RU2773517C2 - Polyethylene copolymer and its production method - Google Patents

Abstract

FIELD: pipe production.

SUBSTANCE: present invention relates to a group of inventions: polyethylene copolymer, a method for the production of polyethylene copolymer, and a pipe. Polyethylene copolymer contains a repeated link obtained from ethylene and a repeated link obtained from alpha-olefin, having from 3 to 10 carbon atoms. Polyethylene copolymer satisfies the equation 1: Index SCG ≤ (a number of carbon atoms of alpha-olefin)^1/2 × 5. Polyethylene copolymer satisfies the equation 2: Comonomer distribution index (CDI) = c/d. The method for the production of polyethylene copolymer includes a stage of polymerization of ethylene monomer and alpha-olefin monomer selected from C_3-10 alpha-olefins in the presence of a hybrid catalyst on substrate. The hybrid catalyst includes: a mixture of transitional metals including the first mixture including the first compound of transitional metal selected from chemical formulas 2 and 3, and the second compound of transitional metal selected from chemical formulas 4-7, or the second mixture including the first compound of transitional metal containing the chemical formula 1, and the second compound of transitional metal containing a compound selected from chemical formulas 4, 6 and 7. Mixtures of transitional metals are applied to substrate. The pipe contains polyethylene copolymer.

EFFECT: development of polyethylene copolymer, which has excellent recyclability and durability and, consequently, is useful for the formation of a hollow pipe or similar product.

15 cl, 2 dwg, 1 tbl, 5 ex

Description

Technical field

Cross-reference to related application(s)

This application claims the benefit of the filing date of Korean Patent Application No. 10-2017-0176416 filed with the Korean Intellectual Property Office on December 20, 2017 and the filing date of Korean Patent Application No. 10-2018-0154616 filed with the Korean Intellectual Property Office. property of the Republic of Korea on December 4, 2018, the entire contents of which are hereby incorporated by reference.

The present invention relates to a polyethylene copolymer and to a process for its preparation.

State of the art

Polyolefin resins used in large diameter high pressure pipes typically require high pressure resistance and excellent processability. High pressure resistance is generally a physical property that can be expressed by a high density area. This is because the modulus increases with the increase in the degree of crystallization in the polyolefin resin, and hence the high pressure capability increases.

However, for conventional pipes, long-term pressure resistance must be guaranteed for at least 50 years. However, when the density is high, there is a disadvantage in that the brittle fracture behavior resistance deteriorates and the long-term pressure resistance performance deteriorates. In addition, when the molecular weight of the polyolefin resin is low or the polydispersity index is narrow, the resin dripping phenomenon occurs during production of the large diameter pipe, and processing is difficult. Thus, in order to solve these problems, it is necessary to use a polyolefin resin having a high molecular weight and a very wide polydispersity index.

In addition, when the molecular weight of the polyolefin resin is high, the extrusion load increases and the pipe processability falls, and hence there is a limitation due to poor appearance.

Thus, there is a constant need to obtain excellent products having an optimal balance between long-term stability and processability.

Detailed description of the invention

Technical task

The object of the present invention is to provide a polyethylene copolymer which is excellent in processability and durability, and hence is useful for molding a hollow pipe or the like.

Another object of the present invention is to develop a method for producing the above-mentioned polyethylene copolymer.

Yet another object of the present invention is to provide a molded article comprising the aforementioned polyethylene copolymer.

Technical solution

In accordance with one embodiment of the invention, there is provided a polyethylene copolymer comprising an ethylene-derived repeating unit and an alpha-olefin-derived repeating unit having 3 or more carbon atoms and satisfying the following Equation 1:

[Equation 1]

SCG index ≤ (alpha-olefin carbon number) ^1/2 × 5.

In Equation 1 above, the SCG index is the value (p/q) obtained by dividing the melt index (p) of the polyethylene copolymer, measured in accordance with ASTM 1238 (load 21.6 kg, 190°C), by the comonomer distribution index (q) of the polyethylene copolymer, and the comonomer distribution index (CDI) is calculated using Equation 2 below based on the molecular weight distribution plot (where x-axis is the molecular weight of the polymer chain and y-axis is the content of the polymer chain) obtained using gel permeation chromatography against a polyethylene copolymer.

[Equation 2]

Comonomer Distribution Index (CDI) = c/d

In Equation 2 above, "c" is the short chain branching (SCB) content (measured by FT-IR) of 2-7 carbons per 1000 carbons of the polymer chain, which is the molecular weight value "m" at which the area (s1) between the molecular weight distribution curve and the x-axis in the area a≤x≤m is 80% of the area (s2) between the molecular weight distribution curve and the x-axis in the area a≤x≤b;

"d" is the content of short chain branching (SCB) (measured by FT-IR) of 2-7 carbon atoms per 1000 carbon atoms of the polymer chain, which is the value of the molecular weight "n" at which the area (s3) between the curve molecular weight distribution and the x-axis in the area a≤x≤n is 20% of the area (s4) between the molecular weight distribution curve and the x-axis in the area a≤x≤b;

"a" is the minimum molecular weight value, which is represented by the x-axis in the molecular weight distribution graph, and "b" is the maximum molecular weight value, which is represented by the x-axis in the molecular weight distribution graph.

The inventors have found through experiments that when a polyethylene copolymer satisfying the condition of Equation 1 is used, excellent processability can be realized due to relatively low melt viscosity, and at the same time, long-term brittle fracture resistance can be improved by controlling the molecular weight distribution of the comonomer, and therefore excellent durability can be realized. The present invention has been made based on such discoveries.

In particular, it is clear that the polyethylene copolymer satisfying the condition of Equation 1 is produced by the polyethylene copolymer production method according to another embodiment described later. More specifically, this can be accomplished by polymerizing an ethylene monomer and an alpha-olefin monomer in the presence of a supported hybrid catalyst that includes: a transition metal mixture comprising a first mixture comprising a first transition metal compound containing at least one compound, selected from the group consisting of the following chemical formulas 2 and 3, and a second transition metal compound containing at least one compound selected from the group consisting of the following chemical formulas 4-7, or a second mixture comprising the first transition metal compound containing the following chemical formula 1, and a second transition metal compound containing at least one compound selected from the group consisting of the following chemical formulas 4, 6 and 7; and a substrate on which mixtures of transition metals are deposited.

An ethylene-derived repeating unit is a repeating unit formed by polymerization of an ethylene monomer, and an alpha-olefin-derived repeating unit means a repeating unit formed by polymerization of an alpha-olefin monomer. The alpha-olefin monomer has 3 or more carbon atoms, or 3 to 20 carbon atoms, or 3 to 10 carbon atoms, and examples thereof include one or more olefins selected from the group consisting of 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-eicosene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinyl-norbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.

In the ethylene/alpha-olefin copolymer, the alpha-olefin content as a comonomer is not particularly limited, and may be appropriately selected depending on the application, purpose, etc. of the copolymer. More specifically, it may be greater than 0 mol%. and 99% mol. or less.

More specifically, Equation 1 can be expressed by Equation 1-1 below.

[Equation 1-1]

SCG index ≤ (alpha-olefin carbon number) ^1/2 × 4.6.

In Equation 2 above, "c" can be the short chain branching (SCB) content of 2-7 carbons per 1000 carbons of the polymer chain (measured by Fourier transform infrared spectroscopy (FT-IR)), which is the molecular weight value "m" at which the area (s1) between the molecular weight distribution curve and the x-axis in the section a≤x≤m is 80% of the area (s2) between the plot of the molecular weight distribution curve and the x-axis in the section a≤x ≤b. The area (s1) between the molecular weight distribution curve and the x-axis in the section a≤x≤m can mean the integral value in the interval a≤x≤m on the molecular weight distribution plot, and the area (s2) between the molecular weight distribution curve and the x-axis in the area a≤x≤b can mean an integral value in the interval a≤x≤b.

In this case, "a" is a positive real number indicating the minimum molecular weight value on the x-axis in the molecular weight distribution plot, "b" is a positive real number indicating the maximum molecular weight value on the x-axis in the graph molecular weight distribution, and "m" is a positive real number satisfying a≤m≤b, and may satisfy the expression s1=0.8×s2. More specifically, the following equation may be satisfied.

[Equation 3]

In addition, in Equation 2, "d" may be the content of short chain branching (SCB) of 2-7 carbons per 1000 carbons of the polymer chain (measured by Fourier transform IR spectroscopy), which is the value of the molecular weight "n", where the area (s3) between the molecular weight distribution curve and the x-axis in the area a≤x≤n is 20% of the area (s4) between the molecular weight distribution curve and the x-axis in the area a≤x≤b. The area (s3) between the molecular weight distribution curve and the x-axis in the area a≤x≤n can mean the integral value in the interval a≤x≤n on the molecular weight distribution plot, and the area (s4) between the molecular weight distribution curve and the x-axis in the area a≤x≤b can mean an integral value in the interval a≤x≤b.

In this case, "a" is a positive real number indicating the minimum molecular weight value, which is represented by the x-axis on the molecular weight distribution plot, "b" is a positive real number indicating the maximum molecular weight value on the x-axis on the molecular weight distribution plot, and "n" is a positive real number satisfying a≤n≤b, and may satisfy the expression s3=0.2×s4. In this case, "n" is a positive real number that satisfies a≤n≤b. More specifically, the following Equation 4 can be satisfied.

[Equation 4]

A specific example of calculating the comonomer distribution index (CDI) according to the above equations 2, 3 and 4 is shown in FIG. 2.

The term "polymer chain(s)" contained(s) in a "polyethylene copolymer" may refer to a plurality of polymer chains obtained during the polymerization and production of the polyethylene copolymer. Molecular weight, etc. such polymer chains can be confirmed using a molecular weight distribution curve (shown by a continuous solid line in FIG 1) using gel permeation chromatography (GPC (GPC)).

The Gel Permeation Chromatography used to plot the molecular weight distribution curve is carried out, for example, using a Polymer Laboratories PLgel MIX-B, 300 mm column, Waters PL-GPC220, where the evaluation temperature is 100 to 200°C, 1 ,2,4-trichlorobenzene is used as a solvent, the flow rate is from 0.1 to 10 ml/min, and a sample having a concentration of 1 to 20 mg/10 ml can be used under feeding conditions in an amount of 100 to 300 µl.

On the other hand, the side chain branching content of 2 to 7 carbon atoms per 1000 carbon atoms that each of the plurality of polymer chains present in the polyethylene copolymer can be confirmed by analyzing the polyethylene copolymer by FTIR spectroscopy.

The Fourier transform IR (FT-IR) method used to measure short chain branching (SCB) is carried out, for example, using a PerkinElmer Spectrum 100 instrument including a DTGS detector (deuterated triglycerol sulfate detector), where the evaluation temperature is from 100 to 200°C, the wave number is from 2000 to 4000 cm ^-1 , the number of scans is from 1 to 20 and the resolution is from 1 to 10 cm ^-1 .

When the SCG index of the polyethylene copolymer in the above embodiment exceeds the value of (number of alpha-olefin carbon atoms) ^1/2 ×5 and does not satisfy Equation 1, there is a limitation that when the melt index of the polyethylene copolymer increases or the comonomer distribution index ( CDI), processability and durability are reduced.

More specifically, the polyethylene copolymer may have an SCG index of 11 or less, 5 to 11, 5 to 10, or 5 to 9.6, and the polyethylene copolymer may have a comonomer distribution index (CDI) of 1.2 to 3.0, 1.2 to 2.6 or 1.23 to 2.56.

Therefore, the polyethylene copolymer may have S.H. modulus (measured at 80°C) 0.85 MPa or more, 0.85 to 1.0 MPa, or 0.90 to 0.97 MPa. In addition, the polyethylene copolymer may have a stress crack resistance (Full Notch Creep Test (FNCT) measured at 4 MPa) of 1000 hours or more, or 1000 to 10000 hours.

Thus, it can be confirmed that the polyethylene copolymer has a high S.H. modulus (work hardening modulus) and high resistance to stress cracking (FNCT), and therefore has excellent long-term brittle fracture resistance.

The polyethylene copolymer has a melt index (measured at 190°C under a load of 2.16 kg in accordance with ASTM D1238) from 0.01 to 0.65 g/10 min, from 0.02 to 0.60 g/10 min, 0.03 to 0.60 g/10 min or 0.036 to 0.591 g/10 min. In addition, the polyethylene copolymer has a melt index (measured at 190°C under a load of 21.6 kg in accordance with ASTM D1238) from 2 to 30 g/10 min, from 9 to 25 g/10 min, or from 9.5 to 24 .5 g/10 min.

The polyethylene copolymer may have a density (ASTM 1505) of 0.930 to 0.945 g/cm ³ or 0.935 to 0.940 g/cm ³ .

The average value of the branching content of side chains (measured by FTIR spectroscopy) of 2-7 carbon atoms per 1000 carbon atoms, which each of the plurality of polymer chains found in the polyethylene copolymer, is characterized by being from 7/1000C to 15 /1000C, 7/1000C to 14/1000C, 7/1000C to 13/1000C, 7/1000C to 12/1000C, or 7/1000C to 11/1000C.

The average amount of branching of 2-7 carbons per 1000 carbons that each of the plurality of polymer chains present in the polyethylene copolymer can be calculated by dividing the total amount of branching of 2-7 carbons by 1000 carbons , which has each of the many polymer chains found in the polyethylene copolymer, by the number of polymer chains found in the polyethylene copolymer.

On the other hand, the average value of the branching content of side chains of 2 to 7 carbon atoms per 1000 carbon atoms that each of the plurality of polymer chains found in the polyethylene copolymer can be obtained in accordance with the above method of calculating the average value after obtaining the distribution curve SCB (shown as a broken dotted line in FIG. 1), where the log value (log M) of the molecular weight (M) obtained by gel permeation chromatography is taken as the x-axis, and the branching content of side chains of 2-7 carbon atoms per 1000 carbon atoms relative to the log value obtained by Fourier IR spectroscopy is taken as the y-axis.

That is, for a polyethylene copolymer, a value obtained by averaging the branching content of side chains of 2-7 carbon atoms per 1000 carbon atoms of each polymer chain with respect to all polymer chains having different molecular weights measured by gel permeation chromatography (GPC) can show results up to 7/1000C to 15/1000C, 7/1000C to 14/1000C, 7/1000C to 13/1000C, 7/1000C to 12/1000C, or 7/1000C to 11/1000C.

Since the average value of side chain branching (SCB) content (measured by Fourier IR spectroscopy) of 2-7 carbon atoms per 1000 carbon atoms that each of the plurality of polymer chains of the polyethylene copolymer rises to 7/1000C or more, the associated molecules such as short chain branches (SCB) are concentrated in the high molecular weight part, which is relatively more responsible for physical properties than the low molecular weight part, thereby realizing excellent physical properties compared to conventional copolymers.

The polyethylene copolymer may have at least one of the above physical properties, and it may have all of the above physical properties in order to exhibit excellent mechanical strength. In this case, the effect of improving mechanical strength and processability can be more noticeable along with excellent durability.

