KR20170075531A - Supported hybrid catalyst and method for preparing olefin polymer using the same - Google Patents

Abstract

The present invention relates to a hybrid supported catalyst and a process for producing an olefin polymer using the same. When the hybrid supported catalyst is used, an olefin polymer improved in bubble stability can be provided. Such an olefin polymer exhibits high porosity and is expected to be utilized as a raw material for various products. In particular, the olefin polymer can be stably produced by the meltblown method and is expected to be usefully used as a raw material for the product produced by the meltblown method.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hybrid supported catalyst and a method for producing the olefin polymer using the hybrid supported catalyst,

The present invention relates to a hybrid supported catalyst and a process for producing an olefin polymer using the same.

Ziegler-Natta catalysts of titanium or vanadium compounds have been widely used for the commercial production of polyolefins. Although the Ziegler-Natta catalysts have high activity, they have a wide molecular weight distribution of the produced polymers because of their high activity, The uniformity of the composition is not uniform and there is a limit in ensuring desired physical properties.

Accordingly, recently, a metallocene catalyst in which a transition metal such as titanium, zirconium, or hafnium and a ligand containing a cyclopentadiene functional group are bonded has been developed and widely used. The metallocene compound is generally activated by using aluminoxane, borane, borate or other activator. For example, a metallocene compound having a ligand containing a cyclopentadienyl group and two sigma chloride ligands uses aluminoxane as an activator. This metallocene catalyst is a single active site catalyst having a single kind of active site. The molecular weight distribution of the produced polymer is narrow and the molecular weight, stereoregularity, crystallinity, and especially the reactivity of the comonomer can be controlled according to the structure of the catalyst and the ligand There are advantages. However, a polyolefin polymerized with a metallocene catalyst has a narrow molecular weight distribution and low bubble stability, so that there is a problem that it is difficult to form a product stably when it is processed by a processing method such as a meltblown method. Therefore, research for improving the processability of a polyolefin polymerized with a metallocene catalyst is needed.

The present invention is to provide a hybrid supported catalyst capable of providing a highly porous olefin polymer.

The present invention also provides a method for producing an olefin polymer using the hybrid supported catalyst.

According to one embodiment of the invention, A crosslinked transition metal compound supported on the support and represented by the following formula (1); And a non-crosslinked transition metal compound supported on the support and represented by the following general formula (2).

[Chemical Formula 1]

(2)

In the general formulas (1) and (2), M ₁ and M ₂ are the same as or different from each other, and are independently Ti, Zr or Hf,

X ₁ , X ₂ , X ₃ and X ₄ are the same or different and each independently represents a halogen, a nitro group, an amido group, a phospho group, a phosphido group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms , An alkoxyalkyl group having 2 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a sulfonate group having 1 to 20 carbon atoms and a sulfone group having 1 to 20 carbon atoms Any one,

T is C, Si, Ge, Sn or Pb,

Q ₁ and Q ₂ are the same or different from each other and each independently represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, a heterocycloalkyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms , A carboxylate having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a heteroaryl group having 5 to 20 carbon atoms,

R ₁ to R ₆ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, A silyloxyalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms,

R ₇ to R ₁₄ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, A silyloxyalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, or at least one pair of substituents adjacent to each other among R ₇ to R ₁₄ , To form a substituted or unsubstituted aliphatic or aromatic ring,

R ₁₅ to R ₂₄ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, A silyloxyalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, or at least one pair of substituents adjacent to each other among R ₁₅ to R ₂₄ , To form a substituted or unsubstituted aliphatic or aromatic ring.

Specifically, in Formula 1, R ₁ to R ₄ each independently represent any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms.

In Formula 1, R ₅ and R ₆ are each independently any one selected from the group consisting of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms.

Wherein R ₇ to R ₁₄ are each independently any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms, or R ₇ to R ₁₄ The adjacent substituents may be connected to each other to form a substituted or unsubstituted aliphatic ring.

In Formula 1, Q ₁ and Q ₂ are each independently any one of an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms.

In Formula 1, X ₁ to X ₄ may each independently be any one of halogen, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms.

Wherein R ₁₅ to R ₂₄ are each independently any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms, or R ₁₅ to R ₂₄ Adjacent substituents may be connected to each other to form a substituted or unsubstituted aliphatic ring.

More specifically, the crosslinkable transition metal compound represented by Formula 1 may be any one of the compounds represented by Chemical Formulas 3 and 4 below.

(3)

[Chemical Formula 4]

In the general formulas (3) and (4), R ₂₅ and R ₂₆ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, An alkylsilyl group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, an alkoxysilyl group having 1 to 20 carbon atoms, a silyloxyalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An alkylaryl group having 1 to 20 carbon atoms and an arylalkyl group having 7 to 20 carbon atoms,

and l is an integer of 0 to 5.

The non-crosslinkable transition metal compound represented by Formula 2 may be any one of compounds represented by Chemical Formulas 5 to 7 below.

[Chemical Formula 5]

[Chemical Formula 6]

(7)

In formulas (5) to (7), R ₂₇ to R ₃₀ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, An alkylsilyl group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, an alkoxysilyl group having 1 to 20 carbon atoms, a silyloxyalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An alkylaryl group having 1 to 20 carbon atoms and an arylalkyl group having 7 to 20 carbon atoms.

The hybrid supported catalyst may further include at least one cocatalyst selected from the group consisting of compounds represented by the following formulas (8) to (10) for activating the crosslinkable and non-crosslinkable transition metal compounds.

[Chemical Formula 8]

R ₃₁ - [Al (R ₃₂ ) -O] _n -R ₃₃

In Formula 8,

R ₃₁ , R ₃₂ and R ₃₃ are each independently any one of hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,

n is an integer of 2 or more,

[Chemical Formula 9]

D ( _R34 ) ₃

In the above formula (9)

D is aluminum or boron,

R ₃₄ are each independently any one of halogen, a hydrocarbyl group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,

[Chemical formula 10]

^{[LH] + [Z (A} ) 4] - or ^{[L] + [Z (A} ) 4] -

In Formula 10,

L is a neutral or cationic Lewis base, H is a hydrogen atom,

Z is a Group 13 element, A is independently a hydrocarbyl group having 1 to 20 carbon atoms; A hydrocarbyloxy group having 1 to 20 carbon atoms; And substituents in which at least one hydrogen atom of these substituents is substituted with at least one substituent selected from the group consisting of halogen, hydrocarbyloxy group having 1 to 20 carbon atoms and hydrocarbylsilyl group having 1 to 20 carbon atoms.

The carrier of the hybrid supported catalyst may be silica, alumina, magnesia, or a mixture thereof.

The crosslinkable transition metal compound represented by Formula 1 and the non-crosslinked transition metal compound represented by Formula 2 may be contained in a molar ratio of 100: 1 to 1: 1.

According to another embodiment of the present invention, there is provided a process for producing an olefin polymer comprising the step of polymerizing an olefin monomer in the presence of the hybrid supported catalyst.

The olefin monomers that can be used in the above process are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, Dodecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-aidocene, norbornene, norbornadiene, ethylidenenorbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, Butadiene, butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.

The use of the hybrid supported catalyst according to one embodiment of the present invention can provide an olefin polymer improved in bubble stability. Such an olefin polymer exhibits high porosity and is expected to be utilized as a raw material for various products. In particular, the olefin polymer can be stably produced by the meltblown method and is expected to be usefully used as a raw material for the product produced by the meltblown method.

