KR101889979B1 - new transition metal complex, catalyst composition containing the same for olefin polymerization and methods for preparing ethylene homopolymers or copolymers of ethylene and α-olefins using the same - Google Patents

Abstract

The present invention relates to a transition metal catalyst composition having a high catalytic activity for preparing a transition metal compound, an ethylene homopolymer containing the same, or a copolymer of ethylene and an? -Olefin, and a process for preparing a copolymer of ethylene homopolymer or ethylene and an? ≪ / RTI >

Description

[0001] The present invention relates to a novel transition metal compound, a transition metal catalyst composition for olefin polymerization containing the same, and a process for preparing a copolymer of ethylene homopolymer or ethylene and an alpha -olefin using the same, preparing ethylene homopolymers or copolymers of ethylene and alpha-olefins using the same}

The present invention relates to a transition metal compound and a transition metal catalyst composition for the production of a copolymer of ethylene homopolymer or ethylene and an? -Olefin containing the same, and a process for producing a copolymer of ethylene homopolymer or ethylene and? -Olefin.

Conventionally, the so-called Ziegler-Natta catalyst system composed of the main catalyst component of a titanium or vanadium compound and the cocatalyst component of an alkyl aluminum compound has been generally used for preparing a copolymer of ethylene with a homopolymer or an? -Olefin. However, although the Ziegler-Natta catalyst system exhibits high activity for ethylene polymerization, the molecular weight distribution of the resulting polymer is generally broad due to the uneven catalytic activity point, and in particular, the disadvantage that the composition distribution is not uniform in the copolymer of ethylene and? .

Since the metallocene catalyst system composed of the metallocene compound of the transition metal of the periodic table group 4, such as titanium, zirconium, and hafnium, and methylaluminoxane, which is a cocatalyst, is a homogeneous catalyst having a single catalytic active site, - It is characterized that the polyethylene having narrow molecular weight distribution and homogeneous composition distribution can be produced compared with the Natta catalyst system. For example, European Patent Publication Nos. 320,762, 372,632 or 63-092621, Nos. 02-84405 and 03-2347 disclose that Cp ₂ TiCl ₂ , Cp ₂ ZrCl ₂ , Cp (Mw / Mn) in the range of 1.5 to 2.0, by polymerizing ethylene in a high activity by activating the metallocene compound with the promoter methyl aluminoxane in the presence of a catalyst such as ₂ ZrMeCl, Cp ₂ ZrMe ₂ , ethylene (IndH ₄ ) ₂ ZrCl ₂ , Polyethylene can be produced. However, it is difficult to obtain a polymer having a high molecular weight in the catalyst system. When applied to a solution polymerization method carried out at a high temperature, the polymerization activity is rapidly reduced and the? -Hydrogenolysis reaction predominates and a high molecular weight Are not suitable for preparing polymers.

On the other hand, as a catalyst capable of producing a polymer having high catalytic activity and high molecular weight by ethylene homopolymerization or copolymerization of ethylene and an -olefin under solution polymerization conditions, a so-called geometrically constrained nonmetalocene catalyst (Aka single-site catalyst). EP 0416815 and EP 0420436 disclose an example in which an amide group is linked in the form of a ring to one cyclopentadiene ligand. In EP 0842939, a phenol-based ligand as an electron donor compound is reacted with a cyclopentadiene ligand An example of a catalyst in the form of a ring is shown. However, since the yield of the ring-forming reaction process between the ligand and the transition metal compound is very low during the synthesis step of the geometric constrained catalyst, there are many difficulties in commercial use.

On the other hand, examples of non-metallocene catalysts that are not geometrically constrained include, but are not limited to, bis-phenoxide ligands in US Pat. No. 5,079,205 and US Pat. No. 5,043,408 in which chelate- Is too low to be commercially used for preparing a copolymer with an ethylene homopolymer or an? -Olefin which is carried out at a high temperature.

Japanese Patent Application Laid-Open Nos. 1996-208732 and 2002-212218 disclose use as an olefin-based polymerization catalyst having an anilido ligand, but an example in a commercially meaningful polymerization temperature range is not disclosed. An example of using an anilido ligand as a non-metallocene catalyst for polymerization was reported in " Organometallics 2002 , 21 , 3043 (Nomura et al.)", But this case was limited to a methyl group as a simple alkyl substituent.

European Patent Publication No. 320,762 (June 21, 1989) European Patent Publication No. 372,632 (June 14, 1990) Japanese Patent Laid-Open No. 63-092621 (Apr. 23, 1988) Japanese Patent Application Laid-Open No. 02-84405 (1990.02.26) Japanese Patent Application Laid-Open No. 03-2347 (1991.01.08) European Patent No. 0416815 (Mar. 13, 1991) European Patent No. 0420436 (Apr. 03, 1991) European Patent No. 0842939 (May 20, 1998) International Patent No. 00/005238 (2000.03.03) U.S. Patent No. 5,079,205 (Jan. 1, 1992) U.S. Patent No. 5,043,408 (Aug. 27, 1991) Japanese Patent Application Laid-Open No. 1996-208732 (Aug. 13, 1996) Japanese Patent Application Laid-Open No. 2002-212218 (July 31, 2002)

 Organometallics 2002, 21, 3043 (Nomura et al.)

