KR102060639B1 - Transition metal compound, catalyst composition comprising the same, and method for preparing polyolefin using the same - Google Patents

Abstract

The present invention relates to a novel transition metal compound, a catalyst composition comprising the transition metal compound, and a method for producing a polyolefin using the catalyst composition. According to the present invention, it is possible to implement a high polymerization performance in the olefin polymerization reaction, it is possible to polymerize a low to medium molecular weight polyolefin having a controlled copolymerization degree.

Description

A transition metal compound, a catalyst composition comprising the same, and a method for producing a polyolefin using the same {TRANSITION METAL COMPOUND, CATALYST COMPOSITION COMPRISING THE SAME, AND METHOD FOR PREPARING POLYOLEFIN USING THE SAME}

The present invention relates to a novel transition metal compound, a catalyst composition comprising the transition metal compound, and a method for producing a polyolefin using the catalyst composition. More specifically, a transition metal compound capable of realizing high polymerization performance in an olefin polymerization reaction and polymerizing a low to medium molecular weight polyolefin having a controlled copolymerization degree, a catalyst composition comprising the same, and a method for producing a polyolefin using the catalyst composition It is about.

Ziegler-Natta catalysts of titanium or vanadium compounds have been widely used in the commercial production process of conventional polyolefins. The Ziegler-Natta catalysts have high activity, but because they are multi-active catalysts, the molecular weight distribution of the resulting polymers is wide and comonomers are used. There is a limit in securing the desired physical properties because the composition distribution is not uniform.

Accordingly, recently, metallocene catalysts in which a ligand including a cyclopentadiene functional group and a transition metal such as titanium, zirconium, and hafnium have been developed have been widely used. Metallocene compounds are generally used by activation with aluminoxanes, boranes, borates or other activators. For example, a metallocene compound having a ligand including a cyclopentadienyl group and two sigma chloride ligands uses aluminoxane as an activator. These metallocene catalysts are single active site catalysts with one type of active site, and have a narrow molecular weight distribution of the produced polymer and can greatly control the molecular weight, stereoregularity, crystallinity, and especially the reactivity of the comonomer, depending on the structure of the catalyst and the ligand. There is an advantage. However, the polyolefin polymerized with a metallocene catalyst has a low melting point and a narrow molecular weight distribution, so when applied to some products, there is a problem in that it is difficult to apply in the field such as productivity decreases significantly due to the extruded load. A lot of efforts have been made to adjust.

In particular, in order to solve the above problems of the metallocene catalyst, a number of transition metal compounds in which a ligand compound including a hetero atom is coordinated have been introduced. Specific examples of the transition metal compound including such a hetero atom include azaferrocene compound having a cyclopentadienyl group including a nitrogen atom, and a structure in which a functional group such as a dialkylamine is connected to a cyclopentadienyl group as an additional chain. The metallocene compound or the titanium (lV) metallocene compound in which the alkylamine functional group of the ring form like piperidine was introduce | transduced, etc. are mentioned.

However, among all these attempts, only a few metallocene catalysts are actually applied in commercial plants, and thus can achieve higher polymerization performance and provide a low molecular weight polyolefin for improved processability. There is still a need for research on metallocene compounds that can be used as catalysts.

The present invention is to provide a novel transition metal compound having a high activity, and can provide a low to low molecular weight polyolefin having a controlled copolymerization degree.

In addition, the present invention is to provide a catalyst composition comprising the transition metal compound.

In addition, the present invention is to provide a method for producing a polyolefin using the catalyst composition.

In order to solve the above problems, an aspect of the present invention provides a transition metal compound represented by the following formula (1):

[Formula 1]

In Chemical Formula 1,

At least one of R 1 to R 8 is — (CH ₂ ) n —OR wherein R is a straight or branched chain alkyl group having 1 to 6 carbon atoms and n is an integer of 2 to 4; Different and each independently, hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms A functional group selected from the group, or two or more adjacent to each other may be connected to each other to form an aliphatic or aromatic ring substituted or unsubstituted with a hydrocarbyl group having 1 to 10 carbon atoms,

Q1 and Q2 are the same as or different from each other, and are each independently a halogen or an alkyl group having 1 to 20 carbon atoms;

M is a Group 4 transition metal,

X1 and X2 are the same as or different from each other, and each independently a halogen or an alkyl group having 1 to 20 carbon atoms,

m is an integer of 0 or 1.

In addition, another aspect of the present invention provides a catalyst composition comprising the transition metal compound.

In addition, another aspect of the present invention provides a method for producing a polyolefin comprising the step of polymerizing the olefin monomer in the presence of the catalyst composition.

According to the transition metal compound of the present invention, a catalyst composition comprising the same, and a method for preparing polyolefin using the catalyst composition, high polymerization performance can be realized in an olefin polymerization reaction, and a low to medium molecular weight polyolefin having a controlled copolymerization degree can be polymerized. have.

1 is a graph showing the GPC-FTIR measurement results of the polyolefin of Example 4. FIG.
2 is a graph showing the GPC-FTIR measurement results of the polyolefin of Example 5. FIG.
3 is a graph showing the GPC-FTIR measurement results of the polyolefin of Comparative Example 4. FIG.

In the present invention, terms such as first and second are used to describe various components, which terms are used only for the purpose of distinguishing one component from other components.

Also, the terminology used herein is for the purpose of describing example embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. As used herein, the terms "comprise", "comprise" or "have" are intended to indicate that there is a feature, number, step, component, or combination thereof, that is, one or more other features, It should be understood that it does not exclude in advance the possibility of the presence or addition of numbers, steps, components, or combinations thereof.

As the invention allows for various changes and numerous modifications, particular embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

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

According to one embodiment of the present invention, there is provided a transition metal compound represented by Formula 1 below:

[Formula 1]

In Chemical Formula 1,

At least one of R 1 to R 8 is — (CH ₂ ) n —OR wherein R is a straight or branched chain alkyl group having 1 to 6 carbon atoms and n is an integer of 2 to 4; Different and each independently, hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms A functional group selected from the group, or two or more adjacent to each other may be connected to each other to form an aliphatic or aromatic ring substituted or unsubstituted with a hydrocarbyl group having 1 to 10 carbon atoms,

Q1 and Q2 are the same as or different from each other, and are each independently a halogen or an alkyl group having 1 to 20 carbon atoms;

M is a Group 4 transition metal,

X1 and X2 are the same as or different from each other, and each independently a halogen or an alkyl group having 1 to 20 carbon atoms,

m is an integer of 0 or 1.

