KR101685663B1 - Method for preparing polyolefin and polyolefin prepared therefrom - Google Patents

Abstract

The present invention relates to a process for producing a polyolefin which makes it possible to produce an ultra-high molecular weight polyolefin which is difficult to produce through a conventional metallocene catalyst more easily and effectively, and a polyolefin produced therefrom. The method for producing a polyolefin includes a metallocene supported catalyst in which a metallocene compound having a specific chemical structure is supported on a support; And polymerizing the olefinic monomer in the presence of a molecular weight modifier.

Description

METHOD FOR PREPARING POLYOLEFIN AND POLYOLEFIN PREPARED THEREFORM Technical Field [1] The present invention relates to a method for producing a polyolefin,

The present invention relates to a process for producing a polyolefin which makes it possible to produce an ultra-high molecular weight polyolefin which is difficult to produce through a conventional metallocene catalyst more easily and effectively, and a polyolefin produced therefrom.

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, both of which have been developed for their respective characteristics. Ziegler-Natta catalysts have been widely applied to commercial processes since the invention of the 50's. However, since the Ziegler-Natta catalyst is a multi-site catalyst having a plurality of active sites, the molecular weight distribution of the polymer is broad, The composition distribution is not uniform and there is a limit in securing desired physical properties. In particular, due to the broad molecular weight distribution, polymer chains having relatively low molecular weights may cause property degradation.

Furthermore, when an ultrahigh molecular weight polyolefin having a weight average molecular weight of 1,000,000 or more is produced using a Ziegler-Natta catalyst, the amount of catalyst residue (Cl component, etc.) is large, and decomposition of polyolefin may occur during molding at high temperature. . For this reason, there is a disadvantage that the excellent physical properties as the ultrahigh molecular weight polyolefin can not be properly manifested.

On the other hand, when a high molecular weight polyolefin is obtained by using a metallocene catalyst, since the molecular weight distribution is relatively small, deterioration of physical properties due to polymer chains having low molecular weight can be reduced, thereby improving impact resistance. Further, since the amount of the Cl residue of the catalyst residue is small, the decomposition of the polyolefin can be largely suppressed during the molding process.

However, in the process of obtaining a high molecular weight polyolefin using a metallocene catalyst, the molecular weight can be controlled by controlling the amount of hydrogen gas input. As the amount of hydrogen gas input increases, the molecular weight of the polyolefin decreases. Furthermore, even if the polymerization is proceeded in the state where no hydrogen gas is introduced, it is difficult to obtain an ultra high molecular weight polyolefin having a weight average molecular weight of 1 million or more because of its excellent hydrogen elimination reaction due to the characteristics of the metallocene catalyst.

Accordingly, there is a continuing need to develop a technique capable of producing the ultrahigh molecular weight polyolefin using a metallocene catalyst.

Accordingly, it is an object of the present invention to provide a process for producing a polyolefin and a polyolefin produced therefrom, which makes it possible to more easily and effectively produce an ultra-high molecular weight polyolefin which is difficult to produce through a conventional metallocene catalyst.

The present invention relates to a metallocene supported catalyst in which at least one metallocene compound represented by the following general formula (1) is supported on a carrier; And

In the presence of a molecular weight modifier,

And polymerizing the olefin-based monomer.

 [Chemical Formula 1]

In Formula 1,

A represents a hydrogen atom, a halogen atom, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, a C7 to C20 arylalkyl group, a C1 to C20 alkoxy group, C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;

D is -O-, -S-, -N (R) - or -Si (R) (R ') -, wherein R and R' are the same or different and each independently hydrogen, halogen, C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group;

L is a straight or branched alkylene group of C1 to C10;

B is carbon, silicon or germanium;

Q is hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group;

M is a Group 4 transition metal;

X ₁ and X ₂ are the same or different and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;

C ₁ And C ₂ are the same or different and each independently represent one of the following structural formulas (2a), (2b) or (2c) except that the case where both of C 1 and C 2 are of the general formula (2c);

 (2a)

(2b)

[Chemical Formula 2c]

Wherein R 1 to R 17 and R 1 'to R 9' are the same or different from each other and each independently represents hydrogen, halogen, a C 1 to C 20 alkyl group, a C 2 to C 20 alkenyl group, a C 1 to C 20 alkyl A silyl group, a C1 to C20 silylalkyl group, a C1 to C20 alkoxysilyl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, Two or more adjacent R10 to R17 may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.

The present invention also provides a polyolefin produced by the above-mentioned process for producing a polyolefin. Such a polyolefin may be an ultra high molecular weight polyolefin having a large weight average molecular weight of 1,500,000 to 5,000,000 g / mol.

Hereinafter, a method for producing a polyolefin according to a specific embodiment of the present invention and a polyolefin produced therefrom will be described.

According to an embodiment of the present invention, there is provided a metallocene supported catalyst comprising at least one metallocene compound represented by the following general formula (1) supported on a carrier; And polymerizing the olefinic monomer in the presence of a molecular weight modifier.

