KR101848365B1

KR101848365B1 - Polyolefine, method for manufacturing the same and metallocene catalyst for manufacturing the same

Info

Publication number: KR101848365B1
Application number: KR1020160028880A
Authority: KR
Inventors: 이인준; 정의갑; 장준호; 김라연; 박혜란; 사공길; 윤성철
Original assignee: 한화케미칼 주식회사
Priority date: 2016-03-10
Filing date: 2016-03-10
Publication date: 2018-04-12
Also published as: KR20170105789A

Abstract

The invention relates to an olefin polymer comprising lamellas having an average thickness of at least 10 nm and not more than 100 nm, to a process for their preparation and to metallocene catalysts for use in the preparation thereof.

Description

POLYOLEFINE, METHOD FOR MANUFACTURING THE SAME AND METALLOCENE CATALYST FOR MANUFACTURING THE SAME Technical Field The present invention relates to a metallocene catalyst for olefin polymerization,

The invention relates to olefin polymers, processes for their preparation and metallocene catalysts for their preparation.

The metallocene compound is a compound in which a ligand such as a cyclopentadienyl group (Cp), an indenyl group, or a cycloheptadienyl group is coordinated to a transition metal or a transition metal halogen compound As a basic form of the sandwich structure.

The metallocene catalyst is a single-site catalyst comprising the metallocene compound as the main catalyst and a promoter such as methylaluminoxane. The metallocene catalyst is a single-site catalyst, The polymerized polymer has a narrow molecular weight distribution, a uniform distribution of comonomers, and a higher copolymerization activity than the Ziegler-Natta catalyst.

Depending on the structure of the ligand, the metallocene catalyst may have a different stereoregularity even when the same monomer is used.

Embodiments of the present invention seek to provide an olefin polymer having excellent thermal stability.

The olefin polymer according to one embodiment of the invention comprises a lamellar having an average thickness of 10 nm to 100 nm. The olefin polymer may have a lamellar thickness distribution index of 1.10 to 3.00. Preferably, the olefin polymer may have a lamellar thickness distribution index ranging from 1.40 to 3.00.

The process for producing an olefin polymer according to another embodiment of the present invention comprises reacting at least one of the metallocene compounds represented by the following formulas M1 to M2 with at least one of the promoter compounds represented by the following formulas AC1-1 to AC2-1 In the presence of a metallocene catalyst, which comprises the olefinic monomers.

Wherein M is one of titanium (Ti), zirconium (Zr) and hafnium (Hf), A is nitrogen or oxygen, Q is at least one element selected from the group consisting of carbon (C), silicon (Si), germanium (Sn). In Formula (M1), X- * are each independently any one of a halogen group, a C _1-10 alkyl group and a C _2-10 alkenyl group, and R ₁ -, R ₂ -, R ₃ -, R ₄ - _{*, R 5 - *, R} 6 - *, R 7 - *, R 8 - *, R 9 - *, R 10 - * and R ₁₁ - * are each independently a hydrogen group (H- *), C _{1 A} C _3-6 cycloalkyl group, and a C _6-14 aryl group.

&Lt; Formula (M2)

M is one of titanium (Ti), zirconium (Zr) and hafnium (Hf), A is nitrogen or oxygen, Q is carbon (C), silicon (Si), germanium (Sn). In formula (M2), X '- are each independently any one of a halogen group, a C _1-10 alkyl group and a C _2-10 alkenyl group, and R' ₁ -, R ' ₂ -, R' ₃ - _{, R '4 - *, R} ' 5 - *, R '6 - *, R' 7 - *, R '8 - *, R' 9 - *, R '10 - * and R' ₁₁ - * are each Is independently one of a hydrogen group (H- *), a C _1-20 alkyl group, a C _3-6 cycloalkyl group, and a C _6-14 aryl group.

<AC1-1>

In Formula AC1-1, N is nitrogen, and H is ^{hydrogen, R 1 - *, R 2} - *, R 3 - * are each independently a hydrogen group (* H-), substituted or unsubstituted C _{1 A} substituted or unsubstituted C _2-20 alkyl group, a substituted or unsubstituted C _2-20 alkenyl group, a substituted or unsubstituted C _6-20 aryl group, a substituted or unsubstituted C _7-40 alkylaryl group and a substituted or unsubstituted C _7-40 Y is one of boron (B), aluminum (Al), gallium (Ga) and indium (In), R ⁴ - is a C _6-20 aryl group substituted or unsubstituted with halogen And a C _1-20 alkyl group substituted or unsubstituted with halogen.

<AC2-1>

In the above formula (AC2-1), N is nitrogen and each of R ¹ -, R ² -, R ³ -, and R ⁵ - is independently a hydrogen group (H- *), a substituted or unsubstituted C _{1 -} ₂₀ alkyl group, a substituted or unsubstituted C _2-20 alkenyl group, a substituted or unsubstituted C _6- ₂₀ aryl group, a substituted or unsubstituted C _7-40 alkylaryl group, a substituted or unsubstituted C _7-40 Y is one of boron (B), aluminum (Al), gallium (Ga) and indium (In), R ⁴ - is a C _6-20 aryl group substituted with halogen, Or a substituted or unsubstituted C _1-20 alkyl group.

The metallocene catalyst according to another embodiment of the present invention is a metallocene catalyst in which at least one of the metallocene compounds represented by the above formulas M1 to M2 and at least two of the catalyst compounds represented by the above formulas AC1-1 to AC2-1 .

According to embodiments of the invention, olefin polymers having excellent thermal stability can be provided.

The effects according to the present invention are not limited by the contents exemplified above, and more various effects are included in the specification.

1 shows a lamellar thickness distribution graph of the olefin polymer of the first embodiment.
Figs. 2 and 3 show graphs comparing the lamellar thickness distribution of the olefin polymer of Example 1 and the olefin polymer of Comparative Example 1. Fig.
FIG. 4 shows an enlarged graph of the lamellar thickness distribution of 10 nm or more in the graph of FIG.
5 shows a graph of the lamellar thickness distribution of an olefin polymer according to the second embodiment.
Figs. 6 and 7 show graphs comparing the lamellar thickness distribution of the olefin polymer of Example 2 and the olefin polymer of Comparative Example 2. Fig.
FIG. 8 shows a graph enlarging the lamellar thickness distribution of 10 nm or more in the graph of FIG. 5; FIG.
9 shows a graph of the lamellar thickness distribution of the olefin polymer of the third embodiment.
Figs. 10 and 11 show graphs comparing the lamellar thickness distribution of the olefin polymer of Example 3 and the olefin polymer of Comparative Example 3. Fig.
Fig. 12 shows an enlarged graph of the lamellar thickness distribution of 10 nm or more in the graph of Fig.

Advantages and features of the present invention and methods of achieving them will become apparent with reference to the embodiments described in detail below. The present invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Is provided to fully convey the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.

Although the first, second, etc. are used to describe various components, it goes without saying that these components are not limited by these terms. These terms are used only to distinguish one component from another.

In the present specification, "C _AB " is defined as a hydrocarbon group or a hydrocarbon derivative group whose carbon number is A or more and B or less, and "A to B" In this specification, "*" means a binding site.

