KR20170076300A - Olefin based polymer - Google Patents

Abstract

(1) Melt Index (MI, 190, under 2.16 kg load 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 a differential scanning calorimeter (DSC); And (4) Mw = -K x log (MI) + Tm (H) x 1000 wherein the K value satisfies 20,000 <K <60,000 and the Tm (H) The olefin polymer according to the present invention exhibits a high molecular weight and a narrow molecular weight distribution and exhibits a higher molecular weight than that having the same melt index, have.

Description

OLEFIN BASED POLYMER &lt; RTI ID = 0.0 &gt;

TECHNICAL FIELD The present invention relates to an olefin-based polymer, and more specifically, to an olefin-based polymer having a high molecular weight and a narrow molecular weight distribution produced by using two kinds of transition metal compound catalysts.

BACKGROUND ART Polyolefins are widely used for extrusion molded articles, blow molded articles and injection molded articles because of their excellent moldability, heat resistance, mechanical properties, hygienic quality, water vapor permeability and appearance characteristics of molded articles. However, polyolefins, particularly polyethylene, have a problem of low compatibility with polar resins such as nylon because of the absence of polar groups in the molecule, and low adhesiveness to polar resins and metals. As a result, it has been difficult to blend the polyolefin with a polar resin or a metal, or to laminate it with these materials. Further, a molded article of polyolefin has a problem of low surface hydrophilicity and antistatic property.

In order to solve such a problem and to increase the affinity for a polar material, 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 in that cross-linking of the polyolefin and molecular chain breakage occur during the grafting reaction, and the viscosity balance of the graft polymer and the polar resin is poor and the miscibility is low. There is also a problem in that the appearance characteristics of a molded article are low due to a gel component produced by intramolecular crosslinking or a foreign substance generated by cleavage of molecular chains.

In addition, a method of producing an olefin polymer such as an ethylene homopolymer, an ethylene / alpha -olefin copolymer, a propylene homopolymer or a propylene / alpha -olefin copolymer can be carried out by copolymerizing a polar monomer with a metal catalyst such as a titanium catalyst or a vanadium catalyst Was used. However, when a polar monomer is copolymerized using the metal catalyst as described above, there is a problem that the molecular weight distribution or the composition distribution is wide and the polymerization activity is low.

As another method, there is known a method of polymerizing in the presence of a metallocene catalyst comprising a transition metal compound such as zircononocene dichloride and an organoaluminum oxy compound (aluminoxane). When a 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.

Alternatively, a metallocene compound having a ligand of a non-crosslinked cyclopentadienyl group, a crosslinked or non-crosslinked bisindenyl group, or an ethylene crosslinked unsubstituted indenyl / fluorenyl group is used as a catalyst to prepare a polyolefin containing a polar group As a method, a method using a metallocene catalyst is also known. However, these methods have a disadvantage in that the polymerization activity is very low. For this reason, although a method of protecting a polar group by a protecting group has been carried out, there is a problem that the process becomes complicated because the protecting group must be removed again after the reaction when a protecting group is introduced.

The ansa-metallocene compound is an organometallic compound containing two ligands connected to each other by a bridge group, in which the rotation of the ligand is prevented by the bridge group, The structure is determined.

These anisometallocene compounds are used as catalysts in the production of olefinic homopolymers or copolymers. In particular, it is known that an anisometallocene compound containing a cyclopentadienyl-fluorenyl ligand can produce a high molecular weight polyethylene, thereby controlling the microstructure of the polypropylene have.

It is also known that an anhydride-metallocene compound containing an indenyl ligand can produce a polyolefin having excellent activity and improved stereoregularity.

As described above, various researches have been made on anthra-metallocene compounds capable of controlling the microstructure of olefin-based polymers while having higher activity, but the degree of such anisotropy is still insufficient.

KR 288272 B1

An object of the present invention is to provide an olefin polymer having a high molecular weight and a narrow molecular weight distribution, which is produced by using two kinds of transition metal compound catalysts.

In order to solve the above problems,

The olefin polymer satisfies the requirements (1) to (4) below.