The inventors have conducted a study on a novel transition metal compound having a high activity and capable of providing a low to low molecular weight polyolefin having a controlled copolymerization degree, whereby a ligand compound having a substituent having a specific structure is bound to the transition metal. The transition metal compound of Formula 1 has high catalytic activity and can easily control the electronic / stereoscopic environment around the transition metal, so that the properties such as chemical structure, molecular weight distribution and mechanical properties of the polyolefin to be synthesized can be easily controlled. It was confirmed through the experiment to complete the invention.

In particular, the transition metal compound of Formula 1 is-(CH ₂ ) n -OR to the substituent of the cyclopentadiene (Cp) or derivatives thereof, wherein R is a linear or branched alkyl group having 1 to 6 carbon atoms, n is 2 To an integer of 4 to 4). In the preparation of a polyolefin using a comonomer, a low to medium copolymer having a low degree of conversion to comonomers compared to other Cp-based catalysts that do not include the substituents, the degree of copolymerization or comonomer distribution is controlled. Polyolefins of molecular weight can be prepared.

As a more specific example, when using as a hybrid catalyst by using the transition metal compound of Formula 1 together with another second transition metal compound for the production of polyolefins in the high molecular weight region, the high molecular weight region by the second transition metal compound In the polyolefin, while exhibiting high copolymerizability, the polyolefin in the low molecular weight region may exhibit low copolymerizability by the action of the transition metal compound of Chemical Formula 1. Accordingly, it is very advantageous to polymerize a polyolefin having a broad orthogonal co-monomer distribution (BOCD) structure in which the content of the comonomer is concentrated in the high molecular weight backbone, that is, the side branch content increases toward the higher molecular weight. .

Hereinafter, the substituents defined in Chemical Formula 1 will be described in more detail.

The alkyl group having 1 to 20 carbon atoms may include a linear or branched alkyl group.

The aryl group is preferably an aromatic ring having 6 to 20 carbon atoms, and specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited thereto.

The alkylaryl group refers to an aryl group having one or more linear or branched alkyl groups of 1 to 20 carbon atoms introduced therein, and the arylalkyl group refers to a straight or branched alkyl group having one or more aryl groups of 6 to 20 carbon atoms introduced thereto.

The hydrocarbyl group refers to a monovalent hydrocarbon compound, and includes an alkyl group, an alkenyl group, an aryl group, an alkylaryl group, an arylalkyl group, and the like.

The halogen group means fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

The Group 4 transition metal defined by M may be Ti (titanium), Zr (zirconium), hafnium (Hf), etc., but is not limited thereto.

Q1 and Q2 are preferably an alkyl group having 1 to 20 carbon atoms, more preferably a methyl group, an ethyl group, or a propyl group.

X1 and X2 may preferably be a halogen group, more preferably Cl.

In the transition metal compound of the above embodiment, at least one of R 1 to R 8 of Formula 1 is-(CH ₂ ) n -OR, wherein R is a linear or branched alkyl group having 1 to 6 carbon atoms, and n is 2 to 4 Is an integer of). In Formula 1,-(CH ₂ ) n -OR may be preferably a tert-butoxybutyl group (tert-butoxybutyl). More preferably, two cyclopentadiene (Cp) derivatives each include a-(CH ₂ ) n-OR group, or only one Cp derivative may include a-(CH ₂ ) n-OR group, wherein- The (CH ₂ ) n-OR group may be tert-butoxybutyl.

When a transition metal compound having such a structure is supported on a carrier, stable supported polymerization can be formed through intimate interaction with silanol groups on the surface of silica, in which a-(CH ₂ ) n -OR group is used as a carrier. This is possible. In addition, the functional groups may affect the copolymerizability of alpha olefin comonomers such as 1-butene, or 1-hexene, where n in-(CH ₂ ) n -OR In the case of having a short alkyl chain of 4 or less, the copolymerization with respect to the alpha olefin comonomer is lowered while maintaining the overall polymerization activity, which is advantageous for the production of polyolefins having controlled copolymerization without deteriorating other physical properties.

The transition metal compound of Formula 1 may be represented by Formula 2 to Formula 5, more specifically.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 2 to 5, R1 to R8, Q1 to Q2, M, and X1 to X2 are the same as those of Formula 1, and R 'and R' 'are the same as or different from each other, and each independently, having 1 to 10 carbon atoms. It is a hydrocarbyl group.

The structure of Formula 2 is a case in which m is 0 in Formula 1, a structure in which two cyclopentadiene (Cp) groups are uncrosslinked, and at least one substituent of R 1 to R 8 is — (CH ₂ ) n —OR.

In Formula 1, when m is 1 in Formula 1, two Cp groups are crosslinked by a SiQ1Q2 bridge, and at least one substituent of R1 to R8 is-(CH ₂ ) n -OR.

The structure of Formula 4 is a case in which m is 0 in Formula 1, a structure in which two indene groups formed by linking adjacent substituents in the Cp group with each other are non-crosslinked, and substituents R1, R2, R5, And any one or more substituents of R 6 is — (CH ₂ ) n —OR, and each indene group may be substituted with a hydrocarbyl group (R ′, R ″) having 1 to 10 carbon atoms.

In the structure of Formula 5, when m is 1 in Formula 1, two indene groups formed by linking adjacent substituents in the Cp group are crosslinked by a SiQ1Q2 bridge, and substituents R1 and R2 of the indene group Any one or more substituents of R 5, R 6, and R 6 may be-(CH ₂ ) n -OR, and each indene group may be substituted with a hydrocarbyl group (R ′, R ″) having 1 to 10 carbon atoms.

Meanwhile, specific examples of the transition metal compound represented by Chemical Formula 1 may include a compound represented by the following structural formulas, but the present invention is not limited thereto.

In addition, the transition metal compound represented by Formula 1 may be formed by reacting in the same manner as in Scheme 1 or Scheme 2, but is not limited thereto, and may be prepared according to a known method for preparing an organic compound and a transition metal compound. have.

Method for preparing a compound represented by Formula 1 will be described in more detail in the following Examples:

Scheme 1

Scheme 2

In Schemes 1 and 2, the definitions of R1 to R8, Q1, Q2, X1, X2 and M are the same as defined in Chemical Formula 1.

