KR20200143277A - Hybride supported metallocene catalyst and method for preparing polypropylene using the same - Google Patents

Abstract

The present invention relates to a hybrid supported metallocene catalyst useful for manufacturing polypropylene having a high melt tension by introducing a long chain branch into a polypropylene molecule and exhibiting high activity in propylene polymerization, and a method for manufacturing polypropylene using the same. The present invention provides the hybrid supported metallocene catalyst comprising at least one first metallocene compound selected from compounds represented by chemical formula 1, at least one second metallocene compound selected from compounds represented by chemical formula 2, and a carrier supporting the first and second metallocene compounds.

Description

Hybrid supported metallocene catalyst and method for producing polypropylene using the same {HYBRIDE SUPPORTED METALLOCENE CATALYST AND METHOD FOR PREPARING POLYPROPYLENE USING THE SAME}

The present invention relates to a hybrid supported metallocene catalyst and a method for producing polypropylene using the same.

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems. These two highly active catalyst systems have been developed to suit their respective characteristics.

Ziegler Natta catalysts have been widely applied to conventional commercial processes since their invention in the 50s, but since they are multi-site catalysts with multiple active points, they are characterized by a wide molecular weight distribution of polymers, and comonomers There is a problem in that there is a limit to securing desired physical properties because the composition distribution of is not uniform.

On the other hand, the metallocene catalyst is composed of a combination of a main catalyst composed of a transition metal compound and a cocatalyst composed of an organometallic compound composed mainly of aluminum. Such a catalyst is a homogeneous complex catalyst and exhibits the characteristics of a single site catalyst. The molecular weight distribution is narrow according to the characteristics of the single active point, and a polymer having a uniform composition distribution of the comonomer is obtained. It has properties that can change the stereoregularity, copolymerization properties, molecular weight, crystallinity, etc. of the polymer according to the modification of the ligand structure and the change of polymerization conditions.

Due to the recent change in environmental awareness, many product groups are seeking to reduce the occurrence of volatile organic compounds (VOC). However, in the case of the Ziegler-Natta catalyst (Z/N, ziegler-natta) used in the production of polypropylene, there was a problem of generating high volatile organic compounds (TVOC). In particular, in the case of various commercialized polypropylenes, products to which Ziegler-Natta catalysts are applied are the mainstream, but recently, the conversion to products to which metallocene catalysts exhibiting low odor and low dissolution characteristics is accelerating.

In particular, conventional polypropylene is a general-purpose resin and has advantages of being light, having high stiffness and heat resistance, and low hygroscopicity due to its low density, but has disadvantages of low impact and low melt tension. Moreover, the current commercialization process for producing polypropylene with high melt tension is mostly a post-treatment step, i.e., post-modification (Irradiation, Grafted polymerization as crosslinking), and a catalytic technology is applied to introduce long chain branches in the reactor. There has been a continuing need for technology to make polypropylene.

Accordingly, there is a need to develop a method for producing polypropylene having a high melt tension by using a metallocene catalyst, showing high activity in propylene polymerization, and introducing a long chain branch (LCB) in the polypropylene molecule.

An object of the present invention is to provide a hybrid supported metallocene catalyst useful for producing polypropylene having a relatively high melt tension and excellent catalytic activity for propylene polymerization.

In addition, the present invention is to provide a method for producing polypropylene using the hybrid supported metallocene catalyst.

The present invention, at least one first metallocene compound selected from the compounds represented by the following formula (1); At least one second metallocene compound selected from compounds represented by the following formula (2); And it provides a hybrid supported metallocene catalyst comprising; and a carrier supporting the first and second metallocene compounds.

[Formula 1]

In Formula 1,

M ₁ is a Group 4 transition metal,

A ₁ is carbon (C), silicon (Si), or germanium (Ge),

Q ₁ and Q ₂ are each independently C _1-20 alkyl,

R ₁ to R ₃ are each independently C _1-20 alkyl,

R ₄ is C _6-20 aryl unsubstituted or substituted with C _1-20 alkyl,

R ₅ to R ₇ are each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-30 aryl, C _7-30 alkylaryl, and C _7-30 arylalkyl Any one of, or two adjacent functional groups are bonded to each other to form an aliphatic cyclic group,

R ₈ is any one of hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-30 aryl, C _7-30 alkylaryl, and C _7-30 arylalkyl,

X ₁ and X ₂ are each independently a single bond, or S or CR _a R _b , but at least one of X ₁ and X ₂ is S, wherein R _a and R _b are each independently hydrogen, C _{1- 20} alkyl, C _2-20 alkenyl, C _6-30 aryl, C _7-30 alkylaryl, and C _7-30 arylalkyl,

Y ₁ and Y ₂ are each independently halogen,

m is an integer from 1 to 4,

[Formula 2]

In Chemical Formula 2,

M ₂ is a Group 4 transition metal;

A ₂ is carbon (C), silicon (Si), or germanium (Ge),

Y ₃ and Y ₄ are each independently halogen,

R ₉ and R ₁₄ are each independently C _1-20 alkyl, or C _6-20 aryl,

R ₁₀ and R ₁₅ are each independently C _6-40 aryl substituted or unsubstituted with C _1-20 alkyl,

R ₁₁ to R ₁₃ and R ₁₆ to R ₁₈ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 Alkoxysilyl, C _1-20 ether, C _1-20 silyl ether, C _1-20 alkoxy, C _6-40 aryl, C _7-20 alkylaryl, and C _7-20 arylalkyl,

Q ₃ and Q ₄ are identical to each other and are C _2-20 alkyl.

And, in Formula 1, Q ₁ and Q ₂ are each C _1-6 alkyl, Y ₁ and Y ₂ are each halogen, A ₁ is silicon (Si), M ₁ is zirconium (Zr) or hafnium ( Hf).

Further, in Formula 1, R ₁ to R ₃ may each be C _1-6 straight-chain alkyl, and specifically, each may be methyl.

And, in Formula 1, R ₄ may be substituted or unsubstituted with C _3-6 branched alkyl, phenyl or naphthyl, specifically phenyl, 4-(tert-butyl) phenyl, 3,5 -Di-(tert-butyl)phenyl, or naphthyl.

Further, in Formula 1, R ₅ to R ₇ may each be hydrogen or two adjacent functional groups may be bonded to each other to form a cyclopentyl group.

And, in Formula 1, any one of X ₁ and X ₂ may be S, and the other may be a single bond.

The first metallocene compound may be represented by one of the following structural formulas.

.

.

Meanwhile, in Formula 2, Y ₃ and Y ₄ may each be halogen, A ₂ may be silicon (Si), and M ₂ may be zirconium (Zr) or hafnium (Hf).

In addition, in Formula 2, R ₉ and R ₁₄ may be the same as or different from each other, and may be C _1-6 or C _1-3 linear or branched alkyl.

Further, in Formula 2, R ₁₀ and R ₁₅ may be the same as or different from each other, and each may be a phenyl group substituted with a C _3-6 branched alkyl group.

Further, in Formula 2, R ₁₁ to R ₁₃ and R ₁₆ to R ₁₈ may each be hydrogen or C _1-6 linear or branched alkyl.

In addition, in Formula 2, Q ₃ and Q ₄ are the same, and may be a C _2-4 linear alkyl group, specifically ethyl.

The second metallocene compound may be a compound represented by the following structural formula.

In addition, the first metallocene compound and the second metallocene compound may be supported in a molar ratio of 1:1 to 1:8.

In addition, the carrier may contain a hydroxy group and a siloxane group on the surface, and preferably may be at least one selected from the group consisting of silica, silica-alumina, and silica-magnesia.

And, the hybrid supported metallocene catalyst of the present invention may further include one or more cocatalysts selected from the group consisting of compounds represented by the following Chemical Formulas 3 to 5.

[Formula 3]

-[Al(R ₃₁ )-O] _c-

In Chemical Formula 3,

Each R ₃₁ is independently halogen, C _1-20 alkyl or C _1-20 haloalkyl,

c is an integer greater than or equal to 2,

[Formula 4]

D(R ₄₁ ) ₃

In Chemical Formula 4,

D is aluminum or boron,

Each R ₄₁ is independently hydrogen, halogen, C _1-20 hydrocarbyl or C _1-20 hydrocarbyl substituted with halogen,

[Formula 5]

^{[LH] + [Q (E} ) 4] - or ^{[L] + [Q (E} ) 4] -

In Chemical Formula 5,

L is a neutral or cationic Lewis base,

[LH] ⁺ is Bronsted acid,

Q is Br ³⁺ or Al ³⁺ ,

E is each independently C _6-40 aryl or C _1-20 alkyl, wherein the C _6-40 aryl or C _1-20 alkyl is unsubstituted or halogen, C _1-20 alkyl, C _1-20 alkoxy, And C _6-40 is substituted with one or more substituents selected from the group consisting of aryloxy.

On the other hand, the present invention provides a method for producing polypropylene, including the step of polymerizing a propylene monomer in the presence of the above-described hybrid supported metallocene catalyst.

At this time, the polypropylene may be a homopolymer, and the polypropylene is polymerized using a catalyst in which a first metallocene compound and a second metallocene compound having a specific substituent and structure are mixedly supported as described above. , It shows high catalytic activity, and the melt tension can be remarkably improved by introducing a long chain branch (LCB) into the polypropylene molecule.

The terms used in the present specification are only used to describe exemplary embodiments, and are not intended to limit the present invention.

Singular expressions include plural expressions unless the context clearly indicates otherwise.

In the present specification, terms such as "comprise", "include" or "have" are used to describe implemented features, numbers, steps, components, or combinations thereof, and one or more other features, numbers, and steps , Components, combinations or additions thereof are not excluded.

In addition, in the present specification, when each layer or element is referred to as being formed “on” or “on” each layer or element, it means that each layer or element is formed directly on each layer or element, or It means that a layer or element may be additionally formed between each layer, on the object, or on the substrate.

The present invention will be described in detail below and exemplify specific embodiments, as various changes can be made and various forms can be obtained. However, this is not to limit the present invention to a specific form disclosed, it should be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

Hereinafter, the present invention will be described in detail.

According to an aspect of the present invention, at least one first metallocene compound selected from compounds represented by the following formula (1); At least one second metallocene compound selected from compounds represented by the following formula (2); And a carrier supporting the first and second metallocene compounds.

