KR102272244B1 - Process for preparing a catalyst for polymerizing an olefin, catalyst for polymerizing an olefin, and polyolefin - Google Patents

Abstract

The present invention relates to a method for preparing a catalyst for olefin polymerization, a catalyst for olefin polymerization, and an olefin-based polymer. Specifically, the present invention relates to a method for preparing a supported metallocene catalyst capable of controlling physical properties such as strength, viscosity, and elasticity of an olefin-based polymer, a supported metallocene catalyst for olefin polymerization prepared using the same, and the present invention in the presence of the catalyst It relates to a polymerized olefinic polymer. The method for producing a metallocene-supported catalyst according to an embodiment of the present invention is an olefin polymerization capable of improving the strength, viscosity, elasticity, etc. of the polymer by increasing the Z average molecular weight without significantly changing other properties of the olefinic polymer. It is possible to provide a metallocene supported catalyst for use.

Description

A method for producing a catalyst for olefin polymerization, a catalyst for olefin polymerization, and an olefin-based polymer

The present invention relates to a method for preparing a catalyst for olefin polymerization, a catalyst for olefin polymerization, and an olefin-based polymer. Specifically, the present invention relates to a method for preparing a supported metallocene catalyst capable of controlling physical properties such as strength, viscosity, and elasticity of an olefin-based polymer, a supported metallocene catalyst for olefin polymerization prepared using the same, and the present invention in the presence of the catalyst It relates to a polymerized olefinic polymer.

A metallocene catalyst, which is one of the catalysts used to polymerize olefins, is coordinated with a transition metal or a transition metal halogen compound with ligands such as cyclopentadienyl, indenyl, and cycloheptadienyl. As a bound compound, it has a sandwich structure in its basic form.

In contrast to the Ziegler-Natta catalyst, which is another catalyst used to polymerize olefins, the active site metal component is dispersed on an inactive solid surface and the properties of the active site are not uniform, the metallocene catalyst has a uniform structure. It is known as a single-site catalyst with all active sites having the same polymerization properties because it is a compound with The polymer polymerized with such a metallocene catalyst has a narrow molecular weight distribution and a uniform distribution of comonomers.

In general, polymers exhibit a distribution consisting of mixtures of large and small molecular weights centered on an average molecular weight. Representative types of average molecular weight include number average molecular weight (Mn), weight average molecular weight (Mw), and Z average molecular weight (Mz). Among them, the Z average molecular weight is the molecular weight that most reflects the contribution of the high molecular weight component in the polymer, and may represent physical properties such as elongation, flexibility, and melt viscosity of the polymer.

For example, in bimodal polyethylene produced by copolymerization, when high molecular weight polyethylene has a high Z average molecular weight, excellent physical properties may be exhibited in terms of mechanical strength and environmental stress cracking resistance (ESCR). That is, since more comonomers are incorporated in the high molecular weight region to have more tie bonds, mechanical properties such as ESCR can be improved.

If the Z average molecular weight can be increased without significantly changing other properties such as melt flow ratio, number average molecular weight, weight average molecular weight, and activity of the polymer, basic physical properties such as processability of the polymer are greatly It is useful because it can finely control physical properties such as strength, viscosity, and elasticity without changing it.

An object of the present invention is to provide a method for preparing a metallocene-supported catalyst capable of improving physical properties such as strength, viscosity, and elasticity without significantly changing other properties of an olefin-based polymer.

Another object of the present invention is to provide a metallocene-supported catalyst capable of improving physical properties, such as strength, viscosity, and elasticity, without significantly changing other properties of an olefin-based polymer.

Another object of the present invention is to provide an olefin-based polymer with improved physical properties, such as strength, viscosity, and elasticity, without significantly changing other properties.

According to one embodiment of the present invention for achieving this object, (1) activating any one of the transition metal compounds represented by Chemical Formulas 1 and 2 below with a first cocatalyst compound and a second cocatalyst compound; and (2) supporting a transition metal compound on a carrier, wherein the second cocatalyst compound is tris(pentafluorophenyl)borane, and the second cocatalyst compound to the first cocatalyst A method for preparing a supported metallocene catalyst for olefin polymerization is provided, wherein the molar ratio of the compound is 0.001 or more and less than 0.07.

