Preparation method of solid catalyst for propylene polymerization

Abstract

Disclosed is a method for preparing a solid catalyst for propylene polymerization, and more specifically, a method for preparing a solid catalyst for propylene polymerization including (1) first reacting dialkoxy magnesium and titanium halide compound under the presence of an organic solvent; (2) adding two kinds of non-aromatic internal electron donors to a product of the step (1) and reacting the mixture; and (3) second reacting the product of the step (2) with a titanium halide compound and washing a reaction product. The catalyst prepared according to the method as described in the present disclosure not only may provide high catalytic activity, but also may provide a propylene polymer having excellent stereoregularity.

Claims

1. A method for preparing a solid catalyst for propylene polymerization, the method comprising: (1) reacting dialkoxy magnesium and titanium halide compounds under presence of an organic solvent; (2) reacting a product of the step (1) with an internal electron donor mixture, wherein the internal electron donor mixture includes a mixture between 1,4-cyclohexadiene-1,2-dicarboxylic acid 1,2-dibutylester (A) and 9,9-bis(methoxymethyl)fluorene (C) or 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (D): ##STR00003## (3) reacting the product of the step (2) with a titanium halide compound, and washing the product thereof.

2. The method of claim 1, wherein the dialkoxy magnesium compound is diethoxy magnesium.

3. The method of claim 1, wherein the titanium halide is represented by a general formula (I):
Ti(OR).sub.aX.sub.(4-a)  (I) where R represents an alkyl group of 1 to 10 carbon atoms, X represents a halogen element, and a is an integer of 0 to 3 to satisfy a valence of the general formula.

Description

DETAILED DESCRIPTION

(1) The present disclosure will be described in more detail through following examples. However, these examples are for illustrative purposes only, and the present disclosure is not limited to these examples.

EXAMPLE

Example 1

(2) [Preparation of Solid Catalyst]

(3) 150 ml of toluene and 20 g of diethoxy magnesium (average particle size: 20 μm) were added to a glass reactor having a 1 liter size and sufficiently substituted with nitrogen and equipped with a stirrer. Then, the reactor was maintained at 10° C. After diluting 40 ml of titanium tetrachloride into 60 ml of toluene, the diluted solution was input to the reactor over 1 hour. Then, while raising the reactor temperature to 110° C., 16.8 mmol (4.71 g) of 1,4-cyclohexadiene-1,2-dicarboxylic acid 1,2-dibutylester (A, R.sub.1=R.sub.2=butyl) and 5.6 mmol (0.84 g) of ethyl benzoate (B) were injected to the reactor. After maintaining the reactor at 110° C. for 2 hours, the reactor temperature was lowered to 90° C. to stop stirring and remove a supernatant. Washing thereof was carried out once using 200 ml of toluene using the same method.

(4) In this connection, 150 ml of toluene and 50 ml of titanium tetrachloride were added to thereto, and a temperature was raised to 110° C. and this state was maintained for 2 hours. A slurry mixture subjected to an aging process was washed with 200 ml of toluene per a single washing time. This washing was conducted twice. Then, the slurry mixture was washed with 200 ml of normal hexane per a single washing time at 40° C. This washing was conducted five times, thereby to obtain a light yellow solid catalyst component.

(5) [Polypropylene Polymerization]

(6) 10 mg of the above solid catalyst and 6.6 mmol of triethylaluminum, 0.66 mmol of dicyclopentyldimethoxysilane were added into a 4-liter sized high-pressure stainless steel reactor. Subsequently, 1000 ml of hydrogen and 2.4 L of propylene in a liquid state were sequentially added thereto, and then a reactor temperature was raised to 70° C. to perform polymerization. At 2 hours after the start of the polymerization, a temperature of the reactor was dropped to room temperature. At the same time, a valve was opened to completely remove propylene inside the reactor. Table 1 shows analysis results of the obtained propylene polymer.

