KR102602239B1 - Polyolefin - Google Patents

Abstract

The present invention relates to polyolefins. More specifically, the present invention relates to a polyolefin that has excellent drop impact strength and can exhibit 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 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 the density is 0.915 g/cm ³ In addition to the above, there is a need for the development of polyethylene that can realize transparency and excellent mechanical properties such as drop impact strength.

Korean Patent Publication No. 2010-0102854

In order to solve the problems of the prior art, the present invention has a density of 0.915 g/cm ³ The object of the present invention is to provide a polyolefin that has improved mechanical properties such as excellent drop impact strength and can exhibit improved transparency during film production.

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

density between 0.915 g/cm ³ and 0.930 g/cm ³ ; and

A polyolefin is provided in which the proportion of chains having an ASL (Average Ethylene Sequence Length) of 20 nm or more in length during SSA (Successive Self-nucleation and Annealing) analysis is 10% to 20% by weight 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 provide polyolefin with an optimal ASL (Average Ethylene Sequence Length) ratio. can do.

Accordingly, it is possible to provide polyolefin that has excellent transparency and 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.
Figure 2 is a graph showing the distribution of ASL of polyolefin according to an embodiment of the present invention.
Figure 3 is a graph showing the distribution of ASL of polyolefin according to a comparative example of the present invention.
Figure 4 is a graph showing the relationship between ASL and drop impact strength of polyolefins prepared in Examples and Comparative Examples 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 has a density of 0.915 g/cm ³ to 0.930 g/cm ³ ; And when analyzing SSA (Successive Self-nucleation and Annealing), the proportion of chains having an ASL (Average Ethylene Sequence Length) of 20 nm or more in length is 10% to 20% by weight 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

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 Not less than 0.919 g/cm ³ and 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 It may be less than /cm ³ . At this time, the density is a value measured according to ASTM D1505.

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-itocene, 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. Among these, 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.

According to one embodiment, in the polyolefin of the present invention, when analyzing SSA (Successive Self-nucleation and Annealing), the proportion of chains having an ASL (Average Ethylene Sequence Length) with a length of 20 nm or more is 10% or more in weight percent with respect to the total chain. % 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).

The inventors of the present invention found that, based on SSA (Successive Self-nucleation and Annealing) analysis, the proportion of chains with an ASL (Average Ethylene Sequence Length) of 20 nm or more in length, in weight percent based on the total chain, is 10% to 20%. The present invention was developed by focusing on the fact that when the density is below, it can have improved transparency and 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 20 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 20 nm or more.

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.

When calculated in the same manner as above, in the polyolefin of the present invention, the proportion of chains having an ASL (Average Ethylene Sequence Length) of 20 nm or more in length is 10% or more, or 11% or more, or 12% by weight relative to the total chain. % or more, but may be 20% or less, or 19% or less, or 18% or less, or 17% or less, or 16% or less.

By having the above ratio, the polyolefin of the present invention can achieve excellent film mechanical properties such as drop impact strength while maintaining a small amount of comonomer, i.e., low density characteristics of 0.930 g/cm ³ or less and high transparency.

In addition, the polyolefin according to one embodiment of the invention satisfies the characteristics as described above and has a melt index (MI _2.16 ) of 0.5 to 1.5 g measured under the temperature of 190 ° C and a load of 2.16 kg according to ASTM D1238 standard. It can be /10min. 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/10min or more. It may be less than 10 min, or less than 1.3 g/10 min.

In addition, the polyolefin according to one embodiment of the present invention is manufactured by using a film forming machine to produce a polyolefin film (BUR 2.3, film thickness 55 to 65㎛), and then the haze of the film measured according to ISO 13468 is It may be less than 12%. More specifically, the haze of the polyolefin according to one embodiment of the present invention may be 12% or less, or 11.5% or less, or 11% or less, or 10.5% or less. Since the lower the haze value, the better, 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 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. It 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, 1,400 g or less, 1,300 g or less, or 1,200 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.

Additionally, the polyolefin according to one 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 can be appropriately adjusted considering the use or application field of the polyolefin.

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,

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

R ₁ to R ₁₄ are the same or different from each other, and are 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 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 ones 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 or different from each other, and are each independently halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkoxyalkyl group, a C6 to C20 aryl group, and a C7 to C20 alkylaryl group. 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} , a C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;

R ₁₅ to R ₂₈ are the same or different from each other, and each independently represents hydrogen, halogen, a C1 to C20 alkyl group, a C1 to C20 haloalkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkoxyalkyl group, or a C1 to C20 alkyl group. 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 or different from each other, and are each independently a C1 to C20 alkyl group, or two or more adjacent R ₁₅ to R ₂₈ are connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring. is to form.

