WO2021060908A1 - Supported hybrid catalyst and method for preparing polyolefin by using same - Google Patents

Abstract

The present invention provides a supported hybrid catalyst, and a method for preparing a polyolefin by using same, the supported hybrid catalyst comprising two or more types of transition metal compounds having a specific chemical structure, and thus a polyolefin, particularly, a high-density polyethylene, having a molecular structure optimized to improve the tensile strength of a chlorinated polyolefin compound can be prepared.

Description

Hybrid supported catalyst and method for producing polyolefin using

Cross-reference with related application(s)

This application is the benefit of priority based on Korean Patent Application Nos. 10-2019-0120102 and 10-2019-0120103 filed September 27, 2019, and Korean Patent Application No. 10-2020-0124243 filed September 24, 2020. All the contents disclosed in the document of the Korean patent application are included as part of this specification.

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

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed according to their respective characteristics. Ziegler Natta catalysts have been widely applied to existing commercial processes since their invention in the 50s, but since they are multi-site catalysts with multiple active points, they are characterized by a wide molecular weight distribution of polymers. There is a problem in that there is a limit to securing desired physical properties because the composition distribution of is not uniform. In particular, physical properties may be deteriorated due to polymer chains having a relatively low molecular weight due to a wide molecular weight distribution.

On the other hand, the metallocene catalyst is composed of a combination of a main catalyst composed of a metallocene compound and a cocatalyst composed of an organometallic compound composed mainly of aluminum. , It has properties that can change copolymerization properties, molecular weight, crystallinity, etc.

U.S. Patent No. 5,032,562 describes a method of preparing a polymerization catalyst by supporting two different transition metal catalysts on one supported catalyst. This is a method of producing a bimodal distribution polymer by supporting a titanium (Ti)-based Ziegler-Natta catalyst producing high molecular weight and a zirconium (Zr)-based metallocene catalyst producing low molecular weight on one support. As a result, the supporting process is complicated, and the morphology of the polymer is deteriorated due to the cocatalyst.

U.S. Patent No. 5,525,678 describes a method of using a catalyst system for olefin polymerization in which a high molecular weight polymer and a low molecular weight polymer can be simultaneously polymerized by simultaneously supporting a metallocene compound and a non-metallocene compound on a carrier. This has a disadvantage in that the metallocene compound and the non-metallocene compound must be separately supported, and the carrier must be pretreated with various compounds for the supporting reaction.

U.S. Patent No. 5,914,289 describes a method of controlling the molecular weight and molecular weight distribution of a polymer using a metallocene catalyst supported on each carrier, but it takes a lot of time and the amount of solvent used to prepare the supported catalyst. In addition, there was a hassle to support each of the metallocene catalysts used on the carrier.

Moreover, according to this prior art, there is a disadvantage in that it is difficult to effectively prepare a polyolefin, in particular, an ethylene (co)polymer that satisfies a desired level of density and a narrow molecular weight distribution at the same time.

On the other hand, chlorinated polyethylene (CPE) is a product obtained by substituting a portion of hydrogen in polyethylene with chlorine, and is used as an impact modifier for polyvinyl chloride (PVC) or crosslinked to manufacture wire coverings or hoses. .

Chlorinated polyethylene, which is used as a material for electric wire coating, is used in a heat-crosslinked structure by a peroxide-based crosslinking agent, which is a crosslinking agent. In order to prevent damage to the coating when the wire is bent, it must have excellent tensile strength in a crosslinked compound state.

In the case of PVC compound products, the strength of the compound varies depending on the properties of the chlorinated polyolefin. In the case of general-purpose chlorinated polyolefins, which are widely known at present, since polyolefins using Ziegler-Natta catalysts are applied, the uniformity of chlorine distribution in the polyolefins is poor according to the wide molecular weight distribution, and the impact strength is insufficient when compounded with PVC.

Recently, in order to improve the tensile strength of chlorinated polyolefin compounds for electric wires, high-density polyethylene (HDPE) resin prepared using a metallocene catalyst is chlorinated to produce chlorinated polyethylene, and then a crosslinking agent is added to prepare a compound.

In general, the higher the Mooney viscosity (MV) of the chlorinated polyolefin and the higher the Mooney viscosity of the compound, the higher the tensile strength of the compound, but there is a problem of lowering the workability during compression.

Accordingly, there is a need for production of high-density polyethylene capable of improving the tensile strength of a compound without deteriorating processability at the same level of Mooney viscosity, and development of a catalyst therefor.

The present invention is to provide a hybrid supported catalyst capable of producing a polyolefin having a molecular structure optimized for improving the tensile strength of a chlorinated polyolefin compound, particularly high density polyethylene.

The present invention is also to provide a method for producing a polyolefin capable of improving the tensile strength of a chlorinated polyolefin compound by using the aforementioned hybrid supported catalyst.

According to an embodiment of the present invention, at least one first transition metal compound represented by the following formula (1); At least one second transition metal compound represented by the following formula (2); And a carrier on which the first and second transition metal compounds are supported.

[Formula 1]

(Cp ¹ R ₁₁ ) _m (Cp ² R ₁₂ ) M ₁ (Z ₁ ) _3-m

In Formula 1,

M ₁ is a Group 4 transition metal;

Cp ¹ and Cp ² are the same as or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals. One, and these may be substituted with _{C 1-20 hydrocarbons;}

R ₁₁ and R ₁₂ are the same as or different from each other, and each independently hydrogen, C _1-20 alkyl, C _1-20 alkoxy, C _2-20 alkoxyalkyl, C _6-20 aryl, C _6-20 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _8-40 arylalkenyl, C _2-20 alkynyl, or selected from the group consisting of N, O and S _{C 2-20} heteroaryl containing one or more heteroatoms;

Z ₁ is halogen, C _1-20 alkyl, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _6-20 aryl, substituted or unsubstituted C _1-20 alkylidene, Substituted or unsubstituted amino group, C _2-20 alkylalkoxy, or C _7-40 arylalkoxy;

m is 1 or 0;

[Formula 2]

In Chemical Formula 2,

A is carbon or silicon,

M ₂ is a Group 4 transition metal,

R ₂₁ is C _6-20 aryl substituted with _{C 1-20 alkyl,}

R ₂₂ is C _3-20 branched alkyl,

R ₂₃ to R ₂₅ are each independently C _1-20 alkyl,

Z ₂₁ and Z ₂₂ are each independently halogen or C _1-10 alkyl,

n is an integer from 1 to 10.

The present invention provides a method for producing a polyolefin, comprising polymerizing an olefin-based monomer in the presence of a catalyst composition including the hybrid supported catalyst.

In the present invention, terms such as first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from other components.

In addition, terms used in the present specification are only used to describe exemplary embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present specification, terms such as "comprise", "include", or "have" are intended to designate the existence of a feature, number, step, element, or combination of the implemented features, but one or more other features or It is to be understood that the possibility of the presence or addition of numbers, steps, elements, or combinations thereof is not preliminarily excluded.

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

Hereinafter, a hybrid supported catalyst according to a specific embodiment of the present invention, and a method for producing a polyolefin using the same will be described in more detail.

Hybrid supported catalyst

High tensile strength is required for chlorinated polyolefins used for covering rubber hoses or wires. The tensile strength of the chlorinated polyolefin can be improved by increasing the Mooney viscosity of the chlorinated polyolefin or the Mooney viscosity of the compound, but in this case, there is a problem that the extrusion processability is deteriorated. In order to solve such a problem, it is necessary to optimize the molecular structure of the polyolefin applied to the chlorinated polyolefin, specifically, high-density polyethylene.

In the present invention, when two kinds of transition metal compounds having a specific structure are used in combination, the produced polyolefin has a structure in which a polymer tail is formed in a molecular weight distribution curve with a minimum low molecular content, and thus a chlorinated polyolefin It was confirmed that the tensile strength can be improved by increasing the degree of crosslinking during the manufacture of, and the present invention was completed.

Specifically, a hybrid supported catalyst according to an embodiment of the present invention includes at least one first transition metal compound represented by Formula 1; At least one second transition metal compound represented by Chemical Formula 2; And a carrier on which the first and second transition metal compounds are supported.

In the hybrid supported catalyst, the substituents of Formulas 1 and 2 will be described in more detail as follows.

The C _1-20 alkyl group includes a linear or branched chain or cyclic alkyl group, and specifically, a methyl group (Me, methyl), an ethyl group (Et, Ethyl), a propyl group (Pr, Propyl), isopropyl group, n -Butyl group (n-Bu, n-Butyl), tert-butyl group (t-Bu, tert-Butyl)), pentyl group (Pt, Pentyl), hexyl group (Hx, Hexyl), heptyl group, octyl group, A cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like, but are not limited thereto.

The C _1-20 alkylene group includes a linear or branched alkylene group, and specifically, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and the like, but are limited thereto. It is not.

The C _4-20 cycloalkyl group refers to a cyclic alkyl group among the alkyl groups as described above, and specifically, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc. may be mentioned, but is not limited thereto. .

The C _2-20 alkenyl group includes a linear or branched alkenyl group, and specifically, an allyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, and the like, but are not limited thereto.

The C _6-20 aryl group includes a monocyclic or condensed aryl group, and specifically, a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, a fluorenyl group, and the like, but are not limited thereto.

Examples of the C _1-20 alkoxy group include, but are not limited to, a methoxy group, an ethoxy group, a phenyloxy group, and a cyclohexyloxy group.

The C _2-20 alkoxyalkyl group is a functional group in which at least one hydrogen of the alkyl group as described above is substituted with an alkoxy group, and specifically, methoxymethyl group, methoxyethyl group, ethoxymethyl group, iso-propoxymethyl group, iso-propoxy Alkoxyalkyl groups such as ethyl group, iso-propoxyhexyl group, tert-butoxymethyl group, tert-butoxyethyl group, and tert-butoxyhexyl group; Or an aryloxyalkyl group such as a phenoxyhexyl group, but is not limited thereto.

The C _1-20 alkylsilyl group or C _1-20 alkoxysilyl _{group is a functional group in which 1 to 3 hydrogens of -SiH 3} are substituted with 1 to 3 alkyl or alkoxy groups as described above, and specifically methylsilyl group, di Alkylsilyl groups such as methylsilyl group, trimethylsilyl group, dimethylethylsilyl group, dimethylmethylsilyl group, or dimethylpropylsilyl group; Alkoxysilyl groups such as methoxysilyl group, dimethoxysilyl group, trimethoxysilyl group, or dimethoxyethoxysilyl group; Alkoxyalkylsilyl groups, such as a methoxydimethylsilyl group, a diethoxymethylsilyl group, or a dimethoxypropylsilyl group, are mentioned, but are not limited thereto.

The C _1-20 silylalkyl group is a functional group in which at least one hydrogen of the alkyl group as described above is substituted with a silyl group, and specifically, -CH ₂ -SiH ₃ , a methylsilylmethyl group or a dimethylethoxysilylpropyl group, etc. may be mentioned. However, it is not limited to this.

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

The sulfonate group has _{a structure of -O-SO 2} -R', and _R'may be a C 1-20 alkyl group. Specifically, the C _1-20 sulfonate group may include a methanesulfonate group or a phenylsulfonate group, but is not limited thereto.

