阅读说明：本技术 基于烯烃的聚合物 (Olefin-based polymers ) 是由 李银精 周炫珍 朴仁成 朴想恩 裴庆馥 李忠勳 于 2018-12-24 设计创作，主要内容包括：本发明涉及一种基于烯烃的聚合物,其具有(1)0.850g/cc至0.865g/cc的密度(d),(2)在190℃在2.16kg负荷条件下0.1g/10min至3.0g/10min的熔体指数(MI),以及(3)在交叉分级色谱(CFC)中在-20℃下10重量％或更多的可溶性级分(SF),其中该级分的重均分子量(Mw)在50,000g/mol至500,000g/mol范围内。根据本发明的基于烯烃的聚合物作为低密度基于烯烃的聚合物显示出改善的抗粘结性。(The present invention relates to an olefin-based polymer having (1) a density (d) of 0.850g/cc to 0.865g/cc, (2) a Melt Index (MI) of 0.1g/10min to 3.0g/10min at 190 ℃ under a 2.16kg load condition, and (3) a Soluble Fraction (SF) of 10 wt.% or more at-20 ℃ in cross-fractionation chromatography (CFC), wherein the weight average molecular weight (Mw) of the fraction is in the range of 50,000g/mol to 500,000 g/mol. The olefin-based polymer according to the present invention exhibits improved blocking resistance as a low density olefin-based polymer.)

1. An olefin-based polymer having

(1) A density (d) of 0.850g/cc to 0.865g/cc,

(2) a melt index (MI, 190 ℃, 2.16kg load conditions) of 0.1g/10min to 3.0g/10min, and

(3) 8% by weight or more of a Soluble Fraction (SF) at-20 ℃ in cross-fractionation chromatography (CFC), wherein the weight average molecular weight (Mw) of the fraction is in the range of 50,000g/mol to 500,000 g/mol.

2. The olefin-based polymer of claim 1, wherein the weight average molecular weight (Mw) of the soluble fraction of the olefin-based polymer at-20 ℃ in cross-fractionation chromatography (CFC) is in the range of 50,000 to 300,000 g/mol.

3. The olefin-based polymer of claim 1, wherein the weight average molecular weight (Mw) of the soluble fraction of the olefin-based polymer at-20 ℃ in cross-fractionation chromatography (CFC) is in the range of 60,000 to 200,000 g/mol.

4. The olefin-based polymer of claim 1, wherein the olefin-based polymer has (4) a Molecular Weight Distribution (MWD) in the range of 1.0 to 3.0.

5. The olefin-based polymer according to claim 1, wherein the olefin-based polymer has a weight average molecular weight (Mw) (5) in the range of 10,000 to 500,000.

6. The olefin-based polymer of claim 1, wherein the olefin-based polymer has (2) a Melt Index (MI) in the range of 0.2g/10min to 2g/10 min.

7. The olefin-based polymer of claim 1, wherein the olefin-based polymer is a copolymer of ethylene and an α -olefin comonomer having 3 to 12 carbon atoms.

8. The olefin-based polymer of claim 7, wherein the α -olefin comonomer comprises any one or a mixture of at least two selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbornadiene, ethylidene norbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, 1, 4-butadiene, 1, 5-pentadiene, 1, 6-hexadiene, styrene, α -methylstyrene, divinylbenzene, and 3-chloromethylstyrene.

9. The olefin-based polymer according to claim 1, wherein the olefin-based polymer is a copolymer of ethylene and 1-octene.

10. The olefin-based polymer according to claim 1, wherein the olefin-based polymer has an elution termination temperature of 60 ℃ or less.

11. The olefin-based polymer of claim 1, wherein the Soluble Fraction (SF) at-20 ℃ in cross-fractionation chromatography (CFC) is 10% by weight or more.

12. The olefin-based polymer of claim 1, wherein the olefin-based polymer has (4) a Molecular Weight Distribution (MWD) in the range of 1.0 to 3.0 and (6) MI₁₀/MI_2.16>7.91(MI_2.16)^-0.188。

13. The olefin-based polymer according to claim 1, wherein the olefin-based polymer is obtained by a method for producing an olefin-based polymer, the method comprising a step of polymerizing an olefin-based monomer in the presence of a catalyst composition for olefin polymerization, the catalyst composition comprising a transition metal compound represented by the following formula 1 and a transition metal compound represented by the following formula 2 in an equivalent ratio of 1:1 to 1: 5:

[ formula 1]

In the formula 1, the first and second groups,

R₁the same or different, each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group, a silyl group, an alkylaryl group, an arylalkyl group or a metalloid group of a group 4 metal substituted with a hydrocarbon group, and two R₁Can be linked together to form a ring by an alkylene group including an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms;

