KR101982190B1 - Method of preparing olefin-based copolymer and olefin-based polymer prepared thereby - Google Patents

Abstract

The method for producing an olefin-based copolymer of the present invention includes copolymerizing two different olefin-based monomers in the presence of a hybrid catalyst composition. The olefin-based copolymer produced using the mixed catalyst composition may have a weight average molecular weight of 200,000 or more and a crystalline region of 90% or more. When the first transition metal compound and the second transition metal compound are used, high molecular weight and high crystallinity Based copolymer of the present invention.

Description

METHOD OF PREPARING OLEFIN-BASED COPOLYMER AND OLEFIN-BASED POLYMER PREPARED THEREBY Technical Field [1] The present invention relates to a process for producing an olefin-based copolymer,

The present invention relates to a method for producing an olefin-based copolymer, and relates to an olefin-based copolymer having a high crystallinity and a high molecular weight by using a hybrid catalyst composition containing different kinds of transition metals.

Metallocene catalysts for olefin polymerization have been developed for a long time. The metallocene compound is generally activated by using aluminoxane, borane, borate or other activator. For example, a metallocene compound having a ligand containing a cyclopentadienyl group and two sigma chloride ligands uses aluminoxane as an activator. When the chloride group of such a metallocene compound is substituted with another ligand (for example, benzyl or trimethylsilylmethyl group (-CH2SiMe3)), there has been reported an example in which the catalytic activity is increased.

European Patent EP 1462464 discloses a polymerization example using a hafnium metallocene compound having a chloride, benzyl, trimethylsilylmethyl group. Also, it has been reported that the production energy of the activated species varies depending on the alkyl ligand bound to the center metal (J. Am. Chem. Soc. 2000, 122, 10358). Korean Patent No. 820542 discloses a catalyst for the polymerization of olefins having a quinoline ligand. This patent relates to a catalyst having a living group containing silicon and germanium atoms other than methyl groups.

Dow has announced the early 1990s [Me2Si (Me4C5) NtBu] TiCl2 (hereinafter abbreviated as CGC) (U.S. Pat. No. 5,064,802), and the copolymerization reaction of ethylene and alpha-olefin The excellent aspects of the CGC over the known metallocene catalysts can be summarized as follows:

(1) High molecular weight polymers are produced with high activity even at high polymerization temperatures,

(2) the copolymerization of alpha-olefins with large steric hindrance such as 1-hexene and 1-octene is also excellent.

On the other hand, the copolymer produced by the CGC catalyst has a lower content of the low molecular weight portion than the copolymer prepared by the conventional Ziegler-Natta catalyst, thereby improving physical properties such as strength.

However, in spite of these advantages, the copolymer prepared by CGC et al. Has a disadvantage in that the processability is lowered compared with the polymer produced by the conventional Ziegler-Natta catalysts.

U. S. Patent No. 5,539, 076 discloses a metallocene / non-metallocene mixed catalyst system for making specific point density high density copolymers. The catalyst system is supported on the inorganic carrier. The problem with the supported Ziegler-Natta and metallocene catalyst systems is that the supported hybrid catalysts are less active than homogeneous single catalysts, making it difficult to produce olefinic polymers having tailored properties. Further, since the olefin-based polymer is produced in a single reactor, there is a fear that the gel generated in the blending method is produced, the insertion of the comonomer into the high molecular weight portion is difficult, and the shape of the resulting polymer is poor. Further, the two polymer components are not uniformly mixed, and quality control may become difficult.

Therefore, development of an olefin-based polymer capable of overcoming the disadvantages of conventional olefin-based polymers and capable of providing improved manufacturing processes and physical properties is still required.

Korean Patent Application No. 10-2012-0143808. US Patent No. 5,064,802 US Patent No. 6,548,686

Chem. Rev. 2003, 103, 283 Organometallics 1997, 16, 5958 Organometallics 2004, 23, 540 Chem. Commun. 2003, 1034 Organometallics 1999, 18, 348 Organometallics 1998, 17, 1652 J. Organomet. Chem. 2000, 608, 71

It is an object of the present invention to provide a process for preparing an olefin-based copolymer using a hybrid catalyst composition which is not less active than when used as a single catalyst, and it is an object of the present invention to provide a process for producing an olefin- Olefin-based copolymer.

In order to solve the above problems, the present invention provides a process for producing an olefin-based copolymer comprising copolymerizing two different olefin-based monomers in the presence of a hybrid catalyst composition.

The hybrid catalyst composition comprises 51 to 99 mole% of the first transition metal compound; And 1 to 49 mol% of the second transition metal compound.

In order to solve the above problems, the present invention provides a copolymer having a weight average molecular weight of 200,000 or more.

In order to solve the above problems, the present invention includes a copolymer having a crystalline region of 90% or more, a weight average molecular weight of 100,000 to 1,000,000, and a molecular weight distribution (MWD) of 1.0 to 4.0.

The olefin-based copolymer of the present invention can be produced by preparing a copolymer using a hybrid catalyst composition that is not less active than that of a single catalyst composition, thereby producing a high molecular weight olefin-based copolymer .

1 is a molecular weight distribution diagram of a copolymer prepared by varying the composition of a hybrid catalyst composition comprising a first transition metal compound and a second transition metal compound.
2 is a molecular weight distribution diagram of a copolymer prepared by varying the composition of a hybrid catalyst composition comprising a first transition metal compound and a conventional transition metal compound.
FIG. 3 is a graph showing the crystallinity measurement results of a copolymer prepared by varying the composition of a hybrid catalyst composition comprising a first transition metal compound and a second transition metal compound.
FIG. 4 is a graph showing crystallization results of a copolymer prepared by varying the composition of a mixed catalyst composition comprising a first transition metal compound and a conventional transition metal compound. FIG.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise.

In this specification, the terms " comprising, " " comprising, " or " having ", and the like are intended to specify the presence of stated features, But do not preclude the presence or addition of one or more other features, integers, steps, components, or combinations thereof.

The present invention provides a process for preparing an olefin-based copolymer comprising copolymerizing two different olefin-based monomers in the presence of a hybrid catalyst composition, and the present invention will be described in more detail below.

≪ Process for producing olefin-based copolymer >

According to another embodiment of the present invention, there is provided a process for producing an olefin-based copolymer comprising copolymerizing two different olefin-based monomers in the presence of the hybrid catalyst composition.

The olefin-based copolymer produced in this manner is superior in catalytic activity as compared with a catalyst composition containing only one transition metal compound or a mixed catalyst composition other than the heterometallic transition metal compound according to one embodiment of the present invention. Ratio may be maintained or higher, and may be a copolymer having a larger molecular weight.

The olefin-based monomer may be an alpha-olefin-based monomer, a cyclic olefin-based monomer, a diene olefin-based monomer, a triene olefin-based monomer, or a styrene-based monomer. Two or more of these monomers may be copolymerized.

The alpha-olefin-based monomer includes an aliphatic olefin having 2 to 24 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms. Specific examples thereof include ethylene, propylene, 1-butene, 1-pentene, 1-heptene, 1-octene, 1-decene, 4,4-dimethyl- 1-pentene, 4,4-diethyl-1-hexene, 3,4-dimethyl-1-hexene and the like. The alpha-olefins may also be homopolymerized or alternating, random, or block copolymerized.

The copolymerization of the alpha-olefins may be carried out by copolymerization of propylene and an alpha-olefin monomer having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms (ethylene and propylene, propylene and 1-butene, propylene and 1-hexene, -Methyl-1-pentene, propylene and 1-octene).

According to one embodiment of the present disclosure, the copolymerization may be a copolymerization of propylene with an alpha-olefin-based monomer having 2 and 4 to 12 carbon atoms.

