KR20150144441A - Metallocene catalyst for olefin polymerization, supported by electroconducting carbon support - Google Patents

Abstract

The present invention provides: a metallocene supported catalyst for olefin polymerization which is supported by an electroconductive carbon support, wherein the electroconductive carbon support is reformed to have functional groups capable of forming a covalent bond, and the functional group on the electroconductive carbon support and an organic functional group except metals among metallocene catalysts are coupled through the covalent bond; a method for manufacturing the catalyst; a complex including a polyolefin-electroconductive carbon support; and a method for manufacturing the complex. If using the novel supported metallocene catalyst in accordance with the present invention, olefin grows on the electroconductive carbon support having excellent electronic, thermal, and mechanical properties such as graphene, thereby easily manufacturing a nanocomplex of the polyolefin-electroconductive carbon support in which an electroconductive carbon structure is excellently dispersed.

Description

[0001] The present invention relates to a metallocene catalyst for olefin polymerization, supported by electroconducting carbon support, supported on an electrically conductive carbon-

The present invention relates to a metallocene catalyst for olefin polymerization supported on an electrically conductive carbon-based carrier; A method for producing the same; Polyolefin-electroconductive carbonaceous carrier-containing complex; And a method for producing the same.

Uses of polyolefins include many things in our real life. For example, there are shopping bags, plastic houses, fishing nets, tobacco wrappers, noodles bags, yogurt bottles, battery cases, automobile bumpers, interior materials, shoe soles, washing machines and the like.

Generally, olefin polymers and copolymers such as ethylene polymers, propylene polymers and ethylene-alpha olefin copolymers have been prepared by heterogeneous catalyst systems consisting of titanium compounds and alkyl aluminum compounds. Recently, a metallocene catalyst, which is a homogeneous catalyst with extremely high catalytic activity, has been developed and a polyolefin is produced using a metallocene catalyst.

The metallocene catalyst is a homogeneous, single-site catalyst. The molecular weight distribution and chemical compositional distribution of the polyolefin produced are very narrow and homogeneous. Depending on the ligand structure of the metallocene catalyst, stereoregularity, comonomer, The responsiveness and the hydrogen responsiveness can be freely controlled, and the physical properties of the polyolefin associated therewith can be greatly improved as compared with the Ziegler-Natta catalyst.

On the other hand, the metallocene-based catalyst is a catalyst in which a transition metal of Group 4 of the periodic table (for example, titanium, zirconium, hafnium) has at least one cycloalkanedienyl group (e.g., cyclopentadienyl Cyclopentadienyls, indenyls, fluorenyls) in the molecule. This type of metallocene catalyst is used for polymerization with a cocatalyst. All olefin polymerization catalysts comprising a transition metal compound such as zirconocene and an organoaluminum-oxy compound (aluminoxane) are known as catalysts capable of producing olefin polymers and copolymers with high polymerization activity.

Immobilization is indispensable for the use of such metallocene catalysts in slurry or gaseous olefin polymerization processes. This is due to the fact that when the homogeneous metallocene catalyst is added to the slurry and the gas phase polymerization process, there is a problem in the process such as agglomerate, fouling, sheeting and plugging of the produced polymer And the shape of the polyolefin polymer particle is very irregular, and the product density is low and the production of the product is impossible.

In order to solve these various problems, researches have been carried out on the support, and a metallocene supported catalyst is supported on a porous inorganic or organic material such as silica, alumina, magnesium dichloride or the like by metallocene alone or metallocene and cocatalyst. A method of polymerizing a polyolefin has been developed.

Recently, researches on polymer nanocomposites having nanostructures having various functions in polyolefins and copolymers have been actively conducted. Among these nanostructures, nanomaterials with the highest electrical conductivity and thermal conductivity are known as graphene. In order to improve the electrical conductivity and thermal conductivity of polymers, graphene-added polymer composites have been developed. Most of them are produced by melt mixing in which graphenes are added in a molten polymer state in an extruder, or by mixing graphene dispersed in a solvent with a polymer solution To prepare a polymer nanocomposite. In the above method, the graphene dispersion is not easy and the graphene has inherent properties. Among a series of studies to solve this problem, the production of polymer nanocomposites has been reported by in situ polymerization method in which graphene is dispersed in a polymerization reactor and polymerized immediately. This method is more effective in dispersing the graphene than the melt mixing method or the solution mixing method, but is not completely dispersed due to graphene agglomeration.