R₂the same or different, each independently represent hydrogen; halogen; an alkyl group having 1 to 20 carbon atoms; an aryl group; an alkoxy group; an aryloxy group; or an amine group, and two or more R₂Can be linked to each other to form an aliphatic or aromatic ring;

R₃the same or different, each independently represent hydrogen; halogen; an alkyl group having 1 to 20 carbon atoms; or an aliphatic or aromatic ring containing nitrogen and substituted or unsubstituted with an aryl group, and when the number of the substituents is plural, two or more of the substituents can be linked to each other to form an aliphatic or aromatic ring;

M₁is a group 4 transition metal;

Q₁and Q₂Each independently represents halogen; an alkyl group having 1 to 20 carbon atoms; an alkenyl group; an aryl group; an alkaryl group; aralkyl group; an alkylamino group having 1 to 20 carbon atoms; an arylamine group; or an alkylene group having 1 to 20 carbon atoms;

[ formula 2]

In the formula 2, the first and second groups,

R₄the same or different, each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group, a silyl group, an alkylaryl group, an arylalkyl group or a metalloid group of a group 4 metal substituted with a hydrocarbon group, and two R₄Can be linked together to form a ring by an alkylene group including an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms;

R₅the same or different, each independently represent hydrogen; halogen; an alkyl group having 1 to 20 carbon atoms; an aryl group; an alkoxy group; an aryloxy group; or an amine group, and two or more R₅Can be linked to each other to form an aliphatic or aromatic ring;

R₆the same or different, each independently represent hydrogen; halogen; an alkyl group having 1 to 20 carbon atoms; or an aliphatic or aromatic ring containing nitrogen and substituted or unsubstituted with an aryl group, and when the number of the substituents is plural, two or more of the substituents can be linked to each other to form an aliphatic or aromatic ring;

M₂is a group 4 transition metal;

Q₃and Q₄Each independently represents halogen; an alkyl group having 1 to 20 carbon atoms; an alkenyl group; an aryl group; an alkaryl group; aralkyl group; an alkylamino group having 1 to 20 carbon atoms; an arylamine group; or an alkylene group having 1 to 20 carbon atoms.

14. The olefin-based polymer according to claim 13, wherein the olefin-based polymer is prepared by a continuous solution polymerization reaction using a continuous stirred tank reactor in the presence of the catalyst composition for olefin polymerization.

Technical Field

[ Cross-reference to related applications ]

This application claims priority and benefit to korean patent application No. 10-2017-0179656 filed in the korean intellectual property office at 26.12.2017, the entire contents of which are incorporated herein by reference.

Background

Polyolefins are widely used for extrusion molded articles, blow molded articles and injection molded articles due to their excellent moldability, heat resistance, mechanical properties, hygienic qualities, water vapor permeability and appearance characteristics of the molded articles. However, polyolefins, particularly polyethylene, have problems of low compatibility with polar resins such as nylon and low adhesion to polar resins and metals due to the absence of polar groups in the molecule. As a result, it is difficult to mix the polyolefin with the polar resin or the metal, or to laminate the polyolefin with these materials. In addition, polyolefin molded articles have problems of low surface hydrophilicity and low antistatic property.

In order to solve such problems and increase the affinity for polar materials, a method of grafting a polar group-containing monomer onto a polyolefin by radical polymerization has been widely used. However, this method has problems in that crosslinking and molecular chain cleavage in polyolefin molecules occur during the grafting reaction, and the viscosity balance of the graft polymer and the polar resin is poor, and thus miscibility is low. There is also a problem that the molded article has poor appearance characteristics due to gel components generated by intramolecular cross-linking or foreign substances generated by molecular chain cleavage.

Further, as a method for preparing an olefin polymer such as an ethylene homopolymer, an ethylene/α -olefin copolymer, a propylene homopolymer or a propylene/α -olefin copolymer, a method of copolymerizing a polar monomer in the presence of a metal catalyst such as a titanium catalyst or a vanadium catalyst is used.

As another method, a method of polymerizing in the presence of a metallocene catalyst including a transition metal compound such as zirconocene dichloride and an organoaluminum oxy compound (aluminoxane) is known. When a metallocene catalyst is used, a high molecular weight olefin polymer is obtained with high activity, and the obtained olefin polymer has a narrow molecular weight distribution and a narrow composition distribution.

Further, as a method for preparing a polar group-containing polyolefin using a metallocene compound having a ligand of an uncrosslinked cyclopentadienyl group, a crosslinked or uncrosslinked bisindenyl group, or an ethylene-crosslinked unsubstituted indenyl/fluorenyl group as a catalyst, a method using a metallocene catalyst is also known. However, these methods have a disadvantage in that the polymerization activity is very low. Therefore, a method of protecting a polar group by a protecting group has been performed, but there are problems as follows: since the protecting group should be removed again after the reaction when the protecting group is introduced, the process becomes complicated.

