KR102071588B1 - Olefin based polymer - Google Patents

Abstract

The present invention (1) Melt Index (Melt Index, MI, 190, 2.16 kg loading conditions): 0.1 to 100 g / 10 min; (2) molecular weight distribution (MWD): 1.0 to 3.0; (3) two or more melting temperatures (Tm) obtained from a DSC curve obtained by measuring with a differential scanning calorimeter (DSC); And (4) Mw = −K × log (MI) + Tm (H) × 1000, wherein the K value satisfies 20,000 <K <60,000, wherein Tm (H) is at least two melts. The present invention relates to an olefin-based polymer showing the highest melting temperature among the temperatures. The olefin-based polymer according to the present invention exhibits high molecular weight and narrow molecular weight distribution, and particularly exhibits higher molecular weight than when having the same melt index. have.

Description

Olefin Polymer {OLEFIN BASED POLYMER}

The present invention relates to an olefin polymer, and more particularly, to an olefin polymer having a high molecular weight and a narrow molecular weight distribution prepared using two transition metal compound catalysts.

Polyolefins are excellent in moldability, heat resistance, mechanical properties, hygiene quality, water vapor permeability, and appearance characteristics of molded articles, and thus are widely used for extrusion molded articles, blow molded articles, and injection molded articles. However, polyolefins, especially polyethylene, have a problem of low compatibility with polar resins such as nylon and low adhesion with polar resins and metals because they do not have polar groups in the molecule. As a result, it has been difficult to blend polyolefins with polar resins or metals or to laminate them with these materials. Moreover, the molded article of polyolefin has a problem that surface hydrophilicity and antistatic property are low.

In order to solve this problem and to improve affinity for polar materials, a method of grafting a polar group-containing monomer onto a polyolefin through radical polymerization has been widely used. However, this method has a problem of low compatibility due to poor molecular balance between the graft polymer and the polar resin due to intramolecular crosslinking and cleavage of the molecular chain of the polyolefin during the graft reaction. In addition, there was a problem that the appearance characteristics of the molded article was low due to the foreign matter produced by the gel component or the molecular chain produced by intramolecular crosslinking.

In addition, a method of preparing an olefin polymer such as an ethylene homopolymer, an ethylene / α-olefin copolymer, a propylene homopolymer or a propylene / α-olefin copolymer may be used to copolymerize a polar monomer under a metal catalyst such as a titanium catalyst or a vanadium catalyst. Method was used. However, when copolymerizing a polar monomer using such a metal catalyst, there exists a problem that molecular weight distribution or composition distribution are large, and polymerization activity is low.

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

In addition, a polyolefin containing a polar group is prepared by using a metallocene compound having a ligand of an uncrosslinked cyclopentadienyl group, a crosslinked or uncrosslinked bis indenyl group, or an ethylene crosslinked unsubstituted indenyl group / fluorenyl group as a catalyst. As a method, a method of using a metallocene catalyst is also known. However, these methods have the disadvantage that the polymerization activity is very low. For this reason, although the method of protecting a polar group by a protecting group is implemented, when a protecting group is introduce | transduced, this process becomes complicated because this protecting group must be removed again after reaction.

Ansa-metallocene compound is an organometallic compound comprising two ligands connected to each other by a bridge group. The ansa-metallocene compound prevents the rotation of the ligand by the bridge group and prevents the activity of the metal center. The structure is determined.

Such ansa-metallocene compound is used as a catalyst for the production of olefinic homopolymers or copolymers. In particular, the ansa-metallocene compound including a cyclopentadienyl-fluorenyl ligand can produce a high molecular weight polyethylene, and thus it is known that the microstructure of the polypropylene can be controlled. have.

In addition, ansa-metallocene compound containing an indenyl ligand is known to be capable of producing a polyolefin having excellent activity and improved stereoregularity.

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

KR 288272 B1

The problem to be solved of the present invention is to provide an olefin polymer having a high molecular weight and a narrow molecular weight distribution prepared using two transition metal compound catalysts.

In order to solve the above problems, the present invention

The olefin polymer which meets the requirements of following (1)-(4) is provided.

(1) melt index (Melt Index, MI, 190, 2.16 kg loading conditions): 0.1 to 30 g / 10 min;

(2) molecular weight distribution (MWD): 1.0 to 3.0;

(3) two or more melting temperatures (Tm) obtained from a DSC curve obtained by measuring with a differential scanning calorimeter (DSC); And

(4) Mw = -K × log (MI) + Tm (H) × 1000

At this time, the K value satisfies 20,000 <K <60,000, and Tm (H) represents the highest melting temperature of two or more melting temperatures.

The olefin polymer according to the present invention exhibits a high molecular weight and a narrow molecular weight distribution, and particularly exhibits a higher molecular weight than when having the same melt index, and thus has excellent physical properties.

The following drawings, which are attached to this specification, illustrate exemplary 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 the drawings. It should not be construed as limited.
1 is a graph showing the weight average molecular weight (Mw) value at a constant melting index (MI) of the copolymers of Examples 1 to 8 and Comparative Examples 1 to 8.
Figure 2 shows the molecular weight distribution (GPC) graph of the olefin polymer prepared in Example 5.

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 being limited to the common or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best describe their invention. It should be interpreted as meanings and concepts corresponding to the technical idea of the present invention based on the principle that the present invention.

As used herein, the term "polymer" means a polymeric compound prepared by the polymerization of monomers of the same or different type. The term "polymer" includes the terms "homopolymer", "copolymer", "terpolymer" as well as "interpolymer". In addition, the "interpolymer" means a polymer prepared by the polymerization of two or more different types of monomers. The term “interpolymer” is commonly used to refer to polymers made from three different types of monomers, as well as to the term “copolymers” (commonly used to refer to polymers made from two different monomers). Used), including the term "terpolymer". This includes polymers made by the polymerization of four or more types of monomers.

When the olefin polymer according to the present invention has the same melt index as the conventional olefin polymer, the olefin polymer has a higher molecular weight and has a characteristic of showing a narrow molecular weight distribution. Specifically, the olefin polymer according to the present invention is (1) Melt Index (Melt Index, MI, 190, 2.16 kg loading conditions): 0.1 to 30 g / 10 min; (2) molecular weight distribution (MWD): 1.0 to 3.0; (3) two or more melting temperatures (Tm) obtained from a DSC curve obtained by measuring with a differential scanning calorimeter (DSC); And (4) Mw = −K × log (MI) + Tm (H) × 1000. At this time, the K value satisfies 20,000 <K <60,000, and Tm (H) represents the highest melting temperature of two or more melting temperatures.

