WO2016153275A1 - Olefin-based polymer - Google Patents

Abstract

The present invention provides an olefin-based polymer exhibiting excellent mechanical strength and, particularly, remarkably improved impact strength by displaying a single peak in gel permeation chromatography analysis and having Te1, Te2 and Te3, which are the elution temperatures of the olefin-based polymer, in a temperature range of -20°C to 120°C during temperature rising elution fractionation.

Description

Olefin Polymer

Citation with Related Applications

This application claims the benefit of priority based on Korean Patent Application No. 2015-0042743 dated March 26, 2015 and Korean Patent Application No. 2016-0021825 dated February 24, 2016. The contents are included as part of this specification.

Technical Field

The present invention relates to olefinic polymers which exhibit good mechanical strength, in particular significantly improved impact strength.

Dow announced [Me ₂ Si (Me ₄ C ₅ ) NtBu] TiCl ₂ (Constrained-Geometry Catalyst, hereinafter abbreviated as CGC) in the early 1990s (US Pat. No. 5,064,802). The superiority of CGC in the copolymerization reaction of -olefin compared to the metallocene catalysts known to the prior art can be broadly summarized as follows:

(1) to produce high molecular weight polymers with high activity even at high polymerization temperatures;

(2) The copolymerization of alpha-olefins with high steric hindrances such as 1-hexene and 1-octene is also excellent.

On the other hand, the copolymer produced by such a CGC catalyst has a lower content of the portion having a lower molecular weight than the copolymer prepared by the conventional Ziegler-Natta-based catalyst is improved physical properties such as strength (strength).

However, in spite of these advantages, the copolymer produced by the CGC or the like has a disadvantage in that the processability is lower than that of the polymer produced by the existing Ziegler-Natta catalysts.

U.S. Patent 5,539,076 discloses a metallocene / nonmetallocene mixed catalyst system for preparing certain peak high density copolymers. The catalyst system is supported on an inorganic support. The problem with the supported Ziegler-Natta and metallocene catalyst systems is that the supported hybrid catalysts are less active than homogeneous homocatalysts, making it difficult to produce olefinic polymers having properties suitable for the application. In addition, since the olefin-based polymer is produced in a single reactor, there is a fear that a gel generated in the blending method is produced, it is difficult to insert a comonomer in a high molecular weight portion, and the shape of the resulting polymer may be poor. In addition, since the two polymer components are not uniformly mixed, there is a fear that quality control becomes difficult.

Accordingly, there is still a need for the development of olefinic polymers that can overcome the disadvantages of conventional olefinic polymers and provide improved physical properties.

The technical problem to be solved by the present invention is to provide an olefin-based polymer and a method for producing the same that can exhibit excellent mechanical strength, in particular significantly improved impact strength through the control of the crystal structure in the polymer.

According to an embodiment of the present invention, a single peak is shown in gel permeation chromatography (GPC) analysis, and the temperature rising elution fraction (TREF) is measured at a temperature range of -20 ° C to 120 ° C. An olefin polymer having three elution temperatures, Elution temperature 1 (Te1), Elution temperature 2 (Te2), and Elution temperature 3 (Te3) is provided.

The olefinic polymer according to the present invention exhibits a single peak in the GPC analysis through control of the crystal structure in the polymer, and has three elution temperatures, namely, Te1, Te2 and Te3 in the temperature rise elution fractionation measurement, thereby providing excellent mechanical strength, In particular, it can exhibit significantly improved impact strength. As a result, it can be used in various fields and uses, such as various packaging, construction, household goods, such as materials for automobiles, electric wires, toys, textiles, and medical.

The following drawings, which are attached to this specification, illustrate preferred embodiments of the present invention, and together with the contents of the present invention serve to further understand the technical spirit of the present invention, the present invention is limited to the matters described in such drawings. It should not be construed as limited.

1 is a graph showing the results of temperature rise elution fractionation (TREF) measurement of the olefin polymer prepared in Example 1. FIG.

2 is a graph showing the results of temperature rise elution fractionation (TREF) measurement of the olefin polymer prepared in Example 2. FIG.

3 is a graph showing the results of temperature rise elution fractionation (TREF) measurement of the olefin polymer prepared in Comparative Example 1.

Figure 4 is a graph showing the results of temperature rise elution fractionation (TREF) measurement of the olefin polymer prepared in Comparative Example 4.

5 is a graph showing the results of gel permeation chromatography (GPC) analysis of the olefin polymer prepared in Example 1. FIG.

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

The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.

Unless specifically defined herein, an alkyl group refers to a straight and branched aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms. Specifically, the alkyl group includes a straight or branched alkyl group having 1 to 20 carbon atoms, more specifically 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, iso-amyl group, hexyl group and the like. Can be mentioned.

In addition, unless specifically defined in this specification, an alkoxy group means the C1-C20 linear or branched alkyl group (-OR) couple | bonded with oxygen. Specifically, the alkoxy group includes an alkoxy group having 1 to 20 carbon atoms, and more specifically 1 to 6 carbon atoms. Specific examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group or t-butoxy group.

In addition, unless specifically defined in this specification, an alkenyl group means a C2-C20 linear and branched aliphatic unsaturated hydrocarbon group containing a carbon-carbon double bond. Specifically, the alkenyl group includes an alkenyl group having 2 to 6 carbon atoms. Specific examples of the alkenyl group include an ethenyl group, propenyl group or butenyl group.

In addition, unless specifically defined in this specification, a cycloalkyl group means a C3-C20 cyclic saturated hydrocarbon group. Specifically, the cycloalkyl group includes a cycloalkyl group having 3 to 6 carbon atoms. As a specific example of the said cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, etc. are mentioned.

In addition, unless specifically defined herein, an aryl group means a carbocyclic aromatic radical having 6 to 20 carbon atoms including one or more rings, and the rings may be attached or fused together in a pendant manner. Specifically, the aryl group includes an aryl group having 6 to 20 carbon atoms, more specifically, 6 to 12 carbon atoms. Specific examples of the aryl group include a phenyl group, a naphthyl group or a biphenyl group.

In addition, unless specifically defined in this specification, an arylalkyl group means the functional group (Ar-R-) in which the aryl group (Ar) which is an aromatic hydrocarbon group was substituted by the carbon of a linear or branched alkyl group (R). Specifically, the arylalkyl group includes an arylalkyl group having 7 to 20 carbon atoms, more specifically, 7 to 12 carbon atoms. Specific examples of the arylalkyl group include benzyl group, phenethyl group and the like.

In addition, unless specifically defined in this specification, an alkylaryl group means the functional group (R-Ar-) in which the linear or branched alkyl group (R) was substituted by the carbon of an aromatic hydrocarbon group (Ar). Specifically, the alkylaryl group includes an alkylaryl group having 7 to 20 carbon atoms, more specifically, 7 to 12 carbon atoms.

In addition, unless specifically defined in the present specification, an aryloxy group means an aryl group (-OAr) bonded with oxygen, wherein the aryl group is as defined above. Specifically, the aryloxy group includes an aryloxy group having 6 to 20 carbon atoms, more specifically, 6 to 12 carbon atoms. Specific examples of the aryloxy group include phenoxy and the like.

In addition, unless specifically defined herein, a silyl group means a -SiH ₃ radical derived from silane, and at least one of hydrogen atoms in the silyl group may be substituted with various organic groups such as an alkyl group or a halogen group. It may be.

In addition, unless specifically defined herein, the alkylamino group means a functional group in which at least one hydrogen in the amino group (-NH ₂ ) is substituted with an alkyl group, wherein the alkyl group is as defined above. Specifically, the alkylamino group is —NR ₂ (wherein R may each be a hydrogen atom or a straight or branched alkyl group having 1 to 20 carbon atoms, but not both R are hydrogen atoms).

In addition, unless specifically defined in the present specification, an arylamino group means a functional group in which at least one hydrogen in the amino group (-NH ₂ ) is substituted with an aryl group, wherein the aryl group is as defined above.

