KR101092572B1 - Method of producing polyolefins using supported catalysts - Google Patents

Abstract

The present invention comprises the steps of: 1) mixing an olefin supported catalyst and an olefin comprising a catalyst for the first olefin polymerization, a promoter and a carrier; And 2) adding a second olefin polymerization catalyst in an unsupported state before or after polymerizing the olefin using the olefin supported catalyst. In preparing the polyolefin, it is possible to easily control the input time, the input amount, the type of the catalyst for the second olefin polymerization, it is possible to make a polyolefin having a variety of molecular weight distribution.

Metallocenes, promoters, carriers, olefin copolymers

Description

Method for producing polyolefin using supported catalyst {METHOD OF PRODUCING POLYOLEFINS USING SUPPORTED CATALYSTS}

1 is a view showing a manufacturing process of a polyolefin according to the present invention.

The present invention relates to a method for producing a polyolefin using a supported catalyst.

The production and application of polyolefins has advanced dramatically with the invention of a catalyst called Ziegler-Natta catalyst, and the production process and the use of the product have been variously developed. In particular, the development of polyolefin products using a single-site catalyst represented by a metallocene catalyst, as well as a dramatic improvement in the activity of the Ziegler-Natta catalyst is also attracting attention in the art. Currently, a polyolefin is produced using a part of the catalyst as a metallocene catalyst in a commercial process using a Ziegler-Natta catalyst, but the amount of production is not high.

Ziegler-Natta catalysts, which are widely applied in the existing commercial processes, are multi-site catalysts, and thus have a wide molecular weight distribution of the resulting polymers. There is a problem.

Metallocene catalysts, on the other hand, are single-site catalysts with one type of active site, which have a narrow molecular weight distribution of polymers and greatly control the molecular weight, stereoregularity, crystallinity, and especially the reactivity of comonomers, depending on the structure of the catalyst and ligand. There are advantages to it. However, polyethylene polymerized with a metallocene catalyst has a narrow molecular weight distribution, so when applied to some products, there is a problem that it is difficult to apply in the field such as productivity decreases significantly due to the extruded load. I've done a lot.

For example, US Pat. No. 4,461,873 discloses controlling molecular weight distribution by physically mixing polyolefins having different molecular weights and comonomer contents. In addition, German Patent No. 28,856,548 and the like is proposed to control the molecular weight distribution by varying the polymerization conditions for each reactor using a multi-stage reactor. Also, U.S. Pat.Nos. 6,444,605 B1, 6,399,531 B1, 6,417,129 B2, 6,399,723 B1 and 5,614,456, and Korean Patent Publication Nos. 1988-045993, 1998-045994, 1999-022334 and No. 2000-0042620 discloses a method of polymerization by mixing two different catalysts in a single reactor or by introducing two or more catalysts in one carrier.

However, the above-described method has to make a supported catalyst every time, and if the result is not good, it is troublesome to find another catalyst system to carry it and confirm the result.

Therefore, in order to solve the above technical problem, the present invention provides an olefin supported catalyst for olefin polymerization carrying a catalyst for the first olefin polymerization, and thereafter, before the polymerization or the polymerization of the olefin using the second olefin, When the catalyst for polymerization was added, it was found that the molecular weight distribution of the resulting polyolefin can be easily controlled. Accordingly, an object of the present invention is to provide a method for producing a polyolefin which can easily control the molecular weight of the polyolefin by separating and adding the first olefin polymerization catalyst and the second olefin polymerization catalyst.

The present invention comprises the steps of: 1) mixing an olefin supported catalyst and an olefin comprising a catalyst for the first olefin polymerization, a promoter and a carrier; And

2) adding a second olefin polymerization catalyst in an unsupported state before or after polymerizing the olefin using the olefin supported catalyst.
It provides a method for producing a polyolefin comprising a.

The present invention provides a polyolefin prepared by the method for producing the polyolefin.

Hereinafter, the present invention will be described in detail.

In the method for preparing polyolefin according to the present invention, after preparing an olefin supported catalyst including a catalyst, a cocatalyst and a carrier for the first olefin polymerization, the prepared olefin supported catalyst is mixed with an olefin monomer in a reactor to polymerize olefin. The olefin is polymerized by adding an unsupported second olefin polymerization catalyst or by mixing the prepared olefin supported catalyst with the olefin monomer in the reactor immediately after adding the unsupported second olefin polymerization catalyst. do.

In detail, the present invention prepares an olefin supported catalyst by supporting a catalyst for the first olefin polymerization and a promoter on a carrier, wherein the catalyst for the first olefin polymerization and the promoter component are strongly bound by Lewis acid group interaction. . After the olefin supported catalyst is added to the single polymerization reactor together with the olefin monomer, the second olefin polymerization catalyst is additionally added immediately or after the olefin polymerization proceeds to some extent. At this time, the co-catalyst on the surface of the olefin supported catalyst for olefin polymerization and the catalyst for the second olefin polymerization are combined to form a polymerization active point to show two or more polymerization active points. This facilitates screen tests in the reactor in an intermediate state by proceeding in-situ without completing all of the supported catalysts as in the prior art, and as a result, many supported catalysts can be tested. Can be. Therefore, the molecular weight distribution of the polymer formed can be adjusted simply by changing the kind of catalyst for the second olefin polymerization, the time to be added and the amount to be added thereto. In addition, after the polymerization is carried out using the olefin supported catalyst for olefin polymerization, when the second olefin polymerization catalyst is added, it is possible to produce a polyolefin having a molecular weight distribution of various forms according to the progress time. In addition, it is possible to significantly increase the content of the comonomer of the polymer portion compared to the prior art using the Ziegler-Natta catalyst, and to control the structure of the polyolefin produced without changing the structure of the metallocene compound.

One embodiment of the method for producing a polyolefin according to the present invention comprises the steps of: a) supporting a catalyst for the polymerization of a first olefin on a carrier; b) preparing an olefin supported catalyst for olefin polymerization in which the cocatalyst is supported by adding a cocatalyst to step a); And c) injecting an olefin monomer into the reactor, mixing with an olefin supported catalyst for olefin polymerization to inject an unsupported second olefin polymerization catalyst before or after the olefin polymerization.

In this case, a metallocene compound may be used as the catalyst for the first olefin polymerization or the catalyst for the second olefin polymerization, and may be the same as or different from each other. Specifically, the metallocene compound may include a compound represented by the following Chemical Formulas 1 to 3.

In Chemical Formulas 1, 2 and 3,

C _p and C _{p ′} are the same or different and each independently one selected from the group cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl;

R ^m and R ⁿ are the same as or different from each other, and each independently hydrogen or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group, an alkylaryl group, An arylalkyl group, an arylalkenyl group, and an alkylsilyl group;

R ¹ and R ² are the same as or different from each other, and are each independently hydrogen or a hydrocarbyl group having 1 to 6 carbon atoms;

a, a ', b and b' are the same as or different from each other, and each independently an integer of 1 to 4;

M is a transition metal of Group 14, 15 or 16 in the periodic table;

Q is selected from a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group, and an alkylidene group having 1 to 20 carbon atoms;

k is 2 or 3;

z is 0 or 1 and z is 0 when k is 3;

B is selected from hydrocarbyl groups containing silicon, germanium, phosphorus, nitrogen, boron or aluminum and alkyl groups of 1 to 4 carbon atoms;

J is selected from NR ^s , O, PR ^s and S, and R ^s is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

On the other hand, in the compound represented by the above formula 2, B is the two C _p is a structural bridge between the rings, C _p rings in a metallocene catalyst essentially in a different manner to give the three-dimensional rigidity to the C _p rings within the catalyst It is preferable to substitute so that there is a steric difference between the two C _p rings. R ¹ _a R ^m _b is preferably selected such that (C _p R ¹ _a R ^m _b ) is a ring that is essentially different from (C _p R ² _a R ⁿ _b ).

In Formulas 1 to 3, at least one of hydrogen present in the R ^m , R ⁿ , B and R ^s is preferably substituted with a substituent selected from substituents represented by the following Formulas 4, 5, and 6.

In Chemical Formula 4,

Z is an oxygen atom or a sulfur atom;

R0 to R3 are the same as or different from each other, and are each independently a hydrogen group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group, an alkylaryl group, and aryl An alkyl group and an arylalkenyl group; R2 and R3 may be linked to each other to form a ring;

G is selected from alkoxy, aryloxy, alkylthio, arylthio and substituted or unsubstituted phenyl having 1 to 20 carbon atoms, or can be linked to R2 or R3 to form a ring;

If Z is a sulfur atom, G is necessarily alkoxy or aryloxy;

If G is alkylthio, arylthio or substituted or unsubstituted phenyl, Z is necessarily an oxygen atom.

