KR101618460B1 - Supported catalyst for olefin polymerization and process for preparing polyolefin using the same - Google Patents

Abstract

The present invention relates to a supported catalyst for polymerizing olefin, and to a method for producing an olefin polymer using the same. According to the present invention, the supported catalyst is produced by supporting, on a carrier, two certain kinds of metallocene catalyst compound along with a co-catalyst compound. More specifically, the purpose of the present invention is to provide a supported catalyst for polymerizing olefin, wherein the supported catalyst has high catalytic activity and is capable of efficiently regulating distribution of molecular weight of the olefin polymer.

Description

Translated fromKorean

올레핀 중합용 담지 촉매 및 이를 이용하여 제조된 올레핀 중합체의 제조방법{SUPPORTED CATALYST FOR OLEFIN POLYMERIZATION AND PROCESS FOR PREPARING POLYOLEFIN USING THE SAME}TECHNICAL FIELD [0001] The present invention relates to a supported catalyst for olefin polymerization, and a process for producing the olefin polymer using the same. BACKGROUND ART < RTI ID = 0.0 >

본 발명은 올레핀 중합용 담지 촉매 및 이를 사용한 올레핀 중합체의 제조방법에 관한 것이다.The present invention relates to a supported catalyst for olefin polymerization and a process for producing an olefin polymer using the same.

종래에는 올레핀 중합체의 제조를 위해, 티타늄 또는 바나듐 화합물의 주촉매 성분과, 알킬알루미늄 화합물의 조촉매 성분으로 이루어진 지글러-나타 촉매가 사용되었다. 그런데, 지글러-나타 촉매는 올레핀 중합체 제조시 고활성을 나타내지만, 불균일한 촉매 활성점으로 인해서 특정 분자량 분포를 갖는 중합체를 얻기 어려웠다.Conventionally, a Ziegler-Natta catalyst composed of a main catalyst component of titanium or a vanadium compound and a cocatalyst component of an alkyl aluminum compound was used for the production of the olefin polymer. However, although the Ziegler-Natta catalyst exhibits high activity when producing the olefin polymer, it is difficult to obtain a polymer having a specific molecular weight distribution due to non-uniform catalytic activity sites.

이를 개선하기 위해, 두 개의 시클로펜타디에닐기(cyclopentadienyl group)-함유 리간드 사이에 Ti, Zr, Hf 등과 같은 전이금속이 개재(介在)된 형태로 결합하고 있는 메탈로센 촉매가 개발되었다. 상기 메탈로센 촉매의 예로는 비스(인데닐)지르코늄디클로라이드, 라세믹-에틸렌비스(테트라하이드로인데닐)지르코늄디클로라이드 등이 있다. 이러한 메탈로센 촉매는 촉매 활성점이 균일하기 때문에, 지글러-나타 촉매를 이용한 경우보다 분자량 분포가 좁고 조성분포가 균일한 중합체를 제조할 수 있었다. 그러나, 중합체는 좁은 분자량 분포로 인해서 성형성이 낮았다.To improve this, a metallocene catalyst has been developed in which a transition metal such as Ti, Zr, Hf or the like is interposed between two cyclopentadienyl group-containing ligands in a form interposed therebetween. Examples of the metallocene catalyst include bis (indenyl) zirconium dichloride, racemic-ethylene bis (tetrahydroindenyl) zirconium dichloride, and the like. Since the metallocene catalysts have uniform catalytic active sites, a polymer having a narrow molecular weight distribution and uniform composition distribution can be produced as compared with the case of using a Ziegler-Natta catalyst. However, the polymer had poor moldability due to its narrow molecular weight distribution.

게다가, 올레핀 중합체는 다양한 분야에 적용됨에 따라 기계적 물성의 저하 없이 다양한 가공 조건을 만족시켜야 한다. 따라서, 종래에는 분자량 분포를 다양하게 조절하기 위해, 중합 조건을 달리하는 반응기를 다단계로 이용하여 분자량 분포를 조절하거나, 또는 다른 분자량을 지닌 고분자를 블렌딩하였다. 그러나, 종래 방법은 효율성 및 경제성 측면에서 문제가 있었으며, 특히 고분자의 블렌딩 방법의 경우 블렌딩 추가 공정과 고분자간의 용융 점도 차이로 인해 가공성이 불안정한 문제가 있었다.In addition, as the olefin polymer is applied to various fields, various processing conditions must be satisfied without deterioration of mechanical properties. Therefore, conventionally, in order to control the molecular weight distribution variously, the molecular weight distribution is controlled using multi-stage reactors having different polymerization conditions, or polymers having different molecular weights are blended. However, the conventional method has a problem in terms of efficiency and economy, and in particular, in the case of the blending method of the polymer, the processability is unstable due to the difference in the melt viscosity between the blending addition process and the polymer.

따라서, 기계적 물성의 저하 없이 성형성이 우수한 올레핀 중합체를 제조하기 위해, 중합체의 용도에 따라 분자량 분포를 효과적으로 조절할 수 있는 새로운 메탈로센 촉매의 개발이 요구된다.Therefore, in order to produce an olefin polymer having excellent moldability without deteriorating mechanical properties, it is required to develop a new metallocene catalyst capable of effectively controlling the molecular weight distribution according to the use of the polymer.

대한민국 등록특허 제10-1166946호Korean Patent No. 10-1166946

본 발명의 목적은 촉매 활성이 높고, 올레핀 중합체의 분자량 분포를 효율적으로 조절할 수 있는 올레핀 중합용 담지 촉매를 제공하고자 한다.An object of the present invention is to provide a supported catalyst for olefin polymerization which has high catalytic activity and can efficiently control the molecular weight distribution of the olefin polymer.

또, 본 발명의 다른 목적은 상기 올레핀 중합용 담지 촉매를 사용하는 올레핀 중합체의 제조방법과 이로부터 제조된 올레핀 중합체를 제공하고자 한다.Another object of the present invention is to provide a process for producing an olefin polymer using the supported catalyst for olefin polymerization and an olefin polymer produced therefrom.

본 발명은The present invention

담체 상에,On the carrier,

(a) (ⅰ) 하기 화학식 1로 표시되는 제1 메탈로센 촉매 화합물과; (ⅱ) 하기 화학식 2로 표시되는 제2 메탈로센 촉매 화합물, 하기 화학식 3으로 표시되는 제3 메탈로센 촉매 화합물 또는 이들 모두를 포함하는 주촉매 화합물, 및(a) (i) a first metallocene catalyst compound represented by the following formula (1); (Ii) a second metallocene catalyst compound represented by the following formula (2), a third metallocene catalyst compound represented by the following formula (3), or both, and

(b) 조촉매 화합물(b) a co-catalyst compound

이 담지된 올레핀 중합용 담지 촉매를 제공한다:Thereby providing a supported catalyst for olefin polymerization:

(상기 화학식 1 내지 3에서,(In the above Formulas 1 to 3,

M¹ 내지 M³은 서로 동일하거나 상이하며, 각각 독립적으로 주기율표 상의 3~10족 원소로 이루어진 군에서 선택되고;M¹ to M³ are the same or different from each other, and each independently selected from the group consisting of Group 3 to Group 10 elements on the periodic table;

X¹ 내지 X³는 서로 동일하거나 상이하며, 각각 독립적으로 C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 실릴(C₁~C₂₀)알킬기, C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, (C₆~C₂₀)아릴실릴기, 실릴(C₆~C₂₀)아릴기, C₁~C₂₀의 알콕시기, (C₁~C₂₀)알킬실록시기, C₆~C₂₀의 아릴옥시기, 할로겐 및 아민기로 이루어진 군에서 선택되며;X¹ to X³ are the same or different and each independently represents a C₁ to C₂₀ alkyl group, a C₁ to C₂₀ cycloalkyl group, a C₁ to C₂₀ alkylsilyl group, a silyl (C₁ to C₂₀ ) alkyl, C aryl group of_{6 ~ C 20, (C 6} ~ C 20) aryl (C₁ ~ C₂₀₎ alkyl, (C₁ ~ C₂₀₎ alkyl (C₆ ~ C₂₀₎ aryl, (C₆ ~ C₂₀₎ aryl silyl group, a silyl group (C₆ ~ C₂₀₎ aryl group, C₁ ~ C₂₀ alkoxy group, (C₁ ~ C₂₀₎ alkyl siloxy, aryloxy C₆ ~ C₂₀ of, halogen and An amine group;

a 내지 c는 각각 1~5의 정수이고;a to c are each an integer of 1 to 5;

B는 탄소(C), 규소(Si), 게르마늄(Ge), 질소(N) 및 인(P)으로 이루어진 군에서 선택되고;B is selected from the group consisting of carbon (C), silicon (Si), germanium (Ge), nitrogen (N), and phosphorus (P);

R¹은 수소, C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 실릴(C₁~C₂₀)알킬기, C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, (C₆~C₂₀)아릴실릴기 및 실릴(C₁~C₂₀)아릴기로 이루어진 군에서 선택되며;R¹ is selected from the group consisting of hydrogen, a C₁ to C₂₀ alkyl group, a C₁ to C₂₀ cycloalkyl group, a C₁ to C₂₀ alkylsilyl group, a silyl (C₁ to C₂₀ ) alkyl group, a C₆ to C₂₀ aryl group (C₆ -C₂₀ ) aryl (C₁ -C₂₀ ) alkyl, (C₁ -C₂₀ ) alkyl (C₆ -C₂₀ ) aryl, (C₆ -C₂₀ ) arylsilyl and silyl₁ ~ C₂₀₎ is selected from the group consisting of an aryl group;

d는 1 또는 2이고;d is 1 or 2;

Cp¹ 및 Cp²는 서로 동일하거나 상이하며, 각각 독립적으로 시클로펜타디에닐 골격-함유 리간드이고,Cp <^1> and Cp <² > are the same or different and are each independently a cyclopentadienyl skeleton-

이때, 상기 Cp¹ 및 Cp²의 시클로펜타디에닐 골격-함유 리간드는 C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 실릴(C₁~C₂₀)알킬기, 할로(C₁~C₂₀)알킬기, C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, (C₆~C₂₀)아릴실릴기, 실릴(C₆~C₂₀)아릴기, 할로겐기, 하기 화학식 4로 표시되는 치환체 및 하기 화학식 5로 표시되는 치환체로 이루어진 군에서 선택된 1종 이상의 치환기로 치환 또는 비치환되거나, 또는 상기 인접하는 치환체들이 서로 결합하여 고리를 형성할 수 있으며,The cyclopentadienyl skeleton-containing ligand of Cp¹ and Cp² may be a C₁ to C₂₀ alkyl group, a C₁ to C₂₀ cycloalkyl group, a C₁ to C₂₀ alkylsilyl group, a silyl (C₁ - C₂₀₎ alkyl, halo (C₁ ~ C₂₀₎ alkyl group, a C aryl group of_{6 ~ C 20, (C 6} ~ C 20) aryl (C₁ ~ C₂₀₎ alkyl, (C₁ ~ C₂₀₎ alkyl ( (C₆ -C₂₀ ) aryl group, a (C₆ -C₂₀ ) arylsilyl group, a silyl (C₆ -C₂₀ ) aryl group, a halogen group, a substituent represented by the following formula Or the adjacent substituents may be bonded to each other to form a ring,

다만, 상기 복수의 시클로펜타디에닐 골격-함유 리간드 중 적어도 하나는 각각 독립적으로 하기 화학식 4로 표시되는 치환체 및 하기 화학식 5로 표시되는 치환체로 이루어진 군에서 선택된 1종 이상의 치환체로 치환되며;Provided that at least one of the plurality of cyclopentadienyl skeleton-containing ligands is independently substituted with at least one substituent selected from the group consisting of a substituent represented by the following formula (4) and a substituent represented by the following formula (5);

Z¹ 및 Z²는 서로 동일하거나 상이하며, 각각 독립적으로 주기율표 15족 및 16족의 원소로 이루어진 군에서 선택되고;Z¹ and Z² are the same or different from each other, and each independently selected from the group consisting of Group 15 and Group 16 elements;

R² 및 R⁴는 서로 동일하거나 상이하며, 각각 독립적으로 수소, C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 실릴(C₁~C₂₀)알킬기, C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, C₁~C₂₀의 아릴실릴기, 및 실릴(C₁~C₂₀)아릴기로 이루어진 군에서 선택되며;R² and R⁴ are the same or different and each independently represents hydrogen, a C₁ to C₂₀ alkyl group, a C₁ to C₂₀ cycloalkyl group, a C₁ to C₂₀ alkylsilyl group, a silyl (C₁ to C₂₀₎ alkyl, C aryl group of_{6 ~ C 20, (C 6} ~ C 20) aryl (C₁ ~ C₂₀₎ alkyl, (C₁ ~ C₂₀₎ alkyl (C₆ ~ C₂₀₎ aryl, C₁ ~ C₂₀ aryl silyl group, and silyl (C₁ ~ C₂₀₎ is selected from the group consisting of an aryl group;

e 및 h는 각각 1 또는 2이고;e and h are each 1 or 2;

f 및 i는 각각 1~5의 정수이며;f and i are each an integer of 1 to 5;

g 및 j는 각각 0~4의 정수이고, 상기 g 및 j가 각각 1~4인 경우, R³ 및 R⁵는 서로 동일하거나 상이하며, 각각 독립적으로 C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 실릴(C₁~C₂₀)알킬기, C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, C₁~C₂₀의 아릴실릴기, 및 실릴(C₁~C₂₀)아릴기로 이루어진 군에서 선택되고;g and j is an integer from 0 to 4, respectively, when the g and j are each 1 ~ 4, R³ and R⁵ are the same or different, each independently represent a C₁ ~ C₂₀ alkyl group, C₁ a - silyl C₂₀ cycloalkyl group, C₁ ~ C₂₀ alkyl group, a silyl group (C₁ ~ C₂₀₎ alkyl, C aryl group of_{6 ~ C 20, (C 6} ~ C 20) aryl (C₁ ~ C₂₀₎ An alkyl group, a (C₁ -C₂₀ ) alkyl (C₆ -C₂₀ ) aryl group, a C₁ -C₂₀ arylsilyl group, and a silyl (C₁ -C₂₀ ) aryl group;

Ar¹ 내지 Ar⁴는 서로 동일하거나 상이하며, 각각 독립적으로 시클로펜타디에닐 골격-함유 리간드이고,Ar¹ to Ar⁴ are the same or different from each other and each independently is a cyclopentadienyl skeleton-containing ligand,

이때, 상기 Ar¹ 내지 Ar⁴의 시클로펜타디에닐 골격-함유 리간드는 C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 실릴(C₁~C₂₀)알킬기, 할로(C₁~C₂₀)알킬기, C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, (C₆~C₂₀)아릴실릴기, 실릴(C₆~C₂₀)아릴기, 및 할로겐기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환 또는 비치환되거나, 또는 상기 인접하는 치환체들이 서로 결합하여 고리를 형성할 수 있음).The cyclopentadienyl skeleton-containing ligand of Ar¹ to Ar⁴ may be a C₁ to C₂₀ alkyl group, a C₁ to C₂₀ cycloalkyl group, a C₁ to C₂₀ alkylsilyl group, a silyl (C₁ to C₂₀ ) C₂₀₎ alkyl, halo (C₁ ~ C₂₀₎ alkyl group, a C aryl group of_{6 ~ C 20, (C 6} ~ C 20) aryl (C₁ ~ C₂₀₎ alkyl, (C₁ ~ C₂₀₎ alkyl ( (C₆ -C₂₀ ) aryl group, a (C₆ -C₂₀ ) arylsilyl group, a silyl (C₆ -C₂₀ ) aryl group, and a halogen group, or Said adjacent substituents may combine with each other to form a ring.

여기서, 상기 화학식 1 ~ 3에서, 상기 M¹ 내지 M³는 서로 동일하거나 상이하며, 각각 독립적으로 주기율표상의 4족 원소 중 하나인 것이 바람직하다.In the general formulas (1) to (3), M¹ to M³ are the same as or different from each other, and independently of each other, are preferably one of the elements of Group 4 of the periodic table.

또, 상기 화학식 4 ~ 5에서, 상기 Z₁ 및 Z₂는 서로 동일하거나 상이하고, 각각 독립적으로 질소(N), 인(P), 비소(As), 산소(O), 황(S), 및 셀레늄(Se)로 이루어진 군에서 선택되는 것이 바람직하다.In the general formulas (4) to (5), Z₁ and Z₂ are the same or different from each other and each independently represents nitrogen, phosphorus, arsenic, oxygen, sulfur, And selenium (Se).

일례에 따르면, 상기 주촉매 화합물(a)로 상기 제1 메탈로센 촉매 화합물과 제2 메탈로센 촉매 화합물을 혼합 사용할 경우, 상기 제1 메탈로센 촉매 화합물과 제2 메탈로센 촉매 화합물의 혼합 비율은 1 : 0.05 ~ 20 몰비율인 것이 바람직하다.According to an example, when the first metallocene catalyst compound and the second metallocene catalyst compound are mixed with the main catalyst compound (a), the ratio of the first metallocene catalyst compound to the second metallocene catalyst compound The mixing ratio is preferably 1: 0.05 to 20 molar ratio.

다른 일례에 따르면, 상기 주촉매 화합물(a)로 상기 제1 메탈로센 촉매 화합물과 제3 메탈로센 촉매 화합물을 혼합 사용할 경우, 상기 제1 메탈로센 촉매 화합물과 제3 메탈로센 촉매 화합물의 혼합 비율은 1 : 0.05 ~ 20 몰비율인 것이 바람직하다.According to another example, when the first metallocene catalyst compound and the third metallocene catalyst compound are mixed with the main catalyst compound (a), the first metallocene catalyst compound and the third metallocene catalyst compound Is preferably in the range of 1: 0.05 to 20 molar ratio.

또 다른 일례에 따르면, 상기 주촉매 화합물(a)로 상기 제1 메탈로센 촉매 화합물, 제2 메탈로센 촉매 화합물 및 제3 메탈로센 촉매 화합물을 혼합 사용할 경우, 상기 제1 메탈로센 촉매 화합물, 제2 메탈로센 촉매 화합물 및 제3 메탈로센 촉매 화합물의 혼합 비율은 1 : 0.05 ~ 20 : 0.05 ~ 20 몰비율인 것이 바람직하다.According to another example, when the first metallocene catalyst compound, the second metallocene catalyst compound and the third metallocene catalyst compound are mixed with the main catalyst compound (a), the first metallocene catalyst The mixing ratio of the compound, the second metallocene catalyst compound and the third metallocene catalyst compound is preferably 1: 0.05 to 20: 0.05 to 20 mole ratio.

상기 조촉매 화합물(b)은 ⅰ) 알루미녹산 화합물, ⅱ) 유기알루미늄 화합물, 및 ⅲ) 메탈로센 촉매 화합물과 반응하여 메탈로센 촉매 화합물이 촉매 활성을 갖게 하는 벌키한 화합물로 이루어진 군으로부터 선택된 것이 바람직하다.The promoter compound (b) is selected from the group consisting of i) aluminoxane compounds, ii) organoaluminum compounds, and iii) a bulky compound that reacts with the metallocene catalyst compound to render the metallocene catalyst compound catalytically active .

이때, 상기 주촉매 화합물과 조촉매 화합물의 사용 비율은 상기 주촉매 화합물에 함유된 전이금속 원자에 대한 조촉매 화합물에 함유된 금속의 몰비가 1 : 0.01 ~ 1000 범위인 것이 바람직하다.At this time, it is preferable that the ratio of the main catalyst compound to the co-catalyst compound is in the range of 1: 0.01 to 1000 in terms of the molar ratio of the metal contained in the co-catalyst compound to the transition metal atom contained in the main catalyst compound.

상기 담체는 실리카(Silica), 알루미나(Alumina), 보오크사이트(Bauxite), 제올라이트(Zeolite), MgCl₂, CaCl₂, MgO, ZrO₂, TiO₂, B₂O₃, CaO, ZnO, BaO, ThO₂, 및 이들의 복합체로 이루어진 군에서 선택되거나, 또는 전분(Starch), 사이클로덱스트린(Cyclodextrin) 및 합성고분자로 이루어진 군에서 선택된 것이 바람직하다.The support is silica (Silica), alumina (Alumina), bauxite (Bauxite), zeolite_{(Zeolite), MgCl 2, CaCl} 2, MgO, ZrO 2, TiO 2, B 2 O 3, CaO, ZnO, BaO, ThO₂ , and a complex thereof, or is selected from the group consisting of starch, cyclodextrin and synthetic polymer.

또, 본 발명은 전술한 올레핀 중합용 촉매의 존재 하에서 하나 이상의 올레핀계 단량체를 중합시키는 단계를 포함하는 올레핀 중합체의 제조방법을 제공한다.The present invention also provides a process for preparing an olefin polymer comprising polymerizing at least one olefin monomer in the presence of the aforementioned catalyst for olefin polymerization.

여기서, 상기 올레핀계 단량체는 C₂~C₂₀의 α-올레핀, C₄~C₂₀의 디올레핀, C₃~C₂₀의 시클로올레핀, C₃~C₂₀의 시클로디올레핀, 스티렌 및 스티렌 유도체로 이루어진 군에서 선택된 것일 수 있다.Here, the olefinic monomer may be a C₂ to C₂₀ α-olefin, a C₄ to C₂₀ diolefin, a C₃ to C₂₀ cycloolefin, a C₃ to C₂₀ cycloolefin, a styrene and a styrene derivative Lt; / RTI >

또한, 본 발명은 전술한 방법에 의해 제조되고, 분자량 분포가 2.0 ~ 30 범위인 올레핀 중합체를 제공한다.The present invention also provides an olefin polymer produced by the above-described method and having a molecular weight distribution ranging from 2.0 to 30.

본 발명에 따른 올레핀 중합용 담지 촉매는 상기 화학식 1로 표시되는 제1 메탈로센 촉매 화합물을 상기 화학식 2로 표시되는 제2 메탈로센 촉매 화합물 및/또는 상기 화학식 3으로 표시되는 제3 메탈로센 촉매 화합물과 혼합 사용하되, 조촉매 화합물과 함께 담체에 담지시킴으로써, 기계적 물성 저하 없이 다양한 가공 조건에 따라 분자량 분포를 효율적으로 조절하여 다양한 올레핀 중합체를 경제적으로 제조할 수 있다.The supported catalyst for olefin polymerization according to the present invention can be obtained by reacting the first metallocene catalyst compound represented by the formula (1) with the second metallocene catalyst compound represented by the formula (2) and / or the third metallocene catalyst represented by the formula The catalyst can be economically manufactured by efficiently controlling the molecular weight distribution according to various processing conditions without deteriorating the mechanical properties of the olefin polymer.

이하, 본 발명에 대하여 설명한다.Hereinafter, the present invention will be described.

메탈로센 촉매 화합물은 두 개의 시클로펜타디에닐기(cyclopentadienyl group)-함유 리간드 사이에 Ti, Zr, Hf 등과 같은 전이금속이 개재(介在)된 형태로 결합하고 있는 촉매 화합물로서, 비스(인데닐)지르코늄디클로라이드 등과 같은 화학식 2의 메탈로센 촉매 화합물이나, 라세믹-에틸렌비스(테트라하이드로인데닐)지르코늄디클로라이드 등과 같은 상기 화학식 3의 메탈로센 촉매 화합물이 알려져 있다.The metallocene catalyst compound is a catalyst compound in which a transition metal such as Ti, Zr, Hf and the like is interposed between two cyclopentadienyl group-containing ligands, and bis (indenyl) Metallocene catalyst compounds of formula (2) such as zirconium dichloride and the like, and metallocene catalyst compounds of formula (3) such as racemic-ethylenebis (tetrahydroindenyl) zirconium dichloride are known.

이러한 메탈로센 촉매 화합물을 이용하여 올레핀 중합체를 제조할 경우, 중합체의 분자량 분포가 상대적으로 좁기 때문에, 중합체의 기계적 물성(예컨대, 강도 등)은 우수하나, 높은 용융 점도로 인해 성형성이 저하되는 문제가 있었다.When the olefin polymer is produced using such a metallocene catalyst compound, the polymer has a relatively narrow molecular weight distribution, so that the mechanical properties (e.g., strength, etc.) of the polymer are excellent, but the moldability is deteriorated due to the high melt viscosity There was a problem.

한편, 본 발명자들은 시클로펜타디에닐기-함유 리간드에 아민기(-NH₂)나 알코올기(-OH) 등으로 치환된 페닐기, 비페닐기가 치환(도입)된 상기 화학식 1의 메탈로센 촉매 화합물(예컨대, 비스-[1-(p-디메틸아미노페닐)-3,4-디메틸시클로펜타디에닐]지르코늄 디클로라이드)을 개발하였는데, 이 메탈로센 촉매 화합물을 알루미녹산 등과 같은 조촉매 화합물과 함께 사용할 경우, 조촉매 화합물과의 상호 작용으로 인해 다중 활성자리를 가지며, 이로 인해 분자량 분포가 넓은 올레핀 중합체를 제조할 수 있다는 것을 알았다.On the other hand, the inventors of the present invention have found that when a metallocene catalyst compound of the above formula (1) in which a phenyl group substituted with an amine group (-NH₂ ) or an alcohol group (-OH) is substituted for a cyclopentadienyl group- (Such as bis- [1- (p -dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride), which metallocene catalyst compound, together with a cocatalyst compound such as aluminoxane, It has been found that, when used, an olefin polymer having multiple active sites due to its interaction with the cocatalyst compound, thereby resulting in a broad molecular weight distribution.

다만, 올레핀 중합체는 다양한 분야에서 사용됨에 따라 기계적 물성 저하 없이 다양한 가공 조건을 만족시켜야 한다. 그러나, 상기 화학식 1의 메탈로센 촉매 화합물을 단독으로 사용할 경우, 상대적으로 더 넓거나 좁은 분자량 분포를 갖는 올레핀 중합체를 제조하는 데 한계가 있었으며, 또한 공단량체의 조성 분포를 조절하기 어려웠다.However, since the olefin polymer is used in various fields, various processing conditions must be satisfied without deteriorating the mechanical properties. However, when the metallocene catalyst compound of Formula 1 is used alone, it is difficult to produce an olefin polymer having a relatively broad or narrow molecular weight distribution, and it is difficult to control the composition distribution of the comonomer.

이에, 본 발명에서는 상기 화학식 1의 메탈로센 촉매 화합물을 상기 화학식 2의 메탈로센 촉매 화합물 및/또는 상기 화학식 3의 메탈로센 촉매 화합물과 혼합 사용하되, 알루미녹산 화합물과 같은 조촉매 화합물과 함께 담체에 담지된 상태로 사용하는 것을 특징으로 한다. 이러한 본 발명의 담지 촉매는 올레핀 중합체의 분자량 분포를 효율적으로 조절할 수 있을 뿐만 아니라, 공단량체의 조성 분포를 유연하게 조절할 수 있다. 따라서, 본 발명의 담지 촉매를 이용할 경우, 기계적 물성 저하 없이 다양한 가공 조건에 따라 분자량 분포를 효율적으로 조절하여 다양한 올레핀 중합체를 경제적으로 제조할 수 있다. 특히, 본 발명의 담지 촉매는 고분자량 영역의 함량이 증가하는 방향으로 중합체의 분자량 분포가 넓어지도록 분자량 및 분자량 분포를 조절할 수 있기 때문에, 기계적 물성 및 성형성이 모두 우수한 올레핀 중합체를 제조할 수 있다.Accordingly, in the present invention, the metallocene catalyst compound of Formula 1 is mixed with the metallocene catalyst compound of Formula 2 and / or the metallocene catalyst compound of Formula 3, And is used in a state of being carried on a carrier. The supported catalyst of the present invention can not only efficiently control the molecular weight distribution of the olefin polymer but also can flexibly control the composition distribution of the comonomer. Therefore, when the supported catalyst of the present invention is used, various olefin polymers can be economically produced by efficiently controlling the molecular weight distribution according to various processing conditions without deteriorating mechanical properties. In particular, since the supported catalyst of the present invention can control the molecular weight and the molecular weight distribution so that the molecular weight distribution of the polymer increases in the direction of increasing the content of the high molecular weight region, the olefin polymer having both excellent mechanical properties and moldability can be produced .

<올레핀 중합용 담지 촉매>&Lt; Supporting catalyst for olefin polymerization >

본 발명에 따른 올레핀 중합용 담지 촉매는 (a) 상기 화학식 1의 제1 메탈로센 촉매 화합물과, 상기 화학식 2의 제2 메탈로센 촉매 화합물 및/또는 상기 화학식 3의 제3 메탈로센 촉매 화합물의 혼합물인 주촉매 화합물; 및 (b) 조촉매 화합물이 담체에 담지된 상태이다.The supported catalyst for olefin polymerization according to the present invention comprises (a) a first metallocene catalyst compound of Formula 1, and a second metallocene catalyst compound of Formula 2 and / or a third metallocene catalyst of Formula 3 A main catalyst compound which is a mixture of compounds; And (b) the co-catalyst compound is supported on the carrier.

이하, 본 발명에 따른 담지 촉매의 각 성분에 대하여 설명한다.Each component of the supported catalyst according to the present invention will be described below.

(a) 주촉매 화합물(a) the main catalyst compound

본 발명의 올레핀 중합용 담지 촉매에서, 주촉매 화합물은 (ⅰ) 상기 화학식 1로 표시되는 제1 메탈로센 촉매 화합물과, (ⅱ) 상기 화학식 2로 표시되는 제2 메탈로센 촉매 화합물 및/또는 상기 화학식 3으로 표시되는 제3 메탈로센 촉매 화합물을 포함한다. 이러한 주촉매 화합물(a)은 하기 담체의 표면에 담지된 상태로, 하기 조촉매 화합물에 의해 활성화되어 올레핀 중합 반응에 활성을 부여한다.In the supported catalyst for olefin polymerization according to the present invention, the main catalyst compound is obtained by (i) a first metallocene catalyst compound represented by the general formula (1) and (ii) a second metallocene catalyst compound represented by the general formula (2) Or a third metallocene catalyst compound represented by the general formula (3). The main catalyst compound (a) is activated by the following promoter compound in the state of being supported on the surface of the following carrier to impart activity to the olefin polymerization reaction.

여기서, 상기 메탈로센 촉매 화합물들 간의 혼합 비율은 화합물의 활성 및 중합 공정의 조건 등을 고려하여 결정할 수 있다.Here, the mixing ratio of the metallocene catalyst compounds can be determined in consideration of the activity of the compound and the conditions of the polymerization process.

일례에 따르면, 상기 주촉매 화합물(a)로 상기 화학식 1의 제1 메탈로센 촉매 화합물과 상기 화학식 2의 제2 메탈로센 촉매 화합물을 혼합 사용할 수 있다. 이때, 상기 화학식 1의 제1 메탈로센 촉매 화합물과 상기 화학식 2의 제2 메탈로센 촉매 화합물의 혼합 비율은 특별히 한정되지 않으나, 1 : 0.05 ~ 20 몰비율일 경우, 중합체의 분자량 분포를 효율적으로 조절할 수 있다.According to an example, the first metallocene catalyst compound of Formula 1 and the second metallocene catalyst compound of Formula 2 may be used as the main catalyst compound (a). In this case, the mixing ratio of the first metallocene catalyst compound of Formula 1 and the second metallocene catalyst compound of Formula 2 is not particularly limited, but when the molar ratio is 1: 0.05 to 20, the molecular weight distribution of the polymer is efficiently .

