KR20230150461A - Mononuclear metallocene compound and metallocene catalyst for preparing polyolefin using the same - Google Patents

Abstract

The present invention relates to a mononuclear metallocene compound with a novel structure and a metallocene catalyst for polyolefin production prepared including the same. One embodiment provides the mononuclear metallocene compound with the novel structure that can produce a supported metallocene catalyst with improved functional effects.

Description

Mononuclear metallocene compound and metallocene catalyst for preparing polyolefin using the same {Mononuclear metallocene compound and metallocene catalyst for preparing polyolefin using the same}

The present disclosure relates to a mononuclear metallocene compound and a metallocene catalyst for producing polyolefin using the same.

Resins polymerized with metallocene catalysts have the advantage of showing a narrow molecular weight distribution and excellent mechanical properties. The stereoregularity, copolymerization characteristics, molecular weight, crystallinity, etc. of the polymer change depending on the modification of the catalyst's ligand structure and changes in polymerization conditions. It has characteristics that can make it happen. Accordingly, efforts are being actively made in the industry to replace the existing Ziegler-Natta catalyst with a metallocene catalyst in the polyolefin polymerization process.

However, there are several problems that need to be improved in order to apply metallocene to actual processes, and one of the important research interests is the technology for producing high molecular weight polyolefins using metallocene catalysts. Although much research is being conducted for this purpose, the ligand synthesis process becomes complicated to produce high molecular weight polyolefin, and unless the process conditions are adjusted, polymerization activity also has limitations.

Therefore, there is a need for the development of a new catalyst that can produce high molecular weight polyolefin while exhibiting excellent activity in polyolefin production.

Korean Patent Publication No. 1549206 (2013.11.18.)

One embodiment provides a mononuclear metallocene compound with a novel structure that can produce a supported metallocene catalyst with improved functional effects.

In addition, one embodiment provides a supported mononuclear metallocene catalyst capable of producing a high molecular weight polymer and having high activity, and a method for producing the same.

Additionally, one embodiment provides a method for producing polyolefin using the supported mononuclear metallocene catalyst.

For the above-described purpose, one embodiment of the present invention provides a mononuclear metallocene compound represented by Formula 1 below.

[Formula 1]

(In Formula 1 above,

Ring A is an aromatic ring or an alicyclic ring;

M ₁ is a Group 4, 5, or 6 transition metal;

Y ₁ is C or Si;

L is a single bond, (C1-C30)alkylene or (C6-C30)arylene;

R ₁ and R ₂ are each independently hydrogen, (C1-C30)alkyl, (C1-C30)alkoxy, or (C6-C30)aryl, or R ₁ and R ₂ are connected to each other to form an alicyclic ring or an aromatic ring. may be formed, and the alicyclic ring and aromatic ring may be further substituted with (C1-C30)alkyl;

R ₃ to R ₆ are each independently hydrogen, (C1-C30)alkyl, (C1-C30)alkoxy, (C2-C30)alkenyl, (C6-C30)aryl, (C6-C30)aryloxy, (C1 -C30)alkyl(C6-C30)aryl, (C6-C30)aryl(C1-C30)alkyl, mono(C1-C30)alkylamino, di(C1-C30)alkylamino, mono(C6-C30)arylamino or di(C6-C30)arylamino;

R ₇ and R ₈ are each independently (C1-C30)alkyl, (C2-C30)alkenyl, tri(C1-C30)alkylsilyl, tri(C6-C30)arylsilyl, or halogen;

R ₉ to R ₁₅ are each independently (C1-C30)alkyl;

n is an integer from 1 to 10.)

The mononuclear metallocene compound may be represented by Formula 2 or Formula 3 below.

[Formula 2]

[Formula 3]

(In Formulas 2 and 3 above,

M ₁ is a Group 4, 5, or 6 transition metal;

Y ₁ is C or Si;

L is a single bond, (C1-C7)alkylene or (C6-C12)arylene;

R ₁ and R ₂ are each independently hydrogen, (C1-C7)alkyl, (C1-C7)alkoxy, or (C6-C12)aryl;

R ₃ to R ₆ are each independently hydrogen, (C1-C7)alkyl, (C1-C7)alkoxy, (C2-C7)alkenyl, (C6-C12)aryl, (C6-C12)aryloxy, (C1) -C7)alkyl(C6-C12)aryl, (C6-C12)aryl(C1-C7)alkyl, mono(C1-C7)alkylamino, di(C1-C7)alkylamino, mono(C6-C12)arylamino or di(C6-C12)arylamino;

R ₇ and R ₈ are each independently (C1-C7)alkyl, (C2-C7)alkenyl, tri(C1-C7)alkylsilyl, tri(C6-C12)arylsilyl, or halogen;

R ₉ to R ₂₁ are each independently (C1-C7)alkyl;

n is an integer from 1 to 6.)

In Formulas 2 and 3, M ₁ may be titanium, hafnium, or zirconium.

The mononuclear metallocene compound may be represented by Formula 4 or Formula 5 below.

[Formula 4]

[Formula 5]

(In Formulas 4 and 5 above,

R ₁ to R ₆ are each independently hydrogen or (C1-C7)alkyl;

R ₇ to R ₈ are each independently (C1-C7)alkyl or halogen;

R ₉ is (C1-C7)alkyl;

n is an integer from 1 to 6.)

The mononuclear metallocene compound according to one embodiment may be selected from the following.

Additionally, one embodiment includes a carrier; and a mononuclear metallocene compound represented by the following formula (1) supported on the carrier.

[Formula 1]

(In Formula 1, R ₁ to R ₁₅ , Y ₁ , M ₁ , A, L and n are the same as the definitions in Formula 1.)

The carrier may be an aluminum compound-carrier complex.

The aluminum compound-support complex is one selected from silica, alumina, magnesium chloride, calcium chloride, bauxite, zeolite, magnesium oxide, zirconium oxide, titanium oxide, boron trioxide, calcium oxide, zinc oxide, barium oxide and thorium oxide. Alternatively, the aluminum compound may form a complex on two or more carriers.

