KR20120075937A - Metallocene compound, catalyst composition including the same, and olefin polymerization process using the same - Google Patents

Metallocene compound, catalyst composition including the same, and olefin polymerization process using the same Download PDF

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KR20120075937A
KR20120075937A KR1020100137855A KR20100137855A KR20120075937A KR 20120075937 A KR20120075937 A KR 20120075937A KR 1020100137855 A KR1020100137855 A KR 1020100137855A KR 20100137855 A KR20100137855 A KR 20100137855A KR 20120075937 A KR20120075937 A KR 20120075937A
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tetrahydroindenyl
zirconium
hafnium
titanium
methyl
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KR101269202B1 (en
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홍사문
최혜선
손병길
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대림산업 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
    • C08F4/6428—Component covered by group C08F4/64 with an organo-aluminium compound with an aluminoxane, i.e. a compound containing an Al-O-Al- group

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
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  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

PURPOSE: A metallocene compound for preparing olefin polymers or copolymers by high polymerization activity is provided to constantly maintain polymerization activity and to ensure excellent catalytic activity. CONSTITUTION: A metallocene compound is denoted by chemical formula 1((4HInd)(Cp')MX_2). A metallocenen catalytic composition contains the metallocene compound and an activator. The activator includes alkyl aluminoxane, organic aluminum compound, bulky alipathic fluorine compounds, modified clay, or Lewis acid inorganic oxide. The metallocene catalytic composition further contains metallocene compound and activator-supported organic or inorganic carriers. A method for polymerizing olefin comprises a step of polymerizing one or more olefin under the presence of the metallocene compounds.

Description

메탈로센 화합물, 이를 포함하는 촉매 조성물 및 이를 이용한 올레핀의 중합 방법{Metallocene compound, catalyst composition including the same, and olefin polymerization process using the same}Metallocene compound, catalyst composition comprising the same and polymerization method of olefin using same {Metallocene compound, catalyst composition including the same, and olefin polymerization process using the same}

본 발명은 메탈로센 화합물에 관한 것으로서, 더욱 상세하게는 높은 중합 활성으로 올레핀계 중합체 또는 공중합체를 중합할 수 있는 메탈로센 화합물, 이를 포함하는 촉매 조성물 및 이를 이용한 올레핀의 중합 방법에 관한 것이다.
The present invention relates to a metallocene compound, and more particularly, to a metallocene compound capable of polymerizing an olefin polymer or copolymer with high polymerization activity, a catalyst composition comprising the same, and a polymerization method of an olefin using the same. .

올레핀의 중합에는 전이금속을 포함하는 촉매가 일반적으로 사용되고 있다. 예를 들면, 독일특허 제2,608,933호, 제3,007,725호 등은 지르코늄, 티타늄, 하프늄 등 주기율표 4B족 전이금속과 싸이클로펜타디엔계 리간드로 이루어진 메탈로센 화합물을 메틸알루미녹산 등의 활성체와 함께 올레핀 중합용 촉매로 사용하는 것을 개시하고 있다. 이러한 공지 기술들에 개시된 싸이클로펜타디엔계 리간드 화합물의 예로는 치환 또는 비치환된 싸이클로펜타디엔(cyclopentadiene), 인덴(indene), 플루오레닐(fluorene) 등이 있다. 많은 종류의 싸이클로펜타디엔계 메탈로센 화합물이 올레핀 중합 촉매로서 사용될 수 있는데, 싸이클로펜타디엔계 메탈로센의 화학적 구조가 중합촉매로서 메탈로센의 적합성에 중요한 영향을 미치는 것으로 알려져 있다. 예를 들어, 싸이클로펜타디에닐 환(ring)에 결합된 치환체의 크기와 위치는 촉매의 활성, 촉매의 입체특이성, 촉매의 안전성, 중합 반응으로 얻어지는 중합체의 물성 등에 큰 영향을 준다. 하이드로카빌기로 치환된 싸이클로펜타디에닐 리간드와 지르코늄으로 이루어진 메탈로센 화합물의 예로는 비스(알킬싸이클로펜타디에닐)지르코늄 디클로라이드(여기서, 알킬은 메틸, 에틸, 이소프로필, tert-프로필 또는 트리메틸실릴이다)(J. Chem. Soc. Dalton Trans., 805(1981)), 비스(펜타메틸싸이클로펜타디에닐)지르코늄 디클로라이드(J. Amer. Chem. Soc., 100, 3078 (1978)), (펜타메틸싸이클로펜타디에닐)(싸이클로펜타디에닐)지르코늄 디클로라이드(J. Amer. Chem. Soc., 106, 6355 (1984)), 비스(디, 트리, 또는 테트라 알킬-싸이클로펜타디에닐)지르코늄 디클로라이드(미국특허 제4,874,880호) 등이 알려져 있고, 그 외에도 치환된 인데닐 리간드를 포함하는 비가교성 메탈로센(미국특허 제5,780,659호), 단일 알킬 치환체를 갖는 싸이클로펜타디에닐 리간드로 이루어진 메탈로센(독일특허 제4,312,270호) 등이 알려져 있다.
For the polymerization of olefins, catalysts containing transition metals are generally used. For example, German Patent Nos. 2,608,933 and 3,007,725 disclose olefin polymerization of metallocene compounds composed of periodic table 4B transition metals such as zirconium, titanium, hafnium and cyclopentadiene ligands with an active agent such as methylaluminoxane. It is disclosed to use as a catalyst for the. Examples of cyclopentadiene-based ligand compounds disclosed in these known techniques include substituted or unsubstituted cyclopentadiene, indene, fluorene, and the like. Many types of cyclopentadiene-based metallocene compounds can be used as the olefin polymerization catalyst, and the chemical structure of the cyclopentadiene-based metallocene is known to have an important effect on the suitability of the metallocene as a polymerization catalyst. For example, the size and position of the substituents bonded to the cyclopentadienyl ring have a great influence on the activity of the catalyst, stereospecificity of the catalyst, safety of the catalyst, and physical properties of the polymer obtained by the polymerization reaction. Examples of metallocene compounds consisting of zirconium and cyclopentadienyl ligands substituted with hydrocarbyl groups include bis (alkylcyclopentadienyl) zirconium dichloride, wherein alkyl is methyl, ethyl, isopropyl, tert-propyl or trimethyl Silyl) (J. Chem. Soc. Dalton Trans., 805 (1981)), bis (pentamethylcyclopentadienyl) zirconium dichloride (J. Amer. Chem. Soc., 100, 3078 (1978)), (Pentamethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride (J. Amer. Chem. Soc., 106, 6355 (1984)), bis (di, tri, or tetra alkyl-cyclopentadienyl) Zirconium dichloride (US Pat. No. 4,874,880) and the like are known, in addition to non-crosslinked metallocenes comprising substituted indenyl ligands (US Pat. No. 5,780,659), consisting of cyclopentadienyl ligands having a single alkyl substituent Metallocene ( One patent has been known, such as the No. 4.31227 million)

최근에는, 전이금속으로서 지르코늄을 포함하는 치환된 싸이클로펜타디엔계 메탈로센과 메틸알루미녹산으로 이루어진 촉매 시스템(조성물)이 올레핀 중합 활성이 우수하다는 것이 밝혀졌다(유럽특허 제129,368호, 미국특허 제4,874,880호, 제5,324,800호, Makromol. Chem. Rapid Commun., 4, 417(1983) 등 참조). 또한, 배위자로서 알킬기 및/또는 할로겐원자를 갖는 메탈로센 화합물과 알루미녹산을 조합한 촉매 시스템들이 α-올레핀의 중합시 활성이 높은 것으로 알려져 있으며, 메탈로센 화합물과 유기보론 화합물을 조합한 촉매계도 α-올레핀의 중합에 있어서 활성이 우수한 것으로 알려져 있다(Macromolecules 1993, 26, 3239; J, Am, chem. Soc. 1991, 113, 3623).
Recently, it has been found that a catalyst system (composition) composed of substituted cyclopentadiene-based metallocenes containing zirconium and methylaluminoxane as transition metals has excellent olefin polymerization activity (European Patent No. 129,368, US Patent No. 4,874,880). No. 5,324,800, Makromol.Chem.Rapid Commun., 4, 417 (1983) and the like). In addition, catalyst systems in which metallocene compounds having an alkyl group and / or halogen atoms as a ligand and aluminoxane are known to have high activity in polymerization of α-olefins, and catalyst systems in which metallocene compounds and organic boron compounds are combined In addition, it is known that the activity is excellent in the polymerization of the α-olefin (Macromolecules 1993, 26, 3239; J, Am, chem. Soc. 1991, 113, 3623).

또한, 일반적으로 알루미녹산 또는 유기보론 화합물과 메탈로센 화합물을 조합한 촉매계는 60 내지 90℃의 중합온도에서 중합 활성도가 가장 높은 것으로 알려져 있다. 그러나, 이러한 높은 온도에서, 촉매의 초기 활성은 높지만, 많은 촉매들이 고온 안정성이 취약하여, 중합시간 경과에 따라 활성이 점점 감소되어 생산성이 떨어질 뿐만 아니라, 그로 인해 폴리머의 물성도 악화되고, 생성된 중합체로 많은 종류의 제품을 성형하기 곤란하다. 중합온도를 낮추면 중합체의 분자량을 증가시킬 수 있지만, 촉매 활성이 저하되어, 충분한 중합 활성도를 얻을 수 없다.
In general, a catalyst system combining aluminoxane or an organoboron compound and a metallocene compound is known to have the highest polymerization activity at a polymerization temperature of 60 to 90 ° C. However, at such high temperatures, although the initial activity of the catalyst is high, many catalysts are poor in high temperature stability, so that the activity decreases gradually with polymerization time, resulting in poor productivity, resulting in deterioration of the physical properties of the polymer, It is difficult to mold many kinds of products with polymers. When the polymerization temperature is lowered, the molecular weight of the polymer can be increased, but the catalytic activity is lowered, and sufficient polymerization activity cannot be obtained.

이와 같은 문제점을 해결하고자 연구를 수행하는 중에, 본 발명자들은, 종래 공지되지 않은 중합 활성이 우수한 메탈로센 화합물을 발견하였고, 이 화합물을 이용하여 올레핀 중합용 촉매 시스템을 구성하고, 올레핀을 중합하여 폴레올레핀을 제조하는 방법을 개발하게 되었다.While conducting research to solve such a problem, the present inventors found a metallocene compound having excellent polymerization activity, which is not known in the prior art, and used this compound to construct a catalyst system for olefin polymerization, and polymerize olefin. A method for preparing polyolefins has been developed.

따라서, 본 발명의 목적은, 높은 중합 온도에서도 중합 활성도 및 안정성이 우수하고, 시간의 경과에 따른 촉매 활성 감소와 폴리머의 물성 변화가 적은 올레핀 중합용 메탈로센 화합물을 제공하는 것이다.Accordingly, an object of the present invention is to provide a metallocene compound for olefin polymerization, which is excellent in polymerization activity and stability even at a high polymerization temperature, and decreases in catalyst activity over time and changes in physical properties of the polymer.

본 발명의 다른 목적은, 다양한 특성을 가지며, 중합체 몰포로지(morphology) 가 우수한 폴리올레핀을 중합할 수 있는 올레핀 중합용 메탈로센 화합물을 제공하는 것이다.Another object of the present invention is to provide a metallocene compound for olefin polymerization capable of polymerizing polyolefin having various properties and excellent polymer morphology.

본 발명의 또 다른 목적은 균일상(용액중합) 또는 불균일상(기상 또는 슬러리 중합)에서 중합체의 분자량을 용이하게 조절할 수 있는 올레핀 중합용 메탈로센 화합물, 이를 포함하는 촉매 조성물 및 이를 이용한 올레핀의 중합 방법을 제공하는 것이다.
Still another object of the present invention is to provide a metallocene compound for olefin polymerization capable of easily controlling the molecular weight of a polymer in a homogeneous phase (solution polymerization) or a heterogeneous phase (gas phase or slurry polymerization), a catalyst composition comprising the same, and an olefin using the same. It is to provide a polymerization method.

상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 1로 표시되는 올레핀 중합용 메탈로센 화합물을 제공한다.In order to achieve the above object, the present invention provides a metallocene compound for olefin polymerization represented by the following formula (1).

[화학식 1]  [Formula 1]

(4HInd)(Cp')MX2 (4HInd) (Cp ') MX 2

여기서, 4HInd는 테트라하이드로인데닐 핵을 가진 기이며, Cp'는 싸이클로펜타디에닐 핵을 가진 기이고, 4HInd와 Cp'는 비치환되거나 하나 이상의 치환체를 가질 수 있으며, 상기 치환체는 서로 동일하거나 다를 수 있고, 탄소수 1 내지 20의 알킬, 알콕시, 알킬실릴(alkylsilyl), 알킬실록시, 알킬아미노 또는 할로알킬, 탄소수 3 내지 20의 싸이클로알킬, 탄소수 6 내지 20의 아릴, 아릴알킬, 아릴실릴, 알킬아릴 또는 아릴옥시, 탄소수 2 내지 20의 디알킬아미노, 할로겐 원자 및 아미노기로 이루어진 군으로부터 선택되는 라디칼이고, M은 주기율표의 IVB, VB 또는 VIB족 전이금속이고, X는 동일하거나 다를 수 있으며, 할로겐, 탄소수 1 내지 20의 알킬 또는 알콕시, 탄소수 2 내지 20의 알케닐 및 탄소수 6 내지 20의 아릴, 알킬아릴, 아릴알킬 또는 아릴옥시 라디칼로 이루어진 군으로부터 선택되는 1종이다. Here, 4HInd is a group having a tetrahydroindenyl nucleus, Cp 'is a group having a cyclopentadienyl nucleus, 4HInd and Cp' may be unsubstituted or have one or more substituents, and the substituents are the same or different from each other. Alkyl, alkoxy, alkylsilyl, alkylsiloxy, alkylamino or haloalkyl, cycloalkyl having 3 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, arylalkyl, arylsilyl, alkyl Aryl or aryloxy, a radical selected from the group consisting of dialkylamino having 2 to 20 carbon atoms, a halogen atom and an amino group, M is a IVB, VB or VIB transition metal of the periodic table, X may be the same or different, halogen , Alkyl or alkoxy having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms and aryl, alkylaryl, arylalkyl or aryloxy radical having 6 to 20 carbon atoms. Is one member selected from the group.

또한, 본 발명은, 상기 메탈로센 화합물 및 활성체로 이루어지거나, 상기 메탈로센 화합물 및 활성체를 유기 또는 무기 담체(캐리어, carrier)에 담지시킨 올레핀 중합용 촉매 조성물을 제공한다. 또한, 본 발명은, 상기 메탈로센 화합물의 존재 하에서, 하나 이상의 올레핀을 중합하는 단계를 포함하는 올레핀의 중합방법을 제공한다.
The present invention also provides a catalyst composition for olefin polymerization comprising the metallocene compound and the activator or supporting the metallocene compound and the activator on an organic or inorganic carrier (carrier, carrier). In addition, the present invention provides a polymerization method of olefins comprising the step of polymerizing at least one olefin in the presence of the metallocene compound.

본 발명에 따른 올레핀 중합용 촉매 조성물은, 중합 시간이 경과함에 따라 중합 활성이 감소하는 종래의 올레핀 중합 촉매와 달리, 촉매 활성이 우수하면서도, 중합 활성이 일정하게 유지되는 특성을 나타내므로, 폴리올레핀의 제조에 있어서 매우 높은 상업적 생산성을 확보할 수 있다. 또한, 본 발명에 따른 메탈로센 화합물을 다양하게 선택함으로써, 균일상(용액중합) 또는 불균일상(기상 또는 슬러리 중합)에서 다양한 특성의 올레핀 중합체 또는 공중합체를 제조할 수 있을 뿐만 아니라, 중합체의 분자량, 분자량 분포 및 조성 분포를 용이하게 조절할 수 있다.
The catalyst composition for olefin polymerization according to the present invention, unlike the conventional olefin polymerization catalysts in which the polymerization activity decreases as the polymerization time elapses, exhibits excellent catalytic activity and maintains constant polymerization activity. Very high commercial productivity can be ensured in manufacturing. In addition, by variously selecting the metallocene compound according to the present invention, it is possible not only to prepare olefin polymers or copolymers of various characteristics in a homogeneous phase (solution polymerization) or a heterogeneous phase (gas phase or slurry polymerization), but also Molecular weight, molecular weight distribution and composition distribution can be easily adjusted.

이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

본 발명에 따른 메탈로센 화합물은 테트라하이드로인데닐 핵을 가진 리간드 (4HInd), 싸이클로펜타디에닐 핵을 가진 리간드(Cp') 및 상기 리간드들이 결합된 전이금속(M)을 포함하는 올레핀 중합용 촉매로서, 하기 화학식 1로 표현된다.The metallocene compound according to the present invention is used for olefin polymerization including a ligand having a tetrahydroindenyl nucleus (4HInd), a ligand having a cyclopentadienyl nucleus (Cp '), and a transition metal (M) to which the ligands are bound. As a catalyst, it is represented by following General formula (1).

[화학식 1][Formula 1]

(4HInd)(Cp')MX2 (4HInd) (Cp ') MX 2

상기 화학식 1에서, 4HInd는 테트라하이드로인데닐 핵을 가진 기, 예를 들면 4,5,6,7-테트라하이드로인데닐 핵을 가진 기이며, Cp'는 싸이클로펜타디에닐 핵을 가진 기로서, 바람직하게는, 싸이클로펜타디에닐, 인데닐(indenyl), 플루오레닐(fluorenyl), 아줄레닐(azulenyl) 등의 싸이클로펜타디에닐 핵을 가진 기이다. 4HInd와 Cp'는 비치환되거나 하나 이상의 치환체를 가질 수 있고, 구체적으로, 4HInd는 1 내지 11개의 치환체로 부분 치환될 수 있으며, Cp'은 하나 이상, 예를 들면 1 내지 5개의 치환체로 부분 치환될 수 있다. 상기 치환체는 서로 동일하거나 다를 수 있으며, 탄소수 1 내지 20의 알킬, 알콕시, 알킬실릴(alkylsilyl), 알킬실록시, 알킬아미노 또는 할로알킬, 탄소수 3 내지 20의 싸이클로알킬, 탄소수 6 내지 20의 아릴, 아릴알킬, 아릴실릴, 알킬아릴 또는 아릴옥시, 탄소수 2 내지 20의 디알킬아미노, 할로겐 원자 및 아미노기로 이루어진 군으로부터 선택되는 라디칼이고, M은 주기율표의 IVB, VB 또는 VIB족 전이금속으로서, 바람직하게는 IVB 족의 티타늄, 지르코늄 및 하프늄으로 이루어진 군으로부터 선택되는 1종이상의 전이금속며, X는 동일하거나 다를 수 있으며, 불소, 염소, 브롬, 요오드 등으로 이루어진 군으로부터 선택되는 할로겐 원자, 탄소수 1 내지 20의 알킬 또는 알콕시, 탄소수 2 내지 20의 알케닐 및 탄소수 6 내지 20의 아릴, 알킬아릴, 아릴알킬 또는 아릴옥시 라디칼로 이루어진 군으로부터 선택되는 1종이다.
In Formula 1, 4HInd is a group having a tetrahydroindenyl nucleus, for example, a group having a 4,5,6,7-tetrahydroindenyl nucleus, and Cp 'is a group having a cyclopentadienyl nucleus. Preferably, the group has a cyclopentadienyl nucleus such as cyclopentadienyl, indenyl, fluorenyl, azulenyl, and the like. 4HInd and Cp 'may be unsubstituted or have one or more substituents, specifically, 4HInd may be partially substituted with 1 to 11 substituents, and Cp' may be partially substituted with one or more, for example, 1 to 5 substituents. Can be. The substituents may be the same or different from each other, alkyl having 1 to 20 carbon atoms, alkoxy, alkylsilyl, alkylsiloxy, alkylamino or haloalkyl, cycloalkyl having 3 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, Arylalkyl, arylsilyl, alkylaryl or aryloxy, a radical selected from the group consisting of dialkylamino having 2 to 20 carbon atoms, a halogen atom and an amino group, M is a transition metal of Group IVB, VB or VIB of the periodic table, preferably Is at least one transition metal selected from the group consisting of titanium, zirconium, and hafnium of the IVB group, X may be the same or different, and a halogen atom selected from the group consisting of fluorine, chlorine, bromine, iodine, etc. 20 alkyl or alkoxy, alkenyl having 2 to 20 carbon atoms and aryl having 6 to 20 carbon atoms, alkylaryl, arylalkyl or aryloxy D is one member selected from the group consisting of a knife.

상기 화학식 1로 표시되는 메탈로센 화합물은 단독 또는 2종 이상 혼합되어 사용될 수 있으며, 상기 메탈로센 화합물의 비한정적인 예로는 이하의 화합물을 예시할 수 있다. The metallocene compound represented by Chemical Formula 1 may be used alone or in mixture of two or more thereof. Non-limiting examples of the metallocene compound may include the following compounds.