다른 일례에 따르면, 상기 주촉매 화합물(a)로 상기 화학식 1의 제1 메탈로센 촉매 화합물과 상기 화학식 3의 제3 메탈로센 촉매 화합물을 혼합 사용할 수 있다. 이때, 상기 화학식 1의 제1 메탈로센 촉매 화합물과 상기 화학식 3의 제3 메탈로센 촉매 화합물의 혼합 비율은 특별히 한정되지 않으나, 1 : 0.05 ~ 20 몰비율일 경우, 중합체의 분자량 분포를 효율적으로 조절할 수 있다.According to another example, the first metallocene catalyst compound of Formula 1 and the third metallocene catalyst compound of Formula 3 may be used as the main catalyst compound (a). In this case, the mixing ratio of the first metallocene catalyst compound of Formula 1 and the third metallocene catalyst compound of Formula 3 is not particularly limited, but when the ratio is 1: 0.05 to 20, the molecular weight distribution of the polymer is efficiently .

또 다른 일례에 따르면, 상기 주촉매 화합물(a)로 상기 화학식 1의 제1 메탈로센 촉매 화합물, 상기 화학식 2의 제2 메탈로센 촉매 화합물 및 상기 화학식 3의 제3 메탈로센 촉매 화합물을 혼합 사용할 수 있다. 이때, 기 화학식 1의 제1 메탈로센 촉매 화합물, 상기 화학식 2의 제2 메탈로센 촉매 화합물 및 상기 화학식 3의 제3 메탈로센 촉매 화합물의 혼합 비율은 1 : 0.05 ~ 20 : 0.05 ~ 20 몰비율일 경우, 중합체의 분자량 분포를 효율적으로 조절할 수 있다.According to another example, the first metallocene catalyst compound of Formula 1, the second metallocene catalyst compound of Formula 2, and the third metallocene catalyst compound of Formula 3 may be used as the main catalyst compound (a) Can be mixed. In this case, the mixing ratio of the first metallocene catalyst compound of Formula 1, the second metallocene catalyst compound of Formula 2, and the third metallocene catalyst compound of Formula 3 is 1: 0.05-20: 0.05-20 Molar ratio, the molecular weight distribution of the polymer can be efficiently controlled.

(ⅰ) 제1 메탈로센 촉매 화합물(I) a first metallocene catalyst compound

본 발명의 제1 메탈로센 촉매 화합물은 상기 화학식 1로 표시되는 메탈로센 촉매 화합물로서, 다른 메탈로센 촉매 화합물 및 조촉매 화합물과의 상호 작용을 통해 분자량 분포를 넓게 조절할 수 있으며, 고분자량의 함량을 증가시킬 수 있다.The first metallocene catalyst compound of the present invention is a metallocene catalyst compound represented by the above-mentioned formula (1), and its molecular weight distribution can be widely controlled through interaction with other metallocene catalyst compounds and cocatalyst compounds. Can be increased.

본 발명에 따르면, 상기 화학식 1의 화합물에서, M¹은 주기율표 상의 3~10족 원소로 이루어진 군에서 선택되고, 바람직하게 주기율표 상의 4족 원소 중 하나이며, 더 바람직하게 지르코늄(Zr), 티타늄(Ti) 또는 하프늄(Hf)이다.According to the present invention, in the compound of Formula 1, M¹ is selected from the group consisting of Group 3 to Group 10 elements in the periodic table, preferably one of Group 4 elements in the periodic table, more preferably zirconium (Zr), titanium Ti) or hafnium (Hf).

또, X¹은 C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 실릴(C₁~C₂₀)알킬기, C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, (C₆~C₂₀)아릴실릴기, 실릴(C₆~C₂₀)아릴기, C₁~C₂₀의 알콕시기, (C₁~C₂₀)알킬실록시기, C₆~C₂₀의 아릴옥시기, 할로겐 및 아민기로 이루어진 군에서 선택된다. 이때, 아민기는 -NH₂뿐만 아니라, (C₁~C₂₀)알킬아민기, (C₁~C₂₀)디알킬아민기, (C₆~C₂₀)아릴아민기, (C₆~C₂₀)디아릴아민기를 포함하는 의미이다.X¹ represents a C₁ to C₂₀ alkyl group, a C₁ to C₂₀ cycloalkyl group, a C₁ to C₂₀ alkylsilyl group, a silyl (C₁ to C₂₀ ) alkyl group, a C₆ to C₂₀ aryl group (C₆ -C₂₀ ) aryl (C₁ -C₂₀ ) alkyl, (C₁ -C₂₀ ) alkyl (C₆ -C₂₀ ) aryl, (C₆ -C₂₀ ) arylsilyl,₆ ~ C₂₀₎ is selected from an aryl group, C₁ ~ C₂₀ alkoxy group, (C₁ ~ C₂₀₎ alkyl siloxy group, an aryloxy group, the group consisting of a halogen and an amine of the C₆ ~ C₂₀ of. At this time, the amine groups, as well as_{-NH 2 (C 1 ~ C 20} ) alkyl amine groups, (C₁ ~ C₂₀₎ dialkyl amine group, (C₆ ~ C₂₀₎ aryl amine group, (C₆ ~ C₂₀ ) Diarylamine group.

여기서, 상기 X¹의 C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 및 실릴(C₁~C₂₀)알킬기의 예로는 메틸기, 에틸기, 프로필기, 부틸기, 펜틸기, 헥실기, 헵틸기, 옥틸기, 노닐기, 데실기, 시클로프로필기, 시클로부틸기, 시클로펜틸기, 시클로헥실기, 시클로옥틸기, 데카하이드로나프탈릴(Decahydronaphthalyl)기, 메틸실릴(Methylsilyl)기, 디메틸실릴(Dimethylsilyl)기, 트리메틸실릴(Trimethylsilyl)기, 에틸실릴(Ethylsilyl)기, 디에틸실릴(Diethylsilyl)기, 트리에틸실릴(Triethylsilyl)기, 프로필실릴(Propylsilyl)기, 디프로필실릴(Dipropylsilyl)기, 트리프로필실릴(Tripropylsilyl)기, 부틸실릴(Butylsilyl)기, 디부틸실릴(Dibutylsilyl)기, 트리부틸실릴(Tributylsilyl)기, (메틸실릴)메틸[(Methylsilyl)methyl]기, (디메틸실릴)메틸[(Dimethylsilyl) methyl]기, (트리메틸실릴)메틸[(Trimethylsilyl)methyl]기, (에틸실릴)메틸[(Ethylsilyl)methyl]기, (디에틸실릴)메틸[(Dethylsilyl)methyl]기, (트리에틸실릴)메틸[(Triethylsilyl)methyl]기, (메틸실릴)에틸[(Methylsilyl)ethyl]기, (디메틸실릴)에틸[(Dimethylsilyl) ethyl]기, (트리메틸실릴)에틸 [(Trimethylsilyl)ethyl]기 등이 있는데, 이에 한정되지 않는다.Here, examples of the X C₁ to alkyl groups of C₂₀ for^1, C cycloalkyl group of₁ to C_20, C group_{of 1} to alkylsilyl of C_20, and silyl (C₁ to C₂₀₎ alkyl group is a methyl group, an ethyl group, A cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a decahydronaphthalyl group, a cyclopentyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, A methylsilyl group, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a propylsilyl ( Propylsilyl group, a dipropylsilyl group, a tripropylsilyl group, a butylsilyl group, a dibutylsilyl group, a tributylsilyl group, a (methylsilyl) methyl [( (Dimethylsilyl) methyl] group, (trimethylsilyl) methyl [(trimethylsilyl) methyl] (Ethylsilyl) methyl] group, (ethylsilyl) methyl] group, (diethylsilyl) methyl] group, (triethylsilyl) Methylsilyl) ethyl] group, (dimethylsilyl) ethyl [(dimethylsilyl) ethyl] group, and (trimethylsilyl) ethyl [(trimethylsilyl) ethyl] group.

또, 상기 X¹의 C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, (C₆~C₂₀)아릴실릴기, 및 실릴(C₆~C₂₀)아릴기의 예로는 페닐기, 바이페닐기, 터페닐기, 나프틸기, 플루오레닐(Fluorenyl)기, 벤질기, 페닐에틸기, 페닐프로필기, 메틸페닐기, 디메틸페닐기, 트리메틸페닐기, 에틸페닐기, 디에틸페닐기, 트리에틸페닐기, 프로필페닐기, 디프로필페닐기, 트리프로필페닐기, 페닐실릴(Phenylsilyl)기, 메틸페닐실릴(Methylphenylsilyl)기, 디메틸페닐실릴(Dimethylphenylsilyl)기, 메틸디페닐실릴(methyl(diphenyl)silyl), 트리페닐실릴(Triphenylsilyl)기, 에틸페닐실릴(Ethylphenylsilyl)기, (메틸페닐)실릴[(Methylphenyl)silyl]기, (에틸페닐)실릴[(Ethylphenyl)silyl]기, 트리플루오로메틸페닐실릴(Trifluoromethylphenylsilyl)기, (메틸실릴)페닐[(Methylsilyl)phenyl]기, (디메틸실릴)페닐[(Dimethylsilyl)phenyl]기, (트리메틸실릴)페닐[(Trimethylsilyl)phenyl]기, (에틸실릴)페닐[(Ethylsilyl)phenyl]기, (디에틸실릴)페닐[(Diethylsilyl)phenyl]기, (트리에틸실릴)페닐[(Triethylsilyl)phenyl]기, (프로필실릴)페닐[(Propylsilyl)phenyl]기, (디프로필실릴)페닐[(Dipropylsilyl)phenyl]기, (부틸실릴)페닐[(Butylsilyl) phenyl]기, (디부틸실릴)페닐[(Dibutylsilyl)phenyl]기 등이 있는데, 이에 한정되지 않는다.In addition, the aryl group of_{^{X 1 C 6 ~ C 20,}} (C 6 ~ C 20) aryl (C₁ ~ C₂₀₎ alkyl, (C₁ ~ C₂₀₎ alkyl (C₆ ~ C₂₀₎ aryl group, (C₆ -C₂₀ ) arylsilyl group and a silyl (C₆ -C₂₀ ) aryl group include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a benzyl group, A phenylphenyl group, a dimethylphenylsilyl group, a dimethylphenylsilyl group, a dimethylphenylsilyl group, a dimethylphenylsilyl group, a dimethylphenylsilyl group, a dimethylphenylsilyl group, a dimethylphenylsilyl group, a dimethylphenylsilyl group, a dimethylphenylsilyl group, Methylphenylsilyl group, methylphenylsilyl group, methylphenylsilyl group, diphenylsilyl group, triphenylsilyl group, ethylphenylsilyl group, methylphenylsilyl group, ethylphenylsilyl group, ) Silyl] group, a trifluoromethylphenylsilyl group, a (methylsilyl) phenyl group, a (dimethylsilyl) phenyl [ (Trimethylsilyl) phenyl group, (trimethylsilyl) phenyl group, (ethylsilyl) phenyl [(ethylsilyl) phenyl] group, (diethylsilyl) phenyl [ (Propylsilyl) phenyl] group, (dipropylsilyl) phenyl group, (butylsilyl) phenyl] group, , (Dibutylsilyl) phenyl] group, but are not limited thereto.

또, 상기 X¹의 C₁~C₂₀의 알콕시기, 및 (C₁~C₂₀)알킬실록시기의 예로는 메톡시(Methoxy)기, 에톡시(Ethoxy)기, 프로폭시(Propoxy)기, 부톡시(Butoxy)기, 펜톡시(Pentoxy)기, 헥실옥시(Hexyloxy)기, 메틸실록시(Methylsiloxy)기, 디메틸실록시(Dimethylsiloxy)기, 트리메틸실록시(Trimethylsiloxy)기, 에틸실록시(Ethylsiloxy)기, 디에틸실록시(Diethylsiloxy)기, 트리에틸실록시(Triethylsiloxy)기 등이 있는데, 이에 한정되지 않는다.Examples of the C₁ -C₂₀ alkoxy group and the (C₁ -C₂₀ ) alkylsiloxy group of X¹ include a methoxy group, an ethoxy group, a propoxy group, (Methoxy) group, a butoxy group, a pentoxy group, a hexyloxy group, a methylsiloxy group, a dimethylsiloxy group, a trimethylsiloxy group, an ethylsiloxy group Ethylsiloxy group, diethylsiloxy group, triethylsiloxy group, and the like, but are not limited thereto.

또, 상기 X¹의 C₆~C₂₀의 아릴옥시기의 비제한적인 예로는 페녹시(Phenoxy)기, 나프톡시(Naphtoxy)기, 메틸페녹시(Methylphenoxy)기, 디메틸페녹시(Dimethylphenoxy)기, 트리메틸페녹시(Trimethylphenoxy)기, 에틸페녹시(Ethylphenoxy)기, 디에틸페녹시(Diethylphenoxy)기, 트리에틸페녹시(Triethylphenoxy)기, 프로필페녹시(Propylphenoxy)기, 디프로필페녹시기(Dipropylphenoxy), 트리프로필페녹시(Tripropylphenoxy)기 등이 있다.Examples of the C₆ -C₂₀ aryloxy group of X¹ include, but are not limited to, a phenoxy group, a naphthoxy group, a methylphenoxy group, a dimethylphenoxy group, , A trimethylphenoxy group, an ethylphenoxy group, a diethylphenoxy group, a triethylphenoxy group, a propylphenoxy group, a dipropylphenoxy group, , Tripropylphenoxy group and the like.

또한, 상기 X¹의 할로겐(Halogen)기의 예로는 플루오로(Fluoro)기, 클로로(Chloro)기, 브로모(Bromo)기, 요오도(Iodo)기 등이 있는데, 이에 한정되지 않는다.Examples of the halogen group of X¹ include a fluoro group, a chloro group, a bromo group, and an iodo group. However, the present invention is not limited thereto.

또, 상기 X¹의 아민(Amine)기는 -NH₂뿐만 아니라, (C₁~C₂₀)알킬아민기, (C₁~C₂₀)디알킬아민기, (C₆~C₂₀)아릴아민기, (C₆~C₂₀)디아릴아민기를 포함하며, 예컨대 디메틸아민(Dimethylamine)기, 디에틸아민(Diethylamine)기, 디프로필아민(Dipropylamine)기, 디부틸아민(Dibutylamine), 디페닐아민(Diphenylamine)기, 디벤질아민(Dibenzylamine)기 등이 있는데, 이에 한정되지 않는다.The amine group of X¹ may include not only -NH₂ but also (C₁ -C₂₀ ) alkylamine group, (C₁ -C₂₀ ) dialkylamine group, (C₆ -C₂₀ ) arylamine group (C₆ -C₂₀ ) diarylamine group, and examples thereof include a dimethylamine group, a diethylamine group, a dipropylamine group, a dibutylamine group, a diphenylamine group Diphenylamine group, and dibenzylamine group, but are not limited thereto.

바람직하게, 상기 X¹은 메틸(Methyl)기, 에틸(Ethyl)기, 프로필(Propyl)기, 페녹시(Phenoxy)기, 나프톡시(Naphtoxy)기, 메틸페녹시(Methylphenoxy)기, 디메틸페녹시(Dimethylphenoxy)기, 트리메틸페녹시(Trimethylphenoxy)기, 에틸페녹시(Ethylphenoxy)기, 디에틸페녹시(Diethylphenoxy)기, 트리에틸페녹시(Triethylphenoxy)기, 프로필페녹시(Propylphenoxy)기, 디프로필페녹시기(Dipropylphenoxy), 트리프로필페녹시(Tripropylphenoxy)기, 클로로(Chloro)기, 브로모(Bromo)기, 디메틸아민(Dimethylamine)기, 디에틸아민(Diethylamine)기, 디프로필아민(Dipropylamine)기, 디부틸아민(Dibutylamine), 디페닐아민(Diphenylamine)기, 및 디벤질아민(Dibenzylamine)기로 이루어진 군에서 선택할 수 있다.Preferably, X¹ is selected from the group consisting of a methyl group, an ethyl group, a propyl group, a phenoxy group, a naphthoxy group, a methylphenoxy group, a dimethylphenoxy group, A dimethoxyphenoxy group, a dimethylphenoxy group, a trimethylphenoxy group, an ethylphenoxy group, a diethylphenoxy group, a triethylphenoxy group, a propylphenoxy group, A dipropylamine group, a tripropylphenoxy group, a chloro group, a bromo group, a dimethylamine group, a diethylamine group, a dipropylamine group, And may be selected from the group consisting of dibutylamine, diphenylamine group, and dibenzylamine group.

상기 화학식 1에서, a는 중심금속(M¹)의 산화수에 따라 변하는 부분으로, 1~5의 정수이다. 예를 들어, M¹이 주기율표상의 4족 원소 중 하나일 경우, a는 2이다.In the general formula (¹ ), a is a part which varies depending on the oxidation number of the center metal (M¹ ) and is an integer of 1 to 5. For example, when M¹ is one of the Group 4 elements on the periodic table, a is 2.

상기 화학식 1에서, Cp¹과 Cp²는 서로 같거나 다르고, 각각 독립적으로 시클로펜타디에닐 골격-함유 리간드(Ligand)이다. 상기 시클로펜타디에닐 골격-함유 리간드의 예로는 시클로펜타디에닐(Cyclopentadienyl)기, 인데닐(Indenyl)기, 플루오레닐(Fluorenyl)기 등이 있는데, 이에 한정되지 않는다.In the above formula (1), Cp¹ and Cp² are the same or different and each independently is a cyclopentadienyl skeleton-containing ligand. Examples of the cyclopentadienyl skeleton-containing ligand include, but are not limited to, cyclopentadienyl group, indenyl group, fluorenyl group, and the like.

이때, 상기 Cp¹ 및 Cp²의 시클로펜타디에닐 골격-함유 리간드는 C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 실릴(C₁~C₂₀) 알킬기, 할로(C₁~C₂₀)알킬기, C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, (C₆~C₂₀)아릴실릴기, 실릴(C₆~C₂₀)아릴기, 할로겐기, 하기 화학식 4로 표시되는 치환체 및 하기 화학식 5로 표시되는 치환체로 이루어진 군에서 선택된 1종 이상의 치환기로 치환 또는 비치환되거나, 또는 상기 인접하는 치환체들이 서로 결합하여 고리를 형성할 수 있다.The cyclopentadienyl skeleton-containing ligand of Cp¹ and Cp² may be a C₁ to C₂₀ alkyl group, a C₁ to C₂₀ cycloalkyl group, a C₁ to C₂₀ alkylsilyl group, a silyl (C₁ - C₂₀₎ alkyl, halo (C₁ ~ C₂₀₎ alkyl group, a C aryl group of_{6 ~ C 20, (C 6} ~ C 20) aryl (C₁ ~ C₂₀₎ alkyl, (C₁ ~ C₂₀₎ alkyl ( (C₆ -C₂₀ ) aryl group, a (C₆ -C₂₀ ) arylsilyl group, a silyl (C₆ -C₂₀ ) aryl group, a halogen group, a substituent represented by the following formula Substituted or unsubstituted with one or more substituents selected from the group consisting of the above-mentioned substituents, or said adjacent substituents may be bonded to each other to form a ring.

다만, 상기 Cp¹ 및 Cp²의 시클로펜타디에닐 골격-함유 리간드들 중 적어도 하나는 상기 화학식 4로 표시되는 치환체 및 상기 화학식 5로 표시되는 치환체로 이루어진 군에서 선택된 1종 이상의 치환체로 치환된다.However, at least one of the cyclopentadienyl skeleton-containing ligands of Cp¹ and Cp² is substituted with at least one substituent selected from the group consisting of the substituent represented by the formula (4) and the substituent represented by the formula (5).

여기서, 상기 C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 실릴(C₁~C₂₀)알킬기, 할로(C₁~C₂₀)알킬기의 비제한적인 예로는 메틸(Methyl)기, 에틸(Ethyl)기, 프로필(Propyl)기, 부틸(Butyl)기, 펜틸(Pentyl)기, 헥실(Hexyl)기, 헵틸(Heptyl)기, 옥틸(Octyl)기, 노닐(Nonyl)기, 데실(Decyl)기, 시클로프로필(Cyclopropyl)기, 시클로부틸(Cyclobutyl)기, 시클로펜틸(Cyclopentyl)기, 시클로헥실(Cyclohexyl)기, 시클로옥틸(Cyclooctyl)기, 데카하이드로나프탈릴(Decahydronaphthalyl)기, 메틸실릴(Methylsilyl)기, 디메틸실릴(Dimethylsilyl)기, 트리메틸실릴(Trimethylsilyl)기, 에틸실릴(Ethylsilyl)기, 디에틸실릴(Diethylsilyl)기, 트리에틸실릴(Triethylsilyl)기, 프로필실릴(Propylsilyl)기, 디프로필실릴(Dipropylsilyl)기, 트리프로필실릴(Tripropylsilyl)기, 부틸실릴(Butylsilyl)기, 디부틸실릴 (Dibutylsilyl)기, 트리부틸실릴(Tributylsilyl)기, (메틸실릴)메틸[(Methylsilyl)methyl]기, (디메틸실릴)메틸[(Dimethylsilyl) methyl]기, (트리메틸실릴)메틸[(Trimethylsilyl)methyl]기, (에틸실릴)메틸[(Ethylsilyl)methyl]기, (디에틸실릴)메틸[(Dethylsilyl)methyl]기, (트리에틸실릴)메틸[(Triethylsilyl)methyl]기, (메틸실릴)에틸[(Methylsilyl)ethyl]기, (디메틸실릴)에틸[(Dimethylsilyl) ethyl]기, (트리메틸실릴)에틸[(Trimethylsilyl)ethyl]기, 트리플루오로메틸(Trifluoromethyl)기, 트리클로로메틸(Trichloromethyl)기 등이 있다.Here, the C₁ ~ C₂₀ alkyl group, C₁ ~ a C₂₀ cycloalkyl group, C₁ ~ alkyl silyl group of C_20, silyl (C₁ ~ C₂₀₎ alkyl, halo (C₁ ~ C₂₀₎ alkyl group of the Non-limiting examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, A cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, A decahydronaphthalyl group, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, A propylsilyl group, a dipropylsilyl group, a tripropylsilyl group, a butylsilyl group, a dibutylsilyl group, a tributylsilyl group, (Trimethylsilyl) methyl group, (ethylsilyl) methyl group, (methylsilyl) methyl group, (dimethylsilyl) methyl group, (Methylsilyl) methyl group, (diethylsilyl) methyl group, (triethylsilyl) methyl group, (methylsilyl) ethyl [(methylsilyl) ethyl] group, Silyl) ethyl [(Dimethylsilyl) ethyl] group, (trimethylsilyl) ethyl [(Trimethylsilyl) ethyl] group, trifluoromethyl group and trichloromethyl group.

또, 상기 C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, (C₆~C₂₀)아릴실릴기, 실릴(C₆~C₂₀)아릴기의 비제한적인 예로는 페닐(Phenyl)기, 바이페닐(Biphenyl)기, 터페닐(Terphenyl)기, 나프틸(Naphtyl)기, 플루오레닐(Fluorenyl)기, 벤질(Benzyl)기, 페닐에틸(Phenylethyl), 페닐프로필(Phenylpropyl)기, 메틸페닐(Methylphenyl)기, 디메틸페닐(Dimethylphenyl)기, 트리메틸페닐(Trimethylphenyl)기, 에틸페닐(Ethylphenyl)기, 디에틸페닐(Diethylphenyl)기, 트리에틸페닐(Triethylphenyl)기, 프로필페닐(Propylphenyl)기, 디프로필페닐(Dipropylphenyl)기, 트리프로필페닐(Tripropylphenyl)기, 페닐실릴(Phenylsilyl)기, 메틸페닐실릴(Methylphenylsilyl)기, 디메틸페닐실릴(Dimethylphenylsilyl)기, 메틸디페닐실릴(methyl(diphenyl)silyl), 트리페닐실릴(Triphenylsilyl)기, 에틸페닐실릴(Ethylphenylsilyl)기, (메틸페닐)실릴[(Methylphenyl)silyl]기, (에틸페닐)실릴[(Ethylphenyl)silyl]기, 트리플루오로메틸페닐실릴(Trifluoromethylphenylsilyl)기, (메틸실릴)페닐[(Methylsilyl)phenyl]기, (디메틸실릴)페닐[(Dimethylsilyl)phenyl]기, (트리메틸실릴)페닐[(Trimethylsilyl)phenyl]기, (에틸실릴)페닐[(Ethylsilyl)phenyl]기, (디에틸실릴)페닐[(Diethylsilyl)phenyl]기, (트리에틸실릴)페닐[(Triethylsilyl)phenyl]기, (프로필실릴)페닐[(Propylsilyl)phenyl]기, (디프로필실릴)페닐[(Dipropylsilyl)phenyl]기, (부틸실릴)페닐[(Butylsilyl) phenyl]기, (디부틸실릴)페닐[(Dibutylsilyl)phenyl]기 등이 있다.In addition, the aryl group of the_{C 6 ~ C 20, (C} 6 ~ C 20) aryl (C₁ ~ C₂₀₎ alkyl, (C₁ ~ C₂₀₎ alkyl (C₆ ~ C₂₀₎ aryl, (C₆ ~ C₂₀₎ aryl silyl group, a silyl group (C₆ ~ C₂₀₎ non-limiting examples of the aryl group are phenyl (phenyl) group, biphenyl (biphenyl) group, a terphenyl (terphenyl) group, a naphthyl (naphtyl) group , A fluorenyl group, a benzyl group, a phenylethyl group, a phenylpropyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, A diethylphenyl group, a diethylphenyl group, a triethylphenyl group, a propylphenyl group, a dipropylphenyl group, a tripropylphenyl group, a phenylsilyl group, , A methylphenylsilyl group, a dimethylphenylsilyl group, a methyl diphenyl silyl group, a triphenylsilyl group, an ethylphenylsilyl group, a (methylphenyl) silyl group, (Ethylphenyl) silyl] group, trifluoromethylphenylsilyl group, (methylsilyl) phenyl [(methylsilyl) phenyl] group, (dimethylsilyl) phenyl [ (Trimethylsilyl) phenyl group, (trimethylsilyl) phenyl group, (ethylsilyl) phenyl [(ethylsilyl) phenyl] group, (diethylsilyl) phenyl [ (Propylsilyl) phenyl] group, (dipropylsilyl) phenyl group, (butylsilyl) phenyl] group, , (Dibutylsilyl) phenyl [(Dibutylsilyl) phenyl] group and the like.

또, 상기 할로겐기의 예로는 플루오로(Fluoro)기, 클로로(Chloro)기, 브로모(Bromo)기, 요오도(Iodo)기 등이 있는데, 이에 한정되지 않는다.Examples of the halogen group include, but are not limited to, a fluoro group, a chloro group, a bromo group, and an iodo group.

상기 화학식 4 내지 5에서, Z¹ 및 Z²는 서로 동일하거나 상이하며, 각각 독립적으로 주기율표 15족 및 16족의 원소로 이루어진 군에서 선택되고, 바람직하게 질소(N), 인(P), 비소(As), 산소(O), 황(S), 및 셀레늄(Se)로 이루어진 군에서 선택될 수 있다.In the general formulas (4) to (5), Z¹ and Z² are the same or different and are independently selected from the group consisting of elements of Group 15 and Group 16 of the periodic table, (As), oxygen (O), sulfur (S), and selenium (Se).

또, R² 및 R⁴는 서로 동일하거나 상이하며, 각각 독립적으로 수소, C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 실릴(C₁~C₂₀)알킬기, C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, C₁~C₂₀의 아릴실릴기, 및 실릴(C₁~C₂₀)아릴기로 이루어진 군에서 선택된다.In addition, R² and R⁴ are the same or different, each independently represent hydrogen, C₁ ~ C₂₀ alkyl group, C₁ ~ C₂₀ cycloalkyl group, C₁ ~ C₂₀ alkyl silyl group, the silyl (C₁ ~ C₂₀₎ alkyl group, C₆ ~ aryl group of_{C 20, (C 6 ~ C} 20) aryl (C₁ ~ C₂₀₎ alkyl, (C₁ ~ C₂₀₎ alkyl (C₆ ~ C₂₀₎ aryl group, A C₁ to C₂₀ arylsilyl group, and a silyl (C₁ to C₂₀ ) aryl group.

또, e 및 h는 각각 Z₁ 및 Z₂의 종류에 따라 달라지고, 각각 1 또는 2이고; f 및 i는 각각 1~5의 정수이다.E and h are each 1 or 2 depending on the kind of Z₁ and Z₂ , respectively; f and i are each an integer of 1 to 5;

또, g 및 j는 각각 0~4의 정수이고, 상기 g 및 j가 각각 0인 경우, 상기 R³및 R⁵는 각각 수소인 것을 의미하며, 상기 g 및 j가 각각 1~4의 정수인 경우, R³ 및 R⁵는 서로 동일하거나 상이하며, 각각 독립적으로 C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 실릴(C₁~C₂₀)알킬기, C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, C₁~C₂₀의 아릴실릴기, 및 실릴(C₁~C₂₀)아릴기로 이루어진 군에서 선택된다.G and j are each an integer of 0 to 4, and when g and j are each 0, R³ and R⁵ are each hydrogen, and when g and j are each an integer of 1 to 4 , R³ and R⁵ are the same or different and each independently represents a C₁ to C₂₀ alkyl group, a C₁ to C₂₀ cycloalkyl group, a C₁ to C₂₀ alkylsilyl group, a silyl (C₁ to C₂₀ ) alkyl, C aryl group of_{6 ~ C 20, (C 6} ~ C 20) aryl (C₁ ~ C₂₀₎ alkyl, (C₁ ~ C₂₀₎ alkyl (C₆ ~ C₂₀₎ aryl group, C₁ ~ aryl silyl group of C_20, and silyl (C₁ ~ C₂₀₎ is selected from the group consisting of an aryl group.

여기서, 상기 R² 내지 R⁵의 C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 및 실릴(C₁~C₂₀)알킬기의 비제한적인 예로는 메틸(Methyl)기, 에틸(Ethyl)기, 프로필(Propyl)기, 부틸(Butyl)기, 펜틸(Pentyl)기, 헥실(Hexyl)기, 헵틸(Heptyl)기, 옥틸(Octyl)기, 노닐(Nonyl)기, 데실(Decyl)기, 시클로프로필(Cyclopropyl)기, 시클로부틸(Cyclobutyl)기, 시클로펜틸(Cyclopentyl)기, 시클로헥실(Cyclohexyl)기, 시클로옥틸(Cyclooctyl)기, 데카하이드로나프탈릴(Decahydronaphthalyl)기, 메틸실릴(Methylsilyl)기, 디메틸실릴(Dimethylsilyl)기, 트리메틸실릴(Trimethylsilyl)기, 에틸실릴(Ethylsilyl)기, 디에틸실릴(Diethylsilyl)기, 트리에틸실릴(Triethylsilyl)기, 프로필실릴(Propylsilyl)기, 디프로필실릴(Dipropylsilyl)기, 트리프로필실릴(Tripropylsilyl)기, 부틸실릴(Butylsilyl)기, 디부틸실릴 (Dibutylsilyl)기, 트리부틸실릴(Tributylsilyl)기, (메틸실릴)메틸[(Methylsilyl)methyl]기, (디메틸실릴)메틸[(Dimethylsilyl) methyl]기, (트리메틸실릴)메틸[(Trimethylsilyl)methyl]기, (에틸실릴)메틸[(Ethylsilyl)methyl]기, (디에틸실릴)메틸[(Dethylsilyl)methyl]기, (트리에틸실릴)메틸[(Triethylsilyl)methyl]기, (메틸실릴)에틸[(Methylsilyl)ethyl]기, (디메틸실릴)에틸[(Dimethylsilyl) ethyl]기, (트리메틸실릴)에틸[(Trimethylsilyl)ethyl]기 등이 있다.Here, the non-limiting examples of the C₁ to C₂₀ alkyl group, C₁ to C₂₀ cycloalkyl group, C₁ to C₂₀ alkylsilyl group, and silyl (C₁ to C₂₀ ) alkyl group of R² to R⁵ Examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, A cyclopentyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a decahydronaphthyl group, a cyclopentyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexyl group, A silane coupling agent such as a decahydronaphthalyl group, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, A propylsilyl group, a dipropylsilyl group, a tripropylsilyl group, a butylsilyl group, a dibutylsilyl group, a tributylsilyl (Tri butylsilyl group, (methylsilyl) methyl group, (dimethylsilyl) methyl [(dimethylsilyl) methyl] group, (trimethylsilyl) methyl [(trimethylsilyl) methyl] (Ethylsilyl) methyl] group, (diethylsilyl) methyl group, (triethylsilyl) methyl group, (methylsilyl) ethyl [ Ethyl [(dimethylsilyl) ethyl] group, and (trimethylsilyl) ethyl [(trimethylsilyl) ethyl] group.