The present invention provides a transition metal compound useful as a catalyst for the production of an ethylene homopolymer or a copolymer of ethylene and an? -Olefin, and also provides a catalyst composition comprising the same.

The present invention also provides an ethylene homopolymer or a copolymer of ethylene and an? -Olefin prepared using a catalyst composition comprising the transition metal compound.

The present invention also relates to a single active site catalyst having a high activity in olefin polymerization as well as a simple synthesis route and a high activity, and to provide a process for producing an ethylene homopolymer or a copolymer of ethylene and an- In the presence of a catalyst.

One aspect of the present invention in order to achieve the above object is to provide a method for preparing a cyclopentadiene derivative and an ortho - A compound having at least one aryl oxide ligand which is advantageous for stability at high temperatures due to the nitrogen atom of the carbazole group being coordinated to the center metal to form a stable catalyst structure and which is not cross-linked with the ligand, alpha-olefin < / RTI >

[Chemical Formula 1]

[In the above formula (1)

M is a transition metal of Group 4 on the Periodic Table;

Cp is a bond that can bond to M and η ⁵ - A fused ring containing a cyclopentadienyl ring or a cyclopentadienyl ring, wherein the fused ring containing the cyclopentadienyl ring or the cyclopentadienyl ring is a (C1-C20) alkyl group, a (C6-C30) aryl group , (C2-C20) alkenyl groups and (C6-C30) aryl (C1-C20) alkyl groups;

R ₁ To R ₃ independently represent a hydrogen atom, (C1-C20) alkyl, (C1-C20) alkoxy, (C3-C20) cycloalkyl, (C6-C30) aryl, (C6-C30) aralkyl (C1- each other C20) alkyl group, (C1-C20) alkyl (C6-C30) aryl, (C1-C20) alkylsilyl group or (C6-C30) arylsilyl group, with or without adjacent fused rings (C3-C12) alkylene or (C3-C12) alkenylene to form an alicyclic ring or may form a monocyclic or polycyclic aromatic ring;

n is an integer from 1 to 3;

o, p and q are integers from 1 to 4;

X is a halogen atom, a (C1-C20) alkyl group, a (C3-C20) cycloalkyl group, a (C6- (C 1 -C 20) alkyl group or a (C 6 -C 30) aryl group, a phosphine group substituted with a (C 1 -C 20) alkyl group, or a Garlic sauce;

The alkyl, alkoxy, cycloalkyl, aryl, aralkyl, alkylsilyl, arylsilyl, alkylene and alkenylene of R ₁ to R ₃ are each independently selected from the group consisting of halogen, (C 1 -C 20) alkyl, (C 3 -C 20) (C6-C30) alkoxy, (C6-C30) aryloxy, (C3-C20) alkylsiloxy, (C6-C30) (C6-C30) arylthio, (C1-C20) alkylphosphine, (C6-C30) alkylthio, (C1-C20) alkylmercapto, (C6-C30) arylmercapto, and the like.

Preferably, in the transition metal compound represented by the formula (1), M is titanium, zirconium or hafnium; Wherein Cp is cyclopentadienyl or pentamethylcyclopentadienyl; And n may be 1 or 2.

Also preferably, X in formula (1) may be selected from chlorine, a methyl group, a methoxy group, an isopropoxy group and a dimethylamino group.

The formula (1) of the present invention may be represented by the following formulas (2) to (8), but is not limited thereto.

 (2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[In the above Chemical Formulas 2 to 9,

Cp is cyclopentadienyl or pentamethylcyclopentadienyl;

M is titanium, zirconium or hafnium;

R ₁₁ to R ₁₄ and R ₂₁ to R ₂₂ independently represent a hydrogen atom, (C 1 -C 20) alkyl group, (C 1 -C 20) alkoxy group, (C 3 -C 20) cycloalkyl group, (C 6 -C 30) C6-C30) ar (C1-C20) alkyl group, (C1-C20) alkylsilyl group or (C6-C30) arylsilyl group;

Wherein n is 1 or 2;

X is selected from a chlorine, a methyl group, a methoxy group, an isopropoxy group and a dimethylamino group.

More specifically, the transition metal compound of Formula 1 according to an embodiment of the present invention may be selected from the following structures, but is not limited thereto.

Wherein: Cp is cyclopentadienyl or pentamethylcyclopentadienyl;

X ₁ and X ₂ independently of one another may be selected from the group consisting of chlorine, methyl, methoxy, isopropoxy, benzyl, fluorenyl, fluorenyloxy and dimethylamino.