In general, as the melt index of the polymer increases, the weight average molecular weight of the polymer decreases, and the reduced weight average molecular weight affects the physical properties of the polymer, thereby deteriorating the mechanical properties of the polymer, but the olefin polymer according to the present invention is a conventional polymer. In contrast, even when the same melt index has a relatively high weight average molecular weight can exhibit more excellent physical properties.

The melt index (MI) can be adjusted by adjusting the amount of the catalyst used for the comonomer used in the polymerization of the olefin polymer, and affects the mechanical properties, impact strength, and moldability of the olefin polymer. In the present specification, the melt index is measured at 190 ° C. and 2.16 kg load conditions according to ASTM D1238 at a low density condition of 0.85 to 0.91 g / cc.

In addition, the olefin polymer according to an example of the present invention has a molecular weight distribution (MWD; Molecular Weight Distribution) of 1.0 to 3.0, specifically 1.5, which is the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn). To 2.8.

In general, when two or more polymers are mixed, the molecular weight distribution (MWD) is usually increased, and as a result, impact strength and mechanical properties are decreased, and blocking phenomenon occurs. The olefinic polymer according to the present invention is polymerized using a catalyst composition comprising two transition metal compounds having a characteristic structure, so that despite mixing two or more polymers, a single peak, i.e., monomodal, in a molecular weight distribution curve when measuring GPC is determined. -type) peak, narrow molecular weight distribution, and as a result can exhibit excellent impact strength.

In addition, the olefin polymer according to an example of the present invention exhibits a low density of 0.85 to 0.91 g / cc as measured according to ASTM D-792, specifically 0.86 to 0.90 g / cc, more specifically 0.86 to 0.89 g / cc It can have a density of.

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, and the copolymer has a large effect by the content of the comonomer. The olefin polymer of the present invention is polymerized using a catalyst composition comprising two transition metal compounds having a characteristic structure, so that a large amount of comonomer can be introduced, so that the olefin polymer of the present invention is in the range described above. It has a low density of and as a result can exhibit excellent impact strength.

Since the olefin-based polymer has a density of 0.85 to 0.91 g / cc, in this case, the effect of maintaining mechanical properties and improving the impact strength according to the density control is more remarkable.

The olefin polymer may have a weight average molecular weight (Mw) of 10,000 to 200,000 g / mol, specifically 20,000 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).

The said olefin polymer has two or more melting temperatures (Tm) obtained from the DSC curve obtained by measuring with a differential scanning calorimeter (DSC). Specifically, the olefin polymer has a melting temperature having the lowest value at two or more melting temperatures (Tm) obtained from a DSC curve obtained by differential scanning calorimetry (DSC), and is referred to as Tm (L). When the melting temperature has a Tm (H), the Tm (H) may be 90 to 150 ℃, more specifically the Tm (H) may be 100 to 140 ℃.

In the olefin polymer according to the present invention, the correlation between the melt index (MI) and the weight average molecular weight (Mw) can be specifically expressed by the relational expression of (4).

(4) Mw = -K × log (MI) + Tm (H) × 1000

At this time, the K value satisfies 20,000 <K <60,000, and Tm (H) represents the highest melting temperature of two or more melting temperatures.

More specifically, the K value may satisfy d × 0.25 × 10,000 <K <d × 5 × 10,000, where d represents the density of the olefin polymer.

Accordingly, when the olefin polymer according to an example of the present invention has a melt index of the same degree, it may have a weight average molecular weight of a value larger than that of the conventional polymer, thereby exhibiting improved physical properties.

The olefin polymer is one homopolymer selected from an olefin monomer, specifically an alpha-olefin monomer, a cyclic olefin equivalent, a diene olefin monomer, a triene olefin monomer, and a styrene monomer. It may be a copolymer of more than one species. More specifically, the olefin polymer may be a copolymer of ethylene and an alpha-olefin having 3 to 12 carbon atoms or 3 to 10 carbon atoms.

The alpha-olefin comonomers are 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-aitocene, norbornene, norbornadiene, ethylidene nobodene, phenyl nobodene, vinyl nobodene, dicyclopentadiene, 1,4-butadiene, 1,5 One or two or more mixtures selected from the group consisting of -pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.

More specifically, the olefin copolymer according to one 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 have.

When the olefinic polymer is a copolymer of ethylene and an alpha-olefin, the amount of the alpha-olefin is 90 wt% or less, more specifically 70 wt% or less, even more specifically 5 to 60 wt% with respect to the total weight of the copolymer. Can be. When included in the above range, it is easy to implement the above-described physical properties, exhibits better miscibility with respect to polypropylene, and as a result can exhibit a more improved impact strength effect.

The olefinic polymer according to an embodiment of the present invention having the above physical properties and constituent features is prepared through a continuous solution polymerization reaction in the presence of a metallocene catalyst composition comprising at least one transition metal compound in a single reactor. Can be. Accordingly, in the olefin polymer according to an embodiment of the present invention, a block formed by linearly connecting two or more repeating units derived from one of the monomers constituting the polymer in the polymer is linearly formed. That is, the olefin polymer according to the present invention does not include a block copolymer, and is selected from the group consisting of random copolymers, alternating copolymers, and graft copolymers. It may be, and more specifically, may be a random copolymer.

Specifically, the olefin copolymer of the present invention is an olefin system in the presence of a catalyst composition for olefin polymerization comprising a transition metal compound of Formula 1 and a transition metal compound of Formula 2 in an equivalent ratio of 1:99 to 99: 1. It can be obtained by a manufacturing method comprising the step of polymerizing a monomer. However, in the preparation of the olefin-based polymer according to an embodiment of the present invention, the scope of the structures of the first transition metal compound and the second transition metal compound is not limited to the specific disclosed form, and the spirit and technical scope of the present invention. It is to be understood that all changes, equivalents, and substitutes included are included.

[Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2,

R ₁ to R ₁₇ are each independently hydrogen, hydrocarbyl having 1 to 20 carbon atoms or heterohydrocarbyl having 1 to 20 carbon atoms, and two or more adjacent functional groups in R ₁ to R ₁₇ are connected to each other to be aliphatic having 3 to 20 carbon atoms. Or form an aromatic ring having 3 to 20 carbon atoms;

n is 0 or 1;

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

Q ₁ to Q ₄ are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, aryl having 6 to 20 carbon atoms and alkyl having 7 to 20 carbon atoms. Aryl, arylalkyl having 7 to 20 carbon atoms, alkylamino having 1 to 20 carbon atoms, arylamino having 6 to 20 carbon atoms, and alkylidene having 1 to 20 carbon atoms;

Each X ₁ is independently hydrogen, hydrocarbyl having 1 to 20 carbon atoms or hetero hydrocarbyl having 1 to 20 carbon atoms;

Each X ₂ is independently hydrogen, halogen, hydrocarbyl having 1 to 20 carbon atoms or hetero hydrocarbyl having 1 to 20 carbon atoms.