The aforementioned polyethylene copolymer can be produced by a production method comprising the step of polymerizing an ethylene monomer and an alpha-olefin monomer in the presence of a supported hybrid catalyst, which comprises: a transition metal mixture comprising a first mixture comprising a first transition metal compound containing at least , one compound selected from the group consisting of the following chemical formulas 2 and 3, and a second transition metal compound containing at least one compound selected from the group consisting of the following chemical formulas 4-7, or a second mixture comprising a first transition metal compound containing the following chemical formula 1, and a second transition metal compound containing at least one compound selected from the group consisting of the following chemical formulas 4, 6 and 7; and a substrate on which mixtures of transition metals are deposited.

[Chemical formula 1]

.

.

In chemical formula 1:

M ₁ is a Group 4 transition metal;

at least one of the R ₁ -R ₈ substituents is -(CH ₂ ) _n -OR _a (where R _a is a linear or branched C _1-6 alkyl group and n is an integer from 2 to 10) , and the rest are the same or different from each other and each independently represents a hydrogen atom, C _1-20 -alkyl, C _2-20 -alkenyl, C _3-20 -cycloalkyl, C _6-20 -aryl, C _7-20 -alkyl-aryl or C _7-20 -arylalkyl, or two or more adjacent groups are connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring, and

X ₁ and X ₂ are the same or different from each other and each independently represents a halogen atom, C _1-20 alkyl, C _2-10 alkenyl, C _3-20 cycloalkyl, C _7-40 alkylaryl, C _{7 -40} arylalkyl, C _6-20 aryl, C _1-20 alkylidene, amino, C _2-20 alkyl alkoxy or C _7-40 arylalkoxy group.

[Chemical Formula 2]

.

.

In chemical formula 2:

M ₂ is a Group 4 transition metal;

X ₃ and X ₄ are the same or different from each other and each independently represents a halogen atom, C _1-20 alkyl, C _2-10 alkenyl, C _3-20 cycloalkyl, C _7-40 alkylaryl, C ₇ a _-40 arylalkyl, C _6-20 aryl, C _1-20 alkylidene, amino, C _2-20 alkyl alkoxy or C _7-40 arylalkoxy group;

at least one of the R ₁₁ -R ₁₄ substituents is -(CH ₂ ) _m -OR _b (wherein R _b is a linear or branched C _1-6 alkyl group and m is an integer from 2 to 10) , and the rest are the same or different from each other and each independently represents a hydrogen atom, C _1-20 -alkyl, C _2-20 -alkenyl, C _3-20 -cycloalkyl, C _6-20 -aryl, C _7-20 -alkylaryl or C _7-20 -arylalkyl, or two or more neighboring groups are connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring,

R ₁₅ and R ₁₆ are the same or different from each other and each independently represents a hydrogen atom, C _1-20 alkyl, C _3-20 cycloalkyl, C _1-10 alkoxy, C _2-20 alkoxyalkyl, C _6-20 aryl, C _6-10 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _8-40 arylalkenyl, or C _2-10 alkynyl ; and

X ₃ and X ₄ are the same or different from each other and each independently represents a halogen atom, C _1-20 alkyl, C _2-10 alkenyl, C _3-20 cycloalkyl, C _7-40 alkylaryl, C _{7 -40} arylalkyl, C _6-20 aryl, C _1-20 alkylidene, amino, C _2-20 alkyl alkoxy or C _7-40 arylalkoxy group.

[Chemical formula 3]

.

.

In chemical formula 3:

M ₃ is a Group 4 transition metal;

X ₅ and X ₆ are the same or different from each other and each independently represents a halogen atom, C _1-20 alkyl, C _2-10 alkenyl, C _3-20 cycloalkyl, C _7-40 alkylaryl, C ₇ a _-40 arylalkyl, C _6-20 aryl, C _1-20 alkylidene, amino, C _2-20 alkyl alkoxy or C _7-40 arylalkoxy group; and

R ₂₀ -R ₂₉ are the same or different from each other and each independently represents a hydrogen atom, C _1-20 -alkyl, C _3-20 -cycloalkyl, C _1-10 -alkoxy group, C _2-20 -alkoxyalkyl, C _6-20 aryl, C _6-10 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _8-40 arylalkenyl, or C _2-10 alkynyl , provided that at least one of the substituents R ₂₀ -R ₂₉ represents the group -(CH ₂ ) _p -OR _c (wherein R _c represents a linear or branched C _1-6 -alkyl group, and p means an integer from 2 to 10).

[Chemical formula 4]

.

.

In chemical formula 4:

A ₁ represents a hydrogen atom, a halogen atom, a C _1-20 alkyl group, a C _2-20 alkenyl group, a C _6-20 aryl group, a C _7-20 alkylaryl group, a C _7-20 arylalkyl group, a C _1-20 alkoxy group, a C _2-20 alkoxyalkyl group, a C _3-20 heterocycloalkyl group, or a C _5-20 heteroaryl group;

D ₁ represents -O-, -S-, -N(R)- or -Si(R)(R')-, where the substituents R and R' are the same or different from each other and each independently represents a hydrogen atom , a halogen atom, a C _1-20 alkyl group, a C _2-20 alkenyl group, or a C _6-20 aryl group;

L ₁ is a linear or branched C _1-10 alkylene group;

Y ₁ represents a carbon, silicon or germanium atom;

Z ₁ represents a hydrogen atom, a halogen atom, a C _1-20 alkyl group, a C _2-20 alkenyl group, a C _6-20 aryl group, a C _7-20 alkylaryl group, or a C _7-20 arylalkyl group;

M ₄ is a Group 4 transition metal;

X ₇ and X ₈ are the same or different from each other and each independently represents a halogen atom, C _1-20 alkyl, C _2-10 alkenyl, C _3-20 cycloalkyl, C _7-40 alkylaryl, C _{7 -40} arylalkyl, C _6-20 aryl, C _1-20 alkylidene, amino, C _2-20 alkyl alkoxy or C _7-40 arylalkoxy group, and

C ₁ is represented by the following chemical formula 4a:

[Chemical formula 4a]

.

.

In this case, C ₂ is -NR ₃₆ -;

the substituents R ₃₀ -R ₃₆ are the same or different from each other and each independently represents a hydrogen atom, a halogen atom, a C _1-20 alkyl group, a C _2-20 alkenyl group, a C _1-20 alkylsilyl group, a C ₁ a _-20 silylalkyl group, a C _1-20 alkoxysilyl group, a C _1-20 alkoxy group, a C _6-20 aryl group, a C _7-20 alkylaryl group, or a C _7-20 arylalkyl group, and two or several adjacent groups from R ₃₀ -R ₃₅ may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.

[Chemical Formula 5]

.

.

In chemical formula 5:

A ₂ is a hydrogen atom, a halogen atom, a C _1-20 alkyl group, a C _2-20 alkenyl group, a C _6-20 aryl group, a C _7-20 alkylaryl group, a C _7-20 arylalkyl group, a C a _1-20 alkoxy group, a C _2-20 alkoxyalkyl group, a C _3-20 heterocycloalkyl group, or a C _5-20 heteroaryl group;

D ₂ is -O-, -S-, -N(R)- or -Si(R)(R')-, where the substituents R and R' are the same or different from each other and each independently represents a hydrogen atom , a halogen atom, a C _1-20 alkyl group, a C _2-20 alkenyl group, or a C _6-20 aryl group;

L ₂ is a linear or branched C _1-10 alkylene group;

Y ₂ represents a carbon, silicon or germanium atom;

Z ₂ represents a hydrogen atom, a halogen atom, a C _1-20 alkyl group, a C _2-20 alkenyl group, a C _6-20 aryl group, a C _7-20 alkylaryl group, or a C _7-20 arylalkyl group;

M ₅ is a Group 4 transition metal;

X ₉ and X ₁₀ are the same or different and each independently represents a halogen atom, C _1-20 alkyl, C _2-10 alkenyl, C _3-20 cycloalkyl, C _7-40 alkylaryl, C ₇ a _-40 arylalkyl, C _6-20 aryl, C _1-20 alkylidene, amino, C _2-20 alkyl alkoxy or C _7-40 arylalkoxy group; and

C ₃ is represented by the following formula 5a:

[Chemical formula 5a]

,

,

in this case C ₄ is -NR ₄₄ -;

the substituents R ₄₀ -R ₄₄ are the same or different from each other and each independently represents a hydrogen atom, a halogen atom, a C _1-20 alkyl group, a C _2-20 alkenyl group, a C _1-20 alkylsilyl group, a C ₁ a _-20 silylalkyl group, a C _1-20 alkoxysilyl group, a C _1-20 alkoxy group, a C _6-20 aryl group, a C _7-20 alkylaryl group, or a C _7-20 arylalkyl group, and two or several adjacent groups from R ₄₀ -R ₄₃ may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.

[Chemical Formula 6]

.

.

In chemical formula 6:

A ₃ is a hydrogen atom, a halogen atom, a C _1-20 alkyl group, a C _2-20 alkenyl group, a C _6-20 aryl group, a C _7-20 alkylaryl group, a C _7-20 arylalkyl group, a C a _1-20 alkoxy group, a C _2-20 alkoxyalkyl group, a C _3-20 heterocycloalkyl group, or a C _5-20 heteroaryl group;

D ₃ is -O-, -S-, -N(R)- or -Si(R)(R')-, where the substituents R and R' are the same or different from each other and each independently represents a hydrogen atom , a halogen atom, a C _1-20 alkyl group, a C _2-20 alkenyl group, or a C _6-20 aryl group;

L ₃ is a linear or branched C _1-10 alkylene group;

Y ₃ represents a carbon, silicon or germanium atom;

Z ₃ represents a hydrogen atom, a halogen atom, a C _1-20 alkyl group, a C _2-20 alkenyl group, a C _6-20 aryl group, a C _7-20 alkylaryl group, or a C _7-20 arylalkyl group;

M ₆ is a Group 4 transition metal;

X ₁₁ and X ₁₂ are the same or different from each other, and each independently represents a halogen atom, C _1-20 -alkyl, C _2-20 -alkenyl, C _3-20 -cycloalkyl, C _7-40 -alkylaryl, C a _7-40 arylalkyl, C _6-20 aryl, C _1-20 alkylidene, amino, C _2-20 alkyl alkoxy or C _7-40 arylalkoxy group; and

C ₅ and C ₆ are the same or different from each other and are each independently represented by one of the following formulas 6a and 6b:

[Chemical formula 6a]

.

.

[Chemical Formula 6b]

.

.

In this case, the substituents R ₅₀ -R ₅₈ and R ₆₀ -R ₆₈ are the same or different from each other and each independently represents a hydrogen atom, a halogen atom, a C _1-20 alkyl group, a C _2-20 alkenyl group, C _1-20 alkylsilyl group, C _1-20 silylalkyl group, C _1-20 alkoxysilyl group, C _1-20 alkoxy group, C _6-20 aryl group, C _7-20 alkylaryl group, or C _{7 -20} -arylalkyl group, and two or more adjacent groups of R ₅₀ -R ₅₈ and R ₆₀ -R ₆₈ can be connected to each other with the formation of a substituted or unsubstituted aliphatic or aromatic ring.

[Chemical formula 7]

.

.

In chemical formula 7:

M ₇ is a Group 4 transition metal;

X ₁₃ and X ₁₄ are the same or different from each other and each independently represents a halogen atom, C _1-20 -alkyl, C _2-10 -alkenyl, C _3-20 -cycloalkyl, C _7-40 -alkylaryl, C _{7 -40} arylalkyl, C _6-20 aryl, C _1-20 alkylidene, amino, C _2-20 alkyl alkoxy or C _7-40 aryl alkoxy group;

at least one of the R ₇₁ -R ₇₄ substituents is -(CH ₂ ) _q -OR _d (wherein R _d is a linear or branched C _1-6 alkyl group and q is an integer from 2 to 10) , and the rest are the same or different from each other and each independently represents a hydrogen atom, C _1-20 -alkyl, C _2-20 -alkenyl, C _3-20 -cycloalkyl, C _6-20 -aryl, C _7-20 -alkyl-aryl or C _7-20 -arylalkyl, or two or more adjacent groups connected to each other with the formation of a substituted or unsubstituted aliphatic or aromatic ring;

the substituents R ₇₅ and R ₇₆ are the same or different from each other and each independently represents a hydrogen atom, C _1-20 -alkyl, C _3-20 -cycloalkyl, C _1-10 -alkoxy group, C _2-20 -alkoxyalkyl , C _6-20 aryl, C _6-10 aryloxy, C _2-20 alkenyl, C _7-40 alkylaryl, C _7-40 arylalkyl, C _8-40 arylalkenyl, or C _2-10 - alkynyl;

X ₁₃ and X ₁₄ are the same or different from each other and each independently represents a halogen atom, C _1-20 -alkyl, C _2-10 -alkenyl, C _3-20 -cycloalkyl, C _7-40 -alkylaryl, C ₇ a _-40 arylalkyl, C _6-20 aryl, C _1-20 alkylidene, amino, C _2-20 alkyl alkoxy or C _7-40 arylalkoxy group; and

Q ₁ and Q ₂ are the same or different from each other and each independently represents a hydrogen atom, a halogen atom, C _1-20 -alkyl, C _2-20 -alkenyl, C _3-20 -cycloalkyl, C _6-20 -aryl , C _7-20 alkylaryl or C _7-20 arylalkyl.

The term C _1-20 alkyl includes straight or branched alkyl, and specific examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, and the like, but are not limited to them.

The term C _2-20 alkenyl includes linear or branched alkenyl, and specific examples thereof include, but are not limited to, allyl, ethenyl, propenyl, butenyl, pentenyl, and the like.

The term C _3-20 cycloalkyl includes cycloalkyl of the monocyclic or fused ring type, and specific examples thereof include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and the like.

The term C _6-20 aryl includes aryl of the monocyclic or fused ring type, and specific examples thereof include, but are not limited to, phenyl, biphenyl, naphthyl, phenanthrenyl, fluorenyl, and the like.

The term C _5-20 heteroaryl includes heteroaryl of the monocyclic or fused ring type, and specific examples thereof include carbazolyl, pyridyl, quinoline, isoquinoline, thiophenyl, furanyl, imidazole, oxazolyl, thiazolyl, triazine, tetrahydropyranyl, tetrahydrofuranyl, and the like, but are not limited to them.

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

Examples of the Group 4 transition metal include, but are not limited to, titanium, zirconium, hafnium, and the like.

"Two or more adjacent groups bonded to each other to form a substituted or unsubstituted aliphatic or aromatic ring" means that the atom(s) of the two substituents and the atom(s) to which the two substituents are bonded are bonded to each other with the formation of a ring.