In Formula 5,

Z1 and Z2 are each independently an oxygen or sulfur atom, at least one of Z1 and Z2 is an oxygen atom,

R4 to R6 are the same as or different from each other, and each independently a hydrogen group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group, an alkylaryl group, Or an arylalkyl group and an arylalkenyl group, or at least two of R4 to R6 may be linked to each other to form a ring.

In Formula 6,

Z 3 is one selected from oxygen, sulfur, nitrogen, phosphorus and arsenic atoms;

R7 and R9 are the same as or different from each other, and are each independently a hydrogen group, an alkyl group having 1 to 40 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group, an alkylaryl group, and aryl An alkyl group and an arylalkenyl group;

R8 is one selected from a hydrogen group or an alkyl group having 1 to 40 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group, an alkylaryl group, an alkylsilyl group, an arylsilyl group and a substituted or unsubstituted phenyl group;

n is 1 or 2; N is 1 if Z 3 is oxygen or sulfur and n is 2 if Z 3 is nitrogen, phosphorus or arsenic.

In the compounds represented by Formulas 1 to 3, M is preferably titanium, zirconium or hafnium, Q is preferably halogen, and chlorine is most preferred.

Representative examples of the metallocene compound represented by Chemical Formula 1 of the present invention include [AO- (CH ₂ ) _d -C ₅ H ₄ ] ₂ ZrCl ₂ or [AO- (CH ₂ ) _d -C ₉ H ₆ ] ZrCl ₃ , including but not limited to. In the above formula, d is an integer of 4-8, A is methoxymethyl, t-butoxymethyl, t-butoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl, and t-butyl.

Representative examples of the metallocene compound represented by Chemical Formula 2 of the present invention are [AO- (CH ₂ ) _e -C ₅ H ₄ ] C (CH ₃ ) ₂ [C ₁₃ H ₈ ] ZrCl _2, [AO- ( CH ₂ ) _e -C ₅ H ₄ ] Si (CH ₃ ) ₂ [C ₁₃ H ₈ ] ZrCl ₂ , [C ₅ H ₅ ] C (CH ₃ ) (AO- (CH ₂ ) _e ) [C ₁₃ H ₈ ] ZrCl ₂ and [C ₅ H ₅ ] Si (CH ₃ ) (AO- (CH ₂ ) _e ) [C ₁₃ H ₈ ] ZrCl ₂ , but are not limited thereto. In this formula, e is an integer of 4 to 8, A is methoxymethyl, t-butoxymethyl, t-butoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl, and t-butyl.

Representative examples of the metallocene compound represented by Chemical Formula 3 of the present invention include [(AD- (CH ₂ ) _f )] (CH ₃ ) X (C ₅ Me ₄ ) (NCMe ₃ )] TiCl ₂ and [(AD -(CH ₂ ) _f )] (CH ₃ ) X (C ₅ Me ₄ ) (NCMe ₃ )] ZrCl ₂ , but is not limited thereto. In this formula, f is an integer of 4 to 8, X is one selected from methylene, ethylene and silicon, D is an oxygen or nitrogen atom, A is hydrogen, alkyl of 1 to 20 carbon atoms, of 1 to 20 carbon atoms Alkenyl, aryl, alkylaryl, arylalkyl, alkylsilyl, arylsilyl, methoxymethyl, t-butoxymethyl, t-butoxymethyl, tetrahydropyranyl, tetrahydrofuranyl , 1-ethoxyethyl, 1-methyl-1-methoxyethyl, and t-butyl.

Specifically, the metallocene compound may include a compound represented by the following structure, but is not limited thereto.

In the above formulas.

a is an integer of 4 to 8,

D is an oxygen or nitrogen atom,

A is hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 1 to 20 carbon atoms, aryl, alkylaryl, arylalkyl, alkylsilyl, arylsilyl, methoxymethyl, t-butoxymethyl , Tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl and t-butyl (t-butyl),

R10 is hydrogen or methyl group,

Q5 and Q6 are each independently selected from methyl, dimethylamido and chloride groups.

The carrier included in the olefin supported catalyst for olefin polymerization of the present invention can be used that includes a hydroxyl group on the surface. More specifically, it is preferable to use those having a highly reactive hydroxyl group and a siloxane group after drying to remove water from the surface. Specifically, silica, silica-alumina, silica-magnesia, etc., dried at a high temperature may be used, and these are usually oxides, carbonates, sulfates, such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg (NO ₃ ) ₂ . And nitrate components. The drying temperature is preferably 200 to 800 ° C, more preferably 300 to 600 ° C, and most preferably 300 to 400 ° C. If the drying temperature is less than 200 ℃ water is too much to react with the surface of the water and the promoter is reacted, if it exceeds 800 ℃ because a lot of hydroxyl groups on the surface of the siloxane group is left only because the reaction site with the promoter decreases Not desirable

The amount of hydroxy groups on the surface of the carrier is preferably 0.1 to 10 mmol / g, more preferably 0.5 to 1 mmol / g. The amount of hydroxyl groups on the surface of the carrier can be controlled by the method and conditions for preparing the carrier or by drying conditions such as temperature, time, vacuum or spray drying. If the amount of the hydroxy group is less than 0.1 mmol / g, the reaction site with the promoter decreases, and if it exceeds 10 mmol / g, it may be due to moisture other than the hydroxy group present on the surface of the silica particles. Not desirable

The dried carrier as described above is impregnated with the catalyst for olefin polymerization represented by Chemical Formulas 1 to 3 above, and further mixed with a cocatalyst to form an olefin supported catalyst for olefin polymerization.

The promoter is preferably a transition metal compound including a Group 13 transition metal in the periodic table. Cocatalysts used in the polymerization of olefins under common metallocene catalysts can be used. Carrying such a promoter results in the formation of a bond between the hydroxyl group on the carrier and the Group 13 transition metal. In addition, the promoter can be present only on the surface of the carrier to show the inherent characteristics of the two catalysts without the fouling phenomenon that the polymer particles are entangled with the reactor wall.

Specifically, the cocatalyst includes, but is not limited to, transition metal compounds represented by the following Chemical Formulas 7, 8, and 9.

-[Al (R11) -O] _n -

In Chemical Formula 7,

R11 is a halogen group or a hydrocarbyl group having 1 to 20 carbon atoms unsubstituted or substituted with halogen,

n is an integer from 2 to 20.

G (R12) ₃

In Chemical Formula 8,

G is aluminum or boron;

R12 is the same as or different from each other, and is a halogen group or a hydrocarbyl group having 1 to 20 carbon atoms unsubstituted or substituted with halogen.

[Formula 9]

[L-H] ⁺ [IE ₄ ] ^-  Or [L] ⁺ [IE ₄ ] ^-

In Chemical Formula 9,

I is a neutral or cationic Lewis acid,

H is a hydrogen atom,

N is a Group 13 element in the periodic table, and is selected from Al, Ga, In, and Ti,

E is an aryl group having 6 to 40 carbon atoms, which is a halogen group, a hydrocarbyl having 1 to 20 carbon atoms, an alkoxy group, a phenoxy group, and having 1 to 20 carbon atoms containing at least one of nitrogen, phosphorus, sulfur and oxygen atoms. It may be substituted with one or more selected from hydrocarbyl groups, the four E are the same or different from each other.

In detail, the compound represented by Chemical Formula 7 includes, but is not limited to, methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane and butyl aluminoxane.

In addition, the compound represented by the formula (8) is trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, dimethyl isobutyl aluminum, dimethyl ethyl aluminum, diethyl chloro aluminum, triiso Propyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum Methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron and tributylboron.

In addition, the compound represented by the formula (9) is triethyl ammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium tetra (p-tolyl) Boron, tripropylammonium tetra (p-tolyl) boron, triethylammonium tetra (o, p-dimethylphenyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p -Trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N-diethylanilinium tetraphenylboron, N, N- Diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylbo , Triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra (p-tolyl) aluminum, tripropyl ammonium tetra (p -Tolyl) aluminum, triethylammonium tetra (o, p-dimethylphenyl) aluminum, tributylammonium tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tri Butyl ammonium tetrapentafluorophenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N-diethylanilinium tetrapentafluorophenyl Aluminum, diethylammonium tetrapentafluorophenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, triethylam Monyumtetraphenylboron, tributylammoniumtetraphenylboron, trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra (p-tolyl) boron, tripropylammoniumtetra (p-tolyl) Boron, triethylammonium tetra (o, p-dimethylphenyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetraphenylboron, N, N -Diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, triphenylcarbonium tetraphenylboron, triphenylcarbonium tetraphenylaluminum, Triphenylca Bonium tetra (p-trifluoromethylphenyl) boron and triphenylcarbonium tetrapentafluorophenylboron.

