KR102434451B1 - Polyolefin - Google Patents

Abstract

The present invention relates to polyolefins. More specifically, the present invention relates to a polyolefin having excellent drop impact strength and capable of exhibiting improved transparency.

Description

Polyolefin {POLYOLEFIN}

The present invention relates to polyolefins. More specifically, the present invention relates to a polyolefin that has improved mechanical properties such as excellent drop impact strength and can exhibit improved transparency during film production.

Linear low density polyethylene (LLDPE) is a resin produced by copolymerizing ethylene and alpha olefin at low pressure using a polymerization catalyst, has a narrow molecular weight distribution, has short chain branches of a certain length, and does not have long chain branches. The linear low-density polyethylene film has high breaking strength and elongation along with the characteristics of general polyethylene, and has excellent tear strength and drop impact strength. are doing

However, the linear low-density polyethylene has disadvantages in that the blown film processability is poor and transparency is inferior compared to excellent mechanical properties. The blown film is a film produced by blowing air into molten plastic to inflate, and is also called an inflation film.

On the other hand, linear low-density polyethylene generally has characteristics of increasing transparency and drop impact strength as the density decreases. However, when a large amount of alpha olefin comonomer is used to prepare low-density polyethylene, there is a problem in that the frequency of occurrence of fouling in the slurry polymerization process increases.

On the other hand, in order to improve processability, processing characteristics can be improved by introducing LCB (Long chain branch) into linear low-density polyethylene, but when there are many LCBs, transparency and drop impact strength are inferior.

Therefore, there is a need for the development of polyethylene capable of implementing excellent mechanical properties, such as drop impact strength, as well as low density and transparency.

Korean Patent Publication No. 2010-0102854

In order to solve the problems of the prior art, the present invention is to provide a polyolefin that has improved mechanical properties such as low density and excellent drop impact strength, and can exhibit improved transparency during film production.

In order to solve the above problems, the present invention,

a density of 0.915 g/cm ³ to 0.930 g/cm ³ ; and

SSA (Successive Self-nucleation and Annealing) analysis, the non-uniformity (inhomogeneity, I) of the ethylene sequence calculated by Equation 1 below is 1.25 to 1.40,

A polyolefin is provided:

[Equation 1]

Inhomogeneity (I) = L _w / L _n

In Equation 1 above,

L _w is a weighted average (unit: nm) of ESL (Ethylene sequence length), and L _n is an arithmetic mean (Unit: nm) of ESL (Ethylene sequence length).

According to the present invention, it is possible to provide a polyolefin having optimal ethylene sequence inhomogeneity by appropriately controlling the length and distribution of the ethylene sequence forming lamellars during polymerization of polyolefin using a metallocene catalyst. have.

Accordingly, it is possible to provide a polyolefin excellent in transparency and having high drop impact strength.

1 is a graph showing the relationship between inhomogeneity and drop impact strength of polyolefins according to Examples and Comparative Examples of the present invention.
2 is a graph showing the temperature profile of the SSA analysis method according to an embodiment of the present invention.

In the present invention, terms such as first, second, etc. are used to describe various components, and the terms are used only for the purpose of distinguishing one component from other components.

In addition, the terminology used herein is used only to describe exemplary embodiments, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present specification, terms such as "comprise", "comprising" or "having" are intended to designate the presence of an embodied feature, number, step, element, or a combination thereof, but one or more other features or It should be understood that the existence or addition of numbers, steps, elements, or combinations thereof is not precluded in advance.

Since the present invention may have various modifications and various forms, specific embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

Hereinafter, the polyolefin of the present invention will be described in detail.

The polyolefin according to an embodiment of the present invention has a density of 0.915 g/cm ³ to 0.930 g/cm ³ ; And SSA (Successive Self-nucleation and Annealing) is characterized in that the heterogeneity (inhomogeneity, I) of the ethylene sequence calculated by Equation 1 below during analysis is 1.25 to 1.40.

[Equation 1]

Inhomogeneity (I) = Lw/Ln

In Equation 1 above,

L _w is a weighted average (unit: nm) of ESL (Ethylene sequence length), and L _n is an arithmetic mean (Unit: nm) of ESL (Ethylene sequence length).

Linear low density polyethylene (LLDPE) is produced by copolymerizing ethylene and alpha olefin at low pressure using a polymerization catalyst, and is a resin having a narrow molecular weight distribution and short chain branches of a constant length. The linear low-density polyethylene film has high breaking strength and elongation along with the characteristics of general polyethylene, and has excellent tear strength and drop impact strength. are doing

On the other hand, linear low-density polyethylene is generally known to increase transparency and drop impact strength as the density decreases. However, when a lot of comonomer is used to produce low-density polyethylene, the frequency of fouling increases in the slurry polymerization process, and the amount of antiblocking agent must be increased due to stickiness when manufacturing a film containing the same. There is a problem of In addition, there is a problem in that the process is unstable during production or the morphology characteristic of the polyethylene produced is lowered, so that the bulk density is reduced.

Therefore, in the present invention, the optimum ASL (Average Ethylene Sequence Length) ratio that can increase transparency and drop impact strength by appropriately adjusting the length and distribution of the ethylene sequence forming lamellar while having low density characteristics An object of the present invention is to provide a polyolefin having

Specifically, the polyolefin according to an embodiment of the present invention has a density of 0.915 g/cm ³ or more and 0.930 g/cm ³ or less. That is, the present invention may be a low-density polyolefin having a density of 0.930 g/cm ³ or less.

According to an embodiment of the present invention, the polyolefin may be, for example, a copolymer of ethylene and alpha olefin. In this case, the alpha olefin is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbornadiene, ethylidene noboden, phenyl noboden, vinyl noboden, dicyclopentadiene, 1,4-butadiene, 1,5- It may be one containing pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene. Among them, the polyolefin may be a copolymer of ethylene and 1-butene, a copolymer of ethylene and 1-hexene, or a copolymer of ethylene and 1-octene.

More specifically, according to one embodiment, the density of the polyolefin of the present invention is 0.915 g/cm ³ or more, or 0.916 g/cm ³ or more, or 0.917 g/cm ³ or more, or 0.918 g/cm ³ or more, or, or 0.919 g/cm ³ or more, and 0.930 g/cm ³ or less, or 0.928 g/cm ³ or less, or 0.925 g/cm ³ or less, or 0.922 g/cm ³ or less, or 0.921 g/cm ³ or less, or 0.920 g /cm ³ or less. In this case, the density is a value measured according to ASTM D1505.

According to one embodiment, the polyolefin of the present invention has an inhomogeneity (I) of 1.25 to 1.40 of an ethylene sequence calculated by Equation 1 below during SSA (Successive Self-nucleation and Annealing) analysis.

[Equation 1]

Inhomogeneity (I) = Lw/Ln

In Equation 1 above,

L _w is a weighted average (unit: nm) of ESL (Ethylene sequence length), and L _n is an arithmetic mean (Unit: nm) of ESL (Ethylene sequence length).

The polyolefin of the present invention is a semi-crystalline polymer, and may include a crystalline portion and an amorphous portion. Specifically, the crystalline portion forms a bundle as the polymer chain including the ethylene repeating unit is folded, thereby forming a lamellar-shaped crystalline block (or segment). The ethylene repeating unit forming the lamellar crystal is an ethylene sequence.

The inventors of the present invention, when the non-uniformity (I) of the ethylene sequence calculated by Equation 1 according to SSA (Successive Self-nucleation and Annealing) analysis is 1.25 to 1.40, compared to the conventional polyolefin of the same density, more It led to the present invention by focusing on being able to have improved transparency and drop impact strength.

SSA (Successive Self-nucleation and Annealing) is a method of preserving crystals crystallized at the temperature in each step by rapidly cooling at the end of each step while lowering the temperature step by step using a Differential Scanning Calorimeter (DSC). to be.

That is, when polyolefin is completely melted by heating, cooled to a specific temperature (T) and annealed slowly, the lamellae that are not stable at the temperature (T) are still melted and only the stable lamellas are crystallizes At this time, the stability to the temperature (T) depends on the thickness of the lamellae, the thickness of the lamella depends on the chain structure. Therefore, by performing this heat treatment step by step, the thickness of the lamella according to the polymer chain structure and its distribution can be quantitatively measured, and accordingly, the distribution of each melting peak area can be measured.

According to an embodiment of the present invention, the SSA is heated to 120 to 124° C. at the first heating temperature using a differential scanning calorimeter, maintained for 15 to 30 minutes, and then cooled to 28 to 32° C. , the n+1th heating temperature is 3 to 7°C lower than the nth heating temperature, and heating-annealing-quenching is performed until the final heating temperature is 50 to 54°C while gradually lowering the heating temperature. This can be done by repetition.

More specifically, the SSA may be performed in the following steps i) to v):

i) heating the polyolefin to 160° C. using a differential scanning calorimeter and maintaining it for 30 minutes to remove all heat history before measurement;

ii) lowering the temperature from 160° C. to 122° C., maintaining it for 20 minutes, and lowering the temperature to 30° C. and maintaining the temperature for 1 minute;

iii) heating to a temperature of 5°C lower than 122°C to 117°C and then maintaining for 20 minutes, lowering the temperature to 30°C and maintaining the temperature for 1 minute;

iv) The n+1th heating temperature should be 5℃ lower than the nth heating temperature, and the heating rate, holding time, and cooling temperature shall be the same, gradually lowering the heating temperature until the heating temperature reaches 52℃. performing; and

v) finally raising the temperature from 30°C to 160°C

The temperature profile of the SSA analysis method according to an embodiment of the present invention is shown in FIG. 2 .

