KR20160057930A - Supported hybrid catalyst and method for preparing of olefin based polymer using the same - Google Patents

Abstract

The present invention relates to a hybrid-supported catalyst and a method for producing an olefin-based polymer using the same. According to the present invention, the hybrid-supported catalyst exhibits high catalytic activity. In addition, it is possible to easily produce an olefin-based polymer having low melting temperature (Tm) and melt index (MI) by using the same. To this end, the hybrid-supported catalyst includes: a compound represented by chemical formula 1; a compound represented by chemical formula 2; and a carrier.

Description

TECHNICAL FIELD [0001] The present invention relates to a hybrid supported catalyst and a method for producing an olefinic polymer using the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a hybrid supported catalyst for producing an olefinic polymer having a low Tm and MI value with a high activity catalyst.

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, both of which have been developed for their respective characteristics. The Ziegler-Natta catalyst has been widely applied to commercial processes since its invention in the 1950's. However, since it is a multi-site catalyst having a plurality of active sites, the molecular weight distribution of the polymer is broad and the composition of the comonomer There is a problem that the desired physical properties can not be secured because the distribution is not uniform.

The metallocene catalyst consists of a combination of a main catalyst, which is the main component of the transition metal compound, and a cocatalyst, which is an organometallic compound mainly composed of aluminum. Such a catalyst is a single site catalyst as a homogeneous complex catalyst, According to the single active site characteristic, the molecular weight distribution is narrow, the polymer having uniform composition distribution of comonomer is obtained, and the stereoregularity of the polymer, copolymerization characteristics, molecular weight, crystallinity And the like.

On the other hand, the ansa-metallocene compound is an organometallic compound containing two ligands connected to each other by a bridge group. The bridge group prevents the rotation of the ligand, Activity and structure are determined.

These anisometallocene compounds are used as catalysts in the production of olefinic homopolymers or copolymers. In particular, it is known that an anisometallocene compound containing a cyclopentadienyl-fluorenyl ligand can produce a high molecular weight polyethylene, thereby controlling the microstructure of the polypropylene have. It is also known that an anisometallocene compound containing an indenyl ligand can produce an olefin polymer having excellent activity and improved stereoregularity.

The present inventors have disclosed an anthra-metallocene compound having a novel structure capable of providing various selectivity and activity to olefin polymers in Korean Patent Publication No. 10-2013-0125311.

On the other hand, in the case of bis-indenyl-ligand in an anisometallocene catalyst, two types of ligand, i.e., racemate and mirror-symmetrical meso-diastereomer, symmetric meso diastereomer) can be formed. In the case of racemates, mirror-symmetric meso-diastereomers are preferred because they produce isotactic polymers with high crystallinity and melting points and high specific gravity and mechanical strength, while atactic polymers It is a catalyst that should be avoided because it is manufactured. However, since the racemate and the mirror-symmetric meso-diastereomer are simultaneously produced in the process of preparing the anisma-metallocene catalyst, the structure of the anthra-metallocene catalyst, in which an excess of the racemate can be produced, Should be considered. In addition, there is a need for an anhydride-metallocene catalyst capable of producing olefinic polymers of higher molecular weight.

Accordingly, the present inventors have carried out various studies on a catalyst capable of producing an olefin-based polymer having a lower Tm and MI value while having higher activity than the catalysts described above, And a catalyst for producing an olefinic polymer having a high molecular weight can be used as the catalyst for the preparation of the olefin-based catalyst, and thus the present invention has been accomplished.

An object of the present invention is to provide a hybrid supported catalyst capable of producing an olefin polymer having high activity and low Tm and MI values.

The present invention also provides a process for producing an olefin polymer using the hybrid supported catalyst.

In order to solve the above problems, the present invention provides a hybrid supported catalyst comprising a compound represented by the following general formula (1), a compound represented by the following general formula (2), and a carrier.