The molar ratio between the mononuclear metallocene compound and the carrier may be 1:2 to 1:5000.

In addition, one embodiment includes reacting an aluminum compound and a support to prepare an aluminum compound-support complex; and preparing a supported mononuclear metallocene catalyst by reacting the aluminum compound-support complex with the mononuclear metallocene compound represented by the following formula (1): to provide.

[Formula 1]

(In Formula 1, R ₁ to R ₁₅ , Y ₁ , M ₁ , A, L and n are the same as the definitions in Formula 1.)

The aluminum compound may be used in an amount of 10 to 50 parts by weight based on 100 parts by weight of the carrier.

Additionally, one embodiment provides a method for producing polyolefin, comprising polymerizing one or more olefin monomers in the presence of the supported mononuclear metallocene catalyst.

The olefin monomer may be one or two or more selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, 1-octene, and mixtures thereof.

A supported mononuclear metallocene catalyst supported with a mononuclear metallocene compound according to one embodiment has excellent catalytic activity and can produce high molecular weight polyolefin.

Additionally, the supported mononuclear metallocene catalyst according to one embodiment can produce polyolefin whose particles are uniform in shape and size.

Accordingly, the supported mononuclear metallocene catalyst according to one embodiment can be easily applied to slurry processes and gas phase processes in which energy consumption is reduced.

In addition, the supported catalyst according to one embodiment does not cause problems in the input of the polyolefin production process and can efficiently produce high-quality polyolefin, thereby significantly improving productivity.

Unless otherwise defined herein, all technical and scientific terms have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. The terminology used in the description herein is merely to effectively describe particular embodiments and is not intended to limit the invention.

As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly dictates otherwise.

In addition, the numerical range used in this specification includes the lower limit and upper limit and all values within the range, increments logically derived from the shape and width of the defined range, all double-defined values, and the upper limit of the numerical range defined in different forms. and all possible combinations of the lower bounds. Unless otherwise specified herein, values outside the numerical range that may occur due to experimental error or rounding of values are also included in the defined numerical range.

As used in this specification, the term “comprises” is an open description with the same meaning as expressions such as “comprises,” “contains,” “has,” or “characterized by” and is not additionally listed. No element, material or process is excluded.

As used herein, the term “alkyl” refers to an alkyl group having 1 to 30 carbon atoms (unless the number of carbon atoms is specifically limited), specifically 1 to 20 carbon atoms, specifically 1 to 15 carbon atoms, specifically 1 to 10 carbon atoms, specifically 1 to 10 carbon atoms. It refers to a saturated straight-chain or branched non-cyclic hydrocarbon with 7. “Lower alkyl” means straight-chain or branched alkyl having 1 to 7 carbon atoms, specifically 1 to 5 carbon atoms. Representative saturated straight-chain alkyls are -methyl, -ethyl, -n-propyl, -n-butyl, -n-pentyl, -n-hexyl, -n-heptyl, -n-octyl, -n-nonyl and -n- Including, but not limited to, decyl. On the other hand, saturated branched alkyls are -isopropyl, -sec-butyl, -isobutyl, -tert-butyl, isopentyl, 2-methylhexyl, 3-methylbutyl, 2-methylpentyl, 3-methylpentyl, 4- Methylpentyl, 2-methylhexyl, 3-methylhexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2, 3-dimethylbutyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, 2,2-dimethylpentyl, 2,2 -dimethylhexyl, 3,3-dimethylpentyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 2-ethylpentyl, 3-ethylpentyl, 2-dethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methyl-2-ethylpentyl, 2-methyl-3-ethylpentyl, 2-methyl-4-ethylpentyl, 2-methyl-2-ethylhexyl, 2-methyl-3-ethylhexyl, 2-methyl-4 -Includes, but is not limited to, ethylhexyl, 2,2-diethylpentyl, 3,3-diethylhexyl, 2,2-diethylhexyl, and 3,3-diethylhexyl.

As used herein, the term "alkenyl" refers to an alkenyl group having 2 to 30 carbon atoms, specifically 2 to 20, specifically 2 to 15, especially 2 to 10, especially 2 to 7 carbon atoms and at least one carbon-carbon doublet. It refers to a saturated straight-chain or branched non-cyclic hydrocarbon containing bonds. Representative straight chain and branched alkenyls include -vinyl, -allyl, -1-butenyl, -2-butenyl, -isobutylenyl, -1-pentenyl, -2-pentenyl, -3-methyl-1 -Butenyl, -2-methyl-2-butenyl, -2,3-dimethyl-2-butenyl, -1-hexenyl, -2-hexenyl, -3-hexenyl, -1- Heptenyl, -2-heptenyl, -3-heptenyl, -1-octenyl, -2-octenyl, -3octenyl, -1-nonenyl, -2-nonenyl, -3- Including, but not limited to, nonenyl, -1-dicenyl, -2-dicenyl, and -3-dicenyl. These alkenyl groups may be optionally substituted.

The term “alkoxy” used in this specification includes -OCH ₃ , -OCH ₂ CH ₃ , -O(CH ₂ ) ₂ CH ₃ , -O(CH ₂ ) ₃ CH ₃ , -O(CH ₂ ) ₄ CH ₃ , means -O-(alkyl), including -O(CH ₂ ) ₅ CH ₃ , and the like, where alkyl is as defined above.

As used herein, the term “aryl” refers to a carbocyclic aromatic group containing 5 to 10 ring atoms. Representative examples include phenyl, tolyl, xylyl, naphthyl, tetrahydronaphthyl, anthracenyl, fluorenyl, indenyl, azulenyl, etc. Including but not limited to this. The carbocyclic aromatic group may be optionally substituted.

As used herein, the term "aryloxy" means RO-, and R is aryl as defined above.

