KR20200132744A - Hafnium compound and catalyst composition comprising the same - Google Patents

Abstract

The present invention relates to a hafnium compound having a novel structure, a catalyst composition containing the same, and a method for manufacturing an olefin polymer using the same. By using the hafnium compound of the present invention as a catalyst, it is possible to perform the method for manufacturing the olefin polymer which is advantageous in controlling the block composition and molecular weight of a polyolefin block and has excellent efficiency.

Description

Hafnium compound and catalyst composition comprising the same TECHNICAL FIELD

The present invention relates to a hafnium compound having a novel structure, a catalyst composition comprising the same, and a method for producing an olefin polymer using the same.

Polyolefin (PO) is a polymer mainly produced using a Ziegler-Natta catalyst. Conventional heterogeneous multi-site Ziegler-Natta catalysts, which have been frequently used in the production of polyolefins, have been replaced by homogeneous single-site catalysts. The use of homogeneous single-site catalysts began with the accidental discovery of methylaluminoxane (MAO) by Kaminsky, in the early days of zirconium-based metallocene catalysts and titanium-based half-metallocene. (Ti-based half-metallocenes) and post-metallocenes catalysts having a non-cyclopentadienyl ligand have been developed.

Titanium-based half-metallocene has a feature that exhibits higher alpha-olefin mixing ability in ethylene/alpha-olefin copolymerization reactions that commercially produce polyolefin elastomers compared to zirconium-based metallocene catalysts. A typical example is [Me ₂ Si(η ⁵ -Me ₄ C ₅ )(N ^t Bu)]TiCl ₂ (Constrained-Geometry Catalyst, CGC) developed by Dow in the early 1990s. As various properties of CGC are gradually becoming known, efforts to synthesize derivatives thereof and use as polymerization catalysts have been actively made in academia and industry. The approach may include modification of a supporting ligand, introduction of various bridges and nitrogen substituents instead of a silicon bridge, and introduction of an oxido ligand instead of the amido ligand of the CGC.

In addition, representative metal compounds known until recently include CGC-structured silicon bridges, phosphorus, ethylene or propylene, methylidene and methylene bridges. However, when applied to ethylene polymerization or copolymerization of ethylene and alpha-olefin, superior results were not shown in terms of polymerization activity or copolymerization performance compared to CGC.

Accordingly, there is still a need for a catalyst showing more improved polymerization performance and a method for simply preparing such catalysts.

US Patent No. 5,064,802

An object of the present invention is to provide a hafnium compound having a novel structure capable of producing an olefin polymer having an ultra-low density and high molecular weight due to excellent copolymerization.

Another object of the present invention is to provide a catalyst composition comprising the hafnium compound and a cocatalyst.

Another object of the present invention is to provide a method of preparing an olefin polymer in the presence of the catalyst composition.

In order to solve the above problems, an embodiment of the present invention provides a hafnium compound represented by the following Formula 1:

[Formula 1]

In Formula 1,

R ₁ to R ₁₁ are each independently hydrogen; An alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; Alkynyl group having 2 to 20 carbon atoms; A cycloalkyl group having 3 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; Arylalkoxy group having 7 to 20 carbon atoms; An alkoxy group having 1 to 20 carbon atoms; An alkylaryl group having 7 to 20 carbon atoms; An alkylsilyl group having 1 to 20 carbon atoms; Or an arylalkyl group having 7 to 20 carbon atoms,

Two or more adjacent ones of R ₁ to R ₁₁ may be connected to each other to form an aliphatic ring having 3 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms,

X ₁ and X ₂ are each independently hydrogen; halogen; Hydroxy group; Amino group; Pyo; Silyl group; Cyano group; Nitro group; An alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; Alkynyl group having 2 to 20 carbon atoms; A cycloalkyl group having 3 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; An alkylaryl group having 7 to 20 carbon atoms; Arylalkyl group having 7 to 20 carbon atoms; A heteroaryl group having 5 to 20 carbon atoms; An alkoxy group having 1 to 20 carbon atoms; Aryloxy group having 6 to 20 carbon atoms; An alkylamino group having 1 to 20 carbon atoms; Arylamino group having 6 to 20 carbon atoms; Alkylthio groups having 1 to 20 carbon atoms; Arylthio groups having 6 to 20 carbon atoms; An alkylsilyl group having 1 to 20 carbon atoms; Or an arylsilyl group having 6 to 20 carbon atoms.

In addition, an embodiment of the present invention provides a catalyst composition comprising a hafnium compound represented by Chemical Formula 1 and a cocatalyst.

In addition, an embodiment of the present invention provides a method for preparing an olefin polymer comprising; polymerizing an olefin monomer in the presence of the catalyst composition.

The hafnium compound represented by Formula 1 of the present invention can efficiently produce an ethylene/alpha-olefin copolymer using high copolymerization, and can perform living polymerization through coordinative chain transfer polymerization (CCTP). There is an advantage that it can be used in the manufacture of block copolymers.

Therefore, by using the hafnium compound of the present invention as a catalyst, it is possible to perform a method for producing an olefin polymer that is advantageous in controlling the composition and molecular weight of a polyolefin block and has excellent efficiency, and the polymer thus prepared can be commercially useful.

1 shows a ¹ H NMR spectrum and a ¹³ C NMR spectrum of the hafnium compound prepared in Preparation Example 1.
2 shows a ¹ H NMR spectrum and a ¹³ C NMR spectrum of the hafnium compound prepared in Preparation Example 2.
3 is a ¹ H NMR spectrum and a ¹³ C NMR spectrum of the hafnium compound prepared in Preparation Example 3.
4 shows a ¹ H NMR spectrum and a ¹³ C NMR spectrum of the hafnium compound prepared in Example 4.
5 shows a ¹ H NMR spectrum and a ¹³ C NMR spectrum of the hafnium compound prepared in Example 5.
6 shows the Thermal Ellipsoid Plot (30% probability level, hydrogen atom omitted) of (a) Preparation Example 1, (b) Preparation Example 2, and (c) Preparation Example 3. FIG.
Figure 7 is a co-catalyst _{[(C 18 H 37) 2} N (H) Me] + [B (C 6 F 5) 4] prepared in the present ^invention shows the ¹ H NMR spectra.
8 is conducted in Preparation Example 1 and shows the ¹ H NMR spectrum of the co-catalyst compound complexes. Fig. 9 shows the ¹ H NMR spectrum of the exemplary preparation 2 and the co-catalyst compound complexes.
10 shows the ¹ H NMR spectrum and the ¹³ C NMR spectrum of the complex of Example 3 and the cocatalyst compound.
11 shows a ¹ H NMR spectrum of the complex of Example 4 and the cocatalyst compound.
12 shows a ¹ H NMR spectrum of the complex of Example 5 and the cocatalyst compound.
13 shows (a) ¹ H NMR spectra of the hafnium compound of Example 3 and (b) Example 3 and the cocatalyst compound complex.
14 shows the ¹ H NMR spectrum of the olefin polymer prepared in Example 3.
15 shows the GPC curve of the olefin polymer obtained by CCTP.

Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.

The terms or words used in the description and claims of the present invention should not be construed as being limited to a conventional or dictionary meaning, and the inventor appropriately defines the concept of terms in order to explain his own invention in the best way. Based on the principle that it can be done, it should be interpreted as a meaning and concept consistent with the technical idea of the present invention.

In the present invention, "alkyl" means a straight or branched chain hydrocarbon residue.

In the present invention, "alkenyl" means a linear or branched alkenyl group.

In the present invention, "aryl" preferably has 6 to 20 carbon atoms, and specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but are not limited thereto.

In the present invention, "alkylaryl" means an aryl group substituted by the alkyl group.

In the present invention, "arylalkyl" refers to an alkyl group substituted by the aryl group.

In the present invention, "alkylsilyl" may be silyl substituted with alkyl having 1 to 20 carbon atoms, for example, trimethylsilyl or triethylsilyl.

In the present invention, "alkylamino" refers to an amino group substituted by the alkyl group, and includes a dimethylamino group and a diethylamino group, but is not limited thereto.

In the present invention, "hydrocarbyl" unless otherwise stated, alkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkylaryl or arylalkyl, regardless of its structure, consisting of only carbon and hydrogen, monovalent monovalent It means a hydrocarbon group.

Hafnium compound

The hafnium compound of the present invention is characterized by represented by the following formula (1).

[Formula 1]

In Formula 1,

R ₁ to R ₁₁ are each independently hydrogen; An alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; Alkynyl group having 2 to 20 carbon atoms; A cycloalkyl group having 3 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; Arylalkoxy group having 7 to 20 carbon atoms; An alkoxy group having 1 to 20 carbon atoms; An alkylaryl group having 7 to 20 carbon atoms; An alkylsilyl group having 1 to 20 carbon atoms; Or an arylalkyl group having 7 to 20 carbon atoms,

Two or more adjacent ones of R ₁ to R ₁₁ may be connected to each other to form an aliphatic ring having 3 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms,

X ₁ and X ₂ are each independently hydrogen; halogen; Hydroxy group; Amino group; Pyo; Silyl group; Cyano group; Nitro group; An alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; Alkynyl group having 2 to 20 carbon atoms; A cycloalkyl group having 3 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; An alkylaryl group having 7 to 20 carbon atoms; Arylalkyl group having 7 to 20 carbon atoms; A heteroaryl group having 5 to 20 carbon atoms; An alkoxy group having 1 to 20 carbon atoms; Aryloxy group having 6 to 20 carbon atoms; An alkylamino group having 1 to 20 carbon atoms; Arylamino group having 6 to 20 carbon atoms; Alkylthio groups having 1 to 20 carbon atoms; Arylthio groups having 6 to 20 carbon atoms; An alkylsilyl group having 1 to 20 carbon atoms; Or an arylsilyl group having 6 to 20 carbon atoms.