[Chemical Formula 1]

In Formula 1,

X is the same or different halogen,

R ₁ is C _{6 -20} aryl substituted with C _{1 -20} alkyl,

R _2, R ₃ and R ₄ are each independently hydrogen, halogen, C _{1 -20} alkyl, C _{2 -20} alkenyl, C _{1 -20} alkyl, silyl, C _{1 -20} alkyl, silyl, C _{1 -20} alkoxysilyl group, and C _{1 -20} ether, C _{1 -20} silyl ether, C _{1 -20} alkoxy, C _{6 -20} aryl, C _{7 -20} alkyl, aryl, or C _{7 -20} arylalkyl,

A is carbon, silicon or germanium,

R ₅ is a substituted C _{1 -20} alkyl with C _{1 -20} alkyl,

R ₆ is hydrogen, C _{1 -20} alkyl or C _{2 -20} alkenyl,

(2)

In Formula 2,

X 'are the same or different halogen,

R ' ₁ is C _{6 -20} aryl substituted with C _{1 -20} alkyl,

R _'2, R' ₃ and R _'4 are each independently hydrogen, halogen, C _{1 -20} alkyl, C _{2 -20} alkenyl silyl, C _1-20 alkyl, C _{1 -20} alkyl, silyl, C _{1 -20} alkoxysilyl group, and C _{1 -20} ether, C _{1 -20} silyl ether, C _{1 -20} alkoxy, C _{6 -20} aryl, C _{7 -20} alkyl, aryl, or C _{7 -20} arylalkyl,

A 'is carbon, silicon or germanium,

R _'5 is a C _{1 -20} alkyl substituted with C _{1 -20} alkyl,

R ' ₆ is hydrogen, C _{1 -20} alkyl or C _{2 -20} alkenyl.

The compounds represented by Chemical Formulas 1 and 2 have an anis-metallocene structure and include two indenyl groups as a ligand. In particular, a bridge group connecting the ligand is substituted with a functional group capable of acting as a Lewis base as an oxygen-donor, thereby maximizing the activity as a catalyst. In addition, since a bulky group such as C _{6 -20} aryl (R ₁ ) substituted with C _{1 -20} alkyl is substituted for the indenyl group, the formation of meso form is inhibited by imparting steric hindrance. Accordingly, when the compounds represented by the formulas (1) and (2) are used as catalysts for preparing olefinic polymers, olefinic polymers having desired physical properties can be prepared more easily.

In addition, the compound represented by the above formula (1) contains zirconium (Zr) as a metal atom, so that the activity of the catalyst is high and the compound represented by the formula (2) contains hafnium (Hf) Polymerization is possible. In particular, when an olefin polymer is prepared by raising the content of a comonomer with a conventional catalyst, the olefin polymer having a high MI value is produced in a difficulty in the process, though the Tm is decreased. However, The advantage of being able to produce an olefin polymer having a low Tm and an MI value is low.

The molar ratio of the compound represented by Formula 1 to the compound represented by Formula 2 is preferably 2: 1 to 1: 5. And exhibits optimum catalytic activity and physical properties at the above-mentioned molar ratio, which is advantageous from the viewpoints of maintaining the activity of the catalyst and economical efficiency.

In the above formula (1), preferably, R ₁ is phenyl substituted with tert-butyl. More preferably, R < _{1 >} is 4-tert-butyl-phenyl.

Also preferably, R ₂ , R ₃ and R ₄ are hydrogen.

Also preferably, A is silicon.

Also preferably, R ₅ is 6-tert-butoxy-hexyl and R ₆ is methyl.

Representative examples of the compound represented by the above formula (1) are as follows:

The present invention also provides a process for preparing a compound represented by the above general formula (1) as shown in the following Reaction Scheme 1:

[Reaction Scheme 1]

Step 1 is a step of reacting a compound represented by Formula 1-2 with a compound represented by Formula 1-3 to prepare a compound represented by Formula 1-4. It is preferable to use alkyllithium (for example, n-butyllithium) in the above reaction, and the reaction temperature is -200 to 0 占 폚, more preferably -150 to 0 占 폚. As the solvent, toluene, THF and the like can be used. At this time, the organic layer may be separated from the product, and then the separated organic layer may be vacuum dried and excess reactant may be removed.

Step 2 is a step of reacting the compound represented by Formula 1-4 with the compound represented by Formula 1-5 to prepare the compound represented by Formula 1. [ It is preferable to use alkyllithium (for example, n-butyllithium) in the above reaction, and the reaction temperature is -200 to 0 占 폚, more preferably -150 to 0 占 폚. As the solvent, ether, hexane and the like can be used.