A hybrid supported catalyst according to a specific embodiment of the present invention and a method for producing an olefin polymer using the catalyst will be described.

According to one embodiment of the invention, A crosslinked transition metal compound supported on the support and represented by the following formula (1); And a non-crosslinked transition metal compound supported on the support and represented by the following general formula (2).

[Chemical Formula 1]

(2)

In the general formulas (1) and (2), M ₁ and M ₂ are the same as or different from each other, and are independently Ti, Zr or Hf,

X ₁ , X ₂ , X ₃ and X ₄ are the same or different and each independently represents a halogen, a nitro group, an amido group, a phospho group, a phosphido group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms , An alkoxyalkyl group having 2 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a sulfonate group having 1 to 20 carbon atoms and a sulfone group having 1 to 20 carbon atoms Any one,

T is C, Si, Ge, Sn or Pb,

Q ₁ and Q ₂ are the same or different from each other and each independently represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, a heterocycloalkyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms , A carboxylate having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a heteroaryl group having 5 to 20 carbon atoms,

R ₁ to R ₆ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, A silyloxyalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms,

R ₇ to R ₁₄ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, A silyloxyalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, or at least one pair of substituents adjacent to each other among R ₇ to R ₁₄ , To form a substituted or unsubstituted aliphatic or aromatic ring,

R ₁₅ to R ₂₄ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, A silyloxyalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, or at least one pair of substituents adjacent to each other among R ₁₅ to R ₂₄ , To form a substituted or unsubstituted aliphatic or aromatic ring.

Unless defined otherwise herein, the following terms may be defined as follows.

The halogen may be fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

The alkyl group having 1 to 20 carbon atoms may be a straight chain, branched chain or cyclic alkyl group. Specifically, the alkyl group having 1 to 20 carbon atoms is preferably a straight chain alkyl group having 1 to 20 carbon atoms; A straight chain alkyl group having 1 to 10 carbon atoms; A straight chain alkyl group having 1 to 5 carbon atoms; Branched or cyclic alkyl group of 3 to 20 carbon atoms; Branched or cyclic alkyl group having 3 to 15 carbon atoms; Or a branched or cyclic alkyl group having 3 to 10 carbon atoms. More specifically, the alkyl group having 1 to 20 carbon atoms is preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a neopentyl group, a cyclohexyl group, or the like.

The heterocycloalkyl group having 2 to 20 carbon atoms may be a cyclic alkyl group containing at least one atom other than carbon exemplified by oxygen, nitrogen or sulfur. Specifically, the heterocycloalkyl group having 2 to 20 carbon atoms may be a heterocycloalkyl group having 2 to 15 carbon atoms, a heterocycloalkyl group having 2 to 10 carbon atoms, or a heterocycloalkyl group having 4 to 7 carbon atoms. More specifically, the heterocycloalkyl group having 2 to 20 carbon atoms may be an epoxy group, a tetrahydrofuranyl group, a tetrahydropyranyl group, a tetrahydrothiophenyl group or a tetrahydropyrrolyl group, have.

The alkoxy group having 1 to 20 carbon atoms may be a straight chain, branched chain or cyclic alkoxy group. Specifically, the alkoxy group having 1 to 20 carbon atoms is preferably a straight chain alkoxy group having 1 to 20 carbon atoms; A straight chain alkoxy group having 1 to 10 carbon atoms; A straight chain alkoxy group having 1 to 5 carbon atoms; A branched or cyclic alkoxy group having 3 to 20 carbon atoms; A branched or cyclic alkoxy group having 3 to 15 carbon atoms; Or a branched or cyclic alkoxy group having 3 to 10 carbon atoms. More specifically, the alkoxy group having 1 to 20 carbon atoms may be a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, - pentoxy group, neo-pentoxy group or cycloheptoxy group, and the like.

The alkoxyalkyl group having 2 to 20 carbon atoms may be a substituent in which at least one hydrogen of the alkyl group (-R ^a ) is substituted with an alkoxy group (-OR ^b ) with a structure including -R ^a -OR ^b . Specifically, the alkoxyalkyl group having 2 to 20 carbon atoms is preferably a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an isopropoxymethyl group, an isopropoxyethyl group, an iso-propoxyhexyl group, A butoxyethyl group or a tert-butoxyhexyl group.

Group is a silyl group having 1 to 20 carbon atoms may be at least one hydrogen of the -SiH ₃ substituents substituted with an alkyl group or an alkoxy group. Specifically, the silyl group having 1 to 20 carbon atoms is preferably a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, a dimethylethylsilyl group, a diethylmethylsilyl group, a dimethylpropylsilyl group, a methoxysilyl group, A silyl group, a trimethoxysilyl group, a dimethoxyethoxysilyl group, a diethoxymethylsilyl group, or a dimethoxypropylsilyl group.

The silylalkyl group having 1 to 20 carbon atoms may be a substituent in which at least one hydrogen of the alkyl group is substituted with a silyl group. Specifically, the silylalkyl group having 1 to 20 carbon atoms may be a dimethoxypropylsilylmethyl group or the like.

The silyloxyalkyl group having 1 to 20 carbon atoms may be a substituent in which at least one hydrogen of the alkyl group is substituted with a silyloxy group. Specifically, the silyloxyalkyl group having 1 to 20 carbon atoms may be a dimethoxypropylsilyloxymethyl group or the like.

The alkenyl group having 2 to 20 carbon atoms may be a straight chain, branched chain or cyclic alkenyl group. Specifically, the alkenyl group having 2 to 20 carbon atoms is preferably a straight chain alkenyl group having 2 to 20 carbon atoms, a straight chain alkenyl group having 2 to 10 carbon atoms, a straight chain alkenyl group having 2 to 5 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, A branched alkenyl group having 3 to 10 carbon atoms, a cyclic alkenyl group having 5 to 20 carbon atoms, or a cyclic alkenyl group having 5 to 10 carbon atoms. More specifically, the alkenyl group having 2 to 20 carbon atoms may be an ethenyl group, a propenyl group, a butenyl group, a pentenyl group or a cyclohexenyl group.

The carboxylate having 1 to 20 carbon atoms may have a structure of -COOR ^c and R ^c may be a hydrocarbyl group having 1 to 20 carbon atoms. The hydrocarbyl group is a monovalent functional group in which a hydrogen atom is removed from a hydrocarbon, and may include an alkyl group and an aryl group. Specifically, the carboxylate having 1 to 20 carbon atoms may be a pivalate or the like.

The aryl group having 6 to 20 carbon atoms may mean a monocyclic, bicyclic or tricyclic aromatic hydrocarbon. In addition, the aryl group may be used to include an aralkyl group in which at least one hydrogen of the alkyl group is substituted with an aryl group. Specifically, the aryl group having 6 to 20 carbon atoms may be a phenyl group, a naphthyl group, an anthracenyl group or a benzyl group.

The heteroaryl group having 5 to 20 carbon atoms may be a cyclic aryl group including at least one atom other than carbon exemplified by oxygen, nitrogen and sulfur. Specifically, the heteroaryl group having 5 to 20 carbon atoms may be a heteroaryl group having 5 to 15 carbon atoms or a heteroaryl group having 5 to 10 carbon atoms. More specifically, the heteroaryl group having 5 to 20 carbon atoms may be a furanyl group, a pyranyl group, a thiophenyl group, or a pyrrolyl group.

