KR20170001424A - Catalyst system and process for preparing polyolefins - Google Patents

Abstract

The present invention relates to a catalyst system for producing polyolefin, which can realize high polymerization performance by improving a polymerization process and can provide polyolefin having a low content of fine particles, and a production method of polyolefin using the same. The catalyst system for producing polyolefin comprises: at least one compound represented by chemical formula 1; and ethoxylated amines.

Description

TECHNICAL FIELD [0001] The present invention relates to a catalyst system for preparing polyolefins,

The present invention relates to a catalyst system for producing polyolefins, which can provide a polyolefin which can improve the polymerization process and achieve a polymerization performance equal to or higher than that of the conventional one without any existing process troubles, .

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 anhydride-metallocene compound containing an indenyl ligand can produce a polyolefin having excellent activity and improved stereoregularity.

However, in the case of olefin polymerization using the conventional anisometallic metallocene compound, a fouling phenomenon often occurs in the polymerization process. This is because the static electricity is generated by the continuous friction between the polymer produced when the reaction occurs and the inside of the reactor or the generated polymers, and a large amount of the generated derivative causes fouling.

Accordingly, it is still necessary to study a catalyst system for producing polyolefins that can solve the problems of generating fine particles during polymerization and further causing problems such as fouling, thereby improving the polymerization process and achieving high polymerization performance Do.

An object of the present invention is to provide a catalyst system for producing polyolefins which can improve the polymerization process and realize a polymerization performance equal to or higher than that of the existing ones without any existing process troubles and to provide a polyolefin having a low content of fine particles.

The present invention also provides a method for producing a polyolefin using the polyolefin catalyst system.

The present invention relates to compounds represented by one or more of the following formula (1): And ethoxylated amines; ≪ RTI ID = 0.0 > a < / RTI > catalyst system for producing polyolefins.

The present invention also provides a process for producing a polyolefin comprising the step of polymerizing at least one or more olefin monomers in the presence of the catalyst system for producing polyolefins.

Hereinafter, a catalyst system for producing a polyolefin according to a specific embodiment of the present invention and a method for producing a polyolefin using the catalyst system will be described in detail.

According to one embodiment of the invention, there is provided a compound represented by one or more of the following formula (1): And

Ethoxylated amines; ≪ / RTI > a catalyst system for the production of polyolefins may be provided:

[Chemical Formula 1]

In Formula 1,

M is a Group 4 transition metal,

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.

The inventors of the present invention have found that, in the case of olefin polymerization using a conventional anisole-metallocene compound, static electricity is generated due to continuous friction between the polymer produced in the polymerization step and the inside of the reactor or generated polymers, And the fouling phenomenon. As a result, it was confirmed that when the catalyst system for producing a polyolefin comprising at least one of the compounds represented by the above-mentioned formula (1) and the ethoxylated amine was used, it was possible to provide a polyolefin having a high polymerization activity, And completed the invention.

The compound represented by Formula 1 has an anis-metallocene structure and includes 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 compound represented by the formula (1) is supported on its own or on a carrier to be used as a catalyst for the production of polyolefins, a polyolefin having desired physical properties can be more easily produced.

The catalyst system for producing a polyolefin according to one embodiment of the present invention may contain one or more compounds represented by the above formula (1). In particular, when two or more compounds represented by the formula (1) are included, it is preferable to include a compound containing a different metal as a transition metal.

For example, when a compound containing zirconium (Zr) and a compound containing hafnium (Hf) are mixed together with ethoxylated amine as the catalyst system for producing polyolefin, the olefin polymer having high molecular weight Lt; / RTI > 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, , There is an advantage that an olefin polymer having both Tm and MI values can be produced.

In Formula 1, M is a Group 4 transition metal, and more preferably zirconium, hafnium, or titanium.

The X may be the same or different from each other and is more preferably fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

In addition, R ₁ is preferably phenyl substituted with t-butyl, more preferably 4-t-butyl-phenyl.

It is preferable that R ₂ , R ₃ and R ₄ are each hydrogen or C _{1 -20} alkyl.

The A may be carbon, silicon or germanium, but is preferably silicon.

It is preferable that R ₅ is 6-t-butoxy-hexyl.

It is preferable that R ₆ is hydrogen or C _{1 -20} alkyl.

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

,

The compound represented by Formula 1 can be synthesized by the following reaction scheme 1, but is not limited thereto. The method for producing the compound represented by the above formula (1) will be described in more detail in the following examples.

[Reaction Scheme 1]

In the above Reaction Scheme 1, R ₁ to R ₆ , A, M, and X are as defined in Formula 1 above.

The step 1 is a step of reacting the compound represented by the formula 2 with the compound represented by the formula 3 to prepare the compound represented by the formula 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.