(1) Melt Index (MI, 190, under 2.16 kg load 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 a differential scanning calorimeter (DSC); And

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

At this time, the K value satisfies 20,000 < K < 60,000 and Tm (H) represents the highest melting temperature among 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 exhibits a higher molecular weight than that having the same melt index, and thus has excellent physical properties.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate exemplary embodiments of the invention and, together with the description of the invention, It should not be construed as limited.
1 is a graph showing the values of the weight average molecular weight (Mw) at a certain melting index (MI) of the copolymers of Examples 1 to 8 and Comparative Examples 1 to 8.
Fig. 2 is a graph showing a molecular weight distribution (GPC) of the olefin-based polymer produced in Example 5. Fig.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

As used herein, the term "polymer" means a polymeric compound prepared by polymerization of the same or different types of monomers. The generic term "polymer" includes the terms " homopolymer ", "copolymer "," terpolymer " The term "interpolymer " also refers to a polymer prepared by polymerization of two or more different types of monomers. The generic term "interpolymer" refers to the term " copolymer "(commonly used to refer to a polymer made from two different monomers) Quot; terpolymer "). &Lt; / RTI &gt; This includes polymers made by polymerization of four or more types of monomers.

The olefin-based polymer according to the present invention has a higher molecular weight and a narrow molecular weight distribution when it has a melt index of the same level as that of the conventional olefin-based polymer. Specifically, the olefinic polymer according to the present invention has (1) a melt index (Melt Index, MI, 190, under a load condition of 2.16 kg) of 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 a differential scanning calorimeter (DSC); And (4) Mw = -K 占 log (MI) + Tm (H) 占 1000. At this time, the K value satisfies 20,000 < K < 60,000 and Tm (H) represents the highest melting temperature among two or more melting temperatures.

Usually, the weight average molecular weight of the polymer is reduced when the melt index of the polymer is increased, and the weight average molecular weight of the polymer is affected by the physical properties of the polymer to deteriorate the mechanical properties of the polymer. However, Even when they have the same melt index as compared to the melt index of the present invention, they have a relatively high weight average molecular weight.

The melt index (MI) can be controlled by adjusting the amount of the catalyst used in the polymerization of the olefin polymer with respect to the comonomer, and affects the mechanical properties, impact strength and moldability of the olefin polymer. In this specification, the melt index is measured under a condition of 190 占 폚 under a load of 2.16 kg according to ASTM D1238 at a low density of 0.85 to 0.91 g / cc.

The olefin polymer according to an example of the present invention has a molecular weight distribution (MWD) of 1.0 to 3.0, specifically 1.5 (Mw / Mn) of a weight average molecular weight (Mw) to a number average molecular weight To 2.8.

Generally, when two or more kinds of polymers are mixed, the molecular weight distribution (MWD) is usually increased, and as a result, the impact strength, mechanical properties, and the like 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 it is possible to obtain a single peak in a molecular weight distribution curve during GPC measurement in spite of mixing of two or more kinds of polymers, -type) peaks, exhibiting a narrow molecular weight distribution, and as a result can exhibit excellent impact strength.

The olefin polymer according to an exemplary embodiment of the present invention has a low density of 0.85 to 0.91 g / cc, more specifically 0.86 to 0.90 g / cc, more specifically 0.86 to 0.89 g / cc as measured according to ASTM D-792 Lt; / RTI &gt; density.

Generally, the density of the olefinic polymer is affected by the type and content of the monomers used in the polymerization, the degree of polymerization, and the copolymer is affected by the content of the comonomer. The olefin-based polymer of the present invention is obtained by polymerizing a catalyst composition containing two transition metal compounds having a characteristic structure, and it is possible to introduce a large amount of comonomer. Thus, the olefin- , And as a result, excellent impact strength can be exhibited.

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

The olefin-based 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-mentioned molecular weight distribution range.

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

The olefin-based polymer has two or more melting temperatures (Tm) obtained from a DSC curve obtained by a differential scanning calorimeter (DSC). Specifically, the olefinic polymer has a melting temperature Tm (L) having the lowest value at two or more melting temperatures (Tm) obtained from a DSC curve obtained by a differential scanning calorimeter (DSC) (H) may be 90 to 150 캜, and more specifically, the Tm (H) may be 100 to 140 캜.

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 expressed specifically by the above-mentioned relational expression (4).

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

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

The K value may more specifically satisfy d x 0.25 x 10,000 < k < d x 5 x 10,000, wherein d represents the density of the olefin polymer.

Accordingly, the olefin polymer according to one example of the present invention can have a weight average molecular weight that is larger than that of the conventional polymer when having the same degree of melt index, and thus can exhibit improved physical properties.

The olefin-based polymer is any homopolymer selected from an olefin-based monomer, specifically, an alpha-olefin-based monomer, a cyclic olefin-based monomer, a dienolefin-based monomer, a triene olefin-based monomer, and a styrene- Or more. More specifically, the olefin-based 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 comonomer may be selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, , 1-tetradecene, 1-hexadecene, 1-aidocene, norbornene, norbornian, ethylidene norbornene, phenyl novodene, vinyl novodene, dicyclopentadiene, A mixture of one or more selected from the group consisting of pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.

