KR20140015666A - Tandem catalyst system comprising transition metal compound for alpha-olefin synthesis, and preparation method for polyethylene using the system - Google Patents

Abstract

The present invention relates to a tandem catalyst system comprising a transition metal compound for alpha-olefin synthesis, and a preparation method of polyethylene using the same. A tandem catalyst system according to the present invention comprises a transition metal compound for alpha-olefin synthesis enabling selective alpha-olefin synthesis from ethylene, thereby manufacturing polyethylene having low density and a uniform composition without using additional comonomers but only ethylene.

Description

TANDEM CATALYST SYSTEM COMPRISING TRANSITION METAL COMPOUND FOR ALPHA-OLEFIN SYNTHESIS, AND PREPARATION METHOD FOR POLYETHYLENE USING THE SYSTEM}

The present invention relates to a tandem catalyst system for polyethylene synthesis comprising a transition metal compound for alpha-olefin synthesis, and a method for producing polyethylene using the same.

Polyethylene is a high molecular compound produced by polymerization of ethylene, and is classified into low density polyethylene (LDPE), high density polyethylene (HDPE) and the like according to its density.

Generally, in the preparation of polyethylene, alpha-olefins such as 1-hexene are used as comonomers for the purpose of controlling the density of the polymer together with ethylene, a catalyst and the like. However, as price fluctuations intensify due to unstable supply and demand of comonomers, various methods for producing polyethylene having required physical properties by controlling a catalyst system without using comonomers have been proposed.

For example, US Pat. No. 6,586,550 discloses a tandem catalyst system comprising an oligomerization catalyst and a polymerization catalyst of ethylene. By the way, the catalyst system has a disadvantage in that the composition may not be constant even when polyethylene of the same density is produced by using the oligomerization catalyst, and it is difficult to control the reaction in which ethylene is oligomerized to form an alpha-olefin. .

As another example, US Pat. No. 7,214,749 discloses that polymers having a microstructure similar to linear LDPE can be obtained when ethylene homopolymerization is carried out using certain Constrained geometry catalysts. The technique according to the patent document has the advantage of using a single species of catalyst, but has a disadvantage in that it is difficult to produce a polymer having uniform properties due to irregular branches generated in the polymer.

As another example, US Patent No. 7,323,524 discloses a tandem catalyst system comprising a tetramerized chromium compound. However, the catalyst system may cause environmental problems in the catalyst recovery process due to the toxicity of chromium, and energy consumption is large because the performance of the catalyst is expressed under high temperature and high pressure conditions.

Therefore, there is an urgent need for the development of a catalyst system capable of producing polyethylene having uniform physical properties without using comonomers.

The present invention is directed to a transition metal compound for the synthesis of alpha-olefins which enables the synthesis of selective alpha-olefins from ethylene and a tandem catalyst system for the production of polyethylene comprising the same.

In addition, the present invention is to provide a method for producing a polyethylene having a uniform physical properties without using a comonomer by using the tandem catalyst system.

According to an embodiment of the present invention,

A first transition metal compound for synthesizing one or more alpha-olefins selected from the group consisting of compounds represented by Formula 1, Formula 2, and Formula 3;

A second transition metal compound for forming a copolymer of alpha-olefin and ethylene; And

Cocatalyst compound for activating the first transition metal compound and the second transition metal compound

Provided is a tandem catalyst system for producing polyethylene comprising:

[Formula 1]

(2)

(3)

In Chemical Formulas 1 to 3,

M is one element selected from Groups 3-10 on the periodic table,

Cp is a ligand having a cyclopentadienyl skeleton,

B is a linking group containing one element selected from Groups 13-16 on the periodic table,

Ar is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 30 carbon atoms,

O is oxygen, N is nitrogen,

n is an integer from 1 to 10, m is an integer from 0 to 5,

X ¹ and X ² are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C20 Alkylsilyl group, substituted or unsubstituted C1-C20 silylalkyl group, substituted or unsubstituted C1-C20 haloalkyl group, substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted C7 -20 arylalkyl groups, substituted or unsubstituted C7-20 alkylaryl groups, substituted or unsubstituted C6-C20 arylsilyl groups, substituted or unsubstituted C6-C20 silylaryl groups, substituted or In the group consisting of an unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C1-C20 alkylsiloxy group, a substituted or unsubstituted C6-C20 aryloxy group, and a tetrahydroborate group Selected Is one or more substituents,

Y ¹ and Y ² are each independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C20 alkylsilyl group , Substituted or unsubstituted C1-20 silylalkyl group, substituted or unsubstituted C6-20 aryl group, substituted or unsubstituted C7-20 arylalkyl group, substituted or unsubstituted C7-20 At least one substituent selected from the group consisting of an alkylaryl group, a substituted or unsubstituted C6-C20 arylsilyl group, and a substituted or unsubstituted C6-C20 silylaryl group,

Q ¹ , Q ² and Q ³ are each independently a linking group represented by the following formula (4),

[Chemical Formula 4]

R of Formulas 1 to 3 and R ¹ and R ² of Formula 4 are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted C1-20 alkyl group, a substituted or unsubstituted C3-20 cyclo Alkyl group, substituted or unsubstituted C1-C20 alkylsilyl group, substituted or unsubstituted C1-C20 silylalkyl group, substituted or unsubstituted C1-C20 haloalkyl group, substituted or unsubstituted C6-C20 20 aryl groups, substituted or unsubstituted C7-20 arylalkyl groups, substituted or unsubstituted C7-20 alkylaryl groups, substituted or unsubstituted C6-C20 arylsilyl groups, substituted or unsubstituted Substituted 6 to 20 carbonyl silylaryl groups, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted alkylsiloxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 20 carbon atoms And substituted or unsubstituted amino groups Is one or more substituents selected from the group consisting of,

p is an integer of 1-10.

According to the present invention, the second transition metal compound may be at least one compound selected from the group consisting of a Ziegler-Natta type catalyst, a chromium-based catalyst, a metallocene catalyst and a constrained geometry catalyst.

The tandem catalyst system may further include a carrier on which the first transition metal compound, the second transition metal compound, and the promoter compound are supported.

On the other hand, according to another embodiment of the present invention, there is provided a method for producing polyethylene comprising the step of polymerizing ethylene in the presence of the tandem catalyst system.

Wherein the polyethylene production method comprises forming an alpha-olefin from ethylene in the presence of the first transition metal compound and a promoter compound; And supplying the second transition metal compound and ethylene to the formation system of the alpha-olefin to form a copolymer of the alpha-olefin and ethylene.

The tandem catalyst system according to the present invention comprises the transition metal compound for the synthesis of alpha-olefins, which enables the synthesis of selective alpha-olefins from ethylene, thereby providing a low density and uniform composition with only ethylene without using a separate comonomer. To enable the preparation of polyethylene having.

Hereinafter, a tandem catalyst system including a transition metal compound for alpha-olefin synthesis according to embodiments of the present invention, and a method of preparing polyethylene using the same will be described.

Prior to that, unless explicitly stated throughout the present specification, the terminology is for reference only, and is not intended to limit the invention. And, the singular forms used herein include plural forms unless the phrases expressly have the opposite meaning.

Also, as used herein, the term " comprises " embodies specific features, regions, integers, steps, operations, elements or components, and does not exclude the presence of other specified features, regions, integers, steps, operations, elements, It does not.

In addition, terms including an ordinal number such as 'first' or 'second' may be used to describe various components throughout the specification, but the components are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may also be referred to as a second component, and similarly, the second component may also be referred to as a first component.

In addition, the term "alpha-olefin" as used throughout this specification means an olefin or alkene having a double bond in the alpha position, preferably C _{2 n} H ₄ n (n is an integer of 2 or more) formed by polymerization of ethylene. It means an olefin or alkene having a double bond in the alpha position while satisfying the general formula.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

The inventors of the present invention, in the course of repeated studies on the catalyst system for producing polyethylene, as shown in the general formula (1) to (3), the ligand having a cyclopentadienyl skeleton in the central metal (M) (m (R) -Cp- (B) The transition metal compound introduced with n-Ar) and a ligand derived from a hydroxyalkyl amine compound (a ligand formed by a combination of O, Q ¹ , Q ² , Q ³ , N, Y ¹ and Y ² ) are derived from ethylene. It was confirmed that the synthesis of selective alpha-olefins can be carried out more effectively.

When the transition metal compound is applied to a tandem catalyst system together with a conventional transition metal compound applied to alpha-olefin and ethylene copolymerization, polyethylene having a low density and uniform composition using only ethylene without using a separate comonomer is used. It was confirmed that it can be prepared.

According to this embodiment of the present invention,

A first transition metal compound for synthesizing one or more alpha-olefins selected from the group consisting of compounds represented by Formula 1, Formula 2, and Formula 3;

A second transition metal compound for forming a copolymer of alpha-olefin and ethylene; And

Cocatalyst compound for activating the first transition metal compound and the second transition metal compound

Provided is a tandem catalyst system for producing polyethylene comprising:

[Formula 1]

(2)

(3)

In Chemical Formulas 1 to 3,

M is one element selected from Groups 3-10 on the periodic table,

Cp is a ligand having a cyclopentadienyl skeleton,

B is a linking group containing one element selected from Groups 13-16 on the periodic table,

Ar is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 30 carbon atoms,

O is oxygen, N is nitrogen,

n is an integer from 1 to 10, m is an integer from 0 to 5,

X ¹ and X ² are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C20 Alkylsilyl group, substituted or unsubstituted C1-C20 silylalkyl group, substituted or unsubstituted C1-C20 haloalkyl group, substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted C7 -20 arylalkyl groups, substituted or unsubstituted C7-20 alkylaryl groups, substituted or unsubstituted C6-C20 arylsilyl groups, substituted or unsubstituted C6-C20 silylaryl groups, substituted or In the group consisting of an unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C1-C20 alkylsiloxy group, a substituted or unsubstituted C6-C20 aryloxy group, and a tetrahydroborate group Selected Is one or more substituents,

Y ¹ and Y ² are each independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C20 alkylsilyl group , Substituted or unsubstituted C1-20 silylalkyl group, substituted or unsubstituted C6-20 aryl group, substituted or unsubstituted C7-20 arylalkyl group, substituted or unsubstituted C7-20 At least one substituent selected from the group consisting of an alkylaryl group, a substituted or unsubstituted C6-C20 arylsilyl group, and a substituted or unsubstituted C6-C20 silylaryl group,

Q ¹ , Q ² and Q ³ are each independently a linking group represented by the following formula (4),

[Chemical Formula 4]

R of Formulas 1 to 3 and R ¹ and R ² of Formula 4 are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted C1-20 alkyl group, a substituted or unsubstituted C3-20 cyclo Alkyl group, substituted or unsubstituted C1-C20 alkylsilyl group, substituted or unsubstituted C1-C20 silylalkyl group, substituted or unsubstituted C1-C20 haloalkyl group, substituted or unsubstituted C6-C20 20 aryl groups, substituted or unsubstituted C7-20 arylalkyl groups, substituted or unsubstituted C7-20 alkylaryl groups, substituted or unsubstituted C6-C20 arylsilyl groups, substituted or unsubstituted Substituted 6 to 20 carbonyl silylaryl groups, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted alkylsiloxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 20 carbon atoms And substituted or unsubstituted amino groups Is one or more substituents selected from the group consisting of,

p is an integer of 1-10.

As described above, the first transition metal compound for synthesizing one or more alpha-olefins selected from the group consisting of the compounds represented by Chemical Formulas 1, 2, and 3 may be selected from ethylene. As a possible catalyst, a ligand derived from a hydroxyalkyl amine compound (O, Q ¹ with a ligand having a cyclopentadienyl skeleton (m (R) -Cp- (B) n-Ar) in the central transition metal (M)) , Q ² , Q ³ , a ligand formed by a combination of N, Y ¹ and Y ² ).

In particular, as the first transition metal compound is introduced with a ligand derived from the hydroxyalkyl amine compound, the first transition metal compound induces a slight change in ligand coordination form and electronic properties around the central transition metal (M), thereby making it more selective from ethylene. -Enables the synthesis of olefins. In addition, as the electron-rich multidentate alcohol amine group is introduced, the first transition metal compound is activated and stabilizes when it becomes a cation, thereby exhibiting high activity to alpha-olefin (particularly 1-hexene). Therefore, only a ligand having a conventional cyclopentadienyl skeleton has higher activity than the introduced compound, and enables the synthesis of more selective alpha-olefins.

Meanwhile, in Chemical Formulas 1 to 3, each M is independently an element selected from Groups 3 to 10 of the periodic table, preferably titanium (Ti), zirconium (Zr), vanadium (V) and tantalum ( Ta) may be one or more elements selected from the group consisting of.

In addition, in Chemical Formulas 1 to 3, X ¹ and X ² are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted C 1-20 alkyl group, a substituted or unsubstituted C 3-20 cycloalkyl group , Substituted or unsubstituted C1-C20 alkylsilyl group, substituted or unsubstituted C1-C20 silylalkyl group, substituted or unsubstituted C1-C20 haloalkyl group, substituted or unsubstituted C6-C20 Aryl groups, substituted or unsubstituted C7-20 arylalkyl groups, substituted or unsubstituted C7-20 alkylaryl groups, substituted or unsubstituted C6-C20 arylsilyl groups, substituted or unsubstituted C6-C20 silylaryl group, substituted or unsubstituted C1-C20 alkoxy group, substituted or unsubstituted C1-C20 alkylsiloxy group, substituted or unsubstituted C6-C20 aryloxy group, And tetrahydrobore Agent may be one or more substituents selected from the group consisting of groups (Tetrahydroborate); Preferably it may be a halogen group.

Meanwhile, in Chemical Formulas 1 to 3, Cp is a ligand having a cyclopentadienyl skeleton, and may be one having a conventional structure in the art to which the present invention pertains, and a non-limiting example is a cyclopentadienyl group It may be an indenyl group or a fluorenyl group.