[Formula 1]

In Formula 1,

M ₁ is a Group 4 transition metal,

A ₁ is carbon (C), silicon (Si), or germanium (Ge),

Q ₁ and Q ₂ are each independently C _1-20 alkyl,

R ₁ to R ₃ are each independently C _1-20 alkyl,

R ₄ is C _6-20 aryl unsubstituted or substituted with C _1-20 alkyl,

R ₅ to R ₇ are each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-30 aryl, C _7-30 alkylaryl, and C _7-30 arylalkyl Any one of, or two adjacent functional groups are bonded to each other to form an aliphatic cyclic group,

R ₈ is any one of hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-30 aryl, C _7-30 alkylaryl, and C _7-30 arylalkyl,

X ₁ and X ₂ are each independently a single bond, or S or CR _a R _b , but at least one of X ₁ and X ₂ is S, wherein R _a and R _b are each independently hydrogen, C _{1- 20} alkyl, C _2-20 alkenyl, C _6-30 aryl, C _7-30 alkylaryl, and C _7-30 arylalkyl,

Y ₁ and Y ₂ are each independently halogen,

m is an integer from 1 to 4,

[Formula 2]

In Chemical Formula 2,

M ₂ is a Group 4 transition metal;

A ₂ is carbon (C), silicon (Si), or germanium (Ge),

Y ₃ and Y ₄ are each independently halogen,

R ₉ and R ₁₄ are each independently C _1-20 alkyl, or C _6-20 aryl,

R ₁₀ and R ₁₅ are each independently C _6-40 aryl substituted or unsubstituted with C _1-20 alkyl,

R ₁₁ to R ₁₃ and R ₁₆ to R ₁₈ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 Alkoxysilyl, C _1-20 ether, C _1-20 silyl ether, C _1-20 alkoxy, C _6-40 aryl, C _7-20 alkylaryl, or C _7-20 arylalkyl,

Q ₃ and Q ₄ are identical to each other and are C _2-20 alkyl.

In the present specification, the following terms may be defined as follows unless there is a specific limitation.

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

Alkyl having 1 to 20 carbon atoms (C _1-20 ) may be linear, branched or cyclic alkyl. Specifically, the alkyl having 1 to 20 carbon atoms is a linear alkyl having 1 to 20 carbon atoms; Straight chain alkyl having 1 to 15 carbon atoms; Straight chain alkyl having 1 to 5 carbon atoms; Branched or cyclic alkyl having 3 to 20 carbon atoms; Branched or cyclic alkyl having 3 to 15 carbon atoms; Or it may be a branched chain or cyclic alkyl having 3 to 10 carbon atoms. For example, the alkyl having 1 to 20 carbon atoms (C _1-20 ) is methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl , Cyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

Alkenyl having 2 to 20 carbon atoms (C _2-20 ) includes linear or branched alkenyl, and specifically allyl, allyl, ethenyl, propenyl, butenyl, pentenyl, etc. It is not limited only.

Examples of the alkoxy having 1 to 20 carbon atoms (C _1-20 ) include methoxy group, ethoxy, isopropoxy, n-butoxy, tert-butoxy, and cyclohexyloxy groups, but are not limited thereto. .

The alkoxyalkyl group having 2 to 20 carbon atoms (C _2-20 ) is a functional group in which at least one hydrogen of the above-described alkyl is substituted with alkoxy, specifically methoxymethyl, methoxyethyl, ethoxymethyl, iso-propoxymethyl, alkoxyalkyl such as iso-propoxyethyl, iso-propoxypropyl, iso-propoxyhexyl, tert-butoxymethyl, tert-butoxyethyl, tert-butoxypropyl, and tert-butoxyhexyl. It is not limited to this.

Examples of aryloxy having 6 to 40 carbon atoms (C _6-40 ) include phenoxy, biphenoxy, and naphthoxy, but are not limited thereto.

The aryloxyalkyl group having 7 to 40 carbon atoms (C _7-40 ) is a functional group in which at least one hydrogen of the above-described alkyl is substituted with aryloxy, and specifically, phenoxymethyl, phenoxyethyl, phenoxyhexyl, etc. may be mentioned. However, it is not limited to this.

Alkylsilyl having 1 to 20 (C _1-20 ) carbon atoms or alkoxysilyl group having 1 to 20 carbon atoms (C _1-20 ) is substituted with 1 to 3 hydrogens of -SiH ₃ as alkyl or alkoxy as described above. It is a substituted functional group, specifically, alkylsilyl, such as methylsilyl, dimethylsilyl, trimethylsilyl, dimethylethylsilyl, diethylmethylsilyl group, or dimethylpropylsilyl; Alkoxysilyl such as methoxysilyl, dimethoxysilyl, trimethoxysilyl or dimethoxyethoxysilyl; Alkoxyalkylsilyl such as methoxydimethylsilyl, diethoxymethylsilyl, or dimethoxypropylsilyl may be mentioned, but the present invention is not limited thereto.

Silylalkyl having 1 to 20 carbon atoms (C _1-20 ) is a functional group in which one or more hydrogens of alkyl as described above are substituted with silyl, specifically -CH ₂ -SiH ₃ , methylsilylmethyl or dimethylethoxysilylpropyl, etc. However, it is not limited thereto.

In addition, the alkylene having 1 to 20 carbon atoms (C _1-20 ) is the same as the above-described alkyl, except that it is a divalent substituent, specifically methylene, ethylene, propylene, butylene, pentylene, hexylene, hep Styrene, octylene, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, and the like, but are not limited thereto.

The aryl having 6 to 20 carbon atoms (C _6-20 ) may be a monocyclic, bicyclic or tricyclic aromatic hydrocarbon. As an example, the aryl having 6 to 20 carbon atoms (C _6-20 ) may include phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, etc., but is not limited thereto.

_Alkylaryl having 7 to 20 carbon atoms (C _7-20 ) may mean a substituent in which at least one hydrogen of the hydrogen of the aromatic ring is substituted by the above-described alkyl. As an example, the alkylaryl having 7 to 20 carbon atoms (C _7-20 ) may include methylphenyl, ethylphenyl, methylbiphenyl, methylnaphthyl, etc., but is not limited thereto.

The arylalkyl having 7 to 20 carbon atoms (C _7-20 ) may mean a substituent in which at least one hydrogen of the above-described alkyl is substituted by the above-described aryl. For example, the arylalkyl having 7 to 20 carbon atoms (C _7-20 ) may include phenylmethyl, phenylethyl, biphenylmethyl, naphthylmethyl, and the like, but is not limited thereto.

In addition, the arylene having 6 to 20 carbon atoms (C _6-20 ) is the same as the aryl described above, except that it is a divalent substituent, and specifically, phenylene, biphenylene, naphthylene, anthracenylene, phenanthrenylene , Fluorenylene, and the like, but are not limited thereto.

In addition, the Group 4 transition metal may be titanium (Ti), zirconium (Zr), hafnium (Hf), or rutherfordium (Rf), and specifically titanium (Ti), zirconium (Zr), or hafnium (Hf) May be, and more specifically, zirconium (Zr) or hafnium (Hf), but is not limited thereto.

In addition, the Group 13 element may be boron (B), aluminum (Al), gallium (Ga), indium (In), or thallium (Tl), specifically boron (B) or aluminum (Al), and However, it is not limited to this.

The above-described substituents are optionally a hydroxy group within a range exhibiting the same or similar effect as the desired effect; halogen; Alkyl or alkenyl, aryl, alkoxy; Alkyl or alkenyl, aryl, alkoxy containing at least one hetero atom among the heteroatoms of groups 14 to 16; Silyl; Alkylsilyl or alkoxysilyl; Phosphine group; Phosphide group; Sulfonate group; And it may be substituted with one or more substituents selected from the group consisting of a sulfone group.

On the other hand, the hybrid supported catalyst of the present invention exhibits high activity in propylene polymerization by hybridly supporting a first metallocene compound forming a double bond at the terminal and a second metallocene compound having high molecular weight characteristics during propylene polymerization. , The introduction of long chain branches (LCBs) into the polypropylene molecule has a useful feature in the production of polypropylene having a high melt tension.

Specifically, the first metallocene compound of Formula 1 contains S having an unshared electron pair in the ligand structure, so that electrons can be more abundantly provided to the metal atom, and thus the empty site of the transition metal included in the bridge group ( vacant site) can be stabilized. As a result, it is possible to induce beta-hydride elimination of the polymer chain to form a macromer having a double bond at the end, and in particular, a vinyl end group that can act as a monomer. By having a high ratio of (vinyl end groups), long chain branches (LCBs) can be introduced into the polypropylene molecule.

In general, in the presence of hydrogen, a polymer having a terminal group or end group saturated by hydrogen is produced upon chain termination. It can be seen that the formation of a polymer containing a double bond as an end group is caused by the structural characteristics of the catalyst.

The formation of a polymer having a double bond at the terminal is performed according to two mechanisms, either beta-hydrogen-elimination or beta-methyl-extraction, as shown in Scheme 1 below.

[Scheme 1]

In Scheme 1, M is a metal element, H is a hydrogen atom, and Me is methyl.

In general, beta-hydrogen-elimination occurs more easily, but since the vinylidene end group produced at this time is substituted by a substituent and loses its role as a monomer, a macromonomer Represents inactive. On the other hand, the vinyl end group generated by the beta-methyl removal reaction is active and may serve as a monomer.

Particularly, the first metallocene compound of Formula 1 includes S having an unshared electron pair in the ligand structure, so that electrons may be more abundantly provided to the metal atom. Accordingly, since the stability can be maintained even when the metal atom has a vacant site, a vinyl end group can be generated. In contrast, in the case of a conventional transition metal compound, when a metal atom has a vacant site, a metal-hydrogen bond is formed to become stable, thereby generating an inactive vinylidene end group. Accordingly, when the transition metal compound according to the present invention is used as a catalyst for preparing a polymer, it is possible to form a polymer having a high vinyl end group ratio and a low vinylidene end group ratio.

In addition, since the first metallocene compound of Formula 1 has two ligand structures different from each other, the first metallocene compound may have various characteristics or selective advantages of the other two ligands, and as a result, excellent catalytic activity Can represent.

In addition, in the case of the first ligand including a cyclopentadienyl group in which a binary ring structure including S is fused among the two ligands in the first metallocene compound of Formula 1, positions 2 and 3 are In the case of a second ligand each substituted with C _1-20 alkyl (R ₁ and R ₂ ) and having an indene structure or a structure in which an aliphatic ring is further fused to the benzene ring of the indene, position 2 is C _1-20 With alkyl (R ₃ ), position 4 is substituted with C _1-20 alkyl or unsubstituted C _6-20 aryl (R ₄ ), respectively. Accordingly, excellent catalytic activity can be exhibited by an inductive effect capable of sufficiently supplying electrons. In addition, when the first metallocene compound is used as a polymerization catalyst for polypropylene, the polypropylene molecular structure The melting point can be lowered by easily controlling the tacticity. In particular, R ₄ substituted at the 4th position of the second ligand includes an aryl group, thereby increasing the aromacity of the first metallocene compound to further enhance catalytic activity.

In addition, the first metallocene compound is a bridging group connecting two ligands, and by including a functional group A ₁ substituted by _{2 with} C _1-20 alkyl (Q ₁ and Q ₂ ), the atom size increases and the usable angle As is increased, the access of the monomer is easy and thus more excellent catalytic activity can be exhibited. In addition, Q ₁ and Q _{2, which} are the substituents of A ₁ , increase the solubility of the transition metal compound, thereby improving the supporting efficiency when prepared as a supported catalyst.

Meanwhile, the second metallocene compound represented by Chemical Formula 2 is a bridge group connecting two ligands including an indenyl group, and includes a divalent functional group A ₂ substituted with the same alkyl group having 2 or more carbon atoms, compared to the existing carbon bridge. As the atom size increases, as the usable angle increases, the access of the monomer is easy, and thus more excellent catalytic activity may be exhibited. In particular, since the second metallocene compound represented by Chemical Formula 2 has superior stereoregularity than the first metallocene compound represented by Chemical Formula 1, it is suitable for propylene polymerization and has excellent catalytic activity and has high molecular weight. It can play a role in polymerizing polymer chains.