When the polymerization reaction is carried out in the presence of an excess chain transfer agent (e.g., (Et) ₂ Zn) compared to the catalyst, the olefin polymer chain causes rapid transalkylation between zinc (Zn) and hafnium (Hf) and grows uniformly from dialkylzinc. Thus, living polymerization can be implemented, and this is called coordinative chain transfer polymerization (CCTP). Metallocene catalysts used in the past cannot be subjected to living polymerization through a β-elimination process, and a few catalysts known to be applicable to CCTP are only capable of single polymerization of ethylene, ethylene and alpha-olefins. Since it was very difficult to carry out the copolymerization of CCTP as a catalyst, it was very difficult to perform living polymerization through CCTP and prepare a block copolymer using a general transition metal compound as a catalyst.

On the other hand, the hafnium compound of the present invention is 1,2,3,4-tetrahydro-1,10-phenanthroline (1,2,3,4-tetrahydro-1,10-phenanthroline) skeleton and Hf-C (aryl ) As a [N ^amido ,N,C ^aryl ]HfMe ₂ -type complex containing a bond, it exhibits excellent alpha-olefin mixing ability in the polymerization reaction of ethylene and alpha-olefin. In particular, depending on the content of the chain transfer agent, the olefin polymer The molecular weight or the content of alpha-olefins varies, indicating that the compounds of the present invention are used successfully in CCTP and that the β-elimination reaction rarely occurs to a negligible degree. That is, it is possible to carry out the copolymerization of ethylene and alpha-olefin monomers by CCTP using the hafnium compound of the present invention to perform living polymerization, and to successfully prepare a block copolymer having various block compositions. In addition, it is possible to synthesize a polyolefin-polystyrene block copolymer by converting the CCTP using the hafnium compound of the present invention into an anionic styrene polymerization reaction.

As described above, the hafnium compound of the present invention can be usefully used as a catalyst for the production of an olefin polymer, which is a unique feature that can be achieved with the novel structure of the compound newly developed in the present invention.

Specifically, in Formula 1, R ₁ to R ₁₁ are each independently hydrogen; An alkyl group having 1 to 20 carbon atoms; A cycloalkyl group having 3 to 20 carbon atoms; Or it may be an aryl group having 6 to 20 carbon atoms, preferably R ₁ to R ₁₀ are hydrogen, and at the same time R ₁₁ is hydrogen; An alkyl group having 1 to 20 carbon atoms; Or it may be an aryl group having 6 to 20 carbon atoms, more preferably, R ₁ to R ₁₀ are hydrogen, and at the same time R ₁₁ is hydrogen; Or it may be an alkyl group having 1 to 20 carbon atoms.

Or, in Formula 1, the R ₁ to R ₁₁ are each independently hydrogen; An alkyl group having 1 to 20 carbon atoms; Or it may be an aryl group having 6 to 20 carbon atoms, in which case, R ₃ and R ₄ may be connected to each other to form an aromatic ring having 5 to 20 carbon atoms, such as a benzene ring, preferably R ₃ and R ₄ are each Is connected to form a benzene ring, and at the same time, R ₁₁ is an alkyl group having 1 to 20 carbon atoms; Or it may be an aryl group having 6 to 20 carbon atoms.

Or, in Formula 1, R ₁ , R ₂ , and R ₅ to R ₁₀ are hydrogen, and R ₃ , R ₄ and R ₁₁ are each independently hydrogen; Or an alkyl group having 1 to 20 carbon atoms, and R ₃ and R ₄ may be connected to each other to form an aromatic ring having 5 to 20 carbon atoms, such as a benzene ring.

Meanwhile, X ₁ and X ₂ are each independently hydrogen; An alkyl group having 1 to 20 carbon atoms; A cycloalkyl group having 3 to 20 carbon atoms; Alternatively, it may be an aryl group having 6 to 20 carbon atoms, and preferably each independently may be an alkyl group having 1 to 20 carbon atoms, and X ₁ and X ₂ may be the same as each other.

More specifically, the hafnium compound represented by Formula 1 may be a hafnium compound represented by Formula 1a or 1b below:

[Formula 1a]

[Formula 1b]

In Formula 1a and Formula 1b,

R ₁₁ is hydrogen; An alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; Alkynyl group having 2 to 20 carbon atoms; A cycloalkyl group having 3 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; Arylalkoxy group having 7 to 20 carbon atoms; An alkoxy group having 1 to 20 carbon atoms; An alkylaryl group having 7 to 20 carbon atoms; An alkylsilyl group having 1 to 20 carbon atoms; Or an arylalkyl group having 7 to 20 carbon atoms,

X ₁ and X ₂ are each independently hydrogen; halogen; Hydroxy group; Amino group; Pyo; Silyl group; Cyano group; Nitro group; An alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; Alkynyl group having 2 to 20 carbon atoms; A cycloalkyl group having 3 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; An alkylaryl group having 7 to 20 carbon atoms; Arylalkyl group having 7 to 20 carbon atoms; A heteroaryl group having 5 to 20 carbon atoms; An alkoxy group having 1 to 20 carbon atoms; Aryloxy group having 6 to 20 carbon atoms; An alkylamino group having 1 to 20 carbon atoms; Arylamino group having 6 to 20 carbon atoms; Alkylthio groups having 1 to 20 carbon atoms; Arylthio groups having 6 to 20 carbon atoms; An alkylsilyl group having 1 to 20 carbon atoms; Or an arylsilyl group having 6 to 20 carbon atoms.

The hafnium compound may be specifically represented by any one of Formulas 1-1 to 1-5, but is not limited thereto, and all hafnium compounds corresponding to Formula 1 are included in the present invention.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

The compound of the present invention may be prepared from a ligand compound represented by the following formula (2).

[Formula 2]

In Chemical Formula 2,

R ₁ to R ₁₁ are each independently hydrogen; An alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; Alkynyl group having 2 to 20 carbon atoms; A cycloalkyl group having 3 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; Arylalkoxy group having 7 to 20 carbon atoms; An alkoxy group having 1 to 20 carbon atoms; An alkylaryl group having 7 to 20 carbon atoms; An alkylsilyl group having 1 to 20 carbon atoms; Or an arylalkyl group having 7 to 20 carbon atoms,

Two or more adjacent ones of R ₁ to R ₁₁ may be connected to each other to form an aliphatic ring having 3 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms.

Method for producing hafnium compound

The hafnium compound of the present invention may be prepared including a step of reacting a compound represented by the following formula (2) and a compound represented by formula (3).

[Formula 2]

[Formula 3]

In the above formula,

The definitions of R ₁ to R ₁₁ , X ₁ and X ₂ are the same as described above.

Meanwhile, when preparing the hafnium compound represented by Formula 1 of the present invention, the steps of preparing a ligand compound may be performed differently as follows according to the structure of the finally prepared hafnium compound.

For example, in the case where R ₃ and R ₄ in the ligand compound do not form a ring with each other and R ₁₁ is a hydrogen atom, hydrogenation is performed under a ruthenium catalyst to prepare a ligand compound and then reacted with the compound represented by Formula 3, which is a hafnium precursor. Hafnium compounds can be prepared.

[Scheme 1]

In addition, when R ₃ and R ₄ in the ligand compound structure do not form a ring with each other and R ₁₁ is a substituent other than a hydrogen atom, R ₁₁ is first introduced using an organolithium compound as shown in Scheme 2 below, and then under a ruthenium catalyst. Hydrogenation produces a ligand compound.

[Scheme 2]

In addition, in the ligand compound structure, when R ₃ and R ₄ are connected to each other to form an aromatic ring having 5 to 20 carbon atoms, and R ₁₁ is a substituent other than a hydrogen atom, R ₁₁ is first introduced using an organolithium compound as follows. Thereafter, in order to prevent hydrogenation of an aromatic ring such as a naphthyl group, a ligand compound may be prepared by hydrogenation under a Pd/C catalyst.

[Scheme 3]

That is, the hafnium compound of the present invention may be prepared by preparing a ligand compound through alkylation and hydrogenation under appropriate reagents and reaction conditions for a compound that is a precursor of the ligand compound, and then introducing hafnium thereto, and specific types of alkylation reagents, reaction The temperature and pressure can be appropriately changed by a person skilled in the art in consideration of the structure and experimental conditions of the final compound.

Catalyst composition

The catalyst composition of the present invention is characterized in that it comprises a hafnium compound represented by Chemical Formula 1 and a cocatalyst.

In the present invention, "composition" includes reaction products and decomposition products formed from the materials of the composition, as well as mixtures of materials comprising the composition.

The cocatalyst may be one known in the art, and for example, one or more selected from the following Formulas 4 to 6 may be used as a cocatalyst.

[Formula 4]

-[Al(R _a )-O] _m-

[Formula 5]

D(R _a ) ₃

[Formula 6]

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

In the above formula,

Each R _a is independently a halogen radical; A hydrocarbyl radical having 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with a halogen,

m is an integer of 2 or more,

D is aluminum or boron,

L is a neutral or cationic Lewis acid,

Z is a group 13 element,

A is each independently an aryl group having 6 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent; Or an alkyl group having 1 to 20 carbon atoms,

The substituent of A is a halogen group; A hydrocarbyl group having 1 to 20 carbon atoms; An alkoxy group having 1 to 20 carbon atoms; Or it is a C6-C20 aryloxy group.

The compound represented by Formula 4 is not particularly limited as long as it is an alkylaluminoxane. Preferred examples include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like, and a particularly preferred compound is methylaluminoxane.

The compound represented by Formula 5 is not particularly limited, but preferred examples include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro 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, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, etc. are included, and particularly preferred compounds are selected from trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum.

