Supported catalyst for propylene polymerization and method for producing polypropylene resin using same

Abstract

The present invention relates to a supported catalyst for propylene polymerization in which a first transition metal compound contributing to the production of crystalline polypropylene and a second transition metal compound contributing to the production of rubbery polypropylene are co-supported, and a method for producing a polypropylene resin using same. By using the supported catalyst, according to the present invention, it is possible to produce, by a single step of propylene polymerization, a polypropylene resin in which crystalline polypropylene and rubbery polypropylene are simultaneously formed.

Claims

1. A supported catalyst for propylene polymerization, comprising: a first transition metal compound represented by Chemical Formula 1 below; a second transition metal compound represented by Chemical Formula 3 below; and a carrier configured to co-support the first and second transition metal compounds, ##STR00022## wherein, in Chemical Formula 1, M.sup.1 is a group 4 transition metal, Q.sup.1 and Q.sup.2 are the same or different, and are each independently: a halogen group; a (C.sub.1-C.sub.20) alkyl group; a (C.sub.2-C.sub.20) alkenyl group; a (C.sub.2-C.sub.20) alkynyl group; a (C.sub.6-C.sub.20) aryl group: a (C.sub.1-C.sub.20) alkyl (C.sub.6-C.sub.20) aryl group; a (C.sub.6-C.sub.20) aryl (C.sub.1-C.sub.20) alkyl group; a (C.sub.1-C.sub.20) alkylamido group; a (C.sub.6-C.sub.20) arylamido group; or a (C.sub.1-C.sub.20) alkylidene group, A.sup.1 is a group 14 element, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, and R.sup.12 are the same or different, and are each independently: hydrogen; a (C.sub.1-C.sub.20) alkyl group unsubstituted or substituted with an acetal group or ether group; a (C.sub.2-C.sub.20) alkenyl group unsubstituted or substituted with an acetal group or ether group; a (C.sub.6-C.sub.20) aryl group unsubstituted or substituted with an acetal group or ether group; a (C.sub.1-C.sub.20) alkyl (C.sub.6-C.sub.20) aryl group unsubstituted or substituted with an acetal group or ether group; a (C.sub.6-C.sub.20) aryl (C.sub.1-C.sub.20) alkyl group unsubstituted or substituted with an acetal group or ether group; or a (C.sub.1-C.sub.20) silyl group unsubstituted or substituted with an acetal group or ether group, two or more groups among R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are capable of forming an aliphatic ring or aromatic ring by being bonded to each other, two or more groups among R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, and R.sup.12 are capable of forming an aliphatic ring or aromatic ring by being bonded to each other, and R.sup.5 and R.sup.6 are the same or different, and are each independently: hydrogen; a (C.sub.1-C.sub.20) alkyl group; a (C.sub.2-C.sub.20) alkenyl group; a (C.sub.2-C.sub.20) alkynyl group; a (C.sub.6-C.sub.20) aryl group; a (C.sub.1-C.sub.20) alkyl (C.sub.6-C.sub.20) aryl group; a (C.sub.6-C.sub.20) aryl (C.sub.1-C.sub.20) alkyl group; a (C.sub.1-C.sub.20) alkylamido group; a (C.sub.6-C.sub.20) arylamido group; or a (C.sub.1-C.sub.20) alkylidene group, ##STR00023## wherein, in Chemical Formula 3, M.sup.3 is a group 4 transition metal, Q.sup.5 and Q.sup.6 are the same or different, and are each independently: a halogen group; a (C.sub.1-C.sub.20) alkyl group; a (C.sub.2-C.sub.20) alkenyl group; a (C.sub.2-C.sub.20) alkynyl group; a (C.sub.6-C.sub.20) aryl group; a (C.sub.1-C.sub.20) alkyl (C.sub.6-C.sub.20) aryl group; a (C.sub.6-C.sub.20) aryl (C.sub.1-C.sub.20) alkyl group; a (C.sub.1-C.sub.20) alkylamido group; a (C.sub.6-C.sub.20) arylamido group; or a (C.sub.1-C.sub.20) alkylidene group, R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29, R.sup.30, R.sup.31, R.sup.32, and R.sup.33 are the same or different, and are each independently: hydrogen; a (C.sub.1-C.sub.20) alkyl group unsubstituted or substituted with an acetal group or ether group; a (C.sub.2-C.sub.20) alkenyl group unsubstituted or substituted with an acetal group or ether group; a (C.sub.6-C.sub.20) aryl group unsubstituted or substituted with an acetal group or ether group; a (C.sub.1-C.sub.20) alkyl (C.sub.6-C.sub.20) aryl group unsubstituted or substituted with an acetal group or ether group; a (C.sub.6-C.sub.20) aryl (C.sub.1-C.sub.20) alkyl group unsubstituted or substituted with an acetal group or ether group; or a (C.sub.1-C.sub.20) silyl group unsubstituted or substituted with an acetal group or ether group; a (C.sub.1-C.sub.20) alkoxy group; or a (C.sub.6-C.sub.20) aryloxy group, and two or more groups among R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.26, and R.sup.27 are capable of forming an aliphatic ring or aromatic ring by being bonded to each other.

