Propylene polymerizing solid catalyst for reducing VOC and method of producing polypropylene using same

Abstract

The present invention relates to a propylene polymerizing solid catalyst for reducing the volatile organic compound (VOC) and a method of producing polypropylene using the propylene polymerizing solid catalyst, the propylene polymerizing solid catalyst including an organic electron donor formed of a combination of a first internal electron donor of titanium, magnesium, halogen and cyclic diester and a second internal electron donor of diether, and has improved hydrogen reactivity of a catalyst compared to a conventional method and has an effect that is capable of producing an eco-friendly polypropylene which has greatly lowered a content of the VOC by using the catalyst.

Claims

1. A propylene polymerizing solid catalyst, the catalyst comprising a carrier produced by making dialkoxymagnesium react with a metal halide, a titanium halide, and an organic electron donor formed of a combination of a first internal electron donor including a compound of a cyclic diester structure and a second internal electron donor including a compound of a diether structure, wherein the first internal electron donor includes a cyclic diester compound that is one of compounds represented by the following structural formulas (II) to (IV), (VII), and (VIII): ##STR00009## ##STR00010## wherein R1 and R2, which are the same as or different from each other, are a linear, branched or cyclic alkyl group, alkenyl group, aryl group, arylalkyl group or alkylaryl group having 1 to 20 carbon atoms; and R3 to R12, which are the same as or different from one another, are hydrogen or a linear, branched or cyclic alkyl group, alkenyl group, aryl group, arylalkyl group or alkylaryl group having 1 to 20 carbon atoms.

2. The propylene polymerizing solid catalyst of claim 1, wherein the second internal electron donor includes a diether compound represented by the following chemical formula (ii):
R13R14C(CH.sub.2OR15)(CH.sub.2OR16)  (ii) wherein, the compound is a 1,3-diether compound in which: R13 and R14, which are the same as or different from each other, are an alkyl radical having 1 to 18 carbon atoms, a cycloalkyl radical having 3 to 18 carbon atoms, an aryl radical having 7 to 18 carbon atoms, or are combined to form a bicyclic or tricyclic unsaturated hydrocarbon, wherein each cyclic hydrocarbon consists of 5, 6, or 7 carbon atoms; and R15 and R16, which are the same as or different from each other, are an alkyl radical having 1 to 4 carbon atoms.

3. A method of producing polypropylene, the method comprising polymerizing propylene in the presence of the propylene polymerizing solid catalyst for reducing the volatile organic compound (VOC) described in claim 1.

4. A method of producing polypropylene, the method comprising polymerizing propylene in the presence of the propylene polymerizing solid catalyst for reducing the volatile organic compound (VOC) described in claim 2.

5. The propylene polymerizing solid catalyst of claim 1, wherein the compound of a diether structure is 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-t-butyl-1,3-dimethoxypropane, 2-cumyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2(1-naphthyl)-1,3-dimethoxypropane, 2(p-fluorophenyl)-1,3-dimethoxypropane, 2(1-decahydronaphthyl)-1,3-dimethoxypropane, 2(pt-butylphenyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-diethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-diethoxypropane, 2,2-dibutyl-1,3-diethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2-methyl-2-methylcyclohexyl-1,3-dimethoxypropane, 2,2-bis(p-chlorophenyl)-1,3-dimethoxypropane, 2,2-bis(2-phenylethyl)-1,3-dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-bis(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-bis(p-methylphenyl)-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropyl, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-dibutoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-di-sec-butyl-1,3-dimethoxypropane, 2,2-di-t-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 9,9-bis(methoxymethyl)fluorene, 9,9-bis(methoxymethyl)-2,3,6,7-tetramethylfluorene, 9,9-bis(methoxymethyl)-2,3,4,5,6,7-hexafluorofluorene, 9,9-bis(methoxymethyl)-2,3-benzofluorene, 9,9-bis(methoxymethyl)-2,3,6,7-dibenzofluorene, 9,9-bis(methoxymethyl)-2,7-diisopropylfluorene, 9,9-bis(methoxymethyl)-1,8-dichlorofluorene, 9,9-bis(methoxymethyl)-2,7-dicyclopentylfluorene, 9,9-bis(methoxymethyl)-1,8-difluorofluorene, 9,9-bis(methoxymethyl)-1,2,3,4-tetrahydrofluorene, 9,9-bis(methoxymethyl)-1,2,3,4,5,6,7,8-octahydrofluorene or 9,9-bis(methoxymethyl)-4-t-butylfluorene.

Description

DETAILED DESCRIPTION

(1) Hereinafter, preferred embodiments of the present invention will be described. However, the scope of the present invention is not limited to the following embodiments.

(2) According to the present invention, a propylene polymerizing solid catalyst is provided, and polypropylene is produced using the propylene polymerizing solid catalyst, in which the propylene polymerizing solid catalyst includes a carrier produced by making dialkoxymagnesium react with a metal halide, a titanium halide, and an organic electron donor formed of a combination of a first internal electron donor including a compound of a cyclic diester structure and a second internal electron donor including a compound of a diether structure.

Example 1

Preparation of Solid Catalyst

(3) 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 filled with nitrogen gas and in which an one liter-sized stirrer was installed, maintaining a mixture of toluene and diethoxymagnesium at 10° C., and injecting a diluted solution obtained by diluting 20 ml of titanium tetrachloride into 30 ml of toluene into the mixture of toluene and diethoxymagnesium over 1 hour to obtain a mixture, 6.90 g of trans-dibutylcyclohexanedicarboxylate was injected into the mixture while heating the reactor to a temperature of 100° C., thereby obtaining a resulting material.

