KR20100087913A - High active and high selective ethylene oligomerization catalyst, and process for preparing hexene or octene using thereof - Google Patents

High active and high selective ethylene oligomerization catalyst, and process for preparing hexene or octene using thereof Download PDF

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KR20100087913A
KR20100087913A KR1020090006977A KR20090006977A KR20100087913A KR 20100087913 A KR20100087913 A KR 20100087913A KR 1020090006977 A KR1020090006977 A KR 1020090006977A KR 20090006977 A KR20090006977 A KR 20090006977A KR 20100087913 A KR20100087913 A KR 20100087913A
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ethylphenyl
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한택규
강상욱
김성관
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에스케이에너지 주식회사
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    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
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    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes

Abstract

PURPOSE: A chrome complex compound for preparing the selective oligomer of ethylene containing chiral ligand is provided to reduce a polymer by-product generation amount and to be used in preparing 1-hexene or 1-octene. CONSTITUTION: A chrome complex compound for preparing the selective oligomer of ethylene contains chiral ligand of chemical formula 1 or 2. The A of chiral ligand is (C1-C5)alkylene or (C1-C5)alkenylene. The chrome complex catalyst composition for preparing the selective oligomer of ethylene contains the chrome complex compound and co-catalyst. The co-catalyst is an organic aluminium compound, organic boron compound, organic salt, or phosphorus.

Description

고활성과 고선택적인 에틸렌 올리머고화 촉매 및 이를 이용한 헥센 또는 옥텐의 제조방법{High Active and High Selective Ethylene Oligomerization Catalyst, and process for preparing hexene or octene using thereof}High Active and High Selective Ethylene Oligomerization Catalyst and Process for Preparing Hexene or Octene

본 발명은 에틸렌의 삼량체화나 사량체화와 같은 올리고머화 반응에 사용하기 위한 고활성과 고선택적인 에틸렌 올리머고화 촉매 및 이를 이용한 1-헥센 또는 1-옥텐의 제조방법에 관한 것으로서, 보다 구체적으로는 크롬 화합물과 특정의 입체이성질체 구조를 갖는 키랄성 리간드로 이루어진 에틸렌의 선택적 올리고머 제조용 크롬 착체 화합물과 에틸렌의 선택적 올리고머 제조용 크롬 착체 화합물에 메틸아루미녹산(MAO) 등의 조촉매를 포함하는 에틸렌의 선택적 올리고머 제조용 크롬 착체 촉매 조성물 및 이들 촉매계를 이용하여 고활성과 고선택적으로 1-헥센 또는 1-옥텐을 제조하는 방법에 관한 것이다.The present invention relates to a highly active and highly selective ethylene oligomerization catalyst for use in oligomerization reactions such as trimerization or tetramerization of ethylene, and to a process for preparing 1-hexene or 1-octene using the same. Is an optional oligomer of ethylene comprising a chromium complex for the selective oligomer preparation of ethylene consisting of a chromium compound and a chiral ligand having a specific stereoisomer structure and a promoter such as methylaluminoxane (MAO) in the chromium complex compound for the selective oligomer preparation of ethylene It relates to a production chromium complex catalyst composition and a method for producing 1-hexene or 1-octene with high activity and high selectivity using these catalyst systems.

1-헥센 및 1-옥텐은 선형저밀도 폴리에틸렌을 만들기 위한 모노머 또는 코모노머로서 중합공정에 광범위하게 사용되는 중요한 상업적 원료로서, 에틸렌의 올리고머화 반응에 의해 생성된 제품을 정제하여 얻어진다. 그러나 기존의 에틸렌 올리고머화 반응은 1-헥센 및 1-옥텐과 함께 상당한 양의 부텐, 고급 올리고머와 폴리 에틸렌을 함께 생성하는 비효율적인 측면이 있었다. 이러한 종래 에틸렌의 올리고머화 기술은 일반적으로 슐쯔-플로리(Schulze-Flory) 또는 포이즌(Poisson) 생성물 분포에 따라 다양한 α-올레핀을 생성하게 되므로, 원하는 생성물의 수율을 제한한다. 1-hexene and 1-octene are important commercial raw materials widely used in the polymerization process as monomers or comonomers for making linear low density polyethylene and are obtained by purifying products produced by oligomerization of ethylene. However, the existing ethylene oligomerization reaction has been an inefficient aspect of producing a considerable amount of butenes, higher oligomers and polyethylene together with 1-hexene and 1-octene. This conventional oligomerization technique of ethylene generally produces a variety of α-olefins depending on the Schulze-Flory or Poisson product distribution, thus limiting the yield of the desired product.

최근에 에틸렌을 전이금속 촉매작용을 통해 선택적으로 삼량체화하여 1-헥센을 생산하거나 또는 선택적으로 사량체화시켜 1-옥텐을 생산하는 것에 대한 연구가 진행되고 있는데, 공지된 대부분의 전이금속 촉매는 크롬계 촉매이다. 국제공개특허 제WO 02/04119호는 에틸렌 삼량체화 촉매로서 일반식 (R1)(R2)X-Y-X(R3)(R4)의 리간드를 사용한 크롬계 촉매를 개시하고 있는바, 여기에서, X는 인, 비소, 또는 안티몬이고, Y는 -N(R5)-와 같은 연결 그룹이며, R1, R2, R3 및 R4중 적어도 하나가 극성 또는 전자 수여 치환체를 가진다. Recently, research has been conducted on the production of 1-hexene by selectively trimerization of ethylene through transition metal catalysis or selectively tetramerization to produce 1-octene. Most known transition metal catalysts are chromium. System catalyst. WO 02/04119 discloses a chromium-based catalyst using a ligand of the general formula (R 1 ) (R 2 ) XYX (R 3 ) (R 4 ) as an ethylene trimerization catalyst, wherein X is phosphorus, arsenic, or antimony, Y is a linking group such as -N (R 5 )-, and at least one of R 1 , R 2 , R 3 and R 4 has a polar or electron-donating substituent.

또 다른 공지 문헌에서는 촉매 조건하에 1-헥센에 대해 촉매 활성을 나타내지 않는 리간드로서 R1, R2, R3 및 R4 중 적어도 하나에 극성 치환체를 가지지 않는 화합물인 (o-에틸페닐)2PN(Me)P(o-에틸페닐)2의 용도를 개시하였다.(Antea Carter et al., Chem. Commun., 2002, p. 858 - 859). Another publication discloses (o-ethylphenyl) 2 PN, a compound that does not have a polar substituent on at least one of R 1 , R 2 , R 3 and R 4 as a ligand that does not exhibit catalytic activity for 1-hexene under catalytic conditions. The use of (Me) P (o-ethylphenyl) 2 is disclosed. (Antea Carter et al., Chem. Commun., 2002, p. 858-859).

또한 한국공개특허 제2006-0002741호에는 (o-에틸페닐)2PN(Me)P(o-에틸페닐)2 과 같이 인에 부착된 페닐환의 오르토 위치상에 비극성 치환체를 함유하는 PNP 리간드를 사용하여 우수한 에틸렌 삼량체화 활성 및 선택성이 실제로 가능하다는 것이 공지되어있다. In addition, Korean Patent Laid-Open Publication No. 2006-0002741 discloses (o-ethylphenyl) 2 PN (Me) P (o-ethylphenyl) 2 as It is known that excellent ethylene trimerization activity and selectivity are indeed possible using PNP ligands containing nonpolar substituents on the ortho position of the phenyl ring attached to phosphorus.

한편, 국제공개특허 제WO 04/056479호에는 인에 부착된 페닐환에 치환체가 생략된 PNP 리간드를 함유하는 크롬계 촉매에 의해 에틸렌을 사량체화하여 1-옥텐을 생성함에 있어서 선택도를 향상시킨다는 것이 공지되었으며, 이들 에틸렌 사량체화를 위한 사량체화 촉매에 사용되는 헤테로 원자 리간드의 예로서 (페닐)2PN(아이소프로필)P(페닐)2 등을 개시하고 있다.On the other hand, WO 04/056479 discloses that the selectivity is improved by tetramerization of ethylene by a chromium-based catalyst containing a PNP ligand in which a phenyl ring attached to phosphorus is omitted. It is known, and (phenyl) 2 PN (isopropyl) P (phenyl) 2 and the like are disclosed as examples of the hetero atom ligands used in the tetramerization catalyst for these ethylene tetramerization.

상기 선행 기술은 질소 및 인을 헤테로 원자로 가지는 헤테로 원자 리간드를 함유하는 크롬계 촉매가 인 원자에 결합된 하이드로카빌 또는 헤테로하이드로카빌 그룹에 대한 극성치환체 없이도 에틸렌을 사량체하여 70 질량%를 초과하는 선택성으로 1-옥텐을 생산할 수 있음을 개시하였다. This prior art has a selectivity of greater than 70% by mass of chromium-based catalysts containing heteroatom ligands having nitrogen and phosphorus as heteroatoms, tetramers of ethylene without polar substituents to hydrocarbyl or heterohydrocarbyl groups bonded to the phosphorus atom. It was disclosed that 1-octene can be produced.

그러나 종래의 선행기술들은 헤테로 원자를 포함하는 리간드의 구조와 관련하여 구체적으로 어떠한 형태가 고선택적으로 에틸렌을 사량체화하여 1-옥텐을 생성하거나 에틸렌을 삼량체화하여 1-헥센을 생성할 수 있는지에 관한 명확한 예를 제시하지 못 하였을 뿐 아니라, 70 질량% 정도의 1-옥텐 선택성을 가지는 리간드로서 (R1)(R2)P-(R5)N-P(R3)(R4)와 같은 PNP형 골격의 구조 밖에 제시하지 못 하였으며, 헤테로 원자 리간드 중 치환 가능한 치환체의 형태도 제한적으로 개시하고 있을 뿐이다. 즉, 사량체화 선택도에 중요한 영향을 미치는 인자는 리간드 골격 구조 중의 P원자와 또 다른 P 원자 사이의 다리 구조가 결정적임에도 불구하고 선행 기술은 다리 구조 양 쪽에 P 원자와 P 원자가 연결되기만 하면 고선택도의 촉매로 기술하였다. However, the prior art is specifically related to the structure of a ligand containing a hetero atom in which form can be highly selectively tetramerized ethylene to produce 1-octene or ethylene trimerized to produce 1-hexene. In addition to not providing a clear example, the ligand having a 1-octene selectivity of about 70% by mass is (R 1 ) (R 2 ) P- (R 5 ) N- P (R 3 ) (R 4 ) and Only the structure of the same PNP-type backbone is shown, and the types of substitutable substituents in the heteroatom ligand are also limited. In other words, the factor which has an important influence on the tetramerization selectivity is that although the bridge structure between P atom and another P atom in the ligand skeleton structure is decisive, the prior art is highly selected as long as the P atom and P atom are connected to both sides of the bridge structure. It is described by the catalyst of FIG.

또한, 종래의 선행기술인 헤테로원자를 포함하는 PNP형 골격의 리간드는 1-옥텐 또는 1-헥센 제조반응에 있어 반응 시간에 따라 그 반응 활성이 일관적으로 유지되지 못하고 반응 속도가 크게 감소하는 문제가 있었다. 이러한 원인은 골격 구조에 포함된 질소 원자는 비공유전자쌍이 존재하여 이로 인해 쉽게 전이 금속과 배위할 수 있어 리간드로서 적합하다고 할 수 있으나 이는 상대적으로 배위력이 약한 인 원자로 하여금 쉽게 전이금속으로부터 해리하도록 유도할 수 있기 때문이다. 공지된 문헌에서는 PNP 골격 리간드는 용매와 치환체의 극성 등 합성 환경에 따라 P-N-P구조가 쉽게 N=P-P 구조로 전환될 수 있음을 개시하였다.(Dalton Trans., 2003, 2772) In addition, the ligand of the PNP-type skeleton containing a hetero atom of the prior art is a problem that the reaction activity is not consistently maintained and reaction rate is greatly reduced depending on the reaction time in 1-octene or 1-hexene production reaction. there was. The reason for this is that the nitrogen atoms included in the skeletal structure are suitable as ligands because of the presence of non-covalent electron pairs, which can be easily coordinated with the transition metals, but this leads to the relatively weak coordination of phosphorus atoms to dissociate from the transition metals easily. Because you can. In the known literature, it has been disclosed that PNP backbone ligands can be easily converted to N = PP structures depending on the synthetic environment such as the polarity of the solvent and substituents ( Dalton Trans. , 2003, 2772).

한편, 또 다른 공지된 문헌에서는 헤테로원자를 포함하는 PNP형 골격의 리간드는 크롬 전구체와 미리 촉매 착체를 합성하여 에틸렌 올리고머화 반응을 실시한 결과 리간드와 크롬 전구체를 따로따로 주입한 결과와 활성 및 선택도가 크게 변화가 없음을 공지된바 있다.(J. Am. Chem. Soc., 2004, 126, 14712) On the other hand, in another known literature, the ligand of the PNP-type skeleton containing a hetero atom synthesizes a chromium precursor and a catalyst complex in advance and performs an ethylene oligomerization reaction to separately inject the ligand and the chromium precursor, and the activity and selectivity. It is known that there is no significant change. ( J. Am. Chem. Soc. , 2004, 126, 14712)

그러나 상기한 수많은 공지문헌에도 불구하고, 이들 공지문헌에는 실질적으로 1-헥센과 1-옥텐을 높은 활성과 높은 선택비로 제조하는 것은 극히 일부의 촉매에 대해서만 개시되어 있을 뿐이고, 활성도 역시 낮아 상업적 활용도에 제한이 있으며, 특히 공지 촉매들은 메틸알루미녹산으로 예시되는 고가의 조촉매를 채용해야 하는 문제점이 있어 더욱 더 상업화에는 제한이 있는 문제가 있다.However, in spite of the numerous publications mentioned above, the preparation of substantially 1-hexene and 1-octene with high activity and high selectivity in these publications is only disclosed for a few catalysts, and the activity is also low, making them commercially viable. There are limitations, and in particular, known catalysts have a problem of employing an expensive promoter exemplified by methylaluminoxane, and thus there is a problem of limitation in commercialization.

본 출원인은 한국 특허출원 제2007-0005688에 상기한 종래의 선행 기술의 촉매 안정성을 극복하기 위해서 원자 P와 P 사이의 구조 뿐 아니라 P 원자의 치환체 R1, R2, R3, R4를 다양하게 변화하면서 에틸렌 올리고머화 반응실험 한 결과, 골격구조 내에 질소를 포함하지 않는 본 발명에 따른 P-C-C-P 골격 구조 리간드를 포함하는 크롬계 촉매계를 이용하여 높은 선택성으로 에틸렌을 삼량체화하거나 사량체화하여 1-헥센이나 1-옥텐을 생성할 수 있을 뿐 아니라, 반응시간에 따라 촉매의 활성이 상당히 안정되어 반응 속도가 지속적으로 유지될 수 있음을 발견하였고, 또한 본 발명에 따른 P-C-C-P 골격 구조의 리간드에서 두 인 원자 사이의 탄소원자에 이웃하는 구조가 입체적으로 달라짐에 따라 삼량체화 및 사량체화 반응의 활성 및 선택도가 크게 향상될 수 있음을 공개 하였다.In order to overcome the catalyst stability of the prior art as described in Korean Patent Application No. 2007-0005688, the applicant has various substituents R 1 , R 2 , R 3 , R 4 as well as the structure between atoms P and P. As a result of the ethylene oligomerization reaction with various changes, 1-hexene was trimerized or tetramerized with ethylene with high selectivity using a chromium-based catalyst system containing the PCCP skeletal structure ligand according to the present invention which does not contain nitrogen in the framework structure. It was found that not only can generate 1-octene, but also that the activity of the catalyst is considerably stable according to the reaction time, so that the reaction rate can be maintained continuously. In addition, two phosphorus atoms in the ligand of the PCCP skeleton structure according to the present invention can be maintained. As the structure adjacent to the carbon atoms in between is stericly changed, the activity and selectivity of the trimerization and tetramerization reaction can be greatly improved. It was published.

그러나 종래의 기술에서는 전이 금속과 P-C-C-P 골격구조의 리간드를 에틸렌 올리고머화 반응 매개체에 따로따로 주입하게 되면 활성과 선택도의 향상이 한계가 있었다. 그 이유는 골격 구조가 탄소 원자로서 비공유 전자쌍이 존재하지 않고 전이금속에 전자 공여 역할을 하는 인 원자 주위가 골격구조 내의 키랄 탄소로 말미암아 전이 금속 배위 방향이 한정되어 있어 반응 매질 내에서 전이금속에 접근하여 배위 결합하는데 어려움이 있는 것으로 인식된다. 결국 이러한 P-C-C-P 골격 구조의 입체적, 전자적 효과는 전이금속 전구체와 P-C-C-P 골격 구조 리간드를 PNP 리 간드의 경우처럼 촉매로서 에틸렌 올리고머화 반응 매개체에 따로따로 주입하게 되면 PNP 리간드의 경우와 달리 실질적으로 촉매 활성점으로 전환될 전이 금속 전구체의 분자 수가 작아지게 되며, 이는 에틸렌의 삼량체 또는 사량체화에 있어서 활성과 선택도 저하를 초래하게 된다.However, in the related art, when the ligand of the transition metal and the P-C-C-P framework is separately injected into the ethylene oligomerization reaction medium, there is a limit in improving the activity and selectivity. The reason for this is that the structure of the transition metal coordination is limited due to the chiral carbon in the skeletal structure around the phosphorus atom in which the skeletal structure does not exist as a carbon atom and there is no lone pair of electrons. It is recognized that there is a difficulty in coordination coupling. As a result, the steric and electronic effects of the PCCP skeleton structure are substantially different from those of the PNP ligand when the transition metal precursor and the PCCP skeleton ligand are separately injected into the ethylene oligomerization reaction medium as a catalyst as in the case of PNP ligand. The number of molecules of the transition metal precursor to be converted to becomes small, which leads to a decrease in activity and selectivity in trimer or tetramerization of ethylene.

본 출원인은 이러한 촉매 활성 향상의 한계를 극복하기 위해서 P-C-C-P 골격 구조의 키랄성 리간드를 전이금속 전구체와 미리 반응시켜 실질적으로 순수한 형태의 전이금속 착체를 합성하고 이를 에틸렌 올리고머화 매개체에 주입한 결과 놀랍게도 촉매의 활성과 선택도가 극적으로 증가하는 것을 확인하였으며, 이를 바탕으로 본 발명을 완성하기에 이르렀다.In order to overcome this limitation of catalytic activity, the Applicant has previously reacted a chiral ligand of PCCP skeleton structure with a transition metal precursor to synthesize a substantially pure transition metal complex and injects it into an ethylene oligomerization medium. It was confirmed that the activity and selectivity increased dramatically, and came to complete the present invention based on this.

따라서 본 발명의 목적은 에틸렌의 삼량체화나 사량체화와 같은 올리고머화 반응에 사용하기 위한 고활성과 고선택적인 에틸렌 올리머고화 촉매로서 P-C-C-P 골격 구조의 키랄성 리간드와 크롬이 결합된 에틸렌의 선택적 올리고머 제조용 크롬 착체 화합물을 제공하는 것이며, 또 다른 목적으로서, 상기 에틸렌의 선택적 올리고머 제조용 크롬 착체 화합물에 메틸아루미녹산(MAO) 등의 조촉매를 포함하는 에틸렌의 선택적 올리고머 제조용 크롬 착체 촉매 조성물 및 이들 촉매계를 이용하여 고활성과 고선택적으로 1-헥센 또는 1-옥텐을 제조하는 방법을 제공하는 것이다.Accordingly, an object of the present invention is to prepare a selective oligomer of ethylene in which chromium is bonded to chiral ligand of PCCP skeleton structure as a highly active and highly selective ethylene oligomerization catalyst for use in oligomerization reactions such as trimerization or tetramerization of ethylene. The present invention provides a chromium complex compound, and as another object, a chromium complex catalyst composition for selective oligomer production of ethylene comprising a promoter such as methylaluminoxane (MAO) in a chromium complex compound for selective oligomer production of ethylene and a catalyst system thereof It is to provide a method for producing 1-hexene or 1-octene with high activity and high selectivity.