2. The supported catalyst of claim 1, wherein the R.sup.9 is a (C.sub.6-C.sub.20) aryl group unsubstituted or substituted with an acetal group or ether group; or a (C.sub.1-C.sub.20) alkyl (C.sub.6-C.sub.20) aryl group unsubstituted or substituted with an acetal group or ether group.

3. The supported catalyst of claim 1, wherein the A.sup.1 is carbon (C) or silicon (Si), and the R.sup.5, and the R.sup.6, are each independently hydrogen or a methyl group.

4. The supported catalyst of claim 1, wherein the Q.sup.1, the Q.sup.2, the Q.sup.5, and the Q.sup.6, are each independently: a halogen group selected from among F, Cl, Br, and I; a methyl group; or an ethyl group.

5. The supported catalyst of claim 1, wherein the compound represented by Chemical Formula 1 is any one of compounds represented by Chemical Formulas 1-1 to 1-6 below, and the compound represented by Chemical Formula 3 is any one of compounds represented by Chemical Formulas 3-1 to 3-8 below ##STR00024## ##STR00025## ##STR00026## ##STR00027##

6. The supported catalyst of claim 1, wherein the first transition metal compound and the second transition metal compound are included in a molar ratio ranging from 50:50 to 10:90.

7. The supported catalyst of claim 1, further comprising one or more cocatalyst compounds selected from the group consisting of a compound having a unit represented by Chemical Formula 5 below, a compound represented by Chemical Formula 6 below, and a compound represented by Chemical Formula 7 below: Chemical Formula 5
[Al(Ra)O].sub.n, wherein, in Chemical Formula 5, n is an integer of 2 or more, Al is aluminum, O is oxygen, and Ra is: a halogen group; or a (C.sub.1-C.sub.20) hydrocarbyl group unsubstituted or substituted with a halogen group, Chemical Formula 6
Q(Rb).sub.3, wherein, in Chemical Formula 6, Q is: aluminum; or boron, and Rbs are the same or different, and are each independently: a halogen group; or a (C.sub.1-C.sub.20) hydrocarbyl group unsubstituted or substituted with a halogen group, Chemical Formula 7
[W].sup.+[Z(Rc).sub.4].sup., wherein, in Chemical Formula 7, [W].sup.+ is: a cationic Lewis acid; or a cationic Lewis acid to which a hydrogen atom is bonded, Z is a group 13 element, and Rcs are the same or different, and are each independently: a (C.sub.6-C.sub.20) aryl group substituted with one or more substituents selected from the group consisting of a halogen group, a (C.sub.1-C.sub.20) hydrocarbyl group, an alkoxy group, and a phenoxy group; or a (C.sub.1-C.sub.20) alkyl group substituted with one or more substituents selected from the group consisting of a halogen group, a (C.sub.1-C.sub.20) hydrocarbyl group, an alkoxy group, and a phenoxy group.

8. A method of producing a polypropylene resin, comprising carrying out a propylene polymerization reaction in the presence of the supported catalyst of claim 1.