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

The C1 to C20 alkyl groups include straight or branched alkyl groups, and specifically include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, An octyl group, etc. may be mentioned, but it is not limited thereto.

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

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

The C1 to C20 alkoxy groups include methoxy group, ethoxy group, phenyloxy group, cyclohexyloxy group, etc., but are not limited thereto.

The C2 to C20 alkoxyalkyl group is a functional group in which one or more hydrogens of the alkyl group described above are replaced with an alkoxy group, and specifically, methoxymethyl group, methoxyethyl group, ethoxymethyl group, iso-propoxymethyl group, and iso-propoxy group. Alkoxyalkyl groups such as 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 replaced with 1 to 3 alkyl groups or alkoxy groups as described above, specifically methylsilyl group, die Alkylsilyl groups such as methylsilyl group, trimethylsilyl group, dimethylethylsilyl group, diethylmethylsilyl group, or dimethylpropylsilyl group; Alkoxysilyl groups such as methoxysilyl group, dimethoxysilyl group, trimethoxysilyl group, or dimethoxyethoxysilyl group; Alkoxyalkylsilyl groups such as methoxydimethylsilyl group, diethoxymethylsilyl group, or dimethoxypropylsilyl group may be included, but are 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 replaced with a silyl group, and specifically includes -CH ₂ -SiH ₃ , methylsilylmethyl group, or dimethylethoxysilylpropyl group. , but is not limited to this.

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

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

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

The above-mentioned substituents are optionally hydroxy groups within the range of achieving the same or similar effects as the desired effect; halogen; Alkyl group or alkenyl group, aryl group, alkoxy group; an alkyl group or alkenyl group, an aryl group, or an alkoxy group containing one or more heteroatoms from groups 14 to 16; silyl group; Alkylsilyl group or alkoxysilyl group; Phosphine group; phosphide group; Sulfonate group; and may be substituted with one or more substituents selected from the group consisting of a sulfone group.

The Group 4 transition metals include titanium (Ti), zirconium (Zr), and hafnium (Hf), but are not limited thereto.

Using the hybrid supported catalyst can maintain the transparency of polyolefin and secure excellent drop impact strength due to specific lamellar distribution, making it possible to manufacture polyolefin with high processability, especially excellent melt blown processability.

Specifically, in the hybrid supported catalyst according to one embodiment of the invention, the first metallocene compound contains long chain branches and is easy to produce low molecular weight polyolefin, and the second metallocene compound is the first metal locene compound. It contains a small amount of long chain branches compared to locene compounds and is easy to produce polyolefins with a relatively high molecular weight. In particular, the melt strength increases when there are many long chain branches in the polymer and the molecular weight is high. However, in the case of the first metallocene compound, there is a limit to improving bubble stability due to the low molecular weight compared to the many long chain branches.

In the present invention, a first metallocene compound that contains relatively many long chain branches and produces a low molecular weight polymer and a second metallocene compound that produces a polymer that contains relatively many short chain branches and a high molecular weight are mixed and supported to provide excellent transparency. Melt strength was improved while maintaining . By carrying the above two types of metallocene compounds in a hybrid form, the long chain branch present in the polymer is located at a relatively low molecular weight, so transparency does not deteriorate.

In particular, the hybrid supported catalyst of the present invention has the characteristic that the long chain branches generated by the first metallocene compound of Chemical Formula 1 and the long chain branches generated by the second metallocene compound of Chemical Formula 2 are entangled with each other at the molecular level. have The tangle between long chain branches requires a large force to be released from the molten state, thereby enhancing the melt strength. When the homopolymers were melted and mixed using each catalyst, no improvement in melt strength was observed, indicating that improvement in melt strength is effective when entanglement occurs from the polymerization stage by the hybrid supported catalyst.

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

Specifically, the cyclopentadienyl ligand in the structure of the metallocene compound represented by Formula 1 may, for example, affect 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 can 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 capable of polymerizing olefin monomers. It can exhibit very high activity in the process.