이하, 본 발명을 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.

본 발명은 키랄성 P-C-C-P 골격 구조 리간드를 전이금속 또는 전이금속 전구체에 배위함으로써 착화 화합물을 합성하고 본 전이금속 착체화합물을, 에틸렌 올리고머화 촉매로 사용하는 것이다. 좀 더 구체적으로는 하기 화학식 1 또는 화학식 2의 키랄성 리간드를 포함하는 에틸렌의 선택적 올리고머 제조용 크롬 착체 화합물.This invention synthesize | combines a complexing compound by coordinating a chiral P-C-C-P skeletal structure ligand to a transition metal or a transition metal precursor, and uses this transition metal complex compound as an ethylene oligomerization catalyst. More specifically, a chromium complex compound for producing a selective oligomer of ethylene comprising a chiral ligand of Formula 1 or Formula 2 below.

[화학식 1][Formula 1]

Figure 112009005732370-PAT00003
Figure 112009005732370-PAT00003

[화학식 2][Formula 2]

Figure 112009005732370-PAT00004
Figure 112009005732370-PAT00004

[상기 화학식 1 또는 화학식 2에서, R1, R2, R3, R4, R7, R8, R9 및 R10은 서로 독립적으로 하이드로카빌, 치환된 하이드로카빌, 헤테로하이드로카빌, 또는 치환된 헤테로하이드로카빌이고; R5, R6, R11및 R12는 서로 독립적으로 하이드로카빌 또는 치환된 하이드로카빌이거나, R5과 R6, R11과 R12가 서로 하이드로카빌렌, 치환된 하이드로카빌렌, 헤테로하이드로카빌렌 또는 치환된 헤테로하이드로카빌렌으로 결합될 수 있으며; X1 내지 X6는 각각 독립적으로 할로겐, -OR21및, -OCOR22 또는 -NR23R24이고, 상기 R21, R22, R23 또는 R24는 수소, 하이드로카빌 또는 헤테로하이드로카빌이며; L은 하이드로카본 또는 헤테로하이드로카본이고; * 및 **는 키랄 탄소 위치로 서로 독립적으로 (S) 또는 (R) 배열을 의미한다. ][In Formula 1 or Formula 2, R 1 , R 2 , R 3 , R 4 , R 7 , R 8 , R 9 and R 10 are each independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted Heterohydrocarbyl; R 5 , R 6 , R 11 and R 12 are each independently hydrocarbyl or substituted hydrocarbyl, or R 5 and R 6 , R 11 and R 12 may be bonded to each other with hydrocarbylene, substituted hydrocarbylene, heterohydrocarbylene or substituted heterohydrocarbylene; Each X 1 to X 6 is independently halogen, —OR 21 and —OCOR 22 or —NR 23 R 24 , wherein R 21 , R 22 , R 23 or R 24 is hydrogen, hydrocarbyl or heterohydrocarbyl; L is hydrocarbon or heterohydrocarbon; * And ** refer to the (S) or (R) configuration independently of one another in the chiral carbon position. ]

상기 하이드로카빌 또는 헤테로하이드로카빌은 하이드로카본 또는 헤테로하이드로카본으로부터 유도되는 1개의 결합위치를 갖는 라디칼을 의미하는 것으로서, 하이드로카빌렌은 하이드로카본으로부터 유도되는 2개의 결합위치를 갖는 라디칼을 의미하며, 헤테로의 의미는 탄소가 O, S, N 원자로 치환된 것을 의미한다.The hydrocarbyl or heterohydrocarbyl means a radical having one binding position derived from a hydrocarbon or a heterohydrocarbon, and the hydrocarbylene means a radical having two binding positions derived from a hydrocarbon, and hetero Means that carbon is substituted with O, S, N atoms.

본 발명에 따른 키랄성 리간드에 있어 * 및 **위치의 키랄 탄소는 키랄성은 (R, R), (R, S), (S, R), (S, S)의 배열 쌍을 가진다.Chiral carbons in the * and ** positions of the chiral ligands according to the present invention have chirality (R, R), (R, S), (S, R), (S, S).

본 발명에 따른 화학식 1 또는 화학식 2의 에틸렌의 선택적 올리고머 제조용 크롬 착체 화합물은 하기 화학식 3 내지 화학식 8의 키랄성 리간드를 포함한다.Chromium complex compounds for the selective oligomer preparation of ethylene of formula 1 or formula 2 according to the present invention include chiral ligands of formulas 3-8.

[화학식 3](3)

Figure 112009005732370-PAT00005
Figure 112009005732370-PAT00005

[화학식 4][Formula 4]

Figure 112009005732370-PAT00006
Figure 112009005732370-PAT00006

[화학식 5][Chemical Formula 5]

Figure 112009005732370-PAT00007
Figure 112009005732370-PAT00007

[화학식 6][Formula 6]

Figure 112009005732370-PAT00008
Figure 112009005732370-PAT00008

[화학식 7][Formula 7]

Figure 112009005732370-PAT00009
Figure 112009005732370-PAT00009

[화학식 8][Formula 8]

Figure 112009005732370-PAT00010
Figure 112009005732370-PAT00010

상기 화학식 2 내지 화학식 6의 치환체는 화학식 1과 화학식 2의 치환체의 정의와 동일하다.The substituents of Chemical Formulas 2 to 6 are the same as the definitions of the substituents of Chemical Formula 1 and Chemical Formula 2.

상기 화학식 1 또는 화학식 2의 에틸렌의 선택적 올리고머 제조용 크롬 착체 화합물은 R5과 R6, R11과 R12가 서로 하이드로카빌렌, 치환된 하이드로카빌렌, 헤테로하이드로카빌렌 또는 치환된 헤테로하이드로카빌렌으로 결합되는 경우 하기 구조의 화학식 8 내지 화학식 10의 화합물을 포함한다.The chromium complex compound for the selective oligomer preparation of ethylene of Formula 1 or Formula 2 is R 5 and R 6 , When R 11 and R 12 are bonded to each other with hydrocarbylene, substituted hydrocarbylene, heterohydrocarbylene or substituted heterohydrocarbylene, the compound of Formula 8 to Formula 10 having the following structure is included.

[화학식 9][Formula 9]

Figure 112009005732370-PAT00011
Figure 112009005732370-PAT00011

[화학식 10][Formula 10]

Figure 112009005732370-PAT00012
Figure 112009005732370-PAT00012

[화학식 11][Formula 11]

Figure 112009005732370-PAT00013
Figure 112009005732370-PAT00013

[화학식 12][Formula 12]

Figure 112009005732370-PAT00014
Figure 112009005732370-PAT00014

[화학식 13][Formula 13]

Figure 112009005732370-PAT00015
Figure 112009005732370-PAT00015

[화학식 14][Formula 14]

Figure 112009005732370-PAT00016
Figure 112009005732370-PAT00016

상기 화학식 9 내지 화학식 14에서 A는 (C1-C5)알킬렌, (C1-C5)알케닐렌로부터 선택되며, 상기 알킬렌과 알케닐렌은 (C3-C5)알킬렌, (C3-C5)알케닐렌의 경우 (C5-C7)시클로알킬 또는 (C6-C10)아릴기가 접한 구조로 융합고리를 형성하는 것도 포함된다.In Formulas 9 to 14, A is selected from (C1-C5) alkylene and (C1-C5) alkenylene, and the alkylene and alkenylene are (C3-C5) alkylene and (C3-C5) alkenylene In this case, it also includes forming a fused ring with a structure in which the (C5-C7) cycloalkyl or (C6-C10) aryl group is in contact.

상기 화학식 1 내지 화학식 14의 에틸렌의 선택적 올리고머 제조용 크롬 착체 화합물에 포함된 키랄성 리간드의 치환체 R1, R2, R3, R4, R7, R8, R9 및 R10은 서로 독립적으로 (C6-C20)아릴, (C6-C20)아르(C1-C10)알킬, (C1-C10)알킬, (C2-C10)알케닐, (C2-C10)알키닐, (C3-C7)시클로알킬, 헤테로(C5-C20)아릴, 헤테로(C3-C7)시클로알킬 또는 -NR23R24이고, R23 또는 R24는 (C1-C10)알킬, (C6-C20)아릴이며, 상기 R1, R2, R3, R4, R7, R8, R9 및 R10의 치환체는 (C1-C10)알킬, (C1-C10)알콕시, (C6-C20)아릴옥시 및 할로겐으로부터 하나 이상이 더 치환될 수 있다. Substituents R 1 , R 2 , R 3 , R 4 , R 7 , R 8 , R 9 and R 10 of the chiral ligands included in the chromium complex compound for preparing the selective oligomer of ethylene of Formula 1 to Formula 14 are mutually Independently (C6-C20) aryl, (C6-C20) ar (C1-C10) alkyl, (C1-C10) alkyl, (C2-C10) alkenyl, (C2-C10) alkynyl, (C3-C7) Cycloalkyl, hetero (C5-C20) aryl, hetero (C3-C7) cycloalkyl or -NR 23 R 24 , R 23 or R 24 is (C1-C10) alkyl, (C6-C20) aryl, wherein R Substituents of 1 , R 2 , R 3 , R 4 , R 7 , R 8 , R 9 and R 10 are one from (C1-C10) alkyl, (C1-C10) alkoxy, (C6-C20) aryloxy and halogen The above may be further substituted.

구체적으로는 상기 키랄성 리간드 중 R1, R2, R3, R4, R7, R8, R9 및 R10은 서로 독립적으로 페닐, 나프틸, 안트라세닐, 메시틸, 크실닐, 메틸, 에틸, 에틸레닐, n-프로필, i-프로필, 프로페닐, 프로피닐, n-부틸, t-부틸, 시클로프로필, 시클로부틸, 시클로펜틸, 시클로헥실, 4-메틸시클로헥실, 4-에틸시클로헥실, 4-아이소프로필시클로헥실, 벤질, 톨릴, 크실릴, 4-메틸페닐, 4-에틸페닐, 4-아이소프로필페닐, 4-t-부틸페닐, 4-메톡시페닐, 4-아이소프로폭시페닐, 큐밀, 메톡시, 에톡시, 페녹시, 톨릴옥시, 디메틸아미노, 티오메틸, 트리메틸실닐, 디메틸히드라질, 2-메틸시클로헥실, 2-에틸시클로헥실, 2-아이소프로필시클로헥실, o-메틸페닐, o-에틸페닐, o-아이소프로필페닐, o-t-부틸페닐, o-메톡시페닐, o-아이소프로폭시페닐, 비페닐, 나프틸 및 안트라세닐로 이루어진 그룹으로부터 선택되며, 바람직하게는 각각 독립적으로 페닐, 벤질, 나프틸, 4-메틸페닐, 4-에틸페닐, 4-아이소프로필페닐, 4-t-부틸페닐, 4-메톡시페닐, 4-아이소프로폭시페닐, 2-메틸시클로헥실, 2-에틸시클로헥실, 2-아이소프로필시클로헥실, o-메틸페닐, o-에틸페닐, o-아이소프로필페닐, o-t-부틸페닐, o-메톡시페닐 및 o-아이소프로폭시페닐로 이루어진 그룹으로부터 선택된다.Specifically, in the chiral ligand, R 1 , R 2 , R 3 , R 4 , R 7 , R 8 , R 9 and R 10 are mutually Independently phenyl, naphthyl, anthracenyl, mesityl, xylyl, methyl, ethyl, ethylenyl, n-propyl, i-propyl, propenyl, propynyl, n-butyl, t-butyl, cyclopropyl, cyclobutyl , Cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-isopropylcyclohexyl, benzyl, tolyl, xylyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4- t-butylphenyl, 4-methoxyphenyl, 4-isopropoxyphenyl, cumyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, thiomethyl, trimethylsilyl, dimethylhydrazyl, 2-methylcyclohexyl 2-ethylcyclohexyl, 2-isopropylcyclohexyl, o- methylphenyl, o -ethylphenyl, o -isopropylphenyl, ot -butylphenyl, o -methoxyphenyl, o -isopropoxyphenyl, biphenyl, Selected from the group consisting of naphthyl and anthracenyl, preferably each independently phenyl, benzyl, naphthyl , 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-t-butylphenyl, 4-methoxyphenyl, 4-isopropoxyphenyl, 2-methylcyclohexyl, 2-ethylcyclohexyl, 2- Isopropylcyclohexyl, o-methylphenyl, o-ethylphenyl, o-isopropylphenyl, ot-butylphenyl, o-methoxyphenyl and o-isopropoxyphenyl.

본 발명에 따른 에틸렌의 선택적 올리고머 제조용 크롬 착체 화합물에 포함되는 키랄성 리간드의 키랄 탄소와 결합되는 R5, R6, R11 및 R12는 서로 독립적으로 (C6-C20)아릴, (C6-C20)아르(C1-C10)알킬, (C1-C10)알킬, (C2-C10)알케닐, (C2-C10)알키닐, (C3-C7)시클로알킬, 헤테로(C5-C20)아릴, 헤테로(C3-C7)시클로알킬, (C1-C10)알콕시, (C6-C20)아릴옥시, 아미노카보닐, 카보닐아미노, 다이(C1-C10)알킬아미노, (C1-C10)알킬실릴 또는 (C6-C20)아릴실릴이며, 상기 R5, R6, R11 및 R12의 치환체는 (C1-C10)알킬, (C1-C10)알콕시, (C6-C20)아릴옥시 및 할로겐으로 치환될 수 있으며, 바람직하게는 메틸, 에틸, 에틸레닐, n-프로필, i-프로필, 프로페닐, 프로피닐, n-부틸, t-부틸, i-부틸, 페닐, 벤질, 톨릴, 크실릴, 메톡시, 에톡시, 페녹시, 메틸아미노, 다이메틸아미노로부터 선택된다. R 5 , R 6 , bonded to the chiral carbon of the chiral ligand contained in the chromium complex compound for the selective oligomer preparation of ethylene according to the present invention R 11 and R 12 independently of one another are (C6-C20) aryl, (C6-C20) ar (C1-C10) alkyl, (C1-C10) alkyl, (C2-C10) alkenyl, (C2-C10) alky Nyl, (C3-C7) cycloalkyl, hetero (C5-C20) aryl, hetero (C3-C7) cycloalkyl, (C1-C10) alkoxy, (C6-C20) aryloxy, aminocarbonyl, carbonylamino, Di (C1-C10) alkylamino, (C1-C10) alkylsilyl or (C6-C20) arylsilyl, wherein R 5 , R 6 , The substituents of R 11 and R 12 may be substituted with (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy, (C 6 -C 20) aryloxy and halogen, preferably methyl, ethyl, ethylenyl, n-propyl , i-propyl, propenyl, propynyl, n-butyl, t-butyl, i-butyl, phenyl, benzyl, tolyl, xylyl, methoxy, ethoxy, phenoxy, methylamino, dimethylamino .

상기 에틸렌의 선택적 올리고머 제조용 크롬 착체 화합물에서 크롬에 배위되는 X1, X2, X3, X4, X5 또는 X6는 Cl, Br, 아세토아세틸 및 2-에틸헥사노일기로부터 선택될 수 있으나, 이들에 제한되는 것은 아니다.X 1 , X 2 , X 3 , X 4 , X 5 or X 6 coordinated with chromium in the chromium complex compound for the selective oligomer preparation of ethylene may be selected from Cl, Br, acetoacetyl and 2-ethylhexanoyl groups, It is not limited to these.

상기 화학식 1에서 크롬에 배위되는 L은 테트라하이드로퓨란, 디에틸에테르, 톨루엔, 클로로벤젠, 디클로로벤젠, 아세틸아세톤 및 2-에틸헥사논으로부터 선택될 수 있으며, 상기 L은 키랄성 리간드와 크롬염의 반응 시 매질인 용매들로부터 기인된다.In Chemical Formula 1, L coordinated with chromium may be selected from tetrahydrofuran, diethyl ether, toluene, chlorobenzene, dichlorobenzene, acetylacetone, and 2-ethylhexanone, wherein L is a reaction of a chiral ligand with a chromium salt. From solvents that are the medium.

본 발명에 따른 에틸렌의 선택적 올리고머 제조용 크롬 착체 화합물에 포함되는 키랄성 리간드는 다음의 화합물을 예시하지만, 하기에 예시되는 화합물이 본 발명을 제한하는 것은 아니다.The chiral ligands included in the chromium complex compound for the selective oligomer preparation of ethylene according to the present invention illustrate the following compounds, but the compounds illustrated below do not limit the present invention.