In the above formula (2), preferably, R ' ₁ is phenyl substituted with tert-butyl. More preferably, R ' ₁ is 4-tert-butyl-phenyl.

Also preferably, R _'2, R' ₃ and R _'4 are hydrogen.

Also preferably, A 'is silicon.

Also preferably, R ' ₅ is 6-tert-butoxy-hexyl and R' ₆ is methyl.

Representative examples of the compound represented by the general formula (2) are as follows:

The present invention also provides a process for preparing a compound represented by the above general formula (2) as shown in the following Reaction Scheme 2:

[Reaction Scheme 2]

Step 1 is a step of reacting a compound represented by Formula 2-2 with a compound represented by Formula 2-3 to prepare a compound represented by Formula 2-4. It is preferable to use alkyllithium (for example, n-butyllithium) in the above reaction, and the reaction temperature is -200 to 0 占 폚, more preferably -150 to 0 占 폚. As the solvent, toluene, THF and the like can be used. At this time, the organic layer may be separated from the product, and then the separated organic layer may be vacuum dried and excess reactant may be removed.

Step 2 is a step of reacting the compound represented by Formula 2-4 with the compound represented by Formula 2-5 to prepare the compound represented by Formula 2. [ It is preferable to use alkyllithium (for example, n-butyllithium) in the above reaction, and the reaction temperature is -200 to 0 占 폚, more preferably -150 to 0 占 폚. As the solvent, ether, hexane and the like can be used.

Further, preferably X and X ', R ₁ and R' _1, R ₂ and R _'2, R ₃ and R' _3, R ₄ and R _'4, A and A', R ₅ and R _'5, and R ₆ and R _'6 are respectively equal to each other. That is, it is preferable that the compound represented by Formula 1 and the compound represented by Formula 2 differ only in the metal atom.

In the hybrid supported catalyst according to the present invention, a carrier containing a hydroxy group on its surface may be used as the carrier, and preferably a carrier having a hydroxyl 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 200 to 800 ° C, more preferably 300 to 600 ° C, and most preferably 300 to 400 ° C. If the drying temperature of the carrier is less than 200 ° C, moisture is excessively large and the surface moisture reacts with the cocatalyst. When the temperature exceeds 800 ° C, the pores on the surface of the carrier are combined to reduce the surface area. And only the siloxane group is left, and the reaction site with the co-catalyst is reduced, which is not preferable.

The amount of hydroxyl groups on the surface of the support is preferably from 0.1 to 10 mmol / g, more preferably from 0.5 to 5 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 0.1 mmol / g, the number of sites of reaction with the co-catalyst is small. If the amount is more than 10 mmol / g, the hydroxyl group may be present in the water other than the hydroxyl group present on the surface of the carrier particle. not.

In the hybrid supported catalyst according to the present invention, the mass ratio of the catalyst (the compound represented by Formula 1 and the compound represented by Formula 2) to the support is preferably 1: 1 to 1: 1000. When the carrier and the catalyst are contained in the above-described mass ratio, they exhibit appropriate supported catalyst activity, which may be advantageous from the standpoint of maintaining the activity of the catalyst and economical efficiency.

In addition to the above catalyst, a promoter may be further used to prepare the olefinic polymer. The cocatalyst may further include at least one of the following promoter compounds represented by the following general formulas (3), (4) and (5).

(3)

_{- [Al (R 30) -O} ] m -

In Formula 3,

R ₃₀ may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;

m is an integer of 2 or more;

[Chemical Formula 4]

J ( _R31 ) ₃

In Formula 4,

R ₃₁ is as defined in Formula 3 above;

J is aluminum or boron;

[Chemical Formula 5]

[EH] ⁺ [ZA ₄ ] ^- or [E] ⁺ [ZA ₄ ] ^-

In Formula 5,

E is a neutral or cationic Lewis base;

H is a hydrogen atom;

Z is a Group 13 element;

A may be the same as or different from each other, and independently at least one hydrogen atom is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy .

Examples of the compound represented by the general formula (3) include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane and the like. A more preferred compound is methylaluminoxane.

Examples of the compound represented by Formula 4 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

Examples of the compound represented by Formula 5 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) Boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (ptrifluoromethylphenyl) boron, trimethylammoniumtetra (ptrifluoromethylphenyl) boron, tributylammoniumtetra N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum (P-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammonium (P-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N , N-diethylanilinium tetrapentafluorophenyl aluminum, diethylammonium tetrapentatetraphenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra (p-tolyl) Boron, triethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (p -trifluoromethylphenyl) boron, triphenylcarboniumtetra (p- Phenyl) boron and the like, triphenylamine car I phenylboronic as Titanium tetra-penta flow.

The hybrid supported catalyst according to the present invention comprises a support having a promoter compound supported thereon, supporting the compound represented by Formula 1 on the support, and supporting the compound represented by Formula 2 on the support And the order of loading can be changed as needed.

In the preparation of the hybrid supported catalyst, a hydrocarbon solvent such as pentane, hexane, heptane or the like, or an aromatic solvent such as benzene, toluene or the like may be used as a reaction solvent. In addition, the metallocene compound and the co-catalyst compound may be used in the form supported on silica or alumina.

The present invention also provides a process for producing an olefin-based polymer comprising polymerizing an olefin-based monomer in the presence of the hybrid supported catalyst.

In the process for preparing an olefin polymer according to the present invention, specific examples of the olefin monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl- Octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-aidocene and the like. Preferably, the olefinic polymer is a random copolymer of propylene and ethylene or a terpolymer of ethylene, propylene and C _{4 -8} olefins (especially 1-butene).

The polymerization reaction may be carried out by homopolymerization using one continuous slurry polymerization reactor, loop slurry reactor, gas phase reactor or solution reactor as one olefin monomer or copolymerization of two or more kinds of monomers.

The hybrid supported catalyst may be an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms such as pentane, hexane, heptane, nonane, decane and isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, chlorine atoms such as dichloromethane and chlorobenzene A substituted hydrocarbon solvent, or the like. 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.

Here, the polymerization may be carried out by reacting at a temperature of 25 to 500 ° C and a pressure of 1 to 100 kgf / cm 2 for 1 to 24 hours. At this time, the polymerization reaction temperature is preferably 25 to 200 ° C, more preferably 50 to 100 ° C. The polymerization reaction pressure is preferably 1 to 70 kgf / cm 2, and more preferably 5 to 40 kgf / cm 2. The polymerization reaction time is preferably 1 to 5 hours.

The above-mentioned polymerization process can control the molecular weight range of the olefin-based polymer finally produced according to the hydrogenation or not-added conditions. In particular, an olefin polymer having a high molecular weight can be produced under hydrogen-free conditions, and if hydrogen is added, a low molecular weight olefin polymer can be produced even with a small amount of hydrogenation. At this time, the hydrogen content added to the polymerization process is 0.07 L to 4 L under 1 atm of the reactor condition, or is supplied at a pressure of 1 bar to 40 bar or in a range of 168 ppm to 8,000 ppm Can be supplied.

The olefin-based polymer prepared by using the compound represented by Formula 1 and the compound represented by Formula 2 as a catalyst according to the present invention has smaller Tm and MI values than conventional metallocene catalysts Lt; / RTI >

The hybrid supported catalyst according to the present invention has high catalytic activity and can easily produce an olefin polymer having a low Tm and MI value when the olefin polymer is produced using the catalyst.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.

Manufacturing example  One

Step 1) Preparation of (6-t-butoxyhexyl) (methyl) -bis (2-methyl-4-tert- butylphenylindenyl)

(20.0 g, 76 mmol) was dissolved in toluene / THF = 10/1 solution (230 mL), and a solution of n-butyllithium (2.5 M in hexane solvent, 22 g) at 0 < 0 > C slowly and then stirred at room temperature for one day. Then, (6-t-butoxyhexyl) dichloromethylsilane (1.27 g) was slowly added dropwise to the mixed solution at -78 ° C, stirred for about 10 minutes, and then stirred at room temperature for one day. Thereafter, water was added to separate the organic layer, and the solvent was distillated under reduced pressure to obtain (6-t-butoxyhexyl) (methyl) -bis (2-methyl-4-tert-butylphenylindenyl) silane.

