KR101355052B1

KR101355052B1 - Process for the preparation of asymmetrical unbridged metallocene compounds

Info

Publication number: KR101355052B1
Application number: KR1020110138174A
Authority: KR
Inventors: 홍사문; 유승택
Original assignee: 대림산업 주식회사
Priority date: 2011-12-20
Filing date: 2011-12-20
Publication date: 2014-01-29
Anticipated expiration: 2031-12-20
Also published as: KR20130070912A

Abstract

올레핀 중합용 촉매로서 사용되는 비대칭성 비가교형 메탈로센 화합물의 제조방법이 개시된다. 상기 비대칭성 비가교형 메탈로센 화합물의 제조방법은 통상적인 하이드로카빌 라디칼로 치환 또는 비치환된 싸이클로펜타디에닐 핵을 포함하는 리간드 및 전이금속을 포함하는 대칭성 비가교형 메탈로센 화합물을 원료로 사용하여, 하기 화학식 5로 표시되는 비대칭성 비가교형 메탈로센 화합물을 쉽게 제조할 수 있다.
[화학식 5]

상기 화학식 5에서, Cp¹ 및 Cp²는 각각 독립적으로 탄소수 1 내지 30의 하이드로카빌 라디칼이 치환 또는 비치환된 싸이클로펜타디에닐 핵을 가진 라디칼이고, Cp¹및 Cp²는 서로 다른 구조를 가지며, M¹은 티타늄, 지르코늄 또는 하프늄이고, X는 할로겐 원자이다.Disclosed is a method for preparing an asymmetric uncrosslinked metallocene compound used as a catalyst for olefin polymerization. The method for preparing the asymmetric non-crosslinked metallocene compound uses a symmetric non-crosslinked metallocene compound including a ligand and a transition metal including a cyclopentadienyl nucleus unsubstituted or substituted with a conventional hydrocarbyl radical as a raw material. Thus, the asymmetric non-crosslinked metallocene compound represented by the following Chemical Formula 5 can be easily prepared.
[Chemical Formula 5]

In Chemical Formula 5, Cp ¹ And Cp ² are each independently a radical having a cyclopentadienyl nucleus substituted or unsubstituted with a hydrocarbyl radical having 1 to 30 carbon atoms, Cp ¹ and Cp ² have different structures, and M ¹ is titanium, zirconium or Hafnium and X is a halogen atom.

Description

Process for the preparation of asymmetrical unbridged metallocene compounds

본 발명은 비대칭성 비가교형 메탈로센 화합물의 제조방법에 관한 것으로서, 더욱 상세하게는, 올레핀 중합용 촉매로서 사용되는 비대칭성 비가교형 메탈로센 화합물의 제조방법에 관한 것이다.
The present invention relates to a method for producing an asymmetric non-crosslinked metallocene compound, and more particularly, to a method for producing an asymmetric non-crosslinked metallocene compound used as a catalyst for olefin polymerization.

올레핀의 중합에는 전이금속을 포함하는 촉매가 일반적으로 사용되고 있으며, 예를 들면, 독일특허 제2,608,933호, 제3,007,725호 등에는 지르코늄, 티타늄, 하프늄 등 주기율표 4족 전이금속과 싸이클로펜타디엔(cyclopentadiene)계 구조의 리간드로 이루어진 메탈로센 화합물을 메틸알루미녹산 등의 활성체와 함께 올레핀 중합용 촉매로 사용하는 것을 개시하고 있다.　상기 싸이클로펜타디엔계 구조를 갖는 리간드 화합물의 예로는 싸이클로펜타디엔(cyclopentadiene), 인덴(indene), 플루오렌(fluorene), 치환된 싸이클로펜타디엔, 치환된 인덴, 치환된 플루오렌 등이 있다.
Catalysts containing transition metals are generally used for the polymerization of olefins. For example, German Patent Nos. 2,608,933, 3,007,725 and the like have zirconium, titanium, hafnium, etc. Group 4 transition metals such as zirconium, titanium, and cyclopentadiene. Disclosed is the use of a metallocene compound composed of a ligand having a structure as an catalyst for olefin polymerization together with an active agent such as methylaluminoxane. Examples of the ligand compound having a cyclopentadiene-based structure include cyclopentadiene, indene, fluorene, substituted cyclopentadiene, substituted indene, substituted fluorene, and the like.

많은 종류의 싸이클로펜타디엔계 메탈로센 화합물이 올레핀 중합을 위한 촉매계에 사용될 수 있는데, 싸이클로펜타디엔계 메탈로센의 화학적 구조 변화는 중합촉매로서 메탈로센의 적합성에 중요한 영향을 미치는 것으로 알려져 왔다.　 예를 들어, 싸이클로펜타디에닐 환(ring)에 결합된 치환체의 크기와 위치는 촉매의 활성, 촉매의 입체특이성, 촉매의 안전성, 중합 반응으로 얻어질 수 있는 중합체의 물성 등에 큰 영향을 준다.　최근에는 전이금속으로서 지르코늄을 포함하는 치환된 싸이클로펜타디엔계 메탈로센과 메틸알루미녹산으로 이루어진 촉매계가 올레핀 중합에서 활성이 높다는 것이 밝혀졌으며, 이러한 내용은 유럽특허 제129,368호, 미국특허 제4,874,880호, 미국특허 제5,324,800호, Makromol. Chem. Rapid Commun., 4, 417(1983) 등 다수의 문헌에 개시되어 있다.
Many types of cyclopentadiene-based metallocene compounds can be used in the catalyst system for olefin polymerization. The chemical structure change of cyclopentadiene-based metallocene has been known to have an important effect on the suitability of metallocene as a polymerization catalyst. . For example, the size and position of the substituents attached 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 that can be obtained by the polymerization reaction. Recently, it has been found that a catalytic system composed of substituted cyclopentadiene-based metallocenes and methylaluminoxanes containing zirconium as transition metals has high activity in olefin polymerization, which is described in European Patent Nos. 129,368 and 4,874,880. U.S. Patent 5,324,800, Makromol. Chem. Rapid Commun., 4, 417 (1983), and the like.

또한, 하이드로카빌기로 치환된 싸이클로펜타디에닐 리간드와 지르코늄으로 이루어진 메탈로센에 관한 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 있으며, 이러한 메탈로센 화합물들은 두 개의 동일한 싸이클로펜타디에닐 리간드를 포함하는 대칭성 비가교형 메탈로센이 대부분이다.
Further, examples of metallocenes composed of zirconium and cyclopentadienyl ligands substituted with hydrocarbyl groups include bis (alkylcyclopentadienyl) zirconium dichloride, wherein alkyl is methyl, ethyl, isopropyl, tert-propyl Or trimethylsilyl) (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-cyclopentadiene Nil) zirconium dichloride (US Pat. No. 4,874,880) and the like are known, and most of these metallocene compounds are symmetric, non-crosslinked metallocenes comprising two identical cyclopentadienyl ligands.

한편, 비대칭성 비가교형 메탈로센으로는 (싸이클로펜타디에닐)(인데닐) 및 (싸이클로펜타디에닐)(플루오레닐)메탈로센(미국특허 제5,541,272호), (치환된 인데닐)(싸이클로펜타디에닐)로 이루어진 메탈로센(미국특허 제5,223,467호 및 제5,780,659호) 등이 알려져 있다.　상기 미국특허 제5,541,272호에 개시된 비대칭성 비가교형 (싸이클로펜타디에닐)(인데닐)지르코늄 디클로라이드는 대칭성 비가교형인 비스(인데닐)지르코늄 디클로라이드 또는 비스(싸이클로펜타디에닐)지르코늄 디클로라이드보다 활성이 우수한 것으로 나타났다.
On the other hand, asymmetric uncrosslinked metallocenes include (cyclopentadienyl) (indenyl) and (cyclopentadienyl) (fluorenyl) metallocene (US Pat. No. 5,541,272), (substituted indenyl) Metallocenes (US Pat. Nos. 5,223,467 and 5,780,659) consisting of (cyclopentadienyl) and the like are known. The asymmetric uncrosslinked (cyclopentadienyl) (indenyl) zirconium dichloride disclosed in U.S. Pat.No. 5,541,272 is higher than bis (indenyl) zirconium dichloride or bis (cyclopentadienyl) zirconium dichloride which is a symmetric uncrosslinked The activity was found to be excellent.

그러나, 이와 같이 공지의 비대칭성 비가교형의 메탈로센 화합물은 그 종류가 한정되어 있으며, 상업적 활용면에서, 기존의 비대칭성 비가교형 메탈로센 화합물 제조 방법은 메탈로센 화합물 제조를 위한 원료가 제한적이거나 제조 과정이 복잡하다는 단점이 있으므로, 다양한 형태의 치환된 싸이클로펜타디에닐 핵을 포함하는 비대칭성 비가교형의 메탈로센 화합물을 얻기 위해서는 새로운 제조 방법이 필요하다.
However, the known asymmetric non-crosslinked metallocene compound is limited in its kind, and in view of commercial application, the conventional method for preparing asymmetric non-crosslinked metallocene compound is a raw material for preparing a metallocene compound. Due to the limitations and limitations of the manufacturing process, new preparation methods are required to obtain asymmetric, non-crosslinked metallocene compounds containing various types of substituted cyclopentadienyl nuclei.

따라서, 본 발명의 목적은 통상적인 하이드로카빌 라디칼로 치환 또는 비치환된 싸이클로펜타디에닐 핵을 포함하는 리간드 및 전이금속을 포함하는 대칭성 비가교형 메탈로센 화합물을 원료로 사용하여, 다양한 형태의 비대칭성 비가교형 메탈로센 화합물을 제조하는 방법을 제공하는 것이다.Accordingly, an object of the present invention is to provide a raw material using a symmetric non-crosslinked metallocene compound containing a transition metal and a ligand comprising a cyclopentadienyl nucleus unsubstituted or substituted with a conventional hydrocarbyl radical, and various forms of asymmetry. It is to provide a method for producing a sex non-crosslinked metallocene compound.

본 발명의 다른 목적은 상업적으로 유용한 높은 활성과 높은 분자량의 폴리올레핀을 제조할 수 있는 비대칭성 비가교형 메탈로센 화합물을 쉽게 제조할 수 있는 방법을 제공하는 것이다.
Another object of the present invention is to provide a method for easily preparing an asymmetric uncrosslinked metallocene compound capable of producing commercially useful high activity and high molecular weight polyolefins.

상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 1로 표시되는 화합물과 하기 화학식 2로 표시되는 화합물을 유기용매 존재 하에 반응시켜 반응 혼합물을 제조하는 단계; 상기 반응 혼합물을 여과하여, 하기 화학식 3으로 표시되는 화합물을 포함하는 여과액을 얻는 단계; 및 상기 여과액의 화학식 3으로 표시되는 화합물과 하기 화학식 4로 표시되는 화합물을 반응시켜 하기 화학식 5로 표시되는 메탈로센 화합물을 제조하는 단계를 포함하는 비대칭성 비가교형 메탈로센 화합물의 제조 방법을 제공한다.In order to achieve the above object, the present invention comprises the steps of preparing a reaction mixture by reacting a compound represented by the formula (1) and a compound represented by the formula (2) in the presence of an organic solvent; Filtering the reaction mixture to obtain a filtrate comprising a compound represented by Formula 3 below; And preparing a metallocene compound represented by Chemical Formula 5 by reacting the compound represented by Chemical Formula 3 with the compound represented by Chemical Formula 4 of the filtrate. To provide.

[화학식 1] [Formula 1]

[화학식 2](2)

[화학식 3](3)

[화학식 4][Chemical Formula 4]

[화학식 5][Chemical Formula 5]

상기 화학식 1 내지 5에서, Cp¹ 및 Cp²는 각각 독립적으로 탄소수 1 내지 30의 하이드로카빌 라디칼이 치환 또는 비치환된 싸이클로펜타디에닐 핵을 가진 라디칼이고, Cp¹ 및 Cp²는 서로 다른 구조를 가지며, M¹은 티타늄, 지르코늄 또는 하프늄이고, X는 할로겐원자이고, M²는 주기율표의 1 또는 2족의 원소이고, R은 탄소수 1 내지 10의 하이드로카빌 라디칼이고, m은 1 또는 2의 정수이고, n은 0 또는 1의 정수이며, m+n은 M²의 원자가와 동일하다.
In Chemical Formulas 1 to 5, Cp ¹ And Cp ² are each independently a radical having a cyclopentadienyl nucleus having a substituted or unsubstituted hydrocarbyl radical having 1 to 30 carbon atoms, and Cp ¹ And Cp ² has a different structure, M ¹ is titanium, zirconium or hafnium, X is a halogen atom, M ² is an element of group 1 or 2 of the periodic table, R is a hydrocarbyl radical having 1 to 10 carbon atoms , m is an integer of 1 or 2, n is an integer of 0 or 1, m + n is equal to the valence of M ² .

본 발명에 따른 비대칭성 비가교형 메탈로센 화합물의 제조방법은 통상적인 하이드로카빌 라디칼로 치환 또는 비치환된 싸이클로펜타디에닐 핵을 포함하는 리간드 및 전이금속을 포함하는 대칭성 비가교형 메탈로센 화합물을 원료로 사용하여, 다양한 형태의 비대칭성 비가교형 메탈로센 화합물을 쉽게 제조할 수 있다.
Method for preparing an asymmetric non-crosslinked metallocene compound according to the present invention is a symmetric non-crosslinked metallocene compound comprising a ligand and a transition metal containing a cyclopentadienyl nucleus unsubstituted or substituted with a conventional hydrocarbyl radical. Using as a raw material, various forms of asymmetric uncrosslinked metallocene compound can be easily prepared.

이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.

본 발명에 따른 비대칭성 비가교형 메탈로센 화합물의 제조방법은, 통상적인 대칭성 비가교형 메탈로센 화합물을 원료로 사용하고, 간단한 공정을 통하여 다양한 형태의 비대칭성 비가교형 메탈로센 화합물을 제조하기 위한 것으로서, 하기 화학식 1로 표시되는 화합물과 하기 화학식 2로 표시되는 화합물을 유기용매 존재 하에 반응시켜 반응 혼합물을 제조하는 단계, 상기 반응 혼합물을 여과하여, 하기 화학식 3으로 표시되는 화합물을 포함하는 여과액을 얻는 단계, 및 상기 여과액의 화학식 3으로 표시되는 화합물과 하기 화학식 4로 표시되는 화합물을 반응시켜 하기 화학식 5로 표시되는 메탈로센 화합물(비대칭성 비가교형 메탈로센 화합물)을 제조하는 단계를 포함한다.Method for producing an asymmetric non-crosslinked metallocene compound according to the present invention, using a conventional symmetric non-crosslinked metallocene compound as a raw material, to prepare various forms of asymmetric non-crosslinked metallocene compound through a simple process For the purpose, to prepare a reaction mixture by reacting the compound represented by the formula (1) and the compound represented by the formula (2) in the presence of an organic solvent, the reaction mixture is filtered, the filtration comprising a compound represented by the formula (3) Obtaining a liquid, and reacting the compound represented by the formula (3) of the filtrate with the compound represented by the following formula (4) to prepare a metallocene compound (asymmetric non-crosslinked metallocene compound) represented by the following formula (5): Steps.

