KR20220076377A - Method for preparing a polyolefin - Google Patents

Abstract

The present invention relates to a method for producing polyolefin in which polymerization stability and productivity of a supported catalyst are improved by using the interaction between a scavenger and a supported catalyst used for polyolefin production.

Description

The manufacturing method of polyolefin {METHOD FOR PREPARING A POLYOLEFIN}

The present invention relates to a method for producing a polyolefin with improved polymerization stability and productivity of a supported catalyst.

In the case of resins used for food containers, excellent processability, mechanical properties, and stress cracking resistance are required. Therefore, there has been a continuous demand for a technology for producing polyolefins that can be preferably used as containers or bottle caps by satisfying a large molecular weight, a broader molecular weight distribution, and a desirable comonomer distribution.

On the other hand, the metallocene catalyst consists of a combination of a main catalyst containing a transition metal compound as a main component and a cocatalyst containing an organometallic compound containing aluminum as a main component. Such a catalyst is a homogeneous complex catalyst and exhibits the characteristics of a single site catalyst. According to the single site characteristic, a molecular weight distribution is narrow, a polymer with a uniform composition distribution of comonomer is obtained, and the catalyst It has the ability to change the stereoregularity, copolymerization characteristics, molecular weight, crystallinity, etc. of the polymer according to the modification of the ligand structure and the change of polymerization conditions. Therefore, morphology control of a polymer prepared using a catalyst supported with a metallocene compound is the most important in a polyolefin polymerization process, and determines polymerization productivity during a commercial process.

To this end, many studies have been conducted to improve the binding force with the carrier by changing the manufacturing conditions of the supported catalyst in slurry polymerization, or to introduce a tether structure to the metallocene precursor compound to create a supported catalyst structure without movement. However, in the case of catalysts that need to support a precursor without a tether, it is difficult to control morphological stability using the above method alone.

Accordingly, there is a need to develop a polyolefin production method that improves polymerization stability by improving interaction with a supported catalyst even when a tether-free precursor compound is used.

An object of the present invention is to provide a method for producing polyolefin in which polymerization stability and productivity of a supported catalyst are improved by using the interaction between a scavenger and a supported catalyst used for polyolefin production.

The present invention relates to a metallocene compound represented by the following formula (1); cocatalyst compounds; and preparing a supported metallocene catalyst comprising a carrier (1);

any one of triisobutylaluminum (TIBAL), triethylaluminum (TEAL) and trioctyl aluminum (TOA); And preparing a polymerization promoter composition comprising a steric hindered phenol (sterically hindered phenol compound) (2); and

Containing; comprising a;

A method for preparing polyolefin is provided:

[Formula 1]

In Formula 1,

R ₁ to R ₈ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkoxy or C _2-20 alkoxyalkyl, or adjacent R ₁ to R ₈ are bonded to each other to form a C _6-60 aromatic ring,

R ₉ and R ₉ ^' are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkoxy or C _2-20 alkoxyalkyl, or R ₉ and R _9' are bonded to each other to form a C _2-10 aliphatic ring or a C _6-60 aromatic ring,

A is silicon (Si) or carbon (C),

k is an integer equal to 0 or 1,

M is a group 4 transition element,

each X is independently halogen or C _1-20 alkyl.

In the polyolefin prepared according to one embodiment of the present invention, additives that react with the polymerization promoter are used in the polymerization process of the polyolefin, so that the polymerization promoter becomes bulky, thereby determining whether the precursor of the supported metallocene catalyst has a tether. Regardless, it shows a stable morphology, forms uniform particles, and has an improved bulk density (BD), thereby improving the stability and productivity of polyolefin polymerization.

The terminology used herein is used to describe exemplary embodiments only, and is not intended to limit the present invention.

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

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

Unless otherwise limited herein, the following terms may be defined as follows.

The halogen may be fluoro (F), chloro (Cl), bromo (Br) or iodo (I).

The alkyl may be straight-chain or branched-chain 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 chain alkyl; C _3-15 branched chain alkyl; or C _3-10 branched chain alkyl. More specifically, C _1-20 alkyl is a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, or iso-pentyl group, etc. but is not limited thereto. Meanwhile, in the present specification, "iPr" refers to an iso-propyl group.

The cycloalkyl may be a cyclic alkyl. Specifically, the C _3-20 cycloalkyl is C _3-20 cyclic alkyl; C _3-15 cyclic alkyl; or C _3-10 cyclic alkyl. More specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto. Meanwhile, in the present specification, "Cy" means cycloalkyl having 3 to 6 carbon atoms.

The alkenyl may 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 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, and the like.

The alkoxy may be a straight-chain, branched-chain or cyclic alkoxy group. Specifically, the C _1-20 alkoxy is a C _1-20 straight-chain alkoxy group; C _1-10 straight chain alkoxy; C _1-5 straight chain alkoxy group; C _3-20 branched or cyclic alkoxy; C _3-15 branched or cyclic alkoxy; or C _3-10 branched or cyclic alkoxy. More specifically, C _1-20 alkoxy is a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, tert-butoxy group, n-pentoxy group, iso- a pentoxy group, a neo-pentoxy group, or a cyclohexoxy group, but is not limited thereto.

The alkoxyalkyl may have a structure including -Ra-O-Rb and may be a substituent in which one or more hydrogens of alkyl (-Ra) are substituted with alkoxy (-O-Rb). Specifically, the C _2-20 alkoxyalkyl is a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an iso-propoxymethyl group, an iso-propoxyethyl group, an iso-propoxyhexyl group, a tert-butoxymethyl group, tert- butoxyethyl group or tert-butoxyhexyl group, but is not limited thereto.