According to another aspect of the present invention, there is provided a transition metal catalyst for an ethylene homopolymer or a copolymer of ethylene and an? -Olefin comprising the transition metal compound and an aluminum compound cocatalyst, a boron compound cocatalyst, or a mixture thereof, ≪ / RTI >

The aluminum compound cocatalyst of the transition metal catalyst composition according to an embodiment of the present invention is selected from the group consisting of methyl aluminoxane, modified methyl aluminoxane, tetraisobutyl aluminoxane, trialkyl aluminum, triethyl aluminum, and triisobutyl aluminum, And the amount of the promoter of the aluminum compound may be 1: 50 to 1: 5,000 based on the mole ratio of the transition metal (M): aluminum atom (Al).

Also, the boron compound cocatalyst of the transition metal catalyst composition according to an embodiment of the present invention may be selected from the group consisting of N, N-dimethylanilinium tetrakispentafluorophenyl borate and triphenylmethylninium tetrakispentafluorophenyl borate, The amount of the transition metal M to be used may be 1: 0.1 to 100: 10 to 1000 based on the molar ratio of the transition metal M: boron atom (B): aluminum atom (Al).

According to another aspect of the present invention, there is provided an ethylene homopolymer or a copolymer of ethylene and an -olefin using the transition metal compound or the catalyst composition, and a process for producing the polymer. The comonomer to be polymerized with ethylene in the process for producing a copolymer of ethylene and an? -Olefin according to an embodiment is at least one selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, Undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-aidocene, or a mixture thereof, and the ethylene content of the copolymer of ethylene and the? -Olefin is 60 to 99 wt% Lt; / RTI >

The pressure in the reactor of the ethylene monomer according to an embodiment of the present invention may be 1 to 1000 atm and the polymerization reaction temperature may be 60 to 300 ° C. The present invention also includes a novel transition metal compound or a novel transition metal A copolymer of ethylene and an? -Olefin or an ethylene-olefin-diene copolymer produced using the transition metal compound catalyst composition.

The transition metal compound or the catalyst composition comprising the transition metal compound according to the present invention can be easily produced by an economical method because of simple synthesis process and excellent thermal stability of the catalyst, It is possible to produce a polymer having a high copolymerization reactivity with olefins and a high molecular weight at a high yield and is more commercially viable than the known metallocene and non-metallocene single-site catalysts.

Therefore, the transition metal and the catalyst composition containing the transition metal according to the present invention can be usefully used for the production of a copolymer with an ethylene homopolymer or an? -Olefin having various physical properties.

The present invention provides a novel transition metal compound, more specifically represented by the following formula (1).

The transition metal compound of the present invention has a better electron-donating effect by directly substituting the nitrogen atom of the carbazole on the cyclopentadiene derivative and the ortho - position around the Group 4 transition metal, The nitrogen atom of the sol is coordinated with the center metal to form a stable catalyst structure so that it has at least one aryl oxide ligand advantageous for stability even at high temperatures and has a structure that is not cross-linked with each other.

[Chemical Formula 1]

[In the above formula (1)

M is a transition metal of Group 4 on the Periodic Table;

Cp is a bond that can bond to M and η ⁵ - A fused ring containing a cyclopentadienyl ring or a cyclopentadienyl ring, wherein the fused ring containing the cyclopentadienyl ring or the cyclopentadienyl ring is a (C1-C20) alkyl group, a (C6-C30) aryl group , (C2-C20) alkenyl groups and (C6-C30) aryl (C1-C20) alkyl groups;

R ₁ To R ₃ independently represent a hydrogen atom, (C1-C20) alkyl, (C1-C20) alkoxy, (C3-C20) cycloalkyl, (C6-C30) aryl, (C6-C30) aralkyl (C1- each other C20) alkyl group, (C1-C20) alkyl (C6-C30) aryl, (C1-C20) alkylsilyl group or (C6-C30) arylsilyl group, with or without adjacent fused rings (C3-C12) alkylene or (C3-C12) alkenylene to form an alicyclic ring or may form a monocyclic or polycyclic aromatic ring;

n is an integer from 1 to 3;

o, p and q are integers from 1 to 4;

X is a halogen atom, a (C1-C20) alkyl group, a (C3-C20) cycloalkyl group, a (C6- (C 1 -C 20) alkyl group or a (C 6 -C 30) aryl group, a phosphine group substituted with a (C 1 -C 20) alkyl group, or a Garlic sauce;

The alkyl, alkoxy, cycloalkyl, aryl, aralkyl, alkylsilyl, arylsilyl, alkylene and alkenylene of R ₁ to R ₃ are each independently selected from the group consisting of halogen, (C 1 -C 20) alkyl, (C 3 -C 20) (C6-C30) alkoxy, (C6-C30) aryloxy, (C3-C20) alkylsiloxy, (C6-C30) (C6-C30) arylthio, (C1-C20) alkylphosphine, (C6-C30) alkylthio, (C1-C20) alkylmercapto, (C6-C30) arylmercapto, and the like.