상기 화학식 1 내지 5에서, Cp¹ 및 Cp²는 각각 독립적으로 (하나 이상의) 탄소수 1 내지 30, 바람직하게는 1 내지 20, 더욱 바람직하게는 1 내지 10의 하이드로카빌 라디칼이 치환 또는 비치환된 싸이클로펜타디에닐 핵을 가진 라디칼(유기기), 예를 들면, 싸이클로펜타디에닐(cyclopentadienyl), 치환된 싸이클로펜타디에닐, 인데닐(indenyl), 치환된 인데닐, 테트라하이드로인데닐(4,5,6,7-테트라하이드로-1-인데닐(4,5,6,7-tetrahydro-1-indenyl)), 치환된 테트라하이드로인데닐, 플루오레닐(fluorenyl), 치환된 플루오레닐 라디칼 등이고, Cp¹ 및 Cp²는 서로 다른 구조를 가진다. M¹은 티타늄, 지르코늄 또는 하프늄이고, X는 할로겐 원자, 바람직하게는 염소 원자(Cl), 브롬 원자(Br) 또는 요오드 원자(I), 더욱 바람직하게는 염소 원자(Cl)이고, 서로 동일하거나 다를 수 있으며, M²는 주기율표의 1 또는 2족의 원소, 바람직하게는 리튬(Li), 소듐(Na), 포타슘(K) 또는 마그네슘(Mg)이고, R은 탄소수 1 내지 10의 하이드로카빌 라디칼이다. m은 1 또는 2의 정수이고, n은 0 또는 1의 정수이며, m+n은 M²의 원자가와 동일하다.
In Chemical Formulas 1 to 5, Cp ¹ And Cp ² are each independently a radical having a cyclopentadienyl nucleus having one or more (one or more) carbon atoms of 1 to 30, preferably 1 to 20, more preferably 1 to 10, substituted or unsubstituted. Instruments), for example cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, tetrahydroindenyl (4,5,6,7-tetrahydro-1 -Indenyl (4,5,6,7-tetrahydro-1-indenyl), substituted tetrahydroindenyl, fluorenyl, substituted fluorenyl radical, and the like, Cp ¹ And Cp ² have different structures. M ¹ is titanium, zirconium or hafnium, X is a halogen atom, preferably chlorine atom (Cl), bromine atom (Br) or iodine atom (I), more preferably chlorine atom (Cl), M ² may be an element of Group 1 or 2 of the periodic table, preferably lithium (Li), sodium (Na), potassium (K) or magnesium (Mg), and R is a hydrocarbyl radical having 1 to 10 carbon atoms to be. m is an integer of 1 or 2, n is an integer of 0 or 1, and m + n is equal to the valence of M ² .

상기 비대칭성 비가교형 메탈로센 화합물의 제조방법에서, 상기 화학식 1로 표시되는 화합물과 상기 화학식 2로 표시되는 화합물의 반응은 하기 반응식 1로 나타낼 수 있고, 상기 화학식 3으로 표시되는 화합물과 상기 화학식 4로 표시되는 화합물의 반응은 하기 반응식 2로 나타낼 수 있다.In the method for preparing the asymmetric non-crosslinked metallocene compound, the reaction of the compound represented by Formula 1 and the compound represented by Formula 2 may be represented by Scheme 1 below, and the compound represented by Formula 3 and the formula The reaction of the compound represented by 4 can be represented by the following scheme 2.

[반응식 1][Reaction Scheme 1]

(Cp¹)₂M¹X₂ + M¹X₄ →2(Cp¹)M¹X₃ (Cp ¹ ) ₂ M ¹ X ₂ + M ¹ X ₄ → 2 (Cp ¹ ) M ¹ X ₃

[반응식 2][Reaction Scheme 2]

(Cp¹)M¹X₃ + (Cp²)_mM²R_n → (Cp¹)(Cp²)M¹X₂ + (Cp²)_pM²R_nX(Cp ¹ ) M ¹ X ₃ + (Cp ² ) _m M ² R _n → (Cp ¹ ) (Cp ² ) M ¹ X ₂ + (Cp ² ) _p M ² R _n X

상기 반응식 1 및 2에서, Cp¹, Cp², M¹, X, M², R, m 및 n은 상기 화학식 1 내지 5에서 정의한 바와 같고, p는 0 또는 1이고, p+n은 1이다.
In Schemes 1 and 2, Cp ¹ , Cp ² , M ¹ , X, M ² , R, m and n are as defined in Formulas 1 to 5, p is 0 or 1, p + n is 1 .

상기 반응식 1에서, 상기 화학식 1로 표시되는 화합물((Cp¹)₂M¹X₂)과 상기 화학식 2로 표시되는 화합물(M¹X₄)의 반응은, 상기 화학식 1로 표시되는 화합물에 대한 상기 화학식 2로 표시되는 화합물의 당량비(화학적 당량비, [M¹X₄]/[(Cp¹)₂M¹X₂])가 0.9 내지 1.1, 바람직하게는 1.0 내지 1.1이 되도록, 상기 화합물들을 서서히 유기용매에 용해시키고 혼합하여 반응시킬 수 있다. 상기 반응은 상기 유기용매 존재 하에서, 25 내지 100℃, 바람직하게는 30 내지 90℃의 반응 온도에서 8 내지 24시간, 바람직하게는 14 내지 24시간의 반응 시간 동안 수행된다. 상기 화학식 1로 표시되는 화합물에 대한 상기 화학식 2로 표시되는 화합물의 당량비가 상기 범위를 벗어날 경우, 미반응물이 남을 우려가 있다. 또한, 상기 반응 온도 및 상기 반응 시간이 상기 범위를 벗어날 경우, 반응이 완전히 되지 않거나, 과도한 반응으로 인하여 부생성물이 생성될 우려가 있다.
In Scheme 1, the reaction of the compound represented by Chemical Formula 1 ((Cp ¹ ) ₂ M ¹ X ₂ ) and the compound (M ¹ X ₄ ) represented by Chemical Formula 2 is performed on the compound represented by Chemical Formula 1 The compounds are slowly added so that the equivalent ratio (chemical equivalent ratio, [M ¹ X ₄ ] / [(Cp ¹ ) ₂ M ¹ X ₂ ]) of the compound represented by Formula 2 is 0.9 to 1.1, preferably 1.0 to 1.1. It can be dissolved in an organic solvent and mixed to react. The reaction is carried out in the presence of the organic solvent for a reaction time of 8 to 24 hours, preferably 14 to 24 hours at a reaction temperature of 25 to 100 ℃, preferably 30 to 90 ℃. When the equivalent ratio of the compound represented by Chemical Formula 2 to the compound represented by Chemical Formula 1 is outside the above range, there is a fear that unreacted material remains. In addition, when the reaction temperature and the reaction time out of the range, there is a fear that the reaction is not complete, or by-products are generated due to excessive reaction.

상기 유기용매로는, 예를 들면, 톨루엔, 디클로로메탄 등을 사용할 수 있다.　상기 반응으로 생성된 상기 화학식 3으로 표시되는 화합물((Cp¹)M¹X₃)을 포함하는 반응 혼합물은 여과하여 얻어진 여과액을 그대로 상기 반응식 2의 반응에 사용할 수 있으며, 여과액의 유기용매 제거하고 재결정 등의 방법으로 상기 화학식 3으로 표시되는 화합물을 정제하여 사용할 수도 있다.
As said organic solvent, toluene, dichloromethane, etc. can be used, for example. The reaction mixture containing the compound represented by Chemical Formula 3 ((Cp ¹ ) M ¹ X ₃ ) produced by the reaction may be used as it is for the reaction of Scheme 2, the filtrate obtained by filtration as it is, and the organic solvent of the filtrate The compound represented by the formula (3) may be purified by removal and recrystallization.

상기 화학식 4로 표시되는 화합물(알칼리 금속염 또는 알칼리 토금속염, (Cp²)_mM²R_n)은 공지된 다양한 방법에 따라 제조할 수 있으며, 예를 들면, 치환된 싸이클로펜타디에닐 화합물을 리튬, 소듐(나트륨), 포타슘(칼륨) 등의 알칼리금속 또는 알칼리 토금속(M²)을 포함하는 화합물, 예를 들면, 부틸리튬과 같은 금속화시약과 반응시켜 제조할 수 있다. 일반적으로 치환된 싸이클로펜타디에닐 화합물의 알칼리금속 화합물로의 전환반응은 질소 등의 불활성 분위기 및 용매 존재 하에서 온도 -78 내지 100℃에서 2 내지 40시간 동안 수행한다.　이때, 상기 용매로는 디에틸에테르, 디에틸렌글리콜디에틸에테르, 테트라하이드로퓨란(THF), 펜탄, 헥산, 헵탄 등을 사용할 수 있으며, 바람직하게는 디에틸에테르, 테트라하이드로퓨란(THF), 펜탄 또는 헥산을 사용할 수 있다. 상기 제조방법 등을 응용하여 얻어진 상기 화학식 4로 표시되는 화합물(예를 들면, 치환된 싸이클로펜타디에닐 화합물의 알칼리 금속염)은 다음 단계의 반응에 반응 혼합물 상태로 직접 사용될 수도 있으며, 고체 분말 형태의 금속 화합물로 수득한 후, 상기 반응식 2의 반응에 사용될 수 있다.
The compound represented by the above formula (4) (an alkali metal salt or alkaline earth metal ^{_{^{salt, (Cp 2) m M 2}}} R n) can be prepared according to various known methods, for example, lithium substituted cyclo pentadienyl compound It may be prepared by reacting a compound containing an alkali metal such as sodium (sodium), potassium (potassium) or alkaline earth metal (M ² ) with a metallization reagent such as butyllithium. In general, the conversion of the substituted cyclopentadienyl compound to the alkali metal compound is carried out for 2 to 40 hours at a temperature of -78 to 100 ° C in the presence of a solvent and an inert atmosphere such as nitrogen. In this case, as the solvent, diethyl ether, diethylene glycol diethyl ether, tetrahydrofuran (THF), pentane, hexane, heptane, and the like may be used. Preferably, diethyl ether, tetrahydrofuran (THF), and pentane are used. Or hexane can be used. The compound represented by Chemical Formula 4 (for example, an alkali metal salt of a substituted cyclopentadienyl compound) obtained by applying the preparation method may be used directly in a reaction mixture state in the next step of reaction, After obtaining as a metal compound, it can be used in the reaction of Scheme 2.

상기 반응식 2에서, 상기 화학식 3으로 표시되는 화합물((Cp¹)M¹X₃)과 상기 화학식 4로 표시되는 화합물((Cp²)_mM²R_n)의 반응은, 상기 반응식 1에 사용된 상기 화학식 1로 표시되는 화합물((Cp¹)₂M¹X₂)에 대한 상기 화학식 4로 표시되는 화합물의 당량비(화학적 당량비, [(Cp²)_mM²R_n]/[(Cp¹)₂M¹X₂])가 1.8 내지 2.2, 바람직하게는 1.9 내지 2.1이 되도록, 상기 화학식 4로 표시되는 화합물을 유기용매의 존재 하에, 상기 반응식 1에서 얻어진 상기 화학식 3으로 표시되는 화합물을 포함하는 여과액 또는 정제된 상기 화학식 3으로 표시되는 화합물에 투입하고 혼합하여 반응 시킬 수 있다. 상기 반응은 25 내지 100℃, 바람직하게는 30 내지 90℃의 반응 온도에서 8 내지 24시간, 바람직하게는 14 내지 24시간의 반응 시간 동안 수행된다. 상기 화학식 1로 표시되는 화합물에 대한 상기 화학식 4로 표시되는 화합물의 당량비가 상기 범위를 벗어날 경우, 여러 가지 불순물이 생성될 우려가 있다. 또한, 상기 반응 온도 및 상기 반응 시간이 상기 범위를 벗어날 경우, 반응이 완전히 진행되지 않거나, 과도한 반응으로 인하여 부생성물이 생성될 우려가 있다. 또한, 상기 유기용매로는, 상기 반응식 1과 동일하게, 톨루엔, 디클로로메탄 등을 사용할 수 있다.
In Scheme 2, the reaction of the compound represented by Formula 3 ((Cp ¹ ) M ¹ X ₃ ) and the compound represented by Formula 4 ((Cp ² ) _m M ² R _n ) is used in Scheme 1 Equivalent ratio of the compound represented by Chemical Formula 4 to the compound represented by Chemical Formula 1 ((Cp ¹ ) ₂ M ¹ X ₂ ) (chemical equivalent ratio, [(Cp ² ) _m M ² R _n ] / [(Cp ¹⁾ ) ₂ M ¹ X ₂ ]) to 1.8 to 2.2, preferably 1.9 to 2.1, the compound represented by the formula (4) comprises a compound represented by the formula (3) obtained in the reaction scheme 1 in the presence of an organic solvent To the filtrate or purified to the compound represented by the formula 3 can be reacted by mixing. The reaction is carried out for a reaction time of 8 to 24 hours, preferably 14 to 24 hours at a reaction temperature of 25 to 100 ℃, preferably 30 to 90 ℃. When the equivalent ratio of the compound represented by Chemical Formula 4 to the compound represented by Chemical Formula 1 is outside the above range, various impurities may be produced. In addition, when the reaction temperature and the reaction time out of the range, there is a fear that the reaction does not proceed completely, or by-products are generated due to excessive reaction. As the organic solvent, toluene, dichloromethane, or the like may be used in the same manner as in Scheme 1.

상기 반응식 2의 반응으로 생성된 상기 화학식 5로 표시되는 메탈로센 화합물(비대칭성 비가교형 메탈로센 화합물)을 포함하는 반응 혼합물은 여과한 후, 얻어진 여과액의 유기용매 제거하고 적절한 용매를 사용하여 재결정 등의 방법으로 상기 화학식 5로 표시되는 메탈로센 화합물을 최종 수득한다.
After the reaction mixture containing the metallocene compound (asymmetric non-crosslinked metallocene compound) represented by Chemical Formula 5 produced by the reaction of Scheme 2 is filtered, the organic solvent of the obtained filtrate is removed and an appropriate solvent is used. To finally obtain a metallocene compound represented by Chemical Formula 5 by recrystallization or the like.