Ansa-metallocene compounds are organometallic compounds containing two ligands linked to each other by a bridge group, in which the rotation of the ligands is inhibited and the activity and structure of the metal center is determined by the bridge group.

The ansa-metallocene compound is used as a catalyst for preparing an olefin-based homopolymer or copolymer. In particular, ansa-metallocene compounds containing cyclopentadienyl-fluorenyl ligands are known to produce high molecular weight polyethylene and thereby control the microstructure of the polypropylene.

Further, it is also known that an ansa-metallocene compound containing an indenyl ligand can produce a polyolefin having excellent activity and improved stereoregularity.

As described above, various studies have been made on an ansa-metallocene compound capable of controlling the microstructure of an olefin-based polymer and having higher activity, but the studies are still insufficient.

Disclosure of Invention

Technical problem

It is an object of the present invention to provide a low density olefin-based polymer prepared using two types of transition metal compound catalysts and exhibiting excellent blocking resistance.

Technical scheme

To achieve this object, the present invention provides an olefin-based polymer having (1) a density (d) of 0.850g/cc to 0.865g/cc, (2) a melt index (MI, 190 ℃, 2.16kg load conditions) of 0.1g/10min to 3.0g/10min, and (3)8 wt% or more of a Soluble Fraction (SF) at-20 ℃ in cross-fractionation chromatography (CFC), wherein the weight average molecular weight (Mw) of the fraction is in the range of 50,000g/mol to 500,000 g/mol.

Advantageous effects

The olefin-based polymer according to the present invention is a low density olefin-based polymer and shows improved blocking resistance by controlling the molecular weight of the ultra-low crystalline region.

Detailed Description

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

The terms used in the specification and claims should not be construed as limited to conventional or literal meanings, and should be construed to have meanings and concepts corresponding to technical ideas of the present invention based on the principle that an inventor can appropriately define the concept of the term to explain his own invention in the most preferable manner.

In the present specification, the term "polymer" means a polymer compound prepared by polymerizing monomers of the same or different types. The generic term "polymer" includes "hybrid polymers" as well as "homopolymers", "copolymers" and "terpolymers". Further, "hybrid polymer" means a polymer prepared by polymerizing at least two different monomers. The generic term "hybrid polymer" refers to "copolymers" (typically used to refer to polymers prepared using two different types of monomers) and "terpolymers" (typically used to refer to polymers prepared using three different types of monomers). "hybrid polymers" include polymers prepared by polymerizing at least four different types of monomers.

The olefin-based polymer according to the present invention satisfies the following conditions (1) to (3):

(1) a density (d) of 0.850g/cc to 0.865g/cc, (2) a melt index (MI, 190 ℃, 2.16kg load conditions) of 0.1g/10min to 3.0g/10min, and (3)8 wt.% or more of a Soluble Fraction (SF) at-20 ℃ in cross-fractionation chromatography (CFC), wherein the weight average molecular weight (Mw) of the fraction is in the range of 50,000g/mol to 500,000 g/mol.

The fractions eluting at low temperature in the cross-fractionation chromatography (CFC) measurements have low crystallinity. In the present specification, a soluble fraction eluting at a temperature of-20 ℃ or lower in cross-fractionation chromatography (CFC) is defined as an ultra-low crystallization region.

Generally, the lower the density of the polymer, the lower the crystallinity, the increased the ultra-low crystalline regions and the improved impact strength. However, it is difficult to prepare a region of ultra-low crystallinity of a certain level or more in the conventional olefin-based polymer, and even if prepared, the molecular weight of the corresponding region is reduced, thereby deteriorating the blocking resistance. The olefin-based polymer according to the present invention can exhibit superior blocking resistance by maintaining a high ultra-low crystalline content at the same density level and maintaining the molecular weight of the region at a high level, as compared to conventional olefin-based polymers.

The olefin-based polymer according to the invention exhibits a density in the range of 0.850g/cc to 0.865g/cc, more specifically, in the range of 0.853g/cc to 0.863g/cc, when measured according to ASTM D-792.

The Melt Index (MI) can be controlled by adjusting the amount of catalyst relative to comonomer used in the polymerization of the olefin-based polymer and affects the mechanical properties, impact strength and moldability of the olefin-based polymer. In the present specification, the melt index is measured at a low density of 0.850g/cc to 0.865g/cc according to ASTM D1238 at 190 ℃, under a load of 2.16kg, and may be in the range of 0.1g/10min to 3g/10min, specifically, in the range of 0.2g/10min to 2g/10min, more specifically, in the range of 0.25g/10min to 1.8g/10 min.