(4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디아이오다이드, (4,5,6,7-tetrahydroindenyl) (indenyl) titanium dichloride, (4,5,6,7-tetrahydroindenyl) (indenyl) zirconium dichloride, (4,5,6 , 7-tetrahydroindenyl) (indenyl) hafnium dichloride, (4,5,6,7-tetrahydroindenyl) (indenyl) titanium difluoride, (4,5,6,7-tetrahydro Indenyl) (indenyl) zirconium difluoride, (4,5,6,7-tetrahydroindenyl) (indenyl) hafnium difluoride, (4,5,6,7-tetrahydroindenyl) ( Indenyl) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (indenyl) zirconium dibromide, (4,5,6,7-tetrahydroindenyl) (indenyl) hafnium dibromide , (4,5,6,7-tetrahydroindenyl) (indenyl) titanium diiodide, (4,5,6,7-tetrahydroindenyl) (indenyl) zirconium diiodide, (4, 5,6,7-tetrahydroindenyl) (indenyl) hafnium diiodide ,

(1-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디아이오다이드,(1-methyl-4,5,6,7-tetrahydroindenyl) (indenyl) titanium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium di Chloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (indenyl) Titanium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (Indenyl) hafnium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (indenyl) titanium dibromide, (1-methyl-4,5,6,7-tetrahydro Indenyl) (indenyl) zirconium dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium dibromide, (1-methyl-4,5,6,7- Tetrahydroindenyl) (indenyl) titanium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium dia Iodide, (1-methyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium diiodide,

(4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디클로라이드, (4,5,6,7-테트라하이드로-인데닐)(1-메틸인데닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디아이오다이드, (4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium dichloride, (4,5,6,7-tetrahydro-indenyl) (1-methylindenyl) zirconium dichloride , (4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium dichloride, (4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium difluor Ride, (4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium difluoride, (4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium Difluoride, (4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (1-methylindenyl) Zirconium Dibromide, (4,5,6,7-tetrahydroindenyl) (1-methylindenyl) Halfnium Dibromide, (4,5,6,7-tetrahydroindenyl) (1-methylindenyl) Titanium Diiodide, (4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium diioda De, (4,5,6,7-inde tetrahydroindenyl) (1-methyl-inde carbonyl) DI hafnium iodide,

(2-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디클로라이드, (2-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디클로라이드, (2-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디클로라이드, (2-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디플루오라이드, (2-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디플루오라이드, (2-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디플루오라이드, (2-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디브로마이드, (2-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디브로마이드, (2-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디브로마이드, (2-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디아이오다이드, (2-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디아이오다이드, (2-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(2-메틸인데닐)티타늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(2-메틸 인데닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(2-메틸인데닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(2-메틸인데닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(2-메틸인데닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(2-메틸인데닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(2-메틸인데닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(2-메틸인데닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(2-메틸인데닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(2-메틸인데닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(2-메틸인데닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(2-메틸인데닐)하프늄 디아이오다이드,(2-methyl-4,5,6,7-tetrahydroindenyl) (indenyl) titanium dichloride, (2-methyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium di Chloride, (2-methyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium dichloride, (2-methyl-4,5,6,7-tetrahydroindenyl) (indenyl) Titanium difluoride, (2-methyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium difluoride, (2-methyl-4,5,6,7-tetrahydroindenyl) (Indenyl) hafnium difluoride, (2-methyl-4,5,6,7-tetrahydroindenyl) (indenyl) titanium dibromide, (2-methyl-4,5,6,7-tetrahydro Indenyl) (indenyl) zirconium dibromide, (2-methyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium dibromide, (2-methyl-4,5,6,7- Tetrahydroindenyl) (indenyl) titanium diiodide, (2-methyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium dia Iodide, (2-methyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium diiodide, (4,5,6,7-tetrahydroindenyl) (2-methylde Nil) titanium dichloride, (4,5,6,7-tetrahydroindenyl) (2-methyl indenyl) zirconium dichloride, (4,5,6,7-tetrahydroindenyl) (2-methylde Nil) hafnium dichloride, (4,5,6,7-tetrahydroindenyl) (2-methylindenyl) titanium difluoride, (4,5,6,7-tetrahydroindenyl) (2-methyl Indenyl) zirconium difluoride, (4,5,6,7-tetrahydroindenyl) (2-methylindenyl) hafnium difluoride, (4,5,6,7-tetrahydroindenyl) (2 -Methylindenyl) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (2-methylindenyl) zirconium dibromide, (4,5,6,7-tetrahydroindenyl) (2 -Methylindenyl) hafnium dibromide, (4,5,6,7-tetrahydroindenyl) (2-methylindenyl) titanium Iodide, (4,5,6,7-tetrahydroindenyl) (2-methylindenyl) zirconium diiodide, (4,5,6,7-tetrahydroindenyl) (2-methylindenyl Hafnium diiodide,

(1-에틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디클로라이드, (1-에틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디클로라이드, (1-에틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디플루오라이드, (1-에틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디플루오라이드, (1-에틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디플루오라이드, (1-에틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디브로마이드, (1-에틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디브로마이드, (1-에틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디브로마이드, (1-에틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디아이오다이드, (1-에틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디아이오다이드, (1-에틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(1-에틸인데닐)티타늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1-에틸인데닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1-에틸인데닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1-에틸인데닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-에틸인데닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-에틸인데닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-에틸인데닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-에틸인데닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-에틸인데닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-에틸인데닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(1-에틸인데닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(1-에틸인데닐)하프늄 디아이오다이드, (2-에틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디클로라이드, (2-에틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디클로라이드, (2-에틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디클로라이드, (2-에틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디플루오라이드, (2-에틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디플루오라이드, (2-에틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디플루오라이드, (2-에틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디브로마이드, (2-에틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디브로마이드, (2-에틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디브로마이드, (2-에틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디아이오다이드, (2-에틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디아이오다이드, (2-에틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(2-에틸인데닐)티타늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(2-에틸 인데닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(2-에틸인데닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(2-에틸인데닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(2-에틸인데닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(2-에틸인데닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(2-에틸인데닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(2-에틸인데닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(2-에틸인데닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(2-에틸인데닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(2-에틸인데닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(2-에틸인데닐)하프늄 디아이오다이드, (1-ethyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium dichloride, (1-ethyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium di Chloride, (1-ethyl-4,5,6,7-tetrahydroindenyl) (indenyl) titanium difluoride, (1-ethyl-4,5,6,7-tetrahydroindenyl) (indenyl ) Zirconium difluoride, (1-ethyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium difluoride, (1-ethyl-4,5,6,7-tetrahydroindenyl ) (Indenyl) titanium dibromide, (1-ethyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium dibromide, (1-ethyl-4,5,6,7-tetrahydro Indenyl) (indenyl) hafnium dibromide, (1-ethyl-4,5,6,7-tetrahydroindenyl) (indenyl) titanium diiodide, (1-ethyl-4,5,6,7 Tetrahydroindenyl) (indenyl) zirconium diiodide, (1-ethyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium di Iodide, (4,5,6,7-tetrahydroindenyl) (1-ethylindenyl) titanium dichloride, (4,5,6,7-tetrahydroindenyl) (1-ethylindenyl) Zirconium Dichloride, (4,5,6,7-tetrahydroindenyl) (1-ethylindenyl) hafnium Dichloride, (4,5,6,7-tetrahydroindenyl) (1-ethylindenyl) Titanium difluoride, (4,5,6,7-tetrahydroindenyl) (1-ethylindenyl) zirconium difluoride, (4,5,6,7-tetrahydroindenyl) (1-ethylde Nil) hafnium difluoride, (4,5,6,7-tetrahydroindenyl) (1-ethylindenyl) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (1-ethyl Indenyl) zirconium dibromide, (4,5,6,7-tetrahydroindenyl) (1-ethylindenyl) hafnium dibromide, (4,5,6,7-tetrahydroindenyl) (1-ethyl Indenyl) titanium diiodide, (4,5,6,7-tetrahydroindenyl) (1-ethylindenyl) zirco Diiodide, (4,5,6,7-tetrahydroindenyl) (1-ethylindenyl) hafnium diiodide, (2-ethyl-4,5,6,7-tetrahydroindenyl) Nil) titanium dichloride, (2-ethyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium dichloride, (2-ethyl-4,5,6,7-tetrahydroindenyl) (Indenyl) hafnium dichloride, (2-ethyl-4,5,6,7-tetrahydroindenyl) (indenyl) titanium difluoride, (2-ethyl-4,5,6,7-tetrahydro Indenyl) (indenyl) zirconium difluoride, (2-ethyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium difluoride, (2-ethyl-4,5,6, 7-tetrahydroindenyl) (indenyl) titanium dibromide, (2-ethyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium dibromide, (2-ethyl-4,5, 6,7-tetrahydroindenyl) (indenyl) hafnium dibromide, (2-ethyl-4,5,6,7-tetrahydroindenyl) (phosphorus Nil) titanium diiodide, (2-ethyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium diiodide, (2-ethyl-4,5,6,7-tetrahydroinde Nil) (indenyl) hafnium diiodide, (4,5,6,7-tetrahydroindenyl) (2-ethylindenyl) titanium dichloride, (4,5,6,7-tetrahydroindenyl) (2-ethyl indenyl) zirconium dichloride, (4,5,6,7-tetrahydroindenyl) (2-ethylindenyl) hafnium dichloride, (4,5,6,7-tetrahydroindenyl) (2-ethylindenyl) titanium difluoride, (4,5,6,7-tetrahydroindenyl) (2-ethylindenyl) zirconium difluoride, (4,5,6,7-tetrahydroinde Nil) (2-ethylindenyl) hafnium difluoride, (4,5,6,7-tetrahydroindenyl) (2-ethylindenyl) titanium dibromide, (4,5,6,7-tetrahydro Indenyl) (2-ethylindenyl) zirconium dibromide, (4,5,6,7-tetrahydroindenyl) ( 2-ethylindenyl) hafnium dibromide, (4,5,6,7-tetrahydroindenyl) (2-ethylindenyl) titanium diiodide, (4,5,6,7-tetrahydroindenyl) (2-ethylindenyl) zirconium diiodide, (4,5,6,7-tetrahydroindenyl) (2-ethylindenyl) hafnium diiodide,

(1-프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디클로라이드, (1-프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디클로라이드, (1-프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디플루오라이드, (1-프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디플루오라이드, (1-프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디플루오라이드, (1-프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디브로마이드, (1-프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디브로마이드, (1-프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디브로마이드, (1-프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디아이오다이드, (1-프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디아이오다이드, (1-프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(1-프로필인데닐)티타늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1-프로필인데닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1- 프로필인데닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1-프로필인데닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-프로필인데닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-프로필인데닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-프로필인데닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-프로필인데닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-프로필인데닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-프로필인데닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(1-프로필인데닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(1-프로필인데닐)하프늄 디아이오다이드, (2-프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디클로라이드, (2-프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디클로라이드, (2-프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디클로라이드, (2-프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디플루오라이드, (2-프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디플루오라이드, (2-프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디플루오라이드, (2-프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디브로마이드, (2-프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디브로마이드, (2-프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디브로마이드, (2-프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디아이오다이드, (2-프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디아이오다이드, (2-프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(2-프로필인데닐)티타늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(2-프로필인데닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(2-프로필인데닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(2-프로필인데닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(2-프로필인데닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(2-프로필인데닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(2-프로필인데닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(2-프로필인데닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(2-프로필인데닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(2-프로필인데닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(2-프로필인데닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(2-프로필인데닐)하프늄 디아이오다이드, (1-propyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium dichloride, (1-propyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium di Chloride, (1-propyl-4,5,6,7-tetrahydroindenyl) (indenyl) titanium difluoride, (1-propyl-4,5,6,7-tetrahydroindenyl) (indenyl ) Zirconium difluoride, (1-propyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium difluoride, (1-propyl-4,5,6,7-tetrahydroindenyl ) (Indenyl) titanium dibromide, (1-propyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium dibromide, (1-propyl-4,5,6,7-tetrahydro Indenyl) (indenyl) hafnium dibromide, (1-propyl-4,5,6,7-tetrahydroindenyl) (indenyl) titanium diiodide, (1-propyl-4,5,6,7 Tetrahydroindenyl) (indenyl) zirconium diiodide, (1-propyl-4,5,6,7-tetrahydro Denyl) (indenyl) hafnium diiodide, (4,5,6,7-tetrahydroindenyl) (1-propylindenyl) titanium dichloride, (4,5,6,7-tetrahydroindenyl) (1-propylindenyl) zirconium dichloride, (4,5,6,7-tetrahydroindenyl) (1-propylindenyl) hafnium dichloride, (4,5,6,7-tetrahydroindenyl) (1-propylindenyl) titanium difluoride, (4,5,6,7-tetrahydroindenyl) (1-propylindenyl) zirconium difluoride, (4,5,6,7-tetrahydroinde Nil) (1-propylindenyl) hafnium difluoride, (4,5,6,7-tetrahydroindenyl) (1-propylindenyl) titanium dibromide, (4,5,6,7-tetrahydro Indenyl) (1-propylindenyl) zirconium dibromide, (4,5,6,7-tetrahydroindenyl) (1-propylindenyl) hafnium dibromide, (4,5,6,7-tetrahydro Indenyl) (1-propylindenyl) titanium diiodide, (4,5, 6,7-tetrahydroindenyl) (1-propylindenyl) zirconium diiodide, (4,5,6,7-tetrahydroindenyl) (1-propylindenyl) hafnium diiodide, (2- Propyl-4,5,6,7-tetrahydroindenyl) (indenyl) titanium dichloride, (2-propyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium dichloride, ( 2-propyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium dichloride, (2-propyl-4,5,6,7-tetrahydroindenyl) (indenyl) titanium difluor Ride, (2-propyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium difluoride, (2-propyl-4,5,6,7-tetrahydroindenyl) (indenyl ) Hafnium difluoride, (2-propyl-4,5,6,7-tetrahydroindenyl) (indenyl) titanium dibromide, (2-propyl-4,5,6,7-tetrahydroindenyl) (Indenyl) zirconium dibromide, (2-propyl-4,5,6,7-tetrahydro ) (Indenyl) hafnium dibromide, (2-propyl-4,5,6,7-tetrahydroindenyl) (indenyl) titanium diiodide, (2-propyl-4,5,6,7-tetra Hydroindenyl) (indenyl) zirconium diiodide, (2-propyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium diiodide, (4,5,6,7-tetra Hydroindenyl) (2-propylinyl) titanium dichloride, (4,5,6,7-tetrahydroindenyl) (2-propylinyl) zirconium dichloride, (4,5,6,7-tetra Hydroindenyl) (2-propylinyl) hafnium dichloride, (4,5,6,7-tetrahydroindenyl) (2-propylinyl) titanium difluoride, (4,5,6,7- Tetrahydroindenyl) (2-propylinyl) zirconium difluoride, (4,5,6,7-tetrahydroindenyl) (2-propylindenyl) hafnium difluoride, (4,5,6, 7-tetrahydroindenyl) (2-propylindenyl) titanium dibromide, (4,5,6, 7-tetrahydroindenyl) (2-propylindenyl) zirconium dibromide, (4,5,6,7-tetrahydroindenyl) (2-propylindenyl) hafnium dibromide, (4,5,6, 7-tetrahydroindenyl) (2-propylindenyl) titanium diiodide, (4,5,6,7-tetrahydroindenyl) (2-propylindenyl) zirconium diiodide, (4,5, 6,7-tetrahydroindenyl) (2-propylindenyl) hafnium diiodide,

(1-이소프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디클로라이드, (1-이소프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디클로라이드, (1-이소프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디플루오라이드, (1-이소프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디플루오라이드, (1-이소프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디플루오라이드, (1-이소프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디브로마이드, (1-이소프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디브로마이드, (1-이소프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디브로마이드, (1-이소프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디아이오다이드, (1-이소프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디아이오다이드, (1-이소프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(1-이소프로필인데닐)티타늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1-이소프로필인데닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1-이소프로필인데닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1-이소프로필인데닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-이소프로필인데닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-이소프로필인데닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-이소프로필인데닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-이소프로필인데닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-이소프로필인데닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-이소프로필인데닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(1-이소프로필인데닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(1-이소프로필인데닐)하프늄 디아이오다이드, (2-이소프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디클로라이드, (2-이소프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디클로라이드, (2-이소프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디클로라이드, (2-이소프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디플루오라이드, (2-이소프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디플루오라이드, (2-이소프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디플루오라이드, (2-이소프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디브로마이드, (2-이소프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디브로마이드, (2-이소프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디브로마이드, (2-이소프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디아이오다이드, (2-이소프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디아이오다이드, (2-이소프로필-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(2-이소프로필인데닐)티타늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(2-이소프로필인데닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(2-이소프로필인데닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(2-이소프로필인데닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(2-이소프로필인데닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(2-이소프로필인데닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(2-이소프로필인데닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(2-이소프로필인데닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(2-이소프로필인데닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(2-이소프로필인데닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(2-이소프로필인데닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(2-이소프로필인데닐)하프늄 디아이오다이드, (1-isopropyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium dichloride, (1-isopropyl-4,5,6,7-tetrahydroindenyl) (indenyl) Hafnium dichloride, (1-isopropyl-4,5,6,7-tetrahydroindenyl) (indenyl) titanium difluoride, (1-isopropyl-4,5,6,7-tetrahydroindenyl ) (Indenyl) zirconium difluoride, (1-isopropyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium difluoride, (1-isopropyl-4,5,6, 7-tetrahydroindenyl) (indenyl) titanium dibromide, (1-isopropyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium dibromide, (1-isopropyl-4, 5,6,7-tetrahydroindenyl) (indenyl) hafnium dibromide, (1-isopropyl-4,5,6,7-tetrahydroindenyl) (indenyl) titanium diiodide, (1- Isopropyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium dia Iodide, (1-isopropyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium diiodide, (4,5,6,7-tetrahydroindenyl) (1-iso Propylindenyl) titanium dichloride, (4,5,6,7-tetrahydroindenyl) (1-isopropylinyl) zirconium dichloride, (4,5,6,7-tetrahydroindenyl) (1 Isopropylindenyl) hafnium dichloride, (4,5,6,7-tetrahydroindenyl) (1-isopropylinyl) titanium difluoride, (4,5,6,7-tetrahydroindenyl ) (1-Isopropylindenyl) zirconium difluoride, (4,5,6,7-tetrahydroindenyl) (1-isopropylinyl) hafnium difluoride, (4,5,6,7- Tetrahydroindenyl) (1-isopropylinyl) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (1-isopropylinyl) zirconium dibromide, (4,5,6, 7-tetrahydroindenyl) (1-isopropylindenyl) hafnium Bromide, (4,5,6,7-tetrahydroindenyl) (1-isopropylindenyl) titanium diiodide, (4,5,6,7-tetrahydroindenyl) (1-isopropylinyl ) Zirconium diiodide, (4,5,6,7-tetrahydroindenyl) (1-isopropylindenyl) hafnium diiodide, (2-isopropyl-4,5,6,7-tetrahydroinde Nil) (indenyl) titanium dichloride, (2-isopropyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium dichloride, (2-isopropyl-4,5,6,7 -Tetrahydroindenyl) (indenyl) hafnium dichloride, (2-isopropyl-4,5,6,7-tetrahydroindenyl) (indenyl) titanium difluoride, (2-isopropyl-4, 5,6,7-tetrahydroindenyl) (indenyl) zirconium difluoride, (2-isopropyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium difluoride, (2 Isopropyl-4,5,6,7-tetrahydroindenyl) Titanium dibromide, (2-isopropyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium dibromide, (2-isopropyl-4,5,6,7-tetrahydroindenyl ) (Indenyl) hafnium dibromide, (2-isopropyl-4,5,6,7-tetrahydroindenyl) (indenyl) titanium diiodide, (2-isopropyl-4,5,6,7 -Tetrahydroindenyl) (indenyl) zirconium diiodide, (2-isopropyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium diiodide, (4,5,6, 7-tetrahydroindenyl) (2-isopropylindenyl) titanium dichloride, (4,5,6,7-tetrahydroindenyl) (2-isopropylinyl) zirconium dichloride, (4,5, 6,7-tetrahydroindenyl) (2-isopropylindenyl) hafnium dichloride, (4,5,6,7-tetrahydroindenyl) (2-isopropylinyl) titanium difluoride, (4 , 5,6,7-tetrahydroindenyl) (2-isopropyl Denyl) zirconium difluoride, (4,5,6,7-tetrahydroindenyl) (2-isopropylindenyl) hafnium difluoride, (4,5,6,7-tetrahydroindenyl) (2 Isopropylindenyl) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (2-isopropylinyl) zirconium dibromide, (4,5,6,7-tetrahydroindenyl) (2-isopropylindenyl) hafnium dibromide, (4,5,6,7-tetrahydroindenyl) (2-isopropylindenyl) titanium diiodide, (4,5,6,7-tetrahydro Indenyl) (2-isopropylindenyl) zirconium diiodide, (4,5,6,7-tetrahydroindenyl) (2-isopropylinyl) hafnium diiodide,

(1-노말부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디클로라이드, (1-노말부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디클로라이드, (1-노말부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디플루오라이드, (1-노말부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디플루오라이드, (1-노말부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디플루오라이드, (1-노말부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디브로마이드, (1-노말부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디브로마이드, (1-노말부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디브로마이드, (1-노말부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디아이오다이드, (1-노말부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디아이오다이드, (1-노말부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(1-노말부틸인데닐)티타늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1-노말부틸인데닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1-노말부틸인데닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1-프로필인데닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-노말부틸인데닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-노말부틸인데닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-노말부틸인데닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-노말부틸인데닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-노말부틸인데닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-노말부틸인데닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(1-노말부틸인데닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(1-노말부틸인데닐)하프늄 디아이오다이드, (2-노말부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디클로라이드, (2-노말부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디클로라이드, (2-노말부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디클로라이드, (2-노말부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디플루오라이드, (2-노말부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디플루오라이드, (2-노말부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디플루오라이드, (2-노말부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디브로마이드, (2-노말부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디브로마이드, (2-노말부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디브로마이드, (2-노말부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디아이오다이드, (2-노말부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디아이오다이드, (2-노말부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(2-노말부틸인데닐)티타늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(2-노말부틸인데닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(2-노말부틸인데닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(2-노말부틸인데닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(2-노말부틸 인데닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(2-노말부틸인데닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(2-노말부틸인데닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(2-노말부틸인데닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(2-노말부틸인데닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(2-노말부틸인데닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(2-노말부틸인데닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(2-노말부틸인데닐)하프늄 디아이오다이드, (1-Normalbutyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium dichloride, (1-normalyl-4,5,6,7-tetrahydroindenyl) (indenyl) Hafnium dichloride, (1-normalbutyl-4,5,6,7-tetrahydroindenyl) (indenyl) titanium difluoride, (1-normalbutyl-4,5,6,7-tetrahydroindenyl ) (Indenyl) zirconium difluoride, (1-normalbutyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium difluoride, (1-normalbutyl-4,5,6, 7-tetrahydroindenyl) (indenyl) titanium dibromide, (1-normalbutyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium dibromide, (1-normalbutyl-4, 5,6,7-tetrahydroindenyl) (indenyl) hafnium dibromide, (1-normalbutyl-4,5,6,7-tetrahydroindenyl) (indenyl) titanium diiodide, (1- Normalbutyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium diiodide, (1-normal part -4,5,6,7-tetrahydroindenyl) (indenyl) hafnium diiodide, (4,5,6,7-tetrahydroindenyl) (1-normalbutylinyl) titanium dichloride, ( 4,5,6,7-tetrahydroindenyl) (1-normallybutylinyl) zirconium dichloride, (4,5,6,7-tetrahydroindenyl) (1-normallybutylinyl) hafnium dichloride , (4,5,6,7-tetrahydroindenyl) (1-propylindenyl) titanium difluoride, (4,5,6,7-tetrahydroindenyl) (1-normalbutylinyl) zirconium Difluoride, (4,5,6,7-tetrahydroindenyl) (1-normallybutylinyl) hafnium difluoride, (4,5,6,7-tetrahydroindenyl) (1-normalbutyl Indenyl) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (1-normal butylindenyl) zirconium dibromide, (4,5,6,7-tetrahydroindenyl) (1- Normalbutylindenyl) hafnium dibromide, (4,5,6,7-tetrahydroindenyl) (1- Malbutylindenyl) titanium diiodide, (4,5,6,7-tetrahydroindenyl) (1-normalbutylindenyl) zirconium diiodide, (4,5,6,7-tetrahydroindenyl ) (1-Normalbutylindenyl) hafnium diiodide, (2-normalbutyl-4,5,6,7-tetrahydroindenyl) (indenyl) titanium dichloride, (2-normalbutyl-4,5 , 6,7-tetrahydroindenyl) (indenyl) zirconium dichloride, (2-normalbutyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium dichloride, (2-normalbutyl -4,5,6,7-tetrahydroindenyl) (indenyl) titanium difluoride, (2-normalbutyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium difluoride , (2-normalbutyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium difluoride, (2-normalbutyl-4,5,6,7-tetrahydroindenyl) Nitrile) titanium dibromide, (2-normalbutyl-4,5,6,7-tetrahydroindenyl) Nil) zirconium dibromide, (2-normalbutyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium dibromide, (2-normalbutyl-4,5,6,7-tetrahydroinde Nil) (indenyl) titanium diiodide, (2-normalbutyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium diiodide, (2-normalbutyl-4,5,6 , 7-tetrahydroindenyl) (indenyl) hafnium diiodide, (4,5,6,7-tetrahydroindenyl) (2-normalbutylinyl) titanium dichloride, (4,5,6, 7-tetrahydroindenyl) (2-normalbutylindenyl) zirconium dichloride, (4,5,6,7-tetrahydroindenyl) (2-normalbutylinyl) halfnium dichloride, (4,5, 6,7-tetrahydroindenyl) (2-normalbutyl indenyl) titanium difluoride, (4,5,6,7-tetrahydroindenyl) (2-normalbutyl indenyl) zirconium difluoride, ( 4,5,6,7-tetrahydroindenyl) (2-normalbutylinyl) hafnium Fluoride, (4,5,6,7-tetrahydroindenyl) (2-normalbutylinyl) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (2-normalbutylinyl ) Zirconium dibromide, (4,5,6,7-tetrahydroindenyl) (2-normallybutylinyl) halfnium dibromide, (4,5,6,7-tetrahydroindenyl) (2-normalyl Indenyl) titanium diiodide, (4,5,6,7-tetrahydroindenyl) (2-normalbutylindenyl) zirconium diiodide, (4,5,6,7-tetrahydroindenyl) ( 2-normal butyl indenyl) hafnium diiodide,