The sulfonate group having 1 to 20 carbon atoms may have the structure of -O-SO ₂ -R ^d , and R ^d may be a hydrocarbyl group having 1 to 20 carbon atoms. Specifically, the sulfonate group having 1 to 20 carbon atoms may be a methanesulfonate group, a phenylsulfonate group or the like.

The sulfone group having 1 to 20 carbon atoms has the structure of -R ^{e '} -SO ₂ -R ^{e "} wherein R ^e' and R ^e" are the same or different and each independently a hydrocarbyl group having 1 to 20 carbon atoms. Specifically, the sulfone group having 1 to 20 carbon atoms may be a methylsulfonylmethyl group, a methylsulfonylpropyl group, a methylsulfonylbutyl group, or a phenylsulfonylpropyl group.

In the present specification, one or more substituents adjacent to each other are connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring. That is, a pair of two substituents adjacent to each other is connected to each other to form an aliphatic or aromatic ring , And the aliphatic or aromatic ring may be substituted by any substituent. For example, a pair of substituents R ₁₆ and R ₁₇ adjacent to each other in the formula (2) may be bonded to each other to form an unsubstituted aromatic ring (when R ₂₈ is hydrogen) or an aromatic ring substituted with R ₂₈ (When R < ₂₈ > is not hydrogen). In addition, the substituents of the pair adjacent to each other in Formula 2 R ₁₆ and R ₁₇ (when R ₂₈ is hydrogen) a are connected to each other as shown in the formula (6) to be described later unsubstituted aliphatic ring or an aliphatic ring is substituted by R ₂₈ (R ₂₈ is not hydrogen) can be formed.

The above substituents may be optionally substituted with one or more substituents selected from the group consisting of a hydroxyl group, a halogen, an alkyl group, a heterocycloalkyl group, an alkoxy group, an alkenyl group, a silyl group, a phospho group, a phosphido group, A carboxyl group, a nitrile group, a sulfonate group, an aryl group, and a heteroaryl group.

The use of a catalyst in which the crosslinkable transition metal compound represented by Chemical Formula 1 and the non-crosslinked transition metal compound represented by Chemical Formula 2 are mixed and supported can be used to improve the chemical structure, molecular weight, molecular weight distribution, mechanical properties, workability and transparency of the olefin polymer The characteristics can be easily adjusted.

In particular, the olefin polymer prepared using a catalyst having one kind of transition metal compound supported therein exhibits poor bubble stability. As a result, it has been difficult to stably form a film when the olefin polymer is produced by using a catalyst having one kind of transition metal compound supported thereon by a melt blown process or the like.

However, when the hybrid supported catalyst according to one embodiment of the present invention is used, the olefin polymer having enhanced melt strength, which is one of important physical properties for determining the foam stability of the olefin polymer, can be produced. Accordingly, when the hybrid supported catalyst according to one embodiment of the present invention is used, an olefin polymer having high porosity suitable for a melt blown process can be provided.

Hereinafter, the structures of the transition metal compounds of the above formulas (1) and (2) will be described in detail.

The cyclopentadienyl ligand in the structure of the crosslinkable transition metal compound represented by the formula (1) may affect, for example, the polymerization activity of the olefin monomer.

Each of R ₁ to R ₄ of the cyclopentadienyl ligand may be independently selected from among hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms. More specifically, R ₁ to R ₄ each independently may be any one of a methyl group, an ethyl group, a propyl group, and a butyl group. In this case, the hybrid supported catalyst can exhibit a very high activity in the polymerization process of the olefin monomer.

The tetrahydroindenyl ligand in the structure of the crosslinkable transition metal compound represented by the above formula (1) can be prepared, for example, by adjusting the molecular weight of the olefin polymer prepared by controlling the degree of the steric hindrance effect depending on the type of the substituted functional group It can be easily adjusted.

Wherein R ₅ and R ₆ are each independently any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms, or R ₇ to R ₁₄ are each independently Is one of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms, or at least one pair of substituents adjacent to each other among R ₇ to R ₁₄ may be substituted or substituted, To form an unsubstituted aliphatic ring. More specifically, R ₅ and R ₆ in Formula 1 are each independently any one of hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alkenyl group having 2 to 4 carbon atoms, or R ₇ to R ₁₄ has one or more pairs of substituents that are each independently a hydrogen, any of an alkoxy group and an alkenyl group having 2 to 4 carbon atoms in the alkyl group of 1 to 4 carbon atoms, 1 to 4 carbon atoms one or or, adjacent to each other of R ₇ to R ₁₄ are each To form a substituted or unsubstituted aliphatic ring. In this case, the hybrid supported catalyst can provide an olefin polymer having excellent processability.

The cyclopentadienyl ligand and the tetrahydroindenyl ligand can be crosslinked by -T (Q ₁ ) (Q ₂ ) - to exhibit excellent stability.

In order to more effectively ensure this effect, transition metal compounds wherein Q ₁ and Q ₂ are each independently any one of an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms can be used. More specifically, transition metal compounds wherein Q ₁ and Q ₂ are the same as each other and are any one of a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group and a benzyl group can be used. And T is C, Si, Ge, Sn or Pb; C or Si; Or Si.

On the other hand, M ₁ (X ₁ ) (X ₂ ) exists between the crosslinked cyclopentadienyl ligand and the tetrahydroindenyl ligand, and M ₁ (X ₁ ) (X ₂ ) is influenced by the storage stability of the metal complex Lt; / RTI >

In order to more effectively ensure this effect, a transition metal compound wherein X ₁ and X ₂ are each independently any one of halogen, an alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 20 carbon atoms can be used. More specifically, transition metal compounds wherein X ₁ and X ₂ are each independently F, Cl, Br or I can be used. And M ₁ is Ti, Zr or Hf; Zr or Hf; Or Zr.

As an example, the crosslinkable transition metal compound capable of providing an olefin polymer having improved processability includes compounds represented by the following formulas (3) and (4).

(3)

[Chemical Formula 4]

In the general formulas (3) and (4), R ₂₅ and R ₂₆ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, An alkylsilyl group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, an alkoxysilyl group having 1 to 20 carbon atoms, a silyloxyalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An alkylaryl group having 1 to 20 carbon atoms and an arylalkyl group having 7 to 20 carbon atoms,

and l is an integer of 0 to 5.

R ₂₅ and R _{26, which} are substituents of the tetrahydroindenyl ligand in the above formulas (3) and (4), are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An alkenyl group having 2 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms; Or an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

On the other hand, two ligands in the structure of the non-crosslinkable transition metal compound represented by the general formula (2) may affect, for example, the polymerization activity of the olefin monomer.

Wherein R ₁₅ to R ₂₄ of the two ligands are each independently any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms, or R ₁₅ to R ₂₄ One or more substituents adjacent to each other may be connected to each other to form a substituted or unsubstituted aliphatic ring. More specifically, the R ₁₅ to R ₂₄ are independently any one of hydrogen, an alkoxy group and an alkenyl group having 2 to 6 carbon atoms in the alkyl group having 1 to 6 carbon atoms, having 1 to 6 carbon atoms, one or or R ₁₅ to R ₂₄ each Adjacent substituents may be connected to each other to form a substituted or unsubstituted aliphatic ring. In this case, the hybrid supported catalyst can exhibit a very high activity in the polymerization process of the olefin monomer.

