TWI667246B - Novel transition metal compound, catalyst composition comprising the same, and method for preparing ethylene homopolymer or copolymer of ethylene and a-olefin using the same - Google Patents

Novel transition metal compound, catalyst composition comprising the same, and method for preparing ethylene homopolymer or copolymer of ethylene and a-olefin using the same Download PDF

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TWI667246B
TWI667246B TW107100550A TW107100550A TWI667246B TW I667246 B TWI667246 B TW I667246B TW 107100550 A TW107100550 A TW 107100550A TW 107100550 A TW107100550 A TW 107100550A TW I667246 B TWI667246 B TW I667246B
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ethylene
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韓龍圭
吳娟鈺
金明一
咸炯宅
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新加坡商沙特基礎工業愛思開奈克斯林恩私人有限公司
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Abstract

提供一種基於環戊[a]萘基的新穎過渡金屬化合物、包含其及具有用於製備乙烯均聚物或乙烯與至少一種α-烯烴的共聚物的高催化活性的過渡金屬催化劑組合物、以及使用其製備乙烯均聚物或乙烯與α-烯烴的共聚物的方法。根據本發明之茂金屬化合物和包含其的催化劑組合物可提供催化劑的高熱穩定性以即使在高溫下也能維持高催化活性、與其它烯烴具有良好的共聚反應性、以及以高產率製備高分子量聚合物。 Provided is a novel transition metal compound based on cyclopenta[a]naphthyl, a transition metal catalyst composition comprising the same and having high catalytic activity for preparing an ethylene homopolymer or a copolymer of ethylene and at least one α -olefin, and A process for preparing an ethylene homopolymer or a copolymer of ethylene and an α -olefin is used. The metallocene compound according to the present invention and a catalyst composition comprising the same can provide high thermal stability of the catalyst to maintain high catalytic activity even at high temperatures, good copolymerization reactivity with other olefins, and high molecular weight production in high yield. polymer.

Description

新穎過渡金屬化合物、包含該化合物的催化劑組合物、以及使用該化合物製備乙烯均聚物或乙烯與 α -烯烴的共聚物的方法Novel transition metal compound, catalyst composition comprising the same, and method for preparing an ethylene homopolymer or a copolymer of ethylene and an α-olefin using the compound

本發明關於一種新穎過渡金屬化合物、包含該化合物及具有用於製備乙烯均聚物或乙烯與至少一種α-烯烴的共聚物的高催化活性的過渡金屬催化劑組合物、以及使用該化合物製備乙烯均聚物或乙烯與α-烯烴的共聚物的方法。 The present invention relates to a novel transition metal compound, a transition metal catalyst composition comprising the same and having a high catalytic activity for preparing an ethylene homopolymer or a copolymer of ethylene and at least one α -olefin, and the use of the compound for preparing ethylene A method of polymer or a copolymer of ethylene and an α -olefin.

通常,由鈦或釩化合物的主催化劑組分和烷基鋁化合物的共催化劑組分組成的所謂齊格勒-納塔(Ziegler-Natta)催化劑系統一般被用於製備乙烯均聚物或乙烯與α-烯烴的共聚物。齊格勒-納塔催化劑系統對乙烯聚合反應呈現高活性。然而,其缺點在於,由於不均勻的催化活化點,所 得聚合物一般的分子量分布廣,特別是乙烯與α-烯烴的共聚物的組成分布不均勻。 Generally, a so-called Ziegler-Natta catalyst system consisting of a main catalyst component of a titanium or vanadium compound and a cocatalyst component of an alkyl aluminum compound is generally used to prepare an ethylene homopolymer or ethylene. a copolymer of an α -olefin. The Ziegler-Natta catalyst system exhibits high activity for ethylene polymerization. However, it is disadvantageous in that the polymer obtained generally has a broad molecular weight distribution due to the uneven catalytic activation point, and in particular, the composition distribution of the copolymer of ethylene and the α -olefin is not uniform.

由於由週期表中第4族過渡金屬(諸如鈦、鋯、鉿等)的茂金屬化合物和作為共催化劑的甲基鋁氧烷組成的茂金屬催化劑系統是具有單一型態催化活化點的均相催化劑,其特徵在於,該茂金屬催化劑系統能夠製備出與現存齊格勒-納塔催化劑系統相比具有更窄分子量分布和均勻組成分布的聚乙烯類。例如,歐洲專利公開第320,762號、第372,632號或日本專利公開公報第S63-092621號、第H02-84405號或第H03-2347號報導可以藉由使用共催化劑,甲基鋁氧烷來活化茂金屬化合物,諸如Cp2TiCl2、Cp2ZrCl2、Cp2ZrMeCl、Cp2ZrMe2、乙烯(IndH4)2ZrCl2等,從而以高活性聚合乙烯來製備其分子量分布(Mw/Mn)範圍為1.5至2.0的聚乙烯類。然而,在催化劑系統中難以獲得高分子量聚合物。特別是,已知當應用於在120℃或更高的高溫下進行的溶液聚合方法時,聚合活性會迅速降低並且β-脫氫反應佔優勢,因此不適合用於製備其中重量平均分子量(Mw)為100,000或更高的高分子量聚合物。 Since the metallocene catalyst system consisting of a metallocene compound of a Group 4 transition metal (such as titanium, zirconium, hafnium, etc.) and a methylaluminoxane as a cocatalyst is a homogeneous phase having a single type catalytic activation point Catalyst characterized in that the metallocene catalyst system is capable of producing polyethylenes having a narrower molecular weight distribution and a uniform composition distribution than existing Ziegler-Natta catalyst systems. For example, European Patent Publication No. 320,762, No. 372,632, or Japanese Patent Laid-Open Publication No. S63-092621, No. H02-84405 or No. H03-2347 can be used to activate molybdenum by using a cocatalyst, methylaluminoxane. Metal compounds such as Cp 2 TiCl 2 , Cp 2 ZrCl 2 , Cp 2 ZrMeCl, Cp 2 ZrMe 2 , ethylene (IndH 4 ) 2 ZrCl 2 , etc., thereby preparing a molecular weight distribution (Mw/Mn) range by polymerizing ethylene with high activity It is a polyethylene of 1.5 to 2.0. However, it is difficult to obtain a high molecular weight polymer in a catalyst system. In particular, it is known that when applied to a solution polymerization method carried out at a high temperature of 120 ° C or higher, the polymerization activity is rapidly lowered and the β-dehydrogenation reaction is dominant, and thus it is not suitable for preparation of a weight average molecular weight (Mw) therein. A high molecular weight polymer of 100,000 or higher.

同時,作為在溶液聚合條件下能夠藉由乙烯均聚反應或乙烯與α-烯烴的共聚反應來製備具有高催化活性和高分子量的聚合物的催化劑,已報導了其中過渡金屬以環狀鏈結的所謂的幾何構形受限非茂金屬系催化劑(所謂的單 一活化點催化劑)。歐洲專利第0416815號和第0420436號提出其中醯胺基以環狀鏈結到一個環戊二烯配位基的實例。歐洲專利第0842939號公開其中作為電子供體化合物的酚系(phenol-based)配位基以環狀與環戊二烯配位基鏈結的催化劑的實例。在幾何構形受限催化劑中,由於催化劑本身降低的空間位阻效應,與高α-烯烴的反應性顯著地改善,但是在商業用途中仍存在許多困難。因此,考慮經濟可行性,包括優異的高溫活性、與高級α-烯烴的優異反應性和能製備高分子量聚合物的能力等,重要的是確保具有作為商業化催化劑所需性質的更具競爭性的催化劑系統。 Meanwhile, as a catalyst capable of preparing a polymer having high catalytic activity and high molecular weight by a homopolymerization reaction of ethylene or a copolymerization reaction of ethylene and an α -olefin under solution polymerization conditions, a transition chain of a transition metal has been reported. The so-called geometric configuration is limited to non-metallocene catalysts (so called single activation point catalysts). European Patent Nos. 0416815 and 0420436 propose examples in which a guanamine group is cyclically linked to a cyclopentadienyl ligand. European Patent No. 0842939 discloses an example of a catalyst in which a phenol-based ligand as an electron donor compound is cyclically bonded to a cyclopentadienyl ligand. In the geometry-constrained catalyst, the reactivity with high alpha -olefins is significantly improved due to the reduced steric hindrance effect of the catalyst itself, but there are still many difficulties in commercial use. Therefore, considering economic feasibility, including excellent high temperature activity, excellent reactivity with higher alpha olefins, and ability to produce high molecular weight polymers, it is important to ensure more competitive properties as a commercial catalyst. Catalyst system.

[相關先前技術文獻] [Related prior art literature]

[專利文獻] [Patent Literature]

專利文獻1:歐洲專利公開第320,762號(1989年6月21日)。 Patent Document 1: European Patent Publication No. 320,762 (June 21, 1989).

專利文獻2:歐洲專利公開第372,632號(1990年6月13日)。 Patent Document 2: European Patent Publication No. 372,632 (June 13, 1990).

專利文獻3:日本專利特許公開公報第S63-092621號(1988年4月23日)。 Patent Document 3: Japanese Patent Laid-Open Publication No. S63-092621 (April 23, 1988).

專利文獻4:日本專利特許公開公報第H02-84405號(1990年3月26日)。 Patent Document 4: Japanese Patent Laid-Open Publication No. H02-84405 (March 26, 1990).

專利文獻5:日本專利特許公開公報第H03-2347號(1991年1月8日)。 Patent Document 5: Japanese Patent Laid-Open Publication No. H03-2347 (January 8, 1991).

專利文獻6:歐洲專利第0416815號(1991年3月13 日)。 Patent Document 6: European Patent No. 0416815 (March 13, 1991).

專利文獻7:歐洲專利第0420436號(1991年4月3日)。 Patent Document 7: European Patent No. 0420436 (April 3, 1991).

專利文獻8:歐洲專利第0842939號(1998年5月20日)。 Patent Document 8: European Patent No. 0842939 (May 20, 1998).

為了克服相關技術的問題,本案發明人進行了廣泛的研究,並且發現一種具有其中在週期表中第4族的過渡金屬作為中心金屬的結構的過渡金屬化合物,其係透過其中複數個苯環稠合到作為具有剛性平面結構及包含大量和廣泛地非定域電子的配位基的環戊二烯環來鏈結;以及能夠容易地導入經芳基或雜芳基(其中有用於改善溶解性和性能的取代基)取代的苯氧基,在乙烯和烯烴的聚合反應中呈現優異的催化活性。基於此發現,本案發明人發展出能夠在高溫下進行的溶液聚合過程中製備具有高活性的高分子量乙烯均聚物或乙烯與α-烯烴的共聚物的催化劑,並且完成本發明。 In order to overcome the problems of the related art, the inventors of the present invention conducted extensive research and found a transition metal compound having a structure in which a transition metal of Group 4 in the periodic table is a central metal, through which a plurality of benzene rings are thick. a cyclopentadiene ring as a ligand having a rigid planar structure and containing a large number of and a wide range of delocalized electrons; and an easy introduction of an aryl or heteroaryl group (which is useful for improving solubility) And a substituted phenoxy group, which exhibits excellent catalytic activity in the polymerization of ethylene and an olefin. Based on this finding, the inventors of the present invention have developed a catalyst capable of preparing a high-activity high molecular weight ethylene homopolymer or a copolymer of ethylene and an α -olefin in a solution polymerization process which is carried out at a high temperature, and completed the present invention.

本發明之一實施例旨在提供一種有用於作為製備乙烯均聚物或乙烯與α-烯烴的共聚物的催化劑的過渡金屬化合物、以及包含該過渡金屬化合物的催化劑組合物。 An embodiment of the present invention is directed to a transition metal compound useful as a catalyst for preparing an ethylene homopolymer or a copolymer of ethylene and an α -olefin, and a catalyst composition comprising the transition metal compound.

本發明之另一實施例考慮到商業態樣旨在提供一種使 用包含過渡金屬化合物的催化劑組合物來經濟地製備乙烯均聚物或乙烯與α-烯烴的共聚物的方法。 Another embodiment of the present invention contemplates a commercial aspect intended to provide a process for economically preparing an ethylene homopolymer or a copolymer of ethylene and an alpha -olefin using a catalyst composition comprising a transition metal compound.

本發明之再一實施例考慮到商業態樣旨在提供一種具有簡單合成路徑以能非常經濟地合成及在烯烴聚合反應中具有高活性的單一活化點催化劑、以及使用催化劑組分來經濟地製備具有各種物理性質的乙烯均聚物或乙烯與α-烯烴的共聚物的聚合方法。 Still another embodiment of the present invention contemplates that the commercial aspect is intended to provide a single activation point catalyst having a simple synthesis route for very economical synthesis and high activity in olefin polymerization, and economical preparation using a catalyst component. A method of polymerizing an ethylene homopolymer having various physical properties or a copolymer of ethylene and an α -olefin.

在一個一般態樣中,提供一種由以下化學式1表示的基於環戊[a]萘基的過渡金屬化合物。更具體地,該過渡金屬化合物可具有其中在週期表中第4族的過渡金屬作為中心金屬的結構,其係透過具有剛性平面結構及包含大量和廣泛地非定域電子的環戊[a]萘基來鏈結;以及能夠容易地導入經芳基或雜芳基(其中有用於改善溶解性和性能的取代基)取代的苯氧基,其中該環戊[a]萘基和該苯氧基係透過矽基鏈結。 In a general aspect, a transition metal compound based on cyclopenta[a]naphthyl group represented by the following Chemical Formula 1 is provided. More specifically, the transition metal compound may have a structure in which a transition metal of Group 4 in the periodic table is a central metal, which is transmitted through a cyclopentane having a rigid planar structure and containing a large amount and a wide range of non-localized electrons [a] a naphthyl linkage; and a phenoxy group which can be easily substituted with an aryl or heteroaryl group having a substituent for improving solubility and properties, wherein the cyclopenta[a]naphthyl group and the phenoxy group The base is transmitted through a thiol chain.

[化學式1] [Chemical Formula 1]

在化學式1中,M是週期表中第4族的過渡金屬;R1至R3各自獨立為氫、(C1-C20)烷基、(C6-C20)芳基、(C3-C20)環烷基、鹵素、(C2-C20)烯基、(C3-C20)雜芳基、(C3-C20)雜環烷基、-ORa1、-SRa2、-NRa3Ra4或-PRa5Ra6,並且R2和R3可以透過具有或不具有芳香環的(C3-C7)伸烷基(alkylene)或(C3-C7)伸烯基鏈結以形成稠合環;R4和R5各自獨立為(C1-C20)烷基、鹵(C1-C20)烷基、(C3-C20)環烷基、(C6-C20)芳基、(C1-C20)烷基(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C3-C20)雜芳基、-ORa1、-SRa2、-NRa3Ra4或-PRa5Ra6,或者R4和R5可以透過(C4-C7)伸烷基鏈結以形成環;R6至R8各自獨立為氫、(C1-C20)烷基、鹵(C1-C20)烷基、鹵素、(C6-C20)芳基、(C3-C20)環烷基、(C2-C20)烯基、(C3-C20)雜芳基、(C1-C20)雜環烷基、-ORa1、-SRa2、 -NRa3Ra4或-PRa5Ra6,或者R6至R8可以透過具有或不具有芳香環的(C4-C7)伸烯基與相鄰取代基鏈結以形成稠合環;Ar1為(C6-C20)芳基或(C3-C20)雜芳基,且Ar1的芳基或雜芳基可進一步經選自氫、(C1-C20)烷基、鹵(C1-C20)烷基、(C6-C20)芳基、(C1-C20)烷基(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、-ORa1、-SRa2、-NRa3Ra4和-PRa5Ra6組成之群組中的至少一個所取代;Ra1至Ra6各自獨立為(C1-C20)烷基或(C6-C20)芳基;R1至R3和R6至R8的烷基、芳基、環烷基、雜芳基或雜環烷基以及Ra1至Ra6的烷基或芳基可進一步經選自鹵素、(C1-C20)烷基、鹵(C1-C20)烷基、(C1-C20)烷氧基、(C6-C20)芳基、(C6-C20)芳氧基、硝基、氰基、-OSiRb1Rb2Rb3、-SRb4、-NRb5Rb6和-PRb7Rb8組成之群組中的至少一個所取代;Rb1至Rb8各自獨立為(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C1-C20)烷基(C6-C20)芳基或(C3-C20)環烷基;X1和X2各自獨立為氫、(C1-C20)烷基、(C3-C20)環烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、((C1-C20) 烷基(C6-C20)芳基)(C1-C20)烷基、(C1-C20)烷氧基、(C6-C20)芳氧基、(C1-C20)烷基(C6-C20)芳氧基、(C1-C20)烷氧基(C6-C20)芳氧基、-OSiRaRbRc、-SRd、-NReRf、-PRgRh或(C1-C20)亞烷基;Ra至Rd各自獨立為(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C1-C20)烷基(C6-C20)芳基或(C3-C20)環烷基;Re至Rh各自獨立為(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C1-C20)烷基(C6-C20)芳基、(C3-C20)環烷基、三(C1-C20)烷基矽基或三(C6-C20)芳基矽基;其限制條件為,當X1和X2中之一個是(C1-C50)亞烷基時,另一個則忽略;以及該雜芳基和該雜環烷基包括至少一個選自N、O和S的雜原子。 In Chemical Formula 1, M is a transition metal of Group 4 of the periodic table; R 1 to R 3 are each independently hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C3-C20) naphthenic , halogen, (C2-C20) alkenyl, (C3-C20)heteroaryl, (C3-C20)heterocycloalkyl, -OR a1 , -SR a2 , -NR a3 R a4 or -PR a5 R a6 And R 2 and R 3 may be through a (C3-C7)alkylene or (C3-C7)alkylene chain with or without an aromatic ring to form a fused ring; each of R 4 and R 5 Independently (C1-C20)alkyl, halo(C1-C20)alkyl, (C3-C20)cycloalkyl, (C6-C20)aryl, (C1-C20)alkyl (C6-C20) aryl , (C6-C20) aryl (C1-C20) alkyl, (C3-C20)heteroaryl, -OR a1 , -SR a2 , -NR a3 R a4 or -PR a5 R a6 , or R 4 and R 5 can be through (C4-C7) alkyl chain to form a ring; R 6 to R 8 are each independently hydrogen, (C1-C20) alkyl, halogen (C1-C20) alkyl, halogen, (C6-C20 Aryl, (C3-C20)cycloalkyl, (C2-C20)alkenyl, (C3-C20)heteroaryl, (C1-C20)heterocycloalkyl, -OR a1 , -SR a2 , -NR a3 R a4 or -PR a5 R a6, or R 6 to R 8 groups may be substituted via (C4-C7) alkenylene with or without an adjacent group having an aromatic ring Junction to form a fused ring; Ar 1 is (C6-C20) aryl or (C3-C20) heteroaryl, and Ar is an aryl group or a heteroaryl group may be further selected from hydrogen, (C1-C20) alkoxy , halo(C1-C20)alkyl, (C6-C20)aryl, (C1-C20)alkyl(C6-C20)aryl, (C6-C20)aryl(C1-C20)alkyl,- At least one of the groups consisting of OR a1 , -SR a2 , -NR a3 R a4 and -PR a5 R a6 is substituted; R a1 to R a6 are each independently (C1-C20)alkyl or (C6-C20) An aryl group; an alkyl group, an aryl group, a cycloalkyl group, a heteroaryl group or a heterocycloalkyl group of R 1 to R 3 and R 6 to R 8 and an alkyl group or an aryl group of R a1 to R a6 may be further selected from the group consisting of Halogen, (C1-C20)alkyl, halo(C1-C20)alkyl, (C1-C20)alkoxy, (C6-C20)aryl, (C6-C20)aryloxy, nitro, cyano , at least one of the group consisting of -OSiR b1 R b2 R b3 , -SR b4 , -NR b5 R b6 and -PR b7 R b8 is substituted; R b1 to R b8 are each independently (C1-C20) alkyl , (C6-C20) aryl, (C6-C20) aryl (C1-C20) alkyl, (C1-C20) alkyl (C6-C20) aryl or (C3-C20) cycloalkyl; X 1 and X 2 are each independently hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C20) aryl, (C6-C20) aryl (C1-C20) alkoxy ((C1-C20) alkyl (C6-C20) aryl) (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryloxy, (C1-C20) alkyl (C6-C20) aryloxy, (C1-C20) alkoxy (C6-C20) aryloxy, -OSiR a R b R c , -SR d , -NR e R f , -PR g R h or (C1-C20)alkylene; R a to R d are each independently (C1-C20)alkyl, (C6-C20)aryl, (C6-C20)aryl(C1-C20)alkyl, (C1 -C20)alkyl (C6-C20) aryl or (C3-C20)cycloalkyl; R e to R h are each independently (C1-C20)alkyl, (C6-C20) aryl, (C6-C20 An aryl (C1-C20) alkyl group, a (C1-C20) alkyl (C6-C20) aryl group, a (C3-C20) cycloalkyl group, a tri(C1-C20)alkyl fluorenyl group or a tris(C6- C20) an aryl fluorenyl group; the restriction is that when one of X 1 and X 2 is a (C1-C50) alkylene group, the other is neglected; and the heteroaryl group and the heterocycloalkyl group include at least A hetero atom selected from N, O and S.

在另一個一般態樣中,提供一種用於製備乙烯均聚物或乙烯與α-烯烴的共聚物的過渡金屬催化劑組合物,其包括由化學式1表示的過渡金屬化合物;以及選自鋁化合物、硼化合物或其混合物的共催化劑。 In another general aspect, a transition metal catalyst composition for preparing an ethylene homopolymer or a copolymer of ethylene and an α -olefin, comprising a transition metal compound represented by Chemical Formula 1; and an aluminum compound, A cocatalyst of a boron compound or a mixture thereof.

在又一個一般態樣中,提供一種使用該催化劑組合物製備乙烯均聚物或乙烯與α-烯烴的共聚物的方法。 In yet another general aspect, a method of making an ethylene homopolymer or a copolymer of ethylene and an alpha -olefin using the catalyst composition is provided.

