WO2015183017A1 - Novel transition metal compound, transition metal catalyst composition for polymerizing olefin, containing same, and method for preparing ethylene homopolymer or copolymer of ethylene and α-olefin by using same - Google Patents

Abstract

The present invention relates to: a novel transition metal compound; a transition metal catalyst composition for preparing an ethylene homopolymer or a copolymer of ethylene and an α-olefin, containing the same; a method for preparing an ethylene homopolymer or a copolymer of ethylene and an α-olefin by using the same; and an ethylene homopolymer or a copolymer of ethylene and an α-olefin prepared thereby.

Description

New transition metal compound, transition metal catalyst composition for olefin polymerization including the same and method for producing ethylene homopolymer or copolymer of ethylene and α-olefin using same

The present invention relates to a novel transition metal compound, an ethylene homopolymer comprising the same or a transition metal catalyst composition for preparing a copolymer of ethylene and an α-olefin, and a method for producing an ethylene homopolymer or a copolymer of ethylene and an α-olefin using the same. .

Background Art In the past, so-called Ziegler-Natta catalyst systems composed of a main catalyst component of a titanium or vanadium compound and a cocatalyst component of an alkylaluminum compound have been generally used for preparing a homopolymer of ethylene or a copolymer of? -Olefin. However, the Ziegler-Natta catalyst system exhibits high activity against ethylene polymerization, but due to its heterogeneous catalytic activity, the molecular weight distribution of the resulting polymer is generally wide, and in particular, the composition distribution is not uniform in the copolymer of ethylene and α-olefin. There was this.

The metallocene catalyst system composed of a metallocene compound of Group 4 transition metal such as titanium, zirconium, and hafnium and methylaluminoxane as a promoter is a homogeneous catalyst having a single catalytic activity point. Compared to other catalyst system, polyethylene has narrower molecular weight distribution and uniform composition distribution. For example, in Japanese Patent Application Laid-Open No. 320,762, 372,632 or Japanese Patent Laid-Open No. 63-092621, Japanese Patent Laid-Open No. 02-84405, or Japanese Patent Laid-Open No. 03-2347, Cp ₂ TiCl ₂ , Cp ₂ ZrCl ₂ , Cp ₂ ZrMeCl, Cp ₂ ZrMe ₂ , Ethylene (IndH ₄ ) ₂ ZrCl _2, etc., by activating the metallocene compound with the cocatalyst methylaluminoxane to polymerize ethylene with high activity so that the molecular weight distribution (Mw / Mn) ranges from 1.5 to 2.0. It has been announced that polyethylene can be prepared. However, it is difficult to obtain a high molecular weight polymer in the catalyst system. Especially, when applied to a solution polymerization method performed at a high temperature of 120 ° C. or higher, the polymerization activity decreases rapidly and the β-hydrogen desorption reaction predominates, resulting in a weight average molecular weight (Mw). It is known to be inadequate to produce high molecular weight polymers of 100,000 or more.

On the other hand, as a catalyst capable of producing a high catalytic activity and a high molecular weight polymer in ethylene homopolymerization or copolymerization of ethylene and α-olefin under solution polymerization conditions, so-called geometric nonmetallocene catalysts in which transition metals are linked in a ring form (Also known as single activity catalysts) have been published. In European Patent No. 0416815 and Patent No. 0420436, an example in which an amide group is linked to one cyclopentadiene ligand in the form of a ring is disclosed. In Patent No. 0842939, a phenol-based ligand is used as an electron donor compound and a cyclopentadiene ligand. An example of a catalyst connected in a cyclic form is shown. However, since the yield of the ring formation reaction between the ligand and the transition metal compound is very low during the synthesis of the geometric catalyst, there are many difficulties in commercial use.

On the other hand, examples of non-metallic non-metallocene catalysts include U.S. Patent No. 6,329,478 and World Patent No. 00/005238. In this patent, it can be seen that a single-site catalyst using at least one phosphineimine compound as a ligand shows high ethylene conversion when copolymerizing ethylene and α-olefin under high temperature solution polymerization conditions of 120 ° C. or higher. US Pat. No. 5,079,205 shows an example of a catalyst having a bis-phenoxide ligand and US Pat. No. 5,043,408 a chelate type bisphenoxide ligand, but such a catalyst is too low in activity to perform ethylene homopolymers or α-olefins. It is difficult to use commercially in the preparation of copolymers.

Japanese Patent Laid-Open Publication Nos. 1996-208732 and 2002-212218 disclose use as an olefin polymerization catalyst having an anilido ligand, but no examples are disclosed in a commercially meaningful polymerization temperature range. In addition, an example of using an anilido ligand as a nonmetallocene catalyst for polymerization has been reported in the article " Organometallics 2002 , 21 , 3043 (Nomura et al.)", But this case was also limited to a methyl group which is a simple alkyl substituent.

Therefore, it is important to secure a more competitive catalyst system based on the economical properties required for commercialization catalysts, that is, excellent high temperature activity, excellent reactivity with higher alpha-olefins, and high molecular weight polymer production ability.

In order to overcome the problems of the prior art, the present inventors have conducted extensive research, and have found cyclopentadiene derivatives around group 4 transition metals; And a fluorenyl group having a chemical structure in which the electron donor function and the oxygen atom connecting the ligand and the transition metal are wrapped to have a function of making the catalyst system more stable and the substituents are easily introduced at the 9-position. A aryloxide ligand substituted with an ortho-position of an oxygen atom that connects the ligand and the transition metal to the derivative; a Group 4 transition metal catalyst having a structure that is not crosslinked between ligands is used for polymerization of ethylene and olefins. Was found to exhibit excellent catalytic activity. In view of these facts, a catalyst capable of producing high molecular weight ethylene homopolymer or copolymer of ethylene and α-olefin in a polymerization process performed at 60 ° C. or higher has been developed, and the present invention has been completed based on this. .

In addition, when preparing a catalyst including one cyclopentadienyl group ligand and only one or two aryl oxide ligands, a species in which the ligand is substituted or less substituted is not produced, which is a limitation in preparing a high purity catalyst. . Moreover, in the case of a catalyst containing one cyclopentadienyl group ligand and only one or two aryl oxide ligands, a halogen anion ligand or an alkyl anion ligand is generally substituted with the remaining ligand. In the case of a catalyst containing a halogen anion ligand, the halogen anion may act as a process corrosive, which causes a high process investment cost. The catalyst containing the alkyl anion ligand may be used to solve the problems caused by the halogen anion ligand, but the catalyst containing the alkyl anion ligand may be easily deteriorated by air. Therefore, in the present invention, by substituting all other ligands other than the cyclopentadienyl ligand with the arylene oxide ligand, it is possible to increase the economical efficiency of the process investment cost, and to prepare the catalyst which is easy to manufacture and relatively stable. The present invention provides a single-site catalyst and a polymerization method capable of economically preparing an ethylene homopolymer or a copolymer of ethylene and an α-olefin using various catalyst properties.

That is, it is an object of the present invention to provide a transition metal compound useful as a catalyst for the production of ethylene homopolymers or copolymers of ethylene and α-olefins, and also to provide catalyst compositions comprising the same.

Another object of the present invention is to provide an ethylene homopolymer or a copolymer of ethylene and an α-olefin prepared using the transition metal compound or the catalyst composition containing the transition metal compound.