본 발명에 사용되는 화학식 1로 표시되는 화합물(메탈로센 화합물, (Cp¹)₂M¹X₂)의 비한정적인 예로는, M¹이 지르코늄이고, X가 할로겐 원자, 특히, 염소 원자이며, 치환 또는 비치환된 싸이클로펜타디에닐 핵을 가진 라디칼((Cp¹))이 싸이클로펜타디에닐, 메틸싸이클로펜타디에닐, 1,2,3,4-테트라메틸싸이클로펜타디에닐, 에틸싸이클로펜타디에닐, 프로필싸이클로펜타디에닐, 부틸싸이클로펜타디에닐, 이소부틸싸이클로펜타디에닐, 옥타데실싸이클로펜타디에닐, 싸이클로펜틸싸이클로펜타디에닐, 싸이클로헥실싸이클로펜타디에닐, 1,3-부틸메틸싸이클로펜타디에닐, 인데닐, 1-메틸인데닐, 2-메틸인데닐, 1-에틸인데닐, 2-에틸인데닐, 1-프로필인데닐, 2-프로필인데닐, 2-페닐인데닐, 3-페닐인데닐, 플루오레닐, 및 이들의 유사체로 이루어지는 군에서 선택되는 라디칼인 것을 예시할 수 있다.
Non-limiting examples of the compound represented by the formula ( ¹ ) (metallocene compound, (Cp ¹ ) ₂ M ¹ X ₂ ) used in the present invention, M ¹ is zirconium, X is a halogen atom, in particular, a chlorine atom , Radicals with a substituted or unsubstituted cyclopentadienyl nucleus ((Cp ¹ )) are cyclopentadienyl, methylcyclopentadienyl, 1,2,3,4-tetramethylcyclopentadienyl, ethylcyclopenta Dienyl, Propylcyclopentadienyl, Butylcyclopentadienyl, Isobutylcyclopentadienyl, Octadecylcyclopentadienyl, Cyclopentylcyclopentadienyl, Cyclohexylcyclopentadienyl, 1,3-butylmethylcyclo Pentadienyl, indenyl, 1-methyl indenyl, 2-methyl indenyl, 1-ethyl indenyl, 2-ethyl indenyl, 1-propyl indenyl, 2-propyl indenyl, 2-phenylindenyl, 3 -Phenylindenyl, fluorenyl, and analogues thereof Illustrative radicals can be mentioned.

본 발명에 사용되는 화학식 4로 표시되는 화합물(알칼리 금속염 또는 알칼리 토금속염, (Cp²)_mM²R_n)의 비한정적인 예로는, 싸이클로펜타디에닐리튬, 메틸싸이클로펜타디에닐리튬, 펜타메틸싸이클로펜타디에닐리튬, 1,2,3,4-테트라메틸싸이클로펜타디에닐리튬, 에틸싸이클로펜타디에닐리튬, 프로필싸이클로펜타디에닐리튬, 부틸싸이클로펜타디에닐리튬, 이소부틸싸이클로펜타디에닐리튬, 옥타데실싸이클로펜타디에닐리튬, 싸이클로펜틸싸이클로펜타디에닐리튬, 싸이클로헥실싸이클로펜타디에닐리튬, 1,3-부틸메틸싸이클로펜타디에닐리튬, 인데닐리튬, 1-메틸인데닐리튬, 2-메틸인데닐리튬, 1-에틸인데닐리튬, 2-에틸인데닐리튬, 1-프로필인데닐리튬, 2-프로필인데닐리튬, 2-페닐인데닐리튬, 3-페닐인데닐리튬, 플루오레닐리튬, 싸이클로펜타디에닐소듐, 메틸싸이클로펜타디에닐소듐, 펜타메틸싸이클로펜타디에닐소듐, 1,2,3,4-테트라메틸싸이클로펜타디에닐소듐, 에틸싸이클로펜타디에닐소듐, 프로필싸이클로펜타디에닐소듐, 부틸싸이클로펜타디에닐소듐, 이소부틸싸이클로펜타디에닐소듐, 옥타데실싸이클로펜타디에닐소듐, 싸이클로펜틸싸이클로펜타디에닐소듐, 싸이클로헥실싸이클로펜타디에닐소듐, 1,3-부틸메틸싸이클로펜타디에닐소듐, 인데닐소듐, 1-메틸인데닐소듐, 2-메틸인데닐소듐, 1-에틸인데닐소듐, 2-에틸인데닐소듐, 1-프로필인데닐소듐, 2-프로필인데닐소듐, 2-페닐인데닐소듐, 3-페닐인데닐소듐, 플루오레닐소듐, 싸이클로펜타디에닐마그네슘메틸, 싸이클로펜타디에닐마그네슘에틸, 싸이클로펜타디에닐마그네슘이소부틸, 싸이클로펜타디에닐마그네슘프로필, 싸이클로펜타디에닐마그네슘헵틸, 싸이클로펜타디에닐마그네슘옥틸, 메틸싸이클로펜타디에닐마그네슘메틸, 메틸싸이클로펜타디에닐마그네슘에틸, 메틸싸이클로펜타디에닐마그네슘이소부틸, 메틸싸이클로펜타디에닐마그네슘프로필, 메틸싸이클로펜타디에닐마그네슘헵틸, 메틸싸이클로펜타디에닐마그네슘옥틸, 펜타메틸싸이클로펜타디에닐마그네슘메틸, 펜타메틸싸이클로펜타디에닐마그네슘에틸, 펜타메틸싸이클로펜타디에닐마그네슘이소부틸, 펜타메틸싸이클로펜타디에닐마그네슘프로필, 펜타메틸싸이클로펜타디에닐마그네슘헵틸, 펜타메틸싸이클로펜타디에닐마그네슘옥틸, 1,2,3,4-테트라메틸싸이클로펜타디에닐마그네슘메틸, 1,2,3,4-테트라메틸싸이클로펜타디에닐마그네슘에틸, 1,2,3,4-테트라메틸싸이클로펜타디에닐마그네슘이소부틸, 1,2,3,4-테트라메틸싸이클로펜타디에닐마그네슘프로필, 1,2,3,4-테트라메틸싸이클로펜타디에닐마그네슘헵틸, 1,2,3,4-테트라메틸싸이클로펜타디에닐마그네슘옥틸, 에틸싸이클로펜타디에닐마그네슘메틸, 에틸싸이클로펜타디에닐마그네슘에틸, 에틸싸이클로펜타디에닐마그네슘이소부틸, 에틸싸이클로펜타디에닐마그네슘프로필, 에틸싸이클로펜타디에닐마그네슘헵틸, 에틸싸이클로펜타디에닐마그네슘옥틸, 프로필싸이클로펜타디에닐마그네슘메틸, 프로필싸이클로펜타디에닐마그네슘에틸, 프로필싸이클로펜타디에닐마그네슘이소부틸, 프로필싸이클로펜타디에닐마그네슘프로필, 프로필싸이클로펜타디에닐마그네슘헵틸, 프로필싸이클로펜타디에닐마그네슘옥틸, 부틸싸이클로펜타디에닐마그네슘메틸, 부틸싸이클로펜타디에닐마그네슘에틸, 부틸싸이클로펜타디에닐마그네슘이소부틸, 부틸싸이클로펜타디에닐마그네슘프로필, 부틸싸이클로펜타디에닐마그네슘헵틸, 부틸싸이클로펜타디에닐마그네슘옥틸, 이소부틸싸이클로펜타디에닐마그네슘메틸, 이소부틸싸이클로펜타디에닐마그네슘에틸, 이소부틸싸이클로펜타디에닐마그네슘이소부틸, 이소부틸싸이클로펜타디에닐마그네슘프로필, 이소부틸싸이클로펜타디에닐마그네슘헵틸, 이소부틸싸이클로펜타디에닐마그네슘옥틸, 옥타데실싸이클로펜타디에닐마그네슘메틸, 옥타데실싸이클로펜타디에닐마그네슘에틸, 옥타데실싸이클로펜타디에닐마그네슘이소부틸, 옥타데실싸이클로펜타디에닐마그네슘프로필, 옥타데실싸이클로펜타디에닐마그네슘헵틸, 옥타데실싸이클로펜타디에닐마그네슘옥틸, 싸이클로펜틸싸이클로펜타디에닐마그네슘메틸, 싸이클로펜틸싸이클로펜타디에닐마그네슘에틸, 싸이클로펜틸싸이클로펜타디에닐마그네슘이소부틸, 싸이클로펜틸싸이클로펜타디에닐마그네슘프로필, 싸이클로펜틸싸이클로펜타디에닐마그네슘헵틸, 싸이클로펜틸싸이클로펜타디에닐마그네슘옥틸, 싸이클로헥실싸이클로펜타디에닐마그네슘메틸, 싸이클로헥실싸이클로펜타디에닐마그네슘에틸, 싸이클로헥실싸이클로펜타디에닐마그네슘이소부틸, 싸이클로헥실싸이클로펜타디에닐마그네슘프로필, 싸이클로헥실싸이클로펜타디에닐마그네슘헵틸, 싸이클로헥실싸이클로펜타디에닐마그네슘옥틸, 1,3-부틸메틸싸이클로펜타디에닐마그네슘메틸, 1,3-부틸메틸싸이클로펜타디에닐마그네슘에틸, 1,3-부틸메틸싸이클로펜타디에닐마그네슘이소부틸, 1,3-부틸메틸싸이클로펜타디에닐마그네슘프로필, 1,3-부틸메틸싸이클로펜타디에닐마그네슘헵틸, 1,3-부틸메틸싸이클로펜타디에닐마그네슘옥틸, 비스(싸이클로펜타디에닐)마그네슘, 비스(알킬-싸이클로펜타디에닐)마그네슘, 비스(인데닐)마그네슘, 비스(알킬-인데닐)마그네슘,　인데닐마그네슘메틸, 인데닐마그네슘에틸, 인데닐마그네슘이소부틸, 인데닐마그네슘프로필, 인데닐마그네슘헵틸, 인데닐마그네슘옥틸, 2-메틸인데닐마그네슘메틸, 2-메틸인데닐마그네슘에틸, 2-메틸인데닐마그네슘이소부틸, 2-메틸인데닐마그네슘프로필, 2-메틸인데닐마그네슘헵틸, 2-메틸인데닐마그네슘옥틸, 3-메틸인데닐마그네슘메틸, 3-메틸인데닐마그네슘에틸, 3-메틸인데닐마그네슘이소부틸, 3-메틸인데닐마그네슘프로필, 3-메틸인데닐마그네슘헵틸, 3-메틸인데닐마그네슘옥틸, 2-페닐인데닐마그네슘메틸, 2-페닐인데닐마그네슘에틸, 2-페닐인데닐마그네슘이소부틸, 2-페닐인데닐마그네슘프로필, 2-페닐인데닐마그네슘헵틸, 2-페닐인데닐마그네슘옥틸, 3-페닐인데닐마그네슘메틸, 3-페닐인데닐마그네슘에틸, 3-페닐인데닐마그네슘이소부틸, 3-페닐인데닐마그네슘프로필, 3-페닐인데닐마그네슘헵틸, 3-페닐인데닐마그네슘옥틸, 플루오레닐마그네슘메틸, 플루오레닐마그네슘에틸, 플루오레닐마그네슘이소부틸, 플루오레닐마그네슘프로필, 플루오레닐마그네슘헵틸, 플루오레닐마그네슘옥틸 및 그의 유사체로 이루어지는 군에서 선택되는 알칼리 금속염 또는 알칼리 토금속염을 예시할 수 있다.
Non-limiting examples of the compound represented by the following general formula (4) used in the present invention (an alkali metal salt or alkaline earth metal ^{_{^{salt, (Cp 2) m M 2}}} R n) , the cyclo-pentadienyl lithium, methyl cyclo pentadienyl lithium, Penta Methylcyclopentadienyl lithium, 1,2,3,4-tetramethylcyclopentadienyl lithium, ethylcyclopentadienyl lithium, propyl cyclopentadienyl lithium, butyl cyclopentadienyl lithium, isobutyl cyclopentadienyl Lithium, Octadecylcyclopentadienyllithium, cyclopentylcyclocyclopentadienyllithium, cyclohexylcyclopentadienyllithium, 1,3-butylmethylcyclopentadienyllithium, indenylithium, 1-methyldenylithium, 2 -Methyl indenylithium, 1-ethylindenylithium, 2-ethylindenylithium, 1-propylindenylithium, 2-propylindenylithium, 2-phenylindenylithium, 3-phenylindenylithium, fluore Nilithium, cyclopentadienyl-so Sodium, methylcyclopentadienylsodium, pentamethylcyclopentadienylsodium, 1,2,3,4-tetramethylcyclopentadienylsodium, ethylcyclopentadienylsodium, propylcyclopentadienylsodium, butylcyclopenta Dienylsodium, isobutylcyclopentadienylsodium, octadecylcyclopentadienylsodium, cyclopentylcyclopentadienylsodium, cyclohexylcyclopentadienylsodium, 1,3-butylmethylcyclopentadienylsodium, indenyl Sodium, 1-methyl indenyl sodium, 2-methyl indenyl sodium, 1-ethyl indenyl sodium, 2-ethyl indenyl sodium, 1-propyl indenyl sodium, 2-propyl indenyl sodium, 2-phenyl indenyl sodium , 3-phenylindenyl sodium, fluorenyl sodium, cyclopentadienyl magnesium methyl, cyclopentadienyl magnesium ethyl, cyclopentadienyl magnesium isobutyl, cyclopentadienyl magnesium propyl, cyclopentadienyl Magnesium heptyl, cyclopentadienyl magnesium octyl, methyl cyclopentadienyl magnesium methyl, methyl cyclopentadienyl magnesium ethyl, methyl cyclopentadienyl magnesium isobutyl, methyl cyclopentadienyl magnesium propyl, methyl cyclopentadiene Heptyl, methyl cyclopentadienyl magnesium octyl, pentamethyl cyclopentadienyl magnesium methyl, pentamethyl cyclopentadienyl magnesium ethyl, pentamethyl cyclopentadienyl magnesium isobutyl, pentamethyl cyclopentadienyl methyl magnesium pentomethyl Pentadienyl magnesiumheptyl, pentamethylcyclopentadienyl magnesium octyl, 1,2,3,4-tetramethylcyclopentadienylmagnesiummethyl, 1,2,3,4-tetramethylcyclopentadienyl magnesiumethyl, 1 , 2,3,4-tetramethylcyclopentadienylmagnesiumisobutyl, 1,2,3,4-tetramethylthio Clopentadienyl magnesium propyl, 1,2,3,4-tetramethylcyclopentadienylmagnesiumheptyl, 1,2,3,4-tetramethylcyclopentadienylmagnesiumoctyl, ethylcyclopentadienylmagnesiummethyl, ethyl Cyclopentadienyl magnesium ethyl, ethyl cyclopentadienyl magnesium isobutyl, ethyl cyclopentadienyl magnesium propyl, ethyl cyclopentadienyl magnesium heptyl, ethyl cyclopentadienyl magnesium octyl, propyl cyclopenta methyl dienyl propyl magnesium Pentadienyl magnesium ethyl, propyl cyclopentadienyl magnesium isobutyl, propyl cyclopentadienyl magnesium propyl, propyl cyclopentadienyl magnesium heptyl, propyl cyclopentadienyl magnesium octyl, butyl cyclopentadienyl butyl magnesium methyl, Dienyl magnesium ethyl, butyl cyclopentadienyl Nesium isobutyl, butyl cyclopentadienyl magnesium propyl, butyl cyclopentadienyl magnesium heptyl, butyl cyclopentadienyl magnesium octyl, isobutyl cyclopentadienyl magnesium methyl, isobutyl cyclopentadienyl butyl magnesium isoethyl ethyl, Dienyl magnesium isobutyl, isobutyl cyclopentadienyl magnesium propyl, isobutyl cyclopentadienyl magnesium heptyl, isobutyl cyclopentadienyl magnesium octyl, octadecyl cyclopentadienyl magnesium methyl, octadecyl ethyl cyclopentane , Octadecylcyclopentadienylmagnesium isobutyl, octadecylcyclopentadienyl magnesium propyl, octadecylcyclopentadienyl magnesiumheptyl, octadecylcyclopentadienyl magnesium octyl, cyclopentylcyclopentanemethyl pentyl methyl pentyl Lopentadienyl magnesium ethyl, cyclopentyl cyclopentadienyl magnesium isobutyl, cyclopentyl cyclopentadienyl magnesium propyl, cyclopentyl cyclopentadienyl magnesium heptyl, cyclopentyl cyclopentadienyl hexane Magnesium methyl, cyclohexylcyclopentadienylmagnesiumethyl, cyclohexylcyclopentadienylmagnesiumisobutyl, cyclohexylcyclopentadienylmagnesiumpropyl, cyclohexylcyclopentadienylmagnesiumheptyl, cyclohexenyldecoxy , 3-butylmethylcyclopentadienylmagnesiummethyl, 1,3-butylmethylcyclopentadienylmagnesiumethyl, 1,3-butylmethylcyclopentadienylmagnesium isobutyl, 1,3-butylmethylcyclopentadienylmagnesium Propyl, 1,3-butylmethylcyclophene Dienylmagnesiumheptyl, 1,3-butylmethylcyclopentadienylmagnesiumoctyl, bis (cyclopentadienyl) magnesium, bis (alkyl-cyclopentadienyl) magnesium, bis (indenyl) magnesium, bis (alkyl-inde Nil) magnesium, indenyl magnesium methyl, indenyl magnesium ethyl, indenyl magnesium isobutyl, indenyl magnesium propyl, indenyl magnesium heptyl, indenyl magnesium octyl, 2-methyl indenyl magnesium methyl, 2-methyl indenyl magnesium ethyl 2-methylindenyl magnesium isobutyl, 2-methyl indenyl magnesium propyl, 2-methyl indenyl magnesium heptyl, 2-methyl indenyl magnesium octyl, 3-methyl indenyl magnesium methyl, 3-methyl indenyl magnesium ethyl, 3-methylindenyl magnesium isobutyl, 3-methyl indenyl magnesium propyl, 3-methyl indenyl magnesium heptyl, 3-methyl indenyl magnesium octyl, 2-phenyl indenyl magnesium methyl, 2-phenyl indenyl magnesium ethyl, 2 -Phenylin Nyl magnesium isobutyl, 2-phenyl indenyl magnesium propyl, 2-phenyl indenyl magnesium heptyl, 2-phenyl indenyl magnesium octyl, 3-phenyl indenyl magnesium methyl, 3-phenyl indenyl magnesium ethyl, 3-phenyl indenyl Magnesium isobutyl, 3-phenyl indenyl magnesium propyl, 3-phenyl indenyl magnesium heptyl, 3-phenyl indenyl magnesium octyl, fluorenyl magnesium methyl, fluorenyl magnesium ethyl, fluorenyl magnesium isobutyl, fluorenyl Alkali metal salts or alkaline earth metal salts selected from the group consisting of magnesium propyl, fluorenyl magnesium heptyl, fluorenyl magnesium octyl and analogs thereof can be exemplified.