The Soluble Fraction (SF) at-20 ℃ in cross-fractionation chromatography (CFC) of the olefin-based polymer according to the present invention is 8% by weight or more, and specifically, in the range of 10% by weight to 50% by weight, and the weight average molecular weight (Mw) of the fraction may be maintained at 50,000 or more. Since the soluble fraction at-20 ℃ in the cross-fractionation chromatography satisfies the above range, the olefin-based polymer according to an embodiment of the present invention has a high ultralow crystalline content, and the molecular weight of the fraction remains high, and thus can exhibit more excellent blocking resistance.

Further, the weight average molecular weight (Mw) of a soluble fraction at-20 ℃ of the olefin-based polymer according to one embodiment of the present invention, which is defined as an ultra-low crystalline region, in cross-fractionation chromatography may satisfy 50,000g/mol to 500,000g/mol, more specifically, 50,000g/mol to 300,000g/mol, more specifically, 60,000g/mol to 200,000 g/mol. The weight average molecular weight (Mw) of the soluble fraction at-20 ℃ in the cross-fractionation chromatography of the olefin-based polymer according to the embodiment of the present invention satisfies the above range, and thus the olefin-based polymer exhibits a high molecular weight ultra-low crystalline content, particularly, satisfies the density (1) and the melt index (2), and the content of the soluble fraction and the weight average molecular weight (Mw) of the soluble fraction, and exhibits a high content of the soluble fraction and a high weight average molecular weight of the soluble fraction at the same level of density and melt index value as compared to the conventional olefin-based polymer, thereby exhibiting excellent blocking resistance.

Further, the olefin-based polymer according to an embodiment of the present invention is a low density polymer exhibiting the above density range, and may have a CFC elution termination temperature of 60 ℃ or less, specifically, may have a CFC elution termination temperature in the range of 20 ℃ to 60 ℃, more specifically, a CFC elution termination temperature in the range of 20 ℃ to 55 ℃, and more specifically, a CFC elution termination temperature in the range of 25 ℃ to 45 ℃ due to its high ultra-low crystalline content.

Further, the olefin-based polymer according to an embodiment of the present invention may have: (4) a Molecular Weight Distribution (MWD) in the range of 1.0 to 3.0, in particular in the range of 1.5 to 2.8, more in particular in the range of 1.8 to 2.6, the Molecular Weight Distribution (MWD) being the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw/Mn). The olefin-based polymer according to the embodiment of the present invention may be polymerized using a catalyst composition comprising two types of transition metal compounds having characteristic structures, thereby exhibiting a narrow molecular weight distribution.

In general, the density of an olefin-based polymer is affected by the type and content of monomers used in polymerization, the degree of polymerization, and the like, and a copolymer is affected by the comonomer content. The olefin-based polymer of the present invention is polymerized using a catalyst composition containing two types of transition metal compounds having a characteristic structure, a large amount of comonomer can be introduced, and the olefin-based polymer of the present invention has a low density within the range as described above, and as a result, can exhibit excellent foam processability.

Within the above molecular weight distribution range, the olefin-based polymer may have: (5) a weight average molecular weight (Mw) in the range of 10,000 to 500,000g/mol, in particular in the range of 30,000 to 300,000g/mol, more particularly in the range of 50,000 to 200,000 g/mol. In the present invention, the weight average molecular weight (Mw) is a molecular weight in terms of polystyrene, which is analyzed by Gel Permeation Chromatography (GPC).

The melting temperature (Tm) of the olefin-based polymer obtained in a Differential Scanning Calorimetry (DSC) curve obtained by DSC measurement may be 100 ℃ or less, specifically 80 ℃ or less, more specifically in the range of 10 ℃ to 60 ℃.

In addition, the olefin-based polymer according to an embodiment of the present invention may have (4) a Molecular Weight Distribution (MWD) in the range of 1.0 to 3.0, and (6) MI₁₀/MI_2.16>7.91(MI_2.16)^-0.188。MI₁₀And MI_2.16Denotes Melt Index (MI) measured according to ASTM D-1238, and can be used as a marker for molecular weight.

The olefin-based polymer is a homopolymer selected from olefin-based monomers, specifically α -olefin-based monomers, cycloolefin-based monomers, diene-olefin-based monomers, triene-olefin-based monomers and styrene-based monomers or a copolymer selected from two or more thereof.

α -the olefin comonomer may include any one or a mixture of two or more selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbornadiene, ethylidene norbornene, phenyl norbornene, vinyl norbornene, dicyclopentadiene, 1, 4-butadiene, 1, 5-pentadiene, 1, 6-hexadiene, styrene, α -methyl styrene, divinylbenzene and 3-chloromethyl styrene.