根據本發明之過渡金屬化合物或包含該過渡金屬化合物的催化劑組合物可以具有簡單的合成過程,以便能夠藉由經濟的方法以高產率容易地製備,並且進一步可以提供催化劑的高熱穩定性,從而能夠在高溫下維持高催化活性,與其它烯烴具有良好的共聚反應性,並能以高產率製備高分子量聚合物,因此商業用途高於先前已知的茂金屬和非茂金屬單一活化點催化劑。因此,根據本發明之過渡金屬和包含其的催化劑組合物可以有效地用於製備具有各種物理性質的乙烯均聚物或乙烯與α-烯烴的共聚物。 The transition metal compound or the catalyst composition comprising the transition metal compound according to the present invention may have a simple synthesis process so as to be easily produced in a high yield by an economical method, and further capable of providing high thermal stability of the catalyst, thereby enabling It maintains high catalytic activity at high temperatures, has good copolymerization reactivity with other olefins, and can produce high molecular weight polymers in high yield, and thus is commercially used higher than previously known metallocene and nonmetallocene single activation point catalysts. Therefore, the transition metal according to the present invention and the catalyst composition comprising the same can be effectively used for preparing an ethylene homopolymer having various physical properties or a copolymer of ethylene and an α -olefin.

在下文中,將更詳細地描述本發明。在此,除非另外定義的技術和科學術語,否則它們具有本發明所屬技術領域中具有通常知識者所理解的含義。在以下的描述中省略可能使本發明的主旨不清楚的已知功能和組分。 Hereinafter, the present invention will be described in more detail. Here, unless otherwise defined in the technical and scientific terms, they have the meaning understood by those of ordinary skill in the art to which the invention pertains. Known functions and components that may obscure the gist of the present invention are omitted in the following description.

根據本發明之示例性實施例的過渡金屬化合物是基於 由以下化學式1表示的環戊[a]萘基的過渡金屬化合物,並且可具有其中在週期表中第4族的過渡金屬作為中心金屬的結構,其係藉由具有剛性平面結構及包含大量和廣泛地非定域電子的環戊[a]萘基來鏈結;以及能夠容易地導入經芳基或雜芳基(其中有用於改善溶解性和性能的取代基)取代的苯氧基,其中該環戊[a]萘基和該苯氧基係透過矽基鏈結,從而提供有利於高效獲得高分子量乙烯聚合物的結構優點。 The transition metal compound according to an exemplary embodiment of the present invention is a transition metal compound based on a cyclopenta[a]naphthyl group represented by the following Chemical Formula 1, and may have a transition metal of Group 4 in the periodic table as a central metal. a structure which is linked by a cyclopenta[a]naphthyl group having a rigid planar structure and containing a large amount and a wide range of delocalized electrons; and an aryl or heteroaryl group which can be easily introduced (which is used for improving dissolution) Substituted and substituted phenoxy groups wherein the cyclopenta[a]naphthyl group and the phenoxy group are passed through a fluorenyl linkage to provide structural advantages that facilitate efficient high molecular weight ethylene polymers.

在化學式1中,M是週期表中第4族的過渡金屬;R1至R3各自獨立為氫、(C1-C20)烷基、(C6-C20)芳基、(C3-C20)環烷基、鹵素、(C2-C20)烯基、(C3-C20)雜芳基、(C3-C20)雜環烷基、-ORa1、-SRa2、-NRa3Ra4或-PRa5Ra6,並且R2和R3可以透過具有或不具有芳香環的(C3-C7)伸烷 基或(C3-C7)伸烯基鏈結以形成稠合環;R4和R5各自獨立為(C1-C20)烷基、鹵(C1-C20)烷基、(C3-C20)環烷基、(C6-C20)芳基、(C1-C20)烷基(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C3-C20)雜芳基、-ORa1、-SRa2、-NRa3Ra4或-PRa5Ra6,或者R4和R5可以透過(C4-C7)伸烷基鏈結以形成環;R6至R8各自獨立為氫、(C1-C20)烷基、鹵(C1-C20)烷基、鹵素、(C6-C20)芳基、(C3-C20)環烷基、(C2-C20)烯基、(C3-C20)雜芳基、(C1-C20)雜環烷基、-ORa1、-SRa2、-NRa3Ra4或-PRa5Ra6,或者R6至R8可以透過具有或不具有芳香環的(C4-C7)伸烯基與相鄰取代基鏈結以形成稠合環;Ar1為(C6-C20)芳基或(C3-C20)雜芳基,且Ar1的芳基或雜芳基可進一步經選自氫、(C1-C20)烷基、鹵(C1-C20)烷基、(C6-C20)芳基、(C1-C20)烷基(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、-ORa1、-SRa2、-NRa3Ra4和-PRa5Ra6組成之群組中的至少一個所取代;Ra1至Ra6各自獨立為(C1-C20)烷基或(C6-C20)芳基;R1至R3和R6至R8的烷基、芳基、環烷基、雜芳基或雜環烷基以及Ra1至Ra6的烷基或芳基可進一步經選自鹵 素、(C1-C20)烷基、鹵(C1-C20)烷基、(C1-C20)烷氧基、(C6-C20)芳基、(C6-C20)芳氧基、硝基、氰基、-OSiRb1Rb2Rb3、-SRb4、-NRb5Rb6和-PRb7Rb8組成之群組中的至少一個所取代;Rb1至Rb8各自獨立為(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C1-C20)烷基(C6-C20)芳基或(C3-C20)環烷基;X1和X2各自獨立為氫、(C1-C20)烷基、(C3-C20)環烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、((C1-C20)烷基(C6-C20)芳基)(C1-C20)烷基、(C1-C20)烷氧基、(C6-C20)芳氧基、(C1-C20)烷基(C6-C20)芳氧基、(C1-C20)烷氧基(C6-C20)芳氧基、-OSiRaRbRc、-SRd、-NReRf、-PRgRh或(C1-C20)亞烷基;Ra至Rd各自獨立為(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C1-C20)烷基(C6-C20)芳基或(C3-C20)環烷基;Re至Rh各自獨立為(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C1-C20)烷基(C6-C20)芳基、(C3-C20)環烷基、三(C1-C20)烷基矽基或三(C6-C20)芳基矽基; 其限制條件為,當X1和X2中之一個是(C1-C50)亞烷基時,另一個則忽略;以及該雜芳基和該雜環烷基包括至少一個選自N、O和S的雜原子。 In Chemical Formula 1, M is a transition metal of Group 4 of the periodic table; R 1 to R 3 are each independently hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C3-C20) naphthenic , halogen, (C2-C20) alkenyl, (C3-C20)heteroaryl, (C3-C20)heterocycloalkyl, -OR a1 , -SR a2 , -NR a3 R a4 or -PR a5 R a6 And R 2 and R 3 may be through a (C3-C7)alkylene group or a (C3-C7)alkylene chain with or without an aromatic ring to form a fused ring; R 4 and R 5 are each independently ( C1-C20)alkyl, halo(C1-C20)alkyl, (C3-C20)cycloalkyl, (C6-C20)aryl, (C1-C20)alkyl(C6-C20)aryl, (C6 -C20) aryl (C1-C20) alkyl, (C3-C20)heteroaryl, -OR a1 , -SR a2 , -NR a3 R a4 or -PR a5 R a6 , or R 4 and R 5 are permeabilizable (C4-C7) alkyl chain to form a ring; R 6 to R 8 are each independently hydrogen, (C1-C20) alkyl, halo (C1-C20) alkyl, halogen, (C6-C20) aryl (C3-C20)cycloalkyl, (C2-C20)alkenyl, (C3-C20)heteroaryl, (C1-C20)heterocycloalkyl, -OR a1 , -SR a2 , -NR a3 R a4 or -PR a5 R a6, or R 6 to R 8 may link substituent via (C4-C7) alkenylene group with or without an adjacent aromatic ring to form Fused ring; Ar 1 is (C6-C20) aryl or (C3-C20) heteroaryl, and Ar is an aryl group or a heteroaryl group may be further selected from hydrogen, (C1-C20) alkyl, halo (C1-C20)alkyl, (C6-C20)aryl, (C1-C20)alkyl(C6-C20)aryl, (C6-C20)aryl(C1-C20)alkyl, -OR a1 , Substituting at least one of the group consisting of -SR a2 , -NR a3 R a4 and -PR a5 R a6 ; R a1 to R a6 are each independently (C1-C20)alkyl or (C6-C20)aryl; The alkyl, aryl, cycloalkyl, heteroaryl or heterocycloalkyl group of R 1 to R 3 and R 6 to R 8 and the alkyl or aryl group of R a1 to R a6 may be further selected from halogen, ( C1-C20)alkyl, halo(C1-C20)alkyl, (C1-C20)alkoxy, (C6-C20)aryl, (C6-C20)aryloxy, nitro, cyano, -OSiR B1 R b2 R b3 , -SR b4 , -NR b5 R b6 and -PR b7 R b8 are substituted by at least one of the groups; R b1 to R b8 are each independently (C1-C20) alkyl, (C6 -C20) aryl, (C6-C20) aryl (C1-C20) alkyl, (C1-C20) alkyl (C6-C20) aryl or (C3-C20) cycloalkyl; X 1 and X 2 Each independently is hydrogen, (C1-C20)alkyl, (C3-C20)cycloalkyl, (C6-C20)aryl, (C6-C20)aryl(C1-C20)alkyl, ((C1-C2) 0) alkyl (C6-C20) aryl) (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryloxy, (C1-C20) alkyl (C6-C20) Aryloxy, (C1-C20)alkoxy(C6-C20)aryloxy, -OSiR a R b R c , -SR d , -NR e R f , -PR g R h or (C1-C20) Alkylene; R a to R d are each independently (C1-C20)alkyl, (C6-C20)aryl, (C6-C20)aryl(C1-C20)alkyl, (C1-C20)alkyl (C6-C20) aryl or (C3-C20)cycloalkyl; R e to R h are each independently (C1-C20)alkyl, (C6-C20)aryl, (C6-C20)aryl (C1 -C20)alkyl, (C1-C20)alkyl (C6-C20) aryl, (C3-C20)cycloalkyl, tri(C1-C20)alkyldecyl or tris(C6-C20)arylhydrazine a limitation; when one of X 1 and X 2 is a (C1-C50) alkylene group, the other is neglected; and the heteroaryl group and the heterocycloalkyl group include at least one selected from the group consisting of N, Heteroatoms of O and S.

本文使用的術語“烷基”是指僅由碳原子和氫原子組成的單價直鏈或支鏈的飽和烴基自由基。烷基自由基的實例包括甲基、乙基、丙基、異丙基、丁基、異丁基、三級丁基、戊基、己基、辛基、壬基等,但本發明不限於此。 The term "alkyl" as used herein, refers to a monovalent straight or branched chain saturated hydrocarbon radical consisting solely of carbon atoms and hydrogen atoms. Examples of the alkyl radical include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group and the like, but the invention is not limited thereto .

本文使用的術語“芳基”是指由芳香族烴除去一個氫所得到的有機自由基,並且包括適當地在每個環中包含4至7個環原子,較佳5個或6個環原子的單環系統或稠合環系統,並且甚至包括其中複數個芳基藉由單鍵連接的形式。稠合環系統可包括脂肪族環諸如飽和環或部分飽和環,並且必須包含至少一個芳香族環。另外,脂肪族環可以在環中包括氮、氧、硫、羰基等。芳基自由基的具體實例包括苯基、萘基、聯苯基、茚基、茀基、菲基、蒽基、三亞苯基、芘基、基(chrysenyl)、稠四苯基、9,10-二氫蒽基等。 The term "aryl" as used herein, refers to an organic radical obtained by the removal of one hydrogen from an aromatic hydrocarbon, and includes suitably 4 to 7 ring atoms, preferably 5 or 6 ring atoms in each ring. A single ring system or a fused ring system, and even includes a form in which a plurality of aryl groups are linked by a single bond. The fused ring system may include an aliphatic ring such as a saturated ring or a partially saturated ring, and must contain at least one aromatic ring. Further, the aliphatic ring may include nitrogen, oxygen, sulfur, a carbonyl group or the like in the ring. Specific examples of the aryl radical include phenyl, naphthyl, biphenyl, anthracenyl, fluorenyl, phenanthryl, anthracenyl, triphenylene, fluorenyl, Chrysenyl, fused tetraphenyl, 9,10-dihydroindenyl, and the like.

本文使用的術語“雜芳基”是指,其包含1至4個選 自N、O和S的雜原子作為芳香族環結構骨架原子並且碳作為剩餘的芳香族環結構骨架原子的芳基,為5員或6員單環雜芳基和與至少一個苯環縮合的多環雜芳基,並且可以是部分飽和的。另外,本發明中的雜芳基可包括其中一個或多個雜芳基經由單鍵鏈結的形式。雜芳基的實例包括吡咯、喹啉、異喹啉、吡啶、嘧啶、噁唑(oxazole)、噻唑、噻二唑、***、咪唑、苯并咪唑、異噁唑、苯并異噁唑、噻吩、苯并噻吩、呋喃、苯并呋喃等,但本發明不限於此。 The term "heteroaryl" as used herein means an aryl group which contains 1 to 4 hetero atoms selected from N, O and S as an aromatic ring structure skeleton atom and carbon as a remaining aromatic ring structure skeleton atom, It is a 5- or 6-membered monocyclic heteroaryl group and a polycyclic heteroaryl group condensed with at least one benzene ring, and may be partially saturated. Additionally, heteroaryl groups in the present invention may include those in which one or more heteroaryl groups are linked via a single bond. Examples of heteroaryl groups include pyrrole, quinoline, isoquinoline, pyridine, pyrimidine, oxazole, thiazole, thiadiazole, triazole, imidazole, benzimidazole, isoxazole, benzisoxazole, Thiophene, benzothiophene, furan, benzofuran, etc., but the invention is not limited thereto.

本文使用的術語“環烷基”是指由一個或多個環組成的單價飽和碳環自由基(carbocyclic radical)。環烷基自由基的實例包括環丙基、環丁基、環戊基、環己基、環庚基等,但本發明不限於此。 The term "cycloalkyl" as used herein, refers to a monovalent saturated carbocyclic radical consisting of one or more rings. Examples of the cycloalkyl radical include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and the like, but the invention is not limited thereto.

本文使用的術語“鹵”或“鹵素”是指氟原子、氯原子、溴原子或碘原子。 The term "halo" or "halogen" as used herein means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

作為實例,本文使用的術語“鹵烷基”是指經一個或多個鹵素取代的烷基,並且可包括三氟甲基等。 As an example, the term "haloalkyl" as used herein, refers to an alkyl group substituted with one or more halogens, and may include trifluoromethyl and the like.

本文使用的術語“烷氧基”和“芳氧基”分別是指-O-烷基自由基和-O-芳基自由基,其中烷基和芳基與上述定義的相同。 The terms "alkoxy" and "aryloxy" as used herein mean -O-alkyl radical and -O-aryl radical, respectively, wherein alkyl and aryl are the same as defined above.

由根據本發明之化學式1表示的過渡金屬化合物可以具有其中具有特定結構的配位基化合物與過渡金屬結合的結構,從而具有高催化活性並且環繞過渡金屬容易控制電子/立體環境,且因此可以容易地控制乙烯均聚物或乙烯與α-烯烴的共聚物的諸如化學結構、分子量分布和機械性能等性質。 The transition metal compound represented by Chemical Formula 1 according to the present invention may have a structure in which a ligand compound having a specific structure is bonded to a transition metal, thereby having high catalytic activity and easily controlling an electron/stereo environment around a transition metal, and thus can be easily Properties such as chemical structure, molecular weight distribution, and mechanical properties of an ethylene homopolymer or a copolymer of ethylene and an α -olefin are controlled.

在本發明之示例性實施例中,由化學式1表示的過渡金屬化合物可以是由以下化學式2或化學式3表示的過渡金屬化合物。 In an exemplary embodiment of the present invention, the transition metal compound represented by Chemical Formula 1 may be a transition metal compound represented by the following Chemical Formula 2 or Chemical Formula 3.

[化學式3] [Chemical Formula 3]

在化學式2和化學式3中,M、R4、R5、R7、R8、Ar1、X1和X2與上述化學式1中所定義的相同;R1至R3各自獨立為氫、(C1-C20)烷基、(C6-C20)芳基、(C3-C20)環烷基、鹵素、(C2-C20)烯基、(C3-C20)雜芳基、(C3-C20)雜環烷基、-ORa1、-SRa2、-NRa3Ra4或-PRa5Ra6;Ra1至Ra6各自獨立為(C1-C20)烷基或(C6-C20)芳基;R1至R3的烷基、芳基、環烷基、雜芳基或雜環烷基和Ra1至Ra6的烷基或芳基可進一步經至少一個選自鹵素、(C1-C20)烷基、鹵(C1-C20)烷基、(C1-C20)烷氧基、(C6-C20)芳基、(C6-C20)芳氧基、硝基、氰基、-OSiRb1Rb2Rb3、-SRb4、-NRb5Rb6和-RRb7Rb8組成之群組中的至少一個所取代;以及Rb1至Rb8各自獨立為(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C1-C20)烷基(C6-C20)芳基或(C3-C20)環烷基。 In Chemical Formula 2 and Chemical Formula 3, M, R 4 , R 5 , R 7 , R 8 , Ar 1 , X 1 and X 2 are the same as defined in the above Chemical Formula 1; R 1 to R 3 are each independently hydrogen, (C1-C20)alkyl, (C6-C20)aryl, (C3-C20)cycloalkyl, halogen, (C2-C20)alkenyl, (C3-C20)heteroaryl, (C3-C20) Cycloalkyl, -OR a1 , -SR a2 , -NR a3 R a4 or -PR a5 R a6 ; R a1 to R a6 are each independently (C1-C20)alkyl or (C6-C20)aryl; R 1 The alkyl, aryl, cycloalkyl, heteroaryl or heterocycloalkyl group to R 3 and the alkyl or aryl group of R a1 to R a6 may further be at least one selected from the group consisting of halogen, (C1-C20) alkyl , halogen (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryl, (C6-C20) aryloxy, nitro, cyano, -OSiR b1 R b2 R b3 , At least one of the group consisting of -SR b4 , -NR b5 R b6 and -RR b7 R b8 is substituted; and R b1 to R b8 are each independently (C1-C20)alkyl, (C6-C20) aryl (C6-C20) aryl(C1-C20)alkyl, (C1-C20)alkyl(C6-C20)aryl or (C3-C20)cycloalkyl.

在本發明之示例性實施例中,Ar1為苯基、聯苯基、萘基、茀基、吡咯基、喹啉基、異喹啉基、吡啶基、嘧啶基或咔唑基,且Ar1的該苯基、聯苯基、萘基、茀基、吡咯基、喹啉基、異喹啉基、吡啶基、嘧啶基或咔唑基可進一步經選自鹵素、(C1-C20)烷基、鹵(C1-C20)烷基、(C6-C12)芳基、(C1-C10)烷基(C6-C12)芳基、(C6-C12)芳基(C1-C10)烷基、(C1-C10)烷氧基、(C6-C12)芳氧基、(C1-C10)烷硫基、(C6-C12)芳硫基、二(C1-C10)烷基胺基、二(C6-C12)芳基胺基、二(C1-C10)烷基膦和二(C6-C12)芳基膦組成之群組中的至少一個所取代。 In an exemplary embodiment of the invention, Ar 1 is phenyl, biphenyl, naphthyl, anthryl, pyrrolyl, quinolyl, isoquinolyl, pyridyl, pyrimidinyl or oxazolyl, and Ar the phenyl, biphenyl, naphthyl, fluorenyl, pyrrolyl, quinolinyl, isoquinolinyl, pyridinyl, pyrimidinyl, or a carbazolyl group may be further selected from halogen, (C1-C20) alkoxy , halo(C1-C20)alkyl, (C6-C12)aryl, (C1-C10)alkyl(C6-C12)aryl, (C6-C12)aryl(C1-C10)alkyl, ( C1-C10) alkoxy, (C6-C12) aryloxy, (C1-C10)alkylthio, (C6-C12) arylthio, di(C1-C10)alkylamino, di(C6- C12) substituted with at least one of the group consisting of an arylamine group, a di(C1-C10)alkylphosphine, and a di(C6-C12)arylphosphine.

在本發明之示例性實施例中,由化學式1表示之過渡金屬化合物更佳可為由以下化學式4或化學式5表示之過渡金屬化合物。 In the exemplary embodiment of the present invention, the transition metal compound represented by Chemical Formula 1 may more preferably be a transition metal compound represented by the following Chemical Formula 4 or Chemical Formula 5.

[化學式5] [Chemical Formula 5]

在化學式4和化學式5中,M、X1和X2與上述化學式1中所定義的相同;R1至R3各自獨立為氫、(C1-C20)烷基或鹵(C1-C20)烷基;R4和R5各自獨立為(C1-C20)烷基、鹵(C1-C20)烷基或(C6-C20)芳基;R7和R8各自獨立為氫、(C1-C20)烷基、鹵(C1-C20)烷基或鹵素,或者R7和R8可以透過 鏈結以形成稠合環;Ar1 m為1至5的整數,且R11為(C1-C10)烷基;R12和R13各自獨立為(C1-C20)烷基;以及R14、R15和R16各自獨立為氫或(C1-C20)烷基。 In Chemical Formula 4 and Chemical Formula 5, M, X 1 and X 2 are the same as defined in the above Chemical Formula 1: R 1 to R 3 are each independently hydrogen, (C1-C20) alkyl or halogen (C1-C20) alkane. R 4 and R 5 are each independently (C1-C20)alkyl, halo(C1-C20)alkyl or (C6-C20)aryl; R 7 and R 8 are each independently hydrogen, (C1-C20) Alkyl, halogen (C1-C20) alkyl or halogen, or R 7 and R 8 can pass through , , or Chaining to form a fused ring; Ar 1 is m is an integer of 1 to 5, and R 11 is (C1-C10)alkyl; R 12 and R 13 are each independently (C1-C20)alkyl; and R 14 , R 15 and R 16 are each independently hydrogen or (C1-C20) alkyl.

在本發明之示例性實施例中,過渡金屬化合物M係週期表中第4族的過渡金屬,且較佳可以是鈦(Ti)、鋯(Zr)或鉿(Hf)。 In an exemplary embodiment of the present invention, the transition metal compound M is a transition metal of Group 4 of the periodic table, and may preferably be titanium (Ti), zirconium (Zr) or hafnium (Hf).

在本發明之示例性實施例中,R1至R3可各自獨立地為氫、甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、正戊基、新戊基、戊基、正己基、正辛基、正癸基、正十二烷基、正十四烷基、正十六烷基、正十五烷基、苯基、吡啶基、甲氧基、乙氧基、丁氧基、甲硫基、乙硫基、二甲基胺基、甲基乙基胺基、二乙基胺基、二苯基胺基、二甲基膦、二乙基膦或二苯基膦,且R2和R3可以透過 鏈結以形成稠合環。 In an exemplary embodiment of the invention, R 1 to R 3 may each independently be hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tri Butyl, n-pentyl, neopentyl, pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-pentadecyl, Phenyl, pyridyl, methoxy, ethoxy, butoxy, methylthio, ethylthio, dimethylamino, methylethylamino, diethylamino, diphenylamino , dimethyl phosphine, diethyl phosphine or diphenyl phosphine, and R 2 and R 3 can pass through , , or Chains to form a fused ring.

