Process of manufacture of catalyst and propylene polymer that use this or copolymer for propylene polymerization

Abstract

The present disclosure relates to a solid catalyst for propylene polymerization and a process for manufacture of a propylene polymer or copolymer using the solid catalyst, and provides a solid catalyst including carriers produced via a reaction between dialkoxy magnesium and metal halide, titanium halide, an organic electron donor, etc. and a process of manufacture of a propylene-based block copolymer via copolymerization of propylene--olefin using the solid catalyst. Particularly, internal electron donors including an ester group and an alkoxy group are used as two kinds of organic electron donors used in the present disclosure, and, thus, a block copolymer having high activity and excellent stereoregularity and a high rubber content via copolymerization with -olefin can be produced using a solid catalyst system suggested in the present disclosure.

Claims

1. A solid catalyst for propylene polymerization, comprising: a titanium halide compound; a magnesium compound; and an internal electron donor including a mixture of a non-aromatic alkoxy ester compound represented by the following General Formula II and phthalic acid ester: ##STR00002## wherein n is 3 to 5; R.sub.1 is a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 4, 5, or 7 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, or a cycloalkenyl group having 5 to 7 carbon atoms; R.sub.2 is a linear alkyl group having 1 to 3 carbon atoms; and R.sub.3 and R.sub.4 are each hydrogen.

2. The solid catalyst for propylene polymerization of claim 1, wherein the solid catalyst includes the magnesium compound in the amount of 5 to 40 wt %, the titanium halide compound in the amount of 0.5 to 10 wt %, a halogen in the amount of 50 to 85 wt %, and internal electron donors in the total amount of 0.2 to 40 wt %.

3. The solid catalyst for propylene polymerization of claim 1, wherein the solid catalyst includes an alkoxy ester internal electron donor in the amount of 0.01 to 20 wt %.

4. The solid catalyst for propylene polymerization of claim 1, wherein two kinds of internal electron donors used in the solid catalyst include alkoxy ester and phthalic acid ester.

5. A process for manufacture of a propylene polymer or copolymer, comprising: polymerization of propylene or copolymerization of propylene with other -olefins in the presence of a solid catalyst of claim 1, AlR.sub.3, wherein R is an alkyl group having 1 to 6 carbon atoms, as a co-catalyst, and R.sup.1.sub.mR.sup.2.sub.nSi(OR.sup.3).sub.(4mn), wherein R.sup.1 and R.sup.2 are identical or different and are each independently a linear or branched or cyclic alkyl or aryl group having 1 to 12 carbon atoms, R.sup.3 is a linear or branched alkyl group having 1 to 6 carbon atoms, m and n are individually 0 or 1, and m+n is 1 or 2, as an external electron donor.

6. A process for manufacture of a propylene polymer or copolymer, comprising: copolymerization of propylene and ethylene or propylene and -olefin after homopolymerization of propylene or copolymerization of propylene and ethylene in the presence of a solid catalyst of claim 1.

7. A process for manufacture of a propylene polymer or copolymer, comprising: polymerization of propylene or copolymerization of propylene with other -olefins in the presence of a solid catalyst of claim 2, AlR.sub.3, wherein R is an alkyl group having 1 to 6 carbon atoms, as a co-catalyst, and R.sup.1.sub.mR.sup.2.sub.nSi(OR.sup.3).sub.(4mn), wherein R.sup.1 and R.sup.2 are identical or different and are each independently a linear or branched or cyclic alkyl or aryl group having 1 to 12 carbon atoms, R.sup.3 is a linear or branched alkyl group having 1 to 6 carbon atoms, m and n are individually 0 or 1, and m+n is 1 or 2, as an external electron donor.

8. A process for manufacture of a propylene polymer or copolymer, comprising: copolymerization of propylene and ethylene or propylene and -olefin after homopolymerization of propylene or copolymerization of propylene and ethylene in the presence of a solid catalyst of claim 4.

Description

DETAILED DESCRIPTION

(1) Example embodiments will now be described more fully.

(2) The illustrative embodiments described in the detailed description and claims are not meant to be limiting. Other embodiments may be utilized, and other changes may be made, without departing from the spirit or scope of the subject matter presented here.

(3) Hereinafter, Examples of the present disclosure and Comparative Examples will be described in detail, but the present disclosure is not limited thereto.

