KR20180062116A - Method for preparing polyolfin - Google Patents

Abstract

The present invention relates to a method for preparing polyolfin. More specifically, the present invention provides a method for preparing polyolfin, which can easily and effectively prepare polyolefin having a high molecular weight and excellent stress crack resistance (full notch creep test, FNCT).

Description

METHOD FOR PREPARING POLYOLFIN [0002]

The present invention relates to a process for producing polyolefins.

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, both of which have been developed for their respective characteristics. Ziegler-Natta catalysts have been widely applied to commercial processes since the invention of the 50's. However, since the Ziegler-Natta catalyst is a multi-site catalyst having a plurality of active sites, the molecular weight distribution of the polymer is broad, The composition distribution is not uniform and there is a limit in securing desired physical properties.

Particularly, when an ultrahigh molecular weight polyolefin having a weight average molecular weight of 1 million or more is produced by using a Ziegler-Natta catalyst, the amount of the catalyst residue (Cl component, etc.) is large and decomposition of the polyolefin may occur during molding at a high temperature. . For this reason, there is a disadvantage that the excellent physical properties as the ultrahigh molecular weight polyolefin can not be properly manifested.

On the contrary, when a high molecular weight polyolefin is obtained by using a metallocene catalyst, the molecular weight distribution is relatively small, and thus the impact resistance can be improved. Further, since the amount of the Cl residue of the catalyst residue is small, the decomposition of the polyolefin can be largely suppressed during the molding process. However, polyolefins prepared using metallocene catalysts suffer from poor processability due to their narrow molecular weight distribution.

Generally, the wider the molecular weight distribution, the higher the degree of decrease in viscosity with shear rate, and the better the workability in the machining area. The polyolefin prepared with the metallocene catalyst, due to the relatively narrow molecular weight distribution, There is a disadvantage in that the extrusion productivity and the bubble stability are greatly reduced at the time of blow molding, and the surface of the produced molded article becomes uneven and the transparency is degraded.

Also, in the process of obtaining a high molecular weight polyolefin using a metallocene catalyst, the molecular weight can be controlled by controlling the amount of hydrogen gas input. As the amount of the hydrogen gas is increased, the molecular weight of the polyolefin is reduced. Furthermore, even if the polymerization is proceeded in the state where no hydrogen gas is introduced, it is difficult to obtain an ultra high molecular weight polyolefin having a weight average molecular weight of 1 million or more because of its excellent hydrogen elimination reaction due to the characteristics of the metallocene catalyst.

On the other hand, the polyolefin resin used in a large-diameter high-pressure pipe is required to have a full-notch creep test (FNCT), which is a characteristic capable of withstanding high temperatures and high pressures. Such FNCT properties depend on the content of ultrahigh molecular weight polyolefin in the polyolefin resin It is very influential.

Korean Patent Laid-Open Publication No. 2015-0037520 discloses a method of polymerizing an ultrahigh molecular weight polyolefin using a multi-stage reactor, and a method of adding a molecular weight modifier and a second olefin monomer in a second step reaction to polymerize. Korean Patent Laid-Open Publication No. 2016-0038589 discloses a method of further polymerizing a metallocene catalyst and a second olefin monomer in a second-step reaction.

However, since the above methods are methods for controlling the molecular weight by adding reactants or catalysts in the second-stage reactor in the multi-stage CSTR reactor, the polymerization process becomes complicated, and the FNCT of the polyolefin resin obtained by the above- It is still necessary to study a polyolefin resin having satisfactory physical properties and having a more excellent FNCT.

Accordingly, it is an object of the present invention to provide a process for producing a polyolefin which enables a polyolefin having a high molecular weight and excellent in full-stress creep test (FNCT) to be produced more easily and effectively.

In order to solve the above-mentioned problems, the present invention provides a process for producing a metallocene catalyst, which comprises, in the presence of a supported metallocene catalyst comprising at least one metallocene compound having a Group 4 transition metal as a central metal, A polymerization reaction in which an olefin monomer is polymerized to produce a polyolefin; And

A post reaction which further converts the unreacted olefin-based monomer present in the reaction mixture of the polymerization reaction to a polyolefin under a pressure of 1.5 to 3.0 kg / cm ³ ;

And a method for producing the polyolefin.

As described above, according to the present invention, the unreacted olefin-based monomer existing in the polymerization product of the olefin-based monomer is further converted into the polyolefin under the controlled pressure condition, so that the polyolefin having improved mechanical properties and stress- Can be manufactured.

Hereinafter, a method for producing a polyolefin according to an embodiment of the present invention will be described.

According to one embodiment of the present invention, in the presence of a supported metallocene catalyst containing at least one metallocene compound having a Group 4 transition metal as a central metal, a promoter compound, and a carrier and hydrogen gas, the olefin monomer To produce a polyolefin; And a post reaction for further converting the unreacted olefin-based monomer present in the reaction mixture of the polymerization reaction to a polyolefin under a pressure of 1.5 to 3.0 kg / cm < ³ >.

In the process for producing a polyolefin of the present invention, the polymerization reaction is carried out in the presence of at least one metallocene compound having a Group 4 transition metal as a central metal, a promoter compound, and a supported metallocene catalyst comprising a carrier and hydrogen gas, And polymerizing the monomer to produce a polyolefin.

The polymerization may be carried out in a single reactor consisting of one reactor, or in a Cascade-CSTR reactor comprising first and second reactors.

During the polymerization reaction, the polyolefin having a desired molecular weight can be polymerized by appropriately controlling the composition of the supported metallocene catalyst, the amount of the comonomer, the molecular weight regulator, the flow rate of the hydrogen gas, the reaction pressure, and the reaction temperature.

