WO2015072658A1 - Olefin-based polymer with excellent processability - Google Patents

Abstract

The present invention relates to an olefin-based polymer with excellent processability. The olefin-based polymer according to the present invention has excellent processability by having high molecular weight and wide molecular weight distribution and exhibits improved transparency such that the olefin-based polymer can be useful for required uses.

Description

 【Specification】

 [Name of invention]

 Ellefin series polymer with excellent processability

 [Detailed Description of the Invention]

 Technical Field

 The present invention relates to an olefin polymer having excellent processability.

 This application is filed with Korean Patent Application No. 10-2013-0139997 filed with the Korean Patent Office on January 18, 2013, and Korean Patent Application No. 10-2014-01 14385 filed with the Korean Patent Office on August 29, 2014. Claims the benefit of the filing date of the issue, the entire contents of which are incorporated herein.

 Background Art

 Ellefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed for their respective characteristics. The Ziegler-Natta catalyst has been widely applied to the existing commercial processes since the invention in the 50s, but is characterized by a wide molecular weight distribution of the polymer due to its multi-site catalyst having many active sites. There is a problem that there is a limit in securing the desired physical properties because the composition distribution is not uniform.

 On the other hand, the metallocene catalyst is composed of a combination of a main catalyst composed mainly of a transition metal compound and a cocatalyst composed of an organometallic compound composed mainly of aluminum, and such a catalyst is a single site catalyst as a homogeneous complex catalyst. The polymer has a narrow molecular weight distribution according to the characteristics of a single active site and a homogeneous composition of the comonomer, and the stereoregularity, copolymerization characteristics, molecular weight, It has the property to change the crystallinity.

U.S. Patent No. 5,914,289 describes a method for controlling the molecular weight and molecular weight distribution of a polymer using a metallocene catalyst supported on each carrier, but the amount of solvent used and the time required for preparing the supported catalyst are high. The hassle of having to support the metallocene catalyst to be used on the carrier, respectively. Korean Patent Application No. 2003-12308 discloses a binuclear metallocene in a carrier A method of controlling molecular weight distribution by supporting a catalyst and a mononuclear metallocene catalyst together with an activator to change and polymerize a combination of catalysts in a reactor is disclosed. However, this method is limited in realizing the characteristics of each catalyst at the same time, and also has the disadvantage that the metallocene catalyst portion is released from the carrier component of the finished catalyst, causing fouling. Therefore, in order to solve the above disadvantages, there is a continuing need for a method of preparing a common supported metallocene catalyst having excellent activity and producing a desired physical property and an olefinic polymer.

 On the other hand, linear low density polyethylene is prepared by copolymerizing ethylene and alpha olefins at low pressure using a polymerization catalyst, and has a narrow molecular weight distribution, a short chain branch of a constant length, and a long chain branch. Linear low density polyethylene film has the characteristics of general polyethylene, and has high breaking strength and elongation, and excellent tear strength and falling layer stratification strength. Therefore, the use of stretch film and overlap film, which is difficult to apply to existing low density polyethylene or high density polyethylene, has increased. Doing.

 By the way, linear low density polyethylene used as 1-butene or 1-nucenol comonomer is mostly produced in a single vapor phase reactor or a single loop slurry semi-unger, and the productivity is high compared to a process using 1-octene comonomer, but such a product In addition, due to limitations of the catalyst technology and the process technology used, physical properties are inferior to those of using 1-octene comonomer, and there is a problem in that workability is poor due to a narrow molecular weight distribution. Many efforts are being made to improve these problems.

US Pat. No. 4,935,474 reports on the preparation of polyethylene having a wide molecular weight distribution using two or more metallocene compounds. U. S. Patent No. 6,828, 394 reports a method for producing polyethylene that has a good comonomer binding property and a good combination thereof, which has good processability and is particularly suitable for films. In addition, US Pat. No. 6,841,631 and US Pat. No. 6,894,128 produce polyethylene having bimodal or polycrystalline molecular weight distribution with a metallocene catalyst using at least two kinds of metal compounds, for use in films, blow molding, pipes, and the like. It is reported to be applicable. However, these products have improved processability, but the molecular weight in the unit particles Since the dispersion state is not uniform, there is a problem that the extrusion tube is rough and the physical properties are not stable even under relatively good extrusion conditions.

 Against this background, there is a constant demand for manufacturing a better product having a balance between physical properties and processability, and further improvement is required.

 [Content of invention]

 [Problem to solve]

 In order to solve the problems of the prior art, the present invention is to provide an olefinic polymer having excellent workability and improved transparency and mechanical properties.

 [Task solution]

 The present invention has a molecular weight distribution (Mw / Mn) of 3 to 20;

 A melt flow rate ratio (MFR10 / MFR2) value measured by ASTM1238 at 19 CTC is from 9 to 15;

 In the graph of complex viscosity (r) * [Pa.s]) according to frequency, co [rad / s], an olefin-based polymer having a slope of -0.55 to -0.35 is provided.

 According to another aspect of the invention, there is provided a film (film) comprising the olefinic polymer.

 【Effects of the Invention】

 The olefin polymer according to the present invention is excellent in processability, mechanical properties and transparency, and can be usefully used for applications such as films.

 [Brief Description of Drawings]

 1 is a graph showing the relationship between the frequency (complex) viscosity of the olefinic polymer in accordance with the Examples and Comparative Examples of the present invention (complex visicosity). Figure 2 is a graph showing the measurement of the molecular weight distribution of the olefin polymer according to an embodiment of the present invention by GPC-FI R.

 [Specific contents to carry out invention]

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

Olefin-based polymer according to the present invention has a molecular weight distribution (Mw / Mn) of 3 to 20, melt flow rate ratio (MFR10 / MFR2) measured by ASTM1238 at 190 ^° C. The value is 9 to I ⁵ , and the slope is -0.55 to -0.35 in the complex viscosity (i [Pa.s]) graph according to the frequency (frequency, co [rad / s]).

 The olefinic polymer of the present invention exhibits a broad molecular weight distribution (Mw / Mn, PDI) of about 3 to about 20, preferably about 4 to about 15, and may exhibit excellent processability.

 According to one embodiment of the present invention, the weight average molecular weight (Mw) of the olefinic polymer may be about 50,000 to about 200,000 g / mol, preferably about 60,000 to about 150,000 g / mol, but is not limited thereto. no. The leulevine-based polymer of the present invention has a high molecular weight and a wide molecular weight distribution and has excellent physical properties and processability.