 [Chemical Formula 1]

In Formula 1,

A represents a hydrogen atom, a halogen atom, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, a C7 to C20 arylalkyl group, a C1 to C20 alkoxy group, C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;

D is -O-, -S-, -N (R) - or -Si (R) (R ') -, wherein R and R' are the same or different and each independently hydrogen, halogen, C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group;

L is a straight or branched alkylene group of C1 to C10;

B is carbon, silicon or germanium;

Q is hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group;

M is a Group 4 transition metal;

X ₁ and X ₂ are the same or different and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a nitro group, an amido group, a C1 to C20 alkylsilyl group , A C1 to C20 alkoxy group, or a C1 to C20 sulfonate group;

C ₁ And C ₂ are the same or different and each independently represent one of the following structural formulas (2a), (2b) or (2c) except that the case where both of C 1 and C 2 are of the general formula (2c);

 (2a)

(2b)

[Chemical Formula 2c]

Wherein R1 to R17 and R1 'to R9' are the same or different from each other and each independently represents hydrogen, halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkyl A silyl group, a C1 to C20 silylalkyl group, a C1 to C20 alkoxysilyl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, Two or more adjacent R10 to R17 may be connected to each other to form a substituted or unsubstituted aliphatic or aromatic ring.

In one embodiment, the polyolefin is prepared by polymerizing an olefin monomer using a metallocene supported catalyst supported on the metallocene compound of Formula 1 and a molecular weight regulator described below.

In this preparation method, the metallocene compound of the above formula (1) forms a structure in which an indeno indole derivative and / or a fluorene derivative is bridged by a bridge and can function as a Lewis base in the ligand structure Having a non-covalent electron pair, it can be supported on the surface having the Lewis acid property of the carrier to exhibit higher polymerization activity. In addition, the activity is high by including an electronically enriched indenoindole group and / or a fluorene group, and the hydrogen reactivity is low and the high activity can be maintained due to the appropriate steric hindrance and the electronic effect of the ligand. In addition, beta-hydrogen elimination can be inhibited by stabilizing beta-hydrogen of the polymer chain in which the nitrogen atom of the indenoindole derivative grows by hydrogen bonding, thereby enabling the production of a polyolefin having a higher molecular weight.

Furthermore, by appropriately using a molecular weight modifier together with the metallocene supported catalyst containing the metallocene compound of the formula (1), it is possible to obtain a catalyst having a weight average molecular weight of about 1 million or more It has been confirmed that an ultra high molecular weight polyolefin having a molecular weight of about 1.5 million or more can be produced.

In the metallocene compound of Formula 1, each substituent will be described in detail as follows.

Examples of the C1 to C20 alkyl group include a linear or branched alkyl group and specific examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, An octyl group, and the like, but are not limited thereto.

The C2 to C20 alkenyl group includes a straight chain or branched alkenyl group, and specific examples include, but are not limited to, an allyl group, an ethenyl group, a propenyl group, a butenyl group, and a pentenyl group.

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

The C5 to C20 heteroaryl group includes a heteroaryl group of a monocyclic or condensed ring and includes a carbazolyl group, a pyridyl group, a quinolinyl group, an isoquinoline group, a thiophenyl group, a furanyl group, an imidazole group, an oxazolyl group, , Triazine group, tetrahydropyranyl group, tetrahydrofuranyl group and the like, but are not limited thereto.

Examples of the C1 to C20 alkoxy groups include, but are not limited to, a methoxy group, an ethoxy group, a phenyloxy group, and a cyclohexyloxy group.

Examples of the Group 4 transition metal include, but are not limited to, titanium, zirconium, and hafnium.

R1 to R17 and R1 'to R9' each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, A halogen atom, a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a triisopropylsilyl group, a trimethylsilyl group, a trimethylsilyl group, a trimethylsilyl group, More preferably a silylmethyl group, a methoxy group or an ethoxy group, but is not limited thereto.

It is more preferable that L in the above formula (1) is a linear or branched alkylene group of C4 to C8, but is not limited thereto. The alkylene group may be substituted or unsubstituted with a C1 to C20 alkyl group, a C2 to C20 alkenyl group, or a C6 to C20 aryl group.

In the above formula (1), A represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a methoxymethyl group, Methoxyethyl group, a tetrahydrofuranyl group, or a tetrahydrofuranyl group, but is not limited thereto.

B in the above formula (1) is preferably silicon, but is not limited thereto.

According to one embodiment of the present invention, a specific example of the structure represented by the formula (2a) includes a structure represented by one of the following structural formulas, but is not limited thereto.

Specific examples of the structure represented by Formula 2b include structures represented by one of the following structural formulas, but the present invention is not limited thereto.

Specific examples of the structure represented by Formula 2c include structures represented by one of the following structural formulas, but the present invention is not limited thereto.

In addition, specific examples of the metallocene compound represented by Formula 1 include compounds represented by one of the following structural formulas, but the present invention is not limited thereto.

The above metallocene compound of formula (1) can produce a polyolefin having excellent activity and a high molecular weight. In particular, even when it is supported on a carrier, it exhibits a high polymerization activity, making it possible to produce a polyolefin having an extremely high molecular weight.

The metallocene compound of Formula 1 may be obtained by ligating an indenoindole derivative and / or a fluorene derivative with a bridging compound to prepare a ligand compound, followed by metallation with a metal precursor compound . The method for producing the metallocene compound will be described in the following Examples.