The polymerization reaction is a step of polymerizing an olefin monomer to form a polyolefin in the presence of a supported metallocene catalyst and hydrogen gas. Because of the high reactivity between the metallocene catalyst and the hydrogen gas, most of the olefin monomer It is converted to polyolefin, and hydrogen gas is also almost consumed. However, inevitably, the olefinic monomer remaining unreacted is present in about 2 to about 5 weight percent.

According to the process for producing a polyolefin of the present invention, the unreacted olefin-based monomer is converted into a polyolefin in the post-reaction so that the conversion is substantially 100%, and the unreacted olefin- So that the FNCT can obtain an improved polyolefin.

The structure of the metallocene compound used in the production process of the polyolefin of the present invention is not limited, but at least one metallocene compound suitable for high molecular weight or ultra high molecular weight polyolefin polymerization can be used.

According to an embodiment of the present invention, the metallocene compound may include a first metallocene compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

A represents a hydrogen atom, a halogen atom, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, a C7 to C20 arylalkyl group, a C1 to C20 alkoxy group, C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;

D is -O-, -S-, -N (R) - or -Si (R) (R ') -, wherein R and R' are the same or different and each independently hydrogen, halogen, C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group;

L is a straight or branched alkylene group of C1 to C10;

B is carbon, silicon or germanium;

Q is hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group;

M is a Group 4 transition metal;

X ¹ and X ² are the same or different and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;

C ¹ And C ² are the same or different and each independently represents one of the following formulas (2a), (2b) or (2c) below, with the proviso that C ¹ And Except that the case where all of C ² is the formula 2c;

 (2a)

(2b)

[Chemical Formula 2c]

Wherein R 1 to R 17 and R 1 'to R 9' are the same or different from each other and each independently represents hydrogen, halogen, a C 1 to C 20 alkyl group, a C 2 to C 20 alkenyl group, a C 1 to C 20 alkyl A silyl group, a C1 to C20 silylalkyl group, a C1 to C20 alkoxysilyl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, Two or more adjacent R10 to R17 may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.

In the above Formula 1, examples of the Group 4 transition metal (M) include, but are not limited to, titanium, zirconium, and hafnium.

In the first metallocene compound of Formula 1, R 1 to R 17 and R 1 'to R 9' in Formula 2a, 2b and 2c are each independently hydrogen, a methyl group, an ethyl group, a propyl group, A halogen atom, a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a triisopropylsilyl group, a trimethylsilyl group, a trimethylsilyl group, a trimethylsilyl group, More preferably a silylmethyl group, a methoxy group or an ethoxy group, but is not limited thereto.

In the first metallocene compound of Formula 1, it is more preferable that L is a C4 to C8 linear or branched alkylene group, but it is not limited thereto. The alkylene group may be substituted or unsubstituted with a C1 to C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group.

In the first metallocene compound of Formula 1, A represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert- butyl group, a methoxymethyl group, An ethoxyethyl group, a 1-methyl-1-methoxyethyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group, but is not limited thereto. B is preferably silicon, but it is not limited thereto.

In addition, B in the above formula (1) is preferably silicon, but it is not limited thereto.

The first metallocene compound of Formula 1 forms a structure in which an indeno indole derivative and / or a fluorene derivative is bridged by a bridge, and a non-covalent electron pair which can act as a Lewis base in the ligand structure Thereby supporting the carrier on the surface having Lewis acid properties and exhibiting high polymerization activity even when carried. In addition, the activity is high due to the electron enrichment of the indenoindole group and / or the fluorene group, and not only the hydrogen reactivity is low due to the appropriate steric hindrance and the electronic effect of the ligand, and the high activity is maintained even in the presence of hydrogen. In addition, it is possible to stabilize the beta-hydrogen of the polymer chain in which the nitrogen atom of the indenoindole derivative grows by hydrogen bonding to inhibit beta-hydrogen elimination and polymerize the ultra-high molecular weight polyolefin.

According to an embodiment of the present invention, specific examples of the first metallocene compound represented by Formula 1 include compounds represented by one of the following structural formulas, but the present invention is not limited thereto.

The first metallocene compound of Formula 1 can polymerize polyolefins having high activity and high molecular weight. In particular, even when the polymer is supported on a carrier, it exhibits a high polymerization activity, and a polyolefin having an extremely high molecular weight can be produced.

In addition, even when used in combination with a catalyst having other properties, it is possible to produce a polyolefin satisfying high molecular weight characteristics without lowering the activity, and to easily produce a polyolefin having a high molecular weight polyolefin and a broad molecular weight distribution Can

The first metallocene compound of Formula 1 is prepared by ligating an indenoindole derivative and / or a fluorene derivative with a bridging compound to prepare a ligand compound, and then adding a metal precursor compound to carry out metallation But is not limited thereto.

The method for producing the first metallocene compound will be described in the following Examples.

According to an embodiment of the present invention, the metallocene compound may further include at least one second metallocene compound selected from compounds represented by the following general formulas (3) to (5).