In the copolymerization of propylene with other alpha-olefinic monomers, the amount of the other alpha-olefin may be selected to be not more than 90 mol% of the total monomer, and in the case of the propylene copolymer, 1 to 90 mol%, preferably 5 to 90 mol %, More preferably 10 to 70 mol%.

For example, when the copolymerization is a copolymerization of propylene with an alpha-olefin monomer having 2 and 4 to 12 carbon atoms, the amount of propylene and the alpha-olefin monomer having 2 and 4 to 12 carbon atoms is 1: 0.01 to 0.5 .

According to one embodiment of the present invention, the physical properties of the olefin-based copolymer according to one embodiment of the present invention may vary depending on the amount of the alpha-olefin-based monomer added to propylene.

For example, when the amount of the propylene and the alpha-olefin monomer is 1: 0.01 to 0.5, preferably 1: 0.05 to 0.2, by weight, a highly crystalline olefin-based copolymer having a crystalline region of 90% or more can be produced , Or an olefin-based copolymer having a molecular weight of 220,000 or more.

The cyclic olefins may have 3 to 24 carbon atoms, preferably 3 to 18 carbon atoms. Specific examples thereof include cyclopentene, cyclobutene, cyclohexene, 3-methylcyclohexene, cyclooctene, tetracyclo Norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6- Dimethyl-2-norbornene, 5,5,6-trimethyl-2-norbornene, ethylene norbornene and the like. The cyclic olefins can be copolymerized with the above-mentioned alpha-olefins, wherein the amount of the cyclic olefin is from 1 to 50 mol%, preferably from 2 to 50 mol%, based on the copolymer.

The dienes and trienes are preferably polyenes having 4 to 26 carbon atoms and having 2 or 3 double bonds. Specific examples thereof include 1,3-butadiene, 1,4-pentadiene, 1,4-hexa Dienes, 1,5-hexadiene, 1,9-decadiene, 2-methyl-1,3-butadiene, etc. The styrenes include styrene or an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms An alkoxy group, a halogen group, an amine group, a silyl group, a halogenated alkyl group or the like.

According to another embodiment of the present disclosure, the polymerizing step may be carried out in a hydrocarbon-based solvent in a liquid phase, a slurry phase, a bulk phase, or a gas phase polymerization.

Slurry phase, bulk phase, or gas phase polymerization, since they exist in the form of carrier-borne or insoluble particles of the carrier as well as the catalyst composition in homogeneous solution state. Further, the respective polymerization conditions may be variously changed depending on the state of the catalyst used (homogeneous or heterogeneous phase (supported type)), polymerization method (solution polymerization, slurry polymerization, gas phase polymerization) . And the degree of modification thereof can be easily modified by anyone skilled in the art.

The most preferred production process using the hybrid catalyst composition is a solution process, and it is also applicable to slurry or gas phase processes when such a composition is used together with an inorganic carrier such as silica.

During the copolymerization reaction using the hybrid catalyst composition, the reaction may be carried out in the presence of a reaction solvent, and the reaction solvent may include an organic solvent and an alkyl aluminum compound.

In the production process, the hybrid catalyst composition may contain a reaction solvent suitable for the olefin copolymerization process, and the organic solvent contained in the reaction solvent may be, for example, an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms such as pentane, , Nonane, decane, and their isomers and aromatic hydrocarbon solvents such as toluene and benzene, hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene, and the like, and they can be dissolved or diluted in such organic solvents and injected.

The organic solvent used herein is preferably used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of an alkylaluminum compound, and it is also possible to use a further cocatalyst.

Examples of the alkyl aluminum compound include trialkyl aluminum, dialkyl aluminum halide, alkyl aluminum dihalide, aluminum dialkyl hydride, and alkyl aluminum sesquihalide. More specific examples thereof include Al (C ₂ H _{5) 3, Al (C 2} H 5) 2 H, Al (C 3 H 7) 3, Al (C 3 H 7) 2 H, Al (iC 4 H 9) 2 H, Al (C 8 H 17) _{3, Al (C 12 H 25} ) 3, Al (C 2 H 5) (C 12 H 25) 2, Al (iC 4 H 9) (C 12 H 25) 2, Al (iC 4 H 9) 2 H , Al (iC ₄ H ₉ ) ₃ , (C ₂ H ₅ ) ₂ AlCl, (iC ₃ H ₉ ) ₂ AlCl or (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ . These organoaluminum compounds can be continuously introduced into each reactor and can be introduced at a rate of about 0.1 to 10 moles per kg of reaction medium introduced into the reactor for proper moisture removal.

According to another embodiment of the present disclosure, the copolymerizing step may be carried out in a batch reactor or a continuous reactor, preferably in a continuous reactor.

According to another embodiment of the present disclosure, the copolymerizing step may be carried out in the presence of an inert gas, for example, an argon or nitrogen gas.

The inert gas may be, for example, a nitrogen gas or a hydrogen gas alone, or a mixture of the gases.

The use of the inert gas serves to prevent moisture or impurities from entering the air and inhibit the catalytic activity. The inert gas may be added such that the mass ratio of the olefin monomer is about 1:10 to 1: 100 But is not limited thereto. If the amount of the inert gas used is too small, the catalytic composition reacts abruptly, making it difficult to produce an olefin polymer having a molecular weight and a molecular weight distribution. When an inert gas is introduced in an excessively large amount, .

In particular, in the method of producing a copolymer by the hybrid catalyst composition described in the present specification, two kinds of transition metal compounds, which can be used as catalysts, are mixed and used as one catalyst, and when one type of the hybrid catalyst composition is used The activity is not lowered, and an alpha-olefin-based copolymer having a larger molecular weight, for example, a propylene alpha-olefin copolymer can be produced.

<Hybrid Catalyst Composition>

The first transition metal compound

The hybrid catalyst composition according to one embodiment of the present invention includes a first transition metal compound represented by the following formula (1).

 [Chemical Formula 1]

N is an integer of 1 to 2, and R ₁ to R ₁₀ are the same or different from each other and each independently represents hydrogen, alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, Alkenyl having 6 to 20 carbon atoms, alkylaryl having 7 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms or silyl, and at least two adjacent ones of R ₁ to R ₁₀ are alkyl having 1 to 20 carbon atoms or carbon number 6 &Lt; / RTI &gt; to about 20 carbon atoms, to form a ring; R ₁₁ is hydrogen, halogen, alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, or aryl of 6 to 20 carbon atoms.

Q is carbon or silicon; M is a Group 4 transition metal; X ₁ and X ₂ are the same or different and are each independently selected from the group consisting of halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, Arylamino of 1 to 20 carbon atoms, arylamino of 6 to 20 carbon atoms, or alkylidene of 1 to 20 carbon atoms.

The method for preparing a first transition metal compound represented by Formula 1 according to an embodiment of the present invention comprises reacting a compound represented by Formula 1a and a compound represented by Formula 1b to prepare a compound represented by Formula 1c Lt; / RTI &gt; And reacting a compound represented by the following formula (1c) or a lithium salt thereof with a compound represented by the following formula (6).

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

&Lt; RTI ID = 0.0 &

(R _{11) 2} QCl ₂

[Formula 1e]

In the above formulas (1a) to (1e), n may be an integer of 1 to 2, and R ₁ to R ₁₀ are the same or different and each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a silyl group, and at least two of R ₁ to R ₁₀ , An alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms to form a ring.

R ₁₁ may be hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, X ₃ may be a halogen group, Q may be carbon or silicon have.

Each of the substituents defined in the above Formulas 1a to 1e will be described in detail as follows.

The alkyl group may include a linear or branched alkyl group, and the alkenyl group may include a linear or branched alkenyl group.

