manufacturing example 1: first Metallocene Preparation of compound

(1) Synthesis of dimethyl(indenyl)(tetramethylcyclopentadienyl)silane

After dissolving tetramethylcyclopentadiene (TMCP, 6.0 mL, 40 mmol) in THF (60 mL) in a dried 250 mL schlenk flask, the solution was cooled to -78. Subsequently, n-BuLi (2.5M, 17 mL, 42 mmol) was slowly added dropwise to the solution, and the resulting solution was stirred at room temperature overnight.

Meanwhile, dichlorodimethylsilane (4.8mL, 40mmol) was dissolved in n-hexane in a separate 250mL schlenk flask, and the solution was cooled to -78. Subsequently, the TMCP-lithiation solution prepared previously was slowly injected into this solution. And the resulting solution was stirred at room temperature overnight.

Thereafter, the obtained solution was depressurized to remove the solvent from the solution. Then, the obtained solid was dissolved in toluene and filtered to remove remaining LiCl to obtain an intermediate (yellow liquid, 7.0g, 33 mmol, 83% yield).

¹ H NMR (500 MHz, CDCl ₃ ): 0.24 (6H, s), 1.82 (6H, s), 1.98 (6H, s), 3.08 (1H, s).

After dissolving indene (0.93mL, 8.0mmol) in THF (30mL) in a dried 250mL schlenk flask, the solution was cooled to -78. Then, n-BuLi (2.5M, 3.4 mL, 8.4 mmol) was slowly added dropwise to the solution, and the resulting solution was stirred at room temperature for about 5 hours.

Meanwhile, in a separate 250 mL schlenk flask, the previously synthesized intermediate (1.7 g, 8.0 mmol) was dissolved in THF, and the solution was cooled to -78. Then, the previously prepared indene-lithiation solution was slowly injected into this solution. And the resulting solution was stirred at room temperature overnight to obtain a purple solution.

Thereafter, water was poured into the reactor to terminate the reaction (quenching), and an organic layer was extracted from the mixture with ether. It was confirmed through ¹ H NMR that the organic layer contained dimethyl(indenyl)(tetramethylcyclopentadienyl)silane and other types of organic compounds. The organic layer was concentrated without purification and used as it is for metallation.

(2) Synthesis of dimethylsilylene (tetramethylcyclopentadienyl) (indenyl) zirconium dichloride

In a 250 mL schlenk flask, previously synthesized dimethyl(indenyl)(tetramethylcyclopentadienyl)silane (1.7g, 5.7mmol) was dissolved in toluene (30mL) and MTBE (3.0mL). Then, after cooling this solution to -78, n-BuLi (2.5M, 4.8 mL, 12 mmol) was slowly added dropwise to the solution, and the resulting solution was stirred at room temperature overnight. However, since a yellow solid was generated in the solution and was not uniformly stirred, MTBE (50 mL) and THF (38 mL) were additionally added.

Meanwhile, ZrCl ₄ (THF) ₂ was dispersed in toluene in a 250 mL schlenk flask prepared separately, and the resulting mixture was cooled to -78. Then, the previously prepared lithiation ligand solution was slowly injected into the mixture. And the resulting mixture was stirred overnight.

Thereafter, the reaction product was filtered to obtain a yellow solid (1.3 g, including LiCl (0.48 g), 1.8 mmol), and after removing the solvent from the filtrate, washing with n-hexane to obtain a yellow solid (320 mg, 0.70 mmol) ( 44% yield).

¹ H NMR (500 MHz, CDCl ₃ ): 0.96 (3H, s), 1.16 (3H, s), 1.91 (3H, s), 1.93 (3H, s), 1.96 (3H, s), 1.97 (3H, s), 5.98 (1H, d), 7.07 (1H, t), 7.23 (1H, d), 7.35 (1H, t), 7.49 (1H, d), 7.70 (1H, d).