An object of the present invention is to provide a metallocene catalyst for olefin polymerization and copolymerization supported on an electrically conductive carbon-based support, on which a polymer chain can grow on the surface of an electrically conductive carbon-based support such as graphene.

It is another object of the present invention to provide a process for producing a polyolefin capable of completely dispersing an electroconductive carbon-based support such as graphene while retaining its inherent properties, using a metallocene catalyst for olefin polymerization supported on the electroconductive carbon- Method.

In a first aspect of the present invention, there is provided a process for preparing a metallocene catalyst for olefin polymerization supported on an electrically conductive carbon-based carrier, which comprises covalently linking an organic compound having a cyclopentadienyl skeleton to an electrically conductive carbon- ; And a second step of reacting the resulting product of the first step with a transition metal compound of the periodic table group IVB containing a cyclopentadienyl skeleton ligand to form a metallocene catalyst supported on the carrier. To provide a supported catalyst production method.

The second aspect of the present invention is a metallocene catalyst for olefin polymerization supported on an electrically conductive carbon-based carrier, wherein the electrically conductive carbon-based carrier is modified to have a covalent bondable functional group, and the electrically conductive carbon- Wherein the functional group and the metallocene catalyst are connected to each other via an organic functional group other than a metal via a covalent bond.

The third aspect of the present invention is a polyolefin-electroconductive carbon-based carrier containing an olefin polymer or a copolymer formed and grown on a metallocene catalyst supported via covalent bond on an electrically conductive carbon- Lt; / RTI >

The fourth aspect of the present invention provides a process for producing a polyolefin, which comprises the step of polymerizing or copolymerizing an olefin under a metallocene catalyst supported via a covalent bond on an electrically conductive carbon-based carrier according to the second aspect do.

The polyolefin-electroconductive carbon-based support containing complex according to the third aspect of the present invention can be provided by the process for producing a polyolefin according to the fourth aspect of the present invention.

Hereinafter, the present invention will be described in detail.

The present inventors have found that when an electrically conductive carbon-based structure such as graphene having excellent electrical, thermal, and mechanical properties is covalently bonded to a support of metallocene catalyst for olefin polymerization, olefin is grown in the graphene, It has been found that dispersed polyolefin-graphene nanocomposite can be easily produced.

Therefore, in order to produce a polyolefin nanostructure in which a nanomaterial having excellent electrical conductivity and thermal conductivity, such as graphene, is uniformly dispersed in a polyolefin and a copolymer, A metallocene supported catalyst for olefin polymerization wherein a carbon-based carrier is used and a metallocene catalyst is covalently bonded to the carbon-based carrier is developed and used.

Also, the present invention relates to a polyolefin-electrically conductive carbon-based carrier containing composite in which an olefin polymer or copolymer is formed and grown on a metallocene catalyst supported via a covalent bond on the carbon-based carrier to uniformly disperse the carbon- .

As shown in Table 2 and Table 3, the novel supported catalyst according to the present invention can more efficiently prepare olefin polymers and copolymers, and exhibits high activity even when a small amount of a cocatalyst is used, It is possible to prepare a polyolefin.

The carbon-based carrier may be graphite, graphite oxide, graphene, graphen oxide, or a mixture thereof.

The graphene and graphite which can be used as an example of the electroconductive carbon-based structure are graphite materials and have very unique characteristics and properties such as high temperature lubrication, heat resistance, corrosion resistance, electric conduction and precision processing which can not be obtained from other materials. Graphite is excellent in heat resistance, softening, not melting, low in vapor pressure, and extremely low in coefficient of thermal expansion compared to ordinary metals, so that dimensional precision at high temperature is excellent. In addition, graphite has a higher thermal conductivity than most metals except gold, silver, copper and aluminum, has a low coefficient of thermal expansion, has a high thermal conductivity, and thus has excellent thermal shock resistance to withstand rapid temperature changes.

