KR20230102135A - A novel transition metal complexes, a transition metal catalyst composition comprising the same, and a method for preparing a copolymer of ethylene and α-olefin using the same - Google Patents

Abstract

The present invention relates to a novel transition metal complex, a transition metal catalyst composition with high catalytic activity for preparing a copolymer of ethylene and α-olefin comprising the same, a method for preparing a copolymer of ethylene and α-olefin using the same, and a copolymer of ethylene and α-olefin manufactured thereby. The transition metal catalyst composition for preparing a copolymer of ethylene and α-olefin comprises: a transition metal compound and a promotor selected from an aluminum compound, a boron compound or a combination of the aluminum compound and boron compound.

Description

A novel transition metal complexes, a transition metal catalyst composition comprising the same, and a method for preparing a copolymer using the same of ethylene and α-olefin using the same}

The present invention is a novel transition metal compound, a transition metal catalyst composition for preparing a copolymer of ethylene and α-olefin containing the same, a method for preparing a copolymer of ethylene and α-olefin using the same, and a copolymer of ethylene and α-olefin prepared It is about.

Conventionally, a so-called Ziegler-Natta catalyst system composed of a main catalyst component of a titanium or vanadium compound and a cocatalyst component of an alkylaluminum compound has been generally used to prepare ethylene homopolymers and copolymers with α-olefins. Although the Ziegler-Natta catalyst system exhibits high activity for ethylene polymerization, the generally produced polymer has a wide molecular weight distribution due to the non-uniform catalytic active point, and the composition distribution is not uniform, especially in the case of copolymers of ethylene and α-olefin. there was

Subsequently, it is a homogeneous catalyst having a single catalytically active site, and metallocenes of transition metals of group 4 of the periodic table such as zirconium and hafnium, which can produce polyethylene with a narrow molecular weight distribution and a uniform composition distribution compared to the existing Ziegler-Natta catalyst system. Various studies have been conducted on the metallocene catalyst system composed of a compound and methylaluminoxane as a cocatalyst.

For example, in European Patent Publication Nos. 320,762 and 372,632 or Japanese Patent Application Laid-Open No. 63-092621, Japanese Patent Application Laid-Open No. 02-84405, or Japanese Patent Application 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 Ethylene is polymerized with high activity by activating the metallocene compound with cocatalyst methylaluminoxane, and the molecular weight distribution (Mw/Mn) is in the range of 1.5~2.0 It was announced that polyethylene can be produced.

However, it was difficult to obtain a high molecular weight polymer with the catalyst system. That is, when applied to a solution polymerization method performed at a high temperature, the polymerization activity is rapidly reduced and the β-dehydrogenation reaction is dominant, and it is known that it is not suitable for preparing a high molecular weight polymer.

A transition metal catalyst in which transition metals are connected in a ring form as a catalyst capable of preparing a high molecular weight polymer with high catalytic activity in ethylene homopolymerization or copolymerization of ethylene and α-olefin under solution polymerization conditions has been announced.

European Patent No. 0416815 and European Patent No. 0420436 suggested an example in which an amide group was connected in a ring form to one cyclopentadiene ligand, and in European Patent No. 0842939, a phenolic ligand as an electron donor compound was combined with a cyclopentadiene ligand. An example of a catalyst connected in a ring form is shown.

In addition, a transition metal catalyst linked to a cyclopentadienyl-fluorenyl ligand connected by a bridge has been disclosed. US6559253 suggests a structure in which a diphenyl-substituted bridge and one cyclopentadiene ligand are connected to unsubstituted fluorene. US6300433 discloses the structure of one or more substituted cyclopentadienyl-fluorenyl ligands with substituted diphenyl methylene bridges.

In the case of these catalysts, the reactivity with α-olefins is significantly improved due to the reduced steric hindrance effect of the catalyst itself, but there are many difficulties in commercial use. Therefore, it is important to secure a more competitive catalyst system, such as the required characteristics of a commercial catalyst based on economic feasibility, that is, excellent high-temperature activity, excellent reactivity with α-olefins, and the ability to produce high molecular weight polymers.

European Patent 0416815 B1 European registered patent 0420436 B2

In order to overcome the problems of the prior art, the present inventors have conducted extensive research and as a result, the group 4 transition metal on the periodic table as a central metal has a cyclopentadienyl group rich in electrons and widely delocalized, and a 2 distant from the active point. , It was found that a transition metal compound having a structure connected by a fluorenyl group substituted at position 7 exhibits excellent catalytic activity and high molecular weight in high-temperature solution polymerization of ethylene and olefins, and based on these results, at high temperature A catalyst capable of preparing a copolymer of high molecular weight ethylene and α-olefin with high activity in a solution polymerization process was developed, and the present invention was completed based on this.

Accordingly, an object of the present invention is to provide a transition metal compound useful as a catalyst for producing a copolymer of ethylene and α-olefin, and also to provide a catalyst composition comprising the same.

Another object of the present invention is to provide an industrially economical and easy method for preparing a copolymer of ethylene and α-olefin using a catalyst composition containing the transition metal compound.

The present invention provides a transition metal compound represented by Formula 1 below.