As used herein, "substituted" in the "substituted or unsubstituted" means "a halogen group at least one hydrogen of the hydrocarbon compound or a hydrocarbon derivatives, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl carbonyl, C _6-20 aryl, C _1-20 alkyl, C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkyl, amido, C _6-20 aryl or C _1-20 amido substituted with alkylidene "means, and" unsubstituted "means" at least one hydrogen of the hydrocarbon compound or a hydrocarbon derivative 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 Quot; means < / RTI > not substituted "

The olefin polymer according to one embodiment of the invention comprises a lamella having an average thickness of 10 nm to 100 nm. Specifically, the olefin polymer has an average thickness of 10 nm to 50 nm, and the lamellar content is 0.10% to 1.99% based on the total lamellas. Further, the olefin polymer has an average thickness of 50 nm to 100 nm, and the lamellar content is 0.00 to 0.01% based on the total lamellas. Further, the olefin polymer has 98.00% to 99.90% of the total lamellar lamellas having an average thickness of more than 0 nm and less than 10 nm.

The olefin polymer may have a lamellar thickness distribution index of 1.10 to 3.00. Preferably, the olefin polymer may have a lamellar thickness distribution index ranging from 1.40 to 3.00. More preferably, the olefin polymer may have a lamellar thickness distribution index of from 1.70 to 3.00.

The olefin polymer preferably has a density of 0.860 g / cm < ³ > To 0.910 g / cm < ³ >. The olefin polymer may have a weight average molecular weight of 60,000 g / mol to 250,000 g / mol. The olefin polymer may have a molecular weight distribution index of 2 to 3. The olefin polymer may have a crystallinity of 20.0 to 45.0. The olefin polymer may have a C ₈ mol% of 3.5 to 12.7.

The olefin polymer may have a melting temperature (Tm) of from 50 캜 to 110 캜. Preferably, the olefin polymer may have a melting temperature (Tm) of from 72 캜 to 110 캜.

In one example, the olefin polymer has a melt index (MI) at 190 ℃ to be 0.9 g / 10 min to 1.1 g / 10 min, and C ₈ mol% to 9.3 is less than the melting temperature (Tm) 65.0 ℃ And the crystallinity may be at least 25.0.

In another example, the olefin polymer, melt index (MI) is 0.4 g / 10 min to 0.6 g / 10 min may be a density of 0.861 g / cm ³ at 190 ℃ To 0.867 g / cm < ³ >, C ₈ mol% may be less than 10.8, the melting temperature (Tm) may be 51.0 DEG C or higher, and the crystallinity may be 20.0 or higher.

In yet another example, the olefin polymer has a melt index (MI) at 190 ℃ may be 0.90 g / 10 min to 1.10 g / 10 min, a density of 0.900 g / cm ³ To be 0.904 g / cm ^3, and has a melting temperature (Tm) greater than or equal to 99.0 ℃, C ₈ mol% and be less than 4.1, the degree of crystallization can be 39.0 or greater.

The olefin polymer can be prepared by polymerizing olefin monomers in the presence of a metallocene-based catalyst, which is a main catalyst, and a metallocene catalyst, which contains a promoter compound for promoting the activity of the metallocene-based compound.

The metallocene compound may be any one of a metallocene, a half-metallocene, and a post-metallocene. The metallocene compound may be at least one of the compounds represented by the following formulas M1 to M2, for example.

M may be one of titanium (Ti), zirconium (Zr), and hafnium (Hf), A may be nitrogen or oxygen, Q may be carbon (C), silicon (Si), germanium Ge) and tin (Sn). In formula (M1), X- may each independently be any one of a halogen group, a C _1-10 alkyl group and a C _2-10 alkenyl group, and R ₁ -, R ₂ -, R ₃ -, R _{4 - *, R 5 - *} , R 6 - *, R 7 - *, R 8 - *, R 9 - *, R 10 - * and R ₁₁ - * is a hydrogen group (* H-), each independently, A C _1-20 alkyl group, a C _3-6 cycloalkyl group, and a C _6-14 aryl group. Wherein R ₁ -, R ₂ -, R ₃ -, R ₄ -, R ₅ -, R ₆ -, R ₇ -, R ₈ -, R ₉ - *, R ₁₀ - *, and R ₁₁ - * may be the same or different. The X- * is desorbed as anions by the co-catalyst compound to cause the center metal (titanium (Ti), zirconium (Zr) and hafnium (Hf)) to become cations.

&Lt; Formula (M2)

M may be one of titanium (Ti), zirconium (Zr) and hafnium (Hf), A may be nitrogen or oxygen and Q may be carbon (C), silicon (Si), germanium Ge) and tin (Sn). In formula M2, X '- * may be either each independently halogen, C _1-10 alkyl and C _2-10 alkenyl _{group, R' 1 - *, R} '2 - *, R' 3 _{- *, R '4 - *} , R' 5 - *, R '6 - *, R' 7 - *, R '8 - *, R' 9 - *, R '10 - * and R' ₁₁ - * Each independently may be one of a hydrogen group (H- *), a C _1-20 alkyl group, a C _3-6 cycloalkyl group, and a C _6-14 aryl group. Wherein R _'1 - *, wherein R' ₂ - *, wherein R _'3 - *, wherein R' ₄ - *, wherein R _'5 - *, wherein R' ₆ - *, wherein R _'7 - *, the R ' ₈ - *, R' ₉ - *, R _'10 - * R' ₁₁ - * may be the same or different. The X '- * is desorbed as an anion by the co-catalyst compound so that the center metal (titanium (Ti), zirconium (Zr) and hafnium (Hf)) becomes a cation.

Examples of the compounds represented by the above formulas M1 to M2 include compounds represented by the following formulas EX1 to EX15. May be - are, each independently, any one of a halogen group, C _1-10 alkyl and C _2-10 alkenyl group-EX1 to EX15 to the formula, X- * and X '.

&Lt; Formula EX1 > < Formula EX2 > < Formula EX3 &

&Lt; Chemical Formula EX4 > < Chemical Formula EX5 &

&Lt; General Formula EX7 > < General Formula EX8 > < General Formula EX9 &

&Lt; General Formula EX10 > < General Formula EX11 > < General Formula EX12 &

The cocatalyst compound may be at least one of the compounds represented by the following formulas AC1 to AC4. In the above formulas AC1 to AC4, each of L, H, Z, A, Al, Ra, O, n, D, Rb, Rc and Rd will be described in detail below.

&Lt; Formula AC1 &

&Lt; Formula AC2 &

&Lt; Formula AC3 &

<AC4>

For example, the promoter compound may be one of the compounds represented by the formula AC1, or may be one of the compounds represented by the formula AC2 (hereinafter referred to as "first example"). , For example, the above-described co-catalyst compound may be a mixture in which two or more of the compounds represented by the above formula (AC1) are mixed in an inert atmosphere of nitrogen or argon, or two or more of the compounds represented by the above formula (AC2) Or an inert atmosphere of argon, or at least one of the compounds represented by the formula AC1 and the compounds represented by the formula AC2 may be a mixture mixed under an inert atmosphere of nitrogen or argon (Hereinafter referred to as "second example").

In the second example, the mixing process may be performed in a liquid mixing manner at a temperature of 0 ° C to 100 ° C, respectively, or may be performed in a solid-phase mixing manner. For example, the mixing process may be performed at a temperature of 10 ° C to 30 ° C May be performed in a mixed manner or may be performed in a solid-phase mixed manner. The liquid phase mixing method is to uniformly dissolve the compounds in an organic solvent and then mix them in a solution state, and the solid phase mixing method is to mix the compounds in a solid powder state.