Therefore, graphene or graphite that is well dispersed in polyolefin can impart properties or physical properties of graphene or graphite to the polyolefin molding used in various fields. Therefore, the polyolefin-electrically conductive carbon- Containing composites can be widely used in various fields such as high temperature heat resistant materials, structural materials, and special mechanical parts.

In one embodiment of the present invention, the metallocene catalyst for olefin polymerization supported on the electrically conductive carbon-based carrier according to the present invention is a metallocene catalyst for olefin polymerization,

A first step of covalently bonding an organic compound having a cyclopentadienyl skeleton to an electrically conductive carbon-based carrier; And a second step of reacting the resulting product of the first step with a transition metal compound of group IVB of the periodic table containing a cyclopentadienyl skeleton ligand to form a supported metallocene catalyst on the support.

Before the first step, the method may further include the step of surface-modifying the electrically conductive carbon-based carrier so as to have a covalent bondable functional group.

Non-limiting examples of the functional group may be a hydroxyl group (OH group), or a carboxy group (COOH group).

It is preferable that the metallocene catalyst covalently bonded to the carbon-based carrier is present in the range of 0.0001 to 100 mmol per 1 g of the carrier before the covalent bond.

The organic compound having a cyclopentadienyl skeleton used in the first step may be selected from the group consisting of the following structural formulas 1 to 3.

[Structural formula 1]

[Structural formula 2]

[Structural Formula 3]

Wherein R1, R6 and R13 are hydrogen atoms,

R2 to R5, R7 to R12, and R14 to R21 are the same or different from each other and each represent a C1 to C20 hydrocarbon, C1 to C20 halogenated hydrocarbon, a silicon-containing group, an oxygen-containing group, a nitrogen- .

Further, the Group IVB transition metal compound of the periodic table containing a ligand having a cyclopentadienyl skeleton used in the second step can be selected from the group consisting of Structural Formulas 4 to 6 below.

[Structural Formula 4]

[Structural Formula 5]

[Structural Formula 6]

In the above formula,

M1 is a transition metal atom of Group IVB of the periodic table,

X1, X2 and X3 are the same or different and each represents a hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a hydrogen atom or a halogen atom,

R22 to R42 are the same or different from each other and each is a hydrocarbon group of C1 to 20, a halogenated hydrocarbon group of C1 to 20, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a phosphorus organic group or a hydrogen atom.

In one embodiment, the metallocene catalyst for olefin polymerization carried on the electrically conductive carbon-based support according to the present invention can be prepared by the following steps:

(I) oxidizing the graphite to form a graphene oxide (Formula A);

(Ii) reacting graphene oxide (Formula A) with SOCl ₂ or the like to form chlorinated graphene (Formula B);

(Iii) reacting chlorinated graphene (Formula B) with an organic compound having a cyclopentadienyl skeleton to form a compound of Formula C; And

Reacting the compound of formula (C) with n-butyllithium (n-BuLi) and reacting the transition metal group IVB transition metal compound containing a cyclopentadienyl skeleton ligand represented by cyclopentadienyl zirconium trichloride to form graphene metal (Iv) forming a rosese catalyst (Formula D).

(A)

[Chemical Formula B]

≪ RTI ID = 0.0 &

[Chemical Formula D]

The metallocene catalyst for olefin polymerization supported on the electrically conductive carbon-based carrier according to the present invention is a catalyst in which the electrically conductive carbon-based carrier is modified to have a covalent bondable functional group, and the functional group on the electrically conductive carbon- It is characterized in that organic functional groups other than metals in the catalyst are connected through covalent bonds.

In the present invention, the metallocene catalyst is not particularly limited as long as it is capable of producing alpha-olefin polymers or copolymers containing ethylene.

Metallocene catalysts are easier to control molecular weight, molecular weight distribution and stereoregularity than previous Ziegler-Natta catalysts. When a metallocene catalyst is used, a copolymer having a narrow molecular weight distribution, high stereoregularity, easy comonomer incorporation property and uniform copolymerization composition can be produced. Unlike the Ziegler-Natta catalyst, the copolymer produced by using the metallocene catalyst exhibits high stereoregularity, narrow molecular weight distribution and various good physical properties because the chain is composed of single active sites and the chain is stably increased. This is because the insertion direction is determined by the specificity of the rossen catalyst structure. The catalytic activity, the structure of the polymer, the composition, and the physical properties of the polymer can be changed according to various polymerization conditions of the coordination polymerization. The present invention is characterized in that a metallocene catalyst for olefin polymerization supported via covalent bonds in an electrically conductive carbon-based carrier is used as one of the polymerization conditions.