(1-이소부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디클로라이드, (1-이소부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디클로라이드, (1-이소부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디플루오라이드, (1-이소부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디플루오라이드, (1-이소부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디플루오라이드, (1-이소부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디브로마이드, (1-이소부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디브로마이드, (1-이소부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디브로마이드, (1-이소부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디아이오다이드, (1-이소부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디아이오다이드, (1-이소부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(1-이소부틸인데닐)티타늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1-이소부틸인데닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1-이소부틸인데닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1-이소부틸인데닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-이소부틸인데닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-이소부틸인데닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-이소부틸인데닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-이소부틸인데닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-이소부틸인데닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-이소부틸인데닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(1-이소부틸인데닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(1-이소부틸인데닐)하프늄 디아이오다이드, (2-이소부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디클로라이드, (2-이소부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디클로라이드, (2-이소부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디클로라이드, (2-이소부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디플루오라이드, (2-이소부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디플루오라이드, (2-이소부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디플루오라이드, (2-이소부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디브로마이드, (2-이소부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디브로마이드, (2-이소부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디브로마이드, (2-이소부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)티타늄 디아이오다이드, (2-이소부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)지르코늄 디아이오다이드, (2-이소부틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(2-이소부틸인데닐)티타늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(2-이소부틸인데닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(2-이소부틸인데닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(2-이소부틸인데닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(2-이소부틸인데닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(2-이소부틸인데닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(2-이소부틸인데닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(2-이소부틸인데닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(2-이소부틸인데닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로-인데닐)(2-이소부틸인데닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로-인데닐)(2-이소부틸인데닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로-인데닐)(2-이소부틸인데닐)하프늄 디아이오다이드, (1-isobutyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium dichloride, (1-isobutyl-4,5,6,7-tetrahydroindenyl) (indenyl) Hafnium dichloride, (1-isobutyl-4,5,6,7-tetrahydroindenyl) (indenyl) titanium difluoride, (1-isobutyl-4,5,6,7-tetrahydroindenyl ) (Indenyl) zirconium difluoride, (1-isobutyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium difluoride, (1-isobutyl-4,5,6, 7-tetrahydroindenyl) (indenyl) titanium dibromide, (1-isobutyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium dibromide, (1-isobutyl-4, 5,6,7-tetrahydroindenyl) (indenyl) hafnium dibromide, (1-isobutyl-4,5,6,7-tetrahydroindenyl) (indenyl) titanium diiodide, (1- Isobutyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium diiodide, (1-isoisopart -4,5,6,7-tetrahydroindenyl) (indenyl) hafnium diiodide, (4,5,6,7-tetrahydroindenyl) (1-isobutylinyl) titanium dichloride, ( 4,5,6,7-tetrahydroindenyl) (1-isobutylindenyl) zirconium dichloride, (4,5,6,7-tetrahydroindenyl) (1-isobutylindenyl) hafnium dichloride , (4,5,6,7-tetrahydroindenyl) (1-isobutylindenyl) titanium difluoride, (4,5,6,7-tetrahydroindenyl) (1-isobutylinyl) Zirconium Difluoride, (4,5,6,7-tetrahydroindenyl) (1-isobutylindenyl) hafnium Difluoride, (4,5,6,7-tetrahydroindenyl) (1-iso Butylindenyl) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (1-isobutylindenyl) zirconium dibromide, (4,5,6,7-tetrahydroindenyl) (1 Isobutylindenyl) hafnium dibromide, (4,5,6,7-tetrahydroindenyl) ( 1-isobutyl indenyl) titanium diiodide, (4,5,6,7-tetrahydroindenyl) (1-isobutylindenyl) zirconium diiodide, (4,5,6,7-tetrahydro Indenyl) (1-isobutyl indenyl) hafnium diiodide, (2-isobutyl-4,5,6,7-tetrahydroindenyl) (indenyl) titanium dichloride, (2-isobutyl-4 , 5,6,7-tetrahydroindenyl) (indenyl) zirconium dichloride, (2-isobutyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium dichloride, (2- Isobutyl-4,5,6,7-tetrahydroindenyl) (indenyl) titanium difluoride, (2-isobutyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium di Fluoride, (2-isobutyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium difluoride, (2-isobutyl-4,5,6,7-tetrahydroindenyl) (Indenyl) titanium dibromide, (2-isobutyl-4,5,6,7-tetrahydroindenyl) ( Denyl) zirconium dibromide, (2-isobutyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium dibromide, (2-isobutyl-4,5,6,7-tetrahydroinde Nil) (indenyl) titanium diiodide, (2-isobutyl-4,5,6,7-tetrahydroindenyl) (indenyl) zirconium diiodide, (2-isobutyl-4,5,6 , 7-tetrahydroindenyl) (indenyl) hafnium diiodide, (4,5,6,7-tetrahydroindenyl) (2-isobutylindenyl) titanium dichloride, (4,5,6, 7-tetrahydroindenyl) (2-isobutylindenyl) zirconium dichloride, (4,5,6,7-tetrahydroindenyl) (2-isobutylindenyl) hafnium dichloride, (4,5, 6,7-tetrahydroindenyl) (2-isobutylindenyl) titanium difluoride, (4,5,6,7-tetrahydroindenyl) (2-isobutylindenyl) zirconium difluoride, ( 4,5,6,7-tetrahydroindenyl) (2-isobutylindenyl) hafnium Difluoride, (4,5,6,7-tetrahydroindenyl) (2-isobutylindenyl) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (2-isobutyl Nil) zirconium dibromide, (4,5,6,7-tetrahydroindenyl) (2-isobutylindenyl) hafnium dibromide, (4,5,6,7-tetrahydro-indenyl) (2- Isobutyl indenyl) titanium diiodide, (4,5,6,7-tetrahydro-indenyl) (2-isobutylindenyl) zirconium diiodide, (4,5,6,7-tetrahydro- Indenyl) (2-isobutyl indenyl) hafnium diiodide,

(1-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(인데닐)하프늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디아이오다이드, (2-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디클로라이드, (2-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디클로라이드, (2-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디클로라이드, (2-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디플루오라이드, (2-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디플루오라이드, (2-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디플루오라이드, (2-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디브로마이드, (2-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디브로마이드, (2-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디브로마이드, (2-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디아이오다이드, (2-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디아이오다이드, (2-메틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-메틸인데닐)티타늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-메틸 인데닐)지르코늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-메틸인데닐)하프늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-메틸인데닐)티타늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-메틸인데닐)지르코늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-메틸인데닐)하프늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-메틸인데닐)티타늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-메틸인데닐)지르코늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-메틸인데닐)하프늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-메틸인데닐)티타늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-메틸인데닐)지르코늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-메틸인데닐)하프늄 디아이오다이드, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1- Methylindenyl) zirconium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (indenyl) hafnium dichloride, (1-methyl-4,5,6,7-tetrahydroinde Nil) (1-methylindenyl) titanium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium difluoride, (1-methyl-4 , 5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium Dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium diiodide, (1-meth -4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl ) Halfnium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium dichloride, (1-methyl-4,5,6,7-tetrahydro Indenyl) (1-methylindenyl) zirconium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium dichloride, (1-methyl-4, 5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium di Fluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl ) (1-methylindenyl) titanium dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1- Methylinyl) titanium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium diiodide, (1-methyl-4,5,6, 7-tetrahydroindenyl) (1-methylindenyl) hafnium diiodide, (2-methyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium dichloride, (2 -Methyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium dichloride, (2-methyl-4,5,6,7-tetrahydroindenyl) (1-methylde Nil) hafnium dichloride, (2-methyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium difluoride, (2-methyl-4,5,6,7-tetra Hydroindenyl) (1-methylindenyl) zirconium difluoride, (2-methyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium difluoro De, (2-methyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium dibromide, (2-methyl-4,5,6,7-tetrahydroindenyl) ( 1-methylindenyl) zirconium dibromide, (2-methyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium dibromide, (2-methyl-4,5,6, 7-tetrahydroindenyl) (1-methylindenyl) titanium diiodide, (2-methyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium diiodide, ( 2-methyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl) (2- Methylinyl) titanium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-methyl indenyl) zirconium dichloride, (1-methyl-4,5,6,7- Tetrahydroindenyl) (2-methylindenyl) hafnium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-methylindenyl) titanium difluor Id, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-methylindenyl) zirconium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-methylindenyl) hafnium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-methylindenyl) titanium dibromide, (1-methyl-4,5, 6,7-tetrahydroindenyl) (2-methylindenyl) zirconium dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-methylindenyl) hafnium dibromide, ( 1-methyl-4,5,6,7-tetrahydroindenyl) (2-methylindenyl) titanium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl) (2- Methylindenyl) zirconium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-methylindenyl) hafnium diiodide,

(1-에틸-4,5,6,7-테트라하이드로인데닐)(1-메틸-인데닐)지르코늄 디클로라이드, (1-에틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디클로라이드, (1-에틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디플루오라이드, (1-에틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디플루오라이드, (1-에틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디플루오라이드, (1-에틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디브로마이드, (1-에틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디브로마이드, (1-에틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디브로마이드, (1-에틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디아이오다이드, (1-에틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디아이오다이드, (1-에틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-에틸인데닐)티타늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-에틸인데닐)지르코늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-에틸인데닐)하프늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-에틸인데닐)티타늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-에틸인데닐)지르코늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-에틸인데닐)하프늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-에틸인데닐)티타늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-에틸인데닐)지르코늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-에틸인데닐)하프늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-에틸인데닐)티타늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-에틸인데닐)지르코늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-에틸인데닐)하프늄 디아이오다이드, (2-에틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디클로라이드, (2-에틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디클로라이드, (2-에틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디클로라이드, (2-에틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디플루오라이드, (2-에틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디플루오라이드, (2-에틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디플루오라이드, (2-에틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디브로마이드, (2-에틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디브로마이드, (2-에틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디브로마이드, (2-에틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디아이오다이드, (2-에틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디아이오다이드, (2-에틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-에틸인데닐)티타늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-에틸인데닐)지르코늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-에틸인데닐)하프늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-에틸인데닐)티타늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-에틸인데닐)지르코늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-에틸인데닐)하프늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-에틸인데닐)티타늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-에틸인데닐)지르코늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-에틸인데닐)하프늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-에틸인데닐)티타늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-에틸인데닐)지르코늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-에틸인데닐)하프늄 디아이오다이드, (1-ethyl-4,5,6,7-tetrahydroindenyl) (1-methyl-indenyl) zirconium dichloride, (1-ethyl-4,5,6,7-tetrahydroindenyl) (1 -Methylindenyl) hafnium dichloride, (1-ethyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium difluoride, (1-ethyl-4,5,6, 7-tetrahydroindenyl) (1-methylindenyl) zirconium difluoride, (1-ethyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium difluoride, ( 1-ethyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium dibromide, (1-ethyl-4,5,6,7-tetrahydroindenyl) (1-methyl Indenyl) zirconium dibromide, (1-ethyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium dibromide, (1-ethyl-4,5,6,7-tetra Hydroindenyl) (1-methylindenyl) titanium diiodide, (1-ethyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium diioda Id, (1-ethyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-ethylindenyl) titanium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-ethylindenyl) zirconium dichloride, (1-methyl-4,5,6 , 7-tetrahydroindenyl) (1-ethylindenyl) hafnium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-ethylindenyl) titanium difluoride, ( 1-methyl-4,5,6,7-tetrahydroindenyl) (1-ethylindenyl) zirconium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1- Ethylindenyl) hafnium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-ethylindenyl) titanium dibromide, (1-methyl-4,5,6,7 -Tetrahydroindenyl) (1-ethylindenyl) zirconium dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-ethylindenyl) hafnium dibro Id, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-ethylindenyl) titanium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-ethylindenyl) zirconium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-ethylindenyl) hafnium diiodide, (2-ethyl-4,5 , 6,7-tetrahydroindenyl) (1-methylindenyl) titanium dichloride, (2-ethyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium dichloride, (2-ethyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium dichloride, (2-ethyl-4,5,6,7-tetrahydroindenyl) (1- Methylinyl) titanium difluoride, (2-ethyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium difluoride, (2-ethyl-4,5,6, 7-tetrahydroindenyl) (1-methylindenyl) hafnium difluoride, (2-ethyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium di Romanide, (2-ethyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium dibromide, (2-ethyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium dibromide, (2-ethyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium diiodide, (2-ethyl-4,5, 6,7-tetrahydroindenyl) (1-methylindenyl) zirconium diiodide, (2-ethyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium diiodide , (1-methyl-4,5,6,7-tetrahydroindenyl) (2-ethylindenyl) titanium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (2 -Ethylindenyl) zirconium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-ethylindenyl) hafnium dichloride, (1-methyl-4,5,6,7 -Tetrahydroindenyl) (2-ethylindenyl) titanium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-ethylindenyl) zirconium Difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-ethylindenyl) hafnium difluoride, (1-methyl-4,5,6,7-tetrahydroinde Nil) (2-ethylindenyl) titanium dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-ethylindenyl) zirconium dibromide, (1-methyl-4,5 , 6,7-tetrahydroindenyl) (2-ethylindenyl) hafnium dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-ethylindenyl) titanium diiodide , (1-methyl-4,5,6,7-tetrahydroindenyl) (2-ethylindenyl) zirconium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl) ( 2-ethylindenyl) hafnium diiodide,

(1-프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디클로라이드, (1-프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디클로라이드, (1-프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디플루오라이드, (1-프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디플루오라이드, (1-프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디플루오라이드, (1-프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디브로마이드, (1-프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디브로마이드, (1-프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디브로마이드, (1-프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디아이오다이드, (1-프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디아이오다이드, (1-프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-프로필인데닐)티타늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-프로필인데닐)지르코늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-프로필인데닐)하프늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-프로필인데닐)티타늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-프로필인데닐)지르코늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-프로필인데닐)하프늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-프로필인데닐)티타늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-프로필인데닐)지르코늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-프로필인데닐)하프늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-프로필 인데닐)티타늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-프로필인데닐)지르코늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-프로필인데닐)하프늄 디아이오다이드, (2-프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디클로라이드, (2-프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디클로라이드, (2-프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디클로라이드, (2-프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디플루오라이드, (2-프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디플루오라이드, (2-프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디플루오라이드, (2-프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디브로마이드, (2-프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디브로마이드, (2-프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디브로마이드, (2-프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디아이오다이드, (2-프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디아이오다이드, (2-프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-프로필인데닐)티타늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-프로필인데닐)지르코늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-프로필인데닐)하프늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-프로필인데닐)티타늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-프로필 인데닐)지르코늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-프로필 인데닐)하프늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-프로필인데닐)티타늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-프로필인데닐)지르코늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-프로필인데닐)하프늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-프로필인데닐)티타늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-프로필인데닐)지르코늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2- 프로필인데닐)하프늄 디아이오다이드, (1-propyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium dichloride, (1-propyl-4,5,6,7-tetrahydroindenyl) (1- Methylindenyl) hafnium dichloride, (1-propyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium difluoride, (1-propyl-4,5,6,7 -Tetrahydroindenyl) (1-methylindenyl) zirconium difluoride, (1-propyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium difluoride, (1 -Propyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium dibromide, (1-propyl-4,5,6,7-tetrahydroindenyl) (1-methylde Nil) zirconium dibromide, (1-propyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium dibromide, (1-propyl-4,5,6,7-tetrahydro Indenyl) (1-methylindenyl) titanium diiodide, (1-propyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl ) Zirconium diiodide, (1-propyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium diiodide, (1-methyl-4,5,6,7-tetra Hydroindenyl) (1-propylindenyl) titanium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-propylindenyl) zirconium dichloride, (1-methyl-4 , 5,6,7-tetrahydroindenyl) (1-propylindenyl) hafnium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-propylindenyl) titanium di Fluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-propylindenyl) zirconium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl ) (1-propylindenyl) hafnium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-propylindenyl) titanium dibromide, (1-methyl-4,5 , 6,7-tetrahydroindenyl) (1-propylindenyl) zirconium dibromide, (1-methyl-4,5,6,7-tetrahai Droindenyl) (1-propyl indenyl) hafnium dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-propyl indenyl) titanium diiodide, (1-methyl- 4,5,6,7-tetrahydroindenyl) (1-propylindenyl) zirconium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-propylindenyl) Hafnium diiodide, (2-propyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium dichloride, (2-propyl-4,5,6,7-tetrahydroinde Nil) (1-methylindenyl) zirconium dichloride, (2-propyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium dichloride, (2-propyl-4,5 , 6,7-tetrahydroindenyl) (1-methylindenyl) titanium difluoride, (2-propyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium difluor Ride, (2-propyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium difluoride De, (2-propyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium dibromide, (2-propyl-4,5,6,7-tetrahydroindenyl) ( 1-methylindenyl) zirconium dibromide, (2-propyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium dibromide, (2-propyl-4,5,6, 7-tetrahydroindenyl) (1-methylindenyl) titanium diiodide, (2-propyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium diiodide, ( 2-propyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl) (2- Propylinyl) titanium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-propylinyl) zirconium dichloride, (1-methyl-4,5,6,7- Tetrahydroindenyl) (2-propylindenyl) hafnium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-propyl Titanium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-propyl indenyl) zirconium difluoride, (1-methyl-4,5,6,7-tetra Hydroindenyl) (2-propyl indenyl) hafnium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-propylinyl) titanium dibromide, (1-methyl- 4,5,6,7-tetrahydroindenyl) (2-propylindenyl) zirconium dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-propylindenyl) hafnium Dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-propylinyl) titanium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl ) (2-propylindenyl) zirconium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-propylindenyl) hafnium diiodide,

(1-이소프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디클로라이드, (1-이소프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디클로라이드, (1-이소프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디플루오라이드, (1-이소프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디플루오라이드, (1-이소프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디플루오라이드, (1-이소프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디브로마이드, (1-이소프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디브로마이드, (1-이소프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디브로마이드, (1-이소프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디아이오다이드, (1-이소프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디아이오다이드, (1-이소프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-이소프로필인데닐)티타늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-이소프로필인데닐)지르코늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-이소프로필인데닐)하프늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-이소프로필인데닐)티타늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-이소프로필인데닐)지르코늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-이소프로필인데닐)하프늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-이소프로필인데닐)티타늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-이소프로필인데닐)지르코늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-이소프로필인데닐)하프늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-이소프로필인데닐)티타늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-이소프로필인데닐)지르코늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-이소프로필인데닐)하프늄 디아이오다이드, (2-이소프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디클로라이드, (2-이소프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디클로라이드, (2-이소프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디클로라이드, (2-이소프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디플루오라이드, (2-이소프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디플루오라이드, (2-이소프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디플루오라이드, (2-이소프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디브로마이드, (2-이소프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디브로마이드, (2-이소프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디브로마이드, (2-이소프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디아이오다이드, (2-이소프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디아이오다이드, (2-이소프로필-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-이소프로필인데닐)티타늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-이소프로필인데닐)지르코늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-이소프로필인데닐)하프늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-이소프로필인데닐)티타늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-이소프로필인데닐)지르코늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-이소프로필인데닐)하프늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-이소프로필인데닐)티타늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-이소프로필인데닐)지르코늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-이소프로필인데닐)하프늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-이소프로필인데닐)티타늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-이소프로필인데닐)지르코늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-이소프로필인데닐)하프늄 디아이오다이드, (1-isopropyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium dichloride, (1-isopropyl-4,5,6,7-tetrahydroindenyl) ( 1-methylindenyl) hafnium dichloride, (1-isopropyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium difluoride, (1-isopropyl-4,5 , 6,7-tetrahydroindenyl) (1-methylindenyl) zirconium difluoride, (1-isopropyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium di Fluoride, (1-isopropyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium dibromide, (1-isopropyl-4,5,6,7-tetrahydroinde Nil) (1-methylindenyl) zirconium dibromide, (1-isopropyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium dibromide, (1-isopropyl-4 , 5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium diiodide, (1-isopro -4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium diiodide, (1-isopropyl-4,5,6,7-tetrahydroindenyl) (1-methylde Nil) hafnium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-isopropylinyl) titanium dichloride, (1-methyl-4,5,6,7- Tetrahydroindenyl) (1-isopropylinyl) zirconium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-isopropylinyl) hafnium dichloride, (1- Methyl-4,5,6,7-tetrahydroindenyl) (1-isopropylindenyl) titanium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-iso Propylindenyl) zirconium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-isopropylinyl) hafnium difluoride, (1-methyl-4,5,6 , 7-tetrahydroindenyl) (1-isopropylindenyl) titanium dibromide, (1-methyl-4,5,6,7-tetra Idroindenyl) (1-isopropylinyl) zirconium dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-isopropylinyl) hafnium dibromide, (1-methyl -4,5,6,7-tetrahydroindenyl) (1-isopropylindenyl) titanium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-isopropyl Indenyl) zirconium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-isopropylindenyl) hafnium diiodide, (2-isopropyl-4,5,6 , 7-tetrahydroindenyl) (1-methylindenyl) titanium dichloride, (2-isopropyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium dichloride, ( 2-isopropyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium dichloride, (2-isopropyl-4,5,6,7-tetrahydroindenyl) (1 -Methylindenyl) titanium difluoride, (2-isopropyl-4,5,6,7-tetrahydrate Rodeninyl) (1-methylindenyl) zirconium difluoride, (2-isopropyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium difluoride, (2- Isopropyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium dibromide, (2-isopropyl-4,5,6,7-tetrahydroindenyl) (1-methyl Indenyl) zirconium dibromide, (2-isopropyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium dibromide, (2-isopropyl-4,5,6,7 -Tetrahydroindenyl) (1-methylindenyl) titanium diiodide, (2-isopropyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium diiodide, ( 2-isopropyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl) (2 Isopropylindenyl) titanium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-iso Propylindenyl) zirconium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-isopropylinyl) hafnium dichloride, (1-methyl-4,5,6,7 -Tetrahydroindenyl) (2-isopropylinyl) titanium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-isopropylinyl) zirconium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-isopropylindenyl) hafnium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) ( 2-isopropylindenyl) titanium dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-isopropylinyl) zirconium dibromide, (1-methyl-4,5, 6,7-tetrahydroindenyl) (2-isopropylindenyl) hafnium dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-isopropylinyl) titanium diioda Id, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-isopropyl ) DI zirconium iodide, (1-methyl-4,5,6,7-inde tetrahydroindenyl) (inde 2-isopropyl-indenyl) hafnium DI iodide,

(1-노말부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디클로라이드, (1-노말부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디클로라이드, (1-노말부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디플루오라이드, (1-노말부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디플루오라이드, (1-노말부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디플루오라이드, (1-노말부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디브로마이드, (1-노말부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디브로마이드, (1-노말부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디브로마이드, (1-노말부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디아이오다이드, (1-노말부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디아이오다이드, (1-노말부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-노말부틸인데닐)티타늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1- 노말부틸인데닐)지르코늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1- 노말부틸 인데닐)하프늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-프로필인데닐)티타늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-노말부틸인데닐)지르코늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-노말부틸인데닐)하프늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-노말부틸인데닐)티타늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-노말부틸인데닐)지르코늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-노말부틸인데닐)하프늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-노말부틸인데닐)티타늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-노말부틸인데닐)지르코늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-노말부틸인데닐)하프늄 디아이오다이드, (2-노말부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디클로라이드, (2-노말부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디클로라이드, (2-노말부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디클로라이드, (2-노말부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디플루오라이드, (2-노말부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디플루오라이드, (2-노말부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디플루오라이드, (2-노말부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디브로마이드, (2-노말부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디브로마이드, (2-노말부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디브로마이드, (2-노말부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디아이오다이드, (2-노말부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디아이오다이드, (2-노말부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-노말부틸인데닐)티타늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-노말부틸인데닐)지르코늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-노말부틸인데닐)하프늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-노말부틸인데닐)티타늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-노말부틸인데닐)지르코늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-노말부틸인데닐)하프늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-노말부틸인데닐)티타늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-노말부틸인데닐)지르코늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-노말부틸인데닐)하프늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-노말부틸인데닐)티타늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-노말부틸인데닐)지르코늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-노말부틸인데닐)하프늄 디아이오다이드, (1-normalbutyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium dichloride, (1-normalbutyl-4,5,6,7-tetrahydroindenyl) ( 1-methylindenyl) hafnium dichloride, (1-normalbutyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium difluoride, (1-normalbutyl-4,5 , 6,7-tetrahydroindenyl) (1-methylindenyl) zirconium difluoride, (1-normalbutyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium di Fluoride, (1-normalbutyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium dibromide, (1-normalbutyl-4,5,6,7-tetrahydro Nil) (1-methylindenyl) zirconium dibromide, (1-normalbutyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium dibromide, (1-normalbutyl-4 , 5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium diiodide, (1-normalbutyl-4,5,6,7-tetrahydro Indenyl) (1-methylindenyl) zirconium diiodide, (1-normalbutyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium diiodide, (1-methyl -4,5,6,7-tetrahydroindenyl) (1-normalbutylindenyl) titanium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-normalbutyl) Yl) zirconium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-normalbutyl indenyl) hafnium dichloride, (1-methyl-4,5,6,7-tetra Hydroindenyl) (1-propylindenyl) titanium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-normalbutylinyl) zirconium difluoride, (1- Methyl-4,5,6,7-tetrahydroindenyl) (1-normal butylindenyl) hafnium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-normal Butyl indenyl) titanium dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-normal butyl indenyl) zirco Nium dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-normal butylindenyl) hafnium dibromide, (1-methyl-4,5,6,7-tetrahydroinde Nil) (1-normalbutylindenyl) titanium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-normalbutylindenyl) zirconium diiodide, (1-methyl -4,5,6,7-tetrahydroindenyl) (1-normalbutylindenyl) hafnium diiodide, (2-normalbutyl-4,5,6,7-tetrahydroindenyl) (1-methyl Indenyl) titanium dichloride, (2-normalbutyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium dichloride, (2-normalbutyl-4,5,6,7 -Tetrahydroindenyl) (1-methylindenyl) hafnium dichloride, (2-normalbutyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium difluoride, (2 -Normal butyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium difluoride, (2-normalbutyl- 4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium difluoride, (2-normalbutyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl Titanium dibromide, (2-normalbutyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium dibromide, (2-normalbutyl-4,5,6,7-tetra Hydroindenyl) (1-methylindenyl) hafnium dibromide, (2-normalbutyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium diiodide, (2-normal Butyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium diiodide, (2-normalbutyl-4,5,6,7-tetrahydroindenyl) (1-methyl Indenyl) hafnium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-normalbutylinyl) titanium dichloride, (1-methyl-4,5,6,7 -Tetrahydroindenyl) (2-normalbutylinyl) zirconium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-normal Butylindenyl) hafnium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-normalbutylinyl) titanium difluoride, (1-methyl-4,5,6, 7-tetrahydroindenyl) (2-normalbutylinyl) zirconium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-normalbutylinyl) hafnium difluoride , (1-methyl-4,5,6,7-tetrahydroindenyl) (2-normalbutylinyl) titanium dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) ( 2-normalbutyl indenyl) zirconium dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-normalbutylinyl) hafnium dibromide, (1-methyl-4,5, 6,7-tetrahydroindenyl) (2-normalbutylindenyl) titanium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-normalbutylinyl) zirconium diai Odide, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-normalbutylinyl) hafnium diioda Droid,