또, 상기 R² 내지 R⁵의 C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, (C₆~C₂₀)아릴실릴기 및 실릴(C₁~C₂₀)아릴기의 비제한적인 예로는 페닐(Phenyl)기, 바이페닐(Biphenyl)기, 터페닐(Terphenyl)기, 나프틸(Naphtyl)기, 플루오레닐(Fluorenyl)기, 벤질(Benzyl)기, 페닐에틸(Phenylethyl), 페닐프로필(Phenylpropyl)기, 메틸페닐(Methylphenyl)기, 디메틸페닐(Dimethylphenyl)기, 트리메틸페닐(Trimethylphenyl)기, 에틸페닐(Ethylphenyl)기, 디에틸페닐(Diethylphenyl)기, 트리에틸페닐(Triethylphenyl)기, 프로필페닐(Propylphenyl)기, 디프로필페닐(Dipropylphenyl)기, 트리프로필페닐(Tripropylphenyl)기, 페닐실릴(Phenylsilyl)기, 메틸페닐실릴(Methylphenylsilyl)기, 디메틸페닐실릴(Dimethylphenylsilyl)기, 메틸디페닐실릴(methyl(diphenyl)silyl), 트리페닐실릴(Triphenylsilyl)기, 에틸페닐실릴(Ethylphenylsilyl)기, (메틸페닐)실릴[(Methylphenyl)silyl]기, (에틸페닐)실릴[(Ethylphenyl)silyl]기, 트리플루오로메틸페닐실릴(Trifluoromethylphenylsilyl)기, (메틸실릴)페닐[(Methylsilyl)phenyl]기, (디메틸실릴)페닐[(Dimethylsilyl)phenyl]기, (트리메틸실릴)페닐[(Trimethylsilyl)phenyl]기, (에틸실릴)페닐[(Ethylsilyl)phenyl]기, (디에틸실릴)페닐[(Diethylsilyl)phenyl]기, (트리에틸실릴)페닐[(Triethylsilyl)phenyl]기, (프로필실릴)페닐[(Propylsilyl)phenyl]기, (디프로필실릴)페닐[(Dipropylsilyl)phenyl]기, (부틸실릴)페닐[(Butylsilyl) phenyl]기, (디부틸실릴)페닐[(Dibutylsilyl)phenyl]기 등이 있다.In addition, the R² to the aryl group of R⁵ a_{C 6 ~ C 20, (C} 6 ~ C 20) aryl (C₁ ~ C₂₀₎ alkyl, (C₁ ~ C₂₀₎ alkyl (C₆ ~ C₂₀₎ Non-limiting examples of the aryl group, the (C₆ -C₂₀ ) arylsilyl group and the silyl (C₁ -C₂₀ ) aryl group include a phenyl group, a biphenyl group, a terphenyl group, A naphthyl group, a fluorenyl group, a benzyl group, a phenylethyl group, a phenylpropyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group A trimethylphenyl group, an ethylphenyl group, a diethylphenyl group, a triethylphenyl group, a propylphenyl group, a dipropylphenyl group, a tripropylphenyl group, (Methylphenylsilyl) group, a dimethylphenylsilyl group, methyl (diphenyl) silyl, a triphenylsilyl group, an ethylphenylsilyl group, a phenylphenylsilyl group, (Methylphenyl) silyl group, (ethylphenyl) silyl group, trifluoromethylphenylsilyl group, (methylsilyl) phenyl group, (methylphenyl) silyl group, (Dimethylsilyl) phenyl group, (trimethylsilyl) phenyl group, (ethylsilyl) phenyl group, (diethylsilyl) phenyl group, (Triethylsilyl) phenyl group, (propylsilyl) phenyl group, (dipropylsilyl) phenyl group, (butylsilyl) phenyl [ (Dibutylsilyl) phenyl] group, and (dibutylsilyl) phenyl] group.

전술한 화학식 1로 표시되는 제1 메탈로센 촉매 화합물의 예로는 비스-[1-(p-디메틸아미노페닐)-3,4-디메틸시클로펜타디에닐]지르코늄 디클로라이드([1-(p-Me₂NC₆H₄)-3,4-Me₂C₅H₂]₂ZrCl₂), 비스-[1-(p-메톡시비페닐)-3,4-디메틸시클로펜타디에닐]지르코늄 디클로라이드([1-(p-MeO C₆H₄C₆H₄)-3,4-Me₂C₅H₂]₂ZrCl₂) 등이 있는데, 이에 한정되지 않는다.Examples of the metallocene catalyst compound of a first metal which is represented by the aforementioned formula (I) is bis - [1-(p - dimethylaminophenyl) -3,4-dimethyl-cyclopentadienyl] zirconium dichloride ([1-(p - Me₂ NC₆ H₄ ) -3,4-Me₂ C₅ H₂ ]₂ ZrCl₂ ), bis- [1- (p -methoxybiphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride ([1- (p -MeO C₆ H₄ C₆ H₄ ) -3,4-Me₂ C₅ H₂ ]₂ ZrCl₂ ).

(ⅱ-1) 제2 메탈로센 촉매 화합물(Ii-1) a second metallocene catalyst compound

본 발명의 제2 메탈로센 촉매 화합물은 양(兩) 시클로펜타디에닐 골격-함유 리간드를 연결하는 리간드가 없는 메탈로센 촉매 화합물로서, 상기 화학식 2로 표시된다.The second metallocene catalyst compound of the present invention is a ligand-free metallocene catalyst compound linking both cyclopentadienyl skeleton-containing ligands, represented by Formula 2 above.

상기 제2 메탈로센 촉매 화합물은 공단량체와의 반응성이 상대적으로 낮지만 촉매 활성이 우수하고 촉매 비용이 싸다. 따라서, 상기 제2 메탈로센 촉매 화합물을 제1 메탈로센 촉매 화합물과 혼합 사용하거나, 또는 제1 및 제3 메탈로센 촉매 화합물과 혼합 사용할 경우, 상기 제2 메탈로센 촉매 화합물로 인해 촉매 활성이 향상될 수 있고, 이로 인해 올레핀 중합체의 합성이 용이하고, 올레핀 중합체를 상업적, 경제적으로 대량 생산할 수 있다. 또한, 상기 제2 메탈로센 촉매 화합물의 경우, 상대적으로 저분자량 영역의 올레핀 중합체를 제조할 수 있기 때문에, 이 메탈로센 촉매 화합물을 제1 메탈로센 촉매 화합물과 혼합 사용하거나 또는 제1 및 제3 메탈로센 촉매 화합물과 혼합 사용할 경우, 제1 메탈로센 촉매 화합물이나 제3 메탈로센 촉매 화합물을 단독으로 사용하는 경우에 비해 상대적으로 더 넓은 분자량 분포를 갖는 올레핀 중합체를 용이하게 제조할 수 있다.The second metallocene catalyst compound has relatively low reactivity with the comonomer, but has excellent catalytic activity and low catalyst cost. Thus, when the second metallocene catalyst compound is used in admixture with the first metallocene catalyst compound, or mixed with the first and third metallocene catalyst compounds, the second metallocene catalyst compound causes the catalyst The activity can be improved, whereby the synthesis of the olefin polymer is easy, and the olefin polymer can be mass-produced commercially and economically. Further, in the case of the second metallocene catalyst compound, since it is possible to prepare an olefin polymer in a relatively low molecular weight region, the metallocene catalyst compound is mixed with the first metallocene catalyst compound, When mixed with a third metallocene catalyst compound, an olefin polymer having a relatively broader molecular weight distribution can be easily prepared compared to using the first metallocene catalyst compound or the third metallocene catalyst compound alone .

본 발명에 따른 상기 화학식 2의 화합물에서, M²는 주기율표 상의 3~10족 원소로 이루어진 군에서 선택되고, 바람직하게 주기율표 상의 4족 원소 중 하나이며, 더 바람직하게 지르코늄(Zr), 티타늄(Ti) 또는 하프늄(Hf)이다.In the compound of Formula 2 according to the present invention, M² is selected from the group consisting of Group 3 to Group 10 elements in the periodic table, preferably one of Group 4 elements in the periodic table, more preferably zirconium (Zr), titanium ) Or hafnium (Hf).

또, X²는 C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 실릴(C₁~C₂₀)알킬기, C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, (C₆~C₂₀)아릴실릴기, 실릴(C₆~C₂₀)아릴기, C₁~C₂₀의 알콕시기, (C₁~C₂₀)알킬실록시기, C₆~C₂₀의 아릴옥시기, 할로겐 및 아민기로 이루어진 군에서 선택된다.X² represents a C₁ to C₂₀ alkyl group, a C₁ to C₂₀ cycloalkyl group, a C₁ to C₂₀ alkylsilyl group, a silyl (C₁ to C₂₀ ) alkyl group, a C₆ to C₂₀ aryl group (C₆ -C₂₀ ) aryl (C₁ -C₂₀ ) alkyl, (C₁ -C₂₀ ) alkyl (C₆ -C₂₀ ) aryl, (C₆ -C₂₀ ) arylsilyl,₆ ~ C₂₀₎ is selected from an aryl group, C₁ ~ C₂₀ alkoxy group, (C₁ ~ C₂₀₎ alkyl siloxy group, an aryloxy group, the group consisting of a halogen and an amine of the C₆ ~ C₂₀ of.

여기서, 상기 X²의 C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 및 실릴(C₁~C₂₀)알킬기의 예로는 메틸기, 에틸기, 프로필기, 부틸기, 펜틸기, 헥실기, 헵틸기, 옥틸기, 노닐기, 데실기, 시클로프로필기, 시클로부틸기, 시클로펜틸기, 시클로헥실기, 시클로옥틸기, 데카하이드로나프탈릴(Decahydronaphthalyl)기, 메틸실릴(Methylsilyl)기, 디메틸실릴(Dimethylsilyl)기, 트리메틸실릴(Trimethylsilyl)기, 에틸실릴(Ethylsilyl)기, 디에틸실릴(Diethylsilyl)기, 트리에틸실릴(Triethylsilyl)기, 프로필실릴(Propylsilyl)기, 디프로필실릴(Dipropylsilyl)기, 트리프로필실릴(Tripropylsilyl)기, 부틸실릴(Butylsilyl)기, 디부틸실릴(Dibutylsilyl)기, 트리부틸실릴(Tributylsilyl)기, (메틸실릴)메틸[(Methylsilyl)methyl]기, (디메틸실릴)메틸[(Dimethylsilyl) methyl]기, (트리메틸실릴)메틸[(Trimethylsilyl)methyl]기, (에틸실릴)메틸[(Ethylsilyl)methyl]기, (디에틸실릴)메틸[(Dethylsilyl)methyl]기, (트리에틸실릴)메틸[(Triethylsilyl)methyl]기, (메틸실릴)에틸[(Methylsilyl)ethyl]기, (디메틸실릴)에틸[(Dimethylsilyl) ethyl]기, (트리메틸실릴)에틸 [(Trimethylsilyl)ethyl]기 등이 있는데, 이에 한정되지 않는다.Here, examples of the alkyl group of X² of_{C 1 ~ C 20, C 1} ~ alkyl silyl group of C₂₀ cycloalkyl group, C₁ ~ C₂₀ of, and silyl (C₁ ~ C₂₀₎ alkyl group is a methyl group, an ethyl group, A cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a decahydronaphthalyl group, a cyclopentyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, A methylsilyl group, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a propylsilyl ( Propylsilyl group, a dipropylsilyl group, a tripropylsilyl group, a butylsilyl group, a dibutylsilyl group, a tributylsilyl group, a (methylsilyl) methyl [( (Dimethylsilyl) methyl] group, (trimethylsilyl) methyl [(trimethylsilyl) methyl] (Ethylsilyl) methyl] group, (ethylsilyl) methyl] group, (diethylsilyl) methyl] group, (triethylsilyl) Methylsilyl) ethyl] group, (dimethylsilyl) ethyl [(dimethylsilyl) ethyl] group, and (trimethylsilyl) ethyl [(trimethylsilyl) ethyl] group.

또, 상기 X²의 C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, (C₆~C₂₀)아릴실릴기, 및 실릴(C₆~C₂₀)아릴기의 예로는 페닐기, 바이페닐기, 터페닐기, 나프틸기, 플루오레닐(Fluorenyl)기, 벤질기, 페닐에틸기, 페닐프로필기, 메틸페닐기, 디메틸페닐기, 트리메틸페닐기, 에틸페닐기, 디에틸페닐기, 트리에틸페닐기, 프로필페닐기, 디프로필페닐기, 트리프로필페닐기, 페닐실릴(Phenylsilyl)기, 메틸페닐실릴(Methylphenylsilyl)기, 디메틸페닐실릴(Dimethylphenylsilyl)기, 메틸디페닐실릴(methyl(diphenyl)silyl), 트리페닐실릴(Triphenylsilyl)기, 에틸페닐실릴(Ethylphenylsilyl)기, (메틸페닐)실릴[(Methylphenyl)silyl]기, (에틸페닐)실릴[(Ethylphenyl)silyl]기, 트리플루오로메틸페닐실릴(Trifluoromethylphenylsilyl)기, (메틸실릴)페닐[(Methylsilyl)phenyl]기, (디메틸실릴)페닐[(Dimethylsilyl)phenyl]기, (트리메틸실릴)페닐[(Trimethylsilyl)phenyl]기, (에틸실릴)페닐[(Ethylsilyl)phenyl]기, (디에틸실릴)페닐[(Diethylsilyl)phenyl]기, (트리에틸실릴)페닐[(Triethylsilyl)phenyl]기, (프로필실릴)페닐[(Propylsilyl)phenyl]기, (디프로필실릴)페닐[(Dipropylsilyl)phenyl]기, (부틸실릴)페닐[(Butylsilyl) phenyl]기, (디부틸실릴)페닐[(Dibutylsilyl)phenyl]기 등이 있는데, 이에 한정되지 않는다.In addition, the aryl group of X² of_{C 6 ~ C 20, (C} 6 ~ C 20) aryl (C₁ ~ C₂₀₎ alkyl, (C₁ ~ C₂₀₎ alkyl (C₆ ~ C₂₀₎ aryl group, (C₆ -C₂₀ ) arylsilyl group and a silyl (C₆ -C₂₀ ) aryl group include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a benzyl group, A phenylphenyl group, a dimethylphenylsilyl group, a dimethylphenylsilyl group, a dimethylphenylsilyl group, a dimethylphenylsilyl group, a dimethylphenylsilyl group, a dimethylphenylsilyl group, a dimethylphenylsilyl group, a dimethylphenylsilyl group, a dimethylphenylsilyl group, Methylphenylsilyl group, methylphenylsilyl group, methylphenylsilyl group, diphenylsilyl group, triphenylsilyl group, ethylphenylsilyl group, methylphenylsilyl group, ethylphenylsilyl group, ) Silyl] group, a trifluoromethylphenylsilyl group, a (methylsilyl) phenyl group, a (dimethylsilyl) phenyl [ (Trimethylsilyl) phenyl group, (trimethylsilyl) phenyl group, (ethylsilyl) phenyl [(ethylsilyl) phenyl] group, (diethylsilyl) phenyl [ (Propylsilyl) phenyl] group, (dipropylsilyl) phenyl group, (butylsilyl) phenyl] group, , (Dibutylsilyl) phenyl] group, but are not limited thereto.

또, 상기 X²의 C₁~C₂₀의 알콕시기, 및 (C₁~C₂₀)알킬실록시기의 예로는 메톡시(Methoxy)기, 에톡시(Ethoxy)기, 프로폭시(Propoxy)기, 부톡시(Butoxy)기, 펜톡시(Pentoxy)기, 헥실옥시(Hexyloxy)기, 메틸실록시(Methylsiloxy)기, 디메틸실록시(Dimethylsiloxy)기, 트리메틸실록시(Trimethylsiloxy)기, 에틸실록시(Ethylsiloxy)기, 디에틸실록시(Diethylsiloxy)기, 트리에틸실록시(Triethylsiloxy)기 등이 있는데, 이에 한정되지 않는다.Examples of the C₁ -C₂₀ alkoxy group and the (C₁ -C₂₀ ) alkylsiloxy group of X² include a methoxy group, an ethoxy group, a propoxy group, (Methoxy) group, a butoxy group, a pentoxy group, a hexyloxy group, a methylsiloxy group, a dimethylsiloxy group, a trimethylsiloxy group, an ethylsiloxy group Ethylsiloxy group, diethylsiloxy group, triethylsiloxy group, and the like, but are not limited thereto.

또, 상기 X²의 C₆~C₂₀의 아릴옥시기의 비제한적인 예로는 페녹시(Phenoxy)기, 나프톡시(Naphtoxy)기, 메틸페녹시(Methylphenoxy)기, 디메틸페녹시(Dimethylphenoxy)기, 트리메틸페녹시(Trimethylphenoxy)기, 에틸페녹시(Ethylphenoxy)기, 디에틸페녹시(Diethylphenoxy)기, 트리에틸페녹시(Triethylphenoxy)기, 프로필페녹시(Propylphenoxy)기, 디프로필페녹시기(Dipropylphenoxy), 트리프로필페녹시(Tripropylphenoxy)기 등이 있다.Examples of the C₆ -C₂₀ aryloxy group of X² include, but are not limited to, a phenoxy group, a naphthoxy group, a methylphenoxy group, a dimethylphenoxy group , A trimethylphenoxy group, an ethylphenoxy group, a diethylphenoxy group, a triethylphenoxy group, a propylphenoxy group, a dipropylphenoxy group, , Tripropylphenoxy group and the like.

또한, 상기 X²의 할로겐(Halogen)기의 예로는 플루오로(Fluoro)기, 클로로(Chloro)기, 브로모(Bromo)기, 요오도(Iodo)기 등이 있는데, 이에 한정되지 않는다.Examples of the halogen group of X² include a fluoro group, a chloro group, a bromo group, and an iodo group. However, the present invention is not limited thereto.

또, 상기 X²의 아민(Amine)기는 -NH₂뿐만 아니라, (C₁~C₂₀)알킬아민기, (C₁~C₂₀)디알킬아민기, (C₆~C₂₀)아릴아민기, (C₆~C₂₀)디아릴아민기를 포함하며, 예컨대 디메틸아민(Dimethylamine)기, 디에틸아민(Diethylamine)기, 디프로필아민(Dipropylamine)기, 디부틸아민(Dibutylamine), 디페닐아민(Diphenylamine)기, 디벤질아민(Dibenzylamine)기 등이 있는데, 이에 한정되지 않는다.The amine group of X² is not only -NH₂ but also a (C₁ -C₂₀ ) alkylamine group, (C₁ -C₂₀ ) dialkylamine group, (C₆ -C₂₀ ) arylamine group (C₆ -C₂₀ ) diarylamine group, and examples thereof include a dimethylamine group, a diethylamine group, a dipropylamine group, a dibutylamine group, a diphenylamine group Diphenylamine group, and dibenzylamine group, but are not limited thereto.

바람직하게, 상기 X²는 메틸(Methyl)기, 에틸(Ethyl)기, 프로필(Propyl)기, 페녹시(Phenoxy)기, 나프톡시(Naphtoxy)기, 메틸페녹시(Methylphenoxy)기, 디메틸페녹시(Dimethylphenoxy)기, 트리메틸페녹시(Trimethylphenoxy)기, 에틸페녹시(Ethylphenoxy)기, 디에틸페녹시(Diethylphenoxy)기, 트리에틸페녹시(Triethylphenoxy)기, 프로필페녹시(Propylphenoxy)기, 디프로필페녹시기(Dipropylphenoxy), 트리프로필페녹시(Tripropylphenoxy)기, 클로로(Chloro)기, 브로모(Bromo)기, 디메틸아민(Dimethylamine)기, 디에틸아민(Diethylamine)기, 디프로필아민(Dipropylamine)기, 디부틸아민(Dibutylamine), 디페닐아민(Diphenylamine)기, 및 디벤질아민(Dibenzylamine)기로 이루어진 군에서 선택할 수 있다.Preferably, X² is selected from the group consisting of a methyl group, an ethyl group, a propyl group, a phenoxy group, a naphthoxy group, a methylphenoxy group, a dimethylphenoxy group, A dimethoxyphenoxy group, a dimethylphenoxy group, a trimethylphenoxy group, an ethylphenoxy group, a diethylphenoxy group, a triethylphenoxy group, a propylphenoxy group, A dipropylamine group, a tripropylphenoxy group, a chloro group, a bromo group, a dimethylamine group, a diethylamine group, a dipropylamine group, And may be selected from the group consisting of dibutylamine, diphenylamine group, and dibenzylamine group.

상기 화학식 2에서, b는 중심금속(M²)의 산화수에 따라 변하는 부분으로, 1~5의 정수이다. 예를 들어, M²가 주기율표상의 4족 원소 중 하나일 경우, b는 2이다.In the formula (² ), b is a moiety varying depending on the oxidation number of the center metal (M² ), and is an integer of 1 to 5. For example, when M² is one of the Group 4 elements on the periodic table, b is 2.

또, Ar¹ 및 Ar²는 서로 동일하거나 상이하며, 각각 독립적으로 시클로펜타디에닐 골격-함유 리간드이다. 상기 시클로펜타디에닐 골격-함유 리간드의 예로는 시클로펜타디에닐(Cyclopentadienyl)기, 인데닐(Indenyl)기, 플루오레닐(Fluorenyl)기 등이 있는데, 이에 한정되지 않는다.Ar¹ and Ar² are the same or different from each other, and each independently is a cyclopentadienyl skeleton-containing ligand. Examples of the cyclopentadienyl skeleton-containing ligand include, but are not limited to, cyclopentadienyl group, indenyl group, fluorenyl group, and the like.

이때, 상기 Ar¹ 및 Ar²의 시클로펜타디에닐 골격-함유 리간드는 C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 실릴(C₁~C₂₀)알킬기, 할로(C₁~C₂₀)알킬기, C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, (C₆~C₂₀)아릴실릴기, 실릴(C₆~C₂₀)아릴기, 및 할로겐기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환 또는 비치환되거나, 또는 상기 인접하는 치환체들이 서로 결합하여 고리를 형성할 수 있다.The cyclopentadienyl skeleton-containing ligand of Ar¹ and Ar² may be a C₁ to C₂₀ alkyl group, a C₁ to C₂₀ cycloalkyl group, a C₁ to C₂₀ alkylsilyl group, a silyl (C₁ to C₂₀ ) C₂₀₎ alkyl, halo (C₁ ~ C₂₀₎ alkyl group, a C aryl group of_{6 ~ C 20, (C 6} ~ C 20) aryl (C₁ ~ C₂₀₎ alkyl, (C₁ ~ C₂₀₎ alkyl ( (C₆ -C₂₀ ) aryl group, a (C₆ -C₂₀ ) arylsilyl group, a silyl (C₆ -C₂₀ ) aryl group, and a halogen group, or The adjacent substituents may combine with each other to form a ring.

여기서, 상기 C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 실릴(C₁~C₂₀)알킬기, 할로(C₁~C₂₀)알킬기의 비제한적인 예로는 메틸(Methyl)기, 에틸(Ethyl)기, 프로필(Propyl)기, 부틸(Butyl)기, 펜틸(Pentyl)기, 헥실(Hexyl)기, 헵틸(Heptyl)기, 옥틸(Octyl)기, 노닐(Nonyl)기, 데실(Decyl)기, 시클로프로필(Cyclopropyl)기, 시클로부틸(Cyclobutyl)기, 시클로펜틸(Cyclopentyl)기, 시클로헥실(Cyclohexyl)기, 시클로옥틸(Cyclooctyl)기, 데카하이드로나프탈릴(Decahydronaphthalyl)기, 메틸실릴(Methylsilyl)기, 디메틸실릴(Dimethylsilyl)기, 트리메틸실릴(Trimethylsilyl)기, 에틸실릴(Ethylsilyl)기, 디에틸실릴(Diethylsilyl)기, 트리에틸실릴(Triethylsilyl)기, 프로필실릴(Propylsilyl)기, 디프로필실릴(Dipropylsilyl)기, 트리프로필실릴(Tripropylsilyl)기, 부틸실릴(Butylsilyl)기, 디부틸실릴 (Dibutylsilyl)기, 트리부틸실릴(Tributylsilyl)기, (메틸실릴)메틸[(Methylsilyl)methyl]기, (디메틸실릴)메틸[(Dimethylsilyl) methyl]기, (트리메틸실릴)메틸[(Trimethylsilyl)methyl]기, (에틸실릴)메틸[(Ethylsilyl)methyl]기, (디에틸실릴)메틸[(Dethylsilyl)methyl]기, (트리에틸실릴)메틸[(Triethylsilyl)methyl]기, (메틸실릴)에틸[(Methylsilyl)ethyl]기, (디메틸실릴)에틸[(Dimethylsilyl) ethyl]기, (트리메틸실릴)에틸[(Trimethylsilyl)ethyl]기, 트리플루오로메틸(Trifluoromethyl)기, 트리클로로메틸(Trichloromethyl)기 등이 있다.Here, the C₁ ~ C₂₀ alkyl group, C₁ ~ a C₂₀ cycloalkyl group, C₁ ~ alkyl silyl group of C_20, silyl (C₁ ~ C₂₀₎ alkyl, halo (C₁ ~ C₂₀₎ alkyl group of the Non-limiting examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, A cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, A decahydronaphthalyl group, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, A propylsilyl group, a dipropylsilyl group, a tripropylsilyl group, a butylsilyl group, a dibutylsilyl group, a tributylsilyl group, (Trimethylsilyl) methyl group, (ethylsilyl) methyl group, (methylsilyl) methyl group, (dimethylsilyl) methyl group, (Methylsilyl) methyl group, (diethylsilyl) methyl group, (triethylsilyl) methyl group, (methylsilyl) ethyl [(methylsilyl) ethyl] group, Silyl) ethyl [(Dimethylsilyl) ethyl] group, (trimethylsilyl) ethyl [(Trimethylsilyl) ethyl] group, trifluoromethyl group and trichloromethyl group.

또, 상기 C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, (C₆~C₂₀)아릴실릴기, 실릴(C₆~C₂₀)아릴기의 비제한적인 예로는 페닐(Phenyl)기, 바이페닐(Biphenyl)기, 터페닐(Terphenyl)기, 나프틸(Naphtyl)기, 플루오레닐(Fluorenyl)기, 벤질(Benzyl)기, 페닐에틸(Phenylethyl), 페닐프로필(Phenylpropyl)기, 메틸페닐(Methylphenyl)기, 디메틸페닐(Dimethylphenyl)기, 트리메틸페닐(Trimethylphenyl)기, 에틸페닐(Ethylphenyl)기, 디에틸페닐(Diethylphenyl)기, 트리에틸페닐(Triethylphenyl)기, 프로필페닐(Propylphenyl)기, 디프로필페닐(Dipropylphenyl)기, 트리프로필페닐(Tripropylphenyl)기, 페닐실릴(Phenylsilyl)기, 메틸페닐실릴(Methylphenylsilyl)기, 디메틸페닐실릴(Dimethylphenylsilyl)기, 메틸디페닐실릴(methyl(diphenyl)silyl), 트리페닐실릴(Triphenylsilyl)기, 에틸페닐실릴(Ethylphenylsilyl)기, (메틸페닐)실릴[(Methylphenyl)silyl]기, (에틸페닐)실릴[(Ethylphenyl)silyl]기, 트리플루오로메틸페닐실릴(Trifluoromethylphenylsilyl)기, (메틸실릴)페닐[(Methylsilyl)phenyl]기, (디메틸실릴)페닐[(Dimethylsilyl)phenyl]기, (트리메틸실릴)페닐[(Trimethylsilyl)phenyl]기, (에틸실릴)페닐[(Ethylsilyl)phenyl]기, (디에틸실릴)페닐[(Diethylsilyl)phenyl]기, (트리에틸실릴)페닐[(Triethylsilyl)phenyl]기, (프로필실릴)페닐[(Propylsilyl)phenyl]기, (디프로필실릴)페닐[(Dipropylsilyl)phenyl]기, (부틸실릴)페닐[(Butylsilyl) phenyl]기, (디부틸실릴)페닐[(Dibutylsilyl)phenyl]기 등이 있다.In addition, the aryl group of the_{C 6 ~ C 20, (C} 6 ~ C 20) aryl (C₁ ~ C₂₀₎ alkyl, (C₁ ~ C₂₀₎ alkyl (C₆ ~ C₂₀₎ aryl, (C₆ ~ C₂₀₎ aryl silyl group, a silyl group (C₆ ~ C₂₀₎ non-limiting examples of the aryl group are phenyl (phenyl) group, biphenyl (biphenyl) group, a terphenyl (terphenyl) group, a naphthyl (naphtyl) group , A fluorenyl group, a benzyl group, a phenylethyl group, a phenylpropyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, A diethylphenyl group, a diethylphenyl group, a triethylphenyl group, a propylphenyl group, a dipropylphenyl group, a tripropylphenyl group, a phenylsilyl group, , A methylphenylsilyl group, a dimethylphenylsilyl group, a methyl diphenyl silyl group, a triphenylsilyl group, an ethylphenylsilyl group, a (methylphenyl) silyl group, (Ethylphenyl) silyl] group, trifluoromethylphenylsilyl group, (methylsilyl) phenyl [(methylsilyl) phenyl] group, (dimethylsilyl) phenyl [ (Trimethylsilyl) phenyl group, (trimethylsilyl) phenyl group, (ethylsilyl) phenyl [(ethylsilyl) phenyl] group, (diethylsilyl) phenyl [ (Propylsilyl) phenyl] group, (dipropylsilyl) phenyl group, (butylsilyl) phenyl] group, , (Dibutylsilyl) phenyl [(Dibutylsilyl) phenyl] group and the like.

또, 상기 할로겐기의 예로는 플루오로(Fluoro)기, 클로로(Chloro)기, 브로모(Bromo)기, 요오도(Iodo)기 등이 있는데, 이에 한정되지 않는다.Examples of the halogen group include, but are not limited to, a fluoro group, a chloro group, a bromo group, and an iodo group.

상기 제2 메탈로센 촉매 화합물의 비제한적인 예로는, 비스(시클로펜타디에닐)지르코늄 디클로라이드, 비스(메틸시클로펜타디에닐)지르코늄 디클로라이드, 비스(1,3-디메틸시클로펜타디에닐)지르코늄 디클로라이드, 비스(에틸시클로펜타디에닐)지르코늄 디클로라이드, 비스(이소-프로필시클로펜타디에닐)지르코늄 디클로라이드, 비스(n-부틸시클로펜타디에닐)지르코늄 디클로라이드, 비스(이소-부틸시클로펜타디에닐)지르코늄 디클로라이드, 비스(1-부틸-3-메틸시클로펜타디에닐)지르코늄 디클로라이드, 비스(펜타메틸시클로펜타디에닐)지르코늄 디클로라이드, 비스(인데닐)지르코늄 디클로라이드, 비스(2-메틸인데닐)지르코늄 디클로라이드, 비스(4,5,6,7-테트라하이드로-1-인데닐)지르코늄 디클로라이드, 비스(n-부틸시클로펜타디에닐)하프늄 디클로라이드 등이 있다.Non-limiting examples of the second metallocene catalyst compound include bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (1,3-dimethylcyclopentadienyl) Zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (isopropylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (Pentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis Zirconium dichloride, bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, bis (n-butylcyclopentadienyl) hafnium dichloride, Id and so on.