Referring to FIG. 2 , the polyolefin is initially heated to 160° C. using a differential scanning calorimeter (device name: DSC8000, manufacturer: PerkinElmer) and then maintained for 30 minutes to remove all the thermal history of the sample before measurement. After lowering the temperature from 160°C to 122°C, hold for 20 minutes, lower the temperature to 30°C, hold for 1 minute, and then increase the temperature again.

Next, after heating to a temperature 5°C lower (117°C) than the initial heating temperature of 122°C, the temperature is maintained for 20 minutes, the temperature is lowered to 30°C, maintained for 1 minute, and then the temperature is increased again. In this way, the n+1-th heating temperature is set to a temperature lower than the n-th heating temperature by 5°C, the holding time and the cooling temperature are the same, and the heating temperature is gradually lowered to 52°C. At this time, the rate of rise and fall of the temperature is controlled at 20 °C/min, respectively. Finally, in order to quantitatively analyze the distribution of crystals formed by repeating heating-annealing-quick cooling, the temperature was increased from 30°C to 160°C at a temperature increase rate of 10°C/min, and the change in calorific value was observed and a thermogram was recorded. measure

In this way, when heating-annealing-quicking is repeated in the SSA method for the polyolefin of the present invention and then the temperature is raised, peaks for each temperature appear, and ethylene sequences of different thicknesses are obtained accordingly. (weighted average, L _w ) and arithmetic mean (L _n ) can be found:

[Equation 2]

In Equation 2 above,

[Equation 3]

In Equations 2 and 3 above,

_Si is the area of each melting peak measured in the SSA thermogram,

L _i is the Average Ethylene Sequence Length (ASL) corresponding to each melting peak in the SSA thermogram.

In addition, the ASL was determined from the measured SSA thermogram in Journal of Polymer Science Part B: Polymer Physics. 2002, vol. 40, 813-821, and Journal of the Korean Chemical Society 2011, Vol. 55, No. It can be calculated with reference to 4.

L _w calculated in the same way as above and The ratio of L _n (L _w / L _n ) is the inhomogeneity (I) of the ethylene sequence, and as the value of I increases, it means that the lamellae are non-uniformly distributed in the polymer chain.

The polyolefin according to an embodiment of the present invention may have the non-uniformity (I) of 1.25 or more, or 1.26 or more, or 1.27 or more, and 1.40 or less, or 1.38 or less, or 1.35 or less, or 1.32 or less.

Since the higher the non-uniformity, the better the drop impact strength. Thus, the polyolefin of the present invention has the above-described non-uniformity, thereby exhibiting improved transparency and drop impact strength than the conventional polyolefin having the same range of densities.

Low-density polyolefin can improve drop impact strength, but melt strength is lowered, making it difficult to manufacture a stable blown film. However, according to the polyolefin of the present invention, it is possible to implement an improved drop impact strength compared to a conventional polyolefin product having the same density.

In addition, the polyolefin according to an embodiment of the present invention has a melt index (MI 2.16) measured under a temperature of 190 ° C and a load of 2.16 kg according to ASTM D1238 standard while satisfying the properties as described above (MI _2.16 ) of 0.5 to 1.5 g /10 min. More specifically, the melt index (MI _2.16 ) is 0.5 g/10min or more, or 0.7 g/10min or more, or 0.8 g/10min or more, or 0.9 g/10min or more, and 1.5 g/10min or less, or 1.4 g/ 10 min or less, or 1.3 g/10 min or less.

In addition, the polyolefin according to an embodiment of the present invention is a polyolefin film (BUR 2.3, film thickness 55 to 65 μm) using a film making machine, and then the haze of the film measured according to ISO 13468 is 11% or less. More specifically, the haze of the polyolefin according to an embodiment of the present invention may be 11% or less, or 10.5% or less, or 10% or less. The lower the haze value, the better, so the lower limit is not particularly limited, but may be, for example, 4% or more, or 5% or more, or 6% or more, or 7% or more.

In addition, the polyolefin according to an embodiment of the present invention is a polyolefin film (BUR 2.3, film thickness 55 to 65㎛) using a film making machine, and then the drop impact strength measured according to ASTM D 1709 [Method A] may be 850 g or more, or 900 g or more, or 950 g or more. The higher the drop impact strength, the better, so the upper limit is not particularly limited, but may be, for example, 1,500 g or less, or 1,400 g or less, or 1,300 g or less, or 1,200 g or less.

In addition, the polyolefin according to an embodiment of the present invention may have a weight average molecular weight (Mw) of 70,000 to 140,000 g/mol. More preferably, the weight average molecular weight may be 80,000 g/mol or more, or 90,000 g/mol or more, and 130,000 g/mol or less, or 120,000 g/mol or less.

The weight average molecular weight (Mw) is measured using gel permeation chromatography (GPC), means a universal calibration value using a polystyrene standard, and may be appropriately adjusted in consideration of the use or application field of the polyolefin.

On the other hand, the polyolefin according to an embodiment of the present invention having the above physical properties can be prepared by a manufacturing method comprising the step of polymerizing an olefin monomer in the presence of a hybrid supported metallocene compound as a catalytically active component. .

More specifically, the polyolefin of the present invention may include, but is not limited to, at least one first metallocene compound selected from compounds represented by the following Chemical Formula 1; at least one second metallocene compound selected from compounds represented by the following formula (2); and a carrier supporting the first and second metallocene compounds, and may be prepared by polymerizing an olefin monomer in the presence of a hybrid supported metallocene catalyst.

[Formula 1]

In Formula 1,

Q ₁ and Q ₂ are the same as or different from each other and are each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkoxyalkyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group;

T ₁ is carbon, silicon, or germanium;

M ₁ is a Group 4 transition metal;

X ₁ and X ₂ are the same as or different from each other, and each independently a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, 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;

R ₁ to R ₁₄ are the same as or different from each other, and each independently hydrogen, halogen, C1 to C20 alkyl group, C1 to C20 haloalkyl group, C2 to C20 alkenyl group, C1 to C20 alkylsilyl group, C1 to C20 of a silylalkyl group, a C1 to C20 alkoxysilyl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, or among R ₁ to R ₁₄ two or more adjacent to each other are connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring;

[Formula 2]

In Formula 2,

Q ₃ and Q ₄ are the same as or different from each other, and are each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkoxyalkyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group;

T ₂ is carbon, silicon, or germanium;

M ₂ is a Group 4 transition metal;

X ₃ and X ₄ are the same as or different from each other, and each independently a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, 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;

R ₁₅ to R ₂₈ are the same as or different from each other, and each independently represents hydrogen, halogen, C1 to C20 alkyl group, C1 to C20 haloalkyl group, C2 to C20 alkenyl group, C2 to C20 alkoxyalkyl group, C1 to C20 an alkylsilyl group, a C1 to C20 silylalkyl group, a C1 to C20 alkoxysilyl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, However, R ₂₀ and R ₂₄ are the same as or different from each other, and each independently a C1 to C20 alkyl group, or two or more adjacent to each other among R ₁₅ to R ₂₈ are connected to each other and a substituted or unsubstituted aliphatic or aromatic ring is to form

In the hybrid supported metallocene catalyst, the substituents of Chemical Formulas 1 and 2 will be described in more detail as follows.

The C1 to C20 alkyl group includes a straight-chain or branched alkyl group, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group, but is not limited thereto.

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

The C6 to C20 aryl group includes a monocyclic or condensed aryl group, and specifically includes, but is not limited to, a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, a fluorenyl group, and the like.

The C1 to C20 alkoxy group may include, but is not limited to, a methoxy group, an ethoxy group, a phenyloxy group, and a cyclohexyloxy group.

The C2 to C20 alkoxyalkyl group is a functional group in which one or more hydrogens of the alkyl group as described above are substituted with an alkoxy group, specifically, a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an iso-propoxymethyl group, an iso-propoxy group alkoxyalkyl groups such as an ethyl group, iso-propoxyhexyl group, tert-butoxymethyl group, tert-butoxyethyl group, and tert-butoxyhexyl group; or an aryloxyalkyl group such as a phenoxyhexyl group, but is not limited thereto.

The C1 to C20 alkylsilyl group or C1 to C20 alkoxysilyl group is a functional group in which 1 to 3 hydrogens of -SiH ₃ are substituted with 1 to 3 alkyl groups or alkoxy groups as described above, specifically methylsilyl group, di alkylsilyl groups such as methylsilyl group, trimethylsilyl group, dimethylethylsilyl group, diethylmethylsilyl group or dimethylpropylsilyl group; Alkoxysilyl groups, such as a methoxysilyl group, a dimethoxysilyl group, a trimethoxysilyl group, or a dimethoxyethoxysilyl group; An alkoxyalkylsilyl group such as a methoxydimethylsilyl group, a diethoxymethylsilyl group, or a dimethoxypropylsilyl group may be mentioned, but is not limited thereto.

The C1 to C20 silylalkyl group is a functional group in which one or more hydrogens of the alkyl group as described above are substituted with a silyl group, specifically -CH ₂ -SiH ₃ , a methylsilylmethyl group, or a dimethylethoxysilylpropyl group. , but is not limited thereto.

The halogen may be fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

The sulfonate group has a structure of -O-SO ₂ -R ^' , and R ^' may be a C1 to C20 alkyl group. Specifically, the C1 to C20 sulfonate group may include, but is not limited to, a methanesulfonate group or a phenylsulfonate group.