In the above formulas AC1 and AC2, as the number of carbon atoms increases, the compounds represented by the formulas AC1 to AC2 increase the solubility in organic solvents and the like and decrease the activity of the promoter compound to increase the average thickness of the lamellar. The heat resistance tends to increase. However, in the above formulas AC1 and AC2, as the number of carbon atoms decreases, the compounds represented by the above formulas AC1 to AC2 decrease in solubility in an organic solvent and the like, and the activity of the promoter compound increases, Polymers tend to have reduced heat resistance. Accordingly, in the case of the first example, the melting point of the olefin polymer is lowered, and in the case of the second example, the microstructure of the olefin polymer is changed to increase the melting point and improve the heat resistance. Therefore, it is preferable that the second example is used as the co-catalyst compound.

In the second example, in the case of a heterogeneous mixture of compound I and compound II, the content of compound I may be from 50 wt% to 80 wt%, and the content of compound II may be from 20 wt% to 50 wt% have. When the content of the compound I is higher than the content of the compound II, the compound I may have a carbon number greater than that of the compound II.

If the content of the compound I exceeds 80% by weight, the olefin polymer is excellent in heat resistance, but the activity of the metallocene catalyst is lowered and is not economical. If the content of the compound I is less than 50% by weight, the activity of the metallocene catalyst increases The heat resistance of the olefin polymer is lowered and the physical properties may be lowered. If the content of the compound II exceeds 50 wt%, the activity of the metallocene catalyst increases, but the heat resistance of the olefin polymer lowers and the physical properties thereof deteriorate. If the content of the compound II is less than 20 wt%, the activity of the metallocene catalyst Is not economical. Thus, for example, the content of the compound I is 60 wt% to 70 wt%, and the content of the compound II is 30 wt% to 40 wt%.

In the second example, in the case of a three-component mixture of compound I, compound II and compound III, the content of the compound I may be 52 wt% to 72 wt%, and the content of the compound II may be 26 wt% to 42 wt% %, And the content of the compound III may be 2 wt% to 6 wt%. The compound I may have a larger number of carbon atoms than the compound II, and the compound II may have a larger number of carbon atoms than the compound III.

If the content of the compound I exceeds 72% by weight, the olefin polymer is excellent in heat resistance, but the activity of the metallocene catalyst is lowered and is not economical. If the content is less than 52% by weight, the activity of the metallocene catalyst is increased The heat resistance of the olefin polymer is lowered and the physical properties may be lowered. If the content of the compound II exceeds 42 wt%, the activity of the metallocene catalyst increases, but the heat resistance of the olefin polymer lowers and the physical properties decrease. When the content of the compound II is less than 26 wt%, the activity of the metallocene catalyst decreases It is not economical. If the content of the compound III exceeds 6% by weight, the activity of the metallocene catalyst increases but the heat resistance of the olefin polymer lowers and the physical properties thereof deteriorate. If the content of the compound III is less than 2% by weight, the activity of the metallocene catalyst is lowered It is not economical. Thus, for example, the content of the compound I is 60 wt% to 68 wt%, the content of the compound II is 28 wt% to 35 wt%, the content of the compound III is 4 wt% to 5 wt% .

On the other hand, for example, the promoter compound may include at least one of the compounds represented by the formulas AC1 to AC2, at least one of the compounds represented by the formula AC3, and at least one of the compounds represented by the formula AC4 Mixture. At least one of the compounds represented by the formulas AC1 to AC2 (Mol ₁ ) and at least one of the compounds represented by the formula AC3 (Mol ₂ ) and the compounds represented by the formula AC ₄ (Mol ₃ ) may be in the range of 20 to 500: 1: 1 to 5: molar ratio (Mol _1: Mol ₂ : Mol ₃ ).

&Lt; Formula AC1 &

Wherein L is a neutral or cationic Lewis acid, Z is a Group 13 element of the Periodic Table of the Elements, H is hydrogen, A is a C _6-20 aryl group substituted or unsubstituted with halogen and a substituted or unsubstituted aryl group, _{Lt; /} RTI > alkyl group.

The compound represented by the formula AC1 may be at least one of the compounds represented by the following formula (AC1-1), for example.

<AC1-1>

In Formula AC1-1, N is nitrogen, and H is ^{hydrogen, R 1 - *, R 2} - *, R 3 - * are each independently a hydrogen group (* H-), substituted or unsubstituted C _{1 A} substituted or unsubstituted C _2-20 alkyl group, a substituted or unsubstituted C _2-20 alkenyl group, a substituted or unsubstituted C _6-20 aryl group, a substituted or unsubstituted C _7-40 alkylaryl group and a substituted or unsubstituted C _7-40 Lt; / RTI > Y may be one of boron (B), aluminum (Al), gallium (Ga) and indium (In), and R ⁴ - * may be either a C _6-20 aryl group substituted with halogen or a C _1-20 alkyl group substituted or unsubstituted with halogen. The halogen group may be one of a fluorine group, a chlorine group, a bromine group and an iodine group. The compounds represented by the formula AC1-1 may exhibit excellent solubility in polymerization solvents by controlling the lengths of alkyl groups of R ¹ -, R ² -, R ³ -, alkoxy groups, and aryl groups have.

Specifically, in Formula AC1-1, R ¹ -, R ² -, and R ³ - may each independently be a C _1-20 alkyl group, wherein R ¹ - , R ² - * and R ³ - * may have the same or different carbon numbers.

The compounds represented by the formula AC1-1 may be at least one of the following compounds 1 to 6, for example. In the following compounds 1-6, C _a is defined as an alkyl group having a carbon number a.

&Lt; Compound 1 >

&Lt; Formula AC2 &

In the formula AC2, L may be a neutral or cationic Lewis acid, Z may be a Group 13 element of the Periodic Table of the Elements, A is a C _6-20 aryl group substituted or unsubstituted with halogen, _{Lt; /} RTI > alkyl group.

The compound represented by the formula AC2 may be at least one of the compounds represented by, for example, the following formula: AC2-1.

<AC2-1>

In the above formula (AC2-1), N is nitrogen and each of R ¹ -, R ² -, R ³ -, and R ⁵ - is independently a hydrogen group (H- *), a substituted or unsubstituted C _{1 -} ₂₀ alkyl group, a substituted or unsubstituted C _2-20 alkenyl group, a substituted or unsubstituted C _6- ₂₀ aryl group, a substituted or unsubstituted C _7-40 alkylaryl group, a substituted or unsubstituted C _7-40 Arylalkyl group. Y may be one of boron (B), aluminum (Al), gallium (Ga) and indium (In), and R ⁴ - * may be one of Group 13 elements of the Periodic Table of Elements. May be one of a C _6-20 aryl group substituted with halogen or a C _1-20 alkyl group substituted or unsubstituted with halogen. The halogen group may be one of a fluorine group, a chlorine group, a bromine group and an iodine group.

A compound represented by the general formula wherein R ¹ are AC2-1 - *, wherein R ² - *, wherein R ³ - * may be, each independently, C _1-20 alkyl group, and in this case, the R ¹ - * , R ² - * and R ³ - * may have the same or different carbon numbers.

The compounds represented by the formula AC2-1 may be, for example, at least one of the following compounds 7 to 16 below. In the following compounds 7 to 16, C _a is defined as an alkyl group having _{a number} of carbon atoms.