(S, S)-, (R, R)- 또는 meso-(페닐)2P-CH(메틸)CH(메틸)-P(페닐)2 (S, S)-, (R, R) -or meso- (phenyl) 2 P-CH (methyl) CH (methyl) -P (phenyl) 2

(S, S)-, (R, R)- 또는 meso-(4-메톡시페닐)2P-CH(메틸)CH(메틸)-P(4-메톡시페닐)2 (S, S)-, (R, R) -or meso- (4-methoxyphenyl) 2 P-CH (methyl) CH (methyl) -P (4-methoxyphenyl) 2

(S, S)-, (R, R)- 또는 meso-(4-메틸페닐)2P-CH(메틸)CH(메틸)-P(4-메틸페닐)2 (S, S)-, (R, R) -or meso- (4-methylphenyl) 2 P-CH (methyl) CH (methyl) -P (4-methylphenyl) 2

(S, S)-, (R, R)- 또는 meso-(4-에틸페닐)2P-CH(메틸)CH(메틸)-P(페닐)2 (S, S)-, (R, R) -or meso- (4-ethylphenyl) 2 P-CH (methyl) CH (methyl) -P (phenyl) 2

(S, S)-, (R, R)- 또는 meso-(4-에틸페닐)2P-CH(에틸)CH(메틸)-P(4-에틸페닐)2 (S, S)-, (R, R) -or meso- (4-ethylphenyl) 2 P-CH (ethyl) CH (methyl) -P (4-ethylphenyl) 2

(S, S)-, (R, R)- 또는 meso-(4-메톡시페닐)2P-CH(에틸)CH(메틸)-P(페닐)2 (S, S)-, (R, R) -or meso- (4-methoxyphenyl) 2 P-CH (ethyl) CH (methyl) -P (phenyl) 2

(S, S)-, (R, R)- 또는 meso-(4-에틸페닐)2P-CH(에틸)CH(에틸)-P(4-에틸페닐)2 (S, S)-, (R, R) -or meso- (4-ethylphenyl) 2 P-CH (ethyl) CH (ethyl) -P (4-ethylphenyl) 2

(S, S)-, (R, R)- 또는 meso-(페닐)2P-CH(에틸)CH(에틸)-P(페닐)2 (S, S)-, (R, R) -or meso- (phenyl) 2 P-CH (ethyl) CH (ethyl) -P (phenyl) 2

(S, S)-, (R, R)- 또는 meso-(페닐)2P-CH(이소프로필)CH(메틸)-P(페닐)2 (S, S)-, (R, R) -or meso- (phenyl) 2 P-CH (isopropyl) CH (methyl) -P (phenyl) 2

(S, S)-, (R, R)- 또는 meso-(4-메톡시페닐)2P-CH(이소프로필)CH(메틸)-P(4-메톡시페닐)2 (S, S)-, (R, R) -or meso- (4-methoxyphenyl) 2 P-CH (isopropyl) CH (methyl) -P (4-methoxyphenyl) 2

(S, S)-, (R, R)- 또는 meso-(4-에틸페닐)2P-CH(이소프로필)CH(메틸)-P(4-에 틸페닐)2 (S, S)-, (R, R) -or meso- (4-ethylphenyl) 2 P-CH (isopropyl) CH (methyl) -P (4-ethylphenyl) 2

(S, S)-, (R, R)- 또는 meso-(페닐)2P-CH(n-프로필)CH(메틸)-P(페닐)2 (S, S)-, (R, R) -or meso- (phenyl) 2 P-CH (n-propyl) CH (methyl) -P (phenyl) 2

(S, S)-, (R, R)- 또는 meso-(4-메톡시페닐)2P-CH(n-프로필)CH(메틸)-P(4-메톡시페닐)2 (S, S)-, (R, R) -or meso- (4-methoxyphenyl) 2 P-CH (n-propyl) CH (methyl) -P (4-methoxyphenyl) 2

(S, S)-, (R, R)- 또는 meso-4(4-에틸페닐)2P-CH(n-프로필)CH(메틸)-P(4-에틸페닐)2 (S, S)-, (R, R) -or meso-4 (4-ethylphenyl) 2 P-CH (n-propyl) CH (methyl) -P (4-ethylphenyl) 2

(S, S)-, (R, R)- 또는 meso-(페닐)2P-CH(이소프로필)CH(에틸)-P(페닐)2 (S, S)-, (R, R) -or meso- (phenyl) 2 P-CH (isopropyl) CH (ethyl) -P (phenyl) 2

(S, S)-, (R, R)- 또는 meso-(4-메톡시페닐)2P-CH(이소프로필)CH(에틸)-P(4-메톡시페닐)2 (S, S)-, (R, R) -or meso- (4-methoxyphenyl) 2 P-CH (isopropyl) CH (ethyl) -P (4-methoxyphenyl) 2

(S, S)-, (R, R)- 또는 meso-(4-에틸페닐)2P-CH(이소프로필)CH(에틸)-P(4-에틸페닐)2 (S, S)-, (R, R) -or meso- (4-ethylphenyl) 2 P-CH (isopropyl) CH (ethyl) -P (4-ethylphenyl) 2

(S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-1,2-디-(P(페닐)2)시클로헥산 (S, S) -trans , (R, R) -trans- or, meso-cis- 1,2-di- (P (phenyl) 2 ) cyclohexane

(S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-1,2-디-(P(4-메톡시페닐)2)시클로헥산 (S, S) -trans , (R, R) -trans- or, meso-cis- 1,2-di- (P (4-methoxyphenyl) 2 ) cyclohexane

(S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-1,2-디-(P(4-에틸페닐)2)시 클로헥산 (S, S) -trans , (R, R) -trans- or, meso-cis- 1,2-di- (P (4-ethylphenyl) 2 ) cyclohexane

(S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-트랜스-1,2-디-(P(페닐)2)시클로펜탄 (S, S) -trans , (R, R) -trans- or, meso-cis-trans- 1,2-di- (P (phenyl) 2 ) cyclopentane

(S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-1,2-디-(P(4-메톡시페닐)2)시클로펜탄 (S, S) -trans , (R, R) -trans- or, meso-cis- 1,2-di- (P (4-methoxyphenyl) 2 ) cyclopentane

(S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-1,2-디-(P(4-에틸페닐)2)시클로펜탄 (S, S) -trans , (R, R) -trans- or, meso-cis- 1,2-di- (P (4-ethylphenyl) 2 ) cyclopentane

(S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-3,4-디-(P(페닐)2)피롤 (S, S) -trans , (R, R) -trans- or, meso-cis- 3,4-di- (P (phenyl) 2 ) pyrrole

(S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-3,4-디-(P(4-메톡시페닐)2)피롤 (S, S) -trans , (R, R) -trans- or, meso-cis- 3,4-di- (P (4-methoxyphenyl) 2 ) pyrrole

(S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-3,4-디-(P(4-에틸페닐)2)피롤 (S, S) -trans , (R, R) -trans- or, meso-cis- 3,4-di- (P (4-ethylphenyl) 2 ) pyrrole

(S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-3,4-디-(P(4-에틸페닐)2)이미다졸 (S, S) -trans , (R, R) -trans- or, meso-cis- 3,4-di- (P (4-ethylphenyl) 2 ) imidazole

(S, S)-, (R, R)- 또는 meso-(4-에틸페닐)2P-CH(디메틸아민)CH(디메틸아민)-P(4-에틸페닐)2 (S, S)-, (R, R) -or meso- (4-ethylphenyl) 2 P-CH (dimethylamine) CH (dimethylamine) -P (4-ethylphenyl) 2

(S, S)-, (R, R)- 또는 meso-(3-메톡시페닐)2P-CH(메틸)CH(메틸)-P(3-메톡시 페닐)2 (S, S)-, (R, R) -or meso- (3-methoxyphenyl) 2 P-CH (methyl) CH (methyl) -P (3-methoxy phenyl) 2

(S, S)-, (R, R)- 또는 meso-(4-에톡시페닐)2P-CH(메틸)CH(메틸)-P(o-에톡시페닐)2 (S, S)-, (R, R) -or meso- (4-ethoxyphenyl) 2 P-CH (methyl) CH (methyl) -P (o-ethoxyphenyl) 2

(S, S)-, (R, R)- 또는 meso-4-(디메틸아민페닐)2P-CH(메틸)CH(메틸)P(4-디메틸아민페닐)2 (S, S)-, (R, R) -or meso- 4- (dimethylaminephenyl) 2 P-CH (methyl) CH (methyl) P (4-dimethylaminephenyl) 2

(S, S)-, (R, R)- 또는 meso-(4-에틸시클로헥실)2PCH(메틸)CH(메틸)P(4-에틸시클로헥실)2 (S, S)-, (R, R) -or meso- (4-ethylcyclohexyl) 2 PCH (methyl) CH (methyl) P (4-ethylcyclohexyl) 2

(S, S)-, (R, R)- 또는 meso-(2-에틸페닐)2PCH(메틸)CH(메틸)P(2-에틸페닐)2 (S, S)-, (R, R) -or meso- (2 - ethylphenyl) 2 PCH (methyl) CH (methyl) P (2 - ethylphenyl) 2

(S, S)-, (R, R)- 또는 meso-(2-이소프로필페닐)2PCH(메틸)CH(메틸)P(2-이소프로필페닐)2 (S, S)-, (R, R) -or meso- (2-isopropylphenyl) 2 PCH (methyl) CH (methyl) P (2-isopropylphenyl) 2

(S, S)-, (R, R)- 또는 meso-(2-메틸페닐)2PCH(메틸)CH(메틸)P(2-메틸페닐)2 (S, S)-, (R, R) -or meso- (2-methylphenyl) 2 PCH (methyl) CH (methyl) P (2-methylphenyl) 2

(S, S)-, (R, R)- 또는 meso-(2-에틸페닐)2PCH(메틸)CH(메틸)P(페닐)2 (S, S)-, (R, R) -or meso- (2-ethylphenyl) 2 PCH (methyl) CH (methyl) P (phenyl) 2

(S, S)-, (R, R)- 또는 meso-(2-에틸페닐)2PCH(에틸)CH(메틸)P(2-에틸페닐)2 (S, S)-, (R, R) -or meso- (2-ethylphenyl) 2 PCH (ethyl) CH (methyl) P (2-ethylphenyl) 2

(S, S)-, (R, R)- 또는 meso-(2-에틸페닐)2PCH(에틸)CH(에틸)P(2-에틸페닐)2 (S, S)-, (R, R) -or meso- (2-ethylphenyl) 2 PCH (ethyl) CH (ethyl) P (2-ethylphenyl) 2

(S, S)-, (R, R)- 또는 meso-(2-에틸페닐)2PCH(이소프로필)CH(메틸)P(2-에틸 페닐)2 (S, S)-, (R, R) -or meso- (2-ethylphenyl) 2 PCH (isopropyl) CH (methyl) P (2-ethyl phenyl) 2

(S, S)-, (R, R)- 또는 meso-(2-에틸페닐)2PCH(n-프로필)CH(메틸)P(2-에틸페닐)2 (S, S)-, (R, R) -or meso- (2-ethylphenyl) 2 PCH (n-propyl) CH (methyl) P (2-ethylphenyl) 2

(S, S)-, (R, R)- 또는 meso-(2-에틸페닐)2PCH(이소프로필)CH(에틸)P(2-에틸페닐)2 (S, S)-, (R, R) -or meso- (2-ethylphenyl) 2 PCH (isopropyl) CH (ethyl) P (2-ethylphenyl) 2

(S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-1,2-디-(P(2-에틸페닐)2)시클로헥산 (S, S) -trans , (R, R) -trans- or, meso-cis- 1,2-di- (P (2-ethylphenyl) 2 ) cyclohexane

(S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-1,2-디-(P(2-에틸페닐)2)시클로펜탄 (S, S) -trans , (R, R) -trans- or, meso-cis- 1,2-di- (P (2-ethylphenyl) 2 ) cyclopentane

(S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-3,4-디-(P(2-에틸페닐)2)피롤 (S, S) -trans , (R, R) -trans- or, meso-cis- 3,4-di- (P (2-ethylphenyl) 2 ) pyrrole

(S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-3,4-디-(P(2-에틸페닐)2)이미다졸 (S, S) -trans , (R, R) -trans- or, meso-cis- 3,4-di- (P (2-ethylphenyl) 2 ) imidazole

(S, S)-, (R, R)- 또는 meso-(2-에틸페닐)2PCH(디메틸아민)CH(디메틸아민)P(2-에틸페닐)2 (S, S)-, (R, R) -or meso- (2-ethylphenyl) 2 PCH (dimethylamine) CH (dimethylamine) P (2-ethylphenyl) 2

(S, S)-, (R, R)- 또는 meso-(2-메톡시페닐)2PCH(메틸)CH(메틸)P(2-메톡시페 닐)2 (S, S)-, (R, R) -or meso- (2-methoxyphenyl) 2 PCH (methyl) CH (methyl) P (2-methoxyphenyl) 2

(S, S)-, (R, R)- 또는 meso-(2-에톡시페닐)2PCH(메틸)CH(메틸)P(2-에톡시페닐)2 (S, S)-, (R, R) -or meso- (2-ethoxyphenyl) 2 PCH (methyl) CH (methyl) P (2-ethoxyphenyl) 2

(S, S)-, (R, R)- 또는 meso-(2-디메틸아민페닐)2PCH(메틸)CH(메틸)P(2-디메틸아민페닐)2 (S, S)-, (R, R) -or meso- (2-dimethylaminephenyl) 2 PCH (methyl) CH (methyl) P (2-dimethylaminephenyl) 2

(S, S)-, (R, R)- 또는 meso-(2-에틸시클로헥실)2PCH(메틸)CH(메틸)P(2-에틸시클로헥실)2 (S, S)-, (R, R) -or meso- (2-ethylcyclohexyl) 2 PCH (methyl) CH (methyl) P (2-ethylcyclohexyl) 2

본 발명에 따른 키랄성 리간드들은 당업자들에게 공지된 다양한 방법을 이용하여 제조될 수 있다. Chiral ligands according to the invention can be prepared using a variety of methods known to those skilled in the art.

본 발명에 따른 상기 리간드의 P-C-C-P형 입체 이성질체 골격구조는 공지된 종래의 (R)nPN(R')P(R)m 헤테로 리간드와는 별개의 독립적인 구조를 띠는 리간드로서 리간드의 골격 구조 내의 헤테로 원자는 단지 인(P) 원자뿐이다. 즉, 본 발명에 따른 촉매계에 사용되는 리간드는 두 개의 인 원자 사이에 질소 원자가 없이 2개의 탄소-탄소 골격 구조로 이루어진 것으로서, 탄소 원자에 붙는 치환체의 배열 방향으로 적당히 공간 구조를 조절함으로써 우수한 촉매활성을 나타낼 뿐만 아니라 70 wt% 이상의 높은 1-헥센 선택도 또는 1-옥텐 선택도를 달성할 수 있고, 반응 활성의 안정성을 유지 할 수 있다. The PCCP type stereoisomeric framework of the ligand according to the present invention is a ligand having a structure independent of the known conventional (R) n PN (R ') P (R) m heteroligand and is a skeleton structure of the ligand. The hetero atoms in the are only phosphorus (P) atoms. That is, the ligand used in the catalyst system according to the present invention is composed of two carbon-carbon skeletal structures without nitrogen atoms between two phosphorus atoms, and has excellent catalytic activity by appropriately adjusting the spatial structure in the arrangement direction of the substituents attached to the carbon atoms. In addition to exhibiting high 1-hexene selectivity or 1-octene selectivity of 70 wt% or more, it is possible to maintain the stability of the reaction activity.

또한, 키랄성 P-C-C-P 골격 구조의 리간드가 배위된 전이 금속 착체는 상온이상에서 불용성이 되게 하기 위하여 폴리머 사슬에 부착되도록 변형될 수 있다. 또한, 실리카, 실리카겔, 폴리실록산 또는 알루미나 등의 백본에 결합시켜 고정화 할 수 있다. In addition, transition metal complexes coordinated with ligands of the chiral P-C-C-P backbone structure can be modified to attach to the polymer chains to render them insoluble above room temperature. It can also be immobilized by binding to a backbone such as silica, silica gel, polysiloxane or alumina.

본 발명은 보다 효과적인 활성 및 고선택도를 위하여 본 발명에 따른 에틸렌의 선택적 올리고머 제조용 크롬 착체 촉매와 공지의 조촉매를 포함하는 에틸렌의 선택적 올리고머 제조용 크롬 착체 촉매 조성물을 포함한다.The present invention comprises a chromium complex catalyst composition for the selective oligomer production of ethylene comprising a chromium complex catalyst for the selective oligomer production of ethylene and a known promoter for more effective activity and higher selectivity.

본 발명에 따른 촉매 조성물에서 채용되는 조촉매는 원칙적으로 키랄성 P-C-C-P 골격 구조의 리간드가 배위된 전이 금속 착체를 활성화하는 임의의 화합물일 수 있다. 활성제는 또한 혼합물로도 사용될 수 있다. 활성제로 적합한 화합물에는 유기 알루미늄 화합물, 유기 붕소 화합물, 유기염이 포함된다. The cocatalyst employed in the catalyst composition according to the invention can in principle be any compound which activates a transition metal complex coordinated with a ligand of the chiral P-C-C-P framework structure. Active agents can also be used in mixtures. Suitable compounds as activators include organoaluminum compounds, organoboron compounds, organic salts.

본 발명에 따른 촉매계에 활성제로 사용되기에 적합한 유기 알루미늄 화합물은 AlR3 (R은 각각 독립적으로 (C1-C12)알킬, 산소 함유 (C1-C12)알킬 또는 할로겐이다.)의 화합물 또는 LiAlH4 등을 포함한다. Organoaluminum compounds suitable for use as activators in the catalyst system according to the invention are AlR 3 (R is each independently (C 1 -C 12) alkyl, oxygen containing (C 1 -C 12) alkyl or halogen.) Or LiAlH 4 and the like. It includes.

본 발명에 따른 촉매 조성물에서 조촉매로는 트라이메틸알루미늄(TMA), 트라이에틸알루미늄(TEA), 트라이아이소부틸알루미늄(TIBA), 트라이-n-옥틸알루미늄, 메틸알루미늄 다이클로라이드, 에틸알루미늄 다이클로라이드, 다이메틸알루미늄 클로라이드, 다이에틸알루미늄 클로라이드, 알루미늄 아이소프로폭사이드, 에틸알루미늄 세스퀴클로라이드, 메틸알루미늄 세스퀴클로라이드 및 알루미녹산이 포함된 다. Promoters in the catalyst composition according to the invention include trimethylaluminum (TMA), triethylaluminum (TEA), triisobutylaluminum (TIBA), tri-n-octylaluminum, methylaluminum dichloride, ethylaluminum dichloride, Dimethylaluminum chloride, diethylaluminum chloride, aluminum isopropoxide, ethylaluminum sesquichloride, methylaluminum sesquichloride and aluminoxanes.

알루미녹산은 당업계에서 전형적으로 물과 알킬알루미늄 화합물, 예를 들어 트리메틸알루미늄에 조절 첨가하여 제조 될 수 있는 올리고머 화합물로서 널리 알려져 있다. 생성된 알루미녹산 올리고머 화합물은 선형, 사이클릭, 케이지(cage) 또는 이들의 혼합물일 수 있다. Aluminoxanes are well known in the art as oligomeric compounds that can typically be prepared by controlled addition to water and alkylaluminum compounds, such as trimethylaluminum. The resulting aluminoxane oligomeric compound may be linear, cyclic, cage, or mixtures thereof.

적합한 유기 붕소 화합물은 보록신, NaBH4, 트리에틸 보란, 트라이페닐보란, 트라이페닐보란 암모니아 착화합물, 트라이부틸보레이트, 트라이아이소프로필보레이트, 트리스(펜타플로로페닐)보란, 트라이틸(테트라펜타플로로페닐)보레이트, 다이메틸페닐암모늄(테트라펜타플로로페닐)보레이트, 다이에틸페닐암모늄(테트라펜타플로로페닐)보레이트, 메틸다이페닐암모늄(테트라펜타플로로페닐)보레이트, 또는 에틸다이페닐암모늄(테트라펜타플로로페닐)보레이트이다. 이들의 유기 붕소 화합물은 상기의 유기 알루미늄 화합물과 혼합물로 사용할 수 있다. Suitable organoboron compounds are boroxine, NaBH 4 , triethyl borane, triphenylborane, triphenylborane ammonia complex, tributylborate, triisopropylborate, tris (pentafluorophenyl) borane, trityl (tetrapentafluoro) Phenyl) borate, dimethylphenylammonium (tetrapentafluorophenyl) borate, diethylphenylammonium (tetrapentafluorophenyl) borate, methyldiphenylammonium (tetrapentafluorophenyl) borate, or ethyldiphenylammonium (tetrapenta) Fluorophenyl) borate. These organoboron compounds can be used in a mixture with the organoaluminum compounds described above.

또한 특히 조촉매 중에서 알루미녹산은 알킬알루미녹산, 예를 들어 메틸알루미녹산(MAO) 및 에틸알루미녹산(EAO)뿐 아니라 변형된 알킬 알루미녹산 예를 들어 변형 메틸알루미녹산(MMAO) 중에서 선택될 수 있다. 변형 메틸 알루미녹산(Akzo Nobel 제조)은 메틸그룹 이외에 이소부틸 또는 n-옥틸그룹과 같은 혼성 알킬 그룹을 함유한다.Also in the cocatalysts in particular the aluminoxanes can be chosen from alkylaluminoxanes such as methylaluminoxane (MAO) and ethylaluminoxane (EAO) as well as modified alkyl aluminoxanes such as modified methylaluminoxane (MMAO). . Modified methyl aluminoxanes (manufactured by Akzo Nobel) contain, in addition to methyl groups, mixed alkyl groups such as isobutyl or n-octyl groups.

상기 조촉매는 메틸알루미녹산(MAO) 또는 에틸알루미녹산(EAO)인 것이 바람직하다.The promoter is preferably methylaluminoxane (MAO) or ethylaluminoxane (EAO).

에틸렌의 선택적 올리고머 제조용 크롬 착체와 알루미녹산의 비율은 알루미늄:크롬 몰비로 기준으로 1:1 내지 10,000:1이며, 바람직하게는 약 1:1 내지 1,000:1이다. The ratio of the chromium complex for producing the selective oligomer of ethylene to the aluminoxane is 1: 1 to 10,000: 1 based on the aluminum: chromium molar ratio, and preferably about 1: 1 to 1,000: 1.