According to one embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically may be phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, It is not.

The alkylaryl group may mean an aryl group substituted by the alkyl group, and the arylalkyl group may mean an alkyl group substituted by the aryl group.

The halogen group may mean a fluorine group, a chlorine group, a bromine group or an iodine group.

The alkylamino group may denote an amino group substituted by the alkyl group, and may be a dimethylamino group, a diethylamino group or the like, but is not limited thereto.

The arylamino group may mean an amino group substituted by the aryl group, and includes, but is not limited to, a diphenylamino group and the like.

The silyl group includes trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triisopropylsilyl, triisobutylsilyl, triethoxysilyl, triphenylsilyl, tris (trimethylsilyl) , But are not limited to these examples.

The aryl group preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited thereto.

In the process for preparing a ligand of the first transition metal compound represented by the formula (1e) described above, the compound represented by the formula (1c) is reacted with the compound represented by the formula (1b) .

More specifically, according to one embodiment of the present invention, the indanyl halide derivative represented by Formula 1a and the indoline or tetrahydroquinoline derivative represented by Formula 1b are subjected to a coupling reaction in the presence of a base and a palladium catalyst To form a CN bond, whereby the compound represented by the above formula (1c) can be prepared.

The palladium catalyst used in this case is not particularly limited and includes, for example, bis (tri (tertiary butyl) phosphine) palladium (((tert-Bu) ₃ P) ₂ Pd), tetrakis ) palladium _{(Pd (PPh 3) 4)} , palladium chloride (PdCl _2), palladium acetate (Pd (OAc) ₂₎ or bis (dibenzylideneacetone) palladium (Pd (DBA) can be used for _2), and the like.

Next, the ligand represented by Formula (1e) can be obtained by reacting the compound represented by Formula (1c) or its lithium salt with the compound represented by Formula (1d).

More specifically, according to one embodiment of the present invention, the compound represented by the formula 1c is reacted with an organic lithium compound such as n-BuLi to prepare a lithium salt of the compound represented by the formula 1c. Next, after the compound represented by the above formula (1d) is mixed, the mixture is reacted by stirring. Thereafter, the reaction product is filtered to wash the resulting precipitate, and dried under reduced pressure to obtain a ligand compound represented by the above formula (1) wherein the indenyl group derivative is C2-symmetrically crosslinked by Q (carbon or silicon).

The compound represented by the formula (1e) obtained according to the production method described in this specification can be a ligand compound capable of forming a chelate with a metal.

According to the production method of the present invention, the ligand compound can be obtained in one of two forms of racemic and meso compounds, or in the form of a mixture of racemic and meso.

According to another aspect of the present invention, a method for preparing a first transition metal compound represented by Formula 1 comprises reacting a ligand compound represented by Formula 1e with a compound represented by Formula 1f.

(1f)

M (X ₁ X ₂ ) ₂

In the above formula (1f), M may be a transition metal of Group 4, for example, Ti, Zr or Hf, but is not limited thereto.

More specifically, the ligand compound represented by Formula 1a is reacted with an organic lithium compound such as n-BuLi to prepare a lithium salt, followed by mixing with the metal source represented by Formula 1f, and then the mixture is reacted by stirring . Thereafter, the reaction product is filtered to wash the resulting precipitate and dried under reduced pressure to obtain a first transition metal compound represented by the general formula (1) in the form of a complex in which a metal atom is bonded to a ligand compound.

Also, according to one embodiment of the present invention, the first transition metal compound represented by Formula 1 may be represented by one of the following structural formulas, but is not limited thereto.

In the above structural formula, Me means a methyl group and Ph means a phenyl group.

The first transition metal compound represented by the general formula (1) can be obtained in two forms of racemic and meso compounds, respectively, or can be obtained in the form of a mixture of racemate and meso.

The first transition metal compound obtained by the production method of the present invention has a structure in which a bisindenyl group is bridged by carbon or silicon, an indolinyl group or a tetrahydroquinoline group is connected to the indenyl group, and a C2 symmetric Crosslinked structure.

As described above, the first transition metal compound according to the production method of the present invention includes an electronically enriched indoline group or a tetrahydroquinoline group, so that the electron density of the center metal increases and the high-temperature stability and high molecular weight polyolefin- Can be advantageously used for synthesizing isotactic polyolefin-based polymers, for example, isotatic polypropylene.

The first transition metal compound obtained according to the preparation method of the present invention can be used as a polymerization reaction catalyst in the production of an olefin-based polymer.

The second transition metal compound

The hybrid catalyst composition according to one embodiment of the present invention includes a second transition metal compound represented by the following formula (2).

(2)

In Formula 2, M is a Group 4 transition metal, Q ₁ and Q ₂ are the same or different from each other and each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 6 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkylamido of 1 to 20 carbon atoms; Arylamido having 6 to 20 carbon atoms; Or an alkylidene of 1 to 20 carbon atoms.

R ₁ to R ₆ are the same or different from each other and each independently hydrogen; Silyl; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl of 1 to 20 carbon atoms; R ₁ and R ₂ may be connected to each other or two or more of R ₃ to R ₆ may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.

R ₇ to R ₁₁ are the same or different from each other and each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms; At least two adjacent to each other of R ₇ to R _{11 may} be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.

The second transition metal compound represented by Formula 2 may be an aromatic ring having 6 to 20 carbon atoms or an aromatic ring having 5 to 20 carbon atoms, wherein R ₁₀ and R ₁₁ may be connected to each other. In the case where an aliphatic ring or an aromatic ring is formed as described above, the second transition metal compound may include a compound represented by the following formula (3).

(3)

In Formula 3, M, Q _1, Q _2, R ₁ to R ₉ have the same meanings as defined in formula 2, Cy is a 5-or 6-membered aliphatic ring, are each independently hydrogen, R, R ₁₆ and R ₁₇ ; An alkyl group having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; An alkylaryl group having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms; m is an integer of 0 to 2 when Cy is a 5-membered aliphatic ring, and may be an integer of 0 to 4 when Cy is a 6-membered aliphatic ring.

The transition metal compound of Formula 3 described in the present specification is structurally linked with a cyclopentadienyl ligand having an amido group linked to a phenylene bridge in a ring form and has a narrow Cp-MN angle, The Q1-M-Q2 angle at which the monomer approaches is characterized by its wide retention. In addition, unlike the CGC structure connected by a silicon bridge, the cyclopentadiene, phenylene bridge, nitrogen and metal sites fused with benzothiophene are linked in the ring structure in the compound structure represented by the above formula (3) Thereby forming a more stable and rigid pentagonal ring structure. Therefore, when these compounds are activated by reacting them with co-catalysts such as methylaluminoxane or B (C ₆ F ₅ ) ₃ and then applied to the olefin polymerization, characteristics such as high activity, high molecular weight and high- &Lt; / RTI &gt;

In particular, because of the structural characteristics of the catalyst, it is possible to prepare an ultra-low density polyolefin copolymer having a density of less than 0.910 g / cc since a large amount of alpha-olefin can be introduced as well as linear low density polyethylene having a density of 0.910 to 0.930 g / cc . Particularly, it is possible to produce a polymer having a narrow MWD as compared to the CGC, excellent copolymerization, and a high molecular weight even in a low-density region by using the catalyst composition comprising the transition metal compound. In addition, various substituents can be introduced into the cyclopentadienyl and quinoline system to which benzothiophene is fused, which can ultimately control the electronic and stereoscopic environment around the metal, thereby controlling the structure and physical properties of the polyolefin produced .

The compound of formula (3) is preferably used to prepare a catalyst for the polymerization of olefin monomers, but is not limited thereto and is applicable to all fields in which the transition metal compound can be used.

