KR102629595B1 - Polyolefin - Google Patents

Abstract

The present invention relates to polyolefins. More specifically, the present invention relates to polyolefins that can exhibit improved mechanical properties, such as excellent drop impact strength.

Description

Polyolefin {POLYOLEFIN}

The present invention relates to polyolefins. More specifically, the present invention relates to polyolefins that can exhibit improved mechanical properties, such as excellent drop impact strength.

Linear low density polyethylene (LLDPE) is manufactured by copolymerizing ethylene and alpha olefin at low pressure using a polymerization catalyst. It is a resin with a narrow molecular weight distribution, short chain branches of a certain length, and no long chain branches. Linear low-density polyethylene film has the characteristics of general polyethylene, as well as high breaking strength and elongation, and has excellent tear strength and drop impact strength, so its use is increasing in stretch films and overlap films where it is difficult to apply existing low-density polyethylene or high-density polyethylene. I'm doing it.

However, linear low-density polyethylene has the disadvantage of poor blown film processability and poor transparency compared to its excellent mechanical properties. Blown film is a film manufactured by blowing air into molten plastic to inflate it, and is also called inflation film.

Linear low-density polyethylene generally has the characteristics of improved transparency and increased drop impact strength as the density decreases. However, when a large amount of alpha olefin comonomer is used to produce low-density polyethylene, there are problems such as an increase in the frequency of fouling in the slurry polymerization process, so many products with a density of 0.915 g/cm ³ or more are produced in the slurry polymerization process. I'm doing it.

Therefore, there is a need for the development of polyethylene that has a density of 0.915 g/cm ³ or more and can provide transparency and excellent mechanical properties such as drop impact strength.

In order to solve the problems of the prior art, the present invention seeks to provide a polyolefin that can exhibit improved mechanical properties such as excellent drop impact strength while having a density of 0.915 g/cm ³ or more.

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

Provided is a polyolefin that satisfies the following conditions 1) to 3):

1) Density measured according to ASTM D1505 is 0.915 g/cm ³ to 0.930 g/cm ³ ;

2) a melt index (MI) of 0.5 to 1.5 g/10 min as measured according to ASTM D1238 at 190°C and a load of 2.16 kg; and

3) When analyzing SSA (Successive Self-nucleation and Annealing), the proportion of chains with an ASL (Average Ethylene Sequence Length) of 22 nm or more in length is more than 16% by weight of the total chain, and ASL (Average Ethylene Sequence Length) of 8 nm or less is determined by weight. The proportion of chains is 38% by weight or more based on the total chain.

According to the present invention, when polymerizing polyolefin using a metallocene catalyst, the length and distribution of the ethylene sequence forming the lamellar are appropriately adjusted to achieve optimal ASL (Average Ethylene Sequence Length) ratio, density, and melting. Polyolefins having an index can be provided.

Accordingly, it is possible to provide polyolefin with high drop impact strength.

Figure 1 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.

Additionally, the terminology used herein is only used to describe exemplary embodiments and is not intended to limit the invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as “comprise,” “comprise,” or “have” are intended to designate the presence of implemented features, numbers, steps, components, or a combination thereof, and are intended to indicate the presence of one or more other features or It should be understood that this does not exclude in advance the possibility of the presence or addition of numbers, steps, components, or combinations thereof.

Since the present invention can be subject to various changes and can take various forms, specific embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to a specific disclosed form, and should be understood to include all changes, equivalents, and substitutes included in the spirit and technical scope of the present invention.

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

The polyolefin according to one embodiment of the present invention satisfies the following conditions 1) to 3): 1) a density measured according to ASTM D1505 of 0.915 g/cm ³ to 0.930 g/cm ³ ; 2) a melt index (MI) of 0.5 to 1.5 g/10 min as measured according to ASTM D1238 at 190°C and a load of 2.16 kg; and 3) When analyzing SSA (Successive Self-nucleation and Annealing), the proportion of chains with an ASL (Average Ethylene Sequence Length) of 22 nm or more in length is 16% by weight or more based on the total chain, and an ASL (Average Ethylene Sequence Length) of 8 nm or less. The proportion of chains having is 38% by weight or more based on the total chain.

Linear low density polyethylene (LLDPE) is manufactured by copolymerizing ethylene and alpha olefin at low pressure using a polymerization catalyst, and is a resin with a narrow molecular weight distribution and short chain branches of a certain length. Linear low-density polyethylene film has the characteristics of general polyethylene, as well as high breaking strength and elongation, and has excellent tear strength and drop impact strength, so its use is increasing in stretch films and overlap films where it is difficult to apply existing low-density polyethylene or high-density polyethylene. I'm doing it.

Meanwhile, linear low-density polyethylene is generally known to have increased transparency and drop impact strength as the density decreases. However, when a large amount of comonomer is used to produce low-density polyethylene, the frequency of fouling increases during the slurry polymerization process, and when manufacturing a film containing it, the amount of antiblocking agent must be increased due to the stickiness phenomenon. There are problems such as Additionally, there are problems such as unstable production processes or a decrease in the bulk density due to a decrease in the morphology characteristics of the polyethylene produced.

Accordingly, in the present invention, the optimal ASL (Average Ethylene Sequence Length) ratio that can increase transparency and drop impact strength by appropriately controlling the length and distribution of the ethylene sequence that forms lamellar while having low density characteristics is found. The object is to provide a polyolefin having

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

1) Density

The polyolefin according to one embodiment of the present invention may be low density polyethylene (LDPE) that satisfies a density of 0.915 g/cm ³ to 0.930 g/cm ³ as measured according to ASTM D1505.

More specifically, the density of the polyolefin of the present invention according to one embodiment 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 0.919 g/cm ³ or more but less than or equal to 0.930 g/cm ³ , or less than or equal to 0.928 g/cm ³ , or less than or equal to 0.925 g/cm ³ , or less than or equal to 0.922 g/cm ³ , or less than or equal to 0.921 g/cm ³ , or less than or equal to 0.920 g/cm 3 It may be cm ³ or less.

Due to the low density characteristics described above, it has high breaking strength and elongation, and has excellent tear strength and drop impact strength, so it can be usefully used as a film for detergent packaging and food packaging that requires these physical properties.

2) Melt Index (MI)

The polyolefin according to one embodiment of the present invention has a melt index (MI) of 0.5 to 1.5 g/10min measured according to ASTM D1238 at 190°C and under a load of 2.16 kg.

More specifically, the melt index (MI) of the polyolefin of the present invention according to one embodiment is 0.5 g/10min or more, or 0.6 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 may be less than or equal to 1.5 g/10min, or less than or equal to 1.4 g/10min, or less than or equal to 1.3 g/10min, or less than or equal to 1.2 g/10min, or less than or equal to 1.1 g/10min.

If the melt index is lower than the above-described range, processing may be difficult, and if the melt index is higher than the above-described range, the mechanical properties of the polyolefin resin may be reduced.

3) Distribution of ASL (Average Ethylene Sequence Length) chains during SSA (Successive Self-nucleation and Annealing) analysis

In the polyolefin according to one embodiment of the present invention, when analyzed by SSA (Successive Self-nucleation and Annealing), the ratio of chains having an ASL (Average Ethylene Sequence Length) of 22 nm or more in length is 16% by weight or more based on the total chain.

More specifically, in the polyolefin of the present invention according to one embodiment, the proportion of chains having an ASL of 22 nm or more is 16% by weight or more, or 17% by weight or more, or 18% by weight or more, and 35% by weight or less, or 30% by weight or less, or 28% by weight or less, or 26% by weight or less, or 24% by weight or less, or 22% by weight or less.