M, which is a transition metal of Group 4 in the Periodic Table of the Chemical Formula 1, is preferably titanium, zirconium or hafnium.

In addition, Cp ⁵ a central metal and η - as fused rings fused ring or a substituted including the cyclopentadienyl ring, such as capable of binding to a cyclopentadiene ring, and inde-substituted cyclopentadienyl ring, a carbonyl, Floresta carbonyl, in which Means that the substituent may be substituted with a (C1-C20) alkyl group, a (C6-C30) aryl group, a (C2-C20) alkenyl group or a (C6-C30) aryl (C1-C20) alkyl group. Specific examples thereof include cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, butylcyclopentadienyl, sec -butylcyclopentadienyl N-butyl, n-butyl, tert -butylmethylcyclopentadienyl, trimethylsilylcyclopentadienyl, indenyl, methylindenyl, dimethylindenyl, ethylindenyl, isopropylindenyl, fluorenyl, methylflorenyl, dimethylflorenyl, ethyl Fluorenyl, isopropylpropenyl, and the like.

And (C1-C20) alkyl groups of the invention include both the linear or non-linear form, for example, methyl, ethyl, n- propyl, isopropyl, n- butyl, sec - butyl, tert - butyl , n-pentyl group, neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group or n-eicosyl group, Is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group or tert -butyl group; (C 1 -C 20) alkylsilyl or (C 6 -C 30) arylsilyl is, for example, a methylsilyl group, an ethylsilyl group, a phenylsilyl group, a dimethylsilyl group, a diethylsilyl group or a diphenylsilyl group, , triethylsilyl group, tri -n- propyl silyl group, triisopropylsilyl group, tri -n--butylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, tri-iso-butylsilyl group , tert - butyldimethylsilyl group, tri -n- pentyl silyl group, tri -n- hexyl silyl group, tri-cyclohexyl-silyl or triphenyl silyl group, it is preferred in a trimethylsilyl group, tert - butyldimethylsilyl group Or a triphenylsilyl group; (C6-C30) aryl group or (C1-C20) alkyl (C6-C30) aryl group is preferably a phenyl group, a 2-tolyl group, a 3-tolyl group, Xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2 , 3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3 , 4, 6-tetra-methylphenyl, 2,3,5,6-tetra methylphenyl, penta-methylphenyl group, ethylphenyl group, n- propyl group, isopropyl group, n- butyl group, a sec - butyl group, a tert - butyl N-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl, n-tetradecylphenyl, biphenyl, fluorenyl, triphenyl, Naphthyl group or anthracenyl group, and among these, preferred are phenyl group, naphthyl group, biphenyl, 2-isopropylphenyl, 3,5-xylyl group, Is a 2,4,6-trimethylphenyl group; (C6-C30) aryl (C1-C10) alkyl group is, for example, a benzyl group, a (2-methylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6- (2,3,6-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, Dimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) Butylphenyl) methyl group, (tert-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (pentylphenyl) (N-pentylphenyl) methyl group, (n-pentylphenyl) methyl group, (n-pentylphenyl) Carbonyl) methyl group, (n- tetradecyl phenyl) methyl group, naphthylmethyl group, or an anthracenyl group, preferred of them is a benzyl group; (C1-C20) alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec -butoxy, tert- - hexyl, n-octyl, n-dodecyl, n-pentadecyl or n-eicosyl. Of these, preferred are methoxy, ethoxy, isopropoxy or tert- to be.

In Formula 1, X is a halogen atom, e.g., fluorine, chlorine, bromine, and iodine atoms; Cyclopentadienyl not a carbonyl derivative (C1-C20) alkyl group, a methyl group as an example, ethyl, n- propyl, isopropyl, n- butyl, sec - butyl, tert - butyl, n- pentyl, neo An n-hexyl group, an n-octyl group, a n-decyl group, a n-dodecyl group, an n-pentadecyl group and an n-eicosyl group, of which a methyl group, a tert -butyl group, or an amyl group; Examples of the (C3-C20) cycloalkyl group include a cyclopropane group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, or an adamantyl group; Examples of (C6-C30) aryl (C1-C20) alkyl groups include benzyl, (2-methylphenyl) methyl, (3- methylphenyl) methyl, (2,4-dimethylphenyl) methyl group, (4,6-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, Trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (Butylphenyl) methyl group, (tert-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (N-decylphenyl) methyl group, (n-decylphenyl) methyl group, (n-pentylphenyl) ) Methyl group, (n- tetradecyl phenyl) methyl group, can be mentioned a naphthyl group or an anthracenyl group, of which preferred is a benzyl group; (C1-C20) alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec -butoxy, tert- - hexyl, n-octyl, n-dodecyl, n-pentadecyl or n-eicosyl. Of these, preferred are methoxy, ethoxy, isopropoxy or tert- ; (C3-C20) trimethyl siloxy group, siloxy triethyl, tri -n- propyl siloxy, triisopropyl siloxy, tri -n- butyl-siloxy group, the tree as an example of alkyl siloxy - sec - butyl-siloxy group, N-hexylsilyl group, tricyclohexylsilyl group, tricyclohexylsiloxy group, tri- tert -butylsiloxy group, tri-isobutylsiloxy group, tert -butyldimethylsiloxy group, Preferred is a trimethylsiloxy group, or tert -butyldimethylsiloxy group.