In Formulas 1 to 3, R is a substituent connected to the Cp, a hydrogen atom, a halogen group, a substituted or unsubstituted C1-20 alkyl group, a substituted or unsubstituted C3-20 cycloalkyl group, Substituted or unsubstituted C1-C20 alkylsilyl group, substituted or unsubstituted C1-C20 silylalkyl group, substituted or unsubstituted C1-C20 haloalkyl group, substituted or unsubstituted C6-C20 Aryl group, substituted or unsubstituted C7-20 arylalkyl group, substituted or unsubstituted C7-20 alkylaryl group, substituted or unsubstituted C6-C20 arylsilyl group, substituted or unsubstituted carbon number 6-20 silylaryl groups, substituted or unsubstituted C1-C20 alkoxy groups, substituted or unsubstituted C1-C20 alkylsiloxy groups, substituted or unsubstituted C6-C20 aryloxy groups, and Substituted or unsubstituted sub It may be one or more substituents selected from the group consisting of minnow groups.

Here, m may be an integer of 0 to 5, wherein when m is 0, it means that all of the substituents bonded to Cp correspond to hydrogen. And, when m is 2 or more, the R may be the same or different.

Meanwhile, in Chemical Formulas 1 to 3, B is a linking group including one element selected from Groups 13 to 16 on the periodic table, and may include one or more heteroatoms or form a ring with adjacent groups. Preferably, the B is one or more selected from the group consisting of boron (B), carbon (C), nitrogen (N), oxygen (O), silicon (Si), phosphorus (P) and sulfur (S) May be a linking group comprising an element; More preferably, an alkylene group having 1 to 20 carbon atoms; Cycloalkylene groups having 3 to 20 carbon atoms; Alkylsilylene group having 1 to 20 carbon atoms; Haloalkylene groups having 6 to 20 carbon atoms; Arylalkylene groups having 6 to 20 carbon atoms; Arylsilylene group having 6 to 20 carbon atoms; Arylene groups having 5 to 40 carbon atoms; And an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an alkylsilylene group having 1 to 20 carbon atoms, and having 6 to 20 carbon atoms between the two arylene groups. Contains a haloalkylene group, an arylalkylene group having 6 to 20 carbon atoms, an arylsilylene group having 6 to 20 carbon atoms, or an alkylarylene group having 7 to 20 carbon atoms It may be one or more linking groups selected from the group consisting of functional groups. In this case, when two or more kinds of substituents are bonded to the carbon or silicon, these substituents may be selected from the group consisting of functional groups capable of being linked to each other to form a ring. For example, since both carbon and silicon are Group 14 elements, when two methyl groups are substituted, the two methyl groups may be linked to form a ring such as cyclopropyl.

And, n may be an integer of 1 to 10.

Meanwhile, in Chemical Formulas 1 to 3, Ar may be a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 30 carbon atoms. That is, Ar may be a conventional carbon atom having 6 to 30 aryl groups in which π-electrons are delocalized, or carbon atoms including hetero atoms such as nitrogen (N) and oxygen (O). It may be a 5 to 30 heteroaryl group.

However, according to the present invention, by way of non-limiting example, Ar is a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, Substituted or unsubstituted naphthalyl groups, substituted or unsubstituted anthracyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyridinyl, substituted or unsubstituted It may be a pyrazinyl group or a substituted or unsubstituted quinolinyl group.

Here, each aryl group corresponding to Ar is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, and an alkylsilyl group having 1 to 20 carbon atoms and having 1 carbon atom. ~ 20 haloalkyl groups, aryl groups of 6-20 carbon atoms, arylalkyl groups of 7-20 carbon atoms, arylsilyl groups of 6-20 carbon atoms, 7-20 carbon atoms Alkylaryl group, C1-C20 alkoxy group, C1-C20 alkylsiloxy group, C6-C20 aryloxy group, Halogen group and amino One or more substituents selected from the group consisting of (amino) groups may be further introduced. However, each aryl group corresponding to Ar may or may not include a substituent, wherein the substituent may be the same as or different from the substituent (R) substituted for Cp described above.

On the other hand, the transition metal compound according to the present invention is derived from a hydroxyalkyl amine compound together with a ligand (m (R) -Cp- (B) n-Ar) having a cyclopentadienyl skeleton described above at the central metal (M). It is characterized in that a ligand (ligand formed by a combination of O, Q ¹ , Q ² , Q ³ , N, Y ¹ and Y ² ) is introduced.

In Formulas 1 to 3, O is oxygen and N is nitrogen.

In addition, in the above Chemical Formulas 1 to 3, each arrow connected from N to M represents a transannular interaction in the form of a coordinating bond, the length of Q ¹ , Q ² and Q ^{3 to be} described later. It may or may not be formed accordingly.

In addition, in Formulas 1 to 3, Y ¹ and Y ² , which may be bonded to N, are each independently a hydrogen atom, a substituted or unsubstituted C 1-20 alkyl group, a substituted or unsubstituted C 3. ˜20 cycloalkyl groups, substituted or unsubstituted C1-C20 alkylsilyl groups, substituted or unsubstituted C1-C20 silylalkyl groups, substituted or unsubstituted C6-C20 aryl groups, substituted or unsubstituted C7-20 arylalkyl group, substituted or unsubstituted C7-20 alkylaryl group, substituted or unsubstituted C6-C20 arylsilyl group, and substituted or unsubstituted C6-C20 silylaryl It may be one or more substituents selected from the group consisting of groups.

In addition, in Chemical Formulas 1 to 3, Q ¹ , Q ^2, and Q ³ may each independently be a linking group represented by Formula 4 below:

[Chemical Formula 4]

In Chemical Formula 4,

R ¹ and R ² are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C20 Alkylsilyl group, substituted or unsubstituted C1-C20 silylalkyl group, substituted or unsubstituted C1-C20 haloalkyl group, substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted C7 -20 arylalkyl groups, substituted or unsubstituted C7-20 alkylaryl groups, substituted or unsubstituted C6-C20 arylsilyl groups, substituted or unsubstituted C6-C20 silylaryl groups, substituted or In the group consisting of an unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C1-C20 alkylsiloxy group, a substituted or unsubstituted C6-C20 aryloxy group, and a substituted or unsubstituted amino group One or more kinds selected Substituents, and

p is an integer of 1-10.

In particular, according to the present invention, in the above formulas (1) to (3), a ligand derived from a hydroxyalkyl amine compound (ligand formed by a combination of O, Q ¹ , Q ² , Q ³ , N, Y ¹ and Y ² ) Each may independently have a form in which hydrogen ions (protons) of a hydroxy group are removed from a monovalent trivalent hydroxyalkylamine compound.

That is, the hydroxyalkylamine compound may be an alkylamine compound having a monovalent hydroxy group (for Formula 1), an alkylamine compound having a divalent hydroxy group (for Formula 2) or an alkyl having a trivalent hydroxy group It may be an amine compound (in the case of Chemical Formula 3), and the structure of each compound is not particularly limited, and oxygen (O) moieties from which hydrogen ions have been removed from each hydroxy group may be bonded to M, respectively. .