The substituents mentioned above may optionally be substituted by a hydroxyl group, a halogen atom, a hydrocarbyl group, a hydrocarbyloxy group, wherein the hydrocarbyl group or hydrocarbyloxy group contains one or more heteroatoms from groups 14-16, -SiH ₃ , hydrocarbyl(oxy)silyl group, phosphine group, phosphide group, sulfonate group and sulfonic group within the range that gives the same or similar effect as the desired effect.

In the supported hybrid catalyst for use in the production of a polyethylene copolymer according to one embodiment of the present invention, the first transition metal compound containing at least one compound selected from the group consisting of chemical formulas 1-3 contributes predominantly to obtain a low molecular weight copolymer having a low content of SCB (side chain branching) and a second transition metal compound containing at least one compound selected from the group consisting of chemical formulas 4-7 can advantageously contribute to the production of a high molecular weight copolymer , which has a high SCB content.

The first transition metal compound represented by the chemical formula 1 mainly contributes to the production of a low molecular weight copolymer having a low SCB content (Side Chain Branching), and its specific examples include compounds represented by the structural formulas shown below, but the present invention is not limited thereto.

In addition, in the chemical formula 1 by introducing the group (CH ₂ ) _n -OR _a (where R _a is a linear or branched C _1-6 -alkyl group and n is an integer from 2 to 10), more specifically tert- butoxyhexyl group, at any of R ₁ -R ₄ substituents and any of R ₅ -R ₈ substituents as a cyclopentadienyl group substituent, the compound shows a low conversion rate during the production of polyolefins using comonomer and can give a low molecular weight polyolefin with a controlled degree of copolymerization or distribution comonomer.

More specifically, the first metallocene compound represented by the chemical formula 1, which exhibits excellent activity, and in particular can also improve the incorporation of 1-octene, 1-butene or 1-hexene comonomer, may be a compound represented by the structural formula shown below.

On the other hand, the first transition metal compound of chemical formula 2 has a structure in which two indene groups are crosslinked by an M ₂ X ₃ X ₄ bridge, where the substituent of any one or more substituents R ₁₁ -R ₁₄ of the indene group is a group -( CH ₂ ) _m -OR _b , and each indene group may be substituted with R ₁₅ and R ₁₆ substituents.

As described above, in the first transition metal compound of chemical formula 2, at least one, more specifically two or more attached groups of the formula -(CH ₂ ) _m -OR _b (wherein R _b represents a linear or branched C _1-6 - an alkyl group and m is an integer from 2 to 10) are introduced into the substituent of an indene or derivative thereof, and therefore it shows a low conversion rate during olefin production using a comonomer compared to another Cp-based catalyst not containing a substituent, and can produce medium and low molecular weight polyolefins with controlled degree of copolymerization or comonomer distribution.

More specifically, any of one or more substituents R ₁₁ -R ₁₄ in the chemical formula 2 has the characteristic -(CH ₂ ) _m -OR _b (wherein R _b represents a linear or branched C _1-6 -alkyl group, and m means an integer from 2 to 10). In the chemical formula 2 group -(CH ₂ ) _m -OR _b specifically may be t-butoxybutyl or t-butoxy-hexyl. More specifically, the two indene groups may each include a -(CH ₂ ) _m -OR _b group, and the -(CH ₂ ) _m -OR _b group may be a t-butoxybutyl group or a t-butoxyhexyl group. When a transition metal compound having such a structure is supported on a substrate, the -(CH ₂ ) _m -OR _b group can form a covalent bond through intimate interaction with the silanol group on the surface of the silica used as the substrate, and hence stable polymerization is possible. on the substrate. In addition, the functional group may affect the comonomer incorporation of alpha-olefin comonomers such as 1-octene, 1-butene, or 1-hexene. In the case of a -(CH ₂ ) _m -OR _b group, where m is a short alkyl chain of 10 or less, more preferably 6 or less, and even more preferably 4 atoms or less, comonomer inclusion relative to alpha-olefin comonomers is reduced, while the overall polymerization activity is retained, which is an advantage for obtaining a polyethylene copolymer having a controlled copolymerization without compromising other physical properties.

The first transition metal compound shown by chemical formula 2 may be, for example, a compound represented by one of the structural formulas shown below, but without limitation.

.

.

In addition, the first transition metal compound represented by the chemical formula 3 has a structure in which an indene group and a cyclopentadiene (Cp) are not crosslinked, which can easily control the electronic/three-dimensional environment around the transition metal. As a result, characteristics such as chemical structure, molecular weight distribution and mechanical properties of the synthesized polyethylene copolymer can be easily controlled. In addition, a substituent group -(CH ₂ ) _p -OR _c (where R _c is a linear or branched C _1-6 alkyl group and p is an integer from 2 to 10) is introduced into any substituent of an indene group or a cyclopentadiene group , and thereby the compound exhibits a low conversion rate during polyolefin production using comonomer compared to other Cp-based catalyst without a substituent, and therefore can produce a low molecular weight polyolefin with controlled degree of copolymerization or comonomer distribution. In addition, when a transition metal compound having such a structure is supported on a substrate, the -(CH ₂ ) _n -OR group among the substituents can form a covalent bond by closely interacting with the silanol group on the surface of the silica used as the substrate, and, therefore, stable polymerization on the substrate is possible.

In the chemical formula 3, M ₃ is a Group 4 transition metal. More specifically, it may be Ti, Zr or Hf, and more preferably Ti or Zr.

In addition, in the chemical formula 3, the R _{20 to} R ₂₉ substituents are generally the same or different from each other, and are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms, provided that at least one of the R ₂₀ -R ₂₉ substituents may be -(CH ₂ ) _p -OR _c (wherein R _c is a linear or branched alkyl group having 1 to 6 carbon atoms and p is an integer from 2 to 10 ). In addition, the functional group -(CH ₂ ) _p -OR _c can affect the comonomer incorporation of alpha-olefin comonomers such as 1-butene or 1-hexene. When p is a short alkyl chain of 4 atoms or less, comonomer inclusion relative to alpha-olefin comonomers is reduced while overall polymerization activity is maintained, and a polyethylene copolymer having controlled copolymerization can be produced without degrading other physical properties. Therefore, in the chemical formula 3, any one or more substituents from R ₂₀ and R ₂₁ or any one or more substituents from R ₂₆ -R ₂₉ cyclopentadiene (Cp) may represent the group -(CH ₂ ) _p -OR _c (wherein R _c is a linear or branched alkyl group having 1 to 6 carbon atoms, and p is an integer from 2 to 10). More specifically, any one or more R ₂₀ and R ₂₁ substituents may represent a -(CH ₂ ) _p -OR _c group (wherein R _c is a linear or branched alkyl group having 1 to 6 carbon atoms and p is an integer number from 2 to 10).

In addition, in the chemical formula 3, X ₅ and X ₆ are the same or different from each other, and each independently represents a halogen atom or an alkyl group having 1 to 20 carbon atoms.

Specific examples of the first transition metal compound represented by the chemical formula 3 include those shown by the structural formulas below, but the present invention is not limited thereto.

On the other hand, in the second transition metal compound represented by the chemical formula 4, the transition metal compound shown by the chemical formula 4 includes an aromatic cyclic compound containing a thiophene as another ligand and a basic compound containing a Group 14 or Group 15 atom, and has a structure in which different ligands are crosslinked with -Y ₁ - and M ₄ (X ₇ )(X ₈ ) lies between the different ligands. A supported catalyst supported with a transition metal compound having a specific structure is applicable to the polymerization reaction of a polyethylene copolymer, and therefore can produce a high molecular weight polyethylene copolymer exhibiting high activity.

More specifically, the C ₁ ligand in the structure of the transition metal compound represented by the chemical formula 4 can affect, for example, the polymerization activity of the olefin and the copolymerization characteristics of the olefin. More specifically, as a C ₁ ligand, the R ₃₀ -R ₃₅ substituents in the chemical formula 4a are the same or different from each other, and each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, the R ₃₀ -R ₃₅ substituents are the same or different from each other, and more specifically include a ligand that is any of alkyl groups having 1 to 10 carbon atoms. In this case, it is possible to obtain a catalyst exhibiting excellent catalytic activity and a high comonomer conversion rate in the polyethylene copolymerization process.

In the structure of the transition metal compound represented by the chemical formula 4, the C ₂ ligand can also affect the polymerization activity of the olefin. In particular, when C ₂ in the chemical formula 4 is —NR ₃₆ — and R ₃₆ is an alkyl group having 1 to 10 carbon atoms, a catalyst having a very high activity in an olefin polymerization process can be obtained.

The C ₁ ligand and the C ₂ ligand can be bridged with -Y ₁ - to exhibit excellent support stability and excellent polymerization activity. In the chemical formula 4, L ₁ is more preferably a linear or branched C ₄ -C ₈ alkylene group, but without limitation. In addition, the alkylene group may be unsubstituted or may be substituted with a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group, or a C ₆ -C ₂₀ aryl group.

In addition, Y ₁ in the chemical formula 4 is preferably silicon, but is not limited to them.

In addition, in the chemical formula 4, A ₁ represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a methoxymethyl group, a t-butoxymethyl group, a 1-ethoxyethyl group, 1 -methyl-1-methoxyethyl group, tetrahydropyranyl group or tetrahydrofuranyl group, but without limitation.

On the other hand, M ₄ (X ₇ )(X ₈ ) is located between the bridged C ₁ ligand and the C ₂ ligand, and the structure of M ₄ (X ₇ )(X ₈ ) may affect the storage stability of the metal complex. To more effectively provide these effects, a transition metal compound in which X ₇ and X ₈ each independently represents any of the halogen atoms can be used.

Specific examples of the second transition metal compound represented by the chemical formula 4 include those shown by the structural formulas below, but the present invention is not limited thereto.

The transition metal compound represented by the chemical formula 4 can be synthesized using known reactions. More detailed synthesis methods are given in the examples described below.

On the other hand, in the second transition metal compound represented by the chemical formula 5, the transition metal compound represented by the chemical formula 5 includes a cyclic compound containing cyclopentadiene as another ligand and a basic compound containing a Group 14 or Group 15 atom, and has the structure , in which different ligands are cross-linked with -Y ₂ - and M ₅ (X ₉ )(X ₁₀ ) is between different ligands. A supported catalyst supported with a transition metal compound having a specific structure is applicable to the polymerization reaction of a polyethylene copolymer, and therefore can produce a high molecular weight polyethylene copolymer exhibiting high activity.

More specifically, the C ₃ ligand in the structure of the transition metal compound represented by formula 5 can influence, for example, the polymerization activity of the olefin and the copolymerization characteristics of the olefin. More specifically, as a C ₃ ligand, the substituents R ₄₀ to R ₄₃ in the chemical formula 5a are the same or different from each other, and each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, substituents R ₄₀ to R ₄₃ are the same or different from each other, and more specifically include a ligand that is any of alkyl groups having 1 to 10 carbon atoms. In this case, it is possible to obtain a catalyst exhibiting excellent catalytic activity and high comonomer conversion in the polyethylene copolymerization process.

In addition, within the structure of the transition metal compound represented by the chemical formula 5, the C ₄ ligand can also affect the polymerization activity of the olefin. In particular, when C ₄ in the chemical formula 5 is —NR ₄₄ — and R ₄₄ is an alkyl group having 1 to 10 carbon atoms, a catalyst exhibiting very high activity in an olefin polymerization process can be obtained.

The C ₃ ligand and the C ₄ ligand can be bridged with -Y ₂ - to obtain excellent application stability and excellent polymerization activity. In the chemical formula 5, L ₂ is preferably a linear or branched C ₄ -C ₈ alkylene group, but is not limited thereto. In addition, the alkylene group may be unsubstituted or may be substituted with a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group, or a C ₆ -C ₂₀ aryl group.

In addition, in the chemical formula 5, Y ₂ is preferably silicon, but is not limited thereto.

In addition, in the chemical formula 5, A ₂ is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a methoxymethyl group, a t-butoxymethyl group, an ethoxyethyl group, a 1- methyl-1-methoxyethyl group, tetrahydropyranyl group or tetrahydrofuranyl group, but without limitation.

On the other hand, M ₅ (X ₉ )(X ₁₀ ) is located between the bridged C ₃ ligand and the C ₄ ligand, and the structure of M ₅ (X ₉ )(X ₁₀ ) may affect the storage stability of the metal complex. To more effectively provide such effects, a transition metal compound in which X ₉ and X ₁₀ each independently represents any of the halogen atoms can be used.

Specific examples of the second transition metal compound represented by the chemical formula 5 include the compound shown by the structural formula below, but the present invention is not limited thereto.

The transition metal compound represented by the chemical formula 5 can be synthesized using known reactions. A more detailed synthesis method is discussed in the examples described below.

On the other hand, in the chemical formula 6, the substituents R ₅₀ -R ₅₈ and R ₆₀ -R ₆₈ of the chemical formulas 6a and 6b, more preferably represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a phenyl group, a halogen atom, a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a triisopropylsilyl group, a trimethylsilylmethyl group, a methoxy group, or an ethoxy group, but are not limited to them.

More preferably, when L ₃ in the chemical formula 6 represents a linear or branched C ₄ -C ₈ -alkylene group, but without limitation. In addition, the alkylene group may be unsubstituted or may be substituted with a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group, or a C ₆ -C ₂₀ aryl group.

In addition, A ₃ in the chemical formula 6 is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a methoxymethyl group, a t-butoxymethyl group, a 1-ethoxyethyl group, 1-methyl-1-methoxyethyl group, tetrahydropyranyl group or tetrahydrofuranyl group, but without limitation.

In addition, Y ₃ in the chemical formula 6 is preferably silicon, but without limitation.

The second transition metal compound of chemical formula 6 forms a structure in which the indenoindole derivative and/or the fluorene derivative are bridged and has a lone pair of electrons that can act as a Lewis base in the ligand structure. Thus, when applied to the surface of a substrate having the characteristics of a Lewis acid, it exhibits high polymerization activity even when applied. In addition, the second transition metal compound has a high activity since it contains an electron-enriched indenoindole group and/or a fluorene group. Due to suitable steric hindrance and the electronic effect of the ligand, not only is the reactivity towards hydrogen low, but also high activity is maintained even in the presence of hydrogen. In addition, since the beta hydrogen of the growing polymer chain is stabilized by the nitrogen atom of the indoloindole derivative through hydrogen bonding, inhibiting beta hydrogen abstraction, an ultra-high molecular weight polyethylene copolymer is obtained by polymerization.

According to an embodiment of the present invention, specific examples of the compound represented by the chemical formula 6a include compounds represented by one of the structural formulas shown below, but the present invention is not limited thereto.

According to one embodiment of the present invention, specific examples of the compound represented by the chemical formula 6b include compounds represented by one of the structural formulas shown below, but the present invention is not limited thereto.

According to one embodiment of the present invention, specific examples of the second transition metal compound represented by chemical formula 6 include, but are not limited to, compounds represented by one of the structural formulas shown below.

.

.