Examples of the amino group which is substituted with (C1-C20) alkyl group or (C6-C30) aryl group which is another example of X in the above formula (1) include dimethylamino group, diethylamino group, di- Di-n-butylamino group, di- sec -butylamino group, di- tert -butylamino group, diisobutylamino group, tert -butylisopropylamino group, di- an n-decylamino group, a diphenylamino group, a dibenzylamino group, a methylethylamino group, a methylphenylamino group, a benzylhexylamino group, a bistrimethylsilylamino group or a bis-tert-butyldimethylsilylamino group; Examples of the phosphine group substituted with a (C1-C20) alkyl group or substituted with a (C6-C30) aryl group include a dimethylphosphine group, a diethylphosphine group, a di-n-propylphosphine group, a diisopropylphosphine group, Butylphosphine group, di- sec -butylphosphine group, di- tert -butylphosphine group, diisobutylphosphine group, tert -butylisopropylphosphine group, di- Di-n-decylphosphine group, diphenylphosphine group, dibenzylphosphine group, methylethylphosphine group, methylphenylphosphine group, benzylhexylphosphine group, bistrimethylsilylphosphine group or bis-tert-butyldimethylsilylphosphine group Among these, preferred are dimethylphosphine group, diethylphosphine group or diphenylphosphine group; Examples of mercapto groups substituted with (C1-C20) alkyl groups are methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, 1-butyl mercaptan, isopentyl mercaptan, preferably ethyl mercaptan, or Isopropylmercaptan.

In the transition metal compound of Formula 1, n is preferably 1 or 2.

The formula (1) of the present invention may be represented by the following formulas (2) to (9), but is not limited thereto.

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[In the above Chemical Formulas 2 to 9,

Cp is cyclopentadienyl or pentamethylcyclopentadienyl;

M is titanium, zirconium or hafnium;

R ₁₁ to R ₁₄ and R ₂₁ to R ₂₂ independently represent a hydrogen atom, (C 1 -C 20) alkyl group, (C 1 -C 20) alkoxy group, (C 3 -C 20) cycloalkyl group, (C 6 -C 30) C6-C30) ar (C1-C20) alkyl group, (C1-C20) alkylsilyl group or (C6-C30) arylsilyl group;

Wherein n is 1 or 2;

X is selected from chlorine, methyl, methoxy, isopropoxy and dimethylamino groups.

More specifically, the transition metal compound of Formula 1 according to an embodiment of the present invention may be selected from the following structures, but is not limited thereto.

Wherein: Cp is cyclopentadienyl or pentamethylcyclopentadienyl;

X ₁ and X ₂ independently of one another may be selected from the group consisting of chlorine, methyl, methoxy, isopropoxy, benzyl, fluorenyl, fluorenyloxy and dimethylamino.

On the other hand, the transition metal compound of the above formula (1) is preferably a transition metal complex in order to be an active catalyst component used in the production of a copolymer of ethylene homopolymer or ethylene and an -olefin, , Or an aluminum compound or a boron compound capable of acting as an anion, or a mixture thereof, as a cocatalyst, and a catalyst composition comprising the transition metal compound and the cocatalyst described above can also act as a cocatalyst, Lt; / RTI >

The boron compound which can be used as a cocatalyst in the present invention is a boron compound which is known in U.S. Patent No. 5,198,401, and can be specifically selected from the compounds represented by the following formulas (11) to (13).