Here, the hydroxyalkylamine-based compound is not particularly limited as long as it satisfies the above-described structure, but preferably N- (2-hydroxyethyl) amine (N- (2-Hydroxyethyl) amine), N, N- Bis- (2-hydroxyethyl) amine (N, N-Bis- (2-hydroxyethyl) amine), N, N, N-tris- (2-hydroxyethyl) amine (N, N, N-Tris- (2-hydroxyethyl) amine), (N- (3-hydroxypropyl) amine, N, N-bis- (3-hydroxypropyl) amine (N, N-Bis -(3-hydroxypropyl) amine), N, N, N-tris- (3-hydroxypropyl) amine (N, N, N-Tris- (3-hydroxypropyl) amine), N- (4-hydroxybutyl N- (4-Hydroxybutyl) amine, N, N-bis- (4-hydroxybutyl) amine N, N-Bis- (4-hydroxybutyl) amine N, N, N-tris (4-hydroxybutyl) amine (N, N, N-Tris- (4-hydroxybutyl) amine), N- (5-hydroxypentyl) amine (N- (5-Hydroxypentyl) amine), N, N- Bis- (5-hydroxypentyl) amine (N, N-Bis- (5-hydroxypentyl) amine), N, N, N-tris- (5-hydroxypentyl) amine (N, N, N-Tris- (5-hydroxypenty l) amine), N- (6-hydroxyhexyl) amine (N- (6-Hydroxyhexyl) amine), N, N-bis- (6-hydroxyhexyl) amine (N, N-Bis- (6- Hydroxyhexyl) amine), N, N, N-tris- (6-hydroxyhexyl) amine (N, N, N-Tris- (6-Hydroxyhexyl) amine), (N-2-hydroxyethyl) methylamine ( N- (2-Hydroxyethyl) methylamine), (N-2-hydroxyethyl) ethylamine (N- (2-Hydroxyethyl) ethylamine), N, N-bis- (2-hydroxyethyl) methylamine (N, N-Bis- (2-hydroxyethyl) methylamine), N, N-bis- (2-hydroxyethyl) ethylamine (N, N-Bis- (2-hydroxyethyl) ethylamine), N-3-hydroxypropyl) Methylamine (N- (3-Hydroxypropyl) methylamine), N-3-hydroxypropyl) ethylamine (N- (3-Hydroxypropyl) ethylamine), N, N-bis- (3-hydroxypropyl) methylamine ( N, N-Bis- (3-hydroxypropyl) methylamine), N, N-bis- (3-hydroxypropyl) ethylamine, N-2-hydroxy Ethyl) dimethylamine (N- (2-Hydroxyethyl) dimethylamine), N-2-hydroxyethyl) diethylamine (N- (2-Hydroxyethyl) diethylamine), N-3-hydroxy Propyl) dimethylamine (N- (3-Hydroxypropyl) dimethylamine), N-3-hydroxypropyl) diethylamine (N- (3-Hydroxypropyl) diethylamine), N- (2-methyl-2-hydroxyethyl) Amine (N- (2-Methyl-2-hydroxyethyl) amine), N- (1-methyl-2-hydroxyethyl) amine (N- (1-Methyl-2-hydroxyethyl) amine), N- (1, 2-dimethyl-2-hydroxyethyl) amine (N- (1.2-Dimethyl-2-hydroxyethyl) amine), N, N-bis- (2-methyl-2-hydroxyethyl) amine (N, N-Bis -(2-methyl-2-hydroxyethyl) amine), N, N-bis- (1-methyl-2-hydroxyethyl) amine (N, N-Bis- (1-methyl-2-hydroxyethyl) amine), N, N-Bis- (1,2-dimethyl-2-hydroxyethyl) amine (N, N-Bis- (1,2-Dimethyl-2-hydroxyethyl) amine), N, N, N-tris- ( 2-methyl-2-hydroxyethyl) amine (N, N, N-Tris- (2-methyl-2-hydroxyethyl) amine), N, N, N-tris- (1-methyl-2-hydroxyethyl ) Amine (N, N, N-Tris- (1-methyl-2-hydroxyethyl) amine), N- (3-methyl-3-hydroxypropyl) amine (N- (3-Methyl-3-hydroxypropyl) amine ), N- (2-methyl-3-hydroxypropyl) amine (N- (2-Methyl-3-hydroxypropyl) am ine), N- (1-methyl-3-hydroxypropyl) amine (N- (1-Methyl-3-hydroxypropyl) amine), N- (2,3-dimethyl-3-hydroxypropyl) amine (N -(2,3-Dimethyl-3-hydroxypropyl) amine), N- (1,3-dimethyl-3-hydroxypropyl) amine (N- (1,3-Dimethyl-3-hydroxypropyl) amine), N- (1,2-dimethyl-3-hydroxypropyl) amine (N- (1,2-Dimethyl-3-hydroxypropyl) amine), N- (1,2,3-trimethyl-3-hydroxypropyl) amine ( N- (1,2,3-Triimethyl-3-hydroxypropyl) amine), N, N-bis- (3-methyl-3-hydroxypropyl) amine (N, N-Bis- (3-methyl-3- hydroxypropyl) amine), N, N-bis- (2-methyl-3-hydroxypropyl) amine (N, N-Bis- (2-methyl-3-hydroxypropyl) amine), N, N-bis- (1 -Methyl-3-hydroxypropyl) amine (N, N-Bis- (1-methyl-3-hydroxypropyl) amine), N, N-bis- (2,3-dimethyl-3-hydroxypropyl) amine ( N, N-Bis- (2,3-dimethyl-3-hydroxypropyl) amine), N, N-bis- (1,3-dimethyl-3-hydroxypropyl) amine (N, N-Bis- (1, 3-dimethyl-3-hydroxypropyl) amine), N, N-bis- (1,2-dimethyl-3-hydroxypropyl) amine (N, N-Bis- ( 1,2-dimethyl-3-hydroxypropyl) amine), N, N-bis- (1,2,3-trimethyl-3-hydroxypropyl) amine (N, N-Bis- (1,2,3-trimethyl -3-hydroxypropyl) amine), N, N, N-tris- (3-methyl-3-hydroxypropyl) amine (N, N, N-Tris- (3-methyl-3-hydroxypropyl) amine), N , N, N-tris- (2-methyl-3-hydroxypropyl) amine (N, N, N-Tis- (2-methyl-3-hydroxypropyl) amine), N, N, N-tris- (1 -Methyl-3-hydroxypropyl) amine (N, N, N-Tris- (1-methyl-3-hydroxypropyl) amine), N, N, N-tris- (2,3-dimethyl-3-hydroxy Propyl) amine (N, N, N-Tris- (2,3-dimethyl-3-hydroxypropyl) amine), N, N, N-tris- (1,3-dimethyl-3-hydroxypropyl) amine (N , N, N-Tris- (1,3-dimethyl-3-hydroxypropyl) amine), N, N, N-tris- (1,2-dimethyl-3-hydroxypropyl) amine (N, N, N- Tris- (1,2-dimethyl-3-hydroxypropyl) amine), N, N, N-tris- (1,2,3-trimethyl-3-hydroxypropyl) amine (N, N, N-Tris- ( 1,2,3-trimethyl-3-hydroxypropyl) amine), N- (2-methyl-2-hydroxyethyl) methylamine (N- (2-Methyl-2-hyroxyethyl) methylamine), N- (1- Me 2-hydroxyethyl) methylamine (N- (1-Methyl-2-hyroxyethyl) methylamine), N- (1,2-dimethyl-2-hydroxyethyl) methylamine (N- (1,2-Dimethyl -2-hyroxyethyl) methylamine), N, N-bis- (2-methyl-2-hydroxyethyl) methylamine (N, N-Bis- (2-methyl-2-hyroxyethyl) methylamine), N, N- Bis- (1-methyl-2-hydroxyethyl) methylamine (N, N-Bis- (1-methyl-2-hyroxyethyl) methylamine), N, N-bis- (1,2-dimethyl-2-hydrate Hydroxyethyl) methylamine (N, N-Bis- (1,2-dimethyl-2-hyroxyethyl) methylamine), N- (2-methyl-2-hydroxyethyl) ethylamine (N- (2-Methyl-2 -hyroxyethyl) ethylamine), N- (1-methyl-2-hydroxyethyl) ethylamine (N- (1-Methyl-2-hyroxyethyl) ethylamine), N- (1,2-dimethyl-2-hydroxyethyl Ethylamine (N- (1,2-Dimethyl-2-hyroxyethyl) ethylamine), N, N-bis- (2-methyl-2-hydroxyethyl) ethylamine (N, N-Bis- (2-methyl -2-hyroxyethyl) ethylamine), N, N-bis- (1-methyl-2-hydroxyethyl) ethylamine (N, N-Bis- (1-methyl-2-hyroxyethyl) ethylamine), N, N- To bis- (1,2-dimethyl-2-hydroxyethyl) Amine (N, N-Bis- (1,2-dimethyl-2-hyroxyethyl) ethylamine), N- (3-methyl-3-hydroxypropyl) methylamine (N- (3-Methyl-3-hydroxypropyl) methylamine ), N- (2-methyl-3-hydroxypropyl) methylamine (N- (2-Methyl-3-hydroxypropyl) methylamine), N- (1-methyl-3-hydroxypropyl) methylamine (N- (1-Methyl-3-hydroxypropyl) methylamine), N- (2,3-dimethyl-3-hydroxypropyl) methylamine (N- (2,3-Dimethyl-3-hydroxypropyl) methylamine), N- (1 , 3-dimethyl-3-hydroxypropyl) methylamine (N- (1,3-Dimethyl-3-hydroxypropyl) methylamine), N- (1,2-dimethyl-3-hydroxypropyl) methylamine (N- (1,2-Dimethyl-3-hydroxypropyl) methylamine), N- (1,2,3-trimethyl-3-hydroxypropyl) amine (N- (1,2,3-Triimethyl-3-hydroxypropyl) methylamine) , N- (3-methyl-3-hydroxypropyl) ethylamine (N- (3-Methyl-3-hydroxypropyl) ethylamine), N- (2-methyl-3-hydroxypropyl) ethylamine (N- ( 2-Methyl-3-hydroxypropyl) ethylamine), N- (1-methyl-3-hydroxypropyl) ethylamine (N- (1-Methyl-3-hydroxypropyl) ethylamine ), N- (2,3-dimethyl-3-hydroxypropyl) ethylamine (N- (2,3-Dimethyl-3-hydroxypropyl) ethylamine), N- (1,3-dimethyl-3-hydroxypropyl ) Ethylamine (N- (1,3-Dimethyl-3-hydroxypropyl) ethylamine), N- (1,2-dimethyl-3-hydroxypropyl) ethylamine (N- (1,2-Dimethyl-3-hydroxypropyl ) ethylamine), N- (1,2,3-trimethyl-3-hydroxypropyl) ethylamine (N- (1,2,3-Triimethyl-3-hydroxypropyl) ethylamine), N, N-bis- (3 -Methyl-3-hydroxypropyl) methylamine (N, N-Bis- (3-methyl-3-hydroxypropyl) methylamine), N, N-bis- (2-methyl-3-hydroxypropyl) methylamine ( N, N-Bis- (2-methyl-3-hydroxypropyl) methylamine), N, N-bis- (1-methyl-3-hydroxypropyl) methylamine (N, N-Bis- (1-methyl-3 -hydroxypropyl) methylamine), N, N-bis- (2,3-dimethyl-3-hydroxypropyl) methylamine, N, N-Bis- (2,3-dimethyl-3-hydroxypropyl) methylamine, N, N-bis- (1,3-dimethyl-3-hydroxypropyl) methylamine (N, N-Bis- (1,3-dimethyl-3-hydroxypropyl) methylamine), N, N-bis- (1,2 -Dimethyl-3-hydroxy Phil) methylamine (N, N-Bis- (1,2-dimethyl-3-hydroxypropyl) methylamine), N, N-bis- (1,2,3-trimethyl-3-hydroxypropyl) methylamine (N , N-Bis- (1,2,3-trimethyl-3-hydroxypropyl) methylamine), N, N-bis- (3-methyl-3-hydroxypropyl) ethylamine (N, N-Bis- (3- methyl-3-hydroxypropyl) ethylamine), N, N-bis- (2-methyl-3-hydroxypropyl) ethylamine (N, N-Bis- (2-methyl-3-hydroxypropyl) ethylamine), N, N -Bis- (1-methyl-3-hydroxypropyl) ethylamine (N, N-Bis- (1-methyl-3-hydroxypropyl) ethylamine), N, N-bis- (2,3-dimethyl-3- Hydroxypropyl) ethylamine (N, N-Bis- (2,3-dimethyl-3-hydroxypropyl) ethylamine), N, N-bis- (1,3-dimethyl-3-hydroxypropyl) ethylamine (N , N-Bis- (1,3-dimethyl-3-hydroxypropyl) ethylamine), N, N-bis- (1,2-dimethyl-3-hydroxypropyl) ethylamine (N, N-Bis- (1, 2-dimethyl-3-hydroxypropyl) ethylamine), N, N-bis- (1,2,3-trimethyl-3-hydroxypropyl) ethylamine (N, N-Bis- (1,2,3-trimethyl- 3-hydroxypropyl) ethylamine), N- (2-methyl-2-hydroxy Methyl) dimethylamine (N- (1-Methyl-2-hyroxyethyl) dimethylamine), N- (1-methyl-2-hydroxyethyl) dimethylamine, N- (1-Methyl-2-hyroxyethyl) dimethylamine -(1,2-dimethyl-2-hydroxyethyl) dimethylamine (N- (1,2-Dimethyl-2-hyroxyethyl) dimethylamine), N- (2-methyl-2-hydroxyethyl) diethylamine ( N- (2-Methyl-2-hyroxyethyl) diethylamine), N- (1-methyl-2-hydroxyethyl) diethylamine (N- (1-Methyl-2-hyroxyethyl) diethylamine), N- (1, 2-dimethyl-2-hydroxyethyl) diethylamine (N- (1,2-Dimethyl-2-hyroxyethyl) diethylamine), N- (3-methyl-3-hydroxypropyl) dimethylamine (N- (3 -Methyl-3-hydroxypropyl) dimethylamine), N- (2-methyl-3-hydroxypropyl) dimethylamine (N- (2-Methyl-3-hydroxypropyl) dimethylamine), N- (1-methyl-3-hydroxy Hydroxypropyl) dimethylamine (N- (1-Methyl-3-hydroxypropyl) dimethylamine), N- (2,3-dimethyl-3-hydroxypropyl) dimethylamine (N- (2,3-Dimethyl-3-hydroxypropyl ) dimethylamine), N- (1,3-dimethyl-3-hydroxypropyl) dimethylamine (N- (1,3-Dimethyl- 3-hydroxypropyl) dimethylamine), N- (1,2-dimethyl-3-hydroxypropyl) dimethylamine (N- (1,2-Dimethyl-3-hydroxypropyl) dimethylamine), N- (1,2,3- Trimethyl-3-hydroxypropyl) dimethylamine (N- (1,2,3-Triimethyl-3-hydroxypropyl) dimethylamine), N- (3-methyl-3-hydroxypropyl) diethylamine (N- (3 -Methyl-3-hydroxypropyl) diethylamine), N- (2-methyl-3-hydroxypropyl) diethylamine (N- (2-Methyl-3-hydroxypropyl) diethylamine), N- (1-methyl-3- Hydroxypropyl) diethylamine (N- (1-Methyl-3-hydroxypropyl) diethylamine), N- (2,3-dimethyl-3-hydroxypropyl) diethylamine (N- (2,3-Dimethyl- 3-hydroxypropyl) diethylamine), N- (1,3-dimethyl-3-hydroxypropyl) diethylamine (N- (1,3-Dimethyl-3-hydroxypropyl) diethylamine), N- (1,2-dimethyl -3-hydroxypropyl) diethylamine (N- (1,2-Dimethyl-3-hydroxypropyl) diethylamine), and N- (1,2,3-trimethyl-3-hydroxypropyl) diethylamine (N -(1,2,3-Triimethyl-3-hydroxypropyl) diethylamine) It may be at least one compound.

The first transition metal compound represented by Chemical Formula 1, Chemical Formula 2 or Chemical Formula 3 satisfies the above-described structure, thereby allowing more selective synthesis of alpha-olefins from ethylene. Here, the alpha-olefin may be 1-butene, 1-hexene, 1-octene, 1-octene, 1-decene, 1-dodecene dodecene), 1-tetradecene (1-tetradecene), 1-hexadecene (1-hexadecene) and 1-octadecene (1-octadecene) may be one or more selected from the group consisting of. In particular, according to the present invention, when using the transition metal compound represented by Formula 1, Formula 2 or Formula 3, 1-hexene, which is a trimer alpha-olefin, may be more selectively synthesized from ethylene.

On the other hand, the tandem catalyst system for producing polyethylene according to the present invention includes a second transition metal compound for copolymer synthesis of alpha-olefin and ethylene together with the aforementioned first transition metal compound.

That is, the catalyst system according to the present invention is a catalyst system usable for synthesizing polyethylene, wherein the first transition metal compound included in the catalyst system is capable of synthesizing a selective alpha-olefin (particularly 1-hexene) from ethylene. In addition, the resulting alpha-olefin can be copolymerized with ethylene by the catalysis of the second transition metal compound to produce polyethylene. Thus, the catalyst system enables the production of polyethylene having a low density and uniform composition with ethylene alone without the use (addition) of separate comonomers.

In the tandem catalyst system, the second transition metal compound may be applied without limitation catalyst compounds that enable copolymerization of ethylene and alpha-olefins in the art. However, according to the present invention, the second transition metal compound is, but is not limited to, one selected from the group consisting of Ziegler-Natta type catalysts, chromium-based catalysts, metallocene catalysts, and constrained geometry catalysts. The above compound may be sufficient.

Here, the Ziegler-Natta catalyst may be a compound such as titanium trichloride, titanium tetrachloride, etc .; The chromium-based catalyst may be a compound such as chromium trioxide, bis (triphenylsilyl) chromate, or the like; The metallocene catalyst may be bis (cyclopentadienyl) zirconium chloride, bis (indenyl) zirconium chloride, or the like; The geometric restraint catalyst may be [Me ₂ Si (Me ₄ C ₅ ) NtBu] TiCl ₂ , manufactured by DOW. However, the exemplified compounds are merely examples of the compounds applicable to the catalyst system, and the examples are not intended to limit the scope of the present invention.

Meanwhile, the tandem catalyst system according to the present invention includes a promoter compound for activating the first transition metal compound and the second transition metal compound.

The cocatalyst compound serves to help the reaction of the central metal and ethylene by cationizing or activating the central metal of the first transition metal compound and the second transition metal compound.

Such promoter compounds may be applied without limitation to conventional promoter compounds in the art to which the present invention pertains; According to the present invention, it may be an alkyl aluminum compound or a weakly coordinated Lewis acid compound; Preferably it may be at least one selected from the group consisting of compounds represented by the following formula (5), (6) and (7):

[Chemical Formula 5]

In Formula 5,

R ³ is an alkyl group having 1 to 10 carbon atoms, n is an integer of 1 to 70;

[Chemical Formula 6]

In Formula 6,

R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or a halogen group, and R ⁴ , R ⁵ and R ⁶ At least one is an alkyl group having 1 to 10 carbon atoms;

[Formula 7]

In Formula 7,

C is Lewis base's proton-bonding cation or an oxidizing metal or nonmetallic compound,

D is a compound of elements and organic substances belonging to groups 5 to 15 of the periodic table.

Here, the compound represented by Formula 5 may have a linear, cyclic, or net structure, and non-limiting examples include methylaluminoxane, ethyl aluminoxane, butyl aluminoxane, butylaluminoxane, hexyl aluminoxane ( Hexylaluminoxane), octyl aluminoxane (Octylaluminoxane), and decyl aluminoxane (Decylaluminoxane) may be at least one compound selected from the group consisting of.

And, the compound represented by the formula (6), non-limiting examples, trimethylaluminum (Trimethylaluminum), triethylaluminum (Triethylaluminum), tributylaluminum, Trihexylaluminum, Trioctyl aluminum (Trioctylaluminum), Tridecylaluminum, Dimethylaluminum methoxide, Diethylaluminum methoxide, Dibutylaluminum methoxide, Dibutylaluminum chloride, Diethylaluminum chloride chloride, Dibutylaluminum chloride, methylaluminum dimethoxide, ethylaluminum dimethoxide, butylaluminum dimethoxide, butylaluminum dimethoxide, methylaluminum dchloride ichloride), ethylaluminum dichloride, and butylaluminum dichloride.