(3) Synthesis of dimethylsilylene (tetramethylcyclopentadienyl) (tetrahydroindenyl) zirconium dichloride

The previously synthesized dimethylsilylene (tetramethylcyclopentadienyl) (indenyl) zirconium dichloride (1.049g, 2.3mmol) was put in a mini bombe in a glove box. In addition, platinum oxide (52.4mg, 0.231mmol) was added to the mini bombe, and after assembling the mini bombe, anhydrous THF (30mL) was added to the mini bombe using a canuula, and hydrogen was added to a pressure of about 30 bar. Filled. Then, the mixture contained in the mini bombe was stirred at about 60 for about 1 day, and then the temperature of the mini bombe was cooled to room temperature, and hydrogen was replaced with argon while gradually lowering the pressure of the mini bombe.

Meanwhile, celite dried in an oven at about 120 for about 2 hours was spread on a schlenk filter, and the reaction product of the mini bombe was filtered under argon using this. The PtO ₂ catalyst was removed from the reaction product by the celite. Subsequently, the reaction product from which the catalyst was removed was decompressed to remove the solvent, and a pale yellow solid product was obtained (0.601 g, 1.31 mmol, Mw: 458.65 g/mol).

¹ H NMR (500 MHz, CDCl ₃ ): 0.82 (3H, s), 0.88 (3H, s), 1.92 (6H, s), 1.99 (3H, s), 2.05 (3H, s), 2.34 (2H, m), 2.54 (2H, m), 2.68 (2H, m), 3.03 (2H, m), 5.45 (1H, s), 6.67 (1H, s).

Manufacturing example 2: first Metallocene Preparation of compound

(1) Synthesis of diphenyl (indenyl) (tetramethylcyclopentadienyl) silane

Tetramethylcyclopentadiene-lithium (TMCP-Li, 1.3g, 10mmol), CuCN (45mg, 5mol%), and THF (10 mL) were added to a dried 250mL schlenk flask. At a temperature of -20°C or less, dichlorodiphenylsilane (2.5g, 10mmol) was added dropwise, followed by stirring at room temperature for 16 hours. The temperature was again cooled to -20 or less, and Indene-Li (1.2 g, 10 mmol in THF 10 mL) was added dropwise.

The mixture was stirred at room temperature for 24 hours and dried in vacuo to remove the solvent. LiCl was removed by filtration with hexane, and the filtered hexane solution was vacuum-dried to obtain a diphenyl (indenyl) (tetramethylcyclopentadienyl) silane intermediate.

(2) Synthesis of diphenylsilylene (indenyl) (tetramethylcyclopentadienyl) zirconium chloride

Diphenyl(indenyl)(tetramethylcyclopentadienyl)silane (4.2 g, 10 mol) synthesized previously in a 250 mL schlenk flask was dissolved in THF (15 mL). Then, after cooling this solution to -20 or less, n-BuLi (2.5M, 8.4 mL, 21 mmol) was slowly added dropwise to the solution, and the resulting solution was stirred at room temperature for 6 hours.

Meanwhile, ZrCl ₄ (THF) ₂ was dispersed in toluene in a 250 mL schlenk flask prepared separately, and the resulting mixture was cooled to -20 or less. Then, the previously prepared lithiation ligand solution was slowly injected into the mixture. Then, the resulting mixture was stirred at room temperature for 48 hours, and then dried under vacuum to remove the solvent.

This was dissolved again in dichloromethane, filtered to remove LiCl, and dichloromethane was removed by vacuum drying.

30 mL of toluene was added thereto, stirred for 16 hours, and filtered to obtain a lemon-colored solid (2.1 g, 3.6 mmol) (36% yield).