The aryl includes monocyclic, bicyclic or tricyclic aromatic hydrocarbons. According to an embodiment of the present invention, the aryl group may have 6 to 60 carbon atoms or 6 to 20 carbon atoms, specifically phenyl, naphthyl, anthracenyl, dimethylanilinyl, anisolyl, etc., but is not limited thereto.

The heteroaryl is a heteroaryl containing at least one of O, N, and S as a heterogeneous element, 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 heteroaryl include xanthene, thioxanthen, thiophene, furan, pyrrole, imidazole, thiazole, oxazole, oxadiazole, triazole, pyridyl, bipyridyl, Pyridinyl group, pyrimidyl group, triazine group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyridopyrazinyl group group, pyrazino pyrazinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, a phenanthroline group, an isoxazolyl group, a thiadiazolyl group, a phenothiazinyl group, a dibenzofuranyl group, and the like, but is not limited thereto.

The hydrocarbyl group refers to a monovalent hydrocarbon compound, and an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, an aralkenyl group, an aralkynyl group, an alkylaryl group, an alkenylaryl group group and an alkynylaryl group; and the like. As an example, the hydrocarbyl group can be a straight chain, branched chain or cyclic alkyl. More specifically, the hydrocarbyl group having 1 to 30 carbon atoms is a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, an n-pentyl group, and a n-hexyl group. straight-chain, branched-chain or cyclic alkyl groups such as a sil group, n-heptyl group, and cyclohexyl group; or an aryl group such as phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, or fluorenyl. In addition, it may be an alkylaryl such as methylphenyl, ethylphenyl, methylbiphenyl, or methylnaphthyl, and may be an arylalkyl such as phenylmethyl, phenylethyl, biphenylmethyl, or naphthylmethyl. In addition, it may be an alkenyl such as allyl, allyl, ethenyl, propenyl, butenyl, pentenyl.

The heterocycle includes both an aliphatic ring including any one or more selected from the group consisting of N, O, and S, and an aromatic ring including any one or more selected from the group consisting of N, O and S.

And, the Group 4 transition metal may be titanium (Ti), zirconium (Zr), hafnium (Hf), or rutherpodium (Rf), specifically, titanium (Ti), zirconium (Zr), or hafnium (Hf) may be, and more specifically, may be zirconium (Zr) or hafnium (Hf), but is not limited thereto.

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

Hereinafter, the present invention will be described in detail.

According to an aspect of the present invention, a metallocene compound represented by the following formula (1); cocatalyst compounds; and preparing a supported metallocene catalyst comprising a carrier (1);

any one of triisobutylaluminum (TIBAL), triethylaluminum (TEAL) and trioctyl aluminum (TOA); And preparing a polymerization promoter composition comprising a steric hindered phenol (sterically hindered phenol compound) (2); and

Containing; comprising a;

A method for preparing a polyolefin is provided:

[Formula 1]

In Formula 1,

R ₁ to R ₈ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkoxy or C _2-20 alkoxyalkyl, or adjacent R ₁ to R ₈ are bonded to each other to form a C _6-60 aromatic ring,

R ₉ and R ₉ ^' are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkoxy or C _2-20 alkoxyalkyl, or R ₉ and R _9' are bonded to each other to form a C _2-10 aliphatic ring or a C _6-60 aromatic ring,

A is silicon (Si) or carbon (C),

k is an integer equal to 0 or 1,

M is a group 4 transition element,

each X is independently halogen or C _1-20 alkyl.

In a typical polyolefin production process, when the metallocene precursor does not have a tether, particle formation may be non-uniform during polymerization of polyolefin due to reactivity with a polymerization cocatalyst input during polyolefin production.

On the other hand, in the polyolefin production method according to an embodiment of the present invention, the polymerization promoter composition having a bulky alkyl aluminum form is formed by first reacting with the additive in step (2) before the polymerization promoter is added. Accordingly, the polymerization cocatalyst is controlled to react with the supported metallocene catalyst, and acts only as an H ₂ O scavenger, resulting in uniform particle formation and improved bulk density during polyolefin polymerization. This change in physical properties improves productivity and also improves polymerization stability in the slurry process for discharging polyolefin powder down the reactor.

Meanwhile, in the present specification, "cocatalyst compound/cocatalyst" and "polymerization cocatalyst" are distinguished. "Cocatalyst compound/cocatalyst" refers to a compound used in the manufacturing process of a supported metallocene catalyst, and "polymerization" “Cocatalyst” refers to a compound (any one of TIBAL (Triisobutylaluminum), TEAL (triethylaluminum) and TOA (trioctyl aluminum)) that is added together with the supported metallocene catalyst during the polyolefin production process, and as described above, the “polymerization tank "Catalyst composition" means a material including the polymerization cocatalyst and additives (steric hindered phenol).

In the present invention, steric hindered phenol (sterically hindered phenol compound) means a phenolic compound including tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl), preferably Pentaerythritol tetrakis (3 -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) Commercially available steric hindered phenols (sterically hindered phenol compounds) include IRGANOX1010 from BASF.

Preferably, R ₁ to R ₈ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy or C _2-10 alkoxyalkyl, or adjacent R ₁ to R ₈ are C _6-20 aromatic when bonded to each other. rings can be formed. More preferably, R ₁ to R ₈ are each independently hydrogen, methyl, ethyl, propyl, butyl, or tertbutoxy hexyl, or adjacent R ₁ to R ₈ may combine with each other to form a benzene ring. Most preferably, R ₁ to R ₈ are each independently hydrogen, butyl, or tertbutoxy hexyl, or adjacent R ₁ to R ₈ may combine with each other to form a benzene ring.