(1-이소부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디클로라이드, (1-이소부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디클로라이드, (1-이소부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디플루오라이드, (1-이소부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디플루오라이드, (1-이소부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디플루오라이드, (1-이소부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디브로마이드, (1-이소부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디브로마이드, (1-이소부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디브로마이드, (1-이소부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디아이오다이드, (1-이소부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디아이오다이드, (1-이소부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-이소부틸인데닐)티타늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-이소부틸인데닐)지르코늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-이소부틸인데닐)하프늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-이소부틸인데닐)티타늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-이소부틸인데닐)지르코늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-이소부틸인데닐)하프늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-이소부틸인데닐)티타늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-이소부틸인데닐)지르코늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-이소부틸인데닐)하프늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-이소부틸인데닐)티타늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-이소부틸인데닐)지르코늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(1-이소부틸인데닐)하프늄 디아이오다이드, (2-이소부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디클로라이드, (2-이소부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디클로라이드, (2-이소부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디클로라이드, (2-이소부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디플루오라이드, (2-이소부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디플루오라이드, (2-이소부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디플루오라이드, (2-이소부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디브로마이드, (2-이소부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디브로마이드, (2-이소부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디브로마이드, (2-이소부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)티타늄 디아이오다이드, (2-이소부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디아이오다이드, (2-이소부틸-4,5,6,7-테트라하이드로인데닐)(1-메틸인데닐)하프늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-이소부틸인데닐)티타늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-이소부틸인데닐)지르코늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-이소부틸인데닐)하프늄 디클로라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-이소부틸인데닐)티타늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-이소부틸인데닐)지르코늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-이소부틸인데닐)하프늄 디플루오라이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-이소부틸인데닐)티타늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-이소부틸인데닐)지르코늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-이소부틸인데닐)하프늄 디브로마이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-이소부틸인데닐)티타늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-이소부틸인데닐)지르코늄 디아이오다이드, (1-메틸-4,5,6,7-테트라하이드로인데닐)(2-이소부틸인데닐)하프늄 디아이오다이드, (1-isobutyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium dichloride, (1-isobutyl-4,5,6,7-tetrahydroindenyl) ( 1-methylindenyl) hafnium dichloride, (1-isobutyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium difluoride, (1-isobutyl-4,5 , 6,7-tetrahydroindenyl) (1-methylindenyl) zirconium difluoride, (1-isobutyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium di Fluoride, (1-isobutyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium dibromide, (1-isobutyl-4,5,6,7-tetrahydroinde Nil) (1-methylindenyl) zirconium dibromide, (1-isobutyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium dibromide, (1-isobutyl-4 , 5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium diiodide, (1-isobutyl-4,5,6,7-tetrahydro Indenyl) (1-methylindenyl) zirconium diiodide, (1-isobutyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium diiodide, (1-methyl -4,5,6,7-tetrahydroindenyl) (1-isobutylindenyl) titanium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-isobutyl Nil) zirconium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-isobutylinyl) hafnium dichloride, (1-methyl-4,5,6,7-tetra Hydroindenyl) (1-isobutylindenyl) titanium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-isobutylindenyl) zirconium difluoride, (1 -Methyl-4,5,6,7-tetrahydroindenyl) (1-isobutylindenyl) hafnium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (1- Isobutyl indenyl) titanium dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-isobutylinyl) zirco Nium dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-isobutylindenyl) hafnium dibromide, (1-methyl-4,5,6,7-tetrahydroinde Nil) (1-isobutylindenyl) titanium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl) (1-isobutylindenyl) zirconium diiodide, (1-methyl -4,5,6,7-tetrahydroindenyl) (1-isobutylindenyl) hafnium diiodide, (2-isobutyl-4,5,6,7-tetrahydroindenyl) (1-methyl Indenyl) titanium dichloride, (2-isobutyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium dichloride, (2-isobutyl-4,5,6,7 -Tetrahydroindenyl) (1-methylindenyl) hafnium dichloride, (2-isobutyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium difluoride, (2 Isobutyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium difluoride, (2-isobutyl- 4,5,6,7-tetrahydroindenyl) (1-methylindenyl) hafnium difluoride, (2-isobutyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl Titanium dibromide, (2-isobutyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium dibromide, (2-isobutyl-4,5,6,7-tetra Hydroindenyl) (1-methylindenyl) hafnium dibromide, (2-isobutyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) titanium diiodide, (2-iso) Butyl-4,5,6,7-tetrahydroindenyl) (1-methylindenyl) zirconium diiodide, (2-isobutyl-4,5,6,7-tetrahydroindenyl) (1-methyl Indenyl) hafnium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-isobutylindenyl) titanium dichloride, (1-methyl-4,5,6,7 -Tetrahydroindenyl) (2-isobutylinyl) zirconium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-iso Butylindenyl) hafnium dichloride, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-isobutylinyl) titanium difluoride, (1-methyl-4,5,6, 7-tetrahydroindenyl) (2-isobutylindenyl) zirconium difluoride, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-isobutylinyl) hafnium difluoride , (1-methyl-4,5,6,7-tetrahydroindenyl) (2-isobutylindenyl) titanium dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) ( 2-isobutyl indenyl) zirconium dibromide, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-isobutylinyl) hafnium dibromide, (1-methyl-4,5, 6,7-tetrahydroindenyl) (2-isobutylindenyl) titanium diiodide, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-isobutylindenyl) zirconium diai Odide, (1-methyl-4,5,6,7-tetrahydroindenyl) (2-isobutylindenyl) hafnium diioda Droid,

(4,5,6,7-테트라하이드로인데닐)(1-페닐인데닐)티타늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1-페닐인데닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1-페닐인데닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1-페닐인데닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-페닐인데닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-페닐인데닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-페닐인데닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-페닐인데닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-페닐인데닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-페닐인데닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(1-페닐인데닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(1-페닐인데닐)하프늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(2-페닐인데닐)티타늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(2-페닐인데닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(2-페닐인데닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(2-페닐인데닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(2-페닐인데닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(2-페닐인데닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(2-페닐인데닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(2-페닐인데닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(2-페닐인데닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(2-페닐인데닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(2-페닐인데닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(2-페닐인데닐)하프늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(1-벤질인데닐)티타늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1-벤질인데닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1-벤질인데닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1-벤질인데닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-벤질인데닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-벤질인데닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-벤질인데닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-벤질인데닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-벤질인데닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-벤질인데닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(1-벤질인데닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(1-벤질인데닐)하프늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(2-벤질인데닐)티타늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(2-벤질인데닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(2-벤질인데닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(2-벤질인데닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(2-벤질인데닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(2-벤질인데닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(2-벤질인데닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(2-벤질인데닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(2-벤질인데닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(2-벤질인데닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(2-벤질인데닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(2-벤질인데닐)하프늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로펜타디에닐)티타늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로펜타디에닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로펜타디에닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로펜타디에닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로펜타디에닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로펜타디에닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로펜타디에닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로펜타디에닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로펜타디에닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로펜타디에닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로펜타디에닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로펜타디에닐)하프늄 디아이오다이드, (4,5,6,7-tetrahydroindenyl) (1-phenylindenyl) titanium dichloride, (4,5,6,7-tetrahydroindenyl) (1-phenylindenyl) zirconium dichloride, (4,5,6,7-tetrahydroindenyl) (1-phenylindenyl) hafnium dichloride, (4,5,6,7-tetrahydroindenyl) (1-phenylindenyl) titanium difluoride , (4,5,6,7-tetrahydroindenyl) (1-phenylindenyl) zirconium difluoride, (4,5,6,7-tetrahydroindenyl) (1-phenylindenyl) hafnium di Fluoride, (4,5,6,7-tetrahydroindenyl) (1-phenylindenyl) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (1-phenylindenyl) zirconium Dibromide, (4,5,6,7-tetrahydroindenyl) (1-phenylindenyl) hafnium dibromide, (4,5,6,7-tetrahydroindenyl) (1-phenylindenyl) titanium Diiodide, (4,5,6,7-tetrahydroindenyl) (1-phenylindenyl) zirconium diioda De, (4,5,6,7-tetrahydroindenyl) (1-phenylindenyl) hafnium diiodide, (4,5,6,7-tetrahydroindenyl) (2-phenylindenyl) titanium Dichloride, (4,5,6,7-tetrahydroindenyl) (2-phenylindenyl) zirconium dichloride, (4,5,6,7-tetrahydroindenyl) (2-phenylindenyl) hafnium Dichloride, (4,5,6,7-tetrahydroindenyl) (2-phenylindenyl) titanium difluoride, (4,5,6,7-tetrahydroindenyl) (2-phenylindenyl) Zirconium difluoride, (4,5,6,7-tetrahydroindenyl) (2-phenylindenyl) hafnium difluoride, (4,5,6,7-tetrahydroindenyl) (2-phenyl Nil) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (2-phenylindenyl) zirconium dibromide, (4,5,6,7-tetrahydroindenyl) (2-phenyl Nil) hafnium dibromide, (4,5,6,7-tetrahydroindenyl) (2-phenylindenyl) titanium diio Id, (4,5,6,7-tetrahydroindenyl) (2-phenylindenyl) zirconium diiodide, (4,5,6,7-tetrahydroindenyl) (2-phenylindenyl) hafnium Diiodide, (4,5,6,7-tetrahydroindenyl) (1-benzylindenyl) titanium dichloride, (4,5,6,7-tetrahydroindenyl) (1-benzylindenyl) Zirconium Dichloride, (4,5,6,7-tetrahydroindenyl) (1-benzylindenyl) halfnium Dichloride, (4,5,6,7-tetrahydroindenyl) (1-benzylindenyl) Titanium difluoride, (4,5,6,7-tetrahydroindenyl) (1-benzylindenyl) zirconium difluoride, (4,5,6,7-tetrahydroindenyl) (1-benzylde Nil) hafnium difluoride, (4,5,6,7-tetrahydroindenyl) (1-benzylindenyl) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (1-benzyl Indenyl) zirconium dibromide, (4,5,6,7-tetrahydroindenyl) (1-benzylindenyl) hafnium di Romaid, (4,5,6,7-tetrahydroindenyl) (1-benzylindenyl) titanium diiodide, (4,5,6,7-tetrahydroindenyl) (1-benzylindenyl) Zirconium Diiodide, (4,5,6,7-tetrahydroindenyl) (1-benzylindenyl) Halfnium Diiodide, (4,5,6,7-tetrahydroindenyl) (2-benzyl Nil) titanium dichloride, (4,5,6,7-tetrahydroindenyl) (2-benzylindenyl) zirconium dichloride, (4,5,6,7-tetrahydroindenyl) (2-benzylde Nil) hafnium dichloride, (4,5,6,7-tetrahydroindenyl) (2-benzylindenyl) titanium difluoride, (4,5,6,7-tetrahydroindenyl) (2-benzyl Indenyl) zirconium difluoride, (4,5,6,7-tetrahydroindenyl) (2-benzylindenyl) hafnium difluoride, (4,5,6,7-tetrahydroindenyl) (2 -Benzylindenyl) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (2-benzylindenyl) zirco Hafnium dibromide, (4,5,6,7-tetrahydroindenyl) (2-benzylindenyl) halfnium dibromide, (4,5,6,7-tetrahydroindenyl) (2-benzylindenyl) Titanium diiodide, (4,5,6,7-tetrahydroindenyl) (2-benzylindenyl) zirconium diiodide, (4,5,6,7-tetrahydroindenyl) (2-benzyl Nil) hafnium diiodide, (4,5,6,7-tetrahydroindenyl) (cyclopentadienyl) titanium dichloride, (4,5,6,7-tetrahydroindenyl) (cyclopentadienyl ) Zirconium dichloride, (4,5,6,7-tetrahydroindenyl) (cyclopentadienyl) hafnium dichloride, (4,5,6,7-tetrahydroindenyl) (cyclopentadienyl) titanium Difluoride, (4,5,6,7-tetrahydroindenyl) (cyclopentadienyl) zirconium difluoride, (4,5,6,7-tetrahydroindenyl) (cyclopentadienyl) hafnium Difluoride, (4,5,6,7-tetrahydroindenyl) (cyclopentadienyl) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (cyclopentadienyl) zirconium dibromide, (4 , 5,6,7-tetrahydroindenyl) (cyclopentadienyl) halfnium dibromide, (4,5,6,7-tetrahydroindenyl) (cyclopentadienyl) titanium diiodide, (4, 5,6,7-tetrahydroindenyl) (cyclopentadienyl) zirconium diiodide, (4,5,6,7-tetrahydroindenyl) (cyclopentadienyl) hafnium diiodide,

(4,5,6,7-테트라하이드로인데닐)(메틸싸이클로펜타디에닐)티타늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(메틸싸이클로펜타디에닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(메틸싸이클로펜타디에닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(메틸싸이클로펜타디에닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(메틸싸이클로펜타디에닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(메틸싸이클로펜타디에닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(메틸싸이클로펜타디에닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(메틸싸이클로펜타디에닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(메틸싸이클로펜타디에닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(메틸싸이클로펜타디에닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(메틸싸이클로펜타디에닐)하프늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(에틸싸이클로펜타디에닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(에틸싸이클로펜타디에닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(에틸싸이클로펜타디에닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(에틸싸이클로펜타디에닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(에틸싸이클로펜타디에닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(에틸싸이클로펜타디에닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(에틸싸이클로펜타디에닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(에틸싸이클로펜타디에닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(에틸싸이클로펜타디에닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(에틸싸이클로펜타디에닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(에틸싸이클로펜타디에닐)하프늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(프로필싸이클로펜타디에닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(프로필싸이클로펜타디에닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(프로필싸이클로펜타디에닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(프로필싸이클로펜타디에닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(프로필싸이클로펜타디에닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(프로필싸이클로펜타디에닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(프로필싸이클로펜타디에닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(프로필싸이클로펜타디에닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(프로필싸이클로펜타디에닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(프로필싸이클로펜타디에닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)( 프로필싸이클로펜타디에닐)하프늄 디아이오다이드,(4,5,6,7-tetrahydroindenyl) (methylcyclopentadienyl) titanium dichloride, (4,5,6,7-tetrahydroindenyl) (methylcyclopentadienyl) zirconium dichloride, (4,5,6,7-tetrahydroindenyl) (methylcyclopentadienyl) hafnium dichloride, (4,5,6,7-tetrahydroindenyl) (methylcyclopentadienyl) titanium difluoride (4,5,6,7-tetrahydroindenyl) (methylcyclopentadienyl) zirconium difluoride, (4,5,6,7-tetrahydroindenyl) (methylcyclopentadienyl) hafnium di Fluoride, (4,5,6,7-tetrahydroindenyl) (methylcyclopentadienyl) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (methylcyclopentadienyl) zirconium Dibromide, (4,5,6,7-tetrahydroindenyl) (methylcyclopentadienyl) hafnium dibromide, (4,5,6,7-tetrahydroinde) (Methylcyclopentadienyl) titanium diiodide, (4,5,6,7-tetrahydroindenyl) (methylcyclopentadienyl) zirconium diiodide, (4,5,6,7-tetrahydro Indenyl) (methylcyclopentadienyl) hafnium diiodide, (4,5,6,7-tetrahydroindenyl) (ethylcyclopentadienyl) zirconium dichloride, (4,5,6,7-tetra Hydroindenyl) (ethylcyclopentadienyl) hafnium dichloride, (4,5,6,7-tetrahydroindenyl) (ethylcyclopentadienyl) titanium difluoride, (4,5,6,7- Tetrahydroindenyl) (ethylcyclopentadienyl) zirconium difluoride, (4,5,6,7-tetrahydroindenyl) (ethylcyclopentadienyl) hafnium difluoride, (4,5,6, 7-tetrahydroindenyl) (ethylcyclopentadienyl) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (ethylcyclopenta Dienyl) zirconium dibromide, (4,5,6,7-tetrahydroindenyl) (ethylcyclopentadienyl) hafnium dibromide, (4,5,6,7-tetrahydroindenyl) (ethylcyclopenta Dienyl) titanium diiodide, (4,5,6,7-tetrahydroindenyl) (ethylcyclopentadienyl) zirconium diiodide, (4,5,6,7-tetrahydroindenyl) (ethyl Cyclopentadienyl) hafnium diiodide, (4,5,6,7-tetrahydroindenyl) (propylcyclopentadienyl) zirconium dichloride, (4,5,6,7-tetrahydroindenyl) ( Propylcyclopentadienyl) hafnium dichloride, (4,5,6,7-tetrahydroindenyl) (propylcyclopentadienyl) titanium difluoride, (4,5,6,7-tetrahydroindenyl) (Propylcyclopentadienyl) zirconium difluoride, (4,5,6,7-tetrahydroindenyl) (propylcyclopentadienyl) Phenium difluoride, (4,5,6,7-tetrahydroindenyl) (propylcyclopentadienyl) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (propylcyclopentadienyl ) Zirconium dibromide, (4,5,6,7-tetrahydroindenyl) (propylcyclopentadienyl) hafnium dibromide, (4,5,6,7-tetrahydroindenyl) (propylcyclopentadienyl Titanium diiodide, (4,5,6,7-tetrahydroindenyl) (propylcyclopentadienyl) zirconium diiodide, (4,5,6,7-tetrahydroindenyl) (propylcyclopenta Dienyl) hafnium diiodide,

(4,5,6,7-테트라하이드로인데닐)(노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(노말부틸싸이클로펜타디에닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(노말부틸싸이클로펜타디에닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(노말부틸싸이클로펜타디에닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(노말부틸싸이클로펜타디에닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(노말부틸싸이클로펜타디에닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(노말부틸싸이클로펜타디에닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(노말부틸싸이클로펜타디에닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(노말부틸싸이클로펜타디에닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(노말부틸싸이클로펜타디에닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(노말부틸싸이클로펜타디에닐)하프늄 디아이오다이드,(4,5,6,7-tetrahydroindenyl) (normal butylcyclopentadienyl) zirconium dichloride, (4,5,6,7-tetrahydroindenyl) (normal butylcyclopentadienyl) hafnium di Chloride, (4,5,6,7-tetrahydroindenyl) (normal butylcyclopentadienyl) titanium difluoride, (4,5,6,7-tetrahydroindenyl) (normal butylcyclopentadienyl ) Zirconium difluoride, (4,5,6,7-tetrahydroindenyl) (normal butylcyclopentadienyl) halfnium difluoride, (4,5,6,7-tetrahydroindenyl) (normal butyl Cyclopentadienyl) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (normal butylcyclopentadienyl) zirconium dibromide, (4,5,6,7-tetrahydroindenyl) ( Normal butylcyclopentadienyl) halfnium dibromide, (4,5,6,7-tetrahydroindenyl) (normal butylcyclopentadienyl) titanium di Iodide, (4,5,6,7-tetrahydroindenyl) (normal butylcyclopentadienyl) zirconium diiodide, (4,5,6,7-tetrahydroindenyl) (normal butylcyclopenta Dienyl) hafnium diiodide,

(4,5,6,7-테트라하이드로인데닐)(이소부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(이소부틸싸이클로펜타디에닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(이소부틸싸이클로펜타디에닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(이소부틸싸이클로펜타디에닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(이소부틸싸이클로펜타디에닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(이소부틸싸이클로펜타디에닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(이소부틸싸이클로펜타디에닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(이소부틸싸이클로펜타디에닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(이소부틸싸이클로펜타디에닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(이소부틸싸이클로펜타디에닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(이소부틸싸이클로펜타디에닐)하프늄 디아이오다이드,(4,5,6,7-tetrahydroindenyl) (isobutylcyclopentadienyl) zirconium dichloride, (4,5,6,7-tetrahydroindenyl) (isobutylcyclopentadienyl) hafnium di Chloride, (4,5,6,7-tetrahydroindenyl) (isobutylcyclopentadienyl) titanium difluoride, (4,5,6,7-tetrahydroindenyl) (isobutylcyclopentadienyl Zirconium difluoride, (4,5,6,7-tetrahydroindenyl) (isobutylcyclopentadienyl) hafnium difluoride, (4,5,6,7-tetrahydroindenyl) (isobutyl Cyclopentadienyl) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (isobutylcyclopentadienyl) zirconium dibromide, (4,5,6,7-tetrahydroindenyl) ( Isobutylcyclopentadienyl) hafnium dibromide, (4,5,6,7-tetrahydroindenyl) (isobutylcyclopentadienyl) titanium di Iodide, (4,5,6,7-tetrahydroindenyl) (isobutylcyclopentadienyl) zirconium diiodide, (4,5,6,7-tetrahydroindenyl) (isobutylcyclopenta Dienyl) hafnium diiodide,