In addition, in one example of the present invention, R ₁ to R ₁₇ , and X ₁ are each independently hydrogen, an alkyl group of 1 to 10 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, an alkynyl group of 2 to 10 carbon atoms, or 1 carbon atom. An alkoxy group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms;

M ₁ and M ₂ may each independently be titanium (Ti), zirconium (Zr) or hafnium (Hf);

Q ₁ to Q ₄ may be each independently halogen or an alkyl group having 1 to 10 carbon atoms;

R ₁ to R ₁₇ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. , A cycloalkyl group having 3 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms;

X ₂ is independently hydrogen, halogen, alkyl group of 1 to 10 carbon atoms, alkenyl group of 2 to 10 carbon atoms, alkynyl group of 2 to 10 carbon atoms, alkoxy group of 1 to 20 carbon atoms, aryl group of 6 to 20 carbon atoms, It may be a cycloalkyl group having 3 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.

In another embodiment of the present invention, in Chemical Formula 1, R ₁ to R ₇ may be each independently hydrogen or an alkyl group having 1 to 10 carbon atoms;

M ₁ may be titanium (Ti), zirconium (Zr) or hafnium (Hf);

Q ₁ and Q ₂ may be each independently halogen or an alkyl group having 1 to 10 carbon atoms;

X ₁ may be an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms;

X ₂ may be each independently hydrogen or halogen.

In addition, in Formula 2, R ₈ to R ₁₇ may be each independently hydrogen or an alkyl group having 1 to 10 carbon atoms;

M ₂ may be titanium (Ti), zirconium (Zr) or hafnium (Hf);

Q ₃ and Q ₄ may be each independently halogen or an alkyl group having 1 to 10 carbon atoms.

The transition metal compound represented by Formula 1 has a structure in which a ketimide ligand is connected to a derivative of cyclopentadiene having a heterocycle including sulfur. The transition metal compound represented by Formula 1 may exhibit high activity and particularly improved copolymerization activity when used as a catalyst for copolymerization of ethylene, octene, hexene, butene, etc., due to the influence of cyclopentadiene derivatives having heterocycles, High molecular weight and low density polyolefin can be produced.

In addition, the transition metal compound represented by Formula 2 has a metal site connected by a cyclopentadienyl ligand in which tetrahydroquinoline is introduced, so that the Cp-MN angle is narrow structurally, and Q ₃ -MQ ₄ angle where the monomer approaches Has the characteristic of keeping wide. In addition, Cp, tetrahydroquinoline, nitrogen and metal sites are sequentially linked by ring-shaped bonds to form a more stable and rigid five-membered ring 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 polymerize the olefin polymer which has.

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

As used herein, the term 'hydrocarbyl group', unless stated otherwise, refers to carbon number consisting only of carbon and hydrogen, regardless of its structure, such as alkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkylaryl or arylalkyl It means the monovalent hydrocarbon group of 1-20.

As used herein, the term "halogen" means fluorine, chlorine, bromine or iodine unless otherwise noted.

As used herein, the term 'alkyl' refers to a straight or branched chain hydrocarbon residue unless otherwise indicated.

As used herein, the term "alkenyl" means a straight or branched alkenyl group unless otherwise indicated.

The branched chain is alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms.

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

The alkylaryl group means an aryl group substituted by the alkyl group.

The arylalkyl group means an alkyl group substituted by the aryl group.

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

The alkyl amino group means an amino group substituted by the alkyl group, and there may be a dimethylamino group, diethylamino group, and the like, but is not limited thereto.

According to one embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited thereto. no.

The compound of Formula 1 is at least one selected from the group consisting of Formulas 1-1 to 1-4, and the compound of Formula 2 is at least one selected from the group consisting of Formulas 2-1 to (2-3) It may be, but is not limited to such.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

Wherein Cy represents cyclohexyl and iPr represents isopropyl.

In addition, it may be a compound having various structures in the range defined in Chemical Formulas 1 and 2.

The transition metal compound of Formula 1 and the transition metal compound of Formula 2 have a density of 0.90 g / cc or less, more specifically, density, since a high density of alpha-olefins as well as low-density polyethylene can be introduced due to the structural characteristics of the catalyst. It is possible to produce low density polyolefin copolymers at the level of 0.85 to 0.90 g / cc. In addition, when the transition metal compound of Formula 1 and the transition metal compound of Formula 2 are used together, an olefin polymer having a high molecular weight and a narrow molecular weight distribution may be prepared.

The transition metal compound of Formula 1 may be prepared by the following method as an example.

Scheme 1

In Formula 1, R ₁ to R ₇ , M, Q ₁ , Q ₂ , X ₁ and X ₂ are the same as defined in Chemical Formula 1, respectively.

Q 'is hydrogen, halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, cycloalkyl of 3 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, of 7 to 20 carbon atoms Arylalkyl, alkylamino having 1 to 20 carbon atoms, arylamino having 6 to 20 carbon atoms, and alkylidene having 1 to 20 carbon atoms;

X ₃ is hydrogen, hydrocarbyl having 1 to 20 carbon atoms or heterohydrocarbyl having 1 to 20 carbon atoms.

The transition metal compound of Formula 2 may be prepared by the following method as an example.

Scheme 2

In Scheme 2, R ₈ to R ₁₇ , n, M ₂ , Q3, and Q4 are the same as defined in Chemical Formula 2.

Since the catalyst composition for olefin polymerization includes the transition metal compound of Formula 1 and the transition metal compound of Formula 2 together, an olefin polymer having a higher molecular weight than a melt index may be prepared.

The catalyst composition for olefin polymerization may include the transition metal compound of Formula 1 and the transition metal compound of Formula 2 in an equivalent ratio of 1:99 to 99: 1, specifically 5:95 to 45:55, more specifically It may be included in the equivalent ratio of 10:90 to 40:60.

The transition metal compound of the formula (1) and the transition metal compound of the formula (2) is a mixture represented by the following formula (5), (6), and (7) alone or in addition to the transition metal compound of the formula (1) and the transition metal compound of the formula (2) In the form of a composition further comprising at least one of the catalyst compounds, it may be used as a catalyst for the polymerization reaction.