In addition, unless specifically defined in this specification, an alkylidene group means the bivalent aliphatic hydrocarbon group from which two hydrogen atoms were removed from the same carbon atom of an alkyl group. Specifically, the alkylidene group includes an alkylidene group having 1 to 20 carbon atoms, more specifically, 1 to 12 carbon atoms. Specific examples of the alkylidene group include a propane-2-ylidene group.

In addition, unless specifically defined in the present specification, a hydrocarbyl group has a carbon number of 1 to 60 containing only carbon and hydrogen regardless of its structure, such as an alkyl group, an aryl group, an alkenyl group, an alkylaryl group, an arylalkyl group, etc. It means a monovalent hydrocarbon group, and a hydrocarbylene group means a divalent hydrocarbon group having 1 to 60 carbon atoms.

In addition, unless specifically defined in this specification, a metalloid radical is a metalloid radical of group 14 (Group 4A) metal substituted by the C1-C20 hydrocarbyl group. Metalloid radicals are electronically unsaturated and can act as Lewis acids. The Group 14 metal may be silicon (Si), germanium (germanium), tin (tin) or arsenic (arsenic) and the like. Specifically, the metalloid radical may include silyl groups such as trimethylsilyl group, triethylsilyl group, triethylsilyl group, ethyldimethylsilyl group and methyldiethylsilyl group; Triphenylgermyl, trimethylgermyl, and the like.

In addition, in the present specification, the term "polymer" means a polymer compound prepared by polymerization of the same or different types of monomers. The generic term "polymer" includes the terms "homopolymer", "copolymer", "terpolymer" as well as "interpolymer". In addition, the "interpolymer" means a polymer produced by the polymerization of two or more different types of monomers. The term "interpolymer" is used generically to refer to polymers made from three different types of monomers, as well as to the term "copolymer" commonly used to refer to polymers made from two different monomers. Terpolymers ". This includes polymers made by the polymerization of four or more types of monomers.

In the present specification, the term "quasicrystalline" refers to primary transition temperature, crystal melting point (Tm), elution point, or the like measured by temperature rising elution fractionation (TREF), differential scanning calorimetry (DSC) or equivalent technique. It refers to a polymer having. As for the semi-crystalline, the density, Tm, elution point, etc. vary depending on the crystallinity. The term “amorphous” refers to a polymer without a crystalline melting point, as measured by elevated temperature elution fractionation (TREF), differential scanning calorimetry (DSC), or equivalent technique.

The olefin-based polymer according to an embodiment of the present invention exhibits a single peak in the gel permeation chromatography analysis, and three elution temperatures in the temperature range of -20 ° C. to 120 ° C. when measuring the temperature rise elution fractionation (TREF), Te1, Te2. And Te3.

In general, when two or more hybrid catalysts are used, two TREF peaks may exist. However, in this case, since it is difficult to predict and control the activity and copolymerizability of each of the hybrid catalysts, it may be difficult to prepare an olefin polymer having properties suitable for the application. In addition, the two or more kinds of the catalyst components are not uniformly mixed, there is a fear that quality control becomes difficult.

In contrast, the present invention shows a single peak in GPC analysis and three elution temperatures in TREF measurement by controlling the crystal structure in the polymer using a catalyst composition containing a heterogeneous transition metal compound having excellent miscibility in preparing an olefin polymer. , Te1, Te2 and Te3 can be provided to provide olefinic polymers with good mechanical strength, in particular significantly improved impact strength.

Specifically, the olefin polymer according to one embodiment of the present invention includes a first semicrystalline olefin polymer, a second semicrystalline olefin polymer, and a third semicrystalline olefin polymer, and temperature rising elution fractionation (TREF) measurement Having a first semicrystalline olefinic polymer peak (P1), a second semicrystalline olefinic polymer peak (P2) and a third semicrystalline olefinic polymer peak (P3) in the -20 ° C to 120 ° C temperature range. At this time, the elution temperature (Te, Elution temperature) of each peak is represented by Te1, Te2 and Te3, respectively.

In general, an olefinic polymer has one semicrystalline peak, whereas an olefinic polymer according to an embodiment of the present invention may have three semicrystalline peaks, thereby increasing mechanical strength, particularly impact strength.

In the present invention, the measurement of the TREF can be measured using, for example, a TREF machine manufactured by PolymerChar, and can be measured while increasing the temperature from -20 ° C to 120 ° C using o-dichlorobenzene as a solvent.

Specifically, when the olefin polymer is measured at a TREF, Te1 is present at a temperature lower than Te2, and Te2 is relatively lower than Te3. Te2 is in the range of -20 ℃ to 100 ℃, Te2 is in the range of 0 ℃ to 120 ℃, Te3 may be present in the range of 20 ℃ to 120 ℃. As used herein, Te (Elution temperature) means the temperature of the highest point of each peak in the TREF elution curve expressed as elution with respect to temperature (dW / dT), fraction ratio can be calculated as the integral value of the temperature-dissolution graph have.

More specifically, the olefin polymer has a density of 0.86 g / cc to 0.88 g / cc when the TREF is measured, the Te1 ranges from -20 ° C to 30 ° C, the Te2 ranges from 10 ° C to 80 ° C, and the Te3 May range from 40 ° C to 120 ° C.

In addition, the olefin polymer has a fraction ratio (area%) of the first semicrystalline olefin polymer peak (P1) of 5% to 90% when measured by TREF, and the second semicrystalline olefin polymer peak (P2) The fractional ratio is 5% to 90%, and the fractional ratio of the third semicrystalline olefin polymer peak (P3) may be 5% to 90%. More specifically, the fractional ratio of the first semicrystalline olefinic polymer peak (P1) is 30% to 80%, the fractional ratio of the second semicrystalline olefinic polymer peak (P2) is 5% to 40%, and the third quaternary The fractional ratio of the crystalline olefinic polymer peak (P3) may be 5% to 50%.

In calculating the fraction ratio, the starting point of each peak in the elution rate (dW / dT) graph with respect to temperature is defined as the point at which the polymer starts to elute based on the base line, and the end point of each peak is based on the base line. The polymer was defined as the point at which elution ends. In this case, when the first semi-crystalline olefin polymer peak (P1) and the second semi-crystalline olefin polymer peak (P2) partially overlap each other, the point where the value of the elution amount (dW / DT) is lowest in the overlap region is determined by the end point of the peak of P1. It can be defined as the starting point of the P2 peak. In addition, since the peak expressed at -20 ° C to -10 ° C appears as a mixture of an amorphous polymer and a low crystalline polymer, the peak appearing at this position can be treated in addition to the fraction ratio of the P1 peak.

In addition, the olefin polymer may include Tc1, Tc2, and Tc3, which are crystallization temperatures (Tc) obtained from a differential scanning calorimetry (DSC) curve. Specifically, the olefin polymer may have a density of 0.850 g / cc to 0.910 g / cc, Tc1 of 5 ° C. or less, Tc2 of 0 ° C. to 60 ° C., and Tc3 of 80 ° C. to 130 ° C.

One Tc is present when preparing a polymer with a common metallocene catalyst. However, when three Tc are present, thermal stability and mechanical strength may increase because the crystals melt and crystallize at different temperatures. As used herein, Tc means the peak of the cooling curve of the heat flow in the temperature-heat flow graph of the differential scanning calorimetry (DSC), that is, the exothermic peak temperature at the time of cooling. Specifically, the Tc is filled with about 0.5 mg to 10 mg of a sample in a measuring container with a differential scanning calorimeter (DSC: Differential Scanning Calorimeter 6000) manufactured by PerKinElmer, and a nitrogen gas flow rate of 20 ml / min. In order to make the heat history equal to, the temperature was raised from 0 ° C to 150 ° C at a heating rate of 20 ° C / min, then maintained for 2 minutes in that state, and again at a temperature of 10 ° C / min from 150 ° C to -100 ° C. It is the peak value of the cooling curve of the heat flow measured by DSC, cooling by.

The olefin polymer according to one embodiment of the present invention exhibits a low density of 0.850 g / cc to 0.910 g / cc as measured according to ASTM D-792.