Examples of the compound represented by Formula 6 are when Z is boron, for example, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate [(C ₁₈ H ₃₇ ) ₂ N(H)Me] ⁺ [B(C ₆ F ₅ ) ₄ ] ^- , Dioctadecylmethylammonium tetrakis(phenyl)borate, dioctadecylmethylammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate tetrakis(phenyl)borate, tri Ethyl ammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, trimethylammonium tetra(o,p-dimethylphenyl)borate, tri Butylammonium tetra(p-trifluoromethylphenyl)borate, trimethylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetrapentafluorophenylborate, N,N-diethylanilideum tetrafetylborate, N ,N-diethylanilidium tetraphenylborate, N,N-diethylanilinium tetrapentafluorophenylborate, diethylammonium tetrapentafluorophenylborate, triphenylphosphonium tetraphenylborate, trimethylphosphonium tetra Phenylborate, trimethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, tripropylammonium tetra(p-tolyl)borate, triethylammonium tetra(o,p-dimethylphenyl)borate , Trimethylammonium tetra(o,p-dimethylphenyl)borate, tributylammonium tetra(p-trifluoromethylphenyl)borate, trimethylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetrapentafluorophenylborate , N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrapentafluorophenylborate, diethylammonium tetrapentafluoro Phenylborate, triphenylphosphonium tetraphenylborate, triphenylcarbonium tetra (p-trifluoromethylphenyl)borate, triphenylcarbonium tetrapentafluorophenylborate, or a combination thereof, Z is aluminum If it is, ecant Liethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra(p-tolyl)aluminum, tripropylammonium tetra(p-tolyl)aluminum, triethyl Ammonium tetra(o,p-dimethylphenyl)aluminum, tributylammonium tetra(p-trifluoromethylphenyl)aluminum, trimethylammonium tetra(p-trifluoromethylphenyl)aluminum, tributylammonium tetrapentafluorophenylaluminum, N ,N-diethylanilinium tetraphenylaluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatentraphenylaluminum , Triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, or a combination thereof, but is not limited thereto.

In particular, the cocatalyst used in the present invention may be a compound represented by Chemical Formula 6, and specifically, may be dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate.

In addition, the cocatalyst used in the present invention may be prepared in anhydrous hydrocarbon solvent. For example, the hydrocarbon solvent may be one or more selected from the group consisting of butane, pentane, neopentane, hexane, cyclohexane, methylcyclohexane, heptane, octane, benzene, toluene, xylene and ethylbenzene, but limited thereto. It is not, and all hydrocarbon solvents available in the art can be used in anhydrous form.

In the present invention, when the cocatalyst is prepared in anhydrous hydrocarbon solvent, in the ¹ H NMR spectrum, at least one peak appears in the range of 1.75 ppm to 1.90 ppm and 1.90 ppm to 2.00 ppm, respectively. This indicates that the protons attached to α\α-carbon adjacent to nitrogen, sulfur, or phosphorus contained in L show different peaks. For example, when the hafnium compound represented by Formula 1 is [(C ₁₈ H ₃₇ ) ₂ N(H)Me] ⁺ [B(C ₆ F ₅ ) ₄ ] ^- , in its ¹ H NMR spectrum, NC H ₂ Each of the two protons present can represent a different signal.

In addition, the hafnium compound and cocatalyst represented by Formula 1 may be used in a form supported on a carrier. Silica or alumina may be used as the carrier, but is not limited thereto.

Method for producing olefin polymer

The method for producing an olefin polymer of the present invention is characterized in that it comprises the step of polymerizing an olefin monomer in the presence of the catalyst composition.

In the present invention, the "polymer" refers to a polymer compound prepared by polymerizing monomers of the same or different types. The generic term polymer in this way encompasses the term homopolymer, which is commonly used to refer to polymers made from only one monomer, and the term interpolymer as defined below.

In the present invention, the "interpolymer" refers to a polymer prepared by polymerization of at least two different monomers. In this way, the generic term interpolymer includes copolymers commonly used to refer to polymers made from two different monomers, and polymers made from two or more different monomers.

In the present invention, the olefin monomer is 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 may be one or more selected from the group consisting of 1-eicosene, but is not limited thereto.

Specifically, the olefin polymer of the present invention may be an olefin homopolymer, an olefin/alpha-olefin copolymer, and preferably an ethylene/alpha-olefin copolymer, depending on the type of olefin monomer. In this case, the content of the alpha-olefin monomer as a comonomer may be appropriately selected by a person skilled in the art according to the use and purpose of the olefin polymer, and may be about 1 to 99 mol%.

The catalyst composition is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the polymerization process of an olefin monomer, such as pentane, hexane, heptane, nonane, decane, and isomers thereof, and an aromatic hydrocarbon solvent such as toluene and benzene, dichloromethane, It can be dissolved or diluted in a hydrocarbon solvent substituted with a chlorine atom such as chlorobenzene and injected. The solvent used here is preferably used after removing a small amount of water or air acting as a catalyst poison by treatment with a small amount of alkyl aluminum, and it is possible to further use a cocatalyst.

The most preferred manufacturing process using the catalyst composition is a solution process, and if such a composition is used together with an inorganic carrier such as silica, it can be applied to a slurry or gas phase process.

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

In addition, during the polymerization reaction, an organic aluminum compound for removing moisture in the reactor is further added, so that the polymerization reaction may proceed in the presence of the organic aluminum compound. Specific examples of such an organoaluminum compound include trialkyl aluminum, dialkyl aluminum halide, alkyl aluminum dihalide, aluminum dialkyl hydride or alkyl aluminum sesqui halide, and more specific examples thereof, Al(C ₂ H ₅ ) ₃ , Al(C ₂ H ₅ ) ₂ H, Al(C ₃ H ₇ ) ₃ , Al(C ₃ H ₇ ) ₂ H, Al(iC ₄ H ₉ ) ₂ H, Al(C ₈ H ₁₇ ) ₃ , Al(C ₁₂ H ₂₅ ) ₃ , Al(C ₂ H ₅ )(C ₁₂ H ₂₅ ) ₂ , Al(iC ₄ H ₉ )(C ₁₂ H ₂₅ ) ₂ , Al(iC ₄ H ₉ ) ₂ H, Al(iC ₄ H ₉ ) ₃ ,(C ₂ H ₅ ) ₂ AlCl, (iC ₃ H ₉ ) ₂ AlCl or (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ . These organoaluminum compounds may be continuously introduced into the reactor, and may be added in a ratio of about 0.1 to 10 moles per 1 kg of the reaction medium introduced into the reactor for proper moisture removal.

According to an embodiment of the present invention, the polymerization of the olefin polymer is performed at a temperature of about 80 to 200°C, specifically about 90 to 200°C, or a temperature of about 130 to 200°C, and a temperature of about 20 to 100 bar. It can be carried out by reacting for about 8 minutes to 2 hours under pressure, specifically, a pressure of about 20 to 50 bar, or a pressure of about 20 to 40 bar.

Example

Hereinafter, the present invention will be described in more detail by examples. However, the following examples are for illustrative purposes only, and the scope of the present invention is not limited thereto.

Reagents and experimental conditions

All experiments were performed in an inert atmosphere using a standard glove box and Schlenk technique. Toluene, hexane and THF were distilled from benzophenone ketyl and used. Methylcyclohexane (anhydrous grade) used in the polymerization reaction was purchased from Tokyo Chemical Industry (TCI) and purified with Na/K alloy. HfCl ₄ (Sublimed-grade) was purchased from Streme and used as it is. The ethylene/propylene mixed gas was purified and used on trioctyl aluminum (0.6 M in methylcyclohexane) in a bomb reactor (2.0 L).

¹ H NMR (600 MHz) and ¹³ C NMR (150 MHz) analysis were performed on a JEOL ECZ 600 instrument. Elemental analysis was performed at Ajou University's Analysis Center. GPC data were obtained with 1,2,4-trichlorobenzene at 160°C using a PL-GPC 220 system equipped with an RI detector and two columns (Varian, PLgel mixed-B 7.5 × 300 mm).

X-ray Crystallographic

Diffraction data of hafnium compounds were collected with a Bruker APEX II CCD with graphite-monochromated Mo K-α radiation (λ = 0.7107 Å). Specifically, specimens of appropriate quality and size were selected, mounted on an X-ray beam, and centered using a video camera. The hemispheres of reflection data were collected in Ψ and ω scan frames with exposure times of 0.5°/frame and 10 s/frame. Cell parameters were determined and purified by the SMART program. Data reduction was performed using the SAINT software, and the data were corrected for Lorentz and polarization effects. The empirical absorption correction was performed using the SADABS program.

The structure of the compound was determined by a direct method and purified by the whole matrix least squares method using the SHELXTL program package with anisotropic thermal parameters for all non-hydrogen atoms. Crystallographic data was deposited with the Cambridge Crystallographic Data Center.

Synthesis of hafnium compounds

Example Preparation Example 1

[Formula 1-1]

MeMgBr (1.24 mL, 3.11 M in diethyl ether) was added dropwise to a stirred suspension (0.300 g, 0.938 mmol) of HfCl ₄ in toluene (8 mL) at -78°C. After stirring for 1 hour at a temperature range of -40°C and -35°C, the solution was cooled to -78°C again.

On the other hand, the ligand compound (9-phenyl-1,2,3,4-tetrahydro-1,10-phenanthroline) was described in [Angew. Chem. Int. Ed. 2013, 52, 7172-7176], a solution (0.24 g, 0.94 mmol) of the ligand compound in toluene (4 mL) was prepared and added dropwise to the solution prepared above.

The resulting solution was stirred for 2 hours at a controlled temperature in the range of -40°C and -35°C, and then stirred overnight at room temperature. The solvent was removed using a vacuum line and the residue was extracted with hexane (60 mL). The solvent was removed to obtain a pure dark red solid compound (0.79g, 53%), ¹ H and ¹³ C NMR spectra were analyzed, and the results are shown in FIG. 1. In addition, after recrystallization in hexane at -30°C to obtain a pure compound for analysis containing a single crystal suitable for X-ray crystallography, X-ray crystallography analysis was performed.

^-1 H NMR (C ₆ D ₆ ): δ 8.47 (d, J = 6.6 Hz, H), 7.63 (d, J = 7.8 Hz, H), 7.57 (d, J = 9.0 Hz, H), 7.47 ( t, J = 6.0 Hz, H), 7.27 (dt, J = 7.8 Hz, H), 7.24 (d, J = 8.4 Hz, H), 7.07 (d, J = 7.2 Hz, H), 6.74 (d, J = 8.4 Hz, H), 3.95 (m, 2H), 2.62 (t, J = 6.6 Hz, 2H), 1.76 (m, 2H), 0.76 (s, 6H, Hf(CH ₃ ) ₂ ) ppm.