The second transition metal compound of the chemical formula 6 exhibits excellent activity and can give a high molecular weight polyethylene copolymer upon polymerization. In particular, even when used by applying to a substrate, it exhibits high polymerization activity and can produce a polyethylene copolymer having an ultra-high molecular weight.

In addition, even when a polymerization reaction involving hydrogen is carried out to obtain a polyethylene copolymer having a high molecular weight and a wide molecular weight distribution, the second transition metal compound of the chemical formula 6 according to the present invention shows a low interaction with hydrogen and still gives at polymerization ultra-high molecular weight polyethylene copolymer with high activity. Therefore, even when used in combination with a catalyst having different properties, it is possible to produce a polyethylene copolymer satisfying high molecular weight characteristics without lowering activity, and thus it is possible to easily produce a polyethylene copolymer having a wide molecular weight distribution when the polyethylene copolymer is included. polymer.

The second transition metal compound of chemical formula 6 can be prepared by bridging an indoloindole derivative and/or a fluorene derivative to form a ligand compound and adding a metal precursor compound thereto to effect metalation. The method for preparing the second transition metal compound is described in detail in the following examples.

On the other hand, the second transition metal compound of chemical formula 7 is a structure in which two indene groups are cross-linked through a bridge SiQ ₁ Q ₂ and any one or more substituents R ₇₁ -R ₇₄ in the indene group are -(CH ₂ ) _q -OR _d (where R _d is a straight or branched C _1-6 alkyl group and q is an integer from 2 to 10) and each indene group may be substituted with R ₇₅ and R ₇₆ substituents.

Thus, in the second transition metal compound of chemical formula 7, at least one, especially two or more, attached groups of the formula -(CH ₂ ) _q -OR _d (wherein R _d is a linear or branched C _1-6 -alkyl group , and q is an integer from 2 to 10) are introduced into the substituent of the indene or its derivative and two indene groups are linked through the bridge SiQ ₁ Q ₂ . As a result, a high molecular weight polyolefin can be produced.

More specifically, any one or more of the substituents R ₇₁ -R ₇₄ in chemical formula 7 has the structure -(CH ₂ ) _q -OR _d (wherein R _d is a linear or branched C _1-6 alkyl group and q is an integer from 2 to 10). In chemical formula 7, the -(CH ₂ ) _q -OR _d group may more specifically be t-butoxybutyl or t-butoxyhexyl. More specifically, each of the two indene groups may include a -(CH ₂ ) _q -OR _d group, and the -(CH ₂ ) _q -OR _d group may be a t-butoxybutyl group or a t-butoxyhexyl group. When a transition metal compound having such a structure is supported on a substrate, the -(CH ₂ ) _q -OR _d group can form a covalent bond through intimate interaction with the silanol group on the surface of the silica used as the substrate, and hence stable polymerization is possible. on the substrate. In addition, the functional group may affect the comonomer incorporation of alpha-olefin comonomers such as 1-octene, 1-butene, or 1-hexene. In the case of a -(CH ₂ ) _q -OR _d group, where q is a short alkyl chain of 10 or less, more preferably 6 or less, even more preferably 4 atoms or less, comonomer inclusion relative to alpha-olefin comonomers is reduced while maintaining the overall polymerization activity, which is an advantage in the case of obtaining a polyethylene copolymer having a controlled copolymerization without compromising other physical properties.

The second transition metal compound represented by the chemical formula 7 may be, for example, the compound shown by one of the structural formulas below, but is not limited thereto.

The supported hybrid catalyst used in the present invention may be a catalyst in which a transition metal mixture comprising a first mixture comprising a first transition metal compound containing at least one compound selected from the group consisting of chemical formulas 2 and 3 and a second transition metal compound containing at least one compound selected from the group consisting of chemical formulas 4-7, or a second mixture comprising a first transition metal compound containing chemical formula 1 and a second transition metal compound containing , at least one compound selected from the group consisting of chemical formulas 4, 6 and 7, is applied to the substrate together with the co-catalyst compound. The transition metal mixture may include any mixture of the first mixture comprising a first transition metal compound containing at least one compound selected from the group consisting of chemical formulas 2 and 3 and a second transition metal compound containing at least one compound selected from the group consisting of chemical formulas 4-7, or a second mixture comprising a first transition metal compound containing chemical formula 1, and a second transition metal compound containing at least one compound selected from the group including chemical formulas 4, 6 and 7.

That is, as the first transition metal compound in the first mixture, one type of chemical formula 2, one type of chemical formula 3, or two types of chemical formula 2 and chemical formula 3 can be used. In addition, as the second transition metal compound in the first mixture, one type of chemical formula 4, one type of chemical formula 5, one type of chemical formula 6, one type of chemical formula 7, two types of chemical formula 4 and chemical formula 5, two types of chemical formula 4 and chemical formula 6, two types of chemical formula 4 and chemical formula 7, two types of chemical formula 5 and chemical formula 6, two types of chemical formula 5 and chemical formula 7, two types of chemical formula 6 and chemical formula 7, three types of chemical formula 4, chemical formula 5 and chemical formula 6, three types of chemical formula 4, chemical formula 5 and chemical formula 7, three types of chemical formula 4, chemical formula 6 and chemical formula 7, three types of chemical formula 5, chemical formula 6 and chemical formula 7, or four types of chemical formula 4, chemical formula 5, chemical formula 6 and chemical formula 7.

On the other hand, as the first transition metal compound in the second mixture, one type of chemical formula 1 can be used. In addition, as the second transition metal compound in the second mixture, one type of chemical formula 4, one type of chemical formula 6, one type of chemical formula 7, two types of chemical formula 4 and chemical formula 6, two types of chemical formula 4 and chemical formula 7, two types of chemical formula 6 and chemical formula 7, and three types of chemical formula 4, chemical formula 6 and chemical formula 7.

Preferably, one type of chemical formula 1 can be used as the first transition metal compound, and one type of chemical formula 4 can be used as the second transition metal compound. In addition, one type of chemical formula 2 can be used as the first transition metal compound, and as the second transition metal compound, one type of chemical formula 5 can be used. In addition, one type of chemical formula 3 can be used as the first transition metal compound, and one type of chemical formula 5 can be used as the second transition metal compound. In addition, as the first transition metal compound, one type of chemical formula 1 can be used, and as the second transition metal compound, two types of chemical formula 6 and chemical formula 7 can be used.

In the mixture of transition metals, the first compound of the transition metal may be present in an amount of from 1 to 80 wt. hours or from 5 to 50 wt. hours based on 100 wt. hours of the second compound of the transition metal. Due to its presence in the above ratio, a polyethylene copolymer having excellent processability and durability can be easily produced.

When the second transition metal compound includes two types of chemical formula 6 and chemical formula 7, the compound of chemical formula 7 may be present in an amount of 10 to 80 wt. hours or from 40 to 60 mass. hours based on 100 wt. including compounds of chemical formula 6.

In the supported hybrid catalyst according to the present invention, a support having a hydroxy group on its surface, and preferably a support including a highly reactive hydroxyl group and a siloxane group, the surface of which is dried to remove moisture, can be used as the support.

For example, silicon dioxide, aluminosilicate, magnesium silicate, and the like, which are dried at a high temperature, may be used, and generally they may contain oxide, carbonate, sulfate, or nitrate such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , Mg(NO ₃ ) ₂ or the like.

The drying temperature of the substrate is preferably 200 to 800°C, more preferably 300 to 600°C and most preferably 300 to 400°C. If the drying temperature is less than 200°C, too much moisture on its surface can lead to interaction with cocatalyst. If the drying temperature is more than 800°C, the pores on the surface of the substrate coalesce with each other to reduce the surface area, hydroxyl groups are lost and only siloxane groups remain on the surface. Thus, the number of reactive sites for the co-catalyst is reduced, which is not preferred.

The amount of hydroxyl groups on the surface of the support is preferably 0.1 to 10 mmol/g and more preferably 0.5 to 5 mmol/g. The amount of hydroxyl groups on the surface of the substrate can be adjusted depending on the production method of the substrate, as well as production conditions or drying conditions such as temperature, time, vacuum and spray drying.

If the number of hydroxyl groups is less than 0.1 mmol/g, the number of reactive sites for the cocatalyst is reduced. If the amount of hydroxyl groups is greater than 10 mmol/g, then the hydroxyl groups may come from moisture in addition to the hydroxyl groups present on the surface of the support particle, which is not desirable.

The supported hybrid catalyst can induce the production of LCBs (Long Chain Branches) in the polyethylene copolymer being produced, more specifically the ethylene/1-hexene or ethylene/1-butene copolymer.

Further, in the supported hybrid catalyst of the present invention, the cocatalyst supported on the support to activate the transition metal compound is an organometallic compound containing a Group 13 metal, and it is not particularly limited as long as it can be used in the polymerization of an olefin by conventional metallocene catalyst.

More specifically, the cocatalyst compound may include one or more of an aluminum-containing primary cocatalyst of the following chemical formula 8 and a boron-containing secondary cocatalyst of the following chemical formula 9.

[Chemical formula 8]

-[Al(R ₇₇ )-O-] _k -

In the chemical formula 8, each R ₇₇ substituent is independently selected from the group consisting of a halogen atom and a halogen-substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, and k is an integer of 2 or more.

[Chemical formula 9]

T ⁺ [BG ₄ ] ^-

In the chemical formula 9, T ⁺ is a polyatomic ion with a +1 valence, B is a boron atom with an oxidation state of +3, and each G is independently selected from the group consisting of a hydride, a dialkylamido group, a halide, an alkoxide, an aryl oxide, a hydrocarbyl, a halocarbyl, and hydrocarbyl substituted with halogen, where G has 20 or fewer carbon atoms, provided that G is a halide in one position or none.

By using the first and second co-catalysts, the polydispersity index of the final polyolefin becomes more uniform and the polymerization activity can be increased.

The first cocatalyst of chemical formula 8 may be an alkylaluminoxane compound in which the repeating units are combined in a linear, circular, or network form. Specific examples of the first co-catalyst include methylaluminoxane (MAO), ethylaluminoxane, isobutyl-aluminoxane, butylaluminoxane, and the like.

In addition, the second cocatalyst of the chemical formula 9 may be a trisubstituted ammonium salt, a dialkyl ammonium salt, or a trisubstituted phosphonium salt of the borate type. Specific examples of the second cocatalyst include a borate-based compound in the form of a trisubstituted ammonium salt, such as trimethylammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripypropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, methyltetradecyloctadecylammonium tetraphenylborate, N,N- tetraphenylborate. dimethylanilinium, N tetraphenylborate, N-diethylanilinium tetraphenylborate N,N-dimethyl-(2,4,6-trimethylanilinium), trimethylammonium tetrakis(pentafluorophenyl)borate, methylditradecyl ammonium tetrakis(pentaphenyl)borate, methyldioctadecylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate, tetrakis(pentafluorophenyl)borate N, N -dimethylanilinium, tetrakis(pentafluorophenyl)borate N, N-diethylanilinium, tetrakis(pentafluorophenyl)borate N, N-dimethyl(2,4,6-trimeth ylaninium), tetrakis(2,3,4,6-tetrafluorophenyl)trimethylammonium borate, tetrakis(2,3,4,6-tetrafluorophenyl)triethylammonium borate, tetrakis(2,3,4,6-tetrafluorophenyl)tripropylammonium borate, tetrakis(2,3,4,6-tetrafluorophenyl)tri(n-butyl)ammonium borate, tetrakis(2,3,4,6-tetrafluorophenyl)dimethyl(tert-butyl)-ammonium borate, tetrakis(2,3,4 ,6-tetrafluorophenyl) borate N, N-dimethyl-anilinium, tetrakis(2,3,4,6-tetrafluorophenyl) borate N, N-diethyl-anilinium or tetrakis-(2,3,4,6-tetrafluorophenyl) borate N , N-dimethyl-(2,4,6-trimethylanilinium) and the like; a borate-based compound in the form of a dialkylammonium salt such as dioctadecylammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetrakis(pentafluorophenyl)borate or dicyclohexylammonium tetrakis(pentafluorophenyl)borate; or a borate-based compound in the form of a trisubstituted phosphonium salt, such as triphenylphosphonium tetrakis(pentafluorophenyl)borate, methyldioctadecylphosphonium tetrakis(pentafluorophenyl)borate, or tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate.

Such a supported hybrid catalyst can be prepared, for example, by a method comprising the steps of supporting the cocatalyst on the support and then supporting the first and second transition metal compounds on the supported cocatalyst. Meanwhile, the order in which the transition metal compounds are deposited is not particularly limited, but the first transition metal compound having a small molecule structure and the second transition metal compound can be deposited in that order.

In addition, in the step of applying the cocatalyst to the support, the cocatalyst supported support can be obtained by adding the cocatalyst to the support dried at high temperature and stirring it at a temperature of about 20 to 120°C.

In addition, in the step of supporting the catalyst precursor on the cocatalyst supported support, the supported catalyst can be obtained by adding a transition metal compound to the cocatalyst supported support obtained in the cocatalyst supporting step and then stirring it at a temperature of about 20 to 120° C. obtaining a catalyst on a substrate.

In the step of applying the catalyst precursor to the cocatalyst supported support, the supported catalyst can be prepared by adding the transition metal compound to the cocatalyst supported support, stirring the mixture, and also adding the cocatalyst.

The content of the support, cocatalyst, supported cocatalyst, and transition metal compound used in the supported hybrid catalyst according to one embodiment of the invention can be appropriately adjusted depending on the physical properties or effects of the supported catalyst desired.

In the supported hybrid catalyst according to one embodiment of the present invention, the weight ratio between the transition metal mixture comprising the first and second transition metal compounds and the support may be from 1:10 to 1:1000, and more particularly from 1:10 to 1: 500. When the substrate and the transition metal mixture are combined in a weight ratio within the range described above, an optimum shape can be developed.

In addition, when the supported hybrid catalyst also includes a cocatalyst, the weight ratio of cocatalyst to support may be from 1:1 to 1:100, and more specifically from 1:1 to 1:50. When the cocatalyst and support are combined in the above weight ratio, the activity and microstructure of the polymer can be optimized.

Hydrocarbon solvents such as pentane, hexane, heptane, etc., or aromatic solvents such as benzene, toluene, and the like can be used as the reaction solvent in the preparation of the supported hybrid catalyst.

With regard to more specific methods for obtaining a supported catalyst, they are presented in the examples described below. However, the production method of the supported catalyst is not limited to the context described here, and in the aforementioned production method, the step that is generally chosen in the technical field to which the invention pertains can also be selected. The production process steps can be modified with modifiable steps.

On the other hand, the polyethylene copolymer according to the present invention can be produced by polymerizing ethylene monomers and alpha-olefin monomers in the presence of the supported hybrid catalyst described above.

Various polymerization processes, known as olefin monomer polymerization reactions, such as a continuous solution polymerization method, a bulk polymerization method, a suspension polymerization method, a paste polymerization method, or an emulsion polymerization method, can be used to polymerize the monomer.