And, the compound represented by the formula (7), non-limiting examples, trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributyl Tributylammonium tetraphenylborate, Trimethylammonium tetrakis (pentafluorophenyl) borate, Triethylammonium tetrakis (pentafluorophenyl) borate, Triethylammonium tetrakis (pentafluorophenyl) borate, Tripropylammonium tetrakis (pentafluorophenyl) borate, Tributylammonium tetrakis (pentafluorophenyl) borate, Aninium tetraphenylborate (A nilinium tetraphenylborate, anilinium tetrakis (pentafluorophenyl) borate, pyridinium tetraphenylborate, pyridinium tetrakis (pentafluorophenyl) borate (Pyridinium tetrakis (pentafluorophenyl) borate borate), ferrocenium tetrakis (pentafluorophenyl) borate, silver tetraphenylborate, silver tetrakis (pentafluorophenyl) borate (Silver tetrakis (pentafluorophenyl) borate ), Tris (pentafluorophenyl) borane, Tris (2,3,5,6-tetrafluorophenyl) borane (Tris (2,3,5,6-tetrafluorophenyl) borane ), Tris (2,3,4,5-tetraphenylphenyl) borane (Tris (2,3,4,5-tetraphenylphenyl) borane), and tris (3,4,5-trifluorophenyl) borane (Tris (3,4,5-trifluorophenyl) borane) selected from the group consisting of May be one or more compounds.

On the other hand, in the catalyst system according to the present invention, since the content of the promoter compound is sufficient to activate the first transition metal compound and the second transition metal compound, the specific content is not particularly limited. It may vary depending on the type and content of each transition metal compound.

However, according to the present invention, the cocatalyst compound has a molar ratio of 1: 1 to 1: 1,000,000, preferably 1: 1 to 1: 100,000, based on the central transition metal atom of the transition metal compound included in the catalyst system. More preferably, it may be included in a molar ratio of 1: 1 to 1: 5,000. That is, it is advantageous in view of the improvement of the reaction efficiency that the promoter compound is included in the above range.

In the catalyst system, the content ratio of the first transition metal compound to the second transition metal compound is in the synthesis reaction of the alpha-olefin by the first transition metal compound and the alpha-olefin and ethylene by the second transition metal compound. It may be adjusted in view of the efficiency of the copolymerization reaction and so on is not particularly limited. However, according to the present invention, the second transition metal compound has a molar ratio of 1: 0.001 to 1: 5, preferably 1: 0.005 to 1, based on the transition metal atom included in each compound with respect to the first transition metal compound. It is advantageous to include the molar ratio of 1: 2.5, more preferably 1: 0.01 to 1: 2 in terms of improving the reaction efficiency.

Meanwhile, the tandem catalyst system may further include a carrier on which the first transition metal compound, the second transition metal compound, and the promoter compound are supported.

The carrier is a porous organic / mu compound having a fine pores (pore) on the surface or inside, it can be applied without limitation those conventional in the art. However, according to the present invention, the carrier is silica, alumina, magnesium chloride, calcium chloride, bauxite, zeolite, magnesium oxide, zirconium oxide, titanium oxide, boron trioxide, calcium oxide, zinc oxide, barium oxide, thorium oxide and these It may be one or more selected from the group consisting of. Here, the composite is a non-limiting example SiO ₂ -MgO, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -CrO ₂ O ₃ , SiO ₂ -TiO _2- MgO and the like.

The method of supporting the transition metal compound and the cocatalyst compound on such a carrier may include a method of directly supporting the transition metal compound on a dehydrated carrier; A method of supporting the transition metal compound after pretreating the carrier with the promoter compound; A method of post-treatment with a cocatalyst compound after supporting the transition metal compound on the carrier; A method of reacting the transition metal compound with the cocatalyst compound and then adding a carrier may be applied.

In addition, as a solvent applicable to the supporting method as described above, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, dodecane Aliphatic hydrocarbon solvents such as Candecane; Aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, and toluene; Halogenated aliphatic hydrocarbon solvents such as dichloromethane, trichloromethane, dichloroethane and trichloroethane; Or mixtures thereof.

In addition, the process of supporting the transition metal compound and the cocatalyst compound on the carrier is advantageous in terms of the efficiency of the supporting process to be carried out at 0 to 120 ℃, preferably 20 to 100 ℃ temperature conditions.

In addition, the tandem catalyst system may further include an organic solvent.

The type of the organic solvent is not particularly limited, and a solvent known to be commonly used in the synthesis of polyethylene in the art to which the present invention belongs may be applied. Suitably, the organic solvent is butane, pentane, hexane, heptane, octane, nonane, decane, undecane, undecane, Aliphatic hydrocarbon solvents such as Dodecane; Aromatic hydrocarbon solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, and toluene; Or a halogenated aliphatic hydrocarbon solvent such as dichloromethane, trichloromethane, dichloroethane, trichloroethane, or the like.

Meanwhile, according to another embodiment of the present invention,

There is provided a process for the preparation of polyethylene comprising the step of polymerizing ethylene in the presence of the tandem catalyst system described above.

As the polyethylene production process proceeds in the presence of the tandem catalyst system described above, low density in a single process using only ethylene as a reaction raw material without using (adding) a separate comonomer or an additional compound for controlling the density of the polymer. And polyethylene having a uniform composition can be prepared.

The method for producing such polyethylene is preferably

Forming an alpha-olefin from ethylene in the presence of said first transition metal compound and a promoter compound; And

Supplying the second transition metal compound and ethylene to the formation system of the alpha-olefin to form a copolymer of the alpha-olefin and ethylene

It may be performed including.

In the forming of the alpha-olefin, the content of the first transition metal compound may be adjusted in view of the synthesis reaction efficiency of the alpha-olefin, and the content of the promoter compound may activate the first transition metal compound. Since the amount is sufficient, the specific content is not particularly limited. However, according to the present invention, the content of the first transition metal compound is 10 ^-8 mol / Kg to 1 mol / Kg, preferably 10 ^-7 mol per unit weight (Kg) of ethylene, based on the transition metal atom. / Kg to 10 ^-1 mol / Kg, more preferably 10 ^-7 mol / Kg to 10 ^-2 mol / Kg.

In addition, the cocatalyst compound has a molar ratio of 1: 1 to 1: 1,000,000, preferably 1: 1 to 1: 500,000 molar ratio, more preferably 1: based on the transition metal atom included in the first transition metal compound. It is advantageous to include the molar ratio of 1 to 1: 50,000 in terms of improving the reaction efficiency.

In the forming of the alpha-olefin from the ethylene, the first transition metal compound, the cocatalyst compound, the ethylene and the solvent may be added to the reactor, and in particular, 1-hexene may be prepared by trimerizing the ethylene. At this time, the type of solvent used in the alpha-olefin forming step is not particularly limited, but according to the present invention may be normal hexane, normal heptane, cyclo hexane, toluene, benzene, or a mixture thereof.

On the other hand, in the step of forming the copolymer, the content of the second transition metal compound is not particularly limited because it can be adjusted in view of the efficiency of the copolymerization reaction of alpha-olefin and ethylene. However, according to the present invention, the second transition metal compound has a molar ratio of 1: 0.001 to 1: 5, preferably 1: 0.005 to 1, based on the transition metal atom included in each compound with respect to the first transition metal compound. It is advantageous to include the molar ratio of 1: 2.5, more preferably 1: 0.01 to 1: 2 in terms of improving the reaction efficiency.

On the other hand, in the step of forming the alpha-olefin, the alpha-olefin is 1-butene (1-butene), 1-hexene (1-hexene), 1-octene (1-octene), 1-decene (1- 1 type selected from the group consisting of decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene It may be abnormal. In particular, according to the present invention, when using the transition metal compound represented by Formula 1, Formula 2 or Formula 3, 1-hexene, which is a trimer alpha-olefin, may be more selectively synthesized from ethylene.

In addition, the forming of the copolymer may be performed by applying a polymerization reaction such as a slurry phase, a liquid phase, a gas phase, a bulk phase, and the like. When the step of forming the copolymer is carried out in a liquid phase or a slurry phase reaction, a solvent or a monomer itself may be used as a medium, and the solvent used is as described above.

And, the step of polymerizing ethylene in the presence of the tandem catalyst system can be carried out under the temperature and pressure conditions applied to the conventional polymerization of polyethylene. However, according to the present invention, the method for producing polyethylene may be carried out under a temperature condition of 0 to 150 ℃, preferably 15 to 150 ℃; It may be carried out under pressure conditions of 1 to 1000 atm, preferably 2 to 200 atm. That is, the method for producing polyethylene is advantageously carried out under the above conditions of temperature and pressure in view of the minimum conditions required for the reactive expression of ethylene monomers, the yield of the resulting polymer, and the like.

According to the production method of the present invention, polyethylene having a low density and uniform composition can be produced in a single process using only ethylene as a reaction raw material without using a separate comonomer or an additional compound for controlling the density of the polymer. . Preferably, the ethylene / alpha-olefin copolymers prepared according to the process may have a density of 0.960 g / cc or less, more preferably 0.920 to 0.955 g / cc.

On the other hand, the method for producing a polyolefin according to the present invention may be carried out in addition to the above-described steps, further comprising steps that can be conventionally performed in the art before or after the step.

Best Mode for Carrying Out the Invention Hereinafter, preferred embodiments are described to facilitate understanding of the present invention. However, the following examples are intended to illustrate the present invention without limiting it thereto.

First, all of the following reactions were carried out under an inert atmosphere such as nitrogen or argon, and a standard Schlenk technique and a glove box technique were used.

In addition, tetrahydrofuran (THF), normal hexane (n-Hexane), normal pentane (n-Pentane), diethyl ether, and methylene chloride (Methylene Chloride, CH ₂ ) used in the synthesis or polymerization reaction. Cl ₂ ), toluene (Toluene) and the like solvent was used to remove the water through an activated alumina column (Activated Alumina Column), and then stored on an activated molecular sieve (Molecular Sieve 5A, Yakuri Pure ChemicalsCo). In addition, double hydrogen substituted chloroform (Chloroform-d, CDCl ₃ ) and deuterated benzene (benzene-d6, C ₆ D ₆ ) used in the NMR structure analysis of the compound were purchased from Cambridge Isotope Laboratories, and then activated molecular sieve ( Molecular Sieve 5A, Yakuri Pure Chemicals Co) was used for drying.

Further, n-Butyllithium (2.5 M Solution in n-Hexane), Phenyllithium (1.8 M solution in Dibutyl ether), 1-Bromo-3,5-dimethylbenzene (1-Bromo- 3,5-dimethylbenzene, 6,6-dimethylfulvene, triethanolamine, triethylamine, 6,6-pentamethylfulvene, trimethyl Trimethylsilyl chloride, titanium chloride (TiCl ₄ ), tantalum chloride (TaCl ₅ ), anhydrous magnesium sulfate (Magnesium sulfate, anhydrous) and the like were purchased from Sigma-Aldrich and used without purification.

In addition, as the second transition metal compound, which is a transition metal compound for ethylene / alpha-olefin copolymer, bis (indenyl) zirconium chloride (Bis (indenyl) zirconium dichloride) was used, which was purchased from Chemtura Organometallics GmbH and used without purification.

In addition, ¹ H NMR was measured using a Bruker Avance 400 Spectrometer at room temperature, and the chemical shift of the NMR spectrum was measured by deuterated chloroform (CDCl ₃ ) and deuterated benzene (C ₆ D ₆ ). ? = 7.24 ppm and 7.16 ppm were expressed based on respective criteria.

Example  1: [η ⁵ - (3- SiMe ₃ ) C ₅ H ₃ CMe ₂ -3,5- Me ₂ C ₆ H ₃ ] Ti (N ( CH ₂ O ) ₃ ) Synthesis of

(1-a) C ₅ H ₃ ( SiMe ₃ ) ₂ CMe ₂ -3,5- Me ₂ C ₆ H ₃  of  synthesis

: Dissolve about 1.15 g (about 5.3 mmol) of [C ₅ H ₄ CMe ₂ -3,5-Me ₂ C ₆ H ₃ ] Li in 50 ml diethyl ether, lower the temperature with ice water, and then add about 0.7 ml (0.6 g). , 5.5mmol) Trimethylsilyl chloride solution was added dropwise and slowly raised to room temperature and stirred for about 12 hours. The white suspension obtained was then cooled to about -30 ° C. and about 5.4 mmol (2.5 M solution in hexanes) of butyllithium solution was added dropwise. The reaction mixture was heated to room temperature, stirred for about 3 hours, and then cooled down with ice water, and then slowly added to a solution of about 0.8 ml (0.7 g, 6.4 mmol) trimethylsilyl chloride dropwise to room temperature for about 12 hours. Stir it. Then, the obtained mixed liquid is poured into ice water (100 ml). Only the organic layer was extracted with diethyl ether (50mlx2), collected, dried over anhydrous magnesium sulfate, and filtered. The solvent was evaporated with a rotary evaporator, and the yellow oil obtained was distilled under 0.4 Torr at 160 ° C. to obtain about 1.26 g of C ₅ H ₃ (SiMe ₃ ) ₂ CMe ₂ -3,5-Me ₂ C ₆ H ₃ Was obtained in a yield of about 66%.

Results of ¹ H NMR confirming the synthesis of C ₅ H ₃ (SiMe ₃ ) ₂ CMe ₂ -3,5-Me ₂ C ₆ H ₃ are as follows.

¹ H NMR (400 MHz, CDCl ₃ ): δ 6.90 (s, 2H, Ar oH), 6.78 (s, 1H, Ar pH), 6.37 (m, 2H, Cp H), 6.19 (m, 1H, Cp H ), 2.24 (s, 6H, ArCH ₃ ), 1.51 (s, 6H, C (CH ₃ ) ₂ ), -0.05 (s, 18H, Si (CH ₃ ) ₃ ).