본 발명에 따른 비대칭성 비가교형 메탈로센 화합물의 제조방법에 의해 제조된 화학식 5로 표시되는 메탈로센 화합물((Cp¹)(Cp²)M¹X₂)의 비한정적인 예로는 (메틸싸이클로펜타디에닐)(싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(에틸싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(노말프로필싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(이소프로필싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(이소부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(터셔리부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(노말펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(이소펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(싸이클로펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(노말헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(이소헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(싸이클로헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(노말헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(이소헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(싸이클로헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(노말옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(이소옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(싸이클로옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(노말노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(이소노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(싸이클로노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(1-메틸,3-노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(펜타메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(테트라메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (메틸싸이클로펜타디에닐)(트리메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(노말프로필싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(이소프로필싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(이소부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(터셔리부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(노말펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(이소펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(싸이클로펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(노말헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(이소헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(싸이클로헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(노말헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(이소헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(싸이클로헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(노말옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(이소옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(싸이클로옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(노말노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(이소노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(싸이클로노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(1-메틸,3-노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(펜타메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(테트라메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (에틸싸이클로펜타디에닐)(트리메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말포로필싸이클로펜타디에닐)(싸이클로펜타디에닐)지르코늄 디클로라이드, (노말프로필싸이클로펜타디에닐)(에틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말프로필싸이클로펜타디에닐)(이소프로필싸이클로펜타디에닐)지르코늄 디클로라이드, (노말프로필싸이클로펜타디에닐)(노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말프로필싸이클로펜타디에닐)(이소부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말프로필싸이클로펜타디에닐)(터셔리부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말프로필싸이클로펜타디에닐)(노말펜틸싸이클로펜타디에닐)지르코늄 디클로라 이드, (노말프로필싸이클로펜타디에닐)(이소펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말프로필싸이클로펜타디에닐)(싸이클로펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말프로필싸이클로펜타디에닐)(노말헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (노말프로필싸이클로펜타디에닐)(이소헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (노말프로필싸이클로펜타디에닐)(싸이클로헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (노말프로필싸이클로펜타디에닐)(노말헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말프로필싸이클로펜타디에닐)(이소헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말프로필싸이클로펜타디에닐)(싸이클로헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말프로필싸이클로펜타디에닐)(노말옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말프로필싸이클로펜타디에닐)(이소옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말프로필싸이클로펜타디에닐)(싸이클로옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말프로필싸이클로펜타디에닐)(노말노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (노말프로필싸이클로펜타디에닐)(이소노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (노말프로필싸이클로펜타디에닐)(싸이클로노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (노말프로필싸이클로펜타디에닐)(1-메틸,3-노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말프로필싸이클로펜타디에닐)(펜타메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말프로필싸이클로펜타디에닐)(테트라메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말프로필싸이클로펜타디에닐)(트리메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (이소프로필싸이클로펜타디에닐)(싸이클로펜타디에닐)지르코늄 디클로라이드, (이소프로필싸이클로펜타디에닐)(에틸싸이클로펜타디에닐)지르코늄 디클로라이드, (이소프로필싸이클로펜타디에닐)(노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (이소프로필싸이클로펜타디에닐)(이소부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (이소프로필싸이클로펜타디에닐)(터셔리부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (이소프로필싸이클로펜타디에닐)(노말펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (이소프로필싸이클로펜타디에닐)(이소펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (이소프로필싸이클로펜타디에닐)(싸이클로펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (이소프로필싸이클로펜타디에닐)(노말헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (이소프로필싸이클로펜타디에닐)(이소헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (이소프로필싸이클로펜타디에닐)(싸이클로헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (이소프로필싸이클로펜타디에닐)(노말헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (이소프로필싸이클로펜타디에닐)(이소헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (이소프로필싸이클로펜타디에닐)(싸이클로헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (이소프로필싸이클로펜타디에닐)(노말옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (이소프로필싸이클로펜타디에닐)(이소옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (이소프로필싸이클로펜타디에닐)(싸이클로옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (이소프로필싸이클로펜타디에닐)(노말노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (이소프로필싸이클로펜타디에닐)(이소노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (이소프로필싸이클로펜타디에닐)(싸이클로노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (이소프로필싸이클로펜타디에닐)(1-메틸,3-노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (이소프로필싸이클로펜타디에닐)(펜타메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (이소프로필싸이클로펜타디에닐)(테트라메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (이소프로필싸이클로펜타디에닐)(트리메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말부틸싸이클로펜타디에닐)(싸이클로펜타디에닐)지르코늄 디클로라이드, (노말부틸싸이클로펜타디에닐)(에틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말부틸싸이클로펜타디에닐)(이소부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말부틸싸이클로펜타디에닐)(터셔리부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말부틸싸이클로펜타디에닐)(노말펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말부틸싸이클로펜타디에닐)(이소펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말부틸싸이클로펜타디에닐)(싸이클로펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말부틸싸이클로펜타디에닐)(노말헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (노말부틸싸이클로펜타디에닐)(이소헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (노말부틸싸이클로펜타디에닐)(싸이클로헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (노말부틸싸이클로펜타디에닐)(노말헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말부틸싸이클로펜타디에닐)(이소헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말부틸싸이클로펜타디에닐)(싸이클로헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말부틸싸이클로펜타디에닐)(노말옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말부틸싸이클로펜타디에닐)(이소옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말부틸싸이클로펜타디에닐)(싸이클로옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말부틸싸이클로펜타디에닐)(노말노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (노말부틸싸이클로펜타디에닐)(이소노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (노말부틸싸이클로펜타디에닐)(싸이클로노닐싸이클로펜타디에닐)지르코늄 디클로 라이드, (노말부틸싸이클로펜타디에닐)(1-메틸,3-노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말부틸싸이클로펜타디에닐)(펜타메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말부틸싸이클로펜타디에닐)(테트라메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (노말부틸싸이클로펜타디에닐)(트리메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (싸이클로펜틸싸이클로펜타디에닐)(싸이클로펜타디에닐)지르코늄 디클로라이드, (싸이클로펜틸싸이클로펜타디에닐)(에틸싸이클로펜타디에닐)지르코늄 디클로라이드, (싸이클로펜틸싸이클로펜타디에닐)(이소부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (싸이클로펜틸싸이클로펜타디에닐)(터셔리부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (싸이클로펜틸싸이클로펜타디에닐)(노말펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (싸이클로펜틸싸이클로펜타디에닐)(이소펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (싸이클로펜틸싸이클로펜타디에닐)(노말헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (싸이클로펜틸싸이클로펜타디에닐)(이소헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (싸이클로펜틸싸이클로펜타디에닐)(싸이클로헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (싸이클로펜틸싸이클로펜타디에닐)(노말헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (싸이클로펜틸싸이클로펜타디에닐)(이소헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (싸이클로펜틸싸이클로펜타디에닐)(싸이클로헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (싸이클로펜틸싸이클로펜타디에닐)(노말옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (싸이클로펜틸싸이클로펜타디에닐)(이소옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (싸이클로펜틸싸이클로펜타디에닐)(싸이클로옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (싸이클로펜틸싸이클로펜타디에닐)(노말노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (싸이클로펜틸싸이클로펜타디에닐)(이소노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (싸이클로펜틸싸이클로펜타디에닐)(싸이클로노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (싸이클로펜틸싸이클로펜타디에닐)(1-메틸,3-노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (싸이클로펜틸싸이클로펜타디에닐)(펜타메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (싸이클로펜틸싸이클로펜타디에닐)(테트라메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (싸이클로펜틸싸이클로펜타디에닐)(트리메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸,3-노말부틸싸이클로펜타디에닐)(싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸,3-노말부틸싸이클로펜타디에닐)(에틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸,3-노말부틸싸이클로펜타디에닐)(이소부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸,3-노말부틸싸이클로펜타디에닐)(터셔리부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸,3-노말부틸싸이클로펜타디에닐)(노말펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸,3-노말부틸싸이클로펜타디에닐)(이소펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸,3-노말부틸싸이클로펜타디에닐)(노말헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸,3-노말부틸싸이클로펜타디에닐)(이소헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸,3-노말부틸싸이클로 펜타디에닐)(싸이클로헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸,3-노말부틸싸이클로펜타디에닐)(노말헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸,3-노말부틸싸이클로펜타디에닐)(이소헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸,3-노말부틸싸이클로펜타디에닐)(싸이클로헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸,3-노말부틸싸이클로펜타디에닐)(노말옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸,3-노말부틸싸이클로펜타디에닐)(이소옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸,3-노말부틸싸이클로펜타디에닐)(싸이클로옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸,3-노말부틸싸이클로펜타디에닐)(노말노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸,3-노말부틸싸이클로펜타디에닐)(이소노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸,3-노말부틸싸이클로펜타디에닐)(싸이클로노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸,3-노말부틸싸이클로펜타디에닐)(펜타메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸,3-노말부틸싸이클로펜타디에닐)(테트라메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸,3-노말부틸싸이클로펜타디에닐)(트리메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (펜타메틸싸이클로펜타디에닐)(싸이클로펜타디에닐)지르코늄 디클로라이드, (펜타메틸싸이클로펜타디에닐)(에틸싸이클로펜타디에닐)지르코늄 디클로라이드, (펜타메틸싸이클로펜타디에닐)(이소부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (펜타메틸싸이클로펜타디에닐)(터셔리부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (펜타메틸싸이클로펜타디에닐)(노말펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (펜타메틸싸이클로펜타디에닐)(이소펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (펜타메틸싸이클로펜타디에닐)(노말헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (펜타메틸싸이클로펜타디에닐)(이소헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (펜타메틸싸이클로펜타디에닐)(싸이클로헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (펜타메틸싸이클로펜타디에닐)(노말헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (펜타메틸싸이클로펜타디에닐)(이소헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (펜타메틸싸이클로펜타디에닐)(싸이클로헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (펜타메틸싸이클로펜타디에닐)(노말옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (펜타메틸싸이클로펜타디에닐)(이소옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (펜타메틸싸이클로펜타디에닐)(싸이클로옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (펜타메틸싸이클로펜타디에닐)(노말노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (펜타메틸싸이클로펜타디에닐)(이소노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (펜타메틸싸이클로펜타디에닐)(싸이클로노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (펜타메틸싸이클로펜타디에닐)(펜타메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (펜타메틸싸이클로펜타디에닐)(테트라메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (펜타메틸싸이클로펜타디에닐)(트리메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라메틸싸이클로펜타디에닐)(싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라메틸싸이클로펜타디에닐)(에틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라메틸싸이클로펜타디에닐)(이소부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라메틸싸이클로펜타디에닐)(터셔리부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라메틸싸이클로펜타디에닐)(노말펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라메틸싸이클로펜타디에닐)(이소펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라메틸싸이클로펜타디에닐)(노말헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라메틸싸이클로펜타디에닐)(이소헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라메틸싸이클로펜타디에닐)(싸이클로헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라메틸싸이클로펜타디에닐)(노말헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라메틸싸이클로펜타디에닐)(이소헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라메틸싸이클로펜타디에닐)(싸이클로헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라메틸싸이클로펜타디에닐)(노말옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라메틸싸이클로펜타디에닐)(이소옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라메틸싸이클로펜타디에닐)(싸이클로옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라메틸싸이클로펜타디에닐)(노말노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라메틸싸이클로펜타디에닐)(이소노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라메틸싸이클로펜타디에닐)(싸이클로노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라메틸싸이클로펜타디에닐)(트리메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (트리메틸싸이클로펜타디에닐)(싸이클로펜타디에닐)지르코늄 디클로라이드, (트리메틸싸이클로펜타디에닐)(에틸싸이클로펜타디에닐)지르코늄 디클로라이드, (트리메틸싸이클로펜타디에닐)(이소부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (트리메틸싸이클로펜타디에닐)(터셔리부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (트리메틸싸이클로펜타디에닐)(노말펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (트리메틸싸이클로펜타디에닐)(이소펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (트리메틸싸이클로펜타디에닐)(노말헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (트리메틸싸이클로펜타디에닐)(이소헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (트리메틸싸이클로펜타디에닐)(싸이클로헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (트리메틸싸이클로펜타디에닐)(노말헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (트리메틸싸이클로펜타디에닐)(이소헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (트리메틸싸이클로펜타디에닐)(싸이클로헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (트리메틸싸이클로펜타디에닐)(노말옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (트리메틸싸이클로펜타디에닐)(이소옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (트리메틸싸이클로펜타디에닐)(싸이클로옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (트리메틸싸이클로펜타디에닐)(노말노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (트리메틸싸이클로펜타디에닐)(이소노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (트리메틸싸이클로펜타디에닐)(싸이클로노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(에틸싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(노말프로필싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(이소프로필싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(이소부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(터셔리부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(노말펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(이소펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(싸이클로펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(노말헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(이소헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(싸이클로헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(노말헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(이소헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(싸이클로헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(노말옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(이소옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(싸이클로옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(노말노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(이소노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(싸이클로노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(1-메틸,3-노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(펜타메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(테트라메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (인데닐)(트리메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(에틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(노말프로필싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(이소프로필싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(이소부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(터셔리부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(노말펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(이소펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(싸이클로펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(노말헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(이소헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(싸이클로헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(노말헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(이소헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(싸이클로헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(노말옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(이소옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(싸이클로옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(노말노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(이소노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(싸이클로노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(1-메틸,3-노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(펜타메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(테트라메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-메틸인데닐)(트리메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(에틸싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(노말프로필싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(이소프로필싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(이소부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(터셔리부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(노말펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(이소펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(싸이클로펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(노말헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(이소헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(싸이클로헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(노말헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(이소헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(싸이클로헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(노말옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(이소옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(싸이클로옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(노말노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(이소노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(싸이클로노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(1-메틸,3-노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(펜타메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(테트라메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (2-메틸인데닐)(트리메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(에틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(노말프로필싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(이소프로필싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(이소부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(터셔리부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(노말펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(이소펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(싸이클로펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(노말헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(이소헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(싸이클로헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(노말헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(이소헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(싸이클로헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(노말옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(이소옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(싸이클로옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(노말노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(이소노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(싸이클로노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(1-메틸,3-노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(펜타메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(테트라메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-에틸인데닐)(트리메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(에틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(노말프로필싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(이소프로필싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(이소부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(터셔리부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(노말펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(이소펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(싸이클로펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(노말헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(이소헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(싸이클로헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(노말헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(이소헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(싸이클로헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(노말옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(이소옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(싸이클로옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(노말노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(이소노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(싸이클로노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(1-메틸,3-노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(펜타메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(테트라메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (1-부틸인데닐)(트리메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(에틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(노말프로필싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(이소프로필싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(이소부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(터셔리부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(노말펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(이소펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(싸이클로펜틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(노말헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(이소헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(싸이클로헥실싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(노말헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(이소헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(싸이클로헵틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(노말옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(이소옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(싸이클로옥틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(노말노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(이소노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(싸이클로노닐싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(1-메틸,3-노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(펜타메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(테트라메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(트리메틸싸이클로펜타디에닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(인데닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(1-메틸인데닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(2-메틸인데닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(1-에틸인데닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(1-부틸인데닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(2-메틸인데닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(2-부틸인데닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(1-페닐인데닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(2-페닐인데닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(메틸벤조인데닐)지르코늄 디클로라이드, (인데닐)(메틸벤조인데닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(플루오레닐)지르코늄 디클로라이드, (인데닐)(플루오레닐)지르코늄 디클로라이드, (인데닐)(5,6-싸이클로펜타-2-메틸-1-인데닐)지르코늄 디클로라이드, (2-메틸인데닐)(5,6-싸이클로펜타-2-메틸-1-인데닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(5,6-싸이클로펜타-2-메틸-1-인데닐)지르코늄 디클로라이드, (인데닐)(2-메틸-4-페닐인데닐)지르코늄 디클로라이드, (2-메틸인데닐)(2-메틸-4-페닐인데닐)지르코늄 디클로라이드, (2-에틸인데닐)(2-메틸-4-페닐인데닐)지르코늄 디클로라이드, (2-이소부틸인데닐)(2-메틸-4-페닐인데닐)지르코늄 디클로라이드, (2-이소프로필인데닐)(2-메틸-4-페닐인데닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(2-메틸-4-페닐인데닐)지르코늄 디클로라이드, (인데닐)(5,6,7,8-테트라하이드로-5,5,8,8-테트라메틸-1H-벤즈[f]인데닐) 지르코늄 디클로라이드, (2-메틸인데닐)(5,6,7,8-테트라하이드로-5,5,8,8-테트라메틸-1H-벤즈[f]인데닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(5,6,7,8-테트라하이드로-5,5,8,8-테트라메틸-1H-벤즈[f]인데닐)지르코늄 디클로라이드, (인데닐)(2-메틸-4-(1-나프틸)인데닐)지르코늄 디클로라이드, (2-메틸인데닐)(2-메틸-4-(1-나프틸)인데닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(2-메틸-4-(1-나프틸)인데닐)지르코늄 디클로라이드, (인데닐)(2-메틸-4-이소프로필인데닐)지르코늄 디클로라이드, (2-메틸인데닐)(2-메틸-4-이소프로필인데닐)지르코늄 디클로라이드, (테트라하이드로인데닐)(2-메틸-4-이소프로필인데닐)지르코늄 디클로라이드, 이들의 유사 화합물 등을 예시할 수 있으며, 상기 화합물의 지르코늄 대신 티타늄, 하프늄 등의 전이금속을 포함하는 메탈로센 화합물들을 예시할 수 있다. 본 발명에 따른 비대칭성 비가교형 메탈로센 화합물은 상기 제시된 예에 한정된 것은 아니며, 상기 예에 제시되지 않은 다른 비대칭성 비가교형 메탈로센 화합물도 본 발명의 예에 포함될 수 있다.Metallocene compound represented by the formula (5) prepared by the method for preparing an asymmetric non-crosslinked metallocene compound according to the present invention ((Cp ^One ) (Cp ² M ^One X ₂ Non-limiting examples of) include (methylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (ethylcyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (normal propylcyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (isopropylcyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (normal butylcyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (isobutylcyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (tertiarybutylcyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (normalpentylcyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (isopentylcyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (cyclopentylcyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (normalhexylcyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (isohexylcyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (cyclohexylcyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (normalheptylcyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (isoheptylcyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (cycloheptylcyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (normaloctylcyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (isooctylcyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (cyclooctylcyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (normal nonylcyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (isononylcyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (cyclononylcyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (1-methyl, 3-normal butylcyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (Methylcyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (normal propylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (isopropylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (normal butylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (isobutylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (tertiarybutylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (normalpentylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (isopentylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (cyclopentylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (normalhexylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (isohexylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (cyclohexylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (normalheptylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (isoheptylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (cycloheptylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (normaloctylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (isooctylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (cyclooctylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (normal nonylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (isononylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (cyclononylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (1-methyl, 3-normal butylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (Ethylcyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, (Normal porphyll cyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (Normal propyl cyclopentadienyl) (ethylcyclopentadienyl) zirconium dichloride, (Normal propyl cyclopentadienyl) (isopropyl cyclopentadienyl) zirconium dichloride, (Normal propyl cyclopentadienyl) (normal butyl cyclopentadienyl) zirconium dichloride, (Normal propyl cyclopentadienyl) (isobutyl cyclopentadienyl) zirconium dichloride, (Normal propyl cyclopentadienyl) (tertiarybutylcyclopentadienyl) zirconium dichloride, (Normal propyl cyclopentadienyl) (normal pentyl cyclopentadienyl) zirconium dichloride, (Normal propyl cyclopentadienyl) (isopentylcyclopentadienyl) zirconium dichloride, (Normal propyl cyclopentadienyl) (cyclopentylcyclopentadienyl) zirconium dichloride, (Normal propyl cyclopentadienyl) (normal hexyl cyclopentadienyl) zirconium dichloride, (Normal propyl cyclopentadienyl) (isohexyl cyclopentadienyl) zirconium dichloride, (Normal propyl cyclopentadienyl) (cyclohexylcyclopentadienyl) zirconium dichloride, (Normal propyl cyclopentadienyl) (normal heptylcyclopentadienyl) zirconium dichloride, (Normal propylcyclopentadienyl) (isoheptylcyclopentadienyl) zirconium dichloride, (Normal propyl cyclopentadienyl) (cycloheptylcyclopentadienyl) zirconium dichloride, (Normal propyl cyclopentadienyl) (normal octylcyclopentadienyl) zirconium dichloride, (Normal propylcyclopentadienyl) (isooctylcyclopentadienyl) zirconium dichloride, (Normal propyl cyclopentadienyl) (cyclooctylcyclopentadienyl) zirconium dichloride, (Normal propyl cyclopentadienyl) (normal nonylcyclopentadienyl) zirconium dichloride, (Normal propylcyclopentadienyl) (isononylcyclopentadienyl) zirconium dichloride, (Normal propyl cyclopentadienyl) (cyclononyl cyclopentadienyl) zirconium dichloride, (Normal propyl cyclopentadienyl) (1-methyl, 3-normal butylcyclopentadienyl) zirconium dichloride, (Normal propyl cyclopentadienyl) (pentamethyl cyclopentadienyl) zirconium dichloride, (Normal propyl cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (Normal propyl cyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, (Isopropylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (Isopropylcyclopentadienyl) (ethylcyclopentadienyl) zirconium dichloride, (Isopropylcyclopentadienyl) (normal butylcyclopentadienyl) zirconium dichloride, (Isopropylcyclopentadienyl) (isobutylcyclopentadienyl) zirconium dichloride, (Isopropylcyclopentadienyl) (tertiarybutylcyclopentadienyl) zirconium dichloride, (Isopropylcyclopentadienyl) (normalpentylcyclopentadienyl) zirconium dichloride, (Isopropylcyclopentadienyl) (isopentylcyclopentadienyl) zirconium dichloride, (Isopropylcyclopentadienyl) (cyclopentylcyclopentadienyl) zirconium dichloride, (Isopropylcyclopentadienyl) (normalhexylcyclopentadienyl) zirconium dichloride, (Isopropylcyclopentadienyl) (isohexylcyclopentadienyl) zirconium dichloride, (Isopropylcyclopentadienyl) (cyclohexylcyclopentadienyl) zirconium dichloride, (Isopropylcyclopentadienyl) (normalheptylcyclopentadienyl) zirconium dichloride, (Isopropylcyclopentadienyl) (isoheptylcyclopentadienyl) zirconium dichloride, (Isopropylcyclopentadienyl) (cycloheptylcyclopentadienyl) zirconium dichloride, (Isopropylcyclopentadienyl) (normaloctylcyclopentadienyl) zirconium dichloride, (Isopropylcyclopentadienyl) (isooctylcyclopentadienyl) zirconium dichloride, (Isopropylcyclopentadienyl) (cyclooctylcyclopentadienyl) zirconium dichloride, (Isopropylcyclopentadienyl) (normal nonylcyclopentadienyl) zirconium dichloride, (Isopropylcyclopentadienyl) (isononylcyclopentadienyl) zirconium dichloride, (Isopropylcyclopentadienyl) (cyclononylcyclopentadienyl) zirconium dichloride, (Isopropylcyclopentadienyl) (1-methyl, 3-normal butylcyclopentadienyl) zirconium dichloride, (Isopropylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (Isopropylcyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (Isopropylcyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, (Normal butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (Normal butylcyclopentadienyl) (ethylcyclopentadienyl) zirconium dichloride, (Normal butyl cyclopentadienyl) (isobutyl cyclopentadienyl) zirconium dichloride, (Normal butylcyclopentadienyl) (tertiarybutylcyclopentadienyl) zirconium dichloride, (Normal butylcyclopentadienyl) (normal pentylcyclopentadienyl) zirconium dichloride, (Normal butylcyclopentadienyl) (isopentylcyclopentadienyl) zirconium dichloride, (Normal butylcyclopentadienyl) (cyclopentylcyclopentadienyl) zirconium dichloride, (Normal butylcyclopentadienyl) (normalhexylcyclopentadienyl) zirconium dichloride, (Normal butylcyclopentadienyl) (isohexylcyclopentadienyl) zirconium dichloride, (Normal butylcyclopentadienyl) (cyclohexylcyclopentadienyl) zirconium dichloride, (Normal butylcyclopentadienyl) (normalheptylcyclopentadienyl) zirconium dichloride, (Normal butylcyclopentadienyl) (isoheptylcyclopentadienyl) zirconium dichloride, (Normal butylcyclopentadienyl) (cycloheptylcyclopentadienyl) zirconium dichloride, (Normal butylcyclopentadienyl) (normaloctylcyclopentadienyl) zirconium dichloride, (Normal butylcyclopentadienyl) (isooctylcyclopentadienyl) zirconium dichloride, (Normal butylcyclopentadienyl) (cyclooctylcyclopentadienyl) zirconium dichloride, (Normal butylcyclopentadienyl) (normal nonylcyclopentadienyl) zirconium dichloride, (Normal butylcyclopentadienyl) (isononylcyclopentadienyl) zirconium dichloride, (Normal butylcyclopentadienyl) (cyclononylcyclopentadienyl) zirconium dichloride, (Normal butylcyclopentadienyl) (1-methyl, 3-normal butylcyclopentadienyl) zirconium dichloride, (Normal butylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (Normal butylcyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (Normal butylcyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, (Cyclopentylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (Cyclopentylcyclopentadienyl) (ethylcyclopentadienyl) zirconium dichloride, (Cyclopentylcyclopentadienyl) (isobutylcyclopentadienyl) zirconium dichloride, (Cyclopentylcyclopentadienyl) (tertiarybutylcyclopentadienyl) zirconium dichloride, (Cyclopentylcyclopentadienyl) (normalpentylcyclopentadienyl) zirconium dichloride, (Cyclopentylcyclopentadienyl) (isopentylcyclopentadienyl) zirconium dichloride, (Cyclopentylcyclopentadienyl) (normalhexylcyclopentadienyl) zirconium dichloride, (Cyclopentylcyclopentadienyl) (isohexylcyclopentadienyl) zirconium dichloride, (Cyclopentylcyclopentadienyl) (cyclohexylcyclopentadienyl) zirconium dichloride, (Cyclopentylcyclopentadienyl) (normalheptylcyclopentadienyl) zirconium dichloride, (Cyclopentylcyclopentadienyl) (isoheptylcyclopentadienyl) zirconium dichloride, (Cyclopentylcyclopentadienyl) (cycloheptylcyclopentadienyl) zirconium dichloride, (Cyclopentylcyclopentadienyl) (normaloctylcyclopentadienyl) zirconium dichloride, (Cyclopentylcyclopentadienyl) (isooctylcyclopentadienyl) zirconium dichloride, (Cyclopentylcyclopentadienyl) (cyclooctylcyclopentadienyl) zirconium dichloride, (Cyclopentylcyclopentadienyl) (normal nonylcyclopentadienyl) zirconium dichloride, (Cyclopentylcyclopentadienyl) (isononylcyclopentadienyl) zirconium dichloride, (Cyclopentylcyclopentadienyl) (cyclononylcyclopentadienyl) zirconium dichloride, (Cyclopentylcyclopentadienyl) (1-methyl, 3-normal butylcyclopentadienyl) zirconium dichloride, (Cyclopentylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (Cyclopentylcyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (Cyclopentylcyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, (1-methyl, 3-normal butylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (1-methyl, 3-normal butylcyclopentadienyl) (ethylcyclopentadienyl) zirconium dichloride, (1-methyl, 3-normal butylcyclopentadienyl) (isobutylcyclopentadienyl) zirconium dichloride, (1-methyl, 3-normal butylcyclopentadienyl) (tertiarybutylcyclopentadienyl) zirconium dichloride, (1-methyl, 3-normal butylcyclopentadienyl) (normal pentylcyclopentadienyl) zirconium dichloride, (1-methyl, 3-normal butylcyclopentadienyl) (isopentylcyclopentadienyl) zirconium dichloride, (1-methyl, 3-normal butylcyclopentadienyl) (normalhexylcyclopentadienyl) zirconium dichloride, (1-methyl, 3-normal butylcyclopentadienyl) (isohexylcyclopentadienyl) zirconium dichloride, (1-methyl, 3-normal butylcyclopentadienyl) (cyclohexylcyclopentadienyl) zirconium dichloride, (1-methyl, 3-normal butylcyclopentadienyl) (normalheptylcyclopentadienyl) zirconium dichloride, (1-methyl, 3-normal butylcyclopentadienyl) (isoheptylcyclopentadienyl) zirconium dichloride, (1-methyl, 3-normal butylcyclopentadienyl) (cycloheptylcyclopentadienyl) zirconium dichloride, (1-methyl, 3-normal butylcyclopentadienyl) (normaloctylcyclopentadienyl) zirconium dichloride, (1-methyl, 3-normal butylcyclopentadienyl) (isooctylcyclopentadienyl) zirconium dichloride, (1-methyl, 3-normal butylcyclopentadienyl) (cyclooctylcyclopentadienyl) zirconium dichloride, (1-methyl, 3-normal butylcyclopentadienyl) (normal nonylcyclopentadienyl) zirconium dichloride, (1-methyl, 3-normal butylcyclopentadienyl) (isononylcyclopentadienyl) zirconium dichloride, (1-methyl, 3-normal butylcyclopentadienyl) (cyclononylcyclopentadienyl) zirconium dichloride, (1-methyl, 3-normal butylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (1-methyl, 3-normal butylcyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (1-methyl, 3-normal butylcyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) (ethylcyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) (isobutylcyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) (tertiarybutylcyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) (normalpentylcyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) (isopentylcyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) (normalhexylcyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) (isohexylcyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) (cyclohexylcyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) (normalheptylcyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) (isoheptylcyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) (cycloheptylcyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) (normaloctylcyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) (isooctylcyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) (cyclooctylcyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) (normal nonylcyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) (isononylcyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) (cyclononylcyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (Pentamethylcyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, (Tetramethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (Tetramethylcyclopentadienyl) (ethylcyclopentadienyl) zirconium dichloride, (Tetramethylcyclopentadienyl) (isobutylcyclopentadienyl) zirconium dichloride, (Tetramethylcyclopentadienyl) (tertiarybutylcyclopentadienyl) zirconium dichloride, (Tetramethylcyclopentadienyl) (normalpentylcyclopentadienyl) zirconium dichloride, (Tetramethylcyclopentadienyl) (isopentylcyclopentadienyl) zirconium dichloride, (Tetramethylcyclopentadienyl) (normalhexylcyclopentadienyl) zirconium dichloride, (Tetramethylcyclopentadienyl) (isohexylcyclopentadienyl) zirconium dichloride, (Tetramethylcyclopentadienyl) (cyclohexylcyclopentadienyl) zirconium dichloride, (Tetramethylcyclopentadienyl) (normalheptylcyclopentadienyl) zirconium dichloride, (Tetramethylcyclopentadienyl) (isoheptylcyclopentadienyl) zirconium dichloride, (Tetramethylcyclopentadienyl) (cycloheptylcyclopentadienyl) zirconium dichloride, (Tetramethylcyclopentadienyl) (normaloctylcyclopentadienyl) zirconium dichloride, (Tetramethylcyclopentadienyl) (isooctylcyclopentadienyl) zirconium dichloride, (Tetramethylcyclopentadienyl) (cyclooctylcyclopentadienyl) zirconium dichloride, (Tetramethylcyclopentadienyl) (normal nonylcyclopentadienyl) zirconium dichloride, (Tetramethylcyclopentadienyl) (isononylcyclopentadienyl) zirconium dichloride, (Tetramethylcyclopentadienyl) (cyclononylcyclopentadienyl) zirconium dichloride, (Tetramethylcyclopentadienyl) (trimethylcyclopentadienyl) zirconium dichloride, (Trimethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (Trimethylcyclopentadienyl) (ethylcyclopentadienyl) zirconium dichloride, (Trimethylcyclopentadienyl) (isobutylcyclopentadienyl) zirconium dichloride, (Trimethylcyclopentadienyl) (tertiarybutylcyclopentadienyl) zirconium dichloride, (Trimethylcyclopentadienyl) (normalpentylcyclopentadienyl) zirconium dichloride, (Trimethylcyclopentadienyl) (isopentylcyclopentadienyl) zirconium dichloride, (Trimethylcyclopentadienyl) (normalhexylcyclopentadienyl) zirconium dichloride, (Trimethylcyclopentadienyl) (isohexylcyclopentadienyl) zirconium dichloride, (Trimethylcyclopentadienyl) (cyclohexylcyclopentadienyl) zirconium dichloride, (Trimethylcyclopentadienyl) (normalheptylcyclopentadienyl) zirconium dichloride, (Trimethylcyclopentadienyl) (isoheptylcyclopentadienyl) zirconium dichloride, (Trimethylcyclopentadienyl) (cycloheptylcyclopentadienyl) zirconium dichloride, (Trimethylcyclopentadienyl) (normaloctylcyclopentadienyl) zirconium dichloride, (Trimethylcyclopentadienyl) (isooctylcyclopentadienyl) zirconium dichloride, (Trimethylcyclopentadienyl) (cyclooctylcyclopentadienyl) zirconium dichloride, (Trimethylcyclopentadienyl) (normal nonylcyclopentadienyl) zirconium dichloride, (Trimethylcyclopentadienyl) (isononylcyclopentadienyl) zirconium dichloride, (Trimethylcyclopentadienyl) (cyclononylcyclopentadienyl) zirconium dichloride, (Indenyl) (cyclopentadienyl) zirconium dichloride, (Indenyl) (ethylcyclopentadienyl) zirconium dichloride, (Indenyl) (normal propyl cyclopentadienyl) zirconium dichloride, (Indenyl) (isopropylcyclopentadienyl) zirconium dichloride, (Indenyl) (normal butyl cyclopentadienyl) zirconium dichloride, (Indenyl) (isobutylcyclopentadienyl) zirconium dichloride, (Indenyl) (tertiarybutylcyclopentadienyl) zirconium dichloride, (Indenyl) (normalpentylcyclopentadienyl) zirconium dichloride, (Indenyl) (isopentylcyclopentadienyl) zirconium dichloride, (Indenyl) (cyclopentylcyclopentadienyl) zirconium dichloride, (Indenyl) (normal hexylcyclopentadienyl) zirconium dichloride, (Indenyl) (isohexylcyclopentadienyl) zirconium dichloride, (Indenyl) (cyclohexylcyclopentadienyl) zirconium dichloride, (Indenyl) (normalheptylcyclopentadienyl) zirconium dichloride, (Indenyl) (isoheptylcyclopentadienyl) zirconium dichloride, (Indenyl) (cycloheptylcyclopentadienyl) zirconium dichloride, (Indenyl) (normal octylcyclopentadienyl) zirconium dichloride, (Indenyl) (isooctylcyclopentadienyl) zirconium dichloride, (Indenyl) (cyclooctylcyclopentadienyl) zirconium dichloride, (Indenyl) (normal nonylcyclopentadienyl) zirconium dichloride, (Indenyl) (isononylcyclopentadienyl) zirconium dichloride, (Indenyl) (cyclononylcyclopentadienyl) zirconium dichloride, (Indenyl) (1-methyl, 3-normal butylcyclopentadienyl) zirconium dichloride, (Indenyl) (pentamethylcyclopentadienyl) zirconium dichloride, (Indenyl) (tetramethylcyclopentadienyl) zirconium dichloride, (Indenyl) (trimethylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (cyclopentadienyl) zirconium dichloride, (1-methylindenyl) (ethylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (normal propylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (isopropylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (normal butylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (isobutylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (tertiarybutylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (normalpentylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (isopentylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (cyclopentylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (normalhexylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (isohexylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (cyclohexylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (normalheptylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (isoheptylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (cycloheptylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (normaloctylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (isooctylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (cyclooctylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (normal nonylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (isononylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (cyclononylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (1-methyl, 3-normal butylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (pentamethylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (tetramethylcyclopentadienyl) zirconium dichloride, (1-methylindenyl) (trimethylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (cyclopentadienyl) zirconium dichloride, (2-methylindenyl) (ethylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (normal propylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (isopropylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (normal butylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (isobutylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (tertiarybutylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (normalpentylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (isopentylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (cyclopentylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (normalhexylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (isohexylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (cyclohexylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (normalheptylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (isoheptylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (cycloheptylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (normaloctylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (isooctylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (cyclooctylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (normal nonylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (isononylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (cyclononylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (1-methyl, 3-normal butylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (pentamethylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (tetramethylcyclopentadienyl) zirconium dichloride, (2-methylindenyl) (trimethylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (cyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (ethylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (normal propylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (isopropylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (normal butylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (isobutylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (tertiarybutylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (normalpentylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (isopentylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (cyclopentylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (normalhexylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (isohexylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (cyclohexylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (normalheptylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (isoheptylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (cycloheptylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (normaloctylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (isooctylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (cyclooctylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (normal nonylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (isononylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (cyclononylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (1-methyl, 3-normal butylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (pentamethylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (tetramethylcyclopentadienyl) zirconium dichloride, (1-ethylindenyl) (trimethylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (cyclopentadienyl) zirconium dichloride, (1-butylindenyl) (ethylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (normal propylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (isopropylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (normal butylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (isobutylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (tertiarybutylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (normalpentylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (isopentylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (cyclopentylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (normalhexylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (isohexylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (cyclohexylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (normalheptylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (isoheptylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (cycloheptylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (normaloctylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (isooctylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (cyclooctylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (normal nonylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (isononylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (cyclononylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (1-methyl, 3-normal butylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (pentamethylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (tetramethylcyclopentadienyl) zirconium dichloride, (1-butylindenyl) (trimethylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (cyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (ethylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (normal propylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (isopropylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (normal butylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (isobutylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (tertiarybutylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (normalpentylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (isopentylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (cyclopentylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (normalhexylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (isohexylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (cyclohexylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (normalheptylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (isoheptylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (cycloheptylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (normaloctylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (isooctylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (cyclooctylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (normal nonylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (isononylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (cyclononylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (1-methyl, 3-normal butylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (pentamethylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (tetramethylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (trimethylcyclopentadienyl) zirconium dichloride, (Tetrahydroindenyl) (indenyl) zirconium dichloride, (Tetrahydroindenyl) (1-methylindenyl) zirconium dichloride, (Tetrahydroindenyl) (2-methylindenyl) zirconium dichloride, (Tetrahydroindenyl) (1-ethylindenyl) zirconium dichloride, (Tetrahydroindenyl) (1-butylindenyl) zirconium dichloride, (Tetrahydroindenyl) (2-methylindenyl) zirconium dichloride, (Tetrahydroindenyl) (2-butylindenyl) zirconium dichloride, (Tetrahydroindenyl) (1-phenylindenyl) zirconium dichloride, (Tetrahydroindenyl) (2-phenylindenyl) zirconium dichloride, (Tetrahydroindenyl) (methylbenzoindenyl) zirconium dichloride, (Indenyl) (methylbenzoindenyl) zirconium dichloride, (Tetrahydroindenyl) (fluorenyl) zirconium dichloride, (Indenyl) (fluorenyl) zirconium dichloride, (Indenyl) (5, 6-cyclopenta-2-methyl-1-indenyl) zirconium dichloride, (2-methylindenyl) (5, 6-cyclopenta-2-methyl-1-indenyl) zirconium dichloride, (Tetrahydroindenyl) (5, 6-cyclopenta-2-methyl-1-indenyl) zirconium dichloride, (Indenyl) (2-methyl-4-phenylindenyl) zirconium dichloride, (2-methylindenyl) (2-methyl-4-phenylindenyl) zirconium dichloride, (2-ethylindenyl) (2-methyl-4-phenylindenyl) zirconium dichloride, (2-isobutylindenyl) (2-methyl-4-phenylindenyl) zirconium dichloride, (2-isopropylindenyl) (2-methyl-4-phenylindenyl) zirconium dichloride, (Tetrahydroindenyl) (2-methyl-4-phenylindenyl) zirconium dichloride, (Indenyl) (5, 6, 7, 8-tetrahydro-5, 5, 8, 8-tetramethyl-1H-benz [f] indenyl) zirconium dichloride, (2-methylindenyl) (5, 6, 7, 8-tetrahydro-5, 5, 8, 8-tetramethyl-1H-benz [f] indenyl) zirconium dichloride, (Tetrahydroindenyl) (5, 6, 7, 8-tetrahydro-5, 5, 8, 8-tetramethyl-1H-benz [f] indenyl) zirconium dichloride, (Indenyl) (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride, (2-methylindenyl) (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride, (Tetrahydroindenyl) (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride, (Indenyl) (2-methyl-4-isopropylindenyl) zirconium dichloride, (2-methylindenyl) (2-methyl-4-isopropylinyl) zirconium dichloride, (Tetrahydroindenyl) (2-methyl-4-isopropylindenyl) zirconium dichloride, Similar compounds thereof and the like can be exemplified, Titanium instead of zirconium of the compound, Metallocene compounds containing transition metals, such as hafnium, can be illustrated. The asymmetric uncrosslinked metallocene compound according to the present invention is not limited to the examples given above, and other asymmetric noncrosslinked metallocene compounds not shown in the above examples may also be included in the examples of the present invention.