In addition, in the present specification, that two substituents adjacent to each other are connected to each other to form an aliphatic or aromatic ring means that the atom(s) of the two substituents and the valence (atoms) to which the two substituents are bonded are connected to each other to form a ring means that Specifically, examples in which R _a and R _b or R _a' and R _{b '} of -NR _a R _b or -NR _a' R _{b '} are linked to each other to form an aliphatic ring include, for example, a piperidinyl group. and R _a and R _b or R _a' and R _{b '} of -NR _a R _b or -NR _a' R _{b '} are linked to each other to form an aromatic ring, for example, a pyrrolyl group can be exemplified.

The above-mentioned substituents are optionally a hydroxyl group within the range of exhibiting the same or similar effect as the desired effect; halogen; an alkyl group, an alkenyl group, an aryl group, an alkoxy group; an alkyl group or an alkenyl group, an aryl group, an alkoxy group containing at least one hetero atom among the heteroatoms of Groups 14 to 16; silyl group; an alkylsilyl group or an alkoxysilyl group; phosphine group; phosphide group; sulfonate group; And it may be substituted with one or more substituents selected from the group consisting of a sulfone group.

Examples of the Group 4 transition metal include, but are not limited to, titanium (Ti), zirconium (Zr), and hafnium (Hf).

When the hybrid supported catalyst is used, it is possible to maintain the transparency of the polyolefin and secure excellent drop impact strength due to the non-uniformity of the lamellar distribution, so that a polyolefin excellent in high processability, particularly melt blown processability, can be manufactured.

Specifically, in the hybrid supported catalyst according to an embodiment of the present invention, the first metallocene compound includes a long chain branch and is easy to prepare a low molecular weight polyolefin, and the second metallocene compound includes the first metal It contains a small amount of long-chain branching compared to the rosene compound and is easy to prepare polyolefins having a relatively high molecular weight. In particular, when there are many long chain branches in the polymer and the molecular weight is high, the melt strength is increased. In the case of the first metallocene compound, there are many long chain branches in the polymer, but the molecular weight is low, so there is a limit in improving bubble stability.

In the present invention, a first metallocene compound containing a relatively large number of long chain branches and producing a low molecular weight polymer and a second metallocene compound producing a polymer having relatively many short chain branches and a high molecular weight are hybridized to support excellent transparency. while maintaining the melt strength was improved. Since the long-chain branch existing in the polymer is located on the relatively low molecular weight side by hybrid supporting the two types of metallocene compounds, transparency is not deteriorated.

In particular, the hybrid supported catalyst of the present invention is characterized in that the long-chain branch generated by the first metallocene compound of Formula 1 and the long-chain branch generated by the second metallocene compound of Formula 2 are entangled with each other at the molecular level. have Because of the entanglement between the long chain branches, a large force is required to be released from the molten state, thereby enhancing the melt strength. When the homopolymer by each catalyst is melted and mixed (melt blending), the improvement of the melt strength does not appear, so it can be seen that the improvement of the melt strength is effective when entanglement occurs from the polymerization stage by the hybrid supported catalyst.

More specifically, in the supported hybrid catalyst according to an embodiment of the present invention, the first metallocene compound represented by Formula 1 is a different ligand, and the metallocene compound is a cyclopentadienyl ligand and tetrahydroindenyl. It includes a ligand, wherein the ligands are cross-linked by -Si(Q ₁ )(Q ₂ )-, and M ₁ (X ₁ )(X ₂ ) has a structure in which M 1 (X 1 )(X 2 ) exists between the ligands. Polymerization of a catalyst having such a structure can obtain a polymer having a small amount of long-chain branching and a relatively narrow molecular weight distribution (PDI, MWD, Mw/Mn) and melt flow rate ratio (MFRR).

Specifically, the cyclopentadienyl ligand in the structure of the metallocene compound represented by Formula 1 may affect, for example, olefin polymerization activity.

In particular, when R ₁₁ to R ₁₄ of the cyclopentadienyl ligand are each independently any one of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, and a C2 to C20 alkenyl group, the metallocene of Formula 1 The catalyst obtained from the compound may exhibit higher activity in the olefin polymerization process, and when R ₁₁ to R ₁₄ are each independently any one of a methyl group, an ethyl group, a propyl group, and a butyl group, the hybrid supported catalyst is the polymerization of an olefin monomer. It can exhibit very high activity in the process.

In addition, by having an unshared electron pair that can act as a Lewis base in the structure of the tetrahydroindenyl ligand in the structure of the metallocene compound represented by Formula 1, it is stable and can exhibit high polymerization activity, and is tetrahydro The nyl ligand can easily control the molecular weight of the prepared polyolefin by, for example, controlling the degree of steric hindrance effect according to the type of the substituted functional group.

Specifically, in Formula 1, R ₁ may be any one of hydrogen, a C1 to C20 alkyl group, a C1 to C20 alkoxy group, and a C2 to C20 alkenyl group. More specifically, in Formula 1, R ₁ may be hydrogen or a C1 to C20 alkyl group, and R ₂ to R ₁₀ may each be hydrogen. In this case, the supported hybrid catalyst may provide a polyolefin having excellent processability.

In addition, in the structure of the metallocene compound represented by Formula 1, the cyclopentadienyl ligand and the tetrahydroindenyl ligand are crosslinked by -Si(Q ₁ )(Q ₂ )- to exhibit excellent stability. have. In order to ensure this effect more effectively, Q ₁ and Q ₂ may each independently be any one of a C1 to C20 alkyl group or a C6 to C20 aryl group. More specifically, a metallocene compound in which Q ₁ and Q ₂ are each independently any one of a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a t-butyl group, a phenyl group, and a benzyl group can be used

M ₁ (X ₁ )(X ₂ ) present between the cyclopentadienyl ligand and the tetrahydroindenyl ligand in the structure of the metallocene compound represented by Formula 1 affects the storage stability of the metal complex. can go crazy In order to ensure this effect more effectively, X ₁ and X ₂ may each independently be any one of a halogen, a C1 to C20 alkyl group, and a C1 to C20 alkoxy group. More specifically, X ₁ and X ₂ may each independently be F, Cl, Br or I, and M ₁ is Ti, Zr or Hf; Zr or Hf; or Zr.

As an example, as a first metallocene compound capable of providing a polyolefin having an increased drop impact strength and a large short-chain branching content and having excellent blown film processability, the metallocene compound of Formula 1 has the following structural formulas It may be a compound represented by, but is not limited thereto.

,

,

,

,

,

,

,

,

,

,

,

,

,

,

The first metallocene compound represented by Formula 1 may be synthesized by applying known reactions. Specifically, the tetrahydroindenyl derivative and the cyclopentadiene derivative are connected with a bridge compound to prepare a ligand compound, and then a metal precursor compound is added to perform metallation, but is not limited thereto. , For more detailed synthesis methods, refer to Examples.

On the other hand, in the hybrid supported catalyst according to an embodiment of the present invention, the metallocene compound represented by Formula 2 is a different ligand and has a cyclopentadienyl ligand and a substituent (R ₂₀ and R ₂₄ ) at specific positions. including an indenyl ligand, wherein the different ligands are crosslinked by -Si(Q ₃ )(Q ₄ )-, and M ₂ (X ₃ )(X ₄ ) exists between the different ligands. have When a metallocene compound having such a specific structure is activated by an appropriate method and used as a catalyst for the polymerization of olefins, it is possible to generate long-chain branches. As described above, by introducing a substituent (R ₂₀ and R ₂₄ ) at a specific position of the indene derivative of Formula 2, the polymerization activity is higher than that of an unsubstituted indene compound or a metallocene compound containing an indene compound substituted at another position. It can have high characteristics.

In particular, in the case of the second metallocene compound represented by Formula 2, it has a molecular weight of about 150,000 to 550,000 during homopolymerization and has a characteristic of having an SCB. There are properties that can be improved.

Specifically, the cyclopentadienyl ligand in the structure of the metallocene compound represented by Formula 2 may affect, for example, olefin polymerization activity.

In particular, R ₂₅ to R ₂₈ of the cyclopentadienyl ligand are each independently hydrogen, a C1 to C20 alkyl group, a C2 to C20 alkoxyalkyl group, or a C6 to C20 aryl group. The catalyst obtained from the metallocene compound may exhibit higher activity in the olefin polymerization process, R ₂₅ and R ₂₈ are each hydrogen, R ₂₆ and R ₂₇ are each independently hydrogen, a C1 to C20 alkyl group, or C2 to In the case of a C20 alkoxyalkyl group, the hybrid supported catalyst may exhibit very high activity in the polymerization process of the olefin monomer.

In addition, in the structure of the metallocene compound represented by Chemical Formula 2, the indenyl ligand can easily control the molecular weight of the produced polyolefin by, for example, controlling the degree of steric hindrance effect according to the type of the substituted functional group. have.

Specifically, a phenyl group is substituted at the 4th position of the indenyl group, R ₂₀ serving as the para position of the phenyl group may be a C1 to C20 alkyl group, and a substituent R ₂₄ or C1 at the 6th position of the indenyl group It is preferable from the viewpoint of increasing the molecular weight to have a C20 alkyl group. In particular, R ₂₀ and R ₂₄ may each independently be a C1 to C4 alkyl group, R ₂₀ may be preferably a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, etc., and R ₂₄ is preferably may be a t-butyl group. In this case, the supported hybrid catalyst may provide a polyolefin having excellent copolymerizability.

The remaining substituents R ₁₅ to R ₁₉ and R ₂₁ to R ₂₃ of the indenyl group are each independently hydrogen, halogen, C1 to C20 alkyl group, C1 to C20 haloalkyl group, C2 to C20 alkenyl group, C2 to C20 alkoxy Alkyl group, C1 to C20 alkylsilyl group, C1 to C20 silylalkyl group, C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to It may be a C20 arylalkyl group.