[Formula 1]

[In Formula 1 above

M is a Group 4 transition metal;

R ₁ to R ₂ are each independently (C11-C20)alkyl;

R ₃ and R ₄ are independently hydrogen or (C6-C20)aryl unsubstituted or substituted with (C1-C10)alkyl;

X ₁ and X ₂ are each independently halogen, (C1-C20)alkyl, (C3-C20)cycloalkyl, (C6-C20)aryl, ((C1-C20)alkyl(C6-C20)aryl)(C1- C20) Alkyl, (C1-C20) Alkoxy, (C6-C20) Aryloxy, (C1-C20) Alkyl (C6-C20) Aryloxy, (C1-C20) Alkoxy (C6-C20) Aryloxy, -OSiR _a R _b R _c , -SR _d , -NR _e R _f , -PR _g R _h or (C1-C20)alkylidene;

R _a to R _d are each independently (C1-C20)alkyl, (C6-C20)aryl, (C6-C2)0aryl(C1-C20)alkyl, (C1-C20)alkyl (C6-C20)aryl, or (C3-C20)cycloalkyl;

R _e to R _h are each independently (C1-C20)alkyl, (C6-C20)aryl, (C6-C20)aryl(C1-C20)alkyl, (C1-C20)alkyl(C6-C20)aryl, ( C3-C20)cycloalkyl, tri(C1-C20)alkylsilyl or tri(C6-C20)arylsilyl;

When either X ₁ or X ₂ is a (C1-C20)alkylidene, the other is absent.]

In one embodiment of the present invention, M in Formula 1 is Ti, Zr or Hf, R ₁ to R ₂ may each independently be (C11-C20)alkyl, and R ₃ and R ₄ are each independently It is hydrogen, or (C6-C20)aryl substituted or unsubstituted with (C1-C10)alkyl, and X ₁ and X ₂ may each independently be halogen, (C1-C20)alkyl or (C6-C20)aryl. .

Further, in one embodiment of the present invention, M in Formula 1 is Hf, R ₁ to R ₂ may each independently be (C11-C20)alkyl, and R ₃ and R ₄ are each independently (C6 -C12) aryl, and X ₁ and X ₂ may each independently be halogen, (C1-C6)alkyl or (C6-C12)aryl.

Preferably, in one embodiment of the present invention, the transition metal compound is [1-(η5-cyclopentadien-1-yl)-1-(η5-2,7-di-n-dodecylfluorenyl) -1,1-diphenyl methane] hafnium dichloro, [1-(η5-cyclopentadien-1-yl)-1-(η5-2,7-di-n-dodecylfluorenyl)-1,1 -diphenyl methane] hafnium dibenzyl or [1-(η5-cyclopentadien-1-yl)-1-(η5-2,7-di-n-dodecylfluorenyl)-1,1-diphenyl methane] hafnium dimethyl.

The present invention provides a catalyst composition for preparing a copolymer of ethylene and α-olefin containing a transition metal compound according to an embodiment of the present invention, wherein the transition metal catalyst composition is selected from aluminum compounds, boron compounds, or mixtures thereof A cocatalyst and a transition metal compound according to an embodiment of the present invention may be included.

The aluminum compound used as the cocatalyst may be one or two or more selected from aluminoxane and organoaluminum, and these aluminum compounds include methylaluminoxane, modified methylaluminoxane, tetraisobutylaluminoxane, trimethylaluminum, triethylaluminum, It may be one or two or more selected from trioctyl aluminum and triisobutyl aluminum.

In addition, the boron compound used as the cocatalyst is dimethylphenylammonium tetra (phenyl) borate, trityltetra (phenyl) borate, dimethylphenylammonium tetra (pentafluorophenyl) borate, trityltetra (pentafluorophenyl) borate , trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) ) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, anilinium tetraphenylborate, anilinium tetrakis (pentafluorophenyl) borate, pyridinium tetra It may be one or two or more selected from kiss (pentafluorophenyl) borate and silver tetrakis (pentafluorophenyl) borate.

The present invention provides a method for preparing a copolymer of ethylene and α-olefin using the catalyst composition according to an embodiment of the present invention, the method comprising: a) the transition metal catalyst composition according to claim 5, ethylene and α-olefin mixing comonomers and b) performing a copolymerization reaction at a temperature of 110° C. to 170° C.

In the above production method, the α-olefin copolymerized with ethylene is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene , 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-aitocene, cyclopentene, cyclohexene, norbonene, phenylnorbornene, styrene, α-methyl It may be one or two or more selected from styrene, p-methylstyrene, and 3-chloromethylstyrene.

Step b) of the method for preparing the copolymer of ethylene and α-olefin may be performed at a temperature of 120 ° C to 160 ° C and a pressure of 10 to 100 bar, and the manufacturing method is carried out in a C5-C12 aliphatic hydrocarbon solvent It can be.

The present invention provides a copolymer of ethylene and α-olefin prepared from the transition metal catalyst composition according to an embodiment of the present invention.

The transition metal compound of the present invention can be easily prepared in high yield by a simple process under mild conditions, and the transition metal compound and a catalyst composition containing the same have excellent thermal stability and can maintain excellent catalytic activity even at high temperatures, and use this It is possible to prepare copolymers of high molecular weight ethylene and α-olefins. This manufacturing method is a very economical method because a high yield of the copolymer can be obtained through a simple process, and can be easily used for industrial mass production.

Hereinafter, the transition metal compound of the present invention, a transition metal catalyst composition comprising the same, and a method for preparing a copolymer of ethylene and α-olefin using the same will be described in detail.

The singular form used in the present invention may be intended to include the plural form as well, unless the context specifically dictates otherwise.

In the present invention, "comprising" is an open description having the same meaning as "comprises", "includes", "has" or "characterized by", and elements and materials not additionally listed. or do not rule out the process.

As used herein, "alkyl" refers to a monovalent straight-chain or branched saturated hydrocarbon radical composed only of carbon and hydrogen atoms, examples of such alkyl radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl , pentyl, hexyl, octyl, nonyl, and the like, but are not limited thereto.