Accordingly, the hybrid supported metallocene catalyst further comprises the second metallocene compound in addition to the first metallocene compound, that is, by including at least two or more different types of metallocene compounds, While exhibiting high activity in propylene polymerization, a long chain branch (LCB) can be introduced into the polypropylene molecule to prepare a polypropylene having excellent physical properties, particularly, improved melt tension.

Specifically, in Formula 1, Q ₁ and Q ₂ are the same as or different from each other, and may be C _1-6 or C _1-5 alkyl, specifically methyl, ethyl, or n-hexyl.

In addition, in Formula 1, Y ₁ and Y ₂ are each halogen, and specifically, may be chlorine.

And, in Formula 1, A ₁ may be silicon (Si).

In addition, in Formula 1, M ₁ may be zirconium (Zr) or hafnium (Hf), and specifically zirconium (Zr). Zr has more orbitals capable of accepting electrons than other Group 4 transition metals such as Hf, so it can easily bind to monomers with higher affinity, and as a result, exhibit better catalytic activity. I can. In addition, the Zr can improve the storage stability of the metal complex.

And, in Formula 1, R ₁ to R ₃ may each independently be C _1-20 , or C _1-12 , or C _1-6 linear or branched alkyl, more specifically methyl, ethyl, It may be a straight chain alkyl of C _1-6 or C _1-4 such as propyl or n-butyl. Even more specifically, R ₁ to R ₃ may each be methyl.

And, in Formula 1, R ₄ may be substituted with C _1-8 straight or branched alkyl or unsubstituted C _6-12 aryl, more specifically substituted with C _3-6 branched alkyl Or unsubstituted, phenyl or naphthyl. In addition, when substituted with the alkyl, the alkyl may be substituted with one or more, more specifically, one or two of the aryl. Specific examples of R ₆ may include phenyl, 4-(tert-butyl)phenyl, 3,5-di-(tert-butyl)phenyl, or naphthyl. In addition, the R ₄ is 4, corresponding to the case of a phenyl group, a phenyl C _3-6 bun for the R ₄ position and a para-substituted alkyl group is the location of the bound carbonyl groups substituted with a C _3-6 branched alkyl location Or it may be the meta position 3 or 5 position.

And, in Formula 1, R ₅ to R ₇ are each independently hydrogen, C _1-12 alkyl, C _2-12 alkenyl, C _6-18 aryl, C _7-20 alkylaryl, and Any one of C _7-20 arylalkyl, or two adjacent functional groups, such as R ₅ and R ₆ , or R ₆ and R ₇ are bonded to each other to each other, such as cyclopentyl, C _3-12 , or C _{4- 8} , or C _5-6 aliphatic cyclic group (or aliphatic cyclic structure) can be formed.

Further, in Formula 1, R ₈ is hydrogen, C _1-12 alkyl, C _2-12 alkenyl, C _6-12 aryl, C _7-15 alkylaryl, and C _7-15 arylalkyl Any one of, and more specifically, may be hydrogen or C _1-6 linear or branched alkyl. Specific examples include hydrogen, methyl, ethyl, propyl, n-butyl or t-butyl, and preferably hydrogen.

In addition, in Formula 1, X ₁ and X ₂ are each independently a single bond, S or CR _a R _b , but one of X ₁ and X ₂ may be S, and more specifically, X ₁ and X Any one of ₂ may be S, and the other may be a single bond. That is, X ₁ may be S, X ₂ may be a single bond, or X ₁ may be a single bond, and X ₂ may be S. In addition, when X ₁ or X ₂ is CR _a R _b , more specifically R _a and R _b are each independently hydrogen, C _1-10 alkyl, C _2-10 alkenyl, C _6-12 It may be any one of aryl of, C _7-13 alkylaryl, and arylalkyl of C _7-13 .

In addition, in Formula 1, Q ₁ and Q ₂ are each independently C _1-6 or C _1-5 straight-chain alkyl, more specifically methyl, ethyl, or n-hexyl, and R ₁ to R ₃ are each Independently, C _1-6 or C _1-4 straight-chain alkyl, more specifically, all of R ₁ to R ₃ are methyl, and R ₄ is unsubstituted or substituted with C _3-6 branched alkyl, Phenyl or naphthyl, more specifically phenyl, 4-tbutylphenyl, 3,5-di-tbutylphenyl, or naphthyl, and R ₅ to R ₇ are each independently hydrogen or R ₅ to R Two adjacent groups of ₇ may be bonded to each other to form a cyclopentyl group, and one of X ₁ and X ₂ may be S, and the other may be a single bond.

In addition, in Formula 1, A ₁ is silicon, M ₁ is zirconium, Q ₁ and Q ₂ are each independently C _1-6 or C _1-5 straight-chain alkyl, more specifically methyl, ethyl, Or n-hexyl, R ₁ to R ₃ are each independently C _1-6 or C _1-4 straight-chain alkyl, more specifically, all of R ₁ to R ₃ are methyl, and R ₄ is C _{3- 6} substituted or unsubstituted with branched alkyl, phenyl or naphthyl, more specifically phenyl, 4-tbutylphenyl, 3,5-di-tbutylphenyl, or naphthyl, and the R ₅ to R ₇ is each independently hydrogen or two adjacent groups of R ₅ to R ₇ may be bonded to each other to form a cyclopentyl group, and any one of X ₁ and X ₂ may be S, and the other may be a single bond. have. In addition, at this time, R ₈ may be hydrogen.

In addition, the first metallocene compound represented by Formula 1 may be represented by one of the following structural formulas.

.

.

Meanwhile, the hybrid supported metallocene catalyst of the present invention further comprises the second metallocene compound in addition to the first metallocene compound described above.

Specifically, in Formula 2, Y ₃ and Y ₄ are each halogen, and specifically, may be chlorine.

In addition, in Formula 2, A ₂ may be silicon (Si).

In addition, in Formula 2, M ₂ may be zirconium (Zr) or hafnium (Hf), and specifically, zirconium (Zr). Zr has more orbitals capable of accepting electrons than other Group 4 transition metals such as Hf, so it can easily bind to monomers with higher affinity, and as a result, exhibit better catalytic activity. I can. In addition, the Zr can improve the storage stability of the metal complex.

And, in Formula 2, R ₉ and R ₁₄ are each independently C _1-20 , or C _1-6 , or C _1-4 straight or branched alkyl or C _6-20 , or C _6-12 It may be an aryl of, and more specifically, it may be a straight-chain or branched alkyl of C _1-6 or C _1-4 such as methyl, ethyl, or i-propyl. Even more specifically, R ₉ and R ₁₄ may each be methyl.

And, in Formula 2, the R ₁₁ to R ₁₃ and R ₁₆ to R ₁₈ are each independently hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, Trimethylsilylmethyl, or the R ₁₁ to R ₁₃ and R ₁₆ to R ₁₈ Among them, two or more adjacent to each other are preferably unsubstituted or substituted with methyl or phenyl, but are not limited thereto.

In addition, in Formula 2, R ₁₀ and R ₁₅ may each be C _6-12 aryl substituted or unsubstituted with C _1-8 linear or branched alkyl, and more specifically, C _3-6 It may be phenyl or naphthyl, unsubstituted or substituted with branched alkyl. Specific examples of R ₁₀ and R ₁₅ may be a phenyl group substituted with a C _3-6 branched alkyl group, preferably tert-butylphenyl. In addition, the R ₁₀ and R ₁₅ is C _3-6 mins if a phenyl group substituted with alkyl group, C _3-6 bun substitution position of alkyl group on the phenyl group R ₁₀ and R ₁₅ are carbonyl groups inde combined position and para It may be the 4th position corresponding to the position.

And, in Formula 2, Q ₃ and Q ₄ are the same, and may be a C _2-4 straight-chain alkyl group, preferably ethyl.

In addition, in Formula 2, Q ₃ and Q ₄ are the same, C _2-4 straight-chain alkyl, more specifically Q ₃ and Q ₄ are ethyl, and R ₉ and R ₁₄ are each independently C _{1 -6} or C _1-3 straight or branched alkyl, more specifically, both R ₉ and R ₁₄ are methyl, and R ₁₀ and R ₁₅ are phenyl substituted with C _3-6 branched alkyl, more Specifically, it is 4-tbutylphenyl, and R ₁₁ to R ₁₃ and R ₁₆ to R ₁₈ are each independently hydrogen or C _1-3 linear or branched alkyl, more specifically R ₁₁ to R ₁₃ and R ₁₆ to R ₁₈ may be hydrogen.

In addition, in Formula 2, A ₂ is silicon, M ₂ is zirconium, Q ₃ and Q ₄ are the same, C _2-4 straight-chain alkyl, more specifically Q ₃ and Q ₄ are ethyl And R ₉ and R ₁₄ are each independently C _1-6 or C _1-3 linear or branched alkyl, more specifically, both R ₉ and R ₁₄ are methyl, and R ₁₀ and R ₁₅ are C Phenyl substituted with _3-6 branched alkyl, more specifically 4-tbutylphenyl, wherein R ₁₁ to R ₁₃ and R ₁₆ to R ₁₈ are each independently hydrogen or C _1-3 linear or branched Alkyl, more specifically, the R ₁₁ to R ₁₃ and R ₁₆ to R ₁₈ may be hydrogen.

In addition, in Formula 2, the second metallocene compound may be a compound represented by the following structural formula, but is not limited thereto.

.

.

Meanwhile, in the present invention, the first metallocene compound and the second metallocene compound may each be a meso isomer, a racemic isomer, or a mixed form thereof.

In the present specification, "racemic form" or "racemic form" or "racemic isomer" means that the same substituent on two cyclopentadienyl moieties is M ₁ or M ₂ in Formula 1 or Formula ₂ It refers to a plane including a transition metal, such as zirconium (Zr) or hafnium (Hf), and a shape on the opposite side to the center of the cyclopentadienyl portion.

And, in the present specification, the term "meso isomer" or "meso isomer" is a stereoisomer of the above-described racemic isomer, and the same substituents on two cyclopentadienyl moieties are used in Formula 1 or Formula 2 The transition metal represented by M ₁ or M ₂ refers to a plane including a transition metal such as zirconium (Zr) or hafnium (Hf) and a shape on the same side with respect to the center of the cyclopentadienyl portion.

In the hybrid supported metallocene catalyst of the present invention, the first metallocene compound and the second metallocene compound may be supported in a molar ratio of about 1:1 to about 1:8. If the supported ratio is less than about 1:1, only the first metallocene compound plays a leading role, and the stereoregularity is remarkably inferior during propylene polymerization, becomes a sticky form, and polymer formation itself may be difficult. In addition, when the loading ratio exceeds about 1:8, only the second metallocene compound plays a leading role, so that the content of long chain branches (LCBs) in the polypropylene molecule is lowered, and the melt tension may be lowered.

Specifically, the first metallocene compound and the second metallocene compound are a mixed supported metal supported in a molar ratio of about 1:1 to about 1:6, or a molar ratio of about 1:1 to about 1:5. While the strong catalyst exhibits high activity in propylene polymerization, it is preferable to introduce a long-chain branch (LCB) into the polypropylene molecule to prepare a polypropylene having excellent physical properties, particularly, improved melt tension.