^-13 C{ ¹ H} NMR (C ₆ D ₆ ): δ 22.82, 26.84, 45.04, 63.72, 112.33, 115.03, 120.11, 124.29, 126.68, 128.62, 130.11, 130.33, 137.32, 141.01, 141.19, 147.77, 151.00, 163.28, 204.57 ppm.

-Anal. Calcd. (C ₂₀ H ₂₀ HfN ₂ ): C, 51.45; H, 4.32; N, 6.00%. Found: C, 51.35; H, 4.31; N, 6.10%.

-C ₂₀ H ₁₈ HfN ₂ , M = 464.85, orthorhombic, a = 12.5672(8), b = 7.8737(5), c = 34.8321(19) Å, V = 3446.6(4) Å ³ , T = 100(2 ) K, space group Pbca , Z = 8, 675 unique(R(int) = 0.0389).

Example Preparation Example 2: Synthesis of hafnium compound of Formula 1-2

[Formula 1-2]

Instead of 9-phenyl-1,2,3,4-tetrahydro-1,10-phenanthroline as a ligand compound, 2-butyl-9-phenyl-1,2,3,4-tetrahydro It was prepared in the same manner as in Example 1, except that -1,10-phenanthroline (0.390 g, 1.23 mmol) was prepared and used.

A dark red solid compound was obtained (0.148 g, 86%), and ¹ H and ¹³ C NMR spectra were analyzed, and the results are shown in FIG. 2. In addition, after recrystallization in hexane at -30°C to obtain a pure compound for analysis containing a single crystal suitable for X-ray crystallography, X-ray crystallography analysis was performed.

^-1 H NMR (C ₆ D ₆ ): δ 8.49 (d, J = 6.6 Hz, H), 7.64 (d, J = 7.2 Hz, H), 7.60 (d, J = 9.0 Hz, H), 7.47 ( t, J = 7.2 Hz, H), 7.27 (m, 2H), 7.14 (d, J = 8.4 Hz, H), 6.77 (d, J = 7.2 Hz, H), 4.29 (m, H, NCH), 2.83 (m, H), 2.52 (td, J = 4.2 Hz, H), 2.03 (m, H), 1.90 (m, H), 1.74 (m, 2H), 1.35 (m, 2H), 0.95 (t , J = 7.2 Hz, 3H), 0.85 (s, 3H, HfCH ₃ ), 0.79 (s, 3H, HfCH ₃ ) ppm.

^-13 C{ ¹ H} NMR (C ₆ D ₆ ): δ 14.48, 22.96, 23.20, 24.57, 28.82, 35.37, 53.14, 63.37, 65.49, 112.21, 115.01, 119.45, 124.21, 126.83, 128.49, 130.21, 130.30, 137.63, 141.24, 147.60, 150.43, 163.25, 204.42 ppm.

-Anal. Calcd. (C ₂₄ H ₂₈ HfN ₂ ): C, 55.12; H, 5.40; N, 5.36%. Found: C, 54.99; H, 5.41; N, 5.27%.

-C _24.70 H _28.60 HfN ₂ , M = 531.98, monoclinic, a = 16.1724(3), b = 16.1772(3), c = 22.6003(4) Å, β = 107.9164(12)°, V = 5626.05(18) Å ³ , T = 100(2) K, space group P2 ₁ , Z = 1, 11111 unique(R(int) = 0.0588).

Example Preparation 3: Synthesis of hafnium compound of Formula 1-3

[Formula 1-3]

(I) Preparation of Ligand Compound

To a stirred suspension (1.00 g, 3.90 mmol) of 2-phenyl-1,10-phenanthroline in toluene (10 mL) was slowly added isopropyllithium (6.13 mL, 0.70 M in pentane) at -30°C. The solution was heated to 0° C. and stirred for 35 minutes. H ₂ O (16 mL) was added, and the organic compound was extracted with dichloromethane (3 × 10 mL). The solvent was removed using a vacuum line and the residue was redissolved in dichloromethane (10 mL). Activated MnO ₂ (3.68 g, 42.3 mmol) was added and the solution was stirred for 12 hours under atmospheric exposure. After filtration over anhydrous MgSO ₄ , the solvent was removed by rotary evaporator. Pure 2-isopropyl-9-phenyl-1,10-phenanthroline was obtained by silica gel column chromatography using ethyl acetate/hexane (1/10, v/v) (1.01 g, 87%).

Obtained 2-isopropyl-9-phenyl-1,10-phenanthroline (1.01 g, 3.39 mmol), Ru (OTf) (TsDPEN) (η6-p-cymene) (TfO- = trifluoromethanesulfonate , TsDPEN = N-toluenesulfonyl-1,2-diphenylethylenediamine) (0.17 mmol) and MeOH (17 mL) were added to the reactor. After charging H ₂ to 50 bar, the reaction mixture was stirred at room temperature for 12 hours. After release of H ₂ , it was further stirred under atmospheric exposure for 12 hours. The solvent was removed by a rotary evaporator, and the residue was purified by silica gel column chromatography using ethyl acetate/hexane (1/50, v/v) to give a light yellow solid compound (0.615 g, 60%).

^-1 H NMR (CDCl ₃ ): δ 8.17 (d, J = 6.6 Hz, 2H), 8.07 (d, J = 9.0 Hz, H), 7.80 (d, J = 8.4 Hz, H), 7.52 (t, J = 7.2 Hz, 2H), 7.45 (t, J = 7.8 Hz, H), 7.15 (d, J = 7.2 Hz, H), 6.98 (d, J = 8.4 Hz, H), 6.26 (s, H, NH), 3.25 (m, H, NCH), 2.99 (m, H), 2.90 (m, H), 2.09 (m, H), 1.91 (m, H), 1.84 (m, 2H, NCCH), 1.16 and 1.09(d, J = 6.0 Hz, 6H, CH(C H ₃ ) ₂ ) ppm.

^-13 C{ ¹ H} NMR (C ₆ D ₆ ): δ 18.54, 18.92, 24.70, 26.86, 32.77, 56.80, 112.96, 116.71, 118.23, 126.85, 127.60, 128.95, 128.99, 129.07, 136.80, 137.74, 140.57, 141.68, 153.70 ppm.

-m/z calcd([M ⁺ ] C ₂₁ H ₂₂ N ₂ ) 302.4210. Found: 302.1785.

(ii) Preparation of hafnium compound

2-isopropyl-9-phenyl-1,2,3,4-tetrahydro prepared above in place of 9-phenyl-1,2,3,4-tetrahydro-1,10-phenanthroline as a ligand compound It was prepared in the same manner as in Preparation Example 1, except that -1,10-phenanthroline (0.20 g, 0.66 mmol) was used.

A dark red solid compound was obtained (0.330 g, 98%), and ¹ H and ¹³ C NMR spectra were analyzed, and the results are shown in FIG. 3. In addition, after recrystallization in hexane at -30°C to obtain a pure compound for analysis containing a single crystal suitable for X-ray crystallography, X-ray crystallography analysis was performed.

^-1 H NMR (C ₆ D ₆ ): δ 8.50 (d, J = 7.2 Hz, H), 7.64 (d, J = 7.2 Hz, H), 7.60 (d, J = 9.0 Hz, H), 7.46 ( t, J = 6.6 Hz, H), 7.26 (m, 2H), 7.10 (d, J = 7.8 Hz, H), 6.75 (d, J = 8.4 Hz, H), 4.00 (m, H, NCH), 2.76(m, H), 2.58(m, 2H), 1.84(m, H), 1.68(m, H), 1.74(m, 2H), 1.05 and 1.01(d, J = 7.2 Hz, 6H, CH( CH ₃ ) ₂ ), 0.88 (s, 3H, HfCH ₃ ), 0.78 (s, 3H, HfCH ₃ ) ppm.

^-13 C{ ¹ H} NMR (C ₆ D ₆ ): δ 18.61, 21.19, 23.12, 25.51, 32.68, 60.75, 63.82, 66.81, 112.40, 114.96, 120.50, 124.15, 126.91, 130.19, 130.31, 140.96, 141.37, 147.36, 150.96, 163.49, 204.30 ppm.

-Anal. Calcd. (C ₂₃ H ₂₆ HfN ₂ ): C, 54.28; H, 5.15; N, 5.50%. Found: C, 54.37; H, 5.01; N, 5.47%.

-C ₂₃ H _26.20 HfN ₂ , M = 509.15, orthorhombic, a = 16.2081(7), b = 24.608(1), c = 27.4705(12) Å, V = 10956.6(8) Å ³ , T = 100(2 ) K, space group P2 ₁ 2 ₁ 2 ₁ , Z = 4, 5542 unique(R(int) = 0.0606).

Example Preparation Example 4: Synthesis of hafnium compound of Formula 1-4

[Formula 1-4]

(I) Preparation of Ligand Compound

To a suspension (0.741 g, 2.42 mmol) of 2-naphthyl-1,10-phenanthroline in toluene (8 mL) being stirred at -10°C was slowly added n-BuLi (1.65 ml, 1.61 M in hexane). . After stirring at room temperature for 3 hours, degassed H ₂ O (3 mL) was added. The aqueous layer was removed by syringe under N ₂ . The solvent was removed using a vacuum line and the residue was dissolved in degassed ethanol (15 mL) and THF (5 mL). The solution was transferred under N ₂ to a bomb reactor containing Pd/C (0.242 mmol, 10 mol %). After charging hydrogen gas to 5 bar, the mixture was stirred at room temperature for 12 hours. Hydrogen gas was released and the catalyst residue was removed by filtration over celite. The solvent was removed, and the residue was purified by silica gel column chromatography using ethyl acetate/hexane (1/3, v/v) to obtain a pale yellow solid compound (0.420 g, 47%).