In addition, the polyolefin according to one embodiment of the present invention has a ratio of chains having an average ethylene sequence length (ASL) of 8 nm or less in length when analyzed by SSA (Successive Self-nucleation and Annealing) of more than 38% by weight based on the total chain.

More specifically, in the polyolefin of the present invention according to one embodiment, the proportion of chains having an ASL of 8 nm or less is 38% by weight or more, or 39% by weight or more, or 40% by weight or more, and 50% by weight or less, Or it may be 48% by weight or less, or 46% by weight or less, or 44% by weight or less.

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 polymer chains containing ethylene repeating units or alpha olefin repeating units are folded, thereby forming a lamellar crystalline block (or segment).

In the polyolefin according to one embodiment of the present invention, according to SSA (Successive Self-nucleation and Annealing) analysis, the proportion of chains having an ASL with a length of 22 nm or more is 16% by weight or more based on the total chain, and the ASL with a length of 8 nm or less is more than 16% by weight. It was confirmed that when the ratio of chains is 38% by weight or more relative to the total chain, it can have significantly improved drop impact strength compared to conventional polyolefin of the same density.

SSA (Successive Self-nucleation and Annealing) is a method of lowering the temperature in stages using a Differential Scanning Calorimeter (DSC) and rapidly cooling at the end of each stage to preserve the crystals crystallized at that temperature at each stage. am.

In other words, when polyolefin is heated and completely melted, then cooled to a specific temperature (T) and slowly annealed, the lamellas that are not stable at that temperature (T) are still melted and only the stable lamellas are melted. It crystallizes. At this time, the stability at the corresponding temperature (T) depends on the thickness of the lamellae, and the thickness of the lamellae depends on the chain structure. Therefore, by carrying out this heat treatment step by step, the lamella thickness and its distribution according to the polymer chain structure can be quantitatively evaluated.

At this time, one melting peak is not only caused by a lamella with the same ethylene sequence length, but by a plurality of lamellaes that have various sequence lengths but can crystallize at the same temperature. do. Therefore, the average length of the ethylene sequence that crystallizes at a specific temperature can be referred to as ASL (Average Ethylene Sequence Length). That is, in the specification of the present invention, ASL with a length of 22 nm or more refers to an ethylene sequence in which the average length of the ethylene sequences showing the same melting peak by SSA analysis is 22 nm or more. In addition, ASL with a length of 8 nm or less refers to an ethylene sequence whose average length of the ethylene sequences showing the same melting peak by SSA analysis is 8 nm or less.

According to one embodiment of the present invention, the SSA heats the polyolefin to a first heating temperature of 120 to 124°C using a differential scanning calorimeter, maintains it for 15 to 30 minutes, and then cools to 28 to 32°C. , the n+1th heating temperature is 3 to 7°C lower than the nth heating temperature, and the heating temperature is gradually lowered, followed by heating-annealing-quenching until the final heating temperature is 50 to 54°C. 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, lowering the temperature to 30°C and maintaining it for 1 minute;

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

iv) The n+1th heating temperature is set to be 5℃ lower than the nth heating temperature, and the heating rate, holding time, and cooling temperature are the same, and the heating temperature is gradually lowered until the heating temperature reaches 52℃. Steps to perform; and

v) Finally, raising the temperature from 30℃ to 160℃.

The temperature profile of the SSA analysis method according to one embodiment of the present invention is shown in Figure 1.

Referring to Figure 1, using a differential scanning calorimeter (device name: DSC8000, manufacturer: PerkinElmer), polyolefin is initially heated to 160°C and maintained for 30 minutes to remove all heat history of the sample before measurement. After lowering the temperature from 160℃ to 122℃ and maintaining it for 20 minutes, lowering the temperature to 30℃ and maintaining it for 1 minute, then increasing the temperature again.

Next, it is heated to a temperature (117°C) that is 5°C lower than the initial heating temperature of 122°C and maintained for 20 minutes. The temperature is lowered to 30°C and held for 1 minute, and then the temperature is increased again. In this way, the n+1th heating temperature is 5°C lower than the nth heating temperature, the holding time and cooling temperature are the same, and the heating temperature is gradually lowered to 52°C. At this time, the temperature rising and falling speeds are each adjusted to 20°C/min. Raise the temperature from 30℃ to 160℃ at a rate of 20℃/min, observe the change in heat amount, and measure the thermogram.

When the temperature of the polyolefin of the present invention is raised after repeated heating-annealing-quenching using the SSA method, peaks for each temperature appear, and the ASL can be calculated from the SSA thermogram measured in this way.

More specifically, ASL can be obtained according to Equation 1 below. In Equation 1 below, CH ₂ mole fraction means the mole ratio of continuous ethylene (consecutive ethylene) in the entire polyolefin, and the mole ratio of ethylene is again as follows: It can be calculated using equation 2:

[Equation 1]

ASL = 0.2534(CH ₂ mole fraction) / (1 - CH ₂ mole fraction)

[Equation 2]

- ln(CH ₂ mole fraction) = -0.331 + 135.5/T _m (K)

T _m is the melting temperature (unit: K) in polyolefin, and in the present invention, it means the peak temperature of peaks for each temperature obtained in SSA analysis.

For an explanation of Equations 1 and 2 above and a more detailed calculation method of ASL, see Journal of Polymer Science Part B: Polymer Physics. 2002, vol. 40, 813-821, and Journal of the Korean Chemical Society 2011, Vol. 55, no. You can refer to 4.

By having the above ASL ratio, the polyolefin of the present invention can achieve excellent film mechanical properties, such as drop impact strength, compared to polyolefins with similar density and SCB content.

4) SBC (Short Chain Branch)

The polyolefin according to an embodiment of the present invention may have SCB (Short Chain Branch) of 22 or more, or 23 or more, and 30 or less, or 28 or less, or 26 or less, or 25 or less per 1000 carbon atoms. there is.

SCB (Short Chain Branch) refers to branches with 2 to 6 carbon atoms attached to the main chain of an olefinic polymer, and are usually comonomers, such as 1-butene, 1-hexene, 1-octene, etc. This refers to the side branches created when using alpha olefins of 4 or more. This SCB content (unit: pieces/1000C) can be measured using GPC-FTIR.

GPC-FTIR preprocessed the sample by dissolving it in 1, 2, 4-Trichlorobenzene containing 0.0125% BHT at 160°C for 10 hours using PL-SP260VS, and then analyzed the sample using a PerkinElmer Spectrum 100 FT connected to a high-temperature GPC (PL-GPC220). -Measured at 160°C using IR.

By having the above SBC number, the polyolefin of the present invention can achieve excellent film mechanical properties, such as drop impact strength, compared to polyethylene of similar density.

5) Other physical properties

The polyolefin according to one embodiment of the present invention may have a molecular weight distribution (PDI, Mw/Mn) of 3.3 to 4.0.

More specifically, the molecular weight distribution of the polyolefin of the present invention according to one embodiment may be 3.3 or more, or 3.4 or more, or 3.5 or more, or 3.6 or more, and 4.0 or less, or 3.9 or less, or 3.8 or less.

In the present invention, since it has a relatively narrow molecular weight distribution compared to the low melt index as described above, both excellent mechanical properties and tensile strength characteristics can be satisfied.

The polyolefin according to one embodiment of the present invention may have a weight average molecular weight (Mw) of 100,000 to 150,000 g/mol. More preferably, the weight average molecular weight is at least 100,000 g/mol, or at least 110,000 g/mol, or at least 120,000 g/mol, and at most 150,000 g/mol, or at most 140,000 g/mol, or at least 130,000 g/mol. It may be below.

In the present invention, the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution of polyolefin are measured using gel permeation chromatography (GPC), respectively. And the ratio of weight average molecular weight to number average molecular weight (Mw/Mn) was calculated as the molecular weight distribution.