Preferably, R ₉ and R ₉ ^′ may each independently be hydrogen, halogen, or C _1-10 alkyl. More preferably, R ₉ and R ₉ ^′ may each independently be methyl, ethyl, propyl, or butyl, and most preferably, R ₉ and R ₉ ^′ may each be methyl.

Preferably, A may be silicon (Si).

Preferably, M may be zirconium.

Preferably, each X can be independently halogen, and more preferably, each X can be chloro.

Preferably, the metallocene compound represented by Formula 1 may be any one of compounds represented by Formulas 1-1 to 1-3, but the present invention is not limited thereto:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

.

.

Specifically, the supported metallocene catalyst according to an embodiment of the present invention may include the metallocene compound of Formula 1 as a single catalyst.

The supported metallocene catalyst includes a promoter compound and a carrier in addition to the metallocene compound described above. The supported metallocene catalyst is in the form of a supported metallocene catalyst comprising the metallocene compound and a carrier. When the supported metallocene catalyst is used, the morphology and physical properties of the polyethylene to be prepared are excellent, and the conventional slurry It can be suitably used for polymerization, bulk polymerization, and gas phase polymerization processes.

Specifically, as the carrier, a carrier having a hydroxyl group, a silanol group, or a siloxane group having a high reactivity on the surface may be used. can be used For example, silica prepared by calcining silica gel, silica dried at high temperature, silica-alumina, and silica-magnesia may be used, and these are typically Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg(NO ₃ ). ₂ and the like oxide, carbonate, sulfate, and nitrate components.

The temperature for calcining or drying the carrier may be from about 200 °C to about 600 °C, or from about 250 °C to about 600 °C. When the calcination or drying temperature for the carrier is low, there is a risk that the surface moisture and the cocatalyst may react because there is too much moisture remaining in the carrier, and the cocatalyst loading rate is relatively low due to the excess hydroxyl groups. It can be increased, but this requires a large amount of co-catalyst. In addition, if the drying or calcination temperature is too high, the surface area decreases as the pores on the surface of the carrier coalesce, a lot of hydroxyl groups or silanol groups disappear on the surface, and only siloxane groups remain, so there is a risk of reducing the reaction site with the promoter. have.

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

If the amount of the hydroxyl group is less than 0.1 mmol/g, there are few reaction sites with the co-catalyst, and if it exceeds 10 mmol/g, it is not preferable because it may be caused by moisture other than the hydroxyl group present on the surface of the carrier particle. not.

For example, the amount of hydroxyl groups on the surface of the carrier may be 0.1 mmol/g to 10 mmol/g or 0.5 mmol/g to 5 mmol/g. The amount of hydroxyl groups on the surface of the carrier can be controlled by the method and conditions or drying conditions of the carrier, such as temperature, time, vacuum or spray drying, and the like. If the amount of the hydroxyl group is too low, there are few reaction sites with the promoter, and if it is too large, it may be due to moisture other than the hydroxyl group present on the surface of the carrier particle.

Among the above-mentioned carriers, silica, especially silica prepared by calcining silica gel, is supported by chemical bonding between the silica carrier and the functional group of the compound of Formula 1, so the catalyst released from the surface of the carrier in the propylene polymerization process is almost non-existent. As a result, when polyethylene is produced by slurry or gas phase polymerization, it is possible to minimize fouling caused by agglomeration of the reactor wall or polymer particles.

In addition, when supported on a carrier, the compound of Formula 1 is present in an amount of, for example, about 10 μmol or more, or about 30 μmol or more, and about 10 mmol or less, or about 8 mmol or less, based on the weight of the carrier, based on about 1 g of silica. It may be supported in a content range. When supported in the above content range, it may exhibit an appropriate supported catalyst activity, which may be advantageous in terms of maintaining the activity of the catalyst and economic feasibility.

In addition, one or more cocatalyst compounds included in the supported metallocene catalyst may be included.

As the promoter compound, any promoter compound used for polymerization of olefins under a general metallocene catalyst may be used. This co-catalyst causes a bond to be formed between the hydroxyl group and the Group 13 transition metal on the carrier. In addition, since the cocatalyst exists only on the surface of the carrier, it can contribute to securing the intrinsic properties of the specific catalyst composition of the present application without a fouling phenomenon in which the polymer particles are agglomerated with each other or on the wall of the reactor.

Preferably, the cocatalyst compound may be at least one selected from the group consisting of compounds represented by the following Chemical Formulas 2 to 4:

[Formula 2]

-[Al(R ₁₀ )-O]a-

In Formula 2,

R ₁₀ is halogen; or C _1-20 hydrocarbyl substituted or unsubstituted with halogen;

a is an integer greater than or equal to 2,

[Formula 3]

D(R ₁₁ ) ₃

In Formula 3,

D is aluminum or boron;

R ₁₁ is halogen; Or halogen-substituted or unsubstituted C _1-20 hydrocarbyl,

[Formula 4]

[LH] ⁺ [ZA ₄ ] ^- or [L] ⁺ [ZA ₄ ] ^-

In Formula 4,

L is a neutral or cationic Lewis base;

H is a hydrogen atom;

Z is a group 13 element;

A is each independently C _6-20 aryl or C _1-20 alkyl in which one or more hydrogen atoms are substituted with halogen, C _1-20 hydrocarbyl, C _1-20 alkoxy, or phenoxy.