在本發明之示例性實施例中,R1、R2和R3可各自獨立為氫、(C1-C20)烷基、(C1-C20)烷氧基或二(C1-C20)烷基胺基,較佳地,R1可為氫或(C1-C10)烷基、(C1-C10)烷氧基或二(C1-C10)烷基胺基,R2和R3可各自獨立為氫或(C1-C10)烷基,或者R2和R3可以透過 鏈結以形成稠合環。 In an exemplary embodiment of the invention, R 1 , R 2 and R 3 may each independently be hydrogen, (C1-C20)alkyl, (C1-C20) alkoxy or di(C1-C20)alkylamine. Further, R 1 may be hydrogen or (C1-C10)alkyl, (C1-C10) alkoxy or di(C1-C10)alkylamino, and R 2 and R 3 may each independently be hydrogen. Or (C1-C10) alkyl, or R 2 and R 3 can pass through , , or Chains to form a fused ring.

在本發明之示例性實施例中,R1可以為氫、甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、甲氧基、乙氧基、丁氧基、二甲基胺基、甲基乙基胺基或二乙基胺基,R2和R3可各自獨立為氫、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基或三級丁基,或者R2和R3可以透過 鏈結以形成稠合環。 In an exemplary embodiment of the invention, R 1 may be hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, methoxy Base, ethoxy, butoxy, dimethylamino, methylethylamino or diethylamino, R 2 and R 3 may each independently be hydrogen, ethyl, n-propyl, isopropyl , n-butyl, isobutyl, secondary butyl or tertiary butyl, or R 2 and R 3 can pass through Chains to form a fused ring.

在本發明之示例性實施例中,R1可以為氫,且R2和R3可以透過 鏈結以形成稠合環。 In an exemplary embodiment of the invention, R 1 may be hydrogen, and R 2 and R 3 may pass through Chains to form a fused ring.

在本發明之示例性實施例中,R1可以為(C1-C10)烷 基、(C1-C10)烷氧基或二(C1-C10)烷基胺基,且R2和R3可各自獨立為氫或(C1-C10)烷基。 In an exemplary embodiment of the present invention, R 1 may be (C1-C10)alkyl, (C1-C10)alkoxy or di(C1-C10)alkylamino, and R 2 and R 3 may each Independently hydrogen or (C1-C10)alkyl.

在本發明之示例性實施例中,R1可以為甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、甲氧基、乙氧基、丁氧基、二甲基胺基、甲基乙基胺基或二乙基胺基,且R2和R3可各自獨立為氫、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基或三級丁基。 In an exemplary embodiment of the invention, R 1 may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tert-butyl, methoxy, Ethoxy, butoxy, dimethylamino, methylethylamino or diethylamino, and R 2 and R 3 may each independently be hydrogen, ethyl, n-propyl, isopropyl, N-butyl, isobutyl, secondary butyl or tertiary butyl.

在本發明之示例性實施例中,R4和R5可以各自獨立地為甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、正戊基、新戊基、戊基、正己基、正辛基、正癸基、正十二烷基、正十四烷基、正十六烷基、正十五烷基、氟甲基、三氟甲基、全氟乙基、全氟丙基、環丙基、環丁基、環戊基、環己基、環庚基、環辛基、苯基、甲苯基、二甲苯基、三甲基苯基、四甲基苯基、五甲基苯基、乙基苯基、正丙基苯基、異丙基苯基、正丁基苯基、二級丁基苯基、三級丁基苯基、正戊基苯基、新戊基苯基、正己基苯基、正辛基苯基、正癸基苯基、正十二烷基苯基、聯苯基、茀基、三苯基、萘基、蒽基、苯甲基、萘基甲基、蒽基甲基、吡啶基、甲氧基、乙氧基、甲硫基、乙硫基、二甲基胺基、甲基乙基胺基、二乙基胺基、二苯基胺基、二甲基膦、二乙基膦或二苯基膦,或者R4和R5可以藉由丁烯或戊烯(pentylene)鏈結以形成環。 In an exemplary embodiment of the invention, R 4 and R 5 may each independently be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl Base, n-pentyl, neopentyl, pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-pentadecyl, fluoro Base, trifluoromethyl, perfluoroethyl, perfluoropropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, tolyl, xylyl, Trimethylphenyl, tetramethylphenyl, pentamethylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, secondary butylphenyl, tertiary Butylphenyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl, biphenyl, anthracenyl, tri Phenyl, naphthyl, anthracenyl, benzyl, naphthylmethyl, decylmethyl, pyridyl, methoxy, ethoxy, methylthio, ethylthio, dimethylamino, methyl Ethylamino, diethylamino, diphenylamino, dimethylphosphine, two Diphenyl phosphine or phosphine groups, or R 4 and R 5 may by butene or pentene (pentylene) link to form a ring.

在本發明之示例性實施例中,R4和R5可以各自獨立地為(C1-C20)烷基,較佳為(C1-C10)烷基、鹵(C1-C20)烷基,較佳為鹵(C1-C10)烷基或(C6-C20)芳基,並且較佳為(C6-C12)芳基。 In an exemplary embodiment of the present invention, R 4 and R 5 may each independently be a (C1-C20) alkyl group, preferably a (C1-C10) alkyl group, a halogen (C1-C20) alkyl group, preferably. It is a halogen (C1-C10) alkyl group or a (C6-C20) aryl group, and is preferably a (C6-C12) aryl group.

在本發明之示例性實施例中,R4和R5可以各自獨立地為甲基、乙基或苯基。 In an exemplary embodiment of the invention, R 4 and R 5 may each independently be a methyl group, an ethyl group or a phenyl group.

在本發明之示例性實施例中,R6至R8可以各自獨立地為氫、甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、正戊基、新戊基、戊基、正己基、正辛基、正癸基、正十二烷基、正十四烷基、正十六烷基、正十五烷基、氟甲基、三氟甲基、全氟乙基、全氟丙基、氯、氟、溴、苯基、聯苯基、茀基、三苯基、萘基、蒽基、苯甲基、萘基甲基、蒽基甲基、吡啶基、甲氧基、乙氧基、甲硫基、乙硫基、二甲基胺基、甲基乙基胺基、二乙基胺基、二苯基胺基、二甲基膦、二乙基膦或二苯基膦,或者R7和R8可以透過 鏈結以形成稠合環。 In an exemplary embodiment of the invention, R 6 to R 8 may each independently be hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tri Butyl, n-pentyl, neopentyl, pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-pentadecyl, Fluoromethyl, trifluoromethyl, perfluoroethyl, perfluoropropyl, chloro, fluoro, bromo, phenyl, biphenyl, decyl, triphenyl, naphthyl, anthracenyl, benzyl, naphthalene Methyl, decylmethyl, pyridyl, methoxy, ethoxy, methylthio, ethylthio, dimethylamino, methylethylamino, diethylamino, diphenyl Amine, dimethylphosphine, diethylphosphine or diphenylphosphine, or R 7 and R 8 can pass through , , or Chains to form a fused ring.

在本發明之示例性實施例中,R6至R8可以各自獨立 地為氫、(C1-C20)烷基,較佳為(C1-C10)烷基、鹵(C1-C20)烷基,並且較佳為鹵(C1-C20)烷基或鹵素。 In an exemplary embodiment of the present invention, R 6 to R 8 may each independently be hydrogen, (C1-C20)alkyl, preferably (C1-C10)alkyl, halo(C1-C20)alkyl, Further, it is preferably a halogen (C1-C20) alkyl group or a halogen.

在本發明之示例性實施例中,R6至R8可各自獨立地為氫、甲基、乙基、三級丁基或氟。 In an exemplary embodiment of the invention, R 6 to R 8 may each independently be hydrogen, methyl, ethyl, tert-butyl or fluoro.

在本發明之示例性實施例中,R6可以為氫,並且R7和R8可以各自獨立地為氫、(C1-C20)烷基,較佳為(C1-C10)烷基、鹵(C1-C20)烷基,並且較佳為鹵(C1-C10)烷基或鹵素,並且R7和R8可以透過 鏈結以形成稠合環。 In an exemplary embodiment of the present invention, R 6 may be hydrogen, and R 7 and R 8 may each independently be hydrogen, (C1-C20) alkyl, preferably (C1-C10) alkyl, halo ( C1-C20) alkyl, and preferably halo(C1-C10)alkyl or halogen, and R 7 and R 8 are permeable , , or Chains to form a fused ring.

在本發明之示例性實施例中,R6和R8可以為氫,R7可以為(C1-C10)烷基或鹵素,或者R7和R8可以透過 鏈結以形成稠合環。 In an exemplary embodiment of the present invention, R 6 and R 8 may be hydrogen, R 7 may be (C1-C10)alkyl or halogen, or R 7 and R 8 may be permeabilized. Chains to form a fused ring.

在本發明之示例性實施例中,R6和R8可以為氫,R7可以為甲基、乙基、三級丁基或氟,並且R7和R8可以透過 鏈結以形成稠合環。 In an exemplary embodiment of the invention, R 6 and R 8 may be hydrogen, R 7 may be methyl, ethyl, tert-butyl or fluoro, and R 7 and R 8 may be permeable. Chains to form a fused ring.

在本發明之示例性實施例中,Ar1可以為 ,m可以為1至5的整數,R11可以為(C1-C10)烷基,R12和R13可以各自獨立為(C1-C20)烷基,以及R14、R15和R16可以各自獨立為氫或(C1-C20)烷基。 In an exemplary embodiment of the invention, Ar 1 may be , or m may be an integer from 1 to 5, R 11 may be (C1-C10)alkyl, R 12 and R 13 may each independently be (C1-C20)alkyl, and R 14 , R 15 and R 16 may each Independently hydrogen or (C1-C20) alkyl.

在本發明之示例性實施例中,R11可以為甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、正戊基、新戊基、戊基、正己基或正辛基,R12和R13可以各自獨立為甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、正戊基、新戊基、戊基、正己基、正辛基、正癸基、正十二烷基、正十四烷基、正十六烷基或正十五烷基,且R14、R15和R16可以各自獨立為氫、甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、正戊基、新戊基、戊基、正己基、正辛基、正癸基、正十二烷基、正十四烷基、正十六烷基或正十五烷基。 In an exemplary embodiment of the present invention, R 11 may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tert-butyl, n-pentyl, Neopentyl, pentyl, n-hexyl or n-octyl, R 12 and R 13 may each independently be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, Tert-butyl, n-pentyl, neopentyl, pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-pentadecyl And R 14 , R 15 and R 16 may each independently be hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tert-butyl, n-pentyl Base, neopentyl, pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-pentadecyl.

在本發明之示例性實施例中,較佳地,R11可以為(C1-C10)烷基,R12和R13可以為(C1-C20)烷基,並且R14、R15和R16可以各自獨立地為氫或(C1-C10)烷基。 In an exemplary embodiment of the present invention, preferably, R 11 may be (C1-C10)alkyl, R 12 and R 13 may be (C1-C20)alkyl, and R 14 , R 15 and R 16 They may each independently be hydrogen or (C1-C10)alkyl.

在本發明之示例性實施例中,R11可以為(C1-C10)烷 基,R12、R13、R15和R16可以各自獨立地為(C1-C20)烷基,較佳為(C1-C15)烷基,且更佳為(C1-C10)烷基,並且R14可以為氫。 In an exemplary embodiment of the present invention, R 11 may be (C1-C10)alkyl, and R 12 , R 13 , R 15 and R 16 may each independently be (C1-C20)alkyl, preferably ( C1-C15) alkyl, and more preferably (C1-C10) alkyl, and R 14 may be hydrogen.

在本發明之示例性實施例中,X1和X2可以各自獨立地為氟、氯、溴、甲基、乙基、異丙基、戊基、環丙基、環丁基、環戊基、環己基、苯基、萘基、苯甲基、甲氧基、乙氧基、異丙氧基、三級丁氧基、苯氧基、4-三級丁基苯氧基、三甲基甲矽烷氧基、三級丁基二甲基甲矽烷氧基、二甲基胺基、二苯基胺基、二甲基膦、二乙基膦、二苯基膦、乙硫基或異丙硫基。 In an exemplary embodiment of the invention, X 1 and X 2 may each independently be fluorine, chlorine, bromine, methyl, ethyl, isopropyl, pentyl, cyclopropyl, cyclobutyl, cyclopentyl. , cyclohexyl, phenyl, naphthyl, benzyl, methoxy, ethoxy, isopropoxy, tert-butoxy, phenoxy, 4-tributylphenoxy, trimethyl Mercaptooxy, tert-butyl dimethylformamoxy, dimethylamino, diphenylamino, dimethylphosphine, diethylphosphine, diphenylphosphine, ethylthio or isopropyl Sulfur based.

在本發明之示例性實施例中,X1和X2可以各自獨立為(C1-C20)烷基,較佳為(C1-C10)烷基或鹵素,並且更佳地,X1和X2可以為(C1-C10)烷基。 In an exemplary embodiment of the present invention, X 1 and X 2 may each independently be a (C1-C20) alkyl group, preferably a (C1-C10) alkyl group or a halogen, and more preferably, X 1 and X 2 . It may be a (C1-C10) alkyl group.

在本發明之示例性實施例中,X1和X2可以各自獨立為甲基或氯,並且較佳地,甲基。 In an exemplary embodiment of the invention, X 1 and X 2 may each independently be methyl or chlorine, and preferably, methyl.

在本發明之示例性實施例中,過渡金屬化合物可以是選自具有以下結構的化合物,但其不限於此: In an exemplary embodiment of the present invention, the transition metal compound may be selected from compounds having the following structure, but is not limited thereto:

其中M是鈦、鋯或鉿。 Wherein M is titanium, zirconium or hafnium.

同時,為了經由使用根據本發明之過渡金屬化合物來製備用於選自乙烯均聚物和乙烯與α-烯烴的共聚物的乙烯系聚合物的製備的活性催化劑組分,較佳地,過渡金屬化合物可以與選自鋁化合物、硼化合物或其混合物的共催化劑一起起作用,該共催化劑作用為具有弱結合力的相對離子,亦即陰離子,同時藉由提取過渡金屬錯合物中的X1和X2配位基使中心金屬陽離子化。包含過渡金屬化合物和共催化劑的催化劑組合物也在本發明的範圍內。 Meanwhile, in order to prepare an active catalyst component for preparation of an ethylene-based polymer selected from the group consisting of an ethylene homopolymer and a copolymer of ethylene and an α -olefin, preferably a transition metal, by using the transition metal compound according to the present invention The compound may function with a cocatalyst selected from the group consisting of an aluminum compound, a boron compound or a mixture thereof, which acts as a relative ion having a weak binding force, that is, an anion, while extracting X 1 in the transition metal complex. And the X 2 ligand cationizes the central metal. Catalyst compositions comprising a transition metal compound and a cocatalyst are also within the scope of the invention.

在根據本發明之示例性實施例的催化劑組合物中,可使用作為共催化劑的鋁化合物可具體地為選自由化學式6或化學式7表示的鋁氧烷(aluminoxane)化合物、由化學式8表示的有機鋁化合物或由化學式9或化學式10表示的有機鋁氧化物化合物中的一種或兩種或更多種。 In the catalyst composition according to an exemplary embodiment of the present invention, the aluminum compound which can be used as a co-catalyst may specifically be an aluminoxane compound represented by Chemical Formula 6 or Chemical Formula 7, organically represented by Chemical Formula 8. One or two or more of an aluminum compound or an organoaluminum oxide compound represented by Chemical Formula 9 or Chemical Formula 10.

[化學式6](-Al(R51)-O-)m [Chemical Formula 6] (-Al(R 51 )-O-) m

[化學式7](R51)2A1-(-O(R51)-)q-(R51)2 (Chemical Formula 7) (R 51 ) 2 A1-(-O(R 51 )-) q -(R 51 ) 2

[化學式8] (R52)rAl(E)3-r (R 52 ) r Al(E) 3-r

[化學式9](R53)2AlOR54 [Chemical Formula 9] (R 53 ) 2 AlOR 54

[化學式10]R53Al(OR54)2 [Chemical Formula 10] R 53 Al(OR 54 ) 2

在化學式6至化學式10中,R51是(C1-C20)烷基,較佳為甲基或異丁基,n和q各自為5至20的整數;R52和R53各自獨立為(C1-C20)烷基;E為氫或鹵素;r為1至3的整數;以及R54為(C1-C20)烷基或(C6-C20)芳基。 In Chemical Formula 6 to Chemical Formula 10, R 51 is a (C1-C20) alkyl group, preferably a methyl group or an isobutyl group, and n and q are each an integer of 5 to 20; and R 52 and R 53 are each independently (C1). -C20)alkyl; E is hydrogen or halogen; r is an integer from 1 to 3; and R 54 is (C1-C20)alkyl or (C6-C20)aryl.

鋁化合物的具體實例可以包括甲基鋁氧烷、修飾(modified)甲基鋁氧烷和四異丁基鋁氧烷作為鋁氧烷化合物;有機鋁化合物的實例可以包括三烷基鋁,包括三甲基鋁、三乙基鋁、三丙基鋁、三異丁基鋁和三己基鋁;二烷基氯化鋁(dialkylaluminumchloride),包括二甲基氯化鋁、二乙基氯化鋁、二丙基氯化鋁、二異丁基氯化鋁和二己基氯化鋁;二氯化烷基鋁(alkylaluminum dichloride),包括二氯化甲基鋁、二氯化乙基鋁、二氯化丙基鋁、二氯化異丁 基鋁和二氯化己基鋁;以及氫化二烷基鋁,包括氫化二甲基鋁、氫化二乙基鋁、氫化二丙基鋁、氫化二異丁基鋁和氫化二己基鋁。 Specific examples of the aluminum compound may include methyl aluminoxane, modified methyl aluminoxane, and tetraisobutyl aluminoxane as the aluminoxane compound; examples of the organoaluminum compound may include trialkyl aluminum, including three Methyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum and trihexyl aluminum; dialkylaluminum chloride, including dimethyl aluminum chloride, diethyl aluminum chloride, two Propyl aluminum chloride, diisobutylaluminum chloride and dihexyl aluminum chloride; alkylaluminum dichloride, including methyl aluminum dichloride, ethyl aluminum dichloride, and polypropylene dichloride Base aluminum, isobutyl aluminum dichloride and hexyl aluminum dichloride; and hydrogenated dialkyl aluminum, including dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutyl aluminum hydride, and Hydrogenated dihexyl aluminum.

在本發明之示例性實施例中,鋁化合物較佳可以為選自烷基鋁氧烷化合物和三烷基鋁中的一種或兩種或更多種的混合物。更佳地,鋁化合物可以為選自甲基鋁氧烷、修飾甲基鋁氧烷、四異丁基鋁氧烷、三甲基鋁、三乙基鋁、三辛基鋁和三異丁基鋁中的一種或兩種或更多種的混合物。 In an exemplary embodiment of the present invention, the aluminum compound may preferably be one or a mixture of two or more selected from the group consisting of an alkyl aluminoxane compound and a trialkyl aluminum. More preferably, the aluminum compound may be selected from the group consisting of methyl aluminoxane, modified methyl aluminoxane, tetraisobutyl aluminoxane, trimethyl aluminum, triethyl aluminum, trioctyl aluminum, and triisobutyl. One or a mixture of two or more of aluminum.

由美國發明專利第5,198,401號已知可使用作為本發明之共催化劑的硼化合物,並且可以為選自由以下化學式11至化學式13表示的硼化合物。 It is known that a boron compound which is a cocatalyst of the present invention can be used, and may be a boron compound selected from the following Chemical Formula 11 to Chemical Formula 13, which is known from the U.S. Patent No. 5,198,401.

[化學式11]B(R41)3 [Chemical Formula 11] B(R 41 ) 3

[化學式12][R42]+[B(R41)4]- [Chemical Formula 12] [R 42 ] + [B(R 41 ) 4 ] -

[化學式13] [(R43)pZH]+[B(R41)4]- [(R 43 ) p ZH] + [B(R 41 ) 4 ] -

在化學式11至化學式13中,B為硼原子;R41為苯基,且該苯基可進一步經3至5個選自氟、未經取代或經氟取代的(C1-C20)烷基和未經取代或經氟取代的(C1-C20)烷氧基的取代基所取代;R42為(C5-C7)芳香族自由基或(C1-C20)烷基(C6-C20)芳基自由基、(C6-C20)芳基(C1-C20)烷基自由基,諸如三苯基甲基鎓(triphenylmethylium)自由基;Z為氮原子或磷原子;以及R43為(C1-C50)烷基自由基或經兩個(C1-C10)烷基與氮原子一起取代的苯胺鎓(anilinium)自由基;以及p為2或3的整數。 In Chemical Formula 11 to Chemical Formula 13, B is a boron atom; R 41 is a phenyl group, and the phenyl group may further be 3 to 5 (C1-C20) alkyl groups selected from fluorine, unsubstituted or fluorine-substituted and Substituted by a substituent of a (C1-C20) alkoxy group which is unsubstituted or substituted by fluorine; R 42 is a (C5-C7) aromatic radical or a (C1-C20) alkyl (C6-C20) aryl group free a (C6-C20) aryl (C1-C20) alkyl radical such as a triphenylmethylium radical; Z is a nitrogen atom or a phosphorus atom; and R 43 is a (C1-C50) alkane a radical or an anilinium radical substituted with two (C1-C10) alkyl groups together with a nitrogen atom; and p is an integer of 2 or 3.