Specifically, polyolefin samples were evaluated using a Waters PL-GPC220 instrument using a Polymer Laboratories PLgel MIX-B 300 mm long column. The evaluation temperature was 160°C, 1,2,4-trichlorobenzene was used as a solvent, and the flow rate was measured at 1 mL/min. The sample was prepared at a concentration of 10 mg/10 mL and then supplied in an amount of 200 μL. The values of Mw and Mn were measured using a calibration curve formed using polystyrene standards. Nine types of molecular weights of polystyrene standards were used: 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.

According to one embodiment of the present invention, the polyolefin may be, for example, a copolymer of ethylene and alpha olefin. At this time, 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-eicocene, norbornene, norbonadiene, ethylidene nobodene, phenylnobodene, vinylnobodene, dicyclopentadiene, 1,4-butadiene, 1,5- It may include pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene. Preferably, 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.

In addition, the polyolefin according to one embodiment of the present invention has a drop impact strength measured according to ASTM D 1709 [Method A] after producing a polyolefin film (BUR 2.3, film thickness 55 to 65 ㎛) using a film forming machine. may be 1,500 g or more, or 1,600 g or more, or 1,700 g or more. The higher the drop impact strength, the better, so the upper limit is not particularly limited, but may be, for example, 2,000 g or less, 1,950 g or less, or 1,900 g or less.

As described above, the polyolefin of the present invention can exhibit improved transparency and drop impact strength compared to conventional polyolefins having the same density range.

On the other hand, the polyolefin according to one embodiment of the invention having the above physical properties can be produced by a production method comprising the step of polymerizing olefin monomers in the presence of a hybrid supported metallocene compound as a catalytically active ingredient. .

More specifically, the polyolefin of the present invention is not limited thereto, but includes at least one first metallocene compound selected from compounds represented by the following 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,

M is a group 4 transition metal,

X ₁ and X ₂ are the same or different from each other and are each independently hydrogen, halogen, C _1-20 alkyl, or QCOO-,

Q is C _1-20 alkyl,

A is carbon, silicon or germanium,

R ₁ and R ₂ are the same or different and are each independently C _1-20 alkyl, C _2-20 alkenyl, C _6-30 aryl,

R ₃ to R ₆ are the same or different, and are each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-30 aryl, C _7-30 alkylaryl, or C _7-30 arylalkyl ego,

R ₇ , and R ₇ 'are the same or different, and are each independently C _1-20 alkyl, C _2-20 alkenyl, C _6-30 aryl, or C _2-20 alkoxy alkyl,

E is any one selected from the group consisting of sulfur (S), oxygen (O) and selenium (Se),

[Formula 2]

In Formula 2,

M' is a group 4 transition metal,

A' is carbon, silicon or germanium,

X ₃ and X ₄ are the same or different from each other and are each independently halogen or C _1-20 alkyl,

R ₈ to R ₁₁ are the same as or different from each other, and are each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, C _7-20 alkylaryl, C _{7- 20} arylalkyl, or at least two of R ₈ to R ₁₁ adjacent to each other are connected to each other to form a substituted or unsubstituted aliphatic ring, an aromatic ring, or at least one selected from the group consisting of N, O, and S. Forming a heteroaromatic ring containing,

R ₁₂ and R ₁₂ 'are the same or different from each other, and are each independently C _1-20 alkyl, C _2-20 alkenyl, C _6-30 aryl, or C _2-20 alkoxy alkyl,

R ₁₃ is C _1-20 alkyl, C _2-20 alkenyl, or C _6-30 aryl.

In the invention, the substituents of the above formula are described in more detail as follows.

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

C _1-20 alkyl can be straight chain, branched chain or cyclic alkyl. Specifically, the C _1-20 alkyl is C _1-20 straight chain alkyl; C _1-10 straight chain alkyl; C _1-5 straight chain alkyl; C _3-20 branched or cyclic alkyl; C _3-15 branched or cyclic alkyl; or C _3-10 branched or cyclic alkyl. More specifically, alkyl with carbon atoms C _1-20 is methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, It may be n-hexyl, or cyclohexyl group.

C _2-20 alkenyl can be straight chain, branched chain or cyclic alkenyl. Specifically, the C _2-20 alkenyl is C _2-20 straight chain alkenyl, C _2-10 straight chain alkenyl, C _2-5 straight chain alkenyl, C _3-20 branched chain alkenyl, C _3-15 branched chain. It may be alkenyl, C _3-10 branched chain alkenyl, C _5-20 cyclic alkenyl or C _5-10 cyclic alkenyl. More specifically, C _2-20 alkenyl may be ethenyl, propenyl, butenyl, pentenyl, or cyclohexenyl.

C _6-30 Aryl can refer to a monocyclic, bicyclic or tricyclic aromatic hydrocarbon. Specifically, C _6-30 aryl may be a phenyl group, naphthyl group, or anthracenyl group.

C _7-20 alkylaryl may refer to a substituent in which one or more hydrogens of aryl are replaced by alkyl. Specifically, the C _7-20 alkylaryl may be methylphenyl, ethylphenyl, n-propylphenyl, iso-propylphenyl, n-butylphenyl, iso-butylphenyl, tert-butylphenyl, or cyclohexylphenyl.

C _7-20 Arylalkyl may refer to a substituent in which one or more hydrogens of alkyl are replaced by aryl. Specifically, the C _7-20 arylalkyl may be a benzyl group, phenylpropyl, or phenylhexyl.

C _2-20 alkoxyalkyl has a structure containing -Ra-O-Rb and may be a substituent in which one or more hydrogens of alkyl (-Ra) are replaced with alkoxy (-O-Rb). Specifically, C _2-20 alkoxyalkyl is methoxymethyl group, methoxyethyl group, ethoxymethyl group, iso-propoxymethyl group, iso-propoxyethyl group, iso-propoxyhexyl group, tert-butoxymethyl group, tert-part It may be a toxyethyl group or a tert-butoxyhexyl group.

The heteroaromatic ring is a heteroaryl containing at least one of O, N, and S as a heteroelement, and the number of carbon atoms is not particularly limited, but may have 2 to 60 carbon atoms or 2 to 20 carbon atoms. Examples of heteroaromatic rings include thiophene, benzothiophene, dibenzothiophene, xanthene, thioxanthen, furan, pyrrole, and imidazole groups. , thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyridinyl group, pyrimidyl group, triazine group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothia Examples include sol group, benzocarbazole group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadiazolyl group, phenothiazinyl group, and dibenzofuranyl group, but are not limited to these.

Group 4 transition metals include titanium, zirconium, and hafnium.

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

The above-mentioned substituents are optionally hydroxy group, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-30 aryl, and C _2-20 within the range of achieving the same or similar effect as the desired effect. It may be substituted with one or more substituents selected from the group consisting of alkoxy alkyl.

By using the hybrid supported catalyst, excellent drop impact strength can be secured due to the specific lamellar distribution of polyolefin, and excellent polyolefin can be manufactured.

Specifically, in the hybrid supported catalyst according to one embodiment of the invention, the first metallocene compound is easy to produce low molecular weight polyolefin and has a small amount of short chain branches. The second metallocene compound contains a larger amount of short chain branches than the first metallocene compound, has a large distribution of short chain branches, and is easy to produce polyolefin with a relatively high molecular weight. In particular, a polymer produced using a hybrid supported catalyst containing a second metallocene and a first metallocene compound can exhibit excellent mechanical properties due to thick lamellae and strong connections between lamellae.

Meanwhile, the metallocene compound represented by Formula 1 forms a structure in which two symmetrical ligand compounds are cross-linked by a bridge compound. The ligand compound contains group 16 elements with lone pairs of electrons. This lone pair of electrons can provide an electron-rich environment for the central metal atom of the metallocene compound, and at the same time can act as a Lewis base and exhibit excellent polymerization activity.