[Formula 1]

[Formula 2]

In the above formulas 1 and 2, n and o are each an integer of 0-5, m and l are each an integer of 0-4,

M is titanium (Ti), zirconium (Zr) or hafnium (Hf),

each X is independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkylidene;

Q is carbon (C), silicon (Si), germanium (Ge) or tin (Sn),

R ¹ to R ⁵ are each independently substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _{1 -20} alkyl C _6-20 aryl, substituted or unsubstituted C _6-20 aryl C _1-20 alkyl, substituted or unsubstituted C _1-20 heteroalkyl, substituted or unsubstituted C _3-20 heteroaryl, substituted or unsubstituted C _1-20 alkylamido, substituted or unsubstituted C _6-20 arylamido, substituted or unsubstituted C _1-20 alkylidene, or substituted or unsubstituted C _1-20 silyl , R ^{1 To} R ⁵ Each independently adjacent groups may be connected to form a substituted or unsubstituted saturated or unsaturated C _4-20 ring,

R ⁶ and R ⁷ are each independently substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _{1 -20} alkyl C _6-20 aryl, substituted or unsubstituted C _6-20 aryl C _1-20 alkyl, substituted or unsubstituted C _1-20 heteroalkyl, substituted or unsubstituted C _3-20 heteroaryl, substituted or unsubstituted C _1-20 alkylamido, substituted or unsubstituted C _6-20 arylamido, substituted or unsubstituted C _1-20 alkylidene, or substituted or unsubstituted C _1-20 silyl.

Preferably, in Formulas 1 and 2, n and o are each an integer of 1 to 3, m and l are each an integer of 1 to 2, X is each independently a halogen or a methyl group, and M is zirconium or hafnium , Q is carbon, R ¹ to R ⁵ are each C _1-20 alkyl, and R ⁶ and R ⁷ are each C _6-20 aryl.

More preferably, the transition metal compounds of Chemical Formulas 1 and 2 are compounds represented by Chemical Formulas 1-1 and 2-1 below, respectively.

[Formula 1-1]

[Formula 2-1]

Meanwhile, the first cocatalyst compound may include at least one of the compounds represented by Formula 3 below.

[Formula 3]

In Formula 3, n is an integer of 2 or more, and R _a is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen.

Specifically, the compound represented by Formula 3 above is a group consisting of methyl aluminoxane (MAO), modified methyl aluminoxane (MMAO), ethyl aluminoxane, isobutyl aluminoxane and butyl aluminoxane at least one selected from

Preferably, the carrier may include at least one selected from the group consisting of silica, alumina, zeolite and magnesia.

More preferably, the transition metal compound, the first cocatalyst compound, and the second cocatalyst compound may be supported on a single type of carrier. Specifically, the transition metal compound, the first promoter compound, and the second promoter compound may be supported on silica.

In this case, the amount of the transition metal compound supported on the carrier may be 0.01 to 3.0 wt % based on the total weight of the supported catalyst, and the total amount of the cocatalyst compound supported on the carrier is 1 to 50 wt % based on the total weight of the supported catalyst. can

According to another embodiment of the present invention, any one of the transition metal compound represented by Formula 1 and Formula 2 below; a first cocatalyst compound and a second cocatalyst compound; and a carrier, wherein the first cocatalyst compound is at least one selected from the group consisting of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and butylaluminoxane, and the second cocatalyst compound This tris(pentafluorophenyl)borane, wherein the molar ratio of the second promoter compound to the first promoter compound is 0.001 or more and less than 0.07 is provided a supported metallocene catalyst for olefin polymerization.

[Formula 1]

[Formula 2]

In Formulas 1 and 2, n, o, m, l, M, X, Q, R ¹ to R ⁷ are as defined above.

According to another embodiment of the present invention, it is polymerized in the presence of the above catalyst for olefin polymerization, the density is 0.88 to 0.95 g/cm 3 , the weight average molecular weight is 2,000 to 1,000,000 g/mole, and the Z average molecular weight is 100,000 to 10,000,000 g/mole, and a Z-average molecular weight to weight-average molecular weight ratio (Mz/Mw) of 1.5 to 50.0 is provided.

Specifically, the olefin-based polymer may be a copolymer of an olefin-based monomer and an alpha-olefin-based comonomer. More specifically, the olefinic monomer is ethylene, and the alpha-olefinic comonomer is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1- It may be at least one selected from the group consisting of decene, 1-undecene, 1-dodecene, 1-tetradecene and 1-hexadecene.

Preferably, the olefinic polymer may be a linear low density polyethylene wherein the olefinic monomer is ethylene and the alpha-olefinic comonomer is 1-hexene.

The method for producing a metallocene-supported catalyst according to an embodiment of the present invention is an olefin polymerization capable of improving the strength, viscosity, elasticity, etc. of the polymer by increasing the Z average molecular weight without significantly changing other properties of the olefinic polymer. It is possible to provide a metallocene supported catalyst for use.

1 is a gel permeation chromatography-3D (GPC-3D) measurement graph of the olefin-based polymer obtained in Examples 1 to 3 of the present invention.
2 is a graph showing the elastic modulus of the olefin-based polymer obtained in Example 2 and Comparative Example 1 of the present invention.

Hereinafter, the present invention will be described in more detail.