(ⅱ-2) 제3 메탈로센 촉매 화합물(Ii-2) a third metallocene catalyst compound

본 발명의 제3 메탈로센 촉매 화합물은 양(兩) 시클로펜타디에닐 골격-함유 리간드를 연결하는 리간드가 있는 메탈로센 촉매 화합물로서, 상기 화학식 3으로 표시된다.The third metallocene catalyst compound of the present invention is a metallocene catalyst compound having a ligand linking both cyclopentadienyl skeleton-containing ligands, and is represented by the above formula (3).

상기 제3 메탈로센 촉매 화합물은 상기 제2 메탈로센 촉매 화합물에 비해 상대적으로 촉매 활성이 낮으나, 공단량체와의 반응성이 우수하다. 따라서, 상기 제3 메탈로센 촉매 화합물을 제1 메탈로센 촉매 화합물과 혼합 사용하거나 또는 제1 및 제2 메탈로센 촉매 화합물과 혼합 사용할 경우, 분자량 분포를 넓게 조절할 수 있을 뿐만 아니라, 공단량체의 조성 분포를 유연하게 조절할 수 있기 때문에, 공단량체의 함량이 높은 올레핀 중합체를 제조할 수 있다.The third metallocene catalyst compound has a lower catalytic activity than the second metallocene catalyst compound, but has excellent reactivity with the comonomer. Accordingly, when the third metallocene catalyst compound is mixed with the first metallocene catalyst compound or mixed with the first and second metallocene catalyst compounds, not only the molecular weight distribution can be widely controlled, but also the comonomer The olefin polymer having a high comonomer content can be produced.

본 발명에 따른 상기 화학식 3의 화합물에서, M³은 주기율표 상의 3~10족 원소로 이루어진 군에서 선택되고, 바람직하게 주기율표 상의 4족 원소 중 하나이며, 더 바람직하게 지르코늄(Zr), 티타늄(Ti) 또는 하프늄(Hf)이다.In the compound of Formula 3 according to the present invention, M³ is selected from the group consisting of Group 3 to Group 10 elements in the periodic table, preferably one of Group 4 elements in the periodic table, more preferably zirconium (Zr), titanium ) Or hafnium (Hf).

또, X³은 C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 실릴(C₁~C₂₀)알킬기, C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, (C₆~C₂₀)아릴실릴기, 실릴(C₆~C₂₀)아릴기, C₁~C₂₀의 알콕시기, (C₁~C₂₀)알킬실록시기, C₆~C₂₀의 아릴옥시기, 할로겐 및 아민기로 이루어진 군에서 선택된다.X³ represents a C₁ to C₂₀ alkyl group, a C₁ to C₂₀ cycloalkyl group, a C₁ to C₂₀ alkylsilyl group, a silyl (C₁ to C₂₀ ) alkyl group, a C₆ to C₂₀ aryl group (C₆ -C₂₀ ) aryl (C₁ -C₂₀ ) alkyl, (C₁ -C₂₀ ) alkyl (C₆ -C₂₀ ) aryl, (C₆ -C₂₀ ) arylsilyl,₆ ~ C₂₀₎ is selected from an aryl group, C₁ ~ C₂₀ alkoxy group, (C₁ ~ C₂₀₎ alkyl siloxy group, an aryloxy group, the group consisting of a halogen and an amine of the C₆ ~ C₂₀ of.

여기서, 상기 X³의 C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 및 실릴(C₁~C₂₀)알킬기의 예로는 메틸기, 에틸기, 프로필기, 부틸기, 펜틸기, 헥실기, 헵틸기, 옥틸기, 노닐기, 데실기, 시클로프로필기, 시클로부틸기, 시클로펜틸기, 시클로헥실기, 시클로옥틸기, 데카하이드로나프탈릴(Decahydronaphthalyl)기, 메틸실릴(Methylsilyl)기, 디메틸실릴(Dimethylsilyl)기, 트리메틸실릴(Trimethylsilyl)기, 에틸실릴(Ethylsilyl)기, 디에틸실릴(Diethylsilyl)기, 트리에틸실릴(Triethylsilyl)기, 프로필실릴(Propylsilyl)기, 디프로필실릴(Dipropylsilyl)기, 트리프로필실릴(Tripropylsilyl)기, 부틸실릴(Butylsilyl)기, 디부틸실릴(Dibutylsilyl)기, 트리부틸실릴(Tributylsilyl)기, (메틸실릴)메틸[(Methylsilyl)methyl]기, (디메틸실릴)메틸[(Dimethylsilyl) methyl]기, (트리메틸실릴)메틸[(Trimethylsilyl)methyl]기, (에틸실릴)메틸[(Ethylsilyl)methyl]기, (디에틸실릴)메틸[(Dethylsilyl)methyl]기, (트리에틸실릴)메틸[(Triethylsilyl)methyl]기, (메틸실릴)에틸[(Methylsilyl)ethyl]기, (디메틸실릴)에틸[(Dimethylsilyl) ethyl]기, (트리메틸실릴)에틸 [(Trimethylsilyl)ethyl]기 등이 있는데, 이에 한정되지 않는다.Here, examples of the alkyl group of X³ of_{C 1 ~ C 20, C 1} ~ alkyl silyl group of C₂₀ cycloalkyl group, C₁ ~ C₂₀ of, and silyl (C₁ ~ C₂₀₎ alkyl group is a methyl group, an ethyl group, A cyclohexyl group, a cyclohexyl group, a cyclohexyl group, a decahydronaphthalyl group, a cyclopentyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, A methylsilyl group, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a propylsilyl ( Propylsilyl group, a dipropylsilyl group, a tripropylsilyl group, a butylsilyl group, a dibutylsilyl group, a tributylsilyl group, a (methylsilyl) methyl [( (Dimethylsilyl) methyl] group, (trimethylsilyl) methyl [(trimethylsilyl) methyl] (Ethylsilyl) methyl] group, (ethylsilyl) methyl] group, (diethylsilyl) methyl] group, (triethylsilyl) Methylsilyl) ethyl] group, (dimethylsilyl) ethyl [(dimethylsilyl) ethyl] group, and (trimethylsilyl) ethyl [(trimethylsilyl) ethyl] group.

또, 상기 X³의 C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, (C₆~C₂₀)아릴실릴기, 및 실릴(C₆~C₂₀)아릴기의 예로는 페닐기, 바이페닐기, 터페닐기, 나프틸기, 플루오레닐(Fluorenyl)기, 벤질기, 페닐에틸기, 페닐프로필기, 메틸페닐기, 디메틸페닐기, 트리메틸페닐기, 에틸페닐기, 디에틸페닐기, 트리에틸페닐기, 프로필페닐기, 디프로필페닐기, 트리프로필페닐기, 페닐실릴(Phenylsilyl)기, 메틸페닐실릴(Methylphenylsilyl)기, 디메틸페닐실릴(Dimethylphenylsilyl)기, 메틸디페닐실릴(methyl(diphenyl)silyl), 트리페닐실릴(Triphenylsilyl)기, 에틸페닐실릴(Ethylphenylsilyl)기, (메틸페닐)실릴[(Methylphenyl)silyl]기, (에틸페닐)실릴[(Ethylphenyl)silyl]기, 트리플루오로메틸페닐실릴(Trifluoromethylphenylsilyl)기, (메틸실릴)페닐[(Methylsilyl)phenyl]기, (디메틸실릴)페닐[(Dimethylsilyl)phenyl]기, (트리메틸실릴)페닐[(Trimethylsilyl)phenyl]기, (에틸실릴)페닐[(Ethylsilyl)phenyl]기, (디에틸실릴)페닐[(Diethylsilyl)phenyl]기, (트리에틸실릴)페닐[(Triethylsilyl)phenyl]기, (프로필실릴)페닐[(Propylsilyl)phenyl]기, (디프로필실릴)페닐[(Dipropylsilyl)phenyl]기, (부틸실릴)페닐[(Butylsilyl) phenyl]기, (디부틸실릴)페닐[(Dibutylsilyl)phenyl]기 등이 있는데, 이에 한정되지 않는다.In addition, the aryl group of_{^{X 3 C 6 ~ C 20,}} (C 6 ~ C 20) aryl (C₁ ~ C₂₀₎ alkyl, (C₁ ~ C₂₀₎ alkyl (C₆ ~ C₂₀₎ aryl group, (C₆ -C₂₀ ) arylsilyl group and a silyl (C₆ -C₂₀ ) aryl group include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a benzyl group, A phenylphenyl group, a dimethylphenylsilyl group, a dimethylphenylsilyl group, a dimethylphenylsilyl group, a dimethylphenylsilyl group, a dimethylphenylsilyl group, a dimethylphenylsilyl group, a dimethylphenylsilyl group, a dimethylphenylsilyl group, a dimethylphenylsilyl group, Methylphenylsilyl group, methylphenylsilyl group, methylphenylsilyl group, diphenylsilyl group, triphenylsilyl group, ethylphenylsilyl group, methylphenylsilyl group, ethylphenylsilyl group, ) Silyl] group, a trifluoromethylphenylsilyl group, a (methylsilyl) phenyl group, a (dimethylsilyl) phenyl [ (Trimethylsilyl) phenyl group, (trimethylsilyl) phenyl group, (ethylsilyl) phenyl [(ethylsilyl) phenyl] group, (diethylsilyl) phenyl [ (Propylsilyl) phenyl] group, (dipropylsilyl) phenyl group, (butylsilyl) phenyl] group, , (Dibutylsilyl) phenyl] group, but are not limited thereto.

또, 상기 X³의 C₁~C₂₀의 알콕시기, 및 (C₁~C₂₀)알킬실록시기의 예로는 메톡시(Methoxy)기, 에톡시(Ethoxy)기, 프로폭시(Propoxy)기, 부톡시(Butoxy)기, 펜톡시(Pentoxy)기, 헥실옥시(Hexyloxy)기, 메틸실록시(Methylsiloxy)기, 디메틸실록시(Dimethylsiloxy)기, 트리메틸실록시(Trimethylsiloxy)기, 에틸실록시(Ethylsiloxy)기, 디에틸실록시(Diethylsiloxy)기, 트리에틸실록시(Triethylsiloxy)기 등이 있는데, 이에 한정되지 않는다.Examples of the C₁ to C₂₀ alkoxy group and the (C₁ to C₂₀ ) alkylsiloxy group of X³ include a methoxy group, an ethoxy group, a propoxy group, (Methoxy) group, a butoxy group, a pentoxy group, a hexyloxy group, a methylsiloxy group, a dimethylsiloxy group, a trimethylsiloxy group, an ethylsiloxy group Ethylsiloxy group, diethylsiloxy group, triethylsiloxy group, and the like, but are not limited thereto.

또, 상기 X³의 C₆~C₂₀의 아릴옥시기의 비제한적인 예로는 페녹시(Phenoxy)기, 나프톡시(Naphtoxy)기, 메틸페녹시(Methylphenoxy)기, 디메틸페녹시(Dimethylphenoxy)기, 트리메틸페녹시(Trimethylphenoxy)기, 에틸페녹시(Ethylphenoxy)기, 디에틸페녹시(Diethylphenoxy)기, 트리에틸페녹시(Triethylphenoxy)기, 프로필페녹시(Propylphenoxy)기, 디프로필페녹시기(Dipropylphenoxy), 트리프로필페녹시(Tripropylphenoxy)기 등이 있다.Examples of the C₆ -C₂₀ aryloxy group of X³ include, but are not limited to, a phenoxy group, a naphthoxy group, a methylphenoxy group, a dimethylphenoxy group, , A trimethylphenoxy group, an ethylphenoxy group, a diethylphenoxy group, a triethylphenoxy group, a propylphenoxy group, a dipropylphenoxy group, , Tripropylphenoxy group and the like.

또한, 상기 X³의 할로겐(Halogen)기의 예로는 플루오로(Fluoro)기, 클로로(Chloro)기, 브로모(Bromo)기, 요오도(Iodo)기 등이 있는데, 이에 한정되지 않는다.Examples of the halogen group of X³ include a fluoro group, a chloro group, a bromo group, and an iodo group. However, the present invention is not limited thereto.

또, 상기 X³의 아민(Amine)기는 -NH₂뿐만 아니라, (C₁~C₂₀)알킬아민기, (C₁~C₂₀)디알킬아민기, (C₆~C₂₀)아릴아민기, (C₆~C₂₀)디아릴아민기를 포함하며, 예컨대 디메틸아민(Dimethylamine)기, 디에틸아민(Diethylamine)기, 디프로필아민(Dipropylamine)기, 디부틸아민(Dibutylamine), 디페닐아민(Diphenylamine)기, 디벤질아민(Dibenzylamine)기 등이 있는데, 이에 한정되지 않는다.The amine group of X &lt;³ &gt; is not only -NH_2, but also (C₁ -C₂₀ ) alkylamine group, (C₁ -C₂₀ ) dialkylamine group, (C₆ -C₂₀ ) (C₆ -C₂₀ ) diarylamine group, and examples thereof include a dimethylamine group, a diethylamine group, a dipropylamine group, a dibutylamine group, a diphenylamine group Diphenylamine group, and dibenzylamine group, but are not limited thereto.

바람직하게, 상기 X³은 메틸(Methyl)기, 에틸(Ethyl)기, 프로필(Propyl)기, 페녹시(Phenoxy)기, 나프톡시(Naphtoxy)기, 메틸페녹시(Methylphenoxy)기, 디메틸페녹시(Dimethylphenoxy)기, 트리메틸페녹시(Trimethylphenoxy)기, 에틸페녹시(Ethylphenoxy)기, 디에틸페녹시(Diethylphenoxy)기, 트리에틸페녹시(Triethylphenoxy)기, 프로필페녹시(Propylphenoxy)기, 디프로필페녹시기(Dipropylphenoxy), 트리프로필페녹시(Tripropylphenoxy)기, 클로로(Chloro)기, 브로모(Bromo)기, 디메틸아민(Dimethylamine)기, 디에틸아민(Diethylamine)기, 디프로필아민(Dipropylamine)기, 디부틸아민(Dibutylamine), 디페닐아민(Diphenylamine)기, 및 디벤질아민(Dibenzylamine)기로 이루어진 군에서 선택할 수 있다.Preferably, X³ is selected from the group consisting of a methyl group, an ethyl group, a propyl group, a phenoxy group, a naphthoxy group, a methylphenoxy group, a dimethylphenoxy group, A dimethoxyphenoxy group, a dimethylphenoxy group, a trimethylphenoxy group, an ethylphenoxy group, a diethylphenoxy group, a triethylphenoxy group, a propylphenoxy group, A dipropylamine group, a tripropylphenoxy group, a chloro group, a bromo group, a dimethylamine group, a diethylamine group, a dipropylamine group, And may be selected from the group consisting of dibutylamine, diphenylamine group, and dibenzylamine group.

상기 화학식 3에서, c는 중심금속(M³)의 산화수에 따라 변하는 부분으로, 1~5의 정수이다. 예를 들어, M³가 주기율표상의 4족 원소 중 하나일 경우, c는 2이다.In the general formula (³ ), c is a part which varies depending on the oxidation number of the center metal (M³ ) and is an integer of 1 to 5. For example, if M³ is one of the Group 4 elements on the periodic table, then c is 2.

또, Ar³ 및 Ar⁴는 서로 동일하거나 상이하며, 각각 독립적으로 시클로펜타디에닐 골격-함유 리간드이다. 상기 시클로펜타디에닐 골격-함유 리간드의 예로는 시클로펜타디에닐(Cyclopentadienyl)기, 인데닐(Indenyl)기, 플루오레닐(Fluorenyl)기 등이 있는데, 이에 한정되지 않는다.Ar³ and Ar⁴ are the same or different from each other, and each independently is a cyclopentadienyl skeleton-containing ligand. Examples of the cyclopentadienyl skeleton-containing ligand include, but are not limited to, cyclopentadienyl group, indenyl group, fluorenyl group, and the like.

이때, 상기 Ar³ 및 Ar⁴의 시클로펜타디에닐 골격-함유 리간드는 C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 실릴(C₁~C₂₀)알킬기, 할로(C₁~C₂₀)알킬기, C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, (C₆~C₂₀)아릴실릴기, 실릴(C₆~C₂₀)아릴기, 및 할로겐기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환 또는 비치환되거나, 또는 상기 인접하는 치환체들이 서로 결합하여 고리를 형성할 수 있다.The cyclopentadienyl skeleton-containing ligand of Ar³ and Ar⁴ may be a C₁ to C₂₀ alkyl group, a C₁ to C₂₀ cycloalkyl group, a C₁ to C₂₀ alkylsilyl group, a silyl (C₁ to C₂₀ ) C₂₀₎ alkyl, halo (C₁ ~ C₂₀₎ alkyl group, a C aryl group of_{6 ~ C 20, (C 6} ~ C 20) aryl (C₁ ~ C₂₀₎ alkyl, (C₁ ~ C₂₀₎ alkyl ( (C₆ -C₂₀ ) aryl group, a (C₆ -C₂₀ ) arylsilyl group, a silyl (C₆ -C₂₀ ) aryl group, and a halogen group, or The adjacent substituents may combine with each other to form a ring.

여기서, 상기 C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 실릴(C₁~C₂₀)알킬기, 할로(C₁~C₂₀)알킬기의 비제한적인 예로는 메틸(Methyl)기, 에틸(Ethyl)기, 프로필(Propyl)기, 부틸(Butyl)기, 펜틸(Pentyl)기, 헥실(Hexyl)기, 헵틸(Heptyl)기, 옥틸(Octyl)기, 노닐(Nonyl)기, 데실(Decyl)기, 시클로프로필(Cyclopropyl)기, 시클로부틸(Cyclobutyl)기, 시클로펜틸(Cyclopentyl)기, 시클로헥실(Cyclohexyl)기, 시클로옥틸(Cyclooctyl)기, 데카하이드로나프탈릴(Decahydronaphthalyl)기, 메틸실릴(Methylsilyl)기, 디메틸실릴(Dimethylsilyl)기, 트리메틸실릴(Trimethylsilyl)기, 에틸실릴(Ethylsilyl)기, 디에틸실릴(Diethylsilyl)기, 트리에틸실릴(Triethylsilyl)기, 프로필실릴(Propylsilyl)기, 디프로필실릴(Dipropylsilyl)기, 트리프로필실릴(Tripropylsilyl)기, 부틸실릴(Butylsilyl)기, 디부틸실릴 (Dibutylsilyl)기, 트리부틸실릴(Tributylsilyl)기, (메틸실릴)메틸[(Methylsilyl)methyl]기, (디메틸실릴)메틸[(Dimethylsilyl) methyl]기, (트리메틸실릴)메틸[(Trimethylsilyl)methyl]기, (에틸실릴)메틸[(Ethylsilyl)methyl]기, (디에틸실릴)메틸[(Dethylsilyl)methyl]기, (트리에틸실릴)메틸[(Triethylsilyl)methyl]기, (메틸실릴)에틸[(Methylsilyl)ethyl]기, (디메틸실릴)에틸[(Dimethylsilyl) ethyl]기, (트리메틸실릴)에틸[(Trimethylsilyl)ethyl]기, 트리플루오로메틸(Trifluoromethyl)기, 트리클로로메틸(Trichloromethyl)기 등이 있다.Here, the C₁ ~ C₂₀ alkyl group, C₁ ~ a C₂₀ cycloalkyl group, C₁ ~ alkyl silyl group of C_20, silyl (C₁ ~ C₂₀₎ alkyl, halo (C₁ ~ C₂₀₎ alkyl group of the Non-limiting examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, A cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, A decahydronaphthalyl group, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, A propylsilyl group, a dipropylsilyl group, a tripropylsilyl group, a butylsilyl group, a dibutylsilyl group, a tributylsilyl group, (Trimethylsilyl) methyl group, (ethylsilyl) methyl group, (methylsilyl) methyl group, (dimethylsilyl) methyl group, (Methylsilyl) methyl group, (diethylsilyl) methyl group, (triethylsilyl) methyl group, (methylsilyl) ethyl [(methylsilyl) ethyl] group, Silyl) ethyl [(Dimethylsilyl) ethyl] group, (trimethylsilyl) ethyl [(Trimethylsilyl) ethyl] group, trifluoromethyl group and trichloromethyl group.

또, 상기 C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, (C₆~C₂₀)아릴실릴기, 실릴(C₆~C₂₀)아릴기의 비제한적인 예로는 페닐(Phenyl)기, 바이페닐(Biphenyl)기, 터페닐(Terphenyl)기, 나프틸(Naphtyl)기, 플루오레닐(Fluorenyl)기, 벤질(Benzyl)기, 페닐에틸(Phenylethyl), 페닐프로필(Phenylpropyl)기, 메틸페닐(Methylphenyl)기, 디메틸페닐(Dimethylphenyl)기, 트리메틸페닐(Trimethylphenyl)기, 에틸페닐(Ethylphenyl)기, 디에틸페닐(Diethylphenyl)기, 트리에틸페닐(Triethylphenyl)기, 프로필페닐(Propylphenyl)기, 디프로필페닐(Dipropylphenyl)기, 트리프로필페닐(Tripropylphenyl)기, 페닐실릴(Phenylsilyl)기, 메틸페닐실릴(Methylphenylsilyl)기, 디메틸페닐실릴(Dimethylphenylsilyl)기, 메틸디페닐실릴(methyl(diphenyl)silyl), 트리페닐실릴(Triphenylsilyl)기, 에틸페닐실릴(Ethylphenylsilyl)기, (메틸페닐)실릴[(Methylphenyl)silyl]기, (에틸페닐)실릴[(Ethylphenyl)silyl]기, 트리플루오로메틸페닐실릴(Trifluoromethylphenylsilyl)기, (메틸실릴)페닐[(Methylsilyl)phenyl]기, (디메틸실릴)페닐[(Dimethylsilyl)phenyl]기, (트리메틸실릴)페닐[(Trimethylsilyl)phenyl]기, (에틸실릴)페닐[(Ethylsilyl)phenyl]기, (디에틸실릴)페닐[(Diethylsilyl)phenyl]기, (트리에틸실릴)페닐[(Triethylsilyl)phenyl]기, (프로필실릴)페닐[(Propylsilyl)phenyl]기, (디프로필실릴)페닐[(Dipropylsilyl)phenyl]기, (부틸실릴)페닐[(Butylsilyl) phenyl]기, (디부틸실릴)페닐[(Dibutylsilyl)phenyl]기 등이 있다.In addition, the aryl group of the_{C 6 ~ C 20, (C} 6 ~ C 20) aryl (C₁ ~ C₂₀₎ alkyl, (C₁ ~ C₂₀₎ alkyl (C₆ ~ C₂₀₎ aryl, (C₆ ~ C₂₀₎ aryl silyl group, a silyl group (C₆ ~ C₂₀₎ non-limiting examples of the aryl group are phenyl (phenyl) group, biphenyl (biphenyl) group, a terphenyl (terphenyl) group, a naphthyl (naphtyl) group , A fluorenyl group, a benzyl group, a phenylethyl group, a phenylpropyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, A diethylphenyl group, a diethylphenyl group, a triethylphenyl group, a propylphenyl group, a dipropylphenyl group, a tripropylphenyl group, a phenylsilyl group, , A methylphenylsilyl group, a dimethylphenylsilyl group, a methyl diphenyl silyl group, a triphenylsilyl group, an ethylphenylsilyl group, a (methylphenyl) silyl group, (Ethylphenyl) silyl] group, trifluoromethylphenylsilyl group, (methylsilyl) phenyl [(methylsilyl) phenyl] group, (dimethylsilyl) phenyl [ (Trimethylsilyl) phenyl group, (trimethylsilyl) phenyl group, (ethylsilyl) phenyl [(ethylsilyl) phenyl] group, (diethylsilyl) phenyl [ (Propylsilyl) phenyl] group, (dipropylsilyl) phenyl group, (butylsilyl) phenyl] group, , (Dibutylsilyl) phenyl [(Dibutylsilyl) phenyl] group and the like.

또, 상기 할로겐기의 예로는 플루오로(Fluoro)기, 클로로(Chloro)기, 브로모(Bromo)기, 요오도(Iodo)기 등이 있는데, 이에 한정되지 않는다.Examples of the halogen group include, but are not limited to, a fluoro group, a chloro group, a bromo group, and an iodo group.

상기 화학식 3에서, B는 전이금속 M³에 직접 배위하지 않고 리간드 Ar³ 및 Ar⁴를 연결하는 부분으로, 탄소(C), 규소(Si), 게르마늄(Ge), 질소(N) 및 인(P)으로 이루어진 군에서 선택되고; R¹은 수소, C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 실릴(C₁~C₂₀)알킬기, C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, (C₆~C₂₀)아릴실릴기 및 실릴(C₁~C₂₀)아릴기로 이루어진 군에서 선택되며; d는 B의 종류에 따라 달라지고, 1 또는 2이다.In the above formula (3), B is a moiety that does not directly coordinate to the transition metal M³ but connects the ligands Ar³ and Ar⁴ and is a moiety of carbon (C), silicon (Si), germanium (Ge), nitrogen P); R¹ is selected from the group consisting of hydrogen, a C₁ to C₂₀ alkyl group, a C₁ to C₂₀ cycloalkyl group, a C₁ to C₂₀ alkylsilyl group, a silyl (C₁ to C₂₀ ) alkyl group, a C₆ to C₂₀ aryl group (C₆ -C₂₀ ) aryl (C₁ -C₂₀ ) alkyl, (C₁ -C₂₀ ) alkyl (C₆ -C₂₀ ) aryl, (C₆ -C₂₀ ) arylsilyl and silyl₁ ~ C₂₀₎ is selected from the group consisting of an aryl group; d depends on the type of B and is 1 or 2.

여기서, 상기 R¹의 C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 및 실릴(C₁~C₂₀)알킬기의 비제한적인 예로는 메틸(Methyl)기, 에틸(Ethyl)기, 프로필(Propyl)기, 부틸(Butyl)기, 펜틸(Pentyl)기, 헥실(Hexyl)기, 헵틸(Heptyl)기, 옥틸(Octyl)기, 노닐(Nonyl)기, 데실(Decyl)기, 시클로프로필(Cyclopropyl)기, 시클로부틸(Cyclobutyl)기, 시클로펜틸(Cyclopentyl)기, 시클로헥실(Cyclohexyl)기, 시클로옥틸(Cyclooctyl)기, 데카하이드로나프탈릴(Decahydronaphthalyl)기, 메틸실릴(Methylsilyl)기, 디메틸실릴(Dimethylsilyl)기, 트리메틸실릴(Trimethylsilyl)기, 에틸실릴(Ethylsilyl)기, 디에틸실릴(Diethylsilyl)기, 트리에틸실릴(Triethylsilyl)기, 프로필실릴(Propylsilyl)기, 디프로필실릴(Dipropylsilyl)기, 트리프로필실릴(Tripropylsilyl)기, 부틸실릴(Butylsilyl)기, 디부틸실릴 (Dibutylsilyl)기, 트리부틸실릴(Tributylsilyl)기, (메틸실릴)메틸[(Methylsilyl)methyl]기, (디메틸실릴)메틸[(Dimethylsilyl) methyl]기, (트리메틸실릴)메틸[(Trimethylsilyl)methyl]기, (에틸실릴)메틸[(Ethylsilyl)methyl]기, (디에틸실릴)메틸[(Dethylsilyl)methyl]기, (트리에틸실릴)메틸[(Triethylsilyl)methyl]기, (메틸실릴)에틸[(Methylsilyl)ethyl]기, (디메틸실릴)에틸[(Dimethylsilyl) ethyl]기, (트리메틸실릴)에틸[(Trimethylsilyl)ethyl]기 등이 있다.Here, the alkyl silyl group of the R¹ of C₁ ~ C_20, C cycloalkyl group of_{1 ~ C 20, C 1 ~} C 20 group, and silyl (C₁ ~ C₂₀₎ Non-limiting examples of alkyl groups are methyl An alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, A decyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a decahydronaphthalyl group, A methylsilyl group, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a propylsilyl ( Propylsilyl group, a dipropylsilyl group, a tripropylsilyl group, a butylsilyl group, a dibutylsilyl group, a tributylsilyl group, (Dimethylsilyl) methyl group, (trimethylsilyl) methyl group, (ethylsilyl) methyl group, (ethylsilyl) methyl group, methylethyl group, (diethylsilyl) methyl group, (triethylsilyl) methyl group, (methylsilyl) ethyl [Methylsilyl] ethyl] group, (dimethylsilyl) ethyl [(Dimethylsilyl) ethyl] group, (trimethylsilyl) ethyl [(Trimethylsilyl) ethyl] group and the like.

또, 상기 R¹의 C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, (C₆~C₂₀)아릴실릴기 및 실릴(C₁~C₂₀)아릴기의 비제한적인 예로는 페닐(Phenyl)기, 바이페닐(Biphenyl)기, 터페닐(Terphenyl)기, 나프틸(Naphtyl)기, 플루오레닐(Fluorenyl)기, 벤질(Benzyl)기, 페닐에틸(Phenylethyl), 페닐프로필(Phenylpropyl)기, 메틸페닐(Methylphenyl)기, 디메틸페닐(Dimethylphenyl)기, 트리메틸페닐(Trimethylphenyl)기, 에틸페닐(Ethylphenyl)기, 디에틸페닐(Diethylphenyl)기, 트리에틸페닐(Triethylphenyl)기, 프로필페닐(Propylphenyl)기, 디프로필페닐(Dipropylphenyl)기, 트리프로필페닐(Tripropylphenyl)기, 페닐실릴(Phenylsilyl)기, 메틸페닐실릴(Methylphenylsilyl)기, 디메틸페닐실릴(Dimethylphenylsilyl)기, 메틸디페닐실릴(methyl(diphenyl)silyl), 트리페닐실릴(Triphenylsilyl)기, 에틸페닐실릴(Ethylphenylsilyl)기, (메틸페닐)실릴[(Methylphenyl)silyl]기, (에틸페닐)실릴[(Ethylphenyl)silyl]기, 트리플루오로메틸페닐실릴(Trifluoromethylphenylsilyl)기, (메틸실릴)페닐[(Methylsilyl)phenyl]기, (디메틸실릴)페닐[(Dimethylsilyl)phenyl]기, (트리메틸실릴)페닐[(Trimethylsilyl)phenyl]기, (에틸실릴)페닐[(Ethylsilyl)phenyl]기, (디에틸실릴)페닐[(Diethylsilyl)phenyl]기, (트리에틸실릴)페닐[(Triethylsilyl)phenyl]기, (프로필실릴)페닐[(Propylsilyl)phenyl]기, (디프로필실릴)페닐[(Dipropylsilyl)phenyl]기, (부틸실릴)페닐[(Butylsilyl) phenyl]기, (디부틸실릴)페닐[(Dibutylsilyl)phenyl]기 등이 있다.The aryl group of C₆ ~ C₂₀ of the_{^{R 1, (C 6 ~ C}} 20) aryl (C₁ ~ C₂₀₎ alkyl, (C₁ ~ C₂₀₎ alkyl (C₆ ~ C₂₀₎ aryl group, (C₆ -C₂₀ ) arylsilyl group and a silyl (C₁ -C₂₀ ) aryl group include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group A naphthyl group, a fluorenyl group, a benzyl group, a phenylethyl group, a phenylpropyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group , An ethylphenyl group, a diethylphenyl group, a triethylphenyl group, a propylphenyl group, a dipropylphenyl group, a tripropylphenyl group, a phenylsilyl group (Methylphenylsilyl) group, a methylphenylsilyl group, a methylphenylsilyl group, a methylphenylsilyl group, a triphenylsilyl group, an ethylphenylsilyl group, a methyl (Methylphenyl) silyl group, (ethylphenyl) silyl group, trifluoromethylphenylsilyl group, (methylsilyl) phenyl group, (dimethylsilyl) Phenyl group, (trimethylsilyl) phenyl group, (ethylsilyl) phenyl group, (diethylsilyl) phenyl group, (Triethylsilyl) phenyl group, (propylsilyl) phenyl [(propylsilyl) phenyl] group, (dipropylsilyl) phenyl group, (butylsilyl) phenyl [ phenyl] group, (dibutylsilyl) phenyl [(Dibutylsilyl) phenyl] group and the like.

