KR20190061652A - Supported hybrid metallocene catalyst, and the method for preparing polyolefin with good processability using the same - Google Patents

Abstract

The present invention relates to a hybrid supported metallocene catalyst and a method for manufacturing a polyolefin with excellent processability using the same. More particularly, the present invention relates to the hybrid supported metallocene catalyst using two different metallocene compounds and the method for manufacturing the polyolefin having improved processability using the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a hybrid supported metallocene catalyst, and a process for producing a polyolefin having excellent processability using the same. BACKGROUND ART [0002]

More particularly, the present invention relates to hybrid supported metallocene catalysts using two different metallocene compounds, and to a process for producing a metallocene catalyst having improved processability using the same. To a process for producing the polyolefin.

Conventionally, the preparation of olefin polymers has generally employed the so-called Ziegler-Natta catalyst system consisting of the main catalyst component of a titanium or vanadium compound and the cocatalyst component of an alkyl aluminum compound. However, although the Ziegler-Natta catalyst system is a multi-active catalyst having a plurality of active species, the molecular weight distribution of the polymer is broad, but the composition distribution of the comonomer is not uniform.

Since the metallocene catalyst system composed of the metallocene compound of the transition metal of the periodic table group 4, such as titanium, zirconium, and hafnium, and methylaluminoxane, which is a cocatalyst, is a homogeneous catalyst having a single catalytic active site, - Natta catalyst system, the molecular weight distribution of the polymer is narrow, the composition distribution of the comonomer is uniform, and the characteristics of the polymer can be changed according to the modification of the ligand structure of the catalyst.

On the other hand, the metallocene catalyst is more expensive than the conventional Ziegler-Natta catalyst but has high activity and is economically valuable. Especially, since the reactivity to the comonomer is good, the amount of the comonomer There is an advantage that the incorporated polymer can be obtained with high activity. Even if the same amount of comonomer is used, a polymer having a higher molecular weight with a more uniform composition distribution can be produced, so that it can be applied as a film or an elastomer having good physical properties. In addition, since the wax-like extract of low molecular weight is hardly generated in the copolymer, it can be applied to applications requiring medical hygiene.

In general, it is known that an anthra-metallocene compound, which is a transition metal compound containing two bridged catalysts, that is, two ligands connected to each other by a bridge group, is excellent in reactivity with respect to comonomers, and is useful for preparing olefin homopolymers or copolymers Have been used as catalysts. In particular, it is known that an anisma-metallocene compound comprising a cyclopentadienyl-fluorenyl ligand can produce a high molecular weight polyethylene, thereby controlling the microstructure of the polypropylene.

Polymers prepared from such metallocene catalysts are known to have excellent mechanical properties. However, metallocene catalysts have a single active site, resulting in polymers with narrow molecular weight distributions. As a result, the olefin polymer prepared from the metallocene catalyst has poor processability due to the extrusion load and the like, and the injection flowability is shortened, resulting in a significant decrease in the productivity. Accordingly, there is a growing demand for a new catalyst capable of producing an olefin polymer having excellent processability while retaining the merits of a metallocene catalyst.

Korean Patent Registration No. 10-0753478 discloses a hybrid supported metallocene catalyst in which two different metallocene catalysts are supported on one support. The above catalyst has an advantage of being able to produce a polyethylene copolymer having an irregular or pseudomolecular weight distribution and excellent in workability and high temperature withstand voltage, but it is not preferable from the standpoint of exhibiting a certain limit for improvement in workability.

DISCLOSURE Technical Problem The present invention has been conceived to solve the problems described above, and it is an object of the present invention to provide a hybrid supported metallocene catalyst in which two different metallocene compounds are supported on the same carrier to produce a polyolefin having improved processability while maintaining mechanical properties .

(A) a transition metal compound represented by the following general formula (1); (B) a transition metal compound represented by the following formula (2); And (C) a carrier.

[Chemical Formula 1]

In formula (1)

M is a Group 4 transition metal;

R1, R2, R3 and R4 are each independently hydrogen; (C1-C20) alkyl, with or without an acetal, ketal or ether group; (C2-C20) alkenyl, with or without an acetal, ketal or ether group; (C1-C20) alkyl (C6-C20) aryl, with or without an acetal, ketal or ether group; (C6-C20) aryl (C1-C20) alkyl, with or without an acetal, ketal or ether group; Or (C1-C20) silyl with or without an acetal, ketal or ether group; Two or more of R1, R2, R3 and R4 may be linked to each other to form an aliphatic ring or an aromatic ring;

R5, R6, R7 and R8 are each independently hydrogen; (C1-C20) alkyl, with or without an acetal, ketal or ether group; (C2-C20) alkenyl, with or without an acetal, ketal or ether group; (C1-C20) alkyl (C6-C20) aryl, with or without an acetal, ketal or ether group;

R9, R10, R11, R12, R13, R14, R15 and R16 are each independently hydrogen; (C1-C20) alkyl, with or without an acetal, ketal or ether group; (C2-C20) alkenyl, with or without an acetal, ketal or ether group; (C1-C20) alkyl (C6-C20) aryl, with or without an acetal, ketal or ether group; (C6-C20) aryl (C1-C20) alkyl, with or without an acetal, ketal or ether group; Or (C1-C20) silyl with or without an acetal, ketal or ether group; Two or more of R9, R10, R11, R12, R13, R14, R15 and R16 may be connected to each other to form an aliphatic ring or aromatic ring;

(C 1 -C 20) alkyl, (C 2 -C 20) alkenyl, (C 2 -C 20) alkynyl, (C 6 -C 20) aryl, (C6-C20) aryl (C1-C20) alkyl, (C1-C20) alkylamido, (C6-C20) arylamido or (C1-C20) alkylidene;

n is an integer of 1 or 2.