^-1 H NMR (C ₆ D ₆ ): δ 8.49 (m, H), 7.75 (d, J = 8.4 Hz, H), 7.70 (m, H), 7.67 (d, J = 7.8 Hz, H), 7.64 (d, J = 7.2 Hz, H), 7.33 (m, 2H), 7.30 (m, 2H), 7.20 (d, J = 7.8 Hz, H), 7.02 (d, J = 8.4 Hz, H), 6.37 (s, H, NH), 3.16 (m, H, NCH), 2.82 (m, H), 2.73 (dt, J = 6.0 Hz, H), 1.79 (m, H), 1.57 (m, H) , 1.27 (m, 2H), 1.12 (m, 4H), 0.77 (d, J = 7.2 Hz, 3H, CH ₃ ) ppm.

^-13 C{ ¹ H} NMR (C ₆ D ₆ ): δ 14.28, 23.11, 26.64, 27.95, 28.25, 36.44, 51.09, 112.87, 116.54, 122.68, 125.59, 126.08, 126.59, 126.65, 126.78, 128.69, 128.99, 129.39, 132.24, 134.64, 136.36, 137.68, 139.93, 141.57, 156.03 ppm.

-m/z calcd([M ⁺ ] C ₂₆ H ₂₆ N ₂ ) 366.5100. Found: 366.2094.

(ii) Preparation of hafnium compound

2-butyl-9-(naphthalen-1-yl)-1,2,3 prepared above instead of 9-phenyl-1,2,3,4-tetrahydro-1,10-phenanthroline as a ligand compound It was prepared in the same manner as in Example 1, except that ,4-tetrahydro-1,10-phenanthroline (0.366 g, 1.00 mmol) was used. Since the product was not dissolved in hexane, the product was extracted with 50 mL of toluene and then pulverized in hexane to obtain a dark brown powder (0.259 g, 45%), and ¹ H and ¹³ C NMR spectra were analyzed and the results are shown in FIG. 4.

^-1 H NMR (C ₆ D ₆ ): δ 8.65 (d, J = 7.2 Hz, H), 8.52 (d, J = 8.4 Hz, H), 7.95 (d, J = 9.0 Hz, H), 7.87 ( d, J = 7.8 Hz, H), 7.77 (d, J = 8.4 Hz, H), 7.64 (d, J = 9.0 Hz, H), 7.41 (t, J = 7.8 Hz, H), 7.32 (t, J = 7.8 Hz, H), 7.18 (d, J = 8.4 Hz, H), 6.81 (d, J = 8.4 Hz, H), 4.33 (m, H), 2.88 (m, H), 2.57 (dt, J = 3.6 Hz, H), 2.11 (m, H), 1.92 (m, H), 1.79 (m, H), 1.38 (m, 4H), 0.96 (t, J = 6.6 Hz, 3H, (CH ₂ ) ₃ CH ₃ ), 0.83 (s, 3H, HfCH ₃ ), 0.82 (s, 3H, HfCH ₃ ) ppm.

^-13 C{ ¹ H} NMR (C ₆ D ₆ ): δ 14.46, 23.20, 24.70, 28.82, 35.47, 53.35, 62.87, 65.21, 112.16, 119.18, 119.65, 124.47, 125.46, 126.69, 127.04, 129.64, 130.00, 130.22, 131.27, 133.32, 135.59, 140.81, 141.69, 144.07, 149.83, 164.16, 208.15 ppm.

-Anal. Calcd. (C ₂₈ H ₃₀ HfN ₂ ): C, 58.69; H, 5.28; N, 4.89%. Found: C, 58.79; H, 5.21; N, 4.87%.

Example Preparation Example 5: Synthesis of the hafnium compound of Formula 1-5

[Formula 1-5]

(I) Preparation of Ligand Compound

As a reactant, isopropyllithium (0.45 mL, 0.36 mmol, 0.79 M in pentane) was used instead of n-BuLi, and 2-naphthyl-1,10-phenanthroline was used instead of 2-naphthyl-1,10-phenanthroline. Except for using (0.789 g, 2.58 mmol), it was prepared in the same manner as in the preparation method of the ligand compound of Preparation Example 4. A pale yellow sticky solid was obtained (0.085 g, 73%).

^-1 H NMR (C ₆ D ₆ ): δ 8.58 (d, J = 7.8 Hz, H), 7.75 (d, J = 9.0 Hz, H), 7.70 (d, J = 9.6 Hz, H), 7.66 ( d, J = 7.2 Hz, H), 7.63 (d, J = 6.6 Hz, H), 7.32 (m, 4H), 7.18 (d, J = 8.4 Hz, H), 6.99 (d, J = 7.8 Hz, H), 6.39 (s, H, NH), 2.93 (m, H), 2.79 (m, H), 2.70 (dt, J = 4.8 Hz, H), 1.70 (m, H), 1.63 (m, H ), 1.47 (m, H), 0.81 (d, J = 7.2 Hz, 3H, CH(CH ₃ ) ₂ ), 0.76 (d, J = 7.2 Hz, 3H, CH(CH ₃ ) ₂ ) ppm.

^-13 C{ ¹ H} NMR (C ₆ D ₆ ): δ 18.34, 18.77, 24.43, 26.78, 32.52, 56.73, 112.78, 116.67, 122.62, 125.59, 126.10, 126.51, 126.61, 126.86, 128.14, 128.69, 129.03, 129.28, 132.20, 134.71, 136.41, 137.64, 139.79, 141.75, 155.92 ppm.

-m/z calcd([M ⁺ ] C ₂₅ H ₂₄ N ₂ ) 352.4800. Found: 352.1942.

(Ii) Preparation of hafnium compound

2-isopropyl-9-(naphthalen-1-yl)-1,2 prepared above in place of 9-phenyl-1,2,3,4-tetrahydro-1,10-phenanthroline as a ligand compound, It was prepared in the same manner as in Example Preparation Example 1, except that 3,4-tetrahydro-1,10-phenanthroline (0.366 g, 1.00 mmol) was used. Since the product was not dissolved in hexane, 50 mL of toluene was extracted and pulverized in hexane to obtain a dark brown powder (0.226 g, 47%), and ¹ H and ¹³ C NMR spectra were analyzed, and the results are shown in FIG. 5.

^{_{- 1 H NMR (C 6 D}} 6): δ 8.66 (d, J = 7.8 Hz, H), 8.50 (d, J = 7.8 Hz, H), 7.92 (d, J = 9.0 Hz, H), 7.83 ( d, J = 7.2 Hz, H), 7.76 (d, J = 8.4 Hz, H), 7.62 (d, J = 7.8 Hz, H), 7.40 (td, J = 7.2 Hz, H), 7.32 (m, H), 7.14 (d, J = 7.8 Hz, H), 6.77 (d, J = 7.2 Hz, H), 4.02 (m, H), 2.80 (m, H), 2.62 (dt, J = 6.0 Hz, H), 2.55(m, H), 1.88(m, H), 1.72(m, H), 1.09 and 1.04(d, J = 6.6 Hz, 6H, CH(CH ₃ ) ₂ ), 0.82(s, 3H , HfCH ₃ ), 0.81 (s, 3H, HfCH ₃ ) ppm.

^-13 C{ ¹ H} NMR (C ₆ D ₆ ): δ 18.55, 21.28, 23.07, 25.44, 32.58, 60.98, 63.06, 66.88, 112.37, 119.64, 120.21, 124.55, 125.48, 126.81, 126.97, 129.31, 129.97, 130.26, 131.25, 133.82, 135.51, 140.97, 141.44, 143.94, 150.14, 164.58, 209.13 ppm.

-Anal. Calcd. (C ₂₇ H ₂₈ HfN ₂ ): C, 58.01; H, 5.05; N, 5.01%. Found: C, 57.91; H, 5.01; N, 5.11%.

Comparative Preparation Example 1

MeMgBr (2.60 mL, 3.11 M in diethyl ether) in a stirred solution of (tetramethylcyclopentadienyl)-1,2,3,4-tetrahydroquinoline (0.500 g, 1.97 mmol) and THF (7 mL) Was added dropwise at room temperature. The solution was stirred at 60° C. for 6 hours, and methane gas produced was simultaneously discharged. After cooling to room temperature, HfCl ₄ (0.632 g, 1.97 mmol) was added to the resulting solution. After the solution was stirred at room temperature for 12 hours, the solvent was removed using a vacuum line, and the residue was extracted with hexane (4 mL×6). Removal of the solvent gave a pure yellow solid (0.794 g, 87%).

^-1 H NMR (C ₆ D ₆ ): δ 7.05 (d, J = 7.8 Hz, 1H), 6.96 (d, J = 6.6 Hz, 1H), 6.82 (t, J = 7.2 Hz, 1H), 3.80 ( t, J = 4.8 Hz, 2H), 2.50 (t, J = 6.6 Hz, 2H), 2.00 (s, 6H), 1.78 (s, 6H), 1.62 (q, J = 6 Hz, 2H), -0.02 (s, Hf(CH ₃ ) ₂ 6H) ppm.

^-13 C{ ¹ H} NMR (C ₆ D ₆ ): δ 10.80, 22.94, 27.19, 43.31, 48.35, 116.67, 118.73, 122.10, 125.57, 129.17, 130.78, 160.69 ppm.

-Anal. Calcd. (C ₂₀ H ₂₇ HfN): C, 52.23; H, 5.92; N, 3.05%. Found: C, 52.21; H, 5.91; N, 3.08%.

Comparative Preparation Example 2

2-methyl-8-(tetramethylcyclopentadienyl)-1,2,3,4-tetrahydroquinoline (0.420 in place of (tetramethylcyclopentadienyl)-1,2,3,4-tetrahydroquinoline) g, 1.57 mmol) was prepared in the same manner as in Comparative Preparation Example 1. A yellow solid compound was obtained (0.594 g, 80%).

^-1 H NMR (C ₆ D ₆ ): δ 7.06 (d, J = 7.2 Hz, 1H), 7.00 (d, J = 7.0 Hz, 1H), 6.82 (t, J = 6.6 Hz 1H), 4.15 (m , 1H, NCH), 2.64(m, 1H), 2.47(tt, J = 5.4 Hz, 1H), 2.00(s, 6H, CH ₃ ), 1.80(s, 3H, CH ₃ ), 1.75(s, 3H , CH ₃ ), 1.48-1.56 (m, 2H), 1.32 (d, J = 6.0 Hz, 3H, NCCH ₃ ), -15.2 (s, 3H, HfCH ₃ ), -27.8 (s, 3H, HfCH ₃ ) ppm.