The method for preparing a supported metallocene catalyst for olefin polymerization according to an embodiment of the present invention includes (1) mixing any one of the transition metal compounds represented by Chemical Formulas 1 and 2 below to a first cocatalyst compound and a second cocatalyst compound. activating with; and (2) supporting a transition metal compound on a carrier, wherein the second cocatalyst compound is tris(pentafluorophenyl)borane, and the second cocatalyst compound to the first cocatalyst The molar ratio of the compound is 0.001 or more and less than 0.07.

In the above step (1), any one of the transition metal compounds represented by the following Chemical Formulas 1 and 2 is activated with the first cocatalyst compound and the second cocatalyst compound.

[Formula 1]

[Formula 2]

In the above formulas A and B, n and o are integers from 0 to 5, respectively, and m and l are integers from 0 to 4, respectively. Specifically, n and o may be integers of 1 to 3, respectively, and m and l may be integers of 1 to 2, respectively.

M is a group 4 transition metal of the periodic table of elements. Specifically, M may be titanium (Ti), zirconium (Zr), or hafnium (Hf), and more specifically, zirconium or hafnium.

each X is independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkylidene. Specifically, each X may be halogen or methyl. More specifically, each of X may be chlorine (Cl).

Q is any one of carbon (C), silicon (Si), germanium (Ge), or tin (Sn). Specifically, Q may be carbon (C).

R ¹ to R ⁵ are each independently substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _{1 -20} alkyl C _6-20 aryl, substituted or unsubstituted C _6-20 aryl C _1-20 alkyl, substituted or unsubstituted C _1-20 heteroalkyl, substituted or unsubstituted C _3-20 heteroaryl, substituted or unsubstituted C _1-20 alkylamido, substituted or unsubstituted C _6-20 arylamido, substituted or unsubstituted C _1-20 alkylidene, or substituted or unsubstituted C _1-20 silyl. However, R ¹ to R ⁵ may be each independently connected to adjacent groups to form a substituted or unsubstituted saturated or unsaturated C _4-20 ring.

Specifically, R ¹ and R ² may each independently be C _1-20 alkyl. Preferably, R ¹ and R ² are each n -butyl or methyl.

Specifically, R ³ may be C _{1-20 alkyl.} More specifically, R ³ may be C _{1-6 alkyl.} Preferably R ³ is n -butyl.

Specifically, R ⁴ and R ⁵ may each be C _1-20 alkyl. More specifically, R ⁴ and R ⁵ may each be C _1-6 alkyl. Preferably R ⁴ and R ⁵ are each t -butyl.

R ⁶ and R ⁷ are each independently substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _{1 -20} alkyl C _6-20 aryl, substituted or unsubstituted C _6-20 aryl C _1-20 alkyl, substituted or unsubstituted C _1-20 heteroalkyl, substituted or unsubstituted C _3-20 heteroaryl, substituted or unsubstituted C _1-20 alkylamido, substituted or unsubstituted C _6-20 arylamido, substituted or unsubstituted C _1-20 alkylidene, or substituted or unsubstituted C _1-20 silyl.

Specifically, R ⁶ and R ⁷ are each C _6-20 aryl. More specifically, R ⁶ and R ⁷ are each phenyl.

In a preferred embodiment of the present invention, the transition metal compound of Chemical Formula 1 and Chemical Formula 2 may be a compound represented by Chemical Formulas 1-1 and 2-1 below, respectively.

[Formula 1-1]

[Formula 2-1]

Meanwhile, in the above step (1), the first cocatalyst compound may include one or more of the compounds represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3, n is an integer of 2 or more, and R _a may be a halogen atom, a hydrocarbon having 1 to 20 carbon atoms, or a hydrocarbon having 1 to 20 carbon atoms substituted with a halogen. Specifically, R _a may be methyl, ethyl, n -butyl or isobutyl.

Examples of the compound represented by Formula 3 above include methyl aluminoxane (MAO), modified methyl aluminoxane (MMAO), ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and the like. and methylaluminoxane is preferred, but is not limited thereto.

In addition, the second cocatalyst compound is tris (pentafluorophenyl) borane represented by Chemical Formula 4 below.

[Formula 4]

In the above step (1), a method of adding the first cocatalyst compound and the second cocatalyst compound to activate the transition metal compound is not particularly limited. As a preferred embodiment, the second promoter compound may be added to a solution in which the first promoter compound is dissolved in an organic solvent and stirred, and then a transition metal compound may be added thereto and mixed.

Here, the organic solvent includes an aliphatic hydrocarbon solvent such as hexane and pentane, an aromatic hydrocarbon solvent such as toluene and benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, an etheric solvent such as diethyl ether and tetrahydrofuran, acetone, It may be most organic solvents such as ethyl acetate, preferably toluene or hexane, but is not particularly limited thereto.

When adding the second promoter compound to the solution of the first promoter compound, the temperature and stirring time are not particularly limited. Specifically, the second promoter compound is added to the solution of the first promoter compound at a temperature of 0 to 150° C., preferably at a temperature of 25 to 80° C., for 1 minute to 24 hours, preferably 1 minute to 15 It is preferred to stir it for a period of time.