 That is, the olefin copolymer of the present invention has a wider molecular weight distribution and a melt flow rate ratio (MFRR) than the conventionally known olefin copolymer, and thus the fluidity is remarkably improved, and thus, it is possible to exhibit more excellent workability.

 The olefin copolymer of the present invention has a melt flow rate ratio (MFRR,

MFR10 / MFR2) is in the range of about 9 to about 15, preferably about 9.5 to about 13. By having the melt flow rate ratio in the above range, the flowability at each load can be appropriately adjusted, and workability and mechanical properties can be improved at the same time. According to one embodiment of the invention, the melt flow index measured at 190 ^° C., 2.16 kg load according to MFR ₂ (ASTM D-1238) may be about 0.1 to about 10 g / 10 min, preferably about 0.2 And from about 5 g / 10 min. In addition, according to one embodiment of the present invention, MFR ₁₀ (melt flow index measured at 19 CTC, 10 kg load according to ASTM D-1238) is from about 0.9 to about 150 g / lOmin, preferably in the range from about 1.9 to about 65 g / lOmin These MFR ₂ and MFR ₁₀ ranges can be appropriately adjusted in view of the use or application of the olefinic polymer. .

In addition, the olefin polymer of the present invention has a slope of about −0.55 to about −0.35, or about − in a complex viscosity (i [Pa.s]) graph according to frequency (co, [rad / s]). 0.45 to about -0.35. Complex Viscosity Graphs with Frequency are related to fluidity and have high complex viscosity at low frequencies. At higher frequencies, the lower the complex viscosity, the higher the fluidity. That is, it may have a negative slope value, and as the absolute value of the slope value is larger, the fluidity may be higher. The olefinic polymers of the present invention exhibit a significantly higher flowability compared to conventional olefinic polymers having similar densities and weight average molecular weights in the range of slopes from about -0.55 to about -0.35 in complex viscosity plots with frequency. This is related to the wide molecular weight distribution of the olefin polymer of the present invention, and thus, despite the high melt index, the shear thinning effect is much superior, and thus may exhibit excellent fluidity and processability.

According to one embodiment of the present invention, the density of the olefinic polymer may be 0.910 to 0.940 g / cm ³ , but is not limited thereto.

 In addition, according to an embodiment of the present invention, the olefin-based polymer has a maximum SCB content value within the range of 0.2 to 0.8 molecular weight distribution when the weight average molecular weight (M) measured by GPC-FTIR is 0.5 Can be.

 SCB (Short Chain Branching) is attached to the main chain

It means a branch having 2 to 6 carbon atoms, usually refers to defects that are made when using alpha olefin having 4 or more carbon atoms such as 1-butene, 1-nuxene, 1-octene as a comonomer.

 In general, GPC-FTIR equipment can be used to continuously measure molecular weight, molecular weight distribution and SCB content simultaneously.

 The olefin polymer of the present invention is characterized by having a maximum SCB content value within the range of 0.2 to 0.8 molecular weight distribution when the weight average molecular weight (M) measured by GPC-FTIR is 0.5.

 Figure 2 is a graph measuring the molecular weight distribution of the ellefin-based polymer according to an embodiment of the present invention by GPC-FTIR.

Referring to FIG. 2, in the molecular weight distribution graph, the maximum SCB content value (arrow point) appears in the middle region of the molecular weight distribution around the point of the weight average molecular weight (M). That is, when the point where the weight average molecular weight (M) is located is called 5, the point where the minimum molecular weight value appears is 0, and the point where the maximum molecular weight value appears is 1, within the interval of 0.2 to 0.8 on the log graph. Maximum SCB content values can be seen. In particular, the maximum SCB content value may appear in the form of an inflection point rather than a divergent value. The characteristic of such molecular weight distribution is that the olefin polymer of the present invention has the highest inflow of comonomers in the middle molecular weight range, that is, the molecular weight distribution region of 30% of the left and right, based on the weight average molecular weight. In the lower 20% low molecular weight region and the upper 20% high molecular weight region, this means that the incorporation of comonomers is less than in the middle molecular weight region.

 The olefin polymer of the present invention may have an SCB content of 5 to 30, preferably 7 to 20, per 1,000 carbons of the olefin polymer.

 In general, the olepin-based polymer has a disadvantage in that the workability is improved as the molecular weight distribution is widened, but the haze property is deteriorated and transparency is lowered. However, the leulevine-based polymer of the present invention may exhibit high transparency despite the wide molecular weight distribution by improving the haze property due to the distribution of comonomers as described above.

 Therefore, the olefin polymer according to the present invention has excellent fluidity, processability, transparency, and the like, and can be variously applied according to a use, and in particular, it is possible to provide a film having improved physical properties.

 The olefinic polymer according to the present invention may be a homopolymer of ethylene, which is an olefinic monomer, or preferably a copolymer of ethylene and an alpha olefinic comonomer.

 Alpha olefins having 4 or more carbon atoms may be used as the alpha olefin-based comonomer. Alpha-olefins having 4 or more carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-nuxadecene, 1-octadecene, 1-eicosene, and the like, but is not limited thereto. Of these, alpha olefins having 4 to 10 carbon atoms are preferable, and one or several kinds of alpha olefins may be used together as comonomers.

 In the copolymer of the ethylene and alpha olefin-based comonomer, the content of the alpha olepin-based comonomer may be about 5 to about 20% by weight, preferably about 7 to about 15% by weight, but is not limited thereto. .

The olefin polymer as described above may be prepared by using a common metallocene catalyst. It can manufacture.

 According to an embodiment of the present invention, the common metallocene catalyst may include a first metallocene compound represented by Formula 1 below; A second metallocene compound comprising at least one compound selected from the following compounds represented by Formula 2 or Formula 3; Cocatalyst compounds; And a common supported metallocene catalyst comprising a carrier.