In addition, within the structure of the metallocene compound represented by Chemical Formula 1, it is stable and can exhibit high polymerization activity by having a lone pair of electrons that can act as a Lewis base in the tetrahydroindenyl ligand structure. The Nyl ligand can easily adjust the molecular weight of the polyolefin produced by, for example, controlling the degree of steric hindrance effect depending on the type of 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 hybrid supported catalyst can provide polyolefin with excellent processability.

In addition, within the structure of the metallocene compound represented by Formula 1, the cyclopentadienyl ligand and the tetrahydroindenyl ligand are cross-linked by -Si(Q ₁ )(Q ₂ )-, thereby showing excellent stability. there is. To ensure this effect more effectively, Q ₁ and Q ₂ may each independently be either 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.

In the _structure of _the metallocene compound represented by Formula 1, M ₁ ( It can go crazy. In order to more effectively ensure this effect, X ₁ and X ₂ may each independently be any one of halogen, C1 to C20 alkyl group, and C1 to C20 alkoxy group. More specifically, X ₁ and X ₂ may each independently be F, Cl, Br, or I, and M ₁ may be Ti, Zr, or Hf; is Zr or Hf; Or it could be Zr.

As an example, as a first metallocene compound that can provide a polyolefin with increased drop impact strength, a large content of short chain branches, and 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 can be synthesized by applying known reactions. Specifically, it can be prepared by connecting a tetrahydroindenyl derivative and a cyclopentadiene derivative with a bridge compound to prepare a ligand compound, and then adding a metal precursor compound to perform metallation, but it is not limited to this. , For more detailed synthesis methods, please refer to the examples.

Meanwhile, in the hybrid supported catalyst according to one embodiment of the invention, the metallocene compound represented by Formula 2 has a cyclopentadienyl ligand as a different ligand and a substituent (R ₂₀ and R ₂₄ ) at a specific position. It contains an indenyl ligand, and the different ligands are cross-linked by -Si(Q ₃ )(Q ₄ )-, and a structure in which M ₂ (X ₃ )(X ₄ ) exists between the different ligands have If a metallocene compound having such a specific structure is activated by an appropriate method and used as a catalyst for the polymerization reaction of olefins, long-chain branches can be created. In this way, by introducing substituents (R ₂₀ and R ₂₄ ) at specific positions of the indene derivative of Formula 2, compared to an unsubstituted indene compound or a metallocene compound containing an indene compound substituted at another position, polymerization activity It can have these high characteristics.

In particular, in the case of the second metallocene compound represented by Formula 2, when polymerized alone, it has a molecular weight of about 150,000 to 550,000 and has the characteristic of having SCB, so when applied to a hybrid catalyst, it has a narrow molecular weight distribution and improves processability. There are characteristics that can be improved.

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

In particular, when 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, Catalysts obtained from metallocene compounds can exhibit higher activity in the olefin polymerization process, and R ₂₅ and R ₂₈ are each hydrogen, and R ₂₆ and R ₂₇ are each independently hydrogen, an alkyl group of C1 to C20, or a C2 to In the case of a C20 alkoxyalkyl group, the hybrid supported catalyst can exhibit very high activity in the polymerization process of olefin monomers.

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

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

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 C20 alkoxy group. It may be a C20 arylalkyl group.

Additionally, within 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 )-, thereby showing excellent stability. In order to more effectively ensure this effect, Q ₃ and Q ₄ may each independently be either a C1 to C20 alkyl group or a C2 to C20 alkoxyalkyl group. More specifically, Q ₃ and Q ₄ are each independently methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, t-butyl group, methoxymethyl group, methoxyethyl group, ethoxymethyl group, iso -A metallocene compound that is any one of propoxymethyl group, iso-propoxyethyl group, iso-propoxyhexyl group, tert-butoxymethyl group, tert-butoxyethyl group, and tert-butoxyhexyl group can be used.

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

This is because the C2 to C20 alkoxyalkyl group may affect the copolymerization of alpha olefin comonomers such as 1-butene or 1-hexene, where the alkoxyalkyl group is C4 or lower. This is because, in the case of having a short alkyl group chain, comonomer incorporation with respect to alpha olefin comonomer is lowered while maintaining overall polymerization activity, making it possible to produce polyolefin with a controlled degree of copolymerization without deterioration of other physical properties.

In addition _, in the structure of _the metallocene compound represented by Formula 2, M ₂ ( It can have an impact. In order to ensure this effect more effectively, X ₃ and X ₄ may each independently be any one of halogen, C1 to C20 alkyl group, and C1 to C20 alkoxy group. More specifically, X ₃ and X ₄ may each independently be F, Cl, Br or I, and M ₂ may be Ti, Zr or Hf; is Zr or Hf; Or it could be Zr.