본 발명에 의해 제조된 비대칭성 비가교형 메탈로센 화합물은 2종 이상 혼합하거나 단독으로 사용될 수 있으며, 적절한 활성체(activator)와 함께 올레핀 단량체의 중합 촉매로서 사용된다.　또한, 필요에 따라서 상기 메탈로센 화합물 및/또는 활성체를 고체 담체에 지지시켜 고체 담지 촉매로 사용할 수도 있다.　상기 활성체의 예로는 메틸알루미녹산(MAO), 변형된(modified) 메틸알루미녹산(MMAO), 에틸알루미녹산, 이소부틸알루미녹산, 부틸알루미녹산, 이들의 혼합물 등을 사용할 수 있으며,　트리(부틸)암모늄 테트라(펜타플루오로페닐)보론, N,N-디메틸아닐리늄 테트라(펜타플루오로페닐)보론 등과 같은 불소로 치환된 방향족 보론계의 이온형 화합물, 또는 N,N-디메틸아닐리늄 몬트모릴로나이트(N,N-dimethylanilinium montmorillonite), N,N-디메틸아닐리늄 헥토라이트(N,N-dimethylanilinium hectorite) 등과 같은 개질된 클레이 등도 상기 활성제로서 사용할 수 있다.The asymmetric non-crosslinked metallocene compound produced by the present invention may be used alone or in combination of two or more, and is used as a polymerization catalyst of an olefin monomer with a suitable activator. If necessary, the metallocene compound and / or the activator may be supported on a solid carrier and used as a solid supported catalyst. Examples of the active agent may include methyl aluminoxane (MAO), modified methyl aluminoxane (MMAO), ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, mixtures thereof, and the like. Fluorine-substituted ionic compounds such as ammonium tetra (pentafluorophenyl) boron, N, N-dimethylanilinium tetra (pentafluorophenyl) boron, or N, N-dimethylanilinium montmo Modified clays such as N, N-dimethylanilinium montmorillonite, N, N-dimethylanilinium hectorite, and the like can also be used as the active agent.