Another object of the present invention is a simple synthesis route, which is very economical in terms of catalytic synthesis, and has a high activity in olefin polymerization, and an ethylene homopolymer or ethylene and α- having various physical properties. An object of the present invention is to provide a polymerization method in which copolymers of olefins can be economically produced from a commercial standpoint.

One aspect of the present invention for achieving the above object is a cyclopentadiene derivative around the Group 4 transition metal, as shown in formula (1); And a fluorenyl group having a chemical structure in which the electron donor function and the oxygen atom connecting the ligand and the transition metal are wrapped to have a function of making the catalyst system more stable and the substituents are easily introduced at the 9-position. Ethylene homopolymer or copolymer of ethylene and α-olefin including derivative; three aryloxide ligands substituted at ortho-position of oxygen atom connecting ligand and transition metal; A Group 4 transition metal compound useful as a catalyst for the preparation of

[Formula 1]

In Chemical Formula 1,

M is a transition metal of Group 4 on the periodic table;

Cp is a fused ring comprising a cyclopentadienyl ring or a cyclopentadienyl ring capable of bonding η ⁵ -with M, and a fused ring containing the cyclopentadienyl ring or cyclopentadienyl ring (C1- C20) alkyl, (C6-C30) aryl, tri (C1-C20) alkylsilyl, tri (C6-C20) arylsilyl, (C1-C20) alkyldi (C6-C20) arylsilyl, (C6-C20) aryl Di (C1-C20) alkylsilyl, (C2-C20) alkenyl and (C6-C30) aryl (C1-C20) alkyl, and may be further substituted with one or more selected from the group consisting of;

Ar is (C6-C14) arylene;

R ¹ and R ² independently of one another are a hydrogen atom, (C1-C20) alkyl or (C6-C30) aryl (C1-C20) alkyl;

m is an integer selected from 0 to 3, provided that when R ¹ and R ² are hydrogen atoms at the same time m is not 0;

R is (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C30) aryl, (C1-C20) alkyl (C6-C30) aryl, (C6-C30) aryl (C1-C20) alkyl or When (C1-C20) alkoxy and m is 2 or 3, each R may be the same or different;

Alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkoxy and arylene of Ar are each independently halogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C30) aryl, (C6-C30) aryl (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C30) aryloxy, (C3-C20) alkylsiloxy, (C6-C30) arylsiloxy, (C1-C20 ) Alkylamino, (C6-C30) arylamino, (C1-C20) alkylphosphine, (C6-C30) arylphosphine, (C1-C20) alkylmercapto and (C6-C30) arylmercapto It may be further substituted with one or more selected substituents, and connected with (C3-C15) alkylene or (C3-C15) alkenylene, with or without fused ring with adjacent substituents of each substituent, to form an alicyclic ring and a monocyclic ring or Polycyclic aromatic rings can be formed.

Another aspect of the present invention for achieving the above object is the transition metal compound; And a cocatalyst selected from an aluminum compound, a boron compound, or a mixture thereof. The present invention relates to an ethylene homopolymer or a catalyst composition for preparing a copolymer of ethylene and an α-olefin.

Another aspect of the present invention for achieving the above object relates to a method for producing an ethylene homopolymer or a copolymer of ethylene and α-olefin using the catalyst composition.

Another aspect of the present invention for achieving the above object relates to an ethylene homopolymer or a copolymer of ethylene and α-olefin prepared using the transition metal compound or the catalyst composition.

The transition metal compound or the catalyst composition including the transition metal compound according to the present invention can be easily prepared by an economical method due to the simple synthesis process, and also has excellent thermal stability of the catalyst, while maintaining high catalytic activity even at high temperatures. Copolymerization with olefins is good and high-molecular weight polymers can be produced in high yields, and thus have high commercial viability compared to known metallocene and nonmetallocene-based single-site catalysts. The transition metal compound of the present invention is a structure in which all other ligands except the cyclopentadienyl ligand are substituted with arylene oxide ligands, and no halogen anion ligand acting as a process corrosion substance or an alkyl anion ligand which is easily modified by air is used. Highly economical, easy to manufacture, relatively stable and high-purity catalysts that are not included in the process. They are single-site catalysts with high activity in olefin polymerization from a commercial point of view and ethylene having various physical properties using these catalyst components. Polymers or copolymers of ethylene and α-olefins can be produced economically. Therefore, the transition metal and the catalyst composition including the same according to the present invention can be usefully used for the preparation of ethylene homopolymer or copolymer with α-olefin having various physical properties.

Hereinafter, the present invention will be described in more detail.

Transition metal compound according to an embodiment of the present invention is a cyclopentadiene derivative around the Group 4 transition metal, as represented by the following formula (1); And a fluorenyl group having a chemical structure in which the electron donor function and the oxygen atom connecting the ligand and the transition metal are wrapped to have a function of making the catalyst system more stable and the substituents are easily introduced at the 9-position. The derivative includes three aryloxide ligands substituted at the ortho-position of the oxygen atom connecting the ligand and the transition metal, and has a structure that is not crosslinked with each other.

[Formula 1]

In Formula 1, M is a transition metal of Group 4 on the periodic table;

Cp is a fused ring comprising a cyclopentadienyl ring or a cyclopentadienyl ring capable of bonding η ⁵ -with M, and a fused ring containing the cyclopentadienyl ring or cyclopentadienyl ring (C1- C20) alkyl, (C6-C30) aryl, tri (C1-C20) alkylsilyl, tri (C6-C20) arylsilyl, (C1-C20) alkyldi (C6-C20) arylsilyl, (C6-C20) aryl Di (C1-C20) alkylsilyl, (C2-C20) alkenyl and (C6-C30) aryl (C1-C20) alkyl, and may be further substituted with one or more selected from the group consisting of;

Ar is (C6-C14) arylene;

R ¹ and R ² independently of one another are a hydrogen atom, (C1-C20) alkyl or (C6-C30) aryl (C1-C20) alkyl;

m is an integer selected from 0 to 3, provided that when R ¹ and R ² are hydrogen atoms at the same time m is not 0;

R is (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C30) aryl, (C1-C20) alkyl (C6-C30) aryl, (C6-C30) aryl (C1-C20) alkyl or When (C1-C20) alkoxy and m is 2 or 3, each R may be the same or different;

Alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkoxy and arylene of Ar are each independently halogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C30) aryl, (C6-C30) aryl (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C30) aryloxy, (C3-C20) alkylsiloxy, (C6-C30) arylsiloxy, (C1-C20 ) Alkylamino, (C6-C30) arylamino, (C1-C20) alkylphosphine, (C6-C30) arylphosphine, (C1-C20) alkylmercapto and (C6-C30) arylmercapto It may be further substituted with one or more selected substituents, and connected with (C3-C15) alkylene or (C3-C15) alkenylene, with or without fused ring with adjacent substituents of each substituent, to form an alicyclic ring and a monocyclic ring or Polycyclic aromatic rings can be formed.

M, which is a transition metal of Formula 1, may be any transition metal of Group 4 on the periodic table. Preferably, M is titanium, zirconium (Zr), or hafnium (Hf).

“Alkyl” as described herein includes both linear and nonlinear forms.

“Aryl” as described herein is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal and includes a single or fused ring system. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like.

