Solid catalyst for propylene polymerization and method of producing block copolymer using the same

Abstract

The present invention relates to a solid catalyst for propylene polymerization and a method of producing a propylene polymer or copolymer using the solid catalyst for propylene polymerization, and provides a solid catalyst which prepares a dialkoxymagnesium carrier and is formed of a carrier produced through a reaction of the carrier with a metal halide, a titanium halide, an organic electron donor, etc., and a method of producing a propylene polymer or copolymer through copolymerization of propylene-alpha olefin using the solid catalyst, wherein the dialkoxymagnesium carrier has an uniform particle size range of 10 to 100 μm and a spherical particle shape by adjusting injection amounts, injection numbers, and reaction temperatures of metal magnesium, alcohol and a reaction initiator during a reaction process of metal magnesium and alcohol.

Claims

1. A method of preparing a solid catalyst for propylene polymerization, the method comprising the steps of: (1) reacting dialkoxymagnesium with a metal halide compound at a reaction temperature of −10 to 60° C. in the presence of an organic solvent; (2) reacting two or more types of the internal electron donors with the reaction product while increasing temperature of a reaction product of the step (1) to obtain a reaction product; and (3) reacting the reaction product of the step (2) with a titanium halide at a reaction temperature of 60 to 150° C., wherein a bulk specific gravity in the dialkoxymagnesium is 0.20 to 0.40 g/ml, an internal electron donor formed of a nonaromatic alkoxyester-based compound represented by the following general formula (II) as a first internal electron donor and phthalic acid ester or 1, 3-diethers as a second internal electron donor: ##STR00006## wherein, B is a compound with a mono ester structure consisting of aliphatic saturated hydrocarbons and cyclic saturated hydrocarbons having 1 to 20 carbon atoms or a compound with a carbamate structure consisting of an amino group and a linear or cyclic amino group, R.sub.1 is a linear alkyl group having 1 to 12 carbon atoms, and R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently hydrogen, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, a linear or branched alkenyl group having 3 to 12 carbon atoms, a linear halogen-substituted alkyl group having 1 to 12 carbon atoms, a branched halogen-substituted alkyl group having 3 to 12 carbon atoms, a linear or branched halogen-substituted alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, a halogen-substituted cycloalkyl group having 3 to 12 carbon atoms, a halogen-substituted cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and wherein the dialkoxymagnesium is obtained by reacting metal magnesium with alcohol and a reaction initiator, the alcohol is divisionally added to the metal magnesium 3 to 6 times, the reaction initiator is injected into a reaction system when starting an initial reaction process, and the reaction initiator is divisionally added to the reaction system 2 to 5 times during an additional reaction process, stirring rate during the reaction process with the metal magnesium and alcohol is 50 to 300 rpm at a reaction temperature of 25 to 110° C.

2. The method of claim 1, wherein a ratio of the metal magnesium to alcohol is 1:5 to 1:100 as a ratio of magnesium weight (g) to alcohol volume (ml).

3. The method of claim 1, wherein the reaction initiator includes a nitrogen halogen compound, a halogen compound, or a magnesium halide.

4. The method of claim 3, wherein the nitrogen halogen compound is one selected from the group consisting of the following general formulas (1) to (4): ##STR00007## in general formula (1) which is an N-halide succinimide based compound, X is a halogen, and R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are hydrogen, a C.sub.1-C.sub.12 alkyl, or a C.sub.6-C.sub.20 aryl ##STR00008## in general formula (2) which is a trihaloisocyanuric acid-based compound, X is a halogen ##STR00009## in general formula (3) which is an N-halophthalimide based compound, X is a halogen, and R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are hydrogen, an C.sub.1-C.sub.12 alkyl, or a C.sub.6-C.sub.20 aryl ##STR00010## in general formula (4) which is a hydantoin-based compound, X is a halogen, and R.sub.1 and R.sub.2 are hydrogen, a C.sub.1-C.sub.12 alkyl, or a C.sub.6-C.sub.20 aryl.