¹ H NMR (500 MHz, CDCl ₃ ): 8.08-8.12 (m, 2H), 7.98-8.05 (m, 2H), 7.77 (d, 1H), 7.47-7.53 (m, 3H), 7.42-7.46 (m) , 3H), 7.37-7.41(m, 2H), 6.94(t, 1H), 6.23(d, 1H), 1.98(s, 3H), 1.95(s, 3H), 1.68(s, 3H), 1.52( s, 3H)

(3) Synthesis of diphenylsilylene (tetramethylcyclopentadienyl) (tetrahydroindenyl) zirconium dichloride

Diphenylsilylene (tetramethylcyclopentadienyl) (indenyl) zirconium dichloride (1.0 g, 1.7 mmol), Pd/C (10 mol%), dichloromethane (40 mL) synthesized previously was added to a 100 mL high-pressure reactor. After injection, H ₂ (60 bar) was filled, and stirred at 80° C. for 24 hours.

Meanwhile, celite dried in an oven of about 120 for about 2 hours was spread on a schlenk filter, and the reaction product was filtered under argon using this. The reduction catalyst was removed from the reaction product by the celite. Subsequently, the reaction product from which the catalyst was removed was decompressed to remove the solvent, and a light yellow solid product was obtained (0.65 g, 1.1 mmol, 65% yield).

¹ H NMR (500 MHz, CDCl ₃ ): 7.90-8.00 (m, 4H), 7.38-7.45 (m, 6H), 6.80 (s, 1H), 5.71 (s, 1H), 3.50-3.15 (m, 1H) ), 2.75-2.85 (m, 1H), 2.50-2.60 (m, 1H), 2.12 (s, 3H), 2.03 (s, 3H), 1.97-2.07 (m, 1H), 1.76 (s, 3H), 1.53-1.70(m, 4H), 1.48(s, 3H)

Manufacturing example 3: second Metallocene Preparation of compound

(1) synthesis of ligand

Under argon, 10.78 g (48.5 mmol) of 2-(6-tert-butoxyhexyl)cyclopenta-1,3-diene and 7.1 ml of acetone were added to a dried 250 mL schlenk flask under an ethanol solvent. After cooling this solution to 0 ℃, pyrrolidine 5.17g (1.5eq., 72.7mmol) was added dropwise. The reaction mixture was slowly warmed to room temperature and then stirred for 24 hours.

50 ml of water and acetic acid were put in another flask, stirred for 30 minutes, and the reaction was worked-up using this solution and ether.

The organic layer was separated, dried over magnesium sulfate, and 2-(6-tert-butoxyhexyl)-5-(propan-2-ylidene)cyclopenta-1,3-diene 8.2 g (31.25 mmol) was obtained (64.4% yield) .

Under argon, 1.6621 g (10 mmol) of fluorene was prepared in another dried 250 mL schlenk flask, and dissolved in 40 mL of ether. After the aqueous solution was cooled to 0° C., 4.8 ml (12 mmol) of a 2.5M nBuLi hexane solution was added dropwise. The reaction mixture was slowly warmed to room temperature and then stirred for 24 hours.

Take 2.6243 g (10 mmol) of 2-(6-tert-butoxyhexyl)-5-(propan-2-ylidene)cyclopenta-1,3-diene synthesized above, dissolve in THF, and add this dropwise to the lithiated fluorene mixture, Stir for 24 hours.

50 ml of water was put in the flask and quenched, and the organic layer was separated and dried over magnesium sulfate to obtain 4.3 g of ligand (10.02 mmol, 100.2% yield).

¹ H NMR (500 MHz, CDC1 ₃ ): 0.98 (6H, m), 1.14 (9H, s), 1.39 (5H, m), 1.54 (5H, m), 2.93, 3.03 (1H, S), 3.29 ( 2H, m), 4.07 (1H, m), 5.67, 5.98, 6.08, 6.51 (total 3H, S), 7.10 (3H, m), 7.31 (3H, m), 7.78 (2H, d).

(2) Synthesis of metallocene compounds

The ligand synthesized above was added to a dried 250 mL schlenk flask, dissolved in 4 equivalents of MTBE and toluene as a solvent, and then 2.1 equivalents of nBuLi solution was added, followed by lithiation until the next day.