In addition, another aspect of the present invention provides a catalyst composition comprising the transition metal compound and a promoter.

The catalyst composition according to the present invention may further include one or more of the cocatalyst compounds represented by the following Chemical Formulas 6, 7, or 8 in addition to the transition metal compound.

[Formula 6]

-[Al (R9) -O] a-

In Chemical Formula 6,

R9 may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;

a is an integer of 2 or more;

[Formula 7]

J (R10) ₃

In Chemical Formula 7,

R 10 is as defined in Formula 6 above;

J is aluminum or boron;

[Formula 8]

_{^{[EH] + [ZA 4]}} - or _{^{[E] + [ZA 4]}} -

In Chemical Formula 8,

E is a neutral or cationic Lewis base;

H is a hydrogen atom;

Z is a Group 13 element;

A may be the same or different from each other, and each independently is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, unsubstituted or substituted with one or more hydrogen atoms, halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy. .

Examples of the compound represented by Chemical Formula 6 include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and the like, and more preferred compound is methyl aluminoxane.

Examples of the compound represented by Chemical Formula 7 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

Examples of the compound represented by Formula 8 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) Boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetra Pentafluorophenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenyl boron, trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, t Ripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra (p-tolyl) aluminum, tripropyl ammonium tetra (p-tolyl) aluminum, triethyl ammonium tetra (o, p-dimethylphenyl) aluminum, tributyl ammonium Tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N , N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatetraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra (p-tolyl) Boron, triethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetra (p-triflo Phenyl) boron and the like, triphenylamine car I phenylboronic as Titanium tetra-penta flow.

Preferably, alumoxane can be used, more preferably methylalumoxane (MAO) which is alkylalumoxane.

The catalyst composition according to the present invention comprises the steps of 1) contacting a transition metal compound represented by Formula 1 with a compound represented by Formula 6 or Formula 7 to obtain a mixture; And 2) it may be prepared by a method comprising the step of adding a compound represented by the formula (8) to the mixture.

In addition, the catalyst composition according to the present invention may be prepared by a method of contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 6 as a second method.

In the case of the first method of the method for preparing the catalyst composition, the molar ratio of the transition metal compound represented by the formula (1) / compound represented by the formula (6) or formula (7) is preferably 1 / 5,000 to 1/2, more Preferably it is 1 / 1,000-1/10, Most preferably, it is 1/500-1/20. When the molar ratio of the transition metal compound represented by Formula 1 / compound represented by Formula 6 or Formula 7 is more than 1/2, the amount of alkylating agent is so small that the alkylation of the transition metal compound does not proceed completely. In the case where the molar ratio is less than 1 / 5,000, alkylation of the metal compound is performed, but there is a problem that activation of the alkylated transition metal compound is not completely performed due to a side reaction between the remaining excess alkylating agent and the activator of Formula 8. . In addition, the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 8 is preferably 1/25 to 1, more preferably 1/10 to 1, and most preferably 1/5. To 1; When the molar ratio of the transition metal compound represented by Chemical Formula 1 to the compound represented by Chemical Formula 8 is greater than 1, the amount of the activator is relatively small, and thus the activity of the catalyst composition generated due to the incomplete activation of the metal compound. If the molar ratio is less than 1/25, the transition metal compound is completely activated, but the excess amount of the activator is not economical unit cost or the purity of the resulting polymer is inferior .

In the second method of the method for preparing the catalyst composition, the molar ratio of the transition metal compound represented by Chemical Formula 1 / Compound 6 is preferably 1 / 10,000 to 1/10, more preferably 1 / 5,000 to 1/100, most preferably 1 / 3,000 to 1/500. If the molar ratio is greater than 1/10, the amount of the activator is relatively small, so that the activation of the metal compound is not fully achieved, resulting in a decrease in the activity of the resulting catalyst composition, and in the case of less than 1 / 10,000, the transition metal compound Although the activation of is completely made, there is a problem that the unit cost of the catalyst composition is not economical or the purity of the resulting polymer is inferior with the excess activator remaining.

In preparing the catalyst composition, a hydrocarbon solvent such as pentane, hexane, heptane, or the like, or an aromatic solvent such as benzene, toluene, or the like may be used.

According to an embodiment of the present invention, the catalyst composition may further include another transition metal compound in addition to the transition metal compound of Formula 1 as the second transition metal compound. That is, the catalyst composition of the present invention may be used as a single supported metallocene catalyst or a hybrid supported metallocene catalyst including the transition metal compound of Chemical Formula 1.

The type of other transition metal compound that is additionally included is not particularly limited, but may be a metallocene catalyst capable of preparing a high molecular weight or ultra high molecular weight polyolefin. As such, when the catalyst composition is a hybrid supported catalyst including the transition metal compound of Formula 1 and a transition metal compound for preparing a high molecular weight or ultra high molecular weight polyolefin as a second transition metal compound, the second transition metal compound may In the polyolefin, while exhibiting high copolymerizability, the polyolefin in the low molecular weight region may exhibit low copolymerizability by the action of the transition metal compound of Chemical Formula 1.

Accordingly, the polyolefin having the BOCD structure, which is a structure in which the content of the comonomer is concentrated in the high molecular weight backbone, that is, the side branch content increases toward the higher molecular weight, can be polymerized with high activity.

The present invention also provides a method for producing a polyolefin polymerizing an olefinic monomer in the presence of a catalyst composition comprising the transition metal compound.

The polymerization reaction may be performed by a solution polymerization process, a slurry process or a gas phase process using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor. It may also proceed by homopolymerization with one olefin monomer or copolymerization with two or more monomers.

The polymerization of the olefin monomer may be carried out by reacting at a temperature of about 25 to about 500 ° C. and about 1 to about 100 kgf / cm ² for about 1 to about 24 hours. Specifically, the polymerization of the olefin monomer may be carried out at a temperature of about 25 to about 500 ℃, preferably about 25 to about 200 ℃, more preferably about 50 to about 100 ℃. The reaction pressure can also be carried out at about 1 to about 100 kgf / cm ² , preferably at about 1 to about 50 kgf / cm ² , more preferably at about 5 to about 40 kgf / cm ² .

In the method for preparing polyolefin according to the present invention, specific examples of the olefin monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, and 1-octene. , 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene and the like, these can be copolymerized by mixing two or more kinds.