^-13 C{ ¹ H} NMR (C ₆ D ₆ ): δ 10.66, 10.87, 10.88, 11.01, 21.50, 23.68, 29.08, 47.40, 47.52, 49.83, 116.31, 117.70, 118.55, 121.32, 125.51, 129.28, 130.15, 130.32, 159.54 ppm.

-Anal. Calcd. (C ₂₁ H ₂₉ HfN): C, 53.22; H, 6.17; N, 2.96%. Found: C, 53.22; H, 6.14; N, 2.98%.

Comparative Preparation Example 3

8-(2,4,5-trimethyl-6H-cyclopenta[b]thiophen-6-yl)-1 in place of (tetramethylcyclopentadienyl)-1,2,3,4-tetrahydroquinoline, It was prepared in the same manner as in Comparative Preparation Example 1, except that 2,3,4-tetrahydroquinoline (0.420 g, 1.36 mmol) was used. A light brown solid compound was obtained (0.530 g, 62%). In addition, after recrystallization in hexane at -30°C to obtain a pure compound for analysis containing a single crystal suitable for X-ray crystallography, X-ray crystallography analysis was performed.

^-1 H NMR (C ₆ D ₆ ): δ 7.15 (dd, J = 6.6 Hz, 1H), 6.95 (dd, J = 7.8 Hz, 1H), 6.78 (t, J = 6.6 Hz, 1H), 6.41 ( quartet, J = 1.2 Hz, 1H, SCCH), 3.80 (m, 1H), 3.75 (m, 1H), 2.46 (t, J = 6.0 Hz, 2H), 2.20 (s, 3H, CH ₃ ), 2.10 ( d, J = 1.8 Hz, 3H, SCCH ₃ ), 1.60 (m, 2H), 0.07 (s, 3H, HfCH ₃ ), -0.29 (s, 3H, HfCH ₃ ) ppm.

^-13 C{ ¹ H} NMR (C ₆ D ₆ ): δ 11.30, 11.58, 16.21, 22.73, 27.12, 43.13, 49.72, 50.53, 106.21, 116.51, 117.20, 118.80, 122.42, 124.57, 129.77, 129.94, 134.89, 136.11, 143.96, 160.81 ppm.

-Anal. Calcd. (C ₂₁ H ₂₅ HfNS): C, 50.25; H, 5.02; N, 2.79; S, 6.39%. Found: C, 50.21; H, 5.01; N, 2.78; S, 6.39%.

Comparative Preparation Example 4

2-methyl-8-(2,4,5-trimethyl-6H-cyclopenta[b]thiophen-6-yl instead of (tetramethylcyclopentadienyl)-1,2,3,4-tetrahydroquinoline )-1,2,4-tetrahydroquinoline (0.420 g, 1.36 mmol) was prepared in the same manner as in Comparative Preparation Example 1. A light brown solid compound was obtained (0.467 g, 67%). In addition, after recrystallization in hexane at -30°C to obtain a pure compound for analysis containing a single crystal suitable for X-ray crystallography, X-ray crystallography analysis was performed.

^-1 H NMR (C ₆ D ₆ ): δ 7.17 and 7.15 (d, J = 6.3 Hz, 1H), 6.99 and 6.98 (d, J = 8.4 Hz, 1H), 6.79 (t, J = 7.8 Hz, 1H ), 6.42 and 6.38 (d, J = 1.2 Hz, 1H, SCCH), 4.21 and 4.14 (m, 1H, NCH), 2.66 and 2.63 (m, 1H), 2.44 and 2.41 (dt, J = 4.8 Hz, H ), 2.21 and 2.20(s, 3H, CH ₃ ), 2.12 and 2.11(s, 3H, SCCH ₃ ), 1.85 and 1.79(s, 3H, CH ₃ ), 1.55(m, 2H), 1.3 and 1.27(d , J = 7.2 Hz, 3H, SCCH ₃ ), 0.09 and 0.08 (s, 3H, HfCH ₃ ), -0.28 and -0.30 (s, 3H, HfCH ₃ ) ppm.

^-13 C{ ¹ H} NMR (C ₆ D ₆ ): δ 11.12, 11.41, 11.58, 11.76, 16.12, 16.23, 21.20, 21.35, 23.07, 23.54, 28.50, 28.73, 46.63, 47.07, 48.71, 49.69, 51.34, 51.71, 105.88, 107.45, 116.47, 116.59, 116.85, 118.62, 121.41, 121.65, 124.63, 129.12, 129.83, 129.92, 131.20, 134.42, 134.67, 135.29, 135.68, 143.86, 144.41 159.47, 159.61 ppm.

-Anal. Calcd. (C ₂₂ H ₂₇ HfNS): C, 51.21; H, 5.27; N, 2.71; S, 6.21%. Found: C, 50.20; H, 5.24; N, 2.73; S, 6.22%.

Comparative Production Example 5

In the same manner as in Comparative Preparation Example 1, except that fluorenyltetrahydroquinoline (0.194 g, 0.651 mmol) was used instead of (tetramethylcyclopentadienyl)-1,2,3,4-tetrahydroquinoline. Was prepared. The product was slightly soluble in hexane and extracted with toluene (2 mL × 3).

^-1 H NMR (C ₆ D ₆ ): δ 7.88 (d, J = 8.4 Hz, 2H), 7.34 (d, J = 6.6 Hz, 1H), 7.22 (d, J = 8.4 Hz, 2H), 7.01 ( t, J = 7.2 Hz, 2H), 6.94 (t, J = 8.4 Hz, 2H), 6.91 (t, J = 7.2 Hz, 1H), 3.60 (m, 2H, NCH ₂ ), 2.53 (t, J = 6.0 Hz, 2H) 1.56 (m, 2H), -0.69 (s, 6H, Hf(CH ₃ ) ₂ ) ppm.

^-13 C{ ¹ H} NMR (C ₆ D ₆ ): δ 22.51, 27.22, 42.89, 52.53, 103.54, 114.32, 118.91, 121.16, 121.84, 122.58, 123.58, 125.13, 128.60, 129.88, 130.24, 136.63, 159.98 ppm .

-Anal. Calcd. (C ₂₄ H ₂₃ HfN): C, 57.20; H, 4.60; N, 2.78%. Found: C, 57.15; H, 4.59; N, 2.79%.

Comparative Production Example 6

Except for using 2-methyl-8-(fluorenyl)tetrahydroquinoline (0.154 g, 0.494 mmol) in place of (tetramethylcyclopentadienyl)-1,2,3,4-tetrahydroquinoline, It was prepared in the same manner as in Comparative Preparation Example 1. The product was slightly soluble in hexane and extracted with toluene (2 mL × 3).

^-1 H NMR (C ₆ D ₆ ): δ 7.88 (d, J = 8.4 Hz, H), 7.86 (d, J = 8.4 Hz, H), 7.34 (d, J = 7.2 Hz, H), 7.24 ( d, J = 9.0 Hz, H), 7.18 (d, J = 8.4 Hz, H), 7.12 (d, J = 7.8 Hz, H), 7.05 (t, J = 7.8 Hz, H), 7.01 (t, J = 7.2 Hz, H), 6.93 (m, 3H), 4.01 (m, H), 2.73 (m, H), 2.48 (dt, J = 4.8 Hz, H), 1.52 (m, 2H), 1.09 ( d, J = 6.6 Hz, 3H, NCCH ₃ ), -0.68 (s, 3H, HfCH ₃ ), -0.71 (s, 3H, HfCH ₃ ) ppm.

^-13 C{ ¹ H} NMR (C ₆ D ₆ ): δ 20.78, 22.89, 28.05, 45.96, 51.32, 54.09, 103.13, 113.66, 115.63, 118.80, 120.85, 120.90, 121.48, 122.42, 122.94, 123.68, 124.86, 125.54, 128.70, 129.99, 130.30, 135.85, 136.20, 158.46 ppm.

-Anal. Calcd. (C ₂₅ H ₂₅ HfN): C, 57.97; H, 4.87; N, 2.70%. Found: C, 57.89; H, 4.79; N, 2.73%.

Structure analysis of hafnium compounds

In the above Example Preparation Example, as a [N ^amido ,N,C ^aryl ]HfMe ₂ -type compound containing a tetrahydrophenanthroline skeleton and an Hf-C (aryl) bond, each ligand compound is composed of MeMgBr and HfCl ₄ Treated with HfMe ₄ produced by the reaction, each hafnium compound was prepared.

The molecular structure of each compound was clearly identified from the X-ray crystallography data for the hafnium compounds of Preparation Examples 1 to 3, and this is shown in FIG. 6.

-Bonding distance (Å) and angle (°) of Preparation Example 1: Hf-N (1), 2.30 (2); Hf-N(2), 2.11(2); Hf-C(1), 2.27(2); Hf-C(19), 2.22(2); Hf-C(20), 2.22(2); N(1)-Hf-C(19), 137.4(7); N(1)-Hf-C(20), 118.9(7); C(19)-Hf-C(20), 103.6(9); N(2)-Hf-C(1), 140.4(8); C(14)-N(2)-Hf, 124.2(1); C(18)-N(2)-Hf, 121.3(2); C(14)-N(4)-C(18), 114.5(2); Hf-N(2)-C(18)-C(17), 29.2. (Fig. 6(a)).

-Coupling distance (Å) and angle (°) of Preparation Example 2: Hf-N (3), 2.30 (2); Hf-N(4), 2.12(2); Hf-C(25), 2.25(2); Hf-C(47), 2.20(2); Hf-C(48), 2.26(2); N(3)-Hf-C(48), 133.5(8); N(3)-Hf-C(47), 124.2(8); C(47)-Hf-C(48), 102.1(1); N(4)-Hf-C(25), 139.7(9); C(38)-N(4)-Hf, 122.0(1); C(42)-N(4)-Hf, 121.2(2); C(38)-N(4)-C(42), 116.6(2); Hf-N(4)-C(42)-C(43), 91.1; Hf-N(4)-C(42)-C(41), 38.4. (Fig. 6(b)).