_{The heteroaryl is a C 2-20} heteroaryl containing at least one of N, O, and S as a heterogeneous element, and specific examples include xanthene, thioxanthene, thiophene group, furan group, Pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, Quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzoimidazole group, Benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadiazolyl group, phenothiazinyl group and dibenzofuranyl group, etc. However, it is not limited to these.

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

In addition, the Group 4 transition metal may include titanium (Ti), zirconium (Zr), hafnium (Hf), and the like, but is not limited thereto.

In the hybrid supported catalyst according to an embodiment of the present invention, the first transition metal compound represented by Formula 1 is easy to prepare a low molecular weight polymer with high polymerization activity, and the second transition metal compound is an ultra-high molecular weight polymer. It is easy to Accordingly, by adjusting the mixing ratio of the first and second transition metal compounds in the hybrid supported catalyst, the low molecular weight content in the prepared polymer is minimized, and the molecular weight distribution may be increased due to the ultra-high molecular weight characteristics of the second transition metal compound. , In addition, it can be easy to adjust the viscosity. In the production of the chlorinated polyolefin using the polymer thus prepared, the crosslinking efficiency is increased, and thus tensile strength may be improved.

Specifically, the first transition metal compound represented by Formula 1 is a non-crosslinked compound including a ligand ^{of Cp 1} and Cp ^2. The ^{ligands of Cp 1} and Cp ² may be the same or different from each other, and each independently a cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radical. It may be any one selected from the group consisting of, and these ligands may be substituted by 1 or more, or 1 to 3 _{, with C 1-20} hydrocarbons, more specifically C _{1-10 alkyl.} As described above, ^{the ligands of Cp 1} and Cp ² may exhibit high polymerization activity by having a non-shared electron pair capable of acting as a Lewis ^{base.In particular, when the ligands of Cp 1} and Cp ² are cyclopentadienyl with relatively little steric hindrance , It exhibits high polymerization activity and low hydrogen reactivity, so that low molecular weight olefin polymers can be polymerized with high activity.

In addition, the ^{ligands of Cp 1} and Cp ² are, for example, the chemical structure, molecular weight, molecular weight distribution, mechanical properties, and transparency of the olefin polymer prepared by controlling the degree of steric hindrance according to the type of substituted functional group. The properties can be easily adjusted. Specifically, the ligand of said Cp ¹ and Cp ² are substituted by R ₁₁ and R _12, respectively, at this time, the R ₁₁ and R ₁₂ are the same or different, each independently, hydrogen, C _1-20 alkyl, C _{It may be 2-20} alkoxyalkyl, C _6-20 aryl, C _7-20 arylalkyl, furanyl, or thiophenyl, and more specifically, C _1-10 alkyl such as n-butyl; _{C 2-10} alkoxyalkyl such as t-butoxyhexyl; _{C 6-20} aryl such as phenyl; _{C 7-20} arylalkyl such as phenylbutyl; It may be furanyl or thiophene. In terms of excellent catalytic activity, R ₁₁ and R ₁₂ may each be a substituent as defined above, but at least one of _{R 11} and R _{12 may be C 2-20} alkoxyalkyl or C _2-10 alkoxyalkyl.

_{M 1} (Z ₁ ) _3-m exists between the ligands of Cp ¹ and Cp ² , and M ₁ (Z ₁ ) _3-m may affect the storage stability of the metal complex. In order to more effectively secure this effect, Z ₁ may each independently be halogen or C _1-20 alkyl, and more specifically, each independently may be F, Cl, Br or I. In addition, M ₁ may be Ti, Zr or Hf, more specifically Zr or Hf, and even more specifically Zr.

More specifically, in the first transition metal compound, M ₁ is Ti, Zr or Hf; Cp ¹ and Cp ² are the same as or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals. One, and these are unsubstituted or substituted with _{C 1-10 alkyl;} R ₁₁ and R ₁₂ are each independently hydrogen, C _1-20 alkyl, C _2-20 alkoxyalkyl, C _6-20 aryl, C _7-20 arylalkyl, furanyl, or thiophenyl, wherein At least one of R ₁₁ and R _{12 is C 2-20} alkoxyalkyl; Z ₁ may be a halogen; phosphorus compound.

The first transition metal compound represented by Formula 1 may be, for example, a compound represented by one of the following structural formulas, but is not limited thereto:

.

Among the first transition metal compounds, in Formula 1, M ₁ is Zr, and Cp ¹ and Cp ² are each independently an unsubstituted cyclopentadienyl group or at least one _{C 1-10 alkyl such as methyl} A substituted cyclopentadienyl group, and R ₁₁ and R ₁₂ are each independently hydrogen, C _1-20 alkyl, C _2-20 alkoxyalkyl, C _7-20 aryl or C _7-20 arylalkyl, wherein At least one or both of R ₁₁ and R _{12 are C 2-20} alkoxyalkyl, more specifically C _2-10 alkoxyalkyl, even more specifically t-butoxyhexyl group, and Z ₁ is halogen Group, and m may be a compound of 1.

The first transition metal compound represented by Formula 1 may be synthesized by applying known reactions. Specifically, a ligand compound is prepared through various synthesis processes, and then a metal precursor compound is added to perform metallation, but it is not limited thereto, and a more detailed synthesis method may be referred to the Examples. .

Meanwhile, in the hybrid supported catalyst, the second transition metal compound represented by Formula 2 forms a ligand structure in which an indene derivative and an amine derivative are crosslinked by a bridge compound, and a non-shared electron pair capable of acting as a Lewis base in the ligand structure By having, excellent polymerization activity can be exhibited. Particularly, structurally stable and electronically rich indene structures may exhibit high catalytic activity, and since the bridging group includes a tether group, excellent support stability for a carrier may be exhibited.

_{In addition, the second transition metal compound is substituted with a functional group (R 22} ) having a branched structure at position 2 of the indene structure, and by stabilizing beta-hydrogen in the polymer chain in which the nitrogen atom of the amine derivative grows by hydrogen bonding. , It is possible to prepare a polymer of a medium molecular weight and a high molecular weight region, and the resulting polymer has a narrow molecular weight distribution, so that excellent mechanical properties can be exhibited. Specifically, R _{22 may be a branched alkyl of C 3-12} or C _3-6 such as isopropyl, isobutyl, t-butyl, isopentyl, and the like, and isopropyl, which is more advantageous in terms of steric effects. have.

In addition, the indene structure is R ₂₁ at the 4 position, specifically, 1 or more, more specifically 1 or 2 C _{6-20 aryl substituted with C 1-20} alkyl is bonded to supply sufficient electrons. Higher catalytic activity may be exhibited by a possible inductive effect. More specifically, in Formula 2, R ₂₁ may be phenyl substituted with one or two _{C 3-6} branched alkyls such as 4-tert-butylphenyl and 3,5-ditert-butyl phenyl.

_{In addition, R 23} bonded to N in Formula 2 may be a C _1-20 linear or branched alkyl, and more specifically, a C _3-12 or C _3-6 branched alkyl such as t-butyl I can. As described above, when R ₂₃ has a branched structure, the transition metal compound is stericly stabilized, and the catalyst is stabilized by an electron supply effect, thereby exhibiting higher catalytic activity.

More specifically, in Formula 2, R ₂₁ is phenyl substituted with one or two _{C 3-6 branched alkyl, and R 22} and R ₂₃ are each independently C _3-6 branched alkyl, and , More specifically, R ₂₂ may be isopropyl.

In addition, in Formula 2, the bridge group includes a tethered group of -(CH ₂ )nOR _{25 capable of tethering to the carrier together with the functional group of R 24} . Accordingly, it is possible to exhibit excellent support stability, and to maintain excellent catalytic activity to prepare a high molecular weight polymer.

Specifically, R ₂₄ may be C _1-12 or C _1-6 linear or branched alkyl. More specifically, it may be C _1-4 straight-chain alkyl or methyl, and in the case of a straight-chain structure or methyl as described above, solubility may be increased to improve loading efficiency.

In addition, R ₂₅ in the tether group may be C _1-12 or C _1-6 linear or branched alkyl. More specifically, it may be C _3-6 branched alkyl or t-butyl, and when it has a branched structure such as t-butyl, it can be easily detached and bonded to the carrier, thereby exhibiting excellent support stability.

In addition, n in the tether group may specifically be 3 to 8, or 4 to 6, and in this case, the tether group may have an appropriate length and thus stably exhibit catalytic activity with superior support stability.

In addition, in the bridge group, A may be more specifically silicon (Si).

More specifically, in Formula 2, A is silicon, R ₂₅ is C _3-6 branched alkyl, and n may be an integer of 4 to 6.

In addition, the second transition metal compound of Formula 2 may include a Group 4 transition metal such as titanium (Ti), zirconium (Zr), and hafnium (Hf) as the _{central metal (M 2 ).} Among these, when the transition metal compound contains Ti as the central metal, the catalyst increases the structural openness compared to the case where other Group 4 transition metals such as Zr and Hf are included, so that the catalyst provides more excellent polymerization activity. And can exhibit high molecular weight by stabilizing the catalyst through an electron supply effect.

In addition, in Formula 2, Z ₂₁ and Z ₂₂ are each independently a halogen such as chloro; Or it may be _{C 1-4} alkyl such as methyl. More specifically, _{both Z 21} and Z ₂₂ may be methyl, and in this case, Z ₂₁ and Z ₂₂ may exhibit better catalytic activity than when they are halogen.

More specifically, in Formula 2, M ₂ is titanium, and Z ₂₁ and Z ₂₂ may each independently be C _1-4 alkyl.

More specifically, in the compound of Formula 2, A is silicon, M ₂ is titanium, R ₂₁ is phenyl substituted with one or two _{C 3-10} branched alkyl such as t-butyl _{, and R 22} Is a C _3-6 branched alkyl _{such as isopropyl, R 23} is a C _3-6 branched alkyl such as t-butyl, R _{24 is a C 1-4} straight chain alkyl such as methyl, _{and R 25} is t- _{C 3-6} branched alkyl such as butyl _{, Z 21} and Z ₂₂ are each independently C _1-4 alkyl such as methyl, and n may be a compound having an integer of 4 to 6.

Representative examples of the second transition metal compound of Formula 2 include compounds having the following structures, but are not limited thereto:

.

The second transition metal compound described above may be prepared by lithiation (or lithium substitution) of the ligand compound of Formula 3 below, and then reacting with a Group 4 transition metal-containing halide:

[Formula 3]

In Formula 3, A, R ₂₁ to R ₂₅ and n are as defined above.

Reaction Scheme 1 below shows a process for preparing the second transition metal compound of Formula 2 according to an embodiment of the present invention. Scheme 1 below is only an example for explaining the present invention, but the present invention is not limited thereto.

[Scheme 1]

In Reaction Scheme 1, A, M ₂ , R ₂₁ to R ₂₅ , Z ₂₁ , Z ₂₂ and n are the same as defined above, and X ₁ and X ₂ are each independently a halogen group.

As in Reaction Scheme 1, the compound (2) of Formula 2 is lithiumized by reacting the ligand compound (3) of Formula 3 with alkyl lithium such as n-butyllithium (NBL), and then, TiCl ₄ or the like. It can be prepared by reacting with the same Group 4 transition metal-containing halide (4). _{In addition, when X 1} and X ₂ in the compound (2) of Formula 2 are each C _1-10 alkyl, after lithiation, an alkylating agent for alkylation of metal M such as MMB (Methyl Magnesium Bromide) is additionally added. Can be put in.