On the other hand, the molar ratio of the Group 13 metal / Group 4 metal in the olefin supported catalyst for olefin polymerization is preferably 1 to 10,000, more preferably 1 to 1,000, most preferably 10 to 100. If the molar ratio is less than 1, the Al content is too small, so that almost no catalytically active species is made, and the activity is very low. If the molar ratio exceeds 10,000, MAO acts as a catalyst poison.

The olefinic monomers usable in the present invention include alpha olefins, cyclic olefins, and the like, and diene olefin monomers or triene olefin monomers having two or more double bonds can also be polymerized. Examples of such monomers are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-decene, 1-undecene, 1-dodecene, 1-tetra Decene, 1-hexadecene, 1-icocene, norbornene, norbornadiene, ethylidenenorbornene, vinylnorbornene, dcclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6- Hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, etc. are included, and these monomers can be mixed and copolymerized 2 or more types.

When the olefin monomers are polymerized together with the olefin supporting catalyst of the present invention and the polymerization catalyst for olefin and second olefin polymerization, the polymerization temperature is preferably 25 to 500 ° C, more preferably 25 to 200 ° C, and 50 to 150 ° C. is most preferred.

In addition, when the olefin monomers are polymerized together with the olefin supported catalyst of the present invention and the polymerization catalyst for the second olefin polymerization, the polymerization pressure is preferably performed at 1 to 100 Kgf / cm 2, and when it is 1 to 70 Kgf / cm 2 More preferably, 5 to 50 Kgf / cm 2 Most preferred at this time. When the polymerization temperature and pressure range is out of range, the reactivity is lowered and the yield is low, or the molecular weight is not controlled by a rapid reaction, so that it is difficult to obtain a polymer having a desired physical property.

The catalyst for the first olefin polymerization according to the present invention may mainly act to produce low molecular weight polyolefins having a molecular weight of 1,000 to 200,000. On the other hand, the second olefin polymerization catalyst further introduced into the polymerization reactor mainly acts to produce a polymer moiety having a molecular weight of 100,000 to 1,000,000, thereby producing polyethylene having a bimodal or wide molecular weight distribution. In the case of the α-olefin, it is possible to produce a high-performance ethylene copolymer in which the α-olefin comonomer is concentrated on the high molecular weight chain side by the second olefin polymerization catalyst.

In this case, the molar ratio of [the catalyst for the first olefin polymerization] / [the catalyst for the second olefin polymerization] is preferably 0.01 to 1000, more preferably 0.1 to 100, in order to variously control the molecular weight distribution of the final polyolefin. Most preferably from 10 to 10.

In the present invention, when the olefin supported catalyst for olefin polymerization is prepared by mixing the first olefin polymerization catalyst, the promoter and the carrier, the reaction may be carried out using a solvent or may be carried out without a solvent. Solvents that can be used include aliphatic hydrocarbon solvents having 5 to 12 carbon atoms, including pentane, hexane, heptane, nonane, decane, isomers thereof, and the like; Aromatic hydrocarbon solvents such as toluene, benzene and the like; Hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and the like; Ether solvents such as diethyl ether and THF; Organic solvents such as acetone, ethyl acetate and the like are preferred, and hexane, heptane and toluene are more preferred. At this time, the solvent used is preferably a small amount of aluminum treatment to remove a small amount of water, air and the like acting as a catalyst poison.

At this time, the reaction temperature of the olefin supported catalyst for olefin polymerization should be -20 because the solvent must be present as a liquid. ℃ 100 ℃ is preferred, -10 ℃ 60 More preferably 0 ° C. Most preferred is from 40 ° C. In the above temperature range, the reaction may proceed optimally. On the other hand, the reaction time may take 10 minutes to 24 hours.

The olefin supported catalyst for olefin polymerization prepared as described above may be used by removing the reaction solvent through filtration or distillation under reduced pressure, and if necessary, soxhlet filtering with an aromatic hydrocarbon such as toluene may be used.

In the reactor according to the present invention, the olefin polymerization process using the olefin supported catalyst and the second olefin polymerization catalyst is preferably a slurry process, more preferably a slurry process in the form of a single reactor. In addition, the olefin supported catalyst may be diluted in the form of a slurry or the like suitable for an olefin polymerization process.

In detail, the first olefin polymerization catalyst for inducing low molecular weight polyolefin is impregnated in the carrier, and then the cocatalyst is impregnated to prepare the olefin supported catalyst for olefin polymerization. Using the olefin supported catalyst for olefin polymerization thus prepared, a second olefin polymerization catalyst is introduced which polymerizes olefins in a reactor or prior to polymerization, and copolymerizes high molecular weight or alpha-olefin well. The injected second olefin polymerization catalyst cannot be polymerized by itself, but is activated by a cocatalyst on the surface of the first olefin supported catalyst for olefin polymerization, thereby polymerized by the first supported olefin polymerization catalyst. A new type of polyolefin is formed between the polymer chains. In addition, it is possible to simply adjust the physical properties and molecular weight distribution of the polyolefin obtained by adjusting the time, type and amount of the catalyst for the second olefin polymerization.

The present invention can produce a polyolefin produced by the method for producing a polyolefin. The prepared polyolefin has a density in the range of 0.9 to 0.97, the melt index is in the range of 0.01 to 100, characterized in that the molecular weight distribution has a range of 3 to 15.

Hereinafter, the present invention will be described in detail through embodiments of the present invention. However, embodiments of the present invention may be modified in various forms, the scope of the present invention should not be construed in a way that is limited by the embodiments described below. Embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art.

In the present examples and comparative examples, the organic reagents and solvents required for catalyst preparation and polymerization are purified by standard methods from Aldrich, and ethylene is purified from high purity products of Applied Gas Technology by water and oxygen. The polymerization was carried out after passing through a filtration device, and proceeded by blocking contact between air and water at all stages of catalyst synthesis, loading, and polymerization.

To verify the structure of the catalyst, spectra were obtained using 300 MHz NMR (Bruker).

Apparent density was measured using an apparent tester (APparent Density Tester 1132, manufactured by APT Institute fr Prftechnik) by the method defined in DIN 53466 and ISO R 60.

Molecular weight and molecular weight distribution were obtained by gel permeation chromatography (GPC) analysis using 150 CV + manufactured by Waters. The analytical temperature was 140 ° C., trichlorobenzene was used as a solvent, and the number average molecular weight (M _n ) and the weight average molecular weight (M _w ) were obtained by standardizing polystyrene. The molecular weight distribution (Polydispersity index, PDI) was obtained by dividing the weight average molecular weight by the number average molecular weight.

The melt index (Melt Index, MI) and flow index (I ₂₁ ) of the polymer were measured by ASTM D-1238 (condition 190 ° C.), and the polymer density was measured by the method of ASTM D-1505-68.

Preparation Example 1 [Me ₃ SiO- (CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂

In a flask containing 9.74 g of 1,6-hexanediol and 15.7 g of p-toluenesulfonyl chloride, 50 ml of pyridine was placed in a refrigerator for one day. 500 ml of 2N HCl was added to the flask, followed by extraction with 100 ml of diethyl ether. The water slightly dissolved in ether was removed with anhydrous MgSO _4, and then the ether was distilled off under reduced pressure by filtration. Column chromatography on a silica gel using a diethyl ether solvent to give 9.00 g of a compound to which only one hydroxyl group was tosylated (yield 40%).

100 ml of anhydrous THF was added to 8.12 g of the obtained compound, and 45 ml of 2 N sodium cyclopentadiene (NaCp) was added to an ice cold bath. After 3 hours, 200 ml of water was added, and extracted with 100 ml of hexane. Column chromatography on silica gel using hexane: diethyl ether (v / v = 1: 1) gave 4.07 g of 6- (hydroxy) hexylcyclopentadiene ((6-hydroxy) -hexylcyclopentadiene) compound ( Yield 82%).

17.9 mmol of the obtained compound was dissolved in 25 mL of THF, and 2.7 mL of chlorotrimethylsilane and 3.00 mL of triethylamine were sequentially added. All volatiles were removed by vacuum and filtered with hexane. Hexane was distilled off under reduced pressure, followed by distillation under reduced pressure (78 ° C./0.2 torr) to obtain 3.37 g of a cyclopentadiene compound having a hydroxyl group protected by trimethylsilyl (yield 79%).

After dissolving 11.4 mmol of the obtained compound in 20 mL THF, 1.22 g of solid lithium diisopropylamide was added without contacting air at -78 ° C. The temperature was slowly raised to room temperature and then stirred for 2 hours. All volatiles were removed with a vacuum pump and 20 mL of THF was added again. 2.15 g of ZrCl ₄ (THF) ₂ were added thereto, and the resultant was stirred at 60 ° C. for 40 hours. After removing all volatiles using a vacuum pump, the mixture was extracted with a mixed solvent of toluene and hexane. 2.0 ml of chlorotrimethylsilane was added thereto, and the mixture was left at room temperature for one hour and then placed in a refrigerator to obtain a white solid as a catalyst for olefin polymerization (yield 70%).