The term "mono-alkylamino" used herein refers to -NHCH ₃ , -NHCH ₂ CH ₃ , -NH(CH ₂ ) ₂ CH ₃ , -NH(CH ₂ ) ₃ CH ₃ , -NH(CH ₂ ) ₄ means -NH(alkyl), including CH ₃ , -NH(CH ₂ ) ₅ CH ₃ , and the like, where alkyl is as defined above.

The term "di-alkylamino" used herein refers to -N(CH ₃ ) ₂ , -N(CH ₂ CH ₃ ) ₂ , -N((CH ₂ ) ₂ CH ₃ ) ₂ , -N(CH ₃ ) -N(alkyl)(alkyl), including (CH ₂ CH ₃ ), and the like, wherein each alkyl is independently an alkyl as defined above.

As used herein, the term “alkylamino” includes mono-alkylamino and di-alkylamino as defined above.

As used herein, the term “arylalkyl” refers to an alkyl radical substituted with at least one aryl, where ‘aryl’ and ‘alkyl’ are as defined above. For example, examples of arylalkyl radicals include, but are not limited to, benzyl, etc.

As used herein, the term “alkylaryl” refers to an aryl radical substituted with at least one alkyl, where ‘alkyl’ and ‘aryl’ are as defined above. Examples of such alkylaryl radicals include, but are not limited to, tolyl and the like.

One embodiment provides a novel mononuclear metallocene compound that has an excellent effect of improving the molecular weight of polyolefin when producing polyolefin and at the same time enables the production of a supported metallocene catalyst with high activity.

A mononuclear metallocene compound according to one embodiment may be represented by Formula 1 below.

[Formula 1]

(In Formula 1 above,

Ring A is an aromatic ring or an alicyclic ring;

M ₁ is a Group 4, 5, or 6 transition metal;

Y ₁ is C or Si;

L is a single bond, (C1-C30)alkylene or (C6-C30)arylene;

R ₁ and R ₂ are each independently hydrogen, (C1-C30)alkyl, (C1-C30)alkoxy, or (C6-C30)aryl, or R ₁ and R ₂ are connected to each other to form an alicyclic ring or an aromatic ring. may be formed, and the alicyclic ring and aromatic ring may be further substituted with (C1-C30)alkyl;

R ₃ to R ₆ are each independently hydrogen, (C1-C30)alkyl, (C1-C30)alkoxy, (C2-C30)alkenyl, (C6-C30)aryl, (C6-C30)aryloxy, (C1 -C30)alkyl(C6-C30)aryl, (C6-C30)aryl(C1-C30)alkyl, mono(C1-C30)alkylamino, di(C1-C30)alkylamino, mono(C6-C30)arylamino or di(C6-C30)arylamino;

R ₇ and R ₈ are each independently (C1-C30)alkyl, (C2-C30)alkenyl, tri(C1-C30)alkylsilyl, tri(C6-C30)arylsilyl, or halogen;

R ₉ to R ₁₅ are each independently (C1-C30)alkyl;

n is an integer from 1 to 10.)

The mononuclear metallocene compound according to one embodiment has the structural features described above, for example, a cyclopentathiophenyl (thiophene-fused cyclopentadienyl) functional group, a branched alkyl group, and a branched alkoxy group at the same time. As a result, it is very useful in producing a supported catalyst with improved physical properties that can be easily applied to slurry processes and gas phase processes among polyolefin processes. Specifically, the supported catalyst prepared from the mononuclear metallocene compound can achieve high activity and effectively improve the molecular weight of the polyolefin produced.

Specifically, in Formula 1, ring A is an aromatic ring; M ₁ is a Group 4, 5, or 6 transition metal; Y ₁ is C or Si; L is a single bond, (C1-C20)alkylene or (C6-C20)arylene; R ₁ and R ₂ are each independently hydrogen, (C1-C20)alkyl, (C1-C20)alkoxy, or (C6-C20)aryl, or R ₁ and R ₂ are connected to each other to form an alicyclic ring or an aromatic ring. may be formed, and the alicyclic ring and aromatic ring may be further substituted with (C1-C30)alkyl; R ₃ to R ₆ are each independently hydrogen, (C1-C20)alkyl, (C1-C20)alkoxy, (C2-C20)alkenyl, (C6-C20)aryl, (C6-C20)aryloxy, (C1) -C20)alkyl(C6-C20)aryl, (C6-C20)aryl(C1-C20)alkyl, mono(C1-C20)alkylamino, di(C1-C20)alkylamino, mono(C6-C20)arylamino or di(C6-C20)arylamino; R ₇ and R ₈ are each independently (C1-C20)alkyl, (C2-C20)alkenyl, tri(C1-C20)alkylsilyl, tri(C6-C20)arylsilyl, or halogen; R ₉ to R ₁₅ are each independently (C1-C20)alkyl; n is an integer from 1 to 10.

As an example, when R ₁ and R ₂ are connected to each other to form an alicyclic ring or an aromatic ring, the alicyclic ring and the aromatic ring are branched (C3-C30) alkyl in order to have better catalytic activity. It can be further replaced with .

More specifically, the mononuclear metallocene compound according to one embodiment may be represented by Formula 2 or Formula 3 below.

[Formula 2]

[Formula 3]

(In Formulas 2 and 3 above,

M ₁ is a Group 4, 5, or 6 transition metal;

Y ₁ is C or Si;

L is a single bond, (C1-C7)alkylene or (C6-C12)arylene;

R ₁ and R ₂ are each independently hydrogen, (C1-C7)alkyl, (C1-C7)alkoxy, or (C6-C12)aryl;

R ₃ to R ₆ are each independently hydrogen, (C1-C7)alkyl, (C1-C7)alkoxy, (C2-C7)alkenyl, (C6-C12)aryl, (C6-C12)aryloxy, (C1) -C7)alkyl(C6-C12)aryl, (C6-C12)aryl(C1-C7)alkyl, mono(C1-C7)alkylamino, di(C1-C7)alkylamino, mono(C6-C12)arylamino or di(C6-C12)arylamino;

R ₇ and R ₈ are each independently (C1-C7)alkyl, (C2-C7)alkenyl, tri(C1-C7)alkylsilyl, tri(C6-C12)arylsilyl, or halogen;

R ₉ to R ₂₁ are each independently (C1-C7)alkyl;

n is an integer from 1 to 6.)