In general, the density of the olefin-based polymer is affected by the type and content of the monomers used in the polymerization, the degree of polymerization, and the like. In the case of the copolymer, the density of the olefin polymer is largely affected by the content of the comonomer. In the present invention, a large amount of comonomers can be introduced by using a mixed catalyst having a heterogeneous structure. As a result, the olefin polymer according to one embodiment of the present invention has a low density in the range as described above, and as a result can exhibit excellent impact strength. More specifically, the olefin-based polymer may have a density of 0.86 g / cc to 0.88 g / cc, in this case, the effect of maintaining the mechanical properties and the impact strength improvement by the density control is more remarkable.

In addition, the olefin polymer according to one embodiment of the present invention has a melt index (MI) of 0.1 g / 10 min to 100 g / 10 min, more specifically 0.1 g measured at 190 ° C. and 2.16 kg load conditions according to ASTM D1238. / 10min to 50 g / 10min, even more specifically 0.1 g / 10min to 30 g / 10min.

In addition, the melt index (MI) affecting the mechanical properties, impact strength, and moldability of the olefin polymer can be controlled by controlling the amount of catalyst used in the polymerization process. The olefin-based polymer according to an embodiment of the present invention may exhibit excellent impact strength by showing a melt index (MI) measured in the low density condition as described above in the above-described range.

In addition, when two or more kinds of polymers are mixed, molecular weight distribution (MWD) is usually increased, and as a result, impact strength and mechanical properties are reduced, and blocking phenomenon occurs. In contrast, the olefin-based polymer according to an embodiment of the present invention has at least three or more crystallization temperatures on a DSC curve by using heterogeneous catalysts having a characteristic structure, but is monomodal in a molecular weight distribution curve when measuring GPC. It has a peak and shows a narrow molecular weight distribution. As a result, excellent impact strength can be exhibited. Specifically, the olefin polymer may have a molecular weight distribution (MWD) of 1.5 to 4.0, specifically 1.5 to 3.0, which is the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn). In addition, the olefin polymer may have a weight average molecular weight (Mw) of 10,000 g / mol to 500,000 g / mol, more specifically 20,000 g / mol to 200,000 g / mol within the above molecular weight distribution range.

In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene equivalent molecular weights analyzed by gel permeation chromatography (GPC).

More specifically, the olefinic polymer according to one embodiment of the present invention may be one that satisfies the following requirements (1) to (4) simultaneously:

(1) Density: 0.850 g / cc to 0.910 g / cc

(2) Melt index measured at 190 ° C. and 2.16 kg loading conditions: 0.1 g / 10 min to 100 g / 10 min,

(3) molecular weight distribution (MWD): 1.5 to 4.0,

(4) Temperature Elution Elution temperature Te1, Te2 and Te3 of three olefinic polymers are included in the temperature range of -20 ° C to 120 ° C for fractional measurement.

Thus, by simultaneously meeting the density, melt index, MWD and elution temperature conditions it can exhibit more excellent impact strength characteristics.

More specifically, the melt index measured at a density of 0.86 g / cc to 0.88 g / cc, 190 ° C., 2.16 kg load conditions, 0.1 g / 10 min to 30 g / 10 min, molecular weight distribution 1.5 to 3.0, Te1 is in the range of -20 ° C to 30 ° C, Te2 is in the range of 10 ° C to 80 ° C, Te3 is in the range of 40 ° C to 120 ° C, and the fractional ratio of the first semicrystalline olefin polymer peak (P1) is 30% to 80%, the fractional ratio of the second semicrystalline olefinic polymer peak (P2) may be 5% to 40%, and the fractional ratio of the third semicrystalline olefinic polymer peak (P3) may be 5% to 50%.

Olefin-based polymers satisfying the above-described physical properties exhibit excellent mechanical strength, particularly impact strength, and thus can be used for various packaging, construction, and household goods such as materials for automobiles, electric wires, toys, textiles, medical, and the like. It is useful for blow molding, extrusion molding or injection molding in various fields and applications.

The olefin polymer as described above may be obtained by polymerizing an olefin monomer using a catalyst composition comprising a transition metal compound of Formula 1 and a transition metal compound of Formula 2. Accordingly, according to another embodiment of the present invention, a method for preparing the olefin polymer is provided.

<Formula 1>

<Formula 2>

In Chemical Formulas 1 and 2,

M ₁ and M ₂ are each independently a Group 4 transition metal,

Q _1, Q ₂ , Q ₃ and Q ₄ each independently represent a hydrogen atom, a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl having 6 to 20 carbon atoms. Group selected from the group consisting of an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkylamido group having 1 to 20 carbon atoms, an arylamido group having 6 to 20 carbon atoms, and an alkylidene group having 1 to 20 carbon atoms Become,

R ₁ to R ₆ are each independently a hydrogen atom, a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 7 carbon atoms. Or a metalloid radical of a Group 14 metal substituted with 20 alkylaryl groups, arylalkyl groups having 7 to 20 carbon atoms, and hydrocarbyl having 1 to 20 carbon atoms; Or at least two adjacent functional groups of R ₁ to R ₆ are connected to each other and selected from a group consisting of a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms; An aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms, unsubstituted or substituted with one substituent;

R ₇ to R ₁₁ are each independently a hydrogen atom, a halogen group, an amino group, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, Or a metalloid radical of a Group 14 metal substituted with an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms and a hydrocarbyl group having 1 to 20 carbon atoms; Or two or more functional groups adjacent to each other in R ₇ to R ₁₁ are connected to each other and selected from the group consisting of a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms An aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms, which is unsubstituted or substituted with a substituent of;

R ₂₁ to R ₂₇ are each independently a group 14 metal substituted with a hydrogen atom, a halogen group, a C1-C20 hydrocarbyl group, a C1-C20 heterohydrocarbyl group, and a C1-C20 hydrocarbyl group It is selected from the group consisting of metalloid radical of, specifically R ₂₁ to R ₂₇ are each independently a hydrogen atom, a halogen group, a silyl group, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, 3 carbon atoms Metalloid radicals of Group 14 metals substituted with a cycloalkyl group of 20 to 20, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, an arylalkyl group of 7 to 20 carbon atoms, and a hydrocarbyl group of 1 to 20 carbon atoms. It is selected from the group consisting of;

X ₁ to X ₃ are each independently selected from the group consisting of a hydrogen atom, a halogen group, a hydrocarbyl group of 1 to 20 carbon atoms and a heterohydrocarbyl group of 1 to 20 carbon atoms, more specifically a hydrogen atom, a halogen group, Silyl group, amino group, (alkyl of 1 to 20 carbon atoms) amino group, alkyl group of 1 to 20 carbon atoms, alkenyl group of 2 to 20 carbon atoms, cycloalkyl group of 3 to 20 carbon atoms, aryl group of 6 to 20 carbon atoms, 7 to 20 carbon atoms An alkylaryl group and an arylalkyl group having 7 to 20 carbon atoms; Or two or more adjacent functional groups of X ₁ to X ₃ are connected to each other, such as a halogen group, a silyl group, an amino group, an (alkyl having 1 to 20 carbon atoms) amino group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and An aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms substituted with at least one substituent selected from the group consisting of 6 to 20 carbon atoms, and

Z is phosphorus (P), arsenic (As) or antimony (Sb).

In the transition metal compound of Formula 1, the metal site is linked by a cyclopentadienyl (Cp) ligand to which an amino group is linked to a phenylene bridge, so that the Cp-M ₁ -N angle is structurally narrow, and a monomer is approached. Q ₁ -M ₁ -Q ₂ angle is characterized by keeping wide. In addition, unlike the CGC structure linked by the silicon bridge, in the compound structure represented by Formula 1, cyclopentadiene (Cp), phenylene bridge, nitrogen, and metal (M ₁ ) in which benzothiophene is fused by a ring-shaped bond. ) The seats are connected in order to form a more stable and rigid five-point ring structure. That is, the nitrogen atom of the amino group is connected to the phenylene bridge by two bonds in the form of a ring to have a more complex complex structure. Therefore, when these compounds are reacted with methylaluminoxane or a cocatalyst such as B (C ₆ F ₅ ) ₃ to be activated and then applied to olefin polymerization, they exhibit characteristics such as high activity, high molecular weight and high copolymerization even at high polymerization temperatures. It is possible to produce polyolefins having. In particular, due to the structural characteristics of the catalyst, low density polyethylene as well as a large amount of alpha-olefins can be introduced, so that a low density polyolefin air having a density of 0.910 g / cc or less, more specifically, a density of 0.855 g / cc to 0.910 g / cc The preparation of the coalescence is possible. In particular, by using the catalyst composition containing the transition metal compound, it is possible to prepare a polymer having a narrow MWD compared to CGC, excellent copolymerizability, and high molecular weight even in a low density region.