[Formula 5]

_{- [Al (R 18) -O} ] a -

[Formula 6]

A (R ₁₈ ) ₃

[Formula 7]

^{[LH] + [W (D} ) 4] - or ^{[L] + [W (D} ) 4] -

In Chemical Formulas 5 to 7,

R ₁₈ may be the same or different from each other, and each independently selected from the group consisting of halogen, hydrocarbyl having 1 to 20 carbon atoms, and hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,

A is aluminum or boron,

D is each independently aryl having 6 to 20 carbon atoms or alkyl having 1 to 20 carbon atoms, at least one hydrogen atom may be substituted with a substituent, wherein the substituent is halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms And at least one selected from the group consisting of aryloxy having 6 to 20 carbon atoms,

H is a hydrogen atom,

L is a neutral or cationic Lewis acid,

W is a group 13 element,

a is an integer of 2 or more.

Examples of the compound represented by Formula 5 include alkyl aluminoxanes such as methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane, and butyl aluminoxane, and the alkyl aluminoxane is mixed with two or more kinds. Modified alkylaluminoxanes, and specifically, may be methylaluminoxane, modified methylaluminoxane (MMAO).

Examples of the compound represented by Chemical Formula 6 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl 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 ethoxide, trimethyl Boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like, and specifically, may be selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

Examples of the compound represented by Formula 7 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N -Diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, dimethyl Aninium tetrakis (pentafluorophenyl) borate, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, tetra Methyl ammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra (p-tolyl) aluminum, tripropylammonium tetra (p-tolyl) aluminum, triethylammonium tetra (o, p-dimethylphenyl) aluminum, tributyl Ammonium tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N -Diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatentraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra (p-tolyl) boron, triethyl Ammonium tetra (o, p-dimethylphenyl) boron, triphenylcarbonium tetra (p-trifluoromethylphenyl) boron or triphenylcarbo Tetra-pentafluoropropane, and the like phenylboronic.

The catalyst composition, as a first method 1) to obtain a mixture by contacting the compound represented by the formula (5) or (6) to the primary mixture of the transition metal compound represented by the formula (1) and the transition metal compound represented by the formula (2) step; And 2) it may be prepared by a method comprising the step of adding a compound represented by the formula (7) to the mixture.

In addition, the catalyst composition may be prepared by contacting the compound represented by Chemical Formula 5 with the primary mixture of the transition metal compound represented by Chemical Formula 1 and the transition metal compound represented by Chemical Formula 2 as a second method. .

In the first method of preparing the catalyst composition, the molar ratio of the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2 / compound represented by Formula 5 or Formula 6 is 1 / 5,000 to 1/2 are preferred, more preferably 1 / 1,000 to 1/10, most preferably 1/500 to 1/20. When the molar ratio of the transition metal compound represented by the formula (1) and the transition metal compound represented by the formula (2) / compound represented by the formula (5) or formula (6) is more than 1/2, the amount of alkylating agent is very small Alkylation of the metal compound is not fully progressed, and when the molar ratio is less than 1 / 5,000, the alkylation of the metal compound is performed, but the alkylated metal compound is due to the side reaction between the remaining excess alkylating agent and the activator of the compound of Formula 7. There is a problem that is not fully activated. In addition, the molar ratio of the transition metal compound represented by the formula (1) and the transition metal compound represented by the formula (2) / compound represented by the formula (7) is preferably 1/25 to 1, more preferably 1/10 to 1, most preferably 1/5 to 1. When the molar ratio of the transition metal compound represented by the formula (1) and the transition metal compound represented by the formula (2) / compound represented by the formula (7) is greater than 1, the amount of the activator is relatively small and activation of the metal compound is If the molar ratio is less than 1/25, the activation of the metal compound is fully performed. However, the excess amount of the remaining activator may result in inefficient or costly production of the catalyst composition. There is a problem that the purity of the polymer is poor.

In the second method of preparing the catalyst composition, the molar ratio of the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2 / compound 5 is represented by 1 / 10,000 to 1 / 10 is preferred, more preferably 1 / 5,000 to 1/100, most preferably 1 / 3,000 to 1/500. If the molar ratio is greater than 1/10, the amount of the activator is relatively small, so that the activation of the metal compound is not fully performed, thereby lowering the activity of the resulting catalyst composition. Although the activation is complete, there is a problem that the unit cost of the catalyst composition is not economical or the purity of the resulting polymer is inferior with the excess activator remaining.

In preparing the catalyst composition, a hydrocarbon solvent such as pentane, hexane, heptane, or the like, or an aromatic solvent such as benzene, toluene, or the like may be used.

In addition, the catalyst composition may include the transition metal compound and the cocatalyst compound in a form supported on a carrier.

The carrier can be used without particular limitation as long as it is used as a carrier in the metallocene catalyst. Specifically, the carrier may be silica, silica-alumina, silica-magnesia, or the like, and any one or a mixture of two or more thereof may be used.

In particular, when the carrier is silica, since the functional group of the silica carrier and the metallocene compound of Chemical Formula 1 forms a chemical bond, few catalysts are liberated from the surface during olefin polymerization. As a result, it is possible to prevent the occurrence of fouling in which the reactor wall surface and the polymer particles are entangled in the production process of the olefin polymer. In addition, the olefin polymer prepared in the presence of a catalyst comprising the silica carrier is excellent in particle form and apparent density of the polymer.

More specifically, the carrier may be a high temperature dried silica or silica-alumina or the like, including a highly reactive siloxane group on the surface through a method such as high temperature drying.

The carrier may further comprise an oxide, carbonate, sulfate or nitrate component such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ or Mg (NO ₃ ) ₂ .

The polymerization reaction for polymerizing the olefinic monomer may be performed by a conventional process applied to the polymerization of olefin monomers such as continuous solution polymerization, bulk polymerization, suspension polymerization, slurry polymerization, or emulsion polymerization.

The polymerization reaction of the olefin monomer may be carried out under an inert solvent, the inert solvent is benzene, toluene, xylene, cumene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene, 1-octene, but is not limited thereto.

Polymerization of the olefinic polymer may be carried out by reacting at a temperature of about 25 to about 500 ℃ and a pressure of about 1 to about 100 kgf / cm ² .

Specifically, the polymerization of the polyolefin may be performed at a temperature of about 25 to about 500 ℃, specifically may be carried out at a temperature of 80 to 250 ℃, more preferably 100 to 200 ℃. The reaction pressure may also be about 1 to about 100 kgf / cm ² , preferably about 1 to about 50 kgf / cm ² , more preferably about 5 to about 40 kgf / cm ² .

Since the olefin polymer of the present invention has improved physical properties, blow molding and extrusion in various fields and applications, such as packaging, construction, household goods, such as materials for automobiles, electric wires, toys, textiles, medical, etc. It is useful for molding or injection molding, and may be particularly useful for automobiles requiring excellent impact strength.

In addition, the olefin polymer of the present invention can be usefully used for the production of shaped articles.