본 발명의 또 다른 범위는 본 발명에 따른 P-C-C-P 골격 구조의 키랄성 리간드를 전이금속 전구체에 미리 배위된 구조의 본 발명에 따른 화학식 1 또는 화학식 2의 에틸렌의 선택적 올리고머 제조용 크롬 착체 화합물을 제조하고, 이를 에틸렌 올리고머화 매개체에 주입하여 에틸렌 올리고머화 반응을 고활성과 고선택도로 올리고머, 특히 1-헥센 또는 1-옥텐을 고활성과 고선택비로 재조하는 방법에 관한 것으로, 고활성 고선택도를 이루기 위한 P-C-C-P 골격 구조 리간드는 (S, S)-, (R, R)- 또는 meso- 이성질체의 선형 리간드, 트랜스- 또는 시스-사이클릭 리간드일 수 있다. 또한 몇 가지 이성질체의 혼합된 형태로서 (S, S)-, (R, R)- 또는 meso-(R1)(R2)P-(R5)CHCH(R6)-P(R3)(R4)가 다중으로 결합되어 구성된 리간드가 사용될 수도 있다.Another scope of the present invention is to prepare a chromium complex compound for the selective oligomer preparation of ethylene of formula 1 or formula 2 according to the present invention having a structure in which the chiral ligand of the PCCP skeleton structure according to the present invention is previously coordinated with a transition metal precursor, The present invention relates to a method for preparing an ethylene oligomerization reaction with high activity and high selectivity by injecting an ethylene oligomerization medium into a high activity and a high selectivity with high activity and high selectivity. The PCCP framework structural ligand can be a linear ligand, trans- or cis- cyclic ligand of the (S, S)-, (R, R) -or meso- isomer. It is also a mixed form of several isomers (S, S)-, (R, R) -or meso- (R 1 ) (R 2 ) P- (R 5 ) CHCH (R 6 ) -P (R 3 ) A ligand composed of multiple bonds of (R 4 ) may be used.

본 발명에 개시된 촉매계의 개별 성분들인 에틸렌의 선택적 올리고머 제조용 크롬 착체와 조촉매는 용매의 존재 또는 부재 하에 동시에 또는 임의의 순서로 순차적으로 배합되어 활성 촉매를 제공할 수 있다. 각 촉매 성분의 혼합은 -20 내지 250 ℃의 온도에서 수행될 수 있으며, 촉매 성분이 혼합되는 동안 올레핀의 존재는 일반적으로 보호 효과를 나타내어 향상된 촉매 성능을 제공할 수 있다. 보다 바람직한 온도의 범위는 20 내지 100 ℃이다. Chromium complexes and cocatalysts for the production of selective oligomers of ethylene, which are the individual components of the catalyst system disclosed herein, may be combined in sequence or in any order in the presence or absence of a solvent to provide an active catalyst. Mixing of each catalyst component can be carried out at a temperature of -20 to 250 ° C., and the presence of the olefins during the mixing of the catalyst components generally exhibits a protective effect to provide improved catalyst performance. The range of more preferable temperature is 20-100 degreeC.

본 발명에 개시된 반응 생성물, 달리 표현하면 에틸렌 올리고머, 특히 1-헥센 또는 1-옥텐은 본 발명에 따른 에틸렌의 선택적 올리고머 제조용 크롬 착체 화합물과 통상적인 장치 및 접촉 기술을 이용하여 불활성 용매의 존재 또는 부재 하에서 균질 액상 반응 또는 촉매 시스템이 일부 용해되지 않거나 전부 용해되지 않는 형태인 슬러리 반응 또는 2상 액체/액체 반응 또는 생성물 올레핀이 주 매질로 작용하는 벌크상 반응 또는 가스상 반응으로 제조될 수 있다.The reaction products disclosed herein, in other words ethylene oligomers, in particular 1-hexene or 1-octene, are in the presence or absence of an inert solvent using chromium complex compounds for the selective oligomer preparation of ethylene according to the invention and conventional apparatus and contacting techniques. A homogeneous liquid phase reaction or catalyst system can be prepared under a bulk reaction or a gas phase reaction in which the slurry reaction or the biphasic liquid / liquid reaction or product olefins serve as the main medium.

본 발명에 따른 선택적 올리고머 제조 방법은 또한 불활성 용매 중에 수행될 수 있다. 즉, 각 촉매 화합물 및 활성제와 반응 하지 않는 임의의 불활성 용매가 사용될 수 있으며, 이들 불활성 용매는 임의의 포화 지방족 및 불포화 지방족 및 방향족 탄화수소 및 할로겐화 탄화수소를 포함할 수 있다. 전형적인 용매에는 벤젠, 톨루엔, 크실렌, 클로로벤젠, 큐멘, 헵탄, 사이클로헥산, 메틸사이클로헥산, 메틸사이클로펜탄, n-헥산, 1-헥센, 1-옥텐 등이 포함되나 이들에만 한정되는 것은 아니다. 특히 상기 화학식 1 화합물을 채용하는 경우 L 리간드와 동일한 화합물을 반응용매로 채용하는 것이 더욱 바람직하다.The selective oligomer preparation process according to the invention can also be carried out in an inert solvent. That is, any inert solvent that does not react with each catalyst compound and active agent may be used, and these inert solvents may include any saturated aliphatic and unsaturated aliphatic and aromatic hydrocarbons and halogenated hydrocarbons. Typical solvents include, but are not limited to, benzene, toluene, xylene, chlorobenzene, cumene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene, 1-octene, and the like. In particular, when employing the compound of Formula 1, it is more preferable to employ the same compound as the L ligand as the reaction solvent.

본 발명의 제조방법에 따른 올리고머화 반응은 -20 내지 250 ℃의 온도, 바람직하게는 15 내지 130 ℃의 온도, 더 바람직하게는 30 내지 70 ℃의 온도에서 수행될 수 있다. The oligomerization reaction according to the preparation method of the present invention may be carried out at a temperature of -20 to 250 ℃, preferably at a temperature of 15 to 130 ℃, more preferably at a temperature of 30 to 70 ℃.

또한, 본 발명에 따른 방법은 대기압 내지 500 bar의 압력에서, 바람직하게는 10 내지 70 bar의 압력, 더 바람직하게는 30 내지 50 bar의 압력에서 수행된다. In addition, the process according to the invention is carried out at atmospheric pressure to a pressure of 500 bar, preferably at a pressure of 10 to 70 bar, more preferably at a pressure of 30 to 50 bar.

본 발명의 구체 예에서 P-C-C-P골격 구조의 입체 이성질체 리간드 배위 복합체 및 반응 조건은 에틸렌으로부터의 1-헥센 수율이 50 질량% 이상, 바람직하게는 70 질량% 이상이 되도록 선택된다. 이 경우 수율은 형성된 총 반응 생성물 100 g당 형성된 1-헥센의 그램수를 의미한다. In an embodiment of the invention the stereoisomeric ligand coordination complex of the P-C-C-P framework structure and the reaction conditions are selected such that the 1-hexene yield from ethylene is at least 50 mass%, preferably at least 70 mass%. Yield in this case means the number of grams of 1-hexene formed per 100 g of total reaction product formed.

본 발명의 또 다른 구체예에서 P-C-C-P 골격 구조의 입체 이성질체 리간드 배위 복합체 및 반응 조건은 에틸렌으로부터의 1-옥텐 수율이 30 질량% 이상, 바람직하게는 50 질량% 이상이 되도록 선택된다. 이 경우 수율은 형성된 총 반응 생성물 100 g당 형성된 1-옥텐의 그램수를 의미한다. In another embodiment of the invention the stereoisomer ligand coordination complex of the P-C-C-P framework structure and the reaction conditions are selected such that the 1-octene yield from ethylene is at least 30 mass%, preferably at least 50 mass%. Yield in this case means the number of grams of 1-octene formed per 100 g of the total reaction product formed.

본 발명에 따른 방법은 또한 P-C-C-P 골격 구조의 리간드 및 반응 조건에 따라 1-헥센 또는 1-옥텐 이외에 상이한 양의 1-부텐, 1-헥센, 메틸사이클로펜탄, 메틸렌사이클로펜탄, 프로필사이클로펜탄 및 다수의 고급 올리고머 및 폴리에틸렌을 제공할 수 있다. The process according to the invention also allows different amounts of 1-butene, 1-hexene, methylcyclopentane, methylenecyclopentane, propylcyclopentane and a number of other than 1-hexene or 1-octene depending on the ligand of the PCCP backbone structure and the reaction conditions. Higher oligomers and polyethylenes can be provided.

본 방법에 따른 방법은 임의 유형의 반응기를 포함하는 플랜트로 수행될 수 있다. 이러한 반응기의 예는 배치식 반응기, 반배치식 반응기 및 연속식 반응기를 포함하나 이들에만 한정하지 않는다. 플랜트는 반응기, 이 반응기 내에 올레핀 반응기 및 촉매 시스템의 주입구, 이 반응기로부터 올리고머화 반응 생성물을 유출을 위한 라인 및 올리고머화 반응 생성물을 분리하기 위한 적어도 하나의 분리기를 조합하여 포함할 수 있으며, 이때 촉매 시스템은 본원에 개시된 전이금속 화합물, 활 성제 및 P-C-C-P 리간드 배위 복합체를 포함할 수 있다. The process according to the method can be carried out in a plant comprising any type of reactor. Examples of such reactors include, but are not limited to, batch reactors, semi-batch reactors and continuous reactors. The plant may comprise a reactor, an inlet of an olefin reactor and a catalyst system therein, a combination of the oligomerization reaction product from the reactor with a line for effluent and at least one separator for separating the oligomerization reaction product, wherein the catalyst The system can include the transition metal compounds, activators, and PCCP ligand coordination complexes disclosed herein.

본 발명에 따른 에틸렌 올리고머화 촉매계를 사용하여 에틸렌을 올리고머화함으로써 1-헥센 또는 1-옥텐을 고활성, 고선택적으로 생산할 수 있다.The oligomerization of ethylene using the ethylene oligomerization catalyst system according to the present invention allows the production of 1-hexene or 1-octene in high activity and high selectivity.

리간드와 크롬 금속 또는 크롬전구체를 따로따로 에틸렌 올리고머화 반응 매개체에 주입하는 경우상당량의 리간드가 크롬 원자에 접근 할 수 없거나 정상적으로 배위하지 못 하여 상업화에 접합할 정도의 활성과 선택도를 갖지 못하는 것에 비하여, 본 발명에 따른 키랄성 P-C-C-P 골격 구조를 갖는 에틸렌의 선택적 올리고머 제조용 크롬착체 화합물을 사용하여 에틸렌을 올리고머화 하는 경우, 키랄성 리간드가 크롬에 정상적으로 배위된 촉매를 채용함으로 인하여 반응 활성이 10배 이상 증가되고, 또한 높은 선택비로 인하여 중합체 부산물의 생성량을 1/10배 이하로 줄일 수 있어, 결과적으로 반응 후 중합체 함량을 0.1 wt%정도로 낮출 수 있는 효과가 있고, 이로 인해 부산물의 적은 생성비는 정제공정을 간단히 할 수 있는 등의 생산을 위한 공정이 매우 간단하게 할 수 있는 경제적 잇점이 있다. 또한 촉매 활성화에 필요한 고가의 조촉매인 MAO의 주입량도 1/10 이하로 줄일 수 있어 경제적인 생산 공정이 될 수 있는 장점이 있다.When the ligand and the chromium metal or chromium precursor are separately injected into the ethylene oligomerization reaction medium, a significant amount of the ligand does not have access or normal coordination to the chromium atom and thus does not have enough activity and selectivity to conjugate to commercialization. In the case of oligomerizing ethylene using a chromium complex compound for the selective oligomer preparation of ethylene having a chiral PCCP skeleton structure according to the present invention, the reaction activity is increased by 10 times or more due to the adoption of a catalyst in which chiral ligands are normally coordinated to chromium. In addition, due to the high selectivity, the amount of polymer by-products can be reduced to 1/10 times or less, and as a result, the polymer content can be lowered to about 0.1 wt% after the reaction. The process for production, such as simple There is an economic advantage that can be simplified. In addition, the injection amount of MAO, which is an expensive promoter required for catalyst activation, can be reduced to less than 1/10, which can be an economical production process.

이하 본 발명에 따른 제조예 및 실시예를 참조하여 본 발명을 좀 더 상세히 기술하지만, 이에 본 발명의 범주가 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Preparation Examples and Examples, but the scope of the present invention is not limited thereto.

[제조예][Manufacturing Example]

[촉매 제조예 1] [Catalyst Preparation Example 1] (( S,S)S, S) -(페닐)-(Phenyl) 22 PCH(메틸)CH(메틸)P(페닐)PCH (methyl) CH (methyl) P (phenyl) 22 (테트라하이드로퓨란)삼염화크롬(Tetrahydrofuran) chromium trichloride

[CrCl[CrCl 33 (THF){(P,P)-(THF) {(P, P)- kk 22 -(-( S,SS, S )-((Ph))-((Ph) 22 P(Me)CH-CH(Me)P(Ph)P (Me) CH-CH (Me) P (Ph) 22 )}])}]

A. 리간드 (A. Ligands ( S,S)S, S) -(페닐)-(Phenyl) 22 PCH(메틸)CH(메틸)P(페닐)PCH (methyl) CH (methyl) P (phenyl) 2 2

[([( S,SS, S )-Ph) -Ph 22 PCH(Me)CH(Me)PPhPCH (Me) CH (Me) PPh 22 ]의 제조Manufacture of

키랄성 리간드인 (S,S)-Ph2PCH(Me)CH(Me)PPh2]는 B. Bosnich et al, J. Am. Chem. Soc. 99(19) (1977) 6262에 개시된 바와 같이 제조하였다. (2R,3R)-부탄디올로부터 (2R,3R)-부탄디올 디-p-톨루엔솔포네이트를 제조했다. 이 제조 방법은 R. B. Mitra et al, J. Am. Chem. Soc 84(1962)에 개시된 바와 같이 하였다. 얼음물 조에 냉각된 1 L 플라스크에 건조된 피리딘 100 mL(1.24 mol)을 넣고 염화-p-톨루엔솔폰닐 100 g(0.525 mol)과 혼합 후, (2R,3R)-부탄디올 22 mL(0.245 mol)을 서서히 적가하였다. 20 분 동안 상온으로 온도를 올린 후, 반 고체상의 혼합물을 상온에서 12 시간 유지하였다. 과량의 얼음 조각을 더하고 덩어리가 형성되지 않도록 격렬하게 흔들었다. 분말 결정이 서서히 분리된 것을 확인 후, 얼음조각과 함께 2 시간 동안 교반하고 이 혼합물에 부서진 얼음조각과 진한 염산 용액 70 ml를 격렬한 교반과 함께 주입하였다. 적출된 슬러리를 여과 후 물로 완전히 세척하고 건조하여 (2R,3R)-부탄디올 디-p-톨루엔솔포네이트 85 g(86.3 %)의 생성물을 얻었다(녹 는점 62 내지 64 ℃).The chiral ligand ( S, S ) -Ph 2 PCH (Me) CH (Me) PPh 2 ] is described in B. Bosnich et al, J. Am. Chem. Soc. Prepared as disclosed in 99 (19) (1977) 6262. (2R, 3R) -butanediol di-p-toluenesolfonate was prepared from (2R, 3R) -butanediol. This method of preparation is described in RB Mitra et al, J. Am. Chem. As disclosed in Soc 84 (1962). Put 100 mL (1.24 mol) of dried pyridine into a cooled 1 L flask in an ice water bath and mix with 100 g (0.525 mol) of chloride- p- toluenesolfonyl, and 22 mL (0.245 mol) of (2R, 3R) -butanediol. Slowly added dropwise. After raising the temperature to room temperature for 20 minutes, the mixture of semi-solid phase was kept at room temperature for 12 hours. Excess ice cubes were added and shaken vigorously to prevent lumps from forming. After confirming that the powder crystals were slowly separated, the mixture was stirred for 2 hours with ice cubes, and 70 ml of broken ice cubes and concentrated hydrochloric acid solution were poured into the mixture with vigorous stirring. The extracted slurry was filtered, washed thoroughly with water and dried to give 85 g (86.3%) of (2R, 3R) -butanediol di-p-toluenesolfonate (melting point 62 to 64 ° C).

250 mL의 적가용 펀넬과 환류 냉각용 콘덴서 및 질소 주입기를 장착한 3구 1 L 둥근 플라스크에 재결정화 된 트리페놀인 95 g과 건조된 테트라하이드로퓨란(THF) 300 mL를 주입했다. 이 용액에 얇은 리튬 조각 5.0 g을 25 ℃에서 교반하며 질소 하에서 가하여 용액 내에 LiPPh2를 형성시켰으며,이때 많은 열이 발생되면서 짙은 적황색으로 변하였다. 온도를 서서히 1 시간 동안 55 ℃로 올리고, 2 시간 동안 다시 25 ℃로 냉각하며 교반하였다. 형성된 페닐리튬은 증류 정제된 t-부틸클로라이드 33 g으로 45 분 동안 적가하여 분해시켰다. 투명한 적황색 용액을 5분 동안 끓인 후 다시 -4 ℃로 냉각하였다. Into a three-neck 1 L round flask equipped with 250 mL of dropping funnel, reflux condenser and nitrogen injector, 95 g of recrystallized triphenol and 300 mL of dried tetrahydrofuran (THF) were injected. 5.0 g of thin lithium flakes were added to the solution under stirring with stirring at 25 ° C. to form LiPPh 2 in the solution, which turned dark red as much heat was generated. The temperature was slowly raised to 55 ° C. for 1 hour and stirred while cooling to 25 ° C. for 2 hours. The formed phenyllithium was decomposed by dropwise addition of 33 g of distilled and purified t-butylchloride for 45 minutes. The clear red yellow solution was boiled for 5 minutes and then cooled to -4 ° C.

여기에 냉각 교반 상태에서 제조한 상기 (2R,3R)-부탄디올 디-p-톨루엔솔포네이트 35 g을 건조된 THF 100 mL에 녹인 후, 1 시간 동안 적가하였다. 서서히 상온으로 올린 후 30 분 간 교반하였다. 질소를 흘린 물 300 mL를 더한 후 THF를 감압으로 증류하여 제거한 결과 무색 오일 형태의 생성물이 추출되었다. 생성물을 에테르 150 mL로 2번 추출 후 Na2SO4에 의해 건조하였다. 에테르 추출물을 질소 하에 에탄올 50 mL에 6수화니켈과염산(nickel perchlorate hexahydrate) 15 g 용액 속에 여과하였다. 여과기에 남아있는 Na2SO4를 에테르로 철저히 세척 후 그 에테르 용액을 니켈용액에 더했다. 때때로 노란 결정을 띠면서 적갈색 오일 형태의 생성물은 [Ni((S,S)-chiraphos)2](ClO4)2이다. 이 오일 결정 혼합물을 뜨거운 에탄올(50 mL)에 녹아 있는 소디움 티오시안나이트(NaNCS) 15 g에 더하고 그 용액을 균일한 황갈 색 고체인 [Ni((S,S)-chiraphos)2NCS]NCS가 형성될 때까지 몇 시간동안 격렬하게 교반하였다. 이 고체 생성물을 에탄올로 완전히 세척 후 마지막으로 에테르로 세척하였다. To this was dissolved 35 g of (2R, 3R) -butanediol di-p-toluenesolfonate prepared in a cold stirring state in 100 mL of dried THF, followed by dropwise addition for 1 hour. After slowly raising to room temperature, the mixture was stirred for 30 minutes. 300 mL of nitrogen-dried water was added, and THF was distilled off under reduced pressure to extract a colorless oil. The product was extracted twice with 150 mL of ether and dried by Na 2 S0 4 . The ether extract was filtered under nitrogen in 50 g of ethanol in a 15 g solution of nickel perchlorate hexahydrate. Na 2 SO 4 remaining in the filter was thoroughly washed with ether, and the ether solution was added to the nickel solution. The product in the form of reddish brown oil, sometimes with yellow crystals, is [Ni ((S, S) -chiraphos) 2 ] (ClO 4 ) 2 . This oil crystal mixture was added to 15 g of sodium thiocyanate (NaNCS) dissolved in hot ethanol (50 mL) and the solution was added to a uniform yellowish brown solid [Ni ((S, S) -chiraphos) 2 NCS] NCS. Stir vigorously for several hours until formation. This solid product was washed thoroughly with ethanol and finally with ether.