硼系共催化劑的較佳實例可包括參(五氟苯基)硼烷、參(2,3,5,6-四氟苯基)硼烷、參(2,3,4,5-四氟苯基)硼烷、參(3,4,5-三氟苯基)硼烷、參(2,3,4-三氟苯基)硼烷、苯基雙(五氟苯基)硼烷、肆(五氟苯基)硼酸酯、肆(2,3,5,6-四氟苯基)硼酸酯、肆(2,3,4,5-四氟苯基)硼酸酯、肆(3,4,5-四氟苯基)硼酸酯、肆(2,2,4-三氟苯基)硼酸酯、苯基雙(五氟苯基)硼酸酯或肆(3,5-雙三氟甲基苯基)硼酸酯。具體組合物的實例包括肆(五氟苯基)硼酸二茂鐵(ferrocenium tetrakis(pentafluorophenyl)borate)、肆(五氟苯基)硼酸1,1’-二甲基二茂鐵(1,1’-dimethylferrocenium tetrakis(pentafluorophenyl)borate)、肆(五氟苯基)硼酸酯 (tetrakis(pentafluorophenyl)borate)、肆(五氟苯基)硼酸三苯基甲基酯(triphenylmethyl tetrakis(pentafluorophenyl)borate)、肆(3,5-雙三氟甲基苯基)硼酸三苯基甲基酯(triphenylmethyl tetrakis(3,5-bistrifluoromethylphenyl)borate)、肆(五氟苯基)硼酸三乙基銨、肆(五氟苯基)硼酸三丙基銨、肆(五氟苯基)硼酸三(正丁基)銨、肆(3,5-雙三氟甲基苯基)硼酸三(正丁基)銨、肆(五氟苯基)硼酸-N,N-二甲基苯銨、肆(五氟苯基)硼酸-N,N-二乙基苯銨、肆(五氟苯基)硼酸-N,N-2,4,6-五甲基苯銨、肆(3,5-雙三氟甲基苯基)硼酸-N,N-二甲基苯銨、肆(五氟苯基)硼酸二異丙基苯銨、肆(五氟苯基)硼酸二環己基苯銨、肆(五氟苯基)硼酸三苯基鏻、肆(五氟苯基)硼酸三(甲基苯基)鏻或肆(五氟苯基)硼酸三(二甲基苯基)鏻。彼等當中,最佳為肆(五氟苯基)硼酸-N,N-二甲基苯銨、肆(五氟苯基)硼酸三苯基甲基酯或參(五氟苯基)硼烷。 Preferable examples of the boron-based co-catalyst may include quinone (pentafluorophenyl)borane, ginseng (2,3,5,6-tetrafluorophenyl)borane, and ginseng (2,3,4,5-tetrafluoro). Phenyl)borane, ginseng (3,4,5-trifluorophenyl)borane, ginseng (2,3,4-trifluorophenyl)borane, phenylbis(pentafluorophenyl)borane, Bis(pentafluorophenyl)borate, bismuth (2,3,5,6-tetrafluorophenyl) borate, bismuth (2,3,4,5-tetrafluorophenyl) borate, hydrazine (3,4,5-tetrafluorophenyl)borate, bismuth(2,2,4-trifluorophenyl)borate, phenylbis(pentafluorophenyl)borate or hydrazine (3, 5-bistrifluoromethylphenyl)borate. Examples of specific compositions include ferrocenium tetrakis (pentafluorophenyl) boronate, quinone (pentafluorophenyl) borate 1,1'-dimethylferrocene (1,1'). -dimethylferrocenium tetrakis(pentafluorophenyl)borate), tetrakis(pentafluorophenyl)borate, triphenylmethyltetrakis(pentafluorophenyl)borate, Triphenylmethyl tetrakis(3,5-bistrifluoromethylphenyl)borate, triethylammonium pentoxide (pentafluorophenyl)borate, lanthanum Fluorophenyl)tripropylammonium borate, tri(n-butyl)ammonium pentium (pentafluorophenyl)borate, tris(n-butyl)ammonium ruthenium (3,5-bistrifluoromethylphenyl)borate, hydrazine (pentafluorophenyl)boronic acid-N,N-dimethylanilinium, quinone (pentafluorophenyl)boronic acid-N,N-diethylanilinium, quinone (pentafluorophenyl)boronic acid-N,N- 2,4,6-pentamethylanilinium, cerium (3,5-bistrifluoromethylphenyl)boronic acid-N,N-dimethylanilinium, decyl (pentafluorophenyl)borate diisopropyl Ammonium benzoate, quinone (pentafluorophenyl)borate dicyclohexyl phenyl ammonium, hydrazine (pentafluorophenyl) boric acid triphenyl Phosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium, or tetrakis (pentafluorophenyl) borate, tris (dimethylphenyl) phosphonium. Among them, the best is quinone (pentafluorophenyl)boronic acid-N,N-dimethylanilinium, quinone (pentafluorophenyl)borate triphenylmethyl ester or ginseng (pentafluorophenyl)borane. .

同時,共催化劑可用作清除劑,用於去除作為反應物中的催化劑毒物的雜質。 At the same time, the cocatalyst can be used as a scavenger for removing impurities as catalyst poisons in the reactants.

在本發明之示例性實施例中,當使用鋁化合物作為共催化劑時,本發明之過渡金屬化合物與共催化劑之間的比率可以具有較佳的範圍,即過渡金屬(M):鋁原子(Al)為1:10至5,000。 In an exemplary embodiment of the present invention, when an aluminum compound is used as a cocatalyst, the ratio between the transition metal compound of the present invention and the cocatalyst may have a preferable range, that is, transition metal (M): aluminum atom (Al) ) is 1:10 to 5,000.

在本發明之示例性實施例中,當鋁化合物和硼化合物同時用作為共催化劑時,本發明之過渡金屬化合物與共催化劑之間的比率可以具有較佳的莫耳比範圍,即過渡金屬(M):硼原子(B):鋁原子(Al)為1:0.1至100:10至3,000,並且更佳為1:0.5至5:100至3,000。 In an exemplary embodiment of the present invention, when the aluminum compound and the boron compound are simultaneously used as a cocatalyst, the ratio between the transition metal compound of the present invention and the cocatalyst may have a preferred molar ratio range, that is, a transition metal ( M): boron atom (B): The aluminum atom (Al) is from 1:0.1 to 100:10 to 3,000, and more preferably from 1:0.5 to 5:100 to 3,000.

當本發明之過渡金屬化合物與共催化劑之間的比率超出上述範圍時,由於共催化劑的量相對較小,所以過渡金屬化合物可能不會完全活化,因此過渡金屬化合物的催化活性可能不足,或者共催化劑的用量超過所需量,則製備成本可能大大增加。在上述範圍內,顯示出用於製備乙烯均聚物或乙烯與α-烯烴的共聚物的優異催化活性,並且該比率的範圍根據反應的純度而變化。 When the ratio between the transition metal compound of the present invention and the cocatalyst is outside the above range, since the amount of the cocatalyst is relatively small, the transition metal compound may not be fully activated, and thus the catalytic activity of the transition metal compound may be insufficient, or a total of If the amount of the catalyst exceeds the required amount, the preparation cost may be greatly increased. Within the above range, excellent catalytic activity for producing an ethylene homopolymer or a copolymer of ethylene and an α -olefin is shown, and the range of the ratio varies depending on the purity of the reaction.

作為本發明之另一態樣,使用過渡金屬催化劑組合物來製備乙烯聚合物的方法可以藉由使過渡金屬催化劑、共催化劑和乙烯或視需要地α-烯烴共聚單體在合適的有機溶劑的存在下接觸而進行。此處,可以將過渡金屬催化劑和共催化劑組分分別導入反應器中,或者可以預先將各自組分混合後並添加到反應器中,其中對混合條件諸如導入順序、溫度、濃度等等沒有特別限定。 As another aspect of the present invention, a method of preparing an ethylene polymer using a transition metal catalyst composition can be carried out by using a transition metal catalyst, a cocatalyst, and optionally an α -olefin comonomer in a suitable organic solvent. It is carried out in the presence of contact. Here, the transition metal catalyst and the cocatalyst component may be separately introduced into the reactor, or the respective components may be mixed and added to the reactor in advance, wherein there is no special mixing condition such as introduction order, temperature, concentration, and the like. limited.

可用於製備方法的較佳有機溶劑可以是(C3-C20)烴,並且其具體實例可以包括丁烷、異丁烷、戊烷、己烷、庚 烷、辛烷、異辛烷、壬烷、癸烷、十二烷、環己烷、甲基環己烷、苯、甲苯、二甲苯等等。 A preferred organic solvent which can be used in the production method may be a (C3-C20) hydrocarbon, and specific examples thereof may include butane, isobutane, pentane, hexane, heptane, octane, isooctane, decane, Decane, dodecane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, and the like.

具體地,在製備乙烯均聚物時,乙烯單獨作為單體使用,其中乙烯的壓力可以適當地為1atm至1000atm,並且更佳10atm至150atm。另外,聚合反應係在聚合反應溫度為25℃至200℃,較佳50℃至180℃,更佳100℃至180℃下有效地進行。 Specifically, in the preparation of the ethylene homopolymer, ethylene is used alone as a monomer, wherein the pressure of ethylene may suitably be from 1 atm to 1000 atm, and more preferably from 10 atm to 150 atm. Further, the polymerization reaction is efficiently carried out at a polymerization temperature of from 25 ° C to 200 ° C, preferably from 50 ° C to 180 ° C, more preferably from 100 ° C to 180 ° C.

另外,當製備乙烯與α-烯烴的共聚物時,可以使用選自C3-C18 α-烯烴、C5-C20環烯烴、苯乙烯和苯乙烯衍生物中的至少一種作為與乙烯一起使用的共聚單體。C3-C18 α-烯烴的較佳實例可以包括丙烯、1-丁烯、1-戊烯、4-甲基-1-戊烯、1-己烯、1-辛烯、1-癸烯、1-十一烯、1-十二烯、1-十四烯、1-十六烯和1-十八碳烯,並且C5-C20環烯烴的較佳實例可以包括環戊烯、環己烯、降冰片烯和苯基降冰片烯。苯乙烯及其衍生物可選自苯乙烯、α-甲基苯乙烯、對甲基苯乙烯和3-氯甲基苯乙烯。在本發明中,乙烯可與上述烯烴共聚合,或者二種或更多種烯烴,且更佳為1-丁烯、1-己烯、1-辛烯或1-癸烯可與乙烯共聚合。在這種情況下,乙烯的較佳壓力及聚合反應溫度可與製備乙烯均聚物的情況相同,並且根據本發明之方法製備的共聚物的乙烯含量通常含有30重量%或更多,較佳為60重量%或更多,且更佳為60重量%至99重量%。 Further, when preparing a copolymer of ethylene and an α -olefin, at least one selected from the group consisting of C3-C18 α -olefin, C5-C20 cyclic olefin, styrene, and styrene derivative can be used as a copolymerization sheet for use together with ethylene. body. Preferred examples of the C3-C18 α -olefin may include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, and 1 -undecene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene, and preferred examples of the C5-C20 cyclic olefin may include cyclopentene, cyclohexene, Norbornene and phenyl norbornene. Styrene and its derivatives may be selected from the group consisting of styrene, α -methylstyrene, p-methylstyrene, and 3-chloromethylstyrene. In the present invention, ethylene may be copolymerized with the above olefin, or two or more olefins, and more preferably 1-butene, 1-hexene, 1-octene or 1-decene may be copolymerized with ethylene. . In this case, the preferred pressure and polymerization temperature of ethylene may be the same as in the case of preparing an ethylene homopolymer, and the copolymer prepared by the method of the present invention usually has an ethylene content of 30% by weight or more, preferably. It is 60% by weight or more, and more preferably 60% by weight to 99% by weight.

如上所述,當使用本發明的催化劑時,可由適當使用C3-C18 α-烯烴作為共聚單體以及乙烯可以簡單且經濟地製備具有0.850克(g)/立方公分(cc)至0.960克/立方公分之密度及0.001公釐/分鐘(dg/min)至15公釐/分鐘之熔流指數之從彈性體至高密度聚乙烯(HDPE)的聚合物。 As described above, when the catalyst of the present invention is used, it can be easily and economically produced by suitably using a C3-C18 α -olefin as a comonomer and ethylene, and has 0.850 g (g) / cubic centimeter (cc) to 0.960 g / cubic. Density of centimeters and polymer from elastomer to high density polyethylene (HDPE) with a melt flow index of 0.001 mm/min (dg/min) to 15 mm/min.

另外,當製備根據本發明之乙烯均聚物或共聚物時,可使用氫作為分子量調節劑,以調節分子量。其重量平均分子量(Mw)通常為5,000克/莫耳至1,000,000克/莫耳的範圍。 Further, when preparing an ethylene homopolymer or copolymer according to the present invention, hydrogen can be used as a molecular weight regulator to adjust the molecular weight. Its weight average molecular weight (Mw) is usually in the range of 5,000 g/m to 1,000,000 g/mole.

由於本發明所提出的催化劑組合物在聚合反應器中係處於均質狀態,因此該催化劑組合物可較佳地使用於在溫度高於相應聚合物熔點下進行的溶液聚合反應法。然而,如美國專利第4,752,597號所揭露,過渡金屬化合物和共催化劑可承載在多孔性金屬氧化物承載物上,以用於漿料聚合反應或氣相聚合反應法,作為非勻相催化劑組合物。 Since the catalyst composition proposed by the present invention is in a homogeneous state in the polymerization reactor, the catalyst composition can be preferably used in a solution polymerization method which is carried out at a temperature higher than the melting point of the corresponding polymer. However, as disclosed in U.S. Patent No. 4,752,597, the transition metal compound and cocatalyst can be supported on a porous metal oxide support for slurry polymerization or gas phase polymerization as a non-homogeneous catalyst composition. .

在下文中,參考以下實例詳細描述本發明。然而,本發明的範圍不受以下實例的限制。 Hereinafter, the present invention will be described in detail with reference to the following examples. However, the scope of the invention is not limited by the following examples.

除非另有說明,否則所有用於合成配位基和催化劑的實驗均在氮氣氛下藉由使用標準舒倫克(Schlenk)或手套箱 (glove-box)技術來進行。將反應中使用的有機溶劑在金屬鈉和二苯甲酮上回流以除去水分,然後在使用之前立即蒸餾。合成的配位基和催化劑的1H-NMR分析藉由在室溫下使用Brucker 500MHz來進行。 Unless otherwise stated, all experiments for the synthesis of ligands and catalysts were carried out under nitrogen atmosphere using standard Schlenk or glove-box techniques. The organic solvent used in the reaction was refluxed on sodium metal and benzophenone to remove moisture, and then distilled immediately before use. 1 H-NMR analysis of the synthesized ligand and catalyst was carried out by using Brucker 500 MHz at room temperature.

在使用之前,將作為聚合反應溶劑的環己烷通過填充有分子篩5埃(Å)和活化性氧化鋁的管,並通以高純度氮氣鼓泡從而充分除去水分、氧氣和其他催化劑毒物。藉由以下描述的測量方法來分析聚合的聚合物。 Prior to use, cyclohexane as a polymerization solvent was passed through a tube filled with molecular sieves of 5 Å (Å) and activated alumina, and was bubbled with high-purity nitrogen gas to sufficiently remove moisture, oxygen, and other catalyst poisons. The polymerized polymer was analyzed by the measurement method described below.

1.分子量和分子量分布 1. Molecular weight and molecular weight distribution

藉由使用Freeslate Rapid GPC,在1,2,3-三氯苯溶劑存在的情況下在135℃以1.0mL/min的速率進行測量,並且藉由使用PL聚苯乙烯標準品來校準分子量。 The measurement was carried out at a rate of 1.0 mL/min at 135 ° C in the presence of 1,2,3-trichlorobenzene solvent by using Freeslate Rapid GPC, and the molecular weight was calibrated by using a PL polystyrene standard.

2.共聚物中α-烯烴的含量(莫耳%) 2. The content of α -olefin in the copolymer (% by mole)

於Bruker Avance 400核磁共振光譜儀中,在125MHz、13C-NMR模式、120℃下,使用1,2,4-三氯苯/C6D6(重量分率7/3)混合溶劑進行測量α-烯烴的含量。(參見Randal,J.C.JMS-Rev.Macromol.Chem.Phys.1980,C29,201) At Bruker Avance 400 NMR spectrometer at 125MHz, 13 C-NMR mode, at 120 deg.] C, using 1,2,4-trichlorobenzene / C 6 D 6 (7/3 weight fraction) mixed solvent was measured α - the content of olefins. (See Randal, JCJMS-Rev. Macromol. Chem. Phys. 1980, C29, 201)

使用紅外光譜儀定量共聚物中乙烯與α-烯烴之間的比率。 The ratio between ethylene and alpha -olefin in the copolymer was quantified using an infrared spectrometer.

3.聚合物的結晶度 3. Crystallinity of the polymer

藉由使用PolymerChar A-CEF分析聚合物的支化分布來測量聚合物的無定形部分(Amorphous Fraction;AF)。 The amorphous portion of the polymer (Amorphous Fraction; AF) was measured by analyzing the branched distribution of the polymer using PolymerChar A-CEF.

[實例1至實例5]根據本發明之過渡金屬催化劑1至過渡金屬催化劑5的製備 [Example 1 to Example 5] Preparation of Transition Metal Catalyst 1 to Transition Metal Catalyst 5 According to the Present Invention

化合物B的製備 Preparation of Compound B

將2-甲基-9H-環戊[a]萘(30.08mmol)加入到THF(112mL)中,然後在-78℃下緩慢加入n-BuLi的己烷溶液(2.5M,31.58mmol)。在n-BuLi的添加完成之後,將溫度緩慢升至室溫,然後將混合物攪拌2小時。攪拌完成之後,將混合物冷卻至-78℃,緩慢滴加(2-(烯丙氧基)-5-取代的-3-(9,9-二取代的-9H-茀-7-基)苯基)氯二甲基矽烷(化合物A,33.09mmol)的甲苯(14mL)溶液,然後將反應混合物的溫度升至室溫。在室溫下進一步攪拌3小時之後,將反應混合物加入到蒸餾水(200mL)中以終止反應。將有機層以甲苯(2×50mL)萃取,以Na2SO4除去水,並經真空蒸餾除去溶劑,以獲得油狀黃色殘餘物。然後,使用填充有矽膠60(40-63μm)的管柱,藉由急速層析法(沖堤液:1:10體積的二氯甲烷/己烷)純化殘餘物,以獲得作為標題化合物的化合物B。 2-Methyl-9H-cyclopenta[a]naphthalene (30.08 mmol) was added to THF (112 mL), and then a solution of n-BuLi in hexane (2.5 M, 31.58 mmol) was slowly added at -78 °C. After the addition of n-BuLi was completed, the temperature was slowly raised to room temperature, and then the mixture was stirred for 2 hours. After the completion of the stirring, the mixture was cooled to -78 ° C, and (2-(allyloxy)-5-substituted-3-(9,9-disubstituted-9H-indol-7-yl)benzene was slowly added dropwise. A solution of chlorodimethylmethane (Compound A, 33.09 mmol) in toluene (14 mL) was then taken and then warmed to room temperature. After further stirring for 3 hours at room temperature, the reaction mixture was added to distilled water (200 mL) to terminate the reaction. The organic layer with toluene (2 × 50mL) and extracted to remove water 2 SO 4 Na, and the solvent removed by vacuum distillation to obtain a yellow oily residue. Then, the residue was purified by flash chromatography (distilled liquid: 1:10 volume of dichloromethane/hexane) using a column packed with silica gel 60 (40-63 μm) to obtain a compound as the title compound. B.

化合物B1(R7=Me,R12=R13=Me):53%產率。1H NMR(CDCl3):δ 8.18(m,1H),7.90(m,1H),7.84(m,1H),7.80-7.82(m,2H),7.62-7.65(m,1H),7.36-7.54(m,7H),7.30(m,1H),7.23(m,1H),7.08(m,1H),5.83(m,1H),5.31(d,1H),5.13(d,1H),4.36(m,1H),4.14(s,1H),2.40(s,3H),2.18(s,3H),1.57(s,6H),0.23(s,3H),0.09(s,3H). Compound B1 (R 7 =Me, R 12 =R 13 =Me): 53% yield. 1 H NMR (CDCl 3 ): δ 8.18 (m, 1H), 7.90 (m, 1H), 7.84 (m, 1H), 7.80-7.82 (m, 2H), 7.62-7.65 (m, 1H), 7.36- 7.54 (m, 7H), 7.30 (m, 1H), 7.23 (m, 1H), 7.08 (m, 1H), 5.83 (m, 1H), 5.31 (d, 1H), 5.13 (d, 1H), 4.36 (m, 1H), 4.14 (s, 1H), 2.40 (s, 3H), 2.18 (s, 3H), 1.57 (s, 6H), 0.23 (s, 3H), 0.09 (s, 3H).

Compound B2(R7=Me,R12=R13=n-Bu):44%產率。1H NMR(CDCl3):δ 8.16(m,1H),7.88(m,1H),7.80(m,1H),7.76(m,1H),7.66(m,1H),7.61(m,1H),7.48-7.52(m,2H),7.43(m,1H),7.32-7.38(m,4H),7.29(m,1H),7.21(m,1H),7.07(m,1H),5.81(m,1H),5.32(m,1H),5.13(m,1H),4.35(m,1H),4.14(m,1H),2.39(s,3H),2.15(s,3H),2.03(m,4H),1.08-1.14(m,4H),0.68(m,6H),0.60-0.67(m,4H),0.21(s,3H),0.06(s,3H). Compound B2 (R 7 =Me, R 12 =R 13 =n-Bu): 44% yield. 1 H NMR (CDCl 3 ): δ 8.16 (m, 1H), 7.88 (m, 1H), 7.80 (m, 1H), 7.76 (m, 1H), 7.66 (m, 1H), 7.61 (m, 1H) , 7.48-7.52 (m, 2H), 7.43 (m, 1H), 7.32-7.38 (m, 4H), 7.29 (m, 1H), 7.21 (m, 1H), 7.07 (m, 1H), 5.81 (m) , 1H), 5.32 (m, 1H), 5.13 (m, 1H), 4.35 (m, 1H), 4.14 (m, 1H), 2.39 (s, 3H), 2.15 (s, 3H), 2.03 (m, 4H), 1.08-1.14 (m, 4H), 0.68 (m, 6H), 0.60-0.67 (m, 4H), 0.21 (s, 3H), 0.06 (s, 3H).

化合物B3(R7=F,R12=R13=Me):60%產率。1H NMR(CDCl3):δ 8.13(m,1H),7.87(m,1H),7.81(m,1H),7.75-7.78(m,2H),7.59(m,1H),7.34-7.52(m,7H),7.20-7.25(m,2H),6.93(m,1H),5.79(m,1H),5.28(m,1H),5.11(m,1H),4.29(m,1H),4.10(m,1H),2.14(s,3H),1.53(s,6H),0.18(s,3H),0.06(s,3H). Compound B3 (R 7 = F, R 12 = R 13 = Me): 60% yield. 1 H NMR (CDCl 3 ): δ 8.13 (m, 1H), 7.87 (m, 1H), 7.81 (m, 1H), 7.75-7.78 (m, 2H), 7.59 (m, 1H), 7.34 - 7.52 ( m,7H), 7.20-7.25 (m, 2H), 6.93 (m, 1H), 5.79 (m, 1H), 5.28 (m, 1H), 5.11 (m, 1H), 4.29 (m, 1H), 4.10 (m, 1H), 2.14 (s, 3H), 1.53 (s, 6H), 0.18 (s, 3H), 0.06 (s, 3H).