상기와 같은 제3 메탈로센 촉매 화합물의 비제한적인 예로, rac-에틸렌비스(1-인데닐)지르코늄 디클로라이드, rac-에틸렌비스(1-인데닐)하프늄 디클로라이드, rac-에틸렌비스(1-테트라하이드로-인데닐)지르코늄 디클로라이드, rac-에틸렌비스(1-테트라하이드로-인데닐)하프늄 디클로라이드, rac-디메틸실란디일비스(2-메틸-테트라하이드로벤즈인데닐)지르코늄 디클로라이드, rac-디메틸실란디일비스(2-메틸-테트라하이드로벤즈인데닐)하프늄 디클로라이드, rac-디페닐실란디일비스(2-메틸-테트라하이드로벤즈인데닐)지르코늄 디클로라이드, rac-디페닐실란디일비스(2-메틸-테트라하이드로벤즈인데닐)하프늄 디클로라이드, rac-디메틸실란디일비스(2-메틸-4,5-벤즈인데닐)지르코늄 디클로라이드, rac-디메틸실란디일비스(2-메틸-4,5-벤즈인데닐)하프늄 디클로라이드, rac-디페닐실란디일비스(2-메틸-4,5-벤즈인데닐)지르코늄 디클로라이드, rac-디페닐실란디일비스(2-메틸-4,5-벤즈인데닐)하프늄 디클로라이드, rac-디메틸실란디일비스(2-메틸-5,6-시클로펜타디에닐인데닐)지르코늄 디클로라이드, rac-디메틸실란디일비스 (2-메틸-5,6-시클로펜타디에닐인데닐)하프늄 디클로라이드, rac-디페닐실란디일비스(2-메틸-5,6-시클로펜타디에닐인데닐)지르코늄 디클로라이드, rac-디페닐실란디일비스(2-메틸-5,6-시클로펜타디에닐인데닐)하프늄 디클로라드, 이드, rac-디메틸실릴비스(2-메틸-4-페닐인데닐)지르코늄 디클로라이드, rac-디메틸실릴비스(2-메틸-4-페닐인데닐)하프늄 디클로라이드, rac-디페닐실릴비스(2-메틸-4-페닐인데닐)지르코늄 디클로라이드, rac-디페닐실릴비스(2-메틸-4-페닐인데닐)하프늄 디클로라이드, 이소-프로필리덴(시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 이소-프로필리덴(시클로펜타디에닐)(9-플루오레닐)하프늄 디클로라이드, 디페닐메틸리덴(시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 디페닐메틸리덴(시클로펜타디에닐)(9-플루오레닐)하프늄 디클로라이드, 이소-프로필리덴(3-메틸시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 이소-프로필리덴(3-메틸시클로펜타디에닐)(9-플루오레닐)하프늄 디클로라이드, 디페닐메틸리덴(3-메틸시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 디페닐메틸리덴(3-메틸시클로펜타디에닐)(9-플루오레닐)하프늄 디클로라이드, 디페닐실릴(시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 디페닐실릴(시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 디페닐메틸리덴(시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)지르코늄 디클로라이드, 디페닐메틸리덴(시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 디페닐메틸리덴(3-터트-부틸시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)지르코늄 디클로라이드, 디페닐메틸리덴(3-터트-부틸시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 디페닐메틸리덴(3-터트-부틸-5-메틸시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)지르코늄 디클로라이드, 디페닐메틸리덴(3-터트-부틸-5-메틸시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 1,2-에틸렌비스(9-플루오레닐)지르코늄 디클로라이드, 1,2-에틸렌비스(9-플루오레닐)하프늄 디클로라이드, rac-[1,2-비스(9-플루오레닐)-1-페닐-에탄]지르코늄 디클로라이드, rac-[1,2-비스(9-플루오레닐)-1-페닐-에탄]하프늄 디클로라이드, [1-(9-플루오레닐)-2-(5,6-시클로펜타-2-메틸-1-인데닐)-에탄]지르코늄 디클로라이드, [1-(9-플루오레닐)-2-(5,6-시클로펜타-2-메틸-1-인데닐)-에탄]하프늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-페닐-테트라하이드로펜타렌]지르코늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-페닐-테트라하이드로펜타렌]하프늄 디클로라이드, 이소-프로필리덴(2-페닐-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 이소-프로필리덴(2-페닐-시클로펜타디에닐)(9-플루오레닐)하프늄 디클로라이드, 디페닐메틸리덴(2-페닐-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 디페닐메틸리덴(2-페닐-시클로펜타디에닐)(9-플루오레닐)하프늄 디클로라이드, 이소프로필리덴(2-페닐-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)지르코늄 디클로라이드, 이소프로필리덴(2-페닐-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 디페닐메틸리덴(2-페닐-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)지르코늄 디클로라이드, 디페닐메틸리덴(2-페닐-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(p-톨릴)-테트라하이드로펜타렌]지르코늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(p-톨릴)-테트라하이드로펜타렌]하프늄 디클로라이드, [이소프로필리덴-(2-(p-톨릴)-시클로펜타디에닐)-(9-플루오레닐)]지르코늄 디클로라이드, [이소프로필리덴-(2-(p-톨릴)-시클로펜타디에닐)-(9-플루오레닐)]하프늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(m-톨릴)-테트라하이드로펜타렌]지르코늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(m-톨릴)-테트라하이드로펜타렌]하프늄 디클로라이드, [이소프로필리덴(2-(m-톨릴)-시클로펜타디에닐)-(9-플루오레닐)]지르코늄 디클로라이드, [이소프로필리덴(2-(m-톨릴)-시클로펜타디에닐)-(9-플루오레닐)]하프늄 디클로라이드, [디페닐메틸리덴(2-(m-톨릴)-시클로펜타디에닐)-(9-플루오레닐)]지르코늄 디클로라이드, [디페닐메틸리덴(2-(m-톨릴)-시클로펜타디에닐)-(9-플루오레닐)]하프늄 디클로라이드, [이소프로필리덴(2-(m-톨릴)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)]지르코늄 디클로라이드, [이소프로필리덴(2-(m-톨릴)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)]하프늄 디클로라이드, [디페닐메틸리덴(2-(m-톨릴)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)]지르코늄 디클로라이드, [디페닐메틸리덴(2-(m-톨릴)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)]하프늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(o-톨릴)-테트라하이드로펜타렌]지르코늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(o-톨릴)-테트라하이드로펜타렌]하프늄 디클로라이드, [이소프로필리덴(2-(o-톨릴)-시클로펜타디에닐)(9-플루오레닐)]지르코늄 디클로라이드, [이소프로필리덴(2-(o-톨릴)-시클로펜타디에닐)(9-플루오레닐)]하프늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(2,3-디메틸페닐)-테트라하이드로펜타렌]지르코늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(2,3-디메틸페닐)-테트라하이드로펜타렌]하프늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(2,4-디메틸페닐)-테트라하이드로펜타렌]지르코늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(2,4-디메틸페닐)-테트라하이드로펜타렌]지르코늄디클로라이드, [이소프로필리덴(2-(2,3-디메틸페닐)-시클로펜타디에닐)(9-플루오레닐)]지르코늄 디클로라이드, [이소프로필리덴(2-(2,3-디메틸페닐)-시클로펜타디에닐)(9-플루오레닐)]하프늄 디클로라이드, [이소프로필리덴(2-(2,4-디메틸페닐)-시클로펜타디에닐)(9-플루오레닐)]지르코늄 디클로라이드, [이소프로필리덴(2-(2,3-디메틸페닐)-시클로펜타디에닐)(9-플루오레닐)]하프늄 디클로라이드, [디페닐메틸리덴(2-(2,3-디메틸페닐)-시클로펜타디에닐)(9-플루오레닐)]지르코늄 디클로라이드, [디페닐메틸리덴(2-(2,3-디메틸페닐)-시클로펜타디에닐)(9-플루오레닐)]하프늄 디클로라이드, [디페닐메틸리덴(2-(2,4-디메틸페닐)-시클로펜타디에닐)(9-플루오레닐)]지르코늄 디클로라이드, [디페닐메틸리덴(2-(2,4-디메틸페닐)-시클로펜타디에닐)(9-플루오레닐)]하프늄 디클로라이드, [이소프로필리덴(2-(2,3-디메틸페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)]지르코늄 디클로라이드, [이소프로필리덴(2-(2,3-디메틸페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)]하프늄 디클로라이드, [이소프로필리덴(2-(2,4-디메틸페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)]지르코늄 디클로라이드, [이소프로필리덴(2-(2,4-디메틸페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)]하프늄 디클로라이드, [디페닐메틸리덴(2-(2,3-디메틸페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)]지르코늄 디클로라이드, [디페닐메틸리덴(2-(2,3-디메틸페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)]하프늄 디클로라이드, [디페닐메틸리덴(2-(2,4-디메틸페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)]지르코늄 디클로라이드, [디페닐메틸리덴(2-(2,4-디메틸 페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)]하프늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(2,6-디메틸페닐)-테트라하이드로펜타렌]지르코늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(2,6-디메틸페닐)-테트라하이드로펜타렌]하프늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(3,5-디메틸페닐)-테트라하이드로펜타렌]지르코늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(3,5-디메틸페닐)-테트라하이드로펜타렌]하프늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-테트라메틸페닐-테트라하이드로펜타렌]지르코늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-테트라메틸페닐-테트라하이드로펜타렌]하프늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(2,4-디메톡시페닐)-테트라하이드로펜타렌]지르코늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(2,4-디메톡시페닐)-테트라하이드로펜타렌]하프늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(3,5-디메톡시페닐)-테트라하이드로펜타렌]지르코늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(3,5-디메톡시페닐)-테트라하이드로펜타렌]하프늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(클로로페닐)-테트라하이드로펜타렌]지르코늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(클로로페닐)-테트라하이드로펜타렌]하프늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(플루오로페닐)-테트라하이드로펜타렌]지르코늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(플루오로페닐)-테트라하이드로펜타렌]하프늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(디플루오로페닐)-테트라하이드로펜타렌]지르코늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(디플루오로페닐)-테트라하이드로펜타렌]하프늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리 메틸-2-(펜타플루오로페닐)-테트라하이드로펜타렌]지르코늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(디플루오로페닐)-테트라하이드로펜타렌]하프늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(터트-부틸-페닐)-테트라하이드로펜타렌]하프늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(3,5-트리플루오로메틸-페닐)-테트라하이드로펜타렌]지르코늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(3,5-트리플루오로메틸-페닐)-테트라하이드로펜타렌]하프늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(3,5-디-터트-부틸페닐)테트라하이드로펜타렌]지르코늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(3,5-디-터트-부틸페닐)테트라하이드로펜타렌]하프늄디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(비페닐)-테트라하이드로펜타렌]지르코늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(비페닐)-테트라하이드로펜타렌]하프늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-나프틸-테트라하이드로펜타렌]지르코늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-나프틸-테트라하이드로펜타렌]하프늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(3,5-디페닐-페닐)-테트라하이드로펜타렌]지르코늄 디클로라이드, [4-(플루오레닐)-4,6,6-트리메틸-2-(3,5-디페닐-페닐)-테트라하이드로펜타렌]하프늄 디클로라이드, 이소프로필리덴(2-테트라메틸페닐-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 이소프로필리덴(2-(2,6-디메틸페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 이소프로필리덴(2-(3,5-디메틸페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 이소프로필리덴(2-(2,4-디메톡시페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 이소프로필리덴(2-(3,5-디메톡시페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 이소프로필리덴(2-(2,3-디메톡시페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 이소프로필리덴(2-(2,6-디메톡시페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 이소프로필리덴(2-(클로로페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 이소프로필리덴(2-(디클로로페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 이소프로필리덴(2-(트리클로로페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 이소프로필리덴(2-(플루오로페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 이소프로필리덴(2-(디플루오로페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 이소프로필리덴(2-(펜타플루오로페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 이소프로필리덴(2-(3,5-트리플루오로메틸-페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 이소프로필리덴(2-(터트-부틸페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 이소프로필리덴(2-(3,5-디-터트-부틸페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 이소프로필리덴(2-(비페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 이소프로필리덴(2-(3,5-디페닐-페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 이소프로필리덴(2-나프틸-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 디페닐메틸리덴(2-테트라메틸페닐-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 디페닐메틸리덴(2-(2,6-디메틸페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디 클로라이드, 디페닐메틸리덴(2-(3,5-디메틸페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 디페닐메틸리덴(2-(2,4-디메톡시페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 디페닐메틸리덴(2-(3,5-디메톡시페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 디페닐메틸리덴(2-(2,3-디메톡시페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 디페닐메틸리덴(2-(2,6-디메톡시페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 디페닐메틸리덴(2-(클로로페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 디페닐메틸리덴(2-(디클로로페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 디페닐메틸리덴(2-(트리클로로페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 디페닐메틸리덴(2-(플루오로페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 디페닐메틸리덴(2-(디플루오로페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 디페닐메틸리덴(2-(펜타플루오로페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 디페닐메틸리덴(2-(3,5-트리플루오로메틸-페닐)-시클로펜타디에닐)(9-플루 오레닐)지르코늄 디클로라이드, 디페닐메틸리덴(2-(터트-부틸페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 디페닐메틸리덴(2-(3,5-디-터트-부틸페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 디페닐메틸리덴(2-(비페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 디페닐메틸리덴(2-(3,5-디페닐-페닐)-시클로펜타디에닐)(9-플루오레닐)지르코늄 디클로라이드, 디페닐메틸리덴(2-나프틸-시클로펜타디에닐)(9-플루오레닐)지르코늄디클로라이드, 이소프로필리덴(2-테트라메틸페닐-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 이소프로필리덴(2-(2,6-디메틸페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 이소프로필리덴(2-(3,5-디메틸페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 이소프로필리덴(2-(2,4-디메톡시페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄디클로라이드, 이소프로필리덴(2-(3,5-디메톡시페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄디클로라이드, 이소프로필리덴(2-(2,3-디메톡시페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄디클로라이드, 이소프로필리덴(2-(2,6-디메톡시페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄디클로라이드, 이소프로필리덴(2-(클로로페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 이소프로필리덴(2-(디클로로페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 이소프로필리덴(2-(트리클로로페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 이소프로필리덴(2-(플루오로페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 이소프로필리덴(2-(디플루오로페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 이소프로필리덴(2-(펜타플루오로 페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 이소프로필리덴(2-(3,5-트리플루오로메틸-페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 이소프로필리덴(2-(터트-부틸페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 이소프로필리덴(2-(3,5-디-터트-부틸페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 이소프로필리덴(2-(비페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 이소프로필리덴(2-(3,5-디페닐-페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 이소프로필리덴(2-나프틸-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 디페닐메틸리덴(2-테트라메틸페닐-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 디페닐메틸리덴(2-(2,6-디메틸 페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 디페닐메틸리덴(2-(3,5-디메틸페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 디페닐메틸리덴(2-(2,4-디메톡시페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 디페닐메틸리덴(2-(3,5-디메톡시페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 디페닐메틸리덴(2-(2,3-디메톡시페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 디페닐메틸리덴(2-(2,6-디메톡시페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 디페닐메틸리덴(2-(클로로페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 디페닐메틸리덴(2-(디클로로페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 디페닐메틸리덴(2-(트리클로로페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 디페닐메틸리덴(2-(플루오로페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 디페닐메틸리덴(2-(디플루오로페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 디페닐메틸리덴(2-(펜타플루오로페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 디페닐메틸리덴(2-(3,5-트리플루오로메틸-페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 디페닐메틸리덴(2-(터트-부틸페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 디페닐메틸리덴(2-(3,5-디-터트-부틸페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 디페닐메틸리덴(2-(비페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 디페닐메틸리덴(2-(3,5-디페닐-페닐)-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드, 디페닐메틸리덴(2-나프틸-시클로펜타디에닐)(2,7-디-터트-부틸플루오렌-9-일)하프늄 디클로라이드 등이 있다.Ethylene bis (1-indenyl) hafnium dichloride, rac-ethylene bis (1-indenyl) zirconium dichloride, rac-ethylene bis Tetrahydroindenyl) zirconium dichloride, rac-ethylene bis (1-tetrahydroindenyl) hafnium dichloride, rac-dimethylsilanediylbis (2-methyl-tetrahydrobenzindenyl) zirconium dichloride, (2-methyl-tetrahydrobenzenylidene) hafnium dichloride, rac-diphenylsilandiylbis (2-methyl-tetrahydrobenzenylenyl) zirconium dichloride, rac-diphenylsilyl (2-methyl-tetrahydrobenzenylidene) hafnium dichloride, rac-dimethylsilanediylbis (2-methyl-4,5-benzindenyl) zirconium dichloride, rac-dimethylsilanediylbis 2-methyl-4,5-benzindenyl) hafnium dichloride, (2-methyl-4,5-benzindenyl) zirconium dichloride, rac-diphenylsilandiylbis (2-methyl-4,5-benzindenyl) hafnium dichloride, (2-methyl-5,6-cyclopentadienylindenyl) zirconium dichloride, rac-dimethylsilanediylbis (2-methyl-5,6-cyclopentadienylindenyl) Diphenylsilanediylbis (2-methyl-5,6-cyclopentadienylindenyl) zirconium dichloride, rac-diphenylsilandiylbis (2-methyl-5,6-cyclo Dimethyl-silylbis (2-methyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylbis (2-methyl-4- phenylindenyl) hafnium dichloride, (2-methyl-4-phenylindenyl) zirconium dichloride, rac-diphenylsilylbis (2-methyl-4-phenylindenyl) hafnium dichloride, isopropylidene Sycelle (9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (9-fluorenyl) hafnium dichloride, diphenylmethylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (cyclopentadienyl) (9-fluorenyl) hafnium dichloride, iso-propylidene (3-methylcyclopentadienyl) (3-methylcyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (3-methylcyclopentadienyl) (9-fluorenyl) zirconium dichloride (Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylsilyl (cyclopentadienyl) zirconium dichloride, diphenylmethylidene (3-methylcyclopentadienyl) Pentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2,7-di-tert-butylfluoren-9-yl) zirconium dichloride, diphenylmethylidene (cyclopentadienyl) (2,7- Zirconium dichloride, diphenylmethylidene (3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) zirconium dichloride, diphenylmethylidene (3- Butyl-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (3-tert- butyl-5-methylcyclopentadienyl) Di-tert-butylfluorene-9-yl) zirconium dichloride, diphenylmethylidene (3-tert- butyl-5-methylcyclopentadienyl) (2,7- (9-fluorenyl) zirconium dichloride, 1,2-ethylenebis (9-fluorenyl) hafnium dichloride, rac- [1,2- Bis (9-fluorenyl) -1-phenyl-ethane] zirconium dichloride, rac- [ Phenyl-ethane] hafnium dichloride, [1- (9-fluorenyl) -2- (5,6-cyclopenta-2-methyl-1-indenyl) Ethane] zirconium dichloride, [1- (9-fluorenyl) -2- (5,6-cyclopenta-2-methyl- ) -4,6,6-trimethyl-2-phenyl-tetrahydropentene] zirconium dichloride, [4- (fluorenyl) (2-phenyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, iso-propylidene (2-phenyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2-phenyl-cyclopentadienyl) (9-fluorenyl) hafnium (2-phenyl-cyclopentadienyl) Dichloride, isopropylidene (2-phenyl-cyclopentadienyl) (2,7-di Zirconium dichloride, isopropylidene (2-phenyl-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, di Cyclopentadienyl) (2-phenyl-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) zirconium dichloride, diphenylmethylidene (7-di-tert-butylfluoren-9-yl) hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- 2- (p- tolyl) -tetrahydropentrene] zirconium (2- (p-tolyl) -tetrahydrofuran] hafnium dichloride, [isopropylidene- (2- (p- tolyl) Cyclopentadienyl) - (9-fluorenyl)] zirconium dichloride, [isopropylidene- (2- (p-tolyl) -cyclopentadienyl) - (9- , [4- (fluorenyl) -4,6,6-trimethyl-2- (m-tolyl) -tetrahydropentrene] (2- (m-tolyl) -tetrahydrofuran] hafnium dichloride, [isopropylidene (2- (m-tolyl) Cyclopentadienyl) - (9-fluorenyl)] zirconium dichloride, [isopropylidene (2- (m-tolyl) -cyclopentadienyl) - (9- [Diphenylmethylidene (2- (m-tolyl) -cyclopentadienyl) - (9-fluorenyl)] zirconium dichloride, [diphenylmethylidene (2- ) - (9-fluorenyl)] hafnium dichloride, [isopropylidene (2- (m-tolyl) -cyclopentadienyl) (2,7- Zirconium dichloride, [isopropylidene (2- (m-tolyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] hafnium dichloride, [diphenylmethylidene (2,7-di-tert-butylfluoren-9-yl)] zirconium dichloride, 2- (m-tolyl) -cyclopentadienyl) [Diphenylmethylidene (2- (m-tolyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] hafnium dichloride, [4- (fluorenyl) (O-tolyl) -tetrahydro-pentalene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- 2- (Isopropylidene (2- (o-tolyl) -cyclopentadienyl) (9-fluorenyl)] zirconium dichloride, [isopropylidene ) -Cyclopentadienyl) (9-fluorenyl)] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- 2- (2,3-dimethylphenyl) -tetrahydropenta (4-fluorenyl) -4,6,6-trimethyl-2- (2,3-dimethylphenyl) -tetrahydropentrene] hafnium dichloride, [4- (fluorenyl) ) -4,6,6-trimethyl-2- (2,4-dimethylphenyl) -tetrahydro-pentalene] zirconium dichloride, [4- (fluorenyl) (2,4-dimethylphenyl) -tetrahydro-pentalene] zirconium dichloride, [isopropylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl) (9- )] Zirconium dichloride, [isopropylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl) (9-fluorenyl)] hafnium dichloride, [isopropylidene (2- (9-fluorenyl) zirconium dichloride, [isopropylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl) (9-fluorenyl)] zirconium dichloride, Zirconium dichloride, [diphenylmethylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl) (9-fluorenyl)] zirconium dichloride, Cyclopentadienyl) (9-fluorenyl)] hafnium dichloride, [diphenylmethylidene (2- (2,4-dimethylphenyl) -cyclopentadienyl) Yl)] zirconium dichloride, [diphenylmethylidene (2- (2,4-dimethoxyphenyl) Phenyl) -cyclopentadienyl) (9-fluorenyl)] hafnium dichloride, [isopropylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl) (2,7- Yl)] zirconium dichloride, [isopropylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren- )] Zirconium dichloride, [isopropylidene (2- (2,4-dimethylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] zirconium dichloride, Diphenylmethylidene (2- (2,4-dimethylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] hafnium dichloride, (2,3-dimethylphenyl) cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] zirconium dichloride, diphenylmethylidene (2- Phenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] hafnium dichloride, diphenylmethylidene (2- (2,4- Cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] zirconium dichloride, diphenylmethylidene (2- (2,4- Yl)] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (2,6-dimethylphenyl) ) - tetrahydropentalene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (2,6- dimethylphenyl) -tetrahydropentrene] hafnium dichloride, [4 - (fluorenyl) -4,6,6-trimethyl-2- (3,5-dimethylphenyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) Tetramethylphenyl) tetrahydropentene] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2-tetramethylphenyl-tetrahydropentrene] zirconium Tetramethylphenyl-tetrahydropentene] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (2,4-dimethoxyphenyl) -tetrahydro-pentalene] zirconium dichloride, [4- (fluorenyl) -4 (3, 6-trimethyl-2- (2,4-dimethoxyphenyl) -tetrahydropentrene] hafnium dichloride, [4- (fluorenyl) Dimethoxyphenyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (3,5- (Fluorenyl) -4,6,6-trimethyl-2- (chlorophenyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) 2- (fluorophenyl) -tetrahydro-pentalene] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- 2- (fluorophenyl) Zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (fluorophenyl) -tetrahydropentrene] half (Fluorenyl) -4,6-dimethyl-2- (difluorophenyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) (6-trimethyl-2- (difluorophenyl) -tetrahydropentrene] hafnium dichloride, [4- (fluorenyl) -4,6,6- Tetrafluoroethylene) hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (difluorophenyl) -tetrahydroperfluorene] zirconium dichloride, [4- (Trifluoromethyl) -4,6,6-trimethyl-2- (tert-butyl-phenyl) -tetrahydro-pentalene] hafnium dichloride, [4- (fluorenyl) Trifluoromethyl-phenyl) -tetrahydro-pentalene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- 2- (3,5- Phenyl) -tetrahydropentrene] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (3,5- (Tert-butylphenyl) tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- Tetrafluoropentene] zirconium dichloride, [4- (fluorenyl) -4,6-dimethyl-2- , 6-trimethyl-2- (biphenyl) -tetrahydropertentalene] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2-naphthyl-tetrahydropentalene] zirconium di (Fluorenyl) -4,6,6-trimethyl-2-naphthyl-tetrahydropentene] hafnium dichloride, [4- (fluorenyl) 2- (3,5-diphenyl-phenyl) -tetrahydropentrene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl- ) -Tetrahydropentrene] hafnium dichloride, isopropylidene (2-tetramethylphenyl-cyclopentadiene Zirconium dichloride, isopropylidene (2- (2,6-dimethylphenyl) cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (9-fluorenyl) zirconium dichloride, isopropylidene (2- (2,4-dimethoxyphenyl) -cyclopentadienyl) (9-fluorenyl) Zirconium dichloride, isopropylidene (2- (2,3-dimethoxyphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (2,6-dimethoxyphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (dichlorophenyl) -cyclopentadienyl) (9- Cyclopentadienyl) zirconium dichloride, isopropylidene (2- (fluorophenyl) -cyclopentene) zirconium dichloride, isopropylidene (2- (trichlorophenyl) Dienyl) zirconium dichloride, isopropylidene (2- (difluorophenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- Fluorophenyl) cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (3,5-trifluoromethyl-phenyl) -cyclopentadienyl) Zirconium dichloride, isopropylidene (2- (3,5-di-tert-butylphenyl) -cyclopentadienyl) zirconium dichloride, isopropylidene -Butylphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (biphenyl) -cyclopentadienyl ) (9-fluorenyl) zirconium dichloride, isopropylidene (2 (3,5-diphenyl-phenyl) -cyclopentadienyl) Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2-tetramethylphenyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (3,5-dimethylphenyl) -cyclopentadienyl) ( Zirconium dichloride, diphenylmethylidene (2- (2,4-dimethoxyphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (2,3-dimethoxyphenyl) -cyclopentadienyl) (9 - Fluorine Zirconium dichloride, diphenylmethylidene (2- (2,6-dimethoxyphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (dichlorophenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (fluorophenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (pentafluorophenyl) -cyclopentadienyl) (9- fluorenyl) zirconium dichloride, diphenylmethylidene (2- (3,5-trifluoromethyl-phenyl) -cyclopentadienyl) Zirconium dichloride, diphenylmethylidene (2- (tert-butylphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (biphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride , Diphenylmethylidene (2- (3,5-diphenyl-phenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2-naphthyl-cyclopentadienyl) (2-tetramethylphenyl-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene ( (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (3,5-dimethylphenyl) -cyclopentadienyl) ) - cyclopentadienyl (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (2,4-dimethoxyphenyl) -cyclopentadienyl) 9-yl) hafnium dichloride, isopropylidene (2- (3,5-dimethoxyphenyl) -cyclopentadienyl) (2,7-di-tert- butylfluorene- (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (2,3-dimethoxyphenyl) -cyclopentadienyl) (2,6-dimethoxyphenyl) cyclopentadienyl) (2,7-di-tert-butylfluoren-9- yl) hafnium dichloride, isopropylidene (2- (chlorophenyl) Cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (dichlorophenyl) (Tert-butylfluorene-9-yl) hafnium dichloride, isopropylidene (2- (trichlorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (fluorophenyl) -cyclopentadienyl) -9-yl) hafnium dichloride, isopropylidene (2- (difluorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropyl (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (3,5-trifuorophenyl) cyclopentadienyl) Cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (tert- butylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluorene-9-yl) hafnium dichloride, isopropylidene (2- (3,5- Di-tert-butylfluorene-9-yl) hafnium dichloride, isopropylidene (2- (biphenyl) Phenyl) -cyclopentadienyl) (2, 3-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2-naphthyl-cyclopentadienyl) Diphenylmethylidene (2-tetramethylphenyl-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (Dimethylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (3,5-dimethylphenyl) Yl) hafnium dichloride, diphenylmethylidene (2- (2,4-dimethoxyphenyl) -cyclopentadienyl) (2,7- di- Di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (3,5-dimethoxyphenyl) Yl) hafnium dichloride, diphenylmethylidene (2- (2,3-dimethoxyphenyl) -cyclopentadienyl) (2,7- di- Di-tert-butylfluorene-9-yl) hafnium dichloride, diphenylmethylidene (2- (2,6- dimethoxyphenyl) -cyclopentadienyl) -9-yl) hafnium dichloride, diphenylmethylidene (2- (chlorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethyl Diphenylmethylidene (2- (trichlorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9- (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (fluorophenyl) -cyclopentadienyl) -Butylfluorene-9-yl) hafnium dichloride, diphenylmethylidene (2- (difluorophenyl) -cyclopentadienyl (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (pentafluorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluorene-9-yl) hafnium dichloride, diphenylmethylidene (2- (3,5- trifluoromethyl- phenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (tert- butylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2 (3,5-di- tert- butylphenyl) cyclopentadienyl) Diphenyl-phenyl) - (cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- Cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2-naphthyl- ) (2,7-di-butyl and the like fluoren-9-yl) hafnium dichloride - tert.

(b) 조촉매 화합물(b) a co-catalyst compound

본 발명에 따른 올레핀 중합용 담지 촉매는 조촉매 화합물을 포함한다. 상기 조촉매 화합물은 전술한 주촉매 화합물(a)과 함께 담체에 담지되어 상기 주촉매 화합물을 활성화시키는 역할을 한다. 따라서, 본 발명에 따른 담지 촉매의 활성을 저하시키지 않으면서 상기 주촉매 화합물을 활성화시킬 수 있는 조촉매 화합물이라면 그 구성에 제한없이 사용될 수 있다.The supported catalyst for olefin polymerization according to the present invention comprises a cocatalyst compound. The promoter compound is supported on the carrier together with the main catalyst compound (a) to activate the main catalyst compound. Therefore, the catalyst can be used without limitation as long as it is a promoter compound capable of activating the main catalyst compound without lowering the activity of the supported catalyst according to the present invention.

다만, 상기 조촉매 화합물(b)로 (ⅰ) 알루미녹산 화합물, (ⅱ) 유기알루미늄 화합물, 및 (ⅲ) 메탈로센 촉매 화합물과 반응하여 메탈로센 촉매 화합물이 촉매 활성을 갖게 하는 벌키한 화합물로 이루어진 군으로부터 선택되는 것이 바람직하다. 이러한 조촉매 화합물은 주촉매 화합물을 활성화시킬 뿐만 아니라, 주촉매 화합물 중에서 제1 메탈로센 촉매 화합물과의 상호 작용을 통해 올레핀 중합체의 분자량 분포를 넓힐 수 있다.However, it is preferable that the co-catalyst compound (b) is reacted with (i) an aluminoxane compound, (ii) an organoaluminum compound, and (iii) a metallocene catalyst compound to produce a bulky compound &Lt; / RTI &gt; Such a co-catalyst compound not only activates the main catalyst compound, but also can broaden the molecular weight distribution of the olefin polymer through interaction with the first metallocene catalyst compound in the main catalyst compound.