(4,5,6,7-테트라하이드로인데닐)(1-메틸-3-노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1-메틸-3-노말부틸싸이클로펜타디에닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(1-메틸-3-노말부틸싸이클로펜타디에닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-메틸-3-노말부틸싸이클로펜타디에닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-메틸-3-노말부틸싸이클로펜타디에닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(1-메틸-3-노말부틸싸이클로펜타디에닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-메틸-3-노말부틸싸이클로펜타디에닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-메틸-3-노말부틸싸이클로펜타디에닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(1-메틸-3-노말부틸싸이클로펜타디에닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(1-메틸-3-노말부틸싸이클로펜타디에닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(1-메틸-3-노말부틸싸이클로펜타디에닐)하프늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(펜타메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(펜타메틸싸이클로펜타디에닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(펜타메틸싸이클로펜타디에닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(펜타메틸싸이클로펜타디에닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(펜타메틸싸이클로펜타디에닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(펜타메틸싸이클로펜타디에닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(펜타메틸싸이클로펜타디에닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(펜타메틸싸이클로펜타디에닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(펜타메틸싸이클로펜타디에닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(펜타메틸싸이클로펜타디에닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(펜타메틸싸이클로펜타디에닐)하프늄 디아이오다이드,(4,5,6,7-tetrahydroindenyl) (1-methyl-3-normalbutylcyclopentadienyl) zirconium dichloride, (4,5,6,7-tetrahydroindenyl) (1-methyl -3-normalbutylcyclopentadienyl) hafnium dichloride, (4,5,6,7-tetrahydroindenyl) (1-methyl-3-normalbutylcyclopentadienyl) titanium difluoride, (4, 5,6,7-tetrahydroindenyl) (1-methyl-3-normalbutylcyclopentadienyl) zirconium difluoride, (4,5,6,7-tetrahydroindenyl) (1-methyl-3 -Normal butylcyclopentadienyl) hafnium difluoride, (4,5,6,7-tetrahydroindenyl) (1-methyl-3-normalbutylcyclopentadienyl) titanium dibromide, (4,5, 6,7-tetrahydroindenyl) (1-methyl-3-normal butylcyclopentadienyl) zirconium dibromide, (4,5,6,7-tetrahydroindenyl) (1-methyl-3-normalbutyl Cyclopentadienyl) hafnium dibromide, (4,5,6 , 7-tetrahydroindenyl) (1-methyl-3-normalbutylcyclopentadienyl) titanium diiodide, (4,5,6,7-tetrahydroindenyl) (1-methyl-3-normalbutyl Cyclopentadienyl) zirconium diiodide, (4,5,6,7-tetrahydroindenyl) (1-methyl-3-normalbutylcyclopentadienyl) hafnium diiodide, (4,5,6, 7-tetrahydroindenyl) (pentamethylcyclopentadienyl) zirconium dichloride, (4,5,6,7-tetrahydroindenyl) (pentamethylcyclopentadienyl) hafnium dichloride, (4,5, 6,7-tetrahydroindenyl) (pentamethylcyclopentadienyl) titanium difluoride, (4,5,6,7-tetrahydroindenyl) (pentamethylcyclopentadienyl) zirconium difluoride, ( 4,5,6,7-tetrahydroindenyl) (pentamethylcyclopentadienyl) hafnium difluoride, (4,5,6,7-tetrahydroindenyl) (pentamethylsa Clopentadienyl) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (pentamethylcyclopentadienyl) zirconium dibromide, (4,5,6,7-tetrahydroindenyl) ( Pentamethylcyclopentadienyl) hafnium dibromide, (4,5,6,7-tetrahydroindenyl) (pentamethylcyclopentadienyl) titanium diiodide, (4,5,6,7-tetrahydroinde) Nil) (pentamethylcyclopentadienyl) zirconium diiodide, (4,5,6,7-tetrahydroindenyl) (pentamethylcyclopentadienyl) hafnium diiodide,

(4,5,6,7-테트라하이드로인데닐)(테트라메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(테트라메틸싸이클로펜타디에닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(테트라메틸싸이클로펜타디에닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(테트라메틸싸이클로펜타디에닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(테트라메틸싸이클로펜타디에닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(테트라메틸싸이클로펜타디에닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(테트라메틸싸이클로펜타디에닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(테트라메틸싸이클로펜타디에닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(테트라메틸싸이클로펜타디에닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(테트라메틸싸이클로펜타디에닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(테트라메틸싸이클로펜타디에닐)하프늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로펜틸싸이클로펜타디에닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로펜틸싸이클로펜타디에닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로펜틸싸이클로펜타디에닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로펜틸싸이클로펜타디에닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로펜틸싸이클로펜타디에닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로펜틸싸이클로펜타디에닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로펜틸싸이클로펜타디에닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로펜틸싸이클로펜타디에닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로펜틸싸이클로펜타디에닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)( 싸이클로펜틸싸이클로펜타디에닐)하프늄 디아이오다이드, (4,5,6,7-tetrahydroindenyl) (tetramethylcyclopentadienyl) zirconium dichloride, (4,5,6,7-tetrahydroindenyl) (tetramethylcyclopentadienyl) hafnium di Chloride, (4,5,6,7-tetrahydroindenyl) (tetramethylcyclopentadienyl) titanium difluoride, (4,5,6,7-tetrahydroindenyl) (tetramethylcyclopentadienyl Zirconium difluoride, (4,5,6,7-tetrahydroindenyl) (tetramethylcyclopentadienyl) hafnium difluoride, (4,5,6,7-tetrahydroindenyl) (tetramethyl Cyclopentadienyl) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (tetramethylcyclopentadienyl) zirconium dibromide, (4,5,6,7-tetrahydroindenyl) ( Tetramethylcyclopentadienyl) hafnium dibromide, (4,5,6,7-tetrahydroindenyl) (tetramethylcyclo Tadienyl) titanium diiodide, (4,5,6,7-tetrahydroindenyl) (tetramethylcyclopentadienyl) zirconium diiodide, (4,5,6,7-tetrahydroindenyl) (Tetramethylcyclopentadienyl) hafnium diiodide, (4,5,6,7-tetrahydroindenyl) (cyclopentylcyclopentadienyl) zirconium dichloride, (4,5,6,7-tetrahydro Indenyl) (cyclopentylcyclopentadienyl) hafnium dichloride, (4,5,6,7-tetrahydroindenyl) (cyclopentylcyclopentadienyl) titanium difluoride, (4,5,6,7 -Tetrahydroindenyl) (cyclopentylcyclopentadienyl) zirconium difluoride, (4,5,6,7-tetrahydroindenyl) (cyclopentylcyclopentadienyl) hafnium difluoride, (4,5 , 6,7-tetrahydroindenyl) (cyclopentylcyclopentadienyl) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (cyclopentylcyclopentadienyl) zirconium dibromide, (4,5,6,7-tetrahydroindenyl) (cyclopentylcyclopentadienyl) hafnium di Bromide, (4,5,6,7-tetrahydroindenyl) (cyclopentylcyclopentadienyl) titanium diiodide, (4,5,6,7-tetrahydroindenyl) (cyclopentylcyclopentadienyl ) Zirconium diiodide, (4,5,6,7-tetrahydroindenyl) (cyclopentylcyclopentadienyl) hafnium diiodide,

(4,5,6,7-테트라하이드로인데닐)(싸이클로헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로헥실싸이클로펜타디에닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로헥실싸이클로펜타디에닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로헥실싸이클로펜타디에닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로헥실싸이클로펜타디에닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로헥실싸이클로펜타디에닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로헥실싸이클로펜타디에닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로헥실싸이클로펜타디에닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로헥실싸이클로펜타디에닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로헥실싸이클로펜타디에닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(싸이클로헥실싸이클로펜타디에닐)하프늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(실라싸이클로부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(실라싸이클로부틸싸이클로펜타디에닐)하프늄 디클로라이드, (4,5,6,7-테트라하이드로인데닐)(실라싸이클로부틸싸이클로펜타디에닐)티타늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(실라싸이클로부틸싸이클로펜타디에닐)지르코늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(실라싸이클로부틸싸이클로펜타디에닐)하프늄 디플루오라이드, (4,5,6,7-테트라하이드로인데닐)(실라싸이클로부틸싸이클로펜타디에닐)티타늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(실라싸이클로부틸싸이클로펜타디에닐)지르코늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(실라싸이클로부틸싸이클로펜타디에닐)하프늄 디브로마이드, (4,5,6,7-테트라하이드로인데닐)(실라싸이클로부틸싸이클로펜타디에닐)티타늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(실라싸이클로부틸싸이클로펜타디에닐)지르코늄 디아이오다이드, (4,5,6,7-테트라하이드로인데닐)(실라싸이클로부틸싸이클로펜타디에닐)하프늄 디아이오다이드, 이들의 혼합물, 및 그 유사 화합물
(4,5,6,7-tetrahydroindenyl) (cyclohexylcyclopentadienyl) zirconium dichloride, (4,5,6,7-tetrahydroindenyl) (cyclohexylcyclopentadienyl) hafnium di Chloride, (4,5,6,7-tetrahydroindenyl) (cyclohexylcyclopentadienyl) titanium difluoride, (4,5,6,7-tetrahydroindenyl) (cyclohexylcyclopentadienyl Zirconium difluoride, (4,5,6,7-tetrahydroindenyl) (cyclohexylcyclopentadienyl) hafnium difluoride, (4,5,6,7-tetrahydroindenyl) (cyclohexyl Cyclopentadienyl) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (cyclohexylcyclopentadienyl) zirconium dibromide, (4,5,6,7-tetrahydroindenyl) ( Cyclohexylcyclopentadienyl) hafnium dibromide, (4,5,6,7-tetrahydroindenyl) Clohexylcyclopentadienyl) titanium diiodide, (4,5,6,7-tetrahydroindenyl) (cyclohexylcyclopentadienyl) zirconium diiodide, (4,5,6,7-tetrahydro Indenyl) (cyclohexylcyclopentadienyl) halfium diiodide, (4,5,6,7-tetrahydroindenyl) (silacyclobutylcyclopentadienyl) zirconium dichloride, (4,5,6, 7-tetrahydroindenyl) (silacyclobutylcyclopentadienyl) hafnium dichloride, (4,5,6,7-tetrahydroindenyl) (silacyclobutylcyclopentadienyl) titanium difluoride, (4 , 5,6,7-tetrahydroindenyl) (silacyclobutylcyclopentadienyl) zirconium difluoride, (4,5,6,7-tetrahydroindenyl) (silacyclobutylcyclopentadienyl) hafnium Difluoride, (4,5,6,7-tetrahydroindenyl) (silacy Chlorobutylcyclopentadienyl) titanium dibromide, (4,5,6,7-tetrahydroindenyl) (silacyclobutylcyclopentadienyl) zirconium dibromide, (4,5,6,7-tetrahydroinde Nil) (silacyclobutylcyclopentadienyl) hafnium dibromide, (4,5,6,7-tetrahydroindenyl) (silacyclobutylcyclopentadienyl) titanium diiodide, (4,5,6, 7-tetrahydroindenyl) (silacyclobutylcyclopentadienyl) zirconium diiodide, (4,5,6,7-tetrahydroindenyl) (silacyclobutylcyclopentadienyl) halfium diiodide, these Mixtures of, and similar compounds thereof

또한, 본 발명에 따른 메탈로센 화합물은 상기 예에 한정되지 않고, 상기 예에 제시되지 않은 다른 치환 또는 비치환된 테트라하이드로인데닐(4HInd) 핵을 가진 리간드를 포함하는 메탈로센 화합물을 포함한다. 본 발명에 따른 메탈로센 화합물은 종래기술에 공지된 통상의 메탈로센 화합물 제조방법에 따라 제조될 수 있다. 예를 들면, 하기 실시예에 기재된 바와 같이, 비스(테트라하이드로인데닐)지르코늄 디클로라이드와 지르코늄 클로라이드를 반응시켜, (테트라하이드로인데닐)지르코늄 트리클로라이드를 얻고, 이를 인데닐 리튬과 반응시켜, (테트라하이드로인데닐)(인데닐)지르코늄 디클로라이드를 얻을 수 있다.
In addition, the metallocene compound according to the present invention is not limited to the above examples, and includes a metallocene compound including a ligand having another substituted or unsubstituted tetrahydroindenyl (4HInd) nucleus not shown in the above examples. do. The metallocene compound according to the present invention may be prepared according to a conventional metallocene compound preparation method known in the art. For example, as described in the Examples below, bis (tetrahydroindenyl) zirconium dichloride and zirconium chloride are reacted to obtain (tetrahydroindenyl) zirconium trichloride, which is reacted with indenyl lithium ( Tetrahydroindenyl) (indenyl) zirconium dichloride can be obtained.

본 발명에 따른 올레핀 중합용 메탈로센 촉매 조성물(시스템)은 상기 메탈로센 화합물 및 상기 메탈로센 화합물과 반응하여 메탈로센 화합물이 촉매 활성을 나타내도록 하는 활성체(activator)를 포함한다. 상기 활성체로는 알킬 알루미녹산, 유기 알루미늄 화합물, 벌키한 방향족 불소화합물, 개질된 클레이(clay), 루이스산 무기산화물 등의 통상의 활성체를 단독 또는 혼합하여 사용할 수 있다. 상기 알킬 알루미녹산은 하기 화학식 2로 표시되는 것으로서, 선상, 환상 또는 그물(Network) 구조를 가지는 통상적으로 시판되는 알킬 알루미녹산을 사용할 수 있으며, 비한정적으로는 하기 화학식 3 및 4로 표시되는 선상 또는 환상 구조 올리고머인 탄화수소(hydrocarbyl) 알루미녹산으로서, 예를 들면, 메틸알루미녹산, 에틸알루미녹산, 부틸알루미녹산, 헥실알루미녹산, 옥틸알루미녹산, 데실알루미녹산, 이들의 혼합물 등을 사용할 수 있으며, 바람직하게는 탄화수소 용액 상태로 시판되는 방향족 탄화수소 용액 알루미녹산을 사용할 수 있고, 더욱 바람직하게는 톨루엔에 용해된 알루미녹산 용액을 사용할 수 있다. 이와 같은 알루미녹산은 단독으로 또는 혼합하여 사용할 수 있다.The metallocene catalyst composition (system) for olefin polymerization according to the present invention includes an activator which reacts with the metallocene compound and the metallocene compound so that the metallocene compound exhibits catalytic activity. As the activator, conventional activators such as alkyl aluminoxanes, organoaluminum compounds, bulky aromatic fluorine compounds, modified clays, and Lewis acid inorganic oxides may be used alone or in combination. The alkyl aluminoxane is represented by the following Chemical Formula 2, and may be used a commercially available alkyl aluminoxane having a linear, cyclic or network structure, but is not limited to linear or represented by the following Chemical Formulas 3 and 4 As a hydrocarbon aluminoxane which is a cyclic oligomer, for example, methylaluminoxane, ethylaluminoxane, butylaluminoxane, hexyl aluminoxane, octyl aluminoxane, decyl aluminoxane, mixtures thereof and the like can be used. Preferably, an aromatic hydrocarbon solution aluminoxane commercially available in a hydrocarbon solution state can be used, and more preferably, an aluminoxane solution dissolved in toluene can be used. Such aluminoxanes may be used alone or in combination.

[화학식 2][Formula 2]

Figure pat00001
Figure pat00001

상기 화학식 2에서, R1은 탄소수 1 내지 10의 탄화수소 라디칼이고, x는 1 내지 70의 정수이다. In Formula 2, R 1 is a hydrocarbon radical of 1 to 10 carbon atoms, x is an integer of 1 to 70.

[화학식 3](3)

Figure pat00002
Figure pat00002

[화학식 4][Formula 4]

Figure pat00003
Figure pat00003

상기 화학식 3 및 4에서, R'은 각각 독립적으로 탄화수소(hydrocarbyl) 라디칼로서, 바람직하게는 탄소수 1 내지 10의 선형 또는 가지형 알킬 라디칼이며, 더욱 바람직하게는 R'의 대부분이 메틸기이고, x는 1 내지 50, 바람직하게는 10 내지 40의 정수이고, y는 3 내지 50, 바람직하게는 10 내지 40의 정수이다. 상기 알킬 알루미녹산의 제조방법으로는, 트리알킬알루미늄에 적량의 물을 첨가하거나, 물을 포함하는 탄화수소 화합물 또는 무기수화물염과 트리알킬알루미늄을 반응시키는 등 통상의 방법으로 제조할 수 있는데, 일반적으로 선형과 원형 알루미녹산이 혼합물의 형태로 얻어진다.
In Formulas 3 and 4, each R 'is independently a hydrocarbon radical, preferably a linear or branched alkyl radical having 1 to 10 carbon atoms, more preferably a majority of R' is a methyl group, and x is It is an integer of 1-50, Preferably it is 10-40, y is an integer of 3-50, Preferably it is 10-40. As the method for producing the alkyl aluminoxane, an appropriate amount of water may be added to trialkylaluminum, or a hydrocarbon compound containing water or an inorganic hydrate salt may be reacted with trialkylaluminum. Linear and circular aluminoxanes are obtained in the form of a mixture.

또한, 본 발명의 촉매 조성물은, 불순물 제거제로서 하기 화학식 5로 표시되는 유기알루미늄 화합물을 포함할 수 있다.In addition, the catalyst composition of the present invention may include an organoaluminum compound represented by the following Formula 5 as an impurity remover.

[화학식 5][Chemical Formula 5]

Figure pat00004
Figure pat00004

상기 화학식 5에서, R2, R3 및 R4는 각각 독립적으로 탄소수 1 내지 10의 알킬기 또는 알콕시기 또는 할라이드기(불소기, 염소기, 브롬기, 요오드기 등)이고, R2, R3 및 R4 중에 적어도 하나 이상은 알킬기이다. 상기 유기 알루미늄 화합물의 비한정적인 예로는, 트리메틸알루미늄, 트리에틸알루미늄, 트리부틸알루미늄, 트리헥실알루미늄, 트리옥틸알루미늄, 트리데실알루미늄 등의 트리알킬알루미늄; 디메틸알루미늄 메톡사이드, 디에틸알루미늄 메톡사이드, 디부틸알루미늄 메톡사이드 등의 디알킬알루미늄 알콕사이드; 디메틸알루미늄 클로라이드, 디에틸알루미늄 클로라이드, 디부틸알루미늄 클로라이드 등의 디알킬알루미늄 할라이드; 메틸알루미늄 디메톡사이드, 에틸알루미늄 디메톡사이드, 부틸알루미늄 디메톡사이드 등의 알킬알루미늄 디알콕사이드; 메틸알루미늄 디클로라이드, 에틸알루미늄 디클로라이드, 부틸알루미늄 디클로라이드 등의 알킬알루미늄 디할라이드, 이들의 혼합물 등을 예시할 수 있다.
In Formula 5, R 2 , R 3 and R 4 are each independently an alkyl group or an alkoxy group or a halide group (fluorine group, chlorine group, bromine group, iodine group, etc.) having 1 to 10 carbon atoms, R 2 , R 3 And at least one of R 4 is an alkyl group. Non-limiting examples of the organoaluminum compound include trialkylaluminum such as trimethylaluminum, triethylaluminum, tributylaluminum, trihexyl aluminum, trioctyl aluminum and tridecyl aluminum; Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum methoxide and dibutylaluminum methoxide; Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride and dibutylaluminum chloride; Alkyl aluminum dialkoxides such as methyl aluminum dimethoxide, ethyl aluminum dimethoxide and butyl aluminum dimethoxide; Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, butylaluminum dichloride, mixtures thereof and the like can be exemplified.

본 발명에 따른 촉매 조성물에 있어서, 활성체로서 사용되는 불소로 치환된 방향족기를 포함하는 벌키한 화합물은 하기 화학식 6으로 표시될 수 있다.In the catalyst composition according to the present invention, a bulky compound including an aromatic group substituted with fluorine used as an activator may be represented by the following formula (6).

[화학식 6][Formula 6]

Figure pat00005
Figure pat00005

상기 화학식 6에서, C는 루이스 염기의 수소 이온 결합 양이온이거나, 산화력이 있는 금속 또는 비금속 화합물이고, D는 주기율표상의 5~15족에 속하는 원소와 유기물질의 화합물이다. 상기 벌키한 방향족 불소 화합물(불소로 치환된 방향족 보론계 이온형 화합물)의 비한정적인 예로는 트리메틸암모늄 테트라키스(펜타플루오로페닐) 보레이트 (Trimethylammonium tetrakis(pentafluorophenyl)borate), 트리에틸암모늄 테트라키스(펜타플루오로페닐)보레이트, 트리프로필암모늄 테트라키스(펜타플루오로페닐) 보레이트, 트리부틸암모늄 테트라키스(펜타플루오로페닐)보레이트, 아닐리늄 테트라키스(펜타플루오로페닐)보레이트, 피리디늄 테트라키스(펜타플루오로페닐)보레이트, 페로세늄 테트라키스(펜타플루오로페닐)보레이트(Ferrocenium tetrakis(pentafluorophenyl) borate), 실버 테트라키스(펜타플루오로페닐)보레이트, 트리스(펜타플루오로페닐)보레인 (Tris(pentafluorophenyl) borane), 트리스(3,4,5-트리플루오로페닐)보레인, 이들의 혼합물 등을 예시할 수 있다.
In Chemical Formula 6, C is a hydrogen ion-bonding cation of a Lewis base or an oxidizing metal or nonmetallic compound, and D is a compound of an element and an organic substance belonging to groups 5 to 15 of the periodic table. Non-limiting examples of the bulky aromatic fluorine compound (fluorine-substituted aromatic boron-based ionic compound) include trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis ( Pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, aninium tetrakis (pentafluorophenyl) borate, pyridinium tetrakis ( Pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, tris (pentafluorophenyl) borane (Tris ( pentafluorophenyl) borane), tris (3,4,5-trifluorophenyl) borane, mixtures thereof, and the like.

또한, 상기 활성체로서 사용될 수 있는 개질된 클레이로는 비한정적으로 N,N-디메틸아닐리늄 몬트모릴로나이트(N,N-dimethylanilinium montmorillonite), N,N-디메틸아닐리늄 헥토라이트(N,N-dimethylanilinium hectorite), 이들의 혼합물 등을 예시할 수 있고, 활성체로서 루이스산 무기산화물(Lewis acid inorganic oxide)로는 불소화된 실리카 알루미나를 예시할 수 있다.
In addition, modified clays that can be used as the activator include, but are not limited to, N, N-dimethylanilinium montmorillonite, N, N-dimethylanilinium hectorite (N, N -dimethylanilinium hectorite), mixtures thereof, and the like, and fluorinated silica alumina as Lewis acid inorganic oxide as an active agent.

본 발명에 따른 올레핀 중합용 촉매 조성물은, 상기 화학식 1로 표시되는 메탈로센 화합물 1몰에 대하여, 상기 화학식 2, 3, 4 등으로 표시되는 알루미녹산의 알루미늄이 1 내지 100,000몰, 바람직하게는 5 내지 5,000몰이 되도록 알루미녹산을 혼합하여 제조할 수 있다. 활성체가 벌키한 불소 치환 방향족 화합물(화학식 6) 중 유기보론 화합물인 경우, 유기보론 화합물과 메탈로센 화합물의 몰비([유기보론화합물]/[전이금속화합물])는 통상 1 내지 1,000, 바람직하게는 1 내지 100의 범위 내인 것이 좋다. 본 발명의 메탈로센 화합물과 상기 유기알루미늄 화합물, 개질된 클레이, 루이스산 무기화합물 등이 혼합될 경우, 그 비율은, 사용 목적, 촉매의 종류 등에 따라 달라질 수 있으며, 통상의 기술에 따라 적절히 설정될 수 있다.
In the catalyst composition for olefin polymerization according to the present invention, 1 to 100,000 moles of aluminum of the aluminoxane represented by the above formulas (2), (3) and (4), etc., is preferably 1 mole of the metallocene compound represented by the above formula (1). It can be prepared by mixing the aluminoxane to 5 to 5,000 moles. When the activator is an organic boron compound in the bulky fluorine-substituted aromatic compound (Formula 6), the molar ratio ([organic boron compound] / [transition metal compound]) of the organic boron compound and the metallocene compound is usually 1 to 1,000, preferably Is preferably in the range of 1 to 100. When the metallocene compound of the present invention and the organoaluminum compound, modified clay, Lewis acid inorganic compound, etc. are mixed, the ratio may vary depending on the purpose of use, the type of catalyst, and the like, and is appropriately set according to conventional techniques. Can be.

상기 촉매 조성물의 혼합은 특별한 제한 없이 임의적으로 수행될 수 있다. 예를 들면, 상기 화학식 1로 표시되는 메탈로센 화합물과 알루미녹산을 5분 내지 10시간, 바람직하게는 15분 내지 4시간 동안 혼합시킬 수 있다. 상기 화합물들의 혼합 방법에는 제한이 없으나, 통상 질소 또는 아르곤의 불활성 분위기 하에서, 용매를 사용하지 않거나, 헵탄, 헥산, 벤젠, 톨루엔, 크실렌(xylene) 등의 불활성 탄화수소 용매 또는 그 혼합물의 존재 하에서, 상기 두가지 화합물을 혼합시키는 것이 바람직하며, 상기 혼합과정의 온도는 0 내지 150℃, 바람직하게는 10 내지 90℃이다. 상기 탄화수소 용매 등에 균일하게 용해된 용액 상태의 촉매는 그대로 사용되거나, 용매를 제거시킨 고체분말 상태로 사용될 수 있으며, 상기 고체분말 상태의 촉매는 용액 상태의 촉매를 침전화 반응시킨 후, 침전된 침전물을 고체화시키는 방법으로 제조할 수도 있다.
Mixing of the catalyst composition may be optionally performed without particular limitation. For example, the metallocene compound represented by Formula 1 and the aluminoxane may be mixed for 5 minutes to 10 hours, preferably 15 minutes to 4 hours. There is no limitation in the method of mixing the compounds, but in the presence of an inert hydrocarbon solvent such as heptane, hexane, benzene, toluene, xylene, or a mixture thereof, in general, in the inert atmosphere of nitrogen or argon, It is preferable to mix the two compounds, and the temperature of the mixing process is 0 to 150 ° C, preferably 10 to 90 ° C. The catalyst in a solution state uniformly dissolved in the hydrocarbon solvent or the like may be used as it is, or may be used in a solid powder state in which the solvent is removed. The catalyst in the solid powder state may precipitate a catalyst in a solution state and then precipitate the precipitate. It can also be prepared by a method of solidifying.