9. The method of claim 8, wherein crystalline polypropylene and rubbery polypropylene are simultaneously formed through the polymerization reaction.

10. The method of claim 9, wherein the rubbery polypropylene includes one or more selected from the group consisting of: a rubbery propylene homopolymer, and a rubbery propylene copolymer polymerized by additionally adding other types of monomers during the polymerization of propylene.

11. The method of claim 10, wherein the other types of monomers include one or more selected from the group consisting of ethylene, butene, hexene, and octene.

12. The method of claim 9, wherein the rubbery polypropylene is included in an amount of 5% and more and 30% or less based on a total weight of the polypropylene resin.

13. The method of claim 8, wherein the polymerization is carried out in a phase selected from the group consisting of a liquid phase, a bulk phase, and a slurry phase.

Description

Example 1: Preparation of Polypropylene Resin

(1) At room temperature, the interior of a stainless steel autoclave (high-pressure reactor) having an internal capacity of 2 L was completely substituted with nitrogen. After injecting 2 ml of triisobutylaluminum (as a 1 M solution in hexane), 500 g of propylene, and 15 g of ethylene into the reactor while maintaining nitrogen purging, a dispersion prepared by dispersing 50 mg of Supported catalyst-1 in 5 ml of hexane was added into the reactor using high pressure nitrogen. Subsequently, polymerization was carried out at 70 C. for 60 minutes. After polymerization was completed, the reactor was cooled to room temperature, and as a result of subsequently removing unreacted propylene and ethylene through a discharge line, a white powdery solid was obtained. The obtained white powdery solid was dried for 15 hours or more while heating at 80 C. using a vacuum oven, and thereby a final polypropylene resin was obtained.

Examples 2 to 16 and Comparative Example 6: Preparation of Polypropylene Resin

(2) Propylene resins were produced in the same manner as in Example 1 except that a propylene loading amount (PL), an ethylene loading amount (EL), and a supported catalyst type were adjusted as shown in Table 3 below.

Comparative Example 1: Preparation of Polypropylene Resin

(3) Polypropylene was produced in the same manner as in Example 1 except that 10 mg of Supported catalyst-9 and 40 mg of Supported catalyst-11 (weight ratio of Supported catalyst-9 and Supported catalyst-11=2:8) instead of 50 mg of Supported catalyst-1 were dispersed in hexane.

Comparative Example 2: Preparation of Polypropylene Resin

(4) Polypropylene was produced in the same manner as in Example 1 except that 10 mg of Supported catalyst-9 and 40 mg of Supported catalyst-12 (weight ratio of Supported catalyst-9 and Supported catalyst-12=2:8) instead of 50 mg of Supported catalyst-1 were dispersed in hexane.

Comparative Example 3: Preparation of Polypropylene Resin

(5) Polypropylene was produced in the same manner as in Example 1 except that 10 mg of Supported catalyst-10 and 40 mg of Supported catalyst-11 (weight ratio of Supported catalyst-10 and Supported catalyst-11=2:8) instead of 50 mg of Supported catalyst-1 were dispersed in hexane.

Comparative Example 4: Preparation of Polypropylene Resin

(6) Polypropylene was produced in the same manner as in Example 1 except that 10 mg of Supported catalyst-10 and 40 mg of Supported catalyst-12 (weight ratio of Supported catalyst-10 and Supported catalyst-12=2:8) instead of 50 mg of Supported catalyst-1 were dispersed in hexane.

Comparative Example 5: Preparation of Polypropylene Resin

(7) Polypropylene was produced in the same manner as in Comparative Example 4 except that ethylene was not added.