(11)

B (R < ^{41 >} ) ₃

[Chemical Formula 12]

[R ⁴² ] ⁺ [B (R ⁴¹ ) ₄ ] ^-

[Chemical Formula 13]

[(R ⁴³ ) _p ZH] ⁺ [B (R ⁴¹ ) ₄ ] ^-

In the formulas (11) to (13), B represents a boron atom; R ⁴¹ is a phenyl group, and the phenyl group is a fluorine atom, (C1-C20) alkyl group, substituted by fluorine atoms (C1-C20) alkyl, (C1-C20) substituted with an alkoxy group or a fluorine atom, (C1-C20 ) Alkoxy group; < / RTI > R ⁴² is a (C5-C7) aromatic radical or a (C1-C20) alkyl (C6-C20) aryl radical or a (C6-C30) arylC1-C20) alkyl radical such as triphenylmethyl radical; Z is a nitrogen or phosphorus atom; R ⁴³ is a (C1-C20) alkyl radical or an anilinium radical substituted with two (C1-C10) alkyl groups together with the nitrogen atom; p is an integer of 2 or 3;

Preferable examples of the boron-based co-catalyst include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluoro (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, tetrakis (triphenylphosphine) borane, (Pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluorophenyl) borate, tetrakis , 5-trifluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate or tetrakis (3,5-bistrifluoromethylphenyl) . Specific examples of these compounds include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1'-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, tri (Pentafluorophenyl) borate, triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis Tri (n-butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium (tetrabutylammonium) N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluoro (Pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) Borate. Of these, N, N-dimethylanilinium tetrakispentafluorophenylborate, triphenylmethylninium tetrakispentafluorophenylborate or trispentafluoroborane are most preferable.

Examples of the aluminum compound that can be used as a cocatalyst in the catalyst composition according to one embodiment of the present invention include aluminoxane compounds represented by Chemical Formulas 14 or 15, organoaluminum compounds represented by Chemical Formula 16 or organoaluminum alkyl oxides represented by Chemical Formula 17 or Chemical Formula 18 Or an organoaluminum aryloxide compound.

 [Chemical Formula 14]

(-Al (R ⁴⁴ ) -O-) _m

[Chemical Formula 15]

(R ⁴⁴ ) ₂ Al - (- O (R ⁴⁴ ) -) _q - (R ⁴⁴ ) ₂

[Chemical Formula 16]

(R ⁴⁵ ) _r Al (E) _3-r

[Chemical Formula 17]

(R < ⁴⁶ >) ₂ AlOR ⁴⁷

[Chemical Formula 18]

R ^{46 is} Al (OR ⁴⁷ ) ₂

In the above formulas 14 to 18, R ⁴⁴ is a (C 1 -C 20) alkyl group, preferably a methyl group or an isobutyl group, m and q are integers of 5 to 20; R ⁴⁵ and R ⁴⁶ are (C 1 -C 20) alkyl groups; E is a hydrogen atom or a halogen atom; r is an integer between 1 and 3; R ⁴⁷ may be selected from a (C 1 -C 20) alkyl group or a (C 6 -C 30) aryl group.

Specific examples of the aluminum compound that can be used include aluminoxane compounds such as methyl aluminoxane, modified methyl aluminoxane, and tetraisobutyl aluminoxane; Examples of the organoaluminum compound include trialkylaluminum including trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum; Dialkyl aluminum chlorides, including dimethyl aluminum chloride, diethyl aluminum chloride, dipropyl aluminum chloride, diisobutyl aluminum chloride, and dihexyl aluminum chloride; Alkylaluminum dichlorides including methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, and hexylaluminum dichloride; Dialkylaluminum hydride including dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride and dihexylaluminum hydride, preferably trialkylaluminum, more preferably trialkylaluminum hydride, Preferably triethylaluminum and triisobutylaluminum.

In the transition metal catalyst composition for preparing the ethylene homopolymer or the copolymer of ethylene and an? -Olefin containing the cocatalyst according to the present invention, the preferable range of the ratio between the transition metal compound of the formula (1) and the cocatalyst is, The ratio of boron atom (B) to aluminum atom (Al) is 1: 0.1 to 100: 10 to 1,000, and more preferably 1: 0.5 to 5: 25 to 500.

In another aspect of the present invention, the process for preparing an ethylene polymer using the transition metal catalyst composition may be carried out by contacting the transition metal catalyst, the cocatalyst, and ethylene or, if desired, a vinyl 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 the respective components may be premixed and introduced into the reactor. There is no particular limitation on the mixing conditions such as the order of introduction, temperature, or concentration.

Preferred organic solvents that may be used in the above process are C3-C20 hydrocarbons. Specific examples thereof include butane, isobutane, pentane, hexane, heptane, octane, isooctane, nonane, decane, dodecane, cyclohexane, methylcyclohexane , Benzene, toluene, xylene, and the like.

Specifically, when ethylene homopolymer is prepared, ethylene alone is used as a monomer, and the pressure of ethylene is suitably 1 to 1000 atm, and more preferably 10 to 150 atm. It is also effective that the polymerization reaction is carried out at a temperature of 60 to 300 ° C, preferably at 80 to 250 ° C.

When a copolymer of ethylene and an? -Olefin is prepared, C3-C18? -Olefins may be used as a comonomer together with ethylene, preferably propylene, 1-butene, 1-pentene, - 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 and ethylene can be copolymerized. In this case, the preferred ethylene pressure and polymerization reaction temperature may be the same as in the case of the ethylene homopolymer production, and the copolymer prepared according to the process of the present invention usually contains not less than 50% by weight of ethylene, preferably not more than 60% % Ethylene, more preferably from 60 to 99 wt%, based on the total weight of the composition.