상기 제조된 니켈 착체 15 g을 에탄올 150 mL로 질소 하에 부유시키고 교반하며 가열하였다. 물 20 g에 시안화나트륨(NaCN) 4 g을 재빠르게 더하였다. 니켈 착체는 서서히 용해되어 맑은 적색의 용액인 [Ni((S,S)-chiraphos)2CN3]-가 생성 된 다음 다시 베이지 색의 탁한 용액으로 변하였다. 뜨거운 용액을 노란색 슬러리가 될 때까지 교반하였다. 슬러리 용액을 냉각하고 고체를 물 25 mL로 두 번 연속해서 세척한 후 얼음으로 냉각한 에탄올로 재빠르게 냉각했다. 불순물이 포함된 베이지 색 고체를 25 ℃에서 건조 후, 끓는 무수 에탄올 125 mL에 더한 후 프리쯔에 의해 여과하였다. 상온으로 프리쯔 여과를 12 시간 유지시켜 무색의 광택성 고체를 수득한 후, 무수 에탄올 60 mL로 다시 결정화하여 완전 무색의 순수한 (S,S)-(페닐)2PCH(메틸)CH(메틸)P(페닐)2 5.5 g을 얻었다.15 g of the nickel complex prepared above were suspended with nitrogen and 150 mL of ethanol, and heated with stirring. 4 g of sodium cyanide (NaCN) were added quickly to 20 g of water. The nickel complex was slowly dissolved to form a clear red solution [Ni ( (S, S) -chiraphos) 2 CN 3 ] - , which was then converted to a beige turbid solution. The hot solution was stirred until a yellow slurry. The slurry solution was cooled and the solid washed twice in succession with 25 mL of water and then quickly cooled with ice-cooled ethanol. The beige solid containing impurities was dried at 25 ° C., added to 125 mL of boiling anhydrous ethanol, and then filtered by fritz. The fritted filtration was kept at room temperature for 12 hours to give a colorless glossy solid, which was then crystallized again with 60 mL of anhydrous ethanol to completely colorless pure (S, S) -(phenyl) 2 PCH (methyl) CH (methyl) 5.5 g of P (phenyl) 2 was obtained.

B.(B. ( S,S)S, S) -(페닐)-(Phenyl) 22 PCH(메틸)CH(메틸)P(페닐)PCH (methyl) CH (methyl) P (phenyl) 22 (테트라하이드로퓨란)삼염화크롬 (Tetrahydrofuran) chromium trichloride

[CrCl[CrCl 33 (THF){(P,P)-(THF) {(P, P)- kk 22 -(-( S,SS, S )-((Ph))-((Ph) 22 P(Me)CH-CH(Me)P(Ph)P (Me) CH-CH (Me) P (Ph) 22 )}] 의 제조)}]

삼테트라하이드로퓨란 삼염화 크롬(CrCl3(THF)3) 1.1 g(3.0 mmol)을 테트라하이드로퓨란 100 mL에 녹인 후 상기에서 제조한 (S,S)-(페닐)2PCH(메틸)CH(메 틸)P(페닐)2 리간드 화합물 1.28 g(3.0 mmol)을 역시 테트라하이드로퓨란 50 mL에 녹여서 서서히 가하고, 상온에서 교반하였다. 반응물을 1 시간 더 교반 후 진공으로 휘발물을 제거한후, 반응 생성물에 페트롤륨 에테르 100 mL를 적가하여 침전된 푸른색 고체를 수득하였다. 페트롤륨 에테르 100 mL으로 2번 세척하여 생성물 1.77 g(수율 90 %)를 얻었다. 1.1 g (3.0 mmol) of tritetrahydrofuran chromium trichloride (CrCl 3 (THF) 3 ) was dissolved in 100 mL of tetrahydrofuran, followed by ( S, S) -(phenyl) 2 PCH (methyl) CH (meth). 1.28 g (3.0 mmol) of the Til) P (phenyl) 2 ligand compound was also dissolved in 50 mL of tetrahydrofuran and added slowly, followed by stirring at room temperature. After the reaction was stirred for an additional hour, the volatiles were removed by vacuum, and then 100 mL of petroleum ether was added dropwise to the reaction product to obtain a precipitated blue solid. Washed twice with 100 mL of petroleum ether to give 1.77 g (90% yield) of product.

[촉매 제조예 2] [Catalyst Preparation Example 2] 비스-[(Bis-[( S,S)S, S) -(페닐)-(Phenyl) 22 PCH(메틸)CH(메틸)P(페닐)PCH (methyl) CH (methyl) P (phenyl) 22 이염화(μ-염화)크롬]Dichloride (μ-chloride) chromium]

[CrCl[CrCl 22 (μ-Cl){(P,P)-(μ-Cl) {(P, P)- kk 22 -(-( S,SS, S )-((Ph))-((Ph) 22 P(Me)CH-CH(Me)P(Ph)P (Me) CH-CH (Me) P (Ph) 22 )}])}] 22

삼테트라하이드로퓨란 삼염화 크롬(CrCl3(THF)3) 1.1 g(3.0 mmol)을 이염화메탄 100 mL에 녹인 후 상기 촉매 제조 예 1에서 제조한 (S,S)-(페닐)2PCH(메틸)CH(메틸)P(페닐)2 리간드 화합물 1.28 g(3.0 mmol)을 역시 이염화메탄 50 mL에 녹여서 서서히 가하였다. 반응물을 1 시간 더 교반 후 진공으로 휘발물을 제거하였다. 생성물에 페트롤륨 에테르 100 mL를 적가하여 푸른색 고체를 침전으로 수득하였다. 페트롤륨 에테르 100 mL으로 2번 세척하여 표제화합물 1.58 g(수율 90 %)를 얻었다. 제조된 착제 화합물의 단일 X선 회절 결정법으로 분석한 결과 도 1과 같은 구조를 보였다.1.1 g (3.0 mmol) of tritetrahydrofuran chromium trichloride (CrCl 3 (THF) 3 ) was dissolved in 100 mL of methane dichloride, and then ( S, S) -(phenyl) 2 PCH (methyl) prepared in Preparation Example 1 1.28 g (3.0 mmol) of (CH) (methyl) P (phenyl) 2 ligand compound was also slowly dissolved in 50 mL of methane dichloride. The reaction was stirred for an additional hour before the volatiles were removed in vacuo. 100 mL of petroleum ether was added dropwise to the product to give a blue solid as a precipitate. Washed twice with 100 mL of petroleum ether to give 1.58 g (90% yield) of the title compound. As a result of analysis by single X-ray diffraction crystallography of the prepared complex compound showed the structure as shown in FIG.

[촉매 제조예 3] [Catalyst Preparation Example 3] [([( S,S)S, S) -(페닐)-(Phenyl) 22 PCH(메틸)CH(메틸)P(페닐)PCH (methyl) CH (methyl) P (phenyl) 22 이아세틸아세토네 이트크롬] Iacetylacetonate Chromium]

[Cr{(O,O)-[Cr {(O, O)- kk 22 -(CH-(CH 33 COCHCOCH 22 COCHCOCH 33 )) 22 }{(P,P)-} {(P, P)- kk 22 -(-( S,SS, S )-((Ph))-((Ph) 22 P(Me)CH-CH(Me)P(Ph)P (Me) CH-CH (Me) P (Ph) 22 )}])}]

상기 촉매 제조예 2에서 삼테트라하이드로퓨란 삼염화 크롬 (CrCl3(THF)3) 대신 삼아세토아세틸 크롬 (Cr(acac)3) 1.1 g(3.0 mmol)을 사용한 것 이외에는 동일하게 반응을 진행하여, 표제 화합물 1.62 g 를 얻었다. The reaction was conducted in the same manner as in Preparation Example 2, except that 1.1 g (3.0 mmol) of triacetoacetyl chromium (Cr (acac) 3 ) was used instead of tritetrahydrofuran chromium trichloride (CrCl 3 (THF) 3 ). 1.62 g of compounds were obtained.

[촉매 제조예 4] [Catalyst Preparation Example 4] [([( S,S)S, S) -(페닐)-(Phenyl) 22 PCH(메틸)CH(메틸)P(페닐)PCH (methyl) CH (methyl) P (phenyl) 22 이(2-에틸 헥사노일)크롬]Di (2-ethyl hexanoyl) chrome]

[Cr{(OOCCH(C[Cr {(OOCCH (C 22 HH 55 )CC 44 HH 99 )) 22 }{(P,P)-} {(P, P)- kk 22 -(-( S,SS, S )-((Ph))-((Ph) 22 P(Me)CH-CH(Me)P(Ph)P (Me) CH-CH (Me) P (Ph) 22 )}])}]

삼테트라하이드로퓨란 삼염화 크롬 (CrCl3(THF)3) 대신 삼(2-에틸)헥사노에이트 크롬 (Cr(OOCCH(C2H5)C4H9)3) 1.44 g(3.0 mmol)을 사용한 것 이외에는 촉매 제조예 2와 동일하게 반응을 진행하여, 표제 화합물 1.82 g를 얻었다. Trichlorohydrofuran chromium trichloride (CrCl 3 (THF) 3 ) instead of tri (2-ethyl) hexanoate chromium (Cr (OOCCH (C 2 H 5 ) C 4 H 9 ) 3 ) 1.44 g (3.0 mmol) The reaction was carried out in the same manner as in Preparation Example 2, except that 1.82 g of the title compound was obtained.

[촉매 제조예 5] [Catalyst Preparation Example 5] 비스-[(Bis-[( R,R)R, R) -(페닐)-(Phenyl) 22 PCH(메틸)CH(메틸)P(페닐)PCH (methyl) CH (methyl) P (phenyl) 22 이염화(μ-염화)크롬]Dichloride (μ-chloride) chromium]

[CrCl[CrCl 22 (μ-Cl){(P,P)-(μ-Cl) {(P, P)- kk 22 -(-( R,R)R, R) -((Ph)-((Ph) 22 P(Me)CH-CH(Me)P(Ph)P (Me) CH-CH (Me) P (Ph) 22 )}])}] 22

A. 리간드 (A. Ligands ( R,R)R, R) -(페닐)-(Phenyl) 22 PCH(메틸)CH(메틸)P(페닐)PCH (methyl) CH (methyl) P (phenyl) 2 2

[([( R,RR, R )-Ph) -Ph 22 PCH(Me)CH(Me)PPhPCH (Me) CH (Me) PPh 22 ]의 제조Manufacture of

출발 반응 물질로 (2R,3R)-부탄디올 대신에 (2S,3S)-부탄디올을 사용하는 것을 제외하고, 사용한 것 이외에는 촉매제조예 1과 동일하게 반응을 진행하여, 표제 화합물 5.1 g을 얻었다. The reaction was carried out in the same manner as in Preparation Example 1, except that (2S, 3S) -butanediol was used instead of (2R, 3R) -butanediol as the starting reaction material, to obtain 5.1 g of the title compound.

B. 비스-[(B. bis-[( R,R)R, R) -(페닐)-(Phenyl) 22 PCH(메틸)CH(메틸)P(페닐)PCH (methyl) CH (methyl) P (phenyl) 22 이염화(μ-염화)크롬] Dichloride (μ-chloride) chromium]

[CrCl[CrCl 22 (μ-Cl){(P,P)-(μ-Cl) {(P, P)- kk 22 -(-( R,R)R, R) -((Ph)-((Ph) 22 P(Me)CH-CH(Me)P(Ph)P (Me) CH-CH (Me) P (Ph) 22 )}])}] 22 의 제조 Manufacture

(S,S)- 대신 (R,R)-(페닐)2PCH(메틸)CH(메틸)P(페닐)2 리간드 화합물 1.28 g(3.0 mmol)을 사용한 것 이외에는 촉매 제조예 2와 동일하게 반응을 진행하여표제화합물 생성물 1.58 g를 얻었다. 이 착제 화합물의 단일 X선 회절 결정법으로 분석한 결과 도 2와 같은 구조를 보였다. (S, S) - instead of (R, R) - (phenyl) 2 PCH (methyl) CH (methyl) P (phenyl) 2 ligand compound 1.28 g was used a (3.0 mmol), the same reaction as prepared in Catalyst Preparation Example 2 Proceed to 1.58 g of the title compound product. Analysis of the complex compound by a single X-ray diffraction crystallography showed the structure as shown in FIG. 2.

[촉매 제조예 6] [Catalyst Preparation Example 6] 비스-[Bis- [ mesomeso -(페닐)-(Phenyl) 22 PCH(메틸)CH(메틸)P(페닐)PCH (methyl) CH (methyl) P (phenyl) 22 이염화(μ-염화)크롬] Dichloride (μ-chloride) chromium]

[CrCl[CrCl 22 (μ-Cl){(P,P)-(μ-Cl) {(P, P)- kk 22 -- mesomeso -((Ph)-((Ph) 22 P(Me)CH-CH(Me)P(Ph)P (Me) CH-CH (Me) P (Ph) 22 )}])}] 22

A. 리간드 A. Ligands mesomeso -(페닐)-(Phenyl) 22 PCH(메틸)CH(메틸)P(페닐)PCH (methyl) CH (methyl) P (phenyl) 2 2

[[ mesomeso -Ph-Ph 22 PCH(Me)CH(Me)PPhPCH (Me) CH (Me) PPh 22 ]의 제조Manufacture of

출발 반응 물질로 (2R,3R)-부탄디올을 사용하는 대신에 meso-부탄디올을 사용하는 것을 제외하고 촉매 제조예 1과 동일한 방법으로 제조하였다. 완전 무색의 순수 meso-(페닐)2PCH(메틸)CH(메틸)P(페닐)2 5.7 g을 얻었다. A catalyst was prepared in the same manner as in Preparation Example 1, except that meso -butanediol was used instead of (2R, 3R) -butanediol as a starting reaction material. 5.7 g of completely colorless pure meso- (phenyl) 2 PCH (methyl) CH (methyl) P (phenyl) 2 was obtained.

B. 비스-[B. bis- [ mesomeso --(페닐)-(Phenyl) 22 PCH(메틸)CH(메틸)P(페닐)PCH (methyl) CH (methyl) P (phenyl) 22 이염화(μ-염화)크롬] Dichloride (μ-chloride) chromium]

[CrCl[CrCl 22 (μ-Cl){(P,P)-(μ-Cl) {(P, P)- kk 22 -- mesomeso -((Ph)-((Ph) 22 P(Me)CH-CH(Me)P(Ph)P (Me) CH-CH (Me) P (Ph) 22 )}])}] 22 의 제조 Manufacture

(S,S)- 대신 meso-(페닐)2PCH(메틸)CH(메틸)P(페닐)2 리간드 화합물 1.28 g(3.0 mmol)을 사용한 것 이외에는 촉매 제조예 2와 동일하게 반응을 진행하여, 표제 화합물 1.43 g를 얻었다. The reaction was carried out in the same manner as in Preparation Example 2, except that 1.28 g (3.0 mmol) of ( S, S) -meso- (phenyl) 2 PCH (methyl) CH (methyl) P (phenyl) 2 ligand compound was used instead. 1.43 g of the title compound were obtained.

[촉매 제조예 7] [Catalyst Preparation Example 7] 비스-[(Bis-[( R,R)R, R) -(4-메톡시페닐)-(4-methoxyphenyl) 22 PCH(메틸)CH(메틸)P(4-메톡시페닐)PCH (methyl) CH (methyl) P (4-methoxyphenyl) 22 이염화(μ-염화)크롬] Dichloride (μ-chloride) chromium]

CrClCrCl 22 (μ-Cl){(P,P)-(μ-Cl) {(P, P)- kk 22 -(-( R,R)R, R) -((4-MeOPh)-((4-MeOPh) 22 P(Me)CH-CH(Me)P(4MeOPh)P (Me) CH-CH (Me) P (4MeOPh) 22 )}])}] 22

A. 리간드 (A. Ligands ( R,R)R, R) -(4-메톡시페닐)-(4-methoxyphenyl) 22 PCH(메틸)CH(메틸)P(4-메톡시페닐)PCH (methyl) CH (methyl) P (4-methoxyphenyl) 2 2

[([( R,RR, R )-(4-MeOPh))-(4-MeOPh) 22 PCH(Me)CH(Me)P(4-MeOPh)PCH (Me) CH (Me) P (4-MeOPh) 22 ]의 제조Manufacture of

B. Bosnich et al, J. Am. Chem. Soc 99(19)(1977)에 개시된 바와 같이 제조하였다. In B. Bosnich et al, J. Am. Chem. Prepared as disclosed in Soc 99 (19) (1977).

(2S,3S)-부탄디올로부터의 (2S,3S)-부탄디올 디-p-톨루엔솔포네이트의 제조는 촉매 제조예 1의 방법대로 하였다. (2S, 3S) - butanediol from (2S, 3S) - Preparation of toluene-butanediol di -p- solpo carbonate was as prepared in Catalyst Preparation Example 1 method.

트리(4-메톡시페닐)인의 제조는 다음과 같이 진행하였다. 마그네슘 조각(91.1 g, 3.75 mol)을 THF 2 L 중의 4-브로모-아니졸 95 mL(0.75 mol)으로 적가 하였다. 격렬히 반응 후 반응 혼합물을 환류 하에 2 시간 동안 가열하여 그리냐드 시약을 수득하였다. 이 그리냐드 시약을 -78 ℃에서 THF 2 L 중의 PCl3 용액 17.5 mL(0.2 mol)에 교반하면서 2 시간에 걸쳐 적가하였다. 적가 완료 후, 드라이아이스/아세톤 조를 제거하고 반응물을 상온으로 올렸다. 반응물을 밤새 교반하고 용매를 진공 중에서 제거하였다. 이 포스핀 생성물은 제거 없이 모두 다음 단계에서 사용되었다. The preparation of tri (4-methoxyphenyl) yne was carried out as follows. A piece of magnesium (91.1 g, 3.75 mol) was added dropwise to 95 mL (0.75 mol) of 4-bromo-anisol in 2 L of THF. After vigorous reaction, the reaction mixture was heated at reflux for 2 hours to obtain Grignard reagent. This Grignard reagent was added dropwise over 2 hours with stirring to 17.5 mL (0.2 mol) of a solution of PCl 3 in 2 L of THF at -78 ° C. After completion of the dropwise addition, the dry ice / acetone bath was removed and the reaction raised to room temperature. The reaction was stirred overnight and the solvent was removed in vacuo. This phosphine product was all used in the next step without removal.

250 mL의 적가용 포넬과 환류 냉각용 콘덴서 및 질소 주입기를 장착한 3 구 1 L 둥근 플라스크에 재결정화 된 트리(4-메톡시페놀)인 70 g과 건조된 테트라하이드로퓨란(THF) 300 mL를 주입했다. 이 용액에 얇은 리튬 조각 2.8 g을 25 ℃에서 교반하며 질소 하에서 넣었다. 용액에 즉시 LiP(4-OMe-Ph)2가 형성되고, 많은 열이 발생되면서 짙은 적황색으로 변하였다. 온도를 서서히 1 시간 동안 55 ℃로 올리고 2 시간 동안 다시 25 ℃로 냉각하며 교반하였다. 형성된 4-메톡시페닐리튬은 증류 정제된 t-부틸클로라이드 18.5 g으로 45 분 동안 적가하여 분해시켰다. 투명한 적황색 용액을 5 분 동안 끓인 후 다시 -4 ℃로 냉각하였다. In a 3-necked 1 L round flask equipped with 250 mL drop-in fornell, reflux condenser and nitrogen injector, 70 g of recrystallized tri (4-methoxyphenol) and 300 mL of dried tetrahydrofuran (THF) Injected. To this solution 2.8 g of thin lithium pieces were placed under nitrogen with stirring at 25 ° C. LiP (4-OMe-Ph) 2 formed immediately in the solution and turned to dark red yellow with much heat. The temperature was slowly raised to 55 ° C. for 1 hour and stirred while cooling to 25 ° C. for 2 hours. The 4-methoxyphenyllithium formed was decomposed by dropwise addition of 18.5 g of distilled and purified t-butylchloride for 45 minutes. The clear red yellow solution was boiled for 5 minutes and then cooled to -4 ° C.