The polymerization temperature may be 25 to 500°C, preferably 25 to 200°C, and more preferably 50 to 150°C. In addition, the polymerization pressure may be 1 to 100 bar, preferably 1 to 50 bar, and more preferably 5 to 30 bar.

Since the first and second transition metal compounds in the present invention have excellent hydrogen reactivity, a polyethylene copolymer having a desired molecular weight and melt index can be effectively produced by controlling the amount of hydrogen gas used in the polymerization step.

More specifically, at the stage of polymerization of ethylene monomer and alpha-olefin monomer, hydrogen gas can be added in an amount of from 0.005 to 0.040 wt. -%, from 0.008 to 0.035 wt. or from 0.005 to 0.020% of the mass. relative to ethylene monomer.

More specifically, when a transition metal compound of chemical formula 1 is used as the first transition metal compound and a transition metal compound of chemical formula 4 is used as the second transition metal compound, hydrogen gas may be added in the polymerization step of the ethylene monomer and the alpha-olefin monomer in the amount of from 0.005 to 0.013% of the mass. relative to ethylene monomer.

In addition, when the transition metal compound of the chemical formula 2 is used as the first transition metal compound and the transition metal compound of the chemical formula 5 is used as the second transition metal compound, hydrogen gas may be added in the polymerization step of the ethylene monomer and the alpha-olefin monomer in the amount from 0.033 to 0.040% of the mass. relative to ethylene monomer.

The above supported metallocene catalyst can be injected after being dissolved or diluted in an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms such as pentane, hexane, heptane, nonane, decane and their isomers, an aromatic hydrocarbon solvent such as toluene and benzene, or a chlorosubstituted hydrocarbon solvent such as dichloromethane and chlorobenzene. The solvent is preferably used after a small amount of water, air or the like acting as a catalyst poison has been removed by treatment with a small amount of aluminum alkyl. An additional cocatalyst may also be used.

According to another embodiment of the present invention, there is provided a molded article produced using the above polyethylene copolymer, preferably a pipe such as a high internal pressure heating pipe, a shaft pipe or a large diameter pipe.

Positive Effects

According to the present invention, a polyethylene copolymer can be obtained which is excellent in processability and durability, and is therefore useful for forming a hollow pipe or the like.

Brief description of the drawings

FIG 1 is a view showing the molecular weight distribution curve (solid line) and the SCB distribution curve (dashed line) of the polyethylene copolymer of Example 1.

FIG 2 is a view showing a method for measuring the comonomer distribution index (CDI) of the polyethylene copolymer of Example 1.

Detailed description of embodiments

The present invention is described in more detail using the examples below. However, these examples are provided only to illustrate the invention and are not intended to limit the scope of the invention.

PREPARATORY EXAMPLES

Preparation Examples of the First Transition Metal Compound

Preparatory examples 1-3

Preparatory example 1

tert-Butyl-O-(CH ₂ ) ₆ -Cl is prepared using 6-chloro-hexanol according to the method proposed in the literature (Tetrahedron Lett. 2951 (1988)), and reacted with NaCp to give tert-butyl -O-(CH ₂ ) ₆ -C ₅ H ₅ (yield 60%, bp 80/0.1 mm Hg).

After that, tert-butyl-O(CH ₂ ) ₆ -C ₅ H ₅ was dissolved in THF (THF) at -78°C, n-butyllithium (n-BuLi) was slowly added to the solution, the reaction temperature was raised to room temperature, and then give the opportunity to respond 8 hours. The solution is again introduced into the reaction, in which a solution of the already synthesized lithium salt is slowly added to a suspension solution of ZrCl ₄ (THF) ₂ (1.70 g, 4.50 mmol)/THF (30 ml) at -78°C and then injected reaction at room temperature for 6 hours.

All volatiles are removed by drying in vacuo, hexane is added as a solvent, an oily liquid is obtained and the mixture is filtered. The filtered solution is vacuum dried and hexane is added to it to cause precipitation at low temperature (-20°C). The precipitate obtained is filtered off at low temperature to give [tert-Bu-O-(CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ in the form of a white solid (92% yield).

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

¹³ C NMR spectrum (CDCl ₃ ): 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.61, 30.14, 29.18, 27.58, 26 .00

Preparatory Example 2

(1) Obtaining a ligand compound

Add 10.8 g (100 mmol) of chlorhexanol to a dry 250 ml Schlenk flask to which 10 g of molecular sieve and 100 ml of MTBE (methyl tert-butyl ether) are added and 20 g of sulfuric acid are added slowly over 30 minutes. The reaction mixture slowly turns pink over time. After 16 hours, it is poured into a saturated sodium bicarbonate solution under ice-cooling. The mixture is extracted four times with 100 ml of ether, the combined organic layer is dried over MgSO ₄ and filtered. The solvent is removed under reduced pressure. This gives 10 g (60% yield) of 1-(tert-butoxy)-6-chlorohexane as a yellow liquid.

¹ H NMR spectrum (500 MHz, CDCl ₃ ): 3.53 (2H, t), 3.33 (2H, t), 1.79 (2H, m), 1.54 (2H, m), 1, 45 (2H, m), 1.38 (2H, m), 1.21 (9H, s).

Add 4.5 g (25 mmol) of 1-(tert-butoxy)-6-chlorohexane synthesized above to a dry 250 ml Schlenk flask and dissolve in 40 ml of THF. 20 ml of a solution of sodium indenide in THF was slowly added to the flask and then stirred for one day. The reaction mixture was quenched by adding 50 ml of water and extracted with ether (50 ml x 3), then the combined organic layer was thoroughly washed with brine. The remaining moisture is removed by drying over MgSO ₄ and the mixture is filtered. The solvent is removed under reduced pressure. As a result, a dark brown viscous product, 3-(6-tert-butoxy-hexyl)-1H-indene, is obtained in quantitative yield.

Mw=272.21 g/mol.

¹ H NMR spectrum (500 MHz, CDCl ₃ ): 7.47 (1H, d), 7.38 (1H, d), 7.31 (1H, t), 7.21 (1H, t), 6, 21 (1H, s), 3.36 (2H, m), 2.57 (2H, m), 1.73 (2H, m), 1.57 (2H, m), 1.44 (6H, m ), 1.21 (9H, s).

(2) Obtaining a transition metal compound

3-(6-tert-butoxyhexyl)-1H-indene was dissolved in THF at -78°C, n-butyllithium (n-BuLi) was added slowly, the reaction temperature was raised to room temperature and then allowed to react for 8 hours. The solution is again introduced into the reaction, in which a solution of the already synthesized lithium salt is slowly added to a suspension solution of ZrCl ₄ (THF) ₂ (1.70 g, 4.50 mmol)/THF (30 ml) at -78°C, and then additionally reacted at room temperature for 6 hours.

All volatiles are removed by drying in vacuo, hexane is added as a solvent to the resulting oily liquid and the mixture is filtered. The filtered solution is dried in vacuo and hexane is added to it to cause precipitation at low temperature (-20°C). The resulting precipitate was filtered off at low temperature to give [3-(6-tert-butoxyhexyl)-1H-indene] ₂ ZrCl ₂ as a white solid (yield 78%).

¹ H NMR spectrum (300 MHz, CDCl ₃ ): 7.47 (2H, d), 7.38 (2H, d), 7.21 (2H, t), 6.95 (2H, m), 6, 10(1H, s), 5.87(1H, s), 5.48(1H, s), 5.36(1H, s) 3.36(4H, m), 2.95(2H, m) , 2.76(2H, m), 1.47(8H, m), 1.30(4H, m), 1.05(18H, s).

Preparatory example 3

(1) Obtaining a ligand compound

Add 10.8 g (100 mmol) of chlorhexanol to a dry 250 ml Schlenk flask to which 10 g of molecular sieve and 100 ml of MTBE (methyl tert-butyl ether) are added and 20 g of sulfuric acid are added slowly over 30 minutes. The reaction mixture slowly turns pink over time. After 16 hours, it is poured into a saturated sodium bicarbonate solution under ice-cooling. The mixture is extracted four times with 100 ml of ether and the combined organic layer is dried over MgSO ₄ and filtered. The solvent is removed under reduced pressure. This gives 10 g (60% yield) of 1-(tert-butoxy)-6-chlorohexane as a yellow liquid.

¹ H NMR spectrum (500 MHz, CDCl ₃ ): 3.53 (2H, t), 3.33 (2H, t), 1.79 (2H, m), 1.54 (2H, m), 1, 45 (2H, m), 1.38 (2H, m), 1.21 (9H, s).

Add 4.5 g (25 mmol) of 1-(tert-butoxy)-6-chlorohexane synthesized above to a dry 250 ml Schlenk flask and dissolve in 40 ml of THF. 20 ml of a solution of sodium indenide in THF was slowly added to the flask and then stirred for one day. The reaction mixture was quenched by adding 50 ml of water and extracted with ether (50 ml x 3), then the combined organic layer was thoroughly washed with brine. The remaining moisture is removed by drying over MgSO ₄ and the mixture is filtered. The solvent is removed under reduced pressure. As a result, a dark brown viscous product, 3-(6-tert-butoxy-hexyl)-1H-indene, is obtained in quantitative yield.

Mw=272.21 g/mol.

¹ H NMR spectrum (500 MHz, CDCl ₃ ): 7.47 (1H, d), 7.38 (1H, d), 7.31 (1H, t), 7.21 (1H, t), 6, 21 (1H, s), 3.36 (2H, m), 2.57 (2H, m), 1.73 (2H, m), 1.57 (2H, m), 1.44 (6H, m ), 1.21 (9H, s).

(2) Preparation of transition metal compounds

Add 5.44 g (20 mmol) of 3-(6-tert-butoxyhexyl)-1H-indene obtained above to a dry 250 ml Schlenk flask and dissolve in 60 ml of ether. 13 ml of a 2.0 M solution of n-BuLi in hexane was added to the flask, stirred for one day and then a solution of n-butylcyclopentadiene-ZrCl ₃ in toluene (concentration 0.378 mmol/g) was slowly added at -78°C. When the reaction mixture is heated to room temperature, it turns into a white suspension with a yellow solid floating in a clear brown solution. After 12 hours, 100 ml of hexane was added to the reaction mixture for further precipitation. The mixture is then filtered under argon to give a yellow filtrate which is dried. As a result, it was confirmed that 3-(6-(tert-butoxyhexyl)-1H-inden-1-yl)(3-butylcyclopenta-2,4-dien-1-yl)zirconium(IV) chloride was obtained as the target compound.

Mw=554.75 g/mol.

¹ H NMR spectrum (500 MHz, CDCl ₃ ): 7.62 (2H, m), 7.24 (2H, m), 6.65 (1H, s), 6.39 (1H, s), 6, 02 (1H, s), 5.83 (1H, s), 5.75 (1H, s), 3.29 (2H, m), 2.99 (1H, m), 2.89 (1H, m ), 2.53(1H, m), 1.68(2H, m), 1.39-1.64(10H, m), 1.14(9H, s), 0.93(4H, m) .

Preparation Example of the Second Transition Metal Compound

Preparatory Examples 4-7

Preparatory example 4

(1) Obtaining ligand A

4.0 g (30 mmol) of 1-benzothiophene are dissolved in THF to give a solution of 1-benzothiophene. Then 14 ml (36 mmol, 2.5 M in hexane) of n-BuLi solution and 1.3 g (15 mmol) of CuCN are added to the 1-benzothiophene solution.

Then, 3.6 g (30 mmol) of tigloyl chloride was slowly added to the solution at -80°C, and the resulting solution was stirred at room temperature for about 10 hours.

Then, a 10% HCl solution was poured into the solution to quench the reaction, and the organic layer was separated with dichloromethane to give (2E)-1-(1-benzothien-2-yl)-2-methyl-2-buten-1-one in as a beige solid.

¹ H NMR spectrum (CDCl ₃ ): 7.85-7.82 (m, 2H), 7.75 (m, 1H), 7.44-7.34 (m, 2H), 6.68 (m, 1H), 1.99 (m, 3H), 1.92 (m, 3H).

With vigorous stirring to a solution in which 5.0 g (22 mmol) of (2E)-1-(1-benzothien-2-yl)-2-methyl-2-buten-1-one was dissolved in 5 ml of chlorobenzene, obtained above, slowly add 34 ml of sulfuric acid. The solution is then stirred at room temperature for approximately 1 hour. Then, ice water was poured into the solution and the organic layer was separated with ether to give 4.5 g (91% yield) of 1,2-dimethyl-l,2-dihydro-3H-benzo[b]-cyclopenta[d]thiophene-3 -it is in the form of a yellow solid.

¹ H NMR spectrum (CDCl ₃ ): 7.95-7.91 (m, 2H), 7.51-7.45 (m, 2H), 3.20 (m, 1H), 2.63 (m, 1H), 1.59 (d, 3H), 1.39 (d, 3H).

To a solution in which 2.0 g (9.2 mmol) of 1,2-dimethyl-l,2-dihydro-3H-benzo[b]cyclopenta[d]thiophen-3-one is dissolved in a mixed solvent of 20 ml of THF and 10 ml of methanol, 570 mg (15 mmol) of NaBH ₄ are added at 0°C. The solution is then stirred at room temperature for approximately 2 hours. Thereafter, HCl solution was added to bring the pH to 1, the organic layer was separated with ether to give the alcohol intermediate.

The alcohol intermediate is dissolved in toluene to give a solution. 190 mg (1.0 mmol) of p-toluenesulfonic acid are then added to the solution and refluxed for approximately 10 minutes. The resulting reaction mixture was separated by column chromatography to give 1.8 g (9.0 mmol, 98% yield) of 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene (Ligand A) as an orange brownish liquid.

¹ H NMR spectrum (CDCl ₃ ): 7.81 (d, 1H), 7.70 (d, 1H), 7.33 (t, 1H), 7.19 (t, 1H), 6.46 (s , 1H), 3.35 (q, 1H), 2.14 (s, 3H), 1.14 (d, 3H).

(2) Obtaining ligand B

Add 13 ml (120 mmol) of tert-butylamine and 20 ml of ether as solvent to a 250 ml Schlenk flask and add 16 g (60 mmol) of (6-tert-butoxyhexyl)dichloro(methyl) to another 250 ml Schlenk flask silane and 40 ml of ether, get a solution of tert-butylamine and a solution of (6-tert-butoxyhexyl)dichloro-(methyl)silane, respectively. The tert-butylamine solution is then cooled to -78° C. and the (6-tert-butoxyhexyl)dichloro(methyl)silane solution is added slowly to the cooled solution, which is stirred at room temperature for about 2 hours. The resulting white suspension is filtered to give 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-chloro-1-methylsilanamine (Ligand B) as a creamy liquid.

¹ H NMR spectrum (CDCl ₃ ): 3.29 (t, 2H), 1.52-1.29 (m, 10H), 1.20 (s, 9H), 1.16 (s, 9H), 0 .40 (s, 3H).