 [

In Chemical Formula 1,

 R1 to R4, R9 and R1 'to R4' are the same as or different from each other, and each independently hydrogen, halogen: C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 Alkylaryl group or C7-C20 arylalkyl group;

 R5 to R8 are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group Adjacent two of R5 to R8 may be linked to each other to form one or more aliphatic rings, aromatic rings, or hetero rings;

 L 1 is a C1 to C10 straight or branched alkylene group;

D1 is -O-, -S-, -N (R)-or -Si (R) (R ')-, wherein R and R' are the same as or different from each other, and are each independently hydrogen, halogen, C1 to C20 alkyl group, An alkenyl group of C2 to C20 or an aryl group of C6 to C20;

 A1 is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, ci to C20 alkoxy group, C2 to C20 A C20 alkoxyalkyl group, C2 to C20 heterocycloalkyl group, or C5 to C20 heteroaryl group;

 ΜΪ is a Group 4 transition metal;

 XI and X2 are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, nitro group, amido group, C1 to C20 alkylsilyl group ,. A C1 to C20 alkoxy group or a C1 to C20 sulfonate group;

 [Formula 2]

 In Chemical Formula 2,

 R10 to R13 and R10 'to R13' are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 An arylalkyl group of C20 to C20 or an amine group of C1 to C20, and two adjacent R10 to R13 and R10 'to R13' may be connected to each other to form one or more aliphatic rings, aromatic rings, or hetero rings; ;

Z1 and Z2 are the same as or different from each other, and each independently hydrogen, an alkyl group of C1 to C20, a cycloalkyl group of C3 to C20, an alkoxy group of C1 to C20, an aryl group of C6 to C20, an aryloxy group of C6 to C10, C2 to C20 alkenyl group, C7 to C40 alkylaryl group, or C7 to C40 arylalkyl group; Q is an alkylene group of CI to C20, a cycloalkylene group of C3 to C20, an arylene group of C6 to C, an alkylarylene group of C7 to C40, or an arylalkylene group of C7 to C40;

 M 2 is a Group 4 transition metal;

 X3 and X4 are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, nitro group, amido group, C1 to C20 alkylsilyl group, A C1 to C20 alkoxy group or a C1 to C20 sulfonate group;

 [Formula 3]

In Chemical Formula 3,

 M 3 is a Group 4 transition metal;

 X5 and X6 are the same as or different from each other, and each independently halogen, C1 to C20 and an alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, nitro group, amido group, C1 to C20 alkylsilyl group, C1 To C20 alkoxy group, or C1 to C20 sulfonate group;

 R14 to R19 are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, C1 to C20 alkylsilyl, C6 to C20 arylsilyl group, or C1 to C20 amine group, two or more adjacent R14 to R17 are connected to each other at least one aliphatic ring , Aromatic rings, or hetero rings;

 L 2 is a straight or branched chain alkylene group of CI to CIO;

D2 is -0-, -S-, -N (R)-or -Si (R) (R ')-, wherein R and R' are the same as or different from each other, and are each independently hydrogen, halogen, C1 to C20 alkyl group An alkenyl group of C2 to C20 or an aryl group of C6 to C20;

 A2 is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, C1 to C20 alkoxy group, C2 to C20 A C20 alkoxyalkyl group, a C2 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;

 B is carbon, silicon, or germanium and is a bridge which binds a cyclopentadienyl series ligand and JR19z-y by a covalent bond;

 J is a periodic table group 15 element or group 16 element;

 z is the oxidation number of the element J;

 y is the number of bonds of the J elements.

 In the metallocene compound according to the present invention, the substituents of Chemical Formulas 1 to 3 will be described in more detail below.

 The C1 to C20 alkyl group includes a linear or branched alkyl group, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, nuclear chamber group, heptyl group, An octyl group etc. are mentioned, but it is not limited to this.

 The alkenyl group of C2 to C20 includes a linear or branched alkenyl group, and specifically, may include an allyl group, ethenyl group, propenyl group, butenyl group, pentenyl group, and the like, but is not limited thereto.

 The C6 to C20 aryl groups include monocyclic or condensed aryl groups, and specifically include phenyl groups, biphenyl groups, naphthyl groups, phenanthrenyl groups, and fluorenyl groups, but are not limited thereto.

 The C5 to C20 heteroaryl group includes a monocyclic or condensed heteroaryl group, and includes a carbazolyl group, a pyridyl group, a quinoline group, an isoquinoline group, a thiophenyl group, a furanyl group, an imidazole group, an oxazolyl group, a thiazolyl group , Triazine group, tetrahydropyranyl group, tetrahydrofuranyl group and the like, but are not limited thereto.

 Examples of the alkoxy group for C 1 to C 20 include a hydroxy group, an hydroxy group, a phenyloxy group, a cyclonuxyloxy group, and the like, but are not limited thereto.

Examples of the Group 4 transition metal include titanium, zirconium, and hafnium. However, the present invention is not limited thereto.

In the common supported metallocene catalyst according to the present invention, R1 to R9 and R1 'to R8' of Formula 1 are each independently hydrogen, methyl group, ethyl group, propyl group, isopropyl group, ^η -butyl group, tert- A butyl group, a pentyl group, a nuclear group, a heptyl group, an octyl group _: or a phenyl group is more preferable, but it is not limited to this.

 In the common supported metallocene catalyst according to the present invention, L1 of Chemical Formula 1 is more preferably a C4 to C8 linear or branched alkylene group, but is not limited thereto. In addition, the alkylene group may be unsubstituted or substituted with an alkyl group of C1 to C20, an alkenyl group of C2 to C20, or an aryl group of C6 to C20.

 In the common supported metallocene catalyst according to the present invention, A1 of Formula 1 is hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, mesoxymethyl group, tert-subspecial The methyl group, 1-hydroxyethyl group, 1-methyl-1-methoxyethyl group, tetrahydropyranyl group, or tetrahydrofuranyl group is more preferable, but is not limited thereto.

 According to an embodiment of the present invention, specific examples of the first metallocene compound represented by Chemical Formula 1 may include a compound represented by the following structural formulas, but is not limited thereto.

In the common supported metallocene catalyst according to the present invention, Q is an alkylene group of CI to C20, Z1 and Z2 are each independently hydrogen, an alkyl group of C1 to C20 or an alkoxy group of C1 to C20, X3 and X4 may be a halogen, but is not limited thereto.

 According to one embodiment of the present invention, specific examples of the second metallocene compound represented by Chemical Formula 2 may include a compound represented by the following structural formulas.

 In the common supported metallocene catalyst according to the present invention, L 2 of Chemical Formula 3 is more preferably a C4 to C8 linear or branched alkylene group, but is not limited thereto. In addition, the alkylene group may be unsubstituted or substituted with an alkyl group of C1 to C20, an alkenyl group of C2 to C20, or an aryl group of C6 to C20.

 In the common supported metallocene catalyst according to the present invention, A2 of Formula 3 is hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, methoxymethyl group, tert-buroxy Methyl group, 1-ethoxyethyl group, 1-methyl-1-methoxyethyl group, tetrahydropyranyl group, or tetrahydrofuranyl group is more preferable, but not limited thereto.

 In addition, B in the general formula (3) is silicon, J is preferably nitrogen, but is not limited thereto.

In addition, R14 to R19 of Formula 3 are each independently hydrogen, an alkyl group of C1 to C20, C2 _. It may be an alkenyl group of C to C20, or an alkoxy group of C1 to C20, but is not limited thereto.