On the other hand, in the process for producing a polyolefin according to one embodiment of the present invention, the metallocene supported catalyst is a metallocene compound in which only the compound belonging to the category of the formula (1) is supported on the carrier and no other metallocene compound is supported . By using the metallocene supported catalyst supported only on the metallocene compound of formula (1), a polyolefin having an ultra-high molecular weight and a narrow molecular weight distribution can be effectively produced.

In the method for producing a polyolefin, a carrier containing a hydroxy group on its surface may be used as the carrier, and preferably a carrier having a hydroxy group and a siloxane group, Can be used.

Silica-alumina, silica-magnesia, and the like, which are usually dried at high temperature, and which are usually made of oxides such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg (NO ₃ ) ₂ , Sulfate, and nitrate components.

The drying temperature of the carrier is preferably about 200 to 800 ° C, more preferably about 300 to 600 ° C, and most preferably about 300 to 400 ° C. If the drying temperature of the carrier is less than about 200 ° C, moisture is too much to cause the co-catalyst to react with moisture on the surface. When the temperature exceeds about 800 ° C, pores on the surface of the carrier are combined to reduce the surface area, The silane group is left only and the siloxane group is left, and the reaction site with the cocatalyst is reduced.

The amount of the hydroxyl group on the surface of the carrier is preferably about 0.1 to 10 mmol / g, more preferably about 0.5 to 1 mmol / g. The amount of the hydroxyl group on the surface of the carrier can be controlled by the preparation method and conditions of the carrier or by drying conditions such as temperature, time, vacuum or spray drying.

If the amount of the hydroxyl group is less than about 0.1 mmol / g, the number of sites of reaction with the co-catalyst is small. If the amount is more than about 10 mmol / g, it may be due to moisture other than hydroxyl groups present on the surface of the carrier particle It is not preferable.

On the other hand, in the method for producing a polyolefin in one embodiment, the olefin monomer is polymerized in the presence of the aforementioned metallocene supported catalyst in the presence of a molecular weight modifier to prepare a polyolefin.

More specifically, the molecular weight modifier may comprise a mixture of a cyclopentadienyl metal compound of formula (VII) and an organoaluminum compound of formula (VIII) or a reaction product thereof:

(7)

Cp ₄ Cp ₅ M'X ' ₂

In Formula 7,

Cp ₄ and Cp ₅ are each independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted indenyl group or a ligand containing a substituted or unsubstituted fluorenyl group, and M 'is a Group 4 transition metal element , X 'is halogen;

[Chemical Formula 8]

R _d R _e R _f Al

In Formula 8,

R _d , R _e and R _f are each independently an alkyl group or a halogen having 4 to 20 carbon atoms, and R _d , R _e and R _f Is an alkyl group having 4 to 20 carbon atoms.

Although such a molecular weight modifier itself does not exhibit a large activity as an olefin polymerization catalyst, it assists the activity of the metallocene supported catalyst to enable the production of a polyolefin having a larger molecular weight and the like. Although the mechanism of the action of the molecular weight modifier is not certain, it seems to be possible to produce a polyolefin having a large molecular weight, etc., by interacting with the metallocene supported catalyst to increase the active sites accessible by the monomer.

Accordingly, in the method for producing a polyolefin in one embodiment, it is possible to more effectively prepare an ultra-high molecular weight polyolefin using such a molecular weight modifier and the above-mentioned metallocene supported catalyst.

In the above molecular weight modifier, specific examples of the cyclopentadienyl metal compound of the formula (7) include biscyclopentadienyl titanium dichloride, biscyclopentadienyl zirconium dichloride, biscyclopentadienyl hafnium dichloride, bisindenyl titanium Dichloride or bis-fluorenyltitanium dichloride. Specific examples of the organoaluminum compound represented by the formula (8) include triisobutylaluminum, trihexylaluminum, trioctylaluminum, diisobutylaluminum chloride, dihexylaluminum chloride and isobutylaluminum dichloride.

The compound of formula (7) and the compound of formula (8) may be used in a molar ratio of metal element (M ') contained in formula (7) and aluminum (Al) contained in formula (8) in the range of about 1: 0.1 to 1: It is preferably used in a molar ratio of about 1: 0.5 to 1:10.

On the other hand, the above-mentioned molecular weight modifier may be used in a state of being supported on the carrier together with the metallocene compound of the above-mentioned formula (1), but may be added to and mixed with the reaction system separately from the metallocene supported catalyst.

The above-mentioned molecular weight modifier may be used in an amount such that the molar ratio of the Group 4 transition metal: the molecular weight modifier contained in the metallocene compound is about 1: 0.1 to 1: 2, or about 1: 0.2 to 1: 1.5 have. If the amount of the molecular weight modifier used is too small, it may be difficult to produce an ultra-high molecular weight polyolefin properly. Conversely, if the amount of the molecular weight modifier used is too large, a polyolefin having a larger molecular weight can be produced, but the catalytic activity may be lowered.

