Solid catalyst for propylene polymerization and method of producing block copolymer using the same
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.
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:
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 1 is a linear alkyl group having 1 to 12 carbon atoms, and R 2 , R 3 , R 4 and R 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):
in general formula (1) which is an N-halide succinimide based compound, X is a halogen, and R 1 , R 2 , R 3 and R 4 are hydrogen, a C 1 -C 12 alkyl, or a C 6 -C 20 aryl
in general formula (2) which is a trihaloisocyanuric acid-based compound, X is a halogen
in general formula (3) which is an N-halophthalimide based compound, X is a halogen, and R 1 , R 2 , R 3 and R 4 are hydrogen, an C 1 -C 12 alkyl, or a C 6 -C 20 aryl
in general formula (4) which is a hydantoin-based compound, X is a halogen, and R 1 and R 2 are hydrogen, a C 1 -C 12 alkyl, or a C 6 -C 20 aryl.
5. The method of claim 3 , wherein the halogen compound includes Br 2 or I 2 , and the magnesium halide is magnesium chloride (MgCl 2 ), magnesium bromide (MgBr 2 ), or magnesium iodide (MgI 2 ).