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

, ,

,

In this way, the hybrid supported metallocene catalyst of one embodiment includes the first and second metallocene compounds, and can produce polyolefin that not only has excellent processability but also 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 10:1, preferably about 1.2:1 to 7.5:1, and more preferably 1.5: It may be 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 controlling physical properties to satisfy both physical properties and processability by adjusting the molecular weight and the amount of SCB and LCB, In terms of ensuring processability, it can be 10:1 or less.

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.

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 can exhibit high drop impact strength along 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 when analyzing SSA (Successive Self-nucleation and Annealing), the proportion of chains with an ASL (Average Ethylene Sequence Length) of 20 nm or more in length is In weight percent relative to the chain, it may be 10% to 20%.

In addition, the polyolefin may have 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 the ASTM D1238 standard.

In addition, the polyolefin may have a haze of 12% or less as measured according to ISO 13468 after producing a polyolefin film (BUR 2.3, film thickness 55 to 65 ㎛) using a film forming machine.

In addition, the polyolefin may have a drop impact strength of 850 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.

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

1-1 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% 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.

1-2 Preparation of metallocene compounds

50 mmol of the ligand compound synthesized in 2-1 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).

Synthesis Example 2: Second metallocene compound

2-1 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 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).

2-2 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 vacuum decompression, and a volume of pentane equivalent to 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)

Synthesis Example 3: First metallocene compound

3-1 Preparation of ligand compounds

Tetramethylcyclopentadiene (TMCP, 3.6 g, 30 mmol) was dissolved in THF (70 mL) in a dried 500 mL schlenk flask, and then the solution was cooled to -78°C. Next, n-BuLi (2.5M, 13mL, 32mmol) was slowly added dropwise to the solution, and the resulting solution was stirred at room temperature overnight.

Meanwhile, dichloro(methyl)propylsilane was dissolved in n-hexane in a separate 500mL schlenk flask, and then this solution was cooled to -78°C. Subsequently, the previously prepared TMCP-lithiation solution was slowly injected into this solution. Then, the resulting solution was stirred at room temperature overnight to obtain an intermediate.

¹ H NMR (500 MHz, CDCl ₃ ): 0.21 (3H, s), 0.94 (3H, t), 1.26-1.42 (4H, m), 1.81 (6H, s), 1.98 (6H, s), 3.10 ( 1H, s).

After dissolving indene (3.5 mL, 30 mmol) in THF (50 mL) in a dried 500 mL schlenk flask, the solution was cooled to -78°C. Next, n-BuLi (2.5M, 13mL, 32mmol) was slowly added dropwise to the solution, and the resulting solution was stirred at room temperature for about 1.5 hours.

Meanwhile, the previously synthesized intermediate was dissolved in THF in a separate 500mL schlenk flask, and this solution was cooled to -78°C. Subsequently, the previously prepared indene-lithiation solution was slowly injected into this solution. Then, the resulting solution was stirred at room temperature for about 2 hours to obtain a purple solution.

Afterwards, water was poured into the reactor to terminate the reaction (quenching), and the organic layer was extracted from the mixture with ether. Then, the organic layer was reduced in pressure to remove the solvent, thereby obtaining a product in the form of a yellow oil (9.7 g, 30 mmol, > 99% yield).

¹ H NMR (500 MHz, CDCl ₃ ): -0.57 (1.5H, s), -0.29 (1.5H, s), -0.11 (3H, s), 0.72 (3H, t), 1.07-1.28 (4H, m), 1.59 (6H, d), 1.66 (6H, d), 2.86-3.06 (1H, m), 3.22-3.25 (1H, m), 6.33 (1H, dd), 6.68 (1H, d), 6.97 -7.12 (2H, m), 7.20-7.36 (2H, m).

3-2 Preparation of metallocene compounds

In a dried 250mL schlenk flask, previously synthesized methylpropyl(indenyl)(tetramethylcyclopentadienyl)silane (9.7g, 30mmol) was dissolved in THF (80mL). Then, this solution was cooled to -78°C, and then n-BuLi (2.5M, 25mL, 63mmol) was slowly added dropwise to the solution, and the resulting solution was stirred at room temperature overnight.