As used herein, "aryl" is an organic radical derived from an aromatic hydrocarbon by removing one hydrogen, and is a single or fused ring system containing 4 to 7, preferably 5 or 6, ring atoms in each ring. Including, including a form in which a plurality of aryls are connected by single bonds. Fused ring systems may include aliphatic rings, such as saturated or partially saturated rings, and necessarily contain at least one aromatic ring. Also, the aliphatic ring may include nitrogen, oxygen, sulfur, carbonyl, and the like in the ring. Specific examples of the aryl radical include phenyl, naphthyl, biphenyl, indenyl, fluorenyl, phenanthrenyl, anthracenyl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, 9,10-dihydro including but not limited to anthracenyl and the like.

As used herein, “cycloalkyl” refers to a monovalent saturated carbocyclic radical composed of one or more rings. Examples of cycloalkyl radicals include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.

As used herein, “halo” or “halogen” refers to a fluorine, chlorine, bromine or iodine atom.

As used herein, "alkoxy" refers to -OCH ₃ , -OCH ₂ CH ₃ , -O(CH ₂ ) ₂ CH ₃ , -O(CH ₂ ) ₃ CH ₃ , -O(CH ₂ ) ₄ CH ₃ , -O (CH ₂ ) ₅ CH ₃ and the like means -O-(alkyl), wherein alkyl is as defined above.

As used herein, “aryloxy” means an -O-aryl radical, respectively, where 'aryl' is as defined above.

As used herein, “alkylidene” refers to a straight or branched chain saturated divalent hydrocarbon group having a valency of 2 on one common carbon atom.

The present invention provides a transition metal compound represented by Formula 1 below.

[Formula 1]

[In Formula 1 above

M is a Group 4 transition metal;

R ₁ to R ₂ are each independently (C11-C20)alkyl;

R ₃ and R ₄ are independently hydrogen or (C6-C20)aryl unsubstituted or substituted with (C1-C10)alkyl;

X ₁ and X ₂ are each independently halogen, (C1-C20)alkyl, (C3-C20)cycloalkyl, (C6-C20)aryl, ((C1-C20)alkyl(C6-C20)aryl)(C1- C20) Alkyl, (C1-C20) Alkoxy, (C6-C20) Aryloxy, (C1-C20) Alkyl (C6-C20) Aryloxy, (C1-C20) Alkoxy (C6-C20) Aryloxy, -OSiR _a R _b R _c , -SR _d , -NR _e R _f , -PR _g R _h or (C1-C20)alkylidene;

R _a to R _d are each independently (C1-C20)alkyl, (C6-C20)aryl, (C6-C2)0aryl(C1-C20)alkyl, (C1-C20)alkyl (C6-C20)aryl, or (C3-C20)cycloalkyl;

R _e to R _h are each independently (C1-C20)alkyl, (C6-C20)aryl, (C6-C20)aryl(C1-C20)alkyl, (C1-C20)alkyl(C6-C20)aryl, ( C3-C20)cycloalkyl, tri(C1-C20)alkylsilyl or tri(C6-C20)arylsilyl;

When either X ₁ or X ₂ is a (C1-C20)alkylidene, the other is absent.]

The transition metal compound represented by Chemical Formula 1 has a cyclopentadienyl group in which the Group 4 transition metal on the periodic table is electron-rich and widely delocalized as a central metal, and a substituent helpful for improving solubility and performance can be easily introduced, It is a transition metal compound having a structure in which substituents are connected by fluorenyl groups at positions 2 and 7 far from the active point, and the cyclopentadienyl group and the fluorenyl group are connected by carbon. Ethylene and α-olefins It can exhibit excellent catalytic activity in the polymerization of

In one embodiment of the present invention, M in Formula 1 is Ti, Zr or Hf, R ₁ to R ₂ may each independently be (C11-C20)alkyl, and R ₃ and R ₄ are each independently It is hydrogen, or (C6-C20)aryl substituted or unsubstituted with (C1-C10)alkyl, and X ₁ and X ₂ may each independently be halogen, (C1-C20)alkyl or (C6-C20)aryl. .

Further, in one embodiment of the present invention, M in Formula 1 is Hf, R ₁ to R ₂ may each independently be (C11-C20)alkyl, and R ₃ and R ₄ are each independently (C6 -C12) aryl, and X ₁ and X ₂ may each independently be halogen, (C1-C6)alkyl or (C6-C12)aryl.

Specifically, in one embodiment of the present invention, X ₁ and X ₂ in Formula 1 may each independently be halogen, (C1-C3)alkyl or (C6-C10)aryl, and more specifically, X ₁ and X ₂ may each independently be Cl, methyl, phenyl or benzyl.

Preferably, in one embodiment of the present invention, the transition metal compound is [1-(η5-cyclopentadien-1-yl)-1-(η5-2,7-di-n-dodecylfluorenyl) -1,1-diphenyl methane] hafnium dichloro, [1-(η5-cyclopentadien-1-yl)-1-(η5-2,7-di-n-dodecylfluorenyl)-1,1 -diphenyl methane] hafnium dibenzyl or [1-(η5-cyclopentadien-1-yl)-1-(η5-2,7-di-n-dodecylfluorenyl)-1,1-diphenyl methane] hafnium dimethyl.

On the other hand, the transition metal compound according to an embodiment of the present invention is preferably used as an active catalyst component used in the preparation of a copolymer of ethylene and α-olefin, X ₁ and X ₂ ligands of the transition metal compound of Formula 1 While extracting and cationizing the central metal, an aluminum compound, a boron compound, or a mixture thereof that can act as a counter ion having a weak binding force, that is, an anion, can act as a cocatalyst, including the above transition metal compound and cocatalyst Catalyst compositions comprising are also within the scope of the present invention.

Therefore, the transition metal catalyst composition of the present invention may include a cocatalyst selected from an aluminum compound, a boron compound, or a mixture thereof, and a transition metal compound according to an embodiment of the present invention.