化合物B4(R7=F,R12=R13=n-Bu):59%產率。1H NMR(CDCl3):δ 8.13(m,1H),7.87(m,1H),7.80(m,1H),7.75(m,1H),7.64(m,1H0,7.59(m,1H),7.48-7.52(m,2H),7.43(m,1H),7.32-7.38(m,3H),7.26(m,1H),7.20-7.23(m,2H),6.94(m,1H),5.79(m,1H),5.31(m,1H),5.14(m,1H),4.30(m,1H),4.13(m,1H),2.15(s,3H),2.02(m,4H),1.03-1.14(m,4H),0.68(m,6H),0.60-0.67(m,4H),0.19(s, 3H),0.06(s,3H). Compound B4 (R 7 = F, R 12 = R 13 = n-Bu): 59% yield. 1 H NMR (CDCl 3 ): δ 8.13 (m, 1H), 7.87 (m, 1H), 7.80 (m, 1H), 7.75 (m, 1H), 7.64 (m, 1H0, 7.59 (m, 1H), 7.48-7.52 (m, 2H), 7.43 (m, 1H), 7.32-7.38 (m, 3H), 7.26 (m, 1H), 7.20-7.23 (m, 2H), 6.94 (m, 1H), 5.79 ( m,1H), 5.31 (m, 1H), 5.14 (m, 1H), 4.30 (m, 1H), 4.13 (m, 1H), 2.15 (s, 3H), 2.02 (m, 4H), 1.03-1.14 (m, 4H), 0.68 (m, 6H), 0.60-0.67 (m, 4H), 0.19 (s, 3H), 0.06 (s, 3H).

化合物B5(R7=Me,R12=R13=n-十四烷基):59%產率。1H NMR(CDCl3):δ 8.18(m,1H),7.90(m,1H),7.84(m,1H),7.80-7.82(m,2H),7.62-7.65(m,1H),7.36-7.54(m,7H),7.30(m,1H),7.23(m,1H),7.08(m,1H),5.79(m,1H),5.31(d,1H),5.14(d,1H),4.30(m,1H),4.13(s,1H),2.40(s,3H),2.18(s,3H),1.27-0.20(m,61H),0.09(s,3H). Compound B5 (R 7 =Me, R 12 =R 13 =n-tetradecyl): 59% yield. 1 H NMR (CDCl 3 ): δ 8.18 (m, 1H), 7.90 (m, 1H), 7.84 (m, 1H), 7.80-7.82 (m, 2H), 7.62-7.65 (m, 1H), 7.36- 7.54 (m, 7H), 7.30 (m, 1H), 7.23 (m, 1H), 7.08 (m, 1H), 5.79 (m, 1H), 5.31 (d, 1H), 5.14 (d, 1H), 4.30 (m, 1H), 4.13 (s, 1H), 2.40 (s, 3H), 2.18 (s, 3H), 1.27-0.20 (m, 61H), 0.09 (s, 3H).

化合物C的製備 Preparation of Compound C

將其中溶解化合物B(10mmol)和Et3N(45mmol)的甲苯(70mL)冷卻至-78℃並向其內加入n-BuLi的己烷溶液(2.5M,22mmol)。在n-BuLi的添加完成之後,將反應混合物升溫至室溫並在室溫下攪拌20小時。將反應混合物再次冷卻至-78℃之後,緩慢滴加TiCl4(15mmol)的甲苯(22mL)溶液。在TiCl4的添加完成之後,將反應混合物緩慢加熱至室溫,並將反應混合物在90℃下進一步攪拌。將反應物的溫度冷卻至室溫,在氮氣氛下經真空除去溶劑。在除去溶劑之後,加入溫熱的甲基環己烷,所得副產物通過矽藻土過濾器分離。將從過濾器得到的濾液真空乾燥,加入甲基環己烷和己烷的混合溶劑,以在-30℃下獲得呈固體形式的標題化合物C,為紅棕色沉澱。 Toluene (70 mL) in which Compound B (10 mmol) and Et 3 N (45 mmol) were dissolved was cooled to -78 ° C, and n-BuLi hexane solution (2.5 M, 22 mmol) was added thereto. After the addition of n-BuLi was completed, the reaction mixture was warmed to room temperature and stirred at room temperature for 20 hr. After the reaction mixture was again cooled to -78 ° C, a solution of TiCl 4 (15 mmol) in toluene (22 mL) was slowly added dropwise. After the addition of TiCl 4 was completed, the reaction mixture was slowly heated to room temperature, and the reaction mixture was further stirred at 90 °C. The temperature of the reaction was cooled to room temperature and the solvent was removed in vacuo under nitrogen. After removal of the solvent, warm methylcyclohexane was added and the resulting by-product was separated by a diatomaceous earth filter. The filtrate obtained from the filter was dried under vacuum, and a mixed solvent of methylcyclohexane and hexane was added to obtain the title compound C as a red-brown precipitate.

化合物C1(R7=Me,R12=R13=Me):71%產率。1H NMR(CD2Cl2):δ 8.31(m,1H),7.84(m,1H),7.72(m,1H),7.62-7.68(m,4H),7.56(m,1H),7.44(m,1H),7.39-7.42(m,2H),7.31-7.35(m,3H),7.28(m,2H),2.50(s,3H),2.49(s,3H),1.41(s,3H),1.43(s,3H),0.83(s,3H),0.77(s,3H). Compound C1 (R 7 =Me, R 12 =R 13 =Me): 71% yield. 1 H NMR (CD 2 Cl 2 ): δ 8.31 (m, 1H), 7.84 (m, 1H), 7.72 (m, 1H), 7.62-7.68 (m, 4H), 7.56 (m, 1H), 7.44 ( m,1H), 7.39-7.42 (m, 2H), 7.31-7.35 (m, 3H), 7.28 (m, 2H), 2.50 (s, 3H), 2.49 (s, 3H), 1.41 (s, 3H) , 1.43 (s, 3H), 0.83 (s, 3H), 0.77 (s, 3H).

化合物C2(R7=Me,R12=R13=n-Bu):71%產率。1H NMR(CD2Cl2):δ 8.31(m,1H),7.83(m,1H),7.73(m,1H),7.63-7.66(m,3H),7.60(m,1H),7.49-7.54(m,2H),7.38-7.44(m,2H),7.32(m,3H),7.26(m,2H),2.51(s,3H),2.49(s,3H),1.89-1.99(m,4H),0.94-1.05(m,4H),0.82(s,3H),0.75(s,3H),0.57-0.61(m,6H),0.42-0.70(m,4H). Compound C2 (R 7 =Me, R 12 = R 13 = n-Bu): 71% yield. 1 H NMR (CD 2 Cl 2 ): δ 8.31 (m, 1H), 7.83 (m, 1H), 7.73 (m, 1H), 7.63-7.66 (m, 3H), 7.60 (m, 1H), 7.49- 7.54 (m, 2H), 7.38-7.44 (m, 2H), 7.32 (m, 3H), 7.26 (m, 2H), 2.51 (s, 3H), 2.49 (s, 3H), 1.89-1.99 (m, 4H), 0.94-1.05 (m, 4H), 0.82 (s, 3H), 0.75 (s, 3H), 0.57-0.61 (m, 6H), 0.42-0.70 (m, 4H).

化合物C3(R7=F,R12=R13=Me):62%產率。1H NMR(CD2Cl2):δ 8.31(m,1H),7.84(m,1H),7.72(m,1H),7.64-7.67(m,4H),7.58(m,1H),7.41(m,2H),7.33-7.35(m,2H),7.28-7.31(m,3H),7.25-7.28(m,1H),2.51(s,3H),1.41(s,3H),1.44(s,3H),0.85(s,3H),0.79(s,3H). Compound C3 (R 7 = F, R 12 = R 13 = Me): 62% yield. 1 H NMR (CD 2 Cl 2 ): δ 8.31 (m, 1H), 7.84 (m, 1H), 7.72 (m, 1H), 7.64 - 7.67 (m, 4H), 7.58 (m, 1H), 7.41 ( m, 2H), 7.33-7.35 (m, 2H), 7.28-7.31 (m, 3H), 7.25-7.28 (m, 1H), 2.51 (s, 3H), 1.41 (s, 3H), 1.44 (s, 3H), 0.85 (s, 3H), 0.79 (s, 3H).

化合物C4(R7=F,R12=R13=n-Bu):74%產率。1H NMR(CD2Cl2):δ 8.32(m,1H),7.85(m,1H),7.74(m,1H),7.68(m,1H),7.65(m,1H),7.63(m,1H),7.55(m,1H),7.51(m,1H),7.37(m,1H),7.28-7.36(m,6H),7.26(m,1H),2.53(s,3H),1.91-1.99(m,4H),0.96-1.07(m,4H),0.84(s,3H), 0.78(s,3H),0.58-0.63(m,6H),0.42-0.70(m,4H). Compound C4 (R 7 = F, R 12 = R 13 = n-Bu): 74% yield. 1 H NMR (CD 2 Cl 2 ): δ 8.32 (m, 1H), 7.85 (m, 1H), 7.74 (m, 1H), 7.68 (m, 1H), 7.65 (m, 1H), 7.63 (m, 1H), 7.55 (m, 1H), 7.51 (m, 1H), 7.37 (m, 1H), 7.28-7.36 (m, 6H), 7.26 (m, 1H), 2.53 (s, 3H), 1.91-1.99 (m, 4H), 0.96-1.07 (m, 4H), 0.84 (s, 3H), 0.78 (s, 3H), 0.58-0.63 (m, 6H), 0.42-0.70 (m, 4H).

化合物C5(R7=Me,R12=R13=n-十四烷基):54%產率。1H NMR(CD2Cl2):δ 8.30(d,1H),7.81(d,1H),7.74-7.24(m,14H),2.43(s,3H),2.02(m,3H),1.93(s,3H),1.27-0.60(m,64H). Compound C5 (R 7 =Me, R 12 =R 13 =n-tetradecyl): 54% yield. 1 H NMR (CD 2 Cl 2 ): δ 8.30 (d, 1H), 7.81 (d, 1H), 7.74-7.24 (m, 14H), 2.43 (s, 3H), 2.02 (m, 3H), 1.93 ( s, 3H), 1.27-0.60 (m, 64H).

化合物1至化合物5的製備 Preparation of Compound 1 to Compound 5

將化合物C(10mmol)溶於***(100mL)中,並在-30℃下緩慢加入MeMgBr(2.9M的***溶液,22mmol)溶液。將反應混合物緩慢加熱至室溫,攪拌22小時,然後在氮氣氛下經真空除去溶劑。加入溫己烷,並通過矽藻土過濾器過濾混合物以獲得濾液。然後,在氮氣氛下真空除去溶劑。將得到的固體溶解於己烷(70m)中,再次以矽藻土過濾器處理,並將所得濾液冷卻至-30℃,以獲得呈黃色固體形式的標題化合物1至標題化合物5。 Compound C (10 mmol) was dissolved in diethyl ether (100 mL), and a solution of MeMgBr (2.9 M in diethyl ether, 22 mmol) was slowly added at -30 °C. The reaction mixture was slowly warmed to room temperature and stirred for 22 hours, then the solvent was removed in vacuo under nitrogen. Warm hexane was added and the mixture was filtered through a diatomaceous earth filter to obtain a filtrate. Then, the solvent was removed under vacuum under a nitrogen atmosphere. The obtained solid was dissolved in hexane (70 m), EtOAc (EtOAc m.

實例1過渡金屬催化劑化合物1(R7=Me,R11=R12=Me),10%產率。1H NMR(C6D6):δ 8.15(m,1H),8.04(m,1H),7.81(m,1H),7.73(m,1H),7.57(m,2H),7.40(m,1H),7.34-7.38(m,3H),7.14-7.27(m,6H),2.31(s,3H),1.77(s,3H),1.45(m,3H),1.39(m,3H),0.78(s,3H),0.57(s,3H),0.55(m,3H),-0.08(s,3H).13C NMR(CD2Cl2):δ 162.62,154.40,153.75,139.54,138.90,138.09,134.39,133.10,132.14,131.88,130.85,130.43,129.76,129.08,128.94,128.51,127.58,127.46,127.33,126.92,124.74,124.43,123.85,122.99,120.29,119.81,111.45,103.53,60.30,51.83,41.30,27.56,21.01,15.72,0.84,-0.75. Example 1 Transition Metal Catalyst Compound 1 (R 7 =Me, R 11 =R 12 =Me), 10% yield. 1 H NMR (C 6 D 6 ): δ 8.15 (m, 1H), 8.04 (m, 1H), 7.81 (m, 1H), 7.73 (m, 1H), 7.57 (m, 2H), 7.40 (m, 1H), 7.34-7.38 (m, 3H), 7.14-7.27 (m, 6H), 2.31 (s, 3H), 1.77 (s, 3H), 1.45 (m, 3H), 1.39 (m, 3H), 0.78 (s, 3H), 0.57 (s, 3H), 0.55 (m, 3H), -0.08 (s, 3H). 13 C NMR (CD 2 Cl 2 ): δ 162.62, 154.40, 153.75, 139.54, 138.90, 138.09 , 134.39, 133.10, 132.14, 131.88, 130.85, 130.43, 129.76, 129.08, 128.94, 128.51, 127.58, 127.46, 127.33, 126.92, 124.74, 124.43, 123.85, 122.99, 120.29, 119.81, 111.45, 103.53, 60.30, 51.83, 41.30 , 27.56, 21.01, 15.72, 0.84, -0.75.

實例2過渡金屬催化劑化合物2(R7=Me,R12=R13=n-Bu),36%產率。1H NMR(C6D6):δ 8.08(m,1H),8.04(m,1H),7.84(m,1H),7.72(m,1H),7.54-7.58(m,2H),7.41(m,1H),7.32-7.35(m,3H),7.25(m,1H),7.18-7.22(m,5H),2.28(s,3H),1.94-2.11(m,4H),1.79(s,3H),0.94-1.05(m,4H),0.85-0.92(m,2H),0.83(s,3H),0.73-0.81(m,2H),0.56(t,J=7.2Hz,3H),0.55(s,3H),0.53(s,3H),0.52(t,J=7.4Hz,3H),-0.07(s,3H).13C NMR(CD2Cl2):δ 162.63,151.35,150.90,141.56,140.11,138.87,138.13,134.30,133.33,132.02,131.86,130.94,130.60,129.67,129.08,129.16,128.40,127.58,127.19,127.07,126.90,126.85,124.56,124.55,123.83,123.29,119.90,119.35,111.62,103.34,60.26,55.54,52.08,40.77,40.62,26.54,26.47,23.44,20.99,15.88,14.06,14.02,0.79,-0.69. Example 2 Transition Metal Catalyst Compound 2 (R 7 =Me, R 12 =R 13 =n-Bu), 36% yield. 1 H NMR (C 6 D 6 ): δ 8.08 (m, 1H), 8.04 (m, 1H), 7.84 (m, 1H), 7.72 (m, 1H), 7.54 - 7.58 (m, 2H), 7.41 ( m, 1H), 7.32-7.35 (m, 3H), 7.25 (m, 1H), 7.18-7.22 (m, 5H), 2.28 (s, 3H), 1.94-2.11 (m, 4H), 1.79 (s, 3H), 0.94-1.05 (m, 4H), 0.85-0.92 (m, 2H), 0.83 (s, 3H), 0.73-0.81 (m, 2H), 0.56 (t, J = 7.2 Hz, 3H), 0.55 (s, 3H), 0.53 (s, 3H), 0.52 (t, J = 7.4 Hz, 3H), -0.07 (s, 3H). 13 C NMR (CD 2 Cl 2 ): δ 162.63, 151.35, 150.90, 141.56,140.11,138.87,138.13,134.30,133.33,132.02,131.86,130.94,130.60,129.67,129.08,129.16,128.40,127.58,127.19,127.07,126.90,126.85,124.56,124.55,123.83,123.29,119.90,119.35, 111.62, 103.34, 60.26, 55.54, 52.08, 40.77, 40.62, 26.54, 26.47, 23.44, 20.99, 15.88, 14.06, 14.02, 0.79, -0.69.

實例3過渡金屬催化劑化合物3(R7=F,R12=R13=Me),8%產率。1H NMR(CD2Cl2):δ 8.27(m,1H),7.96(m,1H),7.83(m,1H),7.77(m,1H),7.73(m,1H),7.60-7.63(m,2H), 7.49-7.56(m,3H),7.43(m,1H),7.38(m,1H),7.30-7.33(m,2H),7.21(m,1H),7.17(m,1H),1.94(s,3H),1.50(s,6H),0.66(s,6H),0.49(s,3H),-0.53(s,3H).13C NMR(CD2Cl2):δ 160.62,159.54,157.13,154.41,153.85,139.31,138.68,138.26,137.67,131.86,130.80,130.56,129.11,128.95,128.59,127.63,127.64,127.36,127.14,127.00,124.52,124.34,123.83,123.00,120.38,119.93,119.26,119.06,118.44,118.21,111.56,103.01,61.17,52.60,47.33,27.50,15.69,0.47,-1.02. Example 3 Transition Metal Catalyst Compound 3 (R 7 =F, R 12 =R 13 =Me), 8% yield. 1 H NMR (CD 2 Cl 2 ): δ 8.27 (m, 1H), 7.96 (m, 1H), 7.83 (m, 1H), 7.77 (m, 1H), 7.73 (m, 1H), 7.60-7.63 ( m, 2H), 7.49-7.56 (m, 3H), 7.43 (m, 1H), 7.38 (m, 1H), 7.30-7.33 (m, 2H), 7.21 (m, 1H), 7.17 (m, 1H) , 1.94 (s, 3H), 1.50 (s, 6H), 0.66 (s, 6H), 0.49 (s, 3H), -0.53 (s, 3H). 13 C NMR (CD 2 Cl 2 ): δ 160.62, 159.54,157.13,154.41,153.85,139.31,138.68,138.26,137.67,131.86,130.80,130.56,129.11,128.95,128.59,127.63,127.64,127.36,127.14,127.00,124.52,124.34,123.83,123.00,120.38,119.93, 119.26, 119.06, 118.44, 118.21, 111.56, 103.01, 61.17, 52.60, 47.33, 27.50, 15.69, 0.47, -1.02.

實例4過渡金屬催化劑化合物4(R7=F,R12=R13=n-Bu),7%產率。1H NMR(C6D6):δ 8.02(m,1H),7.98(m,1H),7.72(m,1H),7.65(m,1H),7.54-7.56(m,2H),7.30-7.35(m,2H),7.17-7.27(m,8H),1.94-2.05(m,4H),1.20-1.25(m,4H),0.94-1.03(m,4H),0.82(s,6H),0.56(t,J=7.3Hz,3H),0.51(t,J=7.3Hz,3H),0.43(s,3H),0.37(s,3H),-0.08(s,3H).13C NMR(CD2Cl2):δ 160.68,159.47,157.06,151.38,151.09,141.35,140.69,138.29,137.69,131.87,131.19,130.91,130.75,129.13,129.06,128.50,127.68,127.40,127.13,126.98,124.36,124.11,123.85,123.33,120.03,119.49,119.17,118.97,118.69,118.46,111.77,102.87,61.21,55.60,52.94,40.73,40.59,26.53,26.46,23.42,15.87,14.05,14.00,0.45,-0.92. Example 4 Transition Metal Catalyst Compound 4 (R 7 =F, R 12 =R 13 =n-Bu), 7% yield. 1 H NMR (C 6 D 6 ): δ 8.02 (m, 1H), 7.98 (m, 1H), 7.72 (m, 1H), 7.65 (m, 1H), 7.54-7.56 (m, 2H), 7.30- 7.35 (m, 2H), 7.17-7.27 (m, 8H), 1.94-2.05 (m, 4H), 1.20-1.25 (m, 4H), 0.94-1.03 (m, 4H), 0.82 (s, 6H), 0.56 (t, J = 7.3 Hz, 3H), 0.51 (t, J = 7.3 Hz, 3H), 0.43 (s, 3H), 0.37 (s, 3H), -0.08 (s, 3H). 13 C NMR ( CD 2 Cl 2 ): δ 160.68, 159.47, 157.06, 151.38, 151.09, 141.35, 140.69, 138.29, 137.69, 131.87, 131.19, 130.91, 130.75, 129.13, 129.06, 128.50, 127.68, 127.40, 127.13, 126.98, 124.36, 124.11 , 123.85, 123.33, 120.03, 119.49, 119.17, 118.97, 118.69, 118.46, 111.77, 102.87, 61.21, 55.60, 52.94, 40.73, 40.59, 26.53, 26.46, 23.42, 15.87, 14.05, 14.00, 0.45, -0.92.