More specifically, the olefin copolymer according to an embodiment of the present invention may be a copolymer of ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 4-methyl-1-pentene, or ethylene and 1-octene, and more specifically, the olefin copolymer according to an embodiment of the present invention may be a copolymer of ethylene and 1-octene.

When the olefin-based polymer is a copolymer of ethylene and α -olefin, the amount of α -olefin can be 90 wt% or less, more specifically 70 wt% or less, still more specifically in the range of 5 wt% to 60 wt%, even more specifically in the range of 20 wt% to 50 wt%, relative to the total weight of the copolymer, the above physical properties are readily achieved when α -olefin is included in the above range.

The olefin-based polymer according to an embodiment of the present invention having the above-described physical properties and composition characteristics may be prepared by a continuous solution polymerization reaction in a single reactor in the presence of a metallocene catalyst composition including at least one type of transition metal compound. Therefore, in the olefin-based polymer according to the embodiment of the invention, a block formed by linearly connecting two or more repeating units derived from one of monomers constituting the polymer is not formed in the polymer. That is, the olefin-based polymer according to the present invention does not include a block copolymer, but may be selected from a random copolymer, an alternating copolymer, and a graft copolymer, and more particularly, may be a random copolymer.

Specifically, the olefin-based copolymer of the present invention can be obtained by a preparation method comprising a step of polymerizing an olefin-based monomer in the presence of a catalyst composition for olefin polymerization comprising a transition metal compound represented by the following formula 1 and a transition metal compound represented by the following formula 2 in an equivalent ratio of 1:1 to 1:5, specifically, 1:1 to 1: 4.

However, in the preparation of the olefin-based polymer according to the embodiment of the present invention, the structural ranges of the first transition metal compound and the second transition metal compound are not limited to the specifically disclosed types, and all modifications, equivalents, or substitutes included in the scope and technical scope of the present invention should be understood to be included in the present invention.

[ formula 1]

In the formula 1, the first and second groups,

R₁may be the same or different, each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group, a silyl group, an alkylaryl group, an arylalkyl group or a metalloid group of a group 4 metal substituted with a hydrocarbon group, and two R₁May be linked together to form a ring by an alkylene group including an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms;

R₂may be the same or different, each independently represents hydrogen; halogen; an alkyl group having 1 to 20 carbon atoms; an aryl group; an alkoxy group; an aryloxy group; or an amine group, and two or more R₂May be linked to each other to form an aliphatic ring or an aromatic ring;

R₃may be the same or different, each independently represents hydrogen; halogen; an alkyl group having 1 to 20 carbon atoms; or an aliphatic or aromatic ring containing nitrogen and substituted or unsubstituted with an aryl group, and when the number of the substituents is plural, two or more of the substituents may be linked to each other to form an aliphatic or aromatic ring;

M₁is a group 4 transition metal;

Q₁and Q₂Each independently represents halogen; an alkyl group having 1 to 20 carbon atoms; an alkenyl group; an aryl group; an alkaryl group; aralkyl group; an alkylamino group having 1 to 20 carbon atoms; an arylamine group; or an alkylene group having 1 to 20 carbon atoms;

[ formula 2]

In the formula 2, the first and second groups,

R₄may be the same or different, each independently represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group, a silyl group, an alkylaryl group, an arylalkyl group or a metalloid group of a group 4 metal substituted with a hydrocarbon group, and two R₄May be linked together to form a ring by an alkylene group including an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms;

R₅may be the same or different, each independently represents hydrogen; halogen; an alkyl group having 1 to 20 carbon atoms; an aryl group; an alkoxy group; an aryloxy group; or an amine group, and two or more R₅May be linked to each other to form an aliphatic ring or an aromatic ring;

R₆may be the same or different, each independently represents hydrogen; halogen; an alkyl group having 1 to 20 carbon atoms; or an aliphatic or aromatic ring containing nitrogen and substituted or unsubstituted with an aryl group, and when the number of the substituents is plural, two or more of the substituents may be linked to each other to form an aliphatic or aromatic ring;

M₂is a group 4 transition metal;

Q₃and Q₄Each independently represents halogen; an alkyl group having 1 to 20 carbon atoms; an alkenyl group; an aryl group; an alkaryl group; aralkyl group; an alkylamino group having 1 to 20 carbon atoms; an arylamine group; or an alkylene group having 1 to 20 carbon atoms.