^{1 H NMR (500 MHz, CDCl} 3, 7.26 ppm): -0.20-0.03 (3H, m), 1.26 (9H, s), 0.50-1.20 (4H, m), 1.20-1.31 (11H, m), 1.40 (2H, m), 7.19-7.61 (14H, m), 1.36 (2H, m), 2.19-2.23 (6H, m), 3.30-3.34 m)

Step 2) Preparation of [(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4-tert-butylphenylindenyl)] zirconium dichloride

(6-t-butoxyhexyl) (methyl) -bis (2-methyl-4-tert-butylphenylindenyl) silane prepared in the above step 1 was dissolved in a toluene / THF = After dissolution, a n-butyllithium solution (2.5 M, hexane solvent, 22 g) was slowly added dropwise at -78 占 폚, and the mixture was stirred at room temperature for one day. To the reaction solution of bis (N, N'- diphenyl-1,3-propane dia shown) dichloro zirconium bis _{(tetrahydrofuran) [Zr (C 5 H 6} NCH 2 CH 2 NC 5 H 6) Cl 2 (C 4 H ₈ O) ₂ ] was dissolved in toluene (229 mL), then slowly added dropwise at -78 ° C, and the mixture was stirred at room temperature for one day. After the reaction solution was cooled to -78 ° C, a HCl ether solution (1 M, 183 mL) was slowly added dropwise thereto, followed by stirring at 0 ° C for 1 hour. After filtration and vacuum drying, hexane was added and stirred to precipitate crystals. The precipitated crystals were filtered off and dried under reduced pressure to obtain 20.5 g of [(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4-tert- butylphenylindenyl)] zirconium dichloride %).

¹ H NMR (500 MHz, CDCl ₃ , 7.26 ppm): 1.20 (9H, s), 1.27 (3H, s), 1.34 (18H, s), 1.20-1.90 , 2.26 (3H, s), 3.38 (2H, t), 7.00 (2H, s), 7.09-7.13 ), 7.59 (2H, d), 7.65 (2H, d)

Manufacturing example  2

Step 1) Preparation of (6-t-butoxyhexyl) (methyl) -bis (2-methyl-4- (4-t- butylphenyl) indenyl)

150 g of 2-methyl-4- (4-t-butylphenyl) indene was placed in a 3 L Schlenk flask and dissolved in toluene / THF (10: 1, 1.73 L) at room temperature . After cooling the solution to -20 캜, 240 mL of n-butyllithium solution (n-BuLi, 2.5 M in hexane) was slowly added dropwise, and the mixture was stirred at room temperature for 3 hours. Thereafter, the reaction solution was cooled to -20 캜, and then 82 g of (6-t-butoxyhexyl) dichloromethylsilane and 512 mg of CuCN were slowly added dropwise. The reaction solution was warmed to room temperature, stirred for 12 hours, and 500 mL of water was added. Thereafter, the treated organic layer was separated, washed, dehydrated, and filtered through a MgSO _4. The filtrate was distilled under reduced pressure to obtain a yellow oil.

^{1 H NMR (500 MHz, CDCl} 3, 7.26 ppm): -0.09 - -0.05 (3H, m), 0.40-0.60 (2H, m), 0.80-1.51 (26H, m), 2.12-2.36 (6H, m ), 3.20-3.28 (2H, m), 3.67-3.76 (2H, m), 6.81-6.83 (2H, m), 7.10-7.51

Step 2) Preparation of rac - [(6-t-butoxyhexylmethylsilanediyl) -bis (2-methyl- 4- (4- t- butylphenyl) indenyl)] hafnium dichloride