That is, in the case of the hybrid supported metallocene catalyst of the present invention in which the first metallocene compound and the second metallocene compound are supported in the molar ratio, the melt tension of polypropylene due to the interaction of two or more catalysts Can be further improved.

In the hybrid supported metallocene catalyst of the present invention, as a carrier for supporting the first metallocene compound and the second metallocene compound, a carrier containing a hydroxy group on the surface may be used, and preferably dried. It may contain a highly reactive hydroxyl group and a siloxane group on the surface from which moisture has been removed from the surface.

For example, silica dried at high temperature, silica-alumina, and silica-magnesia may be used, and these are usually oxides, carbonates, such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg(NO ₃ ) ₂ , It may contain sulfate and nitrate components.

The drying temperature of the carrier is preferably about 200 ^o C to about 800 ^o C, more preferably about 300 ^o C to about 600 ^o C, and most preferably about 300 ^o C to about 400 ^o C. When the drying temperature of the carrier is less than 200 ^o C, there is too much moisture, so that the moisture on the surface and the cocatalyst to be described later react, and when it exceeds 800 ^o C, the pores on the surface of the carrier merge and the surface area decreases. It is not preferable because many hydroxy groups disappear and only siloxane groups remain, so that the reaction site with the cocatalyst decreases.

The amount of hydroxy group on the surface of the carrier is preferably about 0.1 mmol/g to about 10 mmol/g, and more preferably about 0.5 mmol/g to about 5 mmol/g. The amount of hydroxy groups on the surface of the carrier can be controlled by a method and conditions for preparing the carrier or drying conditions such as temperature, time, vacuum or spray drying.

If the amount of the hydroxy group is less than about 0.1 mmol/g, the reaction site with the cocatalyst is small, and if it exceeds about 10 mmol/g, it may be due to moisture other than the hydroxy group present on the surface of the carrier particle. Not desirable.

In addition, the hybrid supported metallocene catalyst may be one in which at least one type of the first metallocene compound and at least one type of the second metallocene compound are supported on a carrier together with a cocatalyst compound. The cocatalyst may be used as long as it is a cocatalyst used when polymerizing olefins under a general metallocene catalyst. This cocatalyst allows the formation of a bond between the hydroxy group in the carrier and the Group 13 transition metal. In addition, since the cocatalyst exists only on the surface of the carrier, it may contribute to securing the intrinsic characteristics of the specific hybrid catalyst configuration of the present application without a fouling phenomenon in which polymer particles are entangled with each other or the reactor wall surface.

Specifically, the hybrid supported metallocene catalyst may further include at least one cocatalyst selected from the group consisting of compounds represented by the following Formulas 3 to 5:

[Formula 3]

-[Al(R ₃₁ )-O] _c-

In Chemical Formula 3,

Each R ₃₁ is independently halogen, C _1-20 alkyl or C _1-20 haloalkyl,

c is an integer greater than or equal to 2,

[Formula 4]

D(R ₄₁ ) ₃

In Chemical Formula 4,

D is aluminum or boron,

Each R ₄₁ is independently hydrogen, halogen, C _1-20 hydrocarbyl or C _1-20 hydrocarbyl substituted with halogen,

[Formula 5]

^{[LH] + [Q (E} ) 4] - or ^{[L] + [Q (E} ) 4] -

In Chemical Formula 5,

L is a neutral or cationic Lewis base,

[LH] ⁺ is Bronsted acid,

Q is Br ³⁺ or Al ³⁺ ,

E is each independently C _6-40 aryl or C _1-20 alkyl, wherein the C _6-40 aryl or C _1-20 alkyl is unsubstituted or halogen, C _1-20 alkyl, C _1-20 alkoxy and It is substituted with one or more substituents selected from the group consisting of phenoxy.

The compound represented by Formula 3 may be, for example, an alkyl aluminoxane such as modified methylaluminoxane (MMAO), methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like.

The alkyl metal compound represented by Formula 4 is, for example, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, dimethyl isobutyl aluminum, dimethyl ethyl aluminum, diethyl chloro. Aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl It may be aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like.

The compound represented by Formula 5 is, for example, triethyl ammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium tetra (p- Tolyl) boron, tripropylammonium tetra (p-tolyl) boron, triethyl ammonium tetra (o,p-dimethylphenyl) boron, trimethyl ammonium tetra (o,p-dimethylphenyl) boron, tributyl ammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenyl boron, N,N-diethylanilinium tetraphenyl boron, N, N-diethylanilinium tetraphenyl boron, N,N-diethylanilinium tetrapentafluorophenyl boron, diethylammonium tetrapentafluorophenyl boron, triphenylphosphonium tetraphenyl boron, trimethylphosphonium tetra Phenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra (p-tolyl) aluminum, tripropyl ammonium tetra (p-tolyl) aluminum, triethyl ammonium tetra (o,p-dimethylphenyl) aluminum, tributyl ammonium tetra (p-trifluoromethylphenyl) aluminum, trimethyl ammonium tetra (p-trifluoromethylphenyl) aluminum ,Tributylammonium tetrapentafluorophenylaluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylanilinium tetrapentafluoro Rophenyl aluminum, diethyl ammonium tetrapentafluorophenyl aluminum, triphenyl phosphonium tetraphenyl aluminum, trimethyl phosphonium tetraphenyl aluminum, triphenyl carbonium tetraphenyl boron, triphenyl carbonium tetraphenyl aluminum, triphenyl Carbonium tetra(p-trifluoromethylphenyl) boron, triphenylcarbonium tetrapentafluorophenyl boron, and the like.

In addition, the hybrid supported metallocene catalyst may include the cocatalyst and the first metallocene compound in a molar ratio of about 1:1 to about 1:10000, and preferably about 1:1 to about 1:1000 It may be included in a molar ratio of, more preferably, it may be included in a molar ratio of about 1:10 to about 1:100.

In addition, the hybrid supported metallocene catalyst may also include the cocatalyst and the second metallocene compound in a molar ratio of about 1:1 to about 1:10000, and preferably about 1:1 to about 1:1000 It may be included in a molar ratio of, more preferably, it may be included in a molar ratio of about 1:10 to about 1:100.

At this time, if the molar ratio is less than about 1, the metal content of the cocatalyst is too small, so that the catalytically active species are not well made, so that the activity may be lowered.If the molar ratio exceeds about 10000, there is a concern that the metal of the cocatalyst acts as a catalyst poison. have.

The supported amount of this cocatalyst may be from about 5 mmol to about 20 mmol based on 1 g of the carrier.

On the other hand, the hybrid supported metallocene catalyst, the step of supporting a cocatalyst on a carrier; Supporting the first metallocene compound on the carrier on which the cocatalyst is supported; And supporting a second metallocene compound on a carrier on which the cocatalyst and the first metallocene compound are supported.

Alternatively, the hybrid supported metallocene catalyst may include: supporting a cocatalyst on a carrier; Supporting a second metallocene compound on a carrier on which the cocatalyst is supported; And supporting the first metallocene compound on a carrier on which the cocatalyst and the second metallocene compound are supported.

Also alternatively, the hybrid supported metallocene catalyst comprises: supporting a first metallocene compound on a carrier; Supporting a cocatalyst on a carrier on which the first metallocene compound is supported; And supporting a second metallocene compound on a carrier on which the cocatalyst and the first metallocene compound are supported.

In the above method, the loading conditions are not particularly limited and can be performed within a range well known to those skilled in the art. For example, it can be carried out by appropriately using high-temperature support and low-temperature support, for example, the support temperature is possible in the range of about -30 ^o C to about 150 ^o C, and preferably about 50 ^o C to about 98 ^o C, or from about 55 ^o C to about 95 ^o C. The loading time may be appropriately adjusted according to the amount of the first metallocene compound to be supported. The reacted supported catalyst may be used as it is by filtration of the reaction solvent or distillation under reduced pressure, and if necessary, a Soxhlet filter with an aromatic hydrocarbon such as toluene may be used.

And, the preparation of the supported catalyst may be carried out in a solvent or no solvent. When a solvent is used, the usable solvents include aliphatic hydrocarbon solvents such as hexane or pentane, aromatic hydrocarbon solvents such as toluene or benzene, hydrocarbon solvents substituted with chlorine atoms such as dichloromethane, diethyl ether or tetrahydrofuran (THF ), and most organic solvents such as acetone and ethyl acetate, and hexane, heptane, toluene, or dichloromethane is preferred.

In the present invention, in the method of producing a metallocene compound or a supported catalyst, the equivalent (eq) means a molar equivalent (eq/mol).

Meanwhile, the present invention provides a method for producing polypropylene, comprising polymerizing a propylene monomer in the presence of the hybrid supported metallocene catalyst.

The polymerization reaction may be carried out by single polymerization of propylene using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.

And, the polymerization temperature is about 25 ^o C to about 500 ^o C, or about 25 ^o C to about 300 ^o C, or about 30 ^o C to about 200 ^o C, or about 50 ^o C to about 150 ^o C, or It may be from about 60 ^o C to about 120 ^o C. In addition, the polymerization pressure is from about 1 kgf/cm2 to about 100 kgf/cm2, or from about 1 kgf/cm2 to about 50 kgf/cm2, or from about 5 kgf/cm2 to about 45 kgf/cm2, or from about 10 kgf/cm2 It may be about 40 kgf/cm 2, or about 15 kgf/cm 2 to about 35 kgf/cm 2.

The supported metallocene catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, hexane, heptane, nonane, decane, and isomers thereof, and an aromatic hydrocarbon solvent such as toluene and benzene, and dichloromethane and chlorobenzene. It can be dissolved or diluted in a hydrocarbon solvent substituted with a chlorine atom and injected. The solvent used here is preferably used after removing a small amount of water or air, which acts as a catalyst poison, by treating a small amount of alkyl aluminum, and it is possible to further use a cocatalyst.

In particular, the hybrid supported metallocene catalyst according to the present invention exhibits high activity in propylene polymerization, and is useful for producing polypropylene having excellent physical properties, particularly improved melt tension by introducing long-chain branches (LCB) into the polypropylene molecule. Specifically, the hybrid supported metallocene polypropylene of the present invention by using a catalyst precursor of Formula 1 for synthesizing a macromer that forms a double bond at the terminal and a catalyst precursor of Formula 2 exhibiting high molecular weight properties during propylene polymerization. The introduction of long chain branches (LCB) in the molecule has an advantage in securing a high melt tension.

For example, the polymerization step, based on the propylene monomer content, hydrogen gas of about 1500 ppm or less or about 200 ppm to about 1500 ppm, about 1000 ppm or less or about 250 ppm to about 1000 ppm, or about 850 ppm or less or about 300 ppm To about 850 ppm.

In such a propylene polymerization process, the transition metal compound of the present invention can exhibit high catalytic activity. As an example, the catalytic activity during propylene polymerization is calculated as the ratio of the weight (kg PP) of the produced polypropylene per the mass (g) of the supported catalyst used based on the unit time (h), about 7.8 kg PP/g cat·hr or more or about 7.8 kg PP/g·cat·hr to about 50 kg PP/g·cat·hr, and specifically 8.5 kg PP/g·cat·hr or more or about 8.5 kg PP/g· cat·hr to about 40 kg PP/g·cat·hr, specifically 9.5 kg PP/g·cat·hr or more or about 9.5 kg PP/g·cat·hr to about 35 kg PP/g·cat·hr days I can.