In addition, various substituents may be introduced into the benzothiophene-fused cyclopentadienyl and quinoline-based compounds, which ultimately control the structure and physical properties of polyolefins produced by easily controlling the electronic and three-dimensional environment around the metal. . The compound of Formula 1 is preferably used to prepare a catalyst for the polymerization of the olefin monomer, but is not limited thereto and may be applicable to all fields in which the transition metal compound may be used.

Meanwhile, the transition metal compound of Formula 2, which is used in combination with the transition metal compound of Formula 1, is an imide-based ligand such as phosphinimide ligands connected to a derivative of cyclopentadiene having a heterocycle including sulfur. Has a structure. As a result, when used as a catalyst when copolymerizing ethylene and olefinic polymers such as octene, hexene or butene, it exhibits high catalytic activity and enables the production of olefinic polymers having excellent physical properties such as high molecular weight and low density. In addition, it is excellent in the miscibility with the transition metal compound of Formula 1 and uniformly mixed in the catalyst composition, it is possible to further improve the catalytic activity of the catalyst composition.

Specifically, in Formula 1, M ₁ may be Ti, Hf or Zr.

In addition, in Formula 1, Q ₁ and Q ₂ may be each independently selected from the group consisting of a hydrogen atom, a halogen group and an alkyl group having 1 to 6 carbon atoms.

In addition, in Formula 1, R ₁ and R ₂ may be an alkyl group having 1 to 20 carbon atoms, more specifically, an alkyl group having 1 to 6 carbon atoms, and even more specifically, a methyl group.

In Formula 1, R ₃ to R ₆ are each independently a hydrogen atom; An alkyl group having 1 to 20 carbon atoms; Or an alkenyl group having 2 to 20 carbon atoms, more specifically a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and even more specifically, a hydrogen atom.

In addition, in Chemical Formula 1, R ₇ to R ₁₀ may be each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In addition, in Formula 1, R ₁₁ may be an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms, wherein the substituent is a halogen group, carbon number It may be any one or two or more selected from the group consisting of an alkyl group of 1 to 20, an alkenyl group of 2 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, and an aryloxy group of 6 to 20 carbon atoms. In addition, in Formula 1, R ₁₁ may be connected to R ₁₀ adjacent to R ₁₁ to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms. In this case, the aliphatic ring or aromatic ring may be substituted with any one or two or more substituents selected from the group consisting of a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. have.

If More specifically, the transition metal compound is R ₁₁ is an aryl group, or an alkyl aryl group having 7 to 20 in the alkyl group of the unsubstituted or substituted, having 1 to 20 carbon atoms, having 6 to 20 carbon atoms represented by the formula 1, e. For example, the compound may be represented by the following Chemical Formula, and any one or a mixture of two or more thereof may be used:

In the case where the transition metal compound represented by the formula (1) are connected to each other and R ₁₀ to R ₁₁ are adjacent to the R ₁₁ form a ring of 5 to 20 carbon atoms aliphatic ring or a carbon number of 6 to 20, to the general formula (3) It may be a compound represented:

<Formula 3>

In Chemical Formula 3,

M ₁ , Q ₁ , Q ₂ , R ₁ to R ₉ are the same as defined in Chemical Formula 1,

Cy is an aliphatic ring group having 4 or 5 carbon atoms including nitrogen (N),

R, R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms. An aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms;

m may be an integer of 0 to 2 when Cy is an aliphatic ring group having 4 carbon atoms, and may be an integer of 0 to 4 when Cy is an aliphatic ring having 5 carbon atoms.

More specifically, the compound of Formula 3 may be a compound of Formula 3a or 3b:

<Formula 3a>

In Formula 3a, R _a to R _d are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, And an arylalkyl group having 7 to 20 carbon atoms, and the remaining substituents are as defined in Chemical Formula 1,

<Formula 3b>

In Chemical Formula 3b,

R _e and R _f each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. It is selected from the group consisting of an alkylaryl group having 7 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms, the remaining substituents are the same as defined in the formula (1).

Specific examples of the transition metal compound of Formula 3 may be a compound represented by the following formula:

The transition metal compound of Formula 1 may be prepared by the following steps a) to d):

a) preparing a compound represented by the following Chemical Formula 5 by reacting an amine compound represented by the following Chemical Formula 4 with alkyllithium, and then adding a compound including a protecting group (-R ₀ );

b) preparing a amine compound represented by the following Chemical Formula 7 by reacting the compound represented by Chemical Formula 5 with alkyllithium, and then adding a ketone compound represented by Chemical Formula 6;

c) preparing a dilithium compound represented by Chemical Formula 8 by reacting the compound represented by Chemical Formula 7 with n-butyllithium; And

d) preparing a transition metal compound represented by Chemical Formula 1 by reacting the compound represented by Chemical Formula 8 with MCl ₄ (M = group 4 transition metal) and an organolithium compound.

<Formula 4>

<Formula 5>

 <Formula 6>

 <Formula 7>

<Formula 8>

In Chemical Formulas 4 to 8,

R 'is a hydrogen atom,

R ₀ is a protecting group,

Other substituents are as defined in formula (1).

The compound including a protecting group in step a) may be trimethylsilyl chloride, benzyl chloride, t-butoxycarbonyl chloride, benzyloxycarbonyl chloride or carbon dioxide.

When the compound including the protecting group is carbon dioxide, the compound of Formula 5 may be a lithium carbamate compound represented by Formula 5a:

<Formula 5a>

Each substituent in Formula 5a is as defined in Formula 1 above.

Specifically, the compound of Formula 1 may be prepared by the following Scheme 1.

<Scheme 1>

In Scheme 1, the description of the substituent is the same as in formula (1).

Meanwhile, the transition metal compound of Formula 2 may be a compound of Formula 2a.

[Formula 2a]

In Chemical Formula 2a,

M ₂ may be the same as defined above, specifically, Ti, Hf or Zr,

Q ₃ and Q ₄ may be the same as defined above, specifically, each independently may be a halogen group or an alkyl group having 1 to 8 carbon atoms,

R ₂₁ to R ₂₇ may be the same as defined above, more specifically, R ₂₁ to R ₂₇ are each independently a hydrogen atom, a halogen group, a silyl group, an alkyl group having 1 to 8 carbon atoms, an alke having 2 to 6 carbon atoms Of a Group 14 metal substituted with a silyl group, a C3-12 cycloalkyl group, a C6-C18 aryl group, a C7-C18 alkylaryl group, a C7-C18 arylalkyl group, and a C1-C8 hydrocarbyl group Selected from the group consisting of metalloid radicals, and more specifically, R ₂₁ to R ₂₇ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms or 1 to 4 carbon atoms;

X ₁ to X ₃ may be the same as defined above, more specifically, X ₁ to X ₃ are each independently a hydrogen atom, a halogen group, a silyl group, an amino group, (alkyl having 1 to 8 carbon atoms), C 1 Selected from the group consisting of an alkyl group of 8 to 8, an alkenyl group of 2 to 6 carbon atoms, a cycloalkyl group of 3 to 12 carbon atoms, an aryl group of 6 to 18 carbon atoms, an alkylaryl group of 7 to 18 carbon atoms, and an arylalkyl group of 7 to 18 carbon atoms Or; Or two adjacent functional groups of X ₁ to X ₃ are connected to each other to form a halogen group, a silyl group, an amino group, an (alkyl having 1 to 8 carbon atoms) amino group, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 6 carbon atoms and a carbon number A cycloalkyl group having 5 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms substituted with at least one substituent selected from the group consisting of 6 to 12 aryl groups, and more specifically X ₁ to X ₃ are each independently It may be selected from the group consisting of a halogen group, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

More specifically, the second transition metal compound of Chemical Formula 2, which is more preferred for controlling the electronic steric environment around the metal, may be the following compounds, and any one or a mixture of two or more thereof may be used.