In addition, in the structure of the metallocene compound represented by Formula 2, the cyclopentadienyl ligand and the indenyl ligand are cross-linked by -Si(Q ₃ )(Q ₄ )- to exhibit excellent stability. In order to ensure this effect more effectively, Q ₃ and Q ₄ may each independently be any one of a C1 to C20 alkyl group or a C2 to C20 alkoxyalkyl group. More specifically, Q ₃ and Q ₄ are each independently a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, t-butyl group, methoxymethyl group, methoxyethyl group, ethoxymethyl group, iso -propoxymethyl group, iso- propoxyethyl group, iso- propoxy hexyl group, tert- butoxymethyl group, tert- butoxyethyl group, tert- butoxy hexyl any one of the metallocene compound can be used.

In particular, in the metallocene compound represented by Formula 2, at least one of a substituent of cyclopentadiene (Cp) or a -Si(Q ₃ )(Q ₄ )-silyl group may be a C2 to C20 alkoxyalkyl group, and , iso-propoxyethyl group, iso-propoxyhexyl group, tert-butoxyethyl group, tert-butoxyhexyl group and the like are more preferable.

This may affect the copolymerizability of the C2 to C20 alkoxyalkyl group of an alpha olefin comonomer such as 1-butene or 1-hexene, wherein the alkoxyalkyl group has C4 or less This is because, in the case of having a short alkyl group chain, the degree of copolymerization can be controlled without deterioration of other physical properties because the copolymerization (comonomer incorporation) of the alpha olefin comonomer is lowered while maintaining the overall polymerization activity.

In addition, in the structure of the metallocene compound represented by Formula 2, M ₂ (X ₃ )(X ₄ ) present between the cyclopentadienyl ligand and the tetrahydroindenyl ligand is dependent on the storage stability of the metal complex. can affect In order to ensure this effect more effectively, X ₃ and X ₄ may each independently be any one of a halogen, a C1 to C20 alkyl group, and a C1 to C20 alkoxy group. More specifically, X ₃ and X ₄ may each independently be F, Cl, Br or I, and M ₂ is Ti, Zr or Hf; Zr or Hf; or Zr.

Meanwhile, specific examples of the second metallocene compound represented by Formula 2 may include compounds represented by the following structural formulas, but the present invention is not limited thereto.

,

,

,

,

As such, the hybrid supported metallocene catalyst of the embodiment includes the first and second metallocene compounds, and thus a polyolefin having excellent processability and excellent physical properties, in particular, drop impact strength, and the like can be prepared.

In particular, the mixing molar ratio of the first metallocene compound and the second metallocene compound is about 1:1 to 10:1, preferably about 1.2:1 to 7.5:1, and more preferably 1.5: 1 to 7.0:1 or 1.8:1 to 6.5:1. The mixing molar ratio of the first metallocene compound and the second metallocene compound may be 1:1 or more in terms of physical property control in order to satisfy both physical properties and processability by controlling the molecular weight and the amounts of SCB and LCB, In terms of securing processability, it may be 10:1 or less.

Meanwhile, the first and second metallocene compounds may have the above-described structural characteristics and may be stably supported on a carrier.

As the carrier, a carrier containing a hydroxyl group or a siloxane group on the surface may be used. Specifically, as the carrier, a carrier containing a hydroxyl group or a siloxane group having high reactivity by drying at a high temperature to remove moisture from the surface may be used. More specifically, silica, alumina, magnesia, or a mixture thereof may be used as the carrier, and among these, silica may be more preferable. The carrier may be dried at high temperature, for example, silica, silica-alumina, and silica-magnesia dried at high temperature may be used, and these are typically Na ₂ O, K ₂ CO ₃ , BaSO ₄ and Mg ( NO ₃ ) ₂ and the like may include oxides, carbonates, sulfates, and nitrates.

The drying temperature of the carrier is preferably about 200 to 800 °C, more preferably about 300 to 600 °C, and most preferably about 300 to 400 °C. When the drying temperature of the carrier is less than about 200 ℃, there is too much moisture and the surface moisture and the cocatalyst react. Since many groups disappear and only siloxane remains, the reaction site with the co-catalyst decreases, which is not preferable.

The amount of hydroxyl groups on the surface of the carrier is preferably about 0.1 to 10 mmol/g, more preferably about 0.5 to 5 mmol/g. The amount of hydroxyl groups on the surface of the carrier can be controlled by the method and conditions or drying conditions of the carrier, such as temperature, time, vacuum or spray drying, and the like.

If the amount of the hydroxyl group is less than about 0.1 mmol/g, there are few reaction sites with the co-catalyst, and if it exceeds about 10 mmol/g, there is a possibility that it is due to moisture other than the hydroxyl group present on the surface of the carrier particle. Not desirable.

In addition, in the hybrid supported metallocene catalyst of the embodiment, the cocatalyst supported together on the support to activate the metallocene compound is an organometallic compound containing a Group 13 metal, and under a general metallocene catalyst. It is not particularly limited as long as it can be used when polymerizing the olefin.

Specifically, the co-catalyst compound may include at least one of an aluminum-containing first co-catalyst of the following Chemical Formula 3 and a borate-based second co-catalyst of the following Chemical Formula 4.

[Formula 3]

R _a -[Al(R _b )-O] _n -R _c

In Formula 3,

R _a , R _b , and R _c are the same as or different from each other and each independently represent hydrogen, halogen, a C1 to C20 hydrocarbyl group, or a halogen substituted C1 to C20 hydrocarbyl group;

n is an integer greater than or equal to 2;

[Formula 4]

T ⁺ [BG ₄ ] ^-

In Formula 4, T ⁺ is a +1 valent polyatomic ion, B is boron in +3 oxidation state, and G is each independently a hydride group, a dialkylamido group, a halide group, an alkoxide group, an aryloxide group, or a hydro selected from the group consisting of a carbyl group, a halocarbyl group and a halo-substituted hydrocarbyl group, wherein G has no more than 20 carbons, but in no more than one position, G is a halide group.

The first cocatalyst of Chemical Formula 3 may be an alkylaluminoxane-based compound to which repeating units are bound in a linear, circular or network form, and specific examples of the first cocatalyst include methylaluminoxane (MAO), ethylalumin and oxane, isobutyl aluminoxane, or butyl aluminoxane.

In addition, the second cocatalyst of Formula 4 may be a borate compound in the form of a trisubstituted ammonium salt, a dialkyl ammonium salt, or a trisubstituted phosphonium salt. Specific examples of the second cocatalyst include trimetalammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, and tri(n-butyl)ammonium tetraphenylborate. , methyltetradecyclooctadecylammonium tetraphenylborate, N,N-dimethylaninium tetraphenylborate, N,N-diethylaninium tetraphenylborate, N,N-dimethyl (2,4,6-trimethylanilium ) tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl)borate, methylditetradecylammonium tetrakis(pentaphenyl)borate, methyldioctadecylammonium tetrakis(pentafluorophenyl)borate, triethylammonium, tetra Kis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammonium tetrakis (Pentafluorophenyl)borate, N,N-dimethylaninium tetrakis(pentafluorophenyl)borate, N,N-diethylaniliumtetrakis(pentafluorophenyl)borate, N,N-dimethyl (2 ,4,6-trimethylanilium)tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, triethylammonium tetrakis(2,3,4 ,6-tetrafluorophenyl)borate, tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(2,3,4,6-, Tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N,N-dimethylaninium tetrakis (2,3,4,6- Tetrafluorophenyl)borate, N,N-diethylaninium tetrakis(2,3,4,6-tetrafluorophenyl)borate or N,N-dimethyl-(2,4,6-trimethylaninium) borate compounds in the form of trisubstituted ammonium salts such as tetrakis-(2,3,4,6-tetrafluorophenyl)borate; Borates in the form of dialkylammonium salts such as dioctadecylammonium tetrakis(pentafluorophenyl)borate, ditetradecylammonium tetrakis(pentafluorophenyl)borate, or dicyclohexylammonium tetrakis(pentafluorophenyl)borate compound; or triphenylphosphonium tetrakis(pentafluorophenyl)borate, methyldioctadecylphosphonium tetrakis(pentafluorophenyl)borate or tri(2,6-, dimethylphenyl)phosphonium tetrakis(pentafluorophenyl ) borate compounds in the form of trisubstituted phosphonium salts such as borate.

In the hybrid supported metallocene catalyst of the embodiment, a mass ratio of the total transition metals to the carrier included in the first metallocene compound and the second metallocene compound may be 1:10 to 1:1000. When the carrier and the metallocene compound are included in the above mass ratio, an optimal shape may be exhibited.

In addition, the mass ratio of the promoter compound to the carrier may be 1:1 to 1:100. When the cocatalyst and the carrier are included in the above mass ratio, the activity and the microstructure of the polymer can be optimized.

The hybrid supported metallocene catalyst of one embodiment may be used for polymerization of olefinic monomers as such. In addition, the hybrid supported metallocene catalyst may be prepared and used as a catalyst prepolymerized by catalytic reaction with an olefinic monomer. It can also be used by preparing a catalyst prepolymerized by contacting it with a system monomer.

On the other hand, the hybrid supported metallocene catalyst of the embodiment includes the steps of supporting a cocatalyst on a support; supporting the first and second metallocene compounds on the support on which the promoter is supported; It can be prepared by a manufacturing method comprising a.