More specifically, the olefin copolymer according to an example of the present invention may be a copolymer of ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 4-methyl- have.

When the olefin-based polymer is a copolymer of ethylene and an alpha-olefin, the amount of the alpha-olefin is 90% by weight or less, more specifically 70% by weight or less, still more preferably 5 to 60% Lt; / RTI &gt; When included in the above range, it is easy to realize the above-mentioned physical properties, exhibits better compatibility with polypropylene, and as a result can exhibit a more improved impact strength effect.

The olefinic polymer according to one embodiment of the present invention having the above-described physical properties and constitutional characteristics can be produced by a continuous solution polymerization reaction in the presence of a metallocene catalyst composition containing at least one transition metal compound in a single reactor . Accordingly, the olefin-based polymer according to an embodiment of the present invention does not have a block formed by connecting two or more monomer-derived repeating units among the monomers constituting the polymer in the polymer. That is, the olefin-based polymer according to the present invention does not contain a block copolymer and is selected from the group consisting of a random copolymer, an alternating copolymer and a graft copolymer And more specifically may be a random copolymer.

Specifically, the olefin-based copolymer of the present invention can be produced by reacting an olefin-based copolymer having a structure represented by the following formula 1 and a transition metal compound represented by the following formula 2 in the presence of a catalyst composition for olefin polymerization comprising an equivalent ratio of 1:99 to 99: And then polymerizing the monomers. However, the scope of the structures of the first transition metal compound and the second transition metal compound in the production of the olefinic polymer according to one embodiment of the present invention is not limited to the specific starting form, It is to be understood that the invention includes all modifications, equivalents, and alternatives included.

[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,

R ₁ to R ₁₇ are each independently hydrogen, a hydrocarbyl of 1 to 20 carbon atoms or a heterohydrocarbyl of 1 to 20 carbon atoms, and two or more functional groups adjacent to each other of R ₁ to R ₁₇ are connected to each other to form an aliphatic Or 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 each independently represent 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, alkyl of 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, a hydrocarbyl having 1 to 20 carbon atoms or a heterohydrocarbyl having 1 to 20 carbon atoms;

X ₂ are each independently hydrogen, halogen, hydrocarbyl of 1 to 20 carbon atoms or heterohydrocarbyl of 1 to 20 carbon atoms.

In one embodiment of the present invention, R ₁ to R ₁₇ and X ₁ each independently represent 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, 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);

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

Each of R ₁ to R ₁₇ independently represents 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, 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 selected from the group consisting of hydrogen, halogen, 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, 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.

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

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

Each of Q ₁ and Q ₂ may independently be a 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;

Each X ₂ may independently be hydrogen or halogen.

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

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

Q ₃ and Q ₄ each independently represent a 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 linked to a derivative of cyclopentadiene having a hetero ring containing 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 with octene, hexene, and butene due to the influence of a cyclopentadiene derivative having a heterocycle, A polyolefin having a high molecular weight and a low density can be produced.

In addition, the transition metal compound represented by the above formula (2) has a structure in which the Cp-MN angle is narrow because the metal sites are connected by the cyclopentadienyl ligand into which the tetrahydroquinoline is introduced, and the Q ₃ -MQ ₄ angle Has a feature to keep it wide. In addition, Cp, tetrahydroquinoline, nitrogen and metal sites are connected in this order by a ring-shaped bond to form a more stable and rigid pentagonal ring structure. Therefore, when these compounds are activated by reacting them with co-catalysts such as methylaluminoxane or B (C ₆ F ₅ ) ₃ and then applied to the olefin polymerization, characteristics such as high activity, high molecular weight and high- Based on the weight of the olefin-based polymer.

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

The term &quot; hydrocarbyl group &quot;, as used herein, unless otherwise indicated, refers to an alkyl group, such as alkyl, aryl, alkenyl, alkynyl, cycloalkyl, alkylaryl or arylalkyl, Means a monovalent hydrocarbon group of 1 to 20 carbon atoms.

The term &quot; halogen &quot;, as used herein, unless otherwise indicated, means fluorine, chlorine, bromine or iodine.

The term &quot; alkyl &quot;, as used herein, unless otherwise indicated, means a linear or branched hydrocarbon residue.

The term &quot; alkenyl &quot;, as used herein, unless otherwise indicated, means a straight chain or branched chain alkenyl group.

Wherein the branched chain is selected from the group consisting of alkyl of 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 embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically includes phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like.