In addition, Cp is a fused ring or a substituted fused ring containing the cyclopentadiene ring, such as a cyclopentadiene ring, a substituted cyclopentadiene ring, indenyl, fluorenyl, etc., capable of bonding to the central metal η ^5- , Wherein “substituted” means (C1-C20) alkyl, (C6-C30) aryl, tri (C1-C20) alkylsilyl, tri (C6-C20) arylsilyl, (C1-C20) alkyldi (C6-C20) aryl May be further substituted with one or more selected from the group consisting of silyl, (C6-C20) aryldi (C1-C20) alkylsilyl, (C2-C20) alkenyl or (C6-C30) aryl (C1-C20) alkyl Means. More specifically, for example, cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, butylcyclopentadienyl, sec -butylcyclopenteti Neyl, tert -butylmethylcyclopentadienyl, trimethylsilylcyclopentadienyl, indenyl, methylindenyl, dimethylindenyl, ethylindenyl, isopropylinyl, fluorenyl, methylfluorenyl, dimethylfluore Nil, ethylfluorenyl, isopropylfluorenyl and the like.

Ar may be (C6-C14) arylene, for example, phenylene, naphthalen-1-yl, naphthalen-2-yl, fluoren-2-yl and fluoren-4-yl, of which Preferred are phenylene and naphthalen-2-yl.

R is independently of one another linear or nonlinear (C1-20) alkyl, more preferably linear or nonlinear (C1-10) alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec- Butyl, tert -butyl, n-pentyl, neopentyl, tert-pentyl, n-hexyl, n-octyl, tert -octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n- Pentadecyl, n-octadecyl or n-icosyl, of which methyl, ethyl, n-propyl, isopropyl, n-butyl, tert -butyl or tert -octyl; (C3-C20) cycloalkyl, more preferably (C3-C10) cycloalkyl, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl or cyclododecyl, these Among them, cyclohexyl is preferable; (C6-C30) aryl or (C1-C20) alkyl (C6-C30) aryl, more preferably (C6-C13) aryl or (C1-C10) alkyl (C6-C13) aryl, for example phenyl, 2- Tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xyl Silyl, 2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3 , 4,5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, sec -butylphenyl, tert -butylphenyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl, n-tetradecylphenyl, biphenyl ), Naphthyl, fluorenyl group, triphenyl or anthracenyl, of which phenyl, naphthyl, biphenyl, 2-isopropylphenyl, 3,5-xylyl or 2,4,6- Trimethylphenyl; (C6-C30) aryl (C1-C20) alkyl, more preferably (C6-C13) aryl (C1-C10) alkyl, such as benzyl, (2-methylphenyl) methyl, (3-methylphenyl) methyl, (4 -Methylphenyl) methyl, (2,3-dimethylphenyl) methyl, (2,4-dimethylphenyl) methyl, (2,5-dimethylphenyl) methyl, (2,6-dimethylphenyl) methyl, (3,4- Dimethylphenyl) methyl, (4,6-dimethylphenyl) methyl, (2,3,4-trimethylphenyl) methyl, (2,3,5-trimethylphenyl) methyl, (2,3,6-trimethyl-phenyl) Methyl, (3,4,5-trimethylphenyl) methyl, (2,4,6-trimethylphenyl) methyl, (2,3,4,5-tetramethylphenyl) methyl, (2,3,4,6-tetra Methylphenyl) methyl, (2,3,5,6-tetramethylphenyl) methyl, (pentamethylphenyl) methyl, (ethylphenyl) methyl, (n-propylphenyl) methyl, (isopropylphenyl) methyl, (n-butylphenyl ) Methyl, (sec-butylphenyl) methyl, (tert-butylphenyl) methyl, (n-pentylphenyl) methyl, (neopentylphenyl) methyl, (n-hexylphenyl) methyl, (n-octylphenyl) methyl, (n-decylphenyl) methyl, (n-dodecylphenyl) methyl, (n-tetradecylphenyl) methyl , Triphenylmethyl, naphthylmethyl or anthracenylmethyl, of which benzyl or triphenylmethyl; (C1-C20) alkoxy, more preferably (C1-C10) alkoxy, for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec -butoxy, tert -butoxy, n-pentoxy, neopentoxy, n-hexoxy, n-octoxy, n-dodecyloxy, n-pentadecyloxy or n-icosyloxy, among which preferred is methoxy or Oxy.

In addition, m is an integer of 0 to 3, when m is 2 or 3, each R may be the same or different from each other.

R ¹ and R ² substituted with the fluorenyl group of the ligand are independently of each other a hydrogen atom; Linear or nonlinear (C1-20) alkyl, more preferably linear or nonlinear (C1-10) alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n -Hexyl, n-octyl, 2-ethylhexyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-pentadecyl, n-octadecyl or n-icosyl, of which preferred Below are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl Or n-octyl; (C6-C30) aryl (C1-C20) alkyl, more preferably (C6-C13) aryl (C1-C10) alkyl, such as benzyl, (2-methylphenyl) methyl, (3-methylphenyl) methyl, (4 -Methylphenyl) methyl, (2,3-dimethylphenyl) methyl, (2,4-dimethylphenyl) methyl, (2,5-dimethylphenyl) methyl, (2,6-dimethylphenyl) methyl, (3,4- Dimethylphenyl) methyl, (4,6-dimethylphenyl) methyl, (2,3,4-trimethylphenyl) methyl, (2,3,5-trimethylphenyl) methyl, (2,3,6-trimethyl-phenyl) Methyl, (3,4,5-trimethylphenyl) methyl, (2,4,6-trimethylphenyl) methyl, (2,3,4,5-tetramethylphenyl) methyl, (2,3,4,6-tetra Methylphenyl) methyl, (2,3,5,6-tetramethylphenyl) methyl, (pentamethylphenyl) methyl, (ethylphenyl) methyl, (n-propylphenyl) methyl, (isopropylphenyl) methyl, (n-butylphenyl ) Methyl, (sec-butylphenyl) methyl, (tert-butylphenyl) methyl, (n-pentylphenyl) methyl, (neopentylphenyl) methyl, (n-hexylphenyl) methyl, (n-octylphenyl) methyl, (n-decylphenyl) methyl, (n-tetradecylphenyl) methyl, triphenylmethyl, na Butyl methyl or anthracenyl methyl, Preferred of them are benzyl.

Alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, alkoxy and arylene of Ar are each independently halogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C30) aryl, (C6-C30) aryl (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C30) aryloxy, (C3-C20) alkylsiloxy, (C6-C30) arylsiloxy, (C1-C20 ) Alkylamino, (C6-C30) arylamino, (C1-C20) alkylphosphine, (C6-C30) arylphosphine, (C1-C20) alkylmercapto and (C6-C30) arylmercapto It may be further substituted with one or more substituents selected, the halogen atoms include fluorine, chlorine, bromine or iodine atoms, examples of (C1-C20) alkyl methyl, ethyl, n-propyl, isopropyl, n- Butyl, sec -butyl, tert -butyl, n-pentyl, neopentyl, amyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl or n-eicosyl, Preferred of these are methyl, ethyl, isopropyl, tert -butyl or amyl, (C3 Examples of cycloalkyl include cyclopropane, cyclobutyl, cyclopentyl, cychlorohexyl, cychloroheptyl or adamantyl; Examples of (C6-C30) aryl or (C6-C30) aryl (C1-C20) alkyl are phenyl, naphthyl, fluorenyl, anthracenyl, benzyl, (2-methylphenyl) methyl, (3-methylphenyl) methyl, (4-methylphenyl) methyl, (2,3-dimethylphenyl) methyl, (2,4-dimethylphenyl) methyl, (2,5-dimethylphenyl) methyl, (2,6-dimethylphenyl) methyl, (3, 4-dimethylphenyl) methyl, (4,6-dimethylphenyl) methyl, (2,3,4-trimethylphenyl) methyl, (2,3,5-trimethylphenyl) methyl, (2,3,6-trimethyl- Phenyl) methyl, (3,4,5-trimethylphenyl) methyl, (2,4,6-trimethylphenyl) methyl, (2,3,4,5-tetramethylphenyl) methyl, (2,3,4,6 -Tetramethylphenyl) methyl, (2,3,5,6-tetramethylphenyl) methyl, (pentamethylphenyl) methyl, (ethylphenyl) methyl, (n-propylphenyl) methyl, (isopropylphenyl) methyl, (n- Butylphenyl) methyl, (sec-butylphenyl) methyl, (tert-butylphenyl) methyl, (n-pentylphenyl) methyl, (neopentylphenyl) methyl, (n-hexylphenyl) methyl, (n-octylphenyl) Methyl, (n-decylphenyl) methyl, (n-decylphenyl) methyl, (n-te La-decyl) methyl, naphthylmethyl or there may be mentioned anthracenyl metilreul, of which preferred is a benzyl; (C1-C20) alkoxy includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec -butoxy, tert -butoxy, n-pentoxy, neopentoxy, n-hexoxy C, n-octoxy, n-dodecyloxy, n-pentadecyloxy or n-icosyloxy, of which methoxy, ethoxy, isopropoxy or tert -butoxy; (C6-C30) aryloxy includes phenoxy, naphthalen-1-yloxy, naphthalen-2-yloxy, fluoren-2-yloxy and fluoren-4-yloxy, of which preferred are Phenoxy and fluoren-2-yloxy; Examples of (C3-C20) alkylsiloxy are trimethylsiloxy, triethylsiloxy, tri-n-propylsiloxy, triisopropylsiloxy, tri-n-butylsiloxy, tri- sec -butylsiloxy, Tri- tert -butylsiloxy, tri-isobutylsiloxy, tert -butyldimethylsiloxy, tri-n-pentylsiloxy, tri-n-hexylsiloxy or tricyclohexylsiloxy, among which Preferred is trimethylsiloxy, or tert -butyldimethylsiloxy; Examples of (C6-C30) arylsiloxy include triphenylsiloxy and trinaphthylsiloxy, of which triphenylsiloxy is preferred; Examples of (C1-C20) alkyl substituted or (C6-C30) aryl substituted amino are dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, di-n-butylamino, di- sec -butyl Amino, di- tert -butylamino, diisobutylamino, tert - butylisopropylamino , di-n-hexylamino, di-n-octylamino, di-n-decylamino, diphenylamino, methylethylamino May be mentioned; Examples of (C1-C20) alkyl substituted or (C6-C30) aryl substituted phosphines are dimethylphosphine, diethylphosphine, di-n-propylphosphine, diisopropylphosphine, di-n-butylphosphine , Di- sec -butylphosphine, di- tert -butylphosphine, diisobutylphosphine, tert - butylisopropylphosphine , di-n-hexylphosphine, di-n-octylphosphine, di-n Decylphosphine, diphenylphosphine, methylethylphosphine, among which dimethylphosphine, diethylphosphine or diphenylphosphine; Examples of (C1-C20) alkyl substituted or (C6-C30) aryl substituted mercapto include methylmercapto, ethylmercapto, propylmercapto, isopropylmercapto, 1-butylmercapto, isopentylmercapto, phenylmercapto , Naphthyl mercapto or biphenyl mercapto, and preferably is ethyl mercapto or isopropyl mercapto.

In addition, examples of (C3-C15) alkylene with or without fused ring with adjacent substituents of each substituent include propylene, butylene, pentylene, hexylene, octylene, decylene, dodecylene or pentadecylene, Preferred of these is butylene; Examples of (C3-C15) alkenylene include propenylene, butenylene, pentenylene, hexenylene, octenylene, desenylene, dodecenylene or pentadecenylene, among which propene Lene or butenylene.

The transition metal compound of Formula 1 may be represented by Formula 2 more preferably.

[Formula 2]

In Formula 2, M, Cp and m are the same as defined in Formula 1;

R ¹ and R ² independently of one another are a hydrogen atom, (C1-C10) alkyl or (C6-C13) aryl (C1-C10) alkyl;

R is (C1-C10) alkyl, (C3-C10) cycloalkyl, (C6-C13) aryl, (C1-C10) alkyl (C6-C13) aryl, (C6-C13) aryl (C1-C10) alkyl or (C1-C10) alkoxy;

R ¹¹ to R ¹³ are each independently hydrogen, halogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C30) aryl, (C6-C30) aryl (C1-C20) alkyl, (C1 -C20) alkoxy, (C6-C30) aryloxy, (C3-C20) alkylsiloxy, (C6-C30) arylsiloxy, (C1-C20) alkylamino, (C6-C30) arylamino, (C1- C20) alkylphosphine, (C6-C30) arylphosphine, (C1-C20) alkylmercapto and (C6-C30) arylmercapto;

Alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl and alkoxy of R are independently of each other halogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C30) aryl, (C6-C30) Aryl (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C30) aryloxy, (C3-C20) alkylsiloxy, (C6-C30) arylsiloxy, (C1-C20) alkylamino, ( C6-C30) arylamino, (C1-C20) alkylphosphine, (C6-C30) arylphosphine, (C1-C20) alkylmercapto and (C6-C30) arylmercapto It may be further substituted, and linked with (C3-C15) alkylene or (C3-C15) alkenylene, which may or may not include adjacent substituents and fused rings of each substituent, to form an alicyclic ring and a monocyclic or polycyclic aromatic ring. Can be formed.

More preferably, R ¹ and R ² substituted with the fluorenyl group of the ligand are independently of each other linear or non-linear (C 1-10) alkyl or (C 6 -C 13) aryl (C 1 -C 10) alkyl.

The transition metal compound of Formula 1 may be selected from compounds having the following structure, but is not limited thereto.

Wherein Cp is cyclopentadienyl or pentamethylcyclopentadienyl.

On the other hand, the transition metal compound of Formula 1 is an ethylene homopolymer or an active catalyst component used in the preparation of copolymers with ethylene and α-olefin, preferably, by extracting a ligand in the transition metal complex to cation the central metal And a counter-ion having a weak binding force, that is, an aluminum compound or a boron compound, or a mixture thereof, which may act as an anion, may act together as a cocatalyst, and the catalyst composition comprising the transition metal compound and the cocatalyst described above may also be In range

The boron compound that can be used as a promoter in the present invention may include a boron compound known from U.S. Patent No. 5,198,401, and specifically, may be selected from compounds represented by the following Chemical Formulas 3 to 5.