In addition, when the transition metal compound is added to the mixed solution of the first co-catalyst compound and the second co-catalyst compound, the temperature and stirring time are not particularly limited. Specifically, the transition metal compound is added to a mixed solution of the first co-catalyst compound and the second co-catalyst compound at a temperature of 0 to 150 ° C, preferably 25 to 80 ° C, for 1 minute to 24 hours, preferably It is preferable to stir it for 5 minutes to 15 hours.

In the above step (1), the molar ratio of the second promoter compound to the first promoter compound is 0.001 or more and less than 0.07. If this molar ratio is less than 0.001, the effect of increasing the Z average molecular weight of the olefin-based polymer prepared using the finally obtained catalyst is insignificant, and if this molar ratio is 0.07 or more, fouling may occur in the reactor during olefin polymerization. it is not preferable to have

In the above step (2), the transition metal compound is supported on a carrier.

Specifically, the transition metal compound may be supported on the carrier by contacting the transition metal compound activated by the addition of the first cocatalyst compound and the second cocatalyst compound in step (1) with the carrier.

Here, the carrier may include a material containing a hydroxyl group on the surface, preferably dried to remove moisture on the surface, a material having a high reactivity hydroxyl group and siloxane group may be used. For example, the carrier may include at least one selected from the group consisting of silica, alumina, zeolite and magnesia. Specifically, silica dried at high temperature, silica-alumina, silica-magnesia, and the like may be used as the carrier, and these are typically oxides such _{as Na 2} O, K ₂ CO ₃ , BaSO ₄ , and Mg(NO ₃ ) _{2 .} , carbonate, sulfate, and nitrate components. They may also contain carbon, magnesium chloride, and the like. However, the carrier is not limited thereto, and is not particularly limited as long as it can support the first and second transition metal compounds and the promoter compound.

The carrier may have an average particle size of 10 to 250 μm, preferably an average particle size of 10 to 150 μm, and more preferably 20 to 100 μm.

The micropore volume of the carrier may be 0.1-10 cc/g, preferably 0.5-5 cc/g, and more preferably 1.0-3.0 cc/g.

The specific surface area of the carrier may be 1 to 1,000 m2/g, preferably 100 to 800 m2/g, and more preferably 200 to 600 m2/g.

In a preferred embodiment, when the carrier is silica, the silica drying temperature may be room temperature ~ 900 ℃. The drying temperature may be preferably from room temperature to 800°C, more preferably from room temperature to 700°C. When the drying temperature is lower than room temperature, there is too much moisture, so that the surface moisture and the cocatalyst react, and when it exceeds 900° C., the structure of the carrier may collapse.

The concentration of hydroxyl groups in the dried silica may be 0.1-5 mmole/g, preferably 0.7-4 mmole/g, and more preferably 1.0-2 mmole/g. When the concentration of the hydroxyl group is less than 0.1 mmole/g, the supported amount of the cocatalyst is lowered, and when it exceeds 5 mmole/g, a problem in that the catalyst component is deactivated may occur.

The process of supporting the transition metal compound on the carrier in step (2) above may be performed in the presence of a solvent. At this time, the solvent is substantially the same as described in step (1) above.

The process of supporting the transition metal compound on the carrier in step (2) may be carried out at a temperature of 0 to 100 °C, preferably at a temperature of room temperature to 90 °C.

In addition, the process of supporting the transition metal compound on the carrier in step (2) may be performed by sufficiently stirring the mixture of the transition metal compound and the carrier for 1 minute to 24 hours, preferably 5 minutes to 15 hours.

Preferably, the transition metal compound, the first cocatalyst compound and the second cocatalyst compound may be supported on a single type of carrier. Specifically, the transition metal compound, the first promoter compound, and the second promoter compound may be supported on silica.

In this case, the amount of the transition metal compound supported on the carrier may be 0.01 to 3.0 wt % based on the total weight of the supported catalyst, and the total amount of the cocatalyst compound supported on the carrier is 1 to 50 wt % based on the total weight of the supported catalyst. can

In the method for preparing a supported metallocene catalyst for olefin polymerization according to an embodiment of the present invention, the order of activation of the transition metal compound and the supporting sequence of the transition metal compound is not particularly limited. That is, as a specific embodiment, after the transition metal compound is activated by adding the first promoter compound and the second promoter compound to the transition metal compound, the transition metal compound may be supported on the carrier. Alternatively, the transition metal compound may be activated by first supporting the transition metal compound on a carrier, and then adding the first cocatalyst compound and the second cocatalyst compound thereto.

Meanwhile, the method for preparing a supported metallocene catalyst for olefin polymerization according to an embodiment of the present invention may further include washing the supported catalyst with a solvent and drying the supported catalyst.