  As described above, the linear low-density polyethylene (LLDPE) prepared by using C4-C10 alpha -olefin as the comonomer has a density region of 0.910 to 0.940 g / cc and an ultra low density polyethylene (VLDPE Or ULDPE) or an olefin elastomeric region. In order to control the molecular weight of the ethylene homopolymer or copolymer according to the present invention, hydrogen may be used as a molecular weight modifier and has a weight average molecular weight (Mw) generally 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 a polymerization reactor, it is preferable to apply to a solution polymerization process carried out at a temperature above the melting point of the polymer. However, it may also be used for slurry polymerization or gas phase polymerization in the form of a non-uniform catalyst composition obtained by supporting the transition metal catalyst and cocatalyst on a porous metal oxide support as disclosed in U.S. Patent No. 4,752,597.

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

Except where otherwise noted, all ligand and catalyst synthesis experiments were carried out using standard Schlenk or glove box techniques under nitrogen atmosphere and organic solvents used in the reaction were refluxed under sodium metal and benzophenone to remove water And used by distillation just before use. ¹ H-NMR analysis of the synthesized ligand and catalyst was carried out using Bruker 500 MHz at room temperature.

Cyclohexane, a polymerization solvent, was used after thoroughly removing moisture, oxygen, and other catalyst poison substances through a pipe filled with 5A molecular sieve and activated alumina and bubbling with high purity nitrogen. The polymerized polymer was analyzed by the method described below.

1. Melt Flow Index (MI)

It was measured according to ASTM D 2839.

2. Density

ASTM D 1505, using a mill tool piping.

[Example 1]

2- (9H-carbazol-9-yl) phenoxy (2,3,4,5-tetramethylcyclopenta-2,4-dien- 1- yl) titanium (IV) dichloride [2- -carbazol-9-yl) phenoxy (2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl) titanium (IV) dichloride

(1) Synthesis of 2- (9H- carbazol-9-yl) phenol [2- (9H- carbazol-9-yl) phenol]

(0.7 mmol, 5%), trans-1, 2-diaminocyclohexane (prepared as described in Example 1) in dioxane (20 ml), in which carbazole (17.9 mmol) and 2-bromoanisole 2.8 mmol, 20%) and potassium phosphate (14 mmol), and the solution is stirred at 100 ^° C for 16 hours. After the reaction, the solution was filtered, and the solvent was removed. The residue was purified by using a silica gel chromatography tube to obtain 14.6 mmol (82%) of 9- (2-methoxyphenyl) -9H-carbazole. Carbazole (14.6 mmol) obtained in this manner and 2 equivalents of tribromoboron (1 M solution of dichloromethane) were added to a dichloromethane solvent and stirred for 5 hours (TLC Control). After the reaction, water is added and the reaction is extracted with ethyl acetate. The remaining water was removed with magnesium sulfate and purified using a silica gel chromatography tube to obtain 11.8 mmol (81%) of 2- (9H-carbazol-9-yl) phenol.

¹ H NMR (CDCl ₃ , 500 MHz)? 4.89 (br s, 1H), 6.68 (m, 1H), 6.84 ), 8.01 (d, 2H, J = 6.6Hz) ppm

( IV) (2) (2- (9H-carbazol-9-yl) phenoxy) (1,2,3,4,5-pentamethylcyclopenta- Synthesis of [(2- (9H-carbazol-9-yl) phenoxy] (1,2,3,4,5-pentamethylcyclopenta-2,4-dien-

N-Butyllithium (2.5 M hexane solution, 1.55 mL) was slowly added to the solution at -78 ° C, and the mixture was stirred at room temperature Stir for 12 hours. Titanium (IV) trichloride (0.94 g, 3.1 mmol) was dissolved in 5 mL of toluene, and the reaction was allowed to proceed at room temperature for 12 hours . After completion of the reaction, the reaction mixture was filtered through celite to remove the solvent. The filtrate was recrystallized with purified toluene and hexane at -35 ° C and then dried under reduced pressure to obtain 2- (9H-carbazol-9-yl) 2 mmol (63%) of (1, 2,3,4,5-pentamethylcyclopenta-2,4-dien-1-yl) titanium (IV) dichloride.