In the present specification, alkyl and alkenyl may each be linear or branched.

In the present specification, the silyl may be a silyl substituted with an alkyl having 1 to 20 carbon atoms, and may be, for example, trimethylsilyl or triethylsilyl.

In the present specification, aryl includes monocyclic or polycyclic aryl, and specifically includes phenyl, naphthyl, anthryl, phenanthryl, klycenyl, pyrenyl, and the like.

According to another embodiment of the present invention, the compound represented by Formula 3 may include a compound represented by Formula 4 or 5 below.

[Chemical Formula 4]

In Formula 4, M, Q ₁ , Q ₂ , R ₁ to R ₉ are as defined in Formula 2, R ₁₂ to R ₁₇ are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms.

[Chemical Formula 5]

In Formula 5, M, Q ₁ , Q ₂ , R ₁ to R ₉ are as defined in Formula 2, and R ₁₈ to R ₂₁ each independently represents hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms.

According to another embodiment of the present disclosure, R ₁ and R ₂ may be alkyl of 1 to 20 carbon atoms, R ₁ and R ₂ may be alkyl of 1 to 6 carbon atoms, and R ₁ and R ₂ may be methyl Lt; / RTI &gt;

According to another embodiment of the present disclosure, R ₃ to R ₆ are the same or different and each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Or alkenyl having 2 to 20 carbon atoms, R ₃ to R ₆ are the same or different from each other, and each independently hydrogen; Or alkyl having 1 to 20 carbon atoms, and R ₃ to R ₆ may be the same or different and each independently hydrogen.

According to another embodiment of the present invention, R ₁₂ to R ₁₇ in Formula 4 are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Or alkenyl having 2 to 20 carbon atoms, and R ₁₂ to R ₁₇ in Formula 4 are each independently hydrogen; Or alkyl having 1 to 20 carbon atoms, and R ₁₂ to R ₁₇ in Formula 3 may be hydrogen.

According to another embodiment of the present invention, R ₁₂ to R ₁₆ in Formula 4 may be hydrogen, R ₁₇ may be alkyl having 1 to 20 carbon atoms, and R ₁₂ to R ₁₆ in Formula 4 may be hydrogen And R &lt; ₁₇ &gt; may be methyl.

According to another embodiment of the present invention, R ₁₈ to R ₂₁ in Formula 5 are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Or alkenyl having 2 to 20 carbon atoms, and R ₁₈ to R ₂₁ in Formula 5 are each independently hydrogen; Or alkyl having 1 to 20 carbon atoms, and R ₁₈ to R ₂₁ in Formula 5 may be hydrogen.

According to another embodiment of the present invention, R ₁₈ to R ₂₀ in Chemical Formula 5 may be hydrogen, and R ₂₁ may be alkyl having 1 to 20 carbon atoms, and R ₁₈ to R ₂₀ in Chemical Formula 5 may be hydrogen And R &lt; ₂₁ &gt; may be methyl.

According to another embodiment of the present disclosure, M may be Ti, Hf or Zr.

According to another embodiment of the present invention, the compound represented by Formula 3 may include the compound represented by Formula 4 or 5, and may specifically include at least one compound selected from the following formulas.

The compounds represented by the structural formulas listed above are not limited to the second transition metal compounds described in the present specification, and the compounds may be an example of the compound represented by the above formula (4) or (5).

The second transition metal compound represented by the general formula (2) is different from the compound represented by the general formula (3) in which R ₁₀ and R ₁₁ are connected to each other to form a cyclic compound. Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms. Thus, when a linear substituent is bonded, the second transition metal compound may include at least one compound selected from the following structural formulas.

The second transition metal compound represented by Formula 2 may include the compound represented by Formula 3, and the second transition metal compound represented by Formula 3 may be represented by, for example, the following (a) to (d) Can be prepared by:

(A) reacting an amine compound represented by the following general formula (3a) with alkyllithium, and then reacting the compound with a protecting group (-R ₀ , protecting group) To prepare a compound represented by the following formula (3b); (b) reacting the compound represented by Formula 3b with alkyllithium and then adding a ketone compound represented by Formula 3c to produce an amine compound represented by Formula 9; (c) reacting the compound represented by the above formula (3d) with n-butyllithium to prepare a di-lithium compound represented by the following formula (9); And (d) reacting the compound represented by Formula 3e with MCl ₄ (M = Group 4 transition metal) and an organolithium compound to prepare a transition metal compound represented by Formula 3 below.

[Chemical Formula 3]

(3b)

[Chemical Formula 3c]

(3d)

[Formula 3e]

In the above formulas (3a) to (3e), R 'is hydrogen and R ₀ is a protecting group, and the other substituents are the same as defined in formula (3).

In the step (a), the protecting group-containing compound may be selected from, for example, trimethylsilyl chloride, benzyl chloride, t-butoxycarbonyl chloride, benzyloxycarbonyl chloride, carbon dioxide, .

When the protecting group-containing compound is carbon dioxide, the formula (3b) may be a lithium carbamate compound represented by the following formula (3b ').

 (3b)

The description of the substituent shown in the above formula (3b) is as defined in the above formula (7).

According to a specific embodiment, the second transition metal compound represented by Formula 3 may be prepared according to the following Reaction Scheme 1.

[Reaction Scheme 1]

In the above Reaction Scheme 1, the substituents of the compounds shown in Reaction Scheme 1 are as shown in Formula 3, and n is 0 or 1.

Hybrid catalyst composition

The hybrid catalyst composition according to one embodiment of the present invention comprises 51 to 99 mol% of the first transition metal compound and 1 to 49 mol% of the second transition metal compound. Preferably 55 to 95 mol% and 5 to 45 mol%, or 60 to 90 mol% and 10 to 40 mol%, respectively, of the first transition metal compound and the second transition metal compound, 1 transition metal compound and the second transition metal compound, respectively, in an amount of 70 to 90 mol% and 10 to 30 mol%.

On the other hand, when a copolymer is produced using a first transition metal compound as a single catalyst, a copolymer having a high crystallinity region can be produced. When a copolymer is prepared using a second transition metal compound as a single catalyst A high molecular weight copolymer can be produced.

When the amount of the second transition metal compound is less than about 1 mol%, the activity of the first transition metal compound is so high that the activity of the second transition metal compound can not be exerted properly, so that the components of the resulting copolymer may not be uniform , The quality of the final product may be deteriorated.

In addition, when the second transition metal compound is contained in an amount exceeding about 49 mol%, the activity of the hybrid catalyst is lowered, and the yield of the finally produced copolymer may be lowered. In addition, the high crystalline area of the copolymer in which the second transition metal compound is produced can be reduced, and the potion of the irregular region can be increased, and the quality of the final product may also deteriorate.

The content of the first transition metal compound and the content of the second transition metal compound are in a complementary relationship, and the change of the catalytic properties or the properties of the olefin-based copolymer depending on the content of the first transition metal compound depends on the content of the second transition metal compound The characteristics change and behavior can be the same.

As described above, the first and second transition metal compounds contained in the hybrid catalyst composition may be a compound of a transition metal element of Group 4, for example, Hf, Zr, Ti, or the like may be applied.

The hybrid catalyst composition described herein may further comprise a cocatalyst. As the cocatalyst, those known in the art can be used.

For example, the catalyst composition may further include at least one of the following formulas (6) to (8) as a cocatalyst.