Specifically, the supported catalyst obtained by supporting the transition metal compound on the carrier is allowed to stand for 3 minutes to 3 hours to precipitate the supported catalyst. Then, the supported catalyst is separated by removing the supernatant, washed with a solvent, and dried at a temperature of room temperature to 80° C. for 6 to 48 hours to obtain a supported catalyst. Here, the solvent is substantially the same as described in step (1) above.

According to another embodiment of the present invention, there is provided a metallocene-supported catalyst for olefin polymerization obtained through the above preparation method. Specifically, the metallocene supported catalyst for olefin polymerization according to another embodiment of the present invention may include any one of the transition metal compounds represented by Chemical Formulas 1 and 2 below; a first cocatalyst compound and a second cocatalyst compound; and a carrier, wherein the first cocatalyst compound is at least one selected from the group consisting of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and butylaluminoxane, and the second cocatalyst compound This is tris(pentafluorophenyl)borane, and the molar ratio of the second promoter compound to the first promoter compound is 0.001 or more and less than 0.07.

[Formula 1]

[Formula 2]

In Formulas 1 and 2, n, o, m, l, M, X, Q, R ¹ to R ⁷ are as defined in the above section on the method for preparing a supported metallocene catalyst for olefin polymerization. In addition, the contents of the first co-catalyst compound, the second co-catalyst compound, and the carrier are substantially the same as those described in the section on the method for preparing a supported metallocene catalyst for olefin polymerization.

According to another embodiment of the present invention, there is provided an olefin-based polymer obtained by polymerizing an olefin-based monomer in the presence of a metallocene-supported catalyst for olefin polymerization. The olefin-based polymer produced in the presence of a metallocene-supported catalyst for olefin polymerization according to an embodiment of the present invention has a weight average molecular weight of 2,000 to 1,000,000 g/mole. Preferably, the weight average molecular weight may be 10,000 to 500,000 g/mole, 50,000 to 100,000 g/mole, 60,000 to 90,000 g/mole, or 60,000 to 80,000 g/mole.

The olefin-based polymer produced in the presence of a metallocene-supported catalyst for olefin polymerization according to an embodiment of the present invention has a Z average molecular weight of 100,000 to 10,000,000 g/mole. Preferably, the Z average molecular weight may be 200,000 to 5,000,000 g/mole, 300,000 to 1,000,000 g/mole, 500,000 to 900,000 g/mole, or 300,000 to 800,000 g/mole.

The olefin-based polymer produced in the presence of a metallocene-supported catalyst for olefin polymerization according to an embodiment of the present invention has a Z average molecular weight to a weight average molecular weight ratio (Mz/Mw) of 1.5 to 50.0. Preferably, the ratio of the Z average molecular weight to the weight average molecular weight (Mz/Mw) may be 2.0-40.0, 2.5-30.0, 3.0-25.0, or 3.0-20.0.

In addition, the olefin-based polymer produced in the presence of a supported metallocene catalyst for olefin polymerization according to an embodiment of the present invention has a density of 0.88 to 0.95 g/cm 3 . Preferably, the density may be 0.90-0.95 g/cm 3 or 0.92-0.95 g/cm 3 .

Here, the olefin-based polymer may be a homopolymer of an olefin-based monomer or a copolymer of an olefin-based monomer and a comonomer.

The olefinic monomer is an alpha-olefin having 2 to 20 carbon atoms, a diolefin having 1 to 20 carbon atoms, a cycloolefin having 3 to 20 carbon atoms, and a cyclodiolefin having 3 to 20 carbon atoms. ) at least one selected from the group consisting of.

For example, the olefinic monomer is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1 - may be dodecene, 1-tetradecene, or 1-hexadecene, and the olefinic polymer may be a homopolymer including only one type of the olefinic monomer exemplified above, or a copolymer including two or more types.

In an exemplary embodiment, the olefin-based polymer may be a copolymer of an olefin-based monomer and an olefin-based comonomer. Specifically, the olefin-based polymer may be a copolymer in which ethylene and an alpha-olefin comonomer having 3 to 20 carbon atoms are copolymerized. More specifically, the olefinic monomer is ethylene, and the alpha-olefinic comonomer is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1- It may be at least one selected from the group consisting of decene, 1-undecene, 1-dodecene, 1-tetradecene and 1-hexadecene.

Preferably, the olefinic polymer may be, but is not limited to, a linear low density polyethylene in which the olefinic monomer is ethylene and the olefinic comonomer is 1-hexene.

In this case, it is preferable that the content of ethylene is 55 to 99.9 weight%, and it is more preferable that it is 90 to 99.9 weight%. The content of the alpha-olefin-based comonomer is preferably 0.1 to 45 wt%, more preferably 0.1 to 30 wt%.

The olefin-based polymer according to an embodiment of the present invention may be polymerized by, for example, a polymerization reaction such as free radical, cationic, coordination, condensation, and addition. However, it is not limited thereto.