The compound represented by Formula 2 may serve as an alkylating agent and an activator, the compound represented by Formula 3 may serve as an alkylating agent, and the compound represented by Formula 4 may serve as an activator have.

The compound represented by Formula 2 is not particularly limited as long as it is an alkylaluminoxane, but may be, for example, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, etc., preferably methylaluminoxane .

The compound represented by Formula 3 is not particularly limited as long as it is an alkyl metal compound, but for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, Tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, etc., preferably selected from trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum can

Examples of the compound represented by Formula 4 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra(p-tolyl) Boron, trimethylammonium tetra(o,p-dimethylphenyl) boron, tributylammonium tetra(p-trifluoromethylphenyl) boron, trimethylammonium tetra(p-trifluoromethylphenyl) boron, tributylammonium tetra Pentafluorophenyl boron, N,N-diethylanilinium tetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenyl boron, trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra (p-tolyl) ) Aluminum, tripropylammonium tetra(p-tolyl)aluminum, triethylammoniumtetra(o,p-dimethylphenyl)aluminum, tributylammonium tetra(p-trifluoromethylphenyl)aluminum, trimethylammonium tetra( p-trifluoromethylphenyl)aluminum, tributylammonium tetrapentafluorophenylaluminum, N,N-diethylaniliniumtetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenylaluminum, di Ethylammonium tetrapentatetraphenylaluminum, triphenylphosphoniumtetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, tripropylammoniumtetra(p-tolyl)boron, triethylammoniumtetra(o,p-dimethylphenyl)boron , tributylammonium tetra(p-trifluoromethylphenyl)boron, triphenylcarboniumtetra(p-trifluoromethylphenyl)boron, triphenylcarboniumtetrapentafluorophenylboron, etc., preferably Alumoxane may be used, and more preferably, methylaluminoxane (MAO), which is an alkylaluminoxane, may be used.

In addition, the catalyst composition may include the cocatalyst and the metallocene compound of Formula 1 in a molar ratio of about 1:1 to about 1:10000, preferably about 1:1 to about 1:1000, respectively. It may be included in a molar ratio of, and more preferably, may be included in a molar ratio of about 1:10 to about 1:100. At this time, if the molar ratio is less than about 1, the metal content of the cocatalyst is too small, so the catalytically active species is not well made, and the activity may be lowered. have.

The supported amount of this cocatalyst is about 0.0001 mmol to about 25 mmol, about 0.001 mmol to about 25 mmol, about 0.01 mmol to about 25 mmol, about 0.1 mmol to about 25 mmol, 1 mmol to about 25 mmol, based on 1 g of carrier. , from about 3 mmol to about 25 mmol, or from about 5 mmol to about 20 mmol.

On the other hand, the supported metallocene catalyst, the step of supporting a cocatalyst on a support; supporting the metallocene compound on the support on which the promoter is supported; and a carrier on which the promoter and the metallocene compound are supported.

In the above method, the supporting conditions are not particularly limited and may be performed within a range well known to those skilled in the art. For example, it can proceed by appropriately using high-temperature loading and low-temperature loading, for example, the loading temperature is possible in the range of about -30 ^o C to about 150 ^o C, preferably about 50 ^o C to about 98 ^o C, or from about 55 ^o C to about 95 ^o C. The loading time may be appropriately adjusted according to the amount of the first metallocene compound to be supported. The supported catalyst reacted may be used as it is by removing the reaction solvent by filtration or distillation under reduced pressure, and if necessary, it may be used after Soxhlet filter with an aromatic hydrocarbon such as toluene.

And, the preparation of the supported catalyst may be carried out in the presence of a solvent or non-solvent. When a solvent is used, the usable solvent includes an aliphatic hydrocarbon solvent such as hexane or pentane, an aromatic hydrocarbon solvent such as toluene or benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, diethyl ether or tetrahydrofuran (THF). ) and most organic solvents such as acetone and ethyl acetate, preferably hexane, heptane, toluene, or dichloromethane.

On the other hand, the polyolefin production method according to the present invention includes the step of polymerizing the olefin monomer in the presence of the above-described supported metallocene catalyst.

Preferably, 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 It may be at least one member selected from the group consisting of -dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene.

The polymerization reaction may be carried out using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor, but it is preferable to use a gas phase reactor or a slurry polymerization reactor.

In addition, according to one embodiment of the present invention, the polymerization reaction may proceed by a method of supplying an olefin-based monomer in the presence of hydrogen gas.

At this time, the hydrogen gas suppresses the rapid reaction of the metallocene catalyst at the initial stage of polymerization, so that a high molecular weight polymer can be produced in a larger amount. Therefore, by controlling the use and amount of hydrogen gas used, the polyolefin (co)polymer of the present invention can be effectively obtained.

The hydrogen gas may be introduced such that the molar ratio of the hydrogen gas: the olefinic monomer is about 1:100 to 1:1,000. If the amount of hydrogen gas used is too small, the effect of inhibiting the reaction in the initial stage of polymerization may hardly appear, and if an excessive amount of hydrogen gas is added, the activity of the catalyst may not be sufficiently implemented.

On the other hand, in the reactor, an organoaluminum compound for removing moisture in the reactor may be added as a polymerization cocatalyst, and the polymerization reaction may proceed in the presence thereof. Specific examples of the organoaluminum compound include trialkylaluminum, dialkyl aluminum halide, alkyl aluminum dihalide, aluminum dialkyl hydride or alkyl aluminum sesqui halide, and more specific examples thereof include Triisobutylaluminum (TIBAL) , TEAL (triethylaluminum) and TOA (trioctyl aluminum) may be any one.