Further, in another embodiment of the present invention, in formula 1, R₁And R₂May be the same or different and each independently may represent hydrogen; an alkyl group having 1 to 20 carbon atoms; an aryl group; or a silyl group,

R₃may be the same or different, and may be an alkyl group having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; an aryl group; an alkaryl group; aralkyl group; alkoxy having 1 to 20 carbon atoms; an aryloxy group; or an amine group; and R is₃Two or more adjacent R in (1)₃May be linked to each other to form an aliphatic or aromatic ring;

Q₁and Q₂May be the same or different, and each may independently represent halogen; an alkyl group having 1 to 20 carbon atoms; an alkylamino group having 1 to 20 carbon atoms; or an arylamine group,

M₁may be a group 4 transition metal.

Further, in formula 2, R₄And R₅May be the same or different, and each may independently represent hydrogen; has 1 to 20An alkyl group of carbon atoms; an aryl group; or a silyl group,

R₆may be the same or different, and may be an alkyl group having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; an aryl group; an alkaryl group; aralkyl group; alkoxy having 1 to 20 carbon atoms; an aryloxy group; or an amine group; and R is₆Two or more adjacent R in (1)₆May be linked to each other to form an aliphatic or aromatic ring;

Q₃and Q₄May be the same or different, and each may independently represent halogen; an alkyl group having 1 to 20 carbon atoms; an alkylamino group having 1 to 20 carbon atoms; or an arylamine group,

M₂may be a group 4 transition metal.

Further, in the transition metal compound represented by formula 1 or formula 2, the metal sites are linked through a cyclopentadienyl ligand having tetrahydroquinoline introduced thereto, and the structure thereof has a narrow Cp-M-N angle and a wide Q toward which the monomer approaches₁-M-Q₂(Q₃-M-Q₄) And (4) an angle. In addition, the Cp, tetrahydroquinoline, nitrogen and metal sites are connected in sequence by a ring bond, forming a more stable and rigid pentagonal ring structure. Thus, when these compounds are reacted with cocatalysts, e.g. methylaluminoxane or B (C)₆F₅)₃When the reaction is activated and then applied to olefin polymerization, an olefin-based polymer having characteristics of high activity, high molecular weight, high copolymerizability, and the like can be polymerized even at a high polymerization temperature.

Each substituent defined in the present specification will be described in detail as follows.

In the present specification, unless otherwise specifically stated, the hydrocarbon group means a monovalent hydrocarbon group having 1 to 20 carbon atoms formed only of carbon and hydrogen, regardless of its structure, such as alkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkaryl, and aralkyl groups.

The term "halogen" as used in this specification refers to fluorine, chlorine, bromine and iodine unless otherwise specified.

The term "alkyl" as used in this specification, unless otherwise specified, refers to a straight or branched chain hydrocarbon group.

The term "alkenyl" as used in this specification refers to straight or branched chain alkenyl groups, unless otherwise specified.

The branch may be an alkyl group having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; an alkaryl group having from 7 to 20 carbon atoms; or an aralkyl group having 7 to 20 carbon atoms.

According to an embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilino, anisyl and the like, but is not limited thereto.

Alkylaryl refers to an aryl group substituted with an alkyl group.

Aralkyl means an alkyl group substituted with an aryl group.

The ring (or heterocyclic group) means a monovalent aliphatic or aromatic hydrocarbon group having 5 to 20 carbon atoms of a ring atom and containing one or more hetero atoms, and may be a single ring or a condensed ring of two or more rings. Furthermore, a heterocyclic group may be unsubstituted or substituted with an alkyl group. Examples thereof include indoline, tetrahydroquinoline, and the like, but the present invention is not limited thereto.

Alkylamino refers to amino substituted with alkyl, and includes dimethylamino, diethylamino, and the like, but is not limited thereto.

According to an embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilino, anisyl and the like, but is not limited thereto.

The compound of formula 1 may be one or more selected from the group consisting of formulae 1-1 and 1-2 below, and the compound of formula 2 may be one or more selected from the group consisting of formulae 2-1 below, but the present invention is not limited thereto.

[ formula 1-1]

[ formulae 1-2]

[ formula 2-1]

In addition, it may be a compound having various structures within the ranges defined in formulas 1 and 2.

The transition metal compound of formula 1 and the transition metal compound of formula 2 allow the introduction of a large amount of α -olefin as well as low density polyethylene due to the structural characteristics of the catalyst, and thus a low density polyolefin copolymer having a density of 0.850g/cc to 0.865g/cc can be prepared, and in addition, when the transition metal compound of formula 1 and the transition metal compound of formula 2 are used together in an equivalent ratio of 1:1 to 1:5, particularly 1:1 to 1:4, an olefin-based polymer having a high molecular weight, a narrow molecular weight distribution, and a low density can be prepared.

For example, the transition metal compounds of formulae 1 and 2 can be prepared by the following methods.

[ reaction formula 1]

In reaction formula 1, R₁To R₃、M₁、Q₁And Q₂Each as defined in formula 1.