The present invention relates to a process for producing a polyolefin-electrically conductive carbon-based catalyst in which an olefin polymer or a copolymer is formed and grown on a metallocene catalyst supported on an electrically conductive carbon-based carrier by using the newly supported metallocene catalyst of the present invention in an olefin polymerization reaction A carrier-containing complex can be produced.

The olefin polymerization and copolymerization method of the present invention can be carried out by homopolymerizing an olefin in the presence of a metallocene catalyst supported on an electroconductive carbon-based support according to the present invention, or by copolymerizing ethylene as a main monomer and another alpha-olefin other than ethylene as a comonomer .

The catalyst system used in the olefin polymerization and copolymerization of the present invention may further comprise, in addition to the supported metallocene catalyst according to the present invention, an alkylaluminoxane cocatalyst, an organoaluminum cocatalyst or a boron compound cocatalyst, or a mixture thereof .

The alkylaluminoxane may be represented by the following formula (1).

[Chemical Formula 1]

Ra is a hydrogen atom, a C1-20 alkyl group, a C3-20 cycloalkyl group, a substituted cycloalkyl group, a C6-40 aryl group, an alkylaryl group, or an arylalkyl group, and n is an integer of 0-100.

Non-limiting examples of alkylaluminoxanes include methylaluminoxane, ethyl-aluminoxane, n-butylaluminoxane, n-hexyl-aluminoxane, ) And modified alkylaluminoxanes. Here, the alkyl group may be (C1-C20).

The molar ratio of the supported metallocene catalyst to the alkylaluminoxane cocatalyst is preferably 1:10 to 1: 10000, more preferably 1:50 to 1: 500, based on the molar ratio of the transition metal M: aluminum atom.

The organoaluminum may be represented by the following formula (2).

(2)

Wherein Rb, Rc and Rd are the same or different from each other and each represents a hydrogen atom, a halogen group, a C1-20 alkyl group, a substituted alkyl group, a C3-20 cycloalkyl group, a substituted cycloalkyl group, a C6-40 aryl group, An aryl group and an arylalkyl group, and at least one of Rb, Rc and Rd is an alkyl group.

The alkylaluminum may be selected from the group consisting of trimethylaluminum, dimethylaluminum chloride, dimethylaluminum methoxide, methylaluminum dichloride, triethylaluminum, diethylaluminum chloride, diethylaluminum methoxide, ethylaluminum dichloride, At least one selected from the group consisting of dinonopropyl aluminum chloride, normal propyl aluminum chloride, trinormal butyl aluminum, tripropyl aluminum, triisopropyl aluminum, triisobutyl aluminum and diisobutyl aluminum hydride.

Examples of the olefin-based monomer that can be used in the production method according to the present invention include ethylene, alpha olefins, cycloolefins and the like, and diene monomers, triene-based, styrene-based and cyclic olefins are also possible.

Examples of such monomers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, Butene, styrene, p-methylstyrene, allylbenzene, divinylbenzene, vinylcyclohexane, vinylcycloheptane, vinylcyclohexane, 1,3-butadiene, 1,4-pentadiene, 1,4-hexadiene and cyclopentadiene, and these monomers may be used singly or in combination of two or more kinds of monomers such as cyclopentene, cycloheptene, norbornene, tetracyclododecene, isoprene, Or more.

In the olefin polymerization method according to the present invention, a conventional polymerization method practiced in the art of olefin polymerization can be applied except for the supported catalyst to be used. For example, the polymerization temperature for polymerizing the olefin polymer and the copolymer is 0 to 150 캜, and preferably 30 to 120 캜. The polymerization reaction can be carried out continuously or batchwise in a known manner by solution, slurry or gas phase process. Further, a homopolymer, a copolymer or a block copolymer can be produced by the polymerization method according to the present invention.