Meanwhile, in the method for producing a polyolefin according to an embodiment, the metallocene supported catalyst may further include a cocatalyst supported on the carrier together with the metallocene compound. The kind of this promoter is not particularly limited, and any promoter known to be usable with a metallocene catalyst, for example, an organometallic compound containing a Group 13 metal, etc., can be used without any limitation. However, it is appropriate to use a borate-based cocatalyst represented by the following formula (6) in order to reduce degradation of the catalytic activity by the molecular weight modifier and to maintain higher catalytic activity.

[Chemical Formula 6]

T ⁺ [BG ₄ ] ^-

In formula (6), T ⁺ is a polyatomic ion of +1 valence, B is boron of +3 oxidation state, and G is each independently selected from the group consisting of hydride group, dialkylamido group, halide group, alkoxide group, aryloxide group, Carbocyclic group, halocarbyl group, and halo-substituted hydrocarbyl group, wherein G has not more than 20 carbons, but G is a halide group in at least one position.

By using such a promoter, a polyolefin having a higher molecular weight can be efficiently produced with high catalytic activity.

Such borate cocatalysts can be tri-substituted ammonium salts, or dialkylammonium salts, borate compounds in the form of trisubstituted phosphonium salts. Specific examples of such a promoter include trimethylammonium tetraphenylborate, methyl dioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, methyl N, N-dimethylanilinium tetraphenylborate, N, N-diethylanilinium tetraphenylborate, N, N-dimethyl (2,4,6-trimethylanilinium) tetra (Pentafluorophenyl) borate, methyldiotetradecylammonium tetrakis (pentaphenyl) borate, methyl dioctadecylammonium tetrakis (pentafluorophenyl) borate, triethylammonium, tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (Pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium (Pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (Pentafluorophenyl) borate, N, N-dimethyl (2,4,6-trimethylanilinium) tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis Tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate , Tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) Borate, N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylanilinium tetrakis (2,3,4,6-tetrafluoro Borate compound in the form of a tri-substituted ammonium salt such as N, N-dimethylformamide, N, N-dimethylformamide or N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis- (2,3,4,6-tetrafluorophenyl) ; A borate-based compound in the form of a dialkylammonium salt such as dioctadecylammonium tetrakis (pentafluorophenyl) borate, ditetradecylammonium tetrakis (pentafluorophenyl) borate or dicyclohexylammonium tetrakis (pentafluorophenyl) compound; (Pentafluorophenyl) borate or tri (2,6-, dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, methyl dioctadecylphosphonium tetrakis ) Borate and the like, and the like.

The cocatalyst may be used in an amount such that the molar ratio of the transition metal to the cocatalyst included in the metallocene supported catalyst is about 1: 0.1 to 1: 5, or about 1: 0.5 to 1: 1.5, High molecular weight polyolefin can be produced more effectively while maintaining high activity of the metallocene supported catalyst.

The metallocene supported catalyst as described above can be prepared by supporting a promoter on a support and further supporting a metallocene compound thereon and optionally the molecular weight regulator is mixed with a metallocene compound or a metallocene compound Or by carrying it before or after the carrying. The supporting method of each component depends on the production process and conditions of a conventional supported metallocene catalyst, and a further description thereof will be omitted.

In the preparation of the metallocene supported catalyst, the mass ratio of the transition metal to the carrier included in the metallocene compound represented by Formula 1 may be about 1:10 to 1: 1,000. When the carrier and the metallocene compound are contained in the above mass ratio, they can exhibit an optimum shape.

Meanwhile, in the process for producing a polyolefin according to an embodiment, the metallocene supported catalyst may be prepared by reacting with an olefin monomer to prepare a prepolymerized catalyst. For example, the catalyst may be ethylene, propylene, 1-butene, -Hexene, 1-octene, or the like, to prepare a prepolymerized catalyst.

The olefin-based monomer may be ethylene, alpha-olefin, cyclic olefin, diene olefin having 2 or more double bonds, or triene olefin.

Specific examples of the olefin-based monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-hexene, 1-hexene, 1-hexene, 1-hexene, 1-hexene, 1-hexene, , 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene. These two or more monomers may be mixed and copolymerized.

The polymerization reaction can be homopolymerized with one olefin monomer or copolymerized with two or more monomers using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor. However, according to the method of one embodiment, it is appropriate to polymerize the olefin-based monomer by slurry polymerization or gas-phase polymerization in the absence of hydrogen gas in order to more effectively obtain the ultra-high molecular weight polyolefin.

The metallocene supported catalyst may be an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms such as pentane, hexane, heptane, nonane, decane, isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, dichloromethane, Or a hydrocarbon solvent substituted with a chlorine atom such as chlorine atom or the like, or may be diluted and injected into the reaction system. The solvent used here is preferably used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkylaluminum, and it is also possible to use a further cocatalyst.

The polyolefin obtained according to the preparation method of one embodiment may be an ultra high molecular weight polyolefin having a weight average molecular weight of about 1,000,000 to 5,000,000 g / mol, or about 1,500,000 to 4,500,000 g / mol, and has a molecular weight distribution (Mw / Mn) Is from about 3.0 to 5.0, and the density is from about 0.92 g / cc to 0.95 g / cc. .