實例5過渡金屬催化劑化合物5(R7=Me,R12=R13=n-十四烷基),5%產率。1H NMR(CD2Cl2):δ 8.30(d,1H),7.81(d,1H),7.74-7.24(m,14H),2.43(s,3H),2.02(m,3H),1.93(s,3H),1.27-0.60(m,64H),0.48(s,3H),-0.57(s,3H).13C NMR(CD2Cl2):δ 163.18,151.36,150.92,141.56,140.06,138.89,138.29,135.07,133.26,135.07,033.26,130.94,130.91,130.85,130.81,129.19,129.02,128.15,127.15,127.05,126.97,126.82,124.72,124.23,123.78,123.29,119.90,119.31,111.78,102.32,60.23,55.60,52.08,40.81,34.57,32.38,30.42,30.11,30.02,29.81,24.37,24.24,23.14,23.05,21.05,15.88,14.34,7.84,5.75,4.87 Example 5 Transition Metal Catalyst Compound 5 (R 7 =Me, R 12 =R 13 =n-tetradecyl), 5% yield. 1 H NMR (CD 2 Cl 2 ): δ 8.30 (d, 1H), 7.81 (d, 1H), 7.74-7.24 (m, 14H), 2.43 (s, 3H), 2.02 (m, 3H), 1.93 ( s, 3H), 1.27-0.60 (m, 64H), 0.48 (s, 3H), -0.57 (s, 3H). 13 C NMR (CD 2 Cl 2 ): δ 163.18, 151.36, 150.92, 141.56, 140.06, 138.89,138.29,135.07,133.26,135.07,033.26,130.94,130.91,130.85,130.81,129.19,129.02,128.15,127.15,127.05,126.97,126.82,124.72,124.23,123.78,123.29,119.90,119.31,111.78,102.32, 60.23, 55.60, 52.08, 40.81, 34.57, 32.38, 30.42, 30.11, 30.02, 29.81, 24.37, 24.24, 23.14, 23.05, 21.05, 15.88, 14.34, 7.84, 5.75, 4.87

[實施例6]根據本發明之過渡金屬催化劑6的製備 [Example 6] Preparation of Transition Metal Catalyst 6 According to the Present Invention

化合物D6的製備 Preparation of Compound D6

將對甲酚(30.0g,277mmol,1當量)溶於MeCN(3000mL)中。將對甲苯磺酸一水合物(p-Toluenesulfonic acid monohydrate;p-TSA)(52.8g,277mmol,1當量)加入反應溶液中並攪拌15分鐘,於其內緩慢加入N-碘代琥珀醯亞胺(NIS)(62.0g,277mmol,1當量)超過30分鐘,並將反應溶液攪拌12小時。攪拌12小時之後,加入相同體積的蒸餾水。將形成的產物以***(200mL×2)萃取,將回收的有機物以Na2SO3水溶液和蒸餾水處理,並以無水Na2SO4乾燥以除去溶劑。所得化合物(2-碘-4-甲基苯酚;56.5g,產率87%)未經進一步純化用於下一步反應。 P-cresol (30.0 g, 277 mmol, 1 eq.) was dissolved in MeCN (3000 mL). P-Toluenesulfonic acid monohydrate (p-TSA) (52.8 g, 277 mmol, 1 equivalent) was added to the reaction solution and stirred for 15 minutes, and N-iodosuccinimide was slowly added thereto. (NIS) (62.0 g, 277 mmol, 1 equivalent) over 30 minutes, and the reaction solution was stirred for 12 hours. After stirring for 12 hours, the same volume of distilled water was added. The product thus formed was extracted with diethyl ether (200 mL × 2), and the recovered organic material was treated with aqueous Na 2 SO 3 and distilled water and dried over anhydrous Na 2 SO 4 to remove solvent. The obtained compound (2-iodo-4-methylphenol; 56.5 g, yield 87%) was used for the next reaction without further purification.

在氮氣氛下,將2-碘-4-甲基苯酚(56.5g,240mmol,1當量)溶於無水THF(250mL)中。依次將N,N-二異丙基乙胺(DIPEA)(62.7mL,360mmol,1.5當量)和氯甲基甲基醚(MOMCl)(27.5mL,360mmol,1.5當量)加入反應溶液中。將反應溶液在60℃下攪拌12小時,然後加入到蒸餾水(500mL)中以終止反應。將反應溶液以己烷(200mL×2)萃取,將得到的有機層以蒸餾水和無水Na2SO4處理,並乾燥,藉此得到粗產物。使用填充有矽膠60(40-63μm)的管柱藉由急速層析法(沖堤液:己烷)純化粗產物以獲得呈黃色油形式的標題化合物D6(65.9g,99%產率)。 2-iodo-4-methylphenol (56.5 g, 240 mmol, 1 eq.) was dissolved in dry THF (250 mL). N,N-Diisopropylethylamine (DIPEA) (62.7 mL, 360 mmol, 1.5 eq.) and chloromethyl methyl ether (MOMCl) (27.5 mL, 360 mmol, 1.5 eq.) were added to the reaction solution. The reaction solution was stirred at 60 ° C for 12 hours and then added to distilled water (500 mL) to terminate the reaction. The reaction solution was extracted with hexane (200 mL × 2), and the obtained organic layer was treated with distilled water and anhydrous Na 2 SO 4 and dried to give a crude product. The crude product was purified by EtOAc EtOAc (EtOAc)

1H NMR(400MHz,CDCl3):δ 7.60(s,1H),7.05-7.08(m,1H),6.94(d,J=8.3Hz,1H),5.19(s,2H),3.50(s,3H),2.25(s,3H). 1 H NMR (400MHz, CDCl 3 ): δ 7.60 (s, 1H), 7.05-7.08 (m, 1H), 6.94 (d, J = 8.3Hz, 1H), 5.19 (s, 2H), 3.50 (s, 3H), 2.25 (s, 3H).

化合物E6的製備 Preparation of Compound E6

將2,7-二-三級丁基-9H-咔唑(24.8g,89.0mmol,1當量)、化合物D6(29.6g,107mmol,1.2當量)、CuI(3.4g,18.0mmol,0.2當量)、K3PO4(57.0g,267mmol,3當量)和N,N’-二甲基-1,2-乙二胺(2.35g,26.7mmol,0.3當量)溶於無水甲苯(180mL)中,並在120℃下攪拌12小時。然後,加入蒸餾水(500mL)以終止反應。有機層以甲苯(100mL×3)萃取,依次以蒸餾水和無水Na2SO4處理,並乾燥以得到粗產物。經由Kugelrohr蒸餾純化粗產物,以獲得標題化合物E6,為黑色油狀物(32.2g,85%產率)。 2,7-di-tertiary butyl-9H-carbazole (24.8 g, 89.0 mmol, 1 eq.), compound D6 (29.6 g, 107 mmol, 1.2 eq.), CuI (3.4 g, 18.0 mmol, 0.2 eq.) K 3 PO 4 (57.0 g, 267 mmol, 3 equivalents) and N,N'-dimethyl-1,2-ethanediamine (2.35 g, 26.7 mmol, 0.3 eq.) were dissolved in anhydrous toluene (180 mL). It was stirred at 120 ° C for 12 hours. Then, distilled water (500 mL) was added to terminate the reaction. The organic layer was extracted with toluene (100 mL×3), and then treated with distilled water and anhydrous Na 2 SO 4 and dried to give a crude product. The crude product was purified by EtOAc EtOAc (EtOAc)

1H NMR(400MHz,CDCl3):δ 8.05(d,J=8.2Hz,2H),7.29-7.41(m,7H),4.98(s,2H),3.24(s,3H),2.45(s,3H),1.42(s,18H). 1 H NMR (400MHz, CDCl 3 ): δ 8.05 (d, J = 8.2Hz, 2H), 7.29-7.41 (m, 7H), 4.98 (s, 2H), 3.24 (s, 3H), 2.45 (s, 3H), 1.42 (s, 18H).

化合物F6的製備 Preparation of Compound F6

在室溫下,將n-BuLi(58.0mL,145mmol,2當量)緩慢加入化合物E6(31.1g,72.0mmol,1當量)的無水***溶液(850mL)中,且混合物在室溫下攪拌2小時。在0℃下將1,2-二溴四氟乙烷(74.8g,288mmol,4當量)緩慢加入到反應溶液中,攪拌12小時,然後加入到蒸餾水(500mL)中以終止反應。回收有機層,以無水Na2SO4處理並乾燥以得到 產物(9-{3-溴-5-甲基-2-(甲氧基甲氧基)苯基}-2,7-二-三級丁基-9H-咔唑;32.1g,88%產率),並且不經進一步純化用於下一步反應。 N-BuLi (58.0 mL, 145 mmol, 2 eq.) was slowly added to a solution of compound E6 (31.1 g, 72.0 mmol, 1 eq. . 1,2-Dibromotetrafluoroethane (74.8 g, 288 mmol, 4 equivalents) was slowly added to the reaction solution at 0 ° C, stirred for 12 hours, and then added to distilled water (500 mL) to terminate the reaction. The organic layer was recovered, treated with anhydrous Na 2 SO 4 and dried to give product (9-{3-bromo-5-methyl-2-(methoxymethoxy)phenyl}-2,7-di- Grade butyl-9H-carbazole; 32.1 g, 88% yield) and was used in the next step without further purification.

將9-{3-溴-5-甲基-2-(甲氧基甲氧基)苯基}-2,7-二-三級丁基-9H-咔唑(32.1g,75.0mmol)加入到甲醇(220mL)和THF(220mL)和鹽酸(12M,2.5mL)的混合溶液中,在60℃下攪拌12小時,然後加入蒸餾水(1000mL)以終止反應。將混合物以***(200mL×2)處理以獲得有機層,並將有機層以無水Na2SO4處理並乾燥以獲得粗產物。使用填充有矽膠60(40-63μm)的管柱藉由急速層析法(沖堤液:己烷/二氯甲烷)純化粗產物,以獲得呈白色固體形式的標題化合物F6(22.2g,64%產率)。 Add 9-{3-bromo-5-methyl-2-(methoxymethoxy)phenyl}-2,7-di-tert-butyl-9H-indazole (32.1 g, 75.0 mmol) To a mixed solution of methanol (220 mL) and THF (220 mL) and hydrochloric acid (12M, 2.5 mL), the mixture was stirred at 60 ° C for 12 hours, and then distilled water (1000 mL) was added to terminate the reaction. The mixture was treated with diethyl ether (200 mL × 2) to give an organic layer, and the organic layer was treated with anhydrous Na 2 SO 4 and dried to give a crude product. The crude product was purified by flash chromatography eluting EtOAc EtOAc (EtOAc:EtOAc %Yield).

1H NMR(400MHz,CDCl3):δ 8.00(dd,J 1 =8.3Hz,J 2 =0.5Hz,2H),7.51(dd,J 1=2.1Hz,J 2=0.6Hz,1H),7.35(dd,J 1 =8.2Hz,J 2 =1.7Hz,2H),7.15(dd,J 1 =2.1Hz,J 2 =0.7Hz,1H),7.08(d,J=1.2Hz,2H),5.42(s,1H),2.37(s,3H),1.36(s,18H). 1 H NMR (400MHz, CDCl 3 ): δ 8.00 (dd, J 1 = 8.3Hz, J 2 = 0.5Hz, 2H), 7.51 (dd, J 1 = 2.1Hz, J 2 = 0.6Hz, 1H), 7.35 (dd, J 1 = 8.2 Hz, J 2 = 1.7 Hz, 2H), 7.15 (dd, J 1 = 2.1 Hz, J 2 = 0.7 Hz, 1H), 7.08 (d, J = 1.2 Hz, 2H), 5.42 (s, 1H), 2.37 (s, 3H), 1.36 (s, 18H).

化合物G6的製備 Preparation of Compound G6

將K2CO3(30mmol)和溴丙烯(30mmol)加入到無水丙酮(200mL)和酚(20mmol)中,隨後回流16小時。經真空除去 丙酮,並加入蒸餾水,隨後以二氯甲烷(50mL×3)萃取。將有機層以無水Na2SO4處理並乾燥,使用填充有矽膠60(40-63μm)的管柱藉由急速層析法(沖堤液:己烷)純化所得的殘餘物,以獲得標題化合物G6(99%產率)。 K 2 CO 3 (30 mmol) and bromopropene (30 mmol) were added to dry acetone (200 mL) and phenol (20 mmol), followed by reflux for 16 hours. The acetone was removed in vacuo, and distilled water was added, followed by extraction with dichloromethane (50 mL×3). The organic layer was treated with anhydrous Na 2 SO 4 and dried, and the residue obtained was purified by flash chromatography (diluent: hexane) using a column packed with silica gel 60 (40-63 μm) to obtain the title compound. G6 (99% yield).

1H NMR(400MHz,CDCl3):δ 8.00(d,J=8.2Hz,2H),7.57(d,J=1.9Hz,2H),7.35(dd,J 1 =8.2Hz,J 2 =1.6Hz,2H),7.25(s,1H),7.20(d,J=1.3Hz,2H),5.40-5.50(m,1H),4.76-4.84(m,2H),3.85(d,J=6.0Hz,2H),2.41(s,3H),1.40(s,18H). 1 H NMR (400MHz, CDCl 3 ): δ 8.00 (d, J = 8.2Hz, 2H), 7.57 (d, J = 1.9Hz, 2H), 7.35 (dd, J 1 = 8.2Hz, J 2 = 1.6Hz , 2H), 7.25 (s, 1H), 7.20 (d, J = 1.3 Hz, 2H), 5.40-5.50 (m, 1H), 4.76-4.84 (m, 2H), 3.85 (d, J = 6.0 Hz, 2H), 2.41 (s, 3H), 1.40 (s, 18H).

化合物H6的製備 Preparation of Compound H6

在-78℃下,將n-BuLi(2.5M於己烷中,91mmol)緩慢加入化合物G6(70mmol)的甲苯(200mL)溶液中,然後升溫至-20℃。將反應溶液再次冷卻至-78℃,迅速加入二氯二乙基矽烷(210mmol),將溫度升至室溫,並將混合物攪拌5小時。藉由矽藻土過濾除去無機鹽。在除去溶劑之後,經真空除去過量的二氯二乙基矽烷,以獲得標題化合物H6(99%產率),且不經進一步純化用於下一步反應。 n-BuLi (2.5 M in hexane, 91 mmol) was slowly added to a solution of compound G6 (70 mmol) in toluene (200 mL) and then warmed to -20 °C. The reaction solution was again cooled to -78 ° C, dichlorodiethyl decane (210 mmol) was quickly added, the temperature was warmed to room temperature, and the mixture was stirred for 5 hr. The inorganic salt was removed by filtration through diatomaceous earth. After the solvent was removed, the excess of dichloromethane was evaporated in vacuo to afford the title compound H6 (99% yield).

1H NMR(400MHz,CDCl3):δ 7.99(d,J=8.0Hz,2H),7.61(s,1H),7.40(s,1H),7.34(d,J=8.2Hz,2H),7.28(s,2H),5.29-5.39(m,1H),4.80(d,J=10.5Hz,1H),4.65(d,J =17.2Hz,1H),3.59(d,J=5.7Hz,2H),2.44(s,3H),1.38(s,18H),1.03-1.31(m,10H). 1 H NMR (400MHz, CDCl 3 ): δ 7.99 (d, J = 8.0Hz, 2H), 7.61 (s, 1H), 7.40 (s, 1H), 7.34 (d, J = 8.2Hz, 2H), 7.28 (s, 2H), 5.29-5.39 (m, 1H), 4.80 (d, J = 10.5 Hz, 1H), 4.65 (d, J = 17.2 Hz, 1H), 3.59 (d, J = 5.7 Hz, 2H) , 2.44 (s, 3H), 1.38 (s, 18H), 1.03-1.31 (m, 10H).

化合物I6的製備 Preparation of Compound I6

在-78℃下,將n-BuLi(2.5M在己烷中,31.6mmol)緩慢滴加到2-甲基-9bH-環戊[a]萘(30.1mmol)的THF(112mL)溶液中。將反應混合物加熱至室溫,並進一步攪拌2小時。當攪拌結束後,將混合物冷卻至-78℃,並透過注射器加入化合物H6(33.1mmol)的甲苯(14mL)溶液。將反應混合物溶液加熱至室溫,進一步攪拌3小時,然後加入蒸餾水(200mL)中以終止反應。將有機層以甲苯(2×50mL)萃取,以Na2SO4除去水,並經真空蒸餾除去溶劑以獲得粗產物。然後,使用填充有矽膠60(40-63μm)的管柱,藉由急速層析法(沖堤液:己烷/二氯甲烷,10/1體積)純化粗產物,以獲得標題化合物I6(65%產率)。 n-BuLi (2.5 M in hexane, 31.6 mmol) was slowly added dropwise to a solution of 2-methyl-9bH-cyclopenta[a]naphthalene (30.1 mmol) in THF (112 mL). The reaction mixture was warmed to room temperature and further stirred for 2 hours. After the end of the stirring, the mixture was cooled to -78 ° C, and a solution of compound H6 (33.1 mmol) in toluene (14 mL) was added through a syringe. The reaction mixture solution was heated to room temperature, further stirred for 3 hours, and then added to distilled water (200 mL) to terminate the reaction. The organic layer with toluene (2 × 50mL) and extracted to remove water 2 SO 4 Na, and the solvent was removed by vacuum distillation to obtain a crude product. Then, using a column packed with silica gel 60 (40-63 μm), the crude product was purified by flash chromatography (diluent: hexane/dichloromethane, 10/1 vol) to give the title compound I6 (65 %Yield).

1H NMR(400MHz,CDCl3):δ 8.21(d,J=8.2Hz,1H),8.10(d,J=8.2Hz,2H),7.94(d,J=8.0Hz,1H),7.54-7.60(m,2H),7.37-7.50(m,7H),7.30(br.s,2H),5.49-5.59(m,1H),4.86-4.94(m,2H),4.42(s,1H),3.74-3.84(m,2H),2.48(s,3H),2.30(s,3H),1.47(s,9H),1.45(s,9H),0.75-1.19(m,10H). 1 H NMR (400 MHz, CDCl 3 ): δ 8.21 (d, J = 8.2 Hz, 1H), 8.10 (d, J = 8.2 Hz, 2H), 7.94 (d, J = 8.0 Hz, 1H), 7.54 - 7.60 (m, 2H), 7.37-7.50 (m, 7H), 7.30 (br.s, 2H), 5.49-5.59 (m, 1H), 4.86-4.94 (m, 2H), 4.42 (s, 1H), 3.74 -3.84 (m, 2H), 2.48 (s, 3H), 2.30 (s, 3H), 1.47 (s, 9H), 1.45 (s, 9H), 0.75-1.19 (m, 10H).

化合物J6的製備 Preparation of Compound J6

將Et3N(45mmol)和化合物I6(10mmol)在甲苯(70mL)中的溶液冷卻至-78℃,並緩慢加入n-BuLi(2.5M,在己烷中,22mmol)。將反應混合物加熱至室溫,攪拌20小時,再次冷卻至-78℃,然後透過注射器緩慢滴加TiCl4(15mmol)的甲苯(22mL)溶液。在TiCl4的添加完成之後,將反應混合物加熱至室溫,並在90℃下攪拌16小時。將混合物冷卻至室溫,然後經真空除去溶劑。除去溶劑之後,加入熱的甲基環己烷以通過矽藻土過濾器除去不溶的無機鹽。將濾液的溶劑在真空中濃縮,隨後以甲基環己烷與己烷的混合溶液再結晶,以獲得標題化合物J6(61%產率)。 The Et 3 N (45mmol) and the compound I6 (10mmol) was cooled in toluene (70 mL) to the -78 ℃, was slowly added n-BuLi (2.5M, in hexanes, 22mmol). The reaction mixture was warmed to room temperature, stirred for 20 hr and then cooled again to -78 ° C, then a solution of TiCl 4 (15 mmol) in toluene (22 mL) was slowly added dropwise through a syringe. After the addition of TiCl 4 was completed, the reaction mixture was heated to room temperature and stirred at 90 ° C for 16 hours. The mixture was cooled to room temperature and then the solvent was removed in vacuo. After removing the solvent, hot methylcyclohexane was added to remove the insoluble inorganic salt through a diatomaceous earth filter. The solvent of the filtrate was concentrated in vacuo, and then crystallised from a mixture of methyl cyclohexane and hexane to give the title compound J6 (61% yield).

1H NMR(400MHz,CDCl3):δ 8.06(d,J=7.5Hz,1H),7.85(d,J=8.2Hz,1H),7.80(d,J=8.2Hz,1H),7.62(d,J=8.0Hz,1H),7.53(td,J1=7.5Hz,J2=1.4Hz,1H),7.45-7.49(m,2H),7.36-7.40(m,3H),7.20-7.23(m,2H),7.12(dd,J1=8.2Hz,J2=1.7Hz,1H),6.95(dd,J1=6.2Hz,J2=1.2Hz,1H),2.55(s,3H),2.36(s,3H),1.32(s,9H),1.27(s,9H),1.11-1.40(m,10H). 1 H NMR (400MHz, CDCl 3 ): δ 8.06 (d, J = 7.5Hz, 1H), 7.85 (d, J = 8.2Hz, 1H), 7.80 (d, J = 8.2Hz, 1H), 7.62 (d , J = 8.0 Hz, 1H), 7.53 (td, J1 = 7.5 Hz, J2 = 1.4 Hz, 1H), 7.45-7.49 (m, 2H), 7.36-7.40 (m, 3H), 7.20-7.23 (m, 2H), 7.12 (dd, J1 = 8.2 Hz, J2 = 1.7 Hz, 1H), 6.95 (dd, J1 = 6.2 Hz, J2 = 1.2 Hz, 1H), 2.55 (s, 3H), 2.36 (s, 3H) , 1.32 (s, 9H), 1.27 (s, 9H), 1.11-1.40 (m, 10H).

化合物6的製備 Preparation of compound 6

將化合物J6(10mmol)溶於二***(100mL)中,並在-30 ℃下緩慢加入MeMgBr(2.9M的***,22mmol)溶液。將反應混合物緩慢加熱至室溫,攪拌22小時,然後經真空除去溶劑。將熱己烷加入到反應物中,並通過矽藻土過濾器除去不溶的無機鹽。經真空乾燥濾液,溶於己烷(70mL)中,然後再次通過矽藻土過濾器除去不溶的無機鹽。將所得濾液在-30℃下儲存12小時以獲得呈黃色固體形式的化合物6(30%產率)。 Compound J6 (10 mmol) was dissolved in diethyl ether (100 mL), and a solution of MeMgBr (2.9 M diethyl ether, 22 mmol) was slowly added at -30 °C. The reaction mixture was slowly warmed to room temperature and stirred for 22 hours then the solvent was evaporated in vacuo. Hot hexane was added to the reaction and the insoluble inorganic salt was removed through a diatomaceous earth filter. The filtrate was dried under vacuum, dissolved in hexanes (70 mL), and then filtered and then passed through a celite filter to remove insoluble inorganic salts. The resulting filtrate was stored at -30 °C for 12 hours to afford compound 6 (30% yield) as a yellow solid.