(6-t-butoxyhexyl) (methyl) bis (2-methyl-4- (4-t-butylphenyl)) indenylsilane prepared previously in a 3 L Schlenk flask, 1 L of ethyl ether was added and dissolved at room temperature. After the solution was cooled to -20 ° C, 240 mL of a n-butyllithium solution (n-BuLi, 2.5 M in hexane) was slowly added dropwise and the mixture was stirred at room temperature for 3 hours. Thereafter, the reaction solution was cooled to -78 deg. C, and then 92 g of hafnium chloride was added thereto. The reaction solution was warmed to room temperature, stirred for 12 hours, and the solvent was removed under reduced pressure. 1 L of dichloromethane was added, and then the insoluble inorganic salts and the like were removed by filtration. The filtrate was dried under reduced pressure, and again 300 mL of dichloromethane was added to precipitate crystals. The precipitated crystals were filtered and dried to obtain 80 g of rac - [(6-t-butoxyhexylmethylsilanediyl) -bis (2-methyl- 4- (4- t- butylphenyl) indenyl)] hafnium dichloride (Rac: meso = 50: 1).

^{1 H NMR (500 MHz, CDCl} 3, 7.26 ppm): 1.19-1.78 (37H, m), 2.33 (3H, s), 2.34 (3H, s), 3.37 (2H, t), 6.91 (2H, s) , 7.05-7.71 (14 H, m)

Example

3 g of silica L203F was preliminarily weighed in a shrinkage flask, and 10 mmol of methylaluminoxane (MAO) was added thereto, followed by reaction at 95 ° C for 24 hours. After precipitation, the upper layer was removed and washed once with toluene. 60 占 퐉 ol of the compound prepared in Preparation Example 2 was dissolved in toluene and reacted at 75 占 폚 for 5 hours. After the completion of the reaction, the upper layer solution was removed and the remaining reaction product was washed once with toluene. Then, 20 mu mol of the compound prepared in Preparation Example 1 was dissolved in toluene, and the mixture was further reacted at 75 DEG C for 2 hours. After the completion of the reaction, the upper layer solution was removed and the remaining reaction product was washed once with toluene. Dimethylanilinium tetrakis (pentafluorophenyl) borate (64 μmol) was added and reacted at 75 ° C for 5 hours. After completion of the reaction, the reaction product was washed with toluene, washed again with hexane and then vacuum dried to obtain a silica-supported metallocene catalyst in the form of solid particles.

Comparative Example  One

3 g of silica L203F was preliminarily weighed in a shrinkage flask, and 10 mmol of methylaluminoxane (MAO) was added thereto, followed by reaction at 95 ° C for 24 hours. After precipitation, the upper layer was removed and washed once with toluene. 60 占 퐉 ol of the compound prepared in Preparation Example 1 was dissolved in toluene and reacted at 75 占 폚 for 5 hours. After the completion of the reaction, the upper layer solution was removed and the remaining reaction product was washed once with toluene. Dimethyl anilinium tetrakis (pentafluorophenyl) borate (48 μmol) was added and reacted at 75 ° C for 5 hours. After completion of the reaction, the reaction product was washed with toluene, washed again with hexane and then vacuum dried to obtain a silica-supported metallocene catalyst in the form of solid particles.

Comparative Example  2

3 g of silica L203F was preliminarily weighed in a shrinkage flask, and 10 mmol of methylaluminoxane (MAO) was added thereto, followed by reaction at 95 ° C for 24 hours. After precipitation, the upper layer was removed and washed once with toluene. 60 占 퐉 ol of the compound prepared in Preparation Example 2 was dissolved in toluene and reacted at 75 占 폚 for 5 hours. After the completion of the reaction, the upper layer solution was removed and the remaining reaction product was washed once with toluene. Dimethyl anilinium tetrakis (pentafluorophenyl) borate (48 μmol) was added and reacted at 75 ° C for 5 hours. After completion of the reaction, the reaction product was washed with toluene, washed again with hexane and then vacuum dried to obtain a silica-supported metallocene catalyst in the form of solid particles.

Experimental Example

1) homopolymerization of propylene

The 2 L stainless steel reactor was vacuum dried at 65 占 폚, cooled, and then 1.5 mmol of triethylaluminum, 2 bar of hydrogen and 770 g of propylene were sequentially added at room temperature. After stirring for 10 minutes, the respective silica-supported metallocene catalysts prepared in the above Examples and Comparative Examples were dissolved in 20 mL of TMA-formulated hexane in the amounts shown in Table 1 below, and the reactor was charged under a nitrogen pressure. The temperature of the reactor was then slowly raised to 70 ° C and then polymerized for 1 hour. After the completion of the reaction, unreacted propylene was bubbled.