The polyolefin may be a polyethylene polymer, but is not limited thereto.

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

The prepared polyolefin may exhibit a low to medium molecular weight.

According to an embodiment of the present invention, the weight average molecular weight (Mw) of the polyolefin may be about 10,000 to about 300,000 g / mol, or about 10,000 to about 150,000 g / mol. In addition, the molecular weight distribution (Mw / Mn) of the polyolefin may be about 2 to about 10, or about 2 to about 8.

In addition, the polyolefin according to the present invention can provide a polyolefin having a low copolymerizability with respect to the comonomer and a degree of copolymerization or comonomer distribution, and may be variously applied according to its use.

Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto.

<Example>

Synthesis Example of Transition Metal Compound

Synthesis Example 1

Preparation of 1-1 Ligand Compound

10.8 g (100 mmol) of chlorobutanol was added to the dried 250 mL Schlenk flask, 10 g of molecular sieve and 100 mL of MTBE were added, and 20 g of sulfuric acid was added slowly over 30 minutes. The reaction mixture slowly turned pink over time and poured into saturated sodium bicarbonate solution, cooled to ice after 16 hours. The mixture was extracted several times by adding ether (100 mL x 4), and the combined organic layers were dried over MgSO ₄ , filtered, and the solvent was removed under vacuum pressure to give 1- (tert butoxy) -4- in the form of a yellow liquid. 10 g (60% yield) of chlorobutane were obtained.

¹ H NMR (500 MHz, CDCl ₃ ): 1.16 (9H, s), 1.67-1.76 (2H, m), 1.86-1.90 (2H, m), 1.94 (1H, m), 3.36 (2H, m), 3.44 (1H, m), 3.57 (3H, m)

4.5 g (25 mmol) of the synthesized 1- (tert butoxy) -4-chlorobutane was added to the dried 250 mL Schlenk flask and dissolved in 40 mL of THF. 20 mL of sodium cyclopentadienylide THF solution was slowly added thereto, followed by stirring for one day. 50 mL of water was added to the reaction mixture for quenching, extraction with ether (50 mL x 3), and the combined organic layers were washed with brine. Dry the remaining moisture with MgSO ₄ , filter, and remove the solvent under vacuum pressure to quantify 2- (4- (tert-butoxy) butyl) cyclopenta-1,3-diene, a dark brown viscous form. Obtained in yield.

¹ H NMR (500 MHz, CDCl ₃ ): 1.16 (9H, s), 1.54-1.60 (4H, m), 1.65 (1H, m), 1.82 (1H, m), 2.37-2.42 (2H, m), 2.87 , 2.92 (2H, s), 3.36 (2H, m), 5.99 (0.5H, s), 6.17 (0.5H, s), 6.25 (0.5H, s), 6.34 (0.5H, s), 6.42 (1H , s)

Preparation of 1-2 transition metal compound

4.1 g (22 mmol) of the ligand compound synthesized in 1-1 was added to a dried 250 mL Schlenk flask, and dissolved in 60 mL of ether and 40 mL of THF. 13 mL of n-BuLi 2.0M hexane solution was added thereto, and the mixture was stirred for one day. Then, a toluene solution of n-butyl cyclopentadiene ZrCl ₂ (concentration 0.378 mmol / g) was slowly added at -78 ° C. When the reaction mixture was raised to room temperature, it changed from a clear brown solution to a white suspension in which a yellow solid floated. After 12 hours, 100 mL of hexane was added to the reaction mixture to generate an additional precipitate. Then filtered under argon to obtain a yellow filtrate, and dried to obtain the desired compound 3- (4- (tert-butoxy) butyl) cyclopenta-1,3-dien-1-yl) (3-butylcylcopenta-2,4 -dien-1-yl) was confirmed to form zirconium (IV) chloride.

¹ H NMR (500 MHz, CDCl ₃ ): 0.88 (3H, m), 1.18 (9H, s), 1.24-1.36 (4H, m), 1.55-1.62 (4H, m), 2.64 (4H, m), 3.35 (2H, m), 6.19 (1.5H, s), 6.29 (1.5H, s)

Synthesis Example 2

4.3 g (23 mmol) of the ligand compound synthesized in 1-1 was added to a dried 250 mL Schlenk flask, and dissolved in 60 mL of THF. To this was added 11 mL of n-BuLi 2.0M hexane solution (28 mmol) and stirred for one day. The solution was then added to a flask containing 3.83 g (10.3 mmol) of ZrCl ₄ (THF) ₂ dispersed in 50 mL of ether. Slowly added at 78 ° C.

When the reaction mixture was raised to room temperature, the pale yellow suspension turned from a pale yellow suspension into a suspension form. After stirring for one day, all the solvents of the reaction mixture were dried, 200 mL of hexane was added to sonication and soaked, and the hexane solution in the upper layer was collected by decantation with cannula. The hexane solution obtained by repeating this process twice was dried under vacuum reduced pressure to give a pale yellow solid, bis (3- (4- (tert-butoxy) butyl-2,4-dien-yl) zirconium (IV) chloride. It was confirmed that the generated.

¹ H NMR (500 MHz, CDCl ₃ ): 0.84 (6H, m), 1.14 (18H, s), 1.55-1.61 (8H, m), 2.61 (4H, m), 3.38 (4H, m), 6.22 (3H , s), 6.28 (3H, s)

Synthesis Example 3

Preparation of 3-1 Ligand Compound

80 mL of ether was injected into a dried 250 mL Schlenk flask under argon containing 4.57 g (20 mmol) of 3- (4-tert-butoxy butyl) -1H-indene. After cooling this ether solution to 0 degreeC, 9.7 mL (24 mmol) of 2.5M nBuLi hexane solution was slowly added dropwise. The reaction mixture was slowly raised to room temperature and stirred until the next day.

After cooling the Schlenk flask to -78 ℃, 1.2 mL (10 mmol) of dimethyldichlorosilicone was injected using a syringe. After the injection, the mixture was slowly raised to room temperature and stirred for one day. 50 mL of water was quenched into the Schlenk flask, the organic layer was separated, and dried over MgSO ₄ . As a result, 5.526 g (10.14 mmol, 101%) of a brown oil of bis (3- (4- (tert-butoxy) butyl) -1H-inden-1-yl) dimethylsilane was obtained. NMR criteria purity (wt%) = 100%, Mw = 544.88

1 H NMR (500 MHz, CDCl ₃ ): -0.15, -0.10, -0.02, 0.06 (6H, s), 0.87 (2H, m), 1.18 (18H, s), 1.70 (5, m), 2.63 (2H, m), 3.49 (4H, m), 6.08, 6.29 (2H, s), 7.17 (3H, m), 7.27 (2H, m), 7.42 (3H, m)

3-2 Preparation of Transition Metal Compound

The ligand compound synthesized in 3-1 was put in a 250 mL Schlenk flask dried in an oven, dissolved in ether, and 2.1 equivalent nBuLi solution (21 mmol, 8.4 mL) was added thereto, followed by lithiation.