Such an ultra high molecular weight polyolefin has a relatively narrow molecular weight distribution and a very high molecular weight, and the amount of the catalyst residue is small due to the characteristics of the polyolefin produced by the metallocene catalyst, so that decomposition of the polyolefin during the high temperature molding can be suppressed. Therefore, it can be preferably used for obtaining high strength super fibers which can exhibit excellent physical properties according to high molecular weight and which can be considered as an engineering plastic or a kebla substitute for manufacturing mechanical parts and the like.

According to the production method of the present invention, an ultra-high molecular weight polyolefin, which has been difficult to produce with conventional metallocene catalysts, can be produced very effectively. Such an ultra high molecular weight polyolefin can suppress the decomposition of polyolefin during the high temperature molding process because the amount of the catalyst residue is small due to the characteristics of the polyolefin produced by the metallocene catalyst. Therefore, it can be preferably used for obtaining high strength super fibers which can exhibit excellent physical properties according to high molecular weight and which can be considered as an engineering plastic or a kebla substitute for manufacturing mechanical parts and the like.

Hereinafter, the present invention will be described in detail with reference to examples. However, these embodiments may be modified in various forms, and the scope of the invention should not be construed as being limited by the embodiments described below.

< Example >

Manufacturing example  One: Metallocene  Preparation of Compound A

1-1 Ligand  Preparation of compounds

fluorene was dissolved in 5 mL of MTBE and 100 mL of hexane, and 5.5 mL of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath and stirred overnight at room temperature. (3.6 g) was dissolved in hexane (50 mL), and the fluorene-Li slurry was transferred for 30 minutes under a dry ice / acetone bath. The mixture was stirred overnight at room temperature. At the same time, 5,8-dimethyl-5,10-dihydroindeno [1,2-b] indole (12 mmol, 2.8 g) was dissolved in 60 mL of THF and 5.5 mL of 2.5 M n-BuLi hexane solution was dissolved in a dry ice / acetone bath And the mixture was stirred at room temperature overnight. dimethyl-5,10-dihydroindeno [1,2-b] indole-2-carboxylic acid was obtained by NMR spectroscopic analysis of the reaction solution of (6- (tert-butoxy) The Li solution was transferred under a dry ice / acetone bath. The mixture was stirred at room temperature overnight. After the reaction, the residue was extracted with ether / water, and the residual water of the organic layer was removed with MgSO ₄ to obtain a ligand compound (Mw = 597.90, 12 mmol). It was confirmed by 1H-NMR that two isomers were formed.

¹ H NMR (500 MHz, d 6 -benzene): -0.30 to -0.18 (3H, d), 0.40 (2H, m), 0.65-1.45 (8H, m), 1.12 D), 3.17 (2H, m), 3.41-3.43 (3H, d), 4.17-4.21 (1H, d), 4.34-4.38

1-2 Metallocene  Preparation of compounds

7.2 g (12 mmol) of the ligand compound synthesized in 1-1 above was dissolved in 50 mL of diethylether, and 11.5 mL of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice / acetone bath and stirred overnight at room temperature. And dried in vacuo to obtain a brown color sticky oil. And dissolved in toluene to obtain a slurry. ZrCl ₄ (THF) ₂ was prepared and 50 mL of toluene was added thereto to prepare a slurry. A 50 mL toluene slurry of ZrCl ₄ (THF) ₂ was transferred in a dry ice / acetone bath. It was changed to violet color by stirring overnight at room temperature. The reaction solution was filtered to remove LiCl. Toluene in the filtrate was removed by vacuum drying, and then hexane was added thereto for sonication for 1 hour. The slurry was filtered to give 6 g of dark violet metallocene compound (Mw 758.02, 7.92 mmol, yield 66 mol%), which was a filtered solid. Two isomers were observed in &lt; 1 &gt; H-NMR.

¹ H NMR (500 MHz, CDCl ₃ ): 1.19 (9H, d), 1.71 (3H, d), 1.50-1.70 (4H, m), 1.79 (2H, m), 3.91 (3H, d), 6.66-7.88 (15H, m)

Manufacturing example  2: Metallocene  Preparation of Compound B

2-1 Ligand  Preparation of compounds

Add 2.63 g (12 mmol) of 5-methyl-5,10-dihydroindeno [1,2-b] indole to a 250 mL flask and dissolve in 50 mL of THF. Add 6 mL of 2.5 M n-BuLi hexane solution to the dr yice / acetone bath And the mixture was stirred at room temperature overnight. In another 250 mL flask, 1.62 g (6 mmol) of (6- (tert-butoxy) hexyl) dichloro (methyl) silane was dissolved in 100 mL of hexane, and then 5-methyl-5,10-dihydroindeno [1,2-b] indole in tetrahydrofuran and slowly stirred at room temperature overnight. After the reaction, the residue was extracted with ether / water. The residual water in the organic layer was removed with MgSO ₄ and vacuum dried to obtain 3.82 g (6 mmol) of a ligand compound.