Specifically, the molded article may be a blow molding molded article, an inflation molded article, a cast molded article, an extruded laminate molded article, an extruded molded article, a foamed molded article, an injection molded article, a sheet, a film, a fiber, a monofilament, a nonwoven fabric, or the like.

Example

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement 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.

Preparation Example 1 Preparation of Transition Metal Compound 1

(1) 1,2,3- Trimethyl -3H- Benzo [b] cyclopenta [d] thiophene (1,2,3- trimethyl Preparation of -3H-benzo [b] cyclopenta [d] thiophene)

1,2-dimethyl-1H-benzo [b] cyclopenta [d] thiophen-3 (2H) -one (15.854 g, 73.3 mmol) was dissolved in THF (180 mL), followed by MeMgBr (50 ml, 146.6 mmol, 2 eq.) Was slowly added dropwise. Then, the mixture was slowly warmed up and stirred at room temperature for 12 hours. After confirming the disappearance of the starting material by thin layer chromatography (TLC), distilled water (10 mL) was slowly added dropwise and stirred for 10 minutes. 6 N HCl (180 mL) was then added and stirred for 12 hours. As a result of TLC, it was confirmed that the starting material of alcohol form was disappeared, hexane (50 mL) was added, the water layer was removed by extraction, the remaining water was removed with MgSO ₄ , and the solvent was filtered under reduced pressure. 1,2,3-trimethyl-3H-benzo [b] cyclopenta [d] thiophene (15.4 g, 98% yield) was obtained.

¹ H-NMR (500 MHz, in benzene): 7.83 (d, 1H), 7.71 (d, 1H), 7.35 (t, 1H), 7.20 (t, 1H), 3.33 (m, 1H), 2.09 (s , 3H), 2.04 (s, 3H), 1.40 (d, 3H)

(2) Trimethyl (1,2,3 -trimethyl-1H-benzo [b] cyclopenta [d] thiophen -1-yl) silane <trimethyl (1,2,3-trimethyl-1H-benzo [b] cyclopenta [d] thiophen-1-yl)> and trimethyl (1,2,3-trimethyl-3H-benzo [b] cyclopenta [d] thiophen-3-yl) silane <trimethyl (1,2,3-trimethyl-3H- Preparation of a mixture of benzo [b] cyclopenta [d] thiophen-3-yl)>

1,2,3-trimethyl-3H-benzo [b] cyclopenta [d] thiophene (14.57 g, 67.98 mmol) prepared in step (1) was dissolved in THF (230 mL) and then n- at 0 ° C. BuLi (28.6 ml, 71.38 mmol, 1.05 eq.) Was slowly added dropwise. Then, the mixture was slowly warmed up and stirred at room temperature for 12 hours. After confirming the disappearance of the starting material by NMR, TMSCl (12.9 mL, 101.97 mmol, 1.5 eq.) At room temperature was added dropwise and stirred at room temperature for 12 hours. The starting material was confirmed by NMR, and THF solvent was filtered under reduced pressure, and the reaction mixture was dissolved in hexane (150 mL). Then filtered to remove LiCl, the solvent was filtered under reduced pressure to trimethyl (1,2,3-trimethyl-1H-benzo [b] cyclopenta [d] thiophen-1-yl) silane and trimethyl (1,2,3 A mixture (18.5 g, 95%) of -trimethyl-3H-benzo [b] cyclopenta [d] thiophen-3-yl) silane was obtained.

¹ H-NMR (500 MHz, in benzene): 8.00 (d, 1H), 7.87-7.84 (m, 2H), 7.73 (d, 1H), 7.37 (t, 1H), 7.32 (t, 1H), 7.25 (t, 1H), 7.18 (t, 1H), 2.38 (s, 3H), 2.14 (s, 3H), 2.05 (s, 3H), 2.02 (s, 3H), 1.66 (s, 3H), 1.49 ( s, 3H), -0.04 (s, 9H), -0.08 (s, 9H)

(3) Preparation of Compound A

Trimethyl (1,2,3-trimethyl-1H-benzo [b] cyclopenta [d] thiophen-1-yl) silane and trimethyl (1,2,3-trimethyl-3H-benzo prepared in step (2) [b] A mixture of cyclopenta [d] thiophen-3-yl) silane (19.65 g, 68.58 mmol) was dissolved in CH ₂ Cl ₂ (175 mL), and then TiCl ₄ (68.60 g, 68.58 mmol, 1.0 at room temperature). eq.) was slowly added dropwise and then stirred at room temperature for 12 hours. Subsequently, the CH ₂ Cl ₂ was removed by filtration under reduced pressure, and Compound A (23.0) was obtained as a black solid. g, 91%).

¹ H-NMR (500 MHz, in benzene): 7.64 (d, 1H), 7.19 (d, 1H), 7.06 (t, 1H), 6.96 (t, 1H), 2.24 (s, 3H), 2.10 (s , 3H), 1.90 (s, 3H)

(4) Preparation of N, N-dicyclohexyl-2,6-dichlorobenzimidamide

4.622 ml of dicyclohexylamine was vacuum dried in a Schlenk flask for 20 minutes, dissolved in diethyl ether, and then 1 equivalent of MeMgBr was added at -78 ° C. When the mixture was stirred at room temperature for about 3 hours, the result was a white slurry, and 1 equivalent (4 g) of 2,6-dichlorobenzonitrile reagent was added at a solid state at 0 ° C. After stirring at room temperature overnight, the mixture was extracted with ethyl acetate and NH ₄ Cl (aq) solution, and the organic layers were collected and dried in vacuo to prepare N, N-dicyclohexyl-2,6-dichlorobenzimidamide.

(5) Preparation of the compound of Formula 1-1

Compound A (1.52 g, 4.14 mmol) prepared in step (3) and Compound B (1.33 g, 4.14 mmol) prepared in step (4) were dissolved in toluene (20 mL), followed by tetraethylammonium (TEA). ) (0.74 ml, 5.28 mmol) was added slowly dropwise. The reaction mixture was then stirred at room temperature for 12 hours. It was confirmed that the starting material was disappeared by NMR, the amine salt was removed by filtration, and the toluene solvent was removed by filtration under reduced pressure. Thereafter, the solid obtained in the glovebox was washed with hexane to obtain a transition orange compound 1 (2.0 g, 75%) represented by the dark orange index of Chemical Formula 1-1.