여기에 냉각 교반 상태에서 위에서 제조한 (2S,3S)-부탄디올 디-p-톨루엔솔포네이트 19.6 g을 건조된 THF 100 mL에 녹인 후, 1 시간 동안 적가하였다. 서서히 상온으로 올린 후 30분간 교반하였다. 질소를 흘린 물 300 mL를 더한 후 THF를 감압으로 증류하여 제거한 결과 무색 오일 형태의 생성물이 추출되었다. 생성물을 에테르 150 mL로 2번 추출 후 Na2SO4에 의해 건조하였다. 에테르 추출물을 질소 하에 에탄올 50 mL에 6수화니켈과염산 (nickel perchlorate hexahydrate) 8.4 g 용액 속에 여과하였다. 여과기에 남아있는 Na2SO4를 에테르로 철저히 세척 후 그 에테르 용액을 니켈용액에 더했다. 적갈색 오일 형태의 생성물은 [Ni((2R,3R)-비스(디-p-메톡시페닐)포스포러스부탄)2](ClO4)2이다. 이 오일 결정 혼합물을 뜨거운 에탄올(50 mL)에 녹아 있는 소디윰 씨오시안나이트(NaNCS) 8.4 g에 더하고 그 용액을 균일한 황갈색 고체인 [Ni((2R,3R)-비스(디-p-메톡시페닐)포스포러스부탄)2NCS]NCS가 형성될 때까지 몇 시간 동안 격렬하게 교반하였다. 이 고체 생성물을 에탄올로 완전히 세척한 후 마지막으로 에테르로 세척하였다. 19.6 g of (2S, 3S) -butanediol di-p-toluenesolfonate prepared above was dissolved in 100 mL of dried THF, and then added dropwise thereto for 1 hour while cooling and stirring. After slowly raising to room temperature, the mixture was stirred for 30 minutes. 300 mL of nitrogen-dried water was added, and THF was distilled off under reduced pressure to extract a colorless oil. The product was extracted twice with 150 mL of ether and dried by Na 2 S0 4 . The ether extract was filtered under a nitrogen into a solution of 8.4 g of nickel perchlorate hexahydrate in 50 mL of ethanol. Na 2 SO 4 remaining in the filter was thoroughly washed with ether, and the ether solution was added to the nickel solution. The product in the form of reddish brown oil is [Ni ( (2R, 3R) -bis (di-p-methoxyphenyl) phosphorusbutane) 2 ] (ClO 4 ) 2 . This oil crystal mixture was added to 8.4 g of Sodyan Thiocyanite (NaNCS) dissolved in hot ethanol (50 mL) and the solution was added to a uniform tan solid [Ni ( (2R, 3R) -bis (di-p-meth). Oxyphenyl) phosphorusbutane) 2 Stirred vigorously for several hours until NCS] NCS was formed. This solid product was washed thoroughly with ethanol and finally with ether.

이 니켈 착체 17 g을 에탄올 150 mL로 질소 하에 부유시키고 교반하며 가열하였다. 물 20 g에 시안화 나트륨(NaCN) 4 g을 재빠르게 더하였다. 니켈 착체는 서서히 용해되어 맑은 적색의 용액인 [Ni((2R,3R)-비스(디-p-메톡시페닐)포스포러스부탄)2CN3]-가 생성 된 다음, 다시 베이지 색의 탁한 용액으로 변하였다. 뜨거운 용액을 노란색 슬러리가 될 때까지 교반하였다. 슬러리 용액을 냉각하고 고체를 물로 25 mL 두 번 연속해서 세척한 후 얼음으로 냉각한 에탄올로 재빠르게 냉각했다. 불순물이 포함된 베이지 색 고체를 25 ℃에서 건조 후, 끓는 무수 에탄올 125 mL로 더한 후 프리쯔에 의해 여과하였다. 상온으로 프리쯔 여과를 12 시간 유지시킨 결과 여과액이 모두 빠지고 무색의 광택나는 고체만 남았다. 무수 에탄올 60 mL로 다시 결정화하여 완전 무색의 순수한 (R,R)-(4-메톡시페닐)2PCH(메틸)CH(메틸)P(4-메 톡시페닐)2 6.2 g을 얻었다. 17 g of this nickel complex was suspended in nitrogen with 150 mL of ethanol and heated with stirring. 4 g of sodium cyanide (NaCN) were added quickly to 20 g of water. The nickel complex was slowly dissolved to form a clear red solution [Ni ( (2R, 3R) -bis (di-p-methoxyphenyl) phosphorusbutane) 2 CN 3 ] - , which was then beige turbid. Turned into. The hot solution was stirred until a yellow slurry. The slurry solution was cooled and the solid washed 25 mL twice in succession with water and then quickly cooled with ice-cooled ethanol. The beige solid containing impurities was dried at 25 ° C., then added to 125 mL of boiling anhydrous ethanol and filtered by frittes. The fritted filtration was maintained at room temperature for 12 hours, and the filtrate was lost and only a colorless, glossy solid remained. Crystallization again with 60 mL of absolute ethanol gave 6.2 g of completely colorless pure (R, R)- (4-methoxyphenyl) 2 PCH (methyl) CH (methyl) P (4-methoxyphenyl) 2 .

B. 비스-[(B. bis-[( R,R)R, R) -(4-메톡시페닐)-(4-methoxyphenyl) 22 PCH(메틸)CH(메틸)P(4-메톡시페닐)PCH (methyl) CH (methyl) P (4-methoxyphenyl) 22 이염화(μ-염화)크롬] Dichloride (μ-chloride) chromium]

[CrCl[CrCl 22 (μ-Cl){(P,P)-(μ-Cl) {(P, P)- kk 22 -(-( R,R)R, R) -((4-MeOPh)-((4-MeOPh) 22 P(Me)CH-CH(Me)P(4MeOPh)P (Me) CH-CH (Me) P (4MeOPh) 22 )}])}] 22 의 제조Manufacture

(S,S)-(페닐)2PCH(메틸)CH(메틸)P(페닐)2 대신 (R,R)-(4-메톡시페닐)2PCH(메틸)CH(메틸)P(4-메톡시페닐)2 리간드 화합물 1.64 g(3.0 mmol)을 사용한 것 이외에는 상기 촉매 제조예 2와 동일하게 진행하여, 표제 화합물 생성물 1.29 g를 얻었다. ( S, S) -(phenyl) 2 PCH (methyl) CH (methyl) P (phenyl) 2 instead of (R, R)- (4-methoxyphenyl) 2 PCH (methyl) CH (methyl) P (4- The procedure was the same as in Preparation Example 2, except that 1.64 g (3.0 mmol) of methoxyphenyl) 2 ligand compound was used to obtain 1.29 g of the title compound product.

[촉매 제조예 8] [Catalyst Preparation Example 8] 비스-[(Bis-[( S,S)S, S) -(4-메틸페닐)-(4-methylphenyl) 22 PCH(메틸)CH(메틸)P(4-메틸페닐)PCH (methyl) CH (methyl) P (4-methylphenyl) 22 이염화(μ-염화)크롬] Dichloride (μ-chloride) chromium]

[CrCl[CrCl 22 (μ-Cl){(P,P)-(μ-Cl) {(P, P)- kk 22 -(-( S,S)S, S) -((4-MePh)-((4-MePh) 22 P(Me)CH-CH(Me)P(4-MePh)P (Me) CH-CH (Me) P (4-MePh) 22 )}])}] 22

A. 리간드 (A. Ligands ( S,S)S, S) -(4-메틸페닐)-(4-methylphenyl) 22 PCH(메틸)CH(메틸)P(4-메틸페닐)PCH (methyl) CH (methyl) P (4-methylphenyl) 22

[([( S,SS, S )-(4-MePh))-(4-MePh) 22 PCH(Me)CH(Me)P(4-MePh)PCH (Me) CH (Me) P (4-MePh) 22 ]의 제조Manufacture of

트리(4-메틸페닐)인을 제조하기 위해 4-톨릴-브로마이드를 사용하는 것을 제외하고는 모든 합성 과정을 촉매 제조예 7의 방법과 동일하게 진행하여, 완전 무색 의 순수 (S,S)-(4-메틸페닐)2P-CH(메틸)CH(메틸)-P(4-메틸페닐)2 3.9 g을 얻었다. Except for the use of 4-tolyl-bromide to prepare tri (4-methylphenyl) yne, all synthesis was carried out in the same manner as in Preparation Example 7 to give completely colorless pure (S, S) -( 3.9 g of 4-methylphenyl) 2 P-CH (methyl) CH (methyl) -P (4-methylphenyl) 2 was obtained.

B. 비스-[(B. bis-[( S,S)S, S) -(4-메틸페닐)-(4-methylphenyl) 22 PCH(메틸)CH(메틸)P(4-메틸페닐)PCH (methyl) CH (methyl) P (4-methylphenyl) 22 이염화(μ-염화)크롬] Dichloride (μ-chloride) chromium]

[CrCl[CrCl 22 (μ-Cl){(P,P)-(μ-Cl) {(P, P)- kk 22 -(-( S,S)S, S) -((4-MePh)-((4-MePh) 22 P(Me)CH-CH(Me)P(4-MePh)P (Me) CH-CH (Me) P (4-MePh) 22 )}])}] 2 2 의 제조Manufacture

(S,S)-(페닐)2PCH(메틸)CH(메틸)P(페닐)2 대신 (R,R)-(4-메틸페닐)2PCH(메틸)CH(메틸)P(4-메틸페닐)2 리간드 화합물 1.45 g (3.0 mmol)을 사용한 것 이외에는 상기 촉매 제조예 2와 동일하게 반응을 진행하여, 표제화합물 1.31 g를 얻었다. ( S, S) -(phenyl) 2 PCH (methyl) CH (methyl) P (phenyl) 2 instead of (R, R)- (4-methylphenyl) 2 PCH (methyl) CH (methyl) P (4-methylphenyl) The reaction was carried out in the same manner as in Preparation Example 2, except that 1.45 g (3.0 mmol) of the two ligand compound was used, thereby obtaining 1.31 g of the title compound.

[촉매 제조예 9] [Catalyst Preparation Example 9] 비스-[(Bis-[( S,S)S, S) -(페닐)-(Phenyl) 22 PCH(페틸)CH(페틸)P(페닐)PCH (Petyl) CH (Petyl) P (phenyl) 22 이염화(μ-염화)크롬] [CrClDichloride (μ-Chloride)] [CrCl 22 (μ-Cl){(P,P)-(μ-Cl) {(P, P)- kk 22 -(-( S,S)S, S) -(Ph-(Ph 22 P(Ph)CH-CH(Ph)PPhP (Ph) CH-CH (Ph) PPh 22 )}])}] 22

A. 리간드 (S,S)-(페닐)A. Ligands (S, S)-(phenyl) 22 P-CH(페닐)CH(페닐)-P(페닐)P-CH (phenyl) CH (phenyl) -P (phenyl) 2 2

[(S,S)-(Ph((S, S)-(Ph 22 P(Ph)CH-CH(Ph)PPhP (Ph) CH-CH (Ph) PPh 22 ]의 제조Manufacture of

출발물질로 (1R,2R)-1,2-디페닐에탄디올을 사용하였으며 촉매 제조예 1과 동일한 방법으로 제조하여, 무색의 표제 화합물 3.3 g을 얻었다.( 1R, 2R ) -1,2-diphenylethanediol was used as a starting material and prepared in the same manner as in Preparation Example 1 to obtain 3.3 g of a colorless title compound.

B. 비스-[(B. bis-[( S,S)S, S) -(페닐)-(Phenyl) 22 PCH(페틸)CH(페틸)P(페닐)PCH (Petyl) CH (Petyl) P (phenyl) 22 이염화(μ-염화)크롬] Dichloride (μ-chloride) chromium]

[CrCl[CrCl 22 (μ-Cl){(P,P)-(μ-Cl) {(P, P)- kk 22 -(-( S,S)S, S) -(Ph-(Ph 22 P(Ph)CH-CH(Ph)PPhP (Ph) CH-CH (Ph) PPh 22 )}])}] 22 의 제조Manufacture

(S,S)-(페닐)2PCH(메틸)CH(메틸)P(페닐)2 대신 (S,S)-(페닐)2P-CH(페닐)CH(페닐)-P(페닐)2 리간드 화합물 1.35 g(3.0 mmol)을 사용한 것 이외에는 상기 촉매 제조 예 2와 동일하게 진행하여, 표제 화합물 0.9 g를 얻었다. ( S, S) -(phenyl) 2 PCH (methyl) CH (methyl) P (phenyl) 2 instead of (S, S) -(phenyl) 2 P-CH (phenyl) CH (phenyl) -P (phenyl) 2 Except for using 1.35 g (3.0 mmol) of ligand compounds, it carried out similarly to the catalyst preparation example 2, and obtained 0.9 g of the title compounds.

[촉매 제조예 10] [Catalyst Preparation Example 10] 비스-[{(Bis-[{( 1S,2S)1S, 2S) -- 트랜스Trance -비스(디페닐포스피노)사이클로헥산}이염화(μ-염화)크롬] [CrCl-Bis (diphenylphosphino) cyclohexane} dichloride (μ-chloride) chromium] [CrCl 22 (μ-Cl){(P,P)-(μ-Cl) {(P, P)- kk 22 -(-( 1S,2S)1S, 2S) -(Ph-(Ph 22 P)P) 22 cyclohexane}]cyclohexane}] 22

A. 리간드 (A. Ligands ( 1S,2S)1S, 2S) -- 트랜스Trance -비스(디페닐포스피노)사이클로헥산[(-Bis (diphenylphosphino) cyclohexane [( 1S,2S)1S, 2S) -(Ph-(Ph 22 P)P) 22 cyclohexane]의 제조preparation of cyclohexane]

출발 반응 물질로 (2R,3R)-부탄디올 대신에 (1R,2R)-트랜스-사이클로헥산디올을 사용하는 것을 제외하고 촉매 제조예 1과 동일한 방법으로 제조하였다. 완전 무색의 순수 표제 화합물 3.6 g을 얻었다. A catalyst was prepared in the same manner as in Preparation Example 1, except that (1R, 2R) -trans -cyclohexanediol was used instead of (2R, 3R) -butanediol as a starting reaction material. 3.6 g of completely colorless pure title compound was obtained.

B. 비스-[{(B. bis-[{( 1S,2S)1S, 2S) -- 트랜스Trance -비스(디페닐포스피노)사이클로헥산}이염화(μ-염화)크롬] [CrCl-Bis (diphenylphosphino) cyclohexane} dichloride (μ-chloride) chromium] [CrCl 22 (μ-Cl){(P,P)-(μ-Cl) {(P, P)- kk 22 -(-( 1S,2S)1S, 2S) -(Ph-(Ph 22 P)P) 22 cyclohexane}]cyclohexane}] 22 의 제조Manufacture

(S,S)-(페닐)2PCH(메틸)CH(메틸)P(페닐)2 대신 (1S,2S)-트랜스-비스(디페닐포스피노)사이클로헥산 리간드 화합물 1.36 g(3.0 mmol)을 사용한 것 이외에는 상기 촉매 제조예 2와 동일하게 진행하여, 생성물 1.07 g를 얻었다.1.36 g (3.0 mmol) of ( 1S, 2S) -trans -bis (diphenylphosphino) cyclohexane ligand compound instead of ( S, S) -(phenyl) 2 PCH (methyl) CH (methyl) P (phenyl) 2 Except for the use, it proceeded in the same manner as in the catalyst preparation example 2 to obtain 1.07 g of the product.

[촉매 제조예 11] [Catalyst Preparation Example 11] 비스-[{(Bis-[{( 3S,4S)3S, 4S) -- 트랜스Trance -비스(디페닐포스피노)1-벤질피롤리딘}이염화(μ-염화)크롬] -Bis (diphenylphosphino) 1-benzylpyrrolidine} dichloride (μ-chloride) chromium]

[CrCl[CrCl 22 (μ-Cl){(P,P)-(μ-Cl) {(P, P)- kk 22 -(-( 3S,4S)3S, 4S) -(Ph-(Ph 22 P)P) 22 1-benzylpyrrolidine}]1-benzylpyrrolidine}] 22

A. 리간드 (A. Ligands ( 3S,4S)3S, 4S) -- 트랜스Trance -비스(디페닐포스피노)1-벤질피롤리딘Bis (diphenylphosphino) 1-benzylpyrrolidine

[([( 3S,4S)3S, 4S) -(Ph-(Ph 22 P)P) 22 1-benzylpyrrolidine]의 제조1-benzylpyrrolidine]

출발 반응 물질로 (2R,3R)-부탄디올 대신에 (3R,4R)-트랜스-1-벤질피롤리딘디올을 사용하는 것을 제외하고 촉매 제조예 1과 동일한 방법으로 제조하여, 무색의 순수 (3S,4S)-트랜스-비스(디페닐포스피노)1-벤질피롤리딘 2.7 g을 얻었다. Colorless pure water ( 3S) was prepared in the same manner as in Preparation Example 1, except that (3R, 4R) -trans -1-benzylpyrrolidinediol was used instead of (2R, 3R) -butanediol as the starting reaction material. , 4S) -2.7 g of trans -bis (diphenylphosphino) 1-benzylpyrrolidine was obtained.

B. 비스-[{(B. bis-[{( 3S,4S)3S, 4S) -- 트랜스Trance -비스(디페닐포스피노)1-벤질피롤리딘}이염화(μ-염화)크롬] -Bis (diphenylphosphino) 1-benzylpyrrolidine} dichloride (μ-chloride) chromium]

[CrCl 2 (μ-Cl){(P,P)- k 2 -( 3S,4S) -(Ph 2 P) 2 1-benzylpyrrolidine}] 2 의 제조 (S,S)-(페닐)2PCH(메틸)CH(메틸)P(페닐)2 대신 (3S,4S)-트랜스-비스(디페닐포스피노)1-벤질피롤리딘 리간드 화합물 1.59 g(3.0 mmol)을 사용한 것 이외에 상기 촉매 제조예 2와 동일하게 진행하여, 생성물 1.15 g를 얻었다. [CrCl 2 (μ-Cl) {(P, P) - k 2 - (3S, 4S) - (Ph 2 P) 2 1-benzylpyrrolidine}] 2 Preparation of (S, S) - (phenyl) 2 PCH ( methyl) CH (methyl) P (phenyl) 2 instead of (3S, 4S) - trans- bis (diphenylphosphino) 1-benzyl-pyrrolidin-ligand compound 1.59 g (for preparation of the catalyst other than that there was used 3.0 mmol) 2 Proceed in the same manner as above to obtain 1.15 g of the product.