1 H NMR (300 MHz, CDCl ₃ ): 6.34 (s, 2 H), 6.25 (s, 2 H), 3.62 (t, 2 H), 2.68 (t, 2 H), 1.6-1.2 (m, 8 H ), 0.17 (s, 9 H).

Preparation Example 2 [ ^t Bu-O- (CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂

6-Chlorohexanol was used to prepare t-Butyl-O- (CH ₂ ) ₆ -Cl using the method presented in Tetrahedron Lett. 2951 (1988), wherein NaCp was prepared above. The reaction was carried out in the same manner as in Example 1, to obtain t-Butyl-O- (CH ₂ ) ₆ -C ₅ H ₅ (yield 60%, bp 80 ℃ / 0.1mmHg). Here, zirconium was added in the same manner as in Production Example 1 to obtain a compound of one of the desired catalysts for olefin polymerization (yield 92%).

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

Preparation Example 3 [ ^t Bu-O- (CH ₂ ) ₆ -C ₅ H ₄ ] ₂ HfCl ₂

6-Chlorohexanol was used to prepare t-Butyl-O- (CH ₂ ) ₆ -Cl using the method presented in Tetrahedron Lett. 2951 (1988), wherein NaCp was prepared above. The reaction was carried out in the same manner as in Example 1, to obtain t-Butyl-O- (CH ₂ ) ₆ -C ₅ H ₅ (yield 60%, bp 80 ℃ / 0.1 mmHg). Hafnium was added in the same manner as that of zirconium in Preparation Example 1 to obtain a compound of one of the desired catalysts for olefin polymerization (yield 92%).

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

Preparation Example 4 ( ^t Bu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ H ₄ ) (9-C ₁₃ H ₉ ) ZrCl ₂

Solution of ^t Bu-O- (CH ₂ ) ₆ MgCl solution, which is a Grignard reagent, from the reaction between ^t Bu-O- (CH ₂ ) ₆ Cl compound and Mg (0) in diethyl ether (Et ₂ O) solvent Mol was obtained. To this was added MeSiCl ₃ compound (24.7 mL, 0.21 mol) at −100 ° C., stirred at room temperature for 3 hours or more, and the filtered solution was dried in vacuo to give ^t Bu-O- (CH ₂ ) ₆ SiMeCl ₂ . The compound was obtained (yield 84%).

Fluorenyllithium (4.82 g, 0.028 mol) / hexane in a solution of ^t Bu-O- (CH ₂ ) ₆ SiMeCl ₂ (7.7 g, 0.028 mol) dissolved in hexane (50 mL) at -78 ° C. 150 mL) was added slowly over 2 hours. Filter out the white precipitate (LiCl) and extract the desired product with hexane to vacuum dry all volatiles to give ( ^t Bu-O- (CH ₂ ) ₆ ) SiMe (9-C ₁₃ H ₁₀ ) as a pale yellow oil Was obtained (yield 99%).

THF solvent (50 mL) was added thereto, and reacted with a C ₅ H ₅ Li (2.0 g, 0.028 mol) / THF (50 mL) solution at room temperature for 3 hours or more, and all volatiles were vacuum dried and extracted with hexane. ( ^T Bu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ H ₅ ) (9-C ₁₃ H ₁₀ ) in the form of an orange oil as a final ligand was obtained (yield 95%). The structure of the ligand was confirmed by ¹ H NMR.

¹ H NMR (400 MHz, CDCl ₃ ): 1.17, 1.15 (t-BuO, 9H, s), -0.15, -0.36 (MeSi, 3H, s), 0.35, 0.27 (CH ₂ , 2H, m), 0.60, 0.70 (CH ₂ , 2H, m), 1.40, 1.26 (CH ₂ , 4H, m), 1.16, 1.12 (CH ₂ , 2H, m), 3.26 (tBuOCH ₂ , 2H, t, 3JH-H = 7 Hz), 2.68 (methyleneCpH, 2H, brs), 6.60, 6.52, 6.10 (CpH, 3H, brs), 4.10, 4.00 (FluH, 1H, s), 7.86 (FluH, 2H, m), 7.78 (FluH, 1H, m) , 7.53 (FluH, 1H, m), 7.43-7.22 (FluH, 4H, m)

Then ( ^t Bu—O— (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ H ₅ ) (9-C ₁₃ H ₁₀ ) (12 g, 0.028 mol) / THF (100 at −78 ° C. 2 mol of n-BuLi was added to the solution and allowed to react for at least 4 hours while raising to room temperature to give ( ^t Bu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ H ₅ Li) ( 9-C ₁₃ H ₁₀ Li) was obtained (yield 81%).

Next, a dilithium salt (2.0 g, 4.5 mmol) / ether (30 mL) was added to a suspension solution of ZrCl ₄ (1.05 g, 4.50 mmol) / ether (30 mL) at -78 ° C. ) Was slowly added to the solution and ( ^t Bu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ H ₅ Li) (9-C ₁₃ H ₁₀ Li) was added thereto for 3 hours at room temperature. Reacted further. All volatiles were vacuum dried and the resulting oily liquid material was filtered off by adding dichloromethane solvent. The filtered solution was dried in vacuo and hexane was added to induce a precipitate. The obtained precipitate was washed several times with hexane to give racemic- ( ^t Bu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ H ₄ ) (9-C ₁₃ H ₉ ) ZrCl ₂ compound as a red solid. Obtained (yield 54%).

¹ H NMR (400 MHz, CDCl ₃ ): 1.19 (t-BuO, 9H, s), 1.13 (MeSi, 3H, s), 1.79 (CH ₂ , 4H, m), 1.60 (CH ₂ , 4H, m), 1.48 (CH ₂ , 2H, m), 3.35 (tBuOCH ₂ , 2H, t, 3JH-H = 7 Hz), 6.61 (CpH, 2H, t, 3JH-H = 3 Hz), 5.76 (CpH, 2H, d, 3JH -H = 3 Hz), 8.13 (FluH, 1H, m), 7.83 (FluH, 1H, m), 7.78 (FluH, 1H, m), 7.65 (FluH, 1H, m), 7.54 (FluH, 1H, m) , 7.30 (FluH, 2H, m), 7.06 (FluH, 1H, m)

¹³ C NMR (400 MHz, CDCl ₃ ): 27.5 (Me ₃ CO, q, 1JC-H = 124 Hz), -3.3 (MeSi, q, 1JC-H = 121 Hz), 64.6, 66.7, 72.4, 103.3, 127.6, 128.4 , 129.0 (7C, s), 61.4 (Me ₃ COCH ₂ , t, 1JC-H = 135 Hz), 14.5 (ipsoSiCH ₂ , t, 1JC-H = 122 Hz), 33.1, 30.4, 25.9, 22.7 (4C, t, 1JC-H = 119 Hz), 110.7, 111.4, 125.0, 125.1, 128.8, 128.1, 126.5, 125.9, 125.3, 125.1, 125.0, 123.8 (FluC and CpC, 12C, d, 1JC-H = 171 Hz, 3JC-H = 10 Hz )

Preparation Example 5 ( ^t Bu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ (CH ₃ ) ₄ ) ( ^t Bu-N) TiCl ₂

50 g of Mg (s) was added to a 10 L-reactor at room temperature, followed by 300 ml of THF. After adding 0.5 g of I ₂ , the reactor temperature was maintained at 50 ° C. After the reactor temperature was stabilized, 250 g of 6-t-butoxyhexyl chloride was added to the reactor at a rate of 5 ml / min using a feeding pump. As the 6-t-butoxyhexyl chloride was added, it was observed that the reactor temperature was increased by 4-5 ° C. The mixture was stirred for 12 hours while adding 6-t-butoxyhexyl chloride. After 12 hours, a black reaction solution was obtained. 2 ml of the resulting black solution was taken and water was added to obtain an organic layer. 6-t-butoxyhexane was confirmed by 1 H-NMR. From the 6-t-butoxyhexane it can be seen that the Grinnard (Gringanrd) reaction proceeded well. Thus, 6-t-butoxyhexyl magnesium chloride was synthesized.

500 g of MeSiCl ₃ and 1 L of THF were added to the reactor, and the reactor temperature was cooled to 20 ° C. 560 g of the synthesized 6-t-butoxyhexyl magnesium chloride was added to the reactor at a rate of 5 mL / min using a feeding pump. After the feeding of the Grignard reagent (feeding) was completed, the reaction mixture was stirred for 12 hours while slowly raising the temperature to room temperature. After 12 hours, it was confirmed that a white MgCl ₂ salt was produced. 4 L of hexane was added to remove salts through labdori to obtain a filter solution. After the obtained filter solution was added to the reactor, hexane was removed at 70 ° C. to obtain a pale yellow liquid. The obtained liquid was confirmed to be the desired methyl (6-t-butoxy hexyl) dichlorosilane} compound through 1 H-NMR.