In a preferred embodiment, the olefin-based polymer may be prepared by a gas phase polymerization method, a solution polymerization method, or a slurry polymerization method. When the olefin-based polymer is prepared by solution polymerization or slurry polymerization, examples of the solvent that can be used include aliphatic hydrocarbon solvents having 5 to 12 carbon atoms such as pentane, hexane, heptane, nonane, decane, and isomers thereof; aromatic hydrocarbon solvents such as toluene and benzene; and mixtures thereof, but is not limited thereto.

Example

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

comparative example One

36 mg of a transition metal compound of Formula 2-1 was added to a glass glass jar, and 5.59 g (Al/Zr = 200) of a 10 wt% toluene solution of methylaluminoxane (MAO) was added thereto, followed by stirring at room temperature for 1 hour. . On the other hand, 1.41 g (13 wt% of Al) of silica (XPO2402, Grace Davison) was added to a 100 ml glass reactor, 50 ml of purified toluene was added, and the solution of the transition metal compound obtained above was added, and at 75 ° C. Stirred for 3 hours. After precipitating the supported catalyst at room temperature, all of the supernatant was removed and washed twice with 30 ml of toluene. The washed supported catalyst was dried in vacuum at room temperature for 30 minutes to obtain a supported catalyst in the form of a free-flowing powder.

Example One

100 mg of tris(pentafluorophenyl)borane (B1) was added to a glass glass, and 5.59 g of a 10 wt% toluene solution of methylaluminoxane (MAO) was added (B1/MAO = 0.02), and then at room temperature for about 1 minute stirred for a while. Then, 36 mg of the transition metal compound of Formula 2-1 was added and stirred at room temperature for 1 hour. Meanwhile, 1.41 g of silica (XPO2402, Grace Davison) was added to a 100 ml glass reactor, and 50 ml of purified toluene was added. The solution of the transition metal compound obtained above was added to the silica slurry and stirred at 75° C. for 3 hours. After precipitating the supported catalyst at room temperature, all of the supernatant was removed and washed twice with 30 ml of toluene. The washed supported catalyst was dried in vacuum at room temperature for 30 minutes to obtain a supported catalyst in the form of a free-flowing powder.

Example 2

A supported catalyst was obtained in the same manner as in Example 1, except that 197 mg of tris(pentafluorophenyl)borane (B1) (B1/MAO = 0.04) was used.

Example 3

100 mg of tris (pentafluorophenyl) borane (B1) was added to a glass glass jar, and 5.59 g of a 10 wt% toluene solution of methylaluminoxane (MAO) (B1/MAO = 0.02) was added thereto, followed by 14 hours at 60 ° C. stirred. After the solution was cooled to room temperature, 36 mg of the transition metal compound of Formula 2-1 was added and stirred for 1 minute. Meanwhile, 1.41 g of silica (XPO2402, Grace Davison) was added to a 100 ml glass reactor, and 50 ml of purified toluene was added. The solution of the transition metal compound obtained above was added to the silica slurry and stirred at 75° C. for 3 hours. After precipitating the supported catalyst at room temperature, all of the supernatant was removed and washed twice with 30 ml of toluene. The washed supported catalyst was dried in vacuum at room temperature for 30 minutes to obtain a supported catalyst in the form of a free-flowing powder.

comparative example 2

A supported catalyst was obtained in the same manner as in Example 1, except that 345 mg of tris(pentafluorophenyl)borane (B1) (B1/MAO = 0.07) was used.

comparative example 3

N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (B2) 77 mg (B2/MAO = 0.01) instead of tris(pentafluorophenyl)borane A supported catalyst was obtained in the same manner as in Example 1, except that

comparative example 4

A supported catalyst was obtained in the same manner as in Comparative Example 1, except that 43 mg (Al/Zr = 100) of the transition metal compound of Formula 1-1 was used instead of the transition metal compound of Formula 2-1.

Example 4

43 mg (Al/Zr = 100) of the transition metal compound of Formula 1-1 was used instead of the transition metal compound of Formula 2-1, and tris(pentafluorophenyl)borane (B1) 197 mg (B1/MAO) = 0.04), except that a supported catalyst was obtained in the same manner as in Example 1.

comparative example 5

43 mg (Al/Zr = 100) of the transition metal compound of Formula 1-1 was used instead of the transition metal compound of Formula 2-1, and N,N-dimethylanilinium instead of tris(pentafluorophenyl)borane A supported catalyst was obtained in the same manner as in Example 1, except that 77 mg of tetrakis(pentafluorophenyl)borate (B2) (B2/MAO = 0.01) was used.