In addition, the ligand compound (3) used in the preparation of the compound (2) of Formula 2 may be prepared through the same manufacturing process as in Scheme 2 below. Scheme 2 below is only an example for explaining the present invention, but the present invention is not limited thereto.

[Scheme 2]

In Reaction Scheme 2, A, R ₂₁ to R ₂₄ , and n are the same as previously defined, and X ₃ and X ₄ are each independently a halogen group.

Referring to Reaction Scheme 2, the ligand compound (3) comprises the steps of reacting an indene-based compound (5) as a Cp unit with an alkyl lithium such as n-butyllithium (NBL) to make lithium; Reacting the resulting reactant with a raw material 6 for providing a tether group to prepare a compound 7 in which a tether group is bonded to an indene structure; And reacting the compound (7) with a primary amine (8) having a substituent of _{R 3} such as _{t-BuNH 2.}

The reaction in each step may be performed by applying known reactions, and a more detailed synthesis method may refer to the preparation example described later.

As described above, the hybrid supported catalyst includes the first and second transition metal compounds, and has a wide molecular weight distribution according to the formation of a polymer tail in a molecular weight distribution curve with a minimized low molecular weight, thereby producing chlorinated polyolefins and compounds. Polyolefin, in particular, high-density polyethylene capable of improving tensile strength according to an increase in crosslinking degree can be produced very effectively. In addition, the above-described effect may be further enhanced by controlling the mixing ratio of the first and second transition metal compounds in the hybrid supported catalyst. Specifically, the mixing molar ratio of the first and second transition metal compounds may be 1:3 to 3:1, or 1:1.5 to 2:1.

In addition, by optimizing the mixing ratio according to the combination of the first and second transition metal compounds, the catalytic activity may be increased, and the physical properties of the polyethylene produced may be further improved. For example, when the second transition metal compound is a compound in which R ₂₁ is _{phenyl substituted with one C 3-10} branched alkyl in Formula 2, the first transition metal compound and the second transition metal compound are 1:1.1 to 1 It is preferably included in a weight ratio of :3, or 1:1.2 to 1:1.5, and in the second transition metal compound, R ₂₁ is substituted with two or more or two _{C 3-10 branched alkyls in Formula 2} In the case of a phenyl compound, the first transition metal compound and the second transition metal compound are preferably included in a weight ratio of 1:1 to 3:1, or 1.5:1 to 2:1.

In addition, in the hybrid supported catalyst, the first and second transition metal compounds are included in a supported form. When the transition metal compound is used in the form of a supported catalyst as described above, the morphology and physical properties of the polyethylene produced may be further improved, and may be suitably used for slurry polymerization, bulk polymerization, and gas phase polymerization processes.

Specifically, silica, alumina, magnesia, or a mixture thereof may be used as the carrier. In addition, it is preferable to have a highly reactive hydroxy group, silanol group, or siloxane group on the surface, and for this purpose, a surface modified by calcination or a surface of which moisture has been removed by drying may be used. For example, silica prepared by calcining silica gel, silica dried at high temperature, silica-alumina, and silica-magnesia may be used. In addition, the carrier may contain oxides, carbonates, sulfates, and nitrate components such as _{Na 2} O, K ₂ CO ₃ , BaSO ₄ , and Mg(NO ₃ ) _2.

When calcining or drying the carrier, the temperature may be 200 to 600°C, and may be 250 to 600°C. When the calcination or drying temperature of the carrier is lower than 200°C, there is a possibility that the moisture on the surface and the cocatalyst may react because there is too much moisture remaining in the carrier. Although the rate may be relatively high, this requires a large amount of cocatalyst. In addition, if the drying or calcination temperature exceeds 600℃, the surface area decreases as the pores on the surface of the carrier are combined, and a lot of hydroxyl groups or silanol groups disappear on the surface, and only siloxane groups remain, reducing the reaction site with the cocatalyst. There is a fear of doing it.

The amount of hydroxy groups on the surface of the carrier can be controlled by a method and conditions for preparing the carrier or drying conditions such as temperature, time, vacuum or spray drying. If the amount of the hydroxy group is too low, the reaction site with the cocatalyst is small, and if it is too large, it may be due to moisture other than the hydroxy group present on the surface of the carrier particles. For example, the amount of hydroxy groups on the surface of the carrier may be 0.1 to 10 mmol/g or 0.5 to 5 mmol/g.

Among the above-described carriers, silica, especially silica prepared by calcining silica gel, is supported by chemical bonding of the transition metal compound to the silica carrier, so that there is hardly any catalyst released from the surface of the carrier in the propylene polymerization process. As a result, when the polyolefin is produced by slurry polymerization or gas phase polymerization, fouling of the reactor wall or polymer particles entangled with each other can be minimized.

In addition, when the transition metal compound is included in the form of a supported catalyst, the total amount of the first and second transition metal compounds is 10 per weight of the carrier, for example, based on 1 g of silica. µmol or more, or 30 µmol or more, or 60 µmol or more, and may be supported in a content range of 120 μmol or less or 100 µmol or less. When supported in the above content range, it may be advantageous in terms of maintaining the activity of the catalyst by exhibiting an appropriate supported catalytic activity.

The hybrid supported catalyst having the above configuration exhibits excellent polymerization activity, and can prepare a chlorinated polyolefin or a polyolefin having an optimized structure for improving the tensile strength of the compound.

Preparation of polyolefin

According to another embodiment of the present invention, a method for producing a polyolefin including polymerizing an olefin-based monomer in the presence of a catalyst composition including the hybrid supported catalyst may be provided.

In the above production method, the catalyst composition includes the aforementioned hybrid supported catalyst.

The hybrid supported catalyst may be introduced into the polymerization reaction system by itself, or a C _5-12 aliphatic hydrocarbon solvent such as pentane, hexane, heptane, nonane, decane, and isomers thereof and aromatic hydrocarbons such as toluene and benzene. It may be dissolved or diluted in a solvent, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, or chlorobenzene, and then introduced into the reaction system. The solvent used here is preferably used after removing a small amount of water or air acting as a catalyst poison by treating a small amount of alkyl aluminum.

In addition, the catalyst composition may further include at least one of a cocatalyst and an antistatic agent.

Specifically, the catalyst composition may further include a cocatalyst in terms of improving high activity and process stability. The cocatalyst may include one or more of the compounds represented by the following Chemical Formula 9, Chemical Formula 10, or Chemical Formula 11.

[Formula 9]

-[Al(R _a )-O] _m-

In Chemical Formula 9,

R _a may be the same as or different from each other, and each independently halogen; Hydrocarbons of C _1-20; Or a halogen-substituted C _1-20 hydrocarbon;

m is an integer of 2 or more;

[Formula 10]

J(R _b ) ₃

In Chemical Formula 10,

R _b may be the same as or different from each other, and each independently halogen; Hydrocarbons of C _1-20; Or a halogen-substituted C _1-20 hydrocarbon;

J is aluminum or boron;

[Formula 11]

_{^{[EH] + [ZQ 4]}} - or _{^{[E] + [ZQ 4]}} -

In Formula 11,

E is a neutral or cationic Lewis base;

H is a hydrogen atom;

Z is a group 13 element;

Q may be the same as or different from each other, and each independently of one or more hydrogen atoms _{is substituted or unsubstituted with halogen, C 1-20} hydrocarbon, alkoxy or phenoxy, C _6-20 aryl group or C _1-20 It is an alkyl group.

_{Examples of the compound represented by Formula 9 include C 1-20} alkylaluminoxane-based compounds such as methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, or butylaluminoxane, and any one or two of them Mixtures of the above can be used.

In addition, examples of the compound represented by Formula 10 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclo Pentyl 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 ethoxide , Trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like. More specifically, it may be selected from trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum.

In addition, examples of the compound represented by Formula 11 include triethyl ammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, trimethyl ammonium tetraphenyl boron, tripropyl ammonium tetraphenyl boron, trimethyl ammonium tetra (p- Tolyl) boron, trimethylammonium tetra (o,p-dimethylphenyl) boron, tributyl ammonium tetra (p-trifluoromethylphenyl) boron, trimethyl ammonium tetra (p-trifluoromethylphenyl) boron, tributyl ammony Um tetrapentafluorophenyl boron, N,N-diethylanilinium tetraphenyl boron, N,N-diethylanilinium tetrapentafluorophenyl boron, diethyl ammonium tetrapentafluorophenyl boron, triphenyl Phosphonium tetraphenyl boron, trimethylphosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra (p -Tolyl) aluminum, tripropyl ammonium tetra (p-tolyl) aluminum, triethyl ammonium tetra (o,p-dimethylphenyl) aluminum, tributyl ammonium tetra (p-trifluoromethylphenyl) aluminum, trimethyl ammonium Tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N,N-diethylanilinium tetraphenyl aluminum, N,N-diethylanilinium tetrapentafluorophenyl aluminum , Diethylammonium tetrapenta tetraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra(p-tolyl) boron, triethylammonium tetra(o,p-dimethylphenyl) ) Boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetra (p-trifluoromethylphenyl) boron, or triphenylcarbonium tetrapentafluorophenyl boron, etc. And any one or a mixture of two or more of them may be used.

Among the above-described cocatalysts, when considering the fact that it can exhibit more excellent catalytic activity when used with the transition metal compound, the cocatalyst is a compound represented by Formula 9, more specifically, C _{1 such as methylaluminoxane. It} may be an alkylaluminoxane-based compound of -20. The alkylaluminoxane-based compound acts as a scavenger of hydroxyl groups present on the surface of the carrier to improve catalytic activity, and converts the halogen group of the catalyst precursor to a methyl group to promote chain growth during polymerization of polyethylene. .

The cocatalyst may be supported in an amount of 0.1 mmol or more, 0.15 mmol or more, or 5 mmol or more, or 8 mmol or more, or 10 mmol or more, 25 mmol or less, or 20 mmol or less per weight of the carrier, for example, based on 1 g of silica. have. When included in the above content range, it is possible to sufficiently obtain the effect of improving the catalytic activity according to the use of the cocatalyst and the effect of reducing the generation of fine particles.

In addition, the catalyst composition may further include an antistatic agent. As such an antistatic agent, an ethoxylated alkyl amine, specifically, a compound represented by the following Formula 12 may be used. When the catalyst composition includes an antistatic agent, generation of static electricity is suppressed in the polyethylene polymerization process, so that the physical properties of the polyethylene produced may be further improved.

[Formula 12]

RN-(CH ₂ CH ₂ OH) ₂

In Formula 12, R may be C _8-30 alkyl, and when R includes an alkyl group having a carbon number in the above range, it may exhibit a fine powder reduction effect through an excellent antistatic action without causing an unpleasant odor.

More specifically, the ethoxylated alkylamine may be a compound in which R in Formula 1 is C _8-22 linear alkyl, C _10-18 linear alkyl, or C _13-15 linear alkyl, , One of these compounds alone or a mixture of two or more may be used. Specific examples include N,N-bis(2-hydroxyethyl)tridecylamine, or N,N-bis(2-hydroxyethyl)pentadecylamine, and the like, commercially available Atmer 163™ (manufactured by CRODA), and the like may be used.