¹ H-NMR (CDCl ₃ ): 3.3 (t, 2H), 1.5 (m, 3H), 1.3 (m, 5H), 1.2 (s, 9H), 1.1 (m, 2H), 0.7 (s, 3H)

1.2 mol (150 g) of tetramethylcyclopentadiene and 2.4 L of THF were added to the reactor, and the reactor temperature was cooled to 20 ° C. 480 mL of n-BuLi was added to the reactor at a rate of 5 mL / min using a feeding pump. After n-BuLi was added, the reaction mixture was stirred for 12 hours while slowly raising the temperature to room temperature. After 12 hours of reaction, an equivalent of methyl (6-t-butoxy hexyl) dichlorosilane (326 g, 350 mL) was added quickly to the reactor. After stirring for 12 hours while slowly raising the temperature of the reactor, the reactor was cooled to 0 ° C., and then 2 equivalents of t-BuNH ₂ was added thereto. Stirring for 12 hours while slowly raising the reactor temperature to room temperature. After 12 hours of reaction, THF was removed, and 4 L of hexane was added thereto to obtain a filter solution from which salts were removed through labdori. After the filter solution was added to the reactor again, hexane was removed at 70 ° C. to obtain a yellow solution. The yellow solution obtained was identified as methyl (6-t-butoxyhexyl) (tetramethylCpH) t-butylaminosilane (Methyl (6-t-buthoxyhexyl) (tetramethylCpH) t-Butylaminosilane) compound through 1H-NMR. .

TiCl ₃ (THF) ₃ (10 mmol) to a dilithium salt of 78 ° C. ligand synthesized from TH-solution from n-BuLi and ligand dimethyl (tetramethylCpH) t-butylaminesilane (Dimethyl (tetramethylCpH) t-Butylaminosilane) Was added quickly. The reaction solution was slowly stirred at 78 ° C. for 12 hours. After stirring for 12 hours, an equivalent amount of PbCl ₂ (10 mmol) was added to the reaction solution at room temperature, followed by stirring for 12 hours. After stirring for 12 hours, a dark black solution was obtained. After removing THF from the reaction solution, hexane was added to filter the product. After removing hexane from the filter solution to be obtained, ( ^t Bu-O- (CH ₂ ) having the desired ([methyl (6-t-buthoxyhexyl) silyl (η ⁵ -tetramethylCp) (t-Butylamido)] TiCl ₂ ) was obtained from 1H-NMR. ) ₆ ) (CH ₃ ) Si (C ₅ (CH ₃ ) ₄ ) ( ^t Bu-N) TiCl ₂ .

¹ H-NMR (CDCl ₃ ): 3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 6H), 1.8 to 0.8 (m), 1.4 (s, 9H), 1.2 (s, 9H) , 0.7 (s, 3H)

<Manufacture example 6>

[(6-Methyl-1,2,3,4-tetrahydroquinolin-8-yl) trimethylcyclopentadienyl-ŋ ⁵ , κ-N] titanium dichloride ([(6-methyl-1,2,3 , 4-tetrahydroquinolin-8-yl) trimethylcyclopentadienyl-ŋ ⁵ , κ-N] titanium dichloride) compound

A solution of 6-methyl-1,2,3,4-tetrahydroquinoline (1.16 g, 7.90 mmol) in carbon tetrachloride (4 mL) was cooled to # 20 ° C. N-bromosuccinimide (1.41 g, 7.90 mml) solid was slowly added thereto, and the reaction temperature was raised to room temperature for 5 hours. The resulting compound was separated by column chromatography using MC and hexane (v: v = 1: 1) solvent to obtain a pale yellow oil, 8-bromo- 1,2,3,4-tetrahydro-6-methyl. Quinoline was obtained (0.71 g, 40%).

2,3-dimethyl-5-oxocyclopent-1-enylboronic acid (1.27 g, 8.26 mmol), Na ₂ CO ₃ (1.25 g, 11.8 mmol), Pd (PPh ₃ ) ₄ (0.182 g, 0.157 mmol) and degassed DME (dimethylether) (21 mL) and distilled water in the mixture of 8-bromo-1,2,3,4-tetrahydro-6-methylquinoline (7.87 mmol). Water (7 mL) was added and the solution was heated at 95 ° C. overnight. The reaction solution was lowered to room temperature and extracted twice with ethyl acetate solvent (50 mL). The obtained compound was separated by column chromatography using hexane and ethyl acetate (2: 1) solvent to give a pale yellow solid, 5- (3,4-dimethyl-2-cyclopenten-l-one) -7-methyl-. 1,2,3,4-tetrahydroquinoline was obtained. (Yield 90%).

Anhydrous _{La (OTf) 3 (21.4 m㏖} ) and TFH (24 ㎖) a cooling to 78 ^o C ℃ solution was added and then MeLi (13.4 ㎖, 21.4 m㏖) was reacted for 1 hour. To this synthesized 5- (3,4-dimethyl-2-cyclopenten-l-one) -7-methyl-1,2,3,4-tetrahydroquinoline (7.13 mmol) compound was added thereto at 78 ° C. The reaction was carried out for 2 hours, and extracted with water and an acetate solvent. The organic layer obtained was shaken with HCl (2N, 20 mL) for 2 minutes, neutralized with NaHCO ₃ aqueous solution (20 mL), and dried over MgSO ₄ . The obtained compound was separated by column chromatography using hexane and ethyl acetate solvent (10: 1) to give pale yellow solid 1,2,3,4-tetrahydro-6-methyl-8- (2,3,5 -Trimethylcyclopenta-1,3-dienyl) quinoline ligand was obtained. (Yield 40%).

1,2,3,4-tetrahydro-6-methyl-8- (2,3,5-trimethylcyclopenta-1,3-dienyl) quinoline ligand (0.696 mmol) and Ti (NMe ₂ ) obtained above ₄ Compound (0.156 g, 0.696 mmol) was dissolved in toluene (2 mL), and the reaction solution was reacted at 80 ° C. for 2 days, and all solvents were removed to obtain a red solid compound [(6-methyl-1,2, 3,4-tetrahydroquinolin-8-yl) trimethylcyclopentadienyl-ŋ ⁵ , κ-N] titanium dichloride was obtained. (100% yield)

Toluene (2 mL) was further added to the red solid compound thus produced, and then Me ₂ SiCl ₂ (0.269 g, 2.09 mmol) was added at room temperature to react the reaction solution for about 4 hours. The resulting compound was recrystallized at 30 ° C. under hexane to give a pure red solid (0.183 g, 66% yield).

¹ H NMR (C ₆ D ₆ ): δ 1.36-1.44 (m, 2H, CH ₂ CH ₂ CH ₂ ), 1.76 (s, 3H, CH ₃ ), 1.85 (s, 3H, CH ₃ ), 2.07 (s , 3H, CH ₃ ), 2.18 (s, 3H, CH ₃ ), 2.12 (t, J = 4 Hz, 2H, CH ₂ ), 4.50-4.70 (m, 2H, N-CH ₂ ), 6.02 (s, 1H , Cp-H), 6.59 (s, 1H, C ₆ H ₂ ), 6.78 (s, 1H, C ₆ H ₂ ) ppm.

¹³ C { ¹ H} NMR (C ₆ D ₆ ): δ 12.76, 14.87, 15.06, 21.14, 22.39, 26.32, 54.18, 117.49, 120.40, 126.98, 129.53, 130.96, 131.05, 133.19, 143.22, 143.60, 160.82 ppm. Anal. Calc.

(C ₁₈ H ₂₁ Cl ₂ NTi): C, 58.41; H, 5.72; N, 3.78%. Found: C, 58.19; H, 5.93; N, 3.89%.

<Manufacture example 7>

[(1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-ŋ ⁵ , κ-N] titanium dimethyl

([(1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-ŋ ⁵ , κ-N] titanium dimethyl) compound

1,2,3,4-tetrahydroquinoline (957 mg, 7.185 mmol) was dissolved in THF (10 mL), stirred at 78 ° C. for 30 minutes, and n-BuLi (2.87 mL, 7.185 mmol) was dissolved in nitrogen. Into the syringe in the atmosphere, it was made into a yellow suspension state. After sufficiently stirring for 3 hours, the gas was removed by raising the temperature to 20 ° C. and lowering the temperature to 78 ° C. before adding CO ₂ gas. At this time, the color of the solution turned to white, which was almost colorless. After raising the temperature to 20 ° C., vacuum was applied to remove the remaining CO ₂ gas for 1 hour, and tert-BuLi (5.07 mL, 8.622 mmol) was added thereto. At this time, the color of the solution turned red. 0.33M CeCl ₃ dissolved in THF after stirring for 2 hours while maintaining at 20 ℃ ^. 2LiCl solution (26.1 mL, 8.622 mmol) and tetramethyl cyclopentenone (1.182 g, 8.622 mmol) were added under nitrogen. After venting while slowly raising the temperature to room temperature, the solvent was removed, titrated with pentane in nitrogen, filtered, and white crystal powder was obtained (yield 41%).

n-BuLi (220 mg, 0.792 mmol, 2.5 M) was slowly added to a cold ether solution of the prepared compound (100 mg, 0.396 mmol) with stirring (-30 ° C). After raising to room temperature and reacting for 6 hours, it was filtered, washed several times with ether, and vacuumed to blow ether to obtain TiCl ₄ DME (90 mg) as a pale yellow solid. Lose.