M ₂ (X ₃ ) (X ₄ ) exists between the two ligands, and M ₂ (X ₃ ) (X ₄ ) may affect the storage stability of the metal complex.

In order to more effectively ensure this effect, a transition metal compound wherein X ₃ and X ₄ are each independently any one of halogen, an alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 20 carbon atoms can be used. More specifically, transition metal compounds wherein X ₃ and X ₄ are each independently F, Cl, Br or I can be used. And M ₂ is Ti, Zr or Hf; Zr or Hf; Or Zr.

As an example, non-crosslinkable transition metal compounds capable of providing an olefin polymer having improved processability include compounds represented by the following formulas (5) to (7).

[Chemical Formula 5]

[Chemical Formula 6]

(7)

In formulas (5) to (7), R ₂₇ to R ₃₀ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, An alkylsilyl group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, an alkoxysilyl group having 1 to 20 carbon atoms, a silyloxyalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An alkylaryl group having 1 to 20 carbon atoms and an arylalkyl group having 7 to 20 carbon atoms.

More specifically, R ₂₇ to R _{30, which} are substituents of two ligands in the above Chemical Formulas 5 to 7, are hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, 10 < / RTI > When a non-crosslinked transition metal compound having such a structure is used, the hybrid supported catalyst can be produced more stably.

The transition metal compounds represented by formulas (1) and (2) can be synthesized by applying known reactions, and a more detailed synthesis method can be referred to the examples.

The hybrid supported catalyst according to one embodiment may further include a cocatalyst to activate the crosslinkable and non-crosslinkable transition metal compound. As the cocatalyst, those conventionally used in the technical field to which the present invention belongs can be applied without particular limitation. As a non-limiting example, the promoter may be at least one compound selected from the group consisting of compounds represented by the following formulas (8) to (10).

[Chemical Formula 8]

R ₃₁ - [Al (R ₃₂ ) -O] _n -R ₃₃

In Formula 8,

R ₃₁ , R ₃₂ and R ₃₃ are each independently any one of hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,

n is an integer of 2 or more,

[Chemical Formula 9]

D ( _R34 ) ₃

In the above formula (9)

D is aluminum or boron,

R ₃₄ are each independently any one of halogen, a hydrocarbyl group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,

[Chemical formula 10]

^{[LH] + [Z (A} ) 4] - or ^{[L] + [Z (A} ) 4] -

In Formula 10,

L is a neutral or cationic Lewis base, H is a hydrogen atom,

Z is a Group 13 element, A is independently a hydrocarbyl group having 1 to 20 carbon atoms; A hydrocarbyloxy group having 1 to 20 carbon atoms; And substituents in which at least one hydrogen atom of these substituents is substituted with at least one substituent selected from the group consisting of halogen, hydrocarbyloxy group having 1 to 20 carbon atoms and hydrocarbylsilyl group having 1 to 20 carbon atoms.

Non-limiting examples of the compound represented by the formula (8) include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and tert-butyl aluminoxane. Non-limiting examples of the compound represented by the formula (9) include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, Triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, or dimethylaluminum in the presence of a catalyst such as a catalyst, Tosid and the like. Finally, non-limiting examples of the compound represented by formula (10) include trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis N, N-dimethylanilinium benzyltris (pentafluorophenyl) borate, N, N-dimethylanilinium n-butyltris (pentafluorophenyl) Tetrakis (4- (t-butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4- (triisopropylsilyl) , 5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium pentafluorophenoxy tris (pentafluorophenyl) borate, N, N-dimethyl- 2,4,6- trimethylanilinium tetrakis (Pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluoro Phenyl) borate, N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, hexadecyldimethylammonium tetrakis (pentafluorophenyl) Silane anilinium tetrakis (pentafluorophenyl) borate or methyldi (dodecyl) ammonium tetrakis (pentafluorophenyl) borate, and the like.

The cocatalyst can be used in an appropriate amount so that the activation of the crosslinkable and non-crosslinkable transition metal compounds can proceed sufficiently.

On the other hand, as the carrier of the hybrid supported catalyst according to one embodiment, a carrier containing a hydroxyl group or a siloxane group on its surface can be used. Specifically, as the carrier, a carrier containing a hydroxyl group or a siloxane group having high reactivity by removing moisture on the surface by drying at a high temperature may be used. More specifically, examples of the carrier include silica, alumina, magnesia, and mixtures thereof. The carrier may be one which has been dried at elevated temperatures and these may typically comprise oxides, carbonates, sulphates and nitrate components such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ and Mg (NO ₃ ) ₂ .

The hybrid supported catalyst according to one embodiment includes, for example, supporting a promoter on a support; And carrying the crosslinkable transition metal compound and the non-crosslinked transition metal compound on the co-catalyst supporting carrier one by one, or simultaneously carrying it, irrespective of order.

Specifically, in the step of supporting the carrier on the carrier, the carrier which is dried at a high temperature and the cocatalyst may be mixed and stirred at a temperature of about 20 to 120 ° C to prepare a cocatalyst-carrying carrier.

In the step of supporting the transition metal compound on the catalyst supporting carrier, a crosslinking type or non-crosslinking transition metal compound is simultaneously added to the catalyst supporting carrier; Or a transition metal compound of a crosslinking type or a non-crosslinking type may be added. Then, the resulting solution can be stirred at a temperature of about 20 to 120 ° C. If only one kind of transition metal compound is added in advance, the remaining one kind of transition metal compound may be added and the resulting solution may be stirred at a temperature of about 20 to 120 ° C to prepare a supported catalyst.

The crosslinkable transition metal compound and the unmodified transition metal compound may be used in a molar ratio of, for example, 100: 1 to 1: 1, a molar ratio of 50: 1 to 1: 1, a molar ratio of 20: 1 to 5: 1. If the crosslinking type transition metal compound exceeds the above range, the melt strength of the olefin polymer produced from the hybrid supported catalyst may be lowered. If the crosslinking type transition metal compound is below the range, the transparency of the film using the olefin polymer produced from the hybrid supported catalyst .

The content of the carrier, co-catalyst, co-catalyst supporting carrier, crosslinking type, and non-crosslinkable transition metal compound used for the use of the hybrid supported catalyst can be appropriately controlled depending on the physical properties or effects of the desired supported catalyst.

Examples of the reaction solvent for preparing the hybrid supported catalyst include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, nonane, decane and isomers thereof; Aromatic hydrocarbon solvents such as toluene, xylene and benzene; Or a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane and chlorobenzene. Since the hybrid supported catalyst is sensitive to moisture or oxygen, it can be produced under an inert atmosphere such as nitrogen or argon.

As a specific method for producing the hybrid supported catalyst, a production example described later and the like can be referred to. However, the manufacturing method of the hybrid supported catalyst is not limited to the description described in the present specification, and the manufacturing method may further employ a step that is conventionally employed in the technical field of the present invention, (S) may typically be altered by alterable step (s).

According to another embodiment of the present invention, there is provided a process for producing an olefin polymer comprising the step of polymerizing an olefin monomer in the presence of the hybrid supported catalyst.

As described above, due to the specific structure of the transition metal compounds of the above formulas (1) and (2), the hybrid supported catalyst can easily exhibit the characteristics such as chemical structure, molecular weight, molecular weight distribution, mechanical properties, workability and transparency of the synthesized olefin polymer Can be adjusted.