Meanwhile, ZrCl ₄ (THF) ₂ (3.7 g, 9.7 mmol) was dispersed in toluene (80 mL) in a separately prepared 250 mL schlenk flask, and the resulting mixture was cooled to -78°C. Subsequently, the previously prepared lithiated ligand solution was slowly injected into the mixture. Then, the resulting mixture was stirred overnight to obtain an orange-colored suspension.

The suspension was reduced in pressure to remove half of the solvent, and the suspension was filtered to remove LiCl contained in the suspension. Afterwards, the solvent was removed from the filtered solution, and the resulting material was precipitated in toluene and pentane to obtain an orange solid product (8.7g, 18mmol, 60% yield).

¹ H NMR (500 MHz, CDCl ₃ ): 0.95 (3H, s), 1.15 (3H, s), 1.22 (2H, t), 1.17 (3H, t), 1.90 (3H, s), 1.74-1.80 ( 2H, m), 1.92 (3H, s), 1.97 (6H, t), 5.98 (1H, d), 7.07 (1H, t), 7.23 (1H, m), 7.35 (1H, t), 7.45-7.50 (1H, m), 7.70 (1H, d).

The previously synthesized methylpropylsilylene (tetramethylcyclopentadienyl)(indenyl)zirconium dichloride (4.837g, 10mmol) was placed in a mini bombe in the glove box. Then, platinum oxide (0.227g, 1.0mmol) was additionally added to the mini bombe, and after assembling the mini bombe, anhydrous THF (50mL) was added to the mini bombe using a canuula, and hydrogen was added to a pressure of about 30 bar. Filled. Next, the mixture contained in the mini bombe was stirred at about 60°C for about 1 day, then the temperature of the mini bombe was cooled to room temperature, and the pressure of the mini bombe was gradually lowered while hydrogen was replaced with argon.

Meanwhile, celite dried in an oven at about 120°C for about 2 hours was spread 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. Next, the reaction product from which the catalyst was removed was subjected to reduced pressure to remove the solvent, and a product as an off-white sticky solid was obtained (2.8 g, 5.75 mmol, Mw: 486.71 g/mol). This solid was prepared as a stock solution by dissolving in toluene and stored in the refrigerator.

¹ H NMR (500 MHz, CDCl ₃ ): 0.80 (3H, s), 0.86 (3H, s), 1.12 (2H, m), 1.32 (2H, m), 1.41 (2H, s), 1.54 (2H, m), 1.65 (2H, m), 1.84 (2H, m), 1.91 (6H, d), 1.93 (3H, s), 1.99 (3H, s), 2.25 (2H, m), 2.37 (2H, m) ), 2.54 (2H, m), 2.99 (2H, m), 5.45 (1H, s), 6.67 (1H, s).

Synthesis Example 4: Second metallocene compound

4-1 Preparation of ligand compounds

6-tert-butoxyhexyl chloride and sodium cyclopentadiene (2 equivalents) were added and stirred under THF. After completion of the reaction, the reaction was worked up 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, 8.8 mL (22 mmol) of 2.5 M n-BuLi Hexane solution was added dropwise, and the mixture was stirred at room temperature overnight.

5.8 g (20 mmol) of 4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-indene was added to a dried 250 mL Schlenk flask, and 33 mL of MTBE was added. The temperature was lowered to -20°C, 8.8 mL (22 mmol) of 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.

The lithiated solution of 6-tert-butoxyhexylcyclopentadiene was added to the above flask and stirred overnight. The ligand synthesized through this process was worked up to obtain a ligand compound.

4-2 Preparation of metallocene compounds

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

Synthesis Example 5: First metallocene compound

5-1 Preparation of ligand compounds

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

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

Afterwards, the resulting solution was reduced in pressure to remove the solvent from the solution. Then, the resulting 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 (0.93mL, 8.0mmol) was dissolved in THF (30mL) in a dried 250mL schlenk flask, and then the solution was cooled to -78°C. Next, 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, the previously synthesized intermediate (1.7 g, 8.0 mmol) was dissolved in THF in a separate 250 mL schlenk flask, and this solution was cooled to -78°C. Subsequently, 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.

Afterwards, water was poured into the reactor to terminate the reaction (quenching), and the organic layer was extracted from the mixture with ether. It was confirmed through ¹ H NMR that the organic layer contained dimethyl(indenyl)(tetramethylcyclopentadienyl)silane and other types of organic compounds. The organic layer was concentrated without purification and used as is for metallation.