In addition, when an antistatic agent is further included, the carrier, for example, 0.5 parts by weight or more, or 1 part by weight or more, or 2 parts by weight or more, 20 parts by weight or less, or 10 parts by weight or less, or 7 It may be included in an amount less than or equal to parts by weight.

The cocatalyst and the antistatic agent may be used in combination with the aforementioned hybrid supported catalyst, respectively, or may be used while being supported on a carrier in the hybrid supported catalyst. If used in a state supported by a carrier in a hybrid supported catalyst, the catalyst composition includes the steps of supporting a cocatalyst compound on the carrier, and supporting a transition metal compound on the carrier; And injecting an antistatic agent in a slurry state and heat-treating the carrier on which the cocatalyst and the transition metal compound are supported. At this time, the loading of the transition metal compound may be carried out after the loading of the first transition metal compound, or may be carried out vice versa. A supported catalyst having a structure determined according to such a supporting sequence may exhibit higher catalytic activity and excellent process stability in the manufacturing process of polyolefin.

The catalyst composition may be used in the form of a slurry or diluted in a solvent depending on the polymerization method, or may be used in the form of a mud catalyst mixed with a mixture of oil and grease.

When used as a slurry or diluted in a solvent, the solvent is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the polymerization process of propylene monomers, such as pentane, hexane, heptane, nonane, decane, and these Isomers and aromatic hydrocarbon solvents such as toluene and benzene, or hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene, and any one or a mixture of two or more of them may be used. In this case, the catalyst composition may further include the above-described solvent, and a small amount of water or air, which may act as a catalyst poison, may be removed by treating the solvent with a small amount of alkyl aluminum before use.

In addition, when a polymerization method such as continuous bulk polymerization is used, the catalyst composition may be used in the form of a mud catalyst mixed with a mixture of oil and grease. In this case, compared to the case of using in a dissolved or diluted state in a solvent, the amount of the volatile organic compound contained in the homopolyethylene to be produced can be further reduced, and as a result, the odor caused by the volatile organic compound can also be reduced. I can.

On the other hand, the polymerization reaction for the production of polyolefin may be performed by homopolymerization with one olefinic monomer or by copolymerization of two or more monomers using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor. However, according to the method of one embodiment, it is more appropriate to polymerize the olefin-based monomer by slurry polymerization or gas phase polymerization in order to more effectively control the molecular weight distribution.

In particular, the polymerization reaction may be carried out in a slurry phase polymerization in a hydrocarbon-based solvent (eg, an aliphatic hydrocarbon-based solvent such as hexane, butane, and pentane). As the first and second transition metal compounds according to the present invention exhibit excellent solubility in aliphatic hydrocarbon-based solvents, they are stably dissolved and supplied to the reaction system, so that the polymerization reaction can proceed effectively.

And, the method of manufacturing a polyolefin according to an embodiment of the present invention may be carried out in a single-CSTR reactor (Single-CSTR Reactor).

In the polymerization reactor, for example, polymerization may proceed in the presence of an inert gas such as nitrogen. The inert gas may play a role of prolonging the reaction activity of the metallocene compound contained in the catalyst by suppressing the rapid reaction of the metallocene catalyst at the beginning of the polymerization reaction.

Further, during the polymerization reaction, hydrogen gas may be used for the purpose of controlling the molecular weight and molecular weight distribution of the polyolefin. Hydrogen gas activates the inert site of the metallocene catalyst and plays a role of controlling the molecular weight by causing a chain transfer reaction.When hydrogen gas is added during the polymerization reaction, 0.1% by volume or more with respect to the total volume of the olefin monomer, Alternatively, it may be added in an amount corresponding to 0.12% by volume or more, 0.2% by volume or less, and 0.18% by volume or less. When hydrogen gas is added in an amount within the above range, processability can be improved by reducing the molecular weight of the polymer to be produced.

In addition, the temperature during the polymerization reaction may be 70 to 100 ℃, or 80 to 90 ℃. If the polymerization reaction temperature is too low, it is not appropriate in terms of the polymerization rate and productivity. Conversely, if the polymerization reaction temperature is higher than necessary, fouling in the reactor may be caused.

In addition, the pressure during the polymerization reaction is 6.8 to 9 kg/cm ² , more specifically 6.8 kg/cm ² or more, or 7.0 kg/cm ² Or more, or 8.0 kg/cm ² Or more, and may be 9 kg/cm ² or less or 8.7 kg/cm ² or less. ^{The polymerization reaction pressure may be 6.8 kg/cm 2} or more in terms of preventing blocking due to excessive generation of high molecular weight and optimizing productivity ^{, and 9 kg/cm 2} or less in consideration of prevention of side reactions under high-pressure polymerization conditions. Can be.

In addition, an organic solvent may be further used as a reaction medium or diluent in the polymerization reaction. Such an organic solvent may be used in an amount such that slurry polymerization or the like can be properly performed in consideration of the content of the olefinic monomer.

In addition, trialkyl aluminum such as triethyl aluminum may be optionally further added during the polymerization reaction.

When moisture or impurities are present in the polymerization reactor, a part of the catalyst is decomposed. The trialkyl aluminum acts as a scavenger to capture moisture or impurities in the reactor or moisture contained in the monomer in advance. The activity of the catalyst used in the preparation can be maximized, and as a result, a homopolyethylene having excellent physical properties, particularly a narrow molecular weight distribution, can be produced more efficiently. Specifically, in the trialkylaluminum, alkyl is as defined above, specifically C _{1-20 alkyl, and more specifically C 1-6} straight or branched chain alkyl, such as methyl, ethyl, isobutyl, etc. I can.

In addition, the trialkyl aluminum (based on 1M) may be added in an amount of 300 ppm or more, or 400 ppm or more, 1500 ppm or less, or 1350 ppm or less based on the total weight of the ethylene monomer, and the presence of trialkyl aluminum in this content range Under the polymerization reaction, it is possible to more easily prepare a homopolyethylene having excellent strength properties.

In addition, the olefinic monomer may be ethylene, alpha-olefin, cyclic olefin, diene olefin or triene olefin having two or more double bonds.

As a specific example of the olefinic monomer, ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-itocene, norbornene, nobornadiene, ethylidene nobornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, 1,4-butadiene , 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, and the like, and two or more of these monomers may be mixed and copolymerized.

The polyolefin prepared by the above-described manufacturing method exhibits a multimodal molecular weight distribution when analyzed by gel permeation chromatography (GPC), and has a broad molecular weight distribution with a minimized low molecular weight. In the molecular weight distribution curve obtained by gel permeation chromatography analysis, the polyolefin has an area ratio occupied by an area of log Mw of 3.5 or less relative to the total area of the distribution curve of 1.4% or less and a molecular weight distribution of 6 to 15.

Specifically, when the polyolefin draws a molecular weight distribution curve with the log value (log Mw) of the weight average molecular weight (Mw) as the x-axis, and the molecular weight distribution (dwt/dlog Mw) with the log value as the y-axis, The area ratio occupied by the area of log Mw of 3.5 or less (log Mw ≤ 3.5) to the total area, that is, the fraction is 1.4% or less, or 1.2% or less, or 1.05% or less, or 1% or less. The area ratio occupied by an area having a log Mw of 3.5 or less means a low molecular weight content of ^{10 3.5 g/mol or less of the weight average molecular weight (Mw) of the polyolefin.} As described above, by minimizing the low molecular weight, excellent crosslinking properties can be displayed.

However, the smaller the low molecular weight content in the polyolefin is, the better the crosslinking degree is.However, when the low molecular weight content is too low and the high molecular weight content is relatively high, there is a concern that processability may decrease due to an increase in Mooney viscosity during manufacture of the chlorinated polyethylene compound. . Accordingly, it has an appropriate Mooney viscosity, and when considering the effect of improving processability in the manufacture of electric wires using chlorinated polyethylene, the fractional ratio in the region of less than 3.5 log Mw should be 0.1% or more, or 0.5% or more, or 0.8% or more. I can.

In addition to the minimized low molecular weight content as described above, the polyolefin has a wide molecular weight distribution (PDI) according to the formation of a polymer tail in the molecular weight distribution curve. Specifically, the PDI of the polyolefin is 6 or more, or 6.1 or more, and 15 or less, or 12 or less.

Meanwhile, in the present invention, the molecular weight distribution (PDI, polydispersity index) of the polyolefin can be calculated by measuring the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polyolefin, and dividing the weight average molecular weight by the number average molecular weight.

In addition, the low molecular weight, weight average molecular weight, and number average molecular weight in the polyolefin can be measured through gel permeation chromatography (GPC, gel permeation chromatography, manufactured by Water Corporation), and a specific measurement method is as described in the following test examples. same.

In addition, the polyolefin may further satisfy the conditions of one or more of the following (i) to (viii), or two or more, or both, along with the low molecular weight content and molecular weight distribution characteristics described above:

(i) In the molecular weight distribution curve according to GPC analysis, the fraction ratio in log Mw greater than 3.5 and less than or equal to 4.0 (3.5 <log Mw ≤ 4.0): 1 to 5%

(ii) In the molecular weight distribution curve according to GPC analysis, the fraction ratio at log Mw 4.0 or less: 6% or less

(iii) Weight average molecular weight: 185,000 to 500,000 g/mol

(iv) Complex viscosity measured at a frequency of 500 rad/s: 790 to 810 Pa·s

(v) Melt flow rate ratio (MFRR, MI _21.6 /MI ₅ ): 10 to 25

(vi) Melt index (MI _5.0 , condition E, 190°C, 5.0 kg load) is 0.5 to 3 g/10min

(vii) Density measured according to ASTM D-1505: 0.94 to 0.96 g/cm ³

(viii) MDR torque (M _H -M _L ): 7.5 to 12 Nm.

Specifically, the polyolefin has a fractional ratio at log Mw of 3.5 to 4.0 or less (3.5 <log Mw ≤ 4.0) to reduce crosslinking efficiency, that is, the weight average molecular weight (Mw) is greater ^{than 10 3.5} g/mol, and 10 ^4.0 g/ The content of the low molecular weight less than or equal to mol may be 5% or less, or 4.8% or less, or 4.5% or less, and may be 1% or more, or 3% or more, and thus the fraction ratio at log Mw 4.0 or less in the polyolefin, that is, the weight average molecular weight (Mw) 10 ^{The content of the low molecular weight of 4.0} g/mol or less may be 6% or less, more specifically 5.5% or less.

When the low molecular weight content in the polyolefin, in particular, the low molecular weight content of Mw 10 ^{4. 0} g/mol or less is high, the low molecular weight component melts and the fluidity increases, which may block the pores of the polyolefin particles, thereby lowering the chlorination productivity. On the other hand, the polyolefin may exhibit an excellent crosslinking degree improvement effect without fear of a decrease in chlorination productivity.

Further, the polyolefin has a high weight average molecular weight (Mw), specifically, Mw is 185,000 g/mol or more, or 190,000 g/mol or more, and 500,000 g/mol or less, or 350,000 g/mol or less. By having the Mw and PDI in the above range, excellent mechanical properties and the effect of improving processability can be exhibited in a good balance. In particular, the difference in molecular weight between the polyolefins after the chlorination reaction is not large, so that chlorine can be uniformly substituted.