The ligand specifically consists of a 5-membered ring containing a Group 16 hetero element, and a structure in which benzene and cyclopentadiene are fused to both sides of the 5-membered ring. Among them, cyclopentadiene is connected to a central metal atom and a bridge compound. In particular, the substituents (R ₁ , R ₂ ) of cyclopentadiene serve as electron donors and provide an electronically rich environment through an inductive effect. In addition, when cyclopentadiene or an additional substituent is added to benzene, steric hindrance is formed and an appropriate range of vacant sites is secured to facilitate access of monomers, thereby increasing polymerization activity.

In addition to the structural characteristics of the ligand, the metallocene compound of the present invention includes a bridge group other than a transition metal compound. The bridge group serves to increase the accessibility of the reactant monomer by increasing the size of the metallocene compound, and can improve support stability by interacting with the carrier and cocatalyst described later.

As described above, the metallocene compound represented by Formula 1 exhibits low copolymerization when used as a catalyst due to the interaction of symmetrical ligands, bridge compounds, and transition metals, and is suitable for producing low molecular weight ethylene polymers, and is manufactured accordingly. The ethylene polymer has a high MI and is highly processable.

The central metal (M) of the metallocene compound represented by Formula 1 may be a Group 4 transition metal, preferably titanium (Ti), zirconium (Zr), or hafnium (Hf).

Preferably, in Formula ₁ , and X ₂ may each independently be halogen, methyl, CH ₃ COO-, or C(CH ₃ ) ₃ COO-.

Preferably, in Formula 1, A may be silicon.

Preferably, in Formula 1, E may be sulfur (S).

Preferably, in Formula 1, R ₁ and R ₂ are the same or different and may each independently be methyl or phenyl.

Preferably, in Formula 1, R ₃ to R ₆ are the same or different, and may each independently be hydrogen, methyl, ethyl, propyl, or butyl.

Preferably, in Formula 1, R ₇ and R ₇ ' are the same or different, and may each independently be methyl, ethyl, phenyl, propyl, hexyl, or tert-butoxyhexyl.

As a first metallocene compound capable of providing a polyolefin exhibiting excellent polymerization activity and increased drop impact strength, the metallocene compound of Formula 1 may be any one selected from the group consisting of the following compounds, The invention is not limited to this:

In the above compounds,

Me is methyl,

Et is ethyl,

nPr is n-profile,

Hx is n-hexyl,

Ph is phenyl,

t-Bu means tert-butyl.

The metallocene compound represented by Chemical Formula 1 may be prepared, for example, by a production method as shown in Scheme 1 below, but is not limited thereto, and may be produced according to known production methods for organic compounds and metallocene compounds. The manufacturing method may be further detailed in the manufacturing examples described later.

[Scheme 1]

In Scheme 1, M, X ₁ , X ₂ , A, R ₁ to R ₇ ', and E is as defined in Formula 1 above.

In one embodiment of the invention, the second metallocene compound represented by Formula 2 includes an aromatic ring compound containing cyclopentadienyl or a derivative thereof and a nitrogen atom, and the aromatic ring compound and the nitrogen atom are bridged with each other. It has a structure that is cross-linked by groups A'R ₁₂ R ₁₂ '. The second metallocene compound having this specific structure can be applied to the polymerization reaction of olefin polymers, exhibits high activity and copolymerization, and can provide high molecular weight olefin polymers.

In particular, the second metallocene compound represented by Chemical Formula 2 has a well-known CGC (constrained geometry catalyst) structure, so it is excellent in introducing comonomers, and in addition, it is excellent in comonomer introduction due to the electronic and steric properties of the ligand. The distribution of monomers is controlled. From these properties, it is easy to manufacture polyolefin that exhibits excellent drop impact strength by controlling the average ethylene sequence length (ASL).

M' of the metallocene compound represented by Formula 2 may be a Group 4 transition metal, preferably titanium (Ti), zirconium (Zr), or hafnium (Hf).

Preferably, A' in Formula 2 may be silicon.

Preferably, in Formula ₂ , and X ₄ may each independently be methyl or chlorine (Cl).

Preferably, in Formula 2, R ₈ to R ₁₁ are the same or different, and may each independently be methyl or phenyl.

Preferably, in Formula 2, two or more of R ₈ to R ₁₁ adjacent to each other are connected to each other to form a substituted or unsubstituted aliphatic ring, an aromatic ring, or any selected from the group consisting of N, O, and S. It may form a heteroaromatic ring containing one or more. For example, in Formula 2, two or more adjacent R ₈ to R ₁₁ are connected to each other to form an aliphatic ring, an aromatic ring, or a heteroaromatic ring, so that an indenyl group is fused with cyclopentadiene; It can form a fluorenyl group, benzothiophene group, or dibenzothiophene group. Additionally, the indenyl group, fluorenyl group, benzothiophene group, and dibenzothiophene group may be substituted with one or more substituents.

Preferably, in Formula 2, R ₁₂ and R ₁₂ 'are the same or different, and may each independently be methyl, ethyl, phenyl, propyl, hexyl, or tert-butoxyhexyl.

Preferably, in Formula 2, R ₁₃ may be methyl, ethyl, n-propyl, iso-propyl, n-butyl, or ter-butyl.

As a second metallocene compound capable of providing a polyolefin exhibiting increased drop impact strength, the metallocene compound of Formula 2 may be any one selected from the group consisting of the following compounds, but the present invention provides this. It is not limited to:

The second metallocene compound represented by Formula 2 can be synthesized by applying known reactions. Specifically, it may be manufactured by connecting a nitrogen compound and a cyclopentadiene derivative with a bridge compound to prepare a ligand compound, and then performing metallation by adding a metal precursor compound, but is not limited to this and is described in more detail. For synthetic methods, refer to the examples.

In this way, the hybrid supported metallocene catalyst of one embodiment includes the first and second metallocene compounds, and can produce a polyolefin that not only has excellent activity but also has excellent physical properties, especially drop impact strength.

In particular, the mixing molar ratio of the first metallocene compound and the second metallocene compound is about 1:1 to about 1:10, preferably about 1:1 to about 1:5, and more preferably It may be about 1:1 to about 1:5 or about 1:1 to about 1:4. When the first metallocene compound and the second metallocene compound are in the molar ratio as described above, the polyolefin produced using them can satisfy the drop impact strength by adjusting the molecular weight, SCB, and ASL content and distribution to a predetermined range. You can.

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

As the carrier, a carrier containing a hydroxy group or a siloxane group on the surface can be used. Specifically, the carrier may be a carrier containing a highly reactive hydroxy group or siloxane group by drying at high temperature to remove moisture from the surface. More specifically, the carrier may be silica, alumina, magnesia, or a mixture thereof, 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 ( It may contain oxides such as NO ₃ ) ₂ , carbonate, sulfate, and nitrate.

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. If the drying temperature of the carrier is less than about 200°C, there is too much moisture, so the moisture on the surface reacts with the cocatalyst. If it exceeds about 800°C, the pores on the surface of the carrier merge and the surface area decreases, and hydroxyl residues form on the surface. This is undesirable because a lot of groups are lost and only siloxane groups remain, which reduces the number of reaction sites with the cocatalyst.

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

If the amount of the hydroxy group is less than about 0.1 mmol/g, there are few reaction sites with the cocatalyst, and if it exceeds about 10 mmol/g, it may be caused by moisture other than the hydroxy group present on the surface of the carrier particle. Not desirable.

In addition, in the hybrid supported metallocene catalyst of the above embodiment, the cocatalyst supported on the carrier to activate the metallocene compound is an organometallic compound containing a Group 13 metal, which can be used under a general metallocene catalyst. There is no particular limitation as long as it can be used when polymerizing olefin.