Specifically, examples of the compound represented by the general formula AC1 to AC2 include methyl dioctadecyl ammonium tetrakis (pentafluorophenyl) borate _{([HNCH 3 (C 18 H} 37) 2] + [B (C 6 F 5) ₄ ] ^- ), trimethylammonium tetrakis (phenyl) borate, triethylammonium tetrakis (phenyl) borate, tripropylammonium tetrakis (phenyl) borate, tributylammonium tetrakis (phenyl) borate, trimethylammonium tetrakis (O, p-dimethylphenyl) borate, triethylammonium tetrakis (o, p-dimethylphenyl) borate, trimethylammonium tetrakis (p-trifluoromethylphenyl) borate, tributylammonium tetrakis (ptrifluoromethylphenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, diethylammonium (Phenyl) borate, N, N-diethylanilinium tetrakis (phenyl) borate, triphenylphosphonium tetrakis (phenyl) borate, trimethylphosphonium tetrakis (Pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (p-trifluoromethylphenyl) borate, triphenylcarbamoyl (Pentafluorophenyl) borate, trimethylammonium tetrakis (phenyl) aluminate, triethylammonium tetrakis (phenyl) aluminate, tripropylammonium tetrakis (phenyl) aluminate, tributylammonium tetrakis ) Aluminate, trimethylammonium tetrakis (p-tolyl) aluminate, tripropylammonium tetrakis (p-tolyl) aluminate, triethylammonium tetra (P-dimethylphenyl) aluminate, tributylammonium tetrakis (p-trifluoromethylphenyl) aluminate, trimethylammonium tetrakis (ptrifluoromethylphenyl) aluminate, tributylammonium tetrakis N, N-diethylanilinium tetrakis (phenyl) aluminate, N, N-diethylanilinium tetrakis (phenyl) aluminate, N, N-diethylanilinium tetrakis (Pentafluorophenyl) aluminate, diethylammonium tetrakis (pentafluorophenyl) aluminate, triphenylphosphonium tetrakis (phenyl) aluminate, trimethylphosphonium tetrakis (phenyl) aluminate, triethylammonium tetrakis (Phenyl) aluminate, tributylammonium tetrakis (phenyl) aluminate, and the like, but are not limited thereto. Preferably, it is preferable to use methyl dioctadecylammonium tetrakis (pentafluorophenyl) borate ([HNMe (C ₁₈ H ₃₇ ) ₂ ] ⁺ [B (C ₆ F ₅ ) ₄ ] ^- ), N, N-dimethylanilinium tetra Kiss (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate, and the like.

&Lt; Formula AC3 &

In the formula AC3, Al is aluminum, O is oxygen, R _a - is a hydrogen atom (H- *), a halogen atom, a substituted or unsubstituted C _1-20 alkyl group, a C _3-20 cycloalkyl group, a halogen-substituted or unsubstituted C _6-40 aryl group, and a halogen-substituted or may be one of the C _6-40 alkyl aryl ring, n is an integer of two or more, for For example, an integer of 2 to 500.

The compound represented by the formula AC3 is aluminoxane, preferably C _1-20 alkylaluminoxane. Examples of the alkyl aluminoxane include, but are not limited to, methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane and the like, preferably methyl aluminoxane. The alkylaluminoxane may be prepared by adding an appropriate amount of water to trialkylaluminum or by reacting a hydrocarbon compound or inorganic hydrate salt containing water with trialkylaluminum, But commercially available alkylaluminoxanes can be purchased and used. When alkylaluminoxane is produced by a common production method, generally, linear and cyclic aluminoxanes can be obtained in a mixed form.

<AC4>

In the above formula (AC4), it may be a Group 13 metal of the Periodic Table of the Elements, for example, aluminum or boron. In the formula AC2, each of R _b - _, R _c - and R _d - is independently a hydrogen group (H- *), a halogen group, a C _1-20 alkyl group substituted or unsubstituted with a halogen, Or an unsubstituted C _3-20 cycloalkyl group, a substituted or unsubstituted C _6-40 aryl group and a substituted or unsubstituted C _6-40 alkylaryl group, and R _b, R _c and R _d may be the same or different from each other.

Non-limiting examples of the compound represented by the formula AC4 include trimethylaluminum, dimethylaluminum chloride, methoxydimethylaluminum, methylaluminum dichloride, triethylaluminum, diethylaluminum chloride, methoxydiethylaluminum, ethylaluminum dichloride, tri Propyl aluminum, diisopropyl aluminum, dipropyl aluminum chloride, propyl aluminum dichloride, triisopropyl aluminum, tributyl aluminum, triisobutyl aluminum, diisobutyl aluminum hydride, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl Aluminum, trioctyl aluminum, ethyl dimethyl aluminum, diethyl (methyl) aluminum, triphenyl aluminum, tri-p-tolyl aluminum, ethoxydimethyl aluminum, trimethyl boron, triethyl boron, triisobutyl boron, Butyl Bo , There may be mentioned such as a phenyl boronic tree pentafluoropropane.

Examples of the olefin monomers include ethylene,? -Olefin monomers, cyclic olefin monomers, diene monomers, trienes monomers, styrenes monomers, and the like.

The alpha -olefin monomers may be C _3-12 aliphatic olefins and include, for example, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, , 1-heptene, 1-octene, 1-decene, 4,4-dimethyl-1-pentene, 4,4-diethyl- -Dimethyl-1-hexene, and the like. The? -Olefin monomers may be homopolymerized, or two or more may be alternating copolymerized, random copolymerized, or block copolymerized. The copolymerization of the? -Olefin monomers may be carried out by copolymerizing ethylene and C _3-12 -olefin monomers (for example, copolymerization of ethylene and propylene, copolymerization of ethylene and 1-butene, copolymerization of ethylene and 1-hexene, And 4-methyl-1-pentene, copolymerization of ethylene and 1-octene), and copolymerization of propylene and C _4-12 alpha-olefin monomers (for example, copolymerization of propylene and 1-butene, copolymerization of propylene with 4 -Methyl-1-pentene, copolymerization of propylene and 4-methyl-1-butene, copolymerization of propylene and 1-hexene, copolymerization of propylene and 1-octene). In the copolymerization of ethylene and C _3-12 -olefin monomers and the copolymerization of propylene and C _4-12 -olefin monomers, the content of the C _3-12 -olefin monomers and the content of the C _4-12 α- The content of olefin monomers may be less than 90 mole% of the total olefin monomers, respectively. Typically, in the case of the ethylene copolymer, the content of the C _3-12 -olefin monomers may be 40 mol% or less, for example, 30 mol% or less, specifically 20 mol% or less. In the case of the propylene copolymer, The content of the C _4-12 alpha-olefin monomers may be 1 mol% to 90 mol%, preferably 5 mol% to 90 mol%, more preferably 10 mol% to 70 mol%, but is not limited thereto .

The cyclic olefin monomers may be C _3-24 cyclic olefins and include, for example, cyclopentene, cyclobutene, cyclohexene, 3-methylcyclohexene, cyclooctene, tetracyclodecene, octaclodecene, Norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene , 5,5,6-trimethyl-2-norbornene, ethylene norbornene, and the like. The cyclic olefin monomers may be copolymerized with the? -Olefin monomers, wherein the content of cyclic olefin monomers is in the range of 1 mol% to 50 mol%, such as 2 mol% to 50 mol% Lt; / RTI >

The diene monomers and triene monomers may also be C _4-26 polyenes having two or three double bonds, for example, 1,3-butadiene, 1,4-pentadiene, 1, 4-hexadiene, 1,5-hexadiene, 1,9-decadiene, 2-methyl-1,3-butadiene and the like. The styrenes monomers are, for example, C _1- ₁₀ halogenated alkyl group, a halogen group, an amine group, a silyl group such as substituted or unsubstituted styrene, C _1- ₁₀ alkyl group, may be a C _1- ₁₀ alkoxy group. Preferred examples of the olefin monomers include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, and mixtures thereof.