In addition, the polymerization step may be a homopolymerization reaction in which a propylene monomer is independently polymerized.

The present invention exhibits high catalytic activity in the polymerization process using a mixed supported metallocene catalyst in which at least two metallocene compounds having a specific substituent and structure as described above are supported on a carrier during polypropylene polymerization, and polypropylene By introducing long-chain branches in the molecule, the melt tension can be significantly improved. Polypropylene having such characteristics can produce products of various grades in a wide range of applications according to hydrogen reactivity.

For example, the polypropylene has a melting point (Tm) of 150°C or less or 115°C to 150°C, or 148°C or less or 118°C to 148°C, or 145°C or less or 120°C to 145°C, or 140°C or less or 125 It may be from ℃ to 140 ℃. The polypropylene may have a melting point (Tm) of 150° C. or less in terms of exhibiting high melt tension through the introduction of long chain branches (LCB) into the polymer molecule. However, in terms of preventing fouling from occurring in the polymerization process, the melting point (Tm) of the polypropylene may be 115°C or higher.

In the present invention, the melting point (Tm) can be measured using a Differential Scanning Calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument). Specifically, after heating the polypropylene polymer to 200 °C by increasing the temperature, it was maintained at that temperature for 5 minutes, then lowered to 30 °C, and the temperature was increased again to obtain a DSC (Differential Scanning Calorimeter, manufactured by TA) curve. The temperature corresponding to the top is the melting point (Tm). At this time, the rate of rise and fall of the temperature is 10 °C/min, and the melting point (Tm) is expressed as the result measured in the section where the second temperature rises and falls. The specific method of measuring the melting point (Tm) is as described in the test examples described later.

In addition, the polypropylene may have a Pentad sequence distribution (mmmm) of 60% to 95.8%, or 65% to 95.5%, or 70% to 95%, or 75% to 94.5%. The polypropylene effectively controls the tacticity of the molecular structure of the polymer through the introduction of long chain branches (LCB) into the molecule and improves the melting tension, in terms of improving the melting tension, the three-dimensional regularity (Pentad sequence distribution, mmmm) in the above-described range. Can keep.

In the present invention, the three-dimensional regularity (Pentad sequence distribution, mmmm) can be measured using quantitative nuclear magnetic resonance (NMR) spectroscopy. Specifically, after measuring the sequence distribution at the pentad level by ¹³ C-NMR analysis, it is expressed as a% of the pentad (mmmm) sequence having stereoregularity for all pentad sequences. will be. mmmm% is a value based on moles. The method of measuring a specific three-dimensional regularity (Pentad sequence distribution, mmmm) is as described in Test Examples to be described later.

The hybrid supported metallocene catalyst according to the present invention exhibits high activity in propylene polymerization and has an excellent effect of producing polypropylene having a high melt tension by introducing long chain branches into the polypropylene molecule.

Hereinafter, the functions and effects of the invention will be described in more detail through specific embodiments of the invention. However, these embodiments are only presented as examples of the invention, and the scope of the invention is not determined thereby.

[Example]

<Preparation of the first metallocene compound>

Synthesis Example 1

1-1 Ligand compound (1,2-dimethyl-3H-benzo[d]cyclopenta[b]thiophen-3-yl)dimethyl(2-methyl-4-(4'-tert-butylphenyl)-1H-inden-1 Preparation of -yl)silane

In the reactor, 1 equivalent of 1,2-dimethyl-3H-benzo[d]cyclopenta[b]thiophene (1,2-dimethyl-3H-benzo[d]cyclopenta[b]thiophene) was added to tetrahydrofuran (THF). After dissolving (0.7 M), n-butyllithium (n-BuLi, 1.05 eq) was slowly added dropwise at -25 ^o C, followed by stirring at room temperature for 3 hours. Thereafter, dichlorodimethylsilane (1.05 eq) was added at -10 ^o C, and then stirred at room temperature for 24 hours to prepare a mono-Si solution.

Separately, in another reactor, 1 equivalent of 4-(4'-tert-butylphenyl)-2-methyl-1H-indene (4-(4'-tert-butylphenyl)-2-methyl-1H-indene) was added to toluene. It was dissolved in a mixed solvent of and THF (mixed volume ratio=5:1, 0.7 M), n-BuLi (1.05 eq) was slowly added dropwise at -25 ^o C, and then stirred at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added and stirred for 30 minutes, and the mono-Si solution prepared above was added in the same amount. Thereafter, the mixture was stirred at room temperature for 24 hours, worked-up with water, and dried to obtain a ligand compound.

1-2 transition metal compounds (1,2-dimethyl-3H-benzo[d]cyclopenta[b]thiophen-3-yl) dimethyl(2-methyl-4-(4'-tert-butylphenyl)-1H-inden- Preparation of 1-yl)silane zirconium dichloride

The ligand compound prepared above was dissolved in a mixed solvent of toluene and ether (mixed volume ratio = 2: 1, 0.7 M), and n-BuLi (2.05 eq) was added at -25 ^o C, followed by 5 at room temperature. Stir for hours.

In a separate flask, ZrCl ₄ (1 eq) was mixed with toluene (0.17 M) to prepare a slurry, and the prepared slurry was added to the ligand solution, followed by stirring at room temperature overnight.

When the reaction was completed, the solvent was dried in vacuo and dichloromethane was re-introduced, followed by filtration to remove LiCl. After drying the filtrate under vacuum, toluene was added and recrystallized at room temperature. Then, the resulting solid was filtered and dried in vacuo to obtain the title transition metal compound.

¹ H-NMR (CDCl ₃ , 500 MHz): 0.66 (4H, m), 0.94 (6H, t), 1.33 (9H, s), 1.79 (6H, s), 2.12 (3H, s), 6.36 (1H , s), 7.30-7.49 (8H, m), 7.93 (1H, d), 8.05 (1H, d), 8.29 (1H, d)

Synthesis Example 2

Instead of 4-(4'-tert-butylphenyl)-2-methyl-1H-indene (4-(4'-tert-butylphenyl)-2-methyl-1H-indene) as a reactant in Synthesis Example 1, 4-(3',5'-di-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacene (4-(3',5'-di-tert- Except for the use of butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacene), it was carried out in the same manner as in Synthesis Example 1 to prepare a transition metal compound having the structure of the title I did.

¹ H-NMR (CDCl ₃ , 500 MHz): 0.22 (6H, s), 1.33 (18H, s) 1.79 (6H, s), 1.95 (2H, q), 2.30 (3H, s) 2.97-3.02 (4H , m), 6.44 (1H, s), 7.38-7.48 (3H, m), 7.73 (1H, d), 7.95 (1H, d) 8.01 (1H, d)

Synthesis Example 3

Instead of 4-(4'-tert-butylphenyl)-2-methyl-1H-indene (4-(4'-tert-butylphenyl)-2-methyl-1H-indene) as a reactant in Synthesis Example 1, Except for the use of 2-methyl-4-naphthy-1H-indene, it was carried out in the same manner as in Synthesis Example 1, and the transition having the structure of the title A metal compound was prepared.

¹ H-NMR (CDCl ₃ , 500 MHz): 0.66 (4H, m), 0.94 (6H, t), 1.79 (6H, s), 2.12 (3H, s), 6.36 (1H, s), 7.39-7.52 (6H, m), 7.77 (1H, t), 7.93 (1H, d), 8.05-8.09 (2H, m), 8.20 (1H, d), 8.29 (1H, d), 8.50 (1H, d), 8.95 (1H,d)

Synthesis Example 4

Instead of 4-(4'-tert-butylphenyl)-2-methyl-1H-indene (4-(4'-tert-butylphenyl)-2-methyl-1H-indene) as a reactant in Synthesis Example 1, A transition metal having the title structure was carried out in the same manner as in Synthesis Example 1, except that 2-methyl-4-phenyl-1H-indene was used. The compound was prepared.

¹ H-NMR (CDCl ₃ , 500 MHz): 0.21 (6H, s), 1.79 (6H, s), 2.12 (3H, s), 6.36 (1H, s), 7.41-7.51 (9H, m), 7.93 (1H, d), 8.05 (1H, d), 8.29 (1H, d)

Synthesis Example 5

Instead of 4-(4'-tert-butylphenyl)-2-methyl-1H-indene (4-(4'-tert-butylphenyl)-2-methyl-1H-indene) as a reactant in Synthesis Example 1, 4-(3',5'-di-tert-butylphenyl)-2-methyl-1H-indene (4-(3',5'-di-tert-butylphenyl)-2-methyl-1H-indene) Except for using, it was carried out in the same manner as in Synthesis Example 1 to prepare a transition metal compound having the title structure.

¹ H-NMR (CDCl ₃ , 500 MHz): 0.66 (4H, m), 0.94 (6H, t), 1.32 (18H, s) 1.79 (6H, s), 2.12 (3H, s), 6.36 (1H, s), 7.42-7.55 (5H, m), 7.73 (2H, s), 7.93 (1H, d), 8.05 (1H, d), 8.29 (1H, d)

Synthesis Example 6

Instead of 4-(4'-tert-butylphenyl)-2-methyl-1H-indene (4-(4'-tert-butylphenyl)-2-methyl-1H-indene) as a reactant in Synthesis Example 1, 4-naphthyl-2-methyl-1,5,6,7-tetrahydro-s-indacene (4-naphthyl-2-methyl-1,5,6,7-tetrahydro-s-indacene) Except that, by performing the same method as in Synthesis Example 1, a transition metal compound having the title structure was prepared.

¹ H-NMR (CDCl ₃ , 500 MHz): 0.21 (6H, s) 1.79 (6H, s), 1.94 (2H, q), 2.12 (3H, s) 2.85-2.90 (4H, m), 6.36 (1H , s), 7.30-7.52 (5H, m), 7.75 (1H, m), 7.93 (1H, d), 8.01-8.05 (2H, m), 8.20 (1H, d), 8.50 (1H, d), 8.95 (1H, d)

Synthesis Example 7

Instead of 4-(4'-tert-butylphenyl)-2-methyl-1H-indene (4-(4'-tert-butylphenyl)-2-methyl-1H-indene) as a reactant in Synthesis Example 1, 4-phenyl-2-methyl-1,5,6,7-tetrahydro-s-indacene (4-phenyl-2-methyl-1,5,6,7-tetrahydro-s-indacene) Except, it was carried out in the same manner as in Synthesis Example 1, to prepare a transition metal compound having the title structure.

¹ H-NMR (CDCl ₃ , 500 MHz): 0.23 (6H, s) 1.77 (6H, s), 1.98 (2H, q), 2.26 (3H, s) 2.97-3.02 (4H, m), 6.40 (1H , s), 7.32-7.52 (8H, m), 7.83 (1H, d), 8.05 (1H, m)

Synthesis Example 8

Instead of 4-(4'-tert-butylphenyl)-2-methyl-1H-indene (4-(4'-tert-butylphenyl)-2-methyl-1H-indene) as a reactant in Synthesis Example 1, 4-(4'-tert-butylphenyl)-2-methyl-1,5,6,7-tetrahydro-s-indacene (4-(4'-tert-butylphenyl)-2-methyl-1,5 ,6,7-tetrahydro-s-indacene) was carried out in the same manner as in Synthesis Example 1, to prepare a transition metal compound having the structure of the title.

