阅读说明：本技术 杂化负载型茂金属催化剂和使用其制备聚丙烯的方法 (Hybrid supported metallocene catalyst and method for preparing polypropylene using the same ) 是由 安相恩 李仁羡 金祏焕 金炳奭 洪大植 李尚勋 于 2020-06-11 设计创作，主要内容包括：本发明提供了一种杂化负载型茂金属催化剂,其在丙烯聚合中表现出高活性并且通过将长链分支引入聚丙烯分子中而有用地应用于制备具有高熔体强度的聚丙烯,本发明还涉及使用上述催化剂制备聚丙烯的方法。(The present invention provides a hybrid supported metallocene catalyst which exhibits high activity in propylene polymerization and is usefully applied to the preparation of polypropylene having high melt strength by introducing long-chain branches into polypropylene molecules, and a method for preparing polypropylene using the same.)

1. A hybrid supported metallocene catalyst comprising: one or more first metallocene compounds selected from the group consisting of compounds represented by the following chemical formula 1; one or more second metallocene compounds selected from the group consisting of compounds represented by the following chemical formula 2; and a carrier supporting the first metallocene compound and the second metallocene compound:

[ chemical formula 1]

In the chemical formula 1, the first and second,

M₁is a transition metal of the group 4, and,

A₁is carbon, silicon or germanium, and is,

Q₁and Q₂Each independently is C_1-20An alkyl group, a carboxyl group,

R₁to R₃Each independently is C_1-20An alkyl group, a carboxyl group,

R₄is unsubstituted or substituted by C_1-20C of alkyl_6-20An aryl group, a heteroaryl group,

R₅to R₇Each independently is hydrogen, C_1-20Alkyl radical, C_2-20Alkenyl radical, C_6-30Aryl radical, C_7-30Alkylaryl orC_7-30Any one of arylalkyl, or R₅To R₇Two adjacent groups of (a) are linked to each other to form an aliphatic ring group,

R₈is hydrogen, C_1-20Alkyl radical, C_2-20Alkenyl radical, C_6-30Aryl radical, C_7-30Alkylaryl or C_7-30Any one of an arylalkyl group or a substituted arylalkyl group,

X₁and X₂Each independently a single bond, S or CR_aR_bWherein X is₁And X₂Is S, and R_aAnd R_bEach independently is hydrogen, C_1-20Alkyl radical, C_2-20Alkenyl radical, C_6-30Aryl radical, C_7-30Alkylaryl or C_7-30Any one of an arylalkyl group or a substituted arylalkyl group,

Y₁and Y₂Each independently is halogen, and

m is an integer of 1 to 4,

[ chemical formula 2]

In the chemical formula 2, the first and second organic solvents,

M₂is a transition metal of the group 4, and,

A₂is carbon (C), silicon (Si) or germanium (Ge),

Y₃and Y₄Each of which is independently a halogen atom,

R₉and R₁₄Each independently is C_1-20Alkyl or C_6-20An aryl group, a heteroaryl group,

R₁₀and R₁₅Each independently is unsubstituted or substituted with C_1-20C of alkyl_6-40An aryl group, a heteroaryl group,

R₁₁to R₁₃And R₁₆To R₁₈Each independently of the others is hydrogen, halogen, C_1-20Alkyl radical, C_2-20Alkenyl radical, C_1-20Alkylsilyl group, C_1-20Silylalkyl group, C_1-20Alkoxysilyl group, C_1-20Ether, C_1-20Silyl ether, C_1-20Alkoxy radical, C_6-40Aryl radical, C_7-20Alkylaryl or C_7-20Any one of arylalkyl, and

Q₃and Q₄Are identical to each other and are C_2-20An alkyl group.

2. The hybrid supported metallocene catalyst of claim 1, wherein Q is₁And Q₂Each is C_1-6Alkyl radical, Y₁And Y₂Each is halogen, A₁Is silicon, and M₁Is zirconium or hafnium.

3. The hybrid supported metallocene catalyst of claim 1, wherein R₁To R₃Each is C_1-6A linear alkyl group.

4. The hybrid supported metallocene catalyst of claim 1, wherein R₁To R₃Each is methyl.

5. The hybrid supported metallocene catalyst of claim 1, wherein R₄Is unsubstituted or substituted by C_3-6Phenyl or naphthyl of branched alkyl groups.

6. The hybrid supported metallocene catalyst of claim 1, wherein R₄Is phenyl, 4- (tert-butyl) phenyl, 3, 5-di (tert-butyl) phenyl or naphthyl.

7. The hybrid supported metallocene catalyst of claim 1, wherein R₅To R₇Each is hydrogen, or R₅To R₇Are linked to each other to form a cyclopentyl group.

8. The hybrid supported metallocene catalyst of claim 1, wherein X₁And X₂One of them is S and the other is a single bond.

9. The hybrid supported metallocene catalyst of claim 1, wherein the first metallocene compound is represented by any one of the following structural formulas:

10. the hybrid supported metallocene catalyst of claim 1, wherein Y is₃And Y₄Each is halogen, A₂Is silicon, and M₂Is zirconium or hafnium.

11. The hybrid supported metallocene catalyst of claim 1, wherein R₉And R₁₄Each is C_1-6Straight or branched chain alkyl.

12. The hybrid supported metallocene catalyst of claim 1, wherein R₉And R₁₄Each is methyl.

13. The hybrid supported metallocene catalyst of claim 1, wherein R₁₀And R₁₅Each being substituted by C_3-6Phenyl for branched alkyl.

14. The hybrid supported metallocene catalyst of claim 1, wherein R₁₀And R₁₅Each is 4- (tert-butyl) phenyl.

15. The hybrid supported metallocene catalyst of claim 1, wherein Q is₃And Q₄Are identical to each other and are C_2-4A linear alkyl group.

16. The hybrid supported metallocene catalyst of claim 1, wherein Q is₃And Q₄Are all ethyl groups.

17. The hybrid supported metallocene catalyst of claim 1, wherein the second metallocene compound is a compound represented by the following structural formula:

18. the hybrid supported metallocene catalyst of claim 1, wherein the first metallocene compound and the second metallocene compound are supported in a molar ratio of 1:1 to 1: 8.

19. The hybrid supported metallocene catalyst of claim 1, wherein the support comprises hydroxyl groups and siloxane groups on its surface.

20. The hybrid supported metallocene catalyst of claim 19, wherein the support is one or more selected from the group consisting of silica, silica-alumina, and silica-magnesia.

21. The hybrid supported metallocene catalyst of claim 1, further comprising one or more cocatalysts selected from the group consisting of compounds represented by the following chemical formulas 3 to 5:

[ chemical formula 3]

-[Al(R₃₁)-O]_c-

In the chemical formula 3, the first and second,

R₃₁each independently is halogen, C_1-20Alkyl or C_1-20A halogenated alkyl group, and

c is an integer of 2 or more,

[ chemical formula 4]

D(R₄₁)₃

In the chemical formula 4, the first and second organic solvents,

d is aluminum or boron, and

R₄₁each independently of the others is hydrogen, halogen, C_1-20Hydrocarbyl or halogen substituted C_1-20A hydrocarbon group,

[ chemical formula 5]

[L-H]⁺[Q(E)₄]^-Or [ L]⁺[Q(E)₄]^-

In the chemical formula 5, the first and second organic solvents,

l is a neutral or cationic Lewis base,

[L-H]⁺is a Bronsted acid and is a Bronsted acid,

q is B³⁺Or Al³⁺And is and

e is each independently C_6-40Aryl or C_1-20Alkyl radical, wherein C_6-40Aryl or C_1-20Alkyl unsubstituted or substituted by one or more members selected from halogen, C_1-20Alkyl radical, C_1-20Alkoxy and C_6-40A substituent of the group consisting of aryloxy.

22. A process for preparing polypropylene comprising the step of polymerizing propylene monomer in the presence of the hybrid supported metallocene catalyst of claim 1.

23. The method of claim 22, wherein the polypropylene is a homopolymer.

Technical Field

Cross Reference to Related Applications

The present application is based on and claims priority from korean patent application nos. 10-2019-0069973, 10-2019-0123776 and 10-2020-0070125, which were filed on day 13 at 2019, 10 at 7 at 2019 and 10 at 6 at 2020, respectively, the disclosures of which are incorporated herein by reference in their entirety.

The present invention relates to hybrid supported metallocene catalysts, and to a process for preparing polypropylene using the catalysts.

Background

Olefin polymerization catalyst systems can be divided into ziegler-natta and metallocene catalyst systems. These high activity catalyst systems have been developed based on their characteristics.

Since the development of the 50 s of the 20 th century, Ziegler-Natta catalysts have been widely used in commercial processes. However, since the Ziegler-Natta catalyst is a multi-active site catalyst in which a plurality of active sites are mixed, it is characterized in that the resulting polymer has a broad molecular weight distribution. Since the composition distribution of the comonomer is not uniform, there is a problem that it is difficult to obtain desired physical properties.

On the other hand, the metallocene catalyst is composed of a combination of a main catalyst having a transition metal compound as a main component and an organometallic compound cocatalyst having aluminum as a main component. Such catalysts are single active site catalysts, which are homogeneous composite catalysts, and due to the single active site nature, provide polymers with narrow molecular weight distribution and uniform comonomer composition distribution. The tacticity, copolymerization characteristics, molecular weight and crystallinity of the obtained polymer can be controlled by changing the ligand structure of the catalyst and polymerization conditions.