1H NMR(400MHz,CDCl3):δ 8.00-8.09(m,1H),7.91(t,J=8.4Hz,2H),7.67(d,J=7.3Hz,1H),7.33-7.48(m,5H),7.18-7.27(m,4H),7.11(m,1H),7.02(m,1H),2.51(s,3H),1.79(s,3H),1.32(s,9H),1.25(s,9H),1.00-1.23(m,10H),-0.29(s,6H),-1.13(s,6H).13C{1H}NMR(101MHz,CDCl3):δ 162.2,148.4,148.3,142.8,142.7,137.4,134.9,131.7,131.1,130.6,130.4,128.5,127.8,127.5,127.0,126.6,126.3,124.4,123.8,123.1,121.1,120.8,119.2,119.0,117.1,117.0,110.4,106.7,105.9,101.7,77.3,77.2,76.7,61.5,52.6,35.0,35.0,31.8,31.7,21.0,15.4,7.7,7.7,5.7,4.8. 1 H NMR (400MHz, CDCl 3 ): δ 8.00-8.09 (m, 1H), 7.91 (t, J = 8.4Hz, 2H), 7.67 (d, J = 7.3Hz, 1H), 7.33-7.48 (m, 5H), 7.18-7.27 (m, 4H), 7.11 (m, 1H), 7.02 (m, 1H), 2.51 (s, 3H), 1.79 (s, 3H), 1.32 (s, 9H), 1.25 (s) , 9H), 1.00-1.23 (m, 10H), -0.29 (s, 6H), -1.13 (s, 6H). 13 C{1H} NMR (101 MHz, CDCl 3 ): δ 162.2, 148.4, 148.3, 142.8 , 142.7, 137.4, 134.9, 131.7, 131.1, 130.6, 130.4, 128.5, 127.8, 127.5, 127.0, 126.6, 126.3, 124.4, 123.8, 123.1, 121.1, 120.8, 119.2, 119.0, 117.1, 117.0, 110.4, 106.7, 105.9 , 101.7, 77.3, 77.2, 76.7, 61.5, 52.6, 35.0, 35.0, 31.8, 31.7, 21.0, 15.4, 7.7, 7.7, 5.7, 4.8.

[比較例1]比較催化劑1的製備 [Comparative Example 1] Preparation of Comparative Catalyst 1

使用上述實例1至實例5的方法製備比較催化劑1。 Comparative Catalyst 1 was prepared using the methods of Examples 1 to 5 above.

1H NMR(CDCl3):δ 7.21(m,1H,Ar-H),7.17(m,1H,Ar-H),2.31(s,3H,Ar-Me),2.02(s,6H,C5Me4),1.95(s,6H,C5Me4),1.36(s,9H,Ar-tBu),0.62(s,3H,Si-Me),0.58(s,3H,Si-Me),0.21(s,3H),0.07(s,3H) 1 H NMR (CDCl 3 ): δ 7.21 (m, 1H, Ar-H), 7.17 (m, 1H, Ar-H), 2.31 (s, 3H, Ar-Me), 2.02 (s, 6H, C 5 ) Me 4 ), 1.95 (s, 6H, C 5 Me 4 ), 1.36 (s, 9H, Ar-tBu), 0.62 (s, 3H, Si-Me), 0.58 (s, 3H, Si-Me), 0.21 (s, 3H), 0.07 (s, 3H)

[比較例2]比較催化劑2的製備 [Comparative Example 2] Preparation of Comparative Catalyst 2

使用上述實例1至實例5的方法製備比較催化劑2。 Comparative Catalyst 2 was prepared using the methods of Examples 1 to 5 above.

1H NMR(CDCl3):δ 8.01(m,1H),7.82(m,1H),7.76(m,1H),7.72(m,1H),7.51(m,1H),7.31-7.39(m,3H),7.23(m,1H),6.25(t,2H),5.99(t,2H),1.77(s,3H),1.45(m,3H),1.39(m,3H),0.78(s,3H),0.57(s,3H),0.55(m,3H) 1 H NMR (CDCl 3 ): δ 8.01 (m, 1H), 7.82 (m, 1H), 7.76 (m, 1H), 7.72 (m, 1H), 7.51 (m, 1H), 7.31-7.39 (m, 3H), 7.23 (m, 1H), 6.25 (t, 2H), 5.99 (t, 2H), 1.77 (s, 3H), 1.45 (m, 3H), 1.39 (m, 3H), 0.78 (s, 3H) ), 0.57 (s, 3H), 0.55 (m, 3H)

[比較例3]比較催化劑3的製備 [Comparative Example 3] Preparation of Comparative Catalyst 3

化合物a的製備 Preparation of compound a

將1-溴-2,6-二異丙基苯(37.1g,154mmol,1.5當量)溶於無水THF(150mL)中,並在-78℃緩慢滴加n-BuLi(68.0mL,170mmol,1.65當量)。將混合物攪拌1小時,於其內快速加入ZnCl2(25.3g,185mmol,1.8當量),且混合物攪拌1小時並加熱至室溫,再另外攪拌1小時。將反應溶液轉移至壓力容器中,然後於其內依序加入Pd(dba)2(0.83g,1.00mmol,0.01當量)、RuPhos[S.Buchwald,J.Am.Chem.Soc.,2004,126(40),13028-13032](1.92g,4.00mmol,0.04當量)和2-溴-1-(甲氧基甲氧基)-4-甲基苯(23.7g,103mmol,1當量)。反應溶液以THF(50mL)和 NMP(100mL)稀釋。將反應溶液在100℃下攪拌12小時,並加入蒸餾水(150mL)以終止反應。所得溶液以***(200mL)萃取兩次。得到的有機材料以蒸餾水處理,以無水Na2SO4乾燥,然後經真空除去溶劑。所得產物以乙醇固化並分離得到的固體,以獲得2’,6’-二異丙基-2-甲氧基甲氧基-5-甲基聯苯(23.1g,72%產率),為白色結晶固體。將獲得的白色固體(23.1g,74.0mmol)溶解於甲醇(220mL)和THF(220mL)的混合溶液中。然後,於其內加入HCl(aq)(12M,2.2mL),將混合物在60℃下攪拌12小時,並加入蒸餾水(1000mL)以終止反應。在反應完成之後,產物以***(200mL×2)萃取,以蒸餾水處理,以無水Na2SO4乾燥,然後除去溶劑,以獲得化合物a,為白色固體(19.3g,97%)。 1-Bromo-2,6-diisopropylbenzene (37.1 g, 154 mmol, 1.5 eq.) was dissolved in anhydrous THF (150 mL), and n-BuLi (68.0 mL, 170 mmol, 1.65) was slowly added dropwise at -78 °C. equivalent). The mixture was stirred for 1 hour, and ZnCl 2 (25.3 g, 185 mmol, 1.8 eq.) was quickly added thereto, and the mixture was stirred for 1 hour and heated to room temperature, and then stirred for additional 1 hour. The reaction solution was transferred to a pressure vessel, and then Pd(dba) 2 (0.83 g, 1.00 mmol, 0.01 equivalent), RuPhos [S. Buchwald, J. Am . Chem . Soc ., 2004, 126) was sequentially added thereto. (40), 13028-13032] (1.92 g, 4.00 mmol, 0.04 eq.) and 2-bromo-1-(methoxymethoxy)-4-methylbenzene (23.7 g, 103 mmol, 1 eq.). The reaction solution was diluted with THF (50 mL) and NMP (100 mL). The reaction solution was stirred at 100 ° C for 12 hours, and distilled water (150 mL) was added to terminate the reaction. The resulting solution was extracted twice with diethyl ether (200 mL). The obtained organic material was treated with distilled water, dried over anhydrous Na 2 SO 4 and then solvent was evaporated in vacuo. The obtained product was solidified with ethanol and the obtained solid was separated to give 2',6'-diisopropyl-2-methoxymethoxy-5-methylbiphenyl (23.1 g, 72% yield) as White crystalline solid. The obtained white solid (23.1 g, 74.0 mmol) was dissolved in a mixed solution of methanol (220 mL) and THF (220 mL). Then, HCl (aq) (12 M, 2.2 mL) was added thereto, and the mixture was stirred at 60 ° C for 12 hours, and distilled water (1000 mL) was added to terminate the reaction. After completion of the reaction, the product (200mL × 2) and extracted with diethyl ether, treated with distilled water, dried over anhydrous Na 2 SO 4, the solvent was removed, to obtain compound a, as a white solid (19.3g, 97%).

1H NMR(400MHz,CDCl3):δ 7.39(t,J=7.8Hz,1H),7.27(d,J=7.7Hz,1H),7.08(d,J=8.3Hz,1H),6.88(d,J=8.3Hz,1H),6.82(s,1H),4.45(s,1H),2.62(m,2H),2.30(s,3H),1.10(d,J=6.9Hz,6H),1.07(d,J=6.8Hz,6H). 1 H NMR (400MHz, CDCl 3 ): δ 7.39 (t, J = 7.8Hz, 1H), 7.27 (d, J = 7.7Hz, 1H), 7.08 (d, J = 8.3Hz, 1H), 6.88 (d , J = 8.3 Hz, 1H), 6.82 (s, 1H), 4.45 (s, 1H), 2.62 (m, 2H), 2.30 (s, 3H), 1.10 (d, J = 6.9 Hz, 6H), 1.07 (d, J = 6.8 Hz, 6H).

化合物b的製備 Preparation of compound b

以與實例6的化合物6F相同的方式製備化合物b(95%產率)。 Compound b (95% yield) was prepared in the same manner as Compound 6F of Example 6.

1H NMR(400MHz,CDCl3):δ 7.41(t,J=7.8Hz,1H), 7.35(s,1H),7.27(d,J=7.8Hz,2H),6.82(s,1H),5.06(s,1H),2.52-2.60(m,2H),2.31(s,3H),1.15(d,J=6.9Hz,6H),1.09(d,J=6.9Hz,6H). 1 H NMR (400MHz, CDCl 3 ): δ 7.41 (t, J = 7.8Hz, 1H), 7.35 (s, 1H), 7.27 (d, J = 7.8Hz, 2H), 6.82 (s, 1H), 5.06 (s, 1H), 2.52-2.60 (m, 2H), 2.31 (s, 3H), 1.15 (d, J = 6.9 Hz, 6H), 1.09 (d, J = 6.9 Hz, 6H).

化合物c的製備 Preparation of compound c

以與實例6的化合物G6相同的方式製備化合物c(79%產率)。 Compound c (79% yield) was prepared in the same manner as Compound G6 of Example 6.

1H NMR(400MHz,CDCl3):δ 7.40(s,1H),7.35(t,J=7.7Hz,1H),7.20(d,J=7.7Hz,2H),6.86(s,1H),5.57-5.67(m,1H),4.97-5.05(m,2H),4.06(d,J=5.4Hz,2H),2.53-2.63(m,2H),2.32(s,3H),1.18(d,J=6.9Hz,6H),1.05(d,J=6.8Hz,6H). 1 H NMR (400MHz, CDCl 3 ): δ 7.40 (s, 1H), 7.35 (t, J = 7.7Hz, 1H), 7.20 (d, J = 7.7Hz, 2H), 6.86 (s, 1H), 5.57 -5.67 (m, 1H), 4.97-5.05 (m, 2H), 4.06 (d, J = 5.4 Hz, 2H), 2.53-2.63 (m, 2H), 2.32 (s, 3H), 1.18 (d, J =6.9 Hz, 6H), 1.05 (d, J = 6.8 Hz, 6H).

化合物d的製備 Preparation of compound d

以與實例6的化合物H6相同的方式製備化合物d(79%產率)。 Compound d (79% yield) was prepared in the same manner as Compound H6 of Example 6.

1H NMR(400MHz,CDCl3):δ 7.47-7.48(m,1H),7.33-7.37(m,1H),7.21(s,1H),7.19(s,1H),6.96-6.97(m,1H),5.51-5.61(m,1H),4.93-5.00(m,2H),3.88(dt,J1=5.6Hz,J2=1.4Hz,2H),2.67(m,2H),2.35(s,3H),1.16(d,J= 6.9Hz,6H),0.98-1.10(m,16H). 1 H NMR (400MHz, CDCl 3 ): δ 7.47-7.48 (m, 1H), 7.33-7.37 (m, 1H), 7.21 (s, 1H), 7.19 (s, 1H), 6.96-6.97 (m, 1H ), 5.51-5.61 (m, 1H), 4.93-5.00 (m, 2H), 3.88 (dt, J1 = 5.6 Hz, J2 = 1.4 Hz, 2H), 2.67 (m, 2H), 2.35 (s, 3H) , 1.16 (d, J = 6.9 Hz, 6H), 0.98-1.10 (m, 16H).

化合物e的製備 Preparation of compound e

以與實例6的化合物I6相同的方式製備化合物e(77%產率)。 Compound e (77% yield) was prepared in the same manners as Compound I6 of Example 6.

1H NMR(400MHz,CDCl3):δ 8.13(d,J=8.2Hz,1H),7.88(d,J=7.9Hz,1H),7.48-7.52(m,2H),7.38-7.45(m,2H),7.25-7.32(m,3H),7.19(s,1H),7.09(d,J=7.9Hz,1H),7.02(d,J=1.8Hz,1H),5.68-5.78(m,1H),5.06-5.15(m,2H),4.31(s,1H),4.06(dd,J1=5.5Hz,J2=1.1Hz,2H),2.83-2.94(m,2H),2.34(s,3H),2.13(s,3H),1.24(d,J=8.9Hz,3H),1.22(d,J=8.9Hz,3H),1.17(d,J=6.8Hz,3H),1.11(d,J=6.8Hz,3H),0.62-1.09(m,10H). 1 H NMR (400MHz, CDCl 3 ): δ 8.13 (d, J = 8.2Hz, 1H), 7.88 (d, J = 7.9Hz, 1H), 7.48-7.52 (m, 2H), 7.38-7.45 (m, 2H), 7.25-7.32 (m, 3H), 7.19 (s, 1H), 7.09 (d, J = 7.9 Hz, 1H), 7.02 (d, J = 1.8 Hz, 1H), 5.68-5.78 (m, 1H) ), 5.06-5.15 (m, 2H), 4.31 (s, 1H), 4.06 (dd, J1 = 5.5 Hz, J2 = 1.1 Hz, 2H), 2.83 - 2.94 (m, 2H), 2.34 (s, 3H) , 2.13 (s, 3H), 1.24 (d, J = 8.9 Hz, 3H), 1.22 (d, J = 8.9 Hz, 3H), 1.17 (d, J = 6.8 Hz, 3H), 1.11 (d, J = 6.8 Hz, 3H), 0.62-1.09 (m, 10H).

化合物f的製備 Preparation of compound f

以與實例6的化合物J6相同的方式製備化合物f(65%產率)。 Compound f (65% yield) was prepared in the same manner as Compound J6 of Example 6.

1H NMR(400MHz,CDCl3):δ 8.19(d,J=8.0Hz,1H),7.71(d,J=7.8Hz,1H),7.63(t,J=7.60Hz,1H),7.55(t,J=7.5Hz,1H),7.45(s,1H),7.35-7.37(m,2H),7.26-7.29(m, 1H),7.16(t,J=7.7Hz,1H),7.08(d,J=7.8Hz,1H),6.98(d,J=2.1Hz,1H),6.94(d,J=7.8Hz,1H),2.53(s,3H),2.45(s,3H),2.37-2.44(m,1H),2.23-2.30(m,1H),1.00-1.39(m,14H),0.97(d,J=6.8Hz,1H),0.70(d,J=6.8Hz,1H). 1 H NMR (400 MHz, CDCl 3 ): δ 8.19 (d, J = 8.0 Hz, 1H), 7.71 (d, J = 7.8 Hz, 1H), 7.63 (t, J = 7.60 Hz, 1H), 7.55 (t , J = 7.5 Hz, 1H), 7.45 (s, 1H), 7.35-7.37 (m, 2H), 7.26-7.29 (m, 1H), 7.16 (t, J = 7.7 Hz, 1H), 7.08 (d, J = 7.8 Hz, 1H), 6.98 (d, J = 2.1 Hz, 1H), 6.94 (d, J = 7.8 Hz, 1H), 2.53 (s, 3H), 2.45 (s, 3H), 2.37-2.44 ( m, 1H), 2.23-2.30 (m, 1H), 1.00-1.39 (m, 14H), 0.97 (d, J = 6.8 Hz, 1H), 0.70 (d, J = 6.8 Hz, 1H).

比較催化劑3的製備 Comparative preparation of catalyst 3

以與實例6的化合物6相同的方式製備比較催化劑3(91%產率)。 Comparative Catalyst 3 (91% yield) was prepared in the same manner as Compound 6 of Example 6.

1H NMR(600MHz,CD2Cl2):δ 8.25(d,J=7.8Hz,1H),7.79(d,J=7.6Hz,1H),7.59(t,J=7.3Hz,1H),7.49-7.53(m,2H),7.42(d,J=9.0Hz,1H),7.25-7.32(m,3H),7.19(d,J=8.1Hz,1H),7.16(d,J=7.9Hz,1H),7.00(br.s.,1H),2.69(m,1H),2.61(m,1H),2.40(s,3H),1.98(s,3H),1.00-1.21(m,19H),0.95(t,J=7.7Hz,3H),0.25(s,3H),-0.79(s,3H).13C{1H}NMR(151MHz,CD2Cl2):δ 186.9,170.9,170.5,160.9,160.1,157.8,156.8,154.9,154.3,153.9,153.7,152.1,151.4,151.0,150.7,150.6,150.1,149.9,147.7,147.0,145.6,134.7,125.2,82.9,77.4,77.2,76.8,76.6,74.6,54.1,54.0,48.4,48.2,46.8,46.7,44.3,38.8,31.0,30.9,29.3,28.5. 1 H NMR (600MHz, CD 2 Cl 2): δ 8.25 (d, J = 7.8Hz, 1H), 7.79 (d, J = 7.6Hz, 1H), 7.59 (t, J = 7.3Hz, 1H), 7.49 -7.53 (m, 2H), 7.42 (d, J = 9.0 Hz, 1H), 7.25-7.32 (m, 3H), 7.19 (d, J = 8.1 Hz, 1H), 7.16 (d, J = 7.9 Hz, 1H), 7.00 (br.s., 1H), 2.69 (m, 1H), 2.61 (m, 1H), 2.40 (s, 3H), 1.98 (s, 3H), 1.00-1.21 (m, 19H), 0.95 (t, J = 7.7 Hz, 3H), 0.25 (s, 3H), -0.79 (s, 3H). 13 C{ 1 H} NMR (151 MHz, CD 2 Cl 2 ): δ 186.9, 170.9, 170.5, 160.9,160.1,157.8,156.8,154.9,154.3,153.9,153.7,152.1,151.4,151.0,150.7,150.6,150.1,149.9,147.7,147.0,145.6,134.7,125.2,82.9,77.4,77.2,76.8,76.6, 74.6, 54.1, 54.0, 48.4, 48.2, 46.8, 46.7, 44.3, 38.8, 31.0, 30.9, 29.3, 28.5.

[實例7至實例20和比較例4至比較例9]乙烯與1-己烯的共聚合 [Example 7 to Example 20 and Comparative Example 4 to Comparative Example 9] Copolymerization of ethylene and 1-hexene

乙烯/1-己烯共聚合製程如下進行。 The ethylene/1-hexene copolymerization process was carried out as follows.

聚合反應在配備有機械攪拌器的溫度可控的連續聚合反應器中進行。將作為清除劑的TiBA/BHT(三異丁基鋁/2,6-二-三級丁基-4-甲基酚,莫耳比為1:1,30μmol,120μL,0.25M甲苯溶液)、1-己烯(120μL,150μL,180μL,200μL或400μL)和甲苯加入到此反應器中以使總體積為5mL。將反應器的溫度調節至聚合溫度(110℃或150℃),然後將攪拌速率設定為800rpm。取決於聚合溫度,將乙烯在150℃下以220psi加入,及在110℃下以200psi加入以保持乙烯恆定。催化劑的用量為5nmol、8nmole、10nmole、15nmole或20nmole,且共催化劑的量相對於聚合催化劑固定為5當量。將聚合催化劑加入反應器中,然後加入5當量的共催化劑肆(五氟苯基)硼酸三苯基甲基酯(TTB)開始聚合。聚合反應進行45秒至5分鐘,或者在待製備的聚合物不超過100mg至200mg時聚合終止。 The polymerization is carried out in a temperature controlled continuous polymerization reactor equipped with a mechanical stirrer. As scavenger TiBA / BHT (triisobutylaluminum / 2,6-di - tert.butyl-4-methylphenol, molar ratio 1: 1,30 μ mol, 120 μ L, 0.25M solution in toluene), 1-hexene (120 μ L, 150 μ L , 180 μ L, 200 μ L or 400 μ L) and toluene was added to this reactor to make a total volume of 5mL. The temperature of the reactor was adjusted to the polymerization temperature (110 ° C or 150 ° C), and then the stirring rate was set to 800 rpm. Depending on the polymerization temperature, ethylene was added at 220 psi at 150 ° C and at 200 ° C at 110 ° C to keep the ethylene constant. The amount of the catalyst used was 5 nmol, 8 nmole, 10 nmole, 15 nmole or 20 nmole, and the amount of the cocatalyst was fixed to 5 equivalents with respect to the polymerization catalyst. The polymerization catalyst was introduced into the reactor, and then polymerization was started by adding 5 equivalents of a co-catalyst triphenylmethyl pentoxide (pentafluorophenyl)borate (TTB). The polymerization is carried out for 45 seconds to 5 minutes, or the polymerization is terminated when the polymer to be prepared does not exceed 100 mg to 200 mg.

聚合完成之後,將反應器溫度冷卻至室溫,並藉由排空緩慢除去反應器中的乙烯。然後將製備的聚合物經真空乾燥。 After the completion of the polymerization, the reactor temperature was cooled to room temperature, and the ethylene in the reactor was slowly removed by evacuation. The prepared polymer was then dried under vacuum.

實例和比較例的聚合反應條件和所得聚合物的物理性質顯示於下表1中。 The polymerization conditions of the examples and comparative examples and the physical properties of the obtained polymer are shown in Table 1 below.

如表1所示,可以理解的是,實例7至實例20的乙烯/1-己烯共聚的活性高於或等於比較例4至比較例9的活性。 As shown in Table 1, it is understood that the activities of the ethylene/1-hexene copolymerization of Examples 7 to 20 are higher than or equal to those of Comparative Examples 4 to 9.

具體而言,可以確認的是,實例20在150℃的聚合溫度下的活性分別比比較例5高15倍,比比較例7高34.5 倍,及比比較例9高6.7倍。另外,該等實例的催化劑在聚合溫度110℃時的聚合活性分別比比較例4高2.7倍,比比較例6高44倍,及比比較例8高1.7倍,且因此該等實例呈現出高聚合性質。 Specifically, it was confirmed that the activity of Example 20 at a polymerization temperature of 150 ° C was 15 times higher than that of Comparative Example 5, 34.5 times higher than Comparative Example 7, and 6.7 times higher than Comparative Example 9. Further, the polymerization activities of the catalysts of the above examples were 2.7 times higher at a polymerization temperature of 110 ° C than that of Comparative Example 4, 44 times higher than Comparative Example 6, and 1.7 times higher than Comparative Example 8, and thus the examples exhibited high Polymerization properties.