[Formula 3]

B (R ⁵ ) ₃

[Formula 4]

[R ⁶ ] ⁺ [B (R ⁵ ) ₄ ] ^-

[Formula 5]

[(R ⁷ ) _p ZH] ⁺ [B (R ⁵ ) ₄ ] ^-

In Chemical Formulas 3 to 5, B is a boron atom;

R ⁵ is a phenyl group, said phenyl group being a fluorine atom, (C1-C20) alkyl, a (C1-C20) alkyl substituted by a fluorine atom, (C1-C20) alkoxy and a (C1-C20) substituted by a fluorine atom May be further substituted with 3 to 5 substituents selected from alkoxy; R ⁶ represents a (C 5 -C 7) aromatic radical or a (C 1 -C 20) alkyl (C 6 -C 20) aryl radical, (C 6 -C 30) aryl C 1 -C 20) alkyl radical, for example triphenylmethylium radical Is; Z is nitrogen or phosphorus atom; R ⁷ is a (C1-C20) alkyl radical or an anninium radical substituted with two (C1-C10) alkyl groups together with a nitrogen atom; p is an integer of 2 or 3.

Preferred examples of the boron-based cocatalysts include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluoro Phenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, triphenyl Methylinium tetrakis (pentafluorophenyl) borate, triphenylmethyllinium tetrakis (2,3,5,6-tetrafluorophenyl) borate, triphenylmethyllinium tetrakis (2,3,4, 5-tetrafluorophenyl) borate, triphenylmethyllinium tetrakis (3,4,5-trifluorophenyl) borate, triphenylmethyllinium tetrakis (2,2,4-trifluorophenyl) borate , Triphenylmethyllinium phenylbis (pentafluorophenyl) borate or triphenylmethyllinium tetrakis (3,5-bistrifluoromethylphenyl) borate The can. Moreover, as a specific compounding example thereof, ferrocenium tetrakis (pentafluorophenyl) borate, 1,1'- dimethyl ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, and triphenyl Triphenylmethylium tetrakis (pentafluorophenyl) borate, triphenylmethyllinium tetrakis (3,5-bistrifluoromethylphenyl) borate, triethylammonium tetrakis (pentafluoro Phenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-bistri Fluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-2,4 , 6-pen Tmethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) Borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, or tri (dimethyl Phenyl) phosphonium tetrakis (pentafluorophenyl) borate, the most preferred of which is N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylmethyllinium tetrakis (pentafluorophenyl) ) Borate or tris (pentafluoro) borate.

As an example of the aluminum compound that can be used as a promoter in the catalyst composition according to one embodiment of the present invention, an aluminoxane compound of Formula 6 or 7, an organoaluminum compound of Formula 8 or an organoaluminum alkyloxide of Formula 9 or Formula 10 Or an organoaluminum aryloxide compound.

[Formula 6]

(-Al (R ⁸ ) -O-) _q

[Formula 7]

(R ⁸ ) ₂ Al-(-O (R ⁸ )-) _r- (R ⁸ ) ₂

[Formula 8]

(R ⁹ ) _s Al (E) _3-s

[Formula 9]

(R ¹⁰ ) ₂ AlOR ¹¹

[Formula 10]

R ¹⁰ Al (OR ¹¹ ) ₂

Wherein R ⁸ is (C1-C20) alkyl, preferably methyl or isobutyl, and q and r are each independently an integer from 5 to 20; R ⁹ and R ¹⁰ are each independently (C 1 -C 20) alkyl; E is a hydrogen atom, a halogen atom or (C1-C20) alkyl; s is an integer between 1 and 3; R ¹¹ is (C1-C20) alkyl or (C6-C30) aryl.

Specific examples of the aluminum compound which may be used include methyl aluminoxane, modified methyl aluminoxane, and tetraisobutyl aluminoxane as aluminoxane compounds; Examples of organoaluminum compounds include trialkylaluminums including trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum and trioctylaluminum; Dialkylaluminum chlorides including dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, and dihexylaluminum chloride; Alkylaluminum dichlorides including methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, and hexylaluminum dichloride; And dialkyl aluminum hydrides including dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutyl aluminum hydride and dihexyl aluminum hydride. Alkylaluminum or mixtures thereof, more preferably methylaluminoxane, modified methylaluminoxane, triethylaluminum, triisobutylaluminum or mixtures thereof.

In the transition metal catalyst composition for preparing an ethylene homopolymer containing a promoter according to the present invention or a copolymer of ethylene and an α-olefin, when the aluminum compound is used as a promoter, the transition metal of Formula 1 (M): aluminum atom ( Al) ratio is 1: 10-5,000 by molar ratio. In addition, in the transition metal catalyst composition for preparing an ethylene homopolymer or a copolymer of ethylene and an α-olefin comprising the promoter according to the present invention, the preferred range of the ratio between the transition metal compound of Formula 1 and the promoter is a central metal on a molar ratio basis. (M): The ratio of a boron atom (B): aluminum atom (Al) is 1: 0.1-200: 10-1,000, More preferably, it is 1: 0.5-5: 25-500. In this ratio, it is possible to prepare an ethylene homopolymer or a copolymer of ethylene and an α-olefin, and the range of the ratio varies depending on the purity of the reaction.

As another aspect of the present invention, a method for preparing an ethylene polymer using the transition metal catalyst composition may be carried out by contacting the transition metal catalyst, the promoter, and ethylene or, if necessary, an α-olefin comonomer in the presence of a suitable organic solvent. . At this time, the transition metal catalyst and the cocatalyst component may be separately introduced into the reactor, or each component may be previously mixed and introduced into the reactor, and mixing conditions such as the order of input, temperature or concentration are not particularly limited.

Preferred organic solvents that can be used in the preparation method are C3-C20 hydrocarbons, specific examples of which are butane, isobutane, pentane, hexane, heptane, octane, isooctane, nonane, decane, dodecane, cyclohexane, methylcyclohexane , Benzene, toluene, xylene and the like.

Specifically, in the production of ethylene homopolymer, ethylene is used alone as a monomer, wherein a suitable ethylene pressure is 1 to 1000 atm and more preferably 1 to 150 atm. In addition, the reactor internal temperature for the polymerization reaction is effective to be carried out at 60 ℃ to 300 ℃, preferably at 80 ℃ to 250 ℃, more preferably 130 ℃ to 220 ℃.

In addition, when preparing a copolymer of ethylene and α-olefin, C3-C18 α-olefin can be used as a comonomer together with ethylene, and preferably propylene, 1-butene, 1-pentene, 4-methyl-1 -Pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, and 1-octadecene. 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 the ethylene homopolymer, and the copolymer prepared according to the method of the present invention usually contains 50 wt% or more of ethylene, preferably 60 wt%. % Or more of ethylene, more preferably 60 to 99% by weight of ethylene.

As described above, linear low density polyethylene (LLDPE) prepared using C3-C18 α-olefin as comonomer has a density range of 0.910 to 0.940 g / cc, and ultra low density polyethylene (VLDPE) of 0.910 g / cc or less. Or ULDPE) or olefin elastomer regions. In addition, hydrogen may be used as a molecular weight regulator to control the molecular weight when preparing the ethylene homopolymer or copolymer according to the present invention, and usually has a weight average molecular weight (Mw) in the range of 80,000 to 500,000.

Since the catalyst composition presented in the present invention is present in a uniform form in the polymerization reactor, it is preferable to apply to the solution polymerization process carried out at a temperature above the melting point of the polymer. However, as disclosed in US Pat. No. 4,752,597, it may be used in slurry polymerization or gas phase polymerization in the form of a heterogeneous catalyst composition obtained by supporting the transition metal catalyst and the promoter on a porous metal oxide support.