According to one embodiment of the present invention, the polymerization promoter is not added alone, but is added in the form of a polymerization promoter composition that is mixed with steric hindered phenol (sterically hindered phenol compound) and reacted.

When the polymerization co-catalyst is added alone, it may react with the polymerization co-catalyst depending on the structure of the metallocene precursor, so that particle formation during polyolefin polymerization may not be uniform. On the other hand, when a polymerization promoter composition is prepared by reacting the polymerization promoter with an additive (steric hindered phenol compound) as described above, the polymerization promoter becomes bulky by the additive, and the supported metallocene catalyst and additional It does not react, and functions only as a H ₂ O scavenger. Accordingly, there is an effect of uniform particle formation and improving bulk density during polyolefin production. Accordingly, stability and productivity during polymerization are improved.

Preferably, the molar ratio of any one of TIBAL (Triisobutylaluminum), TEAL (triethylaluminum) and TOA (trioctyl aluminum) as a polymerization promoter and steric hindered phenol (sterically hindered phenol compound) as an additive is 1:0.5 to 1:100 days can More preferably, the ratio may be 1:0.5 to 1:50, 1:0.5 to 1:20, 1:0.5 to 1:10, 1:0.5 to 1:5, or 1:1 to 1:5. have.

The polymerization co-catalyst composition may be continuously introduced into the reactor, and may be added in a ratio of about 0.1 to 10 moles per 1 kg of the reaction medium input to the reactor for proper moisture removal.

and, the polymerization temperature is from about 25 °C to about 500 °C, or from about 25 °C to about 300 °C, or from about 30 °C to about 200 °C, or from about 50 °C to about 150 °C, or from about 60 °C to about 120 °C. can In addition, the polymerization pressure may be from about 1 kgf/cm 2 to about 100 kgf/cm 2 , or from about 1 kgf/cm 2 to about 50 kgf/cm 2 , or from about 5 kgf/cm 2 to about 45 kgf/cm 2 , or from about 10 kgf/cm 2 to about 10 kgf/cm 2 about 40 kgf/cm 2 , or about 15 kgf/cm 2 to about 35 kgf/cm 2 .

The supported metallocene catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, hexane, heptane, nonane, decane, and isomers thereof and an aromatic hydrocarbon solvent such as toluene and benzene, dichloromethane, chlorobenzene It can be injected by dissolving or diluting in a hydrocarbon solvent substituted with a chlorine atom, such as The solvent used here is preferably used by treating a small amount of alkyl aluminum to remove a small amount of water or air that acts as a catalyst poison, and it is also possible to further use a cocatalyst.

In this polyolefin polymerization process, the catalyst composition including the transition metal compound of the present invention may exhibit high catalytic activity. For example, the catalytic activity during polyolefin polymerization is about 5.0 kg PE when calculated as the ratio of the weight (kg PE) of polyolefin, for example, polyethylene produced per mass (g) of catalyst composition used based on unit time (hr) /g·cat·hr or greater or from about 5.0 kg PE /g·cat·hr to about 50 kg PE /g·cat·hr. Specifically, the activity of the catalyst composition is about 5.5 kg PE /g·cat·hr or more, or about 5.5 kg PE /g·cat·hr or more, or about 40 kg PE /g·cat·hr or less, or about 30 kg PE /g·cat·hr or less, or about 15 kg PE /g·cat·hr or less.

As described above, according to the present invention, polyolefin can be produced through the above-described polyolefin production method.

On the other hand, the polyolefin copolymer obtained according to the production method of the present invention has a weight average molecular weight of about 100,000 g/mol to about 300,000 g/mol, about 120,000 g/mol to about 260,000 g/mol, or about 139,000 g/mol to about 254,000 g/mol.

On the other hand, the polyolefin obtained according to the production method of the present invention may have a molecular weight distribution (MWD) of 2.0 to 4.0, or 2.7 to 3.7.

For example, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polyolefin can be measured using gel permeation chromatography (GPC, gel permeation chromatography, manufactured by Water). The molecular weight distribution (MWD; Mw/Mn) can be obtained by dividing the measured weight average molecular weight by the number average molecular weight.

Specifically, as a gel permeation chromatography (GPC) apparatus, a Waters PL-GPC220 instrument may be used, and a Polymer Laboratories PLgel MIX-B 300 mm long column may be used. At this time, the measurement temperature is 160 °C, 1,2,4-trichlorobenzene (1,2,4-Trichlorobenzene) can be used as a solvent, and the flow rate can be applied at 1 mL/min. Each polyethylene sample was pretreated by dissolving it in trichlorobenzene (1,2,4-Trichlorobenzene) containing 0.0125% of BHT at 160 °C for 10 hours using a GPC analysis device (PL-GP220), and 10 mg/10 mL of It can be measured by preparing the concentration and then supplying it in an amount of 200 μL. In addition, the values of Mw and Mn can be derived using a calibration curve formed using a polystyrene standard specimen. The weight average molecular weight of the polystyrene standard specimen is 2000 g/mol, 10000 g/mol, 30000 g/mol, 70000 g/mol, 200000 g/mol, 700000 g/mol, 2000000 g/mol, 400000 g/mol, 1000000 g Nine types of /mol can be used.

The bulk density of the polyolefin obtained according to the production method of the present invention is 0.3 kg/m ³ to 0.5 kg/m ³ , 0.3 kg/m ³ to 0.4 kg/m ³ , 0.3 kg/m ³ to 0.35 kg/m ³ , or 0.33 kg/m ³ to 0.35 kg/m ³ may be.