[Chemical Formula 6]

- [Al (R ₂₂ ) -O] _a -

In the general formula (6), R ₂₂ is each independently a halogen radical; A hydrocarbyl radical having from 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen; a is an integer of 2 or more;

(7)

D (R _{22) 3}

In Formula 7, D is aluminum or boron; Lt; ₂₂ &gt; are each independently as defined above;

[Chemical Formula 8]

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

Wherein L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; A is independently an aryl having 6 to 20 carbon atoms or an alkyl having 1 to 20 carbon atoms in which at least one hydrogen atom may be substituted with a substituent; The substituent is halogen, hydrocarbyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, or aryloxy of 6 to 20 carbon atoms.

According to one embodiment of the present invention, at least one promoter selected from the above formulas (6) to (8) may be added to the mixed catalyst composition and may be added by the following method.

First, contacting a mixed transition metal compound of a first transition metal compound and a second transition metal compound with a compound represented by the above formula (6) or (7) to obtain a mixture; And a step of adding the compound represented by the formula (8) to the mixture.

Secondly, there is provided a method for preparing a hybrid catalyst composition by bringing a compound represented by the formula (8) into contact with a mixed transition metal compound of a first transition metal compound and a second transition metal compound.

In the first method of the hybrid catalyst composition, the molar ratio of the compound represented by Formula 6 or Formula 7 to the mixed transition metal compound is preferably 1: 2 to 1: 5,000, more preferably 1: : 10 to 1: 1,000, and most preferably from 1:20 to 1: 500.

Meanwhile, the molar ratio of the compound represented by the formula (8) to the mixed transition metal compound is preferably 1: 1 to 1:25, more preferably 1: 1 to 1:10, and most preferably 1: 1: 5.

When the molar ratio of the compound represented by Formula 6 or Formula 7 to the mixed transition metal compound is less than 1: 2, the amount of the alkylating agent is so small that the alkylation of the metal compound can not proceed completely. When the molar ratio exceeds 1: The alkylation of the metal compound is carried out but there is a problem that activation of the alkylated metal compound can not be completely achieved due to the side reaction between the remaining excess alkylating agent and the activating agent of the above formula (8).

When the ratio of the compound represented by the general formula (8) to the mixed transition metal compound is less than 1: 1, the amount of the activating agent is relatively small and the activation of the metal compound is not completely performed. If there is a problem and the ratio exceeds 1:25, the activation of the metal compound is completely performed, but there is a problem that the unit cost of the catalyst composition is insufficient due to the excess activator remaining or the purity of the produced polymer is low.

In the case of the second method among the methods for producing the hybrid catalyst composition, the molar ratio of the compound represented by the formula (8) to the mixed transition metal compound is preferably 1: 1 to 1: 500, more preferably 1: 1:50, and most preferably from 1: 2 to 1:25. When the molar ratio is less than 1: 1, the amount of the activator is relatively small, and the activation of the metal compound is not completely achieved. Thus, there is a problem in that the activity of the mixed catalyst composition is decreased. However, there is a problem that the unit cost of the hybrid catalyst composition is not economically low due to the excess activator remaining or the purity of the produced polymer is low.

As the reaction solvent, hydrocarbon solvents such as pentane, hexane, heptane and the like and aromatic solvents such as benzene and toluene may be used in the preparation of the hybrid catalyst composition, but not always limited thereto, and all solvents Can be used.

Also, the mixed catalyst composition comprising the mixed transition metal compound and the cocatalyst may be used in the form of being supported on a carrier. As the carrier, silica or alumina can be used.

The compound represented by the above formula (6) is not particularly limited as long as it is alkylaluminoxane. Preferred examples thereof include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane, and a particularly preferred compound is methylaluminoxane.

The compound represented by the above formula (7) is not particularly limited, but preferable examples thereof include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri- Tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum Trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like. Particularly preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

Examples of the compound represented by Formula 8 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) Boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (ptrifluoromethylphenyl) boron, trimethylammoniumtetra (ptrifluoromethylphenyl) boron, tributylammoniumtetra N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethyl Ammonium tetramethylammonium tetraphenylborate, ammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenylboron Aluminum, trimethylammonium tetraphenyl aluminum, tripropylammonium tetraphenyl aluminum, trimethylammonium tetra (p-tolyl) aluminum, tripropylammonium tetra (p-tolyl) aluminum, triethylammonium tetra (o, Dimethylphenyl) aluminum, tributylammoniumtetra (p-trifluoromethylphenyl) aluminum, trimethylammoniumtetra (ptrifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetrapentafluorophenyl aluminum, diethylammonium tetrapentatentraphenyl aluminum, triphenyl Phosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum (P-tolyl) boron, triethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammoniumtetra (p-tolyl) boron, tripropylammoniumtetra Phenyl) boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (ptrifluoromethylphenyl) boron, trimethylammoniumtetra (ptrifluoromethylphenyl) boron, tributylammonium N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, Triphenylphosphonium tetraphenylboron, triphenylphosphonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetrapentafluorophenylboron, and the like.

The mixed transition metal compound; And at least one compound selected from the compounds represented by the general formulas (6) to (8) is contacted with two or more different olefinic monomers to produce a copolymer, a high crystalline and high molecular weight olefin based copolymer Lt; / RTI &gt;

Method for preparing hybrid catalyst composition

A method for preparing a hybrid catalyst composition according to an embodiment of the present invention includes the steps of (a) adding a first transition metal compound represented by the following formula (1) and a second transition metal compound represented by the following formula (2) ; And (b) introducing a second transition metal compound solution into the first transition metal compound solution such that the molar ratio of the first transition metal compound and the second transition metal compound is from 9.9: 0.1 to 5.1: 4.9.

The descriptions of the first transition metal compound, the second transition metal compound, the molar ratio thereof, and the reaction solvent are the same as those described above.

The hybrid catalyst composition according to one embodiment of the present invention is not limited to those produced by the above-described production method, but may be a hybrid catalyst comprising a first transition metal compound and a second transition metal compound, and other reaction solvent or co- The method is not particularly limited as long as the composition is produced.

&Lt; Olefinic copolymer >

According to another embodiment of the present disclosure, there is provided a composition comprising a copolymer having a crystalline region of 90% or more, a weight average molecular weight of 100,000 to 1,000,000 g / mol and a molecular weight distribution (MWD) of 1.0 to 4.0 Olefin-based copolymer.

According to the present specification, the olefin-based copolymer produced using the hybrid catalyst composition can have a large weight average molecular weight while retaining the ratio or other activity of the highly crystalline region as compared with the case of using a single catalyst composition.

The olefin-based copolymer may have a crystalline region of 90% or more, and the copolymer having a crystalline region of 90% or more may have a weight average molecular weight of about 100,000 to 1,000,000 g / mol. The molecular weight distribution (MWD; Molecular Weight) of the highly crystalline olefinic polymer Distribution) may be from about 1.0 to about 4.0, preferably from about 1.5 to 3.5, and more preferably from 2.0 to 3.0.

The olefin-based copolymer preferably has a melt index (MI) of from about 0.1 to about 2000 g / 10 min, preferably from about 0.1 to about 1000 g / 10 min, more preferably from about 0.1 to about 1000 g / 10 min as measured according to ASTM D1238 at 190 DEG C under a load of 2.16 kg May be about 0.1 to 500 g / 10 min, but is not limited thereto.

As in the conventional case, when an olefin-based copolymer is prepared using a single catalyst composition containing only the first transition metal compound or a mixed catalyst composition with a transition metal compound other than the hybrid catalyst with the second transition metal compound It has been difficult to produce a copolymer having a low molecular weight, a low crystallinity, or a low content of a crystalline region and satisfactory physical properties.

However, according to one embodiment of the present invention, the olefin-based copolymer produced in the presence of the hybrid catalyst composition has a crystalline region of 90% or more, a weight average molecular weight of 220,000 g / mol or more, 3.0, and it is possible to provide an olefin-based copolymer having improved properties of a copolymer because it has excellent crystallinity, molecular weight, etc. as compared with a copolymer prepared using a conventional catalyst composition or a single catalyst composition can do.