또한, 본 발명은 상기 화학식 1로 표시되는 메탈로센 화합물과 상기 화학식 2로 표시되는 알루미녹산 화합물 등의 활성체가 혼합된 촉매 조성물을 유기 또는 무기 담체(캐리어, carrier)와 더욱 접촉시킨 올레핀 중합용 촉매 조성물을 제공한다. 상기 촉매 및/또는 활성체는 담체에 담지된 형태로 존재하거나 담체의 불용성 입자 형태로 존재할 수 있다. 본 발명에 따른 촉매를 담체에 접촉시키는 방법으로는 다음의 방법을 예시할 수 있다. 먼저, 상기 화학식 1로 표시되는 메탈로센 화합물과 화학식 2로 표시되는 알루미녹산 화합물을 혼합한 용액 상태의 촉매를 다공성 담체(예: 50 내지 500Å의 세공크기 및 0.1 내지 5.0㎤/g의 기공부피를 갖는 실리카 담체)와 접촉시켜 슬러리 상태로 만든다. 다음으로, 상기 혼합물에 1 내지 10,000kHz 주파수 범위의 음향파 또는 진동파를 0℃ 내지 120℃에서 1 내지 6시간 동안 작용시켜, 촉매 성분들을 담체의 미세 세공 깊숙이 균일하게 침투시킨 후, 진공 처리 또는 질소 흐름에서 건조시켜 고체분말 형태의 촉매를 제조할 수 있다. 상기 음향파 또는 진동파는 초음파(ultrasonic waves)인 것이 바람직하며, 20 내지 500kHz의 주파수를 사용하면 더욱 바람직하다. 상기 촉매와 담체의 접촉방법은 상기 음향파 또는 진동파를 가한 다음, 펜탄, 헥산, 헵탄, 이소파라핀, 톨루엔, 크실렌 및 그들의 혼합물로 이루어진 군으로부터 선택된 탄화수소를 사용하여 상기 담지 촉매를 세척하는 공정을 더욱 포함할 수 있다.
In addition, the present invention is an olefin polymerization for further contacting an organic or inorganic carrier (carrier, carrier) with a catalyst composition mixed with an active material such as a metallocene compound represented by the formula (1) and an aluminoxane compound represented by the formula (2) It provides a catalyst composition. The catalyst and / or activator may be present in the form supported on the carrier or in the form of insoluble particles of the carrier. The following method can be illustrated as a method of contacting a catalyst according to the present invention to a carrier. First, a catalyst in a solution state in which the metallocene compound represented by Formula 1 and the aluminoxane compound represented by Formula 2 is mixed with a porous carrier (for example, a pore size of 50 to 500 mm 3 and a pore volume of 0.1 to 5.0 cm 3 / g) Silica carrier) to make a slurry state. Next, an acoustic or vibration wave in the frequency range of 1 to 10,000 kHz is applied to the mixture at 0 ° C. to 120 ° C. for 1 to 6 hours to uniformly infiltrate the catalyst components deep into the micropores of the carrier, followed by vacuum treatment or The catalyst can be prepared in the form of a solid powder by drying in a nitrogen stream. The acoustic wave or vibration wave is preferably ultrasonic waves, more preferably using a frequency of 20 to 500 kHz. The method of contacting the catalyst with the carrier may include applying the acoustic or vibration wave and then washing the supported catalyst using a hydrocarbon selected from the group consisting of pentane, hexane, heptane, isoparaffin, toluene, xylene and mixtures thereof. It may further include.

상기 담체로는 미세한 세공(pore) 및 넓은 표면적을 지닌 다공성 무기물, 무기염 또는 유기 화합물을 제한 없이 사용할 수 있다. 상기 무기 담체의 형태는 상기 담지 촉매 제조를 위한 공정에서 소정의 형태를 얻을 수 있는 것이라면, 제한 없이 사용할 수 있으며, 분말, 입자, 플레이크, 호일, 섬유 등의 형태를 예시할 수 있다. 상기 무기 담체의 형태와 상관없이, 무기 담체의 최대 길이는 5 내지 200㎛, 바람직하게는 10 내지 100㎛이고, 상기 무기 담체의 표면적은 50 내지 1,000㎡/g이고, 공극 체적은 0.05 내지 5㎤/g인 것이 바람직하다. 일반적으로, 상기 무기 담체는 사용 전에 물 또는 하이드록시기 제거 과정을 거쳐야 하는데, 상기 과정은 공기, 질소, 아르곤 등의 불활성 기체 분위기에서 담체를 200℃ 내지 900℃의 온도로 소성시킴으로써 수행될 수 있다. 상기 무기염 또는 무기물 담체의 비한정적인 예로는 실리카, 알루미나, 보오크싸이트(Bauxite), 제올라이트, 염화마그네슘(MgCl2), 염화칼슘(CaCl2), 산화마그네슘(MgO), 산화지르코늄(ZrO2), 산화티탄(TiO2), 산화붕소(B2O3), 산화칼슘(CaO), 산화아연(ZnO), 산화바륨(BaO), 산화토륨(ThO2) 또는 이들의 혼합물로서 실리카-산화마그네슘(SiO2-MgO), 실리카-알루미나(SiO2-Al2O3), 실리카-산화티탄(SiO2-TiO2), 실리카-오산화바나듐(SiO2-V2O5), 실리카-산화크롬 (SiO2-CrO3), 실리카-산화티탄-산화마그네슘(SiO2-TiO2-MgO), 이들의 혼합물 또는 이들 화합물에 소량의 카보네이트(carbonate), 썰페이트(sulfate) 또는 나이트레이트(nitate)가 포함된 화합물을 예시할 수 있고, 상기 유기 화합물 담체의 비한정적인 예로는 전분, 시클로덱스트린, 합성 폴리머 등을 예시할 수 있다.
As the carrier, a porous inorganic material, an inorganic salt or an organic compound having fine pores and a large surface area can be used without limitation. The form of the inorganic carrier can be used without limitation, as long as it can obtain a predetermined form in the process for preparing the supported catalyst, it may be exemplified in the form of powder, particles, flakes, foil, fibers and the like. Regardless of the form of the inorganic carrier, the maximum length of the inorganic carrier is 5 to 200 mu m, preferably 10 to 100 mu m, the surface area of the inorganic carrier is 50 to 1,000 m 2 / g, and the void volume is 0.05 to 5 cm 3. / g is preferred. In general, the inorganic carrier must undergo a water or hydroxy group removal process before use, which can be carried out by calcining the carrier to a temperature of 200 ℃ to 900 ℃ in an inert gas atmosphere such as air, nitrogen, argon, etc. . Non-limiting examples of the inorganic salt or inorganic carrier include silica, alumina, bauxite, zeolite, magnesium chloride (MgCl 2 ), calcium chloride (CaCl 2 ), magnesium oxide (MgO), zirconium oxide (ZrO 2 ) Silica-magnesium oxide as titanium oxide (TiO 2 ), boron oxide (B 2 O 3 ), calcium oxide (CaO), zinc oxide (ZnO), barium oxide (BaO), thorium oxide (ThO 2 ) or mixtures thereof (SiO 2 -MgO), silica-alumina (SiO 2 -Al 2 O 3 ), silica-titanium oxide (SiO 2 -TiO 2 ), silica-vanadium pentoxide (SiO 2 -V 2 O 5 ), silica-chromium oxide (SiO 2 -CrO 3 ), silica-titanium oxide-magnesium oxide (SiO 2 -TiO 2 -MgO), mixtures thereof or a small amount of carbonate, sulfate or nitrate in these compounds It can be exemplified a compound containing, and non-limiting examples of the organic compound carrier may include starch, cyclodextrin, synthetic polymer and the like.

본 발명에 따른 촉매를 상기 담체와 접촉시킬 때 사용되는 용매로는 펜탄, 헥산, 헵탄, 옥탄, 노난, 데칸, 운데칸, 도데칸 등의 지방족 탄화수소계 용매, 벤젠, 모노클로로벤젠, 디클로로벤젠, 트리클로로벤젠, 톨루엔 등의 방향족 탄화수소계 용매, 디클로로메탄, 트리클로로메탄, 디클로로에탄, 트리클로로에탄 등의 할로겐화 지방족 탄화수소 용매를 사용할 수 있다. 상기 담체와 접촉되는 올레핀 중합용 촉매조성물은 특별히 한정되지는 않지만, 상기 화학식 1로 표시되는 메탈로센 화합물 1몰에 대하여, 화학식 2로 표시되는 알루미녹산의 알루미늄이 1 내지 1,000몰, 바람직하게는 1 내지 500몰로 이루어진 것이 바람직하다.
As a solvent used when the catalyst according to the present invention is contacted with the carrier, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, benzene, monochlorobenzene, dichlorobenzene, Aromatic hydrocarbon solvents, such as trichlorobenzene and toluene, and halogenated aliphatic hydrocarbon solvents, such as dichloromethane, trichloromethane, dichloroethane, and trichloroethane, can be used. The catalyst composition for olefin polymerization contacted with the carrier is not particularly limited, but 1 to 1,000 moles of aluminum of the aluminoxane represented by the formula (2) is preferably used with respect to 1 mole of the metallocene compound represented by the formula (1). It is preferable that it consists of 1-500 mol.

본 발명은, 상기 화학식 1로 표시되는 메탈로센 화합물 및, 필요에 따라, 화학식 2로 표시되는 알루미녹산 화합물 등의 활성체, 유기 또는 무기 담체 등을 포함하는 촉매 조성물의 존재 하에서, 하나 이상의 올레핀을 중합하는 단계를 포함하는 올레핀의 중합방법을 제공한다. 즉, 본 발명에 따른 올레핀의 중합방법은, 균일 용액 상태의 촉매뿐 만 아니라, 무기물 담체(예 실리카, 알루미나, 실리카-알루미나 혼합물 등)에 담지된 형태 또는 담체의 불용성 입자 형태로 존재하는 촉매를 이용하는 것을 포함한다. 따라서, 본 발명에 따른 올레핀의 중합방법은, 액상, 슬러리상, 괴상(Bulk Phase) 또는 기상 중합반응으로 수행될 수 있다. 또한 각각의 중합반응 조건은 사용되는 촉매의 상태(균일상 또는 불균일상(담지형)), 중합 방법(용액 중합, 슬러리 중합, 기상 중합), 목적하는 중합결과 또는 중합체의 형태에 따라 다양하게 변형될 수 있다. 상기 중합이 액상 또는 슬러리상에서 실시되는 경우, 용매 또는 올레핀 자체를 매질로 사용할 수 있다. 상기 용매로는 프로판, 부탄, 펜탄, 헥산, 옥탄, 데칸, 도데칸, 시클로펜탄, 메틸시클로펜탄, 시클로헥산, 벤젠, 톨루엔, 자일렌, 디클로로메탄, 클로로에탄, 1,2-디클로로에탄, 클로로벤젠 등을 예시할 수 있으며, 이들 용매를 일정한 비율로 섞어 사용할 수도 있다.
The present invention, at least one olefin in the presence of a catalyst composition comprising an active metal, such as an aluminoxane compound represented by the general formula (2) and an aluminoxane compound represented by the general formula (2), an organic or inorganic carrier, etc. It provides a polymerization method of olefin comprising the step of polymerizing. That is, the polymerization method of the olefin according to the present invention is not only a catalyst in a homogeneous solution state, but also a catalyst present in an inorganic carrier (eg, silica, alumina, silica-alumina mixture, etc.) or in an insoluble particle form of the carrier. It includes use. Therefore, the polymerization method of the olefin according to the present invention may be carried out by liquid phase, slurry phase, bulk phase or gas phase polymerization. In addition, each polymerization condition may vary depending on the state of the catalyst used (homogeneous or heterogeneous phase (supported)), the polymerization method (solution polymerization, slurry polymerization, gas phase polymerization), the desired polymerization result or the shape of the polymer. Can be. When the polymerization is carried out in a liquid phase or a slurry phase, a solvent or olefin itself may be used as a medium. The solvent includes propane, butane, pentane, hexane, octane, decane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, benzene, toluene, xylene, dichloromethane, chloroethane, 1,2-dichloroethane, chloro Benzene etc. can be illustrated and these solvent can also be mixed and used in fixed ratio.

상기 중합에 사용되는 올레핀은 단독 또는 2종 이상 혼합된 것일 수 있다. 즉, 본 발명의 올레핀 촉매는 올레핀 단량체의 단독중합뿐 만 아니라, 올레핀 단량체/공단량체의 공중합에 사용될 수 있으며, 상기 중합 또는 공중합에 바람직한 올레핀류로는 알파-올레핀류, 환상 올레핀류, 디엔류, 트리엔(trienes)류, 스티렌(styrenes)류 등이 있다. 상기 알파-올레핀류는 탄소수 2 내지 12, 바람직하게는 2 내지 8의 지방족 올레핀으로서, 구체적으로는 에틸렌, 프로필렌, 부텐-1, 펜텐-1, 3-메틸부텐-1, 헥센-1, 4-메틸펜텐-1, 3-메틸펜텐-1, 헵텐-1, 옥텐-1, 데센-1(decene-1), 4,4-디메틸-1-펜텐, 4,4-디에틸-1-헥센, 3,4-디메틸-1-헥센 등을 예시할 수 있다. 또한, 상기 알파-올레핀류는 단독 중합되거나 교대(alternating), 랜덤(random), 또는 블록(block) 공중합 될 수 있다. 상기 알파-올레핀류의 공중합은 에틸렌과 탄소수 3 내지 12, 바람직하게는 3 내지 8의 알파-올레핀의 공중합(예를 들면, 에틸렌과 프로필렌, 에틸렌과 부텐-1, 에틸렌과 헥센-1, 에틸렌과 4-메틸펜텐-1, 에틸렌과 옥텐-1 등) 및 프로필렌과 탄소수 4 내지 12, 바람직하게는 4 내지 8의 알파-올레핀의 공중합(예를 들면, 프로필렌과 부텐-1, 프로필렌과 4-메틸펜텐-1, 프로필렌과 4-메틸부텐-1, 프로필렌과 헥센-1, 프로필렌과 옥텐-1 등)을 포함한다. 상기 에틸렌 또는 프로필렌과 다른 알파-올레핀의 공중합에 있어서, 다른 알파-올레핀의 양은 통상 전체 모노머의 90몰% 이하이며, 구체적으로는, 에틸렌 공중합체의 경우 40몰% 이하, 바람직하게는 30몰% 이하, 더욱 바람직하게는 20몰% 이하이고, 프로필렌 공중합체의 경우 1 내지 90몰%, 바람직하게는 5 내지 90몰%, 더욱 바람직하게는 10 내지 70몰%이다.
The olefins used for the polymerization may be one or a mixture of two or more kinds. That is, the olefin catalyst of the present invention can be used not only for the homopolymerization of olefin monomers but also for the copolymerization of olefin monomers / comonomers, and olefins preferred for the polymerization or copolymerization include alpha-olefins, cyclic olefins, and dienes. , Trienes and styrenes. The alpha-olefins are aliphatic olefins having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, specifically ethylene, propylene, butene-1, pentene-1, 3-methylbutene-1, hexene-1, 4- Methylpentene-1, 3-methylpentene-1, heptene-1, octene-1, decene-1 (decene-1), 4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene, 3, 4- dimethyl- 1-hexene etc. can be illustrated. In addition, the alpha-olefins may be homopolymerized or alternating, random, or block copolymerized. Copolymerization of the alpha-olefins is copolymerization of ethylene and alpha-olefin having 3 to 12, preferably 3 to 8 carbon atoms (for example, ethylene and propylene, ethylene and butene-1, ethylene and hexene-1 and ethylene 4-methylpentene-1, ethylene and octene-1, etc.) and copolymerization of propylene with alpha-olefins having 4 to 12, preferably 4 to 8, carbon atoms (e.g. propylene and butene-1, propylene and 4-methyl Pentene-1, propylene and 4-methylbutene-1, propylene and hexene-1, propylene and octene-1, and the like. In the copolymerization of ethylene or propylene with other alpha-olefins, the amount of other alpha-olefins is usually 90 mol% or less of all monomers, specifically 40 mol% or less, preferably 30 mol% for ethylene copolymers. Hereinafter, more preferably 20 mol% or less, and in the case of a propylene copolymer, it is 1-90 mol%, Preferably it is 5-90 mol%, More preferably, it is 10-70 mol%.

상기 환상 올레핀류로는, 탄소수 3 내지 24, 바람직하게는 3 내지 18의 환상 올레핀을 사용할 수 있으며, 구체적으로 싸이클로펜텐(cyclopentene), 싸이클로부텐, 싸이클로헥센, 3-메틸싸이클로헥센, 싸이클로옥텐, 테트라싸이클로데센, 옥타싸이클로데센, 디싸이클로펜타디엔, 노르보르넨, 5-메틸-2-노르보르넨, 5-에틸-2-노르보르넨, 5-이소부틸-2-노르보르넨, 5,6-디메틸-2-노르보르넨, 5,5,6-트리메틸-2-노르보르넨 및 에틸렌노르보르넨 등을 예시할 수 있다. 상기 환상 올레핀류는 상기 알파-올레핀류와 공중합이 가능하며, 이때 환상 올레핀의 양은 공중합체에 대하여 1 내지 50 몰%, 바람직하게는 2 내지 50몰%이다. 또한 상기 디엔류 및 트리엔(triene)은 2개 또는 3개의 이중결합을 갖는 탄소수 4 내지 26의 폴리엔이 바람직하며, 구체적으로 1,3-부타디엔, 1,4-펜타디엔, 1,4-헥사디엔, 1,5-헥사디엔, 1,9-데카디엔, 2-메틸-1,3-부타디엔 등을 예시할 수 있다. 상기 스티렌류의 예로는 스티렌 또는 탄소수 1 내지 10의 알킬기, 알콕시기 또는 할로겐화알킬기, 할로겐기, 아민기, 실릴기 등으로 치환된 스티렌 등을 예시할 수 있다.
As the cyclic olefins, cyclic olefins having 3 to 24 carbon atoms, preferably 3 to 18 carbon atoms, may be used. Specifically, cyclopentene, cyclobutene, cyclohexene, 3-methylcyclohexene, cyclooctene and tetra Cyclodecene, octacyclodecene, dicyclopentadiene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6 -Dimethyl-2-norbornene, 5,5,6-trimethyl-2-norbornene, ethylene norbornene and the like can be exemplified. The cyclic olefins can be copolymerized with the alpha-olefins, wherein the amount of the cyclic olefin is 1 to 50 mol%, preferably 2 to 50 mol% with respect to the copolymer. In addition, the dienes and triene (polyene) is preferably a polyene having 4 to 26 carbon atoms having two or three double bonds, specifically 1,3-butadiene, 1,4-pentadiene, 1,4-hexa Dienes, 1,5-hexadiene, 1,9-decadiene, 2-methyl-1,3-butadiene and the like can be exemplified. Examples of the styrenes may include styrene or styrene substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group or a halogenated alkyl group, a halogen group, an amine group, a silyl group, or the like.

본 발명에 따른 올레핀의 중합 또는 공중합에 있어서, 상기 화학식 1로 표시되는 메탈로센 화합물의 양은 특별히 한정되지 않지만, 중합에 사용되는 반응계 내에서 상기 화학식 1로 표시되는 메탈로센 화합물의 중심 금속 농도가 10-8 내지 101㏖/ℓ인 것이 바람직하며, 10-7 내지 10-2 ㏖/ℓ이면 더욱 바람직하다. 상기 메탈로센 화합물의 사용량이 상기 범위를 벗어나면, 촉매 활성이 부족하거나, 불필요하게 과량의 촉매가 사용되는 단점이 있다. 본 발명에 따른 올레핀의 중합 또는 공중합에 있어서, 중합온도는 반응 물질, 반응 조건 등에 따라 변할 수 있으므로 특별히 한정되지는 않지만, 용액 중합의 경우 0 내지 250℃, 바람직하게는 10 내지 200℃이고, 슬러리 또는 기상 중합의 경우 0 내지 120℃, 바람직하게는 20 내지 100℃이다. 또한 중합압력은 대기압 내지 500 kg/㎠, 바람직하게는 대기압 내지 50 kg/㎠이며, 상기 중합은 배치식, 반연속식 또는 연속식으로 수행 될 수 있다. 상기 중합은 상이한 반응조건을 갖는 두가지 이상의 단계로 수행될 수도 있다. 본 발명의 올레핀 중합용 촉매를 이용하여 제조되는 최종 중합체의 분자량은 중합 온도를 변화시키거나 반응기 내에 수소를 주입하는 등의 방법으로 조절할 수 있다.
In the polymerization or copolymerization of the olefin according to the present invention, the amount of the metallocene compound represented by the formula (1) is not particularly limited, but the concentration of the central metal of the metallocene compound represented by the formula (1) in the reaction system used for the polymerization Is preferably 10 −8 to 10 1 mol / l, and more preferably 10 −7 to 10 −2 mol / l. If the amount of the metallocene compound is out of the above range, there is a disadvantage in that the catalyst activity is insufficient or an excessive amount of the catalyst is unnecessarily used. In the polymerization or copolymerization of the olefin according to the present invention, the polymerization temperature is not particularly limited since it may vary depending on the reaction materials, reaction conditions, and the like, but in the case of solution polymerization, it is 0 to 250 ° C, preferably 10 to 200 ° C, and a slurry Or in the case of gas phase polymerization, 0 to 120 ° C, preferably 20 to 100 ° C. In addition, the polymerization pressure is from atmospheric pressure to 500 kg / ㎠, preferably atmospheric pressure to 50 kg / ㎠, the polymerization can be carried out batch, semi-continuous or continuous. The polymerization may be carried out in two or more stages with different reaction conditions. The molecular weight of the final polymer produced using the catalyst for olefin polymerization of the present invention can be controlled by changing the polymerization temperature or injecting hydrogen into the reactor.

본 발명에 따른 올레핀 촉매는, 올레핀 단량체의 본중합뿐 만 아니라, 예비중합 공정에도 사용될 수 있다. 상기 예비중합 공정에서, 올레핀 중합체 또는 공중합체는 상기 올레핀 촉매 1g당 0.05 내지 500 g, 바람직하게는 0.1 내지 300 g, 더욱 바람직하게는 0.2 내지 100 g으로 제조되는 것이 바람직하다. 상기 예비중합 공정에 사용 가능한 올레핀류로는 에틸렌, 프로필렌, 1-부텐, 1-펜텐, 4-메틸-1-펜텐, 1-헥센, 1-옥텐, 1-데센, 1-도데센, 1-테트라데센, 3-메틸-1-부텐, 3-메틸-1-펜텐 등의 탄소수 2 내지 20의 α-올레핀류 등을 예시할 수 있으며, 본중합에 사용되는 것과 동일한 올레핀을 사용하는 것이 바람직하다.
The olefin catalyst according to the present invention can be used not only for the main polymerization of the olefin monomer but also for the prepolymerization process. In the prepolymerization process, the olefin polymer or copolymer is preferably produced in 0.05 to 500 g, preferably 0.1 to 300 g, more preferably 0.2 to 100 g per 1 g of the olefin catalyst. Olefins usable in the prepolymerization process are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1- C2-C20 alpha olefins, such as tetradecene, 3-methyl-1- butene, 3-methyl-1- pentene, etc. can be illustrated, It is preferable to use the same olefin as used for this polymerization. .