The melt index refers to the weight of resin flowing through a capillary for 10 minutes at a constant load and temperature. In general, the relationship between molecular weight and melt index is inversely proportional. Therefore, in the case of PE, PE having a high molecular weight value has a low melt index value, and conversely, PE having a low molecular weight value has a high melt index value.

The polyolefin-electroconductive carbonaceous carrier-containing composite according to the present invention may have a melt index (g / 10 min) of 0.1 to 50.

Also, Choi et al., &Quot; Generation of Ultra-High-Molecular-Weight Polyethylene from Metallocenes Immobizzed onto N-Doped Graphene Nanoplatelets ", Macromol. Rapid Commun., 2013, 34, 533-538] reported that Cp ₂ ZrCl ₂ was reacted with graphite oxide, and after washing with toluene 10 times, Zr content was 3.2% by weight, , The Zr content was 1.9% by weight and 40% of the metallocene was separated from the support. However, since the catalyst of the present invention is not a simple physical adsorption method but is a chemical method of fixing cyclopentadienyl and derivatives thereof, which are ligands of metallocene, through covalent bonding to graphene oxide, Is the most effective method for preparing the polymer nanocomposite.

According to the present invention, an olefin is grown on an electrically conductive carbon-based carrier (e.g., graphene), so that the electrically conductive carbon-based carrier excellent in electrical, thermal, and mechanical properties is dispersed in an excellent manner. Can be easily produced.

Hereinafter, the present invention will be described in more detail by way of examples. It should be understood, however, that these examples are for illustrative purposes only and are not to be construed as limiting the scope of the invention.

≪ Method for measuring catalytic activity &

The catalytic activity was expressed as the concentration of the central metal of the supported metallocene catalyst using the amount of polyolefin produced per hour.

<Melt Index ( melt index , MI ) Measurement method>

After the polyethylene was heated to 190 ° C and the polypropylene was heated to 230 ° C, the piston to be loaded with 2160g of the cylinder was put in position and the orifice (inner diameter: 2.09mm, length: 8mm) The weight of the resin was measured and converted into the amount of passage for 10 minutes.

Example  1: Preparation of supported catalyst (A)

0.1 g of graphene oxide was placed in a Schlenk tube, 30 ml of thionyl chloride (SOCl ₂ ) was added and dispersed using an ultrasonic device. Thereafter, the reaction vessel was reacted with stirring at 80 DEG C for 24 hours. After completion of the reaction, unreacted thionyl chloride was removed, and the chlorinated graphene was washed with purified tetrahydrofuran. Chlorinated graphene was dispersed in 30 ml of purified tetrahydrofuran, and 10 mmol (5 ml) of cyclopentadienyl sodium was added dropwise at -78 캜, and the mixture was reacted for 24 hours. Thereafter, the precipitate was washed with purified tetrahydrofuran, and washed three times with normal hexane to obtain a graphene carrying compound (cyclopentadienylated graphene) in which cyclopentadienyl was covalently linked to the graphene.

Cyclopentadienylated graphene was added dropwise with 10 mmol (4 ml) of n-butyllithium at -78 ° C by the dropwise addition, and the reaction was allowed to proceed at room temperature for 12 hours. Unreacted normal butyllithium was then washed with normal hexane and vacuum dried. 10 mmol of cyclopentadienyl zirconium trichloride dissolved in tetrahydrofuran was added dropwise at room temperature and reacted for 24 hours. After completion of the reaction, the unreacted cyclopentadienyl zirconium trichloride was removed and washed with purified tetrahydrofuran, followed by vacuum drying to prepare a supported catalyst (A).

Example  2: Preparation of Supported Catalyst (B)

0.1 g of graphene oxide was placed in a Schlenk tube, 30 ml of thionyl chloride was added and dispersed using an ultrasonic device. Thereafter, the reaction vessel was reacted with stirring at 80 DEG C for 24 hours. After completion of the reaction, unreacted thionyl chloride was removed, and the chlorinated graphene was washed with purified tetrahydrofuran. Chlorinated graphene was dispersed in 30 ml of purified tetrahydrofuran, and 10 mmol (5 ml) of sodium decyl adenylate was added thereto at -78 ° C in an excess amount by a dropwise addition method, followed by reaction for 24 hours. Thereafter, the precipitate was washed with purified tetrahydrofuran, and washed three times with normal hexane to obtain a graphen carrying compound (indenylated graphene) in which indenyl was covalently linked to graphene.