2) random polymerization of propylene

The 2 L stainless steel reactor was vacuum dried at 65 占 폚, cooled, and then 1.5 mmol of triethylaluminum and 770 g of propylene were sequentially introduced at room temperature. After stirring for 10 minutes, the respective silica-supported metallocene catalysts prepared in the above Examples and Comparative Examples were dissolved in 20 mL of TMA-formulated hexane in the amounts shown in Table 1 below, and the reactor was charged under a nitrogen pressure. After 15 g of ethylene was added, the temperature of the reactor was slowly raised to 70 ° C., and the reactor was polymerized for 1 hour. After completion of the reaction, unreacted propylene and ethylene were vented.

- Method of measuring physical properties of polymer

Each of the polymers thus prepared was measured for physical properties in the following manner.

(1) Catalytic activity: Calculated as the ratio of the weight of polymer produced (kg PP) per used catalyst (mmol and g of catalyst) based on unit time (h).

(2) Melting point (Tm) of polymer: The melting point of the polymer was measured using a differential scanning calorimeter (DSC, DSC 2920, manufacturer: TA instrument). Specifically, the polymer was heated to 220 ° C., and then the temperature was maintained for 5 minutes. After the temperature was lowered to 20 ° C., the temperature was increased again. The temperature rising rate and the falling rate were controlled at 10 ° C./min.

(3) Crystallization temperature (Tc) of the polymer: The crystallization temperature was determined from the curve obtained by decreasing the temperature under the same conditions as the melting point using DSC.

(4) Melt index (MFR, 2.16 kg): Measuring temperature 230 占 폚, ASTM 1238

- Measurement results of physical properties of polymer

The homo and random polymerization process conditions prepared by using the catalysts prepared in Examples and Comparative Examples and the measurement results of physical properties of the produced polypropylene are shown in Table 1 below.

catalyst Category ^{1 )} Polymerization temperature (캜) Amount of supported catalyst (mg) Yield (g) activation
(kg PP / g Cat.hr) MFR (g / 10 min) Tm (占 폚) T (占 폚) Example H 70 45 437.4 9.7 9.1 152.6 101.1 R 70 30 369.4 12.3 5.1 142.5 89.4 Comparative Example 1 H 70 45 453.9 10.1 7.0 149.9 100.7 R 70 45 519.2 11.5 7.9 141.9 91.3 Comparative Example 2 H 70 60 362.0 6.0 10.7 152.2 105.4 R 70 80 300.5 3.8 1.3 144.6 100.0 1) H: homopolymerization, R: random polymerization

As shown in Table 1, in the case of random polymerization, it was confirmed that the activity and the physical properties of the Example were significantly improved as compared with Comparative Examples 1 and 2 using the catalyst alone. Specifically, in Comparative Example 1, the film had a MFR exceeding 7.0 and could not be used for a film having a low melt flow. In Comparative Example 2, the MFR value was small but the activity was too low. On the other hand, it was confirmed that the Examples are more suitable for use in a film having a low melt flow rate because the catalyst activity is higher than those of Comparative Examples 1 and 2 and the MFR is less than 7.0.

Claims (18)

A compound represented by the following general formula (1)
A compound represented by the following formula (2) and
Hybrid supported catalyst comprising carrier:
[Chemical Formula 1]

In Formula 1,
X is the same or different halogen,
R ₁ is C _{6 -20} aryl substituted with C _{1 -20} alkyl,
R _2, R ₃ and R ₄ are each independently hydrogen, halogen, C _{1 -20} alkyl, C _{2 -20} alkenyl, C _{1 -20} alkyl, silyl, C _{1 -20} alkyl, silyl, C _{1 -20} alkoxysilyl group, and C _{1 -20} ether, C _{1 -20} silyl ether, C _{1 -20} alkoxy, C _{6 -20} aryl, C _{7 -20} alkyl, aryl, or C _{7 -20} arylalkyl,
A is carbon, silicon or germanium,
R ₅ is a substituted C _{1 -20} alkyl with C _{1 -20} alkyl,
R ₆ is hydrogen, C _{1 -20} alkyl or C _{2 -20} alkenyl,
(2)