In addition, the polyolefin has a complex viscosity (η*(ω500), complex viscosity) of 790 Pa·s or more and 810 Pa·s or less, measured at a frequency of 500 rad/s. It is suitable for manufacturing.

In the present invention, the complex viscosity of the polyolefin can be measured at a temperature of 190°C and a frequency (ω) of 0.05 rad/s using ARES (Advanced Rheometric Expansion System). As described.

In addition, the polyolefin has a melt flow rate ratio (MFRR, Melt flow rate ratio, MI _21.6 / MI ₅ ) of 25 or less, or 20 or less, or 18 or less, 10 or more, or 10.3 or more, and a melt index (MI _5.0 , condition E, 190°C, 5.0 kg load) may be 0.5 g/10min or more, or 0.8 g/10min or more, or 1 g/10min or more, and 3 g/10min or less, or 2.5 g/10min or less. As the above range has a melt flow rate and a melt index, it is possible to appropriately control the Mooney viscosity without deteriorating physical properties when producing a chlorinated polyolefin, thereby improving processability.

In the present invention, the melt index (Melt Index, MI _5.0 ) of the polyolefin can be measured according to ASTM D1238 (condition E, 190°C, 5.0 kg load). In addition, the Melt Flow Rate Ratio (MFRR, 21.6/5) can be calculated by dividing _{MFR 21.6} by MFR _{5 , and the MFR 21.6} is measured under a temperature of 190°C and a load of 21.6 kg according to ASTM D 1238. MFR ₅ can be measured under a temperature of 190°C and a load of 5 kg according to ASTM D 1238.

In addition, the polyolefin is 0.94 g/cm ³ or more, or 0.945 g/cm ³ or more, and 0.96 g/cm ³ or less, or 0.955 g/cm ³ It shows the following high density. This means that the content of the crystal structure of the polyolefin is high and dense, and this has a characteristic that it is difficult to change the crystal structure during the chlorination process. In the present invention, the density of the polyolefin can be measured by a method based on ASTM D-1505.

In addition, the polyolefin may have an MDR torque (M _H -M _L ) of 7.5 Nm or more, or 8 Nm or more or 8.5 Nm or more, or 12 Nm or less, or 11.5 Nm or less. By having the MDR torque within the above range, a high degree of crosslinking and excellent mechanical properties can be exhibited.

The MDR torque (M _H -M _L ) of the polyolefin refers to the degree of crosslinking, and the higher the degree of crosslinking, the higher the M _H -M _L , and it means that the crosslinking efficiency is excellent when the same crosslinking agent is applied. The MDR torque of the polyolefin can be measured using a moving die rheometer (MDR) as an example, by measuring the M _H value and the M _L value under conditions of 180°C and 10 min, and subtracting the _{M L} value from the M _H value. Can be calculated. Here, M _H is the maximum vulcanizing torque measured in full cure, and M _L is the stored minimum vulcanizing torque. The specific measurement method is as described in the test examples below.

The polyolefin may be a homopolymer of an olefin that does not contain a separate comonomer, such as an ethylene homopolymer. For example, when the polyolefin is, for example, an ethylene homopolymer, preferably a high-density polyethylene (HDPE) that satisfies the above-described density condition, the above-described physical properties may be more appropriately satisfied. The high-density polyethylene has excellent softening point, hardness, strength, and electrical insulation, and can be used in various containers, packaging films, fibers, pipes, packings, insulating materials, and the like.

As described above, the polyolefin prepared using the hybrid supported catalyst according to the present invention has an optimized molecular structure such as a wide molecular weight distribution with a minimized low molecular content, so that the degree of crosslinking can be increased when preparing a chlorinated polyolefin, As a result, the tensile strength can be greatly improved. This may be particularly useful in the production of chlorinated polyolefins for wires or cables.

Accordingly, according to another embodiment of the present invention, there is provided a method for producing a chlorinated polyolefin comprising the step of chlorinating the polyolefin prepared by the above-described method with chlorine.

The hybrid supported catalyst according to the present invention includes two or more kinds of transition metal compounds having a specific chemical structure, so that a polyolefin having a molecular structure optimized for improving the tensile strength of a chlorinated polyolefin compound, in particular, a high-density polyethylene can be prepared.

The invention will be described in more detail in the following examples. However, the following examples are merely illustrative of the present invention, and the contents of the present invention are not limited by the following examples.

<Preparation of the first transition metal compound>

Synthesis Example 1: [tert-Bu-O-(CH ₂ ) ₆ -C ₅ H ₄ ] ₂ Preparation of ZrCl ₂

_{Using 6-chlorohexanol, tert-Butyl-O-(CH 2} ) ₆ -Cl was prepared by the method suggested in the literature (Tetrahedron Lett. 2951 (1988)), and NaCp was reacted thereto. tert-Butyl-O-(CH ₂ ) ₆ -C ₅ H ₅ was obtained (yield 60%, bp 80°C / 0.1mmHg).

In addition, t-Butyl-O-(CH ₂ ) ₆ -C ₅ H ₅ was dissolved in THF at -78°C, and normal butyllithium (n-BuLi) was slowly added, the temperature was raised to room temperature, and then reacted for 8 hours. . The previously synthesized lithium salt solution was slowly added to the suspension solution of _{ZrCl 4} (THF) ₂ (1.70 g, 4.50 mmol)/THF (30 mL) at -78°C again at room temperature. It was further reacted for 6 hours at.

All volatile substances were vacuum-dried, and a hexane solvent was added to the obtained oily liquid substance to filter it out. After vacuum drying the filtered solution, hexane was added to induce a precipitate at low temperature (-20°C). The obtained precipitate was filtered at low temperature to obtain a white solid [tert-Bu-O-(CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ compound (yield 92%).

¹ H NMR (300 MHz, CDCl ₃ ): 6.28 (t, J = 2.6 Hz, 2 H), 6.19 (t, J = 2.6 Hz, 2 H), 3.31 (t, 6.6 Hz, 2 H), 2.62 ( t, J = 8 Hz), 1.7-1.3 (m, 8H), 1.17 (s, 9H).

¹³ C NMR (CDCl ₃ ): 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.61, 30.14, 29.18, 27.58, 26.00.

<Preparation of the second transition metal compound>

Synthesis Example 2-1

Step 1: Preparation of Ligand Compound

Add 4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-indene (i) (2.9g, 10mmol) as Cp unit to a 100ml Schlenk flask and tetrahydrofuran (THF; 35ml) ) Was added and then cooled to -20°C or less. After stirring the cooled mixed solution for 5 minutes, N-butyllithium (NBL; 4.2ml, 2.5M in hexane) was added and reacted overnight to prepare lithiated Cp (lithiated Cp). I did. When the n-butyllithium was added, the mixed solution had a brown color.

Dichloro(tert-butoxy)hexyl)methylsilane (ii) (2.84g) as tether silane was added to a separate 100ml shrink flask, and MTBE (methyl tert-butyl ether) (35ml) was added. After cooling the shrink flask to -20°C or less, the lithiumated Cp prepared above was added dropwise to react. When the reaction was completed, the solvent in the reaction product was removed by distillation under reduced pressure under vacuum, and the resulting salt was filtered off using hexane (Hex). _{After t-BuNH 2} (4.5ml) was added to the resulting reactant (iii) to react, the resulting precipitate was filtered off using hexane, and 1-(6-(tert-butoxy)hexyl)- A ligand compound of N-(tert-butyl)-1-(4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-inden-1-yl)-1-methylsilanamine (2a) was obtained (yellow oil, 5.50 g, yield 98% (molar basis)).

NMR (400MHz, C6D6) 7.72-7.65 (m, 2H), 7.59-7.21 (m, 5H), 7.05 (s, 1H) 3.73-3.65 (m, 1H), 3.33-3.21 (m, 3H), 3.11- 2.85 (m, 1H), 1.66-1.51 (m, 3H), 1.51-1.34 (m, 4H), 1.26 (s, 9H), 1.12 (s, 9H), 1.24-1.18 (m, 6H), 1.06 ( s, 9H), 1.04-0.99 (m, 1H), 0.64-0.58 (m, 1H), 0.54-0.49 (m, 1H), 0.30 (s, 1.5H), 0.19 (s, 1.5H)

Step 2: Preparation of transition metal compound

The ligand compound (2a) (4.81 g, 8.6 mmol) prepared in step 1 was added to a 100 ml shrink flask, and toluene (43 ml) was added, followed by cooling to -20°C or less. After sufficiently cooling through stirring for 5 minutes, lithiation was performed by adding NBL (7.2ml, 2.5M in Hexane) to the resulting mixed solution. It was confirmed that the color of the mixed solution changed from light yellow to dark yellow after lithiation. After the lithiation reaction was completed, the resulting reaction solution was cooled to 0°C, MMB (Methyl Magnesium Bromide) (8.6ml, 3M in ether) was added, and the temperature was immediately lowered to -20°C and TiCl ₄ (8.6ml, 1M in toluene) was added. When added, smoke was generated and the reaction solution immediately turned brown. After the addition, o/n stirring was performed, and after completion, salt was removed through a filter to obtain a brown oil-like transition metal compound (1a) (brown oil, 4.5g, yield 82% (molar basis)).

NMR (400MHz, C6D6), 7.25-7.75 (m, 8H), 3.20-3.36 (m, 2H), 3.20-2.64 (m, 4H) 2.64-2.74 (m,1H), 1.59-1.71 (m, 4H) , 1.53 (s, 9H), 1.40-1.35 (m, 2H), 1.25 (s, 9H), 1.14 (s, 9H) 1.12 (s, 6H), 0.97 (s, 3H) 0.58 (s, 3H), 0.12 (s, 3H)

Synthesis Example 2-2

Step 1: Preparation of Ligand Compound

In a 50ml shrink flask, add 4-(3,5-di-tert-butylphenyl)-2-isopropyl-1H-indene (1.39g, 4mmol) as a Cp unit, and add THF (13ml) to -20℃ or less. Cooled. After stirring the cooled mixed solution for 5 minutes, NBL (1.7ml, 2.5M in hexane) was added and reacted for overnight to prepare lithiated Cp. When the NBL was added, the mixed solution turned reddish brown.

Dichloro(tert-butoxy)hexyl)methylsilane (1.14g) was added to a separate 100ml shrink flask, and THF (13ml) was added. After cooling the shrink flask to -20°C or less, the lithiumated Cp prepared above was added dropwise to react. When the reaction was completed, the solvent in the reaction product was removed by distillation under reduced pressure under vacuum, and the resulting salt was filtered off using hexane (Hex). After reacting by adding t-BuNH ₂ (1.7 ml) to the resulting reactant, the resulting precipitate was filtered off using hexane, and 1-(6-(tert-butoxy)hexyl)-N-( A ligand compound of tert-butyl)-1-(4-(3,5-di-tert-butylphenyl)-2-isopropyl-1H-inden-1-yl)-1-methylsilanamine was obtained (yellow oil, 2.41g, Yield 97% (molar basis)).