(2)

In Formula 2,

M 'is a Group 4 transition metal,

(C1-C20) alkyl, (C2-C20) alkenyl, (C2-C20) alkynyl, (C1-C20) alkylamido, (C6-C20) arylamido and (C1-C20) alkylidene in the group consisting of Selected,

R19 to R28 are the same as or different from each other, and each independently hydrogen; (C1-C20) alkyl, with or without an acetal, ketal or ether group; (C2-C20) alkenyl, with or without an acetal, ketal or ether group; (C1-C20) alkyl (C6-C20) aryl, with or without an acetal, ketal or ether group; (C6-C20) aryl (C1-C20) alkyl, with or without an acetal, ketal or ether group; And (C1-C20) silyl, with or without an acetal, ketal or ether group,

In this case, R19 and R20 or R21 and R22 may be linked to form a ring, and at least two of R23 and R24, R24 and R25, R25 and R26, R26 and R27 or R27 and R28 may be linked to form a ring Can,

R29 to R31 are the same as or different from each other, and each independently hydrogen; (C1-C20) alkyl, with or without an acetal, ketal or ether group; (C2-C20) alkenyl, with or without an acetal, ketal or ether group; (C1-C20) alkyl (C6-C20) aryl, with or without an acetal, ketal or ether group; (C6-C20) aryl (C1-C20) alkyl, with or without an acetal, ketal or ether group; (C1-C20) silyl with or without an acetal, ketal or ether group; (C1-C20) alkoxy; And (C6-C20) aryloxy,

Here, R29 and R30 or R30 and R31 may be connected to each other to form a ring.

And at least one of R 1, R 2, R 3 and R 4 is hydrogen and the others are each independently selected from the group consisting of (C 1 -C 20) alkyl, (C 2 -C 20) alkenyl, (C 6 -C 20) aryl or acetal, (C1-C20) silyl with or without a group; Wherein at least two of R 1, R 2, R 3 and R 4 may be connected to each other to form an aliphatic ring or an aromatic ring.

Also, at least one of R1, R2, R3, and R4 is hydrogen and the others are independently (C1-C20) alkyl.

(C2-C20) alkenyl, (C6-C20) aryl or an acetal, a ketal or an ether, or a mixture of two or more thereof. (C1-C20) silyl with or without a group; Wherein at least two of R 1, R 2, R 3 and R 4 may be connected to each other to form an aliphatic ring or an aromatic ring.

And at least two of R 1, R 2, R 3 and R 4 are hydrogen and the others are independently of each other (C 1 -C 20) alkyl.

Also, the hybrid supported metallocene catalyst further comprises at least one promoter compound selected from the group consisting of the following chemical formulas (3) to (5):

(3)

- [Al (R32) -O] n-

In the formula (3), R32 is a hydrocarbyl radical having 1 to 20 carbon atoms, which is substituted or unsubstituted with a halogen radical or a halogen; n is an integer of 2 or more.

[Chemical Formula 4]

A (R33) ₃

In Formula 4, A is aluminum or boron; R33 are the same or different and each independently represent a hydrocarbyl radical having 1 to 20 carbon atoms which is substituted or unsubstituted with a halogen radical or a halogen.

[Chemical Formula 5]

^{[LH] + [Z (B} ) 4] - or ^{[L] + [Z (B} ) 4] -

In Formula 5, L is a neutral or cationic Lewis acid; H is a hydrogen atom;

Z is a Group 13 element; B are each independently an aryl or alkyl radical having from 6 to 20 carbon atoms in which at least one hydrogen atom is replaced by halogen, hydrocarbyl having from 1 to 20 carbon atoms, alkoxy, or phenoxy radical.

Wherein the support is a silica, alumina, silica-alumina or silica-magnesia.

The present invention also provides a hybrid supported metallocene catalyst, wherein the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2 are contained in a weight ratio of 9: 1 to 1: 9.

And polymerizing the olefin-based monomer in the presence of the mixed supported metallocene catalyst.

The olefinic monomer may be one or more selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, And at least one member selected from the group consisting of tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, And a manufacturing method thereof.

The novel metallocene catalysts according to the present invention have excellent activity relative to existing catalysts and enable the production of polyolefins with high molecular weight and low melt index. Further, it is possible to provide a method for producing a polyolefin exhibiting improved workability while maintaining mechanical properties.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing a chemical reaction formula for preparing a compound of Chemical Formula 1 in an embodiment of the present invention. FIG.

Hereinafter, preferred embodiments of the present invention will be described in detail. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. Throughout the specification, when an element is referred to as " including " an element, it means that it can include other elements, not excluding other elements, unless specifically stated otherwise.

(A) a transition metal compound represented by the following general formula (1); (B) a transition metal compound represented by the following formula (2); And (C) a carrier.

[Chemical Formula 1]

In formula (1)

M is a Group 4 transition metal;

R1, R2, R3 and R4 are each independently hydrogen; (C1-C20) alkyl, with or without an acetal, ketal or ether group; (C2-C20) alkenyl, with or without an acetal, ketal or ether group; (C1-C20) alkyl (C6-C20) aryl, with or without an acetal, ketal or ether group; (C6-C20) aryl (C1-C20) alkyl, with or without an acetal, ketal or ether group; Or (C1-C20) silyl with or without an acetal, ketal or ether group; Two or more of R1, R2, R3 and R4 may be linked to each other to form an aliphatic ring or an aromatic ring;

R5, R6, R7 and R8 are each independently hydrogen; (C1-C20) alkyl, with or without an acetal, ketal or ether group; (C2-C20) alkenyl, with or without an acetal, ketal or ether group; (C1-C20) alkyl (C6-C20) aryl, with or without an acetal, ketal or ether group;

R9, R10, R11, R12, R13, R14, R15 and R16 are each independently hydrogen; (C1-C20) alkyl, with or without an acetal, ketal or ether group; (C2-C20) alkenyl, with or without an acetal, ketal or ether group; (C1-C20) alkyl (C6-C20) aryl, with or without an acetal, ketal or ether group; (C6-C20) aryl (C1-C20) alkyl, with or without an acetal, ketal or ether group; Or (C1-C20) silyl with or without an acetal, ketal or ether group; Two or more of R9, R10, R11, R12, R13, R14, R15 and R16 may be connected to each other to form an aliphatic ring or aromatic ring;

(C 1 -C 20) alkyl, (C 2 -C 20) alkenyl, (C 2 -C 20) alkynyl, (C 6 -C 20) aryl, (C6-C20) aryl (C1-C20) alkyl, (C1-C20) alkylamido, (C6-C20) arylamido or (C1-C20) alkylidene;

n is an integer of 1 or 2.