As an example, M ₁ may be titanium, hafnium, or zirconium. In terms of having excellent catalytic activity, it may be titanium or zirconium, and more specifically, it may be zirconium.

As an example, L is (C6-C12)arylene, R ₁₀ to R ₂₁ are the same as each other and may be (C1-C7)alkyl, specifically methyl, ethyl or n-propyl, and more specifically methyl. It can be.

As an example, the mononuclear metallocene compound may be represented by Formula 4 or Formula 5 below.

[Formula 4]

[Formula 5]

(In Formulas 4 and 5 above,

R ₁ to R ₆ are each independently hydrogen or (C1-C7)alkyl;

R ₇ to R ₈ are each independently (C1-C7)alkyl or halogen;

R ₉ is (C1-C7)alkyl

n is an integer from 1 to 6.)

In order to further improve catalytic activity, R ₇ and R ₈ are the same as each other and may be (C1-C7)alkyl, specifically methyl, ethyl or n-propyl, and more specifically methyl. .

The mononuclear metallocene compound according to one embodiment may be, for example, selected from the group below, but is not limited thereto.

A mononuclear metallocene compound according to one embodiment can be prepared using materials and reaction conditions known in the art.

Additionally, one embodiment provides a supported mononuclear metallocene catalyst in which the mononuclear metallocene compound of the novel structure is supported on a carrier.

Specifically, the supported mononuclear metallocene catalyst according to one embodiment is,

It may include a carrier and a mononuclear metallocene compound represented by the following formula (1) supported on the carrier.

[Formula 1]

(In Formula 1, R ₁ to R ₁₅ , Y ₁ , M ₁ , A, L and n are the same as the definitions in Formula 1 described above.)

The supported mononuclear metallocene catalyst according to one embodiment includes a mononuclear metallocene compound represented by Formula 1 above, thereby realizing high activity compared to a conventional supported catalyst, and at the same time enabling the production of high molecular weight polyolefin and increasing productivity. It can be improved.

The polymerization activity (number of grams of polymer produced by adding unit g of supported catalyst) of the supported mononuclear metallocene catalyst according to one embodiment is 10 kg-polymer/g-cat.,h or more, or 15 kg-polymer/g. -cat.,h or more, or 18 kg-polymer/g-cat.,h or more, or 40 kg-polymer/g-cat.,h or less, or 30 kg-polymer/g-cat.,h or less. .

Specifically, the carrier may be an aluminum compound-carrier complex in which an aluminum compound forms a complex with the carrier.

The carrier is, for example, one or two selected from silica, alumina, magnesium chloride, calcium chloride, bauxite, zeolite, magnesium oxide, zirconium oxide, titanium oxide, boron trioxide, calcium oxide, zinc oxide, barium oxide and thorium oxide. It may be any of the above inorganic carriers, but is not limited thereto.

For example, the aluminum compound may be selected from an organic aluminum compound represented by Formula 11 or Formula 12 below, but is not limited thereto.

[Formula 11]

-[Al(R ₅₁ )-O] _c -

[Formula 12]

D(R ₅₂ ) ₃

(In Formulas 11 and 12 above,

R ₅₁ is halogen, C1-C30 hydrocarbyl, or C1-C20 hydrocarbyl substituted with halogen, c is an integer of 2 or more,

D is aluminum or boron, and R ₅₂ is C1-C20 hydrocarbyl or C1-C20 hydrocarbyl substituted by halogen.)

Specific examples of the compound represented by Formula 11 include methylaluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butylaluminoxane, hexylaluminoxane, octylaluminoxane, and decyl. Aluminoxane (Decylaluminoxane), etc., and specifically, may be methylaluminoxane.

Specific examples of the compound represented by Formula 12 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloroaluminum, triisopropyl aluminum, tri-s-butyl aluminum, and tricyclopentyl. Aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyldimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide. , trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, and tributyl boron, as well as dimethylaluminum methoxide, diethylaluminum methoxide, and dibutylaluminum methoxide. ), Methylaluminum dimethoxide, Ethylaluminum dimethoxide, Butylaluminum dimethoxide, Dimethylaluminum chloride, Diethylaluminum chloride, D Dibutylaluminum chloride, Methylaluminum dichloride, Ethylaluminum dichloride, Butylaluminum dichloride, etc. Specifically, trimethylaluminum, triethyl aluminum or triiso It may be butyl aluminum.

In the supported mononuclear metallocene catalyst according to one embodiment, the ratio of the metal of the mononuclear metallocene compound and the aluminum of the aluminum compound-support complex (Zr:Al ratio) may be 1:20 to 70, specifically 1: : It may be 30 to 50, and more specifically, it may be 1:35 to 45. When the above range is satisfied, catalyst activity can be further improved.

Additionally, one embodiment provides a method for producing the supported mononuclear metallocene catalyst.

A method for producing a supported mononuclear metallocene catalyst according to one embodiment,

Preparing an aluminum compound-support complex by reacting an aluminum compound and a support; and

It may include preparing a supported mononuclear metallocene catalyst by reacting the aluminum compound-support complex with the mononuclear metallocene compound represented by the following formula (1).

[Formula 1]

(In Formula 1, R ₁ to R ₁₅ , Y ₁ , M ₁ , A, L and n are the same as the definitions in Formula 1 described above.)

The aluminum compound-carrier complex according to one embodiment may be prepared in a hydrocarbon solvent, and specifically, may be prepared by reacting in a toluene solvent at a temperature of 30 to 130° C. for 30 minutes to 5 hours, but there is a limitation thereto. That is not the case.

Additionally, the aluminum aluminum compound may be used in an amount of 30 to 60 parts by weight, specifically 40 to 50 parts by weight, based on 100 parts by weight of the carrier. When an aluminum compound-support complex is manufactured with the above content, the supported catalyst activity can be maximized, and most of the added aluminum compounds are attached to the surface of the silica (support), making the manufacturing process easy and ensuring economic efficiency. It can be advantageous.