Further, as an example, the transition metal compound of formula 2 may be prepared by the following method.

[ reaction formula 2]

In reaction formula 2, R₄To R₆、M₂、Q₃And Q₄Each as defined in formula 2.

Formulae 1 and 2 may be prepared according to the method described in korean patent application laid-open No. 2007 & 0003071, and the entire contents thereof are incorporated herein by reference.

The transition metal compound of formula 1 and the transition metal compound of formula 2 may be used alone or in combination as a catalyst for polymerization, which includes one or more co-catalyst compounds represented by the following formulae 3,4 and 5 in addition to the transition metal compound of formula 1 and the transition metal compound of formula 2.

[ formula 3]

-[Al(R₇)-O]_a-

[ formula 4]

A(R₇)₃

[ formula 5]

[L-H]⁺[W(D)₄]^-Or [ L ]]⁺[W(D)₄]^-

In the case of the formulas 3 to 5,

R₇may be the same or different and are each independently selected from the group consisting of halogen, hydrocarbon group having 1 to 20 carbon atoms and hydrocarbon group having 1 to 20 carbon atoms substituted with halogen,

a is aluminum or boron, and A is aluminum or boron,

d each independently represents an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, wherein at least one hydrogen atom may be substituted by a substituent selected from the group consisting of a halogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and an aryloxy group having 6 to 20 carbon atoms,

h is a hydrogen atom, and (C) is a hydrogen atom,

l is a neutral or cationic Lewis acid,

w is a group 13 element, and

a is an integer of 2 or more.

Examples of the compound represented by formula 3 include alkylaluminoxane such as Methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, etc., and modified alkylaluminoxane in which two or more alkylaluminoxanes are mixed, and specifically, methylaluminoxane and Modified Methylaluminoxane (MMAO) may be mentioned.

Examples of the compound represented by formula 4 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylaluminum chloride, triisopropylaluminum, tri-sec-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri (p-tolyl) aluminum, dimethylmethoxyaluminum, dimethylethoxyaluminum, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, and the like, and specifically, may be selected from trimethylaluminum, triethylaluminum, and triisobutylaluminum.

Examples of the compound represented by formula 5 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetrakis (p-tolyl) boron, trimethylammonium tetrakis (o, p-dimethylphenyl) boron, tributylammonium tetrakis (p-trifluoromethylphenyl) boron, trimethylammonium tetrakis (p-trifluoromethylphenyl) boron, tributylammonium tetrakis (pentafluorophenyl) boron, N-diethylanilinium tetraphenylboron, N-diethylanilinium tetrakis (pentafluorophenyl) boron, diethylammonium tetrakis (pentafluorophenyl) boron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, dimethylanilinium tetrakis (pentafluorophenyl) borate, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammoniuuminium, tripropylammonium tetraphenylaluminum, Trimethylammoniumtetra (p-tolyl) aluminum, tripropylammoniumtetra (p-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammoniumtetra (p-trifluoromethylphenyl) aluminum, trimethylammoniumtetra (p-trifluoromethylphenyl) aluminum, tributylammoniumtetra (pentafluorophenyl) aluminum, N-diethylphenylammoniumtetraphenylaluminum, N-diethylphenylammoniumtetrakis (pentafluorophenyl) aluminum, diethylammoniumtetrakis (pentafluorophenyl) aluminum, triphenylphosphoniumtetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, tripropylammoniumtetra (p-tolyl) boron, triethylammoniumtetra (o, p-dimethylphenyl) boron, triphenylcarboniumtetrakis (p-trifluoromethylphenyl) boron, triphenylcarboniumtetrakis (pentafluorophenyl) boron, and the like.

As a first method, the catalyst composition may be prepared by a process comprising the steps of: 1) contacting a primary mixture of a transition metal compound represented by formula 1 and a transition metal compound represented by formula 2 with a compound represented by formula 3 or 4 to obtain a mixture; 2) adding a compound represented by formula 5 to the mixture.

Further, as a second method, the catalyst composition may be prepared by a method of contacting the transition metal compound represented by formula 1 and the transition metal compound represented by formula 2 with the compound represented by formula 3.