(1-b) [η ⁵ - (3- SiMe ₃ ) C ₅ H ₃ CMe ₂ -3,5- Me ₂ C ₆ H ₃ ] TiCl ₃  of  synthesis

: Ligand C ₅ H ₃ (SiMe ₃ ) ₂ CMe ₂ -3,5-Me ₂ C ₆ H ₃ obtained in Example 1-a was dissolved in about 1.18 g (about 3.3 mmol) in 40 ml dichloromethane, and then -40 The temperature was lowered to ℃ and slowly added an equivalent amount of titanium chloride (1M solution in MC). Then, the temperature was raised to room temperature and then stirred for about 12 hours. Subsequently, after evaporating the volatiles in vacuo, the residue was removed with normal pentane to give light brown crystals of [η ^5- (3-SiMe ₃ ) C ₅ H ₃ CMe ₂ -3,5-Me ₂ C ₆ H _3] TiCl ₃ about 1.02g to give a (2.3mmol, 72% yield).

Results of ¹ H NMR confirming the synthesis of [η ^5- (3-SiMe ₃ ) C ₅ H ₃ CMe ₂ -3,5-Me ₂ C ₆ H ₃ ] TiCl ₃ are as follows.

¹ H NMR (400 MHz, C ₆ D ₆ ): δ 6.96 (m, 1H, Cp H), 6.69 (s, 2H, Ar oH), 6.64 (m, 2H, Cp H and Ar p H), 6.55 ( m, 1H, Cp H), 2.08 (s, 6H, ArCH ₃ ), 1.70 (s, 6H, C (CH ₃ ) ₂ ), 0.13 (s, 9H, Si (CH ₃ ) ₃ ).

(1-c) [η ⁵ - (3- SiMe ₃ ) C ₅ H ₃ CMe ₂ -3,5- Me ₂ C ₆ H ₃ ] Ti (N ( CH ₂ O ) ₃ ) Synthesis of

: [Η ^5- (3-SiMe ₃ ) C ₅ H ₃ CMe ₂ -3,5-Me ₂ C ₆ H ₃ ] TiCl ₃ obtained through Example 1-b was dissolved in 50 ml of toluene, and then stirred at -78 ° C. After lowering the temperature, an equivalent of triethanolamine and three equivalents of triethylamine toluene solution were added dropwise, the temperature was raised to room temperature, and the mixture was heated to 50 ° C. and stirred for about 12 hours. The orange suspension was filtered through Celite, dried in vacuo and washed with hexane, which was ivory-colored solid represented by the following formula [η ^5- (3-SiMe ₃ ) C ₅ H ₃ CMe ₂ -3,5-Me ₂ C ₆ About 1 g (2.095 mmol, yield 35%) of H ₃ ] Ti (N (CH ₂ O) ₃ ) was obtained.

[Chemical Formula]

Results of ¹ H NMR confirming the synthesis of [η ^5- (3-SiMe ₃ ) C ₅ H ₃ CMe ₂ -3,5-Me ₂ C ₆ H ₃ ] Ti (N (CH ₂ O) ₃ ) are as follows. Is the same as

¹ H NMR (400 MHz, CDCl ₃ ): d 6.87 (s, 2H, Ar-o), 6.77 (s, 1H, Ar-p), 6.35-6.37 (q, 3H, Cp), 4.26-4.3 (q , 6H, NCH ₂ CH ₂ O), 2.26-2.96 (t, 6H, NCH ₂ CH ₂ O), 2.27 (s, 6H, ArCH ₃ ), 1.7 (s, 6H, C (CH ₃ ) ₂ ) 0.18 ( s, 9H, Si (CH ₃ ) ₃ ).

Example  2: [η ⁵ - C ₅ H ₄ CMe ₂ Ph ] Ti (N ( CH ₂ CH ₂ O ) ₃ ) Synthesis of

(2-a) C ₅ H ₄ ( SiMe ₃ ) CMe ₂ Ph  synthesis

: Dissolve phenyllithium solution (2.0M sol in dibutyl ether, 7.5ml, 15mmol) in 20ml diethyl ether, lower the temperature to -40 ℃, equivalent of 6,6-dimethylpulbene (1.593g, 15mmol) Was dissolved in 20 ml diethyl ether and slowly added. The reaction mixture was warmed to room temperature and stirred for 1 hour. The solvent was removed in vacuo, washed with hexane (15mlx3) and dried in vacuo to separate white solid.

After dissolving the obtained solid in tetrahydrofuran solution again, the temperature was lowered to 0 ° C., and 2.27 ml of 1.2 equivalents of trimethylsilyl chloride (1.955 g, 18 mmol) was added dropwise and stirred slowly at room temperature. Then, the obtained pale yellow solution was poured into ice water (100 ml). Only the organic layer was extracted with diethyl ether (50 ml x 3), collected, dried over anhydrous magnesium sulfate, and filtered. The solvent was evaporated in a rotary evaporator, and the yellow oil obtained was distilled at 0.4 torr at 180 ° C. to obtain a ligand C ₅ H ₄ (SiMe ₃ ) CMe ₂ Ph of brown oil in a yield of 58%.

Results of ¹ H NMR confirming the synthesis of C ₅ H ₄ (SiMe ₃ ) CMe ₂ Ph are as follows.

¹ H-NMR (400 MHz, 22 ° C., CDCl ₃ ): d 0.29 (s, 9H, SiMe 3), 1.87 (s, 6H, CMe ₂ ), 6.70-6.47 (m, 4H, C ₅ H ₄ ), 7.64 -7.43 (m, 5H, Ph).

(2-b) [η ⁵ - C ₅ H ₄ CMe ₂ Ph )] TiCl ₃  synthesis

: Dissolve the ligand C ₅ H ₄ (SiMe ₃ ) CMe ₂ Ph (about 2.2395g, 6.278mmol) obtained in Example 2-a in 30ml of dichloromethane, lower the temperature to -78 ℃ and the equivalent of titanium chloride (1M sol in dichloromethane) 6.23ml was added slowly, raised to room temperature and stirred overnight. The solvent of the obtained dark red solution was removed in vacuo to obtain about 1.059 g of [η ⁵ -C ₅ H ₄ CMe ₂ Ph)] TiCl _{3 in} oil form (yield about 50%).

Results of ¹ H NMR confirming the synthesis of [η ⁵ -C ₅ H ₄ CMe ₂ Ph)] TiCl ₃ are as follows.

¹ H NMR (400 MHz, C ₆ D ₆ ): δ 7.03 (d, 2H, Ar-m), 6.95 (t, 1H, Ar-p), 6.84 (d, 2H, Ar-o), 1.53 (s, 6H, 2Me).

(2-c) [η ⁵ - C ₅ H ₄ CMe ₂ Ph ] Ti (N ( CH ₂ CH ₂ O ) ₃ ) Synthesis of

: Dissolve about 6 mmol of [η ⁵ -C ₅ H ₄ CMe ₂ Ph)] TiCl ₃ obtained in Example 2-b in 50 ml toluene, lower the temperature to −78 ° C., and give equivalent weight of triethanolamine, three equivalent of tree. Ethylamine toluene solution was added dropwise and then raised to room temperature and then stirred at about 12 hours with heating to 50 ° C. The orange suspension was filtered through Celite, dried in vacuo and washed with hexane, which was ivory-colored solid represented by the following formula [η ⁵ - C ₅ H ₄ CMe ₂ Ph ] Ti (N (CH ₂ CH ₂ O) ₃ ) 1.357 g (3.6 mmol, yield about 60%) were obtained.

[Chemical Formula]

Results of ¹ H NMR confirming the synthesis of [η ⁵ -C ₅ H ₄ CMe ₂ Ph] Ti (TEA) are as follows.

¹ H NMR (400 MHz, CDCl ₃ ): δ 6.70-6.48 (m, 5H, ArH), 4.28 (m, 6H, NCH ₂ CH ₂ O), 3.08 (m, 6H, NCH ₂ CH ₂ O), 1.70 ( s, 6H, C (CH ₃ ) ₂ ).

Example  3: {η ⁵ -C ₅ H ₄ C [( CH ₂ ) ₅ ] Ph } Ti ( TEA ) Synthesis of

(3-a) C ₅ H ₄ ( SiMe ₃ ) C [( CH ₂ ) ₅ ] Ph Synthesis of

: Dissolve phenyl lithium solution (2.0M sol in dibutyl ether, 4g, 48mmol) in 200ml of diethyl ether, lower the temperature to -50 ℃ and 20ml of equivalent 6,6-pentamethylenepulbene (6.95g, 48mmol) It was dissolved in diethyl ether and slowly added. The reaction mixture was warmed to room temperature and stirred for 3 hours. The yellow solution was cooled to 0 ° C. and 2.27 ml of 6.4 ml (5.5 g, 51 mmol) trimethylsilyl chloride (1.955 g, 18 mmol) was added dropwise and stirred slowly to room temperature. The pale yellow solution obtained was then poured into ice water (250 ml). Only the organic layer was extracted with diethyl ether (100 ml × 2), collected, washed with 200 ml brine solution, dried over anhydrous magnesium sulfate, and filtered. The solvent was evaporated with a rotary evaporator, and the resulting yellow oil was distilled at 0.4 torr at 165 ° C. to obtain ligand C ₅ H ₄ (SiMe ₃ ) C [(CH ₂ ) ₅ ] Ph in an isomer mixed state in 63% yield.

Results of ¹ H NMR confirming the synthesis of C ₅ H ₄ (SiMe ₃ ) C [(CH ₂ ) ₅ ] Ph are as follows.

¹ H NMR (400 MHz, CDCl ₃ , main isomer): δ 7.40 (m, 2H, Ph oH), 7.33 (m, 2H, Ph mH), 7.15 (m, 1H, Ph pH), 6.43 (m, 2H , Cp H), 6.15 (s, 1H, Cp H), 3.27 (s, 1H, Cp H), 2.17 (m, 4H, α-CH ₂ ), 1.65-1.40 (m, 6H, β- and γ- CH ₂ ), -0.03 (s, 9H, Si (CH ₃ ) ₃ ).

(3-b) {η ⁵ -C ₅ H ₄ C [( CH ₂ ) ₅ ] Ph } TiCl ₃  of  synthesis

: Dissolve about 3.70 g (12.5 mmol) of ligand C ₅ H ₄ (SiMe ₃ ) C [(CH ₂ ) ₅ ] Ph prepared in Example 3-a in 40 ml methylene chloride, and lower the temperature to -40 ℃ 1.4 ml (2.4 g, 12.7 mmol) of titanium chloride was slowly added thereto, then raised to room temperature and then stirred overnight. The solvents were removed in vacuo and washed with 30 ml of pentane. The supernatant was removed, extracted with methylene chloride from the remaining residue, and recrystallized at a ratio of 1: 1 (v / v) of pentane methylene chloride, reddish brown {η ⁵ -C ₅ H ₄ C [(CH ₂ ) ₅ ] Ph} TiCl ₃ was obtained in a yield of about 78%.

Results of ¹ H NMR confirming the synthesis of {η ⁵ -C ₅ H ₄ C [(CH ₂ ) ₅ ] Ph} TiCl ₃ are as follows.

¹ H NMR (400 MHz, C ₆ D ₆ ): δ 7.16-7.06 (m, 4H, Ph o- and mH), 7.01 (m, 1H, Ph pH), 6.31 (ps t, ³ J _HH = 2.8, 2H, Cp H), 5.97 (ps t, ³ J _HH = 2.8, 2H, Cp H), 2.45 (d, ² J _HH = 13.2, 2H, α-CH _eq ), 1.88 (m, 2H, α-CH _ax ), 1.37 (br, 3H, β- and γ-CH ₂ ), 1.25-1.05 (m, 3H, β- and γ-CH ₂ ).

(3-c) {η ⁵ -C ₅ H ₄ C [( CH ₂ ) ₅ ] Ph } Ti (N ( CH ₂ CH ₂ O ) ₃ ) Synthesis of

: About 1.92 mmol (0.722 g) of {η ⁵ -C ₅ H ₄ C [(CH ₂ ) ₅ ] Ph} TiCl ₃ prepared in Example 3-b was dissolved in 50 ml of toluene, and then heated to -78 ° C. After lowering the equivalent of triethanolamine and three equivalents of triethylamine toluene solution was added dropwise, the mixture was raised to room temperature and heated to 50 ° C. and stirred for about 12 hours. The orange suspension was filtered through Celite and dried in vacuo and washed with hexane, {I ⁵ -C ₅ H ₄ C [(CH ₂ ) ₅ ] Ph} Ti (N (CH ₂ CH) ₂ 0) ₃ ) about 0.48 g (1.152 mmol, yield 60%) was obtained.

[Chemical Formula]

Results of ¹ H NMR confirming the synthesis of {η ⁵ -C ₅ H ₄ C [(CH ₂ ) ₅ ] Ph} Ti (TEA) are as follows.

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.45 (d, 2H, ArH), 7.26 (d, 2H, ArH), 7.15 (m, 1H, ArH), 6.18 (s, 2H, Cp), 6.09 (s , 2H, Cp), 4.17 (m, 6H, NCH ₂ CH ₂ O), 2.85 (m, 6H, NCH ₂ CH ₂ O), 2.65 (d, 2H,-(CH ₂ ) ₅ ), 2.02 (t, 2H,-(CH ₂ ) ₅ ), 1.56 (b, 3H,-(CH ₂ ) ₅ ), 1.39 (m, 3H,-(CH ₂ ) ₅ ).