In the catalyst composition according to an embodiment of the present invention, the aluminum compound used as the cocatalyst may be one or two or more selected from aluminoxane, organoaluminum, and organoaluminum oxide compounds, and the aluminum compound is specifically formulated by the following formula It may be one or two or more selected from the aluminoxane compound of 2 or 3, the organoaluminum compound of formula 4, or the organoaluminum oxide compound of formula 5 or 6.

[Formula 2]

(-Al(R ¹¹ )-O-) _m

[Formula 3]

(R ¹¹ ) ₂ Al-(-O(R ¹¹ )-) _q -(R ¹¹ ) ₂

[Formula 4]

(R ¹² ) _r Al(E) _3-r

[Formula 5]

(R ¹³ ) ₂ AlOR ¹⁴

[Formula 6]

R ¹³ Al (OR ¹⁴ ) ₂

[In Formulas 2 to 6, R ¹¹ is (C1-C20)alkyl, preferably methyl or isobutyl, m and q are each an integer of 5 to 20; R ¹² and R ¹³ are each (C1-C20)alkyl; E is hydrogen or halogen; r is an integer from 1 to 3; R ¹⁴ is (C1-C20)alkyl or (C6-C20)aryl.]

Specific examples that can be used as the aluminum compound include methyl aluminoxane, modified methyl aluminoxane, and tetraisobutyl aluminoxane as the aluminoxane compound; Examples of organoaluminum compounds include trialkylaluminum, including trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum, dimethylaluminum chloride, diethylaluminum chloride, and dipropylaluminum chloride. , dialkyl aluminum chloride including diisobutyl aluminum chloride and dihexyl aluminum chloride, alkyl including methyl aluminum dichloride, ethyl aluminum dichloride, propyl aluminum dichloride, isobutyl aluminum dichloride, and hexyl aluminum dichloride and dialkyl aluminum hydrides including aluminum dichloride, dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutyl aluminum hydride and dihexyl aluminum hydride.

More preferably, the aluminum compound may be one or more selected from methylaluminoxane, modified methylaluminoxane, tetraisobutylaluminoxane, trimethylaluminum, triethylaluminum, trioctylaluminum, and triisobutylaluminum.

In the present invention, the boron compound that can be used as a cocatalyst may be selected from boron compounds represented by Chemical Formulas 7 to 9 below.

[Formula 7]

B(R ²¹ ) ₃

[Formula 8]

[R ²² ] ⁺ [B(R ²¹ ) ₄ ] ^-

[Formula 9]

[(R ²³ ) _p ZH] ⁺ [B(R ²¹ ) ₄ ] ^-

[In Formulas 7 to 9, B is a boron atom; R ²¹ is phenyl, wherein the phenyl is represented by 3 to 5 substituents selected from fluoro, (C1-C20)alkyl optionally substituted with fluoro, and (C1-C20)alkoxy optionally substituted with fluoro. may be further substituted; R ²² is a (C5-C7) aromatic radical or a (C1-C20) alkyl (C6-C20) aryl radical, a (C6-C20) aryl (C1-C20) alkyl radical, such as triphenylmethylium is a radical; Z is a nitrogen or phosphorus atom; R ²³ is a (C1-C50)alkyl radical or an anilinium radical substituted with two (C1-C10)alkyl groups together with a nitrogen atom; and p is an integer of 2 or 3.]

Preferably, the boron compound used as the cocatalyst is dimethylphenylammonium tetra (phenyl) borate, trityltetra (phenyl) borate, dimethylphenylammonium tetra (pentafluorophenyl) borate, trityltetra (pentafluorophenyl) borate , trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) ) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, anilinium tetraphenylborate, anilinium tetrakis (pentafluorophenyl) borate, pyridinium tetra It may be one or two or more selected from kiss (pentafluorophenyl) borate and silver tetrakis (pentafluorophenyl) borate.

On the other hand, the cocatalyst may serve as a scavenger to remove impurities that act as poisons to the catalyst among the reactants.

In one embodiment according to the present invention, when the aluminum compound and the boron compound are simultaneously used as cocatalysts, the preferred range of the ratio between the transition metal compound of the present invention and the cocatalyst is transition metal (M) : aluminum atom (Al) : The molar ratio of boron atoms (B) may be in the range of 1: (10 to 3,000): (1 to 100), more preferably in the range of 1: (100 to 1,000): (3 to 10) .

If the ratio between the transition metal compound and the cocatalyst of the present invention is out of the above range, the activation of the transition metal compound may not be completely achieved due to the relatively small amount of the cocatalyst, so that the catalytic activity of the transition metal compound may not be sufficient or more than necessary. A cocatalyst may be used, which may cause a problem of significantly increasing production costs. It exhibits excellent catalytic activity for preparing a copolymer of ethylene and α-olefin within the above range, and the range of the ratio varies depending on the purity of the reaction.

The present invention provides a method for preparing a copolymer of ethylene and α-olefin using a catalyst composition according to an embodiment of the present invention, the method comprising:

a) mixing the transition metal catalyst composition according to an embodiment of the present invention, ethylene and an α-olefin comonomer; and

b) performing a copolymerization reaction at a temperature of 110 ° C to 170 ° C;

can include

As another aspect of the present invention, the method for preparing an ethylene polymer using the transition metal catalyst composition may be performed by contacting the transition metal catalyst, cocatalyst, α-olefin comonomer, and ethylene in the presence of an appropriate organic solvent. In this case, the transition metal catalyst, cocatalyst, and α-olefin comonomer components may be separately introduced into the reactor or mixed in advance and introduced into the reactor.