For example, if the aluminum compound is added in an amount of 40 parts by weight or less per 100 parts by weight of the support, the activity is low, and if it is added in an amount of 50 parts by weight or more, a significant amount of the added aluminum compound does not adhere to the surface of the support and adheres. The amount itself is smaller than when added at 40 to 50 parts by weight, which may cause problems in realizing high activity.

The step of preparing a supported mononuclear metallocene catalyst by supporting the mononuclear metallocene compound of Formula 1 according to one embodiment on the aluminum compound-support complex. Various types of hydrocarbon solvents can also be used, but specifically, toluene solvent is used. You can use it. There is no particular limitation on the reaction temperature and time, but the supported catalyst can be prepared by reacting at about 20 to 130° C. for about 30 minutes to 5 hours.

As an example, the mononuclear metallocene compound represented by Formula 1 may be used in an amount of 50 to 200 μmol-Metal/g-(aluminum compound-support complex), specifically 50 to 150 μmol relative to the aluminum compound-support complex. It can be used as -Metal/g- (aluminum compound-carrier complex). When the above range is satisfied, the activity of the catalyst (number of grams of polymer produced by adding unit g of supported catalyst) can be further maximized.

Additionally, one embodiment provides a method for producing polyolefin, including the step of polymerizing one or more olefin monomers in the presence of the supported mononuclear metallocene catalyst.

In the polyolefin production method according to one embodiment, polyolefin can be produced by adding the supported dinuclear metallocene catalyst as is or with some modification to an existing commercialized gas phase process or slurry process, or by developing a new process and introducing it. can do. In the gas phase process, the polymerization reaction can be carried out by contacting only the supported mononuclear metallocene catalyst and the olefin monomer without adding a solvent, and the reaction temperature and pressure can be operated according to typical gas phase process conditions. In the slurry process, the reaction can be carried out under a hydrocarbon solvent, but usually an aliphatic hydrocarbon solvent such as hexane isobutane is mainly used, and the reaction temperature and pressure can be operated according to typical slurry process conditions.

The olefin monomer according to one embodiment may be one or two or more selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, and mixtures thereof. It is not limited to this.

Hereinafter, the above-described implementation example will be described in more detail through examples. However, the following examples are for illustrative purposes only and do not limit the scope of rights.

The physical properties of the examples were measured as follows.

1) Polymerization activity

Polymerization was performed using a Parr 450mL high pressure reactor. Reaction solvent is n-Hexane, polymerization temperature is 80 It was carried out under ℃ conditions. Polymerization activity was measured as the ratio of the weight of the polymer produced (kg PE) per catalyst content (g of catalyst) used based on unit time (h).

2) Apparent density (bulk density)

Measured according to ASTM D 1895 Method A.

3) Molecular weight and dispersion

Analysis was performed using gel permeation chromatography (GPC). In the PL-GPC 220 instrument, the standard material was polystyrene, the solvent was 1,2,4-trichlorobenzene, the temperature was 160°C, and the column was PLgel mixed-B 7.5 Х 300 mm from Varian (Polymer Lab).

<Reagents and experimental conditions>

All experiments were performed in an inert atmosphere using a standard glove box and Schlenk technique. Tetrahydrofuran (THF), hexane and toluene were distilled from benzophenone ketyl. Hexane (anhydrous grade) used in the polymerization reaction was purchased from Fisher Scientific Korea and purified using Na/K alloy. Ethylene gas was purified using molecular sieves and copper under 48 bar pressure for more than 12 hours. ¹ H NMR (600 MHz) and ¹³ C NMR (150 MHz) analysis was performed on a JEOL ECZ 600 instrument.

[Preparation Example 1] Preparation of 2,7-di-t-butylfluorenyl-Li salt

After adding 2,7-di-t-butylfluorene (18.0 mmol) and toluene (50 mL) to a one-necked flask, n-BuLi (18.0 mmol, 2.5 M solution in hexane) was slowly added at room temperature. . The mixed solution was heated to 80°C, reacted for 5 hours, and filtered to obtain 2,7-di-t-butylfluorenyl-Li salt.

[Preparation Example 2] Preparation of 2-methyl-4-(4-t-butylphenyl)-indenyl-Li salt

After dissolving 2-methyl-4-(4-t-butylphenyl)-indene (3.00 g, 1.14 mmol) in hexane (30 mL) in a one-necked flask, n-BuLi (3.17 g, 1.14 mmol, 2.5 M solution in hexane) was added slowly. The mixed solution was reacted overnight and filtered to obtain 2-methyl-4-(4-t-butylphenyl)-indenyl-Li salt (2.54 g, 83%).

[Comparative Preparation Example 1] Preparation of fluorenyl-Li salt

Fluorenyl-Li salt was obtained in the same manner as in Preparation Example 1, except that fluorene was used instead of 2,7-di-t-butylfluorene.

[Comparative Preparation Example 2] Preparation of 2-methyl-4-phenyl-indenyl-Li salt

2-methyl-4-phenyl- Indenyl-Li salt was obtained.

<Preparation of mononuclear metallocene compounds>

[Example 1]

Preparation of compound 1-a

To a solution of 2,7-di-t-butylfluorenyl-Li salt (0.853 g, 3.00 mmol) dissolved in hexane (30 mL), tert-butyl methyl ether (0.886 g) was added. Lower the temperature to -78°C, add a solution of tBuO(CH ₂ ) ₆ (Me)SiCl ₂ (0.814 g, 3.00 mmol) dissolved in hexane (7.5 mL), and then raise the temperature of the mixed solution to room temperature. The reaction was allowed to occur overnight. After removing the solvent using a vacuum line, by-products were removed through filtration using Celite, washed several times with hexane, and the solvent was removed again using a vacuum line to obtain compound 1-a (1.51 g, 98%). .