¹ H-NMR (500 MHz, in benzene): 7.92 (d, 1H), 7.41 (d, 1H), 7.02 (m, 1H), 6.91 (t, 1H), 6.86 (t, 1H), 6.42 (m , 2H), 2.49 (s, 3H), 2.16 (s, 3H), 2.11 (s, 3H), 1.84-1.10 (m, 20H)

Preparation Example 2 Preparation of Transition Metal Compound 2

(1) 8- (2,3,4,5-tetramethyl-1,3-cyclopentadienyl) -1,2,3,4-tetrahydroquinoline (8- (2,3,4,5- Preparation of Tetramethyl-1,3-cyclopentadienyl) -1,2,3,4-tetrahydroquinoline)

(i) Preparation of Lithium Carbamate

1,2,3,4-tetrahydroquinoline (13.08 g, 98.24 mmol) and diethyl ether (150 mL) were placed in a Schlenk flask. The Schlenk flask was immersed in a -78 ° C low temperature bath made of dry ice and acetone and stirred for 30 minutes. Then n-BuLi (39.3 mL, 2.5 M, 98.24 mmol) was injected into the syringe under a nitrogen atmosphere to form a pale yellow slurry. Then, after the flask was stirred for 2 hours, the flask was heated to room temperature while removing the generated butane gas. The flask was again immersed in a -78 ° C. low temperature bath to lower the temperature, and then CO ₂ gas was added thereto. As the carbon dioxide gas was added, the slurry disappeared and became a transparent solution. The flask was connected to a bubbler to raise the temperature to room temperature while removing carbon dioxide gas. Thereafter, excess CO ₂ gas and solvent were removed under vacuum. The flask was transferred to a dry box, and then pentane was added thereto, stirred vigorously, and filtered to obtain lithium carbamate, a white solid compound. The white solid compound is coordinated with diethyl ether. The yield is then 100%.

¹ H NMR (C ₆ D ₆ , C ₅ D ₅ N): δ 1.90 (t, J = 7.2 Hz, 6H, ether), 1.50 (br s, 2H, quin-CH ₂ ), 2.34 (br s, 2H , quin-CH ₂ ), 3.25 (q, J = 7.2 Hz, 4H, ether), 3.87 (br, s, 2H, quin-CH ₂ ), 6.76 (br d, J = 5.6 Hz, 1H, quin-CH ) ppm

¹³ C NMR (C ₆ D ₆ ): δ 24.24, 28.54, 45.37, 65.95, 121.17, 125.34, 125.57, 142.04, 163.09 (C = O) ppm

(ii) Preparation of 8- (2,3,4,5-tetramethyl-1,3-cyclopentadienyl) -1,2,3,4-tetrahydroquinoline

The lithium carbamate compound (8.47 g, 42.60 mmol) prepared in step (i) was placed in a Schlenk flask. Then, tetrahydrofuran (4.6 g, 63.9 mmol) and 45 mL of diethyl ether were added sequentially. The Schlenk flask was immersed in a -20 ° C. low temperature bath made of acetone and a small amount of dry ice, stirred for 30 minutes, and then t-BuLi (25.1 mL, 1.7 M, 42.60 mmol) was added thereto. At this time the color of the reaction mixture turned red. Stir for 6 hours while maintaining -20 ° C. CeCl ₃ 2LiCl solution (129 mL, 0.33 M, 42.60 mmol) and tetramethylcyclopentinone (5.89 g, 42.60 mmol) dissolved in tetrahydrofuran were mixed in a syringe and then charged into a flask under nitrogen atmosphere. After slowly raising the temperature of the flask to room temperature, the thermostat was removed after 1 hour, and the temperature was kept at room temperature. Subsequently, water (15 mL) was added to the flask, ethyl acetate was added, and the filtrate was obtained by filtration. The filtrate was transferred to a separatory funnel and hydrochloric acid (2N, 80 mL) was added thereto, followed by shaking for 12 minutes. After neutralizing with saturated aqueous sodium hydrogen carbonate solution (160 mL), the organic layer was extracted. Anhydrous magnesium sulfate was added to this organic layer to remove water and filtered, and the filtrate was taken out and the solvent was removed. The obtained filtrate was purified by column chromatography using hexane and ethyl acetate (v / v, 10: 1) solvent to give a yellow oil. Yield 40%.

¹ H NMR (C ₆ D ₆ ): δ 1.00 (br d, 3H, Cp-CH ₃ ), 1.63-1.73 (m, 2H, quin-CH ₂ ), 1.80 (s, 3H, Cp-CH ₃ ), 1.81 (s, 3H, Cp-CH ₃ ), 1.85 (s, 3H, Cp-CH ₃ ), 2.64 (t, J = 6.0 Hz, 2H, quin-CH ₂ ), 2.84-2.90 (br, 2H, quin -CH ₂ ), 3.06 (br s, 1H, Cp-H), 3.76 (br s, 1H, NH), 6.77 (t, J = 7.2 Hz, 1H, quin-CH), 6.92 (d, J = 2.4 Hz, 1H, quin-CH), 6.94 (d, J = 2.4 Hz, 1H, quin-CH) ppm

(2) [(1,2,3,4- Tetrahydroquinoline  -8- days) Tetramethylcyclopentadienyl - η ⁵ , κ -N] titanium dimethyl ([(1,2,3,4- Tetrahydroquinolin Preparation of -8-yl) tetramethylcyclopentadienyl-eta5, kapa-N] titanium dimethyl)

(i) Preparation of [(1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl- η ⁵ , κ- N] dilithium compounds

8- (2,3,4,5-tetramethyl-1,3-cyclopentadienyl) -1,2,3,4-tetrahydroquinoline (8.07 g) prepared through step (1) in a dry box. , 32.0 mmol) and 140 mL of diethyl ether were added to a round flask, and the temperature was lowered to −30 ° C., and n-BuLi (17.7 g, 2.5 M, 64.0 mmol) was added slowly with stirring. The reaction was carried out for 6 hours while raising the temperature to room temperature. Thereafter, the mixture was washed with diethyl ether several times to obtain a solid. The remaining solvent was removed under vacuum to obtain a dilithium compound (9.83 g) as a yellow solid. Yield 95%.

¹ H NMR (C ₆ D ₆ , C ₅ D ₅ N): δ 2.38 (br s, 2H, quin-CH ₂ ), 2.53 (br s, 12H, Cp-CH ₃ ), 3.48 (br s, 2H, quin-CH ₂ ), 4.19 (br s, 2H, quin-CH ₂ ), 6.77 (t, J = 6.8 Hz, 2H, quin-CH), 7.28 (br s, 1H, quin-CH), 7.75 (brs , 1H, quin-CH) ppm

(ii) Preparation of (1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl- η ⁵ , κ -N] titanium dimethyl

In a dry box, TiCl ₄ DME (4.41 g, 15.76 mmol) and diethyl ether (150 mL) were placed in a round flask, and MeLi (21.7 mL, 31.52 mmol, 1.4 M) was added slowly with stirring at −30 ° C. After stirring for 15 minutes, the [(1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl- η ⁵ , κ- N] dilithium compound prepared in step (i) ( 5.30 g, 15.76 mmol) was added to the flask. Stir for 3 hours while raising the temperature to room temperature. After the reaction was completed, vacuum was applied to remove the solvent, dissolved in pentane, and filtered to obtain a filtrate. Removal of pentane through vacuum yielded a dark brown compound (3.70 g). The yield was 71.3%.