(3)

(Cp ¹ R ^a ) _n (Cp ² R ^b ) M ¹ Z ¹³ _-n

In Formula 3,

M ¹ is a Group 4 transition metal;

Cp ¹ and Cp ² are the same or different and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radical And they may be substituted with hydrocarbons having 1 to 20 carbon atoms;

R ^a and R ^b are the same or different and are each independently selected from the group consisting of hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 C20 to C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;

Z ¹ represents a halogen atom, a C1 to C20 alkyl, a C2 to C10 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C6 to C20 aryl, a substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy;

 n is 1 or 0;

[Chemical Formula 4]

(Cp ³ R ^c ) _m B ¹ (Cp ⁴ R ^d ) M ² Z ² _3-m

In Formula 4,

M ² is a Group 4 transition metal;

Cp < ³ > and Cp < ⁴ > are the same or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radical , Which may be substituted with hydrocarbons having 1 to 20 carbon atoms;

R ^c and R ^d are the same or different and are each independently selected from the group consisting of hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 C20 to C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;

Z ² represents a halogen atom, a C1 to C20 alkyl, a C2 to C10 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C6 to C20 aryl, a substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy;

B ¹ is at least one of a carbon, germanium, silicon, phosphorus, or nitrogen atom containing radical which bridges the Cp ³ R ^c ring and the Cp ⁴ R ^d ring, or cross-links one Cp ⁴ R ^d ring to M ² Or a combination thereof;

m is 1 or 0;

[Chemical Formula 5]

(Cp ⁵ R ^e ) B ² (J) M ³ Z ³ ₂

In Formula 5,

M ³ is a Group 4 transition metal;

Cp < ⁵ > is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radical, which are substituted with hydrocarbons having 1 to 20 carbon atoms ;

R ^e is hydrogen, C 1 to C 20 alkyl, C 1 to C 10 alkoxy, C 2 to C 20 alkoxyalkyl, C 6 to C 20 aryl, C 6 to C 10 aryloxy, C 2 to C 20 alkenyl, C 7 to C 40 alkylaryl , C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;

Z ³ represents a halogen atom, a C1 to C20 alkyl, a C2 to C10 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C6 to C20 aryl, a substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy;

B ² is at least one of a carbon, germanium, silicon, phosphorus, or nitrogen atom-containing radical which cross-links the Cp ⁵ R ^e ring with J, or a combination thereof;

J is any one selected from the group consisting of NR ^f , O, PR ^f and S, and R ^f is a C1 to C20 alkyl, aryl, substituted alkyl or substituted aryl.

In the formula (4), when m is 1, it means that a Cp ³ R ^c ring, a Cp ⁴ R ^d ring or a Cp ⁴ R ^d ring and M ² are bridged by B ¹ , and m is 0 Quot; refers to the structure of the non-crosslinked compound.

The second metallocene compound represented by Formula 3 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto.

The compound represented by the formula (4) may be, for example, a compound represented by the following structural formula, but is not limited thereto.

The compound represented by the formula (5) may be, for example, a compound represented by the following structural formula, but is not limited thereto.

According to one embodiment of the present invention, the supported metallocene catalyst comprises at least one of the first metallocene compounds represented by Formula 1 and a second metal selected from the compounds represented by Chemical Formulas 3 to 5 Or a mixed supported metallocene catalyst in which at least one of the aromatic compounds is mixed and supported together with a promoter compound in a carrier.

The first metallocene compound represented by the formula (1) of the hybrid supported metallocene catalyst contributes mainly to the formation of a high molecular weight copolymer having a high short chain branch (SCB) content, and the second metallocene compound represented by the formula Schengen compounds can contribute to the production of low molecular weight copolymers with low SCB content. In addition, the second metallocene compound represented by the general formula (4) or (5) can contribute to the production of a low molecular weight copolymer having an intermediate SCB content.

According to an embodiment of the present invention, the hybrid supported metallocene catalyst may include at least one first metallocene compound of Formula 1 and at least one second metallocene compound of Formula 3.

According to another embodiment of the present invention, the hybrid supported metallocene catalyst comprises, in addition to at least one first metallocene compound of Formula 1 and at least one second metallocene compound of Formula 3, Or a second metallocene compound of formula (5).

The hybrid supported metallocene catalyst of the present invention comprises a first metallocene compound represented by Formula 1 and a second metallocene compound selected from the compounds represented by Formulas 3 to 5, It is possible to produce a polyolefin which is a high molecular weight polyolefin having a high SCB content and at the same time has a broad molecular weight distribution and is excellent in physical properties as well as in processability.

In the process for producing a polyolefin according to the present invention, the co-catalyst compound to be supported on the carrier for activating the first and second metallocene compounds is an organometallic compound containing a Group 13 metal, Is not particularly limited as long as it can be used in the polymerization of an olefin under a catalyst.

According to one embodiment of the present invention, in particular, the co-catalyst compound may comprise at least one of an aluminum-containing primary co-catalyst of the following formula (6) and a boron-containing secondary co-

[Chemical Formula 6]

_{- [Al (R 18) -O-} ] k -

In Formula (6), R ₁₈ is each independently halogen, halogen-substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, k is an integer of 2 or more,

(7)

T ⁺ [BG ₄ ] ^-

In Formula (7), T ⁺ is a polyatomic ion of +1 valence, B is boron of +3 oxidation state, and G is each independently selected from the group consisting of hydride group, dialkylamido group, halide group, alkoxide group, aryloxide group, Carbocyclic group, halocarbyl group, and halo-substituted hydrocarbyl group, wherein G has not more than 20 carbons, but G is a halide group in at least one position.

By using such first and second co-catalysts, the molecular weight distribution of the finally produced polyolefin becomes more uniform, and the polymerization activity can be improved.

The first cocatalyst of formula (6) may be an alkylaluminoxane compound having a linear, circular or network-like repeating unit bonded thereto. Specific examples of the first catalyst include methylaluminoxane (MAO), ethylaluminium Isobutylaluminoxane, butylaluminoxane, and the like.