-Bonding distance (Å) and angle (°) of Preparation Example 3: Hf-N (1), 2.23 (3); Hf-N(2), 2.14(3); Hf-C(1), 2.39(5); Hf-C(22), 2.28(5); Hf-C(23), 2.27(5); N(1)-Hf-C(22), 136.1(2); N(1)-Hf-C(23), 121.6(2); C(22)-Hf-C(23), 101.5(2); N(2)-Hf-C(1), 141.1(2); C(14)-N(2)-Hf, 122; C(18)-N(2)-Hf, 120; C(14)-N(2)-C(18), 115; Hf-N(2)-C(18)-C(19), 33; Hf-N(2)-C(18)-C(17), 17. (Fig. 6(c)).

As shown in the ¹ H NMR spectrum analysis result of the hafnium compound of Example 3 (a) shown in FIG. 3(a), it was clearly confirmed that the Hf-C(aryl) bond was contained in the hafnium compound. The ortho-metalated phenylene (N=CC ₆ H ₄ -Hf) signal is 8.50 (d), 7.84 (t), with an integral ratio of 1: 1: 1: 1 in the ¹ H NMR spectrum, Clearly observed at 7.46(t) and 7.26(d) ppm, and the phenyl(-C ₆ H ₅ ) signal was observed at 8.18(d), 7.52(t) and 7.45(t) ppm.

As a result of analysis of the coordination geometry, the hafnium compound could be expressed as a distorted trigonal bipyramid. Specifically, the N (pyridine), C (methyl), C (methyl) and Hf atoms form a plane so that the sum of the bonding angles around the Hf atom is 360°, whereas the C (aryl) and N (amido) atoms Was distorted and occupied the axial part, and the C(aryl)-Hf-N(amido) angle was found to be 140°.

In the hafnium compounds of Preparation Examples 1 to 3, the sum of the bonding angles around the N (amido) atoms was 360° or a similar value (360°, 360° and 357°, respectively), which means that the N atoms are N to Hf atoms. It indicates that sp ² -hybridization is being achieved for π-donation. All atoms in the ligand backbone except for the CH ₂ (i.e. NC(R)H CH ₂ ) fragment were located almost in plane with the Hf atom, whereas the C(methyl)-Hf-C(methyl) plane was the plane of the ligand backbone. The angle between the two planes was divided vertically into 87°. The butyl group of Example 2 was directed almost vertically from the plane of the ligand skeleton (Hf-N(4)-C(42)-C(43) dihedral angle, 91°), and Example 3 It was confirmed that the isopropyl group formed a plane (Hf-N(2)-C(18)-C(19) dihedral angle, 33°).

Activation reaction of hafnium compounds

(1) Preparation of cocatalyst

Excess K ⁺ [B(C ₆ F ₅ ) ₄ ] ^- (0.633 g, 0.881 mmol, pure) in toluene (anhydrous, 10 mL) [(C ₁₈ H ₃₇ ) ₂ N(H)Me] ⁺ [Cl ] ^- (0.404 g, 0.705 mmol) and reacted for 1 hour at room temperature in a glove box. After filtration over celite, the solvent was removed using a vacuum line. The residue was dissolved in methylcyclohexane (4 mL) and filtered again over Celite. Anhydride to remove the solvent as a yellow oily compound _{[(C 18 H 37) 2} N (H) Me] + [B (C 6 F 5) 4] - a was generated, which was used without further purification (0.797 g, 93 %). ¹ H NMR spectrum analysis and the results are shown in FIG. 7.

^-1 H NMR (C ₆ D ₆ ): δ 3.15 (br, H, NH), 1.97 (m, 2H, NCH ₂ ), 1.80 (m, H, NCH ₂ ), 1.51 (d, J = 6.0 Hz, 3H, NCH ₃ ), 1.45-1.29 (m, 48H), 1.26 (quintet, J = 7.2 Hz, 4H), 1.13 (quintet, J = 7.2 Hz, 4H), 0.94 (t, J = 7.8 Hz, 6H) , 0.88 (quintet, J = 7.8 Hz, 4H), 0.81 (m, 4H) ppm.

^-19 F NMR (C ₆ D ₆ ): δ -132.09, -161.75, -165.98.

(2) Reaction of hafnium compound and cocatalyst

The prepared cocatalyst [(C ₁₈ H ₃₇ ) ₂ N(H)Me] ⁺ [B(C ₆ F ₅ ) ₄ ] was reacted with the hafnium compounds of Preparation Examples and Comparative Preparation Examples to activate the hafnium compounds. ¹ H NMR spectra of the hafnium compounds of Preparation Examples 1 to 5 stabilized by reacting with the cocatalyst to form an ion pair complex are shown in FIGS. 8 to 12.

The hafnium compound of Example 3 was reacted with the cocatalyst at C ₆ D ₆ , and the resulting complex was stably present at C ₆ D ₆ for several days (FIG. 13).

Polymerization of ethylene/alpha-olefin copolymer

Example 1

The bomb reactor (125 mL) was emptied at 60° C. for 1 hour. After filling with ethylene gas at atmospheric pressure, a solution of Me ₃ Al (28.8 mg, 200 μmol-Al) in methylcyclohexane (15.5 g) was added to the reactor. The mixture was stirred at 100° C. for 1 hour using a mantle, then the solution was removed using a cannula. The reactor was emptied once again to remove residual solvent and recharged with ethylene gas at atmospheric pressure. The catalyst toxicity was purged through this procedure.

The reactor was charged with methylcyclohexane (15.5 g) containing MMAO (methylaluminoxane AkzoNobel, 6.7 wt%-Al in heptane, 20 mg, 50 μmol-Al) as a scavenger, and the temperature was set to 80°C. As a chain transfer agent, a solution of (octyl) ₂ Zn (100 μmol) in methylcyclohexane (10.0 g) was charged, and then the cocatalyst [(C ₁₈ H ₃₇ ) ₂ N(H)Me] ⁺ [B(C) in benzene ₆ F _{5) 4]} ^- was charged with (1.0 eq) was carried Preparation 3 hafnium compound (2.0μmol-Hf) methyl cyclohexane solution (0.30 g containing the activated).

An ethylene/propylene mixed gas (10 bar/10 bar, total 20 bar) was charged from the tank to the reactor at 20 bar, and polymerization was carried out for 50 minutes. The temperature was controlled within the range of 80-90°C. The remaining ethylene/propylene mixture gas was discharged and the reactor was cooled to 75°C. The resulting polymer was collected and dried in a vacuum oven at 160° C. overnight to obtain 6.3 g of an ethylene/alpha-olefin copolymer.

Examples 2 to 10, Comparative Examples 1 to 6

An ethylene/alpha-olefin copolymer was prepared in the same manner as in Example 1, except that the type of catalyst and scavenger and the content of the chain transfer agent were changed as shown in Table 1 below.

Catalyst type Type of scavenger Chain transfer agent (μmol) Example 1 Example Preparation 3 MMAO 100 Example 2 Example Preparation 3 MMAO 200 Example 3 Example Preparation 3 MMAO 300 Example 4 Example Preparation 3 MMAO 400 Example 5 Example Preparation 3 MMAO 0 Example 6 Example Preparation 3 TOA 0 Example 7 Example Preparation Example 1 TOA 0 Example 8 Example Preparation Example 2 MMAO 0 Example 9 Example Preparation Example 2 TOA 0 Example 10 Example Preparation Example 5 TOA 0 Comparative Example 1 Comparative Preparation Example 1 MMAO 0 Comparative Example 2 Comparative Preparation Example 2 MMAO 0 Comparative Example 3 Comparative Preparation Example 3 MMAO 0 Comparative Example 4 Comparative Preparation Example 4 MMAO 0 Comparative Example 5 Comparative Production Example 5 MMAO 0 Comparative Example 6 Comparative Production Example 6 MMAO 0

Experimental Example 1

The polymerization results of the ethylene/alpha-olefin copolymer were analyzed as follows.

(1) Yield (g)

The yield was calculated by measuring the weight of the ethylene/alpha-olefin copolymer prepared through the experiment.

Yield (g) Example 1 6.3 Example 2 6.6 Example 3 5.4 Example 4 3.6 Example 5 7.8 Example 6 7.5 Example 7 1.2 Example 8 5.5 Example 9 5.8 Example 10 3.5 Comparative Example 1 0 Comparative Example 2 0 Comparative Example 3 0 Comparative Example 4 0 Comparative Example 5 0 Comparative Example 6 0

When the polymerization reaction was performed using the catalyst of Comparative Preparation Example, the polymerization reaction did not occur properly in all of Comparative Examples 1 to 6, so that an ethylene/alpha-olefin copolymer could not be obtained.

On the other hand, Examples 1 to 3, which are the hafnium compounds of the present invention, exhibited excellent catalytic activity, and the activity further increased as the three-dimensional volume of the attached substituent increased. In particular, the most in Preparation Example 3 having an isopropyl substituent. High activity appeared. Example ¹ H NMR spectrum of the olefin polymer prepared in Preparation Example 3 is shown in FIG. 14.

(2) Melting temperature (Tm, ℃ )

The melting temperature of the ethylene/alpha-olefin polymer was measured using a differential scanning calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument).

Specifically, the polymer was heated to 150° C. and maintained for 5 minutes, and the temperature was lowered to -100° C. and then the temperature was increased again. At this time, the rate of rise and fall of the temperature were adjusted to 10°C/min, respectively. The melting temperature was taken as the maximum point of the endothermic peak measured in the section where the second temperature rises.

(3) Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (MWD)

Using PL-SP260, dissolve and pretreat in 1,2,4-trichlorobenzene containing 0.0125% BHT at 160°C for 3 hours, and then use PL-GPC220 to dissolve and pretreat weight average molecular weight (Mw) at 160°C. The average molecular weight (Mn) was measured respectively. Each molecular weight was measured by standardizing it with polystyrene. Using the measured Mw and Mn, the Mw value was divided by the Mn value to calculate MWD.