According to another embodiment of the present disclosure, the olefin-based polymer may be used for blow molding, extrusion molding, or injection molding.

Example

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

In the following examples, the term " overnight " or " overnight " means approximately 12 to 16 hours and " normal temperature " refers to a temperature of 20 to 30 ° C. The organic reagents and solvents used were purchased from Aldrich and Merck and purified by standard methods. At every stage of the synthesis, the contact between air and moisture was blocked to improve the reproducibility of the experiment. Spectra were obtained using a 500 MHz nuclear magnetic resonance (NMR) system to demonstrate the structure of the resulting compound.

1. Preparation of Catalyst Composition

Manufacturing example  1: Preparation of first transition metal compound

One) Ligand  Preparation of compounds

Synthesis of 1- (2-methyl-1H-inden-4-yl) -1,2,3,4-tetrahydroquinole

To a 500 ml 2-neck Schlenk flask was added 4-bromo-2-methyl-1H-indene (15.7 g, 75.63 mmol), 1,2,3,4-tetrahydroquinone (11.08 g, 83.19 mmol), LiOtBu (18.16 g, 226.89 mmol ) And Pd (P (tBu) 3) 2 (0.77 g, 1.5 mmol) were added, and 252 mL of dry toluene was added to dissolve the starting material and the mixture was stirred overnight at 110 ° C. in an oil bath. After cooling to room temperature, 151 mL of deionized water was added to terminate the reaction.

The organic layer was separated and the water layer was extracted twice with 50 mL of dichloromethane (DCM). The organic layer was collected, dried with Na2SO4, filtered, distilled and vacuum-dried at 60 DEG C overnight to obtain an orange compound (15.8 g, quantitative yield relative to 4-bromo-2-methyl-1Hindene and yield of 80% relative to the starting material).

7.15-7.10 (d, J = 8.0 Hz, 1H of isomers), 7.15-7.10 (d, J = 7.5 Hz, 2H in isomers), 7.15-7.10 ), 7.10-7.05 (d, J = 8.0 Hz, 1H in isomers), 7.05-7.00 (d, J = 7.5 Hz, 3H in isomers), 7.00-6.95 6.90-6.80 (t, J = 7.5 Hz, 3H in isomers), 6.65-6.58 (m, 3H in isomers), 6.48 J = 8.0Hz, 1H in isomers), 6.25-6.22 (d, J = 8.0Hz, 2H in isomers), 3.62-3.59 (t, J = 5.5Hz, 6H in 2-quinolinyl of isomers), 3.33 , 2H in 1H-indene of isomers), 3.10 (s, 3H in 1H-indene of isomers), 3.00-2.85 (m, 6H in 4-quinolinyl of isomers), 2.22-2.00 2-Me of isomers)

Synthesis of Bis (4- (3,4-dihydroquinolin-1 (2H) -yl) -2-methyl-1H-inden-

BuLi (2.5M in n-Hx) (26.6 g, 60.5 mmol) was added at -78 ° C after dissolving the starting material in 300 mL of dry diethyl ether by adding the compound (15.8 g, 60.5 mmol) mL) was added, and the mixture was stirred at room temperature overnight. Then, it was filtered using glass frit (G4). The solid remaining in the glass frit was vacuum dried to obtain a lithiated product (14.4 g, 89% yield) of a white solid. In the glove box, the lithiated product (14.2 g, 53.1 mmol) was placed in a 500 mL Schlenk flask and dissolved by adding 152 mL of dry toluene and 7.6 mL of THF. After the temperature was lowered to -30 DEG C, Me2SiCl2 (3.2 mL, 26.6 mmol) was added, and the mixture was stirred at room temperature for 1 day. Then, the mixture was stirred for 5 hours under an oil bath at 140 ° C. After cooling to room temperature, 50 mL of deionized water was added to terminate the reaction.

The organic layer was separated and the water layer was extracted twice with 50 mL of dichloromethane (DCM). The organic layers were combined and dried with K2CO3, filtered, distilled and vacuum dried overnight at 60 &lt; 0 &gt; C to obtain a brownish white solid ligand compound (15.8 g, quantitative yield relative to lithiated product, 89% yield based on starting material). H-NMR analysis showed that the ratio of rac: meso was about 1: 1.

7.25 (d, J = 7.5 Hz, 2H, 7,7 ' -H &lt; / RTI &gt; 1H, indenyl of meso-isomer), 7.15 (t, J = 7.5 Hz, 2H, indenyl of rac-isomer of 6,6'- (d, J = 7.5 Hz, 2H, 5,5'-H in quinolinyl of rac-isomer), 7.08 4H, 5,5'-H in indenyl of rac- and meso-isomers), 6.85-6.81 (m, 4H), 7.02 (dd, J1 = 7.0 Hz, J2 = 1.0 Hz, , 7,7'-H in quinolinyl of rac- and mesoisomers), 6.60 (td, J1 = 7.5 Hz, J2 = 1.0 Hz, 4H, 6,6'-H in quinolinyl of rac- and meso-isomers), 6.46 (s, 4H, 3,3'-H in indenyl of rac- and meso-isomers), 6.26 (d, J = 8.0 Hz, 4H, 8,8'-H quinolinyl of racand meso-isomers), 3.81 1H, indenyl of rac-isomer), 3.79 (s, 2H, 1,1'-H indenyl of meso-isomer), 3.69-3.57 (m, 8H, 2.21 (d, J = 0.5 Hz, 1H), 2.92 (t, J = 6.0 Hz, 8H, 4,4'-H in quinolinyl of rac- and meso-isomers) 6H, 2,2'-Me in meso-isomer) , 2.13 (d, J = 1.0 Hz, 6H, 2,2'-Me in rac-isomer), 2.13-2.08 (m, 8H, 3,3'-H quinolinyl of rac- and mesoisomers) s, 3H, SiMe of meso-isomer), -0.29 (s, 6H, SiMe2 of rac-isomer), -0.30

2) Preparation of transition metal compounds

Synthesis of rac-dimethylsilylene-bis (4- (3,4-dihydroquinolin-1 (2H) -yl) -2-methyl-indenyl) hafnium dichloride

(5.2 mmol, rac: meso = 1: 1) was added to a 250 mL Schlenk flask and 85 mL of dry toluene was added to dissolve the starting material. Then, n-BuLi -Hx) was added thereto, and the mixture was stirred at room temperature for 5 hours. The mixture was cooled to -78 ° C, transferred to a Schlenk flask containing 1.7 g (5.2 mmol in 20 mL toluene) of HfCl 4 solution at -78 ° C. prepared in advance, and stirred overnight at room temperature. After completion of the reaction, the mixture was filtered with a glass frit (G4) containing celite. The solid remaining in the glass frit was washed three times with about 3 mL of dry toluene. The toluene solution was vacuum dried to obtain a red solid. The solids remaining in the glass frit were dissolved in dichloromethane (DCM). The DCM filtrate was vacuum dried to give a red solid. H-NMR analysis showed that both solids were Hf complex with rac: meso = 1: 1. The crude product was collected and placed in an oil bath at 45 ° C and dissolved in 50 mL of dry toluene while stirring. This was stored in a -30 ° C freezer for 3 days and recrystallized. The resulting red solid was filtered with glass frit (G4), washed twice with 3 mL of dry n-hexane and dried in vacuo to give 1.0 g (1.2 mmol, 23% yield) of racemic final product.