2.1 equivalents of ZrCl ₄ (THF) ₂ was taken in a glove box, placed in a 250 ml schlenk flask, and a suspension containing ether was prepared.

Both flasks were cooled to -78°C, and ligand anions were slowly added to the zirconium suspension.

After the injection was completed, the reaction mixture was slowly heated to room temperature, stirred for 24 hours, and then the mixture was vacuum decompressed to remove 4 equivalents of MTBE.

Then, the toluene solution was filtered under argon to remove LiCl, which is a filtered solid filter cake.

Toluene remaining as a filtrate was removed through vacuum reduced pressure, and hexane was added to promote crystallization.

Hexane slurry was filtered under argon, and after filtration, both the solid and the filtrate were evaporated under vacuum reduced pressure. Check the remaining filter cake and filtrate by NMR, respectively, to confirm synthesis, weigh in a glove box, sample, and check the yield and purity of the pink solid metallocene compound 3.45g (5.86mmol, 58.6) % yield).

¹ H NMR (500 MHz, CDCl ₃ ): 0.17 (9H, s), 1.26 (5H, m), 1.45 (5H, m), 2.35 (3H, s), 2.37 (3H, s), 3.27 (2H, m), 5.43 (1H, m), 5.67 (1H, m), 6.00 (1H, m), 7.26 (2H, m), 7.54 (2H, q), 7.79-7.85 (2H, dd), 8.15 (2H , m).

Manufacturing example 4: second Metallocene Preparation of compound

(1) synthesis of ligand

Under argon, 1.66g (10mmol) of fluorene and THF were added to a dried 250mL schlenk flask. After the aqueous solution was cooled to 0° C., 4.8 ml (12 mmol) of a 2.5M nBuLi hexane solution was added dropwise. The reaction mixture was slowly warmed to room temperature and then stirred for 24 hours.

In another 250 mL schlenk flask, 3.025 g (10 mmol) of (3-(6-tert-butoxyhexyl) cyclopenta-2,4-dienylidene) cyclopentanone was prepared and dissolved in THF, and this mixture was added dropwise to the lithiation fluorene. It was stirred at room temperature for 24 hours.

Water was put into the flask, quenched, and work-up with ether to separate the organic layer, and then dried over magnesium sulfate to obtain 4.6 g (10 mmol) of ligand.

¹ H NMR (500 MHz, CDCl ₃ ): 1.17-1.20 (9H, m), 1.31-1.55 (12H, m), 1.84 (2H, m), 2.37 (2H, m), 3.34 (2H, m), 3.75 (1H, m), 3.93 (1H, s), 5.63 (1H, s), 5.63-5.92 (total 1H, s), 6.09 (1H, s), 7.13-7.16 (2H, m), 7.29-7.38 (4H, m), 7.62 (1H, m), 7.80 (1H, m).

(2) Synthesis of metallocene compounds

The ligand synthesized above was added to a dried 250 mL schlenk flask, dissolved in 40 mL of ether, and then 2.5 equivalents of nBuLi solution was added thereto, followed by lithiation until the next day.

1.0 equivalent of ZrCl ₄ (THF) ₂ was taken in a glove box, placed in a 250 ml schlenk flask, and a suspension containing ether was prepared.

Both flasks were cooled to -78°C, and ligand anions were slowly added to the zirconium suspension.

After the injection was completed, the reaction mixture was slowly heated to room temperature, stirred for 24 hours, filtered, and filtered to remove LiCl, a solid filter cake.

The solvent remaining as filtrate was removed through vacuum reduced pressure, and hexane was added to promote crystallization.

Hexane slurry was filtered under argon, and after filtration, both the solid and the filtrate were evaporated under vacuum reduced pressure. The remaining filter cake and filtrate were checked by NMR, respectively, to confirm synthesis, weighed in a glove box, and sampled to check the yield and purity. 3.24 g (5.1 mmol, 51) of the red solid metallocene compound % yield).