(2)

In Formula 2,

M 'is a Group 4 transition metal,

(C1-C20) alkyl, (C2-C20) alkenyl, (C2-C20) alkynyl, (C1-C20) alkylamido, (C6-C20) arylamido and (C1-C20) alkylidene in the group consisting of Selected,

R19 to R28 are the same as or different from each other, and each independently hydrogen; (C1-C20) alkyl, with or without an acetal, ketal or ether group; (C2-C20) alkenyl, with or without an acetal, ketal or ether group; (C1-C20) alkyl (C6-C20) aryl, with or without an acetal, ketal or ether group; (C6-C20) aryl (C1-C20) alkyl, with or without an acetal, ketal or ether group; And (C1-C20) silyl, with or without an acetal, ketal or ether group,

In this case, R19 and R20 or R21 and R22 may be linked to form a ring, and at least two of R23 and R24, R24 and R25, R25 and R26, R26 and R27 or R27 and R28 may be linked to form a ring Can,

R29 to R31 are the same as or different from each other, and each independently hydrogen; (C1-C20) alkyl, with or without an acetal, ketal or ether group; (C2-C20) alkenyl, with or without an acetal, ketal or ether group; (C1-C20) alkyl (C6-C20) aryl, with or without an acetal, ketal or ether group; (C6-C20) aryl (C1-C20) alkyl, with or without an acetal, ketal or ether group; (C1-C20) silyl with or without an acetal, ketal or ether group; (C1-C20) alkoxy; And (C6-C20) aryloxy,

Here, R29 and R30 or R30 and R31 may be connected to each other to form a ring.

The term " alkyl " as used herein refers to a monovalent straight or branched saturated hydrocarbon radical consisting solely of carbon and hydrogen atoms. Examples of such alkyl radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, Butyl, pentyl, hexyl, octyl, dodecyl, and the like.

The term " cycloalkyl " as used in the present invention means a monovalent alicyclic alkyl radical consisting of one ring, examples of which include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, But are not limited to, cyclononyl, cyclodecyl, and the like.

The term " alkenyl " as used herein also refers to straight or branched chain hydrocarbon radicals containing one or more carbon-carbon double bonds, including ethenyl, propenyl, butenyl, pentenyl and the like, But is not limited to.

The term " aryl ", as defined in the present invention, is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, including a single or fused ring system. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, fluorenyl, phenanthryl, triphenylenyl, pyreneyl, perylenyle, klycenyl, naphthacenyl, fluoranthenyl and the like.

The term " alkoxy " as used in the present invention means an -O-alkyl radical where 'alkyl' is as defined above. Examples of such alkoxy radicals include, but are not limited to, methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, t-butoxy and the like.

The term " halogen " as used in the present invention means a fluorine, chlorine, bromine or iodine atom.

In the present invention, the transition metal compound represented by Formula 1 is a cyclopentadiene derivative ligand connected with a bridge group of silicon or alkenylene and an anthra-metallocene ligand containing an indenyl derivative ligand in which the aryl is necessarily substituted at the 4-position (ansa-metallocene) structure.

As described above, the transition metal compound of Formula 1 has an aryl-substituted ligand at the 4-position, so that the transition metal compound having a ligand that is not substituted with an aryl group at the 4-position of indene has superior catalytic activity and superior activity Have a synthesis.

Here, the transition metal compound of Formula 1 according to the present invention is a compound wherein at least one or more, preferably two or more, of R1, R2, R3, and R4 are hydrogen and the remaining are independently selected from (C1-C20) C2-C20) alkenyl, (C6-C20) aryl or (C1-C20) silyl, with or without an acetal, ketal or ether group; It is preferable that at least two of R1, R2, R3 and R4 are connected to each other to form an aliphatic ring or aromatic ring, more preferably at least one of R1, R2, R3 and R4, Is a (C1-C20) alkyl, and when the remainder are independently of one another, (C1-C20) alkyl, olefin polymerization using propylene or ethylene as a monomer is excellent and production of a high molecular weight polyolefin is possible.

In the hybrid supported metallocene catalyst of the present invention, the transition metal compound of the formula (1) mainly contributes to the production of isotactic polymers, and the transition metal compound of the above formula (2) mainly contributes to the production of an atatic polymer .

On the other hand, the hybrid supported metallocene catalyst is a catalyst which can be used as an active catalyst component to be used for olefin polymerization by extracting a ligand in the transition metal compound and cationizing the center metal, The compounds represented by the formulas (3) to (5) can act together as a cocatalyst.

Accordingly, the present invention may be characterized in that the hybrid supported metallocene catalyst further comprises at least one cocatalyst compound selected from the group consisting of the following Chemical Formulas 3 to 5:

(3)

- [Al (R32) -O] n-

In the formula (3), R32 is a hydrocarbyl radical having 1 to 20 carbon atoms, which is substituted or unsubstituted with a halogen radical or a halogen; n is an integer of 2 or more.

[Chemical Formula 4]

A (R33) ₃

In Formula 4, A is aluminum or boron; R33 are the same or different and each independently represent a hydrocarbyl radical having 1 to 20 carbon atoms which is substituted or unsubstituted with a halogen radical or a halogen.

[Chemical Formula 5]

^{[LH] + [Z (B} ) 4] - or ^{[L] + [Z (B} ) 4] -

In Formula 5, L is a neutral or cationic Lewis acid; H is a hydrogen atom;

Z is a Group 13 element; B are each independently an aryl or alkyl radical having from 6 to 20 carbon atoms in which at least one hydrogen atom is replaced by halogen, hydrocarbyl having from 1 to 20 carbon atoms, alkoxy, or phenoxy radical.