Specific examples of the second metallocene compound represented by Chemical Formula 3 may include a compound represented by the following structural formula, but is not limited thereto. It is not.

 The method for producing a metallocene compound represented by Chemical Formulas 1 to 3 is described in detail in Examples described later.

 The first metallocene compound of Chemical Formula 1 forms a structure in which a fluorene derivative is crosslinked by a bridge and has a Lewis acid characteristic of the carrier by having a non-covalent electron pair capable of acting as a Lewis base in the ligand structure. It is supported on and shows high polymerization activity even when it is supported. In addition, since the fluorene group, which is electronically rich, has high activity, the high molecular weight olepin-based polymer can be added.

 Common supported metallocene catalyst according to an embodiment of the present invention is a second metal selected from one or more of the first metallocene compound represented by Formula 1 and the compound represented by Formula 2 or Formula 3 One or more of the sen compounds may be commonly supported on the carrier together with the cocatalyst compound.

 The first metallocene compound represented by Formula 1 of the common supported metallocene catalyst mainly contributes to making a high molecular weight copolymer, and the second metallocene compound represented by Formula 2 is a relatively low molecular weight copolymer. It can contribute to making In addition, the second metallocene compound represented by Formula 3 may contribute to making a copolymer of moderate molecular weight.

 Thus, including the metallocene compound of Formula 1 to 3, respectively

When using a common supported metallocene catalyst containing three metallocene compounds, the miscibility of high molecular weight and low molecular weight copolymers is compensated for, resulting in a wide molecular weight distribution resulting in high processability and high transparency. The olefinic polymer of this invention can be manufactured.

According to one embodiment of the present invention, the common supported metallocene catalyst may include at least one first metallocene compound of Formula 1 and at least one second metallocene compound of Formula 2. According to another embodiment of the present invention, the common supported metallocene catalyst may include at least one first metallocene compound of Formula 1 and at least one second metallocene compound of Formula 2, One or more second metallocene compounds may be included.

 Accordingly, in the common supported metallocene catalyst of the present invention, the first metallocene compound represented by Formula 1 and the second metallocene compound selected from the compound represented by Formula 2 or Formula 3 are different from each other. At least two or more metallocene compounds, preferably three different metallocene compounds. Accordingly, the high molecular weight and low molecular weight copolymers are complemented to improve the high molecular weight olefin copolymer, and at the same time, the molecular weight distribution is wide, thereby producing an excellent olefin polymer with excellent physical properties and processability.

 In the common supported metallocene catalyst, a co-catalyst supported on a carrier for activating the metallocene compound is an organometallic compound containing a Group 13 metal, and when the olefin is polymerized under a general metallocene catalyst There is no particular limitation as long as it can be used.

 Specifically, the cocatalyst compound may include one or more of the cocatalyst compounds represented by the following Chemical Formulas 4 to 6.

 [Formula 4]

 -[A1 (R20) -O] n- in Formula 4,

 R20 may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;

 n is an integer of 2 or more;

 [Formula 5]

D (R20) ₃

 In Chemical Formula 5,

 R20 is as defined in Formula 4 above;

D is aluminum or boron; [Formula 6]

[LH] + [ZA ₄ ] -or [L] + [ZA ₄ ]-in Chemical Formula 6,

 L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a group element; A may be the same as or different from each other, and each independently is a C6 to C20 aryl group or a C1 to C20 alkyl group, wherein at least one hydrogen atom is unsubstituted or substituted with halogen, C1 to C20 hydrocarbon, alkoxy or phenoxy.

 Examples of the compound represented by the formula (4) include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane and the like, and more preferred compound is methyl aluminoxane.

 Examples of the compound represented by Formula 5 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri-S-butyl aluminum, tricyclopentyl aluminum , Tripentylaluminum, triisopentylaluminum, trinuclear silaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-P-rylylaluminum, dimethylaluminum mesoxide, dimethylaluminum, trimethyl Boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

 Examples of the compound represented by Formula 6 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, and trimethylammonium tetra (P-lryl) Boron, trimethylammonium tetra (ο, ρ- dimethylphenyl) boron, tributyl ammonium tetra (Ρ-trifluoromethylphenyl) boron, trimethyl ammonium tetra (Ρ-trifluoromethylphenyl) boron,

Tributylammonium tetrapentafluorophenylboron, Ν, Ν- diethylanilinium tetraphenylboron, Ν, Ν-diethylanilinium tetrapentapololophenylboron,

Diethylammonium tetrapentafluorophenyl boron, triphenylphosphonium tetraphenal boron, Trimethylphosphonium tetraphenylboron, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra (P-lryl) aluminum, tri Propyl Ammonium Tetra (P-lryl) Aluminum, Triethyl Ammonium Tetra (ο, ρ-dimethylphenyl) Aluminum, Tributyl Ammonium Tetra (ρ_ Trifluoromethylphenyl) Aluminum, Trimethyl Ammonium Tetra (Ρ- Tripleloro Methylphenyl) aluminum,

Tributylammonium tetrapentafluorophenylaluminum, Ν, Ν- diethylanilinium tetraphenylaluminum, Ν, Ν-diethylanilinium tetrapentafluorophenylaluminum,

Diethylammonium tetrapenta tetraphenylaluminum ，

Triphenylphosphoniumtetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, tripropylammoniumtetra (Ρ-ryll) boron, triethylammoniumtetra (ο, ρ— dimethylphenyl) boron, tributylammoniumtetra (Ρ- Trifluoromethylphenyl) boron, triphenylcarbonium tetra (Ρ-trifluoromethylphenyl) boron,

Triphenylcarbonium tetrapentafluorophenylboron, and the like.

 In the common supported metallocene catalyst, the mass ratio of the transition metal to the carrier of the first and second metallocene compounds is preferably 1: 1 to 1: 1,000. When including the carrier and the metallocene compound in the mass ratio, it may be advantageous in terms of maintaining the activity and economical efficiency of the catalyst by showing the appropriate supported catalytic activity.

 In addition, the mass ratio of the cocatalyst compound of formula 4 or 5 to the carrier is preferably 1:20 to 20: 1, and the mass ratio of the cocatalyst compound of the formula 6 to the carrier is preferably 1:10 to 100: 1.

 Moreover, it is preferable that the mass ratio of the said 1st metallocene compound to the said 2nd metallocene compound is 1: 100-100: 1. When the co-catalyst and the metallocene compound are included in the mass ratio, an appropriate catalytic activity may be exhibited, which may be advantageous in terms of maintaining the activity and economical efficiency of the catalyst.