2H, 7,7'-H indenyl), 6.98 (d, J = 7.5 Hz, 2H, 5,5'-H in quinolinyl ), 6.90 (d, J = 7.0 Hz, 2H, 5,5'-H indenyl), 6.82-6.79 (m, 2H, 7,7'-H in quinolinyl), 6.72 (dd, J1 = 8.5 Hz, 2H, 6,3'-H indenyl), 6.68-6.65 (m, 2H, 6,6'-H in quinolinyl), 6.57 (s, 2H, , 6.51 (d, J = 8.5 Hz, 2H, 8,8'-H in quinolinyl), 3.81-3.66 (m, 4H, 2,2'-H in quinolinyl), 2.63-2.53 4H, 3,3'-H in quinolinyl), 0.82 (s, 6H, SiMe2), 2.03 (s, 6H, 2,2'-Me), 1.87-1.67

Manufacturing example  2: Preparation of second transition metal compound

One) Ligand  Preparation of compounds

Benzo [b] cyclopenta [d] thiophen-3-yl) -2-methyl-1,2,3,4-tetrahydroquinoline (8- (1,2- -dimethyl-1H-benzo [b] cyclopenta [d] thiophen-3-yl) -2-methyl-1,2,3,4-tetrahydroquinoline

NBuLi (14.9 mmol, 1.1 eq) was slowly added dropwise to a solution of 2-methyl-1,2,3,4-tetrahydroquinoline (2 g, 13.6 mmol) in ether (10 mL) at -40 ° C. After slowly raising the temperature to room temperature, the mixture was stirred at room temperature for 4 hours. The temperature was again lowered to -40 ° C (g) and the reaction was maintained at low temperature for 0.5 hour. After slowly warming up, the remaining CO2 (g) was removed through a bubbler. (1.9 g, 8.8 mmol) was dissolved in diethyl ether (20 ml) at -20 ° C, and the mixture was stirred at -20 ° C for 2 hours at -20 ° C with THF (17.6 mmol, 1.4 ml, tBuLi The mixture was stirred at room temperature for 12 hours and then poured into 10 mL of water. The mixture was stirred for 2 minutes with hydrochloric acid (2N, 60 mL), extracted with an organic solvent, neutralized with aqueous NaHCO3 solution, Water was removed with MgSO4. A yellow oil was obtained via a silica gel column (1.83 g, 60% yield).

3H, CH3), 1.89-1.63 (m, 3H, Cp-Hquinoline-CH2), 2.62-2.60 (m, 2H, quinoline (D, 2H, quinoline-NCH2), 3.92 (broad, 1H, NH), 2.61-2.59 (m, 2H, quinoline-NCH2), 2.70-2.57 Aromatic), 7.62-7.60 (m, 2H, aromatic), 6.79-6.76 (t, 1H, aromatic) m, 1H, aromatic) ppm

2) Preparation of transition metal compounds

Benzo [b] cyclopenta [d] thiophen-3-yl) -2-methyl-1,2,3,4- tetrahydroquinoline- titanium dichloride (8- Synthesis of 1,2-dimethyl-1H-benzo [b] cyclopenta [d] thiophen-3-yl) -2-methyl-1,2,3,4-tetrahydroquinoline-titanium dichloride

To the ligand (1.0 g, 2.89 mmol), nBuLi (3.0 mmol, 2.1 eq) was slowly added dropwise at -20 ?. Yellow slurry was observed to form and slowly warmed to room temperature and then stirred at room temperature for 12 hours. TiCl4DME (806 mg, 2.89 mmol, 1.0 eq) was added dropwise thereto, followed by stirring at room temperature for 12 hours. After removal of the solvent, it was extracted with toluene to give a red solid (700 mg, 52% yield).

3H, Cp-CH3), 1.39 (s, 3H, Cp-CH3), 2.39 (s, 3H, Cp- 2H, quinoline-NCH2), 5.22-5.20 (m, 1H, N-CH), 5.26-5.24 (m, 1H), aromatic), 7.89-6.87 (m, 2H, aromatic) 6.99-6.95 (m,

Manufacturing example  3: Preparation of hybrid catalyst composition

The first transition metal compound prepared in Preparation Example 1 was added to a toluene solvent treated with triisobutylaluminum to prepare 0.1 ml of a first transition metal compound solution having a concentration of the first transition metal compound of 1 × 10 ^-6 M And 0.1 ml of the second transition metal compound solution prepared in Preparation Example 2 was prepared in the same manner.

The mixed solution of the second transition metal compound is introduced into the mixed solution of the first transition metal compound and the second transition metal compound to form a mixed catalyst composition at a desired molar ratio (first transition metal compound: second transition metal compound).

Comparative Manufacturing Example

Using the transition metal compound represented by the above structural formula (Patent Document 10-2007-0096465) and the first transition metal compound prepared in Preparation Example 1, the same procedure as in Preparation Example 3 was repeated to obtain a 9: 1 And 8: 2, respectively.

2. Preparation of olefin-based copolymer

Example  One

A 2 L autoclave reactor was charged with 0.8 L of a toluene solvent, and 250 g of propylene and 70 psi of ethylene were added thereto so that the molar ratio of propylene to ethylene was 10.6: 1. Thereafter, the pressure was adjusted to 500 psi under a high pressure argon pressure, Lt; RTI ID = 0.0 &gt; 70 C. &lt; / RTI &gt;

Then, the mixed catalyst composition (molar ratio = 9: 1, 0.1 ml, 1 x 10 ^-6 M) prepared in Preparation Example 3 and dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst (0.2 ml, 5 x 10 &lt; ^-6 &gt; M) were placed in a reactor under a high-pressure argon pressure, and the copolymerization reaction was carried out for 10 minutes. The reaction heat was removed through a cooling coil inside the reactor to keep the polymerization temperature at a maximum. At this time, 10 equivalents of the cocatalyst was added to the mixed catalyst composition.

Next, after the completion of the copolymerization reaction, the remaining gas was taken out, and excess ethanol was added to the polymer solution discharged to the lower portion of the reactor to induce precipitation. The precipitated polymer was washed with ethanol and acetone two to three times, respectively, and then dried in a vacuum oven at 80 캜 for 12 hours or more, and then the physical properties thereof were measured.

Example  2

The copolymerization reaction was carried out in the same manner as in Example 1 to prepare a polymer, and the mixed catalyst composition was used in a molar ratio of the first transition metal compound and the second transition metal compound of 8: 2.

Comparative Example  One

The copolymerization reaction was carried out in the same manner as in Example 1 to prepare a polymer. Instead of using the mixed catalyst composition, a catalyst composition containing only the first transition metal compound prepared in Preparation Example 1 was used.

Comparative Example  2

The copolymerization reaction was carried out in the same manner as in Example 1 to prepare a polymer. Instead of using the hybrid catalyst composition, the molar ratio of the first transition metal compound and the transition metal compound represented by the structural formula in Comparative Preparation Example 1 was 9 : &Lt; / RTI &gt; 1 was used.

Comparative Example  3

The copolymerization reaction was carried out in the same manner as in Example 1 to prepare a polymer. Instead of using the hybrid catalyst composition, the molar ratio of the first transition metal compound and the transition metal compound represented by the structural formula in Comparative Preparation Example 1 was 8 : 2. &Lt; / RTI &gt;

Experimental Example  1: Evaluation of molecular weight and molecular weight distribution

The weight average molecular weight of the polymer was measured by the GPC method, and the molecular weight distribution was also measured by the GPC method. The results are shown in FIGS. 1 and 2. 1 and 2 are the first transition metal compound, B1 is the second transition metal compound, and B2 is the transition metal compound prepared in Comparative Preparation Example 1.