5. The method of claim 3, wherein the halogen compound includes Br.sub.2 or I.sub.2, and the magnesium halide is magnesium chloride (MgCl.sub.2), magnesium bromide (MgBr.sub.2), or magnesium iodide (MgI.sub.2).

Description

DETAILED DESCRIPTION

(1) Hereinafter, Examples and Comparative Examples of the present invention will be described in detail. However, the present invention is not limited thereto.

EXAMPLE 1

(2) [Preparation of a Spherical Carrier]

(3) After sufficiently ventilating a 5 L-sized glass reactor having a stirrer, an oil heater and a cooling refluxer mounted thereon with nitrogen, 4 g of N-bromosuccinimide, 40 g of metal magnesium (a powder-type product having an average particle diameter of 100 μm) and 500 ml of anhydrous ethanol were injected into the reactor, and then temperature of the reactor was maintained to 60° C. while operating the reactor at a stirring rate of 250 rpm. Since hydrogen was generated while a reaction process was being started with the passage of about 10 minutes, pressure of the reactor was maintained at atmospheric pressure in a state that an outlet of the reactor was opened so as to discharge the hydrogen generated. After completing the generation of hydrogen, the reactor was maintained at 60° C. for 1 hour. After injecting 20 g of metal magnesium (a powder-type product having an average particle diameter of 100 μm) along with 300 ml of anhydrous ethanol and 2 g of a reaction initiator into the reactor with the passage of 1 hour, maintaining the reactor for 1 hour, and finally injecting 10 g of metal magnesium (a powder-type product having an average particle diameter of 100 μm), 200 ml of anhydrous ethanol and 1 g of the reaction initiator into the reactor, an aging treatment operation was conducted for 3 hours until a reaction process was terminated. After finishing the aging treatment operation, a resulting material was washed at 50° C. three times using 2,000 ml of n-hexane per time. 263 g of a diethoxymagnesium carrier with a yield of 93.2% as a white powder-type solid product with good flowability was obtained by drying a washed resulting material in the presence of a flowing nitrogen for 24 hours.

(4) As a result of measuring particle sizes of a dried product by a light transmission method using a laser particle analyzer (Mastersizer X manufactured by Malvern Instruments Corporation), an average particle size of the dried product was 25.2 μm.

(5) Particle distribution index (P) (P=(D.sub.90-D.sub.10)/D.sub.50, where D.sub.90 is a particle size corresponding to a cumulative weight 90%, D.sub.50 is a particle size corresponding to a cumulative weight 50%, and D.sub.10 is a particle size corresponding to a cumulative weight 10%) was 0.71, and an apparent density measured in accordance with ASTM D1895 was 0.24 g/cc.

(6) [Preparation of a Solid Catalyst Component]

(7) After injecting 112 ml of toluene and 15 g of diethoxymagnesium having an average particle diameter of 20 μm, a spherical shape, a particle size distribution index of 0.86 and an apparent density of 0.35 g/cc into a glass reactor which was sufficiently substituted with nitrogen and in which an one liter-sized stirrer was installed, and injecting a diluted solution obtained by diluting 20 ml of titanium tetrachloride into 30 ml of toluene into the reactor over 1 hour while maintaining the reactor at 10° C., 2.8 g of 2-ethoxyethyl butanoate, 1.5 g of 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, and 1.0 g of diisobutylphthalate were sequentially injected into the reactor while heating the reactor to a temperature of 100° C. After maintaining the reactor at 100° C. for 2 hours, lowering temperature of the reactor to 90° C., and stopping a stirring operation, a supernatant was removed, and a resulting material was further washed with 200 ml of toluene one time. A process of injecting 120 ml of toluene and 20 ml of titanium tetrachloride into the reactor, increasing temperature of the reactor to 100° C., and maintaining the reactor at 100° C. for 2 hours was repeatedly performed one time to obtain an aging process-completed slurry mixture. A pale yellow solid catalyst component was obtained by washing the aging process-completed slurry mixture two times with 200 ml of toluene per one time and washing a washed resulting material at 40° C. five times with 200 ml of n-hexane per one time. A solid catalyst component obtained by drying the pale yellow solid catalyst component in flowing nitrogen for 18 hours had a titanium content of 2.0 wt %.