(3) Crosslinking of ligands A and B

Add 1.7 g (8.6 mmol) of 1,2-dimethyl-3H-benzo[b]cyclopenta[d]thiophene (ligand A) and 30 ml of THF to a 250 ml Schlenk flask to obtain a solution of ligand A. A solution of ligand A was cooled to -78°C, then 3.6 ml (9.1 mmol, 2.5 M in hexane) of n-BuLi solution was added to the solution of ligand A and stirred at room temperature overnight, a violet-brown solution was obtained. The solvent of the violet-brown solution was replaced with toluene, and a solution dispersed with 39 mg (0.43 mmol) of CuCN in 2 ml of THF was injected into this solution to obtain solution A.

At the same time, 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-chloro-1-methylsilanamine (ligand B) and toluene are injected into a 250 ml Schlenk flask, solution B is obtained, which is then cooled to -78°C. Then solution A, prepared earlier, is slowly added to the cooled solution B, and the mixture of solutions A and B is stirred at room temperature overnight. The resulting solid is filtered off to give 4.2 g of 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-(1,2-dimethyl-3H-benzo[b ]cyclopenta[d]thiophen-3-yl)-1-methylsilanamine (crosslinked product of ligands A and B) (>99% yield).

To confirm the structure of the crosslinked product of ligands A and B, the crosslinked product was lithiated at room temperature and then an H-NMR spectrum was recorded using a sample dissolved in small amounts of pyridine-D ₅ and CDCl ₃ .

¹ H NMR spectrum (pyridine-D ₅ and CDCl ₃ ): 7.81 (d, 1H), 7.67 (d, 1H), 7.82-7.08 (m, 2H), 3.59 (t , 2H), 3.15 (s, 6H), 2.23-1.73 (m, 10H), 2.15 (s, 9H), 1.91 (s, 9H), 1.68 (s, 3H).

(4) Preparation of transition metal compounds

Add 4.2 g (8.6 mmol) of 1-(6-(tert-butoxy)hexyl)-N-(tert-butyl)-1-(1,2-dimethyl-3H-benzo[b]cyclopenta[d ]thiophen-3-yl)-1-methylsilanamine (crosslinked product of ligands A and B) into a 250 ml Schlenk flask and 14 ml of toluene and 1.7 ml of n-hexane are injected into the flask to dissolve the crosslinked product. After cooling the solution to -78°C, 7.3 ml (18 mmol, 2.5 M in hexane) of n-BuLi solution is injected into the cooled solution. The solution is then stirred at room temperature for approximately 12 hours. Then, 5.3 ml (38 mmol) of trimethylamine is added to the solution, and this solution is stirred at about 40°C for about 3 hours, solution C is obtained.

At the same time, 2.3 g (8.6 mmol) TiCl ₄ (THF) ₂ and 10 ml of toluene are added to a separately prepared 250 ml Schlenk flask to obtain solution D, where TiCl ₄ (THF) ₂ is dispersed in toluene. The pre-prepared solution C was added slowly at -78°C to the above solution D, and the mixture of solutions C and D was stirred at room temperature for 12 hours. Thereafter, the solution is subjected to reduced pressure to remove the solvent, and the resulting solutes are dissolved in toluene. Solids that do not dissolve in toluene are filtered off. The solvent was removed from the filtered solution to give 4.2 g (83% yield) of the transition metal compound as a brown solid.

¹ H NMR spectrum (CDCl ₃ ): 8.01 (d, 1H), 7.73 (d, 1H), 7.45-7.40 (m, 2H), 3.33 (t, 2H), 2 .71 (s, 3H), 2.33 (d, 3H), 1.38 (s, 9H), 1.18 (s, 9H), 1.80-0.79 (m, 10H), 0. 79 (d, 3H).

Preparatory example 5

50 g of Mg(s) are added to a 10 L reactor at room temperature, followed by 300 ml of THF. Add approximately 0.5 g of I ₂ and then maintain the temperature of the reactor at 50°C. After the reactor temperature has stabilized, 250 g of 6-tert-butoxyhexyl chloride is added to the reactor at a rate of 5 ml/min using a feed pump. Observe that as soon as add 6-tert-butoxyhexylchloride, the temperature in the reactor rises by about 4-5°C. With continuous addition of 6-tert-butoxyhexyl chloride, the solution was stirred for 12 hours. After reacting for 12 hours, a black reaction solution was obtained. 2 ml of the resulting black solution is taken, water is added, an organic layer is obtained and the presence of 6-tert-butoxyhexane is confirmed by ¹ H NMR. It can be seen from the 6-tert-butoxy-hexane that the Grignard reaction proceeds perfectly. As a result, 6-tert-butoxyhexylmagnesium chloride is synthesized.

500 g of MeSiCl ₃ and 1 l of THF are added to the reactor and the reactor is cooled to -20°C. 560 g of synthesized 6-tert-butoxyhexylmagnesium chloride was added to the reactor at a rate of 5 ml/min using a feed pump. After the supply of the Grignard reagent is completed, the solution is stirred for 12 hours, while the temperature of the reactor is slowly raised to room temperature. After reacting for 12 hours, it was confirmed that a white MgCl ₂ salt had been obtained. 4 L of hexane are added and the salt is removed with Labdori to give a filtered solution. The resulting filtered solution was added to the reactor and then the hexane was removed at 70° C. to give a light yellow liquid. Using the spectrum ¹ H NMR confirm that the resulting liquid is the desired methyl-(6-tert-butoxyhexyl)dichlorosilane.

¹ H NMR spectrum (CDCl ₃ ): 3.3 (t, 2H), 1.5 (m, 3H), 1.3 (m, 5H), 1.2 (s, 9H), 1.1 (m , 2H), 0.7 (s, 3H).

1.2 mol (150 g) of tetramethyl-cyclopentadiene and 2.4 L of THF are added to the reactor, and then the reactor is cooled to -20°C. 480 ml of n-BuLi are added to the reactor at a rate of 5 ml/min using a feed pump. After adding n-BuLi, the solution was stirred for 12 hours while slowly raising the temperature of the reactor to room temperature. After reacting for 12 hours, an equivalent of methyl-(6-tert-butoxyhexyl)dichlorosilane (326 g, 350 ml) was quickly added to the reactor. The solution is stirred for 12 hours while slowly raising the temperature of the reactor to room temperature, then the reactor is again cooled to 0°C and add 2 equivalents of t-BuNH ₂ . While slowly increasing the temperature of the reactor to room temperature, the solution is stirred for 12 hours. After reaction for 12 hours, THF is removed, 4 L of hexane are added and the salts are removed with Labdori to give a filtered solution. The filtered solution is again added to the reactor and then the hexane is removed at 70°C to obtain a yellow solution. Using the ¹ H NMR spectrum, it was confirmed that the yellow solution was methyl-(6-tert-butoxyhexyl)(tetramethyl-CpH)(tert-butylaminosilane).

TiCl ₃ (THF) ₃ (10 mmol) is rapidly added to the dilithium salt of the ligand synthesized from n-BuLi and the ligand dimethyl(tetramethyl-CpH)-tert-butylaminosilane in THF solution at -78°C. The reaction solution was stirred for 12 hours while slowly raising the temperature from -78°C to room temperature. After stirring for 12 hours, an equivalent of PbCl ₂ (10 mmol) was added to the reaction solution at room temperature, and the solution was stirred for 12 hours. After stirring for 12 hours, a brownish-black solution is obtained. In the resulting reaction solution, THF was removed, and then hexane was added to the filter product. After removal of hexane in the resulting filtered solution, it was confirmed by ¹ H NMR spectrum that (tert-Bu-O-(CH ₂ ) ₆ )(CH ₃ )Si(C ₅ (CH ₃ ) ₄ )(tert-Bu-N )TiCl ₂ as target ([methyl-(6-tert-butoxyhexyl)silyl(η5-tetramethyl-Cp)-(tert-butylamido)]TiCl ₂ .

¹ H NMR spectrum (CDCl ₃ ): 3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 6H), 1.8-0.8 (m), 1.4 (s, 9H), 1.2(s, 9H), 0.7 (s, 3H).

Preparatory example 6

(1) Obtaining a ligand compound

102.54 g (376.69 mmol) of 3-limited indene are added to a dry 1 L Schlenk flask and 450 ml of THF are injected under argon. The solution is cooled to -30°C and 173.3 ml (119.56 g, d=0.690 g/ml) of a 2.5 M solution of n-BuLi in hexane are added dropwise to the solution. The reaction mixture is slowly warmed to room temperature and then stirred until the next day. The solution of lithiated 3-restricted indene is cooled to -78° C., then 24.3 g (188.3 mmol) of dimethyldichlorosilane are prepared and added dropwise to the Schlenk flask. After injection, the mixture is slowly warmed to room temperature, stirred for a day and then quenched by adding 200 ml of water to the flask. The organic layer is separated and dried over MgSO ₄ . This gives 115 g (191.4 mmol, 101.6%) of a yellow oil.

NMR spectrum, standard purity (wt %) = 100%.

Mw=600.99.

¹ H NMR spectrum (500 MHz, CDCl ₃ ): -0.53, -0.35, -0.09(6H, t), 1.18(18H, m), 1.41(8H, m), 1.54(4H, m), 1.68(4H, m), 2.58(4H, m), 3.32(4H, m), 6.04(1H, s), 6.26(1H , s), 7.16(2H, m), 7.28(3H, m), 7.41(3H, m).

(2) Preparation of transition metal compounds

Add 191.35 mmol of the ligand compound synthesized above to an oven-dried 2 L Schlenk flask. Dissolve 4 equivalents of MTBE (67.5 g, d=0.7404 g/ml) and 696 g of toluene (d=0.87 g/ml) in solvent, add 2.1 equivalents of n-BuLi solution (160.7 ml ) and lithiated until the next day. 72.187 g (191.35 mmol) of ZrCl ₄ (THF) ₂ were removed from the glove box and placed in a 2 L Schlenk flask to give a toluene-containing suspension. Both flasks are cooled to

-78°C and the ligand anion is slowly added to the Zr suspension. After injection, the reaction mixture is slowly warmed to room temperature. The mixture is stirred for one day, then the thick suspension is filtered under argon and filtered. Both filtered solids and the filtrate are evaporated in vacuo. From 115 g (191.35 mmol) of ligand, 150.0 g (198 mmol, >99%) of catalyst precursor in the filtrate are obtained and stored in a toluene solution (1.9446 g/mol).

NMR spectrum for standard purity (wt %) = 100%.

Mw=641.05.

¹ H NMR spectrum (500 MHz, CDCl ₃ ): 0.87 (6H, m), 1.14 (18H, m), 1.11-1.59 (16H, m), 2.61, 2.81 (4H, m), 3.30 (4H, m), 5.54 (1H, s), 5.74 (1H, s), 6.88 (1H, m), 7.02 (1H, m) , 7.28(1H, m), 7.39(1H, d), 7.47(1H, t), 7.60-7.71(1H, m).

Preparatory Example 7

(1) Obtaining a ligand compound

Add 2.63 g (12 mmol) of 5-methyl-5,10-dihydroindeno[1,2-b]indole to a flask and dissolve in 50 ml of THF. Add dropwise 6 ml of a 2.5 M solution of n-BuLi in hexane in a bath (dry ice)/acetone and stir at room temperature overnight. In another flask with a volume of 250 ml, 1.62 g (6 mmol) of 6-(tert-butoxyhexyl)dichloro(methyl)silane are dissolved in 100 ml of hexane, a lithiated solution of 5-methyl-5,10-dihydroindeno[1, 2-b]indole in a bath (dry ice)/acetone and stirred at room temperature overnight. At the end of the reaction, the mixture is extracted with ether/water, then the remaining water in the organic layer is removed with MgSO ₄ and dried in vacuo to give 3.82 g (6 mmol) of the ligand compound, which is confirmed by ¹ H NMR.

¹ H NMR spectrum (500 MHz, CDCl ₃ ): -0.33 (3H, m), 0.86-1.53 (10H, m), 1.16 (9H, d), 3.18 (2H, m), 4.07(3H, d), 4.12(3H, d), 4.17(1H, d), 4.25(1H, d), 6.95-7.92(16H, m ).

(2) Obtaining a transition metal compound

Dissolve 3.82 g (6 mmol) of the ligand compound synthesized in 2-1 above in 100 ml of toluene and 5 ml of MTBE, then add dropwise 5.6 ml (14 mmol) of a 2.5 M n-BuLi solution in hexane in a bath (dry ice)/acetone and stirred at room temperature overnight. 2.26 g (6 mmol) of ZrCl ₄ (THF) ₂ and 100 ml of toluene are added to another flask, a suspension is obtained. A suspension of ZrCl ₄ (THF) ₂ in toluene is transferred to the lithiated ligand in a (dry ice)/acetone bath. Stir overnight at room temperature, the color changes to purple. The reaction solution is filtered to remove LiCl. The resulting filtrate is dried in vacuo, hexane is added and sonicated. The suspension is filtered to give 3.40 g (71.1 mol % yield) of a dark purple transition metal compound as a filtered solid.

¹ H NMR spectrum (500 MHz, CDCl3): 1.74 (3H, d), 0.85-2.33 (10H, m), 1.29 (9H, d), 3.87 (3H, s) , 3.92(3H, s), 3.36(2H, m), 6.48-8.10(16H, m).

EXAMPLES

Example 1

(1) Preparation of the support with applied co-catalyst

To a 300 ml glass reactor was added 100 ml of toluene and 10 g of silica (SP2410, available from Grace Davison) was added thereto. The mixture is stirred while raising the temperature in the reactor to approximately 40°C. After sufficient dispersion of the silica, 60 ml of a solution of methylaluminoxane (MAO) (10% by weight in toluene) (Albemarle) is added to the reactor. After the reactor temperature was raised to about 60° C., the mixture was stirred at about 200 rpm for about 12 hours. After that, the temperature of the reactor is lowered to approximately 40°C and the stirring is stopped. After stirring for approximately 10 minutes, the reaction solution is decanted. To the resulting reaction mixture was added 100 ml of toluene, the mixture was stirred for approximately 10 minutes and the stirring was stopped. After stirring for 10 minutes, the toluene is decanted. The result is a substrate with a deposited co-catalyst (MAO/SiO ₂ ).

(2) Obtaining a supported catalyst

50 ml of toluene was added to the reactor containing the supported cocatalyst (MAO/SiO ₂ ), 0.8 g of the transition metal compound prepared in Preparation 1 and 10 ml of toluene were added to the reactor, and stirred at 200 rpm for 60 min. 10.0 g of the transition metal compound obtained in Preparation 4 was added to the reactor, 10 ml of toluene was added to the reactor, and stirred at 200 rpm for 12 hours. Then the stirring is stopped, the reaction solution is allowed to stand for 10 min and decanted. 100 ml of hexane are added to the reactor, the resulting mixture is placed in a 200 ml Schlenk flask and the hexane solution is decanted. Thereafter, the mixture was dried under reduced pressure at room temperature (23±5° C.) for 3 hours to obtain a supported hybrid catalyst.