¹ H NMR (500 MHz, CDCl ₃ ): 1.08 (9H, s), 1.19-1.21 (4H, m), 1.37-1.40 (4H, m), 1.98 (4H, s), 2.25-2.27 (2H, m) ), 2.63-2.65 (2H, m), 3.18-3.19 (2H, m), 3.20 (2H, m), 5.30 (1H, s), 5,56 (1H, s), 5.91 (1H, s), 7.18-7.22 (3H, m), 7.48-7.50 (3H, m), 7.60 (2H, d), 8.07-8.08 (2H, m).

<Preparation of supported catalyst>

Comparative example 1 (only supported, Manufacturing example One)

3.0 kg of a toluene solution was put in a 20L sus high-pressure reactor, and 1,000 g of silica (SP2410 manufactured by Grace Davison, calcined at 250° C.) was added, followed by stirring while raising the reactor temperature to 40. After sufficiently dispersing silica for 60 minutes, 2.6 kg of a 30 wt% methylaluminoxane (MAO)/toluene solution was added, the temperature was raised to 80, and then stirred at 200 rpm for 12 hours. After lowering the reactor temperature to 40 again, the stirring was stopped, and after settling for 30 minutes, the reaction solution was decanted.

3.0 kg of toluene was added to the reactor, 50 g of the metallocene compound of Preparation Example 1 and 1,000 mL of toluene were placed in a flask to prepare a solution, and sonication was performed for 30 minutes.

The metallocene compound/toluene solution of Preparation Example 1 thus prepared was added to the reactor and stirred at 200 rpm for 90 minutes. After lowering the reactor temperature to room temperature, the stirring was stopped, and after settling for 30 minutes, the reaction solution was decanted.

3.0 kg of hexane was added to the reactor, the hexane slurry was transferred to a filter dryer, and the hexane solution was filtered. It was dried under reduced pressure at 50 for 4 hours to prepare a 1520g-SiO ₂ supported catalyst.

Comparative example 2

A supported catalyst was prepared in the same manner as in Comparative Example 1, except that the metallocene compound of Preparation Example 2 was used instead of the metallocene compound of Preparation Example 1.

Example 1 (mixed support, Manufacturing example One, Manufacturing example 3)

100 mL of toluene was added to a 350 mL autoclave glass reactor, and 10 heh of silica was added, followed by stirring while raising the reactor temperature to 40°C.

30wt% methylaluminoxane (MAO)/toluene solution 30mL was added, the temperature was raised to 80°C, and the mixture was stirred at 200rpm for 12 hours.

After lowering the reactor temperature to 40 again, the stirring was stopped, and after settling for 30 minutes, the reaction solution was decanted.

50 mL of toluene was added to the reactor, 0.50 g of the metallocene compound of Preparation Example 1 and A solution was prepared by placing 0.10 g of the metallocene compound of Preparation Example 3 and 30 mL of toluene in a flask, followed by sonication for 30 minutes.

The metallocene compound/toluene solution thus prepared was added to the reactor and stirred at 200 rpm for 90 minutes. After lowering the reactor temperature to room temperature, the stirring was stopped, and after settling for 10 minutes, the reaction solution was decanted.

100 mL of hexane was added to the reactor, and the hexane slurry was transferred to a 250 mL schlenk flask, and the hexane solution was decanted. It was dried under reduced pressure at room temperature for 3 hours to prepare a 15.5g-SiO ₂ supported catalyst.

Example 2 (mixed support, Manufacturing example One, Manufacturing example 4)

A supported catalyst was prepared in the same manner as in Example 1, except that 0.06 g of the metallocene compound of Preparation Example 4 was used instead of the metallocene compound of Preparation Example 3.

Example 3 (mixed support, Manufacturing example 2, Manufacturing example 3)

3.0 kg of a toluene solution was added to a 20L sus high-pressure reactor, and 900 g of silica (SP2410 manufactured by Grace Davison, calcined at 250°C) was added, followed by stirring while raising the reactor temperature to 40. After sufficiently dispersing silica for 60 minutes, 2.6 kg of a 30 wt% methylaluminoxane (MAO)/toluene solution was added, the temperature was raised to 80, and then stirred at 200 rpm for 12 hours. After lowering the reactor temperature to 40 again, the stirring was stopped, and after settling for 30 minutes, the reaction solution was decanted.