Step b) of the method for producing a copolymer of ethylene and α-olefin may be performed at a temperature of 120 ° C to 160 ° C and a pressure of 10 to 100 bar, preferably at a temperature of 130 ° C to 150 ° C and 15 to 50 bar can be performed at a pressure of

In addition, the preparation method may be performed in a C5-C12 aliphatic hydrocarbon solvent, specifically, the C5-C12 aliphatic hydrocarbon solvent is butane, isobutane, pentane, hexane, heptane, octane, isooctane, nonane, decane, dodecane, cyclo It may be one or two or more selected from hexane and methylcyclohexane, and may be preferably hexane, cyclohexane, or a mixture thereof.

The method for preparing a copolymer of ethylene and α-olefin according to an embodiment of the present invention does not use toluene, a common solvent commonly used in copolymer production, so that the toluene solvent removal step in the manufacturing process is reduced, resulting in more economical production way.

In the method for preparing a copolymer of ethylene and α-olefin according to an embodiment of the present invention, the α-olefin is selected from (C3~C18)α-olefin, (C5~C20)cycloolefin, styrene and derivatives of styrene One or two or more may be used, and preferred examples of (C3~C18)α-olefins are propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene , It may be selected from the group consisting of 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene, and preferred examples of (C5-C20) cycloolefins include cyclo It may be selected from the group consisting of pentene, cyclohexene, norbonene and phenylnorbornene, and styrene and its derivatives may be selected from styrene, α-methylstyrene, p-methylstyrene and 3-chloromethylstyrene. . More preferably, the α-olefin may be one or two or more selected from 1-butene, 1-hexene, 1-octene and 1-decene.

The present invention provides a copolymer of ethylene and α-olefin prepared from the transition metal catalyst composition according to an embodiment of the present invention, and the copolymer of ethylene and (C3-C18) α-olefin prepared above is 0.850 g / It can be economically and easily manufactured from elastomers having a density of mL to 0.910 g/mL and a melt flow rate of 0.001 to 20 g/10 min to high density polyethylene (HDPE).

In addition, when preparing the ethylene homopolymer or copolymer according to the present invention, hydrogen may be used as a molecular weight regulator to control the molecular weight, and usually has a weight average molecular weight (Mw) in the range of 5,000 to 1,000,000 g/mol.

Since the catalyst composition presented in the present invention exists in a uniform form in a polymerization reactor, it is preferable to apply it to a solution polymerization process performed at a temperature equal to or higher than the melting point of the corresponding polymer. However, as disclosed in U.S. Patent No. 4,752,597, a non-uniform catalyst composition obtained by supporting the transition metal catalyst and cocatalyst on a porous metal oxide support may be used in a slurry polymerization or gas phase polymerization process.

Hereinafter, a novel transition metal compound according to the present invention, a transition metal catalyst composition including the same, and a method for preparing a copolymer of ethylene and α-olefin using the same will be described in more detail through specific examples.

All of the following synthesis reactions were performed under an inert atmosphere such as nitrogen or argon, and standard Schlenk technology and glove box technology were used.

Solvents for synthesis such as tetrahydrofuran (THF), normal hexane (n-Hexane), normal pentane (n-Pentane), diethyl ether, and methylene chloride (CH2Cl2) After removing moisture by passing through an activated alumina column, it was used while being stored on an activated molecular sieve. Most reagents were purchased and used from Sigma-Aldrich, TCI, Alfa, and Strem unless otherwise noted. 1H NMR analysis of the synthesized compound was performed using a Bruker 500 MHz at room temperature.

Molecular weight and copolymerizability of copolymers of ethylene and α-olefins were analyzed according to the following methods.

1. Molecular Weight

MFR analysis was performed by melting the plastic at 190 ° C and measuring the weight of the extrudate flowing through a capillary tube (orifice) of a certain size for 10 minutes at a load of 2.16 (5, 21.6) kg. The measurement standard was expressed (g / 10 min) as a melt index (MI, Melt Index) according to ASTM D1238. When the MI is low, the molecular weight increases and flowability decreases, so processability decreases and physical properties increase.

2. Copolymerization

In the range of 0.850 to 0.910 g/mL density, copolymerizability is higher as the density is closer to 0.85. To measure this, the weight of the resin per unit volume was measured. The density gradient method was used to create a calibration curve for standard column density and column height, and the measurement standard was measured according to ASTM D 1505 (KS M 3016).

[Production Example] [1-(η5-cyclopentadien-1-yl)-1-(η5-2,7-di-n-dodecylfluorenyl)-1,1-diphenyl methane] hafnium dichloro ( Synthesis of compound 1)

Step 1: Synthesis of Compound 1-1

To a Schrank flask, add Pd[P( t -Bu) ₃ ] ₂ (1.1 mol%, 0.26 g, 0.51 mmol) and 2,7-dibromo-9H-fluorene (15 g, 46 mmol). Toluene (200 mL) is added followed by n -Dodecylboronic acid (2.4 equiv, 11.2 g) followed by additional toluene (300 mL). After 2 hours, extract three times with saturated NH ₄ Cl aqueous solution and ether. The organic layer was collected, dried over MgSO ₄ and filtered, and then reduced under reduced pressure. A yellow liquid compound 1-1 was obtained (6.3 g, 49%) through column purification (silica, Hex/Ethyl Acetate = 10:1).

1H NMR (500 MHz, Chloroform- d ) δ 7.90 (d, J = 7.8 Hz, 2H), 7.47 (s, 2H), 7.30 (d, J = 7.8 Hz, 2H), 3.87 (s, 2H), 2.64 (t, J = 7.4 Hz, 4H), 1.61 (t, J = 7.3 Hz, 4H), 1.26 (m, 36H), 0.88 (t, J = 7.3 Hz, 6H)

Step 2: Synthesis of compound 1-2

After dissolving 2,7-di-n-dodecylfluorene (12g, 43.1 mmol) in THF (87 mL), nBuLi (1.6 M in Hex, 27.1 mL, 43.1 mmol) was added and stirred at room temperature. After 3 hours, 6,6-Diphenylfulvene (10 g, 43.1 mmol) is added. After stirring the reaction solution for 16 hours, the reaction is quenched by adding aqueous NH ₄ Cl (40 mL). The product was extracted as an organic layer, dried over MgSO ₄ , filtered, and reduced under reduced pressure. The resulting yellow solid was washed with ethanol to obtain a white solid compound 1-2 (20 g, yield 91%).