¹ H-NMR (CDCl ₃ , 500 MHz): 0.22 (6H, s), 1.33 (9H, s) 1.79 (6H, s), 1.95 (2H, q), 2.30 (3H, s) 2.97-3.02 (4H , m), 6.44 (1H, s), 7.38-7.48 (5H, m), 7.73 (1H, d), 8.01 (1H, d)

Synthesis Example 9

Instead of 1,2-dimethyl-3H-benzo[d]cyclopenta[b]thiophene in Synthesis Example 1, 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene (1,2 Except for the use of -dimethyl-3H-benzo[b]cyclopenta[d]thiophene), it was carried out in the same manner as in Synthesis Example 1, to prepare a transition metal compound having the title structure.

¹ H-NMR (CDCl ₃ , 500 MHz): 0.24 (6H, s), 1.40 (9H, s), 1.79 (6H, s), 2.12 (3H, s), 6.36 (1H, s), 7.30-7.51 (8H, m), 7.70 (1H, d), 7.90 (1H, d), 8.10 (1H, d)

Synthesis Example 10

As a reactant in Synthesis Example 2, In place of 1,2-dimethyl-3H-benzo[d]cyclopenta[b]thiophene, 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene (1,2-dimethyl-3H- Except for the use of benzo[b]cyclopenta[d]thiophene), it was carried out in the same manner as in Synthesis Example 2, to prepare a transition metal compound having the title structure.

¹ H-NMR (CDCl ₃ , 500 MHz): 0.23 (6H, s), 1.32 (18H, s), 1.75 (6H, s), 1.90 (2H, q), 2.28 (3H, s), 2.85 (4H , m), 6.35 (1H, s), 7.45-7.49 (3H, m), 7.74 (3H, m), 7.90 (1H, d)

Synthesis Example 11

Instead of 1,2-dimethyl-3H-benzo[d]cyclopenta[b]thiophene in Synthesis Example 3, 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene (1,2 Except for using -dimethyl-3H-benzo[b]cyclopenta[d]thiophene), it was carried out in the same manner as in Synthesis Example 3, to prepare a transition metal compound having the title structure.

¹ H-NMR (CDCl ₃ , 500 MHz): 0.21 (6H,s), 1.79 (6H, s), 2.18 (6H, s), 6.95 (1H, s), 7.323-7.42 (6H, m), 7.73 -7.79 (2H, m), 7.95 (1H, d), 8.10 (1H, d), 8.18 (1H, d), 8.25 (1H, d), 8.38 (1H, d), 8.59 (1H, d)

Synthesis Example 12

As a reactant in Synthesis Example 4, In place of 1,2-dimethyl-3H-benzo[d]cyclopenta[b]thiophene, 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene (1,2-dimethyl-3H- Except for the use of benzo[b]cyclopenta[d]thiophene), it was carried out in the same manner as in Synthesis Example 4 to prepare a transition metal compound having the title structure.

¹ H-NMR (CDCl ₃ , 500 MHz): 0.24 (6H,s), 1.79 (6H, s), 2.20 (3H, s), 7.30-7.49 (9H, m), 7.79 (1H, d), 7.93 (1H, d), 8.10 (1H, d)

Synthesis Example 13

Instead of 1,2-dimethyl-3H-benzo[d]cyclopenta[b]thiophene as a reactant in Synthesis Example 5, 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene ( Except for the use of 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene), it was carried out in the same manner as in Synthesis Example 5, to prepare a transition metal compound having the title structure.

¹ H-NMR (CDCl ₃ , 500 MHz): 0.24 (6H,s), 1.35 (18H, s), 1.70 (6H, s), 2.17 (3H, s), 6.29 (1H, s), 7.30-7.43 (5H, m), 7.74 (1H, d), 7.80 (1H, d), 8.17 (1H, d)

Synthesis Example 14

As a reactant in Synthesis Example 6, In place of 1,2-dimethyl-3H-benzo[d]cyclopenta[b]thiophene, 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene (1,2-dimethyl-3H- Except for the use of benzo[b]cyclopenta[d]thiophene), it was carried out in the same manner as in Synthesis Example 6 to prepare a transition metal compound having the structure of the title.

¹ H-NMR (CDCl ₃ , 500 MHz): 0.20 (6H,s), 1.74 (6H, s), 1.95 (2H, q), 2.18 (3H, s), 2.80 (4H, m), 6.37 (1H) , s), 7.40-7.43 (5H, m), 7.70 (2H, m), 7.90 (1H, d), 7.99 (1H, d), 8.17 (1H, d), 8.45 (1H, d), 8.79 ( 1H, d)

Synthesis Example 15

Instead of 1,2-dimethyl-3H-benzo[d]cyclopenta[b]thiophene as a reactant in Synthesis Example 7, 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene ( Except for the use of 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene), a transition metal compound having the title structure was prepared in the same manner as in Synthesis Example 7.

¹ H-NMR (CDCl ₃ , 500 MHz): 0.25 (6H,s), 1.79 (6H, s), 1.89 (2H, q), 2.18 (3H, s), 2.80 (4H, m), 6.35 (1H , s), 7.39-7.43 (8H, m), 7.74 (1H, d), 7.93 (1H, d)

Synthesis Example 16

Instead of 1,2-dimethyl-3H-benzo[d]cyclopenta[b]thiophene as a reactant in Synthesis Example 8, 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene ( Except for the use of 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene), it was carried out in the same manner as in Synthesis Example 8, to prepare a transition metal compound having the title structure.

¹ H-NMR (CDCl ₃ , 500 MHz): 0.22 (6H, s), 1.33 (9H, s), 1.71 (6H, s), 1.95 (2H, q), 2.28 (3H, s), 2.85 (4H , m), 6.35 (1H, s), 7.30-7.43 (7H, m), 7.74 (1H, d), 7.90 (1H, d)

Synthesis Example 17

In Synthesis Example 1, a transition metal compound having the title structure was prepared by performing the same method as in Synthesis Example 1, except that dichlorodiethylsilane was used instead of dichlorodimethylsilane. I did.

¹ H-NMR (CDCl ₃ , 500MHz): 0.66 (4H, m), 0.94 (6H, t), 1.33 (9H, s), 1.79 (6H, s), 2.12 (3H, s), 6.36 (1H, s), 7.30-7.49 (8H, m), 7.93 (1H, d), 8.05 (1H, d), 8.29 (1H, d)

Synthesis Example 18

In Synthesis Example 1, a transition metal compound having the title structure was prepared by performing the same method as in Synthesis Example 8, except that dichlorohexylmethylsilane was used instead of dichlorodimethylsilane. I did.

¹ H-NMR (CDCl ₃ , 500 MHz): 0.21 (3H, s), 0.60 (2H, t), 0.88 (2H, t), 1.23-1.29 (6H, m), 1.33 (9H, s), 1.79 (6H, s), 2.12 (3H, s), 6.36 (1H, s), 7.30-7.49 (8H, m), 7.93 (1H, d), 8.05 (1H, d), 8.29 (1H, d)

<Preparation of the second metallocene compound>

Synthesis Example 19

Preparation of 19-1 (diethylsilane-diyl)-bis((2-methyl-4-tert-butyl-phenylindenyl)silane

After dissolving 2-methyl-4-tert-butyl-phenylindene (20.0 g) in a toluene/THF=10/1 solution (220 mL), n-butyllithium solution (2.5 M, hexane solvent, 22.2 g) Was slowly added dropwise at 0 ^o C, and then stirred at room temperature for one day. Then, diethyldichlorosilane (6.2 g) was slowly added dropwise to the mixed solution at -78 degrees Celsius ( ^o C), stirred for about 10 minutes, and then stirred at room temperature for one day. Thereafter, water was added to separate the organic layer, and the solvent was distilled under reduced pressure to obtain (diethylsilane-diyl)-bis((2-methyl-4-tert-butyl-phenylindenyl)silane.

19-2 Preparation of [(diethylsilane-diyl)-bis((2-methyl-4-tert-butyl-phenylindenyl)]zirconium dichloride

After dissolving (diethylsilane-diyl)-bis((2-methyl-4-tert-butyl-phenylindenyl)silane prepared in 19-1 above in toluene/THF=5/1 solution (120 mL) , n-butyllithium solution (2.5 M, hexane solvent, 22.2 g) was slowly added dropwise at -78 ^° C., and then stirred for a day at room temperature. Zirconium chloride (8.9 g) was added to toluene (20 mL). After dilution, it was slowly added dropwise at -78 ^° C. and stirred for a day at room temperature. The solvent of the reaction solution was removed under reduced pressure, dichloromethane was added thereto, filtered, and the filtrate was distilled off under reduced pressure, using toluene and hexane. High purity rac-[(diethylsilane-diyl)-bis((2-methyl-4-tert-butyl-phenylindenyl)]zirconium dichloride (10.1 g, 34%, rac:meso=20: 1) was obtained.

<Preparation of supported catalyst>

Preparation Example 1: Preparation of hybrid supported metallocene catalyst

100 mL of a toluene solution was added to the high-pressure reactor, and the temperature of the reactor was maintained at 40 ^o C. 10 g of dehydrated silica (SP2408HT) was added to a 500 L reactor by applying vacuum for 12 hours at a temperature of 600 ^° C, and then 12 mmol of methylaluminoxane (MAO) was added and reacted at 95 ^° C for 12 hours. Thereafter, 30 μmol of the first metallocene compound prepared in Synthesis Example 1 and 60 μmol of the second metallocene compound prepared in Synthesis Example 17 were dissolved in toluene, followed by stirring at 50 ^o C at 200 rpm for 5 hours. Reacted.

After the reaction was over, the stirring was stopped, washed with a sufficient amount of toluene, 50 mL of toluene was added again, stirred for 10 minutes, stopped, and washed with a sufficient amount of toluene to remove compounds that did not participate in the reaction. Thereafter, 50 mL of hexane was added and stirred, and the hexane slurry was transferred to a filter and filtered.

First drying for 5 hours under reduced pressure at room temperature, and second drying under reduced pressure at 40 ^o C for 4 hours to obtain a hybrid supported catalyst.

Preparation Example 2: Preparation of hybrid supported metallocene catalyst

Hybrid support using the same method as in Preparation Example 1, except that 60 μmol of the metallocene compound prepared in Synthesis Example 1 was added, and 60 μmol of the metallocene compound prepared in Synthesis Example 17 was added. A metallocene catalyst was prepared.

Preparation Example 3: Preparation of hybrid supported metallocene catalyst

Hybrid support using the same method as in Preparation Example 1, except that 12 μmol of the metallocene compound prepared in Synthesis Example 1 was added, and 60 μmol of the metallocene compound prepared in Synthesis Example 17 was added. A metallocene catalyst was prepared.