One equivalent of ZrCl ₄ (THF) ₂ was taken in a glove box and placed in a 250 mL Schlenk flask to prepare a suspension with ether. After cooling both flasks to −78 ° C., ligand anions were slowly added to the Zr suspension. After the injection was over, the reaction mixture was slowly raised to room temperature. After stirring for one day, the ether in the mixture was filtered through a filter under argon to remove the LiCl produced after the reaction. After the removal of the remaining filtrate was removed by vacuum decompression and hexane (hexane) of the volume of the reaction solvent was added to promote the crystallization. This hexane slurry was filtered under argon, and both the filtered solid and the filtrate were evaporated under vacuum reduced pressure. The remaining filter cake (filter cake) and the filtrate (filtrate) for each catalyst was confirmed by NMR, and the yield and purity were checked by metering and sampling in a glove box. As a result, it was confirmed that the transition metal compound catalyst bis (3-4- (tert-butoxy) butyl) -1H-inden-1-yl) dimethylsilyl zirconium (IV) chloride was synthesized in the filtrate. yield: 30.0, purity (wt%) = 100% based on NMR, Mw = 705.0

The synthesized transition metal compound was stored dissolved in toluene (3.678 g / mmol).

1 H NMR (500 MHz, CDCl ₃ ): 0.87 (6H, m), 1.13 (18H, m), 1.33-1.54 (12H, m), 3.30 (4H, m), 5.56 (1H, s), 5.76 (1H , s), 6.87 (2H, t), 7.15 (2H, m), 7.42 (2H, m), 7.49 (2H, m)

Comparative Synthesis Example 1

2.22 g (10 mmol) of 2- (6-tert-butoxyhexyl) cyclopenta-1,3-diene was added to a dried 250 mL Schlenk flask, dissolved in 45 mL of ether, and then 6 mL (1.5 equiv.) Of nBuLi hexane. Solution was added. After 6 hours, 20 g (0.95 equiv.) Of nBuCpZrCl ₃ toluene solution (0.273 g / mmol) was slowly added at −78 ° C., and then warmed to room temperature and then reacted for one day. After the reaction was filtered through a filter, the filtrate was dried under vacuum reduced pressure to give a white solid in a yield of 86%, which was prepared as a toluene solution and stored.

1 H NMR (500 MHz, CDCl ₃ ): 0.93 (3H, s), 1.14 (9H, s), 1.32-1.40 (8H, m), 1.49-1.62 (6H, m), 2.62 (3H, m), 3.31 (2H, m), 6.19 (2H, s), 6.28 (2H, s)

Comparative Synthesis Example 2

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

Further, t-Butyl-O- (CH ₂ ) ₆ -C ₅ H ₅ was dissolved in THF at -78 ° C, n-BuLi was slowly added, and the temperature was raised to room temperature, followed by reaction for 8 hours. The solution was added slowly to the suspension solution of ZrCl ₄ (THF) ₂ (1.70 g, 4.50 mmol) / THF (30 mL) at -78 ° C and further added at room temperature for 6 hours. Reacted.

All volatiles were dried in vacuo and the resulting oily liquid material was filtered off by addition of hexane solvent. The filtered solution was dried in vacuo and hexane was added to induce precipitate at low temperature (-20 ° C). The obtained precipitate was filtered at low temperature to give a [tBu-O- (CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ compound as a white solid (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, 8 H), 1.17 (s, 9 H).

Comparative Synthesis Example 3

Preparation of 3-1 Ligand Compound

3.2 g (12 mmol) of 3- (6-tert-butoxy hexyl) -1H-indene was added to a dried 250 mL Schlenk flask, and 50 mL of ether was injected under argon. After cooling this solution to 0 ° C., 5.6 mL (14 mmol) of 2.5M nBuLi hexane solution was added dropwise. The temperature of the reaction mixture was slowly raised to room temperature and stirred until the next day. After stirring, the reaction mixture solution was cooled to −78 ° C., 0.774 g (6 mmol) of dimethyldichlorosilicone was prepared, and added dropwise to the Schlenk flask containing the reaction mixture solution. After the injection, the temperature of the mixture was slowly raised to room temperature and stirred for one day. After stirring, 50 mL of water was added to the flask and quenched, and the organic layer was separated and dried over MgSO ₄ . As a result, 3.4 g (5.7 mmol, 95%) of the product in the form of a yellow oil was obtained. NMR criteria purity (wt%) = 100%, Mw = 600.99

1 H NMR (500 MHz, CDCl ₃ ): -0.53, -0.35, -0.09 (6H, t), 1.18 (18H, m), 1.41 (8H, m), 1.54 (4H, m), 1.68 (4H, m ), 2.58 (4H, m), 3.32 (4H, m), 6.04 (1H, s), 6.26 (1H, s), 7.16 (2H, m), 7.28 (3H, m), 7.41 (3H, m)

3-2 Preparation of Transition Metal Compound

The ligand compound synthesized in 3-1 was put in a dry 250 mL Schlenk flask, and 4 equivalents of MTBE and toluene solution were dissolved in a solvent, and 2.1 equivalents of nBuLi solution (21 mmol, 8.4 mL) was added to lithiation until the next day.

2.1 equivalent ZrCl ₄ (THF) ₂ was taken in a glove box and placed in a 250 mL Schlenk flask to prepare a suspension with ether. After cooling both flasks to −78 ° C., ligand anions were slowly added to the Zr suspension. After the injection was over, the reaction mixture was slowly raised to room temperature.