The TiCl ₄ DME (66 mg, 0.235 mmol) was added to an ether (−30 ° C.) and placed in a refrigerator for about 1 hour. After 1 hour, MeLi (0.3 mL, 0.470 mmol, 1.4 M) was slowly added while stirring. After stirring for 15 minutes, lithium salt (70 mg, 0.235 mmol) was added thereto, followed by stirring at room temperature for 3 hours, followed by vacuum to remove the solvent and again dissolving with pentane (filter). ). Only soluble in pentane was taken and vacuumed to give pentane to give a dark brown titanium complex (52 mg). (Yield 67%).

¹ H NMR (C ₆ D ₆ ): δ 7.00 (d, J = 7.6 Hz, 1H), 9.92 (d, J = 7.6 Hz, 1H), 6.83 (t, J = 7.6 Hz, 1H), 4.53 (m , 2H), 2.47 (t, J = 6.4 Hz, 2H), 2.05 (s, 6H), 1.66 (s, 6H), 1.76-1.65 (m, 2H), 0.58 (s, 6H).

In Examples 1 to 3 below, an olefin supported catalyst for olefin polymerization was prepared, and in Examples 4 to 45, an olefin copolymer was prepared.

<Example 1> Preparation of olefin supported catalyst for olefin polymerization

(Carrier drying)

Silica (Sylopol 948, Grace Davison) was dehydrated under vacuum at a temperature of 400 ° C. for 12 hours.

(Preparation of olefin supported catalyst for olefin polymerization)

10 g of the dried silica was put in a glass reactor, and 100 ml of toluene solution was added and stirred. 50 ml of a toluene solution in which 2.5 mmol of [Me ₃ SiO- (CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ prepared in Preparation Example 1 was further added, followed by stirring at 100 ° C. for 2 hours. Reacted. After the reaction was completed, the stirring was stopped, the toluene was separated by layers, and then washed three times with 100 ml of toluene solution, and then reduced to remove toluene to obtain a solid powder.

The _{[Me 3 SiO- (CH 2)} 6 -C 5 H 4] 2 ZrCl ₂ was dispersed in a toluene solution to the supported silica powder, was added to methylaluminoxane (MAO) solution containing 120 m㏖ aluminum 40 After slowly reacting with stirring at room temperature, the reaction mixture was washed with a sufficient amount of toluene to remove the unreacted aluminum compound, followed by stirring for 1 hour. After completion of the reaction, stirring was stopped, the toluene layer was separated and removed, and the remaining toluene was removed by reducing the pressure at 50 ° C to prepare an olefin supported catalyst.

Example 2 Preparation of Supported Olefin Catalyst for Olefin Polymerization

[ ^T Bu-O- (CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ of Preparation Example 2 was used instead of [Me ₃ SiO- (CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ of Preparation Example 1. Except that except that the olefin supported catalyst was prepared in the same manner as in Example 1.

Example 3 Preparation of Supported Olefin Catalyst for Olefin Polymerization

[ ^T Bu-O- (CH ₂ ) ₆ -C ₅ H ₄ ] ₂ HfCl ₂ of Preparation Example 3 was used instead of the [Me ₃ SiO— (CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ of Preparation Example ₁ . An olefin supported catalyst was prepared in the same manner as in Example 1 except that it was used.

Example 4 Preparation of Olefin Copolymer

30 mg of the olefin supported catalyst for olefin polymerization prepared in Example 1 was quantified in a dry box, placed in a 50 ml glass bottle, sealed with a rubber diaphragm, and then taken out of the dry box to prepare a catalyst for injection. The polymerization was carried out in a 2 L metal alloy reactor used at high pressure with temperature control equipped with a mechanical stirrer.

1 liter of hexane containing 0.6 mmol moltriethylaluminum and 5 ml of 1-hexene as comonomer were added to the reactor, and then the prepared olefin supported catalyst for polymerization of olefin was introduced into the reactor without air contact. Immediately, 7.5 μmol of ( ^t Bu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ H ₄ ) (9-C ₁₃ H ₉ ) ZrCl ₂ of Preparation Example 4 was dissolved in 50 ml of toluene. Input. Thereafter, the gas ethylene monomer was polymerized at 80 DEG C for 1 hour while continuously adding the pressure at 9 Kgf / cm ² . Termination of the polymerization was completed by first stopping the stirring and then evacuating and removing the unreacted ethylene. The polymer obtained therefrom was filtered to remove most of the polymerization solvent and then dried in an 80 ° C. vacuum oven for 4 hours to prepare an olefin copolymer.

Example 5

5 minutes after the addition of the olefin supported catalyst for olefin polymerization, ( ^t Bu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ H ₄ ) (9-C ₁₃ H ₉ ) of Preparation Example 4 was further added. An olefin copolymer was prepared in the same manner as in Example 4, except that 7.5 μmol of ZrCl ₂ was dissolved in 50 ml of toluene.

<Example 6>

10 minutes after the addition of the olefin supported catalyst for olefin polymerization, ( ^t Bu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ H ₄ ) (9-C ₁₃ H ₉ ) of Preparation Example 4 was further added. An olefin copolymer was prepared in the same manner as in Example 4, except that 7.5 μmol of ZrCl ₂ was dissolved in 50 ml of toluene.

<Example 7>

Immediately after addition of the olefin supported catalyst for olefin polymerization, ( ^t Bu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ H ₄ ) (9-C ₁₃ H ₉ ) ZrCl ₂ of Preparation Example 4 was added. An olefin copolymer was prepared in the same manner as in Example 4, except that 3.75 μmol was dissolved in 50 ml of toluene.

<Example 8>

5 minutes after the addition of the olefin supported catalyst for olefin polymerization, ( ^t Bu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ H ₄ ) (9-C ₁₃ H ₉ ) of Preparation Example 4 was further added. An olefin copolymer was prepared in the same manner as in Example 4, except that 3.75 μmol of ZrCl ₂ was dissolved in 50 ml of toluene.

Example 9

10 minutes after the addition of the olefin supported catalyst for olefin polymerization, ( ^t Bu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ H ₄ ) (9-C ₁₃ H ₉ ) of Preparation Example 4 was further added. An olefin copolymer was prepared in the same manner as in Example 4, except that 3.75 µmol of ZrCl ₂ was dissolved in 50 ml of toluene.

<Example 10>

Immediately after addition of the olefin supported catalyst for olefin polymerization, ( ^t Bu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ H ₄ ) (9-C ₁₃ H ₉ ) ZrCl ₂ of Preparation Example 4 was added. An olefin copolymer was prepared in the same manner as in Example 4, except that 15.0 μmol was dissolved in 50 ml of toluene.

<Example 11>

5 minutes after the addition of the olefin supported catalyst for olefin polymerization, ( ^t Bu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ H ₄ ) (9-C ₁₃ H ₉ ) of Preparation Example 4 was further added. An olefin copolymer was prepared in the same manner as in Example 4, except that 15.0 μmol of ZrCl ₂ was dissolved in 50 ml of toluene.

<Example 12>

10 minutes after the addition of the olefin supported catalyst for olefin polymerization, ( ^t Bu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ H ₄ ) (9-C ₁₃ H ₉ ) of Preparation Example 4 was further added. An olefin copolymer was prepared in the same manner as in Example 4, except that 15.0 µmol of ZrCl ₂ was dissolved in 50 ml of toluene.

Example 13

An olefin supported catalyst for olefin polymerization was added immediately and further ( ^t Bu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ (CH ₃ ) ₄ ) ( ^t Bu-N) TiCl ₂ of Preparation Example 5 An olefin copolymer was prepared in the same manner as in Example 4, except that 3.75 μmol was dissolved in 50 ml of toluene.

<Example 14>

Immediately after addition of the olefin supported catalyst for olefin polymerization, ( ^t Bu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ (CH ₃ ) ₄ ) ( ^t Bu-N) TiCl of Preparation Example 5 _An olefin copolymer was prepared in the same manner as in Example 4, except that ₂ 7.5 mol was dissolved in 50 ml of toluene.