Preparation Example 4: Preparation of hybrid supported metallocene catalyst

Using the same method as in Preparation Example 1, except that the metallocene compound prepared in Synthesis Example 2 was used instead of the first metallocene compound prepared in Synthesis Example 1, a hybrid supported metallocene catalyst was prepared. Was prepared.

Preparation Example 5: Preparation of hybrid supported metallocene catalyst

Using the same method as in Preparation Example 1, except that the metallocene compound prepared in Synthesis Example 3 was used instead of the first metallocene compound prepared in Synthesis Example 1, a hybrid supported metallocene catalyst was prepared. Was prepared.

Preparation Example 6: Preparation of hybrid supported metallocene catalyst

Using the same method as in Preparation Example 1, except that the metallocene compound prepared in Synthesis Example 4 was used instead of the first metallocene compound prepared in Synthesis Example 1, a hybrid supported metallocene catalyst was prepared. Was prepared.

Preparation Example 7: Preparation of hybrid supported metallocene catalyst

Using the same method as in Preparation Example 1, except that the metallocene compound prepared in Synthesis Example 5 was used instead of the first metallocene compound prepared in Synthesis Example 1, a hybrid supported metallocene catalyst was prepared. Was prepared.

Preparation Example 8: Preparation of hybrid supported metallocene catalyst

Using the same method as in Preparation Example 1, except that the metallocene compound prepared in Synthesis Example 6 was used instead of the first metallocene compound prepared in Synthesis Example 1, a hybrid supported metallocene catalyst was prepared. Was prepared.

Preparation Example 9: Preparation of hybrid supported metallocene catalyst

Using the same method as in Preparation Example 1, except that the metallocene compound prepared in Synthesis Example 7 was used instead of the first metallocene compound prepared in Synthesis Example 1, a hybrid supported metallocene catalyst was prepared. Was prepared.

Preparation Example 10: Preparation of hybrid supported metallocene catalyst

Using the same method as in Preparation Example 1, except that the metallocene compound prepared in Synthesis Example 8 was used instead of the first metallocene compound prepared in Synthesis Example 1, a hybrid supported metallocene catalyst was prepared. Was prepared.

Preparation Example 11: Preparation of hybrid supported metallocene catalyst

Using the same method as in Preparation Example 1, except that the metallocene compound prepared in Synthesis Example 9 was used instead of the first metallocene compound prepared in Synthesis Example 1, a hybrid supported metallocene catalyst was prepared. Was prepared.

Preparation 12: Preparation of hybrid supported metallocene catalyst

Using the same method as in Preparation Example 1, except that the metallocene compound prepared in Synthesis Example 10 was used instead of the first metallocene compound prepared in Synthesis Example 1, a hybrid supported metallocene catalyst was prepared. Was prepared.

Preparation Example 13: Preparation of hybrid supported metallocene catalyst

Using the same method as in Preparation Example 1, except that the metallocene compound prepared in Synthesis Example 11 was used instead of the first metallocene compound prepared in Synthesis Example 1, a hybrid supported metallocene catalyst was prepared. Was prepared.

Preparation 14: Preparation of hybrid supported metallocene catalyst

Using the same method as in Preparation Example 1, except that the metallocene compound prepared in Synthesis Example 12 was used instead of the first metallocene compound prepared in Synthesis Example 1, a hybrid supported metallocene catalyst was prepared. Was prepared.

Preparation Example 15: Preparation of hybrid supported metallocene catalyst

Using the same method as in Preparation Example 1, except that the metallocene compound prepared in Synthesis Example 13 was used instead of the first metallocene compound prepared in Synthesis Example 1, a hybrid supported metallocene catalyst was prepared. Was prepared.

Preparation Example 16: Preparation of hybrid supported metallocene catalyst

Using the same method as in Preparation Example 1, except that the metallocene compound prepared in Synthesis Example 14 was used instead of the first metallocene compound prepared in Synthesis Example 1, a hybrid supported metallocene catalyst was prepared. Was prepared.

Preparation Example 17: Preparation of hybrid supported metallocene catalyst

Using the same method as in Preparation Example 1, except that the metallocene compound prepared in Synthesis Example 15 was used instead of the first metallocene compound prepared in Synthesis Example 1, a hybrid supported metallocene catalyst was prepared. Was prepared.

Preparation 18: Preparation of hybrid supported metallocene catalyst

Using the same method as in Preparation Example 1, except that the metallocene compound prepared in Synthesis Example 16 was used instead of the first metallocene compound prepared in Synthesis Example 1, a hybrid supported metallocene catalyst was prepared. Was prepared.

Preparation Example 19: Preparation of hybrid supported metallocene catalyst

Using the same method as in Preparation Example 1, except that the metallocene compound prepared in Synthesis Example 17 was used instead of the first metallocene compound prepared in Synthesis Example 1, a hybrid supported metallocene catalyst was prepared. Was prepared.

Preparation Example 20: Preparation of hybrid supported metallocene catalyst

Using the same method as in Preparation Example 1, except that the metallocene compound prepared in Synthesis Example 18 was used instead of the first metallocene compound prepared in Synthesis Example 1, a hybrid supported metallocene catalyst was prepared. Was prepared.

Comparative Production Example 1: Preparation of a single supported metallocene catalyst

100 mL of a toluene solution was added to the high-pressure reactor, and the temperature of the reactor was maintained at 40 ^o C. 10 g of dehydrated silica (SP2408HT) was added to a 500 L reactor by applying vacuum for 12 hours at a temperature of 600 ^° C, and then 12 mmol of methylaluminoxane (MAO) was added and reacted at 95 ^° C for 12 hours. Thereafter, 90 μmol of the second metallocene compound prepared in Synthesis Example 19 was dissolved in toluene and added, followed by stirring at 50 ^o C at 200 rpm and reacted for 5 hours.

After the reaction was over, the stirring was stopped, washed with a sufficient amount of toluene, 50 mL of toluene was added again, stirred for 10 minutes, stopped, and washed with a sufficient amount of toluene to remove compounds that did not participate in the reaction. Thereafter, 50 mL of hexane was added and stirred, and the hexane slurry was transferred to a filter and filtered.

Primary drying for 5 hours under reduced pressure at room temperature, and secondary drying under reduced pressure at 40 ^° C. for 4 hours to obtain a single supported catalyst.

Comparative Production Example 2: Preparation of a single supported metallocene catalyst

In place of the second metallocene compound prepared in Synthesis Example 19, except that the first metallocene compound prepared in Synthesis Example 1 was used, the same method as in Comparative Preparation Example 1 was used, and independently supported. A metallocene catalyst was prepared.

Comparative Production Example 3: Preparation of a single supported metallocene catalyst

Instead of the second metallocene compound prepared in Synthesis Example 19, except that the first metallocene compound prepared in Synthesis Example 2 was used, using the same method as in Comparative Preparation Example 1, alone supported A metallocene catalyst was prepared.

Comparative Preparation Example 4: Preparation of hybrid supported metallocene catalyst

Instead of the first metallocene compound prepared in Synthesis Example 1, 1-(1-((2,3-dimethyl-3a,8b-dihydro-1H-benzo[b]cyclopenta[d]thiophen-) of the following structural formula 1-yl)dimethylsilyl)-2-methyl-1H-inden-4-yl)-1,2,3,4-tetrahydroquinoline zirconium dichloride, except that the first metallocene compound was used, and Preparation Example 1 Using the same method, a hybrid supported metallocene catalyst was prepared.

Comparative Preparation Example 5: Preparation of hybrid supported metallocene catalyst

Instead of the second metallocene compound prepared in Synthesis Example 19, [(diethylsilane-diyl)-bis(4-tert-butyl-phenylindenyl)]zirconium dichloride of the following structural formula was used as a second metallocene. A hybrid supported metallocene catalyst was prepared in the same manner as in Preparation Example 1, except that the compound was used.

Comparative Preparation Example 6: Preparation of hybrid supported metallocene catalyst

Instead of the second metallocene compound prepared in Synthesis Example 19, [(methyl-tert-butoxyhexylsilane-diyl)-bis((2-methyl-4-tert-butyl-phenylindenyl)] of the following structural formula ] A hybrid supported metallocene catalyst was prepared in the same manner as in Preparation Example 1, except that zirconium dichloride was used as the second metallocene compound.

<Polypropylene polymerization>

Example 1

A 2 L stainless steel reactor was vacuum-dried at 65 ^o C, cooled, and 3 mL of triethylaluminum was added at room temperature, 820 ppm of hydrogen gas was added, and 1.5 L of propylene was added. At this time, the input amount of hydrogen gas is a value based on the propylene monomer content.

After stirring for 10 minutes, 30 mg of the mixed supported metallocene catalyst of Preparation Example 1 and 20 mL hexane slurry were prepared at 20 ^o C, and then added to the reactor under argon (Ar) conditions. After the reactor temperature was gradually raised to 70 ^o C, a homopolymerization process of propylene was performed for 1 hour under a pressure condition of 30 bar, and unreacted propylene was vented.

Examples 2 to 20

Homopoly was used in the same manner as in Example 1, except that the mixed supported metallocene catalyst prepared in Preparation Examples 2 to 20 was used instead of the mixed supported metallocene catalyst prepared in Preparation Example 1. Propylene was prepared.

Comparative Examples 1 to 6

In place of the hybrid supported metallocene catalyst prepared in Preparation Example 1, the above implementation was performed except that the sole supported catalyst of Comparative Preparation Examples 1 to 3 or the hybrid supported metallocene catalyst of Comparative Preparation Examples 4 to 6 were used, respectively. Homo polypropylene was prepared using the same method as in Example 1.

<Test Example: Evaluation of physical properties of polypropylene>

In addition to the activities of the metallocene catalysts each used in the polymerization process according to the Examples and Comparative Examples, the properties of the homopolypropylene prepared using the supported catalyst were evaluated in the following manner. The results are shown in Table 1 below.

(1) Activity (Activity, kg PP/g·cat·hr)

It was calculated as the ratio of the weight (kg PP) of the produced homopolypropylene per mass (g) of the supported catalyst used based on the unit time (h).

(2) Melting point (Tm)

The melting point and melting point (Tm) of the propylene polymer were measured using a Differential Scanning Calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument). Specifically, after heating the polymer to 220 ^o C by raising the temperature, it was maintained at that temperature for 5 minutes, then lowered to 20 ^o C, and the temperature was increased again to show the DSC (Differential Scanning Calorimeter, manufactured by TA) curve. The top was taken as the melting point. At this time, the rate of temperature rise and fall was 10 ^o C/min, and the melting point was measured in the second temperature rise section.

(3) Pentad sequence distribution

As in the paper, V. Busico and R. Cipullo, Progress in Polymer Science, 2001, 26, 443-533, the stereoregularity of propylene polymer was measured using quantitative nuclear magnetic resonance (NMR) spectroscopy.

Specifically, the stereoregularity (Pentad sequence distribution) for homopolypropylene of Examples and Comparative Examples was obtained by measuring the sequence distribution at the pentad level by ¹³ C-NMR analysis, It is expressed as a% of the pentad (mmmm) sequence with stereoregularity for all pentad sequences. mmmm% is a value based on moles.