Examples of olefin monomers polymerizable with the hybrid supported catalyst include ethylene, alpha-olefins, cyclic olefins and the like. Dioene olefin monomers or triene olefin monomers having two or more double bonds can also be polymerized. Specific examples of the monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, Butene, dicyclopentadiene, 1,4-butadiene, 1,4-butadiene, 1,3-butadiene, 1,3-butadiene, Pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene and the like. These two or more monomers may be mixed and copolymerized. When the olefin polymer is a copolymer of ethylene and another comonomer, the comonomer is at least one comonomer selected from the group consisting of propylene, 1-butene, 1-hexene, 4-methyl- .

For the polymerization of the olefin monomer, various polymerization processes known as polymerization of olefin monomers such as a continuous solution polymerization process, a bulk polymerization process, a suspension polymerization process, a slurry polymerization process or an emulsion polymerization process can be employed. Such a polymerization reaction may be carried out at a temperature of about 50 to 110 DEG C or about 60 to 100 DEG C and a pressure of about 1 to 100 bar or a pressure of about 10 to 80 bar.

In addition, in the above polymerization reaction, the hybrid supported catalyst may be used in a state of being dissolved or diluted in a solvent such as pentane, hexane, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene and the like. At this time, by treating the solvent with a small amount of alkylaluminum or the like, a small amount of water or air that can adversely affect the catalyst can be removed in advance.

For example, an olefin polymer having high porosity can be prepared by using the hybrid supported catalyst. For example, olefin polymers prepared via hybrid supported catalysts may exhibit a melt strength of at least 70 mN. The melt strength is a value measured under the conditions described in Test Examples to be described later. Such an olefin polymer is excellent in cell stability and can be usefully used as a raw material for a product produced by the meltblown process.

BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features and advantages of the present invention will be more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG. However, this is provided as an example of the invention, and the scope of the invention is not limited thereto in any sense.

Manufacturing example  1: transition metal compound ( Metallocene  Preparation of Catalyst Precursor A)

Tetramethylcyclopentadiene (TMCP, 6.0 mL, 40 mmol) was dissolved in THF (60 mL) in a dried 250 mL schlenk flask and the solution was cooled to -78 < 0 > C. Then n-BuLi (2.5 M, 17 mL, 42 mmol) was slowly added dropwise to the solution and the resulting solution was stirred at room temperature overnight.

Meanwhile, dichlorodimethylsilane (4.8 mL, 40 mmol) was dissolved in n-hexane in a separate 250 mL Schlenk flask, and the solution was cooled to -78 ° C. Then, the TMCP-lithiation solution prepared in advance was slowly injected into this solution. The resulting solution was stirred at room temperature overnight.

The resulting solution was then depressurized to remove the solvent from the solution. The resulting solid was dissolved in toluene and filtered to remove the remaining LiCl to give an intermediate (yellow liquid, 7.0 g, 33 mmol, 83% yield).

¹ H NMR (500 MHz, CDCl ₃ ): 0.24 (6H, s), 1.82 (6H, s), 1.98 (6H, s), 3.08 (1H, s).

Indene (0.93 mL, 8.0 mmol) was dissolved in THF (30 mL) in a dried 250 mL Schlenk flask, and the solution was cooled to -78 ° C. Then n-BuLi (2.5 M, 3.4 mL, 8.4 mmol) was slowly added dropwise to the solution, and the resulting solution was stirred at room temperature for about 5 hours.

On the other hand, the above-prepared intermediate (1.7 g, 8.0 mmol) was dissolved in THF in a separate 250 mL schlenk flask, and the solution was cooled to -78 ° C. Subsequently, the indene-lithiation solution previously prepared was slowly injected into this solution. The resulting solution was stirred at room temperature overnight to obtain a purple solution.

Thereafter, water was poured into the reactor to quench the reaction, and the organic layer was extracted from the mixture with ether. It was confirmed by ¹ H NMR that the organic layer contained dimethyl (indenyl) (tetramethylcyclopentadienyl) silane and other organic compounds. The organic layer was concentrated without purification and used directly for metallation.

The dimethyl (indenyl) (tetramethylcyclopentadienyl) silane (1.7 g, 5.7 mmol) synthesized above in a 250 mL schlenk flask was dissolved in toluene (30 mL) and MTBE (3.0 mL). After the solution was cooled to -78 ° C, n-BuLi (2.5 M, 4.8 mL, 12 mmol) was slowly added dropwise to the solution, and the resulting solution was stirred at room temperature overnight. However, yellow solids were formed in the solution and were not stirred uniformly, further adding MTBE (50 mL) and THF (38 mL).

Meanwhile, ZrCl ₄ (THF) ₂ was dispersed in toluene in a separately prepared 250 mL schlenk flask, and the resulting mixture was cooled to -78 ° C. The lithiated ligand solution prepared previously in the mixture was then slowly injected. The resulting mixture was then stirred overnight.

Thereafter, the reaction product was filtered to obtain dimethylsilylene (tetramethylcyclopentadienyl) (indenyl) zirconium dichloride (1.3 g, containing 0.48 g, 1.8 mmol) in the form of a yellow solid. The solvent was removed and then washed with n-hexane to give an additional yellow solid (320 mg, 0.70 mmol) (total 44% yield).

¹ H NMR (500 MHz, CDCl ₃ ): 0.96 (3 H, s), 1.16 (3 H, s), 1.91 (3 H, s), 1.93 (1H, d), 5.98 (1H, d), 7.07 (1H, t), 7.23 (1H, d), 7.35

The previously synthesized dimethylsilylene (tetramethylcyclopentadienyl) (indenyl) zirconium dichloride (1.049 g, 2.3 mmol) was placed in a mini bomb in a glove box. The mini bomb was charged with an additional amount of platinum oxide (52.4 mg, 0.231 mmol), and the mini bomb was assembled. An anhydrous THF (30 mL) was added to the mini bomb using a cannula and hydrogen I filled it. Subsequently, the mixture in the mini bombe was stirred at about 60 占 폚 for about 1 day, the temperature of the mini bomb was cooled to room temperature, and the hydrogen was replaced with argon while the pressure of the mini bomb was gradually lowered.

On the other hand, celite dried in an oven at about 120 ° C for about 2 hours was placed on a Schlenk filter, and the reaction product of the mini bombe was filtered using argon. The PtO ₂ catalyst was removed from the reaction product by the celite. Subsequently, the reaction product after the removal of the catalyst is reduced in pressure to remove the solvent, and a pale yellow solid such as dimethylsilylene (tetramethylcyclopentadienyl) (tetrahydroindenyl) zirconium dichloride (hereinafter referred to as a metallocene catalyst precursor A (0.601 g, 1.31 mmol, Mw: 458.65 g / mol).

^{1 H NMR (500 MHz, CDCl} 3): 0.82 (3H, s), 0.88 (3H, s), 1.92 (6H, s), 1.99 (3H, s), 2.05 (3H, s), 2.34 (2H, m), 2.54 (2H, m), 2.68 (2H, m), 3.03 (2H, m), 5.45 (1H, s), 6.67 (1H, s).

Manufacturing example  2: transition metal compound ( Metallocene  Preparation of Catalyst Precursor B)

TMCP-Li (1.3 g, 10 mmol), CuCN (45 mg, 5 mol%) and THF (10 mL) were added to a dry 250 mL schlenk flask. Subsequently, the temperature of the flask was cooled to -20 占 폚 or lower, dichlorodiphenylsilane (2.5 g, 10 mmol) was added dropwise, and the resulting mixture was stirred at room temperature for 16 hours.