(8) [Polypropylene Polymerization]

(9) 10 mg of the solid catalyst, 10 mmol of triethyl aluminum and 1 mmol of dicyclopentylmethyldimethoxysilane were injected into a 4 liter-sized stainless steel reactor for high pressure. Subsequently, a polymerization process was performed by increasing temperature of the reactor to 70° C. after sequentially injecting 7,000 ml of hydrogen and 2.4 L of propylene of a liquid state into the reactor. Propylene within the reactor was completely deaerated to obtain a polymer by opening a valve while lowering the temperature of the reactor to room temperature when 2 hours were elapsed after initiating the polymerization process.

(10) After analyzing the polymer obtained, analysis results of the polymer are represented in Table 1.

(11) Here, catalytic activity, stereoregularity, melt-flowability and polydispersity index were determined by the following methods.

(12) {circle around (1)} Catalytic activity (kg-PP/g-cat)=a production amount of polymer (kg)÷amount of catalyst (g)

(13) {circle around (2)} Stereoregularity (X.I.): wt % of an insoluble component obtained after being crystallized and precipitated in a mixed xylene

(14) {circle around (3)} Melt-flowability (MI, g/10 minutes): a value measured at a temperature of 230° C. and a load of 2.16 kg in accordance with ASTM1238

(15) {circle around (4)} Polydispersity index (PI): a value calculated using the following calculation formula from a modulus separation value obtained using a parallel plate rheometer at a temperature of 200° C.
P.I.=54.6*(modulus separation)−1.76

(16) [Propylene-Based Block Copolymerization]

(17) After putting 5 mg of the solid catalyst into a stirrer-attached stainless steel reactor with a 2 L size filled with nitrogen, injecting 3 mmol of triethylaluminum and 0.3 mmol of dicyclopentyldimethoxysilane (DCPDMS) into the reactor, and then injecting 1.2 L of liquefied propylene and 5,000 ml of hydrogen into the reactor, thereby performing a preliminary polymerization process at 20° C. for 5 minutes, a propylene homopolymerization process was performed at 70° C. for 40 minutes. After finishing the homopolymerization process, purging a monomer while lowering temperature of the reactor to room temperature, injecting a mixed gas to be a molar ratio of ethylene/(ethylene+propylene) of 0.4 into the reactor, and increasing temperature of the reactor to 70° C., thereby performing a polymerization process for 60 minutes, a propylene-based block copolymer could be obtained. After analyzing the propylene-based block copolymer obtained, analysis results of the propylene-based block copolymer are represented in Table 2.

(18) {circle around (1)} Block copolymer activity (ICP activity, kg-PP/g-cat)=a production amount of polymer (kg)÷amount of catalyst (g)

(19) {circle around (2)} Rubber content of ethylene propylene (EPR, wt %): wt % of a component obtained by precipitating a xylene-removed copolymer after removing xylene from the copolymer by extracting a copolymer with xylene

(20) {circle around (3)} Ethylene content in a copolymer (B-C2, wt %): ethylene content obtained after sampling a copolymer and measuring the sampled copolymer by Fourier Transform Infrared Spectrometer (FT-IR) (the ethylene content is calculated based on a calibration curve drawn up by a standard sample)

(21) Ethylene content in EPR (PER-C2, wt %): (ethylene content in the copolymer)/(rubber content of ethylene propylene)*100

EXAMPLE 2

(22) [Preparation of a Spherical Carrier]