Also, the second cocatalyst of formula (7) may be a tri-substituted ammonium salt, or a dialkylammonium salt, or a borate compound in the form of a trisubstituted phosphonium salt. Specific examples of the second cocatalyst include trimethylammonium tetraphenylborate, methyl dioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate , Methyltetradecyclooctadecylammonium tetraphenylborate, N, N-dimethylanilinium tetraphenylborate, N, N-diethylanilinium tetraphenylborate, N, N-dimethyl (2,4,6-trimethylanilinium (Tetrafluoroborate) borate, trimethylammonium tetrakis (pentafluorophenyl) borate, methylditetradecylammonium tetrakis (pentaphenyl) borate, methyl dioctadecylammonium tetrakis (Pentafluorophenyl) borate, triphenyl ammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium (Pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (Pentafluorophenyl) borate, N, N-dimethyl (2,4,6-trimethylanilinium) tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis Tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate , Tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) Borate, N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylanilinium tetrakis (2,3,4,6- Boronate in the form of a tri-substituted ammonium salt such as N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis- (2,3,4,6-tetrafluorophenyl) compound; A borate-based compound in the form of a dialkylammonium salt such as dioctadecylammonium tetrakis (pentafluorophenyl) borate, ditetradecylammonium tetrakis (pentafluorophenyl) borate or dicyclohexylammonium tetrakis (pentafluorophenyl) compound; (Pentafluorophenyl) borate or tri (2,6-, dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, methyl dioctadecylphosphonium tetrakis ) Borate and the like, and the like.

In the mixed supported metallocene catalyst, the mass ratio of the total transition metal to the carrier included in the first metallocene compound represented by Formula 1 and the second metallocene compound represented by Formula 3 to 5 is 1:10 to 1: 1: 1,000. When the carrier and the metallocene compound are contained in the above mass ratio, they can exhibit an optimum shape.

In addition, the mass ratio of the cocatalyst compound to the carrier may be from 1: 1 to 1: 100. The mass ratio of the first metallocene compound represented by Formula 1 to the second metallocene compound represented by Formula 3 to 5 may be 10: 1 to 1:10, preferably 5: 1 to 1: 5. have. When the cocatalyst and the metallocene compound are contained in the mass ratio, the activity and the polymer microstructure can be optimized.

In the hybrid supported metallocene catalyst, a carrier containing a hydroxy group on its surface may be used as the carrier, and preferably a carrier having a hydroxyl group and a siloxane group, Can be used.

Silica-alumina, silica-magnesia, and the like, which are usually dried at high temperature, and which are usually made of oxides such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg (NO ₃ ) ₂ , Sulfate, and nitrate components.

The drying temperature of the carrier is preferably 200 to 800 ° C, more preferably 300 to 600 ° C, and most preferably 300 to 400 ° C. If the drying temperature of the carrier is less than 200 ° C, moisture is excessively large and the surface moisture reacts with the cocatalyst. When the temperature exceeds 800 ° C, the pores on the surface of the carrier are combined to reduce the surface area. And only the siloxane group is left, and the reaction site with the co-catalyst is reduced, which is not preferable.

The amount of hydroxyl groups on the surface of the support is preferably from 0.1 to 10 mmol / g, more preferably from 0.5 to 5 mmol / g. The amount of the hydroxyl group on the surface of the carrier can be controlled by the preparation method and conditions of the carrier or by 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 number of sites of reaction with the co-catalyst is small. If the amount is more than 10 mmol / g, the hydroxyl group may be present in the water other than the hydroxyl group present on the surface of the carrier particle. not.

In the preparation of the hybrid supported metallocene catalyst using the above-mentioned first and second metallocene compounds and the first and second co-catalysts or the like, it is preferable that the carrier is a mixture of a first metallocene compound and a first co- And then the second metallocene compound and the second co-catalyst are supported, but are not limited thereto. Between each of these carrying steps, a washing step using a solvent may be further carried out.

In the process for producing a polyolefin of the present invention, the polymerization reaction for producing a polyolefin is preferably carried out in the presence of a supported metallocene catalyst comprising at least one metallocene compound having a Group 4 transition metal as a central metal, The supported metallocene catalyst may be a single metallocene supported catalyst or a mixed metallocene supported catalyst as described above, in the presence of hydrogen gas.

The polymerization may be carried out in a single reaction or may be divided into a first stage reaction and a second stage reaction using a multi-stage reactor.

Specific examples of the olefinic monomer that can be used include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, 1-undecene, 1-dodecene, norbornene, ethylidene norbornene, styrene, alpha-methylstyrene and 3-chloromethylstyrene. In one example of such a production method, ethylene is used to prepare polyethylene, or propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, , 1-heptene, 1-decene, 1-undecene or 1-dodecene may be copolymerized to prepare an ethylene-alpha olefin copolymer.

When the polymerization reaction is divided into a first step and a second step reaction, in the second step reaction, the supported metallocene catalyst, the molecular weight modifier, and / or the olefin based monomer are added to the reaction mixture of the first step To carry out the polymerization.

According to an embodiment of the present invention, the molecular weight modifier may include a cyclopentadienyl metal compound of the following formula (8), a mixture of an organoaluminum compound of the following formula (9), or a reaction product thereof.

[Chemical Formula 8]

Cp6Cp7M4X'2

In Formula 8,

Cp6 and Cp7 are each independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted indenyl group, or a ligand containing a substituted or unsubstituted fluorenyl group, M4 is a Group 4 transition metal element, X ' Is halogen;

[Chemical Formula 9]

RfRgRhAl

In the above formula (9)

Rf, Rg and Rh are each independently an alkyl group or a halogen having 4 to 20 carbon atoms, and at least one of Rf, Rg and Rh is an alkyl group having 4 to 20 carbon atoms.