Recent changes in environmental awareness are seeking to reduce the production of Volatile Organic Compounds (VOCs) in many product groups. However, the ziegler-natta catalyst (Z/N) used for the preparation of polypropylene has the problem of generating high Total Volatile Organic Compounds (TVOC). In particular, although most of various commercially available polypropylenes are products using ziegler-natta catalysts, the polypropylenes are increasingly converted into products using metallocene catalysts having less odor and low elution characteristics.

In particular, the existing polypropylene is a general-purpose resin and has advantages of light weight due to low density and high rigidity and heat resistance and low moisture absorption, but has disadvantages of low impact strength and melt strength. Furthermore, the current commercial processes for producing polypropylene with high melt strength are mainly carried out in the post-treatment stage, i.e. post-modification (irradiation as cross-linking, graft polymerization). There is a continuing need for a technique for producing polypropylene into which long chain branches are introduced in a reactor by the application of catalyst technology.

Therefore, it is required to develop a method for preparing polypropylene having high melt strength by introducing Long Chain Branches (LCB) into polypropylene molecules using a metallocene-based catalyst exhibiting high activity in propylene polymerization.

Disclosure of Invention

[ problem ] to provide a method for producing a semiconductor device

The present invention provides a hybrid supported metallocene catalyst that can be used to prepare polypropylene having a relatively high melt strength while having excellent catalytic activity in propylene polymerization.

The invention also provides a method for preparing polypropylene by using the hybrid supported metallocene catalyst.

[ technical solution ] A

The invention provides a hybrid supported metallocene catalyst, which comprises: one or more first metallocene compounds selected from the group consisting of compounds represented by the following chemical formula 1; one or more second metallocene compounds selected from the group consisting of compounds represented by the following chemical formula 2; and a support supporting the first and second metallocene compounds:

[ chemical formula 1]

In the chemical formula 1, the first and second,

M₁is a transition metal of the group 4, and,

A₁is carbon (C), silicon (Si) or germanium (Ge),

Q₁and Q₂Each independently is C_1-20An alkyl group, a carboxyl group,

R₁to R₃Each independently is C_1-20An alkyl group, a carboxyl group,

R₄is unsubstituted or substituted by C_1-20C of alkyl_6-20An aryl group, a heteroaryl group,

R₅to R₇Each independently is hydrogen, C_1-20Alkyl radical, C_2-20Alkenyl radical, C_6-30Aryl radical, C_7-30Alkylaryl or C_7-30Any one of arylalkyl, or R₅To R₇Two adjacent groups of (a) are linked to each other to form an aliphatic ring group,

R₈is hydrogen, C_1-20Alkyl radical, C_2-20Alkenyl radical, C_6-30Aryl radical, C_7-30Alkylaryl or C_7-30Any one of an arylalkyl group or a substituted arylalkyl group,

X₁and X₂Each independently a single bond, S or CR_aR_bWherein X is₁And X₂Is S, and R_aAnd R_bEach independently is hydrogen, C_1-20Alkyl radical, C_2-20Alkenyl radical, C_6-30Aryl radical, C_7-30Alkylaryl or C_7-30Aryl alkaneAny one of the above-mentioned groups may be used,

Y₁and Y₂Each independently is halogen, and

m is an integer of 1 to 4,

[ chemical formula 2]

In the chemical formula 2, the first and second organic solvents,

M₂is a transition metal of the group 4, and,

A₂is carbon (C), silicon (Si) or germanium (Ge),

Y₃and Y₄Each of which is independently a halogen atom,

R₉and R₁₄Each independently is C_1-20Alkyl or C_6-20An aryl group, a heteroaryl group,

R₁₀and R₁₅Each independently is unsubstituted or substituted with C_1-20C of alkyl_6-40An aryl group, a heteroaryl group,

R₁₁to R₁₃And R₁₆To R₁₈Each independently of the others is hydrogen, halogen, C_1-20Alkyl radical, C_2-20Alkenyl radical, C_1-20Alkylsilyl group, C_1-20Silylalkyl group, C_1-20Alkoxysilyl group, C_1-20Ether, C_1-20Silyl ether, C_1-20Alkoxy radical, C_6-40Aryl radical, C_7-20Alkylaryl or C_7-20Any one of arylalkyl, and

Q₃and Q₄Are identical to each other and are C_2-20An alkyl group.

Further, in chemical formula 1, Q₁And Q₂Each is C_1-6Alkyl radical, Y₁And Y₂Each is halogen, A₁Is silicon (Si), and M₁Is zirconium (Zr) or hafnium (Hf).

Further, in chemical formula 1, R₁To R₃May each be C_1-6Straight chain alkyl groups, and in particular, may each be methyl.

Further, in chemical formula 1, R₄May be unsubstituted or substituted by C_3-6Phenyl or naphthyl of a branched alkyl group, and specifically phenyl, 4- (tert-butyl) phenyl, 3, 5-di (tert-butyl) phenyl or naphthyl.

Further, in chemical formula 1, R₅To R₇May each be hydrogen, or R₅To R₇Two adjacent groups of (a) may be linked to each other to form a cyclopentyl group.

Further, in chemical formula 1, X₁And X₂Either one of them may be S, and the other may be a single bond.

The first metallocene compound may be represented by any one of the following structural formulae:

meanwhile, in chemical formula 2, Y₃And Y₄Each is halogen, A₂Is silicon (Si), and M₂Is zirconium (Zr) or hafnium (Hf).

Further, in chemical formula 2, R₉And R₁₄Are the same or different from each other, and may each be C_1-6Or C_1-3Straight or branched chain alkyl.

Further, in chemical formula 2, R₁₀And R₁₅Are identical to or different from each other and may each be substituted by C_3-6Phenyl for branched alkyl.

In addition, the method can be used for producing a composite materialIn chemical formula 2, R₁₁To R₁₃And R₁₆To R₁₈May each be hydrogen or C_1-6Straight or branched chain alkyl.

Further, in chemical formula 2, Q₃And Q₄Are identical to each other and may be C_2-4A linear alkyl group, specifically ethyl.

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

the first metallocene compound and the second metallocene compound may be supported at a molar ratio of 1:1 to 1: 8.

Further, the support may include hydroxyl groups and siloxane groups on the surface thereof, and may preferably be one or more selected from the group consisting of silica, silica-alumina, and silica-magnesia.

In addition, 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:

[ chemical formula 3]

-[Al(R₃₁)-O]_c-

In the chemical formula 3, the first and second,

R₃₁each independently is halogen, C_1-20Alkyl or C_1-20A halogenated alkyl group, and

c is an integer of 2 or more,

[ chemical formula 4]

D(R₄₁)₃

In the chemical formula 4, the first and second organic solvents,

d is aluminum or boron, and

R₄₁each independently of the others is hydrogen, halogen, C_1-20Hydrocarbyl or halogen substituted C_1-20A hydrocarbon group,

[ chemical formula 5]

[L-H]⁺[Q(E)₄]^-Or [ L]⁺[Q(E)₄]^-

In the chemical formula 5, the first and second organic solvents,

l is a neutral or cationic Lewis base,

[L-H]⁺is Bronsted acid (Bronsted acid),

q is B³⁺Or Al³⁺And is and

e is each independently C_6-40Aryl or C_1-20Alkyl radical, wherein C_6-40Aryl or C_1-20Alkyl unsubstituted or substituted by one or more members selected from halogen, C_1-20Alkyl radical, C_1-20Alkoxy and C_6-40A substituent of the group consisting of aryloxy.

Meanwhile, the present invention provides a method for preparing polypropylene, which comprises the step of polymerizing propylene monomers in the presence of the hybrid supported metallocene catalyst.

In this regard, the polypropylene may be a homopolymer, and the polypropylene may be polymerized by using a hybrid supported catalyst in which the first and second metallocene compounds having specific substituents and structures are supported to exhibit high catalytic activity and may have significantly improved melt strength by introducing Long Chain Branches (LCB) into the polypropylene molecule.

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

Singular expressions may include plural expressions unless the context clearly dictates otherwise.

It must be understood that the terms "comprises", "comprising", "includes" and "including" in this specification are used merely to indicate the presence of stated features, integers, steps, components or groups thereof, which have an effect, and do not preclude the presence or possibility of one or more other features, integers, steps, components or groups thereof having been previously added.

In the present specification, when a layer or element is referred to as being "on" or "over" the layer or element, it means that each layer or element is directly formed on the layer or element, or other layers or elements may be formed between the layers, bodies, or substrates.

While the invention is susceptible to various modifications and alternative forms, specific exemplary embodiments thereof have been shown and described in detail below. However, it is not intended to limit the present invention to the specific exemplary embodiments, and it must be understood that the present invention includes all modifications, equivalents, and alternatives falling within the spirit and technical scope of the present invention.

Hereinafter, the present invention will be described in detail.