NMR (400MHz, C6D6), 7.70-7.68 (m, 1H), 7.60-7.47 (m, 4H), 7.34-7.19 (m, 2H), 7.07 (s, 0.5H), 6.89 (s, 0.5H), 3.36-3.21 (m, 4H), 3.12 (s, 1H), 2.52-2.44 (m, 0.5H), 2.00-1.92 (m, 0.5H), 1.72-1.39 (m, 8H), 1.39 (s, 9H) ), 1.31 (s, 9H), 1.23 (s, 3H) 1.19 (s, 3H), 1.13 (s, 9H) 0.98 (s, 9H) 0.32 (s, 1H), 0.25 (s, 0.5H), 0.2 0(s, 1H), 0.12 (s, 0.5H)

Step 2: Preparation of transition metal compound

In a 100 ml shrink flask, the ligand compound 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-(4-(3,5-di-tert-butylphenyl) prepared in step 1 -2-isopropyl-1H-inden-1-yl)-1-methylsilanamine (2.4g, 3.9mmol) was added, toluene (13ml) was added, and then cooled to -20°C or less. After sufficiently cooling through stirring for 5 minutes, NBL (5.1ml, 2.5M in Hexane) was added to the resulting mixed solution to perform lithiation. It was confirmed that the color of the mixed solution turned brown after lithiation. After completion of the lithiation reaction, the resulting reaction solution was cooled to 0℃, MMB (13ml, 3M in ether) was added, then the temperature was immediately lowered to -20℃ and TiCl ₄ (3.9ml, 1M in toluene) was added. I did. When added, smoke was generated and the reaction solution immediately turned brown. After the addition, o/n stirring was performed, and after completion, the salt was removed through a filter to obtain a brown oil-like transition metal compound (1b) (brown oil, 2.16 g, yield 80% (molar basis)).

(1b)

NMR (400MHz, C6D6), 7.79-7.76 (m, 2H), 7.64-7.47 (m, 5H), 3.35-3.21 (m, 2H), 2.76-2.49 (s, 2H), 1.99-1.91 (m, 4H) ), 1.70-1.60 (m, 4H), 1.53 (s, 9H), 1.51-1.44 (m, 4H), 1.36 (s, 9H), 1.30 (s, 9H), 1.20 (s, 6H), 1.13 ( s, 9H), 0.59 (s, 3H), 0.12 (s, 3H)

Comparative Synthesis Example 2-1

Step 1: Preparation of Ligand Compound

In a 100ml Schlenk flask, 4-(4-(tert-butyl)phenyl)-2-methyl-1H-indene (2.6g, 10mmol) was added as a Cp unit, and THF (35ml) was added. It cooled to below °C. After stirring the cooled mixed solution for 5 minutes, NBL (4.2ml, 2.5M in hexane) was added and reacted for overnight to prepare lithiated Cp. When the NBL was added, the mixed solution had a brown color.

Dichloro(tert-butoxy)hexyl)methylsilane as Tether silane in a separate 100ml shrink flask (2.84g) was added and MTBE (35ml) was added. After cooling the shrink flask to -20°C or less, the lithiumated Cp prepared above was added dropwise to react. When the reaction was completed, the solvent in the reaction product was removed by distillation under reduced pressure under vacuum, and the resulting salt was filtered off using hexane (Hex). After t-BuNH ₂ (4.5ml) was added to the resulting reactant to react, the resulting precipitate was filtered off using hexane, and 1-(6-(tert-butoxy)hexyl)-N-( A ligand compound of tert-butyl)-1-(4-(4-(tert-butyl)phenyl)-2-methyl-1H-inden-1-yl)-1-methylsilanamine was obtained (yellow oil, 5.2g, yield 98% (molar basis)).

NMR (400MHz, C6D6) 7.78-7.67 (m, 2H), 7.60-7.7.19 (m, 5H), 7.05 (s, 1H) 3.68 (s, 1H), 3.27-3.06 (m, 3H), 2.92- 2.86 (m, 1H), 1.26-1.12 (m, 4H), 1.11 (s, 9H), 1.09 (s, 9H), 1.08 (s, 3H), 1.06 (s, 9H), 1.04-0.99 (m, 4H), 0.54-0.49 (m, 1H), 0.18 (s, 1.5H), 0.05 (s, 1.5H)

Step 2: Preparation of transition metal compound

In a 100 ml shrink flask, the ligand compound prepared in step 1 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-(4-(4-(tert-butyl)phenyl)- Toluene (43ml) was added to 2-methyl-1H-inden-1-yl)-1-methylsilanamine (4.6g, 8.6mmol), and then cooled to -20°C or less. After sufficiently cooling through stirring for 5 minutes, NBL (7.2ml, 2.5M in Hexane) was added to the resulting mixed solution to perform lithiation. It was confirmed that the color of the mixed solution changed from light yellow to dark yellow after lithiation. After completion of the lithiation reaction, the resulting reaction solution was cooled to 0℃, MMB (8.6ml, 3M in ether) was added, and then the temperature was immediately lowered to -20℃, and TiCl ₄ (8.6ml, 1M in toluene) Was put in. When added, smoke was generated and the reaction solution immediately turned brown. After the addition, o/n stirring was performed, and after completion, the salt was removed through a filter to obtain a transition metal compound (A) having the following structure as a brown oil (brown oil, 3.9 g, yield 74% (molar basis)).

(A)

NMR (400MHz, C6D6), 7.75-7.12 (m, 8H), 3.30-3.26 (m, 2H), 2.68-2.45 (m, 1H), 1.76-1.52 (m, 6H), 1.50-1.13 (m, 4H) ), 1.25 (s, 9H), 1.20-1.15 (m, 2H), 1.14 (s, 9H), 1.10 (s, 9H) 0.96 (s, 3H), 0.58 (s, 3H), 0.11 (s, 3H )

Comparative Synthesis Example 2-2

Step 1: Preparation of Ligand Compound

In a 50ml shrink flask, 2-isopropyl-4-phenyl-1H-indene (0.94g, 4mmol) was added as a Cp unit, and THF (13ml) was added, followed by cooling to -20°C or less. After stirring the cooled mixed solution for 5 minutes, NBL (1.7ml, 2.5M in hexane) was added, and lithiated Cp was prepared during overnight. When the NBL was added, the mixed solution turned reddish brown.

Dichloro(tert-butoxy)hexyl)methylsilane as tether silane in a separate 100ml shrink flask (1.16g) was added and THF (13ml) was added. After cooling the shrink flask to -20°C or less, the lithiumated Cp prepared above was added dropwise to react. When the reaction was completed, the solvent in the reaction product was removed by distillation under reduced pressure under vacuum, and the resulting salt was filtered off using hexane (Hex). After reacting by adding t-BuNH ₂ (1.7 ml) to the resulting reactant, the resulting precipitate was filtered off using hexane, and 1-(6-(tert-butoxy)hexyl)-N-( A ligand compound of tert-butyl)-1-(2-isopropyl-4-phenyl-1H-inden-1-yl)-1-methylsilanamine was obtained (yellow oil, 1.98 g, yield 98% (molar basis)).

NMR(400MHz, C6D6), 7.68-7.63(m, 2H), 7.57-7.41 (m, 2H), 7.41-7.16 (m, 4H), 6.98 (s, 1H), 3.67 (s, 1H), 3.30- 3.19 (m, 4H), 3.06-2.99 (m, 0.5H), 2.94-2.87 (m, 0.5H), 2.52-2.42 (m, 0.5H), 2.02-1.92 (m, 0.5H), 1.69-1.38 (m, 8H), 1.13 (s, 9H), 1.05 (s, 6H), 0.98 (s, 9H), 0.27 (s, 1.5H), 0.16 (s, 1.5H)

Step 2: Preparation of transition metal compound

In a 100 ml shrink flask, the ligand compound 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-(4-(3,5-di-tert-butylphenyl) prepared in step 1 -2-isopropyl-1H-inden-1-yl)-1-methylsilanamine (1.98g, 3.9mmol) was added, toluene (13ml) was added, and then cooled to -20°C or less. After sufficiently cooling through stirring for 5 minutes, NBL (5.1ml, 2.5M in Hexane) was added to the resulting mixed solution to perform lithiation. After lithiation, it was confirmed that the color of the mixed solution turned yellow. After the lithiation reaction was completed, the resulting reaction solution was cooled to 0°C, MMB (13 ml, 3M in ether) was added, and then the temperature was immediately lowered to -20°C and TiCl ₄ (3.9ml, 1M in toluene) was added. Was put in. When added, smoke was generated and the reaction solution immediately turned brown. After the addition, o/n stirring was performed, and after completion, the salt was removed through a filter to obtain a brown oil-like transition metal compound (B) (brown oil, 1.79 g, yield 79% (molar basis)).

(B)

NMR (400MHz, C6D6), 7.71-7.69 (m, 2H), 7.52-7.44 (m, 2H), 7.29-7.22 (m, 1H), 7.29-7.17 (s, 4H), 3.38-3.24 (m, 2H) ), 2.88-2.41 (m, 2H), 1.68-1.60 (m, 7H), 1.50 (s, 9H), 1.30-1.20 (m, 5H), 1.19 (s, 6H), 1.14 (s, 9H), 0.58 (s, 3H), 0.07 (s, 3H)

Comparative Synthesis Example 2-3

A transition metal compound (C) having the following structure prepared by a known method was used.

(C)

Comparative Synthesis Example 2-4

A transition metal compound (D) having the following structure prepared by a known method was used.

(D)

<Preparation of hybrid supported catalyst>

Manufacturing Example 1

(1) preparation of carrier

Silica (SYLOPOL 948™, manufactured by Grace Davision) was dehydrated and dried under vacuum at 600° C. for 12 hours.

(2) Preparation of hybrid supported catalyst

10 g of dried silica was put into a glass reactor at room temperature, and 100 mL of toluene was additionally added thereto, followed by stirring. After sufficiently dispersing the silica, 106 ml of a 10 wt% methylaluminoxane (MAO)/toluene solution was added, and the mixture was slowly reacted with stirring at 40° C. at 200 rpm for 14 hours. After the reaction, the stirring was stopped, and the filtrate was decanted by settling for 30 minutes. 100 ml of toluene was added, stirred for 10 minutes, settling for 30 minutes, and decantation of the filtrate. After 50 ml of toluene was added again, 0.15 mmol/gSiO ₂ of the first transition metal compound according to Synthesis Example 1 was dissolved in toluene and added together to react for 1 hour. _{After the reaction was over, 0.18 mmol/gSiO 2} of the second transition metal compound according to Synthesis Example 2-1 was dissolved in toluene and added thereto, and the reaction was further stirred for 2 hours to react. After the reaction was completed, the stirring was stopped, the toluene layer was separated and removed, and then 100 ml of normal hexane was added and the mixture was stirred for 10 minutes. After completion of the stirring, the filtrate was removed by settiling for 30 minutes, and the remaining hexane was removed under reduced pressure to obtain a mixed supported catalyst.

Manufacturing Example 2

Except for using the compound prepared in Synthesis Example 2-2 instead of the second transition metal compound in Preparation Example 1, and using the first and second transition metal compounds in the amounts shown in Table 1 below, In the same manner as in Preparation Example 1, a hybrid supported catalyst was prepared.

Manufacturing Example 3

A hybrid supported catalyst was prepared in the same manner as in Preparation Example 2, except that the first and second transition metal compounds in Preparation Example 2 were used in the amounts shown in Table 1 below.

Comparative Production Example 1

A hybrid supported catalyst was carried out in the same manner as in Preparation Example 1, except that the transition metal compound (A) prepared in Comparative Synthesis Example 2-1 was used instead of the second transition metal compound in Preparation Example 1 Was prepared.