At this time, the first and second metallocene compounds may be supported one by one sequentially, or two types may be supported together. At this time, there is no limitation in the order of loading, but the shape of the hybrid supported metallocene catalyst can be improved by first loading the second metallocene catalyst having a relatively poor morphology, and thus the second metal After the strong catalyst is supported, the first metallocene catalyst may be sequentially supported.

In the above method, the supporting conditions are not particularly limited and may be performed within a range well known to those skilled in the art. For example, it can proceed by appropriately using high-temperature loading and low-temperature loading, for example, the loading temperature is possible in the range of about -30 ℃ to 150 ℃, preferably room temperature (about 25 ℃) to about 100 ℃ , more preferably from room temperature to about 80 °C. The loading time may be appropriately adjusted according to the amount of the metallocene compound to be supported. The reacted supported catalyst may be used as it is by filtering or removing the reaction solvent by distillation under reduced pressure, and if necessary, it may be used after Soxhlet filter with an aromatic hydrocarbon such as toluene.

In addition, the preparation of the supported catalyst may be carried out in the presence of a solvent or non-solvent. When a solvent is used, the usable solvent includes an aliphatic hydrocarbon solvent such as hexane or pentane, an aromatic hydrocarbon solvent such as toluene or benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, an ether-based solvent such as diethyl ether or THF Most organic solvents, such as a solvent, acetone, ethyl acetate, are mentioned, and hexane, heptane, toluene, or dichloromethane is preferable.

Meanwhile, according to another embodiment of the present invention, there may be provided a method for producing a polyolefin comprising the step of polymerizing an olefin monomer in the presence of the hybrid supported metallocene catalyst.

And, the olefin monomer is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dode cene, 1-tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbornadiene, ethylidene noboden, phenyl noboden, vinyl norboden, dicyclopentadiene, 1,4-butadiene, 1, It may be at least one selected from the group consisting of 5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.

For the polymerization reaction of the olefin monomer, various polymerization processes known as polymerization of the olefin monomer, such as a continuous solution polymerization process, a bulk polymerization process, a suspension polymerization process, a slurry polymerization process, or an emulsion polymerization process, may be employed. This polymerization reaction may be carried out at a temperature of about 25 to 500 °C, or about 25 to 200 °C, or about 50 to 150 °C, and a pressure of about 1 to 100 bar or about 10 to 80 bar.

In addition, in the polymerization reaction, the hybrid supported metallocene catalyst may be used in a dissolved or diluted state in a solvent such as pentane, hexane, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene, and the like. In this case, by treating the solvent with a small amount of alkylaluminum or the like, a small amount of water or air that may adversely affect the catalyst may be removed in advance.

In addition, the polyolefin prepared by the above method may exhibit high drop impact strength with low density and excellent transparency.

Specifically, the polyolefin has a density of 0.915 g/cm ³ to 0.930 g/cm ³ , and may have an inhomogeneity (I) of 1.25 to 1.40 of an ethylene sequence during SSA (Successive Self-nucleation and Annealing) analysis.

In addition, the polyolefin may have a melt index (MI _2.16 ) of 0.5 to 1.5 g/10min measured at a temperature of 190° C. and a load of 2.16 kg according to ASTM D1238 standard.

In addition, the polyolefin may have a haze of 11% or less, measured according to ISO 13468, after manufacturing a polyolefin film (BUR 2.3, film thickness 55 to 65 μm) using a film making machine.

In addition, the polyolefin may have a drop impact strength measured according to ASTM D 1709 [Method A] of 850 g or more after manufacturing a polyolefin film (BUR 2.3, film thickness 55 to 65 μm) using a film making machine.

In addition, when the above polyolefin is, for example, an ethylene-alpha olefin copolymer, preferably a copolymer of ethylene and 1-butene or an ethylene-1-hexene copolymer, the above-described physical properties can be more appropriately satisfied. .

Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are only provided for easier understanding of the present invention, and the content of the present invention is not limited thereto.

<Example>

<Synthesis example of metallocene compound>

Synthesis Example 1: First metallocene compound

1-1 Preparation of Ligand Compounds

Tetramethylcyclopentadiene (TMCP) was filtered after lithiation with n-BuLi (1 equivalent) in THF (0.4 M) and used as tetramethylcyclopentyl-Li salts (TMCP-Li salts). Indene was lithiated with Hexane (0.5 M) n-BuLi (1 equivalent), filtered, and used as Ind-Li salts. In a 250 mL Schlenk flask, 50 mmol of tetramethylcyclopentyl-Li salts (TMCP-Li salts) and about 100 mL of tetrahydrofuran (THF) were placed under Ar. 1 equivalent of dichloromethyl-(iso-propyl) silane was added at -20 °C. After about 6 hours, 3 mol% of CuCN and Ind-Li salts (50 mmol, MTBE 1M solution) were added at -20°C and reacted for about 12 hours. The organic layer was separated with water and hexane to obtain a ligand.

1-2 Preparation of metallocene compounds

In a dried 250 mL Schlenk flask, 50 mmol of the ligand compound synthesized in 1-1 was dissolved in 100 mL of MTBE under Ar, and 2 equivalents of n-BuLi was added dropwise at -20 °C. After about 16 hours of reaction, a ligand-Li solution was added to ZrCl ₄ (THF) ₂ (50 mmol, MTBE 1 M solution). After the reaction for about 16 hours, the solvent was removed, dissolved in methylene chloride (MC), and filtered to remove LiCl. After removing the solvent of filtrate, about 50 mL of MTBE and about 100 mL of hexane were added, stirred for about 2 hours, and filtered to obtain a solid metallocene catalyst precursor.

The metallocene catalyst precursor (20 mmol) obtained above, DCM 60 mL, and Pd/C catalyst 5 mol% were added to a high-pressure stainless steel (sus) reactor under an argon atmosphere. Argon in the high-pressure reactor was replaced with hydrogen three times, and hydrogen was filled to a pressure of about 20 bar. The reaction was completed after stirring at 35 °C for 24 hours. After replacing the inside with argon, the DCM solution was transferred to a schlenk flask under an argon atmosphere. The solution was passed through celite under argon to remove the Pd/C catalyst, and the solvent was dried to obtain a solid catalyst precursor.

¹ H NMR (500 MHz, C6D6): 0.62 (3H, s), 0.98 (3H, d), 1.02 (3H, d), 1.16 (2H, dd), 1.32-1.39 (3H, m), 1.78 (3H) , s), 1.81 (3H, s), 1.84-1.94 (3H, m), 2.01 (3H, s), 2.03 (1H, m), 2.04 (3H, s), 2.35 (2H, m), 2.49- 2.55 (1H, m), 3.13-3.19 (1H, m), 5.27 (1H, d), 6.75 (1H, d).

Synthesis Example 2: First metallocene compound

2-1 Preparation of Ligand Compounds

Tetramethylcyclopentadiene (TMCP) was filtered after lithiation with n-BuLi (1 equivalent) in THF (0.4 M) and used as tetramethylcyclopentyl-Li salts (TMCP-Li salts). Indene was lithiated with Hexane (0.5 M) n-BuLi (1 equivalent), filtered, and used as Ind-Li salts. In a 250 mL Schlenk flask, 50 mmol of tetramethylcyclopentyl-Li salts (TMCP-Li salts) and 100 mL of tetrahydrofuran (THF) were placed under Ar. At -20 °C, 1 equivalent of dichloromethylphenyl silane was added. After about 6 hours, 3 mol% of CuCN and Ind-Li salts (50 mmol, MTBE 1M solution) were added at -20°C and reacted for about 12 hours. The organic layer was separated with water and hexane to obtain a ligand.

2-2 Preparation of metallocene compound

In a dried 250 mL Schlenk flask, 50 mmol of the ligand compound synthesized in 2-1 was dissolved in about 100 mL of MTBE under Ar, and 2 equivalents of n-BuLi were added dropwise at -20 °C. After about 16 hours of reaction, a ligand-Li solution was added to ZrCl ₄ (THF) ₂ (50 mmol, MTBE 1 M solution). After the reaction for about 16 hours, the solvent was removed, dissolved in methylene chloride (MC), and filtered to remove LiCl. After removing the solvent of filtrate, about 50 mL of MTBE and about 100 mL of hexane were added, stirred for about 2 hours, and filtered to obtain a solid metallocene catalyst precursor.

The metallocene catalyst precursor (20 mmol) obtained above, DCM 60 mL, and Pd/C catalyst 5 mol% were added to a high-pressure stainless steel (sus) reactor under an argon atmosphere. Argon in the high-pressure reactor was replaced with hydrogen three times, and hydrogen was filled to a pressure of about 20 bar. The reaction was completed after stirring at about 35 °C for about 24 hours. After replacing the inside with argon, the DCM solution was transferred to a schlenk flask under an argon atmosphere. The solution was passed through celite under argon to remove the Pd/C catalyst, and the solvent was dried to obtain metallocene compounds (A, B forms) having different stereoisomers in a ratio of 1.3:1.

¹ H NMR (500 MHz, CDCl ₃ ):

Form A: 0.88 (3H, s), 1.43-1.50 (1H, m), 1.52-1.57 (1H, m), 1.60 (3H, s), 1.62-1.68 (1H, m), 1.87-1.95 (1H, m), 1.95-2.00 (1H, m), 2.00 (3H, s), 2.06 (3H, s), 2.08 (3H, s), 2.41-2.47 (1H, m), 2.72-2.78 (1H, m) , 3.04-3.10 (1H, m), 5.62 (1H, d), 6.73 (1H, d), 7.49 (3H, m), 7.87 (2H, m)

Form B: 0.99 (3H, s), 1.42 (3H, s), 1.60-1.67 (2H, m), 1.90-1.98 (1H, m), 1.95 (3H, s), 2.06 (3H, s), 2.06 -2.10 (1H, m), 2.11 (3H, s), 2.44-2.49 (1H, m), 2.66-2.70 (1H, m), 2.74-2.79 (1H, m), 3.02-3.11 (1H, m) , 5.53 (1H, d), 6.74 (1H, d), 7.48 (3H, m), 7.88 (2H, m).