此外,關於使用比較例1和比較例2的催化劑的比較例4至比較例7中的關於共聚單體即1-己烯的聚合特性,在聚合時添加200μL至400μL的共聚單體能使得共聚物中1-己烯的含量為約10mol%,而在使用實例1至實例5的催化劑的實例7至實例20中,即使添加120μL至150μL的共聚單體,共聚物中也含有等量位準(equivalent level)的共聚單體含量。 Further, regarding the polymerization characteristics of the comonomer, i.e., 1-hexene, in Comparative Example 4 to Comparative Example 7 using the catalysts of Comparative Example 1 and Comparative Example 2, the addition of 200 μL to 400 μL of the comonomer at the time of polymerization enables copolymerization The content of 1-hexene in the product was about 10 mol%, and in Examples 7 to 20 using the catalysts of Examples 1 to 5, even if 120 μL to 150 μL of the comonomer was added, the copolymer contained an equivalent amount. (equivalent level) comonomer content.

此即,證實了當使用實例1至實例5的聚合催化劑時,相較於其中使用比較例1和比較例2的催化劑的情況,其可以藉由加入相當於約30%至75%量的共聚單體來製備含有等量位準的共聚單體的共聚物。此特徵表明,相較於比較例1和比較例2的催化劑,本發明之實例1至實例5的催化劑在結構上對共聚單體具有高度反應性,並且在具有較小含量的共聚單體的濃度下可以製備具有較低密度的產物。 That is, it was confirmed that when the polymerization catalysts of Examples 1 to 5 were used, it was possible to add copolymerization equivalent to about 30% to 75% by using the catalyst of Comparative Example 1 and Comparative Example 2 therein. Monomers are used to prepare copolymers containing equal amounts of comonomer. This feature indicates that the catalysts of Examples 1 to 5 of the present invention are structurally highly reactive toward comonomers and have a lower content of comonomers than the catalysts of Comparative Example 1 and Comparative Example 2. Products with lower densities can be prepared at concentrations.

另外,除了所製備的聚合物中的共聚單體含量之外,作為可能影響聚合物的物理性質的因素,可以考慮聚合物 的分子量分布。可以確認的是,當使用比較例1的催化劑進行聚合時,分子量分布為2.4至2.8(比較例4和比較例5),而當使用實例1至實例5的催化劑進行聚合時,分子量分布為1.9至2.3,這是相對地非常窄的分子量分布(實例7至實例20)。這表明,與由比較例1的催化劑製備的共聚物相比,由實例1至實例5的催化劑製備的共聚物具有均勻的分子量,並且在諸如拉伸強度、衝擊強度等性質方面呈現出更好的特性。 Further, in addition to the comonomer content in the prepared polymer, the molecular weight distribution of the polymer can be considered as a factor that may affect the physical properties of the polymer. It was confirmed that when polymerization was carried out using the catalyst of Comparative Example 1, the molecular weight distribution was 2.4 to 2.8 (Comparative Example 4 and Comparative Example 5), and when polymerization was carried out using the catalysts of Examples 1 to 5, the molecular weight distribution was 1.9. To 2.3, this is a relatively very narrow molecular weight distribution (Examples 7 through 20). This indicates that the copolymer prepared from the catalysts of Examples 1 to 5 has a uniform molecular weight and exhibits better properties such as tensile strength, impact strength and the like as compared with the copolymer prepared by the catalyst of Comparative Example 1. Characteristics.

儘管如上述已經更詳細地描述了本發明的實例,但是本案所屬技術領域中具有通常知識者將理解,可以對本發明進行各種修改而不偏離隨附的本發明申請專利範圍之範圍。因此,在本發明的實例中的進一步修改將不偏離本發明的技術。 While the invention has been described in detail hereinabove, it is understood that the invention may be Therefore, further modifications in the examples of the invention will not depart from the techniques of the invention.

Claims (15)

一種過渡金屬化合物,係由以下化學式1表示: 在化學式1中,M是週期表中第4族的過渡金屬;R1至R3各自獨立為氫、(C1-C20)烷基、(C6-C20)芳基、(C3-C20)環烷基、鹵素、(C2-C20)烯基、(C3-C20)雜芳基、(C3-C20)雜環烷基、-ORa1、-SRa2、-NRa3Ra4或-PRa5Ra6,並且R2和R3可以透過具有或不具有芳香環的(C3-C7)伸烷基或(C3-C7)伸烯基鏈結以形成稠合環;R4和R5各自獨立為(C1-C20)烷基、鹵(C1-C20)烷基、(C3-C20)環烷基、(C6-C20)芳基、(C1-C20)烷基(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C3-C20)雜芳基、-ORa1、-SRa2、-NRa3Ra4或-PRa5Ra6,或者R4和R5可以透過(C4-C7)伸烷基鏈結以形成環;R6至R8各自獨立為氫、(C1-C20)烷基、鹵(C1-C20)烷基、鹵素、(C6-C20)芳基、(C3-C20)環烷基、(C2-C20)烯基、(C3-C20)雜芳基、(C1-C20)雜環烷基、-ORa1、 -SRa2、-NRa3Ra4或-PRa5Ra6,或者R6至R8可以透過具有或不具有芳香環的(C4-C7)伸烯基與相鄰取代基鏈結以形成稠合環;Ar1為茀基或咔唑基,且Ar1的茀基或咔唑基可進一步經選自氫、(C1-C20)烷基、鹵(C1-C20)烷基、(C6-C20)芳基、(C1-C20)烷基(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、-ORa1、-SRa2、-NRa3Ra4和-PRa5Ra6組成之群組中的至少一個所取代;Ra1至Ra6各自獨立為(C1-C20)烷基或(C6-C20)芳基;R1至R3和R6至R8的烷基、芳基、環烷基、雜芳基或雜環烷基以及Ra1至Ra6的烷基或芳基可進一步經選自鹵素、(C1-C20)烷基、鹵(C1-C20)烷基、(C1-C20)烷氧基、(C6-C20)芳基、(C6-C20)芳氧基、硝基、氰基、-OSiRb1Rb2Rb3、-SRb4、-NRb5Rb6和-PRb7Rb8組成之群組中的至少一個所取代;Rb1至Rb8各自獨立為(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C1-C20)烷基(C6-C20)芳基或(C3-C20)環烷基;X1和X2各自獨立為氫、(C1-C20)烷基、(C3-C20)環烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、((C1-C20)烷基(C6-C20)芳基)(C1-C20)烷基、(C1-C20)烷氧基、(C6-C20)芳氧基、(C1-C20)烷基(C6-C20)芳 氧基、(C1-C20)烷氧基(C6-C20)芳氧基、-OSiRaRbRc、-SRd、-NReRf、-PRgRh或(C1-C20)亞烷基;Ra至Rd各自獨立為(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C1-C20)烷基(C6-C20)芳基或(C3-C20)環烷基;Re至Rh各自獨立為(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C1-C20)烷基(C6-C20)芳基、(C3-C20)環烷基、三(C1-C20)烷基矽基或三(C6-C20)芳基矽基;其限制條件為,當X1和X2中之一個是(C1-C50)亞烷基時,另一個則忽略;以及該雜芳基和該雜環烷基包括至少一個選自N、O和S的雜原子。 A transition metal compound represented by the following Chemical Formula 1: In Chemical Formula 1, M is a transition metal of Group 4 of the periodic table; R 1 to R 3 are each independently hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C3-C20) naphthenic , halogen, (C2-C20) alkenyl, (C3-C20)heteroaryl, (C3-C20)heterocycloalkyl, -OR a1 , -SR a2 , -NR a3 R a4 or -PR a5 R a6 And R 2 and R 3 may be through a (C3-C7)alkylene group or a (C3-C7)alkylene chain with or without an aromatic ring to form a fused ring; R 4 and R 5 are each independently ( C1-C20)alkyl, halo(C1-C20)alkyl, (C3-C20)cycloalkyl, (C6-C20)aryl, (C1-C20)alkyl(C6-C20)aryl, (C6 -C20) aryl (C1-C20) alkyl, (C3-C20)heteroaryl, -OR a1 , -SR a2 , -NR a3 R a4 or -PR a5 R a6 , or R 4 and R 5 are permeabilizable (C4-C7) alkyl chain to form a ring; R 6 to R 8 are each independently hydrogen, (C1-C20) alkyl, halo (C1-C20) alkyl, halogen, (C6-C20) aryl (C3-C20)cycloalkyl, (C2-C20)alkenyl, (C3-C20)heteroaryl, (C1-C20)heterocycloalkyl, -OR a1 , -SR a2 , -NR a3 R a4 Or -PR a5 R a6 , or R 6 to R 8 may be through a (C4-C7)-extended alkenyl group with or without an aromatic ring and an adjacent substituent chain a fused ring; Ar 1 is a fluorenyl or oxazolyl group, and the fluorenyl or carbazolyl group of Ar 1 may be further selected from the group consisting of hydrogen, (C1-C20) alkyl, halo (C1-C20) alkyl, ( C6-C20) aryl, (C1-C20)alkyl (C6-C20) aryl, (C6-C20) aryl (C1-C20) alkyl, -OR a1 , -SR a2 , -NR a3 R a4 And at least one of the group consisting of -PR a5 R a6 is substituted; R a1 to R a6 are each independently (C1-C20)alkyl or (C6-C20)aryl; R 1 to R 3 and R 6 are R 8 is alkyl, aryl, cycloalkyl, heteroaryl or heterocycloalkyl and R a1 to R A6 alkyl or aryl group may be further selected from halogen, (C1-C20) alkyl, halo ( C1-C20)alkyl, (C1-C20)alkoxy, (C6-C20)aryl, (C6-C20)aryloxy, nitro, cyano, -OSiR b1 R b2 R b3 , -SR b4 And at least one of the group consisting of -NR b5 R b6 and -PR b7 R b8 is substituted; R b1 to R b8 are each independently (C1-C20)alkyl, (C6-C20) aryl, (C6- C20) aryl (C1-C20) alkyl, (C1-C20) alkyl (C6-C20) aryl or (C3-C20) cycloalkyl; X 1 and X 2 are each independently hydrogen, (C1-C20 An alkyl group, (C3-C20) cycloalkyl group, (C6-C20) aryl group, (C6-C20) aryl (C1-C20) alkyl group, ((C1-C20) alkyl group (C6-C20) (aryl)(C1-C20)alkyl, (C1-C20)alkoxy, (C6-C20)aryloxy, (C1-C20)alkyl(C6-C20)aryloxy, (C1-C20) Alkoxy (C6-C20) aryloxy, -OSiR a R b R c , -SR d , -NR e R f , -PR g R h or (C1-C20) alkylene; R a to R Each d is independently (C1-C20)alkyl, (C6-C20)aryl, (C6-C20)aryl(C1-C20)alkyl, (C1-C20)alkyl(C6-C20)aryl or (C3-C20)cycloalkyl; R e to R h are each independently (C1-C20)alkyl, (C6-C20)aryl, (C6-C20)aryl(C1-C20)alkyl, (C1 -C20)alkyl (C6-C20) aryl, (C3-C20)cycloalkyl, tri(C1-C20)alkyldecyl or tri(C6-C20)arylfluorenyl; When one of X 1 and X 2 is a (C1-C50) alkylene group, the other is omitted; and the heteroaryl group and the heterocycloalkyl group include at least one hetero atom selected from N, O and S. 如請求項1所記載之過渡金屬化合物,其中該過渡金屬化合物由以下化學式2或化學式3表示: 在化學式2和化學式3中,M、R4、R5、R7、R8、Ar1、X1和X2與如請求項1之化學式1中所定義的相同;R1至R3各自獨立為氫、(C1-C20)烷基、(C6-C20)芳基、(C3-C20)環烷基、鹵素、(C2-C20)烯基、(C3-C20)雜芳基、(C3-C20)雜環烷基、-ORa1、-SRa2、-NRa3Ra4或-PRa5Ra6;Ra1至Ra6各自獨立為(C1-C20)烷基或(C6-C20)芳基;R1至R3的烷基、芳基、環烷基、雜芳基或雜環烷基和Ra1至Ra6的烷基或芳基可進一步經至少一個選自鹵素、(C1-C20)烷基、鹵(C1-C20)烷基、(C1-C20)烷氧基、(C6-C20)芳基、(C6-C20)芳氧基、硝基、氰基、-OSiRb1Rb2Rb3、-SRb4、-NRb5Rb6和-PRb7Rb8組成之群組中的至少一個所取代;以及Rb1至Rb8各自獨立為(C1-C20)烷基、(C6-C20)芳基、(C6-C20)芳基(C1-C20)烷基、(C1-C20)烷基(C6-C20)芳基或(C3-C20)環烷基。 The transition metal compound according to claim 1, wherein the transition metal compound is represented by the following Chemical Formula 2 or Chemical Formula 3: In Chemical Formula 2 and Chemical Formula 3, M, R 4 , R 5 , R 7 , R 8 , Ar 1 , X 1 and X 2 are the same as defined in Chemical Formula 1 of Claim 1 ; each of R 1 to R 3 Independently hydrogen, (C1-C20)alkyl, (C6-C20)aryl, (C3-C20)cycloalkyl, halogen, (C2-C20)alkenyl, (C3-C20)heteroaryl, (C3 -C20)heterocycloalkyl, -OR a1 , -SR a2 , -NR a3 R a4 or -PR a5 R a6 ; R a1 to R a6 are each independently (C1-C20)alkyl or (C6-C20) aryl An alkyl group, an aryl group, a cycloalkyl group, a heteroaryl group or a heterocycloalkyl group of R 1 to R 3 and an alkyl group or an aryl group of R a1 to R a6 may be further selected from at least one selected from the group consisting of halogens, (C1- C20) alkyl, halo(C1-C20)alkyl, (C1-C20)alkoxy, (C6-C20)aryl, (C6-C20)aryloxy, nitro, cyano, -OSiR b1 R Substituting at least one of the group consisting of b2 R b3 , -SR b4 , -NR b5 R b6 and -PR b7 R b8 ; and R b1 to R b8 are each independently (C1-C20)alkyl, (C6- C20) aryl, (C6-C20)aryl(C1-C20)alkyl, (C1-C20)alkyl(C6-C20)aryl or (C3-C20)cycloalkyl. 如請求項2所記載之過渡金屬化合物,其中Ar1的該茀基或咔唑基可進一步經選自鹵素、(C1-C20)烷基、鹵(C1-C20)烷基、(C6-C12)芳基、(C1-C10)烷基(C6-C12)芳基、(C6-C12)芳基(C1-C10)烷基、(C1-C10)烷氧基、(C6-C12)芳氧基、(C1-C10)烷硫基、(C6-C12)芳硫基、二(C1-C10)烷基胺基、二(C6-C12)芳基胺基、二(C1-C10)烷基膦和二(C6-C12)芳基膦組成之群組中的至少一個所取代。 The transition metal compound according to claim 2, wherein the thiol or oxazolyl group of Ar 1 is further selected from the group consisting of halogen, (C1-C20) alkyl, halo (C1-C20) alkyl, (C6-C12) Aryl, (C1-C10)alkyl (C6-C12) aryl, (C6-C12) aryl (C1-C10) alkyl, (C1-C10) alkoxy, (C6-C12) aryloxy , (C1-C10)alkylthio, (C6-C12)arylthio, bis(C1-C10)alkylamino, bis(C6-C12)arylamine, bis(C1-C10)alkyl At least one of the group consisting of a phosphine and a di(C6-C12) arylphosphine is substituted. 如請求項3所記載之過渡金屬化合物,其中該過渡金屬化合物由以下化學式4或化學式5表示: 在化學式4和化學式5中,M、X1和X2與如請求項1之化學式1中所定義的相同; R1至R3各自獨立為氫、(C1-C20)烷基或鹵(C1-C20)烷基;R4和R5各自獨立為(C1-C20)烷基、鹵(C1-C20)烷基或(C6-C20)芳基;R7和R8各自獨立為氫、(C1-C20)烷基、鹵(C1-C20)烷基或鹵素,或者R7和R8可以透過鏈結以形成稠合環;Ar1 R12和R13各自獨立為(C1-C20)烷基;以及R14、R15和R16各自獨立為氫或(C1-C20)烷基。 The transition metal compound according to claim 3, wherein the transition metal compound is represented by the following Chemical Formula 4 or Chemical Formula 5: In Chemical Formula 4 and Chemical Formula 5, M, X 1 and X 2 are the same as defined in Chemical Formula 1 of Claim 1 ; R 1 to R 3 are each independently hydrogen, (C1-C20) alkyl or halogen (C1) -C20)alkyl; R 4 and R 5 are each independently (C1-C20)alkyl, halo(C1-C20)alkyl or (C6-C20)aryl; R 7 and R 8 are each independently hydrogen, ( C1-C20) alkyl, halo(C1-C20)alkyl or halogen, or R 7 and R 8 can be permeated , , or Chaining to form a fused ring; Ar 1 is R 12 and R 13 are each independently (C1-C20)alkyl; and R 14 , R 15 and R 16 are each independently hydrogen or (C1-C20)alkyl. 如請求項4所記載之過渡金屬化合物,其中該過渡金屬化合物是選自以下化合物: 其中M是鈦、鋯或鉿。 The transition metal compound according to claim 4, wherein the transition metal compound is selected from the group consisting of: Wherein M is titanium, zirconium or hafnium. 一種過渡金屬催化劑組合物,係用於製備乙烯均聚物或乙烯與α-烯烴的共聚物,該過渡金屬催化劑組合物包括:如請求項1至5中任一項所記載之過渡金屬化合物;以及選自鋁化合物、硼化合物或其混合物的共催化劑。 A transition metal catalyst composition for use in the preparation of an ethylene homopolymer or a copolymer of ethylene and an α-olefin, the transition metal catalyst composition comprising: the transition metal compound according to any one of claims 1 to 5; And a cocatalyst selected from the group consisting of aluminum compounds, boron compounds, or mixtures thereof. 如請求項6所記載之過渡金屬催化劑組合物,其中用作為該共催化劑的該鋁化合物是選自烷基鋁氧烷和有機鋁之一種或兩種或更多種的混合物,且包括選自甲基鋁氧烷、修飾甲基鋁氧烷、四異丁基鋁氧烷、三甲基鋁、三乙基鋁和三異丁基鋁中的一種或其混合物。 The transition metal catalyst composition according to claim 6, wherein the aluminum compound used as the cocatalyst is one or a mixture of two or more selected from the group consisting of alkyl aluminoxanes and organoaluminum, and is selected from the group consisting of One of methylaluminoxane, modified methylaluminoxane, tetraisobutylaluminoxane, trimethylaluminum, triethylaluminum, and triisobutylaluminum or a mixture thereof. 如請求項6或7所記載之過渡金屬催化劑組合物,其中用作為該共催化劑的該鋁化合物具有1:10至5,000的過渡金屬(M)和鋁原子(Al)(M:Al)的莫耳比。 The transition metal catalyst composition according to claim 6 or 7, wherein the aluminum compound used as the cocatalyst has a transition metal (M) of 1:10 to 5,000 and an aluminum atom (Al) (M:Al). Ear ratio. 如請求項6所記載之過渡金屬催化劑組合物,其中用作為該共催化劑的該硼化合物包括選自肆(五氟苯基)硼酸-N,N-二甲基苯銨、肆(五氟苯基)硼酸三苯基甲基酯和參(五氟苯基)硼烷中的一種或其混合物。 The transition metal catalyst composition according to claim 6, wherein the boron compound used as the cocatalyst comprises a group selected from the group consisting of ruthenium (pentafluorophenyl) borate-N,N-dimethylanilinium, ruthenium (pentafluorobenzene) One of or a mixture of triphenylmethyl borate and quinone (pentafluorophenyl)borane. 如請求項6或9所記載之過渡金屬催化劑組合物,其中該過渡金屬化合物與該共催化劑之莫耳比,即過渡金屬(M):硼原子(B):鋁原子(Al)之莫耳比的範圍為1:0.1至100:10至3,000。 The transition metal catalyst composition according to claim 6 or 9, wherein a molar ratio of the transition metal compound to the cocatalyst, that is, a transition metal (M): a boron atom (B): a mole of an aluminum atom (Al) The ratio ranges from 1:0.1 to 100:10 to 3,000. 如請求項10所記載之過渡金屬催化劑組合物,其中該過渡金屬化合物與該共催化劑之莫耳比,即過渡金屬 (M):硼原子(B):鋁原子(Al)之莫耳比的範圍為1:0.5至5:100至3,000。 The transition metal catalyst composition according to claim 10, wherein a molar ratio of the transition metal compound to the cocatalyst, that is, a transition metal (M): boron atom (B): The molar ratio of the aluminum atom (Al) ranges from 1:0.5 to 5:100 to 3,000. 一種使用請求項6所記載之過渡金屬催化劑組合物製備乙烯均聚物或乙烯與α-烯烴的共聚物的方法。 A process for producing an ethylene homopolymer or a copolymer of ethylene and an α-olefin using the transition metal catalyst composition described in claim 6. 如請求項12所記載之方法,其中與乙烯共聚合的α-烯烴是選自丙烯、1-丁烯、1-戊烯、4-甲基-1-戊烯、1-己烯、1-庚烯、1-辛烯、1-癸烯、1-十一烯、1-十二烯、1-十四烯、1-十六烯、1-十八烯、1-二十烯、環戊烯、環己烯、降冰片烯、苯基降冰片烯、苯乙烯,α-甲基苯乙烯、對甲基苯乙烯和3-氯甲基苯乙烯中之至少一者,且該乙烯與α-烯烴的共聚物具有乙烯含量為30重量%至99重量%。 The method of claim 12, wherein the α-olefin copolymerized with ethylene is selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1- Heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, ring At least one of pentene, cyclohexene, norbornene, phenyl norbornene, styrene, α-methylstyrene, p-methylstyrene, and 3-chloromethylstyrene, and the ethylene and The copolymer of the α-olefin has an ethylene content of from 30% by weight to 99% by weight. 如請求項13所記載之方法,其中用於乙烯均聚反應或乙烯單體與α-烯烴的共聚反應之反應器中的壓力為1atm至1000atm,且聚合反應溫度為25℃至200℃。 The method according to claim 13, wherein the pressure in the reactor for ethylene homopolymerization or copolymerization of the ethylene monomer and the α-olefin is from 1 atm to 1000 atm, and the polymerization temperature is from 25 ° C to 200 ° C. 如請求項14所記載之方法,其中用於乙烯均聚反應或乙烯單體與α-烯烴的共聚反應之反應器中的該壓力為10atm至150atm,且該聚合反應溫度為50℃至180℃。 The method of claim 14, wherein the pressure in the reactor for ethylene homopolymerization or copolymerization of the ethylene monomer and the α-olefin is from 10 atm to 150 atm, and the polymerization temperature is from 50 ° C to 180 ° C. .
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