Comparative Production Example 2

Instead of the second transition metal compound in Preparation Example 1, the transition metal compound (B) prepared in Comparative Synthesis Example 2-2 was used, and the first and second transition metal compounds were added in the amounts shown in Table 1 below. Except for using, it was carried out in the same manner as in Preparation Example 1, to prepare a hybrid supported catalyst.

Comparative Production Example 3

Instead of the second transition metal compound in Preparation Example 1, the transition metal compound (C) prepared in Comparative Synthesis Example 2-3 was used, and the first and second transition metal compounds were added in the amounts shown in Table 1 below. Except for using, it was carried out in the same manner as in Preparation Example 1, to prepare a hybrid supported catalyst.

Comparative Production Example 4

Instead of the second transition metal compound in Preparation Example 1, the transition metal compound (D) prepared in Comparative Synthesis Example 2-4 was used, and the first and second transition metal compounds were added in the amounts shown in Table 1 below. Except for using, it was carried out in the same manner as in Preparation Example 1, to prepare a hybrid supported catalyst.

<Production of polyolefin>

Example 1

Under the conditions as shown in Table 1 below, an ethylene homopolymerization reaction was performed using the hybrid supported catalyst of Preparation Example 1 (compounds of Synthesis Examples 1 and 2-1).

In order to prepare an olefin polymer, a 2L metal alloy reactor was prepared, which was equipped with a mechanical stirrer, controlled temperature, and used for high-pressure reaction. After vacuum drying the reactor at 120° C., cooling, 0.9 kg of purified n-hexane was added, and 1350 ppm of triethyl aluminum (1M solution in Hexane) was added at room temperature, and the metallocene supported catalyst prepared in Preparation Example 1 above. 15 mg was added to the reactor. Thereafter, the temperature of the reactor was gradually increased to 80° C. and a polymerization process was performed for 2 hours. At this time, ethylene gas was ^{continuously injected so that the pressure of the reactor was maintained at about 9kgf/cm 2} , and the amount of hydrogen was added at 0.16% by volume compared to the ethylene. After completion of the reaction, unreacted ethylene and hydrogen were vented.

Examples 2 and 3

As shown in Table 1 below, polyethylene was prepared in the same manner as in Example 1, except that the catalyst and polymerization conditions were changed.

Comparative Example 1

High-density polyethylene (CE2080™, manufactured by LG Chem.) prepared using a Ziegler-Natta catalyst was used.

Comparative Examples 2 to 4

As shown in Table 1 below, polyethylene was prepared in the same manner as in Example 1, except that the catalyst and polymerization conditions were changed.

	catalyst			Polymerization conditions
	Catalyst type	First transition metal compound / content (mmol/gSiO 2 )	Second transition metal compound/content (mmol/gSiO 2 )	Temperature (℃)	pressure (bar)	Catalyst input (mg)	H 2 input (Volume% relative to ethylene)	HDPE Yield (g)
Example 1	Manufacturing Example 1	Synthesis Example 1/ 0.15	Synthesis Example 2-1/ 0.18	80	9	15	0.16	207
Example 2	Manufacturing Example 2	Synthesis Example 1/0.24	Synthesis Example 2-2/ 0.12	80	9	11.1	0.12	204
Example 3	Manufacturing Example 3	Synthesis Example 1/0.15	Synthesis Example 2-2/ 0.18	80	9	14.0	0.19	212
Comparative Example 1	-	Ziegler Natta Catalyst	-	-	-	-	-	-
Comparative Example 2	Comparative Production Example 2	Synthesis Example 1/ 0.10	Comparative Synthesis Example 2-2/ 0.25	80	9	17.3	0.25	210
Comparative Example 3	Comparative Production Example 3	Synthesis Example 1/ 0.10	Comparative Synthesis Example 2-3/ 0.10	80	9	19.9	0.23	206
Comparative Example 4*	Comparative Production Example 4	Synthesis Example 1/ 0.15	Comparative Synthesis Example 2-4/ 0.18	80	9	15	0.16	86

* In the case of Comparative Example 4, due to the absence of a tether in the second transition metal compound used in the production of polyethylene, the activity during polymerization was low, and fouling occurred in the reactor due to leaching.

Test Example 1

The activity of the transition metal compound used in the preparation of the hybrid supported catalyst of the present invention as a sole catalyst was evaluated. Specifically, homopolyethylene was prepared by using the transition metal compound prepared in Synthesis Example and Comparative Synthesis Example as a single catalyst, respectively, and the polymerization activity and the weight average molecular weight (Mw) and molecular weight distribution (PDI) of the prepared polymer were respectively It was measured. The results are shown in Table 2 below.

<Preparation of metallocene supported catalyst>

Silica gel (SYLOPOL 952X™, calcinated under 250°C, 7g) was placed in a glass reactor under argon (Ar), and 53.1 mL of a 10 wt% methylaluminoxane (MAO) toluene solution (corresponding to 10 mmol per 1 g of silica) was added at room temperature It was slowly injected and stirred at 95°C for 12 hours. After completion of the reaction, it was cooled to room temperature and left for 15 minutes to decant the solvent using a cannula. 50 mL of toluene was added, stirred for 1 minute, and allowed to stand for 15 minutes, and the solvent was decanted using a cannula. After 50 ml of toluene was added again, 60 μmol of each transition metal compound prepared in Synthesis Example or Comparative Synthesis Example (corresponding to 60 μmol per 1 g of Silica) was dissolved in 10 ml of toluene, and then transferred to the reactor using a cannula. After stirring at 80° C. for 2 hours, it was cooled to room temperature and left for 15 minutes to decant the solvent using a cannula. 50 mL of toluene was added, stirred for 1 minute, left for 15 minutes, and decanted the solvent using a cannula twice. In the same way, 50 mL of hexane was added, stirred for 1 minute, allowed to stand for 15 minutes, decant the solvent using a cannula, and dissolved in nucleic acid (Atmer 163™, manufactured by CRODA) 3.1 ml of solution (antistatic agent content = silica 2 parts by weight relative to 100 parts by weight) was transferred using a cannula. The mixture was stirred at room temperature for 20 minutes and transferred to a glass filter to remove the solvent. It was dried under vacuum at room temperature for 5 hours to obtain a supported catalyst.

<Production of homopolyethylene>

A 600ml metal alloy reactor was prepared that was equipped with a mechanical stirrer, the temperature can be controlled, and can be used for high-pressure reaction. The reactor was vacuum-dried at 120°C, cooled, and 450 ppm of triethylaluminum (1M solution in Hexane) was added at room temperature, and 15 mg of the transition metal compound supported catalyst of Synthesis Example or Comparative Synthesis Example prepared above was added to the reactor. I did. Thereafter, the temperature of the reactor was gradually increased to 80° C. and the polymerization process was performed for 1 hour. At this time, ethylene gas was continuously injected so that ^{the pressure of the reactor was maintained at about 9kgf/cm 2.} After completion of the reaction, unreacted ethylene was vented.

<Evaluation>

(1) Polymerization activity (Activity, kg PE/g cat ^. hr): It was calculated as the ratio of the weight of the produced polymer (kg PE) per mass (g) of the supported catalyst used based on the unit time (h).

(2) Weight average molecular weight (Mw, g/mol) and molecular weight distribution (PDI, polydispersity index): The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured using gel permeation chromatography (GPC), respectively. Then, the molecular weight distribution was calculated with the ratio of Mw/Mn. Specifically, it was measured using a Waters PL-GPC220 instrument using a Polymer Laboratories PLgel MIX-B 300 mm length column. At this time, the evaluation temperature was 160°C, 1,2,4-trichlorobenzene was used as a solvent, and the flow rate was 1 mL/min. The sample was prepared at a concentration of 10 mg/10 mL, and then supplied in an amount of 200 μL. The values of Mw and Mn were derived using a calibration curve formed using polystyrene standards. The molecular weight (g/mol) of the polystyrene standard was 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.

Type of transition metal compound	Polymerization activity (kg PE / g cat. hr )	Mw (g/mol)	PDI
Synthesis Example 1	7.4	87,000	2.4
Synthesis Example 2-1	3.1	1,230,000	2.3
Synthesis Example 2-2	2.6	1,506,000	2.4
Comparative Synthesis Example 2-1	0.9	1,650,000	2.7
Comparative Synthesis Example 2-2	1.1	984,000	2.8
Comparative Synthesis Example 2-3	3.0	940,000	2.9

As a result of the experiment, the first and second transition metal compounds used in the preparation of the hybrid supported catalyst according to the present invention exhibited excellent polymerization activity even when used as a single catalyst. On the other hand, in the case of the transition metal compound prepared in Comparative Synthesis Example 2-1, when used as a sole catalyst, the polymerization activity was 0.9 kg PE/g cat ^. It is very low as hr, and it can be expected that the effect of improving the catalytic activity and the polymer properties accordingly is deteriorated even when used as a hybrid supported catalyst.

Test Example 2

Physical properties of the hybrid supported catalyst used in Examples and Comparative Examples, and polyethylene prepared using the same were measured in the following manner, and the results are shown in Table 3.

(1) Catalyst activity (Activity, kg PE/g cat ^. hr): During polymerization of polyethylene according to Examples and Comparative Examples, the activity of the catalyst was evaluated. It was calculated as the ratio of the weight of the produced polymer (kg PE) per mass (g) of the supported catalyst used based on the unit time (h).

(2) Weight average molecular weight (Mw, g/mol) and molecular weight distribution (PDI, polydispersity index): Using gel permeation chromatography (GPC) for the polyethylene prepared in the above Examples and Comparative Examples, the weight average molecular weight (Mw) ) And the number average molecular weight (Mn) were measured, respectively, and the molecular weight distribution (PDI) was calculated from the ratio of Mw/Mn.

Specifically, it was measured using a Waters PL-GPC220 instrument using a Polymer Laboratories PLgel MIX-B 300 mm length column. At this time, the evaluation temperature was 160°C, 1,2,4-trichlorobenzene was used as a solvent, and the flow rate was 1 mL/min. The sample was prepared at a concentration of 10 mg/10 mL, and then supplied in an amount of 200 μL. The values of Mw and Mn were derived using a calibration curve formed using polystyrene standards. The molecular weight (g/mol) of the polystyrene standard was 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.

(3) MI _5.0 and MFRR (21.6 / 5): Melt Index of the polyethylene prepared in Examples and Comparative Examples (MI _{5. 0)} is according to ASTM D1238 (condition E, 190 ℃, 5.0 kg load) Standards It was measured. In addition, the melt flow rate ratio (MFRR, 21.6/5) to polyethylene was calculated by dividing _{MFR 21.6} by MFR _{5 , and MFR 21.6} was measured under a temperature of 190°C and a load of 21.6 kg according to ASTM D 1238. And, MFR ₅ was measured under a temperature of 190 °C and a load of 5.0 kg according to ASTM D 1238.

(4) Complex viscosity (η*(ω500)): In order to be used as a CPE for wire and cable, the Mooney viscosity must be adjusted. Accordingly, if the complex viscosity (η*(ω500)) measured at a frequency (ω) of 500 rad/s is at the level of 800 Pa·s, the Mooney viscosity is expected to coincide and was set to the same level.