According to the present invention, there is provided a hybrid supported metallocene catalyst comprising: one or more first metallocene compounds selected from the group consisting of compounds represented by the following chemical formula 1; one or more second metallocene compounds selected from the group consisting of compounds represented by the following chemical formula 2; and a support supporting the first and second metallocene compounds:

[ chemical formula 1]

In the chemical formula 1, the first and second,

M₁is a transition metal of the group 4, and,

A₁is carbon (C), silicon (Si) or germanium (Ge),

Q₁and Q₂Each independently is C_1-20An alkyl group, a carboxyl group,

R₁to R₃Each independently is C_1-20An alkyl group, a carboxyl group,

R₄is unsubstituted or substituted by C_1-20C of alkyl_6-20An aryl group, a heteroaryl group,

R₅to R₇Each independently is hydrogen, C_1-20Alkyl radical, C_2-20Alkenyl radical, C_6-30Aryl radical, C_7-30Alkylaryl or C_7-30Any one of arylalkyl, or R₅To R₇Two adjacent groups of (a) are linked to each other to form an aliphatic ring group,

R₈is hydrogen, C_1-20Alkyl radical, C_2-20Alkenyl radical, C_6-30Aryl radical, C_7-30Alkylaryl or C_7-30Any one of an arylalkyl group or a substituted arylalkyl group,

X₁and X₂Each independently a single bond, S or CR_aR_bWherein X is₁And X₂Is S, and R_aAnd R_bEach independently is hydrogen, C_1-20Alkyl radical, C_2-20Alkenyl radical, C_6-30Aryl radical, C_7-30Alkylaryl or C_7-30Any one of an arylalkyl group or a substituted arylalkyl group,

Y₁and Y₂Each independently is halogen, and

m is an integer of 1 to 4,

[ chemical formula 2]

In the chemical formula 2, the first and second organic solvents,

M₂is a transition metal of the group 4, and,

A₂is carbon (C), silicon (Si) or germanium (Ge),

Y₃and Y₄Each of which is independently a halogen atom,

R₉and R₁₄Each independently is C_1-20Alkyl or C_6-20An aryl group, a heteroaryl group,

R₁₀and R₁₅Each independently is unsubstituted or substituted with C_1-20C of alkyl_6-40An aryl group, a heteroaryl group,

R₁₁to R₁₃And R₁₆To R₁₈Each independently of the others is hydrogen, halogen, C_1-20Alkyl radical, C_2-20Alkenyl radical, C_1-20Alkylsilyl group, C_1-20Silylalkyl group, C_1-20Alkoxysilyl group, C_1-20Ether, C_1-20Silyl ether, C_1-20Alkoxy radical, C_6-40Aryl radical, C_7-20Alkylaryl or C_7-20Any one of arylalkyl, and

Q₃and Q₄Are identical to each other and are C_2-20An alkyl group.

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

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

Having 1 to 20 carbons (C)_1-20) The alkyl group of (b) may be a linear, branched or cyclic alkyl group. Specifically, C_1-20The alkyl group may be C_1-20A linear alkyl group; c_1-15A linear alkyl group; c_1-5A linear alkyl group; c_3-20A branched or cyclic alkyl group; c_3-15A branched or cyclic alkyl group; or C_3-10A branched or cyclic alkyl group. E.g. C_1-20The alkyl group may be, but is not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like.

Having 2 to 20 carbons (C)_2-20) The alkenyl group of (b) may include a straight or branched alkenyl group, and specifically, may include an allyl group, a vinyl group, a propenyl group, a butenyl group, a pentenyl group, and the like, but is not limited thereto.

Having 1 to 20 carbons (C)_1-20) The alkoxy group of (b) may include methoxy, ethoxy, isopropoxy, n-butoxy, tert-butoxy, cyclohexyloxy and the like, but is not limited thereto.

Having 2 to 20 carbons (C)_2-20) The alkoxyalkyl group of (a) is a functional group in which one or more hydrogens of the above-mentioned alkyl group is substituted with an alkoxy group, and specifically, an alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an isopropoxymethyl group, an isopropoxyethyl group, an isopropoxypropyl group, an isopropoxyhexyl group, a tert-butoxymethyl group, a tert-butoxyethyl group, a tert-butoxypropyl group, a tert-butoxyhexyl group, and the like can be included, but not limited thereto.

Having 6 to 40 carbons (C)_6-40) The aryloxy group of (b) may include phenoxy, biphenyloxy, naphthyloxy and the like, but is not limited thereto.

Having 7 to 40 carbons (C)_7-40) The aryloxyalkyl group of (a) is a functional group in which one or more hydrogens of the above-mentioned alkyl group are substituted with an aryloxy group, and specifically, mayIncluding, but not limited to, phenoxymethyl, phenoxyethyl, phenoxyhexyl, and the like.

Having 1 to 20 carbons (C)_1-20) Or an alkylsilyl group of 1 to 20 carbons (C)_1-20) The alkoxysilyl group of (a) is wherein-SiH₃A functional group in which 1 to 3 hydrogens of (a) are substituted with the above-mentioned 1 to 3 alkyl or alkoxy groups, and specifically, an alkylsilyl group such as methylsilyl, dimethylsilyl, trimethylsilyl, dimethylethylsilyl, diethylmethylsilyl, dimethylpropylsilyl, etc.; alkoxysilyl groups such as methoxysilyl, dimethoxysilyl, trimethoxysilyl, dimethoxyethoxysilyl and the like; or an alkoxyalkyl silyl group such as a methoxydimethylsilyl group, a diethoxymethylsilyl group, a dimethoxypropylsilyl group, etc., but not limited thereto.

Having 1 to 20 carbons (C)_1-20) The silylalkyl group of (a) is a functional group in which one or more hydrogens of the above alkyl group are substituted with a silyl group, and specifically, may include-CH₂-SiH₃Methylsilylmethyl, dimethylethoxysilylpropyl, and the like, but are not limited thereto.

In addition, having 1 to 20 carbons (C)_1-20) The alkylene group of (a) is the same as the above alkyl group except that it is a divalent substituent, and specifically, may include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and the like, but is not limited thereto.

Having 6 to 20 carbons (C)_6-20) The aryl group of (a) may be a monocyclic, bicyclic or tricyclic aromatic hydrocarbon. For example, having 6 to 20 carbons (C)_6-20) The aryl group of (b) may include phenyl, biphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, and the like, but is not limited thereto.

Having 7 to 20 carbons (C)_7-20) The alkylaryl group of (a) may refer to a substituent in which one or more hydrogens of the aromatic ring are replaced with the above alkyl group. For example, having 7 to 20 carbons (C)_7-20) The alkylaryl group of (A) may include methylPhenyl, ethylphenyl, methylbiphenyl, methylnaphthyl, and the like, but are not limited thereto.

Having 7 to 20 carbons (C)_7-20) The aralkyl group of (a) may refer to a substituent in which one or more hydrogens of the alkyl group are substituted with the above-mentioned aryl group. For example, having 7 to 20 carbons (C)_7-20) The aralkyl group of (a) may include a phenylmethyl group, a phenylethyl group, a biphenylmethyl group, a naphthylmethyl group, etc., but is not limited thereto.

In addition, having 6 to 20 carbons (C)_6-20) The arylene group of (a) is the same as the above-mentioned aryl group except that it is a divalent substituent, and specifically, may include phenylene, biphenylene, naphthylene, anthracenylene, phenanthrenylene, fluorenylene and the like, but is not limited thereto.

The group 4 transition metal may be titanium (Ti), zirconium (Zr), hafnium (Hf) or(Rf), specifically, titanium (Ti), zirconium (Zr) or hafnium (Hf), and more specifically, zirconium (Zr) or hafnium (Hf), but is not limited thereto.

Further, the group 13 element may be boron (B), aluminum (Al), gallium (Ga), indium (In), or thallium (Tl), and specifically boron (B) or aluminum (Al), but is not limited thereto.

The above substituents may be optionally substituted with one or more substituents selected from the group consisting of: a hydroxyl group; halogen; alkyl or alkenyl, aryl, alkoxy; alkyl or alkenyl, aryl, alkoxy containing one or more heteroatoms from groups 14 to 16; a silyl group; an alkylsilyl or alkoxysilyl group; a phosphine group; a phosphorus group; sulfonate groups and sulfone groups to exert the same or similar effects as desired.

Meanwhile, the hybrid supported catalyst of the present invention, in which the first metallocene compound forming a double bond at the terminal during propylene polymerization and the second metallocene compound having a high molecular weight property are hybrid-supported, exhibits high activity in propylene polymerization, and is usefully applied to the preparation of polypropylene having high melt strength by introducing Long Chain Branches (LCB) into the polypropylene molecule.

Specifically, the first metallocene compound of chemical formula 1 includes S having an unshared electron pair in the ligand structure, and thus can provide a metal atom with more abundant electrons, thereby stabilizing the vacancy of the transition metal contained in the bridge group. Thus, β -hydride elimination of the polymer chain can be induced to form a macromonomer having a double bond at the terminal, and particularly, a vinyl terminal group which can be used as a monomer can be included at a high ratio, thereby introducing a Long Chain Branch (LCB) into the polypropylene molecule.

Typically, polymers having end groups (or end groups) saturated with hydrogen are produced when the chain is terminated in the presence of hydrogen. The production of polymers having double bonds as end groups can be caused by the structural features of the catalyst.

The production of polymers having double bonds at the ends proceeds according to two mechanisms: beta-hydro-elimination or beta-methyl-extraction, as shown in reaction scheme 1 below.

[ reaction scheme 1]

In reaction scheme 1, M is a metal element, H is a hydrogen atom, and Me is a methyl group.

In general, beta-hydrogen elimination (beta-hydrogen elimination) occurs more easily, but the vinylidene terminal group generated at this time is replaced with a substituent to lose its role as a monomer, and thus it is inactive as a macromonomer. In contrast, the vinyl end groups produced by β -methyl elimination are reactive and can be used as monomers.

Specifically, the first metallocene compound of chemical formula 1 includes S having an unshared electron pair in the ligand structure, thereby providing a metal atom with more abundant electrons. Therefore, even when the metal atoms have vacancies, they can maintain stability, and thus can generate vinyl end groups. In contrast, with a general transition metal compound, when a metal atom has a vacancy, it forms a metal-hydrogen bond (metal-H bond) to become stable, and thus an inactive vinylidene terminal group is generated. Therefore, when the transition metal compound of the present invention is used as a catalyst for polymer production, a polymer having a high proportion of vinyl end groups and a low proportion of vinylidene end groups can be produced.