The step 2 is a step of reacting the compound represented by the formula 4 with the compound represented by the formula 5 to prepare the compound represented by the 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.

On the other hand, ethoxylated amines included in the catalyst system for producing polyolefins according to one embodiment of the present invention have a characteristic of reducing or eliminating the static electricity to be formed, and are excellent in antistatic effect and are included in the catalyst system for producing polyolefins , The fine powder content of the produced polyolefin can be remarkably reduced, and the fouling phenomenon, which is a process trouble, can be suppressed.

These ethoxylated amines may be represented by the following formula:

(2)

_{RN (C 2 H 4 OH)} 2

In Formula 2,

R is alkyl having 1 to 20 carbon atoms.

The ethoxylated amine may be mixed with the compound represented by the above formula (1) while being dissolved in an aliphatic hydrocarbon-based solvent such as hexane at the time of preparing the catalyst system for producing polyolefins.

In addition, the catalyst system for producing a polyolefin may be a catalyst supported on a carrier.

More specifically, the compound represented by Formula 1 and the ethoxylated amines may be supported on at least one carrier selected from the group consisting of silica, silica-alumina, and silica-magnesia.

The carrier may be any of those generally used in the technical field to which the present invention belongs, so that it is not particularly limited, but preferably at least one carrier selected from the group consisting of silica, silica-alumina and silica-magnesia may be used. On the other hand, when supported on a support such as silica, since the silica carrier and the functional group of the compound represented by the formula (1) are chemically bonded and supported, there is almost no catalyst liberated from the surface in the olefin polymerization process. Therefore, the slurry or the polyolefin The fouling phenomenon of the wall surface of the reactor or the aggregation of the polymer particles tends to be small.

In addition, the polyolefin produced in the presence of such a silica carrier-containing catalyst system is excellent in particle shape and apparent density of the polymer, and thus can be suitably used for a conventional slurry or gas phase polymerization process. Therefore, it is preferable to use a carrier which is dried at a high temperature and has a siloxane group having high reactivity on the surface.

Specifically, silica, silica was dried at high temperature - can be used are alumina and the like, which are typically _{Na 2 O, K 2 CO 3} , BaSO 4, Mg (NO 3) an oxide of _2, such as carbonate, sulfate, nitrate component .

The ethoxylated amine may be added in an amount of 1 to 10 parts by weight, preferably 2 to 8 parts by weight, based on 100 parts by weight of the carrier. When the content of the ethoxylated amine is too large, alcohol groups of the ethoxylated amine may cause catalyst poisoning, and when the content of the ethoxylated amine is too small, the role of suppressing or eliminating static electricity is insufficient, And the occurrence of the process trouble due to this may not be reduced.

In addition, the catalyst system for producing polyolefins may further include a cocatalyst composed of alkylaluminoxane. When such a cocatalyst is used, the catalyst may be used in which X bonded to the metal element (M) of the compound represented by the formula (1) is substituted with an alkyl group, for example, C _{1 -20} alkyl.

The above-mentioned cocatalyst is not particularly limited as it is customary in the technical field to which the present invention belongs, but one or more cocatalysts selected from the group consisting of silica, silica-alumina and organoaluminum compound may be used.

According to another embodiment of the present invention, there is provided a process for producing a polyolefin comprising polymerizing at least one olefin monomer in the presence of the catalyst system for producing polyolefins.

The polyolefin prepared according to the above method has a small amount of fine powder and does not exhibit fouling phenomenon during the reaction of the plant. Since polyolefin having such a small amount of fine particles has excellent morphology as compared with conventional polyolefin, it is easy to produce and easy to polymerize because it does not show fouling phenomenon during the process, It is easy to apply to pilot and factory scale.

The olefin monomer may be selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, , 1-octadecene, 1-eicosene, or a mixture thereof.

Here, the polymerization of the polyolefin 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 , more preferably 5 to 40 kgf / cm ² . The polymerization reaction time is preferably 1 to 5 hours.

The polymerization process can control the molecular weight range of the finally produced polymer product according to the hydrogenation or not added conditions. In particular, a polyolefin having a high molecular weight can be produced under a condition that hydrogen is not added, and a low molecular weight polyolefin can be produced even with a small amount of hydrogen addition by adding hydrogen. 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 in terms of the molar amount of hydrogen relative to the olefin monomer .