^{1 H NMR (500 MHz, CDCl3} ): -0.33 (3H, m), 0.86 ~ 1.53 (10H, m), 1.16 (9H, d), 3.18 (2H, m), 4.07 (3H, d), 4.12 ( 3H, d), 4.17 (1 H, d), 4.25 (1 H, d), 6.95-7.92 (16 H, m)

2-2 Metallocene  Preparation of compounds

After dissolving 3.82 g (6 mmol) of the ligand compound synthesized in 2-1 above in 100 mL of toluene and 5 mL of MTBE, 5.6 mL (14 mmol) of 2.5 M n-BuLi hexane solution was added dropwise in a dryice / acetone bath, Lt; / RTI &gt; 2.26 g (6 mmol) of ZrCl ₄ (THF) ₂ was added to another flask and 100 ml of toluene was added to prepare a slurry. The toluene slurry of ZrCl ₄ (THF) ₂ was transferred to the litigated ligand in a dry ice / acetone bath. It was stirred overnight at room temperature and changed to violet color. The reaction solution was filtered to remove LiCl, and the resulting filtrate was vacuum-dried, and hexane was added thereto for sonication. The slurry was filtered to obtain 3.40 g (yield: 71.1 mol%) of a metallocene compound of dark violet filtered solid.

^{1 H NMR (500 MHz, CDCl3} ): 1.74 (3H, d), 0.85 ~ 2.33 (10H, m), 1.29 (9H, d), 3.87 (3H, s), 3.92 (3H, s), 3.36 (2H , &lt; / RTI &gt; m), 6.48 to 8.10 (16H, m)

Manufacturing example  3: Preparation of molecular weight regulator

1.25 g of bis (cyclopentadienyl) titanium dichloride and 10 mL of toluene were sequentially added to a 250 mL round bottom flask and stirred. 10 mL of triisooctylaluminium (1M in hexane) was added thereto, stirred at room temperature for 3 days, and then the solvent was removed in vacuo to obtain a green mixture, which was oxidized or colored Did not change. Hereinafter, the green mixture was used without purification. Also, it was confirmed by 1 H NMR that the mixture was bis (cyclopentadienyl) octyl titanium and dioctylaluminium chloride.

¹ H NMR (CDCl ₃ , 500 MHz): 7.31 (br s, 10H), 2.43 (d, 4H), 1.95-1.2

Manufacturing example  4 to 8: Metallocene  Preparation of Supported Catalyst

1-1 carrier  dry

Silica (SYLOPOL 2212, Grace Davison) was used as the carrier without firing and dehydrated and dried under vacuum at a temperature of 400 ° C for 15 hours.

1-2 Preparation of supported catalyst

10 g of the dried silica was placed in a glass reactor containing 250 mL of toluene, and 50 mL of toluene was further added thereto, followed by stirring. 20 mL of 10 wt% methylaluminoxane (MAO) / toluene solution was added and stirred at 40 ° C with stirring. Thereafter, the reaction product was washed with a sufficient amount of toluene to remove the unreacted aluminum compound, and the remaining toluene was removed by decompression. After the addition of 100 mL of toluene, 0.1 mmol of the metallocene compound A or B prepared in Preparation Example 1 or 2 was dissolved in 10 mL of toluene, and the mixture was reacted for 1 hour.

After the reaction was completed, the stirring was stopped, and the toluene layer was separated and removed. The reaction was carried out overnight by adding anilinium borate (N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, AB) dissolved in 10 mL of toluene. The reaction products were filtered and dried to prepare the metallocene supported catalysts of Production Examples 4 to 8.

In Production Examples 4 to 8, except that the kind of the metallocene compound used and the supported amount of the anilinium borate (AB) cocatalyst were changed as shown in the following Table 1, A metallocene supported catalyst was prepared.

Metallocene supported catalyst Type of metallocene compound Number of moles of anilinium borate (AB) co-catalyst in the supported metallocene catalyst (mmol) Production Example 4 Production Example 1 (A) 0 Production Example 5 Production Example 2 (B) 0 Production Example 6 Production Example 1 (A) 0.05 Production Example 7 Production Example 1 (A) 0.1 Production Example 8 Production Example 2 (B) 0.1

Manufacturing example  9 to 13: Metallocene  Preparation of Supported Catalyst (Supported with Molecular Weight Regulator)

1-1 carrier  dry

Silica (SYLOPOL 2212, Grace Davison) was used as the carrier without firing and dehydrated and dried under vacuum at a temperature of 400 ° C for 15 hours.

1-2 Preparation of supported catalyst

10 g of the dried silica was placed in a glass reactor containing 250 mL of toluene, and 50 mL of toluene was further added thereto, followed by stirring. 20 mL of 10 wt% methylaluminoxane (MAO) / toluene solution was added and stirred at 40 ° C with stirring. Thereafter, the reaction product was washed with a sufficient amount of toluene to remove the unreacted aluminum compound, and the remaining toluene was removed by decompression. After the addition of 100 mL of toluene, 0.1 mmol of the metallocene compound A or B prepared in Preparation Example 1 or 2 was dissolved in 10 mL of toluene, and the mixture was reacted for 1 hour. Thereafter, the molecular weight regulator obtained in Preparation Example 3 was dissolved in toluene, and the mixture was further reacted for 2 hours.