In addition, since the first metallocene compound of chemical formula 1 includes two ligand structures having different asymmetric structures, it may have various characteristics of two different ligands or may selectively utilize the advantages thereof, and as a result, it may exhibit excellent catalytic activity.

Among the two ligands in the first metallocene compound of chemical formula 1, in the first ligand including a cyclopentadienyl group (in which S is included and two ring structures are fused), C_1-20Alkyl (R)₁And R₂) Substituted in the 2 and 3 positions, respectively, in a second ligand having an indene structure or a structure in which an aliphatic ring is further condensed with the benzene ring of indene, C_1-20Alkyl (R)₃) Substituted in position 2 and unsubstituted or substituted by C_1-20C of alkyl_6-20Aryl (R)₄) Substitution is at the 4-position. Therefore, excellent catalytic activity can be achieved due to the induction effect of providing sufficient electrons, and when the first metallocene compound is used as a catalyst for polypropylene polymerization, the tacticity of the polypropylene molecular structure can be easily controlled to lower the melting point. In particular, R substituted in position 4 of the second ligand₄The aryl group is included to increase the aromaticity of the first metallocene compound, thereby further improving the catalytic activity.

Further, the first metallocene compound comprises a double substituent having C_1-20Alkyl (Q)₁And Q₂) Functional group A of₁As a bridging group connecting two ligands to each other. Therefore, the atomic size increases and the available angle increases, and therefore, the monomer can be easily obtained, thereby achieving excellent catalytic activity. Further, as A₁Q of the substituent(s)₁And Q₂The solubility of the transition metal compound can be increased to improve the loading efficiency in the preparation of the supported catalyst.

Meanwhile, the second metallocene compound represented by chemical formula 2 includes the same alkane disubstituted with two or more carbonsDivalent functional groups A of radicals₂As a bridging group connecting two indenyl ligands to each other. Therefore, the atomic size thereof is increased and the available angle is increased as compared with the existing carbon bridge, and thus, the monomer can be easily obtained, thereby realizing excellent catalytic activity. In particular, since the second metallocene compound represented by chemical formula 2 has a better stereoregularity than the first metallocene compound represented by chemical formula 1, it is suitable for propylene polymerization and has an excellent catalytic activity, and thus plays a role in polymerizing to obtain a polymer chain having a high molecular weight.

Accordingly, the hybrid supported metallocene catalyst includes a second metallocene compound in addition to the first metallocene compound, that is, the hybrid supported metallocene catalyst includes two or more different kinds of metallocene compounds, thereby exhibiting high activity in propylene polymerization, and producing polypropylene having excellent physical properties, particularly improved melt strength, by introducing Long Chain Branches (LCB) into polypropylene molecules.

Specifically, in chemical formula 1, Q₁And Q₂May be the same as or different from each other, and may each be C_1-6Or C_1-5Alkyl, and in particular methyl, ethyl or n-hexyl.

Further, in chemical formula 1, Y₁And Y₂Each may be halogen, and in particular chlorine.

Further, in chemical formula 1, A₁May be silicon (Si).

Further, in chemical formula 1, M₁May be zirconium (Zr) or hafnium (Hf), and specifically zirconium (Zr). Since Zr has more electron accepting orbitals than other group 4 transition metals such as Hf and the like, it can be easily bound to the monomer with higher affinity, thereby obtaining excellent catalytic activity. In addition, Zr can improve the storage stability of the metal complex.

Further, in chemical formula 1, R₁To R₃May each independently be C_1-20Or C_1-12Or C_1-6Straight or branched chain alkyl, and more specifically C_1-6Or C_1-4Straight chainAlkyl groups such as methyl, ethyl, propyl or n-butyl. More specifically, R₁To R₃May each be methyl.

Further, in chemical formula 1, R₄May be unsubstituted or substituted by C_1-8C of straight-chain or branched alkyl_6-12Aryl, more particularly unsubstituted or substituted with C_3-6Phenyl or naphthyl of branched alkyl groups. When substituted with an alkyl group, the aryl group may be substituted with one or more alkyl groups, more specifically, one alkyl group or two alkyl groups. R₆Specific examples of (b) may include phenyl, 4- (tert-butyl) phenyl, 3, 5-di- (tert-butyl) phenyl, naphthyl and the like. In addition, when R is₄Is substituted by C_3-6Phenyl of branched alkyl radicals, C_3-6The substitution position of the branched alkyl-p-phenyl group may be that corresponding to R bound to the indenyl group₄The para position in the 4-position corresponds to the meta position in the 3-or 5-position.

Further, in chemical formula 1, R₅To R₇Can be each independently hydrogen, C_1-12Alkyl radical, C_2-12Alkenyl radical, C_6-18Aryl radical, C_7-20Alkylaryl or C_7-20Any one of arylalkyl groups, or two adjacent functional groups such as R₅And R₆Or R₆And R₇Are connected to each other to form C_3-12Or C_4-8Or C_5-6Alicyclic groups (or alicyclic structures), such as cyclopentyl.

Further, in chemical formula 1, R₈Can be hydrogen or C_1-12Alkyl radical, C_2-12Alkenyl radical, C_6-12Aryl radical, C_7-15Alkylaryl or C_7-15Any one of arylalkyl groups. More specifically, R₈May be hydrogen or C_1-6Any of linear or branched alkyl groups. R₈Specific examples of (b) may be hydrogen, methyl, ethyl, propyl, n-butyl or tert-butyl, etc. Preferably, R₈May be hydrogen.

Further, in chemical formula 1, X₁And X₂May each independently be a single bond, S or CR_aR_bWherein X is₁And X₂Can be S, and more particularlyBody ground, X₁And X₂Any one of which may be S, and the other may be a single bond. For example, X₁Can be S and X₂May be a single bond, or X₁May be a single bond and X₂May be S. In addition, when X₁Or X₂Is CR_aR_bWhen R is_aAnd R_bCan more particularly each independently be hydrogen, C_1-10Alkyl radical, C_2-10Alkenyl radical, C_6-12Aryl radical, C_7-13Alkylaryl or C_7-13Any one of arylalkyl groups.

Further, in chemical formula 1, Q₁And Q₂May each independently be C_1-6Or C_1-5A straight chain alkyl group, and more specifically a methyl, ethyl or n-hexyl group; r₁To R₃May each independently be C_1-6Or C_1-4Straight chain alkyl, and more specifically, R₁To R₃All may be methyl; r₄May be unsubstituted or substituted by C_3-6Phenyl or naphthyl of a branched alkyl group, and more specifically phenyl, 4-tert-butylphenyl, 3, 5-di-tert-butylphenyl or naphthyl; r₅To R₇May each independently be hydrogen, or R₅To R₇Two adjacent groups of (a) are linked to each other to form a cyclopentyl group; and X₁And X₂Any one of which may be S, and the other may be a single bond.

Further, in chemical formula 1, A₁May be silicon, M₁May be zirconium, Q₁And Q₂May each independently be C_1-6Or C_1-5A straight chain alkyl group, and more specifically a methyl, ethyl or n-hexyl group; r₁To R₃May each independently be C_1-6Or C_1-4Straight chain alkyl, and more specifically, R₁To R₃All may be methyl; r₄May be unsubstituted or substituted by C_3-6Phenyl or naphthyl of a branched alkyl group, and more specifically phenyl, 4-tert-butylphenyl, 3, 5-di-tert-butylphenyl or naphthyl; r₅To R₇May each independently be hydrogen, or R₅To R₇Two adjacent groups of (a) are linked to each other to form a cyclopentyl group; and X₁And X₂Any one of which may be S, and the other may be a single bond. In this respect, R₈May be hydrogen.

Further, the first metallocene compound represented by chemical formula 1 may be represented by any one of the following structural formulae:

meanwhile, the hybrid supported metallocene catalyst of the present invention may further include a second metallocene compound in addition to the above-mentioned first metallocene compound.

Specifically, in chemical formula 2, Y₃And Y₄Each may be halogen, and in particular chlorine.

Further, in chemical formula 2, A₂May be silicon (Si).

Further, in chemical formula 2, M₂It may be zirconium (Zr) or hafnium (Hf), in particular zirconium (Zr). Since Zr has more electron accepting orbitals than other group 4 transition metals such as Hf and the like, it can be easily bound to the monomer with higher affinity, thereby obtaining excellent catalytic activity. In addition, Zr can improve the storage stability of the metal complex.

Further, in chemical formula 2, R₉And R₁₄May each independently be C_1-20Or C_1-6Or C_1-4Straight or branched chainAlkyl or C_6-20Or C_6-12Aryl, and more specifically C_1-6Or C_1-4Straight or branched chain alkyl groups such as methyl, ethyl or isopropyl. More specifically, R₉And R₁₄Each may be methyl.

Further, in chemical formula 2, R₁₁To R₁₃And R₁₆To R₁₈Can each independently be hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, trimethylsilylmethyl, or R₁₁To R₁₃And R₁₆To R₁₈Are linked to each other to form an aromatic ring unsubstituted or substituted with a methyl group or a phenyl group, but is not limited thereto.