In the above chemical structures, Cy is a cyclohexyl group, tBu is a t-butyl group, Me is a methyl group and Ph is a phenyl group.

In addition to the compounds exemplified above, the transition metal compound of Formula 2 may have various structures within the range defined in Formula 2, and these compounds may exhibit equivalent functions and effects.

The transition metal compound of Chemical Formula 2 may be prepared using a known synthetic reaction.

The catalyst composition used to prepare the olefin-based polymer may specifically include the transition metal compounds of Formulas 1 and 2 in a weight ratio of 99: 1 to 1:99. When the mixing ratio of the transition metal compounds of Formulas 1 and 2 is outside the above range, it is difficult to prepare an olefin polymer that satisfies the physical property requirements defined above. More specifically, the catalyst composition may mix the transition metal compounds of Formulas 1 and 2 in a weight ratio of 50:50 to 80:20.

In addition, the catalyst composition may further include a promoter.

The promoter may be used without particular limitation as long as it is known in the art such as alkylaluminoxane, alkylaluminum or Lewis acid. Specifically, the promoter may include any one or a mixture of two or more selected from the group consisting of compounds represented by Formulas 9 to 12:

<Formula 9>

-[Al (R ₄₁ ) -O] a-

In Formula 9, R ₄₁ is a halogen group, a C 1-20 hydrocarbyl group or a C 1-20 hydrocarbyl group substituted with halogen, a is an integer of 2 or more,

<Formula 10>

D (R ₄₂ ) ₃

In Formula 10, D is aluminum or boron, each R ₄₂ is independently a halogen group, a hydrocarbyl group having 1 to 20 carbon atoms or a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen.

<Formula 11>

[LH] + [Z (A) ₄ ]-

<Formula 12>

[L] + [Z (A) ₄ ]-

In Chemical Formulas 11 and 12, L is a neutral or cationic Lewis acid, H is a hydrogen atom, Z is a Group 13 element, and each A independently has one to six carbon atoms of 1 to 20 hydrogen atoms may be substituted with a substituent. It is an aryl group or a C1-C20 alkyl group, The said substituent is a halogen group, a C1-C20 hydrocarbyl group, a C1-C20 alkoxy group, or a C6-C20 aryloxy group.

A method of preparing the catalyst composition, comprising: first contacting the catalyst composition with a compound represented by Formula 9 or Formula 10 to obtain a mixture; And adding the compound represented by Formula 11 or 12 to the mixture.

And, second, to provide a method for preparing a catalyst composition by contacting the catalyst composition and the compound represented by the formula (11) or (12).

In the case of the first method of preparing the catalyst composition according to the above-described embodiment, the molar ratio of the compound represented by Formula 9 or Formula 10 with respect to the catalyst composition may be 1: 2 to 1: 5,000, respectively. Specifically 1:10 to 1: 1,000, and even more specifically 1:20 to 1: 500.

In addition, the molar ratio of the compound represented by Formula 11 or 12 with respect to the catalyst composition may be 1: 1 to 1:25, more specifically 1: 1 to 1:10, even more specifically 1: 1 To 1: 5.

When the molar ratio of the compound represented by Formula 9 or Formula 10 to the catalyst composition is less than 1: 2, there is a problem that the alkylation of the metal compound does not proceed completely because the amount of the alkylating agent is very small. Although alkylation of the compound is made, there is a problem that the activation of the alkylated metal compound is not completely performed due to a side reaction between the remaining excess alkylating agent and the activator of Formula 14.

In addition, when the ratio of the compound represented by Formula 11 or 12 with respect to the total amount of the transition metal compounds of Formulas 1 and 2 is less than 1: 1, the amount of the activator is relatively small, resulting in incomplete activation of the metal compound. If there is a problem that the activity of the catalyst composition is deteriorated and if it is greater than 1:25, the metal compound is fully activated, but the excess amount of the activator does not economically cost or the purity of the polymer produced is poor. have.

In addition, in the case of the second method of the catalyst composition preparation method, the molar ratio of the compound represented by the formula (10) relative to the catalyst composition may be 1: 1 to 1: 500, more specifically 1: 1 to 1:50 And even more specifically, 1: 2 to 1:25. When the molar ratio is less than 1: 1, the amount of the activator is relatively small, so that the activation of the metal compound may not be completed, and thus the activity of the resulting catalyst composition may be inferior. Although completely made, there is a problem that the cost of the catalyst composition is economically undesirable or the purity of the resulting polymer is poor with the remaining excess activator.

Aliphatic hydrocarbon solvents having 5 to 12 carbon atoms, such as pentane, hexane or heptane, as a reaction solvent in the preparation of the catalyst composition described above; Hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene; Or aromatic hydrocarbon solvents such as benzene, toluene, etc. may be used, but are not necessarily limited thereto, and all solvents available in the art may be used. The solvent used herein is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating a small amount of alkylaluminum, and may be carried out by further using a promoter.

In addition, the catalyst composition may further include an additive. For example, a compound containing a hetero atom may be included. Specifically, examples of the compound containing a hetero atom include a hetero ring compound; Or alkanes containing heteroatoms.

Examples of the heterocyclic compound include aromatic rings containing heteroatoms; Heterocycloalkanes; Or heterocycloalkene. Examples of the alkanes containing the heteroatom include alkanes containing amine groups or ether groups. The heteroaromatic ring; Heterocycloalkanes; Or heterocycloalkenes include 5- or 6-membered rings. The compound containing the heteroatom may include O, S, Se, N, P or Si as a heteroatom. The compound containing a heteroatom may include one heteroatom. The compound containing the hetero atom may be substituted, and when the compound containing the hetero atom is substituted, it may be substituted with one or two or more from the group consisting of hydrogen, methyl, phenyl and benzyl.

Examples of the compound containing a hetero atom include pyridine, 3,5-dimethylpyridine, 2,4,6-trimethylpyridine, 2,6-dimethylpyridine, 2,4-dimethylpyridine, thiophene, 2-methylthiophene , 2,3-dimethylthiophene, piperidine, phosphinene, pyrrole, 2-methylpyrrole, aniline, para-toluidine, tetrahydrofuran, 2,3-dimethyltetrahydrofuran, 2,5-tetrahydrofuran, Selected from the group consisting of 3,4-dihydro-2H-pyrene, furan, 2-methylfuran, 2,3-dimethylfuran, 2,5-dimethylfuran, diethylether, methyl tertbutyl ether and triethylamine It may include any one or two or more, but is not limited thereto.

In addition, the first and second transition metal compounds and the promoter may be used in a form supported on a carrier. The carrier may be silica-alumina, silica-magnesia, or the like, and other carriers known in the art may be used. In addition, such a carrier may be used in a dry state at a high temperature, and the drying temperature may be, for example, 180 ° C to 800 ° C. If the drying temperature is too low below 180 ° C., an excess portion on the carrier may react with the promoter to degrade the performance. If the drying temperature is too high above 800 ° C., the hydroxy group content on the surface of the carrier may be lowered to promote the promoter. The reaction site with and may decrease.

In addition, the compound represented by Formula 9 may be alkyl aluminoxane, specific examples thereof include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and more specifically, methyl aluminoxane. .

In addition, the compounds represented by the above formula (10) are specifically trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tri Cyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxy Seed, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like, more specifically, may be selected from trimethylaluminum, triethylaluminum, and triisobutylaluminum.

In addition, the compound of Formula 11 or 12 specifically triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) boron, trimethyl Ammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammoniumtetrapentafluorophenylboron, N , N-diethylanilidedium tetrapetyl boron, N, N-diethylanilidedium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron , Triphenyl phosphonium tetraphenyl boron, trimethyl phosphonium tetraphenyl boron, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylarm Aluminum tetramethylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra (p-tolyl) aluminum, tripropylammonium tetra (p-tolyl) aluminum, triethylammonium tetra (o, p-dimethylphenyl) aluminum, tributylammonium Tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N -Diethylanilinium tetraphenylaluminum, N, N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatentraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum , Triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylboron, tripro Ammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) boron, tripropylammonium tetra (p-tolyl) boron, triethylammonium tetra (o, p-dimethylphenyl) boron, trimethylammonium tetra (o, p-dimethylphenyl Boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N-diethylanilinium tetra Phenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, Triphenylcarbonium tetra (p-trifluoromethylphenyl) boron or triphenylcarbonium tetrapentafluorophenylboron and the like.