(3) Production of polyethylene copolymer

By adding 34 kg/hr of hexane, 10 kg/hr of ethylene, 1.06 g/hr of hydrogen, 600 to 720 ml/hr of 1-butene, and 35 g/hr of TEAl to a 200 L continuous high-pressure two-stage reactor, from 7 up to 10 g/hr of the supported hybrid catalyst prepared above is mixed with the hexane solution and added to the reactor.

The mixture is stirred at a pressure of 8.0 bar using a three-stage stirrer and a circulation pump so as to mix the polymerized product. The reactor temperature is maintained at 80°C by a cooling jacket and an external cooler, the reactor level is maintained at 75% and transferred to the last stage of the reactor due to the pressure difference. In the slurry, after completion of the reaction, the hexane is advantageously removed using a centrifugal separator and dried with a dryer through a hot N ₂ purge. The result is approximately 9 kg/hour of polyethylene copolymer.

Example 2

(1) Preparation of the support with applied co-catalyst

The support with the applied co-catalyst (MAO/SiO ₂ ) is prepared in the same way as in example 1.

(2) Obtaining a supported catalyst

50 ml of toluene and 1.5 g of the transition metal compound prepared in Preparation 2 were added to the reactor containing the supported cocatalyst (MAO/SiO ₂ ), 10 ml of toluene were added to the reactor, and stirred at 200 rpm for 60 min. 6.0 g of the transition metal compound obtained in Preparation 5 and 10 ml of toluene were added to the reactor, and stirred at 200 rpm for 12 hours. Then the stirring is stopped, the reaction solution is allowed to stand for 10 min and decanted. 100 ml of hexane are added to the reactor, the resulting mixture is placed in a 200 ml Schlenk flask and the hexane solution is decanted. Thereafter, the mixture was dried under reduced pressure at room temperature (23±5° C.) for 3 hours to obtain a supported hybrid catalyst.

(3) Production of polyethylene copolymer

The polyethylene copolymer was prepared in the same manner as in (3) of Example 1, except that the supported hybrid catalyst obtained in (2) of Example 2 and 3.50 g/hr of hydrogen was used.

Example 3

(1) Preparation of the support with applied co-catalyst

The co-catalyst supported support (MAO/SiO ₂ ) was prepared in the same manner as in point (1) of Example 1.

(2) Obtaining a supported catalyst

50 ml of toluene was added to a reactor containing a supported cocatalyst (MAO/SiO ₂ ) and 1.5 g of the transition metal compound prepared in Preparation 2, and 10 ml of toluene was added to the reactor and stirred at 200 rpm for 60 min. 5.0 g of the transition metal compound obtained in Preparation 5 and 10 ml of toluene were added to the reactor, and stirred at 200 rpm for 12 hours. Then the stirring is stopped, the reaction solution is allowed to stand for 10 min and decanted. 100 ml of hexane are added to the reactor, the resulting mixture is placed in a 200 ml Schlenk flask and the hexane solution is decanted. Thereafter, the mixture was dried under reduced pressure at room temperature (23±5° C.) for 3 hours to obtain a supported hybrid catalyst.

(3) Production of polyethylene copolymer

A polyethylene copolymer was prepared in the same manner as in (3) of Example 2, except that the supported hybrid catalyst obtained in (2) of Example 2 and 3.45 g/hr of hydrogen was used.

Example 4

(1) Preparation of the support with applied co-catalyst

The co-catalyst supported support (MAO/SiO ₂ ) was prepared in the same manner as in point (1) of Example 1.

(2) Obtaining a supported catalyst

Add 50 ml of toluene to the reactor containing the supported cocatalyst (MAO/SiO ₂ ), add 2.1 g of the transition metal compound prepared in Preparation 3 and 10 ml of toluene to the reactor, and stir at 200 rpm for 60 min. 6.7 g of the transition metal compound obtained in Preparation 5 and 10 ml of toluene were added to the reactor, and stirred at 200 rpm for 12 hours. Then the stirring is stopped, the reaction solution is allowed to stand for 10 min and decanted. 100 ml of hexane are added to the reactor, the resulting mixture is placed in a 200 ml Schlenk flask and the hexane solution is decanted. Thereafter, the mixture was dried under reduced pressure at room temperature (23±5° C.) for 3 hours to obtain a supported hybrid catalyst.

(3) Production of polyethylene copolymer

The polyethylene copolymer was prepared in the same manner as in (3) of Example 1, except that the supported hybrid catalyst obtained in (2) of Example 4 and 1.50 g/hr of hydrogen was used.

Example 5

(1) Preparation of the support with applied co-catalyst

The co-catalyst supported support (MAO/SiO ₂ ) was prepared in the same manner as in point (1) of Example 1.

(2) Obtaining a supported catalyst

Add 50 ml of toluene to the reactor containing the supported cocatalyst (MAO/SiO ₂ ), add 2.1 g of the transition metal compound prepared in Preparation 1 and 10 ml of toluene to the reactor, and stir at 200 rpm for 60 min. 1.8 g of the transition metal compound obtained in Preparation 6 and 10 ml of toluene were added to the reactor, and stirred at 200 rpm for 12 hours. In this case, 3.4 g of the transition metal compound obtained in Preparation 7 and 10 ml of toluene were added to the reactor and stirred at 200 rpm for 12 hours. Then the stirring is stopped, the reaction solution is allowed to stand for 10 min and decanted. 100 ml of hexane are added to the reactor, the resulting mixture is placed in a 200 ml Schlenk flask and the hexane solution is decanted. Thereafter, the mixture was dried under reduced pressure at room temperature (23±5° C.) for 3 hours to obtain a supported hybrid catalyst.

(3) Production of polyethylene copolymer

A polyethylene copolymer was prepared in the same manner as in (3) of Example 1, except that the supported hybrid catalyst obtained in (2) of Example 5 and 0.8 g/hr of hydrogen was used.

Comparative examples

Comparative Example 1

An ethylene-1-hexene copolymer (Product XP9000 available from Daelim Industrial) was used.

Comparative Example 2

An ethylene-1-octene copolymer (DX800 available from SK Global Chemical) is used.

Comparative Example 3

(1) Preparation of the support with applied co-catalyst

To a 300 ml glass reactor, add 100 ml of toluene and add 10 g of silica (SP2410, available from Grace Davison). The mixture is stirred while raising the temperature in the reactor to approximately 40°C. After sufficient dispersion of the silica, 60 ml of a solution of methylaluminoxane (MAO) (10% by weight in toluene) (Albemarle) is added to the reactor. After the reactor temperature was raised to about 60° C., the mixture was stirred at about 200 rpm for about 12 hours. After that, the temperature of the reactor is lowered to approximately 40°C and the stirring is stopped. After stirring for approximately 10 minutes, the reaction solution is decanted. To the resulting reaction mixture was added 100 ml of toluene, the mixture was stirred for approximately 10 minutes and the stirring was stopped. After stirring for 10 minutes, the toluene is decanted. The result is a substrate with a deposited co-catalyst (MAO/SiO ₂ ).

(2) Obtaining a supported catalyst

50 ml of toluene are added to the reactor containing the supported cocatalyst (MAO/SiO ₂ ), 2.1 g of a transition metal compound of the following chemical formula A and 10 ml of toluene are added to the reactor and stirred at 200 rpm for 60 minutes. 6.7 g of the transition metal compound obtained in Preparation 5 and 10 ml of toluene were added to the reactor, and stirred at 200 rpm for 12 hours. Then the stirring is stopped, the reaction solution is allowed to stand for 10 min and decanted. 100 ml of hexane are added to the reactor, the resulting mixture is placed in a 200 ml Schlenk flask and the hexane solution is decanted. Thereafter, the mixture was dried under reduced pressure at room temperature (23±5° C.) for 3 hours to obtain a supported hybrid catalyst.

[Chemical Formula A]

(3) Production of polyethylene copolymer

By adding 34 kg/hr of hexane, 10 kg/hr of ethylene, 1.50 g/hr of hydrogen, 600 to 720 ml/hr of 1-butene, and 35 g/hr of TEAL to a 200 L, two-stage continuous high-pressure reactor, from 7 up to 10 g/hr of the supported hybrid catalyst prepared above is mixed with the hexane solution and added to the reactor.

The mixture is stirred at a pressure of 8.0 bar using a three-stage stirrer and a circulation pump so as to mix the polymerized product. The reactor temperature is maintained at 80°C by means of a cooling jacket and an external cooler, the reactor level is maintained at 75% and transferred to the last stage of the reactor due to the pressure difference. In the slurry after completion of the reaction, hexane is advantageously removed using a centrifugal separator and dried with a dryer by blowing hot N ₂ . The result is approximately 9 kg/hour of polyethylene copolymer.

Reference examples

Reference Example 1

(1) Preparation of the support with applied co-catalyst

The co-catalyst supported support (MAO/SiO ₂ ) was prepared in the same manner as in point (1) of Example 1.

(2) Obtaining a supported catalyst

Add 50 ml of toluene to the reactor containing the supported cocatalyst (MAO/SiO ₂ ), add 0.8 g of the transition metal compound prepared in Preparation 1 and 10 ml of toluene to the reactor, and stir at 200 rpm for 60 min. 10 g of the transition metal compound obtained in Preparation 4 and 10 ml of toluene were added to the reactor, and stirred at 200 rpm for 12 hours. Then the stirring is stopped, the reaction solution is allowed to stand for 10 min and decanted. 100 ml of hexane are added to the reactor, the resulting mixture is placed in a 200 ml Schlenk flask and the hexane solution is decanted. Thereafter, the mixture was dried under reduced pressure at room temperature (23±5° C.) for 3 hours to obtain a supported hybrid catalyst.

(3) Production of polyethylene copolymer

The polyethylene copolymer was obtained in the same manner as in (3) of Example 1 except that the supported hybrid catalyst obtained in (2) of Reference Example 1 and 1.50 g/hr of hydrogen was used.

Reference Example 2

(1) Preparation of the support with applied co-catalyst

The co-catalyst supported support (MAO/SiO ₂ ) was prepared in the same manner as in point (1) of Example 1.

(2) Obtaining a supported catalyst

Add 50 ml of toluene to the reactor containing the supported cocatalyst (MAO/SiO ₂ ), add 0.8 g of the transition metal compound prepared in Preparation 1 and 10 ml of toluene to the reactor, and stir at 200 rpm for 60 min. 10 g of the transition metal compound obtained in Preparation 4 and 10 ml of toluene were added to the reactor, and stirred at 200 rpm for 12 hours. Then the stirring is stopped, the reaction solution is allowed to stand for 10 min and decanted. 100 ml of hexane are added to the reactor, the resulting mixture is placed in a 200 ml Schlenk flask and the hexane solution is decanted. Thereafter, the mixture was dried under reduced pressure at room temperature (23±5° C.) for 3 hours to obtain a supported hybrid catalyst.

(3) Production of polyethylene copolymer

The polyethylene copolymer was obtained in the same manner as in (3) of Example 1, except that the supported hybrid catalyst obtained in (2) of Reference Example 2 and 1.40 g/hour of hydrogen was used.

Reference Example 3

(1) Preparation of the support with applied co-catalyst

The co-catalyst supported support (MAO/SiO ₂ ) was prepared in the same manner as in point (1) of Example 1.

(2) Obtaining a supported catalyst

Add 50 ml of toluene to the reactor containing the supported cocatalyst (MAO/SiO ₂ ), add 1.5 g of the transition metal compound prepared in Preparation 2 and 10 ml of toluene to the reactor, and stir at 200 rpm for 60 min. 6.0 g of the transition metal compound obtained in Preparation 5 and 10 ml of toluene were added to the reactor, and stirred at 200 rpm for 12 hours. Then the stirring is stopped, the reaction solution is allowed to stand for 10 min and decanted. 100 ml of hexane are added to the reactor, the resulting mixture is placed in a 200 ml Schlenk flask and the hexane solution is decanted. After that, the mixture is dried under reduced pressure at room temperature (23±5°C) for 3 hours to obtain a hybrid catalyst on the substrate.

(3) Production of polyethylene copolymer

The polyethylene copolymer was obtained in the same manner as in (3) of Example 1, except that the supported hybrid catalyst obtained in (2) of Reference Example 3 and 3.2 g/hour of hydrogen was used.

Test examples

The physical properties of the polyethylene copolymers prepared according to the Examples, Comparative Examples, and Reference Examples were evaluated by the following methods, and the results are shown in Table 1 below.

(1) Density (unit: g/cm ³ ): Measured in accordance with ASTM D1505.

(2) Melt index (MI, units: g/10 min): Mass of molten polyethylene copolymer passing through a 2.1 mm hole at 190° C. for 10 min under force conditions of 2.16 kg or 21. 6 kg in vertical direction with respect to gravity, measured in accordance with ASTM D1238.

(3) Average value of SCB content (side chain branching: branching of 2-7 carbon atoms per 1000 carbon atoms) units: number/1000C)

Molecular weight (M) is determined using Gel Permeation Chromatography (GPC).

More specifically, the logarithm of the molecular weight (log M) is represented using the x-axis.

A molecular weight distribution curve is obtained using gel permeation chromatography (GPC), where the molecular weight (M), more specifically the log value (logM) of the molecular weight, is represented by the x-axis, and the content of polymer chains (dwt/dlogM) relative to the molecular weight masses are represented using the y-axis. The curve is shown as a continuous solid line in FIG. 1.

Then use the FT-IR device connected to the GPC device, in the case of the SCB distribution curve, where the molecular weight (M) obtained by gel permeation chromatography, more precisely the log value (log M) of the molecular weight, is represented by the x-axis, and the content branching of side chains of 2-7 carbon atoms per 1000 carbon atoms relative to the molecular weight value, obtained using Fourier IR spectroscopy, is presented as a y-axis.

The average value of side chain branching content of 2-7 carbon atoms per 1000 carbon atoms that each of the plurality of polymer chains present in the polyethylene copolymer is calculated using the SCB distribution curve.

An average value is obtained by dividing the total amount of side chain branching of 2-7 carbon atoms per 1000 carbon atoms that each of the plurality of polymer chains found in the polyethylene copolymer has by the number of polymer chains found in the polyethylene copolymer.

Meanwhile, the measuring instruments and measurement conditions in the case of gel permeation chromatography are as follows.

Measuring device : column Polymer Laboratories PLgel MIX-B 300 mm, Waters PL-GPX220

Measurement conditions :

The evaluation temperature is 160°C, the solvent is 1,2,4-trichlorobenzene, the flow rate is 1 ml/min, the sample is prepared at a concentration of 10 mg/10 ml and then fed in an amount of 200 μl, and the values of Mw, Mn and PPD (PDI) can be determined using a calibration curve obtained using a polystyrene standard. The molecular weight of the used polystyrene standards has 9 types 2000/10000/30000/70000/200000/700000/2000000/4000000/10000000.