<Example 15>

Immediately after addition of the olefin supported catalyst for olefin polymerization, ( ^t Bu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ (CH ₃ ) ₄ ) ( ^t Bu-N) TiCl of Preparation Example 5 _{2 An} olefin copolymer was prepared in the same manner as in Example 4, except that 15.0 μmol was dissolved in 50 ml of toluene.

<Examples 16 to 18>

Immediately after adding the olefin supported catalyst for olefin polymerization, [(6-methyl-1,2,3,4-tetrahydroquinolin-8-yl) trimethylcyclopentadienyl-ŋ ⁵ , κ-N] titanium dichloride 3.75, of Preparation Example 6 was added. An olefin copolymer was prepared in the same manner as in Example 4, except that 7.5 and 15.0 mol were dissolved in 50 ml of toluene, respectively.

<Examples 19 to 21>

Immediately after the addition of the olefin supported catalyst for olefin polymerization, [(1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-ŋ ⁵ , κ-N] titanium dimethyl 3.75, 7.5, 15.0 μ of Preparation Example 7 An olefin copolymer was prepared in the same manner as in Example 4, except that mol was dissolved in 50 ml of toluene, respectively.

<Examples 22 to 33>

An olefin copolymer was prepared in the same manner as in Examples 4, 7, 10, 13 to 21, except that the olefin supported catalyst for olefin polymerization prepared in Example 2 was used.

<Examples 34 to 45>

An olefin copolymer was prepared in the same manner as in Examples 4, 7, 10, 13 to 21, except that the olefin supported catalyst for olefin polymerization prepared in Example 3 was used.

Comparative Example 1

Using only 30 mg of the olefin supported catalyst for olefin polymerization prepared in Example 1 and further ( ^t Bu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ H ₄ ) (9-C ₁₃ H ₉ An olefin copolymer was prepared in the same manner as in Example 4, except that ZrCl ₂ was not used.

Comparative Example 2

Using only 30 mg of the olefin supported catalyst for olefin polymerization prepared in Example 2 and further ( ^t Bu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ H ₄ ) (9-C ₁₃ H ₉ A polyolefin copolymer was prepared in the same manner as in Example 4, except that ZrCl ₂ was not used.

Comparative Example 3

Using only 30 mg of the olefin supported catalyst for olefin polymerization prepared in Example 3 and further ( ^t Bu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ H ₄ ) (9-C ₁₃ H ₉ Polyolefin copolymer was prepared in the same manner as in Example 4, except that ZrCl ₂ was not used.

The polymerization results of the above examples, that is, the copolymerization activity, density, melt index, molecular weight and molecular weight distribution (MWD) of ethylene and 1-hexene for the catalyst are shown in Tables 1 and 2 below.

When ethylene / 1-hexene copolymerization was carried out using the olefin supported catalyst for olefin polymerization and the second olefin polymerization catalyst (Preparation Examples 4 to 7) added under the conditions of all the examples and comparative examples, the reactor wall or polymer particles There was no fouling between the fields. This is because the catalyst for the first olefin polymerization is bound to the carrier by Lewis acid-base interaction, and the polymerization for the second olefin polymerization is only activated by the promoter attached to the surface of the carrier, so that the polymerization proceeds only on the carrier. to be.

As shown in Tables 1 and 2, the additionally added second catalyst for olefin polymerization used 0.5 to 2 multiples of the first olefin polymerization catalyst supported on the olefin supported catalyst for olefin polymerization, and the input time was used for olefin polymerization. The polymerization was controlled at 0, 5, and 10 minutes after the polymerization was carried out using only the olefin supported catalyst. In the present embodiment, in the case of the first olefin polymerization catalyst supported on the olefin supported catalyst for olefin polymerization, a compound having low molecular weight and low 1-hexene reactivity was used, and in the case of the second olefin polymerization catalyst, a high molecular weight, 1-hexene Highly reactive compounds were used. However, its characteristics and order can be changed at any time.

As a result, as shown in Table 1, the slower the input time of the second olefin polymerization catalyst, the polymer chain polymerized by the first olefin polymerization catalyst wraps around the surface of the carrier, thereby reducing the amount of additional activation. As a result, there were many 1-hexene branches produced by the characteristics of the catalyst for the second olefin polymerization, and the density increased little by little as the amount of the ethylene / 1-hexene copolymer having a high molecular weight was decreased, the melt index was increased, and the molecular weight was Decreased. In the case of adjusting the added amount, the physical properties of the obtained polymer can be easily adjusted by simply increasing the amount of the second olefin polymerization catalyst added to the reactor immediately after adding the olefin supported catalyst for olefin polymerization.

As shown in Comparative Example, when only one olefin polymerization catalyst of Preparation Examples 1 to 3 was used, the weight average molecular weight (M _w ) was 70,000 to 140,000. It can be adjusted to, and the molecular weight distribution was 3.1 to 3.6 narrow width was able to be adjusted to a wide width of 4.1 to 12.1. In addition, it can be seen that the density can be adjusted to 0.946 to 0.930 g / cm 3 even though the use amount of 1-hexene is fixed at 5 ml.

In the case of the olefin supported catalyst, when the olefin supported catalyst for olefin polymerization made in Example 3 is used, the molecular weight is higher than that when using the olefin supported catalyst for olefin polymerization made in Examples 1 to 2, but the 1-hexene reactivity and polymerization The activity was relatively low.

In addition, in the case of the second olefin polymerization catalyst additionally added, when the production example 6 is used, the 1-hexene reactivity is higher than that when the production examples 4 and 5 are used, but the 1-hexene reactivity is similar. I could see.

In conclusion, the method for preparing polyolefin according to the present invention does not spend a lot of time preparing various combinations of catalyst systems as supported catalysts, but also supports olefin supported catalysts, and then proceeds with the polymerization using the second olefin polymerization in the reactor. It is possible to control the physical properties of the polymer prepared by simply adding a catalyst for the.

In the method for preparing polyolefin according to the present invention, when a polyolefin is prepared by mixing a supported olefin catalyst including an olefin polymerization catalyst and an olefin monomer in a reactor, and adding a second olefin polymerization catalyst to the supported catalyst, The activity, density, melt map, molecular weight and molecular weight distribution of the resulting polyolefin can be easily adjusted according to the type of the olefin supported catalyst and the addition time, the type and amount of the catalyst for the second olefin polymerization. In addition, after only preparing the olefin supported catalyst for olefin polymerization, the second and second olefin polymerization catalysts which are introduced later while the polymerization is carried out as necessary can be controlled to reduce the time and effort for preparing the supported catalyst.

Claims (26)

1) mixing an olefin-supported catalyst and an olefin including a first olefin polymerization catalyst, a promoter and a carrier; And 2) adding a second olefin polymerization catalyst in an unsupported state before or after polymerizing the olefin using the olefin supported catalyst. Method for producing a polyolefin comprising a. The method of claim 1, wherein the first olefin polymerization catalyst and the second olefin polymerization catalyst comprise a metallocene compound. The method of claim 2, wherein the metallocene compound is one selected from compounds represented by Chemical Formulas 1 to 3 below: [Formula 1]

[Formula 2]

(3)

In Chemical Formulas 1, 2 and 3, C _p and C _p 같 are the same as or different from each other, and are each independently selected from a cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl group; R ^m and R ⁿ are the same as or different from each other, and each independently hydrogen or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group, and an alkylaryl group , Arylalkyl group, arylalkenyl group and alkylsilyl group; R ¹ and R ² are the same as or different from each other, and are each independently hydrogen or a hydrocarbyl group having 1 to 6 carbon atoms; a, a ', b and b' are the same as or different from each other, and each independently an integer of 1 to 4; M is a transition metal of Group 14, 15 or 16 in the periodic table; Q is selected from a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group and an alkylidene group having 1 to 20 carbon atoms; k is 2 or 3; z is 0 or 1 and z is 0 when k is 3; B is selected from hydrocarbyl groups containing silicon, germanium, phosphorus, nitrogen, boron or aluminum and alkyl groups of 1 to 4 carbon atoms; J is selected from NR ^s , O, PR ^s and S, and R ^s is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. The compound of claim 3, wherein R ^m , R ⁿ , B and R ^s Any one or more of the hydrogen present in the method for producing a polyolefin is a substituent selected from the substituents represented by the following formula (4), (5) and (6): [Formula 4]

In Chemical Formula 4, Z is an oxygen atom or a sulfur atom; R0 to R3 are the same as or different from each other, and are each independently a hydrogen group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group, an alkylaryl group, and aryl An alkyl group and an arylalkenyl group; R2 and R3 may be linked to each other to form a ring; G is selected from alkoxy, aryloxy, alkylthio, arylthio and substituted or unsubstituted phenyl having 1 to 20 carbon atoms, or can be linked to R2 or R3 to form a ring; If Z is a sulfur atom, G is alkoxy or aryloxy; If G is alkylthio, arylthio or substituted or unsubstituted phenyl, Z is an oxygen atom. [Chemical Formula 5]