Example  4: [η ⁵ - (3- SiMe ₃ ) C ₅ H ₃ C [( CH ₂ ) ₅ ] Ph } Ti (N ( CH ₂ CH ₂ O ) ₃ ) Synthesis of

(4-a) C ₅ H ₃ ( SiMe ₃ ) ₂ C [( CH ₂ ) ₅ ] Ph  synthesis

: Dissolve 1.67g (7.3mmol) of {C5H4C [(CH2) 5] Ph} Li in 70ml diethyl ether, lower to 0 ° C, add dropwise 0.8ml (0.7g, 6.4mmol) trimethylsilyl chloride and stir overnight It was. After lowering the white suspension to -30 ° C, 7.3mmol of 2.5M butyllithium hexane solution was added dropwise, and then slowly raised to room temperature and stirred for 3 hours. After the reaction solution was lowered to 0 ° C., 0.9 ml (0.8 g, 7.4 mmol) trimethylsilyl chloride was added dropwise and stirred at room temperature overnight. The reaction solution was poured into 100 ml of iced water, extracted twice with 50 ml of diethyl ether, dried over MgSO 4, blown off with solvent, and distilled at 0.4 ° C. to 160 ° C. to obtain 1.28 g (3.5 mmol, 55% yield) of the product.

Results of ¹ H NMR confirming the synthesis of C ₅ H ₃ (SiMe ₃ ) ₂ C [(CH ₂ ) ₅ ] Ph are as follows.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.45-7.1 (m, 5H, Ph H), 6.50 (m, 1H, Cp H), 6.39 (m, 1H, Cp H), 6.18 (m, 1H, Cp H), 2.2 (m, 4H, α-CH ₂ ), 1.55 (m, 6H, β- and γ-CH ₂ ), -0.07 (s, 18H, Si (CH ₃ ) ₃ )

(4-b) [η ⁵ - (3- SiMe ₃ ) C ₅ H ₃ C [( CH ₂ ) ₅ ] Ph } TiCl ₃  of  synthesis

: 0.34ml (0.6g, 3.2mmol) titanium tetrachloride 40ml dichloromethane solution was lowered to -40 ° C and 1.2g (3.3 mmol) C ₅ H ₃ (SiMe ₃ ) ₂ C [(CH ₂ ) ₅ ] Ph was added dropwise and stirred overnight at room temperature. The volatiles were removed in vacuo and the residue was washed with pentane to remove the residue and extracted with dichloromethane to yield 0.68 g (1.5 mmol, 40%) of reddish brown crystals.

The results of ¹ H NMR confirming the synthesis of [η ^5- (3-SiMe ₃ ) C ₅ H ₃ C [(CH ₂ ) ₅ ] Ph} TiCl ₃ are as follows.

¹ H NMR (300 MHz, C ₆ D ₆ ): δ 7.13 (m, 4H, Ph o- and mH), 7.01 (m, 1H, Cp H), 6.93 (m, 1H, Ph pH), 6.45 (m , 2H, Cp H), 2.54 (m, 2H, α-CH _eq ), 2.07, 1.86 (m, 1H each, α-CH _ax ), 1.4 (br, 3H, β- and γ-CH ₂ ), 1.15 (br, 3H, β- and α-CH ₂ ), 0.13 (s, 9H, Si (CH ₃ ) ₃ )

(4-c) [η ⁵ - (3- SiMe ₃ ) C ₅ H ₃ C [( CH ₂ ) ₅ ] Ph } Ti (N ( CH ₂ CH ₂ O ) ₃ ) Synthesis of

: About 1.94 mmol (0.869 g) of [η ^5- (3-SiMe ₃ ) C ₅ H ₃ C [(CH ₂ ) ₅ ] Ph} TiCl ₃ prepared in Example 4-b was dissolved in 50 ml of toluene, The temperature was lowered to -78 ° C, and an equivalent amount of triethanolamine and three equivalents of triethylamine toluene solution were added dropwise, and then raised to room temperature, followed by heating to 50 ° C and stirring for about 12 hours. The orange suspension was filtered through Celite, dried in vacuo and washed with hexane, which was an ivory-colored solid represented by the following formula: [η ^5- (3-SiMe ₃ ) C ₅ H ₃ C [(CH ₂ ) ₅ ] Ph} Ti _{(N (CH 2 CH 2 O} ) 3) to give the approximately 0.569g (1.164mmol, 60% yield).

[Chemical Formula]

Results of ¹ H NMR confirming the synthesis of [η ^5- (3-SiMe ₃ ) C ₅ H ₃ C [(CH ₂ ) ₅ ] Ph} Ti (N (CH ₂ CH ₂ O) ₃ ) are as follows. .

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.44 (d, 2H, ArH), 7.24 (d, 2H, ArH), 7.08 (t, 1H, ArH), 6.29 (s, 1H, Cp), 6.17 (s , 2H, Cp), 4.14 (m, 6H, NCH ₂ CH ₂ O), 2.82 (m, 6H, NCH ₂ CH ₂ O), 2.71 (d, 1H,-(CH ₂ ) ₅ ), 2.57 (d, 1H,-(CH ₂ ) ₅ ), 2.06 (m, 2H,-(CH ₂ ) ₅ ), 1.53 (br, 3H,-(CH ₂ ) ₅ ), 1.4 (m, 3H,-(CH ₂ ) ₅ )

Example  5: {η ⁵ - (3- SiMe ₃ ) C ₅ H ₃ C [( CH ₂ ) ₅ ] -3,5- Me ₂ C ₆ H ₃ } Ti (N ( CH ₂ CH ₂ O ) ₃ ) Synthesis of

(5-a) {η ⁵ - (3- SiMe ₃ ) C ₅ H ₃ C [( CH ₂ ) ₅ ] -3,5- Me ₂ C ₆ H ₃ } TiCl ₃  of  synthesis

: 1.12g (0.010mol) 3,5-dimethylphenyllithium is dissolved in 50ml diethyl ether and lowered to 0 ° C, then 1.46g (0.010mol) 6,6-pentamethylpulbene is added dropwise and stirred at room temperature for 12 hours, followed by suspension. Filtered, washed with diethyl ether and dried in vacuo. The pale yellow powder was dissolved in 40 ml ether / tetrahydrofuran (5: 1, v / v), lowered to 0 ° C., 1.08 g (0.010 mol) trimethylsilyl chloride was added, and the white suspension was stirred at room temperature for 2 hours. After lowering to 0 ° C., 4.8 ml of 2.5M (0.012 mol) butyllithium hexane solution was added thereto, and the resultant was stirred for 5 hours. Then, 1.52 g (0.014 mol) trimethylsilyl chloride was added thereto. After slowly raising to room temperature, the mixture was stirred overnight. The volatiles were removed in vacuo, then extracted three times with 15 ml of dichloromethane, passed through silica to remove the solvent, and the orange oil was immediately dissolved in 30 ml dichloromethane, lowered to -20 ° C, and then 1.5 g (0.008 mol) tetra Crorotitanium was added. The reaction solution was slowly warmed up to room temperature, stirred for 12 hours, and then volatiles were removed in vacuo and extracted with 30 ml hexane. Lowered to −30 ° C. to 23% of 1.1 g of red crystals {η ^5- (3-SiMe ₃ ) C ₅ H ₃ C [(CH ₂ ) ₅ ] -3,5-Me ₂ C ₆ H ₃ } TiCl ₃ Obtained in the yield.

Results of ¹ H NMR confirming the synthesis of {η ^5- (3-SiMe ₃ ) C ₅ H ₃ C [(CH ₂ ) ₅ ] -3,5-Me ₂ C ₆ H ₃ } TiCl ₃ are as follows. .

¹ H NMR (400 MHz, C ₆ D ₆ ): δ 0.10 (s, 9H), 1.20-1.50 (m, 6H), 1.78-2.10 (m, 2H), 2.10 (s, 6H), 2.64 (m, 2H ), 6.41 (t, 1H, 3JHH = 3.1 Hz), 6.47 (t, 1H, 3JHH = 3.1 Hz), 6.64 (br, 1H), 6.96 (br, 1H), 7.12 (br, 2H)

(5-b) {η ⁵ - (3- SiMe ₃ ) C ₅ H ₃ C [( CH ₂ ) ₅ ] -3,5- Me ₂ C ₆ H ₃ } Ti (N ( CH ₂ CH ₂ O ) ₃ ) Synthesis of

About 1.22 mmol of {η ^5- (3-SiMe ₃ ) C ₅ H ₃ C [(CH ₂ ) ₅ ] -3,5-Me ₂ C ₆ H ₃ } TiCl ₃ prepared in Example 5-a; 0.582 g) was dissolved in 50 ml toluene, and then the temperature was lowered to -78 ° C, and an equivalent amount of triethanolamine and three equivalents of triethylamine toluene solution were added dropwise, and then raised to room temperature, followed by heating to 50 ° C and stirring for about 12 hours. The orange suspension was filtered through Celite and dried in vacuo and washed with hexane, {η ^5- (3-SiMe ₃ ) C ₅ H ₃ C [(CH ₂ ) ₅ ] -3, About 0.378 g (0.732 mmol, 5-60% yield) of 5-Me ₂ C ₆ H ₃ } Ti (N (CH ₂ CH ₂ O) ₃ ) was obtained.

[Chemical Formula]

Synthesis of the above (η ^5- (3-SiMe ₃ ) C ₅ H ₃ C [(CH ₂ ) ₅ ] -3,5-Me ₂ C ₆ H ₃ } Ti (N (CH ₂ CH ₂ O) ₃ ) The result of confirmed ¹ H NMR is as follows.

¹ H NMR (400 MHz, CDCl 3): δ 7.42 (s, 2H, ArH), 6.92 (s, 1H, ArH), 6.5 (s, 1H, Cp), 6.39 (s, 1H, Cp), 6.35 (s, 1H, Cp), 4.38 (m, 6H, NCH ₂ CH ₂ O), 3.24 (m, 6H, NCH ₂ CH ₂ O), 2.85 (d, 1H,-(CH ₂ ) ₅ ), 2.77 (d, 1H ,-(CH ₂ ) ₅ ), 2.46 (s, 6H, 2Me), 2.42 (t, 1H,-(CH ₂ ) ₅ ), 2.16 (t, 1H,-(CH ₂ ) ₅ ), 1.72 (br, 3H,-(CH ₂ ) ₅ ), 1.48 (br, 3H,-(CH ₂ ) ₅ ), 0.25 (s, 9H, SiMe ₃ )

Example  6-a to Example  6-e

[Η ^5- (3-SiMe ₃ ) C ₅ H ₃ CMe ₂ -3,5-Me ₂ C ₆ H ₃ ] Ti (N (CH ₂ O) as a first transition metal compound obtained through Example 1-c. ₃ ) and polymerization characteristics of the tandem catalyst system including bis (indenyl) zirconium chloride as the second transition metal compound were evaluated in the following manner. In this case, the content of the first transition metal compound, the content of the second transition metal compound, the content of the cocatalyst compound, the polymerization activity of the applied catalyst system, the melting point and the density of the produced polymer are shown in Table 1, respectively. It was.

First, a 2 L high pressure reactor was used for the polymerization reaction. After completely replacing the reactor with nitrogen, 1L of toluene, the first transition metal compound obtained through Example 1-c, and methylaluminoxane, a promoter compound, were added thereto, and the temperature of the reactor was maintained at 15 ° C. . And ethylene was supplied enough so that it might become a partial pressure of 7.0 atmosphere, and the polymerization reaction was prepared.

A separate amount of the first transition metal compound and bis (indenyl) zirconium chloride obtained through Example 1-c was supplied through a separate catalyst input container, and maintained for 10 minutes. The pressure of the reactor was maintained constant by the ethylene introduced into the reactor, and after raising the reactor temperature to 70 ℃, the polymerization was carried out for 1 hour. At the completion of the polymerization reaction, the ethylene feed was stopped and the unreacted ethylene was vented out of the reactor. The remaining methylaluminoxane was inactivated by the addition of 20 ml of ethanol. The reaction was filtered to separate the liquid and solid components, washed 1 hour in acidified ethanol and dried at 70 ° C./vacuum to obtain polyethylene.

Comparative Example  One

Polyethylene was prepared in the same manner as in Example 6-a, except that the first transition metal compound obtained in Example 1-c was not added.

Comparative Example  2

Polyethylene was prepared in the same manner as in Example 6-a, except that the compound obtained in Example 1-b was added as the first transition metal compound instead of the compound obtained in Example 1-c.

Comparative Example  3

Polyethylene was prepared in the same manner as in Example 6-b, except that the compound obtained in Example 1-b was added as the first transition metal compound instead of the compound obtained in Example 1-c.

Catalyst system Catalytic activity
(KgPE / gCat.) Copolymer (A) ingredient
(μmol) (B) ingredient
(μmol) (C) component
(mmol) Melting point
(℃) density
(g / cc) Example 6-a 2 One 2 79.84 132.69 0.951 Example 6-b 4 One 2 71.38 131.98 0.949 Example 6-c 8 One 2 68.82 128.03 0.944 Example 6-d 16 One 2 68.24 126.26 0.937 Example 6-e 32 One 2 65.34 121.81 0.922 Comparative Example 1 - One 2 100.12 138.04 0.957 Comparative Example 2 2 One 2 72.35 135.17 0.954 Comparative Example 3 4 One 2 68.35 133.05 0.951

(In Table 1, '(A) component' refers to the first transition metal compound, '(B) component' refers to the second transition metal compound, and '(C) component' means a promoter compound. In Example 2, (A) component has a structure different from that of the compound applied to the Examples.)

As can be seen from Table 1 above, the ethylene / alpha-olefin copolymer according to Examples 6-a to 6-e was polymerized in the presence of a tandem catalyst system according to the present invention to form a separate comonomer. It has been found that it can exhibit a low density of 0.922 to 0.951 g / cc without using.

In contrast, as the copolymer according to Comparative Example 1 was polymerized by applying the previous catalyst system, the density was higher than that of the copolymer according to the embodiments, and it was confirmed that the use of a comonomer is required to further lower the density. there was.