Also, in the first step reaction, the residence time of each starting material can be selected from the range of about 1 to about 3 hours, although it can be selected without particular limitation as long as it can form a polyolefin having an appropriate molecular weight distribution and density distribution. If the residence time in the first step reaction is less than this range, the low molecular weight polyolefin is not properly formed and the molecular weight distribution becomes narrow, so that the processability of the final polyolefin may be deteriorated. On the contrary, if the residence time in the first-step reaction becomes too long, it is not preferable from the viewpoint of productivity.

The polymerization reaction temperature in the first step reaction may be about 70 to about 90 캜. If the polymerization reaction temperature is too low, it is not appropriate in view of the polymerization rate and productivity, and if the polymerization reaction temperature is excessively high, fouling may occur in the reactor.

Also, the polymerization reaction pressure in the first stage reaction can be from about 7 to about 10 kg / cm < ³ > to maintain a stable continuous process state.

After the polymerization reaction in the first stage reaction has proceeded, a second stage reaction can be performed on the slurry reaction mixture in the first stage reaction.

At this time, in the second-stage reaction, the above-mentioned supported metallocene catalyst and / or olefin-based monomer may be added in addition to the slurry reaction mixture transferred from the first-step reaction, , Whereby a high molecular weight polyolefin can be obtained.

In the second step reaction, the residence time of each starting material can be selected within a range capable of forming a polyolefin having an appropriate molecular weight distribution and density distribution, but can be about 1 to about 3 hours. If the residence time in the second-stage reaction is less than this range, the high-molecular-weight polyolefin may not be properly formed and the environmental stress cracking or mechanical properties of the finally prepared polyolefin may be deteriorated. On the contrary, Is excessively long, it is not preferable from the viewpoint of productivity.

The polymerization reaction temperature in the second-step reaction may be about 70 to about 90 캜. If the polymerization reaction temperature is too low, it is not appropriate in view of the polymerization rate and productivity, and if the polymerization reaction temperature is excessively high, fouling may occur in the reactor.

And, the polymerization reaction pressure in the second stage reaction can be from about 6 to about 9 kg / cm < ³ > to maintain stable continuous process conditions.

In addition, the polymerization reaction described above can be carried out by slurry polymerization in an aliphatic hydrocarbon-based solvent such as hexane, butane or pentane. As already mentioned above, since the metallocene catalysts exhibit excellent solubility in such solvents, they can be stably dissolved and supplied to the reaction system, so that the polymerization process can be effectively carried out, and a polyolefin having a large molecular weight and a broad molecular weight distribution Can be effectively produced.

Most of the olefinic monomers, such as about 95 to about 97 wt% of olefinic monomers, are converted to polyolefins by performing a polymerization reaction using a single reactor or multi-stage -CSTR reactor as described above. However, about 2 to about 5% by weight of the olefinic monomer remains unreacted.

In the method for producing a polyolefin of the present invention, the unreacted olefin-based monomer remaining after the polymerization reaction is subjected to a post-reaction to convert substantially unreacted olefin-based monomer to polyolefin. In particular, by controlling the reaction conditions of the second half of the reaction, the unreacted olefin-based monomer is converted into a polyolefin having a high molecular weight, whereby the content of the ultra-high molecular weight polyolefin is further increased to produce a polyolefin resin having excellent FNCT.

There is conventionally known a method for finally producing a polyolefin by further comprising a post reactor for further polymerizing unreacted monomers in the slurry reaction mixture after the polymerization. However, it is not known that the physical properties of the FNCT can be improved by controlling the reaction conditions in the post reactor.

Further, in the case of the conventional polymerization process using a Ziegler-Natta-based catalyst, since the content of hydrogen gas as a molecular weight regulator is high, it is difficult to expect improvement in physical properties due to control of polymerization conditions. Therefore, A method of improving the physical properties was mainly used.

However, according to the polyolefin preparation method of the present invention, the reaction pressure is adjusted to fall within the range of about 1.5 to about 3.0 kg / cm ³ , or about 1.5 to about 2.5 kg / cm ³ in the post-reaction step, Addition reaction can produce an ultra high molecular weight polyolefin. If the reaction pressure in the subsequent reaction step is too low, the effect of improving the FNCT of the finally produced polyolefin may be insignificant. If the reaction pressure is too high, the processability may be deteriorated.

Also, according to one embodiment of the present invention, the reaction temperature may be adjusted to be in the range of about 70 to about 78 ° C, or about 72 to about 78 ° C in the post-reaction step. When the reaction temperature in the post-reaction step is in the range described above, it may be more advantageous to achieve the FNCT improvement effect of the polyolefin.

Also, in the post-reaction, the reaction can proceed without the addition of hydrogen gas.

The polyolefin prepared according to the production method of one embodiment has a high polyolefin resin content of ultra high molecular weight and has a stress cracking resistance (FNCT) measured according to ISO 16770 at a temperature of 80 캜 and a pressure of 4.0 MPa for about 480 hours or more, About 500 hours or more, or about 550 hours or more.