After the reaction was completed, the stirring was stopped, and the toluene layer was separated and removed. The reaction was carried out overnight by adding anilinium borate (N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, AB) dissolved in 10 mL of toluene. The reaction products were filtered and dried to prepare the metallocene supported catalysts of Production Examples 9 to 13.

In Production Examples 9 to 13, except that the type of the metallocene compound used, the loading amount of the anilinium borate (AB) cocatalyst, or the loading amount of the molecular weight modifier was changed as shown in Table 2, Each metallocene supported catalyst was prepared in the same manner.

Metallocene supported catalyst Type of metallocene compound Number of moles of anilinium borate (AB) co-catalyst in the supported metallocene catalyst (mmol) The molar fraction of the molecular weight regulator in the metallocene supported catalyst (the molar number of the molecular weight regulator in the supported catalyst / the number of moles of the transition metal contained in the supported catalyst) Production Example 9 Production Example 1 (A) 0 0.2 Production Example 10 Production Example 1 (A) 0.05 0.5 Production Example 11 Production Example 1 (A) 0.1 1.0 Production Example 12 Production Example 2 (B) 0.05 0.2 Production Example 13 Production Example 2 (B) 0.1 1.0

Comparative Examples 1 and 2: Ethylene-1-hexene copolymerization (using no molecular weight modifier) using the metallocene supported catalysts of Production Examples 4 and 5,

50 mg of each of the supported catalysts prepared in Production Examples 4 and 5 was quantitatively measured in a dry box and loaded in a 50 mL glass bottle as shown in Table 3, sealed with a rubber septum, and taken out from a dry box to prepare a catalyst to be injected. The polymerization was carried out in a temperature controlled, 2 L metal alloy reactor at high pressure equipped with a mechanical stirrer.

1 L of hexane containing 1.0 mmol of triethylaluminum and 1 mL of 1-hexene (5 mL) were fed into the reactor, and the prepared supported catalyst was introduced into the reactor without air contact, and then the gaseous ethylene monomer Was continuously polymerized at a pressure of 9 Kgf / cm &lt; ² &gt; for 1 hour. The termination of the polymerization was completed by first stopping the stirring and then removing ethylene by evacuation.

The resulting polymer was filtered to remove most of the polymer solvent, and then dried in a vacuum oven at 80 DEG C for 4 hours.

The polymerization conditions, the ethylene / 1-hexene polymerization activity, the density, the molecular weight and the molecular weight distribution of the obtained polymer are shown in Table 3 below for each of the catalysts prepared above.

Examples 1 to 6: Ethylene-1-hexene copolymerization using the metallocene supported catalysts of Production Examples 4 to 8 (used in polymerization of molecular weight modifiers)

50 mg of each of the supported catalysts prepared in Production Examples 4 to 8 were quantitatively measured in a dry box and loaded in a 50-mL glass bottle, sealed with a rubber septum, and taken out from a dry box to prepare a catalyst to be injected. The polymerization was carried out in a temperature controlled, 2 L metal alloy reactor at high pressure equipped with a mechanical stirrer.

1 L of hexane containing 1.0 mmol of triethylaluminum and 5 mL of 1-hexene were introduced into the reactor, and the molecular weight regulator of Preparation Example 3 was added to 0.2 mol of 1 mol of the transition metal contained in the supported catalyst To 1.0 mol (actual use: about 0.25 to 1.0 μmol) (see Table 3 below). Subsequently, the prepared supported catalysts were put into the reactor without air contact, and polymerized at 80 DEG C for 1 hour while continuously feeding gaseous ethylene monomer at a pressure of 9 Kgf / cm &lt; ^{2 &} gt ;. The termination of the polymerization was completed by first stopping the stirring and then removing ethylene by evacuation.

The resulting polymer was filtered to remove most of the polymer solvent, and then dried in a vacuum oven at 80 DEG C for 4 hours.

The polymerization conditions, the ethylene / 1-hexene polymerization activity, the density, the molecular weight and the molecular weight distribution of the obtained polymer are shown in Table 3 below for each of the catalysts prepared above.

Examples 7 to 11: Ethylene-1-hexene copolymerization using the metallocene supported catalysts of Production Examples 9 to 13 (used in polymerization of the molecular weight modifier)

Ethylene-1-hexene copolymerization was carried out in the same manner as in Comparative Examples 1 and 2, except that the metallocene supported catalysts of Production Examples 9 to 13 were used as shown in Table 4 below.

The polymerization conditions, the ethylene / 1-hexene polymerization activity, the density, the molecular weight and the molecular weight distribution of the obtained polymer are shown in Table 4 below.