3.0 kg of toluene was added to the reactor, and 50 g of the metallocene compound of Preparation Example 2 and A solution was prepared by putting 6.0 g of the metallocene compound of Preparation Example 3 and 1,000 mL of toluene in a flask, and sonication was performed for 30 minutes.

The metallocene compound/toluene solution thus prepared was added to the reactor and stirred at 200 rpm for 90 minutes. After lowering the reactor temperature to room temperature, the stirring was stopped, and after settling for 30 minutes, the reaction solution was decanted.

3.0 kg of hexane was added to the reactor, the hexane slurry was transferred to a filter dryer, and the hexane solution was filtered. It was dried under reduced pressure at 50 for 4 hours to prepare a 1310g-SiO ₂ supported catalyst.

Example 4 (mixed support, Manufacturing example 2, Manufacturing example 4)

In the same manner as in Example 3, except that 65 g of the metallocene compound of Preparation Example 2 was used, and 5.5 g of the metallocene compound of Preparation Example 4 was used instead of the metallocene compound of Preparation Example 3, a supported catalyst Was prepared.

<Olefin polymerization>

Comparative example 1-1, 2-1, and Example 1-1 to 4-1

TiBAL 2mL (1M, 1 hexane) and 100g of 1-Hexane were added to a 2L autoclave high-pressure reactor, 0.6kg of isobutene was added, and the temperature was raised to 85°C while stirring at 500rpm.

80 mg of the metallocene-supported catalyst obtained in Comparative Examples 1 and 2, and Examples 1 to 4, and 20 mL of n-hexane were added to a 30 mL vial and introduced into the reactor.

Under an ethylene pressure of 40 bar, the reaction was carried out for 1 hour while stirring at 500 rpm, and the temperature was lowered to 60° C., then the stirring was stopped and slowly exhausted.

The obtained polymer was vacuum dried in an oven at 80° C. for 3 hours.

The polymerization conditions and basic physical properties of the copolymer are summarized in Table 1 below.

Example 1-1 Example 2-1 Example 3-1 Example 4-1 Comparative Example 1-1 Comparative Example 2-1 catalyst Manufacturing Example 1
Manufacturing Example 3 Manufacturing Example 1
Manufacturing Example 4 Manufacturing Example 2
Manufacturing Example 3 Manufacturing Example 2
Manufacturing Example 4 Manufacturing Example 1 Manufacturing Example 2 activation
(kgPE/gCat) 2.9 2.6 2.1 3.2 2.6 2.0 H ₂ input
(mol%) 0.07 0.06 0.10 0.10 0.07 0.07 MI _2.16 0.61 0.68 0.94 0.85 1.0 0.94 Tm(℃) 117.0 119.1 117.2 118.2 121.2 121.0 Molecular weight distribution (PDI) 3.0 2.9 2.9 3.0 3.4 3.3 Bulk density
(g/cm ³ ) 0.35 0.36 0.36 0.36 0.32 0.33 Melt strength
(mN) 83 83 66 67 61 60

Comparative example 1-2, Example 3- 2, and 4-2

An isobutene slurry loop continuous polymerization reactor was used as a polymerization reactor. (Reactor volume: 140L, reaction flow rate 8m/s)

Ethylene gas required for polymerization, hydrogen, and 1-hexane, which is a comonomer, were continuously continuously added, and the concentration was confirmed by on-line chromatograph.

The supported catalyst was fed with isobutene slurry, the reactor pressure was maintained at 40 bar, and the temperature was maintained at 84°C.

The polymerization conditions and basic physical properties of the copolymer are summarized in Table 2 below.