Mixing ratio MFR Mw MWD Comparative Example 1 (A1: B2) 10: 0 16.2 209,116 1.94331 Comparative Example 2 (A1: B2) 9: 1 14.0 212,969 2.00783 Comparative Example 3 (A1: B2) 8: 2 12.1 218,924 1.9493 Example 1 (A1: B1) 9: 1 12.3 227,291 2.17287 Example 2 (A1: B1) 8: 2 7.4 227,117 2.015

Experimental Example  2: Crystallinity evaluation

The ratio of the crystalline to amorphous regions of the polymer is TreF. The results are shown in FIGS. 3 and 4. FIG. 3 and 4 are the first transition metal compounds, B1 is the second transition metal compound, and B2 is the transition metal compound prepared in Comparative Preparation Example 1 above.

Mixing ratio
(First: second) Amorphous Crystalline ℃ % ℃ % Comparative Example 1 10: 0 -17.7 4.9 25.8 95.1 Comparative Example 2 9: 1 -17.7 10.5 29.0 89.5 Comparative Example 3 8: 2 -17.7 12.7 27.6 87.3 Example 1 9: 1 -17.5 5.0 33.8 95.0 Example 2 8: 2 -17.5 5.2 26.8 94.8

Referring to Tables 1 and 2 and FIGS. 1 to 4, in Comparative Example 1 using a single catalyst composition, although the crystalline region is 95%, the transition metal compound other than the second transition metal compound has a relatively small molecular weight, And the first transition metal compound were mixed, the molecular weight was also relatively small, and the fraction of the crystalline region was also less than 90%.

On the other hand, in the case of Examples 1 and 2 using the hybrid catalyst composition of the present invention in which the first transition metal compound and the second transition metal compound were mixed, the fraction of the crystalline region was 95%, which was superior to Comparative Examples 2 and 3 And it was confirmed that a copolymer having a relatively large molecular weight was produced in comparison with Comparative Examples 1 to 3 even though the same polymerization conditions and analysis conditions were used.

As a result, when the hybrid catalyst composition of the present invention is used, olefin-based copolymers such as propylene alpha-olefin copolymer have excellent physical properties, and olefin-based copolymers having high crystallinity and high molecular weight Can be produced.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, Of the right.

Claims (23)

Copolymerizing two different olefinic monomers in the presence of a hybrid catalyst composition,
Wherein the mixed catalyst composition comprises 51 to 99 mol% of the first transition metal compound represented by the following formula (1); And 1 to 49 mol% of a second transition metal compound represented by the following formula (2): &lt; EMI ID =
[Chemical Formula 1]

In Formula 1,
n is an integer of 1 to 2,
R ₁ to R ₁₀ are the same or different and each independently represents hydrogen, alkyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, Alkylaryl, arylalkyl or silyl having 7 to 20 carbon atoms, and at least two adjacent ones of R ₁ to R ₁₀ are connected to each other by an alkylidene having 1 to 20 carbon atoms or aryl having 6 to 20 carbon atoms, &Lt; / RTI &gt; R ₁₁ is hydrogen, halogen, alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, or aryl of 6 to 20 carbon atoms;
Q is carbon or silicon;
M is a Group 4 transition metal;
X ₁ and X ₂ are the same or different and are each independently selected from the group consisting of halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, Arylamino of 1 to 20 carbon atoms, arylamino of 6 to 20 carbon atoms, or alkylidene of 1 to 20 carbon atoms.
(2)

In Formula 2,
M is a Group 4 transition metal,
Q ₁ and Q ₂ are the same or different from each other, and each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 6 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkylamido of 1 to 20 carbon atoms; Arylamido having 6 to 20 carbon atoms; Or an alkylidene of 1 to 20 carbon atoms,
R ₁ to R ₆ are the same or different and each independently hydrogen; Silyl; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl of 1 to 20 carbon atoms; R ₁ and R ₂ may be connected to each other or two or more of R ₃ to R ₆ may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, or aryl of 6 to 20 carbon atoms,
R ₇ to R ₁₁ are the same or different from each other, and each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms; At least two adjacent to each other of R ₇ to R _{11 may} be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms. The method according to claim 1,
Wherein the olefin-based copolymer comprises a copolymer having a weight average molecular weight of 200,000 or more. The method according to claim 1,
Wherein the olefin-based copolymer comprises a copolymer having a crystalline region of 90% or more. The method of claim 3,
Wherein the olefin-based copolymer comprises a copolymer having a weight average molecular weight of 100,000 to 1,000,000. The method of claim 3,
Wherein the olefin-based copolymer comprises a copolymer having a molecular weight distribution (MWD) of 1.0 to 4.0. The method according to claim 1,
Wherein the olefin-based copolymer comprises a copolymer of propylene / alpha-olefin. The method according to claim 1,
Wherein the olefinic monomer comprises at least two monomers selected from the group consisting of an alpha-olefin-based monomer, a cyclic olefin-based monomer, a dienolefin-based monomer, and a styrene-based monomer. The method according to claim 1,
Wherein said copolymerization comprises copolymerization of propylene with alpha-olefinic monomers having 2 and 4 to 12 carbon atoms. 9. The method of claim 8,
Wherein the amount of the propylene and the amount of the alpha-olefin monomer having 2 to 4 carbon atoms and 2 to 4 carbon atoms is 1: 0.01 to 1: 0.5 by weight. The method according to claim 1,
Wherein the copolymerization step proceeds in a liquid phase, a slurry phase, a bulk phase, or a gas phase polymerization in a hydrocarbon-based solvent. The method according to claim 1,
Wherein the copolymerization is carried out in a continuous reactor. The method according to claim 1,
Wherein the copolymerizing step is carried out in the presence of an inert gas. delete The method according to claim 1,
The hybrid catalyst composition comprises 60 to 90 mole% of the first transition metal compound; And 10 to 40 mol% of the second transition metal compound. The method according to claim 1,
Wherein the second transition metal compound represented by the general formula (2) comprises a compound represented by the following general formula (3): &lt; EMI ID =
(3)

In Formula 3,
M, Q ₁ , Q ₂ , and R ₁ to R ₉ are the same as defined in Formula 2,
Cy is a 5-or 6-membered aliphatic ring,
R, R ₁₆ and R ₁₇ are each independently hydrogen; An alkyl group having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; An alkylaryl group having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms;
m is an integer of 0 to 2 when Cy is a 5-membered aliphatic ring, and an integer of 0 to 4 when Cy is a 6-membered aliphatic ring. 16. The method of claim 15,
Wherein the compound represented by the formula (3) comprises a compound represented by the following formula (4) or (5):
[Chemical Formula 4]

In Formula 4,
M, Q ₁ , Q ₂ , and R ₁ to R ₉ are the same as defined in Formula 2,
R ₁₂ to R ₁₇ are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or an arylalkyl group having 7 to 20 carbon atoms.
[Chemical Formula 5]

In Formula 5,
M, Q ₁ , Q ₂ , and R ₁ to R ₉ are the same as defined in Formula 2,
R ₁₈ to R ₂₁ are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or an arylalkyl group having 7 to 20 carbon atoms. 16. The method of claim 15,
Wherein the compound represented by Formula 3 comprises at least one compound selected from the following structural formulas:

The method according to claim 1,
Wherein the second transition metal compound represented by Formula 2 comprises at least one compound selected from the following structural formulas:

The method according to claim 1,
Wherein the catalyst composition further comprises at least one cocatalyst. Wherein the crystalline region is 90% or more, the weight average molecular weight is 220,000 to 1,000,000, and the molecular weight distribution (Molecular weight distribution, MWD) is from 1 to 3. delete 21. The method of claim 20,
Wherein the olefin-based copolymer comprises a copolymer of propylene / alpha-olefin. delete

Images