이하, 구체적인 실시예를 통하여 본 발명을 더욱 상세히 설명한다. 하기 실시 예는 본 발명을 설명하기 위한 것으로서, 본 발명의 범위가 하기 실시예에 의하여 한정되는 것은 아니다. 하기 실시예에 있어서, 올레핀 중합용 촉매는 공기와 수분이 완전히 차단된 쉬렌크(Schlenk) 기법 하에서 제조되었고, 불활성 기체로서 정제 건조된 질소를 사용하였다. 또한, 용매는 불활성 질소 분위기의 나트륨 금속 존재 하에서 건조하여 사용하였다. 중합체의 용융지수(MI: Melt Index) 및 HLMI(High Load Melt Index)는 ASTM D1238, 중합체의 밀도(Density)는 ASTM D1505에 따라 측정하였다.
Hereinafter, the present invention will be described in more detail with reference to specific examples. The following examples are provided to illustrate the present invention, but the scope of the present invention is not limited by the following examples. In the following examples, the catalyst for olefin polymerization was prepared under Schlenk technique in which air and moisture were completely blocked, and purified dried nitrogen was used as the inert gas. The solvent was used after drying in the presence of sodium metal in an inert nitrogen atmosphere. Melt Index (MI) and High Load Melt Index (HLMI) of the polymer were measured according to ASTM D1238 and Density of the polymer according to ASTM D1505.

[실시예 1]Example 1

가. (end. ( 테트라하이드로인데닐Tetrahydroindenyl )() ( 인데닐Indenil )지르코늄 )zirconium 디클로라이드의Dichloride 제조 Produce

질소 분위기 하에서, 500ml 용량의 둥근 플라스크에 비스(테트라하이드로인데닐)지르코늄 디클로라이드 1.065g(2.66mmol), 지르코늄 클로라이드 0.66g (2.83mmol) 및 톨루엔 100ml을 넣은 다음, 교반하면서 90℃에서 18시간 동안 반응시켰다. 반응이 완료된 후, 반응 생성물을 여과하여 여과액을 수집하였다. 인데닐 리튬 0.66g(5.406mmol)을 500ml 플라스크에 넣은 다음, 상기 여과액을 넣고, 혼합용액을 교반하면서, 90℃에서 18시간 동안 반응시켰다. 용매를 진공으로 제거하고, 디클로로메탄 100ml로 추출 및 여과한 후, 다시 용매를 제거하였다. 헥산 50mL를 주입하여 반응생성물을 슬러리화시키고, 이를 여과하고 헥산 500mL로 세척한 후, 진공으로 건조시켜, 1.52g(수율 72%)의 (테트라하이드로인데닐)(인데닐)지르코늄 디클로라이드를 얻었다. 수득된 (테트라하이드로인데닐)(인데닐)지르코늄 디클로라이드 화합물의 1H NMR(500MHz,CDCl3) 분석 결과는 1.54-1.50 (m, 2, C9H11), 1.79-1.70 (m, 2, C9H11), 2.44-2.38 (m, 2, C9H11), 2.74-2.68 (m, 2, C9H11), 5.32-5.31 (m, 2, C9H11), 6.05-6.34 (m, 1, C9H11), 6.50-6.46 (m, 2, C9H7), 6.86-6.85 (m, 1, C9H7), 7.24-7.22 (m, 2, C9H7), 7.66-7.64 (m, 2, C9H7) 였다.
Under a nitrogen atmosphere, 1.065 g (2.66 mmol) of bis (tetrahydroindenyl) zirconium dichloride, 0.66 g (2.83 mmol) of zirconium chloride and 100 ml of toluene were added to a 500 ml round flask, followed by stirring at 90 ° C. for 18 hours. Reacted. After the reaction was completed, the reaction product was filtered to collect the filtrate. Indenyl lithium 0.66g (5.406mmol) was put in a 500ml flask, the filtrate was added, and the mixed solution was stirred for 18 hours at 90 ℃. The solvent was removed in vacuo, extracted and filtered with 100 ml of dichloromethane and then the solvent was removed again. 50 mL of hexane was injected to slurry the reaction product, which was filtered, washed with 500 mL of hexane and dried in vacuo to yield 1.52 g (yield 72%) of (tetrahydroindenyl) (indenyl) zirconium dichloride. . 1 H NMR (500 MHz, CDCl 3 ) analysis of the obtained (tetrahydroindenyl) (indenyl) zirconium dichloride compound yields 1.54-1.50 (m, 2, C9H11), 1.79-1.70 (m, 2, C9H11), 2.44-2.38 (m, 2, C9H11), 2.74-2.68 (m, 2, C9H11), 5.32-5.31 (m, 2, C9H11), 6.05-6.34 (m, 1, C9H11), 6.50-6.46 (m, 2, C9H7), 6.86-6.85 (m, 1, C9H7), 7.24-7.22 (m, 2, C9H7), 7.66-7.64 (m, 2, C9H7).

나. 촉매 조성물의 제조I. Preparation of Catalyst Composition

질소 분위기 하에서, 500ml 플라스크에 (테트라하이드로인데닐)(인데닐)지르코늄 디클로라이드 화합물 92mg과 메틸알루미녹산(MAO, Albemarle社, 10% 톨루엔 용액) 20ml를 혼합하고, 30분 동안 반응시켜 촉매 용액을 제조하였다. 제조된 촉매용액에 220℃에서 소성된 실리카 4g을 넣고, 1 시간 동안 초음파를 가한 후, 상층액을 제거하였다. 잔존하는 고체 입자를 헥산으로 1회 세척한 후, 진공으로 건조하여, 자유롭게 흐르는 고체 분말의 담지촉매를 제조하였다.
In a nitrogen atmosphere, 92 mg of (tetrahydroindenyl) (indenyl) zirconium dichloride compound and 20 ml of methylaluminoxane (MAO, Albemarle, 10% toluene solution) were mixed in a 500 ml flask and reacted for 30 minutes. Prepared. 4 g of the calcined silica was added to the prepared catalyst solution at 220 ° C., and ultrasonic waves were applied for 1 hour, and then the supernatant was removed. The remaining solid particles were washed once with hexane and then dried in vacuo to prepare a supported catalyst of free flowing solid powder.

다. 에틸렌/All. Ethylene / 헥센Hexene -1 공중합-1 copolymerization

외부 냉각수를 공급하여 중합 온도 조절할 수 있는 자켓(jacket)을 장착한 1L 스테인레스 오토클레이브(autoclave) 반응기에, 약 110℃에서 이소부탄 및 에틸렌을 각각 1회 및 5회 흘려 보내어 반응기 내의 불순물을 세정한 후, 67℃로 온도를 낮추었다. 세정된 반응기에 이소부탄 400mL 및 불순물 제거제인 트리이소부틸알루미늄 1.0 mmol을 넣고, 75℃에서 교반한 후, 이소부탄 100mL 및 상기 과정에서 제조된 담지 촉매 40mg을 더욱 투입하고, 에틸렌 분압이 130psig가 되도록 에틸렌과 40 ml의 1-헥센을 가하고, 75℃에서 반응기 전체 압력을 290psig로 유지하여 4시간 동안 중합을 수행하였다. 중합이 진행되는 동안 에틸렌 분압은 130psig로 유지하였으며, 추가로 투입되는 에틸렌의 유량을 매스 플로우미터(Mass Flowmeter)로 측정하여 투입되는 에틸렌 대비 10중량%의 1-헥센을 연속적으로 투입시켰다. 중합이 완결된 후, 미반응된 1-헥센과 이소부탄을 배출시키고, 반응기를 열어 자유로운 흐름성을 가진 폴리머 395g을 회수하였다. 중합되는 4시간 동안 중합속도가 저하되지 않고 일정(steady)하게 유지되었다. 상기 촉매의 중합활성은 2,240 g폴리머/g.촉매.시간이었고, 제조된 폴리머의 용융지수(Melt Index : MI)는 1.16 g/10분, 밀도는 0.9277 g/cm3 이었다.
A 1L stainless autoclave reactor equipped with a jacket capable of controlling the polymerization temperature by supplying external cooling water was flowed once and five times by isobutane and ethylene at about 110 ° C to clean impurities in the reactor. The temperature was then lowered to 67 ° C. 400 mL of isobutane and 1.0 mmol of triisobutylaluminum as an impurity remover were added to the reactor, and the mixture was stirred at 75 ° C. Then, 100 mL of isobutane and 40 mg of the supported catalyst prepared in the above procedure were further added, and the ethylene partial pressure was 130 psig. Ethylene and 40 ml of 1-hexene were added, and polymerization was carried out for 4 hours while maintaining the reactor total pressure at 290 psig at 75 ° C. While the polymerization was in progress, the ethylene partial pressure was maintained at 130 psig, and the flow rate of additionally added ethylene was measured by a mass flow meter, and 10 wt% of 1-hexene was continuously added to the injected ethylene. After the polymerization was completed, unreacted 1-hexene and isobutane were discharged, and the reactor was opened to recover 395 g of free flowing polymer. During the 4 hours of polymerization, the polymerization rate was not lowered and remained steady. The polymerization activity of the catalyst was 2,240 g polymer / g. Catalyst. The melt index (Melt Index: MI) of the prepared polymer was 1.16 g / 10 min and the density was 0.9277 g / cm 3 .

[실시예 2][Example 2]

가. (end. ( 테트라하이드로인데닐Tetrahydroindenyl )(2-)(2- 메틸인데닐Methylindenyl )지르코늄 )zirconium 디클로라이드의Dichloride 제조 Produce

질소 분위기 하에서, 500ml 용량의 둥근 플라스크에 비스(테트라하이드로인데닐)지르코늄 디클로라이드 3.184g(8mmol), 지르코늄 클로라이드 1.873g(8.4mmol) 및 톨루엔 150ml을 넣은 다음, 교반하면서 90℃에서 24시간 동안 반응시켰다. 반응이 완료된 후, 반응 생성물을 여과하여 여과액을 수집하였다. 2-메틸인데닐 리튬 2.176g(16mmol)을 500ml 플라스크에 넣은 다음, 상기 여과액을 넣고, 혼합용액을 교반하면서 90℃에서 24시간 동안 반응시켰다. 용매를 진공으로 제거하고 디클로로메탄 100ml로 추출 및 여과한 후, 용매를 다시 제거하였다. 헥산 50mL를 주입하여 반응생성물을 슬러리화시키고, 이를 여과하고 헥산 500mL로 세척한 후, 진공으로 건조시켜 3.45g(수율 52%)의 (테트라하이드로인데닐)(2-메틸인데닐)지르코늄 디클로라이드를 얻었다. 수득된 (테트라하이드로인데닐)(2-메틸인데닐)지르코늄 디클로라이드 화합물의 1H NMR(500MHz,CDCl3) 분석 결과는 1.49-1.42 (m, 2, C9H11), 1.75-1.68 (m, 2, C9H11), 2.28 (s, 3, C10H9), 2.37-2.33 (m, 2, C9H11), 2.69-2.64 (m, 2, C9H11), 5.09-5.08 (m, 2, C10H11), 5.80-5.79 (m, 1, C10H11), 6.236 (s, 2, C10H9), 7.13-7.10 (m, 2, C10H9), 7.55-7.53 (m, 2, C10H9) 였다.
Under a nitrogen atmosphere, 3.184 g (8 mmol) of bis (tetrahydroindenyl) zirconium dichloride, 1.873 g (8.4 mmol) of zirconium chloride and 150 ml of toluene were added to a 500 ml round flask, followed by reaction at 90 ° C. for 24 hours while stirring. I was. After the reaction was completed, the reaction product was filtered to collect the filtrate. 2.176 g (16 mmol) of 2-methylindenyl lithium was placed in a 500 ml flask, and the filtrate was added thereto, and the mixed solution was reacted at 90 ° C. for 24 hours. The solvent was removed in vacuo, extracted and filtered with 100 ml of dichloromethane, and the solvent was removed again. 50 mL of hexane was injected to slurry the reaction product, which was filtered, washed with 500 mL of hexane, and dried in vacuo to give 3.45 g (52% yield) of (tetrahydroindenyl) (2-methylindenyl) zirconium dichloride. Got. 1 H NMR (500 MHz, CDCl 3 ) analysis of the obtained (tetrahydroindenyl) (2-methylindenyl) zirconium dichloride compound shows 1.49-1.42 (m, 2, C9H11), 1.75-1.68 (m, 2, C9H11), 2.28 (s, 3, C10H9), 2.37-2.33 (m, 2, C9H11), 2.69-2.64 (m, 2, C9H11), 5.09-5.08 (m, 2, C10H11), 5.80-5.79 (m , 1, C10H11), 6.236 (s, 2, C10H9), 7.13-7.10 (m, 2, C10H9), 7.55-7.53 (m, 2, C10H9).

나. 촉매 조성물의 제조I. Preparation of Catalyst Composition

질소 분위기 하에서, 500ml 플라스크에 (테트라하이드로인데닐)(2-메틸인데닐)지르코늄 디클로라이드 95mg과 메틸알루미녹산(MAO, Albemarle社, 10% 톨루엔 용액) 20ml를 혼합하고, 30분 동안 반응시켜 촉매 용액을 제조하였다. 제조된 촉매용액에 220℃에서 소성된 실리카 4g을 넣고, 1 시간 동안 초음파를 가한 후, 상층액을 제거하였다. 잔존하는 고체 입자를 헥산으로 1회 세척한 후, 진공으로 건조하여, 자유롭게 흐르는 고체 분말의 담지촉매를 제조하였다.Under a nitrogen atmosphere, 95 mg of (tetrahydroindenyl) (2-methylindenyl) zirconium dichloride and 20 ml of methylaluminoxane (MAO, Albemarle, 10% toluene solution) were mixed in a 500 ml flask, reacted for 30 minutes The solution was prepared. 4 g of the calcined silica was added to the prepared catalyst solution at 220 ° C., and ultrasonic waves were applied for 1 hour, and then the supernatant was removed. The remaining solid particles were washed once with hexane and then dried in vacuo to prepare a supported catalyst of free flowing solid powder.

다. 에틸렌/All. Ethylene / 헥센Hexene -1 공중합-1 copolymerization

상기 촉매 제조 과정에서 제조한 촉매 61mg을 사용한 것을 제외하고는, 상기 실시예 1의 중합 방법과 동일한 방법으로 4시간 동안 올레핀을 중합하여 폴리머 317g을 수득하였다. 중합되는 4시간 동안 중합속도가 저하되지 않고 일정(steady)하게 유지되었다. 상기 촉매의 중합활성은 1,650 g폴리머/g.촉매.시간이었고, 제조된 폴리머의 용융지수(Melt Index : MI)는 0.64 g/10분, 밀도는 0.9287 g/cm3 이었다.
Except for using 61 mg of the catalyst prepared in the catalyst preparation process, olefin was polymerized for 4 hours in the same manner as in the polymerization method of Example 1 to obtain 317 g of a polymer. During the 4 hours of polymerization, the polymerization rate was not lowered and remained steady. The polymerization activity of the catalyst was 1,650 g polymer / g.catalyst.time, and the melt index (Melt Index: MI) of the prepared polymer was 0.64 g / 10 min and the density was 0.9287 g / cm 3 .

[실시예 3][Example 3]

가. (end. ( 테트라하이드로인데닐Tetrahydroindenyl )(1-)(One- 노말부틸인데닐Normal Butyl Indenyl )) 지르코늄디클로라이드의Of zirconium dichloride 제조 Produce

질소 분위기 하에서, 500ml 용량의 둥근 플라스크에 비스(테트라하이드로인데닐)지르코늄 디클로라이드 3.184g(8.0mmol), 지르코늄 클로라이드 1.873g(8.4mmol) 및 톨루엔 150ml을 넣은 다음, 교반하면서 90℃에서 24시간 동안 반응시켰다. 반응이 완료된 후, 반응 생성물을 여과하여 여과액을 수집하였다. 1-노말부틸인데닐 리튬 2.85g(16mmol)을 500ml 플라스크에 넣은 다음, 상기 여과액을 넣고, 혼합용액을 교반하면서, 90℃에서 24시간 동안 반응시켰다. 용매를 진공으로 제거하고, 디클로로메탄 100ml로 추출 및 여과한 후, 다시 용매를 제거하였다. 헥산 50mL를 주입하여 반응생성물을 슬러리화시키고, 이를 여과하고 헥산 500mL로 세척한 후, 진공으로 건조시켜, 3.13g(수율 43%)의 (테트라하이드로인데닐)(1-노말부틸인데닐)지르코늄 디클로라이드를 얻었다. 수득된 (테트라하이드로인데닐)(1-노말부틸인데닐)지르코늄 디클로라이드 화합물의 1H NMR(500MHz,CDCl3) 분석 결과는 0.89-0.91 (m, 3, C11H12), 1.466-1.493 (reactant, m), 1.68-1.72 (reactant, m), 2.325 (m, 1, C9H11), 2.415 (m, 1, C9H11), 2.584 (m, 1, C9H11), 2.703 (m, 1, C9H11), 2.97-2.98 (m, 2, C11H12), 4.931 (m, 2, C9H11), 5.50 (m, 1, C9H11), 6.0 (m, 1, C11H12), 6.328 (m, 1, C11H12), 6.592 (m, 1, C11H12), 7.15-7.19(m, 2, C11H12), 7.53-7.56 (m, 2, C11H12) 였다.
Under a nitrogen atmosphere, 3.184 g (8.0 mmol) of bis (tetrahydroindenyl) zirconium dichloride, 1.873 g (8.4 mmol) of zirconium chloride and 150 ml of toluene were added to a 500 ml round flask, followed by stirring at 90 ° C. for 24 hours. Reacted. After the reaction was completed, the reaction product was filtered to collect the filtrate. 2.85 g (16 mmol) of 1-normal butyl indenyl lithium was placed in a 500 ml flask, the filtrate was added, and the mixed solution was stirred at 90 ° C. for 24 hours. The solvent was removed in vacuo, extracted and filtered with 100 ml of dichloromethane and then the solvent was removed again. 50 mL of hexane was injected to slurry the reaction product, which was filtered, washed with 500 mL of hexane, and dried in vacuo to give 3.13 g (yield 43%) of (tetrahydroindenyl) (1-normal butylindenyl) zirconium Dichloride was obtained. 1 H NMR (500 MHz, CDCl 3 ) analysis of the obtained (tetrahydroindenyl) (1-normalbutylinyl) zirconium dichloride compound yielded 0.89-0.91 (m, 3, C11H12), 1.466-1.493 (reactant, m). ), 1.68-1.72 (reactant, m), 2.325 (m, 1, C9H11), 2.415 (m, 1, C9H11), 2.584 (m, 1, C9H11), 2.703 (m, 1, C9H11), 2.97-2.98 (m, 2, C11H12), 4.931 (m, 2, C9H11), 5.50 (m, 1, C9H11), 6.0 (m, 1, C11H12), 6.328 (m, 1, C11H12), 6.592 (m, 1, C11H12), 7.15-7.19 (m, 2, C11H12), 7.53-7.56 (m, 2, C11H12).

나. 촉매 조성물의 제조I. Preparation of Catalyst Composition

질소 분위기 하에서, 500ml 플라스크에 (테트라하이드로인데닐)(1-노말부틸인데닐)지르코늄 디클로라이드 236mg과 메틸알루미녹산(MAO, Albemarle社, 10% 톨루엔 용액) 50ml를 혼합하고, 30분 동안 반응시켜 촉매 용액을 제조하였다. 제조된 촉매용액에 220℃에서 소성된 실리카 10g을 넣고, 1 시간 동안 초음파를 가한 후, 상층액을 제거하였다. 잔존하는 고체 입자를 헥산으로 1회 세척한 후, 진공으로 건조하여, 자유롭게 흐르는 고체 분말의 담지촉매를 제조하였다.
In a nitrogen atmosphere, 236 mg of (tetrahydroindenyl) (1-normal butyl indenyl) zirconium dichloride and 50 ml of methylaluminoxane (MAO, Albemarle, 10% toluene solution) were mixed in a 500 ml flask and reacted for 30 minutes. Catalyst solution was prepared. 10 g of the calcined silica was added to the prepared catalyst solution at 220 ° C., and ultrasonic waves were applied for 1 hour, and then the supernatant was removed. The remaining solid particles were washed once with hexane and then dried in vacuo to prepare a supported catalyst of free flowing solid powder.

다. 에틸렌/All. Ethylene / 헥센Hexene -1 공중합-1 copolymerization

상기 촉매 제조 과정에서 제조한 촉매 61mg을 사용한 것을 제외하고는, 상기 실시예 1의 중합 방법과 동일한 방법으로 3시간 동안 올레핀을 중합하여 폴리머 213g을 수득하였다. 중합되는 3시간 동안 중합속도가 저하되지 않고 일정(steady)하게 유지되었다. 상기 촉매의 중합활성은 1,170 g폴리머/g.촉매.시간이었고, 제조된 폴리머의 용융지수(Melt Index : MI)는 0.22 g/10분, 밀도는 0.9305 g/cm3 이었다.
Except for using 61 mg of the catalyst prepared in the catalyst preparation process, olefin was polymerized in the same manner as in the polymerization method of Example 1 for 3 hours to obtain 213 g of a polymer. During the 3 hours of polymerization, the polymerization rate was not lowered and remained steady. The polymerization activity of the catalyst was 1,170 g polymer / g catalyst. The melt index (Melt Index: MI) of the prepared polymer was 0.22 g / 10 min and the density was 0.9305 g / cm 3 .

[실시예 4]Example 4

가. (end. ( 테트라하이드로인데닐Tetrahydroindenyl )(1-)(One- 에틸인데닐Ethylindenyl )지르코늄 )zirconium 디클로라이드의Dichloride 제조 Produce

질소 분위기 하에서, 500ml 용량의 둥근 플라스크에 비스(테트라하이드로인데닐)지르코늄 디클로라이드 3.184g(8.0mmol), 지르코늄 클로라이드 1.873g(8.4mmol) 및 톨루엔 150ml을 넣은 다음, 교반하면서 90℃에서 24시간 동안 반응시켰다. 반응이 완료된 후, 반응 생성물을 여과하여 여과액을 수집하였다. 1-에틸틸인데닐 리튬 2.4g(16mmol)을 500ml 플라스크에 넣은 다음, 상기 여과액을 넣고, 혼합용액을 교반하면서, 90℃에서 24시간 동안 반응시켰다. 용매를 진공으로 제거하고, 디클로로메탄 100ml로 추출 및 여과한 후, 다시 용매를 제거하였다. 헥산 50mL를 주입하여 반응생성물을 슬러리화시키고, 이를 여과하고 헥산 500mL로 세척한 후, 진공으로 건조시켜, 3.58g(수율 53%)의 (테트라하이드로인데닐)(1-에틸인데닐)지르코늄 디클로라이드를 얻었다. 수득된 (테트라하이드로인데닐)(1-에틸인데닐)지르코늄 디클로라이드 화합물의 1H NMR(500MHz,CDCl3) 분석 결과는 1.248-1.255 (m, 3, C11H12), 1.466-1.493 (reactant, m), 1.68-1.72 (reactant, m), 2.325 (m, 1, C9H11), 2.415 (m, 1, C9H11), 2.584 (m, 1, C9H11), 2.703 (m, 1, C9H11), 2.97-2.98 (m, 2, C11H12), 4.931 (m, 2, C9H11), 5.50 (m, 1, C9H11), 6.0 (m, 1, C11H12), 6.328 (m, 1, C11H12), 6.592 (m, 1, C11H12), 7.15-7.19(m, 2, C11H12), 7.53-7.56 (m, 2, C11H12) 였다.
Under a nitrogen atmosphere, 3.184 g (8.0 mmol) of bis (tetrahydroindenyl) zirconium dichloride, 1.873 g (8.4 mmol) of zirconium chloride and 150 ml of toluene were added to a 500 ml round flask, followed by stirring at 90 ° C. for 24 hours. Reacted. After the reaction was completed, the reaction product was filtered to collect the filtrate. 2.4 g (16 mmol) of 1-ethylthylindenyl lithium was placed in a 500 ml flask, the filtrate was added, and the mixed solution was stirred at 90 ° C. for 24 hours. The solvent was removed in vacuo, extracted and filtered with 100 ml of dichloromethane and then the solvent was removed again. 50 mL of hexane was injected to slurry the reaction product, which was filtered, washed with 500 mL of hexane and dried in vacuo to give 3.58 g (yield 53%) of (tetrahydroindenyl) (1-ethylindenyl) zirconium di Chloride was obtained. 1 H NMR (500 MHz, CDCl 3 ) analysis of the obtained (tetrahydroindenyl) (1-ethylindenyl) zirconium dichloride compound shows 1.248-1.255 (m, 3, C11H12), 1.466-1.493 (reactant, m) , 1.68-1.72 (reactant, m), 2.325 (m, 1, C9H11), 2.415 (m, 1, C9H11), 2.584 (m, 1, C9H11), 2.703 (m, 1, C9H11), 2.97-2.98 ( m, 2, C11H12), 4.931 (m, 2, C9H11), 5.50 (m, 1, C9H11), 6.0 (m, 1, C11H12), 6.328 (m, 1, C11H12), 6.592 (m, 1, C11H12) ), 7.15-7.19 (m, 2, C11H12), 7.53-7.56 (m, 2, C11H12).