In order to allow the above-mentioned co-catalyst compound to exhibit a more excellent activation effect, the compound represented by the above-mentioned general formula (3) is not particularly limited as long as it is alkylaluminoxane and preferred examples thereof include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, Aluminoxane, and the like. Particularly preferred compounds are methylaluminoxane.

The alkyl metal compound represented by Formula 4 is not particularly limited, and preferable examples thereof include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, t-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p- Particularly preferred compounds are selected from among trimethylaluminum, triethylaluminum and triisobutylaluminum. Preferred examples of the compound include trimethylaluminum, trimethylaluminum, trimethylaluminum, trimethylaluminum, triethylaluminum, have.

Furthermore, in the co-catalyst compound represented by the above formula (5), the [LH] + is dimethylanilinium cation dimethyl, wherein [Z (A) _4] ^- is [B (C6F5) _4] ^-, and it is preferably, the [ L] ⁺ is [(C ₆ H ₅ ) ₃ C] ⁺ and [Z (A) ₄ ] ^- is [B (C ₆ F ₅ ) ₄ ] ^- . Herein, the co-catalyst compound represented by Formula 4 is not particularly limited, but examples thereof include triethylammonium tetraphenyl borate, tributylammonium tetraphenyl borate, trimethylammonium tetraphenyl borate, tripropylammonium tetraphenyl (O, p-dimethylphenyl) borate, triethylammoniumtetra (p-tolyl) borate, tripropylammoniumtetra (p- tolyl) borate, trimethylammoniumtetra Phenyl) borate, tributylammoniumtetra (ptrifluoromethylphenyl) borate, trimethylammoniumtetra (p-trifluoromethylphenyl) borate, tributylammonium tetrapentafluorophenylborate, N, Amylidium tetraphenylborate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrapentafluorophenyl Borate, diethylammonium tetrapentafluorophenylborate, triphenylphosphonium tetraphenylborate, trimethylphosphonium tetraphenylborate, triphenylcarboniumtetra (p-trivoloromethylphenyl) borate, triphenylcarbonium Tetrapentafluorophenyl borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, and the like.

The addition amount of the above-mentioned co-catalyst compound can be determined in consideration of the addition amount of the transition metal compound represented by the above-mentioned formula (1) and the amount necessary for sufficiently activating the above promoter compound. The content of the co-catalyst compound may be 1: 1 to 100,000, based on the molar ratio of the metal contained in the co-catalyst compound to 1 mole of the transition metal contained in the transition metal compound represented by the formula (1) 1: 1 to 10,000, more preferably 1: 1 to 5,000.

More specifically, as a first method, the compound represented by Formula 3 is preferably used in a molar ratio of 1: 10 to 5,000, more preferably 1: 50 to 1,000, Preferably in a molar ratio of 1: 100 to 1,000. When the molar ratio of the compound represented by the formula (2) to the transition metal compound represented by the formula (1) is less than 1:10, the amount of the aluminoxane is so small that the activation of the metal compound may not proceed completely, The excess aluminoxane acts as a catalyst poison to prevent the polymer chain from growing well.

In the second method, when A is boron in the promoter compound represented by Formula 4, the transition metal compound represented by Formula 1 is used in a ratio of 1: 1 to 100, preferably 1: 1 to 10, Preferably in a molar ratio of 1: 1-3. In the co-catalyst compound represented by Formula 3, when A is aluminum, the amount of water may vary depending on the amount of water in the polymerization system. However, the amount of the transition metal compound represented by Formula 1 is preferably 1: 1 to 1000, : 1 to 500, and more preferably 1: 1 to 100.

The promoter compound represented by Formula 4 is supported on the transition metal compound represented by Formula 5 at a molar ratio of 1: 0.5 to 30, preferably 1: 0.7 to 20, more preferably 1: 1 to 10, . When the ratio of the promoter compound represented by Formula 4 is less than 1: 0.5, the amount of the activator is relatively small and activation of the metal compound is not completely performed, : 30, the activation of the metal compound is completely performed. However, there is a problem that the unit cost of the catalyst composition is not economical due to an excess amount of the remaining activator, or the purity of the produced polymer is lowered.

In the present invention, inorganic or organic carriers used in the production of catalysts can be used without limitation in the technical field of the present invention. Examples of the carrier include SiO2, Al2O3, MgO, MgCl2, CaCl2, ZrO2, TiO2, B2O3, SiO2-TiO2-MgO, bauxite, zeolite, starch, cyclodextrin, SiO2-TiO2, SiO2-V2O5, SiO2-TiO2-MgO, CaO, ZnO, BaO, ThO2, SiO2-Al2O3, SiO2- , Synthetic polymers, and the like. Preferably, the carrier comprises a hydroxy group on the surface, and may be at least one carrier selected from the group consisting of silica, silica-alumina and silica-magnesia.

In the present invention, the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2 may be contained in a weight ratio of 9: 1 to 1: 9, preferably 7: 3 to 3: 7, Most preferably from 6: 4 to 4: 6.

In the present invention, the method for preparing the hybrid supported metallocene catalyst is not particularly limited. The method of supporting the transition metal compound and the promoter compound of Formula 1 or 2 on the carrier includes a method of directly supporting the transition metal compound of Formula 1 and Formula 2 on a dehydrated carrier, A method of supporting the transition metal compound of the above formulas (1) and (2) after the pretreatment with the aforementioned promoter compound, a method of post-treating the transition metal compound of the above formulas (1) and (2) A method in which a transition metal compound of the general formulas (1) and (2) is reacted with a cocatalyst compound and then a carrier is added to react them.