[촉매 제조예 12] [Catalyst Preparation Example 12] 비스-[(Bis-[( S,S)S, S) -(페닐)-(Phenyl) 22 PCH(메틸)CH(메틸)P(페닐)PCH (methyl) CH (methyl) P (phenyl) 22 염화(μ-염화)크롬(II)] [Cr(II)Cl(μ-Cl){(P,P)-Chloride (μ-chloride) (II)] [Cr (II) Cl (μ-Cl) {(P, P)- kk 22 -(-( S,SS, S )-((Ph))-((Ph) 22 P(Me)CH-CH(Me)P(Ph)P (Me) CH-CH (Me) P (Ph) 22 )}])}] 22

삼테트라하이드로퓨란 삼염화 크롬 (CrCl3(THF)3) 대신 Cr(II)Cl2 1.02 g(3.0 mmol)을 사용한 것 이외에는 촉매 제조예 2와 동일하게 반응을 진행하여, 표제 화합물 1.51 g를 얻었다.The reaction was carried out in the same manner as in Preparation Example 2, except that 1.02 g (3.0 mmol) of Cr (II) Cl 2 was used instead of tritetrahydrofuran chromium trichloride (CrCl 3 (THF) 3 ) to obtain 1.51 g of the title compound.

[실시예 1] 상기 제조한 촉매 및 MAO를 사용한 에틸렌 올리고머화 반응 Example 1 Ethylene Oligomerization Reaction Using the Prepared Catalyst and MAO

600 mL 스텐레스 스틸 반응기를 질소, 진공으로 세척 후 사이클로 헥산을 200 mL 가하고 MAO 1.5 m㏖-Al을 더한 후 45 ℃로 온도 상승시켰다. 글로브 상자에서 50 mL Schlenk 용기에 사이클로헥산 10 mL에 촉매 제조예 1의 (S,S)-(페닐)2PCH(메틸)CH(메틸)P(페닐)2(테트라하이드로퓨란)삼염화크롬 3.3 mg(0.005m㏖)을 혼합하여 반응기에 더했다. 압력 반응기에 에틸렌을 30 bar로 충진하고, 300 rpm의 교반속도로 교반하였다. 120 분 후 반응기에 에틸렌 공급을 중단하고, 교반을 멈추어 반응을 중단하고 반응기를 10 ℃ 아래로 냉각하였다.The 600 mL stainless steel reactor was washed with nitrogen and vacuum, 200 mL of cyclohexane was added, 1.5 mmol-MAO was added, and the temperature was raised to 45 ° C. Catalyst Preparation Example 1 in 10 mL of cyclohexane in a 50 mL Schlenk vessel in a glove box ( S, S) -(phenyl) 2 PCH (methyl) CH (methyl) P (phenyl) 2 (tetrahydrofuran) 3.3 mg (0.005 mmol) of chromium trichloride were mixed and added to the reactor. The pressure reactor was filled with ethylene at 30 bar and stirred at a stirring speed of 300 rpm. After 120 minutes the ethylene feed to the reactor was stopped, the stirring was stopped to stop the reaction and the reactor was cooled down below 10 ° C.

반응기 내의 과량의 에틸렌을 방출한 후 반응기에 함유된 액체에 10 vol% 염산이 섞인 에탄올을 주입하였다. 액상을 GC-FID로 분석하기 위해 내부 표준물로 노난을 첨가하였다. 소량의 유기층 샘플을 무수황산마그네슘 상에 통과하여 건조시킨 후, GC-FID로 분석하였다. 나머지 유기층을 여과하여 고체 왁스/폴리머 생성물을 분리하였다. 이들 고체 생성물을 100 ℃ 오븐에서 밤새 건조한 후, 중량을 재어 폴리에틸렌 1.2 g을 수득하였다. GC 분석하여 반응 혼합물의 총질량이 116.2 g임을 확인하였다. 본 실시예의 생성물 분포를 표 1에 요약하였다.After releasing excess ethylene in the reactor, ethanol mixed with 10 vol% hydrochloric acid was injected into the liquid contained in the reactor. Nonan was added as an internal standard to analyze the liquid phase by GC-FID. A small amount of organic layer sample was dried over anhydrous magnesium sulfate and analyzed by GC-FID. The remaining organic layer was filtered to separate the solid wax / polymer product. These solid products were dried overnight in a 100 ° C. oven and then weighed to give 1.2 g of polyethylene. GC analysis confirmed that the total mass of the reaction mixture was 116.2 g. The product distribution of this example is summarized in Table 1.

[실시예 2 내지 실시예 12] 상기 제조한 촉매 및 MAO를 사용한 에틸렌 올리고머화 반응 추가 실시 [Examples 2 to 12] Further ethylene oligomerization reaction using the catalyst and MAO prepared above

촉매로서 촉매 제조예 2 내지 촉매 제조예 12을 각각 취하여 적정량 사용하 고 MAO 양과 반응 시간도 적정하게 선택하는 것 이외에는 실시 예 1과 같은 방법으로 실시하였다. 취해진 조건과 얻어진 결과를 표 1에 요약하였다. The catalysts were prepared in the same manner as in Example 1, except that each of Catalyst Preparation Examples 2 to 12 was used as the catalyst, and the MAO amount and the reaction time were appropriately selected. The conditions taken and the results obtained are summarized in Table 1.

[비교예] CrCl 3 (테트라하이드로퓨란) 3 , (S, S)- (페닐) 2 PCH(메틸)CH(메틸)P(페닐) 2 및 MAO를 사용한 에틸렌 사량체화 반응 [Comparative Example] Ethylene tetramerization reaction using CrCl 3 (tetrahydrofuran) 3 , (S, S)- (phenyl) 2 PCH (methyl) CH (methyl) P (phenyl) 2 and MAO

상기 촉매 제조 예 1의 리간드 (S,S)-(페닐)2PCH(메틸)CH(메틸)P(페닐)2 [(S,S)-Ph2PCH(Me)CH(Me)PPh2] 2.2 mg(0.005 mmol)와 CrCl3(테트라하이드로퓨란)3 1.88 mg(0.005 m㏖)을 취한 것 이외에는 실시 예 1과 같은 방법으로 실시 하였다. 취해진 조건과 얻어진 결과를 표 1에 요약하였다. Ligand ( S, S) -(phenyl) 2 PCH (methyl) CH (methyl) P (phenyl) 2 [( S, S ) -Ph 2 PCH (Me) CH (Me) PPh 2 ] of Catalyst Preparation Example 1 The same procedure as in Example 1 was carried out except that 2.2 mg (0.005 mmol) and 1.88 mg (0.005 mmol) of CrCl 3 (tetrahydrofuran) 3 were taken. The conditions taken and the results obtained are summarized in Table 1.

[표 1] 에틸렌 올리고머화 반응 실시 결과Table 1 Results of Ethylene Oligomerization Reaction

Figure 112009005732370-PAT00017
Figure 112009005732370-PAT00017

위 실시예 및 비교예를 참고로 하면, 본 발명에 따른 촉매를 이용한 올리고머의 제조방법은 종래 방법인 리간드와 촉매 전구체를 각각 따로따로 주입한 비교예 결과보다 산출량이 약 15배 정도 까지 증대되었음을 확인할 수 있으며, 폴리머 중합체 부산물의 양이 5.3 %에서 0.5 %이하까지 감소하였음을 확인할 수 있다. Referring to the above Examples and Comparative Examples, the method for preparing an oligomer using the catalyst according to the present invention confirmed that the output was increased by about 15 times than the result of Comparative Example in which the ligand and the catalyst precursor were separately injected in the conventional method. It can be seen that the amount of polymer by-products decreased from 5.3% to less than 0.5%.

한편, 실시예의 결과들은 촉매 착체를 합성함에 있어서 합성 용매와 조건에 따라 얻어지는 착제의 구조가 다르고 이들 착제의 활성능도 상당히 차이가 있음을 알 수 있다.On the other hand, the results of the examples in the synthesis of the catalyst complex can be seen that the structure of the complex obtained according to the solvent and the conditions are different and the activity of these complexes is also significantly different.

도 1은 촉매 제조예 2에서 제조한 화합물의 X-선 회절 구조를 나타낸 것이다.1 shows the X-ray diffraction structure of the compound prepared in Preparation Example 2.

도 2는 촉매 제조예 5에서 제조한 화합물의 X-선 회절 구조를 나타낸 것이다.Figure 2 shows the X-ray diffraction structure of the compound prepared in Preparation Example 5.

Claims (17)