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

[Formula 3]

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

In Formula 3 above,

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

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 the +3 oxidation state, and G is each independently a hydride group, a dialkylamido group, a halide group, an alkoxide group, an aryloxide group, and a hydro group. is selected from the group consisting of a carbyl group, a halocarbyl group and a halo-substituted hydrocarbyl group, wherein G has up to 20 carbons, but at no more than one position G is a halide group.

The first cocatalyst of Formula 3 may be an alkylaluminoxane-based compound in which repeating units are bonded in a linear, circular, or network form. Specific examples of such first cocatalyst include methylaluminoxane (MAO), ethyl aluminoxane, Examples include oxalic acid, isobutyl aluminoxane, or butyl aluminoxane.

Additionally, the second cocatalyst of Formula 4 may be a borate-based compound in the form of a trisubstituted ammonium salt, dialkyl ammonium salt, or trisubstituted phosphonium salt. Specific examples of such second cocatalysts include trimetlammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, and tri(n-butyl)ammonium tetraphenylborate. , Methyltetradecyclooctadecylammonium tetraphenylborate, N,N-dimethylaninium tetraphenylborate, N,N-diethylanilium tetraphenylborate, N,N-dimethyl (2,4,6-trimethylaninium ) Tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl)borate, methylditetradecylammonium tetrakis(pentaphenyl)borate, methyldioctadecylammonium tetrakis(pentafluorophenyl)borate, triethylammonium, tetra Kiss(pentafluorophenyl)borate, Tripropylammonium tetrakis(pentafluorophenyl)borate, Tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, Tri(sec-butyl)ammonium tetrakis (pentafluorophenyl)borate, N,N-dimethylaninium tetrakis(pentafluorophenyl)borate, N,N-diethylanylniumtetrakis(pentafluorophenyl)borate, N,N-dimethyl(2 , 4,6-trimethylaninium) 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-diethylanilium tetrakis(2,3,4,6-tetrafluorophenyl)borate or N,N-dimethyl-(2,4,6-trimethylaninium) Borate-based 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-based compounds in the form of trisubstituted phosphonium salts such as borate.

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

Additionally, the mass ratio of co-catalyst compound to carrier may be 1:1 to 1:100. When the cocatalyst and carrier are included in the above mass ratio, the activity and polymer microstructure can be optimized.

The hybrid supported metallocene catalyst of one embodiment can be used as such for polymerization of olefin-based monomers. In addition, the hybrid supported metallocene catalyst may be prepared and used as a catalyst prepolymerized by contact reaction with an olefinic monomer. For example, the catalyst may be separately prepared with olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, etc. It can also be prepared and used as a catalyst prepolymerized by contact with a monomer.

Meanwhile, the hybrid supported metallocene catalyst of one embodiment includes the steps of supporting a cocatalyst on a carrier; Supporting the first and second metallocene compounds on a carrier carrying the cocatalyst; It can be manufactured by a manufacturing method comprising a.

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

In the above method, the loading conditions are not particularly limited and can be performed within a range well known to those skilled in the art. For example, high-temperature loading and low-temperature loading can be appropriately used. For example, the loading temperature can be 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 can be appropriately adjusted depending on the amount of metallocene compound to be loaded. The reacted supported catalyst can be used as is by removing the reaction solvent by filtration or distillation under reduced pressure. If necessary, it can be used after Soxhlet filtering with an aromatic hydrocarbon such as toluene.

In addition, the preparation of the supported catalyst may be performed under a solvent or without a solvent. When a solvent is used, usable solvents include aliphatic hydrocarbon solvents such as hexane or pentane, aromatic hydrocarbon solvents such as toluene or benzene, hydrocarbon solvents substituted with chlorine atoms such as dichloromethane, and ether-based solvents such as diethyl ether or THF. Solvents include most organic solvents such as acetone and ethyl acetate, and hexane, heptane, toluene, or dichloromethane are preferred.

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

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-dodene cen, 1-tetradecene, 1-hexadecene, 1-eicocene, norbornene, norbonadiene, ethylidene nobodene, phenylnobodene, vinylnobodene, dicyclopentadiene, 1,4-butadiene, 1, It may be one or more 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 the polymerization reaction of the olefin monomer may be employed, such as a continuous solution polymerization process, bulk polymerization process, suspension polymerization process, slurry polymerization process, or emulsion polymerization process. 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.

Additionally, in the polymerization reaction, the hybrid supported metallocene catalyst may be used dissolved or diluted in a solvent such as pentane, hexane, heptane, nonane, decane, toluene, benzene, dichloromethane, chlorobenzene, etc. At this time, by treating the solvent with a small amount of alkyl aluminum, etc., a small amount of water or air that may adversely affect the catalyst can be removed in advance.

In addition, polyolefin manufactured by the above method satisfies the predetermined physical properties described above and can exhibit low density and excellent transparency as well as high drop impact strength.

In addition, when the above-described 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-mentioned physical properties can be more appropriately satisfied. .

Below, preferred embodiments are presented to aid understanding of the present invention. However, the following examples are provided only to make the present invention easier to understand, and the content of the present invention is not limited thereto.

<Example>

Synthesis Example 1: First metallocene compound

Preparation of Ligand Compounds

Level 1:

Preparation of Bis(2,3-dimethyl-1H-benzo[b]cyclopenta[d]thiophen-1-yl)dimethylsilane

Dissolve 2,3-dimethyl-1H-benzo[b]cyclopenta[d]thiophene (1 equiv) in Toluene/THF (10/1, 0.5M) and then slowly add n-BuLi (1.05 eq) dropwise at -25℃. Then, it was stirred at room temperature for 3 hours. Afterwards, CuCN (3 mol%) was added and stirred for 30 minutes, dichloro dimethyl silane (0.5 eq) was added at -10°C, and then stirred at room temperature overnight. When the reaction was completed, work-up was performed using water and then dried to prepare a ligand.

Preparation of metallocene compounds

Step 2: Preparation of Dimethylsilane-diylbis(2,3-dimethyl-1H-benzo[b]cyclopenta[d]thiophen-1-yl)zirconium chloride

The ligand prepared in step 1 was dissolved in Toluene/Ether (2/1, 0.53M), n-BuLi (2.05 eq) was added at -25°C, and stirred at room temperature for 5 hours. ZrCl ₄ (1 eq) was added to the flask as a slurry in toluene (0.17 M) and stirred at room temperature overnight. When the reaction is completed, the solvent is vacuum dried, dichloromethane (DCM) is reintroduced, LiCl is removed through a filter, etc., the filtrate is vacuum dried, recrystallized using Hexane/DCM, and the resulting solid is filtered. A solid metallocene compound was obtained by vacuum drying.

¹ H-NMR (500 MHz, CDCl ₃ ): 7.88 (d, 2H), 7.77 (d, 2H) 7.29-7.33 (m, 4H), 2.38 (s, 6H), 1.78 (s, 6H), 0.21 ( s, 6H)ppm

Synthesis Example 2: First metallocene compound

Preparation of Ligand Compounds

Step 1: Preparation of Bis(6-butyl-2,3-dimethyl-1H-benzo[b]cyclopenta[d]thiophen-1-yl)dimethylsilane

6-butyl-2,3-dimethyl-1H-benzo[b]cyclopenta[d]thiophene (1 equiv) was dissolved in Toluene/THF (10/1, 0.5M) and then n-BuLi (1.05 eq) at -25°C. ) was slowly added dropwise and stirred at room temperature for 3 hours. Afterwards, CuCN (3 mol%) was added and stirred for 30 minutes, dichloro dimethyl silane (0.51 eq) was added at -10°C, and then stirred at room temperature overnight. When the reaction was completed, work-up was performed using water and then dried to prepare a ligand.