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 carbon atoms and containing at least one hetero atom, and may be a single ring or a condensed ring of two or more rings. The heterocyclic group may be substituted or unsubstituted with an alkyl group. Examples thereof include indoline, tetrahydroquinoline and the like, but the present invention is not limited thereto.

The alkylamino group means an amino group substituted by the alkyl group, and includes, but is not limited to, dimethylamino group, diethylamino group, and the like.

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, dimethylanilinyl, anisolyl and the like, 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 compound selected from the group consisting of the following Formulas 2-1 to 2-3: But is not limited thereto.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In the above formula, Cy represents cyclohexyl and iPr represents isopropyl.

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

The transition metal compound of the formula (1) and the transition metal compound of the formula (2) have a density of 0.90 g / cc or less, more specifically, a density of 0.90 g / cc or less because of the structural characteristics of the catalyst and low density polyethylene as well as a large amount of alpha-olefin It is possible to prepare low density polyolefin copolymers at a level of 0.85 to 0.90 g / cc. 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 can be prepared.

The transition metal compound represented by the above formula (1) can be produced, for example, by the following method.

[Reaction Scheme 1]

Wherein R ₁ to R ₇ , M, Q ₁ , Q ₂ , X _1, and X ₂ are as defined in Formula 1,

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, Arylalkyl, alkylamino of 1 to 20 carbon atoms, arylamino of 6 to 20 carbon atoms, and alkylidene of 1 to 20 carbon atoms;

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

The transition metal compound of the above formula (2) can be produced by the following method as an example.

[Reaction Scheme 2]

Wherein R ₈ to R ₁₇ , n, M ₂ , Q 3, and Q 4 are as defined in Formula 2 above.

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

The catalyst composition for olefin polymerization may contain 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, May be included in an equivalent ratio of 10:90 to 40:60.

The transition metal compound represented by the formula (1) and the transition metal compound represented by the formula (2) may be used alone or in combination with the transition metal compound represented by the formula (1) and the transition metal compound represented by the formula (2) In the form of a composition further comprising at least one of the catalyst compounds, can be used as a catalyst for the polymerization reaction.

[Chemical Formula 5]

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

[Chemical Formula 6]

A (R ₁₈ ) ₃

(7)

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

In the above formulas 5 to 7,

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

A is aluminum or boron,

D is independently an aryl having 6 to 20 carbon atoms or an alkyl having 1 to 20 carbon atoms in which at least one hydrogen atom may be substituted with a substituent selected from the group consisting of halogens, hydrocarbons having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms 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.

Examples of the compound represented by the general formula (5) include alkylaluminoxanes such as methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane and butylaluminoxane, and mixtures of two or more of the alkylaluminoxanes Modified alkyl aluminoxane, and specifically may be methyl aluminoxane and modified methyl aluminoxane (MMAO).

Examples of the compound represented by Formula 6 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron 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 (p-dimethylphenyl) boron, tributylammonium tetra (ptrifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N -Diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, dimethyl Anilinium tetrakis (pentafluorophenyl) borate, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, Trimethylammonium tetra (p-tolyl) aluminum, tripropylammonium tetra (p-tolyl) aluminum, triethylammonium tetra (o, p-dimethylphenyl) aluminum, tributyl (P-trifluoromethylphenyl) aluminum, trimethylammonium tetra (ptrifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N-diethylaniliniumtetraphenylaluminum, N, N - diethyl anilinium tetrapentafluorophenyl aluminum, diethyl ammonium tetrapentatetraprapaluminum aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra (p-tolyl) boron, triethyl Ammonium tetra (o, p-dimethylphenyl) boron, triphenylcarbonium tetra (p-trifluoromethylphenyl) boron or triphenylcarbamoyl Tetra-pentafluoropropane, and the like phenylboronic.

The catalyst composition comprises, as a first method, 1) contacting a first mixture of a transition metal compound represented by the formula (1) and a transition metal compound represented by the formula (2) to a compound represented by the formula (5) or (6) step; And 2) adding the compound represented by Formula 7 to the mixture.

The catalyst composition may be prepared by a method comprising contacting the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2 with a compound represented by Formula 5 as a second method .