상기 메틸알루미녹산(MAO) 또는 변형된 메틸알루미녹산(MMAO) 활성체로는 상업적으로 판매되는 어떠한 알루미녹산도 사용할 수 있으며, 트리알킬알루미늄에 적량의 물을 첨가하거나, 물을 포함하는 탄화수소 화합물 또는 무기수화물염과 트리알킬알루미늄을 반응시키는 등 공지된 방법으로 제조하여 사용할 수도 있다.　상기 알루미녹산은 일반적으로 하기 화학식 6 및 7에 각각 나타낸 바와 같은 선형과 원형 알루미녹산이 혼합물의 형태로 얻어지며, 본 발명에서는 이와 같은 선형 또는 원형알루미녹산을 단독으로 또는 혼합하여 사용할 수 있다.　이와 같은 알루미녹산은 여러 가지 형태의 탄화수소 용액상태로 시판되고 있는데, 그 중에서 방향족 탄화수소 용액 알루미녹산을 사용하는 것이 바람직하며, 더욱 바람직하게는 톨루엔에 용해된 알루미녹산 용액을 사용하는 것이 좋다.As the methyl aluminoxane (MAO) or modified methyl aluminoxane (MMAO) activator any commercially available aluminoxane may be used, and an appropriate amount of water is added to trialkylaluminum, or a hydrocarbon compound or inorganic containing water. It can also be manufactured and used by a well-known method, such as making a hydrate salt and a trialkyl aluminum react. The aluminoxane is generally obtained in the form of a mixture of linear and circular aluminoxanes as shown in formulas (6) and (7), respectively. In the present invention, such linear or circular aluminoxanes may be used alone or in combination. Such aluminoxanes are commercially available in various forms of hydrocarbon solution. Among them, aromatic hydrocarbon solution aluminoxane is preferably used, and more preferably, aluminoxane solution dissolved in toluene.