In addition, the copolymer according to Comparative Example 2 was polymerized using a transition metal compound to which a ligand derived from a hydroxyalkyl amine compound was not introduced, so that the amount of alpha-olefin was relatively low, compared to the polymer of Examples. The melting point and the density were high, and the polymerization activity was also low.

Claims (23)

A first transition metal compound for synthesizing one or more alpha-olefins selected from the group consisting of compounds represented by Formula 1, Formula 2, and Formula 3;
A second transition metal compound for forming a copolymer of alpha-olefin and ethylene; And
Cocatalyst compound for activating the first transition metal compound and the second transition metal compound
Tandem catalyst system for the production of polyethylene comprising:
[Chemical Formula 1]

(2)

(3)

In Chemical Formulas 1 to 3,
M is one element selected from Groups 3-10 on the periodic table,
Cp is a ligand having a cyclopentadienyl skeleton,
B is a linking group containing one element selected from Groups 13-16 on the periodic table,
Ar is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 30 carbon atoms,
O is oxygen, N is nitrogen,
n is an integer from 1 to 10, m is an integer from 0 to 5,
X ¹ and X ² are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C20 Alkylsilyl group, substituted or unsubstituted C1-C20 silylalkyl group, substituted or unsubstituted C1-C20 haloalkyl group, substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted C7 -20 arylalkyl groups, substituted or unsubstituted C7-20 alkylaryl groups, substituted or unsubstituted C6-C20 arylsilyl groups, substituted or unsubstituted C6-C20 silylaryl groups, substituted or In the group consisting of an unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C1-C20 alkylsiloxy group, a substituted or unsubstituted C6-C20 aryloxy group, and a tetrahydroborate group Selected Is one or more substituents,
Y ¹ and Y ² are each independently a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C20 alkylsilyl group , Substituted or unsubstituted C1-20 silylalkyl group, substituted or unsubstituted C6-20 aryl group, substituted or unsubstituted C7-20 arylalkyl group, substituted or unsubstituted C7-20 At least one substituent selected from the group consisting of an alkylaryl group, a substituted or unsubstituted C6-C20 arylsilyl group, and a substituted or unsubstituted C6-C20 silylaryl group,
Q ¹ , Q ² and Q ³ are each independently a linking group represented by the following formula (4),
[Chemical Formula 4]

R of Formulas 1 to 3 and R ¹ and R ² of Formula 4 are each independently a hydrogen atom, a halogen group, a substituted or unsubstituted C1-20 alkyl group, a substituted or unsubstituted C3-20 cyclo Alkyl group, substituted or unsubstituted C1-C20 alkylsilyl group, substituted or unsubstituted C1-C20 silylalkyl group, substituted or unsubstituted C1-C20 haloalkyl group, substituted or unsubstituted C6-C20 20 aryl groups, substituted or unsubstituted C7-20 arylalkyl groups, substituted or unsubstituted C7-20 alkylaryl groups, substituted or unsubstituted C6-C20 arylsilyl groups, substituted or unsubstituted Substituted 6 to 20 carbonyl silylaryl groups, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted alkylsiloxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 20 carbon atoms And substituted or unsubstituted amino groups Is one or more substituents selected from the group consisting of,
p is an integer of 1-10.
The method of claim 1,
Wherein M is one or more elements selected from the group consisting of titanium (Ti), zirconium (Zr), vanadium (V) and tantalum (Ta) tandem catalyst system for producing polyethylene.
The method of claim 1,
Wherein Cp is a cyclopentadienyl (cyclopentadienyl) group, indenyl (indenyl) or fluorenyl (fluorenyl) tandem catalyst system for producing polyethylene.
The method of claim 1,
B is an alkylene group having 1 to 20 carbon atoms; Cycloalkylene groups having 3 to 20 carbon atoms; Alkylsilylene group having 1 to 20 carbon atoms; Haloalkylene groups having 6 to 20 carbon atoms; Arylalkylene groups having 6 to 20 carbon atoms; Arylsilylene group having 6 to 20 carbon atoms; Arylene groups having 5 to 40 carbon atoms; And an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an alkylsilylene group having 1 to 20 carbon atoms, and having 6 to 20 carbon atoms between the two arylene groups. Contains a haloalkylene group, an arylalkylene group having 6 to 20 carbon atoms, an arylsilylene group having 6 to 20 carbon atoms, or an alkylarylene group having 7 to 20 carbon atoms Tandem catalyst system for producing polyethylene, which is at least one linking group selected from the group consisting of functional groups.
The method of claim 1,
Ar is a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthalyl group, Substituted or unsubstituted anthracyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyrazinyl group or substituted or unsubstituted Tandem catalyst system for producing polyethylene, which is a quinolinyl group.
The method of claim 5, wherein
Ar is a hydrogen atom, an alkyl group of 1 to 20 carbon atoms (alky), a cycloalkyl group of 3 to 20 carbon atoms, an alkylsilyl group of 1 to 20 carbon atoms, haloalkyl of 1 to 20 carbon atoms Groups, aryl groups having 6 to 20 carbon atoms, arylalkyl groups having 7 to 20 carbon atoms, arylsilyl groups having 6 to 20 carbon atoms, alkylaryl groups having 7 to 20 carbon atoms, and carbon atoms Selected from the group consisting of 1-20 alkoxy groups, alkylsiloxy groups of 1-20 carbon atoms, aryloxy groups of 6-20 carbon atoms, halogen groups and amino groups Tandem catalyst system for producing polyethylene comprising at least one substituent.
The method of claim 1,
Ligands formed by the combination of O, Q ¹ , Q ² , Q ³ , N, Y ¹ and Y ² are each independently removed from hydrogen ions (protons) of hydroxy groups from monovalent trivalent hydroxyalkylamine compounds. Has a modified form;
The hydroxyalkylamine compound is N- (2-hydroxyethyl) amine (N- (2-Hydroxyethyl) amine), N, N-bis- (2-hydroxyethyl) amine (N, N-Bis- (2-hydroxyethyl) amine), N, N, N-tris- (2-hydroxyethyl) amine (N, N, N-Tris- (2-hydroxyethyl) amine), (N- (3-hydroxypropyl ) Amine (N- (3-hydroxypropyl) amine), N, N-bis- (3-hydroxypropyl) amine (N, N-Bis- (3-hydroxypropyl) amine), N, N, N-tris- (3-hydroxypropyl) amine (N, N, N-Tris- (3-hydroxypropyl) amine), N- (4-hydroxybutyl) amine (N- (4-Hydroxybutyl) amine), N, N- Bis- (4-hydroxybutyl) amine (N, N-Bis- (4-hydroxybutyl) amine), N, N, N-tris- (4-hydroxybutyl) amine (N, N, N-Tris- (4-hydroxybutyl) amine), N- (5-hydroxypentyl) amine (N- (5-Hydroxypentyl) amine), N, N-bis- (5-hydroxypentyl) amine (N, N-Bis- (5-hydroxypentyl) amine), N, N, N-tris- (5-hydroxypentyl) amine (N, N, N-Tris- (5-hydroxypentyl) amine), N- (6-hydroxyhexyl) Amine (N- (6-Hydroxyhexyl) amine), N, N-bis- (6-hydroxyhexyl) amine (N, N -Bis- (6-Hydroxyhexyl) amine), N, N, N-tris- (6-hydroxyhexyl) amine (N, N, N-Tris- (6-Hydroxyhexyl) amine), (N-2-hydride Hydroxyethyl) methylamine (N- (2-Hydroxyethyl) methylamine), (N-2-hydroxyethyl) ethylamine (N- (2-Hydroxyethyl) ethylamine), N, N-bis- (2-hydroxyethyl Methylamine (N, N-Bis- (2-hydroxyethyl) methylamine), N, N-bis- (2-hydroxyethyl) ethylamine (N, N-Bis- (2-hydroxyethyl) ethylamine), N- 3-hydroxypropyl) methylamine (N- (3-Hydroxypropyl) methylamine), N-3-hydroxypropyl) ethylamine (N- (3-Hydroxypropyl) ethylamine), N, N-bis- (3-hydroxy Hydroxypropyl) methylamine (N, N-Bis- (3-hydroxypropyl) methylamine), N, N-bis- (3-hydroxypropyl) ethylamine (N, N-Bis- (3-hydroxypropyl) ethylamine), N-2-hydroxyethyl) dimethylamine (N- (2-Hydroxyethyl) dimethylamine), N-2-hydroxyethyl) diethylamine (N- (2-Hydroxyethyl) diethylamine), N-3-hydroxypropyl ) Dimethylamine (N- (3-Hydroxypropyl) dimethylamine), N-3-hydroxypropyl) diethylamine (N- (3- Hydroxypropyl) diethylamine), N- (2-methyl-2-hydroxyethyl) amine (N- (2-Methyl-2-hydroxyethyl) amine), N- (1-methyl-2-hydroxyethyl) amine (N -(1-Methyl-2-hydroxyethyl) amine), N- (1,2-dimethyl-2-hydroxyethyl) amine (N- (1.2-Dimethyl-2-hydroxyethyl) amine), N, N-bis- (2-methyl-2-hydroxyethyl) amine (N, N-Bis- (2-methyl-2-hydroxyethyl) amine), N, N-bis- (1-methyl-2-hydroxyethyl) amine ( N, N-Bis- (1-methyl-2-hydroxyethyl) amine), N, N-bis- (1,2-dimethyl-2-hydroxyethyl) amine (N, N-Bis- (1,2- Dimethyl-2-hydroxyethyl) amine), N, N, N-tris- (2-methyl-2-hydroxyethyl) amine (N, N, N-Tris- (2-methyl-2-hydroxyethyl) amine), N, N, N-tris- (1-methyl-2-hydroxyethyl) amine (N, N, N-Tris- (1-methyl-2-hydroxyethyl) amine), N- (3-methyl-3- Hydroxypropyl) amine (N- (3-Methyl-3-hydroxypropyl) amine), N- (2-methyl-3-hydroxypropyl) amine (N- (2-Methyl-3-hydroxypropyl) amine), N -(1-methyl-3-hydroxypropyl) amine (N- (1-Methyl-3-hydroxypropyl) amine), N- (2,3-dimethyl-3-hydroxy Hydroxypropyl) amine (N- (2,3-Dimethyl-3-hydroxypropyl) amine), N- (1,3-dimethyl-3-hydroxypropyl) amine (N- (1,3-Dimethyl-3-hydroxypropyl ) amine), N- (1,2-dimethyl-3-hydroxypropyl) amine (N- (1,2-Dimethyl-3-hydroxypropyl) amine), N- (1,2,3-trimethyl-3- Hydroxypropyl) amine (N- (1,2,3-Triimethyl-3-hydroxypropyl) amine), N, N-bis- (3-methyl-3-hydroxypropyl) amine (N, N-Bis- ( 3-methyl-3-hydroxypropyl) amine), N, N-bis- (2-methyl-3-hydroxypropyl) amine (N, N-Bis- (2-methyl-3-hydroxypropyl) amine), N, N-Bis- (1-methyl-3-hydroxypropyl) amine (N, N-Bis- (1-methyl-3-hydroxypropyl) amine), N, N-bis- (2,3-dimethyl-3- Hydroxypropyl) amine (N, N-Bis- (2,3-dimethyl-3-hydroxypropyl) amine), N, N-bis- (1,3-dimethyl-3-hydroxypropyl) amine (N, N -Bis- (1,3-dimethyl-3-hydroxypropyl) amine), N, N-bis- (1,2-dimethyl-3-hydroxypropyl) amine (N, N-Bis- (1,2-dimethyl -3-hydroxypropyl) amine), N, N-bis- (1,2,3-trimethyl-3-hydroxypropyl) amine (N, N-Bis- (1, 2,3-trimethyl-3-hydroxypropyl) amine), N, N, N-tris- (3-methyl-3-hydroxypropyl) amine (N, N, N-Tris- (3-methyl-3-hydroxypropyl ) amine), N, N, N-tris- (2-methyl-3-hydroxypropyl) amine (N, N, N-Tis- (2-methyl-3-hydroxypropyl) amine), N, N, N -Tris- (1-methyl-3-hydroxypropyl) amine (N, N, N-Tris- (1-methyl-3-hydroxypropyl) amine), N, N, N-tris- (2,3-dimethyl -3-hydroxypropyl) amine (N, N, N-Tris- (2,3-dimethyl-3-hydroxypropyl) amine), N, N, N-tris- (1,3-dimethyl-3-hydroxy Propyl) amine (N, N, N-Tris- (1,3-dimethyl-3-hydroxypropyl) amine), N, N, N-tris- (1,2-dimethyl-3-hydroxypropyl) amine (N , N, N-Tris- (1,2-dimethyl-3-hydroxypropyl) amine), N, N, N-tris- (1,2,3-trimethyl-3-hydroxypropyl) amine (N, N, N-Tris- (1,2,3-trimethyl-3-hydroxypropyl) amine), N- (2-methyl-2-hydroxyethyl) methylamine (N- (2-Methyl-2-hyroxyethyl) methylamine, N- (1-methyl-2-hydroxyethyl) methylamine (N- (1-Methyl-2-hyroxyethyl) methylamine), N- (1,2-dimethyl-2-hydroxy N- (1,2-Dimethyl-2-hyroxyethyl) methylamine, N, N-bis- (2-methyl-2-hydroxyethyl) methylamine (N, N-Bis- (2- methyl-2-hyroxyethyl) methylamine), N, N-bis- (1-methyl-2-hydroxyethyl) methylamine (N, N-Bis- (1-methyl-2-hyroxyethyl) methylamine), N, N -Bis- (1,2-dimethyl-2-hydroxyethyl) methylamine (N, N-Bis- (1,2-dimethyl-2-hyroxyethyl) methylamine), N- (2-methyl-2-hydroxy Ethyl) ethylamine (N- (2-Methyl-2-hyroxyethyl) ethylamine), N- (1-methyl-2-hydroxyethyl) ethylamine (N- (1-Methyl-2-hyroxyethyl) ethylamine), N -(1,2-dimethyl-2-hydroxyethyl) ethylamine (N- (1,2-Dimethyl-2-hyroxyethyl) ethylamine), N, N-bis- (2-methyl-2-hydroxyethyl) Ethylamine (N, N-Bis- (2-methyl-2-hyroxyethyl) ethylamine), N, N-bis- (1-methyl-2-hydroxyethyl) ethylamine (N, N-Bis- (1- methyl-2-hyroxyethyl) ethylamine), N, N-bis- (1,2-dimethyl-2-hydroxyethyl) ethylamine (N, N-Bis- (1,2-dimethyl-2-hyroxyethyl) ethylamine) , N- (3-methyl-3-hydroxypropyl) methylamine (N- (3 -Methyl-3-hydroxypropyl) methylamine), N- (2-methyl-3-hydroxypropyl) methylamine (N- (2-Methyl-3-hydroxypropyl) methylamine), N- (1-methyl-3-hydroxy Hydroxypropyl) methylamine (N- (1-Methyl-3-hydroxypropyl) methylamine), N- (2,3-dimethyl-3-hydroxypropyl) methylamine (N- (2,3-Dimethyl-3-hydroxypropyl N- (1,3-dimethyl-3-hydroxypropyl) methylamine N- (1,2-dimethyl-3-hydroxy) Hydroxypropyl) methylamine (N- (1,2-Dimethyl-3-hydroxypropyl) methylamine), N- (1,2,3-trimethyl-3-hydroxypropyl) amine (N- (1,2,3- Triimethyl-3-hydroxypropyl) methylamine), N- (3-methyl-3-hydroxypropyl) ethylamine (N- (3-Methyl-3-hydroxypropyl) ethylamine), N- (2-methyl-3-hydroxy Propyl) ethylamine (N- (2-Methyl-3-hydroxypropyl) ethylamine), N- (1-methyl-3-hydroxypropyl) ethylamine (N- (1-Methyl-3-hydroxypropyl) ethylamine), N -(2,3-dimethyl-3-hydroxypropyl) ethylamine (N- (2,3-Dimethyl-3-hydroxypropyl) ethylamine), N- (1,3- Methyl-3-hydroxypropyl) ethylamine (N- (1,3-Dimethyl-3-hydroxypropyl) ethylamine), N- (1,2-dimethyl-3-hydroxypropyl) ethylamine (N- (1, 2-Dimethyl-3-hydroxypropyl) ethylamine), N- (1,2,3-trimethyl-3-hydroxypropyl) ethylamine (N- (1,2,3-Triimethyl-3-hydroxypropyl) ethylamine), N , N-bis- (3-methyl-3-hydroxypropyl) methylamine (N, N-Bis- (3-methyl-3-hydroxypropyl) methylamine), N, N-bis- (2-methyl-3- Hydroxypropyl) methylamine (N, N-Bis- (2-methyl-3-hydroxypropyl) methylamine), N, N-bis- (1-methyl-3-hydroxypropyl) methylamine (N, N-Bis -(1-methyl-3-hydroxypropyl) methylamine), N, N-bis- (2,3-dimethyl-3-hydroxypropyl) methylamine (N, N-Bis- (2,3-dimethyl-3- hydroxypropyl) methylamine), N, N-bis- (1,3-dimethyl-3-hydroxypropyl) methylamine (N, N-Bis- (1,3-dimethyl-3-hydroxypropyl) methylamine), N, N -Bis- (1,2-dimethyl-3-hydroxypropyl) methylamine (N, N-Bis- (1,2-dimethyl-3-hydroxypropyl) methylamine), N, N-bis- (1,2, 3-trimethyl-3-hydrate Hydroxypropyl) methylamine (N, N-Bis- (1,2,3-trimethyl-3-hydroxypropyl) methylamine), N, N-bis- (3-methyl-3-hydroxypropyl) ethylamine (N, N-Bis- (3-methyl-3-hydroxypropyl) ethylamine), N, N-bis- (2-methyl-3-hydroxypropyl) ethylamine (N, N-Bis- (2-methyl-3-hydroxypropyl) ) ethylamine), N, N-bis- (1-methyl-3-hydroxypropyl) ethylamine (N, N-Bis- (1-methyl-3-hydroxypropyl) ethylamine), N, N-bis- (2 , 3-dimethyl-3-hydroxypropyl) ethylamine (N, N-Bis- (2,3-dimethyl-3-hydroxypropyl) ethylamine), N, N-bis- (1,3-dimethyl-3-hydroxy Hydroxypropyl) ethylamine (N, N-Bis- (1,3-dimethyl-3-hydroxypropyl) ethylamine), N, N-bis- (1,2-dimethyl-3-hydroxypropyl) ethylamine (N, N-Bis- (1,2-dimethyl-3-hydroxypropyl) ethylamine), N, N-bis- (1,2,3-trimethyl-3-hydroxypropyl) ethylamine (N, N-Bis- (1 , 2,3-trimethyl-3-hydroxypropyl) ethylamine), N- (2-methyl-2-hydroxyethyl) dimethylamine (N- (2-Methyl-2-hyroxyethyl) dimethylamine), N- (1-methyl 2-hydroxyethyl) dimethyla (N- (1-Methyl-2-hyroxyethyl) dimethylamine), N- (1,2-dimethyl-2-hydroxyethyl) dimethylamine (N- (1,2-Dimethyl-2-hyroxyethyl) dimethylamine), N -(2-methyl-2-hydroxyethyl) diethylamine (N- (2-Methyl-2-hyroxyethyl) diethylamine), N- (1-methyl-2-hydroxyethyl) diethylamine (N- ( 1-Methyl-2-hyroxyethyl) diethylamine), N- (1,2-dimethyl-2-hydroxyethyl) diethylamine (N- (1,2-Dimethyl-2-hyroxyethyl) diethylamine), N- (3 -Methyl-3-hydroxypropyl) dimethylamine (N- (3-Methyl-3-hydroxypropyl) dimethylamine), N- (2-methyl-3-hydroxypropyl) dimethylamine (N- (2-Methyl-3 -hydroxypropyl) dimethylamine), N- (1-methyl-3-hydroxypropyl) dimethylamine (N- (1-Methyl-3-hydroxypropyl) dimethylamine), N- (2,3-dimethyl-3-hydroxypropyl ) Dimethylamine (N- (2,3-Dimethyl-3-hydroxypropyl) dimethylamine), N- (1,3-dimethyl-3-hydroxypropyl) dimethylamine (N- (1,3-Dimethyl-3-hydroxypropyl ) dimethylamine), N- (1,2-dimethyl-3-hydroxypropyl) dimethylamine (N- (1,2-dimethyl-3-hyd roxypropyl) dimethylamine), N- (1,2,3-trimethyl-3-hydroxypropyl) dimethylamine (N- (1,2,3-Triimethyl-3-hydroxypropyl) dimethylamine), N- (3-methyl- 3-hydroxypropyl) diethylamine (N- (3-Methyl-3-hydroxypropyl) diethylamine), N- (2-methyl-3-hydroxypropyl) diethylamine (N- (2-Methyl-3- hydroxypropyl) diethylamine), N- (1-methyl-3-hydroxypropyl) diethylamine (N- (1-Methyl-3-hydroxypropyl) diethylamine), N- (2,3-dimethyl-3-hydroxypropyl ) Diethylamine (N- (2,3-Dimethyl-3-hydroxypropyl) diethylamine), N- (1,3-dimethyl-3-hydroxypropyl) diethylamine (N- (1,3-Dimethyl-3) -hydroxypropyl) diethylamine), N- (1,2-dimethyl-3-hydroxypropyl) diethylamine (N- (1,2-Dimethyl-3-hydroxypropyl) diethylamine), and N- (1,2,3 -Trimethyl-3-hydroxypropyl) diethylamine (N- (1,2,3-Triimethyl-3-hydroxypropyl) diethylamine) A tandem catalyst system for producing polyethylene, which is at least one compound selected from the group consisting of:
The method of claim 1,
The alpha-olefin may be 1-butene, 1-hexene, 1-octene, 1-decene, 1-decene, 1-dodecene 1-tetradecene (1-tetradecene), 1-hexadecene (1-hexadecene) and 1-octadecene (1-octadecene) at least one selected from the group consisting of tandem catalyst system for producing polyethylene.
The method of claim 1,
The second transition metal compound is at least one compound selected from the group consisting of a Ziegler-Natta type catalyst, a chromium-based catalyst, a metallocene catalyst, and a constrained geometry catalyst.
The method of claim 1,
The cocatalyst compound is at least one selected from the group consisting of compounds represented by the following formula (5), (6) and (7) tandem catalyst system for producing polyethylene:
[Chemical Formula 5]