¹ H NMR (C ₆ D ₆ ): δ 0.59 (s, 6H, Ti-CH ₃ ), 1.66 (s, 6H, Cp-CH ₃ ), 1.69 (br t, J = 6.4 Hz, 2H, quin-CH ₂ ), 2.05 (s, 6H, Cp-CH ₃ ), 2.47 (t, J = 6.0 Hz, 2H, quin-CH ₂ ), 4.53 (m, 2H, quin-CH ₂ ), 6.84 (t, J = 7.2 Hz, 1H, quin-CH), 6.93 (d, J = 7.6 Hz, quin-CH), 7.01 (d, J = 6.8 Hz, quin-CH) ppm

¹³ C NMR (C ₆ D ₆ ): δ 12.12, 23.08, 27.30, 48.84, 51.01, 119.70, 119.96, 120.95, 126.99, 128.73, 131.67, 136.21 ppm

Example  One

After the 1.5 L autoclave continuous process reactor was charged with hexane solvent (5.1 kg / h) and 1-octene (0.87 kg / h), the temperature at the top of the reactor was preheated to 150 ° C. A mixture of a transition metal compound (0.5 μmol) in which a triisobutylaluminum compound (0.03 mmol / min), the transition metal compound 1 obtained in Preparation Example 1 and the transition metal compound 2 obtained in Preparation Example 2 were mixed in a molar ratio of 30:70. / min), and dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst (1.5 μmol / min) were simultaneously introduced into the reactor. Subsequently, ethylene (0.87 kg / h) was introduced into the autoclave reactor and maintained at 150 ° C. or more in a continuous process at a pressure of 89 bar for 30 minutes or longer to obtain a copolymer. 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

A copolymer was prepared in the same manner as in Example 1, except that the amount of 1-octene introduced into the continuous process reactor was changed to 1.4 kg / h.

Example 3

A copolymer was prepared in the same manner as in Example 1, except that the amount of the dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst introduced into the continuous process reactor was changed to 0.75 μmol / min.

Example 4

The above procedure was performed except that the amount of 1-octene introduced into the continuous process reactor was 1.4 kg / h and the amount of dimethylanilinium tetrakis (pentafluorophenyl) borate promoter was 1.8 μmol / min. The copolymer was manufactured by the method similar to Example 1.

Example 5

The above procedure was performed except that the amount of 1-octene introduced into the continuous process reactor was 1.4 kg / h, and that of the dimethylanilinium tetrakis (pentafluorophenyl) borate promoter was 2.0 μmol / min. The copolymer was manufactured by the method similar to Example 1.

Example 6

The above procedure was performed except that the amount of 1-octene introduced into the continuous process reactor was 1.4 kg / h and the amount of dimethylanilinium tetrakis (pentafluorophenyl) borate promoter was 3.0 μmol / min. The copolymer was manufactured by the method similar to Example 1.

Example 7

The above procedure was performed except that the amount of 1-octene introduced into the continuous process reactor was 1.3 kg / h and that of the dimethylanilinium tetrakis (pentafluorophenyl) borate promoter was 1.8 μmol / min. The copolymer was manufactured by the method similar to Example 1.

Example 8

The above procedure was performed except that the amount of 1-octene introduced into the continuous process reactor was 1.6 kg / h and the amount of dimethylanilinium tetrakis (pentafluorophenyl) borate promoter was 3.0 μmol / min. The copolymer was manufactured by the method similar to Example 1.

Comparative Example 1

A copolymer was prepared in the same manner as in Example 1, except that the mixture of the transition metal compound introduced into the continuous process reactor was 1.5 μmol / min and the amount of 1-octene was 0.75 kg / h. .

Comparative Examples 2 to 6

As Comparative Examples 2 to 6, LC170, LC370, LC670, LL600, and LL700, which are commercial products of LG Chemical, were purchased and used, respectively.

Comparative Example 7

A copolymer was prepared in the same manner as in Example 1, except that the mixture of the transition metal compound introduced into the continuous process reactor was 1.5 μmol / min and the amount of 1-octene was 1.35 kg / h. .

Comparative Example 8

As a comparative example 8, LC770, a commercial product of LG Chemical, was purchased and used.

Experimental Example

The copolymers of Examples 1 to 8 and Comparative Examples 1 to 8 were evaluated according to the following methods, and are shown in Table 2 below.

Density of the polymer; Measured by ASTM D-792.

Melt Index (MI) of the polymer was measured by ASTM D-1238 (Condition E, 190 ° C., 2.16 Kg load).

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 was calculated.

Crystallization temperature (Tc) was measured using a differential scanning calorimeter (DSC: Differential Scanning Calorimeter 6000) manufactured by PerKinElmer. Specifically, using DSC, the temperature was increased to 200 ° C. for 5 minutes in a nitrogen atmosphere, and then cooled to 30 ° C., and the temperature was increased again to observe the DSC curve. At this time, the temperature increase rate and cooling rate were 10 degreeC / min, respectively.

density
(g / mL) MI
(g / 10min) Mw MWD logMW logMI Tm (L) Tm (H) Example 1 0.872 0.4 137930 2.21 5.140 -0.398 34.6 114.1 Example 2 0.873 0.7 132012 2.2 5.121 -0.155 21.9 113.4 Example 3 0.884 2.3 103648 2.12 5.016 0.362 20.3 113.7 Example 4 0.868 3.5 95305 1.98 4.979 0.544 25.1 113.9 Example 5 0.868 5.1 95121 1.93 4.978 0.708 24.4 113 Example 6 0.875 8.3 85899 2.05 4.934 0.91 6.5 113.1 Example 7 0.868 10.5 77285 1.85 4.888 1.021 41.4 114.1 Example 8 0.864 15.7 73059 1.97 4.864 1.196 5.6 111.9 Comparative Example 1 0.884 0.41 111993 2.29 5.049 -0.387 75.1 - Comparative Example 2 0.872 0.9 105909 2.14 5.025 -0.046 50.9 - Comparative Example 3 0.868 2.73 86512 2.12 4.937 0.436 57.0 - Comparative Example 4 0.869 5.1 75817 2.34 4.880 0.708 56.9 - Comparative Example 5 0.904 7.05 75581 2.53 4.878 0.848 93.2 - Comparative Example 6 0.903 8.66 58978 2.12 4.771 0.938 91.0 - Comparative Example 7 0.856 11.2 71052 2.01 4.852 1.049 31.4 - Comparative Example 8 0.871 14.54 63131 2.16 4.800 1.163 53.7 -

As can be seen in Table 1, the copolymers prepared in Examples 1 to 8 have a higher weight average molecular weight (when having the same degree of melt index (MI) as compared to the copolymers of Comparative Examples 1 to 8 Mw) was confirmed to have.