구체적으로, 본 발명의 제1 메탈로센 촉매 화합물은 조촉매 화합물과 상호 작용을 할 수 있는 헤테로 원자-함유 작용기를 갖고 있는데, 이는 Lewis base로 조촉매에서 Lewis acid 성질을 갖는 알루미늄 등의 금속 자리와 부분적인 배위결합을 하고, 이로 인해 제1 메탈로센 촉매 화합물의 시클로펜타디에닐 골격-함유 리간드는 느리게 회전한다. 이로써, 단일 활성자리를 갖는 다른 메탈로센 촉매 화합물과 달리, 본 발명의 제1 메탈로센 촉매 화합물은 다중 활성자리를 갖는다. 이로 인해, 본 발명의 담지 촉매를 이용하여 올레핀 중합체를 제조할 경우, 넓은 분자량 분포를 갖는 올레핀 중합체가 제조될 수 있다. 이러한 제1 메탈로센 촉매 화합물과 조촉매 화합물 간의 상호작용 효과는 상기 조촉매 화합물이 벌키할수록 효과가 커지며, 예컨대 벌키한 올리고머 형태로 알려진 알루미녹산 화합물의 경우 최대 효과를 발휘할 수 있다.Specifically, the first metallocene catalyst compound of the present invention has a heteroatom-containing functional group capable of interacting with the cocatalyst compound, which is a Lewis base and has a Lewis acid- , Which causes the cyclopentadienyl skeleton-containing ligand of the first metallocene catalyst compound to rotate slowly. Thus, unlike other metallocene catalyst compounds having a single active site, the first metallocene catalyst compound of the present invention has multiple active sites. Thus, when an olefin polymer is produced using the supported catalyst of the present invention, an olefin polymer having a broad molecular weight distribution can be produced. The effect of the interaction between the first metallocene catalyst compound and the cocatalyst compound increases as the promoter compound is energized. For example, the aluminoxane compound, which is known as a bulky oligomer form, exhibits the maximum effect.

본 발명에서 사용 가능한 알루미녹산 화합물의 예로는 하기 화학식 6으로 표시되는 알루미녹산 화합물 등이 있는데, 이에 한정되지 않는다.Examples of aluminoxane compounds usable in the present invention include aluminoxane compounds represented by the following formula (6), but are not limited thereto.

상기 화학식 6에서,In Formula 6,

R⁶은 C₁~C₁₀의 알킬기이고,R⁶ is a C₁ to C₁₀ alkyl group,

q는 1~70의 정수이다.q is an integer of 1 to 70;

상기 알루미녹산 화합물의 구체적인 예로는 메틸알루미녹산(Methylaluminoxane), 에틸알루미녹산(Ethylaluminoxane), 부틸알루미녹산(Butylaluminoxane), 헥실알루미녹산(Hexylaluminoxane), 옥틸알루미녹산(Octylaluminoxane), 데실알루미녹산(Decylaluminoxane) 등이 있는데, 이에 한정되지 않는다. 이들은 단독으로 또는 2종 이상이 혼합되어 사용될 수 있다.Specific examples of the aluminoxane compound include methylaluminoxane, ethylaluminoxane, butylaluminoxane, hexylaluminoxane, octylaluminoxane, decylaluminoxane, and the like. But is not limited thereto. These may be used alone or in combination of two or more.

또, 본 발명에서 사용 가능한 유기알루미늄 화합물의 예로는 하기 화학식 7로 표시되는 유기알루미늄화합물 등이 있는데, 이에 한정되지 않는다.Examples of organoaluminum compounds usable in the present invention include organoaluminum compounds represented by the following formula (7), but are not limited thereto.

상기 화학식 7에서,In Formula 7,

R⁷ 내지 R⁹은 서로 동일하거나 상이하며, 각각 독립적으로 C₁~C₁₀의 알킬기, C₁~C₁₀의 알콕시기 또는 할로겐이고,R⁷ to R⁹ are the same or different and are each independently a C₁ to C₁₀ alkyl group, a C₁ to C₁₀ alkoxy group or a halogen,

다만 R⁷ 내지 R⁹ 중 적어도 하나는 C₁~C₁₀의 알킬기이다.Provided that at least one of R⁷ to R⁹ is a C₁ to C₁₀ alkyl group.

상기 유기알루미늄 화합물의 구체적인 예로는 트리메틸알루미늄(Trimethylaluminum), 트리에틸알루미늄(Triethylaluminum), 트리부틸알루미늄(Tributylaluminum), 트리헥실알루미늄(Trihexylaluminum), 트리옥틸알루미늄(Trioctylaluminum), 트리데실알루미늄(Tridecylaluminum), 디메틸알루미늄 메톡사이드(Dimethylaluminum methoxide), 디에틸알루미늄 메톡사이드(Diethylaluminum methoxide), 디부틸알루미늄 메톡사이드(Dibutylaluminum methoxide), 디메틸알루미늄 클로라이드(Dimethylaluminum chloride), 디에틸알루미늄 클로라이드(Diethylaluminum chloride), 디부틸알루미늄 클로라이드(Dibutylaluminum chloride), 메틸알루미늄 디메톡사이드(Methylaluminum dimethoxide), 에틸알루미늄 디메톡사이드(Ethylaluminum dimethoxide), 부틸알루미늄 디메톡사이드(Butylaluminum dimethoxide), 메틸알루미늄 디클로라이드(Methylaluminum dichloride), 에틸알루미늄 디클로라이드(Ethylaluminum dichloride), 및 부틸알루미늄 디클로라이드(Butylaluminum dichloride) 등이 있는데, 이에 한정되지 않는다. 이들은 단독으로 또는 2종 이상이 혼합되어 사용될 수 있다.Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, dimethyl Examples of the organic peroxide include dimethylaluminum methoxide, diethylaluminum methoxide, dibutylaluminum methoxide, dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride But are not limited to, dibutylaluminum chloride, methylaluminum dimethoxide, ethylaluminum dimethoxide, butylaluminum dimethoxide, methylaluminum dichloride, ethylaluminum There are such as titanium dichloride (Ethylaluminum dichloride), and butylaluminum dichloride (Butylaluminum dichloride), not limited to this. These may be used alone or in combination of two or more.

또, 본 발명에서 사용 가능한 벌키한 화합물의 예로는 하기 화학식 8로 표시되는 화합물이 있는데, 이에 한정되지 않는다.Examples of the bulky compounds usable in the present invention include compounds represented by the following formula (8), but are not limited thereto.

상기 화학식 8에서,In Formula 8,

C는 루이스 염기(Lewis Base)의 수소이온(Proton) 결합 양이온이거나, 또는 산화력이 있는 금속 또는 비금속 화합물이고,C is a proton-binding cation of Lewis Base, or is a metal or non-metal compound having oxidizing power,

D는 주기율표상의 5~15족의 원소로 이루어진 군에서 선택된 원소와 유기물질의 화합물이다.D is a compound of an organic substance and an element selected from the group consisting of elements of Groups 5 to 15 on the periodic table.

상기 벌키한 화합물의 비제한적인 예로는 보레이트계 화합물 등이 있다. 구체적인 예로는 트리페닐 카베니움 테트라키스(펜타플루오로페닐)보레이트(Triphenylcarbenium tetrakis(pentafluorophenyl)borate), 트리메틸암모늄 테트라페닐보레이트(Trimethylammonium tetraphenylborate), 트리에틸암모늄 테트라페닐보레이트(Triethylammonium tetraphenylborate), 트리프로필암모늄 테트라페닐보레이트(Tripropylammonium tetraphenylborate), 트리부틸암모늄 테트라페닐보레이트(Tributylammonium tetraphenylborate), 트리메틸암모늄 테트라키스(펜타플루오로페닐)보레이트(Trimethylammonium tetrakis(pentafluorophenyl)borate), 트리에틸암모늄 테트라키스(펜타플루오로페닐)보레이트(Triethylammonium tetrakis(pentafluorophenyl)borate), 트리프로필암모늄 테트라키스(펜타플루오로페닐)보레이트(Tripropylammonium tetrakis(pentafluorophenyl)borate), 트리부틸암모늄 테트라키스(펜타플루오로페닐)보레이트(Tributylammonium tetrakis(pentafluorophenyl)borate), 아닐리늄 테트라페닐보레이트(Anilinium tetraphenylborate), 아닐리늄 테트라키스(펜타플루오로페닐)보레이트(Anilinium tetrakis(pentafluorophenyl)borate), N,N-디메틸 아닐리늄 테트라키스(펜타플루오로페닐)보레이트(N,N-Dimethylanilinium tetrakis(pentafluorophenyl)borate), 피리디늄 테트라페닐보레이트(Pyridinium tetraphenylborate), 피리디늄 테트라키스(펜타플루오로페닐)보레이트(Pyridinium tetrakis(pentafluorophenyl)borate), 페로세늄 테트라키스(펜타플루오로페닐)보레이트(Ferrocenium tetrakis(pentafluorophenyl)borate), 실버 테트라페닐보레이트(Silver tetraphenylborate), 실버 테트라키스(펜타플루오로페닐)보레이트(Silver tetrakis(pentafluorophenyl)borate), 트리스(펜타플루오로페닐)보레인(Tris(pentafluorophenyl)borane), 트리스(2,3,5,6-테트라플루오로페닐)보레인(Tris(2,3,5,6-tetrafluorophenyl)borane), 트리스(2,3,4,5-테트라페닐페닐)보레인(Tris(2,3,4,5-tetraphenylphenyl)borane), 및 트리스(3,4,5-트리플루오로페닐)보레인(Tris(3,4,5-trifluorophenyl)borane) 등이 있는데, 이에 한정되지 않는다. 이들은 단독으로 또는 2종 이상이 혼합되어 사용될 수 있다.Non-limiting examples of the bulky compounds include borate compounds and the like. Specific examples thereof include triphenylcarbenium tetrakis (pentafluorophenyl) borate, trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, Examples thereof include tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, (Tetrafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tributylammonium tetr (pentafluorophenyl) (pentafluorophenyl) borate, anilinium tetraphenylborate, anilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, pyridinium tetraphenylborate, pyridinium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (Pentafluorophenyl) borate, Silver tetraphenylborate, Silver tetrakis (pentafluorophenyl) borate, Tris (pentafluorophenyl) borate, ), Boron (Tris (pentafluorophenyl) borane), tris (2,3,5,6-tetrafluorophenyl) borane, (2,3,4,5-tetraphenylphenyl) borane, and tris (3,4,5-trifluorophenyl) borane (Tris (3,4,5-trifluorophenyl) borane), but are not limited thereto. These may be used alone or in combination of two or more.

상기 조촉매 화합물의 함량은 상기 주촉매 화합물의 담지량 및 상기 주촉매 화합물을 충분히 활성화시키는 데 필요한 양 등을 고려하여 결정할 수 있다.The content of the co-catalyst compound may be determined in consideration of the amount of the main catalyst compound, the amount required for sufficiently activating the main catalyst compound, and the like.

상기 주촉매 화합물과 조촉매 화합물의 사용 비율은 특별히 한정되지 않고 주촉매 화합물 및 조촉매 화합물의 종류에 따라 조절하며, 상기 주촉매 화합물에 함유된 전이금속 원자에 대한 조촉매 화합물에 함유된 금속의 몰비를 1 : 0.01 ~ 1000 범위, 바람직하게 1 : 0.1 ~ 1000 범위로 조절하여 주촉매 화합물과 조촉매 화합물을 혼합 사용할 경우, 주촉매 화합물가 다중 활성 자리를 갖게 되고, 이로 인해 분자량 분포가 다양한 올레핀 중합체를 제조할 수 있다.The ratio of the main catalyst compound to the co-catalyst compound is not particularly limited and may be adjusted depending on the kind of the main catalyst compound and the co-catalyst compound, and the ratio of the metal contained in the co- When the main catalyst compound and the co-catalyst compound are mixedly used in a molar ratio of 1: 0.01 to 1000, preferably 1: 0.1 to 1000, the main catalyst compound has multiple active sites. As a result, the olefin polymer Can be produced.

일례에 따르면, 상기 조촉매 화합물이 상기 알루미녹산 화합물 또는 유기알루미늄 화합물인 경우, 상기 주촉매 화합물과 조촉매 화합물은 상기 주촉매 화합물에 함유된 전이금속 원자에 대한 조촉매 화합물에 함유된 금속의 몰비를 1 : 10 ~ 1000 범위, 바람직하게 1 : 50 ~ 1000 범위, 더 바람직하게 1 : 100 ~ 1000 범위로 혼합하여 사용할 수 있다.According to one example, when the co-catalyst compound is the aluminoxane compound or the organoaluminum compound, the main catalyst compound and the co-catalyst compound have a molar ratio of the metal contained in the co-catalyst compound to the transition metal atom contained in the main catalyst compound In the range of 1: 10 to 1000, preferably 1: 50 to 1000, more preferably 1: 100 to 1000.

또한, 다른 일례에 따르면, 상기 조촉매 화합물이 상기 벌키한 화합물, 예컨대 벌키한 보레이트계 화합물인 경우, 상기 주촉매 화합물과 조촉매 화합물은 상기 주촉매 화합물에 함유된 전이금속 원자에 대한 조촉매 화합물에 함유된 금속의 몰비를 1 : 0.01 ~ 10 범위, 바람직하게 1 : 0.1 ~ 3 범위로 혼합하여 사용할 수 있다.According to another example, when the promoter compound is a bulky compound such as a bulky borate compound, the main catalyst compound and the co-catalyst compound may be prepared by reacting the promoter compound with respect to the transition metal atom contained in the main catalyst compound May be used in a molar ratio of 1: 0.01 to 10, preferably 1: 0.1 to 3, in molar ratio.

(c) 담체(c)

본 발명에 따른 올레핀 중합용 담지 촉매는 전술한 주촉매 화합물(a) 및 조촉매 화합물(b)을 담지하는 담체(c)를 포함한다.The supported catalyst for olefin polymerization according to the present invention comprises the above-mentioned main catalyst compound (a) and the carrier (c) carrying the cocatalyst compound (b).

이와 같이, 주촉매 화합물 및 조촉매 화합물을 담체에 담지하여 사용함으로써, 주촉매 화합물 및 조촉매 화합물을 비담지 상태로 사용하는 경우에 비해 더 높은 고분자량을 갖는 올레핀 중합체를 제조할 수 있다. 또한, 기상 및 슬러리 공정에서 올레핀 중합체의 제조시, 상기 주촉매 화합물 및 조촉매 화합물을 담지된 형태로 사용할 경우, 제조되는 올레핀 중합체 입자를 효율적으로 유동화시킬 수 있다.As described above, by using the main catalyst compound and the promoter compound supported on the carrier, it is possible to produce an olefin polymer having a higher molecular weight than that in the case where the main catalyst compound and the promoter compound are used in a non-supported state. In addition, when the main catalyst compound and the promoter compound are used in the supported form in the production of the olefin polymer in the gas phase and slurry process, the produced olefin polymer particles can be efficiently fluidized.

상기 담체(c)는 표면 또는 내부에 미세한 구멍(pore)을 갖는 다공성 유기 화합물 및/또는 무기 화합물로서, 당 업계에서 일반적으로 알려진 것이라면 특별한 제한 없이 사용될 수 있다.The carrier (c) is a porous organic compound and / or an inorganic compound having a fine pore on the surface or inside thereof, and can be used without any particular limitation as long as it is generally known in the art.

상기 무기 화합물의 예로는 실리카(silica), 알루미나(alumina), 염화마그네슘(MgCl₂), 염화칼슘(CaCl₂), 보오크싸이트(bauxite), 제올라이트(xeolite), 산화마그네슘(MgO), 산화지르코늄(ZrO₂), 산화티타늄(TiO₂), 삼산화붕소(B₂O₃), 산화칼슘(CaO), 산화아연(ZnO), 산화바륨(BaO), 산화토륨(THO₂) 및 이들의 복합체 등이 있는데, 이에 한정되지 않는다. 상기 복합체의 비제한적인 예로는 SiO₂-MgO, SiO₂-Al₂O₃, SiO₂-TiO₂, SiO₂-V₂O₅, SiO₂-Cr₂O₃, SiO₂-TiO₂-MgO 등일 수 있다. 또, 상기 유기화합물의 예로는 전분(Starch), 사이클로덱스트린(Cyclodextrin), 합성 고분자 등이 있는데, 이에 한정되지 않는다. 이러한 담체는 단독으로 또는 2종 이상이 혼합하여 사용될 수 있다.Examples of the inorganic compound include silica, alumina, magnesium chloride (MgCl₂ ), calcium chloride (CaCl₂ ), bauxite, xeolite, magnesium oxide (MgO), zirconium oxide ZrO₂ ), titanium oxide (TiO₂ ), boron trioxide (B₂ O₃ ), calcium oxide (CaO), zinc oxide (ZnO), barium oxide (BaO), thorium oxide (THO₂ ) However, the present invention is not limited thereto. Particular examples of the composite_{SiO 2 -MgO, SiO 2 -Al 2} O 3, SiO 2 -TiO 2, SiO 2 -V 2 O 5, SiO 2 -Cr 2 O 3, SiO 2 -TiO 2 -MgO And so on. Examples of the organic compound include starch, cyclodextrin, synthetic polymer, and the like, but are not limited thereto. These carriers may be used alone or in combination of two or more.

이와 같은 담체(c)에 전술한 주촉매 화합물(a) 및 조촉매 화합물(b)을 담지시키는 방법은 특별히 한정되지 않는다. 예를 들어, (ⅰ) 수분이 제거된(dehydrated) 담체에 상기 주촉매 화합물(a) 및 상기 조촉매 화합물(b)의 혼합물을 직접 담지시키는 방법; (ⅱ) 상기 담체를 상기 조촉매 화합물(b)로 전처리한 후 주촉매 화합물(a)을 담지시키는 방법; (ⅲ) 상기 담체에 상기 주촉매 화합물(a)을 담지 시킨 후 조촉매 화합물(b)로 후처리하는 방법; (ⅳ) 상기 주촉매 화합물(a)과 조촉매 화합물(b)을 반응시킨 후 담체에 담지시키는 방법 등이 적용될 수 있다. 이때, 상기 주촉매 화합물을 담지 시키는 방법에 있어, 순차적으로 제1 메탈로센 촉매 화합물, 제2 메탈로센 촉매 화합물, 및 제3 메탈로센 촉매 화합물을 담지시킬 수 있으며, 또는 이들의 순서를 변경하여 담지시킬 수 있고, 나아가 2종 또는 3종을 한 번에 혼합하여 담지시킬 수 있다.The method of supporting the main catalyst compound (a) and the promoter compound (b) described above on the carrier (c) is not particularly limited. For example, (i) a method in which a mixture of the main catalyst compound (a) and the above-mentioned co-catalyst compound (b) is directly supported on a dehydrated carrier; (Ii) a method in which the carrier is pretreated with the co-catalyst compound (b) and then the main catalyst compound (a) is supported thereon; (Iii) carrying the main catalyst compound (a) on the carrier and then post-treating it with the co-catalyst compound (b); (Iv) a method in which the main catalyst compound (a) is reacted with the co-catalyst compound (b) and then supported on a carrier can be applied. At this time, in the method of supporting the main catalyst compound, the first metallocene catalyst compound, the second metallocene catalyst compound, and the third metallocene catalyst compound may be carried sequentially, And further, two or three kinds can be mixed and carried at a time.

본 발명의 주촉매 화합물 및 조촉매 화합물을 담체에 담지시킬 때 용매를 사용할 수 있다.A solvent may be used when the main catalyst compound and the cocatalyst compound of the present invention are supported on a carrier.

본 발명에서 사용 가능한 용매의 예로는 펜탄(Pentane), 헥산(Hexane), 헵탄(Heptane), 옥탄(Octane), 노난(Nonane), 데칸(Decane), 운데칸(Undecane), 도데칸(Dodecane) 등의 지방족 탄화수소계 용매; 벤젠(Benzene), 모노클로로벤젠(Monochlorobenzene), 디클로로벤젠(Dichlorobenzene), 트리클로로벤젠(Trichlorobenzene), 톨루엔(Toluene) 등의 방향족 탄화수소계 용매; 디클로로메탄(Dichloromethane), 트리클로로메탄(Trichloromethane), 디클로로에탄(Dichloroethane), 트리클로로에탄(Trichloroethane) 등의 할로겐화 지방족 탄화수소계 용매 등이 있는데, 이에 한정되는 것은 아니며, 담지 반응시 단독으로 또는 2종 이상 혼합하여 사용할 수 있다.Examples of the solvent usable in the present invention include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, Aliphatic hydrocarbons; Aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene and toluene; and aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene and toluene; But are not limited to, halogenated aliphatic hydrocarbon solvents such as dichloromethane, trichloromethane, dichloroethane, and trichloroethane. These solvents may be used alone or in combination of two or more species Or more.

또, 상기 주촉매 화합물과 조촉매 화합물을 담체에 담지시키는 공정은 약 - 20 내지 120 ℃, 바람직하게 약 0 내지 100 ℃ 범위의 조건하에서 수행되는 것이 담지 공정의 효율면에서 유리하다.The step of carrying the main catalyst compound and the co-catalyst compound on the carrier is advantageously carried out under the condition of about -20 to 120 ° C, preferably about 0 to 100 ° C from the viewpoint of efficiency of the supporting process.

상기 담체은 주촉매 화합물 및 조촉매 화합물과의 사용 비율은 특별히 한정되지 않으며, 중합 반응계에 따라 적절히 조절될 수 있다.
The ratio of the carrier to the main catalyst compound and the cocatalyst compound is not particularly limited and can be appropriately adjusted according to the polymerization reaction system.

<올레핀 중합체의 제조방법 및 올레핀 중합체>&Lt; Process for producing olefin polymer and olefin polymer &

본 발명은 전술한 올레핀 중합용 담지 촉매의 존재 하에서 하나 이상의 올레핀계 단량체를 중합 반응시키는 단계를 포함하는 올레핀 중합체의 제조방법을 제공한다.The present invention provides a process for producing an olefin polymer comprising the step of polymerizing at least one olefin monomer in the presence of the aforementioned supported catalyst for olefin polymerization.

상기 올레핀 중합체의 제조시, 상기 올레핀 중합용 담지 촉매의 함량을 조절함으로써, 올레핀 중합체의 중량평균분자량(Mw)이 약 500 ~ 3,000,000 범위, 바람직하게 약 50,000 ~ 500,000 범위로 조절되고, 분자량 분포가 약 2.0 ~ 30 범위, 바람직하게 약 3.0 ~ 10 범위로 효율적으로 조절될 수 있고, 이로 인해 제조된 올레핀 중합체의 성형성이 향상될 수 있다.The weight average molecular weight (Mw) of the olefin polymer is controlled in the range of about 500 to 3,000,000, preferably about 50,000 to 500,000, by controlling the content of the supported catalyst for olefin polymerization in the production of the olefin polymer, Can be efficiently controlled in the range of 2.0 to 30, preferably in the range of about 3.0 to 10, and the moldability of the olefin polymer thus produced can be improved.

일례에 따르면, 본 발명에 따른 올레핀 중합용 담지 촉매의 존재 하에서 1종의 올레핀계 단량체를 중합 반응시켜 올레핀의 단독 중합체를 얻을 수 있다.According to one example, in the presence of the supported catalyst for olefin polymerization according to the present invention, one kind of olefin-based monomer is polymerized and a homopolymer of olefin can be obtained.

다른 일례에 따르면, 본 발명에 따른 올페핀 중합용 담지 촉매의 존재하에서 2종 이상의 올레핀계 단량체를 중합 반응시켜 올레핀의 공중합체를 얻을 수 있다. 이때, 상기 공중합체는 교호 공중합체(alternating copolymer), 랜덤 공중합체(random copolymer), 블록 공중합체(block copolymer), 그래프트 공중합체(graft copolymer) 등일 수 있다.According to another example, in the presence of the supported catalyst for olefin polymerization according to the present invention, at least two olefin monomers may be polymerized to obtain a copolymer of olefins. At this time, the copolymer may be an alternating copolymer, a random copolymer, a block copolymer, a graft copolymer, or the like.

여기서, 상기 올레핀 중합체는 중합체 내부에 전술한 담지 촉매를 함유할 수 있다.Here, the olefin polymer may contain the above-mentioned supported catalyst inside the polymer.

본 발명에서 사용 가능한 올레핀계 단량체의 예로는 에틸렌(Ethylene), 프로필렌(Propylene), 1-부텐(1-Butene), 1-펜텐(1-Pentene), 1-헥센(1-Hexene) 등의 C₂~C₂₀의 α-올레핀(α-Olefin); 1,3-부타디엔(1,3-Butadiene), 1,4-펜타디엔(1,4-Pentadiene), 2-메틸-1,3-부타디엔(2-Methyl-1,3-butadiene) 등의 C₄~C₂₀의 디올레핀(Diolefin); 시클로펜텐(Cyclopentene), 시클로헥센(Cyclohexene), 시클로펜타디엔(Cyclopentadiene), 시클로헥사디엔(Cyclohexadiene), 노르보넨(Norbonene), 메틸-2-노르보넨(Methyl-2-Norbonene) 등의 C₃~C₂₀의 시클로올레핀(Cycloolefin); C₃~C₂₀의 시클로디올레핀(Cyclodiolefin); 스티렌; 스티렌 유도체 등이 있는데, 이에 한정되지 않는다. 여기서, 상기 스티렌 유도체는 스티렌의 벤젠 고리(phenyl ring)에 C₁~C₁₀의 알킬기, C₁~C₁₀의 알콕시기, 할로겐기, 아민기, 실릴기, 할로(C₁~C₁₀)알킬기 등에서 선택된 1종 이상의 치환기로 치환된 것이다. 이러한 올레핀계 단량체는 단독으로 또는 2종 이상이 혼합되어 사용될 수 있다.Examples of the olefin-based monomer that can be used in the present invention include olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene,₂ to C₂₀ alpha -olefins (alpha -olefin); Such as 1,3-butadiene, 1,4-pentadiene, and 2-methyl-1,3-butadiene,₄ to C₂₀ diolefins; C₃ to C₆ hydrocarbons such as cyclopentene, cyclohexene, cyclopentadiene, cyclohexadiene, norbonene, and methyl-2-norbornene, C₂₀ cycloolefin; C₃ to C₂₀ cyclodiolefins; Styrene; Styrene derivatives, and the like, but are not limited thereto. Here, the styrene derivative may be a styrene derivative in which a benzene ring of styrene is substituted with a C₁ -C₁₀ alkyl group, a C₁ -C₁₀ alkoxy group, a halogen group, an amine group, a silyl group, a halo (C₁ -C₁₀ ) And the like. These olefin-based monomers may be used alone or in combination of two or more.

상기 중합 반응의 예로는 액상(Liquid Phase), 기상(Gas Phase), 괴상(Bulk Phase), 슬러리상(Slurry Phase) 등이 있다.Examples of the polymerization reaction include a liquid phase, a gas phase, a bulk phase, and a slurry phase.

상기 중합 반응이 액상 또는 슬러리상에서 실시될 경우, 용매 또는 올레핀 자체를 매질로 사용할 수 있다.When the polymerization reaction is carried out in a liquid phase or a slurry, the solvent or the olefin itself may be used as a medium.

상기 중합 반응시 사용 가능한 용매로는 당 업계에서 올레핀 중합체의 제조시 사용되는 것이라면 특별히 한정되지 않는다. 예를 들어, 부탄(Butane), 이소부탄(Isobutane), 펜탄(Pentane), 헥산(Hexane), 시클로헥산(Cyclohexane), 헵탄(Heptane), 옥탄(Octane), 노난(Nonane), 데칸(Decane), 운데칸(Undecane), 도데칸(Dodecane) 등의 지방족 탄화수소계 용매; 벤젠(Benzene), 모노클로로벤젠(Monochlorobenzene), 디클로로벤젠(Dichlorobenzene), 트리클로로벤젠(Trichlorobenzene), 톨루엔(Toluene) 등의 방향족 탄화수소계 용매; 디클로로메탄(Dichloromethane), 트리클로로메탄(Trichloromethane), 디클로로에탄(Dichloroethane), 트리클로로에탄(Trichloroethane) 등의 할로겐화 지방족 탄화수소 용매 등이 있는데, 이에 한정되지 않는다. 이들은 중합 반응시 단독으로 또는 2종 이상이 혼합되어 사용될 수 있다.The solvent usable in the polymerization reaction is not particularly limited as long as it is used in the production of olefin polymers in the art. For example, butane, isobutane, pentane, hexane, cyclohexane, heptane, octane, nonane, decane, An aliphatic hydrocarbon-based solvent such as undecane, dodecane and the like; Aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene and toluene; and aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene and toluene; Halogenated aliphatic hydrocarbon solvents such as dichloromethane, trichloromethane, dichloroethane, and trichloroethane, but are not limited thereto. These may be used singly or in combination of two or more in the polymerization reaction.

상기 올레핀 중합용 담지 촉매의 함량은 특별히 한정되지 않으며, 슬러리상, 기상 또는 괴상 등의 중합 반응의 종류나 규모, 촉매의 활성 등에 따라 올레핀계 단량체의 중합 반응이 충분히 일어날 수 있는 범위 내로 조절하는 것이 바람직하다.The content of the supported catalyst for olefin polymerization is not particularly limited and may be controlled within a range in which the polymerization reaction of the olefin monomer can sufficiently take place depending on the type and scale of the polymerization reaction such as slurry phase, desirable.

상기 중합 반응 단계는 배치식(Batch Type), 반연속식(Semi-continuous Type) 또는 연속식(Continuous Type)으로 수행할 수 있다.The polymerization reaction may be carried out in a batch type, a semi-continuous type, or a continuous type.

또, 상기 중합 반응 단계의 온도 및 압력은 특별히 제한되지 않으며, 적용하고자 하는 반응의 종류 및 반응기의 종류에 따라 중합 반응의 효율을 고려하여 조절한다.The temperature and pressure of the polymerization reaction step are not particularly limited, and the polymerization reaction may be controlled according to the type of reaction to be applied and the type of the reaction.

일례에 따르면, 상기 중합 반응 단계는 약 0 ~ 200 ℃ 범위, 바람직하게 약 20 ~ 100 ℃ 범위의 온도 하에서 수행될 수 있다. 또, 상기 중합 반응 단계는 약 1 ~ 100 bar 범위, 바람직하게 약 5 ~ 60 bar 범위의 압력 하에서 수행될 수 있다.According to one example, the polymerization reaction step can be carried out at a temperature in the range of about 0 to 200 ° C, preferably in the range of about 20 to 100 ° C. In addition, the polymerization reaction step can be carried out under a pressure in the range of about 1 to 100 bar, preferably about 5 to 60 bar.

한편, 본 발명에 따른 올레핀 중합체의 제조방법은 전술한 단계 이외에도, 상기 단계의 이전 또는 이후에 당 업계에서 통상적으로 수행될 수 있는 단계를 더 포함할 수 있다.Meanwhile, the method for producing an olefin polymer according to the present invention may further include a step that can be carried out conventionally in the art before or after the above step, in addition to the above-mentioned step.