하기 화학식 1 또는 화학식 2의 키랄성 리간드를 포함하는 에틸렌의 선택적 올리고머 제조용 크롬 착체 화합물.Chromium complex compound for the selective oligomer preparation of ethylene comprising a chiral ligand of formula (1) or (2). [화학식 1][Formula 1]
Figure 112009005732370-PAT00018
Figure 112009005732370-PAT00018
 [화학식 2][Formula 2]
Figure 112009005732370-PAT00019
Figure 112009005732370-PAT00019
 [상기 화학식 1 또는 화학식 2에서, R1, R2, R3, R4, R7, R8, R9 및 R10은 서로 독립적으로 하이드로카빌, 치환된 하이드로카빌, 헤테로하이드로카빌, 또는 치환된 헤테로하이드로카빌이고;[In Formula 1 or Formula 2, R 1 , R 2 , R 3 , R 4 , R 7 , R 8 , R 9 and R 10 are each independently hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted Heterohydrocarbyl; R5, R6, R11및 R12는 서로 독립적으로 하이드로카빌 또는 치환된 하이드로카빌이거나, R5과 R6, R11과 R12가 서로 하이드로카빌렌, 치환된 하이드로카빌렌, 헤테 로하이드로카빌렌 또는 치환된 헤테로하이드로카빌렌으로 결합될 수 있으며; X1 내지 X6는 각각 독립적으로 할로겐, -OR21및, -OCOR22 또는 -NR23R24이고, 상기 R21, R22, R23 또는 R24는 수소, 하이드로카빌 또는 헤테로하이드로카빌이며;R 5 , R 6 , R 11 and R 12 are each independently hydrocarbyl or substituted hydrocarbyl, or R 5 and R 6 , R 11 and R 12 may be bonded to each other with hydrocarbylene, substituted hydrocarbylene, heterohydrocarbylene or substituted heterohydrocarbylene; Each X 1 to X 6 is independently halogen, —OR 21 and —OCOR 22 or —NR 23 R 24 , wherein R 21 , R 22 , R 23 or R 24 is hydrogen, hydrocarbyl or heterohydrocarbyl; L은 하이드로카본 또는 헤테로하이드로카본이고;L is hydrocarbon or heterohydrocarbon; * 및 **는 키랄 탄소 위치로 서로 독립적으로 (S) 또는 (R) 배열을 의미한다.]* And ** refer to the (S) or (R) configuration independently of one another in the chiral carbon position.] 제 1항에 있어서, The method of claim 1, 하기 화학식 3 내지 화학식 8의 키랄성 리간드를 포함하는 에틸렌의 선택적 올리고머 제조용 크롬 착체 화합물.Chromium complex compound for the selective oligomer preparation of ethylene comprising a chiral ligand of formula 3 to formula 8. [화학식 3](3)
Figure 112009005732370-PAT00020
Figure 112009005732370-PAT00020
 [화학식 4][Formula 4]
Figure 112009005732370-PAT00021
Figure 112009005732370-PAT00021
 [화학식 5][Chemical Formula 5]
Figure 112009005732370-PAT00022
Figure 112009005732370-PAT00022
 [화학식 6][Formula 6]
Figure 112009005732370-PAT00023
Figure 112009005732370-PAT00023
 [화학식 7][Formula 7]
Figure 112009005732370-PAT00024
Figure 112009005732370-PAT00024
 [화학식 8][Formula 8]
Figure 112009005732370-PAT00025
Figure 112009005732370-PAT00025
 상기 화학식 2 내지 화학식 6의 치환체는 제 1항의 정의와 같다.Substituents of Formulas 2 to 6 are the same as defined in claim 1. 제 1항에 있어서,The method of claim 1, 키랄성 리간드의 치환체 R1, R2, R3, R4, R7, R8, R9 및 R10은 서로 독립적으로 (C6-C20)아릴, (C6-C20)아르(C1-C10)알킬, (C1-C10)알킬, (C2-C10)알케닐, (C2-C10)알키닐, (C3-C7)시클로알킬, 헤테로(C5-C20)아릴, 헤테로(C3-C7)시클로알킬 또는 -NR23R24이고, R23 또는 R24는 (C1-C10)알킬, (C6-C20)아릴이며, 상기 R1, R2, R3, R4, R7, R8, R9 및 R10의 치환체는 (C1-C10)알킬, (C1-C10)알콕시, (C6-C20)아릴옥시 및 할로겐으로부터 하나 이상이 더 치환될 수 있으며, R5, R6, R11 및 R12는 서로 독립적으로 (C6-C20)아릴, (C6-C20)아르(C1-C10)알킬, (C1-C10)알킬, (C2-C10)알케닐, (C2-C10)알키닐, (C3-C7)시클로알킬, 헤테로(C5-C20)아릴, 헤테로(C3-C7)시클로알킬, (C1-C10)알콕시, (C6-C20)아릴옥시, 아미노카보닐, 카보닐아미노, 디(C1-C10)알킬아미노, (C1-C10)알킬실릴 또는 (C6-C20)아릴실릴이며, 상기 R5, R6, R11 및 R12의 치환체는 (C1-C10)알킬, (C1-C10)알콕시, (C6-C20)아릴옥시 및 할로겐으로 치환될 수 있는 것을 특징으로 하는 에틸렌의 선택적 올리고머 제조용 크롬 착체 화합물.Substituents R 1 , R 2 , R 3 , R 4 , R 7 , R 8 , R 9 and R 10 of chiral ligands Independently (C6-C20) aryl, (C6-C20) ar (C1-C10) alkyl, (C1-C10) alkyl, (C2-C10) alkenyl, (C2-C10) alkynyl, (C3-C7) Cycloalkyl, hetero (C5-C20) aryl, hetero (C3-C7) cycloalkyl or -NR 23 R 24 , R 23 or R 24 is (C1-C10) alkyl, (C6-C20) aryl, wherein R Substituents of 1 , R 2 , R 3 , R 4 , R 7 , R 8 , R 9 and R 10 are one from (C1-C10) alkyl, (C1-C10) alkoxy, (C6-C20) aryloxy and halogen Or more may be further substituted, R 5 , R 6 , R 11 and R 12 independently of one another are (C6-C20) aryl, (C6-C20) ar (C1-C10) alkyl, (C1-C10) alkyl, (C2-C10) alkenyl, (C2-C10) alky Nyl, (C3-C7) cycloalkyl, hetero (C5-C20) aryl, hetero (C3-C7) cycloalkyl, (C1-C10) alkoxy, (C6-C20) aryloxy, aminocarbonyl, carbonylamino, Di (C1-C10) alkylamino, (C1-C10) alkylsilyl or (C6-C20) arylsilyl, wherein R 5 , R 6 , The substituents of R 11 and R 12 may be substituted with (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy, (C 6 -C 20) aryloxy and halogen. 제 3항에 있어서, The method of claim 3, wherein 상기 키랄성 리간드 중 R1, R2, R3, R4, R7, R8, R9 및 R10은 서로 독립적으로 페닐, 나프틸, 안트라센닐, 메시틸, 크실닐, 메틸, 에틸, 에틸레닐, n-프로필, i-프로필, 프로페닐, 프로피닐, n-부틸, t-부틸, 시클로프로필, 시클로부틸, 시클로펜틸, 시클로헥실, 4-메틸시클로헥실, 4-에틸시클로헥실, 4-이소프로필시클로헥실, 벤질, 톨릴, 크실릴, 4-메틸페닐, 4-에틸페닐, 4-이소프로필페닐, 4-t-부틸페닐, 4-메톡시페닐, 4-이소프로폭시페닐, 큐밀, 메톡시, 에톡시, 페녹시, 톨릴옥시, 디메틸아미노, 티오메틸, 트리메틸실닐, 디메틸히드라질, 2-메틸시클로헥실, 2-에틸 시클로헥실, 2-이소프로필시클로헥실, o-메틸페닐, o-에틸페닐, o-이소프로필페닐, o-t-부틸페닐, o-메톡시페닐, o-이소프로폭시페닐, 비페닐, 나프틸 및 안트라세닐로 이루어진 그룹으로부터 선택되며, R5, R6, R11 및 R12는 서로 독립적으로 메틸, 에틸, 에틸레닐, n-프로필, i-프로필, 프로페닐, 프로피닐, n-부틸, t-부틸, i-부틸, 페닐, 벤질, 톨릴, 크실릴, 메톡시, 에톡시, 페녹시, 메틸아미노, 디메틸아미노로부터 선택되는 것을 특징으로 하는 에틸렌의 선택적 올리고머 제조용 크롬 착체 화합물.Of the chiral ligands, R 1 , R 2 , R 3 , R 4 , R 7 , R 8 , R 9 and R 10 are mutually Independently phenyl, naphthyl, anthracenyl, mesityl, xylyl, methyl, ethyl, ethylenyl, n-propyl, i-propyl, propenyl, propynyl, n-butyl, t-butyl, cyclopropyl, cyclobutyl , Cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-isopropylcyclohexyl, benzyl, tolyl, xylyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4- t-butylphenyl, 4-methoxyphenyl, 4-isopropoxyphenyl, cumyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, thiomethyl, trimethylsilyl, dimethylhydrazyl, 2-methylcyclohexyl , 2-ethyl cyclohexyl, 2-isopropylcyclohexyl, o- methylphenyl, o- ethylphenyl, o -isopropylphenyl, ot -butylphenyl, o -methoxyphenyl, o- isopropoxyphenyl, biphenyl, Selected from the group consisting of naphthyl and anthracenyl, and R 5 , R 6 , R 11 and R 12 independently of one another are methyl, ethyl, ethylenyl, n-propyl, i-propyl, propenyl, propynyl, n-butyl, t-butyl, i-butyl, phenyl, benzyl, tolyl, xylyl , Methoxy, ethoxy, phenoxy, methylamino, dimethylamino chromium complex compound for the selective oligomer production of ethylene, characterized in that selected from. 제 4항에 있어서, The method of claim 4, wherein 상기 키랄성 리간드 중 R1, R2, R3, R4, R7, R8, R9 및 R10이 각각 독립적으로 페닐, 벤질, 나프틸, 4-메틸페닐, 4-에틸페닐, 4-이소프로필페닐, 4-t-부틸페닐, 4-메톡시페닐, 4-이소프로폭시페닐, 2-메틸시클로헥실, 2-에틸시클로헥실, 2-이소프로필시클로헥실, o-메틸페닐, o-에틸페닐, o-이소프로필페닐, o-t-부틸페닐, o-메톡시페닐 및 o-이소프로폭시페닐로 이루어진 그룹으로부터 선택되는 것을 특징으로 하는 에틸렌의 선택적 올리고머 제조용 크롬 착체 화합물.Of the chiral ligands, R 1 , R 2 , R 3 , R 4 , R 7 , R 8 , R 9 and R 10 are Each independently phenyl, benzyl, naphthyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-t-butylphenyl, 4-methoxyphenyl, 4-isopropoxyphenyl, 2-methylcyclohexyl From 2-ethylcyclohexyl, 2-isopropylcyclohexyl, o-methylphenyl, o-ethylphenyl, o-isopropylphenyl, ot-butylphenyl, o-methoxyphenyl and o-isopropoxyphenyl Chromium complex compound for selective oligomer preparation of ethylene, characterized in that it is selected. 제 1항에 있어서, The method of claim 1, 상기 키랄성 리간드 중 A는 (C1-C5)알킬렌, (C1-C5)알케닐렌로부터 선택되는 것을 특징으로 하는 에틸렌의 선택적 올리고머 제조용 크롬 착체 화합물.A in the chiral ligand A is selected from (C1-C5) alkylene, (C1-C5) alkenylene chromium complex compound for the selective oligomer production of ethylene. 제 1항에 있어서, The method of claim 1, 상기 화학식 1 또는 화학식 2의 키랄성 리간드는 (S, S)-, (R, R)- 또는 meso-(페닐)2P-CH(메틸)CH(메틸)-P(페닐)2, (S, S)-, (R, R)- 또는 meso-(4-메톡시페닐)2P-CH(메틸)CH(메틸)-P(4-메톡시페닐)2, (S, S)-, (R, R)- 또는 meso-(4-메틸페닐)2P-CH(메틸)CH(메틸)-P(4-메틸페닐)2, (S, S)-, (R, R)- 또는 meso-(4-에틸페닐)2P-CH(메틸)CH(메틸)-P(페닐)2, (S, S)-, (R, R)- 또는 meso-(4-에틸페닐)2P-CH(에틸)CH(메틸)-P(4-에틸페닐)2, (S, S)-, (R, R)- 또는 meso-(4-메톡시페닐)2P-CH(에틸)CH(메틸)-P(페닐)2, (S, S)-, (R, R)- 또는 meso-(4-에틸페닐)2P-CH(에틸)CH(에틸)-P(4-에틸페닐)2, (S, S)-, (R, R)- 또는 meso-(페닐)2P-CH(에틸)CH(에틸)-P(페닐)2, (S, S)-, (R, R)- 또는 meso-(페닐)2P-CH(이소프로필)CH(메틸)-P(페닐)2, (S, S)-, (R, R)- 또는 meso-(4-메톡시페닐)2P-CH(이소프로필)CH(메틸)-P(4-메톡시페닐)2, (S, S)-, (R, R)- 또는 meso-(4-에틸페닐)2P-CH(이소프로필)CH(메틸)-P(4-에틸페닐)2, (S, S)-, (R, R)- 또는 meso-(페닐)2P-CH(n-프로필)CH(메틸)-P(페닐)2, (S, S)-, (R, R)- 또는 meso-(4-메톡시페닐)2P-CH(n-프로필)CH(메틸)-P(4-메톡시페닐)2, (S, S)-, (R, R)- 또는 meso-4(4-에틸페닐)2P-CH(n-프로필)CH(메 틸)-P(4-에틸페닐)2, (S, S)-, (R, R)- 또는 meso-(페닐)2P-CH(이소프로필)CH(에틸)-P(페닐)2, (S, S)-, (R, R)- 또는 meso-(4-메톡시페닐)2P-CH(이소프로필)CH(에틸)-P(4-메톡시페닐)2, (S, S)-, (R, R)- 또는 meso-(4-에틸페닐)2P-CH(이소프로필)CH(에틸)-P(4-에틸페닐)2, (S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-1,2-디-(P(페닐)2)시클로헥산, (S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-1,2-디-(P(4-메톡시페닐)2)시클로헥산, (S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-1,2-디-(P(4-에틸페닐)2)시클로헥산, (S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-트랜스-1,2-디-(P(페닐)2)시클로펜탄, (S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-1,2-디-(P(4-메톡시페닐)2)시클로펜탄, (S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-1,2-디-(P(4-에틸페닐)2)시클로펜탄, (S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-3,4-디-(P(페닐)2)피롤, (S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-3,4-디-(P(4-메톡시페닐)2)피롤, (S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-3,4-디-(P(4-에틸페닐)2)피롤, (S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-3,4-디-(P(4-에틸페닐)2)이미다졸, (S, S)-, (R, R)- 또는 meso-(4-에틸페닐)2P-CH(디메틸아민)CH(디메틸아민)-P(4-에틸페닐)2, (S, S)-, (R, R)- 또는 meso-(3-메톡시페닐)2P-CH(메틸)CH(메틸)-P(3-메톡시페닐)2, (S, S)-, (R, R)- 또는 meso-(4-에톡시페닐)2P-CH(메틸)CH(메틸)-P(o-에톡시페닐)2, (S, S)-, (R, R)- 또는 meso-4-(디메틸아민페닐)2P-CH(메틸)CH(메틸)P(4-디메틸아민페닐)2, (S, S)-, (R, R)- 또는 meso-(4-에틸시클로헥실)2PCH(메틸)CH(메틸)P(4-에틸시클로헥실)2, (S, S)-, (R, R)- 또는 meso-(2-에틸페닐)2PCH(메틸)CH(메틸)P(2-에틸페닐)2, (S, S)-, (R, R)- 또는 meso-(2-이소프로필페닐)2PCH(메틸)CH(메틸)P(2-이소프로필페닐)2, (S, S)-, (R, R)- 또는 meso-(2-메틸페닐)2PCH(메틸)CH(메틸)P(2-메틸페닐)2, (S, S)-, (R, R)- 또는 meso-(2-에틸페닐)2PCH(메틸)CH(메틸)P(페닐)2, (S, S)-, (R, R)- 또는 meso-(2-에틸페닐)2PCH(에틸)CH(메틸)P(2-에틸페닐)2, (S, S)-, (R, R)- 또는 meso-(2-에틸페닐)2PCH(에틸)CH(에틸)P(2-에틸페닐)2, (S, S)-, (R, R)- 또는 meso-(2-에틸페닐)2PCH(이소프로필)CH(메틸)P(2-에틸페닐)2, (S, S)-, (R, R)- 또는 meso-(2-에틸페닐)2PCH(n-프로필)CH(메틸)P(2-에틸페닐)2, (S, S)-, (R, R)- 또는 meso-(2-에틸페닐)2PCH(이소프로필)CH(에틸)P(2-에틸페닐)2, (S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-1,2-디-(P(2-에틸페닐)2)시클로헥산, (S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-1,2-디-(P(2-에틸페닐)2)시클로펜탄, (S, S)-트렌 스, (R, R)-트랜스- 또는, meso-시스-3,4-디-(P(2-에틸페닐)2)피롤, (S, S)-트렌스, (R, R)-트랜스- 또는, meso-시스-3,4-디-(P(2-에틸페닐)2)이미다졸, (S, S)-, (R, R)- 또는 meso-(2-에틸페닐)2PCH(디메틸아민)CH(디메틸아민)P(2-에틸페닐)2, (S, S)-, (R, R)- 또는 meso-(2-메톡시페닐)2PCH(메틸)CH(메틸)P(2-메톡시페닐)2, (S, S)-, (R, R)- 또는 meso-(2-에톡시페닐)2PCH(메틸)CH(메틸)P(2-에톡시페닐)2, (S, S)-, (R, R)- 또는 meso-(2-디메틸아민페닐)2PCH(메틸)CH(메틸)P(2-디메틸아민페닐)2, 및 (S, S)-, (R, R)- 또는 meso-(2-에틸시클로헥실)2PCH(메틸)CH(메틸)P(2-에틸시클로헥실)2로부터 선택되는 것을 특징으로 하는 하기 화합물로부터 선택되는 것을 특징으로 하는 에틸렌의 선택적 올리고머 제조용 크롬 착체 화합물.The chiral ligand of Formula 1 or Formula 2 is (S, S)-, (R, R) -or meso- (phenyl) 2 P-CH (methyl) CH (methyl) -P (phenyl) 2 , (S, S)-, (R, R) -or meso- (4-methoxyphenyl) 2 P-CH (methyl) CH (methyl) -P (4-methoxyphenyl) 2 , (S, S)-, ( R, R) -or meso- (4-methylphenyl) 2 P-CH (methyl) CH (methyl) -P (4-methylphenyl) 2 , (S, S)-, (R, R) -or meso- ( 4-ethylphenyl) 2 P-CH (methyl) CH (methyl) -P (phenyl) 2 , (S, S)-, (R, R) -or meso- (4-ethylphenyl) 2 P-CH ( Ethyl) CH (methyl) -P (4-ethylphenyl) 2 , (S, S)-, (R, R) -or meso- (4-methoxyphenyl) 2 P-CH (ethyl) CH (methyl) -P (phenyl) 2 , (S, S)-, (R, R) -or meso- (4-ethylphenyl) 2 P-CH (ethyl) CH (ethyl) -P (4-ethylphenyl) 2 , (S, S)-, (R, R) -or meso- (phenyl) 2 P-CH (ethyl) CH (ethyl) -P (phenyl) 2 , (S, S)-, (R, R) -or meso- (phenyl) 2 P-CH (isopropyl) CH (methyl) -P (phenyl) 2 , (S, S)-, (R, R) -or meso- (4-methoxyphenyl) 2 P-CH (isopropyl) CH (Methyl) -P (4-methoxyphenyl) 2 , (S, S)-, (R, R) -or meso- (4-ethylphenyl) 2 P-CH (isopropyl) CH (methyl) -P (4-ethylphenyl) 2 , (S, S)-, (R, R) -or meso- (phenyl) 2 P-CH (n-propyl) CH (methyl) -P (phenyl) 2 , (S, S)-, (R, R) -or meso- (4-methoxyphenyl) 2 P-CH (n-propyl) CH (methyl) -P (4-methoxyphenyl) 2 , (S, S)- , (R, R) -or meso-4 (4-ethylphenyl) 2 P-CH (n-propyl) CH (methyl) -P (4-ethylphenyl) 2 , (S, S)-, (R , R) -or meso- (phenyl) 2 P-CH (isopropyl) CH (ethyl) -P (phenyl) 2 , (S, S)-, (R, R) -or meso- (4-methoxy phenyl) 2 P-CH (isopropyl) CH (ethyl) -P (4- methoxyphenyl) 2, (S, S) -, (R, R) - or meso- (4- ethyl Fe ) 2 P-CH (isopropyl) CH (ethyl) -P (4- ethylphenyl) 2, (S, S) - trans, (R, R) - trans - or, meso- cis-1,2- -(P (phenyl) 2 ) cyclohexane, (S, S) -trans , (R, R) -trans -or, meso-cis- 1,2-di- (P (4-methoxyphenyl) 2 ) Cyclohexane, (S, S) -trans , (R, R) -trans- or, meso-cis- 1,2-di- (P (4-ethylphenyl) 2 ) cyclohexane, (S, S)- Trans , (R, R) -trans- or, meso-cis-trans- 1,2-di- (P (phenyl) 2 ) cyclopentane, (S, S) -trans , (R, R) -trans- Or meso-cis- 1,2-di- (P (4-methoxyphenyl) 2 ) cyclopentane, (S, S) -trans , (R, R) -trans- or meso-cis- 1, 2-di- (P (4-ethylphenyl) 2 ) cyclopentane, (S, S) -trans , (R, R) -trans- or, meso-cis- 3,4-di- (P (phenyl) 2 ) pyrrole, (S, S) -trans , (R, R) -trans- or, meso-cis- 3,4-di- (P (4-methoxyphenyl) 2 ) pyrrole, (S, S) -Trans , (R, R) -trans- or, meso-cis- 3,4-di- (P (4-ethylphenyl) 2 ) pyrrole, (S, S) -trans , (R, R) -trans- or meso-cis- 3,4-di- (P (4-ethylphenyl) 2 ) imidazole, (S, S)-, (R, R) -or meso- ( 4-ethylphenyl) 2 P-CH (dimethylamine) CH (dimethylamine) -P (4-ethylphenyl) 2 , (S, S)-, (R, R) -or meso- (3-methoxyphenyl ) 2 P-CH (methyl) CH (methyl) -P (3-methoxyphenyl) 2 , (S, S)-, (R, R) -or meso- (4-ethoxyphenyl) 2 P-CH (Methyl) CH (methyl) -P (o-ethoxyphenyl) 2 , (S, S)-, (R, R) -or meso- 4- (dimethylaminephenyl) 2 P-CH (methyl) CH ( Methyl) P (4-dimethylaminephenyl) 2 , (S, S)-, (R, R) -or meso- (4-ethylcyclohexyl) 2 PCH (methyl) CH (methyl) P (4-ethylcyclo Hexyl) 2, (S, S)-, (R, R) -or meso- (2 - ethylphenyl) 2 PCH (methyl) CH (methyl) P (2 - ethylphenyl) 2 , (S, S)- , (R, R) -or meso- (2-isopropylphenyl) 2 PCH (methyl) CH (methyl) P (2-isopropylphenyl) 2 , (S, S)-, (R, R) -or meso- (2-methylphenyl) 2 PCH (methyl) CH (methyl) P (2-methylphenyl) 2 , (S, S)-, (R, R) -or meso- (2-ethylphenyl) 2 PCH (methyl ) CH (methyl) P (phenyl) 2 , (S , S)-, (R, R) -or meso- (2-ethylphenyl) 2 PCH (ethyl) CH (methyl) P (2-ethylphenyl) 2 , (S, S)-, (R, R) - or meso- (2- ethylphenyl) 2 PCH (ethyl) CH (ethyl) P (2- ethylphenyl) 2, (S, S) -, (R, R) - or meso- (2- ethylphenyl) 2 PCH (isopropyl) CH (methyl) P (2-ethylphenyl) 2 , (S, S)-, (R, R) -or meso- (2-ethylphenyl) 2 PCH (n-propyl) CH ( Methyl) P (2-ethylphenyl) 2 , (S, S)-, (R, R) -or meso- (2-ethylphenyl) 2 PCH (isopropyl) CH (ethyl) P (2-ethylphenyl) 2 , (S, S) -trans , (R, R) -trans- or, meso-cis- 1,2-di- (P (2-ethylphenyl) 2 ) cyclohexane, (S, S) -trans , (R, R) -trans -or, meso-cis- 1,2-di- (P (2-ethylphenyl) 2 ) cyclopentane, (S, S) -trans , (R, R) -trans Or, meso-cis- 3,4-di- (P (2-ethylphenyl) 2 ) pyrrole, (S, S) -trans , (R, R) -trans- or, meso-cis- 3,4 -Di- (P (2-ethylphenyl) 2 ) imidazole, (S, S)-, (R, R) -or meso- (2-ethylphenyl) 2 PCH (dimethylamine) CH (dimethylamine) P (2-ethylphenyl) 2 , (S, S)-, (R, R) -or meso- (2-methoxyphenyl) 2 PCH (methyl) CH (methyl) P (2-methoxyphenyl) 2 , (S, S)- , (R, R) -or meso- (2-ethoxyphenyl) 2 PCH (methyl) CH (methyl) P (2-ethoxyphenyl) 2 , (S, S)-, (R, R) -or meso- (2-dimethylaminephenyl) 2 PCH (methyl) CH (methyl) P (2-dimethylaminephenyl) 2 , and (S, S)-, (R, R) -or meso- (2-ethylcyclo Hexyl) 2 PCH (methyl) CH (methyl) P (2-ethylcyclohexyl) 2 Chromium complex compound for the selective oligomer preparation of ethylene, characterized in that it is selected from the following compounds. 제 1항에 있어서, The method of claim 1, X1, X2, X3, X4, X5 또는 X6는 Cl, Br, 아세토아세틸 및 2-에틸헥사노일기로부터 선택되는 것을 특징으로 하는 에틸렌의 선택적 올리고머 제조용 크롬 착체 화합물.X 1 , X 2 , X 3 , X 4 , X 5 or X 6 is selected from Cl, Br, acetoacetyl and 2-ethylhexanoyl groups. Chromium complex compounds for the production of selective oligomers of ethylene. 제 1항에 있어서, The method of claim 1, L은 테트라하이드로퓨란, 디에틸에테르, 톨루엔, 클로로벤젠, 디클로로벤젠, 아세틸아세톤 및 2-에틸헥사논으로부터 선택되는 것을 특징으로 하는 에틸렌의 선택적 올리고머 제조용 크롬 착체 화합물.L is selected from tetrahydrofuran, diethyl ether, toluene, chlorobenzene, dichlorobenzene, acetylacetone and 2-ethylhexanone chromium complex compound for the selective oligomer preparation of ethylene. 제 1항 내지 제 9항 중 어느 한 항에 따른 올리고머 제조용 크롬 착체 화합물과 조촉매를 포함하는 에틸렌의 선택적 올리고머 제조용 크롬 착체 촉매 조성물.A chromium complex catalyst composition for producing a selective oligomer of ethylene comprising a chromium complex compound for producing an oligomer and a promoter according to any one of claims 1 to 9. 제 10항에 있어서, The method of claim 10, 상기 조촉매는 유기 알루미늄 화합물, 유기 붕소 화합물, 유기염 또는 인 것을 특징으로 하는 에틸렌의 선택적 올리고머 제조용 크롬 착체 촉매 조성물.The promoter is a chromium complex catalyst composition for producing a selective oligomer of ethylene, characterized in that the organoaluminum compound, organoboron compound, organic salt or phosphate. 제 11항에 있어서, The method of claim 11, 상기 조촉매는 메틸알루미녹산(MAO), 개선된 메틸알루미녹산 (MMAO), 에틸알루미녹산(EAO), 트리메틸알루미늄(TMA), 트리에틸알루미늄(TEA), 트리이소부틸알루미늄(TIBA), 트리-n-옥틸알루미늄, 메틸알루미늄 디클로라이드, 에틸알루미늄 디클로라이드, 디메틸알루미늄 클로라이드, 디에틸알루미늄 클로라이드, 알루미늄 이소프로폭사이드, 에틸알루미늄 세스퀴클로라이드 또는 메틸알루미늄 세스퀴클로라이드인 것을 특징으로 하는 에틸렌의 선택적 올리고머 제조용 크롬 착체 촉매 조성물.The promoters are methylaluminoxane (MAO), improved methylaluminoxane (MMAO), ethylaluminoxane (EAO), trimethylaluminum (TMA), triethylaluminum (TEA), triisobutylaluminum (TIBA), tri- Selective oligomers of ethylene characterized by n-octylaluminum, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride, diethylaluminum chloride, aluminum isopropoxide, ethylaluminum sesquichloride or methylaluminum sesquichloride Chromium complex catalyst composition for preparation. 제 11항에 있어서, The method of claim 11, 에틸렌의 선택적 올리고머 제조용 크롬 착체와 알루미녹산의 비율은 알루미늄:크롬 몰비로 기준으로 1:1 내지 10,000:1인 것을 특징으로 하는 에틸렌의 선택적 올리고머 제조용 크롬 착체 촉매 조성물.The chromium complex catalyst composition for selective oligomer production of ethylene is characterized in that the ratio of the chromium complex and aluminoxane for the production of ethylene is 1: 1 to 10,000: 1 based on aluminum: chromium molar ratio. 제 1항 내지 제 10항 중 어느 한 항에 따른 에틸렌의 선택적 올리고머 제조용 크롬 착체 화합물을 이용하여 에틸렌으로부터 선택적으로 1-헥센을 제조하는 방법.A process for selectively producing 1-hexene from ethylene using chromium complex compounds for the selective oligomer preparation of ethylene according to any one of claims 1 to 10. 제 1항 내지 제 10항 중 어느 한 항에 따른 에틸렌의 선택적 올리고머 제조용 크롬 착체 화합물을 이용하여 에틸렌으로부터 선택적으로 1-옥텐을 제조하는 방법.A process for selectively producing 1-octene from ethylene using a chromium complex compound for the selective oligomer preparation of ethylene according to any one of claims 1 to 10. 제 14항에 있어서, 15. The method of claim 14, 반응용매는 디에틸에테르, 톨루엔, 클로로벤젠, 디클로로벤젠 또는 아세틸아세톤, 또는 이들의 혼합물인 것을 특징으로 하는 1-헥센을 제조하는 방법.The reaction solvent is diethyl ether, toluene, chlorobenzene, dichlorobenzene or acetylacetone, or a mixture thereof. 제 15항에 있어서, The method of claim 15, 반응용매는 디에틸에테르, 톨루엔, 클로로벤젠, 디클로로벤젠 또는 아세틸아세톤, 또는 이들의 혼합물인 것을 특징으로 하는 1-옥텐을 제조하는 방법.The reaction solvent is diethyl ether, toluene, chlorobenzene, dichlorobenzene or acetylacetone, or a mixture thereof.
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CN109906229B (en) * 2016-11-02 2022-07-29 亚州大学校产学协力团 Chromium compounds, catalytic systems using the same and process for preparing ethylene oligomers

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