In addition, the copolymers prepared in Examples 1 to 8 have two or more melting temperatures (Tm) when the density is in the range of 0.85 to 0.91 g / cc, wherein Tm (H) is in the range of 90 to 150 ° C. Satisfaction could be confirmed.

In addition, the copolymers prepared in Examples 1 to 8 had a molecular weight distribution (MWD) of 1.0 to 3.0, and showed a narrow molecular weight distribution on a level equivalent to that of the copolymers of Comparative Examples 1 to 8.

Meanwhile, the molecular weight distribution (GPC) graph of the copolymer prepared in Example 5 is shown in FIG. 2, and referring to FIG. 2, the copolymer according to Example 5 of the present invention shows a single peak on GPC. have.

Claims (12)

In the presence of a catalyst composition for olefin polymerization that satisfies the following requirements (1) to (4) and comprises a transition metal compound of Formula 1 and a transition metal compound of Formula 2 in an equivalent ratio of 1:99 to 99: 1. An olefin polymer which is a copolymer of an ethylene monomer with an alpha 3 -olefin co-monomer having 3 to 12 carbon atoms, obtained by a process comprising the step of polymerizing an ethylene monomer and an alpha -olefin comonomer having 3 to 12 carbon atoms:
(1) Melt Index (Melt Index, MI, 190 ° C., 2.16 kg loading conditions): 0.1 to 30 g / 10 min;
(2) molecular weight distribution (MWD): 1.0 to 3.0;
(3) two or more melting temperatures (Tm) obtained from a DSC curve obtained by measuring with a differential scanning calorimeter (DSC); And
(4) Mw = -K × log (MI) + Tm (H) × 1000
At this time, the K value satisfies 20,000 <K <60,000, and Tm (H) represents the highest melting temperature of two or more melting temperatures,
Tm (L), which is the lowest of the two or more melting temperatures, is between 5.6 ° C. and 34.6 ° C.,
[Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2,
R ₁ to R ₁₇ are each independently hydrogen, hydrocarbyl having 1 to 20 carbon atoms or heterohydrocarbyl having 1 to 20 carbon atoms, and two or more adjacent functional groups in R ₁ to R ₁₇ are connected to each other to be aliphatic having 3 to 20 carbon atoms. Or form an aromatic ring having 3 to 20 carbon atoms;
n is 0 or 1;
M ₁ and M ₂ are each independently a Group 4 transition metal;
Q ₁ to Q ₄ are each independently hydrogen, halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, aryl having 6 to 20 carbon atoms and alkyl having 7 to 20 carbon atoms. Aryl, arylalkyl having 7 to 20 carbon atoms, alkylamino having 1 to 20 carbon atoms, arylamino having 6 to 20 carbon atoms, and alkylidene having 1 to 20 carbon atoms;
Each X ₁ is independently hydrogen, hydrocarbyl having 1 to 20 carbon atoms or hetero hydrocarbyl having 1 to 20 carbon atoms;
X ₂ is each independently hydrogen, halogen, hydrocarbyl having 1 to 20 carbon atoms or hetero hydrocarbyl having 1 to 20 carbon atoms.
The method of claim 1,
The olefinic polymer has two or more melting temperatures (Tm) at a density in the range of 0.85 to 0.91 g / cc,
The Tm (H) is in the range of 90 to 150 ℃ olefin polymer.
The method of claim 1,
The olefinic polymer has two or more melting temperatures (Tm) at a density in the range of 0.85 to 0.91 g / cc,
The Tm (H) is an olefin polymer, which is in the range of 100 to 140 ℃.
The method of claim 1,
The olefinic polymer has a density ranging from 0.85 to 0.91 g / cc,
O is a olefin polymer, wherein K satisfies d × 0.25 × 10,000 <K <d × 5 × 10,000:
In this case, the d means the density of the olefin polymer.
The method according to any one of claims 1 to 4,
The olefin polymer has a weight average molecular weight (Mw) of 10,000 to 200,000 g / mol, olefin polymer.
The method according to any one of claims 1 to 4,
The olefinic polymer exhibits a monomodal-type peak in a molecular weight distribution curve when measured by gel permeation chromatography.
delete The method of claim 1,
The alpha-olefin comonomers are 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-aitocene, norbornene, norbornadiene, ethylidene nobodene, phenyl nobodene, vinyl nobodene, dicyclopentadiene, 1,4-butadiene, 1,5 -An olefinic polymer comprising any one or two or more selected from the group consisting of -pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.
delete The method of claim 1,
The compound of Formula 1 is at least one member selected from the group consisting of Formulas 1-1 to 1-4, and the compound of Formula 2 is at least one member selected from the group consisting of Formulas 2-1 to (2-3) Olefin-Based Polymers:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

Where
Cy represents cyclohexyl and iPr represents isopropyl.
The method of claim 1,
The olefin polymer further comprises any one or two or more co-catalyst selected from the group consisting of a compound of the formula 5 to 7 the olefin polymerization catalyst:
[Formula 5]
_{- [Al (R 18) -O} ] a -
[Formula 6]
A (R ₁₈ ) ₃
[Formula 7]
^{[LH] + [W (D} ) 4] - or ^{[L] + [W (D} ) 4] -
In Chemical Formulas 5 to 7,
R ₁₈ may be the same as or different from each other, and are each independently selected from the group consisting of halogen, hydrocarbyl having 1 to 20 carbon atoms, and hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,
A is aluminum or boron,
D is each independently aryl having 6 to 20 carbon atoms or alkyl having 1 to 20 carbon atoms, at least one hydrogen atom may be substituted with a substituent, wherein the substituent is halogen, hydrocarbyl having 1 to 20 carbon atoms, having 1 to 20 carbon atoms At least one selected from the group consisting of alkoxy and aryloxy having 6 to 20 carbon atoms,
H is a hydrogen atom,
L is a neutral or cationic Lewis acid,
W is a group 13 element,
a is an integer of 2 or more.
The method of claim 1,
The step of polymerizing the olefinic monomer is carried out by a method of continuous solution polymerization of the olefinic monomer in the presence of the catalyst composition for olefin polymerization, olefinic polymer.

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