In Formula 5,
R ³ is an alkyl group having 1 to 10 carbon atoms, n is an integer of 1 to 70;
[Chemical Formula 6]

In Formula 6,
R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or a halogen group, and R ⁴ , R ⁵ and R ⁶ At least one is an alkyl group having 1 to 10 carbon atoms;
(7)

In Formula 7,
C is Lewis base's proton-bonding cation or an oxidizing metal or nonmetallic compound,
D is a compound of elements and organic substances belonging to groups 5 to 15 of the periodic table.
11. The method of claim 10,
The compound of Formula 5 is made of methylaluminoxane (Methylaluminoxane), ethyl aluminoxane (Ethylaluminoxane), butyl aluminoxane (Butylaluminoxane), hexyl aluminoxane (Hexylaluminoxane), octyl aluminoxane (Octylaluminoxane), and decylaluminoxane (Decylaoxane) Tandem catalyst system for producing polyethylene, which is at least one compound selected from the group.
11. The method of claim 10,
The compound of Chemical Formula 6 is trimethylaluminum, triethylaluminum, tributylaluminum, tributylaluminum, trihexylaluminum, trioctyl aluminum, tridecylaluminum, tridecylaluminum, dimethylaluminum methoxide Dimethylaluminum methoxide, Diethylaluminum methoxide, Dibutylaluminum methoxide, Dimethylaluminum chloride, Diethylaluminum chloride, Dibutylaluminum chloride ), Methylaluminum dimethoxide, ethylaluminum dimethoxide, ethylaluminum dimethoxide, butylaluminum dimethoxide, methylaluminum dichloride, ethylaluminum dichloride A tandem catalyst system for producing polyethylene, which is at least one compound selected from the group consisting of hylaluminum dichloride, and butylaluminum dichloride.
11. The method of claim 10,
The compound of Formula 7 is trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethyl Ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate Borate (Tripropylammonium tetrakis (pentafluorophenyl) borate), Tributylammonium tetrakis (pentafluorophenyl) borate, Anilinium tetraphenylborate, Anilinium tete Anilinium tetrakis (pentafluorophenyl) borate, Pyridinium tetraphenylborate, Pyridinium tetrakis (pentafluorophenyl) borate, Ferrocenium tetra Ferrosicenium tetrakis (pentafluorophenyl) borate, Silver tetraphenylborate, Silver tetrakis (pentafluorophenyl) borate, Tris (pentafluorophenylborate) Phenyl) borane (Tris (pentafluorophenyl) borane), tris (2,3,5,6-tetrafluorophenyl) borane (Tris (2,3,5,6-tetrafluorophenyl) borane), tris (2,3 , 4,5-tetraphenylphenyl) borane (Tris (2,3,4,5-tetraphenylphenyl) borane), and tris (3,4,5-trifluorophenyl) borane (Tris (3,4, Polyethylene, one or more compounds selected from the group consisting of 5-trifluorophenyl) borane) Quiet tandem catalyst system.
The method of claim 1,
The second transition metal compound is included in a molar ratio of 1: 0.001 to 1: 5 based on the transition metal atom included in each compound with respect to the first transition metal compound;
The cocatalyst compound is a tandem catalyst system for producing polyethylene is included in a molar ratio of 1: 1 to 1: 1,000,000 based on the transition metal atoms contained in the first transition metal compound.
The method of claim 1,
The tandem catalyst system for producing polyethylene further comprising a carrier on which the first transition metal compound, the second transition metal compound and the promoter compound are supported.
The method of claim 15,
The carrier is selected from the group consisting of silica, alumina, magnesium chloride, calcium chloride, bauxite, zeolite, magnesium oxide, zirconium oxide, titanium oxide, boron trioxide, calcium oxide, zinc oxide, barium oxide, thorium oxide and complexes thereof Tandem catalyst system for producing polyethylene, which is at least one.
A process for producing polyethylene comprising polymerizing ethylene in the presence of a tandem catalyst system according to claim 1.
The method of claim 17,
Forming an alpha-olefin from ethylene in the presence of said first transition metal compound and a promoter compound; And
Supplying the second transition metal compound and ethylene to the formation system of the alpha-olefin to form a copolymer of the alpha-olefin and ethylene
Method for producing a polyethylene comprising a.
The method of claim 18,
In the alpha-olefin forming step, the promoter compound is included in a molar ratio of 1: 1 to 1: 1,000,000 based on the transition metal atom included in the first transition metal compound,
In the forming of the copolymer, the second transition metal compound is a method for producing polyethylene in a molar ratio of 1: 0.001 to 1: 5 based on the transition metal atom contained in each compound relative to the first transition metal compound.
The method of claim 18,
The alpha-olefin may be 1-butene, 1-hexene, 1-octene, 1-decene, 1-decene, 1-dodecene 1-tetradecene (1-tetradecene), 1-hexadecene (1-hexadecene) and 1-octadecene (1-octadecene) A method for producing a polyetherene at least one selected from the group consisting of.
The method of claim 17,
The polymerization step is a method for producing polyethylene is carried out under a temperature of 0 to 150 ℃ and pressure conditions of 1 to 1000 atm.
The method of claim 17,
The copolymer has a density of 0.960 g / cc or less.
The method of claim 17,
The copolymer has a density of 0.920 to 0.955 g / cc.