Synthesis Example 3: First metallocene compound

3-1 Preparation of Ligand Compound

After dissolving tetramethylcyclopentadiene (TMCP, 6.0 mL, 40 mmol) in THF (60 mL) in a dried 250 mL schlenk flask, the solution was cooled to -78 °C. Then, n-BuLi (2.5M, 17mL, 42mmol) was slowly added dropwise to the solution, and the resulting solution was stirred at room temperature overnight.

Meanwhile, in a separate 250mL schlenk flask, dichlorodimethylsilane (4.8mL, 40mmol) was dissolved in n-hexane, and the solution was cooled to -78°C. Then, the previously prepared TMCP-lithiation solution was slowly injected into this solution. And the resulting solution was stirred at room temperature overnight.

Thereafter, the resulting solution was depressurized to remove the solvent from the solution. Then, the obtained solid was dissolved in toluene and filtered to remove the remaining LiCl to obtain an intermediate (yellow liquid, 7.0 g, 33 mmol, 83% yield).

¹ H NMR (500 MHz, CDCl ₃ ): 0.24 (6H, s), 1.82 (6H, s), 1.98 (6H, s), 3.08 (1H, s).

Indene (0.93 mL, 8.0 mmol) was dissolved in THF (30 mL) in a dried 250 mL schlenk flask, and the solution was cooled to -78 °C. Then, n-BuLi (2.5M, 3.4mL, 8.4mmol) was slowly added dropwise to the solution, and the resulting solution was stirred at room temperature for about 5 hours.

Meanwhile, in a separate 250mL schlenk flask, the previously synthesized intermediate (1.7g, 8.0mmol) was dissolved in THF, and the solution was cooled to -78°C. Then, the previously prepared indene-lithiation solution was slowly injected into this solution. Then, the resulting solution was stirred at room temperature overnight to obtain a purple solution.

Thereafter, the reaction was terminated by pouring water into the reactor (quenching), and the organic layer was extracted with ether from the mixture. It was confirmed through ¹ H NMR that the organic layer contained dimethyl (indenyl) (tetramethylcyclopentadienyl) silane and other organic compounds. The organic layer was concentrated without purification and used as it was for metallation.

3-2 Preparation of metallocene compound

Dimethyl (indenyl) (tetramethylcyclopentadienyl) silane (1.7 g, 5.7 mmol) synthesized previously in a 250 mL schlenk flask was dissolved in toluene (30 mL) and MTBE (3.0 mL). Then, the solution was cooled to -78°C, n-BuLi (2.5M, 4.8 mL, 12 mmol) was slowly added dropwise to the solution, and the resulting solution was stirred at room temperature overnight. However, a yellow solid was generated in the solution and was not uniformly stirred, so MTBE (50 mL) and THF (38 mL) were additionally added.

On the other hand, after dispersing ZrCl ₄ (THF) ₂ in toluene in a 250mL schlenk flask prepared separately, the resulting mixture was cooled to -78°C. Then, the previously prepared lithiation ligand solution was slowly injected into the mixture. Then, the resulting mixture was stirred overnight.

Thereafter, the reaction product was filtered to obtain a yellow solid (1.3 g, including LiCl (0.48 g), 1.8 mmol). After removing the solvent from the filtrate, it was washed with n-hexane to add a yellow solid (320 mg, 0.70 mmol) obtained (total 44% yield).

¹ H NMR (500 MHz, CDCl ₃ ): 0.96 (3H, s), 1.16 (3H, s), 1.91 (3H, s), 1.93 (3H, s), 1.96 (3H, s), 1.97 (3H, s), 5.98 (1H, d), 7.07 (1H, t), 7.23 (1H, d), 7.35 (1H, t), 7.49 (1H, d), 7.70 (1H, d).

Dimethylsilylene (tetramethylcyclopentadienyl) (indenyl) zirconium dichloride (1.049 g, 2.3 mmol) synthesized earlier was placed in a mini bombe in a glove box. Then, add platinum oxide (52.4mg, 0.231mmol) to the mini bombe, assemble the mini bombe, put anhydrous THF (30mL) in the mini bombe using a canuula, and hydrogen to a pressure of about 30 bar filled Then, the mixture contained in the mini bombe was stirred at about 60° C. for about 1 day, the temperature of the mini bombe was cooled to room temperature, and hydrogen was replaced with argon while gradually lowering the pressure of the mini bombe.

Meanwhile, celite dried in an oven at about 120° C. for about 2 hours was laid on a schlenk filter, and the reaction product of the mini bombe was filtered under argon using this. The PtO ₂ catalyst was removed from the reaction product by the celite. Then, the catalyst was removed from the reaction product under reduced pressure to remove the solvent to obtain a product as a pale yellow solid (0.601 g, 1.31 mmol, Mw: 458.65 g/mol).

¹ H NMR (500 MHz, CDCl ₃ ): 0.82 (3H, s), 0.88 (3H, s), 1.92 (6H, s), 1.99 (3H, s), 2.05 (3H, s), 2.34 (2H, m), 2.54 (2H, m), 2.68 (2H, m), 3.03 (2H, m), 5.45 (1H, s), 6.67 (1H, s).

Synthesis Example 4: Second metallocene compound

4-1 Preparation of Ligand Compounds

11.618 g (40 mmol) of 4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-indene was added to a dried 250 mL schlenk flask, and 100 mL of THF was injected under argon. After the diethylether solution was cooled to 0 °C, 18.4 mL (46 mmol) of 2.5 M nBuLi hexane solution was slowly added dropwise. The reaction mixture was slowly raised to room temperature and stirred until the next day. In another 250 mL schlenk flask, prepare a solution of 12.0586 g (40 mmol, purity of 90%) of dichloromethyltethersilane and 100 mL of hexane, cool the Schlenk flask to -30 °C, and then add the lithiated solution dropwise thereto. After the injection was completed, the mixture was slowly raised to room temperature and stirred for one day. The next day, 33.6 mL of NaCp in 2M THF was added dropwise and stirred for one day, quenched by adding 50 mL of water into the flask, and the organic layer was separated and dried over MgSO ₄ . As a result, 23.511 g (52.9 mmol) of an oil were obtained (purity based on NMR/wt%=92.97%. Mw=412.69).

4-2 Preparation of metallocene compound

Ligand was placed in a 250 mL schlenk flask dried in an oven, dissolved in 80 mL of Toluene and 19 mL of MTBE (160 mmol, 4 equiv.), and then 2.1 equivalents of nBuLi solution (84 mmol, 33.6 mL) was added for lithiation until the next day. In a glove box, 1 equivalent of ZrCl ₄ (THF) ₂ was taken and placed in a 250 mL schlenk flask to prepare a suspension containing Ether. After both flasks were cooled to -20 °C, ligand anion was slowly added to the Zr suspension. After the injection was completed, the reaction mixture was slowly raised to room temperature. After stirring for one day, MTBE in the mixture was immediately filtered through a Schlenk Filter under argon to remove LiCl produced after the reaction. After the removal, the remaining filtrate was removed through vacuum and reduced pressure, and pentane of the same volume as the reaction solvent was added to a small amount of dichloromethane. At this time, the reason for adding pentane is that the synthesized catalyst precursor has poor solubility in pentane and promotes crystallization. The slurry was filtered under argon, and the filter cake and filtrate remaining above were checked for catalyst synthesis through NMR, respectively, and weighed in a glove box and sampled to check the yield and purity (Mw = 715.04).

¹ H NMR (500 MHz, CDCl ₃ ): 0.60 (3H, s), 1.01 (2H, m), 1.16 (6H, s), 1.22 (9H, s), 1.35 (4H, m), 1.58 (4H, m), 2.11 (1H, s), 3.29 (2H, m), 5.56 (1H, s), 5.56 (2H, m), 5.66 (2H, m), 7.01 (2H, m), 7.40 (3H, m) ), 7.98 (2H, m)

Synthesis Example 5: Second metallocene compound

5-1 Preparation of Ligand Compounds

6-tert-butoxyhexyl chloride and sodium Cyclopentadiene (2 equivalents) were added under THF and stirred. After completion of the reaction, workup was carried out with water, and excess cyclopentadiene was removed by distillation. 27 mL of toluene was added to 4.45 g (20 mmol) of 6-tert-butoxyhexylcyclopentadiene obtained through the above process. The temperature was lowered to -20 °C, and 8.8 mL (22 mmol) of a 2.5 M n-BuLi Hexane solution was added dropwise, followed by stirring at room temperature overnight.

In a dried 250 mL Schlenk flask, 5.8 g (20 mmol) of 4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-indene was added, and 33 mL of MTBE was added. The temperature was lowered to -20 °C, 8.8 mL (22 mmol) of a 2.5M n-BuLi Hexane solution was added dropwise, and the mixture was stirred at room temperature overnight. The temperature was lowered to -20 °C and 1.5 equivalents of dichlorodimethyl silane was added. The mixture was stirred at room temperature overnight and distilled to remove excess dichlorodimethyl silane.

A solution obtained by lithiation of 6-tert-butoxyhexylcyclopentadiene was added to the flask above and stirred overnight. A ligand compound was obtained by working up the ligand synthesized by this process.