In the first method of the catalyst composition, 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 or Formula 6 is 1 / Is preferably from 5,000 to 1/2, more preferably from 1/1000 to 1/10, and most preferably from 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) / the compound represented by the formula (5) or (6) exceeds 1/2, the amount of the alkylating agent is very small, And when the molar ratio is less than 1/5000, the alkylation of the metal compound is carried out, but the alkylated metal compound due to the side reaction between the excess of the alkylating agent and the activating agent, Is not fully activated. The molar ratio of the transition metal compound represented by the formula (1) and the transition metal compound represented by the formula (2) / the compound represented by the formula (7) is preferably 1/25 to 1, 1, and 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) / the compound represented by the formula (7) is more than 1, the amount of the activator is relatively small, However, when the molar ratio is less than 1/25, the activation of the metal compound is completely carried out. However, since the excess amount of the activator causes the cost of the catalyst composition to be low, There is a problem in that the purity of the polymer becomes poor.

In the second method, the molar ratio of the transition metal compound represented by the formula (1) to the transition metal compound represented by the formula (2) / the compound represented by the formula (5) is 1 / 10,000 to 1 / 10, more preferably from 1/5000 to 1/100, and most preferably from 1/3000 to 1/500. When the molar ratio exceeds 1/10, the amount of the activating agent is relatively small, and the activation of the metal compound is not completely achieved. Thus, there is a problem in that the activity of the catalyst composition is decreased. When the molar ratio is less than 1 / 10,000, Although the activation is completely performed, there is a problem that the unit cost of the catalyst composition is not economical due to the excess activator remaining or the purity of the produced polymer is low.

In the preparation of 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 as a reaction solvent.

In addition, the catalyst composition may contain the transition metal compound and the cocatalyst compound in the form of being carried on a carrier.

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

In the case where the support is silica, there are few catalysts liberated from the surface during the olefin polymerization process because the functional groups of the silica carrier and the metallocene compound of Chemical Formula 1 form a chemical bond. As a result, it is possible to prevent the occurrence of fouling of the wall surface of the reactor or the polymer particles entangled with each other during the production process of the olefin-based polymer. Further, the olefin-based polymer produced in the presence of the catalyst containing the silica carrier has excellent particle shape and apparent density of the polymer.

More specifically, the carrier may be a high-temperature dried silica or silica-alumina containing a siloxane group having high reactivity on its surface through a method such as high temperature drying.

The carrier may further comprise _{Na 2 O, K 2 CO 3} , BaSO 4 or Mg (NO _{3) 2} added as oxides, carbonates, sulfates or nitrates as components.

The polymerization reaction for polymerizing the olefin-based monomer can be carried out 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 of the olefin monomer may be carried out in an inert solvent. Examples of the inert solvent include benzene, toluene, xylene, cumene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-octene, but is not limited thereto.

The polymerization of the olefinic polymer may be carried out by reacting at a temperature of about 25 to about 500 DEG C and a pressure of about 1 to about 100 kgf / cm &lt; ² &gt;.

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

Since the olefin polymer of the present invention has improved physical properties, the olefin polymer of the present invention can be suitably used for blow molding, extrusion molding, and extrusion in various fields and applications such as packaging materials for automobiles, wires, toys, fibers, It is useful for molding or injection molding, and can be particularly useful for automobiles in which an excellent impact strength is required.

Further, the olefin-based polymer of the present invention can be usefully used for the production of a molded article.

The molded article may be specifically a blow molding molded article, an inflation molded article, a cast molded article, an extrusion laminated molded article, an extrusion molded article, an expanded molded article, an injection molded article, a sheet, a film, a fiber, a monofilament,

Example

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Preparation Example 1: Preparation of transition metal compound 1

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

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

^{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) silane and trimethyl (1,2,3-trimethyl-3H-benzo [b] benzo [b] cyclopenta [d] thiophen-3-yl)

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

^{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 (s, 3H), 2.38 (s, 3H), 2.14 (s, 3H), 2.05 s, 3H), -0.04 (s, 9H), -0.08 (s, 9H)

(3) Preparation of Compound A

Benzo [b] cyclopenta [d] thiophen-1-yl) silane and trimethyl (1,2,3-trimethyl-3H- benzoyl) silane prepared in step (2) (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 (bp) eq.) was slowly added dropwise, followed by stirring at room temperature for 12 hours. The CH ₂ Cl _{2 was} then removed by vacuum filtration and the solid compound A (23.0 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 , &Lt; / RTI &gt; 3H), 1.90 (s, 3H)

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

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

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

The compound A (1.52 g, 4.14 mmol) prepared in the above step (3) and the compound B (1.33 g, 4.14 mmol) prepared in the above step 4 were dissolved in toluene (20 mL), tetraethylammonium ) (0.74 ml, 5.28 mmol) was slowly added dropwise. The reaction mixture was then stirred at ambient temperature for 12 hours. NMR showed that the starting material was absent, the amine salt was removed by filtration, and the toluene solvent was removed by filtration under reduced pressure. Thereafter, the solid obtained in a globebox was washed with hexane to obtain a transition metal compound 1 (2.0 g, 75%) represented by the above formula 1-1 as a dark orange.