In Formula 2,
X 'are the same or different halogen,
R ' ₁ is C _{6 -20} aryl substituted with C _{1 -20} alkyl,
R _'2, R' ₃ and R _'4 are each independently hydrogen, halogen, C _{1 -20} alkyl, C _{2 -20} alkenyl silyl, C _1-20 alkyl, C _{1 -20} alkyl, silyl, C _{1 -20} alkoxysilyl group, and C _{1 -20} ether, C _{1 -20} silyl ether, C _{1 -20} alkoxy, C _{6 -20} aryl, C _{7 -20} alkyl, aryl, or C _{7 -20} arylalkyl,
A 'is carbon, silicon or germanium,
R _'5 is a C _{1 -20} alkyl substituted with C _{1 -20} alkyl,
R ' ₆ is hydrogen, C _{1 -20} alkyl or C _{2 -20} alkenyl.
The method according to claim 1,
Wherein R < ₁ > is phenyl substituted with tert-butyl.
Hybrid supported catalyst.
The method according to claim 1,
R < _{1 >} is 4-tert-butyl-phenyl.
Hybrid supported catalyst.
The method according to claim 1,
R ₂ , R ₃ and R ₄ are hydrogen.
Hybrid supported catalyst.
The method according to claim 1,
Wherein A is silicon.
Hybrid supported catalyst.
The method according to claim 1,
R <_5> is 6-tert-butoxy-hexyl and R <_6> is methyl.
Hybrid supported catalyst.
The method according to claim 1,
The compound represented by the formula (1) is the following compound.
Hybrid Supporting Catalyst:

.
The method according to claim 1,
Lt; ₁ &gt; is phenyl substituted with tert-butyl.
Hybrid supported catalyst.
The method according to claim 1,
R &lt; _{1 &gt;} is 4-tert-butyl-phenyl.
Hybrid supported catalyst.
The method according to claim 1,
R ' ₂ , R ' ₃ and R ' ₄ are hydrogen.
Hybrid supported catalyst.
The method according to claim 1,
A 'is silicon.
Hybrid supported catalyst.
The method according to claim 1,
R ' ₅ is 6-tert-butoxy-hexyl and R ' ₆ is methyl.
Hybrid supported catalyst.
The method according to claim 1,
Wherein the compound represented by the general formula (2) is the following compound:
Hybrid Supporting Catalyst:

.
The method according to claim 1,
X and X ', R ₁ and R' _1, R ₂ and R _'2, R ₃ and R' _3, R ₄ and R _'4, A and A', R ₅ and R _'5, and R ₆ and R ' ₆ are identical to each other,
Hybrid supported catalyst.
The method according to claim 1,
Wherein the hybrid supported catalyst further comprises at least one compound selected from the group consisting of a compound represented by the following general formula (3), a compound represented by the general formula (4) and a compound represented by the general formula (5)
Hybrid Supporting Catalyst:
(3)
_{- [Al (R 30) -O} ] m -
In Formula 3,
R ₃₀ may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;
m is an integer of 2 or more;
[Chemical Formula 4]
J ( _R31 ) ₃
In Formula 4,
R ₃₁ is as defined in Formula 3 above;
J is aluminum or boron;
[Chemical Formula 5]
[EH] ⁺ [ZA ₄ ] ^- or [E] + [ZA ₄ ] ^-
In Formula 5,
E is a neutral or cationic Lewis base;
H is a hydrogen atom;
Z is a Group 13 element;
A may be the same as or different from each other, and independently at least one hydrogen atom is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy .
A method for producing an olefin-based polymer, which comprises polymerizing at least one olefin monomer in the presence of the hybrid supported catalyst according to any one of claims 1 to 15.
17. The method of claim 16,
The olefins may be selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, Octadecene, 1-octadecene, 1-eicosene, and mixtures thereof.
Gt;
17. The method of claim 16,
Characterized in that the at least one olefin monomer comprises ethylene or propylene or comprises ethylene, propylene and C _{4 -8} olefins.
Gt;