On the other hand, the monomers usable in the production of the olefin polymers include, for example, alpha-olefin monomers, cyclic olefin equivalents, diene olefin monomers, triene olefin monomers or styrene monomers. One type of monomer may be homopolymerized, or two or more types may be mixed and copolymerized.

The alpha-olefin monomers include aliphatic olefins having 2 to 12 carbon atoms, specifically 2 to 8 carbon atoms, and more specifically ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 4,4-dimethyl-1-pentene, 4,4 -Diethyl-1-hexene, 3,4-dimethyl-1-hexene, etc. can be illustrated. In addition, the alpha-olefins may be homopolymerized or alternating, random, or block copolymerized.

In addition, the copolymerization of the above-mentioned alpha-olefins is copolymerization of ethylene and an alpha-olefin having 2 to 12 carbon atoms, specifically 2 to 8 carbon atoms (ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 4 -Methyl-1-pentene, ethylene and 1-octene) and copolymerization of propylene with alpha-olefins having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms (propylene and 1-butene, propylene and 4-methyl-1-pentene , Propylene and 4-methyl-1-butene, propylene and 1-hexene, propylene and 1-octene).

In the copolymerization of ethylene or propylene with other alpha-olefins, the amount of other alpha-olefins may be up to 90% by weight of the total monomers. More specifically, the ethylene copolymer is 70% by weight or less, specifically 60% by weight or less, more specifically 50% by weight or less, and 1% to 90% by weight, specifically 5% by weight, for the propylene copolymer. To 90% by weight, more specifically 10% to 70% by weight.

The cyclic olefins may be used having 3 to 24 carbon atoms, specifically 3 to 18, more specifically cyclopentene (cyclopentene), cyclobutene, cyclohexene, 3-methylcyclohexene, cyclooctene, tetracyclo Decene, octacyclodecene, dicyclopentadiene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6- Dimethyl-2-norbornene, 5,5,6-trimethyl-2-norbornene or ethylene norbornene and the like. The cyclic olefins may be copolymerized with the alpha-olefins, wherein the amount of the cyclic olefin may be 1 to 50 mol%, specifically 2 to 50 mol% with respect to the copolymer.

In addition, the dienes and triene may be a polyene having 4 to 26 carbon atoms having two or three double bonds, specifically 1,3-butadiene, 1,4-pentadiene, 1,4- Hexadiene, 1,5-hexadiene, 1,9-decadiene, 2-methyl-1,3-butadiene, and the like. In addition, the styrenes may be styrene or styrene substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen group, an amine group, a silyl group, or a halogenated alkyl group.

The polymerization step may be carried out in solution phase, slurry phase, bulk phase or gas phase polymerization in a hydrocarbon solvent.

Since the catalyst composition is present in the form of a carrier or insoluble particles of the carrier, as well as the catalyst composition in a homogeneous solution, it may be carried out in a solution phase, a slurry phase, a bulk phase, or a gas phase polymerization. In addition, each polymerization condition may vary depending on the state of the catalyst used (homogeneous or heterogeneous phase (supported)), the polymerization method (solution polymerization, slurry polymerization, gas phase polymerization), the desired polymerization result or the shape of the polymer. Can be. The degree of deformation thereof can be easily modified by anyone skilled in the art.

The hydrocarbon solvents include aliphatic hydrocarbon solvents having 5 to 12 carbon atoms, for example, pentane, hexane, heptane, nonane, decane, and isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene; Alternatively, any one or two or more dissolved or diluted in a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane or chlorobenzene may be mixed and injected. The solvent used herein is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating a small amount of alkylaluminum, and may be carried out by further using a promoter.

Examples of the alkylaluminum include trialkylaluminum, dialkyl aluminum halides, alkyl aluminum dihalides, aluminum dialkyl hydrides or alkyl aluminum sesqui halides, and more specifically, Al (C ₂ H ₅ ) ₃ , Al (C ₂ H ₅ ) ₂ H, Al (C ₃ H ₇ ) ₃ , Al (C ₃ H ₇ ) ₂ H, Al (iC ₄ H ₉ ) ₂ H, Al (C ₈ H ₁₇ ) ₃ , Al (C ₁₂ H ₂₅ ) ₃ , Al (C ₂ H ₅ ) (C ₁₂ H ₂₅ ) ₂ , Al (iC ₄ H ₉ ) (C ₁₂ H ₂₅ ) ₂ , Al (iC ₄ H ₉ ) ₂ H, Al ( iC ₄ H ₉ ) ₃ , (C ₂ H ₅ ) ₂ AlCl, (iC ₃ H ₉ ) ₂ AlCl, or (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ . Such organoaluminum compounds may be introduced continuously into each reactor and may be introduced at a rate of about 0.1 mole to 10 moles per kilogram of reaction medium introduced into the reactor for proper water removal.

In addition, the polymerization step may be carried out in a batch reactor or a continuous reactor, more specifically, may be performed in a continuous reactor.

In addition, the polymerization step may be carried out in the presence of an inert gas, such as arcon or nitrogen gas.

The inert gas, for example, may be used alone or in combination with nitrogen gas or hydrogen gas.

The use of the inert gas serves to prevent the activity of the catalyst due to the inflow of moisture or impurities in the air, and may be added so that the mass ratio of the inert gas to the olefin monomer is about 1:10 to 1: 100. It is not limited to this. When the amount of inert gas is used too little, the catalyst composition reacts rapidly, making it difficult to manufacture an olefin polymer having a molecular weight and molecular weight distribution, and when the amount of the inert gas is added, the activity of the catalyst composition is sufficiently realized. It may not be.

The polymerization temperature when copolymerizing alpha olefin as a comonomer with the catalyst may range from about 130 ° C. to about 250 ° C., specifically from about 140 ° C. to about 200 ° C.

In addition, the polymerization pressure may be about 1 bar to about 150 bar, specifically about 1 bar to about 120 bar, more specifically about 10 bar to about 120 bar.

The olefin polymer prepared by the above production method may be surface treated with an inorganic material such as talc, Ca or Si based on a conventional method. Accordingly, the olefin polymer according to the present invention may further include a coating layer including an inorganic material such as talc, Ca or Si based on the surface thereof.

According to another embodiment of the present invention, a catalyst composition including the transition metal compound of Formula 1 and the transition metal compound of Formula 2 is useful for preparing the olefin polymer.

The catalyst composition is the same as described in the method for preparing the olefin polymer.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

Synthesis of Ligands and Transition Metal Compounds

Organic reagents and solvents were purchased from Aldrich and purified by standard methods unless otherwise noted. At all stages of the synthesis, the contact between air and moisture was blocked to increase the reproducibility of the experiment.

Preparation Example 1

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

To a solution of 2-methyl-1,2,3,4-tetrahydroquinoline (2 g, 13.6 mmol) in 10 mL of Ether was slowly added dropwise nBuLi (14.9 mmol, 1.1 eq) at -40 ° C. After gradually warming up to room temperature, the mixture was stirred at room temperature for 4 hours. The reaction was maintained at low temperature for 0.5 hours after injecting CO ₂ (g) having the temperature lowered to -40 ° C. After slowly warming up, the remaining CO ₂ (g) was removed through a bubbler. THF (17.6mmol, 1.4ml and tBuLi (10.4mmol, 1.3eq) was injected at -20 ° C, and then aged at low temperature for 2 hours at -20 ° C. The ketone (1.9g, 8.8mmol) was diethyl ether (Diethyl ether). After stirring for 12 hours, the mixture was stirred at room temperature for 12 hours, 10mL of water was added, hydrochloric acid (2N, 60mL) was added, stirred for 2 minutes, organic solvent was extracted, neutralized with NaHCO ₃ aqueous solution, and the organic solvent was extracted. Water was removed with MgSO _{4. A} yellow oil (1.83 g, 60% yield) was obtained through a silica gel column.