Further, in chemical formula 2, R₁₀And R₁₅May each be unsubstituted or substituted by C_1-8C of straight-chain or branched alkyl_6-12Aryl, more particularly unsubstituted or substituted with C_3-6Phenyl or naphthyl of branched alkyl groups. R₁₀And R₁₅May include substitution with C_3-6The phenyl group of the branched alkyl group is preferably a tert-butylphenyl group. In addition, when R is₁₀And R₁₅Is substituted by C_3-6Phenyl of branched alkyl radicals, C_3-6The substitution position of the branched alkyl-p-phenyl group may be that corresponding to R bound to the indenyl group₁₀And R₁₅Position is para to 4 bits.

Further, in chemical formula 2, Q₃And Q₄May be identical to each other, and may be C_2-4Straight chain alkyl, preferably ethyl.

Further, in chemical formula 2, Q₃And Q₄May be identical to each other, and may be C_2-4Straight chain alkyl, and more specifically, Q₃And Q₄May be ethyl, R₉And R₁₄May each independently be C_1-6Or C_1-3Straight or branched chain alkyl, and more specifically, R₉And R₁₄All may be methyl, R₁₀And R₁₅May be substituted by C_3-6Phenyl substituted by a branched alkyl group, andand more particularly 4-tert-butylphenyl, R₁₁To R₁₃And R₁₆To R₁₈May each independently be hydrogen or C_1-3Straight or branched chain alkyl, and more specifically, R₁₁To R₁₃And R₁₆To R₁₈May be hydrogen.

Further, in chemical formula 2, A₂May be silicon, M₂May be zirconium, Q₃And Q₄May be identical to each other, and may be C_2-4Straight chain alkyl, and more specifically, Q₃And Q₄May be ethyl, R₉And R₁₄May each independently be C_1-6Or C_1-3Straight or branched chain alkyl, and more specifically, R₉And R₁₄All may be methyl, R₁₀And R₁₅May be substituted by C_3-6Phenyl of a branched alkyl group, and more particularly 4-tert-butylphenyl, R₁₁To R₁₃And R₁₆To R₁₈May each independently be hydrogen or C_1-3Straight or branched chain alkyl, and more specifically, R₁₁To R₁₃And R₁₆To R₁₈May be hydrogen.

Further, in chemical formula 2, the second metallocene compound may include 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 mixture thereof.

As used herein, "racemic form", "racemate" or "racemic isomer" means that the same substituents on both cyclopentadienyl moieties are present relative to a compound containing M in formula 1 or formula 2₁Or M₂The plane of the represented transition metal (e.g., zirconium (Zr) or hafnium (Hf)) and the opposite side of the center of the cyclopentadienyl moiety.

As used hereinBy the term "meso form" or "meso isomer" (which is a stereoisomer of racemic form) is meant that the same substituents on both cyclopentadienyl moieties are present relative to the inclusion of M in formula 1 or formula 2₁Or M₂The plane of the represented transition metal (e.g., zirconium (Zr) or hafnium (Hf)) is on the same side as the center of the cyclopentadienyl moiety.

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. When the loading ratio is less than about 1:1, only the first metallocene compound plays a dominant role, and thus the tacticity is significantly reduced during propylene polymerization, and the catalyst becomes highly viscous, which may make it difficult to form the polymer itself. Further, when the loading ratio is higher than about 1:8, only the second metallocene compound plays a dominant role, and the content of Long Chain Branches (LCB) in the polypropylene molecule is reduced, which may reduce the melt strength.

Specifically, the hybrid supported metallocene catalyst in which the first metallocene compound and the second metallocene compound are supported at a molar ratio of about 1:1 to about 1:6 or at a molar ratio of about 1:1 to about 1:5 can introduce Long Chain Branches (LCB) in a polypropylene molecule while exhibiting high activity in propylene polymerization, thereby preferably preparing polypropylene having excellent physical properties, particularly improved melt strength.

In other words, the hybrid supported metallocene catalyst of the present invention in which the first metallocene compound and the second metallocene compound are supported at the above molar ratio can further improve the melt strength of polypropylene due to the interaction between two or more catalysts.

In the hybrid supported metallocene catalyst of the present invention, a support including hydroxyl groups on the surface thereof may be used as a support for supporting the first metallocene compound and the second metallocene compound, and preferably, the support may be a support including highly reactive hydroxyl groups or siloxane groups, the surface of which is dried and moisture is removed.

For example, silica-alumina and silica-magnesia dried at high temperature may be used. These carriers may generally include oxide, carbonate, sulfate and nitrate components, such as Na₂O、K₂CO₃、BaSO₄、Mg(NO₃)₂And the like.

The temperature at which the support is dried may preferably be from about 200 ℃ to about 800 ℃, more preferably from about 300 ℃ to about 600 ℃, and most preferably from about 300 ℃ to about 400 ℃. When the temperature at which the support is dried is lower than 200 ℃, the moisture is so excessive that the moisture on the surface can react with a cocatalyst described below, and when the temperature is higher than 800 ℃, the pores on the surface of the support combine to reduce the surface area, and many hydroxyl groups on the surface are lost, so that only siloxane groups are left. Therefore, the reaction site with the cocatalyst can be reduced, which is not preferable.

The amount of hydroxyl groups on the surface of the support may preferably be about 0.1mmol/g to about 10mmol/g, more preferably about 0.5mmol/g to about 5 mmol/g. The amount of hydroxyl groups on the surface of the carrier can be adjusted by the preparation method and the preparation conditions of the carrier or drying conditions such as temperature, time, vacuum or spray drying, etc.

When the amount of the hydroxyl group is less than about 0.1mmol/g, the number of reaction sites with the co-catalyst is small, and when the amount is more than about 10mmol/g, the hydroxyl group may be generated by moisture other than the hydroxyl group present on the surface of the carrier particle, which is not preferable.

Further, in the hybrid supported metallocene catalyst, one or more first metallocene compounds and one or more second metallocene compounds are supported on a carrier together with a cocatalyst compound. The cocatalyst may be any cocatalyst as long as it is a cocatalyst for olefin polymerization in the presence of a conventional metallocene catalyst. Such a cocatalyst is capable of forming a bond between the hydroxyl group on the support and the group 13 transition metal. Furthermore, since the cocatalyst is present only at the surface of the support, it can help to obtain the inherent characteristics of the specific hybrid catalyst composition of the present invention without fouling phenomena, wherein the polymer particles adhere to the wall surface of the reactor or to each other.

Specifically, the hybrid supported metallocene catalyst may further include one or more cocatalysts selected from the group consisting of compounds represented by the following chemical formulas 3 to 5:

[ chemical formula 3]

-[Al(R₃₁)-O]_c-

In the chemical formula 3, the first and second,

R₃₁each independently is halogen, C_1-20Alkyl or C_1-20A halogenated alkyl group, and

c is an integer of 2 or more,

[ chemical formula 4]

D(R₄₁)₃

In the chemical formula 4, the first and second organic solvents,

d is aluminum or boron, and

R₄₁each independently of the others is hydrogen, halogen, C_1-20Hydrocarbyl or halogen substituted C_1-20A hydrocarbon group,

[ chemical formula 5]

[L-H]⁺[Q(E)₄]^-Or [ L]⁺[Q(E)₄]^-

In the chemical formula 5, the first and second organic solvents,

l is a neutral or cationic Lewis base,

[L-H]⁺is a Bronsted acid and is a Bronsted acid,

q is B³⁺Or Al³⁺And is and

e is each independently C_6-40Aryl or C_1-20Alkyl radical, wherein C_6-40Aryl or C_1-20Alkyl unsubstituted or substituted by one or more members selected from halogen, C_1-20Alkyl radical, C_1-20Alkoxy and phenoxy groups.

The compound represented by chemical formula 3 may be exemplified by alkylaluminoxane such as Modified Methylaluminoxane (MMAO), Methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane and butylaluminoxane.

The metal alkyl compound represented by chemical formula 4 may be, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylaluminum chloride, dimethylaluminum isobutyl, dimethylethylaluminum, diethylaluminum chloride, triisopropylaluminum, tri-sec-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron.

The compound represented by chemical formula 5 may be, for example, triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetrakis (p-tolyl) boron, tripropylammonium tetrakis (p-tolyl) boron, triethylammonium tetrakis (o, p-dimethylphenyl) boron, trimethylammonium tetrakis (o, p-dimethylphenyl) boron, tributylammonium tetrakis (p-trifluoromethylphenyl) boron, trimethylammonium tetrakis (p-trifluoromethylphenyl) boron, tributylammonium tetrakis (pentafluorophenyl) boron, N-diethylanilinium tetraphenylboron, N-diethylanilinium tetrakis (pentafluorophenyl) boron, diethylammonium tetrakis (pentafluorophenyl) boron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, Trimethylammoniumtetra (p-tolyl) aluminum, tripropylammoniumtetra (p-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammoniumtetra (p-trifluoromethylphenyl) aluminum, trimethylammoniumtetra (p-trifluoromethylphenyl) aluminum, tributylammoniumtetra (pentafluorophenyl) aluminum, N-diethylaniliniumtetraphenylaluminum, N-diethylaniliniumtetrakis (pentafluorophenyl) aluminum, diethylammonium tetrakis (pentafluorophenyl) aluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, triphenylcarbonium tetraphenylboron, triphenylcarbonium tetraphenylaluminum, triphenylcarbonium tetrakis (p-trifluoromethylphenyl) boron, triphenylcarbonium tetrakis (pentafluorophenyl) boron, and the like.

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

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

In this regard, when the molar ratio is less than 1, the metal content in the co-catalyst is too low, so that the catalytically active species are not well formed, and the activity may be lowered. When the molar ratio is greater than about 10000, it is understood that the metal of the co-catalyst may act more as a catalyst poison.