Experimental example

Polyolefin was polymerized in an autoclave reactor using each supported catalyst obtained in Examples 1 to 4 and Comparative Examples 1 to 5. Specifically, in the presence of 30 mg of the transition metal compound supported catalyst of Formula 2-1 or 50 mg of the transition metal compound supported catalyst of Formula 1-1 and 0.5 ml of 1M triisobutyl aluminum (TIBAL) as a scavenger, respectively, ethylene and 1 -Hexene was copolymerized for 1 hour. The temperature in the reactor was maintained at about 80° C., and the polymerization degree of the ethylene/1-hexene copolymer prepared by adding hydrogen in addition to ethylene and 1-hexene was controlled. The pressure of ethylene was 14 kgf/cm 2 , and the amount of 1-hexene and the initial and additional injection amounts of hydrogen are as shown in Table 1 below.

transition metal compounds Second cocatalyst compound (B) B/MAO
(molar ratio) catalytic activity
(gPE/gCat-hr) 1-hexene
(ml) Hydrogen Early
(ml) Add
(ml/min) Comparative Example 1 2-1 - 0 4,933 20 100 10 Example 1 2-1 B1 0.02 4,300 20 100 10 Example 2 2-1 B1 0.04 5,633 20 100 10 Example 3 2-1 B1 0.04 5,233 20 100 10 Comparative Example 2 2-1 B1 0.07 fouling 20 100 10 Comparative Example 3 2-1 B2 0.01 fouling 20 100 10 Comparative Example 4 1-1 - 0 1,840 15 0 One Example 4 1-1 B1 0.04 2020 15 0 One Comparative Example 5 1-1 B2 0.01 fouling 15 0 0

The physical properties of the olefin-based polymers prepared using each supported catalyst obtained in Examples 1 to 4 and Comparative Examples 1 to 5 were measured as follows. The measurement results are shown in Table 2 and FIG. 1 below.

(1) melt flow ratio (MFR)

According to ASTM D 1238, the melt index was measured at 190° C. under a load of 2.16 kg and a load of 21.6 kg, and the ratio (MI _21.6 /MI _2.16 ) was obtained.

(2) molecular weight and molecular weight distribution

It was measured using gel permeation chromatography-3D (GPC-3D) under 160°C trichlorobenzene solution.

(3) modulus of elasticity

The storage modulus and loss modulus were measured using MCR702 (Anton Parr) in a frequency range of 0.1 to 500 rad/s and a strain condition of 5% at 190°C.

MFR Density (g/cm3) Mn Mw Mz Mz/Mw Comparative Example 1 26.7 0.935 23,036 72,873 217,483 2.98 Example 1 26.2 0.935 10,522 65,200 350,372 5.37 Example 2 25.1 0.937 20,309 73,681 664,614 9.02 Example 3 26.2 0.936 18,554 81,802 824,393 10.08 Comparative Example 2 - - - - - - Comparative Example 3 - - - - - - Comparative Example 4 21.0 0.941 36,573 99,867 221,065 2.21 Example 4 19.0 0.940 30,650 109,872 720,973 6.56 Comparative Example 5 - - - - - -

Comparing Examples 1 to 3 and Comparative Example 1 according to an embodiment of the present invention, in the case of Examples 1 to 3, the Mz/Mw of the produced olefin-based polymer is significantly increased compared to Comparative Example 1, and strength and viscosity and increased elasticity. The molecular weight distribution of the olefin-based polymer obtained in Examples 1 to 3 is as shown in FIG. 1 . In addition, comparing Example 4 and Comparative Example 4, in the case of Example 4, the Mz/Mw of the produced olefin-based polymer was significantly increased compared to Comparative Example 4, and strength, viscosity, and elasticity were increased.

In particular, when comparing the elastic modulus of Comparative Example 1 and Example 2, it is confirmed that the value of Example 2 is significantly increased compared to Comparative Example 1 (see FIG. 2).

On the other hand, in Comparative Example 2, the molar ratio of tris(pentafluorophenyl)borane, which is the second cocatalyst compound, was 0.07 or more, which was out of the scope of the present invention, fouling occurred in the reactor. In addition, in Comparative Examples 3 and 5 in which N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate was used instead of tris(pentafluorophenyl)borane as the second cocatalyst compound, fouling occurred in the reactor did.

The supported catalyst prepared according to the preparation method of the embodiment of the present invention can improve physical properties such as strength, viscosity and elasticity by increasing Mw without significantly changing other physical properties during olefin polymerization.