Preparation of metallocene compounds

Step 2: Preparation of Dimethylsilane-diylbis(6-butyl-2,3-dimethyl-1H-benzo[b]cyclopenta[d]thiophen-1-yl)zirconium chloride

The ligand prepared in step 1 was dissolved in Toluene/Ether (2/1, 0.53M), n-BuLi (2.05 eq) was added at -25°C, and stirred at room temperature for 5 hours. ZrCl ₄ (1 eq) was added to the flask as a slurry in toluene (0.17 M) and stirred at room temperature overnight. When the reaction is completed, the solvent is vacuum dried, dichloromethane (DCM) is reintroduced, LiCl is removed through a filter, etc., the filtrate is vacuum dried, recrystallized using Hexane/DCM, and the resulting solid is filtered. A solid metallocene compound was obtained by vacuum drying.

¹ H-NMR (500 MHz, CDCl ₃ ): 7.79 (m, 4H), 7.46 (d, 2H), 2.64 (t, 4H), 2.18 (s, 6H), 1.79 (s, 6H), 1.56 (m) , 4H), 1.40 (m, 4H), 1.32 (m, 4H), 0.89 (t, 6H), 0.21 (s, 6H) ppm

Synthesis Example 3: Second metallocene compound

Preparation of Ligand Compounds

1.2 mol (150 g) of tetramethylcyclopentadiene and 2.4 L of THF were added to the reactor, and then the temperature of the reactor was cooled to -20°C. 480 mL of n-BuLi was slowly added dropwise to the reactor. After adding n-BuLi, the reactor temperature was slowly raised to room temperature and stirred for 12 hours. After 12 hours of reaction, an equivalent amount of methyl(6-tert-butoxyhexyl)dichlorosilane (326 g) was quickly added to the reactor. The reactor temperature was slowly raised to room temperature and stirred for 12 hours, then the reactor temperature was cooled to 0°C, and 2 equivalents of t-BuNH ₂ was added. The reactor temperature was slowly raised to room temperature and stirred for 12 hours. After 12 hours of reaction, THF was removed, 4L of hexane was added, and a filter solution from which salts were removed was obtained through labrador. After adding the filter solution back to the reactor, hexane was removed at 70°C to obtain a yellow solution.

Preparation of metallocene compounds

THF was added to the ligand, cooled to -20°C, and n-BuLi was added. After reacting at room temperature for 4 hours, the reaction mixture was cooled to -78°C and TiCl ₂ (THF) ₂ was quickly added. The reaction solution was slowly raised to room temperature and stirred for 12 hours. Afterwards, an equivalent amount of PbCl ₂ was added to the reaction solution at room temperature and stirred for 12 hours. After stirring for 12 hours, a dark black solution with a blue tinge was obtained. After THF was removed from the resulting reaction solution, hexane was added and the product was filtered. Hexyne was removed from the obtained filter solution to obtain a metallocene compound.

1 H NMR (500 MHz, CDCl3): 3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 6H), 1.8 ~ 0.8 (m), 1.4 (s, 9H), 1.2 (s, 9H) , 0.7 (s,3H)

Synthesis Example 4: Second metallocene compound

Preparation of Ligand Compounds

11.1 mmol of 2,3-dimethyl-1H-benzo[b]cyclopenta[d]thiophene was dissolved in 55mL of THF, and n-BuLi (1.05eq, 4.7mL) was added dropwise at -78°C. After overnight reaction at RT, tether silane (1.05eq, 3.2g) was quantified in another Schlenk, then 30mL of THF was added and the temperature was lowered to 0°C. After transfer to the reaction solution, it was left overnight at RT. The solvent was dried, filtered with hexane, concentrated, and 30 mL of t-BuNH ₂ was added and reacted overnight at RT. After solvent drying, the product was filtered and concentrated with hexane, and 5g of brown syrup was obtained with a yield of 100%.

Preparation of metallocene compounds

5.4 mmol of the ligand compound obtained above was quantified in Schlenk and then dissolved in 30 mL of THF. n-BuLi (2.05eq, 4.4 mL) was added dropwise at -78°C and reacted overnight at RT. MMB (2.5eq, 4.5 mL) and TiCl ₄ (1eq, 5.4 mL) were added dropwise at -78°C and reacted overnight at RT. After vacuum drying and filtering with hexane, DME (3eq, 1.7 mL) was added dropwise. After overnight reaction at RT, the solvent was vacuum dried, filtered with hexane, and concentrated to obtain 2.2 g of catalyst.

1H NMR (500MHz, CDCl3): 7.9(d, 1H), 7.7(d, 1H), 7.5(dd, 1H), 7.4(dd, 1H), 3.3 (t, 2H), 2.1(s, 3H) , 1.8(s, 3H), 1.5-1.2(m, 8H), 1.2 (s, 9H), 1.1 (s, 9H), 0.9 (s, 6H), 0.1 (s,3H)

Comparative Synthesis Example 1

Preparation of Ligand Compounds

After dissolving 2-methyl-4-tert-butylphenylindene (20.0 g, 76 mmol) in toluene/THF=10/1 solution (230 mL), n-BuLi solution (2.5 M in hexane, 22g) was added. It was added slowly dropwise at 0°C, and then stirred at room temperature for one day. Afterwards, (6-tert-butoxyhexyl)dichloromethylsilane (1.27 g) was slowly added dropwise to the mixed solution at -78°C, stirred for about 10 minutes, and then stirred at room temperature for one day. Afterwards, water was added to separate the organic layer, and the solvent was distilled under reduced pressure to obtain (6-t-butoxyhexyl)(methyl)-bis(2-methyl-4-tert-butyl-phenylindenyl)silane.

Preparation of metallocene compounds

After dissolving the above ligand compound in toluene/THF=5/1 solution (95 mL), n-BuLi solution (22 g) was slowly added dropwise at -18°C and stirred at room temperature for one day. To the reaction solution, bis(N,N'-diphenyl-1,3,-propanediamido)dichlorozirconium bis(tetrahydrofuran) was dissolved in toluene (229 mL), then slowly added dropwise at -78°C and incubated at room temperature for one day. It was stirred for a while. After filtering and vacuum drying, hexane was added and stirred to precipitate crystals. The precipitated crystals were filtered and dried under reduced pressure to obtain a metallocene compound.

1H NMR (300 MHz, CDCl3): 1.20 (9H, s), 1.27 (3H, s), 1.34 (18H, s), 1.20-1.90 (10H, m), 2.25 (3H, s), 2.26 (3H, s), 3.38 (2H, t), 7.00 (2H, s), 7.09-7.13 (2H, m), 7.38 (2H, d), 7.45 (4H, d), 7.58 (4H, d), 7.59 (2H) , d), 7.65 (2H, d)

Comparative Synthesis Example 2

Preparation of Ligand Compounds

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

Preparation of metallocene compounds

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

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

^1H 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 3

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. This reaction mixture was quenched by adding 50 mL of water, extracted with ether (50 mL x 3), and the collected organic layer was thoroughly washed with brine. The remaining moisture was dried with MgSO ₄ and filtered, and the solvent was removed under reduced pressure to obtain a dark brown, viscous product, 2-butyl-cyclopenta-1,3-diene, in quantitative yield.

Preparation of metallocene compounds

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

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

^1H NMR (500MHz, 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)

Comparative Synthesis Example 4

Preparation of Ligand Compounds

Tetramethylcyclopentadiene (TMCP) was lithiated with n-BuLi (1 equivalent) in THF (0.4 M), filtered, 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. 50 mmol of tetramethylcyclopentyl-Li salts (TMCP-Li salts) and 100 mL of tetrahydrofuran (THF) were added to a 250 mL Schlenk flask under Ar. 1 equivalent of dichloromethylphenyl silane was added at -20°C. After about 6 hours, 3 mol% 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 the ligand.