The catalyst system for producing polyolefins according to the present invention can provide a polyolefin with improved polymerization performance, which can realize a high polymerization performance and has a low fine content.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

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) was slowly added dropwise at 0 占 폚 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 (14H, m)

Example  One

3 g of silica was preliminarily weighed in a shrinking flask, and then 52 mmol of methylaluminoxane (MAO) was added thereto, followed by reaction at 90 ° C for 24 hours. After precipitation, the upper layer was removed and washed twice with toluene. 180 μmol of the anisma-metallocene compound [(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4-tert-butylphenylindenyl)] zirconium dichloride synthesized in Preparation Example 1 Was dissolved in toluene and reacted at 70 ° C for 5 hours. After completion of the reaction, the upper layer solution was removed, and the remaining reaction product was washed with toluene. Then, the upper layer solution was removed, and Atmer 163 dissolved in hexane was added to the reaction product in the contents of Tables 1 to 3 and stirred for 10 minutes. The upper layer solution was removed and vacuum dried to obtain 5 g of silica-supported metallocene catalyst in the form of solid particles.

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 μmol of rac - [(6-t-butoxyhexylmethylsilanediyl) -bis (2-methyl-4- (4-t-butylphenyl) indenyl)] hafnium dichloride prepared in Preparation Example 2 Dissolved in toluene, and reacted at 75 ° C 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. Subsequently, 20 μmol of [(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4-tert-butylphenylindenyl)] zirconium dichloride prepared in Preparation Example 1 was dissolved in toluene, And 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, and Atmer 163 dissolved in hexane was added to the reaction product in the contents of Tables 1 to 3 and stirred for 10 minutes. The upper layer solution was removed and vacuum dried to obtain a silica-supported metallocene catalyst in the form of solid particles.

Example  3

3 g of silica was preliminarily weighed in a shrinkage flask, and 52 mmol of methylaluminoxane (MAO) was added thereto, followed by reaction at 90 ° C. for 24 hours. After precipitation, the upper layer was removed and washed twice with toluene. (2-methyl-4- (4-t-butylphenyl) indenyl) - (6-t-butoxyhexylmethylsilanediyl) -bis 240 탆 ol of hafnium dichloride was dissolved in toluene, and the reaction was carried out at 70 캜 for 5 hours. After completion of the reaction, the upper layer solution was removed, and the remaining reaction product was washed with toluene. Then, the upper layer solution was removed, and Atmer 163 dissolved in hexane was added to the reaction product in the contents of Tables 1 to 3 and stirred for 10 minutes. The upper layer solution was removed and vacuum dried to obtain 5 g of silica-supported metallocene catalyst in the form of solid particles.

Comparative Example  One

A silica-supported metallocene catalyst was obtained in the same manner as in Example 1 except that Atmer 163, which is an antistatic agent, was not added.

Comparative Example  2

A silica-supported metallocene catalyst was obtained in the same manner as in Example 2 except that Atmer 163, which is an antistatic agent, was not added.

Comparative Example  3

A silica-supported metallocene catalyst was obtained in the same manner as in Example 3 except that Atmer 163, which is an antistatic agent, was not added.

Experimental Example

(1) homopolymerization of propylene

A 2 L stainless steel reactor was vacuum dried at 65 占 폚 and cooled. Triethylaluminum 1.5 mmol and a constant content of hydrogen and 770 g of propylene according to the reaction conditions shown in the following Table 1 or 2 were sequentially added at room temperature. After stirring for 10 minutes, 0.048 g of each metallocene catalyst prepared in the above Examples and Comparative Examples was dissolved in 20 mL of TMA-prescribed hexane and introduced into the reactor 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

A 2 L stainless steel reactor was vacuum dried at 65 占 폚 and cooled. Triethylaluminum 1.5 mmol and a constant content of hydrogen and 770 g of propylene according to the reaction conditions shown in the following Table 1 or 2 were sequentially added at room temperature. After stirring for 10 minutes, 0.048 g of each metallocene catalyst prepared in the above Examples and Comparative Examples was dissolved in 20 mL of TMA-prescribed hexane and introduced into the reactor under a nitrogen pressure. Then, the reactor temperature was slowly raised to 70 ° C. while 12,000 cc of ethylene was added, and the reactor was polymerized for 1 hour. After completion of the reaction, unreacted propylene and ethylene were vented.

(3) Method of measuring physical properties of polymer

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

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 further cooled to 20 ° C., the temperature was increased again. The temperature rising rate and the falling rate were adjusted to 10 ° C./min Respectively.

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): Measured at 230 ° C according to ASTM D1238 at a load of 2.16 kg and expressed as the weight (g) of the polymer that has been melted for 10 minutes.

5) Particle size

A sample was injected into a hopper of an optical diffraction particle size analyzer (symatec HELOS), and the method was set in the range of 50 to 3500 μm to confirm APS (Average Particle Size), Span value and content of 75 μm or less (fine powder).