(23) After sufficiently ventilating a 5 L-sized glass reactor having a stirrer, an oil heater and a cooling refluxer mounted thereon with nitrogen, 3 g of N-bromosuccinimide, 10 g of metal magnesium (a powder-type product having an average particle diameter of 120 μm) and 300 ml of anhydrous ethanol were injected into the reactor, and then temperature of the reactor was maintained to 70° C. that was an ethanol reflux state while operating the reactor at a stirring rate of 250 rpm. Since hydrogen was generated while a reaction process was being started with the passage of about 5 minutes, pressure of the reactor was maintained at atmospheric pressure in a state that an outlet of the reactor was opened so as to discharge generated hydrogen. After the generation of hydrogen, 1 g of N-bromosuccinimide, 20 g of metal magnesium (a powder-type product having an average particle diameter of 120 μm) and 250 ml of ethanol were additionally injected into the reactor. After finishing hydrogen generation caused by a reaction process between metal magnesium and ethanol due to the secondary additional injection process, an aging treatment process was performed by additionally thirdly injecting 3 g of N-bromosuccinimide, 450 g of metal magnesium (a powder-type product having an average particle diameter of 120 μm) and 560 ml of ethanol into the reactor, and maintaining a reactor temperature and a stirring rate in a reflux state for 2 hours. After finishing the aging treatment process, a resulting material was washed at 50° C. three times using 2,000 ml of n-hexane per one time of a washing process. 336 g of a diethoxymagnesium carrier with a yield of 95.2% as a white powder-type solid product with good flowability was obtained by drying a washed resulting material in the presence of a flowing nitrogen for 24 hours.

(24) As results of measuring by the same methods as in Example 1, the dried carrier suspended in n-hexane had the average particle size of 32.1 μm, the particle distribution index of 0.89, and the apparent density of 0.27 g/cc.

(25) [Preparation of a Solid Catalyst Component]

(26) After sequentially injecting a solution prepared by mixing 1.0 g of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane with 3 g of 2-methoxyethyl pivalate instead of 2-ethoxyethyl butylate and 2.0 g of diisobutylphthalate into a reactor in the preparation of a solid catalyst of Example 1, the catalyst was prepared while increasing temperature of the reactor. A solid catalyst component had a titanium content of 2.1 wt %. Next, after performing a polypropylene polymerization process by the same method as in Example 1, results of the polypropylene polymerization process are represented in Table 1, and after producing a propylene-based block copolymer by the same method as in Example 1, production results are represented in Table 2.

EXAMPLE 3

(27) [Preparation of a Spherical Carrier]

(28) After sufficiently ventilating a 5 L-sized glass reactor having a stirrer, an oil heater and a cooling refluxer mounted thereon with nitrogen, 2 g of N-bromosuccinimide, 10 g of metal magnesium (a powder-type product having an average particle diameter of 120 μm) and 250 ml of anhydrous ethanol were injected into the reactor, and then temperature of the reactor was maintained to 80° C. that was an ethanol reflux state while operating the reactor at a stirring rate of 200 rpm. Since hydrogen was generated while a reaction process was being started with the passage of about 5 minutes, pressure of the reactor was maintained at atmospheric pressure in a state that an outlet of the reactor was opened so as to discharge generated hydrogen. After the generation of hydrogen, 3 g of N-bromosuccinimide, 30 g of metal magnesium (a powder-type product having an average particle diameter of 120 μm) and 450 ml of ethanol were additionally injected into the reactor. After finishing hydrogen generation caused by a reaction process between metal magnesium and ethanol due to the secondary additional injection process, an aging treatment process was performed by additionally thirdly injecting 2 g of N-bromosuccinimide, 20 g of metal magnesium (a powder-type product having an average particle diameter of 120 μm) and 300 ml of ethanol into the reactor, and maintaining a reactor temperature and a stirring rate in a reflux state for 2 hours. After finishing the aging treatment process, a resulting material was washed three times using 2,000 ml of n-hexane per one time of a washing process at 50° C. 271 g of a diethoxymagnesium carrier with a yield of 95.8% as a white powder-type solid product with good flowability was obtained by drying a washed resulting material in the presence of a flowing nitrogen for 24 hours.