Comparative Example 7: Preparation of Polypropylene Resin

(8) At room temperature, the interior of a stainless steel autoclave (high-pressure reactor) having an internal capacity of 2 L was completely substituted with nitrogen. After injecting 2 ml of triisobutylaluminum (as a 1 M solution in hexane) and 400 g of propylene into the reactor while maintaining nitrogen purging, a dispersion prepared by dispersing 50 mg of Supported catalyst-9 in 5 ml of hexane was added into the reactor using high pressure nitrogen. Subsequently, polymerization was carried out at 70 C. for 60 minutes. After subsequently removing unreacted propylene through a discharge line, the reactor was set at a temperature of 80 C. and a pressure of 12 bar, 33 g of ethylene was added into the reactor, and a gas-phase reaction was carried out for 30 minutes. After polymerization was completed, the reactor was cooled to room temperature, and as a result of subsequently removing unreacted propylene and ethylene through a discharge line, a white powdery solid was obtained. The obtained white powdery solid was dried for 15 hours or more while heating at 80 C. using a vacuum oven, and thereby a final polypropylene resin was obtained.

(9) <Evaluation Methods>

(10) (1) Ethylene Content (EL in PP and EL in Rubber)

(11) The ethylene content was analyzed through .sup.13C-NMR analysis using Bruker 300 MHz. In Table 3 below, EL in PP refers to the amount of ethylene included in crystalline polypropylene, and EL in rubber refers to the amount of ethylene included in rubbery polypropylene.

(12) (2) Proportion of Rubbery Polypropylene (Proportion of Rubber)

(13) The proportion of rubbery polypropylene was determined by measuring the amount of a polypropylene resin component dissolved in xylene, that is, the amount of atactic polypropylene soluble in xylene.

(14) Specifically, after drying 2 g of each of the final polypropylene resins produced according to Examples 1 to 16 and Comparative Examples 1 to 7 in a 80 C., 1 kPa vacuum oven for 20 minutes, the polypropylene resin A was input into a flask containing 200 ml of xylene, and was heated with stirring while being refluxed in the flask. When the solution contained in the flask became transparent, the solution was cooled to room temperature for 30 minutes, and the contents were filtered with filter paper. The filtered solution was dried in a 200 C. oven and then dried under vacuum, and thus a reaction product B in a solid form was obtained, and the weight of the reaction product was measured. The ratio of the reaction product B in a solid form to the dried polypropylene resin A is shown as the proportion of rubber (proportion of rubbery polypropylene) in Table 3 below.

(15) (3) Melting Point (Tm)

(16) The melting point was measured at a rate of 10 C./min under a nitrogen atmosphere and second heating conditions using a DuPont DSC 2910.

(17) (4) Melt Index (MI)

(18) The weight (g) of resin discharged through an orifice (inner diameter: 2.09 mm, length: 8 mm) for 10 minutes at a temperature of 230 C. under a load of 2.16 kg in accordance with ASTM D1238 was measured and shown as the melt index.

(19) (5) Activity

(20) After measuring the weight (kg) of a polypropylene resin produced for one hour per weight (g) of a catalyst used, catalytic activity was calculated according to Mathematical Formula 1 below.

(21) [Mathematical Formula 1]

(22) Activity (Kg/gCat.Math.hr)=Amount of polypropylene produced (kg/hr)/Amount of catalyst (g)