Hereinafter, the present invention will be described in detail with reference to Examples, but the scope of the present invention is not limited by the following Examples.

Except where noted, all ligand and catalyst synthesis experiments were performed using standard Schlenk or glovebox techniques under nitrogen atmosphere and the organic solvent used in the reaction was refluxed under sodium metal and benzophenone to remove moisture Distilled immediately before use. ¹ H-NMR analysis of the synthesized ligand and catalyst was performed using Bruker 500 MHz at room temperature.

Cyclohexane, a polymerization solvent, was used after passing through a tube filled with molecular sieve 5Å and activated alumina and bubbling with high purity nitrogen to sufficiently remove moisture, oxygen, and other catalyst poisons. The polymerized polymer was analyzed by the method described below.

1. Melt Flow Index (MI)

It measured according to ASTM D 2839.

2. Density

According to ASTM D 1505, it was measured using a density gradient tube.

Example 1 Synthesis of Tris (2- (9 ', 9''-dimethylfluorene-2'-yl) phenoxy) (pentamethylcyclopentadienyl ) titanium (IV)

1) Synthesis of 2-bromo-9,9'-dimethylfluorene

2-bromofluorene (25 g, 102.0 mmol), iodine methane (43.4 g, 306.0 mmol) and 300 mL of DMSO were added to a 1000 mL three necked round flask, and the mixture was dissolved in a nitrogen atmosphere by stirring. Potassium-tert-butoxide (32.1 g, 285.6 mmol) was dissolved in 400 mL of DMSO and slowly added dropwise. After stirring at room temperature for 12 hours, the mixture was stirred at 80 ° C. for 1 hour, and then lowered to room temperature. It was mixed with 1000 mL of water and extracted with normal hexane. The organic mixture was washed three times with distilled water, and then dried with anhydrous magnesium sulfate (MgSO ₄₎ , and then the solvent was removed using a rotary evaporator. 27.0 g (96.9% yield) of phosphorus 2-bromo-9,9'-dimethylfluorene was obtained.

¹ H-NMR (CDCl ₃ ) δ = 1.65 (s, 6H), 7.35-7.39 (m, 2H), 7.44-7.50 (m, 2H), 7.58-7.62 (m, 2H), 7.72-7.73 (m, 1H) ppm

2) Synthesis of 2- (2 ''-methoxyphenyl) -9,9'-dimethylfluorene

2-bromo-9,9'-dimethylfluorene (27.0 g, 98.8 mmol), 2-methoxyphenylboronic acid (18.0 g, 118.6 mmol), palladium acetate (0.13 g, 0.6 mmol), triphenylphosphate To a flask containing pin (0.94 g, 3.6 mmol) and potassium phosphate (40.9 g, 177.9 mmol) was added 70 ml of water and 150 mL of dimethoxyethane mixed solution and refluxed for 6 hours. After cooling to room temperature, an aqueous ammonium chloride solution (150 mL) and 200 mL of diethyl ether were added, the organic layer was separated, the residue was extracted with diethyl ether, the collected organic layer was dried over magnesium sulfate, and volatiles were removed. Purification with hexane using a silica gel chromatography tube yielded 28.0 g (94.0%) of 2- (2 ''-methoxyphenyl) -9,9'-dimethylfluorene as a solid.

¹ H-NMR (CDCl ₃ ) δ = 1.56 (s, 6H), 3.88 (s, 3H), 7.04-7.06 (d, 1H), 7.08-7.11 (t, 1H), 7.33-7.39 (m, 3H) , 7.43-7.45 (d, 1H), 7.47-7.48 (d, 1H), 7.56-7.58 (d, 1H), 7.63 (s, 1H), 7.76-7.840 (t, 2H) ppm

3) Synthesis of 2- (9 ', 9' '-dimethylfluorene-2'-yl) phenol

2- (2 ''-methoxyphenyl) -9,9'-dimethylfluorene (25.0 g, 83.2 mmol) was dissolved in 400 mL of methylene chloride and then 100 mL of borontribromide (1M-methylene at -78 ° C). Chloride solution) was added dropwise, and slowly raised to room temperature to react for 3 hours. After the reaction, a mixture of ice (150 g) and diethyl ether (300 mL) was added, the organic layer was separated, the aqueous layer was extracted with diethyl ether, the collected organic layer was dried over magnesium sulfate, volatiles were removed, and silica gel chromatography was performed. Purification with a mixture of hexane and methylene chloride using a graphitic tube yielded 18.0 g (yield 75.5%) of 2- (9 ', 9' '-dimethylfluorene-2'-yl) phenol as a white solid.

¹ H-NMR (CDCl ₃ ) δ = 1.55 (s, 6H), 7.04-7.07 (m, 2H), 7.30-7.40 (m, 4H), 7.47-7.50 (m, 2H), 7.55 (s, 1H) , 7.78-7.80 (d, 1H), 7.85-7.87 (d, 1H) ppm

4) Synthesis of Tris (2- (9 ', 9''-dimethylfluorene-2'-yl) phenoxy) (pentamethylcyclopenta dienyl) titanium (IV)

Dissolve 2- (9 ', 9' '-dimethylfluorene-2'-yl) phenol (15.0 g, 51.3 mmol) in 200 mL toluene, lower the temperature of the solution to -78 ° C, and then normalbutyllithium (2.5 M hexane solution, 20.7 mL) was slowly added. When the injection was completed, the reaction temperature was raised to room temperature, followed by stirring for 12 hours. After 12 hours, the temperature of the reaction solution was lowered to -78 ° C, and then (pentamethylcyclopentadienyl) titanium (IV) trichloride (4.7 g, 16.3 mmol) was slowly added to 100 mL of toluene, followed by reaction. After raising the temperature to room temperature, the reaction was performed by stirring for 12 hours. When the reaction was completed, the salt was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and then recrystallized with purified toluene and hexane at -35 ℃. The precipitated solid was filtered and dried under reduced pressure to give a yellow solid tris (2- (9 ', 9' '-dimethylfluorene-2'-yl) phenoxy) (pentamethylcyclopentadienyl) titanium (IV ) 10.8 g (yield 63.9%) was obtained.

¹ H-NMR (C ₆ D ₆ ) δ = 1.38 (s, 15H), 1.42 (s, 18H), 6.92 (dd, 3H), 7.14 (m, 3H), 7.23 (m, 6H), 7.29 (m , 6H), 7.40 (d, 3H), 7.56 (s, 6H), 7.63 (m, 3H), 7.71 (d, 3H) ppm

Comparative Preparation Example 1 Synthesis of (dichloro) (pentamethylcyclopentadienyl) (2- (9 ', 9''-dimethylfluorene-2'-yl) phenoxy) titanium (IV)

Dissolve 2- (9 ', 9' '-dimethylfluorene-2'-yl) phenol (5.0 g, 17.1 mmol) in 100 mL toluene, lower the temperature of the solution to -78 ° C, and then add normalbutyllithium (2.5 M hexane solution, 6.9 mL) was slowly added. When the injection was completed, the reaction temperature was raised to room temperature, followed by stirring for 12 hours. After 12 hours, the temperature of the reaction solution was lowered to -78 ° C, and then (pentamethylcyclopentadienyl) titanium (IV) trichloride (4.7 g, 16.3 mmol) was slowly added to 100 mL of toluene, followed by reaction. After raising the temperature to room temperature, the reaction was performed by stirring for 12 hours. When the reaction was completed, the salt was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and then recrystallized with purified toluene and hexane at -35 ℃. The precipitated solid was filtered and dried under reduced pressure to give (dichloro) (pentamethylcyclopentadienyl) (2- (9 ', 9' '-dimethylfluorene-2'-yl) phenoxy) titanium as a red solid component. (IV) 5.6 g (yield 63.9%) were obtained.