[화학식 6] [Chemical Formula 6]

[화학식 7] [Formula 7]

상기 화학식 6 및 7에서, R′은 하이드로카빌(hydrocarbyl) 라디칼로서, 바람직하게는 1 내지 10의 탄소 원자로 이루어진 선형 또는 분지형 알킬 라디칼, 더욱 바람직하게는 메틸기이고, x는 1 내지 50의 정수, 바람직하게는 10 내지 40의 정수이고, y는 3 내지 50의 정수, 바람직하게는 10 내지 40의 정수이다.
In Formulas 6 and 7, R 'is a hydrocarbyl radical, preferably a linear or branched alkyl radical consisting of 1 to 10 carbon atoms, more preferably a methyl group, x is an integer of 1 to 50, Preferably it is an integer of 10-40, y is an integer of 3-50, Preferably it is an integer of 10-40.

본 발명에 의해 제조된 메탈로센 화합물과 함께 사용되는 활성체의 양은 넓은 범위에서 변화시킬 수 있는데, 메탈로센 화합물의 전이금속에 대한 알루미녹산의 알루미늄의 몰비([알루미늄]:[전이금속])는 1:1 내지 100,000:1 범위에서 선택될 수 있으며, 바람직하게는 5:1 내지 15,000:1의 몰비로 사용할 수 있다.
The amount of the active agent used with the metallocene compound prepared by the present invention can be varied within a wide range, where the molar ratio of aluminum of aluminoxane to the transition metal of the metallocene compound ([aluminum]: [transition metal] ) May be selected in the range of 1: 1 to 100,000: 1, preferably in a molar ratio of 5: 1 to 15,000: 1.

본 발명에 의해 제조된 메탈로센 촉매 조성물은 메탈로센 화합물과 활성체가 탄화수소 용매 등에 균일하게 용해된 용액 상태에서 폴리올레핀의 중합에 사용될 수도 있으며, 메탈로센 화합물 및/또는 활성체가 무기산화물 담체(예; 실리카, 알루미나, 실리카-알루미나 혼합물 등)에 담지된 형태 또는 그들의 불용성의 입자 형태로서 사용될 수도 있다.　따라서, 본 발명의 메탈로센 화합물 및 활성체로 이루어진 올레핀 중합용 촉매 조성물은 올레핀의 용액, 슬러리 또는 기상 중합에도 모두 적용될 수 있으며, 각각의 중합 반응 조건은 사용하는 메탈로센 화합물의 종류, 메탈로센/활성체로 이루어진 촉매의 상태(균일상 또는 불균일상(담지형)), 중합 방법(용액중합, 슬러리중합, 기상중합), 얻고자 하는 중합결과 또는 중합체의 형태에 따라 다양하게 변형하여 설정할 수 있다.The metallocene catalyst composition prepared according to the present invention may be used for polymerization of polyolefin in a solution state in which a metallocene compound and an activator are uniformly dissolved in a hydrocarbon solvent and the like, and the metallocene compound and / or the activator may be an inorganic oxide carrier ( (For example, silica, alumina, silica-alumina mixtures, etc.) or as insoluble particle forms thereof. Therefore, the catalyst composition for olefin polymerization composed of the metallocene compound and the active agent of the present invention can be applied to both solution, slurry or gas phase polymerization of olefin, and each polymerization reaction condition is a kind of metallocene compound to be used, metallo It can be set in various ways depending on the state of the catalyst composed of sen / active material (uniform or heterogeneous phase (support type)), polymerization method (solution polymerization, slurry polymerization, gas phase polymerization), desired polymerization result or polymer type. have.

본 발명에 의해 제조된 메탈로센 화합물은 알루미녹산 활성체와 함께 여러 가지 다른 올레핀의 존재 하에서 에틸렌을 중합할 수 있는데, 상기 다른 올레핀으로는 탄소수 2 내지 12, 바람직하게는 3 내지 10의 α-올레핀 탄화수소, 예를 들어 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, 이들의 유도체, 이들 올레핀의 혼합물 등을 포함한다.The metallocene compound prepared according to the present invention can polymerize ethylene together with an aluminoxane activator in the presence of various other olefins. The other olefins include α- of 2 to 12 carbon atoms, preferably 3 to 10 carbon atoms. Olefin hydrocarbons such as 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, derivatives thereof, mixtures of these olefins, and the like do.

상기 올레핀 중합 반응은 액상 또는 기상 매질(diluents)의 존재 하에 수행될 수 있으며, 상기 매질은 촉매계에 악영향을 주지 않는 비반응성 물질이어야 하며, 예를 들면, 프로판, 부탄, 이소부탄, 펜탄, 헥산, 헵탄, 옥탄, 싸이클로헥산, 메틸싸이클로헥산, 톨루엔, 크실렌, 이들의 유도체, 이들의 혼합물 등을 사용할 수 있으며, 반응 매질 내에 존재하는 촉매의 피독물질은 올레핀을 중합하기 전에 제거하는 것이 바람직하다.The olefin polymerization reaction can be carried out in the presence of liquid or gaseous media (diluents), the media must be a non-reactive material that does not adversely affect the catalyst system, for example, propane, butane, isobutane, pentane, hexane, Heptane, octane, cyclohexane, methylcyclohexane, toluene, xylene, derivatives thereof, mixtures thereof, and the like can be used, and the poisoning material of the catalyst present in the reaction medium is preferably removed before the olefin is polymerized.

상기 올레핀 중합반응 온도는 반응물질, 반응 조건 등에 따라 변할 수 있으며, 통상적인 중합 온도는 약 20 내지 200℃이고, 중합 압력은 10 내지 7000 psig이다. 본 발명의 중합용 촉매를 사용하여 제조되는 중합체의 분자량은 중합온도를 변화시키거나, 반응기 내에 수소를 주입하는 방법으로 조절할 수 있다.
The olefin polymerization temperature may vary depending on reactants, reaction conditions, and the like, and a typical polymerization temperature is about 20 to 200 ° C., and a polymerization pressure is 10 to 7000 psig. The molecular weight of the polymer produced using the polymerization catalyst of the present invention can be controlled by changing the polymerization temperature or by injecting hydrogen into the reactor.

이하, 구체적인 실시예를 통하여 본 발명을 더욱 상세히 설명한다. 하기 실시예는 본 발명을 예시하기 위한 것으로서, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to specific examples. The following examples illustrate the present invention and are not intended to limit the scope of the present invention.

하기 실시예에서, 본 발명의 메탈로센 화합물은 공기와 수분이 완전하게 차단된 쉬렌크(Schlenk) 기법 하에서 제조하였고, 불활성기체로서 정제 건조된 질소를 사용하였다.　또한, 용매는 불활성 질소 분위기 하에서 대부분 나트륨금속 존재 하에 건조하고, 디클로로메탄의 경우는 칼슘하이드라이드 존재 하에 건조하여 사용하였다.　핵자기분광분석용 중수소화 용매(Deuterated solvent)는 분자체(Molecular sieve)를 넣어 보관하여 사용하였다.
In the following examples, the metallocene compound of the present invention was prepared under Schlenk technique in which air and moisture were completely blocked, and purified dried nitrogen was used as an inert gas. In addition, the solvent was mostly dried in the presence of sodium metal in an inert nitrogen atmosphere, and dichloromethane was dried in the presence of calcium hydride. Deuterated solvent for nuclear magnetic spectroscopic analysis was used by storing a molecular sieve.

[실시예 1] ( 노말부틸싸이클로펜타디에닐 )( 테트라메틸싸이클로펜타디에닐 )지르코늄 디클로라이드의 제조 Example 1 Preparation of (n-butyl-cyclo-pentadienyl) (tetramethyl-cyclo-pentadienyl) zirconium dichloride

질소 분위기 하에서, 500ml 용량의 둥근 플라스크에 비스(노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드 2.8g(6.94mmol), 지르코늄 클로라이드 1.7g(7.29mmol) 및 톨루엔 100ml을 넣은 다음, 교반하면서 90℃에서 24시간 동안 반응시켰다. 반응이 완료된 후, 반응 생성물을 여과하여 여과액을 수집하였다. 테트라메틸싸이클로펜타디에닐리튬 1.78g(13.9mmol)을 500ml 플라스크에 넣은 다음, 상기 여과액을 넣고, 혼합용액을 교반하면서, 80~90℃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, 3.71g의 (테트라메틸싸이클로펜타디에닐)(노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드를 얻었다{수율: 64%, 1H NMR(500MHz,CDCl₃) 분석 결과: 0.86-0.89(t, 3, CH3), 1.28-1.35(m, 2, -CH2-), 1.47-1.53(m, 2, -CH2-), 1.93-2.0(s, 12, 4CH3 of Me4Cp), 2.56-2.6(t, 2, -CH2-), 5.89(s, 1, C5H-Me4), 6.1(m, 4, -C5H4)}.
Under a nitrogen atmosphere, 2.8 g (6.94 mmol) of bis (normalbutylcyclopentadienyl) zirconium dichloride, 1.7 g (7.29 mmol) of zirconium chloride and 100 ml of toluene were added to a 500 ml round flask, followed by stirring at 24 DEG C. at 90 ° C. The reaction was carried out for a time. After the reaction was completed, the reaction product was filtered to collect the filtrate. 1.78 g (13.9 mmol) of tetramethylcyclopentadienyl lithium was placed in a 500 ml flask, and the filtrate was added thereto. The mixture was stirred at 80-90 ° 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 3.71 g of (tetramethylcyclopentadienyl) (normalbutylcyclopentadienyl) zirconium dichloride. Yield: 64%, 1 H NMR (500 MHz, CDCl ₃ ) Analysis Result: 0.86-0.89 (t, 3, CH 3), 1.28-1.35 (m, 2, -CH 2-), 1.47-1.53 (m, 2, -CH2-), 1.93-2.0 (s, 12, 4CH3 of Me4Cp), 2.56-2.6 (t, 2, -CH2-), 5.89 (s, 1, C5 H- Me4), 6.1 (m, 4,- C5 H 4)}.