The solvent usable in the above carrying method may be an aromatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated aliphatic hydrocarbon solvent or a mixture thereof. The aliphatic hydrocarbon solvent may include, but is not limited to, pentane, hexane, heptane, octane, nonane, decane, undecane, Dodecane and the like. Examples of the aromatic hydrocarbon solvents include, but are not limited to, benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, and toluene. Examples of the halogenated aliphatic hydrocarbon solvent include, but are not limited to, dichloromethane, trichloromethane, dichloroethane, and trichloroethane

Also, the step of supporting the transition metal compound of Formula 1 and the promoter compound on the carrier may be carried out at a temperature of -70 to 200 ° C, preferably -50 to 150 ° C, more preferably 0 to 100 ° C Is advantageous in view of the efficiency of the deposition process.

The hybrid supported metallocene catalyst produced according to the above production method cooperates with one catalyst for polymerizing an isotactic polymer and one catalyst for polymerizing an atactic polymer, Can be used to prepare the improved polyolefins.

According to an embodiment of the present invention, the polymer produced through the polymerization process carried out by directly contacting the olefin monomer compound is a polymer which is relatively insoluble in the catalyst moiety and / or is stable so that the polymer chain is immobilized rapidly according to this information. Can be prepared by polymerization. Such immobilisation can be carried out, for example, by using a solid insoluble catalyst, by carrying out the polymerization in a medium in which the resulting polymer is generally insoluble, and keeping the polymerization reactants and products below the crystalline melting point of the polymer.

The above-mentioned hybrid supported metallocene catalyst is preferable for olefin polymerization. Accordingly, the present invention discloses a method for producing a polyolefin comprising polymerizing an olefin-based monomer in the presence of the hybrid supported metallocene catalyst. That is, the process for producing a polyolefin according to the present invention is carried out by polymerizing an olefin-based monomer compound in the presence of the mixed supported metallocene catalyst.

Suitable polymerization processes for polyolefin polymerization are well known to those skilled in the art and include bulk polymerization, solution polymerization, slurry polymerization and low pressure gas phase polymerization. Hybrid supported metallocene catalysts are particularly useful in known operating forms using fixed bed, moving bed or slurry processes carried out in single, series or parallel reactors.

When the polymerization reaction is carried out in a liquid phase or a slurry, the solvent or the olefin-based monomer itself can be used as a medium.

Since the hybrid supported metallocene catalysts present in the present invention are present in a homogeneous form in the polymerization reactor, it is preferable to apply the present invention to a solution polymerization process carried out at a temperature above the melting point of the polymer.

The solvent usable in the polymerization reaction may be an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated aliphatic hydrocarbon solvent or a mixture thereof. The aliphatic hydrocarbon solvent may include, but is not limited to, butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, Decane, undecane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, and the like can be given. The aromatic hydrocarbon solvent may include, but not limited to, benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene, chlorobenzene, (Chlorobenzene), and the like. The halogenated aliphatic hydrocarbon solvent may include, but not limited to, dichloromethane, trichloromethane, chloroethane, dichloroethane, trichloroethane, 1,2-dichloroethane, 1,2-dichloroethane, and the like.

In the present invention, the olefin-based monomer may be at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexane, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1 -Tetradecene, 1-petadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-hexadecene, 1-nonadecene, 1-eicosene, or a mixture thereof. Preferably, propylene may be used alone, or propylene and other monomers may be mixed and used.

On the other hand, the amount of the catalyst added in the polymerization reaction of the present invention is not particularly limited because it can be determined within a range in which the polymerization reaction of the monomers can sufficiently take place in accordance with slurry, liquid, vapor or massive processes. However, the amount of the catalyst and is based on the concentration of the central metal (M) in the main catalyst compound per unit volume (L) of the monomer (transition metal compound) 10 ^-8 to preferably a 1 mol / L, 10 ^-7 To 10 ^{- 1} mol / L, and even more preferably from 10 ^-7 to 10 ^{- 2} mol / L.

At this time, in the step of polymerizing the olefin-based monomer, hydrogen can be introduced and the chain length of the polyolefin can be controlled according to the amount of hydrogen to be added. That is, when the amount of introduced hydrogen is large, a polyolefin having a small molecular weight can be produced, and when the amount of hydrogen to be introduced is small, a polyolefin having a large molecular weight can be produced. The preferred amount of hydrogen to serve in this role may be from 0.1 to 50 mg, preferably from 1 to 30 mg, more preferably from 5 to 20 mg, most preferably from 10 to 15 mg.

The polymerization reaction of the present invention may be carried out in a batch type, a semi-continuous type or a continuous type, preferably a continuous reaction.

The temperature and pressure conditions of the polymerization reaction of the present invention can be determined in consideration of the efficiency of the polymerization reaction depending on the kind of the reaction to be applied and the type of the reaction. However, the polymerization temperature is preferably 40 to 150 ° C, And the pressure may be 1 to 100 atm, preferably 5 to 50 atm.

Hereinafter, a specific embodiment of the present invention will be described.

Except where otherwise noted, all ligand and catalyst synthesis experiments were performed using standard Schlenk or glovebox techniques under a nitrogen atmosphere, and organic solvents used in all reactions were refluxed under sodium metal and benzophenone to yield water And the product was distilled immediately before use. 1H-NMR analysis of the synthesized ligand and catalyst was carried out at room temperature using a Bruker 300 MHz.

Toluene as a polymerization solvent was used after passing through a tube filled with 5A molecular sieve and activated alumina and bubbling with high purity nitrogen to sufficiently remove moisture, oxygen and other catalyst poison substances. All the polymerization was carried out by introducing the required amount of solvent, co-catalyst, monomers to be polymerized, etc. in a high-pressure reactor (autoclave) completely blocked with the external air and then adding the catalyst.