아울러, 본 발명은 전술한 방법을 통해 제조된 올레핀 중합체를 제공한다. 다만, 본 발명의 올레핀 중합체는 전술한 바와 같이 제조시 2종 이상의 메탈로센 촉매 화합물과 조촉매 화합물이 담체에 담지되어 있는 상기 올레핀 중합용 담지 촉매를 이용함으로써, 종래 올레핀 중합체와 달리, 중량평균분자량(Mw)이 약 500 ~ 3,000,000 범위, 바람직하게 약 50,000 ~ 500,000 범위로 제어되면서, 분자량 분포가 약 2.0 ~ 30 범위, 바람직하게 약 3 ~ 10 범위로 조절될 수 있다.
In addition, the present invention provides an olefin polymer produced by the above-described method. However, by using the supported catalyst for olefin polymerization in which two or more metallocene catalyst compounds and a cocatalyst compound are supported on the carrier during the production as described above, unlike the conventional olefin polymers, the weight average The molecular weight distribution can be controlled in the range of about 2.0 to 30, preferably about 3 to 10, while controlling the molecular weight (Mw) in the range of about 500 to 3,000,000, preferably about 50,000 to 500,000.

이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예들을 제시한다. 그러나 하기의 실시예들은 본 발명을 예시하기 위한 것일 뿐, 본 발명을 이들만으로 한정하는 것은 아니다.Best Mode for Carrying Out the Invention Hereinafter, preferred embodiments are described to facilitate understanding of the present invention. However, the following examples are intended to illustrate the present invention without limiting it thereto.

<합성예> - 제1 메탈로센 촉매 화합물의 합성Synthesis Example - Synthesis of first metallocene catalyst compound

하기 모든 합성 단계는 질소 또는 아르곤 등의 비활성 분위기(Inert Atmosphere)에서 진행되었고, 표준 쉴렌크(Standard Schlenk) 기술과 글러브 박스(Glove Box) 기술을 이용하였다.All the following synthesis steps were carried out in an inert atmosphere such as nitrogen or argon, using the standard Schlenk technique and the glove box technique.

테트라하이드로퓨란(Tetahydrofuran, THF), 톨루엔(Toluene), 노르말헥산(n-Hexane), 디에틸에테르(Diethyl Ether), 메틸렌클로라이드(Methylene Chloride, CH₂Cl₂) 등의 합성용 용매(Sigma Aldrich사, Anhydrous Grade)는 활성화된 알루미나 층(Activated Alumina Column)을 통과시켜 수분을 제거한 다음, 활성화된 분자체(Mol·ecular Sieve 5A, Yakuri Pure Chemicals Co) 상에서 보관하면서 사용하였으며, 유기금속화합물의 NMR 구조 분석에 사용된 이중수소치환클로로포름(Chloroform-d, CDCl₃)(Cambridge Isotope Laboratories사)은 활성화된 분자체(Molecular Sieve 5A, Yakuri Pure Chemicals Co) 상에서 건조하여 사용하였다.Tetrahydrofuran (Tetahydrofuran, THF), toluene (Toluene), normal hexane solvent for synthesis, such as(n -Hexane), diethyl ether (Diethyl Ether), methylene chloride_{(Methylene Chloride, CH 2 Cl 2} ) (Sigma Aldrich Co. , Anhydrous Grade) was used by passing through an activated alumina column to remove moisture and then stored on activated molecular sieve (Mol · ecular Sieve 5A, Yakuri Pure Chemicals Co). The NMR structure of the organometallic compound the double substitution of hydrogen used in the analysis chloroform_{(Chloroform- d, CDCl 3) (} Cambridge Isotope Laboratories , Inc.) was used and dried over activated molecular sieves (Molecular sieve 5A, Yakuri Pure Chemicals Co).

에탄올, 노르말펜탄(n-Pentane), 에틸아세테이트, 노르말부틸리튬(2.5 M Solution inn-Hexane), 메틸리튬(1.6 M solution in Diethyl ether), 4-브로모-4'-메톡시비페닐, 4-브로모-N,N-디메틸아닐린(4-Bromo-N,N-dimethylaniline), 염화암모늄, 무수 황산마그네슘(Magnesium sulfate, anhydrous), 파라-톨루엔술폰산 수화물(p-TsOH·H₂O) 등의 물질(Sigma-Aldrich사)은 정제 없이 사용하였고, 테트라클로로비스(테트라하이드로퓨란)지르코늄[Tetrachlorobis(tetrahydrofuran)zirconium, ZrCl₄·2C₄H₈O](Strem사)도 정제 없이 사용하였으며, 3,4-디메틸시글로펜타-2-에논(3,4-Dimethylcyclopent-2-enone, 3,4-Me₂-C₅H₄O)은 문헌에 수록된 방법대로 합성하여 사용하였다.Ethanol, and n-pentane(n -Pentane), ethyl acetate, n-butyl lithium(2.5 M Solution in n -Hexane) , methyl lithium (1.6 M solution in Diethyl ether) , 4- bromo-4'-methoxy-phenyl fertilization, 4-bromo-N, N-dimethylaniline(4-Bromo- N, N -dimethylaniline ), ammonium chloride, anhydrous magnesium sulfate (magnesium sulfate, anhydrous), para-toluenesulfonic acid hydrate(p -TsOH · H₂ O), etc. (Sigma-Aldrich) was used without purification and tetrachlorobis (tetrahydrofuran) zirconium (ZrCl₄ .2C₄ H₈ O) (Strem) was also used without purification and 3 , 4-dimethylvaleronitrile during post-penta-2-enone (3,4-Dimethylcyclopent-2-enone , 3,4-Me 2 -C 5 H 4 O) was used in the synthesis methods, as listed in the literature.

¹H NMR 및¹³C NMR은 상온에서 Bruker Avance 400 Spectrometer를 사용하여 측정하였고, NMR 스펙트럼(Spectrum)의 화학적 이동값(Chemical Shift)은 중수소화클로로포름(CDCl₃)이 나타내는 화학적 이동값(¹H NMR의 경우, δ=7.24 ppm,¹³C NMR의 경우, δ=77.0 ppm)을 기준으로 표시하였다. 또한, 원소 분석은 EA 1110-FISION(CE Instruments)를 사용하여 측정하였다.¹ H NMR and¹³ C NMR were measured using a Bruker Avance 400 Spectrometer at room temperature and the chemical shift of the NMR spectrum was determined by chemical shifts (¹ H NMR (CDCl₃ )) as indicated by deuterated chloroform ? = 7.24 ppm in the case of¹³ C NMR,? = 77.0 ppm in the case of¹³ C NMR). Elemental analysis was also performed using EA 1110-FISION (CE Instruments).

[합성예 1] 비스-[1-([Synthesis Example 1] Synthesis of bis- [1- (pp-디메틸아미노페닐)-3,4-디메틸시클로펜타디에닐]지르코늄 디클로라이드(Bis-[1-(-Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- (pp-Dimethylaminophenyl)-3,4-dimethylcyclopentadienyl]zirconium dichloride, [1-(-Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- (pp-Me-Me₂₂NCNC₆₆HH₄₄)-3,4-Me) -3,4-Me₂₂CC₅₅HH₂₂]]₂₂ZrClZrCl₂₂)의 합성) Synthesis of

[단계 1] 1-([Step 1] 1- (pp-디메틸아미노페닐)-3,4-디메틸시클로펜타디엔(1-(-Dimethylaminophenyl) -3,4-dimethylcyclopentadiene (1- (pp-Dimethylaminophenyl)-3,4-dimethylcyclopentadiene, (-Dimethylaminophenyl) -3,4-dimethylcyclopentadiene, (pp-Me-Me₂₂NCNC₆₆HH₄₄)-3,4-Me) -3,4-Me₂₂CC₅₅HH₃₃)의 합성) Synthesis of

4-브로모-N,N-디메틸아닐린(4.00 g, 20 mmol)을 50 mL의 디에틸에테르에 녹인 뒤, 0 ℃ 에서 1 당량의 노르말부틸리튬(8.0 mL)을 첨가하였다. 상온에서 2시간 동안 교반시킨 후, - 78 ℃로 온도를 낮춘 다음, 1 당량의 3,4-디메틸시클로펜타-2-에논(2.20 g, 20 mmol)을 용해시킨 20 mL의 테트라하이드로퓨란 용액을 적가한 후, 상온으로 천천히 승온시킨 후 밤새 교반시켰다. 이후, 얻은 오렌지색의 용액에 포화된 염화암모늄 수용액을 적당량 가하여 반응을 종결시켰다.4-Bromo-N ,N -dimethylaniline (4.00 g, 20 mmol) was dissolved in 50 mL of diethyl ether and then 1 equivalent of n-butyllithium (8.0 mL) was added at 0 ° C. After stirring at room temperature for 2 hours, the temperature was lowered to -78 ° C, and 20 mL of tetrahydrofuran solution in which 1 equivalent of 3,4-dimethylcyclopenta-2-enone (2.20 g, 20 mmol) After the dropwise addition, the mixture was slowly warmed to room temperature and stirred overnight. Thereafter, an appropriate amount of a saturated ammonium chloride aqueous solution was added to the obtained orange solution to terminate the reaction.

이어서, 디에틸에테르(50 mL)로 유기 용액층만 추출한 후, 무수황산마그네슘으로 건조하여 여과시켰다. 여과된 용액을 회전 증발기에서 용매를 제거하여 노란색의 오일을 얻었다. 상기 오일을 메틸렌클로라이드(30 mL)에 용해시킨 후, 파라-톨루엔술폰산 수화물(ca. 0.1 g)을 넣고, 상온에서 1 시간 동안 교반하여 아이보리색의 고체를 얻었다. 이후, 용매를 회전 증발기로 증발시킨 다음, 30 mL의 노르말헥산으로 침전시킨 후, Glass Filter를 이용하여 걸려내었다. 걸러진 고체를 에탄올(30 mL), 디에틸에테르(30 mL), 노르말펜탄(30 mL)로 씻어낸 후, 진공 건조하여 1-(p-디메틸아미노페닐)-3,4-디메틸시클로펜타디엔(수율: 63 %)을 얻었다.Then, the organic solution layer was extracted with diethyl ether (50 mL), dried over anhydrous magnesium sulfate, and filtered. The filtered solution was stripped of solvent in a rotary evaporator to give a yellow oil. The oil was dissolved in methylene chloride (30 mL), para-toluenesulfonic acid hydrate (ca. 0.1 g) was added thereto, and the mixture was stirred at room temperature for 1 hour to obtain an ivory solid. Then, the solvent was evaporated with a rotary evaporator, and then precipitated with 30 mL of n-hexane, and then the glass filter was hung. The filtered solid was rinsed with ethanol (30 mL), diethyl ether (30 mL) and n-pentane (30 mL) and then vacuum dried to obtain 1- (p -dimethylaminophenyl) -3,4-dimethylcyclopentadiene Yield: 63%).

상기에서 얻은 1-(p-디메틸아미노페닐)-3,4-디메틸시클로펜타디엔의¹H NMR 결과는 다음에 나타내었다.¹ H NMR results of the 1- (p -dimethylaminophenyl) -3,4-dimethylcyclopentadiene obtained above are shown below.

¹H NMR (400.13 MHz, CDCl₃): d 7.33 (d, 2H), 6.69 (d, 2H), 6.45 (s, 1H), 3.21 (s, 2H), 2.93 (s, 6H), 1.94 (s, 3H), 1.86 (s, 3H).^{1 H NMR (400.13 MHz, CDCl} 3): d 7.33 (d, 2H), 6.69 (d, 2H), 6.45 (s, 1H), 3.21 (s, 2H), 2.93 (s, 6H), 1.94 (s , &Lt; / RTI &gt; 3H), 1.86 (s, 3H).

[단계 2] 비스[1-([Step 2] Synthesis of bis [1- (pp-디메틸아미노페닐)-3,4-디메틸시클로펜타디에닐]지르코늄 디클로라이드(Bis-[1-(-Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- (pp-Dimethylaminophenyl)-3,4-dimethylcyclopentadienyl]zirconium dichloride, [1-(-Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- (pp-Me-Me₂₂NCNC₆₆HH₄₄)-3,4-Me) -3,4-Me₂₂CC₅₅HH₂₂]]₂₂ZrClZrCl₂₂)의 합성) Synthesis of

상기 합성예 1의 [단계 1]에서 합성된 1-(p-디메틸아미노페닐)-3,4-디메틸시클로펜타디엔(1.280 g, 6.0 mmol)을 디에틸에테르(30 mL)에 녹인 후, - 78 ℃에서 1 당량의 노르말부틸리튬(2.4 mL)을 첨가한 다음, 상온으로 승온시킨 후 4 시간 동안 교반하였다. 이후, 용매를 모두 증발시켜 얻은 흰색의 리튬염을 반당량의 테트라클로로비스(테트라하이드로퓨란)지르코늄(1.132g, 3 mmol)과 혼합한 후, - 78 ℃에서 톨루엔(50 mL)에 용해시킨 다음, 상기 용액을 천천히 상온으로 올린 후, 60 ℃로 밤새 가열하면서 교반시켰다. 이어서, Celite 여과로 반응 부산물로 생긴 염화리튬(LiCl)을 제거하고 용매를 모두 증발시킨 후, 노르말헥산으로 씻고 건조하여 비스[1-(p-디메틸아미노페닐)-3,4-디메틸시클로펜타디에닐]지르코늄 디클로라이드(0.968 g, 수율: 55%)를 얻었다. 또, 상기 결과물을 메틸렌클로라이드/노르말헥산 용액으로 - 20 ℃에서 재결정하여 빨간색의 결정성 고체를 얻었다.1- (p -Dimethylaminophenyl) -3,4-dimethylcyclopentadiene (1.280 g, 6.0 mmol) synthesized in [Step 1] of Synthesis Example 1 was dissolved in diethyl ether (30 mL) One equivalent of n-butyllithium (2.4 mL) was added at 78 DEG C, and then the mixture was warmed to room temperature and stirred for 4 hours. Thereafter, the white lithium salt obtained by evaporating all of the solvent was mixed with half-equivalent amount of tetrachlorobis (tetrahydrofuran) zirconium (1.132 g, 3 mmol) and dissolved in toluene (50 mL) at -78 ° C. , The solution was slowly warmed to room temperature, and stirred while heating to 60 DEG C overnight. Subsequently, lithium chloride (LiCl) formed as a reaction by-product was removed by Celite filtration, and all of the solvent was evaporated, followed by washing with normal hexane and drying to obtain bis [1- (p- dimethylaminophenyl) -3,4-dimethylcyclopentadienyl Yl] zirconium dichloride (0.968 g, yield: 55%). The resultant was recrystallized in methylene chloride / n-hexane at -20 ° C to obtain a red crystalline solid.

상기에서 얻은 비스[1-(p-디메틸아미노페닐)-3,4-디메틸시클로펜타디에닐]지르코늄 디클로라이드의¹HNMR 결과는 다음에 나타내었다.The¹ H of the bis [1- (p -dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride obtained above NMR results are shown below.

¹H NMR (400.13 MHz, CDCl₃): d 7.34 (d, 4H), 6.77 (d, 4H), 6.14 (s, 4H), 2.99 (s, 12H), 1.77 (s, 12H).
¹ H NMR (400.13 MHz, CDCl₃ ): d 7.34 (d, 4H), 6.77 (d, 4H), 6.14 (s, 4H), 2.99 (s, 12H), 1.77 (s, 12H).

[합성예 2] 비스-[1-([Synthesis Example 2] Synthesis of bis- [1- (pp-메톡시비페닐)-3,4-디메틸시클로펜타디에닐]지르코늄 디클로라이드(Bis-[1-(-Methoxybiphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- (pp-methoxybiphenyl)-3,4-dimethylcyclopentadienyl]zirconium dichloride, [1-(-methoxybiphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- (pp-MeO C-MeO C₆₆HH₄₄CC₆₆HH₄₄)-3,4-Me) -3,4-Me₂₂CC₅₅HH₂₂]]₂₂ZrClZrCl₂₂)의 합성) Synthesis of

[단계 1] 1-([Step 1] 1- (pp-메톡시페닐)-3,4-디메틸시클로펜타디엔(1-(-Methoxyphenyl) -3,4-dimethylcyclopentadiene (1- (pp-methoxyphenyl)-3,4-dimethylcyclopentadiene, (-methoxyphenyl) -3,4-dimethylcyclopentadiene, (pp-MeOC-MeOC₆₆HH₄₄CC₆₆HH₄₄)-3,4-Me) -3,4-Me₂₂CC₅₅HH₃₃)의 합성) Synthesis of

4-브로모-4'-메톡시비페닐(2.631 g, 10 mmol)을 디에틸에테르(50 mL)에 녹인 후, 0 ℃에서 1 당량의 노르말부틸리튬(4.0 mL)을 첨가하였다. 이후, 상온으로 온도를 승온시킨 다음, 2시간 동안 교반시킨 후, - 78 ℃로 온도를 낮추고, 1 당량의 3,4-디메틸시클로펜타-2-에논(1.10 g, 10 mmol)을 용해시킨 테트라하이드로퓨란 용액(20 mL)을 적가한 후, 상온으로 천천히 올려 밤새 교반하였다. 이후, 얻은 오렌지색의 용액에 포화된 염화암모늄 수용액을 적당량 가하여 반응을 종결시켰다.4-Bromo-4'-methoxybiphenyl (2.631 g, 10 mmol) was dissolved in diethyl ether (50 mL), and then 1 equivalent of n-butyllithium (4.0 mL) was added at 0 ° C. Thereafter, the temperature was raised to room temperature, and the mixture was stirred for 2 hours. Then, the mixture was cooled to -78 ° C, and tetrahedra (1.10 g, 10 mmol) in which 1 equivalent of 3,4-dimethylcyclopenta- A solution of hydrofuran (20 mL) was added dropwise, then slowly raised to room temperature and stirred overnight. Thereafter, an appropriate amount of a saturated ammonium chloride aqueous solution was added to the obtained orange solution to terminate the reaction.

이어서, 디에틸에테르(50 mL)로 유기 용액층만을 추출한 후, 무수황산마그네슘으로 건조하여 여과한 다음, 여과된 용액을 회전 증발기에서 용매를 제거하여 노란색 오일을 얻었다. 이후, 상기 오일을 메틸렌클로라이드(30 mL)에 용해시킨 후, 파라-톨루엔술폰산 수화물(ca. 0.1 g)을 넣고, 상온에서 1 시간 동안 교반하여 아이보리색의 고체를 얻었다. 이어서, 용매를 회전증발기로 증발시켜 얻은 고체에 에탄올(30 mL)을 붓고, Glass Filter를 이용하여 걸러내었다. 이어서, 디에틸에테르(10 mL), 노르말펜탄(10 mL)로 씻어낸 후, 진공 건조하여 1-(p-메톡시비페닐)-3,4-디메틸시클로펜타디엔(수율: 55 %)을 얻었다.Then, only the organic solution layer was extracted with diethyl ether (50 mL), dried with anhydrous magnesium sulfate and filtered, and then the solvent was removed from the filtered solution using a rotary evaporator to obtain a yellow oil. Thereafter, the oil was dissolved in methylene chloride (30 mL), para-toluenesulfonic acid hydrate (ca. 0.1 g) was added thereto, and the mixture was stirred at room temperature for 1 hour to obtain an ivory solid. Subsequently, the solvent was evaporated on a rotary evaporator, and ethanol (30 mL) was poured into the obtained solid and filtered using a glass filter. Subsequently, the resultant was washed with diethyl ether (10 mL) and n-pentane (10 mL), and then vacuum dried to obtain 1- (p -methoxybiphenyl) -3,4-dimethylcyclopentadiene (yield: 55% .

상기 1-(p-메톡시비페닐)-3,4-디메틸시클로펜타디엔의¹H NMR 결과는 다음에 나타내었다.¹ H NMR results of the above 1- (p -methoxybiphenyl) -3,4-dimethylcyclopentadiene are shown below.

¹H NMR (400.13 MHz, CDCl₃): d 7.52 (dd, 2H), 7.47 (s, 4H), 6.95 (dd, 2H), 6.68 (s, 1H), 3.83 (s, 3H), 3.29 (s, 2H), 1.98 (s, 3H), 1.90 (s, 3H).^{1 H NMR (400.13 MHz, CDCl} 3): d 7.52 (dd, 2H), 7.47 (s, 4H), 6.95 (dd, 2H), 6.68 (s, 1H), 3.83 (s, 3H), 3.29 (s , 2H), 1.98 (s, 3H), 1.90 (s, 3H).

[단계 2] 비스-[1-([Step 2] Synthesis of bis- [1- (pp-메톡시비페닐)-3,4-디메틸시클로펜타디에닐]지르코늄 디클로라이드(Bis-[1-(-Methoxybiphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- (pp-methoxybiphenyl)-3,4-dimethylcyclopentadienyl]zirconium dichloride, [1-(-methoxybiphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- (pp-MeOC-MeOC₆₆HH₄₄CC₆₆HH₄₄)-3,4-Me) -3,4-Me₂₂CC₅₅HH₂₂]]₂₂ZrClZrCl₂₂)의 합성) Synthesis of

상기 합성예 2의 [단계 1]에서 합성된 1-(p-메톡시비페닐)-3,4-디메틸시클로펜타디엔(0.829 g, 3.0 mmol)을 이용하는 것을 제외하고는, 상기 합성예 1의 [단계 2]에서와 동일한 방법으로 반응을 진행시켜 노란색 고체인 비스-[1-(p-메톡시비페닐)-3,4-디메틸시클로펜타디에닐]지르코늄 디클로라이드(수율: 60%)를 얻었다. 또한, 상기 결과물을 디클로로메탄/헥산 용액으로 - 20 ℃에서 재결정하여 노란색의 결정성 고체를 얻었다.The procedure of Synthesis Example 1 was repeated except that 1- (p -methoxybiphenyl) -3,4-dimethylcyclopentadiene (0.829 g, 3.0 mmol) synthesized in [Step 1] (P -methoxybiphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride as a yellow solid (yield: 60%) was obtained in the same manner as in [Step 2]. Further, the resultant was recrystallized with dichloromethane / hexane solution at -20 占 폚 to obtain a yellow crystalline solid.

상기에서 얻은 비스-[1-(p-메톡시비페닐)-3,4-디메틸시클로펜타디에닐]지르코늄 디클로라이드의¹HNMR 결과는 다음에 나타내었다.The¹ H of the bis- [1- (p -methoxybiphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride obtained above NMR results are shown below.

¹H NMR (400.13 MHz, CDCl₃): d 7.64 (d, 4H), 7.58 (d, 4H), 7.51 (d, 4H), 7.00 (d, 4H), 6.31 (s, 4H), 3.86 (s, 6H), 1.80 (s, 12H).
¹ H NMR (400.13 MHz, CDCl₃ ): d 7.64 (d, 4H), 7.58 (d, 4H), 7.51 , &Lt; / RTI &gt; 6H), 1.80 (s, 12H).

<담지 촉매 합성예> - 올레핀 중합용 담지 촉매의 합성&Lt; Synthesis Example of supported catalyst > - Synthesis of supported catalyst for olefin polymerization

모든 합성 반응은 질소 또는 아르곤 등의 비활성 분위기(Inert Atmosphere)에서 진행되었고, 표준 쉴렌크(Standard Schlenk) 기술과 글러브 박스(Glove Box) 기술을 이용하였다.All synthesis reactions proceeded in an inert atmosphere such as nitrogen or argon, using the standard Schlenk technique and the glove box technique.

톨루엔(Sigma-Aldrich사, Anhydrous Grade)을 활성화된 분자체(Molecular Sieve, 4A) 또는 활성화된 알루미나(Alumina)층을 통과시켜 추가로 건조한 다음 사용하였다.Toluene (Sigma-Aldrich, Anhydrous Grade) was further dried by passing through an activated molecular sieve( Molecular Sieve, 4A) or an activated alumina layer.

또, MAO(메틸알루미녹산)는 Albemarle사의 10 % 톨루엔 용액(HS-MAO-10%)을 구매하여 사용하였으며, Silica는 Grace사의 XPO2410을 추가 처리 없이 사용하였다.In addition, MAO (methyl aluminoxane) was purchased from Albemarle's 10% toluene solution (HS-MAO-10%) and Silica used Grace's XPO2410 without further processing.

또한, 비교예로 사용된 비스(n-부틸시클로펜타디에닐)지르코늄 디클로라이드[Bis(n-butylcyclopentadienyl)zirconium dichloride], 비스(인데닐)지르코늄 디클로라이드[Bis(indenyl)zirconium dichloride] 및 라세믹-에틸렌비스(테트라하이드로인데닐)지르코늄 디클로라이드[rac-ethylenebis(tetrahydroindenyl)zirconium dichloride]는 Chemtura Organometallics GmbH에서 구매하여 정제없이 사용하였다.In addition, it is also possible to use bis (n-butylcyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, and racemic Ethylene bis (tetrahydroindenyl) zirconium dichloride was purchased from Chemtura Organometallics GmbH and used without purification.

[담지 촉매 합성예 1][Supported Catalyst Synthesis Example 1]

Glove Box 안에서 [합성예 1]에서 합성된 촉매 화합물([1-(p-Me₂NC₆H₄)-3,4-Me₂C₅H₂]₂ZrCl₂) 및 라세믹-에틸렌비스(테트라하이드로인데닐)지르코늄디클로라이드를 1:1의 몰비율로 혼합한 혼합 촉매 화합물(60 mg), 및 Silica(1.0 g)를 각각 250 mL의 RBf(둥근바닥 플라스크) 담아 Glove Box 밖으로 꺼냈다. 이후, 혼합 촉매 화합물에 톨루엔(10 mL)을 가하여 완전히 용해시킨 후, 상온에서 MAO(5.3 mL)를 촉매 화합물 용액에 천천히 가한 다음, 1 시간 동안 교반하였다. 이어서, Silica에는 톨루엔(10 mL)을 가하고, 상기 슬러리 상태인 실리카의 온도를 0 ℃로 낮춘 뒤, 여기에 혼합 촉매 화합물과 MAO의 혼합 반응 용액을 천천히 가하였다. 이후, 1 시간 동안 교반 한 뒤, 70 ℃로 승온하여 6 시간 동안 더 반응시켰다. 반응이 끝난 후, 교반을 멈춘 다음, 톨루엔층을 분리하여 제거한 후, 노르말헥산으로 세척하고, 진공 하에서 톨루엔을 모두 제거여 옅은 갈색의 자유 유동 분말(Free Flowing Powder)인 올레핀 중합용 담지 촉매를 얻었다.
Glove Box in [Synthesis Example 1] The catalytic compound_{([1- (p -Me 2 NC} 6 H 4) -3,4-Me 2 C 5 H 2] 2 ZrCl 2) and synthesis from racemic-ethylene bis ( Zirconium dichloride in a molar ratio of 1: 1, and Silica (1.0 g) were taken out of the glove box with 250 mL of RBf (round bottom flask). Then, toluene (10 mL) was added to completely dissolve the mixed catalyst compound, MAO (5.3 mL) was slowly added to the catalyst compound solution at room temperature, and the mixture was stirred for 1 hour. Subsequently, toluene (10 mL) was added to the silica, and the temperature of the silica in the slurry state was lowered to 0 ° C, and then the mixed reaction solution of the mixed catalyst compound and MAO was slowly added thereto. Thereafter, the mixture was stirred for 1 hour, then heated to 70 DEG C and further reacted for 6 hours. After the completion of the reaction, the stirring was stopped, and the toluene layer was separated and removed. Then, the solution was washed with normal hexane and then toluene was removed under vacuum to obtain a pale brown free flowing powder (supported catalyst for olefin polymerization) .

[담지 촉매 합성예 2][Supported Catalyst Synthesis Example 2]

[담지 촉매 합성예 1]에서 사용된 [합성예 1]에서 합성된 촉매 화합물 대신 [합성예 1]에서 합성된 촉매 화합물을 사용하고, 라세믹-에틸렌비스(테트라하이드로인데닐)지르코늄디클로라이드 대신 비스(인데닐)지르코늄 디클로라이드를 사용한 것을 제외하고는, 담지 촉매 합성예 1과 동일하게 실시하여 올레핀 중합용 담지 촉매를 합성하였다.
Instead of the racemic-ethylene bis (tetrahydroindenyl) zirconium dichloride using the catalyst compound synthesized in [Synthesis Example 1] instead of the catalyst compound synthesized in [Synthesis Example 1] used in [Supported Catalyst Synthesis Example 1] A supported catalyst for olefin polymerization was synthesized in the same manner as in the supported catalyst Synthesis Example 1 except that bis (indenyl) zirconium dichloride was used.

[담지 촉매 합성예 3][Supported Catalyst Synthesis Example 3]

[담지 촉매 합성예 2]에서 사용된 비스(인데닐)지르코늄 디클로라이드 대신 비스(n-부틸시클로펜타디에닐)지르코늄 디클로라이드를 사용한 것을 제외하고는, 담지 촉매 합성예 2와 동일하게 실시하여 올레핀 중합용 담지 촉매를 합성하였다.
Except that bis (n-butylcyclopentadienyl) zirconium dichloride was used instead of bis (indenyl) zirconium dichloride used in [Supported Catalyst Synthesis Example 2], olefin A supported catalyst for polymerization was synthesized.

[담지 촉매 합성예 4][Supported Catalyst Synthesis Example 4]

[담지 촉매 합성예 2]에서 사용된 [합성예 1]에서 합성된 촉매 화합물 대신 [합성예 2]에서 합성된 촉매 화합물을 사용한 것을 제외하고는, 담지 촉매 합성예 2와 동일하게 실시하여 올레핀 중합용 담지 촉매를 제조하였다.
Except that the catalyst compound synthesized in [Synthesis Example 2] was used instead of the catalyst compound synthesized in [Synthesis Example 1] used in [Supported Catalyst Synthesis Example 2], olefin polymerization To prepare a supported catalyst.

[담지 촉매 합성예 5][Supported Catalyst Synthesis Example 5]

[담지 촉매 합성예 1]에서 사용된 [합성예 1]의 촉매 화합물과 라세믹-에틸렌비스(테트라하이드로인데닐)지르코늄디클로라이드 대신 [합성예 1]의 촉매 화합물, 비스(인데닐)지르코늄디클로라이드 및 라세믹-에틸렌비스(테트라하이드로인데닐)지르코늄 디클로라이드를 1:2:2 몰비율로 혼합하여 사용한 것을 제외하고는, 담지 촉매 합성예 1과 동일하게 실시하여 올레핀 중합용 담지 촉매를 제조하였다.
The catalyst compound of [Synthesis Example 1] used in [Supported Catalyst Synthesis Example 1] and the catalyst compound of [Synthesis Example 1] instead of Racemic-ethylene bis (tetrahydroindenyl) zirconium dichloride, bis (indenyl) zirconium di The supported catalyst for olefin polymerization was prepared in the same manner as in the supported catalyst Synthesis Example 1 except that the catalyst was used in the ratio of 1: 2: 2 molar ratio of dichloromethane, dichloromethane, dichloromethane, dichloromethane, chlorine, and racemic-ethylene bis (tetrahydroindenyl) zirconium dichloride Respectively.

[담지 촉매 비교예 1][Supported Catalyst Comparative Example 1]

[담지 촉매 합성예 1]에서 사용된 [합성예 1]의 촉매 화합물과 라세믹-에틸렌비스(테트라하이드로인데닐)지르코늄디클로라이드 대신 비스(인데닐)지르코늄디클로라이드(0.039 g)만을 사용한 것을 제외하고는, 담지 촉매 합성예 1과 동일하게 실시하여 올레핀 중합용 담지 촉매를 제조하였다.
Except that only the catalyst compound of [Synthesis Example 1] used in [Supported Catalyst Synthesis Example 1] and bis (indenyl) zirconium dichloride (0.039 g) were used in place of racemic-ethylene bis (tetrahydroindenyl) zirconium dichloride Was carried out in the same manner as in the supported catalyst Synthesis Example 1 to prepare a supported catalyst for olefin polymerization.