In the common supported metallocene catalyst, a carrier containing a hydroxyl group on the surface can be used, and preferably, The carrier which has the semi-permanent hydroxyl group and siloxane group from which the water was removed to the surface can be used.

For example, silica, silica-alumina, silica-magnesia, etc., dried at a high temperature may be used, which are typically oxides, carbonates, such as Na ₂ O, K ₂ C0 ₃ , BaS0 ₄ , and Mg (0 ₃ ) ₂ , Sulfate, and nitrate components. The drying temperature of the carrier is preferably 100 to 800. If the drying temperature of the carrier is less than 100 ^° C, the moisture is too much and the surface of the carrier reacts with the promoter, and if it exceeds 800 ^° C, the surface area decreases as the pores on the surface of the carrier are combined, and the surface is hydroxy. It is not preferable because there is a lot of groups and only siloxane groups are left to decrease the reaction space with the promoter.

 The amount of hydroxyl groups on the surface of the carrier is preferably 0.1 to 10 mmol / g, more preferably 0.2 to 5 mmol / g. The amount of hydroxyl groups on the surface of the carrier can be controlled by the method and conditions for preparing the carrier or by drying conditions such as temperature, time, vacuum or spray drying.

 If the amount of the hydroxy group is less than 0.1 mmol / g, there is little reaction space with the cocatalyst. If the amount of the hydroxy group is more than 10 mmol / g, it may be due to moisture other than the hydroxy group present on the surface of the carrier particle. not.

 The common supported metallocene catalyst is prepared by supporting a cocatalyst compound on a carrier, supporting the first metallocene compound on the carrier, and supporting the second metallocene compound on the carrier. can do. In the method for preparing the common supported metallocene catalyst, the order of the steps of supporting the first and second metallocene compounds may be changed as necessary. That is, the first metallocene compound is first supported on the carrier, and then the second metallocene compound is further supported to prepare a common supported metallocene catalyst, or the second metallocene compound is first supported on the carrier. After that, the first metallocene compound may be supported. Alternatively, the first and second metallocene compounds may be added and supported at the same time.

Pentane, nucleic acid, as a reaction solvent in the preparation of the common supported metallocene catalyst Hydrocarbon solvents such as heptanes, or aromatic solvents such as benzene, toluene and the like can be used. The metallocene compound and the cocatalyst compound can also be used in the form of silica or alumina.

 The olefin polymer according to the present invention can be produced by polymerizing an olefin monomer in the presence of the above-described common supported metallocene catalyst. In the method for preparing the olefin polymer, specific examples of the olefin polymer may include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-nuxene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-ikocene, and the like, and two or more thereof may be mixed and copolymerized.

 The olefin polymer is more preferably an ethylene / alpha olefin copolymer, but is not limited thereto.

In the case where the olepin-based polymer is an ethylene / alpha olefin copolymer, the content of alpha olepin, which is the comonomer, is not particularly limited, and may be appropriately selected according to the use, purpose, and the like of the olepin-based polymer. More specifically, it may be up to more than 0 to 99 mole ^_0/0.

 The polymerization reaction can be carried out by homopolymerization with one olefinic monomer or copolymerization with two or more monomers using one continuous slurry polymerization reaction, loop slurry reaction, gas phase reaction or solution reaction.

The common supported metallocene catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, hexane, heptane, nonane, decan, and isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, dichloromethane and chlorobenzene. It may be dissolved or liquefied and injected into a hydrocarbon solvent substituted with a chlorine atom such as. The solvent used herein is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating a small amount of alkyl aluminum, and may be carried out by further using a promoter. By using the common supported metallocene catalyst, it is possible to produce an urepin-based copolymer having a molecular weight distribution curve of two or more. When using the common supported metallocene catalyst, a relatively high molecular weight olepin-based polymer can be prepared by the first metallocene compound, and the second metallocene Relatively low molecular weight olepin-based polymers can be prepared by the compounds. In particular, the common supported metallocene catalyst may include at least one first metallocene compound of Formula 1, at least one second metallocene compound of Formula 2, and

When one or more of the second phthalocene compounds of 3 are contained, high molecular weight, low molecular weight, and medium molecular weight olepin-based polymers are produced to have broad molecular weight distribution and improve the compatibility between high molecular weight and low molecular weight polymers. Olefin-based polymers showing transparency can be produced.

Using the common supported metallocene catalyst of the present invention, the polymerization temperature may be about 25 to about 500 ^° C., preferably about 25 to about 200 ^° C., more preferably about 50 to about 150 ^° C. In addition, the polymerization pressure is about 1 to about 100 Kgf / cm ² , preferably about 1 to about 70 Kgf / cm ² , more preferably about 5 to about 50

Kgf / cm ² can be.

 The leulevine-based polymer according to the present invention is a polymer having a high molecular weight and a wide molecular weight distribution as described above by homopolymerization of ethylene or copolymerization of ethylene and alpha olepin using the above common supported metallocene compound as a catalyst. Can be prepared.

 Accordingly, the olefin polymer of the present invention is excellent in mechanical properties such as tensile strength and tear strength, processability, haze, and the like, and can be variously applied according to a use, and particularly, a film having improved physical properties Can provide.

 Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto. <Example>

 Synthesis Example 1 Preparation of First Metallocene Compound

Preparation of "ert-Bu-0- (CH _? V> MeSi (9-C _n H _Q ) ₇ ZrCl ₇

 1) Preparation of Ligand Compound

1.0 mole of a Grignard reagent tert-Bu-0- (CH ₂ ) ₆ MgCl solution was obtained from reaction between tert-Bu-0- (CH ₂ ) ₆ Cl compound and Mg (0) in THF solvent. The prepared Grignard compound MeSiCl _{3 in} the state of -30 ^° C OZ

^ ^ Next z IK -z I P-g. οε

(P 'HZ' H-nd L '(P' HS 쒜

'(PP' H1 09 ^' L' (∞ 'Ht' H_ ⁿ Id) iVL '0' BZ 'HD 06 ^' 9 '0 ¾3' H ^ Id) 98 ^' 9

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[(i ^m ooi) t-rl aoe- 'ir ^ aoe- ui ς · ζ) nng-ΐΐ ^ μι' ir # i (lourai QI 'qui ζ · ι' jsq iXjnq ^ sj iXqjaui) gaiW 5

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T8t ⁷ 800 / M0ZaM / X3d J. AM. CHEM. SOC. VOL. 126, No. 46, 2004 pp. L, 2-ethylene bis (indenyl) ZrCl ₂ compound was synthesized as disclosed in 15231 15244. Synthesis Example 3 Preparation of Second Metallocene Compound