1H NMR (500 MHz, Chloroform- d ) δ 6.96~7.34 (m, 20H), 5.43 (s, 1H), 2.64 (t, J =7.4 Hz, 4H), 1.61 (t, J = 7.3 Hz, 4H) , 1.26 (m, 36H), 0.88 (t, J = 7.3 Hz, 6H)

Step 3: [1-(η5-cyclopentadien-1-yl)-1-(η5-2,7-di-n-dodecylfluorenyl)-1,1-diphenyl methane] hafnium dichloro (compound 1) Synthesis of

After compound 1-2 (5 g, 9.82 mmol) was dissolved in 60 mL of ether, nBuLi (1.6 M in Hex, 13.5 mL, 21.6 mmol) was added and stirred for 16 hours. After completion of the reaction, ether was removed by vacuum drying, and then a hexane solution was added and decanted to reduce pressure. Lithium solids (5.1 g, 9.79 mmol) and HfCl4 (3.13 g, 9.79 mmol) are dissolved in 80 mL of ether in a glove box. After stirring at room temperature for 16 hours, removing ether by vacuum drying, adding 80 mL of toluene, heating at 50 °C for 2 hours, precipitating by-product LiCl and filtering. The filtrate was vacuum-dried and crystalline to obtain yellow crystalline Compound 1 (4.5 g) (recrystallized with Toluene, yield 60%).

1H NMR (500 MHz, Chloroform- d ) δ 8.02 (d, J = 8.5 Hz, 2H), 7.96 (dd, J = 8.0, 2.0 Hz, 2H), 7.87 (dt, J = 7.0, 1.0 Hz, 2H) , 7.46 (m, 2H), 7.36 (m, 6H), 6.32 (t, J = 2.5 Hz, 2H), 6.16 (s, 2H), 5.70 (t, J = 2.5 Hz, 2H), 2.64 (t, J = 7.4 Hz, 4H), 1.61 (t, J = 7.3 Hz, 4H), 1.26 (m, 36H), 0.88 (t, J = 7.3 Hz, 6H)

[Comparative Preparation Example 1] Synthesis of [1-(η5-cyclopentadien-1-yl)-1-(η5-fluorenyl)-1,1-diphenyl methane]hafnium dichloro (Compound 2)

[1-(η5-cyclopentadien-1-yl)-1-(η5-fluorenyl)-1,1-diphenyl methane] hafnium dichloro (Compound 2) is described in [A. Razavi, J. L. Atwood, J. Organometallic. Chen, 459 (1993), 117-123].

1H NMR (500 MHz, Chloroform- d ) δ 8.19 (d, J = 8.5 Hz, 2H), 7.95 (d, J = 8.3 Hz, 2H), 7.88 (d, J = 8.5 Hz, 2H), 7.55 (t , J = 8.0 Hz, 2H), 7.44 (t, J = 8.2 Hz, 2H), 7.31 (m, 4H), 7.01 (t, J = 8.1 Hz, 2H), 6.47 (d, J = 7.1 Hz, 2H) ), 6.33 (s, 2H), 5.75 (s, 2H)

[Comparative Production Example 2] [1-(η5-cyclopentadien-1-yl)-1-(η5-2,7-di-n-butylfluorenyl)-1,1-diphenyl methane] hafnium dichloro Preparation of (Compound 3)

Step 1: Synthesis of Compound 3-1

Pd[P( t -Bu) ₃ ] ₂ (1.1 mol%, 0.26 g, 0.51 mmol), 2,7-dibromo-9H-fluorene (15 g, 46 mmol) and toluene (200 mL) were added to a Schrank flask. After addition, n -Butylboronic acid (2.4 equiv, 11.2 g) and additional toluene (300 mL) are added. After 2 hours, extract three times with saturated NH ₄ Cl aqueous solution and ether. The organic layer was collected, dried over MgSO ₄ and filtered, and then reduced under reduced pressure. After column purification (silica, Hex:Ethyl Acetate = 10:1), yellow liquid compound 3-1 was obtained (6.3 g, 49%).

1H NMR (500 MHz, Chloroform- d ) δ 7.68 (d, J = 7.7 Hz, 2H), 7.38 (s, 2H), 7.21 (d, J = 7.7 Hz, 2H), 3.86 (s, 2H), 2.72 (t, J =7.5 Hz, 4H), 1.70 (app. p, J = 7.2 Hz, 4H), 1.44 (app. h, J = 7.0 Hz, 4H), 1.00 (t, J = 7.2 Hz, 6H)

Step 2: Synthesis of Compound 3-2

After dissolving 2,7-di-n-butylfluorene (12g, 43.1 mmol) in THF (87 mL), nBuLi (1.6 M in Hex, 27.1 mL, 43.1 mmol) was added and stirred at room temperature. After 3 hours, 6,6-Diphenylfulvene (10 g, 43.1 mmol) is added. After stirring the reaction solution for 16 hours, the reaction is quenched by adding aqueous NH ₄ Cl (40 mL). The product was extracted as an organic layer, dried over MgSO ₄ , filtered, and reduced under reduced pressure. The resulting yellow solid was washed with ethanol to obtain compound 3-2 as a white solid (20 g, yield 91%).