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

Meanwhile, the hybrid supported metallocene catalyst can be prepared by the following preparation method, which comprises the following steps: supporting the cocatalyst on a support; supporting a first metallocene compound on a cocatalyst-supported carrier; and supporting the second metallocene compound on the cocatalyst and the first metallocene compound-supported carrier.

Alternatively, the hybrid supported metallocene catalyst may be prepared by a preparation method comprising the steps of: supporting the cocatalyst on a support; supporting a second metallocene compound on a cocatalyst-supported carrier; and supporting the first metallocene compound on a support on which the cocatalyst and the second metallocene compound are supported.

Alternatively, the hybrid supported metallocene catalyst may be prepared by a preparation method comprising the steps of: supporting a first metallocene compound on a support; supporting a cocatalyst on a first metallocene compound-supported carrier; and supporting the second metallocene compound on the cocatalyst and the first metallocene compound-supported carrier.

In the above method, the loading conditions are not particularly limited, and the loading may be performed within a range known to those skilled in the art. For example, the loading may be suitably performed at high and low temperatures. For example, the loading temperature may be in the range of about-30 ℃ to 150 ℃, and may preferably be about 50 ℃ to about 98 ℃, or about 55 ℃ to about 95 ℃. The supporting time may be appropriately controlled according to the amount of the first metallocene compound to be supported. The supported catalyst after the reaction may be used as it is, after removing the reaction solvent by filtration or distillation under reduced pressure, or if necessary, subjected to Soxhlet filtration using an aromatic hydrocarbon such as toluene.

The preparation of the supported catalyst can be carried out in the presence or absence of a solvent. When a solvent is used, it may include an aliphatic hydrocarbon solvent such as hexane or pentane, an aromatic hydrocarbon solvent such as toluene or benzene, a chlorinated hydrocarbon solvent such as methylene chloride, an ether solvent such as diethyl ether or Tetrahydrofuran (THF), and a commonly used organic solvent such as acetone or ethyl acetate. Preferred are hexane, heptane, toluene and dichloromethane.

In the present invention, in the process for preparing a metallocene compound or a supported catalyst, the equivalent (eq) means a molar equivalent (eq/mol).

Meanwhile, the present invention provides a method for preparing polypropylene, which comprises the step of polymerizing propylene monomers in the presence of the hybrid supported metallocene catalyst.

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

Further, the polymerization temperature may be from about 25 ℃ to about 500 ℃, or from about 25 ℃ to about 300 ℃, or from about 30 ℃ to about 200 ℃, or from about 50 ℃ to about 150 ℃, or from about 60 ℃ to about 120 ℃. Further, the polymerization pressure may be about 1kgf/cm²To about 100kgf/cm²Or about 1kgf/cm²To about 50kgf/cm²Or about 5kgf/cm²To about 45kgf/cm²Or about 10kgf/cm²To about 40kgf/cm²Or about 15kgf/cm²To about 35kgf/cm²。

The supported metallocene catalyst can be dissolved or diluted in C₅-C₁₂In an aliphatic hydrocarbon solvent such as pentane, hexane, heptane, nonane, decane and isomers thereof, in an aromatic hydrocarbon solvent such as toluene and benzene or in a chlorinated hydrocarbon solvent such as dichloromethane and chlorobenzene. The solvent used herein is preferably used after removing a small amount of water or air serving as a catalyst poison by treatment with a small amount of aluminum alkyl. A cocatalyst may be further used.

In particular, the hybrid supported metallocene catalyst of the present invention exhibits high activity in propylene polymerization and is usefully applied to the preparation of polypropylene having excellent physical properties, particularly improved melt strength, by introducing Long Chain Branches (LCB) into polypropylene molecules. In particular, since the catalyst precursor of chemical formula 2, which exhibits high molecular weight properties during propylene polymerization, is used together with the catalyst precursor of chemical formula 1 to synthesize a macromonomer having a double bond at the terminal, the hybrid supported metallocene catalyst of the present invention facilitates achievement of high melt strength by introducing Long Chain Branches (LCB) into a polypropylene molecule.

For example, the polymerization step may be carried out by injecting hydrogen in an amount of about 1500ppm or less, or about 200ppm to about 1500ppm, about 1000ppm or less, or about 250ppm to about 1000ppm, or about 850ppm or less, or about 300ppm to about 850ppm based on the propylene monomer content.

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

The polymerization step may be a step of homopolymerizing the propylene monomer alone.

In the present invention, when a hybrid supported metallocene catalyst in which two or more metallocene compounds having the specific substituents and structures are supported on a carrier is used during the polymerization of polypropylene, high catalytic activity can be achieved during the polymerization, and the melt strength can be significantly improved by introducing long-chain branches into the polypropylene molecule. Polypropylene with this property can be applied to a wide range of products with different grades, depending on the hydrogen reactivity.

For example, the polypropylene may have a melting point (Tm) of 150 ℃ or less, or 115 ℃ to 150 ℃, or 148 ℃ or less, or 118 ℃ to 148 ℃, or 145 ℃ or less, or 120 ℃ to 145 ℃, or 140 ℃ or less, or 125 ℃ to 140 ℃. The melting point (Tm) of polypropylene may be 150 ℃ or less in terms of exhibiting high melt strength by introducing Long Chain Branches (LCB) into the polymer molecule. However, the melting point (Tm) of polypropylene may be 115 ℃ or higher in terms of preventing the occurrence of fouling during polymerization.

In the present invention, the melting point (Tm) can be measured using a differential scanning calorimeter (DSC, equipment name: DSC 2920, manufacturer: TA instruments). In detail, the polypropylene polymer was heated to 200 ℃ by increasing the temperature, and then maintained at the same temperature for 5 minutes, followed by decreasing the temperature to 30 ℃. Then, the temperature was increased again, and the temperature corresponding to the peak in the DSC (differential scanning calorimeter, manufactured by TA) curve was determined as the melting point (Tm). In this regard, the temperature is increased and decreased at a rate of 10 ℃/min, respectively, and the melting point (Tm) is the result measured between the second temperature increase and decrease intervals. The detailed method for measuring the melting point (Tm) is described in the following experimental examples.

Further, the polypropylene may have a tacticity (mmmm) of 60% to 95.8%, or 65% to 95.5%, or 70% to 95%, or 75% to 94.5%. The polypropylene can maintain the tacticity (pentad sequence distribution, mmmm) within the above range in terms of effectively controlling the tacticity of the polymer molecular structure and improving the melt strength by introducing Long Chain Branches (LCB) into the polypropylene molecule.

In the present invention, the tacticity (pentad sequence distribution, mmmm) can be measured using quantitative Nuclear Magnetic Resonance (NMR) spectroscopy. In detail, in the process of¹³After C-NMR analysis measured the sequence distribution at the pentad level, it was expressed as% of the pentad (mmmm) sequences having tacticity with respect to all the pentad sequences. mmmm% is a value based on moles. The detailed method for measuring the tacticity (pentad sequence distribution, mmmm) is described in the following experimental examples.

[ PROBLEMS ] the present invention

The hybrid supported metallocene catalyst of the present invention can exhibit high activity in propylene polymerization, and can prepare polypropylene having high melt strength by introducing long chain branches into polypropylene molecules.

Detailed Description

Hereinafter, the action and effect of the present invention will be described in more detail with reference to specific exemplary embodiments. However, these exemplary embodiments are provided only for illustrating the present invention, and the scope of the present invention is not limited thereto.

< example >

< preparation of first metallocene Compound >

Synthesis example 1

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

In the reactor, 1 equivalent of 1, 2-dimethyl-3H-benzo [ d ] cyclopenta [ b ] thiophene was dissolved in Tetrahydrofuran (THF) (0.7M), and n-butyllithium (n-BuLi, 1.05 equivalents) was slowly added dropwise at-25 ℃ and then stirred at room temperature for 3 hours. Thereafter, dichlorodimethylsilane (1.05 eq) was added at-10 ℃ and 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 was dissolved in a mixed solvent of toluene and THF (mixing volume ratio ═ 5:1, 0.7M), and n-BuLi (1.05 equivalents) was slowly added dropwise at-25 ℃, followed by stirring at room temperature for 3 hours. Thereafter, CuCN (2 mol%) was added, followed by stirring for 30 minutes. Then, the same equivalent of the previously prepared mono-Si solution was added, followed by stirring at room temperature for 24 hours. After treatment with water, the product is dried to give the ligand compound.

1-2 preparation of transition Metal Compound (1, 2-dimethyl-3H-benzo [ d ] cyclopenta [ b ] thiophen-3-yl) dimethyl (2-methyl-4- (4' -tert-butylphenyl) -1H-inden-1-yl) silanylzirconium dichloride

The prepared ligand compound was added to and dissolved in a mixed solvent of toluene and diethyl ether (mixed volume ratio ═ 2:1, 0.7M), and n-BuLi (2.05 equivalents) was added at-25 ℃, followed by stirring at room temperature for 5 hours.

In a separate flask, ZrCl was added₄(1 eq.) was mixed with toluene (0.17M) to prepare a slurry, and the prepared slurry was added to the ligand solution, followed by stirring at room temperature overnight.

When the reaction is complete, the solvent is dried under vacuum. Dichloromethane was added again and then LiCl was removed by filtration. The filtrate was dried in vacuo, and toluene was added thereto, followed by recrystallization at room temperature. The resulting solid was filtered and dried in vacuo to give the title transition metal compound.