The promoter compound may be present in the form of a homogeneous solution in the activated state of the metallocene compound, may exist in a form supported on the carrier, or may exist in the form of an insoluble particle of the carrier. The production method can be carried out by a liquid phase polymerization reaction, a slurry phase polymerization reaction, a bulk phase polymerization reaction or a gas phase polymerization reaction. The conditions of the respective polymerization reactions can be selected depending on the state of the metallocene catalyst (homogeneous or heterogeneous phase (supported type)), polymerization method (liquid phase polymerization, slurry phase polymerization, gas phase polymerization) And the like. The degree of deformation thereof can be easily performed by a person skilled in the art.

For example, in the case of the liquid phase polymerization or the slurry phase polymerization, it is possible to use a polymerization initiator such as propane, butane, pentane, hexane, octane, decane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, Organic solvents such as dichloromethane, chloroethane, dichloroethane, and chlorobenzene, or mixtures thereof, or the olefin monomers may be used as a medium.

In the case of the above-mentioned liquid phase polymerization, the final polymer is obtained by, for example, vaporizing the unreacted starting material and the solvent at a temperature of about 180 ° C to 230 ° C and a pressure of 3 bar to 8 bar, May be transferred to a solvent separator to remove the solvent. The solvent separator can completely remove the residual solvent by a vacuum pump. Further, after the residual solvent is removed, the final polymer may be granulated using a cutter.

The amount of the metallocene catalyst to be used is not particularly limited. For example, in the polymerization system, the central metal (titanium (Ti), zirconium (Zr), and hafnium can be a ⁵ mol / L ^- the concentration of the ^{(Hf)) 1 × 10 -} 5 mol / L to about 9 × 10. The polymerization temperature and pressure may be 0 ° C to 200 ° C, for example, 100 ° C to 180 ° C, in the case of liquid phase polymerization, although the temperature and pressure during polymerization may vary depending on the reactants, reaction conditions, In the case of slurry phase polymerization or gas phase polymerization, it may be from 0 캜 to 120 캜, for example, from 60 캜 to 100 캜. The polymerization pressure may also be from 1 bar to 150 bar, preferably from 20 bar to 90 bar, more preferably from 20 bar to less than 50 bar. The pressure may be by injection of an olefin monomer gas (e.g., ethylene gas).

For example, the polymerization can be carried out batchwise, semi-continuously or continuously. The polymerization can also be carried out in two or more stages having different reaction conditions, and the molecular weight of the final polymer can be controlled by varying the polymerization temperature or by injecting hydrogen into the reactor.

The method for producing the olefin polymer is a scavenger for removing moisture at the time of polymerization. The scavenger may be a polymer or a mixture of two or more members selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Cu, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, Ge, Sn, Pb, As, Sb or B can be further added. For example, the molar concentration ratio of the scavenger to the metallocene catalyst may be 1:50 or higher to 1: 200 or lower.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

Manufacturing example 1: Synthesis of compound 1

4.68 mL of 1.0 M HCl solution was added slowly to 200 mL of hexane containing 2 g of (C ₁₈ H ₃₇ ) ₂ N (CH ₃ ) 2 at 0 ° C, and then stirred at room temperature for 2 hours. After 2 h, (C ₁₈ H ₃₇ ) ₂ N (CH ₃ ) H ⁺ Cl ^- which was a white solid was prepared via filtration. 2.5 equivalents of LiB (C ₆ F ₅ ) ₄ were mixed with (C ₁₈ H ₃₇ ) ₂ N (CH ₃ ) H ⁺ Cl ^- and 48 mL of water was added and stirred for 1 hour. Then 32 mL of toluene was added and stirred for 10 minutes. Compound 1, which was a white solid, was obtained through extraction (yield: 82%).

_{1H NMR (C 6 D 6)} : δ = 3.45 (br s, 1H), 2.12 (m, 1H), 2.05 (br s, 1H), 1.89 (br s, 1H), 1.25 ~ 1.62 (br s, 56H ), 1.21-1.32 (br s, 4H), 0.82-1.05 (m, 14H) ppm.

Manufacturing example 2: Synthesis of Compound 2

Compound 2 was prepared in the same manner as in Production Example 1, except that 4.68 mL of a 1.0 M HCl solution was slowly added to 200 mL of hexane containing 2 g of (C ₁₆ H ₃₃ ) ₂ N (CH ₃ ) at 0 ° C (Yield: 90%).

_{1H NMR (C 6 D 6)} : δ = 3.42 (br s, 1H), 2.11 (m, 1H), 2.02 (br s, 1H), 1.81 (br s, 1H), 1.23-1.64 (br s, 52H ), 1.25-1.34 (br s, 4H), 0.80-1.08 (m, 14H) ppm.

Manufacturing example 3: Synthesis of Compound 3

Compound 3 was prepared in the same manner as in Production Example 1, except that 4.68 mL of a 1.0 M HCl solution was slowly added to 200 mL of hexane containing 2 g of (C ₁₄ H ₂₉ ) ₂ N (CH ₃ ) at 0 ° C (Yield: 87%).

_{1H NMR (C 6 D 6)} : δ = 3.44 (br s, 1H), 2.14 (m, 1H), 2.01 (br s, 1H), 1.83 (br s, 1H), 1.25-1.68 (br s, 52H ), 1.25-1.34 (br s, 4H), 0.79-1.02 (m, 14H) ppm. pm.

Manufacturing example 4: Synthesis of Compound 9

Compound 9 was prepared in the same manner as in Production Example 1, except that 4.68 mL of a 1.0 M HCl solution was slowly added to 200 mL of hexane containing 2 g of (C ₁₈ H ₃₇ ) ₃ N (CH ₃ ) at 0 ° C (Yield: 82%).

_{1H NMR (C 6 D 6)} : δ = 3.45 (br s, 1H), 2.12 (m, 1H), 2.05 (br s, 1H), 1.89 (br s, 1H), 1.25-1.62 (br s, 52H ), 1.21-1.32 (br s, 4H), 0.82-1.05 (m, 14H) ppm. pm.

Manufacturing example 5: Synthesis of Compound 10

Except that 4.68 mL of a 1.0 M HCl solution was slowly added to 200 mL of hexane containing ₂ g of (C ₁₈ H ₃₇ ) ₂ N (CH ₃ ) ₂ at 0 ° C, 10 (yield: 83%).

_{1H NMR (C 6 D 6:} δ = 3.45 (br s, 1H), 2.12 (br s, 1H), 2.05 (br s, 1H), 1.89 (br s, 1H), 1.25-1.62 (br s, 52H ), 1.21-1.32 (br s, 4H), 0.82-1.05 (m, 14H) ppm.

Manufacturing example 6: Example 1 to 3

Methylcyclohexane, 1-octene and ethylene monomer were fed at 40 bar to a 0.75 L continuously stirred reactor preheated to 120-140 占 폚. Dimethylsilyl (t-butylamido) (2-methylbenz [e] indenyl) titanium dimethyl) (In the above EX1, X- is methyl group , A co-catalyst compound represented by the compound 6, and aluminum (Al) were fed to a continuous stirred tank reactor to conduct a copolymerization reaction. The solvent was removed from the polymer as a result of the copolymerization reaction at a pressure of 5 bar at the end of the continuous stirred reactor, and the residual solvent was completely removed by using a vacuum pump to prepare an ethylene-alpha olefin copolymer. Specific conditions are shown in Table 1 below.