In the first of the above-described preparation methods of the catalyst composition, the molar ratio of the transition metal compound represented by formula 1 and the transition metal compound represented by formula 2/the compound represented by formula 3 or 4 may be in the range of 1/5,000 to 1/2, particularly in the range of 1/1000 to 1/10, more particularly in the range of 1/500 to 1/20. When the molar ratio of the transition metal compound represented by formula 1 to the transition metal compound represented by formula 2/the compound represented by formula 3 or 4 exceeds 1/2, the amount of the alkylating agent is very small, and thus alkylation of the metal compound does not proceed completely. When the molar ratio is less than 1/5000, alkylation of the metal compound is performed, but activation of the alkylated metal compound cannot be completely achieved due to a side reaction between the remaining excess alkylating agent and the activator which is the compound of formula 5. Further, the molar ratio of the transition metal compound represented by formula 1 and the transition metal compound represented by formula 2/the compound represented by formula 5 may be in the range of 1/25 to 1, particularly in the range of 1/10 to 1, more particularly in the range of 1/5 to 1. When the molar ratio of the transition metal compound represented by formula 1 to the transition metal compound represented by formula 2/the compound represented by formula 5 is greater than 1, the amount of the activator is relatively small, so that the metal compound is not completely activated, and thus the activity of the resulting catalyst composition may be reduced. When the molar ratio is less than 1/25, the activation of the metal compound is completely performed, but the unit cost of the catalyst composition may be uneconomical due to the excess activator remaining, or the purity of the produced polymer may be lowered.

In the second one of the above-described preparation methods of the catalyst composition, the molar ratio of the transition metal compound represented by formula 1 and the transition metal compound represented by formula 2/the compound represented by formula 3 may be in the range of 1/10,000 to 1/10, particularly in the range of 1/5000 to 1/100, more particularly in the range of 1/3000 to 1/500. When the molar ratio is more than 1/10, the amount of the activator is relatively small, so that activation of the metal compound is not completely achieved, and thus the activity of the resulting catalyst composition may be lowered. When the molar ratio is less than 1/10,000, the activation of the metal compound is completely performed, but the unit cost of the catalyst composition may be uneconomical due to the excess activator remaining, or the purity of the produced polymer may be lowered.

In the preparation of the catalyst composition, a hydrocarbon-based solvent such as pentane, hexane, heptane or the like, or an aromatic solvent such as benzene, toluene or the like may be used as a reaction solvent.

Further, the catalyst composition may include a transition metal compound and a co-catalyst compound in a form supported on a carrier.

The support that can be used is not particularly limited as long as it is used as a support in a metallocene catalyst. Specifically, the support may be silica, silica-alumina, silica-magnesia, or the like, and any one thereof or a mixture of two or more thereof may be used.

In the case where the support is silica, since the silica support and the functional group of the metallocene compound of formula 1 form a chemical bond, there is little catalyst released from the surface during olefin polymerization. As a result, it is possible to prevent the fouling of the wall surface of the reactor or the entanglement of polymer particles with each other during the production of the olefin-based polymer. In addition, the olefin-based polymer produced in the presence of the catalyst containing a silica carrier has excellent particle shape and polymer apparent density.

More specifically, the support may be high-temperature-dried silica or silica-alumina containing siloxane groups having high reactivity on the surface by a method such as high-temperature drying.

The carrier may further comprise an oxide, carbonate, sulphate or nitrate component, for example Na₂O、K₂CO₃、BaSO₄、Mg(NO₃)₂And the like.

The polymerization reaction for polymerizing the olefin-based monomer may be performed by a conventional method applied to olefin monomer polymerization, such as continuous solution polymerization, bulk polymerization, suspension polymerization, slurry polymerization, emulsion polymerization, and the like.

The polymerization of the olefin monomer may be carried out in the presence of an inert solvent, and examples of the inert solvent include benzene, toluene, xylene, cumene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene and 1-octene, but the present invention is not limited thereto.

The olefin-based polymer may be polymerized by heating at a temperature of about 25 ℃ to about 500 ℃ and about 1kgf/cm²To about 100kgf/cm²Under pressure of (b).

In particular, the polymerization of the olefin-based polymer may be carried out at a temperature of about 25 ℃ to about 500 ℃, particularly at a temperature in the range of 80 ℃ to 250 ℃, more preferably at a temperature in the range of 100 ℃ to 200 ℃. Further, the reaction pressure during the polymerization may be 1kgf/cm²To 150kgf/cm²In the range of (1), preferably 1kgf/cm²To 120kgf/cm²In the range of 5kgf/cm, more preferably 5kgf/cm²To 100kgf/cm²Within the range.

The olefin-based polymer of the present invention can be used for blow molding, extrusion molding or injection molding in various fields, and applications including packaging, construction, daily necessities, etc., such as materials for automobiles, electric wires, toys, fibers, medicines, etc., due to having improved physical properties. In particular, olefin-based polymers are useful for automobiles requiring excellent impact strength.

Further, the olefin-based polymer of the present invention can be effectively used for the production of molded articles.

The molded article may include, in particular, blow molded articles, inflation molded articles, casting molded articles, extrusion laminate molded articles, extrusion molded articles, foam molded articles, injection molded articles, sheets, films, fibers, monofilaments, nonwoven fabrics and the like.