4) Measurement results of physical properties of polymer

Polypropylene was prepared using the respective catalyst systems prepared in the above Examples and Comparative Examples, and the polymerization process conditions at this time and the measurement results of the physical properties of the resulting polypropylene were shown in the following Table 1 (Examples) and Table 2 For example). Whether or not the fouling phenomenon occurred when the catalyst system prepared in the above-described Examples and Comparative Examples was applied to the pilot scale was observed, and the results are shown in Table 3 below.

Category ^{1 )} Atmer
(wt% / SiO ₂₎ Hydrogen
(ppm) yield
(g) activation
(kg PP / g Cat.hr) MFR
(g / 10 min) Tm
(° C) Tc
(° C) Example 1 / Comparative Example 1 H 0 331 324.8 7.2 14.2 151.2 98.8 2 375.6 8.3 8.3 150.3 99.2 0 1157 384.8 8.6 56.9 2 426.6 9.5 34.2 150.1 102.7 5 426.6 9.5 59.2 150.2 101.5 R 0 0 392.5 8.7 9.8 2 332.0 7.4 6.6 143.3 93.5 Example 2 / Comparative Example 2 H 0 331 409.4 9.1 7.1 152.1 100.7 3 408.4 9.1 3.3 152.8 99.4 R 0 0 429.4 9.5 4.4 144.4 93.9 3 445.6 9.9 3.3 143.4 92.8 Example 3 / Comparative Example 3 H 0 331 393.9 8.8 6.2 152.8 102.3 3 497.6 11.1 4.8 R 0 0 364.5 8.1 2.2 144.9 87.8 3 381.2 8.5 3.6 1) H: homopolymerization, R: random polymerization

division Atmer
(wt% / SiO ₂₎ Hydrogen
(ppm) APS
(탆) Span <74 μm <210 μm <500 μm Example 1 / Comparative Example 1 H 0 200 934 0.78 0.80 1.75 4.40 500 1067 0.65 0.95 1.45 3.37 1500 971 0.72 0.78 2.04 5.57 3 200 938 0.63 0.78 0.78 2.22 500 1028 0.63 0.65 1.20 1.89 1500 975 0.63 0.54 1.19 1.95 Example 2 / Comparative Example 2 H 0 200 1015 0.75 0.92 2.58 5.25 500 1108 0.82 1.82 3.25 4.85 R 200 1275 0.80 1.25 2.78 4.27 H 2 200 1095 0.62 0.53 0.53 1.56 500 1080 0.63 1.19 1.19 1.95 R 200 1315 0.58 0.04 0.04 0.63 Example 3 / Comparative Example 3 H 0 150 658 0.91 0.91 1.84 22.0 3 150 725 0.68 0.72 1.02 1.75 R 0 250 813 0.72 0.94 1.63 8.52 3 250 875 0.62 0.68 1.20 1.95

division Atmer (wt% / SiO ₂ ) Fouling phenomenon Example 1 / Comparative Example 1 H 0 ○ 3 X R 0 ○ 3 X Example 2 / Comparative Example 2 H 0 ○ 3 X R 0 ○ 3 X Example 3 / Comparative Example 3 H 0 ○ 3 X R 0 ○ 3 X

As shown in Table 1, Examples 1 to 3 using a catalyst system containing ethoxylated amines exhibited the same or superior activity as those of Comparative Examples 1 to 3 containing no ethoxylated amine.

Further, referring to Tables 2 to 3 above, the polypropylene of Examples 1 to 3 prepared using the catalyst system containing ethoxylated amine had a fine particle content of 74 占 퐉 or less as compared with the polypropylene of Comparative Examples 1 to 3 And it is confirmed that the fouling phenomenon due to the differential does not appear in the pilot process.

Claims (8)

At least one compound represented by the following formula (1); And
Ethoxylated amines; &Lt; tb &gt;&lt; tb &gt;
[Chemical Formula 1]

In Formula 1,
M is a Group 4 transition metal,
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.
The method according to claim 1,
Wherein M is zirconium, hafnium, or titanium.
The method according to claim 1,
Wherein X is fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).
The method according to claim 1,
Wherein the ethoxylated amines are represented by the following Formula 2:
(2)
_{RN (C 2 H 4 OH)} 2
In Formula 2,
R is alkyl having 1 to 20 carbon atoms.
The method according to claim 1,
Wherein the compound represented by Formula 1 and the ethoxylated amines are supported on at least one carrier selected from the group consisting of silica, silica-alumina, and silica-magnesia.
6. The method of claim 5,
Wherein the ethoxylated amine comprises 1 to 10 parts by weight based on 100 parts by weight of the carrier.
A process for producing a polyolefin comprising polymerizing at least one or more olefin monomers in the presence of the catalyst system for producing a polyolefin according to claim 1.
8. The method of claim 7,
The olefins may be selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, Octadecene, 1-octadecene, and 1-eicosene.