(7) In this connection, catalytic activity and stereoregularity were determined based on the following equations:
{circle around (1)}Catalytic activity (kg-PP/g-catalyst)=polypropylene production amount (kg)÷amount of catalyst as injected(g)
{circle around (2)}Stereoregularity(X.I.)=weight % of an insoluble component precipitated via crystallization in mixed xylene, relative to 100 g of polymer

Example 2

(8) A solid catalyst was prepared in the same manner as in Example 1 except that 5.6 mmol (1.42 g) of 9,9-bis(methoxymethyl)fluorene (C) was used instead of 5.6 mmol (0.84 g) of ethyl benzoate (B) in the [Preparation of solid catalyst] step of Example 1. Then, polypropylene polymerization was performed in the same manner as in Example 1. Table 1 shows analysis results of the obtained propylene polymer.

Example 3

(9) A solid catalyst was prepared in the same manner as in Example 1 except that instead of 5.6 mmol (0.84 g) of ethyl benzoate (B), 5.6 mmol (1.13 g) of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (D) was used in the [Preparation of solid catalyst] step of Example 1. Then, polypropylene polymerization was performed in the same manner as in Example 1, Table 1 shows analysis results of the obtained propylene polymer.

Example 4

(10) [Preparation of Solid Catalyst]

(11) 150 ml of toluene and 20 g of diethoxy magnesium (average particle size: 20 μm) were added to a glass reactor having a 1 liter size and sufficiently substituted with nitrogen and equipped with a stirrer. Then, the reactor was maintained at 10° C. After diluting 40 ml of titanium tetrachloride into 60 ml of toluene, the diluted solution was input to the reactor over 1 hour. Then, while raising the reactor temperature to 110° C., 16.8 mmol (3.77 g) of 1,4-cyclohexadiene-1,2-dicarboxylic acid 1,2-diethylester (A, R.sub.1=R.sub.2=ethyl) and 5.6 mmol (0.84 g) of ethyl benzoate (B) were injected to the reactor. After maintaining the reactor at 110° C. for 2 hours, the reactor temperature was lowered to 90° C. to stop stirring and remove a supernatant. Washing thereof was carried out once using 200 ml of toluene using the same method.

(12) In this connection, 150 ml of toluene and 50 ml of titanium tetrachloride were added to thereto, and a temperature was raised to 110° C. and this state was maintained for 2 hours. A slurry mixture subjected to an aging process was washed with 200 ml of toluene per a single washing time. This washing was conducted twice. Then, the slurry mixture was washed with 200 ml of normal hexane per a single washing time at 40° C. This washing was conducted five times, thereby to obtain a light yellow solid catalyst component.

(13) [Polypropylene Polymerization]

(14) Using the solid catalyst, polypropylene polymerization was performed in the same manner as in Example 1. Table 1 shows analysis results of the obtained propylene polymer.

Example 5

(15) A solid catalyst was prepared in the same manner as in Example 1 except for using 5.6 mmol (1.42 g) of 9,9-bis(methoxymethyl)fluorene (C) instead of 5.6 mmol (0.84 g) of ethyl benzoate (B) in the [Preparation of solid catalyst] step of Example 4. Then, polypropylene polymerization was performed in the same manner as in Example 1. Table 1 shows the analysis results of the obtained propylene polymer.

Example 6

(16) A solid catalyst was prepared in the same manner as in Example 4 except that instead of 5.6 mmol (0.84 g) of ethyl benzoate (B), 5.6 mmol (1.13 g) of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (D) was used in the [Preparation of solid catalyst] step of Example 4. Then, polypropylene polymerization was performed in the same manner as in Example 1. Table 1 shows analysis results of the obtained propylene polymer.

Comparative Example 1

(17) 150 ml of toluene and 20 g of diethoxy magnesium (average particle size: 20 μm) were added to a glass reactor having a 1 liter size and sufficiently substituted with nitrogen and equipped with a stirrer. Then, the reactor was maintained at 10° C. After diluting 40 ml of titanium tetrachloride into 60 ml of toluene, the diluted solution was input to the reactor over 1 hour. Then, while raising the reactor temperature to 110° C., 22.4 mmol of 1,4-cyclohexadiene-1,2-dicarboxylic acid 1,2-dibutylester (A, R.sub.1=R.sub.2=butyl) was injected to the reactor. After maintaining the reactor at 110° C. for 2 hours, the reactor temperature was lowered to 90° C. to stop stirring and remove a supernatant. Washing thereof was carried out once using 200 ml of toluene using the same method.