[담지 촉매 비교예 2][Supported Catalyst Comparative Example 2]

[담지 촉매 합성예 1]에서 사용된 [합성예 1]의 촉매 화합물과 라세믹-에틸렌비스(테트라하이드로인데닐)지르코늄디클로라이드 대신 [합성예 1]의 촉매 화합물(0.059 g)만을 사용한 것을 제외하고는, 담지 촉매 합성예 1과 동일하게 실시하여 올레핀 중합용 담지 촉매를 제조하였다.
Except that only the catalyst compound of Synthesis Example 1 used in [Supported Catalyst Synthesis Example 1] and the catalyst compound (0.059 g) of [Synthesis Example 1] were used in place of racemic-ethylenebis (tetrahydroindenyl) zirconium dichloride Was carried out in the same manner as in the supported catalyst Synthesis Example 1 to prepare a supported catalyst for olefin polymerization.

[담지 촉매 비교예 3][Supported Catalyst Comparative Example 3]

[담지 촉매 합성예 1]에서 사용된 [합성예 1]의 촉매 화합물과 라세믹-에틸렌비스(테트라하이드로인데닐)지르코늄디클로라이드 대신 라세믹-에틸렌비스(테트라하이드로인데닐)지르코늄디클로라이드(43 ㎎)만을 사용한 것을 제외하고는, 담지 촉매 합성예 1과 동일하게 실시하여 올레핀 중합용 담지 촉매를 제조하였다.
Ethylenebis (tetrahydroindenyl) zirconium dichloride (43) instead of the racemic-ethylene bis (tetrahydroindenyl) zirconium dichloride was used instead of the catalyst compound of [Synthesis Example 1] used in [Supported Catalyst Synthesis Example 1] Was used in place of the catalyst used in Example 1 to prepare a supported catalyst for olefin polymerization.

[담지 촉매 비교예 4][Supported Catalyst Comparative Example 4]

[담지 촉매 합성예 1]에서 사용된 [합성예 1]의 촉매 화합물과 라세믹-에틸렌비스(테트라하이드로인데닐)지르코늄디클로라이드 대신 비스(인데닐)지르코늄디클로라이드와 라세믹-에틸렌비스(테트라하이드로인데닐)지르코늄디클로라이드를 1:1 몰비율로 혼합 사용한 것을 제외하고는, 담지 촉매 합성예 1과 동일하게 실시하여 담지 촉매를 제조하였다.
(Indenyl) zirconium dichloride instead of racemic-ethylene bis (tetrahydroindenyl) zirconium dichloride and racemic-ethylene bis (tetra hydroquinone) instead of the catalyst compound of [Synthesis Example 1] used in [Supported Catalyst Synthesis Example 1] Hydroindenyl) zirconium dichloride was mixed at a molar ratio of 1: 1, the supported catalyst was prepared in the same manner as in the supported catalyst Synthesis Example 1.

<중합 실시예> - 올레핀 중합체의 제조&Lt; Polymerization Examples > - Preparation of olefin polymer

모든 중합은 외부 공기와 완전히 차단된 반응기(Autoclave) 내에서 필요량의 용매, 촉매, 에틸렌 및 알파-올레핀 코단량체 등을 주입한 후, 일정한 에틸렌 압력을 유지하면서 진행되었다.All the polymerization proceeded while maintaining constant ethylene pressure after injecting the required amount of solvent, catalyst, ethylene and alpha-olefin comonomer, etc. in a reactor completely blocked with outside air (Autoclave).

중합에 사용된 톨루엔, 노르말헥산 등의 용매(Sigma-Aldrich사, Anhydrous Grade)는 활성화된 분자체(Molecular Sieve, 4A) 또는 활성화된 알루미나(Alumina) 층을 통과시켜 추가로 건조하여 사용하였고, 1.0 M의 트리이소부틸알루미늄(Triisobutylaluminum) 용액은 Sigma-Aldrich사로부터 구매하여 그대로 사용하였다.The solvent (Sigma-Aldrich, Anhydrous Grade) used in the polymerization such as toluene and n-hexane was further dried by passing through an activated molecular sieve (Molecular Sieve, 4A) or an activated alumina layer, Triisobutylaluminum solution of M was purchased from Sigma-Aldrich and used as is.

중합 후 생성된 올레핀 공중합체의 분자량 및 분자량 분포는 GPC(Gel Permeation Chromatography, PL-GPC220)법으로 측정하였고, 녹는점은 DSC(Differential Scanning Calorimetry, TA Instruments)법으로 측정하였다.The molecular weight and molecular weight distribution of the resulting olefin copolymer after polymerization were measured by GPC (Gel Permeation Chromatography, PL-GPC220) method and the melting point was measured by DSC (Differential Scanning Calorimetry, TA Instruments) method.

[중합 실시예 1][Polymerization Example 1]

스테인레스 스틸 반응기의 내부를 질소로 치환한 후, 노르말헥산(1L)을 넣은 다음, 여기에 트리이소부틸알루미늄(2 mmol) 및 1-헥센(10 mL)를 첨가한 후, [담지 촉매 합성예 1]에서 합성된 올레핀 중합용 담지 촉매(50 mg)을 주입하였다.After replacing the interior of the stainless steel reactor with nitrogen, normal hexane (1 L) was added and triisobutylaluminum (2 mmol) and 1-hexene (10 mL) were added thereto. (50 mg) of the synthesized olefin polymerization catalyst.

이후, 승온하여 70 ℃가 되면, 7 bar의 압력으로 에틸렌 가스를 공급하고, 70 ℃의 온도를 유지하면서 1 시간 동안 중합 반응을 실시하였다. 이후, 중합 반응이 완료된 시점에서 에틸렌 공급을 멈추고, 반응기의 온도를 20 ℃로 냉각한 뒤, 미반응 에틸렌을 반응기 외부로 벤트(Vent)하였다. 남아있는 촉매의 활성, 알킬 알루미늄 및 메틸알루미녹산은 산성화된 에탄올(20 mL)을 첨가하여 비활성화시켰다. 이후, 반응물을 여과하여 고체 성분으로 분리한 후, 80 ℃의 온도로 진공 조건하에서 건조하여 올레핀 공중합체를 얻었다.
Thereafter, when the temperature was elevated to 70 deg. C, ethylene gas was supplied at a pressure of 7 bar, and polymerization was carried out for 1 hour while maintaining the temperature at 70 deg. Thereafter, when the polymerization reaction was completed, the supply of ethylene was stopped, the temperature of the reactor was cooled to 20 DEG C, and unreacted ethylene was vented to the outside of the reactor. The activity of the remaining catalyst, alkyl aluminum and methyl aluminoxane was deactivated by the addition of acidified ethanol (20 mL). Thereafter, the reaction product was separated by filtration into a solid component and then dried under a vacuum condition at a temperature of 80 캜 to obtain an olefin copolymer.

[중합 실시예 2][Polymerization Example 2]

담지 촉매 합성예 2에서 합성된 올레핀 중합용 담지 촉매를 사용하는 것을 제외하고는, 중합 실시예 1과 동일하게 수행하여 폴리에틸렌 공중합체를 제조하였다.
Supported Catalyst A polyethylene copolymer was prepared in the same manner as in Polymerization Example 1, except that the supported catalyst for olefin polymerization synthesized in Synthesis Example 2 was used.

[중합 실시예 3][Polymerization Example 3]

담지 촉매 합성예 3에서 합성된 올레핀 중합용 담지 촉매를 사용하는 것을 제외하고는, 중합 실시예 1과 동일하게 수행하여 폴리에틸렌 공중합체를 제조하였다.
Supported Catalyst A polyethylene copolymer was prepared in the same manner as in Polymerization Example 1 except that the supported catalyst for olefin polymerization synthesized in Synthesis Example 3 was used.

[중합 실시예 4][Polymerization Example 4]

담지 촉매 합성예 4에서 합성된 올레핀 중합용 담지 촉매를 사용하는 것을 제외하고는, 중합 실시예 1과 동일하게 수행하여 폴리에틸렌 공중합체를 제조하였다.
Supported Catalyst A polyethylene copolymer was prepared in the same manner as in Polymerization Example 1 except that the supported catalyst for olefin polymerization synthesized in Synthesis Example 4 was used.

[중합 실시예 5][Polymerization Example 5]

담지 촉매 합성예 5에서 합성된 올레핀 중합용 담지 촉매를 사용하는 것을 제외하고는, 중합 실시예 1과 동일하게 수행하여 폴리에틸렌 공중합체를 제조하였다.
Supported Catalyst A polyethylene copolymer was prepared in the same manner as in Polymerization Example 1 except that the supported catalyst for olefin polymerization synthesized in Synthesis Example 5 was used.

[중합 비교예 1][Polymerization Comparative Example 1]

담지 촉매 비교예 1에서 합성된 올레핀 중합용 담지 촉매를 사용하는 것을 제외하고는, 중합 실시예 1과 동일하게 수행하여 폴리에틸렌 공중합체를 제조하였다.
Supported Catalyst A polyethylene copolymer was prepared in the same manner as in Polymerization Example 1 except that the supported catalyst for olefin polymerization synthesized in Comparative Example 1 was used.

[중합 비교예 2][Polymerization Comparative Example 2]

담지 촉매 비교예 2에서 합성된 올레핀 중합용 담지 촉매를 사용하는 것을 제외하고는, 중합 실시예 1과 동일하게 수행하여 폴리에틸렌 공중합체를 제조하였다.
Supported Catalyst A polyethylene copolymer was prepared in the same manner as in Polymerization Example 1 except that the supported catalyst for olefin polymerization synthesized in Comparative Example 2 was used.

[중합 비교예 3][Polymerization Comparative Example 3]

담지 촉매 비교예 3에서 합성된 올레핀 중합용 담지 촉매를 사용하는 것을 제외하고는, 중합 실시예 1과 동일하게 수행하여 폴리에틸렌 공중합체를 제조하였다.
Supported Catalyst A polyethylene copolymer was produced in the same manner as in Polymerization Example 1 except that the supported catalyst for olefin polymerization synthesized in Comparative Example 3 was used.

[중합 비교예 4][Polymerization Comparative Example 4]

담지 촉매 비교예 4에서 합성된 올레핀 중합용 담지 촉매를 사용하는 것을 제외하고는, 중합 실시예 1과 동일하게 수행하여 폴리에틸렌 공중합체를 제조하였다.
Supported Catalyst A polyethylene copolymer was produced in the same manner as in Polymerization Example 1 except that the supported catalyst for olefin polymerization synthesized in Comparative Example 4 was used.

<실험예 1> - 폴리에틸렌 공중합체의 물성&Lt; Experimental Example 1 > - Physical Properties of Polyethylene Copolymer

중합 실시예 1 ~ 5와 중합 비교예 1 ~ 3에서 중합된 폴리에틸렌 공중합체의 물성을 하기 표 1에 나타내었다.Polymerization Examples 1 to 5 and Polymerization Properties of the polyethylene copolymer polymerized in Comparative Examples 1 to 3 are shown in Table 1 below.

중량평균분자량(Mw)(x10⁴)Weight average molecular weight (Mw) (x 10⁴ )분자량 분포(Mw/Mn)Molecular weight distribution (Mw / Mn)Tm(℃)Tm (占 폚)실시예 1Example 152524.644.64126.5126.5실시예 2Example 226263.733.73127.6127.6실시예 3Example 321215.325.32126.9126.9실시예 4Example 425253.693.69126.1126.1실시예 5Example 523233.673.67127.7127.7비교예 1Comparative Example 118183.013.01126.8126.8비교예 2Comparative Example 262623.463.46128.2128.2비교예 3Comparative Example 328283.183.18124.8124.8비교예 4Comparative Example 423233.513.51128.6128.6

상기 표 1을 통해 알 수 있는 바와 같이, 중합 실시예 1 내지 5에서 각각 제조된 폴리올레핀 공중합체의 경우, 중합 비교예 1 내지 4에서 각각 제조된 폴리올레핀 공중합체에 비해 분자량 분포가 효율적으로 조절되었다.As can be seen from the above Table 1, in the case of the polyolefin copolymers prepared in Polymer Examples 1 to 5, the molecular weight distribution was more effectively controlled than in the polyolefin copolymers prepared in Polymerization Comparative Examples 1 to 4, respectively.

이로부터, 높은 분자량과 넓은 분자량 분포의 올레핀 중합체를 제조할 수 있는 화학식 1의 메탈로센 촉매 화합물을 상대적으로 낮은 분자량과 좁은 분자량 분포의 올레핀 중합체를 제조할 수 있는 화학식 2, 3의 메탈로센 촉매 화합물과 함께 주촉매로 사용하는 본 발명의 올레핀 중합용 담지 촉매는 이들의 혼합 비율을 조절하여 분자량 분포 및 분자량를 효율적으로 조절할 수 있다는 것을 확인할 수 있었다.From this, it can be seen that the metallocene catalyst compound of formula (1), which is capable of producing olefin polymers of high molecular weight and broad molecular weight distribution, can be produced by reacting metallocene catalysts of the general formulas (2) and (3) which can produce olefin polymers of relatively low molecular weight and narrow molecular weight distribution It was confirmed that the molecular weight distribution and molecular weight of the supported catalyst for olefin polymerization of the present invention used as the main catalyst together with the catalyst compound can be controlled by controlling the mixing ratio thereof.

Claims (11)

Translated fromKorean

담체 상에,
(a) (ⅰ) 하기 화학식 1로 표시되는 제1 메탈로센 촉매 화합물과; (ⅱ) 하기 화학식 2로 표시되는 제2 메탈로센 촉매 화합물, 하기 화학식 3으로 표시되는 제3 메탈로센 촉매 화합물 또는 이들 모두를 포함하는 주촉매 화합물, 및
(b) 조촉매 화합물
이 담지된 올레핀 중합용 담지 촉매:
[화학식 1]

[화학식 2]

[화학식 3]

(상기 화학식 1 내지 3에서,
M¹ 내지 M³은 서로 동일하거나 상이하며, 각각 독립적으로 주기율표 상의 3~10족 원소로 이루어진 군에서 선택되고;
X¹ 내지 X³는 서로 동일하거나 상이하며, 각각 독립적으로 C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 실릴(C₁~C₂₀)알킬기, C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, (C₆~C₂₀)아릴실릴기, 실릴(C₆~C₂₀)아릴기, C₁~C₂₀의 알콕시기, (C₁~C₂₀)알킬실록시기, C₆~C₂₀의 아릴옥시기, 할로겐 및 아민기로 이루어진 군에서 선택되며;
a 내지 c는 각각 1~5의 정수이고;
B는 탄소(C), 규소(Si), 게르마늄(Ge), 질소(N) 및 인(P)으로 이루어진 군에서 선택되고;
R¹은 수소, C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 실릴(C₁~C₂₀)알킬기, C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, (C₆~C₂₀)아릴실릴기 및 실릴(C₁~C₂₀)아릴기로 이루어진 군에서 선택되며;
d는 1 또는 2이고;
Cp¹ 및 Cp²는 서로 동일하거나 상이하며, 각각 독립적으로 시클로펜타디에닐 골격-함유 리간드이고,
이때, 상기 Cp¹ 및 Cp²의 시클로펜타디에닐 골격-함유 리간드는 C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 실릴(C₁~C₂₀)알킬기, 할로(C₁~C₂₀)알킬기, C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, (C₆~C₂₀)아릴실릴기, 실릴(C₆~C₂₀)아릴기, 할로겐기, 하기 화학식 4로 표시되는 치환체 및 하기 화학식 5로 표시되는 치환체로 이루어진 군에서 선택된 1종 이상의 치환기로 치환 또는 비치환되거나, 또는 상기 인접하는 치환체들이 서로 결합하여 고리를 형성할 수 있으며,
다만, 상기 복수의 시클로펜타디에닐 골격-함유 리간드 중 적어도 하나는 각각 독립적으로 하기 화학식 4로 표시되는 치환체 및 하기 화학식 5로 표시되는 치환체로 이루어진 군에서 선택된 1종 이상의 치환체로 치환되며;
[화학식 4]

[화학식 5]

Z¹ 및 Z²는 서로 동일하거나 상이하며, 각각 독립적으로 질소(N), 인(P), 비소(As), 산소(O), 황(S), 및 셀레늄(Se)로 이루어진 군에서 선택되고;
R² 및 R⁴는 서로 동일하거나 상이하며, 각각 독립적으로 수소, C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 실릴(C₁~C₂₀)알킬기, C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, C₁~C₂₀의 아릴실릴기, 및 실릴(C₁~C₂₀)아릴기로 이루어진 군에서 선택되며;
e 및 h는 각각 1 또는 2이고;
f 및 i는 각각 1~5의 정수이며;
g 및 j는 각각 0~4의 정수이고, 상기 g 및 j가 각각 1~4인 경우, R³ 및 R⁵는 서로 동일하거나 상이하며, 각각 독립적으로 C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 실릴(C₁~C₂₀)알킬기, C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, C₁~C₂₀의 아릴실릴기, 및 실릴(C₁~C₂₀)아릴기로 이루어진 군에서 선택되고;
Ar¹ 내지 Ar⁴는 서로 동일하거나 상이하며, 각각 독립적으로 시클로펜타디에닐 골격-함유 리간드이고,
이때, 상기 Ar¹ 내지 Ar⁴의 시클로펜타디에닐 골격-함유 리간드는 C₁~C₂₀의 알킬기, C₁~C₂₀의 시클로알킬기, C₁~C₂₀의 알킬실릴기, 실릴(C₁~C₂₀)알킬기, 할로(C₁~C₂₀)알킬기, C₆~C₂₀의 아릴기, (C₆~C₂₀)아릴(C₁~C₂₀)알킬기, (C₁~C₂₀)알킬(C₆~C₂₀)아릴기, (C₆~C₂₀)아릴실릴기, 실릴(C₆~C₂₀)아릴기, 및 할로겐기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환 또는 비치환되거나, 또는 상기 인접하는 치환체들이 서로 결합하여 고리를 형성할 수 있음).On the carrier,
(a) (i) a first metallocene catalyst compound represented by the following formula (1); (Ii) a second metallocene catalyst compound represented by the following formula (2), a third metallocene catalyst compound represented by the following formula (3), or both, and
(b) a co-catalyst compound
Supported catalyst for olefin polymerization:
[Chemical Formula 1]

(2)

(3)

(In the above Formulas 1 to 3,
M¹ to M³ are the same or different from each other, and each independently selected from the group consisting of Group 3 to Group 10 elements on the periodic table;
X¹ to X³ are the same or different and each independently represents a C₁ to C₂₀ alkyl group, a C₁ to C₂₀ cycloalkyl group, a C₁ to C₂₀ alkylsilyl group, a silyl (C₁ to C₂₀ ) alkyl, C aryl group of_{6 ~ C 20, (C 6} ~ C 20) aryl (C₁ ~ C₂₀₎ alkyl, (C₁ ~ C₂₀₎ alkyl (C₆ ~ C₂₀₎ aryl, (C₆ ~ C₂₀₎ aryl silyl group, a silyl group (C₆ ~ C₂₀₎ aryl group, C₁ ~ C₂₀ alkoxy group, (C₁ ~ C₂₀₎ alkyl siloxy, aryloxy C₆ ~ C₂₀ of, halogen and An amine group;
a to c are each an integer of 1 to 5;
B is selected from the group consisting of carbon (C), silicon (Si), germanium (Ge), nitrogen (N), and phosphorus (P);
R¹ is selected from the group consisting of hydrogen, a C₁ to C₂₀ alkyl group, a C₁ to C₂₀ cycloalkyl group, a C₁ to C₂₀ alkylsilyl group, a silyl (C₁ to C₂₀ ) alkyl group, a C₆ to C₂₀ aryl group (C₆ -C₂₀ ) aryl (C₁ -C₂₀ ) alkyl, (C₁ -C₂₀ ) alkyl (C₆ -C₂₀ ) aryl, (C₆ -C₂₀ ) arylsilyl and silyl₁ ~ C₂₀₎ is selected from the group consisting of an aryl group;
d is 1 or 2;
Cp &lt;^1&gt; and Cp &lt;² &gt; are the same or different and are each independently a cyclopentadienyl skeleton-
The cyclopentadienyl skeleton-containing ligand of Cp¹ and Cp² may be a C₁ to C₂₀ alkyl group, a C₁ to C₂₀ cycloalkyl group, a C₁ to C₂₀ alkylsilyl group, a silyl (C₁ - C₂₀₎ alkyl, halo (C₁ ~ C₂₀₎ alkyl group, a C aryl group of_{6 ~ C 20, (C 6} ~ C 20) aryl (C₁ ~ C₂₀₎ alkyl, (C₁ ~ C₂₀₎ alkyl ( (C₆ -C₂₀ ) aryl group, a (C₆ -C₂₀ ) arylsilyl group, a silyl (C₆ -C₂₀ ) aryl group, a halogen group, a substituent represented by the following formula Or the adjacent substituents may be bonded to each other to form a ring,
Provided that at least one of the plurality of cyclopentadienyl skeleton-containing ligands is independently substituted with at least one substituent selected from the group consisting of a substituent represented by the following formula (4) and a substituent represented by the following formula (5);
[Chemical Formula 4]

[Chemical Formula 5]

Z¹ and Z² are the same or different and are each independently selected from the group consisting of nitrogen (N), phosphorus (P), arsenic (As), oxygen (O), sulfur (S), and selenium Being;
R² and R⁴ are the same or different and each independently represents hydrogen, a C₁ to C₂₀ alkyl group, a C₁ to C₂₀ cycloalkyl group, a C₁ to C₂₀ alkylsilyl group, a silyl (C₁ to C₂₀₎ alkyl, C aryl group of_{6 ~ C 20, (C 6} ~ C 20) aryl (C₁ ~ C₂₀₎ alkyl, (C₁ ~ C₂₀₎ alkyl (C₆ ~ C₂₀₎ aryl, C₁ ~ C₂₀ aryl silyl group, and silyl (C₁ ~ C₂₀₎ is selected from the group consisting of an aryl group;
e and h are each 1 or 2;
f and i are each an integer of 1 to 5;
g and j is an integer from 0 to 4, respectively, when the g and j are each 1 ~ 4, R³ and R⁵ are the same or different, each independently represent a C₁ ~ C₂₀ alkyl group, C₁ a - silyl C₂₀ cycloalkyl group, C₁ ~ C₂₀ alkyl group, a silyl group (C₁ ~ C₂₀₎ alkyl, C aryl group of_{6 ~ C 20, (C 6} ~ C 20) aryl (C₁ ~ C₂₀₎ An alkyl group, a (C₁ -C₂₀ ) alkyl (C₆ -C₂₀ ) aryl group, a C₁ -C₂₀ arylsilyl group, and a silyl (C₁ -C₂₀ ) aryl group;
Ar¹ to Ar⁴ are the same or different from each other and each independently is a cyclopentadienyl skeleton-containing ligand,
The cyclopentadienyl skeleton-containing ligand of Ar¹ to Ar⁴ may be a C₁ to C₂₀ alkyl group, a C₁ to C₂₀ cycloalkyl group, a C₁ to C₂₀ alkylsilyl group, a silyl (C₁ to C₂₀ ) C₂₀₎ alkyl, halo (C₁ ~ C₂₀₎ alkyl group, a C aryl group of_{6 ~ C 20, (C 6} ~ C 20) aryl (C₁ ~ C₂₀₎ alkyl, (C₁ ~ C₂₀₎ alkyl ( (C₆ -C₂₀ ) aryl group, a (C₆ -C₂₀ ) arylsilyl group, a silyl (C₆ -C₂₀ ) aryl group, and a halogen group, or Said adjacent substituents may combine with each other to form a ring.제1항에 있어서,
상기 M¹ 내지 M³는 서로 동일하거나 상이하며, 각각 독립적으로 주기율표상의 4족 원소 중 하나인 것이 특징인 올레핀 중합용 담지 촉매.The method according to claim 1,
And M &^lt;¹ &gt; to M &lt;³ &^gt; are the same as or different from each other, and each independently is one of the Group 4 elements on the periodic table.삭제delete제1항에 있어서,
상기 주촉매 화합물로,
상기 제1 메탈로센 촉매 화합물과 제2 메탈로센 촉매 화합물의 혼합 사용할 경우, 상기 제1 메탈로센 촉매 화합물과 제2 메탈로센 촉매 화합물의 혼합 비율은 1 : 0.05 ~ 20 몰비율이고,
상기 제1 메탈로센 촉매 화합물과 제3 메탈로센 촉매 화합물의 혼합 사용할 경우, 상기 제1 메탈로센 촉매 화합물과 제3 메탈로센 촉매 화합물의 혼합 비율은1 : 0.05 ~ 20 몰비율이며,
상기 제1 메탈로센 촉매 화합물, 제2 메탈로센 촉매 화합물 및 제3 메탈로센 촉매 화합물을 혼합 사용할 경우, 상기 제1 메탈로센 촉매 화합물, 제2 메탈로센 촉매 화합물 및 제3 메탈로센 촉매 화합물의 혼합 비율은 1 : 0.05 ~ 20 : 0.05 ~ 20 몰비율인 것이 특징인 올레핀 중합용 담지 촉매.The method according to claim 1,
As the main catalyst compound,
When the first metallocene catalyst compound and the second metallocene catalyst compound are mixed, the mixing ratio of the first metallocene catalyst compound to the second metallocene catalyst compound is 1: 0.05 to 20 molar ratio,
When the first metallocene catalyst compound and the third metallocene catalyst compound are used in combination, the mixing ratio of the first metallocene catalyst compound to the third metallocene catalyst compound is 1: 0.05 to 20 molar ratio,
When the first metallocene catalyst compound, the second metallocene catalyst compound and the third metallocene catalyst compound are used in combination, the first metallocene catalyst compound, the second metallocene catalyst compound, and the third metallocene catalyst compound Wherein the mixing ratio of the catalyst component is from 1: 0.05 to 20: 0.05 to 20 molar ratio.제1항에 있어서,
상기 조촉매 화합물은 ⅰ) 알루미녹산 화합물, ⅱ) 유기알루미늄 화합물, 및 ⅲ) 메탈로센 촉매 화합물과 반응하여 메탈로센 촉매 화합물이 촉매 활성을 갖게 하는 벌키한 화합물로 이루어진 군으로부터 선택된 것이 특징인 올레핀 중합용 담지 촉매.The method according to claim 1,
Wherein the promoter compound is selected from the group consisting of i) aluminoxane compounds, ii) organoaluminum compounds, and iii) a bulky compound that reacts with the metallocene catalyst compound to render the metallocene catalyst compound catalytically active. Supported catalyst for olefin polymerization.제1항에 있어서,
상기 조촉매 화합물은 하기 화학식 6로 표시되는 화합물 내지 화학식 8로 표시되는 화합물 중에서 선택된 것이 특징인 올레핀 중합용 담지 촉매:
[화학식 6]

[화학식 7]

[화학식 8]

(상기 화학식 6 내지 8에서,
R⁶은 C₁~C₁₀의 알킬기이고;
q는 1~70의 정수이며;
R⁷ 내지 R⁹는 서로 동일하거나 상이하며, 각각 독립적으로 C₁~C₁₀의 알킬기, C₁~C₁₀의 알콕시기 또는 할로겐이고, 다만 R⁵ 내지 R⁷ 중 적어도 하나는 C₁~C₁₀의 알킬기이며;
C는 루이스 염기의 수소 이온 결합 양이온이거나, 또는 산화력이 있는 금속 또는 비금속 화합물이고;
D는 주기율표상의 5~15족의 원소로 이루어진 군에서 선택된 원소와 유기물질의 화합물임).The method according to claim 1,
Wherein the promoter compound is selected from a compound represented by the following general formula (6) to a compound represented by the general formula (8):
[Chemical Formula 6]

(7)

[Chemical Formula 8]

(In the above formulas 6 to 8,
R⁶ is a C₁ to C₁₀ alkyl group;
q is an integer from 1 to 70;
R⁷ to R⁹ are the same or different and are each independently a C₁ to C₁₀ alkyl group, a C₁ to C₁₀ alkoxy group or a halogen, provided that at least one of R⁵ to R⁷ is a C₁ to C₁₀ Lt; / RTI &gt;
C is a hydrogen ion-binding cation of a Lewis base, or is a metal or non-metal compound having an oxidizing power;
D is a compound of an organic substance and an element selected from the group consisting of elements of Groups 5 to 15 on the periodic table).제1항에 있어서,
상기 주촉매 화합물과 조촉매 화합물의 사용 비율은 상기 주촉매 화합물에 함유된 전이금속 원자에 대한 조촉매 화합물에 함유된 금속의 몰비가1 : 0.01 ~ 1000 범위인 것이 특징인 올레핀 중합용 담지 촉매.The method according to claim 1,
The ratio of the main catalyst compound to the co-catalyst compound is such that the molar ratio of the metal contained in the co-catalyst compound to the transition metal atom contained in the main catalyst compound is 1: 0.01 to 1000. &lt; / RTI &gt;제1항에 있어서,
상기 담체는 실리카(Silica), 알루미나(Alumina), 보오크사이트(Bauxite), 제올라이트(Zeolite), MgCl₂, CaCl₂, MgO, ZrO₂, TiO₂, B₂O₃, CaO, ZnO, BaO, ThO₂, 및 이들의 복합체로 이루어진 군에서 선택되거나, 또는 전분(Starch), 사이클로덱스트린(Cyclodextrin) 및 합성고분자로 이루어진 군에서 선택된 것이 특징인 올레핀 중합용 담지 촉매.The method according to claim 1,
The support is silica (Silica), alumina (Alumina), bauxite (Bauxite), zeolite_{(Zeolite), MgCl 2, CaCl} 2, MgO, ZrO 2, TiO 2, B 2 O 3, CaO, ZnO, BaO, ThO₂ , and a complex thereof, or selected from the group consisting of starch, cyclodextrin, and a synthetic polymer.제1항, 제2항 및 제4항 내지 제8항 중 어느 한 항에 기재된 올레핀 중합용 담지 촉매의 존재 하에 서 하나 이상의 올레핀계 단량체를 중합시키는 단계를 포함하는 올레핀 중합체의 제조방법.10. A process for producing an olefin polymer comprising polymerizing at least one olefin monomer in the presence of the supported catalyst for olefin polymerization according to any one of claims 1, 2 and 4 to 8.제9항에 있어서,
상기 올레핀계 단량체는 C₂~C₂₀의 α-올레핀, C₄~C₂₀의 디올레핀, C₃~C₂₀의 시클로올레핀, C₃~C₂₀의 시클로디올레핀, 스티렌 및 스티렌 유도체로 이루어진 군에서 선택된 것으로,
상기 스티렌 유도체는 벤젠 고리(phenylring)에 C₁~C₁₀의 알킬기, C₁~C₁₀의 알콕시기, 할로겐기, 아민기, 실릴기 및 할로(C₁~C₁₀)알킬기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환된 것이 특징인 올레핀 중합체의 제조방법.10. The method of claim 9,
Wherein the olefinic monomer comprises a C₂ to C₂₀ alpha-olefin, a C₄ to C₂₀ diolefin, a C₃ to C₂₀ cycloolefin, a C₃ to C₂₀ cycloolefin, a styrene and a styrene derivative &Lt; / RTI &gt;
The styrene derivative is selected from the group consisting of a C₁ -C₁₀ alkyl group, a C₁ -C₁₀ alkoxy group, a halogen group, an amine group, a silyl group, and a halo (C₁ -C₁₀ ) alkyl group in a benzene ring Wherein the substituent is substituted with at least one substituent.제9항에 기재된 방법에 의해 제조되고, 중량평균분자량(Mw)이 500 ~ 3,000,000이고, 분자량 분포가 3 ~ 10 범위인 올레핀 중합체.An olefin polymer produced by the method according to claim 9, having a weight average molecular weight (Mw) of 500 to 3,000,000 and a molecular weight distribution of 3 to 10.