Claims (14)

(1) activating any one of the transition metal compounds represented by Chemical Formulas 1 and 2 below with a first cocatalyst compound and a second cocatalyst compound; and (2) supporting a transition metal compound on a carrier, wherein the second promoter compound is tris (pentafluorophenyl) borane, and the second promoter compound to the first promoter Method for producing a metallocene-supported catalyst for olefin polymerization, wherein the molar ratio of the compound is 0.001 or more and less than 0.07
[Formula 1]

[Formula 2]

In the above formulas 1 and 2, n and o are each an integer of 0-5, m and l are each an integer of 0-4,
M is titanium (Ti), zirconium (Zr) or hafnium (Hf),
each X is independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkylamido, or C _6-20 arylamido;
Q is carbon (C), silicon (Si), germanium (Ge) or tin (Sn),
R ¹ to R ⁵ are each independently substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _{1 -20} alkyl C _6-20 aryl, substituted or unsubstituted C _6-20 aryl C _1-20 alkyl, substituted or unsubstituted C _1-20 heteroalkyl, substituted or unsubstituted C _3-20 heteroaryl, substituted or unsubstituted C _1-20 alkylamido, substituted or unsubstituted C _6-20 arylamido, or substituted or unsubstituted C _1-20 silyl, wherein R ¹ to R ⁵ are each independently an adjacent group. may be linked to form a substituted or unsubstituted saturated or unsaturated C _4-20 ring,
R ⁶ and R ⁷ are each independently substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _{1 -20} alkyl C _6-20 aryl, substituted or unsubstituted C _6-20 aryl C _1-20 alkyl, substituted or unsubstituted C _1-20 heteroalkyl, substituted or unsubstituted C _3-20 heteroaryl, substituted or unsubstituted C _1-20 alkylamido, substituted or unsubstituted C _6-20 arylamido, or substituted or unsubstituted C _1-20 silyl. The method of claim 1, wherein in Formulas 1 and 2, n and o are each an integer of 1 to 3, m and l are each an integer of 1 to 2, X is each independently a halogen or a methyl group, and M is zirconium. or hafnium, Q is carbon, R ¹ to R ⁵ are each C _1-20 alkyl, and R ⁶ and R ⁷ are each C _6-20 aryl. A method for preparing a supported metallocene catalyst for olefin polymerization. The method according to claim 2, wherein the transition metal compounds of Chemical Formulas 1 and 2 are compounds represented by Chemical Formulas 1-1 and 2-1 below, respectively, the method for preparing a supported metallocene catalyst for olefin polymerization:
[Formula 1-1]

[Formula 1-2]

. The method of claim 1, wherein the first cocatalyst compound comprises at least one of the compounds represented by Formula 3 below:
[Formula 3]

In Formula 3, n is an integer of 2 or more, and R _a is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen. 5. The method of claim 4, wherein the compound represented by Formula 3 consists of methyl aluminoxane (MAO), modified methyl aluminoxane (MMAO), ethyl aluminoxane, isobutyl aluminoxane and butyl aluminoxane. A method for preparing a supported metallocene catalyst for olefin polymerization, which is at least one selected from the group consisting of: The method of claim 1, wherein the carrier comprises at least one selected from the group consisting of silica, alumina, zeolite and magnesia. The method according to claim 6, wherein the transition metal compound, the first cocatalyst compound, and the second cocatalyst compound are supported on a single type of carrier. The method according to claim 7, wherein the transition metal compound, the first cocatalyst compound, and the second cocatalyst compound are supported on silica. The method according to claim 7, wherein the amount of the transition metal compound supported on the carrier is 0.01 to 3.0% by weight based on the total weight of the supported catalyst, and the total amount of the promoter compound supported on the carrier is 1 to 50 based on the total weight of the supported catalyst. A method for preparing a metallocene-supported catalyst for olefin polymerization in wt%. any one of the transition metal compounds represented by Formula 1 and Formula 2 below; a first cocatalyst compound and a second cocatalyst compound; and a carrier, wherein the first cocatalyst compound is at least one selected from the group consisting of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and butylaluminoxane, and the second cocatalyst compound This is tris(pentafluorophenyl)borane, wherein the molar ratio of the second promoter compound to the first promoter compound is 0.001 or more and less than 0.07 supported metallocene catalyst for olefin polymerization:
[Formula 1]

[Formula 2]

In Formulas 1 and 2, n, o, m, l, M, X, Q, R ¹ to R ⁷ are as defined in claim 1. A method for producing an olefin-based polymer comprising the step of polymerizing an olefin-based monomer in the presence of the catalyst for olefin polymerization of claim 10, wherein the olefin-based polymer has a density of 0.88 to 0.95 g/cm 3 and a weight average molecular weight of 2,000 to 1,000,000 g /mole, the Z-average molecular weight is 100,000 to 10,000,000 g/mole, and the ratio of the Z-average molecular weight to the weight-average molecular weight (Mz/Mw) is 1.5 to 50.0. The method according to claim 11, wherein the olefinic polymer is a copolymer of an olefinic monomer and an alpha-olefinic comonomer. 13. The method of claim 12, wherein the olefinic monomer is ethylene and the alpha-olefinic comonomer is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene; A method for producing at least one olefinic polymer selected from the group consisting of 1-decene, 1-undecene, 1-dodecene, 1-tetradecene and 1-hexadecene. 14. The method according to claim 13, wherein the olefinic polymer is a linear low density polyethylene wherein the olefinic monomer is ethylene and the alpha-olefinic comonomer is 1-hexene.

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