(23) TABLE-US-00003 TABLE3 EL in EL in Proportion PL EL PP rubber of rubber Tm MI Activity Occurrence Supported catalyst (g) (g) (%) (%) (%) ( C.) (g/10 min) (kg/gCat .Math. hr) of fouling Example 1 Supported catalyst-1 500 15 2.3 12 12 136 8.9 4.1 x Example 2 Supported catalyst-2 500 15 2.0 13 18 138 7.1 2.9 x Example 3 Supported catalyst-1 500 12 152 1.0 3.7 x Example 4 Supported catalyst-2 500 16 152 0.6 3.0 x Example 5 Supported catalyst-3 500 15 2.2 13 13 136 9.1 4.3 x Example 6 Supported catalyst-4 500 15 2.0 13 19 137 7.2 3.0 x Example 7 Supported catalyst-3 500 13 152 0.9 3.9 x Example 8 Supported catalyst-4 500 16 152 0.6 2.4 x Example 9 Supported catalyst-5 500 15 1.1 15 12 146 0.6 3.8 x Example 10 Supported catalyst-6 500 15 1.0 15 20 146 0.8 2.8 x Example 11 Supported catalyst-5 500 12 152 0.2 4.9 x Example 12 Supported catalyst-6 500 17 152 0.3 4.0 x Example 13 Supported catalyst-7 500 15 1.0 15 13 146 0.6 3.8 x Example 14 Supported catalyst-8 500 15 1.0 15 19 146 0.7 2.7 x Example 15 Supported catalyst-7 500 12 152 0.2 4.7 x Example 16 Supported catalyst-8 500 19 152 0.3 4.0 x Comparative Supported catalyst-9 + 500 15 2.5 10 9 134 9.2 2.1 Example 1 Supported catalyst-11 Comparative Supported catalyst-9 + 500 15 2.4 10 10 134 9.1 2.1 Example 2 Supported catalyst-12 Comparative Supported catalyst-10 + 500 15 1.1 12 11 145 0.7 1.4 Example 3 Supported catalyst-11 Comparative Supported catalyst-10 + 500 15 1.1 12 11 145 0.7 1.4 Example 4 Supported catalyst-12 Comparative Supported catalyst-10 + 500 152 0.4 1.0 Example 5 Supported catalyst-12 Comparative Supported catalyst-9 500 15 4.1 125 10 4.0 x Example 6 Comparative Supported catalyst-9 400 33 18 9 152 6.7 2.9 x Example 7

(24) Referring to Table 3, in the case of Examples 1 to 16 in which a supported catalyst in which first and second transition metal compounds of the present invention are co-supported, it can be seen that polypropylene resins with a higher proportion of rubbery polypropylene than in the case of Comparative Examples 1 to 7 were produced, and a fouling phenomenon did not occur.

(25) However, in the case of using a combination of a supported catalyst in which only a first transition metal compound is supported and a supported catalyst in which only a second transition metal compound is supported, when ethylene was additionally added (Comparative Examples 1 to 4), the formed rubbery polypropylene was separated, and thus a fouling phenomenon occurred, and when ethylene was not additionally added (Comparative Example 5), rubbery polypropylene was not formed, and a fouling phenomenon occurred. In addition, in the case of Comparative Example 6 in which a polyester resin was produced only using a supported catalyst in which only a first transition metal compound is supported, rubbery polypropylene was not formed.

(26) In addition, in the case of using supported catalysts in which first and second transition metal compounds are co-supported as in Examples 1 to 16, higher catalytic activity was exhibited than in the case of using a combination of a supported catalyst in which only a first transition metal compound is supported and a supported catalyst in which only a second transition metal compound is supported as in Comparative Examples 1 to 5. From this, it can be seen that when a combination of a supported catalyst in which only a first transition metal compound is supported and a supported catalyst in which only a second transition metal compound is supported is used, activity decreases due to the combined use.

(27) Meanwhile, in the case of Examples 3, 4, 7, 8, 11, 12, 15, and 16 of the present invention, it can be seen that a polypropylene resin with a high proportion of rubbery polypropylene was produced even though ethylene was not added. In addition, in the case of Examples 1, 2, 5, 6, 9, 10, 13, and 14 in which ethylene was added, it can be seen that rubbery polypropylene was formed with only one polymerization step without an additional process for ethylene. On the other hand, in the case of Comparative Example 7, it can be seen that, even though more ethylene was added than in Examples and an additional gas-phase reaction was carried out, a polypropylene resin with a lower proportion of rubbery polypropylene than in Examples was produced.

(28) In addition, referring to Table 3, it can be seen that the proportion of rubbery polypropylene varied according to the ratio between the co-supported first and second transition metal compounds. From this, it can be seen that when the ratio between the co-supported transition metal compound are appropriately adjusted according to the present invention, a polypropylene resin including rubbery polypropylene at an appropriate proportion for use can be easily produced.

(29) As described above, although the present invention has been described through a limited number of exemplary embodiments and drawings, the present invention is not limited thereto, and it goes without saying that various modifications and changes can be made by those of ordinary skill in the art to which the present invention pertains within the scope of the technical spirit of the present invention and the scope of the claims to be described below and equivalents thereof.