Preparation of compound 1-b

2,4,5-trimethyl-4H-cyclopenta[b]thiophene (2,4,5-Me ₃ C ₇ H ₃ S) was prepared by referring to a method known in European Polymer Journal 144 (2021) 110243. . Potassium hydride (KH, 0.104 g, 2.6 mmol) and tetrahydrofuran (THF, 2.0 mL) were added to a schlenk flask, and the 2,4,5- Me ₃ C ₇ H ₃ S (0.325 g, A solution of 2.00 mmol) dissolved in THF (2.0 mL) was added and reacted overnight at room temperature (25°C). After removing the remaining KH through Celite filtration, a solution of compound 1-a (1.02 g, 2.00 mmol) dissolved in THF (15 mL) and copper cyanide (CuCN, 1.8 mg, 1 mol%) were added. The temperature of the mixed solution was lowered to -30°C, then raised to room temperature and reacted overnight. After removing the solvent using a vacuum line, it was washed several times with hexane and filtered through Celite. After removing the solvent, silica gel column chromatography (hexane:diethyl ether=30:1, v/v) was performed to obtain Compound 1-b in the form of a yellow-brown oil (0.854 g, 67%).

Preparation of mononuclear metallocene compound 1

Compound 1-b (0.347 g, 0.541 mmol) and THF (2 mL) obtained above were added to a one-necked flask, the temperature was lowered to -30°C, and n-BuLi (0.300 g, 2.5 M, 1.08 mmol) was added. was added slowly. The temperature of the mixed solution was slowly raised to room temperature and then reacted for 1 hour. Afterwards, the reaction was cooled to -30°C again, methylmagnesium bromide (0.91 mL, 1.24 mmol, 1.37 M solution in THF-toluene) and ZrCl ₄ (THF) ₂ (0.200 g, 0.530 mmol) were added, and the temperature was brought to room temperature. The reaction was allowed to take place overnight. After removing the solvent using a vacuum line, extraction was performed with hexane, by-products were removed through filtration using Celite, and the solvent was removed again using a vacuum line to obtain mononuclear metallocene compound 1 (0.379 g, 94 %).

¹ H NMR (C ₆ D ₆ ): δ 7.97 and 7.95 (d, J = 1.4 Hz, 1H), 7.87 (d, J = 8.3 Hz, 1H), 7.79 and 7.78 (s, 1H), 7.64 and 7.62 ( s, 1H), 7.51 and 7.50 (dd, J = 3.4 Hz and 1.4 Hz, 1H), 7.44 and 7.42 (dd, J = 8.7 Hz and 1.4 Hz, 1H), 6.23 (q, J = 1.4 Hz, 1H) , 3.31 and 3.30 (q, J = 6.2 Hz, 2H), 2.13 (d, J = 1.4 Hz, 3H, SiCH ₃ ), 2.03 (s, 3H, CH ₃ ), 1.93 and 1.89 (s, 3H, CH ₃ ), 1.39, 1.36, 1.34, and 1.32 (s, 18H, tBu), 1.26 and 1.08 (s, 3H, Si-CH ₃ ), 1.15 and 1.14 (s, 9H, OtBu), -1.07 and -1.08 (s , 3H, ZrCH ₃ ), -1.58 (s, 3H, ZrCH ₃ ) ppm.

[Example 2]

Same as Example 1 except that 2-methyl-4-(4-t-butylphenyl)-indenyl-Li salt was used instead of 2,7-di-t-butylfluorenyl-Li salt. This was performed to obtain mononuclear metallocene compound 2 (92%).

¹ H NMR (C ₆ D ₆ ): δ 7.90-7.87 and 7.86-7.84 (m, 2H, 4-tBuPh-H), 7.73, 7.70, 7.39, and 7.37 (d, J = 8.7 Hz, 1H), 7.49 , 7.42, 7.29, and 7.27 (d, J = 8.3 Hz, 1H), 7.42-7.38 (m, 2H, 4-tBuPh-H), 7.31 and 7.29 (s, 1H, indenyl-H), 6.96-6.89 ( m, 1H), 6.37 and 6.25 (m, 1H, thiophene-H), 3.33-3.29 (m, 2H, OCH ₂ ), 2.26, 2.24, 2.15, and 2.14 (s, 3 H, CH ₃ ), 2.19, 2.18, 2.09, and 2.08 (d, J = 1.4 Hz, 3H, SCCH ₃ ), 2.07, 2.03, and 2.00 (s, 3H, CH ₃ ), 1.88, 1.86, 1.84, and 1.78 (s, 3H, indenyl -CH ₃ ), 1.75-1.25 (m, 10H, CH ₂ ), 1.24, 1.23, and 1.23 (s, 9H, tBu), 1.16, 1.16, 1.16, and 1.15 (s, 9H, tBu), 1.08, 0.89 , 0.84, and 0.73 (s, 3H, SiCH ₃ ), 0.18 and -0.37 (s, 3H, Zr-CH ₃ ), -0.84, -0.85, -1.31, and -1.32 (s, 3H, Zr-CH ₃ ).

[Comparative Example 1]

Mononuclear metallocene compound C1 was obtained in the same manner as Example 1, except that fluorenyl-Li salt was used instead of 2,7-di-t-butylfluorenyl-Li salt.

¹ H NMR (C ₆ D ₆ ): δ 7.95 (d, J = 8.3 Hz, 1H), 7.85 (d, J = 8.3 Hz, 1H), 7.74 (d, J = 8.3 Hz, 1H), 7.45 (d , J = 8.3 Hz, 1H), 7.34 (t, J = 8.3 Hz, 1H), 7.23 (t, J = 8.3 Hz, 1H), 7.01 (td, 3 J = 8.3 Hz, 4 J = 1.4 Hz, 1H) ), 7.00 (td, 3 J = 8.3 Hz, 4 J = 1.4 Hz, 1H), 6.18 (q, J = 1.4 Hz, 1H), 3.31 and 3.30 (q, J = 6.2 Hz, 2H), 2.13 (d , J = 1.4 Hz, 3H, SCCH ₃ ), 2.03 (s, 3H, CH ₃ ), 1.93 and 1.89 (s, 3H, CH ₃ ), 1.26 and 1.08 (s, 3H, Si-CH ₃ ), 1.15 and 1.14 (s, 9H, OtBu), -1.06 and -1.07 (s, 3H, ZrCH ₃ ), -1.57 (s, 3H, ZrCH ₃ ) ppm.