Example 1 Example 2 Example 3 Methylcyclohexane 2.95 (kg / hr) 2.49 (kg / hr) 2.95 (kg / hr) Ethylene 0.26 (kg / hr) 0.26 (kg / hr) 0.51 (kg / hr) 1-octene 0.62 (kg / hr) 1.03 (kg / hr) 0.62 (kg / hr) The metallocene compound 0.089 (μmol / min) 0.089 (μmol / min) 0.178 (μmol / min) Co-catalyst compound 0.534 (μmol / min) 0.534 (μmol / min) 1.068 (μmol / min) aluminum 8.9 (μmol / min) 8.9 (μmol / min) 17.8 (μmol / min) Temperature 130 ℃ 150 ℃ 150 ℃ pressure 40bar 40bar 40bar

Manufacturing example 7: Comparative Example 1 to 7

The ethylene-alpha olefin copolymers of Comparative Examples 1 to 7 used ENGAGE ^TM of DOW as shown in Table 2 below.

Comparative Example 1 DOW ENGAGE ^TM 8100 Comparative Example 2 DOW ENGAGE ^TM 8180 Comparative Example 3 DOW ENGAGE ^TM 8480 Comparative Example 4 DOW ENGAGE ^TM 8540 Comparative Example 5 DOW ENGAGE ^TM 8003 Comparative Example 6 DOW ENGAGE ^TM 8452 Comparative Example 7 DOW ENGAGE ^TM 8200

Experimental Example One

The average lamellar thickness and lamellar thickness distribution (Lw / Ln) of the ethylene-alpha olefin copolymers of Examples 1 to 3 and Comparative Examples 1 to 7 were measured and summarized in Table 3 below.

Fig. 1 shows a lamellar thickness distribution graph of the olefin polymer (PC141015) of the first embodiment. Figs. 2 and 3 show graphs comparing lamellar thickness distributions of the olefin polymer (PC141015) of Example 1 and the olefin polymer (DOW engage 8100) of Comparative Example 1. Fig. FIG. 4 shows an enlarged graph of the lamellar thickness distribution of 10 nm or more in the graph of FIG.

Fig. 5 shows a lamellar thickness distribution graph of the olefin polymer (PC150205-1) according to the second embodiment. Figs. 6 and 7 show graphs comparing lamellar thickness distributions of the olefin polymer (PC150205-1) of Example 2 and the olefin polymer (DOW engage 8180) of Comparative Example 2. Fig. FIG. 8 shows a graph enlarging the lamellar thickness distribution of 10 nm or more in the graph of FIG. 5; FIG.

9 shows a graph of the lamellar thickness distribution of the olefin polymer (PC140821-1) according to the third embodiment. Figs. 10 and 11 show graphs comparing lamellar thickness distributions of the olefin polymer (PC140821-1) of Example 3 and the olefin polymer (Engage 8480) of Comparative Example 2. Fig. Fig. 12 shows an enlarged graph of the lamellar thickness distribution of 10 nm or more in the graph of Fig.

The measurement results of FIGS. 1 to 12 are summarized in Table 4.

Measurements were performed by differential scanning calorimetry (DSC) and the successive self-nucleation and annealing (SSA) method was used in which step crystallization (SC) was applied with stepwise cooling and a series of heating and cooling cycles were used .

The partial melting of SSA is annealed in the next step, leaving only the most stable crystals intact, while the molten chains are separated during self-nucleation and crystallization during cooling. That is, in each successive cycle of the SSA process, heat energy is supplied to melt the incomplete crystals by heating scans, while annealing and complete crystal growth occur in the preformed lamellas. Thus, all melting and crystallization processes that occur during standard DSC operation are promoted in each partial-stage heating scan, and the remaining crystals after SSA treatment are closer to equilibrium. Thus, in the SSA thermal separation method, the main parameters are selected as follows.

The interval between the fractionation window or the self-nucleation temperature (Ts) was 5, the retention time at Ts was 5 minutes, and the heating and cooling scan rate at the heat treatment step was 10 / min.

Each peak in the SSA-DSC endothermic curve represents a chain segment with a similar methylene sequence length (MSL). DSC data are difficult to quantify because the heat flow, which is the signal strength of the DSC measurement, is the product of the mass of the crystalline polymer melted at a particular temperature times the heat of fusion. Therefore, in addition to the calibration curve for converting the melting temperature to the short chain branch (SCB), another calibration curve is required to convert the heat flow to the mass fraction. However, since such a calibration curve depends on the nature of the polymer, a normalized heat flow was used for quantitative analysis, assuming that the dependence of the heat of fusion on the melt temperature was negligible in order to overcome the drawbacks.

To measure the amount of material that melts at a specific temperature, the temperature axis is converted to lamellar thickness or MSL (methylene sequence length). The first is to use the Thomson-Gibbs equation and the second one can be obtained by using a suitable calibration curve (see equation (2) below). First, the following Thompson-Gibbs equation (see equation (1) below) was used to establish the relationship between temperature and lamellar thickness.

&Lt; Formula (1) >

Is the lamellar thickness (nm), DELTA Hv is the fusion enthalpy for the lamellar of infinite thickness (here, substituted by 288 x 106 J / m ² ), and sigma is the lamellar surface free energy × 10 ^-3 J / m ² ), T m is the melting temperature, and T ⁰ m is the equilibrium melting temperature for the linear PE of infinite thickness (here, T ⁰ m value, 418.7K substituted).

The equilibrium melting temperature for the random copolymer, i.e. the thermodynamic melting temperature T ^c m for crystals of infinite thickness in the random copolymer, is calculated using the following Flory's equation (see equation (2) below) ) Were calculated.

&Lt; Formula (2) >

In the above formula (2), T ⁰ m is the equilibrium melting temperature of the lamellar of infinite thickness in the linear PE, R is the ideal gas constant,? Hu is the molar calorific value of the repeating units in the crystal, And the mole fraction of the crystalline units in the random copolymer using the determined weight average short chain branch (SCB).

The lamellar thickness distribution was measured using the following formulas (3) to (5).

&Lt; Formula (3) >

In Equation (3), Lw is a weighted average of the ESL (Ethylene Sequence Length), and Ln is an arithmetic mean of the ESL (Ethylene Sequence Length).

&Lt; Expression (4) >

In the above equation (4), n _i Is the normalized partial area of the final DSC scan, and L _i is the lamellar thickness.

&Lt; Equation (5) >

In the above equation (5), n _i Is the normalized partial area of the final DSC scan, and L _i is the lamellar thickness.

The average lamellar thickness (nm) Lamellar thickness distribution (Lw / Ln) Example 1 3.72 2.40 Example 2 3.04 1.15 Example 3 5.30 1.10 Comparative Example 1 3.13 1.04 Comparative Example 2 2.92 1.04 Comparative Example 3 5.20 1.09 Comparative Example 4 5.93 1.09 Comparative Example 5 3.95 1.05 Comparative Example 6 3.54 1.04 Comparative Example 7 3.42 1.04

Lamella Size Ratio (%) More than 0 nm and not more than 10 nm 10 nm or more and less than 50 nm 50 nm or more and 100 nm or less Example 1 99.36 0.56 0.08 Example 2 99.72 0.28 0 Example 3 99.77 0.23 0 Comparative Example 1
100 0 0 Comparative Example 2
100 0 0 Comparative Example 3
100 0 0

Experimental Example 2

The density, melt index, C ₈ mol%, melt temperature and crystallinity of the ethylene-alpha olefin copolymers of Examples 1 to 3 and Comparative Examples 1 to 3 were measured and are summarized in Table 5 below. Referring to the following Table 5, it can be confirmed that the melting temperature of Example 1 is higher than that of Comparative Example 1 having a similar density and a same melt index. Further, it can be confirmed that the melting temperature of Example 2 is higher than that of Comparative Example 2 having a similar density and a same melt index. In addition, it can be confirmed that the melting temperature of Example 3 is higher than that of Comparative Example 3 having a similar density and a same melt index. That is, it can be confirmed that Example 1 is superior in thermal stability to Comparative Example 1, and Example 2 is superior to Comparative Example 2, and Example 3 is superior to Comparative Example 3 in thermal stability.