^{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)

Production Example 2: Preparation of transition metal compound 2

(1) Synthesis of 8- (2,3,4,5-tetramethyl-1,3-cyclopentadienyl) -1,2,3,4-tetrahydroquinoline (8- (2,3,4,5- 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 shlenk flask. The above-mentioned 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 added via syringe under a nitrogen atmosphere and a pale yellow slurry was formed. Then, after the flask was stirred for 2 hours, the temperature of the flask was raised to room temperature while removing the produced butane gas. The flask was again immersed in a low-temperature bath at -78 ° C, the temperature was lowered, and then CO ₂ gas was introduced. As the carbon dioxide gas was introduced, the slurry disappeared and became a clear solution. The flask was connected to a bubbler to remove the carbon dioxide gas and raise the temperature to room temperature. After that, excess CO ₂ gas and solvent were removed under vacuum. The flask was transferred to a dry box, and pentane was added thereto, followed by vigorous stirring, followed by filtration to obtain a white solid compound, lithium carbamate. The white solid compound is coordinated with diethyl ether. The yield is 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 2H, quin-CH ₂ ), 6.76 (br d, J = 5.6 Hz, 1H, quin -CH ₂ ), 3.25 (q, J = 7.2 Hz, 4H, ) 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 prepared in step (i) (8.47 g, 42.60 mmol) was placed in a Schlenk flask. Then, tetrahydrofuran (4.6 g, 63.9 mmol) and 45 mL of diethyl ether were added in sequence. The Schlenk flask was immersed in acetone and a small amount of dry ice at -20 ° C in a low-temperature bath and stirred for 30 minutes. Then, t-BuLi (25.1 mL, 1.7 M, 42.60 mmol) was added. At this time, the color of the reaction mixture turned red. The mixture was stirred for 6 hours while keeping the temperature at -20 ° C. A solution of CeCl ₃ 2LiCl (129 mL, 0.33 M, 42.60 mmol) dissolved in tetrahydrofuran and tetramethylcyclopentinone (5.89 g, 42.60 mmol) were mixed in a syringe and then charged into a flask under a nitrogen atmosphere. The temperature of the flask was slowly raised to room temperature. After 1 hour, the thermostat was removed and the temperature was maintained at room temperature. Subsequently, water (15 mL) was added to the flask, and ethyl acetate was added thereto, followed by filtration to obtain a filtrate. The filtrate was transferred to a separatory funnel, followed by addition of hydrochloric acid (2 N, 80 mL) and shaking for 12 minutes. A saturated aqueous solution of sodium hydrogencarbonate (160 mL) was added to neutralize and then the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer to remove moisture, followed by filtration, and the filtrate was taken to remove the solvent. The obtained filtrate was purified by column chromatography using hexane and ethyl acetate (v / v, 10: 1) to obtain yellow oil. The yield was 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,

(2) [(1,2,3,4- Tetrahydroquinoline  -8-yl) Tetramethylcyclopentadienyl - η ⁵ , κ -N] titanium dimethyl (([(1,2,3,4- Tetrahydroquinoline -8-yl) tetramethylcyclopentadienyl-eta 5, kapa-N] titanium dimethyl

(i) Preparation of [(1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl- ? ⁵ ,? -N]

8- (2,3,4,5-tetramethyl-1,3-cyclopentadienyl) -1,2,3,4-tetrahydroquinoline (8.07 g, , 32.0 mmol) and diethyl ether (140 mL) were placed in a round-bottom flask, and the temperature was lowered to -30 ° C. and n-BuLi (17.7 g, 2.5 M, 64.0 mmol) was slowly added with stirring. The reaction was allowed to proceed for 6 hours while the temperature was raised to room temperature. Thereafter, the solid was obtained by filtration while washing with diethyl ether several times. Vacuum was applied to remove the remaining solvent to obtain a yellow solid di-lithium compound (9.83 g). The yield was 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, (br s, 2H, quin-CH ₂ ), 6.77 (t, J = 6.8 Hz, 2H, quin-CH ₂ ), 4.19 , 1H, quin-CH) ppm