Then, the temperature of the flask was cooled to -20 占 폚 or lower, and an indene-lithiation solution (1.2 g, 10 mmol in THF 10 mL) was added dropwise. The obtained mixture was stirred at room temperature for 24 hours.

The resulting solution was then dried under reduced pressure to remove the solvent from the solution. The resulting solid was dissolved in hexane and filtered to remove residual LiCl. The filtrate was dried under reduced pressure to remove hexane from the filtrate to obtain diphenyl (indenyl) (tetramethylcyclopentadienyl) silane.

Diphenyl (indenyl) (tetramethylcyclopentadienyl) silane (4.2 g, 10 mmol) synthesized above was dissolved in THF (15 mL) in a 100 mL schlenk flask. After the solution was cooled to -20 占 폚 or lower, n-BuLi (2.5 M in hexane, 8.4 mL, 21 mmol) was slowly added dropwise to the solution, and the resulting solution was stirred at room temperature for 6 hours.

Meanwhile, ZrCl ₄ (THF) ₂ (3.8 g, 10 mmol) was separately dispersed in toluene (15 mL) in a separately prepared 250 mL schlenk flask, and the resulting mixture was stirred at -20 캜. The lithiated ligand solution prepared previously in the mixture was then slowly injected. The resultant mixture was stirred at room temperature for 48 hours.

The resulting solution was then dried under reduced pressure to remove the solvent from the solution. The resulting solid was dissolved in dichloromethane (DCM), filtered to remove residual LiCl, and the filtrate was dried under reduced pressure to remove DCM. Subsequently, the resulting solid was added to 30 mL of toluene and stirred for 16 hours, followed by filtration to obtain diphenylsilylene (tetramethylcyclopentadienyl) (indenyl) zirconium dichloride (2.1 g, 3.6 mmol) in the form of a lemon solid (36% yield).

¹ H NMR (500 MHz, CDCl ₃ ): 8.08-8.12 (2H, m), 7.98-8.05 (2H, m), 7.77 (1H, d), 7.47-7.53 (3H, m), 7.42-7.46 3H, s), 1.68 (3H, s), 1.52 (3H, s), 7.37-7.41 (2H, m), 6.94 3H, s).

(1.0 g, 1.7 mmol), Pd / C (10 mol%) and DCM (40 mL) were injected into a 100 mL high-pressure reactor, And filled with hydrogen to a pressure of about 60 bar. The mixture in the high pressure reactor was then stirred for about 24 hours at about < RTI ID = 0.0 > 80 C. < / RTI > When the reaction is completed, the reaction product is passed through a celite pad to remove the solid from the reaction product, and diphenylsilylene (tetramethylcyclopentadienyl) (tetrahydroindenyl) zirconium dichloride (hereinafter referred to as' Precursor B ') (0.65 g, 1.1 mmol, 65% yield).

^{1 H NMR (500 MHz, CDCl} 3): 7.90-8.00 (4H, m), 7.38-7.45 (6H, m), 6.80 (1H, s), 5.71 (1H, s), 3.15-3.50 (1H, m ), 2.75-2.85 (1H, m), 2.50-2.60 (1H, m), 2.12 (3H, s), 2.03 1.53-1.70 (4H, m), 1.48 (3H, s).

Manufacturing example  3: transition metal compound ( Metallocene  Preparation of Catalyst Precursor C)

6.0 mL (40 mmol) of tetramethylcyclopentadiene (TMCP) was added to a dry 250 mL schlenk flask and 60 mL of THF was added to dissolve the tetramethylcyclopentadienes in THF and the solution was cooled to -78 ° C. Then, 17 mL (42 mmol) of n-BuLi (2.5 M in THF) was slowly added dropwise to the flask, and the obtained solution was stirred at room temperature overnight.

On the other hand, 4.8 mL (40 mmol) of dichlorodimethylsilane was added to a separate 250 mL schlenk flask, and n-hexane was added to dissolve the dichlorodimethylsilane in n-hexane, and the solution was cooled to -78 ° C.

The TMCP-lithiation solution prepared above was slowly injected into the solution containing dichlorodimethylsilane. The resulting solution was then stirred at room temperature overnight.

Thereafter, the solution was depressurized to remove the solvent, and the remaining reaction product was dissolved in toluene. Then, the toluene solution was filtered to remove LiCl not dissolved in toluene to obtain 7.0 g (33 mmol, 83% yield) of a yellow liquid intermediate.

¹ H NMR (500 MHz, CDCl ₃ ): 0.24 (6H, s), 1.82 (6H, s), 1.98

To a dried 250 mL schlenk flask was added 0.93 mL (8.0 mmol) of indene and 30 mL of THF to dissolve the indene in THF, and then the solution was cooled to -78 ° C. 34 mL (8.4 mmol) of n-BuLi (2.5 M in THF) was slowly added dropwise to the flask, and the resulting solution was stirred at room temperature for about 5 hours.

On the other hand, 1.7 g (8.0 mmol) of the synthesized intermediate and THF were added to a separate 250 mL schlenk flask to dissolve the intermediate in THF, and the solution was cooled to -78 캜.

The indene-lithiation solution prepared above was slowly injected into the solution containing the intermediate. The resulting solution was then stirred overnight at ambient temperature to give a purple solution. Water was added to the purple solution to quench the reaction. The organic layer was then separated from the solution using an ether solvent. Then, the organic layer was reduced in pressure to obtain 1.7 g of a yellow liquid mixture containing the following ligand.

1.7 g (5.7 mmol) of a mixture containing the ligand was added to a 250 mL schlenk flask, and 30 mL of THF and 3.0 mL of MTBE (methyl t-butyl ether) were added to dissolve the mixture in the mixed solvent. Then, the resulting solution was cooled to -78 占 폚, 4.8 mL (12 mmol) of n-BuLi (2.5 M) was added to the solution, and the resulting solution was stirred overnight. Then, 50 mL of MTBE and 38 mL of THF were added to the solution to obtain a yellow solution.

Meanwhile, ZrCl ₄ (THF) ₂ and THF were added to a separately prepared 250 mL schlenk flask to disperse ZrCl ₄ (THF) ₂ in THF. The solution was cooled to -78 ° C., and a yellow solution Were injected slowly. Then, it was stirred overnight. Thereafter, the obtained reaction product was filtered to obtain dimethylsilylene (tetramethylcyclopentadienyl) (indenyl) zirconium dichloride (hereinafter, referred to as 'metallocene catalyst precursor C') as a yellow solid (44% yield).

¹ H NMR (500 MHz, CDCl ₃ ): 0.96 (3H, s), 1.16 (3H, s), 1.91 (3H, s), 1.93 (1H, d), 5.98 (1H, d), 7.07 (1H, t), 7.23

Manufacturing example  4: transition metal compound ( Metallocene  Preparation of Catalyst Precursor F)

(2.0 g, 5.1 mmol) of bis (indenyl) zirconium dichloride (CAS Number: 12148-49-1, manufactured by Strem, hereinafter referred to as "metallocene catalyst precursor E"), PtO ₂ (40 mL) was charged to a 100 mL high pressure reactor and charged with hydrogen to a pressure of about 60 bar. Subsequently, the mixture contained in the high-pressure reactor was stirred at room temperature for about 24 hours. When the reaction was completed, the reaction product was passed through a celite pad to remove the solid from the reaction product to obtain bis (tetrahydroindenyl) zirconium dichloride (hereinafter referred to as "metallocene catalyst precursor F") (1.4 g, 3.5 mmol, 69% yield).