Metallocene supported catalyst Molar fraction of molecular weight regulator used in polymerization (molar number of molecular weight regulator / number of moles of transition metal contained in supported catalyst) Active (kgPE / g catalyst) Density (g / cc) Molecular weight distribution (Mw / Mn) Mw Comparative Example 1 Production Example 4 0 8.9 0.9434 3.8 1112000 Comparative Example 2 Production Example 5 0 3.6 0.9412 4.0 1450000 Example 1 Production Example 4 One 2.8 0.9234 3.5 3673000 Example 2 Production Example 4 0.5 4.2 0.9275 3.2 2973000 Example 3 Production Example 5 0.2 2.3 0.9260 3.8 3204000 Example 4 Production Example 6 0.5 7.1 0.9274 3.7 3015000 Example 5 Production Example 7 0.5 10.4 0.9277 4.0 3424000 Example 6 Production Example 8 0.5 12.5 0.9226 4.2 4523000

Metallocene supported catalyst Active (kgPE / g catalyst) Density (g / cc) Molecular weight distribution (Mw / Mn) Mw Example 7 Production Example 9 7.1 0.9364 3.8 2322000 Example 8 Production Example 10 7.0 0.9282 4.0 2970000 Example 9 Production Example 11 6.8 0.9279 3.5 3538000 Example 10 Production Example 12 4.3 0.9280 3.2 3371000 Example 11 Production Example 13 3.5 0.9265 3.8 3824000

Referring to the Tables 3 and 4, it is confirmed that the ultra-high molecular weight polyolefin having an extremely high molecular weight can be easily produced in the Examples as compared with Comparative Examples.

Claims (15)

A metallocene supported catalyst in which at least one metallocene compound represented by the following general formula (1) is supported on a carrier; And
In the presence of a molecular weight modifier,
A method for producing a polyolefin comprising polymerizing an olefin monomer,
[Chemical Formula 1]

In Formula 1,
A is a C1 to C20 alkyl group;
D is -O-;
L is a straight or branched alkylene group of C1 to C10;
B is silicon;
Q is an alkyl group of C1 to C20;
M is a Group 4 transition metal;
X ₁ and X ₂ are the same or different from each other, and each independently is a halogen or a C 1 to C 20 alkyl group;
C ₁ and C ₂ are the same or different and each independently represent one of the following structural formulas (2a), (2b) or (2c) except that the case where both of C 1 and C 2 are of the general formula (2c);
(2a)

(2b)

[Chemical Formula 2c]

Wherein R1 to R17 and R1 'to R9' are the same or different from each other and each independently represents hydrogen, a C1 to C20 alkyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group , A C1 to C20 alkoxysilyl group, a C1 to C20 alkoxy group, or a C6 to C20 aryl group, and two or more adjacent two of R10 to R17 are connected to each other to form a substituted or unsubstituted aliphatic ring .
The method according to claim 1, wherein the metallocene compound represented by Formula 1 is selected from the group consisting of the following structural formulas:

The process for producing a polyolefin according to claim 1, wherein the metallocene supported catalyst is a metallocene compound in which only the metallocene compound of Formula 1 is supported on a support.
The method of claim 1, wherein the carrier is selected from the group consisting of silica, silica-alumina, and silica-magnesia.
The process for producing a polyolefin according to claim 1, wherein the molecular weight modifier comprises a cyclopentadienyl metal compound represented by the following general formula (7), a mixture of an organoaluminum compound represented by the following general formula (8)
(7)
Cp ₄ Cp ₅ M'X ' ₂
In Formula 7,
Cp ₄ and Cp ₅ are each independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted indenyl group or a ligand containing a substituted or unsubstituted fluorenyl group, and M 'is a Group 4 transition metal element , X 'is halogen;
[Chemical Formula 8]
R _d R _e R _f Al
In Formula 8,
R _d , R _e and R _f are each independently an alkyl group or a halogen having 4 to 20 carbon atoms, and R _d , R _e and R _f Is an alkyl group having 4 to 20 carbon atoms.
The process for producing a polyolefin according to claim 1, wherein the molecular weight modifier is carried on a carrier together with the metallocene compound or mixed with the metallocene supported catalyst.
The method of producing a polyolefin according to claim 1, wherein the molecular weight modifier is used so that the molar ratio of the Group 4 transition metal: the molecular weight modifier contained in the metallocene compound is 1: 0.1 to 1: 2.
The method of producing a polyolefin according to claim 1, wherein the metallocene supported catalyst further comprises a cocatalyst supported on a carrier together with the metallocene compound.
9. The process for producing a polyolefin according to claim 8, wherein the promoter comprises a borate-based promoter represented by the following formula (6): &lt; EMI ID =
[Chemical Formula 6]
T ⁺ [BG ₄ ] ^-
In formula (6), T ⁺ is a polyatomic ion of +1 valence, B is boron of +3 oxidation state, and G is each independently selected from the group consisting of hydride group, dialkylamido group, halide group, alkoxide group, aryloxide group, Carbocyclic group, halocarbyl group, and halo-substituted hydrocarbyl group, wherein G has not more than 20 carbons, but G is a halide group in at least one position.
The process for producing a polyolefin according to claim 8, wherein the cocatalyst is used so that the molar ratio of the transition metal to the cocatalyst contained in the metallocene supported catalyst is 1: 0.1 to 1: 5.
The method for producing a polyolefin according to claim 1, wherein the olefinic monomer is polymerized by slurry polymerization or gas phase polymerization in the absence of hydrogen gas.
The olefinic monomer according to claim 1, wherein the olefinic monomer is at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, , At least one monomer selected from the group consisting of 1-undecene, 1-dodecene, norbornene, ethylidene norbornene, styrene, alpha-methylstyrene and 3-chloromethylstyrene.
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