(ii) Preparation of (1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl- ? ⁵ ,? -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 slowly added with stirring at -30 ° C. After stirring for 15 minutes, [(1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl- ? ⁵ ,? -N] di lithium compound prepared in step (i) 5.30 g, 15.76 mmol) were placed in a flask. The mixture was stirred for 3 hours while the temperature was raised to room temperature. After completion of the reaction, the solvent was removed by vacuum, dissolved in pentane, and filtered to remove the filtrate. Vacuum was applied to remove the pentane to obtain 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 = (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

A 1.5 L autoclave continuous reactor was filled with hexane solvent (5.1 kg / h) and 1-octene (0.87 kg / h), and the temperature at the top of the reactor was preheated to 150 ° C. A mixture (0.5 μmol (mol) of transition metal compound obtained by mixing triisobutyl aluminum 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 in a molar ratio of 30:70 / min), and dimethylanilinium tetrakis (pentafluorophenyl) borate promoter (1.5 μmol / min) were simultaneously introduced into the reactor. Ethylene (0.87 kg / h) was then charged into the autoclave reactor and maintained at 150 ° C for 30 minutes or more at a pressure of 89 bar in a continuous process, followed by copolymerization to obtain a copolymer. Next, the remaining ethylene gas was taken out, and the polymer solution was dried in a vacuum oven for 12 hours or more, and the physical properties were measured.

Example 2

Copolymer was prepared in the same manner as in Example 1 except that the amount of 1-octene charged 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 dimethylanilinium tetrakis (pentafluorophenyl) borate promoter added to the continuous process reactor was changed to 0.75 μmol / min.

Example 4

Except that the amount of 1-octene introduced into the continuous process reactor was changed to 1.4 kg / h, and the amount of dimethylanilinium tetrakis (pentafluorophenyl) borate promoter was changed to 1.8 μmol / min, respectively. A copolymer was prepared in the same manner as in Example 1.

Example 5

Except that the amount of 1-octene introduced into the continuous process reactor was changed to 1.4 kg / h, and the amount of dimethylanilinium tetrakis (pentafluorophenyl) borate promoter was changed to 2.0 μmol / min, respectively. A copolymer was prepared in the same manner as in Example 1.

Example 6

Except that the amount of 1-octene introduced into the continuous process reactor was changed to 1.4 kg / h, and the amount of dimethylanilinium tetrakis (pentafluorophenyl) borate promoter was changed to 3.0 μmol / min, respectively. A copolymer was prepared in the same manner as in Example 1.

Example 7

Except that the amount of 1-octene charged into the continuous process reactor was changed to 1.3 kg / h, and the amount of dimethylanilinium tetrakis (pentafluorophenyl) borate promoter was changed to 1.8 μmol / min, respectively. A copolymer was prepared in the same manner as in Example 1.

Example 8

Except that the amount of 1-octene introduced into the continuous process reactor was changed to 1.6 kg / h, and the amount of dimethylanilinium tetrakis (pentafluorophenyl) borate promoter was changed to 3.0 μmol / min, respectively. A copolymer was prepared in the same manner as in Example 1.

Comparative Example 1

Copolymer was prepared in the same manner as in Example 1 except that the mixture of the transition metal compound to be fed into the continuous process reactor was changed to 1.5 μmol / min and the amount of 1-octene was changed to 0.75 kg / h .

Comparative Examples 2 to 6

LC170, LC370, LC670, LL600, and LL700 commercially available from LG Chemical were used as Comparative Examples 2 to 6, respectively.

Comparative Example 7

Copolymer was prepared in the same manner as in Example 1 except that the mixture of the transition metal compound to be fed into the continuous process reactor was changed to 1.5 μmol / min and the amount of 1-octene was changed to 1.35 kg / h .

Comparative Example 8

As Comparative Example 8, LC770, a commercial product of LG Chemical, was purchased and used.

Experimental Example

The properties of 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.

The density of the polymer; ASTM D-792.

The melt index (MI) of the polymer was measured by ASTM D-1238 (condition E, 190 ° C, 2.16 Kg load).

(Mn) and weight average molecular weight (Mw) were measured by gel permeation chromatography (GPC), and the number average molecular weight (Mw) and the weight average molecular weight (Mw) The molecular weight distribution was calculated by dividing the weight average molecular weight by the number average molecular weight.

- The crystallization temperature (Tc) was measured using a Differential Scanning Calorimeter (DSC) 6000 manufactured by PerKinElmer. Specifically, the temperature of the copolymer was increased to 200 ° C in a nitrogen atmosphere using a DSC, maintained at that temperature for 5 minutes, cooled to 30 ° C, and then the temperature was increased and the DSC curve was observed. At this time, the heating rate and the cooling rate were set at 10 ° C / min.

density
(g / mL) MI
(g / 10 min) 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 from the above Table 1, the copolymers prepared in Examples 1 to 8 had a higher weight average molecular weight (Mw) when they had the same degree of melt index (MI) as the copolymers of Comparative Examples 1 to 8 Mw).