In Formula 5, Z1 and Z2 are each independently an oxygen or sulfur atom, at least one of Z1 and Z2 is an oxygen atom, R4 to R6 are the same as or different from each other, and are each independently a hydrogen group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group, an alkylaryl group, and aryl Or an arylalkenyl group, or at least two of R4 to R6 may be linked to each other to form a ring. [Formula 6]

In Formula 6, Z 3 is one selected from oxygen, sulfur, nitrogen, phosphorus and arsenic atoms; R7 and R9 are the same as or different from each other, and are each independently a hydrogen group, an alkyl group having 1 to 40 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group, an alkylaryl group, and aryl An alkyl group and an arylalkenyl group; R8 is one selected from a hydrogen group or an alkyl group having 1 to 40 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group, an alkylaryl group, an alkylsilyl group, an arylsilyl group and a substituted or unsubstituted phenyl group; n is 1 or 2; N is 1 if Z 3 is oxygen or sulfur and n is 2 if Z 3 is nitrogen, phosphorus or arsenic. The method of claim 3, wherein the metallocene compound represented by Formula 1 is [AO- (CH ₂ ) _d -C ₅ H ₄ ] ₂ ZrCl ₂ or [AO- (CH ₂ ) _d -C ₉ H ₆ ] ZrCl ₃ ego, In the above formula, d is an integer of 4-8, A is methoxymethyl, t-butoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1- Method for producing a polyolefin is one selected from methyl-1-methoxyethyl (1-methyl-1-methoxyethyl) and t-butyl (t-butyl). The method of claim 3, wherein the metallocene compound represented by Formula 2 is [AO- (CH ₂ ) _e -C ₅ H ₄ ] C (CH ₃ ) ₂ [C ₁₃ H ₈ ] ZrCl _2, [AO- (CH ₂ ) _e -C ₅ H ₄ ] Si (CH ₃ ) ₂ [C ₁₃ H ₈ ] ZrCl ₂ , [C ₅ H ₅ ] C (CH ₃ ) (AO- (CH ₂ ) _e ) [C ₁₃ H ₈ ] ZrCl ₂ and [C ₅ H ₅ ] Si (CH ₃ ) (AO- (CH ₂ ) _e ) [C ₁₃ H ₈ ] ZrCl ₂ ; In the above formula, e is an integer of 4-8, A is methoxymethyl, t-butoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl A method for producing a polyolefin, which is one selected from -1-methoxyethyl (1-methyl-1-methoxyethyl) and t-butyl (t-butyl). The method of claim 3, wherein the metallocene compound represented by Chemical Formula 3 is [(AD- (CH ₂ ) _f )] (CH ₃ ) X (C ₅ Me ₄ ) (NCMe ₃ )] TiCl ₂ or [(AD- (CH ₂ ) _f )] (CH ₃ ) X (C ₅ Me ₄ ) (NCMe ₃ )] ZrCl ₂ , In the above formula, f is an integer of 4 to 8, X is one selected from methylene, ethylene and silicon, D is an oxygen or nitrogen atom, A is hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 1 to 20 carbon atoms, aryl, alkylaryl, arylalkyl, alkylsilyl, arylsilyl, methoxymethyl, t-butoxymethyl , Tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl and t-butyl (t-butyl) is one of the polyolefin manufacturing method. The method of claim 2, wherein the metallocene compound comprises a compound represented by any one of the following structural formulas.

In the above formulas. a is an integer of 4 to 8, D is an oxygen or nitrogen atom, A is hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 1 to 20 carbon atoms, aryl, alkylaryl, arylalkyl, alkylsilyl, arylsilyl, methoxymethyl, t-butoxymethyl , Tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl and t-butyl (t-butyl), R10 is hydrogen or methyl group, Q5 and Q6 are each independently one selected from methyl, dimethylamido and chloride groups. The method of claim 1, wherein the promoter is a transition metal compound including a Group 13 transition metal in the periodic table. The method of claim 9, wherein the transition metal compound comprises one selected from compounds represented by Formulas 7, 8, and 9 below. [Formula 7] -[Al (R11) -O] _n - In Chemical Formula 7, R11 is a halogen group or a hydrocarbyl group having 1 to 20 carbon atoms unsubstituted or substituted with halogen, n is an integer from 2 to 20, [Formula 8] G (R12) ₃ In Chemical Formula 8, G is aluminum or boron; R12 is the same as or different from each other, a halogen group or a hydrocarbyl group having 1 to 20 carbon atoms unsubstituted or substituted with halogen, [Formula 9] [L-H] ⁺ [IE ₄ ] ^-  Or [L] ⁺ [IE ₄ ] ^- In Chemical Formula 9, L is a neutral or cationic Lewis acid, H is a hydrogen atom, N is one selected from Al, Ga, In and Ti, E is an aryl group having 6 to 40 carbon atoms, which is a halogen group, a hydrocarbyl having 1 to 20 carbon atoms, an alkoxy group, a phenoxy group, and having 1 to 20 carbon atoms containing at least one of nitrogen, phosphorus, sulfur and oxygen atoms. It may be substituted with one or more selected from hydrocarbyl groups, the four E are the same or different from each other. The method of claim 10, wherein the compound represented by Chemical Formula 7 is at least one compound selected from the group consisting of methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane and butyl aluminoxane. The compound represented by the formula (8) is trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum, diethylchloroaluminum , Triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum And dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron and tributyl boron. The compound represented by the formula (9) is triethyl ammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium tetra (p -Tolyl) boron, tripropylammonium tetra (p-tolyl) boron, triethylammonium tetra (o, p-dimethylphenyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium Tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N-diethylanilinium tetraphenylboron, N , N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium Tetraphenylboron, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra (p-tolyl) aluminum, tripropylammonium Tetra (p-tolyl) aluminum, triethylammonium tetra (o, p-dimethylphenyl) aluminum, tributylammonium tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) Aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N-diethylanilinium tetrapenta Florophenyl aluminum, diethyl ammonium tetrapentafluorophenyl aluminum, triphenyl phosphonium tetraphenyl aluminum, trimethyl phosphonium tetraphenyl aluminium , Triethyl ammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium tetra (p-tolyl) boron, tripropyl ammonium tetra (p -Tolyl) boron, triethylammonium tetra (o, p-dimethylphenyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethyl Ammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, triphenylcarbonium tetraphenylboron, triphenylcarbonium tetra Phenyl Alumi , Triphenyl car I Titanium tetra (p- methylphenyl to triple) boron and triphenyl ka I 1 A method for producing a polyolefin or more compounds selected from the group consisting of Titanium tetra-penta flow phenylboronic to. The method according to claim 1, wherein the molar ratio of [the catalyst for the first olefin polymerization] / [the catalyst for the second olefin polymerization] is 0.01 to 1000. The method according to claim 1, wherein the solvent is added to the step of mixing the olefin supported catalyst and olefin in the step 1). The method of claim 15, wherein the solvent is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms; Aromatic hydrocarbon solvents; Hydrocarbon solvents substituted with chlorine atoms; Ether solvents; And one, or a mixture of two or more thereof in an organic solvent. The reaction temperature for preparing the olefin supported catalyst for olefin polymerization is -20. ℃ 100 Process for producing a polyolefin is ℃. The method according to claim 1, wherein the cocatalyst is a method of producing a polyolefin containing 1 to 10,000 moles of the Group 13 transition metal contained in the cocatalyst relative to 1 mol of Group 4 transition metals contained in the metallocene compound. The method of claim 1, wherein the carrier is dried at 200 to 800 ℃ to contain a hydroxyl group and a siloxane group on the surface. The method of claim 19, wherein the carrier is one selected from silica, silica-alumina, and silica-magnesia. The method for producing a polyolefin according to claim 19, wherein the amount of hydroxyl groups on the surface of the carrier is 0.1 to 10 mmol / g. The method of claim 1, wherein the olefin supporting catalyst for olefin polymerization is added to an olefin monomer in a slurry state prepared by diluting in a solvent. The method of claim 1, wherein the olefin comprises one or a mixture of two or more selected from alpha olefins, cyclic olefins, diene olefin monomers and triene olefin monomers. The method of claim 1, wherein the olefin is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-icocene, norbornene, norbornadiene, ethylidenenorbornene, vinylnorbornene, dcclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1 A method for producing a polyolefin, wherein one or two or more of 6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene are mixed. The method of claim 1, wherein step 2) is carried out at a temperature of 25 to 500 ℃. The method of claim 1, wherein step 2) is performed at a pressure of 1 to 100 Kgf / cm 2.

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