Manufacturing example  5: Preparation of supported catalyst

Silica (SP 952 manufactured by Grace Davison) was dried at a temperature of 600 캜 and under vacuum for 12 hours. Then, 20 g of dried silica was added to the glass reactor. Subsequently, a methylaluminoxane (MAO) solution containing 13 mmol of aluminum in toluene was charged into the glass reactor, and the resulting solution was stirred at 40 DEG C for 1 hour. Thereafter, stirring was stopped to allow the reaction product to stand, decantation was performed to remove the aluminum compound, and the aluminum compound was completely removed again by washing with a sufficient amount of toluene several times. Then, the obtained reaction product was dried under reduced pressure at 50 캜 to remove remaining toluene, thereby preparing 32 g of a catalyst-supported carrier. The obtained MAO / SiO ₂ contained 17% aluminum.

12 g of the support carrying the above promoter was placed in a glass reactor, and then 70 mL of toluene was injected and stirred. Then, a toluene solution in which the metallocene catalyst precursor A (1.2 mmol) prepared in Preparation Example 1 was dissolved was injected into the reactor and stirred at 40 ° C for 1 hour. Then, a toluene solution in which the metallocene catalyst precursor E (0.12 mmol) was dissolved was injected into the reactor and stirred again at 40 ° C for 1 hour. Thereafter, the obtained reaction product was washed with a sufficient amount of toluene, and then subjected to reduced pressure preheating to obtain a supported catalyst in the form of a solid powder.

Manufacturing example  6: Preparation of Supported Catalyst

A supported catalyst was obtained in the same manner as in Production Example 5, except that the metallocene catalyst precursor A was used instead of the metallocene catalyst precursor A in Production Example 5.

Manufacturing example  7: Preparation of Supported Catalyst

A supported catalyst was obtained in the same manner as in Production Example 5, except that the metallocene catalyst precursor F prepared in Preparation Example 4 was used in place of the metallocene catalyst precursor E.

Manufacturing example  8: Preparation of Supported Catalyst

A supported catalyst was obtained in the same manner as in Production Example 6, except that the metallocene catalyst precursor F prepared in Preparation Example 4 was used in place of the metallocene catalyst precursor E in Production Example 6. [

Manufacturing example  9: Preparation of supported catalyst

(N-butylcyclopentadienyl) zirconium dichloride (CAS Number: 73364-10-0, manufactured by Sigma-Aldrich, hereinafter referred to as " metallocene catalyst precursor E Catalyst precursor G ') (0.09 mmol) was used as a catalyst precursor.

Manufacturing example  10: Preparation of supported catalyst

A supported catalyst was obtained in the same manner as in Production Example 5, except that the metallocene catalyst precursor E (0.12 mmol) was not used in Production Example 5.

Manufacturing example  11: Preparation of supported catalyst

A supported catalyst was obtained in the same manner as in Production Example 6, except that the metallocene catalyst precursor E (0.12 mmol) was not used in the above Production Example 6.

Manufacturing example  12: Preparation of supported catalyst

A supported catalyst was obtained in the same manner as in Production Example 5, except that the metallocene catalyst Precursor C prepared in Preparation Example 3 was used in place of the metallocene catalyst Precursor A in Production Example 5.

Manufacturing example  13: Preparation of supported catalyst

In the above Production Example 5, dimethylsilylenebis (indenyl) zirconium dichloride (CAS Number: 121009-93-6, manufactured by Strem, hereinafter referred to as 'metallocene catalyst precursor D') was used instead of the metallocene catalyst precursor A, The supported catalyst was obtained in the same manner as in Production Example 5.

Manufacturing example  14: Preparation of supported catalyst

A supported catalyst was obtained in the same manner as in Production Example 5 except that the metallocene catalyst precursor E was used instead of the metallocene catalyst precursor D in Production Example 5. [

Example  1: Preparation of olefin copolymer

10 mg of the supported catalyst prepared in Preparation Example 5 was quantitatively measured in a dry box, packed in a 50 mL glass bottle, and sealed with a rubber septum. Polymerization of the olefin monomer was carried out in a 600 mL metal alloy reactor equipped with a mechanical stirrer and temperature controllable and capable of withstanding high pressures. To the reactor was added 400 mL of hexane containing 1.0 mmol of triethylaluminum, the supported catalyst prepared above and 1-hexene (33 mL) without air contact. When the temperature of the reactor reached 70 DEG C, ethylene gas was continuously fed to the reactor at a pressure of 30 kgf / cm < ² > for 1 hour. Thereafter, stirring was stopped and unreacted ethylene gas was exhausted. The reaction product was filtered to remove the solvent and then dried in a vacuum oven at 80 ° C for 4 hours to obtain an ethylene-1-hexene copolymer.

Example  2 to 5 and Comparative Example  1 to 5: Preparation of olefin copolymer

An olefin copolymer was prepared in the same manner as in Example 1, except that the catalyst described in Table 1 was used instead of the supported catalyst of Example 1.

Test Example : Activity of Supported Catalysts and Evaluation of Properties of Olefin Copolymer

Table 1 shows the activity of the catalysts used in Examples 1 to 5 and Comparative Examples 1 to 5 and the properties of the olefin copolymers prepared using the catalysts.

Specifically, the activity of the catalyst used in each of the Examples and Comparative Examples was calculated by measuring the mass of the catalyst used in the polymerization reaction and the mass of the polymer calculated from the reaction, and the results are shown in Table 1 below .

Melt Index (MI _{2. 16)} was measured in accordance with ASTM D1238 (condition E, 190 ℃, 2.16kg load) standard. Melt Flow Rate Ratio (MFRR (21.6 / 2.16)) was calculated by dividing the MFR _{21 .6} to MFR _{2 .16,} MFR _{21 .6} is measured under a load of 21.6kg and the temperature of 190 ℃ according to ISO 1133, and MFR _{2 16} was measured under a load of 2.16kg and temperature of 190 ℃ according to ISO 1133.

Melt Strength was measured using Goettfert Rheotens 71.97 with a Model 3211 Instron capillary rheometer. The olefin copolymer melts were discharged through a capillary die (plane die, 180 degree angle) with a ratio of length (L) to diameter (D) of 15 (L / D) After equilibrating the sample at 190 for 10 minutes, the piston was moved at a rate of 1 inch / minute (2.54 cm / min). The standard test temperature is 190. The sample was uniaxially pulled into a set of accelerating nips located below the die 100 mm at an acceleration of 1.2 mm / s ² . The tension was recorded as a function of the pulling speed of the nip roll. The melt strength was defined as the mean value of the force (mN) at pulling forces of 100 mm / s and 150 mm / s. The following conditions were used for melt strength measurement.