5-2 Preparation of metallocene compound

11.4 g (20 mmol) of the ligand compound synthesized in 5-1 was dissolved in 50 mL of toluene, and about 16.8 mL (42 mmol) of a 2.5M nBuLi hexane solution was added dropwise, followed by stirring at room temperature overnight. 20 mmol of ZrCl ₄ (THF) ₂ was added, stirred overnight, and when the reaction was completed, filtration was performed to remove LiCl. All solvents were removed, crystallized with hexane, and purified to obtain metallocene compounds (A, B forms) having different stereoisomers in a ratio of 1.3:1.

¹ H NMR (500 MHz, C ₆ D ₆ ):

Form A: 0.58 (3H,s), 0.55 (3H,s), 0.93-0.97(3H,m), 1.12 (9H,s), 1.28 (9H,s), 1.27 (3H,d), 1.35-1.42 (1H,m), 1.45-1.62(4H,m), 2.58-2.65 (1H,m), 2.67-2.85(2H,m), 3.20 (2H,t), 5.42 (1H,m), 5.57 (1H) , m), 6.60 (1H, m), 6.97 (1H, dd), 7.27 (1H, d), 7.39-7.45 (4H, m), 8.01 (2H, dd)

Form B: 0.60 (3H,s), 0.57 (3H,s), 0.93-0.97(3H,m), 1.11 (9H,s), 1.28 (9H,s), 1.32 (3H,d), 1.35-1.42 (1H,m), 1.45-1.62(4H,m), 2.58-2.65 (1H,m), 2.67-2.85(2H,m), 3.23 (2H,t), 5.24 (1H,m), 5.67 (1H) , m), 6.49 (1H, m), 6.97 (1H, dd), 7.32 (1H, d), 7.39-7.45 (4H, m), 8.01 (2H, dd)

Comparative Synthesis Example 1: Second metallocene compound

1-1 Preparation of Ligand Compounds

t-Butyl-O-(CH ₂ ) ₆ -Cl was prepared by the method presented in the literature (Tetrahedron Lett. 2951 (1988)) using 6-chlorohexanol, and NaCp was reacted therewith t-Butyl-O-(CH ₂ ) ₆ -C ₅ H ₅ was obtained (yield 60%, bp 80°C /0.1 mmHg)

1-2 metallocene Preparation of compounds

t-Butyl-O-(CH ₂ ) ₆ -C ₅ H ₅ was dissolved in THF at -78°C, n-butyllithium (n-BuLi) was slowly added thereto, and then the temperature was raised to room temperature, followed by reaction for 8 hours. The solution was again slowly added to a previously synthesized lithium salt solution to a suspension solution of ZrCl ₄ (THF) ₂ (1.70 g, 4.50 mmol)/THF (30 mL) at -78°C, and then at room temperature. was further reacted for 6 hours.

All volatile substances were vacuum-dried, and a hexane solvent was added to the obtained oily liquid substance and filtered. After the filtered solution was vacuum dried, hexane was added to induce a precipitate at low temperature (-20 °C). The obtained precipitate was filtered at low temperature to obtain a white solid [tBu-O-(CH ₂ ) ₆ -C ₅ H ₄ ] ₂ ZrCl ₂ compound (yield 92%).

¹ H NMR (300 MHz, CDCl3): 6.28 (t, J = 2.6 Hz, 2H), 6.19 (t, J = 2.6 Hz, 2H), 3.31 (t, 6.6 Hz, 2H), 2.62 (t, J = 8 Hz), 1.7 - 1.3 (m, 8H), 1.17 (s, 9H)

Comparative Synthesis Example 2: Second metallocene compound

2-1 Preparation of Ligand Compounds

3.7 g (40 mmol) of 1-chlorobutane was added to a dried 250 mL Schlenk flask and dissolved in 40 mL of THF. 20 mL of sodium cyclopentadienylide THF solution was slowly added thereto and stirred for one day. The reaction mixture was quenched by adding 50 mL of water, extracted with ether (50 mL x 3), and then the collected organic layer was sufficiently washed with brine. The remaining moisture was dried with MgSO ₄ , filtered, and the solvent was removed under vacuum to obtain 2-butyl-cyclopenta-1,3-diene, a dark brown viscous product, in quantitative yield.

2-2 Preparation of metallocene compound

About 4.3 g (23 mmol) of the ligand compound synthesized in 5-1 was added to a dried 250 mL Schlenk flask and dissolved in about 60 mL of THF. About 11 mL of n-BuLi 2.0M hexane solution (28 mmol) was added thereto, stirred for one day, and this solution was dispersed in about 50 mL of ether with 3.83 g (10.3 mmol) of ZrCl ₄ (THF) ₂ in a flask. was slowly added at -78 °C.

When the reaction mixture was raised to room temperature, it changed from a pale brown suspension to a cloudy yellow suspension. After stirring for one day, all the solvents of the reaction mixture were dried, and about 200 mL of hexane was added to sink by sonication, and the hexane solution floating on the upper layer was decanted by cannula and collected. The hexane solution obtained by repeating this process twice was dried under vacuum under reduced pressure to confirm that bis(3-butyl-2,4-dien-yl) zirconium(IV) chloride, a compound in the form of a pale yellow solid, was produced.

¹ H NMR (500 MHz, CDCl ₃ ): 0.91 (6H, m), 1.33 (4H, m), 1.53 (4H, m), 2.63 (4H, t), 6.01 (1H, s), 6.02 (1H, s) ), 6.10 (2H, s), 6.28 (2H, s)

<Preparation example of hybrid supported metallocene catalyst>

Preparation Example 1

2.0 kg of toluene and 1000 g of silica (Grace Davison, SP2410) were put into a 20L SUS high-pressure reactor, and the reactor was stirred while raising the temperature to 40 °C. 5.4 kg of methylaluminoxane (10wt% in toluene, manufactured by Albemarle) was added to the reactor, and the temperature was raised to 70° C., followed by stirring at about 200 rpm for about 12 hours. After that, the temperature of the reactor was lowered to 40 °C, and stirring was stopped. Then, the reaction product was allowed to stand for about 10 minutes, followed by decantation. Again, 2.0 kg of toluene was added to the reaction product and stirred for about 10 minutes, the stirring was stopped, and the mixture was left still for about 30 minutes, followed by decantation.

2.0 kg of toluene was introduced into the reactor, and then the compound (60 mmol) prepared in Synthesis Example 1, the compound (10 mmol) prepared in Synthesis Example 4 (10 mmol), and 1000 mL of toluene were added. The temperature of the reactor was raised to 85 °C and stirred for about 90 minutes.

Thereafter, the temperature of the reactor was lowered to room temperature, stirring was stopped, and the reaction product was allowed to stand for about 30 minutes, and then the reaction product was decantation. Then, 3 kg of hexane was put into the reactor, the hexane slurry solution was transferred to a 20L filter dryer, the solution was filtered, and the solution was dried under reduced pressure at 50° C. for about 4 hours to obtain 1.5 kg of a supported catalyst.

Preparation 2

A hybrid supported metallocene catalyst was prepared in the same manner as in Preparation Example 1, except that the metallocene compound of Synthesis Example 2 (60 mmol) and Synthesis Example 4 (10 mmol) was used.

Preparation 3

A hybrid supported metallocene catalyst was prepared in the same manner as in Preparation Example 1, except that the metallocene compound of Synthesis Example 3 (60 mmol) and Synthesis Example 5 (10 mmol) was used.

Comparative Preparation Example 1

A supported metallocene catalyst was prepared in the same manner as in Preparation Example 1, except that only the metallocene compound of Synthesis Example 1 (70 mmol) was used.

Comparative Preparation Example 2

A hybrid supported metallocene catalyst was prepared in the same manner as in Preparation Example 1, except that the metallocene compound of Synthesis Example 1 (60 mmol) and Comparative Synthesis Example 1 (10 mmol) was used.

Comparative Preparation Example 3

A supported metallocene catalyst was prepared in the same manner as in Preparation Example 1, except that the metallocene compound of Synthesis Example 2 (60 mmol) and Comparative Synthesis Example 2 (10 mmol) was used.

The main configurations of the Preparation Examples and Comparative Preparation Examples are shown in Table 1 below.

Preparation Example 1 Preparation 2 Preparation 3 Comparative Preparation Example 1 Comparative Preparation Example 2 Comparative Preparation Example 3 support type concoction
support concoction
support concoction
support single
support concoction
support concoction
support Metallocene compound composition Synthesis Example 1 / Synthesis Example 4 Synthesis Example 2 /
Synthesis Example 4 Synthesis Example 3 /
Synthesis Example 5 Synthesis Example 1 Synthesis Example 1
/ Comparative Synthesis Example 1 Synthesis Example 2
/ Comparative Synthesis Example 2 Metallocene Compound Ratio
(molar ratio) 6:1 6:1 6:1 6:1 6:1

<Production of polyolefins Example >

Ethylene-1-hexene copolymerization

The isobutene slurry loop process is possible as a polymerization reactor, and a 140L continuous polymerization reactor operated at a reaction flow rate of about 7 m/s was prepared. Then, as shown in Table 2, the reactants necessary for olefin polymerization were continuously added to the reactor.

The supported catalyst used in each olefin polymerization reaction was prepared in the preparation examples shown in Table 1, and the supported catalyst was mixed with the isobutene slurry and added.

The olefin polymerization reaction was carried out under a pressure of about 40 bar and a temperature of about 84 °C.