¹ H NMR (CDCl ₃ , 500 MHz)? 1.50 (s, 15 H), 6.79 (m, 1 H), 7.02 , 7.36 (t, 2 H, J = 7.7 Hz), 7.65 (d, 1 H, J = 8.2 Hz), 8.08 (d, 2 H, J = 7.8 Hz) ppm

[Example 2]

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

To a 2 L stainless steel reactor thoroughly dried and replaced with nitrogen, 1100 mL of cyclohexane and 100 mL of 1-octene were charged, and then 54.3 mM (alumina) of modified methylaluminoxane-7 (Akzo Nobel, modified MAO-7, 7 wt% Al Isopar solution) 22.1 mL of toluene solution was added to the reactor. Thereafter, the temperature of the reactor was heated to 80 DEG C, and then a solution of (2- (9H-carbazol-9-yl) phenoxy) (2,3,4,5-tetramethylcyclopenta- (4-dien-1-yl) titanium (IV) chloride (0.37 μM toluene solution) and 2.0 ml of triphenylmethylnitium tetrakispentafluorophenylborate (99%, Boulder Scientific) And then the pressure in the reactor was filled up to 30 kg / cm ² with ethylene, and the reactor was continuously fed to polymerize. The reaction reached a maximum temperature of 164 占 폚 for 3 minutes. After 1 minute, 100 ml of ethanol containing 10 vol% hydrochloric acid aqueous solution was added to terminate the polymerization. The reaction mixture was stirred with 10 L of ethanol for 1 hour, . 83 g of a polymer was thus obtained, the density of the polymer being 0.8922 (g / cc) and the melt flow index (MI) being 1.83.

[Comparative Example 1]

The procedure of Example 3 was repeated except that (2-phenylphenoxy) (pentamethylcyclopentadienal) titanium (IV) dichloride was used as a catalyst. The maximum temperature reached 138 占 폚 for a reaction time of 3 minutes, and 60 g of a polymer was obtained. The polymer had a density of 0.8854 (g / cc) and a melt flow index (MI) of 5.5.

According to Example 2, polymers having a high 1-octene content and a large weight average molecular weight could be produced even at a high temperature (120 ° C or higher). Particularly, from Example 2, a low-density copolymer was successfully obtained.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be construed as limiting the scope of the invention as defined by the appended claims. It will be possible to carry out various modifications. Therefore, modifications of the embodiments of the present invention will not depart from the scope of the present invention.

Claims (15)

delete delete delete A transition metal compound represented by the following formula (2).
(2)

[In the formula (2)
Cp is cyclopentadienyl or pentamethylcyclopentadienyl;
M is titanium;
R ₁₁ , R ₁₂ and R ₂₁ are each independently a hydrogen atom or a (C 1 -C 20) alkyl group;
Wherein n is 1;
X is selected from a chlorine, a methyl group, a methoxy group, an isopropoxy group and a dimethylamino group. 5. The method of claim 4,
Wherein the transition metal compound is selected from the following.

Wherein: Cp is cyclopentadienyl or pentamethylcyclopentadienyl; M is titanium;
X ₁ and X ₂ independently of one another can be selected from the group consisting of chlorine, methyl, methoxy, isopropoxy and dimethylamino. A transition metal compound of claim 4 or 5; And
An aluminum compound promoter, a boron compound promoter, or a mixture thereof;
Or a transition metal catalyst composition for the production of a copolymer of ethylene and an? -Olefin. The method according to claim 6,
Wherein the aluminum compound co-catalyst is an ethylene homopolymer or a transition metal catalyst composition for the production of a copolymer of ethylene and an? -Olefin, which is selected from methyl aluminoxane, modified methyl aluminoxane, tetraisobutyl aluminoxane and trialkyl aluminum, . The method according to claim 6,
Wherein the aluminum compound co-catalyst is an ethylene homopolymer having a molar ratio of transition metal (M): aluminum of 1:50 to 1: 5,000, or a transition metal catalyst composition for the production of a copolymer of ethylene and an? The method according to claim 6,
Wherein the boron compound cocatalyst is selected from the group consisting of N, N-dimethylanilinium tetrakispentafluorophenyl borate and triphenylmethylninium tetrakispentafluorophenyl borate, or an ethylene homopolymer or a mixture of ethylene and an alpha -olefin ≪ / RTI > The method according to claim 6,
The promoter of the aluminum compound and the promoter of the boron compound may be an ethylene homopolymer or an ethylene homopolymer having a molar ratio of transition metal M: boron atom (B): aluminum atom (Al) Transition metal catalyst composition for the preparation of a copolymer of olefins. A process for producing a copolymer of ethylene homopolymer or ethylene and an? -Olefin, including using the transition metal catalyst composition according to claim 6 12. The method of claim 11,
The comonomer to be polymerized with ethylene is at least one selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, -Hexadecene and 1-aicosene, or a mixture thereof, wherein the content of ethylene in the copolymer of ethylene and olefin is 60 to 99% by weight, or a process for producing a copolymer of ethylene and an? -Olefin. 12. The method of claim 11,
Wherein the pressure of the ethylene monomer in the reactor is 1 to 1000 atm and the polymerization reaction temperature is 60 to 300 占 폚. delete delete