The bulk density may be measured using a bulk density meter. First, weigh the 100 ml measuring vessel for bulk density measurement, pour the polymerized powder into the bulk density measuring vessel, and then remove the excess PE powder from the top of the measuring vessel and measure the measuring vessel weight. The bulk density of the polymerized PE powder can be obtained by dividing the measured weight by 100 ml.

The SPAN of the polyolefin obtained according to the production method of the present invention may be 1.15 or less, or 1.13 or less, and may be 1.0 or more, 1.05 or more, or 1.07 or more. The SPAN value means the width of the particle size distribution, and the polyolefin has a small SPAN value of 1.2 or less, so that the particles are uniform. The SPAN can be measured with an optical diffraction particle size analyzer (HELOS particle size analyzer, SYMPATEC GbmH).

Hereinafter, it will be described in more detail to help the understanding of the present invention. However, the following examples only illustrate the present invention, and the content of the present invention is not limited by the following examples.

[Preparation of metallocene compound]

Synthesis Example 1: Catalyst Precursor 1

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

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

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

¹ H NMR (300 MHz, CDCl ₃ ): 6.28 (t, J = 2.6 Hz, 2 H), 6.19 (t, J = 2.6 Hz, 2 H), 3.31 (t, 6.6 Hz, 2 H), 2.62 ( t, J = 8 Hz), 1.7 - 1.3 (m, 8 H), 1.17 (s, 9 H).

[Preparation of supported metallocene catalyst and polymerization co-catalyst composition]

Preparation Example 1: Preparation of Supported Metallocene Catalyst 1

49.7 ml of a 10 wt% methylaluminoxane (MAO)/toluene solution was put into a glass reactor, 9.1 g of silica was added at 40 °C, the reactor temperature was raised to 60 °C, and the mixture was stirred at 200 rpm for 16 hours. After lowering the temperature to 40 °C, 550 mg (0.1 mmol/gSiO ₂ ) of the catalyst precursor 1 prepared in Synthesis Example 1 was dissolved in 20 ml of toluene, and then put into a supported catalyst reactor and stirred for two hours. After the reaction was completed, stirring was stopped, the toluene layer was separated and removed, and then the pressure was reduced at 40° C. and the remaining toluene was removed to prepare a supported metallocene catalyst 1.

Preparation Example 2: Preparation of supported metallocene catalyst 2

It was prepared in the same manner as in Preparation Example 1, except that the following catalyst precursor 2 was used instead of the catalyst precursor 1 of Synthesis Example 1. The following catalyst precursor 2 is a commercially available compound (CAS No. 73364-10-0).

Preparation Example 3: Preparation of supported metallocene catalyst 3

It was prepared in the same manner as in Preparation Example 1, except that the following catalyst precursor 3 was used instead of the catalyst precursor 1 of Synthesis Example 1. The following catalyst precursor 3 is a commercially available compound (CAS No. 121009-93-6).

Preparation Example 4: Preparation of polymerization co-catalyst composition 1

In a round bottom flask filled with argon, 20 mmol of IRGANOX1010 (BASF) was added to TIBAL (Triisobutylaluminum) 1M Solution in Hx 20 ml, and stirred for one day to prepare a polymerization cocatalyst composition.

Preparation Example 5: Preparation of polymerization co-catalyst composition 2

In a round bottom flask filled with argon, 20 mmol of IRGANOX1010 (BASF) was added to 20 ml of TOA (trioctyl aluminum) 1M Solution in Hx, and stirred for one day to prepare a polymerization cocatalyst composition.

Comparative Preparation Example 1: Preparation of Comparative Polymerization Cocatalyst Composition 1

In a round-bottom flask filled with argon, 40 mmol of BHT (Butylhydroxytoluene) was added to 20 ml of TEAL (triethylaluminum) 1M Solution in Hx, and stirred for one day to prepare a comparative polymerization cocatalyst composition.

Comparative Preparation Example 2: Preparation of Comparative Supported Metallocene Catalyst 1 (hereinafter, Comparative Catalyst 1)

49.7 ml of a 10 wt% methylaluminoxane (MAO)/toluene solution was put into a glass reactor, 9.1 g of silica was added at 40 °C, and the reactor was stirred while raising the temperature to 60 °C, followed by stirring at 200 rpm for 16 hours. After lowering the temperature to 40 °C, IRGANOX1010 (1.07 g, 0.1 mmol/gSiO ₂ ) was added as a toluene solution, followed by stirring for 1 hour. After that, TIBAL 1M Solution (9.8 ml, 0.2 mmol/gSiO ₂ ) was added and stirred for 1 hour. Then, the catalyst precursor 3 (0.1 mmol/gSiO ₂ ) of Preparation Example 3 was dissolved in a solution state and then put into a supported catalyst reactor and stirred for two hours. After the reaction was completed, the stirring was stopped, the toluene layer was separated and removed, and the remaining toluene was removed under reduced pressure at 40° C., thereby preparing a comparative supported metallocene catalyst 1.

[Polyethylene Polymerization]

Example 1

Using a Parr reactor, 400 ml of hexane was put into an isolated system filled with argon, 1 g of trimethylaluminium was added, the inside of the reactor was dried, and all of the hexane was removed. After filling again with 400 ml of hexane, 0.5 g of the polymerization co-catalyst composition 1 prepared in Preparation Example 4 was added. In a glove box filled with argon, 7 mg of the supported metallocene catalyst 2 prepared in Preparation Example 2 was measured and put into the reactor. Thereafter, ethylene was filled up to 20 bar at 78 °C with an argon vent, and after polymerization at 80 °C for 1 hour, unreacted C2 was vented and polyethylene was obtained.