Plunger speed: 0.423 mm / s

Capillary die L / D: 15

Shear rate: 72 / s

Wheel initial speed: 18 mm / s

Wheel acceleration: 1.2 mm / s ²

Barrel diameter = 9.52 mm

Supported catalyst Metallocene catalyst precursor composition Mixing Molar Ratio of Metallocene Catalyst Precursor Catalytic activity
[kgPE / gCat] H ₂ input
[mol%] MI _2.16
[g / 10 min] MFRR
(21.6 / 2.16) Melt strength
[mN] Example 1 Production Example 5 A / E 10/1 8.3 0.07 0.80 29 77 Example 2 Production Example 6 B / E 10/1 4.1 0.04 0.24 25 95 Example 3 Production Example 7 A / F 10/1 5.4 0.05 0.68 27 88 Example 4 Production Example 8 B / F 10/1 3.8 0.09 0.92 25 75 Example 5 Production Example 9 A / G 13/1 6.8 0.10 1.20 25 73 Comparative Example 1 Production Example 10 A One 7.5 0.05 0.94 33 54 Comparative Example 2 Production Example 11 B One 3.5 0.04 0.54 30 58 Comparative Example 3 Production Example 12 C / E 10/1 7.2 0.07 1.12 28 60 Comparative Example 4 Production Example 13 D / E 10/1 6.5 0.08 1.05 27 63 Comparative Example 5 Production Example 14 A / D 10/1 7.9 0.07 0.98 31 66

Since the melt strength value is influenced by the MI and the MFRR which are related to the molecular weight of the olefin polymer and the like, the olefin polymer having an MI and an MFRR value in a specific range according to Examples 1 to 5 and Comparative Examples 1 to 5 A polymer was prepared.

Referring to Table 1, it is confirmed that the olefin polymers produced according to Examples 1 to 5 exhibit a higher melt strength than the olefin polymers of Comparative Examples 1 to 5 having similar MI and MFRR values. Thus, it is confirmed that the bubble stability of the olefin polymer is improved by using the hybrid supported catalyst according to one embodiment of the present invention, and the processability is improved. In particular, when the hybrid supported catalyst according to an embodiment of the present invention is used, it is expected that olefin polymers having high porosity suitable for the melt blown process can be provided.

Claims (14)

carrier; A crosslinked transition metal compound supported on the support and represented by the following formula (1); And a non-crosslinked transition metal compound supported on the support and represented by the following general formula (2):
[Chemical Formula 1]

(2)

In the general formulas (1) and (2), M ₁ and M ₂ are the same as or different from each other, and are independently Ti, Zr or Hf,
X ₁ , X ₂ , X ₃ and X ₄ are the same or different and each independently represents a halogen, a nitro group, an amido group, a phospho group, a phosphido group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms , An alkoxyalkyl group having 2 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a sulfonate group having 1 to 20 carbon atoms and a sulfone group having 1 to 20 carbon atoms Any one,
T is C, Si, Ge, Sn or Pb,
Q ₁ and Q ₂ are the same or different from each other and each independently represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, a heterocycloalkyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms , A carboxylate having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a heteroaryl group having 5 to 20 carbon atoms,
R ₁ to R ₆ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, A silyloxyalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms,
R ₇ to R ₁₄ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, A silyloxyalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, or at least one pair of substituents adjacent to each other among R ₇ to R ₁₄ , To form a substituted or unsubstituted aliphatic or aromatic ring,
R ₁₅ to R ₂₄ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, A silyloxyalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, or at least one pair of substituents adjacent to each other among R ₁₅ to R ₂₄ , To form a substituted or unsubstituted aliphatic or aromatic ring.
The hybrid supported catalyst according to claim 1, wherein R ₁ to R ₄ are each independently any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms.
The hybrid supported catalyst according to claim 1, wherein R ₅ and R ₆ are each independently any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms.
The method of claim 1, wherein, R ₇ to R ₁₄ is any one or or, R ₇ to R ₁₄ of each independently represent a hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms an alkoxy group and having 2 to 20 carbon atoms in the Wherein at least one of the substituents adjacent to each other is linked to form a substituted or unsubstituted aliphatic ring.
The hybrid supported catalyst according to claim 1, wherein Q ₁ and Q ₂ are each independently any one of an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms.
The hybrid supported catalyst according to claim 1, wherein X ₁ to X ₄ are each independently any one of halogen, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms.
The method of claim 1, wherein, R ₁₅ to R ₂₄ are each independently selected from hydrogen, any of an alkoxy group and an alkenyl group having 2 to 20 carbon atoms in the alkyl group having 1 to 20 carbon atoms, having 1 to 20 carbon atoms in one or, R ₁₅ to R ₂₄ Wherein at least one pair of substituents adjacent to each other are connected to each other to form a substituted or unsubstituted aliphatic ring.
The hybrid supported catalyst according to claim 1, wherein the crosslinkable transition metal compound represented by the formula (1) is any one of compounds represented by the following formulas (3) and (4)
(3)

[Chemical Formula 4]

In the general formulas (3) and (4), R ₂₅ and R ₂₆ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, An alkylsilyl group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, an alkoxysilyl group having 1 to 20 carbon atoms, a silyloxyalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An alkylaryl group having 1 to 20 carbon atoms and an arylalkyl group having 7 to 20 carbon atoms,
and l is an integer of 0 to 5.
The hybrid supported catalyst according to claim 1, wherein the non-crosslinked transition metal compound represented by the general formula (2) is any one of compounds represented by the following general formulas (5) to (7)
[Chemical Formula 5]

[Chemical Formula 6]

(7)

In formulas (5) to (7), R ₂₇ to R ₃₀ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, An alkylsilyl group having 1 to 20 carbon atoms, a silylalkyl group having 1 to 20 carbon atoms, an alkoxysilyl group having 1 to 20 carbon atoms, a silyloxyalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An alkylaryl group having 1 to 20 carbon atoms and an arylalkyl group having 7 to 20 carbon atoms.
The hybrid supported catalyst according to claim 1, further comprising at least one cocatalyst selected from the group consisting of compounds represented by the following formulas (8) to (10):
[Chemical Formula 8]
R ₃₁ - [Al (R ₃₂ ) -O] _n -R ₃₃
In Formula 8,
R ₃₁ , R ₃₂ and R ₃₃ are each independently any one of hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,
n is an integer of 2 or more,
[Chemical Formula 9]
D ( _R34 ) ₃
In the above formula (9)
D is aluminum or boron,
R ₃₄ are each independently any one of halogen, a hydrocarbyl group having 1 to 20 carbon atoms, and a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,
[Chemical formula 10]
^{[LH] + [Z (A} ) 4] - or ^{[L] + [Z (A} ) 4] -
In Formula 10,
L is a neutral or cationic Lewis base, H is a hydrogen atom,
Z is a Group 13 element, A is independently a hydrocarbyl group having 1 to 20 carbon atoms; A hydrocarbyloxy group having 1 to 20 carbon atoms; And substituents in which at least one hydrogen atom of these substituents is substituted with at least one substituent selected from the group consisting of halogen, hydrocarbyloxy group having 1 to 20 carbon atoms and hydrocarbylsilyl group having 1 to 20 carbon atoms.
The hybrid supported catalyst according to claim 1, wherein the carrier is silica, alumina, magnesia or a mixture thereof.
The hybrid supported catalyst according to claim 1, wherein the crosslinking type transition metal compound represented by Formula 1 and the non-crosslinked transition metal compound represented by Formula 2 are contained in a molar ratio of 100: 1 to 1: 1.
A process for producing an olefin polymer comprising the step of polymerizing an olefin monomer in the presence of the hybrid supported catalyst of claim 1.
The method of claim 13, wherein the olefin monomer is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, Dodecene, 1-tetradecene, 1-hexadecene, 1-aidosene, norbornene, norbornadiene, ethylidenenorbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, 1,4- A process for producing an olefin polymer comprising at least one member selected from the group consisting of butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.