¹ H-NMR (C ₆ D ₆ ) δ = 1.61 (s, 6H), 1.77 (s, 15H), 7.03-7.05 (t, 1H), 7.16-7.19 (t, 1H), 7.32-7.34 (m, 2H), 7.37-7.39 (d, 1H), 7.42-7.44 (d, 1H), 7.46-7.47 (d, 1H), 7.71-7.77 (m, 3H), 7.82-7.84 (d, 1H) ppm

Comparative Preparation Example 2 Synthesis of (2- (9 ', 9''-dimethylfluorene-2'-yl) phenoxy) dimethyl (pentamethyl cyclopentadienyl) titanium (IV)

(Dichloro) (pentamethylcyclopentadienyl) (2- (9 ', 9' '-dimethylfluorene-2'-yl) phenoxy) titanium (IV) (5 g, prepared by the method of Comparative Preparation Example 1) 9.3 mmol) was dissolved in 100 ml toluene and the temperature was lowered to -78 ° C. Methyl lithium (1.6 M diethyl ether solution, 17.4 mL) was slowly injected at the same temperature, and when the injection was completed, the temperature was raised to room temperature and stirred for 12 hours. When the reaction was completed, the salt was filtered off, the filtrate was distilled under reduced pressure to remove the solvent and recrystallized at -35 ℃ with purified hexane. At this time, the precipitated solid was filtered and dried under reduced pressure to obtain a yellow solid (2- (9 ', 9' '-dimethylfluorene-2'-yl) phenoxy) dimethyl (pentamethylcyclopentadienyl) titanium ( IV) 3.5 g (yield 55.8%) were obtained.

¹ H-NMR (C ₆ D ₆ ) δ = 0.81 (s, 6H), 1.53 (s, 6H), 1.63 (s, 15H), 7.12 (m, 2H), 7.21 (m, 1H), 7.33 (m , 2H), 7.51 (d, 1H), 7.25 (m, 2H), 7.80 (d, 1H) ppm

[Examples 3 to 4 and Comparative Examples 1 to 4] Copolymerization of ethylene and 1-octene

Copolymerization of ethylene and 1-octene was carried out using a batch polymerization apparatus as follows.

After sufficiently drying, 1200 mL of methylcyclohexane and 1-octene were added to a 2000 mL stainless steel reactor substituted with nitrogen, and then modified methylaluminoxane-7 (Akzo Nobel, modified MAO-7, 7 wt% Al Isopar solution). 11.1 mL of a 54.2 mM toluene solution was added to the reactor. Then, the temperature of the reactor was heated to 140 ° C., followed by 0.08 mL of titanium (IV) compound (27 mM toluene solution) and 0.6 mL of triphenylmethyllinium tetrakis (penta) synthesized in Examples 1 and Comparative Preparation Examples 1 and 2 Fluorophenyl) borate (99%, Boulder Scientific) 10 mM toluene solution was added sequentially, and the reactor was charged with ethylene to 20 kg / cm ² and then fed continuously to allow polymerization. After the reaction was performed for 10 minutes, ethanol containing 100 mL of 10 vol% aqueous hydrochloric acid solution was added to terminate the polymerization, and then stirred for 1 hour with 1.5 L of ethanol. The reaction product was filtered and separated. The recovered reaction product was dried for 8 hours in a vacuum oven at 60 ℃.

In the case of Example 4, Comparative Example 3 and Comparative Example 4, the titanium (IV) compound prepared in Example 1, Comparative Preparation Example 1 and Comparative Preparation Example 2 was used as a catalyst after standing in air for 24 hours. The content of octene, catalytic activity, melt flow index (MI) and density used in Table 1 are described.

Table 1

	catalyst		Octene Used (mL)	Catalyst Activity (Polymer Weight (Kg) / Catalyst Usage (mmol))	MI	Density (g / cc)
	Kinds	24 hours left in the air
Example 3	Example 1	X	20	15.38	5.2	0.9161
Example 4	Example 1	O	20	15.01	4.6	0.9161
Comparative Example 1	Comparative Production Example 1	X	20	14.73	9.5	0.9165
Comparative Example 2	Comparative Production Example 2	X	20	15.21	7.8	0.9158
Comparative Example 3	Comparative Production Example 1	O	20	14.98	8.1	0.9168
Comparative Example 4	Comparative Production Example 2	O	20	10.24	10.3	0.9166

As can be seen from the above examples, Examples 3 to 4 have low MI values compared to the MI values of the comparative examples to produce polymers having a large weight average molecular weight even under the condition of high temperature (140 ° C. or higher). there was. In particular, high molecular weight and low density copolymers were successfully obtained with ethylene and 1-octene.

[Example 5 and Comparative Example 5] Copolymerization of ethylene and 1-octene

Copolymerization of ethylene and 1-octene was carried out using a continuous polymerization apparatus as follows.

The titanium (IV) compound synthesized in Example 1 and Comparative Preparation Example 1 was used as a single active site catalyst, methylcyclohexane was used as a solvent, and the amount of catalyst used was as described in Table 2 below. Modified methylaluminoxane-7 (Akzo Nobel, modified MAO-7, 7 wt% Al Isopar solution) as an aluminum promoter, triphenylmethylnium tetrakis (pentafluorophenyl) borate (99%) as a boron promoter Boulder Scientific). Each catalyst was dissolved and injected into toluene at a concentration of 0.3 g / l, and polymerization was performed using 1-octene as the α-olefin comonomer. The conversion of the reactor was determined by gas chromatography analysis of the process stream after the reaction. The molecular weight was controlled as a function of reactor temperature and 1-octene content for a single site catalyst, and detailed polymerization conditions and polymerization results are described in Table 2 below.

TABLE 2

	division	Example 5	Comparative Example 5
Polymerization condition	catalyst	Example 1	Comparative Production Example 1
	Total solution flow rate (kg / h)	5	5
	Ethylene Charge (wt%)	10	10
	1-octene input ratio (1-octene / ethylene)	0.19	0.19
	Ti input amount (μmol / kg)	5.5	9.5
	Al / Ti ratio	30	30
	B / Ti ratio	3	3
	Reaction temperature (℃)	150.5	150.4
Polymerization Result	Ethylene Conversion (%)	95	95
	MI	3.242	26.600
	Density (g / cc)	0.9136	0.9164
Ti stands for Ti in a single site catalyst. Al: represents an aluminum (Al) atom in modified methylaluminoxane-7 (Akzo Nobel, modified MAO-7, 7 wt% Al Isopar solution) as a promoter. Represents a boron (B) atom in triphenylmethylnium tetrakis (pentafluorophenyl) borate.