[Comparative Example 2]

A mononuclear metallocene compound was prepared in the same manner as in Example 1 except that 2-methyl-4-phenyl-indenyl-Li salt was used instead of 2,7-di-t-butylfluorenyl-Li salt. C2 was obtained.

[Comparative Example 3]

Instead of 2,7-di-t-butylfluorenyl-Li salt, 2-methyl-4-(4-t-butylphenyl)-indenyl-Li salt is used, and tBuO(CH ₂ ) ₆ (Me) Mononuclear metallocene compound C3 was prepared in the same manner as Example 1, except that dimethyldichlorosilane was used instead of SiCl ₂ .

¹ H NMR (C ₆ D ₆ ): δ 7.88 (d, J = 8.3 Hz, 2H), 7.64 (d, J = 8.3 Hz, 1H), 7.41 (d, J = 8.3 Hz, 2H), 7.25 (d , J = 8.3 Hz, 1H), 7.24 (s, 1H), 6.87 (dd, J = 9.0 Hz and 6.9 Hz, 1H), 6.26 (s, 1H), 2.14 (s, 3H, CH ₃ ), 2.09 ( s, 3H, CH ₃ ), 1.98 (s, 3H, CH ₃ ), 1.83 (s, 3H, CH ₃ ), 1.25 (s, 9H, tBu), 1.00 (s, 3H, SiCH ₃ ), 0.65 (s , 3H, SiCH ₃ ), 0.12 (s, 3H, ZrCH ₃ ), -1.38 (s, 3H, ZrCH ₃ ) ppm.

<Preparation of supported catalyst and ethylene polymerization>

[Example 3] Preparation of supported catalyst using mononuclear metallocene compound 1 and ethylene polymerization using the same

Preparation of silica-aluminoxane composite (MAO-silica)

Dried silica (Grace, SYLOPOL 2410, 1.0 g), methylaluminoxane (MAO, Grace, 5 g, 10% by weight solution in toluene), and toluene (10 mL) were added to a one-necked round flask, and incubated at 70°C. It was stirred for 3 hours. Afterwards, unreacted methylaluminoxane was removed by filtration while washing with toluene (10 mL) to obtain silica-aluminoxane complex (MAO-silica).

Preparation of supported mononuclear metallocene catalyst

The silica-aluminoxane complex (1.0 g), mononuclear metallocene compound 1 (150 μmol) of Example 1, and toluene (10 mL) were added to a round-necked flask and reacted at 70°C for 1 hour. Afterwards, it was filtered and washed with toluene (20 mL), and the solvent was removed using a vacuum line to obtain supported mononuclear metallocene catalyst 1.

ethylene polymerization

The high pressure reactor (internal capacity: 450 mL, stainless steel) was evacuated at 120°C for 4 hours and the interior was purged with nitrogen. Triethylaluminum (Et ₃ Al, 0.20 mL) and hexane (300 mL) were added to the reactor and stirred at 80°C for 1 hour. Afterwards, the solution was removed with a cannula, the reactor was evacuated again at 120°C for 4 hours, and the interior was purged with nitrogen. Afterwards, hexane (300 mL) was added to the reactor again, the temperature was set to 80°C, triethyl aluminum (0.2 mL) and 1-hexene (3.0 mL) solution, and the supported mononuclear metallocene catalyst were added. 1 (6.0 mg) was prepared in a syringe and then added to each in order. The ethylene valve was opened to fill the internal ethylene pressure to 20 bar, and then polymerization was performed for 30 minutes while maintaining the pressure of 20 bar and the temperature of 80°C. Afterwards, the supply of ethylene was stopped, and the ethylene was exhausted when the temperature dropped to room temperature. The reaction product was filtered to remove the solvent, and then ethylene polymer was obtained. The physical properties of the catalyst and ethylene polymer are shown in Table 1 below.

[Example 4]

The same procedure as Example 3 was performed except that mononuclear metallocene compound 2 was used instead of mononuclear methyllocene compound 1. The physical properties of the catalyst and ethylene polymer are shown in Table 1 below.

[Comparative Examples 4 to 6]

The same procedure as Example 3 was performed except that mononuclear metallocene compounds C1 to C3 were used instead of mononuclear methyllocene compound 1. The physical properties of the catalyst and ethylene polymer are shown in Table 1 below.

compound
No. polymerization activity
(kg-PE/g-cat.,h) Apparent density
(g/ ^cm3 ) 1-hexene
(NMR, weight %) M _w
(KDa) PDI
( _Mw / _Mn ) Example 3 One 19.6 0.35 0.79 37.3 4.1 Example 4 2 23.2 0.36 1.08 19.6 5.2 Comparative Example 4 C1 4.7 0.34 0.6 31 3.8 Comparative Example 5 C2 5.6 0.35 0.85 21.4 3.8 Comparative Example 6 C3 5.6 0.35 1.78 24.6 3.5

Referring to Table 1, it can be seen that the supported catalyst prepared from the compounds of the examples can realize high activity, has excellent comonomer response, and can polymerize high molecular weight polyethylene. Specifically, the supported catalyst according to one embodiment is 10 kg-PE/g-cat.,h or more, or 15 kg-PE/g-cat.,h or more, or 15 kg-PE/g-cat.,h to It can be seen that it has a polymerization activity of 30 kg-PE/g-cat.,h and can produce high molecular weight polyethylene in the range of 15 KDa to 40 KDa.

On the other hand, the polymerization activity of the supported catalyst prepared from the compound of the comparative example that does not contain a t-butyl substituent and/or a 6-butoxy-hexyl substituent was significantly reduced to 10 kg-PE/g-cat., or less.