After stirring for one day, the vacuum in the mixture was removed to about 1/5 of the ether in the mixture and 5 times the volume of hexane of the remaining solvent was added to promote crystallization. This hexane slurry was filtered under argon, and both the filtered solid and the filtrate were evaporated under vacuum reduced pressure. The remaining filter cake (filter cake) and the filtrate (filtrate) for each catalyst was confirmed by NMR, and the yield and purity were checked by weighing and sampling in a glove box. As a result, 3.6 g (5.58 mmol, 98.02% yield) of the transition metal compound catalyst bis (3-6- (tert-butoxy) hexyl) -1H-inden-1-yl) dimethylsilyl zirconium (IV) chloride was synthesized. It was. NMR-based purity (wt%) = 100%, Mw = 641.05

The synthesized transition metal compound was stored dissolved in toluene at a concentration of 0.45 mmol / g.

1 H NMR (500 MHz, CDCl ₃ ): 0.87 (6H, m), 1.14 (18H, m), 1.11-1.59 (16H, m), 2.61, 2.81 (4H, m), 3.30 (4H, m), 5.54 (1H, s), 5.74 (1H, s), 6.88 (1H, m), 7.02 (1H, m), 7.28 (1H, m), 7.39 (1H, d), 7.47 (1H, t), 7.60- 7.71 (1 H, m)

<Synthesis of transition metal compound for producing high molecular weight polyolefin>

Reference Synthesis Example 1

Preparation of 1-1 Ligand Compound

2.331 g (10 mmol) of Indenoindole was added to a dried 250 mL schlenk flask, and 40 mL of ether was injected under argon. After the ether solution was cooled to 0 ° C., 4.8 mL (12 mmol) of 2.5 M nBuLi hexane solution was slowly added dropwise. The reaction mixture was slowly raised to room temperature and stirred until the next day. Another 250 mL schlenk flask was charged with 20 mL of ether and 3.6 mL (30 mmol) of dichloromethyl (tertbutoxyhexyl) silane was injected. After cooling the flask to -78 ℃, a lithiated solution of Indenoindole was injected through the cannula. After the injection, the mixture was slowly raised to room temperature, stirred for about 5 hours, stirred for one day, quenched with 50 ml of water in the Flask, and the organic layer was separated and dried over MgSO ₄ . The ether used as solvent was removed under reduced pressure. This was confirmed by NMR and 10-((6- (tert-butoxy) hexyl) chloro (methyl) silyl) -5,8-dimethyl-5,10-dihydroindeno [1,2-b] indole having a purity of about 95% or more. Got.

After the synthesis of the indenoindole part was confirmed, 1.7 g (10 mmol) of ((1H-inden-3-yl) methyl) trimethylsilane was injected into a dried 100 mL schlenk flask and dissolved in 40 mL of ether. Then 4.8 ml (12 mmol) of 2.5 M nBuLi hexane solution was slowly added dropwise at -78 ° C and stirred for one day. Dissolve 10-((6- (tert-butoxy) hexyl) chloro (methyl) silyl) -5,8-dimethyl-5,10-dihydroindeno [1,2-b] indole synthesized in 40 mL of ether , Lithiated solution of ((1H-inden-3-yl) methyl) trimethylsilane was added dropwise at -78 ° C. After about 20 hours, 50 mL of water was added to the flask, quenched, and the organic layer was separated and dried over MgSO ₄ . The mixture obtained through filtration evaporated the solvent under vacuum reduced pressure conditions. As a result, 6.5 g (10.2 mmol, 100%) of 10-((6- (tert-butoxy) hexyl) (methyl) (3-((trimethylsilyl) methyl) -1H-inden-1-yl) silyl)- Yellow oil of 5,8-dimethyl-5,10-dihydroindeno [1,2-b] indo was obtained.

Mw: 634.05, Purity (wt%) = 100%

1 H NMR (500 MHz, CDCl 3): -0.40, -0.37 (3H, d), 0.017 (9H, m), 1.10 (4H, m), 1.18 (9H, s), 1.34 (6H, m), 2.41 ( 3H, m), 3.25 (2H, m), 3.25 (1H, m), 3.53 (1H, m), 4.09 (3H, s), 5.62, 5.82, 5.95, 5.95, 6.11 (1H, s), 7.04- 7.32 (9H, m), 7.54 (1H, m), 7.75 (1H, m).

Preparation of 1-2 metallocene compound

Ligated in a 250 mL schlenk flask dried in an oven, dissolved in ether, 2.1 equivalent nBuLi solution was added and lithiation was performed until the next day. One equivalent of ZrCl ₄ (THF) ₂ was taken in a glove box and placed in a 250 ml schlenk flask to prepare a suspension containing ether or toluene. After cooling both flasks to -78 ℃, ligand anion was slowly added to the Zr suspension. After the injection was over, the reaction mixture was slowly raised to room temperature. In this process, when metallization was successful, it was confirmed that an index purple peculiar to the catalyst precursor appeared. After stirring for one day, toluene or ether in the mixture was removed by vacuum depressurization to about 1/5 volume and hexane was added at about 5 times the volume of the remaining solvent. In this case, the reason for adding hexane is to promote crystallization because the synthesized catalyst precursor has poor solubility in hexane. The hexane slurry was filtered under argon, and after filtration, both the filtered solid and the filtrate were evaporated under vacuum reduced pressure. The remaining filter cake was weighed and sampled in the glove box to confirm the synthesis, yield, and purity. Ether was used as the solvent for metallization and 6.08 g (76.5%) of a purple solid was obtained from 6.4 g (10 mmol) of ligand.

NMR criteria purity (wt%) = 100%. Mw = 794.17.

1 H NMR (500 MHz, CDCl 3): -0.23, -0.16 (9H, d), 0.81 (3H, m), 1.17 (9H, m), 1.20-1.24 (3H, m), 1.31 (2H, s), 1.62 to 1.74 (5H, m), 1.99 to 2.11 (2H, m), 2.55 (3H, d), 3.33 (2H, m), 3.95, 4.13 (3H, s), 5.17, 5.21, 5.32 (1H, s ), 6.89-7.07 (3H, m), 7.12-7.21 (3H, m), 7.29 (1H, m), 7.36 (1H, m), 7.44 (1H, m), 7.84 (1H, m).