EXAMPLES

Example 1

(4) 1. Preparation of Solid Catalyst

(5) To an 1 L-volume glass reactor of which atmosphere was sufficiently substituted by nitrogen, equipped with a stirrer, 112 ml of toluene and 15 g of spherical-shaped diethoxy magnesium (having an average particle diameter of 20 m, particle distribution index of 0.86, apparent density of 0.35 g/cc) were added, and then 20 ml of titanium tetrachloride diluted in 30 ml of toluene was further added thereto and allowed to react for 1 hour while maintaining the temperature at 10 C. Then, a mixture of 3.6 g of diisobutylphthalate and 1.4 g of methyl 4-methoxybutanoate was added thereto while increasing the reactor temperature to 100 C. After maintaining the temperature at 100 C. for 2 hours and then lowering it to 90 C., stirring was halted, a supernatant was removed, and the resultant product was washed once with additional 200 ml of toluene. Then, 120 ml of toluene and 20 ml of titanium tetrachloride were added thereto, and the temperature was raised to 100 C. and maintained for 2 hours, and this process was repeated once. After the completion of the aging process, the slurry mixture was washed twice with 200 ml of toluene per washing, and then washed 5 times at 40 C. with 200 ml of normal hexane per washing, thereby obtaining a pale yellow solid catalyst component. The obtained solid catalyst component was dried for 18 hours under a nitrogen stream, and the titanium content in the obtained solid catalyst component was 2.2 wt %.

(6) 2. Polypropylene Polymerization

(7) Into a 4 L-volume high-pressure stainless reactor, 10 mg of the obtained solid catalyst, 10 mmol of triethyl aluminum, and 1 mmol of dicyclopentylmethyldimethoxysilane were added. Then, 3000 ml of hydrogen and 2.4 L of liquid propylene were added in sequence and polymerization was carried out at an elevated temperature of 70 C. After 2 hours from the start of polymerization, the remaining propylene inside the reactor was completely removed by opening the valve while lowering the reactor temperature to room temperature.

(8) The polymer thus obtained was analyzed, and the result of the analysis is given in Table 1.

(9) Herein, the catalytic activity and stereoregularity were determined by the following method.

(10) {circle around (1)} Catalytic activity(kg-PP/g-cat)=the amount of polymer produced (kg)the amount of catalyst (g)

(11) {circle around (2)} Stereoregularity (X.I.): the amount of insolubles crystallized and precipitated in mixed xylene (wt %)

(12) {circle around (3)} Melt-flowability (g/10 min): a value measured with ASTM1238 at 230 C. under a load of 2.16 kg

(13) 3. Propylene-Based Block Copolymerization

(14) Into a 2.0 L-stainless reactor filled with nitrogen and equipped with a stirrer, 5 mg of the solid catalyst, 3 mmol of triethyl aluminum, and 0.3 mmol of dicyclopentyldimethoxysilane (DCPDMS) were added. Then, 1.2 L of liquid propylene and 3000 ml of hydrogen were added thereto and pre-polymerization was carried out at 20 C. for 5 minutes and homopropylene polymerization was carried out at 70 C. for 40 minutes. After the completion of homopolymerization, a monomer was purged while lowering the reactor temperature to room temperature. Then, a mixed gas in which the molar ratio of ethylene/(ethylene+propylene) is 0.4 was added into the reactor and polymerization was carried out at an elevated temperature of 70 C. for 60 minutes. Thus, a propylene-based block copolymer was obtained.

(15) {circle around (1)} Block copolymer activity (ICP activity, kg-PP/g-cat)=the amount of polymer produced (kg)the amount of catalyst (g)

(16) {circle around (2)} Ethylene propylene rubber content (EPR, wt %): the amount of precipitates after sampling a copolymer with xylene and removing xylene (wt %)

(17) {circle around (3)} Ethylene content in copolymer (B-C2): the amount of ethylene measured with an infrared spectrometer (FT-IR) from a sampled copolymer (calculated on the basis of a calibration curve derived from a standard sample)

(18) {circle around (4)} Ethylene content in EPR (PER-C2, wt %): (ethylene content in copolymer)/(ethylene propylene rubber content)100

Example 2

(19) A catalyst was prepared according to the method for preparation of a solid catalyst in Example 1-1 except that 3.3 g of diisobutylphthalate and 2.1 g of ethyl 4-ethoxybutanoate were added instead of a mixture of diisobutylphthalate and methyl 4-methoxybutanoate. The titanium content in the solid catalyst component was 2.1 wt %. Then, polypropylene polymerization and propylene-based copolymerization were carried out by the same method as in Example 1, and the results thereof are given in Table 1.