(1) Density: Measured by ASTM D792 analysis method.

(2) Melt Index (MI): Measured using the ASTM D1238 analysis method.

(3) C ₈ mol%: 13 C-NMR.

(4) Melting temperature: Measured by differential scanning calorimetry (DSC). The heating and cooling scan rate was 10 / min.

(5) Crystallinity: Measured by differential scanning calorimetry (DSC). The heating and cooling scan rate was 10 / min.

Example 1 Comparative Example 1 Example 2 Comparative Example 2 Example 3 Comparative Example 3 Density (g / cm ³⁾ 0.872 0.870 0.865 0.863 0.902 0.900 Melt Index
(190 DEG C, g / 10 min) One One 0.5 0.5 0.95 One C ₈ mol% 8.9 9.3 10.4 10.8 3.9 4.1 Melting temperature (占 폚), 66.2 63.7 52.7 49.8 100.2 98.3 Crystallinity 26.1 24.5 20.8 19.4 42.3 38.1

Manufacturing example 8: Example 4 to 15, Comparative Example 8 to 15

0.5 L hexane and 1-octene 0.4 M were added to a 1.0 L reactor and the temperature of the reactor was raised to 90 占 폚. At the same time, the reactor was charged with 20 bar of ethylene. Dimethylsilyl (t-butylamido) (2-methylbenz [e] indenyl) titanium dimethyl) (treated with triisobutyl aluminum) 4 mmol of a metallocene compound in which X- is a methyl group) was charged into a reactor and then introduced into a reactor using argon. 24 占 퐉 ol of the co-catalyst compounds shown in Table 6 were introduced into the reactor using argon Thereafter, the polymerization reaction was carried out for 5 minutes. The polymer was dried at 80 DEG C and weighed to compare the catalytic activity.

Co-catalyst compound Composition ratio (% by weight) Example 4 A mixture of compounds 1 to 3 Compound 1: Compound 2: Compound 3 = 72: 26: 2 Example 5 A mixture of compounds 1 to 3 Compound 1: Compound 2: Compound 3 = 52: 42: 6 Example 6 A mixture of compounds 1 to 3 Compound 1: Compound 2: Compound 3 = 65: 30: 5 Example 7 A mixture of compounds 1 and 3 Compound 1: Compound 3 = 80: 20 Example 8 A mixture of compounds 1 and 6 Compound 1: Compound 6 = 80: 20 Example 9 A mixture of compounds 1 and 6 Compound 1: Compound 6 = 50: 50 Example 10 A mixture of compounds 1 and 9 Compound 1: Compound 9 = 50: 50 Example 11 A mixture of compounds 1 and 10 Compound 1: Compound 10 = 50: 50 Example 12 Compound 1 Compound 1 = 100 Example 13 Compound 2 Compound 2 = 100 Example 14 Compound 3 Compound 3 = 100 Example 15 Compound 6 Compound 6 = 100 Comparative Example 8 A mixture of compounds 1 to 3 Compound 1: Compound 2: Compound 3 = 79: 20: 1 Comparative Example 9 A mixture of compounds 1 to 3 Compound 1: Compound 2: Compound 3 = 40: 50: 10 Comparative Example 10 A mixture of compounds 1 and 3 Compound 1: Compound 3 = 90: 10 Comparative Example 11 A mixture of compounds 1 and 6 Compound 1: Compound 6 = 90: 10 Comparative Example 12 A mixture of compounds 1 and 6 Compound 1: Compound 6 = 40: 60 Comparative Example 13 A mixture of compounds 1 and 6 Compound 1: Compound 6 = 10: 90 Comparative Example 14 A mixture of compounds 1 and 17 Compound 1: Compound 17 = 50: 50 Comparative Example 15 A mixture of compounds 1 and 18 Compound 1: Compound 18 = 50: 50

Experimental Example 3

The average lamellar thickness, the lamellar thickness distribution (Lw / Ln), the catalytic activity, the melting point, and the C ₈ weight% were measured using the examples 4 to 15 and the comparative examples 8 to 15,

(1) Active unit: kg of olefin polymer per kg of catalyst used per hour, kg (olefin polymer) / gCat · hr.

(2) 1-Octene content (unit: wt%): 1-octene content in polyolefin obtained through 13C NMR spectrum analysis.

(3) Weight average molecular weight (Mw, unit: g / mol): Measured by GPC (gel permeation chromatography) based on polystyrene.

(4) Measurement of melting temperature (Tm, unit: 占 폚): Measured using differential scanning calorimeter (DSC: 2920) manufactured by TA Corporation. Specifically, the temperature was increased to 200 占 폚, held at that temperature for 5 minutes, then lowered to 30 占 폚, and the temperature was again raised to the top of the DSC curve as the melting temperature. At this time, the rate of rise and fall of the temperature is 10 ° C / min, and the melting temperature is obtained while the second temperature rises.

activation C ₈ (wt%) Tm (占 폚) Lamella Average Thickness (nm) Lamella distribution Example 4 263.4 26.2 73 2.31 2.01 Example 5 255.2 25.9 81 2.45 2.05 Example 6 260.1 26.0 80 2.38 2.03 Example 7 257.5 26.0 77 2.31 1.82 Example 8 242.8 25.9 77 2.39 1.83 Example 9 240.7 25.7 82 2.52 1.72 Example 10 277.0 26.1 80 2.38 2.02 Example 11 272.3 26.0 79 2.40 2.00 Example 12 272.1 26.1 60 2.23 1.25 Example 13 257.1 26.2 64 2.52 1.26 Example 14 252.3 26.3 69 2.67 1.24 Example 15 238.1 25.8 71 2.82 1.28 Comparative Example 8 265.0 26.1 62 2.25 1.28 Comparative Example 9 260.2 25.9 66 2.55 1.31 Comparative Example 10 264.1 26.1 63 2.28 1.29 Comparative Example 11 258.3 26.1 65 2.32 1.29 Comparative Example 12 242.5 25.9 69 2.75 1.30 Comparative Example 13 242.5 25.9 69 2.75 1.30 Comparative Example 14 213.0 26.4 57 2.10 1.30 Comparative Example 15 192.0 24.8 68 2.80 1.27

Referring to Table 7, although the comonomer incorporation characteristics are similar depending on the structure of the promoter compound, the melting point of the olefin polymer is different according to the lamellar thickness and the lamellar distribution, and by mixing several promoter compounds during the catalyst activation The heat resistance of the olefin polymer can be improved. From the results of Examples 4 to 11, it can be seen that the activity is increased and the heat resistance is improved when the single co-catalyst is used according to the mixing ratio of the co-catalyst.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims

A lamellar having an average thickness of 10 nm to 100 nm,
The lamellas having an average thickness of not less than 10 nm and not more than 50 nm have a ratio of not less than 0.10% to not more than 1.99% with respect to all the lamellas,
The lamellas having an average thickness of more than 0 nm to less than 10 nm have a ratio of 98.00% to 99.90% to the total lamellas,
When the melting temperature (Tm) is 110 占 폚 or less,
At least one of the metallocene compounds represented by the following formulas M1 to M2 and both of the promoter compounds represented by the following formula AC1-1 and the promoter compounds represented by the following formula AC2-1, , The content of Compound I, which is one of the two compounds among the above-mentioned co-catalyst compounds, is 20% by weight to 50% by weight, Wherein the compound (I) is formed by polymerization under a metallocene catalyst having a higher number of carbon atoms than the compound (II).