Table 2 shows the main conditions of the polymerization reaction.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 catalyst Preparation Example 1 Preparation 2 Preparation 3 Comparative Preparation Example 1 Comparative Preparation Example 2 Comparative Preparation Example 3 Ethylene input (kg/hr) 40 40 40 40 40 40 Hydrogen input (ppm) 15 17 19 22 11.5 9 Hexene dosage 13 12.5 15 16 14 14.5 Slurry Density (g/L) 560 560 563 560 559 558 Activity (kgPE/kgSiO ₂ hr) 6.5 5.4 5.1 4.9 6.9 6.6 Bulk density (g/mL) 0.40 0.42 0.39 0.38 0.40 0.41 Settling efficiency (%) 40 40 40 40 40 40

< Experimental example >

The physical properties of the polyolefins prepared in Examples and Comparative Examples were measured as follows, and the results are shown in Table 3 below.

During extrusion to measure haze and drop impact strength, an antioxidant (Irganox 1010 + Igafos 168, CIBA) was prescribed to the obtained polyolefin, and then 180 using a twin screw extruder (W&P Twin Screw Extruder, 75 pie, L/D=36) It was granulated at an extrusion temperature of ~ 210 °C.

(1) Density: It was measured according to ASTM D1505 standard.

(2) Melt Index (MI _2.16 ): Measured according to ASTM D1238 (Condition E, 190°C, load 2.16kg).

(4) Haze: A single screw extruder (Yujin Engineering Single Screw Extruder, Blown Film M/C, 50 pie) was used and inflation was performed at an extrusion temperature of 130 ~ 170℃ to a thickness of 60㎛. At this time, the die gap (Die Gap) was 2.0mm, and the blown-up ratio was 2.3. The thus-prepared film was measured according to ISO 13468 standard. At this time, each specimen was measured 10 times and the average value was taken.

(4) Drop impact strength: After preparing a polymer film under the same conditions as in (3), it was measured 20 times or more per film sample according to ASTM D1709 [Method A], and the average value was taken.

(5) SSA thermogram

Using a differential scanning calorimeter (device name: DSC8000, manufacturer: PerkinElmer), the polyolefin was initially heated to 160° C. and then maintained for 30 minutes to remove all the thermal history of the sample before measurement.

After lowering the temperature from 160 °C to 122 °C, holding for 20 minutes, lowering the temperature to 30 °C, holding for 1 minute, and then increasing the temperature again. Next, after heating to a temperature 5°C lower (117°C) than the initial heating temperature of 122°C, the temperature was maintained for 20 minutes, the temperature was lowered to 30°C, maintained for 1 minute, and then the temperature was increased again. In this way, the n+1-th heating temperature was set to a temperature lower than the n-th heating temperature by 5°C, the holding time and the cooling temperature were the same, and the heating temperature was gradually lowered to 52°C. At this time, the rate of rise and fall of the temperature was adjusted to 20 °C/min, respectively. Finally, the temperature was increased from 30°C to 160°C at a temperature increase rate of 10°C/min, and the change in calorific value was observed and the SSA thermogram was measured.

(6) Inhomogeneity (I) of the ethylene sequence

The heterogeneity of the ethylene sequence calculated according to Equation 1 was calculated:

[Equation 1]

Inhomogeneity (I) = L _w / L _n

In Equation 1 above,

L _w is a weighted average (unit: nm) of ESL (Ethylene sequence length), and L _n is an arithmetic mean (Unit: nm) of ESL (Ethylene sequence length).

The weighted average (L _w ) and the arithmetic mean (L _n ) of the ethylene sequence of Equation 1 were calculated by Equations 2 and 3 below:

[Equation 2]

In Equation 2 above,

[Equation 3]

In Equations 2 and 3 above,

_Si is the area of each melting peak measured in the SSA thermogram,

L _i is the Average Ethylene Sequence Length (ASL) corresponding to each melting peak in the SSA thermogram.

In addition, the ASL was obtained from the SSA thermogram measured as described above in Journal of Polymer Science Part B: Polymer Physics. 2002, vol. 40, 813-821 and Journal of the Korean Chemical Society 2011, Vol. 55, No. It was calculated with reference to 4.

In addition, FIG. 1 shows a graph showing the relationship between inhomogeneity and drop impact strength of polyolefins according to Examples and Comparative Examples of the present invention.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Density (g/cm ³ ) 0.918 0.918 0.917 0.918 0.918 0.918 MI _2.16 (g/10min) 0.96 1.09 0.99 1.23 1.03 1.13 L _n (nm) 10.54 13.27 11.46 10.48 10.34 10.62 L _w (nm) 11.18 14.45 14.77 12.697 12.81 13.19 I ( L _w / L _n ) 1.26 1.29 1.29 1.24 1.24 1.24 drop impact strength
(g) 1,390 1,250 1,210 960 1,050 1,010 Haze (%) 8.5 9.1 10.9 9.4 12.2 11.6

Referring to Table 3 and FIG. 1, the polyolefins of Examples 1 to 3 of the present invention had a haze of 11% or less and excellent drop impact strength compared to Comparative Examples 1 to 3 having the same density.

Claims (12)

a density of 0.915 g/cm ³ to 0.930 g/cm ³ ; and
SSA (Successive Self-nucleation and Annealing) analysis, the non-uniformity (inhomogeneity, I) of the ethylene sequence calculated by Equation 1 below is 1.25 to 1.40,
Polyolefin:
[Equation 1]
Inhomogeneity (I) = L _w / L _n
In Equation 1 above,
L _w is a weighted average (unit: nm) of ESL (Ethylene sequence length), and L _n is an arithmetic mean (Unit: nm) of ESL (Ethylene sequence length).
The method of claim 1,
The L _n is calculated by the following formula 2, the L _w is calculated by the following formula 3, polyolefin:
[Equation 2]

[Equation 3]

In 2 and 3 above,
_Si is the area of each melting peak measured in the SSA thermogram,
L _i is the Average Ethylene Sequence Length (ASL) corresponding to each melting peak in the SSA thermogram.
The method of claim 1,
The SSA is, using a differential scanning calorimeter, the polyolefin is heated to 120 to 124 ° C. at the first heating temperature, maintained for 15 to 30 minutes, cooled to 28 to 32 ° C., and the n+1th heating temperature is Polyolefin, which is performed by repeating heat-annealing-quenching until the final heating temperature is 50 to 54°C while stepwise lowering the heating temperature to a temperature 3 to 7°C lower than the n-th heating temperature.
The method of claim 1,
A polyolefin having a melt index (MI _2.16 ) of 0.5 to 1.5 g/10 min, measured at a temperature of 190° C. and a load of 2.16 kg according to ASTM D1238 standard.
The method of claim 1,
After preparing a polyolefin film (BUR 2.3, film thickness 55 to 65 μm) using a film making machine, the polyolefin having a haze of 11% or less measured according to ISO 13468.
The method of claim 1,
A polyolefin having a drop impact strength of 850 g or more measured according to ASTM D 1709 [Method A] after manufacturing a polyolefin film (BUR 2.3, film thickness 55 to 65 μm) using a film making machine.
The method of claim 1,
The polyolefin is a copolymer of ethylene and alpha olefin, polyolefin.
8. The method of claim 7,
The alpha olefin is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1 -Tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbornadiene, ethylidene noboden, phenyl noboden, vinyl noboden, dicyclopentadiene, 1,4-butadiene, 1,5-penta A polyolefin comprising at least one selected from the group consisting of diene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene.
The method of claim 1,
The polyolefin may include at least one first metallocene compound selected from compounds represented by the following Chemical Formula 1; at least one second metallocene compound selected from compounds represented by the following formula (2); and a polyolefin prepared by polymerizing an olefin monomer in the presence of a hybrid supported metallocene catalyst comprising a carrier supporting the first and second metallocene compounds:
[Formula 1]

In Formula 1,
Q ₁ and Q ₂ are the same as or different from each other and are each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkoxyalkyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group;
T ₁ is carbon, silicon, or germanium;
M ₁ is a Group 4 transition metal;
X ₁ and X ₂ are the same as or different from each other, and each independently a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, 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;
R ₁ to R ₁₄ are the same as or different from each other, and each independently hydrogen, halogen, C1 to C20 alkyl group, C1 to C20 haloalkyl group, C2 to C20 alkenyl group, C1 to C20 alkylsilyl group, C1 to C20 of a silylalkyl group, a C1 to C20 alkoxysilyl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, or among R ₁ to R ₁₄ two or more adjacent to each other are connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring;
[Formula 2]

In Formula 2,
Q ₃ and Q ₄ are the same as or different from each other, and are each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkoxyalkyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group;
T ₂ is carbon, silicon, or germanium;
M ₂ is a Group 4 transition metal;
X ₃ and X ₄ are the same as or different from each other, and each independently a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, 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;
R ₁₅ to R ₂₈ are the same as or different from each other, and each independently hydrogen, halogen, C1 to C20 alkyl group, C1 to C20 haloalkyl group, C2 to C20 alkenyl group, C2 to C20 alkoxyalkyl group, C1 to C20 an alkylsilyl group, a C1 to C20 silylalkyl group, a C1 to C20 alkoxysilyl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, However, R ₂₀ and R ₂₄ are the same as or different from each other and each independently represent a C1 to C20 alkyl group.
10. The method of claim 9,
The compound represented by Formula 1 is any one of the compounds represented by the following structural formula, polyolefin:

,

,

,

,

,

,

,

10. The method of claim 9,
The compound represented by Formula 2 is any one of the compounds represented by the following structural formula, polyolefin:

,

,

10. The method of claim 9,
The molar ratio of the first and second metallocene compounds is 1:1 to 10:1, polyolefin.

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