Example 3

(20) A catalyst was prepared according to the method for preparation of a solid catalyst in Example 1-1 except that a mixture of 4.2 g of diisobutylphthalate and 2.8 g of methyl 5-methoxypentanoate was used instead of a mixture of diisobutylphthalate and methyl 4-methoxybutanoate. The titanium content in the solid catalyst component was 2.3 wt %. Then, polypropylene polymerization and propylene-based copolymerization were carried out by the same method as in Example 1, and the results thereof are given in Table 1.

Example 4

(21) A catalyst was prepared according to the method for preparation of a solid catalyst in Example 1-1 except that 4.5 g of diisobutylphthalate was added and then 1.8 g of ethyl 5-ethoxypentanoate was added instead of a mixture of diisobutylphthalate and methyl 4-methoxybutanoate while increasing the temperature. The titanium content in the solid catalyst component was 2.0 wt %. Then, polypropylene polymerization and propylene-based copolymerization were carried out by the same method as in Example 1, and the results thereof are given in Table 1.

Example 5

(22) A catalyst was prepared according to the method for preparation of a solid catalyst in Example 4 except that 3 g of diisobutylphthalate and 1.2 g of methyl 5-ethoxypentanoate were separately added instead of a mixture of diisobutylphthalate and ethyl 5-ethoxypentanoate. The titanium content in the solid catalyst component was 2.3 wt %. Then, polypropylene polymerization was carried out by the same method as in Example 1, and the results thereof are given in Table 1.

Comparative Example 1

(23) A catalyst was prepared according to the method for preparation of a solid catalyst in Example 1-1 except that 4.7 g of diisobutylphthalate was used instead of a mixture of diisobutylphthalate and 2-ethoxyethyl butyrate. The titanium content in the solid catalyst component was 2.2 wt %. Then, polypropylene polymerization was carried out by the same method as in Example 1, and the result thereof is given in Table 1.

Comparative Example 2

(24) 1. Preparation of Solid Catalyst

(25) To an 1 L-volume glass reactor of which atmosphere was sufficiently substituted by nitrogen, equipped with a stirrer, 150 ml of toluene, 12 ml of tetrahydrofuran, 20 ml of butanol, and 21 g of magnesium chloride were added, and the temperature was raised to 110 C. and maintained for 1 hour, thereby obtaining a homogenous solution. The solution was cooled to 15 C. and then added with 25 ml of titanium tetrachloride, and then, the reactor temperature was raised to 60 C. over 1 hour. After aging for 10 minutes, the mixture was stood still for 15 minutes to precipitate the carriers, and a supernatant was removed. The slurry remained in the reactor was added with 200 ml of toluene, and stirring, standing still, and removal of the supernatant was repeated twice for washing.

(26) The obtained slurry was added with 150 ml of toluene and then, 25 ml of titanium tetrachloride diluted in 50 ml of toluene was further added at 15 C. over 1 hour. Then, the reactor temperature was raised to 30 C. at a speed of 0.5 C. per minute. The reaction mixture was maintained at 30 C. for 1 hour and then, 7.5 ml of diisobutylphthalate was added thereto. Then, its temperature was raised to 110 C. at a speed of 0.5 C. per minute.

(27) After maintaining the temperature at 110 C. for 1 hour, the temperature was lowered to 90 C. and stirring was halted. Further, the supernatant was removed and the resultant product was washed once with additional 200 ml of toluene in the same way. Then, 150 ml of toluene and 50 ml of titanium tetrachloride were added thereto and the temperature was raised to 110 C. and maintained for 1 hour. After the completion of the aging process, the slurry mixture was washed twice with 200 ml of toluene per washing, and then washed 5 times at 40 C. with 200 ml of hexane per washing, thereby obtaining a pale yellow solid catalyst component. The obtained catalyst component was dried for 18 hours under a nitrogen stream, and the titanium content in the obtained solid catalyst component was 3.3 wt %.

(28) TABLE-US-00001 TABLE 1 HOMO polymerization Activity Propylene-based copolymerization (g-PP/g cat X/S MI ICP activity EPR B-C2 PER-C2 2 h) (wt %) (g/10 min) (g-PP/g cat) (wt %) (wt %) (wt %) Example 1 72,000 0.6 5.3 56,000 33 17 52 Example 2 75,000 0.5 4.8 58,000 35 18 51 Example 3 86,000 0.6 6.8 53,000 32 17 53 Example 4 83,000 0.5 5.4 55,000 30 16 53 Example 5 90,000 0.4 6.1 52,000 30 16 53 Comparative 83,000 1.5 6.7 48,000 23 12 52 Example 1 Comparative 66,000 1.9 7.8 41,000 29 14 48 Example 2

(29) 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.