The indenylated graphene was added with 10 mmol (4 ml) of n-butyllithium at -78 ° C by the dropwise addition method, and the reaction was carried out for 12 hours. Subsequently, unreacted normal butyllithium was removed, and 10 mmol of indenyl zirconium trichloride was added in an excess amount using a solution dropping method at room temperature, followed by reaction for 24 hours. After completion of the reaction, unreacted indenyl zirconium trichloride was removed and washed with purified tetrahydrofuran, followed by vacuum drying to prepare a supported catalyst (B).

Example  3: Preparation of Supported Catalyst (C)

0.1 g of graphene oxide was placed in a Schlenk tube, 30 ml of thionyl chloride was added and dispersed using an ultrasonic device. Thereafter, the reaction vessel was reacted with stirring at 80 DEG C for 24 hours. After completion of the reaction, unreacted thionyl chloride was removed, and the chlorinated graphene was washed with purified tetrahydrofuran. Chlorinated graphene was dispersed in 30 ml of purified tetrahydrofuran, and 10 mmol (5 ml) of sodium butylcyclopentadienylated sodium was added at -78 캜 in an excess amount by a dropwise addition method, followed by reaction for 24 hours. Thereafter, the resultant was washed with purified tetrahydrofuran and washed three times with normal hexane to obtain a graphen carrying compound (normal butyl cyclopentadienylated graphene) linked with covalent bond to graphene by n-butylcyclopentadienyl .

N-butylcyclopentadienylated graphene was added dropwise with 10 mmol (4 ml) of n-butyllithium at -78 ° C by the dropwise addition, and the mixture was reacted for 12 hours. Thereafter, unreacted normal butyllithium was removed, and 10 mmol of normal butylcyclopentadienyl zirconium trichloride was added thereto at room temperature in an excess amount by a dropwise addition method, followed by reaction for 24 hours. After completion of the reaction, the unreacted normal butyl cyclopentadienyl zirconium trichloride was removed, washed with purified tetrahydrofuran, and vacuum dried to prepare a supported catalyst (C).

Table 1 below shows the results of analysis of zirconium content in the supported metallocene catalysts prepared in Examples 1, 2 and 3 by ICP-AES.

catalyst Zirconium (wt%) Supported catalyst A 3.5 Supported catalyst B 3.2 Supported catalyst C 3.4

Comparative Example  1: Ethylene polymerization

For comparison with the supported catalyst, the ethylene polymerization was carried out using the same zirconocene dichloride as the metallocene structure before carrying out of Example 1 as a catalyst.

The polymerization was carried out in a 1 liter high-pressure reactor. 400 ml of toluene was used, and methylaluminoxane was added as a cocatalyst so that the ratio of Al / Zr was 5000, and zirconocene dichloride (0.00001 mol) was added. The ethylene polymerization was carried out for 1 hour at an ethylene pressure of 8 atm and a polymerization temperature of 50 &lt; 0 &gt; C.

Example  4: polymerization of ethylene

Ethylene was polymerized using the supported catalysts prepared in Examples 1, 2 and 3.

Ethylene polymerization was carried out in a 1 liter high-pressure reactor. 400 ml of n-hexane was used, and methylaluminoxane was added as a cocatalyst so that the ratio of Al / Zr was 500, and 0.05 g of the supported metallocene catalyst was added. The ethylene polymerization was carried out for 1 hour at an ethylene pressure of 8 atm and a polymerization temperature of 50 &lt; 0 &gt; C.

Table 2 below shows the results of ethylene polymerization of Example 4 and Comparative Example 1.

catalyst The ratio of cocatalyst Catalytic activity
(Kg-PE / mol-Zr-hr) Melt Index
(g / 10 min) Cp ₂ ZrCl ₂ (Comparative Example 1) Al / Zr = 5000 1,100 2.5 The supported catalyst A (Example 1) Al / Zr = 500 240 0.9 Supported catalyst B (Example 2) Al / Zr = 500 310 0.6 Supported catalyst C (Example 3) Al / Zr = 500 625 0.7

As can be seen from the above Table 2, the activity of the graphene supported metallocene catalyst is somewhat lower than that of zirconocene dichloride, but the activity of the supported metallocene using a small amount of aluminoxane is relatively high Respectively. The molecular weight of the produced polyethylene was higher when the graphene supported metallocene was used.