Example 2

Polyethylene was polymerized in the same manner as in Example 1, except that the supported metallocene catalyst 3 prepared in Preparation Example 3 was used instead of the supported metallocene catalyst 2.

Example 3

Polyethylene was polymerized in the same manner as in Example 1, except that polymerization promoter composition 2 prepared in Preparation Example 5 was used instead of polymerization promoter composition 1.

Example 4

Except for using the polymerization promoter composition 2 prepared in Preparation Example 5 instead of the polymerization promoter composition 1, and using the supported metallocene catalyst 3 prepared in Preparation Example 3 instead of the supported metallocene catalyst 2, Example 1 and Polyethylene was polymerized in the same way.

Comparative Example 1

Using a Parr reactor, 400 ml of hexane was put into an isolated system filled with argon, 1 g of trimethylaluminium was added, the inside of the reactor was dried, and all of the hexane was removed. After filling 400 ml of hexane again, 0.3 g of 1M TEAL (triethylaluminum) solution was added as a polymerization cocatalyst. In a glove box filled with argon, 7 mg of the supported metallocene catalyst 2 prepared in Preparation Example 2 was measured and put into the reactor. Thereafter, ethylene was filled up to 20 bar at 78 °C with an argon vent, and after polymerization at 80 °C for 1 hour, unreacted C2 was vented and polyethylene was obtained.

Comparative Examples 2 to 6

Polyethylene was polymerized in the same manner as in Comparative Example 1, except that the polymerization cocatalyst and the supported metallocene catalyst were added as shown in Table 1.

Comparative Example 7

Polyethylene was polymerized in the same manner as in Example 1, except that the comparative polymerization promoter composition 1 prepared in Comparative Preparation Example 1 was used instead of the polymerization promoter composition 1.

Comparative Example 8

Example except that the comparative polymerization promoter composition 1 prepared in Comparative Preparation Example 1 was used instead of the polymerization promoter composition 1, and the supported metallocene catalyst 3 prepared in Preparation Example 3 was used instead of the supported metallocene catalyst 2 Polyethylene was polymerized in the same manner as in 1.

Comparative Example 9

Polyethylene was polymerized in the same manner as in Comparative Example 1, except that the polymerization cocatalyst and the supported metallocene catalyst were added as shown in Table 1.

Experimental example

The physical properties of the polyethylene polymerized in Examples and Comparative Examples were measured and shown in Table 1 below.

(1) Polymerization activity (activity, kg PE/g cat·hr)

It was calculated as the ratio of the weight (kg PE) of the polyethylene copolymer produced per content of the supported catalyst used (g Cat) per unit time (hr).

(2) weight average molecular weight (Mw, g/mol) and molecular weight distribution

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polyethylene copolymer were measured using gel permeation chromatography (GPC, gel permeation chromatography, manufactured by Water). The molecular weight distribution (MWD; Mw/Mn) was obtained by dividing the measured weight average molecular weight by the number average molecular weight.

Specifically, as a gel permeation chromatography (GPC) apparatus, a Waters PL-GPC220 instrument was used, and a Polymer Laboratories PLgel MIX-B 300 mm long column was used. At this time, the measurement temperature was 160 °C, 1,2,4-trichlorobenzene (1,2,4-Trichlorobenzene) was used as a solvent, and the flow rate was 1 mL/min. Each polyethylene sample was pretreated by dissolving it in trichlorobenzene (1,2,4-Trichlorobenzene) containing 0.0125% BHT at 160 °C for 10 hours using a GPC analysis device (PL-GP220), and 10 mg/10 mL of After preparing to a concentration, it was supplied in an amount of 200 μL. In addition, the value of Mw was derived using a calibration curve formed using a polystyrene standard specimen. The weight average molecular weight of the polystyrene standard specimen 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, 1000000 g Nine species of /mol were used.

(3) Bulk density (BD, kg/m ³ )

Bulk density was measured using a bulk density meter. First, a 100 ml measuring container for bulk density measurement was weighed, the polymerized powder was poured into the bulk density measuring container, and the excess PE powder on the top of the measuring container was removed by shaving off, and then the measuring container weight was measured. The measured weight was divided by 100 ml to obtain the bulk density of the polymerized PE powder.

(4) Particle size (μm) and Span

After injecting the sample into the hopper with an optical diffraction particle size analyzer (HELOS particle size analyzer, SYMPATEC GbmH), a method in the range of 50 ~ 3500 μm was set to check the particle size (APS, Average Particle Size) and SPAN values.