Preparation of tBu-Q- (CH 1/2) (CH ₁ ) Si (Cs (CH ^ 4 tBu-N ^' ) TiCl

50 g of Mg (s) was added to a 10 L reaction vessel at room temperature, followed by 300 mL of THF. After adding 0.5 g of I ₂ , the reaction was maintained at 50 ^° C. After the reactor temperature was stabilized, 250 g of 6-t-buthoxyhexyl chloride was added to the reactor at a rate of 5 mL / min using a feeding pump. It was observed that the reactor temperature was increased by 4 to 5 ^° C. with the addition of 6-t-butoxynuclear chloride. Subsequently, the mixture was stirred for 12 hours while adding 6-t-subspecification chamber chloride. After 12 hours, a black reaction solution was obtained. 2 mL of the resulting black solution was taken, water was added thereto, an organic layer was obtained, and 6-t-buthoxyhexane was confirmed by 1 H-NMR. The Gringanrd reaction proceeded well from the 6-t- appendic acid. Thus, 6-t-buthoxyhexyl magnesium chloride-!-Was synthesized.

After adding 500 g of MeSiCl ₃ and 1 L of THF to the reaction vessel, the reaction was conducted to -20 ^° C. 560 g of the synthesized 6-t-butoxynuclear magnesium chloride was added to the reaction vessel at a rate of 5 mL / min using a feeding pump. After the feeding of the Grannard reagent (feeding) was completed, the reaction mixture was stirred for 12 hours while slowly raising the temperature to room temperature. After 12 hours, it was confirmed that a white MgCl ₂ salt was produced. 4 L of nucleic acid was added to remove the salt through a labdori to obtain a filter solution. The obtained filter solution was added to the reactor and the nucleic acid was removed at 70 ^° C to obtain a pale yellow liquid. The obtained liquid was confirmed to be the desired methyl (6-t-buthoxy hexyl) dichlorosilane} compound through 1 H-NMRol.

 1 H-NMR (CDC13): 3.3 (t, 2H), 1.5 (m, 3H), 1.3 (m, 5H), 1.2 (s, 9H), 1.1 (m, 2H), 0.7 (s, 3H)

1.2 mol (150 g) of tetramethylcyclopentadiene and After adding 2.4 L of THF to the reactor, the reactor was cooled to -20 ^° C. The reactor was added at a rate of 5 mL / min using an n-BuLi 480 mL feeding pump. After n-BuLi was added, the reaction mixture was stirred for 12 hours while slowly raising the temperature of the reactor. After 12 hours of reaction, an equivalent of methyl (6-t-buthoxy hexyl) dichlorosilane (326 g, 350 mL) was added quickly to the reactor. After stirring for 12 hours while slowly raising the reactor temperature to silver, the reaction mixture was again cooled down to 0 ^° C., and 2 equivalents of t-BuN¾ was added thereto. Banunggi Silverware was stirred for 12 hours while slowly quenching with Silver. After 12 hours of reaction, THF was removed and 4 L of nucleic acid was added to obtain a filter solution from which salt was removed through a labdori. After adding the filter solution to the reactor again, the nucleic acid was removed at 70 ^° C to obtain a yellow solution. The yellow solution obtained was identified to be methyl (6-t-butoxynucleosil) (tetramethyl CpH) t-butylaminosilane (Methyl (6-t-buthoxyhexyl) (tetramethylCpH) t-Butylaminosilane) compound through 1H-NMRol. .

TiCl ₃ (THF) ₃ (10) to the dilithium salt of -78 ^° C ligand synthesized in THF solution from n-BuLi and ligand dimethyl (tetramethyl CpH) t-butylaminesilane (Dimethyl (tetramethylCpH) t-Butylaminosilane) mmol) was added rapidly. The reaction solution was slowly stirred at 78 ^° C. for 12 hours while eluting with silver. After stirring for 12 hours, an equivalent amount of PbCl ₂ (10 mmol) was added to the semi-aqueous solution at room temperature, followed by stirring for 12 hours. After stirring for 12 hours, a dark black solution was obtained. After removing THF from the reaction solution, nucleic acid was added to filter the product. After removing the nucleic acid from the filter solution obtained, the desired ([methyl (6-t-buthoxyhexyl) silyl (n5-tetramethylCp) (t-Butylamido)] TiC¾ (tBu-O- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ (CH ₃ ) ₄ ) (tBu-N) TiCl ₂ .

 1 H-NMR (CDCls): 3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 6H), 1.8 to 0.8 (m), 1.4 (s, 9H), 1.2 (s, 9H), 0.7 (s, 3H)

<Example of preparing supported catalyst>

 Preparation Example 1

Into a 20 L sus high pressure reaction vessel, 3.0 kg of aluene solution was added, and 1,000 g of silica (SP952X, manufactured by Grace Davison, 200 degree firing) was added, and then the reaction temperature was adjusted. Stirred to 40 ^° C. After silica was dispersed in 60 minutes, 6.0 kg of 10 wt% methylaluminoxane (MAO) / luene solution was added, and the temperature was reduced to 60 ^° C., followed by stirring at 200 rpm for 12 hours. After the reactor temperature was lowered to 40 ° C. again, the stirring was stopped and settling for 30 minutes was followed by decantation of the reaction solution. 3.0 kg of toluene was added and stirred for 10 minutes, and then stirring was stopped, settling for 30 minutes, and decantation of the toluene solution.

 2.0 kg of toluene was added to the reactor, a solution was prepared by placing a flask of metallocene compound of Synthesis Example 1 and 1,000 mL of toluene in a flask, and sonication was performed for 30 minutes. The metallocene compound / luene solution of Synthesis Example 1 thus prepared was added to the reactor and stirred at 200 rpm for 90 minutes. After stirring was settled and settling for 30 minutes, the reaction solution was decantation.

 2.0 kg of toluene was added to the reactor, and the solution was prepared by polarizing the metallocene compound of Synthesis Example 2 and 1,500 mL of toluene, and sonication was performed for 30 minutes. The metallocene compound / luene solution of Synthesis Example 2 prepared as described above was added to the reactor and stirred at 200 rpm for 90 minutes. After the reactor temperature was lowered to room temperature, stirring was stopped, settling for 30 minutes, and the reaction solution was decantation. .

 2.0 kg of toluene was added thereto, stirred for 10 minutes, the stirring was stopped, settling for 30 minutes, and the toluene solution was decantation.