In Comparative Example 5 and Example 5 of Table 2, it can be seen that the amount of catalyst required to achieve the same ethylene conversion of 95% is smaller in Example 5, since the Ti catalyst input amount is lower in Example 5. . In other words, it was found that the activity of the catalyst was higher in Example 5. In addition, while the density of the polymer prepared in Comparative Example 5 and Example 5 is similar, the MI value of the polymer produced at the same reaction temperature is lower in Example 5, so that the catalyst of Example 5 is heated at 150 ^° C. It can be seen that the polymer produces a higher molecular weight.

Although described in detail with respect to embodiments of the present invention as described above, those of ordinary skill in the art, without departing from the spirit and scope of the invention as defined in the appended claims Various modifications may be made to the invention. Therefore, changes in the future embodiments of the present invention will not be able to escape the technology of the present invention.

The transition metal compound or the catalyst composition including the transition metal compound according to the present invention can be easily prepared by an economical method due to the simple synthesis process, and also has excellent thermal stability of the catalyst, while maintaining high catalytic activity even at high temperatures. Copolymerization with olefins is good and high-molecular weight polymers can be produced in high yields, and thus have high commercial viability compared to known metallocene and nonmetallocene-based single-site catalysts. The transition metal compound of the present invention is a structure in which all other ligands except the cyclopentadienyl ligand are substituted with arylene oxide ligands, and no halogen anion ligand acting as a process corrosion substance or an alkyl anion ligand which is easily modified by air is used. Highly economical, easy to manufacture, relatively stable and high-purity catalysts that are not included in the process. They are single-site catalysts with high activity in olefin polymerization from a commercial point of view and ethylene having various physical properties using these catalyst components. Polymers or copolymers of ethylene and α-olefins can be produced economically. Therefore, the transition metal and the catalyst composition including the same according to the present invention can be usefully used for the preparation of ethylene homopolymer or copolymer with α-olefin having various physical properties.

Claims (15)

1. The transition metal compound of Formula 1

   [Formula 1]

   

   In Formula 1, M is a transition metal of Group 4 on the periodic table;

   Cp is a fused ring comprising a cyclopentadienyl ring or a cyclopentadienyl ring capable of bonding η ⁵ -with M, and a fused ring containing the cyclopentadienyl ring or cyclopentadienyl ring (C1- C20) alkyl, (C6-C30) aryl, tri (C1-C20) alkylsilyl, tri (C6-C20) arylsilyl, (C1-C20) alkyldi (C6-C20) arylsilyl, (C6-C20) aryl Di (C1-C20) alkylsilyl, (C2-C20) alkenyl and (C6-C30) aryl (C1-C20) alkyl, and may be further substituted with one or more selected from the group consisting of;

   Ar is (C6-C14) arylene;

   R ¹ and R ² independently of one another are a hydrogen atom, (C1-C20) alkyl or (C6-C30) aryl (C1-C20) alkyl;

   m is an integer selected from 0 to 3, provided that when R ¹ and R ² are hydrogen atoms at the same time m is not 0;

   R is (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C30) aryl, (C1-C20) alkyl (C6-C30) aryl, (C6-C30) aryl (C1-C20) alkyl or When (C1-C20) alkoxy and m is 2 or 3, each R may be the same or different;

   Alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkoxy and arylene of Ar are each independently halogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C30) aryl, (C6-C30) aryl (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C30) aryloxy, (C3-C20) alkylsiloxy, (C6-C30) arylsiloxy, (C1-C20 ) Alkylamino, (C6-C30) arylamino, (C1-C20) alkylphosphine, (C6-C30) arylphosphine, (C1-C20) alkylmercapto and (C6-C30) arylmercapto It may be further substituted with one or more selected substituents, and connected with (C3-C15) alkylene or (C3-C15) alkenylene, with or without fused ring with adjacent substituents of each substituent, to form an alicyclic ring and a monocyclic ring or Polycyclic aromatic rings can be formed.
2. The method of claim 1,

   Ar is a transition metal compound, characterized in that selected from the group consisting of phenylene, naphthylene and fluorene.
3. The method of claim 1,

   M is a transition metal compound, characterized in that titanium, zirconium or hafnium.
4. The method of claim 2,

   The transition metal compound is selected from the following transition metal compound.

   

   

   

   Wherein Cp is cyclopentadienyl or pentamethylcyclopentadienyl.
5. A transition metal compound according to any one of claims 1 to 4; And

   A promoter selected from aluminum compounds, boron compounds or mixtures thereof;

   Ethylene homopolymer or a transition metal catalyst composition for producing a copolymer of ethylene and α-olefin comprising a.
6. The method of claim 5,

   The ratio of the transition metal compound and the aluminum compound promoter is in the range of 1: 10 to 5,000 based on the molar ratio of transition metal (M) to aluminum (Al), or the air of ethylene homopolymer or ethylene and α-olefin. Transition metal catalyst composition for preparation of coalescing.
7. The method of claim 5,

   The aluminum compound promoter is one or two or more mixtures selected from alkylaluminoxane or organoaluminum, and includes methylaluminoxane, improved methylaluminoxane, tetraisobutylaluminoxane, trimethylaluminum, triethylaluminum and triisobutylaluminum, tri A transition metal catalyst composition for producing an ethylene homopolymer or a copolymer of ethylene and an α-olefin, which is selected from octyl aluminum alone or as a mixture of two or more thereof.
8. The method of claim 5,

   The ratio of the transition metal compound, the aluminum compound promoter and the boron compound promoter is in the range of 1: 0.1 to 200: 10 to 1000 based on the molar ratio of the transition metal (M): boron atom (B): aluminum atom (Al). A transition metal catalyst composition for producing an ethylene homopolymer or a copolymer of ethylene and an α-olefin.
9. The method of claim 5,

   The boron compound promoter is selected from tris (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and triphenylmethyllinium tetrakis (pentafluorophenyl) borate alone, Or a mixture thereof, a transition metal catalyst composition for producing an ethylene homopolymer or a copolymer of ethylene and an α-olefin.
10. Method for producing an ethylene homopolymer or copolymer of ethylene and α-olefin using the transition metal catalyst composition according to claim 5.
11. The method of claim 10,

    The α-olefin polymerized with ethylene is propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, Ethylene homopolymer or ethylene, characterized in that the ethylene content is selected from 1-hexadecene and 1-atocene alone or a mixture of two or more, wherein the ethylene content in the copolymer of ethylene and α-olefin is included in 50 to 99% by weight Method for producing a copolymer of α-olefins.
12. The method of claim 10,

    The ethylene homopolymerization or copolymerization of ethylene monomers and α-olefins in the reactor is 1 to 1,000 atm, polymerization reaction temperature is 60 ~ 300 ℃ characterized in that the copolymerization of ethylene homopolymer or ethylene and α-olefin Way.
13. The method of claim 12,

    The ethylene homopolymerization or copolymerization of ethylene monomer and α-olefin in the reactor is 1 to 150 atm and polymerization reaction temperature is 80 ~ 250 ℃ characterized in that the copolymerization of ethylene homopolymer or ethylene and α-olefin Way.
14. Ethylene homopolymer or copolymer of ethylene and α-olefin prepared using the transition metal compound catalyst according to any one of claims 1 to 4.
15. Ethylene homopolymer or copolymer of ethylene and α-olefin prepared by using the transition metal compound according to claim 5 catalyst composition.