1 H NMR (C ₆ D ₆ ): δ 1.30 (s, 3H, CH ₃ ), 1.35 (s, 3H, CH ₃ ), 1.89 to 1.63 (m, 3H, Cp-H quinoline-CH ₂ ), 2.62 to 2.60 (m, 2H, quinoline-CH ₂ ), 2.61-2.59 (m, 2H, quinoline-NCH ₂ ), 2.70-2.57 (d, 2H, quinoline-NCH ₂ ), 3.15-3.07 (d, 2H, quinoline-NCH ₂ ), 3.92 (broad, 1H, NH), 6.79 ~ 6.76 (t, 1H, aromatic), 7.00 ~ 6.99 (m, 2H, aromatic), 7.30 ~ 7.23 (m, 2H, aromatic), 7.54 ~ 7.53 (m , 1H, aromatic), 7.62 ~ 7.60 (m, 1H, aromatic) ppm

8- (1,2-dimethyl-1H- Benzo [b] cyclopenta [d] thiophene -3- days) -2- methyl -1,2,3,4- Tetrahydroquinoline Of titanium dichloride (8- (1,2-dimethyl-1H-benzo [b] cyclopenta [d] thiophen-3-yl) -2-methyl-1,2,3,4-tetrahydroquinoline-titanium dichloride) Produce

Ligand of 8- (1,2-dimethyl-1H-benzo [b] cyclopenta [d] thiophen-3-yl) -2-methyl-1,2,3,4-tetrahydroquinoline prepared above 1.0 g, 2.89 mmol) was slowly added dropwise n-BuLi (3.0 mmol, 2.1 eq) at -20 ° C. It was observed that a yellow slurry (slurry) was formed, gradually warmed up to room temperature, and stirred at room temperature for 12 hours. DME solution of TiCl ₄ (806mg, 2.89mmol, 1.0eq) was added dropwise and stirred at room temperature for 12 hours. The solvent was removed and then extracted with toluene to give a red solid (700 mg, 52% yield).

1 H NMR (C ₆ D ₆ ): δ 1.46-1.467 (t, 2H, quinoline-NCH ₂ ), 1.85 (s, 3H, Cp-CH ₃ ), 1.79 (s, 3H, Cp-CH ₃ ), 2.39 ( s, 3H, Cp-CH ₃ ), 2.37 (s, 3H, Cp-CH ₃ ), 2.10-2.07 (t, 2H, quinoline-NCH ₂ ), 5.22-5.20 (m, 1H, N-CH), 5.26 ~ 5.24 (m, 1H, N-CH), 6.89 ~ 6.87 (m, 2H, aromatic) 6.99 ~ 6.95 (m, 1H, aromatic), 7.19 ~ 7.08 (m, 2H, aromatic), 7.73 ~ 7.68 (m, 1H, aromatic) ppm

Preparation Example 2

After dissolving the compound represented by the formula (i) (1.30g, 2.37mmol) in toluene (20ml), MeMgBr (1.62ml, 4.86mmol, 2.05eq) was slowly added dropwise at room temperature (23 ℃), then 12 at room temperature Stir for hours. The starting material was confirmed by NMR, and the toluene solvent was filtered under reduced pressure, and then the reaction mixture was dissolved in hexane (30 ml). Thereafter, the solid was removed through filtration, and the hexane solvent in the resulting solution was filtered under reduced pressure to obtain a transition metal compound represented by the following Chemical Formula (ii).

1 H NMR (500 MHz, C ₆ D ₆ ): δ 7.62 (d, 1H), 7.48 (d, 1H), 7.13 (t, 1H), 7.03 (t, 1H), 2.30 (s, 3H), 2.09 (s , 3H), 2.02 (s, 3H), 1.28 (d, 27H), -0.24 (s, 3H), -0.27 (s, 3H)

<Production of Olefin Polymer>

Example 1

After the 1.5 L autoclave continuous process reactor was charged with hexane solvent (4.67 kg / h) and 1-octene (1.42 kg / h), the temperature at the top of the reactor was preheated to 160 ° C. Triisobutylaluminum compound (0.03 mmol / min), a mixture of the transition metal compound prepared in Preparation Example 1 and the compound prepared in Preparation Example 2 (mixed weight ratio = 75: 25, 0.675 μmol / min), and dimethylaniyl Linium tetrakis (pentafluorophenyl) borate cocatalyst (2.03 μmol / min) was simultaneously introduced into the reactor. Subsequently, ethylene (0.87 kg / h) was introduced into the autoclave reactor and maintained at 160 ° C. for 30 minutes or more in a continuous process at a pressure of 89 bar, followed by a copolymerization reaction to produce an ethylene-1 octene copolymer as an olefin polymer. Got. Next, the remaining ethylene gas was removed and the polymer solution was dried in a vacuum oven for at least 12 hours, and then physical properties were measured.

Example 2

1-octene (1.55 kg / h), triisobutylaluminum compound (0.03 mmol / min), a mixture of the transition metal compound prepared in Preparation Example 1 and the compound prepared in Preparation Example 2 (mixed weight ratio = 75: 25 , 0.75 μmol / min), and a olefin polymer was prepared in the same manner as in Example 1, except that dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst (2.25 μmol / min) was used.

Example 3

1-octene (1.51 kg / h), triisobutylaluminum compound (0.05 mmol / min), a mixture of the transition metal compound prepared in Preparation Example 1 and the compound prepared in Preparation Example 2 (mixed weight ratio = 75: 25 , 0.75 μmol / min), and a olefin polymer was prepared in the same manner as in Example 1, except that dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst (2.25 μmol / min) was used.

Example 4

1-octene (1.30 kg / h), triisobutylaluminum compound (0.04 mmol / min), a mixture of the transition metal compound prepared in Preparation Example 1 and the compound prepared in Preparation Example 2 (mixed weight ratio = 75: 25 , 0.58 μmol / min), and a olefin polymer was prepared in the same manner as in Example 1, except that dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst (1.40 μmol / min) was used.

Example 5

1-octene (1.30 kg / h), triisobutylaluminum compound (0.04 mmol / min), a mixture of the transition metal compound prepared in Preparation Example 1 and the compound prepared in Preparation Example 2 (mixed weight ratio = 75: 25 , 0.70 μmol / min), and a olefin polymer was prepared in the same manner as in Example 1, except that dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst (2.0 μmol / min) was used.

Comparative Example 1

Prepared using only one metallocene catalyst, an ethylene-1 octene copolymer (product name: Eg8407) manufactured by Dow having a talc coating layer was prepared.

Comparative Example 2

Dow's ethylene-1 octene copolymer (product name: Eg8200) prepared using only one metallocene catalyst was prepared.

Comparative Example 3

LG Chem's ethylene-1 octene copolymer (product name: LC170) prepared using only one metallocene catalyst was prepared.

Comparative Example 4

After the 1.5 L autoclave continuous process reactor was charged with hexane solvent (4.67 kg / h) and 1-octene (1.42 kg / h), the temperature at the top of the reactor was preheated to 160 ° C. Triisobutylaluminum compound (0.03 mmol / min), [(1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-η5, κ-N] titaniumdimethyl ([(1, 2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-η5, κ-N] titanium dimethyl) compound with tert-butyl (((1,2-dimethyl-3H-benzo [b] cyclopenta [d] thiophene -3-yl) dimethylsilyl) amino) dimethyl titanium (tert-butyl (((1,2-dimethyl-3H-benzo [b] cyclopenta [d] thiophen-3-yl) dimethylsilyl) amino) dimethyl titanium) (Mixed weight ratio = 75: 25, 0.675 µmol / min) and dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst (2.03 µmol / min) were simultaneously introduced into the reactor. Subsequently, ethylene (0.87 kg / h) was introduced into the autoclave reactor and maintained at 160 ° C. for 30 minutes or more in a continuous process at a pressure of 89 bar, followed by a copolymerization reaction to produce an ethylene-1 octene copolymer as an olefin polymer. Got. Next, the remaining ethylene gas was removed and the polymer solution was dried in a vacuum oven for at least 12 hours, and then physical properties were measured.