(29) As results of measuring by the same methods as in Example 1, the dried carrier suspended in n-hexane had the average particle size of 42.2 μm, the particle distribution index of 0.62, and the apparent density of 0.27 g/cc.

(30) [Preparation of a Solid Catalyst Component]

(31) After preparing a solid catalyst using the prepared spherical carrier by the same method as in Example 1, the solid catalyst was measured in the same manner as in Example. As a result of measurement, the solid catalyst had a titanium content of 2.33 wt %, and an average particle size of 45.2 μm. After performing a polypropylene polymerization process by the same method as in Example 1, results of the polypropylene polymerization process are represented in Table 1, and after producing a propylene-based block copolymer by the same method as in Example 1, production results are represented in Table 2.

EXAMPLE 4

(32) [Preparation of a Spherical Carrier]

(33) After sufficiently ventilating a 5 L-sized glass reactor having a stirrer, an oil heater and a cooling refluxer mounted thereon with nitrogen, 3.5 g of N-bromosuccinimide, 15 g of metal magnesium (a powder-type product having an average particle diameter of 150 μm) and 450 ml of anhydrous ethanol were injected into the reactor, and then an ethanol refluxing state was maintained by increasing temperature of the reactor to 85° C. while operating the reactor at a stirring rate of 150 rpm. Since hydrogen was generated while a reaction process was being started with the passage of about 5 minutes, pressure of the reactor was maintained at atmospheric pressure in a state that an outlet of the reactor was opened so as to discharge generated hydrogen. After the generation of hydrogen, 2.0 g of N-chlorosuccinimide, 20 g of metal magnesium (a powder-type product having an average particle diameter of 150 μm) and 300 ml of anhydrous ethanol were additionally injected into the reactor. After finishing hydrogen generation caused by a reaction process between metal magnesium and ethanol due to the secondary additional injection process, an aging treatment process was performed by additionally thirdly injecting 0.5 g of N-chlorosuccinimide, 27 g of metal magnesium (a powder-type product having an average particle diameter of 150 μm) and 375 ml of anhydrous ethanol into the reactor, and maintaining a reactor temperature and a stirring rate in a reflux state for 2 hours. After finishing the aging treatment process, a resulting material was washed three times using 2,000 ml of n-hexane per one time of a washing process at 50° C. 285 g of a diethoxymagnesium carrier with a yield of 97.6% as a white powder-type solid product with good flowability was obtained by drying a washed resulting material in the presence of a flowing nitrogen for 24 hours.

(34) As results of measuring by the same methods as in Example 1, the dried carrier suspended in n-hexane had the average particle size of 61.4 μm, the particle distribution index of 0.83, and the apparent density of 0.26 g/cc.

(35) [Preparation of a Solid Catalyst Component]

(36) The catalyst was prepared by sequentially injecting 1.8 g of diisobutylphthalate and 1.5 g of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane respectively into 2.8 g of 2-ethoxyethyl dimethylcarbamate instead of 2-ethoxyethyl butylate in the preparation of a solid catalyst of Example 1. A solid catalyst component had a titanium content of 2.1 wt %. Next, after performing a polypropylene polymerization process by the same method as in Example 1, results of the polypropylene polymerization process are represented in Table 1

EXAMPLE 5

(37) [Preparation of a Solid Catalyst Component]

(38) The catalyst was prepared by sequentially injecting 3.2 g of diisobutylphthalate respectively into 2.8 g of 2-methoxyethyl butylate as an internal electron donor when preparing a solid catalyst using a spherical carrier prepared by the same method as in Example 3. A solid catalyst component had a titanium content of 2.0 wt %. Next, after performing a polypropylene polymerization process by the same method as in Example 1, results of the polypropylene polymerization process are represented in Table 1, and after producing a propylene-based block copolymer by the same method as in Example 1, production results are represented in Table 2. The average particle size was 45.2 μm.