Reference Synthesis Example  2

tBu-O- (CH ₂ ) ₆ ) (CH ₃ Si (C ₅ (CH ₃ ) ₄ ) (tBu-N) TiCl ₂  Manufacture

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, the reactor temperature was observed to rise by about 4 to 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, water was added thereto, an organic layer was obtained, and 6-t-butoxyhexane was identified through 1H-NMR. From the 6-t-butoxyhexane it can be seen that the 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. The reactor was added at a rate of 5 mL / min using an n-BuLi 480 mL 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 quickly added 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 salt was 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) ) Quickly. The reaction solution was slowly stirred at -78 ° C to room temperature 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, (tBu-O- (CH ₂ ) _{6 which} is desired ([methyl (6-t-buthoxyhexyl) silyl (η5-tetramethylCp) (t-Butylamido)] TiCl ₂ ) from 1H-NMR. It was confirmed that (CH ₃ ) Si (C ₅ (CH ₃ ) ₄ ) (tBu-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, 3 H)

<Example of preparing a single supported catalyst>

Preparation Example 1

1-1 Drying the Carrier

Silica (Grace Davison, XPO 2410) was dehydrated under vacuum at a temperature of 300 ° C. for 12 hours.

Preparation of 1-2 Supported Catalyst

20 g of the silica dried in 1-1 was placed in a glass reactor, a toluene solution including metal aluminoxane (MAO) containing 13 mmol of aluminum was added thereto, and the reaction was slowly stirred at 40 ° C. for 1 hour. It was then washed with sufficient toluene to remove unreacted aluminum compound. Next, the remaining toluene was removed by reducing the pressure to 40 ° C., and 32 g of a carrier carrying methylaluminoxane was obtained. The obtained carrier contained 17 weight% aluminum.

12 g of the carrier having the methyl aluminoxane loaded therein were placed in a glass reactor, and 70 mL of toluene was added thereto. Then, a toluene solution containing 1 mmol (Zr based) of the transition metal compound prepared in Synthesis Example 1 was added to the glass reactor, followed by 1 at 40 ° C. The reaction was stirred for an hour. After the reaction was completed, the metallocene supported catalyst in the form of a solid powder was prepared by washing with a sufficient amount of toluene and vacuum drying.

Preparation Example 2

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

Preparation Example 3

A metallocene supported catalyst was prepared in the same manner as in Preparation Example 1, except that the transition metal compound of Synthesis Example 3 was used instead of the transition metal compound prepared in Synthesis Example 1.

Manufacture Comparative Example 1

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

Manufacture Comparative Example 2

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

Manufacture Comparative Example 3

A metallocene supported catalyst was prepared in the same manner as in Preparation Example 1, except that the transition metal compound of Comparative Synthesis Example 3 was used instead of the transition metal compound prepared in Synthesis Example 1.

<Example of Preparation of Hybrid Supported Catalyst>

Preparation Example 4

50 mL of toluene solution was put into a 300 mL glass reactor, 10 g of dried silica (SP 2410, manufactured by Grace Davison) was added, followed by stirring while raising the reactor temperature to 40 ° C. 60 mL of 10 wt% methylaluminoxane (MAO) / toluene solution was added thereto, the temperature was raised to 60 ° C., and the mixture was stirred at 200 rpm for 12 hours. After the reactor temperature was lowered to 40 ° C., stirring was stopped and settling for 10 minutes was followed by decantation of the reaction solution. 100 mL of toluene was added again and stirred for 10 minutes, and then the stirring was stopped and settling for 10 minutes, followed by decantation of the toluene solution.

50 mL of toluene was added to the reactor, 0.50 g of the transition metal compound of Reference Synthesis Example 1 and 10 mL of toluene were added to the reactor as a high molecular weight catalyst precursor, and stirred at 200 rpm for 60 minutes. 0.5 g of the transition metal compound of Synthesis Example 2 and 10 mL of toluene were added to the reactor as a low molecular weight catalyst precursor, followed by stirring at 200 rpm for 12 hours.

After stirring was stopped and settling for 10 minutes, the reaction solution was decanted. 100 mL of hexane was added to the reactor, the hexane slurry was transferred to a 250 mL schlenk flask, and the hexane solution was decanted and dried under reduced pressure at room temperature for 3 hours to prepare a mixed supported metallocene catalyst.

Preparation Example 5

A hybrid supported metallocene catalyst was prepared in the same manner as in Preparation Example 4, except that the transition metal compound of Reference Synthesis Example 2 was used instead of the transition metal compound of Reference Synthesis Example 1 as the high molecular weight catalyst precursor.

Manufacture Comparative Example 4

A hybrid supported metallocene catalyst was prepared in the same manner as in Preparation Example 4, except that the transition metal compound of Comparative Synthesis Example 2 was used instead of the transition metal compound prepared in Synthesis Example 2 as the low molecular weight catalyst precursor. .

<Example of Olefin Polymerization Using Single Supported Catalyst>

Example 1

The supported catalyst prepared in Preparation Example 1 was quantitated in a glove box, placed in a 50 mL glass bottle, sealed with a rubber septum, and taken out of the glove box to prepare a catalyst to be injected into the polymerization. The polymerization was carried out in a 600 mL metal alloy reactor equipped with a mechanical stirrer, temperature controlled and usable at high pressure.

400 mL of hexane containing 1.0 mmol of triethylaluminum and the supported catalyst prepared above were introduced into the reactor without contacting the reactor, and then 4 g of 1-butene was added at 80 ° C. The gas ethylene monomer was polymerized for 1 hour while continuously adding gas ethylene monomer at a pressure of 9 kgf / cm ² . Termination of the polymerization was completed by first stopping the reaction and then evacuating and removing the unreacted ethylene.

The resulting polymer product was filtered to remove most of the solvent and then dried in an 80 ° C. vacuum oven for 4 hours.

Example 2

In Example 1, polymerization was carried out in the same manner as in Example 1, except that the supported catalyst of Preparation Example 2 was used instead of the supported catalyst of Preparation Example 1.

Example 3

In Example 1, polymerization was carried out in the same manner as in Example 1, except that the supported catalyst of Preparation Example 3 was used instead of the supported catalyst of Preparation Example 1.

Comparative Example 1

In Example 1, polymerization was carried out in the same manner as in Example 1, except that the supported catalyst of Preparation Comparative Example 1 was used instead of the supported catalyst of Preparation Example 1.

Comparative Example 2

In Example 1, the polymerization was carried out in the same manner as in Example 1 except that the supported catalyst of Preparation Comparative Example 2 was used instead of the supported catalyst of Preparation Example 1.

Comparative Example 3

In Example 1, polymerization was carried out in the same manner as in Example 1, except that the supported catalyst of Preparation Comparative Example 3 was used instead of the supported catalyst of Preparation Example 1.