Comparative Example  2: Ethylene / 1- Hexen  Copolymerization

For comparison with the supported catalyst, ethylene and 1-hexene copolymerization were carried out using the same zirconocene dichloride as the metallocene structure before carrying out of Example 1 as a catalyst. Copolymerization was carried out in the same manner as in Comparative Example 1, except that 10 ml of purified 1-hexene was added.

Example  5: Ethylene / 1- Hexen  Copolymerization

Ethylene and 1-hexene copolymerization were carried out using the supported catalysts prepared in Examples 1, 2 and 3 above. The polymerization was carried out in a 1 liter high-pressure reactor, where 400 ml of n-hexane was used and 10 ml of refined 1-hexene was added. The polymerization was carried out under the same conditions as in Example 4 above.

catalyst The ratio of cocatalyst 1-hexene content
(mol%) Catalytic activity
(Kg-PE / mol-Zr-hr) Melt Index
(g / 10 min) Cp ₂ ZrCl ₂ (Comparative Example 2) Al / Zr = 5000 6.2 1,050 3.1 The supported catalyst A (Example 4) Al / Zr = 500 5.9 250 1.0 Supported catalyst B (Example 4) Al / Zr = 500 6.0 335 0.8 Supported Catalyst C (Example 4) Al / Zr = 500 6.3 590 0.9

Claims (13)

A method of producing a metallocene catalyst for olefin polymerization carried on an electrically conductive carbon-based carrier,
A first step of covalently bonding an organic compound having a cyclopentadienyl skeleton to an electrically conductive carbon-based carrier; And
And a second step of reacting the resultant product of the first step with a transition metal compound of group IVB of the periodic table containing a cyclopentadienyl skeleton ligand to form a metallocene catalyst supported on the carrier. Catalyst.
The method of claim 1, wherein the carbon-based carrier is selected from the group consisting of graphene, graphite oxide, graphite, and graphite oxide.
The method of claim 1, wherein the organic compound having a cyclopentadienyl skeleton is represented by a structural formula selected from the group consisting of Structural Formulas 1 to 3 below.
[Structural formula 1]

[Structural formula 2]

[Structural Formula 3]

Wherein R1, R6 and R13 are hydrogen atoms,
R2 to R5, R7 to R12, and R14 to R21 are the same or different from each other and each represent a C1 to C20 hydrocarbon, C1 to C20 halogenated hydrocarbon, a silicon-containing group, an oxygen-containing group, a nitrogen- .
The method for preparing a metallocene supported catalyst according to claim 1, wherein the transition metal compound of Group IVB of Periodic Table IV containing a ligand having a cyclopentadienyl skeleton is represented by a structural formula selected from the group consisting of Structural Formulas 4 to 6.
[Structural Formula 4]

[Structural Formula 5]

[Structural Formula 6]