In summary, the supported catalyst prepared from a novel mononuclear metallocene compound according to one embodiment can be used as a polyolefin polymerization catalyst to produce high molecular weight polyolefin with excellent efficiency, and productivity can also be improved.

As described above, the present invention has been described with specific details and limited embodiments, but these are provided only to facilitate a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and the field to which the present invention belongs is not limited to the above embodiments. Those skilled in the art can make various modifications and variations from this description.

Accordingly, the spirit of the present invention should not be limited to the described embodiments, and the scope of the patent claims described below as well as all modifications that are equivalent or equivalent to the scope of this patent claim shall fall within the scope of the spirit of the present invention. .

Claims (13)

A mononuclear metallocene compound represented by Formula 1:
[Formula 1]

In Formula 1,
Ring A is an aromatic ring or an alicyclic ring;
M ₁ is a Group 4, 5, or 6 transition metal;
Y ₁ is C or Si;
L is a single bond, (C1-C30)alkylene or (C6-C30)arylene;
R ₁ and R ₂ are each independently hydrogen, (C1-C30)alkyl, (C1-C30)alkoxy, or (C6-C30)aryl, or R ₁ and R ₂ are connected to each other to form an alicyclic ring or an aromatic ring. may be formed, and the alicyclic ring and aromatic ring may be further substituted with (C1-C30)alkyl;
R ₃ to R ₆ are each independently hydrogen, (C1-C30)alkyl, (C1-C30)alkoxy, (C2-C30)alkenyl, (C6-C30)aryl, (C6-C30)aryloxy, (C1 -C30)alkyl(C6-C30)aryl, (C6-C30)aryl(C1-C30)alkyl, mono(C1-C30)alkylamino, di(C1-C30)alkylamino, mono(C6-C30)arylamino or di(C6-C30)arylamino;
R ₇ and R ₈ are each independently (C1-C30)alkyl, (C2-C30)alkenyl, tri(C1-C30)alkylsilyl, tri(C6-C30)arylsilyl, or halogen;
R ₉ to R ₁₅ are each independently (C1-C30)alkyl;
n is an integer from 1 to 10. According to clause 1,
The mononuclear metallocene compound is represented by the following Chemical Formula 2 or Chemical Formula 3:
[Formula 2]

[Formula 3]

In Formulas 2 and 3,
M ₁ is a Group 4, 5, or 6 transition metal;
Y ₁ is C or Si;
L is a single bond, (C1-C7)alkylene or (C6-C12)arylene;
R ₁ and R ₂ are each independently hydrogen, (C1-C7)alkyl, (C1-C7)alkoxy, or (C6-C12)aryl;
R ₃ to R ₆ are each independently hydrogen, (C1-C7)alkyl, (C1-C7)alkoxy, (C2-C7)alkenyl, (C6-C12)aryl, (C6-C12)aryloxy, (C1) -C7)alkyl(C6-C12)aryl, (C6-C12)aryl(C1-C7)alkyl, mono(C1-C7)alkylamino, di(C1-C7)alkylamino, mono(C6-C12)arylamino or di(C6-C12)arylamino;
R ₇ and R ₈ are each independently (C1-C7)alkyl, (C2-C7)alkenyl, tri(C1-C7)alkylsilyl, tri(C6-C12)arylsilyl, or halogen;
R ₉ to R ₂₁ are each independently (C1-C7)alkyl;
n is an integer from 1 to 6. According to clause 2,
In Formulas 2 and 3, M ₁ is titanium, hafnium, or zirconium. According to clause 2,
The mononuclear metallocene compound is a mononuclear metallocene compound represented by the following Chemical Formula 4 or Chemical Formula 5.
[Formula 4]

[Formula 5]

In Formulas 4 and 5 above,
R ₁ to R ₆ are each independently hydrogen or (C1-C7)alkyl;
R ₇ and R ₈ are each independently (C1-C7)alkyl or halogen;
R ₉ is (C1-C7)alkyl;
n is an integer from 1 to 6. According to clause 4,
The mononuclear metallocene compound is selected from the following.

carrier; and
A supported mononuclear metallocene catalyst comprising a mononuclear metallocene compound represented by the following formula (1) supported on the carrier:
[Formula 1]

In Formula 1, R ₁ to R ₁₅ , Y ₁ , M ₁ , A, L and n are the same as defined in Formula 1 of claim 1. According to clause 6,
The supported mononuclear metallocene catalyst is an aluminum compound-support complex. According to clause 7,
The aluminum compound-support complex is one selected from silica, alumina, magnesium chloride, calcium chloride, bauxite, zeolite, magnesium oxide, zirconium oxide, titanium oxide, boron trioxide, calcium oxide, zinc oxide, barium oxide and thorium oxide. Or, a supported mononuclear metallocene catalyst in which an aluminum compound forms a complex on two or more supports. According to clause 6,
A supported mononuclear metallocene catalyst, wherein the molar ratio of the mononuclear metallocene compound and the carrier is 1:2 to 1:5000. Preparing an aluminum compound-support complex by reacting an aluminum compound and a support; and
Preparing a supported mononuclear metallocene catalyst by reacting the aluminum compound-support complex with the mononuclear metallocene compound represented by the following formula (1): A method for producing a supported mononuclear metallocene catalyst, comprising:
[Formula 1]

In Formula 1, R ₁ to R ₁₅ , Y ₁ , M ₁ , A, L and n are the same as defined in Formula 1 of claim 1. According to clause 10,
A method for producing a supported mononuclear metallocene catalyst, wherein the aluminum compound is used in an amount of 10 to 50 parts by weight based on 100 parts by weight of the support. A method for producing polyolefin, comprising the step of polymerizing one or more olefin monomers in the presence of a supported mononuclear metallocene catalyst selected from claims 6 to 9. According to clause 12,
The olefin monomer is one or more selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, 1-octene, and mixtures thereof.