[catalyst Manufacturing example  One]

Transition metal compound ( Tetramethylcyclopentadienyl Dimethylsilyl  2- methyl -4- (4-t- Butylphenyl ) Indenylzirconium Ditetrahydroborate  ( Tetramethylcyclopentadienyl  dimethylsilyl 2-methyl-4- (4- tert - butylphenyl ) indenyl Zr ditetrahydrobrate ) synthesis

1) Synthesis of dimethyl tetramethylcyclopentadienyl chlorosilane (dimethyl tetramethylcyclopentadienyl chlorosilane)

N-BuLi (2.5 M hexane solution) (170 ml) was slowly added dropwise at -10 ° C under a nitrogen atmosphere, followed by dropwise addition of 12 (trimethylsilyl) methylene chloride Lt; / RTI > for 1 hour. The temperature of the reaction solution was lowered to -10 ° C again, and then dimethyldichlorosilane (170 g) was added thereto. The mixture was stirred at room temperature for 12 hours for reaction, and then the reaction product was vacuum-dried. Hexane (500 ml) was added thereto to dissolve the reaction product. The reaction product was filtered through a Celite filter, and the filtered solution was vacuum-dried to obtain 70 g of dimethyl tetramethylcyclopentadienyl chlorosilane in the form of yellow oil (yield: 80%).

2) Synthesis of dimethyl tetramethylcyclopentadienyl 2-methyl-4- (4-t-butylphenyl) indenyl silane (Dimethyl tetramethylcyclopentadienyl 2-methyl-4- (4-tert-butylphenyl) indenyl silane)

The flask charged with toluene (200 ml), tetrahydrofuran (40 ml) and 2-methyl-4- (4-t-butylphenyl) indene (50 g) was cooled to -10 ° C and n-BuLi M hexane solution) (76 ml) was slowly added dropwise thereto, followed by stirring at room temperature for 12 hours. The temperature of the reaction mixture was lowered to -10 DEG C again, and then dimethyltetramethylcyclopentadienylchlorosilane (38 g) was added thereto, followed by stirring at room temperature for 12 hours. After completion of the reaction, water (400 ml) was added thereto, and the mixture was stirred at room temperature for 1.5 hours. Then, the mixture was extracted with toluene and vacuum dried to obtain dimethyltetramethylcyclopentadienyl 2- -Butylphenyl) indenylsilane (yield: 95%).

3) Synthesis of tetramethylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t-butylphenyl) indenylzirconium dichloride (Tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4- synthesis

Dimethyl tetramethylcyclopentadienyl 2-methyl-4- (4-t-butylphenyl) indenylsilane (50 g), toluene (300 ml) and diethyl ether (100 ml) , And n-BuLi (2.5 M hexane solution) (90 ml) was slowly added dropwise. After dropwise addition, the reaction temperature was raised to room temperature, stirred for 48 hours, and then filtered. The obtained filtrate was vacuum-dried to obtain 40 g (yield 80%) of tetramethylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t-butylphenyl) indenyldilithium salt as a solid, And used immediately in the next reaction.

Tetramethylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t-butylphenyl) indenyldilithium salt (40 g), toluene (40 ml) and ether (10 ml) were placed in a flask . In Flask # 2, a mixture of toluene (30 ml) and ZrCl ₄ (20 g) was prepared. The mixture of flask # 2 was slowly dropped into flask # 1 with a cannula, and then stirred at room temperature for 24 hours. After stirring, the mixture was vacuum-dried, extracted with methylene chloride (500 ml), filtered through a Celite filter, and then the filtrate was vacuum-dried. The resulting solid was washed with a 1: 3 mixture of methylene chloride and n-hexane (50 ml) and vacuum dried to obtain tetramethylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t -Butylphenyl) indenyl zirconium dichloride (yield: 60%).

4) Synthesis of tetramethylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t-butylphenyl) indenylzirconium ditetrahydroburate (Tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4- ) synthesis

5.2 g of tetramethylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t-butylphenyl) indenylzirconium dichloride, 1.5 g of sodium tetraborate and 100 ml of tetrahydrofuran were placed in a flask And reacted at room temperature for 12 hours. Thereafter, the solid portion was filtered out, and the obtained solution portion was vacuum dried to obtain a white solid. The resulting white solid was transferred to a flask containing 500 ml of diethyl ether, and stirred at room temperature for 5 hours. Thereafter, the insoluble portion was removed using a filter, and diethyl ether was blown off under vacuum to obtain 3.3 g of tetramethylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t-butylphenyl) indenylzirconium ditetrahydroborate .

[catalyst Manufacturing example  2]

The transition metal compound (2-methyl-3-H-4,5- dimethyl (2-methyl-2,3,4,5-tetrahydroquinolin-8-yl) -4H-cyclopenta [b] thiophene titanium

A method for preparing the transition metal compound of the above formula (2) can be found in Korean Patent Publication No. KR 10-2017-003195A.

In the present invention, the transition metal compound of Formula 2 was synthesized according to the reaction scheme shown in FIG. The specific synthesis procedure is as follows.

Methyl lithium (1.63 g, 3.55 mmol, 1.6M diethyl ether solution) was added dropwise to a diethyl ether solution (10 mL) having Compound 1 (0.58 g, 1.79 mmol) shown in FIG. 1 dissolved therein at -30 ° C To prepare a mixed solution. The resulting mixed solution was stirred at room temperature overnight, cooled to -30 ° C, and then Ti (NMe ₂ ) ₂ Cl ₂ (0.37 g, 1.79 mmol) was added. The solution to which Ti (NMe ₂ ) ₂ Cl ₂ was added was stirred for 3 hours, and then all of the solvent was removed using a vacuum pump to obtain a solid reaction product. The resulting solid reaction product was dissolved in toluene (8 mL) and Me2SiCl2 (1.16 g, 8.96 mmol) was added to the solution. Wherein Me ₂ SiCl ₂ is added to the solution and then stirred at 80 ℃ 3 days The solvent is removed using a vacuum pump to obtain a red solid compound 2 (Fig. 1) (0.59 g, 75% yield).