Specifically, the complex viscosity of polyethylene was measured at a frequency (ω) of 0.05 rad/s with ARES (Advanced Rheometric Expansion System, ARES G2) of TA instruments. Samples were made to have a gap of 2.0 mm using parallel plates with a diameter of 25.0 mm at 190°C. The measurement was performed in a dynamic strain frequency sweep mode, where the strain was 5%, the frequency was from 0.05 rad/s to 500 rad/s, and a total of 41 points were measured with 10 points in each decade.

(5) Density: The density (g/cm ³ ) of polyethylene was measured by the method of ASTM D-1505.

(6) Fraction (%): GPC analysis was performed, and the fraction was calculated as the area (%) occupied by log Mw section relative to the total area in the resulting molecular weight distribution curve. The sum of the fractions is 100±1, not exactly 100.

The GPC analysis was specifically performed under the following conditions.

A Waters PL-GPC220 instrument was used as the GPC device, and a Polymer Laboratories PLgel MIX-B 300 mm long column was used. At this time, the measurement temperature was 160°C, 1,2,4-trichlorobenzene was used as a solvent, and the flow rate was 1 mL/min. Polyethylene samples according to Examples and Comparative Examples were pretreated by dissolving in trichlorobenzene (1,2,4-Trichlorobenzene) containing 0.0125% BHT for 10 hours at 160° C. using a GPC analyzer PL-GP220, respectively, and 10 mg After preparing to a concentration of /10 mL, it was supplied in an amount of 200 μL. Values of Mw and Mn were derived using a calibration curve formed using a polystyrene standard specimen. The weight average molecular weight of the polystyrene standard specimen is 2000 g/mol, 10000 g/mol, 30000 g/mol, 70000 g/mol, 200000 g/mol, 700000 g/mol, 2000000 g/mol, 4000000 g/mol, 10000000 g 9 types of /mol were used.

(7) MDR torque (M _H -M _L ):

In order to evaluate the degree of crosslinking of polyethylene, the MDR torque value of each polyethylene sample was measured using Alpha Technologies Production MDR (Moving Die Rheometer).

Specifically, 100 g of each sample of polyethylene prepared in Examples and Comparative Examples, 0.4 g of a phenolic antioxidant (AO), and 1.2 g of a crosslinking agent (DCP, Dicumyl Peroxide) were mixed at 80° C. and then at 140° C. _{A sample sheet was prepared for min, and M H} values and M _L values were measured under conditions of 180° C. and 10 min using a moving die rheometer (MDR) for the prepared sample sheet. MDR torque (M _H -M _L ) was calculated _{by subtracting the M L} value from the measured M _{H value.} Here, M _H is the maximum vulcanizing torque measured in full cure, and M _L is the stored minimum vulcanizing torque.

	Catalytic activity (kg PE/g cat 2hr)	PE
		Mw (g/mol)	PDI	MI 5.0 (g/10min)	MFRR (21.6/5)	η*(ω500) (Pa·s)	density (g/cm 3 )	Fraction(%)		MDR torque (M H -M L ) (Nm)
								log Mw 3.5 or less	log Mw more than 3.5 ~ less than 4.0
Example 1	13.8	245,000	8.9	1.34	15.2	796	0.950	0.96	4.32	8.7
Example 2	18.4	196,000	6.1	2.41	10.3	800	0.949	0.80	3.93	11.5
Example 3	11.2	277,000	10.3	0.81	18.6	810	0.953	1.20	4.65	7.7
Comparative Example 1	-	177,000	9.1	1.30	15.2	800	-	2.64	8.89	5.6
Comparative Example 2	12.1	148,000	5.8	0.69	19.0	794	-	2.19	8.43	6.5
Comparative Example 3	10.4	155,000	5.7	0.77	18.4	804	0.955	1.55	5.77	7.3

As a result of the experiment, the hybrid supported catalysts used in Examples 1 to 3 exhibited superior catalytic activity at an equivalent level or higher compared to the catalysts used in Comparative Examples, and in particular, the hybrid supported catalysts in Examples 1 and 2 were It showed a higher catalytic activity than that.

In addition, the polyethylenes of Examples 1 to 3 prepared using the hybrid supported catalyst had a fraction ratio of less than or equal to 3.5 in log Mw of 3.5 or less, and a fractional ratio of more than 3.5 to less than or equal to 4.0 of log Mw was also 4.65% or less, compared Compared to the examples, it exhibited a significantly reduced low molecular weight, and at the same time exhibited a broad molecular weight distribution of 6.1 or more. In addition, it can be seen that the MDR torque is 7.7 or more, which has a higher degree of crosslinking than the comparative example.

On the other hand, in the case of Example 3, it was superior to the comparative example, but exhibited the effect of reducing the low molecular weight and improving the crosslinking degree slightly lower than in Examples 1 and 2. This result is due to the difference in the catalyst used in the production of polyethylene, and Example 3 contains the same combination of transition metal compounds as in Example 2, but the mixing ratio is different, and the first and second examples are different from those of Example 1. 2 The conditions for the mixing ratio of the transition metal compound are the same, but the structure of the second transition metal compound is different. Accordingly, the hybrid supported catalyst comprising a combination of the first and second transition metal compounds according to the present invention exhibits more excellent effects in terms of improving catalytic activity and polyethylene properties compared to the conventional catalyst, and the first and second transition metal compounds It can be seen that when the mixing ratio is optimized according to the combination of, the catalytic activity and physical properties of the polyethylene to be produced can be further improved.

Claims (17)

1. At least one first transition metal compound represented by the following formula (1);

   At least one second transition metal compound represented by the following formula (2); And

   Containing; a carrier on which the first and second transition metal compounds are supported

   Hybrid supported catalyst:

   [Formula 1]

   (Cp ¹ R ₁₁ ) _m (Cp ² R ₁₂ ) M ₁ (Z ₁ ) _3-m

   In Formula 1,

   M ₁ is a Group 4 transition metal;

   Cp ¹ and Cp ² are the same as or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals. One, and they are unsubstituted or substituted with _{C 1-20 hydrocarbons;}

   R ₁₁ and R ₁₂ are the same as or different from each other, and each independently hydrogen, C _1-20 alkyl, C _1-20 alkoxy, C _2-20 alkoxyalkyl, C _6-20 aryl, C _6-20 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _8-40 arylalkenyl, C _2-20 alkynyl, or selected from the group consisting of N, O and S _{C 2-20} heteroaryl containing one or more heteroatoms;

   Z ₁ is halogen, C _1-20 alkyl, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _6-20 aryl, C _1-20 alkylidene, amino group, C _{2- 20} alkylalkoxy, or C _7-40 arylalkoxy;

   m is 1 or 0;

   [Formula 2]

   

   In Chemical Formula 2,

   A is carbon or silicon,

   M ₂ is a Group 4 transition metal,

   R ₂₁ is C _6-20 aryl substituted with _{C 1-20 alkyl,}

   R ₂₂ is C _3-20 branched alkyl,

   R ₂₃ to R ₂₅ are each independently C _1-20 alkyl,

   Z ₂₁ and Z ₂₂ are each independently halogen or C _1-10 alkyl,

   n is an integer from 1 to 10.
2. The method of claim 1,

   M ₁ is Ti, Zr or Hf;

   Cp ¹ and Cp ² are the same as or different from each other, and each independently selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl, and fluorenyl radicals. One, and these are unsubstituted or substituted with _{C 1-10 alkyl;}

   R ₁₁ and R ₁₂ are each independently hydrogen, C _1-20 alkyl, C _2-20 alkoxyalkyl, C _6-20 aryl, C _7-20 arylalkyl, furanyl, or thiophenyl, R At least one of ₁₁ and R _{12 is C 2-20} alkoxyalkyl;

   Z ₁ is halogen; phosphorus,

   Hybrid supported catalyst.
3. The method of claim 1,

   The first transition metal compound is a compound selected from the group consisting of compounds of the following structure,

   Hybrid supported catalyst:

   

   .
4. The method of claim 1,

   M ₂ is titanium,

   Z ₂₁ and Z ₂₂ are each independently C _1-4 alkyl,

   Hybrid supported catalyst.
5. The method of claim 1,

   R ₂₁ is phenyl substituted with 1 or 2 _{C 3-6 branched alkyl,}

   R ₂₂ and R ₂₃ are each independently, C _3-6 branched alkyl,

   Hybrid supported catalyst.
6. The method of claim 1,

   A is silicon,

   R ₂₅ is C _3-6 branched alkyl,

   n is an integer of 4 to 6,

   Hybrid supported catalyst.
7. The method of claim 1,

   R ₂₂ is isopropyl, a transition metal compound.
8. The method of claim 1,

   The second transition metal compound is selected from the group consisting of compounds of the following structure,

   Hybrid supported catalyst:

   

   .
9. The method of claim 1,

   The first and second transition metal compounds are included in a molar ratio of 1:3 to 3:1,

   Hybrid supported catalyst.
10. The method of claim 1,

    The carrier comprises any one or a mixture of two or more selected from the group consisting of silica, alumina and magnesia,

    Hybrid supported catalyst.
11. In the presence of a catalyst composition comprising the hybrid supported catalyst according to any one of claims 1 to 10, comprising the step of polymerizing an olefinic monomer,

    Method for producing polyolefin.
12. The method of claim 11,

    The catalyst composition further comprises at least one of a cocatalyst and an antistatic agent,

    Manufacturing method.
13. The method of claim 12,

    The cocatalyst includes a compound selected from the group consisting of compounds of the following formulas 9 to 11,

    Manufacturing method:

    [Formula 9]

    -[Al(R _a )-O] _m-

    In Chemical Formula 9,

    R _a are the same as or different from each other, and each independently halogen; Hydrocarbons of C _1-20; Or a halogen-substituted C _1-20 hydrocarbon;

    m is an integer of 2 or more;

    [Formula 10]

    J(R _b ) ₃

    In Chemical Formula 10,

    R _b is the same as or different from each other, and each independently halogen; Hydrocarbons of C _1-20; Or a halogen-substituted C _1-20 hydrocarbon;

    J is aluminum or boron;

    [Formula 11]

    _{^{[EH] + [ZQ 4]}} - or _{^{[E] + [ZQ 4]}} -

    In Formula 11,

    E is a neutral or cationic Lewis base;

    H is a hydrogen atom;

    Z is a group 13 element;

    Q is the same as or different from each other, and each independently one or more hydrogen atoms _{is substituted or unsubstituted with halogen, C 1-20} hydrocarbon, alkoxy or phenoxy, C _6-20 aryl group or C _1-20 alkyl group to be.
14. The method of claim 12,

    The antistatic agent is an ethoxylated alkylamine,

    Manufacturing method.
15. The method of claim 11,

    The polymerization is carried out under the introduction of 0.1 to 0.2% by volume of hydrogen gas based on the total volume of the olefin monomer,

    Manufacturing method.
16. The method of claim 11,

    The olefin monomer is ethylene,

    Manufacturing method.
17. The method of claim 11,

    The polyolefin, in the molecular weight distribution curve by gel permeation chromatography analysis, has an area ratio occupied by an area of log Mw of 3.5 or less relative to the total area of the distribution curve of 1.4% or less, and a molecular weight distribution of 6 to 15,

    Manufacturing method.