<Formula M1>

In the formula (M1)
M is one of titanium (Ti), zirconium (Zr), and hafnium (Hf)
A is nitrogen,
Q is one of carbon (C), silicon (Si), germanium (Ge), and tin (Sn)
X- are each independently any one of a halogen group, a C _1-10 alkyl group and a C _2-10 alkenyl group,
R ₈ -, R ₉ -, R ₁₀ - and R ₈ - are each independently selected from the group consisting of R ₁ -, R ₂ -, R ₃ -, R ₄ -, R ₅ -, R ₆ -, R ₇ - R ₁₁ - are each independently one of a hydrogen group (H- *), a C _1-20 alkyl group, a C _3-6 cycloalkyl group and a C _6-14 aryl group,

&Lt; Formula (M2)

In the above formula (M2)
M is one of titanium (Ti), zirconium (Zr), and hafnium (Hf)
A is nitrogen,
Q is one of carbon (C), silicon (Si), germanium (Ge), and tin (Sn)
X '- are each independently any one of a halogen group, a C _1-10 alkyl group and a C _2-10 alkenyl group,
_{R '1 - *, R'} 2 - *, R '3 - *, R' 4 - *, R '5 - *, R' 6 - *, R '7 - *, R' 8 - *, R ' _{9 - *, R '10 -} * and R' ₁₁ - * are each independently a hydrogen group (H- *), C _1-20 alkyl, C _3-6 cycloalkyl group (cycloalkyl group) and a C _6-14 aryl group, lt; / RTI > is an aryl group,

<AC1-1>

In the formula AC1-1,
N is nitrogen,
H is hydrogen,
R ¹ -, R ² -, and R ³ - are each independently a substituted or unsubstituted C _1-20 alkyl group, a substituted or unsubstituted C _2-20 alkenyl group, a substituted or unsubstituted C _6-20 An aryl group, a substituted or unsubstituted C _7-40 alkylaryl group and a substituted or unsubstituted C _7-40 arylalkyl group,
Y is one of boron (B), aluminum (Al), gallium (Ga) and indium (In)
R ⁴ - is one of a C _6-20 aryl group substituted with halogen or a C _1-20 alkyl group substituted or unsubstituted with halogen,

<AC2-1>

In the above formula (AC2-1)
N is nitrogen,
R ¹ -, R ² -, R ³ -, and R ⁵ - are each independently a substituted or unsubstituted C _1-20 alkyl group, a substituted or unsubstituted C _2-20 alkenyl group, a C _6-20 aryl group, a substituted or unsubstituted C _7-40 alkylaryl group, a substituted or unsubstituted C _7-40 aryl group,
Y is one of boron (B), aluminum (Al), gallium (Ga) and indium (In)
R ⁴ - is one of a C _6-20 aryl group substituted with halogen or a C _1-20 alkyl group substituted or unsubstituted with halogen.

delete

The method according to claim 1,
Wherein the lamellar having an average thickness of 50 nm to 100 nm is in the range of 0.00 to 0.01% by weight relative to the total lamellar.

delete

The method according to claim 1,
The distribution index (I = L _w / L _n ) of lamellar thickness is 1.10 to 3.00.

6. The method of claim 5,
Olefin polymer having a lamellar thickness distribution index (I = L _w / L _n ) of from 1.40 to 3.00.

The method according to claim 1,
Wherein the melting temperature (Tm) is 72 占 폚 to 110 占 폚.

The method according to claim 1,
A melt index at 190 占 폚 of 0.90 g / 10 min to 1.10 g / 10 min,
A density of 0.860 g / cm < ³ > to 0.910 g / cm < ³ &
The olefin polymer has a melting temperature (Tm) of 65.0 DEG C or higher.

9. The method of claim 8,
An olefin polymer having a crystallinity of at least 25.0.

The method according to claim 1,
A melt index (MI) at 190 캜 of 0.40 g / 10 min to 0.60 g / 10 min,
Density of 0.861 g / cm < ³ > To 0.867 g / cm ³ Lt;
And an olefin polymer having a melting temperature (Tm) of 51.0 DEG C or higher.

11. The method of claim 10,
An olefin polymer having a crystallinity of 20.0 or more.

The method according to claim 1,
A melt index (MI) at 190 캜 of from 0.90 g / 10 min to 1.10 g / 10 min,
Density of 0.900 g / cm < ³ > To 0.904 g / cm ³ Lt;
An olefin polymer having a melting temperature (Tm) of 99.0 DEG C or higher.

13. The method of claim 12,
An olefin polymer having a crystallinity of at least 39.0.

At least one of the metallocene compounds represented by the following formulas M1 to M2; At least one of the cocatalyst compounds represented by the following formula: AC1-1; And a metallocene catalyst comprising at least one of the promoter compounds represented by the following formula: AC2-1:
<Formula M1>

15. The method of claim 14,
The metallocene catalyst comprises a mixture of two compounds out of the compounds represented by the above formulas AC1-1 to AC2-1, wherein the content of one of the two compounds is 50 wt% to 80 wt% %, And the compound I, which is another one of the two compounds, is 20 wt% to 50 wt%, and the compound I has a carbon number greater than that of the compound II.

15. The method of claim 14,
The metallocene catalyst comprises a mixture of three of the compounds represented by the above formulas AC1-1 to AC2-1, wherein the content of one of the three compounds is 52 wt% to 72 wt% %, And the content of Compound II, which is another of the three compounds, is 26 wt% to 42 wt%, and the content of Compound III, which is another one of the three compounds, is 2 wt% to 6 wt% Wherein the compound (I) has a smaller number of carbon atoms than the compound (II), and the compound (II) has a larger number of carbon atoms than the compound (III).

15. The method of claim 14,
The olefin monomers may be selected from the group consisting of ethylene and at least one of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, Olefin, wherein the polymerization pressure inside the polymerization reactor is from 20 bar to less than 50 bar.

At least one of the metallocene compounds represented by the following formulas M1 to M2; At least one of the cocatalyst compounds represented by the following formula: AC1-1; And a cocatalyst compound represented by the following formula: AC2-1, wherein the content of one of the two compounds among the two cocatalyst compounds is 50% by weight to 80% by weight, The compound II content, which is the other of the two compounds, is 20 wt% to 50 wt%, and the compound I is a metallocene catalyst having a higher number of carbon atoms than the compound II:
<Formula M1>

19. The method of claim 18,
The compound I further comprises a compound III having more carbon atoms than the compound II among the compounds represented by the above formulas AC1-1 to AC2-1, and the content of Compound I, which is one of the three compounds, is 52 wt% to 72 wt% And the content of the compound II, which is another one of the three compounds, is 26 wt% to 42 wt%, and the content of the compound III, which is another one of the three compounds, is 2 wt% to 6 wt% Sen catalyst.

19. The method of claim 18,
Wherein one of the compounds I and II is one of the compounds represented by the formula AC1-1 and the other is one of the compounds represented by the formula AC2-1.