Also, due to the large molecular weight and the broad molecular weight distribution, excellent mechanical properties and processability can be exhibited at the same time.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

<Examples>

Synthesis Example of First Metallocene Compound

Synthesis Example 1

Preparation of 1-1 ligand compounds

fluorene was dissolved in 5 mL of MTBE and 100 mL of hexane, and 5.5 mL of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath and stirred overnight at room temperature. (3.6 g) was dissolved in hexane (50 mL), and the fluorene-Li slurry was transferred for 30 minutes under a dry ice / acetone bath. The mixture was stirred overnight at room temperature. At the same time, 5,8-dimethyl-5,10-dihydroindeno [1,2-b] indole (12 mmol, 2.8 g) was dissolved in 60 mL of THF and 5.5 mL of 2.5 M n-BuLi hexane solution was dissolved in a dry ice / acetone bath And the mixture was stirred at room temperature overnight. dimethyl-5,10-dihydroindeno [1,2-b] indole-2-carboxylic acid was obtained by NMR spectroscopic analysis of the reaction solution of (6- (tert-butoxy) The Li solution was transferred under a dry ice / acetone bath. The mixture was stirred at room temperature overnight. After the reaction, the residue was extracted with ether / water, and the residual water of the organic layer was removed with MgSO ₄ to obtain a ligand compound (Mw = 597.90, 12 mmol). It was confirmed by 1H-NMR that two isomers were formed.

¹ H NMR (500 MHz, d 6 -benzene): -0.30 to -0.18 (3H, d), 0.40 (2H, m), 0.65-1.45 (8H, m), 1.12 D), 3.17 (2H, m), 3.41-3.43 (3H, d), 4.17-4.21 (1H, d), 4.34-4.38

Preparation of 1-2 metallocene compounds

7.2 g (12 mmol) of the ligand compound synthesized in 1-1 above was dissolved in 50 mL of diethylether, and 11.5 mL of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath and stirred overnight at room temperature. And dried in vacuo to obtain a brown color sticky oil. And dissolved in toluene to obtain a slurry. ZrCl ₄ (THF) ₂ was prepared and 50 mL of toluene was added thereto to prepare a slurry. A 50 mL toluene slurry of ZrCl ₄ (THF) ₂ was transferred in a dry ice / acetone bath. It was changed to violet color by stirring overnight at room temperature. The reaction solution was filtered to remove LiCl. Toluene in the filtrate was removed by vacuum drying, and then hexane was added thereto for sonication for 1 hour. The slurry was filtered to give 6 g of dark violet metallocene compound (Mw 758.02, 7.92 mmol, yield 66 mol%), which was a filtered solid. Two isomers were observed in &lt; 1 &gt; H-NMR.

¹ H NMR (500 MHz, CDCl ₃ ): 1.19 (9H, d), 1.71 (3H, d), 1.50-1.70 (4H, m), 1.79 (2H, m), 3.91 (3H, d), 6.66-7.88 (15H, m)

Synthesis Example 2

2-1 Preparation of ligand compound

Add 2.63 g (12 mmol) of 5-methyl-5,10-dihydroindeno [1,2-b] indole to a 250 mL flask and dissolve in 50 mL of THF. Add 6 mL of 2.5 M n-BuLi hexane solution to the dr yice / acetone bath And the mixture was stirred at room temperature overnight. In another 250 mL flask, 1.62 g (6 mmol) of (6- (tert-butoxy) hexyl) dichloro (methyl) silane was dissolved in 100 mL of hexane, and then 5-methyl-5,10-dihydroindeno [1,2-b] indole in tetrahydrofuran and slowly stirred at room temperature overnight. After the reaction, the residue was extracted with ether / water. The residual water in the organic layer was removed with MgSO ₄ and vacuum dried to obtain 3.82 g (6 mmol) of a ligand compound.

^{1 H NMR (500 MHz, CDCl3} ): -0.33 (3H, m), 0.86 ~ 1.53 (10H, m), 1.16 (9H, d), 3.18 (2H, m), 4.07 (3H, d), 4.12 ( 3H, d), 4.17 (1 H, d), 4.25 (1 H, d), 6.95-7.92 (16 H, m)

2-2 Preparation of metallocene compound

After dissolving 3.82 g (6 mmol) of the ligand compound synthesized in 2-1 above in 100 mL of toluene and 5 mL of MTBE, 5.6 mL (14 mmol) of 2.5 M n-BuLi hexane solution was added dropwise in a dryice / acetone bath, Lt; / RTI &gt; 2.26 g (6 mmol) of ZrCl ₄ (THF) ₂ was added to another flask and 100 ml of toluene was added to prepare a slurry. The toluene slurry of ZrCl ₄ (THF) ₂ was transferred to the litigated ligand in a dry ice / acetone bath. It was stirred overnight at room temperature and changed to violet color. The reaction solution was filtered to remove LiCl, and the resulting filtrate was vacuum-dried, and hexane was added thereto for sonication. The slurry was filtered to obtain 3.40 g (yield: 71.1 mol%) of a metallocene compound of dark violet filtered solid.

^{1 H NMR (500 MHz, CDCl3} ): 1.74 (3H, d), 0.85 ~ 2.33 (10H, m), 1.29 (9H, d), 3.87 (3H, s), 3.92 (3H, s), 3.36 (2H , &lt; / RTI &gt; m), 6.48 to 8.10 (16H, m)

Production example of second metallocene compound

Synthesis Example 3

(CH ₂ ) ₆ -Cl was prepared by the method described in Tetrahedron Lett. 2951 (1988) using 6-chlorohexanol, which was reacted with NaCp t-Butyl-O- (CH ₂ ) ₆ -C ₅ H ₅ (yield 60%, bp 80 ° C / 0.1 mmHg).

Further, t-Butyl-O- (CH ₂ ) ₆ -C ₅ H ₅ was dissolved in THF at -78 ° C, and then normal butyl lithium (n-BuLi) was slowly added thereto. . The solution was again at -78 ℃ ZrCl ₄ (THF) ₂ (1.70 g, 4.50 mmol) / THF (30 mL) was added slowly and further reacted at room temperature for 6 hours.