1H NMR (500 MHz, Chloroform- d ) δ 6.96~7.34 (m, 20H), 5.43 (s, 1H), 2.72 (m, 4H), 1.70 (m, 4H), 1.44 (m, 4H), 0.90 ( t, J = 7.2 Hz, 6H)

Step 3: [1-(η5-cyclopentadien-1-yl)-1-(η5-2,7-di-n-butylfluorenyl)-1,1-diphenyl methane] hafnium dichloro (Compound 3 ) synthesis of

After dissolving compound 3-2 (5 g, 9.82 mmol) in 60 mL of ether, nBuLi (1.6 M in Hex, 13.5 mL, 21.6 mmol) was added and stirred for 16 hours. After completion of the reaction, ether is removed by vacuum drying, and then a hexane solution is added and decanted to reduce the pressure. Lithium solid (5.1 g, 9.79 mmol) and HfCl ₄ (3.13 g, 9.79 mmol) are dissolved in 80 mL of ether in a glove box. After stirring at room temperature for 16 hours, ether was removed by vacuum drying, then 80 mL of toluene was added, heated at 50 °C for 2 hours, and LiCl as a by-product was precipitated and filtered. The filtrate was vacuum-dried and crystalline to obtain yellow crystalline Compound 3 (4.5 g) (recrystallized with Toluene, yield 60%).

1H NMR (500 MHz, Chloroform- d ) δ 8.02 (d, J = 8.5 Hz, 2H), 7.96 (dd, J = 8.0, 2.0 Hz, 2H), 7.87 (dt, J = 7.0, 1.0 Hz, 2H) , 7.46 (m, 2H), 7.36 (m, 6H), 6.32 (t, J = 2.5 Hz, 2H), 6.16 (s, 2H), 5.70 (t, J = 2.5 Hz, 2H), 2.38 (m, 4H), 1.38 (m, 4H), 1.23 (m, 4H), 0.86 (t, J = 7.2 Hz, 6H)

[Example 1] Preparation of a copolymer of ethylene and α-olefin

1 L of hexane and triisobutylaluminum (1M, 2 mL) were added to a 4 L reactor at room temperature, followed by 1-octene (100 mL). After dissolving Preparation Example (3.9 μmol) in triisobutylaluminum (0.1 M in Hex, 2mL) in a glove box, 5 mL of hexane was added to the dissolved Preparation Example and injected into the reactor inlet. Dissolve trityl borate (19.5 μmol) in 5 mL of hexane in a glove box and introduce it into the inlet. After raising the temperature of the reactor to 140 ° C, the solution is pushed through the inlet with high-pressure nitrogen. Ethylene injection was performed at 300 psig for 15 minutes, showing an increase in initial temperature proportional to activity. After the polymerization was completed, the temperature of the reactor was cooled to 30° C., and the ethylene pressure inside the reactor was slowly exhausted to remove it. After washing the polymer in the solution with ethanol and acetone, it was filtered and vacuum dried. The results of the polymer thus obtained are shown in Table 1.

[Example 2]

The procedure of Example 1 was performed in the same manner, except that anilinium borate was used instead of trityl borate. The results of the polymer thus obtained are shown in Table 1.

[Comparative Example 1]

The procedure of Example 1 was performed in the same manner, except that Comparative Preparation Example 1 was used instead of Preparation Example. The results of the polymer thus obtained are shown in Table 1.

[Comparative Example 2]

The procedure of Example 1 was performed in the same manner, except that Comparative Preparation Example 1 was used instead of Preparation Example, and anilinium borate was used instead of trityl borate. The results of the polymer thus obtained are shown in Table 1.

[Comparative Example 3]

The procedure of Example 1 was performed in the same manner, except that Comparative Preparation Example 2 was used instead of Preparation Example. The results of the polymer thus obtained are shown in Table 1.

[Comparative Example 4]

The procedure of Example 1 was performed in the same manner, except that Comparative Preparation Example 2 was used instead of Preparation Example and anilinium borate was used instead of trityl borate. The results of the polymer thus obtained are shown in Table 1.

transition metal
compound co-catalyst activation
(kg/g cat) MI
(g/10min) Density
(g/mL) Example 1 manufacturing example trityl borate 18.4 0.0118 0.8628 Example 2 manufacturing example anilinium borate 18.3 0.0256 0.8671 1 to compare Comparative Preparation Example 1 trityl borate 3.6 0.1584 0.8598 Comparative Example 2 Comparative Preparation Example 1 anilinium borate 4.1 0.1055 0.8679 Comparative Example 3 Comparative Preparation Example 2 trityl borate 10.1 0.266 0.8606 Comparative Example 4 Comparative Preparation Example 2 anilinium borate 10.4 0.497 0.8653

As shown in Table 1, it can be seen that the catalytic activity of Examples 1 and 2 was 1.8 to 5.1 times higher than the catalytic activity of Examples 1 to 4 in comparison.

In addition, the copolymers prepared in Examples had higher molecular weight than the copolymers in Comparative Examples, and high elasticity copolymers were prepared. Therefore, it can be seen that the catalyst composition according to an embodiment of the present invention is a catalyst composition capable of obtaining a polymer of a polymer exhibiting excellent physical properties under high temperature and high pressure polymerization conditions.

The transition metal compound of the present invention, as a central metal, is a cyclopentadienyl group in which the group 4 transition metal on the periodic table is electron-rich and widely delocalized, and a fluorene having substituents substituted at positions 2 and 7 far from the active point. Since it has a structure linked by a yl group, it can exhibit excellent catalytic activity and high molecular weight in high-temperature solution polymerization of ethylene and olefins.

Therefore, when the catalyst composition containing the transition metal compound is used, a high molecular weight copolymer can be produced in high yield in the production of a copolymer of ethylene and α-olefin, and when applied to industrial mass production, it is very Economical manufacturing may be possible.