(4) After maintaining the reactor at 100° C. for 2 hours, and lowering temperature of the reactor to 90° C., thereby stopping a stirring process to obtain a reaction product, a supernatant of the reaction product was removed, and the supernatant-removed product was washed one time by additionally using 200 ml of toluene.

(5) 120 ml of toluene and 20 ml of titanium tetrachloride were injected into the product, the reactor was heated to a temperature of 100° C., and the temperature of the reactor was maintained for 2 hours. A slurry mixture was obtained by repeatedly performing this process two times, thereby aging a resulting material.

(6) A light yellowish solid catalyst was prepared by washing the slurry mixture passing through the aging process two times using 200 ml of toluene per one time, and washing the slurry mixture five times at 40° C. using 200 ml of n-hexane per one time.

(7) 3.6 wt % of titanium was included in a solid catalyst obtained by drying the solid catalyst in flowing nitrogen for 18 hours.

Propylene Polymerization

(8) 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 to prepare a mixture.

(9) Subsequently, a polymerization process was performed by increasing temperature of the reactor to 70° C. after sequentially injecting 1,000 ml of hydrogen and 2.4 L of propylene of a liquid state into the mixture. 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 had elapsed after initiating the polymerization process.

(10) Analysis results of the polymer are represented in Table 1.

Example 2

(11) When preparing the solid catalyst of Example 1, a solid catalyst was prepared by injecting a mixture of 5.24 g of cis-dibutylcyclohexane dicarboxylate and 1.61 g of isopentylisopropyldimethoxypropane instead of trans-dibutylcyclohexanedicarboxylate.

(12) 3.6 wt % of titanium was included in the prepared solid catalyst.

(13) Next, a polypropylene polymerization process was performed in the same manner as in Example 1 to prepare polypropylene, and analysis results of polypropylene are represented in Table 1.

Example 3

(14) When preparing the solid catalyst of Example 1, a solid catalyst was prepared by using a mixture of 4.18 g of cis-dibutylcyclohexane dicarboxylate and 3.42 g of isopentylisopropyldimethoxypropane instead of trans-dibutylcyclohexanedicarboxylate.

(15) 3.6 wt % of titanium was included in the prepared solid catalyst.

(16) Next, a polypropylene polymerization process was performed in the same manner as in Example 1 to prepare polypropylene, and analysis results of polypropylene are represented in Table 1.

Comparative Example 1

(17) When preparing the solid catalyst of Example 1, a solid catalyst was prepared by injecting 7.41 g of diisobutylphthalate instead of trans-dibutylcyclohexanedicarboxylate.

(18) 3.1 wt % of titanium was included in the prepared solid catalyst.

(19) Next, a polypropylene polymerization process was performed in the same manner as in Example 1 to prepare polypropylene, and analysis results of polypropylene are represented in Table 1.

(20) TABLE-US-00001 TABLE 1 Activity MI X.S Tm Catalyst (Kg-PP/g-cat 2 h) (g/10 min) (wt %) (° C.) PI Example 1 55 2.7 2.0 162.3 6.8 Example 2 63 5.0 1.05 161.4 4.3 Example 3 72 6.2 1.5 161.4 4 Comparative 78 78 1.6 163.1 4.2 Example 1 {circle around (1)} Catalytic activity (kg-PP/g-cat) = a production amount of polymer (kg) ÷ amount of catalyst (g) {circle around (2)} Melt-flowability (g/10 minute): a value measured at a temperature of 230° C. and a load of 2.16 kg in accordance with ASTM1238 {circle around (3)} Stereoregularity (X.S, wt %): wt % of a component melted after being crystallized and precipitated in a mixed xylene {circle around (4)} Polydispersity index (PI): defined as PI = 106/Gc in case of unit of dyne/cm.sup.2 when defining an elastic modulus value when G′ and G″ intersect as Gc

Example 4

(21) When performing a polypropylene polymerization process on the solid catalyst of Example 1 to produce a polymerized polymer, 15,000 ml of hydrogen instead of 1,000 ml of hydrogen was injected, and the other conditions were the same as in Example 1.

(22) Analysis and VOC content results of the polymerized polymer are represented in Table 2.

Example 5

(23) When performing a polypropylene polymerization process on the solid catalyst of Example 2 to produce a polymerized polymer, 10,000 ml of hydrogen instead of 1,000 ml of hydrogen was injected, and the other conditions were the same as in Example 2.

(24) Analysis and VOC content results of the polymerized polymer are represented in Table 2.

Example 6

(25) When performing a polypropylene polymerization process on the solid catalyst of Example 3 to produce a polymerized polymer, 7,000 ml of hydrogen instead of 1,000 ml of hydrogen was injected, and the other conditions were the same as in Example 3.

(26) Analysis and VOC content results of the polymerized polymer are represented in Table 2.

Comparative Example 2

(27) When performing a polypropylene polymerization process on the solid catalyst of Comparative Example 1 to produce a polymerized polymer, 15,000 ml of hydrogen instead of 1,000 ml of hydrogen was injected, and the other conditions were the same as in Comparative Example 1.

(28) Analysis and VOC content results of the polymerized polymer are represented in Table 2.

(29) TABLE-US-00002 TABLE 2 Activity MI T-VOC content Catalyst (Kg-PP/g-cat 2 h) (g/10 min) (ppm) Example 4 65 90 250 Example 5 70 100 190 Example 6 80 95 150 Comparative 85 106 315 Example 2 ※ T-VOC content (ppm): The collected gases are measured by Headspace-GC by collecting gases for the number of carbon atoms 12 to 18 within the vial after containing 1 g of a PP sample in a 20 ml of a vial, sealing the vial containing the PP sample, and heating the sealed vial containing the PP sample at 180° C. for 1 hour.

(30) 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.