At this time, Bruker's 500 MHz NMR was used as a measuring instrument, and polypropylene was dissolved in a 1.1.2.2-tetrachloroethane (TCE-d ₂ ) solvent and measured at an absolute temperature of 393 K ( ¹³ C; pulse sequence = zgig30, ns=4096, d ₁ =10 sec, ¹ H; pulse sequence=zg30, ns=128, d ₁ =3 sec), analyze the sequence distribution by referring to the analysis method AMT-3989-0k, and The regularity (mmmm%) was calculated according to the thesis, V. Busico and R. Cipullo, Progress in Polymer Science, 2001, 26, 443-533.

catalyst Catalyst precursor
Molar ratio* activation
(kg PP/g Cat.hr) Tm
( ^o C) Pentad sequence distribution (mmmm, %) Example 1 Manufacturing Example 1 1:2 13.3 137.2 88 Example 2 Manufacturing Example 2 1:1 9.8 125.3 76.8 Example 3 Manufacturing Example 3 1:5 13.8 146.6 94.2 Example 4 Manufacturing Example 4 1:2 12.2 138.7 89.6 Example 5 Manufacturing Example 5 1:2 12.5 136.8 88.8 Example 6 Manufacturing Example 6 1:2 13.1 137.2 87.9 Example 7 Manufacturing Example 7 1:2 13.5 136.2 88.7 Example 8 Manufacturing Example 8 1:2 12.5 138.1 87.4 Example 9 Manufacturing Example 9 1:2 13.5 136.5 88.9 Example 10 Manufacturing Example 10 1:2 12.7 135.8 89.1 Example 11 Manufacturing Example 11 1:2 12.9 136.2 87.9 Example 12 Manufacturing Example 12 1:2 13.1 136.8 87.6 Example 13 Manufacturing Example 13 1:2 12.8 137.1 89.1 Example 14 Manufacturing Example 14 1:2 13.2 136.1 87.4 Example 15 Manufacturing Example 15 1:2 12.2 135.9 87.8 Example 16 Manufacturing Example 16 1:2 13.2 135.4 88.8 Example 17 Manufacturing Example 17 1:2 12.8 134.8 88.0 Example 18 Manufacturing Example 18 1:2 13.8 136.1 89.1 Example 19 Manufacturing Example 19 1:2 13.4 136.0 88.1 Example 20 Manufacturing Example 20 1:2 13.6 135.8 87.8 Comparative Example 1 Comparative Production Example 1 Alone 13.0 153 98 Comparative Example 2** Comparative Production Example 2 Alone 12.1 Not measurable 24.8 Comparative Example 3** Comparative Production Example 3 Alone 11.0 Not measurable 25.6 Comparative Example 4 Comparative Production Example 4 1:2 7.6 153 97.7 Comparative Example 5 Comparative Production Example 5 1:2 6.5 154 45.5 Comparative Example 6 Comparative Production Example 6 1:2 7.0 151 96.8 *The catalyst precursor molar ratio is expressed as the molar ratio of the first metallocene compound: the first metallocene compound.
** In Comparative Examples 2 and 3, the polymer was in a sticky form, making it impossible to evaluate physical properties.

Referring to Table 1, in Examples 1 to 20 using the hybrid supported metallocene catalysts of Preparation Examples 1 to 20 according to an embodiment of the present invention, while exhibiting high activity in propylene polymerization, 125.3 ^o C to 138.7 ^o By indicating the melting point of C, it can be confirmed that homopolypropylene with improved melt tension was prepared by effectively controlling the tacticity of the polypropylene molecular structure and introducing long chain branches (LCB) into the molecule.

On the other hand, in the case of Comparative Example 1 in which only the second metallocene compound of Formula 2 was supported alone, the long-chain branch (LCB) was not introduced into the polypropylene molecule, so that the melt tension was lowered and a high melting point of 153 ^o C was shown. In addition, it can be seen that in the case of Comparative Examples 2 and 3 in which only the first metallocene compound of Formula 1 was supported alone, the stereoregularity was remarkably inferior during propylene polymerization, became a sticky form, and was atactic. have.

In addition, Comparative Example 4 in which a compound having different substituents of an indene ligand in Formula 1 was used as a first precursor, and a compound having different substituents of an indene ligand in Formula 2 or a compound having different bridge substituents as a second precursor In the case of 5 and 6, the content of long chain branches (LCB) in the polypropylene molecule was lowered, resulting in lower melt tension, and high melting points of 153 ^o C, 154 ^o C, and 151 ^o C, respectively, and catalytic activity was 7.6, respectively. It can be seen that the significantly decreased to kg PP/g Cat.hr, 6.5 kg PP/g Cat.hr, and 7.0 kg PP/g Cat.hr.

Claims (23)

At least one first metallocene compound selected from compounds represented by the following formula (1);
At least one second metallocene compound selected from compounds represented by the following formula (2); And
A carrier supporting the first and second metallocene compounds;
A hybrid supported metallocene catalyst comprising:
[Formula 1]

In Formula 1,
M ₁ is a Group 4 transition metal,
A ₁ is carbon (C), silicon (Si), or germanium (Ge),
Q ₁ and Q ₂ are each independently C _1-20 alkyl,
R ₁ to R ₃ are each independently C _1-20 alkyl,
R ₄ is C _6-20 aryl unsubstituted or substituted with C _1-20 alkyl,
R ₅ to R ₇ are each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-30 aryl, C _7-30 alkylaryl, and C _7-30 arylalkyl Any one of, or two adjacent functional groups are bonded to each other to form an aliphatic cyclic group,
R ₈ is any one of hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-30 aryl, C _7-30 alkylaryl, and C _7-30 arylalkyl,
X ₁ and X ₂ are each independently a single bond, or S or CR _a R _b , but at least one of X ₁ and X ₂ is S, wherein R _a and R _b are each independently hydrogen, C _{1- 20} alkyl, C _2-20 alkenyl, C _6-30 aryl, C _7-30 alkylaryl, and C _7-30 arylalkyl,
Y ₁ and Y ₂ are each independently halogen,
m is an integer from 1 to 4,
[Formula 2]

In Chemical Formula 2,
M ₂ is a Group 4 transition metal;
A ₂ is carbon (C), silicon (Si), or germanium (Ge),
Y ₃ and Y ₄ are each independently halogen,
R ₉ and R ₁₄ are each independently C _1-20 alkyl, or C _6-20 aryl,
R ₁₀ and R ₁₅ are each independently C _6-40 aryl substituted or unsubstituted with C _1-20 alkyl,
R ₁₁ to R ₁₃ and R ₁₆ to R ₁₈ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 Alkoxysilyl, C _1-20 ether, C _1-20 silyl ether, C _1-20 alkoxy, C _6-40 aryl, C _7-20 alkylaryl, and C _7-20 arylalkyl,
Q ₃ and Q ₄ are identical to each other and are C _2-20 alkyl.
The method of claim 1,
Q ₁ and Q ₂ are each C _1-6 alkyl,
Y ₁ and Y ₂ are each halogen,
A ₁ is silicon (Si),
M ₁ is zirconium (Zr) or hafnium (Hf),
Hybrid supported metallocene catalyst.
The method of claim 1,
R ₁ to R ₃ are each C _1-6 straight-chain alkyl,
Hybrid supported metallocene catalyst.
The method of claim 1,
R ₁ to R ₃ are each methyl,
Hybrid supported metallocene catalyst.
The method of claim 1,
R ₄ is phenyl or naphthyl, unsubstituted or substituted with C _3-6 branched alkyl,
Hybrid supported metallocene catalyst.
The method of claim 1,
R ₄ is phenyl, 4-(tert-butyl)phenyl, 3,5-di-(tert-butyl)phenyl, or naphthyl,
Hybrid supported metallocene catalyst.
The method of claim 1,
R ₅ to R ₇ are each hydrogen or two adjacent functional groups are bonded to each other to form a cyclopentyl group,
Hybrid supported metallocene catalyst.
The method of claim 1,
_One of X ₁ and X ₂ is S, and the other is a single bond,
Hybrid supported metallocene catalyst.
The method of claim 1,
The first metallocene compound is represented by one of the following structural formulas,
Hybrid supported metallocene catalyst:

.
The method of claim 1,
Y ₃ and Y ₄ are each halogen,
A ₂ is silicon (Si),
M ₂ is zirconium (Zr) or hafnium (Hf),
Hybrid supported metallocene catalyst.
The method of claim 1,
R ₉ and R ₁₄ are each C _1-6 straight or branched alkyl,
Hybrid supported metallocene catalyst.
The method of claim 1,
R ₉ and R ₁₄ are each methyl,
Hybrid supported metallocene catalyst.
The method of claim 1,
R ₁₀ and R ₁₅ are each a phenyl group substituted with a C _3-6 branched alkyl group,
Hybrid supported metallocene catalyst.
The method of claim 1,
R ₁₀ and R ₁₅ are each 4-(tert-butyl)phenyl,
Hybrid supported metallocene catalyst.
The method of claim 1,
Q ₃ and Q ₄ are the same and are C _2-4 straight-chain alkyl groups,
Hybrid supported metallocene catalyst.
The method of claim 1,
Q ₃ and Q ₄ are both ethyl,
Hybrid supported metallocene catalyst.
The method of claim 1,
The second metallocene compound is a compound represented by the following structural formula,
Hybrid supported metallocene catalyst:

.
The method of claim 1,
The first metallocene compound and the second metallocene compound are supported in a molar ratio of 1:1 to 1:8,
Hybrid supported metallocene catalyst.
The method of claim 1,
The carrier contains a hydroxy group and a siloxane group on the surface,
Hybrid supported metallocene catalyst.
The method of claim 19,
The carrier is at least one selected from the group consisting of silica, silica-alumina, and silica-magnesia,
Hybrid supported metallocene catalyst.
The method of claim 1,
Further comprising one or more cocatalysts selected from the group consisting of compounds represented by the following formulas 3 to 5,
Hybrid supported metallocene catalyst:
[Formula 3]
-[Al(R ₃₁ )-O] _c-
In Chemical Formula 3,
Each R ₃₁ is independently halogen, C _1-20 alkyl or C _1-20 haloalkyl,
c is an integer greater than or equal to 2,
[Formula 4]
D(R ₄₁ ) ₃
In Chemical Formula 4,
D is aluminum or boron,
Each R ₄₁ is independently hydrogen, halogen, C _1-20 hydrocarbyl or C _1-20 hydrocarbyl substituted with halogen,
[Formula 5]
^{[LH] + [Q (E} ) 4] - or ^{[L] + [Q (E} ) 4] -
In Chemical Formula 5,
L is a neutral or cationic Lewis base,
[LH] ⁺ is Bronsted acid,
Q is Br ³⁺ or Al ³⁺ ,
E is each independently C _6-40 aryl or C _1-20 alkyl, wherein the C _6-40 aryl or C _1-20 alkyl is unsubstituted or halogen, C _1-20 alkyl, C _1-20 alkoxy, And C _6-40 is substituted with one or more substituents selected from the group consisting of aryloxy.
In the presence of the hybrid supported metallocene catalyst of claim 1, comprising the step of polymerizing a propylene monomer, a method for producing polypropylene.
The method of claim 22,
The polypropylene is a homopolymer,
Method for producing polypropylene.