3.0 kg of nucleic acid was added to the reaction vessel, the nucleic acid slurry was transferred to a filter dryer, and the nucleic acid solution was filtered. Drying under reduced pressure at 50 ^° C. for 4 hours to prepare a 700g-SiO ₂ hybrid supported catalyst. Preparation Example 2

 20L sus high pressure reaction machine add 3.0 kg of toluene solution to silica (Grace

1,000 g of Davison Co., Ltd. SP2410) was added thereto, followed by stirring while stirring the reaction temperature at 40 ^° C. After the silica was dispersed in 60 minutes, 5.4 kg of 10 wt% methylaluminoxane (MAO) / luene solution was added thereto, the temperature was raised to 60 ^° C., and the mixture was stirred at 200 rpm for 12 hours. After the reaction was lowered back to 40 ^° C., the stirring was stopped and settling for 30 minutes was followed by decantation of the reaction solution. 3.0 kg of toluene was added and stirred for 10 minutes, and then stirring was stopped, settling for 30 minutes, and decantation of the toluene solution.

 2.0 kg of toluene was added to the reaction vessel, a solution was prepared by putting a flask of metallocene compound of Synthesis Example 1 and 1,000 mL of toluene into a flask, and sonication was performed for 30 minutes. The metallocene compound / toluene solution of Synthesis Example 1 prepared as described above was added to the reactor and stirred at 200 rpm for 90 minutes. After stirring, the mixture was settling for 30 minutes and the reaction solution was decantation.

 2.0 kg of toluene was added to the reaction machine, the solution was prepared by putting a flask of metallocene compound of Synthesis Example 3 and 1,000 mL of toluene into a flask, and sonication was performed for 30 minutes. The metallocene compound / luene solution of Synthesis Example 3 prepared as described above was added to the reactor and stirred at 200 rpm for 90 minutes. After stirring was stopped and settling for 30 minutes, the reaction solution was decantation.

 2.0 kg of Bungung-Gise Toluene was added, a solution was prepared by placing a flask of 300 mL of the metallocene compound and Synthesis Example 2 in the Synthesis Example 2 and sonication was performed for 30 minutes. The metallocene compound / luene solution of Synthesis Example 2 prepared as described above was added to the reactor and stirred at 200 rpm for 90 minutes. After the reaction temperature was lowered to room temperature, stirring was stopped and settling was performed for 30 minutes, followed by decantation of the reaction solution.

 2.0 kg of toluene was added and stirred for 10 minutes, and then stirring was stopped, settling for 30 minutes, and decantation of the toluene solution.

3.0 kg of nucleic acid was added to the reaction vessel, the nucleic acid slurry was transferred to a filter dryer, and the nucleic acid solution was filtered. Drying under reduced pressure at 50 ^° C. for 4 hours to prepare a 830 g-SiO ₂ common soak catalyst. <Elefin Polymerization Example>

 Example 1

The common supported metallocene catalyst obtained in Preparation Example 1 was introduced into an isobutane slurry loop process continuous polymerization reactor (reactor volume 140 L, reaction volume flow rate 7 m / s) to prepare an olefin polymer. 1-hexene was used as comonomer, the reaction pressure was maintained at 40 bar, the polymerization temperature was 88 ^° C. Example 2

 An olefin polymer was prepared in the same manner as in Example 1 except that the amount of 1-nuxene used in Example 1 was changed. Example 3

 An olefin polymer was prepared in the same manner as in Example 1, except that the amount of 1-hexene used in Example 1 was changed. Example 4

The common supported metallocene catalyst obtained in Preparation Example 2 was introduced into an isobutane slurry loop process continuous polymerization reactor (reactor volume 140 L, reaction volume flow rate 7 m / s) to prepare an olefin polymer. As a comonomer, 1-nucleenol was used, the reactor pressure was maintained at 40 bar, and the polymerization temperature was maintained at 88 ^° C. Example 5

 An olefin polymer was prepared in the same manner as in Example 1 except that the amount of 1-nuxene used in Example 4 was changed. Comparative Example 1

LG Chem's LUCENE ^™ SP310, a commercial mLLDPE prepared using slurry loop process, was prepared.

Experimental Example

 Manufacture of film

The olefin polymers of Examples 1 to 5 and Comparative Example 1 were analyzed after granulation with a biaxial extruder after prescribed an antioxidant (Iganox 1010 + Igafos 168, CIBA). Film molding was performed using a single screw extruder (Shinhwa Industrial Single Screw Extruder, Blown Film M / C, 50 pie, L / D = 20) and extrusion was inflation-molded to a thickness of 0.05 mm at 165 ~ 200 ^° C. Die gap is 2.0 mm, Blow-Up Ratio was set to 23. Polymer and film and physical property evaluation

 The physical properties of the olefin polymers of Examples 1 to 5 and Comparative Example 1 and the films prepared using the same were measured according to the following evaluation method, and the results are shown in Table 1 below.

 In addition, a graph showing the relationship between the frequency-complex viscosity (complex visicosity) of the olefin polymers according to Examples, 2 and Comparative Example 1 of the present invention is shown in FIG.

 1) Density: ASTM 1505

2) Melt Index (Ml, 2.16 kg / 10 kg): Measuring Temperature 190 ^° C, ASTM 1238

3) MFRR (MFRio / MFR ₂ ): MFR ₁₀ melt index (MI, 10kg load) divided by MFR ₂ (MI, 2.16kg load).

4) Molecular weight, molecular weight distribution: The number average molecular weight, the weight average molecular weight, and the Z average molecular weight were measured using a measurement temperature of 160 ^° C. and gel permeation chromatography-GFT-Al (GPC-FTIR). It is expressed as ratio of number average molecular weight ᅳ

 5) Haze: The film was molded to a thickness of 0.05 mm and measured based on ASTM D 1003. At this time, 10 measurements were taken per specimen and the average was taken.

6) Slope of the graph (complex visicosity, i [Pa.s]) according to frequency (o [md / s]) 1: The complex viscosity is 190 ^° C using Advanced R eometric Expansion System (ARES). , Measured in the linear viscoelastic region.

 Table 1

Weight average 15.0 11.4 12.2 14.8 12.8 1 1.2 Self weight

(* 10 ⁴

 g / mol)

 Molecular weight distribution 5.5 12.2 5.3 4.8 5.9 2.8 Haze 38 44 46 17 20 15 -0.36 -0.39 -0.36 -0.35 -0.37 -0.24

Of the beam, c j graph ^"

 Gradient Referring to Table 1 and the graphs of FIG. 1, the ellefin-based polymer according to the present invention exhibits a wider molecular weight distribution than a conventional olefin-based polymer having a similar density and weight average molecular weight, and thus has a high melt index. It can be seen that the shear thinning effect is much better and shows excellent flowability and processability.