In addition, the measuring instruments for FT-IR and the measurement conditions are as follows.

Gauge : PerkinElmer Spectrum 100

Measurement conditions :

Wave number: 2700 to 3000 cm ^-1

Number of scans: 16

Resolution: 8 cm ^-1

Detector: DTGS (deuterated triglycerol sulfate detector).

(4) SCG index (unit: g/10 min): is defined as the value (p/q) obtained by dividing the melt index measured in accordance with ASTM 1238 (load 21.6 kg, 190°C) by the CDI(q) index below.

(5) Comonomer Distribution Index (CDI): Considering FIG 2, a molecular weight distribution curve (shown as a continuous solid line in FIG 2) is obtained using gel permeation chromatography (GPC), where molecular weight (M), more precisely log value ( log M) molecular weight, represented by the x-axis, and the content of polymer chains (dwt/dlog M) relative to the value of the molecular weight, represented by the y-axis. The content of SCB (side chain branching) (c) of the polymer chain, which is the molecular weight value "m", satisfying the following equation 2, and the content of SCB (side chain branching) (d) of the polymer chain, which is the molecular weight value "n ”satisfying the following equation 3 is measured using an FT-IR device connected to the GPC device. The contents by GPC and FT-IR are the same as those described in paragraph "(3) Average content of side chain branching (SCB) (branching of 2-7 carbon atoms per 1000 carbon atoms) units: number/1000C)" .

Equation 2

Equation 3

In equations 2 and 3, "a" represents the minimum molecular weight, which is represented by the x-axis on the GPC molecular weight distribution curve, "b" represents the maximum molecular weight, which is represented by the x-axis on the molecular weight distribution curve according to GPC, f(x) is the formula of the function of the molecular weight distribution curve obtained using gel permeation chromatography (GPC), where the molecular weight (M), and more specifically the log value (log M) of the molecular weight, is represented by the x-axis, and the polymer chain content (dwt/dlog M) relative to the molecular weight value is represented by the y-axis.

Then, the value (c/d) obtained by dividing the content of SCB (side chain branching) (c) polymer chain, which is the molecular weight "m" satisfying Equation 2, by the content of SCB (side chain branching) (d) polymer chain, which is the molecular weight that satisfies Equation 3, is taken as the comonomer distribution index (CDI) and calculated.

(6) S.H. Modulus (strain hardening modulus, unit: MPa): measured according to ISO 18488.

(7) Stress cracking resistance (Full Notch Creep Test (FNCT), units: hour (hour)): measured in accordance with ISO 16770 under conditions of 80°C, 4 MPa and 10%- IGEPAL CA-630 solution.

Table 1

Example 1 Example 2 Example 3 Example 4 Example 5 Compar. example 1 Compar. example 2 Compar. example 3 Reference Example 1 Reference Example 2 Reference Example 3 transition metal compound Will prepare. example 1/ Prepare. example 4 Will prepare. example 2/ Prepare. example 5 Will prepare. example 2/ Prepare. example 5 Will prepare. example 3/ Prepare. example 5 Will prepare. example 1/ Prepare. example 6/ Prepare. example 7 - - Formula A/ Prepare. example 5 Will prepare. example 1/ Prepare. example 4 Will prepare. example 1/ Prepare. example 4 Will prepare. example 2/ Prepare. example 5 Comonomer 1-butene 1-butene 1-butene 1-butene 1-butene 1-hexene 1-octene 1-butene 1-butene 1-butene 1-butene Added amount of hydrogen (g/h) 1.06 3.50 3.45 1.50 0.80 - - 1.50 1.50 1.40 3.20 Density 0.9383 0.9370 0.9355 0.9397 0.9365 0.9346 0.9337 0.9341 0.9365 0.9362 0.9375 IR (2.16 kg) 0.226 0.502 0.591 0.174 0.036 0.600 0.640 0.653 0.604 0.439 0.765 IR (21.6 kg) 15.965 17.076 24.458 9.644 9.574 13,200 20,500 22.0 42.060 21.824 32.791 Average SCB content [number/1000C] 7.2 8.7 10.1 7.3 7.2 6.5 6.8 6.7 8.5 8.4 9.5 CDI 1.80 2.20 2.56 1.91 1.23 1.05 0.94 0.87 1.85 1.56 2.17 SCG Index 8.9 7.8 9.6 5.0 7.8 12.6 21.8 17.6 22.7 14.0 15.1 Index SCG/ (number of carbon atoms of the comonomer) ^1/2 4.45 3.9 4.8 2.5 3.9 5.14 7.71 6.57 11.35 7 7.55 S.H. Module (80°C) 0.92 0.92 0.90 0.97 0.97 0.76 0.76 0.77 0.77 0.84 0.82 FNCT(4 MPa) more than 2527 1963 More than 2915 More than 3118 More than 8615 twenty 425 350 71 155 130

As shown in Table 1, the polyethylene copolymers obtained in Examples 1 to 5 can satisfy the conditions that SCG is 5 to 9.6, CDI is 1.23 to 2.56, S.H. modulus (measured at 80°C) is 0.90 to 0.97 MPa, stress crack resistance (FNCT, measured at 4 MPa) is 1963 hours or more, melt index (measured at 190°C under load 2.16 according to ASTM D1238) is from 0.036 to 0.591 g/10 min, the melt index (measured at 190°C under a load of 21.6 kg according to ASTM D1238) is from 9.574 to 24.458 g/10 min, and the average the value of SCB content is from 7.2/1000C to 10.1/1000C.

In addition, in the polyethylene copolymers obtained in examples 1-5, the values of the SCG index, as shown, are respectively 4.45, 3.9, 4.8, 2.5 and 3.9 times greater than the square root of the number of carbon atoms of the alpha-olefin used as the comonomer, confirming that they satisfy a multiple of 5 or less compared to the value of the square root of the number of carbon atoms.

On the other hand, in the polyethylene copolymers obtained in Comparative Examples 1 to 3, the SCG index values were shown to be 5.14 times, 7.71 times, and 6.57 times greater than the square root value of the alpha-olefin carbon number. used as a comonomer, which is 5 times the square root of the number of carbon atoms.

In addition, in the polyethylene copolymers obtained in Comparative Examples 1 to 3, the SCG index was shown to be 12.6 to 21.8, which is higher than that in Examples, S.H. the modulus (measured at 80°C) is shown to be 0.76 to 0.77 MPa, which is lower than the value of the modulus in the examples, and the stress cracking resistance (FNCT, measured at 4 MPa) is shown to be from 20 to 425 hours, which is lower than in the examples, confirming as a result that the physical properties deteriorate in comparison with the examples.

Claims (98)

1. A polyethylene copolymer containing an ethylene-derived repeating unit and an alpha-olefin-derived repeating unit having 3 to 10 carbon atoms and satisfying the following Equation 1: [Equation 1] SCG index ≤ (alpha-olefin carbon number) ^1/2 × 5 , where in the above equation 1 the SCG index is the value (p/q) obtained by dividing the melt index (p) of the polyethylene copolymer, measured in accordance with ASTM 1238 (load 21.6 kg, 190°C), by the comonomer distribution index (q) of the polyethylene copolymer , and The comonomer distribution index (CDI) is calculated from the following equation 2 based on a plot of the molecular weight distribution curve (where x-axis denotes polymer chain molecular weight and y-axis denotes polymer chain content) obtained by gel permeation chromatography against a polyethylene copolymer: [Equation 2] Comonomer Distribution Index (CDI) = c/d , where in Equation 2 above, "c" is the side chain branching (SCB) content (measured by Fourier IR spectroscopy) of 2-7 carbons per 1000 carbons of the polymer chain, which is the molecular weight "m", at where the area (s1) between the molecular weight distribution curve and the x-axis in the area a≤x≤m is 80% of the area (s2) between the molecular weight distribution curve and the x-axis in the area a≤x≤b, "d" is the side chain branching (SCB) content (measured by Fourier IR spectroscopy) of 2-7 carbons per 1000 carbons of the polymer chain, which is the value of the molecular weight "n" at which the area (s3) between the molecular weight distribution curve and the x-axis in the area a≤x≤n is 20% of the area (s4) between the molecular weight distribution curve and the x-axis in the area a≤x≤b, and "a" represents the minimum value of the molecular weight, which is represented by the x-axis in the plot of the molecular weight distribution curve, and "b" is the maximum value of the molecular weight, which is represented by the x-axis in the plot of the molecular weight distribution. 2. The polyethylene copolymer according to claim 1, wherein the polyethylene copolymer has S.H. modulus (measured at 80°C) 0.85 MPa or more. 3. The polyethylene copolymer according to claim 1, wherein the polyethylene copolymer has a stress crack resistance (FNCT, measured at 4 MPa) of 1000 hours or more. 4. The polyethylene copolymer of claim 1, wherein the polyethylene copolymer has a melt index (measured at 190° C. under a load of 2.16 kg according to ASTM D1238) of 0.01 to 0.65 g/10 min. 5. The polyethylene copolymer of claim 1, wherein the polyethylene copolymer has a melt index (measured at 190° C. under a load of 21.6 kg according to ASTM D1238) of 2 to 30 g/10 min. 6. The polyethylene copolymer according to claim 1, wherein the polyethylene copolymer has a comonomer distribution index (CDI) of 1.2 to 3.0. 7. The polyethylene copolymer according to claim 1, wherein the polyethylene copolymer has an SCG index of 11 or less. 8. The polyethylene copolymer according to claim 1, wherein the polyethylene copolymer has a density (ASTM 1505) of 0.930 to 0.945 g/cm ³ . 9. The polyethylene copolymer according to claim 1, in which the average value of the branching content of the side chains (measured using Fourier IR spectroscopy) of 2-7 carbon atoms per 1000 carbon atoms, which each of the plurality of polymer chains found in the polyethylene copolymer, is 7/1000C or more and 15/1000C or less. 10. A method for producing a polyethylene copolymer according to claim 1, including the step of polymerizing an ethylene monomer and an alpha-olefin monomer selected from C _3-10 alpha-olefins in the presence of a supported hybrid catalyst, which includes: a mixture of transition metals, including a first mixture, comprising a first transition metal compound containing at least one compound selected from the group consisting of the following chemical formulas 2 and 3, and a second transition metal compound containing at least one compound selected from the group consisting of the following of formulas 4-7, or a second mixture comprising a first transition metal compound containing the following chemical formula 1 and a second transition metal compound containing at least one compound selected from the group consisting of the following chemical formulas 4, 6 and 7; and a substrate on which mixtures of transition metals are deposited: [Chemical Formula 1]

, where in the chemical formula 1 M ₁ is Zr; at least one of the R ₁ -R ₈ substituents is -(CH ₂ ) _n -OR _a (where R _a is a branched C _1-6 alkyl group and n is an integer from 2 to 10), and the rest are the same and each represents a hydrogen atom; X ₁ and X ₂ are the same and each represents a halogen atom, [Chemical Formula 2]

, where in the chemical formula 2 M ₂ is Zr; X ₃ and X ₄ are the same and each represents a halogen atom; at least one of the R ₁₁ -R ₁₄ substituents is -(CH ₂ ) _m -OR _b (wherein R _b is a branched C _1-6 alkyl group and m is an integer from 2 to 10), and the rest are the same and each represents a hydrogen atom; substituents R ₁₅ and R ₁₆ are the same and each represents a hydrogen atom; [Chemical formula 3]

, where in the chemical formula 3 M ₃ is Zr; X ₅ and X ₆ are the same and each represents a halogen atom; substituents R ₂₀ - R ₂₉ are hydrogen atoms, R ₂₉ is C _1-20 -alkyl, R ₂₁ is -(CH ₂ ) _p -OR _c (where R _c is a branched C _1-6 -alkyl group and p means an integer from 2 to 10), [Chemical formula 4]

, where in the chemical formula 4 A ₁ is a C _1-20 alkyl group; D ₁ is -O-; L ₁ is a linear C _1-10 alkylene group; Y ₁ represents a silicon atom; Z ₁ is a C _1-20 alkyl group; M ₄ is Ti; X ₇ and X ₈ are the same and each represents a halogen atom; C ₁ is represented by the following formula 4a [Chemical formula 4a]

, R ₃₀ - R ₃₅ in the chemical formula 4a are the same or different, and each independently represents hydrogen or a C _1-10 alkyl group; C ₂ is -NR ₃₆ -; and R ₃₆ is a C _1-10 alkyl group, [Chemical Formula 5]

, where in the chemical formula 5 A ₂ is a C _1-20 alkyl group; D ₂ is -O-; L ₂ is a linear C _1-10 alkylene group; Y ₂ represents a silicon atom; Z ₂ is a C _1-20 alkyl group; M ₅ is Ti; X ₉ and X ₁₀ are the same and each represents a halogen atom; C ₃ is represented by the following formula 5a [Chemical formula 5a]

; C ₄ is -NR ₄₄ -; substituents R ₄₀ -R ₄₄ are the same and each represents a C _1-20 -alkyl group, [Chemical formula 6]

, where in the chemical formula 6 M ₇ is Zr; X ₁₃ and X ₁₄ are the same and each represents a halogen atom; substituents R ₇₅ and R ₇₆ are the same and each represents a hydrogen atom; Q ₁ and Q ₂ are the same and are each independently C _1-20 alkyl, at least one of the R ₇₁ -R ₇₄ substituents is -(CH ₂ ) _q -OR _d (wherein R _d is a branched C _1-6 alkyl group and q is an integer from 2 to 10), and the rest are the same or different from each other and each independently represents a hydrogen atom; [Chemical formula 7]

, where A ₃ represents a C _1-20 -alkyl group; D ₃ is -O-; L ₃ is a linear C _1-10 alkylene group; Y ₃ represents a silicon atom; Z ₃ is a C _1-20 alkyl group; M ₆ is Zr; X ₁₁ and X ₁₂ are the same and each represents a halogen atom; C ₅ and C ₆ are the same and are each independently represented by one of the following formulas 6a and 6b [Chemical formula 6a]

, [Chemical Formula 6b]

, the substituents R ₅₀ -R ₅₈ and R ₆₀ -R ₆₈ are the same or different from each other and each independently represents a hydrogen atom, a halogen atom, a C _1-20 alkyl group. 11. A method for producing a polyethylene copolymer according to claim 10, in which the first transition metal compound is in an amount of from 1 to 80 wt. hours based on 100 wt. hours of the second compound of the transition metal. 12. A method for producing a polyethylene copolymer according to claim 10, in which hydrogen is added in an amount of from 0.005 to 0.040 wt% at the stage of polymerization of ethylene monomer and alpha-olefin monomer. relative to ethylene monomer. 13. The method for producing a polyethylene copolymer according to claim 10, in which the substrate is silicon dioxide, alumina, magnesium oxide, or a mixture thereof. 14. The method for producing a polyethylene copolymer according to claim 10, in which the alpha-olefin monomer includes one or more monomers selected from the group including propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene. 15. A pipe containing a polyethylene copolymer according to claim 1.

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