Preparation of metallocene compounds

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

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

Comparative Synthesis Example 5

Preparation of Ligand Compounds

Tetramethylcyclopentadiene (TMCP) was lithiated with n-BuLi (1 equivalent) in THF (0.4 M), filtered, 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. 50 mmol of tetramethylcyclopentyl-Li salts (TMCP-Li salts) and about 100 mL of tetrahydrofuran (THF) were added to a 250 mL Schlenk flask 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 the ligand.

Preparation of metallocene compounds

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

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

^1H 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).

Comparative Synthesis Example 6

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 cooling the diethylether solution to 0°C, 18.4 mL (46 mmol) of 2.5 M nBuLi hexane solution was slowly added dropwise. The reaction mixture was slowly brought to room temperature and stirred until the next day. In another 250 mL Schlenk flask, a solution of 12.0586 g of dichloromethyltethersilane (40 mmol, calculated purity 90%) and 100 mL of hexane was prepared. This Schlenk flask was cooled to -30°C, and the lithiated solution was added dropwise thereto. The injected mixture was slowly raised to room temperature and stirred for a day. The next day, 33.6 mL of NaCp in 2M THF was added dropwise and stirred for a day. 50 mL of water was added to the flask for quenching, and the organic layer was separated and dried with MgSO ₄ . As a result, 23.511 g (52.9 mmol) of oil was obtained (NMR-based purity / wt% = 92.97%. Mw = 412.69).

Preparation of metallocene compounds

The ligand was placed in a 250 mL schlenk flask dried in an oven, dissolved in 80 mL of toluene and 19 mL (160 mmol, 4 equiv.) of MTBE, and then 2.1 equivalents of nBuLi solution (84 mmol, 33.6 mL) was added and lithiation was performed until the next day. 1 equivalent of ZrCl ₄ (THF) ₂ was taken from the glove box, placed in a 250 mL schlenk flask, and a suspension was prepared with Ether added. After cooling both flasks to -20°C, the ligand anion was slowly added to the Zr suspension. After injection was completed, the reaction mixture was slowly raised to room temperature. After stirring for a day, the MTBE in the mixture was immediately filtered under argon using a Schlenk Filter to remove LiCl produced after the reaction. After removal, the remaining filtrate was removed through reduced pressure under vacuum, and a volume of pentane equivalent to that of the reaction solvent was added to a small amount of dichloromethane. The reason for adding pentane at this time is that the synthesized catalyst precursor has low solubility in pentane, thereby promoting crystallization. This slurry was filtered under argon, and the remaining filter cake and filtrate were checked for catalyst synthesis through NMR, respectively, and the yield and purity were confirmed by weighing and sampling in a glove box (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)

<Preparation example of hybrid supported metallocene catalyst>

Manufacturing Example 1

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

2.0 kg of toluene was added to the reactor, and then the compound prepared in Synthesis Example 1 (17.5 mmol) and the compound prepared in Synthesis Example 3 (52.5 mmol) and 1000 mL of toluene were added. The temperature of the reactor was raised to 85°C and stirred for about 90 minutes.

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

Production example 2

A hybrid supported metallocene catalyst was prepared in the same manner as Preparation Example 1, except that the metallocene compounds of Synthesis Example 2 (17.5 mmol) and Synthesis Example 3 (52.5 mmol) were used.

Production example 3

A hybrid supported metallocene catalyst was prepared in the same manner as Preparation Example 1, except that the metallocene compounds of Synthesis Example 1 (17.5 mmol) and Synthesis Example 4 (52.5 mmol) were used.

Comparative Manufacturing Example 1

A hybrid supported metallocene catalyst was prepared in the same manner as Preparation Example 1, except that the metallocene compounds of Comparative Synthesis Example 2 (23.3 mmol) and Synthesis Example 3 (46.7 mmol) were used.

Comparative Manufacturing Example 2

A hybrid supported metallocene catalyst was prepared in the same manner as Preparation Example 1, except that the metallocene compounds of Comparative Synthesis Example 3 (23.3 mmol) and Synthesis Example 3 (46.7 mmol) were used.

Comparative Manufacturing Example 3

A hybrid supported metallocene catalyst was prepared in the same manner as Preparation Example 1, except that the metallocene compounds of Comparative Synthesis Example 1 (42.0 mmol) and Comparative Synthesis Example 4 (28.0 mmol) were used.

Comparative Manufacturing Example 4

A hybrid supported metallocene catalyst was prepared in the same manner as Preparation Example 1, except that the metallocene compounds of Comparative Synthesis Example 5 (60 mmol) and Comparative Synthesis Example 6 (10 mmol) were used.

<Polyolefin production 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, the reactants required for olefin polymerization were continuously added to the reactor as shown in Table 1.

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

The olefin polymerization reaction was carried out at a pressure of about 40 bar and a temperature of about 85 °C.

The main conditions of the polymerization reaction are shown in Table 1.

Example 1 Example 2 Example
3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative example
4 Comparative Example 5 catalyst Manufacturing Example 1
(Synthesis Example 1/Synthesis Example 3) Production example 2
(Synthesis Example 2/Synthesis Example 3) Manufacturing example
3
(Synthesis Example 1/Synthesis Example 4) Comparative Manufacturing Example 1
(Comparative Synthesis Example 2/Synthesis Example 3) Comparative Manufacturing Example 2
(Comparative Synthesis Example 3/Synthesis Example 3) Comparative Manufacturing Example 3
(Comparative Synthesis Example 1/Comparative Synthesis Example 4) Comparative Manufacturing Example 4
(Comparative Synthesis Example 5/Comparative Synthesis Example 6) Comparative Manufacturing Example 3
(Comparative Synthesis Example 1/Comparative Synthesis Example 4) Ethylene dosage (kg/hr) 25 25 25 25 25 25 25 24 Hydrogen input amount (ppm) 32 35 90 27 20 5 8 5 1-Hexene input amount (wt%) 13 13 14 12 12.5 13 12.5 13.0 Slurry Density (g/L) 556 557 560 560 554 555 558 555 activation
(kgPE/kgSiO ₂ ·hr) 5.7 6.0 7.8 4.3 3.2 5.1 3.0 4.4 Bulk density
(g/mL) 0.38 0.37 0.36 0.43 0.41 0.33 0.38 0.33 Settling efficiency
(%) 40 40 42 40 43 45 40 48

<Experimental example>

The physical properties of the polyolefin prepared in Examples and Comparative Examples were measured as follows, and the results are shown in Table 2 below.

(1) Density: Measured according to ASTM D1505 standards.

(2) Melt Index (MI): Measured according to ASTM D1238 (Condition E, 190 ℃, 2.16 kg load) standard.

(3) Molecular weight (Mn, Mw, g/mol) and molecular weight distribution (PDI, Mw/Mn)

The weight average molecular weight (Mw) and number average molecular weight (Mn) of polyolefin were measured using gel permeation chromatography (GPC, manufactured by Agilent), and the weight average molecular weight was divided by the number average molecular weight to obtain molecular weight distribution (PDI). ) was calculated.

Specifically, an Agilent PL-GPC220 instrument was used as a gel permeation chromatography (GPC) device, and a 300 mm long column from Polymer Laboratories PLgel MIX-B was used. At this time, the measurement temperature was 160°C, 1,2,4-trichlorobenzene was used as a solvent, and the flow rate was 1 mL/min. The polyolefin samples obtained in Examples and Comparative Examples were pretreated by dissolving them in 1,2,4-Trichlorobenzene (1,2,4-Trichlorobenzene) containing 0.0125% BHT at 160°C for 10 hours using a GPC analysis device (PL-GP220). , prepared at a concentration of 10 mg/10mL and then supplied in an amount of 200 μL. The values of Mw and Mn were derived using a calibration curve formed using a polystyrene standard specimen. The weight average molecular weight of polystyrene standard specimens is 2000 g/mol, 10000 g/mol, 30000 g/mol, 70000 g/mol, 200000 g/mol, 700000 g/mol, 2000000 g/mol, 4000000 g/mol, 10000000 g. Nine types of /mol were used.