Example 3-2 Example 4-2 Comparative Example 1-2 catalyst Manufacturing Example 2
Manufacturing Example 3 Manufacturing Example 2
Manufacturing Example 4 Manufacturing Example 1 Ethylene load
(kg/hr) 25 25 24 Hydrogen input
(ppm) 12 9 10 1-hexene
input
(wt%) 10.5 10.0 12.3 Slurry density
(g/L) 560 562 563 activation
(kgPE/kgCat/hr) 3.7 3.1 2.5 Bulk density
(g/cm ³ ) 0.44 0.43 0.40 Settling efficiency
(%) 55 54 52 density
(g/cm ³ ) 0.919 0.921 0.921 MI _2.16 1.02 1.07 1.09 Molecular Weight
(10 ⁴ g/mol) 11.3 11.0 10.7 Molecular weight distribution (PDI) 2.9 2.8 3.2 Melt strength
(mN) 65 63 58

< Experimental example >

Production of film

Using the olefin polymers of Examples 3-2, 4-2, and Comparative Example 1-2, films were prepared by the method of Film Blowing.

It proceeded under conditions of 170° C., 35 rpm, and a blown-up ratio of 2.3.

Evaluation of physical properties of polymers and films

The physical properties of the olefin polymer and the physical properties of the film were measured according to the following evaluation method, and the results are shown in Table 3.

1) Density: ASTM 1505

2) Melt Index (MI, 2.16kg/10kg): Measurement Temperature 190, ASTM 1238

3) Melt strength: It was measured under the following conditions.

Capillary: die L/D=15, shear rate: 72/s

Wheel: Initial speed=18mm/s, acceleration=12mm/s ²

4) Molecular weight, molecular weight distribution: The number average molecular weight, the weight average molecular weight, and the Z average molecular weight were measured using a measurement temperature of 160 and gel permeation chromatography-FTIR (GPC-FTIR). The molecular weight distribution was expressed by the ratio of the weight average molecular weight and the number average molecular weight.

5) Tensile strength (Tensile strength at break), elongation (Elongation at break): Measured based on ASTM D 882. At this time, the test speed was 500 mm/min, and the average value was taken by measuring 10 times per specimen.

6) Elmedorf tear strength: A film of a certain thickness was cut into a test piece with a die cutter, and then measured according to ASTM D 1922. At this time, the test speed was 500 mm/min, and the average value was taken by measuring 10 times per specimen.

7) Dart impact: Measured at least 20 times per film based on ASTM D 1709 [Method A] to determine the impact strength of the falling fall.

8) Cloudiness: It was measured based on ASTM D 1003. At this time, it was measured 10 times per specimen and the average value was taken.

Example 3-2 Example 4-2 Comparative Example 1-2 thickness
(㎛) 53 55 56 Haze
(%) 11 12 14 Fall impact strength
(g) 550 530 450 Tensile strength (MD)
(kgf/cm ² ) 475 478 466 Tensile strength (TD)
(kgf/cm ² ) 459 459 450 Tear strength (MD)
(kg/cm) 169 165 165 Tear strength (TD)
(kg/cm) 168 165 167

Referring to Tables 2 and 3, in the case of mLLDPE of Comparative Example 1-2 prepared using a solely supported metallocene catalyst, the basic physical properties of the polymer, such as molecular weight or molecular weight distribution, are partially similar to those of the Examples, but melt strength It can be confirmed that the back is slightly lowered, the haze value is high, and optical properties are poor, and it can be clearly confirmed that mechanical properties such as tensile strength and tear strength, especially the fall impact strength, are very poor.

On the other hand, the olefin polymer prepared by using the hybrid supported catalyst of Examples of the present invention exhibited harmonized physical properties due to good transparency, processability and mechanical properties. In particular, it can be seen that mechanical properties such as fall impact strength are very improved, and transparency is also good, so that contradicting physical properties that have not been solved in the prior art can be achieved simultaneously.