All volatile materials were vacuum dried, and hexane solvent was added to the obtained oily liquid substance to be filtered. The filtered solution was vacuum dried, and hexane was added thereto to induce a precipitate at a low temperature (-20 ° C). The white solid precipitate was filtered out at a low temperature _{[tBu-O- (CH 2)} 6 -C 5 H 4] 2 ZrCl ₂ to obtain the compound (92% yield).

^{1 H NMR (300 MHz, CDCl} 3): 6.28 (t, J = 2.6 Hz, 2 H), 6.19 (t, J = 2.6 Hz, 2 H), 3.31 (t, 6.6 Hz, 2 H), 2.62 ( t, J = 8 Hz), 1.7-1.3 (m, 8 H), 1.17 (s, 9 H).

_{^{13 C NMR (CDCl 3):}} 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.61, 30.14, 29.18, 27.58, 26.00.

&Lt; Preparation Example of Supported Catalyst >

Production Example 1

1-1 Carrier Drying

Silica (SYLOPOL 948, Grace Davison) was dehydrated under vacuum at a temperature of 400 ° C for 15 hours.

1-2 Preparation of supported catalyst

Add 10 g of dried silica to a glass reactor, add 100 mL of toluene and stir. 50 mL of 10 wt% methylaluminoxane (MAO) / toluene solution was added, and the mixture was slowly reacted at 40 ° C with stirring. Thereafter, the reaction product was washed with a sufficient amount of toluene to remove the unreacted aluminum compound, and the remaining toluene was removed by decompression. After the addition of 100 mL of toluene, 0.25 mmol of the metallocene catalyst prepared in Synthesis Example 2 was dissolved in toluene, and the mixture was reacted for 1 hour. After the reaction was completed, 0.25 mmol of the metallocene catalyst of Synthesis Example 1 was dissolved in toluene, and the reaction was further conducted for 1 hour. Finally, 0.25 mmol of the metallocene catalyst prepared in Synthesis Example 3 was dissolved in toluene, and the reaction was further performed for 1 hour. After the reaction was completed, stirring was stopped and the toluene layer was separated and removed. 1.0 mmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (AB) was added thereto and stirred for 1 hour. Toluene was removed to prepare a supported catalyst.

<Polymerization Examples>

Example 1

A single CSTR reactor of 0.2 m ³ capacity was used.

The reactor was charged with 31 kg / hr of hexane, 10 kg / hr of ethylene, 0.3 kg / hr of 1-butene, 1.5 g / hr of hydrogen, and 23 mmol / hr of triethylaluminum (TEAL) And the metallocene supported catalyst prepared in Production Example 1 was injected at 0.65 g SiO ₂ / hr. At this time, the reactor was maintained at 80 ° C., the pressure was maintained at 8 kg / cm ³ , the residence time of the reactant was maintained at 3.0 hours, and the slurry reaction mixture containing polyolefin was continuously fed to the post reactor and the post reaction was carried out.

The post reactor was maintained at 78 DEG C and the pressure was maintained at 2.5 kg / cm &lt; ³ &gt;, and the residence time of the reactant was maintained at 2.0 hours without introduction of hydrogen gas to polymerize unreacted monomers. The polymerization product was then made into the final polyethylene via a solvent removal unit and dryer.

Example 2

In Example 1, the polyolefin polymerization process was carried out in the same manner as in Example 1, except that the pressure in the post reactor was 1.5 kg / cm &lt; ^{3 &} gt ;.

Example 3

In Example 1, the polyolefin polymerization process was carried out in the same manner as in Example 1 except that the temperature of the post reactor was changed to 75 캜.

Example 4

In Example 1, the pressure of the post reactor was changed to 1.5 kg / cm &lt; ³ &gt; The polyolefin polymerization process was carried out in the same manner as in Example 1, except that the temperature was changed to 75 캜.

Comparative Example 1

In Example 1, the polymerization process was carried out in the same way except that the post-reaction in the post reactor was not carried out.

<Experimental Example>

The properties of the polyethylene prepared in Examples 1 to 4 and Comparative Example 1 were measured by the following methods, and the results are shown in Table 1 below.

1) Density: ASTM 1505

2) HLMI: The melt index was measured according to ASTM 1238 at a measurement temperature of 190 占 폚 and a load of 21.6 kg.

3) Stress cracking resistance (FNCT, unit: hour): Measured according to ISO 16770 at a temperature of 80 캜 and a pressure of 4.0 MPa.

HLMI
(g / 10 min) density
(g / cm ³⁾ FNCT
(Hr) Example 1 7.0 0.939 550 Example 2 7.1 0.939 480 Example 3 6.9 0.939 580 Example 4 7.0 0.939 500 Comparative Example 1 7.2 0.939 450

Referring to Table 1, the polyolefins of Examples 1 to 4, which were post-reacted at a constant pressure and temperature range, exhibited high resistance to stress cracking without deteriorating other physical properties.