5-2 Preparation of metallocene compounds

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

Meanwhile, ZrCl ₄ (THF) ₂ was dispersed in toluene in a separately prepared 250mL schlenk flask, and the resulting mixture was cooled to -78°C. Subsequently, the previously prepared lithiated ligand solution was slowly injected into the mixture. Then, the resulting mixture was stirred overnight.

Afterwards, the reaction product was filtered to obtain a yellow solid (1.3g, including LiCl (0.48g), 1.8mmol). After removing the solvent from the filtrate, it was washed with n-hexane to obtain a yellow solid (320mg, 0.70mmol). 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 previously was placed in a mini bombe in a glove box. Then, platinum oxide (52.4 mg, 0.231 mmol) was added to the mini bombe, and after assembling the mini bombe, anhydrous THF (30 mL) was added to the mini bombe using a canuula, and hydrogen was added to a pressure of about 30 bar. Filled. Next, the mixture contained in the mini bombe was stirred at about 60°C for about 1 day, then the temperature of the mini bombe was cooled to room temperature, and the pressure of the mini bombe was gradually lowered while hydrogen was replaced with argon.

Meanwhile, celite dried in an oven at about 120°C for about 2 hours was spread 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. Next, the reaction product from which the catalyst was removed was subjected to reduced pressure to remove the solvent, and a light yellow solid product was obtained (0.601g, 1.31mmol, Mw: 458.65g/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).

Comparative Synthesis Example 1: Second metallocene compound

1-1 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)

1-2 metallocene Preparation of Compounds

In addition, 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 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. 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.

2-2 Preparation of metallocene compounds

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. 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)

<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. 5.7 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 (60 mmol), the compound prepared in Synthesis Example 2 (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.

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 3 (60 mmol) and Synthesis Example 2 (10 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 3 (60 mmol) and Synthesis Example 4 (10 mmol) were used.

Production example 4

A hybrid supported metallocene catalyst was prepared in the same manner as Preparation Example 1, except that the metallocene compounds of Synthesis Example 5 (60 mmol) and Synthesis Example 4 (10 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 Synthesis Example 3 (60 mmol) and Comparative Synthesis Example 1 (10 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 Synthesis Example 1 (60 mmol) and Comparative Synthesis Example 2 (10 mmol) were used.

Comparative Manufacturing Example 3

A hybrid supported metallocene catalyst was prepared in the same manner as Preparation Example 1, except that only the metallocene compound of Synthesis Example 3 (70 mmol) was used.

The main components of the above preparation examples and comparative preparation examples are shown in Table 1 below.

Manufacturing Example 1 Production example 2 Production example 3 Production example 4 Comparative Manufacturing Example 1 Comparative Manufacturing Example 2 Comparative Manufacturing Example 3 Support
form concoction
Support concoction
Support concoction
Support concoction
Support concoction
Support concoction
Support single
Support Metallocene compound composition Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 4 Synthesis Example 3 Comparative Synthesis Example 1 Synthesis Example 1 Comparative Synthesis Example 2 Synthesis Example 3 Transition metal compound ratio (molar ratio) 6:1 6:1 6:1 6:1 6:1 6:1 -

<Polyolefin manufacturing Example >

Ethylene-1-hexene copolymerization

The supported catalyst (90 mg) prepared in the examples and comparative examples was weighed in a dry box, placed in a 50 mL glass bottle, sealed with a rubber septum, and taken out of the dry box to prepare the catalyst for injection. Polymerization was carried out in a 2 L autoclave high pressure reactor equipped with a mechanical stirrer, temperature controlled, and available at high pressure.

2 mL of triethylaluminum (1M in Hexane) was added to the reactor, 0.6 kg of hexane was added, and the temperature was raised to 80°C while stirring at 500 rpm. The hybrid supported metallocene catalyst (90 mg) and hexane (20 mL) prepared above were placed in a vial and added to the reactor, followed by 50 g of 1-hexene and 0.2 kg of hexane. When the temperature inside the reactor reached 80°C, the reaction was performed for 1 hour while stirring at 500 rpm under an ethylene pressure of 30 bar. After completion of the reaction, hexane was first removed from the polymer obtained through a filter, and then dried in an oven at 80°C for 3 hours to obtain an ethylene-1hexene copolymer.