[실시예 2] (1- 메틸 ,3- 노말부틸싸이클로펜타디에닐 )( 테트라메틸싸이클로펜타디에닐 )지르코늄 디클로라이드의 제조 Example 2 Preparation of (1-methyl, 3-n-butyl-cyclo-pentadienyl) (tetramethyl-cyclo-pentadienyl) zirconium dichloride

질소 분위기 하에서, 500ml 용량의 둥근 플라스크에 비스(1-메틸,3-노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드 1.5g(3.468mmol), 지르코늄 클로라이드 0.9g(3.814mmol) 및 톨루엔 100ml을 넣은 다음, 교반하면서 90℃에서 24시간 동안 반응시켰다. 반응이 완료된 후, 반응 생성물을 여과하여 여과액을 수집하였다. 테트라메틸싸이클로펜타디에닐리튬 0.93g(7.28mmol)을 500ml 플라스크에 넣은 다음, 상기 여과액을 넣고, 혼합용액을 교반하면서, 80~90℃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, 1.955g의 (1-메틸,3-노말부틸싸이클로펜타디에닐)(테트라메틸싸이클로펜타디에닐)지르코늄 디클로라이드를 얻었다{수율: 68%, 1H NMR(500MHz,CDCl₃) 분석 결과: 0.87-0.92(t, 3, CH3), 1.30-1.35(m, 2, -CH2-), 1.45-1.51(m, 2, -CH2-), 1.99-2.1(s, 12, 4CH3 of Me4Cp), 2.16(s, 3, CH3- of CH3BuC5H3), 2.38-2.6(m, 2, -CH2-), 5.75(s, 1, H- of MeBuC5H3), 5.79(s, 1, H- of MeBuC5H3), 5.9(s, 1, H-of C5H-Me4), 6.1(s, 1, H- of MeBuC5H3)}.
Under a nitrogen atmosphere, 1.5 g (3.468 mmol) of bis (1-methyl, 3-normalbutylcyclopentadienyl) zirconium dichloride, 0.9 g (3.814 mmol) of zirconium chloride and 100 ml of toluene were placed in a 500 ml round flask. The reaction was carried out at 90 ° C. for 24 hours while stirring. After the reaction was completed, the reaction product was filtered to collect the filtrate. 0.93 g (7.28 mmol) of tetramethylcyclopentadienyllithium was added to a 500 ml flask, the filtrate was added, and the mixed solution was stirred at 80 to 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 1.955 g of (1-methyl, 3-normalbutylcyclopentadienyl) (tetramethylcyclopentadiene). Nile) zirconium dichloride was obtained {yield: 68%, 1H NMR (500MHz, CDCl ₃ ) Analysis: 0.87-0.92 (t, 3, CH3), 1.30-1.35 (m, 2, -CH2-), 1.45- 1.51 (m, 2, -CH2-), 1.99-2.1 (s, 12, 4CH3 of Me4Cp), 2.16 (s, 3, CH3- of C H3 BuC5H3), 2.38-2.6 (m, 2, -CH2-) , 5.75 (s, 1, H- of MeBuC5 H3 ), 5.79 (s, 1, H- of MeBuC5 H3 ), 5.9 (s, 1, H-of C5 H -Me4), 6.1 (s, 1, H- of MeBuC5 H3 )}.

[실시예 3] (1- 메틸 ,3- 노말부틸싸이클로펜타디에닐 )( 인데닐 )지르코늄 디클로라이드의 제조 [Example 3] (1-methyl, 3-n-butyl-cyclo-pentadienyl) (indenyl) zirconium dichloride Preparation of

질소 분위기 하에서, 500ml 용량의 둥근 플라스크에 비스(1-메틸,3-노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드 4.0g(9.247mmol), 지르코늄 클로라이드 2.37g(10.172mmol) 및 톨루엔 100ml을 넣은 다음, 교반하면서 90℃에서 24시간 동안 반응시켰다. 반응이 완료된 후, 반응 생성물을 여과하여 여과액을 수집하였다. 인데닐리튬 2.37g(19.42mmol)을 500ml 플라스크에 넣은 다음, 상기 여과액을 넣고, 혼합용액을 교반하면서, 80~90℃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, 4.8g의 (1-메틸,3-노말부틸싸이클로펜타디에닐)(인데닐)지르코늄 디클로라이드를 얻었다{수율: 63%, 1H NMR(500MHz,CDCl₃) 분석 결과: 0.87-0.91(t, 3, CH3), 1.27-1.32(m, 2, -CH2-), 1.39-1.45(m, 2, -CH2-), 2.11(s, 3, CH3- of CH3BuC5H3), 2.36-2.6(m, 2, -CH2-), 5.53(s, 1, H- of MeBuC5H3), 5.61(s, 1, H- of MeBuC5H3), 5.95(s, 1, H- of MeBuC5H3), 6.468(s, 2, C9H7), 6.82(d, 1, C9H7), 7.26-7.30(m, 2, C9H7), 7.64-7.66(m, 2, C9H7)}.
Under a nitrogen atmosphere, 4.0 g (9.247 mmol) of bis (1-methyl, 3-normalbutylcyclopentadienyl) zirconium dichloride, 2.37 g (10.172 mmol) of zirconium chloride and 100 ml of toluene were placed in a 500 ml round flask. The reaction was carried out at 90 ° C. for 24 hours while stirring. After the reaction was completed, the reaction product was filtered to collect the filtrate. 2.37 g (19.42 mmol) of indenylithium was placed in a 500 ml flask, the filtrate was added, and the mixed solution was stirred at 80 to 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 4.8 g of (1-methyl, 3-normalbutylcyclopentadienyl) (indenyl) zirconium di Chloride was obtained {yield: 63%, 1 H NMR (500 MHz, CDCl ₃ ) Assay: 0.87-0.91 (t, 3, CH 3), 1.27-1.32 (m, 2, -CH 2-), 1.39-1.45 (m, 2, -CH2-), 2.11 (s, 3, CH3- of C H3 BuC5H3), 2.36-2.6 (m, 2, -CH2-), 5.53 (s, 1, H- of MeBuC5 H3 ), 5.61 (s , 1, H- of MeBuC5 H3 ), 5.95 (s, 1, H- of MeBuC5 H3 ), 6.468 (s, 2, C9H7), 6.82 (d, 1, C9H7), 7.26-7.30 (m, 2, C9H7 ), 7.64-7.66 (m, 2, C9H7)}.

[실시예 4] ( 노말부틸싸이클로펜타디에닐 )(1- 노말부틸인데닐 )지르코늄 디클로라이드의 제조 Example 4 (n-butyl-cyclo-pentadienyl) (1-inde n-butyl-indenyl) zirconium dichloride Preparation of

질소 분위기 하에서, 500ml 용량의 둥근 플라스크에 비스(노말부틸싸이클로펜타디에닐)지르코늄 디클로라이드 2.08g(5.16mmol), 지르코늄 클로라이드 1.326g(5.69mmol) 및 톨루엔 50ml을 넣은 다음, 교반하면서 90℃에서 24시간 동안 반응시켰다. 반응이 완료된 후, 반응 생성물을 여과하여 여과액을 수집하였다. 1-노말부틸인덴리튬 1.84g(10.32mmol)을 500ml 플라스크에 넣은 다음, 상기 여과액을 넣고, 혼합용액을 교반하면서, 80~90℃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, 2.56g의 (노말부틸싸이클로펜타디에닐)(1-노말부틸인데닐)지르코늄 디클로라이드를 얻었다{수율: 55%, 1H NMR(500MHz,CDCl₃) 분석 결과: 0.91-0.94(t, 3, CH3), 0.94-0.96(t, 3, CH3), 1.26-1.33(m, 2, -CH2-), 1.35-1.43(m, 2, -CH2-), 1.43-1.49(m, 2, -CH2-), 1.59-1.65(m, 2, -CH2-), 2.48-2.53(t, 2, -CH2-), 2.85-3.02(t, 2, -CH2-), 5.70-5.9(m, 4, -C5H4), 6.4(d, 2, -C9H6), 6.65(d, 2, -C9H6), 7.22-7.28 (m, 2, C9H6), 7.60-7.64 (m, 2, C9H6)}.
Under a nitrogen atmosphere, 2.08 g (5.16 mmol) of bis (normalbutylcyclopentadienyl) zirconium dichloride, 1.326 g (5.69 mmol) of zirconium chloride and 50 ml of toluene were placed in a 500 ml round flask, followed by stirring at 24 DEG C. at 90 ° C. The reaction was carried out for a time. After the reaction was completed, the reaction product was filtered to collect the filtrate. 1.84 g (10.32 mmol) of 1-normal butyl indene lithium was placed in a 500 ml flask, the filtrate was added, and the mixed solution was stirred at 80 to 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 2.56 g of (normal butylcyclopentadienyl) (1-normal butylindenyl) zirconium dichloride. Yield: 55%, 1 H NMR (500 MHz, CDCl ₃ ) Analysis Results: 0.91-0.94 (t, 3, CH3), 0.94-0.96 (t, 3, CH3), 1.26-1.33 (m, 2, -CH2) 1.35-1.43 (m, 2, -CH2-), 1.43-1.49 (m, 2, -CH2-), 1.59-1.65 (m, 2, -CH2-), 2.48-2.53 (t, 2, -CH2-), 2.85-3.02 (t, 2, -CH2-), 5.70-5.9 (m, 4, -C5H4), 6.4 (d, 2, -C9H6), 6.65 (d, 2, -C9H6), 7.22-7.28 (m, 2, C9H6), 7.60-7.64 (m, 2, C9H6)}.

[실시예 5] ( 테트라하이드로인데닐 )( 인데닐 )지르코늄 디클로라이드의 제조 [Example 5] (inde tetrahydroindenyl) (inde indenyl) zirconium dichloride Preparation of

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. 인데닐리튬 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, 1.52g의 (테트라하이드로인데닐)(인데닐)지르코늄 디클로라이드를 얻었다{수율: 72%, 1H NMR(500MHz,CDCl₃) 분석 결과: 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)}.
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 placed in 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. 0.66 g (5.406 mmol) of indenylithium was placed in a 500 ml flask, and the filtrate was added thereto, and the mixed solution was stirred for 18 hours at 90 ° C. 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 of (tetrahydroindenyl) (indenyl) zirconium dichloride {yield: 72% , 1 H NMR (500 MHz, CDCl ₃ ) Assay: 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)}.

[실시예 6] ( 테트라하이드로인데닐 )(2- 메틸인데닐 )지르코늄 디클로라이드의 제조 Example 6 (inde tetrahydroindenyl) (inde 2-methyl-indenyl) zirconium dichloride Preparation of

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-메틸인데닐리튬 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 3.45g의 (테트라하이드로인데닐)(2-메틸인데닐)지르코늄 디클로라이드를 얻었다{수율 52%, 1H NMR(500MHz,CDCl₃) 분석 결과: 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)}.
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-methylindenylithium 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 with stirring. 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 yield 3.45 g of (tetrahydroindenyl) (2-methylindenyl) zirconium dichloride {yield 52 %, 1 H NMR (500 MHz, CDCl ₃ ) Assay: 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)}.

[실시예 7] ( 테트라하이드로인데닐 )(1- 노말부틸인데닐 )지르코늄 디클로라이드의 제조 Example 7 (inde tetrahydroindenyl) (1-inde n-butyl-indenyl) zirconium dichloride Preparation of

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-노말부틸인데닐리튬 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, 3.13g의 (테트라하이드로인데닐)(1-노말부틸인데닐)지르코늄 디클로라이드를 얻었다{수율: 43%, 1H NMR(500MHz,CDCl₃) 분석 결과: 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)}.
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 indenylithium was placed in a 500 ml flask, and then the filtrate was added 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 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 3.13 g of (tetrahydroindenyl) (1-normalbutylinyl) zirconium dichloride { Yield: 43%, 1 H NMR (500 MHz, CDCl ₃ ) Assay: 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)}.

[실시예 8] ( 테트라하이드로인데닐 )(1- 에틸인데닐 )지르코늄 디클로라이드의 제조 [Example 8] (tetrahydro-inde carbonyl) (inde 1-ethyl-indenyl) zirconium dichloride Preparation of

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, 3.58g의 (테트라하이드로인데닐)(1-에틸인데닐)지르코늄 디클로라이드를 얻었다{수율 53%, 1H NMR(500MHz,CDCl₃) 분석 결과: 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)}.
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 yield 3.58 g of (tetrahydroindenyl) (1-ethylindenyl) zirconium dichloride {yield 53%, 1 H NMR (500 MHz, CDCl ₃ ) Assay: 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)}.

[실시예 9] ( 테트라하이드로인데닐 )(2- 페닐인데닐 )지르코늄 디클로라이드의 제조 [Example 9] (inde tetrahydroindenyl) zirconium dichloride Preparation of (2-phenyl-inde carbonyl)

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 0.9g의 (테트라하이드로인데닐)(2-페닐인데닐)지르코늄 디클로라이드를 얻었다{수율: 39%, 1H NMR(500MHz,CDCl₃) 분석 결과: 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)}.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 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 yield 0.9 g of (tetrahydroindenyl) (2-phenylindenyl) zirconium dichloride {yield: 39%, 1 H NMR (500 MHz, CDCl ₃ ) Assay: 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)}.

Claims

Preparing a reaction mixture by reacting the compound represented by Formula 1 with the compound represented by Formula 2 in the presence of an organic solvent;
Filtering the reaction mixture to obtain a filtrate comprising a compound represented by Formula 3 below; And
A method for preparing an asymmetric non-crosslinked metallocene compound comprising the step of preparing a metallocene compound represented by Chemical Formula 5 by reacting the compound represented by Chemical Formula 3 with the compound represented by Chemical Formula 4 of the filtrate: .
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In Chemical Formulas 1 to 5, Cp ¹ And Cp ² are each independently a radical having a cyclopentadienyl nucleus having a substituted or unsubstituted hydrocarbyl radical having 1 to 30 carbon atoms, and Cp ¹ And Cp ² has a different structure, M ¹ is titanium, zirconium or hafnium, X is a halogen atom, M ² is an element of group 1 or 2 of the periodic table, R is a hydrocarbyl radical of 1 to 10 carbon atoms , m is an integer of 1 or 2, n is an integer of 0 or 1, m + n is equal to the valence of M ² .

The method of claim 1, wherein the Cp ¹ or Cp ² is a tetrahydroindenyl radical having a substituted or unsubstituted hydrocarbyl radical having 1 to 10 carbon atoms.

The method of claim 1, wherein M ¹ is zirconium.

The method of claim 1, wherein X is a chlorine atom.

The method of claim 1, wherein M ² is lithium, sodium, potassium or magnesium.

The equivalent ratio of the compound represented by Formula 2 to the compound represented by Formula 1 is 0.9 to 1.1, and the equivalent ratio of the compound represented by Formula 4 to the compound represented by Formula 1 is 1.8. To 2.2, which is a method for producing an asymmetric non-crosslinked metallocene compound.

The method of claim 1, wherein the organic solvent is toluene or methylene chloride.

The reaction temperature of claim 1, wherein the reaction of the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 and the reaction of the compound represented by Chemical Formula 3 and the compound represented by Chemical Formula 4 is 25 to 100 ° C. 7. That is, a method for producing an asymmetric non-crosslinked metallocene compound.

According to claim 1, The reaction time of the reaction of the compound represented by Formula 1 and the compound represented by Formula 2 and the reaction of the compound represented by Formula 3 and the compound represented by Formula 4 is 8 to 24 hours That is, a method for producing an asymmetric non-crosslinked metallocene compound.

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