Claims

【Patent Claims】

【Claim 1】

molecular weight distribution (Mw/Mn) is 3 to 20;

The melt flow rate ratio (MFR ₁₀ /MFR ₂ ) measured by ASTM1238 at 190 ^° C is 9 to 15;

An olefin-based polymer with a slope of -0.55 to -0.35 in a graph of complex viscosity (r)*[Pa.s]) according to frequency (oo[rad/s]).

[Claim 2]

The olefin-based polymer according to claim 1, wherein the olefin polymer has a density of 0.910 to 0.940 g/cm ³ .

【Claim 3】

The olefin-based polymer according to claim 1, wherein the olefin-based polymer has the maximum SCB (Short Chain Branching) content within the range of 0.2 to 0.8 when the weight average molecular weight (M) measured by GPC-FTIR is 0.5.

【Claim 4】

The olefin-based polymer according to claim 1, wherein the olefin-based polymer has a weight average molecular weight of 50,000 to 200,000 g/m.

[Claim 5]

The olefin-based polymer according to claim 11, which is a copolymer of ethylene and an alpha olefin-based comonomer.

【Claim 6】

In clause 1,

A first metallocene compound represented by the following formula (1); An olefin-based polymer prepared by polymerizing an olefin-based monomer in the presence of a common metallocene catalyst comprising a second metallocene compound containing at least one selected from the following compounds represented by Formula 2 or Formula 3: [Formula 1]

In Formula 1,

R1 to R4, R9 and R1' to R4' are the same or different from each other, and are each independently hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkyl It is an aryl group, or a C7 to C20 arylalkyl group;

R5 to R8 are the same or different from each other, and are each independently hydrogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group. and two adjacent ones of R5 to R8 may be connected to each other to form one or more aliphatic rings, aromatic rings, or hetero rings;

L1 is a straight or branched C1 to C10 alkylene group;

D1 is -0-, -S-, -N(R)- or -Si(R)(R')-, where R and R' are the same or different from each other, and are each independently hydrogen, halogen, C1 to It is a C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group;

A1 is hydrogen, halogen, C1 alkyl group of C20, alkenyl group of C2 to C20, aryl group of C6 to C20, alkylaryl group of C7 to C20, arylalkyl group of C7 to C20, alkoxy group of C1 to C20, C2 to It is a C20 alkoxyalkyl group, a C2 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;

Ml is a group 4 transition metal; XI ^and a C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;

[Formula 2]

In Formula 2,

R10 to R13 and R10' to R13' are the same or different from each other, and are each independently hydrogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, and C7. to C20 arylalkyl group, or C1 to C20 amine group, the two adjacent ones of R10 to R13 and R10' to R13' may be connected to each other to form one or more aliphatic rings, aromatic rings, or hetero rings. There is;

Z1 and Z2 are the same or different from each other, and are each independently hydrogen, a C1 to C20 alkyl group, a C3 to C20 cycloalkyl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C6 to C10 aryloxy group, C2 to C20 alkenyl group, C7 to C40 alkylaryl group, or C7 to C40 arylalkyl group;

Q is a C1 to C20 alkylene group, a C3 to C20 cycloalkylene group, a C6 to C20 arylene group, a C7 to C40 alkylarylene group, or a C7 to C40 arylalkylene group;

M2 is a group 4 transition metal;

X3 and A nitro group, an amido group, a C1 to C20 alkylsilyl group, a C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;

Formula 3]

In Formula 3 above,

M3 is a group 4 transition metal;

X5 and to C20 alkoxy group, or C1 to C20 sulfonate group;

R14 to R19 are the same or different from each other, and are each independently hydrogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, C1 to C20 alkylsilyl, C6 to C20 arylsilyl group, or C1 to C20 amine group, and two or more adjacent R14 to R17 groups are connected to each other to form one or more aliphatic rings. , may form an aromatic ring, or a hetero ring;

L2 is a straight or branched C1 to C10 alkylene group;

D2 is -0-, -S-, -N(R)- or -Si(R)(R')-, where R and R' are the same or different from each other and are each independently hydrogen, halogen, C1 to It is a C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group;

A2 is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, C1 to C20 alkoxy group, C2 to C20 It is a C20 alkoxyalkyl group, a C2 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;

Carbon, silicon, or germanium, and cyclopentadienyl It is a bridge that binds the ligand and JR19z-y by covalent bonding;

J is a group 15 or 16 element of the periodic table;

z is the oxidation number of element J;

y is the bond number of the J element.

【Claim 7】

The method of claim 16, wherein L1 of Formula 1 is a C4 to C8 straight-chain or branched alkylene group, and A1 is hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, me An olefin-based polymer that is a toxymethyl group, _tert -butoxymethyl group, i-eroxyethyl group, _μmethyl -μmethoxyethyl group, tetrahydropyranyl group, or tetrahydrofuranyl group.

^•

【Claim 8】

The method of claim 6, wherein Q in Formula 2 is a C1 to C20 alkylene group, Z1 and Ζ2 are each independently hydrogen, a C1 to C20 alkyl group, or a C1 to C20 alkoxy group, and Χ3 and Χ4 are halogen olefins. based polymer.

[Canggu Port 9]

The method of claim 6, wherein in Formula 3, Β is silicon, J is nitrogen, and R14 to R19 are each independently hydrogen, an olefin group that is a C1 to C20 alkyl group, a C2 to C20 alkenyl group, or a C1 to C20 alkoxy group. based polymer.

【Claim 10】

The olefin-based polymer according to claim 6, wherein the cocatalyst compound includes at least one compound represented by the following Chemical Formula 4, Chemical Formula 5, or Chemical Formula 6:

[Formula ⁴ ]

-[A1(R20)-O]n- In chemical chain 4,

R20 may be the same or different from each other and are each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; or halogen-substituted carbon atoms of 1 to 20 It is a hydrocarbon;

n is an integer greater than or equal to 2;

[Formula 5]

D(R20)3

In Formula 5 above,

R20 is as defined in Formula 4 above;

D is aluminum or boron;

[Formula 6]

[L-H]+[ZA4]- or [L] + [ZA4]- In Formula 6,

L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a group 13 element; A may be the same or different from each other, and each independently represents a C6 to C20 aryl group or a C1 to C20 alkyl group in which one or more hydrogen atoms are substituted or unsubstituted with halogen, C1 to C20 hydrocarbon, alkoxy, or phenoxy.

【Claim 11】

A film comprising the olefin-based polymer of any one of claims 1 to 10.