EXAMPLE 6

(39) [Preparation of a Solid Catalyst Component]

(40) The catalyst was prepared by sequentially injecting 2.5 g of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane respectively into 3.8 g of 2-methoxyethyl butylate as an internal electron donor when preparing a solid catalyst using a spherical carrier prepared by the same method as in Example 3. A solid catalyst component had a titanium content of 2.2 wt %. Next, after performing a polypropylene polymerization process by the same method as in Example 1, results of the polypropylene polymerization process are represented in Table 1, and after producing a propylene-based block copolymer by the same method as in Example 1, production results are represented in Table 2. The average particle size was 45.2 μm.

COMPARATIVE EXAMPLE 1

(41) [Preparation of a Spherical Carrier]

(42) After sufficiently ventilating a 5 L-sized glass reactor having a stirrer, an oil heater and a cooling refluxer mounted thereon with nitrogen, 7 g of N-bromosuccinimide, 60 g of metal magnesium (a powder-type product having an average particle diameter of 120 μm) and 900 ml of anhydrous ethanol were injected into the reactor, and then temperature of the reactor was maintained to 70° C. that was an ethanol reflux state while operating the reactor at a stirring rate of 250 rpm. Since hydrogen was generated while a reaction process was being started with the passage of about 5 minutes, pressure of the reactor was maintained at atmospheric pressure in a state that an outlet of the reactor was opened so as to discharge generated hydrogen. After the generation of hydrogen, an aging treatment process was performed by maintaining a reactor temperature and a stirring rate in a reflux state for 2 hours. After finishing the aging treatment process, a resulting material was washed at 50° C. three times using 2,000 ml of n-hexane per one time of a washing process. 328 g of a diethoxymagnesium carrier with a yield of 92.8% as a white powder-type solid product with good flowability was obtained by drying a washed resulting material in the presence of a flowing nitrogen for 24 hours.

(43) As results of measuring by the same methods as in Example 1, the dried carrier suspended in n-hexane had the average particle size of 20.6 μm, the particle distribution index of 1.37, and the apparent density of 0.33 g/cc.

(44) [Preparation of a Solid Catalyst Component]

(45) The catalyst was prepared by using 4.7 g of diisobutylphthalate as an internal electron donor when preparing a solid catalyst of Example 1. A solid catalyst component had a titanium content of 2.2 wt %. After performing a polypropylene polymerization process by the same method as in Example 1, the results are represented in Table 1.

COMPARATIVE EXAMPLE 2

(46) [Preparation of a Spherical Carrier and a Solid Catalyst Component]

(47) After injecting 150 ml of toluene, 12 ml of tetrahydrofuran, 20 ml of butanol and 21 g of magnesium chloride into an 1 L-sized glass reactor which was sufficiently substituted with nitrogen, in which a stirrer was installed, increasing temperature of the reactor to 110° C., and maintaining the reactor at 110° C. for 1 hour, a homogeneous solution was obtained. After cooling temperature of the solution to 15° C., injecting 25 ml of titanium tetrachloride into the solution, increasing temperature of the reactor to 60° C. over 1 hour, performing an aging treatment process for 10 minutes, and performing a settling process for 15 minutes to settle a carrier, a supernatant of a resulting material was removed from a resulting material. After injecting 200 ml of toluene into a slurry remained in the reactor, and repeating stirring, settling, and supernatant removal processes two times, a resulting material was washed to obtain a slurry.

(48) After injecting 150 ml of toluene into such obtained slurry, and injecting a diluted solution prepared by diluting 25 ml of titanium tetrachloride into 50 ml of toluene at 15° C. into the slurry over 1 hour, temperature of the reactor was increased to 30° C. in a rate of 0.5° C./min. After maintaining a reaction mixture at 30° C. for 1 hour, 4.5 ml of diisobutylphthalate and 3 ml of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane were injected into the reaction mixture, and temperature of the reactor was increased to 110° C. again in a rate of 0.5° C./min.