supported metallocene catalyst polymerization cocatalyst Polymerization activity (kgPE/gCat hr) Mw
(10 ³ g/mol) MWD BD
(kg/m ³ ) granularity
(μm) Span Comparative Example 1 Catalyst 2 TEAL 3.3 165 2.7 0.34 459 1.25 Comparative Example 2 Catalyst 2 TIBAL 6.5 143 2.8 0.32 516 1.21 Comparative Example 3 Catalyst 2 TOA 6.0 157 2.7 0.33 512 1.16 Comparative Example 4 catalyst 3 TEAL 3.2 275 3.4 0.33 450 1.38 Comparative Example 5 catalyst 3 TIBAL 6.0 243 3.9 0.30 476 1.21 Comparative Example 6 catalyst 3 TOA 5.4 251 3.7 0.31 471 1.18 Comparative Example 7 Catalyst 2 TEAL+BHT
(Comparative polymerization cocatalyst composition 1) 3.4 161 2.6 Fouling - - Comparative Example 8 catalyst 3 TEAL+BHT
(comparative polymerization
Cocatalyst composition 1) 3.3 283 3.5 0.33 467 1.18 Comparative Example 9 Comparative catalyst 1 TIBAL 6.4 235 3.7 0.33 512 1.25 Example 1 Catalyst 2 TIBAL+IRGANOX
(Polymerization co-catalyst
Composition 1) 7.8 139 2.7 0.35 537 1.07 Example 2 catalyst 3 TIBAL+IRGANOX
(Polymerization co-catalyst
Composition 1) 6.7 238 3.7 0.33 523 1.09 Example 3 Catalyst 2 TOA+IGANOX
(Polymerization co-catalyst
composition 2) 6.2 157 2.7 0.33 508 1.13 Example 4 catalyst 3 TOA+IRGANOX
(Polymerization co-catalyst
composition 2) 5.7 254 3.6 0.33 496 1.15

As shown in Table 1, the catalytic activity and BD of Example 1 prepared using the polymerization cocatalyst composition including the additive were increased compared to Comparative Example 2 using the supported metallocene catalyst 2 including the precursor 2 And, it can be confirmed that the Span is reduced, the catalytic activity of Example 2 prepared using a polymerization cocatalyst composition containing an additive compared to Comparative Example 5 using the supported metallocene catalyst 3 containing the precursor 3, BD It can be seen that increases and Span decreases.

In addition, the catalytic activity and BD of Example 1 prepared using the polymerization co-catalyst composition were increased compared to Comparative Example 9, in which the catalyst was prepared by adding the polymerization co-catalyst and additives to the catalyst precursor without using the polymerization co-catalyst composition. , it can be seen that the span is reduced.

Claims (13)

a metallocene compound represented by the following formula (1); cocatalyst compounds; and preparing a supported metallocene catalyst comprising a carrier (1);
any one of triisobutylaluminum (TIBAL), triethylaluminum (TEAL) and trioctyl aluminum (TOA); And preparing a polymerization promoter composition comprising a steric hindered phenol (sterically hindered phenol compound) (2); and
Containing; comprising a;
Method for preparing polyolefin:
[Formula 1]

In Formula 1,
R ₁ to R ₈ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkoxy or C _2-20 alkoxyalkyl, or adjacent R ₁ to R ₈ are bonded to each other to form a C _6-60 aromatic ring,
R ₉ and R ₉ ^' are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkoxy or C _2-20 alkoxyalkyl, or R ₉ and R _9' are bonded to each other to form a C _2-10 aliphatic ring or a C _6-60 aromatic ring,
A is silicon (Si) or carbon (C),
k is an integer equal to 0 or 1,
M is a group 4 transition element,
each X is independently halogen or C _1-20 alkyl.
According to claim 1,
steric hindered phenol is Pentaerythritol tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate),
Method for producing polyolefin.
According to claim 1,
R ₁ to R ₈ are each independently hydrogen, methyl, ethyl, propyl, butyl, or tertbutoxy hexyl, or adjacent R ₁ to R ₈ are bonded to each other to form a benzene ring,
Method for producing polyolefin.
According to claim 1,
R ₉ and R ₉ ^' are each independently methyl, ethyl, propyl, or butyl;
Method for producing polyolefin.
According to claim 1,
A is Si;
Method for producing polyolefin.
According to claim 1,
M is zirconium,
Method for producing polyolefin.
According to claim 1,
each X is independently halogen;
Method for producing polyolefin.
According to claim 1,
The metallocene compound represented by Formula 1 is any one of the compounds represented by Formula 1-1 to Formula 1-3,
A process for preparing an olefin polymer:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

.
According to claim 1,
Any one of the TIBAL (Triisobutylaluminum), TEAL (triethylaluminum) and TOA (trioctyl aluminum): the molar ratio of steric hindered phenol (sterically hindered phenol compound) is 1:0.5 to 1:100,
A process for the production of polyolefins.
According to claim 1,
The promoter compound is at least one selected from the group consisting of compounds represented by the following Chemical Formulas 2 to 4,
Method for preparing polyolefin:
[Formula 2]
-[Al(R ₁₀ )-O]a-
In Formula 2,
R ₁₀ is halogen; or C _1-20 hydrocarbyl substituted or unsubstituted with halogen;
a is an integer greater than or equal to 2,
[Formula 3]
D(R ₁₁ ) ₃
In Formula 3,
D is aluminum or boron;
R ₁₁ is halogen; Or halogen-substituted or unsubstituted C _1-20 hydrocarbyl,
[Formula 4]
[LH] ⁺ [ZA ₄ ] ^- or [L] ⁺ [ZA ₄ ] ^-
In Formula 4,
L is a neutral or cationic Lewis base;
H is a hydrogen atom;
Z is a group 13 element;
A is each independently C _6-20 aryl or C _1-20 alkyl in which one or more hydrogen atoms are substituted with halogen, C _1-20 hydrocarbyl, C _1-20 alkoxy, or phenoxy.
According to claim 1,
The carrier is at least one selected from silica, silica-alumina and silica-magnesia,
A process for the production of polyolefins.
According to claim 1,
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-dodecene, At least one selected from the group consisting of 1-tetradecene, 1-hexadecene and 1-eicosene,
A process for the production of polyolefins.
According to claim 1,
The polyolefin has a SPAN of 1.15 or less,
A process for the production of polyolefins.