(4) SCB (Short Chain Branch) content (content of side branches with 2 to 6 carbons per 1,000 carbons, unit: pieces/1,000C)

Samples were pretreated using PL-SP260VS by dissolving them in 1, 2, 4-Trichlorobenzene containing 0.0125% BHT at 160°C for 10 hours, then used PerkinElmer Spectrum 100 FT-IR connected to high temperature GPC (PL-GPC220). It was measured at 160°C.

(5) ASL (Average Ethylene Sequence Length)

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

The temperature was lowered from 160°C to 122°C, maintained for 20 minutes, lowered to 30°C, maintained for 1 minute, and then increased again. Next, it was heated to a temperature (117°C) that was 5°C lower than the initial heating temperature of 122°C and maintained for 20 minutes. The temperature was lowered to 30°C and maintained for 1 minute, and then the temperature was increased again. In this way, the n+1th heating temperature was 5°C lower than the nth heating temperature, the holding time and cooling temperature were the same, and the heating temperature was gradually lowered to 52°C. At this time, the temperature increase and decrease rates were adjusted to 20°C/min, respectively. Finally, the SSA thermogram was measured by increasing the temperature from 30℃ to 160℃ at a rate of 20℃/min and observing the change in heat quantity.

(6) Drop impact strength:

The polyolefin resin was inflation molded to a thickness of 60㎛ using a single screw extruder (Eugene Engineering Single Screw Extruder, Blown Film M/C, 50 Pie) at an extrusion temperature of 130 to 170°C. At this time, the die gap was set to 2.0 mm and the blow-up ratio was set to 2.3.

For the film manufactured in this way, measurements were taken at least 20 times per film sample according to the ASTM D1709 [Method A] standard, and the average value was taken.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Density (g/cm ³ ) 0.918 0.917 0.917 0.919 0.917 0.920 0.918 0.920 MI _2.16 (g/10min) 1.06 1.02 1.09 0.60 1.14 0.6 0.96 0.3 Mw(g/mol) 124,000 124,000 123,000 126,000 123,000 138,000 122,000 136,000 PDI 3.72 3.54 3.71 2.79 2.72 2.85 2.88 2.88 ASL≥22nm(wt%) 18 16 16 5 2 37 13 38 ASL≤8nm(wt%) 41 40 42 34 36 22 18 21 SCB 22.4 22.9 23.6 21.9 21.1 22.8 22.5 22.0 Drop impact strength
(g) 1,790 1,650 1,870 1,300 1,230 440 1,390 380

Referring to Table 2, the polyolefins of Examples 1 to 3 of the present invention showed very excellent drop impact strength of 1,650 g or more compared to Comparative Examples 1 to 5 having similar densities.

Claims (12)

A polyolefin that satisfies the conditions 1) to 3) below, comprising at least one first metallocene compound selected from compounds represented by the following formula (1); At least one second metallocene compound selected from compounds represented by the following formula (2); A polyolefin prepared by polymerizing olefin monomers in the presence of a hybrid supported metallocene catalyst comprising a carrier supporting the first and second metallocene compounds:
1) Density measured according to ASTM D1505 is 0.915 g/cm ³ to 0.930 g/cm ³ ;
2) a melt index (MI) of 0.5 to 1.5 g/10 min as measured according to ASTM D1238 at 190°C and a load of 2.16 kg; and
3) When analyzing SSA (Successive Self-nucleation and Annealing), the proportion of chains with an ASL (Average Ethylene Sequence Length) of 22 nm or more in length is 16% by weight or more relative to the total chain, and ASL (Average Ethylene Sequence Length) of 8 nm or less is measured. The proportion of chains is 38% by weight or more based on the total chain,
[Formula 1]

In Formula 1,
M is a group 4 transition metal,
_{X 1 and _}
A is carbon, silicon or germanium,
R ₁ and R ₂ are the same or different and are each independently C _1-20 alkyl, C _2-20 alkenyl, C _6-30 aryl,
R ₃ to R ₆ are the same or different, and are each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-30 aryl, C _7-30 alkylaryl, or C _7-30 arylalkyl ego,
R ₇ , R ₇ 'are the same or different, and are each independently C _1-20 alkyl, C _2-20 alkenyl, C _6-30 aryl, or C _2-20 alkoxy alkyl,
E is any one selected from the group consisting of sulfur (S), oxygen (O) and selenium (Se),
[Formula 2]

In Formula 2,
M' is a group 4 transition metal,
A' is carbon, silicon or germanium,
X ₃ and X ₄ are the same or different from each other and are each independently halogen or C _1-20 alkyl,
R ₈ to R ₁₁ are the same or different from each other, and are each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _6-20 aryl, C _7-20 alkylaryl, C _{7- 20} arylalkyl, or at least two of R ₈ to R ₁₁ adjacent to each other are connected to each other to form a substituted or unsubstituted aliphatic ring, an aromatic ring, or at least one selected from the group consisting of N, O, and S. Forming a heteroaromatic ring containing,
R ₁₂ and R ₁₂ 'are the same or different from each other, and are each independently C _1-20 alkyl, C _2-20 alkenyl, C _6-30 aryl, or C _2-20 alkoxy alkyl,
R ₁₃ is C _1-20 alkyl, C _2-20 alkenyl, or C _6-30 aryl.
According to paragraph 1,
The SSA heats the polyolefin to 120 to 124°C as the first heating temperature using a differential scanning calorimeter, maintains it for 15 to 30 minutes, and then cools to 28 to 32°C, and the n+1th heating temperature is Lower the heating temperature step by step to a temperature 3 to 7°C lower than the nth heating temperature, repeat heating-annealing-quenching until the final heating temperature is 50 to 54°C, and finally from 30°C to 160°C. Polyolefin, which is carried out by increasing the temperature to.
According to paragraph 1,
Polyolefin with SCB (Short Chain Branch) content of 22 pieces/1000C or more.
According to paragraph 1,
A polyolefin with a molecular weight distribution (PDI, Mw/Mn) of 3.3 to 4.0.
According to clause 1,
A polyolefin having a drop impact strength of 1,500 g or more as measured according to ASTM D 1709 [Method A] after producing a polyolefin film (BUR 2.3, film thickness 55 to 65 ㎛) using a film forming machine.
According to paragraph 1,
The polyolefin is a copolymer of ethylene and alpha olefin.
According to clause 6,
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-eicocene, norbornene, norbonadiene, ethylidene nobodene, phenylnobodene, vinylnobodene, dicyclopentadiene, 1,4-butadiene, 1,5-penta A polyolefin containing at least one member selected from the group consisting of diene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.
delete According to paragraph 1,
The compound represented by Formula 1 is a polyolefin, which is any one of the compounds represented by the following structural formula:

In the above compounds,
Me is methyl,
Et is ethyl,
nPr is n-profile,
Hx is n-hexyl,
Ph is phenyl,
t-Bu means tert-butyl.
According to paragraph 1,
The compound represented by Formula 2 is a polyolefin, which is any one of the compounds represented by the following structural formula:

According to paragraph 1,
A polyolefin wherein the molar ratio of the first and second metallocene compounds is 1:1 to 1:10.
According to paragraph 1,
The carrier is a polyolefin that is silica, alumina, magnesia, or a mixture thereof.