나. 촉매 조성물의 제조I. Preparation of Catalyst Composition

질소 분위기 하에서, 500ml 플라스크에 (테트라하이드로인데닐)(1-에틸인데닐)지르코늄 디클로라이드 130mg과 메틸알루미녹산(MAO, Albemarle社, 10% 톨루엔 용액) 25ml를 혼합하고, 30분 동안 반응시켜 촉매 용액을 제조하였다. 제조된 촉매용액에 220℃에서 소성된 실리카 5g을 넣고, 1 시간 동안 초음파를 가한 후, 상층액을 제거하였다. 잔존하는 고체 입자를 헥산으로 1회 세척한 후, 진공으로 건조하여, 자유롭게 흐르는 고체 분말의 담지촉매를 제조하였다.Under a nitrogen atmosphere, 130 mg of (tetrahydroindenyl) (1-ethylindenyl) zirconium dichloride and 25 ml of methylaluminoxane (MAO, Albemarle, 10% toluene solution) were mixed in a 500 ml flask, and reacted for 30 minutes to form a catalyst. The solution was prepared. 5 g of the calcined silica was added to the prepared catalyst solution at 220 ° C., and ultrasonic waves were applied for 1 hour, and then the supernatant was removed. The remaining solid particles were washed once with hexane and then dried in vacuo to prepare a supported catalyst of free flowing solid powder.

다. 에틸렌/All. Ethylene / 헥센Hexene -1 공중합-1 copolymerization

상기 촉매 제조 과정에서 제조한 촉매 59mg을 사용한 것을 제외하고는, 상기 실시예 1의 중합 방법과 동일한 방법으로 4시간 동안 올레핀을 중합하여 폴리머 190g을 수득하였다. 중합되는 4시간 동안 중합속도는 약간 감소(decay)되었다. 상기 촉매의 중합활성은 790 g폴리머/g.촉매.시간이었고, 제조된 폴리머의 용융지수(Melt Index : MI)는 0.18 g/10분, 밀도는 0.9309 g/cm3 이었다.
Except that 59 mg of the catalyst prepared in the catalyst preparation process was used, olefin was polymerized for 4 hours in the same manner as in the polymerization method of Example 1 to obtain 190 g of a polymer. The polymerization rate decreased slightly during the 4 hours of polymerization. The polymerization activity of the catalyst was 790 g polymer / g catalyst. The melt index (Melt Index: MI) of the prepared polymer was 0.18 g / 10 min and the density was 0.9309 g / cm 3 .

[실시예 5][Example 5]

가. (end. ( 테트라하이드로인데닐Tetrahydroindenyl )(2-)(2- 페닐인데닐Phenylindenyl )지르코늄 )zirconium 디클로라이드의Dichloride 제조 Produce

질소 분위기 하에서, 500ml 용량의 둥근 플라스크에 비스(테트라하이드로인데닐)지르코늄 디클로라이드 1.0g(2.5mmol), 지르코늄 클로라이드 0.61g(2.75mmol) 및 톨루엔 150ml을 넣은 다음, 교반하면서 90℃에서 24시간 동안 반응시켰다. 반응이 완료된 후, 반응 생성물을 여과하여 여과액을 수집하였다. 2-페닐인데닐 리튬 0.991g (5.0mmol)을 500ml 플라스크에 넣은 다음, 상기 여과액을 넣고, 혼합용액을 교반하면서, 90℃에서 24시간 동안 반응시켰다. 용매를 진공으로 제거하고, 디클로로메탄 100ml로 추출 및 여과한 후, 다시 용매를 제거하였다. 헥산 50mL를 주입하여 반응생성물을 슬러리화시키고, 이를 여과하고 헥산 500mL로 세척한 후, 진공으로 건조시켜 0.9g(수율 39%)의 (테트라하이드로인데닐)(2-페닐인데닐)지르코늄 디클로라이드를 얻었다. 수득된 (테트라하이드로인데닐)(2-페닐인데닐)지르코늄 디클로라이드 화합물의 1H NMR(500MHz,CDCl3) 분석 결과는 1.47-1.49 (m, 2, C9H11), 1.68-1.70 (m, 2, C9H11), 2.41-2.49 (m, 2, C9H11), 2.68-2.72 (m, 2, C9H11), 5.29-5.31 (d, 2, C9H11), 5.80-5.84 (m, 1, C9H11), 7.20-7.25 (m, 2, C15H11), 7.30-7.33 (m, 1, C15H11), 7.4-7.42 (m, 2, C15H9), 7.58-7.61 (m, 2, C15H9), 7.67-7.70 (m, 2, C15H9) 였다.
Under a nitrogen atmosphere, 1.0 g (2.5 mmol) of bis (tetrahydroindenyl) zirconium dichloride, 0.61 g (2.75 mmol) of zirconium chloride and 150 ml of toluene were placed in a 500 ml round flask, followed by stirring at 90 ° C. for 24 hours. Reacted. After the reaction was completed, the reaction product was filtered to collect the filtrate. 0.991 g (5.0 mmol) of 2-phenylindenyl lithium was added to a 500 ml flask, and the filtrate was added thereto. The mixture was stirred at 90 ° C. for 24 hours. The solvent was removed in vacuo, extracted and filtered with 100 ml of dichloromethane and then the solvent was removed again. 50 mL of hexane was injected to slurry the reaction product, which was filtered, washed with 500 mL of hexane and dried in vacuo to give 0.9 g (yield 39%) of (tetrahydroindenyl) (2-phenylindenyl) zirconium dichloride. Got. 1 H NMR (500 MHz, CDCl 3 ) analysis of the obtained (tetrahydroindenyl) (2-phenylindenyl) zirconium dichloride compound shows 1.47-1.49 (m, 2, C9H11), 1.68-1.70 (m, 2, C9H11), 2.41-2.49 (m, 2, C9H11), 2.68-2.72 (m, 2, C9H11), 5.29-5.31 (d, 2, C9H11), 5.80-5.84 (m, 1, C9H11), 7.20-7.25 (m, 2, C15H11), 7.30-7.33 (m, 1, C15H11), 7.4-7.42 (m, 2, C15H9), 7.58-7.61 (m, 2, C15H9), 7.67-7.70 (m, 2, C15H9 )

나. 촉매 조성물의 제조I. Preparation of Catalyst Composition

질소 분위기 하에서, 500ml 플라스크에 (테트라하이드로인데닐)(2-페닐인데닐)지르코늄 디클로라이드 124mg과 메틸알루미녹산(MAO, Albemarle社, 10% 톨루엔 용액) 25ml를 혼합하고, 30분 동안 반응시켜 촉매 용액을 제조하였다. 제조된 촉매용액에 220℃에서 소성된 실리카 5g을 넣고, 1 시간 동안 초음파를 가한 후, 상층액을 제거하였다. 잔존하는 고체 입자를 헥산으로 1회 세척한 후, 진공으로 건조하여, 자유롭게 흐르는 고체 분말의 담지촉매를 제조하였다.Under a nitrogen atmosphere, 124 mg of (tetrahydroindenyl) (2-phenylindenyl) zirconium dichloride and 25 ml of methylaluminoxane (MAO, Albemarle, 10% toluene solution) were mixed in a 500 ml flask, reacted for 30 minutes The solution was prepared. 5 g of the calcined silica was added to the prepared catalyst solution at 220 ° C., and ultrasonic waves were applied for 1 hour, and then the supernatant was removed. The remaining solid particles were washed once with hexane and then dried in vacuo to prepare a supported catalyst of free flowing solid powder.

다. 에틸렌/All. Ethylene / 헥센Hexene -1 공중합-1 copolymerization

상기 촉매 제조 과정에서 제조한 촉매 60mg을 사용한 것을 제외하고는, 상기 실시예 1의 중합 방법과 동일한 방법으로 3시간 동안 올레핀을 중합하여 폴리머 70g을 수득하였다. 중합되는 3시간 동안 중합속도가 저하되지 않고 일정(steady)하게 유지되었다. 상기 촉매의 중합활성은 400 g폴리머/g.촉매.시간이었고, 제조된 폴리머의 용융지수(Melt Index : MI)는 0.11 g/10분, 밀도는 0.9257 g/cm3 이었다.
Except that 60 mg of the catalyst prepared in the catalyst preparation process was used, olefin was polymerized in the same manner as in the polymerization method of Example 1 for 3 hours to obtain 70 g of a polymer. During the 3 hours of polymerization, the polymerization rate was not lowered and remained steady. The polymerization activity of the catalyst was 400 g polymer / g. Catalyst. Time, the melt index (Melt Index: MI) of the prepared polymer was 0.11 g / 10 min, and the density was 0.9257 g / cm 3 .

[비교예][Comparative Example]

가. 촉매 조성물의 제조end. Preparation of Catalyst Composition

질소 분위기 하에서, 500ml 플라스크에 비스(테트라하이드로인데닐)지르코늄 디클로라이드 84mg과 메틸알루미녹산(MAO, Albemarle社, 10% 톨루엔 용액) 20ml를 혼합하고, 30분 동안 반응시켜 촉매 용액을 제조하였다. 제조된 촉매용액에 220℃에서 소성된 실리카 4g을 넣고, 1 시간 동안 초음파를 가한 후, 상층액을 제거하였다. 잔존하는 고체 입자를 헥산으로 1회 세척한 후, 진공으로 건조하여, 자유롭게 흐르는 고체 분말의 담지촉매를 제조하였다.
In a nitrogen atmosphere, 84 ml of bis (tetrahydroindenyl) zirconium dichloride and 20 ml of methylaluminoxane (MAO, Albemarle, 10% toluene solution) were mixed in a 500 ml flask, and reacted for 30 minutes to prepare a catalyst solution. 4 g of the calcined silica was added to the prepared catalyst solution at 220 ° C., and ultrasonic waves were applied for 1 hour, and then the supernatant was removed. The remaining solid particles were washed once with hexane and then dried in vacuo to prepare a supported catalyst of free flowing solid powder.

나. 에틸렌/I. Ethylene / 헥센Hexene -1 공중합-1 copolymerization

상기 촉매 제조 과정에서 제조한 촉매 105mg을 사용한 것을 제외하고는, 상기 실시예 1의 중합 방법과 동일한 방법으로 1시간 동안 올레핀을 중합하여 폴리머 123g을 수득하였다. 중합되는 1시간 동안, 초기에는 높은 촉매 활성을 보였지만, 중합속도가 급격히 감소(very decay)되었다. 상기 촉매의 중합활성은 1170 g폴리머/g.촉매.시간이었고, 제조된 폴리머의 용융지수(Melt Index : MI)는 0.11 g/10분, 밀도는 0.9226 g/cm3 이었다.Except for using 105 mg of the catalyst prepared in the catalyst preparation process, olefin was polymerized for 1 hour in the same manner as in the polymerization method of Example 1 to obtain 123 g of a polymer. During the one hour of polymerization, the catalyst showed initially high catalytic activity, but the rate of polymerization was very decay. The polymerization activity of the catalyst was 1170 g polymer / g catalyst. The melt index (Melt Index: MI) of the prepared polymer was 0.11 g / 10 min and the density was 0.9226 g / cm 3 .

Claims (12)

하기 화학식 1로 표현되는 메탈로센 화합물.
[화학식 1]
(4HInd)(Cp')MX2
여기서, 4HInd는 테트라하이드로인데닐 핵을 가진 기이며, Cp'는 싸이클로펜타디에닐 핵을 가진 기이고, 4HInd와 Cp'는 비치환되거나 서로 동일하거나 다른 하나 이상의 치환체를 가질 수 있고, 상기 치환체는 탄소수 1 내지 20의 알킬, 알콕시, 알킬실릴(alkylsilyl), 알킬실록시, 알킬아미노 또는 할로알킬, 탄소수 3 내지 20의 싸이클로알킬, 탄소수 6 내지 20의 아릴, 아릴알킬, 아릴실릴, 알킬아릴 또는 아릴옥시, 탄소수 2 내지 20의 디알킬아미노, 할로겐 원자 및 아미노기로 이루어진 군으로부터 선택되는 라디칼이고, M은 주기율표의 IVB, VB 또는 VIB족 전이금속이며, X는 동일하거나 다를 수 있으며, 할로겐, 탄소수 1 내지 20의 알킬 또는 알콕시, 탄소수 2 내지 20의 알케닐 및 탄소수 6 내지 20의 아릴, 알킬아릴, 아릴알킬 또는 아릴옥시 라디칼로 이루어진 군으로부터 선택되는 1종이다. Metallocene compound represented by the following formula (1).
[Formula 1]
(4HInd) (Cp ') MX 2
Here, 4HInd is a group having a tetrahydroindenyl nucleus, Cp 'is a group having a cyclopentadienyl nucleus, 4HInd and Cp' may be unsubstituted, have the same or different substituents, and the substituent is Alkyl, alkoxy, alkylsilyl, alkylsiloxy, alkylamino or haloalkyl of 1 to 20 carbon atoms, cycloalkyl of 3 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, arylalkyl, arylsilyl, alkylaryl or aryl Oxy, a radical selected from the group consisting of dialkylamino having 2 to 20 carbon atoms, a halogen atom and an amino group, M is a group IVB, VB or VIB transition metal of the periodic table, X may be the same or different, halogen, 1 carbon From the group consisting of alkyl or alkoxy of 20 to 20, alkenyl of 2 to 20 carbon atoms and aryl, alkylaryl, arylalkyl or aryloxy radical of 6 to 20 carbon atoms It is the one selected. 제1항에 있어서, 상기 4HInd는 4,5,6,7-테트라하이드로인데닐 핵을 가진 기이고, Cp'는 싸이클로펜타디에닐, 인데닐(indenyl), 플루오레닐(fluorenyl) 및 아줄레닐(azulenyl)로 이루어진 군으로부터 선택되는 싸이클로펜타디에닐 핵을 가진 기인 것인 메탈로센 화합물.The compound of claim 1, wherein 4HInd is a group having a 4,5,6,7-tetrahydroindenyl nucleus, and Cp 'is cyclopentadienyl, indenyl, fluorenyl and azule. Metallocene compound that is a group having a cyclopentadienyl nucleus selected from the group consisting of azulenyl. 제1항에 있어서, 상기 M은 티타늄, 지르코늄 및 하프늄으로 이루어진 군으로부터 선택되는 전이금속이고, X는 불소, 염소, 브롬 및 요오드로 이루어진 군으로부터 선택되는 할로겐 원자인 것인 메탈로센 화합물.The metallocene compound of claim 1, wherein M is a transition metal selected from the group consisting of titanium, zirconium and hafnium, and X is a halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine. 하기 화학식 1로 표현되는 메탈로센 화합물; 및
상기 메탈로센 화합물과 반응하여 메탈로센 화합물이 촉매 활성을 나타내도록 하는 활성체(activator)를 포함하는 메탈로센 촉매 조성물,
[화학식 1]
(4HInd)(Cp')MX2
여기서, 4HInd는 테트라하이드로인데닐 핵을 가진 기이며, Cp'는 싸이클로펜타디에닐 핵을 가진 기이고, 4HInd와 Cp'는 비치환되거나 서로 동일하거나 다른 하나 이상의 치환체를 가질 수 있고, 상기 치환체는 탄소수 1 내지 20의 알킬, 알콕시, 알킬실릴(alkylsilyl), 알킬실록시, 알킬아미노 또는 할로알킬, 탄소수 3 내지 20의 싸이클로알킬, 탄소수 6 내지 20의 아릴, 아릴알킬, 아릴실릴, 알킬아릴 또는 아릴옥시, 탄소수 2 내지 20의 디알킬아미노, 할로겐 원자 및 아미노기로 이루어진 군으로부터 선택되는 라디칼이고, M은 주기율표의 IVB, VB 또는 VIB족 전이금속이며, X는 동일하거나 다를 수 있으며, 할로겐, 탄소수 1 내지 20의 알킬 또는 알콕시, 탄소수 2 내지 20의 알케닐 및 탄소수 6 내지 20의 아릴, 알킬아릴, 아릴알킬 또는 아릴옥시 라디칼로 이루어진 군으로부터 선택되는 1종이다. A metallocene compound represented by Formula 1 below; And
A metallocene catalyst composition comprising an activator reacting with the metallocene compound to cause the metallocene compound to exhibit catalytic activity,
[Formula 1]
(4HInd) (Cp ') MX 2
Here, 4HInd is a group having a tetrahydroindenyl nucleus, Cp 'is a group having a cyclopentadienyl nucleus, 4HInd and Cp' may be unsubstituted, have the same or different substituents, and the substituent is Alkyl, alkoxy, alkylsilyl, alkylsiloxy, alkylamino or haloalkyl of 1 to 20 carbon atoms, cycloalkyl of 3 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, arylalkyl, arylsilyl, alkylaryl or aryl Oxy, a radical selected from the group consisting of dialkylamino having 2 to 20 carbon atoms, a halogen atom and an amino group, M is a group IVB, VB or VIB transition metal of the periodic table, X may be the same or different, halogen, 1 carbon From the group consisting of alkyl or alkoxy of 20 to 20, alkenyl of 2 to 20 carbon atoms and aryl, alkylaryl, arylalkyl or aryloxy radical of 6 to 20 carbon atoms It is the one selected. 제4항에 있어서, 상기 활성체는 알킬 알루미녹산, 유기 알루미늄 화합물, 벌키한 방향족 불소화합물, 개질된 클레이(clay) 및 루이스산 무기산화물로 이루어진 군으로부터 선택되는 것인, 메탈로센 촉매 조성물.5. The metallocene catalyst composition of claim 4, wherein the activator is selected from the group consisting of alkyl aluminoxanes, organoaluminum compounds, bulky aromatic fluorides, modified clays, and Lewis acid inorganic oxides. 제5항에 있어서, 상기 활성체는 하기 화학식 3 및 4로 표시되는 선상 또는 환상 구조 올리고머인 탄화수소(hydrocarbyl) 알루미녹산인 것인, 메탈로센 촉매 조성물,
[화학식 3]
Figure pat00006

[화학식 4]
Figure pat00007

여기서, R'은 각각 독립적으로 탄소수 1 내지 10의 선형 또는 가지형 알킬 라디칼이며, x는 1 내지 50의 정수이고, y는 3 내지 50의 정수이다.The metallocene catalyst composition of claim 5, wherein the active agent is a hydrocarbon (hydrocarbyl) aluminoxane, which is a linear or cyclic oligomer represented by the following Chemical Formulas 3 and 4,
(3)
Figure pat00006

[Chemical Formula 4]
Figure pat00007

Are each independently a linear or branched alkyl radical having 1 to 10 carbon atoms, x is an integer from 1 to 50, and y is an integer from 3 to 50. 제6항에 있어서, 상기 화학식 1로 표시되는 메탈로센 화합물 1몰에 대하여, 상기 알루미녹산의 알루미늄이 1 내지 100,000몰이 되도록 상기 알루미녹산이 혼합되는 것인, 메탈로센 촉매 조성물.The metallocene catalyst composition of claim 6, wherein the aluminoxane is mixed so that aluminum of the aluminoxane is 1 to 100,000 moles with respect to 1 mole of the metallocene compound represented by Formula 1. 제5항에 있어서, 상기 벌키한 방향족 불소화합물은 트리메틸암모늄 테트라키스(펜타플루오로페닐) 보레이트, 트리에틸암모늄 테트라키스(펜타플루오로페닐)보레이트, 트리프로필암모늄 테트라키스(펜타플루오로페닐) 보레이트, 트리부틸암모늄 테트라키스(펜타플루오로페닐)보레이트, 아닐리늄 테트라키스(펜타플루오로페닐)보레이트, 피리디늄 테트라키스(펜타플루오로페닐)보레이트, 페로세늄 테트라키스(펜타플루오로페닐)보레이트, 실버 테트라키스(펜타플루오로페닐)보레이트, 트리스(펜타플루오로페닐)보레인, 트리스(3,4,5-트리플루오로페닐)보레인 및 이들의 혼합물로 이루어진 군으로부터 선택되고, 상기 개질된 클레이는 N,N-디메틸아닐리늄 몬트모릴로나이트, N,N-디메틸아닐리늄 헥토라이트 및 이들의 혼합물로 이루어진 군으로부터 선택되는 것인, 메탈로센 촉매 조성물.The method of claim 5, wherein the bulk aromatic fluorine compound is trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate Tributylammonium tetrakis (pentafluorophenyl) borate, anilinium tetrakis (pentafluorophenyl) borate, pyridinium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, Silver tetrakis (pentafluorophenyl) borate, tris (pentafluorophenyl) borane, tris (3,4,5-trifluorophenyl) borane and mixtures thereof; Clay is selected from the group consisting of N, N-dimethylanilinium montmorillonite, N, N-dimethylanilinium hectorite and mixtures thereof Will be, metallocene catalyst composition. 제4항에 있어서, 상기 메탈로센 화합물 및 활성체가 담지된 유기 또는 무기 담체를 더욱 포함하는 메탈로센 촉매 조성물.The metallocene catalyst composition of claim 4, further comprising an organic or inorganic carrier on which the metallocene compound and the activator are supported. 하기 화학식 1로 표시되는 메탈로센 화합물의 존재 하에서, 하나 이상의 올레핀을 중합하는 단계를 포함하는 올레핀의 중합방법,
[화학식 1]
(4HInd)(Cp')MX2
여기서, 4HInd는 테트라하이드로인데닐 핵을 가진 기이며, Cp'는 싸이클로펜타디에닐 핵을 가진 기이고, 4HInd와 Cp'는 비치환되거나 서로 동일하거나 다른 하나 이상의 치환체를 가질 수 있고, 상기 치환체는 탄소수 1 내지 20의 알킬, 알콕시, 알킬실릴(alkylsilyl), 알킬실록시, 알킬아미노 또는 할로알킬, 탄소수 3 내지 20의 싸이클로알킬, 탄소수 6 내지 20의 아릴, 아릴알킬, 아릴실릴, 알킬아릴 또는 아릴옥시, 탄소수 2 내지 20의 디알킬아미노, 할로겐 원자 및 아미노기로 이루어진 군으로부터 선택되는 라디칼이고, M은 주기율표의 IVB, VB 또는 VIB족 전이금속이며, X는 동일하거나 다를 수 있으며, 할로겐, 탄소수 1 내지 20의 알킬 또는 알콕시, 탄소수 2 내지 20의 알케닐 및 탄소수 6 내지 20의 아릴, 알킬아릴, 아릴알킬 또는 아릴옥시 라디칼로 이루어진 군으로부터 선택되는 1종이다. In the presence of a metallocene compound represented by the formula (1), a polymerization method of an olefin comprising the step of polymerizing at least one olefin,
[Formula 1]
(4HInd) (Cp ') MX 2
Here, 4HInd is a group having a tetrahydroindenyl nucleus, Cp 'is a group having a cyclopentadienyl nucleus, 4HInd and Cp' may be unsubstituted, have the same or different substituents, and the substituent is Alkyl, alkoxy, alkylsilyl, alkylsiloxy, alkylamino or haloalkyl of 1 to 20 carbon atoms, cycloalkyl of 3 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, arylalkyl, arylsilyl, alkylaryl or aryl Oxy, a radical selected from the group consisting of dialkylamino having 2 to 20 carbon atoms, a halogen atom and an amino group, M is a group IVB, VB or VIB transition metal of the periodic table, X may be the same or different, halogen, 1 carbon From the group consisting of alkyl or alkoxy of 20 to 20, alkenyl of 2 to 20 carbon atoms and aryl, alkylaryl, arylalkyl or aryloxy radical of 6 to 20 carbon atoms It is the one selected. 제10항에 있어서, 상기 올레핀은 탄소수 2 내지 12의 지방족 알파-올레핀인 것인, 올레핀의 중합방법.The method of claim 10, wherein the olefin is an aliphatic alpha-olefin having 2 to 12 carbon atoms. 제10항에 있어서, 상기 중합방법은 액상, 슬러리상, 괴상(Bulk Phase) 또는 기상 중합반응으로 수행되는 것인, 올레핀의 중합방법.The polymerization method of olefin according to claim 10, wherein the polymerization method is performed by liquid phase, slurry phase, bulk phase or gas phase polymerization.
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