1H, NMR (C6D6):? 7.10 (t, J = 4.4 Hz, 1H), 6.90 (d, J = 4.4 Hz, 2H), 5.27 and 5.22 3H), 1.94 and 1.93 (s, 3H), 1.89 and 1.84 (s, 3H), 2.03 (s, 1.72-1.58 (m, 2H, CH 2), 1.36-1.28 (m, 2H, CH 2), 1.17 and 1.14 (d, J = 6.4, 3H, CH 3) ppm.

13C {1H) NMR (C6D6): 162.78, 147.91, 142.45, 142.03, 136.91, 131.12, 130.70, 130.10, 128.90, 127.17, 123.39, 121.33, 119.87, 54.18, 26.48, 21.74, 17.28, 14.46, 14.28, ppm.

[ Example  One]

Preparation of Supported Catalyst Formula 1: Formula 2  = 9: 1 ratio)

Silica (manufacturer: Grace, product name: XPO-2412, 2.0 g) was placed in a Schlenk flask (100 ml) in a glove box, and 10 ml of anhydrous toluene solution was added thereto. Then, about 10.2 ml of methylaluminoxane (10 wt% solution of methylaluminoxane in toluene, 15 mmol of Al, manufactured by Albemarle) was slowly added dropwise at 10 DEG C, and the mixture was stirred at 0 DEG C for about 1 hour, , Stirred for 3 hours and cooled to 25 < 0 > C. Separately, another transition metal compound (0.046 g, 81 [mu] mol) synthesized in Example 1 of the catalyst and the transition metal compound (0.003 g, 9 [mu] mol) Taken out of the glove box in a Schrenk flask, and then added with 10 ml of an anhydrous toluene solution. The solution containing the transition metal compound was slowly added to the solution containing silica and methylaluminoxane at 10 DEG C, and then the temperature was raised to 70 DEG C and stirred for 1 hour, then cooled to 25 DEG C for about 24 hours Lt; / RTI > The resulting reaction product was dried in a vacuum to obtain 2.70 g of a supported catalyst of Free Flowing.

Polypropylene polymerization

The inside of a stainless steel autoclave having an internal capacity of 2 L at room temperature was completely replaced with nitrogen. After purging triisobutylaluminum (2 ml of 1M solution in hexane) and 500 g of propylene while maintaining the nitrogen purging, 70 mg of the supported catalyst compound was dispersed in 5 ml of hexane and added to the reactor using high pressure nitrogen. Thereafter, polymerization was carried out at 70 DEG C for 60 minutes. After completion of the polymerization, the reactor was cooled to room temperature and the excess propylene was removed through a discharge line to obtain a white powdery solid. The resulting white solid powder was dried for 15 hours or more while heating to 80 캜 using a vacuum oven to prepare a final polypropylene resin.

[ Example  2]

(0.0028 g, 21 μmol) of the transition metal compound (0.028 g, 49 μmol) synthesized in the first step of the catalyst preparation 1 and the compound 2 synthesized in the second step of the catalyst preparation example 2 were added to prepare a supported catalyst A polypropylene resin was prepared in the same manner as in Example 1 except that the polypropylene resin (1) was supported at a ratio of 7: 3.

[ Example  3]

The transition metal compound (0.020 g, 35 μmol) synthesized in the first step of the catalyst of Example 1 and the transition metal compound (0.013 g, 35 μmol) of the general formula 2 synthesized in Example 2 of the catalyst were added to prepare a supported catalyst A polypropylene resin was prepared in the same manner as in Example 1 except that the polypropylene resin (1) was supported at a ratio of 5: 5.

[ Comparative Example  One]

The transition metal compound (0.057 g, 100 μmol) of the formula (1) synthesized in the first step of the catalyst was prepared in the same manner as in Example 1 except that the transition metal compound of the formula (2) , A polypropylene resin was prepared in the same manner as in Example 1 above.

[ Comparative Example  2]

In the preparation of the supported catalyst in Example 1, tetramethylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t-butylphenyl) propane was used instead of the transition metal compound synthesized in Preparation 1 of Catalyst 1 and Catalyst Preparation 2, Except that the transition metal compound (0.060 g, 100 占 퐉 ol) was added to the reaction solution in the same manner as in Example 1, except that tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4- (4-tert-butylphenyl) indenyl Zr dichloride To prepare a polypropylene resin.

[ Experimental Example ]

The properties of the polypropylene resin prepared in the above Examples and Comparative Examples were evaluated by the following methods, and the results are shown in Table 1.

(1) Flexural strength: The flexural strength was measured in accordance with ASTM D790 at 10 mm / min.

(2) IZOD impact strength: The notch impact strength of a 1/8 "specimen was measured according to ASTM D256.

 (3) Processability: The torque of the extruder was measured by a torsion measuring device (measuring method using a load cell device) equipped in an extruder.

(4) Spiral flow distance: The total length of the spiral flow specimen injected at the same injection speed and injection pressure at 230 ° C was measured.

(5) Heat resistance (HDT): The temperature at which the deformation due to the temperature rise was measured when a constant load was applied according to ASTM D648 was measured.

Referring to Table 1, the polypropylene resin prepared using the hybrid supported metallocene catalyst according to the present invention (Examples 1 to 3), the polypropylene resin prepared using the catalyst having only one kind of transition metal It was confirmed that the torque value applied to the extruder was lower than that of the propylene resin (Comparative Example 1), and the injection flowability was longer and the processability was better. It was also found that this effect is far superior to that of the conventionally known metallocene catalyst (Comparative Example 2).

The preferred embodiments of the present invention have been described in detail above. It will be understood by those of ordinary skill 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.

Accordingly, the scope of the present invention is defined by the appended claims rather than the foregoing detailed description, and all changes or modifications derived from the meaning, range, and equivalence of the claims are included in the scope of the present invention Should be interpreted.