In the above formula,
M1 is a transition metal atom of Group IVB of the periodic table,
X1, X2 and X3 are the same or different and each represents a hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a hydrogen atom or a halogen atom,
R22 to R42 are the same or different from each other and each is a hydrocarbon group of C1 to 20, a halogenated hydrocarbon group of C1 to 20, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a phosphorus organic group or a hydrogen atom.
A metallocene catalyst for olefin polymerization supported on an electrically conductive carbon-based carrier,
The electrically conductive carbon-based carrier is modified to have a covalent bond functional group, and the functional group on the electrically conductive carbon-based carrier and the organic functional group in the metallocene catalyst are covalently linked. Supported catalyst.
The process of claim 5, wherein the metallocene catalyst is selected from the group consisting of bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium methyl chloride, bis (cyclopentadienyl) zirconium dimethyl, bis (Methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis Zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (N-butyl-cyclopentadienyl) zirconium dichloride, bis (n-butyl-cyclopentadienyl) zirconium dichloride Zirconium dichloride, bis (indenyl) zirconium methyl chloride, bis (indenyl) zirconium dimethyl, bis (2-methyl- Indenyl) zirconium dichloride, bis (2-phenyl-indenyl) zirconium dichloride, bis (2-methyl-indenyl) zirconium dichloride, bis (Cyclopentadienyl) zirconium dichloride, dimethylsilylbis (cyclopentadienyl) zirconium methyl chloride, dimethylsilylbis (cyclopentadienyl) zirconium dichloride, dimethylsilylbis (Indenyl) zirconium dichloride, dimethylsilyl (indenyl) zirconium methyl chloride, dimethylsilyl (indenyl) zirconium dichloride, Zirconium dichloride, dimethylsilylbis (2-methyl-indenyl) zirconium methyl chloride, dimethylsilylbis (2-methyl-indenyl) zirconium dimethyl, dimethylsilyldimethylsilylbis (Indenyl cyclopentadienyl) zirconium dichloride, dimethylsilyl (indenyl cyclopentadienyl) zirconium methyl chloride, dimethylsilyl (indenyl cyclopentadienyl) zirconium dimethyl, dimethylsilyl (fluorenylcyclopentane (Cyclopentadienyl) zirconium dichloride, ethylenbis (cyclopentadienyl) zirconium dichloride, dimethylsilyl (fluorenylcyclopentadienyl) zirconium dichloride, (Cyclopentadienyl) zirconium methyl chloride, ethylene bis (cyclopentadienyl) zirconium dimethyl, ethylene bis (indenyl) (2-methyl-indenyl) zirconium dichloride, ethylene bis (indenyl) zirconium dichloride, ethylene bis (indenyl) zirconium dimethyl, ethylene bis (Indenyl cyclopentadienyl) zirconium dichloride, ethylene (indenyl cyclopentadienyl) zirconium methyl chloride, enylene (including indenyl cyclopentadienyl) zirconium dichloride, ethylene Zirconium dichloride, ethylene (fluorenylcyclopentadienyl) zirconium dichloride, ethylene (fluorenylcyclopentadienyl) zirconium dimethyl, ethylene (fluorenylcyclopentadienyl) zirconium dichloride, ethylene (Cyclopentadienyl) zirconium dichloride, isopropylbis (cyclopentadienyl) zirconium methyl chloride, isopropylbis (Indenyl) zirconium dichloride, isopropyl bis (indenyl) zirconium methyl chloride, isopropyl bis (indenyl) zirconium dimethyl, isopropyl bis (indenyl) zirconium dichloride, (2-methyl-indenyl) zirconium dichloride, isopropyl (indenyl cyclopentadienyl) zirconium dichloride, isopropyl (2-methyl-indenyl) zirconium dichloride, isopropyl (Cyclopentadienyl) zirconium dichloride, isopropyl (fluorenylcyclopentadienyl) zirconium dichloride, isopropyl (fluorenylcyclopentadienyl) zirconium dichloride, isopropyl Dienyl) zirconium methyl chloride, isopropyl (fluorenylcyclopentadienyl) zirconium dimethyl, and the like. Jingin olefin polymerization catalyst to a metallocene supported for.
The metallocene supported catalyst for olefin polymerization according to claim 5, wherein the carbon-based carrier is graphite or graphene.
6. The metallocene supported catalyst for olefin polymerization according to claim 5, wherein the electrically conductive carbon-based carrier modified to have a covalent bondable functional group is graphen oxide.
The metallocene supported catalyst for olefin polymerization according to claim 5, which is produced by the process according to any one of claims 1 to 4.
The polyolefin-electrically conductive carbon-based carrier according to any one of claims 5 to 8, wherein the olefin polymer or copolymer is formed and grown on the metallocene catalyst supported on the electrically conductive carbon- Containing complex.
8. A process for producing a polyolefin according to any one of claims 5 to 8, which comprises polymerizing or copolymerizing an olefin under a metallocene catalyst supported via covalent bond on an electrically conductive carbon-based carrier.
12. The process for producing a polyolefin according to claim 11, wherein the olefin is an alpha -olefin or a cycloolefin having 2 to 12 carbon atoms.
12. The method for producing a polyolefin according to claim 11, wherein the polyolefin to be produced is the polyolefin-electroconductive carbon-based carrier-containing complex according to claim 10.