Comparative Example 5

1-octene (1.39 kg / h), triisobutylaluminum compound (0.04 mmol / min), [(1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-η5, κ -N] titanium dimethyl compound and dimethyl (1,2,3,4,5-pentamethylcyclopenta-2,4-dien-1-yl) ((tri-tert-butyl-15-phosphanilidene) A mixture of amino) titanium (dimethyl (1,2,3,4,5-pentamethylcyclopenta-2,4-dien-1-yl) (tri-tert-butyl-15-phosphanylidene) amino) titanium) : 25, 0.70 μmol / min), and a copolymer was prepared in the same manner as in Comparative Example 4 except for using the dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst (2.0 μmol / min). .

Experimental Example 1 Evaluation of Physical Properties of Olefin Polymer

Various physical properties were measured and evaluated for the olefin polymers prepared in Examples 1 to 5 and Comparative Examples 1 to 5 in the following manner.

(1) Density (g / cc) of the polymer; Measured by ASTM D-792.

(2) Melt index of polymer (Melt Index, MI, g / 10min): Measured by ASTM D-1238 (Condition E, 190 ° C, 2.16 Kg load).

(3) Weight average molecular weight (Mw, g / mol) and molecular weight distribution (MWD): The number average molecular weight (Mn) and the weight average molecular weight (Mw) were respectively measured by gel permeation chromatography (GPC). Moreover, the weight average molecular weight was divided by the number average molecular weight, and molecular weight distribution (MWD) was calculated.

(4) TREF (temperature rising elution fractionation)

TREF was measured using PolymerChar's TREF machine and measured in the range of -20 ° C to 120 ° C using o-dichlorobenzene as a solvent.

Specifically, 40 mg of polymer sample was dissolved for 30 minutes at 135 ° C. under 20 ml of o-dichlorobenzene solvent and then stabilized at 95 ° C. for 30 minutes. After introducing this into a TREF column, the mixture was cooled to −20 ° C. at a temperature lowering rate of 0.5 ° C./min and held for 2 minutes. Thereafter, the concentration of the polymer eluted was measured while flowing o-dichlorobenzene, a solvent, in a column at a flow rate of 0.5 mL / min while heating at a temperature decrease rate of 1 ° C / min from -20 ° C to 120 ° C.

(5) GPC peak number: Observed through gel permeation chromatography (GPC) analysis.

The results are shown in Table 1 below and FIGS. 1 to 5.

1 to 4 are temperature rise elution fractionation (TREF) graphs of the olefin polymers prepared in Examples 1 and 2 and Comparative Examples 1 and 4, respectively, and FIG. 5 is a gel of the olefin polymers prepared in Example 1. FIG. It is a graph showing the results of permeation chromatography (GPC) analysis.

	density	MI	Mw	MWD	TREF			TREF peak count	GPC peak count
unit	g / cc	g / 10min	g / mol		Te1	Te2	Te3	dog	dog
					℃ (%)	℃ (%)	℃ (%)
Example 1	0.869	10	98525	2.34	0.5 (70%)	41.4 (18%)	89.0 (12%)	3	One
Example 2	0.867	24.5	64738	2.68	-6.7 (58%)	38.8 (22%)	87.6 (20%)	3	One
Example 3	0.871	6.3	85088	2.60	0.3 (45%)	41.0 (22%)	88.0 (33%)	3	One
Example 4	0.873	1.7	103827	2.51	-20.0 (44%)	30.1 (14%)	89.6 (42%)	3	One
Example 5	0.872	5.6	89932	2.51	-20.0 (46%)	24.9 (13%)	88.9 (41%)	3	One
Comparative Example 1	0.871	27.9	62115	2.28	33.2 (100%)	-	-	One	One
Comparative Example 2	0.873	4.9	97635	2.31	34.8 (100%)	-	-	One	One
Comparative Example 3	0.872	1.1	100147	2.29	28.4 (100%)	-	-	One	One
Comparative Example 4	0.871	4.7	109031	2.55	1.4 (61%)	65.6 (39%)	-	2	One
Comparative Example 5	0.864	30.7	72836	2.91	-5.0 (84%)	98.8 (16%)	-	2	One

As a result, the olefinic polymers of Examples 1 to 5 according to the present invention showed three peaks of Te1, Te2 and Te3 on the TREF within a density of 0.850 g / cc to 0.910 g / cc. On the other hand, the polymers of Comparative Examples 1 to 5 only found one or two peaks within the same density range.

In addition, the olefin polymers of Examples 1 to 5 according to the present invention showed a single peak on GPC and had a molecular weight distribution (MWD) of 2.3 to 2.7, which showed a narrow molecular weight distribution on the same level as the polymers of Comparative Examples 1 to 5. It was.

Claims (11)

1. An olefinic polymer which exhibits a single peak upon gel permeation chromatography analysis and comprises the elution temperatures Te1, Te2 and Te3 of the three olefinic polymers in the temperature range of -20 ° C to 120 ° C upon elution fractional measurement.
2. The method of claim 1,

   Olefin-based polymers meeting the requirements of the following (1) to (4):

   (1) Density: 0.850 g / cc to 0.910 g / cc

   (2) Melt index measured at 190 ° C. and 2.16 kg loading conditions: 0.1 g / 10min to 100 g / 10min

   (3) molecular weight distribution: 1.5 to 4.0

   (4) Temperature Elution Elution temperature Te1, Te2 and Te3 of the three olefinic polymers in the temperature range of -20 ° C to 120 ° C in the fractionation measurement.
3. The method of claim 1,

   In the temperature-eluting fractional measurement, Te1 is present at a temperature lower than Te2, and Te2 is lower than Te3, and Te1 is -20 ° C to 100 with a density of an olefin polymer of 0.850 g / cc to 0.910 g / cc. ° C range, wherein Te2 is in the range 0 ° C to 120 ° C, and Te3 is in the range of 20 ° C to 120 ° C.
4. The method of claim 1,

   Wherein the density of the olefin polymer is 0.86 g / cc to 0.88 g / cc Te1 is in the range of -20 ℃ to 30 ℃, Te2 is in the range of 10 ℃ to 80 ℃, Te3 is in the range of 40 ℃ to 120 ℃ An olefin polymer.
5. The method of claim 1,

   The olefin polymer includes a first semicrystalline olefin polymer, a second semicrystalline olefin polymer and a third semicrystalline olefin polymer,

   The fractional ratio of the first semicrystalline olefinic polymer peak is 5% to 90%, the fractional ratio of the second semicrystalline olefinic polymer peak is 5% to 90%, and the third quaternary The fractional ratio of crystalline olefinic polymer peaks is 5% to 90% olefinic polymer.
6. The method of claim 1,

   The olefin polymer includes a first semicrystalline olefin polymer, a second semicrystalline olefin polymer and a third semicrystalline olefin polymer,

   The fractional ratio of the first semicrystalline olefinic polymer peak in the temperature eluting fractional measurement is 30% to 80%, the fractional ratio of the second semicrystalline olefinic polymer peak is 5% to 40%, and the third quaternary The fractional ratio of crystalline olefinic polymer peak is 5% to 50% olefinic polymer.
7. The method of claim 1,

   When the differential scanning calorimetry is measured at a density of 0.850 g / cc to 0.910 g / cc of the olefinic polymer, it includes three crystallization temperatures Tc1, Tc2 and Tc3, wherein Tc1 is in the range of 5 ° C or less, and Tc2 is in the range of 0 ° C to An olefinic polymer in the range of 60 ° C. and Tc 3 in the range of 80 ° C. to 130 ° C.
8. The method of claim 1,

   An olefin polymer having a melt index of 0.1 g / 10 min to 30 g / 10 min measured at 190 ° C. and 2.16 kg loading conditions.
9. The method of claim 1,

   An olefin polymer having a weight average molecular weight of 20,000 g / mol to 200,000 g / mol.
10. The method of claim 1,

    An olefin polymer having a molecular weight distribution of 1.5 to 3.0.
11. The method of claim 1,

    Olefin polymer for blow molding, extrusion molding or injection molding.

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