[C ₃ H ₆ ] (mol%) Tm(℃) Mn(×10 ³ ) Mw/Mn Example 1 9.0 100-117 58 1.8 Example 2 11 100-112 33 1.6 Example 3 13 97-110 22 1.6 Example 4 15 94-108 11 1.8 Example 5 11 102-117 190 3.4 Example 6 13 102-120 124 3.2 Example 7 10 86-129 16 11.0 Example 8 10 105-120 266 2.1 Example 9 12 101-120 87 1.5 Example 10 11 99-115 26 2.0

As shown in Table 3, the catalyst of Example Preparation Example was able to prepare the ethylene/alpha-olefin copolymer of Example by incorporating propylene into the copolymer with excellent mixing ability.

On the other hand, the number average molecular weight of the ethylene/alpha-olefin copolymer tended to increase more when using MMAO as a scavenger than when using TOA. This is thought to be because TOA is involved in the chain transfer process through transalkylation between Al and Hf centers and induces low molecular weight, and by using MMAO as a scavenger, this chain child reaction is suppressed and a high molecular weight copolymer is prepared. It was confirmed that it can be done.

In addition, it was confirmed that the hafnium compound represented by Formula 1 of the present invention can be used for CCTP when a chain transfer agent is added. Specifically, in Examples 1 to 4, a copolymerization reaction was performed by adding a chain transfer agent, and the number average molecular weight of the prepared copolymer was adjusted according to the content of the chain transfer agent and the molecular weight distribution was narrow. It was found that the polymerization was carried out successfully.

Claims (11)

Hafnium compound represented by the following Formula 1:
[Formula 1]

In Formula 1,
R ₁ to R ₁₁ are each independently hydrogen; An alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; Alkynyl group having 2 to 20 carbon atoms; A cycloalkyl group having 3 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; Arylalkoxy group having 7 to 20 carbon atoms; An alkoxy group having 1 to 20 carbon atoms; An alkylaryl group having 7 to 20 carbon atoms; An alkylsilyl group having 1 to 20 carbon atoms; Or an arylalkyl group having 7 to 20 carbon atoms,
Two or more adjacent ones of R ₁ to R ₁₁ may be connected to each other to form an aliphatic ring having 3 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms,
X ₁ and X ₂ are each independently hydrogen; halogen; Hydroxy group; Amino group; Pyo; Silyl group; Cyano group; Nitro group; An alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; Alkynyl group having 2 to 20 carbon atoms; A cycloalkyl group having 3 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; An alkylaryl group having 7 to 20 carbon atoms; Arylalkyl group having 7 to 20 carbon atoms; A heteroaryl group having 5 to 20 carbon atoms; An alkoxy group having 1 to 20 carbon atoms; Aryloxy group having 6 to 20 carbon atoms; An alkylamino group having 1 to 20 carbon atoms; Arylamino group having 6 to 20 carbon atoms; Alkylthio groups having 1 to 20 carbon atoms; Arylthio groups having 6 to 20 carbon atoms; An alkylsilyl group having 1 to 20 carbon atoms; Or it is a C6-C20 arylsilyl group.
The method according to claim 1,
R ₁ to R ₁₁ are each independently hydrogen; An alkyl group having 1 to 20 carbon atoms; A cycloalkyl group having 3 to 20 carbon atoms; Or an aryl group having 6 to 20 carbon atoms,
Two or more adjacent of R ₁ to R ₁₁ may be connected to each other to form an aromatic ring having 5 to 20 carbon atoms,
X ₁ and X ₂ are each independently hydrogen; An alkyl group having 1 to 20 carbon atoms; A cycloalkyl group having 3 to 20 carbon atoms; Or a hafnium compound which is an aryl group having 6 to 20 carbon atoms.
The method according to claim 1,
Wherein R ₁ , R ₂ , and R ₅ to R ₁₀ are hydrogen,
R ₃ , R ₄ and R ₁₁ are each independently hydrogen; Or an alkyl group having 1 to 20 carbon atoms,
The R ₃ and R ₄ may be connected to each other to form an aromatic ring having 5 to 20 carbon atoms,
X ₁ and X ₂ are each independently hydrogen; Or a hafnium compound which is an alkyl group having 1 to 20 carbon atoms.
The method according to claim 1,
The hafnium compound represented by Formula 1 is a hafnium compound represented by Formula 1a:
[Formula 1a]

In Formula 1a,
R ₁₁ is hydrogen; An alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; Alkynyl group having 2 to 20 carbon atoms; A cycloalkyl group having 3 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; Arylalkoxy group having 7 to 20 carbon atoms; An alkoxy group having 1 to 20 carbon atoms; An alkylaryl group having 7 to 20 carbon atoms; An alkylsilyl group having 1 to 20 carbon atoms; Or an arylalkyl group having 7 to 20 carbon atoms,
X ₁ and X ₂ are each independently hydrogen; halogen; Hydroxy group; Amino group; Pyo; Silyl group; Cyano group; Nitro group; An alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; Alkynyl group having 2 to 20 carbon atoms; A cycloalkyl group having 3 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; An alkylaryl group having 7 to 20 carbon atoms; Arylalkyl group having 7 to 20 carbon atoms; A heteroaryl group having 5 to 20 carbon atoms; An alkoxy group having 1 to 20 carbon atoms; Aryloxy group having 6 to 20 carbon atoms; An alkylamino group having 1 to 20 carbon atoms; Arylamino group having 6 to 20 carbon atoms; Alkylthio groups having 1 to 20 carbon atoms; Arylthio groups having 6 to 20 carbon atoms; An alkylsilyl group having 1 to 20 carbon atoms; Or it is a C6-C20 arylsilyl group.
The method according to claim 1,
The hafnium compound represented by Formula 1 is a hafnium compound represented by Formula 1b:
[Formula 1b]

In Formula 1b,
R ₁₁ is hydrogen; An alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; Alkynyl group having 2 to 20 carbon atoms; A cycloalkyl group having 3 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; Arylalkoxy group having 7 to 20 carbon atoms; An alkoxy group having 1 to 20 carbon atoms; An alkylaryl group having 7 to 20 carbon atoms; An alkylsilyl group having 1 to 20 carbon atoms; Or an arylalkyl group having 7 to 20 carbon atoms,
X ₁ and X ₂ are each independently hydrogen; halogen; Hydroxy group; Amino group; Pyo; Silyl group; Cyano group; Nitro group; An alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; Alkynyl group having 2 to 20 carbon atoms; A cycloalkyl group having 3 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; An alkylaryl group having 7 to 20 carbon atoms; Arylalkyl group having 7 to 20 carbon atoms; A heteroaryl group having 5 to 20 carbon atoms; An alkoxy group having 1 to 20 carbon atoms; Aryloxy group having 6 to 20 carbon atoms; An alkylamino group having 1 to 20 carbon atoms; Arylamino group having 6 to 20 carbon atoms; Alkylthio groups having 1 to 20 carbon atoms; Arylthio groups having 6 to 20 carbon atoms; An alkylsilyl group having 1 to 20 carbon atoms; Or it is a C6-C20 arylsilyl group.
The method according to claim 1,
The hafnium compound represented by any one of the following formulas 1-1 to 1-5.
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

A method for preparing a hafnium compound represented by Formula 1 of claim 1, comprising: reacting a compound represented by Formula 2 below and a compound represented by Formula 3 below:
[Formula 2]

[Formula 3]

In Chemical Formula 2,
R ₁ to R ₁₁ are each independently hydrogen; An alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; Alkynyl group having 2 to 20 carbon atoms; A cycloalkyl group having 3 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; Arylalkoxy group having 7 to 20 carbon atoms; An alkoxy group having 1 to 20 carbon atoms; An alkylaryl group having 7 to 20 carbon atoms; An alkylsilyl group having 1 to 20 carbon atoms; Or an arylalkyl group having 7 to 20 carbon atoms,
Two or more adjacent ones of R ₁ to R ₁₁ may be connected to each other to form an aliphatic ring having 3 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms,
In Chemical Formula 3,
X ₁ and X ₂ are each independently hydrogen; halogen; Hydroxy group; Amino group; Pyo; Silyl group; Cyano group; Nitro group; An alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; Alkynyl group having 2 to 20 carbon atoms; A cycloalkyl group having 3 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; An alkylaryl group having 7 to 20 carbon atoms; Arylalkyl group having 7 to 20 carbon atoms; A heteroaryl group having 5 to 20 carbon atoms; An alkoxy group having 1 to 20 carbon atoms; Aryloxy group having 6 to 20 carbon atoms; An alkylamino group having 1 to 20 carbon atoms; Arylamino group having 6 to 20 carbon atoms; Alkylthio groups having 1 to 20 carbon atoms; Arylthio groups having 6 to 20 carbon atoms; An alkylsilyl group having 1 to 20 carbon atoms; Or it is a C6-C20 arylsilyl group.
A catalyst composition comprising the hafnium compound of any one of claims 1 to 6 and a cocatalyst.
The method of claim 8,
The cocatalyst is one comprising at least one selected from the following formulas 4 to 6, the catalyst composition:

[Formula 4]
-[Al(R _a )-O] _m-
[Formula 5]
D(R _a ) ₃
[Formula 6]
^{[LH] + [Z (A} ) 4] - or ^{[L] + [Z (A} ) 4] -

In the above formula,
Each R _a is independently a halogen radical; A hydrocarbyl radical having 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with a halogen,
m is an integer of 2 or more,
D is aluminum or boron,
L is a neutral or cationic Lewis acid,
Z is a group 13 element,
Each A is independently aryl having 6 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent; Or alkyl having 1 to 20 carbon atoms,
The substituent of A is halogen; Hydrocarbyl having 1 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Or aryloxy having 6 to 20 carbon atoms.
The method of claim 9,
The co-catalyst comprises a formula (6), and the [Z (A) _4] contained in the formula (6) ^-bis tetrakis (phenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis [3,5- ( Trifluoromethyl) phenyl] borate and at least one selected from the group consisting of derivatives thereof, the catalyst composition.
A method for producing an olefin polymer comprising; polymerizing an olefin monomer in the presence of the catalyst composition of claim 8.

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