As described above, the present invention has been described by specific details, limited examples and comparative examples, but these are only provided to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and the present invention Those skilled in the art can make various modifications and variations from these descriptions.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and it will be said that not only the claims to be described later, but also all modifications equivalent or equivalent to these claims belong to the scope of the present invention. .

Claims (13)

A transition metal compound represented by Formula 1 below.
[Formula 1]

[In Formula 1 above
M is a Group 4 transition metal;
R ₁ to R ₂ are each independently (C11-C20)alkyl;
R ₃ and R ₄ are independently hydrogen or (C6-C20)aryl unsubstituted or substituted with (C1-C10)alkyl;
X ₁ and X ₂ are each independently halogen, (C1-C20)alkyl, (C3-C20)cycloalkyl, (C6-C20)aryl, ((C1-C20)alkyl(C6-C20)aryl)(C1- C20) Alkyl, (C1-C20) Alkoxy, (C6-C20) Aryloxy, (C1-C20) Alkyl (C6-C20) Aryloxy, (C1-C20) Alkoxy (C6-C20) Aryloxy, -OSiR _a R _b R _c , -SR _d , -NR _e R _f , -PR _g R _h or (C1-C20)alkylidene;
R _a to R _d are each independently (C1-C20)alkyl, (C6-C20)aryl, (C6-C2)0aryl(C1-C20)alkyl, (C1-C20)alkyl (C6-C20)aryl or (C3-C20)cycloalkyl;
R _e to R _h are each independently (C1-C20)alkyl, (C6-C20)aryl, (C6-C20)aryl(C1-C20)alkyl, (C1-C20)alkyl(C6-C20)aryl, ( C3-C20)cycloalkyl, tri(C1-C20)alkylsilyl or tri(C6-C20)arylsilyl;
When either X ₁ or X ₂ is a (C1-C20)alkylidene, the other is absent.] According to claim 1,
M in Formula 1 is Ti, Zr or Hf;
R ₁ to R ₂ are each independently (C11-C20)alkyl;
R ₃ and R ₄ are independently hydrogen or (C6-C20)aryl unsubstituted or substituted with (C1-C10)alkyl;
X ₁ and X ₂ are each independently halogen, (C1-C20)alkyl or (C6-C20)aryl, a transition metal compound. According to claim 1,
M in Formula 1 is Hf;
R ₁ to R ₂ are each independently (C11-C20)alkyl;
R ₃ and R ₄ are each independently (C6-C12)aryl;
X ₁ and X ₂ are each independently halogen, (C1-C6)alkyl or (C6-C12)aryl, a transition metal compound. According to claim 1,
The transition metal compound is [1-(η5-cyclopentadien-1-yl)-1-(η5-2,7-di-n-dodecylfluorenyl)-1,1-diphenyl methane] hafnium dichloro , [1-(η5-cyclopentadien-1-yl)-1-(η5-2,7-di-n-dodecylfluorenyl)-1,1-diphenyl methane] hafnium dibenzyl or [1 A transition metal compound, which is -(η5-cyclopentadien-1-yl)-1-(η5-2,7-di-n-dodecylfluorenyl)-1,1-diphenyl methane] hafnium dimethyl. The transition metal compound according to any one of claims 1 to 4; and
A cocatalyst selected from an aluminum compound, a boron compound, or a mixture thereof;
Transition metal catalyst composition for preparing a copolymer of ethylene and α-olefin comprising a. According to claim 5,
The aluminum compound used as the cocatalyst is one or two or more selected from aluminoxane and organoaluminum, a transition metal catalyst composition for preparing a copolymer of ethylene and α-olefin. According to claim 6,
The aluminum compound used as the cocatalyst is ethylene and α, which is one or two or more selected from methylaluminoxane, modified methylaluminoxane, tetraisobutylaluminoxane, trimethylaluminum, triethylaluminum, trioctylaluminum and triisobutylaluminum. -Transition metal catalyst composition for preparing copolymers of olefins. According to claim 5,
The boron compound used as the cocatalyst is dimethylphenylammonium tetra (phenyl) borate, trityltetra (phenyl) borate, dimethylphenylammonium tetra (pentafluorophenyl) borate, trityltetra (pentafluorophenyl) borate, trimethyl Ammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate , Tripropylammonium tetrakis (pentafluorophenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, anilinium tetraphenyl borate, anilinium tetrakis (pentafluorophenyl) borate, pyridinium tetrakis ( Pentafluorophenyl) borate or silver tetrakis (pentafluorophenyl) borate, one or more selected from, a transition metal catalyst composition for preparing a copolymer of ethylene and α-olefin. a) mixing the transition metal catalyst composition according to claim 5, ethylene and an α-olefin comonomer; and
b) performing a copolymerization reaction at a temperature of 110 ° C to 170 ° C;
Method for producing a copolymer of ethylene and α-olefin comprising a. According to claim 9,
The α-olefin copolymerized with ethylene is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1- Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-aitocene, cyclopentene, cyclohexene, norbonene, phenylnorbornene, styrene, alpha-methylstyrene, p -Method for preparing a copolymer of ethylene and α-olefin, which is one or two or more selected from methylstyrene and 3-chloromethylstyrene. According to claim 9,
Wherein step b) is performed at a temperature of 120 ° C to 160 ° C and a pressure of 10 to 100 bar, a method for producing a copolymer of ethylene and α-olefin. According to claim 9,
The method for preparing a copolymer of ethylene and α-olefin, which is performed in a C5-C12 aliphatic hydrocarbon solvent. A copolymer of ethylene and α-olefin prepared with the transition metal catalyst composition according to claims 5 to 8.