Claims (10)

(A) a transition metal compound represented by the following formula (1); (B) a transition metal compound represented by the following formula (2); And (C) a carrier.
[Chemical Formula 1]

In formula (1)
M is a Group 4 transition metal;
R1, R2, R3 and R4 are each independently hydrogen; (C1-C20) alkyl, with or without an acetal, ketal or ether group; (C2-C20) alkenyl, with or without an acetal, ketal or ether group; (C1-C20) alkyl (C6-C20) aryl, with or without an acetal, ketal or ether group; (C6-C20) aryl (C1-C20) alkyl, with or without an acetal, ketal or ether group; Or (C1-C20) silyl with or without an acetal, ketal or ether group; Two or more of R1, R2, R3 and R4 may be linked to each other to form an aliphatic ring or an aromatic ring;
R5, R6, R7 and R8 are each independently hydrogen; (C1-C20) alkyl, with or without an acetal, ketal or ether group; (C2-C20) alkenyl, with or without an acetal, ketal or ether group; (C1-C20) alkyl (C6-C20) aryl, with or without an acetal, ketal or ether group;
R9, R10, R11, R12, R13, R14, R15 and R16 are each independently hydrogen; (C1-C20) alkyl, with or without an acetal, ketal or ether group; (C2-C20) alkenyl, with or without an acetal, ketal or ether group; (C1-C20) alkyl (C6-C20) aryl, with or without an acetal, ketal or ether group; (C6-C20) aryl (C1-C20) alkyl, with or without an acetal, ketal or ether group; Or (C1-C20) silyl with or without an acetal, ketal or ether group; Two or more of R9, R10, R11, R12, R13, R14, R15 and R16 may be connected to each other to form an aliphatic ring or aromatic ring;
(C 1 -C 20) alkyl, (C 2 -C 20) alkenyl, (C 2 -C 20) alkynyl, (C 6 -C 20) aryl, (C6-C20) aryl (C1-C20) alkyl, (C1-C20) alkylamido, (C6-C20) arylamido or (C1-C20) alkylidene;
n is an integer of 1 or 2.
(2)

In Formula 2,
M 'is a Group 4 transition metal,
(C1-C20) alkyl, (C2-C20) alkenyl, (C2-C20) alkynyl, (C1-C20) alkylamido, (C6-C20) arylamido and (C1-C20) alkylidene in the group consisting of Selected,
R19 to R28 are the same as or different from each other, and each independently hydrogen; (C1-C20) alkyl, with or without an acetal, ketal or ether group; (C2-C20) alkenyl, with or without an acetal, ketal or ether group; (C1-C20) alkyl (C6-C20) aryl, with or without an acetal, ketal or ether group; (C6-C20) aryl (C1-C20) alkyl, with or without an acetal, ketal or ether group; And (C1-C20) silyl, with or without an acetal, ketal or ether group,
In this case, R19 and R20 or R21 and R22 may be linked to form a ring, and at least two of R23 and R24, R24 and R25, R25 and R26, R26 and R27 or R27 and R28 may be linked to form a ring Can,
R29 to R31 are the same as or different from each other, and each independently hydrogen; (C1-C20) alkyl, with or without an acetal, ketal or ether group; (C2-C20) alkenyl, with or without an acetal, ketal or ether group; (C1-C20) alkyl (C6-C20) aryl, with or without an acetal, ketal or ether group; (C6-C20) aryl (C1-C20) alkyl, with or without an acetal, ketal or ether group; (C1-C20) silyl with or without an acetal, ketal or ether group; (C1-C20) alkoxy; And (C6-C20) aryloxy,
Here, R29 and R30 or R30 and R31 may be connected to each other to form a ring. The method according to claim 1,
At least one of said R1, R2, R3 and R4 is hydrogen and the others are each independently selected from the group consisting of (C1-C20) alkyl, (C2-C20) alkenyl, (C6-C20) aryl or an acetal, ketal or ether group (C1-C20) silyl; Wherein at least two of R 1, R 2, R 3 and R 4 are connected to each other to form an aliphatic ring or an aromatic ring. The method according to claim 1,
Wherein at least one of R1, R2, R3 and R4 is hydrogen and the others are independently of each other (C1-C20) alkyl. The method according to claim 1,
(C2-C20) alkenyl, (C6-C20) aryl or an acetal, ketal or ether group, optionally substituted with at least one substituent selected from the group consisting of (C1-C20) silyl; Wherein at least two of R 1, R 2, R 3 and R 4 are connected to each other to form an aliphatic ring or an aromatic ring. The method according to claim 1,
Wherein at least two of R 1, R 2, R 3 and R 4 are hydrogen and the others are independently of each other (C 1 -C 20) alkyl. The method according to claim 1,
Wherein the mixed supported metallocene catalyst further comprises at least one promoter compound selected from the group consisting of the following Chemical Formulas 3 to 5:
(3)
- [Al (R32) -O] n-
In the formula (3), R32 is a hydrocarbyl radical having 1 to 20 carbon atoms, which is substituted or unsubstituted with a halogen radical or a halogen; n is an integer of 2 or more.
[Chemical Formula 4]
A (R33) ₃
In Formula 4, A is aluminum or boron; R33 are the same or different and each independently represent a hydrocarbyl radical having 1 to 20 carbon atoms which is substituted or unsubstituted with a halogen radical or a halogen.
[Chemical Formula 5]
^{[LH] + [Z (B} ) 4] - or ^{[L] + [Z (B} ) 4] -
In Formula 5, L is a neutral or cationic Lewis acid; H is a hydrogen atom;
Z is a Group 13 element; B are each independently an aryl or alkyl radical having from 6 to 20 carbon atoms in which at least one hydrogen atom is replaced by halogen, hydrocarbyl having from 1 to 20 carbon atoms, alkoxy, or phenoxy radical. The method according to claim 1,
Wherein the carrier is silica, alumina, silica-alumina or silica-magnesia. The method according to claim 1,
Wherein the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2 are contained in a weight ratio of 9: 1 to 1: 9. 9. A process for producing a polyolefin comprising polymerizing an olefin monomer in the presence of a hybrid supported metallocene catalyst according to any one of claims 1 to 8. 10. The method of claim 9,
Wherein the olefinic monomer is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, And at least one member selected from the group consisting of tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, Way.

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