(18) In this connection, 150 ml of toluene and 50 ml of titanium tetrachloride were added to thereto, and a temperature was raised to 110° C. and this state was maintained for 2 hours. A slurry mixture subjected to an aging process was washed with 200 ml of toluene per a single washing time. This washing was conducted twice. Then, the slurry mixture was washed with 200 ml of normal hexane per a single washing time at 40° C. This washing was conducted five times, thereby to obtain a light yellow solid catalyst component. Then, polypropylene polymerization was performed in the same manner as in Example 1. Table 1 shows analysis results of the obtained propylene polymer.

Comparative Example 2

(19) 150 ml of toluene and 20 g of diethoxy magnesium (average particle size: 20 μm) were added to a glass reactor having a 1 liter size and sufficiently substituted with nitrogen and equipped with a stirrer. Then, the reactor was maintained at 10° C. After diluting 40 ml of titanium tetrachloride into 60 ml of toluene, the diluted solution was input to the reactor over 1 hour. Then, while raising the reactor temperature to 110° C., 22.4 mmol of 1,4-cyclohexene-1,2-dicarboxylic acid 1,2-diethylester (A, R.sub.1=R.sub.2=ethyl) was injected to the reactor. After maintaining the reactor at 110° C. for 2 hours, the reactor temperature was lowered to 90° C. to stop stirring and remove a supernatant. Washing thereof was carried out once using 200 ml of toluene using the same method.

(20) In this connection, 150 ml of toluene and 50 ml of titanium tetrachloride were added to thereto, and a temperature was raised to 110° C. and this state was maintained for 2 hours. A slurry mixture subjected to an aging process was washed with 200 ml of toluene per a single washing time. This washing was conducted twice. Then, the slurry mixture was washed with 200 ml of normal hexane per a single washing time at 40° C. This washing was conducted five times, thereby to obtain a light yellow solid catalyst component. Then, polypropylene polymerization was performed in the same manner as in Example 1. Table 1 shows analysis results of the obtained propylene polymer.

(21) TABLE-US-00001 TABLE 1 Activity (kg-PP/ Stereoregularity Examples Internal electron donor g-catalyst) (X.I., Weight %) Example 1 A (R.sub.1 = R.sub.2 = butyl, 81.3 99.4 16.8 mmol)/B (5.6 mmol) Example 2 A (R.sub.1 = R.sub.2 = butyl, 82.6 99.2 16.8 mmol)/C (5.6 mmol) Example 3 A (R.sub.1 = R.sub.2 = butyl, 80.5 99.5 16.8 mmol)/D (5.6 mmol) Example 4 A (R.sub.1 = R.sub.2 = ethyl, 63.4 98.7 16.8 mmol)/B (5.6 mmol) Example 5 A (R.sub.1 = R.sub.2 = ethyl, 61.8 98.8 16.8 mmol)/C (5.6 mmol) Example 6 A (R.sub.1 = R.sub.2 = ethyl, 62.5 98.5 16.8 mmol)/D (5.6 mmol) Comp.Ex. 1 A (R.sub.1 = R.sub.2 = butyl, 71.0 99.0 22.4 mmol) Comp.Ex. 2 A (R.sub.1 = R.sub.2 = ethyl, 51.2 97.5 22.4 mmol)

(22) As shown in Table 1, Examples 1 to 6 according to the present disclosure in which a mixture between 1,4-cyclohexadiene-1,2-dicarboxylic acid 1,2-dibutylester (A, R.sub.1=R.sub.2=butyl) or 1,4-cyclohexene-1,2-dicarboxylic acid 1,2-diethylester (A, R.sub.1=R.sub.2=ethyl) and one selected from the group consisting of ethyl benzoate (B), 9,9-bis(methoxymethyl)fluorene (C), and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (D) was used as the internal electron donor exhibited higher catalytic activity of the catalyst and higher stereoregularity of the polymer, than those of Comparative Examples 1 to 2 in which 1,4-cyclohexadiene-1,2-dicarboxylic acid 1,2-dibutylester (A, R.sub.1=R.sub.2=butyl) or 1,4-cyclohexene-1,2-dicarboxylic acid 1,2-diethylester (A, R.sub.1=R.sub.2=ethyl) was used alone as the internal electron donor.

(23) 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.