¹H-NMR(CDCl₃,500MHz):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 2

A transition metal compound having the title structure was prepared in the same manner as in synthesis example 1, except that 4- (3',5' -di-tert-butylphenyl) -2-methyl-1, 5,6, 7-tetrahydro-s-indacene was used as a reactant instead of 4- (4' -tert-butylphenyl) -2-methyl-1H-indene in synthesis example 1.

¹H-NMR(CDCl₃,500MHz):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

A transition metal compound having the title structure was prepared in the same manner as in synthesis example 1, except that 2-methyl-4-naphthyl-1H-indene was used as a reactant instead of 4- (4' -tert-butylphenyl) -2-methyl-1H-indene in synthesis example 1.

¹H-NMR(CDCl₃,500MHz):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

A transition metal compound having the title structure was prepared in the same manner as in synthesis example 1, except that 2-methyl-4-phenyl-1H-indene was used as a reactant instead of 4- (4' -tert-butylphenyl) -2-methyl-1H-indene in synthesis example 1.

¹H-NMR(CDCl₃,500MHz):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

A transition metal compound having the title structure was prepared in the same manner as in synthesis example 1, except that 4- (3',5' -di-tert-butylphenyl) -2-methyl-1H-indene was used as a reactant in place of 4- (4' -tert-butylphenyl) -2-methyl-1H-indene in synthesis example 1.

¹H-NMR(CDCl₃,500MHz):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

A transition metal compound having the title structure was prepared in the same manner as in synthesis example 1, except that 4-naphthyl-2-methyl-1, 5,6, 7-tetrahydro-s-indacene was used as a reactant instead of 4- (4' -tert-butylphenyl) -2-methyl-1H-indene in synthesis example 1.

¹H-NMR(CDCl₃,500MHz):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

A transition metal compound having the title structure was prepared in the same manner as in synthesis example 1, except that 4-phenyl-2-methyl-1, 5,6, 7-tetrahydro-s-indacene was used as a reactant instead of 4- (4' -tert-butylphenyl) -2-methyl-1H-indene in synthesis example 1.

¹H-NMR(CDCl₃,500MHz):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

A transition metal compound having the title structure was prepared in the same manner as in synthesis example 1, except that 4- (4 '-tert-butylphenyl) -2-methyl-1, 5,6, 7-tetrahydro-s-indacene was used as a reactant instead of 4- (4' -tert-butylphenyl) -2-methyl-1H-indene in synthesis example 1.

¹H-NMR(CDCl₃,500MHz):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

A transition metal compound having the title structure was prepared in the same manner as in Synthesis example 1, except that 1, 2-dimethyl-3H-benzo [ b ] cyclopenta [ d ] thiophene was used as a reactant instead of 1, 2-dimethyl-3H-benzo [ d ] cyclopenta [ b ] thiophene in Synthesis example 1.

¹H-NMR(CDCl₃,500MHz):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

A transition metal compound having the title structure was prepared in the same manner as in Synthesis example 2, except that 1, 2-dimethyl-3H-benzo [ b ] cyclopenta [ d ] thiophene was used as a reactant instead of 1, 2-dimethyl-3H-benzo [ d ] cyclopenta [ b ] thiophene in Synthesis example 2.

¹H-NMR(CDCl₃,500MHz):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

A transition metal compound having the title structure was prepared in the same manner as in Synthesis example 3, except that 1, 2-dimethyl-3H-benzo [ b ] cyclopenta [ d ] thiophene was used as a reactant instead of 1, 2-dimethyl-3H-benzo [ d ] cyclopenta [ b ] thiophene in Synthesis example 3.

¹H-NMR(CDCl₃,500MHz):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

A transition metal compound having the title structure was prepared in the same manner as in Synthesis example 4, except that 1, 2-dimethyl-3H-benzo [ b ] cyclopenta [ d ] thiophene was used as a reactant instead of 1, 2-dimethyl-3H-benzo [ d ] cyclopenta [ b ] thiophene in Synthesis example 4.

¹H-NMR(CDCl₃,500MHz):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

A transition metal compound having the title structure was prepared in the same manner as in Synthesis example 5, except that 1, 2-dimethyl-3H-benzo [ b ] cyclopenta [ d ] thiophene was used as a reactant instead of 1, 2-dimethyl-3H-benzo [ d ] cyclopenta [ b ] thiophene in Synthesis example 5.

¹H-NMR(CDCl₃,500MHz):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

A transition metal compound having the title structure was prepared in the same manner as in Synthesis example 6, except that 1, 2-dimethyl-3H-benzo [ b ] cyclopenta [ d ] thiophene was used as a reactant instead of 1, 2-dimethyl-3H-benzo [ d ] cyclopenta [ b ] thiophene in Synthesis example 6.

¹H-NMR(CDCl₃,500MHz):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

A transition metal compound having the title structure was prepared in the same manner as in Synthesis example 7, except that 1, 2-dimethyl-3H-benzo [ b ] cyclopenta [ d ] thiophene was used as a reactant instead of 1, 2-dimethyl-3H-benzo [ d ] cyclopenta [ b ] thiophene in Synthesis example 7.

¹H-NMR(CDCl₃,500MHz):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

A transition metal compound having the title structure was prepared in the same manner as in Synthesis example 8, except that 1, 2-dimethyl-3H-benzo [ b ] cyclopenta [ d ] thiophene was used as a reactant instead of 1, 2-dimethyl-3H-benzo [ d ] cyclopenta [ b ] thiophene in Synthesis example 8.

¹H-NMR(CDCl₃,500MHz):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

A transition metal compound having the title structure was prepared in the same manner as in synthesis example 1, except that dichlorodiethylsilane was used instead of dichlorodimethylsilane in synthesis example 1.

¹H-NMR(CDCl₃,500MHz):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

A transition metal compound having the title structure was prepared in the same manner as in synthesis example 8, except that dichlorohexylmethylsilane was used instead of dichlorodimethylsilane in synthesis example 1.

¹H-NMR(CDCl₃,500MHz):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 second metallocene Compound >

Synthesis example 19

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

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

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

(diethylsilane-diyl) -bis ((2-methyl-4-tert-butyl-phenylindenyl) silane prepared in 19-1 was dissolved in a toluene/THF-5/1 solution (120mL), and then an n-butyllithium solution (2.5M, a hexane solvent, 22.2g) was slowly added dropwise at-78 ℃ followed by stirring at room temperature for one day to the resultant reaction solution, a solution prepared by diluting zirconium chloride (8.9g) with toluene (20mL) was slowly added dropwise at-78 ℃ and stirred at room temperature for one day, the solvent was removed from the reaction solution under reduced pressure, dichloromethane was added, then filtered, the filtrate was removed by reduced pressure distillation, recrystallization was performed using toluene and hexane to obtain high-purity rac- [ (diethylsilane-diyl) -bis ((2-methyl-4-tert-butyl-phenylindenyl) ] zirconium dichloride (10.1g, 34%, rac: meso ═ 20: 1).

< preparation of Supported catalyst >

Preparation example 1: preparation of hybrid supported metallocene catalysts

100mL of toluene solution was placed in the high pressure reactor and the reactor temperature was maintained at 40 ℃. 10g of silica (SP2408HT) dehydrated in vacuo at a temperature of 600 ℃ for 12 hours was placed in a 500L reactor, and 12mmol of Methylaluminoxane (MAO) was added and allowed to react at 95 ℃ for 12 hours. Thereafter, 30. mu. mol of the first metallocene compound of Synthesis example 1 and 60. mu. mol of the second metallocene compound of Synthesis example 17 were dissolved in toluene and reacted at 50 ℃ for 5 hours with stirring at 200 rpm.

When the reaction was complete, stirring was stopped and then washed with sufficient toluene. Then, 50mL of toluene was added again and stirred for 10 minutes. Then, the stirring was stopped, and washing was performed using a sufficient amount of toluene to remove compounds that did not participate in the reaction. Thereafter, 50mL of hexane was added, followed by stirring. The hexane slurry was transferred to a filter for filtration.

The resulting product was first dried at room temperature under reduced pressure for 5 hours, and then secondarily dried at 40 ℃ under reduced pressure for 4 hours to obtain a hybrid supported catalyst.

Preparation example 2: preparation of hybrid supported metallocene catalysts

A hybrid supported metallocene catalyst was prepared in the same manner as in preparation example 1, except that 60. mu. mol of the metallocene compound prepared in Synthesis example 1 was added, and 60. mu. mol of the metallocene compound prepared in Synthesis example 17 was added.

Preparation example 3: preparation of hybrid supported metallocene catalysts

A hybrid supported metallocene catalyst was prepared in the same manner as in preparation example 1, except that 12. mu. mol of the metallocene compound prepared in Synthesis example 1 was added, and 60. mu. mol of the metallocene compound prepared in Synthesis example 17 was added.

Preparation example 4: preparation of hybrid supported metallocene catalysts

A hybrid supported metallocene catalyst was prepared in the same manner 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.

Preparation example 5: preparation of hybrid supported metallocene catalysts

A hybrid supported metallocene catalyst was prepared in the same manner 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.

Preparation example 6: preparation of hybrid supported metallocene catalysts

A hybrid supported metallocene catalyst was prepared in the same manner 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.

Preparation example 7: preparation of hybrid supported metallocene catalysts

A hybrid supported metallocene catalyst was prepared in the same manner 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.

Preparation example 8: preparation of hybrid supported metallocene catalysts

A hybrid supported metallocene catalyst was prepared in the same manner 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.

Preparation example 9: preparation of hybrid supported metallocene catalysts

A hybrid supported metallocene catalyst was prepared in the same manner 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.

Preparation example 10: preparation of hybrid supported metallocene catalysts

A hybrid supported metallocene catalyst was prepared in the same manner 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.