Claims (9)

A polymerization reaction in which an olefin monomer is polymerized in the presence of a supported metallocene catalyst containing at least one metallocene compound having at least one transition metal selected from the group consisting of a transition metal and a carrier and a carrier and a hydrogen gas to produce a polyolefin ; And
A post-reaction which further converts the unreacted olefin-based monomer present in the reaction mixture of the polymerization reaction to a polyolefin under a pressure of 1.5 to 3.0 kg / cm ³ ;
&Lt; / RTI &gt;
The process according to claim 1, wherein the polymerization reaction is conducted in a single reactor or a Cascade-CSTR reactor.
The process according to claim 1, wherein the post-reaction is carried out in the absence of hydrogen gas.
The process according to claim 1, wherein the post-reaction is carried out at a temperature of from 70 to 78 ° C.
The olefinic monomer according to claim 1, wherein the olefinic monomer is at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, , At least one monomer selected from the group consisting of 1-undecene, 1-dodecene, norbornene, ethylidene norbornene, styrene, alpha-methylstyrene and 3-chloromethylstyrene.
The method of claim 1, wherein the metallocene compound comprises a first metallocene compound represented by the following formula (1): &lt; EMI ID =
[Chemical Formula 1]

In Formula 1,
A represents a hydrogen atom, a halogen atom, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, a C7 to C20 arylalkyl group, a C1 to C20 alkoxy group, C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;
D is -O-, -S-, -N (R) - or -Si (R) (R ') -, wherein R and R' are the same or different and each independently hydrogen, halogen, C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group;
L is a straight or branched alkylene group of C1 to C10;
B is carbon, silicon or germanium;
Q is hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group;
M is a Group 4 transition metal;
X ¹ and X ² are the same or different and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;
C ¹ And C ² are the same or different and each independently represents one of the following formulas (2a), (2b) or (2c) below, with the proviso that C ¹ And Except that the case where all of C ² is the formula 2c;
(2a)

(2b)

[Chemical Formula 2c]

Wherein R 1 to R 17 and R 1 'to R 9' are the same or different from each other and each independently represents hydrogen, halogen, a C 1 to C 20 alkyl group, a C 2 to C 20 alkenyl group, a C 1 to C 20 alkyl A silyl group, a C1 to C20 silylalkyl group, a C1 to C20 alkoxysilyl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, Two or more adjacent R10 to R17 may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.
The method for producing a polyolefin according to claim 6, wherein the metallocene compound further comprises at least one second metallocene compound selected from compounds represented by the following general formulas (3) to (5)
(3)
(Cp ¹ R ^a ) _n (Cp ² R ^b ) M ¹ Z ¹³ _-n
In Formula 3,
M ¹ is a Group 4 transition metal;
Cp ¹ and Cp ² are the same or different and are each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radical And they may be substituted with hydrocarbons having 1 to 20 carbon atoms;
R ^a and R ^b are the same or different and are each independently selected from the group consisting of hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 C20 to C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;
Z ¹ represents a halogen atom, a C1 to C20 alkyl, a C2 to C10 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C6 to C20 aryl, a substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy;
n is 1 or 0;
[Chemical Formula 4]
(Cp ³ R ^c ) _m B ¹ (Cp ⁴ R ^d ) M ² Z ² _{3 -m}
In Formula 4,
M ² is a Group 4 transition metal;
Cp &lt; ³ &gt; and Cp &lt; ⁴ &gt; are the same or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radical , Which may be substituted with hydrocarbons having 1 to 20 carbon atoms;
R ^c and R ^d are the same or different and are each independently selected from the group consisting of hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 C20 to C20 alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;
Z ² represents a halogen atom, a C1 to C20 alkyl, a C2 to C10 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C6 to C20 aryl, a substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy;
B ¹ is at least one of a carbon, germanium, silicon, phosphorus, or nitrogen atom containing radical which bridges the Cp ³ R ^c ring and the Cp ⁴ R ^d ring, or cross-links one Cp ⁴ R ^d ring to M ² Or a combination thereof;
m is 1 or 0;
[Chemical Formula 5]
(Cp ⁵ R ^e ) B ² (J) M ³ Z ³ ₂
In Formula 5,
M ³ is a Group 4 transition metal;
Cp &lt; ⁵ &gt; is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radical, which are substituted with hydrocarbons having 1 to 20 carbon atoms ;
R ^e is hydrogen, C 1 to C 20 alkyl, C 1 to C 10 alkoxy, C 2 to C 20 alkoxyalkyl, C 6 to C 20 aryl, C 6 to C 10 aryloxy, C 2 to C 20 alkenyl, C 7 to C 40 alkylaryl , C7 to C40 arylalkyl, C8 to C40 arylalkenyl, or C2 to C10 alkynyl;
Z ³ represents a halogen atom, a C1 to C20 alkyl, a C2 to C10 alkenyl, a C7 to C40 alkylaryl, a C7 to C40 arylalkyl, a C6 to C20 aryl, a substituted or unsubstituted C1 to C20 alkylidene , A substituted or unsubstituted amino group, a C2 to C20 alkylalkoxy, or a C7 to C40 arylalkoxy;
B ² is at least one of a carbon, germanium, silicon, phosphorus, or nitrogen atom-containing radical which cross-links the Cp ⁵ R ^e ring with J, or a combination thereof;
J is any one selected from the group consisting of NR ^f , O, PR ^f and S, and R ^f is a C1 to C20 alkyl, aryl, substituted alkyl or substituted aryl.
The method according to claim 6, wherein the first metallocene compound represented by Formula 1 is one of the following structural formulas:

The process for producing a polyolefin according to claim 1, wherein the co-catalyst compound comprises at least one selected from the group consisting of a first catalyst of formula (6) and a second catalyst of formula (7)
[Chemical Formula 6]
_{- [Al (R 18) -O-} ] k -
In Formula (6), R ₁₈ is each independently halogen, halogen-substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, k is an integer of 2 or more,
(7)
T ⁺ [BG ₄ ] ^-
In Formula (7), T ⁺ is a polyatomic ion of +1 valence, B is boron of +3 oxidation state, and G is each independently selected from the group consisting of hydride group, dialkylamido group, halide group, alkoxide group, aryloxide group, Carbocyclic group, halocarbyl group, and halo-substituted hydrocarbyl group, wherein G has not more than 20 carbons, but G is a halide group in at least one position.