In addition, the copolymers produced in Examples 1 to 8 had a melting temperature (Tm) of 2 or more when the density was in the range of 0.85 to 0.91 g / cc, wherein the Tm (H) Respectively.

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

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

Claims (12)

An olefin polymer satisfying the following requirements (1) to (4):
(1) Melt Index (MI, 190, under 2.16 kg load 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 a differential scanning calorimeter (DSC); And
(4) Mw = -K 占 log (MI) + Tm (H) 占 1000
At this time, the K value satisfies 20,000 < K < 60,000 and Tm (H) represents the highest melting temperature among two or more melting temperatures.
The method according to claim 1,
Wherein the olefinic polymer has two or more melt temperatures (Tm) at a density ranging from 0.85 to 0.91 g / cc,
Wherein the Tm (H) is in the range of 90 to 150 占 폚.
The method according to claim 1,
Wherein the olefinic polymer has two or more melt temperatures (Tm) at a density ranging from 0.85 to 0.91 g / cc,
Wherein the Tm (H) is in the range of 100 to 140 占 폚.
The method according to claim 1,
Wherein the olefinic polymer has a density in the range of 0.85 to 0.91 g / cc,
Wherein K satisfies d x 0.25 x 10,000 < K < d x 5 x 10,000;
Here, d represents the density of the olefin-based polymer.
5. The method according to any one of claims 1 to 4,
The olefin-based polymer has a weight average molecular weight (Mw) of 10,000 to 200,000 g / mol.
5. The method according to any one of claims 1 to 4,
Wherein the olefinic polymer exhibits a monomodal-type peak in the molecular weight distribution curve when measured by gel permeation chromatography.
The method according to claim 1,
Wherein the olefinic polymer comprises ethylene or propylene monomer; And an alpha-olefin comonomer having 3 to 12 carbon atoms.
8. The method of claim 7,
The alpha-olefin comonomer may be selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, , 1-tetradecene, 1-hexadecene, 1-aidocene, norbornene, norbornian, ethylidene norbornene, phenyl novodene, vinyl novodene, dicyclopentadiene, -Olefin-based polymer comprising at least one member selected from the group consisting of pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.
The method according to claim 1,
The olefin polymer is obtained by polymerizing an olefin 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 1:99 to 99: 1 Olefin-based polymer obtained by the production method comprising:
[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,
R ₁ to R ₁₇ are each independently hydrogen, a hydrocarbyl of 1 to 20 carbon atoms or a heterohydrocarbyl of 1 to 20 carbon atoms, and two or more functional groups adjacent to each other of R ₁ to R ₁₇ are connected to each other to form an aliphatic Or 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 each independently represent 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, alkyl of 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, a hydrocarbyl having 1 to 20 carbon atoms or a heterohydrocarbyl having 1 to 20 carbon atoms;
X ₂ are each independently hydrogen, halogen, hydrocarbyl of 1 to 20 carbon atoms or heterohydrocarbyl of 1 to 20 carbon atoms.
10. The method of claim 9,
The compound of Formula 1 is at least one selected from the group consisting of the following Formulas 1-1 to 1-4, and the compound of Formula 2 is at least one compound selected from the group consisting of the following Formulas 2-1 to 2-3: , Olefin-based polymer:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In this formula,
Cy represents cyclohexyl, and iPr represents isopropyl.
10. The method of claim 9,
Wherein the olefin polymerization catalyst composition further comprises at least one promoter selected from the group consisting of compounds represented by the following formulas (5) to (7):
[Chemical Formula 5]
_{- [Al (R 18) -O} ] a -
[Chemical Formula 6]
A (R ₁₈ ) ₃
(7)
^{[LH] + [W (D} ) 4] - or ^{[L] + [W (D} ) 4] -
In the above formulas 5 to 7,
R ₁₈ may be the same or different 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 independently an aryl having 6 to 20 carbon atoms or an alkyl having 1 to 20 carbon atoms in which at least one hydrogen atom may be substituted with a substituent selected from the group consisting of halogen, hydrocarbyl having 1 to 20 carbon atoms, 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.
10. The method of claim 9,
Wherein the step of polymerizing the olefin-based monomer is carried out by a continuous solution polymerization of the olefin-based monomer in the presence of the catalyst composition for olefin polymerization.

Images