Preparation example 11: preparation of hybrid supported metallocene catalysts

A hybrid supported metallocene catalyst was prepared in the same manner 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.

Preparation example 12: preparation of hybrid supported metallocene catalysts

A hybrid supported metallocene catalyst was prepared in the same manner 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.

Preparation example 13: preparation of hybrid supported metallocene catalysts

A hybrid supported metallocene catalyst was prepared in the same manner 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.

Preparation example 14: preparation of hybrid supported metallocene catalysts

A hybrid supported metallocene catalyst was prepared in the same manner 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.

Preparation example 15: preparation of hybrid supported metallocene catalysts

A hybrid supported metallocene catalyst was prepared in the same manner 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.

Preparation example 16: preparation of hybrid supported metallocene catalysts

A hybrid supported metallocene catalyst was prepared in the same manner 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.

Preparation example 17: preparation of hybrid supported metallocene catalysts

A hybrid supported metallocene catalyst was prepared in the same manner 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.

Preparation example 18: preparation of hybrid supported metallocene catalysts

A hybrid supported metallocene catalyst was prepared in the same manner 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.

Preparation example 19: preparation of hybrid supported metallocene catalysts

A hybrid supported metallocene catalyst was prepared in the same manner 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.

Preparation example 20: preparation of hybrid supported metallocene catalysts

A hybrid supported metallocene catalyst was prepared in the same manner 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.

Comparative preparation example 1: preparation of single supported metallocene catalyst

100mL of toluene solution was placed in the high pressure reactor and the reactor temperature was maintained at 40 ℃. 10g of silica (SP2408HT) dehydrated in vacuo at a temperature of 600 ℃ for 12 hours was placed in a 500L reactor, and 12mmol of Methylaluminoxane (MAO) was added and allowed to react at 95 ℃ for 12 hours. Thereafter, 90. mu. mol of the second metallocene compound prepared in Synthesis example 19 was dissolved in toluene, and added thereto, and allowed to react at 50 ℃ for 5 hours with stirring at 200 rpm.

When the reaction was complete, stirring was stopped and then washed with sufficient toluene. Then, 50mL of toluene was added again and stirred for 10 minutes. Then, the stirring was stopped, and washing was performed using a sufficient amount of toluene to remove compounds that did not participate in the reaction. Thereafter, 50mL of hexane was added, followed by stirring. The hexane slurry was transferred to a filter for filtration.

The resulting product was first dried at room temperature under reduced pressure for 5 hours, and then secondarily dried at 40 ℃ under reduced pressure for 4 hours to obtain a single supported catalyst.

Comparative preparation example 2: preparation of single supported metallocene catalyst

A single supported metallocene catalyst was prepared in the same manner as in comparative preparation example 1, except that the first metallocene compound prepared in synthesis example 1 was used instead of the second metallocene compound prepared in synthesis example 19.

Comparative preparation example 3: preparation of single supported metallocene catalyst

A single supported metallocene catalyst was prepared in the same manner as in comparative preparation example 1, except that the first metallocene compound prepared in synthesis example 2 was used instead of the second metallocene compound prepared in synthesis example 19.

Comparative preparation example 4: preparation of hybrid supported metallocene catalysts

A hybrid supported metallocene catalyst was prepared in the same manner as in preparation example 1, except that 1- (1- ((2, 3-dimethyl-3 a,8 b-dihydro-1H-benzo [ b ] cyclopenta [ d ] thiophen-1-yl) dimethylsilyl) -2-methyl-1H-inden-4-yl) -1,2,3, 4-tetrahydroquinoline zirconium dichloride having the following structural formula was used as the first metallocene compound in place of the first metallocene compound prepared in Synthesis example 1.

Comparative preparation example 5: preparation of hybrid supported metallocene catalysts

A hybrid supported metallocene catalyst was prepared in the same manner as in preparation example 1, except that [ (diethylsilane-diyl) -bis- (4-tert-butyl-phenylindenyl) ] zirconium dichloride having the following structural formula was used as the second metallocene compound in place of the second metallocene compound prepared in synthesis example 19.

Comparative preparation example 6: preparation of hybrid supported metallocene catalysts

A hybrid supported metallocene catalyst was prepared in the same manner as in preparation example 1, except that [ (methyl-t-butoxyhexylsilane-diyl) -bis- (2-methyl-4-t-butyl-phenylindenyl) ] zirconium dichloride having the following structural formula was used as the second metallocene compound in place of the second metallocene compound prepared in synthesis example 19.

< polymerization of Polypropylene >

Example 1

A2L stainless steel reactor was vacuum dried at 65 ℃ and cooled. 3mL of triethylaluminum was placed in the reactor at room temperature, 820ppm of hydrogen was injected, and then 1.5L of propylene was added. In this regard, the injection amount of hydrogen is a value based on the propylene monomer content.

After stirring for 10 minutes, 30mg of the hybrid supported metallocene catalyst of preparation 1 and 20mL of hexane slurry were prepared at 20 ℃ and charged to the reactor under argon (Ar) conditions. After the reactor temperature was gradually increased to 70 ℃, homopolymerization of propylene was carried out at a pressure of 30 bar for 1 hour, and unreacted propylene was discharged.

Examples 2 to 20

Each homopolypropylene was prepared in the same manner as in example 1, except that each hybrid supported metallocene catalyst prepared in preparation examples 2 to 20 was used instead of the hybrid supported metallocene catalyst prepared in preparation example 1.

Comparative examples 1 to 6

Each homopolypropylene was prepared in the same manner as in example 1, except that each single supported metallocene catalyst prepared in comparative preparation examples 1 to 3 or each hybrid supported metallocene catalyst prepared in comparative preparation examples 4 to 6 was used instead of the hybrid supported metallocene catalyst prepared in preparation example 1.

< experimental examples: evaluation of physical Properties of Polypropylene >

The activity of the metallocene catalysts used in the polymerization methods of examples and comparative examples and the physical properties of homopolypropylene prepared using the supported catalyst were evaluated in the following manner. The results are shown in table 1 below.

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

The activity was calculated by the ratio of the weight of homopolypropylene produced per unit time (h) (kg PP) to the weight of supported catalyst used (g).

(2) Melting Point (Tm)

The melting point (Tm) of the propylene polymer was measured using a differential scanning calorimeter (DSC, equipment name: DSC 2920, manufacturer: TA instruments). In detail, the polymer was heated to 220 ℃ by increasing the temperature, then held at the same temperature for 5 minutes, and then the temperature was decreased to 20 ℃. Then, the temperature was increased again, and the temperature corresponding to the peak in the DSC (differential scanning calorimeter, manufactured by TA) curve was determined as the melting point. In this regard, the temperature was increased and decreased at a rate of 10 ℃/min, respectively, and the melting point was the result of measurement in the second temperature increase and decrease interval.

(3) Tacticity (quintuple sequence distribution)

The tacticity of propylene polymers was measured using quantitative Nuclear Magnetic Resonance (NMR) spectroscopy, documented in the literature (V.Busico and R.Cipullo, Progress in Polymer Science,2001,26, 443) -533.

In detail, in the process of¹³After C-NMR analysis to measure the sequence distribution at the pentad level, the stereoregularity (pentad sequence distribution) of the homopolypropylenes of examples and comparative examples was expressed as% of the pentad (mmmm) sequences having the stereoregularity with respect to all the pentad sequences. mmmm% is a value based on moles.

In this regard, polypropylene was dissolved in 1.1.2.2-tetrachloroethane (TCE-d) using Bruker 500MHz NMR as a measuring instrument₂) In a solvent and measured at an absolute temperature of 393K: (¹³C; zgig30, ns 4096, d₁The time is 10 seconds, namely 10 seconds,¹h; pulse sequence zg30, ns 128, d₁3 seconds). Sequence distribution was analyzed with reference to analytical method AMT-3989-0k, and tacticity (mmmm%) was calculated according to literature (V.Busico and R.Cipullo, Progress in Polymer Science,2001,26, 443-533).

TABLE 1

Referring to table 1, examples 1 to 20, which respectively use the hybrid supported metallocene catalysts of preparation examples 1 to 20 according to exemplary embodiments of the present invention, exhibited melting points of 125.3 ℃ to 138.7 ℃ while exhibiting high activity during propylene polymerization, indicating that homopolypropylene having improved melt strength was prepared by effectively controlling the tacticity of the molecular structure of polypropylene and introducing Long Chain Branches (LCB) into the molecule.

In contrast, comparative example 1, which supports the second metallocene compound of chemical formula 2 alone, shows a reduced melt strength because Long Chain Branches (LCB) are not introduced into the polypropylene molecule and shows a high melting point of 153 ℃. In addition, comparative examples 2 and 3, which separately supported the first metallocene compound of chemical formula 1, showed much lower stereoregularity during propylene polymerization, and the resulting polypropylene had a high-viscosity atactic form.

Further, comparative example 4, in which a compound prepared by changing a substituent of an indene ligand in chemical formula 1 was used as a first precursor, and comparative examples 5 and 6, in which a compound prepared by changing a substituent of an indene ligand in chemical formula 2 or a compound prepared by changing a bridge substituent was used as a second precursor, showed decreased melt strength due to a decrease in the content of Long Chain Branches (LCB) in a polypropylene molecule, and showed high melting points of 153 ℃, 154 ℃, and 151 ℃, respectively, and showed significantly decreased catalytic activities of 7.6kg PP/g cat. hr, 6.5kg PP/g cat. hr, and 7.0kg PP/g cat. hr, respectively.