(49) After maintaining a resulting material at 110° C. for 1 hour, lowering temperature of the resulting material to 90° C. to stop a stirring process, and performing a supernatant removal process, a resulting material was additionally washed one time by the same method using 200 ml of toluene to obtain a slurry. After injecting 150 ml of toluene and 50 ml of titanium tetrachloride into the slurry and increasing temperature of a slurry mixture to 110° C., the slurry mixture was maintained at 110° C. for 1 hour. After performing a process of aging the slurry mixture, washing an aging process-completed slurry mixture two times with 200 ml of toluene per time of the washing process, and washing the washed slurry mixture five times at 40° C. with 200 ml of hexane per time of the washing process to obtain a pale yellow solid catalyst component. A solid catalyst component obtained by drying the pale yellow solid catalyst component in flowing nitrogen for 18 hours had a titanium content of 3.3 wt %. Next, after performing a polypropylene polymerization process by the same method as in Example 1, results of the polypropylene polymerization process are represented in Table 1, and after producing a propylene-based block copolymer by the same method as in Example 1, production results are represented in Table 2.

COMPARATIVE EXAMPLE 3

(50) [Preparation of a Solid Catalyst Component]

(51) The catalyst was prepared using 6.5 g of 2-isopropyl-2-(3-methylbutyl)-1,3-dimethoxypropane as an internal electron donor in preparation of the solid catalyst of Example 1 using the carrier prepared in Comparative Example 1. A solid catalyst component had a titanium content of 3.0 wt %. Next, after performing a polypropylene polymerization process by the same method as in Example 1, results of the polypropylene polymerization process are represented in Table 1, and after producing a propylene-based block copolymer by the same method as in Example 1, production results are represented in Table 2.

COMPARATIVE EXAMPLE 4

(52) [Preparation of a Solid Catalyst Component]

(53) The catalyst was prepared using 4.8 g of 2-methoxyethyl acetate as an internal electron donor in preparation of the solid catalyst of Example 1 using the carrier prepared in Comparative Example 1. A solid catalyst component had a titanium content of 3.1 wt %. Next, after performing a polypropylene polymerization process by the same method as in Example 1, results of the polypropylene polymerization process are represented in Table 1, and after producing a propylene-based block copolymer by the same method as in Example 1, production results are represented in Table 2.

(54) TABLE-US-00001 TABLE 1 Catalytic activity X.I. MI (g-PP/g-cat 2 h) (wt %) (g/10 min) P.I. Example 1 73,000 98.9 65 4.1 Example 2 76,000 98.8 63 4.2 Example 3 81,000 98.8 71 4.1 Example 4 82,000 98.9 73 4.1 Example 5 78,000 98.8 660 4.3 Example 6 72,000 99.0 110 3.9 Comparative 65,000 98.7 13 4.2 Example 1 Comparative 56,000 98.0 25 4.0 Example 2 Comparative 53,000 98.5 125 3.5 Example 3 Comparative 34,000 96.4 100 4.3 Example 4

(55) TABLE-US-00002 TABLE 2 Propylene-based copolymerization ICP activity EPR B-C2 PER-C2 (g-PP/g-cat) (wt %) (wt %) (wt %) Example 1 56,000 38 20 56 Example 2 58,000 37 21 57 Example 3 53,000 39 21 55 Example 4 55,000 38 21 55 Example 5 58,000 37 20 54 Example 6 50,500 35 19 54 Comparative 48,000 23 12 52 Example 1 Comparative 41,000 29 14 48 Example 2 Comparative 47,000 25 13 52 Example 3 Comparative 27,000 27 14 52 Example 4

(56) The foregoing description of the embodiments has been provided for purposes of illustration and description. It is not intended to be exhaustive or to limit the disclosure. Individual elements or features of a particular embodiment are generally not limited to that particular embodiment, but, where applicable, are interchangeable and can be used in a selected embodiment, even if not specifically shown or described. The same may also be varied in many ways. Such variations are not to be regarded as a departure from the disclosure, and all such modifications are intended to be included within the scope of the disclosure.