The main conditions of the polymerization reaction are shown in Table 2.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative example 3 catalyst Manufacturing Example 1 Production example 2 Production example 3 Production example 4 Comparative Manufacturing Example 1 Comparative Manufacturing Example 2 Comparative Manufacturing Example 3 Ethylene dosage (kg/hr) 40 40 40 40 40 40 40 Hydrogen input amount (ppm) 15 15 18 17 11 11 17 Hexene input amount (wt%) 10 11 11 12 13 12.5 14 Slurry Density (g/L) 557 560 560 562 561 558 561 Activity (kgPE/kgSiO2·hr) 5.0 5.2 7.1 6.5 7.0 6.9 4.1 Bulk density (g/mL) 0.43 0.41 0.42 0.42 0.40 0.42 0.39

< Experiment example >

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

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

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

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

(4) Haze: Using a single screw extruder (Eugene Engineering Single Screw Extruder, Blown Film M/C, 50 pi), inflation molding was performed to a thickness of 60㎛ at an extrusion temperature of 130 ~ 170℃. At this time, the die gap was set to 2.0 mm and the blow-up ratio was set to 2.3. The film prepared in this way was measured according to ISO 13468 standards. At this time, each specimen was measured 10 times and the average value was taken.

(4) Drop impact strength: After manufacturing the polymer film under the same conditions as (3), the average value was taken by measuring at least 20 times per film sample according to the ASTM D1709 [Method A] standard.

(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.

A graph showing the distribution of the ASL of the polyolefin according to Example 3 of the present invention according to the length is shown in FIG. 2, and a graph showing the distribution of the ASL of the polyolefin according to Comparative Example 2 according to the length is shown in FIG. 3.

In addition, a graph showing the relationship between ASL and drop impact strength of polyolefins prepared in Examples and Comparative Examples of the present invention is shown in Figure 4.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Density (g/cm ³ ) 0.920 0.920 0.920 0.920 0.920 0.920 0.918 MI _2.16 (g/10min) 1.25 1.25 1.00 1.07 1.40 1.03 1.0 Haze (%) 10.4 10.6 10.1 10.8 9.6 10.5 22.0 ASL ≥ 20nm
(%) 13 13 11 14 7 9 29 Drop impact strength
(g) 920 950 1,020 1,040 760 830 1,000

Referring to Table 3 and Figures 2 to 4, the polyolefins of Examples 1 to 4 of the present invention have a haze of 12% or less and a drop impact strength of 850 g or more compared to Comparative Examples 1 to 3 having the same density. It showed high transparency and excellent drop impact strength in terms of density.

In particular, referring to Figure 4, it can be seen that there is a close relationship between the proportion of ASLs with a length of 20 nm or more and the drop impact strength, and even at the same density, the drop impact strength is significantly improved when the ASL with a length of 20 nm or more is 10% or more. there is.

Claims (11)

density between 0.915 g/cm ³ and 0.930 g/cm ³ ; and
When analyzing SSA (Successive Self-nucleation and Annealing), the proportion of chains with an ASL (Average Ethylene Sequence Length) of 20 nm or more in length is 10% to 20% in weight percent based on the total chain,
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); 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,
Polyolefin:
[Formula 1]

In Formula 1,
Q ₁ and Q ₂ are the same or different from each other, and are each independently halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkoxyalkyl group, a C6 to C20 aryl group, and a C7 to C20 alkylaryl group. 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} , a C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;
R ₁ to R ₁₄ are the same or different from each other, and are 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 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 ones 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 or different from each other, and are each independently halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkoxyalkyl group, a C6 to C20 aryl group, and a C7 to C20 alkylaryl group. 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} , a C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;
R ₁₅ to R ₂₈ are the same or different from each other, and each independently represents hydrogen, halogen, a C1 to C20 alkyl group, a C1 to C20 haloalkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkoxyalkyl group, or a C1 to C20 alkyl group. 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 or different from each other and are each independently a C1 to C20 alkyl group.
According to clause 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 clause 1,
A polyolefin having a melt index (MI _2.16 ) of 0.5 to 1.5 g/10 min, measured according to the ASTM D1238 standard at a temperature of 190° C. and a load of 2.16 kg.
According to clause 1,
After producing a polyolefin film (BUR 2.3, film thickness 55 to 65㎛) using a film forming machine, the polyolefin has a haze of 12% or less as measured according to ISO 13468.
According to clause 1,
A polyolefin having a drop impact strength of 850 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 clause 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-itocene, 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 and 1,6-hexadiene.
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:
, , , ,
, , ,
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 10:1.