Physical properties of the polyolefins prepared in Examples and Comparative Examples are shown in Table 1 below.

Support Recipe Catalytic activity
(kgPE / gcat) Weight average molecular weight (Mw)
(Unit: g / mol) Molecular weight distribution
(PDI) Comonomer
(Mol: mol%) MAO Transition metal
compound mmol / g-SiO ₂ mmol / g-SiO ₂ Example 1 8 0.1 2.8 150,000 2.3 0.4 Comparative Example 1 8 0.1 6.3 120,000 2.3 1.0 Example 2 8 0.1 5.0 112,500 2.4 0.7 Comparative Example 2 8 0.1 10.1 104,000 2.4 1.1 Example 3 8 0.1 1.1 55,200 6.2 1.1 Comparative Example 3 8 0.1 3.3 53,300 3.3 1.7

From Table 1, the polyolefin prepared using the transition metal compound catalyst of the present invention exhibits low comonomer conversion and low to medium molecular weight, thereby eliminating the limitation of the metallocene catalyst, which has not been easy to prepare a low molecular weight polyolefin. It is expected that the processability can be improved.

<Example of Olefin Polymerization Using Hybrid Supported Catalyst>

Example 4

The mixed supported catalyst prepared in Preparation Example 4 was quantified in a glove box and placed in a 50 mL glass bottle, sealed with a rubber septum, and taken out of the glove box to prepare a catalyst to be injected into the polymerization. The polymerization was carried out in a 600 mL metal alloy reactor equipped with a mechanical stirrer, temperature controlled and usable at high pressure.

400 mL of hexane containing 1.0 mmol of triethylaluminum and the mixed supported catalyst prepared above were introduced into the reactor without air contact, and then 4 g of 1-butene was added at 80 ° C. The gas ethylene monomer was polymerized for 1 hour while continuously adding gas ethylene monomer at a pressure of 9 kgf / cm ² . Termination of the polymerization was completed by first stopping the reaction and then evacuating and removing the unreacted ethylene.

The resulting polymer product was filtered to remove most of the solvent and then dried in an 80 ° C. vacuum oven for 4 hours.

Example 5

In Example 4, the polymerization was carried out in the same manner as in Example 4 except that the hybrid supported catalyst of Preparation Example 5 was used instead of the hybrid supported catalyst of Preparation Example 4.

Comparative Example 4

In Example 4, polymerization was carried out in the same manner as in Example 4 except that the hybrid supported catalyst of Preparation Comparative Example 4 was used instead of the hybrid supported catalyst of Preparation Example 4.

The physical properties of the polyolefins prepared in Examples and Comparative Examples are shown in Table 2 below.

Support Recipe Catalytic activity
(kgPE / gcat) Weight average molecule
Mw
(Unit: g / mol) Molecular weight distribution
(PDI)
MAO Transition metal
compound mmol / g-SiO ₂ mmol / g-SiO ₂ Example 4 8 0.1 10.5 132,100 14.6 Example 5 8 0.1 8.4 121,000 20.2 Comparative Example 4 8 0.1 12.8 127,000 15.5

In addition, the GPC-FTIR measurement results of the polyolefins of Examples 4, 5 and Comparative Example 4 are shown in Figs.

From Table 2 and FIGS. 1 to 3, polyolefins prepared by using a hybrid supported metallocene catalyst carrying the transition metal compound catalyst of the present invention as a low molecular weight catalyst have a comonomer content concentrated in a high molecular weight backbone. It can be seen that the structure, namely, the BOCD structure, which is a structure in which the side branch content increases toward the higher molecular weight, is clearly shown.

Claims (9)

A transition metal compound represented by Formula 1 below:
[Formula 1]

In Chemical Formula 1,
At least one of R1 to R8 is tert-butoxybutyl, the others are the same or different from each other, and each independently, hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and carbon atoms An aliphatic group selected from the group consisting of an alkylaryl group having 7 to 20 carbon atoms and an arylalkyl group having 7 to 20 carbon atoms, or two or more adjacent groups connected to each other and substituted or unsubstituted with a hydrocarbyl group having 1 to 10 carbon atoms; Or to form an aromatic ring,
Q1 and Q2 are the same as or different from each other, and are each independently a halogen or an alkyl group having 1 to 20 carbon atoms;
M is a Group 4 transition metal,
X1 and X2 are the same as or different from each other, and each independently a halogen or an alkyl group having 1 to 20 carbon atoms,
m is an integer of 0 or 1.
The transition metal compound of claim 1, wherein the transition metal compound of Formula 1 is represented by any one of the following Formulas 2 to 5:
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Chemical Formulas 2 to 5,
The definitions of R1 to R8, Q1 to Q2, M, and X1 to X2 are the same as those of Formula 1;
R 'and R''are the same as or different from each other and are each independently a hydrocarbyl group having 1 to 10 carbon atoms.
delete The method of claim 1,
The transition metal compound represented by Formula 1 is a compound represented by one of the following structural formulas, a transition metal compound:

A transition metal compound represented by Chemical Formula 1 of claim 1; And
A catalyst composition comprising a promoter comprising at least one selected from the group consisting of compounds represented by Formulas 6 to 8:
[Formula 6]
-[Al (R9) -O] a-
In Chemical Formula 6,
R9 may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;
a is an integer of 2 or more;
[Formula 7]
J (R10) ₃
In Chemical Formula 7,
R 10 is as defined in Formula 6 above;
J is aluminum or boron;
[Formula 8]
[EH] + [ZA4]-or [E] + [ZA4]-
In Chemical Formula 8,
E is a neutral or cationic Lewis base;
H is a hydrogen atom;
Z is a Group 13 element;
A may be the same or different from each other, and each independently is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, unsubstituted or substituted with one or more hydrogen atoms, halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy. .
The method of claim 5,
The transition metal compound and the promoter compound are supported catalysts and catalyst compositions supported on a carrier.
The method of claim 6,
A catalyst composition which is a hybrid supported catalyst further comprising a transition metal compound other than the transition metal compound represented by the formula (1).
A process for producing a polyolefin, comprising the step of polymerizing an olefinic monomer in the presence of the catalyst composition of claim 5.
The method of claim 8,
The olefinic monomers are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene , 1-tetradecene, 1-hexadecene, and 1-eicosene comprising at least one member selected from the group consisting of, polyolefin production method.

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