Claims (12)

A first metallocene compound represented by the following formula (1);
A second metallocene compound represented by the following formula (2);
Cocatalyst compounds; And
A method for producing an olefin-based polymer, comprising polymerizing an olefin-based monomer in the presence of a mixed supported metallocene catalyst including a carrier,
The olefin-based polymer has a fall impact strength value of 500 g or more according to ASTM D 1709 [Method A], a method for producing an olefin-based polymer:
[Formula 1]

In Formula 1,
M1 is a Group 4 transition metal;
X11 and X12 are the same as or different from each other, and each independently a halogen, a nitro group, an amido group, a sulfonate group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a silyl group, or an aryl group having 6 to 20 carbon atoms. ;
B1 is carbon (C), silicon (Si), or germanium (Ge);
Q11 and Q12 are the same as or different from each other, and each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms;
R1 to R14 are the same as or different from each other, and each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, a silyl group, a silylalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms;
[Formula 2]

In Formula 2,
M2 is a Group 4 transition metal;
X21 and X22 are the same as or different from each other, and each independently a halogen, a nitro group, an amido group, a sulfonate group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a silyl group, or an aryl group having 6 to 20 carbon atoms. ;
B2 is carbon (C), silicon (Si), or germanium (Ge);
Q21 and Q22 are the same as or different from each other, and each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, or are linked to each other to form an aliphatic ring having 4 to 10 ring atoms. Can be formed;
R21 to R31 are the same as or different from each other, and each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, a silyl group, a silylalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms;
n is the number of repeating alkylene units, and is an integer of 1 to 10;
R32 is hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.
The method of claim 1,
M1 in Formula 1 is zirconium (Zr) or hafnium (Hf);
X11 and X12 are the same as or different from each other, and each independently, chlorine (Cl) or bromine (Br), a method for producing an olefin-based polymer.
The method of claim 1,
B1 in Formula 1 is silicon (Si) or germanium (Ge);
Q11 and Q12 are the same as or different from each other, and each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, a method for producing an olefin-based polymer.
The method of claim 1,
N in Formula 2 is an integer of 4 to 8;
R32 is hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, or a tert-butyl group.
The method of claim 1,
M2 in Formula 2 is zirconium (Zr) or hafnium (Hf);
X21 and X22 are the same as or different from each other, and each independently, chlorine (Cl) or bromine (Br), a method for producing an olefin-based polymer.
The method of claim 1,
B2 in Formula 2 is carbon (C) or silicon (Si);
Q21 and Q22 are the same as or different from each other, and each independently hydrogen or an alkyl group having 1 to 10 carbon atoms, or are linked to each other to form an aliphatic ring having 4 to 10 ring atoms, a method for producing an olefin polymer.
The method of claim 1,
The cocatalyst compound is a method for producing an olefin-based polymer comprising at least one of compounds represented by the following Formula 3, Formula 4, or Formula 5:
[Formula 3]
-[Al(R40)-O] _n-
In Chemical Formula 3,
R40 may be the same as or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a halogen-substituted C 1 to C 20 hydrocarbon;
n is an integer of 2 or more;
[Formula 4]
D(R50) ₃
In Chemical Formula 4,
R50 may be the same as or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a halogen-substituted C 1 to C 20 hydrocarbon;
D is aluminum or boron;
[Formula 5]
_{^{[LH] + [ZA 4]}} - or _{^{[L] + [ZA 4]}} -
In Chemical Formula 5,
L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a group 13 element; A may be the same as or different from each other, and each independently one or more hydrogen atoms is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy. .
delete The method of claim 1,
The olefinic monomer is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene , 1-tetradecene, 1-hexadecene, and a method for producing an olefin-based polymer comprising at least one selected from the group consisting of 1-eicosene.
The method of claim 1,
The olefin polymer has a weight average molecular weight of 50,000 to 500,000 g/mol.
The method of claim 1,
The molecular weight distribution (PDI) value of the olefin-based polymer is 2 to 4, the method for producing an olefin polymer. delete